Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

Laser-induced changes on the complex refractive indices of phase-change thin film

The refractive indices of crystalline phase-change films are usually obtained by thermal-induced crystallization. However, this is not accurate, because the crystallization of phase-change film in rewritable optical disks is laser induced. In this study, we use the initializer to crystallize the phase-change films. The dependence of the refractive index n and the extinction coefficient k of the phase-change films on the initialization conditions are studied. Remarkable changes of the refractive indices (especially k) are found when the initialization laser power density is 6.63 mW/mum(2) and the initialization velocity is 4.0 m/s. At the same time, the structure changes of the phase-change films are also studied. This dependence is explained by the structure change of the films. These results are significant in improving the accuracy of optical design and the thermal simulation of phase-change optical disks, as well as in the study of phase-change optical disks at shorter wavelengths. (C) 2003 Society of Photo-Optical Instrumentation Engineers.

Optical properties and structure of Sb-rich AgInSbTe phase change thin films

A new composition content quaternary-alloy-based phase change thin film, Sb-rich AgInSbTe, has been prepared by DC-magnetron sputtering on a K9 glass substrate. After the film has been subsequently annealed at 200degreesC for 30 min, it becomes a crystalline thin film. The diffraction peak of antimony (Sb) are observed by shallow (0.5 degree) x-ray diffraction in the quaternary alloy thin film. The analyses of the measurement from differential scanning calorimetry (DSC) show that the crystallization temperature of the phase change thin film is about 190degreesC and increases with the heating rate. By Kissinger plot, the activation energy for crystallization is determined to be 3.05eV. The reflectivity, refractive index and extinction coefficient of the crystalline and amorphous phase change thin films are presented. The optical absorption coefficient of the phase change thin films as a function of photon energy is obtained from the extinction coefficient. The optical band gaps of the amorphous and crystallization phase change thin films are 0.265eV and 1.127eV, respectively.

Temperature dependence of thermal properties of Ag8In14Sb55Te23 phase-change memory materials

The dependence of thermal properties of Ag8In14Sb55Te23 phase-change memory materials in crystalline and amorphous states on temperature was measured and analyzed. The results show that in the crystalline state, the thermal properties monotonically decrease with the temperature and present obvious crystalline semiconductor characteristics. The heat capacity, thermal diffusivity, and thermal conductivity decrease from 0.35 J/g K, 1.85 mm(2)/s, and 4.0 W/m K at 300 K to 0.025 J/g K, 1.475 mm(2)/s, and 0.25 W/m K at 600 K, respectively. In the amorphous state, while the dependence of thermal properties on temperature does not present significant changes, the materials retain the glass-like thermal characteristics. Within the temperature range from 320 K to 440 K, the heat capacity fluctuates between 0.27 J/g K and 0.075 J/g K, the thermal diffusivity basically maintains at 0.525 mm(2)/s, and the thermal conductivity decreases from 1.02 W/m K at 320 K to 0.2 W/m K at 440 K. Whether in the crystalline or amorphous state, Ag8In14Sb55Te23 are more thermally active than Ge2Sb2Te5, that is, the Ag8In14Sb55Te23 composites bear stronger thermal conduction and diffusion than the Ge2Sb2Te5 phase-change memory materials.

Numerical and experimental analysis on green laser crystallization of amorphous silicon thin films

The effect of laser fluence on the crystallization of amorphous silicon irradiated by a frequency-doubled Nd:YAG laser is studied both theoretically and experimentally. An effective numerical model is set up to predict the melting threshold and the optimized laser fluence for the crystallization of 200-nm-thick amorphous silicon. The variation of the temperature distribution with time and the melt depth is analyzed. Besides the model, the Raman spectra of thin films treated with different fluences are measured to confirm the phase transition and to determine the optimized fluence. The calculating results accord well with those obtained from the experimental data in this research. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of lithium-sodium mixed-alkali on phase transformation kinetics in Er3+/Yb3+ co-doped aluminophosphate glasses

Er3+ doped aluminophosphate glasses with various Na2O/Li2O ratios were prepared at 1250 degrees C using a silica crucible to study mixed alkali effect (MAE). The effect of relative alkali content on glass transition temperature, crystallization temperature and thermal stability were investigated using differential scanning calorimetry (DSC). In addition, apparent activation energies for crystallization, E, were determined employing the Kissinger equation. The effect of Al2O3 content on the magnitude of MAE was also discussed. No mixed-alkali effect is observed on crystallization temperature. (c) 2006 Elsevier B.V. All rights reserved.

