Effect of oxygen on the radiation of silicone rubber determined by gaseous chromatograph and DFT calculation

Lei Yu , Shuai Liu , Bo Liu , Zhenghao Mao , Wei Huang , Jing Peng , Yinyong Ao
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引用次数: 1

Abstract

The radiation effects of silicone rubber under different atmospheres are of great significance to evaluate the aging behavior of materials, and to assess their practical application life. The radiation-induced cross-linking and degradation of polydimethylsiloxane rubber were confirmed firstly by 1H NMR and high-temperature GPC, respectively. By using the established gas collecting system and gaseous chromatography method, we systematically investigated the gaseous products of irradiated silicone rubber at different oxygen concentrations. With the increase of oxygen concentration, the yield of CH4 decreases sharply, while the yield of hydrogen changes slightly. It can be further demonstrated that the reduction of CH4 concentration in the irradiated silicone rubber system is mainly due to the inhibition of CH4 formation, instead of the CH4 degradation, indicating that oxygen directly influences the conversion process of methyl radicals. Similarly, by monitoring the oxygen consumption, it is proved that oxygen is directly involved in the degradation process of silicone rubber, and oxygen scavenged the methyl radicals, which supressed the conversion process of methyl radicals to CH4. Finally, the radiation-induced crosslinking and degradation mechanism of raw silicone rubber was deduced by combining the gaseous products analysis and DFT calculation. It is demonstrated that the release of CH4 can be used to assess the radiation effect of silicone rubber. This work provides a novel method to understand deeply the radiation-induced crosslinking and degradation mechanism of silicone rubber under different atmospheres.

Abstract Image

气相色谱仪测定氧对硅橡胶辐射的影响及DFT计算
硅橡胶在不同大气环境下的辐射效应对评价材料的老化行为和评定材料的实际使用寿命具有重要意义。首先通过1H NMR和高温GPC证实了聚二甲基硅氧烷橡胶的辐射诱导交联和降解。利用所建立的气体收集系统和气相色谱法,系统地研究了不同氧浓度下辐照硅橡胶的气体产物。随着氧浓度的增加,CH4的产率急剧下降,而氢的产率变化不大。进一步证明辐照硅橡胶体系中CH4浓度的降低主要是由于抑制了CH4的生成,而不是由于抑制了CH4的降解,说明氧直接影响了甲基自由基的转化过程。同样,通过对耗氧量的监测,证明了氧直接参与硅橡胶的降解过程,氧清除甲基自由基,抑制了甲基自由基向CH4的转化过程。最后,结合气态产物分析和DFT计算,推导了生硅橡胶辐射诱导交联降解机理。结果表明,CH4的释放量可以用来评价硅橡胶的辐射效应。本研究为深入了解硅橡胶在不同气氛下的辐射诱导交联和降解机理提供了一种新的方法。
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