Polymer Crystallization Dynamics and Morphological Control

Polymer crystallization involves the organisation of macromolecular chains into ordered regions through nucleation and lamellar growth, a process that unfolds over multiple length and time scales. Initial nuclei form within a supercooled melt or solution and propagate as stacked lamellae whose thickness, orientation and branching govern the ultimate morphology. The interplay of chain connectivity, entanglements and external conditions such as temperature, concentration and confinement dictates whether structures evolve into dense lamellar arrays, spherulitic aggregates or more complex architectures. Control over these parameters enables tuning of mechanical stiffness, optical properties and barrier performance in applications ranging from biomedical carriers to high-performance composites. Advances in experimental methods, simulation and interfacial engineering have revealed routes to direct crystal habit, induce symmetry breaking and stabilise non-equilibrium forms, thereby opening prospects for bespoke nanostructures with precise functional attributes.

Research from Nature Portfolio

Directed polymer crystallization within curved interfaces has been exploited to generate nanoscale single-crystal capsules. By conducting miniemulsion crystallisation of poly(L-lactic acid) at a water/oil boundary, researchers produced “crystalsomes” whose lamellar shells mimic liposomal geometry and yield a two- to three-order enhancement in bending modulus, illustrating how curvature guides lamellar registry and capsule mechanics. Thermally induced phase separation under nanoconfinement has yielded semicrystalline nanocapsules with finely tunable diameters and shell thicknesses. A one-step quench of a dilute polymer solution in sub-500 nm droplets directs crystallisation within emulsified domains, affording control over crystalline fraction and membrane rigidity for potential drug-delivery vehicles. Investigations of bottlebrush polymers have uncovered spontaneous translational-symmetry breaking in hollow spherical crystals. Local chain overcrowding at the crystallisation front induces lamella bending and formation of “molecular crystalsomes”, demonstrating a new principle for designing asymmetric nanostructures and extending strategies for morphological control beyond classical lamellar assemblies.

Polymer Crystallization Dynamics and Morphological Control publication trend

The graph below shows the total number of articles in polymer crystallization dynamics and morphological control across all publications each year (not limited to Nature Index journals).

Technical terms

Crystalsome: A hollow, capsule-like structure formed by curved lamellar crystals of polymers, combining features of vesicles and single crystals.

Lamellae: Thin, plate-like crystalline layers resulting from ordered polymer chain folding and stacking during growth.

Spherulite: Radial aggregates of lamellae that grow from a common nucleus, often exhibiting birefringent banded patterns under polarised light.

Nucleation: The initial formation of a stable, ordered cluster of polymer chains that serves as a seed for subsequent crystal growth.

Tie chain: Polymer segments that connect crystalline regions, mediating stress transfer and influencing mechanical properties.

Entanglement: Topological interlocking of polymer chains that affects mobility in the melt and dynamics during crystallisation.

References

1. Highly robust crystalsome via directed polymer crystallization at curved liquid/liquid interface. Nature Communications (2016).
2. Synthesis of semicrystalline nanocapsular structures obtained by Thermally Induced Phase Separation in nanoconfinement. Scientific Reports (2016).
3. Breaking translational symmetry via polymer chain overcrowding in molecular bottlebrush crystallization. Nature Communications (2020).
4. Molecular Chirality of Biosynthesized PHB Translates into Uniformly Curved Single Crystals in Langmuir Films. Small (2024).
5. Molecular dynamics simulation of linear polyethylene blends: Effect of molar mass bimodality on topological characteristics and mechanical behavior. Polymer (2019).
6. Concepts of Nucleation in Polymer Crystallization. Crystals (2021).