Magnesium-Induced Strain and Immobilized Radical Generation on the Boron Oxide Surface Enhances the Oxidation Rate of Boron Particles: A DFTB-MD Study.

Despite their high gravimetric and volumetric energy densities, boron (B) particles suffer from poor oxidative energy release rates as the boron oxide (B 2 O 3 ) shell impedes the diffusivity of O 2 to the particle interior. Recent experiemental studies have shown that the addition of metals with a lower free energy of oxidation, such as Mg, can reduce the oxide shell of B and enhance the energetic performance of B by ∼30-60%. However, the exact underlying mechanism behind the reactivity enhancement is unknown. Here, we performed DFTB-MD simulations to study the reaction of Mg vapor with a B 2 O 3 surface. We found that the Mg becomes oxidized on the B 2 O 3 surface, forming a MgB x O y phase, which induces a tensile strain in the B-O bond at the MgB x O y -B 2 O 3 interface, simultaneously reducing the interfacial B and thereby developing dangling bonds. The interfacial bond straining creates an overall surface expansion, indicating the presence of a net tensile strain. The B with dangling bonds can act as active centers for gas-phase O 2 adsorption, thereby increasing the adsorption rate, and the overall tensile strain on the surface will increase the diffusion flux of adsorbed O through the surface to the particle core. As the overall B particle oxidation rate is dependent on both the O adsorption and diffusion rates, the enhancement in both of these rates increases the overall reactivity of B particles.