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24 pages, 3020 KB  
Article
Thermomechanical Tailoring of a DLP-Printable Shape Memory Polyurethane for Vascular Graft Applications
by Ozan Azğüler and Mihrigül Ekşi Altan
Materials 2026, 19(9), 1862; https://doi.org/10.3390/ma19091862 - 1 May 2026
Viewed by 347
Abstract
The increasing prevalence of cardiovascular diseases highlights the need to develop vascular grafts that match the mechanics of native vascular tissue and offer functional adaptability. This study reports the development and systematic optimization of a shape-memory polyurethane acrylate (PUA)-based photocurable resin for digital [...] Read more.
The increasing prevalence of cardiovascular diseases highlights the need to develop vascular grafts that match the mechanics of native vascular tissue and offer functional adaptability. This study reports the development and systematic optimization of a shape-memory polyurethane acrylate (PUA)-based photocurable resin for digital light processing (DLP)-based four-dimensional printing (4DP) applications. Resin formulations were designed by controlling hard/soft segment ratios, reactive diluent content, and crosslink density to position the glass transition temperature (Tg) within the physiological range (25–40 °C). Thermomechanical characterization was performed via dynamic mechanical analysis (DMA) and tensile testing, while a full-factorial Design of Experiments (DoE) approach was applied to optimize DLP process parameters—namely layer thickness, exposure time, and post-curing time. The developed resin formulation yielded a Tg of 38 °C as determined by DMA. Following process optimization, regression models showed high statistical fit (R2 > 99%), and experimental validation under optimal conditions (layer thickness: 82.83 µm, exposure time: 11 s, post-curing: 2 min) resulted in an elongation at break of 64.0 ± 3.4%, a Young’s modulus of 10.9 ± 0.1 MPa, and a tensile strength of 6.2 ± 0.3 MPa. The optimized system exhibited thermally triggerable shape memory behavior at near-body temperature, with mechanical properties consistent with natural arterial tissue benchmarks. These findings demonstrate a promising material design strategy for DLP-based 4D-printed vascular structures. Full article
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20 pages, 3511 KB  
Article
Organic–Inorganic Triethylenediamine Cu(I)-Iodides as Reusable Photoluminescent Sensors for Waterborne Pollutants
by Victoria Martín, Giulia Bardelli, Julián Ávila Durán and Pilar Amo-Ochoa
Molecules 2026, 31(9), 1384; https://doi.org/10.3390/molecules31091384 - 22 Apr 2026
Viewed by 266
Abstract
Luminescent organic–inorganic Cu(I) halide hybrid molecular crystals exhibit remarkable structural diversity and photophysical properties, but their application in aqueous environments is often limited by insufficient stability. Herein, we report portable and reusable photoluminescent sensors based on Cu(I)–I triethylenediamine derivatives [Cu4I6 [...] Read more.
Luminescent organic–inorganic Cu(I) halide hybrid molecular crystals exhibit remarkable structural diversity and photophysical properties, but their application in aqueous environments is often limited by insufficient stability. Herein, we report portable and reusable photoluminescent sensors based on Cu(I)–I triethylenediamine derivatives [Cu4I6(pr-ted)2] and [Cu3I5(bz-ted)2] (pr-ted = 1-propyl-1,4-diazabicyclo[2.2.2]octan-1-ium; bz-ted = 1-benzyl-1,4-diazabicyclo[2.2.2]octan-1-ium). Their submicrometric particles exhibit intense UV-excited emissions and high photoluminescence quantum yields but limited water stability. To address this limitation, ultrasound sonication was employed to control particle size and produce stable suspensions that can be incorporated into polymeric matrices via 3D printing with photocurable resins or polylactic acid (PLA) films by drop-casting, yielding mechanically robust composites that retain their structural and optical properties. The devices used act as selective turn-off luminescent sensors for Fe3+ in aqueous media, with nanomolar detection limits (1.33–1.58 nM) below regulatory thresholds for drinking water. Moreover, [Cu3I5(bz-ted)2] enables tetracycline detection in river water with a limit of detection of 0.038 nM. Mechanistic studies indicate that reversible photoinduced electron transfer is the primary quenching pathway, while composites maintain sensing performance over multiple reuse cycles. Full article
(This article belongs to the Special Issue Innovative Catalysts and Multimodal Strategies for Water Remediation)
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25 pages, 27527 KB  
Article
Initial Study of Feedstock Material Compositions for 3D Printing of Hybrid Metal–Polymer Components via Electrodeposition and Photopolymerization in an Electroplating Bath Environment
by Dawid Kiesiewicz, Karolina Syrek, Paweł Niezgoda, Szymon Żydowski, Sylwia Łagan and Maciej Pilch
Molecules 2026, 31(8), 1316; https://doi.org/10.3390/molecules31081316 - 17 Apr 2026
Cited by 1 | Viewed by 362
Abstract
Hybrid metal–polymer components are used in many industries, such as in aerospace, automotives, and electronics, due to the possibility of reducing the weight of the final part while maintaining mechanical properties comparable to components made entirely of metal. Conventional 3D printing processes do [...] Read more.
