Pub Date : 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111897
Ziying Zheng , Keqing Zhou , Changhao Wang , Yulun Zhang , Bin Yu , Sheng Zhang
Epoxy resin (EP) is extensively employed in construction on account of its exceptional comprehensive performance. However, its inherent fire hazards and insufficient mechanical properties pose significant safety issues. In this study, a CPM (CeHPP@PDA@MoS₂) hybrid material with hierarchical architectures was constructed using electrostatically driven self-assembly technology. Following the introduction of 2D rare-earth metal phenylphosphate (CeHPP) into the graphene analogue MoS₂ via PDA surface functionalization, the PDA-induced hierarchical structure effectively mitigated the stacking and re-agglomeration of MoS₂. Moreover, it significantly enhanced the interfacial adhesion between MoS₂ and EP, thus leading to notable improvements in the thermal stability, flame retardancy, and mechanical performance of EP composites. Relative to pure EP, the peak heat release rate (PHRR), total heat release (THR), peak smoke production rate (PSPR), and total smoke production (TSP) of the EP/CPM 2.0 composite showed marked decreases, by 46.6 %, 21.1 %, 39.8 %, and 45.4 %, respectively. Furthermore, the char yield of the EP composites demonstrated a growth to 25 %, up from an initial 7 %. The flexural and tensile strengths of the EP/CPM 2.0 composites were reinforced by 40.8 % and 31.6 %, respectively. The flame retardant and mechanical reinforcement mechanisms were explored. This research identifies a novel methodological avenue for engineering high-performance epoxy composites.
{"title":"Construction of hierarchical architectures with 2D rare earth metal phenylphosphate and graphene analogues for high-performance flame-retardant epoxy composites","authors":"Ziying Zheng , Keqing Zhou , Changhao Wang , Yulun Zhang , Bin Yu , Sheng Zhang","doi":"10.1016/j.polymdegradstab.2025.111897","DOIUrl":"10.1016/j.polymdegradstab.2025.111897","url":null,"abstract":"<div><div>Epoxy resin (EP) is extensively employed in construction on account of its exceptional comprehensive performance. However, its inherent fire hazards and insufficient mechanical properties pose significant safety issues. In this study, a CPM (CeHPP@PDA@MoS₂) hybrid material with hierarchical architectures was constructed using electrostatically driven self-assembly technology. Following the introduction of 2D rare-earth metal phenylphosphate (CeHPP) into the graphene analogue MoS₂ via PDA surface functionalization, the PDA-induced hierarchical structure effectively mitigated the stacking and re-agglomeration of MoS₂. Moreover, it significantly enhanced the interfacial adhesion between MoS₂ and EP, thus leading to notable improvements in the thermal stability, flame retardancy, and mechanical performance of EP composites. Relative to pure EP, the peak heat release rate (PHRR), total heat release (THR), peak smoke production rate (PSPR), and total smoke production (TSP) of the EP/CPM 2.0 composite showed marked decreases, by 46.6 %, 21.1 %, 39.8 %, and 45.4 %, respectively. Furthermore, the char yield of the EP composites demonstrated a growth to 25 %, up from an initial 7 %. The flexural and tensile strengths of the EP/CPM 2.0 composites were reinforced by 40.8 % and 31.6 %, respectively. The flame retardant and mechanical reinforcement mechanisms were explored. This research identifies a novel methodological avenue for engineering high-performance epoxy composites.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111897"},"PeriodicalIF":7.4,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111881
Shuangjiang He , Zhong Zeng , Hui Liu , Shaowei Chen , Lin Gan , Youquan Ling , Shuai Li , Long Ni , Xiaowen Zhao , Mei Liang , Yang Chen , Huawei Zou
To overcome the inherent limitations of conventional low-molecular-weight antioxidants for rubber, such as pronounced migration propensity, inadequate long-term antioxidative efficiency, and potential toxicological or environmental hazards, this work, for the first time, reports the synthesis of a biomass-derived poly(tannic acid)-based antioxidant (PTRB) featuring hierarchical antioxidative moieties (aniline groups from N-phenyl-p-phenylenediamine, phenolic hydroxyls from tannic acid, and thioether-based secondary antioxidative moieties from 2-mercaptobenzimidazole). Comprehensive characterizations, which combining experimental methodologies, molecular dynamics (MD) simulations, and quantum mechanics (QM) simulations, elucidated the regulatory roles of PTRB on the thermo-oxidative aging resistance, solubility, dispersibility, diffusivity, and protective mechanisms of nitrile butadiene rubber (NBR). In comparison with commercial antioxidants, PTRB significantly enhances the aging resistance of NBR composites, with the aging performance exhibiting improvements ranging from 24% to 267% (quantified by the aging coefficient K following accelerated aging at 121°C for 120 h). QM simulations demonstrated that the aniline moiety significantly enhances the radical-scavenging capacity of the PTRB. Meanwhile, the thioether moiety offers additional synergistic protection through the degradation of peroxyl radicals (ROO·) into stable alcohols. MD simulations further confirmed that the PTRB/NBR composites display superior interfacial interactions, resulting in higher binding energy. This, in turn, this improves the solubility and dispersibility of PTRB within the NBR matrix and reduces its diffusion coefficient. Furthermore, PTRB effectively promotes the vulcanization of NBR by regulating the sulfide cross-linking structure and further enhances the interfacial compatibility between the filler and the rubber. Consequently, this study introduces a sustainable, biomass-derived, multi-mechanistic antioxidant. This antioxidant possesses considerable significance for the fabrication of NBR composites with long-term and high aging resistance, thereby addressing the crucial challenges encountered by conventional low-molecular-weight antioxidants in practical applications.
