Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Insulator-metal transition

A theory of the insulator-metal transition in transition-metal compounds is developed in terms of the collapse of the effective energy gap which is a function of the thermally excited electron-hole pairs. This dependence is shown to arise from the hole-lattice interaction. The reaction of the lattice is found to be equivalent to generating an internal positive pressure (strain). Estimates show that the observed typical behaviour of the conductivity jump and the change of volume at the transition temperature can be explained by the present theory.

Comparison of elasticity and shell-theory solutions for finite circular cylindrical shells

A finite circular cylindrical shell subjected to a band of uniform pressure on its outer rim was investigated, using three-dimensional elasticity theory and the classical shell theories of Timoshenko (or Donnell) and Flügge. Detailed comparison of the resulting stresses and displacements was carried out for shells with ratios of inner to outer shell radii equal to 0.80, 0.85, 0.90 and 0.93 and for ratios of outer shell diameter to length of the shell equal to 0.5, 1 and 2. The ratio of band width to length of the shell was 0.2 and Poisson's ratio used was equal to 0.3. An Elliot 803 digital computer was used for numerical computations.

Experimental evidence of the cavity theory of sorption-desorption hysteresis by a study of the effect of electric discharge on entrapped water in silica gel

With the use of the quartz fiber spring balance, sorptions and desorptions of water on silica gel at 30°C were studied and the permanent and reproducible hysteresis loop was obtained. At different points on the desorption curve forming the loop, the gel was subjected to high tension glow electric discharge. As a result of the electric discharge, the gel at any point on the desorption curve shifts to a corresponding point on the sorption curve. This is due to the release from the cavities of gel of the entrapped water held in a metastable state. The electric discharge has no effect on the gel at different points on portions of the desorption curve which coincide with the sorption curve and also on the sorption curve itself, indicating the absence of entrapped water in the gel in these regions. The results afford direct experimental evidence of the reality of the cavity theory of sorption-desorption hysteresis.

Pressure dependence of chlorine nuclear quadrupole resonance in sodium chlorate

The pressure dependence of the chlorine NQR frequency in NaClo3 has been investigated up to 20 k bar hydrostatic pressure. A distinct break in slope in the pressure dependence of the resonance frequency is observed near 11 k bar. This is attributed to a phase transition reported earlier by Bridgman in this pressure region.

Positional dependence of material flow in friction stir welding: analysis of joint line remnant and its relevance to dissimilar metal welding

Understanding material flow in friction stir welding is important for production of sound dissimilar metal welding that control the intermixing of two alloys being welded and consequent formation of new constituents which influences the weld properties. In the present experimental investigation material flow patterns are visualised using dissimilar and similar aluminium alloys using a simple innovative ,experiment. The experimental results reveal that only a portion of material transported from the leading edge undergoes chaotic flow and the remaining is deposited systematically in the trailing edge of the weld. Using this information it is shown that the formation of a friction stir welding defect, joint line remnant, does not occur only when the weld interface is on the advancing side. The material flow visualisation study has been utilised to analyse the mechanism of weld formation and its usefulness in improving fatigue properties and for dissimilar metal welds.

Four-dimensional current algebra from Chern-Simons theory

We study an abelian Chern-Simons theory on a five-dimensional manifold with boundary. We find it to be equivalent to a higher-derivative generalization of the abelian Wess-Zumino-Witten model on the boundary. It contains a U(1) current algebra with an operational extension.

Rotation sensitivity of Lau fringes: an analysis based on coherence theory

An analysis based on coherence theory is presented, which explains the experimentally observed rotation sensitivity of the contrast of Lau fringes obtained under spatially incoherent illumination.

