Polymer Degradation and Stability最新文献

Gravity-induced asymmetric gradient PVA-based films with superior radiative cooling and flame retardancy for energy-saving building 节能建筑用重力致不对称梯度聚乙烯醇基辐射冷却阻燃膜

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-28 DOI: 10.1016/j.polymdegradstab.2026.111964

Lian Yin , Yuanyuan Zhang , Yizhi Liu , Sheng Zhang , Keqing Zhou

Polymer-based radiative cooling materials show great promise for green building and carbon neutrality by offering passive cooling. However, their effectiveness is limited by absorption of ambient heat radiation, and inherent flammability, which poses a serious challenge to meeting building safety regulations. Hence, this study modified TiO₂ surfaces using KH-550 and phytic acid to prepare silicon/phosphorus co-modified TiO₂ nanohybrids (KH-TiO₂-PA), which were incorporated into a polyvinyl alcohol (PVA) matrix. Through gravity-induced self-assembly, an asymmetrically gradient multifunctional composite film was formed, exhibiting effective radiative cooling, flame retardancy, and enhanced mechanical strength. Owing to its unique gravity-induced asymmetric gradient structure and the vibrational characteristics of C-C, Ti-O-Ti, Si-O-Si, P-O, and P=O bonds, the PVA/37.5%KH-TiO₂-PA composite film achieved a solar reflectivity of 84.7% and an infrared emissivity of 91.1%. Furthermore, the film demonstrated remarkable cooling performance, reducing temperature by up to 10.4°C in outdoor tests, with daytime and nighttime cooling power values of 61.1 W·m⁻² and 98.1 W·m⁻², respectively. According to EnergyPlus simulations, deploying the film on buildings significantly reduced energy consumption (up to 88.24% savings) and cut CO₂ emissions (up to 2.69 tons and $ 486.97 per year). Meanwhile, the incorporation of KH-TiO₂-PA facilitated gas-phase radical quenching and condensed-phase barrier effects, leading to a 40.5% reduction in peak heat release rate and a 58.6% suppression of peak CO₂ production, which substantially enhanced fire safety. Notley, when reinforced with the nanoparticles, the PVA/12.5%KH-TiO₂-PA composite achieved a tensile strength of 113.28 MPa and a Young’s modulus of 4.82 GPa, demonstrating 39.9% and 56.5% enhancements, respectively. This study offers a viable strategy for addressing climate challenges and supporting safe green building development, thereby promoting the application of multifunctional materials in energy-efficient buildings.

聚合物基辐射冷却材料通过提供被动冷却，在绿色建筑和碳中和方面显示出巨大的前景。然而，它们的有效性受到环境热辐射的吸收和固有的可燃性的限制，这对满足建筑安全法规提出了严重的挑战。因此，本研究利用KH-550和植酸对TiO2表面进行改性，制备了硅/磷共改性TiO2纳米杂化物（KH-TiO2-PA），并将其掺入聚乙烯醇（PVA）基体中。通过重力诱导的自组装，形成了一种不对称梯度的多功能复合膜，具有有效的辐射冷却、阻燃和增强的机械强度。由于其独特的重力诱导不对称梯度结构和C-C、Ti-O-Ti、Si-O-Si、P-O和P=O键的振动特性，PVA/37.5%KH-TiO2-PA复合膜的太阳反射率为84.7%，红外发射率为91.1%。此外，该薄膜表现出显著的冷却性能，在室外测试中降低温度高达10.4°C，白天和夜间冷却功率分别为61.1 W·m−2和98.1 W·m−2。根据EnergyPlus的模拟，在建筑物上部署该薄膜可显着降低能耗（节省高达88.24%）并减少二氧化碳排放（每年高达2.69吨和486.97美元）。同时，h - tio2 - pa的掺入促进了气相自由基猝灭和凝聚相势垒效应，峰值放热率降低40.5%，峰值CO2产量降低58.6%，大大提高了防火安全性。结果表明，PVA/12.5%KH-TiO2-PA复合材料的抗拉强度为113.28 MPa，杨氏模量为4.82 GPa，分别提高了39.9%和56.5%。本研究为应对气候挑战和支持安全绿色建筑发展提供了可行的策略，从而促进多功能材料在节能建筑中的应用。

