Detection of the quadruple point in the CuSO4·5H2O and BaCl2·2H2O systems: effect of experimental parameters

The effects of sample mass, particle size, and furnace heating rate were studied for the detection of the quadruple point in the CuSO₄·5H₂O system using the simultaneous differential thermal analysis—electrical conductivity (DTA—EC) technique. As the sample mass decreased, both the DTA and EC peak amplitudes decreased. Increasing the furnace heating rate caused an increase in the peak splitting for the first DTA peak. In the case of particle size, an optimum size of about 80 mesh was found to give a maximum in the EC curve peak. The simultaneous DTA—EC curves for BaCl₂·2H₂O are also given.     

Nanoporous alumina (γ- and α-phase) gel cast thick film for the development of trace moisture sensor

In this study, erbia (Er₂O₃)-doped Bi₂O₃ ceramics were prepared from sol–gel derived nanocrystalline powders. The morphological properties were investigated by scanning electron microscopy. X-ray diffraction (XRD) analysis was carried out in order to characterize the phase and crystal structure of the powder samples. Temperature dependent electrical properties were determined by thermogravimetry/differential thermal analyzer (TG/DTA) and 4-point probe techniques. The stable fluorite face centered cubic δ-type phase was observed at room temperature from the XRD result, which was supported by the DTA and temperature dependent electrical conductivity measurements. Electrical conductivity results indicate that there is a transition approximately at 650 °C, which can be attributed to an order–disorder transition (ODT). The activation energy values obtained from the Arrhenius approach for heating and cooling process were presented. Two regimes, corresponding to high temperature region (HTR) and low temperature region (LTR), were observed. As a result of morphological changes during the ODT, the electrical conductivity modifies and the activation energies are different for studied sample at HTR and LTR.     

Electrical conductivity—differential thermal analysis measurements on some MnHgI4 complexes

The electrical conductivity (EC) and differential thermal analysis (DTA) curves of M_nHgI₄ complexes (M = Ag¹⁺, Cu¹⁺, Hg₂²⁺, Tl¹⁺ and Pb²⁺) and HgI₂ and AgI are reported. The EC—DTA curves were obtained for each of the following heating—cooling modes: (a) initial heating; (b) cooling; and (c) reheating. Each set of curves is discussed. The effect of sample history was also studied.     

MeV Si ions bombardments effects on thermoelectric properties of SiO2/SiO2+Ge nanolayers

The performance of the thermoelectric materials and devices is shown by a dimensionless figure of merit, ZT=S²σT/K, where S is the Seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature and K is the thermal conductivity. ZT can be increased by increasing S, increasing σ, or decreasing K. We have prepared the thermoelectric generator device of SiO₂/SiO₂+Ge multilayer superlattice films using the ion beam assisted deposition (IBAD). The 5 MeV Si ion bombardments have been performed using the AAMU Pelletron ion beam accelerator at five different fluences to make quantum structures (nanodots and/or nanoclusters) in the multilayer superlattice thin films to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric generator devices before and after MeV Si ions bombardments at the different fluences we have measured the cross-plane Seebeck coefficient, the cross-plane electrical conductivity, and the cross-plane thermal conductivity, Raman spectra to get some information about the sample structure and bond structures among the used elements in the superlattice thin film systems.     

Preparation and thermoelectric properties of AgPbmSbSem+2 materials

Hydrothermally synthesized AgPb_mSbSe_m+2 (m=10, 12, 16, 18) nanoparticles with diameters of 20-50 nm were compacted by pressureless sintering. The Seebeck coefficient and electrical conductivity of the samples were measured from room temperature up to ∼750 K. The samples show large and positive values of the Seebeck coefficient and moderate electrical conductivity. The thermoelectric properties of Ag_xPb₁₈SbSe₂₀ (x=0.8, 0.85) and AgPb₁₈SbSe_20−yTe_y (y=1, 3) samples have also been studied. It has been found that Ag_0.85Pb₁₈SbSe₂₀ sample has a higher thermoelectric power factor. A significant difference in thermoelectric properties has also been observed for the AgPb₁₈SbSe₂₀ samples prepared with pressureless sintering and spark plasma sintering.     

