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Chemical degradation of crosslinked ethylene-propylene-diene rubber in an acidic environment: part I: effect on accelerated sulphur crosslinks

机译:交联乙烯 - 丙烯 - 二烯橡胶在酸性环境中的化学降解:第一部分:对加速硫交联的影响

摘要

The time-dependent chemical degradation of accelerated sulphur cured ethylene propylene diene rubber containing 5-ethylidene-2-norbornene as diene in an acidic environment (20% Cr/H2SO4) was investigated. Two different rubbers with a similar ethylene to propylene ratio and diene content but with a significant difference in molar mass and level of long chain branching were used in the study. The molecular mechanisms of the chemical degradation occurring at the surface were determined using surface analysis (X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy). The results reveal formation of several oxygenated species on the surface as a consequence of the acid attack. Furthermore, the crosslink sites of the exposed rubber samples are also found vulnerable to hydrolytic attack as evidenced by the decrease in crosslink density. The extent of surface degradation was strong enough to affect the bulk mechanical properties. Changes in mechanical properties were also monitored through determining retention in tensile strength, (%) elongation at break, modulus at 50% elongation, and change in micro-hardness. A negative correlation is also established between retention in modulus at 50% elongation and decrease in crosslink density. Scanning electron microscopy reveals the topographical damage at the surface due to the aqueous acid induced chemical degradation. The results indicate that the chemical degradation proceeds mainly via hydrolysis of crosslinks but upon prolonged exposure, the oxygenated species tend to combine with each other. The effect of molar mass and level of long chain branching also influences the chemical degradation.
机译:研究了在酸性环境(20%Cr / H2SO4)中,以5-亚乙基-2-降冰片烯为二烯的加速硫磺硫化乙烯丙烯二烯橡胶随时间的化学降解。在研究中使用了两种不同的橡胶,它们的乙烯/丙烯比和二烯含量相似,但摩尔质量和长链支化水平却有显着差异。使用表面分析(X射线光电子能谱和衰减全反射傅里叶变换红外光谱法)确定了发生在表面的化学降解的分子机理。结果表明,由于酸侵蚀,表面上形成了几种氧化物质。此外,还发现暴露的橡胶样品的交联位点易受水解侵蚀,如交联密度的降低所证明。表面降解的程度足以影响整体机械性能。还通过确定拉伸强度的保持率,断裂伸长率(%),50%伸长率的模量和显微硬度的变化来监测机械性能的变化。在50%伸长率下模量保持率和交联密度降低之间也建立了负相关关系。扫描电子显微镜揭示了由于含水酸诱导的化学降解而导致的表面形貌损伤。结果表明,化学降解主要通过交联键的水解进行,但长时间暴露后,含氧物质往往会相互结合。摩尔质量和长链支化水平的影响也影响化学降解。

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