石川 毅彦

Rare earth aluminum garnets are important materials in optical, dielectric, and thermal barrier applications. To advance the understanding of their melt processing and glass forming ability, we report the atomic structure of molten Yb3Al5O12 over 1770–2630 K, which spans the equilibrium and supercooled liquid regimes. The melt density at Tm = 2283 K is 5.50 g cm−3, measured via silhouette imaging of electrostatically levitated drops over 1010–2420 K. Four separate structure measurements were made with aerodynamically levitated melts using x-ray and neutron diffraction with isotope substitution of Yb (172Yb, 174Yb, or natYb). Empirical potential structure refinement models were developed, which are in excellent agreement with the experiments. Coordination environments for Al–O are predominantly 4- and 5-coordinate, with a mean coordination of nAlO = 4.43(8), while Yb–O environments mostly range from 5- to 8-coordinate, with nYbO = 6.26(8). The cation–oxygen polyhedra are connected primarily by corner-sharing, with edge-sharing constituting up to ∼1/3 of the connectivity among polyhedra with Yb or higher-coordinated Al–O. Structurally, the –Al–O– network in molten Yb3Al5O12 appears conducive to glass formation: nOAl = 1.85(3), there are 1.86 AlOx–AlOx connections per Al atom (e.g., a mixture of Q3 and Q4 units), and the modal ring size is six cations. These characterize a network that is somewhat less constrained compared to SiO2 glass, yet Yb3Al5O12 cannot be quenched into crystal-free glass. Aluminum garnet compositions with larger rare earth cations do form glass, so these characterizations help reveal the structural characteristics corresponding to the limit of glass forming ability in rare earth aluminates.

Abstract Possible existence of dense iron-rich silicate melt layer above Mars’ core is important in understanding the nature and evolution of Mars. However, gravitational stability of iron-rich silicate melt in the Mars’ interior has not been well constrained, due to experimental difficulties in measuring density of iron-rich peridotitic melt. Here we report density measurements of iron-rich peridotitic melts up to 2465 K by using electrostatic levitation furnace at the International Space Station. Our experimentally obtained densities of iron-rich peridotitic melts are markedly higher than those calculated by first principles simulation, and are distinct from those estimated by extrapolating a density model for SiO₂-rich basaltic melts. Our determined density model suggests that peridotitic melt with the Fe/(Mg+Fe) ratio more than 0.4-0.5 has higher density than that at the base of the Mars’ mantle, which indicates gravitational stability of the iron-rich peridotitic melt at the core-mantle boundary in Mars.