Phase equilibria at sub-solidus conditions in the Fe-Mg-Zn-O system in air

The phase equilibria in the Fe-Mg-Zn-O system in the temperature range 1100-1550degreesC in air have been experimentally studied using equilibration and quenching followed by electron probe X-ray microanalysis. The compositions of condensed phases in equilibrium in the binary MgO-ZnO system and the ternary Fe-Mg-O system have been reported at sub-solidus in air. Pseudo-ternary sections of the quaternary Fe-Mg-Zn-O system at 1100, 1250 and 1400degreesC in air were constructed using the experimental data. The solid solution of iron oxide, MgO and ZnO in the periclase (Mg, Zn, Fe)O, spinel (Mg2+, Fe2+, Zn2+)(x)Fe(2+y)3+O4 and zincite (Zn, Mg, Fe)O phases were found to be extensive under the conditions investigated. A continuous spinel solid solution is formed between the magnesioferrite (Mg2+, Fe2+)(x)Fe(2+y)3+O4 and franklinite (Zn2+, Fe2+)(x)Fe(2+y)3+O4 end-members at 1100 and 1250degreesC, extending to magnetite (Fe2+)(x)Fe(2+y)3+O4 at 1400degreesC in air. The compositions along the spinel boundaries were found to be non-stoichiometric, the magnitude of the non-stoichiometry being a function of composition and temperature in air. It was found that hematite dissolves neither MgO nor ZnO in air.

The Bazhanov-Stroganov model from 3D approach

We apply a three-dimensional approach to describe a new parametrization of the L-operators for the two-dimensional Bazhanov-Stroganov (BS) integrable spin model related to the chiral Potts model. This parametrization is based on the solution of the associated classical discrete integrable system. Using a three-dimensional vertex satisfying a modified tetrahedron equation, we construct an operator which generalizes the BS quantum intertwining matrix S. This operator describes the isospectral deformations of the integrable BS model.

Crystallization behavior of (Cu60Zr30Ti10)(99)Sn-1 bulk metallic glass

The crystallization behavior and crystallization kinetics Of (CU60Zr30Ti10)(99)Sn-1 bulk metallic glass was studied by X-ray diffractometry and differential scanning calorimetry. It was found that a two-stage crystallization took place during continuous heating of the bulk metallic glass. Both the glass transition temperature T-g and the crystallization peak temperatures T-p displayed a strong dependence on the heating rate. The activation energy was determined by the Kissinger analysis method. In the first-stage of the crystallization, the transformation of the bulk metallic glass to the phase one occurred with an activation energy of 386 kJ/mol; in the second-stage, the formation of the phase two took place at an activation energy of 381 kJ/mol.

Microstructures of ISF sinters in air

The microstructures of industrial ISF and synthetic sinters were examined. The principle phases present were found to consist of zincite, spinel and glass. The morphologies of the zincite phase in these complex multiphase materials were shown to relate directly to the bulk chemical compositions and thermal histories of the sinters. The conditions favouring the formation of plate-like zincite, essential for the development of refractory networks in the ISF sinters, were identified. The proportion of framework zincite present in the sinters was found to increase with increasing peak bed temperature and an increasing CaO/SiO2 ratio. The aspect ratio of the zincite increases by increasing iron in the solid solution in zincite.

The role of carbon in fuel cells

Carbon possesses unique electrical and structural properties that make it an ideal material for use in fuel cell construction. In alkaline, phosphoric acid and proton-exchange membrane fuel cells (PEMFCs), carbon is used in fabricating the bipolar plate and the gas-diffusion layer. It can also act as a support for the active metal in the catalyst layer. Various forms of carbon - from graphite and carbon blacks to composite materials - have been chosen for fuel-cell components. The development of carbon nanotubes and the emergence of nanotechnology in recent years has therefore opened up new avenues of matenials development for the low-temperature fuel cells, particularly the hydrogen PEMFC and the direct methanol PEMFC. Carbon nanotubes and aerogels are also being investigated for use as catalyst support, and this could lead to the production of more stable, high activity catalysts, with low platinum loadings (< 0.1 Mg cm(-2)) and therefore low cost. Carbon can also be used as a fuel in high-temperature fuel cells based on solid oxide, alkaline or molten carbonate technology. In the direct carbon fuel cell (DCFC), the energy of combustion of carbon is converted to electrical power with a thermodynamic efficiency close to 100%. The DCFC could therefore help to extend the use of fossil fuels for power generation as society moves towards a more sustainable energy future. (c) 2006 Elsevier B.V. All rights reserved.

