DeFelice Jeffrey, Lipson Jane E G
Department of Chemistry, Dartmouth College, Hanover, NH 03755, USA.
Soft Matter. 2021 Jan 22;17(2):376-387. doi: 10.1039/d0sm01634a.
In the region near an interface, the microscopic properties of a glass forming liquid may be perturbed from their equilibrium bulk values. In this work, we probe how the interfacial effects of additive particles dispersed in a matrix can influence the local mobility of the material and its glass transition temperature, Tg. Experimental measurements and simulation results indicate that additives, such as nanoparticles, gas molecules, and oligomers, can shift the mobility and Tg of a surrounding polymer matrix (even for relatively small concentrations of additive; e.g., 5-10% by volume) relative to the pure bulk matrix, thus leading to Tg enhancement or suppression. Additives thus provide a potential route for modifying the properties of a polymer material without significantly changing its chemical composition. Here we apply the Limited Mobility (LM) model to simulate a matrix containing additive species. We show that both additive concentration, as well as the strength of its very local influence on the surrounding matrix material, will determine whether the Tg of the system is raised or lowered, relative to the pure matrix. We demonstrate that incorporation of additives into the simple LM simulation method, which has successfully described the behavior of bulk and thin film glassy solids, leads to direct connections with available experimental and simulation results for a broad range of polymer/additive systems.
在界面附近的区域,玻璃形成液体的微观性质可能会偏离其平衡体相值。在这项工作中,我们探究了分散在基质中的添加剂颗粒的界面效应如何影响材料的局部流动性及其玻璃化转变温度Tg。实验测量和模拟结果表明,添加剂,如纳米颗粒、气体分子和低聚物,相对于纯体相基质,可以改变周围聚合物基质的流动性和Tg(即使添加剂浓度相对较低;例如,体积分数为5 - 10%),从而导致Tg升高或降低。因此,添加剂为在不显著改变聚合物材料化学成分的情况下改变其性能提供了一条潜在途径。在此,我们应用有限流动性(LM)模型来模拟含有添加剂物种的基质。我们表明,添加剂浓度及其对周围基质材料的局部影响强度,将决定相对于纯基质,系统的Tg是升高还是降低。我们证明,将添加剂纳入已成功描述体相和薄膜玻璃态固体行为的简单LM模拟方法中,能够与广泛的聚合物/添加剂系统的现有实验和模拟结果建立直接联系。