Pub Date : 2026-05-01Epub Date: 2026-01-28DOI: 10.1016/j.polymdegradstab.2026.111965
Lu Liu , Hongfei He , Xiaming Feng , Bin Yu , Hongyu Yang , Benjamin Tawiah
Wood is a ubiquitous construction material, however, its inherent flammability requires the development of effective and environmentally friendly fire-protection strategies. Herein, we present a transparent, self-healing, and bio-based supramolecular intumescent coating for wood protection. The coating was synthesized via a solvent-free multi-step process, integrating a gelatin–phytic acid precursor with a boron–nitrogen coordination complex through controlled melamine reaction. Such coating exhibits good interfacial adhesion to wood, as evidenced by a shear strength of 5.84 MPa. Moreover, it also demonstrated excellent moisture-triggered self-healing ability, which improved scratch resistance and reduced moisture uptake. The coated wood shows significantly improved thermal stability and fire resistance, including a reduction in peak heat release rate (∼57 %) and total heat release (∼42 %), along with an increased limiting oxygen index (35.5 %) and a UL-94 V-0 rating. Based on burnt surface analysis and chemical characterization, the flame-retardant mechanism is elucidated, highlighting synergistic effects in both gas and condensed phases. This work provides a sustainable and effective strategy for wood fire protection and underscores the potential of bio-derived supramolecular architectures in addressing critical safety challenges for bio-based construction materials.
{"title":"Bio-based supramolecular intumescent coatings for wood fire protection","authors":"Lu Liu , Hongfei He , Xiaming Feng , Bin Yu , Hongyu Yang , Benjamin Tawiah","doi":"10.1016/j.polymdegradstab.2026.111965","DOIUrl":"10.1016/j.polymdegradstab.2026.111965","url":null,"abstract":"<div><div>Wood is a ubiquitous construction material, however, its inherent flammability requires the development of effective and environmentally friendly fire-protection strategies. Herein, we present a transparent, self-healing, and bio-based supramolecular intumescent coating for wood protection. The coating was synthesized via a solvent-free multi-step process, integrating a gelatin–phytic acid precursor with a boron–nitrogen coordination complex through controlled melamine reaction. Such coating exhibits good interfacial adhesion to wood, as evidenced by a shear strength of 5.84 MPa. Moreover, it also demonstrated excellent moisture-triggered self-healing ability, which improved scratch resistance and reduced moisture uptake. The coated wood shows significantly improved thermal stability and fire resistance, including a reduction in peak heat release rate (∼57 %) and total heat release (∼42 %), along with an increased limiting oxygen index (35.5 %) and a UL-94 V-0 rating. Based on burnt surface analysis and chemical characterization, the flame-retardant mechanism is elucidated, highlighting synergistic effects in both gas and condensed phases. This work provides a sustainable and effective strategy for wood fire protection and underscores the potential of bio-derived supramolecular architectures in addressing critical safety challenges for bio-based construction materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111965"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171987","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 : 2026-05-01Epub Date: 2026-02-02DOI: 10.1016/j.polymdegradstab.2026.111980
René D. Boisseau Gomez , Md Razaul Karim , Jesus A. Anaya, Jaeyoung Cho
The present study aims to provide a fundamental understanding of the structure-property relationship that determines the char yield (YC) of polymeric ablative materials (PAM) for spacecraft thermal protection systems. We selected phenolic resin (PR) and poly(p-phenylene oxide) (PPO) as a model system for their similarity in molecular structure while having drastically different YC (55 wt.% for PR and 25 wt.% for PPO). First, a graph neural network (GNN) was trained to predict the YC of polymers, while statistically estimating how each bond in a polymer contributes to its YC. The GNN model indicated that PPO’s low YC comes from the para-substituted structure and two methyl groups attached to the aromatic. Second, an experimental study using a pyrolizer and gas-chromatography/mass-spectrometry (Py-GC/MS) revealed that PR forms tricyclics during pyrolysis, while PPO does not, which may be related to PPO’s lower YC. Next, theoretical analysis on the pyrolysis mechanism of PR and PPO revealed that the para-substituted structure of PPO increases the energy barrier for cyclization reactions to form tricyclics. In addition, the methyl groups cannot promote cyclization due to their significant spatial separation from adjacent aromatic rings, which collectively reduces the yield of the tricyclic species. Following the MD simulation, it was confirmed that tricyclics at the initial stage of pyrolysis are key to accelerating the growth of char precursors, explaining the higher YC of PR compared to PPO. The comprehensive insights into the structure-property relationships of YC will facilitate the discovery of novel PAM for superior thermal protection performance.
