Surface effects on stacking fault and twin formation in fcc nanofilms: A first-principles study

The free surface effects on stacking fault and twin formation in fcc metals (Al, Cu, and Ni) were examined by first-principles calculations based on density functional theory (DFT). It is found that the generalized planar fault (GPF) energies of Ni are much larger than bulk Ni with respect to Al and Cu. The discrepancy is attributed to the localized relaxation of Ni nanofilm to accommodate the large expansion of the inter-planar separation induced at the fault plane. The localized relaxation can be coupled to the electronic structure of Ni nanofilms. (C) 2011 Elsevier B.V. All rights reserved.

Utilizing an ionic liquid for synthesizing a soft matter polymer ``gel'' electrolyte for high rate capability lithium-ion batteries

A cross-linked polymer ``gel'' electrolyte obtained from free radical polymerization of a vinyl monomer (acrylonitrile; AN) in a room temperature ionic liquid electrolyte (N,N-methyl butyl pyrrolidinium-bis (trifluoromethanesulphonyl)imide-lithium bis(trifluoromethanesulphonyl) imide;LiTFSI-[Py(1,4)-TFSI]) for application in high rate capability rechargeable lithium-ion batteries is discussed here. This is a novel alternative compared to the often employed approach of using a molecular liquid as the medium for performing the polymerization reaction. The polymer ``gel'' electrolytes (AN:Py(1,4)-TFSI = 0.16-0.18, w/w) showed remarkable compliable mechanical strength and higher thermal stability compared to LiTFSI-[Py(1,4)-TFSI]. Despite two orders increase in magnitude of viscosity of polymer ``gels'', the room temperature ionic conductivity of the ``gels'' (1.1 x 10(-3)-1.7 x 10(-3) Omega(-1) cm(-1)) were nearly identical to that of the ionic liquid (1.8 x 10(-3) Omega(-1) cm(-1)). The present ``gel'' electrolytes did not exhibit any ageing effects on ionic conductivity similar to the conventional polymer gel electrolytes (e.g. high molecular weight polymer + salt + high dielectric constant molecular solvent). The disorder (ionic liquid) to a relative order (cross-linked polymer electrolyte) transformation does not at all influence the concentration of conducting species. The polymer framework is still able to provide efficient pathways for fast ion transport. Unlike the ionic liquid which is impossible to assemble without a conventional separator in a cell, the polymer ``gel'' electrolyte could be conveniently assembled without a separator in a Li vertical bar lithium iron phosphate (LiFePO(4)) cell. Compared to the ionic liquid, the ``gel'' electrolyte showed exceptional cyclability and rate capability (current density: 35-760 mA g(-1) with LiFePO(4) electronically wired with carbon (amorphous or multiwalled nanotube [MWCNT]).

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.

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.

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.−% Zn, in equilibrium with ZnO, ZnAl2O4+Al2O3(χ) and ZnCr2O4+Cr2O3, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y2O3 ThO2 pellet was sandwiched between a CaOZrO2 crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations, The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl2O4, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.

Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites

The standard Gibbs free energy of formation of magnesium and cadmiumchromites have been determined by potentiometric measurements on reversiblesolid-state electrochemical cells [dformula (Au-5%Cd, , Au-5%Cd; Pt, + , CaO-ZrO[sub 2], + ,Pt; CdO, , CdCr[sub 2]O[sub 4] + Cr[sub 2]O[sub 3])] in the temperature range 500°–730°C, and [dformula Pt, Cr + Cr[sub 2]O[sub 3]/Y[sub 2]O[sub 3]-ThO[sub 2]/Cr + MgCr[sub 2]O[sub 4] + MgO, Pt] in the temperature range 800°–1200°C. The temperature dependence of the freeenergies of formation of the ternary compounds can be represented by theequations [dformula CdO(r.s.) + Cr[sub 2]O[sub 3](cor) --> CdCr[sub 2]O[sub 4](sp)] [dformula Delta G[sup 0] = - 42,260 + 7.53T ([plus-minus]400) J] and [dformula MgO(r.s.) + Cr[sub 2]O[sub 3](cor) --> MgCr[sub 2]O[sub 4](sp)] [dformula Delta G[sup 0] = - 45,200 + 5.36T ([plus-minus]400) J] The entropies of formation of these spinels are discussed in terms of cationdisorder and extent of reduction of Cr3+ ions to Cr2+ ions. Thermodynamicdata on the chromates of cadmium and magnesium are derived by combiningthe results obtained in this study with information available in the literatureon high temperature, high pressure phase equilibria in the systems CdO-Cr2O3-O2 and MgO-Cr2O3-O2.

Gibbs free energy of formation of magnesium stannate

he thermodynamic properties of the spinel Mg2SnO4 have been determined by emf measurements on the solid oxide galvanic cell,View the MathML source in the temperature range 600 to 1000°C. The Gibbs' free energy of formation of Mg2SnO4 from the component oxides can be expressed as View the MathML source,View the MathML source These values are in good agreement with the information obtained by Jackson et al. [Earth Planet. Sci. Lett.24, 203 (1974)] on the high pressure decomposition of magnesium stannate into component oxides at different temperatures. The thermodynamic data suggest that the spinel phase is entropy stabilized, and would be unstable below 207 (±25)°C at atmospheric pressure. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that the stannates of nickel and copper(II) are unstable.