Ameslon Yasin, Liu Hao, Harting Jens, Ronsin Olivier J J, Wodo Olga
Helmholtz-Institute Erlangen-Nürnberg for Renewable Energy (IET-2), Forschungszentrum Jülich, Cauerstr. 1, 91058, Erlangen, Germany.
Department of Chemical and Biological Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstr. 1, 91058, Erlangen, Germany.
Phys Chem Chem Phys. 2025 May 14;27(19):9998-10010. doi: 10.1039/d5cp00335k.
Understanding phase diagrams is essential for material selection and design, as they provide a comprehensive representation of the thermodynamics of mixtures. This work delivers a broad and systematic overview of possible ternary phase diagrams for amorphous systems representative of polymers, small organic molecules, and solvents. Thanks to computationally efficient methods, an unprecedented library of >80 000 ternary phase diagrams is generated based on a systematic screening of interaction parameters. Twenty-one phase diagram types, including unreported ones, are identified. They are classified according to simple rules related to the number of immiscible material pairs, of miscibility gaps, and of three-phase regions. They are mapped onto the three-dimensional interaction parameters space, providing a clear picture of their likelihood and existence conditions. Four well-known phase-diagram types with 0, 1, 2, or 3 immiscible pairs are found to be the most likely. The numerous uncommon phase diagrams are mostly observed within a small parameter window around the critical interaction parameter values. For the most common phase diagram types, we show that the size of the processability window becomes sensitive to interaction parameter variations close to critical values. The sensitivity decreases for materials with increasing molar size. Finally, successful comparisons of simulated and experimental phase diagrams showcase the real-world relevance of this theoretical analysis. The presented results lay a robust foundation for rational design of solution processing conditions and for blend morphology control. Immediate applications include organic thin films and the identification of green solvents for sustainable processing.
理解相图对于材料的选择和设计至关重要，因为它们全面地呈现了混合物的热力学性质。这项工作对代表聚合物、小分子有机物和溶剂的非晶体系可能的三元相图进行了广泛而系统的概述。借助计算效率高的方法，基于对相互作用参数的系统筛选，生成了一个包含超过80000个三元相图的前所未有的库。识别出了21种相图类型，包括未报道过的类型。它们根据与不混溶材料对的数量、混溶间隙的数量和三相区域的数量相关的简单规则进行分类。它们被映射到三维相互作用参数空间，清晰地展示了它们的可能性和存在条件。发现具有0、1、2或3个不混溶对的四种著名相图类型是最有可能的。众多不常见的相图大多在临界相互作用参数值附近的一个小参数窗口内观察到。对于最常见的相图类型，我们表明可加工性窗口的大小在接近临界值时对相互作用参数变化变得敏感。对于摩尔尺寸增加的材料，这种敏感性降低。最后，模拟相图与实验相图的成功比较展示了这种理论分析在现实世界中的相关性。所呈现的结果为合理设计溶液加工条件和控制共混物形态奠定了坚实的基础。直接应用包括有机薄膜以及识别用于可持续加工的绿色溶剂。
