XPS and XAES studies of surface segregation and oxidation of Cu-Ge alloy

Surface segregation of Ge is seen in the Cu-5at%Ge alloy with an activation enthalpy equal to 17 kJ/mol. Oxidation of the alloy in the temperature range 400 to 600 K shows the formation of Cu2O and GeO which on further heating in vacuum at 650 K converts to GeO2 with the reduction of Cu2O to Cu.

Surface segregation and oxidation studies of Cu-Sn and Cu-Pd alloys by x-ray photoelectron and auger spectroscopy

X-ray photoelectron and Auger spectroscopic techniques have been employed to study surface segregation and oxidation of Cu-1 at%Sn, Cu-9at%Pd and Cu-25at%Pd alloys. Both Cu-Pd(9%) and Cu-Pd(25%) alloys show segregation of Cu when heated above 500 K. The Pd concentration was reduced by 50% at 750 K compared to the bulk composition; the enthalpy of segregation of Cu is around - 6kJ/mol. Sn segregation is seen from 470 to 650 K in the Cu-Sn(1%) alloy, and a saturation plateau of Sn concentration above 650 K is observed. Surface oxidation of Cu-Sn(1%) and Cu-Pd(9%) alloys at 500 K showed the formation of Cu2O on the surface with total suppression of Sn or Pd on the respective alloy surfaces. On vacuum annealing the oxidised Cu-Sn alloy surface at 550 K, a displacement reaction 2Cu2O+Sn→4Cu+SnO2 was observed. However, under similar annealing of the oxidised Cu-Pd(9%) alloy surface at 500 K, oxide oxygen was totally desorbed leaving the Cu-Pd alloy surface clean. In the case of the Cu-Pd(25%) alloy, only dissociatively chemisorbed oxygen was seen at 500 K which desorbed at the same temperature. Oxygen spill-over from copper to palladium is suggested as the mechanism of oxygen desorption from the oxidised Cu-Pd alloy surfaces.

Mercury Segregation and Diselenide Self-Assembly on Gold

We have investigated the self-assembly of didecyldiselenide on gold containing mercury using X-ray photoelectron spectroscopy, cyclic voltammetry and infrared spectroscopy. The analysis of intensity and chemical shift of selected Se, Hg, and Au photoelectron lines on samples with increasing Hg content, show that didecyldiselenide adsorption strongly contributed to segregation of bulk Hg to the surface. The voltammetry results support this conclusion and suggest the formation of Hg-Au surface amalgam. The Hg surface segregation effect must be related to the restructuring of the surface following initial adsorption, and to the strong selenophilicity of Hg. The reflectance absorbance infrared spectroscopy studies show that the molecular layer on Hg-Au substrates lacks good order.

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu3Ti4O12 (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250K, in addition to the well-investigated dielectric relaxation close to 100K. The effect of sintering and doping (La3+) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La2/3Cu3Ti4O12, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers. (C) 2007 Elsevier Ltd. All rights reserved.

Investigation of Annealing Induced Yttria Segregation in Sputtered Yttria-Stabilized Zirconia Thin Films

8mol% yttria-stabilized zirconia (8YSZ) is an extensively studied solid electrolyte. But there is no consistency in the reported ionic conductivity values of 8YSZ thin films. Interfacial segregation in YSZ thin films can affect its ionic conductivity by locally altering the surface chemistry. This article presents the effects of annealing temperature and film thickness on free surface yttria segregation behavior in 8YSZ thin film by Angle Resolved XPS and its influence on the ionic conductivity of sputtered 8YSZ thin films. Surface yttria concentration of about 32, 20, and 9mol% have been found in 40nm 8YSZ films annealed at 1273, 1173, and 1073K, respectively. Yttria segregation is found to increase with increase in annealing temperature and film thickness. Ionic conductivities of 0.23, 0.16, and 0.08Scm(-1) are observed at 923K for 40nm 8YSZ films annealed at 1073, 1173, and 1273K, respectively. The decrease in conductivity with increase in annealing temperature is attributed to the increased yttria segregation with annealing. Neither segregation nor film thickness is found to affect the activation energy of oxygen ion conduction. Target purity is found to play a key role in determining free surface yttria segregation in 8YSZ thin films.