{"title":"Multi-mechanism biomass-derived poly(tannic acid)-based antioxidant (PTRB) for enhanced the thermo-oxidative resistance of NBR: Insights from experiments and molecular simulations","authors":"Shuangjiang He , Zhong Zeng , Hui Liu , Shaowei Chen , Lin Gan , Youquan Ling , Shuai Li , Long Ni , Xiaowen Zhao , Mei Liang , Yang Chen , Huawei Zou","doi":"10.1016/j.polymdegradstab.2025.111881","DOIUrl":"10.1016/j.polymdegradstab.2025.111881","url":null,"abstract":"<div><div>To overcome the inherent limitations of conventional low-molecular-weight antioxidants for rubber, such as pronounced migration propensity, inadequate long-term antioxidative efficiency, and potential toxicological or environmental hazards, this work, for the first time, reports the synthesis of a biomass-derived poly(tannic acid)-based antioxidant (PTRB) featuring hierarchical antioxidative moieties (aniline groups from N-phenyl-p-phenylenediamine, phenolic hydroxyls from tannic acid, and thioether-based secondary antioxidative moieties from 2-mercaptobenzimidazole). Comprehensive characterizations, which combining experimental methodologies, molecular dynamics (MD) simulations, and quantum mechanics (QM) simulations, elucidated the regulatory roles of PTRB on the thermo-oxidative aging resistance, solubility, dispersibility, diffusivity, and protective mechanisms of nitrile butadiene rubber (NBR). In comparison with commercial antioxidants, PTRB significantly enhances the aging resistance of NBR composites, with the aging performance exhibiting improvements ranging from 24% to 267% (quantified by the aging coefficient <em>K</em> following accelerated aging at 121°C for 120 h). QM simulations demonstrated that the aniline moiety significantly enhances the radical-scavenging capacity of the PTRB. Meanwhile, the thioether moiety offers additional synergistic protection through the degradation of peroxyl radicals (ROO·) into stable alcohols. MD simulations further confirmed that the PTRB/NBR composites display superior interfacial interactions, resulting in higher binding energy. This, in turn, this improves the solubility and dispersibility of PTRB within the NBR matrix and reduces its diffusion coefficient. Furthermore, PTRB effectively promotes the vulcanization of NBR by regulating the sulfide cross-linking structure and further enhances the interfacial compatibility between the filler and the rubber. Consequently, this study introduces a sustainable, biomass-derived, multi-mechanistic antioxidant. This antioxidant possesses considerable significance for the fabrication of NBR composites with long-term and high aging resistance, thereby addressing the crucial challenges encountered by conventional low-molecular-weight antioxidants in practical applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111881"},"PeriodicalIF":7.4,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-27DOI: 10.1016/j.polymdegradstab.2025.111899
Nannan Xu , Jizhe Xiao , Zheng Kuang , Tian Niu , Na Zhang , Yuetao Liu , Chuanhui Gao
Poly(vinyl chloride) (PVC) is inherently rigid due to strong interchain dipole–dipole interactions, and therefore requires plasticizers to improve its flexibility and processability. Conventional small-molecule plasticizers such as dioctyl phthalate (DOP) and tributyl citrate (TBC) offer high plasticizing efficiency but suffer from severe migration and poor flame retardancy. In this study, phosphate groups were introduced via a phosphorus oxychloride–hydroxyl substitution strategy, and the plasticizing behavior was further tuned by tailoring the ester-bond density to achieve a synergy between flexibility and flame retardancy. Results reveal that a balanced distribution of polar groups is crucial for effective plasticization: overly dense polar sites restrict chain mobility, whereas overly sparse sites weaken interfacial interactions. Polyester plasticizer poly(butylene adipate) (PBA), featuring an optimal balance of polarity and chain flexibility, increased the plasticizing efficiency to 156.8% and enabled simultaneous enhancement of tensile strength and elongation. After incorporating phosphate units, the efficiency further rose to 172.7%, while the limiting oxygen index improved from 28% to 32%. The synergistic interactions between ester and P=O groups effectively attenuate PVC dipole–dipole forces, promote chain unlocking, and thus realize cooperative improvements in flexibility and flame retardancy. This work provides new insight for developing high-efficiency flame-retardant PVC plasticizers.
