Supercooling of the disordered vortex lattice in Bi(2)Sr(2)CaCu(2)O(8+delta)

Time-resolved local induction measurements near the vortex lattice order-disorder transition in optimally doped Bi(2)Sr(2)CaCu(2)O(8+delta) crystals show that the high-field, disordered phase can be quenched to fields as low as half the transition field. Over an important range of fields, the electrodynamical behavior of the vortex system is governed by the coexistence of ordered and disordered vortex phases in the sample. We interpret the results as supercooling of the high-field phase and the possible first-order nature of the order-disorder transition at the "second magnetization peak."     

The Electronic Structure of Pristine and Doped (100) Tilt Grain Boundaries in SrTiO3

To understand the electronic properties of doped grain boundaries, we reviewed the atomic scale techniques currently available to study the electronic structure at pristine SrTiO₃ grain boundaries. The knowledge gained from the pristine boundaries is used to interpret experimental and theoretical results from a Mn doped 5 SrTiO₃ grain boundaries. Mn atoms are shown to preferentially substitute at specific Ti sites at the grain boundary core. Furthermore, the formal oxidation state of the Mn atoms at the grain boundary core was found to be reduced compared to the Mn atoms substituting for Ti in the bulk. This change of valence did not, however, significantly affect the atomic structure of the grain boundary, as determined by Z-contrast imaging and electron energy-loss spectroscopy, which revealed similar fine-structure features at both the doped and pristine grain boundary. We conclude, therefore, that composition and atomic structure have different effects on the local electronic structure and should be treated separately in any segregation and electrical conductivity models for grain boundaries.     

Preparation and characterisation of electrodeposited amorphous Sn-Co-Fe ternary alloys

Electrochemical deposition was investigated as a process to obtain alloys of Sn-Co-Fe, which to date have not been reported in the literature. A constant current technique was used to electrochemically deposit tin-cobalt-iron alloys from a gluconate electrolyte. The gluconate system was chosen as an electrolyte, which could potentially provide an environmentally safe process. The effect of plating parameters such as current density, deposition time, temperature and pH are discussed. Results are reported for current density and plating time using an electrolyte temperature of 20-60 °C and pH of 7.0 in relation to phase composition, crystal structure and magnetic anisotropy of the deposited alloys.Investigations were conducted using ⁵⁷Fe conversion electron Mössbauer spectroscopy (CEMS), ¹¹⁹Sn CEMS, transmission Mössbauer Spectroscopy and XRD. The ⁵⁷Fe and ¹¹⁹Sn CEMS spectra and XRD showed that the dominant phase in the deposits was amorphous Sn-Co-Fe. The relative area of the 2nd and 5th lines of the sextets representing the magnetic iron containing phases was found to decrease continuously with increasing current density while at the same time no significant changes in the magnetic anisotropy was found with plating time. Magnetically split ¹¹⁹Sn spectra reflecting a transferred hyperfine field were also observed.A range of good quality amorphous Sn-Co-Fe ternary alloys was obtained over a range of operating conditions from an environmentally acceptable gluconate electrolyte.     

Ab initio study of the effect of doping on stacking faults in GaN

The influence of impurities on the basal plane stacking fault energy in GaN is investigated using density functional theory. It is found that silicon, indium, magnesium and carbon impurities each reduce the stacking fault energy by introducing changes to the bonding properties of the material. These bonding properties are analysed in terms of Mulliken charges and bond populations. It is found that the reduction in stacking fault energy correlates both with a reduction in the average anion charge and with an increase in the overlap population.     

Addition of alkynes to aldehydes and activated ketones catalyzed by rhodium-phosphine complexes

A mixture of 2-(di-tert-butylphosphino)biphenyl and dicarbonylacetonato rhodium(I) provides an effective catalyst system for the addition of alkynes to aldehydes and activated ketones. In contrast to the more common zinc-catalyzed processes, enolizable 1,2-dicarbonyls are excellent substrates for these rhodium-catalyzed additions. This reaction allows for the formation of propargylic alcohols under mild conditions, tolerating many functional groups (such as carboxylic acids) that are incompatible with other methods. Little selectivity was observed in cases of unsymmetrical 1,2-diketones. Addition of alkynes to aldehydes with an adjacent chirality center usually provides the Felkin addition product with excellent selectivity in some cases. Studies on the catalyst structure show that both the beta-diketonate and a carbon monoxide ligand appear to be bound to the active catalyst. The use of chiral phosphines to induce asymmetry in the propargyl alcohol products provided low enantioselectivity, which may be due to the phosphine having a distal relationship to the reacting centers. Modification of other ligands, such as the beta-diketonate, appears to be a more promising avenue for the development of an enantioselective variant.     

Synthesis and Characterization of PS-PIB-PS Triblock Copolymers

Abstract

Poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers synthesized via living carbocationic polymerization using a di- or tricumyl chloride/TiCl₄/pyridine initiating system in 60/40 (v/v) hexane/methyl chloride cosolvents. The kinetics of formation of the PIB block at ? 80°C were found to be first order in isobutylene (IB) concentration, first order in the concentration of initiating sites, second order in TaiCl₄ concentration, and a negative fractional order with respect to the pyridine concentration. The rate of polymerization was found to decrease with increasing temperature, indicating an equilibrium between dormant, covalent and active, ionized chain ends, and chain-end concentration studies suggested that there was no contribution by free ions to the rate of propagation. Diagnosis of the livingness of the IB polymerization indicated that at high (≥90%) monomer conversion, β-proton elimination becomes important, causing the timing of addition of styrene to be critical. Addition of styrene at an IB reaction time significantly exceeding the time necessary for complete IB consumption resulted in contamination of the product with a substantial amount of homo-PS; conversely, addition at intermediate IB conversion resulted in slow copolymerization between IB and styrene and the formation of a tapered block copolymer. Addition of styrene at an IB conversion of about 90% resulted in well-defined block copolymers which displayed ordered, phase-separated morphologies consisting of cylinders of PS in a continuous phase of PIB. The block copolymers possessed properties consistent with those of physically crosslinked rubbers. Dynamic mechanical spectroscopy revealed two glass transitions with a broad rubbery plateau extending from about 0 to 100°C, and tensile strengths of up to 25 MPa and elongations to 1000% were observed for some samples.     

Optimal doping control of magnetic semiconductors via subsurfactant epitaxy

"Subsurfactant epitaxy" is established as a conceptually new approach for introducing manganese as a magnetic dopant into germanium. A kinetic pathway is devised in which the subsurface interstitial sites on Ge(100) are first selectively populated with Mn, while lateral diffusion and clustering on or underneath the surface are effectively suppressed. Subsequent Ge deposition as a capping layer produces a novel surfactantlike phenomenon as the interstitial Mn atoms float towards newly defined subsurface sites at the growth front. Furthermore, the Mn atoms that failed to float upwards are uniformly distributed within the Ge capping layer. The resulting doping levels of order 0.25 at. % would normally be considered too low for ferromagnetic ordering, but the Curie temperature exceeds room temperature by a comfortable margin. Subsurfactant epitaxy thus enables superior dopant control in magnetic semiconductors.