Ball milling as an effective route for the preparation of doped bornite: synthesis, stability and thermoelectric properties

Bornite, Cu5FeS4, is a naturally-occuring mineral with an ultralow thermal conductivity and potential for thermoelectric power generation. We describe here a new, easy and scalable route to synthesise bornite, together with the thermoelectric behaviour of manganese-substituted derivatives, Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10). The electrical and thermal transport properties of Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10), which are p-type semiconductors, were measured from room temperature to 573 K. The stability of bornite was investigated by thermogravimetric analysis under inert and oxidising atmospheres. Repeated measurements of the electrical transport properties confirm that bornite is stable up to 580 K under an inert atmosphere, while heating to 890 K results in rapid degradation. Ball milling leads to a substantial improvement in the thermoelectric figure of merit of unsusbtituted bornite (ZT = 0.55 at 543 K), when compared to bornite prepared by conventional high-temperature synthesis (ZT < 0.3 at 543 K). Manganese-substituted samples have a ZT comparable to that of unsubstituted bornite.

Combined cycle versus one thousand diesel power plants: pollutant emissions, ecological efficiency and economic analysis

The increase in the use of natural gas in Brazil has stimulated public and private sectors to analyse the possibility of using combined cycle systems for generation of electrical energy. Gas turbine combined cycle power plants are becoming increasingly common due to their high efficiency, short lead times, and ability to meet environmental standards. Power is produced in a generator linked directly to the gas turbine. The gas turbine exhaust gases are sent to a heat recovery steam generator to produce superheated steam that can be used in a steam turbine to produce additional power. In this paper a comparative study between a 1000 MW combined cycle power plant and 1000 kW diesel power plant is presented. In first step, the energetic situation in Brazil, the needs of the electric sector modification and the needs of demand management and integrated means planning are clarified. In another step the characteristics of large and small thermoelectric power plants that use natural gas and diesel fuel, respectively, are presented. The ecological efficiency levels of each type of power plant is considered in the discussion, presenting the emissions of particulate material, sulphur dioxide (SO2), carbon dioxide (CO2) and nitrogen oxides (NOx). (c) 2006 Elsevier Ltd. All rights reserved.

Thermoelectric effects in quantum dots

We report a numerical renormalization-group study of the thermoelectric effect in the single-electron transistor (SET) and side-coupled geometries. As expected, the computed thermal conductance and thermopower curves show signatures of the Kondo effect and of Fano interference. The thermopower curves are also affected by particle-hole asymmetry. © 2009 Elsevier B.V. All rights reserved.

Mathematical decomposition technique applied to the probabilistic power flow problem

In this paper a framework based on the decomposition of the first-order optimality conditions is described and applied to solve the Probabilistic Power Flow (PPF) problem in a coordinated but decentralized way in the context of multi-area power systems. The purpose of the decomposition framework is to solve the problem through a process of solving smaller subproblems, associated with each area of the power system, iteratively. This strategy allows the probabilistic analysis of the variables of interest, in a particular area, without explicit knowledge of network data of the other interconnected areas, being only necessary to exchange border information related to the tie-lines between areas. An efficient method for probabilistic analysis, considering uncertainty in n system loads, is applied. The proposal is to use a particular case of the point estimate method, known as Two-Point Estimate Method (TPM), rather than the traditional approach based on Monte Carlo simulation. The main feature of the TPM is that it only requires resolve 2n power flows for to obtain the behavior of any random variable. An iterative coordination algorithm between areas is also presented. This algorithm solves the Multi-Area PPF problem in a decentralized way, ensures the independent operation of each area and integrates the decomposition framework and the TPM appropriately. The IEEE RTS-96 system is used in order to show the operation and effectiveness of the proposed approach and the Monte Carlo simulations are used to validation of the results. © 2011 IEEE.

Thermoelectric assessment of laser peening induced effects on a metallic biomedical Ti6Al4V

Laser peening has recently emerged as a useful technique to overcome detrimental effects associated to another well-known surface modification processes such as shot peening or grit blasting used in the biomedical field. It is worth to notice that besides the primary residual stress effect, thermally induced effects might also cause subtle surface and subsurface microstructural changes that might influence corrosion resistance. Moreover, since maximum loads use to occur at the surface, they could also play a critical role in the fatigue strength. In this work, plates of Ti-6Al-4V alloy of 7 mm in thickness were modified by laser peening without using a sacrificial outer layer. Irradiation by a Q-switched Nd-YAG laser (9.4 ns pulse length) working in fundamental harmonic at 2.8 J/pulse and with water as confining medium was used. Laser pulses with a 1.5 mm diameter at an equivalent overlapping density (EOD) of 5000 cm-2 were applied. Attempts to analyze the global induced effects after laser peening were addressed by using the contacting and non-contacting thermoelectric power (TEP) techniques. It was demonstrated that the thermoelectric method is entirely insensitive to surface topography while it is uniquely sensitive to subtle variations in thermoelectric properties, which are associated with the different material effects induced by different surface modification treatments. These results indicate that the stress-dependence of the thermoelectric power in metals produces sufficient contrast to detect and quantitatively characterize regions under compressive residual stress based on their thermoelectric power contrast with respect to the surrounding intact material. However, further research is needed to better separate residual stress effects from secondary material effects, especially in the case of low-conductivity engineering materials like titanium alloys.