Effects of chloride substitution on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses

Effect of the substitutions of chloride for fluoride on the chemical and physical properties and the crystallization behavior in heavy metal fluoride glasses has been investigated. The characteristic temperature of the glass does not changed obviously when the fluoride was taken place by chloride. Compared with samples of being free of ErF3, the doping samples are more inclined to be surface crystallization. Optical basicity in the glass system increases with increasing the negative charge provided by the chloride atoms and the absorption peak red shifted is observed in absorption spectra. XRD measurements show that not a single crystalline phase appears in the heated glass samples, which indicate the substitutions of chloride for fluoride with a variety of crystalline precipitation trends. (c) 2007 Elsevier B.V All rights reserved.

Mother structures related to the hexagonal and cubic close packing in Cu24 clusters: solvent-influenced derivatives

Artículo científico CrystEngComm

EBSD characterisation of Y2Ba4CuUOx phase in melttextured YBCO with addition of depleted uranium oxide

Melt-textured YBCO samples processed with added Y2O3 and depleted uranium oxide (DU) contain nano-particles, which have been identified previously as Y2Ba4CuUOx (U-411). This phase has a cubic unit cell, which is clearly distinct from the orthorhombic Y-123 and Y-211 phases within the YBCO system. In samples with a high amount of DU addition (0.8 wt-% DU), U-2411 particles have sizes between 200 nm and several νm, so identification of the Kikuchi patterns of this phase becomes possible. Together with a parallel EDX analysis, the particles embedded in the Y-123 matrix can be identified unambiguously. In this way, a three-phase EBSD scan becomes possible, allowing also the identification of nanometre-sized particles in the sample microstructure. © 2006 IOP Publishing Ltd.

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications.

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range -125 to 125 °C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular.

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range-125 to 125°C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular. © 2012 Macmillan Publishers Limited. All rights reserved.

Development of accurate, robust liquid equations of state for multi-phase CFD simulations with a modified AUSM+-up scheme

Eight equations of state (EOS) have been evaluated for the simulation of compressible liquid water properties, based on empirical correlations, the principle of corresponding states and thermodynamic relations. The IAPWS-IF97 EOS for water was employed as the reference case. These EOSs were coupled to a modified AUSM+-up convective flux solver to determine flow profiles for three test cases of differing flow conditions. The impact of the non-viscous interaction term discretisation scheme, interfacial pressure method and selection of low-Mach number diffusion were also compared. It was shown that a consistent discretisation scheme using the AUSM+-up solver for both the convective flux and the non-viscous interfacial term demonstrated both robustness and accuracy whilst facilitating a computationally cheaper solution than discretisation of the interfacial term independently by a central scheme. The simple empirical correlations gave excellent results in comparison to the reference IAPWS-IF97 EOS and were recommended for developmental work involving water as a cheaper and more accurate EOS than the more commonly used stiffened-gas model. The correlations based on the principles of corresponding-states and the modified Peng-Robinson cubic EOS also demonstrated a high degree of accuracy, which is promising for future work with generic fluids. Further work will encompass extension of the solver to multiple dimensions and to account for other source terms such as surface tension, along with the incorporation of phase changes. © 2013.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Chemical liquid phase deposition of thin aluminum oxide films

Thin aluminum oxide films were deposited by a new and simple physicochemical method called chemical liquid phase deposition (CLD) on semiconductor materials. Aluminum sulfate with crystallized water and sodium bicarbonate were used as precursors for film growth, and the control of the system's pH value played an important role in this experiment. The growth rate is 12 nm/h with the deposition at [Al-2(SO4)(3)]=0.0837 mol.L-1, [NaHCO3]=0.214 mol.L-1, 15 degreesC. Post-growth annealing not only densifies and purifies the films, but results in film crystallization as well. Excellent quality of Al2O3 films in this work is supported by electron dispersion spectroscopy, Fourier transform infrared spectrum, X-ray diffraction spectrum and scanning electron microscopy photograph.

Selective area growth of GaN on GaAs(001) substrates by metalorganic vapor-phase epitaxy

Selective area growth (SAG) of GaN on SiO2 stripe-patterned GaN/GaAs(001) substrates was carried out by metalorganic vapor-phase epitaxy. The SAG samples were investigated by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). SEM observations showed that the morphology of SAG GaN is strongly dependent on the window stripe orientation and slightly affected by the orientation relationship between the window stripes and the gas flow. The (I 1 1)B sidewalls formed on the SAG GaN stripes are found to be stable. XRD measurements indicated the full-widths at half-maximum (FWHMs) of cubic GaN (0 0 2) rocking curves are reduced after SAG. The measured FWHMs with omega-axis parallel to [1(1) over bar 0] are always larger than the FWHM values obtained with omega-axis parallel to [I 10], regardless of the orientation relationship between the w-axis and the GaN stripes. (C) 2003 Elsevier Science B.V. All rights reserved.