Marco Sangermano

• Professor
• Polytechnic University of Turin

Since aquaculture is playing an increasingly important role in food supply, ensuring the healthiness of aquatic environments is a fundamental issue. Anthropogenic activities are often a source of contamination for water and, among the pollutants released, potentially toxic elements (PTEs) represent a well‐known hazard to human health and ecosystem...

The photopolymerization process in 3D printing is considered greener once it involves a fast reaction and low energy consumption. Various reactions for photopolymerization can be used nowadays, but a special one is the thiol-ene “click” reaction that occurs in equimolar concentrations of thiol and alkene groups. In this sense, solvent-free photopol...

In this study, we present novel, vitrimeric and biobased scaffolds that are designed for hard tissue applications, composed of acrylated, epoxidized soybean oil (AESO) and reinforced with bioactive glass that is Tellurium doped (BG-Te) and BG-Te silanized, to tune the mechanical and antibacterial properties. The manufacture’s method consisted of a...

Additive manufacturing (AM) is a well‐established technique that allows for the development of complex geometries and structures with multiple applications. While considered a more environmentally‐friendly method than traditional manufacturing, a significant challenge lies in the availability and ease of synthesis of bio‐based alternative resins. I...

Numerous strategies have been developed for the corrosion protection of steel; however, most of them have a significant environmental impact and employ toxic compounds. Tannins are a green and promising solution for sustainable corrosion protection strategies. In this context, this work was focused on natural (condensed and hydrolysable) tannin lay...

Diglycidylether of vanillyl alcohol (DGEVA), in combination with mechanically recycled carbon fibers (RCFs), was used to make, via Radical-Induced Cationic Frontal Photopolymerization (RICFP), fully sustainable and bio-based conductive composites with good electrical conductivity and consequent Joule effect proprieties. Three different fiber length...

The development of 3D printing technologies and the requirement for more sustainable 3D printing materials is constantly growing. However, ensuring both sustainability and performance of the new materials is crucial to replace current fossil‐based polymers. Here, a bio‐based UV‐curable resin is produced in high yield from gallic acid (GA), a natura...

Additive manufacturing (AM) has revolutionised the manufacturing industry, offering versatile capabilities for creating complex geometries directly from a digital design. Among the various 3D printing methods for polymers, vat photopolymerisation combines photochemistry and 3D printing. Despite the fact that single-epoxy 3D printing has been explor...

Among the additive manufacturing techniques, UV-curing processes are of special interest, as they allow for the fabrication of thermosetting materials with high resolutions and optical clarity. Traditionally, these processes require the use of formulations, consisting of polyester or polyurethane oligomers, combined with photoinitiators and reactiv...

We utilized the combination of heterogeneous photocatalysis with enzymatic reactions as to allow reaching the degradation of refractory pollutants. Soybean peroxidase (SBP) was chosen as an enzyme, due to its...

The scientific strategies reported in the literature for developing biobased epoxy vitrimers are summarized. Biomass resources such as lignin, cellulose, or different vegetable oils can be exploited as biobased building blocks for epoxy thermosets as an alternative to the bisphenol‐A‐based ones. Biorenewable resources have been synthesized introduc...

3D‐printable vitrimers processed by digital light processing (DLP) have been recently developed, based on the transesterification reaction of β‐hydroxyester structures from mono‐ and diacrylate monomers employed in the formulation. These materials show promising repairability and recyclability, in addition to other interesting features such as shap...

In this study, a bio-based acrylate resin derived from soybean oil was used in combination with a reactive diluent, isobornyl acrylate, to synthetize a composite scaffold reinforced with bioactive glass particles. The formulation contained acrylated epoxidized soybean oil (AESO), isobornyl acrylate (IBOA), a photo-initiator (Irgacure 819) and a bio...

Four isosorbide-based photocurable resins were designed to reveal correlations between the composition and chemical structure, digital light processing (DLP) three-dimensional (3D) printability, thermoset properties, and recyclability. Especially, the role of functional groups, i.e., the concentration of ester groups vs the combination of ester and...

3D-printing technologies for polymeric formulations are experiencing a huge development due to the complex and specific geometries that can be covered employing additive manufacturing. However, to ensure sustainable growth, it is essential to replace the currently used fossil-based resins with new bio-sourced alternatives. In this study, tunable bi...

