Lin Chen, Meng‐Zhen Zhou, Ning Wang, Zhikai Tu, Yan‐Chan Wei, Shuangquan Liao
ABSTRACT In the conventional vulcanization of rubber, heavy reliance on zinc oxide (ZnO) results in resource waste and significant environmental pollution. Consequently, developing green and efficient strategies to reduce ZnO usage remains critical. In this study, lecithin, a bio‐based activator, is introduced into rubber to reduce ZnO usage during vulcanization. The addition of only 1.2 phr lecithin enables a 60% reduction in ZnO content while still maintaining the vulcanization efficiency and mechanical strength of natural rubber (NR). Notably, under reduced ZnO content, the NR sample with lecithin shows tensile strength increasing from 2.14 to 11.75 MPa compared to the sample without lecithin. Mechanistic investigations reveal that lecithin coordinates with Zn 2+ , which greatly improves dispersion of ZnO in the NR and enhances its utilization efficiency. Moreover, density functional theory (DFT) calculations confirm that lecithin‐Zn 2+ chelates increase the nucleophilicity of sulfur atoms in the accelerator toward elemental sulfur (S 8 ), lowering the Gibbs free energy for zinc polysulfide formation (Δ G is reduced from 71.59 to 55.68 kJ/mol) and accelerating vulcanization. In summary, lecithin acts as an effective bio‐based activator to enable a significant reduction in ZnO content without compromising the properties of NR. This approach provides a sustainable, efficient, and practical strategy for the development of low‐ZnO rubber composites.
{"title":"Mechanistic Investigation of Lecithin Enabled Efficient Vulcanization of Rubber With Reduced Zinc Oxide","authors":"Lin Chen, Meng‐Zhen Zhou, Ning Wang, Zhikai Tu, Yan‐Chan Wei, Shuangquan Liao","doi":"10.1002/pen.70343","DOIUrl":"https://doi.org/10.1002/pen.70343","url":null,"abstract":"ABSTRACT In the conventional vulcanization of rubber, heavy reliance on zinc oxide (ZnO) results in resource waste and significant environmental pollution. Consequently, developing green and efficient strategies to reduce ZnO usage remains critical. In this study, lecithin, a bio‐based activator, is introduced into rubber to reduce ZnO usage during vulcanization. The addition of only 1.2 phr lecithin enables a 60% reduction in ZnO content while still maintaining the vulcanization efficiency and mechanical strength of natural rubber (NR). Notably, under reduced ZnO content, the NR sample with lecithin shows tensile strength increasing from 2.14 to 11.75 MPa compared to the sample without lecithin. Mechanistic investigations reveal that lecithin coordinates with Zn 2+ , which greatly improves dispersion of ZnO in the NR and enhances its utilization efficiency. Moreover, density functional theory (DFT) calculations confirm that lecithin‐Zn 2+ chelates increase the nucleophilicity of sulfur atoms in the accelerator toward elemental sulfur (S 8 ), lowering the Gibbs free energy for zinc polysulfide formation (Δ G is reduced from 71.59 to 55.68 kJ/mol) and accelerating vulcanization. In summary, lecithin acts as an effective bio‐based activator to enable a significant reduction in ZnO content without compromising the properties of NR. This approach provides a sustainable, efficient, and practical strategy for the development of low‐ZnO rubber composites.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lili Zhao, JunShuai Xue, Dan Xing, Yubo Tao, J. Zhang, Fanjie Kong, Peng Li, Jianlong Wang, Ahmed Koubaa
ABSTRACT Polylactic acid (PLA), a degradational plastic, faces challenges in additive manufacturing due to high cost and low toughness. This study developed an innovative PLA random copolymer‐based composite system by incorporating maleic anhydride‐grafted polyethylene‐octene (MA‐POE) and bamboo powder to achieve a composite with low cost and superb mechanical strength for high‐speed 3D printing. Furthermore, a fused deposition modeling 3D‐printing approach was employed with a speed of 200 mm/s to enhance both processing efficiency and mechanical performance. The tensile and impact strength of the resulting composites increased by 33% and 24% after the incorporation of bamboo powders, respectively. The addition of MA‐POE significantly enhanced the toughness up to 17.36 KJ/m 2 , a 50% improvement compared to PLA/bamboo composites. Both bamboo powder and MA‐POE decreased the melt flow index from 67.2 g/10 min of pure PLA to 13.5 g/10 min of the resulting composites with 15% POE and 15% bamboo fiber. The entanglement effect of polymer molecular chains between PLA and bamboo powder, as well as MA‐POE, reduced die swell of the extruded filament, enabling more consistent strand dimensions, thereby improving printing accuracy and quality.
