纺织学报 ›› 2026, Vol. 47 ›› Issue (1): 151-158.doi: 10.13475/j.fzxb.20250502501

• 染整工程 • 上一篇    下一篇

高强聚酰亚胺织物在多环境因素下的老化行为

兰含宇1,2, 陈欣1,2, 梁东旭1,2, 赵昕1,2(), 张清华1,2   

  1. 1.东华大学 材料科学与工程学院, 上海 201620
    2.东华大学 先进纤维材料全国重点实验室, 上海 201620
  • 收稿日期:2025-05-16 修回日期:2025-12-18 出版日期:2026-01-15 发布日期:2026-01-15
  • 通讯作者: 赵昕(1985—),女,教授,博士。主要研究方向为高性能有机纤维等。E-mail: xzhao@dhu.edu.cn
  • 作者简介:兰含宇(2001—),女,博士生。主要研究方向为高性能有机纤维的表面改性。
  • 基金资助:
    重点新材料研发及应用国家科技重大专项(2024ZD0602600)

Aging behavior of high-strength polyimide fabrics under various environmental factors

LAN Hanyu1,2, CHEN Xin1,2, LIANG Dongxu1,2, ZHAO Xin1,2(), ZHANG Qinghua1,2   

  1. 1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
    2. State Key Laboratory of Advanced Fiber Materials, Donghua University, Shanghai 201620, China
  • Received:2025-05-16 Revised:2025-12-18 Published:2026-01-15 Online:2026-01-15

摘要:

为评估高强聚酰亚胺织物在复杂严苛环境中的长期安全可靠性、预测其服役寿命,并进一步优化生产工艺、开发性能更稳定和耐久性更强的新一代纤维,选取霉菌侵蚀、氙灯辐照、盐雾及机械磨损4种环境条件,系统模拟聚酰亚胺织物在大气、太阳辐射等多种工况下的老化过程。借助电子万能材料试验机、光电子能谱分析以及场发射扫描电子显微镜对老化前后试样的拉伸强度、化学结构和微观形貌进行表征分析,并初步探究其老化机制。结果表明:选择的4种加速老化条件均导致聚酰亚胺织物试样的力学性能和耐热性能出现不同程度的下降;其中,氙灯辐照和盐雾处理对材料造成的损伤尤为显著,引发了明显的表面缺陷;进一步机制分析显示,老化过程中聚酰亚胺大分子链中相对脆弱的化学键被破坏,是导致材料性能退化的原因。

关键词: 聚酰亚胺, 霉菌, 氙灯, 盐雾, 老化, 服役性能, 高性能纤维

Abstract:

Objective As a representative of advanced polymer materials, polyimide fibers show irreplaceability in extreme service environments such as military and aerospace with their unique molecular structure and performance synergy. However, the outstanding properties of polyimide will inevitably be affected by prolonged exposure to extreme conditions such as high-energy irradiation and atomic oxygen. This research is an attempt to explore in-depth the aging mechanism of polyimide fibers and fabrics under multiple environmental factors, so as to further improve the stability and reliability of the materials for the intended applications.

Method The aging test chamber was used to evaluate the radiation resistance, corrosion resistance and other properties of materials by simulating and accelerating environmental factors, from which the performance degradation of products in extreme environments was predicted. According to the GJB 150.10A-2009 standard, polyimide fabrics were placed in an aging test chamber with different experimental conditions to separately simulate mold, xenon lamp and salt spray aging environment before they were cleaned to remove surface contaminants by washing. In addition to the environmental aging tests, the fabrics underwent another abrasion aging test using a Martindale abrasion tester, referring to the GB/T 21196.2—2007 standard. The properties and structure of fabrics were analyzed by mechanical property testing, thermos gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM).