Structural behavior and thermoelectric properties of the brownmillerite system Ca2(ZnxFe2−x)O5

The Ca₂(Zn_xFe_2−x)O₅ series was synthesized and characterized to determine the influence of zinc dopant on the brownmillerite structure for thermoelectric applications. All single-phase compounds exhibited Pnma symmetry at room temperature up to the solubility limit at x=0.10. High-temperature X-ray powder diffraction was used to show that the nature of the Pnma-Imma(0 0 γ)s00 transition in Ca₂Fe₂O₅ is modified by the presence of zinc. While the Zn-free composition transitions to an incommensurate phase, the Zn-containing phases transition instead to a commensurate phase, Imma(0 0 γ)s00 with γ=1/2. Both the Néel temperature and the onset temperature of the Pnma-Imma(0 0 γ)s00 phase transition decreased with increasing zinc concentration. Rietveld analysis of the in situ diffraction pattern for the x=0 sample at 1300 °C demonstrates that the structure contains statistically disordered chain orientations as described by space group Imma. Thermoelectric properties were analyzed in air from 100 to 800 °C. The positive Seebeck coefficient revealed hole-type conduction for all compositions. Doped samples exhibited electrical conductivities up to 3.4 S/cm and thermal conductivity of 1.5 W/mK. Transport analysis revealed thermally activated mobility consistent with polaron conduction behavior for all compositions.     

Electrophysical properties of layered perovskites LnBaCo<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>5 + δ</Subscript> (Ln = Sm,Nd) for solid oxide fuel cells

The influence of doping with copper oxide on the phase composition, electric conductivity, and linear thermal expansion coefficient (LTEC) of SmBaCo₂O_{5 + δ} and NdBaCo₂O_{5 + δ} was studied. The sample homogeneity region has been determined with using XRD. The samples conductivity decreased as the dopant concentration increased. The character of the temperature dependence of conductivity changed at high copper contents. In a reductive atmosphere, the conductivity of the samples at first decreased and then remained constant. The linear thermal expansion coefficient decreased as the amount of the incorporated dopant increased.     

A new method of determining the thermal conductivities of energetic materials by microcalorimeter

A device of measuring the thermal conductivity of pellet of propellants and explosives has been constructed. A method and a calculation formula for determining the thermal conductivity of pellet of propellants and explosives under constant radial heat flow conditions by use of Joule effect is presented. Using this device and a microcalorimeter, type RD496-II, and two standard samples with known thermal conductivity, two instrument constant have been determined and the thermal conductivities of seven materials: plexiglass, teflon, DB propellant DB-2 (nitrocellulose(NC)/nitroglycerine(NG)/dinitrotoluene/dimethyl centralite/vaseline/PbO/CaCO₃, 59.6/25/8.8/3/1.2/1.2/1.2), DB propellant SQ(NC/NG/diethyl phthalate(DEP)/binder, 59/29/7/5), DB propellant RHN-149 (NC/NG/triacetin (TA)/binder-I, 52/25/8/15), DB propellant RHN-190 (NC/NG/TA/ binder-II, 52/26/7/15), 2, 4, 6-trinitrotoluene (TNT) at 298 K are measured. The results show that (1) the reproducibility of measurement for the heat (q) retained in investigated system after cutting the Joule current and the amount of heat flux through the wall of the investigated cylinder (Q _s) are less than 0.50% and within 0.10%, respectively; (2) the standard deviation of the thermal conductivity determined by using this method is less than 1.0%; (3) the values ofq, Q _s and internal radius of the cylinder are three principal factors affecting the magnitude of the thermal conductivity of these materials.     

