Fifteen mechanochemical phenomena observed under compression and plastic shear of materials in a rotational diamond anvil cell (RDAC) are systematized. They are related to strain-induced structural changes (SCs) under high pressure, including phase transformations (PTs) and chemical reactions. A simple, three-scale continuum thermodynamic theory and closed-form solutions are developed which explain these phenomena. At the nanoscale, a model for strain-induced nucleation at the tip of a dislocation pile-up is suggested and studied. At the microscale, a simple strain-controlled kinetic equation for the strain-induced SCs is thermodynamically derived. A macroscale model for plastic flow and strain-induced SCs in RDAC is developed. These models explain why and how the superposition of plastic shear on high pressure leads to (a) a significant (by a factor of 3-5) reduction of the SC pressure, (b) reduction (up to zero) of pressure hysteresis, (c) the appearance of new phases, especially strong phases, which were not obtained without shear, (d) strain-controlled (rather than time-controlled) kinetics, or (e) the acceleration of kinetics without changes in the PT pressure. Also, an explanation was obtained as to why a nonreacting matrix with a yield stress higher (lower) than that for reagents significantly accelerates (slows down) the reactions. Some methods of characterization and controlling the SCs are suggested and the unique potential of plastic straining to produce high-strength metastable phases is predicted.

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An unexpected mechanism for fast reaction of Al nanoparticles covered by a thin oxide shell during fast heating is proposed and justified theoretically and experimentally. For nanoparticles, the melting of Al occurs before the oxide fracture. The volume change due to melting induces pressures of 1–2 GPa and causes dynamic spallation of the shell. The unbalanced pressure between the Al core and the exposed surface creates an unloading wave with high tensile pressures resulting in dispersion of atomic scale liquid Al clusters. These clusters fly at high velocity and their reaction is not limited by diffusion (this is the opposite of traditional mechanisms for micron particles and for nanoparticles at slow heating). Physical parameters controlling the melt dispersion mechanism are found by our analysis. In addition to an explanation of the extremely short reaction time, the following correspondence between our theory and experiments are obtained: (a) For the particle radius below some critical value, the flame propagation rate and the ignition time delay are independent of the radius; (b) damage of the oxide shell suppresses the melt dispersion mechanism and promotes the traditional diffusive oxidation mechanism; (c) nanoflakes react more like micron size (rather than nanosize) spherical particles. The reasons why the melt dispersion mechanism cannot operate for the micron particles or slow heating of nanoparticles are determined. Methods to promote the melt dispersion mechanism, to expand it to micron particles, and to improve efficiency of energetic metastable intermolecular composites are formulated. In particular, the following could promote the melt dispersion mechanism in micron particles: (a) Increasing the temperature at which the initial oxide shell is formed; (b) creating initial porosity in the Al; (c) mixing of the Al with a material with a low (even negative) thermal expansion coefficient or with a phase transformation accompanied by a volume reduction; (d) alloying the Al to decrease the cavitation pressure; (e) mixing nano- and micron particles; and (f) introducing gasifying or explosive inclusions in any fuel and oxidizer. A similar mechanism is expected for nitridation and fluorination of Al and may also be tailored for Ti and Mg fuel.

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An unexpected mechanism for fast oxidation of Al nanoparticles covered by a thin oxide shell (OS) is proposed. The volume change due to melting of Al induces pressures of 0.1–4GPa and causes spallation of the OS. A subsequent unloading wave creates high tensile pressures resulting in dispersion of liquid Al clusters, oxidation of which is not limited by diffusion (in contrast to traditional mechanisms). Physical parameters controlling this process are determined. Methods to promote this melt dispersion mechanism, and consequently, improve efficiency of energetic nanothermites are discussed.