Manning Gerald S
Department of Chemistry and Chemical Biology, Rutgers University, New Brunswick, New Jersey 08854, United States.
ACS Omega. 2018 Dec 31;3(12):18857-18866. doi: 10.1021/acsomega.8b02950.
We present a theory for a universal gel based on a McMillan-Mayer treatment of a solute-solvent fluid as a generalization of the universal van der Waals equation of state for a pure liquid/vapor system. The elastic resilience of the networked gel is modeled by a universal Langevin function. This combination of van der Waals interactions and nonlinear Langevin elasticity produces an abrupt onset of large-amplitude density fluctuations deep in the interior of the gel at a critical temperature. Then, at a second, lower, critical temperature, the entire swollen gel collapses to a high-density phase. The universal gel has an "upper" critical temperature behavior, meaning that the gel transition to high density occurs on decreasing the temperature. At the cost of loss of universality, the theory is generalized to predict lower critical temperature dependence, whereby an aqueous hydrophobic gel exhibits phase coexistence when the temperature is raised. The theory is consistent with the Gibbs phase rule, suitably generalized to coexisting phases that are not at the same pressure in equilibrium conditions.
我们基于对溶质 - 溶剂流体的麦克米兰 - 迈耶处理方法,提出了一种通用凝胶理论,作为纯液体/蒸汽系统通用范德华状态方程的推广。网络凝胶的弹性恢复力由通用朗之万函数建模。范德华相互作用和非线性朗之万弹性的这种结合,在临界温度下,会在凝胶内部深处引发大振幅密度涨落的突然出现。然后,在第二个更低的临界温度下,整个溶胀的凝胶会坍缩成高密度相。通用凝胶具有“上”临界温度行为,即凝胶向高密度的转变是在温度降低时发生的。以失去通用性为代价,该理论被推广以预测较低临界温度依赖性,据此,当温度升高时,水性疏水凝胶会出现相共存现象。该理论与吉布斯相律一致,吉布斯相律经过适当推广后适用于平衡条件下压力不同的共存相。