Study on the ternary synergistic extraction of uranium/VI/ by chelating-chelating-neutral extractant

The synergic extraction of uranyl nitrate from chloroform media with 1-phenyl-3-methyl-4-benzoyl-pyrazonole-5 /PMBP/, tributylphosphate /TBP/ and thenoyltrifluorylacetone /TTA/ was studied. It was found that synergic effect occurs during the extraction of uranyl nitrate with the chloroform solution of PMBP-TTA-TBP. The formation of the ternary extracted complex UO₂AA'B was confirmed by the usual slope method. A method was proposed for the calculation of the ternary equilibrium constant which was evaluated to be 1gK₁₁₁=2.65. Also the binary synergic extractions of uranyl nitrate with PMBP-TBP and TTA-TBP were studied. The binary equilibrium constants were found to be 1gK₂₀₁=3.07 and 1gK₀₂₁=1.39, respectively. An attempt has been made to interpret the data mainly on the basis of statistical factor.     

Thermal anomaly in LiKSO4 crystals in the temperature range 300–800 K

Thermal analysis, DTA, TG, TMA and DSC were performed on LiKSO₄ in the temperature range 300 to 800 K, using a Heraeus TA 500 thermal analyser. The thermal expansion coefficients measured along the three fundamental crystallogrpahic axes, together with the specific heatC _p, show anomalous behaviour around the phase transition temperature of these crystals atT _c=705 K. Anisotropy in the thermal expansion coefficient as well as endothermic peaks aroundT _c were also observed, while no loss of weight was detected. The temperature-dependence of the thermal conductivity of LiKSO₄ crystals has been estimated, using the temperature-variation of the thermal diffusivity.     

Raman spectroscopy of powders: Effects of light absorption and scattering

New expressions are derived from Kubelka—Munk theory to describe the Raman intensities observed by back-scattering from powder samples. The equations relate the Raman intensity to the diffuse reflectance R_∞ of the sample for two cases: (i) for a series of samples having constant values of the scattering coefficient, s, but which vary in their values of the absorption coefficient, k; and (ii) for a series of samples having constant values of k, but differing in their values of s. The predicted intensity dependences are compared with the results of experiment.     

Thermoelectric properties of polycrystalline La1−xSrxCoO3

Thermoelectric properties of polycrystalline La_1−xSr_xCoO₃, where Sr²⁺ is substituted in La³⁺ site in perovskite-type LaCoO₃, have been investigated. Sr-doping increases the electrical conductivity (σ) of La_1−xSr_xCoO₃, and also decreases the Seebeck coefficient (S) for 0.01?x?0.40. A Hall coefficient measurement reveals that the increase in electrical conductivity arises from increases in both carrier concentration and the Hall mobility. The decrease in the Seebeck coefficient is caused by a decrease in carrier effective mass as well as increase in carrier concentration. The highest power factor (σS²) is 3.7×10⁻⁴ W m⁻¹ K⁻² at 250 K for x=0.10. The thermal conductivity (κ) is about 2 W m⁻¹ K⁻¹ at 300 K for 0?x?0.04, and increases for x?0.05 because of an increase in heat transport by conductive carrier. The thermoelectric properties of La_1−xSr_xCoO₃ are improved by Sr-doping, and the figure of merit (Z=σS² κ⁻¹) reaches 1.6×10⁻⁴ K⁻¹ for x=0.06 at 300 K (ZT=0.048). For heavily Sr-doped samples, the thermoelectric properties diminish mainly because of the decrease in the Seebeck coefficient and the increase in thermal conductivity.     

Influence of fluorine on thermal properties of lead oxyfluoride glass

Oxyfluoride glasses are the basic materials for obtaining transparent glass–ceramic (TGC) which can be used in a wide range of optoelectronics devices such as: amplifiers, up-conversion, telescopes, laser sources. Oxyfluoride TGC is obtained by the control heat treatment of the parent glass due to low phonon nanocrystalline phases. The oxyfluoride glasses from the sodium–lead–silica system were the object of investigation. The influence of fluoride content on the thermal properties of glasses was analyzed. Thermal characteristics of glasses like the transition temperature T _g, the temperature for the crystallization onset T _x, and the maximum crystallization temperature T _c, thermal stability parameter were determined by DTA/DSC method. The linear expansion coefficients of oxyfluoride glasses as a function of temperature were measured using a thermo-mechanical analyzer (TMA 7 Perkin-Elmer). The effect of crystallization on the thermal expansion coefficient and softening temperature T _s was found.     

