Nonisothermal densification in 8% yttria doped zirconia (8YSZ) particulate matter of 250 nm median particle size was studied under 215 V/cm dc electric field and 9 °C/min heating rate, using time-resolved in-situ high temperature energy dispersive x-ray diffractometry with a polychromatic 200 keV synchrotron probe. Densification occurred in the 876–905 °C range, which resulted in 97% of the theoretical density. No local melting at particle-particle contacts was observed in scanning electron micrographs, implying densification was due to solid state mass transport processes. The maximum current draw at 905 °C was 3 A, corresponding to instantaneous absorbed power density of 570 W/cm3. Densification of 8YSZ was accompanied by anomalous elastic volume expansions of the unit cell by 0.45% and 2.80% at 847 °C and 905 °C, respectively. The anomalous expansion at 905 °C at which maximum densification was observed is characterized by three stages: (I) linear stage, (II) anomalous stage, and (III) anelastic recovery stage. The densification in stage I (184 s) and II (15 s) was completed in 199 s, while anelastic relaxation in stage III lasted 130 s. The residual strains (ε) at room temperature, as computed from tetragonal (112) and (211) reflections, are ε(112) = 0.05% and ε(211) = 0.13%, respectively. Time dependence of (211) and (112) peak widths (β) show a decrease with both exhibiting a singularity at 905 °C. An anisotropy in (112) and (211) peak widths of {β(112)/β(211)} = (3:1) magnitude was observed. No phase transformation occurred at 905 °C as verified from diffraction spectra on both sides of the singularity, i.e., the unit cell symmetry remains tetragonal. We attribute the reduction in densification temperature and time to ultrafast ambipolar diffusion of species arising from the superposition of mass fluxes due to Fickian diffusion, thermodiffusion (Soret effect), and electromigration, which in turn are a consequence of a superposition of chemical, temperature, and electrical potential gradients. On the other hand, we propose defect pile-up at particle-particle contacts and subsequent tunneling as a mechanism creating the “burst-mode” discontinuous densification at the singularities observed at 847 and 905 °C.
Zirconium diboride (ZrB2) is an attractive material due to its thermal and electrical properties. In recent years, ZrB2 has been investigated as a superior replacement for sapphire when used as a substrate for gallium nitride devices. Like sapphire, ZrB2 has an anisotropic hexagonal structure which defines its directionally dependent properties. However, the anisotropic behavior of ZrB2 is not well understood. In this paper, we use energy-dispersive synchrotron X-ray diffraction to measure the thermal expansion of polycrystalline ZrB2 powder from 300 to 1150 K. Nine Bragg reflections are fit using Pseudo-Voigt peak profiles and used to compute the and lattice parameters using a nonlinear least-squares approximation. The temperature-dependent instantaneous thermal expansion coefficients are determined for each -axis and -axis direction and are described by the following equations: = ( + × )/( × + ) and = ( + )/( + ). Our results are within range of previously reported values but describe the temperature anisotropy in more detail. We show that anisotropic expansion coefficients converge to the same value at about 780 K and diverge at higher temperatures. Results are compared with other reported values.