Interfacial coupling and its size dependence in PbTiO3 and PbMg1/3Nb2/3O3 multilayers

Multilayers of Pb(Mg1/3Nb2/3)O-3 (PMN)-PbTiO3 (PT) were deposited through pulsed laser ablation deposition with different periodicities (d=10, 20, 30, 40, 50, 60, and 70 nm) for a constant total thickness of the film. The presence of superlattice reflections in the x-ray diffraction pattern clearly showed the superlattice behavior of the fabricated structures over a periodicity range of 20-50 nm. Polarization hysteresis and the capacitance-voltage characteristics of these films show clear size dependent ferroelectric and antiferroelectric (AFE) characteristics. Presence of long-range coupling and strain in multilayers with lower periodicity (similar to 10 nm) exhibited a clear ferroelectric behavior similar to a solid solution of PMN and PT. Multilayers with higher periodicities (20-50 nm) exhibited antiferroelectric behavior, which could be understood from the energy arguments. On further increase of periodicity, they again exhibit ferroelectric behavior. The polarization studies were carried out beyond the Curie temperature T-c of PMN to understand the interlayer interaction. The interaction is changed to a ferroelectric-paraelectric interlayer and tends to lose its antiferroelectric behavior. The behavior of remnant polarization P-r and dP(r)/dT with temperature clearly proves that the AFE coupling of these superlattices is due to the extrinsic interfacial coupling and not an intrinsic interaction as in a homogeneous conventional AFE material. The evidence of an averaged behavior at a periodicity of similar to 10 nm, and the behavior of individual materials at larger periodicities were further confirmed through dielectric phase transition studies. The presence of AFE interfacial coupling was insignificant over the dielectric phase transition of the multilayers.

Temperature and pressure dependence of direct current electrical resistivity in the Na2O-ZnO-B2O3 glass system

Two series of glasses were prepared, xNa2O, yZnO, 100 - x - yB2O3 and 30 - xNa2O, xZnO, 70B2O3 (mol%). The temperature dependence of the direct current resistivity was measured from room temperature to about 700 K and in both series of glasses we observed a simple Arrhenius type of temperature dependence. However, the resistivity of the binary alkali glass increased steeply by as much as two orders of magnitude with the addition of even a small quantity of ZnO and remained virtually unaffected by further addition of ZnO. The resistivity decreases gradually with increasing pressure in Na2O-B2O3 but increases with increasing pressure with the addition of ZnO.

Molecular theory of solvation and solvation dynamics of a classical ion in a dipolar liquid

A microscopic theory of equilibrium solvation and solvation dynamics of a classical, polar, solute molecule in dipolar solvent is presented. Density functional theory is used to explicitly calculate the polarization structure around a solvated ion. The calculated solvent polarization structure is different from the continuum model prediction in several respects. The value of the polarization at the surface of the ion is less than the continuum value. The solvent polarization also exhibits small oscillations in space near the ion. We show that, under certain approximations, our linear equilibrium theory reduces to the nonlocal electrostatic theory, with the dielectric function (c(k)) of the liquid now wave vector (k) dependent. It is further shown that the nonlocal electrostatic estimate of solvation energy, with a microscopic c(k), is close to the estimate of linearized equilibrium theories of polar liquids. The study of solvation dynamics is based on a generalized Smoluchowski equation with a mean-field force term to take into account the effects of intermolecular interactions. This study incorporates the local distortion of the solvent structure near the ion and also the effects of the translational modes of the solvent molecules.The latter contribution, if significant, can considerably accelerate the relaxation of solvent polarization and can even give rise to a long time decay that agrees with the continuum model prediction. The significance of these results is discussed.

Exotic dielectric behavior of polar liquids

We present a report of our analysis of wave vector dependence of the static dielectric function of a dipolar liquid obtained by a microscopic calculation. At low values of the wave vector (k), the longitudinal dielectric function ϵ(k) increases with k, in contradiction to some assumptions reported in the literature. As the value of k is increased, ϵ(k) diverges at a critical value kc which depends on the value of the long wavelength static dielectric constant (ϵ0) of the liquid. The dielectric function is negative for values of k greater than kc. At large values of k, the calculated ϵ(k) fails to attain the limiting value of unity. We attribute this result to the failure of the point dipole assumption made in the evaluation of the polarization correlation function required by the theory. The behavior of ϵ(k) for the dipolar liquid is compared with that of one component plasma for which reliable results can be obtained over the full range of wave vectors. For both systems, the stability conditions are fulfilled at all values of k. A plausible explanation of this rather exotic behavior of ϵ(k) is given.