Structure of molten ytterbium aluminum garnet

Abstract

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.