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Cotton/Wool Printing with Natural Dyes Nano-Particles

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In the present work, cotton/wool 50/50 blended fabric is printed via three natural dyes nanoparticles namely: turmeric, madder and rhubarb. Dye powder of the three plants was milled for 30 days after which it was exposed to ultrasound for 6 hours. Cotton/wool substrate is mordanted prior to printing process using two mordants separately: tartaric acid and potassium aluminium sulphate (alum). All parameters that are found to influence colour intensity as well as fastness levels of the prints are investigated in detail. Moreover, all required measurements that show the impact of milling and sonication on dye particles are carried out.
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J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
90
Cotton/Wool Printing with Natural Dyes Nano-Particles
D. Maamoun1,, H. Osman2, S. H. Nassar3
1Textile Printing, Dyeing & Finishing Dept., Faculty of Applied Arts, Helwan University, Giza, Egypt; 2Textile
Printing, Dyeing & Finishing Dept., Faculty of Applied Arts, Benha University, Benha, Egypt; 3Textile Research
Division, National Research Center, Giza, Egypt
Received December 22, 2013; Accepted February 02, 2014
Abstract: In the present work, cotton/wool 50/50 blended fabric is printed via three
natural dyes nanoparticles namely: turmeric, madder and rhubarb. Dye powder of
the three plants was milled for 30 days after which it was exposed to ultrasound for
6 hours. Cotton/wool substrate is mordanted prior to printing process using two
mordants separately: tartaric acid and potassium aluminium sulphate (alum). All
parameters that are found to influence colour intensity as well as fastness levels of
the prints are investigated in detail. Moreover, all required measurements that show
the impact of milling and sonication on dye particles are carried out.
Keywords: Ball miller, blended fabric, colour intensity, fastness levels, mordant,
nanoparticles, natural dyes and sonication.
Introduction
Natural dyes are as old as textiles themselves (Siva 2007). They have been used by humans for
purposes varying from coloration of food, cosmetics and textiles to imparting other functions to them
(Yi and Cho 2008). Nowadays, a revival interest in the use of natural coloration has been growing.
This is a result of the stringent environmental standards imposed by many countries in response to the
toxic and allergic reactions associated with synthetic dyes (Nagia & El-Mohamedy 2007). Natural
dyes are chemically safer than their synthetic analogous in handling and use because of their
compatibility with the environment, their non-carcinogenic and biodegradable nature (Baishya et al.
2012). Natural dyes can be used to dye different natural and man-made materials (Wakida et al. 1998).
Textile coloration using natural dyes is found to yield poor colour, have inadequate fastness
properties. To overcome such hassle, mordants are used. Metal ions of mordants act as electron
acceptors for electron donors to form co-ordination bonds with the dye molecule (Mogkholrattanasit et
al. 2011). Because of the chemistry associated with dyes from natural materials, it is necessary to
utilize fibres which have dye sites that can bond molecularly with these dyes (Bliss 1981). Cotton has
no inherent affinity for most natural dyes. However the affinity of cotton can be modified to make it
dyeable with natural dyes by the use of metallic salts (mordants) or the process of cationization which
creates positively charged sites on cotton or by addition of NaOH or enzymes (Gupta and Gupta
2002). Further, these dyes can directly dye protein fabrics under acidic pH since they have basic amino
groups in the same manner as synthetic acid dyes. Textiles can also be mordanted to give dye-metal
complexes. Hence, it is not only an acid dye but also a mordant dye (Gupt,a 2002).
Nanotechnology is concerned with materials whose structures exhibit significantly novel and
improved physical and biological properties, phenomena, and functionality due to their nanoscaled
size (Wang, 2000). It can provide high durability to fabrics, because nano-particles have a large
surface area-to-volume ratio and high surface energy, thus presenting better affinity for fabrics and
leading to an increase in durability of the function (Wong, 2006).
When matter is reduced in size, it changes its characteristics, such as colour and interaction with
other matter i.e., chemical activity. The change in characteristics is caused by the change of the
electronic properties. By particle size reduction, the surface area of the material is increased. Due to
this, a higher percentage of the atoms can interact with other matter, i.e. with the matrix of resins.
Agglomeration and aggregation blocks surface area from contact with other matter. Since most nano-
materials are available in a dry state, the particles need to be mixed into liquid formulations. This is
where most nano-particles form agglomerates during their wetting. Therefore, effective means of
deagglomerating and dispersing are required to overcome the bonding forces after wetting the micron
powder or nano-powder (URL-1).
Corresponding: E-Mail: daliamaamoun@gmail.com; Tel: +201001454214
J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
91
The application of mechanical press, generated by ultrasonic cavitations, breaks the particles
agglomerates apart. Also, liquid is pressed between the particles. Different technologies are commonly
used for dispersing powders into liquids such as high intensity sonication. It is particularly suitable for
particle treatment in the nano-size range in order to achieve the required results. Intense cavitational
forces allow for dispersing and milling particles. Ultrasonic milling and dispersing narrows the particle
size distribution curve significantly. Thus, particle characteristics and product's quality are greatly
enhanced.
The present work addresses utilizing three different plant species (turmeric, madder and rhubarb)
to be printed on cotton/wool substrate. Printing characteristics are optimized via dyes-particle size
reduction through milling as well as sonication. Subsequently, all parameters that may improve the
performance of the dyes are studied.
Materials and Methods
Materials
Substrates: The used substrate in the present work is: 50/50 mill scoured cotton/wool fabric, having a
weight of 210 g/m2 and is purchased from Golden Tex Co., Cairo, Egypt.
Natural dyes: Clean, dry, ground turmeric, madder and rhubarb plants, having the following
specifications, are used throughout the present study:
Table 1. Technical specifications of turmeric, madder and rhubarb natural dyes
Mordants and other chemicals: All the used chemicals are of analytical grade:
Tartaric acid: C4H6O6
Potassium aluminium sulphate: KAl(SO4)2.12H2O
Mypro gum NP-16 (Meyhall): which is a non-ionic thickening agent based on modified plant seeds
gum that is capable of withstanding the acidity required in printing.