Effects of cation substitutions on the physical properties of M2M1T2O6 pyroxenes

In this PhD study, the effects of the cation substitutions on the physical properties of pyroxenes have been discussed. The results of this work extend the knowledge on pyroxenes with different chemical compositions. These properties might be used in the development of ceramic pigments, advanced materials and for the mineralogical phase identification. First of all, the crystallographic differences between Ge and Si pyroxenes have been examined. The structure of C2/c Ca rich Ge clinopyroxenes is very close to the low pressure C2/c structural configuration found in Ca-rich Si-pyroxenes. The shear of the unit cell is very similar, and the difference between a Ge end member and the corresponding Si-rich one is less than 1°. Instead, a remarkable difference exists between Ca-poor Si and Ge clinopyroxenes. First, Ca-poor Ge pyroxenes do not display a P21/c symmetry, but retain the C2/c symmetry; second, the observed C2/c structure shows, at room pressure, the configuration with highly kinked tetrahedral chains characteristic of the high pressure C2/c symmetry of Si Ca-poor pyroxenes. In orthopyroxenes, with Pbca symmetry, Ge-pyroxenes have volume larger than Si-pyroxenes. Samples along the system CaCoGe2O6 - CoCoGe2O6 have been synthesized at three different temperatures: 1050 °C, 1200 °C and 1250 °C. The aim of these solid state syntheses was to obtain a solid solution at ambient pressure, since the analogues Si-system needs high pressure. Unfortunately, very limited solution occurs because the structure forms of the two end member (high temperature for CaCoGe2O6 and high pressure CoCoGe2O6) are incompatible. The phase diagram of this system has been sketched and compared to that of Si. The cobalt end member (CoCoGe2O6) is stable at ambient pressure in two symmetries: at 1050 °C C2/c and 1200 °C Pbca. The impurity phase formed during these experiments is cobalt spinel. Raman spectroscopy has been used to investigate the vibrational properties of Ca-pyroxenes CaCoGe2O6, CaMgGe2O6, CaMgSi2O6 and CaCoSi2O6. A comparison between silicate and germanate pyroxenes shows significant changes in peak positions of the corresponding modes caused mainly by the difference of the Ge-Si atomic weight along with the distortion and compression of the coordination polyhedra. Red shift in Raman spectra of germanates has been calculated by a rough scale factor calculated by a simple harmonic oscillator model, considering the different bond lengths for 4-coordinated Si ~ 1.60- 1.65 Å vs Ge–O distance ~1.70 - 1.80 Å. The Raman spectra of CaMgGe2O6 and CaCoGe2O6 have been classified, in analogy with silicate (Wang et al., 2001) counterparts, in different ranges: - R1 (880-640 cm-1): strong T-O stretching modes of Ge and non-bridging O1 and O2 atoms within the GeO4 tetrahedron; - R2 (640-480 cm-1): stretching/bending modes of Ge-Obr-Ge bonds (chain stretching and chain bending); - R4 (480-360 cm-1): O-Ge-O vibrations; - R3 (360-240 cm-1): motions of the cations in M2 and M1 sites correlated with tetrahedral chain motion and tilting tetrahedra; - R5 (below 240 cm-1): lattice modes. The largest shift with respect to CaMgSi2O6 - CaCoSi2O6 is shown by the T-O stretching and chain modes. High-pressure Raman spectroscopy (up to about 8 GPa) on the same samples of Ca-pyroxenes using an ETH-type diamond anvil cell shows no phase transition within the P-ranges investigated, as all the peak positions vary linearly as a function of pressure. Our data confirm previous experimental findings on Si-diopside (Chopelas and Serghiou, 2000). In the investigated samples, all the Raman peaks shift upon compression, but the major changes in wavenumber with pressure are attributed to the chain bending (Ge-Obr-Ge bonds) and tetrahedra stretching modes (Ge-Onbr). Upon compression, the kinking angle, the bond lengths and T-T distances between tetrahedra decrease and consequently the wavenumber of the bending chain mode and tetrahedra stretching mode increases. Ge-pyroxenes show the higher P-induced peak-position shifts, being more compressible than corresponding silicates. The vibrational properties of CaM2+Ge2O6 (M2+ =Mg, Mn, Fe, Co, Ni, Zn) are reported for the first time. The wavenumber of Ge-Obr-Ge bending modes decreases linearly with increasing ionic radius of the M1 cation. No simple correlation has been found with M1 atomic mass or size or crystallographic parameters for the peak at ~850 cm-1 and in the low wavenumber regions. The magnetic properties of the system CaCoSi2O6 - CoCoSi2O6 have been investigated by magnetometry. The join is always characterized by 1 a.p.f.u. of cobalt in M1 site and this causes a pure collinear antiferromagnetic behaviour of the intra-chain superexchange interaction involving Co ions detected in all the measurements, while the magnetic order developed by the cobalt ions in M2 site (intra-chain) is affected by weak ferromagnetism, due to the non-collinearity of their antiferromagnetic interaction. In magnetically ordered systems, this non-collinearity effect promotes a spin canting of anti-parallel aligned magnetic moments and thus is a source of weak ferromagnetic behaviour in an antiferromagnetic. The weak ferromagnetism can be observed only for the samples with Co content higher than 0.5 a.p.f.u. in M2, when the concentration is sufficiently high to create a long range order along the M2 chain which is magnetically independent of M1 chain. The ferromagnetism was detected both in the M(T) at 10 Oe and M(H).

