4.7 Article

Activation Volume of the Elastic-Plastic Transition in Molecular Crystals

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CRYSTAL GROWTH & DESIGN
卷 21, 期 9, 页码 5183-5191

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AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.1c00543

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  1. A*STAR, Singapore, via the Structural Metals and Alloys Programme [A18B1b0061]

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Nanoindentation experiments were conducted on several molecular crystals to measure the load at which elastic-to-plastic transition occurs and determine the activation volume. The results showed a linear relationship between activation volume and molecular size, suggesting a close correlation between plastic deformation and molecular dimensions in molecular crystals.
Nanoindentation experiments with a spherical indenter tip were performed on the major faces of L-alanine, p-nitroaniline, DL-tartaric acid, and sulfathiazole single crystals to measure the load at which an elastic-to-plastic deformation transition occurs, which is marked by a discrete displacement burst or pop-in. Large data sets (containing more than 100 points each) of the experimentally measured first pop-in loads, P-1, were generated. By assuming that the statistical distribution in P-1 is a consequence of the thermal fluctuations affecting the nucleation rate of incipient plastic events underneath the indenter, the activation volumes, Lambda, for the elastic-plastic transition are determined. For the four molecular crystals examined, Lambda values vary between 106 and 173 angstrom(3), which are more than an order of magnitude than those in crystalline metals. However, they are similar to the molecular volume, psi. A linear relationship between Lambda and psi suggests that the plastic deformation in molecular crystals is intimately linked to the size of the molecules. These results are discussed in the context of slip planes and their orientations to the indentation direction, interplanar spacings, intermolecular interactions, etc.

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