Synthesis and characterization of La2Mo2O9 obtained from freeze-dried precursors

La₂Mo₂O₉ ceramics have been prepared from freeze-dried precursors and their properties compared to those of lantanum molybdate obtained by conventional solid state (SS) reaction. All materials have been characterized by X-ray diffraction, scanning electron microscopy and thermal analysis (TGA/DTA/DSC and dilatometry) to characterize the phase formation and phase transition. When the freeze-dried method was applied, the synthesis temperature required to obtain dense samples was much lower than that for powders obtained by SS reaction. The morphology and structure of the oxide particle are significantly dependent on the synthesis method. The grain size is smaller, whereas the density of sintered pellets is higher for the freeze-dried precursor powder when compared with the SS reaction method. Impedance spectroscopy was used to measure the electrical conductivity of La₂Mo₂O₉ from 548 to 1123 K, in air, and to characterize the blocking effects of grain boundaries.     

Anisotropic thermoelectric properties of Bi1.9Lu0.1Te2.7Se0.3 textured via spark plasma sintering

Spark plasma sintering method was applied to prepare bulk n-type Bi_1.9Lu_0.1Te_2.7Se_0.3 samples highly textured along the 001 direction parallel to the pressing direction. The texture development is confirmed by X-ray diffraction analysis and scanning electron microscopy. The grains in the textured samples form ordered lamellar structure and lamellar sheets lie in plane perpendicular to the pressing direction. The average grain size measured along the pressing direction is much less as compared to the average grain size measured in the perpendicular direction (∼50 nm against ∼400 nm). A strong anisotropy in the transport properties measured along directions parallel and perpendicular to the pressing direction within the 290 ÷ 650 K interval was found. The specific electrical resistivity increases and the thermal conductivity decreases for the parallel orientation as compared to these properties for the perpendicular orientation. The Seebeck coefficient for both orientations is almost equal. Increase of the electrical resistivity is stronger than decrease of the thermal conductivity resulting in almost three-fold enhancement of the thermoelectric figure-of-merit coefficient for the perpendicular orientation (∼0.68 against ∼0.24 at ∼420 K). The texturing effect can be attributed to (i) recovery of crystal structure anisotropy typical for the single crystal Bi₂Te₃-based alloys and (ii) grain boundary scattering of electrons and phonons. An onset of intrinsic conductivity observed above T_d ≈ 410 K results in appearance of maxima in the temperature dependences of the specific electrical resistivity, the Seebeck coefficient and the thermoelectric figure-of-merit coefficient and minimum in the temperature dependence of the total thermal conductivity. The intrinsic conductivity is harmful for the thermoelectric efficiency enhancement since thermal excitation of the electron-hole pairs reduces the Seebeck coefficient and increases the thermal conductivity.     

p-Type thermoelectric properties of the oxygen-deficient perovskite Ca2Fe2O5 in the brownmillerite structure

Brownmillerite calcium ferrite was synthesized in air at 1573 K and thermoelectric properties (direct current electrical conductivity σ, Seebeck coefficient α, thermal conductivity κ, thermal expansion α_L) were measured from 373 to 1050 K in air. Seebeck coefficient was positive over all temperatures indicating conduction by holes, and electrical properties were continuous through the Pnma-Imma phase transition. Based on the thermopower and conductivity activation energies as well as estimated mobility, polaron hopping conduction was found to dominate charge transport. The low electrical conductivity, <1 S/cm, limits the power factor (α²σ), and thus the figure of merit for thermoelectric applications. The thermal conductivity values of ∼2 W/mK and their similarity to Ruddlesden-Popper phase implies the potential of the alternating tetrahedral and octahedral layers to limit phonon propagation through brownmillerite structures. Bulk linear coefficient of thermal expansion (∼14×10⁻⁶ K⁻¹) was calculated from volume data based on high-temperature in situ X-ray powder diffraction, and shows the greatest expansion perpendicular to the alternating layers.     