Results The initial polyimide fabric showed a warp tensile strength of 705.66 N/cm and an elongation at break of 9%. After undergoing mold, xenon lamp, abrasion, and salt-spray aging respectively, the tensile strength and elongation at break of the fabric decreased to various degrees. The retention rates of fabrics warp tensile strength were 91.44%, 89.35%, 87.48%, and 85.29%, respectively, still remaining at a relatively high level. The elongation at break of the different aged samples all decreased to around 7%, indicating that the flexibility of the fabric has declined. The thermal decomposition temperatures of the polyimide fabrics decreased after aging. The correlation between mechanical properties and heat resistance of fabric demonstrated that the experimental aging schemes indeed caused damage to the actual performance of the polyimide fabric to some extent. Subsequently, the chemical structures of the fabric before and after aging were investigated. The positions of different characteristic absorption peak in the FT-IR spectra of these samples did not change. In the characteristic XPS spectra of C 1s for the initial fabric, the proportions of C—O and C—N were 4.19% and 5.05%, respectively, and after different aging treatments, the proportions of both decreased. In contrast, an increase in the peak area of the C=N and the emergence of C*—C=O peak were observed, confirming that all three aging conditions affected the chemical structure of the polyimide. Mould, xenon lamp, and salt-spray aging treatments have no significant effect on the overall macroscopic morphology of the fabrics. The original surface morphology of the fiber was smooth, but the surface roughness increased after the above three aging treatments, displaying obvious etching grooves and partial peeling. After abrasion and stretching, the regularity of fabrics in warp direction deteriorated significantly. For the sample after abrasion aging, fibers showed obvious bending, the smooth surface structure was completely destroyed, and a structure similar to microfibrils emerged. For the fabric after warp tensile test, the longitudinal fibers exhibited obvious layered fracture morphology and “V-shaped” fracture notches. Finally, the possible aging mechanisms of polyimide fabrics under different environmental conditions were explored.

Conclusion The research results show that mold, xenon lamp, salt spray and abrasion aging negatively affected the mechanical properties and heat resistance of the high-strength polyimide fabrics to various degrees, and salt spray aging appears to be the most significantly damaging factor which reduced the tensile strength and elongation at break of the fabrics by 14.71% and 28.44%, respectively, and caused decrease in thermal weight loss temperature. After aging under different environmental conditions, the surface smoothness of fibers decreased, and microscopic defects such as grooves and peeling appeared. The chemical structure of fiber before and after experiment was analyzed, and the aging mechanism may be related to the destruction of chemical bonds such as C—N and C—O, as well as long molecular chains or conjugated structures in the polyimide macromolecular chain.

Key words: polyimide, mould, xenon lamp, salt-spray, aging, service performance, high performance fiber

中图分类号: 

  • TS151

图1

不同条件老化前后聚酰亚胺织物的力学性能"

图2

不同条件老化前后聚酰亚胺织物的耐热性能变化"

表1

不同老化条件处理后聚酰亚胺织物的耐热性能"

处理条件 Td5%/℃ Td10%/℃ Tdmax/℃ 残炭量/%
未处理 570.1 595.6 616.1 62.2
霉菌 569.5 592.7 614.9 60.9
氙灯 563.2 589.3 612.7 61.8
盐雾 554.4 585.2 609.1 62.3

图3

不同条件老化前后聚酰亚胺织物的红外光谱图"

图4

不同条件老化前后聚酰亚胺织物表面各元素的XPS谱图"

图5

不同条件老化前后聚酰亚胺织物的表面形貌"

图6

聚酰亚胺织物经磨损和拉伸处理后的表面形貌"

图7

聚酰亚胺织物的老化机制"

