Versatile semi-batch apparatus for manometric measurement of gas-solid reaction rates.

We describe the design, construction, operation, and performance of a simple and versatile semi-batch reactor that is especially useful for measurement of gas/solid reaction rates at pressures in the range of 1 mTorr to 1500 Torr. The reactor operates by repeatedly imposing small AC modulations of reactant gas pressure on top of a much larger DC pressure background. Based on the rate of pressure relaxation following each AC pulse, the reaction rate is determined. Our design is characterized by modular construction from off-the-shelf, ultra-high-vacuum-compatible components, which facilitate easy retrofitting and adaptation to a range of experimental conditions. Automated experiment control and data acquisition is accomplished via a custom National Instruments© LabView virtual instrument. Data analysis is automated using a custom series of Mathworks© Matlab scripts. We demonstrate reactor performance through measurements of hydrogenation kinetics for a composite H2 getter material consisting of 1,4-bis(phenylethynyl)benzene mixed with a palladium/carbon catalyst.

Anisotropic thermal conductivity in uranium dioxide.

The thermal conductivity of uranium dioxide has been studied for over half a century, as uranium dioxide is the fuel used in a majority of operating nuclear reactors and thermal conductivity controls the conversion of heat produced by fission events to electricity. Because uranium dioxide is a cubic compound and thermal conductivity is a second-rank tensor, it has always been assumed to be isotropic. We report thermal conductivity measurements on oriented uranium dioxide single crystals that show anisotropy from 4 K to above 300 K. Our results indicate that phonon-spin scattering is important for understanding the general thermal conductivity behaviour, and also explains the anisotropy by coupling to the applied temperature gradient and breaking cubic symmetry.

Role of antisite disorder on preamorphization swelling in titanate pyrochlores.

Ion irradiation experiments and atomistic simulations were used to demonstrate that irradiation-induced lattice swelling in a complex oxide, Lu2Ti2O7, is due initially to the formation of cation antisite defects. X-ray diffraction revealed that cation antisite formation correlates directly with lattice swelling and indicates that the volume per antisite pair is approximately 12 Å3. First principles calculations revealed that lattice swelling is best explained by cation antisite defects. Temperature accelerated dynamics simulations indicate that cation Frenkel defects are metastable and decay to form antisite defects.

Superconductivity in the Einstein solid VAl(10.1).

We used magnetic susceptibility, resistivity and heat capacity measurements to characterize the superconducting state in the Einstein solid VAl(10.1). We find that VAl(10.1) is a weak-coupling, type-II superconductor with T(c) = 1.53 K and an upper critical field of H(c2)(0) = 800 Oe. The heat capacity data in the range 0.07 K < T < 1.53 K are consistent with an isotropic energy gap of Δ(0) = 0.23 meV.

Order-parameter coupling in the improper ferroelectric lawsonite.

Low-temperature specific heat and thermal expansion measurements are used to study the hydrogen-based ferroelectric lawsonite over the temperature range 1.8 K ≤ T ≤ 300 K. The second-order phase transition near 125 K is detected in the experiments, and the low-temperature phase is determined to be improper ferroelectric and co-elastic. In the ferroelectric phase T ≤ 125 K, the spontaneous polarization P(s) is proportional to (1) the volume strain e(s), and (2) the excess entropy ΔS(e). These proportionalities confirm the improper character of the ferroelectric phase transition. We develop a structural model that allows the off-centering of hydrogen positions to generate the spontaneous polarization. In the low-temperature limit we detect a Schottky anomaly (two-level system) with an energy gap of Δ âˆ¼ 0.5 meV.

Determination of iron sites and the amount of amorphization in radiation-damaged titanite (CaSiTiO5).