{"title":"Polyolefin Elastomer Toughened Polylactic Acid Composites With Low Extrusion Expansion for Quick Fused Deposition Modeling Additive Manufacturing","authors":"Lili Zhao, JunShuai Xue, Dan Xing, Yubo Tao, J. Zhang, Fanjie Kong, Peng Li, Jianlong Wang, Ahmed Koubaa","doi":"10.1002/pen.70309","DOIUrl":"https://doi.org/10.1002/pen.70309","url":null,"abstract":"ABSTRACT Polylactic acid (PLA), a degradational plastic, faces challenges in additive manufacturing due to high cost and low toughness. This study developed an innovative PLA random copolymer‐based composite system by incorporating maleic anhydride‐grafted polyethylene‐octene (MA‐POE) and bamboo powder to achieve a composite with low cost and superb mechanical strength for high‐speed 3D printing. Furthermore, a fused deposition modeling 3D‐printing approach was employed with a speed of 200 mm/s to enhance both processing efficiency and mechanical performance. The tensile and impact strength of the resulting composites increased by 33% and 24% after the incorporation of bamboo powders, respectively. The addition of MA‐POE significantly enhanced the toughness up to 17.36 KJ/m 2 , a 50% improvement compared to PLA/bamboo composites. Both bamboo powder and MA‐POE decreased the melt flow index from 67.2 g/10 min of pure PLA to 13.5 g/10 min of the resulting composites with 15% POE and 15% bamboo fiber. The entanglement effect of polymer molecular chains between PLA and bamboo powder, as well as MA‐POE, reduced die swell of the extruded filament, enabling more consistent strand dimensions, thereby improving printing accuracy and quality.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenxing Liu, Min Zhang, Xiaolin Zhao, Song Gao, Guangyong Liu
ABSTRACT This study investigated the effects of thermo‐oxidative aging on the swelling behavior and evolution of network structure for the brominated butyl rubber (BBR) and silicone rubber (SR) in lithium battery electrolytes through dynamic swelling kinetic tests. The swelling mechanism was elucidated combined with the Flory–Rehner theory and Flory–Huggins interaction parameter under simulated battery conditions, namely high‐temperature electrolyte immersion test. The results showed that thermo‐oxidative aging induced secondary crosslinking and caused a significantly increase in the crosslink density for BBR from 2.57 × 10 4 to 3.46 × 10 4 mol/cm 3 and SR from 6.14 × 10 4 to 6.75 × 10 4 mol/cm 3 . Despite the superior transport coefficients of SR due to its flexible siloxane chains, BBR exhibited an 11.2% higher swelling ratio at 80°C owing to the diminished elastic retraction of the crosslinking network. Furthermore, ethylene carbonate‐dominated electrolytes with higher polarity reduced the swelling by 18.3%–25.7% compared with that of Diethyl carbonate/Methyl ethyl carbonate ‐dominated electrolytes. It has been tried to correlate the swelling ratios of SR and BBR with the Flory–Huggins interaction parameter to quantify solvent compatibility and establish the theoretical guidance for predicting fluid resistance of battery seals.