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引用次数: 0

Boosting the flame retardancy of vinyl ester resins via a DE@DMMP hybrid: Reducing migration and improving fire performance 通过DE@DMMP混合物提高乙烯基酯树脂的阻燃性：减少迁移和提高防火性能

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-27 DOI: 10.1016/j.polymdegradstab.2026.111963

Jinxin Xie , Akhmetova Marzhan , Zhanturina Nurgul , Yanbei Hou , Bekeshev Amirbek , Weizhao Hu , Xin Wang , Yuan Hu , Fukai Chu

Vinyl ester resins (VER) require flame-retardant modification for safe application, but conventional additives face limitations. To overcome the high volatility and migration tendency of the effective liquid phosphorus flame retardant dimethyl methylphosphonate (DMMP), this study develops a novel composite by confining DMMP within the micro-nano porous structure of diatomite (DE) to form a DE@DMMP hybrid. This hybrid was incorporated into VER to create flame-retardant composites. Successful DMMP adsorption onto DE was confirmed through FTIR and SEM analysis. Compared with the physically mixed DE/DMMP system, the VER composite containing 25 wt% DE@DMMP exhibited better thermal stability and more char residues. It achieved superior flame retardancy, with a limiting oxygen index of 26% and a UL-94 V-0 rating. Cone calorimetry tests revealed a remarkable 50.54% reduction in the peak heat release rate and a 58.30% decrease in total heat release versus pure VER, alongside suppressed total smoke production. The enhanced performance is attributed to a synergistic phosphorus-silicon effect. The immobilized DMMP provides efficient gas-phase radical quenching, whereas the silica framework of DE promotes the formation of a compact, thermally stable char layer enriched with Si-O-P crosslinking structures, as evidenced by XPS analysis. This work presents an effective strategy to mitigate additive migration and develop high-performance, halogen-free, flame-retardant VER with balanced fire safety.

乙烯基酯树脂（VER）需要阻燃改性才能安全应用，但传统添加剂存在局限性。为了克服有效液态磷阻燃剂甲基膦酸二甲酯（DMMP）的高挥发性和迁移倾向，本研究通过将DMMP限制在硅藻土（DE）的微纳多孔结构中形成DE@DMMP杂化物，开发了一种新型复合材料。这种混合物被加入到VER中以制造阻燃复合材料。通过FTIR和SEM分析证实了DMMP在DE上的成功吸附。与物理混合DE/DMMP体系相比，含有25 wt% DE@DMMP的VER复合材料具有更好的热稳定性和更多的炭残。它达到了优异的阻燃性，具有26%的极限氧指数和UL-94 V-0等级。锥形量热测试显示，与纯VER相比，峰值热释放率降低了50.54%，总热释放率降低了58.30%，同时总烟产量受到抑制。性能的增强是由于磷硅的协同效应。固定化的DMMP提供了有效的气相自由基猝灭，而DE的二氧化硅框架促进形成致密、热稳定的富含Si-O-P交联结构的炭层，这一点得到了XPS分析的证实。这项工作提出了一个有效的策略，以减轻添加剂迁移和开发高性能，无卤，阻燃VER与平衡的防火安全。

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引用次数: 0

Self-Defending Pseudomorphic Glass Against Atomic Oxygen for LEO Flexible Photovoltaic Encapsulation 用于低轨柔性光伏封装的防原子氧伪晶玻璃

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-25 DOI: 10.1016/j.polymdegradstab.2026.111960

Huiyang Zhao , Wenhao Shen , Weinan Zhang , Dandan Ju , Songtao Lu , Yiyong Wu

The degradation of polymer materials in the atomic oxygen (AO) environment of low Earth orbit (LEO) significantly limits their application in lightweight spacecraft power systems. In this work, we investigate self-defending pseudomorphic glass (PMG) designed for flexible photovoltaic encapsulation. PMG exhibits an erosion rate only 13% of that of Kapton® after 2 × 10²¹ atoms /cm² of AO exposure. PMG encapsulation effectively maintained the critical photovoltaic cell parameters, with negligible degradation in open-circuit voltage (Voc, 0.10%) and short-circuit current (Isc, 0.21%), as well as a stable external quantum efficiency over the entire measured spectral range. During AO exposure, PMG forms a protective SiO_X layer that functions as a self-defending barrier through continuous oxidative cross-linking, thereby minimizing optical degradation and preserving the power-generation performance of encapsulated solar cells. The inclusion of glass beads further enhances AO resistance by acting both as a reinforcing phase and as sites for energy dissipation. This study provides a viable strategy for fabricating high-performance, AO-resistant polymer composites for space photovoltaic encapsulation applications.