{"title":"AI-experiment-theory integrated study on char formation kinetics of polymeric ablative materials: Comparative study of phenolic resin vs. poly(p-phenylene oxide)","authors":"René D. Boisseau Gomez , Md Razaul Karim , Jesus A. Anaya, Jaeyoung Cho","doi":"10.1016/j.polymdegradstab.2026.111980","DOIUrl":"10.1016/j.polymdegradstab.2026.111980","url":null,"abstract":"<div><div>The present study aims to provide a fundamental understanding of the structure-property relationship that determines the char yield (<em>Y<sub>C</sub></em>) of polymeric ablative materials (PAM) for spacecraft thermal protection systems. We selected phenolic resin (PR) and poly(p-phenylene oxide) (PPO) as a model system for their similarity in molecular structure while having drastically different <em>Y<sub>C</sub></em> (55 wt.% for PR and 25 wt.% for PPO). First, a graph neural network (GNN) was trained to predict the <em>Y<sub>C</sub></em> of polymers, while statistically estimating how each bond in a polymer contributes to its <em>Y<sub>C</sub></em>. The GNN model indicated that PPO’s low Y<sub>C</sub> comes from the para-substituted structure and two methyl groups attached to the aromatic. Second, an experimental study using a pyrolizer and gas-chromatography/mass-spectrometry (Py-GC/MS) revealed that PR forms tricyclics during pyrolysis, while PPO does not, which may be related to PPO’s lower <em>Y<sub>C</sub></em>. Next, theoretical analysis on the pyrolysis mechanism of PR and PPO revealed that the para-substituted structure of PPO increases the energy barrier for cyclization reactions to form tricyclics. In addition, the methyl groups cannot promote cyclization due to their significant spatial separation from adjacent aromatic rings, which collectively reduces the yield of the tricyclic species. Following the MD simulation, it was confirmed that tricyclics at the initial stage of pyrolysis are key to accelerating the growth of char precursors, explaining the higher <em>Y<sub>C</sub></em> of PR compared to PPO. The comprehensive insights into the structure-property relationships of <em>Y<sub>C</sub></em> will facilitate the discovery of novel PAM for superior thermal protection performance.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111980"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171918","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}
Biodegradable plastics can help reduce marine plastic pollution. However, most studies have tested biodegradability at only one site; therefore, distinguishing material effects from seawater conditions is difficult. In this study, we evaluated the location-dependent marine biodegradability of two representative aliphatic polyesters, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(butylene succinate-co-adipate) (PBSA), under identical laboratory conditions using seawater collected from 12 coastal sites in Japan. Film mass loss, biochemical oxygen demand (BOD) -based mineralization (BOD/theoretical oxygen demand, ThOD), and plastisphere composition were assessed, with polyethylene serving as a non-biodegradable reference. PHBV degraded in all seawater samples, and achieving substantial BOD-based mineralization (52–86%). In contrast, PBSA degraded only in seawater from Isumi, Chiba (CI), Japan, and no measurable mineralization was detected. Amplicon sequencing indicated that PHBV formed a consistent material-specific plastisphere containing members of Alteromonadaceae, Colwelliaceae, and Oceanospirillaceae, independent of the sampling location. PBSA plastispheres varied among sites. Although genera previously linked to polyester degradation (e.g., Pseudomonas, Halopseudomonas, Alcanivorax) were detected, their involvement in the biofilm community observed at CI remains speculative. Collectively, these findings demonstrate that PHBV biodegradability is robust across locations, whereas PBSA degradation is site-dependent under the same laboratory conditions.
