In-doped multifilled n-type skutterudites with ZT=1.8

In this paper we maximize the thermoelectric (TE) figure of merit, ZT, of n-type skutterudites, (In,Sr,Ba,Yb)(y)Co4Sb12, via three different routes: (i) find the optimum fraction of In as fourth filler (ii) check the influence of powder particle, grain, and crystallite size on the TE properties and (iii) check thermal stability. Filled n-type (Sr, Ba, Yb)(y)Co4Sb12 was mixed in three different proportions with In0.4Co4Sb12, ball milled (regular or high-energy (HB) ball milling) and hot-pressed. Particle size analyses and SEM pictures of the broken surfaces of the hot pressed samples document that only HB produces uniform particles/grains with average crystallite sizes similar to 100 nm, proven by transmission electron microscopy. X-ray Rietveld refinements combined with EDX indicate that in all cases indium entered the icosahedral voids of the skutterudite. Temperature dependent physical properties of all three regularly ball-milled samples show that increasing In-content infers an increasing electrical resistivity, increasing Seebeck coefficient but a decreasing total thermal conductivity. Although ZT (823 K) is in the same range as for the sample without In, the ZT values in the whole temperature range are higher and consequently the TE-conversion efficiency, eta is at least 10% higher. Annealing the samples at 600 degrees C for three days shows minor changes in structure and thermoelectric properties, indicating TE stability. The HB sample, due to uniformly small particles, equally sized grains and crystallites, exhibits a high power factor (4.4 mW/m K-2 at 730 K) and a very low thermal conductivity leading to an outstanding high ZT = 1.8 at 823 K (eta(max) = 17.5%). (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thermal conductivity of beta-FeSi2/Si endogenous composites formed by the eutectoid decomposition of alpha-Fe2Si5

Thermoelectric properties of semiconducting beta-FeSi2 containing a homogeneous distribution of Si secondary phase have been studied. The synthesis was carried out using arc melting followed by the densification by uniaxial hot pressing. Endogenous beta-FeSi2/Si composites were produced by the eutectoid decomposition of high-temperature alpha-Fe2Si5 phase. The aging heat treatments have been carried out at various temperatures below the equilibrium eutectoid temperature for various durations in order to tune the size of the eutectoid product. Thermal properties of the samples were studied in the temperature range of 100-350 A degrees C. The microstructural investigations support the fact that the finest microstructure generated through the eutectoid decomposition of the alpha-Fe2Si5 metastable phase is responsible of the phonon scattering. The results suggest an opportunity to produce bulk iron silicide alloys with reduced thermal conductivity in order to enhance its thermoelectric performance.

Fly ash cenospheres as reinforcement in different polymer composites - a comparative study of physical and mechanical properties

The work reports the preparation of fly ash cenospheres bearing polymer composites, using various polymer matrix materials namely, low density polyethylene, high density polyethylene, polystyrene and polymethylmethacrylate followed by evaluation of properties. The composites are synthesized by including about 18% by weight fly ash cenospheres, into various polymer matrices using brabender facility in the temperature range 120-160 degrees C and at a mixing pressure of 50 MPa. Subsequently, they are cast into sheets through compression moulding. The test samples, made from the sheets, are characterized for physical as well as mechanical properties such as density, hardness, compression strength, impact response, wear and friction. The investigation reveals that the addition of fly ash cenospheres to various polymer matrices results in reduction of density. Further, improvements in the slide wear resistance and decrease in the co-efficient of friction values are noticed. As for interpreting the slide wear data, recourse to examination under scanning electron microscope is made in this paper. As regards the mechanical properties, hardness increases while the compression strength and impact energy decreases with inclusion of cenospheres in all the four types of samples investigated.

