Photocurable Polymers Research Articles

Capillary trapping of various nanomaterials on additively manufactured scaffolds for 3D micro-/nanofabrication

High-precision additive manufacturing technologies, such as two-photon polymerization, are mainly limited to photo-curable polymers and currently lacks the possibility to produce multimaterial components. Herein, we report a physically bottom-up assembly strategy that leverages capillary force to trap various nanomaterials and assemble them onto three-dimensional (3D) microscaffolds. This capillary-trapping strategy enables precise and uniform assembly of nanomaterials into versatile 3D microstructures with high uniformity and mass loading. Our approach applies to diverse materials irrespective of their physiochemical properties, including polymers, metals, metal oxides, and others. It can integrate at least four different material types into a single 3D microstructure in a sequential, layer-by-layer manner, opening immense possibilities for tailored functionalities on demand. Furthermore, the 3D microscaffolds are removable, facilitating the creation of pure material-based 3D microstructures. This universal 3D micro-/nanofabrication technique with various nanomaterials enables the creation of advanced miniature devices with potential applications in multifunctional microrobots and smart micromachines.

β-Lactoglobulin-based aerogels: Facile preparation and sustainable removal of organic contaminants from water

Economically and efficiently removing organic pollutants from water is still a challenge in wastewater treatment. Utilizing environmentally friendly and readily available protein-based natural polymers to develop aerogels with effective removal performance and sustainable regeneration capability is a promising strategy for adsorbent design. Here, a robust and cost-effective method using inexpensive β-lactoglobulin (BLG) as raw material was proposed to fabricate BLG-based aerogels. Firstly, photocurable BLG-based polymers were synthesized by grafting glycidyl methacrylate. Then, a cross-linking reaction, including photo-crosslinking and salting-out treatment, was applied to prepared BLG-based hydrogels. Finally, the BLG-based aerogels with high porosity and ultralight weight were obtained after freeze-drying. The outcomes revealed that the biocompatible BLG-based aerogels exhibited effective removal performance for a variety of organic pollutants under perfectly quiescent conditions, and could be regenerated and reused many times via a simple and rapid process of acid washing and centrifugation. Overall, this work not only demonstrates that BLG-based aerogels are promising adsorbents for water purification but also provides a potential way for the sustainable utilization of BLG.

Synthesis and Properties of Photocurable Polymers Derived from the Polyesters of Glycerol and Aliphatic Dicarboxylic Acids.

The rapid development of 3D printing technology and the emerging applications of shape memory elastomer have greatly stimulated the research of photocurable polymers. In this work, glycerol (Gly) was polycondensed with sebacic, dodecanedioic, or tetradecanedioic acids to provide precursor polyesters with hydroxyl or carboxyl terminal groups, which were further chemically functionalized by acryloyl chloride to introduce sufficient, photocurable, and unsaturated double bonds. The chemical structures of the acrylated polyesters were characterized by FT IR and NMR spectroscopies. The photoinitiated crosslinking behavior of the acrylated polyesters under ultraviolet irradiation without the addition of any photoinitiator was investigated. The results showed that the precursor polyesters that had a greater number of terminated hydroxyls and a less branched structure obtained a relatively high acetylation degree. A longer chain of aliphatic dicarboxylic acids (ADCAs) and higher ADCA proportion lead to a relatively lower photopolymerization rate of acrylated polyesters. However, the photocured elastomers with a higher ADCA proportion or longer-chain ADCAs resulted in better mechanical properties and a lower degradation rate. The glass transition temperature (Tg) of the elastomer increased with the alkyl chain length of the ADCAs, and a higher Gly proportion resulted in a lower Tg of the elastomer due to its higher crosslinking density. Thermal gravimetric analysis (TGA) showed that the chain length of the ADCAs and the molar ratio of Gly to ADCAs had less of an effect on the thermal stability of the elastomer. As the physicochemical properties can be adjusted by choosing the alkyl chain length of the ADCAs, as well as changing the ratio of Gly:ADCA, the photocurable polyesters are expected to be applied in multiple fields.

