Polymer Degradation and Stability最新文献_第7页

Degradation mechanism for epoxy resins under combined electric, thermal and compressive stresses 环氧树脂在电、热和压缩综合应力作用下的降解机理

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-13 DOI: 10.1016/j.polymdegradstab.2024.111038

Gaoyi Shang , Yingman Sun , Hao Tang , Xining Li , Shuqi Zhang , Jinzhong Li , Xuandong Liu

Epoxy resins are widely used in equipment such as ultra-high voltage dry-type bushings, which are subjected to severe electric, thermal, and compressive stresses. Some physical mechanisms have already been proposed to explain the degradations generated by these different stresses, however their effects have not yet been quantified.. The degradation characteristics of epoxy resin under combined stresses of 8 kV/mm, 40 °C-120 °C, and 0–60 MPa were investigated in experiments. The results showed that the degradation characteristics turned significantly with the increase of compressive stress. With the increase in compressive stress, initially the partial discharge initiation voltage, tree initiation voltage and time to breakdown increased, and fractal dimension decreased. While the compressive stress exceeded the turning point, the characteristics were reversed. It can be suggested that opposing mechanisms exist. The free volume and phase field theories dominate at lower and higher stresses, respectively. A novel degradation model of the epoxy resin was proposed based on the theories above. When the compressive stress was low, the reduction of free volume played a dominant role in slowing down the degradation. When the compressive stress was high, the partial energy density concentration accelerated the degradation and played a dominant role. The molecular dynamics and finite element simulation of degradation process stress was carried out and proved consistent with experiments. It confirmed the proposed degradation model reliable and valid.

环氧树脂广泛应用于超高压干式套管等设备中，这些设备需要承受严重的电、热和压缩应力。人们已经提出了一些物理机制来解释这些不同应力产生的降解，但尚未对其影响进行量化。实验研究了环氧树脂在 8 kV/mm、40 ℃-120 ℃ 和 0-60 MPa 的综合应力下的降解特性。结果表明，降解特性随着压缩应力的增加而显著改变。随着压应力的增加，开始时局部放电起始电压、树状起始电压和击穿时间增加，分形尺寸减小。当压应力超过转折点时，特性发生了逆转。这表明存在相反的机制。自由体积理论和相场理论分别在较低和较高应力下占主导地位。根据上述理论，我们提出了一种新的环氧树脂降解模型。当压缩应力较低时，自由体积的减少在减缓降解过程中起主导作用。当压应力较高时，部分能量密度集中加速了降解并起主导作用。对降解过程应力进行了分子动力学和有限元模拟，结果与实验结果一致。这证实了所提出的降解模型是可靠和有效的。

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引用次数: 0

The effect of carbon black on degradation of pipe grade black polyethylene in high concentration chlorine dioxide solutions 炭黑对管道级黑色聚乙烯在高浓度二氧化氯溶液中降解的影响

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-12 DOI: 10.1016/j.polymdegradstab.2024.111031

Amirhosein Sarafpour, Gholamreza Pircheraghi

In this research, the impact of carbon black on the accelerated degradation of pipe grade polyethylene (PE100) exposed to high levels of chlorine dioxide (150 ppm) is examined. Tensile testing reveals a faster degradation rate in black samples compared to neat samples, indicating a detrimental effect of carbon black aggregates on the polymer's aging process. Rheological analysis shows changes in molecular weight and structure due to chemical degradation and chain scission and can be a reliable method for detecting slight changes in molecular structure. Isothermal crystallization shows a slowdown in crystallization kinetics at first, explained by gel-formation due to crosslinking which hinder the crystallization, and then an increase in the kinetics as apparently the chain scission gets dominant again. Neat samples exhibit a higher density of tie molecules, indirectly revealed by much more fibrils in crack wall observed in FESEM images, suggesting better resistance to chemical degradation while the black sample shows a much less fibrillar crack wake and becomes almost completely devoid of any fibrils at later stages of aging. The fibrils, which essentially offer a load-bearing role against the widening and growth of the crack play a key role in resistance to slow crack growth (SCG). Therefore, the higher SCG resistance is expected for neat grade compared to black samples. The study proposes a dual-layer pipe design with a UV-resistant black outer layer and an oxidation-resistant neat inner layer to prolong the lifespan of PE100 pipes by protecting against UV radiation and chemical reactions. This solution offers increased durability, lower maintenance costs, and environmental sustainability benefits.

