We combine small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) with aerodynamic levitation techniques to study in situ phase transitions in the liquid state under contactless conditions. At very high temperatures, yttria-alumina melts show a first-order transition, previously inferred from phase separation in quenched glasses. We show how the transition coincides with a narrow and reversible maximum in SAXS indicative of liquid unmixing on the nanoscale, combined with an abrupt realignment in WAXS features related to reversible shifts in polyhedral packing on the atomic scale. We also observed a rotary action in the suspended supercooled drop driven by repetitive transitions (a polyamorphic rotor) from which the reversible changes in molar volume (1.2 ± 0.2 cubic centimeters) and entropy (19 ± 4 joules mole–1kelvin–1) can be estimated.
The neutron scattering structure factor for a 40 mg drop of molten alumina ( ) held at 2500 K, using a laser-heated aerodynamic levitation furnace, is measured for the first time. A 1700 atom model of liquid alumina is generated from these data using the technique of empirical potential structural refinement. About of the aluminum sites are 4-fold coordinated, matching the mostly triply coordinated oxygen sites, but some of the aluminum sites are 5-fold coordinated. The octahedral aluminum sites found in crystalline occur only at the level in liquid alumina.
In the present work the structural properties of low silica content calcium aluminosilicate melts with concentration ratio CaO/Al2O3 = 1 are investigated in the liquid and undercooled states by neutron diffraction experiments and ab initio molecular dynamics simulations. The results show the presence of AlO5 units and triclusters as well as non-bridging oxygen in the fully charge balanced compositions. Moreover, our findings allow us to identify a possible interplay between these structural units. Finally, we discuss the influence of these defective structural units on the properties of tetrahedral network and more particularly their implication on the evolution of the viscosity and the fragility.
5 August 2005 in Journal of Physics: Condensed Matter
Carbon supported Pt nanoparticles with diameters ranging from 2 to 28 nm have been studied using X-ray diffraction. The unit cell parameter of synthesized Pt/C nanoparticles is always lower than that of bulk Pt. By decreasing the average particle size D to approximately 2 nm, the unit cell parameter a nonlinearly decreases by about 0.03 Å which corresponds to a variation of 0.7% in comparison to bulk Pt, and the size effect is predominant for sizes ranging from 2 to 10 nm. The dependence a(1/D) is approximated well using a straight line with a slope of −0.0555 ± 0.0067 nm−1 and an intercept of −3.9230 ± 0.0017 Å. For interpreting the obtained experimental dependence of the unit cell parameter of Pt/C nanoparticles, four different theoretical approaches such as the thermal vacancy mechanism, continuous-medium model, Laplace pressure, and bond order–length–strength correlation mechanism, were used. Comparison of the calculated dependencies, based on the above models, with the experimental ones, shows that the continuous-medium model agrees best with the experimentally found unit cell parameter dependence of our carbon supported Pt nanoparticles.