Thermoelectric properties of a Mn substituted synthetic tetrahedrite

Tetrahedrite compounds Cu12-xMnxSb4S13 (0 <= x <= 1.8) were prepared by solid state synthesis. A detailed crystal structure analysis of Cu10.6Mn1.4Sb4S13 was performed by single crystal X-ray diffraction (XRD) at 100, 200 and 300 K confirming the noncentrosymmetric structure (space group I (4) over bar 3m) of a tetrahedrite. The large atomic displacement parameter of the Cu2 atoms was described by splitting the 12e site into a partially and randomly occupied 24g site (Cu22) in addition to the regular 12e site (Cu21), suggesting a mix of dynamic and static off-plane Cu2 atom disorder. Rietveld powder XRD pattern and electron probe microanalysis revealed that all the Mn substituted samples showed a single tetrahedrite phase. The electrical resistivity increased with increasing Mn due to substitution of Mn2+ at the Cu1+ site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. Even though the thermal conductivity decreased as a function of increasing Mn, the thermoelectric figure of merit ZT decreased, because the decrease of the power factor is stronger than the decrease of the thermal conductivity. The maximum ZT = 0.76 at 623 K is obtained for Cu12Sb4S13. The coefficient of thermal expansion 13.5 +/- 0.1 x 10(-6) K-1 is obtained in the temperature range from 460 K to 670 K for Cu10.2Mn1.8Sb4S13. The Debye temperature, Theta(D) = 244 K for Cu10.2Mn1.8Sb4S13, was estimated from an evaluation of the elastic properties. The effective paramagnetic moment 7.45 mu(B)/f.u. for Cu10.2Mn1.8Sb4S13 is fairly consistent with a high spin 3d(5) ground state of Mn.

Thermoelectric properties of Co substituted synthetic tetrahedrite

Transition metal atom (Co) substituted synthetic tetrahedrite compounds Cu12-xCoxSb4S13 (x = 0, 0.5, 1.0, 1.5, 2.0) were prepared by solid state synthesis. X-Ray Diffraction (XRD) patterns revealed tetrahedrite as the main phase, whereas for the compounds with x = 0, 0.5 a trace of impurity phase Cu3SbS4 was observed. The surface morphology showed a large grain size with low porosity, which indicated appropriate compaction for the hot pressed samples. The phase purity, as monitored by Electron Probe Micro Analysis (EPMA) is in good agreement with the XRD data. The elemental composition for all the compounds almost matched with the nominal composition. The X-ray Photoelectron Spectroscopy (XPS) data showed that Cu existed in both +1 and +2 states, while Sb exhibited +3 oxidation states. Elastic modulus and hardness showed a systematic variation with increasing Co content. The electrical resistivity and Seebeck coefficient increased with increase in the doping content due to the decrease in the number of carriers caused by the substitution of Co2+ on the Cu1+ site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. A combined effect of resistivity and Seebeck coefficient leads to the maximum power factor of 1.76 mW m(-1) K-2 at 673 K for Cu11.5Co0.5Sb4S13. This could be due to the optimization in the carrier concentration by the partial substitution of Co2+ on both the Cu1+ as well as Cu2+ site at the same doping levels, which is also supported by the XPS data. The total thermal conductivity systematically decreased with increase of doping content as it is mainly influenced by the decrease of carrier thermal conductivity. The maximum thermoelectric figure of merit zT = 0.98 was obtained at 673 K for Cu11.5Co0.5Sb4S13. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

LDPE/carbon black conductive composites: Influence of radiation crosslinking on PTC and NTC properties

The electrical resistivity of low-density polyethylene/carbon black composites irradiated by Co-60 gamma-rays was investigated as a function of temperature. The experimental results obtained by scanning electron microscopy, solvent extraction techniques, and pressure-specific volume-temperature analysis techniques showed that the positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects of the composites were influenced by the irradiation dose, network forming (gel), and soluble fractions (Sol). The NTC effect was effectively eliminated when the radiation dose reached 400 kGy. The results showed that the elimination of the NTC effect was related to the difference in the thermal expansion of the gel and Sol regions. The thermal expansion of the sol played an important role in both increasing the PTC intensity and decreasing the NTC intensity at 400 kGy.