{"title":"Performance-synergistic polyester plasticizers for achieving a flexibility–flame-retardancy balance in PVC","authors":"Nannan Xu , Jizhe Xiao , Zheng Kuang , Tian Niu , Na Zhang , Yuetao Liu , Chuanhui Gao","doi":"10.1016/j.polymdegradstab.2025.111899","DOIUrl":"10.1016/j.polymdegradstab.2025.111899","url":null,"abstract":"<div><div>Poly(vinyl chloride) (PVC) is inherently rigid due to strong interchain dipole–dipole interactions, and therefore requires plasticizers to improve its flexibility and processability. Conventional small-molecule plasticizers such as dioctyl phthalate (DOP) and tributyl citrate (TBC) offer high plasticizing efficiency but suffer from severe migration and poor flame retardancy. In this study, phosphate groups were introduced via a phosphorus oxychloride–hydroxyl substitution strategy, and the plasticizing behavior was further tuned by tailoring the ester-bond density to achieve a synergy between flexibility and flame retardancy. Results reveal that a balanced distribution of polar groups is crucial for effective plasticization: overly dense polar sites restrict chain mobility, whereas overly sparse sites weaken interfacial interactions. Polyester plasticizer poly(butylene adipate) (PBA), featuring an optimal balance of polarity and chain flexibility, increased the plasticizing efficiency to 156.8% and enabled simultaneous enhancement of tensile strength and elongation. After incorporating phosphate units, the efficiency further rose to 172.7%, while the limiting oxygen index improved from 28% to 32%. The synergistic interactions between ester and <em>P</em>=<em>O</em> groups effectively attenuate PVC dipole–dipole forces, promote chain unlocking, and thus realize cooperative improvements in flexibility and flame retardancy. This work provides new insight for developing high-efficiency flame-retardant PVC plasticizers.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111899"},"PeriodicalIF":7.4,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922156","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-25DOI: 10.1016/j.polymdegradstab.2025.111886
Songbo Zhang , Lingfeng Dan , Jincheng Zhang , Mingxu Wu , Pibo Liu , Qizhou Yu , Yanming Hu
Despite significant progress in vitrimer technology, it remains highly challenging to integrate excellent mechanical properties, desired creep-resistance, and flame retardancy. Herein, we report a reprocessable ethylene vinyl acetate (EVA) vitrimer that simultaneously achieves these properties, fabricated by reactive blending of commercial amino-functionalized siloxane (APTS) with a hybrid aluminum diethyl phosphinate/ammonium polyphosphate (ADP/APP) flame-retardant system. The ADP/APP system and the cross-linker APTS exhibited a synergistic interplay that ADP/APP accelerated the formation of the dynamic silyl-ether network, while APTS concurrently improved the dispersion of the ADP/APP within the EVA matrix. Through optimization of the flame-retardant formulation, the resulting EVA/APTS/ADP9APP21 vitrimer exhibits an 80% increase in tensile strength (8.1 MPa) compared with the raw EVA, and achieves a UL-94 V-0 rating, exceptional creep resistance with a mere 2.1% permanent deformation at 150 °C. Furthermore, the EVA vitrimer displays excellent reprocessability and recyclability, with retaining nearly identical mechanical properties and V-0 flame retardancy after three recycling cycles. This work offers a viable strategy for creating high-performance vitrimer with integrated mechanical robustness, creep resistance, reprocessability, and fire safety, which is expected to significantly expedite the practical application of vitrimer.
