Thermal Properties of Amorphous and Semicrystalline Polymers
Summary
Amorphous and semicrystalline polymers exhibit thermal behaviours governed by the interplay of three distinct microstructural phases: the crystalline fraction (CF), the rigid amorphous fraction (RAF) and the mobile amorphous fraction (MAF). The CF comprises ordered lamellae that melt at characteristic temperatures, while the RAF forms a constrained interphase around crystals with limited chain mobility. The MAF represents the bulk amorphous regions capable of segmental motion above the glass transition temperature (Tg). Thermal analysis techniques such as differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC) enable precise measurement of melting enthalpies, glass transitions and phase populations. Control over phase composition is central to tuning modulus, toughness, thermal expansion and barrier properties in applications ranging from biodegradable packaging to high‐performance engineering plastics. Advances in in situ spectroscopy and modelling have deepened understanding of phase formation kinetics, enabling the rational design of polymers with tailored thermal stability, energy storage capabilities and responsive mechanical performance.
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Thermal Properties of Amorphous and Semicrystalline Polymers publication trend
The graph below shows the total number of articles in thermal properties of amorphous and semicrystalline polymers across all publications each year (not limited to Nature Index journals).
Technical terms
Crystalline fraction (CF): The ordered polymer regions forming lamellae with a defined melting temperature.
Rigid amorphous fraction (RAF): The non‐crystalline interphase with restricted chain mobility adjacent to crystals.
Mobile amorphous fraction (MAF): The disordered polymer domains capable of segmental mobility above Tg.
Glass transition temperature (Tg): The temperature at which amorphous regions transition between glassy and rubbery states.
Differential scanning calorimetry (DSC): A technique measuring heat flow associated with thermal transitions.
References
- Dependence of the crystal structure on the d-units amount in semi-crystalline poly(lactic acid). International Journal of Biological Macromolecules (2024).
- Constrained amorphous interphase in plasticized poly(lactic acid): Composition and tensile elastic modulus estimation. Polymer Testing (2024).
- The 3-Phase Structure of Polyesters (PBT, PET) after Isothermal and Non-Isothermal Crystallization. Polymers (2022).
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