Studies on the PTC/NTC effect of carbon black filled low density polyethylene composites

The positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effect of carbon black (CB) filled low density polyethylene (LDPE) composites was studied using electrical resistivity spectra, DSC, tensile mechanical analysis (TMA) and small-angle X-ray scattering (SAXS) techniques. The three LDPEs used have a similar crystallinity and different melting index (MI). The experimental results indicate that the CB has no significant effect on the crystallinity and the long spacing of crystalline domains of LDPE. Based upon the TMA and dynamic elastic modulus spectra, it can be concluded that the PTC effect is related to the thermal expansion of the polymer matrix, and the NTC effect is caused by a decrease of the elastic modulus of the polymer at high temperatures. The NTC effect can be reduced by enhancing either the elastic modulus or the interaction between carbon black and matrix. (C) 1997 Elsevier Science Ltd.

Structural and electrical characterization of semiconducting barium-lead-titanate ceramics

BaTiO3 is usually doped to achieve the temperature stability required by device applications, as well as to obtain a large positive temperature coefficient anomaly of resistivity (PTCR). Uniform distribution of dopants among the submicron dielectric particles is the key for optimal control of grain size and microstructure to maintain a high reliability. The system Ba0.84Pb0.16TiO3 was synthesized from high purity BaCO3, TiO2, PbO oxide powders as raw materials. Sb2O3, MnSO4 and ZnO were used as dopants and Al2O3, TiO2 and SiO2 as grain growth controllers. Phase composition was analyzed by using XRD and the microstructure was investigated by SEM. EDS attached to SEM was used to analyze phase composition specially related to abnormal grain growth. Electrical resistivities were measured as a function of temperature and the PTCR effect characterized by an abrupt increase on resistivity.

1H NMR and a study of the anomalous temperature dependence of the 35Cl NQR frequencies in 2-chloro-3-pyridinol

A 35Cl NQR study of 2-chloro-3-pyridinol showed the presence of four NQR signals at 77 K. One of the lines showed a positive temperature coefficient of the NQR frequency. 1H NMR studies showed the presence of intramolecular hydrogen bonding, and the anomalous NQR temperature dependence has been explained in terms of Bayer and hydrogen bond effects. The room temperature x-ray structure and the low-temperature NQR data suggest the presence of a phase transition.

Varistors based on barium titanate-graphite-rubber composites

This paper describes the experimental and theoretical studies carried out on particulate composites consisting of BaTiO3, graphite, and rubber. It is shown that such composites exhibit a positive voltage coefficient of resistance beyond a certain voltage. A theoretical model developed to explain the observed V-R characteristics and their dependence on parameters of the composite like composition and grain size of the particles is also described. These composites seem to be useful as varistors with positive voltage coefficient of resistance and may find applications as voltage-regulating devices. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Dielectric properties of barium magnesiotitanate ceramics, BaMg6Ti6O19

Phase-pure samples of barium magnesiotitanate, BaMg6Ti6O19 (BMT) are prepared by the wet chemical `gel-carbonate' method wherein the formation of BMT is complete below 950 degrees C as a result of the reaction between nanoparticles of BaCO3, MgO and TiO2. BMT powders are sintered at 1350-1450 C to dense ceramics. Extensive melting is noticed when the bulk composition falls between 0.4MgTiO(3)+0.6BaTiO(3)) and (0.6MgTiO(3)+0.4BaTiO(3)) along the MgTiO3-BaTiO3 tie-line in BaO-MgO-TiO2, phase diagram. Dielectric properties of sintered (BMT) ceramics have been investigated which showed epsilon similar or equal to 39 at 2 GHz, quality factor Q >= 10,000 and positive temperature coefficient of dielectric constant around 370 ppm degrees C-1.