本研究探讨了炭黑对暴露于高浓度二氧化氯（150 ppm）的管材级聚乙烯（PE100）加速降解的影响。拉伸测试表明，与纯样品相比，黑色样品的降解速度更快，这表明炭黑聚集体对聚合物的老化过程有不利影响。流变分析表明化学降解和链裂导致分子量和结构发生变化，是检测分子结构细微变化的可靠方法。等温结晶显示结晶动力学起初会减慢，原因是交联导致凝胶形成，阻碍了结晶，但随后动力学又会加快，因为显然链裂解又占据了主导地位。整齐的样品显示出更高的绑扎分子密度，这从 FESEM 图像中观察到的裂纹壁上更多的纤维状物可以间接看出，这表明样品具有更强的抗化学降解能力，而黑色样品显示出更少的纤维状裂纹，在老化的后期几乎完全没有任何纤维状物。纤丝主要起承重作用，防止裂纹扩大和增长，在抗慢速裂纹增长（SCG）方面起着关键作用。因此，与黑色样品相比，纯净级样品的抗慢速裂纹生长能力更强。该研究提出了一种双层管材设计，即外层为抗紫外线的黑色管材，内层为抗氧化的纯净管材，通过防止紫外线辐射和化学反应来延长聚乙烯 100 管材的使用寿命。这种解决方案可提高耐用性，降低维护成本，并有利于环境的可持续发展。

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引用次数: 0

An understanding of component-properties relationship of high-temperature resistant addition-cure liquid silicone rubber: A review 了解耐高温加成固化液体硅橡胶的成分属性关系：综述

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-10 DOI: 10.1016/j.polymdegradstab.2024.111034

Yue Xing , Hailan Kang , Donghan Li , Feng Yang , Qinghong Fang

The demand for addition-cure liquid silicone rubber (ALSR) with high temperature resistance in various fields is continuously surging, propelled by the rapid advancement of industries such as aerospace, electronics, and transportation. However, the intricate relationship between the structure and performance of ALSR remains unclear. Therefore, this present study aims to conduct a comprehensive review of recent research advancements in ALSR. More specifically, it pertains to the thermal degradation behavior of silicone rubber; providing a comprehensive review of four components in high-temperature resistant ALSR, including basic polymers, crosslinking agents, fillers, and catalysts; elucidating the relationship between each component and heat resistance properties; as well as addressing the future challenges about high-temperature resistant ALSR. This review provides valuable insights into the design of a high-temperature resistant ALSR.

随着航空航天、电子和交通运输等行业的快速发展，各领域对耐高温加成固化液体硅橡胶（ALSR）的需求不断激增。然而，ALSR 结构与性能之间的复杂关系仍不清楚。因此，本研究旨在全面回顾 ALSR 的最新研究进展。具体而言，本研究涉及硅橡胶的热降解行为；全面综述耐高温 ALSR 的四种成分，包括基本聚合物、交联剂、填料和催化剂；阐明每种成分与耐热性能之间的关系；以及应对耐高温 ALSR 的未来挑战。本综述为耐高温 ALSR 的设计提供了宝贵的见解。

引用次数: 0

Preparation and characterization of HNTs@ZIF enhanced intrinsic flame retardant RTV silicone rubber HNTs@ZIF 增强型本征阻燃 RTV 硅橡胶的制备与表征

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-10 DOI: 10.1016/j.polymdegradstab.2024.111036

