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- ItemQuantifying Rate-and Temperature-Dependent Molecular Damage in Elastomer Fracture(College Park, Md. : APS, 2020) Slootman, Juliette; Waltz, Victoria; Yeh, C. Joshua; Baumann, Christoph; Göstl, Robert; Comtet, Jean; Creton, CostantinoElastomers are highly valued soft materials finding many applications in the engineering and biomedical fields for their ability to stretch reversibly to large deformations. Yet their maximum extensibility is limited by the occurrence of fracture, which is currently still poorly understood. Because of a lack of experimental evidence, current physical models of elastomer fracture describe the rate and temperature dependence of the fracture energy as being solely due to viscoelastic friction, with chemical bond scission at the crack tip assumed to remain constant. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we are able to quantitatively detect, with high spatial resolution and sensitivity, the scission of covalent bonds as ordinary elastomers fracture at different strain rates and temperatures. Our measurements reveal that, in simple networks, bond scission, far from being restricted to a constant level near the crack plane, can both be delocalized over up to hundreds of micrometers and increase by a factor of 100, depending on the temperature and stretch rate. These observations, permitted by the high fluorescence and stability of the mechanophore, point to an intricate coupling between strain-rate-dependent viscous dissipation and strain-dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative, and spatially resolved detection of bond scission to assess material damage in a variety of soft materials and their applications. © 2020 authors. Published by the American Physical Society.
- ItemGoing with the Flow : Tunable Flow-Induced Polymer Mechanochemistry(Weinheim : Wiley-VCH, 2020) Willis-Fox, Niamh; Rognin, Etienne; Baumann, Christoph; Aljohani, Talal A.; Göstl, Robert; Daly, RonanMechanical forces can drive chemical transformations in polymers, directing reactions along otherwise inaccessible pathways, providing exciting possibilities for developing smart, responsive materials. The state-of-the-art test for solution-based polymer mechanochemistry development is ultrasonication. However, this does not accurately model the forces that will be applied during device fabrication using processes such as 3D printing or spray coating. Here, a step is taken toward predictably translating mechanochemistry from molecular design to manufacturing by demonstrating a highly controlled nozzle flow setup in which the shear forces being delivered are precisely tuned. The results show that solvent viscosity, fluid strain rate, and the nature of the breaking bond can be individually studied. Importantly, it is shown that the influence of each is different to that suggested by ultrasonication (altered quantity of chain breakage and critical polymer chain length). Significant development is presented in the understanding of polymer bond breakage during manufacturing flows to help guide design of active components that trigger on demand. Using an anthracene-based mechanophore, the triggering of a fluorescence turn-on is demonstrated through careful selection of the flow parameters. This work opens the avenue for programmed chemical transformations during inline manufacturing processes leading to tunable, heterogeneous final products from a single source material. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim