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An atomistic mechanism for elasto-plastic bending in molecular crystals.

ABSTRACT: Mechanically flexible single crystals of molecular materials offer potential for a multitude of new directions in advanced materials design. Before the full potential of such materials can be exploited, insight into their mechanisms of action must be better understood. Such insight can be only obtained through synergistic use of advanced experimentation and simulation. We herein report the first detailed mechanistic study of elasto-plastic flexibility in a molecular solid. An atomistic origin for this mechanical behaviour is proposed through a combination of atomic force microscopy, μ-focus synchrotron X-ray diffraction, Raman spectroscopy, ab initio simulation, and computed elastic tensors. Our findings suggest that elastic and plastic bending are intimately linked and result from extensions of the same molecular deformations. The proposed mechanism bridges the gap between contested mechanisms, suggesting its applicability as a general mechanism for elastic and plastic bending in organic molecular crystals.

SUBMITTER: Bhattacharya B

PROVIDER: S-EPMC10056064 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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An atomistic mechanism for elasto-plastic bending in molecular crystals.

Bhattacharya Biswajit B Michalchuk Adam A L AAL Silbernagl Dorothee D Yasuda Nobuhiro N Feiler Torvid T Sturm Heinz H Emmerling Franziska F

Chemical science 20230213 13

Mechanically flexible single crystals of molecular materials offer potential for a multitude of new directions in advanced materials design. Before the full potential of such materials can be exploited, insight into their mechanisms of action must be better understood. Such insight can be only obtained through synergistic use of advanced experimentation and simulation. We herein report the first detailed mechanistic study of elasto-plastic flexibility in a molecular solid. An atomistic origin fo ...[more]

PMID: 37006676

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Project description:As an emerging class of flexible materials, mechanically bendable molecular crystals are broadly classified as elastic or plastic. Nevertheless, flexible organic crystals with mutually exclusive elastic and plastic traits, with contrasting structural requirements, co-existing under different stress settings are exceptional; hence, it is imperative to establish the concurring factors that beget this rare occurrence. We report a series of halogen-substituted benzil crystals showing elastic bending (within ∼2.45% strain), followed by elastoplastic deformation under ambient conditions. Under higher stress settings, they display exceptional plastic flexibility that one could bend, twist, or even coil around a capillary tube. X-ray diffraction, microscopy, and computational data reveal the microscopic and macroscopic basis for the exciting co-existence of elastic, elastoplastic, and plastic properties in the crystals. The layered molecular arrangement and the weak dispersive interactions sustaining the interlayer region provide considerable tolerance towards breaking and making upon engaging or releasing the external stress; it enables restoring the original state within the elastic strain. Comparative studies with oxalate compounds, wherein the twisted diketo moiety in benzil was replaced with a rigid and coplanar central oxalate moiety, enabled us to understand the effect of the anisotropy factor on the crystal packing induced by the C[double bond, length as m-dash]O⋯C tetral interactions. The enhanced anisotropy depreciated the elastic domain, making the oxalate crystals more prone to plastic deformation. Three-point bending experiments and the determined Young's moduli further corroborate the co-existence of the elastic and plastic realm and highlight the critical role of the underlying structural elements that determine the elastic to plastic transformation. The work highlights the possible co-existence of orthogonal mechanical characteristics in molecular crystals and further construed the concurrent role of microscopic and macroscopic elements in attaining this exceptional mechanical trait.

Project description:Background: Plate osteosynthesis is a widely used technique for bone fracture fixation; however, complications such as plate bending remain a significant clinical concern. A better understanding of the failure mechanisms behind plate osteosynthesis is crucial for improving treatment outcomes. This study aimed to develop finite element (FE) models to predict plate bending failure and validate these against in vitro experiments using literature-based and experimentally determined implant material properties. Methods: Plate fixations of seven cadaveric tibia shaft fractures were tested to failure in a biomechanical setup with various implant configurations. FE models of the bone-implant constructs were developed from computed tomography (CT) scans. Elasto-plastic implant material properties were assigned using either literature data or the experimentally derived data. The predictive capability of these two FE modelling approaches was assessed based on the experimental ground truth. Results: The FE simulations provided quantitatively correct prediction of the in vitro cadaveric experiments in terms of construct stiffness [concordance correlation coefficient (CCC) = 0.97, standard error of estimate (SEE) = 23.66, relative standard error (RSE) = 10.3%], yield load (CCC = 0.97, SEE = 41.21N, RSE = 7.7%), and maximum force (CCC = 0.96, SEE = 35.04, RSE = 9.3%), when including the experimentally determined material properties. Literature-based properties led to inferior accuracies for both stiffness (CCC = 0.92, SEE = 27.62, RSE = 19.6%), yield load (CCC = 0.83, SEE = 46.53N, RSE = 21.4%), and maximum force (CCC = 0.86, SEE = 57.71, RSE = 14.4%). Conclusion: The validated FE model allows for accurate prediction of plate osteosynthesis construct behaviour beyond the elastic regime but only when using experimentally determined implant material properties. Literature-based material properties led to inferior predictability. These validated models have the potential to be utilized for assessing the loads leading to plastic deformation in vivo, as well as aiding in preoperative planning and postoperative rehabilitation protocols.

Project description:Although many examples of mechanically flexible crystals are currently known, their utility in all-flexible devices is not yet adequately demonstrated, despite their immense potential for fabricating high performance flexible devices. Here, we report two alkylated diketopyrrolopyrrole (DPP) semiconducting single crystals, one of which displays impressive elastic mechanical flexibility whilst the other is brittle. Using the single crystal structures and density functional theory (DFT) calculations, we show that the methylated diketopyrrolopyrrole (DPP-diMe) crystals, with dominant π-stacking interactions and large contributions from dispersive interactions, are superior in terms of their stress tolerance and field-effect mobility (μ FET) when compared to the brittle crystals of the ethylated diketopyrrolopyrrole derivative (DPP-diEt). Periodic dispersion-corrected DFT calculations revealed that upon the application of 3% uniaxial strain along the crystal growth (a)-axis, the elastically flexible DPP-diMe crystal displays a soft energy barrier of only 0.23 kJ mol-1 while the brittle DPP-diEt crystal displays a significantly larger energy barrier of 3.42 kJ mol-1, in both cases relative to the energy of the strain-free crystal. Such energy-structure-function correlations are currently lacking in the growing literature on mechanically compliant molecular crystals and have the potential to support a deeper understanding of the mechanism of mechanical bending. The field effect transistors (FETs) made of flexible substrates using elastic microcrystals of DPP-diMe retained μ FET (from 0.019 cm2 V-1 s-1 to 0.014 cm2 V-1 s-1) more efficiently even after 40 bending cycles when compared to the brittle microcrystals of DPP-diEt which showed a significant drop in μ FET just after 10 bending cycles. Our results not only provide valuable insights into the bending mechanism, but also demonstrate the untapped potential of mechanically flexible semiconducting crystals for designing all flexible durable field-effect transistor devices.

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An atomistic mechanism for elasto-plastic bending in molecular crystals.

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An atomistic mechanism for elasto-plastic bending in molecular crystals.

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