Methodology
Fabric mordanting
The used substrate (50/50 cotton/wool fabric) is mordanted prior to printing process. The mordanting
bath is set with different concentrations of both mordants, tartaric acid and potassium aluminium
sulphate, separately on weight of fabric at L.R. 1:40. Mordanting is carried out at 60 oC for 30 min.
after which the samples are washed with distilled water and air-dried.
Preparation of dye nano-particles
The three natural dyes under investigation are ground using an energy Ball Mill with a speed of 50
cycles/min. The dye powder was sealed in a hardened steel vial (AISI 44°C stainless steel) using
English name
Latin
name
Colour
component
Colour
Index
Chemical structure
Turmeric
(Cai et al.
2004)
Curcuma
longa
Curcumin
(Diferuloye-
Methane)
Yellow
Natural
Yellow 3
Indian
Madder
(Deo and Paul
2003)
Rubia
Cardifolia
Munjistin
(Acid/Mordant/
Disperse)
Red
Natural
Red
8,16
Rhubarb
(Dolu)
(Gupta, 2000)
Rheum
emodi
1-Chryosophanic
Quinone
(Anthraquinone)
Mordant/Disperse
Yellow
Natural Yellow
23
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92
hardened steel balls of 6 mm diameter. Milling was performed using a ball : powder mass ratio of 4:1.
The dye was milled at different intervals, after each milling interval the particle size of the resulted
dye powder was measured. The smallest particle size of 40, 42 and 48 nm of turmeric, madder and
rhubarb respectively, is chosen to be used in the present study and was obtained from milling the dye
powder for 30 days.
A stock solution was prepared using the milled dye particles of a concentration of 3% where 3g dye
powder was dispersed in 97 cm3 of distilled water. The suspension was irradiated afterwards with
ultrasound waves (720 kHz) and stirred at 80 oC for different periods of time (4, 6 and 8 hours.) from
which the ultrasound treatment of 8hrs. was chosen to proceed with since it gave best K/S values.
Printing procedures
To investigate each factor of the present work, a printing paste having the following formula was
applied for all dyes:
20 g Stock dye mixture
80 g Mypro gum thickener
10 g Urea
X ml Water
1000 g Total weight of paste
The pH is adjusted according to each required value using acetic acid solution. The printing paste is
applied to fabric through flat screen printing technique then, the prints are left to dry at room
temperature. Fixation of the dye is carried out via steaming at 120°C for 20 min. for all dyes. The
samples are finally washed off using 2g/l non-ionic detergent: Sera-Wash M-RK (manufactured by
Dystar Textilfarben, Germany) at a liquor ratio of 1:50. Washing is carried out at 60°C for 10 min.
Measurements
Colour Strength
The colour strength of the printed specimens expressed as K/S is evaluated by a light reflectance
technique at maximum. The spectrophotometer used is of the model ICS-Texicon Ltd., England (Judd
and Wyszecki 1975)
Scanning Electron Microscope (SEM)
The surface morphology, structure and particle size of dye samples without milling and milled for 30
days are investigated by a Scanning Electron Microscope (SEM) Philips XL 30 attached with an EDX
unit; with an accelerating voltage of 30 K.V., magnifications range 1500-2000x and a resolution of
200 A. Before examinations, the fabric surface was prepared on an appropriate disk and coated
randomly by a spray of gold.
Transmission Electron Microscopic analysis (TEM)
The observation of the dye particle shape and the measurement of the particle size distribution of the
precipitate were performed using a JSM-5200 Scanning Electron Microscope (JEOL) using
conductive carbon paint. Transmission Electron Microscope (TEM) is a good tool to study the particle
size and morphology of dyes. TEM gives a good resolution down to a nanometer scale. Photographs
were taken using JEOL-2010.
Fourier Transition Infrared spectroscopy (FT-IR)
Fourier Transition Infrared spectroscopy (FT-IR) of the samples was recorded using a Brucker-FTIR.
The method includes mixing few mgs. of a fine powder of the sample with KBr powder in a gate
mortar. The mixture was then pressed by means of hydraulic press. The absorbance was automatically
registered against wave number (cm-1).
Optical properties (UV-Visible spectra)
The optical absorption of dye particles dissolved in distilled water were recorded in the wave length
range 400-800 nm employed using a Shimadzu spectrophotometer, at room temperature.
Fastness properties
Fastness properties of cotton/wool prints to rubbing, washing and perspiration are assessed according
to standard methods (Iso Test for Colour Fastness of Textile Substrates 1969).
Tensile mechanical testing
The samples are cut into strips and every data point is the average of 3 tests. Tensile strength
measurement is carried out using a Textile Tensile Strength tester No: 6202, 1987, type: Asano
Machine MFG, Japan.
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93
Results and Discussion
Mordant concentration
Natural dyes have limited substantivity for fibres and require the use of a mordant to enhance fixation
of the natural colorant on fibres by the formation of a complex with the dye (Maulik and Padhan
2005). Metallic mordants anchored to any fibre, chemically combine with certain mordantable
functional groups present in the natural dye and bind by coordinated/covalent bonds or hydrogen
bonds and other interactional forces as shown below (URL-2):
Mechanism of fixation of natural dyes through mordants
The influence of mordant type as well as concentration on colour intensity of printed cotton/wool
substrate with the three natural dyes nanoparticles is studied through using different concentrations (0,
20, 40, 60 and 80 g/l) of both mordants (tartaric acid and alum) and the results are plotted in Figure 1.
Figure 1. Effect of mordant type and concentration on K/S values of cotton/wool fabrics printed with
the three dye nanoparticles
It is obvious from the figure that, optimum K/S values may be achieved on premordanting the
substrates with 60 g/l mordant regardless of the mordant type and dye used. The latter result is due to
obtaining developments in colour intensity of the prints by 49.4, 40 and 65.3 % for turmeric, madder
and rhubarb dyes respectively, premordanted with tartaric acid compared with the typical
unmordanted substrate. On the other hand, for printed cotton/wool substrate with turmeric, madder and
rhubarb dyes premordanted with alum, K/S improvements by 66, 38.1 and 77.5 % are accomplished
respectively, all compared with the unmordanted substrates printed also with dyes nanoparticles.