Vibrational dynamics and structure of natural feldspars

The present study gives a contribution to the knowledge on the Na-feldspar and plagioclases, extending the database of the Raman spectra of plagioclases with different chemical compositions and structural orders. This information may be used for the future planetary explorations by “rovers”, for the investigation of ceramics nanocrystal materials and for the mineralogical phase identification in sediments. Na-feldspar and plagioclase solid solution have been investigated by Raman spectroscopy in order to determine the relationships between the vibrational changes and the plagioclase crystal chemistry and structure. We focused on the Raman micro-spectroscopy technique, being a non-destructive method, suited for contactless analysis with high spatial resolution. Chemical and structural analyses have been performed on natural samples to test the usefulness of Raman spectroscopy as a tool in the study of the pressure-induced structural deformations, the disordering processes due to change in the Al-Si distribution in the tetrahedral sites and, finally, in the determination of the anorthitic content (Anx) in plagioclase minerals. All the predicted 39 Ag Raman active modes have been identified and assigned to specific patterns of atomic vibrational motion. A detailed comparison between experimental and computed Raman spectra has been performed and previous assignments have been revised, solving some discrepancies reported in recent literature. The ab initio calculation at the hybrid HF/DFT level with the WC1LYP Hamiltonian has proven to give excellent agreement between calculated and experimentally measured Raman wavenumbers and intensities in triclinic minerals. A short digression on the 36 infrared active modes of Na-feldspar has been done too. The identification of all 39 computed Raman modes in the experimentally measured spectra of the fully ordered Na-feldspar, known as low albite, along with the detailed description of each vibrational mode, has been essential to extend the comparative analysis to the high pressure and high temperature structural forms of albite, which reflect the physical–chemical conditions of the hosting rocks. The understanding of feldspar structure response to pressure and temperature is crucial in order to constrain crustal behaviour. The compressional behaviour of the Na-feldspar has been investigated for the first time by Raman spectroscopy. The absence of phase transitions and the occurrence of two secondary compression mechanisms acting at different pressures have been confirmed. Moreover, Raman data suggest that the internal structural changes are confined to a small pressure interval, localized around 6 GPa, not spread out from 4 to 8 GPa as suggested by previous X-rays studies on elasticity. The dominant compression mechanisms act via tetrahedral tilting, while the T-O bond lengths remain nearly constant at moderate compressional regimes. At the spectroscopic level, this leads to the strong pressure dependencies of T-O-T bending modes, as found for the four modes at 478, 508, 578 and 815 cm-1. The Al-Si distribution in the tetrahedral sites affects also the Raman spectrum of Na-feldspar. In particular, peak broadening is more sensitive than peak position to changes in the degree of order. Raman spectroscopy is found to be a good probe for local ordering, in particular being sensitive to the first annealing steps, when the macroscopic order parameter is still high. Even though Raman data are scattered and there are outliers in the estimated values of the degree of order, the average peak linewidths of the Na-feldspar characteristic doublet band, labelled here as υa and υb, as a function of the order parameter Qod show interesting trends: both peak linewidths linearly increase until saturation. From Qod values lower than 0.6, peak broadening is no more affected by the Al-Si distribution. Moreover, the disordering process is found to be heterogeneous. SC-XRD and Raman data have suggested an inter-crystalline inhomogeneity of the samples, i.e., the presence of regions with different defect density on the micrometric scale. Finally, the influence of Ca-Na substitution in the plagioclase Raman spectra has been investigated. Raman spectra have been collected on a series of well characterized natural, low structural plagioclases. The variations of the Raman modes as a function of the chemical composition and the structural order have been determined. The number of the observed