Field-swept pulsed electron paramagnetic resonance of Cr3+-doped ZBLAN fluoride glass

Field-swept pulsed electron paramagnetic resonance (EPR) spectra of a ZBLAN fluoride glass doped with a low concentration of Cr3+ are obtained using echo-detected EPR and hole-burning free induction decay detection. We review the utility of the pulsed EPR technique in generating field-swept EPR spectra, as well as some of the distorting effects that are peculiar to the pulsed detection method. The application of this technique to Cr3+-doped ZBLAN reveals that much of the broad resonance extending from g(eff) = 5.1 to g(eff) = 1.97, characteristic of X-band continuous wave EPR of Cr3+ in glasses, is absent. We attribute this largely to the variation in nutation frequencies across the spectrum that result from sites possessing large fine structure interactions. The description of the spin dynamics of such sites is complicated and we discuss some possible approaches to the simulation of the pulsed EPR spectra.

Modeling of columnar-to-equiaxed transition in solidified Al-Si alloys

A Cellular-Automaton Finite-Volume-Method (CAFVM) algorithm has been developed, coupling with macroscopic model for heat transfer calculation and microscopic models for nucleation and growth. The solution equations have been solved to determine the time-dependent constitutional undercooling and interface retardation during solidification. The constitutional undercooling is then coupled into the CAFVM algorithm to investigate both the effects of thermal and constitutional undercooling on columnar growth and crystal selection in the columnar zone, and formation of equiaxed crystals in the bulk liquid. The model cannot only simulate microstructures of alloys but also investigates nucleation mechanisms and growth kinetics of alloys solidified with various solute concentrations and solidification morphologies.

LiI-doped N,N-dimethyl-pyrrolidinium iodide, an archetypal rotator-phase ionic conductor

N,N-Dimethyl-pyrrolidinium iodide, and the effect of doping with LiI, has been investigated using DSC, NMR, and impedance spectroscopy. It was found that the addition of a small amount of LiI enhances the ionic conductivity by LIP to 3 orders of magnitude for this ionic solid. Furthermore, a slight decrease in phase transition onset temperatures, as well as the appearance of a superimposed narrow line in the H-1 NMR spectra with dopant, suggest that the LiI facilitates the mobility of the matrix material, possibly by the introduction of vacancies within the lattice. Li-7 NMR line width measurements reveal a narrow Li line width, decreasing in width and increasing in intensity with temperature, indicating mobile Li ions.

Effects of Si content on defect band formation in hypoeutectic Al-Si die castings

Al-3-11% Si alloys have been high-pressure die-cast and characterized microstructurally. Alstruc was used to calculate the solidification characteristics and fraction of eutectic. Defect bands were observed at all Si contents, although their constitution, position and distinctiveness were a function of Si content. The defect bands contain a higher fraction Al-Si eutectic than the surroundings in all alloys, and porosity was additionally found in the band in AlSi3. With decreasing Si content, the defect bands formed closer to the casting surface, became more prevalent and also the width of the bands decreased. These differences are discussed by considering the effect of Si content on the distribution of solid in the mushy wall layers and on the feeding potentials of the alloys. The observations are consistent with the mechanism proposed by Gourlay et al. in which bands form due to deformation within the solidifying mushy wall layers. (c) 2005 Elsevier B.V. All rights reserved.

Eutectic modification and microstructure development in Al-Si alloys

Recent increasing applications for cast Al-Si alloys are particularly driven by the need for lightweighting components in the automotive sector. To improve mechanical properties, elements such as strontium, sodium and antimony can be added to modify the eutectic silicon from coarse and plate-like to fine and fibrous morphology. It is only recently being noticed that the morphological transformation resulting from eutectic modification is also accompanied by other, equally significant, but often unexpected changes. These changes can include a 10-fold increase in the eutectic grain size, redistribution of low-melting point phases and porosity as well as surface finish, consequently leading to variations in casting quality. This paper shows the state-of-the-art in understanding the mechanism of eutectic nucleation and growth in Al-Si alloys, inspecting samples, both quenched and uninterrupted, on the macro, micro and nano-scale. It shows that significant variations in eutectic nucleation and growth dynamics occur in AI-Si alloys as a function of the type and amount of modifier elements added. The key role of AIP particles in nucleating silicon is demonstrated. (c) 2005 Elsevier B.V. All rights reserved.