{"title":"Swelling Kinetics and Flory–Huggins Interactions in Thermally Aged Brominated Butyl Rubber and Silicone Rubber","authors":"Zhenxing Liu, Min Zhang, Xiaolin Zhao, Song Gao, Guangyong Liu","doi":"10.1002/pen.70322","DOIUrl":"https://doi.org/10.1002/pen.70322","url":null,"abstract":"ABSTRACT This study investigated the effects of thermo‐oxidative aging on the swelling behavior and evolution of network structure for the brominated butyl rubber (BBR) and silicone rubber (SR) in lithium battery electrolytes through dynamic swelling kinetic tests. The swelling mechanism was elucidated combined with the Flory–Rehner theory and Flory–Huggins interaction parameter under simulated battery conditions, namely high‐temperature electrolyte immersion test. The results showed that thermo‐oxidative aging induced secondary crosslinking and caused a significantly increase in the crosslink density for BBR from 2.57 × 10 4 to 3.46 × 10 4 mol/cm 3 and SR from 6.14 × 10 4 to 6.75 × 10 4 mol/cm 3 . Despite the superior transport coefficients of SR due to its flexible siloxane chains, BBR exhibited an 11.2% higher swelling ratio at 80°C owing to the diminished elastic retraction of the crosslinking network. Furthermore, ethylene carbonate‐dominated electrolytes with higher polarity reduced the swelling by 18.3%–25.7% compared with that of Diethyl carbonate/Methyl ethyl carbonate ‐dominated electrolytes. It has been tried to correlate the swelling ratios of SR and BBR with the Flory–Huggins interaction parameter to quantify solvent compatibility and establish the theoretical guidance for predicting fluid resistance of battery seals.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147330989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yudong Lian, Cuicui Wang, Zhaolong Sun, Quan Ji, Jinglong Tang, Xiaomei Ma
ABSTRACT Hydrogels of exopolysaccharide gellan gum (GG) show great potential in biomedical areas. However, their weak mechanical properties and lack of functionality impede the practical applications. To address this, zeolitic imidazolate framework‐8 (ZIF‐8) nanoparticles were integrated into GG hydrogels via physical blending. X‐ray diffraction confirms the successful incorporation and even distribution of ZIF‐8 within the GG matrix. The novel composite hydrogels exhibit excellent mechanical properties without compromising the GG hydrogel's inherent thermoreversibility. Specifically, they achieve a maximum compressive strength and fracture energy of 0.85 MPa and 6.91 kJ·m −3 , and tensile strength and fracture energy of 95.09 kPa and 12.89 kJ·m −3 , respectively. They also display outstanding elasticity, resilience, and fatigue resistance, recovering approximately 86% after 10 compression cycles at 70% strain and over 70% after 10 stretching cycles at 200% strain. Notably, the composite hydrogels exhibit excellent swelling resistance in physiological saline, good biocompatibility, and enzymatic degradation by specific enzymes, with the equilibrium ratio lower than 56% and the minimum NIH3T3 cell viability higher than 86% after 24 h' incubation in the hydrogel extract. The excellent mechanics, eco‐friendliness, and unique thermoreversibility and rheological properties suggest their suitability for applications in biomedical fields like 3D printable and repairable tissue engineering materials.
{"title":"Biocompatible and Enzymatically Degradable Zeolitic Imidazolate Framework‐8 Reinforced Gellan Gum Hydrogels With Low Swelling in Physiological Saline","authors":"Yudong Lian, Cuicui Wang, Zhaolong Sun, Quan Ji, Jinglong Tang, Xiaomei Ma","doi":"10.1002/pen.70276","DOIUrl":"https://doi.org/10.1002/pen.70276","url":null,"abstract":"ABSTRACT Hydrogels of exopolysaccharide gellan gum (GG) show great potential in biomedical areas. However, their weak mechanical properties and lack of functionality impede the practical applications. To address this, zeolitic imidazolate framework‐8 (ZIF‐8) nanoparticles were integrated into GG hydrogels via physical blending. X‐ray diffraction confirms the successful incorporation and even distribution of ZIF‐8 within the GG matrix. The novel composite hydrogels exhibit excellent mechanical properties without compromising the GG hydrogel's inherent thermoreversibility. Specifically, they achieve a maximum compressive strength and fracture energy of 0.85 MPa and 6.91 kJ·m −3 , and tensile strength and fracture energy of 95.09 kPa and 12.89 kJ·m −3 , respectively. They also display outstanding elasticity, resilience, and fatigue resistance, recovering approximately 86% after 10 compression cycles at 70% strain and over 70% after 10 stretching cycles at 200% strain. Notably, the composite hydrogels exhibit excellent swelling resistance in physiological saline, good biocompatibility, and enzymatic degradation by specific enzymes, with the equilibrium ratio lower than 56% and the minimum NIH3T3 cell viability higher than 86% after 24 h' incubation in the hydrogel extract. The excellent mechanics, eco‐friendliness, and unique thermoreversibility and rheological properties suggest their suitability for applications in biomedical fields like 3D printable and repairable tissue engineering materials.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"66 2","pages":"1272-1283"},"PeriodicalIF":0.0,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/pen.70276","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heng Hu, Ru Liu, Yuhui Sun, Mingchang Zhang, Ling Long
ABSTRACT As the wood‐based panel market expands, impregnated paper is a key surface‐decoration material for furniture, flooring, and construction panels, with melamine‐formaldehyde (MF) adhesive‐impregnated paper prevailing for its adhesion, water resistance, and abrasion resistance. The intrinsic brittleness of MF adhesive, however, makes decorative plywood prone to surface cracking, and moisture fluctuations under hot–cold cycling or extreme climates further shorten service life. We synthesized a hyperbranched polysiloxane (HBPSi‐NH 2 ) from 3‐aminopropyltriethoxysilane (APTES) and 2‐methyl‐1,3‐propanediol (MPD) and used it to toughen MF adhesive. The modified MF adhesive‐impregnated paper was hot pressed onto plywood to evaluate the adhesive, the impregnated paper, and the resulting decorative plywood. Mechanistically, HBPSi‐NH 2 provides SiOC flexible segments that offer low‐energy rotational pathways, while surface SiOH groups form reversible hydrogen bonds with MF NH 2 and OH groups, creating recoverable energy‐dissipation units within the three‐dimensional network. This architecture strengthens HBPSi‐NH 2 /MF interfacial interactions and promotes stress redistribution and energy dissipation under tension, thereby enhancing toughness. At 2 wt% HBPSi‐NH 2 , the 4HBPSi‐NH 2 /MF adhesive‐impregnated paper reached 20.2% elongation at break, nearly double the neat MF counterpart (10.2%). After hot‐press lamination to plywood, the surface showed no detectable cracking. Collectively, these results demonstrate that HBPSi‐NH 2 effectively toughens MF adhesive and helps prevent cracking in decorative plywood.