[1] 宋晓峰. 聚酰亚胺的研究与进展[J]. 纤维复合材料, 2007, 24(3): 33-37.
SONG Xiaofeng. Research and progress of polyimide[J]. Fiber Composites, 2007, 24(3): 33-37.
[2] ZHENG S S, DONG J, ZHOU X Y, et al. High-strength and high-modulus polyimide fibers with excellent UV and ozone resistance[J]. ACS Applied Polymer Materials, 2022, 4(6): 4558-4567.
doi: 10.1021/acsapm.2c00550
[3] JIANG S H, UCH B, AGARWAL S, et al. Ultralight, thermally insulating, compressible polyimide fiber assembled sponges[J]. ACS Applied Materials & Interfaces, 2017, 9(37): 32308-32315.
[4] 方国平, 杨艳, 何建忠. 聚酰亚胺8121高性能纤维技术及应用研究[J]. 针织工业, 2024(4): 6-11.
FANG Guoping, YANG Yan, HE Jianzhong. Technology and application of polyimide 8121 high-performance fiber[J]. Knitting Industries, 2024(4): 6-11.
[5] CHEN J, DING N W, LI Z F, et al. Organic polymer materials in the space environment[J]. Progress in Aerospace Sciences, 2016, 83: 37-56.
doi: 10.1016/j.paerosci.2016.02.002
[6] MINTON T K, ROUSSEL J F. Materials in a space environment[J]. ACS Applied Materials & Interfaces, 2010, 2(10): 2687-2688.
[7] XU S Q, LIN D L, LI R Y, et al. Effect of chemical structures and environmental factors on the thermal degradation mechanism of polyimide: experiments and molecular dynamics simulations[J]. Materials Today Chemistry, 2024, 40: 102242.
doi: 10.1016/j.mtchem.2024.102242
[8] ZHANG J L, ZHOU X Y, DONG J, et al. Intrinsically UV-resistant copolyimide: exploring the impact of UV-absorbing groups on degradation and comprehensive performance[J]. Macromolecules, 2024, 57(3): 1266-1276.
doi: 10.1021/acs.macromol.3c02170
[9] 杨传超, 徐鸿杰, 田国峰, 等. 高强高模聚酰亚胺纤维的空间环境适应性研究及在航天领域的应用前景分析[J]. 材料导报, 2022, 36(22): 184-188.
YANG Chuanchao, XU Hongjie, TIAN Guofeng, et al. Research on space environment adaptability of polyimide fiber with high-strength and high-modulus and analysis of its application prospects in aerospace field[J]. Materials Reports, 2022, 36(22): 184-188.
[10] 琚丹丹, 王馨敏, 孙承月, 等. PI纤维在空间带电粒子辐照下的力学性能损伤[J]. 装备环境工程, 2020, 17(3): 1-7.
JU Dandan, WANG Xinmin, SUN Chengyue, et al. Mechanical properties of polyimide fibers under the irradiation of space charged particles[J]. Equipment Environmental Engineering, 2020, 17(3): 1-7.
[11] HOQUE M S, DOLEZ P I. Impact of photochemical aging on high-performance fabrics used in firefighters' protective clothing[J]. Journal of Polymer Science, 2024, 62(23): 5347-5371.
doi: 10.1002/pola.v62.23
[12] EVANS S. Estimation of the uncertainties associated with XPS peak intensity determination[J]. Surface and Interface Analysis, 1992, 18(5): 323-332.
doi: 10.1002/sia.v18:5
[13] 马杰. 临近空间模拟环境下Kevlar和Vectran纤维织物损伤行为研究[D]. 天津: 河北工业大学, 2022.
MA Jie. Damage behavior of kevlar and vectran fibers in near space simulation environment[D]. Tianjin: Hebei University of Technology, 2022.