Yaxuan Huang, Jiyu He, Rongjie Yang

Phenylphosphonyl dichloride (BPOD) and 3-aminopropyltriethoxysilane (APTES) were used to prepare phosphorus-nitrogen hexaethoxysilane (BPTES). BPTES was then used for cross-linking and curing hydroxyl‑terminated room-temperature vulcanized (RTV) silicone rubber, providing intrinsic flame retardancy. In addition, halloysite (HNTs) is a kind of tubular silicate, taking advantage of its large aspect ratio, HNTs were used as a template to load ZIF67 on the surface of halloysite to obtain HNTs@ZIF tubular filler. It was added to the above system as a reinforcing and flame-retardant filler by physical blending, and the RTV elastomer with excellent performance was prepared. The successful preparation of phosphorus-containing crosslinkers (BPTES) was demonstrated by FT-IR. After the introduction of the new crosslinker, RTV not only has improved flame retardant performance, but also improved mechanical properties. The tensile strength and elongation at break of RTV with 20 wt.% BPTES are increased by 151 % and 211 %, respectively. The peak heat release rate (pHRR) and the peak of smoke production rate (pSPR) are reduced by 55.9 % and 48.6 %, respectively, and the thermal stability is also improved. In addition, the successful preparation of HNTs@ZIF was confirmed by FT-IR, XRD, XPS, and TEM. By introducing 2 wt.% HNTs@ZIF into 20 wt.% BPTES cured RTV, the intrinsically flame-retardant RTVs with enhanced performance were prepared. It is worth noting that when 2 wt.% HNTs@ZIF is added, the flame retardant and smoke suppression properties of phosphorus-containing silicone rubber are further improved. Because the ZIF contains cobalt metal ions that can be catalyzed into carbon. The pHRR and pSPR decrease by 18.3 % and 16.3 %, respectively, and the total heat release (THR) and total smoke production (TSP) decrease by 23.6 % and 24.4 %, respectively. This work will provide enlightenment for the study of intrinsic flame-retardant RTVs enhanced by modified halloysite.

使用苯基二氯化膦（BPOD）和 3-氨基丙基三乙氧基硅烷（APTES）制备磷氮六乙氧基硅烷（BPTES）。然后用 BPTES 交联和固化羟基封端室温硫化（RTV）硅橡胶，使其具有内在阻燃性。此外，埃洛石（HNTs）是一种管状硅酸盐，利用其长径比大的优势，以 HNTs 为模板，在埃洛石表面负载 ZIF67，得到 HNTs@ZIF 管状填料。通过物理混合的方法，将其作为增强和阻燃填料添加到上述体系中，制备出了性能优异的 RTV 弹性体。傅立叶变换红外光谱证明了含磷交联剂（BPTES）的成功制备。引入新的交联剂后，RTV 不仅提高了阻燃性能，还改善了机械性能。含有 20 wt.% BPTES 的 RTV 拉伸强度和断裂伸长率分别提高了 151 % 和 211 %。热释放率峰值（pRR）和烟雾产生率峰值（pSPR）分别降低了 55.9 % 和 48.6 %，热稳定性也得到了改善。此外，FT-IR、XRD、XPS 和 TEM 也证实了 HNTs@ZIF 的成功制备。通过在 20 wt.% BPTES 固化 RTV 中引入 2 wt.% HNTs@ZIF，制备出了性能更高的本征阻燃 RTV。值得注意的是，当加入 2 wt.% HNTs@ZIF 时，含磷硅橡胶的阻燃和抑烟性能得到进一步改善。因为 ZIF 中含有可催化成碳的钴金属离子。pHRR 和 pSPR 分别降低了 18.3% 和 16.3%，总放热量 (THR) 和总产烟量 (TSP) 分别降低了 23.6% 和 24.4%。这项工作将为研究改性埃洛石增强的本征阻燃 RTV 提供启示。

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引用次数: 0

Ablation behavior and mechanism of Ti3SiC2 modified carbon fiber/boron phenolic resin ceramizable composite Ti3SiC2 改性碳纤维/硼酚醛树脂可陶瓷化复合材料的烧蚀行为与机理

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-10 DOI: 10.1016/j.polymdegradstab.2024.111035

Zhixiong Huang , Guoqin Jiang , Xueyuan Yang , Yanbing Wang , Zongyi Deng

Carbon fiber/phenolic resin composite is prone to oxidation failure. In this work, Ti₃SiC₂ modified carbon fiber/boron phenolic resin ceramizable composite with excellent oxidation corrosion and ablation resistance was fabricated. It exhibited near-zero ablation characteristics with the linear ablation rate at 3000 °C for 20 s being -0.00859 mm/s. The ablation mechanism was investigated based on the ablation behavior, microstructure evolution, phase evolution and thermodynamic analysis. A thermal protection barrier composed of carbon-containing multiphase ceramics was in-situ constructed during ablation by sacrificing Ti₃SiC₂ and exerting the functions of oxygen consumption, oxygen inhibition, self-healing, carbon fixation and reaction heat absorption.