Synthesis and characterization of magnetic and conductive nickel ferrite-polyaniline nanocomposites

Conducting polymer/ferrite nanocomposites with an organized structure provide a new functional hybrid between organic and inorganic materials. The most popular among the conductive polymers is the polyaniline due to its wide application in different fields. In the present work nickel ferrite nanoparticles were prepared by sol-gel citrate-nitrate method. Polyaniline/nickel ferrite nanocomposites were synthesized by a simple general and inexpensive in-situ polymerization in the presence of nickel ferrite nanoparticles. The effects of nickel ferrite nanoparticles on the DC-electrical and magnetic properties of polyaniline were investigated. The structural, morphological and thermal stability of nanocomposites were characterized by X-ray diffraction, FTIR, scanning electron micrograph and TGA. The DC conductivity of polyaniline/nickel ferrite nanocomposites have been measured as a function of temperature in the range of 80K to 300K. The magnetic properties of the nanocomposites were measured using vibrating sample magnetometer in the temperature range 300-10K up to 30 kOe magnetic field.

Tuning of dielectric, pyroelectric and ferroelectric properties of 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) ceramic by internal clamping

This study systematically investigates the phenomenon of internal clamping in ferroelectric materials through the formation of glass-ceramic composites. Lead-free 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) (BNT-BT-ST) bulk ferroelectric ceramic was selected for the course of investigation. 3BaO - 3TiO(2) - B2O3 (BTBO) glass was then incorporated systematically to create sintered samples containing 0%, 2%, 4% and 6% glass (by weight). Upon glass induction features like remnant polarization, saturation polarization, hysteresis losses and coercive field could be varied as a function of glass content. Such effects were observed to benefit derived applications like enhanced energy storage density similar to 174 k J/m(3) to similar to 203 k J/m(3) and pyroelectric coefficient 5.7x10(-4) Cm-2K-1 to 6.8x10(-4) Cm-2K-1 by incorporation of 4% glass. Additionally, BNT-BT-ST depolarization temperature decreased from 457K to 431K by addition of 4% glass content. Glass incorporation could systematically increases diffuse phase transition and relaxor behavior temperature range from 70 K to 81K and 20K to 34 K, respectively when 6% and 4% glass content is added which indicates addition of glass provides better temperature stability. The most promising feature was observed to be that of dielectric response tuning. It can be also used to control (to an extent) the dielectric behavior of the host ceramic. Dielectric permittivity and losses decreased from 1278 to 705 and 0.109 to 0.107 for 6% glass, at room temperature. However this reduction in dielectric constant and loss increases pyroelectric figures of merit (FOMs) for high voltage responsivity (F-v) high detectivity (F-d) and energy harvesting (F-e) from 0.018 to 0.037 m(2)C(-1), 5.89 to 8.85 mu Pa-1/2 and 28.71 to 61.55 Jm(-3)K(-2), respectively for 4% added ceramic-glass at room temperature. Such findings can have huge implications in the field of tailoring ferroelectric response for application specific requirements. (C) 2015 Author(s).

Exciton-phonon scattering and nonradiative relaxation of excited carriers in hydrothermally synthesized CdTe quantum dots

Naturally formed CdTe/CdS core/shell quantum dot (QD) structures in the presence of surface stabilizing agents have been synthesized by a hydrothermal method. Size and temperature dependent photoluminescence (PL) spectra have been investigated to understand the exciton-phonon interaction, and radiative and nonradiative relaxation of carriers in these QDs. The PL of these aqueous CdTe QDs (3.0-4.8 nm) has been studied in the temperature range 15-300 K. The strength of the exciton-LO-phonon coupling, as reflected in the Huang-Rhys parameter `S' is found to increase from 1.13 to 1.51 with the QD size varying from 4.8 to 3.0 nm. The PL linewidth (FWHM) increases with increase in temperature and is found to have a maximum in the case of QDs of 3.0 nm in size, where the exciton-acoustic phonon coupling coefficient is enhanced to 51 mu eV K-1, compared to the bulk value of 0.72 mu eV K-1. To understand the nonradiative processes, which affect the relaxation of carriers, the integrated PL intensity is observed as a function of temperature. The integrated PL intensity remains constant until 50 K for relatively large QDs (3.9-4.8 nm) beyond which a thermally activated process takes over. Below 150 K, a small activation energy, 45-19 meV, is found to be responsible for the quenching of the PL. Above 150 K, the thermal escape from the dot assisted by scattering with multiple longitudinal optical (LO) phonons is the main mechanism for the fast quenching of the PL. Besides this high temperature quenching, interestingly for relatively smaller size QDs (3.4-3.0 nm), the PL intensity enhances as the temperature increases up to 90-130 K, which is attributed to the emission of carriers from interface/trap states having an activation energy in the range of 6-13 meV.