It is important to notify that, both mordants lead to almost similar K/S enhancements with all
dyes. Besides, huge K/S developments are achieved on comparing the printed substrates with regular
dyes and nano-scaled dyes, all treated with both mordants separately. For cotton/wool substrate
premordanted using tartaric acid and printed with turmeric, madder and rhubarb dyes, improvements
in colour intensities by 226.9, 171.2 and 144.8 % respectively are observed. While for similar prints
premordanted by alum, developments in colour intensities by 287.3, 195.5 and 144.8 % respectively
are noticed. The former results are referred to the influence of both milling as well as sonication of dye
powders that lead to particle size reduction. Grinding increases the specific surface area (ssa) of the
ground particles due to particle size reduction (Franco et al. 2004). A feasible technique for particle-
J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
94
size reduction is ultrasound. Cavitational collapse sonication in solids leads to microjet and shock-
wave-impacts on the surface, together with interparticle collisions, which can result in particle-size
reduction (Peters, 1996).
Urea concentration
Urea is an essential auxiliary in printing pastes because during the steaming process, particularly
during the use of superheated steam, it is mainly used to swell the fibres so that the dye can rapidly
penetrate the fibres (Achwal 2002, Chen et al. 2002). Urea acts as a solvent for the dye as it performs
as a moisture-absorbing agent to increase the moisture regain during the steaming process. Thus, urea
accelerates the migration of dye from the thickener film into the fibres. The influence of urea
concentration on colour intensity of cotton/wool printed substrate with the three natural dyes
nanoparticles is studied through adding different concentrations to their recipes (0, 5, 10, 20 and 30
g/kg) and the results are plotted in Figure 2.
Figure 2. Effect of urea concentration on K/S values of cotton/wool fabrics pretreated with tartaric
acid as well as alum, separately, and printed with the three dye nanoparticles
It can be concluded from the figure that, best K/S values can be obtained by adding 10 g/kg urea
to printing recipes regardless of the mordant or the dye used with the substrate. Enhancements in K/S
by 7.8, 13.6 and 10.2 % can be achieved for prints with turmeric, madder and rhubarb dyes
respectively, premordanted with tartaric acid compared with similar printed substrates without urea
addition to their recipes. On the other hand, similar enhancements by 8.6, 2.4 and 3 % are observed for
premordanted substrates with alum.
The above results are explained by the fact that, urea enhances the solubility of dyes in the
printing paste due to its salvation and disaggregating action on dye molecules (Labarthe 1975). This
action varies from one dye to another according to its ability to dissolve in the printing paste.
Therefore, the hydrophobic/hydrophilic balance of the dye molecule will determine its ability to
dissolve under the action of urea. Hydrophobic dyes such as disperse dyes are not affected by urea
addition as the more hydrophilic dyes. Therefore, increasing the hydrophobic character of the used
natural dyes may diminish the solvolysis effect of urea and reduces its role in the printing paste.
Printing paste pH
Coloration of textiles with natural dyes can be carried out in alkaline, acidic or neutral medium
depending on both: the used substrate and dye. Wool is a natural protein fibre that has a complex
chemical structure and is very much susceptible to alkali attack (at pH>9). Hence, printing of the
cotton/wool substrate used in the present work needs special care to avoid fibre damage by alkaline
pH. Moreover, wool contains equal number of amino and carboxylic groups held together as salt
linkages which bridges the main peptide chains (Bird 1951). Printing paste pH is considered as an
effective factor in colour variation and subsequently, the influence of printing paste pH on colour
intensity of the prints is studied by applying values (4, 5, 6, 6.5 and 7) and the results are exhibited in
Figure 3.
J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
95
Figure 3. Effect of printing paste pH on K/S values of cotton/wool fabrics pretreated with tartaric acid
as well as alum, separately, and printed with the three dye nanoparticles
It is clear from the figure that, maximum K/S values can be obtained at pH 6, 5 and 6.5 for
cotton/wool substrate printed with turmeric, madder and rhubarb nanoparticles respectively, regardless
of the mordant used prior to printing process. These results confirm well with literature provided that
printing is expected to be carried out at weak acidic medium which slightly varies according to natural
dye structure.
Scanning Electron Microscopic (SEM) and Transmission Electron Microscopic (TEM) studies
Figure 4 shows the surface morphology, structure and particle size of dye samples without milling and
milled for 30 days. Figure 4 (a, c and e) show the SEM images of the unground dye which indicate
that, dye particles have different shapes like breaking dishes shape, spherical shape and tiny sprinkled
dots. The micrographs in Figure 4 (b, d and f) indicate uniform spherical dye nanoparticles. The
difference in particle size after grinding is referred to their dissociation due to the impact of shear
forces that act on dye particles in the ball miller which converted the particle size gradually from 60,
80 and 113 nm (before milling) to 40, 34 and 48 nm (after 30 days of milling) for turmeric, madder
and rhubarb dyes respectively.
Figure 4. SEM images of dye particles: a) turmeric before milling, b) turmeric after milling, c)
madder before milling, d) madder after milling, e) rhubarb before milling, f) rhubarb after milling
Fourier Transition Infrared spectroscopy (FT-IR)
FT-IR spectra of the unground and ground madder, turmeric and rhubarb particles are shown in Figure
5. FTIR spectra is measured to investigate the effect of milling on the functional groups of materials.
Madder contains several polyphenolic compounds like 1,3-Dihydroxy-anthraquinone
(purpuroxanthin), 1,4-Dihydroxyanthraquinone (quinizarin), 1,2,4-Trihydroxyanthraquinone
(purpurin) and 1,2-dihydroxyanthraquinone (alizarin) (Dorland's Illustrated Medical Dictionary). FT-
IR spectrum of the unground madder (a) shows absorption at peaks 3450, 2925, 1634, 1318, 1035 and
518 cm-1. The bands at 1636, 1035 and 518 cm-1 can be attributed to the carbonyl groups, the in-plane
and out-of-plane CH bending, respectively. The bands at 3450 and 2927 cm-1 are attributed to OH
groups of polyphenols in the dye. The spectrum of the ground madder (b) exhibits a very slight shift in
the peak at 1636 cm-1 which may be attributed to particle size reduction.
