Electrochemical Properties of Li3N Dissolved in Molten LiCl at 900 K

Thermodynamic properties of Li3N dissolved in the molten LiCl salt at 900 K were explored using electrochemical methods. It was difficult to determine precisely the decomposition voltage of Li3N dissolved in the molten salt by cyclic voltammetry. The oxidation wave of N3��� ion could not be located with high accuracy. However, the lithium activity of the Pb-Li alloy in equilibrium with the molten salt containing dissolved Li3N under nitrogen atmosphere could be measured electrochemically with high accuracy using the Li/Li + reference electrode. Under the conditions used in this study, the potential of the Li-Pb electrode is equal to the decomposition voltage of Li3N. The activity of Li3N in molten LiCl was determined for anionic fractions of N3��� ranging from xN3��� = 10���4 to 0.028. The nitride ion concentration in the salt was determined by chemical titration. The activity coefficient of the Li3N at high dilution was found to be very low, around 10���4. The activity coefficient increases sharply with composition and has a value of 0.25 at xN3��� = 0.028. ��2001 The Electrochemical Society. All rights reserved.

Stability of the flow of a fluid through a flexible tube at high Reynolds number

The stability of the Hagen-Poiseuille flow of a Newtonian fluid in a tube of radius R surrounded by an incompressible viscoelastic medium of radius R < r < HR is analysed in the high Reynolds number regime. The dimensionless numbers that affect the fluid flow are the Reynolds number Re = (��VR / ��), the ratio of the viscosities of the wall and fluid ��r = (��s/��), the ratio of radii H and the dimensionless velocity �� = (��V2/G)1/2. Here �� is the density of the fluid, G is the coefficient of elasticity of the wall and Vis the maximum fluid velocity at the centre of the tube. In the high Reynolds number regime, an asymptotic expansion in the small parameter �� = (1/Re) is employed. In the leading approximation, the viscous effects are neglected and there is a balance between the inertial stresses in the fluid and the elastic stresses in the medium. There are multiple solutions for the leading-order growth rate do), all of which are imaginary, indicating that the fluctuations are neutrally stable, since there is no viscous dissipation of energy or transfer of energy from the mean flow to the fluctruations due to the Reynolds strees. There is an O(��1/2) correction to the growth rate, s(1), due to the presence of a wall layer of thickness ��1/2R where the viscous stresses are O(��1/2) smaller than the inertial stresses. An energy balance analysis indicates that the transfer of energy from the mean flow to the fluctuations due to the Reynolds stress in the wall layer is exactly cancelled by an opposite transfer of equal magnitude due to the deformation work done at the interface, and there is no net transfer from the mean flow to the fluctuations. Consequently, the fluctuations are stabilized by the viscous dissipation in the wall layer, and the real part of s(1) is negative. However, there are certain values of �� and wavenumber k where s(l) = 0. At these points, the wail layer amplitude becomes zero because the tangential velocity boundary condition is identically satisfied by the inviscid flow solution. The real part of the O(��) correction to the growth rate s(2) turns out to be negative at these points, indicating a small stabilizing effect due to the dissipation in the bulk of the fluid and the wall material. It is found that the minimum value of s(2) increases [is proportional to] (H ��� 1)���2 for (H ��� 1) [double less-than sign] 1 (thickness of wall much less than the tube radius), and decreases [is proportional to] (H���4 for H [dbl greater-than sign] 1. The damping rate for the inviscid modes is smaller than that for the viscous wall and centre modes in a rigid tube, which have been determined previously using a singular perturbation analysis. Therefore, these are the most unstable modes in the flow through a flexible tube.

Structural, optical and nanomechanical properties of (1���1���1) oriented nanocrystalline ZnTe thin films

Structural, optical and nanomechanical properties of nanocrystalline Zinc Telluride (ZnTe) films of thickness upto 10 microns deposited at room temperature on borosilicate glass substrates are reported. X-ray diffraction patterns reveal that the films were preferentially oriented along the (1���1���1) direction. The maximum refractive index of the films was 2.74 at a wavelength of 2000 nm. The optical band gap showed strong thickness dependence. The average film hardness and Young's modulus obtained from load-displacement curves and analyzed by Oliver-Pharr method were 4 and 70 GPa respectively. Hardness of (1���1���1) oriented ZnTe thin films exhibited almost 5 times higher value than bulk. The studies show clearly that the hardness increases with decreasing indentation size, for indents between 30 and 300 nm in depth indicating the existence of indentation size effect. The coefficient of friction for these films as obtained from the nanoscratch test was ~0.4.

Lubricity of an oil in water emulsion in metal cutting: The effect of hydrophilic/lypophilic balance of emulsifiers

A steel disc is cut using a single point tool. The coefficient of friction of the nascent cut surface is measured by a spherical steel pin situated in close proximity of the point of cutting. The tool, disc and the friction pin are immersed in an oil in water emulsion bath during the experiment. The purpose of the experiments conducted here is to record the effect of hydrophilic/lypophilic balance (HLB) of the emulsifier on the lubricity experienced in the cutting operation. The more lypophilic emulsifiers were found to give greater lubricity than what is recorded when the emulsifier is more hydrophilic. XPS and FTIR spectroscopy are used to explore the tribofilm generated on the nascent cut surface to indicate a possible rationale for the effect. (C) 2011 Elsevier B.V. All rights reserved.

