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Elastic and thermal expansion asymmetry in dense molecular materials

Nature Materials volume 15, pages 974–980 (2016)Cite this article

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Abstract

The elastic modulus and coefficient of thermal expansion are fundamental properties of elastically stiff molecular materials and are assumed to be the same (symmetric) under both tension and compression loading. We show that molecular materials can have a marked asymmetric elastic modulus and coefficient of thermal expansion that are inherently related to terminal chemical groups that limit molecular network connectivity. In compression, terminal groups sterically interact to stiffen the network, whereas in tension they interact less and disconnect the network. The existence of asymmetric elastic and thermal expansion behaviour has fundamental implications for computational approaches to molecular materials modelling and practical implications on the thermomechanical strains and associated elastic stresses. We develop a design space to control the degree of elastic asymmetry in molecular materials, a vital step towards understanding their integration into device technologies.

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Figure 1: Elastic asymmetry is fundamentally related to network connectivity.
Figure 2: Terminal O atoms control the free volume change asymmetry in the molecular matrix.
Figure 3: The asymmetric coefficient of thermal expansion is related to a resistive entropic force.
Figure 4: Nanoscale porosity decreases the degree of elastic asymmetry.
Figure 5: The design space for the degree of elastic asymmetry is controlled by network connectivity and density.

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Acknowledgements

We thank the US Department of Energy, Office of Basic Energy Sciences, for their financial support under Contract No. DE-FG02-07ER46391.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA

    Joseph A. Burg & Reinhold H. Dauskardt

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  1. Joseph A. Burg
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J.A.B. designed and performed simulations, analysed data, and wrote the manuscript. R.H.D. wrote the manuscript and supervised the research.

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Correspondence to Reinhold H. Dauskardt.

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The authors declare no competing financial interests.

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Burg, J., Dauskardt, R. Elastic and thermal expansion asymmetry in dense molecular materials. Nature Mater 15, 974–980 (2016). https://doi.org/10.1038/nmat4674

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