Thermodynamics of oxygen in liquid copper, lead and copper lead alloys

Solid oxide galvanic cells of the type Pt, Ni-NiO I Solid electrolyte ( Ometa,, Cermet. Pt were used to measure the activity coefficient of oxygen in liquid copper at 11 00 and 1 300eC, and in lead at 11 00'C. Similar cells were used to study the activity coefficient of oxygen in the whole range of Cu + Pb alloys at 1100'C and in lead-rich alloys at 900 and 750'C.The results obtained are discussed in terms of proposed solution models. An equation based on the formation of 'species' of the form M,O in solutions of oxygen in binary alloys is shown to fit the experimental data.

Thermodynamic study of oxygen in liquid lead tin alloys

The activity coefficients of oxygen in liquid lead-tin alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells Pt, Ni-NiO I Zr02 Solid electrolyte I 0 (Pb + Sn), Cermet, Pt Pt, Fe-FeO I Zr02 Solid electrolyte I O(Pb + Sn), Cermet, Pt Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys.The relative partial molar enthalpy and entropy of oxygen ?t 1 atom per cent in the alloys have been calculated from ttva variation of the activity coefficient with temperature. The addition of tin to an unsaturated solution of oxygen in lead is shown to decrease significantly both the partial molar enthalpy and entropy of oxygen. As the measurements were restricted to a narrow range between 750-1100'C in lead-rich alloys, however, the pronounced variation of the partial molar enthalpy of oxygen with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.

Study of embedded lead-tin nanoparticles in aluminum matrix

Nanoembedded lead-tin alloys in aluminum matrix were synthesized by rapid solidification processing. These melt-spun aluminum alloys were then investigated using XRD, EDX and TEM. The XRD study reveals that the melt-spun samples contain elemental aluminum, lead and tin. The TEM analysis shows that embedded particles in aluminium matrix have a distinct two-phase contrast of lead and tin. The lead and tin in these nanoalloys exhibit an orientation relationship with the matrix aluminum and with each other. DSC studies were conducted to reveal the melting and solidification characteristics of these embedded nanoalloys. DSC thermograms exhibit features of multiple solidification exotherms on thermal cycling, which can be attributed to sequential melting and solidification of lead and tin in the respective alloys.

Activities of oxygen and lead in Pb-Ag O solutions

The reversible e.m.f. of galvanic cells: stainlesssteel,Ir,Pb+PbO|CaO+ZrO2|Ag+Pb+PbO,Ir,stainlesssteel,I and Pt,Ni+NiO|CaO+ZrO2|O(Pb+Ag),Cermet,Pt,II incorporating solid oxide electrolytes were measured as a function of alloy composition. In lead-rich alloys, the temperature dependence of the e.m.f. of cell I was also investigated. Since the solubility of oxygen in the alloy is small, the relative partial molar properties of lead in the binary Ag + Pb system can be calculated from the e.m.f. of this cell. The Gibbs free energies obtained in this study are combined with selected calorimetric data to provide a complete thermodynamic discription of liquid Ag + Pb Alloys. The activity coefficient of oxygen in the whole range of Ag + Pb alloys at 1273 K have been obtained from the e.m.f. of cell II; and these are found to deviate positively from Alcock and Richardson's quasichemical equation when the average co-ordination number of all the atoms is assigned a value of 2.

Thermoelectric properties of indium doped PbTe1-ySey alloys

Lead telluride and its alloys are well known for their thermoelectric applications. Here, a systematic study of PbTe1-ySey alloys doped with indium has been done. The powder X-Ray diffraction combined with Rietveld analysis confirmed the polycrystalline single phase nature of the samples, while microstructural analysis with scanning electron microscope results showed densification of samples and presence of micrometer sized particles. The temperature dependent transport properties showed that in these alloys, indium neither pinned the Fermi level as it does in PbTe, nor acted as a resonant dopant as in SnTe. At high temperatures, bipolar effect was observed which restricted the zT to 0.66 at 800 K for the sample with 30% Se content. (C) 2014 AIP Publishing LLC.