In the quest toward sustainable thermosets, research has been conducted on various polymer classes like epoxy, benzoxazines, acryl-/methacrylates, etc. One particular group that can also be utilized as sustainable inks for additive manufacturing is itaconic acid-based unsaturated polyester resins. However, due to increased viscosity of the resins,...

Lithium-oxygen batteries, with their very high energy density (3500 Wh kg⁻¹), could represent a real breakthrough in the envisioned strategies towards more efficient energy storage solutions for a less and less carbonated energy mix. However, the problems associated with this technology are numerous. A first one is linked to the high reactivity of...

The substitution of fossil resources by alternatives derived from biomass is a reality that is taking on a growing relevance in the chemical and energy industries. In this sense, fats, oils, and their derived products have become indispensable inputs due to their broad functional attributes, stable price and sustainable character. Acrylated vegetab...

Additive manufacturing is one of the most promising processing techniques for fabricating customized 3D objects. For the 3D printing of functional and stimuli-triggered devices, interest is steadily growing in processing materials with magnetic properties. Synthesis routes for magneto-responsive soft materials typically involve the dispersion of (n...

Corrosion is recognized as an unavoidable phenomenon and steel, particularly carbon steel, is strongly susceptible to corrosion. Corrosion damages cause serious material, energy, and economic losses as well as negative impacts on the environment. As a result, research interest has been focused on the development of effective corrosion prevention st...

A N‐hydroxy succinimide (NHS) ester substituted bis(acyl)phosphane oxide (ACTIVE‐BAPO) was prepared by phospha‐Michael addition and used for an easy one‐step BAPO ligation with substrates containing primary amino groups, such as amino acids, proteins, and poly(amidoamine) (PAMAM) dendrimers. Thereby, a range of new molecular and polymeric photoinit...

Vitrimers brought new properties in thermosets by allowing their reshaping, self-healing, reprocessing, and network rearrangement without changing structural integrity. In this study, epoxidized castor oil (ECO) was successfully used for the straightforward synthesis of a bio-based solvent-free vitrimer. The synthesis was based on a UV-curing proce...

The paradigm shift from traditional petroleum‐based non‐recyclable thermosets to biobased repeatedly recyclable materials is required to move toward circular bioeconomy. Here, two mechanically and chemically recyclable extended vanillin‐derived epoxy thermosets are successfully fabricated by introduction of Schiff‐base/imine covalent dynamic bonds....

A new system that exploits optical fiber distributed sensing for the detection of hydrocarbons is presented. The system relies on a custom-designed silica core/thin silicone cladding optical fiber to provide a quick and selective absorption of oil products through the cladding; moreover, it exhibits insensitivity to water. Optical fiber sensor inte...

The rise of 3D printing gave an important pulse into the medical field, envisaging the possibility to create artificial engineered tissues/organs perfectly suiting the patients’ tissues defects while using their...

Biomass feedstocks are playing a crucial role toward the development of new sustainable materials with the aim to replace the fossil-based ones limiting the emissions and waste. Among the other, cellulose, and hemicellulose are gaining interest as a source of new bio-based building blocks such as furan derivatives. In this study, two furan derivati...

Every year millions of people worldwide undergo surgical interventions, with the occurrence of mild or severe post-treatment consequences meaning that rehabilitation plays a key role in modern medicine. Considering the cases of burns and plastic surgery, the pressing need for new materials that can be used for wound patches or body fillers and are...

In this work, a new environmentally friendly material for the removal of heavy metal ions was developed to enhance the adsorption efficiency of photocurable chitosan-based hydrogels (CHg). The acknowledged affinity of tannic acid (TA) to metal ions was investigated to improve the properties of hydrogels obtained from natural and renewable sources (...

The removal of oil from water is a worldwide challenge that must be faced to avoid irreversible marine habitat destruction. A novel fast and simple technique to obtain polydimethylsiloxane (PDMS) membranes is developed using the photopolymerization technique. The high reactivity of the acrylated PDMS formulation towards photo‐induced free radical p...

Magnetoresponsive polymers have gained increased attention in the design of soft actuators as they can be spatially as well as temporally activated and enable an external noninvasive control of movement. By introducing the magnetoresponsive properties in photocurable resins, one can fabricate personalized and complex structures (via vat photopolyme...

The introduction of Hot Lithography has opened new perspective in the field of additive manufacturing especially with regard to high viscous formulations. The access to elevated temperature in the 3D printing process not only reduce the viscosity of resin but it allows to achieve higher curing kinetics and degree of conversion. Therefore, it is pos...

