From Structural Kinematics to Thermomechanical Degradation in Polymer and Hybrid Negative Thermal Expansion Metamaterials

Metamaterials with tailored structural architectures enable negative thermal expansion through geometric mechanisms that counteract constituent-level positive expansion. This study evaluates the thermomechanical performance and structural limits of polymer and hybrid NTE lattices. We systematically classify the dominant kinematic mechanisms, including bimetallic bending, rotational squares, and re-entrant honeycombs, and quantify the inherent trade-offs between effective thermal contraction, structural stiffness, and mass efficiency. The analysis demonstrates that reliance on idealized linear–elastic and rigid-lever models leads to significant predictive discrepancies when evaluating the physical response of polymeric and hybrid prototypes. We establish that these deviations are fundamentally governed by localized stress singularities at multi-material interfaces and the profound thermoviscoelastic softening of polymers as they approach the glass transition temperature (Tg). We conclude that accurate prediction of the cyclic lifespan and dimensional stability of these systems requires a transition to coupled multiphysics frameworks. Specifically, integrating temperature-dependent cohesive zone modeling and time–temperature superposition principles is essential for capturing interfacial delamination and thermal ratcheting in high-performance polymeric NTE metamaterials.