Grain Growth and Coarsening Dynamics in a Compositionally Asymmetric Block Copolymer Revealed by X-ray Photon Correlation Spectroscopy

Ronald M. Lewis, Grayson L. Jackson, Michael J. Maher, Kyungtae Kim, Suresh Narayanan, Timothy P. Lodge, Mahesh K. Mahanthappa, Frank S. Bates

Research output: Contribution to journalArticlepeer-review

Abstract

The dynamics of nanostructured soft materials crucially impact their associated macroscopic material properties, yet they are often difficult to measure due to spatiotemporal limitations of conventional instrumentation. Herein, we use X-ray photon correlation spectroscopy to directly observe particle-scale dynamics during grain growth and coarsening in a body-centered cubic-forming diblock polymer melt, with specific attention to the distribution of structural relaxation times associated with the interplanar (110) distance. Following sample quenching from the disordered state, these dynamical phenomena surprisingly exhibit little dependence on time and thermal quench depth. We posit that these relaxations stem from collective particle motions during grain rotation. We also observe unusual internally referenced heterodyne correlations, which enable measurements of speed distributions within the sample. These speeds are significantly slower and appear at much longer annealing times than those previously reported during grain nucleation and growth in microphase-separated block polymer melts. Drawing on analogies between polycrystalline hard and soft materials, we ascribe these speed distributions to misorientation-dependent grain boundary migration during ordered domain coarsening and anomalously fast, cooperative stringlike particle motion along the grain boundaries. Thus, these coherent X-ray measurements provide new opportunities to interrogate grain boundary structure and dynamics in polycrystalline soft materials.

Original languageEnglish (US)
Pages (from-to)8233-8243
Number of pages11
JournalMacromolecules
Volume53
Issue number19
DOIs
StatePublished - Oct 13 2020

Bibliographical note

Funding Information:
Support for this work was provided by the National Science Foundation under Grants DMR-1801993 (R.M.L., M.J.M., K.K., and F.S.B.), CHE-1608115 and CHE-1807330 (G.L.J. and M.K.M.). SAXS experiments were conducted at the 8-ID-E and 5-ID-D Advanced Photon Source (APS). Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.

Publisher Copyright:
Copyright © 2020 American Chemical Society.

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