Refractory materials for high-temperature thermoelectric energy conversion

Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity

Hall-Effect Sign Anomaly and Small-Polaronic Conduction in (La_{1-x}Gd_x)_{0.67}Ca_{0.33}MnO_3

The Hall coefficient of Gd-doped La_{2/3}Ca_{1/3}MnO_3 exhibits Arrhenius behavior over a temperature range from 2T_c to 4T_c, with an activation energy very close to 2/3 that of the electrical conductivity. Although both the doping level and thermoelectric coefficient indicate hole-like conduction, the Hall coefficient is electron-like. This unusual result provides strong evidence in favor of small-polaronic conduction in the paramagnetic regime of the manganites.Comment: 11 pages, 4 figures, uses revtex.st

Thermal conductivity behavior of boron carbides

Knowledge of the thermal conductivity of boron carbides is necessary to evaluate its potential for high temperature thermoelectric energy conversion applications. The thermal diffusivity of hot pressed boron carbide B/sub 1-x/C/sub x/ samples as a function of composition, temperature and temperature cycling was measured. These data in concert with density and specific heat data yield the thermal conductivities of these materials. The results in terms of a structural model to explain the electrical transport data and novel mechanisms for thermal conduction are discussed

Extensions of Picard 2-Stacks and the cohomology groups Ext^i of length 3 complexes

The aim of this paper is to define and study the 3-category of extensions of Picard 2-stacks over a site S and to furnish a geometrical description of the cohomology groups Ext^i of length 3 complexes of abelian sheaves. More precisely, our main Theorem furnishes (1) a parametrization of the equivalence classes of objects, 1-arrows, 2-arrows, and 3-arrows of the 3-category of extensions of Picard 2-stacks by the cohomology groups Ext^i, and (2) a geometrical description of the cohomology groups Ext^i of length 3 complexes of abelian sheaves via extensions of Picard 2-stacks. To this end, we use the triequivalence between the 3-category of Picard 2-stacks and the tricategory T^[-2,0](S) of length 3 complexes of abelian sheaves over S introduced by the second author in arXiv:0906.2393, and we define the notion of extension in this tricategory T^[-2,0](S), getting a pure algebraic analogue of the 3-category of extensions of Picard 2-stacks. The calculus of fractions that we use to define extensions in the tricategory T^[-2,0](S) plays a central role in the proof of our Main Theorem.Comment: 2 New Appendix: in the first Appendix we compute a long exact sequence involving the homotopy groups of an extension of Picard 2-stacks, and in the second Appendix we sketch the proof that the fibered sum of Picard 2-stacks satisfies the universal propert

Infrared spectroscopy of the charge ordering transition in Na0.5_{0.5}CoO2_2

We report infrared spectra of a Na$_{0.5}$CoO$_2$ single crystal which exhibits a sharp metal-insulator transition near 50 K due to the formation of charge ordering. In comparison with x=0.7 and 0.85 compounds, we found that the spectral weight associated with the conducting carriers at high temperature increases systematically with decreasing Na contents. The charge ordering transition only affects the optical spectra below 1000 cm$^{-1}$. A hump near 800 cm$^{-1}$ develops below 100 K, which is accompanied by the appearance of new lattice modes as well as the strong anti-resonance feature of phonon spectra. At lower temperature $T_{co}$, an optical gap develops at the magnitude of 2$\Delta\approx3.5k_BT_{co}$, evidencing an insulating charge density wave ground state. Our experimental results and analysis unequivocally point towards the importance of charge ordering instability and strong electron-phonon interaction in Na$_x$CoO$_2$ system.Comment: 4 pages, 3 figure