Structural, optical and nanomechanical properties of (1���1���1) oriented nanocrystalline ZnTe thin films

Structural, optical and nanomechanical properties of nanocrystalline Zinc Telluride (ZnTe) films of thickness upto 10 microns deposited at room temperature on borosilicate glass substrates are reported. X-ray diffraction patterns reveal that the films were preferentially oriented along the (1���1���1) direction. The maximum refractive index of the films was 2.74 at a wavelength of 2000 nm. The optical band gap showed strong thickness dependence. The average film hardness and Young's modulus obtained from load-displacement curves and analyzed by Oliver-Pharr method were 4 and 70 GPa respectively. Hardness of (1���1���1) oriented ZnTe thin films exhibited almost 5 times higher value than bulk. The studies show clearly that the hardness increases with decreasing indentation size, for indents between 30 and 300 nm in depth indicating the existence of indentation size effect. The coefficient of friction for these films as obtained from the nanoscratch test was ~0.4.

Thermal cycling of Mg-MMCs

Creep resistant Mg alloy QE22 reinforced with maftec(R), saffil(R) or supertec(R) short fibres is cycled between room temperature and 308degreesC at different ramp rates in the longitudinal and transverse directions. From the careful analysis of the strain vs. temperature thermal cycling curves true material behaviour and artifacts from the dilatometer are deciphered. From this analysis true coefficient of thermal expansion and relaxation processes are deduced. Hysteresis at higher temperatures is attributed to the relaxation process, whereas hysteresis at low temperatures giving a tilt-ground shape to the thermal cycling curves is again an artifact due to the instrument. The change in ramp rate highlights this effect. Finally, the effect of thermal cycling on microstructure is examined.

Uncertainty analysis of vibrational frequencies of an incompressible liquid in a rectangular tank with and without a baffle using polynomial chaos expansion

Polynomial chaos expansion (PCE) with Latin hypercube sampling (LHS) is employed for calculating the vibrational frequencies of an inviscid incompressible fluid partially filled in a rectangular tank with and without a baffle. Vibration frequencies of the coupled system are described through their projections on the PCE which uses orthogonal basis functions. PCE coefficients are evaluated using LHS. Convergence on the coefficient of variation is used to find the orthogonal polynomial basis function order which is employed in PCE. It is observed that the dispersion in the eigenvalues is more in the case of a rectangular tank with a baffle. The accuracy of the PCE method is verified with standard MCS results and is found to be more efficient.

A Reliable method of obtaining Breakthrough Curves of ions in Soils using Transport Equation

Molecular diffusion plays a dominant role in transport of contaminants through fine-grained soils with low hydraulic conductivity. Attenuation processes occur while contaminants travel through the soils. Effective diffusion coefficient (De) is expected to take into consideration various attenuation processes. Effective diffusion coefficient has been considered to develop a general approach for modelling of contaminant transport in soils.The effective diffusion coefficient of sodium in presence of sulphate has been obtained using the column test.The reliability of De, has been checked by comparing theoretical breakthrough curves of sodium ion in soils obtained using advection diffusion equation with the experimental curve.

Impact of Sulphate counter ion in the migration of sodium ion through soils

Laboratory advection-diffusion tests are performed on two regional soils-Brown Earth and Red Earth-in order to assess their capacity to control contaminant migration with synthetic contaminant solution of sodium sulphate with sodium concentration of 1000 mg/L. The test was designed to study the transport/attenuation behaviour of sodium in the presence of sulphate. Effective diffusion coefficient (De) that takes into consideration of attenuation processes is used. Cation exchange capacity is an important factor for the attenuation of cationic species. Monovalent sodium ion cannot usually replace other cations and the retention of sodium ion is very less. This is particularly true when chloride is anion is solution. However, sulphate is likely to play a role in the attenuation of sodium. Cation exchange capacity and type of exchangeable ions of soils are likely to play an important role. The effect of sulphate ions on the effective diffusion coefficient of sodium, in two different types of soils, of different cation exchange capacity has been studied. The effective diffusion coefficients of sodium ion for both the soils were calculated using Ogata Bank���s equation. It was shown that effective diffusion coefficient of sodium in the presence of sulphate is lower for Brown Earth than for Red Earth due to exchange of sodium with calcium ions from the exchangeable complex of clay. The soil with the higher cation exchange retained more sodium. Consequently, the breakthrough times and the number of pore volumes of sodium ion increase with the cation exchange capacity of soil.