Electroconductive hydrogels (ECHs) have attracted interest for tissue engineering applications due to their ability to promote the regeneration of electroactive tissues. Hence, ECHs with tunable electrical and mechanical properties, bioactivity, biocompatibility and biodegradability are demanded. In this work, ECHs based on photo-crosslinked blends...

The revolution of 4D printing allows combining smart materials to additive processes to create behavioral objects able to respond to external stimuli, such as temperature, light, electrical, or magnetic fields. Here, a modified commercial digital light processing (DLP) 3D printer is used to obtain complex macroscopic remotely controlled gear‐based...

To date, the 3D printing of polymers with heterogeneous and locally controlled material properties is still a challenging area in additive manufacturing. In terms of vat photopolymerization 3D printing, the fabrication of multi-material objects typically relies on an automatic material exchange of different resin vats. However, along with the high...

Among the new generation of green polymers, furan monomers are occupying a strategic role to produce both innovative biobased thermoplastic and thermoset. Herein, furfuryl glycidyl ether (FGE) was used as monomer to design two steps cured coating. Linear polymer chains were firstly produced by means of cationic UV technique. The UV reactivity of FG...

In this study, new photocurable biobased hydrogels deriving from chitosan and gelatin are designed and tested as sorbents for As(V) and Pb(II) removal from water. Those renewable materials were modified by a simple methacrylation reaction in order to make them light processable. The success of the reaction was evaluated by both ¹H-NMR and FTIR spec...

Composites reinforced with micro-particles are widely used in engineering fields. Unfortunately, the traditional manufacturing processes do not allow customization and shape complexity achievable with additive manufacturing technologies. In particular, VAT polymerization enables the highest printing resolution. Here, we demonstrate the fabrication...

Bio‐based photocurable polymers are increasingly demanded as environmentally friendly materials for advanced applications. Together with functional fillers, represent a next step for the generation of functional and active smart materials, compatible with additive manufacturing technologies. This work reports on, acrylated epoxidized soybean oil (A...

Video demonstration of UV induced frontal polymerization

Radical induced cationic frontal polymerization is a promising route to achieve rapid curing of epoxy-based thermosets, requiring only a localised exposure with (ultraviolet) light. In the presence of a diaryliodonium based photoinitiator and a thermal radical initiator, a self-sustaining hot front cures epoxide monomer via a cationic mechanism. Ho...

Through a well targeted design, vitrimers are able to reorganise their three-dimensional covalently crosslinked network structure by associative exchange reactions when the so-called topology freezing transition temperature (T v ) is exceeded....

Kurt Dietliker, Robert Liska and Marco Sangermano introduce the Polymer Chemistry themed collection on photopolymer science dedicated to Ewa Andrezejewska.

The residue of acrylate functions after the DLP-printing of formulations containing multifunctional monomers is here taken as a potential advantage for post-functionalization purposes. The unreacted acrylates exposed on the surface...

The radical-induced cationic frontal photopolymerization (RICFP) of fully biobased epoxy composites is successfully demonstrated. This curing strategy considerably reducess the curing time and improves the efficiency of the composite fabrication. Two different natural fibre fabrics made of cellulose and flax fibres are embedded in two epoxy matrice...

Light processable natural polymers are highly attractive for 3D printing of biomedical hydrogels with defined geometries and sizes. However, functionalization with photo-curable groups, such as methacrylate or acrylate groups, is required. Here, we investigated a microwave-assisted process for methacrylation of chitosan to replace conventional meth...

Biorenewable “all-starch”-derived organo/hydrogels (OHGs) were prepared via “green” and fast UV-curing and tested as bio-adsorbents for the removal of methylene blue from water. Methacrylated starch (MS) and acrylated starch derivative, γ-cyclodextrin (ACy), were synthetized for use as OHG precursors for the photopolymerization process. Real-time p...

The possibility to 3D shape hydrogels is attracting an enormous interest in the biomedical field both for their application as scaffold or for the design of new medical hydrogels. Digital light processing (DLP) printing can create layer-by-layer models with high resolution and printing speed. Herein, a hybrid natural-synthetic hydrogel is propsed u...

The 3D printability of cold-water fish gelatin used as co-initiating species for the crosslinking of PEGDA monomers in presence of camphorquinone (through a Norrish II reaction) is evaluated. The 3D digital light processing (DLP) leads to the creation of biocompatible printed structures able to support cell viability and proliferation.

