Taxonomy of amorphous ternary phase diagrams: the importance of interaction parameters

TL;DR

This work systematically classifies and maps over 80,000 amorphous ternary phase diagrams, revealing key interaction parameters that influence phase behavior and processability in material design.

Contribution

It provides the first large-scale computational library and classification of amorphous ternary phase diagrams based on interaction parameters.

Findings

21 phase diagram types identified, including new ones.

Most common types involve 0-3 immiscible pairs.

Processability window size is sensitive near critical interaction values.

Abstract

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.