Hybrid metal–polymer components are used in many industries, such as in aerospace, automotives, and electronics, due to the possibility of reducing the weight of the final part while maintaining mechanical properties comparable to components made entirely of metal. Conventional 3D printing processes do not enable the direct fabrication of hybrid structures consisting of solid metal and polymer parts due to the significant differences in the processing temperatures of both materials. A solution to this problem is the integration of two processes, electrodeposition and photopolymerization, which allow fabrication to be carried out at room temperature. This paper presents preparatory studies aimed at developing a new 3D printing technology that uses the simultaneous application of electrodeposition and photopolymerization to manufacture hybrid metal–polymer elements in a single, integrated 3D printing process. Here, a hybrid metal–polymer element is defined as a component composed of at least two bonded parts, including at least one metal part fabricated by electrodeposition and at least one polymer part produced by photopolymerization. Thus, it is not a polymer component merely coated with an electrodeposited metal layer, but a true hybrid structure consisting of functional metallic and polymeric parts. Such components can be manufactured using the world’s first hybrid 3D printer, which integrates electrodeposition and photopolymerization to produce metal–polymer hybrid parts within a single 3D printing process (the device has been submitted to the Polish Patent Office). However, its design and operating principle are beyond the scope of this paper. The presented research focuses on initial study of selected feedstock materials for this printer, namely photocurable resins and electroplating baths. Since the entire hybrid printing process occurs in an electroplating bath environment, studies of these materials for 3D printing under such conditions were essential. This work includes a screening study of photocurable formulations with respect to rheological properties, 3D printing tests in a model copper electroplating bath, and selection of a suitable bath brightener to maximize the quality (fine grain size, homogeneous grain distribution) of additively deposited copper layers. The study was conducted using copper electrodeposition and acrylate resin photopolymerization as model processes for evaluating the proposed hybrid metal–polymer 3D printing technology. Finally, the most suitable feedstock materials for producing metal–polymer hybrid parts via the proposed 3D printing method were selected. Full article
(This article belongs to the Special Issue 30th Anniversary of Molecules—Recent Advances in Electrochemistry)
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16 pages, 1392 KB  
Article
The Effect of PDMS Incorporation on the Physicochemical Properties of Acrylate-Based Resins for SLA-Based 3D Printing
by Yura Choi, Jayoung Hyeon, Jinyoung Kim, Eunsu Park and Namchul Cho
Polymers 2026, 18(7), 827; https://doi.org/10.3390/polym18070827 - 28 Mar 2026
Viewed by 1455
Abstract
A photo-curable silicone-modified resin system based on polydimethylsiloxane (PDMS) was developed and systematically evaluated for stereolithography (SLA)-based 3D printing applications. The resin formulation consisted of bisphenol A ethoxylate dimethacrylate (Bis-EMA) and trimethylolpropane triacrylate (TMPTMA) as reactive monomers, with methacrylate-terminated PDMS (PDMS-MMA) incorporated at [...] Read more.