{"title":"Super‐Tough Impregnating Adhesive and Its Impregnated Decorative Materials: Highly Crack‐Resistant Surface Layers Suitable for Extreme Climate Variations","authors":"Heng Hu, Ru Liu, Yuhui Sun, Mingchang Zhang, Ling Long","doi":"10.1002/pen.70265","DOIUrl":"https://doi.org/10.1002/pen.70265","url":null,"abstract":"ABSTRACT As the wood‐based panel market expands, impregnated paper is a key surface‐decoration material for furniture, flooring, and construction panels, with melamine‐formaldehyde (MF) adhesive‐impregnated paper prevailing for its adhesion, water resistance, and abrasion resistance. The intrinsic brittleness of MF adhesive, however, makes decorative plywood prone to surface cracking, and moisture fluctuations under hot–cold cycling or extreme climates further shorten service life. We synthesized a hyperbranched polysiloxane (HBPSi‐NH 2 ) from 3‐aminopropyltriethoxysilane (APTES) and 2‐methyl‐1,3‐propanediol (MPD) and used it to toughen MF adhesive. The modified MF adhesive‐impregnated paper was hot pressed onto plywood to evaluate the adhesive, the impregnated paper, and the resulting decorative plywood. Mechanistically, HBPSi‐NH 2 provides SiOC flexible segments that offer low‐energy rotational pathways, while surface SiOH groups form reversible hydrogen bonds with MF NH 2 and OH groups, creating recoverable energy‐dissipation units within the three‐dimensional network. This architecture strengthens HBPSi‐NH 2 /MF interfacial interactions and promotes stress redistribution and energy dissipation under tension, thereby enhancing toughness. At 2 wt% HBPSi‐NH 2 , the 4HBPSi‐NH 2 /MF adhesive‐impregnated paper reached 20.2% elongation at break, nearly double the neat MF counterpart (10.2%). After hot‐press lamination to plywood, the surface showed no detectable cracking. Collectively, these results demonstrate that HBPSi‐NH 2 effectively toughens MF adhesive and helps prevent cracking in decorative plywood.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"66 2","pages":"1128-1140"},"PeriodicalIF":0.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT The development of elastomer composite is persistently challenged by the difficulty in balancing its mutually conflicting properties, namely tensile strength, toughness, rolling resistance, wet skid resistance, and abrasion resistance. Inspired by ultrasound‐induced self‐strengthening strategies, this study developed high‐performance natural rubber (NR) composites by employing ultrasound to reconstruct the silica (SiO 2 ) filler network. The results demonstrated that appropriate ultrasonic treatment effectively broke down the original SiO 2 aggregates and facilitated the formation of a newly generated, more uniform filler network with a porous morphology. This reconstructed filler network was characterized by weakened filler‐filler interactions, evidenced by a reduced Payne effect, and significantly enhanced filler‐rubber interactions, indicated by an increase in bound rubber content from 31.7% to 43.9% and improved SiO 2 dispersion. Consequently, the optimized composite (NR/SiO 2 ‐P900‐A80) achieved a simultaneous enhancement in tensile strength (from 23.3 to 30.5 MPa) and toughness (from 47.1 to 79.0 J/cm 2 ). Remarkably, this method successfully improved wet skid resistance (tan δ at 0°C increased) and abrasion resistance (reduced abrasion volume from 0.87 to 0.57 cm 3 ) without compromising rolling resistance. This work presents a simple, effective, and industrially compatible ultrasound‐assisted strategy for fabricating high‐performance tread rubber by synergistically enhancing key properties through filler network reconstruction.