Ferromagnetism, paramagnetism, and a Curie-Weiss metal in an electron-doped Hubbard model on a triangular lattice

Motivated by the unconventional properties and rich phase diagram of NaxCoO2 we consider the electronic and magnetic properties of a two-dimensional Hubbard model on an isotropic triangular lattice doped with electrons away from half-filling. Dynamical mean-field theory (DMFT) calculations predict that for negative intersite hopping amplitudes (t < 0) and an on-site Coulomb repulsion, U, comparable to the bandwidth, the system displays properties typical of a weakly correlated metal. In contrast, for t > 0 a large enhancement of the effective mass, itinerant ferromagnetism, and a metallic phase with a Curie-Weiss magnetic susceptibility are found in a broad electron doping range. The different behavior encountered is a consequence of the larger noninteracting density of states (DOS) at the Fermi level for t > 0 than for t < 0, which effectively enhances the mass and the scattering amplitude of the quasiparticles. The shape of the DOS is crucial for the occurrence of ferromagnetism as for t > 0 the energy cost of polarizing the system is much smaller than for t < 0. Our observation of Nagaoka ferromagnetism is consistent with the A-type antiferromagnetism (i.e., ferromagnetic layers stacked antiferromagnetically) observed in neutron scattering experiments on NaxCoO2. The transport and magnetic properties measured in NaxCoO2 are consistent with DMFT predictions of a metal close to the Mott insulator and we discuss the role of Na ordering in driving the system towards the Mott transition. We propose that the Curie-Weiss metal phase observed in NaxCoO2 is a consequence of the crossover from a bad metal with incoherent quasiparticles at temperatures T > T-* and Fermi liquid behavior with enhanced parameters below T-*, where T-* is a low energy coherence scale induced by strong local Coulomb electron correlations. Our analysis also shows that the one band Hubbard model on a triangular lattice is not enough to describe the unusual properties of NaxCoO2 and is used to identify the simplest relevant model that captures the essential physics in NaxCoO2. We propose a model which allows for the Na ordering phenomena observed in the system which, we propose, drives the system close to the Mott insulating phase even at large dopings.

A low-temperature insulating phase at v=1.5 for 2D holes in high-mobility SiSi1-xGex heterostructures with Landau level degeneracy

Magneto-transport measurements of the 2D hole system (2DHS) in p-type Si-Si1-xGex heterostructures identify the integer quantum Hall effect (IQHE) at dominantly odd-integer filling factors v and two low-temperature insulating phases (IPs) at v = 1.5 and v less than or similar to 0.5, with re-entrance to the quantum Hall effect at v = 1. The temperature dependence, current-voltage characteristics, and tilted field and illumination responses of the IP at v = 1.5 indicate that the important physics is associated with an energy degeneracy of adjacent Landau levels of opposite spin, which provides a basis for consideration of an intrinsic, many-body origin.

Electron paramagnetic resonance of Ni(II) doped tris(ethylenediamine)zinc(II) dinitrate

Variable temperature electron paramagnetic resonance spectra of tris(ethylenediamine)zinc(II) dinitrate single crystals doped with NI(II) have been measured. The host crystal undergoes a trigonal to monoclinic phase transition at 146 K. Above the transition temperature the zero field splitting tensor is axially symmetric with D = -0.831 cm(-1) and below it becomes rhombic with D = -0.785 cm(-1), E = -0.088 cm(-1). The low temperature spectrum is characterised by the pattern repeating every 60 degrees when the crystal is rotated about the high temperature c axis. The analysis shows that the Zn(II) site retains a C-2 symmetry axis and that the distortion away from the D-3 site symmetry observed for high temperatures is small, the principal axes being tilted by 2.6 degrees. This implies that the phase transition involves the flipping of the C-C backbone in one of the ethylenediamine ligands of the complex, resulting in a A delta delta delta to Lambda delta delta lambda type conformational change.

