Polymer Degradation and Stability最新文献

{"title":"Mechanisms of enhanced durability in fluorinated polyimide based on POSS during electro-thermal aging","authors":"Shengrui Zhou,&nbsp;Li Zhang,&nbsp;Guan Wang,&nbsp;Bilal Iqbal Ayubi,&nbsp;Yiwei Wang","doi":"10.1016/j.polymdegradstab.2025.111402","DOIUrl":"10.1016/j.polymdegradstab.2025.111402","url":null,"abstract":"<div><div>Fluorinated polyimide (FPI) is widely used in high-frequency electronic devices and aerospace applications due to its outstanding insulation properties and chemical stability. However, its degradation mechanisms under electro-thermal aging remain poorly understood. Polyhedral oligomeric silsesquioxane (POSS), as a nanofiller, offers excellent thermal stability and flame retardancy, yet studies on the electro-thermal aging resistance and chemical transformation mechanisms of FPI/POSS nanocomposites are still limited. This study employs reactive molecular dynamics (ReaxFF-MD) simulations, combined with vibrational energy distribution analysis, to investigate the electro-thermal aging mechanisms of FPI/POSS nanocomposites. Additionally, density functional theory (DFT) is used to examine the electron transfer pathways of FPI molecules and the reactive site changes in POSS cages under electric fields. The results demonstrate that POSS achieves higher vibrational energy and structural stability under electro-thermal conditions, significantly raising the thermal decomposition threshold of FPI molecular chains. This reduces the release of volatile products and substantially enhances the electro-thermal aging resistance of the composites.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111402"},"PeriodicalIF":6.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927629","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}

{"title":"Reaction retardancy and nonuniformity of polyacrylonitrile fibers by tow sizes during oxidative stabilization","authors":"Qiufei Chen ,&nbsp;Hongqiang Zhu ,&nbsp;Min Li ,&nbsp;Jian He ,&nbsp;Hamza Malik ,&nbsp;Baolin Fan ,&nbsp;Hui Zhang ,&nbsp;Yong Liu ,&nbsp;Jianyong Yu","doi":"10.1016/j.polymdegradstab.2025.111401","DOIUrl":"10.1016/j.polymdegradstab.2025.111401","url":null,"abstract":"<div><div>Large-tow carbon fibers (CFs) possess more advantageous of cost than small-tow CFs, however, the uneven heat release during oxidative stabilization affects the chemical and physical performance of subsequent large-tow CFs. In this work, we prepared 12–48 K PAN oxidative stabilized fibers with continuous stabilization method, and the microstructural evolutions were investigated. The heat transfer and oxygen diffusion were inhibited and lagged in large-tow PAN fibers during oxidative stabilization, resulting in less cyclization reaction and oxygen-uptake reaction, and the small-tow stabilized fibers presented higher R_D, oxygen content, and more uniform degree of chemical reactions. Thermal behavior revealed that 48 K stabilized fibers demonstrated lower T_onset and higher Δ_H as they remained relatively more uncyclized linear structures. The cross-section morphologies were refined with the generation of oxidized structures, and the skin-core structures were induced, large-tow fibers demonstrated more radial heterogeneity related to the inhibited oxygen diffusion and uncompleted cyclization. Furthermore, less amorphous transformation occurred in large-tow fibers. Part of the heat generated by cyclization and oxidation reactions transferred into the inner layer and contribute to the chemical reactions, and some of it flew out, the ununiform extent of reactions made larger fluctuation in microvoid variations according to the SAXS results.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111401"},"PeriodicalIF":6.3,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898877","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}