A photo-curable silicone-modified resin system based on polydimethylsiloxane (PDMS) was developed and systematically evaluated for stereolithography (SLA)-based 3D printing applications. The resin formulation consisted of bisphenol A ethoxylate dimethacrylate (Bis-EMA) and trimethylolpropane triacrylate (TMPTMA) as reactive monomers, with methacrylate-terminated PDMS (PDMS-MMA) incorporated at concentrations ranging from 0 to 15 wt%. The influence of PDMS-MMA content on key physicochemical properties relevant to SLA processing, including viscosity, mechanical performance, thermal stability, optical transmittance, and curing shrinkage, was systematically investigated. Moderate incorporation of PDMS-MMA improved the mechanical flexibility of the resin, with the tensile strength reaching a maximum value of 5.95 MPa at 5 wt% PDMS-MMA. However, further increases in PDMS-MMA content resulted in a gradual decrease in tensile strength and optical transmittance, indicating the importance of optimizing the formulation composition. Thermogravimetric analysis (TGA) indicated improved thermal stability with increasing PDMS-MMA content, while curing shrinkage decreased progressively as the PDMS fraction increased. Structural printing tests confirmed that the developed resin system exhibited stable layer adhesion and shape fidelity during SLA fabrication, enabling the successful printing of complex three-dimensional structures. These results demonstrate that PDMS-modified acrylate resins provide a promising strategy for balancing mechanical flexibility, dimensional stability, and printability in SLA-based additive manufacturing. Full article
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24 pages, 375 KB  
Review
Next-Generation Orthodontics: Functional Resins, Biomechanics, Biocompatibility, and Current Clinical Reality of Direct 3D-Printed Aligners
by Yulong Zhang and Benjamin M. Wu
J. Funct. Biomater. 2026, 17(3), 129; https://doi.org/10.3390/jfb17030129 - 9 Mar 2026
Viewed by 1393
Abstract
The orthodontic landscape is currently witnessing a significant technological evolution with the emergence of direct 3D-printed aligners (DPAs), which promise to close the digital workflow loop by eliminating the geometric limitations and solid model waste inherent to traditional thermoformed clear aligners (TCAs). This [...] Read more.
The orthodontic landscape is currently witnessing a significant technological evolution with the emergence of direct 3D-printed aligners (DPAs), which promise to close the digital workflow loop by eliminating the geometric limitations and solid model waste inherent to traditional thermoformed clear aligners (TCAs). This review provides a comprehensive analysis of the material science governing this transition from inert thermoplastic sheets to reactive photocurable resins. We explore the fundamental chemistry of DPA materials, and the pivotal role of post-processing in ensuring mechanical integrity and biocompatibility. Beyond passive mechanics, this review highlights preclinical research in functional material engineering, detailing how experimental DPAs are being investigated for the integration of antibacterial agents, remineralization fillers, and drug delivery systems. Furthermore, we evaluate the limited but emerging clinical data on DPAs, contrasting their shape-memory properties and force delivery profiles with conventional appliances, while critically addressing emerging safety concerns regarding monomer elution and microplastic generation. We conclude that while DPA technology offers superior dimensional control, comprehensive life cycle assessments and long-term in vivo trials are essential to fully substantiate their clinical efficacy, overall sustainability, and potential as advanced orthodontic appliances. Full article
(This article belongs to the Special Issue Dental Biomaterials in Implantology and Orthodontics)
7 pages, 625 KB  
Proceeding Paper
Surface Hydrophilicity of Dental Copolymer Modified with Dimethacrylates Possessing Quaternary Ammonium Groups
by Patryk Drejka and Izabela Barszczewska-Rybarek
Eng. Proc. 2026, 124(1), 16; https://doi.org/10.3390/engproc2026124016 - 4 Feb 2026
Viewed by 269
Abstract
Dental composite reconstructive materials (DCRMs) used in caries treatment possess satisfactory functional properties but lack antimicrobial activity, which may lead to secondary caries. This research aimed to modify the DCRM matrix with urethane-dimethacrylate monomers derived from cycloaliphatic and aromatic diisocyanates bearing quaternary ammonium [...] Read more.
Dental composite reconstructive materials (DCRMs) used in caries treatment possess satisfactory functional properties but lack antimicrobial activity, which may lead to secondary caries. This research aimed to modify the DCRM matrix with urethane-dimethacrylate monomers derived from cycloaliphatic and aromatic diisocyanates bearing quaternary ammonium groups. The diisocyanates used were 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (CHMDI), and 1,1′-methylenebis(4-isocyanatobenzene) (MDI). As a result, eight modified copolymers were obtained and tested for the surface water contact angle (WCA), water sorption (WS), and water solubility (SL). The WCA results indicated predominantly hydrophilic surfaces, while the WS and SL values were generally satisfactory. Full article
(This article belongs to the Proceedings of The 6th International Electronic Conference on Applied Sciences)
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15 pages, 2307 KB  
Article
Navigation and Load Adaptability of a Flatworm-Inspired Soft Robot Actuated by Staggered Magnetization Structure
by Zixu Wang, Miaozhang Shen, Chunying Li, Pengcheng Li, Anran Zheng and Shuxiang Guo
Biomimetics 2026, 11(1), 41; https://doi.org/10.3390/biomimetics11010041 - 6 Jan 2026
Viewed by 852
Abstract
This study presents a magnetically actuated soft robot inspired by the peristaltic locomotion of flatworms, designed to replicate the biological locomotion of worms to achieve robust maneuverability. Fabricated entirely from photocurable soft resin, the robot features a flexible elastomeric body and two webbed [...] Read more.