{"title":"A self-catalyzed cross-linking strategy for recyclable and fire-safe EVA vitrimer","authors":"Songbo Zhang , Lingfeng Dan , Jincheng Zhang , Mingxu Wu , Pibo Liu , Qizhou Yu , Yanming Hu","doi":"10.1016/j.polymdegradstab.2025.111886","DOIUrl":"10.1016/j.polymdegradstab.2025.111886","url":null,"abstract":"<div><div>Despite significant progress in vitrimer technology, it remains highly challenging to integrate excellent mechanical properties, desired creep-resistance, and flame retardancy. Herein, we report a reprocessable ethylene vinyl acetate (EVA) vitrimer that simultaneously achieves these properties, fabricated by reactive blending of commercial amino-functionalized siloxane (APTS) with a hybrid aluminum diethyl phosphinate/ammonium polyphosphate (ADP/APP) flame-retardant system. The ADP/APP system and the cross-linker APTS exhibited a synergistic interplay that ADP/APP accelerated the formation of the dynamic silyl-ether network, while APTS concurrently improved the dispersion of the ADP/APP within the EVA matrix. Through optimization of the flame-retardant formulation, the resulting EVA/APTS/ADP<sub>9</sub>APP<sub>21</sub> vitrimer exhibits an 80% increase in tensile strength (8.1 MPa) compared with the raw EVA, and achieves a UL-94 V-0 rating, exceptional creep resistance with a mere 2.1% permanent deformation at 150 °C. Furthermore, the EVA vitrimer displays excellent reprocessability and recyclability, with retaining nearly identical mechanical properties and V-0 flame retardancy after three recycling cycles. This work offers a viable strategy for creating high-performance vitrimer with integrated mechanical robustness, creep resistance, reprocessability, and fire safety, which is expected to significantly expedite the practical application of vitrimer.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111886"},"PeriodicalIF":7.4,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-25DOI: 10.1016/j.polymdegradstab.2025.111885
Jiachen Zhu , Hongfei He , Chuanshen Wang , Donghai Zhu , Na Sun , Bicheng Lin , Lingxin He , Chao Ding , Keqing Zhou , Bin Yu
Thermoplastic elastomers (TPEs) present a critical challenge in balancing flame retardancy with mechanical integrity. Conventional intumescent flame retardants (IFRs), while effective in suppressing flame propagation, often yield limited improvements in the limiting oxygen index (LOI) and induce severe mechanical degradation at the high loadings required for adequate fire safety. To overcome these limitations, we developed a novel synergistic system by incorporating surface-modified magnesium borate whiskers (MBW) into a TPE matrix containing piperazine pyrophosphate (PAPP). The composite with only 3 wt% MBW and 32 wt% PAPP achieved a UL-94 V-0 rating and a notably high LOI of 30.1%. This remarkable LOI enhancement is directly linked to the condensed-phase char reinforcement effect imparted by MBW. Remarkably, the TPE/32PAPP-3MBW composite also exhibited outstanding fire hazard suppression, reducing the peak heat release rate (PHRR), peak smoke production rate (PSPR), and peak CO production rate (PCOPR) by 78.7%, 69.2%, and 68.3%, respectively, relative to neat TPE. Moreover, the tensile strength reached 12.2 MPa—a 27.1% increase over the composite containing PAPP alone—demonstrating concurrent improvements in both flame retardancy and mechanical performance. The enhanced fire safety is attributed to a dual-phase mechanism: gas-phase radical quenching by phosphorus-containing species from PAPP and condensed-phase reinforcement through the formation of a compact, continuous, and highly graphitized char layer facilitated by MBW. This work elucidates the mechanism responsible for the significant LOI enhancement and provides an effective strategy for designing high-safety TPE composites without significant sacrifice of mechanical properties.
{"title":"Unveiling the mechanism of remarkable enhancement in LOI for Mg2B2O5-whisker in intumescent flame retardant thermoplastic elastomers","authors":"Jiachen Zhu , Hongfei He , Chuanshen Wang , Donghai Zhu , Na Sun , Bicheng Lin , Lingxin He , Chao Ding , Keqing Zhou , Bin Yu","doi":"10.1016/j.polymdegradstab.2025.111885","DOIUrl":"10.1016/j.polymdegradstab.2025.111885","url":null,"abstract":"<div><div>Thermoplastic elastomers (TPEs) present a critical challenge in balancing flame retardancy with mechanical integrity. Conventional intumescent flame retardants (IFRs), while effective in suppressing flame propagation, often yield limited improvements in the limiting oxygen index (LOI) and induce severe mechanical degradation at the high loadings required for adequate fire safety. To overcome these limitations, we developed a novel synergistic system by incorporating surface-modified magnesium borate whiskers (MBW) into a TPE matrix containing piperazine pyrophosphate (PAPP). The composite with only 3 wt% MBW and 32 wt% PAPP achieved a UL-94 V-0 rating and a notably high LOI of 30.1%. This remarkable LOI enhancement is directly linked to the condensed-phase char reinforcement effect imparted by MBW. Remarkably, the TPE/32PAPP-3MBW composite also exhibited outstanding fire hazard suppression, reducing the peak heat release rate (PHRR), peak smoke production rate (PSPR), and peak CO production rate (PCOPR) by 78.7%, 69.2%, and 68.3%, respectively, relative to neat TPE. Moreover, the tensile strength reached 12.2 MPa—a 27.1% increase over the composite containing PAPP alone—demonstrating concurrent improvements in both flame retardancy and mechanical performance. The enhanced fire safety is attributed to a dual-phase mechanism: gas-phase radical quenching by phosphorus-containing species from PAPP and condensed-phase reinforcement through the formation of a compact, continuous, and highly graphitized char layer facilitated by MBW. This work elucidates the mechanism responsible for the significant LOI enhancement and provides an effective strategy for designing high-safety TPE composites without significant sacrifice of mechanical properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111885"},"PeriodicalIF":7.4,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-25DOI: 10.1016/j.polymdegradstab.2025.111889
Xiang Zhang , Jingjing Wang , Rongbo Li , Weiyu Hao , Xia Dong , Qian Xing
To enhance the toughening efficiency of polyamide elastomer (PAE) in polylactide (PLA) and improve interfacial compatibility, polyvinyl acetate (PVAc) was introduced as a compatibilizer, and PLA/PAE/PVAc blends were prepared via melt blending. The influence of PVAc on the crystallization, mechanical, rheological, and shape-memory properties of the PLA/PAE blends was comprehensively examined. SEM analysis showed that PAE formed dispersed island-like domains within the PLA matrix, reflecting limited interfacial compatibility. SEM analysis showed that PAE formed dispersed island-like domains within the PLA matrix, reflecting limited interfacial compatibility. The incorporation of PVAc markedly reduced the size of the dispersed PAE domains and blurred the interfacial boundaries, reflecting enhanced interfacial adhesion. Surface energy analysis suggested that PVAc was preferentially localized at the PLA/PAE interface. Moreover, the addition of an appropriate amount of PVAc promoted the melt crystallization of PLA. The ternary blends exhibited higher storage modulus, loss modulus, and complex viscosity, implying improved viscoelastic behavior. Enhanced interfacial bonding and stress transfer also led to a substantial increase in elongation at break, reaching 50.3 %. Notably, when the PVAc content was 10 wt%, the shape-memory recovery ratio reached a maximum of 94.2 % after three deformation–recovery cycles, demonstrating the synergistic effect of PVAc on both mechanical and functional performance.