{"title":"Location-dependent marine biodegradability of aliphatic polyesters under simulated seawater conditions","authors":"Miwa Suzuki , Moeka Noguchi , Tomoya Suzuki , Phouvilay Soulenthone , Shun Tsuboi , Masa-aki Yoshida , Shun’ichi Ishii , Hiroyuki Kashima , Hidetaka Nomaki , Noriyuki Isobe , Keiji Numata , Yuya Tachibana , Ken-ichi Kasuya","doi":"10.1016/j.polymdegradstab.2026.111975","DOIUrl":"10.1016/j.polymdegradstab.2026.111975","url":null,"abstract":"<div><div>Biodegradable plastics can help reduce marine plastic pollution. However, most studies have tested biodegradability at only one site; therefore, distinguishing material effects from seawater conditions is difficult. In this study, we evaluated the location-dependent marine biodegradability of two representative aliphatic polyesters, poly(3-hydroxybutyrate-<em>co</em>-3-hydroxyvalerate) (PHBV) and poly(butylene succinate-<em>co</em>-adipate) (PBSA), under identical laboratory conditions using seawater collected from 12 coastal sites in Japan. Film mass loss, biochemical oxygen demand (BOD) -based mineralization (BOD/theoretical oxygen demand, ThOD), and plastisphere composition were assessed, with polyethylene serving as a non-biodegradable reference. PHBV degraded in all seawater samples, and achieving substantial BOD-based mineralization (52–86%). In contrast, PBSA degraded only in seawater from Isumi, Chiba (CI), Japan, and no measurable mineralization was detected. Amplicon sequencing indicated that PHBV formed a consistent material-specific plastisphere containing members of <em>Alteromonadaceae, Colwelliaceae</em>, and <em>Oceanospirillaceae</em>, independent of the sampling location. PBSA plastispheres varied among sites. Although genera previously linked to polyester degradation (e.g., <em>Pseudomonas, Halopseudomonas, Alcanivorax</em>) were detected, their involvement in the biofilm community observed at CI remains speculative. Collectively, these findings demonstrate that PHBV biodegradability is robust across locations, whereas PBSA degradation is site-dependent under the same laboratory conditions.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111975"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171988","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 : 2026-05-01Epub Date: 2026-02-04DOI: 10.1016/j.polymdegradstab.2026.111984
Khalida Naseem , Jingling Zhu , Jun Li
Polymer-based nanocomposite hydrogels have received much attention due to their versatile properties and wide-ranging applications across different fields. Poly(vinyl alcohol) (PVA), rich in hydroxyl groups, readily forms physical and/or chemical bonds with both polymeric and non-polymeric materials, enabling the design of composite hydrogels that exhibit synergistic enhancements in properties. These composite hydrogels can be synthesized in various forms, including bulks, membranes, films, fibers, sponges, and beads, depending on their intended applications. Specifically, nanocomposite hydrogels incorporating metal nanoparticles (mNPs) have been fabricated via diverse approaches, such as chemical and green synthesis. These resulting nanocomposite hydrogels exhibit several crucial functionalities. They demonstrate responsiveness to external stimuli, including changes in pH, temperature, and ionic strength, depending on the nature of the hydrogel, as well as catalytic and antimicrobial properties attributed to the incorporated mNPs. This review discusses the various strategies employed in the design of PVA-based hydrogels, with a specific focus on nanocomposite hydrogels. This study also specifically emphasizes their applications as adsorbents for removing pollutants from water and their innovative roles as catalysts and antimicrobial agents for treating wastewater contaminated with dyes, nitroarenes, and various microorganisms. Finally, the article highlights future directions for research in previously unexplored areas.