Thermal characterisation of the non-stoichiometry and catalytic activity of BaxLn1−xCoO3 (Ln = La,Nd, Sm and Dy) compounds

The compounds Ba_xLn_1?xCoO₃ (Ln = La, Nd, Sm and Dy) were prepared by ceramic technique. They were characterised for oxygen non-stoichiometry using isothermal DTA under varying oxygen partial pressure and TG in air. Isothermal DTA was also employed to study the catalytic activity of the compounds towards CO oxidation. For a given compound, the oxygen deficiency increases with increasing temperature and decreasing oxygen partial pressure. For a given Ba_xLn_1?xCoO₃ series, in general barium-rich compounds were more oxygen deficient. Isothermal DTA study of CO oxidation over Ba_xLa_1?xCoO₃ compounds at 600 K suggested that the carbon monoxide takes up lattice-labile oxygen from the sample and is oxidised to CO₂, the percent CO conversion being higher for barium-rich samples.     

Transport coefficients of titanium-doped Sb2Te3 single crystals

Titanium-doped single crystals (c_Ti=0-2×10²⁰ atoms cm⁻³) were prepared from the elements Sb, Ti, and Te of 5 N purity by a modified Bridgman method. The obtained crystals were characterized by measurements of the temperature dependence of the electrical resistivity, Hall coefficient, Seebeck coefficient and thermal conductivity in the temperature range of 3-300 K. It was observed that with an increasing Ti content in the samples the electrical resistivity, the Hall coefficient and the Seebeck coefficient increase. This means that the incorporation of Ti atoms into the Sb₂Te₃ crystal structure results in a decrease in the concentration of holes in the doped crystals. For the explanation of the observed effect a model of defects in the crystals is proposed. The data of the lattice thermal conductivity were fitted well assuming that phonons scatter on boundaries, point defects, charge carriers, and other phonons.     

Synthesis and evaluation of lead telluride/bismuth antimony telluride nanocomposites for thermoelectric applications

Heterogeneous nanocomposites of p-type bismuth antimony telluride (Bi_2−xSb_xTe₃) with lead telluride (PbTe) nanoinclusions have been prepared by an incipient wetness impregnation approach. The Seebeck coefficient, electrical resistivity, thermal conductivity and Hall coefficient were measured from 80 to 380 K in order to investigate the influence of PbTe nanoparticles on the thermoelectric performance of nanocomposites. The Seebeck coefficients and electrical resistivities of nanocomposites decrease with increasing PbTe nanoparticle concentration due to an increased hole concentration. The lattice thermal conductivity decreases with the addition of PbTe nanoparticles but the total thermal conductivity increases due to the increased electronic thermal conductivity. We conclude that the presence of nanosized PbTe in the bulk Bi_2−xSb_xTe₃ matrix results in a collateral doping effect, which dominates transport properties. This study underscores the need for immiscible systems to achieve the decreased thermal transport properties possible from nanostructuring without compromising the electronic properties.     

Propriétés electriques et magnétiques des solutions solides LaxEu1−xB6

The electric and magnetic properties of the La_xEu_1?xB₆ solid solutions have been investigated. A sharp evolution from semiconducting to metallic character is observed between x = 0 and x = 0.01. Evolution with x of the atomic volume, conductivity, Seebeck coefficient and magnetic properties are discussed in terms of a band model in which the conduction band is the 5d or 6s band of the rare-earth-atom sublattice. It is argued that chemical inhomogeneities produce a finite range of compositions over which the Seebeck coefficient changes from metallic character toward small-polaron character with decreasing x, whereas the metal-to-semiconductor transition appears more sharply defined.