Light processable hydrogels were successfully fabricated by utilizing maize starch as raw material. Increasing the starch content from 10 to 15 wt% increased the compressive stiffness from 13 to 20 kPa, which covers the stiffness of different body tissues.

The 3D printability of cold-water fish gelatin used as co-initiating species for the crosslinking of PEGDA monomers in presence of camphorquinone (through a Norrish II reaction) is evaluated. The 3D digital light processing leads to the creation of biocompatible printed structures able to support cell viability and proliferation.

An in‐depth investigation on novel electro‐activated shape memory polymer composites (SMPCs) for digital light processing 3D‐Printing, consisting of a poly(ethylene glycol) diacrylate/poly(hydroxyethyl methacrylate) matrix embedding multi‐walled carbon nanotubes (CNTs), is reported here. The composition of the photocurable (meth)acrylate system is...

The use of toxic crosslinking agents and reagents in the fabrication of hydrogels is a frequent issue which is particularly concerning for biomedical or food packaging applications. In this study, novel antibacterial bionanocomposite films were obtained through a simple solvent casting technique without using any crosslinking substance. Films were...

When a lipid membrane approaches a material/nanomaterial, nonspecific adhesion may occur. The interactions responsible for nonspecific adhesion can either preserve the membrane integrity or lead to its disruption. Despite the importance of the phenomenon, there is still a lack of clear understanding of how and why nonspecific adhesion may originate...

UV-initiated cationic frontal polymerization is exploited as a solvent-free, extremely fast, and low-temperature technique to obtain epoxy-based adhesives. Epoxy formulations are prepared by blending commercial resins at different weight ratios and adding photo and thermal initiators at different percentages. In addition, the influence of other cri...

The ability to program the behavior of magneto-reactive polymers requires the fine control of their magnetic microstructure during each step of the printing process. Here, a systematic study of magnetically driven self-assembly of Fe3O4 nanoparticles into chain-like structures is presented and used in a 3D printable formulation. The kinetics of cha...

New fully biobased formulation was developed and UV cured to obtain a polymer network useful for coating applications. Lipoic acid and isosorbide diallyl were used as functional monomer for thiol-ene chemistry. Radical UV curing was used to get the network from the liquid resin. The fully biobased formulation was UV cured and tested. Photorheology...

The present work highlights the synthesis and post-modification of silica-based micro-particles containing photo-responsive polymer brushes with photolabile o-nitrobenzyl ester (o-NBE) chromophores. For the synthesis of the polymer brushes, two different...

Thermal conductivity is a key property in many applications from electronic to informatics. The interaction of fillers with Sylgard 184 was studied; this study explores new composites and the influence of metal particles (copper and nickel), carbon-based materials (carbon nanotubes and carbon black), and ceramic nanoparticles (boron nitride) as fil...

In this paper a simple three-components photopolymerizable system based on 2-hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol methyl ether methacrylate) (PEGMEMA) is used for the fabrication of thermoset H-bond stabilized shape memory polymers (SMPs) via digital light processing (DLP) three-dimensional (3D) printing. A bis(acyl)phosphane o...

Ultrafiltration membranes with antifouling and antibacterial properties are greatly beneficial for all industrial applications and to supply safe water worldwide. Improving these properties while maintaining both high productivity and high product water quality remains a challenge. This work proposes the surface functionalization of an ultrafiltrat...

In the study of conductive conjugated polymers, electrical doping has long played an important role. A new polymeric gas sensor has been successfully fabricated by means of an ink-jet printer using a conductive aqueous formulation of poly(3,4-ethylenedioxythiophene) poly(styrene-sulfonate) (PEDOT:PSS). A simple yet robust treatment method for the i...

Bio-based monomers represent the future market for polymer chemistry, since the political economics of different states promote green ventures toward more sustainable materials and processes. Industrial pulp and paper processing represent a large market that could advance the use of by-products to avoid waste production and reduce pollution. Lignin...

This work addresses the integration of ceramic matrix composites (CMCs) and an Al alloy to obtain mechanically reliable and in-service durable CMC-Al alloy joints for high-performance road brake discs. Such a braking system is based on the use of CMC discs mounted onto a hub or stub axle by means of a mounting bell, manufactured in aluminium alloy....

Removal of contaminants from wastewater is one key element for the development of sustainable society. Here, innovative “all-lignocellulose” derived photo-curable hydrogel nanocomposites based on methacrylated carboxymethyl cellulose (M-CMC) and lignosulfonate-derived carbonaceous products were successfully designed. The carbon products were synthe...