Turmeric contains curcumin which incorporates several functional groups. The aromatic ring
systems, which are phenols, are connected by two α, β-unsaturated carbonyl groups. The diketons
form stable enols and are readily deprotonated to form enolates; the α,β-unsaturated carbonyl group is
a good Michael acceptor and undergoes nucleophilic addition. FT-IR spectrum of the unground
J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
96
turmeric (c) shows absorption at peaks 3450, 2925, 2854, 1637, 1458, 1155 and 1031, 572 cm-1. The
bands at 1637, 1155 and 578 cm-1 can be attributed to the carbonyl groups, the in-plane and out-of-
plane CH bending, respectively. The bands at 3450, 2927 cm-1 are attributed to OH groups of
turmeric dye. While the spectrum of the ground turmeric (d) exhibits shift in the peaks at 1158cm-1
and appearing of 2854 and 1514 cm-1 which is may be attributed to decreasing the particle size.
FT-IR spectrum of the unground rhubarb (e) shows absorption at peaks 3450, 2927, 1633, 1384, 1050
and 578 cm-1. The bands at 1633, 1050 and 578 cm-1 can be attributed to the carbonyl groups, the in-
plane and out-of-plane CH bending, respectively. The bands at 3450, 2927 cm-1 are attributed to OH
groups of polyphenols in the dye. The spectrum of the ground rhubarb (f) exhibits shifts in the peaks
1633, 1448 cm-1 which is may be attributed to particle size reduction.
Figure 5. FT-IR spectra of: a) Unground madder, b) Ground madder, c) Unground turmeric, d)
Ground turmeric, e) Unground rhubarb, f) Ground rhubarb
UVVisible spectroscope
UVvisible spectroscopy was employed to characterize the optical properties of the ground and
unground natural plants such as madder, turmeric and rhubarb and the data are represented in Figure 6.
Turmeric (Dorland's Illustrated Medical Dictionary) is a diarylheptanoid. Turmeric's other two
curcuminoids are desmethoxycurcumin and bis-desmethoxycurcumin. The curcuminoids are natural
phenols that are responsible for the yellow colour of turmeric. Turmeric can exist in several tautomeric
forms, including a 1,3-diketon form and two equivalent enol forms. The enol form is more
energetically stable in the solid phase and in solution (Tsonko et al. 2005). Figure (6a, b) show the
results of optical absorption spectra of turmeric in visible region. It can be seen from UV-visible
spectra (a) that, the unground turmeric particles show an absorption band around 554 nm
characteristics of yellow colour. Turmeric, bis (4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-
dione, is a natural yellow-orange dye derived from the rhizome of curcuma longa. On the other hand,
the UV-visible spectra (a) of ground turmeric particles reveal a strong change in their optical
absorption when their size is reduced. The spectra of ground turmeric particles show blue shift of the
main bands (to a lower wave length) that appears at 535 nm. This is may be attributed to the lowering
of the particle size as a result of milling due to quantum confinement effect.
Figure (6c, d) show the results of optical absorption spectra of madder in visible region. It can be
seen from UV-visible spectra (c) that, the unground madder particles show absorption band in the
range from 400 to 490 nm characteristics of red colour. The red colour is referred to that madder
contains polyphenols, compounds like 1,3-Dihydroxy-anthraquinone (purpuroxanthin), 1,4-
Dihydroxyanthraquinone (quinizarin), 1,2,4-Trihydroxyanthraquinone (purpurin) and 1,2-
dihydroxyanthraquinone (alizarin). The spectra of ground madder particles show red shift of
absorption (to a higher wave length) that appears at 501-592 nm. This is may be attributed to particle
size lowering due to milling.
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Figure (6e, f) show the results of optical absorption spectra of rhubarb in visible region. It can be
seen in UV-visible spectra (f) that, the unground rhubarb particles show two main absorption bands
around 444 and 411nm characteristics of red brown colour. The red colour is referred to that rhubarb
contains polyphenols, compounds such as lycopene and anthocyanin. Rhubarb also contains
glycosides- especially rhein, glucorhein, and emodin, which impart cathartic and laxative properties
(Diaz 1990). On the other hand, the UV-visible spectra (e) of ground rhubarb particles reveal a strong
change in their optical absorption when their size is reduced. The spectra of ground rhubarb particles
show blue shift of the main bands (to a lower wave length) and appear at 440 and around 400 nm. This
is may be attributed to particle size lowering due to milling because of quantum confinement effect.
Fastness properties
The overall fastness properties of printed cotton/wool substrate with the three dyes (in the blank
regular form as well as the nanoparticle form) are tested and evaluated in terms of rubbing, washing,
perspiration and tensile strength, using optimum conditions of both premordanting as well as printing
recipes, and the results are exhibited in the following table:
Fastness properties of cotton/wool substrate printed with turmeric, madder and rhubarb regular dye
particles (blank) as well as dyes nanoparticles using optimum pretreatment as well as paste conditions.
Table 2. Fastness properties of cotton/wool substrate printed with turmeric, madder and rhubarb
regular dye particles (blank) as well as dyes nanoparticles using optimum pretreatment as well as paste
conditions
Substrate Status
K/S
Values
Rubbing
Washing
Perspiration
Tensile strength
Tenacity
(kg)
Elongation
(%)
Acidic
Alkaline
Dry
Wet
St.
Alt.
St.
Alt.
St.
Alt.
