论文标题
基于扭曲的键和渐近匹配的概念,用于聚合物链分裂的统计力学框架
A statistical mechanics framework for polymer chain scission, based on the concepts of distorted bond potential and asymptotic matching
论文作者
论文摘要
为了设计越来越坚硬,弹性和抗疲劳的弹性体和水凝胶,必须确定分子水平的可控网络参数与必须建立控制损害和故障的宏观量之间的关系。基于统计力学的组成型模型使用了具有刚性链接的自由接头链(FJC)模型的变体。但是,由于聚合物链的自由能状态由焓键失真效应主导,因为该链接近其破裂点,因此,如果该模型旨在捕获链破裂,则应考虑键的可扩展性。为此,将新的键势补充为FJC模型(在Buche及其同事的UFJC框架中得出),我们已经扩展了该模型,以产生一种可易于处理的封闭形式模型,该模型可与组成型模型开发相提并论。灵感来自渐近匹配的UFJC模型响应,得出了简单的,准多项式和非谐键势能函数的启发。使用这种键势,建立了依赖于链伸的键拉伸和链力的近似但高度准确的分析函数。然后,使用此聚合物链模型,开发了随机热波动驱动的链破裂框架。该框架是基于力修饰的倾斜键电势,该键可以解释扭曲键势能,从而计算消散的链分离能量。该模型适合从原子力显微镜拉伸测试收集的单链机械响应数据,以验证并更深入地了解发生的分子物理学。由于它们的分析性质,可以直接实现此聚合物链模型和相关的破裂框架,以占多分散弹性体网络中断裂和疲劳的有限元模型。
To design increasingly tough, resilient, and fatigue-resistant elastomers and hydrogels, the relationship between controllable network parameters at the molecular level to macroscopic quantities that govern damage and failure must be established. Constitutive models based upon statistical mechanics have used variants of the freely jointed chain (FJC) model with rigid links. However, since the free energy state of a polymer chain is dominated by enthalpic bond distortion effects as the chain approaches its rupture point, bond extensibility ought to be accounted for if the model is intended to capture chain rupture. To that end, a new bond potential is supplemented to the FJC model (as derived in the uFJC framework of Buche and colleagues), which we have extended to yield a tractable, closed-form model that is amenable to constitutive model development. Inspired by the asymptotically matched uFJC model response, a simple, quasi-polynomial, and anharmonic bond potential energy function is derived. Using this bond potential, approximate yet highly-accurate analytical functions for bond stretch and chain force dependent upon chain stretch are established. Then, using this polymer chain model, a stochastic thermal fluctuation-driven chain rupture framework is developed. This framework is based upon a force-modified tilted bond potential that accounts for distortional bond potential energy, allowing for the calculation of dissipated chain scission energy. The model is fit to single-chain mechanical response data collected from atomic force microscopy tensile tests for validation and to glean deeper insight into the molecular physics taking place. Due to their analytical nature, this polymer chain model and the associated rupture framework can be straightforwardly implemented in finite element models accounting for fracture and fatigue in polydisperse elastomer networks.