Sustainable Vat Photopolymerization-Based 3D-Printing through Dynamic Covalent Network Photopolymers.

Vat photopolymerization (VPP) based three-dimensional (3D) printing, including stereolithography (SLA) and digital light projection (DLP), is known for producing intricate, high-precision prototypes with superior mechanical properties. However, the challenge lies in the non-recyclability of covalently crosslinked thermosets used in these printing processes, limiting the sustainable utilization of printed prototypes. This review paper examines the recently explored avenue of VPP 3D-printed dynamic covalent network (DCN) polymers, which enable reversible crosslinks and allow for the reprocessing of printed prototypes, promoting sustainability. These reversible crosslinks facilitate the rearrangement of crosslinked polymers, providing printed polymers with chemical/physical recyclability, self-healing capabilities, and degradability. While various mechanisms for DCN polymer systems are explored, this paper focuses solely on photocurable polymers to highlight their potential to revolutionize the sustainability of VPP 3D printing.

A shape-predictive model for the spreading of photo-curable polymers in material extrusion additive manufacturing

Recently, there is a growing interest in material extrusion to print thermoset resins to manufacture large format and high-performance parts. However, the fidelity and mechanical integrity of the printed parts are limited by challenges such as uncontrolled spreading of individual beads (filament/droplet) after deposition and during cure. There is a considerable lack of experimental and theoretical studies on the spreading of reactive beads on solid substrates. In this work, we studied the simultaneous spreading and photo-curing of the photopolymerizable thermoset beads via experiment and numerical simulations. We used a novel experimental setup to track the spreading of droplets and filaments during photopolymerization and validate a moving mesh computational fluid dynamics (CFD) model. The CFD model was used to develop an approach (predictive model) to accurately predict the final spreading coefficient of cured resin beads without the need for full numerical simulations. The predictive model combines the generalized theory of a Newtonian spreading filament with a characteristic viscosity μave and time to gelation, τgel. Interestingly, μave is shown to be a material parameter that does not depend on processing conditions, but only on the material’s chemorheology. The predictive model is tested against a wide range of chemorheology and cure kinetic parameters and found to be in excellent agreement with the full numerical CFD simulations. This work will be very useful in estimating the final shape of beads during the material extrusion printing process, as well as a model to successfully parameterize extrusion-based 3D printers to control the shape of printed beads a-priori.

Photocuring 3D Printing of Hydrogels: Techniques, Materials, and Applications in Tissue Engineering and Flexible Devices.

Photocuring 3D printing of hydrogels, with sophisticated, delicate structures and biocompatibility, attracts significant attention by researchers and possesses promising application in the fields of tissue engineering and flexible devices. After years of development, photocuring 3D printing technologies and hydrogel inks make great progress. Herein, the techniques of photocuring 3D printing of hydrogels, including direct ink writing (DIW), stereolithography (SLA), digital light processing (DLP), continuous liquid interface production (CLIP), volumetric additive manufacturing (VAM), and two photon polymerization (TPP) are reviewed. Further, the raw materials for hydrogel inks (photocurable polymers, monomers, photoinitiators, and additives) and applications in tissue engineering and flexible devices are also reviewed. At last, the current challenges and future perspectives of photocuring 3D printing of hydrogels are discussed.