Blank prints of turmeric
pretreated with tartaric
acid
1.60
4
4
4
4
4
4
4
4
41.155
0.183
Prints of nano-turmeric
pretreated with tartaric
acid
5.23
4-5
4
4-5
4-5
4
4
4-5
4-5
41.155
0.183
Blank prints of turmeric
pretreated with alum
1.69
4
4
4-5
4-5
4-5
4-5
4-5
4-5
50.46
0.193
Prints of nano-turmeric
pretreated with alum
5.81
4-5
4
4-5
4-5
4-5
4-5
4-5
4-5
50.46
0.193
Blank prints with madder
pretreated with tartaric
acid
2.22
4
4
4
4
4
4
4
4
48.58
0.177
Prints with nano-madder
pretreated with tartaric
acid
6.02
4-5
4-5
4-5
4-5
4
4
4
4
48.58
0.177
Blank prints of madder
pretreated with alum
2.01
4
4
4
4
4
4
4
4
61.395
0.197
Prints of nano-madder
pretreated with alum
5.94
4-5
4-5
4-5
4-5
4
4
4
4
61.395
0.197
Blank prints of rhubarb
pretreated with tartaric
acid
2.70
4
4
4
4
3-4
3-4
3-4
3-4
44.08
0.183
Prints of nano-rhubarb
pretreated with tartaric
acid
6.61
4-5
4-5
4-5
4-5
3-4
3-4
3-4
3-4
44.08
0.183
Blank prints of rhubarb
pretreated with alum
2.90
4
4
4
4
3-4
3-4
3-4
3-4
56.54
0.200
Prints of nano-rhubarb
pretreated with alum
7.10
4-5
4-5
4-5
4-5
3-4
3-4
3-4
3-4
56.54
0.200
St. = Staining on cotton, Alt. = Alteration
J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
98
Figure 6. UV-Visible spectra of: a) Unground turmeric, b) Ground turmeric, c) Unground madder, d)
Ground madder, e) Ground rhubarb, f) Unground rhubarb,
From the previous table it can be concluded that, colourfastness ratings of all prints in question range
from good to excellent, which ensures the existence of strong bonds between dye molecules and the
fibres leading to making them quite satisfactory for practical application purposes. On the other hand,
considerable improvements in fastness levels are observed comparing printing with dye nanoparticles
to printing with the regular dye. Concerning the influence of premordanting on tensile strength of the
substrate it should be noted that, a slight reduction is detected in fibres' tenacity for both mordants but
can be ignored since it is within the allowed limit.
Conclusion
Three natural dyes namely, turmeric, madder and rhubarb are milled and exposed to ultrasound
waves in order to reduce their particle size to the nano-scale and to accelerate fibres' chemical
reactivity.
Cotton/wool blended substrate is padded using two mordants separately [tartaric acid or potassium
aluminium sulphate (alum)] to increase the affinity as well as dye fixation onto fibres via formation
of complex bonds.
The aforementioned dyes are successfully used in printing the substrate i.e., huge colour intensity
developments are achieved comparing printing using the regular dye with the nanoparticle dye.
Also, printing is carried out incorporating urea in printing recipes at weak acidic medium.
Different measurements are employed to illustrate the influence of milling and sonication on dye
particles are included such as: SEM, FT-IR and UV-visual spectroscopes. Besides, assessment of
fastness properties is carried out.
The investigated parameters imply that, optimization of printing performance using the three
natural colorants is fulfilled which is referred to particle size reduction due to the effect of milling
and sonication.
References
Achwal WB, (2002) Textile Chemical Principles of Digital Textile Printing (DTP). Colourage. 49, 33-
34.
Baishya D, Talkdar J, Sandhya S, (2012) Cotton dyeing with Natural Dye Extracted from Flower of
Bottlebrush (Callistemon Citrinus). Univer. J. Environ. Res. & Techno., 2, 377-378.
Bird CL, (1951) The Theory and Practice of Wool Dyeing, 2nd Ed. Society of Dyers and Colourists.
Bliss A, (1981) A Handbook of Dyes from Natural Materials. McGraw-Hill Inc., New York.
Cai Y, Sun M, Xing J, Corke H, (2004) Antioxidant Phenolic Constituents in Roots of ReumOfficinale
and Rubia Cordifolia: Structure-Radical Scavening Activity Relationships. Journal of
Agricultural and Food Chemistry, 52, 7884-7890.
Chen W, Wang G, Bai Y, (2002) Best for Wool Fabric Printing-Digital ink-jet. Textile Asia, 33, 37-39.
J. Int. Environmental Application & Science, Vol. 9(1): 90-99 (2014)
99
Deo HT, Paul R, (2003) Eco-Friendly Mordant for Natural Dyeing of Denim. Int. Dyer, 188, 49-52.
Diaz AN, (1990) Absorption and Emission Spectroscopy and Photochemistry of 1, 10-Anthraquinone
Derivatives: A Review. J. Photochem. & Photobiology, 53, 141 167.
Dorland's Illustrated Medical Dictionary, (2011) 2nd Ed. Elsevier, UK.
Franco F, Perez-Maqueda LA, Perez-Rodriguez TL, (2004) The Effect of Ultrasound on Particle Size
and Structural Disorder of a Well-Ordered Kaolinite. J. Colloid & Interf. Sci., 274, 107-117.
Gupta D, Gupta P, (2002) Convention on Natural Dyes. Colourage, 49, 87-89.
Gupta D, (2000) Mechanism of Dyeing Synthetic Fibres with Natural Dyes. Clourage, 47, 23- 24.
Gupta S, (2002) Natural Dyes-A Real Alternative. International Dyer. 187, 17-19.
URL-1 http://www.hielscher.com/ultrasonics/nano_00.htm, (accessed in 20/11/2013).
URL-2 Samanta AK, Konar A. Dyeing of Textiles with Natural Dyes www.intechopen.com, (accessed
in 23/12/2013).
Iso Test for Colour Fastness of Textile Substrates, (1969) Rio 5171. Iso Technical Committees.
Judd BD, Wyszecki H, (1975) Colour in Business: Science and Industry. 3rd Ed., John Wiley & Sons.
Labarthe J, (1975) Elements of Textiles, Macmillan Publishing Co., New York.
Maulik SR, Padhan SC, (2005) Dyeing Wool and Silk with Hinjal Bark, Jujube Bark and Himalaya
Rhubarb, Man-Made Textiles in India, 48, 396-400.
Mogkholrattanasit R, Krystufek J, Weiner J, Vikova M, (2011) Dyeing Fastness and UV Protection
Properties of Silk and Wool Fabrics Dyed with Eucalyptus Leaf Extract by the Exhausion
Process. Fibres and Textiles, 19, 94-99.
Nagia FA, and El-Mohamedy R, (2007) Dyeing of Wool with Natural Anthraquinone Dyes from
Fusarium Oxisporum. Dyes and Pigments, 75, 550-555.
Peters D, (1996) Ultrasound in Materials Chemistry. J. Material Chem., 6, 1605.
