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Advanced Structured Materials
VisakhP.M.Editor
Biodegradable and
Environmental
Applications
ofBionanocomposites
Advanced Structured Materials
Volume 177
Series Editors
Andreas Öchsner, Faculty of Mechanical Engineering, Esslingen University of
Applied Sciences, Esslingen, Germany
Lucas F. M. da Silva, Department of Mechanical Engineering, Faculty of
Engineering, University of Porto, Porto, Portugal
Holm Altenbach , Faculty of Mechanical Engineering, Otto von Guericke
University Magdeburg, Magdeburg, Sachsen-Anhalt, Germany
Common engineering materials are reaching their limits in many applications, and
new developments are required to meet the increasing demands on engineering mate-
rials. The performance of materials can be improved by combining different materials
to achieve better properties than with a single constituent, or by shaping the material
or constituents into a specific structure. The interaction between material and struc-
ture can occur at different length scales, such as the micro, meso, or macro scale,
and offers potential applications in very different fields.
This book series addresses the fundamental relationships between materials and
their structure on overall properties (e.g., mechanical, thermal, chemical, electrical,
or magnetic properties, etc.). Experimental data and procedures are presented, as
well as methods for modeling structures and materials using numerical and analyt-
ical approaches. In addition, the series shows how these materials engineering and
design processes are implemented and how new technologies can be used to optimize
materials and processes.
Advanced Structured Materials is indexed in Google Scholar and Scopus.
Visakh P . M.
Editor
Biodegradable
and Environmental
Applications
of Bionanocomposites
Editor
Visakh P. M.
Department of Physical Electronics
Tomsk State University of Control Systems
and Radioelectronics
Tomsk, Russia
ISSN 1869-8433 ISSN 1869-8441 (electronic)
Advanced Structured Materials
ISBN 978-3-031-13342-8 ISBN 978-3-031-13343-5 (eBook)
https://doi.org/10.1007/978-3-031-13343-5
© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature
Switzerland AG 2023
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Preface
Biodegradable polymers and their bionanocomposites based on layered silicates:
Environmental applications are given in Chap. 1. Chapter 2 offers a review of
chitosan/poly (ethylene glycol)/ZnO bionanocomposite for wound healing appli-
cation. This chapter covers the introduction to chitosan, its properties, and some
novel potential applications of chitosan bionanocomposite for wound healing
application. Preparation and applications of chitosan–gold bionanocomposites are
described in Chap. 3. Preparation strategies for chitosan–gold nanocomposite
and applications of chitosan–gold nanocomposites are described in this chapter.
Different applications of chitosan–gold bionanocomposites such as textile industry,
improvement in textile functionalities by chitosan–gold nanocomposite, wound
healing by chitosan graft scaffoldings composite, and wound healing by peptide
conjugate-chitosan/derivatives are also described.
Chapter 4 deals with the environmental properties and applications of cellulose
and chitin-based bionanocomposites. In this chapter, the sources and properties as
well as the extraction and preparation methods of the corresponding cellulose and
chitin bionanocomposites are introduced. The environmental characterizations of
cellulose and chitin-based bionanocomposites and their applications in various fields
are reported.
Chapter 5 discusses the polylactic acid/halloysite nanotube bionanocomposite
films for food packaging. In addition, the polylactic acid/halloysite nanotube
bionanocomposite preparation and characterizations are also described. Food pack-
aging application of polylactic acid/halloysite nanotube bionanocomposite is also
discussed. A detailed review of preparation of ZnO/chitosan nanocomposite is
covered in Chap. 6.
“Polymer Composites Scaffolds for Bone Implants: A Review” is discussed in
Chap. 7. In this chapter, strategies and techniques to engineer new kind of polymer
surface to promote osteoconduction with host tissues will be discussed. Also, bene-
fits and applications of polymeric composite scaffolds for orthopedic surgery will be
discussed. Biodegradable polyvinyl alcohol/starch/halloysite nanotube bionanocom-
posite are discussing in final chapter, Preparation and Characterization of Biodegrad-
able nanocomposites are also reported.
v
vi Preface
In this book, chapter authors have reviewed different aspects of biodegradable
polymers and their bionanocomposites. This book is a valuable reference source for
faculties, professionals, research fellows, senior graduate students, and researchers
working in the field of biodegradable polymers and their bionanocomposites. The use
of biodegradable bionanocomposites is considered as a promising area of research;
a lot of research activities are going on, and some knowledge of bionanocomposites
is helpful to bring a change in the current techniques and applications. Finally, we
would like to express our sincere gratitude to all the contributors of this book, who
made excellent support to the successful completion of this venture. We also thank
the publisher Springer for recognizing the demand and importance of biodegradable
bionanocomposites.
Tomsk, Russia Visakh P. M.
Contents
1 Biodegradable Polymers and Their Bionanocomposites Based
on Layered Silicates: Environmental Applications ................. 1
Julia Martín, María del Mar Orta, Santiago Medina-Carrasco,
Juan Luis Santos, Irene Aparicio, and Esteban Alonso
1.1 Introduction ............................................... 2
1.2 Biodegradable Polymers ..................................... 3
1.3 Biodegradable Polymer-Based Bionanocomposites .............. 4
1.3.1 Chitosan/Clay Nanocomposites ........................ 9
1.3.2 Starch/Clay Nanocomposites .......................... 10
1.3.3 Alginate–Clay Nanocomposites ........................ 11
1.3.4 Cellulose/Clay Nanocomposites ........................ 12
1.3.5 Protein–Clay Nanocomposites ......................... 13
1.3.6 Polylactic Acid/Clay Nanocomposites .................. 14
1.4 Preparation of Biopolymer–Clay Nanocomposites ............... 14
1.4.1 Solution-Blending Method ............................ 15
1.4.2 Melt-Blending Method ................................ 15
1.4.3 In Situ Polymerization Method ......................... 16
1.5 Characterization Techniques ................................. 17
1.6 Environmental Applications .................................. 20
1.6.1 Bionanocomposites with Layered Silicates in Soil
and Water Treatment ................................. 20
1.6.2 Bionanocomposites with Layered Silicates for Food
Packaging ........................................... 22
1.6.3 Bionanocomposites with Layered Silicates
for Agricultural Applications .......................... 23
1.7 Conclusion ................................................ 23
References ..................................................... 24
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite
for Wound Healing Application .................................. 31
Zahra Emam-Djomeh and Mehdi Hajikhani
vii
viii Contents
2.1 Introduction ............................................... 31
2.2 Chitosan .................................................. 32
2.3 Poly (Ethylene Glycol) ...................................... 41
2.4 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite ........ 44
2.5 Wound Healing Application .................................. 47
2.6 Conclusion ................................................ 53
References ..................................................... 53
3 Preparation and Applications of Chitosan–Gold
Bionanocomposites ............................................. 67
Rishabh Anand Omar and Monika Jain
3.1 Introduction ............................................... 67
3.2 Chitosan–Gold Nanocomposite ............................... 69
3.3 Preparation Strategies for Chitosan–Gold Nanocomposite ........ 70
3.3.1 General Synthesis .................................... 71
3.3.2 Physical Methods .................................... 71
3.3.3 Radiolysis, Sonochemistry and Photochemical (UV,
Near-IR) Strategies ................................... 71
3.3.4 Chemical Synthesis .................................. 72
3.3.5 Reduction by Borohydride ............................ 72
3.3.6 Citrate Reduction .................................... 73
3.3.7 Synthesis by Seeding Growth Technique ................ 73
3.3.8 Biosynthesis Technique ............................... 73
3.4 Applications of Chitosan–Gold Nanocomposites ................ 74
3.4.1 Textile Industry ...................................... 74
3.4.2 Improvement in Textile Functionalities
by Chitosan–Gold Nanocomposite ...................... 77
3.4.3 Effluent Treatment Application ........................ 78
3.4.4 Bioremediation ...................................... 79
3.4.5 Application in Biomedical Field ........................ 80
3.5 Future Applications ......................................... 86
References ..................................................... 87
4 Environmental Properties and Applications of Cellulose
and Chitin-Based Bionanocomposites ............................ 99
Renyan Zhang and Hui Xu
4.1 Introduction ............................................... 99
4.1.1 Cellulose ........................................... 99
4.1.2 Chitin .............................................. 104
4.2 Environmental Properties .................................... 106
4.2.1 Mechanical Properties ................................ 107
4.2.2 Thermal Properties ................................... 107
4.2.3 Barrier Properties .................................... 108
4.2.4 Biodegradability ..................................... 108
4.2.5 Antibacterial and Antifungal Properties ................. 109
4.3 Applications of Cellulose-Based Bionanocomposites ............ 109
Contents ix
4.3.1 Electronics Device Industry ........................... 110
4.3.2 Biomedicine Industry ................................. 111
4.3.3 Food Industry ....................................... 116
4.3.4 Environmental Protection ............................. 117
4.4 Applications of Chitin-Based Bionanocomposites ............... 120
4.4.1 Biomedicine Industry ................................. 120
4.4.2 Environmental Protection ............................. 122
4.4.3 Food Industry ....................................... 124
4.4.4 Agriculture .......................................... 126
4.4.5 Cosmetics ........................................... 126
4.5 Conclusion ................................................ 127
References ..................................................... 128
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films
for Food Packaging ............................................. 141
Zahra Emam-Djomeh and Hajikhani Mehdi
5.1 Introduction ............................................... 141
5.2 Polylactic Acid ............................................. 143
5.3 Polylactic Acid/Halloysite Nanotube Bionanocomposite ......... 148
5.4 Food Packaging Application of Polylactic Acid/Halloysite
Nanotube Bionanocomposite ................................. 152
5.5 Conclusion ................................................ 158
References ..................................................... 158
6 Preparation of ZnO/Chitosan Nanocomposite and Its
Applications to Durable Antibacterial, UV-Blocking,
and Textile Properties .......................................... 169
Tanmoy Dutta, Abdul Ashik Khan, Nabajyoti Baildya,
Palas Mondal, and Narendra Nath Ghosh
6.1 Introduction ............................................... 169
6.2 Preparation of ZnO/Chitosan Nanocomposite ................... 173
6.2.1 General Mechanism of the Formation of ZnO/Chitosan
Nanocomposite ...................................... 176
6.3 Antibacterial Activity of ZnO/Chitosan Nanocomposite .......... 176
6.3.1 Probable Mechanism of the Antibacterial Activity
of ZnO/Chitosan Nanocomposite ....................... 180
6.4 Applications of ZnO/Chitosan Nanocomposite in Textiles ........ 181
6.5 Applications of ZnO/Chitosan Nanocomposite
as a UV-Blocker ............................................ 182
6.6 Conclusion ................................................ 183
References ..................................................... 183
7 Polymeric Nano-Composite Scaffolds for Bone Tissue
Engineering: Review ............................................ 189
Lokesh Kumar and Dheeraj Ahuja
7.1 Introduction ............................................... 190
xContents
7.1.1 Scaffold for Bone Tissue Engineering ................... 190
7.2 Properties of Scaffold ....................................... 192
7.2.1 Biocompatibility ..................................... 193
7.2.2 Biodegradability ..................................... 194
7.2.3 Porosity ............................................ 195
7.2.4 Targetability ......................................... 195
7.2.5 Binding Affinity ..................................... 195
7.2.6 Stability ............................................ 196
7.2.7 Loading Capability and Deliverance .................... 196
7.2.8 Mechanical Properties ................................ 196
7.2.9 Scaffold Architecture ................................. 197
7.3 2Dimesional (2D) Versus 3Dimensional (3D) Culture Scaffold .... 197
7.4 Polymer Scaffold and Processing Techniques ................... 198
7.4.1 Conventional Techniques .............................. 198
7.4.2 Rapid Prototyping Technique .......................... 202
7.4.3 Combination of Techniques ............................ 203
7.5 Biomaterials for Tissue Engineering Polymeric Scaffold
Manufacturing ............................................. 204
7.5.1 Ceramics ........................................... 204
7.5.2 Natural Polymers .................................... 205
7.5.3 Synthetic Polymers ................................... 206
7.5.4 Composites ......................................... 206
7.6 Applications ............................................... 207
7.7 Conclusion and Future Prospective ............................ 208
References ..................................................... 209
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube
Bionanocomposite: Preparation and Characterization ............. 221
P. Manju and P. Santhana Gopala Krishnan
8.1 Introduction ............................................... 221
8.2 Poly(Vinyl Alcohol) ........................................ 222
8.3 Starch .................................................... 223
8.4 Halloysite ................................................. 224
8.5 PVOH/ST/HNT Bionanocomposite: Preparation ................ 226
8.5.1 Solution Casting ..................................... 226
8.5.2 Electrospinning ...................................... 226
8.5.3 Melt Processing ...................................... 228
8.6 PVOH/ST/HNT Bionanocomposite: Characterization ............ 228
8.6.1 Chemical Interaction Analysis ......................... 228
8.6.2 XRD Analysis ....................................... 229
8.6.3 Morphological Analysis ............................... 229
8.6.4 Mechanical Properties ................................ 230
8.6.5 Thermal Analysis .................................... 232
8.6.6 Water Absorption Capacity ............................ 233
8.7 Conclusions ............................................... 233
Contents xi
References ..................................................... 234
9 Environmentally Friendly Bionanocomposites in Food Industry .... 237
Subajiny Sivakanthan and Podduwala Hewage Sathiska Kaumadi
9.1 Introduction ............................................... 237
9.2 Environmentally Friendly Bionanocomposites .................. 238
9.2.1 Properties and Applications of Bionanocomposites ........ 240
9.3 Bionanocomposites in the Food Industry ....................... 241
9.4 Properties of a Bionanocomposite that Make It Suitable
as a Food Packaging Material ................................ 243
9.4.1 Mechanical Properties ................................ 243
9.4.2 Barrier Properties .................................... 245
9.4.3 Thermal Properties ................................... 246
9.5 Application of Bionanocomposites in the Packaging of Food ...... 249
9.5.1 Dairy Products ...................................... 249
9.5.2 Fruit and Vegetable ................................... 250
9.5.3 Meat and Poultry .................................... 251
9.5.4 Application of Bionanocomposites in Novel Food
Packaging Systems ................................... 252
9.6 Safety Concerns ............................................ 258
9.7 Conclusion ................................................ 258
References ..................................................... 259
Chapter 1
Biodegradable Polymers and Their
Bionanocomposites Based on Layered
Silicates: Environmental Applications
Julia Martín, María del Mar Orta, Santiago Medina-Carrasco,
Juan Luis Santos, Irene Aparicio, and Esteban Alonso
Abstract Bionanocomposites are hybrid materials comprising inorganic nanopar-
ticles or nanofillers disposed in a biopolymer matrix. Different functional materials
have been prepared using a wide type of biopolymers (naturally or synthetic) and inor-
ganic particles (silica, metal, carbon nanotubes, cellulose nanowhiskers or layered
silicate clays) with different compositions and topologies. In this chapter, special
attention is paid in layered silicates because of their availability, low cost and their
easy intercalation chemistry. The natural polysaccharides (chitosan, starch and algi-
nate), proteins and the synthetic polylactic acid incorporating to layered silicates of
the smectite group constitute the bionanocomposites most studied for environmental
applications. In this work, the physicochemical and structural properties of devel-
oped bionanocomposites including the different methods of preparation and char-
acterization techniques have been discussed. Finally, environmental applications of
bionanocomposites based on layered silicates in the field of food, agriculture, soil
and water treatments, both in cleaning and desalination, are contemplated.
Keywords Bionanocomposites ·Biopolymers ·Layered silicates ·Adsorption ·
Water remediation
J. Martín (B) · J. L. Santos · I. Aparicio · E. Alonso
Departamento de Química Analítica, Escuela Politécnica Superior, Universidad de Sevilla, C/
Virgen de África 7, 41011 Sevilla, España
e-mail: jbueno@us.es
M. del Mar Orta
Departamento de Química Analítica, Facultad de Farmacia, Universidad de Sevilla, C/ Profesor
García, González 2, 41012 Sevilla, España
S. Medina-Carrasco
Laboratorio de Rayos-X (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes 4B, 41012
Sevilla, España
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_1
1
2J. Martín et al.
1.1 Introduction
An important part of the increase in well-being in developed countries produced
by technological development is due to the incorporation of fossil fuels, the main
source of production of plastic products, which are in part responsible of the expo-
nential environmental deterioration. Plastics from fossils are synthetic polymeric
products that are chemically inert and therefore resistant to degradation. Reversing
this damage is only possible through the use of knowledge. The advancement of
polymer technology has allowed the development of renewable resources, giving
rise to sustainable green products made from natural and synthetic materials. These
compounds have the ability to be metabolically degraded in the environment.
Biodegradable polymers are those in which chain cleavage occurs leading to
mineralization. For this, specific conditions are required in terms of pH, humidity,
oxygenation and the presence of some metals to ensure its biodegradation. Properties
such as greater mechanical strength and rigidity, light weight, adjustable shapes,
easy handling, durability and low susceptibility to environmental degradation make
biopolymers the right choice to be used as matrices for a wide range of applications
[1].
Much of the properties of biodegradable polymers are excellent when compared
to petroleum-based plastics. Being easily biodegradable, they can be a real alter-
native to basic plastics. Therefore, biodegradable polymers have great commercial
potential for bioplastic, but some of the properties, such as brittleness, low distortion
due to increased temperature, high gas permeability, low melt viscosity for further
processing, etc., could restrict its use in a wide range of applications. Nanoreinforce-
ment of pristine polymers to prepare nanocomposites has already proven to be an
effective way to further enhances these properties [2]. Therefore, the modification of
biodegradable polymers by innovative technology is a great challenge for materials
scientists.
The utility of inorganic nanoparticles as additives to improve polymer perfor-
mance has been demonstrated in last years [2–9].
Organically modified layered silicate and polymers are of particular interest due
to their demonstrated significant enhancement of a large number of nanocomposites
physical properties, including barrier, flammability resistance, thermal and envi-
ronmental stability, solvent absorption, and biodegradability rate of biodegradable
polymers relative to an unmodified polymeric resin [2].
The main reason for the improvement of these properties of the polymer/silicate
in nanocomposites layers is the strong interfacial interactions between the polymer
matrix and the layered silicates [10]. Among the layered silicates commonly used
for the preparation of bionanocomposites belong to the same general family of 2:1
layers or phyllosilicates [ 11, 12]. Its crystalline structure consists of layers formed
by two tetrahedrally coordinated silicon atoms and central octahedral sheets with a
shared edge of either aluminum or magnesium hydroxide. The thickness of the layer
is around 1 nm, and the lateral dimensions of these layers can vary from 30 nm to
several microns or more, depending on the particular layered silicate. The s tacking
1 Biodegradable Polymers and Their Bionanocomposites Based … 3
Fig. 1.1 Structure of 2:1 phyllosilicates (from [13] with permission)
of the sheets leads to a van der Waals space between the layers called the middle
layer or gallery. Isomorphic substitutions within the layers are possible; thus, the
tetrahedral silicon can be partly substituted by Al3+ or Fe3+ and Al3+ of octahedral
sheet can be replaced by Mg2+ or Fe2+ and more rarely by others cations as Li+,etc.
This generates negative charges that are counteracted by alkali and alkaline earth
cations located inside the galleries. The local surface charge that is generated is not
constant in all the layers of the silicate; it is considered an average value that is known
as cation exchange capacity (CEC) and is generally expressed as mequiv/100 g.
Montmorillonite (MMT), hectorite and saponite are the most widely used phyl-
losilicates 2:1. In the case of substituted tetrahedral silicates in the layer, the negative
charge is on the surface of the silicate layers and therefore the polymer can more
easily interact with the matrices than in the case of the material with substitutions in
the octahedral layer. A scheme of the structure of these layered silicates is shown in
Fig. 1.1.
1.2 Biodegradable Polymers
According to the preparation of nanocomposites, biopolymers can be classified as
follows [14, 15].
4J. Martín et al.
Naturally occurring biopolymers are those produced from biosources including
polysaccharides (cellulose (CELL), chitosan (CTS), starch (ST), alginate (ALG),
gums, carrageenan etc.), proteins originated from plants or animals (zein, gelatin,
collagen, egg proteins, milk proteins, etc.) and lipids (triacylglycerides and waxes,
etc.).
Biopolymers derived from microorganism products such as polyhydroxybutyrate
and polyhydroxyvalerate, poly (hydroxyalkanoates) or poly (3 hydroxybutyrate-co-
3-hydroxyvalerate), among others.
Synthetic biodegradable polymers are those manufactured by industrial technologies
such as polylactic acid (PLA), polyglycolic acid, polyvinyl alcohol, polybutylene
succinate or polycaprolactone. Studies have shown its potential to improve physical
(strength, flexibility, durability, etc.), optical (photosensitivity, color, gloss, etc.) and
thermal (glass transition, conductivity, melting) properties.
1.3 Biodegradable Polymer-Based Bionanocomposites
Because biopolymers have poor mechanical and barrier properties, its reinforcement
with nanosized materials have attracted the interest of material researchers achieving
notable enhancements of their native properties. Bionanocomposites consist of
a hybrid materials derived from a biopolymer matrix reinforced with inorganic
nanofillers [16]. Three types of nanocomposites can be differentiated based on the
shape and dimensions of the dispersed particles [17]: (i) particulate nanocomposites
(isodimensional silica, metal or metal oxide nanoparticles); (ii) elongated-particle-
nanocomposites (two dimensions in the nanometer scale such as carbon nanotubes or
cellulose nanowhiskers); and (iii) layered-particle-nanocomposites (one dimension
in nanometer range such as layered silicate clays). The introduction of nanoparticles
in the polymer matrix has improved the properties of virgin polymers in terms of
mechanical (strength, elastic modulus, stability), heat (resistance) and permeability
(gases and water) properties [15, 18–20].
For environmental applications, layered silicate clays have been commonly
studied owing to their properties of availability, affordability, high surface area and
ionic exchange capacity. Recent studies have proven that the intercalation of polymers
and organic molecules in the interlayer space enhance their mechanical, thermal and
adsorption properties. The extent of nanofiller dispersion and intercalation depends
on the affinity between the silicate and the polymer matrix, as well as the preparation
technique [17, 21–23]. Four different morphologies can be obtained one mixed both
components (Fig. 2.2).
Phase-separated microcomposites (conventional microcomposite): The polymer is
unable to penetrate and intercalate between the silicate layers, acting as microparticles
dispersed in the polymeric matrix. Their properties are particularly poor due to the
lack of uniform dispersion.
1 Biodegradable Polymers and Their Bionanocomposites Based … 5
Intercalated nanocomposites: The polymer is penetrated and inserted between the
silicate layers giving rise to a significantly expansion in the interlayer distance of the
layers.
Flocculated nanocomposites: Slightly similar to the intercalated structure and appear
when there is hydroxyl interactions between the silicate sheets.
Exfoliated nanocomposites: The individual sheets are separated completely and
uniformly dispersed in a continuous polymer matrix. To get a complete exfolia-
tion is desirable since provide materials with enhanced mechanical, thermal, and
barrier properties (Fig. 1.2).
Table 1.1 shows the biopolymers and clays most commonly used for the prepara-
tion of bionanocomposites as adsorbent materials in environmental applications for
water remediation.
Fig. 1.2 Illustration of four possible polymer–clay morphologies (adapted from [13] with permis-
sion)
6J. Martín et al.
Table 1.1 Biopolymers and clays used in the synthesis of bionanocomposites (modified from [13] with permission)
Biopolymer Clay/organoclay Preparation methods References
Chitosan Montmorillonite Solution blending method [24–30]
Bentonite Solution blending method
and microwave heating
[31–34]
Vermiculite Solution blending method and
solution blending involving
ultrasound irradiation
[35–37]
Hexadecyl trimethyl ammonium-
Vermiculite
Solution blending method
involving ultrasound
irradiation
[36]
Na-mica-n Solution blending method [38]
LDH Solution blending method [39]
Attapulgite Solution blending method [40]
Carboxymethyl chitosan Montmorillonite Solution blending method [41]
Modified chitosan (ethylenediaminetetraacetic acid, glutaraldehyde,
sodium dodecyl sulfate and cetyltrimethyl ammonium bromide)
Gluconite Solution blending and
crosslinking method
[42]
Starch Montmorillonite Solution blending method;
Melt intercalation method
[26, 43, 44]
Organomontmorillonite Melt intercalation method [43]
Kaolinite and Kaolinite/ dimethyl
sulfoxide
Solution blending method [45]
[46]
Bentonite Solution blending method [47]
Palygorskite Solution blending method [37]
LDH Solution blending method;
Hydrothermal treatment
[48, 49]
(continued)
1 Biodegradable Polymers and Their Bionanocomposites Based … 7
Table 1.1 (continued)
Biopolymer Clay/organoclay Preparation methods References
Starch acetate Organomontmorillonite Melt intercalation method [50]
Cationic starch Montmorillonite Solution blending method [51, 47]
Bentonite Solution blending method [47]
Carboxymethyl cellulose LDH Solution blending method [52]
Carboxymethyl cellulose-Starch LDH Solution blending method [53]
Carboxymethyl cellulose-CTS Exfoliated montmorillonite Hydrogen-bond, amidation
and chains interleaving
interaction
[54]
Alginate Montmorillonite Solution blending method [26, 55–57]
Mica Solution blending method [58]
Palygorskite Solution blending method [37]
LDH Solution blending method [59]
Alginate/Xylan Bentonite Solution blending method [59]
Halloysite Solution blending method [59]
Hydroxyethylcellulose Montmorillonite Solution blending method [60]
C16-hydroxyethylcellulose Montmorillonite Solution blending method [60]
Cellulose-graft-Polychloromethylstyrene-graft-Polyacrylonitrile Organomontmorillonite Radical polymerization and
solvent blending methods
[61]
Cellullose Mica Solution blending method [62]
Cellullose Montmorillonite Solution blending method [63, 64]
Guar gum Bentonite Solution blending method [65]
Xanthan gum/n-acetyl cysteine Mica Solution blending method [66]
(continued)
8J. Martín et al.
Table 1.1 (continued)
Biopolymer Clay/organoclay Preparation methods References
Sacram Sepiolite Solution blending method [37]
Zein Palygorskite Solution blending method [67]
Sepiolite Solution blending method [67]
Montmorillonite Solution blending method [68]
Gelatin Montmorillonite Solution blending method [26]
Polylactic acid Montmorillonite Melt-blending method [69, 70]
Organomontmorillonite Solution blending method
and melt-blending method
[71, 72]
LDH Solution blending method [73]
Polylactic acid-chitosan Organomontmorillonite Solution blending method [74]
Polylactic-co-glycolic acid Montmorillonite Solution blending method [75]
1 Biodegradable Polymers and Their Bionanocomposites Based … 9
1.3.1 Chitosan/Clay Nanocomposites
CTS (poly-alfa(1,4)-2-amino-2-deoxy-d-glucose) is the second most abundant
polysaccharide in nature derived from N-deacetylation of chitin. CTS contains chem-
ically amine and hydroxyl groups in their structure which are potentials that has been
harnessed in the field of adsorption of substances when it is intercalated onto clay
minerals [27, 29, 30, 76]. CTS requires an acidic medium to be dissolved and, at
this pH CTS the protonated amine groups (−NH3+) promoting strong electrostatic
bonds with the clay by replacing a exchangeable cations of the pristine clay located
in the interlayer space [77].
The most intensive researches on CTS-based nanocomposites are focused on 2:1-
type layered silicates, especially on MMT. Darder et al. [29, 30] discovered that CTS
chains can form mono- or bilayer structures within the MMT interlayer depending
on the relative amount of CTS with respect to the CEC of the clay. Authors observed
an increase in d spacing from 1.20 nm to 1.45 nm and 2.04 nm, mono- or bilayer
structures, respectively. The CTS interaction mechanism resulted different; the first
CTS layer is adsorbed through a cationic exchange mechanism, while the second
one is adsorbed in the acetate salt form [29]. Authors also observed that when there
is an exchange higher than the CEC of the MMT, the adsorption mechanism shifts
to an anionic exchange capacity (AEC) since the protonated amino groups of CTS,
not involved in the interaction with the MMT, act as anionic exchangers improving
the adsorption of anions [27, 77, 78].
The structure of the CTS-based nanoncomposites is also affected by the concen-
tration of clay in the CTS matrix. Wang et al. [78] prepared CTS/MMT nanocompos-
ites using clay quantities from 2.5 to 10 wt%. The X-ray diffraction (XRD) pattern
and transmission electron microscopy (TEM) images corroborated the formation of
intercalated and exfoliated morphologies when the content of MMT was low and an
intercalated and flocculated structure at higher concentrations. Later, same authors
[41] studied the structures and properties using three different CTS derivatives (CTS,
carboxymethyl CTS, and N, N, N-trimethyl CTS). The carboxymethyl groups in the
CTS matrix increased the interaction with the hydroxylated edge groups of MMT
through hydrogen-bonding reaction. Intercalation and slight flocculation structure
was observed for the CTS/MMT nanocomposites. The use of carboxymethyl CTS
enhanced the extent of flocculation, and the quaternization of the amino group of
CTS gives a nearly exfoliated structure.
Other 2:1 layered silicates have also been prepared using CTS. For example,
Chen et al. [35] prepared a CTS/vermiculite bionanocomposite using epichlorohy-
drin (ECH) as crosslinking agent. According to the characterization results, CTS
cannot intercalate into the interlayer space of the vermiculite but crosslink with the
external surface of clay. ECH produces an improvement of the mechanical resistance,
chemical stability, pore size and adsorption/desorption properties of the bionanocom-
posite establishing covalent bonds with the carbon atoms of the OH groups of CTS
[79]. More recently, Alba et al. [38] synthesized several CTS/mica (2–4)-based
bionanocomposites by ion-exchange reaction. The bionanocomposite prepared using
10 J. Martín et al.
Na-Mica-4 contains more CTS than those from Na-Mica-2. Both bionanocompos-
ites exhibited higher thermal stability than the pure CTS. The characterization results
indicated that the adsorption of CTS in the interlayer space was successful, although
a CTS portion remains in the outer surface being hydrogen-bonded to the mica.
The zeta-potential values change from negative to positive for both bionanocom-
posites. More recently, da Silva et al. [31] prepared CTS/Bentonite nanocomposites
(at different CTS proportions, from 50 to 300%) using microwave heating. Various
types of nanocomposites (in the interlayer space) were obtained varying the CTS
proportions: monolayer for 50% of CTS; bilayer for 100–200% of CTS; mono- and
bilayer for 300% of CTS. Increasing the heating reaction time up to 30 min improved
the CTS intercalation efficiency without altering the morphology.
LDHs are classified as negative clays and have been previously assessed as effec-
tive adsorbents of anions [80]. Li et al. [39] prepared CTS/LDH bionanocomposites
by two methods: direct mixing of LDH nanopowder with CTS gel and in situ method
by adding LDH into CTS gel. A better dispersion of the nanoparticles was observed
with the second method, which resulted in better adsorption properties.
1.3.2 Starch/Clay Nanocomposites
ST combined two types of polymers: amylase (10–30%) and amylopectin (70–
90%) [46, 81]. It is a neutral molecule containing hydroxyl groups (susceptible
to substitution reactions) and acetal groups (susceptible to chain breakage). The
reinforcement of ST with clays produces a better dispersion of the structure and
enhanced its mechanical, thermal stability, and barrier properties without altering the
biodegradability [44, 46, 50]. Chivrak et al. [43] compared the properties of MMT
and organomodified montmorillonite (OMMT) incorporated into the ST matrix by a
melt blending process. Characterization results showed that MMT leads to interca-
lated bionanocomposites, while OMMT allowed the elaboration of well-exfoliated
bionanocomposites displaying better mechanical properties. Ruamcharoen et al. [45]
prepared two nanocomposites incorporating various amount of kaolinite and kaoli-
nite modified with dimethyl sulfoxide into sago starch via solution blending method.
The XRD and TEM images revealed intercalate and exfoliate structures attesting
well-dispersed kaolinite layers in the ST matrix. Authors observed a decreased of
the water vapor transmission of the native ST and an improvement in the tensile
strength and modulus of ST-based bionanocomposites.
The modification of ST matrix with cationic groups has been proposed to get
functional bionanocomposites for the removal of contaminants of anionic char-
acter from aqueous media [51, 82]. Koriche et al. [47, 83] revealed that the incor-
poration of cationic quaternary ammonium groups in the modified ST facilitated
its intercalation in MMT through a cationic exchange mechanism. The excess of
positively charge from ST produced an enhancement in the adsorption capacity of
nanocomposite toward anionic pollutants. Similar results were reported recently by
1 Biodegradable Polymers and Their Bionanocomposites Based … 11
Lawchoochaisakul et al. [51] whose use cationic ST/MMT as potential adsorbents
for basic dyes.
ALG-nanocomposites based on synthetic LDH clays have been studied although
to a lesser extent than natural clays. Chung et al. [49] synthesized LDH crystallites
into the ST (or acid-modified ST) matrices by hydrothermal treatment obtaining
well-dispersed structures. Wu et al. [53] synthetized first LDH with carboxymethyl
cellulose (CMCELL) as the stabilizer and then used it to prepare LDH/CMCELL/ST
nanocomposites. The incorporation of CMCELL in LDH enhanced the stability in
water giving its hydrophilic character which were also helpful to get a uniform
dispersion of the LDH/CMCELL/ST.
1.3.3 Alginate–Clay Nanocomposites
ALG is a biopolymer formed by linear copolymers units of 1,4-β-d-mannuronic acid
and 1,4-β-l-guluronic acid. It is negatively charged polymer containing carboxylate
groups in its structure. Reported studies indicate that the incorporation of clays into
ALG beads matrix improves the mechanical and thermal stabilities of the ALG beads
[55, 56, 84–86].
Alcântara et al. [37] carried out a study to compare the preparation and interac-
tion mechanisms of bionanocomposites using sepiolite and palygorskite fibrous clays
and polysaccharides of neutral (ST), cationic (CTS) and anionic (ALG) character.
Overall, in the three cases the interaction of the OH groups present in the biopoly-
mers backbone and the SiOH groups on the silicate surface is observed. Moreover, in
the case of ALG and CTS biopolymers, the presence of negatively carboxylate and
positively amino groups, respectively, may be also implicated leading to strong inter-
actions between both components. The resulted bionanocomposites displayed good
mechanical properties, improved water resistance and reduction of water absorption,
which make them very attractive as adsorbents for water remediation. Recently, Naidu
and Jhon [59] prepared xylan/ALG/bentonite or halloysite nanocomposites by solu-
tion blending method. When the load of lays was 5 wt% a significant decrease (49%)
of the water vapor, permeability was observed explained by the impermeable nature
of the silicate layers. Overall, nanocomposites prepared with bentonite clays exhib-
ited superior mechanical and optical properties than halloysite-based nanocomposite
and native ALG. Thermal stability and solubility were not significantly influenced
by the intercalation of the clays.
Reese et al. [87] prepared five LDH/ALG hybrid composites, four possessing
different guluronic/mannuronic acid ratios ALG and one acetylated ALG by copre-
cipitation method. Aluminum nitrate and zinc nitrate were used as a LDH precursor
to form hybrid composites with ALG solution. An increase in the d spacing was
observed by XRD when increasing guluronic acid content (1.28–1.85 nm) and
acetylated ALG (to 1.72 nm). The nuclear magnetic resonance (NMR) spectroscopy
revealed the interaction of negatively charged carboxylic groups from the biopolymer
with the positively charged inorganic main layer while, scanning electron microscopy
12 J. Martín et al.
(SEM) confirmed the highly flexible nanofoil morphology of the hybrid composites
which could function as reinforcement to the concrete applications.
1.3.4 Cellulose/Clay Nanocomposites
CELL is the most abundant biopolymer in nature consisting of linear beta-1,4-
linked d-glucopyranose monomers. CELL aerogels have been applied as adsorbents
in various contaminant treatments [54]. Despite its biodegradability, affordability,
biocompatibility and its absence of toxicity, CELL is insoluble in water or in common
solvents doing complex its processing. Moreover, CELL has chains very packed
through inter- and intramolecular hydrogen bonds and suffers poor dimensional
stability, mechanical strength and functionality [13, 54, 61]. The chemical modi-
fication of its structure is necessary to improve its properties [88]. To that end, graft
copolymerization is a method commonly used. Park et al. [89] synthesized maleic
anhydride grafted CELL acetate butyrate (CAB-g-MA) as the compatibilizer in order
to obtain a better interaction between CELL acetate and the OMMT. A mixture of
exfoliated and intercalated structures is obtained when the compatibilizer is used
at 5 wt%, while without it an intercalated structure was observed. Because CELL
tends to decompose at Tª < 260–270 °C (below its melting point), the free radical
polymerization and solution-casting techniques instead of melt compounding are
currently used to prepare grafted CELL/clay bionanocomposites. Abbasian et al. [61]
prepared a CELL-graft-polychloromethylstyrene-graft-polyacrylonitrile/organoclay
through metal catalyzed radical polymerization and solvent blending methods.
Other simply and most advantageous, for economic reasons, modification of
CELL is the production of CMCELL. CMC is an anionic polymer, which contains a
hydrophobic polysaccharide backbone and numerous hydrophilic carboxyl groups,
hence showing an amphiphilic characteristic. Cukrowicz et al. [90] prepared two
nanocomposites using CMCELL of different viscosity to modify the structure of
MMT. The FTIR and XRD analysis confirmed the constituent materials react by the
hydrogen bonds formation, which results in the polymer adsorption on the surface of
mineral particles and results also showed that MMT forms a more stable s ystem with
the lower viscosity CMCELL. However, both types of CMCELL caused a partial or
full delamination of the MMT structure, which may be related to the similarity of
mineral surface and polymer charges or to the rigidity of the polymer chain back-
bone making it difficult to change its conformation. Yadollahi et al. [52] intercalated
CMC into Mg–Al LDH and Ni–Al LDH by coprecipitation methods. XRD pattern
revealed an increase in d spacing from 0.862 to 1.73 nm for Mg–Al LDH and from
0.816 to 2.23 nm for Ni–Al LDH. TEM images showed the presence of interca-
lated and non-intercalated layers in both Mg–Al LDH/CMC and Ni–Al LDH/CMC
nanocomposites, while the thermal stability was higher for Mg–Al LDH/CMC than
Ni–Al LDH/CMC nanocomposites. The introduction of long alkyl chains has also
been proposed to modified CELL making hydrophobic derivatives. Simon et al. [60]
introduced a low amount of C16 alkyl groups in hydroxyethyl CELL that presented
1 Biodegradable Polymers and Their Bionanocomposites Based … 13
a higher affinity for the MMT surface than its precursor hydroxyethyl CELL. More
recently, Wang et al. [54] prepared a CMCELL/CTS/ exfoliated MMT nanosheets
(MMTNS) composite hydrogel very effective as adsorbent for dye effluent remedia-
tion. The hybrid material was synthesized via hydrogen bond, amidation and chains
interleaving interaction. MMT is first mechanically exfoliated into nanosheets with
single or few layers, which improve its adsorption performance. MMTNS present
some properties (positive charge on edge and negative charge on surface, small size
or strong dispersion among others), which make possible that MMTNS could then
be fully dispersed in the CELL matrix.
1.3.5 Protein–Clay Nanocomposites
Proteins (zein, collagen, gelatin, wheat gluten, soy, etc.) are hetero-biopolymers
containing different kinds of amino acids. Protein molecules are amphoteric
molecules and present good gas barrier properties but lower water vapor perme-
abilities. The incorporation of proteins into clays has been used to improve the water
vapor barrier properties or with the end of reduce the hydrophilic character of original
clays. Alcântara et al. [67] prepared Zein/sepiolite and palygorskite. Fibrous clays do
not present intercalation properties but exhibit a large specific surface area, micro-
porosity, the ability to adsorb a large variety of molecules. Zein is a hydrophobic
molecule that was assembled on the external surface of clays through the interaction
of its amide groups with the OH groups at their external surface. The quantity of zein
in the clay affects the structure. Zein/Sepiolite showed a larger amount of assembled
protein than those based on Zein/Palygorskite due to its higher external surface area.
Authors also tested that improved properties of water resistance are obtained when
ALG is incorporated as bioadditive. The resulting ALG/Zein/Zlay nanocomposite
improved some properties like flexibility and good water vapor barrier properties
and reduced the water uptake. Same authors [68] prepared a Zein/MMT nanocom-
posite with excellent compatibility, homogeneity and mechanical properties and
without the need to add compatibilizers or plasticizers. Azhar et al. [26] prepared
a gelatin/MMT nanocomposites, and the coexistence of both intercalated and floc-
culated structures was observed. TEM images showed that a large amount of MMT
was stacked together in gelatin–MMT nanocomposite, while a few intercalated clay
platelets were observed.
During the protein intercalation process by clays, it is very important to adjust
and control the pH below the isoelectric point of the biopolymer. For example, the
incorporation of smectite clays in the gelatin matrix occurs at low pH values when
the protonated amine groups of the protein can replace totally or partially the cations
situated in the interlayer space of the smectites [77]. Overall, proteins have the ability
to form a good film that makes them an ideal material for biodegradable packaging
and make them best suited for packaging and biomedical applications rather than
environmental remediation.
14 J. Martín et al.
1.3.6 Polylactic Acid/Clay Nanocomposites
PLA is a synthetic biopolymer derived from cornstarch by fermentation. Its basic
unit is lactic acid. PLA presents promising qualities of strength, thermal plasticity,
biodegradability and biocompatibility. However, its brittleness, low miscibility, gas
permeability and slow crystallization rate may limit its use. Clays have been proposed
to improve some of these last properties without affect its natural one [15, 91].
To enhance the miscibility with PLA by the solution blending method, some
researches have proposed the modifications of the clay surface [72, 74, 92]. Wu and
Wu [74] get exfoliated structures enhancing the interaction between PLA and OMMT.
First, authors carried out the organofunctionalization of the MMT with n-hexadecyl
trimethylammonium bromide cations and then modifying it with CTS. McLauchlin
and Thomas [72] used of a novel surfactant to modify the MMT, cocamidopropyl
betaine (CAB) containing both quaternary ammonium and carboxyl moieties, which
resulted in a proper dispersion in the PLA matrix. CAB presents a negative charge
in basic conditions and a positive charge at lower pH values. The XRD pattern and
TEM images showed an ordered intercalated structure. To improve the chemical
compatibility between PLA and LDH, Chiang and Wu [73] modified the surface of
LDH using PLA with carboxyl end group through an ion-exchange process. XRD
pattern and TEM images of synthesized nanocomposites denote that modified LDHs
are randomly dispersed and exfoliated into t he PLA matrix.
Recently, Gomez-Gamez et al. [69] studied the technical properties of PLA/MMT
nanocomposites (using different clay loadings). Authors observed an increase in
thermal stability and Young’s modulus at increasing clay loading. Similar results
were obtained by Lopes Alves et al. [71] when incorporated different OMMTs in PLA
matrix. Neppalli et al. [70] compared the structure and morphological changes when
different types of clays (cationic (MMT) and anionic (perkalite)) are incorporated
in PLA matrix. The results showed that perkalite-based nanocomposites presented
a faster crystallization rate and a higher crystallinity, besides a faster degradation,
while the MMT-based nanocomposites resulted in disordered lamellar stacks.
1.4 Preparation of Biopolymer–Clay Nanocomposites
In order to improve the intercalation/exfoliation process in a polymeric matrix, it is
very common to carry out a change in the chemical composition of clays on their
surface to make its polarity coincide with that of the polymer [17]. In order to achieve
this purpose, the most used technique is cationic exchange and has been employed
mechanisms among which we can highlight adsorption of block copolymers [93],
grafting of organosilane [94], ionomers applications [95], as reported in previous
works [22, 23].
1 Biodegradable Polymers and Their Bionanocomposites Based … 15
Areviewwork[23] showed a detailed analysis of the ways of working established
to develop bionanocomposites based on polysaccharides with MMT, explaining their
state of dispersion and properties.
There are three main techniques commonly used to carry out biopolymer/layered
silicate bionanocomposites [15, 17, 23, 81], which are involved in the incorporation
of clay in a polymer previously swollen with solvent. These methods are: (i) solution
blending [2], (ii) polymer melt (or melt blending) [96] or (iii) adding modified clay
to a polymerization reaction (in situ polymerization method) [97]. The analysis of
the data presented in Table 1.1 shows that the most used and generally the most
appropriate method is the first one on the list.
1.4.1 Solution-Blending Method
For this way of preparation, a solution containing the polymer is initially prepared
by using a solvent that allows it, being water the most used in case of biopolymers.
At the same time, the layered silicate is dissolved in the solvent used or in another if
necessary to achieve a miscible solution. Once this step is completed, the polymer
solution is mixed with the phyllosilicate dispersion, allowing an intercalation of both
structures and the resulting solution is allowed to homogenize, to finally evaporate
the solvent [22]. In the case of non-water-soluble polymers, the method is carried
out with the use of organic solvents in large quantities, therefore with a high cost
both economically and for the environment [81]. An added drawback is that a very
low amount of solvent can be kept in the final product at the polymer–clay interface,
which as has been shown in previous work will result in less interactions between
the surfaces of the clay and the polymer [98]. It has been previously commented
that the solution blending method is the most widely used (as shown in Table 1.1),
and this is a consequence of the fact that biopolymeric materials that are used in the
production process of bionanocomposites (such as be CELL, pectin or CTS) do not
allow the possibility of being processed by fusion due to high thermal degradation or
by the thermomechanical process. Preparing the polymers in situ also has limitations
in the way they are obtained, since in practice most biopolymers are available from
natural formation processes showing generally in polymeric form compared to the
much less common monomeric form [23]. Figure 1.3a represents a schematic view
of the preparation procedure by solution-blending.
1.4.2 Melt-Blending Method
This preparation technique makes a better mix possible of the clay materials and
biopolymer in comparison with the solution-blending. The procedure involves a
process where high temperatures are reached in which the clay material is placed at
the same time into the heated polymeric material matrix in an equipment where the
16 J. Martín et al.
Fig. 1.3 Bionanocomposite preparation methods: a solution blending, b melt blending and c in situ
polymerization (adapted from [13] with permission)
mixture is produced by melting and the resulting compound is prepared by kneading
to obtain a final product of high homogeneity [22]. By controlling two conditions,
the residence time and the shearing, the dispersion of the clay can be optimized
[99]. The residence time is necessary to enable the chains of polymeric material to
diffuse into the interlaminar spacings of the clay to obtain a highly exfoliated and
disorderly morphology. The shearing collaborates in the delamination of clays. This
technique has advantages for the conservation of the environment because no solvent
is used, but the thermal or thermomechanical treatments cause partial degradation
of the compounds and, as long residence times are necessary for the exfoliation of
the clay, a degradation in the matrix is caused. These disadvantages make this mode
of operation unsuitable for preparing biopolymeric materials, with the exception of
additive modified ST thermoplastic or PLA. [70, 100, 101]. Figure 1.3b schematizes
a representation of the melt-blending preparation method.
1.4.3 In Situ Polymerization Method
In a first stage of this method, the clays swell in a monomer solution where polymer-
ization begins and from that situation it propagates [23]. Heat or a suitable chemical
can be used to start the polymerization process [99]. With polymerization, there is
an increase in the molecular weight of the macromolecules, producing an increase in
the basal spacing d001 and, on occasions, to a morphology exfoliated practically in
1 Biodegradable Polymers and Their Bionanocomposites Based … 17
its entirety [2]. This technique has been used as another way of preparation instead
of melt blending method as a mechanism for an in situ polymerization preparation of
intercalated lactide monomers for the production of compounds in exfoliated form
[102]. As previously explained, the polysaccharide chains are obtained from nature
itself in the growth process of plants and are obtained from these already in their
polymeric conformation. Because of that, this way of preparation is not suitable
to obtain bionanocompounds that are prepared from a polysaccharide base [23]. In
Fig. 1.3c, a representation of the in situ polymerization preparation method can be
seen.
There are other ways to obtain this type of materials using a mode that does
not involve the traditional way, such as microwave induction, intermatrix synthesis,
self-assembly, template targeting, electrospinning or preparation under supercritical
conditions (e.g., supercritical CO2) to obtain the final compound [81].
1.5 Characterization Techniques
One of the main aspects in the research of polymer–clay nanocomposites is the
characterization and understanding of the physicochemical properties enveloped with
adsorption capacity, such as expansion properties, morphology, layer loading and
charge distribution, structure and pore size. The most commonly applied techniques
for the characterization of clays are XRD, TEM, SEM, Fourier transform infrared
(FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and thermal
gravimetric analysis (TGA) [17].
The study of lamellar spacing by XRD has been used to a great extent to study the
resulting biopolymer–clay structure after the possible preparation methods indicated
in the previous section, allowing the technique also to obtain crystallographic struc-
tural and microstructural information [21]. By evaluating the position and possible
displacements of the basal planes can be determined the type of nanocomposite in
terms of its structure, which can be separated by phases, with the biopolymer and the
clay intercalated or with exfoliated sheets in general. XRD could be used as a way to
see and understand the kinetic properties of the molten polymer mixture. The study
of the intensity and shape of the peaks corresponding to the basal planes is a way
of interpreting the degree of dispersion of the clay inserted in the matrix containing
the polymer or polymers in more complex cases. One of the characteristics that can
be understood for exfoliated or disordered structures is that the disappearance of the
reflections leads as the most likely interpretation the complete distribution of the
phyllosilicate sheets in the matrix formed by the biopolymeric part with the break-
down of the structure of the sheets or layers of the phyllosilicate or clay. For this
technique in general and applying it to intercalated structures, spacing expansion is
observed through the displacement of peaks corresponding basal spaces toward lower
2Theta diffraction angles, and it is so observed after intercalation of the polymer.
On the contrary, for conventional microcomposite structures, the d values and conse-
quently those of 2Theta will not change. This is interpreted to mean that the clay
18 J. Martín et al.
compound retain its laminar conformation since the chains of polymeric material are
not adsorbed in the interlaminar space [21].
Nevertheless, sometimes the use of XRD analysis alone does not allow determine
with certainty the structure of the nanocomposite because in general it only provides
information on the orientation and spacing of the clay sheets, which makes it difficult
to interpret the diffractogram. Another additional problem is that when there are
mixtures of different clays, the value obtained from the spacing can be inaccurate
due to the overlapping of the peaks of the different contributions. Furthermore, the
possible absence of peaks corresponding to reflections of intercalated clays that are
randomly distributed could lead to the erroneous interpretation that the structures are
exfoliated. Finally, dilution of the clay can also be causing broadening or no peaks
even without a delamination phenomenon [21].
The XRD technique is usually complemented by TEM to a large extent because
this microscopic technique has the possibility of providing qualitative information
on the spatial arrangement and morphological characteristics of the clay, in addition
to allowing any internal defects to be observed visually. Combining the visualization
of the samples with the contribution of diffraction data, the main advantage of TEM
is its magnification (between 50,000 and 10,000,000x). The micrographs obtained
by TEM allow the direct observation of the spatial distribution of the phyllosilicate
sheets, which is not possible by other microscopic techniques. In the images obtained,
the clay sheets show a strong contrast because they are basically composed of Si,
Al and O with higher atomic numbers than those of the polymer containing C, H
and N. In this way, the interlaminar spaces of clay layers are usually represented as
dark lines, while the presence of heavier atoms as lighter areas. In this sense, TEM
images of separated phase compounds are represented as darker due to the presence
of clay aggregates, while for exfoliated composites brighter images are obtained. In
the same way as the TEM technique, SEM also allows to obtain micrographs of the
surface areas of solid samples, in addition to providing information on their disper-
sion, structural conformation and elemental composition [21]. Notwithstanding, the
magnification of the SEM technique is of the order of 1 nm, making it difficult to
obtain detailed and precise information on the distribution of nanoparticles in the
polymeric matrix, although it is useful for obtaining images of surfaces that are frac-
tured. There is also the possibility of a combined use of SEM with the technique
of energy dispersion X-ray spectroscopy to study the dispersion range of nanosized
particles on bionanocomposites surfaces that are fractured [15].
The FTIR technique, like those previously described, is widely used and is a well-
accepted method to study the structure of the nanocomposite polymer, which makes
it possible to differentiate whether the chemical bonds belong to the nanocomposite
or are simply part of the polymer. As a drawback, the differentiation of the chemical
bonds that appear can present complexity in the interpretation and understanding even
though the intercalation has already been carried out. As previously explained, many
studies have been conducted using FTIR to characterize the biopolymer introduced
into the clays structure [29, 38, 78]. It is a characterization technique with great
capacity and utility to determine electrostatic relationships and interactions between
clays and biopolymers. Darder et al. [19] used this spectroscopic technique to evaluate
1 Biodegradable Polymers and Their Bionanocomposites Based … 19
the interactions between sepiolite, starch and alginate and were able to observe an
appreciable change in the vibration band of the silanol-type groups placed on the
surface of the clay, results that seem to indicate that the Interaction relationships occur
between the OH groups on the external surface of the clay and the groups belonging
to the polysaccharide that have hydroxyl character. The FTIR results showed that
the corresponding band appeared displaced showing a decrease in the frequency
values, which implies a lower value of absorbance with respect to that assigned to
the Mg–OH stretching vibration in which no changes were observed. Other work
done by Darder et al. [80] and Leroux et al. [103] were able to find high-intensity
bands by FTIR corresponding to the interactions that occurred between carboxylate
groups that were negatively charged from pectin biopolymers and ALG and LDH
sites presenting positive charge, while a weak interaction was observed between
LDH and i-carrageenan.
