No abstract

No abstract

Birefringence is a major source of difficulty in sintering of transparent polycrystalline alumina ceramics, especially as the grain size exceeds a few hundred nanometers, which ultimately leads to complete opacity, mainly due to scattering of light. Recent studies have made it clear that by application of a strong magnetic field, alumina grains can be aligned along a particular crystallographic orientation, which minimizes scattering due to birefringence, and enhances transparency. Defects that cause spin delocalization are known to induce a paramagnetic behavior in alumina ceramics. Therefore, such defects have become a focal point of research for magnetic field assisted sintering of transparent polycrystalline alumina, in order to reduce the necessary magnetic field strength during production process. In light of recent studies on paramagnetic potentials of transition metal doped alumina, we have applied Spin Polarized Density Functional Theory (SP-DFT) calculations on manganese and chromium doped and co-doped alumina to calculate the magnetic moments, density of states and defect formation energies, which should be expected from this system of dopants, along with their interactions with oxygen vacancies. The results clearly indicate that formation of a point defect comprised of chromium and manganese positioned substitutionally at adjacent aluminum sites, in vicinity of an oxygen vacancy can induce a magnetic moment equivalent to 5 Bohr magnetons (μβ), outperforming previously reported defects. Based on this study we find it likely that chromium and manganese co-doping in alumina can further reduce the required magnetic field strength for production of transparent polycrystalline alumina.

A significant proportion of mined natural corundum (ruby and sapphire) contain fractures, which negatively affects a gemstone’s clarity and value. Over the past decades, heat treatment techniques have been developed for either fracture healing, or filling to make such gems marketable. The clarity enhancement processes are mainly based on techniques which are either not durable, as in the case of lead silicate fillers, or do not yield perfect transmittance through a fracture, as in the case of borax based fluxes. Therefore, the gemstone treatment community is actively in pursuit of better techniques for clarity enhancement in corundum. Given that application of pressure is a recent advancement in the heat treatment processes of natural sapphire, it is essential to explore the possibilities regarding different outcomes such treatments can have. In this perspective paper, we have briefly described how application of pressure during heat treatments can lead to in-situ sintering of transparent polycrystalline ceramics within the fractures of corundum, which can result in clarity enhancement. Spinel-structure based fillers can be tailored to mimic corundum in terms of tribological, chemical and optical properties. Therefore, gemstones treated with such fillers will be durable, unlike currently used glass-based filler material. We also provide a possible explanation for ghost-fissures in sapphires heated under pressure, as being a by-product of in-situ sintering process of ceramic fillers that are thermodynamically compatible with Al2O3. The prospect of transparent polycrystalline ceramics in the gem and jewelry industry opens a new field of research in this area, given that ceramic fillers can outperform currently used methods and material for clarity enhancement in gemstones. In essence, we present a novel application for sintered transparent polycrystalline ceramics.

No abstract