Piezomagnetism and magnetoelastic memory in uranium dioxide.

The thermal and magnetic properties of uranium dioxide, a prime nuclear fuel and thoroughly studied actinide material, remain a long standing puzzle, a result of strong coupling between magnetism and lattice vibrations. The magnetic state of this cubic material is characterized by a 3-k non-collinear antiferromagnetic structure and multidomain Jahn-Teller distortions, likely related to its anisotropic thermal properties. Here we show that single crystals of uranium dioxide subjected to strong magnetic fields along threefold axes in the magnetic state exhibit the abrupt appearance of positive linear magnetostriction, leading to a trigonal distortion. Upon reversal of the field the linear term also reverses sign, a hallmark of piezomagnetism. A switching phenomenon occurs at ±18 T, which persists during subsequent field reversals, demonstrating a robust magneto-elastic memory that makes uranium dioxide the hardest piezomagnet known. A model including a strong magnetic anisotropy, elastic, Zeeman, Heisenberg exchange, and magnetoelastic contributions to the total energy is proposed.The nuclear fuel uranium dioxide is of intrinsic interest due to its industrial applications but it also exhibits intriguing electronic and magnetic properties. Here, the authors demonstrate how its complex magnetic structure and interactions give rise to a strong piezomagnetic effect.

Mechanisms for pressure-induced crystal-crystal transition, amorphization, and devitrification of SnI4.

The pressure-induced amorphization and subsequent recrystallization of SnI4 have been investigated using first principles molecular dynamics calculations together with high-pressure (119)Sn nuclear resonant inelastic x-ray scattering measurements. Above ∼8 GPa, we observe a transformation from an ambient crystalline phase to an intermediate crystal structure and a subsequent recrystallization into a cubic phase at ∼64 GPa. The crystalline-to-amorphous transition was identified on the basis of elastic compatibility criteria. The measured tin vibrational density of states shows large amplitude librations of SnI4 under ambient conditions. Although high pressure structures of SnI4 were thought to be determined by random packing of equal-sized spheres, we detected electron charge transfer in each phase. This charge transfer results in a crystal structure packing determined by larger than expected iodine atoms.

Quantum criticality in a uniaxial organic ferroelectric.

Tris-sarcosine calcium chloride (TSCC) is a highly uniaxial ferroelectric with a Curie temperature of approximately 130 K. By suppressing ferroelectricity with bromine substitution on the chlorine sites, pure single crystals were tuned through a ferroelectric quantum phase transition. The resulting quantum critical regime was investigated in detail and was found to persist up to temperatures of at least 30-40 K. The nature of long-range dipole interactions in uniaxial materials, which lead to non-analytical terms in the free-energy expansion in the polarization, predict a dielectric susceptibility varying as 1/T(3)close to the quantum critical point. Rather than this, we find that the dielectric susceptibility varies as 1/T(2) as expected and observed in better known multi-axial systems. We explain this result by identifying the ultra-weak nature of the dipole moments in the TSCC family of crystals. Interestingly, we observe a shallow minimum in the inverse dielectric function at low temperatures close to the quantum critical point in paraelectric samples that may be attributed to the coupling of quantum polarization and strain fields. Finally, we present results of the heat capacity and electro-caloric effect and explain how the time dependence of the polarization in ferroelectrics and paraelectrics should be considered when making quantitative estimates of temperature changes induced by applied electric fields.

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.

Thermal avalanches near a Mott transition.

We probe the volume collapse transition (ΔV/Vo âˆ¼ 15%) between the isostructural γ and α phases (T âˆ¼ 100 K) of Ce0.9Th0.1 using the Hall effect, three-terminal capacitive dilatometry, and electrical resistivity measurements. Hall effect measurements confirm the itinerant ground state as the carrier concentration increases by a factor of 7 in the α phase, γ phase (nH = 5.28 × 10(26) m(-3)), and the α phase (nH = 3.76 × 10(27) m(-3)). We were able to detect a noise spectrum consisting of avalanches while slowly varying the temperature through the hysteretic region. We surmise that the avalanches originate from intergranular stresses at the interfaces between partially transformed high-volume and low-volume phases. The statistical distribution of avalanches obey power laws with energy exponent ϵ ≃ 1.5. Hall effect measurements, combined with universal critical exponents, point to short electron mean-free percolation pathways and carrier localization at phase interfaces. Carrier localization was predicted many years ago for elemental cerium by Johansson (1974 Phil. Mag. 30 469).

