Observation of the strongly anomalous temperature and composition dependence of (δp/δT)s in liquid Li/Pb alloys

(δp/δT)_s which is proportional to the specific heat has been measured between the liquidus temperature and 1250 K for the whole concentration range of liquid Li/Pb alloys. For all concentrations it shows a positive deviation from the values expected for an ideal solution and it exhibits a narrow peak close to the composition Li₄Pb. The variation of T(δp/δT)_s with T is linear only for pure Pb. At 0.2 < x_Li < 0.6 a fall-off after melting is followed by a broad maximum at about 1000 K.     

Electron theory of long-wavelength concentration fluctuations in liquid metal alloys

Summary It is shown that long-wavelength concentration fluctuations in a binary liquid metal alloy are determined by a pair interchange free energyw, which is exactly given by the sum of an elastic strain term and of the concentration-concentration direct correlation function. The latter is evaluated in an alloy of homovalent components by electron screening theory in the pseudopotential approach of Shaw and Harrison and shown to be entirely determined by nonlocal terms reflecting charge transfer to the more electronegative alloy component. Numerical calculations for the liquid Na−K alloy show strong cancellation between the two contributions tow at all concentrations, in qualitative agreement with experiment.     

Superconducting transition temperatures of amorphous binary alloy systems based on Bi,Pb, Ga and Be

Quench condensed binary alloy films are produced by evaporation from two separated furnaces. The films contain the whole composition range of the respective alloy system in well defined arrangement.T _c is measured as a function of concentration. Eight predominantly amorphous alloy systems are studied: Bi—Ga, Pb—Ga, Pb—Bi, Be—Bi, Be—Pb, Be—Ga, Be—Al, Be—Li. In Bi—Ga and Pb—GaT _c is a linear function of concentration in the amorphous composition range. In Pb—BiT _c has a maximum. All Be-alloys show lower transition temperatures than pure quench condensed Be. Except for Be—Li all systems have aT _c minimum. The experiments are compared to aT _c calculation using tunelling spectroscopy data. Except for the Be-alloys the agreement is satisfying.     

The effect of alloy composition on the interaction of NO2 with tin-lead alloys

The interaction of NO₂ with SnPb alloys is presented. Five different compositions of the alloy were used with an NO₂ concentration of 140 ppm. A plot of the rate of weight gain versus sample composition is presented which indicates that NO₂ interacts with all compositions tested with the rate of weight gain decreasing slightly as the percent of lead goes from zero to 100 percent. Reaction products obtained were Pb(NO₃)₂ and an amorphous tin containing product which is probably tin nitrate. The alloys undoubtedly contain mixtures of the two materials.     

Ordering potential: the anomalous structure and properties of liquid KPb alloy

The anomalous structure and related properties of liquid KPb alloy are presented through an ab initio evaluated ordering potential as a function of concentration. It appears that considerable ordering occurs and it maximizes at the stoichiometric composition (c_k∼0.5). We then use the model to obtain the Bhatia-Thornton(BT) structure factors at different compositions (c_k=0.1,0.3,0.5 and 0.8). The calculations of concentration fluctuation and other related thermodynamic properties show that this ordering potential approach works reasonably for this compound forming liquid alloy.     

Transverse collective modes in liquid binary alloys

Transverse current correlations in binary liquid alloys are investigated by molecular dynamics simulation. The study includes several Li-Mg, Li-Na and Li-Pb alloys. The characteristics of both shear and transverse optic-like modes are discussed. The former modes are associated with the number density fluctuations whereas the latter are related to the concentration fluctuations. Special attention is paid to the dependence of the results on the mass ratio and composition of the alloy.     

Concentration fluctuations in adsorbed layers

The temperature and coverage dependence of the mean square concentration fluctuations in a small open domain of an adsorbed layer is discussed for various situations. It is shown that fluctuations decrease with increasing temperature and reach a limiting value when attractive interactions predominate, but increase and reach a limiting value when repulsive interactions predominate, if a single non-ideal two -dimensional phase exists. Deviations from ideal gas behavior are strongest at half coverage. At very low coverage (low particle concentration) and very high coverage (low hole concentration) ideal behavior is approached. If the layer consists of a two phase system, for instance a two-dimensional liquid or solid in equilibrium with a two-dimensional gas, fluctuations far below the critical temperature are dominated by fluctuations in the partition between phases. As the critical temperature is approached fluctuations first decrease because the mean concentrations in the two phases approach each other, and then increase very sharply near T_c. Detailed calculations for the single phase situation are given for several approximations: a dilute gas; a mean field approximation; a lattice gas in both the Bragg-Williams and the BethePeierls-Weiss approximations. The latter which takes some account of correlations between adsorbate particle positions seems to explain reasonably the presently available experimental observations on chemisorbed layers.     