This study presents a magnetically actuated soft robot inspired by the peristaltic locomotion of flatworms, designed to replicate the biological locomotion of worms to achieve robust maneuverability. Fabricated entirely from photocurable soft resin, the robot features a flexible elastomeric body and two webbed fins with embedded soft magnets. By applying a vertically oscillating magnetic field, the robot achieves forward crawling through the coordinated bending and lifting of fins, converting oscillating magnetic fields into continuous undulatory motion that mimics the gait of flatworms. The experimental results demonstrate that the system maintains consistent bidirectional velocities in the range of 4–7 mm/s on flat surfaces. Beyond linear locomotion, the robot demonstrates effective terrain adaptability, navigating complex topographies, including curved obstacles up to 16 times its body thickness, by autonomously adopting a high-lifting kinematic strategy to overcome gravitational resistance. Furthermore, load-carrying tests reveal that the robot can transport a 6 g payload without velocity degradation. These findings underscore the robot’s efficacy in overcoming mobility constraints, highlighting promising applications in fields requiring non-invasive intervention, such as biomedical capsule endoscopy and industrial pipeline inspection. Full article
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10 pages, 1806 KB  
Article
Deformation Behaviour of Optimised Three-Dimensional Axisymmetric Chiral Auxetic Structures
by Nejc Novak, Alen Grebo, Matej Borovinšek, Lovre Krstulović-Opara, Zoran Ren and Matej Vesenjak
Biomedicines 2025, 13(11), 2816; https://doi.org/10.3390/biomedicines13112816 - 18 Nov 2025
Viewed by 820
Abstract
Background/Objectives: Developing functional tissue constructs via 3D bioprinting relies heavily on scaffold architecture, demanding precise mechanical tunability and high-resolution feature fidelity. Methods: This paper presents a novel approach utilising photocurable resins and resin 3D printing to fabricate auxetic axisymmetric chiral structures (ACSs), which [...] Read more.
Background/Objectives: Developing functional tissue constructs via 3D bioprinting relies heavily on scaffold architecture, demanding precise mechanical tunability and high-resolution feature fidelity. Methods: This paper presents a novel approach utilising photocurable resins and resin 3D printing to fabricate auxetic axisymmetric chiral structures (ACSs), which can be used for advanced scaffold engineering. Results: The experimental tests showed that the optimised ACS (optACS) possess superior mechanical properties compared to their non-optimised counterpart. Both analysed structures possess an auxetic behaviour up to 40% longitudinal strain, with a Poisson’s ratio of about −0.1. Conclusions: This auxetic capability is promising for biomedical applications, particularly in developing enhanced stents or tissue scaffolds. Full article
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18 pages, 1595 KB  
Article
Effect of Nanosilica Fillers on Photopolymerisation Behaviour and Mechanical Performance of Dental Resin Composites
by Mariola Robakowska and Łukasz Gierz
Coatings 2025, 15(11), 1316; https://doi.org/10.3390/coatings15111316 - 11 Nov 2025
Cited by 2 | Viewed by 849
Abstract
The performance of dental composites is strongly dependent on the type and content of ceramic fillers incorporated into the resin matrix. In this study, the effect of nanosilica (NS) fillers on the curing kinetics, physicochemical, thermal, and mechanical properties of Bis-GMA/TEGDMA-based dental composites [...] Read more.