弹性体复合材料的发展一直面临着难以平衡其相互冲突的性能的挑战，即拉伸强度、韧性、抗滚动性、湿滑性和耐磨性。受超声诱导的自我强化策略的启发，本研究通过超声重建二氧化硅（sio2）填充网络，开发了高性能天然橡胶（NR）复合材料。结果表明，适当的超声处理有效地破坏了原有的sio2聚集体，促进了新生成的、更均匀的、具有多孔形态的填料网络的形成。这种重构的填料网络的特点是填料与填料之间的相互作用减弱，证明了Payne效应的降低；填料与橡胶之间的相互作用显著增强，表明结合橡胶的含量从31.7%增加到43.9%，并且改善了sio2的分散。因此，优化后的复合材料（NR/ sio2‐P900‐A80）的抗拉强度（从23.3提高到30.5 MPa）和韧性（从47.1提高到79.0 J/ cm2）同时得到了提高。值得注意的是，该方法在不影响滚动阻力的情况下成功地提高了湿滑性（0°C时的tan δ增加）和耐磨性（将磨损体积从0.87减少到0.57 cm 3）。这项工作提出了一种简单、有效和工业兼容的超声辅助策略，通过填充物网络重建协同提高关键性能来制造高性能胎面橡胶。
{"title":"Ultrasound‐Driven Filler Network Reconstruction for High‐Performance Self‐Strengthening Elastomer","authors":"Guixiang Liu, Yan‐Chan Wei, Zhikai Tu, Shuangquan Liao","doi":"10.1002/pen.70258","DOIUrl":"https://doi.org/10.1002/pen.70258","url":null,"abstract":"ABSTRACT The development of elastomer composite is persistently challenged by the difficulty in balancing its mutually conflicting properties, namely tensile strength, toughness, rolling resistance, wet skid resistance, and abrasion resistance. Inspired by ultrasound‐induced self‐strengthening strategies, this study developed high‐performance natural rubber (NR) composites by employing ultrasound to reconstruct the silica (SiO 2 ) filler network. The results demonstrated that appropriate ultrasonic treatment effectively broke down the original SiO 2 aggregates and facilitated the formation of a newly generated, more uniform filler network with a porous morphology. This reconstructed filler network was characterized by weakened filler‐filler interactions, evidenced by a reduced Payne effect, and significantly enhanced filler‐rubber interactions, indicated by an increase in bound rubber content from 31.7% to 43.9% and improved SiO 2 dispersion. Consequently, the optimized composite (NR/SiO 2 ‐P900‐A80) achieved a simultaneous enhancement in tensile strength (from 23.3 to 30.5 MPa) and toughness (from 47.1 to 79.0 J/cm 2 ). Remarkably, this method successfully improved wet skid resistance (tan δ at 0°C increased) and abrasion resistance (reduced abrasion volume from 0.87 to 0.57 cm 3 ) without compromising rolling resistance. This work presents a simple, effective, and industrially compatible ultrasound‐assisted strategy for fabricating high‐performance tread rubber by synergistically enhancing key properties through filler network reconstruction.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"66 2","pages":"1039-1046"},"PeriodicalIF":0.0,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT To date, shape memory polymer composites (SMPCs) have made significant progress in terms of material design, driving methods, and application fields. Despite these exciting achievements, the performance of most previous SMPCs remains suboptimal for realizing their full potential in stimuli‐responsive actuators due to their limited single‐stimulus responsiveness and restricted controlling capability. Herein, we report novel dual‐stimuli responsive SMPCs fabricated by embedding PDA@HNTs into a thermoplastic polyurethane (TPU) and poly (ε‐caprolactone) (PCL) blend. The incorporation of PDA@HNTs can not only endow TPU/PCL blends with photo‐thermal conversion capability, but also enhance thermally induced shape memory performance of SMPCs. Specifically, TPU50/PCL50‐PDA@HNTs‐2.0 blend exhibits superior dual shape memory property as manifested by shape fixing ratio of 99.3% and shape recovery ratio of 96.8% in water bath at 65°C, which takes only 10s for recovering permanent shape. Besides, under 808 nm NIR irradiation, the shape fixity ratio and shape recovery ratio of TPU50/PCL50‐PDA@HNTs‐2.0 blend can even reach 99.3% and 99.7%, respectively. More interestingly, we design a laminated‐structure composite to achieve tunable shape recovery time, which allows SMPCs to be customizable in different situations. This work may offer insights into the development of multiresponsive SMPCs, which expands the potential application of shape memory polymers.
