Liquid Sb Research Articles

Hump phenomenon on resistivity–temperature curve in liquid Bi, Sb and their alloys

The electrical resistivities of liquid Bi, Sb, and some of their alloys Pb–Bi, Pb–Sb have been investigated as a function of temperature, and the effect of heating-rate on the turning points of liquid Bi has also been investigated. Obvious and interesting hump phenomena are observed on resistivity–temperature curves of liquid Bi, Sb, and Pb–Bi, Pb–Sb alloys on heating at the temperature far above their liquidus. Moreover, the transition temperature of liquid Bi increases with heating-rate increasing, which shows that this kind of transition is in accordance with kinetic characteristics. However, comparing the heating curve with the cooling one, we found that the anomalous hump phenomenon is irreversible in liquid Bi, Sb, and Pb–Bi, Pb–Sb alloys.

Liquid Film Migration in a Cu-5 At.% Sb Alloy

Liquid film migration was studied in a Cu-5 at % Sb alloy by both down-quenching and up-quenching from the initial liquation temperature in the two-phase, α + liquid, field. The time and temperature dependence of the migration distance and the rate of migration were studied in the temperature range of 440 to 760 °C. A near parabolic growth behaviour was observed. The coherency strain energy as calculated from the composition of the trailing grain was observed to be one order of magnitude higher than the interfacial energy of the cylindrical liquid film. The total chemical free energy was calculated to be one to three orders of magnitude higher than the coherency strain energy. A substantial part of the total chemical free energy is used for volume diffusion in front of the liquid film in the receding grain. The diffusion coefficients and the activation energy calculated at 730 to 760 °C correspond to those of the diffusion of Sb in liquid Cu. The activation energy is close to those of self diffusion in liquid Sb and Cu.

Liquid Film Migration in a Cu-5 At.% Sb Alloy

Liquid film migration was studied in a Cu-5 at % Sb alloy by both down-quenching and up-quenching from the initial liquation temperature in the two-phase, α + liquid, field. The time and temperature dependence of the migration distance and the rate of migration were studied in the temperature range of 440 to 760 °C. A near parabolic growth behaviour was observed. The coherency strain energy as calculated from the composition of the trailing grain was observed to be one order of magnitude higher than the interfacial energy of the cylindrical liquid film. The total chemical free energy was calculated to be one to three orders of magnitude higher than the coherency strain energy. A substantial part of the total chemical free energy is used for volume diffusion in front of the liquid film in the receding grain. The diffusion coefficients and the activation energy calculated at 730 to 760 °C correspond to those of the diffusion of Sb in liquid Cu. The activation energy is close to those of self diffusion in liquid Sb and Cu.

Thermal chemistry and short-range order in Co-Sb melts

The enthalpies of mixing for the liquid Co-Sb alloys are measured by isoperibolic calorimetry at 1600 K over the whole concentration range relative to liquid Sb and undercooled liquid Co. The minimal integral enthalpy of mixing is −6.3 ± 0.6 kJ/ mole at xCo = 0.50. Activity of components, Gibbs energy, and the entropy of mixing are calculated using a short-range ordering model considering CoSb associates formed in molten Co-Sb alloys.

Liquid-state semiconductor p-n junction at 903K

A liquid-state semiconductor p-n junction has been fabricated by applying the liquid phase separation of the monotectic Sb-Sb2S3 system at 903K. Electrical conduction types of liquid semiconductor of Sb–S alloy and S2S3-x consisting of the immiscible system are found to be p and n types, respectively, from measured absolute Seebeck coefficients. The p-n junction was formed by the liquid Sb–-S alloy and Sb2S3−x; this is confirmed from the asymmetric current-voltage characteristics or its behavior is rectified. The formation of the liquid-state p-n junction in liquid semiconductors has great prospects in the next-generation direct thermal-to-electrical energy conversion materials.

