A 105K superconductor with three Cu---O layers in the bismuth cuprate system : Bi1.5Pb0.5Ca2.5Sr1.5Cu3O10+delta

The n=3 member of the Bi1.5Pb0.5 (Ca, Sr) n+1CunO2n+4+δ system has been prepared and characterized by X-ray diffraction and electron microscopy. High-Tc superconductivity in the n=3 member has been established by resistivity, AC susceptibility and microwave absorption measurements. It has a Tc of not, vert, similar 105K compared to a Tc of not, vert, similar 82K of the corresponding n=2 member.

Microstructural study of rapidly solidified titanium eutectoid alloysstar, open

Rapid solidification of Ti-7.3wt.%Cu (near-eutectoid composition), Ti-36.2wt.%Ni and Ti-34.3wt.% Ni-5.8wt.%Si alloys has been carried out by electron beam melting and splat quenching on a water-cooled rotating copper disc. The product obtained was in the form of thin ribbons 60–100 μm thick. Transmission electron microscopy studies of Ti---Cu alloy splats showed that the microstructure consisted of a mixture of martensite and a lamellar eutectoid product. The formation of the intermetallic compound Ti2Cu involved a diffusionless ω transformation and spinodal clustering. In the case of Ti---Ni alloy the as-quenched microstructure is complex, consisting of α, transformed β and intermetallic phases. This could have arisen possibly as a result of local variation in cooling rates. Rapid solidification of Ti---Ni---Si alloy resulted in partial quenching of an amorphous phase. The amorphous phase was seen to be extremely hard (a Vickers hardness of about 800 HV).

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.

Role of Mn impurity in the deterioration of ZnS:Cu, Br electroluminescent phosphors

ZnS:Cu, Br powder EL phosphors showed 6-line EPR signal at 25°C whose intensity increases with Cu content and on annealing in Zn-vapour. The signal arises from native Mn impurity. The starting material does not show any EPR signal since Mn2+ acts as an affinity potential well for a hole in ZnS, forming Mn3+ - a chemically uncommon situation in sulfides. In doped ZnS, holes are trapped at Cu such that Mn2+ persists. Deterioration of EL brightness is accompanied by the decrease in EPR signal intensity due to field assisted hole transference to Mn2+. Intentional addition of Mn in ZnS:Cu, Br decreases the brightness and shortens life time. Stable phosphors require ZnS with Mn content less than 1014 cm−3.

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.

Geochemistry of meta-anorthosites from Holénarasipur, Karnataka, South India

Geochemical and Rb---Sr isotope studies indicate that the meta-anorthosites of Holénarasipur, occurring as minor differentiates in ultramafic-mafic complex are igneous intrusives with cumulus character, emplaced around 3095 m.y. ago. The fine-grained nature is secondary; relict cumulus features are preserved in less deformed bodies. In major element chemistry, they compare well with other Archean anorthosites. Abundance levels of Ti, Zr, Y and P indicate the evolution through crystal fractionation of a parental magma; cumulus olivine and pyroxenes dominated chemistry for ultramafites, cumulus plagioclase and possibly clinopyroxene controlled chemistry for anorthosite-gabbros and cumulus magnetite in magnetite-gabbros. Magnetite is not an early cumulate. REE geochemistry is dominated by plagioclase with low abundance levels, slightly LREE enriched and variable positive Eu anomaly. Sr and Image values vary with An content in plagioclase. Isotopic studies show low initial Image (=0.7016) indicating that Rb---Sr isochron age represents the time of intrusion rather than the time of metamorphism.

Micromechanisms of damage in a hypereutectic Ti-6Al-4V-B alloy

The tensile stress–strain response and fracture in a hypereutectic Ti–6Al–4V–1.7B (weight percent) alloy were investigated by employing interrupted tensile tests combined with acoustic emission measurements, with the aim to identify the cause for the observed low ductility in this alloy. These tests were complemented with microscopy. The alloy contains TiB whiskers of different length scales, the majority of which include micro-whiskers ( 5–10 μm length) and a few primary-whiskers ( 200–300 μm length). Although the fracture of both types of whiskers occur during deformation, the former leads to a gradual decrease in the secant modulus whereas initiation of the latter leads to a drastic drop in the modulus along with failure of the specimen, limiting the ductility.