The NMR technique is also used to study the morphology, the surface at the chem-
ical level and the dispersion of the clay using the signals of spin–lattice relaxation
time for 1H, 13C, 23 Na, 27Al or 29Si [2]. NMR (1H and 13 C) was used to obtain values
that allowed quantifying the degree of exfoliation of nylon 6-MMT nanocomposites
and established a possible correlation between obtained results and the quality of
the clay dispersion. For cases where the phyllosilicate is stacked and not sufficiently
dispersed in the polymer matrix, the polymer–clay average distances are higher and
the average paramagnetic contribution shows a lower value [2]. NMR (29Si and 23Na)
spectroscopy was used to demonstrate the assimilation of chitosan into mica, while
chemical bonds of chitosan are formed to Al–O and Si–O of the basal sheets [38].
Combined use of FTIR and 13C NMR measurements allow to verify the ability of the
chitosan–clay nanocomposite to act as an anion exchanger when the biopolymeric
material is distributed in the form of a bilayer in the interbasal zone (using in this
case smectite) [30].
As the last of the techniques presented, TGA gives information on thermal
behavior of bionanocomposites, where many works have allowed understand the
greater stability of biopolymeric materials that are part of bionanocomposites. The
introduction of biopolymeric materials between sheets of phyllosilicates causes an
increase i n the decomposition temperature in the order of 40–50 °C. This is because
the layered silicate works as a thermal shield when the bionanocomposite is struc-
turally formed, causing a greater thermal stability of the entire system and helping a
greater carbon formation once the thermal decomposition is completed [2]. The TGA
results obtained demonstrate decomposition or degradation, in the form of weight
loss, depending on time or temperature, such as isothermal or dynamic heating.
Between room temperature and around 170 °C, a weight loss is observed, which
is interpreted as the loss of water that can come from the interlayers or from the
surface of the phyllosilicate, from the water retained in the biopolymeric materials
or the interstitial water. The origin of the water described above will depend on the
thermal decomposition in the layered silicates or biopolymeric materials used. As a
normal mechanism, the decomposition of the system starts at about 250 °C with the
degradation of components of organic origin and ends at about 600–630 °C with the
decomposition of the crystalline structure and the phyllosilicate [2, 19, 26, 39, 48]. To
20 J. Martín et al.
finish this section, different works have studied the thermal stability of starch-based
nanobiocomposites to understand the i nteractions that take place from the evaluation
of the thermal stability and the behavior of the system once the clay dispersion occurs.
For example, thermal analysis was used to highlight the increase in temperature at
which the degradation of potato starch-MMT system occurs in comparison to the
laminar silicate material. In the same sense, the system with organically modified
MMT was analyzed and compared with the previous one. It should also be taken
into account that the stability as a function of temperature of the potato starch-MMT
system was greater than in the case with organically modified MMT, which could be
explained as a relationship between the dispersion of MMT and the stability of the
system as a function temperature [44].
1.6 Environmental Applications
The development of bionanobiocomposite materials systematically and tailor fashion
based on layered silicates have offered improved functionality and properties, such
as enhanced barrier properties, elasticity, strength, optical clarity and antimicrobial
properties, and which make them optimal for a large number of environmental appli-
cations in the field of food, agriculture, soil and water treatment, besides in the
biomedical field, sensor technology, drug delivery and applied sciences [13, 16, 77,
82]. The main environmental applications of bionanocomposites based on layered
silicates are shown below.
1.6.1 Bionanocomposites with Layered Silicates in Soil
and Water Treatment
The better adsorption capacity, selectivity and stability of bionanocomposites with
respect to nanoparticles give them numerous applications in many areas, such as soil
and water treatment among others.
Bionanocomposites prepared from 2:1-type layered silicates and natural polymers
by cation-exchange reaction are especially interesting in the removal of anionic
contaminants [27]. The interaction between the polymer in the cationic state and the
surface of the mineral clay changes the nature of the clay surface from hydrophilic
to hydrophobic. Acidic pesticides, at the pH of soil and natural waters, are in an
ionic state. This modification with organic cations is a strategy to favor the affinity
between the bionanocomposite and the anionic pesticides [104–110].
The concern of heavy metal contamination due to its magnitude, toxicity and
non-biodegradability is high. Industrial wastewater derived from paints, pigments,
fertilizers, fungicides, the manufacture of metals and batteries are the potential origin
of the presence of heavy metal ions in soils and waters. There are many investigations
1 Biodegradable Polymers and Their Bionanocomposites Based … 21
that show the advantage of bionanocomposites with layered silicates in cleaning
polluted waters. So, as examples, CTS/vermiculite biocomposite has the potential
to be utilized as an ecofriendly adsorbent for removing Cd(II) and Pb(II) [35]. The
ecofriendly novel ALG-Au-mica bionanocomposite was also found to exhibit good
adsorption capacity for the adsorption of Pb(II), Cu(II) in single and binary system
from aqueous solution [58]. Xanthan gum-glutathione/ zeolite bionanocomposite
has been proved to be a promising adsorbent of Ni (II) (85%), Pb (II) (93%) and
Congo red (80%) from aqueous solution, Guar gum/bentonite for Pb (II) and crystal
violet dye and Xanthan gum/ n-acetyl cysteine-modified mica bionanocomposite for
Pb(II), Ni(II) and Cu(II) [58, 65].
Water is considered the most essential natural resource; however, freshwater
systems are directly threatened by various human and industrial activities that cause
pollution by different agents such as sewage and domestic waste, heavy metals, deter-
gents and soaps, fertilizers, industrial effluents, pesticides, etc.… The use of advanced
technology for water purification that is cost effective has been and continues to be
the subject of research by the scientific community. The membranes show attrac-
tive characteristics due to the minimum energy consumption, easy operation, control
and maintenance, great selectivity and permeability, good adaptability, satisfactory
performance and stability in various conditions. Important advances have been made
in water management with the improvement of the characteristics and performance of
membranes prepared with clays and various types of polymers, generally presenting
a synergistic effect in the elimination of contaminants. Membranes prepared from
different polymers and layered silicates are useful in the removal of heavy metals,
dyes, and organic and inorganic contaminants from water, as well as for desali-
nation and as superabsorbents [111]. Mavrova et al. [112] proposed new hybrid
process of electro-coagulation/membrane filtration with very good results of Se As,
Cu, Pb removal and others metals in the treatment of industrial wastewater. Ma
et al. [113] prepared for the first time zeolite-polyamide thin film nanocomposite
membranes on a porous polysulfide substrate for use in forward osmosis for water
decontamination, reported that incorporation of zeolite-polyamide in the range of
0.02–0.1 wt/v% caused an increase in the permeability of the membrane possibly
due to the porous nature of the zeolite. These membranes also exhibit antimicro-
bial, antifungal and antifouling properties. However, there is a need to improve these
membranes such as reduce membrane fouling, improve selectivity, shelf life and
permeability. Thermal, mechanical and chemical resistance can be improved and
help reduce energy consumption. Research should be focused on assessing prof-
itability of nanomaterials, perfecting techniques for incorporating nanoclay in the
polymer matrix and monitor the long-term stability of these membranes. The devel-
opment of a single effective membrane should be advanced for the largest possible
number of contaminants from a specific source [114].
22 J. Martín et al.
1.6.2 Bionanocomposites with Layered Silicates for Food
Packaging
The use of bionanocomposites for food packaging can, in addition to protect food and
increase shelf life, due to improved mechanical, thermal and gas barrier properties,
be seen as a green solution to the growing problem of food packaging waste disposal
on a global scale [115–117].
By varying the quantity of the components of the formulations in the bionanocom-
posites based on layered silicates, it is possible to improve the stability and biodegrad-
ability of the resulting materials. This is especially important for modulating the
mechanical properties, but also another important property of food packaging mate-
rials, such as their ability as a mass transfer barrier to and from food products,
permeability of gases, such as oxygen and carbon dioxide, as well as water vapor,
are essential in many food packaging. Applications, such as modified atmosphere
packaging and its consideration for the packaging of carbonated beverages, may
also be key. Its use can be extended to foods with high moisture content. It can also
spread to foods with high moisture content. Barrier functions can be enhanced by
incorporating lipids and/or polysaccharides. The incorporation of nanoparticles for
the improvement of physicochemical and barrier properties has been investigated
[118–120].
The barrier properties of gases that do not interact in nanocomposites depend
mainly on two factors: (1) the aspect ratio of the layered silicate particles and (2)
the extent of dispersion of the silicate within the polymer matrix [121]. When the
nanoclays are used at moderate levels (4–7% by weight) and processed correctly, the
degree of dispersion of the layered organoclay is maximized (and consequently an
exfoliated morphology is achieved); the barrier properties depend only on the aspect
ratio of the particles. In most cases, the reduction of oxygen permeability through
the incorporation of organoclay falls in the range of 50–60%, and up to 65% in the
case of synthetic fluorinated mica at 4% by weight [122].
Equally interesting results have been obtained for the water vapor permeability
(WVP), increasing the permeability linearly with the increase in the proportion of
layered silicate in the formulation [123, 124].
The mechanical and functional characteristics of bionanocomposites based on
lamellar silicates can present the following advantages for food packaging:
• Improved organoleptic characteristics of foods such as appearance, odor and
flavor.
• Reduction of volume, weight and packaging waste.
• Longer shelf life and improved quality of items generally not packaged.
• Control over intercomponent.
• Individual food containers with small particles, such as nuts and raisins.
• They function as carriers of antimicrobial agents and antioxidants.
• Controlled release of active ingredients.
• Materials from renewable resources.
• Biodegradability.
1 Biodegradable Polymers and Their Bionanocomposites Based … 23
These unique characteristics of nanobiocomposites allow the development of new
products in the food industry [125, 126].
1.6.3 Bionanocomposites with Layered Silicates
for Agricultural Applications
The high worldwide consumption of plastics for improving agricultural production
and crop protection causes a large amount of plastics waste into the environment,
which are buried in the ground or burned by farms that release harmful substances.
Bionanocomposites prepared with nanomaterial additives such as TiO2 and MMT
have been a good alternative to non-biodegradable plastics since they can be directly
disposed of in the soil or in a composting system at the end of their useful life
[127, 128].
Some advantages of these nanobiocomposites films are [129]:
• They are biodegradable in the soil by microorganisms such as bacteria, fungi and
algae.
• They are degraded by the action of sunlight and water.
• They control the release of active substances such as pesticides and insecticides.
• Controlled degradation allows optimal crop development.
• They have a greater durability against UV, visible and infrared light radiation.
• Materials from renewable resources.
1.7 Conclusion
The possibility of assembly biopolymers with clay minerals affords the prepara-
tion of new materials with favorable properties for environmental applications. Clay
minerals are well known for their adsorption properties, while biopolymers can be
great allies regarding their biocompatibility and biodegradability. The reinforcement
of biopolymers with layered silicates produce a better dispersion of the structure
and enhanced its mechanical, thermal and adsorption properties without altering the
biodegradability. The natural polysaccharides (CTS, ST, ALG or CELL) together
with the synthetic PLA incorporating into layered silicates of the smectite group and
the synthetic LDH clays have the materials more relevant for environmental applica-
tions. Published results highlight the high influence of both types of materials as well
as their quantities in their structure and morphologies as well as the need to explore
other adsorption parameters and operating conditions. Therefore, a holistic approach
must be taken to optimize the use of certain biopolymer/clay nanocomposites for a
specific contaminant.
24 J. Martín et al.
The techniques or methods that have been used for obtaining layered silicates that
are functionalized are of vital importance to obtain a correct dispersion of clay mate-
rials in the polymeric matrices. Clay nanocomposites have properties and character-
istics that are due in the first place to the methods and therefore to the mechanisms
used for the modification of layered silicates. As shown in this work, the solution-
blending method provides, in general, the best dispersion of clays in the polymeric
matrix compared to melt-blending method and is the most widely used in the litera-
ture. This can be associated mainly with high agitation power and the low viscosity
associated with solution-blending method. From another point of view, melt-blending
proves to be the most ecofriendly and viable technique from an industrial perspective
while providing good economic potential.
The potential applications of materials based on layered silicate nanobiocom-
posites in the food packaging industry offer a real alternative to the problem of
packaging and waste disposal. In agriculture, the use of these biodegradable and
renewable plastic materials is also a way to improve crop production and protection.
Applications of bionanocomposites in soil and water treatment, both in cleaning
and desalination, are being studied extensively by materials science researchers
due to its promising future. Reported studies have shown that its efficiency and
effectiveness in the recovery of organic and inorganic pollutants through adsorption
processes are very high. There is a clear trend in the study of the design of effective
membranes in comprehensive water treatment. However, most of these applications
have been assessed at the laboratory scale, but their use must be extended to industrial
applications and large-scale production.
The potential applications of materials based on layered silicate nanobiocompos-
ites in the food packaging industry offer a real alternative to the problem of packaging
and waste disposal.
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Chapter 2
Chitosan/Poly (Ethylene Glycol)/ZnO
Bionanocomposite for Wound Healing
Application
Zahra Emam-Djomeh and Mehdi Hajikhani
2.1 Introduction
The rapid growth of science and technology has led us to see new achievements in the
field of biomedical every day. Recent studies have identified polymers as an impor-
tant member of the biomedical sciences used in various fields and various forms [1,
2]. In general, polymers can be classified into two groups: biopolymers and synthetic
polymers [3]. Synthetic polymers have advantages such as easy production, process-
ability, and lower cost than biopolymers [4]. Common synthetic polymers include
polyethylene, polypropylene, polytetrafluoroethylene, and polymethyl methacrylate
[5]. The next group of polymers is biopolymers that originate from living organisms
[6, 7]. In simpler terms, these polymer compounds are biological molecules. These
biomolecules can be of plant origins such as corn or beans, animal origin, or even
bacterial origin [8]. Biopolymers can be classified as follows. Based on monomeric
units, they can be divided into the following three categories: The first group is
polynucleotides, which are long polymers and consist of 13 nucleotide monomers
or more. The first group includes RNA and DNA. The second group is polypep-
tides, which are short polymers of amino acids. The second group includes collagen,
actin, and fibrin. The last group is polysaccharides, which are polymeric structures
of carbohydrates, which generally have a linear structure. The third group includes
starch and cellulose [9].
Biopolymers can also be classified into five categories based on their origin,
including [9, 10]: The first category includes polyesters such as polylactic acid and
Z. Emam-Djomeh (B) · M. Hajikhani
Department of Food Science and Engineering, University of Tehran, 16th Azar Street, Enghelab
Square, Tehran, Iran
e-mail: emamj@ut.ac.ir
M. Hajikhani
e-mail: hajikhani.mehdi@ut.ac.ir
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_2
31
32 Z. Emam-Djomeh and M. Hajikhani
polyhydroxyalkanoates. The second category includes proteins, which are divided
into two categories, plant, and animal. In the case of plant proteins, gluten and zein can
be mentioned, and in the case of animal proteins, we can mention collagen, gelatin,
elastin, and serum albumin. The third category includes polysaccharides, which are
divided into four subcategories. The first subcategories contain bacterial polysaccha-
rides that include xanthan, dextran, dellan, levan, curdlan, polygalactosamine, and
cellulose. Fungal polysaccharides such as pullulan and elsinan glucans are divided
into the second subcategories. The third subcategories belong to polysaccharides
of plant or algal origin, including starch, cellulose, agar, alginate, carrageenan,
pectin, konjac, and various gums. Finally, animal polysaccharides such as chitin
and hyaluronic acid are divided into the fourth subcategories. The fourth category
includes lipids/surfactants, among which are acetoglycerides, waxes, and emulsions.
The last category includes polyphenols, which include lignin, tannin, and humic acid
[11]. Over the last decade, numerous studies by researchers on wounds and wound
healing have shown the importance of this issue. Biocompatibility, biodegradability,
non-toxicity, and non-allergenicity are considerations for polymers used in wound
healing research [12–14].
Zinc oxide is an inorganic compound that has various applications in industry.
This substance is found naturally, but most of it is produced synthetically [15].
It is also used in many skin diseases [16]. Various studies have shown t hat topical
application of zinc oxide regenerates epithelium, reduces infection, and heals wounds
[17]. Zinc oxide also accelerates wound healing [18]. In this chapter, we have tried
to introduce different properties of two polymers, chitosan, and polyethylene glycol,
which are among the common polymers used to prepare different types of wound
dressings. Biocompatibility, availability, reasonable price, and processability have
led to these polymers being considered in wound dressing. Also, the production
of bionanocomposites from chitosan/PEG containing zinc oxide nanoparticles for
wound healing has been studied in this chapter.
2.2 Chitosan
The main component in the exoskeleton of insects and crustaceans such as shrimp
is composed of chitin [19]. Chitin is an abundant mucopolysaccharide, which ranks
second after cellulose in terms of biosynthesis per year [20]. However, less atten-
tion has been paid to chitin than cellulose [21]. As shown in Fig. 6.1, chitin is a
large, structural polysaccharide made from glucose-modified N-acetyl-glucosamine
chains [22]. Chitin is converted to a copolymer called chitosan by alkaline deacety-
lation [23]. Chitosan is a linear polysaccharide consists of 2 acetamido-2-deoxy-
d-glucopyranose (acetylated unit) and 2-amino-2-deoxy d-glucopyranose (deacety-
lated unit), which they randomly distributed by β-(1 → 4) linked [24]. Chitosan has
many structural similarities to cellulose, but unlike cellulose, it is considered a new
source. Chitosan is insoluble in water and organic solvent. However, it is soluble
in dilute aqueous acetic, lactic, malic, formic, and succinic acids (acidic solution
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 33
pH < 6.5) [25]. Unlike most commercial polysaccharides (such as starch, cellulose,
dextran, pectin, agar, and agarose) that are neutral or negatively charged (acidic),
chitosan has a polycationic structure and is known as a weak base. Chitosan at neutral
or base pH contains free amino groups that prevent the solubility of this polysaccha-
ride in water, whereas these amino groups in glucosamine units are protonation at an
acidic pH and cause the solubility of chitosan in water [26]. In general, the solubility
of chitosan in water depends on the distribution of free amine and N-acetyl groups in
the molecule. Differences in chitosan (polycationic structure) electrostatic properties
at pH < 6.5 make this polysaccharide interact with anionic polysaccharides such as
carrageenan and alginate. This tendency to interact with other negatively charged
molecules, such as proteins, fatty acids, bile acids, and phospholipids, also applies
[27]. Recent studies show that chitosan tends to chelate metal ions such as iron,
copper, cadmium, and magnesium [28]. In biomedical research, natural materials are
always preferred to synthetic materials due to their high compatibility. Properties such
as biocompatibility, non-toxicity, biodegradability, and antibacterial effect have made
chitosan an interesting polymer in biomedical applications [29]. Numerous studies
have been published on the effect of chitosan on accelerating wound healing. Studies
have shown that chitosan regenerates wound tissue by stimulating homeostasis [30].
In recent years, chitosan has been proposed as an ideal polymer in the fabrication
of tissue engineering scaffolds because N-acetylglucosamine, the monomers that
make up chitosan, is common in hyaluronic acid, which is an extracellular macro-
molecule that plays an essential role in tissue repair [31]. On the other hand, chitosan
polysaccharide can be degraded by some human enzymes such as lysozyme, so its
biodegradability properties apply [32]. Various methods have been developed for
the preparation of chitosan nanocomposites, some of which are mentioned below
(Fig. 2.1).
The physical method in the preparation of polymer composites is the simplest
method that has been widely used in the last two decades [34]. In this simple method,
two or more polymers are mixed to modify properties such as mechanical properties,
permeability, biodegradability, antimicrobial properties, and other properties, and the
resulting composite has properties between the constituent polymers [34]. Using this
method, the properties of polymers can be directed to the required direction based
on the need. This feature is a significant feature of the industry. The most common
methods of preparing polymer composites include cast polymer molding, annealing
method, and extrusion method [35, 36]. Nanotechnology has been used to improve the
properties and create more properties of composites and has led to the manufacture
of nanocomposites with unique properties. Numerous studies have been conducted
in recent years to prepare chitosan nanocomposites and use them in various fields
such as food packaging [37], medical applications [38], drug delivery [19], wound
dressing [39], preparation of membrane filters [40], and other applications [41].
Numerous methods such as photochemical methods, radiolysis, ultrasound, and
application of electrospray technology can be used to synthesize nanoparticles
required to prepare nanocomposites and homogenize them in the chitosan matrix
[42]. Silver nanoparticles have been used for antioxidant and antibacterial prop-
erties in nanocomposites prepared from chitosan or chitosan combined with other
34 Z. Emam-Djomeh and M. Hajikhani
Fig. 2.1 Chemical structure of chitin polymer which is converted to chitosan polymer by
deacetylation [33]
polymers [43]. Zinc oxide is also known as another common nanoparticle used in
nanocomposites prepared for wound healing [44]. The critical point in preparing
nanocomposites is how to prepare nanoparticles and how to add them to the polymer
matrix. The nanoparticles used must have a normal distribution in their particle diam-
eter. Uniformity in size leads to uniform release patterns and better performance of
nanocomposites [45]. They also play an important role in the dispersion of nanoparti-
cles in the polymer matrix. In order to disperse nanoparticles properly in the polymer
matrix, the concentration of the polymer solution should not exceed a certain limit,
and the nanoparticles should first be properly homogenized in a secondary solution
and then added to the polymer solution to homogenize properly. The use of physical
methods such as ultra-turrax homogenizers and ultrasound is another way to homog-
enize nanoparticles. If nanoparticles have non-uniform sizes, it is more difficult to
homogenize them in nanocomposites [46].
In an innovative method published by Qiu et al. [47], chitosan and zinc oxide
flexible nanocomposites were prepared (Fig. 3.2). In this study, zinc ions were
dispersed in a chitosan polymer solution and then prepared by the chitosan/zinc film
casting method. The film’s treatment with sodium hydroxide at a high temperature
(80 °C) causes zinc oxidation and conversion to ZnO. Microscopic examination and
AFM showed good dispersion in zinc oxide nanoparticles. Studies have shown that
ZnO nanoparticles were successfully synthesized in situ in chitosan films. The main
purpose of this work is to provide an easy and green way to make chitosan/ZnO
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 35
nanocomposite films with good compatibility and antibacterial properties, which
shows applications as antibacterial packaging and dressing [47].
The most important property of chitosan that is highly regarded is the antimicrobial
properties of this polycationic polymer. The molecular weight of chitosan, the degree
of acetylation, the degree of substitution, and the properties of the microorganism
wall are among the influential factors in the antimicrobial power of chitosan [48].
Nanocomposites made of chitosan polymer have a positive surface charge that bonds
better to the mucosa [49]. A positive surface charge causes chitosan to attach to the
cell wall of microorganisms negatively charged by phosphate groups in phospholipids
[50]. The amino groups in chitosan bind to the microorganism wall, causing a change
in cell permeability, resulting in osmotic disruption by the influx of ions and proteins
between the cytoplasm and extracellular space, and ultimately inhibiting microbial
activity [51]. The main factor in the antimicrobial activity of chitosan is the positive
charge density of this polymer and its electrostatic interaction with the negative
charge of the cell wall surface of microorganisms [52]. Other properties such as the
degree of deacetylation and degree of substitution affect the positive charge density
of the polymer [53]. Since many free amine groups are available in the polymer
backbone, polymer modification and preparation of chitosan nanocomposites have
shown acceptable results [54]. Recent studies have shown that a decrease in pH
and molecular weight can exacerbate the antimicrobial properties of chitosan by
considering the degree of protonation [55]. This fact means that the higher the degree
of protonation, the lower the pH, and the lower molecular weight of chitosan should
be used to achieve antimicrobial properties [56]. Other studies on chitosan have
shown that low molecular weight in chitosan has a more significant antimicrobial
effect on gram-negative bacteria than gram-positive bacteria [57] (Fig. 2.2).
Numerous studies have been performed on the positive effect of chitosan on
wound healing. For example, hydrogels made from chitosan and polyacrylic acid on
rats showed that wounds healed within 14 days, and regular cell formation was seen
[58, 59]. Further results showed that chitosan increases adhesion between cells and
therefore accelerates healing [60, 61]. The surface properties of the chitosan films
can be modified with the help of different treatments that create different applications
for this biopolymer [54]. For example, the chemical modification of chitosan with
stearoyl increases protein adsorption due to increased hydrophobicity.
On the other hand, the chemical modification of chitosan with phthalic/succinic
anhydride increases the absorption of lysozyme due to increasing the hydrophilicity
of this biopolymer [59]. Studies also show that the use of heparin stimulates growth
factor-related healing at the wound site and accelerates wound healing [62]. Chitosan-
sericin nanofibers were prepared using electrospinning technology to investigate their
effect on wound healing [63]. A polymer solution is charged under very high voltage
in the electrospinning technique and flies to the opposite pole. The polymer solution
undergoes many twists during the movement between the two poles, which causes
it to stretch and narrow the small flow of the polymer [64].
For this reason, nanofibers are formed with a very small diameter, and the solvent
evaporates rapidly due to the ratio of surface to the large volume of nanofibers
(Fig. 2.3). The resulting scaffolds are usually much more effective than films due
36 Z. Emam-Djomeh and M. Hajikhani
Fig. 2.2 Structure of the chitosan film containing zinc oxide nanoparticles is shown in the vicinity
of the control chitosan film. Also, the steps of chitosan nanocomposite treatment with sodium
hydroxide to oxidation Zn nanoparticles within the chitosan matrix can be seen [47]
to the high surface-to-volume ratio [65]. For example, chitosan–sericin nanofibers
have been shown to have high antimicrobial properties against gram-positive and
gram-negative bacteria [63]. Alginate and chitosan nanocomposites along with silver
sulfadiazine nanoparticles show acceptable performance in wound healing [59]. It
was observed that if the alginate content to chitosan is 50%, the release of nanoparti-
cles will be longer and more common, and therefore, the effectiveness of the wound
dressing will be longer [59, 66]. The alginate and chitosan nanocomposite had suffi-
cient swelling ability and showed good compatibility with cells [59]. The effect of
this nanocomposite on fibroblast cells in mice and humans did not show any signs
of adverse effects and caused the formation of fresh epithelium, which leads to
wound healing. Chitosan alginate scaffolding showed antimicrobial effects against
Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli.
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 37
a
b
c
d
Fig. 2.3 a Macroscopic image, b fibrous mat, and c and d structure and dispersion of chitosan
scaffold nanofibers for use in tissue engineering [67]
Further studies also indicate the high compatibility and non-toxicity of this
nanocomposite [59]. In another study, a chitosan hydrogel patch containing encap-
sulated silver nanoparticles was investigated. Chitosan hydrogel is highly swollen,
effectively increases blood clotting efficiency, and non-toxic [68]. This hydrogel
showed a good effect against S. aureus and E. coli microorganisms [69]. Having
suitable mechanical properties such as elasticity is one of the properties of this
hydrogel [59]. Other nanocomposites studied include gelatin–chitosan scaffolds and
polyvinyl alcohol–chitosan nanocomposites with similar results in antimicrobial,
biocompatibility, and non-allergenic properties [70].
Zinc oxide nanoparticles and castor oil in chitosan film were used to evaluate the
effect of inhibiting gram-positive and gram-negative bacteria. Results showed that
the wound dressing and antibacterial properties have properties such as water absorp-
tion, biodegradation, biocompatibility, and wound healing [71]. The results showed
that increasing the concentration of zinc oxide nanoparticles increases the inhibitory
power of nanocomposites against the growth of microorganisms. Plant extracts such
as Juglans regia and Salix alba encapsulated in chitosan hydrogel were studied
to evaluate the effect on wound healing. Studies have shown that the compounds
obtained from the above plants positively affect wound healing, but due to the lack
of inhibition of microorganisms, there i s a possibility of infection in the wound [59].
38 Z. Emam-Djomeh and M. Hajikhani
Chitosan/Aloe vera nanocomposite was proposed as a suitable option due to its anti-
inflammatory and moisturizing properties [72]. The resulting nanocomposite showed
higher efficiency and had more adhesion to wound surface fibroblasts. In uncomfort-
able wounds, chitosan/A. vera nanocomposite can be used as a good dressing [73]. In
other studies, adding bioactive substances such as lupeol, cinnamonic acid, salicylic
acid, phenols, and sulfur on the growth inhibitor of microorganisms was investigated
[59]. Insolubility or low solubility in water at biological pHs is considered to be
the biggest problem of chitosan. Therefore, many efforts have been made to modify
the properties of chitosan through the chemical modification of this biopolymer.
Carboxymethyl chitosan, trimethyl chitosan, and carboxymethyltrimethyl chitosan
are among these modified polymers widely used in targeted drug delivery systems
to improve solubility and water absorption properties [74, 75].
Further studies have identified modified chitosan as a suitable dressing due to its
strong cationic properties derived from trimethylation derivatives [76]. This chitosan-
derived biopolymer also showed excellent mucosal adhesion and a good drug loading
effect [77]. The binding of the carboxymethyl moiety to the chitosan backbone
increases the solubility and biocompatibility of the nanocomposite. The addition
of the carboxymethyl group causes the polymer to have good solubility in a wide
range of pH and creates an excellent gel-forming ability [78].
Chitosan/polyethylene oxide scaffold was fabricated using the electrospinning
technique to investigate the effect on wound healing. Scanning electron microscopy
evaluation showed that with an increasing amount of chitosan, the diameter of
nanofibers increased, and also the elongation strength of the scaffold decreased,
but increasing the amount of chitosan increased the tensile strength. On the other
hand, the amount of polyethylene oxide determined the solubility of the scaffold.
Bioburden studies showed that the 2:1 ratio of polyethylene oxide and chitosan has
a sufficient inhibitory effect against the growth of S. aureus. This polymer ratio also
showed good compatibility in in vivo tests and caused fibroblast proliferation in mice
[79, 80].
In 2015, Shahzad et al. examined the complex of polyvinyl alcohol, hydroxyap-
atite, and chitosan in the preparation of nanofibers, hydrogels, mats, and films [81].
It was observed that the morphology of the polymer complex changes under heat
treatment. SEM studies have shown that the polymer matrix has a porous texture. It
was also found that hydrogel has higher water absorption in phosphate buffer salt
solution at pH 7.4 than other forms. Studies of encapsulation drug release showed that
lyophilized hydrogels did not have a suitable drug release pattern. Microbial studies
showed that polymer composites have suitable antimicrobial activities against E.
coli and S. aureus. At the end of the study, it was concluded that the composite of
polyvinyl alcohol, hydroxyapatite, and chitosan with high biocompatibility, proper
drug release, and high microbial inhibition capacity has a high potential for use in
the manufacture of various wound dressings [81].
The high viscosity of the chitosan solution makes it difficult to use this polymer
in the production of scaffolds with electrospinning technology because the polymer
has low spinning capacity due to its high viscosity and does not tend to form jets
during the process [82]. Various solutions have been introduced to overcome this
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 39
problem in chitosan, including reducing the polymer solution concentration, using
modified chitosan, and using a copolymer with chitosan [83]. The most suitable
way is to use polymers with high spinning properties in the mixture with chitosan,
which causes the physical properties of the chitosan polymer solution to be modified
and spinning [84]. Different copolymers such as polyethylene oxide and polyvinyl
alcohol have been used to produce scaffolds with chitosan in various studies [85]. The
results showed that high compatibility between polymers is observed in nanofibers,
and nanofibers’ morphology is appropriate. The use of copolymers increases the
mobility of ions and increases the electrical conductivity by reducing the viscosity
of chitosan. Electrical conductivity is considered one of the most important physical
properties of the polymer solution in the electrospinning process and has a high
impact on the morphology and diameter of nanofibers. By reducing the diameter of
the nanofibers, the surface-to-volume ratio in the scaffold increases and improves
the efficiency of the wound dressing in attaching to the tissue [82]. Encapsulation of
wound healing compounds in nanofibers causes the release to be done from a larger
surface and in the form of a linear and controllable pattern [86].
In 2013, Archana et al. developed a chitosan/polyvinyl pyrrolidone nanocom-
posite with titanium oxide nanoparticles [87]. Thermodynamic properties, chemical
structure, were investigated by differential scanning calorimetry and Fourier trans-
form infrared spectroscopy. Observation of the microstructure with the help of SEM
reported the proper dispersion of titanium oxide nanoparticles in the nanocomposite.
Nanocomposite mechanical strength studies showed that titanium oxide nanoparti-
cles have a direct effect on increasing tensile strength. The study of the effect of
nanocomposites to inhibit the growth of pathogens had a very positive result. The
use of nanocomposites in the wounds of albino mice to study the effectiveness of
wound healing showed that the chitosan/polyvinylpyrrolidone nanocomposite with
titanium oxide nanoparticles has excellent biological compatibility against fibrob-
lasts and accelerates wound healing. High water vapor transfer rate, good compati-
bility, excellent antimicrobial properties make this nanocomposite ideal as a wound
dressing [59, 87].
Gels consist of two phases, liquid and solid, which in the case of hydrogels, the
liquid phase consists of water [88]. Hydrogels have many applications for use in
living tissues due to their high water content [89]. The hydrogel’s high flexibility and
soft structure make it possible to tolerate the hydrogel on the damaged tissue for a
long time, while the adjacent tissues suffer the least damage [90]. Chitosan does not
require any additives to form a gel and can form a gel network by inhibiting repulsion
between amino groups in its chain and creating hydrogen bonds and hydrophobic
interactions [91]. Hydrogel scaffolds have received a great deal of attention in the field
of tissue engineering in the last decade due to their biodegradability, high biocompat-
ibility, high drug delivery ability, and controlled release. Wang et al. [92] produced
honey/gelatin/chitosan hydrogels and evaluated the properties of this product. The
antimicrobial activity against S. aureus and E. coli was completely successful, and
the hydrogel was safe against the growth of microorganisms. The effect of hydrogel
on the healing of burn wounds during 12 days was investigated, and MEBOVR
ointment was used as a control sample [92]. Honey/gelatin/chitosan hydrogels were
40 Z. Emam-Djomeh and M. Hajikhani
found to accelerate the healing of burn wounds, but these results were not repeated
in the control sample. Histological studies showed the non-toxicity of this hydrogel
to wound tissue [59]. Therefore, it could be concluded that this hydrogel has a high
potential for use as a wound dressing due to its appropriate effect on wound healing,
non-toxicity, biocompatibility, and biodegradability [92, 93]. Lih et al. tested poly
(ethylene glycol)/tyramine/chitosan hydrogels along with hydrogen peroxide and
horseradish peroxidase for use as tissue adhesives [94]. It was observed that polyethy-
lene glycol can increase the solubility of this biopolymer through cross-linking with
chitosan [94]. The study on the mechanical properties of hydrogels showed that by
creating these transverse pins, the adhesion property was strengthened between 3 and
20 times. The study of the effect of hydrogel on the wound for two weeks showed that
polyethylene glycol increases the hemostatic properties of chitosan and accelerates
wound healing [59, 94].
The casting method is known as a simple method in designing various nanocom-
posites. This method uses a high proportion of solvents, which are generally
organic [95]. For example, sodium carboxymethylcellulose (CMC) and propyl-3
trimethylammonium chitosan chloride (HTCC) nanocomposite films were prepared
in combination with PVA N-(2-hydroxyl) [96, 97]. This nanocomposite’s physic-
ochemical and mechanical properties were evaluated, and it was concluded that
hydrogen bonds bonded together with the polymer matrix. It was observed that
moisture permeability, mechanical properties, swelling properties, and water absorp-
tion of composite films change significantly with changes in CMC content [97].
Thus, increasing CMC permeability to water, the percentage of swelling and water
absorption capacity increased, and mechanical properties such as flexibility and
tensile strength were strengthened [96]. Antimicrobial studies on nanocomposite
films showed good antimicrobial activity. In a similar study, the properties of
chitosan/bentonite nanocomposites were investigated. The films were evaluated for
physicochemical properties, including WVTR, water absorption capacity, flexibility,
and thickness. The interaction of positively charged chitosan and negatively charged
bentonite was also investigated by FTIR and film surface morphology using SEM. It
was observed that the hydrophilic nature of bentonite increases the water absorption
capacity and mechanical strength of the films [98]. Antibacterial studies examined
the positive effect of films on the growth of gram-positive and gram-negative bacteria
and found that the films potentially inhibited the growth of microbes, making them
ideal for use in wound dressings [98]. Another study conducted in 2015 by Archana
et al. [99] examined the physicochemical, mechanical, thermal, and microbial prop-
erties of chitosan/polyvinyl pyrrolidone films along with silver oxide nanoparticles.
Due to silver nanoparticles and chitosan polymer, it had high antimicrobial activity
for nanocomposites, and the films also had a high swelling capability. In vivo studies
of the wound showed that the film containing silver oxide nanoparticles had a higher
wound healing ability than the pure chitosan film, which the author identified a
synergistic ability between silver nanoparticles and the chitosan polymer [99].
The use of organic solvents to prepare films by the casting method makes it
possible to prepare the desired polymer matrix easily and even use polymers with
different polarity properties in a polymer solution. The high ability to dissolve
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 41
different polymers makes it possible to produce countless different composites.
However, the toxicity of these solvents is one of the limiting problems of this method.
Solvent residue in the final dressing is an important point that is rarely mentioned
in studies, but due to the rapid absorption and high toxicity of these compounds
must be considered. For example, in the preparation of dressings from composites
containing collagen, the hexafluoro-2-propanol solvent is used, which is highly toxic
and carcinogenic [100]. Various other forms such as membranes, sponges, and emul-
sions with chitosan polymer have been studied for use in dressings with the aim of
accelerating the wound healing process. In addition, loading of bioactive compounds
into chitosan composites yielded acceptable results such as high encapsulation effi-
ciency and a suitable release pattern, which introduces chitosan as a suitable polymer
for use in dressings.
2.3 Poly (Ethylene Glycol)
Polyethylene glycol is a polyether compound derived from petroleum with many
applications in various industries, including the medical industry [101]. This polymer
is named depending on its molecular weight. When the molecular weight of this
polymer is less than 20,000 g/mol, it is called polyethylene glycol or PEG, but
when the molecular weight is higher than 20,000 g/mol, it is called polyethylene
oxide or PEO. Polyoxyethylene or POE is another name for PEO [101, 102]. As
shown in Fig. 3.4, PEG structure is usually expressed as H(OCH2CH2)nOH, which
is the average repetition of oxyethylene groups in the polymer chain, and n can
vary from 4 to 180 [103]. The properties of this polymer vary depending on its
molecular structure, but they are all jointly soluble in water. Other properties of
polyethylene glycol include non-toxic, odorless, neutral, lubricating, non-volatile,
and non-irritating properties that can be used in many pharmaceutical products [104].
PEG, for example, can reduce protein uptake and prevent the formation of the protein
corona, which is critical in drug delivery systems [105]. PEGylation or pegylation
is another application of this polymer in which PEG is covalently or non-covalently
bonded to a macromolecule such as a protein [106]. This phenomenon keeps the
drug functional groups hidden from the immune system and prevents immune and
allergic responses. It also increases the hydrodynamic size of the drug in solution,
which reduces drug clearance due to increased circulatory time [107]. Also, with the
help of this technique, hydrophobic drugs can be converted into the water-soluble
form [107] (Fig. 2.4).
Various studies have shown the solubility of polyethylene glycol in water, ethanol,
dichloromethane, acetonitrile, and benzene. Also, this polymer is insoluble in hexane
and diethyl ether [109]. The polyethylene oxide molecule has a semi-crystalline
structure and is easily soluble in water due to its high affinity for hydrogen bonding
with the water molecule [110]. High solubility and adhesion properties have led to
the use of polyethylene oxide as an essential material in the design of bioadhesive
and mucoadhesive systems, especially in drug delivery systems and wound healing
42 Z. Emam-Djomeh and M. Hajikhani
Fig. 2.4 Different forms of ethylene glycol polymerization [108]
[61]. The big problem in using PEO is the lack of sufficient mechanical strength and
hydrophobicity properties [111]. Numerous studies have been published on polymer
composite with PEO in which attempts have been made to modify this polymer’s
physicochemical and mechanical properties [112]. In this regard, conducted studies
on the properties of chitosan/polyethylene oxide composites [112]. It was observed
that a 50/50 ratio of two polymers reduces the tendency to spherulitic crystallization.
As a result, the transparency of the films is reduced, and the films are seen as opaque.
The study on the mechanical properties of chitosan/polyethylene oxide film showed
that the addition of chitosan is significantly effective in improving mechanical prop-
erties such as tensile strength (TS), elongation (E), and puncture strength (PuSt).
Also, by doubling the ratio of chitosan to polyethylene oxide, PuSt and TS increased
by 80% and 56%, respectively. The barrier properties of the film were also tested.
Compared to PEO control films, the results are a tenfold increase in water vapor
permeability (WVP) in chitosan/polyethylene oxide films [113].
The reason for this is the compactness of the film structure and the better place-
ment of the polymer chains in the PEO in a special region. However, the addition
of secondary polymers disrupts the order in PEO polymer chains and increases the
intermolecular distance, so water vapor permeability should be increased. Finally, the
author described the presence of chitosan as essential for the mechanical properties
of PEO [113, 114]. Polyethylene glycol is known in biomedicine as an antifouling
polymer [115]. According to research, PEO, with its surface hydration ability and
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 43
steric hindrance effect, prevents sedimentation. PEG is attached to the surface of
the material from one side, and due to its high solubility in water, it increases the
solubility of materials in water [116]. Polyethylene glycol is widely used to prepare
dressings due to its biocompatibility, low toxicity, hydrophilicity, flexibility, and non-
immunogenic properties [117]. PEG macromers can bind to growth factors such
as epidermal growth factor, which delivers this polymer to the wound site. PEG-
based dressings have been widely used to heal diabetic wounds by strengthening and
inducing skin cell growth and collagen deposition [5]. Acceleration of wound healing
by collagen deposition also reduces scar formation. The biggest problem in making
a dressing from this polymer, as mentioned above, is its poor mechanical proper-
ties, which can be eliminated with the help of a copolymer [118]. Combining PEG
with other polymers significantly enhances the mechanical properties of PEG-based
dressings and even alters the thermodynamic properties of this polymer. Improving
thermodynamic properties can be helpful in drug delivery systems by encapsulating
bioactive compounds that are sensitive to environmental conditions [119].
In another study by Rengifo et al. [120], chitosan/polyethylene oxide nanofibers
were used to treat skin cancer. Carboxymethyl-hexanoyl chitosan and dodecyl sulfate
nanoparticles were used in the preparation of nanofibers (Fig. 2.5). Pyrazoline was
loaded into the nanoparticles as an anticancer agent and then added to the polymer
solution. Morphological studies showed a homogeneous structure of nanoparticles
within chitosan/polyethylene glycol scaffolds. The release pattern of nanoparticles
and pyrazoline was investigated for 120 h. It was observed that when carboxymethyl-
hexanoyl chitosan and dodecyl sulfate nanoparticles are used as carriers, the rate
of pyrazoline transport through the epidermis should also be increased. Therefore,
chitosan/polyethylene oxide scaffolds can be used for controlled drug release in
topical chemotherapy for skin cancer [120].
Fig. 2.5 Steps for preparing a scaffold from a polymer mixture of chitosan and polyethylene oxide.
These nanofibers contain carboxymethyl-hexanoyl chitosan/sodium dodecyl sulfate nanoparticles
loaded with pyrazoline to treat skin cancer [120]
44 Z. Emam-Djomeh and M. Hajikhani
2.4 Chitosan/Poly (Ethylene Glycol)/ZnO
Bionanocomposite
Zinc oxide is an inorganic compound, insoluble in water and the form of a white
powder. The chemical formula of this substance is ZnO, and it is used as an additive
in countless products such as food, medicine, and even building materials [121].
Zinc oxide is a natural form of zinc in nature, but most of it is produced in synthetic
form worldwide [122]. ZnO is considered a non-toxic and non-allergenic substance
that is used in skin and eye care products. The use of ZnO in skin wounds has been
shown to inhibit IgE secretion and suppress allergic reactions [123]. The effects
of ultraviolet light absorption and refraction have been demonstrated by zinc oxide
nanoparticles, which is why zinc oxide nanoparticles are used in sunscreen prod-
ucts. Recent studies have reported the toxic effects of high doses of zinc oxide
nanoparticles on human skin [124]. The study showed that if ZnO nanoparticles
are too small, it disrupts intramolecular biomolecules, causing protein unfolding,
fibrillation, thiol cross-linking, and ultimately loss of enzymatic activity [125]. Zinc
oxide can inhibit the growth of microorganisms through the process of photoinduced
oxidation. Numerous studies have shown the positive effect of ZnO against the inac-
tivation of gram-positive and gram-negative bacteria [126]. The use of ZnO and
other metals also improves the efficiency of solar energy and enhances the antibac-
terial effect of other metals [127]. For example, the effect of Fe/ZnO nanowires in
comparison with ZnO and TiO2 against the growth of E. coli was studied [128]. Their
results showed that ZnO/Fe nanowires have higher photocatalytic activity than pure
ZnO. The addition of cobalt to Fe/ZnO nanoparticles increased the particle size and
showed antibacterial activity against four strains of bacteria. Attractive properties of
zinc oxide cause it to be used in the form of nanoparticles in polymer composites to
improve the film’s functional properties such as mechanical, barrier, and antibacterial
properties [129].
The attractive properties of zinc oxide due to its application in the form of
nanoparticles in polymer composites improve the film’s functional properties such
as mechanical properties, barrier, and antibacterial [130]. Liu and Kim [131] studied
the properties of genipin-cross-linked chitosan (GC) and polyethylene glycol (PEG)
composites along with zinc oxide and silver nanoparticles on wound healing. It
was observed that at high doses of nanoparticles, there is a good dispersion in
the composite. The swelling properties of the nanocomposite were completely pH-
dependent, which is due to chitosan. On the other hand, the nanoparticles significantly
improved the mechanical strength of the nanocomposite. It was observed that with
increasing ZnO content, the antimicrobial activity of the films increased [131]. The
antibacterial activity of GC/PEG nanocomposite samples was tested in the form of
containing and without nanoparticles against the bacterial species E. coli, P. aerugi-
nosa, S. aureus, and Bacillus subtilis. It was observed that GC/PEG composite films
containing zinc oxide and silver nanoparticles had higher antibacterial activity than
GC/PEG nanocomposite films without nanoparticles and GC/PEG containing zinc
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 45
oxide [132]. This antimicrobial effect is intensified by silver, which is due to the
doping of zinc oxide with silver [133].
In 2020, Sithique and Sakthiguru [134] investigated the physicochemical prop-
erties of carboxymethyl chitosan nanocomposites and zinc oxide and lawsone
intending to be used as wound dressings. The chemical properties and bonding
between nanoparticles and carboxymethyl chitosan were investigated by Fourier
transfer infrared spectroscopy (FT-IR). The amorphous and crystalline properties of
the nanocomposite were investigated using X-ray diffraction (XRD). As shown in
Fig. 2.7, the microstructure of the nanocomposite and the distribution of nanoparticles
in the film were investigated using scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM). Finally, thermogravimetric analysis (TGA) was
used to analyze the temperature resistance of the film. Encapsulation and release
patterns in phosphate buffer saline were investigated, and it was observed that the
nanocomposite has efficient properties in encapsulation and release. In vivo studies
showed no signs of allergenic properties, and the nanocomposite had high biocompat-
ibility. Microbiological studies showed high antimicrobial properties for nanocom-
posites. These biological properties indicate that the carboxymethyl chitosan/zinc
oxide/lawsones nanocomposite has a high potential for acting as an excellent biolog-
ical material in wound healing applications [134]. In a recent study by Masud
et al. [12], the bionanocomposite properties of cross-linked polyethylene glycol
with sodium tri polyphosphate containing chitosan-ZnO nanoparticles were investi-
gated to act on wound healing. The antibiotic gentamicin was used as a widely used
substance in preventing wound infection and assisting wound healing in bionanocom-
posite, and the release of this antibiotic was investigated. Cytotoxicity analysis was
performed on Vero cells and BHK 21 cells, and both confirmed the biocompatibility
results of the bionanocomposite. Studies on antimicrobial properties have reported
the ability of bionanocomposites against the growth of E. coli and Salmonella
enterica. In vivo evaluation showed that drug-containing bionanocomposite has
better therapeutic properties than natural dressing and drug-free bionanocomposite
due to the synergistic effect of drug and ZnO nanoparticles (Fig. 2.6). Bionanocom-
posite showed an optimal loading efficiency of 76% with a drug concentration of
300 ppm, which is a significant efficiency among similar studies. High compatibility,
biodegradability, high resistance to microorganism growth, good release pattern, and
high encapsulation capability make this bionanocomposite suitable for use in wound
dressings [12].
In another study by Preethi et al. [135], Solanum lycopersicum leaf extract was
loaded into a chitosan/zinc oxide nanocomposite. Characteristics of the obtained
nanocomposite were examined by various tests such as visible, ultraviolet spec-
troscopy, X-ray diffraction (XRD), field irradiation scanning electron microscopy
(FE-SEM), transmission electron microscopy (TEM), and scattered energy X-ray
spectroscopy (EDS). Chitosan/zinc oxide nanocomposite showed significant antibac-
terial activity against S. aureus-induced skin infection, making this nanocomposite an
ideal wound dressing. In addition, chitosan/zinc oxide nanocomposite was studied
for antibacterial activity against S. aureus, B. subtilis, and E. coli, which showed
acceptable results in inhibiting the growth of microorganisms [135].
46 Z. Emam-Djomeh and M. Hajikhani
Fig. 2.6 Demonstration of effect of chitosan/polyethylene glycan nanocomposite containing zinc
oxide nanoparticles on wound tissue repair in an animal model [12]
Fig. 2.7 Dispersion of zinc oxide nanoparticles in the chitosan/polyethylene glycol bionanocom-
posite by FESEM [12]
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 47
Teicoplanin-containing PEO/chitosan scaffold was developed by Amiri et al.
[136] using electrospinning technology. The purpose of this scaffold was to create
antibiotic-loaded drug delivery systems to overcome several antibiotic-related limi-
tations. The antibiotic-loaded scaffold can be applied topically for skin and wound
healing and post-operation implants to prevent abdominal adhesion and prophylaxis
and treat infections in orthopedic surgery. The author recommends doses of 2 and
4 wt% teicoplanin for bead-free nanofibers. The antibiotic release study showed that
the scaffold was able to release teicoplanin within 12 days. This long period of time
increases the lifespan of the wound dressing and makes it cost-effective to use due
to the small number of dressings required in a treatment period. Antibacterial testing
against S. aureus showed that loading teicoplanin into the chitosan-PEO nanofibers
maintained the antibiotic’s antibacterial activity and increased it by 1.5–2 times.
Cellular studies did not show any toxicity against human fibroblasts. In addition, an
in vivo study of a wound model in a rat confirmed the efficacy of teicoplanin-loaded
nanofibers. It was observed that a significant improvement in wound closure was
created, especially with nanofibers containing 4% teicoplanin [136]. The pattern of
sustained-release, intensified drug activity, cell compatibility, and significant wound
healing activity confirm the potential applications of teicoplanin-rich nanofibers in
wound healing and topical antibiotic delivery [137].
2.5 Wound Healing Application
The skin is the largest organ in the body that protects the body from damage caused
by external stress [64]. The skin protects our body from microorganisms, helps
regulate body temperature, and creates a sense of touch, heat, and cold. As shown in
Fig. 2.8, the skin generally consists of three layers: the epidermis, the dermis, and the
hypodermis [138]. As the name implies, the epidermis layer is located in the most
superficial part of the skin and creates the color of the skin [139]. This layer also
provides waterproof insulation of the skin. Below the epidermis is the dermis layer,
made up of connective tissue and contains hair follicles and sweat glands. Finally, the
last layer, the hypodermis, is the deepest layer of the skin [140]. This layer consists
of adipose tissue and connective tissue. Skin pigmentation is caused by special cells
called melanocytes that produce melanin pigment [141]. Melanocytes are located in
the epidermal layer, so the epidermal layer is responsible for skin color [142].
The process of replacing damaged or destroyed tissue with new tissue is called
wound healing. In intact skin, the epidermis and dermis provide a protective barrier
against the external environment [144]. Damage to the skin creates a series of
biochemical events to repair the damage. Blood clotting (homeostasis), inflamma-
tion, tissue growth (cell proliferation), and tissue regeneration (cell maturation and
differentiation) are the four stages of wound healing [145]. In the homeostasis stage,
which is in the first minutes of injury, blood platelets begin to stick to the affected
area [146]. In this phase, the platelets become amorphous to better participate in the
structure of the clot, and also in this state, it creates a signal that causes the secretion
48 Z. Emam-Djomeh and M. Hajikhani
Fig. 2.8 Different layers of skin in a cross section of human skin [143]
of fibrin, and the fibrin acts as an adhesive and strengthens the structure of the clot
[147]. The hemostasis phase causes blood clots to form to reduce the severity of the
bleeding and stop it [148]. Inflammation stage white blood cells by phagocytosis
swallow damaged or dead cells along with bacteria and other pathogens [149]. At
the end of this phase, platelet-derived growth factors are released into the wound,
causing cells to migrate and divide into the next stage, the proliferative stage [150].
In the reproduction stage, which is the most complex stage, different processes occur
together. Angiogenesis or regeneration of blood vessels is the stage that causes the
regeneration of new vascular endothelial cells [151]. In fibroplasia and granulation
tissue formation, fibroblasts grow and form a new temporary extracellular matrix
by secreting collagen and fibronectin [152, 153]. At the same time, epithelial cells
proliferate and move to the wound surface to re-epithelialize the epidermis [153]. In
the contraction phase, which has a mechanism similar to that of smooth muscle cells,
myofibroblasts reduce the size of the wound by gripping the edges of the wound and
contracting [154]. Cells that have fulfilled their role suffer from cell death or apop-
tosis. During puberty and regeneration, which is the final stage of wound healing,
collagen is adjusted along the stretch lines, and cells that are no longer needed are
removed with programmed cell death or apoptosis [155]. Numerous biopolymers are
used today for wound healing, including chitosan and polyethylene glycol. Chitosan,
which is known as an antimicrobial polymer, has several other properties in wound
healing.