Raman bands at each composition gives information about the unit-cell symmetry: moving away from the C1 structures, the number of the Raman bands enhances, as the number of formula units in the unit cell increases. The modification from an “albite-like” Raman spectrum to a more “anorthite-like” spectrum occurs from sample An78 onwards, which coincides with the appearance of c reflections in the diffraction patterns of the samples. The evolution of the Raman bands υa and υb displays two changes in slope at ~An45 and ~An75: the first one occurs between e2 and e1 plagioclases, the latter separates e1 and I1 plagioclases with only b reflections in their diffraction patterns from I1 and P1 samples having b and c reflections too. The first variation represents exactly the e2→e1 phase transitions, whereas the second one corresponds in good approximation to the C1→I1 transition, which has been determined at ~An70 by previous works. The I1→P1 phase transition in the anorthite-rich side of the solid solution is not highlighted in the collected Raman spectra. Variations in peak broadening provide insights into the behaviour of the order parameter on a local scale, suggesting an increase in the structural disorder within the solid solution, as the structures have to incorporate more Al atoms to balance the change from monovalent to divalent cations. All the information acquired on these natural plagioclases has been used to produce a protocol able to give a preliminary estimation of the chemical composition of an unknown plagioclase from its Raman spectrum. Two calibration curves, one for albite-rich plagioclases and the other one for the anorthite-rich plagioclases, have been proposed by relating the peak linewidth of the most intense Raman band υa and the An content. It has been pointed out that the dependence of the composition from the linewidth can be obtained only for low structural plagioclases with a degree of order not far away from the references. The proposed tool has been tested on three mineralogical samples, two of meteoric origin and one of volcanic origin. Chemical compositions by Raman spectroscopy compare well, within an error of about 10%, with those obtained by elemental techniques. Further analyses on plagioclases with unknown composition will be necessary to validate the suggested method and introduce it as routine tool for the determination of the chemical composition from Raman data in planetary missions.

Outlook and application status of the Rolls-Royce Fuel Cell Systems SOFC

Rolls-Royce fuel cell systems is developing megawatt scale power systems based on solid oxide fuel cell technology. The hybrid design promises to meet challenging energy efficiency, cost and performance targets in a grid friendly fashion. Analysis and testing to date indicate that those targets can be met and enable a wealth of fuel cell applications to meet customer and existing grid and modern grid requirements. Working with a global development team, a series of laboratory tests and evaluations are completed and future field test and evaluation and demonstration planned.

The influence of composition on the optical properties of electrodeposited gold

In industry the colour of a gold alloy electrodeposit is checked by visual comparison with standard panels. The aims of the present work have been to access the application of spectrophotmetric techniques to the measurement of the colour of gold alloy electrodeposits and to examine the factors that influence the colour of thin deposits. The minimum thickness of deposit required to produce its final colour and completely hide the underlying substrate was measured and found to depend on the nature of the substrate, the plating solution and the operating conditions. Bright and matt electrodeposits were studied. The influence of alloying gold by adding copper, silver and indium to the plating solution were investigated. CIE chromaticity coordinates were calculated from spectrophotometric data using a computer programme written for the purpose. The addition of silver to a simple gold bath caused the colour of the deposit to change from yellow through green to near white in a smooth progression as the amount of silver in solid solution steadily increased. The colour of deposits formed when additions of copper were made was complicated by the formation of intermediate phases. À colour in the blue region of the spectrum was obtained in a few experiments investigating the influence of indium additions to the gold bath.

