Nanostructuration via solid state transformation as a strategy for improving the thermoelectric efficiency of PbTe alloys

The approach taken in this paper in order to modify the scattering features of electrons and phonons and improve the figure of merit (ZT) of thermoelectric PbTe is to alter the microstructure at constant chemistry. A lamellar pattern of PbTe/GeTe at the nano- and microscale was produced in Pb(0.36)Ge(0.64)Te alloy by the diffusional decomposition of a supersaturated solid solution. The mechanism of nanostructuration is most likely a discontinuous spinodal decomposition. A simple model relating the interface velocity to the observed lamellar spacing is proposed. The effects of nanostructuration in Pb(0.36)Ge(0.64)Te alloy on the electrical and thermal conductivity, thermopower and ZT were investigated. It was shown that nanostructuration through the formation of a lamellar pattern of PbTe/GeTe is unlikely to provide a significant improvement due to the occurrence of discontinuous coarsening. However, the present study allows an analysis of possible strategies to improve thermoelectric materials via optimal design of the microstructure and optimized heat treatment. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Some studies on a solid state sulphur probe for coal gasification system

Measurements on the solid electrolyte cell(Ar -b H2 ~ H2S/CaS + CaF2 ~- ( P t ) / / C a F 2 / / ( P t )-~- CaF2 ~ CaS/H2S ~- H2 ~- At) show that the emf of the cell is directly related through the Nernst equation to the difference in sulfur potentials established at the two Ar ~- H2 ~ H2S/electrode interfaces. The electrodes are designed to convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient with the aid of the reaction, CaF2(s) ~ 1~ S2(g)-e CaS(s) ~- F2(g). The response time of the probe varies from approximately 9 hr at 990~ to 2.5 hr at 1225~ The conversion of calcium sulfide and/or calcium fluoride into calcium oxide should not be a problem in anticipated commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.

A solid-state probe for SO2/SO3 based on Na2SO4 I electrolyte

Conductivity measurements as a function of temperature and partial pressures of SOs, SO2, and O2, and transference experiments indicate that the transport number of Na + ions is unity in Na2SO4-I. A concentration cell based on this electrolyte Pt, O2' + SO2' + SOs'/Na2SO4-I/SOa" + SO~" + O~", Pt produces emf's that are in agreement with those calculated from the Nernst equation when equilibrium is assumed between the gas species at the electrodes. The cell can be used for monitoring the SO#SOs pollution in air, and in combination with an oxygen probe can be used for the determination of SO=/SOs concentrations in coal combustion reactors, for the evaluation of the partial pressure of $2 in coal gasification systems, and for emission control in nonferrous smelters using sulfide ores. The probe is similar to that developed recently by Gauthier et aL (4, 5) using K=SO4 as the electrolyte, but can operate at higher pressures of SO3. Because of the greater polarizing power of the Na+ ion compared to the K + ion, Na2S207 is less stable and can be formed only at a considerably higher pressure of S03 than that required for K~20~.

Some recent developments in solid state galvanic sensors

A critical revi<:w of the possibilities of measuring the ~artlal pressure of sulfur using solid state galvanic cells )'n;;cd on AgI, C" , B-alumina, CaO-Zr02' Na2S04-I and doped ;:":;, ,,,Ilil "Iltl ,,11: auxiliary "jectrodes are presentlOu. SOIll..., df tllc!iL' sYHtcmH h,}vu inherent limltntlol1$ when <:xl'o" ...d to environments contilining both oxygen and sulfur. Electrode polarization due to electronic conduction in the solid electrolyte is a significant factor limiting the ;lC'e,"'acy of isotlwrm:l1 cell",. The electrochemical flux of{lit' !'\)ndlwl Ill}: Ion LhnHO',h tht' ('!('ctrojyt(~ C:Ul },(,! llIinlnliz(,{j pfUjJL!f cell. dL:~) i.t',11. Noni!:iot.herm~ll cells \.Jlth temperaLure compensated reference electrodes have a number of advantages over thC'ir isothermal counterparts.

Phase relations in the system Sr–Ir–O and thermodynamic measurements on SrIrO3, Sr2IrO4 and Sr4IrO6 using solid-state cells with buffer electrodes

The standard Gibbs energies of formation of SrIrO3, Sr2IrO4 and Sr4IrO6 have been determined in the temperature range from 975 to 1400 K using solid-state cells with (Y2O3) ZrO2 as the electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sr–Ir–O were investigated at 1350 K. The only stable oxide detected along the binary Ir–O was IrO2. Three ternary oxides, SrIrO3, Sr2IrO4 and Sr4IrO6, compositions of which fall on the join SrO–IrO2, were found to be stable. Each of the oxides coexisted with pure metal Ir. Therefore, three working electrodes were prepared consisting of mixtures of Ir+SrO+Sr4IrO6, Ir+Sr4IrO6+Sr2IrO4, and Ir+Sr2IrO4+SrIrO3. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. Used for the measurements was a novel apparatus, in which a buffer electrode was introduced between reference and working electrodes to absorb the electrochemical flux of oxygen through the solid electrolyte. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The standard Gibbs energies of formation of the compounds, obtained from the emf of the cells, can be represented by the following equations: View the MathML sourcem View the MathML source View the MathML source where Δf (ox)Go represents the standard Gibbs energy of formation of the ternary compound from its component binary oxides SrO and IrO2. Based on the thermodynamic information, chemical potential diagrams for the system Sr–Ir–O were developed.