Bulk and surface properties of liquid X-Zr (X=Ag, Cu) compound forming alloys

The phase diagrams of the Ag-Zr and Cu-Zr systems exhibit the existence of different intermetallic compounds in the solid state, and since the structure of a liquid alloy is in some respects similar to that of a crystal, the compound formation phenomenon in these liquid alloy systems has been analysed through the study of surface properties (surface tension and surface composition), dynamic properties (chemical diffusion and viscosity) and microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the frame of the compound formation model (CFM). Moreover, the associative tendency between unlike constituent elements qualitatively expressed by the microscopic functions indicates the glass-forming ability of both systems at higher Zr-concentrations. These results are in agreement with reported experimental data and confirm the applicability of a statistical mechanical theory in conjunction with the CFM to describe the mixing behaviour of compound forming alloys.     

Structural asymmetry in liquid Fe–Si alloys

The thermodynamic properties and microscopic structure of liquid Fe–Si alloys at 1873 K were studied by using the regular associated solution model. The model was utilized to determine the complex concentration in a regular associated solution of Fe, Si and Fe₂Si. The complex concentration was then used to calculate the integral excess free energy of mixing, activity, concentration fluctuations in the long-wavelength limit, S_CC (0), and the Warren–Cowley short-range parameter α ₁. The analysis suggests that heterocoordination leading to the formation of complex Fe₂Si is likely to exist in the liquid and is of a strongly interacting nature. The theoretical analysis reveals that the alloy is more ordered towards the Fe-rich region. The observed asymmetry in the properties of mixing of Fe–Si alloys in the molten state is successfully explained on the basis of the regular associated solution model.     

Surface tension of liquid Al-Cu and wetting at the Cu/Sapphire solid-liquid interface

For the study of the interaction of a liquid alloy with differently oriented single crystalline sapphire surfaces precise surface tension data of the liquid are fundamental. We measured the surface tension of liquid Al-Cu contactlessly on electromagnetically levitated samples using the oscillating drop technique. Data were obtained for samples covering the entire range of composition and in a broad temperature range. The surface tensions can be described as linear functions of temperature with negative slopes. Moreover, they decrease monotonically with an increase of aluminium concentration. The observed behaviour with respect to both temperature and concentration is in agreement with a thermodynamic model calculation using the regular solution approximation. Surface tensions were used to calculate interfacial energies from the contact angles of liquid Cu droplets, deposited on the C(0001), A(11-20), R(1-102) surfaces of an α-Al₂O₃ substrate. The contact angles were measured by means of the sessile drop method at 1380?K. In the Cu/α-Al₂O₃ system, no anisotropy is evident neither for the contact angles nor for the interfacial energies of different surfaces. The work of adhesion of this system is isotropic, too.     

Prediction of thermodynamic and surface properties of Pb−Hg liquid alloys at different temperatures

The thermodynamic properties, such as free energy of mixing, heat of mixing, activity and structural properties, such as concentration fluctuation in long wavelength limit, short-range order parameter of Pb–Hg liquid alloy at 600 K have been calculated using theoretical modelling. It has then been correlated with modified Butler model to compute the surface tension of the alloys at different temperatures. The Pb–Hg system at 600 K is found to be ordering at higher concentration of Pb.     

Surface and transport properties of Au-In liquid alloys

Thermodynamic quantities on Au-In liquid alloys have been used as the input data for the interaction parameter calculations in the framework of the complex formation model (CFM). Once the interaction energies are computed the surface (surface tension and surface composition) and transport properties (chemical diffusion and viscosity) as well as the microscopic functions (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) have been calculated. The concentration and temperature dependent surface tension values have been compared with our new set of experimental data, obtained by the large drop method in the temperature range of T = 1273-1493 K. The anomalous change of surface tension for some alloy compositions may be attributed to a retention of order in the Au-In melts which is similar to the atomic arrangement in solid Au-In.     

Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys

The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation S _cc(0) and the Warren-Cowley short-range order parameter (α ₁) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In-Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn₂ could be present in the Sb-Sn alloy at a temperature of about 770 K.     

Local order in the bulk and surface of liquid K-Pb alloy

Ordering in the bulk and surface of liquid K-Pb alloy has been studied throughout the bulk concentration range. At low K concentrations, the liquid alloy is strongly ordered both in the bulk and on the surface. The existence of the zintl structure in the liquid alloy is predicted to be predominant below 0.6 atomic fraction of K. While above this concentration a complex of the form K₃Pb₂ is suggested to be present. PACS  28.52.Fa; 65.70.+y; 61.20.-p; 61.82.Bg     

Concentration dependence of thermodynamic,transport and surface properties in Ag–Cu liquid alloys

Thermodynamic, transport and surface properties of Ag–Cu liquid alloys have been investigated on the basis of a simple statistical model. The free energy of mixing, heat of mixing and entropy of mixing have been computed to understand the thermodynamic properties of Ag–Cu alloys in liquid state at 1,423 K. The concentration–concentration fluctuations in the long wavelength limit and the chemical short range order parameter have been determined to comprehend the microscopic and structural information of the alloy. The viscosity and surface tension of the alloy have been evaluated to analyze the transport and surface properties. The theoretical analysis reveals that the energy parameter is temperature dependent, and that Ag–Cu liquid alloy is a weakly interacting-phase separating system.     