{"title":"Dual‐Stimuli Shape Memory Thermoplastic Polyurethane/Poly (ε‐Caprolactone) Polymer Composites With Polydopamine‐Coated Halloysite Nanotubes for Enhanced Photo‐Responsive Actuation","authors":"Shilong Wang, Zhicheng Zhang, Yunhao Bao, Yun Chen Wu, Tianyi Wang, Pinghou Sheng, Simin Xu, Yun Ding","doi":"10.1002/pen.70237","DOIUrl":"https://doi.org/10.1002/pen.70237","url":null,"abstract":"ABSTRACT To date, shape memory polymer composites (SMPCs) have made significant progress in terms of material design, driving methods, and application fields. Despite these exciting achievements, the performance of most previous SMPCs remains suboptimal for realizing their full potential in stimuli‐responsive actuators due to their limited single‐stimulus responsiveness and restricted controlling capability. Herein, we report novel dual‐stimuli responsive SMPCs fabricated by embedding PDA@HNTs into a thermoplastic polyurethane (TPU) and poly (ε‐caprolactone) (PCL) blend. The incorporation of PDA@HNTs can not only endow TPU/PCL blends with photo‐thermal conversion capability, but also enhance thermally induced shape memory performance of SMPCs. Specifically, TPU50/PCL50‐PDA@HNTs‐2.0 blend exhibits superior dual shape memory property as manifested by shape fixing ratio of 99.3% and shape recovery ratio of 96.8% in water bath at 65°C, which takes only 10s for recovering permanent shape. Besides, under 808 nm NIR irradiation, the shape fixity ratio and shape recovery ratio of TPU50/PCL50‐PDA@HNTs‐2.0 blend can even reach 99.3% and 99.7%, respectively. More interestingly, we design a laminated‐structure composite to achieve tunable shape recovery time, which allows SMPCs to be customizable in different situations. This work may offer insights into the development of multiresponsive SMPCs, which expands the potential application of shape memory polymers.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"66 2","pages":"813-825"},"PeriodicalIF":0.0,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Sajjad, Muhammad Kamran, Salman Qadir, K. Ramki, S. Dharani, Shao‐Tao Bai
ABSTRACT Enhancing the flame retardancy and toughness of epoxy thermosets without compromising glass transition temperature ( T g ) or mechanical strength is a critical challenge. In this study, the graft copolymer, SEBS‐g‐PEG was prepared by chemically grafting polyethylene glycol (PEG) to the terminal blocks of polystyrene‐block‐poly(ethylene‐ co ‐butylene)‐block‐polystyrene (SEBS). These block copolymers (BCPs) along with various loading levels of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) were covalently incorporated into the epoxy thermosets to enhance their properties. The resulting composites exhibited excellent matrix compatibility, achieving up to a 200% improvement in fracture toughness and a 70% increase in flame retardancy at higher DOPO loadings (e.g., 8 wt%) without plasticizing effects. Notably, T g and tensile strength were preserved, enabling balanced high‐performance composites.
在不影响玻璃化转变温度（tg）或机械强度的情况下增强环氧热固性材料的阻燃性和韧性是一个关键的挑战。在本研究中，将聚乙二醇（PEG）化学接枝到聚苯乙烯-嵌段-聚（乙烯- co -丁烯）-嵌段-聚苯乙烯（SEBS）的末端嵌段上，制备了接枝共聚物SEBS - g - PEG。这些嵌段共聚物（bcp）与不同负载水平的9,10 -二氢- 9 -氧- 10 -磷酸菲- 10 -氧化物（DOPO）共价结合到环氧热固性树脂中，以提高其性能。所得到的复合材料表现出优异的基体相容性，在没有塑化效应的情况下，在更高DOPO负载（例如8 wt%）下，断裂韧性提高了200%，阻燃性提高了70%。值得注意的是，T g和抗拉强度保持不变，实现了高性能复合材料的平衡。
{"title":"Enhancing Toughness and Flame Retardancy of Epoxy Thermosets Using <scp>SEBS</scp> ‐g‐ <scp>PEG</scp> / <scp>DOPO</scp> Blends","authors":"Muhammad Sajjad, Muhammad Kamran, Salman Qadir, K. Ramki, S. Dharani, Shao‐Tao Bai","doi":"10.1002/pen.70232","DOIUrl":"https://doi.org/10.1002/pen.70232","url":null,"abstract":"ABSTRACT Enhancing the flame retardancy and toughness of epoxy thermosets without compromising glass transition temperature ( T g ) or mechanical strength is a critical challenge. In this study, the graft copolymer, SEBS‐g‐PEG was prepared by chemically grafting polyethylene glycol (PEG) to the terminal blocks of polystyrene‐block‐poly(ethylene‐ co ‐butylene)‐block‐polystyrene (SEBS). These block copolymers (BCPs) along with various loading levels of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) were covalently incorporated into the epoxy thermosets to enhance their properties. The resulting composites exhibited excellent matrix compatibility, achieving up to a 200% improvement in fracture toughness and a 70% increase in flame retardancy at higher DOPO loadings (e.g., 8 wt%) without plasticizing effects. Notably, T g and tensile strength were preserved, enabling balanced high‐performance composites.