Rah Kyunil
Institute of Battery R and D, LG Energy Solution, 188 Moonji-ro, Yuseong-gu, Daejeon, 34122, South Korea.
ACS Omega. 2024 Dec 26;10(1):1303-1307. doi: 10.1021/acsomega.4c08891. eCollection 2025 Jan 14.
It remains, as yet, far from satisfactory to account for the explicit role of the solvent effect on the transport behaviors of various polymer solutions, especially depending upon the polymer concentration. Here, we exploit the statistical mechanical free-volume theory to describe the diffusivity of polymer solutions in an analytical form in terms of the solvent-solvent, particle-particle, and solvent-particle pair correlation functions as a function of the polymer concentration. To be specific, we introduce a particle size scaling parameter as a measure of the effective polymer-solvent interaction that leads to different polymer globular states, depending on the embedding solvents. Upon applying the theory to the polystyrene (PS) in various organic solvents, the agreement between the theory and experiment is found to be very good over the entire PS volume fraction ϕ investigated by the experiment, i.e., up to ϕ ∼ 0.50. The scaling parameter determined is discussed in association with the Flory-Huggins polymer-solvent interaction parameter χ available in the literature.
对于溶剂效应在各种聚合物溶液传输行为中所起的明确作用，目前仍远不能令人满意，尤其是这还取决于聚合物浓度。在此，我们利用统计力学自由体积理论，根据溶剂 - 溶剂、粒子 - 粒子以及溶剂 - 粒子对关联函数，以解析形式描述聚合物溶液的扩散系数，这些关联函数是聚合物浓度的函数。具体而言，我们引入一个粒径缩放参数，作为有效聚合物 - 溶剂相互作用的一种度量，该相互作用会导致不同的聚合物球状状态，这取决于所嵌入的溶剂。将该理论应用于各种有机溶剂中的聚苯乙烯（PS）时，发现在实验所研究的整个聚苯乙烯体积分数ϕ范围内，即直至ϕ ∼ 0.50，理论与实验之间的吻合度非常好。所确定的缩放参数与文献中可得的弗洛里 - 哈金斯聚合物 - 溶剂相互作用参数χ相关联进行了讨论。