Anisotropic Small-Polaron Hopping In W:Bivo4 Single Crystals

DC electrical conductivity, Seebeck and Hall coefficients are measured between 300 and 450 K on single crystals of monoclinic bismuth vanadate that are doped n-type with 0.3% tungsten donors (W:BiVO4). Strongly activated small-polaron hopping is implied by the activation energies of the Arrhenius conductivities (about 300 meV) greatly exceeding the energies characterizing the falls of the Seebeck coefficients' magnitudes with increasing temperature (about 50 meV). Small-polaron hopping is further evidenced by the measured Hall mobility in the ab-plane (10(-1) cm(2) V-1 s(-1) at 300 K) being larger and much less strongly activated than the deduced drift mobility (about 5 x 10(-5) cm(2) V-1 s(-1) at 300 K). The conductivity and n-type Seebeck coefficient is found to be anisotropic with the conductivity larger and the Seebeck coefficient's magnitude smaller and less temperature dependent for motion within the ab-plane than that in the c-direction. These anisotropies are addressed by considering highly anisotropic next-nearest-neighbor (approximate to 5 angstrom) transfers in addition to the somewhat shorter (approximate to 4 angstrom), nearly isotropic nearest-neighbor transfers. (C) 2015 AIP Publishing LLC.U.S. Department of Energy (DOE), DE-FG02-09ER16119Welch Foundation Grant F-1436Hemphill-Gilmore Endowed FellowshipNSF MIRT DMR 1122603Chemical EngineeringTexas Materials InstituteChemistr

Breakdown of the lattice polaron picture in La0.7Ca0.3MnO3 single crystals

When heated through the magnetic transition at Tc, La0.7Ca0.3MnO3 changes from a band metal to a polaronic insulator. The Hall constant R_H, through its activated behavior and sign anomaly, provides key evidence for polaronic behavior. We use R_H and the Hall mobility to demonstrate the breakdown of the polaron phase. Above 1.4Tc, the polaron picture holds in detail, while below, the activation energies of both R_H and the mobility deviate strongly from their polaronic values. These changes reflect the presence of metallic, ferromagnetic fluctuations, in the volume of which the Hall effect develops additional contributions tied to quantal phases.Comment: 11 pages, 3 figures, final version to appear in Phys. Rev. B Rapi

Systematic Observations of the Availability and Use of Instructional Technology in Urban Middle School Classrooms

The present study uses systematic observations to investigate the availability and use of instructional technology in 64 middle school classrooms serving predominantly minority students from economically disadvantaged families. The T3 Overall Classroom Observation Measure, a high-inference walk-through instrument, was developed to examine: (a) types and use of technology present in the classroom, (b) teachers’ technology usage, (c) students’ technology usage, (d) teachers’ general instructional behaviors, and (e) students’ general behaviors. The results revealed that instructional technology was widely available in the classrooms, but most teachers and students were only using it to “some extent.

Berry phases and pairing symmetry in Holstein-Hubbard polaron systems

We study the tunneling dynamics of dopant-induced hole polarons which are self-localized by electron-phonon coupling in a two-dimensional antiferro- magnet. Our treatment is based on a path integral formulation of the adia- batic approximation, combined with many-body tight-binding, instanton, con- strained lattice dynamics, and many-body exact diagonalization techniques. Our results are mainly based on the Holstein-$tJ$ and, for comparison, on the Holstein-Hubbard model. We also study effects of 2nd neighbor hopping and long-range electron-electron Coulomb repulsion. The polaron tunneling dynamics is mapped onto an effective low-energy Hamiltonian which takes the form of a fermion tight-binding model with occupancy dependent, predominant- ly 2nd and 3rd neighbor tunneling matrix elements, excluded double occupan- cy, and an effective intersite charge interactions. Antiferromagnetic spin correlations in the original many-electron Hamiltonian are reflected by an attractive contribution to the 1st neighbor charge interaction and by Berry phase factors which determine the signs of effective polaron tunneling ma- trix elements. In the two-polaron case, these phase factors lead to polaron pair wave functions of either $d_{x^2-y^2}$-wave symmetry or p-wave symme- try with zero and nonzero total pair momentum, respectively. Implications for the doping dependent isotope effect, pseudo-gap and Tc of a superconduc- ting polaron pair condensate are discussed/compared to observed in cuprates.Comment: 23 pages, revtex, 13 ps figure