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 49
Chitosan activates leukocytes and macrophages for phagocytosis and the produc-
tion of IL-1, TGF-β, and PDGF [156]. This biopolymer also stimulates cell prolif-
eration, which in turn accelerates wound healing [157]. Stimulation of fibroblast
proliferation is another advantage of using chitosan as a dressing [119]. The degree
of chitosan acetylation is considered a significant factor in fibroblast stimulation
[158]. In order to modify and optimize the properties of chitosan, various copolymers
have been used in the production of scaffolding, hydrogels, films, and nanocompos-
ites. The combination of chitosan with other biopolymers, in addition to modifying
the properties of this polymer, has shown promising results in wound healing. For
example, study on the performance of carboxymethyl chitosan in patients under-
going plastic surgery showed that chitosan promotes better-organized skin tissue
and reduces abnormal healing [7]. The chitosan and polyethylene glycol complex
also improved chitosan properties by intensifying adhesion, protein adsorption, and
stimulating cell growth [159]. Several studies have been performed on diabetic
wound healing and burns in mice. Surface binding of growth factors to chitosan and
binding of EGF and bFGF to chitosan were observed, improving wound healing by
increasing wound contraction and increasing epithelialization, respectively [160].
The polycationic properties of chitosan make it an ideal carrier for encapsulating
drug compounds. The addition of curcumin to chitosan increased collagen synthesis
in vitro and in vivo [161].
Zinc is an essential trace element in the human body of great importance in times
of health and illness [162]. Zn acts as a cofactor in various transcription systems and
is also involved in zinc-dependent enzyme systems, including metalloproteinases,
which increase the autoimmune degradation and migration of keratinocytes during
wound healing [163]. Zinc protects the cell against reactive oxygen species and
bacterial toxins through its antioxidant activity [164]. Zinc’s antioxidant activity is
probably mediated by cysteine-rich metallothioneins, eventually leading to resistance
to epithelial apoptosis [165]. It has been observed that delays in wound healing are
caused by a lack of zinc in the diet or hereditary reasons [163]. Zinc protects the cell
against reactive oxygen species and bacterial toxins through its antioxidant activity
[166]. Zinc’s antioxidant activity is probably mediated by cysteine-rich metalloth-
ioneins, eventually leading to resistance to epithelial apoptosis [167]. It has been
observed that delays in wound healing are caused by a lack of zinc in the diet or
hereditary reasons [163]. Further studies have shown that topical zinc administration
is more effective in reducing infection than oral administration because it strengthens
local defense systems, collagenolytic activity, and continuous release of zinc ions,
ultimately stimulating wound epithelialization in normoglycemic individuals [18].
The use of zinc oxide in wound dressings reduces skin inflammation and soothes
wounds [18].
Metallothioneins (MT) can complex with intracellular zinc up to 20%. MT is a
family of proteins attached to minor metals highly protected and rich in cysteine
[168]. This protein is considered for zinc homeostasis, protection against oxidative
stress, and buffer against toxic heavy metals [169]. MTs regulate gene regulatory
molecules and zinc stores within the cell and protect cells from the damaging effects
of exposure to high zinc levels [170]. Each MT molecule can bind to seven zinc
50 Z. Emam-Djomeh and M. Hajikhani
molecules [171]. The addition of zinc ion supplementation causes fragmentation
in many biochemical and molecular events related to wound healing through over-
regulation of MTs and metalloenzymes. Also, defective mRNA encoding of growth
factors is usually associated with the expression of finger zinc transcription factors
that impair wound healing [18]. Atomic absorption spectroscopy and immunohisto-
chemical techniques can be used to show the quantitative and qualitative distribution
of zinc in skin wounds. These techniques can be used to determine zinc-binding
proteins such as MT [18].
Differential regulation of the MT gene is performed by a family of proteins
called interleukin-1 (IL-1), a group of 11 cytokines. IL-1 creates a complex network
of proinflammatory cytokines regulating and initiating inflammatory responses by
expressing integrins on leukocytes and endothelial cells [172]. This mechanism may,
to some extent, cause a significant increase in zinc in the early inflammatory stage
of wounds. An initial increase in zinc levels is associated with high MT in marginal
keratinocytes, macrophages, and cutaneous fibroblasts [163]. In later stages, the
population of epidermal basal cells increases, while this increase coincides with MT
deposits [173]. In the final stages of wound healing, the zinc level in the wound
decreases, which is associated with decreased mitotic activity and scar maturation
[163]. Demonstrations of zinc metalloenzymes such as alkaline phosphatase, RNA
and DNA polymerases, and MMP can be used to demonstrate evidence for the func-
tional role of zinc in repair systems [174]. Alkaline phosphatase, which is present
in the early stages of angiogenesis, is a sensitive marker for small cutaneous blood
vessels and increases inflammatory activity and connective tissue proliferation [175].
DNA polymerases also act as precise markers of cell proliferation [18].
Matrix metalloproteinases (MMPs), also called matrixes, are calcium-dependent
metalloproteinases zinc endopeptidases [176]. MMPs themselves are subsets of a
family of proteases called the metzincin superfamily. About 25 MMPs with similar
human characteristics have been identified so far, all of which have an N-terminal
hydrophobic domain, a propeptide domain, and a catalytic zinc-binding domain
[176]. The catalytic domain of MMPs consists of a slot containing a catalyst with a
tight connection to Zn2+ to which the substrate is initially attached before cleavage
[177]. This domain also has an additional Zn2+ structure [18]. MMPs generally have
various proteolytic properties and are capable of destroying all components of the
extracellular matrix [178]. MMPs react with a wide range of protein and glycoprotein
substrates, including cytokines, cytokine receptors, adhesion molecules, and latent
MMPs [179]. MMPs are synthesized under specific conditions and by different cell
types in the wound [180]. Keratinocytes in wound margins, macrophages, fibroblasts,
and endothelial cells usually synthesize MMPs differently under the influence of
extracellular matrix–cell contact and soluble intermediates [181]. MMPs are synthe-
sized as the inactive proenzyme or cysteine residue [182]. The proenzymes form a
predomain to cover the catalytic site. Disruption of this predomain exposes zinc ions
to catalytic binding to the s ubstrate [177]. Among the MMPs, some are involved
in wound healing, including collagenases, stromelysin, gelatinase A, and gelatinase
B. Collagenases, including MMP-1, MMP-8, and MMP-13, break down the triple
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 51
helix collagen [180]. MMP-2 and MMP-9, which contain gelatinase A and gelati-
nase B, destroy interstitial and denatured collagen, subcutaneous type IV collagen,
and gelatin. Stromelicins, including MMP-3 and MMP-10, contain a wide range of
substrates in the wound bed [183].
Zinc is directly involved in regulating the mechanism of action of MMPs in
wound destruction, proteolytic characterization, modulation of cell migration, and
regeneration of extracellular matrix. The inherent mechanisms of regulation of most
endogenous enzymes depend on zinc ions [184]. The integrin genes α2β1, α3β1,
α6β4, and αvβ5 are responsible for keratinization and keratinocyte migration in the
skin; the expression of these genes requires the presence of zinc ions [185]. Zinc
can modulate epithelialization in skin wounds through the expression of integrin in
keratinocytes [163]. Zinc supplementation induces the α2, α3, αv, and α6integrin
subunits, which affect the movement of keratinocytes during the recovery phase
[186, 187].
Recent studies in rats have shown that topical zinc therapy effectively reduces
wound debris and promotes epithelialization in surgical wounds [163]. It was
concluded that topical application of zinc and zinc oxide reduces wound residues and
necrotic material in wounds caused by various causes by contributing to the activity
of MMPs. Conversely, inhibition of MMP due to lack of zinc ions significantly delays
wound healing [163, 188, 189].
Further studies in mice showed that reducing zinc ions from the diet delayed
wound healing in laboratory mice compared to regular diets [190]. However, this
reduction in zinc in the diet did not deplete the zinc stores in the skin unless zinc
was wholly removed from the rats’ diet for a long time. It was observed that collagen
biosynthesis due to the reduction of zinc in the diet of mice occurs at a slower rate
[191]. The decrease in zinc ions also disrupted the function of metalloproteinases,
which cleave the peptide of procollagen molecules, and affected collagen synthesis
[192]. By adding zinc to the mice’s diet, the wound healing process returned to
normal. It was observed that the use of topical zinc oxide regardless of the status
of zinc in the diet of mice healed the wound within 12 days [163]. Improvement of
epithelialization by zinc supplementation treatment can be concluded from different
perspectives [163]. Involvement of zinc ions in DNA polymerase in mitosis is
observed through increased nuclear MT in wound peripheral keratinocytes and active
mitotic cells of the basal epidermis [193]. Another reason is the ability of zinc to
regulate endogenous growth factors, which mimics the function of growth factors
by increasing intracellular mitogenic signaling pathways [187]. For example, zinc
ions increase insulin-like growth factor I, which can increase epithelialization [163].
The following reason is probably due to the properties of zinc ions in protecting the
cell against oxidative stress and bacterial toxins, which have an anti-apoptotic effect
on the epithelium [126]. It was observed that zinc increased locally in keratinocyte
proliferation in adult rat wounds by about 30% compared to resident epidermal
keratinocytes and localized zinc oxide [163].
Numerous studies have been performed to investigate the effect of zinc ions on
non-skin lesions such as gastrointestinal wounds (stomach and intestines) [194].
Increasing the dose of zinc in serum collagen deposition in the gastrointestinal wound,
52 Z. Emam-Djomeh and M. Hajikhani
especially anastomotic wound, should increase significantly. In a similar study, daily
zinc intake in rabbits was investigated to affect colon anastomosis healing. It was
observed that 2 mg/kg body weight of zinc ion daily could increase fibroblast pene-
tration and increase epithelialization [195]. Regarding gastric wounds in rats, it was
observed that zinc deficiency could affect mucosal regeneration, and increasing the
amount of zinc ions improved the wound of normal and diabetic rats compared to
the control samples [18]. The function of zinc ions in all stages of wound healing is
summarized in Fig. 2.9.
Today, zinc is used in various forms to heal various wounds. The standard form
of zinc consumption is topical and used in zinc chloride, zinc sulfate, and zinc oxide.
Further studies further elucidated the antimicrobial properties of zinc [196]. Topical
application of zinc significantly reduced the use of oral antibiotics compared to oral
therapy. It was also observed that S. aureus could grow in wounds treated with zinc
oxide significantly less than untreated samples [197, 198].
Numerous studies have been performed on zinc’s antimicrobial properties, and
it has been found that this substance has an inhibitory effect against the growth of
some microorganisms. The growth ability of gram-negative microorganisms is higher
than gram-positive in the presence of zinc ions, but the dose of growth inhibitor is
different in different microorganisms [126]. The inhibitory effect of zinc ion on
S. aureus, Streptococcus, E. coli, Enterobacter, Klebsiella, Proteus, Enterococcus,
and P. aeruginosa was investigated, and it was found that zinc ion can inhibit the
Fig. 2.9 Function of zinc ions in all stages of wound healing [163]
2 Chitosan/Poly (Ethylene Glycol)/ZnO Bionanocomposite for … 53
growth of all organisms in sufficient concentration [199, 200]. Zinc oxide also had an
inhibitory effect against S. aureus and an aerobic and anaerobic endodontic pathogen
[201]. Zinc is naturally thought to be an essential regulator of macrophages and
multinucleated leukocytes in the bone marrow, thymus, and tissues with high cell
turnover [202]. Antioxidant activities of zinc ions against sulfhydryl groups have
been reported [167]. The use of different forms of zinc in various dressings such as
biofilms, scaffolds, hydrogels, and nanocomposites has shown high effectiveness in
wound healing, anti-inflammatory and antimicrobial properties, which makes zinc
a suitable option for use in dressings [203]. A significant point about zinc, which
causes the widespread use of this compound in skin treatment products, is the rarity
of zinc allergy in people using this substance [163, 204].
2.6 Conclusion
All of the above points to the increasing importance of chitosan polymer in designing
efficient dressings in wound healing. Properties such as abundant availability, strong
antimicrobial properties, biodegradability, and biocompatibility can be seen in
chitosan dressings. Among these, polyethylene glycol was proposed as an inex-
pensive, biocompatible, low toxic, flexible, non-immunogenic properties and avail-
able polymer to modify the properties of chitosan, which can improve the solu-
bility of chitosan in water. Also, the mechanical strength of polyethylene glycol is
strengthened in combination with chitosan. Increasing the solubility in water in the
chitosan/polyethylene glycol composite improves the encapsulation properties of the
polymer matrix, so different compounds are easily dissolved and dispersed in this
matrix. It has been shown that PEG macromers can bind to growth factors such as
epidermal growth factor that deliver this polymer to the wound site, so the appli-
cation of this polymer in the delivery systems of healing compounds seems to be
very useful. The information mentioned above about the effect of zinc ion on wound
healing makes this mineral ion a suitable option for use in wound healing. Therefore,
chitosan/polyethylene glycol nanocomposite containing zinc oxide nanoparticles is
introduced as an ideal option in dressing preparation.
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Chapter 3
Preparation and Applications
of Chitosan–Gold Bionanocomposites
Rishabh Anand Omar and Monika Jain
3.1 Introduction
The advancement in new technologies, industrial development and dramatic popula-
tion explosion has resulted in the environment pollution. As a consequence, a sharp
enhancement in the utilization of freshwater has been experienced in the last few
decades leading to the generation of huge amount of wastewater. The effluents from
various sources (industries, dye houses) are directly discharged into the ambient
environment without any treatment. A survey indicated that due to consumption
of freshwater, the gross per capita availability of freshwater would decrease in the
coming 30 years [1]. Approximately, partial population of the world would face the
infirmity and crises caused due to freshwater storages and generation of huge amount
of wastewater [2]. The main cause behind the steady downturn of quality of water is
the discharge of various heavy metals and dyes which are emitted directly into the
environment from industrial productions of various things. Effluent from numerous
industries such as paint, leather, textile and paper making is the key source of heavy
metals, dyes and other toxic pollutants. Heavy metals and dyes can find their way
into human body through food chains and accumulate there. Accumulation of these
contaminants is toxic to human brain cells, growing foetus and may also lead to
other diseases such as anaemia, gastric dysfunction, brain damage, bone softening
and cancer [3]. Therefore, it has become the need of the hour to develop such mate-
rials which could remove these harmful contaminants from water before discharging
R. A. Omar
Centre for Environmental Sciences and Engineering, Indian Institute of Technology,
Kanpur 208016, India
M. Jain (B)
Department of Natural Resource Management, College of Forestry, Banda University of
Agriculture and Technology, Banda 210001, India
e-mail: monika.biorem@gmail.com
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_3
67
68 R. A. Omar and M. Jain
into the environment so that the treated water can be recycled and reused for various
other purposes.
In the past, several wastewater treatment methods have been developed, viz.
advanced oxidation [4], membrane filtration [5], coagulation [6], adsorption [7] and
biodegradation [8]. Among them, the adsorption has been contemplated as the most
efficient method for treating wastewater due to some remarkable advantages such
as cost-effective operations, highly efficient, diverse and simple design [9]. In order
to treat heavy metal and dye-laden wastewater, various adsorbents such as porous
organic polymers (POPs), carbonaceous materials, clays, biopolymers like chitosan,
cellulose and lignin have been successfully fabricated and modified efficiently for
their application in wastewater treatment [10].
Recently, chitosan and its derivatives (metal nanoparticle-doped chitosan
composite) have been used successfully in heavy metal and dye removal applica-
tions as a different class of adsorbents because of their characteristics such as high
surface area, surface hydrophilicity, surface electronegativity, cation exchange selec-
tivity and cation exchange capacity (CEC). These properties have developed a keen
interest among the researchers to use the metal-chitosan composites in environment
remediation applications [11, 12].
Chitosan is a derivative of chitin, formed by deacetylation of chitin (Fig. 3.1).
It is mainly composed of two subunits, namely deacylated d—glucosamine and
acylated N—acetyl—d—glucosamine. These two subunits are joined together by
β (1–4) linkages. The beauty of the chitosan lies in the fact that it has abundant
amino and hydroxyl groups which forms strong bonds with heavy metals and dyes
via co-ordination bond. This amino group of chitosan gets protonated at low pH and
interacts with anionic pollutants via electrostatic interactions. In recent years, several
studies have been carried out on the removal of heavy metals and dye contaminants
from wastewater using chitosan and its derivatives as an efficient adsorbent. Thus,
chitosan-based nanocomposites such as foams, films, hollow fibres and hydrosols
could be used as an efficient material for the wastewater treatment applications.
Chitosan has some unique properties of, such as biocompatibility, excellent film
formation and good mechanical strength due to which it is widely used in various
applications like wastewater treatment [13].
Removal of heavy metals and dyes using chitosan and metal-doped chitosan
nanocomposite has been exhaustively explicated in this chapter. Firstly, a brief intro-
duction to the various studies structure and applications of heavy metals and dyes
removal using chitosan and chitosan metal/gold nanocomposite is presented. Then
different procedures for synthesis of chitosan and chitosan–gold nanocomposite are
given. In continuation with that, various application and mechanism of the chitosan–
gold nanocomposites for the removal of heavy metal and dye are explained. This
chapter provides brief information on the removal of dyes and heavy metals using
the chitosan and chitosan–gold nanocomposite.
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 69
Fig. 3.1 Structures of chitin and chitosan
3.2 Chitosan–Gold Nanocomposite
A functionalized polymer such as chitosan incorporated with any inorganic nanopar-
ticle is called polymer nanocomposite. Polymer nanocomposite represents a tremen-
dous pathway to achieve benefits from two constituents in one entry. Also, sometimes
polymer nanocomposite personifies the new features which are not present in its
components due to the formation of a new product [14]. These tempting properties
of polymer nanocomposites open up a wide variety of implementation in various
fields such as waste management, treatment of wastewater, catalysis, energy, drug
delivery, biomedical, semiconductor and others [15–21].
In recent studies, nano-sized reduced gold nanoparticles (AuNPs) showed
outstanding catalytic activity in mild physical parameters like pressure and tempera-
ture, because of their tiny size, which provides high surface-to-volume ratio and high
chemical potential [22–25]. AuNPs also showed some drawbacks in past studies,
which i nclude mainly (i) In solution, AuNPs encounter several hassles during the
actual applications, (ii) AuNPs have high surface energy, which leads to instability
and aggregation, resulting in remarkable reduction in their catalytic activity [26,
27], (iii) at last, the AuNPs cannot be recaptured and reused, which makes them
cost-inefficient for large industrial applications [28].
Incorporation of these NPs into a solid matrix for a support could be the best
solution for these problems. They provide a competent way to remove the NPs from
the spent solution for their reusability, which makes the whole process cost-efficient
[29]. In addition, the hybrid composite (matrix/AuNPs) gains some unique properties
because of combining nanoparticles to solid matrix structures. These properties are
not present in individual components of the composite.
In past studies, several solid matrices have been developed by doping the nanopar-
ticles as nanocatalyst, like metal oxides [30], carbonaceous such as carbon beads,
nanofibers and nanotubes [31–33], graphene oxides [34, 35], sand [36], silica [37]
and polymers [38]. The polymeric materials as a matrix have been widely used due
to several reasons including, (i) a variety of their structures which makes the surface
70 R. A. Omar and M. Jain
of the material multifunctional, (ii) ease of preparation in different forms such as
hydrogel, aerogels, fibres and films, (iii) easy to separate from the spent reaction
medium and (iv) at the last, cost efficiency.
3.3 Preparation Strategies for Chitosan–Gold
Nanocomposite
Synthesis of chitosan-based nanocomposites is simple and quite successful because
it uses certain blending agents such as chemical agents, aqueous extract and some
biological reducing agents. In nanocomposites synthesis, sometimes the compo-
nents of the nanocomposite (NPs or matrix) are synthesized individually and then all
the components are mixed to achieve the final product as a nanocomposite. But in
others, a final nanocomposite (metal-polymeric product) is achieved by a single step
process. This section discusses the different methods of preparation of chitosan–
gold nanocomposite. Figure 3.2 briefly describes various methods of synthesis of
chitosan–gold nanocomposite.
Fig. 3.2 Various methods of synthesis of chitosan–gold nanocomposites
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 71
3.3.1 General Synthesis
Generally, the nanocomposites can be synthesized through common dry and wet
methods. The polymeric material and the nanoparticles can be used as a nanocoating
material that is coating of a nanoscale layer on the solicited substrate to get the
specific/desired surface performance [39]. There are many different kinds of phys-
ical and chemical strategies, such as electrochemical, thermal decomposition, laser
ablation and microwave irradiation for the synthesis of nanocomposites [40, 41].
Among all the synthesis methods, chemical synthesis is widely used because it does
not require any harsh conditions such as high temperature and pressure. It also does
not require any sophisticated conditions and is environmentally safe, low cost, non-
toxic, less energy requirement, therefore also called green synthesis [42–46]. In this
kind of synthesis, the metal salts could be reduced by a chemical reducer such as
sodium borohydride (NaBH4).
3.3.2 Physical Methods
Another method for the fabrication of polymer-based metal nanocomposite is phys-
ical method that is mostly accomplished by combining of two or more polymers,
leading to a new product which is a blend of both the materials but with different phys-
ical properties [47]. The mechanical, structural, chemical, morphological, biological
properties can be optimized in blending method to produce new materials leading to
economically favoured products. An additional benefit of blended material is that it
develops unique properties which are required in many individual polymers. Also,
the process is time-efficient [48]. Various compositions of starting material result in
the product with different dynamic properties. There are several physical methods
for the synthesis of chitosan–gold nanocomposites [49]. A gelation method has been
employed for the fabrication of hydrophobic polymers using ion by Alonso and
co-workers (1997). In this method, trivial synthesis array of two aqueous phases
has been involved. One phase circumscribes chitosan and polyethyleneoxide and
the second one is TPP (polyanion sodium tripolyphosphate). The zeta potential and
particle size of nanocomposites of chitosan are found in between +20 to +60 mV
and 200–1000 nm, respectively.
3.3.3 Radiolysis, Sonochemistry and Photochemical (UV,
Near-IR) Strategies
Another set of methods involves the photochemical synthesis of nanoparticles such
as photochemical degradation and light-mediated degradation of a metal salt through
radiolysis. The radiolysis can control the size of NPs during the synthesis AuNPs
72 R. A. Omar and M. Jain
[50]. Size and shape of Au nanoparticles could be enhanced using UV-irradiation
especially when used in combination of micelles [51]. Near-infrared laser irradiation
results in the formation of thiol-stabilized Au nanoparticles [52]. Sonochemistry is
widely used for the formation of Au nanoparticles inside the silica pores [53]. Laser
photolysis can be used for the formation of Au nanoparticles in form of micelles of
block copolymer [54]. Small AuNPs can be produced by power ultrasound method.
Approximately 5-nm-sized NPs can be synthesized through surface of pre-prepared
silica sub-microspheres. In sonochemical reductions, ultrasonic irradiation at room
temperature, argon gas is required for the formation of gold nanoparticles [55].
3.3.4 Chemical Synthesis
Metal-containing nanoparticles synthesis of was carried out through various tech-
niques including thermal decomposition, electrochemical irradiation and chemical
reduction through green chemistry techniques [56–60]. Huang et al. [39] fabricated a
nanocomposite of chitosan and metal in aqueous solution using sodium borohydride
(NaBH4). Green synthesis is on priority in solvent system due to its eco-friendly
nature and forms a non-toxic preservative at the time of synthesis [61]. In addition,
Wei et al. have reduced the silver nitrate (AgNO3) salts using biodegradable and
non-toxic chitosan (Cts) in Cts-based silver NCs [62]. Huang et al., have devel-
oped a sustainable method to eliminate NaBH4, thus making a “greener” method in
comparison with other approaches. Chemical methodologies are pivotal in synthe-
sizing nanocrystals of different materials [63]. For these methods, the primary need is
mild conditions. Uniform size and shape is a necessary factor which decides the great-
ness of synthetic methodologies of synthesized nanoparticles. Various reductants,
like hydrogen peroxide sodium hydroxide, sodium citrate, trisodium citrate, ascorbic
acid and sodium borohydride, are capable to reduce trivalent Au (III) ions to nascent
Au (0) [64–66]. Source of energy for this reduction process is mainly ultrasound
irradiation, photoirradiation, or heating in the presence of surfactants, water-soluble
polymers and reducing/capping agents. This method provides remarkable uniformity
in size and shape of scattered particles. Furthermore, the surface-modifying agents
and capping controllers reduce aggregation of nanoparticles and support colloidal
stabilization [64]. NPs show improved colloidal stability upon covalent bonding of
ligands at the surface of the nanoparticles.
3.3.5 Reduction by Borohydride
Sodium borohydride (NaBH4) is an effective, intensive, low cost and broadly used
reducing agent. NaBH4 is widely used for the reduction of silver nitrate by ice-cold
to synthesize silver NPs. NaBH4 is needed in a very high amount for the ionic silver
reduction for the stability of prepared NPs. Graphene oxides were directly prepared
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 73
from graphite using Hummer’s method [67, 68]. However, the AuNPs modified
graphene synthesis is possible by NaBH4 reduction procedure. Chemical reduction
in aqueous organic solvent of metallic ions is the basic need for synthesis of metal NPs
[69, 70]. NaBH4 reduction method is also broadly used in the AuNPs synthesis. In
another way, some other reducing agents such as superhydride and hexadecylaniline
have also been used for Au(III) reduction, in the formation of thiol-stabilized AuNPs
[71, 72]. These synthesis methods are efficient but some impurities of boron and
difficult to reproduce (mainly in liquid medium) in the final product are still a major
issue allied with the reduction of borohydride [73].
3.3.6 Citrate Reduction
In this method, AuNPs are prepared by adding sodium citrate of chloroauric acid
solution at its boiling stage [55]. Citrates are generally used to prepare AuNPs with a
property of citrate stabilization. However, due to these NPs showed various disadvan-
tageous. Some of the recent studies suggested that reducing solutions of Au/citrate
with NaBH4 can maintain the average core size (>10 nm) of nanoparticles. The
method is efficient for producing metal NPs, however, having some drawbacks
mainly: nanoparticles cannot be stored in solid state because it is difficult to isolate
them from the solution. The other one is variation in ionic strength, or pH slightly
affects the stability.
3.3.7 Synthesis by Seeding Growth Technique
Seeding growth method is an old technique, used since many years. Approximately,
5 to 40-nm-sized NPs can be prepared using this technique. Size of nanoparticles
is manageable by altering the proportion of metal salts and seed [74]. Step-by-step
enlargement of particle is more efficient process than one-step-seeding due to the
formation of secondary nucleation [75]. Seeding growth technique was successfully
used mainly for gold nanorods preparation [76]. The technique involves a growth
solution prepared using a feeble reducing agent, a surfactant and Au(III) salt, which is
used as a commanding agent that is cherished with pre-prepared “seed” nanoparticles
[77].
3.3.8 Biosynthesis Technique
Biosynthesis method uses mainly vitamins, carbohydrates, enzymes, biopolymers
and microorganisms, between others. AuNPs have also been synthesized using
biological method in some studies [78]. In one-pot synthesis method, achieved
74 R. A. Omar and M. Jain
particle size depending on the concentration of reducing agent as in chitosan oligosac-
charide, ratio of chitosan and gold should be maintained to synthesize different size
particle, chitosan molecular weight also being a dominant factor in size and shape
distribution of nanoparticles.
3.4 Applications of Chitosan–Gold Nanocomposites
Chitosan–gold nanocomposite was used in various applications (Fig. 3.3), and some
of them are given below .
3.4.1 Textile Industry
For the development of multifunctional fabrics, the enhancement of prevailing
property and the synthesis of novel materials with potent features are the prior
aims of current textile industries [79]. Due to poor conjugation, the nanoparticle
bonding becomes weak on multiple washes. Therefore, to overcome this problem
some alternatives are needed. Due to which qualities and properties of fabrics were
not stable and durable. Moreover, the emancipation of nanoparticles to the envi-
ronment from fabric acts as a contaminant. These disadvantages motivated the
researchers to focus on polymeric nanocomposites instead of nanoparticles alone
due to their stability and durability. The nanocomposites of polymer improve the
bonding among the nanoparticles with the textile surfaces due to which the dura-
bility of the fabric is increased also, making the environment safe by inhibiting the
liberation of weakly bound nanoparticles into the environment [80]. In addition,
nanocomposites polymer not only offers the chance to amend the dimensions and
Fig. 3.3 Application of chitosan–gold nanocomposites
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 75
chemistry of fabric by changing fillers among them but also permits to add various
inorganic and organic substances to prepare the multifunctional fabric. The utilization
of multiple hydrophilic/hydrophobic functional matrices of polymer as the dissemi-
nation medium for various nanoparticles will provide new characteristics to desired
nanocomposites of polymer with an enhanced bonding. This will also convey required
wettability with varied functional applications such as microbicidal property, conduc-
tivity, resistance to ultraviolet and flame retardancy. These eccentric characteristic
properties of different nanocomposites develop a new category of fabrics which is
demand of textile industry in nowadays [81]. Chitosan nanocomposites are one of the
broadly used nanocomposites in the textile industry nowadays. Chitosan appertains
to polysaccharides family formed from β-(1 4)-linkage of N-acetyl-d-glucosamine
and d-glucosamine biomolecules [82]. The most ordinary source to achieve chitosan
is the exoskeleton of marine entities. However, nowadays chitosan is also produced
from fungi or insects [83, 84]. Because of various attractive characteristics, such
as biocompatibility, biodegradability, magnificent and scope for structural modifi-
cation at chemical and mechanical levels, have made chitosan a favourite material
for research community [85, 86]. Chitosan is amidst the amplest natural polysac-
charide found in nature, incorporating numerous utilitarian features that could be
accomplished for the advancement of textile such as biodegradability, antimicrobial
activity, and biocompatibility and non-toxicity to synthesize higher-grade fabrics
[87, 88]. Chitosan nanocomposites are also preferred for the medical use such as
bandages, gauze and threads because of hygiene maintenance and high antimicro-
bial property [89]. The hydrophobic/hydrophilic functional polymers incorporated
with nanoparticles enhance reinforcement property of the fabric. Incorporation of
chitosan nanocomposites enhances the hydrophobicity and rigidness at the surface
of the fabric. Moreover, the chitosan nanocomposites maintain the hysteresis of
contact angle that leads to control repellence of water or the absorbance among the
fabrics. Maintaining that low contact angle through a change in the structure of the
nanocomposites of chitosan allows the i ndustrialist to produce good grade sportswear
with a property of moisture management and fabric relay soothing experience to the
people. In addition, the chemical stability at high temperature is also enhanced by
chitosan nanocomposites [90]. Chitosan nanocomposites incorporated with inorganic
UV-blockers like TiO2,SiO
2, ZnO and Al2O3 which improves the property of UV
protection in fabrics by controlling Rayleigh’s scattering, thus increasing the fabric’s
stability [91]. Likewise, the bactericidal efficiency of the fabrics is also enhanced by
the incorporation of zinc oxide, titanium oxide and nanosilver in nanocomposites of
chitosan [92]. Metal chitosan-loaded fabrics are very active and sensitive against the
microbial activities because when microbe comes in contact with the fabric, metal
nanoparticles abruptly retard the metabolism and inhibit the growth of cells also
rupture the cell walls of the microbes [93]. In a study, it was found that the TiO2
nanoparticle provides protection against microbial strain through photo-catalytic
discoloration of microbes [94].
76 R. A. Omar and M. Jain
3.4.1.1 Wool Industry
Wool is the paramount category of fibre, which broadly employs in the fabrication of
good quality garments. Wool fibre has cuticle structure due to which it has a tendency
to shrink, under mechanical action, commonly at the time of washing, still it is one of
the most commonly used fabrics. Using nanotechnology and other processes machine
washable wool fiver has been also developed [95]. In past time, chlorine–Hercosett
process (in this process, chlorine treatment is followed by polyamine resin treatment)
was employed to reduce wool fibre felting, which provided finishing to the fibre. The
process is efficient but there are two major disadvantages of using this process: the
first one is strength loss in wool fabric and yellowing leads to compromise quality and
the second one is release of absorptive organohalogens in the effluvium discharged
by the process, acting as environment pollutant causing risk to the environment
and human health [96]. On considering these problems, an alternative method, i.e.
additive treatment, was used in which water-borne polyurethanes were included that
offered a substitute which was free from chlorine to eliminate wool fabric felting [97].
However, the polyurethanes postulate strong inter-fibre bonds leading to enhance the
strength of fabric. But, due to large polyurethanes dosage, the smoothness of the fabric
was lost [98]. In later studies, polyurethanes have been modified with chitosan and
investigated. The manipulation in polyurethanes and chitosan showed a breakthrough
due to enhanced fabrics mechanical strength also provided non-toxic discharge of
the effluent [99]. Basically, at the time of polyurethane synthesis chitosan was added.
The use of chitosan and chitosan nanocomposites improved the mechanical strength
by amplifying the inter-fibre bonding inside the fabric.
3.4.1.2 Silk Industry
Silk fibre is a biomaterial extracted from Bombyx mori, which has always become
interested for mankind. This material possesses outstanding mechanical strength,
biocompatibility and shows sluggish degradation. These properties have made it a
material of choice in textile industry [100]. The fibre is made up of approximately
seventeen amino acids having a large porous sponge form which induces the fabri-
cation of b-sheets of protein. It is difficult to achieve the dimensional stability in
silk fabric by self [101, 102]. Also, to reduce this problem, various additives have
been used but the use of chitosan nanocomposites has made it possible to overcome
this problem. The chitosan nanocomposites on silk have two unique features: firstly,
the scattering of nanochitosan with different nanoparticles in the matrix of silk fibre
is similar and secondly, the fabric’s dimensional stability is improved superbly and
provides an additional benefit by providing magnificent compression strength [103].
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 77
3.4.1.3 Application in Cotton
The antimicrobial fabrics are the need of the hour due to hygienic and detrimental
effects of microorganisms [104]. The cotton is considered as one of the comfortable
and soothing fabrics. Cotton is a cellulosic fabric anchored with several hydroxyl
groups. The dimensional stability and antimicrobial efficiency of cotton could be
enhanced by applying multifunctional cross-linking agents. The nanomaterials are
widely used nowadays in textile industries for the development of required t extile
features as per the demand of the people. Chitosan-nanomaterials are one of the
highly considered nanoparticles because of their exotic features like biocompatibility
and antimicrobial potential. These nanomaterials are having high surface area-to-
volume ratio and huge surface energy that provide a better amalgamation of textile
substrates could be achieved along with improving its durability, breathability and
mechanical strength. In general, chitosan-nanomaterials are used as catalyst and
improve recovery also the wrinkle resistance of fabric. During finishing process,
chitosan nanomaterial decreases the internal stresses created at the time of spinning
and weaving, therefore relaxing the fabric which results in increased durability [105].
3.4.2 Improvement in Textile Functionalities
by Chitosan–Gold Nanocomposite
3.4.2.1 Chitosan–Gold Nanocomposites in Enriched Dyeing
and Antimicrobial Property
Chitosan is widely known for its microbicidal activity. Therefore, it has gained
compelling attention in various research fields. Degree of acetylation and substi-
tution, molecular weight, physical properties and structural compositions of the
cell wall of the desired microorganisms are the main parameters to decide the
antimicrobial property of chitosan. The chitosan alone cannot provide antimicro-
bial activity; therefore, a complex of chitosan with other active elements like natural
compounds, metals and drugs is an efficient approach to increase its antimicro-
bial activity. Metal-doped (Ag, Cu, Au, etc.) chitosan nanocomposites possess natu-
rally occurring positive charge which results in peculiar properties like permeability,
antimicrobial activity and improvement in mucosal adhesiveness which leads to its
possible utilization in different areas [106, 107]. Microorganisms contain negative
charge on their cell wall so positive charge on chitosan molecule due to amine groups
of can easily attach to the target organism effectively. This results in the modifica-
tion in cell permeability, thus creating an osmotic deterioration with the effluence
of ions and proteins between extracellular space and cytoplasm which inhibits the
further microorganism’s activity [108]. The bactericidal effect is because of the posi-
tive charge and different inherent factors or incorporation of other metals such as
Au and Ag. Some other parameters like degree of s ubstitution and deacetylation on
78 R. A. Omar and M. Jain
amino groups intrinsically affect positive charge density on chitosan [109]. Degree
of deacetylation affects the number of free amino groups on polymers backbone of
chitosan nanocomposites giving excellent antibacterial activity [110, 111]. In addi-
tion to this, solvent, its pH and molecular weight are also required to be controlled
because they could affect the activity of molecule. In a study, it was found that the
bactericidal activity of chitosan changes with change in its pH and molecular weight
[112]. Also, in the same study, it was suggested that at lower pH value, antibacterial
property of chitosan was higher because of higher protonation degree in that partic-
ular condition [113]. The antimicrobial property also differs from species to species.
In gram positive bacteria, a higher molecular weight chitosan is more preferred in
comparison with gram negative bacteria [114]. Chitosan’s molecular weight, degree
of acetylation and pH are all important for antifungal activity. The efficacy of chitosan
can also be improved by changing its structure, i.e. by substituting it with some
other functional groups. The properties of fabric can be changed by N-modification
on chitosan molecule by quaternarization, alkylation, acylation, metallization and
saccharization. Due to these changes, hydrophilic/hydrophobic character of chitosan
molecule is manipulated and it provides a new property in the fabric [115]. When
the amino group of chitosan molecule is quaternized with aromatic groups or short
alkyl chains, it boosts the antimicrobial efficacy of chitosan [116, 117].
Chitosan nanocomposite is also used for the dye removal applications because
amino groups of chitosan molecule are cationized easily, resulting in anionic dye
adsorption using electrostatic forces in liquid [118].
3.4.2.2 Activity in Wrinkle Resistance
The wrinkle resistance in the fabric can be maintained by several conventional mate-
rials. However, the materials have several disadvantages such as decrease in abrasion
resistance, fabric tensile strength, water absorbance and dyeing potency. To remove
these limitations, the nanomaterials have been used into the matrix of fibre which
improves the actual features as per the need [119]. However, instead of using the
nanoparticles, some other techniques such as exhaustion and padding have been
also used on the fabrics to get the wrinkle resistance property [120]. Moreover, the
microwave treatment on fabrics also helps to increase the wrinkle resistance property
in fibre same as the oven curing, where it generates higher volumetric heating and
frequency to enhance resistance activity which is not good [121].
3.4.3 Effluent Treatment Application
The discharge of wastewater from various industries has become a serious threat
nowadays. The wastewater discharged from various industries like leather tanning,
fibres, textile, pharmaceutical, wools food technology, paper, plastic produces large
amount of contaminants in water [122, 123]. Industrial effluent contains many organic
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 79
pollutants, ions of heavy metals and dyes which contaminate the water resources
[124]. There are several methods or techniques that have been used to treat indus-
trial wastewater such as osmosis [125], adsorption [126], filtration through activated
charcoal [127], electrochemical oxidation [128], incineration [129], organic resin and
biodegradable nanocomposites [130]. Adsorption is one of the efficient techniques
used for treatment of wastewater. In recent years, the interest in nanotechnology
and nanomaterials resulting in fabrication of a number of adsorbents to battle the
wastewater hazard. Chitosan–gold nanocomposite is one of the efficient adsorbents
because of its environment-friendly nature, biodegradability, non-toxic effect, easy
handling cost efficiency and effectiveness in scavenging heavy metals and dyes [131].
In addition, of use of chitosan nanocomposites for wastewater treatment application
is advantageous due to insoluble nature of chitosan in H2O, organic solvent and
also in alkaline solutions which is due to hydrogen bonding among the molecules.
Solubility of chitosan is only found in acidic medium because of protonation from
its amine group. Based on these properties, capability of chitosan-based nanocom-
posite is increased as compared to other adsorbents in wastewater treatment applica-
tions [132, 133]. Changes in degree of acetylation also play a crucial role in pollu-
tants removal efficiency. Chitosan-based absorbents are reported to remove dyes like
Reactive Blue, Acid Green, Acid Blue, Direct Blue, Food Yellow effectively [134].
3.4.4 Bioremediation
Environmental pollution has become a matter of serious concern nowadays, and
action against it should be taken in priority to inhibit the upcoming environmental dis-
balance. Various technologies such as ion exchange, adsorption, electroprecipitation,
floatation and coagulation–flocculation were developed to solve this problem [135].
Another technique based on nanotechnology, i.e. bionanopolymers, has come into
picture which is the emerging and the most promising material in the field of water
pollution management. In addition, biopolymers are biodegradable, cost-efficient
and eco-friendly and have high surface area [136, 137]. Chitosan nanocomposites
have been successful in removing inorganic, organic and xenobiotic compounds,
which have developed peculiar interest of researchers in this. In addition, chitosan
nanocomposites can work under broad pH range due to the presence of several coor-
dinating moieties in their structure. These properties of chitosan have made it an
eligible candidate t o be applied in bioremediation applications [138]. Deacetylation
and change in the molecular weight could increase the performance of nanocom-
posites of chitosan as per the requirement. These nanocomposites can be easily
functionalized, thus increasing the selectivity of the material to interact with the
contaminant [139]. In some studies, chitosan-based materials were already reported
for the effective nitrates and phosphates removal from water. In one of the studies, the
material was prepared by doping Cu (II) in chitosan nano-matrix ligand exchanger
and utilized for the eradication of phosphate. Chitosan nanocomposites were also
used to enhance the biodegradation of oil contaminants using osmocote fertilizer
80 R. A. Omar and M. Jain
[140, 141]. It has been found that, chitosan-based nanocomposites are the cheapest
materials as compared to activated charcoal or other materials in the removal of
chromium [142]. Nanocomposites of chitosan can also be used successfully for the
eradication of tungsten by altering the net surface charge from negative to positive
[143]. A complex of chitosan nanocomposites and green chelating agents was used
for the removal of heavy metals like cadmium (Cd), zinc (Zn), copper (Cu) and
lead (Pb) xenobiotic compounds and dying chemicals from the industrial effluents
[144]. The chitosan nanocomposites can also act as substitute against synthetic poly-
electrolytes used as natural coagulant to eradicate turbidity from the drinking water
[145]. Chitosan nanocomposites also reduce soil erodibility by improving the cohe-
sive forces of inter-particle in among the soil particles that in turn revitalize the soil
[146]. They also improve the mechanical strength and intercept the water-induced
degradation of the construction’s materials [147]. Another application is their use
like an eco-friendly mixture or like an exo-coating agent in construction works [148].
3.4.5 Application in Biomedical Field
3.4.5.1 Drug Delivery Applications
The antimicrobial properties of chitosan lead to inhibition of growth or microorgan-
isms death which are pathogenic. Studies suggested that antimicrobial property of
chitosan depending on certain parameters like source and nature of chitosan, chelating
capability, stage of cell polymer concentration, solubility, environmental conditions
and degree of acetylation [149–152]. Chitosan also responds to outer impetus such as
temperature, pH, magnetic and electric field due to its cationic nature [151]. Reported
studies concluded that the mechanism behind the antimicrobial property of chitosan
is mainly due to two reasons: (i) Increase in the –NH3 + ions (positive charge) on
the polymer leading to binding of chitosan to the bacterial cell walls and (ii) RNA
inhibition and disrupted protein synthesis which can be achieved by insertion of
chitosan with their oligomers (low molecular weight) inside the cell’s nuclear cores
[153]. It is reported that chitosan plays a vital role in pathogenicity and cell-to-cell
communication by disrupting the formation of HAQs (4-hydroxy-2-alkylquinolines)
along allied metabolite [151]. It is still not known that chitosan is responsible for
cellular toxicity or inhibits only the growth of microorganism. The antimicrobial
efficiency of chitosan can be changed on the basis of side chain functional groups
and molecular weight. Relationship between degree of deacetylation and antimicro-
bial efficiency of chitosan is still unknown and needs to be investigated. Some of
the studies have been done on the association between microbial diversity (till strain
level) and antimicrobial efficacy of chitosan nanocomposites [154, 155]. Chitosan
nanocomposite retards growth of broad range of microorganisms through binding
them within liquid form in in vivo and in vitro experiment and act as broad range
antibiotic [156]. Both types of bacteria (gram positive and negative) are influenced by
quaternized chitosan (QCS) absorbed photo-cross-linked electrospun, portending the
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 81
use of chitosan nanocomposites electrospun matrix for dressing material for wounds
[157].
3.4.5.2 Wound Healing Applications
Scaffolds Mixed with Chitosan/Synthetic/Natural Used in Wound Healing
Chitin–PAA (polyacrylic acid)-based implantable hydrogel system was prepared
for the generation of suitable dressing material for wound healing. On chitin–poly-
acrylic acid sheath, a regular cellular morphology was observed after 14 days [158].
Chitosan-based hydrogel also promotes some toxicological effects due to hydrogel
which is used in rat’s fibroblast cells signifying induction of cellular adhesion and
proliferation between cells [159]. Cell toxicity was studied on mouse fibroblast
(L929) cells. The prepared film was slightly toxic confirming its application in wound
dressing [160]. Determined and accurately measured antigen delivery was achieved
using chitosan and its porous microspheres derivatives together [161]. Mucoadhe-
sion property in chitosan and some of its cationic derivatives were also observed
which is effective in normal pH for drug adsorption capacity. The positively charged
N-trimethyl chitosan chloride reacts with negative charged cell surface leading to
reduction in microbial load [162]. Chemical modification in chitosan biopolymer can
change surface characteristics of films like synthesis of stearoyl ingrained chitosan
film conveying hydrophobic nature leads to improve adsorption of proteins. However,
phthalic/succinic anhydride treatment leads to the formation of hydrophilic films
used for lysozyme adsorption [163]. Some of the nanocomposites of PVA-clove
extract, PVA-bentonite, PVA-cellulose hydrogel and PVA-Ag NPs were synthe-
sized by Gonzalez et al. A drawback of non-uniform texture and poor spreading
was recorded in formulation of PVA-clove; however, considerable moisture carrying
capacity and solidity besides enhanced antimicrobial capability was observed in
formulation of nanocomposite gel of PVA-bentonite and nanoparticles of PVA-Ag
for E. coli after inserting fillers (clay and silver nanoparticles) [164]. The movement
of growth factor can be promoted by incorporation of heparin which is related to
healing on the site of wound leading to enhance rate of wound healing [165].
Wound Healing by Chitosan Graft Scaffoldings Composite
A technique known as electrospinning has been used for the formation of nanofibers
of chitosan–sericin, size ranging from 240 to 380 nm with uniform structure. The
nanocomposite showed enhanced cellular proliferation and considerable antibac-
terial activity against gram positive and negative bacteria with adequate dressing
efficiency. After 24 h, approximately 90% viability was observed in the cells in
all the test concentrations, and after 72 h, approximately 100% viability recorded
in the cells when compared with control [166]. Chitosan sulphurylation at o2 and
o3 position formed sturdy antiviral agent that leads to efficient inhibition of AIDS
82 R. A. Omar and M. Jain
virus [167]. Chitosan with silver sulfadiazine with act as a stable drug, released
with an increased cytocompatibility and adequate swelling ability also enhanced
antimicrobial effect [168]. Chitosan alginate mixed with silver sulfadiazine provides
good durability. It was observed that long duration release of drug happens approx-
imately 50% of alginate concentration proving its dependency on alginate [169]. A
combination of alginate and calcium chloride coacervate on chitosan alginate PEC
membrane is used for enhancing the property of wound healing. Instant wounds
healing accompanying fresh epidermis development were observed in fabricated
membrane. It was not harmful to fibroblast cell of human and mouse [170]. Dual-
sided dense matrix silver sulfadiazine bandage showed in vivo bactericidal property
against Pseudomonas aeruginosa and Staphylococcus aureus with reduced drug
release [171]. A chitosan/CM chitosan membrane showed good homeostatic and
bactericidal activity against E. coli. CPC found to be an efficient dressing item with a
property of non-toxicity and good histocompatibility to skin impeding keloid forma-
tion instant healing wounds [172]. A polythiolated chitosan–ciprofloxacin conjugate
was utilized for the synthesis of chitosan film having property of heat sensitiveness.
The composite was focused to separate easily from wound subject to low temperature
[173]. A chitosan–silver–hydroxyapatite (CS-Ag-Hap) biomembrane was prepared
on a substrate of anodized titanium encompassing silver, chitosan and hydroxyapatite
through electrochemical synthesis procedure. An increased antimicrobial activity and
good cell adhesion were noticed in synergistic action of chitosan nanocomposite due
to the porous nature of the surface. An enhanced antibacterial and cell adhesiveness
reduced the problem of infection concluding their applicability in dressing mate-
rials [174]. A silver encapsulated patch of chitosan hydrogel was responsible for
high antimicrobial activity. The produced hydrogel manifest improved the swelling
ability, blood clotting efficiency and also non-toxicity. Hydrogel showed non-toxic
nature in cytocompatibility against Vero cells. It was observed that hydrogel showed
a vital role in healing of wounds by retarding E. coli and S. aureus (gram negative and
positive bacterium, respectively) [175, 176]. A composite of CS-γ PGA was noticed
to be appropriate with enhanced tensile strength and ability that able to remove
easily from injured surface, without harming the injured tissues. CS-γ PGA treated
wounds showed rapid healing in comparison with controls. Approximately <50% of
re-epithelial cells were observed by using a complex of CS-γ PGA polyelectrolyte
[177]. Electrospinning method is also used for the fabrication of chitosan–gelatin
blend nanocomposite. Robustness and substantial tensile strength were conveyed
to the fabricated fibre miscellany by coherent nanocomposite (Fe3O4) dispersed
uniformly in overall matrix fibre ensuring the effective liberate from the matrix of
chitosan–gelatin. Inhibition of E. coli and S. aureus has been noted by the use of
Fe3O4 nanoparticle. Antibacterial activities and physiochemical properties indicated
its application in acute wound dressing material [178]. A freeze–thaw technique is
also used to prepare stable nanocomposite and to circumscribe, chitosan polyvinyl
alcohol is the compatible dressing material. In future prospects, a nanocomposite
should have property of swelling nature, enhanced tensile strength and antimicrobial
activity which could be applicable as dressing material [179].
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 83
Wound Healing by Chitosan–Oil Ingrained Grafts
Zinc oxides chitosan nanoparticle in different concentrations, soaked with castor oil
film could be used in the process of solution casting. Increment in the concentra-
tion chitosan–ZnO antibacterial property against gram positive and negative (both)
strains was also improved. Due to desirable properties of material such as absorption
of water, biodegradability, cytocompatibility, antimicrobial activity and property of
wound healing, it could be used as potential dressing bandages material [180].
Wound Healing by Plant Extract Entrenched Chitosan Films
Extracts of hydrogel plant can also be utilized in microbicidal activity but they have
some drawbacks such as incompetence problem and discharge of less quantity of
active materials that directly affect formulation capacity. Plant extract contains some
bioactive substances which help in instant wound healing naturally. Gentamycin
sulphate-infused hydrogel films along extracts of Salix alba and Juglans regia plant
showed antifungal and antimicrobial properties. These properties are required for the
process of wound healing [181–184]. Open (uncovered) wounds have higher chances
of contamination from microorganisms such as bacteria, fungi and viruses. So, there
is a requirement to develop an efficient material for wound healing with some bioac-
tive compounds to circumvent sepsis and also other contamination from the wound
area. Aloevera has anti-inflammatory and moisturizing property due to which it could
be a better alternative to be prepared with wound dressing bandage. Conjugating
chitosan/aloevera has been reported for highly efficient dressing membrane. Because
of high antibacterial activity, huge amount of aloevera is used in aloe/chitosan
nanocomposite bandages. A better proliferation and adhesion property of chitosan
was also observed. Enhanced adherence property was observed in the spindle-shaped
fibroblast and uniform distribution (day 1 to day 7), however, on seventh-day cells
attached to membrane on both of the sides. Use of chitosan/aloevera could be a better
material for dressing [185]. Some of the chemicals in aloevera like glycoprotein and
polysaccharide have more wound healing capability [186]. Acemannan is also liable
for retarding growth of microbes and showed high activity of microphages [187].
The antibacterial property in some bioactive materials like cinnamic acid, lupeol,
phenols, sulphur and salicylic acid is also observed [188].
Healing of Wound by Chitosan Modified Products
Chitosan and its derivatives with some modifications are broadly used in delivery
of drugs because of their improved solubility in acidic medium, which lead to
cell definite targeted delivery and enhanced cellular uptake [152, 189]. Chitosan
has a drawback of less solubility in physiological pH [190]. Thus, there is a need
to produce derivatives of chitosan soluble in aqueous medium like carboxymethyl
chitosan, carboxymethyl trimethyl chitosan and trimethyl chitosan for the application
84 R. A. Omar and M. Jain
in healing of wounds and drug delivery. Carboxymethyl trimethyl chitosan is also
used in cosmetics, to maintain its moisture-capturing efficiency and use it as an essen-
tial element [191]. Derivatives of trimethylated have shown outstanding mucosal
attachment and capability of loading drug due to strong cationic characteristics of it
[192].