Improvement of electrical conductivity in Pb0.96-yMn0.04SnyTe alloys for high temperature thermoelectric applications

Lead-tin-telluride is a well-known thermoelectric material in the temperature range 350-750 K. Here, this alloy doped with manganese (Pb0.96-yMn0.04SnyTe) was prepared for different amounts of tin. X-ray diffraction showed a decrease of the lattice constant with increasing tin content, which indicated solid solution formation. Microstructural analysis showed a wide distribution of grain sizes from <1 mu m to 10 mm and the presence of a SnTe rich phase. All the transport properties were measured in the range of 300-720 K. The Seebeck coefficient showed that all the samples were p-type indicating holes as dominant carriers in the measurement range. The magnitude increased systematically on reduction of the Sn content due to possible decreasing hole concentration. Electrical conductivity showed the degenerate nature of the samples. Large values of the electrical conductivity could have possibly resulted from a large hole concentration due to a high Sn content and secondly, due to increased mobility by sp-d orbital interaction between the Pb1-ySnyTe sublattice and the Mn2+ ions. High thermal conductivity was observed due to higher electronic contribution, which decreased systematically with decreasing Sn content. The highest zT = 0.82 at 720 K was obtained for the alloy with the lowest Sn content (y = 0.56) due to the optimum doping level.

Elastic Properties Of Sulphur And Selenium Doped Ternary PbTe Alloys By First Principles

Lead telluride (PbTe) is an established thermoelectric material which can be alloyed with sulphur and selenium to further enhance the thermoelectric properties. Here, a first principles study of ternary alloys PbSxTe(1-x) and PbSexTe(1-x) (0 <= x <= 1) based on the Virtual Crystal Approximation (VCA) is presented for different ratios of the isoelectronic atoms in each series. Equilibrium lattice parameters and elastic constants have been calculated and compared with the reported data. Anisotropy parameter calculated from the stiffness constants showed a slight improvement in anisotropy of elastic properties of the alloys over undoped PbTe. Furthermore, the alloys satisfied the predicted stability criteria from the elastic constants, showing stable structures, which agreed with the previously reported experimental results.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Thermoelectric properties of Pb0.75-xMnxSn0.25Te alloys with variable manganese content

Lead tin telluride is one of the well-established thermoelectric materials in the temperature range 350-750 K. In the present study, Pb0.75-xMnxSn0.25Te1.00 alloys with variable manganese (Mn) content were prepared by solid state synthesis and the thermoelectric properties were studied. X-ray diffraction, (XRD) showed that the samples followed Vegard's law, indicating solid solution formation and substitution of Mn at the Pb site. Scanning Electron Microscopy (SEM) showed that the grain sizes varied from <1 mu m to more than 10 mu m and MnTe rich phase was present for higher Mn content. Seebeck coefficient, electrical resistivity and thermal conductivity were measured from room temperature to 720 K. At 300 K, large Seebeck values were obtained, possibly due to increased effective mass on Mn substitution and low carrier concentration of the samples. At higher temperatures, transition from n-type to p-type indicated the presence of thermally generated carriers. Temperature dependent electrical resistivity showed the transition from degenerate to non-degenerate behavior. For thermal conductivity, low values (similar to 1 W/m-K at 300 K) were obtained. At higher temperatures bipolar conduction was observed, in agreement with the Seebeck and resistivity data. Due to low power factor, the maximum thermoelectric figure of merit (zT) was limited to 0.23 at 329 K for the sample with lowest Mn content (x=0.03). (C) 2015 Elsevier Ltd. All rights reserved.

Electric field induced short range to long range structural ordering and its influence on the Eu+3 photoluminescence in the lead-free ferroelectric Na1/2Bi1/2TiO3

Eu+3 was incorporated into the lattice of a lead-free ferroelectric Na1/2Bi1/2TiO3 (NBT) as per the nominal formula Na0.5Bi0.5-xEuxTiO3. This system was investigated with regard to the Eu+3 photoluminescence (PL) and structural behaviour as a function of composition and electric field. Electric field was found to irreversibly change the features in the PL spectra and also in the x-ray diffraction patterns below the critical composition x = 0.025. Detailed analysis revealed that below the critical composition, electric field irreversibly suppresses the structural heterogeneity inherent of the host matrix NBT and brings about a long range ferroelectric state with rhombohedral (R3c) distortion. It is shown that the structural disorder on the nano-scale opens a new channel for radiative transition which manifests as a new emission line branching off from the main D-5(0)-> F-7(0) line along with a concomitant change in the relative intensity of the other crystal field induced Stark lines with different J values. The study suggests that Eu+3 luminescence can be used to probe the relative degree of field induced structural ordering in relaxor ferroelectrics and also in high performance piezoelectric alloys where electric field couples very strongly with the lattice and structural degrees of freedom. (C) 2015 AIP Publishing LLC.