Steric stabilization and dissolution characteristics of aqueous suspensions of pharmaceutical interest

The adsorption of two qroups of nonionic surface active agents and a series of hiqh molecular weiqht hydrophilic polymer fractions onto a polystyrene latex and a drug substance diloxanide furoate B.P. has been investigated. The presence of pores within the drug surface has been demonstrated and this is shown to increase the adsorption of low molecular weight polymer species. Differences in the maximum amount of polymer adsorbed at both solid-solution interfaces have been ascribed to the different hydrophobicities of the surface as determined by contact angle measurements. Adsorbed layer thicknesses of polymer on polystyrene latex have been determined by three techniques: microelectrophoresis, intensity fluctuation spectroscopy and by viscometric means. These results, in combination with adsorption data, were used to interpret the configuration of the adsorbed polymer molecules at the interface. The type of druq suspension produced on adsorbing the different polymers in the absence of electrostatic stabilization was correlated with theoretical prediuctions of suspension characteristics deduced from potential energy diagrams, The agreement was good for the adsorption of short chain length surfactants, but for the polyvinylalcohols, discrepancies were found between experiment and theory. This was attributed to the inappropriate use of a mean segment density approximation within the adsorbed layer to calculate attractive potentials between particles. A maximum in the redispersibility values for suspensions coated with adsorbed nonylphenylethoxylates was attributed to "partial static stabilization" of the particles in conjunction with the attractive forces operating in the sediment between bare surface patches on neighbouring particles. No significant change in the dissolution of the drug was observed when nonylphenylethoxylates were adsorbed due to desorption upon contact with the dissolution medium. Pluronic F68 and all the polyvinylalcohol fractions caused a reduction in the dissolution rate which is explained by the decreased diffusion of drug' through the adsorbed polymer layer.

The metamorphic environments of the Strontian, Foyers and Dalbeattie intrusions, Scotland

Three metamorphic aureoles around intrusions of the Caledonian 'Newer Granite' suite are described. Each represents a different orogenic environment. The Strontian complex is intruded into sillimanite grade Moinian metasediments at the core of the orogen. The aureole comprises three zones; a transitional muscovite + sillimanite + K-feldspar zone, a sillimanite + K-feldspar zone and an inner cordierite + K-feldspar zone. Contact migmatization occurs in the inner part of the aureole. Zoning profiles from garnets in both regional and aureole assemblages show retrograde Mn-rich rims. Fe and Mg compositions are re-equilibrated to contact conditions. Apparent re-equilibration of Ca compositions results from increasingly ideal solid solution behaviour of Ca in plagioclase and garnet with increasing temperature. Temperatures of 690°C at 4.1 kbar (XH2O = 0.53) are estimated in the cordierite + K-feldspar zone, dropping to 630°C (XH2O = 0.69) at the sillimanite + K-feldspar isograd. The zones increase in width to the east, influenced by the regional thermal gradient at the time of intrusion. The timer-scale of the contact event, t2, relative to the regional, tl, - is estimated as t2/t1 = 101.1+ -0.7 and is consistent with Intrusion at an early stage of regional uplift and cooling. The Foyers complex intrudes Moinian rocks at a higher structural level. Regional assemblages range from garnet to sillimanite grade. Three contact zones are recognised; a sillimanite zone, a sillimanite + K-feldspar zone and an inner cordierite + K-feldspar zone. The limit of the aureole is marked by the breakdown of garnet which shows disequilibrium, both texturally, and in complex zoning profiles, within it. Temperatures of 660°C at 3.9 kbar (XH20 = 0.14) are estimated in the cordierite + K-feldspar zone? The Dalbeattie complex is at the margin of the orogen, intruded into low grade Silurian metasediments. Two zones are recognised; a biotite zone and an inner hornblende zone. Cordierite and diopside are present in the inner zone.

