Microgravity effects on nonequilibrium melt processing of neodymium titanate: thermophysical properties, atomic structure, glass formation and crystallization.

The relationships between materials processing and structure can vary between terrestrial and reduced gravity environments. As one case study, we compare the nonequilibrium melt processing of a rare-earth titanate, nominally 83TiO2-17Nd2O3, and the structure of its glassy and crystalline products. Density and thermal expansion for the liquid, supercooled liquid, and glass are measured over 300-1850 °C using the Electrostatic Levitation Furnace (ELF) in microgravity, and two replicate density measurements were reproducible to within 0.4%. Cooling rates in ELF are 40-110 °C s-1 lower than those in a terrestrial aerodynamic levitator due to the absence of forced convection. X-ray/neutron total scattering and Raman spectroscopy indicate that glasses processed on Earth and in microgravity exhibit similar atomic structures, with only subtle differences that are consistent with compositional variations of ~2 mol. % Nd2O3. The glass atomic network contains a mixture of corner- and edge-sharing Ti-O polyhedra, and the fraction of edge-sharing arrangements decreases with increasing Nd2O3 content. X-ray tomography and electron microscopy of crystalline products reveal substantial differences in microstructure, grain size, and crystalline phases, which arise from differences in the melt processes.

Lattice dynamics and heat transport in zeolitic imidazolate framework glasses.

The glassy state of zeolitic imidazolate frameworks (ZIFs) has shown great potential for energy-related applications, including solid electrolytes. However, their thermal conductivity (κ), an essential parameter influencing thermal dissipation, remains largely unexplored. In this work, using a combination of experiments, atomistic simulations, and lattice dynamics calculations, we investigate κ and the underlying heat conduction mechanism in ZIF glasses with varying ratios of imidazolate (Im) to benzimidazolate (bIm) linkers. The substitution of bIm for Im tunes the node-linker couplings but exhibits only a minor impact on the average diffusivity of low-frequency lattice modes. On the other hand, the linker substitution induces significant volume expansion, which, in turn, suppresses the contributions from lattice vibrations to κ, leading to decreased total heat conduction. Furthermore, spatial localization of internal high-frequency linker vibrations is promoted upon substitution, reducing their mode diffusivities. This is ascribed to structural deformations of the bIm units in the glasses. Our work unveils the detailed influences of linker substitution on the dual heat conduction characteristics of ZIF glasses and guides the κ regulation of related hybrid materials in practical applications.

Probing spin waves in Co3O4 nanoparticles for magnonics applications.

The magnetic properties of spinel nanoparticles can be controlled by synthesizing particles of a specific shape and size. The synthesized nanorods, nanodots and cubic nanoparticles have different crystal planes selectively exposed on the surface. The surface effects on the static magnetic properties are well documented, while their influence on spin waves dispersion is still being debated. Our ability to manipulate spin waves using surface and defect engineering in magnetic nanoparticles is the key to designing magnonic devices. We synthesized cubic and spherical nanoparticles of a classical antiferromagnetic material Co3O4 to study the shape and size effects on their static and dynamic magnetic proprieties. Using a combination of experimental methods, we probed the magnetic and crystal structures of our samples and directly measured spin wave dispersions using inelastic neutron scattering. We found a weak, but unquestionable, increase in exchange interactions for the cubic nanoparticles as compared to spherical nanoparticle and bulk powder reference samples. Interestingly, the exchange interactions in spherical nanoparticles have bulk-like properties, despite a ferromagnetic contribution from canted surface spins.

Revealing the relationship between liquid fragility and medium-range order in silicate glasses.

Despite decades of studies, the nature of the glass transition remains elusive. In particular, the sharpness of the dynamical arrest of a melt at the glass transition is captured by its fragility. Here, we reveal that fragility is governed by the medium-range order structure. Based on neutron-diffraction data for a series of aluminosilicate glasses, we propose a measurable structural parameter that features a strong inverse correlation with fragility, namely, the average medium-range distance (MRD). We use in-situ high-temperature neutron-scattering data to discuss the physical origin of this correlation. We argue that glasses exhibiting low MRD values present an excess of small network rings. Such rings are unstable and deform more readily with changes in temperature, which tends to increase fragility. These results reveal that the sharpness of the dynamical arrest experienced by a silicate glass at the glass transition is surprisingly encoded into the stability of rings in its network.

Octahedral oxide glass network in ambient pressure neodymium titanate.

