耐原子氧聚酰亚胺复合纤维的制备与性能

doi:10.19894/j.issn.1000-0518.250292

摘要/Abstract

摘要：

设计并合成了季铵盐修饰的聚倍半硅氧烷纳米粒子（QA-POSS），并将其添加到聚酰胺酸纺丝液中，纺制了一系列不同Si含量的QA-POSS/PI复合纤维。结果表明，复合纤维具有良好的耐热性能，其5%热失重温度（T_5%）和玻璃化转变温度（T_g）平均值分别为558和395 ℃。经X射线光电子能谱（XPS）以及电感耦合等离子体光谱（ICP）测试结果表明，复合纤维整体的Si元素含量比复合纤维表面的Si元素含量低，说明Si元素在复合纤维体系呈现梯度分布。当QA-POSS添加质量分数从0%增加到15%时，经3.17×10²⁰ atoms/cm²的原子氧辐照之后，复合纤维表面形貌由粗糙逐渐变得致密完整，质量损失下降明显，从1.40 mg/cm²降低为0.10 mg/cm²。经原子氧辐照之后，QA-POSS-5%的复合纤维显示出最低的力学性能损失（断裂强度保持率为89.36%，初始模量保持率为89.35%，强度衰减率为1.58×10^-13 Pa·cm²/atom）。

关键词: 聚酰亚胺纤维, 笼型聚倍半硅氧烷, 耐原子氧

Abstract:

Herein， polyhedral oligomeric silsesquioxane （POSS） nanoparticles were modified by quaternary ammonium， followed by adding into polyamic acid （PAA） spinning solution. Then series of QA-POSS/PI composite fibers were afforded via wet-spinning process. The as-prepared composite fibers showed good thermal properties with 5% thermal decomposition temperature（T_5%） and glass transition temperature （T_g） values of 558 ℃ and 395 ℃. Based on X-ray photoelectron spectroscopy （XPS） and inductively coupled plasma （ICP） measurement results， the silicon contents on fiber surface were higher than those in total fiber， which indicated that silicon showed gradient distribution in composite fibers. When additive amount of QA-POSS nanoparticles was raised from 0% to 15%， the surface topographies of composite fibers displayed a clear change from roughness to compact， and mass loss decreased obviously from 1.40 mg/cm² to 0.10 mg/cm² after AO erosion with the fluence of 3.17×10²⁰ atoms/cm². Actually， the lowest loss of mechanical properties was seen for the composite fibers when 5% QA-POSS particles were added. Fracture strength and initial modulus retentions of the fibers were 89.36% and 89.35%， respectively. And the corresponding decay rate of the strength was seen as 1.58×10^-13 Pa·cm²/atom.

Key words: Polyimide fibers, Polyhedral oligomeric silsesquioxanes, Anti-atomic oxygen

中图分类号:

O631

刘芳芳, 姚海波, 李国民, 王立朋, 董志鑫, 邱雪鹏. 耐原子氧聚酰亚胺复合纤维的制备与性能[J]. 应用化学, 2026, 43(1): 31-40.

Fang-Fang LIU, Hai-Bo YAO, Guo-Min LI, Li-Peng WANG, Zhi-Xin DONG, Xue-Peng QIU. Preparation and Atomic Oxygen-Resistant Properties of Quaternary Ammonium Salt Modified Polyhedral Oligomeric Silsesquioxane/Polyimide Composite Fibers[J]. Chinese Journal of Applied Chemistry, 2026, 43(1): 31-40.

图/表 10

图1 纺丝液以及复合纤维的制备过程

Fig.1 Preparation process of spinning solution and composite fibers

图2 空白PI纤维和QA-POSS/PI复合纤维的FT-IR光谱图

Fig.2 FT-IR spectra of blank PI fiber and QA-POSS/PI composite fibers

表1 复合纤维Si元素含量的理论计算与测试结果

Table 1 Theoretical and test results of silicon content in the composite fibers

Sample	w（QA-POSS）/% in PAA	Calculated w（silicon）/%	w（silicon）/% measured by XPS	w（silicon）/% measured by ICP
1	2.5	0.50	1.75	0.65
2	5.0	1.00	2.35	0.71
3	7.5	1.50	2.92	1.23
4	10.0	2.00	3.18	1.69
5	15.0	3.00	5.99	2.73

图3 QA-POSS添加量为2.5%（A1、A2）、5.0%（B1、B2）、10%（C1、C2）的复合纤维的断面形貌图。纤维中心区域（A1、B1、C1）和边缘区域（A2、B2、C2）的Si元素含量定量分析

Fig.3 Cross-sectional morphology images of composite fibers with QA-POSS additions of 2.5% （A1， A2）， 5% （B1， B2）， and 10% （C1， C2）. Quantitative analysis of Si element content in the central regions （A1， B1， C1） and edge regions （A2， B2， C2） of the fibers

图4 空白PI纤维和QA-POSS/PI复合纤维的TGA和DMA曲线

Fig.4 TGA and DMA curves of blank PI fiber and QA-POSS/PI composite fibers

图5 原子氧侵蚀后Kapton薄膜和复合薄膜的质量损失结果

Fig.5 Mass loss of Kapton and composite films after AO erosion

图6 空白PI纤维和复合纤维经原子氧侵蚀前后的表面形貌变化

Fig.6 Surface morphologies of （A0-A3） blank PI fiber， composite fibers with （B0-B3） 2.5% QA-POSS，（C0-C3） 5% QA-POSS，（D0-D3） 7.5% QA-POSS，（E0-E3） 10% QA-POSS， and （F0-F3） 15% QA-POSS additive amount before and after AO erosion

图7 原子氧辐照前后复合纤维（QA-POSS添加量为5%和15%）XPS结果

Fig.7 XPS spectra of composite fibers with 5% and 15% QA-POSS additive amount before and after AO erosion

表3 复合纤维经原子氧侵蚀前后表面元素含量

Table 3 Surface elemental content of the composite fibers before and after exposure to AO

Element type	Surface elemental mass fraction by XPS/%
	Composite fibers with 5% QA-POSS additive amount		Composite fibers with 15% QA-POSS additive amount
	Before AO exposure	After AO exposure	Before AO exposure	After AO exposure
C	77.68	39.04	75.27	20.37
O	15.93	38.62	15.64	50.71
Si	2.35	20.57	5.99	27.82

图8 复合纤维经原子氧侵蚀前后的（A）强度、（B）模量和（C）强度衰减率的变化

Fig.8 Variation on （A） strength，（B） modulus and （C） strength decay rate of composite fibers before and after AO erosion

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