Advanced 3D printing of graphene oxide nanocomposites: A new initiator system for improved dispersion and mechanical performance

The integration of nanoparticles, such as Graphene Oxide (GO), with photo-curable polymers in 3D printing has garnered significant interest in recent years due to the potential to create functional nanocomposite materials. This study explores the challenges of achieving optimal dispersion of GO nanoparticles within the polymer matrix and the crucial role of photoinitiators in overcoming these limitations. Traditional photoinitiators, like TPO, commonly used for GO/polymer resins, have raised concerns about high toxicity and limited sensitivity to visible light, prompting the need for alternative initiating systems. In this research, we propose a two-component initiator system based on bis-(4-t-butylphenyl)iodonium hexafluorophosphate and photosensitizer N-{4-[(E)-2-(pentafluorophenyl)ethenyl]phenyl}-2,1,3-benzothiadiazol-4-amine (IOD/PS1) as a promising solution. This new initiating system not only ensures a more environment-friendly resin but also exhibits enhanced polymerization kinetics and compatibility with GO nano fillers. This study investigated the effect of the addition of nano-GO on the kinetics of the radical photopolymerization process, 3D printing, and final mechanical and thermal properties of the received products. TPO and PEGDA/H2O were used as reference systems. In addition, a new two-component initiator system was synthesized, which is an interesting alternative to the commercial TPO initiator that is widely employed in additive techniques. This publication presents the research procedure involving various techniques: real-time FTIR and photoreology. In addition, the possibility of creating three-dimensional structures from the newly developed photo-curable resins was verified. Finally, the morphologies and mechanical properties of the resulting 3D structures were compared. Within the work, we demonstrate the advantages of the two-component initiator in achieving uniform distribution of GO and fabricating high-quality materials. By applying IOD/PS1 initiating system we facilitated a more controlled and efficient polymerization process, reducing shrinkage-induced stresses and enhancing interlayer bonding. The result was the fabrication of high-quality, well-dispersed materials with tailored properties suitable for various applications, particularly in the biomedical field.

Simultaneously Enhanced Chain Flexibility, Three Dimensional Printability, and Reduction of Shrinkage Stress in Biodegradable and Photocurable Multiblock Copolymers

A library of biodegradable and photocurable poly(propylene fumarate)-co-poly(trimethylene carbonate) (PPF-co-PTMC) multiblock copolymers encompassing the entire composition range and various block lengths has been designed and synthesized. By combining experiments and atomistic molecular dynamics simulations, we reveal the effects of chain architectures such as composition and block lengths on the thermal, rheological, and printing properties of these copolymers. The introduction of flexible PTMC blocks, which are found to be highly miscible with PPF blocks, into the unentangled copolymer backbone dramatically expedites chain relaxation, lowers the activation energy, and enhances the solubility in toluene. The chain flexibility of the copolymers is positively correlated with the composition of PTMC, while the block length of either PPF or PTMC affects little. Thus, lower values in glass transition temperature Tg, zero-shear viscosity η0, printing speed, and shrinkage stress in photocuring are consistently seen at higher compositions of PTMC. Photocurable PPF-co-PTMCs can be printed into high-precision 3D objects. This study provides a series of novel biopolymers and also a guideline to design photocurable polymers used in biomedical implants.

Gold metallization of hybrid organic-inorganic polymer microstructures 3D printed by two-photon polymerization

Two-photon polymerization is a femtosecond laser-based technique enabling printing of three-dimensional structures down to submicron resolution within photocurable polymers. Rendering the dielectric 3D printed structures conductive can be of great benefit for various applications in domains such as energy, photonics, or multifunctional devices. In this work, the microstructures of interest are made of a silicon-zirconium hybrid organic-inorganic polymer exhibiting low shrinkage during development. A simple and efficient metallization method by electroless plating is investigated to deposit a gold layer on the surface of the printed microstructures. The influence of the method parameters on the quality and properties of the deposited layer is studied. Among these parameters, the surface modification agent concentration and step duration, as well as the seeding solution concentration, must be adapted to the specific case of the considered hybrid microstructures. The concentration of metal ions in the plating bath is the most influential parameter on the morphology of the deposited gold layers. In particular, higher concentrations lead to smooth and continuous layers with electrical conductivities higher than half that of bulk gold. Finally, the deposited layers are shown to coat 3D printed microstructures of arbitrary shapes, thus confirming the conformality of the method at the micrometric scale.