Comprehensive study of surface chemistry of MCM-41 using Si-29 CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)(3)Si-OH, hydrogen-bonded, (SiO)(3)Si-OH-OH-Si(SiO)(3), and geminal, (SiO)(2)Si(OH)(2), can be observed. The number of silanol groups/nm(2), alpha(OH), as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol(-1), respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.

Ni(II)-doped CsCdBrCl2: Variation of spectral and structural properties via mixed-halide coordination

A new addition to the family of single-molecule magnets is reported: an Fete cage stabilized with benzoate and pyridonate ligands. Monte Carlo methods have been used to derive exchange parameters within the cage, and hence model susceptibility behavior.

A purple acid phosphatase from sweet potato contains an antiferromagnetically coupled binuclear Fe-Mn center

A purple acid phosphatase from sweet potato is the first reported example of a protein containing an enzymatically active binuclear Fe-Mn center. Multifield saturation magnetization data over a temperature range of 2 to 200 K indicates that this center is strongly antiferromagnetically coupled. Metal ion analysis shows an excess of iron over manganese. Low temperature EPR spectra reveal only resonances characteristic of high spin Fe(III) centers (Fe(III)-apo and Fe(III)-Zn(II)) and adventitious Cu(II) centers. There were no resonances from either Mn(II) or binuclear Fe-Mn centers. Together with a comparison of spectral properties and sequence homologies between known purple acid phosphatases, the enzymatic and spectroscopic data strongly indicate the presence of catalytic Fe(III)-Mn(II) centers in the active site of the sweet potato enzyme. Because of the strong antiferromagnetism it is likely that the metal ions in the sweet potato enzyme are linked via a mu -oxo bridge, in contrast to other known purple acid phosphatases in which a mu -hydroxo bridge is present. Differences in metal ion composition and bridging may affect substrate specificities leading to the biological function of different purple acid phosphatases.

Coupled experimental and thermodynamic study of the Zn-Fe-Si-O system

Experimental and thermodynamic modeling studies have been carried out on the Zn-Fe-Si-O system. This research is part of a wider program to characterize zinc/lead industrial slags and sinters in the PbO-ZnO-SiO2-CaO-FeO-Fe2O3 system. Experimental investigations involve high-temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures and solid solubilities of the crystalline phases were measured in the temperature range from 1200 °C to 1450 °C (1473 to 1723 K) in the zinc ferrite, zincite, willemite, and tridymite primary-phase fields in the Zn-Fe-Si-O system in air. These equilibrium data for the Zn-Fe-Si-O system in air, combined with previously reported data for this system, were used to obtain an optimized self-consistent set of parameters of thermodynamic models for all phases.

Determination of eutectic solidification mode in Sr-modified hypoeutectic Al-Si alloys by EBSD

The effect of eutectic modification by strontium on nucleation and growth of the eutectic in hypoeutectic Al-Si foundry alloys has been investigated by electron back-scattering diffraction (EBSD) mapping. Specimens were prepared from three hypoeutectic AlSi base alloys with 5, 7 and 10 mass%Si and with different strontium contents up to 740 ppm for modification of eutectic silicon. By comparing the orientation of the aluminium in the eutectic to that of the surrounding primary aluminium dendrites? the growth mode of the eutectic could be determined. The mapping results indicate that the eutectic grew from the primary phase in unmodified alloys. When the eutectic was modified by strontium, eutectic grains nucleated separately from the primary dendrites. However, in alloys with high strontium levels, the eutectic again grew from the primary phase. These observed effects of strontium additions on the eutectic solidification mode are independent of silicon content in the range between 5 and 10 mass%Si.