Neutron powder diffraction study of Ba3ZnRu2-xIrxO9 (x=0, 1, 2) with 6H-type perovskite structure

The triple perovskites Ba3ZnRu2-xIrxO9 with x = 0, 1, and 2 are insulating compounds in which Ru(Ir) cations form a dimer state. Polycrystalline samples of these materials were studied using neutron powder diffraction (NPD) at 10 and 295 K. No structural transition nor evidence of long range magnetic order was observed within the investigated temperature range. The results from structural refinements of the NPD data and its polyhedral analysis are presented, and discussed as a function of Ru/Ir content. (C) 2015 Elsevier Masson SAS. All rights reserved.

Solution processible Cu2SnS3 thin films for cost effective photovoltaics: Characterization

Thin films of Cu2SnS3 (CTS) were deposited by the facile solution processed sol-gel route followed by a low-temperature annealing. The Cu-Sn-thiourea complex formation was analysed using Fourier Transform Infrared spectrophotometer (FTIR). The various phase transformations and the deposition temperature range for the initial precursor solution was determined using Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC). X-Ray Diffraction (XRD) studies revealed the tetragonal phase formation of the CTS annealed films. Raman spectroscopy studies further confirmed the tetragonal phase formation and the absence of any deterioratory secondary phases. The morphological investigations and compositional analysis of the films were determined using Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) respectively. Atomic Force Microscopy (AFM) was used to estimate the surface roughness of 1.3 nm. The absorption coefficient was found to be 10(4) cm(-1) and bandgap 1.3 eV which qualifies CTS to be a potential candidate for photovoltaic applications. The refractive index, extinction coefficient and relative permittivity of the film were measured by Spectroscopic ellipsometry. Hall effect measurements, indicated the p type nature of the films with a hole concentration of 2 x 10(18) cm(-3), electrical conductivity of 9 S/cm and a hole mobility of 29 cm(2)/V. The properties of CTS as deduced from the current study, present CTS as a potential absorber layer material for thin film solar cells. (C) 2015 Elsevier B.V. All rights reserved.

Thermal, magnetic and electrical properties of Tb1-xDyxMnO3 multiferroics

A series of multiferroic materials with the compositional formula, Tb1 - xDyxMnO3 (where x=0, 0.1, 0.2, 0.3 and 0.4) were prepared by the sol gel method. After characterizing the samples structurally, a systematic investigation of specific heat, magnetization and dielectric properties over the temperature range, 4-300 K, was undertaken. Based on these studies, it was found that all the samples exhibit a transition at 40 K and the observed behavior may be attributed to the ordering of Mn3+ ions. Further, all the five samples are found to exhibit a ferroelectric transition in the temperature range 20-24 K. Finally, yet another transition was also exhibited by all the samples at temperatures below 10 K and is attributed to the antiferromagnetic (AF) ordering of rare-earth ionic moments. The magnetic entropy of all the samples was also computed with the help of their heat capacity data. (C) 2015 Elsevier B.V. All rights reserved.

Experimental solubilities of two lipid derivatives in supercritical carbon dioxide and new correlations based on activity coefficient models

The solubilities of two lipid derivatives, geranyl butyrate and 10-undecen-1-ol, in SCCO2 (supercritical carbon dioxide) were measured at different operating conditions of temperature (308.15 to 333.15 K) and pressure (10 to 18 MPa). The solubilities (in mole fraction) ranged from 2.1 x 10(-3) to 23.2 x 10(-3) for geranyl butyrate and 2.2 x 10(-3) to 25.0 x 10(-3) for 10-undecen-1-ol, respectively. The solubility data showed a retrograde behavior in the pressure and temperature range investigated. Various combinations of association and solution theory along with different activity coefficient models were developed. The experimental data for the solubilities of 21 liquid solutes along with geranyl butyrate and 10-undecen-1-ol were correlated using both the newly derived models and the existing models. The average deviation of the correlation of the new models was below 15%.