Mechanical and surface properties of a 3D-printed dental resin reinforced with graphene

Objectives: Commercial photocurable polymers used in dental additive manufacturing still have mechanical limitations. The incorporation of graphene may provide interesting advantages in this field. This study aimed to evaluate in vitro the effect of adding graphene nanoparticles to a 3D-printed polymethylmethacrylate dental resin in terms of surface roughness, flexural properties, and hardness. Methods: A 3D-printed dental resin (Dental Sand, Harz Lab) was loaded with four different graphene nanoplatelet (Graphenest) concentrations: 0.01wt%, 0.1wt%, 0.25wt%, and 0.5wt%. The neat resin was used as the control group. The surface roughness was measured with a contact profilometer using bar-shaped specimens (50x10x4mm). The flexural strength of specimens (80x10x4mm) from each group was calculated using the 3-point bending test in a Universal Test Machine. Hardness shore D was measured using a manual durometer on round-shaped specimens (12x6mm). Data were evaluated using the Kruskall-Wallis test followed by post-hoc Bonferroni corrected pairwise inter-group comparisons. Statistical significance was set at p<0.05. Results: Graphene improved 3D-printed PMMA resin hardness with statistical significance at a concentration of 0.01wt% (p=0.043). Surface roughness increased with graphene concentrations above 0.01wt%, with statistically significant differences at 0.25wt% (p=0.006) and 0.5wt% (p=0.005) concentrations. Flexural properties worsened with increased graphene concentrations, and these differences were significant in the concentrations of 0.25wt% (p=0.028) and 0.5wt% (p=0.006). Conclusions: The use of graphene as a mechanical reinforcement nanomaterial seems to be viable at low concentrations without prejudice to the surface roughness of a 3D-printed polymethylmethacrylate resin.

Highly Porous Gas-Blown Hydrogels for Direct Cell Encapsulation with High Cell Viability.

Cell transplant therapies show potential as treatments for a large number of diseases. The encapsulation of cells within hydrogels is often used to mimic the extracellular matrix and protect cells from the body's immune response. However, cell encapsulation can be limited in terms of both scaffold size and cell viability due to poor nutrient and waste transport throughout the bulk of larger volume hydrogels. Strategies to address this issue include creating prevascularized or porous structured materials. For example, cell-laden hydrogels can be formed by porogen leaching or three-dimensional printing, but these techniques involve the use of multiple materials, long preparation times, and/or specialized equipment. Postfabrication cell seeding in porous scaffolds can result in inconsistent cell density throughout scaffold volumes and typically requires a bioreactor to ensure even cell distribution. In this study, we developed a highly cytocompatible direct cell encapsulation method during the rapid fabrication of porous hydrogels. Using sodium bicarbonate and citric acid as blowing agents, we employed photocurable polymers to produce highly porous materials within a matter of minutes. Cells were directly encapsulated within methacrylated poly(vinyl alcohol), poly(ethylene glycol), and gelatin hydrogels at viabilities as high as 93% by controlling solution variables, such as citric acid content, viscosity, pH, and curing time. Cell viability within the resulting porous constructs was high (>80%) over 14 days of analysis with multiple cell types. This work provides a simple, versatile, and tunable method for cell encapsulation within highly porous constructs that can be built upon in future work for the delivery of cell-based therapies. Impact Statement This simple method to obtain cell-laden hydrogel foams allows direct cell encapsulation within biomaterials without the need for porogens or microcarriers, while maintaining high cell viability. The successful encapsulation of multiple cell types into gas-blown hydrogels with varied chemistries shows the versatility of this method. While this work focuses on photocrosslinkable polymers, any quick gelling material could be used for foam fabrication in expansion of this work. The potential future impact of this work on the treatment of diseases and injuries that utilize cell therapies is wide-ranging.