Structural study of liquid Sb–S mixtures

The local atomic structures of liquid Sb 40S 60, Sb 44Sb 56 and Sb 90S 10 were investigated by the neutron diffraction method. The characteristic features of the structure factor, S( q), of liquid Sb 40S 60 are as follows: (i) a prepeak is observed at around q=1.2 Å −1, (ii) heights of the first and second peaks in S( q) are similar, (iii) oscillations in S( q) are persisted over the 25 Å −1. The overall feature of S( q) for liquid Sb 44S 56 is similar to that for liquid Sb 40S 60. On the other hand, the feature of S( q) for liquid Sb 90S 10 is quite different from those of liquid Sb 40S 60 and Sb 44S 56. The prepeak is not observed in S( q) for liquid Sb 90S 10 while oscillation of S( q) still remains over 20 Å −1. The height of the first peak in S( q) becomes larger than that of the second peak. These results suggest that there exists the short-range order for these liquid Sb–S mixtures and also exists the middle-range order in the liquid Sb 40S 60 and Sb 44S 56. The local atomic structure of liquid Sb 90S 10 seems to be quite different from that of liquid Sb 40S 60, which can be related to the metal–non-metal transition and the existence of the two-phase region between the composition of Sb 40S 60 and Sb.

Structure and properties of liquid InSb alloy below and above the melting point: ab initiomolecular dynamics simulations

Using ab initio molecular dynamics simulations, we have investigated the structure,diffusion and electronic properties of liquid InSb alloy below and above the melting point.A large gap in value or a ‘flat shape’ between the position of the first and second peak ofthe calculated pair correlation function, and an asymmetry of the first peak, were displayedin our simulations. There is a small hump between the first and second peak of the partialpair correlation function of Sb atoms, which gradually disappears with increasingtemperature. Analysis of the compositional disorder number suggests that heterogeneousbonds still play a predominant role in liquid InSb alloy. With increasing temperature, theopened chain-like Sb–Sb bonds are broken and the Peierls distortion of Sb atoms in liquidInSb alloy is weakened. With the change of temperature, the diffusion coefficientsobtained from the average mean-square displacement can be fitted by the Arrheniusequation. The fit yields an activation energy of 0.20 eV and a pre-exponential factor of2.01 × 10−8 m2 s−1.

Pressure and temperature dependence of the structure of liquid InSb

We investigate the structure of liquid InSb over a wide pressure range up to 20 GPa and a wide temperature range up to 1570 K by synchrotron x-ray diffraction. With increasing pressure along the melting curve, the local structure, which is anisotropic near the ambient pressure, becomes more isotropic. However, at pressures higher than about 10 GPa, the pressure-induced change becomes less prominent, and the local structure contracts almost uniformly. Structural parameters deviate significantly from those in simple liquid metals in this pressure region, revealing a stable liquid form with an anisotropic local structure. The analysis of $g(r)$ reveals that the liquid is possibly interpreted by the local structure of a single species, whose $g(r)$ is apparently expressed by a linear combination of $g(r)$ for $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{Sn}$-like and bcc-like local structures in a one-to-one ratio. This local structure is completely different from those present in its crystalline counterpart. Pressure and temperature dependence of the local structure is discussed in the relation to Rapoport two species model [J. Chem. Phys. 46, 2891 (1967)].

Structural and electronic properties of liquid InSb alloy: An ab initio molecular-dynamics simulation

The structural and electronic properties of liquid InSb have been simulated by using ab initio molecular dynamics. The calculated results indicate that the covalent bonds of In–Sb similar to those of c-InSb are preserved in liquid state, and the Sb clusters have open structure while the In clusters have close-packed structure.