The performance of dental composites is strongly dependent on the type and content of ceramic fillers incorporated into the resin matrix. In this study, the effect of nanosilica (NS) fillers on the curing kinetics, physicochemical, thermal, and mechanical properties of Bis-GMA/TEGDMA-based dental composites was systematically investigated. A series of nanocomposites containing various weight fractions of NS was prepared and evaluated. The photocuring behaviour was analysed using differential scanning calorimetry (DSC), enabling the determination of polymerisation rate coefficients (propagation kp and bimolecular termination ktb) and double bond conversion. The presence of nanosilica was found to influence chain mobility, as evidenced by changes in glass transition temperature (Tg). Rheological measurements provided insight into viscosity changes induced by NS incorporation, while mechanical tests confirmed reinforcement effects. A moderate but statistically significant correlation was observed between the NS content and mechanical performance. The results obtained correlate the rheological, kinetic, thermal, and mechanical properties of multiple types of silica in a single resin system using a consistent methodology. In addition, the results highlight the role of nanosilica in the regulation of the curing dynamics and the increase in the mechanical integrity of methacrylate-based dental composites, representing a promising strategy for the development of next-generation restorative materials. Full article
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13 pages, 2407 KB  
Article
Mechanical Performance of Laminated Polymer Composites Fabricated via Stereolithography (SLA) 3D Printing
by Ans Al Rashid, Ambreen Afridi and Muammer Koç
Chemistry 2025, 7(6), 179; https://doi.org/10.3390/chemistry7060179 - 10 Nov 2025
Viewed by 1247
Abstract
Laminated polymer composites have emerged as a promising class of materials that provide exceptional mechanical and functional properties owing to multilayered architectures. In addition, additive manufacturing (AM) offers boundless opportunities to fabricate complex and intricate geometries with a wide variety of materials. Utilizing [...] Read more.
Laminated polymer composites have emerged as a promising class of materials that provide exceptional mechanical and functional properties owing to multilayered architectures. In addition, additive manufacturing (AM) offers boundless opportunities to fabricate complex and intricate geometries with a wide variety of materials. Utilizing AM processes for producing laminated polymer composites can open new pathways for producing these intricate structures with fine control over geometry, layer thickness, and material distribution. In this study, we demonstrate the use of the stereolithography (SLA) process to fabricate laminated polymer composites to overcome the limitations of extrusion-based AM processes, i.e., challenges in high precision, strong interlayer bonding and uniform particle distribution. Photocurable polymer composites were prepared by adding different reinforcing particles, i.e., cobalt iron oxide (CoFe2O4), graphene (G), magnesium (Mg) and iron (II,III) oxide (Fe3O4), into the photocurable resin. Ultrasonication and mechanical mixing processes were used to prepare stable photocurable composites suitable for the SLA process. SLA process was also optimized, varying the process parameters (exposure time, bottom exposure time and bottom layer count) to achieve optimum dimensional accuracy and surface quality. Microscopic analysis confirmed the distinct and well-adhered composite layer sandwiched between the unfilled resin, validating the structural integrity of the multilayer design. Mechanical testing revealed significant improvement in the tensile properties of the laminated composites compared to pure resin, with resin/CoFe2O4 exhibiting 35.6% and 50.1% improvement in tensile strength and Young’s modulus compared to the pure resin, respectively. These results highlight the feasibility of SLA for producing multilayered polymer composites with improved mechanical performance and controlled architecture, broadening its potential for advanced engineering and biomedical applications. Full article
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17 pages, 6471 KB  
Article
Bio-Adhesive Lignin-Reinforced Epoxy Acrylate (EA)-Based Composite as a DLP 3D Printing Material
by Jeonghong Ha and Jong Wan Ko
Polymers 2025, 17(21), 2833; https://doi.org/10.3390/polym17212833 - 23 Oct 2025
Viewed by 1612
Abstract
Digital light processing (DLP) 3D printing is a powerful additive manufacturing technique but is limited by the relatively low mechanical strength of cured neat resin parts. In this study, a renewable bio-adhesive lignin was introduced as a reinforcing filler into a bisphenol A-type [...] Read more.