Development of Bisphenol-A-Glycidyl-Methacrylate- and Trimethylolpropane-Triacrylate-Based Stereolithography 3D Printing Materials

The main advantages of the three-dimensional (3D) printing process are flexible design, rapid prototyping, multi-component structures, and minimal waste. For stereolithography (SLA) 3D printing, common photocurable polymers, such as bisphenol-A glycidyl methacrylate (Bis-EMA), trimethylolpropane triacrylate (TMPTMA), as well as urethane oligomers, have been widely used. For a successful 3D printing process, these photocurable polymers must satisfy several requirements, including transparency, a low viscosity, good mechanical strength, and low shrinkage post-ultraviolet curing process. Herein, we investigated SLA-type photocurable resins prepared using Bis-EMA, TMPTMA, and urethane oligomers. The flexural strength, hardness, conversion rate, output resolution, water absorption, and solubility of the printed materials were investigated. The degree of conversion of the printed specimens measured by infrared spectroscopy ranged from 30 to 60%. We also observed that 64-80 MPa of the flexural strength, 40-60 HV of the surface hardness, 15.6-29.1 MPa of the compression strength, and 3.3-14.5 MPa of the tensile strength. The output resolution was tested using three different structures comprising a series of columns (5-50 mm), circles (0.6-6 mm), and lines (0.2-5 mm). In addition, we used five different pigments to create colored resins and successfully printed complex models of the Eiffel Tower. The research on resins, according to the characteristics of these materials, will help in the design of new materials. These results suggests that acrylate-based resins have the potential for 3D printing.

Recent Advances in 3D Printing of Photocurable Polymers: Types, Mechanism, and Tissue Engineering Application.

The conversion of liquid resin into solid structures upon exposure to light of a specific wavelength is known as photopolymerization. In recent years, photopolymerization-based 3D printing has gained enormous attention for constructing complex tissue-specific constructs. Due to the economic and environmental benefits of the biopolymers employed, photo-curable 3D printing is considered an alternative method for replacing damaged tissues. However, the lack of suitable bio-based photopolymers, their characterization, effective crosslinking strategies, and optimal printing conditions are hindering the extensive application of 3D printed materials in the global market. This review highlights the present status of various photopolymers, their synthesis, and their optimization parameters for biomedical applications. Moreover, a glimpse of various photopolymerization techniques currently employed for 3D printing is also discussed. Furthermore, various naturally derived nanomaterials reinforced polymerization and their influence on printability and shape fidelity are also reviewed. Finally, the ultimate use of those photopolymerized hydrogel scaffolds in tissue engineering is also discussed. Taken together, it is believed that photopolymerized 3D printing has a great future, whereas conventional 3D printing requires considerable sophistication, and this review can provide readers with a comprehensive approach to developing light-mediated 3D printing for tissue-engineering applications.

Bio‐Based Piezo‐ and Thermoresistive Photocurable Sensing Materials from Acrylated Epoxidized Soybean Oil

AbstractBio‐based photocurable polymers are increasingly in demand as environmentally friendly materials for advanced applications. Together with functional fillers, these represent a next step for the generation of functional and active smart materials, compatible with additive manufacturing technologies. Herein, acrylated epoxidized soybean oil (AESO) mixed with different amounts of reduced graphene oxide (rGO) up to 6 wt% in order to obtain UV‐curable piezoresistive and thermoresistive materials, is reported. It is shown that the addition of rGO to AESO hinders the curing process, but always maintains double bond conversions higher than 50%. Composites are characterized by a good dispersion of micrometric filler clusters. Further, the thermal stabilities are close to 300 °C and crosslinking degrees are above 1.75 mmol cm–3. The Young modulus of the composites decreases with the addition of the rGO fillers, in particular for the higher filler contents, and electrical conductivities up to 0.13 S m–1 are obtained for the composites with the highest rGO content. UV‐curable composites with piezoresistive and thermoresistive responses suitable for applications are thus obtained, characterized by gauge factors around 26 for deformations up to 2% and maximum thermoresistive sensitivity of S = 0.43, values similar to the values obtained for petroleum‐based materials.

