Sample seal-and-drop device and methodology for high temperature oxide melt solution calorimetric measurements of PuO2.

Thermodynamic properties of refractory materials, such as standard enthalpy of formation, heat content, and enthalpy of reaction, can be measured by high temperature calorimetry. In such experiments, a small sample pellet is dropped from room temperature into a calorimeter operating at high temperature (often 700 °C) with or without a molten salt solvent present in an inert crucible in the calorimeter chamber. However, for hazardous (radioactive, toxic, etc.) and/or air-sensitive (hygroscopic, sensitive to oxygen, pyrophoric, etc.) samples, it is necessary to utilize a sealed device to encapsulate and isolate the samples, crucibles, and solvent under a controlled atmosphere in order to prevent the materials from reactions and/or protect the personnel from hazardous exposure during the calorimetric experiments. We have developed a sample seal-and-drop device (calorimetric dropper) that can be readily installed onto the dropping tube of a calorimeter such as the Setaram AlexSYS Calvet-type high temperature calorimeter to fulfill two functions: (i) load hazardous or air-sensitive samples in an air-tight, sealed container and (ii) drop the samples into the calorimeter chamber using an "off-then-on" mechanism. As a case study, we used the calorimetric dropper for measurements of the enthalpy of drop solution of PuO2 in molten sodium molybdate (3Na2O·4MoO3) solvent at 700 °C. The obtained enthalpy of -52.21 ± 3.68 kJ/mol is consistent with the energetic systematics of other actinide oxides (UO2, ThO2, and NpO2). This capability has thus laid the foundation for thermodynamic studies of other Pu-bearing phases in the future.

Resonant ultrasound spectroscopy: The essential toolbox.

Resonant Ultrasound Spectroscopy (RUS) is an ultrasound-based minimal-effort high-accuracy elastic modulus measurement technique. RUS as described here uses the mechanical resonances (normal modes of vibration or just modes) of rectangular parallelepiped or cylindrical specimens with a dimension of from a fraction of a millimeter to as large as will fit into the apparatus. Provided here is all that is needed so that the reader can construct and use a state-of-the-art RUS system. Included are links to open-source circuit diagrams, links to download Los Alamos National Laboratory open-source data acquisition software, links to request free analysis software, procedures for acquiring measurements, considerations on building transducers, 3-D printed stage designs, and a full mathematical explanation of how the analysis software extracts elastic moduli from resonances.

Origin of the multiple configurations that drive the response of δ-plutonium's elastic moduli to temperature.

The electronic and thermodynamic complexity of plutonium has resisted a fundamental understanding for this important elemental metal. A critical test of any theory is the unusual softening of the bulk modulus with increasing temperature, a result that is counterintuitive because no or very little change in the atomic volume is observed upon heating. This unexpected behavior has in the past been attributed to competing but never-observed electronic states with different bonding properties similar to the scenario with magnetic states in Invar alloys. Using the recent observation of plutonium dynamic magnetism, we construct a theory for plutonium that agrees with relevant measurements by using density-functional-theory (DFT) calculations with no free parameters to compute the effect of longitudinal spin fluctuations on the temperature dependence of the bulk moduli in δ-Pu. We show that the softening with temperature can be understood in terms of a continuous distribution of thermally activated spin fluctuations.

Avoided valence transition in a plutonium superconductor.

The d and f electrons in correlated metals are often neither fully localized around their host nuclei nor fully itinerant. This localized/itinerant duality underlies the correlated electronic states of the high-Tc cuprate superconductors and the heavy-fermion intermetallics and is nowhere more apparent than in the 5f valence electrons of plutonium. Here, we report the full set of symmetry-resolved elastic moduli of PuCoGa5--the highest Tc superconductor of the heavy fermions (Tc = 18.5 K)--and find that the bulk modulus softens anomalously over a wide range in temperature above Tc. The elastic symmetry channel in which this softening occurs is characteristic of a valence instability--therefore, we identify the elastic softening with fluctuations of the plutonium 5f mixed-valence state. These valence fluctuations disappear when the superconducting gap opens at Tc, suggesting that electrons near the Fermi surface play an essential role in the mixed-valence physics of this system and that PuCoGa5 avoids a valence transition by entering the superconducting state. The lack of magnetism in PuCoGa5 has made it difficult to reconcile with most other heavy-fermion superconductors, where superconductivity is generally believed to be mediated by magnetic fluctuations. Our observations suggest that valence fluctuations play a critical role in the unusually high Tc of PuCoGa5.

Bounding the pseudogap with a line of phase transitions in YBa2Cu3O6+δ.

