Coefficient of Linear Thermal Expansion of Polymers and Polymer Composites: A Comprehensive Review

This work presents a comprehensive literature review of the coefficient of linear thermal expansion (CLTE) of polymers and polymer composite materials (PCMs). It systematizes CLTE measurement methods for isotropic and anisotropic materials, including contact techniques such as dilatometry and thermomechanical analysis and non-contact methods such as digital image correlation, laser interferometry, diffraction-based techniques, and strain-gauge methods, with attention to their accuracy and fields of applicability. Furthermore, the review describes the principal mathemaical modeling approaches used to predict the CLTE of polymers and PCMs. The review also provides a comparative analysis of CLTE values for a broad range of thermoplastics (commodity, engineering, and high-performance grades) and thermosets, identifying the key factors that govern CLTE, such as the transition from the glassy to the viscous-flow state, the presence and anisotropy of a crystalline phase, and related structure–property effects. Special consideration is given to the factors determining the CLTE of polymer composites, including the properties of the polymer matrix, the nature, size, orientation and surface treatment of the filler, the architecture and reinforcement scheme of the composite, and the manufacturing process. The review also outlines application areas in which PCMs with controlled or reduced CLTE are required and illustrates these with specific examples. Thus, the article provides integrated view of the CLTE of polymers and PCMs, compiles reference data for CLTE values of various polymers and common composite fillers and offers practical recommendations for selecting polymer materials for fabricating goods that require high thermal dimensional stability.