A reaction-diffusion framework for hydrolytic degradation of amorphous polymers based on a discrete chain scission model.
A reaction-diffusion framework for hydrolytic degradation of amorphous polymers based on a discrete chain scission model.
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基于离散断链模型的无定形聚合物水解降解的反应扩散框架。
DOI：
10.1016/j.actbio.2023.06.021
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发表时间：
2023
影响因子：
9.7
通讯作者：
Pan Z
中科院分区：
文献类型：
--
作者：
Pan Z
聚合物的水解降解涉及长链分子的断裂，导致分子量降低和质量损失。然而，精确的降解响应取决于沿着聚合物主链沿着的各个键的断裂概率。特别是，认为靠近链端的键比内部键更容易水解。在本文中，我们将一个离散断链模型，可以处理任意键断概率连续反应扩散框架内。整体水解动力学（包括自催化）独立的断链模型。通过解耦的断链机制的动力学的描述，我们的框架，使断链机制的分子量减少和质量损失曲线通常在实验降解研究中报告的识别。我们进一步提出了一个简化的连续模型，它更适合于大规模的模拟，同时保留了完整的离散连续模型的预测能力。该模型的能力是说明在代表性的案例研究的基础上，从文献中的实验数据为不同的材料和geometris.Statement的significanceMany模型已被提出来预测的分子量和质量损失在生物降解聚合物进行水解降解的演变。然而，现有的模型仍然是有限的，在他们的能力来描述降解机制，自催化动力学和短链扩散同时。而且，现有的模型往往依赖于经验关系和大量的拟合参数。在这里，我们提出了一个概念上简单的离散-连续数学框架与少量的参数，都有一个明确的物理意义。对实验数据的模型校准被简化，并且进一步提供了对起作用的降解机制的见解，即随机断裂、链端断裂或两者的组合。该框架可以作为未来概括的基础，包括对结晶度演变或其他降解机制（如热氧化或光降解）的描述。
Hydrolytic degradation of polymers involves the scission of long chain molecules, leading to molecular weight reduction and mass loss. The precise degradation response however depends on the scission probability of individual bonds along the polymer backbone. In particular, bonds near the chain ends are considered to be more susceptible to hydrolysis than inner bonds. In this paper, we incorporate a discrete chain scission model that can handle arbitrary bond scission probabilities within a continuum reaction-diffusion framework. Overall hydrolysis kinetics (including autocatalysis) is described independently of the chain scission model. By decoupling the description of the chain scission mechanism from kinetics, our framework enables the identification of the chain scission mechanism from molecular weight reduction and mass loss curves commonly reported in experimental degradation studies. We further propose a reduced continuum model which is better suited for large-scale simulations while retaining the predictive capability of the full discrete-continuum model. The model capability is illustrated in representative case studies based on experimental data from the literature for different materials and geometries.Statement of significanceMany models have been proposed to predict the evolution of molecular weight and mass loss in biodegradable polymers undergoing hydrolytic degradation. However, existing models remain limited in their ability to describe the degradation mechanism, autocatalytic kinetics and short chains diffusion simultaneously. Moreover, existing models often rely on empirical relations and a large number of fitting parameters. Here, we propose a conceptually simple discrete-continuum mathematical framework with a small number of parameters which all have a clear physical meaning. Model calibration against experimental data is simplified, and further provides insights into the degradation mechanisms at play, namely random scission, chain-end scission, or a combination of both. The framework can serve as a basis for future generalisations, including a description of evolving crystallinity, or other degradation mechanisms, such as thermal oxidation or photo-degradation.
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影响因子：
4.7
作者：
Wang，Jiang;Wang，Tian -Tian;Zhou，Yin-Ning
通讯作者：
Zhou，Yin-Ning
使用固定枢轴技术对同时链端和随机断裂进行建模
影响因子：
2.1
作者：
Yong Kuen Ho;P. Doshi;H. K. Yeoh
通讯作者：
H. K. Yeoh
生物可吸收聚合物分子量演变的动力学断裂模型
DOI：
10.1002/pen.26131
发表时间：
2022
期刊：
Polymer Engineering & Science
影响因子：
--
作者：
Aoife Hill;W. Ronan
通讯作者：
W. Ronan
影响因子：
5.3
作者：
Zhouzhou Pan;L. Brassart
通讯作者：
Zhouzhou Pan;L. Brassart
影响因子：
14
作者：
Soares, Joao S.;Zunino, Paolo
通讯作者：
Zunino, Paolo