Siva R, (2007) Status of Natural Dyes and Dye-Yielding Plants in India. Current Sci., 92, 916-925.
Tsonko KM, Evelina VA, Bistra SA, Michael S, (2005) DFT and Experimental Studies of the
Structure and Vibrational Spectra of Curcumin. Int. J. Quantum Chem., 102, 10691079.
Wakida T, Choi S, Tokino S, (1998) Effect of Low Temperature Plasma Treatment on Colour of Wool
and Nylon 6 Fabric Dyed with Natural Dyes. Textile Research J., 68, 848-853.
Wang ZL, (2000) Characterization of Nanophase Materials, Weinheim: Wiley-VCH Veslag GmbH,
London (UK).
Wong YWT, Yuen CWM, Leung MYS, Ku SKA, Lam HLI, (2006) Selected Applications on
Nanotechnology in Textiles. AUTEX Research J., 6, 1-8.
Yi E, Cho J, (2008) Colour Analysis of Natural Colorant-Dyed Fabrics. Colour Res. & Appl., 23, 148-
160.
... Most natural dyes are extracted from plant roots, stems, leaves, and flowers, and they are widely used in fabric dyeing due to the advantages of large reserves and rich colors [1]. Compared with the synthetic dyes, natural dyes have many excellent characteristics including low toxicity, anti-oxidation, anti-bacterial and anti-ultraviolet properties [2,3]. With the enhancement of environmental protection awareness, the development and utilization of natural dyes have been paid more and more attention by some researchers. ...
... On the basis of measured CIE color measurement, the color differences (∆E) of the dyed cotton fabrics were calculated [Equation (2)]. The ∆E value is used to analyze the levelness of the dyed cotton fabric. ...
... The polycarboxylic As shown in Figure 2, the absorption peak at 3410 cm −1 was assigned to -OH stretching vibration and the band at 2900 cm −1 was due to C-H stretching vibration [21]. It could be observed that all dyed cotton fabrics appeared a similar anthraquinone ring vibration peak of madder dye at 1597 cm −1 [2], indicating the madder dye could dye in the cotton fabrics. And all cross-linked dyed cotton fabrics appeared the ester carbonyl absorption As shown in Figure 2, the absorption peak at 3410 cm −1 was assigned to -OH stretching vibration and the band at 2900 cm −1 was due to C-H stretching vibration [21]. ...
Article
Full-text available
Cotton fabrics were dyed with the madder and compounds of citric acid (CA) and dicarboxylic acids [tartaric acid (TTA), malic acid (MLA), succinic acid (SUA)] as cross-linking agents and sodium hypophosphite (SHP) as the catalyst. The molecular structures and crystal structures of the dyed cotton fabrics were analyzed using Fourier-transform infrared spectroscopy (FTIR) and X-ray diffractometry (XRD), respectively. The results showed that the polycarboxylic acids esterified with the hydroxyl groups in the dye and cellulose, respectively, and the reaction mainly occurred in the amorphous region of the cotton fabric. Compared with the direct dyed cotton fabric, the surface color depth (K/S) values of the CA, CA+TTA, CA+MLA, CA+SUA cross-linked dyed cotton fabrics increased by approximately 160%, 190%, 240%, 270%, respectively. The CA+SUA cross-linked dyed cotton fabric achieved the biggest K/S value due to the elimination of the negative effect by α-hydroxyl in TTA and MLA on esterification reaction, and the cross-linked dyed cotton fabrics had great levelness property. The washing and rubbing fastness of the cross-linked cotton fabrics were above four levels. The light resistance stability and the antibacterial property of the cross-linked dyed cotton fabrics was obviously improved. The sum of warp and weft wrinkle recovery angle (WRA) of the CA+SUA cross-linked dyed cotton fabric was 55° higher than that of raw cotton fabric, and its average UV transmittance for UVA was less than 5% and its UPF value was 50+, showing a great anti-wrinkle and anti-ultraviolet properties.
... Several studies on printing of different textile fabrics with natural dyes have been reported in different literature (Salem et al., 2013;Maamoun et al., 2014;Rekaby et al., 2009;Chattopadhyay and Pan, 2018). Polyester fabric can be printed with the extracts from different plants like turmeric (Curcuma longa), alkanet (A. ...
... tinctoria), and rhubarb (Rheum rhabarbarum) using natural and synthetic thickeners at various processing conditions of transfer printing, and satisfactory fastness properties can be achieved (Salem et al., 2013). Cotton/wool blended fabric printed with nanoparticles of turmeric, madder, and rhubarb was found to have excellent wash, rubbing, and perspiration fastness (Maamoun et al., 2014). Rekaby et al. (2009) applied different fixation techniques for cotton, wool, silk, and flax substrates printed with extracts of alkanet and rhubarb colorants. ...
Chapter
Until the middle of the nineteenth century, only natural colorants were used for textile colouration. After the advent of synthetic dyes, the use of declined drastically and today only a small fraction of textiles that commercially traded are coloured with natural dyes. However, there is a potentiality of increasing the use of natural colourants for textile applications. The natural dyes can be sourced from plants, insects and minerals. This chapter gives an overview of the classifications and examples of natural dyes and a brief synopsis of research and developments in textile colouration with them. https://www.sciencedirect.com/science/article/pii/B9780128035818116686
... Urea considered an essential auxiliary in most printing pastes because of its ability to swell the fabrics that accelerate penetrating dye inside the fabrics [34]. In addition, it acts as a solvent for the dye i.e., used as moisture-absorbing agent and accelerates the migration of dye from the thickener film into the fabrics. ...
... Urea considered an essential auxiliary in most printing pastes because of its ability to swell the fabrics that accelerate penetrating dye inside the fabrics [34]. In addition, it acts as a solvent for the dye i.e., used as moisture-absorbing agent and accelerates the migration of dye from the thickener film into the fabrics. ...