Density of states features in some anomalous melting elements.

Valence band photoemission measurements have been made on crystalline and supercooled liquid gallium, and across the liquid and solid phases of bismuth and indium. Measurements are angle integrated and made using photon excitations of 21.21 and 40.81 eV. In all cases the Bloch states are destroyed upon melting and the free electron gas is constrained by a charge-neutral liquid. The spectra of indium show little change upon solidification, indicating a common electronic structure for crystalline and liquid phases. In contrast, the energy distribution curves for supercooled gallium and bismuth show large changes in the electronic structure from solid to liquid phases, giving rise to the formation of pseudogaps in the density of states at the Fermi energy, EF. Observations of this kind enable us to distinguish normal or anomalous melting from photoemission measurements.

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.

Understanding the complex phase diagram of uranium: the role of electron-phonon coupling.

We report an experimental determination of the dispersion of the soft phonon mode along [100] in uranium as a function of pressure. The energies of these phonons increase rapidly, with conventional behavior found by 20 GPa, as predicted by recent theory. New calculations demonstrate the strong pressure (and momentum) dependence of the electron-phonon coupling, whereas the Fermi-surface nesting is surprisingly independent of pressure. This allows a full understanding of the complex phase diagram of uranium and the interplay between the charge-density wave and superconductivity.

Thermal expansion and transformation behavior of cerium and plutonium alloys: an application of the Aptekar-Ponyatovsky regular solution model.

In this paper we apply the Aptekar-Ponyatovsky (AP) regular solution thermodynamic model to the analysis of experimental data for the coefficient of thermal expansion (CTE) and determine the AP model parameters for unalloyed cerium metal, Ce-Th-La alloys, and Pu-Ga alloys. We find that the high temperature CTE of cerium metal follows the predictions of the AP model based on low temperature, high pressure data. For Ce-Th-La alloys we use the AP parameters to track the suppression of the first-order γ-α cerium transition. We show the AP model accounts for the negative CTE observed for Pu-Ga alloys and is equivalent to an earlier invar model. Finally, we apply the AP parameters obtained for Pu-Ga alloys to rationalize the observed δ-α transformation pressures of these alloys. We show that the anomalous values of the Grüneisen and Grüneisen-Anderson parameters are important features of the thermal properties of plutonium. A strong analogy between the properties of plutonium and cerium is confirmed.

Excess vibrational modes and high thermoelectric performance of the quenched and slow-cooled two-phase alloy Cu0.2Ag2.8SbSeTe2.

In this article we examine the low-temperature specific heat of slow-cooled Cu(0.2)Ag(2.8)SbSeTe(2) and the thermoelectric performance of quenched samples. We find that the low-temperature specific heat is dominated by two Einstein terms of approximate energies of 2.5 and 5 meV. The specific-heat behavior is consistent with the amorphous low-temperature thermal conductivity behavior and validates the glassy nature of the structure. We performed the synthesis of quenched samples in an attempt to eliminate the presence of micro-cracks, whose existence presumably enhances electronic scattering. We find that quenching eliminates the presence of micro-cracks but does not result in an improvement of the figure of merit. Specifically, the highest ZT obtained in the quenched samples (ZT = 1.5), though very competitive, is still significantly less that the ZT obtained in the slow-cooled samples (ZT = 1.75).

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.

Observation of a continuous phase transition in a shape-memory alloy.

Elastic neutron-scattering, inelastic x-ray scattering, specific-heat, and pressure-dependent electrical transport measurements have been made on single crystals of AuZn and Au0.52Zn0.48. Elastic neutron scattering detects new commensurate Bragg peaks (modulation) appearing at Q =(1.33,0.67,0) at temperatures corresponding to each sample's transition temperature (TM = 64 and 45 K, respectively). Although the new Bragg peaks appear in a discontinuous manner in the Au0.52Zn0.48 sample, they appear in a continuous manner in AuZn. Surprising us, the temperature dependence of the AuZn Bragg peak intensity and the specific-heat jump near TM are in favorable accord with a continuous transition. A fit to the pressure dependence of TM suggests the presence of a critical end point in the AuZn phase diagram located at TM* = 2.7 K and p* = 3.1 GPa.

Combined experimental and theoretical investigation of the premartensitic transition in Ni2MnGa.