{"title":"Design of poly(vinyl alcohol)-based nanocomposite hydrogels for removal and degradation of pollutants in wastewater: A critical review","authors":"Khalida Naseem , Jingling Zhu , Jun Li","doi":"10.1016/j.polymdegradstab.2026.111984","DOIUrl":"10.1016/j.polymdegradstab.2026.111984","url":null,"abstract":"<div><div>Polymer-based nanocomposite hydrogels have received much attention due to their versatile properties and wide-ranging applications across different fields. Poly(vinyl alcohol) (PVA), rich in hydroxyl groups, readily forms physical and/or chemical bonds with both polymeric and non-polymeric materials, enabling the design of composite hydrogels that exhibit synergistic enhancements in properties. These composite hydrogels can be synthesized in various forms, including bulks, membranes, films, fibers, sponges, and beads, depending on their intended applications. Specifically, nanocomposite hydrogels incorporating metal nanoparticles (mNPs) have been fabricated via diverse approaches, such as chemical and green synthesis. These resulting nanocomposite hydrogels exhibit several crucial functionalities. They demonstrate responsiveness to external stimuli, including changes in pH, temperature, and ionic strength, depending on the nature of the hydrogel, as well as catalytic and antimicrobial properties attributed to the incorporated mNPs. This review discusses the various strategies employed in the design of PVA-based hydrogels, with a specific focus on nanocomposite hydrogels. This study also specifically emphasizes their applications as adsorbents for removing pollutants from water and their innovative roles as catalysts and antimicrobial agents for treating wastewater contaminated with dyes, nitroarenes, and various microorganisms. Finally, the article highlights future directions for research in previously unexplored areas.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111984"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171920","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 : 2026-05-01Epub Date: 2026-02-05DOI: 10.1016/j.polymdegradstab.2026.111979
Guangyong Jiang , Yaqi Cai , Jiayu Chang , Zhou Gui , Yixin Hu , Weiyi Xing , Lei Song , Bin Fei
The application of semi-aromatic polyimide (PI) is limited by its relatively high dielectric constant (Dk) and flame retardancy. To address this problem, a novel fluorophenoxy-based linear polyphosphazene (FB-PDCP) was synthesized as a multifunctional additive and incorporated into a PI matrix to fabricate a series of high-performance FB-PDCP/PI composite films. The introduction of FB-PDCP establishes strong interfacial interactions within PI matrix, significantly increasing the glass transition temperature (Tg) of the composite films from 299 °C to 345 °C. The unique structural effects of FB-PDCP concurrently optimized the overall performance of the composites. At 1 kHz, the FB-PDCP-7/PI film exhibited an ultralow Dk of 2.24, a 33.92% reduction compared to neat PI. In terms of flame retardancy, the composite films achieved a high limiting oxygen index (LOI) of 30.0% and passed the UL-94 through V-0 rating, demonstrating exceptional fire safety. Meanwhile, Thermogravimetry-infrared spectroscopy (TG-IR) revealed the incorporation of FB-PDCP suppressed the release of fluorine-containing substances from PI composites, indicating superior toxic gas suppression. Furthermore, the FB-PDCP-7/PI composite films obtain a tensile strength of 103 MPa, with a storage modulus of 3.93 GPa and an elongation at break of 13.1%. This study provides an integrated solution to the conflict between achieving low Dk and high flame retardancy in PI materials, and the developed FB-PDCP/PI composite films show great potential for applications in electronic packaging.
{"title":"Molecular engineering of polyphosphazene for low toxicity, flame retardant and low dielectric semi-aromatic polyimide composites","authors":"Guangyong Jiang , Yaqi Cai , Jiayu Chang , Zhou Gui , Yixin Hu , Weiyi Xing , Lei Song , Bin Fei","doi":"10.1016/j.polymdegradstab.2026.111979","DOIUrl":"10.1016/j.polymdegradstab.2026.111979","url":null,"abstract":"<div><div>The application of semi-aromatic polyimide (PI) is limited by its relatively high dielectric constant (D<sub>k</sub>) and flame retardancy. To address this problem, a novel fluorophenoxy-based linear polyphosphazene (FB-PDCP) was synthesized as a multifunctional additive and incorporated into a PI matrix to fabricate a series of high-performance FB-PDCP/PI composite films. The introduction of FB-PDCP establishes strong interfacial interactions within PI matrix, significantly increasing the glass transition temperature (<em>T</em><sub>g</sub>) of the composite films from 299 °C to 345 °C. The unique structural effects of FB-PDCP concurrently optimized the overall performance of the composites. At 1 kHz, the FB-PDCP-7/PI film exhibited an ultralow D<sub>k</sub> of 2.24, a 33.92% reduction compared to neat PI. In terms of flame retardancy, the composite films achieved a high limiting oxygen index (LOI) of 30.0% and passed the UL-94 through V-0 rating, demonstrating exceptional fire safety. Meanwhile, Thermogravimetry-infrared spectroscopy (TG-IR) revealed the incorporation of FB-PDCP suppressed the release of fluorine-containing substances from PI composites, indicating superior toxic gas suppression. Furthermore, the FB-PDCP-7/PI composite films obtain a tensile strength of 103 MPa, with a storage modulus of 3.93 GPa and an elongation at break of 13.1%. This study provides an integrated solution to the conflict between achieving low D<sub>k</sub> and high flame retardancy in PI materials, and the developed FB-PDCP/PI composite films show great potential for applications in electronic packaging.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111979"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171922","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 : 2026-05-01Epub Date: 2026-02-10DOI: 10.1016/j.polymdegradstab.2026.112000