System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.

An advanced design of the solid-state cell for accurate thermodynamic measurements on ternary oxides: system Sm–Pd–O

An advanced design of the solid-state cell incorporating a buffer electrode has been developed for high temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The application of the novel design and its advantages have been demonstrated by measuring the standard Gibbs energies of formation of ternary oxides of the system Sm–Pd–O. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sm–Pd–O were investigated at 1273 K. The two ternary oxides, Sm4PdO7 and Sm2Pd2O5, compositions of which fall on the Sm2O3–PdO join, were found to coexist with pure metal Pd. The thermodynamic properties of the ternary oxides were measured using three-phase electrodes in the temperature range 950–1425 K. During electrochemical measurements a third ternary oxide, Sm2PdO4, was found to be stable at low temperature. The standard Gibbs energies of formation (Δf(ox)Go) of the compounds from their component binary oxides Sm2O3 and PdO, can be represented by the equations: Sm4PdO7: Δf(ox)Go (J mol−1)=−34,220+0.84T(K) (±280); Sm2PdO4: Δf(ox)Go (J mol−1)=−33,350+2.49T(K) (±230); Sm2Pd2O5: Δf(ox)Go (J mol−1)=−59,955+1.80T(K) (±320). Based on the thermodynamic information, three-dimensional P–T–C and chemical potential diagrams for the system Sm–Pd–O were developed.

Solid-state cells with buffer electrodes for accurate thermodynamic measurements: system Nd-Ir-O

A new design for the solid-state cell incorporating a buffer electrode for high-temperature thermodynamic measurements is presented. The function of the buffer electrode, placed between the reference and working electrodes, is to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevents polarization of the measuring electrode and ensures accurate data. The application of this novel design and its advantages are demonstrated by measurement of the standard Gibbs energies of formation of Nd6Ir2O13 (low-temperature form) and Nd2Ir2O7 in the temperature range from 975 to 1450 K. Yttria-stabilized zirconia is used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system NdIrO were investigated at 1350 K. The two ternary oxides, Nd6Ir2O13 and Nd2Ir2O7, compositions of which fall on the join Nd2O3IrO2, were found to coexist with pure metal Ir. Therefore, two working electrodes were prepared consisting of mixtures of Ir+Nd2O3+Nd6Ir2O13 and Ir+Nd6Ir2O13+ Nd2Ir2O7. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. The standard Gibbs energies of formation (ΔG°f (ox)) of the compounds from their component binary oxides Nd2O3 and IrO2, obtained from the emf of the cells, can be represented by the equations:View the MathML source View the MathML source Based on the thermodynamic information, chemical potential diagrams for the system NdIrO are developed.

Solid state electrochemical sensor for monitoring Mg in Al refining process

Novel solid-state electrochemical sensors have been designed using the Mg2+ cation conductors incorporating novel solid-state reference electrodes for in-line monitoring of Mg in molten Al during the refining process and also for in-line monitoring of Mg content in molten Al in the alloying process. In this paper we report the preparation of Mg2+ ion conductors, MgAl2O4 and MgZr4(PO4)6, by the solid state ceramic synthesis route, measurement of their electrical properties using ac-impedance spectroscopy and application of the above cation conductors for designing novel electrochemical sensors for monitoring Mg dissolved in molten Al. The activation energy for Mg2+ ion conduction in MgAl2O4 is 2.08 eV and in MgZr4(PO4)6 is 1.7 eV, respectively. The sensors have been found to respond rapidly to change in Mg content in molten aluminium around 1000 K.

Developments in solid-state under-frequency relays

Simpler circuits for frequency-sensitive relays responding to change and rate of change of system frequency have been developed employing phase-locked loops. A new relay responding to time intergral of the fall in system frequency has also been developed and its performance has been compared with those responding to change and rate of change of system frequency. The relays have been tested and calibrated with the help of a specially designed calibration kit.

Towards sustainability: a new, solid-state synthetic route for supported metal nanocatalysts

Noble metal ions like Pt(IV) and Pd(II) were impregnated on gamma-alumina and aerosol 300 silica surfaces. Reduction of these ions using ammonia borane in the solid state resulted in the formation of the respective metal nanoparticles embedded in BNHx polymer which is dispersed on the oxide support. Removal of the BNH polymer was accomplished by washing the samples repeatedly with methanol. In this process the polymer undergoes solvolysis to release H-2 accompanied by the formation of ammonium methoxy borate salt, which has been removed by repeated methanol washings. As a result, metal nanoparticles well dispersed on gamma-alumina and aerosol 300 silica were obtained. These samples have been characterized by a combination of techniques, including electron microscopy, powder X-ray diffraction, NMR spectroscopy and surface area analyser.

Combining adiabatic and Hartmann-Hahn cross-polarization for sensitivity enhancement in solid state separated local field 2D-NMR experiments of partially ordered systems

In this Letter, we examine magnetization in double- and zero-quantum reservoirs of an ensemble of spin-1/2 nuclei and describe their role in determining the sensitivity of a class of separated local field NMR experiments based on Hartmann-Hahn cross-polarization. We observe that for the liquid crystal system studied, a large dilute spin-polarization, obtained initially by the use of adiabatic cross-polarization, can enhance the sensitivity of the above experiment. The signal enhancement factors, however, are found to vary and depend on the local dynamics. The experimental results have been utilized to obtain the local order-parameters of the system. (C) 2012 Elsevier B. V. All rights reserved.