3.4.5.3 Toxicological Effects of Trimethyl Chitosan
Methylated trimethyl chitosan has widely been used in drugs absorption. The in vitro
evaluation was significantly done using COA-1 and Caco-2 cells [193]. TMC concen-
tration was directly proportional to its cellular toxicity behold in cell line of HeLa
cells which leads to complete depredation in concentration >10 mg/mL [194]. By
increasing the cationic charge and decreasing molecular weight also increase the
toxic effects. Lower toxicity in in vitro cell lines was observed using COS7 (monkey’s
fibroblast cell line of) and TMC (<55% trimethylation grade) with low molecular
weight for MCF7 (human). However, TMC (trimethylation degree = 94%) resulted
in less IC50 against COS7 (2.2 mg/mL) and MCF7 (1.4 mg/mL) [195]. Various
molecular weighted chitosan (5, 25, 50, 100 and 400 kDa) have been applied on
L929 fibroblast cells resulted in IC50 values >1000, 270, 90, 70 and 30 g/ml, respec-
tively, and keep constant degree of methylation [196]. In a study, it is reported that
positively charged polyethyleneimine is more toxic than TMC [197]. TMC is cationic
in nature. Due to this property, in healing of wounds, TMC plays a vital role, also in
various drug delivery applications by complexing with DNA and RNA (anionic).
Wound Healing by Trimethyl Chitosan (TMC)
TMC was synthesized in bilayer through sandwiched with collagen and attached with
DNA (which encodes for EGF and VEGF) increasing rejuvenation and angiogenesis
of affected area by the resulting product [152]. A complex of TMC and DNA enhances
growth factor stimulation, endocytosis, which also defends against the degradation of
nuclease [198]. Incision wounds treatment using same technique resulted in increased
vascular vessel production and mature RBCs movement because of ferocity of wound
obtained close to adjoining cells and blood vessels abutting burn wounds [199].
3.4.5.4 Carboxymethyl and Carboxymethyl Trimethyl Functionalized
Chitosan Applications
An increment in biological compatibility and liquid solubility of CMC can be
obtained by the adherence of moiety of carboxymethyl to the polymer backbone
[200]. CMC synthesis from chitosan by s ingle catalytic reaction in which NaOH,
(C3H8O) and water (H2O) mixed slowly with the chitosan-containing reaction
mixture, and after that, mixture was treated by chloroacetic (ClCH2CO2H) acid.
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 85
CMC is soluble in a variety of pH range and possesses enormous gelling ability and
also has no issue of histocompatibility. CMC increases the rate of wound healing by
enhancing fibroblast proliferation, thus showing exceptional ability of binding with
drug/ligand and renders uncommon bandage of dressing [201]. Some of the physical
parameters such as pH, molecular weight, degree of deacetylation, concentration and
charge of cations on the polymer affect antimicrobial activity and capability of CMC
[202]. Liu et al. had tested the antibacterial efficiency against E. coli in order of
N, O-carboxymethyl chitosan >chitosan >O-carboxymethylated chitosan [203]. An
increased keloid formation and proliferation of fibroblast were recorded to maximize
cytocompatibility. At pH 10.0, a treatment using CH3COOH and NMP with TMC
showed the establishment of O-carboxymethyl-N, N, N-trimethyl chitosan [204].
Chitosan beset C3 and C6 as sites for carboxymethylation that might get hindered
through O-methylation posing hindrance for appended substitutions therefore intact
and appropriate monitoring is needed at every step of reaction [205].
Wound Healing by Peptides Conjugates-Chitosan/Derivatives
An exclusive method can speed up the wound healing process. In this method, satu-
ration with biochemical factors is replaced by the peptide functionalization of the
scaffolds. Peptide-associated scaffold material can enhance the bonding of dressing
material along extracellular materials of skin. In complete and fast traumatic wounds
healing, cell differentiation increases with enriched proliferation monitored in L929
fibroblast (mouse). A conjugation between extracellular matrix and RGD (argi-
nine/glycine/aspartate) signalling peptides improves the cell attachment and acti-
vates pathway of Rho GTPase resulting in integrin activation which enhances the
cellular attachment [184, 185]. The scaffolds of chitosan impregnated with RGD
sequence enhances cell attachment and biocompatibility, which was identified by
the receptors [206]. So that, the 3D functionalized chitosan scaffold can be used
as an ECM accessory [207]. Carboxymethyl trimethyl and tryptophan impregnated
chitosan are used in delivery of the genetic material and also for bonding of two or
more peptides as well as site-targeted drug delivery [208]. TMC conjugate with CMC
by succeeding derivatization results in more optimized and stable product [209].
Polyelectrolyte complex (PEC) was a product produced by addition of Gly–Arg–
Gly–Asp–Ser (GRGDS) peptide and carboxymethyl trimethyl chitosan (CMTMC)
and has the capability to enhance cell adhesion and migration. Another methods
known as ionic complexation procedure were also utilized for nanoparticles forma-
tion impregnated with chondroitin sulphate showed wound-healing capability [210].
Active peptide-functionalized scaffolds showed improved adhesion of dermal fibrob-
last and fibroblast. The previous studies suggested impact of biologically active and
modified chitosan and its derivatives in facilitating the tissue engineering.
86 R. A. Omar and M. Jain
3.4.5.5 Chitosan Blend in Commercial Dressing Bandages
Naturally originated chitosan and its derivatives are an efficient biopolymer used in
form of dressing bandage. Some of the efficient and popular commercial dressing
bandages are Chitipack P (Eisai Co.) (Bloated chitin fortified over poly (ethylene
terephthalate) and ChitipackS. ChitipackS is capable of promoting early granulation,
so that it is used for the traumatic wound and defects of surgical tissue treatment.
Marine polymer technologies have been used to develop Syvek–Patch (reinforced
chitin fibrils), used to enhance the processes of haemostasis [211]. HemCon (a freeze-
dried salt of chitosan) is efficient for prevention of supra-infection and production of
haemostatic effect, also at the time of civil medical emergency is used exceedingly
[212–214]. Chitosan is efficient to be used as dressing patch (with anti-infective prop-
erty) of burns and management of wounds and keeps the structural probity, and also
at the injury site, the mucosal adhesiveness of chitosan is efficient. Meshed chitosan
membrane had shown a remarkable development in tissues structural rearrangement,
accelerated wound healing [215]. A reinforced heparin–chitosan membrane has been
developed by Kratz et al. to determine the wound healing capability in skin of donors
[216]. A novel approach has been developed by Damour et al. to substitute dermis
of skin using a dermal substrate [217] used for promoting neo-vascularization also
for unambiguous and measured colonization of the fibroblast manifolds [218].
3.5 Future Applications
Metal-doped nanocomposites of chitosan have s pecial properties which make it
useful for various applications. Its biological origin and biodegradable nature gained
attention in wastewater treatment applications. Nanocomposites of chitosan are
hydrophilic, non-toxic, biocompatible, biodegradable and cost-effective in nature.
In addition, these are effective in basic and neutral pH also, due to which it can
be used for various applications. Modification and renewability in the chitosan as
per the requirement enhance the research in the field of bio-polymers. Chitosan
nanocomposite synthesis methods and surface functionalization develop the pecu-
liarity of further applications. Coagulation–flocculation efficiency plays a keen role
in the activity of chitosan-based nanocomposites which can be leading to improved
several applications such as biosensor development, wastewater treatment and biore-
mediation. People can establish cost-effective techniques for various contaminants
and eliminate different pollutants efficiently. The bactericidal efficiency of the fabric
could also be increased by differing the functional groups of nanocomposites. The
scope of improvement is still left as per the various applications of chitosan compos-
ites without harming the environment due to biodegradable nature of chitosan. There
is still an economical challenge to introduce commercial viability of sustainable
biopolymer in real market as the techniques and innovations executed at indus-
trial scales. However, manufacturing and fabrication of these nanocomposites into
functional groups of bioactive component enriched textile is a promising hope.
3 Preparation and Applications of Chitosan–Gold Bionanocomposites 87
Further, for industrial realism an insightful investigation of these biopolymers is
still needed. These investigations towards acquisition of novel sources, economic-
efficient intensive extraction process and execution of innovative techniques would
impart substitute to harmful synthetic microbicidal products. Hence, the metals such
as Au, Ag-doped chitosan nanocomposite or biopolymer are a potential material
for the wastewater application, especially in heavy metals and dyes removal due
to its biodegradable, stable, economically efficient nature and easy to synthesize
properties. These gold/silver-doped chitosan-based materials could be scaled up for
industrial application, after some modification.
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Clin. Mater. 15, 273 (1994)
Chapter 4
Environmental Properties
and Applications of Cellulose
and Chitin-Based Bionanocomposites
Renyan Zhang and Hui Xu
Abstract Bionanocomposites are class of bio-based nanostructured hybrid mate-
rials, which exhibit at least one dimension on the nanometer scale. In general,
bionanocomposites are comprised of biopolymers and other organic or inorganic
sources. Cellulose and chitin are the two most abundant biological polymers in
nature. In recent decades, cellulose and chitin-based bionanocomposites have trig-
gered a great deal of attention to understand such composite materials and their
applications. Thanks to their renewable, biodegradable, biocompatible, low-cost,
low-density, eco-friendly properties, and low energy consumption, cellulose and
chitin-based bionanocomposites are excellent green technology materials. Currently,
cellulose and chitin-based bionanocomposites are widely used in a variety of fields,
such as environmental protection, electronics device industry, biomedicine industry,
food industry, and agriculture industry. In this chapter, the sources and properties
as well as the extraction and preparation methods of the corresponding cellulose
and chitin bionanocomposites are introduced. The environmental characteristics of
cellulose and chitin-based bionanocomposites and their applications in various fields
are reported.
4.1 Introduction
4.1.1 Cellulose
Cellulose is the most abundant renewable biodegradable polymer on earth, with
global production estimated at 1010 –1011 tons per year [1]. This biopolymer is widely
distributed in higher plants, marine animals, algae, fungi, bacteria, and invertebrates
R. Zhang · H. Xu (B)
School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center
for Advanced Materials, Institute of Advanced Synthesis, Nanjing Tech University,
Nanjing 211816, China
e-mail: ias_hxu@njtech.edu.cn
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_4
99
100 R. Zhang and H. Xu
and even found in protozoa. In 1838, it was discovered and isolated in plant tissues
by Anselme Paine, a French chemist.
Cellulose microfibers are the basic structural components of cellulose, consisting
of 36 individual cellulose molecules [2]. Microfibrils are then packaged into larger
units to form microfibrillated cellulose. Microfibrinolytic cellulose is reassembled
into familiar cellulose fibers, as shown in Fig. 4.1. Microfibrillated cellulose (also
known as nanofibrillated cellulose) has a diameter of 20–50 nm. The diameter of a
single cellulose microfibril ranges from 2 to 20 nm [3, 4], which can be regarded as
a flexible hair filament, and the fiber crystals are connected along the microfibrils
axis through disordered amorphous structural domains [3]. The ordered regions are
wrapped in cellulose chains and stabilized by a strong and complex network of
hydrogen bonds [2], similar to nanocrystalline rods. Cellulose is composed of linear
oligosaccharides consisting of β-d-glucopyranose units linked together by β-1–4-
linkages [5]. The repeating unit structure of cellulose is depicted at bottom panel of
Fig. 4.1. It shows a dimer called fibrinolytic sugar in the form of repeated fragments.
The monomer, known as the anhydroglucose unit (AGU), has three hydroxyl groups.
These groups form strong hydrogen bonds, thus offering cellulose the most important
properties, in particular (i) multi-scale micro-fibrosis structures, (ii) graded structures
(crystalline and non-crystalline areas), and (iii) high cohesion (vitrification transition
temperatures are higher than their degradation temperatures) [1]. In the process of
biosynthesis, hydrogen bonds between adjacent hydroxyl and oxygen molecules
induce the formation of parallel accumulation of multiple cellulose chains.
Fig. 4.1 Schematic demonstration of cellulose hierarchical architecture from the cellulose sources
present in nature. Reprinted from Ref. [1]. (Copyright (2012) Elsevier Publishing Group)
4 Environmental Properties and Applications of Cellulose … 101
Cellulose has four different kinds of polymorphs: cellulose I, II, III, and IV.
Cellulose I is a form found in nature and occurs in two different forms, Iα and Iβ.
Attala et al. [6] propose that most natural cellulose is a mixture of the two variant
forms. Triclinic Iα is predominant in algal–bacterial cellulose, while monoclinic
Iβ form is a variant present in typical cellulose of annual plants [7]. Cellulose II
is prepared by precipitation in an alkaline solution. These represent the two main
polycrystalline forms of cellulose. Main difference is that two kinds of cellulose II
with antiparallel accumulation, and chain run in parallel to the direction of cellulose
I[
8–10]. It is important to note that cellulose II in each glucose residues of additional
hydrogen bonds makes this variant the most stable form of thermodynamics [10].
Cellulose IIII and IIIII are obtained by ammonia treatment of cellulose I and II, and
through the modification of cellulose III, eventually produce cellulose IV [1]. Among
them, due to its high crystallinity and modulus, the cellulose I is responsible for the
mechanical properties, through the tradition of lignocellulose bleaching processing
after extraction, used for the preparation of cellulose nanofiller.
Nanoscale cellulose has been found to be very promising enhancement element.
There are basically two types of nanocellulose particles: (i) cellulose nanocrystals
(CNCs) and (ii) cellulose microfibers (CMFs) [11].
In 1870, Nageli and Schwendener first discovered definite crystalline zones in the
amorphous structure of cellulose materials, which is the earliest description of CNCs.
In 1947, CNCs were first produced by Nickerson and Harble [12]. In the experiment,
it was observed that the degradation of cellulose fibers caused by boiling in acidic
solution reached its limit after a certain period of treatment. This is the first literature
on the separation of CNCs available. In 1950, Rånby and Ribi produced colloidal
cellulose crystals (i.e., CNCs) through hydrolysis of wood and cotton cellulose by
sulfuric acid. They further observed for the first time the existence of acicular particle
aggregates under transmission electron microscopy (TEM) images [13]. It is also the
first time that such crystalline regions have been called “cellulose micelles.”
The exploration of CNCs has been going on for a long time. In addition to the
discovery process described above, the preparation of CNCs has entered a new stage
since the 1990s. And with the progress of the research, a growing number of terms
used to refer to CNCs, such as nanocrystalline cellulose, cellulose whiskers, rod-like
colloidal particles, cellulose microfibrils, and cellulose microcrystallites. Until 2017,
the international organization for standardization issued cellulose standard terms and
definitions of nanomaterials, and specified the term “cellulose nanocrystals.” One
of the breakthroughs was the discovery of the properties of liquid crystals in 1992.
Revol et al. [14] reported an in vitro system in which only cellulose exists in the form
of fibrous fragments dispersed in water.
In the following years, cellulose nanocrystals received more and more atten-
tion and development. In 1995, Favier et al. [15] were inspired by the extracellular
high-performance skeleton biological complexes composed of matrix reinforced by
fibrous biopolymer synthesized in animals or plants and tried to simulate the biolog-
ical complexes by mixing cellulose whiskers. They obtained lab-scale nanocom-
posite structures through enhancement experiments using whiskers extracted from
rare cellulose samples. In 1998, Dong et al. [16] found for the first time that chiral
102 R. Zhang and H. Xu
nematic ordering in cellulose microcrystalline suspensions was highly dependent
on hydrolysis and preparation conditions. Among them, the particle size, surface
charge, and polydispersity of cellulose microcrystals vary with the degree of hydrol-
ysis. Longer hydrolysis time leads to shorter single crystal and higher surface charge.
In 2001, Araki et al. [17] successfully prepared spatially stable cellulose microcrys-
talline suspension by grafting polyethylene glycol (PEG) through carboxylation-
amidation process. The grafted cellulose microcrystals are more stable and have the
ability to disperse from the lyophilized state to aqueous or non-aqueous solvents.
These characteristics are beneficial to the industrial application of microcrystalline
cellulose. In 2006, Bondeson et al. [18] employed response surface methodology
to optimize the process on the basis of previous studies, aiming to find a faster and
higher yield method to obtain water-stabilized colloidal suspensions of CNCs. It
was found that the optimized crystal separation required the increase of sulfuric acid
concentration and hydrolysis time. In recent years, the development of commercial
production of CNCs is still under study [19]. In 2019, Song et al. [20] reported
the extraction of CNCs from Calotropis procera biomass by classical sulfuric acid
hydrolysis (Fig. 4.2).
Microfibrillated celluloses (MFCs), also known as microfibrillar celluloses, cellu-
lose microfibrils, or nanofibrillated celluloses (NFCs), are a relatively new type of
cellulose materials. MFCs are getting more favor of the researchers than CNCs. In
fact, scientific papers were published almost every two days in 2011. In contrast to
straight CNCs, MFCs are long and flexible nanoparticles. They are composed of
alternating crystalline and amorphous regions and vary in size, ranging from 10 to
100 nm in diameter and usually in the micron scale in length [4, 21]. In addition,
Fig. 4.2 Preparation procedure of CNCs from Calotropis procera fiber. Reprinted from Ref. [1].
(Copyright (2019) Springer Nature Publishing Group)
4 Environmental Properties and Applications of Cellulose … 103
MFCs have a very high L/D ratio, which gives them a very low percolation threshold,
and therefore a very good ability to form rigid networks.
MFCs are obtained through the fibrillation process of cellulose fibers. There are
several different pathways for the production and preparation of MFCs. Generally,
the first step is always to soak the pulp and disperse it in water. The cellulose fibers
are then carefully separated into microfibers under high shear forces. To generate this
shear force, different intensive mechanical processing methods can be used, such as
high-pressure homogenizers [22], grinding [23, 24], low-temperature crushing [25],
high-intensity ultrasound, electrospinning [26], and some other methods. Depending
on the raw material and degree of processing, necessary chemical treatments, such
as enzyme treatments, can also be carried out prior to mechanical fibrillation.
In 1983, Herrick et al. [] and Tubark et al. [22] first produced MFCs by means of
a mechanical homogenizer with diluted cellulosic wood pulp-water suspension, in
which a large pressure drop was conducive to micro-fibrosis. In 1997, Dufresne et al.
[25] conducted a freeze grinding process to generate MFCs from beet pulp. MFCs
can also be produced by electrostatic spinning. In 2003, Huang et al. [26] summarized
the electrostatic spinning technology and its application in the production of polymer
nanofibers. With the achievements in processing and collecting continuous uniaxial
nanofibers, their more critical applications as reinforcements for the fabrication of
primary loaded nanocomposite elements can be realized. In 2004, Zimmermann et al.
[27] proposed a mechanical fibrillation process in the homogenization step using a
microfluidizer. It imposes a very high shear rate, resulting in the formation of quite
thin MFCs. However, the mechanical refining method did not fully pulverize the
pulp fibers. Therefore, a finishing process was added before homogenization. This
is essentially internal fibrillation, which loosens the fiber walls and prepares for
subsequent homogenization. In 2006, Saito et al. [28, 29] proposed a new method
to obtain MFCs through 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated
oxidation. According to studies, TEMPO-mediated oxidation pretreatment signifi-
cantly reduces energy consumption compared with repeated cycle energy consump-
tion of high-pressure homogenizer [30]. After the free radical-mediated oxidation of
TEMPO, the undried natural cellulose was decomposed into individual microfibers,
which were then treated mechanically with homogenization. The combination of
oxidation and homogenization has been found to be advantageous, using a much
lower energy input to break down the cellulose into microfilaments of smaller width.
Another pretreatment is enzymatic hydrolysis which is usually used in conjunc-
tion with mechanical shearing. Henriksson et al. [31] developed an environmentally
friendly enzyme-assisted method for the synthesis of MFCs in 2007. It had been found
that the pretreatment of pure C-type endoglucanase contributed to the disintegration
of cellulose wood fiber pulp into MFCs in more environmentally friendly process
without solvent or chemical reactants, compared to the acid hydrolysis method. The
resulting MFCs showed high average molar weight and large aspect ratio, which
indicated that the enzyme treatment increased the swelling of MFC fibers in water,
and thus facilitated the preparation of MFC nanofibers.
104 R. Zhang and H. Xu
4.1.2 Chitin
Chitin, second only to cellulose, is the second most abundant polymer in nature,
mainly found in the exoskeletons of shellfish and insects and in the cell walls of
mushrooms, and is synthesized by mollusks, crustaceans, insects, fungi, algae, and
related organisms at a rate of 1010 to 1011 tons per year [32, 33]. Chitin is the
main component of the shell and is widely distributed in nature. Shrimp and crab
shells are the main raw materials for chitin extraction. Braconno, a French scholar,
first discovered it in 1811. And it was extracted from crustacean shells by Odier in
1823. Chitin is also structurally similar to cellulose, except that it has an acetamide
group at the C2 position. In other words, chitin is composed of (1-4)-linked 2-
acetamido-2-deoxy-B-d-glucopyranose unit [33], which is the homopolymer of N-
acetylglucosamine (Fig. 4.3).
Due to its linear structure of one acetamide group and two hydroxyl groups, chitin
is a biopolymer with highly expanded hydrogen-bonded semicrystalline structure,
which usually appears as nanoscale ordered fibrils in living tissues. Chitin can be
classified as α, β,or γ-chitin according to species origin and unit arrangement. α-
Chitin is commonly found in the shell of shrimps and crabs, and it is the most stable
and common form. The repeating units of chitin macromolecules are antiparallel, and
they are connected to each other by hydrogen bonds to the maximum extent possible,
resulting in a crystallinity of more than 80%. β-Chitin, found in squid, has molecular
units arranged in parallel. The fiber can reach 70% crystallinity. γ-Chitin, on the
other hand, is formed by the combination of α and β and is alternately assembled by
Fig. 4.3 Schematic demonstration of chitin hierarchical architecture from t he crab shell. Reprinted
from Ref. [32]. (Copyright (2012) RSC Publishing Group)
4 Environmental Properties and Applications of Cellulose … 105
two parallel chains, one of which is antiparallel. Natural chitin with strong hydrogen
bonds in crustacean shells is highly crystalline and arranged in an antiparallel fashion
as R-chitin microfilaments. These microfibers consist of nanoscale fibers with a diam-
eter of about 2–5 nm and a length of about 300 nm embedded in the protein matrix
[34]. Its structural hierarchy is shown in Fig. 4.3. The chitin with high crystallinity is
often referred to as chitin nanocrystals (CTNs), chitin whiskers, or chitin nanofibers.
Because crab shells and shrimp shells have fractionated structures composed of
nanofibers, the researchers believe that the separation method of CNCs is also suitable
for the preparation of CTNs. The main method is acidic or enzymatic hydrolysis of
chitin. However, the specific processing process of chitin varies with its sources, such
as crab shells, shrimp s hells, and mushrooms. Next, we will introduce the preparation
of CTNs from different sources.
CTNs are produced from crab shells through a decomposition process. The usual
procedure is to purify the shells by chemical treatment, followed by mechanical
treatment, and then by sodium hydroxide aqueous solution and hydrochloric acid
treatment to remove proteins and minerals from the shells [35, 36]. Ifuku et al. [34]
studied the extraction of natural CTNs with a width of 10–20 nm from crab shells
(Fig. 4.4a). It is made by simply grinding dry crab shells under acidic conditions after
removing proteins and minerals. Fan et al. [37] successfully prepared dispersed CTNs
in water from crab shells by TEMPO-mediated oxidation technology. These methods
enable to obtain large quantities of chitin nanocrystals from discarded crab shells,
and the resulting CTNs still have their original chemical and crystalline structures.
The method of preparing CTNs from crab shells is suitable for all kinds of shrimp
shells because the shells are also composed of the same hierarchical structures. Ifuku
et al. [38] prepared CTNs from shrimp shells through a simple grinding process
after removing proteins and minerals. The CTNs prepared in an acid-free chemical
environment are highly homogeneous and have a diameter of 10–20 nm, which is
similar to that of crab shell nanofibers treated in acidic conditions.
CTNs can also be obtained from the cell wall of mushroom [39, 40]. Ifuku et al.
[41] isolated CTNs of different widths from the cell walls of five different types of
mushrooms by removing dextrans, minerals, and proteins and then simply grinding
them under acidic conditions (Fig. 4.4b). Homogenous CTNs produced from mush-
rooms are important dietary fibers. With the development on mushroom nanofibers,
they are now of great interest as functional food ingredient as well as for medical
applications.
β-chitin is widely present in squid. Fan and Isogai et al. [42] prepared individual-
ized CTNs with a cross section width of 3–4 nm and a length of at least a few microns
from squid pen β-chitin. It was found that N-deacetylation of chitin molecules did not
occur during the transformation of nanofibers. Although the crystallinity index was
reduced, the β-chitin retained its original crystal structure. The authors suggested
that the cationization of C2-amino on the surface of β-chitin of squid pen should be
a necessary condition for the preparation of CTNs under acidic conditions.
106 R. Zhang and H. Xu
Fig. 4.4 Schematic extraction of CTNs from a crab or prawn shells, and b mushrooms. Reprinted
from Ref. [34, 41]. (Copyright (2009) ACS Publishing Group and Copyright (2011) MDPI
Publishing Group)
4.2 Environmental Properties
Environmental properties refer to those physical properties, such as solvent solu-
bility, heat conductivity, mechanical and electrical properties, which relate to the
environment. Due to the shortage of natural resources and increased energy needs,
renewable, biodegradable, and eco-friendly materials received widespread attention.
The accumulation of synthetic plastics used in packaging applications is causing
serious environmental problems. This challenge has prompted the researchers to
explore the use of polysaccharides such as starch, cellulose, chitin/chitosan, alginate,
and animal protein polymers materials, because these biological materials are often
renewably sourced and degradable via naturally existing pathways [43, 44]. Cellu-
lose and chitin-based materials are known to be biodegradable. They can degrade
in the presence of microorganisms or are susceptible to hydrolysis. Cellulose and
chitin-based biomaterials offer opportunities to reduce the utilization of landfills and
environmental accumulation of plastics. Therefore, it is not difficult to understand
4 Environmental Properties and Applications of Cellulose … 107
that the environmental properties of cellulose and chitin-based nanocomposites have
been studied more and more.
4.2.1 Mechanical Properties
The large specific surface area and high crystalline arrangement of cellulose and
chitin nanofibers lead to impressive mechanical properties, making them potential
candidates for improving the mechanical properties of pure substrates. It is generally
believed that the nanofibers form percolation networks at critical concentrations, in
which the aspect ratio of the fibrils and the high crystalline morphology play an
important role, resulting in higher mechanical properties of the composites.
Favier et al. [15] firstly reported the synthesis of CNC-based nanocomposites. The
researchers obtained lab-scale nanocomposites by reinforcing the latex with whiskers
extracted from cellulose samples. The unusual mechanical property is due to the
hydrogen-bonding systems in the composites, which hold the percolating network of
the fibers. Wongpanit et al. [45] investigated the effect of CTNs on the dimensional
stability of silk fibroin sponge nanofillers. Water suspensions of 4.63wt% CTNs
were added to the solution in different proportions. The sponges produced by this
method showed a network of interconnecting holes which were clearly observed by
scanning electron microscopy (SEM). Compression tests showed that the mechanical
properties were significantly improved by hydrogen-bonding interactions between
the substrate and the chitosan nanofibers. Choi et al. [46] studied CNCs as fillers of
carboxymethyl cellulose to prepare a novel hydrogel composite. The experimental
results showed that CNCs significantly improved the strength and stiffness of the
composites.
4.2.2 Thermal Properties
The thermal properties of materials are crucial to determine the temperature range of
processing and use. With the introduction of cellulose and chitin nanoparticles into
the composites, the thermal properties of the composite materials can be enhanced.
Lu et al. [47] evaluated the thermal properties of polyvinyl alcohol (PVA) matrix rein-
forced with MFCs, which was isolated from kraft pulp by a mechanical process. The
thermal stability of the MFC–PVA composite films was slightly improved with the
addition of MFCs. Hariraksapitak et al. [48] prepared bone scaffolds by freeze-drying
α-chitin whiskers in combination of hyaluronan and gelatin. Mechanical and thermal
analyses of the scaffolds were characterized. It was confirmed that the mechanical
properties of the scaffolds were enhanced by increasing the content of CTNs, and
the increase of CTNs also improved the thermal stability.
108 R. Zhang and H. Xu
On the other hand, surface modification of CNCs or CTNs with functional groups
may lead to improved thermal properties. Ifuku et al. [49, 50] studied surface maley-
lation and naphthalylation of CTNs to enhance thermo-responsive properties. The
experiment was accomplished by reacting with phthalic anhydride in an aqueous
medium, where the phthaloyl group was quantitatively introduced onto the surface
of deacetylated CTNs. The unique structure of the nanofiber network was maintained
after phthaloacylation. The phthaloylated nanofibers were homogeneously dispersed
in aromatic solvents and exhibited reversible thermal responses. Tingaut et al. [51]
developed bionanocomposite materials using acetylated MFCs as reinforcing agent
in poly(lactic acid) (PLA) matrix. Comparing to the PLA matrix blended with unmod-
ified MFCs, the thermal stability was improved upon acetylation. The grafted acetyl
groups reduced the hydrogen-bonding interactions among the MFCs, thus allowing
better dispersion in the PLA matrix. And the acetylated MFCs could be stored in dry
form, making it possible to achieve large-scale industrial production.
4.2.3 Barrier Properties
Many membranes with high barrier properties may prevent the permeation of gases,
vapors, hydrophilic water, and hydrophobic toxic chemicals. Cellulose nanofillers
including CNCs and MFCs can be designed into the most effective barrier membranes
due to the ease of processability and their good barrier properties. For example,
TEMPO-oxidized CNCs extracted from Whatman paper were used as barrier
membranes in a PVA matrix. The integration of the oxidized CNCs into the nanocom-
posite provided a physical barrier through the creation of a tortuous path for the
permeating moisture. Hence, the introduced CNCs decreased the water vapor trans-
mission rate of the matrix. The best membrane barrier performance was achieved by
the addition of 10 wt% CNCs with 10 wt% PAA.
Surface chemical modification of MFCs provided another route to improving
barrier properties from the perspective of packaging applications. For example,
Rodionova et al. [52] conducted research on heterogeneous acetylation of MFCs to
produce membranes with good barrier properties. Compared with those of common
packaging materials, the acetylated MFC films showed a similar oxygen transmission
rate.
4.2.4 Biodegradability
Biodegradability is the capacity for biological degradation of materials down to the
base substances such as water, methane, carbon dioxide, basic elements, and biomass.
Cellulose and chitin-based products are made from natural raw materials, which are
biodegradable with the help of microorganisms.
4 Environmental Properties and Applications of Cellulose … 109
Bras et al. [53] mixed cellulose whiskers with natural rubber to study the effect
of CNC content on biodegradation of the nanocomposites. They observed that the
biodegradation rate increased sharply with the increase of CNC content compared
to pure natural rubber. The rapid degradation of cellulose components leads to
increased porosity, void formation, and integrity loss of natural rubber matrix, and
thus, the overall decomposition rate of nanocomposite membranes containing CNCs
was faster than that of pure rubber membranes. Miller et al. [54] investigated the
biodegradation of three PLA thin-film reinforced CTN composites used for pack-
aging applications. The results showed that the biodegradability of all the PLA-CTN
composites was faster than that of pure PLA. The faster biodegradation was attributed
to the presence of CTN on the surface of the composites. At the same time, the
biodegradation was accelerated with the increase of filler content.
4.2.5 Antibacterial and Antifungal Properties
Antibacterial and antifungal properties are another very important properties for
cellulose and chitin-based materials. Recently, the antibacterial and antifungal activ-
ities of cellulose and chitin and their derivatives have received considerable attention.
Ciecha´nska et al. [55] obtained modified bacterial cellulose in a form of hydrogel
from acetic bacterium Acetobacter xylinum. The resulting hydrogels had many valu-
able characteristics, such as good mechanical property, high moisturizing property,
and most importantly, good antibacterial bactericidal activity. These features make
these modified bacterial cellulose hydrogels good dressing materials for all kinds of
wounds, burns, and ulcers. Dutta et al. [56] prepared N-halamine CTN films through
the reaction of CTNs with sodium hypochlorite solution. The surface N-chlorination
of chitin nanofiber rendered them antibacterial and antifungal activity. Gram-negative
bacteria (i.e., Escherichia coli) and gram-positive bacteria (i.e., Staphylococcus
aureus) as well as two examples of fungi (i.e., Alternaria alternata and Penicil-
lium digitatum) were investigated to evaluate the antibacterial property and anti-
fungal activity of the chlorinated CTN films, respectively. The N-halamine CTN
films showed strong efficacies against those above bacteria and fungi.
4.3 Applications of Cellulose-Based Bionanocomposites
Cellulose-based bionanocomposites have attracted extensive attention due to their
low density, low cost, non-abrasive, flammable, non-toxic, and biodegradable
properties. This section specifically discusses the applications of cellulose-based
bionanocomposites in various fields, including electronics device, biomedicine
industry, food industry, and environmental protection.
110 R. Zhang and H. Xu
4.3.1 Electronics Device Industry
Cellulose-based biological nanocomposites have been increasingly used in the fields
of electronics industry, such as earphone diaphragm, electronic display screen,
membrane electronic components, batteries, and so on.
4.3.1.1 Electronic Paper
Transmission and presentation of information have always been an important work
in human communication. Among all the existing display information technologies,
printed paper using cellulose as raw material has played an extremely important role
since ancient times. It is still the most important and accepted media for information
display owing to its high reflectivity, high contrast, high flexibility, and low cost.
Along with the rapid development of computer and Internet, the traditional form of
printing paper display technology clearly wasn’t enough to bear the huge amount of
information transmission; therefore, the standard of the digital media display tech-
nology arises at the historic moment, mainly including liquid–crystal display (LCD),
cathode-ray tube (CRT), organic light-emitting diode (OLED), and plasma screen.
In recent years, more and more research groups are working to combine the optical
properties of paper with traditional digital screens and promote the development
of the dynamic display technology of analog paper, commonly known as “elec-
tronic paper.” Techniques used in so-called electronic paper include electrophoresis,
bicolor beads, cholesterol-type liquid crystals, and electrowetting methods [57, 58].
A current research direction is to achieve paper-like properties with real cellulose
substrates, thereby directly achieving the desired optical properties of paper.
In the past, the largest source of cellulose used in paper was plant cell walls, and
the paper produced by this method was not pure enough to meet the requirements
of electronic paper, until 1886 when researchers studied Acetobacter and discovered
that this bacterium produces a tough gel film of pure cellulose [59–61]. On the basis
of these studies, the Shah et al. [62] the preparation of the size stability has the
paper shape as well as the unique microfibrils nanostructures of bacterial cellulose
membrane, and through the surrounding sedimentary microfiber ions to provide a
conductive path, then electrically induced color dye [63] fixed within the microstruc-
ture, thus making cellulose conductive or semiconductive films, and drive circuit,
using the standard back or to build using cellulose as a substrate of high-resolution
dynamic display device. The device with high reflectivity, flexibility, contrast and
pattern biodegradability, and many other advantages has the potential to expand to
a variety of applications, such as e-books, tablet computer, electronic newspapers,
wallpapers, rewritable maps and learning tools, and even show on textiles, looking
forward to providing the world with a highly adaptive and spread the effective medium
of communication and education.
4 Environmental Properties and Applications of Cellulose … 111
4.3.1.2 Organic Light-Emitting Diodes (OLEDs)
Organic light-emitting diodes (OLEDs), also known as organic electromechanical
laser display or organic light-emitting semiconductor, have the advantages of self-
illumination, high reaction speed, low power consumption, almost infinite high
contrast, wide viewing angle, and a variety of emission colors can be selected through
the molecular design of organic materials. Commercial OLEDs are made on a glass
substrate. In recent years, the rapid development of optoelectronic technology makes
flexible display possible, and flexible organic light-emitting display (FOLED) tech-
nology based on OLED has attracted wide attention because of its attractive display
application characteristics. This technology may make highly portable and folding
display technology possible in the future. The use of a suitable biocompatible flex-
ible substrate is essential to the development of such a device. Among them, the
bacterial cellulose has received a lot of attention and applications due to its unique
properties and high purity [62, 64–70]. More importantly, bacterial cellulose rein-
forced nanocomposites have a very low coefficient of thermal expansion [65, 70, 71],
which can effectively prevent strain and eventual cracking due to the mismatch of
thermal expansion coefficients caused by thermal cycling when different materials
are deposited on the substrate through heat treatment [72]. It is also worth noting
that bacterial cellulose is an excellent enhancer for the design of renewable and
biodegradable nanocomposites. Legnani et al. [73] fabricated a flexible substrate
for OLEDs using bacterial cellulose film produced by Gluconacetobacter xylinus.
They used radio frequency magnetron sputtering to deposit the thin film of indium
tin oxide onto a dry bacterial cellulose film at room temperature and characterized
the structure, optical, and electrical properties of the functionalized substrate. Then,
they prepared the small molecule thin film with tri(8-hydroxyquinoline) aluminum
(AlQ3) compound as the luminescent layer. The results clearly showed that func-
tionalized bacterial cellulose membranes that were biodegradable and biocompat-
ible could be used as flexible substrates in FOLED devices. Ummartyotin et al. [74]
also successfully prepared transparent flexible nanocomposites composed of bacte-
rial cellulose and polyurethane resin and used them as substrates for OLEDs. The
nanocomposite material prepared by thermal evaporation deposition showed good
flexible performance. Even when it was bent, it could emit light (Fig. 4.5). This work
can also demonstrate that bacterial cellulose-based nanocomposites are a promising
candidate for FOLEDs.
4.3.2 Biomedicine Industry
In recent years, rapid progress has been made in the field of biomedical mate-
rials, using natural or synthetic polymers for a variety of applications. Due to their
unique nanostructure and properties, cellulose-based nanomaterials have proven to
be natural candidates used in a very wide range of medical applications, including
112 R. Zhang and H. Xu
Fig. 4.5 OLEDs on bacterial cellulose nanocomposite. Reprinted from Ref. [77]. (Copyright (2012)
Elsevier Publishing Group)
wound healing, vascular grafts, and scaffolds for tissue engineering in vitro or in vivo
[75–80].
4.3.2.1 Wound Healing and Artificial Skin
The healing of large areas of skin wounds and even the development of artificial
skin are significant medical advances [81]. Wound healing is a complex interaction
involving many aspects and a series of processes, in which the healing of chronic
wounds, such as ulcers, is particularly important in a series of steps. Various types of
wound dressings have been developed and used over a long period of time in order to
eliminate adverse environments in chronic wounds and promote proper healing [82–
84]. Similarly, burns are an injury that causes extensive and complex damage to skin
tissues, and many different wound dressings have been developed [85–90]. Cellulose-
based pads, membranes, films have been found to be very effective for improving
the healing process by reducing pain and accelerating granulation growth, which is
very important for proper wound healing.
Fontana et al. [91] reported that a thick, smooth, and floating cellulose film
prepared from Acetobacter cultured in a specific medium could be applied to exudate
or bleeding tissue as a biological dressing. It is therefore concluded that it is valuable
as a temporary skin substitute in the treatment of skin wounds, such as burns and
ulcers, as well as an adjunct in the treatment of severe abrasions. Czaja et al. [92]
used never-dried microbial cellulose membranes to treat patients with severe second-
degree burns and found that the wound healed significantly faster than conventional
dressings. Moreover, these cellulose membranes can be made in any shape and size,
which is good for treating large wounds and some hard-to-cover areas.
4 Environmental Properties and Applications of Cellulose … 113
Bacterial cellulose membranes can accelerate the healing process, resulting in a
more effective wound dressing material without any change in its beneficial prop-
erties. Barud’s team [93] developed a biofilm containing bacterial cellulose and
standardized propolis, showing a good treatment for burns and chronic wounds.
Legeza et al. [94] investigated the effect of a novel bacterial cellulose wound dressing
impregnated with superoxide dismutase and PVA on the repair process of deep skin
burns in rats. Studies have shown that the healing effect of the burns is significantly
accelerated.
4.3.2.2 Tissue Engineering
Tissue engineering looks for new materials and devices that can actively interact
with biological tissue as an in vitro basis for cell growth, or for rearranging and
developing the tissue to be implanted. Therefore, biocompatible and biodegradable
cellulosic materials have come into the attention of scientists and have been employed
for in vitro tissue reconstruction or cell scaffolds [95–97]. The chemical surface of
cellulose can determine the reaction of cells by interfering with cell adhesion and
proliferation, and effectively overcome the mutual repulsion between surface cells,
and even be absorbed or biodegradable after a period of time [98–100].
Atherosclerotic vascular diseases continue to be one of the leading causes of death
in today’s society. Treatment methods and means for cardiovascular diseases have
been studied and explored by several generations [101–107]. Surgical treatment of
atherosclerosis began in 1952 when Voorhees et al. [101] hypothesized the replace-
ment of diseased vessels with synthetic fibers. However, the small-diameter grafts
ultimately failed due to occlusion. Synthetic implants are still found to cause low
levels of foreign body reaction and chronic inflammation, and as artificial materials,
they increase the risk of microbial infection. Therefore, artificial blood vessel is a
biomaterial with characteristics tailored for specific cardiovascular device applica-
tions, while taking characteristics such as durability, biocompatibility, prothrombin,
and hypocalcification into account [108–112].
Millon et al. [113] developed a PVA-bacterial cellulose nanocomposite with prop-
erties similar to heart valve tissue. PVA can be converted into solid hydrogels with
good mechanical properties by physical cross-linking using a freeze–thaw cycle [111,
114–120]. It is combined with the bacterial cellulose produced by the bacterium
Acetobacter xylostella through the fermentation process to form a nanocomposite
material showing mechanical properties similar to soft tissue and extensive perfor-
mance control. Therefore, the PVA-bacterial cellulose nanocomposite is a promising
alternative material for cardiovascular soft tissue.
Cellulose nanocomposites such as the above used in wound dressings, artifi-
cial skin, and vascular stents are also promising materials as potential scaffolds for
cartilage tissue engineering [121–125]. In the past studies, hydroxyapatite-collagen
nanocomposites have been used for a large proportion [126–129]. However, in
contrast to the high cost and difficult to control cross infection of many factors, such
as collagen, the combination of natural polymer composites with hydroxyapatite is
114 R. Zhang and H. Xu
expected to provide high mechanical properties, enough, controllable pore diameter
and porosity in situ formability, high water-holding ability, excellent biocompati-
bility and biodegradability of adjustable and good bone conduction and bone union
and other significant features [130–133]. The tight attachment or integration between
cartilage tissue and implant surface is a key factor for the successful implantation of
biomaterials in orthopedic applications. The key points for the normal functioning
of biomaterials are good biocompatibility, bioactivity conducive to bone attachment,
and sufficient mechanical properties [134–140].
Normal cartilage can be considered as a multifunctional hydrogel, so the use of
hydrogels to develop cartilage substitutes is also a potential direction for the devel-
opment of artificial cartilage [141–147]. Yasuda et al. [148] developed a cellulose/
polydimethylacrylamide (PDAAM) gel composed of bacterial cellulose and PDAAM
and confirmed the wear properties of the novel double-network hydrogels using a
plain wear test. The studies indicated that this unique gel material has great potential
as an artificial cartilage.
Applications of tissue engineering are also seen in the field of ophthalmology
[149], nasal reconstruction [150], and tooth tissue regeneration [151–155]. Jia et al.
[149] explored the potential of nanocellulose as a tissue-engineered corneal scaffold.
They studied the growth of human corneal stromal cells on nanocellulose. The results
indicated the potential of the biomaterial as a tissue engineering scaffold for corneal
prosthesis. Amorim et al. [150] studied the tissue response of rabbit nasal dorsum
to cellulose. After six months, the histological evaluation of the treatments revealed
that the cellulose blanket of Acetobacter xylostacter had good biocompatibility and
remained stable throughout the study. So it could be used as good materials for
nasal dorsal enhancement. Novaes et al. [152] reported that a nanocellulose called
Gengiflex was used in the dental tissue regeneration. Gengiflex was composed of
inner microbial cellulose layer and outer chemically modified alkaline cellulose layer.
The inner layer offered rigidity to the membrane. The synthetic hydroxyapatite was
utilized as grafting material in the dental cavities, and the Gengiflex membrane was
employed to cover the implant. After 6-month reentry, a complete restoration of the
defect was observed (Fig. 4.6).
4.3.2.3 Drug Delivery
Cellulose materials have excellent compaction performance when mixed with other
pharmaceutical excipients, which makes the tablet carrier form a dense matrix suit-
able for oral administration [156–158]. On the other hand, nanocellulose has poten-
tial advantages as an excipient for drug delivery. Its relatively large surface area and
negative charge give it a high payload and the potential for optimal dose control. The
rate of tablet disintegration and drug release can be controlled by particle inclusion,
excipient delamination, or tablet coating. For example, Baumann et al. [159] reported
the development of a series of physical hydrogel mixtures composed of hyaluronic
acid (HA) and methylcellulose (MC), which are planned for independent delivery of
one or more drugs and ultimately for spinal cord injury repair (Fig. 4.7). In a similar
4 Environmental Properties and Applications of Cellulose … 115
Fig. 4.6 A nanocellulose called Gengiflex used in dental tissue regeneration. Reprinted from Ref.
[96]. (Copyright (2011) Hindawi Publishing Corporation)
manner, Jeganathan’s team [160] prepared pH-dependent and modified release tablets
using anion hypromellose acetate succinate polymers and cationic Eudragit E poly-
mers to deliver DS in the lower GI tract via an LBL adsorption method. They found
that the release of the drug from the polymer coating is pH-dependent and found that
the addition of citric acid helps to change the microenvironmental pH of the drug
preparation, thus controlling the release of the drug from the drug preparation, such
as non-ionized and hydrophobic drugs.
Fig. 4.7 An intrathecal drug delivery system by HA/MC composite hydrogel. Reprinted from R ef.
[159]. (Copyright (2009) Elsevier Publishing Group)
116 R. Zhang and H. Xu
4.3.3 Food Industry
Nanocellulose and its derivatives have developed their applications in the food
industry because of their high surface area, length–diameter ratio, rheological prop-
erties, hydroscopicity, and non-cytotoxicity and genotoxicity. This part mainly intro-
duces three different applications: (1) as food additives, (2) as functional food
ingredients, and (3) in food packaging applications.
4.3.3.1 Food Additives
Since Turbak and his colleagues [161] first considered nanocellulose as a food addi-
tive in 1983, nanocellulose and its derivatives have become increasingly widely used
in food additives. It has been found that nanocellulose tends to stabilize oil-in-water
emulsions because it is wetted by water more easily than oil. It is not only an excellent
suspension medium for other solids, but also an emulsifying substrate for organic
liquids. Therefore, nanocellulose and its derivatives can be used to stabilize oil or
fat in food and are widely used in the preparation of cake icing, salad dressings and
sauces, as well as stabilizers in cream, etc. [162–166].
In the preparation of surimi-based product, such as traditional Chinese fish balls,
lard is usually added to make the heated product smoother mouthfeel. However, Lard
is considered to be less healthy because it has about half as much saturated fat as
butter. Considering both health and taste requirements, the scientists tried to find lard
alternatives. Yoon et al. [167] used vegetable gum and cellulose gel instead of lard
to enhance gel intensity and cooking tolerance. Later, Lin et al. [168] added a highly
absorbent bacterial cellulose to Dolphin-Fish Surimi to evaluate the properties of
the composite gel. The results showed that alkali treatment changed the structure of
bacterial cellulose and formed a dense porous network. This alkali-treated bacterial
cellulose showed high water retention. Therefore, it is speculated that the use of
alkali-treated bacterial cellulose as a fat substitute and additional dietary fiber source
in processed fish surimi products is feasible. Chen et al. [169] modified the surface of
nanocrystalline cellulose with food-grade octenyl succinic acid to improve its surface
hydrophobicity and significantly improve its emulsification performance, which is
conducive to the preparation of Pickering high internal phase emulsion. Stable and
gelatinous Pickering high internal phase emulsions with fine droplets can be easily
prepared using nanocrystalline cellulose modified by this method, even at very low
particle concentrations in the aqueous phase. This will promote a wide application
of nanocrystalline cellulose in emulsion formulation in food fields.
4.3.3.2 Food Ingredients
Turbak and his colleagues also discovered the potential of nanocellulose in preparing
fat-reducing formulations, demonstrating that nanocellulose could replace oil in the
4 Environmental Properties and Applications of Cellulose … 117
production of low-calorie salad dressings [163]. In addition, Dell Chemical Indus-
tries has also developed the invention of using nanocellulose as a functional food
ingredient that uses nanocellulose and water-soluble sugars to treat intestinal diseases
[170].
At the same time, nanocellulose is a dietary fiber that has a beneficial effect on
the overall health of adults, helping to decrease the risk of chronic diseases as well
as promote beneficial physiological effects, such as lowering blood cholesterol and
blood sugar [171–179]. Nanocellulose can be considered as a potential functional
cellulose with dietary fiber properties for the treatment of intestinal diseases.
Nanocellulose can be used to produce low-calorie foods to treat abnormal weight
[180–182]. Nanocrystalline cellulose can be used as non-nutritive fillers and high-
calorie materials such as sugar and fat substitutes in functional foods. Nanocrystalline
cellulose has good emulsification and can be treated in a specific way to obtain a
greasy feeling similar to fat, so it can be used as a fat substitute [166].
4.3.3.3 Food Packaging
The current food packaging market requires high performance, biodegradable films
with good mechanical properties, optical transparency, thermal stability, and high
gas resistance [183]. And the barrier property is critical for evaluating and predicting
the shelf life of packaged products. Because of their positive impact on mechanical
properties and low permeability to oxygen, cellulose nanoparticles have been used
as fillers for pure thin films to produce sustainable packaging [184–191].
Ashori et al. [192] chemically modified cellulose nanofibers (CNFs) with acetic
anhydride using pyridine as catalyst to change their surface properties. Contact angle
measurements confirmed that the surface properties of acetylated CNFs changed
from hydrophilic to hydrophobic. Through such chemical treatment, the water barrier
performance of the CNFs was improved. Rodionova et al. [52] used acetic anhydride
to heterogeneous acetylation of MFCs, which reacted with hydroxyl groups on the
cellulose molecules, thus making the hydrophilic surface change into hydrophobic.
The surface acetylation of the MFCs appears to be a promising method to develop
MFC films with good barrier performance for liquid water and excellent resistance
to oxygen. These surface modification methods can improve the barrier performance
of the cellulose materials, which is very important for sustainable food packaging.
4.3.4 Environmental Protection
With the consumption of primary energy, the concept of green chemistry of chemical
fiber products is gradually moving away. Therefore, the development and utilization
of cellulose-based bionanocomposites as the main body are also in line with the goal
of sustainable development and environmental friendliness. Therefore, the applica-
tion prospect of cellulose modification technology is broad, and it is mostly used for
118 R. Zhang and H. Xu
the adsorption treatment of sewage, such as the adsorption treatment of N, P, As, Cr
in water. At the same time, the research and application in the field of air purification
are also increasing gradually.
4.3.4.1 Water Purification
Nowadays, the world is faced with the severe problem of water shortage. In addition,
the production of a large amount of wastewater also brings great pressure to human
beings. Traditional wastewater treatment technologies such as coagulation, oxida-
tion, electroprecipitation, ion exchange, membrane separation, floating evaporation
are not enough to deal with the increasingly serious problem of water pollution.
Therefore, the development of new wastewater treatment technologies has become
an urgent problem to be solved. It is well known that adsorption is one of the best tech-
nologies for water purification. Although activated carbon filtration is a commonly
used technology based on the adsorption of contaminants onto its surface, it does not
save money or energy. Therefore, adsorption using low-cost adsorbents has become
a new research direction.
New f unctional materials based on biopolymer have come into people’s sight.
Cellulose is an attractive choice because it is rich in sources, renewable, non-toxic to
the environment, low-cost, biodegradable, and biocompatible. With the progress of
nanoscience, it is possible to develop cellulose-based materials with nanoscale size.
Cellulose-based nanocomposites have been widely used in the adsorption of heavy
metal ions in wastewater to achieve the purpose of removal, enrichment, and recovery.
Compared with the general heavy metal treatment methods, the modified cellulose
adsorbent for adsorption, separation, and extraction of heavy metal ions in wastew-
ater has the advantages of large adsorption capacity, fast adsorption speed, low cost,
simple operation, and no secondary pollution [193–203]. Gouda et al. [204] success-
fully synthesized cellulose-graft-polyacrylonitrile (cellulose-g-PAN) nanofibers. The
cellulose-g-PAN nanofibers loaded with silver nanoparticles (AgNPs) have excel-
lent antimicrobial activity against Staphylococcus aureus, Salmonella typhi, and
Escherichia coli. So the cellulose-g-PAN/AgNPs bionanocomposites can be used
for water disinfection. Liu et al. [205] studied the introduction of phosphate groups
on nanocellulose as biological adsorbents aimed at removing metal ions (e.g., Ag+,
Cu2+, and Fe3+ ) from industrial wastewater (Fig. 4.8). Studies have shown that phos-
phorylated nanocellulose was a highly effective biomaterial for simultaneous removal
of various metal ions from industrial wastewater.
At present, clays such as montmorillonite are of particular research interest as
dye adsorbents, but they have proved ineffective in the treatment of anionic dyes
[206, 207]. Zhao et al. [208] prepared carboxymethyl cellulose/montmorillonite
nanocomposites by solution intercalation. It was found that the higher temperature
and acidic conditions are favorable for the adsorption of chromium on carboxymethyl
cellulose/montmorillonite nanocomposites.