Ultraviolet-photoemission (UPS) measurements and supporting specific-heat, thermal-expansion, resistivity, and magnetic-moment measurements are reported for the magnetic shape-memory alloy Ni2MnGa over the temperature range 100T(PM) is due to the Ni d minority-spin electrons. Below T(M) this peak disappears, resulting in an enhanced density of states at energies around 0.8 eV. This enhancement reflects Ni d and Mn d electronic contributions to the majority-spin density of states.

Heat capacity and thermal expansion of the itinerant helimagnet MnSi.

The heat capacity and thermal expansion of a high quality single crystal of MnSi were measured at ambient pressure at zero and high magnetic fields. The calculated magnetic entropy change in the temperature range 0-30 K is less than 0.1R, a low value that emphasizes the itinerant nature of magnetism in MnSi. A linear temperature term dominates the thermal expansion coefficient in the range 30-150 K, which correlates with an enhancement of the linear electronic term in the heat capacity. A surprising similarity among the variations of the heat capacity, thermal expansion coefficient and temperature derivative of the resistivity is observed through the phase transition in MnSi. Specific forms of the heat capacity, thermal expansion coefficient and temperature derivative of resistivity at the phase transition to a helical magnetic state near 29 K are interpreted as the combination of sharp first-order features and broad peaks or shallow valleys of as yet unknown origin. The appearance of these broad satellites probably hints at a frustrated magnetic state slightly above the transition temperature in MnSi.

Formation of a new dynamical mode in -uranium observed by inelastic x-ray and neutron scattering.

Phonon dispersion curves were obtained from inelastic x-ray and neutron scattering measurements on alpha-uranium single crystals at temperatures from 298 to 573 K. Both measurements showed a softening and an abrupt loss of intensity in the longitudinal optic branch along [00zeta] above 450 K. Above the same temperature a new dynamical mode of comparable intensity emerges along the [01zeta] zone boundary with energy near the top of the phonon spectrum. The new mode forms without a structural transition but coincides with an anomaly in the mechanical deformation behavior. We argue that the mode is an intrinsically localized vibration and formed as a result of a strong electron-phonon interaction.

Pinning frequencies of the collective modes in alpha-uranium.

Uranium is the only known element that features a charge-density wave (CDW) and superconductivity. We report a comparison of the specific heat of single-crystal and polycrystalline alpha-uranium. In the single crystal we find excess contributions to the heat capacity at 41 K, 38 K, and 23 K, with a Debye temperature ThetaD = 265 K. In the polycrystalline sample the heat capacity curve is thermally broadened (ThetaD = 184 K), but no excess heat capacity was observed. The excess heat capacity Cphi (taken as the difference between the single-crystal and polycrystal heat capacities) is well described in terms of collective-mode excitations above their respective pinning frequencies. This attribution is represented by a modified Debye spectrum with two cutoff frequencies, a pinning frequency V0 for the pinned CDW (due to grain boundaries in the polycrystal), and a normal Debye acoustic frequency occurring in the single crystal.

Tricritical phenomena at the gamma-->alpha transition in Ce0.9-xLaxTh0.1 alloys.

The gamma-->alpha isostructural transition in the Ce0.9-xLaxTh0.1 system is measured as a function of La alloying using specific heat, magnetic susceptibility, resistivity, thermal expansivity or striction measurements. A line of discontinuous transitions, as indicated by the change in volume, decreases exponentially from 118 K to close to 0 K with increasing La doping, and the transition changes from being first-order to continuous at a critical concentration, x(c) approximately 0.14. At the tricritical point, the coefficient of the linear T term in the specific heat gamma and the magnetic susceptibility increase rapidly near x(c) and approach large values at x=0.35 signifying that a heavy Fermi-liquid state evolves at large doping. The Wilson ratio reaches a value above 2 for a narrow range of concentrations near x(c), where the specific heat and susceptibility vary most rapidly with the doping concentration.

Catastrophic Fermi surface reconstruction in the shape-memory alloy AuZn.

AuZn undergoes a shape-memory transition at 67 K. The de Haas-van Alphen effect persists to 100 K enabling the observation of a change in the quantum oscillation spectrum indicative of a catastrophic Fermi surface reconstruction at the transition. The coexistence of both Fermi surfaces at low temperatures suggests an intrinsic phase separation in the bulk of the material. In addition, Dingle analysis reveals a sharp change in the scattering mechanism at a threshold cyclotron radius, attributable to the underlying microstructure driving the shape-memory effect.