高分子材料在近地轨道原子氧环境下的降解严重限制了其在航天器轻量化动力系统中的应用。在这项工作中，我们研究了用于柔性光伏封装的自卫伪晶玻璃（PMG）。在2 × 1021个原子/cm2的AO暴露后，PMG的侵蚀率仅为Kapton®的13%。PMG封装有效地保持了光伏电池的关键参数，开路电压（Voc, 0.10%）和短路电流（Isc, 0.21%）的退化可以忽略不计，并且在整个测量光谱范围内具有稳定的外量子效率。在AO暴露过程中，PMG形成一个保护性的SiOX层，通过持续的氧化交联起到自我防御屏障的作用，从而最大限度地减少光学退化并保持封装太阳能电池的发电性能。玻璃微珠的加入通过作为增强相和能量耗散位点进一步增强了AO阻力。该研究为制造高性能、抗ao聚合物复合材料提供了可行的策略，用于空间光伏封装应用。

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引用次数: 0

Synergistic thermal shielding and corrosion protection via Al2O3@HAP-reinforced polypropylene 通过Al2O3@HAP-reinforced聚丙烯协同热屏蔽和防腐

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-25 DOI: 10.1016/j.polymdegradstab.2026.111958

Salman Khalid , Mohammad Tabish , Yifang Hua , Muhammad Mubeen , Xinyu Chen , Libo Li , H.M. Ahsen Ilyas , Jun Sun , Xiaoyu Gu , Ghulam Yasin , Sheng Zhang

Achieving simultaneous flame retardancy and anti-corrosion properties in advanced polypropylene (PP) composites and coatings presents a significant challenge. In this work, porous alumina microspheres (Al₂O₃) were prepared via a hydrothermal method and subsequently calcined at 600°C for 3 hours (h). Al₂O₃ was then hybridized with hydroxyapatite (HAP) nanosheets through sonication followed by simple stirring at ambient temperature for 24 h to obtain the Al₂O₃@HAP nanohybrid. The synthesized Al₂O₃ and Al₂O₃@HAP, together with melamine polyphosphate (MPP) and piperazine pyrophosphate (PAPP), were incorporated into PP as fillers to enhance flame-retardant properties. An MPP/PAPP intumescent flame-retardant (IFR) system was employed due to its high char-forming efficiency and environmentally friendly characteristics, offering a promising alternative to halogenated flame-retardants. The PP/12%IFR/3%Al₂O₃@HAP composite exhibited excellent flame retardancy, as demonstrated by a high limiting oxygen index (LOI) of 28.2%, a V-0 rating in the vertical burning test (UL-94), and substantial reductions in peak heat release rate (pHRR, 86%), total heat release (THR, 43%), and total smoke production (TSP, 44%) compared with the control PP. Furthermore, the Al₂O₃@HAP nanohybrid effectively protected Zn-Al-Mg (ZAM) coated-steel against corrosion. The PP/PP-g-MAH/Al₂O₃@HAP nanocomposite coating maintained a high impedance (|Z|_{0.01 Hz}) of 5.46 × 10⁸ Ω cm² after 60 days of immersion in 3.5 wt% NaCl solution, indicating excellent long-term stability. Pull-off adhesion tests demonstrated that the incorporation of the fillers significantly enhanced the adhesion strength compared with the pristine PP/PP-g-MAH coating. Overall, this research presents an efficient strategy for fabricating advanced PP-based materials with simultaneously improved flame retardancy and corrosion resistance, offering substantial potential for diverse industrial applications.