The introduction of magnetic particles into cellulose matrix has been explored as
a promising modification method for removing arsenate. Nata et al. [209] prepared
4 Environmental Properties and Applications of Cellulose … 119
Fig. 4.8 Adsorption of metal ions Ag+,Cu
2+,and Fe
3+ (≈100%) from industrial wastewater by
phosphorylated nanocellulose. Reprinted from Ref. [205]. (Copyright (2015) Elsevier Publishing
Group)
surface-functionalized bacterial cellulose nanofibers with aminated magnetite
nanoparticles by one-pot solvothermal reaction of 1,6-hexanediamine, FeCl3·6H2O
and bacterial cellulose, significantly improved the thermal and mechanical proper-
ties of nanostructured bacterial cellulose films. The amine-rich magnetic cellulose
nanocomposite can be used as an efficient recyclable absorbent for the removal of
arsenate.
Printing and dyeing wastewater is a kind of important pollutants that cause serious
environmental problems and harmful to humans. Therefore, the removal of pollutant
dyes from wastewater is critical to the environment. Cellulose-based nanocompos-
ites containing polyhedral oligomeric silsesquioxane can be used as new biological
adsorbents for organic dyes. Xie et al. [210] investigated the adsorption properties
of nanocellulose hybrid materials for reactive dyes in aqueous solution. It was found
that the removal ability of the nanocomposites was much higher than that of the
control cellulose. Therefore, it is concluded that nano-cellulose hybrid material as
a biological adsorbent has potential application value in low concentration printing
and dyeing wastewater.
4.3.4.2 Air Purification
In addition to water purification, in the field of air purification, activated carbon
particles or fibers have been used as air adsorption filtration materials for a long
120 R. Zhang and H. Xu
time. Although activated carbon has the characteristics of a wide range of appli-
cation, because its adsorption process is physical behavior, so it is not suitable for
high temperature, high humidity conditions. At the same time, its adsorption of
some polar gas molecules (such as SO2,NH
3, and H2S) is often completed after
impregnation with a variety of chemical catalysts, so the reproductivity is very poor,
usually belongs to the disposable non-renewable materials. In contrast, the natural
fiber-modified ion exchanger is a reversible chemical reaction to complete the sepa-
ration and enrichment of various polar molecules. Moreover, it can be prepared into
the appropriate fabric shape, so that it can provide a considerable filtration area in
a small volume operating unit, giving it excellent permeability stability, low resis-
tance to airflow characteristics. Therefore, it can be used in air purification units or
gas masks and masks in the form of packed exchange columns or woven fabrics to
achieve the purpose of air purification.
4.4 Applications of Chitin-Based Bionanocomposites
Chitin shows significant similarities to cellulose. So besides cellulose, the applica-
tion of chitin-based nanocomposites is also attracting attention. This section specifi-
cally discusses the applications of chitin-based bionanocomposites in various fields,
including biomedicine industry, environmental protection, food industry, agriculture,
and cosmetics.
4.4.1 Biomedicine Industry
Due to their non-toxicity, biocompatibility, bioabsorbability, low antigenicity, and
good antimicrobial property, chitin and its derivatives are proved to have extensive
applications in wound healing and dressing, scaffolds for tissue engineering as well
as hydrogels for drug delivery systems in biomedicine industry [211–218].
4.4.1.1 Wound Healing and Dressing
Chitin has special biochemical significance, especially it can accelerate the migra-
tion of macrophages and the proliferation of fibroblasts, and promote the formation
of granulation and blood vessels. When the chitin salt and chitin nanofibers acted
synergistically, the wound healing ability was significantly enhanced. Muzzarelli
et al. [219] prepared three forms of wound medicaments (i.e., spray, gel, and gauze)
by combination of chitin nanofibrils, chitosan glycolate, and chlorhexidine. The
gauze was found to be the most effective in all the dressings. It could induce better
epithelial differentiation and keratinization as well as better reorganization of the
basal lamina in healing injuries or ulcers (Fig. 4.9).
4 Environmental Properties and Applications of Cellulose … 121
Fig. 4.9 Gangrenous pyoderma on the surface of the tibia healed within 40 days treated by the
gauze made from composite of chitin nanofibrils, chitosan glycolate, and chlorhexidine. Reprinted
from Ref. [219]. (Copyright (2007) Elsevier Publishing Group)
Naseri et al. [217] successfully prepared electrospun chitosan-based random-
oriented fiber containing 50 wt% chitin nanocrystals as reinforcers. The results show
that due to the uniform dispersion of chitin nanocrystals in the chitosan matrix, there
are no defects in the prepared electrospinning porous random felt, which indicates that
the matrix has good chemical compatibility with chitin. At the same time, the addition
of chitin nanocrystals improved the water stability of primary felt and promoted the
water-mediated cross-linking process. This nanocomposite with improved mechan-
ical properties and flexibility, combined with its biocompatibility, was considered as
potential candidates for wound dressing applications.
4.4.1.2 Tissue Scaffolds
Tissue scaffolds made from natural polymers exhibit poor mechanical properties,
which may limit their practical application in some demanding areas. In essence,
chitin is a kind of scaffold material that is beneficial to cell adhesion and growth.
Therefore, chitin nanofibers, the product of acid treatment, can be used as both
122 R. Zhang and H. Xu
enhanced nanofillers and bioactive reagents to prepare scaffolds in tissue engineering.
That means the addition of chitin nanofibers or whiskers to the scaffolds can improve
their mechanical properties, thermal stability, and biodegradability. Along this line
of thought, Hariraksapitak et al. [48] successfully prepared continuously enhanced
hyaluronic acid gel nanocomposite scaffolds by freeze-drying method. It was found
that the properties of the composite scaffolds could be adjusted by changing the
amount of chitin whiskers, so as to achieve an optimal balance between their physical,
chemical, mechanical, and biological properties. It was finally proved that the high
proportion of chitin whiskers added enhanced the thermal stability and biodegra-
dation resistance of the scaffolds, while the relatively low proportion of cellulose
whiskers enhanced the tensile strength and increased the biocompatibility of adhe-
sion and proliferation of human osteosarcoma cells, showing a promising prospect
as a bone cell culture medium.
4.4.1.3 Drug Delivery and Release Control
Zhang et al. [220] were the first to incorporate cellulose and chitin nanocrys-
tals into supramolecular hydrogels combined with cyclodextrin/polymer inclusion
complexes. The data showed that the elastic modulus of these composite hydrogels
was increased to 50 times than that of natural hydrogels. The addition of polysaccha-
ride nanocrystals has shown many advantages, such as accelerated gelation, enhanced
mechanical strength, improved corrosion resistance of the solution, and promoted
long-term sustained drug release. In addition, the cell viability assessment confirmed
that the addition of polysaccharide nanocrystals to supramolecular nanocomposite
hydrogels does not induce additional cytotoxicity, which is the basis for biomed-
ical application. Therefore, the supramolecular nanocomposite hydrogels doped with
polysaccharide nanocrystals seem to be good candidates for drug delivery and release
control systems with injection and implantation functions.
4.4.2 Environmental Protection
Environmental protection has become an increasingly important global issue, and
all industries are concerned about the development of technologies to solve envi-
ronmental problems. Chitin-based bionanocomposites for environmental protection
have attracted more and more considerable attention. This part mainly introduces the
applications of chitin-based bionanocomposites in the removal of dyes, organic and
inorganic pollutants, and the remediation of metal pollution.
4 Environmental Properties and Applications of Cellulose … 123
4.4.2.1 Removal of Organic Pollutants
Chitin as organic pollutant adsorbents can also be used to treat colored wastewater by
adsorption. However, the use of chitin for dye removal has extensively been studied
because of its low surface area, high porosity, and high crystallinity. Therefore, it is
very necessary to find a technology that can change the physical structure of chitin
to expand its application as dye adsorbents [221–228].
Tang et al. [229] successfully prepared a chitin-based hydrogel from a concentra-
tion of 3% chitin solution dissolved in 8% sodium hydroxide and 4% urea aqueous
solution as raw material and then cross-linked with 5% epichlorohydrin at low
temperature. The experimental results showed that the chitin-based hydrogel had
a high removal capacity on malachite green dye in aqueous solution because of its
microporous structure, large surface area, and strong affinity to the dye (Fig. 4.10).
Wang et al. [230] prepared a solar photocatalyst for the in situ synthesis of cuprous
oxide in a regenerated chitin/graphene oxide composite membrane using porous
chitin membrane as a microreactor. Cuprous oxide in the matrix excited and gener-
ated free photoelectrons and electron holes, leading to the degradation of dyes. The
graphene oxide sheets promoted the transfer of photoelectrons, leading to a signif-
icant increase in photocatalytic activity under sunlight. The results show that the
porous chitin film can support cuprous oxide and graphene at the same time and
make the photocatalyst easy to recover and reuse. This portable solar photocatalyst
has the advantages of high efficiency and easy recovery and is expected to be used
in water treatment.
In addition, organic contaminants such as melanoids, which are widely distributed
in food and beverage, also need to be addressed. Dolphen’s team [231] studied the
adsorption of synthetic melanoids by CTNs prepared from shrimp shell waste, and the
results showed that chitin nanofibers have a promising application in the adsorption of
melanoids. The results of Fourier transform infrared spectroscopy and elution studies
Fig. 4.10 Adsorption of malachite green in wastewater by a chitin-based hydrogel. Reprinted from
Ref. [229]. (Copyright (2012) Elsevier Publishing Group)
124 R. Zhang and H. Xu
also confirm that the interaction between melanoid and chitin nanofibers includes
electrostatic adsorption and chemical adsorption. The authors also suggested that
chitin nanofibers could be used to adsorb melanoids and other pigments in syrup in
sugar industry.
4.4.2.2 Removal of Inorganic Pollutants
Metal is the main inorganic pollutant in the world. Removing toxic metals from water
is very important in water treatment. Trace toxic metal ions are difficult to remove
from aqueous solution. The use of low-cost adsorbents attracts considerable attention
[232–242]. Biosorption of biogenic materials such as chitin-based nanocomposites is
also considered an emerging technology for treating water containing heavy metals.
Gandhi et al. prepared a polymer composite composed of hydroxyapatite (HAP)
and chitin and studied its ability to remove Cu2+ from aqueous solution. The adsorp-
tion capacities of N-HAPC and N-HAP/chitin composites were 4.7 and 5.4, respec-
tively, indicating that the adsorption capacity of N-HAPC composites was relatively
higher than that of HAP. Kousalya et al. [243] modified chitin appropriately, such
as protonated chitin, carboxylated chitin, and grafted chitin, to improve the metal
adsorption capacity and investigated their adsorption properties for copper and iron
ions. The results show that these adsorbents can effectively remove copper and iron.
Saravanan [244] conducted a batch adsorption study of hexavalent chromium in
aqueous solution using a chitin complex. The results show that chitin complex can
be used as an efficient biological adsorbent with good metal binding ability to remove
chromium ions from aqueous solution. It is also suggested that this adsorbent is not
only suitable for the adsorption of chromium ions, but also suitable for other heavy
metal ions in wastewater. Karthik et al. in situ synthesized polypyrrole functionalized
chitin for its application in the removal of hexavalent chromium from aqueous solu-
tions. The results showed that the polypyrrole functionalized chitin had a medium
adsorption capacity to remove chromium ions from aqueous solution. Hanh [245]
grafted acrylonitrile onto deacetylated chitin by radiation-induced polymerization
method to produce PAN-grafted chitin bionanocomposites. The nitrile groups on
the surface of chitin were further converted into amidoxime which greatly enhanced
the adsorption capacity of metal ions. These PAN-grafted chitin bionanocomposites
could also be used to treat arsenic contamination in groundwater or drinking water.
4.4.3 Food Industry
Chitin and its derivatives occupy an important position in the application of food
industry. Previous studies have fully proved that chitin and its derivatives are non-
toxic. They are natural macromolecular compounds with special amino and hydroxyl
functional groups on the molecular chains. Therefore, compared with many synthetic
macromolecular compounds, they are more suitable for use in food industry.
4 Environmental Properties and Applications of Cellulose … 125
Chitin can stabilize the oil–water interface because of its amphiphilic structure of
sugar ring and thus can be used as food additive to adjust the texture of food. High
internal phase emulsions (HIPEs) have become an ideal choice not only for food,
but also for porous material templates, multiphase soft materials, tissue engineering,
and other fields [246–249]. Emulsions can be stabilized by Pickering stabilization of
colloidal particles, which effectively prevents droplet coalescence. Compared with
surfactant stabilized emulsions, Pickering emulsions provide superior stability at a
relatively low particle dosage [250, 251]. Chitin stands out as food grade, biodegrad-
able, biocompatible, and non-toxic. For example, chitin nanocrystals prepared by
hydrochloric acid hydrolysis can be used as a Pickering stabilizer for cetane water
coating [252]. Zhu et al. [253] successfully prepared a stable oil-in-water high internal
phase Pickering emulsion using a simple two-step strategy. The results show that
chitin nanocrystalline stable HIPEs can meet the requirements of food and green
material cleaning labeling.
Ge et al. [254] reported that CTNs as a reinforcing nanofiller were integrated into
gelatin to the enhancement of mechanical properties and gelling ability of the gelatin.
The resulting gelatin/CTN composite hydrogels had more compact network struc-
ture because of strong hydrogen bonding and electrostatic interaction between chitin
nanocrystals and gelatin. Thus, the nanocomposite hydrogels showed better stability
than pure gelatin hydrogel. The authors assume that these improved gelatin/CTN
composite hydrogels will be widely used in the food industry. Yuan et al. [255]
prepared stable positively charged CTN suspensions by a simple microfluidization
method without changing the chemical structure. A novel soybean protein gel with
adjustable texture properties was obtained by cross-linking with glutamine transam-
inase, which is attributed to the high mechanical properties of CTNs and their strong
interaction with soybean protein. On the other hand, studies have found that after
moderate deacetylation of CTNs, more amino group exposure will lead to stronger
antibacterial activity. Therefore, partial deacetylation of nano-chitin as material rein-
forcement agent can also give certain antibacterial properties to the composites,
which has a great application prospect in the food industry [256].
Chitin and its derivatives can also be used in functional foods. Hyperlipidemia is
a major cause of coronary atherosclerosis and subsequent associated cardiovascular
disease, which has been associated to some extent with obesity. The traditional treat-
ment for hyperlipidemia is lipid-lowering drugs. These synthetic drugs are effective,
but they can also cause adverse reactions. Therefore, the lipid-lowering activity of
many bioactive ingredients extracted from natural materials such as polysaccharides
and dietary fiber has been explored [257–260]. Studies have shown that chitin and its
derivatives can reduce plasma cholesterol, which plays a crucial role in the preven-
tion and treatment of cardiovascular diseases. Ye et al. [261] prepared a partially
deacetylated α-chitin nanofiber/nanowhisker mixture (DEChNs) using 35% sodium
hydroxide and followed by hydrolysis at pH 3–4. To study the hypolipidemic effects
of different doses of DEChNs on male Kunming mice. Histopathological exami-
nation of liver cells showed that DEChNs effectively reduced the accumulation of
lipids in the liver and prevented the development of fatty liver. The results showed
126 R. Zhang and H. Xu
that DEChNs reduced the absorption of dietary fat and cholesterol and effectively
reduced hypercholesterolemia in mice.
4.4.4 Agriculture
Chitin coming from a wide variety of sources is safe and non-toxic and has a
wide range of use in agriculture. Chitin-based bionanocomposites can be employed
as plant growth regulator, soil improver, plant disease inducer, seed coat agent,
drought-resistant agent or water-retaining agent, fruit and vegetable preservative,
feed additive, pesticide carrier, degradable mulching film, and so on.
As early as 1963, Michele et al. directly added lobster shells or chitin to the
soil, and they found that doing so could effectively reduce plant diseases caused
by pathogenic bacteria in the soil. The chitin-breaking bacteria in the soil that the
researchers analyzed produce the enzyme chitin, which not only reduces the biolog-
ical activity of some fungi but also kills nematode eggs. And microbes can not only
break down chitin to provide nutrients for plants, but also use it to improve their
systems. Once the microbial flora is improved, soil aggregates can also be improved.
Chitin and chitosan can be used as seed coating materials because of their excel-
lent film-forming properties. Researchers at the University of Washington coated
wheat seeds with chitosan and found that the treatment not only protected them from
damage by soil fungi during the winter, but also prevented them from a disease that
rots the roots of wheat.
4.4.5 Cosmetics
Chitin derivatives, especially chitin-based bionanocomposites, have been used in the
field of cosmetics because of their safety, non-toxicity, good biocompatibility, film
forming permeability, anti-static, and moisturizing properties. Many countries have
used chitin and its derivatives as matrix to produce cosmetics, and more than 70 kinds
of products have been sold. They are mainly used for shampoo, hair lotion, hair gel,
skin care night cream, sunscreen, advanced antiseptic bath liquid, advanced soap,
lipstick, skin disease health cream, and so on. For example, CTNs functionalized with
quaternary ammonium salt are integrated into shampoo to obtain the characteristics
of anti-static, dustproof, easy to comb, and promoting hair growth. Baths, hand
cleaners, and face cleaners prepared with 2–15% CTNs have the effect of preventing
skin diseases such as rough skin and prickly heat. Moreover, they are also very
effective in the removal of body odor, antipruritic, antibacterial, and other aspects.
Shervani et al. [262] explored possible application of CTNs loaded with gold
nanoparticles (AuNPs) in different fields including cosmetics. As CTNs and AuNPs
both have antibacterial properties, the obtained organic–inorganic hybrid CTN-
AuNPs composites may double dose effect when CTNs are conjugated with the
4 Environmental Properties and Applications of Cellulose … 127
Fig. 4.11 Chitin nanofibrils for advanced cosmeceuticals by maintaining cutaneous homeostasis.
Reprinted from Ref. [263]. (Copyright (2008) Elsevier Publishing Group)
metallic nanoparticles. The composites molded in thin film would be as suitable for
use in cosmetics. Morganti et al. [263] also studied CTNs for advanced cosmeceu-
ticals in terms of promoting health and beauty. They suggested that CTNs appear
to help maintain the stability of the skin’s internal environment and the activity of
neutralizing free radicals and represented a natural carrier conducive to transdermal
penetration of many active ingredients (Fig. 4.11).
4.5 Conclusion
The growing demands for new functional materials have encouraged the use of bio-
based materials. Due to environmental factors and their biocompatibility, biodegrad-
ability, and renewable source, biopolymers, in particular cellulose and chitin may
serve as attractive biomaterials for many applications. The ease of physical processing
and chemical modification of these biopolymers attracts more and more attention to
engineer new biomaterials and their based bionanocomposites. A wide variety of
studies focused on improvement strategies to enhance the properties and functions
of the bionanocomposites. The main advantage is that the nanocomposite mate-
rials always exhibit stronger mechanical, physical, and chemical properties than
128 R. Zhang and H. Xu
their constituent materials. The development of new biomimetic composites from
cellulose and chitin can be foreseen in the future.
Although cellulose- and chitin-based materials have been extensively investi-
gated and performed well in numerous applications, the research of their based
bionanocomposites has not yet made significant discoveries and breakthroughs, and
thus, further explorations are still needed. Moreover, there are still many challenges
regarding control of mechanical and physical properties of these bionanocompos-
ites. For further applications, potential risk of acute and chronic toxic effects is the
foremost challenge to face.
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Chapter 5
Polylactic Acid/Halloysite Nanotube
Bionanocomposite Films for Food
Packaging
Zahra Emam-Djomeh and Hajikhani Mehdi
5.1 Introduction
The average production of agricultural products globally has reached 23.7 million
tons of food per day in recent years, while the destruction and waste of food annu-
ally account for a significant amount of this reform [1]. The Food and Agriculture
Organization (FAO) estimates that about 1.3 billion tons of food is wasted annually,
or about 15% of total annual production [2]. This number is equivalent to 33% of the
average daily consumption of an adult. The U.S. Department of Agriculture (USDA)
says a significant portion of this food spoilage occurs at the retail level, most related
to vegetables and fruits [3]. Smarter use of food packaging can significantly reduce
the waste of various foods [4].
Today, a wide range of polymers are used to produce food packaging films [5].
Among these materials, synthetic polymers (of petroleum origin) are among the most
popular materials used in the food industry for packaging various types of food [6,
7]. These polymers include polyethylene terephthalate (PET), low- and high-density
polyethylene (LDPE and HDPE, respectively), polypropylene (PP), polyvinyl chlo-
ride (PVC), and polystyrene (PS) [8]. Synthetic polymers have advantages such
as good strength, optimal flexibility, chemical inertness, and resistance to all types
of chemical degradation [9]. In addition to these advantages, petroleum polymers
have disadvantages such as using toxic substances for preparation, high migration of
packing monomers, and very low degradability, leading to environmental pollution
[10].
Z. Emam-Djomeh (B) · H. Mehdi
Department of Food science and Engineering, University of Tehran, 5th Aref Nasab Street, Vali
Asre Avenue, 1961743811, Tehran, Iran
e-mail: emamj@ut.ac.ir
H. Mehdi
e-mail: hajikhani.mehdi@ut.ac.ir
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_5
141
142 Z. Emam-Djomeh and H. Mehdi
On the other side are biopolymers that, unlike the previous group, are of non-
petroleum origin [11]. These polymers can either exist naturally or be synthe-
sized from organic materials [12]. Naturally occurring organic polymers include
carbohydrates (homopolysaccharides, such as starch, cellulose, and glycogen, and
heteropolysaccharides such as gums) [13], proteins (proteins of animal origin such
as whey, casein, collagen, and gelatin and plant-based proteins such as gluten and
zein) [14], and fats (such as waxes and fats) [15]. Another class of organic polymers
is not found naturally in nature and is made from materials found in nature [16].
These polymers may be synthesized chemically, such as polylactic acid (PLA), or
they may be synthesized by microorganisms such as polyhydroxyalkanoate (PHA)
and polyhydroxybutyrate (PHB) [17].
A significant issue about polymers is the packaging of the degradability of
these polymers in nature [18]. The very positive point of biopolymers compared to
petroleum polymers is their short biodegradability, making these polymers attractive
for use in food packaging [19]. Not all biopolymers have biodegradability (Fig. 5.1),
and the same is valid for petroleum polymers, meaning that some of these polymers
have biodegradability properties [12]. Biodegradable polymers of bio-origin include
PLA and PHA, and petroleum-derived polymers include polybutylene adipate tereph-
thalate (PBAT) and polybutylene succinate (PBS) [20]. On the other hand, polymers
such as bio-derived polyethylene, polyamide (PA), and polytrimethylene terephtha-
late (PTT) are bio-originating but lack biodegradability. PP, PS, and PET are also
standard petroleum and non-biodegradable polymers [21].
Among the proposed polymers, polylactic acid (PLA) has received consider-
able attention in recent decades [23]. PLA is an aliphatic polyester that is gener-
ally obtained through the synthesis of lactic acid [24]. Corn, starch, sugar, or other
renewable sources can produce lactic acid [25]. PLA is a biodegradable thermoplastic
polyester with a unique property, so this polymer has high potential in various appli-
cations such as surgical and medical applications, paper coatings, fibers, films, and
packaging [26]. The unique properties of polylactic acid led the Food and Drug
Administration (PDA) to FDA-approved PLA in 2008 as a Generally Recognized
as Safe (GRAS) [27]. Modifying the properties of polymers to cover the weak-
nesses of a polymer and strengthening them to produce ideal packaging films are
one of the standard measures in optimizing packaging films [28]. Polymers can be
modified by chemical modification of the polymer structure or by using various phys-
ical methods in their preparation [29]. Mixing polymers with different properties to
produce composites that have intermediate properties of primary polymers is one
of the most common ways to improve the properties of packaging films [20, 30].
The addition of nanoscale reinforcements such as different types of nanoparticles
can significantly affect the properties of packaging nanocomposites compared to the
control film [31].
Regarding PLA polymer, the results indicate the weakness of this polymer in
oxygen permeability, which is a major weakness for use in food packaging polymers
because the contact of oxygen causes oxidation in food [32]. Numerous studies have
been performed to improve the barrier properties of PLA in permeability to various
gases [33]. Halloysite is a clay mineral composed of aluminum silicate and exists in
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 143
Fig. 5.1 Types of bioplastics, both biodegradable and non-biodegradable [22]
the form of mostly hollow nanotubes [34]. Al2Si2O5(OH)4 is the chemical formula of
halloysite, composed of oxygen, silicon, aluminum, and hydrogen in ratios of 55.78,
21.76, 20.90, and 1.56% [35]. It has been observed that this mineral has a high
potential in improving the properties of packaging films. Strengthening the barrier
properties and increasing the mechanical strength are among the advantages of using
halloysite nanotubes to prepare packaging nanocomposites [36]. Therefore, we have
tried to introduce polylactic acid as an ideal polymer in food packaging in this study
and also show the potentials of halloysite nanotubes in modifying the undesirable
physicochemical properties of this polymer.
5.2 Polylactic Acid
Polylactic acid (PLA), formed from the polymerization of lactic acid, is a biodegrad-
able, biocompatible, and renewable thermoplastic polyester [26]. The lactic acid used
in the preparation of this polymer is mainly obtained from the bacterial fermenta-
tion of corn, sugarcane, potato, and other biomass [37]. Good mechanical proper-
ties and good processing capability are convenient features of PLA, which makes
this polymer a suitable candidate for replacement with petroleum polymers [23].
144 Z. Emam-Djomeh and H. Mehdi
Fig. 5.2 Chemical structure of a PLLA and b PDLA
In addition to the appropriate properties, this biopolymer has weaknesses such as
high hydrophobicity, high oxygen permeability, poor strength, slow degradation rate,
reactive side chain groups, and low thermal stability [38]. However, easy access to
polylactic acid monomers has resulted in a lower cost than other biodegradable poly-
mers [39]. As showninFig. 5.2, PLA has two forms, PLLA and PDLA. Lactic acid
(2-hydroxypropanoic acid) has two enantiomers l and d [40]. Lactic acid l is a
common compound in human metabolism, but lactic acid d is produced by some
microorganism strains or some less related metabolic pathways [41]. Lactic acid l is
an endogenous compound, but lactic acid d is a harmful enantiomer [41]. l-lactide
is produced if the main acid is l-lactic acid, and if the primary acid is d-lactic acid,
d-lactide is produced.
The difference in these two enantiomers determines the final form of PLA [42].
PLA properties are highly dependent on the ratio between forms l and d. l-PLA or
PLLA shows higher crystallization, which can lead to increased melting temperature
and brittleness [43]. Pure PLA in either l or D form has a melting point of 180 °C and a
glass transition temperature of 60 °C [44]. It has been observed that the crystallization
of PLA can be reduced entirely after combining 15% d-lactide in poly l-lactide [42].
Copolymerization of l and d forms leads to forming an amorphous structure in the
final polymer [45]. High molecular weight PLA is usually obtained by open-loop
polymerization of lactide monomer or bacterial fermentation of cornstarch or sugar
beet [46]. In order to better integrate the polymer, PLA with a longer chain is needed,
and the introduction of a branch in the PLA structure can be a good option for this [47].
Numerous studies introduce polylactic acid properties as intermediate properties
required for fully stable polymers’ product stability and essential properties [42].
Also, high research activity is dedicated to overcoming common PLA weaknesses
such as low impact resistance, low heat distortion temperature, and creating user-
friendly PLA grades for use in specific applications [48].
Lactic acid and lactide (cyclic diester) are the most common monomers in PLA
synthesis [49]. There are several ways to synthesize PLA, not all of which are cost-
effective. The most common ways to obtain PLA are cyclic polymerization of lactide
with various metal catalysts (usually tin octave) in solution (or as a suspension) and
direct condensation of lactic acid monomers [40]. In the direct condensation method,
the reaction temperature must be below 200 °C to prevent the formation of the entrop-
ically favored lactide monomer [40]. During the polymerization of lactic acid or
lactide, a molecule of water is produced in the reaction, leading to disruption of the
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 145
reaction, so it is necessary to remove water from the environment [42]. Using vacuum
systems to remove water is very efficient. The most important goal in polymerization
is to obtain polymers with long chains and high molecular weight [50]. It has been
observed that the removal of water molecules in the PLA polymerization process
increases the molecular weight of the final product [42]. Accurate crystallization of
the polymer from the melt also directly affects increasing the molecular weight but
prolongs the processing time [51, 52]. Different enantiomers in polymer synthesis
also have a significant effect on the final chains [40]. Using this variable, PLA can be
converted to different degrees of crystalline and amorphous, which can be selected
based on the purpose of polymer production [42]. Other industrial methods in the
chemical synthesis of this polymer include lactonitrile, acrylonitrile, and propionic
acid [42]. The price of raw materials is considered the main factor for choosing
between different polylactic acid production methods [42]. For example, the propi-
onic acid method is less used in industries due to the high cost of raw materials
[42, 53].
By controlling the degree of crystallinity and amorphous, polylactic acid can
be changed from a completely amorphous glass polymer to a semi-crystalline, the
highly crystalline polymer [54]. This change in the chemical structure of PLA causes
this polymer to have a glass transition temperature between 60 and 65 °C, a melting
temperature between 130 and 180 °C, and a tensile modulus between 2.7 and 16
GPa [55]. For example, by combining different l and d enantiomer ratios, the PLLA
melting point can be increased by 60 °C and brought closer to the PDLA melting point
[56]. The combination of these two polymers causes the formation of a regular struc-
ture and increases crystallization [57]. PLDA acts as a nuclear agent and increases the
rate of crystallization [58]. The most suitable structure is observed in the ratio of 1:1
of polymers. Studies have shown that the mechanical properties of PLA are interme-
diate to the properties of polyethylene terephthalate and polystyrene polymers [59].
Many solvents are used to dissolve PLA. The solubility of PLA is generally related
to its degree of crystallization [60]. The higher the crystalline structure in PLA, the
harder it is to solve and the higher the temperature required [60].
Conversely, increasing the amorphous structure results in better solubility of
this polymer [61]. This polymer’s hydrophobic and organic structure makes many
organic solvents capable of dissolving PLA [61]. Chloroform, dichloromethane, ethyl
acetate, and propylene carbonate are the most common organic solvents used to
dissolve PLA [62]. Ethyl acetate is more popular due to its ease of access and low risk
of use. Ethylbenzene, toluene, acetone, and tetrahydrofuran can also partially dissolve
PLA [63]. Increasing production of packaging waste prepared with petroleum poly-
mers has led to the use of biodegradable polymers obtained from renewable sources
to be prioritized [64]. Thermodynamic properties, mechanical strength, barrier, and
biodegradability are critical points in the packaging industry. Polylactic acid has
been proposed as a qualified substance due to its suitable properties [65]. In 1932,
DuPont first developed PLA by a chemist named Wallace Carothers. This product
was not cost-effective due to its low molecular weight. The company was able to
produce this high molecular weight polymer in 1954, which is the beginning of PLA
in the world [20, 42]. In the ‘60s, after various studies on PLA, this polymer was
146 Z. Emam-Djomeh and H. Mehdi
introduced as a suitable raw material for making supplies and raw materials for the
medical industry [42]. Finally, after FDA approval in 2008, polylactic acid became
a common and widely used polymer in the food and medical industries [46].
The unique physical properties of polylactic acid make it suitable for use in various
plastic products for food packaging, such as packaging films and food boxes [66].
Suitable tensile strength and ductility make it suitable for various processing tools
such as melt extrusion mold, injection mold, blown film mold, foam mold, and
vacuum mold [67]. In addition, the excellent biocompatibility of PLA has led to its
widespread use in biochemical medicine [67]. Studies on the degradation of poly-
lactic acid have shown that the degree of crystallization affects the rate of PLA
degradation [68]. Various factors can affect the degree of crystallization of PLA, the
most important of which is the molecular weight of this polymer [69]. Highly crys-
talline polymers last for several months, and metabolism takes place only after a few
years, while polymers with low crystallinity and amorphous structure can decom-
pose in a few weeks [42]. The following property that can affect the performance of
materials according to the type of polymer processing is the glass transition temper-
ature or Tg [70]. This factor, unlike biodegradability, is not related to the degree of
crystallization of the polymer [69]. Due to its molecular weight, PLA has a glass
transition temperature between 55 and 60 °C and a melting temperature between
130 and 180 °C [71]. The study of mechanical properties has shown that the tensile
strength of PLA can increase up t o 50 MPa by increasing the degree of crystalliza-
tion and molecular weight [72]. PLA undergoes hydrolysis at temperatures above
200 °C, lactide recombination, major oxidative chain cleavage, and intermolecular
or transmolecular transesterification [38, 59]. This series of reactions cause the PLA
to have sufficient thermal stability to reduce degradation and maintain molecular
weight and function [42].
The biodegradation of PLA is related to several factors, including time, temper-
ature, low molecular weight impurities, and catalyst concentration [39]. Further
research has shown that modification and purification of this polymer can be effective
in its biodegradation [42]. Hydroxyl terminal acetylation increases the decomposi-
tion temperature by about 26 °C by reducing the molecular weight of PLA [42]. A
theory about the biodegradation phenomenon of PLA introduces a simple proton-
catalyzed hydrolysis chain as an influential factor in PLA biodegradation [73]. This
reaction is reversible, so the purity of the polymer can be affected by explaining the
degradation kinetics of PLA on the degradation process during the synthesis reaction
process [42]. Another factor determining the degree of autocatalysis and biodegra-
dation is the degree of crystallization of the polymer [74]. Enzymes also play a role
in the degradation of PLA, but the enzyme’s exact mechanism is already unknown
to us [75]. This fact means that it cannot be said with certainty that enzymes directly
catalyze the degradation process of the polymer or indirectly contribute to the reac-
tion by removing the by-products. However, assuming that PLA is mainly degraded
by hydrolysis, its degradation is divided into two main stages: (1) non-enzymatic
melting of ester groups and (2) random cutting of low molecular weight polymers
by microorganisms to produce Co2 and H2O[42].
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 147
Apart from the attractive properties of polylactic acid, this polymer is not free of
defects. The high hydrophobic properties make this polymer unsuitable as a carrier
for various compounds such as bioactive compounds and antioxidants in delivery
systems [76]. Low mechanical strength compared to other polymers and brittleness
of PLA limit the use of this polymer [77]. The oxygen permeability of PLA is known
as one of the most significant disadvantages of this polymer [78]. Many efforts
have been made to improve the weaknesses of PLA, and many findings have been
published in recent years [79, 80]. Various methods have been proposed to increase
the efficiency of PLA, some of which are mentioned below. The preparation of
nanocomposites from this polymer has had positive results; for example, the addition
of different nanoparticles during the synthesis of PLA or during its processing can
significantly modify and improve the properties of this polymer [81]. The use of
different copolymers had the same results, so that the use of low Tg polymers in
combination with PLA can improve the flexibility properties of this polymer and
make it possible to use this polymer at lower temperatures [42]. In one study, the
properties of polylactic acid/polyglycolic acid copolymers were investigated [78,
82]. Since PGA has a high melting point of about 228 °C and Tg of about 38 °C,
PLA/PGA polymer composite has a low Tg point and amorphous structure, which
has higher flexibility than pure PLA [82]. In addition to thermodynamic properties,
PGA has higher hydrophilicity, which in addition to making this polymer suitable
for delivery systems also increases the rate of biodegradation because it has a higher
hydrolysis rate than PLA [78]. Poly (ε-caprolactone) and polylactic acid composites
were evaluated in another study [83]. The Tg point in poly (ε-caprolactone) is about
−60 °C, and its melting point is 59.5 °C. The composite has high flexibility and
crystallization with a high melting point. It was observed that this polymer has
variable mechanical properties [83, 84].
The use of additives such as low molecular weight citric acid, succinic acid,
tartaric acid, and oxalate to PLA as a plasticizer can partially alter this polymer’s
mechanical and thermodynamic properties [85]. There are also reports of a positive
effect of montmorillonite on the strength and flexibility properties of PLA [86].
Plasticizers increase flexibility and reduce brittleness by reducing the Tg in the
polymer [87]. In PLA, the addition of a plasticizer can reduce the Tg by up to
26 °C [88]. On the other hand, the addition of montmorillonite and polyethylene
glycol could make the PLA structure more agglomerated and keep the elongation
below 5% [89–91]. Adding starch to PLA is the simplest and cheapest way to change
this polymer’s physicochemical properties and dramatically increases the biocom-
patibility of this polymer [42]. Combining starch with PLA reduces tensile strength
by increasing water absorption [92]. This feature has many advantages, but it also
has disadvantages, such as increased fragility, which can be slightly eliminated using
plasticizers. Polyether and PLA copolymers also recorded good results in modifying
the degree of hydrophilicity, degradability, biocompatibility, and flexibility [93].
The mechanical properties of PLA/polycaprolactone and PLA/polyethylene oxide
composites did not show a significant difference, but the high hydrophilic proper-
ties of polyethylene oxide increase the degree of hydrophilicity in the composite,
which accelerates biodegradation [93, 94]. Recent studies have shown that the use of
148 Z. Emam-Djomeh and H. Mehdi
polyethylene-polypropylene copolymer produces longer polymer chains than PEO
[95, 96]. Other methods of modifying polylactic acid include the use of crosslinkers.
These compounds work by altering the rheological and thermodynamic properties
of the material by creating crosslinks between the polymer chains [38]. Crosslinking
compounds often act as an intermediate compound that binds two polymer chains
together [97]. Oxepane or 5,5'-bis(oxepane-2-one) is a common crosslinker known in
the polymer industry [42]. The use of this material for crosslinking has been reported
in PLA, which has also yielded positive results. Other common crosslinkers used in
PLA polymers include silane, dicumyl peroxide, and triallyl isocyanurate [ 98]. This
method is known as an efficient and relatively simple method that, unlike previous
methods, does not require the addition of copolymers or nanoparticles [99].
High compatibility and good biodegradation are the prominent features of this
polymer. Also, PLA metabolism in the human body does not cause the formation
of toxic compounds, which leads to the widespread use of this polymer in the food
and medical industries [42]. Polylactic acid is used today in various fields such as
tissue engineering, drug delivery systems, encapsulation of bioactive compounds,
controlled release, and active food packaging [91]. Thelow priceofraw materials
in the production of this polymer has made the use of PLA in the food industry cost-
effective [64]. On the other hand, ideal properties such as thermoplastic properties
and suitable ductility make it possible to use this polymer differently. High quality
and high compatibility are other suitable properties of this polymer, but another
important point is the prevention of PLA against the passage of ultraviolet light,
which can reduce the adverse effect of food absorption by ultraviolet light [100]. All
of these properties make PLA an ideal polymer in food packaging. PLA classification
in the GRAS group makes this polymer suitable for packaging in direct contact
with food. Also, the thermoplastic properties of PLA are very similar to common
polymers such as PET, so the use of PLA in the form of thermoforming looks pretty
appropriate. Other forms of PLA food packaging products that have been used in
recent years include extruded containers, oriented and flexible films, and cast films.
These methods are used to prepare typical packagings such as food and beverage
containers, bottles, glasses, packaging films, and coated paper and boards [42].
5.3 Polylactic Acid/Halloysite Nanotube Bionanocomposite
Polylactic acid polymer and many properties also have weaknesses, some of which
were mentioned above. Numerous studies have been performed in recent years
to correct the weaknesses of this polymer and strengthen its favorable properties.
Polymer composites have always received more attention than other polymer modi-
fication methods due to their simplicity in preparation [101]. The use of nanoscale
additives to PLA will lead to much better results [102]. The very small size of the
nanomaterials makes it easy to fit between the polymer chains and perform better
due to the high surface-to-volume ratio. The placement of nanomaterials between
the polymer chains creates crosslinks between the chains and can affect the film’s
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 149
mechanical, barrier, and even solubility properties [86]. In this section, the properties
of PLA bionanocomposites containing halloysite nanotubes are investigated.
Halloysite is known as a derivative of kaolin [103]. The name of this substance
is derived from the name of the Belgian geologist Jean Baptiste Julien d’Omalius
d’Halloy, who discovered it in 1826 [104]. As seen in Fig. 5.3, the natural form
of this rare material is in the form of nanotubes. These nanotubes are formed by
weathering plate-like kaolin particles [105]. In this way, plate-like kaolin particles
roll due to weathering, and in the meantime, the impurities in kaolin are leached out
to produce high purity nanotubes [106]. Halloysite nanotubes have a length of about
1–15 microns, and the inner diameter of the nanotubes varies from 10 to 150 nm
[107]. Halloysite properties are a combination of excellent mechanical properties,
tubular microstructure, high biocompatibility, flame retardancy, and diverse surface
chemistry [108]. The use of this material in combination with various polymers
and the preparation of polymer nanocomposites to modify the polymer properties
are widely used [31]. Today, halloysite is used in various polymer matrices such as
thermoplastics, thermosets, and elastomers to make various nanocomposites [109].
Halloysite nanoparticles effectively modify various properties of polymer nanocom-
posites such as thermodynamic, mechanical, permeability, solubility and surface
properties, degree of swelling, biodegradability, and other properties [110]. Other
suitable properties of halloysite include the abundance of this substance and the easy
solubility in water and other organic solvents, which causes the proper dispersion of
this substance and simplifies its use [111]. Every year, various studies are published
on the different effects of halloysite on the properties of polymer packaging films
[112]. In general, the two factors of halloysite dispersion and surface interactions
between halloysite and polymer matrices are known as the main factors in the impact
of this clay mineral [113]. Unlike layered silicates such as nano-silica, halloysites
have more hydrophobic properties due to the lower density of surface hydroxyl
groups but are generally hydrophilic in nature [109]. This degree of hydrophobicity
provides a better dispersion for halloysite nanotubes in polymer matrices [114].
Various studies have shown that halloysite nanotubes can be covalently bonded with
hydrophilic polymers s uch as polyethylene alcohol and chitosan, increasing surface
adhesion and improving the interaction between the polymer and the nanotube [108].
On the other hand, due to the hydrophilic nature of halloysite nanotubes, any inter-
action between these materials and non-polar polymers is not done properly [115].
Various strategies have been proposed to overcome this challenge, including the
use of various surfactants to form covalent bonds, the use of polymers with lower
hydrophobicity, and the use of intermediates such as polar macromolecules [116,
117].
In addition to the mentioned features, halloysite nanotubes have other applica-
tions in the preparation of active packaging. One of their most critical applications
is carrying bioactive compounds in food packaging films [119]. Food packaging
plays a vital role in maintaining food quality. Maintaining food quality is difficult
despite environmental phenomena such as oxidation, rancidification, and the growth
of microorganisms [100, 120]. By using bioactive compounds such as antimicro-
bial and antioxidant compounds, there is the ability to control these undesirable
150 Z. Emam-Djomeh and H. Mehdi
Fig. 5.3 a The raw halloysite and b ground halloysite; c TEM and d SEM photos of HNTs mined
from Hunan Province, China; e schematic illustration of the crystalline structure of HNTs [118]
phenomena in food [100]. Direct use of bioactive substances increases the consump-
tion dose and increases food packaging costs [121]. Also, due to the high sensi-
tivity of bioactive compounds to environmental factors such as light, temperature,
and oxygen, a significant part of these materials are degraded and lose their effec-
tiveness quickly [122]. Encapsulation of bioactive compounds greatly reduces the
required dose of these substances and protects them from degradation by various
environmental factors [122]. Halloysite nanotubes have high potential in bioactive
compounds’ carriers due to their hydrophobicity and geometric properties [123].
Numerous studies have been performed on the effectiveness of halloysite nanotubes
in encapsulating various compounds to be used in food packaging, all of which indi-
cate the positive effects of this clay mineral [119]. A noteworthy point about active
packaging is controlling the release rate of bioactive materials encapsulated in the
polymer matrix [91, 124]. With this information, the release pattern of bioactive
substances can be identified and the best shelf life of food (the best time for effective
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 151
packaging) can be obtained. With the help of this information, it is possible to design
food packaging according to the expiration date of the product. Using the release
rate control feature, food packaging can be designed to store food in short periods or
very long intervals [125]. In this way, the food is kept in the best quality conditions
during the storage period and has the maximum quality at consumption.
The use of nanotechnology is an excellent way to improve the properties and cover
the weaknesses of biopolymers [10]. In general, nanotechnology is the use of scales
of 1–100 nm in engineering designs. In the case of food packaging composites, the
use of nanomaterials with at least one of their dimensions at the scale of 1–100 nm
creates packaging nanocomposites [126]. Composites consist of a polymer matrix or
a continuous phase and a discontinuous phase or filler, which in the case of nanocom-
posites are fillers at the nanoscale [127]. High differentiation by nanotechnology in
food packaging has made nanocomposites a viable alternative to conventional pack-
aging. Biopolymers are sensitive to the passage of water vapor due to their hydrophilic
nature [128]. Oxygen and carbon dioxide permeability is also higher in biopolymers
than in petroleum polymers [129]. Undoubtedly, this defect is one of the most limiting
factors for biopolymers in the food packaging industry. Modifying and enhancing the
barrier properties of packaging films with the help of nanotechnology have shown
promising results in the last decade [130]. Other ways to improve the barrier proper-
ties of packaging films include the use of polymer blends [131], high barrier coatings
[132], and multilayer films containing a high barrier film [133]. However, various
studies indicate a higher impact of nanocomposites than composites; on the other
hand, using several techniques simultaneously will bring much better results. There
are concerns about the toxic properties of nanoparticles, and further studies have
shown that if the nanoparticles are smaller than a specific size, they can cross the
cell barrier into the bloodstream without endocytosis [134, 135]. The nanoparticles
pass t hrough the cell barrier due to their small size without a specific mechanism
and through the cells of the small intestine (villi) [136]. Passage through villus cells
can interfere with the main mechanism of material transport that is diffuse (Active
Transport, Facilitated Diffusion, Osmosis, and Simple Diffusion) [137].
Today, due to the increasing demand for food with minimal processing and long
shelf life, it has created a large market for food packaging [138]. To gain more
market share, creativity in the production of packaging materials is of great impor-
tance. Nanocomposites undoubtedly have a large share of this market. The use of
such packaging enhances the inhibitory properties of packaging films and prevents
the migration of oxygen, carbon dioxide, water vapor, and flavoring compounds
[139]. Reinforcement barrier properties ultimately lead to more excellent retention of
freshness and quality of packaged food, impacting its shelf life [140]. As mentioned
above, the main disadvantage of biopolymers is water vapor permeability due to
their hydrophilic nature. Reduction in water vapor permeability rate is of particular
importance in biopolymers. Studies have shown that with the help of nanocomposite
technology, this inherent defect of polymer-based packaging materials can be largely
covered [141]. In many cases, it has been reported that the barrier properties can be
improved by up to 50% compared to the properties of the control polymer film [142].
152 Z. Emam-Djomeh and H. Mehdi
Part of this reduction in permeability rate is increased tortuosity, which increases the
motion of gas molecules, thus reducing permeability and increasing barrier properties
[143].
Another noteworthy point is the adverse effect of ultraviolet rays on food quality
and even the content of bioactive compounds in food. Polylactic acid is known as a
protective polymer against ultraviolet light [144]. So far, many studies have shown
the positive effect of PLA in reducing the adverse effects of ultraviolet light [100].
On the other hand, the use of nanomaterials in the preparation of nanocomposites
increasingly gives the ability to repel the properties of ultraviolet light to food pack-
aging [145]. Halloysite nanotubes also can refract ultraviolet light and prevent the
direct contact of this harmful radiation on the surface of food [115]. The combined
use of PLA and halloysite nanotubes can be highly effective in protecting from
ultraviolet light. The last important point is the thermal resistance of polymers.
The thermal resistance factor is mostly used in the production of active packaging
films [139]. Bioactive compounds such as antioxidants and antimicrobial compounds
are degraded due to their high sensitivity to process temperatures in the preparation
of packaging films (in thermoforming methods) during the packaging production
process [125]. Degradation of these bioactive substances in active packaging causes
the quality of the packaged food to be adequately maintained during storage in the
packaging [125]. Encapsulation of bioactive compounds can significantly affect the
preservation of these compounds during the packaging preparation process [146].
Halloysite nanotubes can be loaded with bioactive compounds due to their spatial
structure. This phenomenon increases the thermal resistance of these temperature-
sensitive compounds and prevents their thermal degradation during the process [147].
In addition, the increase in thermal resistance in the packaging polymer is also
increased by the use of nanoparticles. Numerous studies concerning Differential
Scanning Calorimetry (DSC) have shown that the thermal degradation temperature
of the packaging polymer shifts to a higher temperature zone when using different
nanoparticles, especially mineral nanoparticles [148, 149]. In this section, we tried to
express some of the positive points of nanocomposites simply compared to compos-
ites. Improving the properties of packaging films in various aspects, some of which
were mentioned above, has made nanocomposites one of the most widely used fields
of research and study in recent years.
5.4 Food Packaging Application of Polylactic
Acid/Halloysite Nanotube Bionanocomposite
In recent years, various studies have been published focusing on nano-biocomposites.
Each, in turn, has examined the characteristics of packaging films from a different
perspective. In this section, an attempt has been made to introduce the strengths and
weaknesses of packaging nanocomposites with the help of this research. However, the
main focus is on polylactic acid polymer and halloysite nanotubes. A study conducted
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 153
Fig. 5.4 FESEM images of a halloysite nanotubes (HNTs), b neat polylactic acid film and poly-
lactic acid/HNT bionanocomposite film incorporated with c 3wt% and d 6 wt% HNTs and TEM
micrographs showing the distribution of HNTs in PLA matrix for e 3.0 wt% and f 6.0 wt% HNTs
with 15,000× magnification [150]
154 Z. Emam-Djomeh and H. Mehdi
last year by Risyon et al. attempted to modify limiting factors such as poor mechanical
properties, low thermal stability, and low barrier properties in biopolymers [150]. The
author proposed using nanoscale fillers and the preparation of nano-biocomposites
to solve the problem of these biopolymers. In this regard, polylactic acid/halloysite
nanotube nano-biocomposite prepared using the casting method was introduced.
Doses of 1.5–6.0 wt% were used to evaluate the effect of different concentrations
of halloysite (Fig. 5.4). The results of various experiments were evaluated with a
halloysite-free PLA control film. The effects of different halloysite concentrations
on the dispersion, chemical bonding, and average molecular weight of bionanocom-
posite films were investigated to observe changes in their mechanical, thermal, and
barrier properties [150]. Field emission scanning electron microscopy (FESEM)
imaging showed good dispersion for a concentration of 3.0 wt% of halloysite in the
PLA polymer matrix. This suitable dispersion is probably due to the good interaction
between PLA and halloysite due to hydrogen bonds between PLA hydroxyl groups
and halloysite siloxane groups [151]. As shown in Fig. 5.5, the carboxyl group in the
PLA structure can form a hydrogen bond with the hydrogen atoms of the hydroxyl
group in the halloysite due to the negative charge [152]. On the other hand, hydrogen
bonds can be formed by the negative charges of oxygen atoms on the halloysite
surface, attracting the positive charges of hydrogen atoms in the PLA matrix [153].
These bonds indicate a good interaction between PLA and halloysite, which can be
seen by Fourier-transform infrared spectroscopy (FT-IR). Further magnification in
FESEM showed that halloysite nanotubes fill the pores in the structure of PLA film.
Thus, it can increase thermal stability, barrier reinforcement, and increasing mechan-
ical strength in nanocomposites [150]. It was observed that at higher doses of about
6.0 wt% halloysite, nanotubes tend to form aggregated structures in the polymer
Fig. 5.5 Schematic diagram of the interaction mechanism between PLA and halloysite nanotube
[166]
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 155
matrix. Probably at high concentrations due to more collisions between molecules,
the adhesion between halloysite nanotubes increases due to van der Waals inter-
actions, which lead to the formation of aggregated structures [154]. Thus, a dose
of 3.0% by weight to achieve the best dispersion in halloysite was introduced as
the optimal dose. The study of the film’s mechanical properties showed that the
addition of halloysite at a concentration of 3.0% could lead to an increase in tensile
strength and Young’s modulus while decreasing elongation at break [150]. Increasing
the dose of halloysite to 4.5 and 6.0 wt% reduces the tensile strength and Young’s
modulus while increasing the elongation at break. Weakening of tensile strength due
to increasing halloysite dose may be due to the formation of aggregated structures at
high concentrations. At low doses of about 1.5–3.0 wt%, dispersion is well-formed,
and a large hydrogen bond is formed between the halloysite nanotube and PLA,
thus enhancing mechanical properties such as tensile strength and Young’s modulus.
The results showed that the concentration of halloysite greatly affects the proper-
ties of the nanocomposite. Increasing the density of the hydrogen bond reduces the
mobility of the PLA polymer chains, which in turn hardens and reduces the elas-
ticity of the packaged film and reduces the elongation at break [155]. This reduction
in elongation at break can also be achieved with the help of FT-IR at the peak of
1050–1250 cm−1, which is related to the C–O–C band [156]. It was observed that
increasing the halloysite concentration leads to a decrease at the peak of 1050–
1250 cm−1, which is consistent with a decrease in elongation at break [150]. The
results of the thermal stability test showed that the concentration of 3.0 wt% could be
effective in increasing the thermal stability of nanocomposites due to proper disper-
sion in the PLA matrix and the formation of hydrogen bridges. However, higher
doses such as 6.0 wt% have lower thermal stability due to the formation of aggre-
gated forms of halloysite nanotubes and the presence of free hydroxyl groups in PLA.
