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.

Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.

ac susceptibility and electrical resistivity in Fe80-xNixCr20 (21 \leq x \leq 30) alloys

ac susceptibility and electrical resistivity studies on polycrystalline Fe80-xNixCr20 (21 \leq x \leq 30) alloys, with x=21, 23, 26, and 30, between 4.2 and 80 K, are reported. A previous dc magnetization study indicated the presence of ferro-spin-glass mixed-phase behavior in x=23 and 26 alloys while the alloys with x=21 and 30 were found to be spin-glass and ferromagnetic, respectively. The present ac susceptibility results support the above picture. In the electrical resistivity study, a low-temperature minimum in the resistivity-temperature curve is observed in all the alloys except the ferromagnetic one.

Effect of Load on Dry Sliding Wear of Aluminum-Silicon Alloys

Aluminum-silicon alloy pins were slid against steel disks under nominally dry condition at a speed of 0.6 m s-1. Each pin was slid at a constant load for 5 min, the load being increased in suitable steps from 2 to 65 N. The results show the wear to increase almost monotonically with load, to be sensitive to the presence of silicon in the alloy, and to be insensitive to actual silicon content. The monotonic nature of wear rate-load characteristic suggests that one dominant wear mechanism prevails over the load range studied. Morphological studies of the pin surface and the debris support this contention and point to delamination as being the dominant mode of wear.

Wear resistance of cast graphitic aluminium alloys

Wear rates of several cast aluminium base alloys have been measured for lubricated rubbing against a rotating hardened steel disk. Wear rates of cast graphitic aluminium-silicon-nickel alloys were lower than those of pure Al, Al-Si and Al-Si-Ni alloys especially above pressures of 0.02 kg/mm2. The high wear resistance is attributed to the presence of graphite particles in the matrix which act as a solid lubricant. Additions of nickel alone to Al-Si alloys decrease the wear resistance. Graphitic aluminium-silicon-nickel alloys containing above 2% graphite can be mated unlubricated against the rotating steel disk after a one minute lubricated run-in period. Graphite particles may be potentially suitable to replace part of all of the tin in aluminium-tin bearing alloys.

Behaviour of ultrasonic velocities in amorphous Se90Ge10 and Se85Ge15 alloys near their glass transition

Precise measurements of 10 MHz frequency longitudinal and shear wave velocities are reported in amorphous SeGe alloys near their glass transition temperature T g . There is a sharp decrease of the velocities near T g , but the reduction in velocities appears smaller than expected.

Effect of microstructure and mechanical properties on the seizure resistance of cast aluminium alloys

Seizure resistance of several cast aluminium base alloys has been examined using a standard Hohman Wear Tester. Disks of aluminium base alloys were run against a standard aluminium 12% silicon base alloy. The seizure resistance of the alloys (as measured by the lowest bearing parameter reached before seizure) increased with hardness, yield and tensile strength. In Al-Si-Ni alloys where silicon and nickel have little solid solubility in α-aluminium and Si and Ni Al3 hard phases are formed, the minimum bearing parameter decreased with the parameter V (The product of vol. % of hard phases in the disk and the shoe). Apparently the silicon and NiAl3 particles provided discontinuities in the matrix and reduced the probability (1 − V) of the α-aluminium phase in the disk coming into contact with the α-aluminium phase in the shoe. The copper and magnesium containing Al-Si-Ni alloys with lesser volumes of hard phases exhibit considerably better seizure resistance indicating that a slight increase in the solute content or the hardness of the primary α-phase leads to a considerable increase in seizure resistance. Deformation during wear and seizure leads to fragmentation of the original hard particles into considerably smaller particles uniformly dispersed in the deformed α-aluminium matrix.

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

Wear resistance of cast graphitic aluminium alloys

Wear rates of several cast aluminium base alloys have been measured for lubricated rubbing against a rotating hardened steel disk. Wear rates of cast graphitic aluminium-silicon-nickel alloys were lower than those of pure Al, Al-Si and Al-Si-Ni alloys especially above pressures of 0.02 kg/mm2. The high wear resistance is attributed to the presence of graphite particles in the matrix which act as a solid lubricant. Additions of nickel alone to Al-Si alloys decrease the wear resistance. Graphitic aluminium-silicon-nickel alloys containing above 2% graphite can be mated unlubricated against the rotating steel disk after a one minute lubricated run-in period. Graphite particles may be potentially suitable to replace part of all of the tin in aluminium-tin bearing alloys.

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.

Ultrasonic velocities and thermal expansion coefficients of amorphous Se80Te20 and Se90Te10 alloys near glass transitions

Precise measurements of the ultrasonic velocities and thermal expansivities of amorphous Se80Te20 and Se90Te10 alloys are reported near the glass transition. The samples are produced by liquid quenching. The longitudinal and transverse velocities are measured at 10 MHz frequency using the McSkimin pulse superposition technique. The thermal expansivities,agr, are measured using a three-terminal capacitance bridge. Theagr-values show a sharp maximum near the glass transition temperature,T g. The ultrasonic velocities also show a large temperature derivative, dV/dT nearT g. The data are discussed in terms of existing theories of the glass transition. The continuous change inagr shows that the glass transition is not a first-order transition, as suggested by some theories. The samples are found to be deformed by small loads nearT g. The ultrasonic velocities and dV/dT have contributions arising from this deformation.

Resistance Minimum in Dilute Magnetic Alloys in the Absence of Impurity Moments

A possible mechanism for the resistance minimum in dilute alloys in which the localized impurity states are non-magnetic is suggested. The fact is considered that what is essential to the Kondo-like behaviour is the interaction of the conduction electron spin s with the internal dynamical degrees of freedom of the impurity centre. The necessary internal dynamical degrees of freedom are provided by the dynamical Jahn-Teller effect associated with the degenerate 3d-orbitals of the transition-metal impurities interacting with the surrounding (octahedral) complex of the nearest-neighbour atoms. The fictitious spin I characterizing certain low-lying vibronic states of the system is shown to couple with the conduction electron spin s via s-d mixing and spin-orbit coupling, giving rise to a singular temperature-dependent exchange-like interaction. The resistivity so calculated is in fair agreement with the experimental results of Cape and Hake for Ti containing 0.2 at% of Fe.