在高级聚丙烯（PP）复合材料和涂层中实现同时阻燃和防腐性能是一个重大挑战。在这项工作中，通过水热法制备多孔氧化铝微球（Al2O3），随后在600°C下煅烧3小时(h)。通过超声将Al2O3与羟基磷灰石（HAP）纳米片杂交，然后在室温下简单搅拌24 h，得到Al2O3@HAP纳米杂化物。将合成的Al2O3和Al2O3@HAP与三聚氰胺聚磷酸（MPP）和焦磷酸哌嗪（PAPP）作为填料掺入PP中，以提高阻燃性能。采用MPP/PAPP膨胀型阻燃剂（IFR）体系，由于其高成炭效率和环保特性，为卤化阻燃剂提供了一个有前途的替代品。PP/12%IFR/3%Al2O3@HAP复合材料表现出优异的阻燃性能，其极限氧指数（LOI）高达28.2%，垂直燃烧试验（UL-94）的V-0等级较高，峰值放热率（pHRR, 86%）、总放热率（THR, 43%）和总产烟率（TSP, 44%）均显著降低。此外，Al2O3@HAP纳米杂化材料还能有效地保护Zn-Al-Mg （ZAM）涂层钢免受腐蚀。在3.5 wt% NaCl溶液中浸泡60天后，PP/PP-g- mah /Al2O3@HAP纳米复合涂层保持5.46 × 108 Ω cm2的高阻抗（|Z|0.01 Hz），具有良好的长期稳定性。拉拔附着力测试表明，与原始PP/PP-g- mah涂层相比，填料的掺入显著提高了附着力。总的来说，这项研究提出了一种制造先进pp基材料的有效策略，同时提高了阻燃性和耐腐蚀性，为各种工业应用提供了巨大的潜力。

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引用次数: 0

Multifunctional coating for polyester/spandex fabrics with carbon black/melamine polyphosphate/aluminum diethylphosphinate dispersion: flame retardancy and antistatic protection 炭黑/聚磷酸三聚氰胺/二乙基膦酸铝分散体聚酯/氨纶织物多功能涂料：阻燃和抗静电保护

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-24 DOI: 10.1016/j.polymdegradstab.2026.111956

Xian-Wei Cheng , Jia-Yi Song , Zheng-Yi Wang , Ying-Jie He , Jun Wu , Jun-Hui Yang , Kang Tao , Jin-Ping Guan

The development of sustainable, multifunctional polyester/spandex (T/S) protective fabrics is of increasing importance for advanced textile applications. In this study, a stable and multifunctional dispersion comprising melamine polyphosphate (MPP), aluminum diethylphosphinate (ADP), and carbon black (CB) was prepared via zirconia bead-assisted grinding and subsequently applied to T/S fabrics using a roll-bake coating process with the aid of polyacrylate adhesive. The coated T/S fabrics were systematically evaluated for color characteristics, antistatic performance, flame retardancy, combustion behavior, and underlying flame-retardant mechanisms. The results revealed that the coated T/S fabrics exhibited stable black coloration and excellent antistatic property, with minimal impact on tensile strength and air permeability. Furthermore, the coated T/S fabrics demonstrated self-extinguishing behavior, with a significantly reduced damaged length of about 7.1 cm and no molten dripping. The limiting oxygen index reached 27.5%, indicating enhanced flame resistance. They also displayed significantly suppressed heat release capacity. Mechanistically, MPP and ADP promoted the formation of a stable char layer through acid catalysis and carbonization, while releasing phosphorus-containing radicals and inert gases that disrupted flame-propagating reactions and reduced local oxygen concentration, effectively inhibiting combustion.

开发可持续、多功能的涤纶/氨纶（T/S）防护织物对于高级纺织品的应用越来越重要。在本研究中，通过氧化锆珠辅助研磨制备了由三聚氰胺聚磷酸（MPP）、二乙基膦酸铝（ADP）和炭黑（CB）组成的稳定多功能分散体，随后使用聚丙烯酸酯粘合剂辅助辊烘涂覆工艺将其应用于T/S织物。系统地评估了涂层T/S织物的颜色特性、抗静电性能、阻燃性、燃烧性能和潜在的阻燃机理。结果表明，涂层后的T/S织物呈现稳定的黑色着色，抗静电性能优异，对拉伸强度和透气性的影响最小。此外，涂层的T/S织物表现出自熄行为，显著减少了约7.1 cm的损坏长度，没有熔融滴水。极限氧指数达到27.5%，阻燃性增强。它们也表现出明显抑制的放热能力。从机理上讲，MPP和ADP通过酸催化和碳化作用促进稳定炭层的形成，同时释放含磷自由基和惰性气体，破坏火焰传播反应，降低局部氧浓度，有效抑制燃烧。