Research
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Hiren alkanet dye nanoparticles were successfully prepared by using simple ball milling technique at room temperature. UV-vis. absorption, XRD, TEM, FT-IR spectroscopy and SEM were used to characterize alkanet dye nanoparticles. The prepared alkanet dye nanoparticles were used as active ingredient for printing cotton, wool and polyester fabrics via dye printing technique and pigment printing technique. Factors of printing process were studied such as Mordanting of Substrates, thickeners type, urea concentration and Printing Paste pH for first paste and urea concentration, Printing Paste pH and binder concentration for second paste. Results shows fabrics printed with alkanet dye nanoparticles via mentioned two methods shows very good to excellent fastness properties with full green method. These data indicated that printed samples have high quality for colour strength without any environmental hazards compared with other conventual and nanotechnological aspects.
... Negative environmental impacts of synthetic dyes have aroused extensive interest in the use of natural colorants during the last few decades. Besides textile dyeing, certain natural dyes have been applied by printing technique as mentioned in previous works, for example, alkanet and rhubarb (Rekaby et al., 2009), red mangrove bark (Nakpathom et al., 2011), eucalyptus leaves and bark (Ellams et al., 2014), turmeric, madder, and rhubarb (Maamoun et al., 2014), catechu, turmeric, and marigold (Teli et al., 2014), annatto seed, manjistha root, and ratnajot bark (Chattopadhyay & Pan, 2019). In our earlier study, the printing pastes were prepared from an aqueous solution extracted from Camellia oleifera fruit shell with commercial thickener and binder and then screen printed on cotton fabric (Nakpathom et al., 2017). ...
Article
Natural colorant extracted from the fruit shell of Camellia oleifera was applied to PP spunbond nonwoven fabric by pigment printing method. The printing pastes containing natural dye, a thickener, an acrylate binder, and ferrous sulfate were applied to the substrate via flat screen technique. The printed fabrics were evaluated in terms of colorimetric measurements, color fastness properties as well as mechanical behaviors. The increase in color strength and the change in color hues from light brown to greyish black were observed by varying the amounts of dye, binder and ferrous sulfate. Increasing binder concentration led to an improvement in tensile strength and elongation in most cases, but had a negative impact on tear strength. The printed nonwoven possessed fair to moderate light fastness and fair to excellent crock fastness.
Article
Cotton fabric dyed with natural madder dye exhibits poor dyeing properties. Although mordant improves the dyeing property of cotton fabric, it changes the madder dye colour tonality (the hue angle). In this study, ethylene glycol diglycidyl ether (EGDE) was used as a crosslinking agent to dye cotton fabrics with natural madder dye and improve the surface colour depth (K/S) and colour fastness. The molecular structure, crystal structure and surface morphology of crosslinked dyed cotton were analysed using Fourier Transform–infrared spectroscopy, X-ray diffractometry and scanning electron microscopy, respectively. The results showed that crosslinked dyed cotton fabric had two different ether bonds, and that crosslinked dyeing mainly occurred in the amorphous area. Compared with direct dyed cotton fabric, the hue angle (h°) of crosslinked dyed cotton fabric did not undergo an obvious change, K/S increased by 5, and the rubbing fastness, washing fastness and light fastness increased by 2-3 levels, indicating that the dyeing property of cotton fabric with natural madder dye could be improved by using EGDE as a crosslinking agent. Compared with raw cotton fabric, the bending length of crosslinked dyed cotton fabric was reduced by 2.28 cm, the wrinkle recovery angle increased by 80.7° and the ultraviolet protection factor value was more than 40, indicating that crosslinked dyed cotton fabric had great softness, wrinkle resistance and excellent ultraviolet resistance. In addition, the water contact angle of the cotton fabric only changed slightly after crosslinking dyeing, and the crosslinked dyed cotton fabric still had good hydrophilicity. Therefore, EGDE was a viable crosslinking agent for cotton fabric with madder dye.
Chapter
Biotechnology is expected to be a one stop solution for many problems associated with the production of many materials and products. The application of biotechnology in industry is termed as “white biotechnology” where enzymes and microorganisms are used as tools to replace hazardous materials and substances. The textile wet processing industry is vast and being accused for usage of huge quantities of water, chemicals and energy. Textile printing is a technique by which colours (dyes/pigments) are applied as specific patterns or designs on the fabric. Dyes need to be imparted to the textiles during colouration and the same dyes (unfixed) need to be removed from the waste water during effluent treatment. The use of enzymes in both fixation and removal of dyes have replaced many hazardous chemicals in a sustainable way. This chapter discusses the biotechnological approaches in textile printing.
Chapter
Natural dyes and pigments could be obtained from insects, plants, and animals. Natural dyes have been utilized in the dyeing of wool, cotton, and silk since the prehistoric ages. The first applications of natural dyes on textile fibers are estimated to have started in Mesopotamia and India in 4000 BC. In these first dyeing trials, it is thought that pigments were used for dyeing process and these pigments could be easily removed from fabrics by friction and washing because of their weak mechanical bonding onto the fibers, and therefore, dyeing process was not really successful. It is thought that mordant dyeing method may have been accidentally discovered. In many countries, such as India, Egypt, Anatolia, and China, many historical natural dyed fabrics were found. One of the first synthetic dyes, mauveine (also known as aniline purple), was accidentally synthesized by W.H. Perkin (at the age of 18) in 1856 during attempts to make quinine. The discovery of the first synthetic dye changed the natural dyeing habits and synthetic dyes replaced almost all natural dyes. However, it is known that the wastewater produced in the production steps of synthetic dyes and the chemicals used in the textile dyeing process can have toxic and pollutant effects on human and environmental health. Nowadays, the effects of environmental awareness, organic products, and the tendency toward healthy lifestyle also reflect on the textile sector. Disagreements on the risks of the usage of synthetic dyestuffs and increasing environmental awareness result in an enhanced interest in natural resources, environmentally friendly products, and new strategies. That is one of the reasons why the use of natural dyes came back to the agenda due to an increased ecological and sustainable awareness. Unlike non-renewable raw materials of synthetic dyes, natural dyes are mostly renewable and sustainable. Natural dye sources are agriculturally renewable sustainable vegetable-plant-based colorant sources. In terms of sustainability, synthetic dyes are produced from non-renewable resources; however, natural dyes are extracted from renewable sources. The ability to obtain the dye from renewable natural sources makes natural dyes an attractive dye class for more sustainable world. Natural dyes can be applied on the fibers not only with dyeing method but also with printing method. Textile printing is one of the most important and versatile methods among the methods used to design and colorize textile fabrics. Ancient men and women mixed the colorants such as coal or soil paint with oils and used them with their fingers in lines on various materials. The staining of the plant extracts and fabrics has provided different approaches. The patterns can be produced by the wax applications to provide resistant dye liquor, or the surrounding areas provide a tightly attached and reserved area. The word of print is referred to a process that uses pressure to impart colorant to the material. And there is no doubt that the first textile printing was occurred by the blocks with embossed printing surfaces, then these blocks were inked and printed on the fabric. Some of the first blocks were made of clay or terracotta, while others were made of carved wood. In this chapter, the information about various eco-friendly prints and different printing techniques which were applied to different kinds of fibers and fabrics using sustainable natural dyes and natural pigments are given in detail.
