The present study demonstrates the possibility of fabricating zirconia parts with a complex shape and internal architecture using a low-cost stereolithography-based technique. One of the critical steps in ceramics stereolithography is the preparation of a photo-curable slurry with properties that fulfill specific requirements, such as having a low viscosity, high solids loading and appropriate curing characteristics. Slurries with different acrylic monomers and ceramic fillers were studied concerning their rheological and curing behavior. New formulations based on mono- and tri-functional acrylic monomers revealed the following excellent rheological properties: The viscosity of the mono-/tri-acrylate-based slurry with 75 wt.% of zirconia was 1.6 Pa·s at 30 s−1. Zirconia stabilized with 3 mol.% yttria was found to be more favorable than zirconia with 8 mol.% yttria for slurry preparation, because of its lower surface area and higher tapped density. It was shown that the cure depth of the suspensions was suitable for printing objects with a 50 µm layer thickness, good interlayers connection and surface finishing.
A synthesis route to rock-salt zinc oxide (rs-ZnO), high-pressure phase metastable at ambient conditions, has been developed. High-purity bulk nanocrystalline rs-ZnO has been synthesized from wurtzite (w) ZnO nanopowders at 7.7 GPa and 770-820 K and for the first time recovered at normal conditions. Structure, phase composition and thermal phase stability of recovered rs-ZnO have been studied by synchrotron X-ray powder diffraction and X-ray absorption spectroscopy (XANES and EXAFS) at ambient pressure. Phase purity of rs-ZnO was achieved by usage of w-ZnO nanoparticles with narrow size distribution as a pristine material synthesized by various chemical methods. At ambient pressure rs-ZnO could be stable up to 360 K. The optical properties of rs-ZnO have been studied by conventional cathodoluminescence in high vacuum at room and liquid-nitrogen temperatures. The nanocrystalline rs-ZnO at 300 and 77 K has shown bright blue luminescence at 2.42 and 2.56 eV, respectively. KEYWORDS cubic zinc oxide, nanocrystals, high-pressure synthesis, phase transition, luminescent properties.
Kinetics of the wurtzite-to-rock-salt transformation in ZnO has been studied in the 5-7 GPa pressure range at temperatures below the activation of diffusion processes. The detailed analysis of non-isothermal experimental data using the general evolution equation describing the kinetics of direct phase transformations in solids allowed us to study the kinetic particularities of both nucleation and growth of the rock-salt phase in parent wurtzite ZnO. The main rate-limiting processes are thermally activated nucleation (E(N) = 383 kJ mol(-1) at 6.9 GPa) and thermally nonactivated (most probably quasi-martensitic) growth (k(G) = 0.833 min(-1) at 6.9 GPa). The high impact of thermal deactivation of nucleation places has been evidenced in the case of slow heating, which indirectly indicates that the rs-ZnO nucleation places are mainly produced by pressure-induced stresses in the parent phase.
Thermal decomposition of graphite oxide into nanocarbons at pressures from ambient to 5 GPa has been studied by using X-ray diffraction, Raman spectroscopy and TEM. The temperature of graphite oxide decomposition at 5 GPa is close to the temperature of graphite oxide exfoliation at ambient pressure; however, materials formed are strongly dependent on pressure. High-pressure conditions favor formation of rounded graphitic nanoparticles, while exfoliation at ambient pressure results in preservation of paper-like wrinkled micrometer size sheets (with thickness of a few graphene layers) typical for pristine graphite oxide.
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