[14] ZHANG W X, JING X F, BAI Y Q, et al. Study on the aging behavior of an ultra-high molecular weight polyethylene fiber barrier net in a marine environment[J]. Materials, 2022, 15(16): 5599.
doi: 10.3390/ma15165599
[15] CHEN M H, LIANG B, GUO Y H, et al. Pyrolysis mechanism of polyimide containing bio-molecule adenine building block[J]. Polymer Degradation and Stability, 2020, 175: 109124.
doi: 10.1016/j.polymdegradstab.2020.109124
[16] 徐诗琴, 蔺道雷, 李闰月, 等. 聚酰亚胺薄膜老化过程中的结构与性能演变机理研究[J]. 化工新型材料, 2023, 51(9): 156-160, 167.
doi: 10.19817/j.cnki.issn1006-3536.2023.09.029
XU Shiqin, LIN Daolei, LI Runyue, et al. Evolution mechanism of structure and properties of polyimide films during aging[J]. New Chemical Materials, 2023, 51(9): 156-160, 167.
doi: 10.19817/j.cnki.issn1006-3536.2023.09.029
[17] ROY R, SARKAR B K, BOSE N R. Effects of moisture on the mechanical properties of glass fibre reinforced vinylester resin composites[J]. Bulletin of Materials Science, 2001, 24(1): 87-94.
doi: 10.1007/BF02704845
[18] LIU L L, JIN F, JI J, et al. Research on the quasi-static/dynamic mechanical properties and impact resistance of 3D woven composites under salt spray aging[J]. Composites Part A: Applied Science and Manufacturing, 2025, 194: 108923.
doi: 10.1016/j.compositesa.2025.108923
[19] GU J D, FORD T E, MITCHELL R. Susceptibility of electronic insulating polyimides to microbial degradation[J]. Journal of Applied Polymer Science, 1996, 62(7): 1029-1034.
doi: 10.1002/(ISSN)1097-4628
[1] 罗家俊, 何耀权, 赵振鸿, 黎锦稻, 赵景, 黄钢, 王先锋. 苯乙烯-乙烯-丁烯-苯乙烯/氟化聚酰亚胺防水透湿纤维膜的制备及其性能[J]. 纺织学报, 2026, 47(1): 38-45.
[2] 史芷丞, 陈凤翔, 王梦云, 白洁, 李娟, 白濛, 伏广伟, 徐卫林. 面向空天应用的高性能无机纤维及制品发展现状及趋势[J]. 纺织学报, 2025, 46(12): 233-242.
[3] 袁颖, 滕凤冬, 曹煜彤, 于俊荣, 李娜, 胡祖明, 王彦. 高模量对位芳纶研究进展[J]. 纺织学报, 2025, 46(11): 238-246.
[4] 吴晋瑶, 钟毅, 张琳萍, 徐红, 毛志平. 基于聚苯胺的柔性红外隐身薄膜的制备与性能[J]. 纺织学报, 2025, 46(09): 1-8.
[5] 刘旭东, 宋政吉, 陈世昌, 陈文兴. 改性环氧树脂涂覆聚酰亚胺纤维的表面性能[J]. 纺织学报, 2025, 46(08): 18-27.
[6] 贾琳, 杨奥杰, 张芳铖, 王西贤, 张海霞. 共聚型聚酰亚胺纳米纤维膜的制备及其性能[J]. 纺织学报, 2025, 46(08): 37-44.
[7] 张毅, 沈殷, 高金霞, 郁崇文. 棕榈纤维吸声复合材料的老化性能[J]. 纺织学报, 2025, 46(06): 127-134.
[8] 郭羽晴, 屈芸, 张利平, 孙洁. 芳纶纳米纤维制备及其可纺性[J]. 纺织学报, 2025, 46(04): 1-10.
[9] 严艺, 朱达辉. 老年智能服装研究现状与发展趋势[J]. 纺织学报, 2025, 46(04): 244-254.
[10] 王彪, 李源, 董杰, 张清华. 热亚胺化中应力对聚酰亚胺纤维结构和性能的影响[J]. 纺织学报, 2025, 46(03): 1-8.
[11] 李慧敏, 刘淑强, 杜琳琳, 张曼, 吴改红. 玄武岩/聚酰亚胺三维间隔机织物的参数化建模及高温环境传热数值模拟[J]. 纺织学报, 2025, 46(01): 87-94.
[12] 刘欢欢, 孟虎, 王朝晖. 适老化智能可穿戴设计研究进展及发展趋势[J]. 纺织学报, 2024, 45(03): 236-243.
[13] 南静静, 杜明娟, 孟家光, 余灵婕, 支超. 海水老化下类填充微穿孔板结构水下吸声材料的性能及其寿命预测[J]. 纺织学报, 2024, 45(02): 85-92.
[14] 夏良君, 曹根阳, 刘欣, 徐卫林. 高性能纤维及其制品颜色构建的研究进展[J]. 纺织学报, 2023, 44(06): 1-9.
[15] 缪莹, 熊诗嫚, 郑敏博, 唐建东, 张慧霞, 丁彩玲, 夏治刚. 高光洁处理对聚酰亚胺短纤纱及其织物性能的影响[J]. 纺织学报, 2023, 44(02): 118-127.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!