Electrical resistivity of NaPb compound-forming liquid alloy using abinitio pseudopotentials

The study of electrical resistivity of compound-forming liquid alloy, NaPb, is presented as a function of concentration. Hard sphere diameters of Na and Pb are obtained through the interionic pair potentials evaluated using Troullier and Martinsab initio pseudopotential, which have been used to calculate the partial structure factors S(q). Considering the liquid alloy to be a ternary mixture, Ziman formula, modified for complex formation has been used for calculating resistivity of binary liquid alloys. Form factors are calculated usingab initio pseudopotentials. The results suggest that Ziman formalism, when used withab initio pseudopotentials, are quite successful in explaining the electrical resistivity data of compound-forming binary liquid alloys.     

Crystallization behaviour in a new multicomponent Ti16.6Zr16.6Hf16.6Ni20Cu20Al10 metallic glass developed by the equiatomic substitution technique

A new amorphous Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ alloy has been developed using the novel equiatomic substitution technique. Melt spinning Ti_16.6Zr_16.6Hf_16.6Ni₂₀Cu₂₀A1₁₀ forms an amorphous phase with a large supercooled liquid region, ΔT=70°C. After isothermal annealing within the supercooled liquid region for 3 h at 470°C, the amorphous alloy crystallizes to form a fine-scale distribution of 2–5 nm nanocrystals, and the supercooled liquid region increases to ΔT=108°C. Atomic-scale compositional analysis of this partially crystalline material using a three-dimensional atom probe (3DAP) is unable to detect any compositional difference between the nanocrystals and the remaining amorphous phase. After annealing for 1 hr at 620°C, the amorphous alloy crystallizes to form 20–50nm equiaxed grains of a hexagonal-type C14 Laves phase with lattice parameters a = 5.2Å and c = 9.0 Å. 3DAP analysis shows that this Laves phase has a composition very close to that of the initial amorphous phase, suggesting that the alloy crystallizes via a polymorphic rather than a primary crystallization mechanism, despite the complexity of the alloy composition.     

Chemical Structure of Fe<Subscript>78</Subscript>B<Subscript>13</Subscript>Si<Subscript>9</Subscript> Alloy Surface Layers in the Solid and Liquid States

The chemical structure of Fe₇₈B₁₃Si₉ alloy in the solid and liquid states and local atomic environment are studied in situ by X-ray photoelectron spectroscopy (XPS). The chemical bonds between elements in the melt are analyzed during a temperature increase. Two temperature regions are identified. The liquid surface in the first temperature region is shown to contain clusters of Fe-Si and (Fe-O _x )-Si types. In the second one, clusters of Fe-B and (Fe-O _x )-B types dominate. It is impossible to determine the composition of the clusters definitively using XPS data only. A jump-like change in the composition of the surface layers of the melt is detected, which is interpreted as structural transformations within the liquid state.     

Sliding Wear Studies on Aluminium–Copper Composites

Metal–metal composites are prepared by dispersing copper particulates in an aluminium matrix using stir-cast technique. Behaviour of the same is compared with the alloy having similar composition. Wear behaviour of the alloy in the cast condition is superior to the homogenized condition, though cast structure exhibit low hardness compared to the other. This is attributed to the easy crack propagation along the CuAl₂ precipitates in the homogenized condition, compared to the grain boundary in the as-cast structure. Wear properties of the resultant composite are superior to the alloy. Effect of particulate composition is studied by varying the copper concentration between 5 and 15 wt%. Composites with high copper content exhibit better wear resistance than the dilute ones, which is attributed to the increased hardness due to large population of intermetallics.     

Electron relaxation mechanisms in n-Bi-Sb semiconducting alloys

The magnetic field dependence of diffusion thermal electromotive force α₂₂(H) (?T ∥ C ₁) in degenerate n-Bi-Sb semiconducting alloys, in which only L electrons participate in transfer phenomena, had a maximum at H ∥ C ₃. The electron relaxation time was determined from the magnetic field value corresponding to this maximum. The dependences of the electron relaxation time on temperature and the concentration of alloy components and the dopant (on the concentration of electrons) were used to separate electron relaxation time components corresponding to scattering by phonons, ionized impurities, and component concentration fluctuations. The latter (“alloy”) mechanism of electron scattering by concentration fluctuations was for the first time considered for Bi-Sb alloys; its contribution was found to be comparable with those of the other scattering mechanisms. The obtained relaxation times were used to calculate theoretical magnetic field dependences of thermal electromotive force and the Nernst-Ettingshausen coefficient. The calculation results were in satisfactory agreement with experiment.