Ab initiomolecular-dynamics simulations of liquid GaSb and InSb

We report results for the structural, dynamical, and electronic properties of liquid GaSb $(l\text{\ensuremath{-}}\mathrm{Ga}\mathrm{Sb})$ and liquid InSb $(l\text{\ensuremath{-}}\mathrm{In}\mathrm{Sb})$ simulated by using ab initio molecular dynamics. Our calculated structure factors and pair correlation functions for $l\text{\ensuremath{-}}\mathrm{Ga}\mathrm{Sb}$ and $l\text{\ensuremath{-}}\mathrm{In}\mathrm{Sb}$ are in good agreement with available experimental data. The calculated results indicate that covalent heteroatomic bonds similar to those of the crystalline phase are preserved in the liquid state, and the local structures of Ga (In) and Sb atoms in $l\text{\ensuremath{-}}\mathrm{Ga}\mathrm{Sb}$ and $l\text{\ensuremath{-}}\mathrm{In}\mathrm{Sb}$ are analogous with those in pure-element liquids.

Local structures of liquid semi-metal Sb studied by in-situ XAFS

The local structures of semi-metal Sb have been studied by in-situ XAFS in the temperature range of 298 and 913 K. The radial structural functions of Sb atoms reveal that the local structure of the pre-molten Sb (893 K) is similar to that of crystalline Sb (298 K), except the increase of thermal disorder degree. With the temperature increasing up to 913 K, the position of the first peak located at 2.63 Å in the liquid Sb is kept the same as that in the pre-molten Sb, while the intensity of the first peak is strongly reduced by about 30% during the solid-liquid transition. This feature indicates that the melting results in a large increase of disorder degree of the liquid Sb, and that there exists covalent bonded clusters (Sb)n in the liquid Sb (913 K).

Thermodynamic and surface properties of Ge–Ga and Ge–Sb liquid alloys

Thermodynamic and surface properties of Ge–Ga and Ge–Sb liquid alloys have been studied using statistical mechanical formulations based on complex formation and that based on the concept of layered structure near the interface. The study showed that low level of complex formation of the form Ge 2 Sb exists in Ge–Sb toward the Ge-rich end of the concentration range and the surface properties of Ge–Ga are almost equal to their corresponding bulk equivalent.

Obtaining GaSb/InAs heterostructures by liquid phase epitaxy

Features of liquid phase epitaxy of GaSb/InAs heterostructures are considered. A modified method of pulse cooling of saturated solution-melt is offered. This method allows us to avoid InAs substrate dissolution during contact with a Ga–Sb liquid phase. Also it is shown that forming InxGa1−xAsySb1−y solid solutions due to GaSb epitaxial layer dissolution by InAs substrate is energetically unfavourable.

Thermodynamic properties of liquid silver–antimony alloys determined from emf measurements

The thermodynamic properties of the liquid Ag–Sb alloys were determined using solid oxide galvanic cells with zirconia electrolyte. The emfs of the cells: Ag x Sb (1−x), Sb 2 O 3/ O 2−/ air were measured in the temperatures range 950–1100 K in the whole range of the alloy compositions. First, the Gibbs free energy of formation of liquid Sb 2O 3 from pure elements was derived: ΔG° f( Sb 2 O 3) ( J/ mol)=−687100+243.23T. Next, the activities of antimony were measured as a function of the alloy compositions, x. Redlich–Kister polynomial expansion was used to describe the thermodynamic properties of the liquid phase. From the model equations the limiting value of the logarithm of activity coefficient of antimony in silver was obtained as a function of temperature: ln γ Sb 0=−3812.5/T+0.4112. The obtained results were compared with the experimental values reported in the literature.

Structural Changes and Compound Forming Effects in the Molten Sb–Te System Investigated by Molar Volume and Sound Velocity Measurements

Molar volume and sound velocity measurements were carried out in the liquid Sb–Te system as a function of temperature and composition. Results obtained have been used to deduce the compressibility and thermal expansion coefficient. Molar volume and adiabatic compressibility show a distinct cusp at the Sb 2 Te 3 composition, which suggests the persistence of stable association in the liquid. At low temperatures near the liquidus line, mentioned thermodynamic parameters show behaviour characteristic of structural changes with temperature. Large specific heat anomaly reported previously can be ruled out from the present experiments.