碳纤维/酚醛树脂复合材料容易发生氧化失效。在这项工作中，制备了具有优异抗氧化腐蚀性和抗烧蚀性的 Ti3SiC2 改性碳纤维/硼酚醛树脂可陶瓷化复合材料。该复合材料具有近乎零的烧蚀特性，在 3000 °C 下 20 秒的线性烧蚀率为 -0.00859 mm/s。根据烧蚀行为、微观结构演变、相演变和热力学分析研究了烧蚀机理。通过牺牲 Ti3SiC2，在烧蚀过程中原位构建了由含碳多相陶瓷组成的热保护屏障，发挥了耗氧、抑氧、自愈、固碳和反应吸热的功能。

引用次数: 0

Preparation of novel and efficient arylphosphonate flame retardants for simultaneously enhancement of fire safety and UV-shielding properties of transparent thermoplastic polyurethane 制备新型高效芳基膦酸盐阻燃剂，同时提高透明热塑性聚氨酯的防火安全性能和紫外线屏蔽性能

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-09 DOI: 10.1016/j.polymdegradstab.2024.111029

Wenjia Zhang , Yue Xu , Chentao Yan , Yue Gang , Ao Qin , Kai Xu , Miaojun Xu , Bin Li , Lubin Liu

Thermoplastic polyurethane (TPU) is highly flammable and UV aging, limiting its application in the field of new energy and electronic device. In this work, a novel macromolecular aromatic phosphonate Bis(4-(((diphenylphosphinyl)oxy)methyl)phenyl)phenylphosphonate (DMP) containing both P-C and P=O was successfully prepared by nucleophilic substitution reaction. The DMP was introduced into the TPU matrix to prepare multifunctional TPU composites. Condensed and gas phase analysis have shown that the flame retardant mechanism of DMP was mainly influenced by flame retardant inhibition and the barrier effect of char layer. Only 5 wt% DMP enabled TPU to obtain the UL-94V-0 rating with the LOI of 27.6 %. Compared with pure TPU, the HRR and THR of TPU/5 wt% DMP were decreased by 19.8 % and 13.2 %. Meanwhile, the matching of the melting point for DMP and the processing temperature for TPU increased its dispersion in TPU matrix. Due to the excellent compatibility between DMP and TPU, TPU/DMP composites almost retained their original transparency and ductility. In addition, TPU/DMP composites exhibited excellent UV resistance, obtaining 100 % UV shielding at UV-B wavelengths and up to 97 % UV isolation at UV-A wavelengths. The study introduced a novel approach for preparing multifunctional flame retardant additives, and opened up wide application prospects for high-performance flame retardant TPU composites in emerging fields such as rail transit and electronic packaging.

热塑性聚氨酯（TPU）具有高易燃性和紫外线老化性，限制了其在新能源和电子设备领域的应用。本研究通过亲核取代反应成功制备了一种新型大分子芳香族膦酸盐双(4-(((二苯基膦酰)氧基)甲基)苯基)苯基膦酸盐（DMP），其中同时含有 P-C 和 P=O。将 DMP 引入热塑性聚氨酯基体中可制备多功能热塑性聚氨酯复合材料。冷凝和气相分析表明，DMP 的阻燃机理主要受阻燃剂抑制和炭层阻隔效应的影响。仅 5 wt% 的 DMP 就能使热塑性聚氨酯达到 UL-94V-0 级，LOI 为 27.6%。与纯热塑性聚氨酯相比，热塑性聚氨酯/5 wt% DMP 的 HRR 和 THR 分别降低了 19.8 % 和 13.2 %。同时，DMP 的熔点与热塑性聚氨酯的加工温度相匹配，增加了其在热塑性聚氨酯基体中的分散性。由于 DMP 与热塑性聚氨酯之间的兼容性极佳，热塑性聚氨酯/DMP 复合材料几乎保持了原有的透明度和延展性。此外，热塑性聚氨酯/DMP 复合材料还具有优异的抗紫外线性能，在紫外线-B 波长下的紫外线屏蔽率为 100%，在紫外线-A 波长下的紫外线隔离率高达 97%。该研究介绍了一种制备多功能阻燃添加剂的新方法，为高性能阻燃热塑性聚氨酯复合材料在轨道交通和电子包装等新兴领域开辟了广阔的应用前景。