{"title":"Randomly methylated β-cyclodextrin as a modifier in PBAT/PLA-based films: Stability and crystallinity evaluation","authors":"Khadar Duale ,&nbsp;Wanda Sikorska ,&nbsp;Marta Musioł ,&nbsp;Henryk Janeczek ,&nbsp;Marcin Godzierz ,&nbsp;Andrzej Marcinkowski ,&nbsp;Marek Kowalczuk ,&nbsp;Iza Radecka ,&nbsp;Abhishek Gupta ,&nbsp;Cristian Peptu ,&nbsp;Joanna Rydz","doi":"10.1016/j.polymdegradstab.2025.111399","DOIUrl":"10.1016/j.polymdegradstab.2025.111399","url":null,"abstract":"<div><div>The poly(butylene adipate-<em>co</em>-butylene terephthalate)/polylactide (PBAT/PLA) have attracted a great deal of attention in recent years due to their excellent (bio)degradability. In this study, the PBAT/PLA-based films with and without randomly methylated β-cyclodextrin (RM-β-CD) were prepared using solvent-casting and pressing techniques to evaluate the physiochemical and degradation properties of the obtained films. The characterisation of PBAT/PLA-based films was conducted by using microscopes (optical and AFM), GPC, DSC, and XRD measurements. In addition, degradation tests in water at 37 and 70 °C were conducted under abiotic conditions for 70 days. The research revealed that the addition of RM-β-CD resulted in shifts in the glass transition temperature and greater ordering of PBAT/PLA-based films as well as a slight decrease in cytocompatibility. However, antimicrobial activity and cytotoxicity studies performed did not reveal any risks for their possible applications. Analysis of the degradation progress showed that at 37 °C a slight molar mass loss for solvent-cast films and a slightly higher loss for solvent-cast films with RM-β-CD were noticed. No changes were observed in the more ordered pressed films. Hydrolytic degradation of all PBAT/PLA-based films during incubation at 70 °C resulted in a continuous decrease in the molar mass. Solvent-cast films are characterised by poor miscibility and phase separation, resulting in high roughness. However, the higher temperature during degradation and generally the addition of RM-β-CD to the polymer matrix improved their miscibility.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111399"},"PeriodicalIF":6.3,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143916918","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}

{"title":"Development of stabilizer formulations for Poly(4-methyl-1-pentene) via high-throughput chemiluminescence imaging and genetic algorithm","authors":"Kyo Yanagiyama,&nbsp;Toru Wada,&nbsp;Emi Sawade,&nbsp;Toshiaki Taniike","doi":"10.1016/j.polymdegradstab.2025.111389","DOIUrl":"10.1016/j.polymdegradstab.2025.111389","url":null,"abstract":"<div><div>A combination of high-throughput chemiluminescence imaging and a genetic algorithm was implemented to develop stabilizer formulations for preventing the thermo-oxidative degradation of poly(4-methyl-1-pentene) (PMP). The identified best-performing formulation significantly enhanced the stability of PMP, extending its lifetime at 160 °C. Additionally, the results were compared to those previously obtained for polypropylene (PP) to identify commonalities and differences in stabilizer formulations between these polymers. It was found that both PMP and PP require synergistic combinations of stabilizers, though PMP tends to favor higher proportion of secondary antioxidants. This difference is likely attributed to processing temperatures and diffusion efficiency of molecules in the matrix polymers. Findings from a total of 160 samples (PMP: 90, PP: 70) highlight the importance of iterative optimization of stabilizer formulations.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111389"},"PeriodicalIF":6.3,"publicationDate":"2025-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143891851","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}

{"title":"Space environment exposure effects on polyimide aerogels","authors":"Sadeq Malakooti ,&nbsp;Stephanie L. Vivod ,&nbsp;Kim K. de Groh ,&nbsp;Jessica L. Cashman ,&nbsp;Mary Ann B. Meador ,&nbsp;DanielA. Scheiman ,&nbsp;Jonathan A. Salem ,&nbsp;Sylvie F. Crowell ,&nbsp;Linda S. McCorkle","doi":"10.1016/j.polymdegradstab.2025.111398","DOIUrl":"10.1016/j.polymdegradstab.2025.111398","url":null,"abstract":"<div><div>As part of the Materials International Space Station Experiment (MISSE) missions, polyimide aerogel samples as prepared and atomic oxygen plasma treated with bulk densities of 0.09 and 0.15 g/cm³ were exposed on the exterior of the International Space Station (ISS) during MISSE-9, 12, and 15 missions for 0.77, 0.89, and 0.44-year direct space exposure times, respectively. The aerogel samples were synthesized from a combination of the diamines 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane (BAPN) and 2,2′-dimethylbenzidine (DMBZ), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), and 1,3,5-triaminophenoxybenzene (TAB) as the crosslinker. At low Earth orbit (LEO), spacecraft are subjected to extreme environmental conditions such as thermal cycling, solar radiation, cosmic rays, solar wind charged particles and atomic oxygen (AO). A post-flight analysis of aerogel physical, chemical, mechanical, thermal and optical properties were performed using a series of non-destructive techniques. The polyimide aerogels exhibited a notably higher AO erosion yield compared to nonporous Kapton H or HN polyimides, attributed to their order of magnitude lower bulk density and much higher surface area. Yet, the post-flight characterizations reveal no significant degradation in material properties. For example, in terms of material’s structural integrity, the post-flight Young’s moduli at both low and high densities were not statistically changed. Similar observations were obtained for thermal and optical properties in terms of changes in the materials’ thermal conductivity and solar absorptance. The aerogel flight samples with pre-flight surface treatments using atomic oxygen plasma showed a higher susceptibility to the LEO environment compared to as-prepared aerogel flight samples. Despite their high AO erosion yield, this study shows that polyimide aerogels maintain remarkable stability throughout extended space missions and explorations and therefore can be considered as a space-rated material.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111398"},"PeriodicalIF":6.3,"publicationDate":"2025-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895215","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}