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"66 1","pages":"487-496"},"PeriodicalIF":0.0,"publicationDate":"2025-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331754","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Tri‐layered ASA core–shell toughening particles with controlled grafting ratios were synthesized to simultaneously improve the mechanical properties of poly(styrene‐co‐acrylonitrile) (SAN). Poly(butyl acrylate) (PBA) cores with different grafting agent distributions were synthesized via semicontinuous emulsion polymerization. ASA particles were then prepared by the grafting emulsion polymerization at different conditions. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) revealed particle sizes of 395–471 nm, uniform dispersion, and stable morphology. Samples with a moderate grafting ratio (11.5%) exhibited the best property balance, with 11.5 kJ/m 2 impact strength, 15% elongation at break, and a Vicat softening point of 101.2°C. At 0.15% t‐dodecyl mercaptan (TDDM) loading, rubber cores achieved optimal flexibility and stability, yielding the highest toughness. Incorporating 10% methyl methacrylate (MMA) increased the grafting ratio to 15.2%, improving whiteness (66%), brightness (91.3%), gloss (83.6%), and tensile strength (54 MPa); the toughening ability of ASA particles was limited when the grafting ratio reached certain levels. These findings demonstrate that controlling the tri‐layer core–shell architecture, TDDM concentration, and MMA fraction allows for simultaneous optimization of toughness, thermal stability, and surface properties in ASA resins.
合成了具有可控接枝率的三层ASA核壳增韧颗粒，同时改善了聚苯乙烯- co -丙烯腈（SAN）的力学性能。采用半连续乳液聚合法制备了不同接枝剂分布的聚丙烯酸丁酯（PBA）芯材。然后在不同条件下通过接枝乳液聚合法制备ASA颗粒。动态光散射（DLS）和扫描电子显微镜（SEM）显示，颗粒尺寸为395 ~ 471 nm，分散均匀，形貌稳定。中等接枝率（11.5%）的样品表现出最佳的性能平衡，其冲击强度为11.5 kJ/ m2，断裂伸长率为15%，维卡软化点为101.2℃。在0.15%的t -十二烷基硫醇（TDDM）载荷下，橡胶芯获得了最佳的柔韧性和稳定性，并产生了最高的韧性。加入10%的甲基丙烯酸甲酯（MMA）后，接枝率提高到15.2%，白度提高66%，亮度提高91.3%，光泽度提高83.6%，抗拉强度提高54 MPa；当接枝率达到一定水平时，ASA颗粒的增韧能力受到限制。这些发现表明，控制三层核壳结构、TDDM浓度和MMA分数可以同时优化ASA树脂的韧性、热稳定性和表面性能。
{"title":"Fabrication of Tri‐Layered Core‐Shell Structure Acrylonitrile–Styrene–Acrylate ( <scp>ASA</scp> ) Particles for Toughening Poly(Styrene‐Co‐Acrylonitrile) Resin","authors":"Xinyu Yao, Haowei Shen, Baijun Liu, Mingyao Zhang","doi":"10.1002/pen.70195","DOIUrl":"https://doi.org/10.1002/pen.70195","url":null,"abstract":"ABSTRACT Tri‐layered ASA core–shell toughening particles with controlled grafting ratios were synthesized to simultaneously improve the mechanical properties of poly(styrene‐co‐acrylonitrile) (SAN). Poly(butyl acrylate) (PBA) cores with different grafting agent distributions were synthesized via semicontinuous emulsion polymerization. ASA particles were then prepared by the grafting emulsion polymerization at different conditions. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) revealed particle sizes of 395–471 nm, uniform dispersion, and stable morphology. Samples with a moderate grafting ratio (11.5%) exhibited the best property balance, with 11.5 kJ/m 2 impact strength, 15% elongation at break, and a Vicat softening point of 101.2°C. At 0.15% t‐dodecyl mercaptan (TDDM) loading, rubber cores achieved optimal flexibility and stability, yielding the highest toughness. Incorporating 10% methyl methacrylate (MMA) increased the grafting ratio to 15.2%, improving whiteness (66%), brightness (91.3%), gloss (83.6%), and tensile strength (54 MPa); the toughening ability of ASA particles was limited when the grafting ratio reached certain levels. These findings demonstrate that controlling the tri‐layer core–shell architecture, TDDM concentration, and MMA fraction allows for simultaneous optimization of toughness, thermal stability, and surface properties in ASA resins.