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引用次数: 0

Preparation of high transparency, thermal stability, flame retardant polymethyl methacrylate nanocomposite via gamma-radiation polymerization 通过伽马辐射聚合制备高透明度、热稳定性和阻燃性聚甲基丙烯酸甲酯纳米复合材料

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-09 DOI: 10.1016/j.polymdegradstab.2024.111033

Chunlei Dong , Xuanzhi Mao , Nannan Zheng , Maojiang Zhang , Jianbing Chen , Jiangtao Hu , Guozhong Wu

Achieving flame retardancy and thermal stability in poly(methyl methacrylate) (PMMA) while maintaining its inherent high transparency presents a significant challenge. In this work, we successfully fabricated an exceptional composite (P-SiO₂-PMMA) with high transparency, flame retardancy, and thermal stability using ⁶⁰Co γ-ray irradiation-induced copolymerization of methyl methacrylate (MMA), 2-hydroxyethyl 2-methyl-2-propenoate phosphate (HEMAP), and nano-silica (SiO₂). The impact of the HEMAP on the crystal, optical, thermal stability, and combustion behavior properties of P-SiO₂-PMMA has been investigated. P-SiO₂/PMMA forms a three-dimensional network cross-linked molecular chain structure, enhancing the thermal decomposition temperature (T_di), maximum thermal decomposition temperature (T_max), glass transition temperature (T_g), and reducing the coefficient of thermal expansion (CTE). HEMAP and SiO₂ significantly enhance the flame retardancy of the material. The limiting oxygen index (LOI) value of transparent flame-retardant 20-P-SiO₂/PMMA composite material increased from 17.5% for PMMA to 23.2%, with a 47.3% decrease in peak heat release rate (PHRR). The flame retardant mechanism was also investigated. This study offers a novel approach for the industrial application of high transparency, thermal stability, and halogen-free flame-retardant PMMA composite.

实现聚甲基丙烯酸甲酯（PMMA）的阻燃性和热稳定性，同时保持其固有的高透明度是一项重大挑战。在这项工作中，我们利用 60Co γ 射线辐照诱导甲基丙烯酸甲酯 (MMA)、2-羟乙基 2-甲基-2-丙烯酸酯磷酸酯 (HEMAP) 和纳米二氧化硅 (SiO2) 的共聚，成功制备了一种具有高透明度、阻燃性和热稳定性的特殊复合材料（P-SiO2-PMMA）。研究了 HEMAP 对 P-SiO2-PMMA 的晶体、光学、热稳定性和燃烧行为特性的影响。P-SiO2/PMMA 形成了三维网络交联分子链结构，提高了热分解温度 (Tdi)、最大热分解温度 (Tmax)、玻璃化转变温度 (Tg)，并降低了热膨胀系数 (CTE)。HEMAP 和 SiO2 能显著提高材料的阻燃性。透明阻燃 20-P-SiO2/PMMA 复合材料的极限氧指数 (LOI) 值从 PMMA 的 17.5% 提高到 23.2%，峰值热释放率 (PHRR) 降低了 47.3%。此外，还研究了阻燃机理。这项研究为高透明度、热稳定性和无卤阻燃 PMMA 复合材料的工业应用提供了一种新方法。

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引用次数: 0

Degradation of thermoplastic polymers for fused filament fabrication under (S)TEM electron beam irradiation 用于熔融长丝制造的热塑性聚合物在 (S)TEM 电子束辐照下的降解情况

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-09 DOI: 10.1016/j.polymdegradstab.2024.111030