Rare-earth titanates form very fragile liquids that can be made into glasses with useful optical properties. We investigate the atomic structure of 83TiO2-17Nd2O3 glass using pair distribution function (PDF) analysis of X-ray and neutron diffraction with double isotope substitutions for both Ti and Nd. Six total structure factors are analyzed (5 neutron + 1 X-ray) to obtain complementary sensitivities to O and Ti/Nd scattering, and an empirical potential structure refinement (EPSR) provides a structural model consistent with the experimental measurements. Glass density is estimated as 4.72(13) g cm-3, consistent with direct measurements. The EPSR model indicates nearest neighbor interactions for Ti-O at [Formula: see text] = 1.984(11) Å with coordination of [Formula: see text] = 5.72(6) and for Nd-O at [Formula: see text] = 2.598(22) Å with coordination of [Formula: see text] = 7.70(26), in reasonable agreement with neutron first order difference functions for Ti and Nd. The titanate glass network comprises a mixture of distorted Ti-O5 and Ti-O6 polyhedra connected via 71% corner-sharing and 23% edge-sharing. The O-Ti coordination environments include 15% nonbridging O-Ti1, 51% bridging O-Ti2, and 32% tricluster O-Ti3. This structure is highly unusual for oxide glasses melt-quenched at ambient pressure, as it consists of Ti-Ox predominantly in octahedral (with nearly no tetrahedral) coordination.

Experimental method to quantify the ring size distribution in silicate glasses and simulation validation thereof.

Silicate glasses have no long-range order and exhibit a short-range order that is often fairly similar to that of their crystalline counterparts. Hence, the out-of-equilibrium nature of glasses is largely encoded in their medium-range order. However, the ring size distribution-the key feature of silicate glasses' medium-range structure-remains invisible to conventional experiments and, hence, is largely unknown. Here, by combining neutron diffraction experiments and force-enhanced atomic refinement simulations for two archetypical silicate glasses, we show that rings of different sizes exhibit a distinct contribution to the first sharp diffraction peak in the structure factor. On the basis of these results, we demonstrate that the ring size distribution of silicate glasses can be determined solely from neutron diffraction patterns, by analyzing the shape of the first sharp diffraction peak. This method makes it possible to uncover the nature of silicate glasses' medium-range order.

In Situ High-Temperature Synchrotron Diffraction Studies of (Fe,Cr,Al)3O4 Spinels.

The modeling of a loss-of-coolant-accident scenario involving nuclear fuels with FeCrAl cladding materials in consideration to replace a Zircaloy requires knowledge of the thermodynamics of oxidized structures. At temperatures higher than 1500 °C, oxidation of FeCrAl alloys forms (Fe,Cr,Al)3O4 spinels. In situ high-energy X-ray diffraction in a conical nozzle levitator installed at beamline 6-ID-D of the APS was used to study the structural evolution of the oxides as a function of the temperature. Single-phase (spinel) and multiphase (spinel-corundum-FeAlO3) regions are mapped as a function of the temperature for three different compositions of FeCrAl oxidation products. The thermal expansion coefficients and cation distribution in the spinel structure have been refined. The temperature at which complete melting of the fuel cladding is expected has been determined by the liquidus temperatures of the oxidized products to be between 1657 and 1834 °C in a 20% O2/Ar atmosphere using the cooling trace method. The liquidus temperature increases with increasing Al and Cr content in the spinel phase.

Synthesis and structure of synthetically pure and deuterated amorphous (basic) calcium carbonates.

It is generally believed that H2O and OH- are the key species stabilizing and controlling amorphous calcium carbonate "polyamorph" forms, and may in turn control the ultimate crystallization products during synthesis and in natural systems. Yet, the locations and hydrogen-bonding network of these species in ACC have never been measured directly using neutron diffraction. We report a synthesis route that overcomes the existing challenges with respect to yield quantities and deuteration, both of which are critically necessary for high quality neutron studies.

Sodium Ion Transport Mechanisms in Antiperovskite Electrolytes Na3OBr and Na4OI2: An in Situ Neutron Diffraction Study.

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-state battery. In this work, the sodium ionic transport pathways of the parent compound Na3OBr, as well as the modified layered antiperovskite Na4OI2, were studied and compared through temperature-dependent neutron diffraction combined with the maximum entropy method. In the cubic Na3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions hop within and among oxygen octahedra, and Br(-) ions are not involved. In the tetragonal Na4OI2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. The transport of sodium ions along the c axis is assisted by I(-) ions.

Intricate short-range ordering and strongly anisotropic transport properties of Li(1-x)Sn(2+x)As2.