Article
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A renewed international interest has arisen in natural dyes due to increased awareness of the environmental and health hazards associated with the synthesis, processing and use of synthetic dyes. The present investigation was carried out to extract natural dye from Callistemon citrinus plant. The dye was extracted by boiling method. A part of the extract was autoclaved. Both the autoclaved and non-autoclaved Callistemon citrinus flower dye was used for dying the scoured cotton cloth using two mordants viz. Copper sulphate and ferrous sulphate. Study about fastness tests of dyed clothes was undertaken. The relative colour strength of the dye was determined in terms of K/S value with respect to autoclaved and non-autoclaved extract. Good light fastness, rub fastness and wash fastness was observed in fabrics mordanted with ferrous sulphate. The relative colour strength of the dye was found to be more in case of cotton clothes mordanted with ferrous sulphate.
Article
Full-text available
This research was concerned with dye extraction from the leaves of eucalyptus and with the application of this dye for silk and wool fabric dyeing by the exhaustion process. Optimal results were achieved when dyeing at 90 °C for 40 minutes and at pH 4. Silk and wool fab- rics dyed in a solution composed of eucalyptus extract from leaves in combination with a mordant compound showed a shade of yellowish-brown. An exception was when the fabrics were dyed with FeSO4 mordant, resulting in a shade of dark grayish-brown. The colour fastness to light and rubbing after dyeing the silk and wool fabrics treated with the mordant was investigated, the results of which showed fair to good fastness, whereas the colour fast- ness to washing was at a good to very good level. The results confirmed that natural dyes from eucalyptus leaf extract have potential applications for fabric dyeing and producing ultraviolet (UV) protective silk and wool fabrics.
Article
The spectral characteristics, photophysical parameters and photochem-ical reactivities of l,lO-anthraquinone derivatives are reported. The effects of various parameters (substituents, intramolecular and intermolecular hydrogen bonds, solvents, concentration and chemical reaction) on the absorption and emission properties are described. The photochemical reactivities , photo-oxidations and photoreductions displayed by the various derivatives are given and compared.
Article
Reports on dye-fibre combinations that have been studied to develop understanding of the behaviour of natural dyes when used with synthetic fibres: nylon and polyester with various vegetable dyes one based on carotenoid molecule the others quinone; and acrylic fibre with Berberis dye. Evaluation of results is made using isotherms which graphically represent the equilibrium dye distribution between dye bath and substrate. The 3 most important types are Nernst, Freundlich and Langmuir. Results show it is possible to dye nylon, polyester and acrylic with selected natural dyes, and bright and deep shades can be achieved. All processes are endothermic as dyes are hydrophobic. Quinone based dyes exhibit exceptional fastness.
Article
This is a review of a convention hosted by the Department of Textile Technology at the Indian Institute of Technology in Delhi. Five sessions were available and a total of fifteen papers, discussed in detail in this article, were presented. The papers ranged from a discussion of available technology in the use of natural dyes to the use of natural dyes in modern fashion. One speaker estimated the export market for natural dyes at 1000 tonnes with one Indian company having a 300-tonnes/y production capacity. The increased cost of the natural dyeing processes compared with chemical dyes is said to be easily compensated for by higher end product prices. With Indian export of cotton textiles estimated at $1 billion annually a value addition of 10%, due to natural dye processes could significantly increase India's income from textiles. One interesting observation is that cotton "has no inherent affinity" for the majority of natural dyes.
Article
The process of digital ink-jet printing is described together with the advantages it confers, not least the elimination of several traditional processes such as colour separation, drawing and screen preparation. On the subject of wool the author quotes authorities who estimate that only 1% of wool fabric is printed. Two main reasons for the low figure are identified as the high cost of wool fabric and the short runs required for this upmarket fabric. Conventional printing techniques are wasteful of fabric and more suitable for long print runs. The conclusion is that digital ink-jet printing is the best technology for printing on wool. It is said that a clear market for printed wool fabric exists. The article discloses the preparation of wool fabrics for digital ink-jet printing, the inks used and the technology involved. Key to the technology is the use of computer control in both printing and design of the printed patterns.
Article
The Second National Convention on Natural Dyes, held at IIT Delhi, indicated a vast scope for research and development in the techniques of cultivation, processing, and dyeing of natural dyes. Natural dyes are extracted from vegetable matter and put to a variety of uses, including the coloration of textiles, cosmetics, and health products. The raw materials for the production of natural dyes are extracted from seeds, leaves, bark, or the heartwood of the plants which are renewable and easily available in large quantities. Natural dyes can be classified on the basis of their application properties into acid, basic, disperse or vat class. Mordants are an important support to dyes, which not only help improve affinity but also enhance the color and improve the fastness of dyes. Research and promotional efforts are continuing, which will result in the emergence of dyes as an environmental friendly alternative for the coloring of textiles.
Article
Dyeing of ecru denim with natural dyes like turmeric and Indian madder was carried out using tartaric acid, an eco-friendly mordant The results were compared with those obtained when highly polluting metallic mordants like copper sulphate and stannous chloride, and a less polluting metallic mordant, potassium alum were used. The study aims at the elimination of metallic mordants and the development of eco-friendly natural dyed denim.
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The use of nanotechnology in the textile industry has increased rapidly due to its unique and valuable properties. The present status of nanotechnology use in textiles is reviewed, with an emphasis on improving various properties of textiles.