宽温域下氟醚橡胶的加速老化行为和机理研究

doi:10.11949/0438-1157.20201624

摘要/Abstract

摘要：

基于氟醚橡胶使用环境的特殊性，从物理和化学角度，在宽温域（-40～225℃）条件下对某国产氟醚橡胶在4050航空润滑油中老化后的质量、力学性能、化学结构、元素组成及热稳定性等有关参数进行了研究，分析了老化温度和老化时间对氟醚橡胶性能的影响规律。结果表明：在相对较宽温域-25～200℃内氟醚橡胶的耐介质老化性能优异，其物化性能在长期老化过程中保持稳定；当老化温度达200℃以上时，溶胀和氧化反应增强，随着老化时间的增加，材料逐渐由软而韧变为硬而脆；特别是在高温225℃下，脱氟化氢反应导致大量C—F键断裂，F元素含量显著减少，同时氧化反应增强并生成CO键，导致O元素含量增多；低温老化过程中氟醚橡胶的质量、化学结构及元素含量基本不变，但-40℃时的玻璃化转变行为会导致力学性能的下降。

关键词: 氟醚橡胶, 老化, 宽温域, 力学性能, 化学性质

Abstract:

Based on the particularity of the use environment of fluoroether rubber, from a physical and chemical point of view, the quality, mechanical properties, and chemical related parameters such as structure, element composition and thermal stability were studied, and the influence of aging temperature and aging time on the properties of fluoroether rubber was analyzed. The influence of temperature and aging time on the properties of fluoroether rubber is analyzed. The results show that: fluoroether rubber has excellent resistance to lubricating oil aging, and its physical and chemical properties remain stable during long-term aging in the temperature range of -25—200℃; When aging temperature reaches 200℃ and above, the swelling and oxidation reaction accelerate, the material will gradually change from soft and tough to hard and brittle with the aging time. Especially at the extremely high temperature of 225℃, dehydrofluorination reaction causes the fracture of C—F bonds, the content of F element significantly decreases. Meanwhile, the oxidation reaction is enhanced, forming the CO bonds, so that the content of O element increases; The quality, chemical structure and element content of fluoroether rubber basically remain unchanged at low aging temperatures, and glass transition occurred at -40℃, resulting in the reduction of mechanical properties.

Key words: fluoroether rubber, aging, wide temperature range, mechanical properties, chemical properties

中图分类号:

TQ 330.14

余成明, 彭旭东, 江锦波, 马艺, 王玉明. 宽温域下氟醚橡胶的加速老化行为和机理研究[J]. 化工学报, 2021, 72(6): 3399-3410.

YU Chengming, PENG Xudong, JIANG Jinbo, MA Yi, WANG Yuming. Investigation on accelerated aging behavior and mechanism of fluoroether rubber under wide temperature range[J]. CIESC Journal, 2021, 72(6): 3399-3410.

图/表 15

图1 不同温度下FM-1D交联密度特征值的时变曲线图

Fig.1 Eigenvalue of crosslink density varying with time for FM-1D at different aging temperatures

图2 不同温度下FM-1D质量变化率的时变曲线图

Fig.2 Mass changes with aging time at different temperatures for FM-1D

图3 不同温度下FM-1D硬度变化率的时变曲线

Fig.3 Hardness changes with aging time at different temperatures for FM-1D

图4 不同温度下FM-1D拉伸强度、拉断伸长率的时变曲线

Fig.4 Changes of tensile strength and elongation at break with aging time at different temperatures for FM-1D

图5 不同老化时间下FM-1D拉伸强度、拉断伸长率随温度的变化曲线

Fig.5 Changes of tensile strength and elongation at break with aging temperature at different times for FM-1D

图6 老化时间1、14和35 d下FM-1D应力-应变随温度的变化曲线

Fig.6 Stress-strain curves of different temperatures for FM-1D at 1, 14 and 35 d

图7 老化温度225℃、23℃和-40℃下FM-1D应力-应变随时间的变化曲线

Fig.7 Stress-strain curves of different aging time for FM-1D at 225℃, 23℃ and -40℃

图8 不同温度下FM-1D压缩永久变形率的时变曲线

Fig.8 Compression set changes with aging time at different temperatures for FM-1D

图9 不同温度下FM-1D断口形貌

Fig.9 Morphology of the fracture surface at different temperatures for FM-1D

图10 FM-1D断口形貌随时间的变化

Fig.10 Morphological changes of the fracture surface with aging time for FM-1D

图11 FM-1D老化35 d拉伸断口元素含量

Fig.11 Element content of the tensile fracture surface at 35 d for FM-1D

图12 -40℃与225℃下FM-1D傅里叶变换衰减全反射红外光谱图

Fig.12 ATR-FTIR spectra of FM-1D after aging at -40℃ and 225℃

图13 -40℃与225℃下FM-1D的TGA和DTG曲线

Fig.13 TGA and DTG curves of FM-1D at -40℃ and 225℃

图14 -40℃与225℃下FM-1D的二次升温DSC曲线

Fig.14 Secondary heating DSC curves of FM-1D at -40℃ and 225℃

图15 Tg随老化时间的变化曲线

Fig.15 Curves of Tg varying with aging time

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