Xueqian Fan , Ao Qin , Shuhui Liang , Peirui Song , Yukun Tang , Chentao Yan , Yue Xu , Lubin Liu
Intumescent flame retardant styrene thermoplastic elastomers (TPS) are widely used in new energy and electronic appliance sectors. However, the poor flame retardant efficiency, compatibility and bio-modification of the intumescent flame retardants (IFRs) used for TPS restrict their application in high-end fields. In this study, acid source ammonium polyphosphate (APP) is used as the carrier, and a positively charged bio-based char-foaming agent (MAEP) is constructed on the APP surface by electrostatic assembly technology, thereby preparing monomolecular IFRs (EAPP). EAPP not only decreases the dependence of IFRs on petroleum-based raw materials, but also enhances the flame retardant efficiency of triazine-based IFRs and their compatibility with TPS composites. Compared to conventional IFR blends, 30 wt.% electrostatically assembled EAPP enabled the TPS to achieve UL-94 V-0 rating. The flame retardancy mechanism of TPS/EAPP composites primarily relies on the synergy of catalytic charring and physical barrier effects. Consequently, the total heat and smoke release from TPS/EAPP composites are 27.7% and 74.7% lower than that of pure TPS. Besides, electrostatically assembled EAPP reduces its surface polarity, and demonstrates better compatibility with the TPS matrix. Compared to the TPS/MAEP/APP composites, the mechanical properties of TPS/EAPP composites improved by 31.5%. Electrostatically assembled bio-based IFRs offer a promising strategy for the preparation of high-performance TPS with excellent fire safety, mechanical and sustainable properties.
{"title":"Surface electrostatic assembly for enhancing the fire safety, compatibility and mechanical performance of triazin-based intumescent flame retardant systems in styrene thermoplastic elastomers","authors":"Xueqian Fan , Ao Qin , Shuhui Liang , Peirui Song , Yukun Tang , Chentao Yan , Yue Xu , Lubin Liu","doi":"10.1016/j.polymdegradstab.2026.112000","DOIUrl":"10.1016/j.polymdegradstab.2026.112000","url":null,"abstract":"<div><div>Intumescent flame retardant styrene thermoplastic elastomers (TPS) are widely used in new energy and electronic appliance sectors. However, the poor flame retardant efficiency, compatibility and bio-modification of the intumescent flame retardants (IFRs) used for TPS restrict their application in high-end fields. In this study, acid source ammonium polyphosphate (APP) is used as the carrier, and a positively charged bio-based char-foaming agent (MAEP) is constructed on the APP surface by electrostatic assembly technology, thereby preparing monomolecular IFRs (EAPP). EAPP not only decreases the dependence of IFRs on petroleum-based raw materials, but also enhances the flame retardant efficiency of triazine-based IFRs and their compatibility with TPS composites. Compared to conventional IFR blends, 30 wt.% electrostatically assembled EAPP enabled the TPS to achieve UL-94 V-0 rating. The flame retardancy mechanism of TPS/EAPP composites primarily relies on the synergy of catalytic charring and physical barrier effects. Consequently, the total heat and smoke release from TPS/EAPP composites are 27.7% and 74.7% lower than that of pure TPS. Besides, electrostatically assembled EAPP reduces its surface polarity, and demonstrates better compatibility with the TPS matrix. Compared to the TPS/MAEP/APP composites, the mechanical properties of TPS/EAPP composites improved by 31.5%. Electrostatically assembled bio-based IFRs offer a promising strategy for the preparation of high-performance TPS with excellent fire safety, mechanical and sustainable properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 112000"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171483","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 : 2026-05-01Epub Date: 2026-02-10DOI: 10.1016/j.polymdegradstab.2026.112001
Guoqin Jiang , Zhixiong Huang , Yuzhan Lu , Zongyi Deng
Carbon fiber/phenolic resin (CF/Ph) composites are widely used in aerospace thermal protection materials (TPMs) due to their excellent performance. However, their inherent susceptibility to oxidation in high-temperature and oxidative environments severely limits their application. In this study, a dual-modification strategy, combining matrix modification and fiber coating, was employed to fabricate Al-coated carbon fiber/boron phenolic resin ceramizable composites (ACF/BPRC) modified with Ti3SiC2 and CaB6. Owing to the synergistic effect of Ti3SiC2, CaB6, and Al coating, the resulting ceramizable composites exhibit significantly enhanced oxidation and ablation resistance along with high-temperature insulation performance. The linear ablation rate (LAR) and backside temperature at 3000°C were 0.004 mm/s and 108.3°C, respectively, corresponding to reductions of 91.4% in LAR and 23.3% in backside temperature compared with conventional CF/Ph composites. Furthermore, after 900 s of butane torch flame ablation, the backside temperature remained as low as 396.6°C. These superior properties position the developed ceramizable composites as highly promising candidates for TPMs in solid rocket motors.