Impurity states in Sb-doped amorphous semiconductors

A systematic investigation of the effects of antimony dopant on the electronic transport properties of amorphous (GeSe3.5)100−xSbx under high pressure (up to 120 kbar) has been carried out down to liquid-nitrogen temperature for the first time. Differential thermal analysis and x-ray diffraction methods were used for the characterization of freshly prepared and pressure-quenched materials which indicated the presence of structural phase transition in both GeSe3.5 and (GeSe3.5)100−xSbx around 105 kbar pressure. Electrical transport data revealed the strong compositional dependence of the electronic conduction process. A distinct kink in the conductivity temperature plot at pressures>15 kbar was observed in the Sb-doped compositions indicating the presence of different conduction processes. An attempt has been made to interpret the pressure-induced effect in the transport properties of these glasses considering the possible presence of both thermally activated conduction in the extended states and hopping process in the localized tail states. However, the interpretation of the transport data is not straightforward and the pressure dependence of the thermoelectric power will be needed to complete the picture. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Origin of carrier-type reversal in Pb-Ge-Se glasses: A detailed thermal, electrical, and structural study

A long-standing and important problem in glass science has been carrier-type reversal (CTR) in semiconducting glasses. This phenomenon is exhibited by Pb-Ge-Se glasses also. It has been addressed here by carrying out detailed electrical, thermal, and spectroscopic investigations. PbxGe42-xSe58 (x = 0-20) glasses were prepared by a two stage melt-quenching process and characterized using x-ray diffraction, high-resolution electron microscropy, and energy dispersive analysis of x-rays. Thermoelectric power and high-pressure electrical resistivity have been measured. IR, Raman, and X-ray adsorption near edge structure spectroscopies have been used for examining the glass structures as well as differential scanning calorimetry (DSC) for studying the thermal properties. A structural model based on the chemical nature of the constituents has been proposed to account for the observed properties of these glasses. Effect of Pb incorporation on local structures and qualitative consequences on the energy band structures of Ge-Se glasses has been considered. The p -->n transition has been attributed to the energetic disposition of the sp(3)d(2) band of Pb atoms, which is located closely above the lone pair band of selenium. This feature makes Pb unique in the context of p -->n transition of chalcogenide glasses. The model can be extended successfully to account for the CTR behavior observed in Bi containing chalcogenide glasses also.

Structural, thermal, and electrical properties of CrSi2

Stoichiometric CrSi2 was prepared by arc melting and compacted by uniaxial hot pressing for property measurements. The crystal structure of CrSi2 was investigated using the powder x-ray diffraction method. From the Rietveld refinement, the lattice parameters were found to be a = 4.427 57 (7) and c = 6.368 04 (11) Å, respectively. The thermal expansion measurement revealed an anisotropic expansion in the temperature range from room temperature 800 K with αa = 14.58×10−6/K, αc = 7.51×10−6/K, and αV = 12.05×10−6/K. The volumetric thermal expansion coefficient shows an anomalous decrease in the temperature range of 450–600 K. The measured electrical resistivity ρ and thermoelectric power S have similar trends with a maxima around 550 K. Thermal conductivity measurements show a monotonic decrease with increasing temperature from a room temperature value of 10 W m−1 K−1. The ZT values increase with temperature and have a maximum value of 0.18 in the temperature range studied. An analysis of the electronic band structure is provided.

Band structure and transport properties of simple cubic tellurium-base alloys

The electrical transport properties and lattice spacings of simple cubic Te-Au, Te-Au-Fe, and Te-Au-Mn alloys, prepared by rapid quenching from the liquid state, hove been measured and correlated with a proposed bond structure. The variations of superconducting transition temperature, absolute thermoelectric power, and lattice spacing with Te concentration all showed related anomalies in the binary Te-Au alloys. The unusual behavior of these properties has been interpreted by using nearly free electron theory to predict the effect of the second Brillouin zone boundary on the area of the Fermi surface, and the electronic density of states. The behavior of the superconducting transition temperature and the lattice parameter as Fe and Mn ore added further supports the proposed interpretation as well as providing information on the existence of localized magnetic states in the ternary alloys. In addition, it was found that a very distinct bond structure effect on the transition temperatures of the Te-Au-Fe alloys could be identified.