The inhibitory properties of PLA films with different ratios of halloysite nanotubes
to the permeability of water vapor and oxygen were evaluated [157]. It was observed
that at doses below 3.0 wt%, the effectiveness of nanotubes in reducing the rate of
water vapor permeability is not significant. On the other hand, doses of 3.0–4.0%
wt% could significantly reduce the rate of water vapor permeability. The results
showed that at lower doses, due to the inadequacy of nanotubes in filling the PLA
film structure’s pores and the lack of hydrogen bonds, water vapor permeability rate
reduction is non-significant. At doses of 3.0 and 4.0 wt% of nanotubes, due to the
proper dispersion in the polymer matrix, which leads to the formation of tortuous
paths, the formation of high hydrogen bonds, and the filling of microscopic cavities,
the rate of water vapor permeability is significantly reduced [158, 159]. Lack of
proper dispersion in the polymer matrix at doses of 6.0 wt% and the formation of an
aggregate form increase the rate of water vapor permeability. Insufficient hydrogen
bonds and non-filling of microscopic cavities are some of the factors that can explain
this phenomenon. On the other hand, the lack of proper dispersion in the polymer
matrix prevents the formation of tortuous paths, which is the main factor in reducing
the rate of water vapor permeability. Halloysite nanotubes have a negative charge due
to the presence of hydroxyl groups on the surface and are naturally hydrophilic in
nature. However, the placement of the halloysite nanotube in the PLA matrix results
156 Z. Emam-Djomeh and H. Mehdi
in the establishment of a negatively charged hydrogen bond between the oxygen at
the nanotube surface and the hydrogen in the PLA hydroxyl group [150]. In this
way, the desire for water permeability through nanotubes is not increased and also
water vapor permeability in nanocomposites is not increased. It can be assumed
that the formation of tortuous pathways is formed by the establishment of hydrogen
bridges between the halloysite nanotubes and the PLA polymer, so the greater the
hydrogen interactions between the two materials, the greater the expectation of a
reduction in the rate of water vapor permeability [150]. As previously mentioned,
halloysite nanotubes are hydrophilic in nature, so increasing the dose of this mate-
rial increases the tendency of the nanocomposite to absorb water and increases its
water vapor permeability. A dose of 3.0 wt% of the nanotube was selected as the
optimal nanocomposite sample due to its mechanical and barrier properties, and its
oxygen permeability was evaluated. It was observed that the nanocomposite has a
33% lower rate of oxygen permeability than the control PLA film. As before, the
formation of tortuous paths can be effective in penetrating other gases such as oxygen
[143]. Therefore, the obtained results are expected to be consistent with the results
of water vapor permeability experiment. In other similar studies, titanium oxide and
montmorillonite nanoparticles were used to modify the barrier properties of PLA
film and similar results were obtained [33, 160]. Therefore, it was concluded that
increasing the winding paths has a great impact on reducing the permeability to
various gases. The presence of oxygen in food packaging can lead to food spoilage
such as loss of nutrients, discoloration, flavor, and microbial growth. This study
showed that the use of nanomaterials can greatly improve the barrier properties of
PLA films to the extent that it is suitable for use as food packaging. In order to show
the potential of the prepared films (PLA bionanocomposite film/halloysite nanotube
with a concentration of 3.0% wt% with control PLA film), these films were used
for packing cherries to evaluate the shelf life of packaged food [150]. Weight loss
and firmness of tomatoes were assessed for nine days. The results showed that the
firmness of tomato tissue packed in bionanocomposite decreased by 16% during nine
days, while this decrease was calculated up to 25% in the control PLA film. Tomato
weight loss during nine days due to water vapor permeability in bionanocomposite
was measured at about 1.9% and in control PLA film 2.8%. Thus, it can be concluded
that the use of PLA bionanocomposite containing 3.0 wt% of halloysite nanotubes
can reduce the loss of agricultural products during storage in packaging [150].
In a similar study by Therias et al., halloysite nanotubes were used as fillers up
to 12.0 wt% in PLA film [161]. Filler nanomaterials were added to the PLA film
in both melt-compounded and dry-mixed forms. Key properties of nanocompos-
ites, such as mechanical properties and nanotube distribution in the polymer matrix,
were evaluated. Morphological analysis was performed by transmission electron
microscopy (TEM) through nanocomposite samples containing 6.0 and 12.0 wt%
of nanofillers. Adequate distribution in the dispersion of nanofillers was observed
in both melt-compounded and dry-mixed forms at a dose of 6.0 wt% but at a dose
of 12.0 wt% showed signs of aggregates of nanofillers [161]. The formation of
aggregated structures due to van der Waals interactions is due to high collisions
between nanofillers at high concentrations [162]. Studies on mechanical properties
5 Polylactic Acid/Halloysite Nanotube Bionanocomposite Films … 157
have shown that the tensile strength and Young’s modulus change under the influ-
ence of nanofiller content. The maximum tensile strength for different samples was
estimated to be almost constant at about 60 MPa, but Young’s modulus increased
with increasing nanoparticle dose [161]. According to Hooke’s law, an increase in
Young’s modulus means a decrease in elasticity, and more force must be applied to
the body to create the deformation, so nanocomposites with a higher load percentage
than nanofillers have a harder texture [163]. Weaknesses in PLA include sensitivity
to photooxidation [59]. PLA can protect food from the sun’s ultraviolet rays at the
cost of degradation and photooxidation of the polymer itself [59, 164]. In this study,
the author investigated the effect of photooxidation on nanocomposites compared to
PLA control film without nanofillers. To evaluate photooxidation, IR absorption in
the range of 1845 cm−1 can be used for different nanocomposite samples, and the
peak intensity is related to the oxidation intensity, because the absorption range of
1845 cm−1 is related to the products of photooxidation and reducing the intensity at
this peak means reducing photooxidation [165]. It was observed that the rate of PLA
oxidation in the presence of halloysite nanotubes after 240 h is significantly higher
than the control PLA film. Also, the intensity of adsorption at the peak of 1845 cm−1
was not significantly different between samples with different doses of nanofillers,
which means that the effects were the same in samples with different concentrations
of nanofillers. Undoubtedly, halloysite nanotubes have a destructive effect on PLA
photooxidation, which can be related to chromophore impurities, which can have an
induced effect on the mechanism of radical oxidation of PLA [161]. Another reason
could be due to the presence of iron impurities, as reported in natural clays, which
cause higher degradation of nanocomposites. Higher photooxidative degradation can
increase the biodegradation rate of this polymer and also cause it to absorb more of
the harmful energy of sunlight during use as food packaging and prevent it from
coming into contact with food [161].
PLA/halloysite nanotube films were fabricated using the soluble casting method
to investigate their properties for packaging applications by De Silva et al. [151].
Concentrations of 2.5 and 10 wt% of halloysite were used, and their effect on mechan-
ical properties such as tensile strength and tensile strength was evaluated. The results
were compared with the control film (PLA without halloysite tubules). The results
showed that the addition of 5.0% by weight of nanotubes could enhance the tensile
strength of the nanocomposite. Infrared spectra showed that the hydroxyl groups of
PLA have chemically interacted through hydrogen bonding with the surface siloxane
groups of halloysite. The contact angle value of the water droplet does not change
significantly with the addition of the halloysite, so it does not absorb more moisture
in the PLA film. TGA results showed that thermal stability is significantly increased
by adding halloysite due to char residue and lumens of halloysite. The author intro-
duces PLA/halloysite nanotube nanocomposite as a suitable alternative to petroleum
packaging [151].
158 Z. Emam-Djomeh and H. Mehdi
5.5 Conclusion
This chapter tried to introduce the advantages and problems of polylactic acid as a
biodegradable biopolymer in food packaging. Excessive use of petroleum polymers
leads to bio-pollution, so the use of biodegradable polymers is a priority. On the
other hand, the destruction of a significant portion of food during storage encour-
ages us to use more efficient packaging. Direct use of PLA biopolymers is limited
due to weaknesses such as brittleness, high hydrophobicity, poor mechanical prop-
erties, high permeability to oxygen and water vapor, and high cost compared to
petroleum polymers. Various solutions such as chemical and physical modification
were proposed to improve the properties of PLA. The use of nanomaterials due to
the high surface-to-volume ratio showed a much higher effect. Halloysite nanotubes
are used as fillers in PLA structures. Halloysite, as a mineral, has a tubular struc-
ture and a polar nature. Surface hydroxyl groups in the halloysite structure can form
hydrogen bonds with the hydroxyl group in PLA. The establishment of abundant
hydrogen bonds increases the nano-biocomposite’s mechanical strength and reduces
the permeability of the nano-biocomposite to oxygen and water vapor by reducing
the mobility of the chains. It was observed that concentrations less than 5.0 wt% of
halloysite were not effective enough, and concentrations higher than 5.0 wt% were
not effective due to the formation of aggregated structures, so a concentration of
5.0 wt% halloysite was introduced as the optimal concentration. In addition to the
mentioned advantages, the use of nanotubes increases the loading capacity of bioac-
tive compounds in the packaging film because PLA, due to its high hydrophobicity,
is not able to encapsulate polar compounds properly. The polar nature of halloysite
improves the encapsulation properties of nanocomposites.
On the other hand, studying the release pattern and controlling the release of
encapsulated bioactive compounds can be effective for preparing active packaging to
maximize effectiveness during shelf life. In this chapter, an attempt was made to intro-
duce PLA/halloysite nanotube nano-biocomposites as an alternative to petroleum
polymers. Solutions have also been introduced to address the challenges facing
it. Undoubtedly, the desirable properties of this bionanocomposite will be more
welcomed in the future for the preparation of various food packaging.
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Chapter 6
Preparation of ZnO/Chitosan
Nanocomposite and Its Applications
to Durable Antibacterial, UV-Blocking,
and Textile Properties
Tanmoy Dutta, Abdul Ashik Khan, Nabajyoti Baildya, Palas Mondal,
and Narendra Nath Ghosh
6.1 Introduction
During the last few decades, scientists are engaged to develop cost-effective and eco-
friendly synthetic natural therapeutic materials. Despite remarkable development of
pharmaceutical and medical technology, harmful multidrug-resistant bacteria are a
great threat and day-by-day bacterial infection attracts the attention of researchers due
to increasing the number of multidrug-resistant bacteria [1]. Large pharmaceutical
industries are showing less interest to find out new antibiotics as it is time-consuming,
expensive, and risky [2]. On the other hand, the rise of multidrug-resistant bacteria
decreases the rate of approval of the antibacterial agent [3]. Hence, resources and
attention both are devoted to finding out smart solutions which will be effective and
inexpensive [2]. The demand for antibacterial finishes on textile goods as consumers
are more aware nowadays of the potential utilization of these materials [4]. Various
types of toxic chemicals are used in textile processes, but these are not easily degrad-
able in the environment [4]. There is a huge demand for non-toxic, eco-friendly,
T. Dutt a
Department of Chemistry, JIS College of Engineering, Kalyani 741235, India
A. A. Khan
Department of Chemistry, Darjeeling Government College, Darjeeling 734101, India
N. Baildya
Department of Chemistry, University of Kalyani, Kalyani 741235, India
P. Mondal
Department of Chemistry, Baruipara High School (H.S), Murshidabad 742165, India
N. N. Ghosh (B)
Department of Chemistry, University of Gour Banga, Mokdumpur, Malda 732103, India
e-mail: ghosh.naren13@gmail.com
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_6
169
170 T. Dutta et al.
antibacterial materials as a replacement for toxic textile chemicals. Sun protec-
tion creams and textiles are two common choices for the protection against UV
radiation [5]. There are organic and inorganic UV-blockers. The organic blockers
generally absorb the UV rays, and the inorganic blockers (e.g., ZnO, TiO2)effi-
ciently scatter both UV-A and UV-B radiations, mainly responsible for skin cancer.
Compared to organic UV absorbers, inorganic UV-blockers are more preferable due
to their chemical stability under UV illumination [6–8]. Due to harmful multidrug-
resistant bacteria, an increasing demand has been observed to the food industries for
the production of high-performance packing materials. Synthetic packaging mate-
rials are a big headache for the food industry as they left a huge amount of toxic
waste materials in the environment. Nowadays, biopolymers are being explored as
environment-friendly packaging materials [9]. There is a huge demand for antimi-
crobial packaging, achieved by the utilization of antimicrobial polymeric materials
or adding antimicrobial ingredients to the packaging materials [9]. Generally, fouling
on biofilms is formed by the colonization on pipelines, ship hulls, medical devices,
drinking water treatment. Frequently formed fouling in membrane technologies
results a decrease in permeate waterflux with an increase in energy consumption.
It also decreases the extent of the membrane life period [10]. Therefore, novel strate-
gies are required to decrease the microorganism growth on membranes. A better
remedy for biofouling is the use of antimicrobial membranes [10].
In the year 1859, chitosan was discovered and first time discussed by Rouget [11].
In the early 1990s, chitosan entered the pharmaceuticals industries, which motivated
industrialists and researchers to create a more effective therapeutic system based
on it. The presence of active amino groups makes chitosan applicable in versatile
fields. Structurally, it is composed of (copolymer) d-glucosamine and N-acetyl-d-
glucosamine units with two hydroxyl (–OH) groups and one amino (–NH2) group
as shown in Fig. 6.1 [12].
Chitosan (Fig. 6.2a), the most abundant polysaccharide, is produced commer-
cially through the deacetylation of chitin [1]. Chitosan remains as a polycationic
species at low pH, because of the protonation in the amino group (Fig. 6.2b) with
an increased solubility property. Initially, chitosan was used in medical applica-
tions like wound dressing, tissue engineering, and slimming. However, with time,
it debuted as a prominent candidate for the drug delivery system [13]. Chitosan is
Fig. 6.1 Structure of d-glucosamine and N-acetyl-d-glucosamine
6 Preparation of ZnO/Chitosan Nanocomposite and Its Applications … 171
Fig. 6.2 a Structure of chitosan; b structure of chitosan at different pH
172 T. Dutta et al.
widely used in industries starting from foods to textiles, water treatment, agriculture,
cosmetics, pharmaceuticals. Due to its unique biological characteristics, like non-
toxicity, biodegradability, etc. [14]. However, the poor solubility of chitosan above
pH 6.5 limits its practical applications [2]. On the other hand, antibacterial properties
of chitosan decreases with decreasing pH of the medium [15]. Another strategy to
retain the antibacterial property of chitosan even in low pH is its combination with
metal (oxide) nanoparticles (NPs) [16].
Nanotechnology, a research hot spot of modern materials science can provide
miscellaneous applications in different fields like food processing, textile industry,
UV-blocker, fabric compounds, agricultural production, medicinal techniques [17]. It
is a new horizon of research that deals with the synthesis, characterization, and appli-
cations of nanometer (nm) scaled (1–100 nm) materials. In this area, the pertinent
materials show new and considerably enhanced physicochemical properties with a
distinct phenomenon due to nanoscale size [18]. NPs generally offer larger surface
areas compared to the macro-sized particles [19]. NPs are basically manipulated
particles at the atomic level (1–100 nm). Metal NPs gained more attention due to
their specificity and higher chemical reactivity as compared to their bulk state. The
large surface-to-volume ratio of NPs makes nanoscale materials attractive for a large
number of applications [20]. NPs provide extremely active centers, but they oxidize in
air or agglomerates easily due to their high energy and extra-large surface area which
leads to inactivation of both reactive and adsorption sites of NPs [20]. It reduces the
contact between metal NPs and target molecules [21]. Over the past decades, scien-
tists have adopted several approaches to achieve this goal. Metal NPs capping with
biopolymers or natural compounds are the most common process to stabilize it for
long-term utilization [22–26]. Nowadays, nanocomposite term is most common due
to its versatile applications and long-term stability. The term nanocomposite indicates
dispersed NPs in filled polymers [22]. Nowadays, ZnO/chitosan nanocomposite has
attracted the attention of researchers due to its versatile application in various fields.
Zinc oxide (ZnO) presents in the earth’s crust as a mineral zincite, while most of
the ZnO used commercially is produced through different types of synthetic methods
[27]. It is non-toxic and compatible with human skin with creating an additive for
textile surfaces that are in touch with the flesh [27]. In comparison to bulk, zinc oxide
nanoparticles (ZnO-NPs) have unique properties [28]. ZnO-NPs are portrayed as
strategic, functional, versatile, promising, and inorganic materials with a wide range
of applications [29]. The synthesis of ZnO-NPs has led to the exploration of its use as
an antibacterial agent. With its unique antibacterial properties, ZnO-NPs also possess
high optical absorption in the UV-A (315–400 nm) and UV-B (280–315 nm) regions
and for that reason, it is used as a UV-blocker in cosmetics [30]. ZnO-NPs seem to
powerfully resist microorganisms, and several reports showed its sizeable antibac-
terial drug activities that are attributed to reactive oxygen species (ROS) generation
on the surface of these oxides [31]. Antibacterial activities of ZnO-NPs are also used
in textile industries [32]. ZnO-NPs work on biocidal effects on bacterial species and
exhibit marked antibacterial activity at low concentrations in neutral pH region (~7)
[33]. To enhance the different activities (e.g., antibacterial, UV-blocker), biocompat-
ibility, and stability of ZnO-NPs, recent studies have focused on the effective coating
6 Preparation of ZnO/Chitosan Nanocomposite and Its Applications … 173
Fig. 6.3 Chitosan-capped ZnO-NPs
Fig. 6.4 Deacetylation of chitin to chitosan
of ZnO-NPs with biopolymers [34]. Chitosan is the suitable one for the effective
coating of the ZnO-NPs. Due to the presence of active functional groups (i.e., amine,
hydroxyl), chitosan can bind ZnO-NPs to form stable ZnO/chitosan nanocomposite
which allows us to formulate new environment-friendly composite-based biomaterial
in a cost-effective manner using natural resources[1, 20, 35]. This organic–inorganic
hybrid materials (Fig. 6.3) show excellent antibacterial and UV-blocking properties
which increase its application in textile industries [34].
6.2 Preparation of ZnO/Chitosan Nanocomposite
Saad et al. followed a common route for the preparation of ZnO/chitosan nanocom-
posite by using extracted chitosan [36]. The fresh shells of shrimp are washed thor-
oughly with double distilled water and dry in a vacuum. Powder form is produced
by grinding in a mortar, and then, it is soaked for 24 h in 1 M NaOH solution. After
that, it is again washed and dried. Then, the powder is deproteinized, demineralized,
discolored using 1 M NaOH, 1 M HCl, and acetone, respectively. Then, deacetylation
of the obtained chitin is followed using 50% NaOH at 115 °C for 2 h. For a higher
degree of deacetylation, the process is repeated (Fig. 6.4). The resulting chitosan is
then rinsed with distilled water followed by filtered and dried for 24 h.
Zn(NO3)2·6H2O, ethanol, (NH4)2CO3, and deionized water are used as the starting
materials to prepare ZnO-NPs. At first, (NH4)2CO3 and zinc nitrate are dissolved
in deionized water to form solutions. Zinc nitrate solution is slowly added into the
174 T. Dutta et al.
Fig. 6.5 Preparation of ZnO/chitosan nanocomposite by precipitation method
(NH4)2CO3 solution with continuous stirring at 40 °C for 60 min. The precipitates
are collected by filtration with a micrometer filter paper and rinsed with deionized
water followed by ethanol. Precipitates are dried at 80 °C and calcined at 550 °C
temperature for 2 h in the muffle furnace to get white ZnO-NPs. One gm of ZnO-NPs
powder is added in acetic acid (1%, 100 mL) solution followed by the addition of
chitosan (1.0 gm). NaOH solution (0.10 M) is added after keeping the solution in
a sonicator bath for 30 min to maintain the pH 7. After that, the resulting solution
is filtered and washed with distilled water then dried at 50 °C to get ZnO/chitosan
nanocomposite (Fig. 6.5).
X-ray powder diffraction (XRD) study of the ZnO-NPs (Fig. 6.6b) reflects nine
characteristic peaks (28 = 68.97°, 67.90°, 66.38°, 62.720°, 56.54°, 47.47°, 36.24°,
34.44°, and 31.74°). Li et al. also support this kind of observations [37]. The synthe-
sized ZnO/chitosan nanocomposite (Fig. 6.1a) is amorphous in nature and exert of
strong diffraction peaks at 28 = 47.470°, 34.440°, and 31.740° reveal that the ZnO-
NPs are well coated by chitosan with peaks between 28 of 20° and 10° and it is well
supported by the studies of Sivaraj et al. [38]. Formation of globular morphology
of ZnO/chitosan nanocomposite is well supported by the field emission scanning
electron microscope (FESEM) and bright-field (BF) scanning transmission electron
microscopy (STEM) studies (Fig. 6.6c). Transmission electron microscope (TEM)
study also shows the spherical nature of the particles with an average size of 58 nm
(Fig. 6.6d).
Fourier Transform infrared spectroscopy (FTIR) study describes that hydroxyl
and amine groups are mainly responsible for the stabilization of ZnO/chitosan
nanocomposite [1].
6 Preparation of ZnO/Chitosan Nanocomposite and Its Applications … 175
Fig. 6.6 XRD pattern of a ZnO/chitosan nanocomposite, b ZnO-NPs; c FESEM and bright-field
STEM images and d TEM image of ZnO/chitosan nanocomposite [36]
In another study, Saeed et al. synthesized ZnO/chitosan nanocomposite in a
different manner [35]. Different amounts of ZnO are dissolved into acetic acid
followed by the addition of high-molecular-weight chitosan. Acetic acid is added
for increasing the volume of the solution. A continue stirring is very much needed
to dissolve the chitosan flakes. 1N NaOH may be added to maintain the pH 10 of the
solution. After heating in a water bath and cooling at room temperature, the mixture
is filtered. The obtained white precipitate is washed with distilled water and dried at
60 °C for getting ZnO/chitosan nanocomposite. TEM study suggests that synthesized
ZnO/chitosan nanocomposite is in the range of 20 nm.
176 T. Dutta et al.
Dananjaya et al. [34] also followed almost the same process for the synthesis of
ZnO-NPs as followed by Saad et al. In this case to get ZnO/chitosan nanocomposite,
the mixture (synthesized ZnO-NPs, acetic acid, and chitosan) is sonicated with the
addition of NaOH. Two sets of diffraction peaks (for ZnO and chitosan) confirm
the successful formation of ZnO/chitosan nanocomposite. The purity of the synthe-
sized ZnO/chitosan nanocomposite can be confirmed by the absence of peaks due
to the impurities like Zn or Zn(OH)2. The mean crystalline size of the synthesized
ZnO/chitosan nanocomposite can be estimated by using Scherrer’s formula [39], and
it is found in the region of 22 nm. Spherical-shaped ZnO-NPs can be determined from
the FESEM image (Fig. 6.7a). The inset TEM image (Fig. 6.7a) also reflects good
dispersion of the ZnO-NPs. Zn and oxygen dominate the energy-dispersive X-ray
spectroscopy (EDS) profile (Fig. 6.7b) indicating the absence of elemental impurities
present. If carbon tape is used for the sample loading, then there is a chance of getting
a carbon peak in the EDS profile. A cluster-like morphology is generally observed
in the FESEM image (Fig. 6.7c) of ZnO/chitosan nanocomposite. The inset TEM
image (Fig. 6.7c) of ZnO/chitosan nanocomposite reflects irregular shape of clus-
ters having randomly aggregated NPs. The EDS profile (Fig. 6.7d) of ZnO/chitosan
nanocomposite further confirms the formation of ZnO/chitosan nanocomposite. The
presence of nitrogen in Fig. 6.7d is probably due to the presence of amine (–NH2)
group of chitosan.
The UV–Vis absorption spectroscopic (UV–Vis) study (Fig. 6.8) of ZnO-NPs and
ZnO/chitosan nanocomposite displays a similar pattern of absorption spectra with
a slight variation of absorption maxima. ZnO-NPs exhibits an absorption maxima
around 365 nm, but it shifts to 355 nm in ZnO/chitosan nanocomposite due to the
presence of the interaction between chitosan and ZnO-NPs (Fig. 6.8).
6.2.1 General Mechanism of the Formation of ZnO/Chitosan
Nanocomposite
In acidic medium (pH: 6–9), at first ZnO converts to Zn2+ followed by the formation
of Zn(OH)2. As the –NH2 and –OH groups of chitosan can form a co-ordination
bond with metal ions [40], with increasing the pH of the solution (generally by the
addition of NaOH), a stable complex of ZnO/chitosan nanocomposite is formed [5].
6.3 Antibacterial Activity of ZnO/Chitosan Nanocomposite
ZnO-NPs are quite attractive due to their significant antibacterial properties. Biocom-
patibility of the ZnO-NPs increases when it is capped by chitosan [41]. For this
reason, the scope of versatile biomedical application of ZnO/chitosan nanocom-
posite increases. Furthermore, the antibacterial action ZnO/chitosan nanocomposite
178 T. Dutta et al.
improves significantly with respect to its reference material (only ZnO-NPs or
chitosan) [10, 42–44]. Theodoridou et al. made an antibacterial assay of ZnO/chitosan
nanocomposite against Escherichia coli (E. coli) BL21(DE3), Corynebacterium
glutamicum (C. glutamicum) ATCC 21,253, and Brevibacterium lactofermentum (B.
lactofermentum) ATCC 21799 [41]. This study reflects that the antibacterial activity
of ZnO/chitosan nanocomposite is high against B.lactofermentum, moderate against
E. coli and almost absent against C.glutamicum. The observed differences may be
related to the compositional and structural differences in cell membrane of each
bacterium [10]. Rahman et al. prepared ZnO/chitosan nanocomposite film to increase
its utility in the food industry as a food packaging material [45]. For this reason, they
checked the antibacterial effect of the film against Staphylococcus Aureus (S. aureus,
MTCC 737) and Escherichia Coli (E. coli, MTCC 1687) bacteria by colony-forming
units (CFU/gm) method. As per this observation, the composite film shows significant
antibacterial activity with respect to the control chitosan. ZnO/chitosan nanocom-
posite film showed higher antibacterial activity against E. coli than S. aureus. This
investigation also reveals that antibacterial activity is directly related to the amount
of ZnO-NPs particles in the composite films. The decreased activity of composite
film toward S. aureus bacteria is due to the presence of thick peptide glycan layer in
its cell wall [46]. Another research work also reflected same kind of results (Table
6.1) at different concentrations of ZnO/chitosan nanocomposite against E. coli and
S. aureus [5].
Vaseeharan et al. also reported the antibacterial activity of ZnO/chitosan nanocom-
posite against Gram-positive Bacillus lechiniformis (B. lechiniformis; accession
No-HQ693275) and Gram-negative Vibrio parahaemolyticus (V. parahaemolyticus;
accession No-HQ235407) isolated from aquatic environments by broth culture and
zone inhibition methods in the pH range of 6–7 [47]. In that study, the growth curves of
the B. lechiniformis and V. parahaemolyticus without ZnO/chitosan nanocomposite
showed increased level of bacterial growth up to 150 min. On the other hand, V. para-
haemolyticus and B. lechiniformis treated with ZnO/chitosan nanocomposite show a
significant reduction in growth (Fig. 6.9). Furthermore, growth of the tested bacteria
decreases after treating with ZnO/chitosan nanocomposite from 30 to 150 min. Zone
inhibition test also shows that there is no zone of inhibition against the tested bacteria.
Inhibitory activity of ZnO/chitosan nanocomposite may vary with the pH of the
medium and the percentage of the –NH2 functional group on the chitosan surface [47].
Table 6.1 Antibacterial activity of ZnO/chitosan nanocomposite at different concentrations [5]
Concentration of ZnO/chitosan nanocomposite (%) Inhibition zone (mm)
S. aureus E. coli
0.5 5 7
1 9 10
211 12
411 13
6 Preparation of ZnO/Chitosan Nanocomposite and Its Applications … 179
Fig. 6.9 Growth curves of B. lechiniformis and V. parahaemolyticus in the presence of
ZnO/chitosan nanocomposite and without ZnO/chitosan nanocomposite. (The error bars indicated
the standard deviation, and CS/ZnO represents ZnO/chitosan nanocomposite) [47]
Vaseeharan et al. also studied the antibiofilm efficiency of ZnO/chitosan nanocom-
posite [47]. Light microscopy (Fig. 6.10) and confocal laser scanning microscopic
(CLSM) images (Fig. 6.11) showed the bacterial growth inhibition with disrup-
tion of biofilm growth after 24 h of treatment with ZnO/chitosan nanocomposite.
ZnO/chitosan nanocomposite inhibits the biofilm formation of B. lechiniformis and V.
parahaemolyticus at the concentrations of 20–60 µg/ml. Antibiofilm efficacy results
show higher colonization in control V. parahaemolyticus and B. lechiniformis biofilm
growth, whereas in the presence of ZnO/chitosan nanocomposite, a greater reduction
of colony and a gradual decrease in the biofilm growth are observed (Fig. 6.10a and
b).
Fig. 6.10 Light microscopic images (×40); antibiofilm efficacy of different concentrations (20–
60 µg/ml) of ZnO/chitosan nanocomposite against a B. lechiniformis b V. parahaemolyticus [47]
180 T. Dutta et al.
Fig. 6.11 CLSM images; antibiofilm efficacy of different concentrations (20–60 µg/ml) of
ZnO/chitosan nanocomposite against a B. lechiniformis and b V. parahaemolyticus [47]
The thickness of the biofilm is reflected in the CLSM images (Fig. 6.11). CLSM
studies establish that V. parahaemolyticus and B. lechiniformis biofilm growth is
completely arrested at a concentration of 40 mg/ml and 60 mg/ml, respectively
(Fig. 6.11 a and b).
6.3.1 Probable Mechanism of the Antibacterial Activity
of ZnO/Chitosan Nanocomposite
The suggested mode of antibacterial action of the ZnO-NPs includes (a) the dissolu-
tion of ZnO-NPs followed by the release of Zn2+ antibacterial ions, (b) penetration of
nanosized particles with cell membrane damaging, and (c) reactive oxygen species
formation on the surface of the ZnO-NPs which destroys bacterial cells [29, 48,
49]. The antibacterial activity of ZnO-NPs depends on the size due to the internal-
ization and accumulation of NPs inside the cells [ 29]. Rahman et al. also suggest
a probable mechanism of antibacterial activity, similar to the previous study [45].
ZnO-NPs release ROS. The ROS and Zn2+ ions attack negatively charged cell wall
which causes cell leakage and ultimately the death of bacteria [50]. On the other
hand, ZnO-NPs enhance the positive charge on the –NH2 group of chitosan which
accelerates the interaction with the anionic components on the bacterial cell wall
[50].
6 Preparation of ZnO/Chitosan Nanocomposite and Its Applications … 181
6.4 Applications of ZnO/Chitosan Nanocomposite
in Textiles
Nowadays, there is a huge demand for antibacterial finishes on textiles as the textiles
are considered as the ideal environment for bacterial growth. Significant antibacte-
rial activities and UV-blocking properties of ZnO/chitosan nanocomposite increase
its demand in textile industries. Farouk et al. selected cellulosic fabrics to check
the antibacterial activity of ZnO/chitosan nanocomposite against E. coli, and M.
lutues and they observed that, in case of both M. lutues and E. coli there was nearly
100% reduction of the colonies after 3 h in case of cotton 100% treated fabrics with
ZnO/chitosan nanocomposite against M. lutues and E. coli bacteria [51].
SEM micrographs (Fig. 6.12) reflect that the surface of the treated fabric becomes
smoother compared to the untreated fabrics due to the homogeneous distribution of
ZnO/chitosan nanocomposite within the coating layer. Cotton/polyester fabric treated
with ZnO/chitosan nanocomposite shows a lower absorbance value of formazan
with respect to the formazan absorbance value of untreated cotton/polyester fabric.
The tensile strength of fabric samples treated with ZnO/chitosan nanocomposite is
significantly increased. This increase may be attributed to penetration of the chitosan
molecule which makes some kind of sizing to the treated fabrics and improves the
tensile strength. Air permeability is considered an important factor in the performance
of textile materials. Coating to the fabrics by ZnO/chitosan nanocomposite does not
cause decreasing of air permeability.
Arafat et al. used ZnO/chitosan nanocomposite as an adsorbent to remove reac-
tive dyes (Black HN and Magenta HB) from textile dyeing industry effluent [52].
As per their observation, ZnO/chitosan nanocomposite has a dye removal effi-
ciency of 95–99%. They also claim that color adsorption ability increases with
Fig. 6.12 Scanning electron microscope (SEM) images of the a untreated cotton/polyester
(65/35%) fabric and b ZnO/chitosan nanocomposite-treated cotton/polyester (65/35%) fabric [51]
182 T. Dutta et al.
increasing the dosage of ZnO/chitosan nanocomposite. This study also reflects 2
gm of ZnO/chitosan nanocomposite per liter of effluent at an ambient temperature
(50 °C) and 60 min of contact; it is possible to remove approximately 99% of the
original color of the effluent. Petkova et al. also used ZnO/chitosan nanocomposite
for sonochemical coating of textiles to get rid of microorganisms [53]. This coating
improves the durability, biocompatibility, and antibacterial activity (against S. aureus
and E. coli) of the textile.
6.5 Applications of ZnO/Chitosan Nanocomposite
as a UV-Blocker
Due to the depletion of the ozone layer in the earth’s atmosphere, the effect of
UV radiation increases on human skin. This UV irradiation has a cytotoxic effect
on the skin cells (keratinocytes and fibroblasts) and causes of skin cancer with the
damage of the epidermis [54, 55]. Therefore, researchers are interested to focus on
the development of textiles with UV protection functionality [56]. With sunscreen,
UV-absorbing compounds are also in other personal care products, like lipstick, hair
spray, shampoo, toilet soap, body wash, and insect repellent [57]. UV is the part of
invisible light which are categorized with three different part according to their wave-
length: UV-A (320–400 nm), UV-B (280–320 nm), and UV-C (200–280 nm) [58].
Chemically, two types of UV-blockers are available in the most recent decades—inor-
ganic and organic. The mechanistic pathway of UV-blockers is either absorbing or
scattering the UV radiation [57, 59]. Especially, organic materials (known as chem-
ical filters) act as an absorber, mainly UV-B radiation, whereas inorganic materials
(known as physical UV filters) follow the scattering and reflection pathway to block
the UV radiation [60]. The presence of nano-oxides in sunscreens plays a vital role
in the generation of reactive oxygen species (ROS), and this process is based on the
photogeneration of electron–hole pairs followed by the interfacial electron transfer
(IFET) or energy transfer process [61]. During the energy transfer process, singlet
oxygen (1O2) is produced, and while superoxide (O2 •–), hydroxyl radicals (OH•), and
hydrogen peroxide (H2O2) are formed through IFET process [62, 63]. The produced
singlet oxygen and hydroxyl radicals are responsible to show cytotoxicity and muta-
genicity [64]. The above phenomenon leads to the oxidation of organic ingredients
in cosmetics and ultimately, interacts with the protein, DNA, and lipids and finally,
photodamaged the cell [65, 66]. Recently, researchers are trying to minimize the
photoactivity of ZnO-NP through surface modification with different antioxidants
[63]. Polymer coating with natural antioxidant like chitosan is the most preferable
and interesting way surface modification [67].
To check the applicability of ZnO/chitosan nanocomposite as a UV-blocker, the
following method can be used. 0.5–4% (by weight) of ZnO/chitosan nanocomposite
powder is suspended in water followed by the sonication of 10 min. In this suspen-
sion, bleached cotton fabric samples are padded in two dips and nip followed by
6 Preparation of ZnO/Chitosan Nanocomposite and Its Applications … 183
Fig. 6.13 UPF rating of bleached cotton fabric treated with ZnO/chitosan nanocomposite [5]
squeezing to a wet pick-up of 100%. The samples are dried at 100°C1(10 min) and
cured at 170 °C (5 min). The treated cotton fabrics are washed with distilled water
and finally dry [5]. Figure 6.13 reflects UV protection of bleached cotton fabric
treated by ZnO/chitosan nanocomposite. The ultraviolet protection factor (UPF) of
the treated samples is higher than that of untreated cotton fabric. UPF rating very
much depends on the concentration of ZnO/chitosan nanocomposite which reflects
its UV absorption capacity on the surface of the cotton fabric [68].
6.6 Conclusion
In summary, ZnO/chitosan nanocomposite is a good option to the textile indus-
tries for a coating over textiles to improve its antibacterial and UV-blocking prop-
erties. Various methods are available to synthesize ZnO/chitosan nanocomposite.
UV–Vis, FTIR, TEM, SEM, XRD studies can be used to characterize synthesized
ZnO/chitosan nanocomposite. The size and stability of ZnO/chitosan nanocomposite
depend on its synthesis route. Depending on the application of the ZnO/chitosan
nanocomposite, its synthesis route should be selected. The antibacterial properties of
ZnO-NPs depend on their size. Coating of textiles with ZnO/chitosan nanocomposite
also increases its durability and biocompatibility.
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Chapter 7
Polymeric Nano-Composite Scaffolds
for Bone Tissue Engineering: Review
Lokesh Kumar and Dheeraj Ahuja
Abstract Bone tissues have an amazing ability to repair and regenerate. However,
complex bone fractures and defects still present a significant challenge to the
researchers in biomedical field. Current treatments center on autograft-allograft and
metal implant to substitute bone loss. While metal implant and allograft treatments
are associated with several complications such as donor site morbidity and limited
supply of material. Therefore, scaffolds can provide a new method to resolve such
problems by restoring and improving tissue functions. An ideal scaffold should
have biocompatible and biodegradable, as well as suitable 3D porous interconnected
structure to facilitate cells and tissues in growth with proper circulation of bone
mineralization. To date, various biomaterials are available for bone tissue engi-
neering including ceramics, polymers and composites composed by calcium and
phosphate bone minerals. Polymeric scaffolds can be modified to improve bioac-
tivity and osseointegration mechanical strength in order to tailoring biological prop-
erties. In this chapter, strategies and techniques to engineer new kind of polymer
surface to promote osteoconduction with host tissues will be discussed. Also, bene-
fits and applications of polymeric composite scaffolds for orthopedic surgery will be
discussed.
Keywords Tissue engineering ·Polymer scaffold ·Osteoconductive ·
Biodegradable
Abbreviations
HA Hydroxyapatite
L. Kumar
Dr. K.N Modi Institute of Engineering and Technology, Modinagar, Uttar Pradesh 201204, India
D. Ahuja (B)
Chemical Engineering Department, Deen Bandhu Sir Chhotu Ram, Government Polytechnic
Education Society, Sampla, Rohtak, Haryana 124501, India
e-mail: dheerajahuja84@gmail.com
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_7
189
190 L. Kumar and D. Ahuja
TE Tissue engineering
PLA Polylactic acid
PU Polyurethane
ECM Extracellular matrix
PCL Poly(caprolactone)
PGA Poly(glycolic acid)
PMMA Polymethylmethacrylate
PA Polyamide
PLGA Poly(l-lactic-co-glycolic acid)
TIPS Thermally induced phase separation
PLA Polylactide
TCP Tri-calcium phosphate
TEA Triethanolamine
DEA Diethanolamine
PEG Poly(ethyleneglycol)
7.1 Introduction
7.1.1 Scaffold for Bone Tissue Engineering
An extensive variety of clinical methods have been utilized for replacement or repair
of bone or tissue damaged due to any disease or injury. Currently, the most widely
utilized healing practice is based on three types of donor graft tissues: allograft, auto-
graft and xenografts. The major limitation of utilizing these healing practices is less
availability of donor and donor sites, higher morbidity rate, chances of disease trans-
mission and rejection of grafts [ 1]. This limitation can be overcome by tissue engi-
neering. Tissue engineering reproduces the damaged tissue by developing biolog-
ical substitutes rather than restoring them with grafts. This helps in reviving and
improving tissue function [2–4]. The first article on tissue replacement was published
by Gaparo tagliacozzi in 1597 [5]. Tissue repair and regeneration are natural healing
processes that take place after damage on patient’s body. For example, liver is one of
the organs of human body that can be regenerated after fractional noxiousness [6].
The tissues can be reproduced in two different ways. The first way includes
isolation of cells from patient’s body and growing them on three-dimensional scaf-
folds under controlled conditions. The tissues so cultured are then replaced with the
defected tissue, and the scaffold is degraded over the time. Another way is directly
growing tissue in vivo utilizing scaffold that instigates and targets growth of tissue.
The in vivo method, i.e., direct growth of tissue in patient body, is beneficial over
in vitro, i.e., growing tissue in culture and then replacing as for in vivo tissue grows
in situ and patient’s cells are not required. The combination of both in vivo and
in vitro is known as tissue engineering triad and is shown in Fig. 7.1. This triad
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 191
generally works on three fundamentals, i.e., signaling mechanism, cells and extra-
cellular matrix (ECM). ECM holds the cells and helps in regeneration and devel-
opment of tissues [7]. The fundamental conception is to utilize inherent biological
responses to tissue damage in conjunction with engineering fundamentals [8]. In
tissue engineering, regeneration of bone tissue is widely studied area. As per bone
tissue engineering fundamentals, bone tissue equivalents are developed by targeting
osteogenic differentiation of multipotent mesenchymal stem cell of bone marrow
[9]. It is being utilized for implant surgery, where the objective is to harvest the ideal
tissue engineered bone construct [10, 11].
Tissue regeneration process is generally achieved by implying three steps that
help in attainment of entire process. The first steps involve inoculation or transporta-
tion of grown cells to a damaged or injured site followed by transmission of tissue
producing biomolecules to a targeted tissue. The final and third step involves growth
and differentiation of a required cell type in 3D scaffolds. Among all these three
steps or approach, tissue engineering based on scaffold is gaining attention as it has
the possibility of assimilating chemical, physical and biological stimuli with scale
variation for cell activity.
Therefore, in the last two decades research in the arena of scaffold-based tissue
engineering has increased at a rapid rate [12, 13]. Among the varieties of scaffolds,
research on biodegradable polymeric scaffolds for tissue engineering is gaining much
attention as they cater sensual and structural surroundings for growth of cells and
tissue [14–17]. Scaffold is central component that is utilized for delivering drugs, cells
Fig. 7.1 Tissue engineering system (triad)
192 L. Kumar and D. Ahuja
Fig. 7.2 Different types of polymeric scaffolds for cell and drug delivery
and genes into the patient’s body. On the basis of this, scaffolds are classified as cell
delivery scaffold and drug delivery scaffold. Implantation of cells into fabricated
arrangement capable to support 3D tissue formation is referred as “cell delivery
scaffolds,” while fabricated arrangements capable of high drug loading efficiency
and drug release for longer duration are known as “drug delivery scaffolds” [18, 19].
Polymeric scaffolds being utilized for cell or drug delivery application include 3D
porous matrix, a nanofibrous matrix, a thermoresponsive sol–gel transition hydrogel
and a porous microsphere as shown in Fig. 7.2 [20–23]. These all are being utilized for
constant drug discharge formulations and have been practiced in tissue engineering
for their possible usage as a cell delivery carrier or supportive matrix [24].
7.2 Properties of Scaffold
Scaffolds are three-dimensional structures formed by the implantation of cells that
helps in cell formation. They also help in repositioning of contained structure and
generating adequate mechanical settings for the proper healing of the organ by
providing mechanical support. Also, they help in growth and attachment of cell,
thereby leading to cell formation. Further, it also drops and absorbs cells and biome-
chanical factors, enables diffusion of vital cell nutrients and expressed products along
with exerting specified mechanical and biological influences to change the perfor-
mance of cell phase. Once the patient’s body part or organs is healed, the extraneous
part is required to be detached from human body together with clinical and biome-
chanical point of view. Hence, there are some of the key characteristics that must
be considered while fabricating 3D scaffolds for tissue engineering. Generally, the
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 193
Table 7.1 Essential properties required for smooth functioning of cell delivery scaffolds and drug
delivery scaffolds for tissue engineering
Cell delivery scaffolds Drug delivery scaffolds
• Tolerable tensile properties to defense cells
from tensile forces [32]
• Uniform distribution of drug all over the
scaffold [33]
• Desired volume, mechanical strength and
shape [34]
• Capability to deliver the drug at fixed
interval of time [35]
• Admissible biocompatibility [14]• Low drug abiding affinity so as to allow
stable drug delivery during scaffold injection
at a physiological temperature [36]
• Bioadsorption at fixed interval of time [37]• Dimensionally, structurally and biologically
balanced activity for longer duration [36]
• Biocompatible chemical combination with
minimum allergic and immune responses
[38]
• An extremely porous and interrelated open
pore architecture to concede high cell
seeding density and tissue in growth [39, 40]
• Physical architecture to hold cell
adhesiveness and propagation [41]
scaffold should be biocompatible and possibly biodegradable with desirable surface
properties for cell adhesion, mitigation and normal functionality persuaded by the
desired mechanical strength and porosity to be able to integrate with the surrounding
tissue [17, 25, 26]. In addition, size of scaffold must be identical to the injured surface.
Furthermore, biological signals from scaffolds such as small drug molecule, growth
factors and cytokines in vitro and in vivo should be delivered in controlled manner
as they are important parameters for foundation and enrichment of tissue morpho-
genesis, viability and functionalities [27–29]. Hence, fabrication should take into
account the physico-chemical properties for the release of required biomolecules to
direct and regulate biological responses of the cells into particular tissue.
As described in the above section that scaffolds for bone tissue engineering are
classified as cell delivery scaffolds and drug delivery scaffolds. Some of the important
properties that both types of scaffolds should possess for effective tissue engineering
are mentioned in Table 7.1 [30, 31].
Apart from the abovementioned properties for cell delivery and drug delivery
scaffolds, some of other important properties that should be considered for scaffold
tissue engineering are discussed below:
7.2.1 Biocompatibility
It is referred as the ability of a material to meet the desired application without
performing an allergic or harmful immune effect. The scaffold prepared to be seeded
194 L. Kumar and D. Ahuja
should have admissible biocompatibility and toxicity profile [42]. Also,itmusthave
sufficient surface chemistry for cellular attachment, differentiation and proliferation
[43]. Further, it should adhere to the cells with minimal interruption of surrounding
tissues. Variety of tissue responses are attained from seeding of scaffolds depending
upon their composition [44]. When the scaffold seeded is nontoxic and degradable,
new tissue is generated while the nontoxic and biologically effective scaffold assimi-
lates with the neighboring tissues. In case the scaffold is biologically inactive, it may
be enclosed with fibrous capsule, whereas it is rejected from the body resulting in
the death of neighboring tissue when it is toxic [45–48]. Samandari and Samandari
[49] studied the biocompatibility of prepared chitosan-graft-poly(acrylic acid-co-
acrylamide)/hydroxyapatite nanocomposite scaffold using multistep model by MTT
assays on HUGU cells. It was found that scaffold has good cytocompatibility and cell
viability and proliferation enhanced with reinforcement of hydroxyapatite. Kumar
and Ahuja [50] synthesized aliphatic polyurethane nanocomposite utilizing modified
hydroxyapatite and performed cell culture and in vitro studies in simulated body fluid.
It was observed that surface was partially hydrolyzed and prepared nanocomposite
was suitable for bone tissue engineering.
7.2.2 Biodegradability
It is referred as the chemical disintegration of a biomaterial by bacteria or other
biological molecules inclusive of hormones, acids and body fluids [51]. The devel-
oped scaffold shall be degradable. Products resulting from the degradation of scaffold
control the response of immune system. Therefore, the degradation products of scaf-
folds shall be nontoxic and should be easily exterminated from the implanted spot
of the body so as to get rid of further surgery to remove it. Further, the rate of degra-
dation of scaffold shall be adjustable so that it can be balanced with the rate of tissue
production so that it completely dissipates from the body after the tissue production.
Hence, currently the scaffolds are developed from the familiar degradable polymers
for scaffold tissue engineering. To impart the above-desired properties, the scaffold
shall be able to tune mechanical properties, degradation kinetics and release kinetics
for different purposes. The degradable polymers to be utilized for orthopedic injuries
must fulfill series requirements like mechanical support during tissue growth, orga-
nized degradation to biocompatible breakdown products and controlled release of
biomolecules and shall maintain osteoconductive and osteoinductive surroundings.
In the recent past, a great deal of attention is being focused on utilization of
biodegradable polymers for the development of scaffolds. The reason for this is their
well-acknowledged biocompatibility in vivo in addition to the two major reasons.
Firstly, the scaffold prepared using degradable polymers can be tuned for their
mechanical properties along with their controlled degradation. Secondly, with the
passage of time after complete healing of the injury the architecture of scaffolds
completely degrades eliminating the need of second surgery for the rehabilitation of
the implant, thereby resulting in the fast recovery of the i njured site. Among various
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 195
degradable polymeric scaffolds such as polyglycolic acid (PGA) [52], polylactic acid
(PLA) [53], polyurethanes (PU) [54] and polycaprolactone (PCL) [55], polyurethane
is best delivery scaffolds and offers several benefits in the design of injectable and
biodegradable polymer composition [56–59].
7.2.3 Porosity
It is degree of material void space and is a part of void volume by absolute volume
and is also referred as “void fraction”[
60]. Competent porosity, pore size distribution
and inter-pore connectivity support vascularization and cell growth [61, 62]. Mondal
et al. in 2014 synthesized surface modified and aligned mesoporous anatase titania
nanofibers-based mats for esterified cholesterol detection and found that around 61%
enzyme molecules were loaded in the mat due to its high porosity of fibers [63].
7.2.4 Targetability
It is the capability of the formulation system to influence their prearranged spot
and release their enclosed substances on the injured spot [64]. Formulation systems
composed of nanofibers have magnificent capacity to transport their enclosed
substances to the injured spot and escape from their side effects. This effective target
ability results in the reduction of the dose and frequency of enclosed substances
[65, 66]. Gong et al. encapsulated amphiphilic peptide developed by transformation
of nanoparticles to nanofibers for growth of immune system after cancer treatment.
It was observed that amphiphilic peptide had antitumor properties and low toxi-
city in mammalian cell indicating good biocompatibility in addition to antibacterial
properties, to prevent from bacterial contamination [67].
7.2.5 Binding Affinity
As the name suggests, it is the capacity of the drug to bind the scaffold. It should be
low enough to deliver the drug [68]. Varieties of scaffolds have been developed by
different researchers utilizing various nanomaterials having binding affinity [69–71].
However, among them scaffold formulation of nanofibers has proved to be having
adequate binding efficiency for continuous delivery of the enclosed substance for
longer duration or accommodating of cells in their pore structure [72, 73].
196 L. Kumar and D. Ahuja
7.2.6 Stability
Assessment of physical, chemical and biological activities of the developed
scaffold at different environment condition is referred to as stability of the
scaffold. The developed scaffolds must have chemical and biological stability
along with dimensional stability for longer duration of time. Nanocompos-
ites of scaffold exhibit magnificent stability at physiological temperatures, and
their activity is sustained for prolonged period [74–76]. Polyvinylidene fluo-
ride (PVDF)/poly(methylmethacrylate) (PMMA)/hydroxyapatite (HA)/titanium
oxide (TiO2) (PHHT) film scaffold nanocomposites with surface morphology
nanowhiskers were developed by Arumugam et al. [77]. The prepared nanocom-
posites were explored for mechanical stability and in vitro studies for biomedical
application. Results showed that nanocomposite scaffolds were mechanically stable
and can be used for biomedical applications.
7.2.7 Loading Capability and Deliverance
It is the quantity of drug that can be immersed into the scaffold. The scaffold should
possess high drug loading capability in order to deliver the drug for prolonged period
after seeding of the scaffold in the body [78]. The drug from the scaffold should be
delivered in controlled manner to allow the adequate amount of dose to be delivered
to the cells over a given duration [79, 80].
7.2.8 Mechanical Properties
The assessment of developed scaffolds characteristics over different types of forces
such as stress, strain, break, dent, stretch or scratch is referred as mechanical prop-
erties of the scaffolds [81]. These properties are influenced by the interior structure
design of scaffold. Till date, plenty of porous scaffolds have been developed that
have strength in the range of 10–30 Mpa. The strength can be altered by varying
the porosity of the scaffold [82, 83]. So that during implantation, these properties
of the scaffolds are competent with that of tissue at the seeding spot or they are
able to protect the cells from ruining tensile and compressive forces and to sustain
under physiological conditions [84]. Once the scaffold is implanted, it should impart
minimal level of biomechanical function that should continuously recover till normal
tissue function has been achieved [85].
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 197
7.2.9 Scaffold Architecture
Pore size and shape, pore tortuosity, degree of porosity and surface area constitute
the architecture of scaffold [86]. Microstructure of scaffold is utilized to examine the
movement of nutrients, waste and biological chemicals within scaffold and reciprocal
action of cell on scaffold. Movement of cells within the scaffolds is adamant by degree
of porosity and interconnectivity of pores [87, 88]. A scaffold with an undefended
and interconnected pore arrangement and a high degree of porosity (>90%) is perfect
to interconnect and assimilate with the host tissue [33, 89, 90].
7.3 2Dimesional (2D) Versus 3Dimensional (3D) Culture
Scaffold
The scaffolds developed are seeded into two types of cultures, i.e., 2D and 3D culture.
In the former culture, the cells are grown in a single layer on a glass or plastic over
slip. They communicate only in two dimensions, i.e., x and y, while in case of 3D
culture, cells are developed on a 3D porous matrix and are capable of connecting in
multiple directions. 3D scaffold permits cells to regenerate and retain extracellular
matrix (ECM) that is not possible in 2D [91]. In 2D, cells cannot clone the properties
of nutrient gradients, signal propagation or the development of bulk mechanical
properties [92]. 3D model gives more appropriate understanding of biochemical
and biophysical signaling responses of the cells, especially of the outward response
appearing in the ECM along with mechanical and chemical responses arising from
both adjacent and distant cells. This approach leads to the generation of adequate
cell-based assays for manufacturing of suitable biomaterials utilized to examine the
cell material communication [93, 94]. The 2D and 3D scaffold with culture is shown
in Fig. 7.3.