Surface chemical studies of Thiobacillus ferrooxidans with reference to copper tolerance

A strain of Thiobacillus ferrooxidans was adapted to grow at higher concentrations of copper by single step culturing in the presence of 20 g/L (0.314 mol/L) cupric ions added to 9K medium. Exposure to copper results in change in the surface chemistry of the microorganism. The isoelectric point of the adapted strain (pI=4.7) was observed to be at a higher pH than that of the wild unadapted strain(pI=2.0). Compared to the wild strain, the copper adapted strain was found to be more hydrophobic and showed enhanced attachment efficiency to the pyrite mineral. The copper adsorption ability of the adapted strain was also found to be higher than that of the wild strain. Fourier transform infrared spectroscopy of adapted cells suggested that a proteinaceous new cell surface component is synthesized by the adapted strain. Treatment of adapted cells with proteinase-K, resulted in complete loss of tolerance to copper, reduction in copper adsorption and hydrophobicity of the adapted cells. These observations strongly suggest a role played by cell surface modifications of Thiobacillus ferrooxidans in imparting the copper tolerance to the cells and bioleaching of sulphide minerals.

On the measurement of the surface energy budget over a land surface during the summer monsoon

The measurement of surface energy balance over a land surface in an open area in Bangalore is reported. Measurements of all variables needed to calculate the surface energy balance on time scales longer than a week are made. Components of radiative fluxes are measured while sensible and latent heat fluxes are based on the bulk method using measurements made at two levels on a micrometeorological tower of 10 m height. The bulk flux formulation is verified by comparing its fluxes with direct fluxes using sonic anemometer data sampled at 10 Hz. Soil temperature is measured at 4 depths. Data have been continuously collected for over 6 months covering pre-monsoon and monsoon periods during the year 2006. The study first addresses the issue of getting the fluxes accurately. It is shown that water vapour measurements are the most crucial. A bias of 0.25% in relative humidity, which is well above the normal accuracy assumed the manufacturers but achievable in the field using a combination of laboratory calibration and field intercomparisons, results in about 20 W m(-2) change in the latent heat flux on the seasonal time scale. When seen on the seasonal time scale, the net longwave radiation is the largest energy loss term at the experimental site. The seasonal variation in the energy sink term is small compared to that in the energy source term.

Surface chemical studies on mica and galena using dextrin

The interactions of dextrin with biotite mica and galena have been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of dextrin onto mica continuously increase with increase of pH, while those onto galena show a maximum at pH 11.5. It is observed that the adsorption density of dextrin onto galena is quite high compared to that on mica. Both the adsorption isotherms exhibit Langmuirian behavior. Electrokinetic measurements portray conformational rearrangements of macromolecules with the loading, resulting in a shift of the shear plane, further away from the interface. Dissolution experiments indicate release of the lattice metal ions from mica and galena. Coprecipitation tests confirm polymer-metal ion interaction in the bulk solution. Dextrin does not exhibit any depressant action toward mica, whereas, with galena, the flotation recovery is decreased with an increase in pH beyond 9, in the presence of dextrin, complementing the adsorption results. Differential flotation results on a synthetic mixture of mica and galena show that mica can be selectively separated from galena using dextrin as a depressant for galena above pH 10. Possible mechanisms of interaction between dextrin and mica/galena are discussed.

The effect of surface tension in porous wave maker problems

Using a mixed-type Fourier transform of a general form in the case of water of infinite depth and the method of eigenfunction expansion in the case of water of finite depth, several boundary-value problems involving the propagation and scattering of time harmonic surface water waves by vertical porous walls have been fully investigated, taking into account the effect of surface tension also. Known results are recovered either directly or as particular cases of the general problems under consideration.

Unsteady flow over a stretching surface with a magnetic field in a rotating fluid

The effect of the magnetic field on the unsteady flow over a stretching surface in a rotating fluid has been studied. The unsteadiness in the flow field is due to the time-dependent variation of the velocity of the stretching surface and the angular velocity of the rotating fluid. The Navier-Stokes equations and the energy equation governing the flow and the heat transfer admit a self-similar solution if the velocity of the stretching surface and the angular velocity of the rotating fluid vary inversely as a linear function of time. The resulting system of ordinary differential equations is solved numerically using a shooting method. The rotation parameter causes flow reversal in the component of the velocity parallel to the strerching surface and the magnetic field tends to prevent or delay the flow reversal. The surface shear stresses dong the stretching surface and in the rotating direction increase with the rotation parameter, but the surface heat transfer decreases. On the other hand, the magnetic field increases the surface shear stress along the stretching surface, but reduces the surface shear stress in the rotating direction and the surface heat transfer. The effect of the unsteady parameter is more pronounced on the velocity profiles in the rotating direction and temperature profiles.

