混合平衡/不平衡效应控制了聚合物玻璃中的表面流动性
Jianquan Xu1, Asieh Ghanekarade2, Li Li1
1School of Chemistry and Chemical Engineering, Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province, Zhejiang Sci-Tech University, Hangzhou 310018, China.
聚合物玻璃过渡温度 (Tg) 在表面较低. 模拟中的非平衡条件产生了线性Tg梯度,与实验结果相匹配,并揭示了对聚合物表面行为的洞察力.
科学领域:
- 聚合物科学 聚合物科学
- 材料科学 材料科学 材料科学
- 表面科学是一门学科.
背景情况:
- 众所周知,聚合物的玻璃化过渡温度 (Tg) 在自由表面附近较低.
- 实验和模拟Tg梯度之间存在差异,这是由于确定Tg的方法不同.
研究的目的:
- 调和实验和模拟中观察到的Tg梯度的不同深度依赖.
- 为了研究非平衡效应对聚合物玻璃表面Tg的影响.
主要方法:
- 利用角度分辨率的X射线光电子光谱,总频率生成振动光谱,接触角度测量和分子动力学模拟.
- 将平衡模拟与非平衡模拟进行比较,通过减少热回火时间.
- 研究了Tg对不同厚度的聚合物薄膜加热/冷却速度的依赖性.
主要成果:
- 实验Tg梯度显示出与深度的线性变化,而平衡模拟显示出双重指数依赖.
- 非平衡模拟,减少了回火时间,产生了与实验数据一致的线性Tg梯度.
- 模拟还显示,在非平衡条件下,放松时间减少,质量密度降低.
结论:
- 非平衡效应显著影响到聚合物表面附近的Tg梯度的确定.
- 实验观察到的线性Tg梯度归因于测量过程中玻璃状状态的动态停止,非平衡性质.
- 模拟必须考虑非平衡条件,以准确复制表面Tg的实验观测.
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