Can five chemically different lamellar crystals self-assemble in a single spherulite?

Year: 2025

Type: article

Abstract: Semicrystalline polymers with multiple crystallizable blocks provide opportunities to develop materials with hierarchical structures and customized properties, but they also pose unique challenges for understanding their crystallization. In this work, we investigate the crystallization from a miscible melt of a pentablock quintopolymer composed of five potentially crystallizable and biocompatible blocks, composed of polyethylene (PE), poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), poly(L-lactide) (PLLA), and polyglycolide (PGA), with a composition optimized to allow the crystallization of all blocks. Using Differential Scanning Calorimetry, synchrotron Fourier Transform Infrared Spectroscopy, synchrotron in situ Wide-angle and Small-angle X-Ray Scattering, Transmission Electron Microscopy, and Polarized Light Optical Microscopy, we demonstrate that upon cooling from the melt, all covalently linked blocks crystallize in a well-defined sequence: PGA > PLLA > PE > PCL > PEO. During crystallization, well-developed pentacrystalline positive spherulites are produced. This unprecedented level of self-assembly reveals the potential of complex block polymers to design multifunctional crystalline materials. Understanding the mechanisms of block copolymer crystallization is fundamentally important. Here the authors investigated the crystallization behavior from a miscible melt of a polymeric material composed of five potentially crystallizable and biocompatible, chemically distinct blocks.

Source: Nature Communications

DOI: 10.1038/s41467-025-64845-6

Authors: Eider Matxinandiarena, Ricardo A. Pérez-Camargo, Víctor Sebastián, Pengfei Zhang, Viko Ladelta, Nikos Hadjichristidis, Alejandro J. Müller

Institutions: University of the Basque Country, Polymat, Consejo Superior de Investigaciones Científicas, Universidad de Zaragoza, Instituto de Nanociencia y Materiales de Aragón, Cornell University, King Abdullah University of Science and Technology, Ikerbasque

Language: English

Topic: Polymer crystallization and properties

Subfield: Polymers and Plastics

Field: Materials Science

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,990

Funders: Ministerio de Ciencia, Innovación y Universidades, European Commission, Eusko Jaurlaritza, King Abdullah University of Science and Technology, Horizon 2020 Framework Programme, Agencia Estatal de Investigación, Interreg

OpenAlex ID: W4416092372