Remobilisation of uranium and thorium by ore-forming fluids: a mineralogical study. Available in 2 volumes.

Mineralogical investigations have determined the sites of u and Th associated with two radioelement-enriched granites from different geological settings. In the Ririwai ring complex, Nigeria, the u- and Th-bearing accessories have been greatly affected by post-magmatic alteration of the biotite granite. Primary thorite, zircon and monazite were altered to Zr(±Y)-rich thorite, partially metamict zircon (enriched in Th, U, Y, P, Fe, Mn, Ca) and an unidentified LREE-phase respectively, by pervasive fluids which later precipitated Zr-rich coffinite. More intense, localised alteration and albitisation completely remobilised primary accessories and gave rise to a distinctive generation of haematite- and uranothorite-enriched zircon with clear, Hi-enriched rims and xenotime overgrowths. In the Ririwai lode, microclinisation and later greisenisation locally remobilised or altered zircon and deposited Y-ricl1 coffinite and Y(±Zr)-rich thorite which was overgrown by traces of xenotime and LREE-phase(s) of complex and variable composition. Compositions indicating extensive solid-solution among thorite, coffinite, xenotime and altered zircon are probably metastable and formed at low temperatures. The widespread occurrence of REE-rich fluorite suggests that F-complexing aided the mobility of REE, Y, U, Th and Zr during late-magmatic to post-magmatic alteration, while uranyl-carbonate complexing may have occurred during albitisation. The Caledonian, Helmsdale granite in northern Scotland has undergone pervasive and localised hydrothermal alteration associated with U enrichment. Zircon xenocrysts, primary sphene and apatite contain a small.proportion of this U which is largely adsorbed on to secondary iron-oxide, TiOand phyllosilicates.Additional sites for U in the overlying, Lower Devonian Ousdale arkose include coffinite, secondary uranyl phosphates, hydrocarbon and traces of xenotime and unidentified LREE-phases. U may have been leached from the granite and deposited in the arkose, along channelways associated with the Helmsdale fault, by convecting, hydrothermal fluids

The effect of barium substitution on the ferroelectric properties of Sr2 Nb2 O7 Ceramics

This work revealed that the solid solution compounds of Sr 2-xBaxNb2O7 are promising lead-free materials for high-temperature piezoelectric sensor application. These compounds were confirmed as ferroelectric materials with high Curie points (> 900°C) by their piezoelectric activity after poling, ferroelectric domain switching in their P-E hysteresis loops and thermal depoling behavior. The effect of Ba substitution on the structure and properties of Sr 2-xBaxNb2O7 (x < 1.0) was investigated. The solid solution limit of Sr2-xBaxNb 2O7 was determined by XRD as x < 0.6. The a-, b-, c- axes, and cell volume increase with Ba addition. The textured ceramics of Sr2-xBaxNb2O7 were prepared for the first time. The highest d33 was measured as 3.6 ± 0.1 pC/N for Sr1.8Ba0.2Nb2O7. © 2012 The American Ceramic Society.

Nonlinear integral equation methods for the reconstruction of an acoustically sound-soft obstacle

The problem considered is that of determining the shape of a planar acoustically sound-soft obstacle from knowledge of the far-field pattern for one time-harmonic incident field. Two methods, which are based on the solution of a pair of integral equations representing the incoming wave and the far-field pattern, respectively, are proposed and investigated for finding the unknown boundary. Numerical resultsare included which show that the methods give accurate numerical approximations in relatively few iterations.

Optimization of relay selection in DF cooperative systems with outdated CSI

Relay selection has been considered as an effective method to improve the performance of cooperative communication. However, the Channel State Information (CSI) used in relay selection can be outdated, yielding severe performance degradation of cooperative communication systems. In this paper, we investigate the relay selection under outdated CSI in a Decode-and-Forward (DF) cooperative system to improve its outage performance. We formulize an optimization problem, where the set of relays that forwards data is optimized to minimize the probability of outage conditioned on the outdated CSI of all the decodable relays’ links. We then propose a novel multiple-relay selection strategy based on the solution of the optimization problem. Simulation results show that the proposed relay selection strategy achieves large improvement of outage performance compared with the existing relay selection strategies combating outdated CSI given in the literature.