Crystallization Behavior of Block Copolymers

Block copolymers combine distinct polymer segments covalently linked into one macromolecule. When one or more blocks crystallise, a complex interplay arises between microphase separation and ordered chain folding. Crystallisation drives the formation of lamellar crystals within individual domains, while incompatibility between blocks induces periodic nanostructures such as spheres, cylinders or lamellae on the 10–100 nm scale. The sequence of block crystallisation, determined by melting temperatures and kinetic factors, governs final morphology: early‐crystallising blocks can template or confine the later‐crystallising segments, leading to spherulitic, microspherulitic or non‐spherulitic textures. Control over crystallisation and phase separation enables the design of materials with tailored mechanical strength, barrier properties, biodegradability and functional nanostructures for applications in membranes, drug delivery, nanolithography and high‐performance composites. Advances in in situ techniques such as synchrotron SAXS/WAXS, solid‐state NMR and AFM have elucidated crystallisation pathways, domain confinement effects and epitaxial alignment, fostering the rational design of multicrystalline block architectures.

Research from Nature Portfolio

Recent studies have demonstrated the synthesis of a multiblock quintopolymer comprising polyethylene, polyethylene oxide, poly(ε-caprolactone), poly(L-lactide) and polyglycolide blocks, each exhibiting a distinct crystalline phase. By employing a fluoroalcohol-assisted catalyst-switch strategy coupled with complementary polymerisation methods, researchers achieved precise sequence control and incorporation of a high‐melting‐point polyglycolide segment. Solid‐state NMR, X-ray diffraction and differential scanning calorimetry revealed well‐resolved melting and crystallisation transitions for all five blocks, providing a versatile platform for tuning thermal and mechanical performance through block composition and arrangement.

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Crystallization Behavior of Block Copolymers publication trend

The graph below shows the total number of articles in crystallization behavior of block copolymers across all publications each year (not limited to Nature Index journals).

Technical terms

Block copolymer: A macromolecule composed of two or more covalently linked homopolymer segments that can microphase separate into ordered nanodomains.

Crystallisation: The process by which polymer chains fold into ordered lamellar structures, yielding regions of high density and anisotropic properties.

Microphase separation: Self-assembly of chemically distinct blocks into periodic nanostructures due to thermodynamic incompatibility.

Lamella(e): Plate-like crystalline regions formed by folded polymer chains within semicrystalline polymers.

Spherulite: Radial aggregate of lamellar crystals, often observed in bulk‐crystallising polymers as Maltese‐cross patterns under polarized light.

References

1. Catalyst switch strategy enabled a single polymer with five different crystalline phases. Nature Communications (2023).
2. Adsorption and Structuration of PEG Thin Films: Influence of the Substrate Chemistry. Polymers (2024).
3. Double Crystallization and Phase Separation in Polyethylene—Syndiotactic Polypropylene Di-Block Copolymers. Polymers (2021).