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"66 1","pages":"140-150"},"PeriodicalIF":0.0,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Double‐network hydrogels exhibit extensive applications within the biomedical domain, encompassing various aspects such as tissue engineering, drug delivery systems, and wound dressings. Their notable characteristics, including high mechanical strength, superior adhesiveness, exceptional water retention capacity, and antibacterial properties, offer innovative solutions for numerous challenges faced in the biomedical field. In this study, tannic acid (TA) was employed as a crosslinking agent, and mixed solutions of water and glycerol with different mass ratios were adopted, resulting in the successful synthesis of a polyvinyl alcohol (PVA)/gelatin (GEL) organic hydrogel with remarkable mechanical properties. The incorporation of TA facilitates the formation of robust hydrogen bonds with the PVA chains, thereby enhancing the mechanical strength of the hydrogel. The maximum tensile strength, elongation at break, and toughness value of the hydrogel are 2.5 MPa, 800%, and 1.1 MJ/m 3 . The lap shear adhesive performance test demonstrated that the hydrogel possesses excellent adhesion properties, capable of adhering to various substrates (with the highest adhesion strength observed on wood, reaching 76.8 kPa). Furthermore, the hydrogel can adhere to skin without leaving any residue upon removal. Results from in vitro coagulation tests revealed that the hydrogel fortified with TA effectively promotes blood coagulation on its surface. Antibacterial tests indicated that the TA‐containing organic hydrogel exhibits a significant inhibitory effect on Staphylococcus aureus . Additionally, TA can be gradually released from the hydrogel into a phosphate‐buffered saline (PBS) solution. Consequently, TA‐loaded hydrogels hold promising potential for application as wound dressings.
{"title":"The Drug‐Loaded Dual‐Network Hydrogels Possessing Both Adhesive and Antibacterial Properties for Skin Dressings","authors":"X. Chen, Huirong Li, Huiqing Liu, Shida Feng, Shuai Wang, Shaokang Fang, Yong Yuan, Xue Wang, Jintong Li, Yue Yu, Hong Zhang, Jing Guo","doi":"10.1002/pen.70173","DOIUrl":"https://doi.org/10.1002/pen.70173","url":null,"abstract":"ABSTRACT Double‐network hydrogels exhibit extensive applications within the biomedical domain, encompassing various aspects such as tissue engineering, drug delivery systems, and wound dressings. Their notable characteristics, including high mechanical strength, superior adhesiveness, exceptional water retention capacity, and antibacterial properties, offer innovative solutions for numerous challenges faced in the biomedical field. In this study, tannic acid (TA) was employed as a crosslinking agent, and mixed solutions of water and glycerol with different mass ratios were adopted, resulting in the successful synthesis of a polyvinyl alcohol (PVA)/gelatin (GEL) organic hydrogel with remarkable mechanical properties. The incorporation of TA facilitates the formation of robust hydrogen bonds with the PVA chains, thereby enhancing the mechanical strength of the hydrogel. The maximum tensile strength, elongation at break, and toughness value of the hydrogel are 2.5 MPa, 800%, and 1.1 MJ/m 3 . The lap shear adhesive performance test demonstrated that the hydrogel possesses excellent adhesion properties, capable of adhering to various substrates (with the highest adhesion strength observed on wood, reaching 76.8 kPa). Furthermore, the hydrogel can adhere to skin without leaving any residue upon removal. Results from in vitro coagulation tests revealed that the hydrogel fortified with TA effectively promotes blood coagulation on its surface. Antibacterial tests indicated that the TA‐containing organic hydrogel exhibits a significant inhibitory effect on Staphylococcus aureus . Additionally, TA can be gradually released from the hydrogel into a phosphate‐buffered saline (PBS) solution. Consequently, TA‐loaded hydrogels hold promising potential for application as wound dressings.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 12","pages":"6890-6903"},"PeriodicalIF":0.0,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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