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      Shape-memory effects in molecular crystals

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          Abstract

          Molecular crystals can be bent elastically by expansion or plastically by delamination into slabs that glide along slip planes. Here we report that upon bending, terephthalic acid crystals can undergo a mechanically induced phase transition without delamination and their overall crystal integrity is retained. Such plastically bent crystals act as bimorphs and their phase uniformity can be recovered thermally by taking the crystal over the phase transition temperature. This recovers the original straight shape and the crystal can be bent by a reverse thermal treatment, resulting in shape memory effects akin of those observed with some metal alloys and polymers. We anticipate that similar memory and restorative effects are common for other molecular crystals having metastable polymorphs. The results demonstrate the advantage of using intermolecular interactions to accomplish mechanically adaptive properties with organic solids that bridge the gap between mesophasic and inorganic materials in the materials property space.

          Abstract

          Molecular crystals can be bent elastically by expansion or contraction on opposite faces, or plastically by delamination into slabs that glide along slip planes. Here the authors report crystals that can be bent plastically while undergoing a mechanically induced phase transition without delamination.

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          An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments

          The indentation load-displacement behavior of six materials tested with a Berkovich indenter has been carefully documented to establish an improved method for determining hardness and elastic modulus from indentation load-displacement data. The materials included fused silica, soda–lime glass, and single crystals of aluminum, tungsten, quartz, and sapphire. It is shown that the load–displacement curves during unloading in these materials are not linear, even in the initial stages, thereby suggesting that the flat punch approximation used so often in the analysis of unloading data is not entirely adequate. An analysis technique is presented that accounts for the curvature in the unloading data and provides a physically justifiable procedure for determining the depth which should be used in conjunction with the indenter shape function to establish the contact area at peak load. The hardnesses and elastic moduli of the six materials are computed using the analysis procedure and compared with values determined by independent means to assess the accuracy of the method. The results show that with good technique, moduli can be measured to within 5%.
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            Photochromism of diarylethene molecules and crystals: memories, switches, and actuators.

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              Rapid and reversible shape changes of molecular crystals on photoirradiation.

              The development of actuators based on materials that reversibly change shape and/or size in response to external stimuli has attracted interest for some time. A particularly intriguing possibility is offered by light-responsive materials, which allow remote operation without the need for direct contact to the actuator. The photo-response of these materials is based on the photoisomerization of constituent molecules (typically trans-cis isomerization of azobenzene chromophores), which gives rise to molecular motions and thereby deforms the bulk material. This effect has been used to create light-deformable polymer films and gels, but the response of these systems is relatively slow. Here we report that molecular crystals based on diarylethene chromophores and with sizes ranging from 10 to 100 micrometres exhibit rapid and reversible macroscopic changes in shape and size induced by ultraviolet and visible light. We find that on exposure to ultraviolet light, a single crystal of 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene changes from a square shape to a lozenge shape, whereas a rectangular single crystal of 1,2-bis(5-methyl-2-phenyl-4-thiazolyl)perfluorocyclopentene contracts by about 5-7 per cent. The deformed crystals are thermally stable, and switch back to their original state on irradiation with visible light. We find that our crystals respond in about 25 microseconds (that is, about five orders of magnitude faster than the response time of the azobenzene-based polymer systems) and that they can move microscopic objects, making them promising materials for possible light-driven actuator applications.
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                Author and article information

                Contributors
                pance.naumov@nyu.edu
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                19 August 2019
                19 August 2019
                2019
                : 10
                : 3723
                Affiliations
                [1 ]GRID grid.440573.1, New York University Abu Dhabi, ; PO Box 129188, Abu Dhabi, UAE
                [2 ]ISNI 0000 0004 1764 0696, GRID grid.18785.33, Diamond Light Source, ; Didcot, Oxfordshire, OX11 0DE UK
                [3 ]ISNI 000000041936754X, GRID grid.38142.3c, Radcliffe Institute for Advanced Study, , Harvard University, ; 10 Garden St, Cambridge, MA 02138 USA
                Author information
                http://orcid.org/0000-0002-3676-2950
                http://orcid.org/0000-0001-5956-6496
                http://orcid.org/0000-0003-1326-0744
                Article
                11612
                10.1038/s41467-019-11612-z
                6700106
                31427570
                5c11cd21-9e4a-4eb4-a1a4-733c9eae38fb
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 31 October 2018
                : 19 July 2019
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                Custom metadata
                © The Author(s) 2019

                Uncategorized
                mechanical properties,organic molecules in materials science
                Uncategorized
                mechanical properties, organic molecules in materials science

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