A new ternary compound, Li(1-x)Sn(2+x)As2, 0.2 < x < 0.4, was synthesized via solid-state reaction of elements. The compound crystallizes in a layered structure in the R3̅m space group (No. 166) with Sn-As layers separated by layers of jointly occupied Li/Sn atoms. The Sn-As layers are comprised of Sn3As3 puckered hexagons in a chair conformation that share all edges. Li/Sn atoms in the interlayer space are surrounded by a regular As6 octahedron. Thorough investigation by synchrotron X-ray and neutron powder diffraction indicate no long-range Li/Sn ordering. In contrast, the local Li/Sn ordering was revealed by synergistic investigations via solid-state (6,7)Li NMR spectroscopy, HRTEM, STEM, and neutron and X-ray pair distribution function analyses. Due to their different chemical natures, Li and Sn atoms tend to segregate into Li-rich and Sn-rich regions, creating substantial inhomogeneity on the nanoscale. The inhomogeneous local structure has a high impact on the physical properties of the synthesized compounds: the local Li/Sn ordering and multiple nanoscale interfaces result in unexpectedly low thermal conductivity and highly anisotropic resistivity in Li(1-x)Sn(2+x)As2.

The bound coherent neutron scattering lengths of the oxygen isotopes.

The technique of neutron interferometry was used to measure the bound coherent neutron scattering length b(coh) of the oxygen isotopes (17)O and (18)O. From the measured difference in optical path between two water samples, either H(2)(17)O or H(2)(18)O versus H(2)(nat)O, where nat denotes the natural isotopic composition, we obtain b(coh,(17)O) = 5.867(4) fm and b(coh,(18)O) = 6.009(5) fm, based on the accurately known value of b(coh,(nat)O) = 5.805(4) fm which is equal to b(coh,(16)O) within the experimental uncertainty. Our results for b(coh,(17)O) and b(coh,(18)O) differ appreciably from the standard tabulated values of 5.6(5) fm and 5.84(7) fm, respectively. In particular, our measured scattering-length contrast of 0.204(3) fm between (18)O and (nat)O is nearly a factor of 6 greater than the tabulated value, which renders feasible neutron diffraction experiments using (18)O isotope substitution and thereby offers new possibilities for measuring the partial structure factors of oxygen-containing compounds, such as water.

Isotope effects in water as investigated by neutron diffraction and path integral molecular dynamics.

The structures of heavy and light water at 300 K were investigated by using a joint approach in which the method of neutron diffraction with oxygen isotope substitution was complemented by path integral molecular dynamics simulations. The diffraction results, which give intra-molecular O-D and O-H bond distances of 0.985(5) and 0.990(5) Å, were found to be in best agreement with those obtained by using the flexible anharmonic TTM3-F water model. Both techniques show a difference of  ≃ 0.5% between the O-D and O-H intra-molecular bond lengths, and the results support a competing quantum effects model for water in which its structural and dynamical properties are governed by an offset between intra-molecular and inter-molecular quantum contributions. Further consideration of the O-O correlations is needed in order to improve agreement with experiment.

Oxygen as a site specific probe of the structure of water and oxide materials.

The method of oxygen isotope substitution in neutron diffraction is introduced as a site specific structural probe. It is employed to measure the structure of light versus heavy water, thus circumventing the assumption of isomorphism between H and D as used in more traditional neutron diffraction methods. The intramolecular and intermolecular O-H and O-D pair correlations are in excellent agreement with path integral molecular dynamics simulations, both techniques showing a difference of ≃0.5% between the O-H and O-D intramolecular bond distances. The results support the validity of a competing quantum effects model for water in which its structural and dynamical properties are governed by an offset between intramolecular and intermolecular quantum contributions.

Mechanisms of metal ion transfer into room-temperature ionic liquids: the role of anion exchange.

The structure and stoichiometry of the lanthanide(III) (Ln) complexes with the ligand 2-thenoyltrifluoroacetone (Htta) formed in a biphasic aqueous room-temperature ionic liquid system have been studied by complementary physicochemical methods. Equilibrium thermodynamics, optical absorption and luminescence spectroscopies, high-energy X-ray scattering, EXAFS, and molecular dynamics simulations all support the formation of anionic Nd(tta)4(-) or Eu(tta)4(-) complexes with no water coordinated to the metal center in 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (C4mim+Tf2N(-)), rather than the hydrated, neutral complexes, M(tta)(3)(H2O)n)(n = 2 or 3), that form in nonpolar molecular solvents, such as xylene or chloroform. The presence of anionic lanthanide complexes in C4mim+Tf2N(-) is made possible by the exchange of the ionic liquid anions into the aqueous phase for the lanthanide complex. The resulting complexes in the ionic liquid phase should be thought of as weak C4mim+Ln(tta)4(-) ion pairs which exert little influence on the structure of the ionic liquid phase.