{"title":"Interfacial localization of PVAc and its synergistic effect on the toughness and shape-memory behavior of PLA/PAE blends","authors":"Xiang Zhang , Jingjing Wang , Rongbo Li , Weiyu Hao , Xia Dong , Qian Xing","doi":"10.1016/j.polymdegradstab.2025.111889","DOIUrl":"10.1016/j.polymdegradstab.2025.111889","url":null,"abstract":"<div><div>To enhance the toughening efficiency of polyamide elastomer (PAE) in polylactide (PLA) and improve interfacial compatibility, polyvinyl acetate (PVAc) was introduced as a compatibilizer, and PLA/PAE/PVAc blends were prepared via melt blending. The influence of PVAc on the crystallization, mechanical, rheological, and shape-memory properties of the PLA/PAE blends was comprehensively examined. SEM analysis showed that PAE formed dispersed island-like domains within the PLA matrix, reflecting limited interfacial compatibility. SEM analysis showed that PAE formed dispersed island-like domains within the PLA matrix, reflecting limited interfacial compatibility. The incorporation of PVAc markedly reduced the size of the dispersed PAE domains and blurred the interfacial boundaries, reflecting enhanced interfacial adhesion. Surface energy analysis suggested that PVAc was preferentially localized at the PLA/PAE interface. Moreover, the addition of an appropriate amount of PVAc promoted the melt crystallization of PLA. The ternary blends exhibited higher storage modulus, loss modulus, and complex viscosity, implying improved viscoelastic behavior. Enhanced interfacial bonding and stress transfer also led to a substantial increase in elongation at break, reaching 50.3 %. Notably, when the PVAc content was 10 wt%, the shape-memory recovery ratio reached a maximum of 94.2 % after three deformation–recovery cycles, demonstrating the synergistic effect of PVAc on both mechanical and functional performance.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111889"},"PeriodicalIF":7.4,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-25DOI: 10.1016/j.polymdegradstab.2025.111883
Xiaodong Jin , Xiangyun Feng , Shufan Song , Shibing Sun , Wanfu Wang , Yichen Chen , Wufei Tang
An efficient flame retardant coating was developed for rigid polyurethane foam (RPUF) through the integration of layer-by-layer (LBL) self-assembly and UV curing. The RPUF surface was first activated by UV ozone to enable covalent grafting of branched polyethyleneimine (BPEI) as the initial layer. Subsequently, L-serine intercalated Kaolinite (K*aol), diethylene triamine penta (methylene phosphonic acid) (DTPMPA), and BPEI were alternately assembled to form two bilayers, followed by the application of a UV curing phosphorus/nitrogen-containing topcoat to construct a dense protective network. The optimized sample (R-K*5D30-P8N3) exhibited a limiting oxygen index (LOI) of 36.9 % and achieved a V-0 rating in UL-94, accompanied by a 31.8 % reduction in peak heat release rate (pHRR) and a 30 % decrease in total smoke production compared to neat RPUF. Even after 12 h of water leaching, it maintained a LOI of 34.0 % and displayed a 300 % increase in time to ignition and 18.6 % reduction in pHRR compared with neat RPUF during cone calorimetry. The rapid formation of continuous physical barriers accounted for the enhanced flame retardancy, while UV curing immobilized the coating layers, imparting long-term water resistance. This facile “LBL plus UV curing” strategy provides an effective pathway toward robust, low-smoke, and flame retardant coatings for polymeric foams.