{"title":"Matrix modification and fiber coating strategy for synergistic enhancing ablation resistance and high-temperature insulation performance of CF/Ph composites","authors":"Guoqin Jiang , Zhixiong Huang , Yuzhan Lu , Zongyi Deng","doi":"10.1016/j.polymdegradstab.2026.112001","DOIUrl":"10.1016/j.polymdegradstab.2026.112001","url":null,"abstract":"<div><div>Carbon fiber/phenolic resin (CF/Ph) composites are widely used in aerospace thermal protection materials (TPMs) due to their excellent performance. However, their inherent susceptibility to oxidation in high-temperature and oxidative environments severely limits their application. In this study, a dual-modification strategy, combining matrix modification and fiber coating, was employed to fabricate Al-coated carbon fiber/boron phenolic resin ceramizable composites (ACF/BPRC) modified with Ti<sub>3</sub>SiC<sub>2</sub> and CaB<sub>6</sub>. Owing to the synergistic effect of Ti<sub>3</sub>SiC<sub>2</sub>, CaB<sub>6</sub>, and Al coating, the resulting ceramizable composites exhibit significantly enhanced oxidation and ablation resistance along with high-temperature insulation performance. The linear ablation rate (LAR) and backside temperature at 3000°C were 0.004 mm/s and 108.3°C, respectively, corresponding to reductions of 91.4% in LAR and 23.3% in backside temperature compared with conventional CF/Ph composites. Furthermore, after 900 s of butane torch flame ablation, the backside temperature remained as low as 396.6°C. These superior properties position the developed ceramizable composites as highly promising candidates for TPMs in solid rocket motors.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 112001"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171485","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}
The preparation of high-performance, multifunctional, eco-friendly non-isocyanate polyurethanes remains a challenging task. Herein, we designed a bio-based five-membered ring carbonate containing O-Si-O and constructed a poly(hydroxy)urea-epoxy hybrid polymer (SNIPU) through its hybrid cross-linking with epoxy resin. Hybrid cross-linking endows SNIPU with a lower curing energy requirement, facilitating the formation of the cross-linked network. SNIPU with a microphase-separated hybrid cross-linked network exhibits excellent mechanical properties, with tensile strength, strain, and notched impact strength reaching 112.78 MPa, 13.72 %, and 46.57 kJ/m2, respectively. The hybrid cross-linked network and abundant hydroxyl groups confer excellent cohesive strength and interfacial bonding drive to SNIPU, enabling it to exhibit outstanding bonding strength (lap-shear strength of 14.61 MPa) and bonding universality when used as an adhesive. The presence of O-Si-O confers excellent flame-retardant, dielectric, and hydrophobic properties to SNIPU, providing potential support of high-performance, multifunctional non-isocyanate polyurethanes for its application in adhesives. This study provides a new technical approach for the preparation.