Cu (DPM)2-initiated vinyl polymerization

The behavior of cupric dipivaloylmethide in vinyl polymerization systems was investigated with a view to understanding the mechanism of polymerization initiation. Results of polymerization reactions together with spectral investigation data are presented. Polymerization in the presence of the chelate proceeds through a free-radical process. The corresponding kinetic and transfer constants and activation energy values suggest a normal propagation step. With the help of spectral data an attempt is made to suggest a plausible mechanism of initiation.

Interfacial structure and crystallographic studies of transformations in betat' and beta Cu---Zn alloys-II. martensitic formation of alpha1' plates in beta'

A TEM study of the interphase boundary structure of 9R orthorhombic alpha1' martensite formed in beta' Cu---Zn alloys shows that it consists of a single array of dislocations with Burgers vector parallel to left angle bracket110right-pointing angle beta and spaced about 3.5 nm apart. This Burgers vector lies out of the interface plane; hence the interface dislocations are glissile. Unexpectedly, though, the Burgers vectors of these dislocations are not parallel when referenced to the matrix and the martensite lattices. This finding is rationalized on published hard sphere models as a consequence of relaxation of a resultant of the Bain strain and lattice invariant shear displacements within the matrix phase.

Structural transitions in (La,Ln)2CuO4 and La2(Cu,Ni)O4 systems

Solid solutions of the formula La2−xLnxCuO4 (Ln = Pr, Nd) possess the orthorhombic structure of La2CuO4 for small values of x and transform to the tetragonal Nd2CuO4 structure at a critical value of x. At the critical composition, there is an abrupt change in specific volume as well as the Image ratio. The material exhibits temperature-independent electrical resistivity below the critical value x and semiconducting behaviour above it. The specific volume and Image ratio smoothly decrease with increase in x in the La2Cu1−xNixO4 system, although the solid solution possess the tetragonal K2NiF4 structure when x>0.1. Compositions with x>0.1 exhibit a gradual semiconductor metal transition similar to that of La2NiO4, the transition temperature decreasing with increasing

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

2-Thioacetamido thiazole as an ambidentate ligand. Complexes of Zn(II), Cd(II), Hg(II) and Cu(I)

Metal complexes of thiazoles have been studied in recent years[I-3] because of their biochemical importance[4,5]. However, data on metal complexes of thiazole derivatives containing another coordinating function are limited[2]. We have synthesized and examined the donor characteristics of a new ligand, 2-thioacetamide thiazole (TATZ)(I) towards chlorides and bromides of Zn(II), Cd(II), Hg(II) and Cu(I). The presence of four potential donor atoms and extensive charge delocalization should render TATZ a versatile ligand.

A Comparative Study of Electrochemical Kinetic Parameters by the Potential Step Method. Electrode Reactions of CyDTA and EDTA Complexes of Cu(II) at DME

By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

Transformation microstructures in a Ti-31A1-13Mo alloy

Some initial results are presented on the formation of the y phase, based on the intermetallic TiA1 (LIo, c/a = 1.02) from the phase, based on the intermetallic TidAl (DOts , c/a = 0.801) in a Ti-31wt. Al-13wt Mo alloy. The study is part of a programme to evaluate microstractures and properties of alloys containing the y phase in the Ti-Mo-AI ternary system.

Elastic modulus of Ti-6Al-4V-xB alloys with B up to 0.55 wt.%

An anomalous variation in the experimental elastic modulus, E, of Ti-6Al-4V-xB (with x up to 0.55 wt.%) is reported. Volume fractions and moduli of the constituent phases were measured using microscopy and nanoindentation,respectively. These were used in simple micromechanical models to examine if the E values could be rationalized. Experimental E values higher than the upper bound estimates suggest complex interplay between microstructural modifications, induced by the addition of B, and properties.