Thermoelectric properties of indium filled and germanium doped Co4Sb12 skutterudites

In-filled and Ge-doped Co4Sb12 skutterudites materials were synthesized by an induction melting process which was followed by annealing at 650 degrees C for 7 days. A structural, compositional, and morphological study was carried out by X-ray diffraction (XRD), electron probe micro analysis (EPMA), and scanning electron microscopy (SEM). The formation of a single skutterudite phase (delta-CoSb3) was confirmed by XRD and the composition of all the samples was verified by EPMA. The homogeneity and morphology of the samples was observed by potential Seebeck microprobe (PSM) and SEM, respectively. The PSM result confirmed the inhomogeneity of the samples. The temperature dependence of the Seebeck coefficient, electrical conductivity, and thermal conductivity were measured in the temperature range of 300-650 K. The samples of In0.16Co4Sb12-xGex (x = 0.05, 0.1, and 0.2) show a negative Seebeck coefficient confirming an n-type conductivity and the In0.16Co4Sb11.7Ge0.3 sample shows a positive Seebeck coefficient confirming a p-type conductivity. There was a change in the Seebeck coefficient from an n-type to a p-type at the doping concentration of x = 0.3 due to the excess Ge which increases in hole carrier concentration. Electrical conductivity decreases with an increase in Ge doping concentrations and with increases in temperature due to the bipolar effect. Thermal conductivity increases with an increase in carrier concentration and decreases when the temperature is increased. The highest ZT = 0.58 was achieved by In0.16Co4 Sb11.95Ge0.05 at 673K and In-filled and Ge-doped Co4Sb12 was not effective in improving the figure of merit. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3677982]

Lithium D-Isoascorbate Monohydrate, a New Nonlinear Optical Material

Single crystals of lithium D-isoascorbate monohydrate (LDAM), (C6H7O6Li center dot H2O), are grown by a solution growth method. The crystal structure of LDAM is solved using single crystal X-ray diffraction. The space group is orthorhombic P2(1)2(1)2(1) with four formula units per unit cell and lattice parameters a = 7.7836(3) angstrom, b = 8.7456(3) angstrom, and c = 11.0368(4) angstrom. Solubility of the material in water is determined thermogravimetrically and found to have a positive temperature coefficient of solubility. Large optical quality single crystals are subsequently grown from aqueous solution by a slow cooling method. The crystal has a bulky prismatic habit and among the prominent faces the c face appears as the only principal morphological face. The crystal exhibits a (010) cleavage. Dielectric spectroscopy reveals a nearly Debye type Cole-Cole behavior with anisotropy in relaxation. Optical transmission range is found to be from 300 to 1400 nm. The principal refractive indices of this biaxial crystal, measured using Brewster's angle method, at wavelengths 405, 543, and 632.8 nm, show high dispersion. The crystal is negative biaxial with 2V(z) = 107.8 degrees (405 nm) and belongs to the Hobden class 3. Theoretically generated type 1 and type 2 second order phase matching curves match very well with the experimental results. The second-order nonlinear coefficient d(14) was determined to be 7 x 10(-13) m/V. For the optimum phase matching direction (type 2), the second-order effective nonlinear coefficient and the walk off angle are determined to be 0.84 times d(14) and 3.5 degrees respectively. The crystal possesses high multiple surface damage thresholds of 18 GW/cm(2) and 8 GW/cm(2) at laser wavelengths 1064 and 532 nm, respectively.

Studies on lithium L-ascorbate dihydrate: An interesting chiral nonlinear optical crystal

Lithium L-Ascorbate dihydrate (LLA) is a new metal organic nonlinear optical crystal belonging to the saccharide family. Single crystals of LLA were grown from aqueous solution. Solubility of the crystal has a positive temperature coefficient facilitating growth by slow cooling. Rietveld refinement was used to confirm the phase formation. The crystal has prismatic habit with (010), (001) and (10-1) prominent faces. Thermal analysis shows that the crystal is stable up to 102 degrees C. Transmission spectrum of the crystal extends from 302 nm to 1600 nm. Dielectric spectroscopic analysis revealed Cole Cole behaviour and prominent piezoelectric resonance peaks were observed in the range of 100-200 kHz. Second harmonic generation (SHG) conversion efficiency of up to 2.56 times that of a phase matched KDP crystal was achieved when the (010) plate of LLA single crystal was rotated about the +ve c axis, by 9.4 degrees in the clockwise direction. We also observed SHG conical sections which were attributed to noncollinear phase matching. The observation of the third conical section suggests very high birefringence and large nonlinear coefficients. A detailed study of surface laser damage showed that the crystal has high multiple damage thresholds of 9.7 GW cm(-2) and 42 GW cm(-2) at 1064 nm and 532 nm radiation respectively. (C) 2012 Elsevier B.V. All rights reserved.