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引用次数: 0

Organic-inorganic epoxy-polysilazane hybrid adhesives: High-temperature structural stability and self-reinforced interfaces 有机-无机环氧-聚硅氮烷杂化粘合剂：高温结构稳定性和自增强界面

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-22 DOI: 10.1016/j.polymdegradstab.2026.111955

Haochen Guo , Haotian Xiao , Weigui Kang , Xiaoqing Sun , Zijie Xu , Jian Xu , Xiaoxiao Zhang , Tianhao Li , Chongwen Yu , Yujie Song

High-temperature stability in epoxy adhesives often relies on rigid structures, such as benzene rings, which increase brittleness and limit polar group mobility, deteriorating adhesion performance. However, good adhesion performance requires flexible segments and polar groups, which lowers high-temperature stability. Such limitations restrict the use of epoxy adhesives in extreme environments. In this work, we cured E44 epoxy resin with organic-inorganic hybrid polysilazane (PSZ). PSZ forms a densely crosslinked network with epoxy molecular segments while simultaneously generating Si-O-Si inorganic structures within the network. The inorganic structure Si-N and Si-O in this network exhibits better thermal stability than that of benzene-ring-containing epoxies. Furthermore, the hybrid network shows unique dynamic behavior at high temperatures: The organic epoxy structure contributes to high adhesion ability, while the inorganic siloxane backbone provides high-temperature stability. The siloxane backbone also exhibits flexibility at elevated temperatures, which allows the crosslinked molecular segments to undergo relaxation and rearrangement. This process optimizes their conformation, giving the polymer chains better interfacial adaptability and increasing their Van der Waals forces with the substrate. This high-temperature interface self-enhancement effect results in the system retaining up to 35% of its adhesion strength at 250°C and retaining up to 80% after 250°C high-temperature aging. The inorganic structure's protection of the carbon chains also enables the system to meet flame retardancy requirements. This work expands applications of epoxy resin adhesives in extreme environments.

环氧胶粘剂的高温稳定性通常依赖于苯环等刚性结构，这会增加脆性并限制极性基团的迁移，从而降低粘合性能。然而，良好的粘附性能需要柔性段和极性基团，这降低了高温稳定性。这些限制限制了环氧胶粘剂在极端环境中的使用。本研究以有机-无机杂化聚硅氮烷（PSZ）固化E44环氧树脂。PSZ与环氧分子段形成紧密交联的网络，同时在网络内生成Si-O-Si无机结构。该网络中的无机结构Si-N和Si-O表现出比含苯环环氧树脂更好的热稳定性。此外，混合网络在高温下表现出独特的动态行为：有机环氧树脂结构有助于提高粘接能力，而无机硅氧烷主链提供高温稳定性。硅氧烷主链在高温下也表现出灵活性，这使得交联的分子片段能够进行松弛和重排。该工艺优化了它们的构象，使聚合物链具有更好的界面适应性，并增加了它们与衬底的范德华力。这种高温界面自增强效应使体系在250°C时保持高达35%的附着强度，在250°C高温时效后保持高达80%的附着强度。无机结构对碳链的保护也使体系能够满足阻燃要求。这项工作扩大了环氧树脂胶粘剂在极端环境中的应用。

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引用次数: 0

A multi-scale porous design enabling in-situ α-ZrP growth for high flame-retardant SLA-printed photopolymers 一种多尺度多孔设计，使高阻燃sla印刷光聚合物的α-ZrP原位生长成为可能

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-22 DOI: 10.1016/j.polymdegradstab.2026.111954

Zehua Zhuo , Rui Wang , Shaoyun Chen , Jianhong Gao , Cuifang Cai , Yanyu Zheng , Xiaoying Liu , Bo Qu , Qinghui Chen , Dongxian Zhuo

Stereolithography (SLA) is highly valued in high-end manufacturing for its exceptional design flexibility. However, the inherent flammability of photosensitive resins significantly limits their safe application. This study designed and synthesized an intrinsically flame-retardant photosensitive resin (TPH) containing phosphorus and sulfur elements. The TPH resin was blended with a phosphorus-containing reactive diluent and an ionic liquid (TFS) to prepare a photosensitive resin (TPHP) suitable for SLA technology. An innovative approach was employed where macroscopic pore structures were constructed through 3D printing, and due to phase separation between the ionic liquid and the 3D-printed samples, microscopic pores were incorporated within the SLA-printed specimens, a porous framework was formed. These pores served as reaction sites for in-situ growth of a nano-zirconium phosphate (α-ZrP) layer on the surface. Thermogravimetric and flame retardancy tests demonstrated that the incorporation of α-ZrP significantly enhanced the material's thermal stability, flame retardancy, and smoke suppression properties. Compared with unmodified samples, the char residue was increased to 47.3%, the limiting oxygen index reached 29.0%, and the UL-94 rating achieved V-0. Cone calorimetry tests showed reductions in peak heat release rate, total heat release, and total smoke production by 42.1%, 65.4%, and 75.1%, respectively. The results indicate that this work provides a new strategy for flame-retardant 3D printing. It resolves the intrinsic conflict between flame retardancy and printability by combining surface pore engineering with in situ growth to achieve surface functionalization without sacrificing printability.

立体光刻（SLA）因其独特的设计灵活性在高端制造业中受到高度重视。然而，光敏树脂固有的可燃性极大地限制了它们的安全应用。设计并合成了一种含磷、硫元素的本燃型光敏树脂（TPH）。将TPH树脂与含磷活性稀释剂和离子液体（TFS）混合，制备出适合SLA技术的光敏树脂（TPHP）。采用了一种创新的方法，通过3D打印构建宏观孔隙结构，并且由于离子液体与3D打印样品之间的相分离，微观孔隙被纳入sla打印样品中，形成多孔框架。这些孔是在表面原位生长纳米磷酸锆（α-ZrP）层的反应位点。热重和阻燃试验表明，α-ZrP的加入显著提高了材料的热稳定性、阻燃性和抑烟性。与未改性样品相比，炭渣率提高到47.3%，极限氧指数达到29.0%，UL-94等级达到V-0。锥量热测试表明，峰值放热率、总放热率和总烟雾产量分别降低了42.1%、65.4%和75.1%。结果表明，本工作为阻燃3D打印提供了一种新的策略。将表面孔隙工程与原位生长相结合，在不牺牲印刷性的前提下实现表面功能化，解决了阻燃性与印刷性之间的内在矛盾。

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引用次数: 0

Green and thermostable bio-based flame retardant system: A new strategy for preparing flame-retardant polyvinyl alcohol materials via melt processing 绿色耐热生物基阻燃体系：熔体法制备阻燃聚乙烯醇材料的新策略

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-21 DOI: 10.1016/j.polymdegradstab.2026.111953

Ziyi Xuan , Wenzong Xu , Zhongqiong Qin , Jiayan Zhang , Julan Liu

In recent years, with the deepening of sustainable development concepts, polyvinyl alcohol (PVA) has garnered widespread attention as a biodegradable, non-toxic material. However, its inherent flammability significantly limits its practical applications. Developing flame-retardant PVA materials suitable for melt processing while maintaining their tensile properties remains a major challenge for practical PVA applications. This study synthesized a novel, highly thermally stable, eco-friendly bio-based flame retardant, CADCM, which was incorporated into the PVA matrix via melt processing. Results indicated that with the addition of just 12.5 wt% CADCM, the PVA composite achieved a limiting oxygen index (LOI) value of 30.3 % and a vertical combustion test UL-94 rating of V-0. Reductions of 66.1 % in the peak heat release rate (pHRR) and 31.7 % in total heat release (THR) were observed compared to PVA0. This demonstrates that the synthesized flame retardant CADCM is suitable for preparing PVA composites with excellent flame retardancy via melt processing. Regarding mechanical properties, the composite exhibited improvements of 27.4 % in tensile strength and 285.2 % in elastic modulus. In terms of processing performance, the processing melting temperature of the PVA composite with CADCM addition remained suitable for processing requirements, maintaining good processability. The bio-based melt-processable flame-retardant PVA composite prepared in this study provides a feasible pathway and new insights for further expanding the scope of practical application fields of PVA materials.