Fig. 7.3 2D versus 3D culture scaffold
198 L. Kumar and D. Ahuja
7.4 Polymer Scaffold and Processing Techniques
An ideal scaffold for tissue engineering application should possess various important
characteristics such as high porosity, surface area, structural strength and specific
shapes (3D or 2D) [95, 96]. These characteristics depend on the manufacturing
techniques of scaffolds. Till now, numerous manufacturing techniques have been
utilized for development of natural and synthetic scaffolds for tissue engineering
and regenerative medicines applications. The manufacturing techniques of scaf-
folds are generally divided into two categories, i.e., conventional manufacturing
techniques and rapid prototyping. The former technique is also referred as “non-
designed controlled fabrication” method and is used to synthesize scaffolds with
irregular microporous structure [97], whereas the latter is also known as “designed
controlled scaffold fabrication”; it facilitates fabrication of microporous structure
scaffolds with controlled dimensions, location and geometry of pores [98, 99]. In
the recent past, a new fabrication technique which is combination of conventional
and modern manufacturing method has been used for the generation of porous scaf-
folds and is referred as combined manufacturing technique [100–103]. The above
section summarizes the various fabrication techniques for the development of porous
scaffolds (Fig. 7.4).
7.4.1 Conventional Techniques
Conventional techniques inclusive of particulate leaching and solvent extraction
[104], emulsion and phase separation [105], gas foaming [106], electrospinning
[107], freeze drying [108] or a combination of techniques [109] have been utilized
for the fabrication of scaffolds for tissue engineering applications. These techniques
Fig. 7.4 Various manufacturing techniques of scaffold fabrication
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 199
Fig. 7.5 Scaffolds with different pores arrangements
lead to the formation of porous scaffolds with irregular pores and structured pores
as shown in Fig. 7.5.
7.4.1.1 Particulate Leaching and Solvent Casting
The technique particulate leaching can be used alone or in combination with solvent
casting. Particulate leaching is widely utilized scaffold fabrication technique in bone
tissue engineering and regenerative medicines. For this, initially the salt, sugar or wax
of specified size is poured into the mold; thereafter, the polymer mixture is poured
into the mold followed by hardening and crosslinking of polymer [110]. The scaf-
folds obtained have the pore size and shape identical to the dimensions of salt, sugar
or wax [111, 112]. Gorna and Gogolewski [113] prepared 3D polyurethane scaffolds
using salt leaching process for tissue repair and regeneration. In this, new elas-
tomeric biodegradable polyurethanes having an enhanced affinity toward cells and
tissues were synthesized using aliphatic diisocyanate, poly(caprolactone) diol and
biologically active 1,4:3,6-dianhydro-d-sorbitol (isosorbide diol) as chain extender.
The three-dimensional scaffolds showed poor water permeability. By loading the
three-dimensional porous polyurethane scaffolds with calcium phosphate salts such
as hydroxyapatite or tri-calcium phosphate, their osteoconductive properties can
be additionally promoted, thus making them promising candidates for bone graft
substitutes.
Solvent casting particulate leaching involves dissolution of polymer solution by
homogeneously distributing salt, sugar or wax of specified size in combination with
solvent. During the process, solvent evaporates leaving the matrix with salt parti-
cles. The matrix so obtained is then immersed in water where salt leaches out to
develop a structure with high porosity [114, 115]. This method can be applied for
thin membranes of thin wall three-dimensional samples, and under other conditions,
the soluble particles are difficult to be separated from the polymer matrix. The major
200 L. Kumar and D. Ahuja
benefits of this fabrication method are low cost and easy processing in addition to
its high porosity with capability of controlling of pore size that make it an ideal
technique for the development of 3D scaffolds [116–118]. However, the major limi-
tation of this technique is that the scaffolds synthesized do not have any control on
inter-pore connectivity and the pore structure. Moreover, it is time consuming as
evaporation of solvent takes days or weeks [119, 120].
7.4.1.2 Emulsion and Phase Separation Method
Thermal-induced phase separation [121, 122] or liquid induced-phase separation
[123–125] is other type of manufacturing method for development of scaffolds with
interconnected irregular pores. A two-phase uniform mixture of polymer can be
unsterilized thermally by changing the temperature leading to liquid/liquid or liquid–
solid phase separation. For liquid phase separation, polymer is dissolved in solvent;
thereafter, the solvent is separated by decreasing the temperature, resulting in the
formation of porous polymer scaffold. This method is known as thermally induced
phase separation (TIPS). The scaffolds prepared utilizing these methods have high
porosity. Also, their pore size can be adjusted by variation in freezing temperature,
type of solvents used, polymeric material and its concentration [126, 127]. Despite of
its advantages, the major limitation is their small pore size that can be reproducibly
obtained by this process. Furthermore, the technique utilizes organic solvents that
may leach some residual after processing, and hence, complete monitoring of the
process is required for the complete removal of solvents prior to biological analysis.
In emulsion phase separation, polymer is dissolved in solvent and then freeze dried
to induce crystallization of the solvent that acts as mold for the pores. These crystals
are then removed by freeze drying to yield porous structure. Alteration in processing
parameters induces different pore sizes and pore distribution. This technique gener-
ates relatively thick scaffolds with porosity greater than 90% and with medium and
larger pore sizes [128].
Thermally induced phase separation method was utilized by Guan et al. [126]
for preparation of polyurethane scaffolds. Effect of polymer concentration, melting
temperature and monomer type effect on porosity and pore architecture were studied.
The results showed that polyurethane scaffolds prepared with poly(ether ester
urethane) urea monomer have better cell adhesion and growth. Cai et al. [129]devel-
oped biodegradable scaffold by blending polylactide (PLA) with natural dextran
using phase separation method. The results showed that pore size of the films was
around 5–10 mm.
7.4.1.3 Gas Foaming
Gas foaming technique is used to fabricate scaffold without using solvent. In this,
gaseous porogens produced by chemical reaction or by release of gases such as
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 201
high-pressure carbon dioxide and ammonia are used to foam polymers. This tech-
nique results in the formation of scaffolds with sponge-like structure with a pore
size of 100–500 μm and a porosity up to 93% that leads to the formation of porous
structure. This large pore size and high porosity give expeditious production of
fibrocartilaginous tissue and best in growth of mesenchymal tissue along with least
inflammatory response [130–132]. Therefore, this method is best suited for the fabri-
cation of polyurethane scaffolds for tissue engineering [58]. One of the major limi-
tations with this method is that scaffolds so obtained may have closed pore struc-
ture or a solid polymeric skin [99, 132, 133]. However, combination with articulate
leaching can lead to improvement in interconnectivity of pores. Porous nanohydrox-
yapatite/polyurethane composite scaffold was developed using foaming method by
Dong et al. [134]. The prepared scaffolds were studied for biocompatibility and degra-
dation along with morphology, strength and chemical structure. Results revealed
that porosity and compressive strength of scaffolds are improved. Manavitehrani
et al. [135] synthesized poly(propylene carbonate)-based porous scaffolds using gas
foaming technique. Pore size was found to be within 100–500 μm, and biological
studies showed biocompatibility and tissue infiltration in the scaffolds.
7.4.1.4 Freeze Drying
This manufacturing technique of scaffold fabrication is based on principle of subli-
mation. For this, polymers or ceramics are dissolved in water or organic solvents
persuaded by emulsification in water phase. The solution containing polymers is
dropped in the mold, and the solvent is evaporated by freeze drying to obtain a
polymer scaffold with porous structure [136, 137]. Freeze drying is performed by
freezing the material and thereafter reducing the surrounding pressure using vacuum
and adding sufficient amount of heat to allow the frozen water in the material to
sublime directly from solid phase to the gas phase. This technique can be applied
to variety of polymers such as silk proteins, PEG, poly(l-lactic) acid (PLLA) and
PLGA/poly(propylene fumarate) blends [138, 139].
7.4.1.5 Electrospinning
This method uses electricity for making fibers from a solution and is the most
commonly utilized manufacturing method for preparation of nanofiber (NF) poly-
mers and composite [140]. This technique can be used to generate small diameter
fibers ranging from 5 μm to 50 nm with large surface area. For fabricating elec-
trospinning fibers, polymer solution is charged using a capillary tip or needle with
mechanical pressure through high voltage of around 10–30 kV. The polymer droplets
coming out from the needle grow persuaded by evaporation of solvent, resulting in
the generation of fine fibers which twin mat into porous scaffolds [141–143].
The diameter of fibers obtained using electrospinning can be varied by changing
the different parameters of electrospinning inclusive of electric field voltage, space
202 L. Kumar and D. Ahuja
among the capillary tip and solution parameters and feeding rates such concen-
tration, solvent, surface tension, molecular weight and viscosity of polymers
[144, 145]. In the recent past, this technique has been used to develop nanofiber
meshes from a variety of polymers including poly(ethylene-co-vinylacetate) [146],
poly(glycolic acid) [147], poly(d,l-lactide-coglycolide) [148], poly(d,l-lactic acid)
[149], poly(ethylene oxide) [150], poly(l-lactic acid) [151], poly(ε-caprolactone)
[152, 153] and silk [154]. Spider dragline silk protein and collagen-based composite
fibers were fabricated by Bofan et al. using this technique [155]. The prepared
composite was explored for mechanical properties and biomedical applications.
The results showed that tensile strength of fiber improved with increase in silk
percentage while a mall reduction was observed in its elasticity. Chitosan and poly-
lactic acid-based blend nanofibers were synthesized to study the combined effect
of natural and synthetic polymers [156, 157]. Karchin et al. [158] used melt elec-
trospinning technique to prepare polyurethane scaffold. For this, the biodegradable
segmented polyurethanes were synthesized using polycaprolactone diol, 1, 4-butane
diisocyanate and 1,4-butanediol which were then melt electrospinned for the prepa-
ration of scaffold. The mechanical properties of the resulted scaffolds were similar
to in vivo tissue and therefore can be used in bone tissue applications.
The major benefit of using this manufacturing method for scaffold fabrication is
that scaffold developed is suitable for cell growth and tissue regeneration. Further,
it generates superfine fibers with particular direction, high aspect ratio and surface
area that favor the cell growth both in vivo and in vitro. Furthermore, this technique
is simple and efficient and can produce both sheet and cylindrical shape [159–161].
Apart from this, there are some of limitations of using this method such as organic
solvents used for electrospinning are sometimes toxic that is not good for cells and
limited control over pore size [162, 163]. Hence, it is a big challenge to manufacture
3D scaffold with different pore geometry utilizing electrospinning method.
7.4.2 Rapid Prototyping Technique
Although conventional techniques are most widely used for the fabrication of scaf-
folds, due to their limitations these conventional techniques are being replaced by
modern or rapid prototype technique inclusive of stereolithography, selective laser
sintering, bioprinting, fused deposition modeling and solvent-based extrusion free
forming because these techniques result in the development of 3D scaffolds through
layer-by-layer assembly [164–168]. Also, pore size, porosity and shape of the manu-
factured scaffold can be altered that enhances the cell migration, proliferation and
nutrient perfusion as compared to scaffold prepared utilizing conventional techniques
[169].
Modern techniques or rapid prototyping methods are also referred as solid free-
form fabrication and use computer-aided design (CAD) model to develop a 3D struc-
ture with controlled morphology, chemical composition and mechanical properties.
The machine used in developing scaffolds using this technique generates the polymer
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 203
scaffold in layer-by-layer fashion. For this, the initial layer of the physical scaffold
is developed persuaded by thickness of next layer. At last, the fabricated scaffold is
detached from the base platform of the machine. CAD program containing scaffold
structure design and modeling is used for controlling the layers in the manufac-
turing machine. For building CAD model of particular tissue regeneration, magnetic
resonance imaging (MRI) scans and computed tomography (CT) data are utilized.
These techniques are classified on the basis of printing fundamental or on the type
of material used for printing [170].
Decreased starting time for producing prototype components, enhanced capa-
bility for anticipating part geometry due to its physical existence, prior exposure and
contraction of design errors and elaborate calculation of assembling characteristics
of components and assemblies are some of the major benefits of these techniques.
However, resolution limit that inhibits the designing of scaffold with fine microstruc-
ture, use of toxic binders and low quality arrangement are the major drawbacks of
these technologies [171, 172].
7.4.3 Combination of Techniques
The abovementioned technologies can be combined to fabricate specific polymer
scaffold. For example, phase separation can be combined with particulate leaching
[173], electrospinning with freeze drying [174], fused deposition in combination
with gas foaming [109], etc. Song et al. [109] developed hierarchical bionanocom-
posite scaffolds with tunable micro/macroporosity structure utilizing fused deposi-
tion modeling in combination with gas foaming to control the pores. The above-
prepared scaffold was explored for bone tissue engineering and found that they can
be successfully used for bone tissue regeneration. PLA-based scaffolds for tissue
engineering application were developed by Salerno et al. [173] utilizing phase sepa-
ration technology in combination with porogen leaching and scCO2 drying. Scaffolds
prepared consisted of large pores and nanoscale pore walls.
Porous scaffolds with nanotopography can be fabricated by combining modern
techniques with conventional technologies. In the recent past, progress in the develop-
ment of tissue engineering scaffolds using combination of modern and conventional
techniques was outlined by Giannitelli et al. [175]. The fabricated scaffolds on the
basis of achieved level of integration were categorized as assembly, fabrication and
technique level.
The various manufacturing technologies for scaffold with their advantages and
disadvantages are shown in Fig. 7.6.
204 L. Kumar and D. Ahuja
Fig. 7.6 Various Scaffold manufacturing techniques with advantages and disadvantages
7.5 Biomaterials for Tissue Engineering Polymeric Scaffold
Manufacturing
A variety of biomaterials inclusive of ceramic, polymers (natural and synthetic) and
composite material are used for the preparation of scaffolds for tissue engineering.
As the scaffolds are aimed to use for healthcare applications, some of the important
characteristics of biomaterials such as biocompatibility, biodegradability, cytotox-
icity, adequate mechanical strength and mucoadhesive nature must be taken into
consideration for their utilization. A variety of biomaterials like ceramics, natural
and synthetic polymer and composites are widely utilized biomaterials for fabricating
tissue engineering scaffolds.
7.5.1 Ceramics
Ceramics are inorganic biomaterials that can be categorized as bioinert and bioac-
tive. Alumina and zirconia are bioinert materials while calcium phosphate [176],
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 205
bioglass and glass ceramics [177, 178] constitute bioactive materials. Bioceramics
may either be osteoinductive (stimulate bone develop) or osteoconductive (support
bone develop). All the bioceramics are osteoconductive as all help in bone formation
but not osteoinductive. Some of the ceramic biomaterials most commonly used for
scaffold fabrication include calcium phosphate-based bioglass and glass ceramics as
their composition is alike mineral part of bone [179].
Two most widely used calcium phosphate bioceramics used in tissue engineering
scaffolds are tri-calcium phosphate and hydroxyapatite (HA) [180, 181]. Tri-calcium
phosphate is very frequently used as degradable scaffold material; on the other
hand, HA is non-resorbable and osteoinductive used for coating biomedical implants.
Osteoinductivity leads to bone regeneration, thus enabling the implant to assimilate
with the surrounding tissue. Further, HA shows improved densification and improved
sinterability because to their better surface area, that can expand fracture hardiness
as well as other mechanical properties [182].
Henceforth, HA is most widely used bioceramics for scaffold fabrication. It can
be prepared by using numerous technologies such as sol–gel processing, emulsion,
batch hydrothermal process, mechano-chemical method, chemical vapor deposition,
bio-mimetic techniques and ultrasonic spray pyrolysis [183, 184]. Among these tech-
niques, sol–gel is generally used due to its low processing temperature, homogeneous
molecular mixing and capability to produce bulk amorphous monolithic solids and
nano-crystalline powders [185, 186].
7.5.2 Natural Polymers
Natural polymers represent a convenient alternative to synthetic polymeric material
systems as their structure is similar to human bone matrix of tissues. Chitosan and
alginate are two most commonly used polysaccharides that have wide application in
tissue engineering scaffolds, which do not exist in the human body. But they exhibit
good bioactivity and can approach to cell in growth. Alginate is water soluble and
has simple gelatin chemistry with calcium ions, thus finding applications to synthesis
of scaffolds for bone tissue engineering and liver disease treatment [187]. Chitosan
is a derivative of chitin which naturally occurs in the exoskeletons of arthropods.
Chitosan with composite scaffolds has been found suitable for skin and bone tissue
engineering applications [188].
Fibrin is one of the most attractive natural proteins applied in tissue engineering
arena. Fibrin can be used in the treatment of ordinary wound repair and has wide
applications as an adhesive in ortho-surgery. It must be produced from human
blood vessels, to utilize as an autologous scaffold. Fibrin is not degradable itself
unless a protein inhibitor is used to control degradation. Fibrin hydrogels have been
used to regenerate soft tissues with chondrocytes [189] Gelatin is the derivative
of collagen that is produced by collagen molecules breaking it into single-phase
molecule. Further, disadvantages of gelatin are poor mechanical strength and hence
206 L. Kumar and D. Ahuja
are crosslinked with hyaluronic acid for skin tissue engineering and with alginate for
wound healing applications [190, 191].
7.5.3 Synthetic Polymers
Synthetic polymers are preferred over natural properties as their physical, biological
and mechanical properties can be adjusted. This can be done by altering the r atio of
monomers units or by adding particular groups (e.g., RGD peptide (arginylglycylas-
partic acid) that can be successfully recognized by human cells after the implanta-
tion in to human body. The products of degradation and degradation kinetics must
also be controlled by adequate selection of the segment to form product that can
either be released from the body by renal filtration system or can be metabolized
into nontoxic products [192]. This can be done by utilizing biodegradable polymers
such as polyglycolic acid (PGA), polylactic acid (PLA) and their copolymers like
poly(dl-lactic-co-glycolic acid) (PLGA), approved by food and drug administration
[193–195]. These synthetic polymers can be degraded hydrolytically and employed
regularly due to their by-product degradation that can be easily expelled from the
body as water and carbon dioxide. But, decreased pH in the localized area leads to
inflammation during degradation. One of the other synthetic polymers, polycapro-
lactone (PCL), whose structure is analogous to PLA and PGA can also be degraded
biologically at physiochemical condition and is generally being used for drug delivery
applications as it degrades at a slower rate as compared to PGA and PLA [196–198].
Another most commonly used degradable synthetic polymer that is biocompatible,
nontoxic and water-soluble polymer which is liquid at lower temperature and takes
the form of elastic gel at body temperature (37 °C) is poly(ethyleneglycol) (PEG)
[199]. The polymers based on PEG have been widely used as injectable scaffolds for
tissue engineering applications [200]. The hydrophilicity and rate of degradation of
PEG and PLA-based scaffolds can be controlled by tailoring the ratio of monomers.
Polyurethane (PU) is another synthetic polymer being utilized as scaffold for tissue
engineering applications. The physical, chemical and mechanical properties of PU in
addition to their biocompatibility and biodegradability can be altered in a controlled
way by changing the composition of hard and soft segment [201]. Biodegradability of
PU is generally achieved by integrating hydrolyzable moieties and labile soft segment
or by combining with degradable polymers like poly(glycolic acid), poly(lactic-co-
glycolic acid), polylactic acid, polycaprolactone, etc., for soft tissue engineering
applications [202].
7.5.4 Composites
Scaffolds synthesized from single material show poor properties in terms of
biocompatibility, mechanical strength and biodegradability. But composites scaffolds
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 207
Table 7.2 Different biomaterials for scaffold fabrication with their advantages and disadvantages
Sr. No Scaffolds biomaterials Advantages Disadvantages
1Bioceramics
(hydroxyapatite)
• Biocompatible
• Biodegradable
• Nonresorbable
2Synthetic polymers
(polylactic acid,
polyglycolic acid and their
copolymers)
• Biocompatible
• Hydrophilic
• Degradation products are
CO2 and H2O creating
local acidic conditions
3Natural polymers
(collagen and alginate)
• Biocompatible
• Good cell recognition
• Simple gelation methods
• Poor mechanical
properties
4 Composites
(polymer-ceramics,
polymer–polymer)
• Capability of altering
mechanical and biological
properties
• Compromise between
“best” qualities of
individual components
with overall scaffold
properties
including two or more bioactive materials enhance the biological properties in addi-
tion to mechanical properties of newly developed material. Polymer-hydroxyapatite
(HA) (ceramics) composites, PLA/PLGA, PMMA/HA and hydroxyapatite (HA)
reinforced with TiO2 have been developed for application in tissue engineering
[203–205]. In this approach, usually the composite matrix is prepared by biocompat-
ible polymer and inclusions of bioceramic (HA, BG, tri-calcium phosphate) parti-
cles/fibers. Polymeric composites with ceramics, such as HA, can be used as coating
on composites. Scaffolds represent an appropriate alternative of allograft or autograft
and they combine the properties of polymers (degradability) and ceramics (bioactive)
for tissue engineering application [30, 206, 207]. Advantages and disadvantages of
various types of scaffolds are tabulated in Table 7.2.
7.6 Applications
Polymeric scaffold is most commonly used for cell delivery [208], drug delivery
[209], genes delivery [179], wound healing and bone tissue engineering applications
[210, 211]. For cell delivery application, cells are injected into the scaffolds and
administered into the body, whereas for gene delivery application, polymeric scaf-
folds are used. Polymer scaffolds are architecture in such a way so as to deliver the
genetic material as polyplexes, thereby transfecting to seeded cells and expressing
the growth of cells to activate morphogenesis of particular cells to create the required
tissue [212]. Drugs with low molecular weight that proliferate or differentiate the cells
are fused into the scaffolds to activate cellular differentiation and cellular modeling
[213]. In the recent past, dexamethasone (DEX) and green tea polyphenols (GTP)
were delivered through electrospun polymer ultrafine fibers to attain a adequate
balance between effective treatment of keloid and safety to skin [214]. Scaffolds have
208 L. Kumar and D. Ahuja
shown excellent cell attachment, proliferation and penetration and thus are suitable
for tissue engineering applications. The studies show that scaffolds can be used in
blood vessels, bones, muscles, skins, neural tissue and other stem cells such as heart,
cartilage, ligament and urinary tract [212, 215, 216]. Polymeric fibrous scaffolds due
to high porosity, porous architecture, well interconnectivity and high surface area
can be utilized for wound dressing. They not only heal the wound but also expel
out the extra fluid from the wound area. Further, they also support rinsing of exoge-
nous microorganism, thereby speeding the healing process [217–219]. Thus, all these
make porous polymeric scaffolds an ideal biomaterial to be as tissue engineering and
regenerative medicine biomaterial.
7.7 Conclusion and Future Prospective
In reviewing the published literature on polymeric composite scaffolds with bioactive
properties, it was revealed that, in the recent past, new polymeric scaffold nanocom-
posite has been fabricated utilizing conventional, modern and combination of tech-
niques. New materials and combination of composite scaffolds designs based on
new fabrication method are being proposed continuously to advance bioactive and
biocompatibility of composites. Combination of techniques methods is being widely
used as it gives scaffold with required pore size and high porosity. Further, this review
article highlights required properties of the scaffolds for bone tissue engineering and
the numerous biomaterials being utilized for scaffold and its composite preparation.
It is found that bioceramics, hydroxyapatite (HA), can be used as filler in polymer
matrices to develop nanocomposite of scaffold. This has been found that HA is
significantly associated to produce bionanocomposite scaffolds with similar struc-
ture and composition to human bones. It is well known that homogeneous dispersion
of filler in polymer matrix plays a key role and mainly enhances osteoconductivity and
mechanical properties. Moreover, nanoscale organized composites provide a better
microenvironment for cell in growth in terms of cell adherence and proliferation.
Hence, ceramics/polymer composites can be developed to enhance the mechanical
and biological properties for biomedical applications. Overall, it was concluded that
polymer scaffold composites can be used as tissue engineering scaffolds.
Despite of the well-known utilization of scaffolds, if we look into practicality and
convenience, still there is a need to develop new degradable polymer composites that
can meet all the needs of surgical implants, drug and cell delivery.
Acknowledgements Authors LK and DA are thankful to University grants commission for
providing RGNF fellowship. Prof. AK is thankful to DST grant vide SEED/TIASN/008/2018 dated:
06/06/2018 and CSIR for Project Sanction no. 22(0798)/19/ EMR-II dated 24.7.2019. SM is thankful
to DST for providing Inspire fellowship. All the authors are also grateful to TEQIP-III for providing
financial assistance.
7 Polymeric Nano-Composite Scaffolds for Bone Tissue Engineering: Review 209
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Chapter 8
Biodegradable Polyvinyl
Alcohol/Starch/Halloysite Nanotube
Bionanocomposite: Preparation
and Characterization
P. Manju and P. Santhana Gopala Krishnan
8.1 Introduction
The researchers’ attention has been drawn to the need to replace petroleum-based
polymers with appropriate alternatives derived from biomass due to growing envi-
ronmental and sustainability concerns [1]. As a result, biopolymers have gained
widespread acceptance and have experienced significant growth in a variety of indus-
tries during the previous few decades [2]. Biopolymers are an important component
of bionanocomposites that have piqued the interest of researchers. They are an excel-
lent alternative for the matrix of bionanocomposites and provide numerous benefits
that have helped bionanocomposites gain widespread acceptance [3]. Biopolymers
are an excellent alternative to petroleum-based polymers, because they are renew-
able in nature and reduce carbon footprint and solve degradability difficulties because
they are mostly biodegradable in nature. Important biopolymers widely being used
are poly(lactic acid) (PLA), starch (ST), poly(butylene succinate) (PBS), poly(vinyl
alcohol) (PVOH), chitosan, etc. [4–10].
Researchers from different areas of science are investigating the use of nanotech-
nology for different material property improvements [11]. For this, nanostruc-
tures such as nanoclay, nanowhiskers, nanocrystals and nanofibres are being used.
Halloysite nanotubes (HNTs) are now the most widely used nanostructure in the
development of bionanocomposites [4]. This is due to the benefits provided by this
nanomaterial, which include its tubular structure, nano-scale lumen, high aspect ratio,
hydrophilic nature, low cost, abundant availability, ease of dispersion in polymer
matrix by applying shear force, environmental friendliness and cytocompatibility
P. Manju · P. Santhana Gopala Krishnan (B)
Department of Plastics Technology, Central Institute of Petrochemicals Engineering and
Technology: Institute of Petrochemicals Technology (IPT), Guindy, Chennai, Tamil Nadu 600032,
India
e-mail: psgkrishnan@hotmail.com
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_8
221
222 P. Manju and P. Santhana Gopala Krishnan
properties [12]. As a result, it improves the thermal, mechanical, flame and barrier
properties of bionanocomposites, culminating in the creation of a hybrid class of
bionanocomposites. The use of these materials has spread to a variety of fields,
including biomedical, tissue engineering scaffolds, drug delivery, cancer cell isola-
tion, bone implant, cosmetics, etc. [1]. Bionanocomposites are being studied in order
to find out a solution to the disadvantages of biopolymers such as weak mechanical
strength, limited thermal stability and poor barrier qualities, among others [13]. As
a result of the synergy between nanotechnology and renewable resources, a large
range of applications in various industries with better features emerged. Since poly-
mers made from renewable resources are more environmentally friendly, their use is
being increased nowadays. Preparation and characterization of bionanocomposites
using halloysite nanotubes (HNT), starch (ST) and poly(vinyl alcohol) (PVOH) are
discussed in this chapter.
8.2 Poly(Vinyl Alcohol)
PVOH is a biopolymer made by hydrolysis of polyvinyl acetate, which degrades
through microbial degradation and hydrolysis [8, 14]. The chemical and physical
properties of PVOH depend upon the initial length of vinyl acetate polymer and
the degree of hydrolysis. Properties of PVOH are given in Table 8.1. The repeating
unit of PVOH is given in Fig. 8.1. PVOH has good mechanical properties, oxygen
barrier properties and film forming ability. Limited biodegradability and high water
permeability are the disadvantages of PVOH [15].
PVOH is mainly classified into two: partially hydrolysed and fully hydrolysed
PVOH. Partially hydrolysed PVOH is mainly used in food applications. It is also
used in the synthesis of poly(vinyl butyral) and vinylon fibres [16]. Vinylon or
Vinalon is heat and chemical resistant fibre fabricated from PVOH and is used in
textiles, ropes and shoes. PVOH is also widely used in membranes, packaging, textile
industry, paper industry, adhesives, coatings and biomedical applications [17]. PVOH
Table 8.1 Properties of PVOH and ST
Property PVOH ST
Appearance Creamytowhitishpowder White powder
Density (g/cc) 1.19–1.31 1.5
Molecular weight (g/mol) 20,000–400,000 3.12–5.52 × 106
Glass transition temperature
(°C)
75–85 Varies according to moisture
content and source in the range
of 20–150
Melting temperature (°C) 180–190 for partially
hydrolysed and 230 for fully
hydrolysed
160–210
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube Bionanocomposite … 223
Fig. 8.1 Structure of PVOH
is biocompatible with human tissue and can absorb protein molecules and undergo
cell adhesion without any toxicity. The global producers of PVOH are DuPont,
Nippon synthetic chemical industry, Eastman chemical company, Sekisui chemical
company and Anhui Wanwei Group [17].
ST can be considered as the best material candidate to be blended with PVOH
because it is a completely biodegradable, cheap and widely abundant biopolymer [7,
15]. PVOH/ST blends have been investigated for decades in terms of blend ratio and
plasticizer content to achieve good material compatibility and properties [15].
8.3 Starch
ST is an important food resource, which belongs to the polysaccharide family, widely
present in leaves, stems, roots, tubers and fruits in the form of water-insoluble gran-
ules [18]. ST is the end product of photosynthesis which is the chemical storage of
energy. ST can be extracted from food products such as potato, wheat, rice, barley,
maize, banana and mango [19]. The dimensions of the ST granules vary according
to the source ranging from 0.5 to 175 μm.
ST is a semi-crystalline polymer consisting of 20–30% amylose and 70–80%
amylopectin (Fig. 8.2). The ratio of amylose and amylopectin varies according to
the difference in the plant resource. Amylose is a linear polymer, in which α-d-
glucose units linked by α-(1,4) glycosidic bond linkages, while the amylopectin is the
branched counterpart with α-(1–4) linked backbone and α-(1–6) linked branches [20].
The properties of ST are given in Table 8.1. ST completely biodegrades in soil and
compost, is non-toxic and has a low cost. The processability of ST is difficult because
of its inherent brittleness and less flexibility. Besides, the melting and degradation
temperatures of ST are very nearby which is very difficult during the processing of
ST. Therefore, gelatinized, plasticized and thermoplastic starch (TPS) is generally
used [7].
The important applications of ST include textiles, adhesives and paper binders,
textiles, chemical productions and fermentation. The major global producers of ST
are Cargill, Ingredion, Tate and Lyle, Archer Daniels Midland Company, Riddhi
Siddhi Gluco Biols and Gulshan Polyols [21].
224 P. Manju and P. Santhana Gopala Krishnan
Fig. 8.2 Chemical structure of ST, amylose and amylopectin
8.4 Halloysite
HNT is a clay mineral belonging to the kaolin group that was called after Baron
Omalius d’Halloy (1707–1789), a Belgian geologist who originally discovered
it [4, 5, 22]. HNT is a two-layered aluminosilicate with the chemical formula
Al2Si2O5(OH)4.nH2O, and it shares chemical similarities with other clays such as
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube Bionanocomposite … 225
kaolinite, dickite and nacrite [23]. However, the shape of crystals of unit layers sepa-
rated by a monolayer of water molecule differs primarily. It can be found in a variety
of worn rocks and soils. HNT is extracted from natural sources and is typically white
in colour, making it easy to grind into powder. The specific gravity of HNT is in
the range of 2–2.65, and the cation exchange capacity varies in the range between
2–60 meq/100 g. The surface area of HNT is about 184.9 m2/g. HNT is mined in
China, New Zealand, America, South Africa, Brazil and France, among other places
[12].
HNT comes in a variety of shapes and sizes, including spheroidal, short tubular
and platy particles. The hollow tubular structure, with a diameter of less than 100 nm,
is the most prevalent, in which the aluminosilicate sheets are rolled up like a scroll
(Fig. 8.3). The length of HNTs ranges from 0.2 to 1.2 μm, with inner and outer
diameters of 10–30 and 40–70 nm, respectively. The structural unit of HNT is made up
of two sheets: Si-tetrahedra and Al-octahedra arranged in a hexagonal pattern. Inner
aluminol (Al–OH) and outer siloxane (Si–O-Si) hydroxyl groups are located between
layers and on the surface of the nanotubes, respectively. These hydroxyl groups can
be used to attach various functional groups by surface modification techniques. The
interlayer space of the HNT mineral contains a layer of water, resulting in a layer
thickness of up to 1.1 nm. Since these water molecules are bound together by weak
interactions, they can be easily removed by drying HNT. This results in the production
of HNT in a range of 0.7–1.1 nm interlayer spacing. As a result, it is assumed that
hydrated HNT has a diameter of 1.1 nm and dehydrated HNT has a diameter of
0.7 nm. [12].
Fig. 8.3 Structure of HNT
226 P. Manju and P. Santhana Gopala Krishnan
8.5 PVOH/ST/HNT Bionanocomposite: Preparation
The most common methods employed for the preparation of PVOH/HNTs are solu-
tion casting technique, melt processing and electrospinning. As literatures discussing
the PVOH/ST/HNT are limited, the methods for preparing PVOH/HNT and ST/HNT
will also be discussed in this section.
8.5.1 Solution Casting
Solution casting is a suitable method to be performed on a laboratory scale. The
thermal degradation of polymers used for solution casting will be minimum because
of the absence of higher temperatures and shear in this method [15]. The polymer
is dissolved in a suitable organic solvent, and the solution is casted on mould plates
in different thicknesses to obtain the films. In the case of PVOH/ST/HNT films,
PVOH and ST shall be mixed in powder form at room temperature. This mixture
was dissolved in 200 mL deionized water at 35 °C which was then vigorously mixed
using a magnetic stirrer at 500 rpm and 85 °C for 3 h. Then, equal amounts of these
clear solutions were poured into casting moulds and dried at 50 °C for 24 h [15].
In addition, the PVOH/ST films shall be plasticized with 30 wt% glycerol (GLY) to
fabricate PVOH/ST/GLY films. The amount of ST and GLY was determined through
trial-and-error methods. For the preparation of PVOH/ST/GLY/HNT films, the HNT
suspension was prepared by mixing weighted amounts of HNT with 100 mL of deion-
ized water using a mechanical mixer at 500 rpm for 2 h at 50 °C, followed by sonica-
tion for 1 h in degas mode for preparing a dispersed and bubble-free HNT suspension.
This suspension was added drop by drop to 100 mL of PVOH/ST/GL solution at
50 °C by continuous mixing for 30 min using a mechanical stirrer. This solution was
further homogenized using a magnetic stirrer for 30 min proceeded by a final soni-
cation procedure to remove any bubbles. Then, the films were dried at 50 °C for 24 h
and stored in a desiccator [15]. A modified solution casting technique was performed
for developing a non-woven membrane comprising of chitosan/PVOH/HNT for air
filtration purposes. To begin, the chitosan/PVOH blend casting solution was prepared
by dissolving chitosan and PVOH in a 200 m mol adipic acid solution. Then, polymer
solutions were cast onto a glass plate to obtain films with several thickness. Finally,
100 mL of the HNT dispersion was vacuum filtered onto the polymer side of the
composite membranes to develop the hybrid non-woven membranes [24].
8.5.2 Electrospinning
Electrospinning is a technique to synthesize fibres, in which a high electric voltage
is applied to a continuous flux of polymer solution. The fibres thus formed will be in
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube Bionanocomposite … 227
micro/nanosize. A schematic representation of electrospinning is given in Fig. 8.4.
PVOH/HNT bionanocomposites are spun into fibres using this technique. Cheng
et al. prepared PVOH/HNT nanofibres by electrospinning technique with 10 wt%
PVOH solutions with a concentration of HNT being varied from 5 to 25 wt%. The
electrospinning device was maintained with a voltage of 15 kV and an injection rate
of 0.2 mL/min. The collector was a paper-wrapped rotating metal drum, and the
distance from the needle was maintained at 15–20 cm [14]. PVOH/HNT/chitosan
nanofibres were produced by electrospinning technique, in which the chitosan and
PVOH were mixed in a ratio of 30/70 with 3 and 5% of HNT [25].
Electrospinning of ST is difficult because of achieving ST in fibre form because
of its lower strength, water resistibility, thermal instability and poor processing
behaviour. Also, it has to be noted that electrospinning of ST is only possible from ST
having high amylose content [26]. But with the advent of electrospinning and modi-
fying the conventional electrospinning technique, researches for electrospinning of
ST have also commenced recently [27]. In addition, electrospinning of ST with other
biopolymers such as PVOH, PLA and polycaprolactone was widely accepted so that
the disadvantages of both the biopolymers can be overcome to develop a hybrid
system [28–30]. Solution of 7 wt% PVOH in water was formed, and ST ranging
from 1 to 5 wt% was added to this. This solution was electrospun in an electro-
spinning device maintained in a specific voltage [31]. Bubble electrospinning is a
recent technique developed to produce fibres from aqueous solutions. Liu and He
produced nanofibres from PVOH/ST blends using this method [29]. If a polymer
Fig. 8.4 Representation of
electrospinning
228 P. Manju and P. Santhana Gopala Krishnan
bubble ruptures under an electrostatic force, the surface tension leads to surface
minimization of film fragments along with the formation of some daughter bubbles.
If the electrostatic force ejects some fragments upwards, the process can be called
as bubble electrospinning. If a stream of blowing air is used instead of electrostatic
force to pull up the polymer bubble, the process is termed as blown bubble spinning
[29].
8.5.3 Melt Processing
Melt processing is a technique that specializes in large-scale manufacturing with
more productivity and efficiency. Even though solution casting seems to be the
easy processing technique for ST/HNT bionanocomposites, this is not practical
in polymer processing industries. Studies about melt processing of plasticized
ST/HNT bionanocomposites have commenced recently only. Generally, ST/HNT
bionanocomposites are being fabricated by following two steps. ST and plasticizer
such as GLY and HNT were blended in mechanical stirrer for 3 h at room temperature,
followed by processing in a twin-screw extruder at a screw speed of 60–150 rpm with
temperature from hopper to die which was set as 110, 115 and 120 °C [32–34]. Melt
processing of ST/PVOH was also reported by different researchers. ST, PVOH and
plasticizers were mixed in a high-speed mixer at room temperature for 3 min. After
conditioning for 12 h, the mixture was charged into a torque rheometer and mixed
further at 105 °C, for 10 min and 80 rpm. These mixtures were then compression
moulded to obtain the ST/PVOH films [35]. Further, they extended their research to
synthesize ST/PVOH/MMT films by a similar processing method [36].
8.6 PVOH/ST/HNT Bionanocomposite: Characterization
8.6.1 Chemical Interaction Analysis
The chemical interactions present between HNT and ST or PVOH matrix are iden-
tified using Fourier transform infrared (FT-IR) analysis. FT-IR analysis also helps
in identifying the characteristic peaks of ST, PVOH and HNT. Thus, any changes in
characteristic peak values of ST or PVOH or HNT can be concluded as the interac-
tions between them. This might be evident by the red shift or blue shift phenomenon
of the peaks [33]. As reported by Schmitt et al., the peak corresponding to the internal
and external hydroxyl groups of HNT was shifted to lower wavenumbers in ST/HNT
bionanocomposites which was due to the formation of interactions between OH
groups of HNT and C-O-C groups of ST [33]. Similar findings were reported by Ren
et al. for potato ST/HNT bionanocomposites [34].
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube Bionanocomposite … 229
8.6.2 XRD Analysis
From the XRD pattern of the bionanocomposites, the incorporation of HNT can be
confirmed by the presence of characteristic peaks of HNT. The intensity of the peaks
was found to increase with HNT concentration. The presence of the characteristic
peaks of both ST/PVOH and HNT confirms its dispersion of HNT in the polymer
matrix. The appearance of any new peaks may pave light for the evidence of inter-
action t hat occurred between ST/PVOH with HNT [34]. XRD analysis also helps
in studying the changes in the microstructure of ST/PVOH by the addition of HNT
[33]. The addition of HNT has been reported to change the crystalline structure of
HNT as reported by Schmitt et al. Incorporation of 2 wt% HNT was found to induce
the formation of B-type structure of ST by reducing the formation of VH-type struc-
tures. In the B-type structure, the double helices of amylopectin are packed in the
hexagonal unit cell with 36 water molecules per unit cell, whereas in VH type, the
single helices of amylopectin are packed in the orthorhombic unit cell with 16 water
molecules per unit cell. Moreover, the VH-type crystals are formed by the addition
of any complexing agent to amylose [33]. Upon addition of 0.25 and 0.5 wt% of
HNT into PVOH, shifts in the characteristic peaks of PVOH were observed in the
XRD pattern of PVOH/HNT bionanocomposites. These shifts can be considered
as slight intercalation of PVOH into HNT as reported by Abdullah et al. [15]. In
contrast, Cheng et al. reported that there were no changes for the characteristic peaks
of PVOH by the addition of higher concentrations of HNT in the range 5–25 wt%
[14].
8.6.3 Morphological Analysis
For the morphological analysis, the specimens will be mounted on the stub using
double side tape and coated with a thin layer of gold/platinum. The images will
be collected at the specified operating voltage and magnification. In the processing
of ST, a plasticizer is an inevitable component, and hence, the percentage of plas-
ticizer that has to be added shall be optimized during the fabrication of ST/HNT
bionancomposites. This is because plasticizer in a higher percentage might affect the
dispersion of HNT and hence the properties also. Similarly, the dispersion of HNT in
ST/PVOH matrix is an inevitable factor in determining the mechanical and thermal
properties of the bionanocomposites. As a result, characterization of bionanocom-
posites through microscopic techniques such as scanning and transmission electron
microscopy (SEM and TEM) and atomic force microscopy (AFM) has importance in
modifying the properties by examining the dispersion of HNT [33]. A figure showing
the agglomeration of HNT as obtained from TEM analysis is given (Fig. 8.5). A
typical AFM image for PVOH/ST/GLY/HNT is comprised of three major areas, in
which the black area corresponds to the amorphous phase of the bionanocomposite,
230 P. Manju and P. Santhana Gopala Krishnan
Fig. 8.5 Agglomeration of
HNT as evident from TEM
analysis (micrograph from
authors collection)
light and dark brown area corresponds to the crystalline phase, and light and yellow
areas correspond to the fully and partially embedded HNT in the matrix [37].
8.6.4 Mechanical Properties
The mechanical reinforcement performance of nanoparticles on bionanocomposites
depends on the effective load transfer from the matrix to the nanoparticles. This
will be more effective when there are strong interactions at the nanofiller matrix
interface and if the nanofillers are dispersed uniformly in the matrix. The three main
interactions between matrix and fillers are micromechanical interlocking, chemical
bonding and van der Waals force [14]. The HNTs are held together in bundles with van
der Waals force. Hence, it is vital to disperse nanotubes well in the polymer matrix to
achieve improved mechanical properties for the composites. Thus, the applied force
can be shifted to HNTs, bringing the improvement of mechanical properties [14].
Tensile strength, Young’s modulus and elongation-at-break shall be determined
employing Universal Testing Machine (UTM) [34]. The incorporation of 7 wt%
HNT in ST matrix has increased the tensile strength of bionanocomposites by 47%
as reported by Ren et al. A figure representing the mechanical properties of ST/HNT
bionanocomposites as observed by Ren et al. is given in Fig. 8.6 [34]. They also
reported that, besides the presence of HNT, the selection of plasticizers can affect the
mechanical properties of the bionanocomposites. The use of a mixture of plasticizers
was found to be a promising way to optimize the mechanical properties of these ST-
based bionanocomposites. Bionanocomposites which used a mixture of plasticizer
such as GLY and sorbitol have better mechanical properties such as tensile strength,
Young’s modulus and elongation-at-break than all the other bionanocomposites [34].
HNT can enhance storage modulus and Young’s modulus by maintaining ductility
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube Bionanocomposite … 231
also. Generally, for all ST bionanocomposites, a reinforcement effect is observed
by the addition of HNT along with an increase in modulus. This is because of the
effect of HNT which has a high elastic modulus of about 140 GPa [38, 39]. The
segmented motion of the ST chains helps in enhancing the storage modulus of the
bionanocomposite with an increase in HNT. Young’s modulus was increased by 84%
by the addition of 4 wt% HNT [33]. By the addition of modified HNT, the tensile
strength of ST/HNT bionanocomposites was increased by up to 144% and Young’s
modulus was improved up to 29% without compromising ductility [33]. The tensile
strength of PVOH/ST/HNT was found to be improved by 20 and 3.4%, respectively,
with the incorporation of 0.25 and 0.5 wt% HNTs. Young’s modulus was enhanced
by 148% with the addition of 1 wt% of HNT. However, strength was decreased
beyond the HNT loading of 0.5 wt% due to agglomeration of HNT as evidenced by
SEM analysis [15].
Zhou et al. reported that PVOH-HNT films have higher tensile strength and
elongation-at-break values than PVOH films. Tensile strength and elongation-at-
break values for films containing 5% HNT were 56 MPa and 320%, respectively,
Fig. 8.6 Mechanical properties of ST/HNT bionanocomposites
232 P. Manju and P. Santhana Gopala Krishnan
which were higher than those for neat PVOH films. However, as the HNT concen-
tration is increased beyond 7%, the mechanical characteristics are shown to decline,
which could be due to HNT particle agglomeration [40].
8.6.5 Thermal Analysis
The incorporation of nanofillers in the polymer matrix induces two main effects on
the thermal stability of the bionanocomposites.
(i) a barrier effect that improves the thermal stability.
(ii) a promoter effect which increases the thermal degradation process [34].
The barrier effect of nanofiller increases the thermal stability of polymer matrix
by the fine dispersion of nanofiller in the polymer matrix and through the strong
interactions developed between nanofiller and polymer matrix. The better dispersion
of nanofiller increases the pathways for the escape of combustion gases developed
and the formation of char residue at the surface of the matrix [41]. The presence of
many hydroxyl groups on the edges of nanofillers catalyses the degradation of the
polymer through which the nanofiller acts as a promoter for polymer degradation
[42, 43]. But the barrier effect will be predominant when the nanofillers are well
dispersed in the matrix [43]. Thus, the thermal stability will be increased [15].
The primary stage of degradation of PVOH and PVOH/HNT bionanocompos-
ites was reported to be in the range of 280–300 °C, due to the elimination of water
molecules. During this stage, the acetate groups remaining in the PVOH, due to
incomplete hydrolysis of PVOH, will form polyenes. During this stage, degradation
of bionanocomposites will be higher than that of neat PVOH, because of the plas-
ticization effect of HNT on PVOH chains, and the degradation will be accelerated.
During the second stage of degradation in the range, 350–460 °C, chain scission
occurs. But during this stage, the thermal stability of bionanocomposites will be
higher than that of PVOH because of the barrier effect of HNT in the PVOH matrix.
The residue yield, which is formed by the degradation of polyenes formed during
the primary stage, will also be higher for bionanocomposites, and these residues
will provide enhanced thermal stability [44]. For ST/HNT bionanocomposites, the
degradation occurs in three stages [7]. The primary stage below 100 °C corresponds
to the evaporation of water and the plasticizer used. The second and third stage
(100–400 °C) corresponds to the degradation of amylose and amylopectin chains.
By the addition of HNT, the degradation temperatures were shifted to higher values
for the second stage. The values were higher for bionanocomposites having a higher
concentration of HNT [33, 34].
The addition of HNT improves the thermal stability of ST and PVOH [33, 34]. This
is because of the high thermal stability of HNT and the interactions between HNT
and ST and PVOH. The incorporation of 7 wt% HNT has led to the enhancement
of maximum degradation temperature for ST/HNT bionanocomposites which was
due to the good dispersion of HNT [33]. As reported by Abdullah et al., the addition
8 Biodegradable Polyvinyl Alcohol/Starch/Halloysite Nanotube Bionanocomposite … 233
of HNTs increased the thermal stability of PVOH/ST/GLY/HNT bionanocompos-
ites which was evident from the increase in decomposition temperature and reduced
weight loss. The decomposition temperature at 5% weight loss was increased to
468 °C from 460 °C by the addition of 1 wt% of HNT. A similar trend was observed
for T50 and T90, where the HNT loading was increased from 0.25 to 1 wt% [15].
Because of the hydrogen bonding in between hydroxyl groups of PVOH, interchain
and intrachain interactions occur between polymer chains of PVOH. Thus, the addi-
tion of HNT will interrupt the intermolecular and intramolecular interactions between
the polymer chains and changes the physical structure and crystallization behaviour
of PVOH. With the increase in the concentration of HNT, Tc of PVOH also shifts to
higher temperatures [45]. The Tc of poly(lactic acid)-HNT bionanocomposites was
also found to increase with respect to increase in concentration of HNT [5]. The Tg
of PVOH was found to increase by 5.72 °C from 74.83 to 80.55 °C by incorporation
of 25 wt% of HNT as reported by Cheng et al. Similarly, Tm was increased from 221
to 226 °C by the incorporation of 25 wt% of HNT [14].
8.6.6 Water Absorption Capacity
PVOH and ST have higher sensitivity towards water always. Studies have reported
that the incorporation of HNT can reduce the water absorption of PVOH and ST. This
was explained based on the structure of HNT which inhibits the diffusion of water
molecules in PVOH/ST and thereby decreases the water absorption capacity [15].
The water vapour transmission rate of PVOH/ST/GLY/HNT films was reduced by
52.34% with increasing the HNT content from 0 to 5 wt%. The decrease in value was
less pronounced when the HNT content increased from 1 to 5 wt% resulting from
the agglomeration of HNT at the high concentrations [37]. The moisture absorption
capacity of ST was increased with the addition of HNT, and with further increase in
the HNT, the moisture absorption capacity was found to decrease which might be
due to the agglomeration of HNT [46].
8.7 Conclusions
ST is an important promising biopolymer of the polysaccharide family. Similarly,
PVOH also is a significant biopolymer with many advantages. Naturally, occurring
HNT shall be incorporated into ST or PVOH or ST/PVOH. The different prepa-
ration methods and characterization techniques of the nanocomposites were anal-
ysed in detail. The effect of HNT on the mechanical and thermal properties of
different systems was also investigated. Moreover, investigations on ST/PVOH/HNT
bionanocomposites are yet to be explored to widen its applications in different fields.
234 P. Manju and P. Santhana Gopala Krishnan
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Chapter 9
Environmentally Friendly
Bionanocomposites in Food Industry
Subajiny Sivakanthan and Podduwala Hewage Sathiska Kaumadi
9.1 Introduction
Petroleum-based (fossil fuel-based) materials found versatile applications in human
life. However, there are rising concerns over the use of petroleum-based products
such as their adverse effects on the environment and human and animal health.
In recent years, there is a mounting interest in developing bio-based materials as
alternative sources for petroleum-based (fossil fuel-based) chemicals to protect the
environment as well as the well-being of humans and animals. However, biopolymers
in industrial applications have some drawbacks primarily due to their hydrophilicity
and poor barrier properties [1]. The use of composite materials, engineered materials
made from two or more constituent materials with significantly different physical
or chemical properties from their constituent molecules [2], is widely practiced in
various applications.
Nowadays, bionanocomposites are gaining popularity in various industrial
applications. Bionanocomposites are materials consisting of natural or synthetic
biodegradable polymers of biological origin and nanomaterials (1–100 nm). In
these materials, the biopolymer matrix makes up the continuous phase, and the
nanomaterials (organic and/or inorganic materials) are the dispersed phase [1, 3].
Composite materials exhibit robust physical, chemical, and mechanical prop-
erties compared to their constituent materials. However, conventional composite
materials, which do not have nanomaterials, differ from nanocomposites in their
S. Sivakanthan (B)
Department of Agricultural Chemistry, Faculty of Agriculture, University of Jaffna, Jaffna, Sri
Lanka
e-mail: ssubajiny@univ.jfn.ac.lk
P. H. S. Kaumadi
Department of Biosystems Technology, Faculty of Technology, University of Jaffna, Jaffna, Sri
Lanka
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023
Visakh P. M. Biodegradable and Environmental Applications
of Bionanocomposites, Advanced Structured Materials 177,
https://doi.org/10.1007/978-3-031-13343-5_9
237
238 S. Sivakanthan and P. H. S. Kaumadi
mechanical properties due to the high surface to volume. Consequently, many vari-
eties of nanocomposites have been developed using different polymer matrices and
nanofillers. Bionanocomposites are found to be promising candidates in many appli-
cations, including the food industry, biomedicine, tissue engineering, paint, pack-
aging, coating, solar energy, etc. [2–4]. This chapter aims to give an insight into the
applications of bionanocomposites in food industries.
9.2 Environmentally Friendly Bionanocomposites
Growing concern about environmental pollution due to the high impact of plastic
waste has led industries and academic researchers to develop sustainable and green
polymers extracted from natural resources. Due to the deleterious consequences of
plastic pollution, biodegradable polymers started to receive an enormous level of
attention concerning non-degradable polymers based on petroleum sources [5].
Synthetic polymers are used widely by humans in their day-to-day lives in s ectors
such as agriculture, construction, food industry, and biomedicine. Factors such as
low cost, convenience, good performance, durability, superior mechanical, and other
properties make these petrochemical-based plastics popular in commercial and indus-
trial markets [6]. Due to the inability of these plastics to degrade naturally, issues have
arisen with the accumulation of plastic as waste [7]. These fossil-based sources are
finite in quantity and will reach an endpoint due to the higher consumption. Because
of this, these polymers cannot be regenerated fast enough when compared to the rate
of consumption [8].