{"title":"A “layer by layer plus UV curing” strategy for low-smoke, flame retardant polyurethane foams","authors":"Xiaodong Jin , Xiangyun Feng , Shufan Song , Shibing Sun , Wanfu Wang , Yichen Chen , Wufei Tang","doi":"10.1016/j.polymdegradstab.2025.111883","DOIUrl":"10.1016/j.polymdegradstab.2025.111883","url":null,"abstract":"<div><div>An efficient flame retardant coating was developed for rigid polyurethane foam (RPUF) through the integration of layer-by-layer (LBL) self-assembly and UV curing. The RPUF surface was first activated by UV ozone to enable covalent grafting of branched polyethyleneimine (BPEI) as the initial layer. Subsequently, L-serine intercalated Kaolinite (K*aol), diethylene triamine penta (methylene phosphonic acid) (DTPMPA), and BPEI were alternately assembled to form two bilayers, followed by the application of a UV curing phosphorus/nitrogen-containing topcoat to construct a dense protective network. The optimized sample (R-K*<sub>5</sub>D<sub>30</sub>-P<sub>8</sub>N<sub>3</sub>) exhibited a limiting oxygen index (LOI) of 36.9 % and achieved a V-0 rating in UL-94, accompanied by a 31.8 % reduction in peak heat release rate (pHRR) and a 30 % decrease in total smoke production compared to neat RPUF. Even after 12 h of water leaching, it maintained a LOI of 34.0 % and displayed a 300 % increase in time to ignition and 18.6 % reduction in pHRR compared with neat RPUF during cone calorimetry. The rapid formation of continuous physical barriers accounted for the enhanced flame retardancy, while UV curing immobilized the coating layers, imparting long-term water resistance. This facile “LBL plus UV curing” strategy provides an effective pathway toward robust, low-smoke, and flame retardant coatings for polymeric foams.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111883"},"PeriodicalIF":7.4,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-25DOI: 10.1016/j.polymdegradstab.2025.111890
Jing Sun , Jian Li , Juan Li , Anrong Huang , Zhu Luo , Yanru Shan
The intrinsic friability of poly(L-lactic acid) (PLLA) significantly restricts its practical application. In this study, a facile melt-processing approach was developed to concurrently improve both the strength and toughness of PLLA by introducing oriented stereocomplex crystal (SC) nanofibrillar structures under a high shear extensional flow field through blending with poly(D-lactic acid) (PDLA). Highly oriented SC nanofibrils owning a distinct "pearl-necklace" morphology were formed at low PDLA concentrations (2–4 wt%), exhibiting an average diameter of 70 nm. These structures with increasing PDLA content (6–10 wt%) evolved into a more densely packed shish-kebab architecture. These hierarchical crystalline structures not only acted as efficient nucleating agents but also formed a rigid three-dimensional reinforcing framework within the PLLA matrix. Consequently, the tensile strength increases by 84% (from 63.6 to 117.0 MPa), and the elongation at break improves by 6.5-fold (from 6.0% to 39.4%) compared to neat PLLA. This work offers noble perspectives on the structure–property relationships of PLLA/PDLA blends, highlighting the potential for tailoring material performance through precise control of crystalline morphology.
{"title":"Fabrication of strong and tough PLLA/PDLA composites via constructed stereocomplex crystal nanofibrils under an intense shear extensional flow field","authors":"Jing Sun , Jian Li , Juan Li , Anrong Huang , Zhu Luo , Yanru Shan","doi":"10.1016/j.polymdegradstab.2025.111890","DOIUrl":"10.1016/j.polymdegradstab.2025.111890","url":null,"abstract":"<div><div>The intrinsic friability of poly(L-lactic acid) (PLLA) significantly restricts its practical application. In this study, a facile melt-processing approach was developed to concurrently improve both the strength and toughness of PLLA by introducing oriented stereocomplex crystal (SC) nanofibrillar structures under a high shear extensional flow field through blending with poly(D-lactic acid) (PDLA). Highly oriented SC nanofibrils owning a distinct \"pearl-necklace\" morphology were formed at low PDLA concentrations (2–4 wt%), exhibiting an average diameter of 70 nm. These structures with increasing PDLA content (6–10 wt%) evolved into a more densely packed shish-kebab architecture. These hierarchical crystalline structures not only acted as efficient nucleating agents but also formed a rigid three-dimensional reinforcing framework within the PLLA matrix. Consequently, the tensile strength increases by 84% (from 63.6 to 117.0 MPa), and the elongation at break improves by 6.5-fold (from 6.0% to 39.4%) compared to neat PLLA. This work offers noble perspectives on the structure–property relationships of PLLA/PDLA blends, highlighting the potential for tailoring material performance through precise control of crystalline morphology.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111890"},"PeriodicalIF":7.4,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-24DOI: 10.1016/j.polymdegradstab.2025.111887
Yuming Cui , Qinglan Xue , Haoyi Hu , Kai Wang , Yuhao Liu , Jiaojiao Shang , Jianwu Lan , Shaojian Lin