Thermoelectric Properties of In-Doped Cu2ZnGeSe4

Recently, much research has been focused on finding new thermoelectric materials. Cu-based quaternary chalcogenides that belong to A(2)BCD(4) (A = Cu; B = Zn, Cd; C = Sn, Ge; D = S, Se, Te) are wide band gap materials and one of the potential thermoelectric materials due to their complex crystal structures. In this study, In-doped quaternary compounds Cu2ZnGe1-xInxSe4 (x = 0, 0.025, 0.05, 0.075, 0.1) were prepared by a solid state synthesis method. Powder x-ray diffraction patterns of all the samples showed a tetragonal crystal structure (space group I-42m) of the main phase with a trace amount of impurity phases, which was further confirmed by Rietveld analysis. The elemental composition of all the samples showed a slight deviation from the nominal composition with the presence of secondary phases. All the transport properties were measured in the temperature range 373-673 K. The electrical resistivity of all the samples initially decreased up to similar to 470 K and then increased with increase in temperature upto 673 K, indicating the transition from semiconducting to metallic behavior. Positive Seebeck coefficients for all the samples revealed that holes are the majority carriers in the entire temperature range. The substitution of In3+ on Ge4+ introduces holes and results in the decrease of resistivity as well as the Seebeck coefficient, thereby leading to the optimization of the power factor. The lattice thermal conductivity of all the samples decreased with increasing temperature, indicating the presence of phonon-phonon scattering. As a result, the thermoelectric figure of merit (zT) of the doped sample showed an increase as compared to the undoped compound.

Simultaneous enhancement of electrical conductivity and thermopower in Bi2S3 under hydrostatic pressure

The inverse coupled dependence of electrical conductivity and thermopower on carrier concentration presents a big challenge in achieving a high figure of merit. However, the simultaneous enhancement of electrical conductivity and thermopower can be realized in practice by carefully engineering the electronic band structure. Here by taking the example of Bi2S3, we report a simultaneous increase in both electrical conductivity and thermopower under hydrostatic pressure. Application of hydrostatic pressure enables tuning of electronic structure in such a way that the conductivity effective mass decreases and the density of states effective mass increases. This dependence of effective masses leads to simultaneous enhancement in electrical conductivity and thermopower under n-type doping leading to a huge improvement in the power factor. Also lattice thermal conductivity exhibits very weak pressure dependence in the low pressure range. The large power factor together with low lattice thermal conductivity results in a high ZT value of 1.1 under n-type doping, which is nearly two times higher than the previously reported value. Hence, this pressure-tuned behaviour can enable the development of efficient thermoelectric devices in the moderate to high temperature range. We further demonstrate that similar enhancement can be observed by generating chemical pressure by doping Bi2S3 with smaller iso-electronic elements such as Sb at Bi sites, which can be achieved experimentally.

Thermoelectric properties of indium doped Cu2CdSnSe4

Recently, research in copper-based quaternary chalcogenide materials has been found to be interesting for the study of thermoelectric properties because of their low thermal conductivity due to complex crystal structures. In the present work, stoichiometric quaternary chalcogenide compounds Cu2CdSn1-xInxSe4(x = 0, 0.025, 0.05, 0.1) were prepared by solid state synthesis. The powder X-ray diffraction patterns of all the samples showed a tetragonal crystal structure with the space group I (4) over bar 2m of the main phase. In addition to this phase, a small amount of impurity phase CdSe was present in all the samples, as confirmed by Rietveld analysis. The elemental composition of all the samples characterized by an Electron Probe Micro Analyzer showed a slight deviation from the nominal composition. The transport properties were measured in the temperature range of 350 K-723 K. The positive Seebeck coefficient of all the compounds indicate that the majority carriers are holes. The Seebeck coefficient and electrical resistivity did not follow the trend in the expected manner with In doping, which could be influenced by the presence of the impurity phases. The total thermal conductivity of all the samples was dominated by the lattice thermal conductivity, while the electronic contribution was very small due to the low carrier contribution. A lattice thermal conductivity decrease with an increase of temperature indicates the dominance of phonon-phonon scattering at higher temperatures. The maximum figure of merit zT = 0.30 at 723 K was obtained for the compound Cu2CdSn0.9In0.1Se4. (C) 2016 Elsevier Ltd. All rights reserved.