Polymer mechanochemistry is an exciting, rapidly developing field; however, it lacks detailed studies on the link between lab-scale mechanical activation and how the chemistry will translate to the complex flows and forces experienced during fluid-based molding and additive manufacturing techniques. This is especially important for polymers, which are the functional material of choice for applications such as organic electronics, biological scaffolds, and drug-delivery coatings, because there is the highest likelihood of mechanical activation. This review examines the most recent development in force-sensitive molecules known as mechanophores by re-categorizing them by material phase and method of activation and discussing the forces involved in such flow systems and where activation may occur in relevant manufacturing processes. The overall finding of this review is that for real, practical, and scalable industrial applications of these exciting mechanochemical materials, there must be a concurrent study of the forces experienced and their effect on the detailed chemistry.
This study aims to establish the effects of equal channel angular pressing (ECAP) processing on the corrosion behavior and hardness values of the AZ31 Mg alloy. The AZ31 billets were processed through ECAP successfully at 250 °C and their microstructural evolution was studied using optical and field emission scanning electron microscopy. The corrosion resistance of the AZ31 alloy was studied before and after processing through ECAP. The homogeneity of the hardness distribution was studied using both sections cut parallel and perpendicular to the extrusion direction. ECAP processing resulted in highly deformed central regions with elongated grains aligned parallel to the extrusion direction, whereas the peripheral regions showed an ultra-fine-grain recrystallized structure. After processing, small ultra-fine secondary particles were found to be homogeneously dispersed alongside the grain boundaries of the α-Mg matrix. Regarding the corrosion properties, measurements showed that ECAP processing through 1-P and 2-Bc resulted in decreasing their corrosion rate to 67.7% and 78.3%, respectively, of their as-annealed counterpart’s. The corrosion resistance of the ECAPed Mg alloy increased with the number of processing passes. This was due to the refinement of the grain size of the α-Mg matrix and secondary phases till ultra-fine size, caused by the accumulation of strain during processing. On the other hand, ECAP processing through 2-Bc resulted in increasing the Vickers hardness values by 132% and 71.8% at the peripheral and central areas, respectively, compared to the as-annealed counterpart.
Mechanical 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.
In this study, billets of the ZK30 (Mg-3Zn-0.6 Zr-0.4 Mn, wt%) alloy were Equal Channel Angle Pressing (ECAP) processed for up to four passes of routes Bc (with rotating the sample 90° in the same direction between the subsequent passes), A (without sample rotation), and C (with sample rotating 180°) after each pass at a temperature of 250 °C and a ram speed of 10 mm/min using a die with an internal channel angle of 90°. The microstructural evolution and the crystallographic texture were investigated using a Scanning Electron Microscope (SEM) equipped with the Electron Back-Scatter Diffraction (EBSD) technique. Corrosion measurements were conducted in ringer lactate which is a simulated body fluid. The Vickers microhardness test and tensile tests were conducted for the alloy before and after processing. The as-annealed billets exhibited a bimodal structure as fine grains (more than 3.39 µm) coexisted with almost-equiaxed coarse grains (less than 76.73 µm); the average grain size was 26.69 µm. Further processing until four passes resulted in enhanced grain refinement and full Dynamic Recrystallization (DRX). ECAP processing through 4-Bc, 4-A, and 4-C exhibited significant reductions in grain size until they reached 1.94 µm, 2.89 µm, and 2.25 µm, respectively. Four-pass processing also resulted in the transformation of low-angle grain boundaries into high-angle grain boundaries. The previous conclusion was drawn from observing the simultaneous decrease in the fraction of low-angle grain boundaries and an increase in the fraction of high-angle grain boundaries. The pole figures revealed that 4-Bc, 4-A, and 4-C reduced the maximum texture intensity of the as-annealed billets. The potentiodynamic polarization findings revealed that route Bc is the most effective route in improving the corrosion rate, whereas the Electrochemical Impedance Spectroscopy (EIS) revealed that routes A and Bc improved the corrosion resistance with nearly identical values. Finally, 4-Bc resulted in the highest increase in Vickers hardness, yield stress, and ultimate tensile strength with values of 80.8%, 19.3%, and 44.5%, alongside a 31% improvement in ductility, all compared to the AA condition.
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