Riemann shock tube: 1D normal shocks in air, simulations and experiments

This paper presents numerical simulation of the evolution of one-dimensional normal shocks, their propagation, reflection and interaction in air using a single diaphragm Riemann shock tube and validate them using experimental results. Mathematical model is derived for one-dimensional compressible flow of viscous and conducting medium. Dimensionless form of the mathematical model is used to construct space-time finite element processes based on minimization of the space-time residual functional. The space-time local approximation functions for space-time p-version hierarchical finite elements are considered in higher order GRAPHICS] spaces that permit desired order of global differentiability of local approximations in space and time. The resulting algebraic systems from this approach yield unconditionally positive-definite coefficient matrices, hence ensure unique numerical solution. The evolution is computed for a space-time strip corresponding to a time increment Delta t and then time march to obtain the evolution up to any desired value of time. Numerical studies are designed using recently invented hand-driven shock tube (Reddy tube) parameters, high/low side density and pressure values, high- and low-pressure side shock tube lengths, so that numerically computed results can be compared with actual experimental measurements.

The effect of Cu addition on the thermoelectric properties of Cu2CdGeSe4

Recently, research in copper based quaternary chalcogenide materials has focused on the study of thermoelectric properties due to the complexity in the crystal structure. In the present work, stoichiometric quaternary chalcogenide compounds Cu2+xCd1-x,GeSe4 (x = 0, 0.025, 0.05, 0.075, 0.1, 0.125) 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-42m of the main phase, whereas the samples with x = 0 and x = 0.025 revealed the presence of an orthorhombic phase in addition to the main phase as confirmed by Rietveld analysis. The elemental composition of all the samples characterized by Electron Probe Micro Analyzer showed a slight deviation from the nominal composition. The transport properties were measured in the temperature range of 300 K-723 K. The electrical conductivity of all the samples increased with increasing Cu content due to the enhancement of the hole concentration caused by the substitution of Cd (divalent) by Cu (monovalent). The positive Seebeck coefficient of all the samples in the entire temperature ranges indicates that holes are the majority carriers. The Seebeck coefficient of all the samples decreased with increasing Cu content and showed a reverse trend to the electrical conductivity. The total thermal conductivity of all the samples decreased with increasing temperature which was dominated by the lattice contribution. The maximum figure of merit ZT = 0.42 at 723 K was obtained for the compound Cu2.1Cd0.9GeSe4. (C) 2014 Elsevier Ltd. All rights reserved.

Study of distribution, growth and reproduction polychaetes Nereidae in intertidal zone of Bandar Abbas and effect dominant species on white Indian shrimp brood stocks (Fenneropenaeus indicus)

Distribution of polychaetes worms Nereidae in intertidal zone of Bandar Abbass indicated that distribution rate of worms from the west to east for the reason status of seabed type, habitat and feeding substrate used to worms increased. Also investigation description that last-mentioned worms are belong to Nereididae family, Perinereis genus and species of Perinereis nuntia. By viewpoint seabed soil types experiments implement indicated Nereididae worms have higher survival with sandy clay loam soil texture. Statistical analysis showed positive relation coefficient correlation of Pearson between substrate type to frequency of worms and too substrate type with soil organic matter value (P<0.05). By viewpoint feeding also experiments with different feed treatment indicated that Nereid worms is Omnivore but in natural condition more utilized algae substrate special Entermorpha and survival rate had the worms last-mentioned in dietary treatments on this algae 93/3% different significant with other treatments (P<0.05). In this project pond-reared white Indian shrimp (Fenneropenaeus indicus) were used in four maturation and spawning trials lasting 60 days. one group of shrimps was fed a formulated pelleted special of broodstock diet only, a second group was fed squid meat diet; a third group of shrimps with mollusca (Solen vagina) meat diet and fourth group was fed polychaete worms Nereidae family, collected in intertidal zone of Bandar Abbass. Four types of dietary treatments (M1, M4) were given to separate batches that were run in three duplicate. Results of experiments demonstrate that more grew rate and maturation and spawning rate and we found that shrimps fed with polychaete worms have the best condition and then shrimps fed with solen. This is demonstrate furthermore environmental circumstance, endocrine hormone, types of feed important of maturation and spawning of shrimps and in polychaete worms used HUFA help to maturation ovarian in shrimp.