近年来，随着可持续发展理念的深入，聚乙烯醇（PVA）作为一种可生物降解的无毒材料受到了广泛关注。然而，其固有的可燃性极大地限制了其实际应用。开发适合熔体加工的阻燃聚乙烯醇材料，同时保持其拉伸性能仍然是聚乙烯醇实际应用的主要挑战。本研究合成了一种新型的、高度热稳定的、环保的生物基阻燃剂CADCM，该阻燃剂通过熔体加工加入到PVA基体中。结果表明，仅添加12.5%的CADCM， PVA复合材料的极限氧指数（LOI）为30.3%，垂直燃烧测试UL-94等级为V-0。与PVA0相比，峰值放热率（pHRR）降低了66.1%，总放热率（THR）降低了31.7%。这表明合成的阻燃剂CADCM适合通过熔体加工制备阻燃性能优良的PVA复合材料。力学性能方面，复合材料抗拉强度提高27.4%，弹性模量提高285.2%。在加工性能方面，添加CADCM的PVA复合材料的加工熔融温度仍然适合加工要求，保持了良好的加工性。本研究制备的生物基熔融可加工阻燃PVA复合材料为进一步扩大PVA材料的实际应用领域范围提供了可行的途径和新的见解。

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引用次数: 0

In-situ synergistic enhancement of interlayer bonding strength and flame retardancy in 3D printed CF/PEEK composites via Nano-POSS under elevated chamber temperature 高温下纳米poss原位协同增强3D打印CF/PEEK复合材料层间结合强度和阻燃性

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-20 DOI: 10.1016/j.polymdegradstab.2026.111952

Shouao Zhu , Zhe Peng , Ruoqi Guo , Wei Zhao , Binling Chen , Bo Xu

3D printed carbon fiber reinforced polyether ether ketone (CF/PEEK) composites have the potential for a wide range of applications, including in the electrical and electronic appliances, automotive, and aerospace industries. Understanding how to enhance the interlayer bonding strength and the combustion behavior of carbon fiber composites are prerequisites for these applications. In this study, a high-performance anti-static CF/PEEK ESD composite for material extrusion (ME) 3D printing was prepared using recycled carbon fibers (rCF), carbon nanotubes (CNTs), and polyhedral oligomeric silsesquioxane (T₇-POSS). The interlayer adhesion and combustion of 3D printed CF/PEEK ESD at a high chamber temperature (255 °C) were enhanced in situ by the combined action of gas-phase and condensed-phase materials obtained by pyrolyzing POSS and aligned CF. The interlayer adhesion of CF/PEEK ESD reaches 46 MPa, and its time to ignition (TTI) is extended to 606 s, while the peak heat release rate (pHRR) is as low as 93 kW/m². Furthermore, during the printing process, POSS decomposes to produce substances with a large number of benzene rings and -OH groups. These substances are π-π conjugated and hydrogen-bonded to the PEEK molecular chain, promoting the ordering of the PEEK molecular chains and enhancing the interlayer bonding and combustion properties. This meets the needs of the aerospace and electrical and electronic industries for materials that are high-strength, flame-retardant, and anti-static. It also provides technical support for the development of high-performance 3D printing materials.

