Abstract

No abstract

Investigations are performed on low-temperature oxygen diffusion in the carbon vacancy ordered ZrC(0.6)and thus induced formation of the oxygen atom ordered ZrC(0.6)O(0.4). Theoretically, a superstructure of Zr(2)CO can be constructed via the complete substitution of carbon vacancies with O atoms in the Zr(2)C model. In the ordered ZrC(0.6), the consecutive arrangement of vacancies forms the vacancy channels along some zone axes in the C sublattice. Through these vacancy channels, the thermally activated oxygen diffusion is significantly facilitated. The oxygen atoms diffuse directly into and occupy the vacancies, producing the ordered ZrC(0.6)O(0.4). Relative to the ordered ZrC(0.6), the Zr positions are finely tuned in the ordered ZrC(0.6)O(0.4) because of the ionic Zr-O bonds. Because of this fine adjustment of Zr positions and the presence of oxygen atoms, the superstructural reflections are always observable in a selected area electron diffraction (SAED) pattern, despite the invisibility of superstructural reflections in ZrC(0.6) along some special zone axes. Similar to the vacancies in ordered ZrC(0.6), the ordering arrangement of O atoms in the ordered ZrC(0.6)O(0.4) is in nanoscale length, thus forming the nano superstructural domains with irregular shapes.

Twinning structures in ordered nonstoichiometric ZrC 0.6 have been investigated experimentally and theoretically. Via transmission electron microscopy and selected area electron diffraction measurements, {111}-specific twins have been observed. Interestingly, two special types of twinning interfaces, i.e. (111) C and (111) Zr interfaces, are recognized to be formed as a result of the presence of ordered carbon vacancies. In contrast to the high stacking fault energy for twinning formation in stoichiometric ZrC, first-principles calculations indicate that the presence of ordered carbon vacancies leads to a great reduction in the twinning interfacial energy, thus favouring the stabilization of twinning structures in the ordered ZrC 0.6 .

Zirconia (ZrO 2 ) nanocrystals with average size of 4 nm are fabricated by oxidation of the nonstoichiometric ZrC 0.6 with ordered carbon vacancies at 450 °C under atmosphere. The nanocrystals are predominantly tetragonal (t) phase and spherical in shape, and their exposed surfaces are constructed by the {011} and {001} facets. After annealing at 700 °C under atmosphere, the coalescence of adjacent t-ZrO 2 nanocrystals is observed, and most of the annealed t-ZrO 2 nanoparticles are found to exhibit the {011}-specific twins. The dominant cyclic twins as well as a small number of the single and lamellar twins are recognized in the twinned nanoparticles. The cyclic-twinned nanoparticles are identified to have the 5-fold symmetry of either decahedron or icosahedron. In contrast to the single and lamellar twins which are formed via the coalescence of adjacent nanocrystals on the well-developed {011} surfaces, the cyclic-twinned nanoparticles are developed from the coalescence on the disoriented contact surfaces, in which the emission of partial dislocations and induced deformation are recognized to play the key role.