Iron is a ubiquitous impurity in metamict (radiation-damaged and partially amorphized) materials such as titanite (CaSiTiO(5)). Using (57)Fe Mössbauer spectroscopy we find that iron in metamict titanite is partitioned between amorphous and crystalline regions based on valence. Trivalent iron exists in the crystalline titanite matrix whereas divalent iron exists almost exclusively in radiation-amorphized regions. We find that the relative abundances of the oxidation states correlate with the volume fraction of amorphous and crystalline regions. Our data also show that oxidation of iron proceeds along with the recrystallization of the amorphized regions. Recrystallization is confirmed to occur over the range 700 °C < T < 925 °C, and no further structural changes are observed at higher temperatures. It is surprising that our Mössbauer measurements show divalent iron to be surrounded by titanite with a high degree of short-range structural order in the amorphized regions. This observation is fundamentally different from other metamict materials such as zircon (ZrSiO(4)), where amorphized regions show no short-range order.

Band structure of SnTe studied by photoemission spectroscopy.

We present an angle-resolved photoemission spectroscopy study of the electronic structure of SnTe and compare the experimental results to ab initio band structure calculations as well as a simplified tight-binding model of the p bands. Our study reveals the conjectured complex Fermi surface structure near the L points showing topological changes in the bands from disconnected pockets, to open tubes, and then to cuboids as the binding energy increases, resolving lingering issues about the electronic structure. The chemical potential at the crystal surface is found to be 0.5 eV below the gap, corresponding to a carrier density of p=1.14 × 10(21) cm(-3) or 7.2 × 10(-2) holes per unit cell. At a temperature below the cubic-rhombohedral structural transition a small shift in spectral energy of the valance band is found, in agreement with model predictions.

Composition dependence of the elastic constants of beta-phase and (alpha+beta)-phase PdHx.

We have measured the composition and temperature dependence of the shear moduli C' and C(44) for two-phase (alpha+beta)- and single-phase beta-PdH(x). In the two-phase region, the alpha- and beta-phases are coherent. Here, the composition dependence of C(44) and C' deviate negatively from a Vegard-type volume average. We attribute the deviations to two effects: (1) the partly in-series arrangement of the precipitate and matrix phases, relative to the externally applied stress, and (2) thermally activated anelastic relaxations involving the rapid motion of H interstitial atoms, leading to slight changes in the shape of coherent precipitates. The first effect is present for both C' and C(44) and is temperature-independent, whereas the second is present only for C' and is strongly temperature-dependent.

Similarities in the Cp/T3 peaks in amorphous and crystalline metals.

A low-temperature peak in C(p)/T(3) vs is ubiquitous to glasses. It arises from an abundance of low-frequency vibrations, the origin of which remains unclear. A comparable C(p)/T(3) vs peak is observed in crystals due to the dispersion of acoustic phonons and/or the excitation of optical phonons. We compared the C(p)/T(3) vs peaks in metallic and oxide glasses to elemental crystals by analyzing specific heat, phonon density of states, and elastic constant data. We observe no clear distinction in the peak temperature or amplitude between metallic glasses and crystals. Surprisingly, the peak is larger in single crystal Pd(40)Cu(40)P(20) than in glassy Pd(40)Cu(40)P(20).

The nucleation rate of crystalline ice in amorphous solid water.

The kinetics of crystalline ice nucleation and growth in nonporous, molecular beam deposited amorphous solid water (ASW) films are investigated at temperatures near 140 K. We implement an experimental methodology and corresponding model of crystallization kinetics to decouple growth from nucleation and quantify the temperature dependence and absolute rates of both processes. Nucleation rates are found to increase from approximately 3x10(13) m(-3) s(-1) at 134 K to approximately 2x10(17) m(-3) s(-1) at 142 K, corresponding to an Arrhenius activation energy of 168 kJ/mol. Over the same temperature range, the growth velocity increases from approximately 0.4 to approximately 4 A s(-1), also exhibiting Arrhenius behavior with an activation energy of 47 kJ/mol. These nucleation rates are up to ten orders of magnitude larger than in liquid water near 235 K, while growth velocities are approximately 10(9) times smaller. Crystalline ice nucleation kinetics determined in this study differ significantly from those reported previously for porous, background vapor deposited ASW, suggesting the nucleation mechanism is dependent upon film morphology.