3D打印碳纤维增强聚醚醚酮（CF/PEEK）复合材料具有广泛的应用潜力，包括电气和电子电器、汽车和航空航天工业。了解如何提高碳纤维复合材料的层间结合强度和燃烧性能是这些应用的先决条件。本研究以再生碳纤维（rCF）、碳纳米管（CNTs）和多面体低聚硅氧烷（T7-POSS）为材料，制备了用于材料挤出（ME） 3D打印的高性能抗静电CF/PEEK ESD复合材料。在高温（255°C）下，通过热解POSS和定向CF得到的气相和凝聚相材料的共同作用，原位增强了3D打印CF/PEEK ESD的层间附着力和燃烧性能。CF/PEEK ESD的层间附着力达到46 MPa，点火时间延长至606 s，峰值放热率（pHRR）低至93 kW/m²。此外，在印刷过程中，POSS分解产生含有大量苯环和-OH基团的物质。这些物质与PEEK分子链呈π-π共轭和氢键结合，促进了PEEK分子链的有序，增强了层间键合和燃烧性能。这满足了航空航天和电气电子工业对高强度、阻燃和防静电材料的需求。为高性能3D打印材料的开发提供技术支持。

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引用次数: 0

On the resistance of PEKK to degradation during multiple recycling cycles for additive manufacturing 增材制造中PEKK在多次循环中的抗降解性能研究

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2026-01-20 DOI: 10.1016/j.polymdegradstab.2026.111951

F. Malekpour , M. Hojjati

The recyclability of high-performance poly(ether ketone) (PEKK) is critical for sustainable additive manufacturing and future in-space resource utilization. This study systematically evaluates the thermal, mechanical, and chemical stability of PEKK subjected to multiple recycling loops to elucidate potential degradation mechanisms. Thermogravimetric analysis revealed negligible (<1%) mass loss after 5 h of isothermal exposure below 450 °C, confirming the polymer’s excellent thermal resistance under extrusion and printing conditions. Cyclic differential scanning calorimetry (DSC) demonstrated stable melting and cold-crystallization behavior across six thermal cycles, indicating preserved crystallization kinetics. Tensile testing showed that the amorphous strength remained within 83–91 MPa across all cycles, while annealed samples maintained strengths of 102–116 MPa. Flexural strength similarly remained consistent, ranging from 112 to 127 MPa (amorphous) and 147–160 MPa (annealed), and dynamic mechanical analysis (DMA) results indicated minimal changes in viscoelastic properties. Together, these mechanical and thermomechanical analyses confirm that PEKK retains its structural integrity after three complete recycling sequences involving shredding, pulverization, extrusion, and reprinting. Fourier transform infrared spectroscopy detected no new carbonyl or hydroxyl bands, excluding oxidative chain scission, while X-ray fluorescence (XRF) revealed only trace (<0.5 wt%) metallic contamination. Scanning electron microscopy (SEM) of fracture surfaces further confirmed well-fused interlayer morphology and minimal porosity evolution. Collectively, these results demonstrate that PEKK maintains its molecular and microstructural integrity during repeated thermal–mechanical cycles, highlighting its exceptional thermal-oxidative stability and its suitability for circular, high-performance, and extended-lifetime polymer applications.

高性能聚醚酮（PEKK）的可回收性对于可持续增材制造和未来空间资源利用至关重要。本研究系统地评估了PEKK在多次循环下的热、力学和化学稳定性，以阐明潜在的降解机制。热重分析显示，在低于450°C的等温暴露5小时后，质量损失可以忽略不计（<1%），证实了该聚合物在挤压和印刷条件下具有优异的耐热性。循环差示扫描量热法（DSC）在6个热循环中显示出稳定的熔融和冷结晶行为，表明结晶动力学保持不变。拉伸试验表明，在所有循环过程中，非晶态强度保持在83 ~ 91 MPa之间，而退火后的非晶态强度保持在102 ~ 116 MPa之间。弯曲强度同样保持一致，范围从112到127兆帕（非晶）和147-160兆帕（退火），动态力学分析（DMA）结果表明粘弹性性能变化很小。总之，这些机械和热机械分析证实，PEKK在粉碎、粉碎、挤压和重印三个完整的回收过程后，仍保持其结构完整性。傅里叶变换红外光谱未检测到新的羰基或羟基带，不包括氧化链断裂，而x射线荧光（XRF）仅显示微量（<0.5 wt%）金属污染。断口表面的扫描电镜进一步证实了层间形态融合良好，孔隙度演化最小。总的来说，这些结果表明，PEKK在重复的热机械循环中保持了其分子和微观结构的完整性，突出了其卓越的热氧化稳定性，以及其适用于圆形、高性能和延长寿命的聚合物应用。

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引用次数: 0