Nowadays, the development of environmentally sound “green” materials has
become a growing trend globally to reduce plastic waste accumulation as a conse-
quence of the issues caused by non-degradable plastics. Biodegradable polymers
such as cellulose, starch, poly(lactic acid) (PLA), and polycaprolactone have
gained great attention as raw materials for making environmentally friendly plas-
tics. Factors including abundance, low cost, biodegradability, and renewability of
these biopolymers make them suitable to replace non-biodegradable plastics [9-
10]. Biodegradable polymers have the ability to undergo at least one step of the
degradation process through the metabolism of naturally occurring organisms, mois-
ture, oxygen availability, and temperature without leaving any harmful residues to
the environment. Categories of biopolymers consist of (a) natural polymers; plant
carbohydrates including starch, cellulose, chitosan, agar, etc., and animal or plant
proteins such as soy protein, corn zein, gluten, collagen, whey protein, casein,
(b) biodegradable synthetic polymers; poly(lactic acid) (PLA), poly(glycolic) acid
(PGA), poly(caprolactone) (PCL), etc., (c) microbial polymers derived via micro-
bial fermentation such as microbial polyesters including poly (hydroxy alkanoates)
(PHA) and microbial polysaccharides such as pullulan and curdlan. Though biopoly-
mers are posing the ability to replace non-degradable plastics, their poor mechanical
and barrier properties such as low heat distortion, brittleness, high gas and vapor
permeability, and poor resistance to protracted processing have caused limitations in
9 Environmentally Friendly Bionanocomposites in Food Industry 239
the applications [11]. To overcome these shortcomings, biocomposites are considered
promising candidates.
Materials that consist of two or more constituents with different physical and
chemical properties are recognized as composites. If materials with various properties
are combined creating a matrix consisting of enhanced traits than the separated
component individually, it falls into the frame of a composite. Composites are a
combination of two constituents: matrix and reinforcement. The continuous phase is
called a matrix which generally includes a polymer, metal, or ceramic, etc. The matrix
plays a role in maintaining fibers in the proper direction/arrangement in space and
protects them from abrasion or environment. Enhancement of physical or mechanical
properties of the matrix gets done by using reinforcement materials. Composites are
better in strength, electrical, biological, thermal, and environmental applications [12].
There are three main categories of composite: (1) laminated composites, (2) fibrous
composites, and (3) particulate composites. Fillers used in polymer matrix help in
the reduction of costs, decrease shrinkage of the matrix, lower the coefficient of
linear expansion, increase thermal conductivity, and lower resistivity. Filler’s shape,
size, and orientation in the polymer matrix play a role in improving the mechanical
properties of the matrix.
Composites with at least one phase in the dimensions of nanometers (about 1–
100 nm in length) get categorized as nanocomposites. Nanotechnology used in these
composites influences the characterization, preparation, and structure of the materials
[13]. Based on matrix materials, nanocomposites can be classified into three classes:
(1) nanocomposites of a polymer matrix, (2) nanocomposites with a metal matrix,
and (3) nanocomposites with a ceramic matrix. Nanocomposites get occupied for
improving the mechanical, optical, and barrier properties of the composites. Large
surface-to-volume ratio and surface activity of nano-sized materials are some of the
factors that contribute to the enhancement of properties of the polymer nanocom-
posites [13]. These nanocomposites are inexpensive, light in weight, exhibit sound
processability, transparent with enhanced barrier attributes to water/gasses, etc. The
demerits of these matrices include increasing viscosity, difficulties in dispersion,
increasing sedimentation rates, converting into black if different carbon-containing
nanoparticles get employed, etc. Fabrication of nanocomposites is a challenge
with both pre-polymerization and post-polymerization methods. Direct release of
nanoparticles into the aquatic resources during industrial discharge and indirectly
through surface runoff to the soil is common. Via many chemical–physical proces-
sors, the transformation of nanoparticles takes place in the environment. Many organ-
isms (both aquatic and terrestrial organisms) ingest these nanoparticles. Mentioned
downsides of the nanocomposites triggered the formation of bionanocomposites [12].
Materials comprise particles with at least one dimension that falls between 1 and
100 nm, and a constituent of the biological origin or biopolymers gets defined as
bionanocomposites [1]. Generally, composites consist of two or more components
that exhibit different properties both physically and chemically after combining
that when they were individual components. In the case of bionanocomposites,
they are made up of biopolymers and inorganic solids such as metal oxides that
lie in the nanometer range with novel and multifunctional properties including
240 S. Sivakanthan and P. H. S. Kaumadi
biodegradability, biocompatibility, and antimicrobial activity [14]. Nanofillers such
as nanoclay, zinc oxide, and titanium dioxide have a large surface-to-volume ratio that
improves the polymer matrix–filler interaction to enhance the overall performance
of the material including thermal and barrier properties [1]. When compared with
neat polymer matrixes and early composites, bionanocomposites exhibit enhanced
mechanical and barrier properties, where they withstand thermal, storage, and
transportation stresses [15].
Based on the matrix type, the origin, shape, and size of the reinforcement
bionanocomposites can be classified. Based on the shape of the particle reinforce-
ment, these can be classified into particulate, elongate, and layered.
Elongated particle bionanocomposites
Elongated particles such as carbon nanotubes and cellulose nanofibrils are utilized to
reinforce this type of bionanocomposites and exhibit superior mechanical properties
than other composites [12]. A higher aspect ratio of the reinforcement is caused by
the enhancements of the properties of elongated particle bionanocomposites [15].
Particulate bionanocomposites
Isodimensional particles are commonly used in reinforcement. Due to the low aspect
ratio and the reinforcing effect being moderate, it aids in enhancing the resistance to
flammability and reduces the permeability and the cost of the composites.
Bionanocomposites reinforced with layered particles
Layer polymer nanocomposite can be classified into three subclasses based on
the dispersion of particles in the matrix. When there is no partition between the
layers of the matrix due to the particle–particle interaction, flocculated/phase-
separated nanocomposites are generated. Since individual laminas are not sepa-
rated, these composites are called microcomposites [14]. Intercalated nanocompos-
ites are obtained when polymer chains are intercalated between sheets of the layered
nanoparticles. When there are partitions in between individual layers, exfoliated
nanocomposites are produced [12].
9.2.1 Properties and Applications of Bionanocomposites
Properties of bionanocomposites such as mechanical properties, biocompatibility,
biodegradability, and antimicrobial activities are highly dependent on their high
surface area, morphology, and shape. Parameters such as the process used in
bionanocomposite fabrication, type of fillers and their orientation, type of adhe-
sion at the matrix interface, degree of mixing of two phases, nanoparticle char-
acteristics, the volume fraction of nanoparticles, size and shape of nanofillers,
name of the interphase developed at the matrix interface, and the morphology
of the system affect the nature of the properties of the bionanocomposites [14].
Bionanocomposites exhibit improvements in modulus, solvent or gas resistance, and
9 Environmentally Friendly Bionanocomposites in Food Industry 241
dimensional stability than the neat polymers. These composites also offer bene-
fits such as transparency, low density, better surface properties, and recyclability.
Nanoparticles use in bionanocomposites help in achieving uniform dispersion of
the particles in the biopolymer matrix leading to an ultra-large interfacial area
between the constituents. A large organic or inorganic interface alters the relax-
ation behavior, molecular mobility, and consequent thermal and mechanical prop-
erties of bionanocomposite materials [16]. Effective dispersion of nanoparticles in
the bionanocomposites enhances the performance of the material. Various factors
such as choice of solvent, size of nanoparticles, and type of mixing govern the
uniformity of distribution of nanoparticles in the biopolymer matrix. Techniques
including plasma modification, chemical modification, grafting, or coasting with
bio-moieties are used in surface modification of the nanofillers to enhance their
dispersion in the matrix. Biocompatibility and hydrophobicity/hydrophilicity of the
bionanocomposites can be also improved by using surface modification techniques.
Criteria including controlled crystallinity of nanoparticles and fixing their size and
shape are also important when it comes to the development of high-performance
bionanocomposites [3].
Bionanocomposites exhibit various applications in sectors such as automo-
tive, electrics, pharmacy, paper/packaging, and biomedicals [17]. Bionanocom-
posites developed employing biopolymers such as PLA, poly-(butylene succinate)
(PBS), and polyhydroxybutyrate (PHB) are optically transparent; therefore, they are
commonly utilized in the food industry. Due to the factors such as less expense,
less pollution, and antimicrobial activities, bionanocomposite films are used in the
production of food packaging [14]. For the development of durable load bearings,
automotive parts, and car building blocks, cellulose nanofibers are utilized in automo-
bile industries [18]. Nanocellulose-based biocomposites also are used in water treat-
ment industries to remove contaminants such as fluorides and chlorophenols [19].
Bionanocomposites are used in the biomedical industry such as drug release systems,
wound dressings, vaccination, and bioengineering due to their biocompatibility and
non-toxic properties. Electrical, magnetic, and optical properties of bionanocom-
posites make them include in the diodes, displays, solar cells, sensing and medical
devices, etc. [14]. When considering the various properties of bionanocomposites,
the present chapter focuses on the application of these materials in the food industry.
9.3 Bionanocomposites in the Food Industry
In the industry of food, for the applications such as food packaging, chemically
synthesized polymeric materials are employed widely [20]. Simplicity, lower produc-
tion cost, higher durability, and the flexibility of these synthetic plastic materials
manage to gather special attention toward becoming the most utilized packaging
material. However, non-biodegradability has become the major drawback of these
synthetic polymers.
242 S. Sivakanthan and P. H. S. Kaumadi
Environmental concerns about non-degradable plastic have raised interest toward
biodegradable alternatives in the food industry [21]. In food industries, to extend
the shelf life and to enhance the quality of the food, the packaging is occupied [11].
More than 40% of plastics get employed as packaging, including food packaging
such as films, sheets, bottles, cups, tubs, and trays. The environmental impact of
long-lasting plastic packaging waste is becoming an alarming concern among the
public due to the limitations of their waste disposal methods. After plastic packages
complete their usage life, it is desirable if they possess the ability to get degraded
under natural conditions [22].
Exploration of bio-based and or biodegradable materials from renewable sources
would be a sound solution i n the substation of synthetic plastic materials t o reduce
the growing waste problems. Biodegradable packaging materials developed from
renewable biological resources exhibit excellent qualities including biodegradability
at the end of their life. Bioplastic materials consider being one of the most poten-
tial eco-friendly substitutes for non-degradable, non-renewable plastic packaging
materials [23].
Nevertheless, as conventional packaging, biopolymer-based packaging must
provide various functions such as containment and protection of food to maintain its
sensory quality and safety and provide information about the food to the consumer
[24]. So far, the utilization of biodegradable plastics in the food packaging sector
is minimum due to several factors, such as poor barrier properties and mechanical
properties. Before the commercial use of biodegradable primary packaging materials,
factors including degradation rate under various conditions, changes that occur during
the storage, the potential for microbial growth, and the release of harmful compounds
to the food products must be concerned. In real applications, high hydrophilic prop-
erties with poor processability of biopolymer-based packaging materials generate
severe limitations for their usage at the industrial level. Biopolymers frequently get
blended with synthetic or less frequently get chemically modified to eliminate the
mentioned problems.
Recently, hybrid of organic/inorganic systems, particularly material with layered
silicate dispersed at a nanometric level in a polymeric matrix, has gathered greater
attention. Nanocomposite incorporated with biopolymers exhibits enhanced prop-
erties such as good mechanical properties, oxidation stability, decreased solvent
uptake, and biodegradability compared to the neat polymers. The application of
bionanocomposites in the packaging sector expands the use of biodegradable poly-
mers which helps in the reduction of waste products associated with food industries
[16]. Compared to the base polymer class, bionanocomposites are exhibiting much
improved properties due to the high aspect ratio and high surface area of nanopar-
ticles incorporated. Thus, these advances provide a base for the development of
bionanocomposites as packaging material posing improved properties [25].
The utilization of biopolymers in food packaging applications poses both positive
and negative outcomes. The ability to get degraded under natural conditions, degrada-
tion without the release of toxic substances, minimum alteration of food components,
ability to incorporate active components, and ability to develop as edible packages
are some of the benefits of biopolymers in food packaging. The limitations of these
9 Environmentally Friendly Bionanocomposites in Food Industry 243
biopolymers in food packaging are poor barrier properties, low tensile strength,
brittleness, low thermal properties, higher gas/water permeability, etc.
The incorporation of nanomaterials into polymer matrixes is a novel technique in
food packaging. Bionanocomposites are used to extend the shelf life of fresh products
such as fruits and vegetables by controlling the respiration of the products. The quality
of meat, poultry, and seafood products in fresh or frozen states can be enhanced due
to the retardation of moisture loss, reduced lipid oxidation, etc., using the packages
developed with bionanocomposites. Several benefits of bionanocomposites in food
packaging are included below [26].
•Biodegrade under natural conditions.
•Can be developed as edible packages.
•Help in enhancing the shelf life of the food products.
•Improve quality and the properties of food.
•Enhance properties of barrier including oxygen and moisture.
•Protection against lipid rancidity.
•Facilitate incorporation of an active agent such as antioxidant and antimicrobials.
•Facilitate controlled release of active agents.
•Can be used in multilayer food packages together with nonedible films.
•Facilitate the use of biosensors and nanochips for food quality checking.
•Low in cost and effective in waste utilization.
9.4 Properties of a Bionanocomposite that Make It Suitable
as a Food Packaging Material
9.4.1 Mechanical Properties
Packages are prone to various types of stresses during their usage. Hence, char-
acterization of mechanical properties of bionanocomposites which get occupied in
the development of food packaging is necessary [27]. Tensile strength (TS), elastic
modulus (E), and elongation at break (
1
) are the main mechanical properties in the
usage of food packaging applications [28]. The capability of the material to resist
stress before its ruptures is called TS. The TS of these materials affects the physical
integrity and barrier properties. Fracture strain or
1
is the ability of a material to
stretch before breaking. This helps to determine the extensibility or the flexibility of
the packaging materials [29].
Starch and PLA are the widely used materials in food packaging due to their
desired properties and availability and production at an industrial scale. PLA exhibits
an acceptable level of mechanical properties for the incorporation in the production
of packaging materials. Biodegradable polymers including starch, whey protein,
soy protein, and chitosan do not exhibit improved mechanical properties up to an
acceptable level for packaging material development. As a result, the incorporation
244 S. Sivakanthan and P. H. S. Kaumadi
of different compositions of nanoparticles into biodegradable films has been initi-
ated. The mechanical properties of bionanocomposites are highly dependent on the
biopolymer type, nanoparticle type, and nanoparticle content.
Different reinforcement effects of nanoparticles in bionanocomposites can be
achieved based on the nanoparticle dispersion state, surface area, polydispersity,
and organo-modification, etc., which would lead to their grafting to the matrix of
polymer to expand the mechanical properties [30]. Characteristics of bionanocom-
posites such as Young’s (E) and shear (G) moduli, thermal expansion coefficient
(α), and electrical conductivity (σ ) can be influenced by the effects of the above-
mentioned factors. The affinity between biopolymers and nanoparticles is the key
factor for the homogeneous distribution of nanofillers in the polymer matrix. TS of
bionanocomposites gets increased at lower nanofiller contents, where biopolymer
length gets increased with increasing nanofiller content. This is highly dependent on
the type and the content of the nanofiller used. Some studies state that aggregated
nanofiller facilitates the movement of polymer chains as ball bearings [31]. Soft
polymer matrices adjacent to stiffer filler become mechanically more constrained.
Furthermore, effects of greater reinforcement can be achieved using fillers with higher
specific surface area resulting in enhanced mechanical properties of the materials.
The molecular weight of polymer matrices also bears an impact on the reinforcement
and the mechanical properties such as TS of the bionanocomposites [32]. Changes in
mechanical properties of various bionanocomposites of various studies are discussed
below.
According to the study of Arrieta et al. [33], PLA reinforcement with nano-TiO2
(nano-titanium dioxide) (1–5%) showed improved TS and
1
by 80%. PLA which
is reinforced with cellulose nanofibers (5%) exhibited no observable difference in
TS, decreased
1
by 36%, and E increased by 40% [33]. As stated in the study of
Hassannia-Kolaee et al., biopolymer of whey protein–pullulan reinforced with nano-
SiO2 (nano-silicon dioxide) (1–5%) improved the TS of the material by 70% and
1
decreased by 32%. MMT (Montmorillonite) (1–5%) reinforced whey protein–
pullulan biopolymer matrix exhibited increased TS up to threefold and decreased
1
up to 4.5-fold [34]. Chitosan reinforced with cellulose (5–40%) exhibited reduced
1
of high molecular weight chitosan up to threefold,
1
of low molecular weight
chitosan reduced up to 12-fold, in high molecular weight chitosan, TS increased up
to 75%, in low molecular weight chitosan, TS increased up to 60%, and E of high
molecular weight chitosan and low molecular weight chitosan increased up to 40 and
75%, respectively [35]. Kefiran reinforced with nano-ZnO (nano-zinc oxide) (1–3%)
exhibited increased TS up to 100% and increased elongation at break up to 12-fold.
Kefiran which is reinforced with nano-TiO2 (1–5%) improved elongation at break up
to fourfold, reduced TS by around 45%, and reduced E by 50% [36-37]. Starch–PVA
biopolymer matrix reinforced with nano-SiO2 (0.05–0.5%) caused an improvement
of TS of the matrix up to 70% and reduced the
1
up to 60%. Starch–PVA matrix with
MMT (1–5%) improved the TS and E by 80% and fourfold, respectively [38].
9 Environmentally Friendly Bionanocomposites in Food Industry 245
9.4.2 Barrier Properties
In general, food is kept in a package after production before consumption to serve a
number of functions. Packaging provides protection to the product to eliminate the
harm that might occur due to the factors dirt, light, oxygen, microorganisms, moisture,
etc. The packaging materials must be safe, inert, cheap, light, and easy to dispose of.
Good packaging material must have the ability to withstand stress during the process
and be resistant to stress during storage. The presence of oxygen inside packaged food
is one of the major causes of food deterioration. The reactions coupled with oxygen,
including nutrient loss, rancidity, color change, aerobic microbial growth, effects on
respiration rates, and production of ethylene, are some of the many causes of the
deterioration of packaged food. Therefore, the permeability of packaging materials
to gases and other small molecules is one of the major factors that must be considered
in the case of barrier properties [34].
Determination of the permeability of polymeric materials, including bionanocom-
posites, can be done by using the adsorption rate of gas molecules hooked on the
matrix at the atmosphere-polymer boundary and the diffusion rate of adsorbed gas
molecules through the matrix. The rate of formation of free volume holes in the
polymer by the random or thermal motion of polymer chains is the dependent factor
of the absorption rate. Diffusion occurs due to the hurdles of gas molecules to adjacent
voids (empty holes). Therefore, the penetrability of polymeric materials is reliant on
allowed hole size, grade of polymer motion, exact polymer–polymer, and polymer–
gas interaction. These mentioned factors are highly reliant on the intrinsic polymer
chemistry and external properties such as structural features, the polarization of the
polymeric chains, hydrogen bonding structures, additional intermolecular connec-
tions, polydispersity, molecular weight, grade of cross-linking, crystallinity, temper-
ature, and pressure. The overall gas diffusion is also directly dependent on the film’s
thickness [31].
No polymer displays the necessary barrier and mechanical properties to all pack-
aging submissions. Therefore, polymer mixtures or compound multilayer schemes
are broadly occupied. As an instance, material such as ethylene vinyl alcohol
(EVOH), which is highly subtle toward water yet blockade to oxygen gets sand-
wiched with bilayers of the hydrophobic polymer as polyethylene (PE) to provide
a higher barricade to oxygen in a very moist situation. Polymer direct blending can
also be used in enhancing blockade properties that do not get gained through single
layers of polymers. Nonetheless, polymer blends provide packages with improved
barricade properties, and these arrangements pose higher manufacture costs, need
the use of superior adhesives which complicate their instruction, and are problem-
atic in recycling. Hence, the polymer industry tries to improve these properties of
monolayer polymer materials using technologies such as nanocomposites [37].
In nanocomposites and or bionanocomposites, there are nanofiller dispersed into
a homogeneous polymer matrix. This diffusion of nanofillers to the polymer matrix
246 S. Sivakanthan and P. H. S. Kaumadi
distresses the blockade properties of similar materials in two ways, first by the forma-
tion of a “tortuous path” for the dissemination of gas. Since nanofillers are imper-
meable in nature, the molecules of gas have to diffuse around them instead of taking
a straight path perpendicular to the surface of the film. Due to this reason, the mean
pathway for the dissemination of the gas via the film is elongated. Out of all dissim-
ilar forms of nanomaterials, including spheres, fibers, rods, tubes, and plates, layered
nanomaterials are the greatest suitable to recover the blockade properties. Other than
the nanofiller content and the aspect ratio, the state of exfoliation also moves the
blockade properties of nanocomposites.
In the second way of dispersion of nanofillers, nanomaterials can impact the
barricade properties by producing changes in the polymeric matrix. The polymer
chains in the vicinity of the nanomaterials get partially stopped if the interactions
of nanomaterial–polymer are favorable. Thus, the gas molecules which pass via
these interfacial zones will have weakened movement. Interfacial region effects are
important on these polymeric materials that exhibit high permeability to gases. When
related to micrometric fillers, the nanofillers consist of an advanced aspect ratio than
a higher surface area-to-volume ratio which in terms help to enhance the properties
of the composites/biocomposites. Barrier properties of various bionanocomposites
are shown in Table 9.1.
9.4.3 Thermal Properties
The processing of polymers and biopolymers is highly dependent on thermal proper-
ties such as glass transition temperature, and melting point. Molecules of the amor-
phous region of the polymers stay frozen under lower temperatures called “glassy
state”. This is the state where polymers are hard, rigid, and brittle. Once the polymers
are heated under higher temperatures, their chains wiggle making those polymers
more flexible giving the name “rubbery state”. The temperature where the shift occurs
from the glassy state to the rubbery state of the polymer is recognized as glass tran-
sition temperature. The amorphous region is the place where glass transition occurs.
The crystalline state stays without getting affected. The melting point of the polymer
is combined with the region of crystalline. At the temperature above the melting point
of a certain polymer, the viscosity of the polymer reduces fast and it improved the
ability to process the polymer. Various studies have reported the thermal properties
of different bionanocomposites, and some of them are summarized below.
•Bionanocomposites of starch reinforced nano-ZnO (2–4%) exhibited glass tran-
sition temperatures in uppers polymer around 39.1 °C, in lower polymer around
36.6 °C, and neat polymer around 34.7 °C [44].
•Starch reinforced with MMT at ratios of 1–7% exhibited melting points around
243.0, 221.5 °C, and 191.7, respectively, in upper, lower, and neat polymers [49].
9 Environmentally Friendly Bionanocomposites in Food Industry 247
Table 9.1 Effects of nano-reinforcing agents on barrier properties of various bionanocomposites
Biopolymer Nano-reinforcing agent Improvements/changes in
biopolymer properties (on
water vapor permeability
(WVP), water vapor
transmission rate (WVTR),
and oxygen transmission rate
(OTR)
References
PLA Nano–ZnO2Nano-ZnO2 resulted in about
37% decrease of WVP with
increased ZnO2 content from
1–3%
[31]
PLA Cellulose nanocrystals Reductions of 34% in WVP
were obtained for the cast
films containing 1 wt.% of
surfactant-modified cellulose
nanocrystals while OTR for
nano-biocomposites with
both 5 wt.% of
surfactant-modified cellulose
nanocrystals decreased by
48%
[40]
Whey protein–pullulan Nano-SiO2WVP of the film decreased
around 33% with the
increase of nano-SiO2
contentupto5%
[41]
Chitosan Cellulose nanofibers WVP reduced by 27%. For
the film with glycerol at the
concentration of 18% and
and cellulose nanofibers at
15%
[42]
Chitosan Nano-TiO2WVP decreased significantly
TiO2 concentration of 1%
and 2%
[43]
Starch Nano-ZnO2WVP reduced by 50% with
increased ZnO content up to
3%
[44]
Starch–PVA Nano-SiO2WVP decreased by 30% at
the nano-SiO2 concentration
up to 2%
[45]
Chitosan Cellulose nanocrystals By the addition of 3% of
cellulose nanocrystals,
WVTR reduced by 45% and
OTR decreased by 38%
[46]
Alginate Cellulose nanocrystals By the addition of 5% of
cellulose nanocrystals,
WVTR reduced by 15% and
OTR decreased by 45%
[46]
(continued)
248 S. Sivakanthan and P. H. S. Kaumadi
Table 9.1 (continued)
Biopolymer Nano-reinforcing agent Improvements/changes in
biopolymer properties (on
water vapor permeability
(WVP), water vapor
transmission rate (WVTR),
and oxygen transmission rate
(OTR)
References
Whey protein isolate MMT Addition of 15% (w/w
protein) MMT into 10%
(w/w dispersion) whey
protein isolate-based cast
films or coatings resulted in
reduction of OTR by 91%
for glycerol-plasticized and
84% for sorbitol-plasticized
coatings and reduction of
WVTR by 58% for
sorbitol-plasticized cast films
[47]
Whey protein isolate Nanoclays At the filler ratio of 9%,
WVTR and OTR were
reduced by approximately
50%
[48]
Kefiran Nano-ZnO WVP decreased about 17%
with increasing content of
nano-ZnO up to 2%
[36]
•Chitosan developed incorporating cellulose nanofibers provided glass transition
temperatures around 125.3, 138.1 and 130.1 °C in upper, lower, and neat polymers
[42].
•Whey protein consisting bionanocomposite reinforced with nano-SiO2 exhibited
glass transition temperatures around 34.06, 27.09, 29.08 °C, and melting points
of 117.34, 115.64 and 117.68 °C in upper, lower, and neat polymers [41].
•PLA reinforced with nanofibers exhibited glass transition temperatures and
melting points in upper, lower, and neat polymers 57.2, 56.3, 56.9, 168.0, 167.9
and 168.1 °C, respectively [50].
9 Environmentally Friendly Bionanocomposites in Food Industry 249
9.5 Application of Bionanocomposites in the Packaging
of Food
9.5.1 Dairy Products
The application of bionanocomposites as a packaging material is limited in the dairy
industry due to the shortcoming of the high sensitivity of biopolymers toward mois-
ture. Packaging of high moisture-containing dairy products such as yogurt, milk,
and ice cream employing biopolymer packaging is not possible due to the mentioned
cause. Therefore, the utilization of biopolymers as a packaging material in the dairy
industry is limited to low moisture-containing products only including cheese. Few
researchers have reported the application of bionanocomposites in the packaging of
different dairy products.
Gammariello et al. (2011) evaluated the effects of bio-based coating that consisted
of silver (Ag)/MMT nanoparticles together with modified atmosphere packaging on
sensory and microbial decay of the Fior Di cheese. Various concentrations (0.25,
0.50, 1.00 mg/mL) of Ag nanoparticles were incorporated in a sodium alginic acid
solution (8 wt./vol %) before the coating of the cheese. Up to 30% CO2,5%O
2, and
65% nitrogen were included in the modified atmospheric packaging. According to
the study, modified atmospheric packaging combined with Ag-based nanocomposite
induced the shelf life of the Fior Di cheese. Cheese stored in conventional packaging
exhibited a shelf life of around three days. Coated cheese stored in modified atmo-
spheric packaging achieved a shelf life of more than five days regardless of the Ag
nanoparticle concentration. This study stated that the strategy for shelf life prolon-
gation using this method could get practiced by the industries due to its simplified
application. Somehow, it is necessary to remove the developed coating containing
nanoparticles before eating the Fior Di latte. By some means, further studies must
be conducted to evaluate the safety of silver that migrates to the food [51].
Meira et al. (2016) have developed starch/halloysite/nisin nanocomposite films as
active antimicrobial packaging. Scanning electron microscopic image exhibited that
the films were homogeneous and halloysite nanotubes dispersed in a starch matrix.
The surface of films was aggregated as higher levels of nisin were added. According
to the X-ray diffraction (XRD) spectra, a decrease in polymer crystallization occurred
due to the alteration of starch peaks after halloysite nanotube and nisin incorporation.
The incorporation of HNT caused increased mechanical properties of the developed
films. By some means, addition of nisin causes a decrease in E and TS values.
The thermal stability of biofilms consisting of nisin was decreased. They showed a
Tmax value around 20–26 °C lower than the films without nisin. The antimicrobial
activity of the films was tested, against the microbes including Clostridium perfrin-
gens, Staphylococcus aureus, and Listeria monocytogenes present in skimmed milk
agar. Nisin consisted films were capable of inhibiting all mentioned microorganisms.
Minas Frescal cheese surface was applied with inoculated Listeria monocytogenes,
and, after four days, 2 g/100 g nisin-containing bionanocomposite caused a reduc-
tion in the initial microbial count of the bacterium. About 6 g/100 g nisin-containing
250 S. Sivakanthan and P. H. S. Kaumadi
films were able to inhibit Listeria monocytogenes completely. Results of this study
exhibited that nisin in starch/halloysite films could be a barrier control for the dairy
products such as cheese [52].
In a study by Incoronato et al. (2011), Ag/MMT embedded agar, antimicrobial
packaging material was developed and texted the effectiveness of the packaging
material toward the quality and the deterioration of Fior Di latte cheese. The presence
of spoilage-causing and beneficial microbes was observed during the study. The
sensory quality of the cheese was evaluated via a panel test. The result of this study
exhibited improved shelf life of the tested cheese. Ag cations hinder the proliferation
of microorganisms without affecting the beneficial microbiota and the quality of the
sensory traits of Fior Di latte. According to this study, the active packaging system
is suitable for the quality and the shelf life enhancement of the tested cheese product
[53].
Youssef and El-sayed (2018) prepared novel bionanocomposites using
chitosan/polyvinyl alcohol (PVA)/titanium nanoparticles. These bionanocompos-
ites were tested as packaging materials for soft white cheese. Characterization of
developed biofilms was done using a scanning electron microscope (SEM), Fourier
transform infrared spectroscopy (FTIR), and XRD. Chitosan/PVA/titanium nanopar-
ticles containing films posed excellent mechanical properties. Improved antimi-
crobial activities especially against gram-positive bacteria such as Staphylococcus
aureus, gram-negative bacteria such as Pseudomonas aeruginosa/Escherichia coli,
and fungi such as Candida albicans were also recorded. During the experiment,
soft white cheese was packed in developed bionanocomposite material and stored at
7 °C for about 30 days. The results of microbial analysis of bionanocomposite with
chitosan/PVA/titanium nanoparticles exhibited decreased total bacterial count, mold,
yeast, and coliform activities. This study concluded that these chitosan/PVA/titanium
nanoparticles consisting of bionanocomposites can be used in food packaging
applications including, cheese [13].
9.5.2 Fruit and Vegetable
Increasing demand for healthy and nutritious food has promoted the urge to circulate
fresh fruits and vegetables for consumption. Fresh products are highly vulnerable
to spoilage and physical damage, moisture loss, chemical alterations, and microbial
deterioration. The post-harvest life of the fruits and vegetables can be improved using
packaging including plastic films and coating. Though plastic is used as packaging
for many fruits and vegetable, they have become a global concern due to its non-
degradable nature. Due to the aforementioned issue, bioplastic films/coatings are
used as eco-friendly alternatives to conventional packaging. Generally, bioplastics
alone do not pose superior properties; therefore, they can be reinforced with nanopar-
ticles to improve this shortcoming. The nanoparticles employed in this process can
also exhibit antimicrobial, antioxidant activities. Many studies have been reported
9 Environmentally Friendly Bionanocomposites in Food Industry 251
on reviewing the effects of biopolymer-based nanocomposite films and coatings in
packaging whole or cut fruit and vegetables to extend their shelf life [54].
The effects of bionanocomposites on the preservation of fruits and vegetables
were experimented with by employing chitosan-based nanocomposites. As the study
concluded, chitosan is one of the excellent bioplastic materials which contributes to
improving the shelf life of fresh products, including fruits, vegetables, and meat. The
addition of nanoparticles of ZnO, Ag, and TiO2b together with phytochemicals such
as essential oils and fruit extracts in the matrix of chitosan increases the properties of
antimicrobial, mechanical, and barrier. The utilization of these bionanocomposites in
food packaging can improve the shelf life of various food products while contributing
to a reduction of non-degradable plastics and additive usage [55].
In a study by Maneerat and Hayata (2006), the antifungal activity of TiO2 photo-
catalytic reaction on plastic films upon Penicillium expansum was studied in vitro as
well as on fruits. The TiO2 photocatalytic reaction caused a reduction in the conidial
germination of fungi. The amount of TiO2 added was correlated to the actions of
the pathogen fungi, Penicillium expansum. The presence of the number of viable
colonies of Penicillium expansum was reduced as the amount of TiO2 increased.
The development of Penicillium rot on apples was reduced by the application of
bionanocomposite films with TiO2 photocatalytic reaction. Tomato fruits applied
with the same bionanocomposite exhibited no rot after a week of storage. Brown
lesions rot on lemons has decreased since the application of bionanocomposites with
TiO2. Findings from this experiment suggest that the TiO2 photocatalytic reaction is
effective in providing antifungal activity against Penicillium expansum that can be
utilized for disease control post-harvest [56].
Negatively charged polysaccharide, alginate matrices reinforced with sepiolite
and palygorskite fibrous clay were developed. Fibrous clay surface created strong
bonds between hydroxyl and carboxyl groups of the polysaccharide. The primary
interaction mechanism to obtain the stability of the bionanocomposite was the
hydrogen bonding between the –OH groups of biopolymers and the silanol groups of
the fibrous silicate. The improvement of mechanical and barrier properties, stability,
and water absorption reduction was achieved via the compatibility of the biopolymer
and the clay. Tested fillers of zein together with fibrous clay were also tested as fillers
for these films. Zein employment decreased the hydrophilic nature of pristine clay,
resulting in improved properties in biohybrid fillers. These biohybrid fillers incor-
porated films that exhibited excellent barrier properties to vapor and gas, reducing
the water uptake at higher humidity. As concluded by this study, these modified
bionanocomposites can be employed in packaging fruits and vegetables such as
apples. They will be a sustainable eco-friendly alternative in the food industry [57].
9.5.3 Meat and Poultry
Microbial contaminations, oxidation of lipid, and protein make products such as
meat poultry highly vulnerable to spoilage. Growing demand for healthy, safe, and
252 S. Sivakanthan and P. H. S. Kaumadi
nutritious food has increased the need to pack these products as a processing step.
The utilization of packaging technologies assists in keeping the quality and safety of
food products. Fresh food packaging helps to reduce microbial spoilage, lipid/protein
oxidation, and enzymatic deterioration of the food. By this, the tenderness, color,
aroma, etc., can be preserved. Currently, most packaging materials used in food
production industries are not biodegradable, which causes environmental concerns
[58].
The development of biopolymer-based packaging materials can help in reducing
fossil fuel-based materials in the industry. Bionanocomposites open a new road for
high-performance, lightweight green composite to substitute the non-degradable
packaging materials. When it comes to food packaging, special considerations
must be provided to obtain higher barrier properties. For that, nanostructures can
be employed to improve the active or intelligent properties of the food pack-
ages. According to many studies, use of bionanocomposites can be effective in the
extension of the shelf life of meat products. Below it has discussed the effects of
bionanocomposites on the quality of meat and poultry products [11].
In a study by Nagarajan et al. (2015), Tilapia and squid skin, gelatin biofilm
together with cloisite Na+ nano clay, and ethanolic extract of coconut husk was
developed. These films were utilized as a packaging material for mackerel meat
powder and stored for 30 days at 28–30 °C. Meat powder packaged in bionanocom-
posites exhibited lower moisture content, total volatile base, peroxide value, and pH
than meat powder packed in polyethylene films [59].
In a study by Morsy et al. (2014), turkey breast and beef were stored in pullulan
film consisting ZnO and Ag nanoparticles and oregano/rosemary extract for three
weeks at 4 °C. An inhibitory effect of pathogens such as S. aureus, L. monocytogenes,
and E. coli was observed. Ag nanoparticles exhibited a better effect on microbes when
compared to ZnO and extracts [60].
Bionanocomposite developed with chitosan and nanocellulose was employed in
storing ground meat for 6 days at 3 and 25 °C. The meat exhibited reduced color
change and lipid oxidation. A reduction in the growth of mesophilic aerobes and
psychrotrophic microbes was observed. Added carbon nanotubes contents assisted
in the improvement of the antimicrobial activities of these biofilms [61].
9.5.4 Application of Bionanocomposites in Novel Food
Packaging Systems
Active packaging
The urge for the utilization of food products up to a maximum level became essential
with the growing population and the land resource reduction. This is where packaging
came into play as an important material that assists in improving the shelf life of food
products throughout the food supply chain. Further, several improvements in pack-
aging systems enable various food products around the world with maximum shelf
9 Environmentally Friendly Bionanocomposites in Food Industry 253
life and safety [62]. According to significant demand changes of today’s consumers
and market trends, novel packaging systems such as active packaging became impor-
tant; when compared to the conventional packaging materials, this packaging system
is developed to interact with both internal and external environments of the pack-
aging and the food product [63]. Active packaging is defined as a package that alters
the conditions of the packaged food to improve the shelf life or to increase the food
safety and sensory properties, together with maintaining the quality of the packaged
food. Here the conditions inside the package get controlled to improve the quality
of the food product that has been packed [64]. In this section, it has been focused on
the employment of bionanocomposites as active packaging systems.
Antioxidant packaging
Lipid oxidation of food products with higher lipid content especially, with a higher
degree of unsaturated fatty acids, is prone to deterioration. Lipid oxidation of food
items, such as nuts, oils, fish, and meat products, results in giving off flavor due to
rancidity and makes the products less suitable for human consumption. Degradation
of polyunsaturated fatty acids as a part of lipid oxidation causes the formation of
toxic aldehydes and loss of nutrients in the foods.
Increasing demands for safer and healthier food products have taken the atten-
tion toward developing novel technologies such as the addition of antioxidants to
foods or packaging material. Novel food packaging technologies such as vacuum
packaging and modified atmosphere packaging get used to eliminate the presence of
oxygen inside the packaging system to minimize the food spoilages such as oxida-
tion. Nonetheless in scenarios where food products such as meat which cannot be
stored without oxygen, the application of antioxidants on the surfaces of the food or
incorporation into the packaging material can be an alternative [65].
Antioxidant packaging is a type of active packaging method in which antioxidant
properties get incorporated or coated with the packaging material to minimize the
oxidation of the food components. According to many studies, the release of incorpo-
rated antioxidants from packaging materials such as butylated hydroxytoluene (BHT)
and tocopherol from polythene films to foods with higher lipid contents delays the
oxidation of fats and the denaturation of the proteins. The utilization of natural antiox-
idants instead of synthetic additives in antioxidant packaging became a new trend.
Tocopherols, plant extracts, and essential oils present in herbs including rosemary,
tea, etc., are used as natural antioxidants in these kinds of packaging [66].
Bionanocomposites consisting of antioxidants are developed together with
nanoparticles and the bioactive molecules in a matrix of natural polymer. In
bionanocomposites, natural or synthetic antioxidants can be employed. Nanoparticles
get used to reinforce the polymer matrix and, in some cases, to release antioxidants
into the food system. Bionanocomposite films containing antioxidant components
are produced via casting or extrusion methods. These developed films get occupied
as packaging for fatty foods [31].
Many studies have developed numbers of antioxidants consisting of bionanocom-
posites; in the study of Infurna et al. (2020), bionanocomposite films were developed
based on natural chitosan, pectin, halloysite nanotubes, and antioxidants via solvent
254 S. Sivakanthan and P. H. S. Kaumadi
casting method. Halloysite nanotubes and antioxidants consisting of halloysite
nanotubes (quercetin and vanillic acid) effects on optical properties, mechanical
properties, photo-oxidation, and wettability were determined. The optical properties
and morphology of the films were not negatively affected by the halloysite nanotubes
and antioxidant containing halloysite nanotubes presented. The halloysite nanotubes
created a decreased water contact angle, and quercetin and vanillic presented in
halloysite nanotubes did not change the wettability of the films. The rigidity of the
films was decreased due to halloysite nanotubes in the chitin: pectin blend. With
the addition of halloysite nanotubes: quercetin and halloysite nanotubes: vanillic,
the rigidity of the system improved. Halloysite nanotubes played in improving
the compatibility of the bionanocomposite and provided antioxidant properties to
the matrix. The presented halloysite nanotubes cause a higher resistance toward
photo-oxidation [67].
Hybrid chitosan, nano-silver bionanocomposite films (CSSNC) were developed
using synthesized nanoparticles together with chitosan through the green ex situ
method out of the extracts of fruit waste. Around six films of different composi-
tions of CSSNCs were made using techniques including FTIR spectroscopy, ther-
mogravimetric analysis, XRD, SEM, and UV–visible spectroscopy. Out of all devel-
oped CSSNCs, the film of CS9AGEI was optimized for further biological assays
where the antimicrobial activity exhibited a high zone of inhibition t oward E.
coli and S. aureus. According to the antioxidant activities of the CSSNCs, radical
scavenging against nitric oxide, 2,2-diphenyl-l-picrylhydrazyl (DPPH), and total
reduction capacity was determined [68].
Bionanocomposite of polylactic acid nanofibers together with antibacterial prop-
erty containing silver nanoparticles and antioxidant activity bearing Vitamin E has
developed through electrospinning technology. In the study of Munteanu et al.,the
characteristics including structure and morphology of the bionanocomposies were
carried out in the study using SEM, XRD, and transmission electron microscope
(TEM). Nanofibers employed assisted in inhibiting the growth of E. coli, Salmonella
typhymurium, and Listeria monocytogenes. According to the results obtained from
the test of DPPH (2,2-diphenyl-l-picrylhydrazyl), the antioxidant activity was around
94%. Test on fresh apple and apple juice exhibited PLA/Ag/Vitamin E bionanocom-
posites’ ability to reduce the polyphenol oxidase activity. Silver nanoparticles
incorporated multifunctional electro-spun PLA nanofibers together with antioxidant
Vitamin E can be used as food packaging since they pose a higher surface area of
nanofibers together with antimicrobial and antioxidant activities. As concluded, this
developed type of bionanocomposites can be utilized as food packaging for fruits
and juices [69].
Polymethylmethacrylate (PMMA) and nano-hydroxyapatite (nHA) incorpo-
rated polymer-ceramic nanocomposite/composites were developed in the study of
Do˘gan et al. Nanocomposite showed different enzyme activities when compared to
the composites. Samples synthesized in acetone exhibited increased enzyme activ-
ities on glutathione reductase and glucose-6 phosphate dehydrogenase enzymes.
These samples also inhibited glutathione peroxidase and catalase enzyme activities.
9 Environmentally Friendly Bionanocomposites in Food Industry 255
Samples synthesized tetrahydrofurans were given inhibitory actions for glucose-6
phosphate dehydrogenase enzymes and catalase [70].
Binary/ternary polylactic acid-based bionanocomposites consisting of nano-
lignin and metal oxide particles (Ag2O, TiO2,) were developed in the experiment
of Lizundia et al. (2020) through solvent casting technique. Antioxidant activity of
ternary-based bionanocomposites was performed and obtained a synergic effect of
lignin and metal oxides. According to the study, these developed bionanocomposites
pose s triking renewable additives for food packaging and the biomedical industry
with higher antioxidant and antimicrobial properties [71].
Antimicrobial active packaging
Food products undergo different deterioration mechanisms such as microbial, phys-
ical, chemical, biochemical, and textural deterioration, based on the ingredients,
production methods, packaging systems, etc. Microbial deterioration is more domi-
nant when compared to other deteriorations and causes more damage to the food
products. While techniques such as canning, heat treatment, and dehydration are
used in improving the shelf life of the food, special attention must be given to the
packaging since it also plays an important role in protecting the products from envi-
ronmental hazards (e.g., moisture gain, dust, insects, etc.). Based on the factors such
as reduction of demand for chemical usage in food products, growing demand for
fresh-like, nutrient-rich foods, increasing food demand due to the world popula-
tion growth, and new packaging techniques such as active packaging, intelligent
packaging came to the play to secure the food safety. Since microbial spoilage is
dominant among many food products, the incorporation of antimicrobial agents into
the packaging became a promising technique in the active packaging system [72].
According to the intended use, the design of the antimicrobial can differ. When
developing antimicrobial packaging, the following factors should be considered.
•Residue antimicrobial actions, the processing method of the packaging, and the
chemical nature of the packaging material—the selection of an antimicrobial
agent is dependent on the processing method of the package including extrusion,
printing, etc., and its compatibility with the material. As an example, since higher
processing temperature may affect the antimicrobial agents, it is important to carry
out the processing methods such as extrusion at a low temperature.
•Traits of the antimicrobial agent and the food product—physicochemical char-
acteristics such as pH and the water activity of food have a great effect on the
antimicrobial agent. The pH of food ionizes the active site of the antimicrobial
agent, causing an alteration of its biological activities. Unique microflora of the
foods must also be considered when selecting the antimicrobial agent.
•Temperate during storage—this has a direct effect on the activity of the antimicro-
bial agents. Increased storage temperature increases the migration of antimicrobial
agents. Temperature is also related to the activity of residual antimicrobial activity.
•Physical properties of the packaging material.
The product, the container, and the space between them create the packaging
system. In antimicrobial packaging systems, active agents are put into packaging
256 S. Sivakanthan and P. H. S. Kaumadi
material: films, edible coating, bilayers, sachets, etc., there are several forms of
antimicrobial packaging as mentioned below [73].
As mentioned in Macromolecular Symposia, a chitosan-based bionanocomposite
was developed incorporating carvacrol as the antimicrobial agent [74]. In the study
of Youssef et al. a chitosan/PV-based bionanocomposite was developed incorpo-
rating TiO2 as the antimicrobial agent [75]. A PLA/NC bionanocomposite consisting
Mentha piperita and Buniun percicum was developed in the work of Talebi et al. [76].
Thymol incorporated PLA bionanocomposite was developed by Zhu et al. [77]. TiO2
nanoparticles incorporated chitosan film was developed in the study of Kaewklin
et al. [78]. Bionanocomposites-consisting antimicrobial agent ZnO was employed in
controlling Staphylococcus aureus and Candida albicans [79]. Halloysite, Ag NP,
Titania, layered silicate, and cellulose nanofibers incorporated PLA bionanocom-
posites were able to control Listeria monocytogenes, E. coli, and Bacillus subtilis
[80]. S. aureus, Bacillus cereus, E. coli 0157:H7 P. aeruginosa, and S. typhimurium
were controlled by the bionanocomposite developed of soybean polysaccharide with
zataria multiflora boiss and mentha pulegium essential oil [81–82].
Since the urge of replacing plastics with alternative materials becoming more
popular, scientists have put special focus on biopolymers. Cellulose, chitosan, lignin,
starch, polylactic acids, etc., are used as biopolymers due to their availability and
abundance to get used as food packages; these biopolymers must pose non-toxic
and must have the preferable level of properties. In each biopolymer, polymeric
chain configuration, substituents, and hydrogen bonds play an important role in
improving the properties. Most of the biopolymers exhibit antimicrobial activity
including chitosan. Most of the biodegradable non-toxic biopolymers including
cellulose, starch, chitosan, alginate, etc., answer the ecological problems. However,
biopolymers such as polysaccharides pose several shortcomings such as inferior
properties (mechanical, barrier). This is where nanomaterials come to the act to over-
come these issues. The incorporation of nanomaterials into the biopolymer matrixes
assists in improving mechanical properties and barrier properties. The most common
nanomaterials used in the field are montmorillonites, kaolinite, ZnO, TiO2, etc.
Intelligent packaging
The major role of packaging is to provide safety to a product against spoilage that
occurs due to exposure to different external environments. Packages can be seen
in different sizes and shapes to provide ease and convenience to the customer or
consumer. Some of the functions of packaging systems include providing defense,
convenience, containment, and information. In the current food industry, conven-
tional packaging no longer holds sufficient play due to upraising consumer demands
and product complexity. Within two decades, packaging systems including active
packaging and intelligent/smart packaging came into play to provide enhanced
protection, convenience, etc., to the food product as well as the customer [83].
According to the European Commission, intelligent packaging systems are “mate-
rials that monitor the conditions of packaged food or the environment that surrounds
the food”. Intelligent packaging is a technology that employs communication roles
to make decisions to enhance the shelf life, safety, and quality of the food product.
9 Environmentally Friendly Bionanocomposites in Food Industry 257
These packaging systems provide information and indicate issues that occur due
to the changes in the internal and external environment of the package. Intelligent
packaging systems monitor product quality and track the product for traceability.
These packages have become capable of providing information regarding both food
products and the integrity of the packaging. Indicators, sensors, and data carriers
are the main technologies utilized in these packages. Information supply is done by
sensors as well as indicators, while the data carriers offer management of logistics in
the supply chain. Intelligent packaging systems can be adopted by various packaging
types, including primary, secondary, and tertiary [84].
Bionanocomposite is considered a reliable candidate for the production of smart
packaging due to the properties they offer such as better electrical properties, easy
to handle, lightweight, and biocompatibility. Nanomaterials can be employed in the
detection of gases, contaminants, and microorganisms or to obtain responses that
occur due to environmental changes. A range of polymeric composites reinforced
with magnetic, electric, optical, and mechanical sensitive nanofillers get exploited
as sensors [31].
Microbial and gas detection
The quality of packaged food can be determined using indicators via the reac-
tions between metabolites generated during the multiplication of the microbes in
the product and the indicator. In many cases, the utilization of natural dyes in bio-
packaging for the determination of colorimetry is done. In a biofilm of chitosan, a
time–temperature indicator consisting of an anthocyanin pH indicator was employed
to determine deviations in the temperature during the storage time of the products.
Gas indicators including oxygen and carbon dioxide can also be used as intelligent
packages. These packaging systems indicate the presence of these gases based on the
color changes due to the chemical or enzymatic reactions and the amounts of gases
present. Essential oxygen detectors are recognized as methylene blue indicators,
which change the color due to oxidation or reduction. Silver and titanium dioxide
are nanostructures indicators used to a greater extent due to their higher sensitivity
and stability. Cytotoxicity in metal particles makes them unsuitable in the packages
of food. UV-activated oxygen detector consisting of redox dyes, an electron donor
glycerol, and UV absorbing nanoparticles including TiO2 in the film of carrageenan
is one of the developed studies for the gas detecting intelligent packaging [85].
Intelligent packaging also gives signals if the food system inside the package
is contaminated with microorganisms ensuring food protection and stability some-
times by releasing antimicrobial agents from the packaging. κ-Carrageenan/locust
bean gum-based films consisting of thermosensitive poly (N-isopropyl acrylamide)
nanohydrogels were developed in the study of Fuciños et al. (2015), which releases
natamycin in the packaging system as a response to environmental triggers. Yeast
and the Penicillium commune were employed as indicator microbes. Natamycin
consisting of biofilms exhibited more antimicrobial activity than the films without
it. As the study stated, this difference might be occurred due to the natamycin’s
protection from degradation in the biofilm enabling its release when the temperature
increases [86].
258 S. Sivakanthan and P. H. S. Kaumadi
9.6 Safety Concerns
Currently, consideration of the safety of food packaging systems consisting of nano-
materials gets a concern as these nanomaterials get leached into food products with
increased time and storage temperature. In three ways, nanoparticles in these food
packaging systems can affect humans: contact, ingestion, and inhalation. The degree
of migration of nanomaterials, rate of toxicity of nanomaterials utilized, and particle
size may determine the health effects of the packaging material with nanomaterials.
The release of nanomaterials from degrading bionanocomposites might also cause
harm to the environment [87].
The evolution of toxicological effects of nanoparticles in food packaging is done
in vitro and in vivo. Smaller particles of food packages get absorbed easily and
distributed into the organ to cause damage to the cells such as active oxygen species
development in the cells. Studies included mice have exhibited carbon nanotubes
generated asbestos, length-dependent toxicity when injected into the animals [88].
According to risk assessment regulations of Europe Union No. 10/2011 on plastic
materials, different toxicological properties of nanomaterials must be assessed on a
case-by-case basis. GRAS (generally recognized as safe) is important when nanopar-
ticles are incorporated in the packaging materials. Prior to confirming the safety of
nanomaterials, as suggested by the Institute of Food Science and Technology, the
nanoparticles should be treated as “potentially dangerous materials” to minimize
their toxic effects on humans [89].
9.7 Conclusion
Today, a number of studies have been carried out with the intention of development
and improvement of bionanocomposites for utilization in food packaging appli-
cations. These studies upon bionanocomposites aim to improve and develop eco-
friendly, greener plastic packaging materials that would help to improve the shelf life
of the food product by preserving them while reducing the waste generation coupled
around the food industry. Though there are various types of experiments performed
around biopolymers at the laboratory and industrial levels, still, there is a need for
a better understanding of the compositions, structures, and processing properties of
bionanocomposites for the utilization in various sectors. Though there are topics
discussed regarding the incorporation of nanomaterials into polymer complexes,
there are still enough space for the variations and the improvement in the develop-
ment of bionanocomposites. In this section, it is discussed that bionanocomposites
bear great potential as a greener solution in replacing conventional non-degradable
plastics materials. However, it is still necessary to further analyze the functional
properties of these bionanocomposites before they get used in the food industry to
give better competition against conventional plastics.
9 Environmentally Friendly Bionanocomposites in Food Industry 259
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