Response of Materials during sliding on various surface textures

In the present investigation, basic studies were conducted using Inclined pin-on-plate sliding Tester to understand the role of surface texture of hard material against soft materials during sliding. Soft materials such as Al-Mg alloy, pure Al and pure Mg were used as pins and 080 M40 steel was used as plate in the tests. Two surface parameters of steel plates ��� roughness and texture ��� were varied in tests. It was observed that the transfer layer formation and the coefficient of friction which has two components, namely adhesion and plowing component, are controlled by the surface texture of harder material. For the case of Al-Mg alloy, stick-slip phenomenon was absent under both dry and lubricated conditions. However, for the case of Al, it was observed only under lubricated conditions while for the case of Mg, it was observed under both dry and lubricated conditions. Further, it was observed that the amplitude of stick-slip motion primarily depends on plowing component of friction. The plowing component of friction was highest for the surface that promotes plane strain conditions near the surface and was lowest for the surface that promotes plane stress conditions near the surface.

The role of surface texture on friction and transfer layer formation during repeated sliding of Al-4Mg against steel

In the present investigation, various kinds of textures, namely, unidirectional, 8-ground, and random were attained on the die surfaces. Roughness of the textures was varied using different grits of emery papers or polishing powders. Then pins made of Al-4Mg alloys were slid against steel plates at various numbers of cycles, namely, 1, 3, 5, 10 and 20 using pin-on-plate reciprocating sliding tester. Tests were conducted at a sliding velocity of 2 minis in ambient conditions under both dry and lubricated conditions. A constant normal load of 35 N was applied in the tests. The morphologies of the worn surfaces of the pins and the formation of transfer layer on the counter surfaces were observed using a scanning electron microscope. Surface roughness parameters of the plates were measured using an optical profilometer. In the experiments, it was observed that the coefficient of friction and formation of the transfer layer depend on the die surface textures under both dry and lubricated conditions. More specifically, the coefficient of friction decreases for unidirectional and 8-ground surfaces while for random surfaces it increases with number of cycles. However, the coefficient of friction is highest for the sliding perpendicular to the unidirectional textures and least for the random textures under both dry and lubricated conditions. The difference in friction values between these two surfaces decreases with increasing number of cycles. The variation in the coefficient of friction under both dry and lubrication conditions is attributed to the change in texture of the surfaces during sliding. (C) 2011 Elsevier B.V. All rights reserved.

Wear behavior of plasma electrolytic oxidation (PEO) and hybrid coatings of PEO and laser on MRI 230D magnesium alloy

Wear resistant coatings were produced on a permanent mould cast MRI 230D Mg alloy by (a) PEO in silicate based electrolyte, (b) PEO in phosphate based electrolyte, (c) hybrid coatings of silicate PEO followed by laser surface alloying (LSA) with Al and Al(2)O(3), and (d) hybrid coatings of phosphate PEO followed by LSA with Al and Al(2)O(3). Microstructural characterization of the coatings was carried out by scanning electron microscopy (SEM) and X(ray diffraction. The tribological behavior of the coatings was investigated under dry sliding condition using linearly reciprocating ball-on-flat wear test. Both the PEO coatings exhibited a friction coefficient of about 0.8 and hybrid coatings exhibited a value of about 0.5 against the AISI 52100 steel ball as the friction partner, which were slightly reduced with the increase in applied load. The PEO coatings sustained the test without failure at 2 N load but failed at 5 N load due to micro-fracture caused by high contact stresses. The hybrid coatings did not get completely worn off at 2 N load but were completely removed exposing the substrate at 5 N load. The PEO coatings exhibited better wear resistance than the hybrid coatings and silicate PEO coatings exhibited better wear resistance than the phosphate PEO coatings. Both the PEO coatings melted/decomposed on laser irradiation and all the hybrid coatings exhibited similar microstructure and wear behavior irrespective of the nature of the primary PEO coating or laser energies. SEM examination of worn surfaces indicated abrasive wear combined with adhesive wear for all the specimens. The surface of the ball exhibited a discontinuous transfer layer after the wear test. (C) 2011 Elsevier B.V. All rights reserved.

Friction and transfer layer formation in polymer-steel tribo-system: Role of surface texture and roughness parameters

In the present investigation, various kinds of surface textures were attained on the steel plates. Roughness of the textures was varied using various grinding or polishing methods. The surface textures were characterized in terms of roughness parameters using an optical profilometer. Then experiments were conducted using an inclined pin-on-plate sliding apparatus to identify the role of surface texture and its roughness parameters on coefficient of friction and transfer layer formation. In the experiments, a soft polymer (polypropylene) was used for the pin and hardened steel was used for the plate. Experiments were conducted at a sliding velocity of 2 minis in ambient conditions under both dry and lubricated conditions. The normal load was varied from 1 to 120 N during the tests. The morphologies of the worn surfaces of the pins and the formation of a transfer layer on the steel plate surfaces were observed using a scanning electron microscope. Based on the experimental results, it was observed that the transfer layer formation and the coefficient of friction along with its two components, namely adhesion and plowing, were controlled by the surface texture of the harder mating surfaces and were less dependent of surface roughness (R(a)) of the harder mating surfaces. The effect of surface texture on the friction was attributed to the variation of the plowing component of friction for different surfaces. Among the various surface roughness parameters studied, the mean slope of the profile, Delta(a), was found to most accurately characterize variations in the friction and wear behavior. (C) 2011 Elsevier B.V. All rights reserved.

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.

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.