High-resolution and electrically conductive three-dimensional printing of carbon nanotube-based polymer composites enabled by solution intercalation

Incorporating multi-walled carbon nanotubes (MWCNT) as conductive nanofillers is attractive for improving electrical conductivity of 3D-printed photocurable polymers. However, poor dispersion of MWCNT in the resin significantly degrades electrical conductivity and dimensional accuracy. Herein, the rational strategy for promoting dispersion employing a solution intercalation method is presented, thereby contributing to high electrical conductivity and dimensional accuracy in stereolithography process. For the mask-image-projection-based stereolithography, optimal dispersion and corresponding curing conditions (e.g., UV dose) of the MWCNT-incorporated resin were investigated with respect to various concentration. Commercial polyurethane-based resin was used as a matrix mixed with varying MWCNT concentrations of up to 0.6 wt%; an electrical conductivity of 0.071 S/m was achieved while maintaining a high dimensional accuracy verified with the International Tolerance (IT) grade. Quantitative comparison of the dimensional accuracy using standardized benchmark artifact could prove the effectiveness of the developed methods on the 3D printing quality. Complex 3D metamaterial structures and micro-to-macro sized capacitive sensors have been fabricated to demonstrate their fine quality in terms of the conductivity and physical dimension. This work can highly improve the 3D-printing qualities in the nanocomposites with high concentration fillers, thereby extending their applications to multi-functional/multi-scale structures, such as metamaterials, sensing components, and mechanical interfaces.

Capturing Free-Radical Polymerization by Synergetic Ab Initio Calculations and Topological Reactive Molecular Dynamics.

Photocurable polymers are used ubiquitously in 3D printing, coatings, adhesives, and composite fillers. In the present work, the free radical polymerization of photocurable compounds is studied using reactive classical molecular dynamics combined with a dynamical approach of the nonequilibrium molecular dynamics (D-NEMD). Different concentrations of radicals and reaction velocities are considered. The mechanical properties of the polymer resulting from 1,6-hexanediol dimethacrylate systems are characterized in terms of viscosity, diffusion constant, and activation energy, whereas the topological ones through the number of cycles (polymer loops) and cyclomatic complexity. Effects like volume shrinkage and delaying of the gel point for increasing monomer concentration are also predicted, as well as the stress-strain curve and Young's modulus. Combining ab initio, reactive molecular dynamics, and the D-NEMD method might lead to a novel and powerful tool to describe photopolymerization processes and to original routes to optimize additive manufacturing methods relying on photosensitive macromolecular systems.

Thermal and dielectric properties enhancement of photocurable acrylate polymers for digital light processing 3D printed electronics

AbstractDigital light processing 3D printing has been rapidly evolving conventional manufacturing industry with the most meticulous resolution and strongest layer‐to‐layer adhesion among all additive manufacturing techniques. In this study, to improve poor polymer thermal stability and dielectric properties from prevailing methyl methacrylate‐based resin, tri‐functional trimethylolpropane tri‐acrylate (TMPTA) is introduced to form a stable polymer network. Meanwhile, monomers carrying non‐polar, bulky adamantane are added to eradicate poly‐TMPTA's notorious high cracking and warping tendency. Test results showed both high 1‐adamantyl methacrylate and 1, 3‐adamantyl di‐acrylate (ADDA) additions can print crack‐free samples. However, only ADDA addition keeps low CTE (82.86 ppm/oC, 200 ~ 260°C) and cuts down Df (0.02, 10 GHz). TMPTA polymer network modifications of both additions are explored. By contrast, poly‐MMA exhibits much higher CTE (323.44 ppm/oC) and Df (0.035). A 3D‐printed curvilinear circuit board from above resin formulation with electroplated copper circuits successfully passes lead‐free level reflow without deformation.