Nonlinear Enzyme Kinetics Can Lead to High Metabolic Flux Control Coefficients: Implications for the Evolution of Dominance

In a classic study, Kacser & Burns (1981, Genetics 97, 639-666) demonstrated that given certain plausible assumptions, the flux in a metabolic pathway was more or less indifferent to the activity of any of the enzymes in the pathway taken singly. It was inferred from this that the observed dominance of most wild-type alleles with respect to loss-of-function mutations did not require an adaptive, meaning selectionist, explanation. Cornish-Bowden (1987, J. theor. Biol. 125, 333-338) showed that the Kacser-Burns inference was not valid when substrate concentrations were large relative to the relevant Michaelis constants. We find that in a randomly constructed functional pathway, even when substrate levels are small, one can expect high values of control coefficients for metabolic flux in the presence of significant nonlinearities as exemplified by enzymes with Hill coefficients ranging from two to six, or by the existence of oscillatory loops. Under these conditions the flux can be quite sensitive to changes in enzyme activity as might be caused by inactivating one of the two alleles in a diploid. Therefore, the phenomenon of dominance cannot be a trivial ''default'' consequence of physiology but must be intimately linked to the manner in which metabolic networks have been moulded by natural selection.

Synthesis by mechanical alloying and thermoelectric properties of Cu2Te

Hexagonal Cu-2 Te has been synthesised by mechanical alloying from elemental powders. The milling time required for the synthesis is longer than that reported for other tellurides. The mechanical grinding of the bulk Cu2Te obtained by the melting route does not change the structure. Prolonged milling as well as grinding beyond 40 h lead to a decrease in grain size to nanometer level. The cold compaction of milled or ground powders exhibit much smaller Seebeck coefficient (thermopower). However, cold compaction of samples milled for longer time (>150 h) lead to the thermopower values close to that of the bulk indicating significant improvement of rheological properties at room temperature for powders milled for long times.

Glass forming ability and stability: Ternary Cu bearing Ti, Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr25Ti25Cu50, Zr34Ti16Cu50, Zr25Hf25Cu50 and Ti25Hf25Cu50 have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after meltspinning. In the Zr34Ti16Cu50 alloy localized precipitation of cF24 Cu5Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank-Kasper polyhedra.

Growth and study of antiferroelectric lead zirconate thin films by pulsed laser ablation

Antiferroelectric lead zirconate (PZ) thin films were deposited by pulsed laser ablation on platinum-coated silicon substrates. Films showed a polycrystalline pervoskite structure upon annealing at 650 degrees C for 5-10 min. Dielectric properties were investigated as a function of temperature and frequency. The dielectric constant of PZ films was 220 at 100 kHz with a dissipation factor of 0.03. The electric field induced transformation from the antiferroelectric phase to the ferroelectric phase was observed through the polarization change, using a Sawyer-Tower circuit. The maximum polarization value obtained was 40 mu C/cm(2). The average fields to excite the ferroelectric state, and to reverse to the antiferroelectric state were 71 and 140 kV/cm, respectively. The field induced switching was also observed through double maxima in capacitance-voltage characteristics. Leakage current was studied in terms of current versus time and current versus voltage measurements. A leakage current density of 5x10(-7) A/cm(2) at 3 V, for a film of 0.7 mu m thickness, was noted at room temperature. The trap mechanism was investigated in detail in lead zirconate thin films based upon a space charge limited conduction mechanism. The films showed a backward switching time of less than 90 ns at room temperature.

Lowering of relaxor transition temperature in Lead-based perovskites under pressure

The dielectric constants of lead iron niobate (PFN) and 40% lead zinc niobate (PZN) added to lead iron niobate (PFN0.6-PZN(0.4)) have been measured as a function of pressure up to 6 GPa under isothermal conditions between room temperature and 348 K. The relaxer transition temperature measured at 1 kHz excitation frequency varies at a rate -24.5 K/GPa for PFN and at a rate of - 28.8 K/GPa for the PFN0.6-PZN(0.4) composition.