Digital light processing (DLP) 3D printing is a powerful additive manufacturing technique but is limited by the relatively low mechanical strength of cured neat resin parts. In this study, a renewable bio-adhesive lignin was introduced as a reinforcing filler into a bisphenol A-type epoxy acrylate (EA) photocurable resin to enhance the mechanical performance of DLP-printed components. Lignin was incorporated at low concentrations (0–0.5 wt%), and three dispersion methods—magnetic stirring, planetary mixing, and ultrasonication—were compared to optimize the filler distribution. Cure depth tests and optical microscopy confirmed that ultrasonication (40 kHz, 5 h) achieved the most homogeneous dispersion, yielding a cure depth nearly matching that of the neat resin. DLP printing of tensile specimens demonstrated that as little as 0.025 wt% lignin increased tensile strength by ~39% (from 44.9 MPa to 62.2 MPa) compared to the neat resin, while maintaining similar elongation at break. Surface hardness also improved by over 40% at this optimal lignin content. However, higher lignin loadings (≥0.05 wt%) led to particle agglomeration, resulting in diminished mechanical gains and impaired printability (e.g., distortion and incomplete curing at 1 wt%). Fractographic analysis of broken specimens revealed that well-dispersed lignin particles act to deflect and hinder crack propagation, thereby enhancing fracture resistance. Overall, this work demonstrates a simple and sustainable approach to reinforce DLP 3D-printed polymers using biopolymer lignin, achieving significant improvements in mechanical properties while highlighting the value of bio-derived additives for advanced photopolymer 3D printing applications. Full article
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10 pages, 3119 KB  
Article
Printable Silicone-Based Emulsions as Promising Candidates for Electrically Conductive Glass-Ceramic Composites
by Annalaura Zilio and Enrico Bernardo
Crystals 2025, 15(10), 885; https://doi.org/10.3390/cryst15100885 - 14 Oct 2025
Cited by 1 | Viewed by 755
Abstract
The Na2O-SrO-SiO2 system shows promise in the development of glasses that can be transformed into electrically conductive glass ceramics. The conventional processing of such materials usually involves the synthesis of a parent glass, followed by a complex devitrification treatment. This [...] Read more.
The Na2O-SrO-SiO2 system shows promise in the development of glasses that can be transformed into electrically conductive glass ceramics. The conventional processing of such materials usually involves the synthesis of a parent glass, followed by a complex devitrification treatment. This study proposes a simplified approach based on the use of preceramic polymers, namely silicone resins combined with oxide fillers. These systems yield silicate-based ceramics through direct heat treatment, replicating the phase assembly of traditional glass ceramics with no need for prior glass melting. A printable formulation was developed by mixing a silicone resin with an acrylate-based photocurable resin, sodium nitrate and strontium carbonate. The resulting ‘suspension-emulsion’ was later shaped into monolithic components using digital light processing. After pyrolysis in nitrogen atmosphere, the components transformed into SrSiO3 crystals embedded in a composite matrix, in turn composed of glass and turbostratic carbon (the latter specifically offered by the silicone polymer). This combination of crystalline silicates and carbon resulted in measurable electrical conductivity. This study confirms that silicone-derived systems can serve as effective precursors for conductive glass-ceramic analogues, providing an alternative to conventional methods with single-step processing. This approach enables structural shaping through 3D printing and the development of functional properties suitable for electronic or electrochemical applications. Full article
(This article belongs to the Special Issue Advances in Glass-Ceramics)
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24 pages, 2527 KB  
Article
Three-Dimensional Printable Photocurable Elastomer Composed of Hydroxyethyl Acrylate and Hydroxy Fatty Acid Derived from Waste Cooking Oil: An Innovative Strategy for Sustainable, Highly Flexible Resin Development
by Fangping Shen, Chuanyang Tang, Yang Yang, Guangzhi Qin, Minghui Li, Haitian Jiang, Mengyao Wu and Shuoping Chen
Molecules 2025, 30(19), 4000; https://doi.org/10.3390/molecules30194000 - 6 Oct 2025
Viewed by 1286
Abstract
Waste cooking oil (WCO), a significant urban waste stream, presents untapped potential for synthesizing high-value materials. This study introduces an innovative “epoxidation-hydrolysis-blending” strategy to conveniently transform WCO into a highly flexible, photocurable elastomer suitable for 3D printing. Initially, WCO is converted into WCO-based [...] Read more.