Thermoplastic polyamide elastomers (TPAEs) are an important class of thermoplastic elastomers (TPEs). However, improving their flame retardancy remains challenging, because such enhancement often leads to adverse effects on the intrinsic thermal stability and mechanical performance of the materials. In this study, a series of intrinsically flame-retardant TPAEs (PAE6-xDPPSA) were synthesized via a one-step melt polycondensation route by incorporating 2- (diphenylphosphinyl methyl) succinic acid (DPPSA) into a TPAE composed of polyamide 6 (PA6) as the hard segment and poly (tetramethylene glycol) (PTMG) as the soft segment. Importantly, the incorporation of DPPSA did not compromise the thermal stability of PA6 elastomers, all PAE6-xDPPSA samples exhibited 5 % weight-loss temperatures above 360 °C, indicating excellent thermal stability. As expected, the flame retardancy of PAE6-xDPPSA was enhanced with increasing DPPSA content, achieving a V-0 rating in UL-94 test and a limiting oxygen index (LOI) above 28 % at 8 wt% of DPPSA. This improvement in flame retardancy resulting from the existence of DPPSA promoted dual-action flame-retardant effects in both the gas phase and the condensed phase. Moreover, PAE6-xDPPSA displayed excellent spinnability and mechanical performance within an appropriate DPPSA content range. In particular, the elastic fibers derived from PAE6–8DPPSA exhibited a tensile strength of 1.82 cN/dtex and an elongation at break of 208.5 %, together with superior flame retardancy. Overall, this study presents an effective strategy for designing intrinsically flame-retardant TPAEs with balanced thermal stability, mechanical properties, and spinnability, paving the way for their potential applications in advanced flame-retardant elastic fibers and engineering materials.
{"title":"One-step synthesis of intrinsically flame-retardant polyamide 6 elastomers with excellent thermal stability and spinnability","authors":"Yuming Cui , Qinglan Xue , Haoyi Hu , Kai Wang , Yuhao Liu , Jiaojiao Shang , Jianwu Lan , Shaojian Lin","doi":"10.1016/j.polymdegradstab.2025.111887","DOIUrl":"10.1016/j.polymdegradstab.2025.111887","url":null,"abstract":"<div><div>Thermoplastic polyamide elastomers (TPAEs) are an important class of thermoplastic elastomers (TPEs). However, improving their flame retardancy remains challenging, because such enhancement often leads to adverse effects on the intrinsic thermal stability and mechanical performance of the materials. In this study, a series of intrinsically flame-retardant TPAEs (PAE6-xDPPSA) were synthesized via a one-step melt polycondensation route by incorporating 2- (diphenylphosphinyl methyl) succinic acid (DPPSA) into a TPAE composed of polyamide 6 (PA6) as the hard segment and poly (tetramethylene glycol) (PTMG) as the soft segment. Importantly, the incorporation of DPPSA did not compromise the thermal stability of PA6 elastomers, all PAE6-xDPPSA samples exhibited 5 % weight-loss temperatures above 360 °C, indicating excellent thermal stability. As expected, the flame retardancy of PAE6-xDPPSA was enhanced with increasing DPPSA content, achieving a V-0 rating in UL-94 test and a limiting oxygen index (LOI) above 28 % at 8 wt% of DPPSA. This improvement in flame retardancy resulting from the existence of DPPSA promoted dual-action flame-retardant effects in both the gas phase and the condensed phase. Moreover, PAE6-xDPPSA displayed excellent spinnability and mechanical performance within an appropriate DPPSA content range. In particular, the elastic fibers derived from PAE6–8DPPSA exhibited a tensile strength of 1.82 cN/dtex and an elongation at break of 208.5 %, together with superior flame retardancy. Overall, this study presents an effective strategy for designing intrinsically flame-retardant TPAEs with balanced thermal stability, mechanical properties, and spinnability, paving the way for their potential applications in advanced flame-retardant elastic fibers and engineering materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111887"},"PeriodicalIF":7.4,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-24DOI: 10.1016/j.polymdegradstab.2025.111884
Bin Zou , Jingwen Wang , Xiaochuan Li , Xiangliang Tian , Fei Ren , Siyu Zhu , Shuilai Qiu , Yingnan Li , Wufan Xuan , Yuan Hu
Enhancing the thermal stability and fire safety of polymer materials is fundamental for managing fire risks and ensuring public safety. Traditional phosphorus-based flame retardants exhibit a contradictory effect, they reduce heat release but increase the production of toxic smoke during polymer combustion. This work proposes an “interfacial autocatalytic” strategy to guide the sequential incorporation of novel boron (B) nanosheets and UiO-66-NH2 (ZrMOFs) to modify black phosphorus (BP) via a facile ball-milling process. The B nanosheets and ZrMOFs hybrid BP (BP-B-Zr) via P-O-B bonding and coordination between metal vacant orbitals and lone-pair electrons, while each component maintains its crystal structure. The synergistic stabilizing effect of BP-B-Zr components enables the polycarbonate composite to achieve superior thermal stability, resulting in a 20.57 °C increase in T-5% than pure polycarbonate. Furthermore, PC/BP-B-Zr composite demonstrates reductions of 71.83% in peak heat release rate, 51.52% in total heat release, 30.54% in total smoke production, 56.83% in peak CO production rate and 53.77% in total CO production, signifying synergistic mitigation of both combustion heat and smoke hazards. The char residue of PC/BP-B-Zr generates new synergistic species of BPO4 and Zr2O(PO4)2 in the interface of condensed phase, achieving the fixation and stabilization of the char layer to block heat and mass transfer, completely suppressing the release of [P4]+ cations derived from the pyrolysis of BP to reduce combustion smoke and CO release via weakened gas-phase effect. This work paves the way for the design of flame-retardant polycarbonate composites with high thermal stability and fire safety.