{"title":"High-strength, flame-retardant, dielectric Si-functionalized biomass hybrid crosslinked non-isocyanate polyurethane-epoxy for general-purpose adhesive","authors":"Junbo Zang , Jiahui Qi , Jiaxu Zhang , Hao Liu , Chunhong Zhang , Chengyue Zhang , Runtian Wu , Xiaochao Xu , Lei Shang","doi":"10.1016/j.polymdegradstab.2026.111997","DOIUrl":"10.1016/j.polymdegradstab.2026.111997","url":null,"abstract":"<div><div>The preparation of high-performance, multifunctional, eco-friendly non-isocyanate polyurethanes remains a challenging task. Herein, we designed a bio-based five-membered ring carbonate containing O-Si-O and constructed a poly(hydroxy)urea-epoxy hybrid polymer (SNIPU) through its hybrid cross-linking with epoxy resin. Hybrid cross-linking endows SNIPU with a lower curing energy requirement, facilitating the formation of the cross-linked network. SNIPU with a microphase-separated hybrid cross-linked network exhibits excellent mechanical properties, with tensile strength, strain, and notched impact strength reaching 112.78 MPa, 13.72 %, and 46.57 kJ/m<sup>2</sup>, respectively. The hybrid cross-linked network and abundant hydroxyl groups confer excellent cohesive strength and interfacial bonding drive to SNIPU, enabling it to exhibit outstanding bonding strength (lap-shear strength of 14.61 MPa) and bonding universality when used as an adhesive. The presence of O-Si-O confers excellent flame-retardant, dielectric, and hydrophobic properties to SNIPU, providing potential support of high-performance, multifunctional non-isocyanate polyurethanes for its application in adhesives. This study provides a new technical approach for the preparation.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111997"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171486","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 : 2026-05-01Epub Date: 2026-01-31DOI: 10.1016/j.polymdegradstab.2026.111978
Yuanchuan Ren , Yuhang Lin , Xuejun Zhu , Shiyong Zhao , Renjie Huang , Tingfeng Su , Cheng Wang , Nanqi Ren
With the increasing complexity of fire safety requirements, intelligent material design is undergoing a paradigm shift from passive protection to active response. This review systematically reviews the progress and challenges in this field from the dual perspectives of material response mechanisms and machine learning empowerment in research and development. The traditional "trial and error method" is difficult to effectively analyze and optimize the multi-scale response mechanism of smart materials under external thermal and smoke stimuli, including the physical and chemical processes such as phase transition, expansion, and carbonization of intrinsic materials, as well as the synergistic pathways of multiple components (such as flame retardants, carbonization agents, and catalysts) in composite materials. The introduction of machine learning is profoundly transforming this research paradigm: on the one hand, through supervised learning models (such as random forests, deep neural networks), quantitative structure-activity relationships are established between material composition, microstructure, and flame retardant properties (such as heat release rate, residual carbon rate), revealing key characteristic variables that affect response efficiency; On the other hand, unsupervised learning and generative models can be used to uncover implicit structure-activity relationships and reverse engineer novel molecular or composite material formulations with target response characteristics. However, this interdisciplinary field still faces core challenges such as deep integration of mechanisms and data-driven approaches, scarcity of high-quality specialized datasets, insufficient model interpretability, and the gap from virtual design to engineering applications. Future research needs to focus on developing interpretable machine learning frameworks that integrate prior knowledge of physics and chemistry, constructing standardized databases of material fire behavior, and promoting the formation of a closed-loop research and development ecosystem of "intelligent design high-throughput preparation precise verification", thereby accelerating the innovation and application of next-generation intelligent fire-resistant materials.
{"title":"The paradigm shift of intelligent material design and development for fire safety: progress, challenges, and machine learning","authors":"Yuanchuan Ren , Yuhang Lin , Xuejun Zhu , Shiyong Zhao , Renjie Huang , Tingfeng Su , Cheng Wang , Nanqi Ren","doi":"10.1016/j.polymdegradstab.2026.111978","DOIUrl":"10.1016/j.polymdegradstab.2026.111978","url":null,"abstract":"<div><div>With the increasing complexity of fire safety requirements, intelligent material design is undergoing a paradigm shift from passive protection to active response. This review systematically reviews the progress and challenges in this field from the dual perspectives of material response mechanisms and machine learning empowerment in research and development. The traditional \"trial and error method\" is difficult to effectively analyze and optimize the multi-scale response mechanism of smart materials under external thermal and smoke stimuli, including the physical and chemical processes such as phase transition, expansion, and carbonization of intrinsic materials, as well as the synergistic pathways of multiple components (such as flame retardants, carbonization agents, and catalysts) in composite materials. The introduction of machine learning is profoundly transforming this research paradigm: on the one