L.M. Valencia , J. Hernández-Saz , S.I. Molina , M. Herrera

The structural characterization of polymers and, in particular, of those used in Additive Manufacturing (AM) technologies, is essential to improve the understanding of their structure-property relationship for promising high-performance applications. For this, (scanning) transmission electron microscopy-electron energy loss spectroscopy, (S)TEM-EELS is an outstanding tool for exploring materials chemical and structural characteristics at high spatial resolution. However, the high beam-sensitivity of soft materials, such as polymers, hinders the possibility of probing in-depth analysis provided by (S)TEM-EELS. In this work, we analyse the electron beam irradiation damage of four polymers commonly used in Fused Filament Fabrication (FFF), namely polylactic acid (PLA), polycaprolactone (PCL), acrylonitrile butadiene styrene (ABS) and acrylonitrile styrene acrylate (ASA). For this, sequential low-loss and core-loss EEL spectra have been recorded, and the related signals have been monitored as a function of the accumulated dose. Our results show that the critical electron doses using the specimen thickness variations are larger for polymers containing aromatic groups (ABS and ASA) than for aliphatic polymers (PLA and PCL). Regarding the different elements, a larger sensitivity to the electron beam of oxygen regarding carbon and nitrogen is also evidenced. Our results have shown that polymer degradation occurs to a larger extent in the initial steps of electron irradiation, for very low accumulated electron doses, meaning that care should be taken in the selection of the microscopy settings to avoid artefacts produced by the electron beam. Degradation pathways for the four polymers studied are discussed.

聚合物的结构表征，尤其是增材制造（AM）技术中使用的聚合物的结构表征，对于更好地了解其结构与性能之间的关系以实现有前途的高性能应用至关重要。为此，（扫描）透射电子显微镜-电子能量损失光谱（(S)TEM-EELS）是以高空间分辨率探索材料化学和结构特征的杰出工具。然而，聚合物等软材料的高光束灵敏度阻碍了（S）TEM-EELS 所提供的深入分析的可能性。在这项工作中，我们分析了熔融长丝制造（FFF）中常用的四种聚合物（即聚乳酸（PLA）、聚己内酯（PCL）、丙烯腈-丁二烯-苯乙烯（ABS）和丙烯腈-苯乙烯-丙烯酸酯（ASA））的电子束辐照损伤。为此，我们记录了连续的低损耗和核心损耗电子能谱，并监测了相关信号与累积剂量的函数关系。结果表明，对于含有芳香族基团的聚合物（ABS 和 ASA），利用试样厚度变化得出的临界电子剂量要大于脂肪族聚合物（PLA 和 PCL）。在不同元素方面，氧对电子束的敏感度也高于碳和氮。我们的研究结果表明，在电子辐照的初始阶段，即使累积电子剂量很低，聚合物的降解程度也较大，这意味着在选择显微镜设置时应注意避免电子束产生的假象。本文讨论了所研究的四种聚合物的降解途径。

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引用次数: 0

Improving poly(lactic acid) fire performances via blending with benzoxazine 通过与苯并恶嗪混合改善聚（乳酸）防火性能

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-09 DOI: 10.1016/j.polymdegradstab.2024.111032

Marie-Odile Augé , Daniele Roncucci , Fanny Bonnet , Serge Bourbigot , Sabyasachi Gaan , Gaëlle Fontaine

Improving the mechanical performance of PLA via reactive blending with thermosets is an interesting approach, however, not well explored for its fire performance improvement. With our approach, the fire performances of PLA were improved by blending PLA with a commercially available bisphenol-F-based benzoxazine. To establish the proof of concept, the benzoxazine was initially pre-cured at either 100 °C or 150 °C for a pre-selected time i.e. 60′, 80′, or 120′. The benzoxazine samples were then blended with PLA matrix via an extrusion process at 10 wt.% or 20 wt.% loadings. Detailed thermal and chemical investigations via Differential Scanning Calorimetry (DSC) and Size Exclusion Chromatography (SEC), and the evaluation of the mechanical properties, confirmed that the addition of benzoxazine does not influence the intrinsic properties of PLA. The fire performance was tested by Mass Loss Cone (MLC) calorimetry. PLA formulation with 20 wt.% of the benzoxazine cured 80′ at 150 °C, lead to a 43 % reduction of the peak of heat release rate compared to neat PLA. This was attributed to increased char formation during the combustion process. Also, the char formation permits a significant delay in the temperature increase of the sample.