提高高分子材料的热稳定性和防火安全性是管理火灾风险和确保公共安全的基础。传统的磷系阻燃剂表现出矛盾的效果，在聚合物燃烧过程中，它们减少了热量释放，但增加了有毒烟雾的产生。本研究提出了一种“界面自催化”策略，指导新型硼(B)纳米片和UiO-66-NH2 （ZrMOFs）的顺序结合，通过简单的球磨工艺修饰黑磷（BP）。B纳米片与ZrMOFs通过P-O-B键和金属空轨道与孤对电子之间的配位杂化BP (BP-B- zr)，同时各组分保持各自的晶体结构。BP-B-Zr组分的协同稳定作用使聚碳酸酯复合材料具有优异的热稳定性，其T-5%比纯聚碳酸酯提高20.57℃。此外，PC/BP-B-Zr复合材料的峰值放热率降低了71.83%，总放热率降低了51.52%，总产烟率降低了30.54%，峰值CO产率降低了56.83%，总CO产烟率降低了53.77%，表明燃烧热和烟雾危害协同缓解。PC/BP- b - zr的焦渣在缩合相界面生成了新的协同物质BPO4和Zr2O(PO4)2，实现了焦层的固定和稳定，阻断了传热传质，完全抑制了BP热解产生的[P4]+阳离子的释放，通过减弱气相效应减少了燃烧烟气和CO的释放。这项工作为设计具有高热稳定性和防火安全性的阻燃聚碳酸酯复合材料铺平了道路。
{"title":"Interface in-situ generated two-component phosphates derived from black phosphorus nanohybrid endow outstanding thermal stability and fire safety to polycarbonate composites","authors":"Bin Zou , Jingwen Wang , Xiaochuan Li , Xiangliang Tian , Fei Ren , Siyu Zhu , Shuilai Qiu , Yingnan Li , Wufan Xuan , Yuan Hu","doi":"10.1016/j.polymdegradstab.2025.111884","DOIUrl":"10.1016/j.polymdegradstab.2025.111884","url":null,"abstract":"<div><div>Enhancing the thermal stability and fire safety of polymer materials is fundamental for managing fire risks and ensuring public safety. Traditional phosphorus-based flame retardants exhibit a contradictory effect, they reduce heat release but increase the production of toxic smoke during polymer combustion. This work proposes an “interfacial autocatalytic” strategy to guide the sequential incorporation of novel boron (B) nanosheets and UiO-66-NH<sub>2</sub> (ZrMOFs) to modify black phosphorus (BP) via a facile ball-milling process. The B nanosheets and ZrMOFs hybrid BP (BP-B-Zr) via P-O-B bonding and coordination between metal vacant orbitals and lone-pair electrons, while each component maintains its crystal structure. The synergistic stabilizing effect of BP-B-Zr components enables the polycarbonate composite to achieve superior thermal stability, resulting in a 20.57 °C increase in T<sub>-5%</sub> than pure polycarbonate. Furthermore, PC/BP-B-Zr composite demonstrates reductions of 71.83% in peak heat release rate, 51.52% in total heat release, 30.54% in total smoke production, 56.83% in peak CO production rate and 53.77% in total CO production, signifying synergistic mitigation of both combustion heat and smoke hazards. The char residue of PC/BP-B-Zr generates new synergistic species of BPO<sub>4</sub> and Zr<sub>2</sub>O(PO<sub>4</sub>)<sub>2</sub> in the interface of condensed phase, achieving the fixation and stabilization of the char layer to block heat and mass transfer, completely suppressing the release of [P<sub>4</sub>]<sup>+</sup> cations derived from the pyrolysis of BP to reduce combustion smoke and CO release via weakened gas-phase effect. This work paves the way for the design of flame-retardant polycarbonate composites with high thermal stability and fire safety.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"245 ","pages":"Article 111884"},"PeriodicalIF":7.4,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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