Ruiz de Luzuriaga Alaitz, Grande Hans J, Pomposo José A
Department of New Materials, CIDETEC-Centre for Electrochemical Technologies, Paseo Miramon 196, Donostia-San Sebastian E-20009, Spain.
J Chem Phys. 2009 Feb 28;130(8):084905. doi: 10.1063/1.3078248.
A compressible regular solution free energy model for describing the phase behavior of weakly interacting binary blends comprising nonrigid polymer nanoparticles and linear-polymer chains (i.e., all-polymer nanocomposites) has been developed by incorporating specific nanoparticle-nanoparticle and nanoparticle-polymer contributions into the original free volume theory for binary polymer blends of Ruzette et al. [J. Chem. Phys. 114, 8205 (2001)]. The extended model allows predicting phase behavior for weakly interacting polymer-nanoparticle/linear-polymer nanocomposites using only pure component properties (nanoparticle and polymer sizes, mass densities, coefficients of thermal expansion, and solubility parameters). The effect of polymer and nanoparticle size, as well as those arising from nanoparticle rigidity, exchange interaction energy and composition on the phase behavior of all-polymer nanocomposites have been systematically investigated. A rich variety of phase diagrams (including upper critical solution temperature-type, lower critical solution temperature-type, and hour-glass shape) are illustrated. Predicted phase diagrams for nonrigid poly(styrene)-nanoparticle (PS-np)/linear-poly(styrene) (l-PS), and branched poly(ethylene)-nanoparticle (PE-np)/l-PS nanocomposites were in excellent agreement with available experimental data.
通过将特定的纳米颗粒-纳米颗粒和纳米颗粒-聚合物相互作用项纳入Ruzette等人[《化学物理杂志》114, 8205 (2001)]提出的二元聚合物共混物原始自由体积理论中，已开发出一种可压缩正则溶液自由能模型，用于描述由非刚性聚合物纳米颗粒和线性聚合物链组成的弱相互作用二元共混物（即全聚合物纳米复合材料）的相行为。扩展后的模型能够仅使用纯组分性质（纳米颗粒和聚合物的尺寸、质量密度、热膨胀系数和溶解度参数）来预测弱相互作用聚合物-纳米颗粒/线性聚合物纳米复合材料的相行为。系统地研究了聚合物和纳米颗粒尺寸的影响，以及纳米颗粒刚性、交换相互作用能和组成对全聚合物纳米复合材料相行为的影响。展示了丰富多样的相图（包括上临界溶液温度型、下临界溶液温度型和沙漏形状）。非刚性聚苯乙烯纳米颗粒（PS-np）/线性聚苯乙烯（l-PS）以及支化聚乙烯纳米颗粒（PE-np）/l-PS纳米复合材料的预测相图与现有实验数据高度吻合。