The influence of a grain boundary on the thermal transport properties of bulk, melt-processed Y-Ba-Cu-O

We report the dependence of thermal conductivity, thermoelectric power and electrical resistivity on temperature for a bulk, large grain melt-processed Y-Ba-Cu-O (YBCO) high temperature superconductor (HTS) containing two grains separated by a well-defined grain boundary. Transport measurements at temperatures between 10 and 300 K were carried out both within one single grain (intra-granular properties) and across the grain boundary (inter-granular properties). The influence of an applied external magnetic field of up to 8 T on the measured sample properties was also investigated. The presence of the grain boundary is found to affect strongly the electrical resistivity of the melt-processed bulk sample, but has almost no effect on its thermoelectric power and thermal conductivity, within experimental error. The results of this study provide direct evidence that the heat flow in multi-granular melt-processed YBCO bulk samples should be virtually unaffected by the presence of grain boundaries in the material. © 2013 IOP Publishing Ltd.

Magnetotransport study of MgB2 superconductor

Precise magnetotransport studies of heat and charge carriers in polycrystalline MgB2 show that magnetic fields up to 8 T remarkably influence electrical resistivity, thermoelectric power and thermal conductivity. The superconducting transition temperature shifts from 39 K to 19 K at 8 T as observed on electric signals. The temperature transition width is weakly broadened. Electron and phonon contributions to the thermal conductivity are separated and discussed. The Debye temperature calculated from a phonon drag thermoelectric power component is inconsistent with values derived through other effects.

Magneto-transport study of Nb-doped Bi/Pb2223 superconductor

The magneto-transport properties of Bi1.5Pb0.4Nb0.1Sr2Ca2Cu 3O10-x polycrystalline, superconducting ceramic are reported. The material was found to be chemically homogeneous and partially textured. The mixed state properties were investigated by measuring the electrical resistivity, longitudinal and transverse (Nernst effect) thermoelectric power, and thermal conductivity. The magnetization and AC susceptibility measurements were also performed. The variation of these characteristics for magnetic fields up to 5 T are discussed and compared to those of the zero field case. The transport entropy and thermal Hall angle are extracted and quantitatively compared to previously reported data of closely related systems. © 2003 Elsevier Science B.V. All rights reserved.

A new combined joules supercritical rankine cycle exergetic analysis and optimization

The application of a supercritical Rankine cycle in combined cycles does not happen in today’s thermoelectric power stations. Nevertheless, the most recent development in gas turbines, that allows a high efficiency and high exhaust gases temperatures, and the improvement of high pressure and temperature alloys, makes this cycle possible. This study’s intent is to prove the viability of this combined cycle, since it can break the 60% efficiency barrier, which is the plafond in actual power stations. To attain this target, several configurations for this cycle have been simulated, optimized and analyzed [1]. The simulations were done with the computational program IPSEpro [2] and the optimizations were effectuated with software developed for the effect, using the DFP method [3]. In parallel with the optimization that claims the cycle’s efficiency maximization, an exergetic analysis was also made [4] to all the cycle components. In opposite to what happens in subcritical combined cycles, it was demonstrated that in supercritical combined cycles the higher efficiency takes place with a single steam pressure in the heat recovery steam generator (HRSG).

Pressure dependence of superconductivity in amorphous Ni x Zr 100-x alloys

Pressure variations of the superconducting transition temperature Ic of a series of amorphous NixZr 1 OO-x alloys have been studied under quasmydrostatic pressures upto 8 G Pa. For amorphous samples having Ni-concentration less than 40%, i)Tc/dP is positive in sign and it decreases non linearly with increase in I. whereasdTcldP is negative in sign for Ni concentration of 45%. Comparison with the Hall coefficient (I) and the thermoelectric power (2) results for the same amorphous alloys leads to the conclusion that s-d hybridization nature of the d-band (Nil plays a central role in the sign reversal behaviour. Application of pressures greater than 2 G Pa to Ni20ZrgO led to the formation of a new phase, w-Zr. which retains its form after the pressure is released.

Transparent p-AgCoO2/n-ZnO diode heterojunction fabricated by pulsed laser deposition

Transparent diode heterojunction on ITO coated glass substrates was fabricated using p-type AgCoO2 and n-type ZnO films by pulsed laser deposition (PLD). The PLD of AgCoO2 thin films was carried out using the pelletized sintered target of AgCoO2 powder, which was synthesized in-house by the hydrothermal process. The band gap of these thin films was found to be ~3.89 eV and they had transmission of~55% in the visible spectral region. Although Hall measurements could only indicate mixed carrier type conduction but thermoelectric power measurements of Seebeck coefficient confirmed the p-type conductivity of the grown AgCoO2 films. The PLD grown ZnO films showed a band gap of ~3.28 eV, an average optical transmission of ~85% and n-type carrier density of~4.6×1019 cm− 3. The junction between p-AgCoO2 and n-ZnO was found to be rectifying. The ratio of forward current to the reverse current was about 7 at 1.5 V. The diode ideality factor was much greater than 2.