Close to optimal doping, the copper oxide superconductors show 'strange metal' behaviour, suggestive of strong fluctuations associated with a quantum critical point. Such a critical point requires a line of classical phase transitions terminating at zero temperature near optimal doping inside the superconducting 'dome'. The underdoped region of the temperature-doping phase diagram from which superconductivity emerges is referred to as the 'pseudogap' because evidence exists for partial gapping of the conduction electrons, but so far there is no compelling thermodynamic evidence as to whether the pseudogap is a distinct phase or a continuous evolution of physical properties on cooling. Here we report that the pseudogap in YBa2Cu3O6+δ is a distinct phase, bounded by a line of phase transitions. The doping dependence of this line is such that it terminates at zero temperature inside the superconducting dome. From this we conclude that quantum criticality drives the strange metallic behaviour and therefore superconductivity in the copper oxide superconductors.

Rhenium diboride's monocrystal elastic constants, 308 to 5 K.

The five independent moduli required to construct the complete monocrystal elastic modulus tensor of the hexagonal-symmetry superhard compound ReB(2) were measured from 308 to 5 K using resonant ultrasound spectroscopy on a special-texture polycrystal. This is possible because, confirmed by X-ray diffraction, the specimen measured was composed of grains with hexagonal axes parallel so that its polycrystal elastic response is identical to a monocrystal and because hexagonal-symmetry solids are elastically isotropic in the plane perpendicular to the hexagonal axis. Along the hexagonal (c) axis, C(33) (0) = 1021 GPa, nearly equal to C(11) of diamond, and consistent with the superhard properties. However, in the (softer) isotropic plane, C(11) (0) = 671 GPa, much lower than diamond. The changes of C(ij) with temperature are very small and smooth. The Debye temperature was computed to be 738 K, and using a high-temperature approximation, the Grüneisen parameter is γ = 1.7.

Dielectric saturation of liquid propylene carbonate in electrical energy storage applications.

Dielectric characteristics of a molecular model of liquid propylene carbonate are evaluated for utilization in molecular scale simulation of electrochemical capacitors based on nanotube forests. The linear-response dielectric constant of the bulk liquid, and its temperature dependence, is in good agreement with experiment. Dielectric saturation is studied by simulations with static uniform electric fields as large as 4 V/nm. The observed polarization is well described by the Langevin equation with the low-field/high-field crossover parameter of 0.09 V/nm. Simulation of liquid propylene carbonate confined between charged parallel graphite electrodes yields a capacitance that depends on the electric potential difference across those thin films. An effective dielectric constant inferred from the capacitance is significantly less than the uniform liquid dielectric constant, but is consistent with the nonlinear dielectric response at the strong fields applied to the electrode film. Those saturation effects reduce the weak-field capacitance.

Alpha-plutonium's Grüneisen parameter.

Reported Grüneisen parameters γ of alpha-plutonium range from 3.0 to 9.6, which is remarkable because typical Grüneisen parameter uncertainty seldom exceeds ± 0.5. Our six new estimates obtained by different methods range from 3.2 to 9.6. The new estimates arise from Grüneisen's rule, from Einstein model and Debye model fits to low-temperature ΔV/V, from the bulk modulus temperature dependence, from the zero-point-energy contribution to the bulk modulus, and from another Grüneisen relationship whereby γ is estimated from only the bulk modulus and volume changes with temperature (or pressure). We disregard several high estimates because of the itinerant-localized 5f-electron changes during temperature changes and pressure changes. Considering all these estimates, for alpha-plutonium, we recommend γ = 3.7 ± 0.4, slightly high compared with values for all elemental metals.

Molecular simulation of electric double-layer capacitors based on carbon nanotube forests.

Described here are the first simulations of electric double-layer capacitors based on carbon nanotube forests modeled fully at a molecular level. The computations determine single-electrode capacitances in the neighborhood of 80 F/g, in agreement with experimental capacitances of electric double-layer capacitors utilizing carbon nanotube forests or carbide-derived carbons as electrode material. The capacitance increases modestly with the decrease of the pore size through radii greater than 1 nm, which is consistent with recent experiments on carbide-derived carbon electrodes. Because the various factors included in these simulations are precisely defined, these simulation data will help to disentangle distinct physical chemical factors that contribute to the performance of these materials, e.g., pore geometry, variable filling of the pores, pseudocapacitance, and electronic characteristics of the nanotubes.

Signature of optimal doping in Hall-effect measurements on a high-temperature superconductor.

High-temperature superconductivity is achieved by doping copper oxide insulators with charge carriers. The density of carriers in conducting materials can be determined from measurements of the Hall voltage--the voltage transverse to the flow of the electrical current that is proportional to an applied magnetic field. In common metals, this proportionality (the Hall coefficient) is robustly temperature independent. This is in marked contrast to the behaviour seen in high-temperature superconductors when in the 'normal' (resistive) state; the departure from expected behaviour is a key signature of the unconventional nature of the normal state, the origin of which remains a central controversy in condensed matter physics. Here we report the evolution of the low-temperature Hall coefficient in the normal state as the carrier density is increased, from the onset of superconductivity and beyond (where superconductivity has been suppressed by a magnetic field). Surprisingly, the Hall coefficient does not vary monotonically with doping but rather exhibits a sharp change at the optimal doping level for superconductivity. This observation supports the idea that two competing ground states underlie the high-temperature superconducting phase.