聚合物-粘土纳米复合材料形貌演变的多尺度模拟研究。

IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Parvez Khan*, Ankit Patidar and Gaurav Goel*, 
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引用次数: 0

摘要

分子模拟为研究含有层状硅酸盐如蒙脱土(MMT)的聚合物-粘土纳米复合材料(PCNCs)的形态演变和结构-性能关系提供了有效途径。蒙脱土是一类重要的材料,在一些性能上比组成聚合物有显著的增强。然而,较长的松弛时间和较大的系统尺寸要求限制了它们在实际系统中的应用。在这项工作中,我们开发了一个与MARTINI力场兼容的有机修饰MMT (oMMT)的粗粒度(CG)模型,这是一个具有高可转移性的化学特异性相互作用模型。利用四甲基铵(TMA)为间隙离子的MMT的解理能、基间距和力学性能的色散和极性分量,根据官能团的极性,对粘土颗粒MARTINI头类型进行了合理的估计。CG模型为PE/TMA-MMT PCNC中聚乙烯(PE)的结构、热力学和动力学特性提供了准确的同时估计,与所有原子(AA)模拟的偏差小于4%。利用已开发的CG模型研究了PCNCs中由粘土引起的聚乙烯-聚乙二醇嵌段共聚物(PE-b-PEG)的缓慢重分布,其构象变化发生在微秒时间尺度上。利用PE-b-PEG各块的优先相互作用系数和聚类分析,研究了黏土排列方式(剥离型和粘滞型)对共聚物在黏土表面重定向和组装的影响。我们发现涂有PE-b- peg的oMMT作为一个中性表面(聚合物-聚合物和聚合物-oMMT + PE-b- peg的焓相互作用差异很小),纳米填料的主要影响是粘土片对PE链的约束和空间效应。最后,从长时间CG模拟中获得的几种不同的PCNC形态被反向映射到AA分辨率,以便准确计算机械和物理性能。这项工作提供了一个计算效率高的多尺度模拟框架,用于精确确定PCNCs的形态和机械性能,从而实现合理的材料设计。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Characterization of Morphology Evolution in a Polymer–Clay Nanocomposite Using Multiscale Simulations

Characterization of Morphology Evolution in a Polymer–Clay Nanocomposite Using Multiscale Simulations

Molecular simulations provide an effective route for investigating morphology evolution and the structure–property relationship in polymer–clay nanocomposites (PCNCs) incorporating layered silicates like montmorillonite (MMT), an important class of materials that show a significant enhancement over the constituent polymer for several properties. However, long relaxation times and large system size requirements limit their application to systems of practical interest. In this work, we developed a coarse-grained (CG) model of organically modified MMT (oMMT) compatible with the MARTINI force field, a chemically specific interaction model with high transferability. The dispersive and polar components of cleavage energy, basal spacing, and mechanical properties of MMT with tetramethylammonium (TMA) as intergallery ions were used to obtain a rational estimate for clay particle MARTINI bead types in accordance with the polarity of the functional group. The CG model provided accurate concurrent estimates for the structural, thermodynamic, and dynamical properties of polyethylene (PE) in a PE/TMA-MMT PCNC, with less than a 4% deviation from all atom (AA) simulations. The slow clay-induced redistribution of the polyethylene–polyethylene glycol block copolymer (PE-b-PEG) in the PCNCs was investigated using the developed CG model, with conformational changes occurring over a microsecond time scale. The preferential interaction coefficient and cluster analysis of individual blocks of PE-b-PEG were used to study the effect of clay arrangement (exfoliated vs tactoid) on copolymer reorientation and assembly at the clay surface. We find that the oMMT coated with PE-b-PEG acts as a neutral surface (small difference in polymer–polymer and polymer-oMMT + PE-b-PEG enthalpic interactions), and the primary influence of the nanofiller is a result of confinement and steric effect of the clay sheets on the PE chains. Finally, several different PCNC morphologies obtained from long CG simulations were backmapped to AA resolution for the accurate calculation of mechanical and physical properties. This work offers a computationally efficient multiscale simulation framework for the accurate determination of the morphology and mechanical performance of PCNCs, enabling a rational material design.

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来源期刊
Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation 化学-物理:原子、分子和化学物理
CiteScore
9.90
自引率
16.40%
发文量
568
审稿时长
1 months
期刊介绍: The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
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