通过与热固性塑料进行反应共混来改善聚乳酸的机械性能是一种有趣的方法，但在改善其防火性能方面还没有很好的探索。我们采用的方法是通过将聚乳酸与市售的基于双酚 F 的苯并恶嗪混合来改善聚乳酸的防火性能。为了验证概念，首先将苯并恶嗪在 100 ℃ 或 150 ℃ 的温度下进行预固化，预固化时间为 60′、80′或 120′。然后通过挤压工艺将苯并恶嗪样品与聚乳酸基质混合，添加量为 10 重量%或 20 重量%。通过差示扫描量热法（DSC）和尺寸排阻色谱法（SEC）进行的详细热学和化学研究以及机械性能评估证实，添加苯并恶嗪不会影响聚乳酸的内在性能。质量损失锥（MLC）量热法测试了聚乳酸的防火性能。与纯聚乳酸相比，添加了 20 wt.% 苯并恶嗪的聚乳酸配方在 150 °C 下固化 80′后，热释放率峰值降低了 43%。这归因于燃烧过程中炭的形成增加。此外，焦炭的形成也使样品的温度上升明显延迟。

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引用次数: 0

A simple strategy to significantly improve the anticorrosion and aging resistance of epoxy coatings by adding polyaniline modified multi-walled carbon nanotubes 通过添加聚苯胺改性多壁碳纳米管大幅提高环氧涂料防腐和抗老化性能的简单策略

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability

Pub Date : 2024-10-08 DOI: 10.1016/j.polymdegradstab.2024.111027

Yijian Gao , Shasha He , Jinyi Hu , Chonggang Wu , Zhenyu Chen , Hongyu Cen

Epoxy coatings are widely used for corrosion protection of metals, but under extremely harsh environments, the epoxy polymer chains such as the CO bonds of epoxy ether and aromatic ether, and the -OH in the epoxy chain structure can also undergo aging and degradation, leading to the failure of the coating in service. How to extend the anti-aging capability of epoxy resins while maintaining their other properties unchanged has become a major challenge in the practical application of epoxy coatings. In this study, the polyaniline (PANI) modified multi-walled carbon nanotubes (MWCNT@PANI) were synthesized by polymerization in-situ and added to epoxy resin as an anti-aging filler. The various measurements have been adopted to characterize the composition and structure of MWCNT@PANI, and the anticorrosive performance of the composite coating for carbon steel were evaluated via salt spray, chemical aging and UV light aging. Results showed that the impedance value of the blank epoxy coating decreases by at least two orders of magnitude after the salt spray tests, and the contact angle decreases by about 30° and gradually changes from hydrophobic to hydrophilic, indicating a significant decline in corrosion resistance. In contrast, the composite coating confirmed the excellent anti-aging performance, while the impedance values increased by approximately 2–5 orders of magnitude compared to that in blank epoxy coatings, and remained around 10¹⁰ Ω·cm². Given the dense encapsulation of MWCNT@PANI, the dispersion stability between the filler and EP can be improved, and the effective corrosion resistance performance was also supported by molecular dynamic simulation. Besides that, the ability of free radical quenching along with the labyrinth effect and hydrophobic interaction have also been investigated to explain the anticorrosion and anti-aging mechanism.

环氧涂料被广泛应用于金属防腐，但在极端恶劣的环境下，环氧聚合物链，如环氧醚和芳香醚的 CO 键以及环氧链结构中的 -OH 也会发生老化和降解，导致涂层在使用中失效。如何在保持环氧树脂其他性能不变的情况下延长其抗老化能力，已成为环氧涂料实际应用中的一大难题。本研究采用原位聚合法合成了聚苯胺（PANI）改性多壁碳纳米管（MWCNT@PANI），并将其添加到环氧树脂中作为抗老化填料。采用多种测量方法表征了 MWCNT@PANI 的组成和结构，并通过盐雾、化学老化和紫外光老化评估了碳钢复合涂层的防腐性能。结果表明，盐雾试验后，空白环氧涂层的阻抗值至少下降了两个数量级，接触角下降了约 30°，并逐渐从疏水变为亲水，表明耐腐蚀性能显著下降。相比之下，复合涂层证实了其优异的抗老化性能，而阻抗值则比空白环氧涂层增加了约 2-5 个数量级，并保持在 1010 Ω-cm2 左右。鉴于 MWCNT@PANI 的致密包覆，填料与 EP 之间的分散稳定性得以提高，分子动力学模拟也支持其有效的耐腐蚀性能。此外，还研究了自由基淬灭能力以及迷宫效应和疏水相互作用，以解释其防腐和抗老化机理。

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