ABSTRACT
The preparation and reprocessing of an epoxy vitrimer material is performed in a fully biocatalyzed process wherein network formation and exchange reactions are promoted by a lipase enzyme. Binary phase diagrams are introduced to select suitable diacid/diepoxide monomer compositions overcoming the limitations (phase separation/sedimentation) imposed by curing temperature inferior than 100 °C, to protect the enzyme. The ability of lipase TL, embedded in the chemical network, to catalyze efficiently exchange reactions (transesterification) is demonstrated by combining multiple stress relaxation experiments at 70-100 °C and complete recovery of mechanical strength after several reprocessing assays (up to 3 times). Complete stress relaxation ability disappears after heating at 150 °C, due to enzyme denaturation. Transesterification vitrimers thus designed are complementary to those involving classical catalysis (e.g., using the organocatalyst triazabicyclodecene) for which complete stress relaxation is possible only at high temperature.
ABSTRACT
Oscillatory shear tests are widely used in rheology to characterize the linear and non-linear mechanical response of complex fluids, including the yielding transition. There is an increasing urge to acquire detailed knowledge of the deformation field that is effectively present across the sample during these tests; at the same time, there is mounting evidence that the macroscopic rheological response depends on the elusive microscopic behavior of the material constituents. Here we employ a strain-controlled shear-cell with transparent walls to visualize and quantify the dynamics of tracers embedded in various cyclically sheared complex fluids, ranging from almost-ideal elastic to yield stress fluids. For each sample, we use image correlation processing to measure the macroscopic deformation field, and echo-differential dynamic microscopy to probe the microscopic irreversible sample dynamics in reciprocal space; finally, we devise a simple scheme to spatially map the rearrangements in the sheared sample, once again without tracking the tracers. For the yield stress sample, we obtain a wave-vector dependent characterization of shear-induced diffusion across the yielding transition, which is accompanied by a three-order-of-magnitude speed-up of the dynamics and by a transition from localized, intermittent rearrangements to a more spatially homogeneous and temporally uniform activity. Our tracking free approach is intrinsically multi-scale, can successfully discriminate between different types of dynamics, and can be automated to minimize user intervention. Applications are many, as it can be translated to other imaging modes, including fluorescence, and can be used with sub-resolution tracers and even without tracers, for samples that provide intrinsic optical contrast.
ABSTRACT
Differential Dynamic Microscopy (DDM) analyzes traditional real-space microscope images to extract information on sample dynamics in a way akin to light scattering, by decomposing each image in a sequence into Fourier modes, and evaluating their time correlation properties. DDM has been applied in a number of soft-matter and colloidal systems. However, objects observed to move out of the microscope's captured field of view, intersecting the edges of the acquired images, can introduce spurious but significant errors in the subsequent analysis. Here we show that application of a spatial windowing filter to images in a sequence before they enter the standard DDM analysis can reduce these artifacts substantially. Moreover, windowing can increase significantly the accessible range of wave vectors probed by DDM, and may further yield unexpected information, such as the size polydispersity of a colloidal suspension.