{"title":"Lignocellulosic nanofibers composite films reinforced with green-synthesized copper oxide nanoparticles for active packaging","authors":"Yihan Gao,&nbsp;Yu-I Hsu,&nbsp;Hiroshi Uyama","doi":"10.1016/j.polymdegradstab.2025.111400","DOIUrl":"10.1016/j.polymdegradstab.2025.111400","url":null,"abstract":"<div><div>The search for alternatives to traditional petroleum-based packaging materials has increasingly focused on high-value utilization of agricultural waste. This study aims to maximize the use of tea waste components as raw materials or green reagents for the preparation of sustainable active packaging materials. Copper oxide nanoparticles were synthesized via a green route using tea waste extract, while tea waste-derived nanofibers were prepared through a simple and environmentally friendly one-step H₂O₂ alkaline treatment and homogenization. These two components were added to polyvinyl alcohol (PVA) to prepare composite films. The results showed that the hydrogen bonding interactions between the components significantly enhanced the physical properties of the composite films. The maximum tensile strength and Young’s modulus reached 43.5 MPa and 311.5 MPa, representing increases of 77.6 % and 223.8 %, respectively, compared to pure PVA films. Furthermore, the composite films exhibited excellent thermal stability and water resistance, with the main degradation peak increasing by 55.3 °C, swelling ratio decreasing by 60.8 %, and the time to reach maximum swelling increased by 21 min. The water contact angle of the composite film reached 93° Additionally, antibacterial tests using the colony counting method and practical packaging tests on fresh chicken meat demonstrated the potential application of the composite film in active packaging, providing a more environmentally friendly alternative to traditional petroleum-based plastic packaging.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111400"},"PeriodicalIF":6.3,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895214","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}

{"title":"Synergistic effects of different component on flame retardant poly(lactic acid) composites based on modified ammonium polyphosphate","authors":"Lijuan Long ,&nbsp;Xiang Nie ,&nbsp;Xin Wang ,&nbsp;Chunyan Shan ,&nbsp;Juan Xie ,&nbsp;Lianjun Shi ,&nbsp;Yi Yang ,&nbsp;Qian Lin ,&nbsp;Hai Fu ,&nbsp;Wei Gong ,&nbsp;Shuhao Qin ,&nbsp;Jie Yu","doi":"10.1016/j.polymdegradstab.2025.111397","DOIUrl":"10.1016/j.polymdegradstab.2025.111397","url":null,"abstract":"<div><div>Synergistic effect between modified oligomeric ammonium polyphosphate with p-methyl benzenesulfonate aluminum (APP@MeAl) and different component including copper oxide (CuO), charring agent (CFA) and hydroxyl group-containing phosphaphenanthrene derivative (DH) on flame-retardant poly(lactic acid) (PLA) were investigated. The results showed that PLA composites with the incorporation of 10 wt%APP@MeAl and 5 wt%DH achieved UL-94 V-0 rating and a LOI value of 28.4 %, superior than those of single APP@MeAl, and the combination by APP@MeAl with CuO or CFA. Thus, synergistic effect of APP@MeAl and DH was more effectively in the flame retardancy of PLA. The synergistic mechanism between APP@MeAl and DH in flame-retarding PLA were discussed in detail. As a result, this strategy provides a convenient and effect way to expand the application of oligomeric APP in preparing highly performance flame retardant polymer composites.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111397"},"PeriodicalIF":6.3,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143906382","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}

{"title":"Modification, degradation, stabilisation of polymers","authors":"Professor Sahar Al-Malaika","doi":"10.1016/j.polymdegradstab.2025.111395","DOIUrl":"10.1016/j.polymdegradstab.2025.111395","url":null,"abstract":"","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111395"},"PeriodicalIF":6.3,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143877118","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}

{"title":"Improving oxidation resistance of Polyphenylene Sulfide fibers by adding Antioxidant loaded Halloysite Nanotubes","authors":"Tian Qiu ,&nbsp;Zexu Hu ,&nbsp;Liping Zhu ,&nbsp;Xu Jin ,&nbsp;Hengxue Xiang ,&nbsp;Zhe Zhou ,&nbsp;Meifang Zhu","doi":"10.1016/j.polymdegradstab.2025.111396","DOIUrl":"10.1016/j.polymdegradstab.2025.111396","url":null,"abstract":"<div><div>The polyphenylene sulfide (PPS) fiber, renowned for its exceptional heat and chemical resistance, finds extensive applications in high-temperature filtration, protective clothing, electronics, automobile and aircraft sectors. However, the oxidation susceptibility of PPS fiber at elevated temperature significantly restricts its practical applications. In this study, a PPS nanocomposite fiber with improved oxidation resistance is prepared by incorporating a low content of antioxidant TH-1790 loaded halloysite nanotubes (T-HNTs) via melt spinning. The successful loading of TH-1790 into HNTs is demonstrated through TEM, TGA and FT-IR. The PPS/T-HNTs nanocomposite fiber with 0.6 wt% of T-HNTs performs the best during the mechanical test, showing a higher breaking strength (4.63 cN/dtex) than others. In addition, an increase of 16.9 °C is found for the maximum weight loss temperature (T_max) of the 0.4 wt% T-HNTs loading sample by TGA, suggesting a better thermal stability. Most importantly, the retention rate of breaking strength is found to be 91.0 % for PPS/T-HNTs-0.6 nanocomposite fibers while that of the pure PPS is only 79.1 % after thermo-oxidative aging. This work provides an effective and accessible method for improving the thermal stability and oxidation resistance of PPS fibers, which thereby helps to extend the applications of PPS fibers in high temperature environment.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111396"},"PeriodicalIF":6.3,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143906383","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}

{"title":"Eugenol-derived trifunctional epoxy resin: Intrinsic phosphorus-free flame retardancy and mechanical reinforcement for sustainable polymer alternatives","authors":"Haiyan Ou,&nbsp;Jianbo Li,&nbsp;Ming Jin,&nbsp;Jie Ren","doi":"10.1016/j.polymdegradstab.2025.111394","DOIUrl":"10.1016/j.polymdegradstab.2025.111394","url":null,"abstract":"<div><div>While conventional epoxy resins exhibit outstanding adhesion and mechanical robustness, their inherent limitations in flame retardancy become critically pronounced under the harsh service environment driven by rapid iteration of advanced technologies. Concurrently, bio-based polymers are gaining prominence in advanced materials research due to their ecological benignity, life-cycle sustainability, and structural tunability. In this study, we developed a trifunctional eugenol-derived epoxy precursor (TEPEU), which upon curing with 4,4′-diaminodiphenyl sulfone (DDS) yields an intrinsically flame-retardant bio-based epoxy system (TEPEU/DDS). Benefiting from its rigid aromatic backbone and high-density epoxy functionalities, TEPEU/DDS exhibits exceptional thermal stability (glass transition temperature of 294.5 °C, char yield of 29.8 % at 700 °C in N₂) and superior fire resistance (limiting oxygen index (LOI) of 28.7 %, total heat release (THR) of 15.9 kJ·g⁻¹). Additionally, remarkable mechanical enhancements are observed, with the storage modulus (4.091 GPa), Young's modulus (4.693 GPa), and hardness (0.407 GPa) being higher than those of petroleum-based DGEBA (diglycidyl ether of bisphenol A)/DDS by 48.3 %, 41.1 %, and 49.1 %, respectively. This halogen-free, zero-additive, high-performance bio-epoxy resin presents a sustainable solution for fire-critical applications such as electronic packaging and aerospace composites.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"239 ","pages":"Article 111394"},"PeriodicalIF":6.3,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143868646","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}