Waste cooking oil (WCO), a significant urban waste stream, presents untapped potential for synthesizing high-value materials. This study introduces an innovative “epoxidation-hydrolysis-blending” strategy to conveniently transform WCO into a highly flexible, photocurable elastomer suitable for 3D printing. Initially, WCO is converted into WCO-based hydroxy fatty acids (WHFA) via epoxidation and hydrolysis, yielding linear chains functionalized with multiple hydrogen-bonding sites. Subsequently, blending WHFA with hydroxyethyl acrylate (HEA) yields a novel photocurable WHFA/HEA elastomer. This elastomer exhibits excellent dimensional accuracy during vat photopolymerization 3D printing. Within the WHFA/HEA system, WHFA acts as a dual-functional modifier: its flexible alkyl chains enhance conformational freedom through plasticization while serving as dynamic hydrogen-bonding cross-linking sites that synergize with HEA chains to achieve unprecedented flexibility via reversible bond reconfiguration. Mechanical testing reveals that the optimized WHFA/HEA elastomer (mass ratio 1:3) exhibits ultra-high flexibility, with an elongation at break of 1184.66% (surpassing pure HEA by 360%). Furthermore, the elastomer demonstrates significant weldability (44.23% elongation retention after 12 h at 25 °C), physical reprocessability (7.60% elongation retention after two cycles), pressure-sensitive adhesion (glass interface adhesion toughness: 32.60 J/m2), and notable biodegradability (14.35% mass loss after 30-day soil burial). These properties indicate broad application potential in flexible electronics, biomedical scaffolds, and related fields. This research not only pioneers a low-cost route to multifunctional photocurable 3D printing materials but also provides a novel, sustainable solution for the high-value valorization of waste cooking oil. Full article
(This article belongs to the Section Macromolecular Chemistry)
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20 pages, 5226 KB  
Article
Design and Performance of 3D-Printed Hybrid Polymers Exhibiting Shape Memory and Self-Healing via Acrylate–Epoxy–Thiol–Ene Chemistry
by Ricardo Acosta Ortiz, Alan Isaac Hernández Jiménez, José de Jesús Ku Herrera, Roberto Yañez Macías and Aida Esmeralda García Valdez
Polymers 2025, 17(19), 2594; https://doi.org/10.3390/polym17192594 - 25 Sep 2025
Cited by 2 | Viewed by 1678
Abstract
This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol [...] Read more.
This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing. Full article
(This article belongs to the Section Smart and Functional Polymers)
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15 pages, 2419 KB  
Article
Development and 3D Printing of AESO-Based Composites Containing Olive Pit Powder
by Giovanna Colucci, Francesca Sacchi, Marta Checchi, Marianna Barbalinardo, Francesca Chiarini, Federica Bondioli, Carla Palumbo and Massimo Messori
J. Compos. Sci. 2025, 9(9), 479; https://doi.org/10.3390/jcs9090479 - 3 Sep 2025
Cited by 1 | Viewed by 1389
Abstract
Bio-based polymeric composites were prepared by dispersing different amounts of olive pit (OP) powder within an acrylate epoxidized soybean oil (AESO) photocurable resin using tetrahydrofurfuryl acrylate (THFA) as diluent and (2,4,6-trimethylbenzoyl), phosphine oxide (BAPO) as photo-initiator, and they were photocured by Vat Photopolymerization [...] Read more.
Bio-based polymeric composites were prepared by dispersing different amounts of olive pit (OP) powder within an acrylate epoxidized soybean oil (AESO) photocurable resin using tetrahydrofurfuryl acrylate (THFA) as diluent and (2,4,6-trimethylbenzoyl), phosphine oxide (BAPO) as photo-initiator, and they were photocured by Vat Photopolymerization (VP) using a Liquid Crystal Display (LCD) 3D printer. Formulation viscosity was studied because of its important role in a VP process able to influence the printability of the final parts. Different 3D printed architectures were successfully realized with good resolution and accuracy, high level of detail, and flexibility. The effect of OP addition was investigated by thermal (TGA and DSC), morphological (SEM and PSD), viscoelastic (DMA), and mechanical (tensile testing) characterization. The filler led to an increase in the Tg, storage modulus, and tensile properties, underlining the stiffening effect induced by the OP particles onto the polymeric starting resin. This underlines the possibility to apply these bio-based composites in many application fields by valorizing agro-wastes, developing more sustainable materials, and taking advantages of VP 3D printing, such as low costs, minimal wastage, and customized geometry. Biocompatibility tests were also successfully carried out. The results clearly indicate that the AESO-based composites promote cell adhesion and viability. Full article
(This article belongs to the Special Issue Sustainable Polymer Composites: Waste Reutilization and Valorization)
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