Genesis of workpiece roughness generated in surface grinding and polishing of metals

Assuming the grinding wheel surface to be fractal in nature, the maximum envelope profile of the wheel and contact deflections are estimated over a range of length scales. This gives an estimate of the 'no wear' roughness of a surface ground metal. Four test materials, aluminum, copper, titanium, and steel are surface ground and their surface power spectra were estimated. The departure of this power spectra from the 'no wear' estimates is studied in terms of the traction-induced wear damage of the surfaces. The surface power spectra in grinding are influenced by hardness and the power is enhanced by wear damage. No such correlation with hardness was found for the polished surface, the roughness of which is insensitive to mechanical properties and appears to be influenced by microstructure and physical properties of the material.

Finite Element Solution Of Surface-Tension Driven Flows In Laser Surface-Melting

Lasers are very efficient in heating localized regions and hence they find a wide application in surface treatment processes. The surface of a material can be selectively modified to give superior wear and corrosion resistance. In laser surface-melting and welding problems, the high temperature gradient prevailing in the free surface induces a surface-tension gradient which is the dominant driving force for convection (known as thermo-capillary or Marangoni convection). It has been reported that the surface-tension driven convection plays a dominant role in determining the melt pool shape. In most of the earlier works on laser-melting and related problems, the finite difference method (FDM) has been used to solve the Navier Stokes equations [1]. Since the Reynolds number is quite high in these cases, upwinding has been used. Though upwinding gives physically realistic solutions even on a coarse grid, the results are inaccurate. McLay and Carey have solved the thermo-capillary flow in welding problems by an implicit finite element method [2]. They used the conventional Galerkin finite element method (FEM) which requires that the pressure be interpolated by one order lower than velocity (mixed interpolation). This restricts the choice of elements to certain higher order elements which need numerical integration for evaluation of element matrices. The implicit algorithm yields a system of nonlinear, unsymmetric equations which are not positive definite. Computations would be possible only with large mainframe computers.Sluzalec [3] has modeled the pulsed laser-melting problem by an explicit method (FEM). He has used the six-node triangular element with mixed interpolation. Since he has considered the buoyancy induced flow only, the velocity values are small. In the present work, an equal order explicit FEM is used to compute the thermo-capillary flow in the laser surface-melting problem. As this method permits equal order interpolation, there is no restriction in the choice of elements. Even linear elements such as the three-node triangular elements can be used. As the governing equations are solved in a sequential manner, the computer memory requirement is less. The finite element formulation is discussed in this paper along with typical numerical results.

Nanoporous Pt with High Surface Area by Reaction-Limited Aggregation of Nanoparticles

Nanoporous structures with high active surface areas are critical for a variety of applications. Here, we present a general templateless strategy to produce such porous structures by controlled aggregation of nanostructured subunits and apply the principles for synthesizing nanoporous Pt for electrocatalytic oxidation of methanol. The nature of the aggregate produced is controlled by tuning the electrostatic interaction between surfactant-free nanoparticles in the solution phase. When the repulsive force between the particles is very large, the particles are stabilized in the solution while instantaneous aggregation leading to fractal-like structures results when the repulsive force is very low. Controlling the repulsive interaction to an optimum, intermediate value results in the formation of compact structures with very large surface areas. In the case of Pt, nanoporous clusters with an extremely high specific surface area (39 m(2)/g) and high activity for methanol oxidation have been produced. Preliminary investigations indicate that the method is general and can be easily extended to produce nanoporous structures of many inorganic materials.

Hardness of a surface containing uniformly spaced pyramidal asperities

Pyramidal asperities of different apical angle were machined on a flat copper surface. Hardness was estimated from the load-displacement graphs obtained by pressing a spherical rigid indenter onto the asperities. The variation of hardness with apical angle and pitch was recorded with a view to contributing to the development of a general framework for relating measured hardness to the surface roughness.