The three-component photoinitiating systems based on flavonol sulfonate and application in 3D printing

Three-dimensional (3D) printed photocurable shape-shifting polymers based on a three-component photoinitiated system (PIS) (flavonol sulfonate/triethanolamine/iodonium salt) were studied. The flavonol sulfonate (3HF–F) with charge transfer ability and long-wavelength absorption was designed and prepared using the Algar–Flynn–Oyamada method which is an important component of the oxidation–reduction PIS initiating the polymerization of polyethylene glycol (600) diacrylate (PEGDA) under 405 nm LED. For light absorption (active absorber) and electron/proton transfer, the three-component PIS has high-function conversion, and short induction period during the photopolymerization of PEGDA. As the same time, 3HF–F could also undergo passive absorption to obtain high-resolution DLP 3D-printed polymers. The printed polymers could be reversibly modified by means of hydrophilic and thermal responses caused by the stimuli-responsiveness of the polymer chains to activate the shifting of shape.

Three-Dimensional (3D) Printing Implemented by Computer-Generated Holograms for Generation of 3D Layered Images in Optical Near Field

Photocurable three-dimensional (3D) printing is a stepwise layer-by-layer fabrication process widely used in the manufacture of highly specialized objects. Current 3D printing techniques are easily implemented; however, the build rate is slow and the surface quality is less than ideal. Holographic 3D display (3DHD) technology makes it possible to reform planar wavefronts into a 3D intensity distribution, which appears as a 3D image in space. This paper examined the application of holographic imaging technology to 3D printing based on photocurable polymers. The proposed system uses a 3DHD diffractive optics system based on a liquid-crystal-on-silicon spatial light modulator (LCoS-SLM), wherein a 3D layered image is created in the optical near field, based on a computer-generated hologram (CGH) optimized using the iterative angular spectrum algorithm (IASA) and a circular IASA. From a single CGH, multiple 2D sliced images are created in space to form a 3D optical image used to initiate the photopolymerization of photocurable resin to form 3D objects. In experiments, the proposed 3D printing system was used to create five polymer objects with a maximum axial length of 25 mm and minimum feature width of 149 μm. The phase-only CGH reformed the incident light into a distribution of optical intensity with high diffraction efficiency suitable for photocuring. Despite limitations pertaining to fabrication area and axial complexity in this initial study, the proposed method demonstrated high light efficiency, high resolution in the lateral direction, rapid fabrication, and good object continuity.

The Effect of Heat Treatment toward Glycerol-Based, Photocurable Polymeric Scaffold: Mechanical, Degradation and Biocompatibility.

Photocurable polymers have become increasingly important for their quick prototyping and high accuracy when used in three dimensional (3D) printing. However, some of the common photocurable polymers are known to be brittle, cytotoxic and present low impact resistance, all of which limit their applications in medicine. In this study, thermal treatment was studied for its effect and potential applications on the mechanical properties, degradability and biocompatibility of glycerol-based photocurable polymers, poly(glycerol sebacate) acrylate (PGSA). In addition to the slight increase in elongation at break, a two-fold increase in both Young’s modulus and ultimate tensile strength were also observed after thermal treatment for the production of thermally treated PGSA (tPGSA). Moreover, the degradation rate of tPGSA significantly decreased due to the increase in crosslinking density in thermal treatment. The significant increase in cell viability and metabolic activity on both flat films and 3D-printed scaffolds via digital light processing-additive manufacturing (DLP-AM) demonstrated high in vitro biocompatibility of tPGSA. The histological studies and immune staining indicated that tPGSA elicited minimum immune responses. In addition, while many scaffolds suffer from instability through sterilization processes, it was proven that once glycerol-based polymers have been treated thermally, the influence of autoclaving the scaffolds were minimized. Therefore, thermal treatment is considered an effective method for the overall enhancement and stabilization of photocurable glycerol-based polymeric scaffolds in medicine-related applications.