Investigation of the surface topography and double layer characteristics of variously pre-treated antimony single crystal electrodes

The geometrical roughness factor, root mean square departure of the surface from flatness, the medium lateral correlation length and other parameters have been obtained for variously pre-treated Sb(1 1 1) and Sb(0 0 1) electrodes. Atomic resolution was achieved for cleaved at liquid nitrogen temperature Sb(1 1 1) surface using UHV-STM method. The surface pits with various depths and widths on the surface of electrochemically and chemically etched Sb(1 1 1) electrodes, and deep furrows on the surface of cleaved Sb(0 0 1) have been observed. Electrical double layer characteristics of variously pre-treated Sb(1 1 1) and Sb(0 0 1) electrodes were studied in terms of the Debye length dependent roughness theory (i.e., non-linear Poisson–Boltzmann theory), recently developed by Daikhin et al. [Phys, Rev. E 53 (1996) 6192; Electrochim. Acta 42 (1997) 2853 and J. Chem. Phys. 108 (1998) 1715]. According to the experimental data and results of theoretical calculation, the surface roughness increases in the order of Sb electrodes: cleaved at the temperature of liquid nitrogen Sb(1 1 1) < electrochemically polished single crystal Sb(1 1 1) < electrochemically etched Sb(1 1 1) < chemically etched Sb(1 1 1) < cleaved at temperature of liquid nitrogen Sb(0 0 1). This order of the electrode surface roughness is in agreement with the data obtained from STM, AFM and impedance measurements.

Precise measurement of the densities of liquid Bi, Sn, Pb and Sb

The densities of liquid Bi, Sn, Pb and Sb have been precisely measured from themelting point up to about 1100 K using an improved Archimedean method. Thedensities at the melting point for liquid Bi, Sn, Pb and Sb are 10.042 × 103, 6.983 × 103,10.635 × 103and 6.454 × 103 kg m−3,respectively. Comparisons between our data and those from the literature havebeen made and they show the present results to be more reliable. Rather than alinear fit for the temperature dependence of the density, a slight deviation fromlinearity in the temperature dependence of the densities has been observed.

Thermodynamic properties of the ternary system InSb–NiSb–Sb in the temperature range 640–860 K

The ternary InSb–NiSb–Sb system has been studied by X-ray diffraction and by potentiometry. The electromotive forces (EMF) have been measured in the temperature range 640<T/K<860 by using the following galvanic cell:−In/InClinKCl+LiClliqInxNiySb1−x-y+with x (0.075<x<0.498) and y (0<y<0.359). The investigated samples are located on the following lines of the Gibbs triangle: InSb–Ni0.33Sb0.66, InSb–Ni0.48Sb0.52, InSb–NiSb, Sb–(InSb)0.75(NiSb)0.25, Sb–(InSb)0. 5(NiSb)0.5, Sb–(InSb)0.25(NiSb)0.75. From these measurements, the values of the partial molar thermodynamic functions (Δμ°m,In, ΔH°m,In, ΔS°m,In) (data at reference pressure p0=105 Pa), for the liquid InSb alloy, for the three solid heterogeneous regions InSb–NiSb2–Sb, InSb–NiSb1±δ?–NiSb2, InSb–NiSb1±δ, for six ternary liquid–solid alloys, have been calculated.

Electrical Conductivity of Liquid Sb and Bi Doped with 3d Transition Metals

The electrical conductivity of liquid Sb and Bi doped with 3d transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) was measured. The results demonstrate that small (≤3 at. %) additions of these metals reduce the conductivity of the melts by up to 4%, except for Ni and Cu, which slightly raise the conductivity of liquid Sb. This finding is interpreted in terms ofs–d hybridization. The scattering of electrons is considered using the Friedel–Anderson approach, based on the concept of virtual bound states.

Structure of liquid Sb–Zn alloys

Using neutron diffraction, the structure factor and pair correlation function of molten Sb 25Zn 75, Sb 43Zn 57 and Sb 70Zn 30 were determined as function of temperature. The first atomic distance as well as the number of nearest neighbors increase with increasing temperature. Most atoms are associated in clusters with covalent bonds.