hand, through supervised learning models (such as random forests, deep neural networks), quantitative structure-activity relationships are established between material composition, microstructure, and flame retardant properties (such as heat release rate, residual carbon rate), revealing key characteristic variables that affect response efficiency; On the other hand, unsupervised learning and generative models can be used to uncover implicit structure-activity relationships and reverse engineer novel molecular or composite material formulations with target response characteristics. However, this interdisciplinary field still faces core challenges such as deep integration of mechanisms and data-driven approaches, scarcity of high-quality specialized datasets, insufficient model interpretability, and the gap from virtual design to engineering applications. Future research needs to focus on developing interpretable machine learning frameworks that integrate prior knowledge of physics and chemistry, constructing standardized databases of material fire behavior, and promoting the formation of a closed-loop research and development ecosystem of \"intelligent design high-throughput preparation precise verification\", thereby accelerating the innovation and application of next-generation intelligent fire-resistant materials.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111978"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171488","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 : 2026-05-01Epub Date: 2026-02-09DOI: 10.1016/j.polymdegradstab.2026.111993
Sarah Elfadil Ali, Jianhui Li, Yuanqing Shen, Xiaochun Chen
With global plastic production soaring, developing efficient chemical recycling methods for polyethylene terephthalate (PET) is critical. While synergistic systems of ionic liquids and metal salts have shown promise for PET glycolysis, they often face significant challenges in catalyst separation and recyclability, hindering practical application. To address these limitations, this study introduces a heterogeneous catalyst [P66614]Cl-ZnO, synthesized through an ultrasonication-assisted method. Comprehensive characterization reveals that the ionic liquid forms a stable composite through electrostatic interactions, creating a bifunctional acid catalyst with both Lewis and Brønsted acid sites, as confirmed by pyridine-FTIR. Critically, the mesoporous architecture of [P66614]Cl-ZnO (surface area = 57.5 m2/g, mean pore diameter = 35.48 nm) is more than double that of pure ZnO and specifically designed to facilitate rapid diffusion of bulky PET polymer chains through catalyst pores, overcoming typical mass-transport limitations in polymer depolymerization. Under optimized conditions (195°C, 80 min), the catalyst achieves complete PET conversion and an 89.89% yield of bis(2-hydroxyethyl) terephthalate (BHET), while reducing the activation energy to 102.3 kJ·mol−1. The heterogeneous nature of the catalyst allows for easy recovery, demonstrating consistent performance in ten consecutive cycles. The high purity of the BHET product was verified by NMR, MS, and elemental analysis. This work provides a robust, efficient, and reusable catalytic system for PET glycolysis, highlighting the importance of tailored textural and acidic properties in catalyst design.
{"title":"Phosphonium ionic liquids-ZnO heterogeneous catalyst for PET glycolysis: Ultrasonication-assisted synthesis and performance evaluation","authors":"Sarah Elfadil Ali, Jianhui Li, Yuanqing Shen, Xiaochun Chen","doi":"10.1016/j.polymdegradstab.2026.111993","DOIUrl":"10.1016/j.polymdegradstab.2026.111993","url":null,"abstract":"<div><div>With global plastic production soaring, developing efficient chemical recycling methods for polyethylene terephthalate (PET) is critical. While synergistic systems of ionic liquids and metal salts have shown promise for PET glycolysis, they often face significant challenges in catalyst separation and recyclability, hindering practical application. To address these limitations, this study introduces a heterogeneous catalyst [P<sub>66614</sub>]Cl-ZnO, synthesized through an ultrasonication-assisted method. Comprehensive characterization reveals that the ionic liquid forms a stable composite through electrostatic interactions, creating a bifunctional acid catalyst with both Lewis and Brønsted acid sites, as confirmed by pyridine-FTIR. Critically, the mesoporous architecture of [P<sub>66614</sub>]Cl-ZnO (surface area = 57.5 m<sup>2</sup>/g, mean pore diameter = 35.48 nm) is more than double that of pure ZnO and specifically designed to facilitate rapid diffusion of bulky PET polymer chains through catalyst pores, overcoming typical mass-transport limitations in polymer depolymerization. Under optimized conditions (195°C, 80 min), the catalyst achieves complete PET conversion and an 89.89% yield of bis(2-hydroxyethyl) terephthalate (BHET), while reducing the activation energy to 102.3 kJ·mol<sup>−1</sup>. The heterogeneous nature of the catalyst allows for easy recovery, demonstrating consistent performance in ten consecutive cycles. The high purity of the BHET product was verified by NMR, MS, and elemental analysis. This work provides a robust, efficient, and reusable catalytic system for PET glycolysis, highlighting the importance of tailored textural and acidic properties in catalyst design.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"247 ","pages":"Article 111993"},"PeriodicalIF":7.4,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171480","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号