Internal nitride formation during gas-phase thermal nitridation of titanium

Titanium nitride surface layers were prepared by gas-phase thermal nitridation of pure titanium in an ammonia atmosphere at 1373 K for different times. In addition to the surface nitride layer, nitride/hydride formation was observed in the bulk of the specimen. The cross-section of the specimen was characterized by various techniques such as optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, secondary ion mass spectrometry and nanomechanical testing, and the mechanism of formation of these phases is discussed.

Stress-induced phase transformation and pseudo-elastic/pseudo-plastic recovery in intermetallic Ni-Al nanowires

Extensive molecular dynamics (MD) simulations have been performed in a B2-NiAl nanowire using an embedded atom method (EAM) potential. We show a stress induced B2 -> body-centered-tetragonal (BCT) phase transformation and a novel temperature and cross-section dependent pseudo-elastic/pseudo-plastic recovery from such an unstable BCT phase with a recoverable strain of similar to 30% as compared to 5-8% in polycrystalline materials. Such a temperature and cross-section dependent pseudo-elastic/pseudo-plastic strain recovery can be useful in various interesting applications of shape memory and strain sensing in nanoscale devices. Effects of size, temperature, and strain rate on the structural and mechanical properties have also been analyzed in detail. For a given size of the nanowire the yield stress of both the B2 and the BCT phases is found to decrease with increasing temperature, whereas for a given temperature and strain rate the yield stress of both the B2 and the BCT phase is found to increase with increase in the cross-sectional dimensions of the nanowire. A constant elastic modulus of similar to 80 GPa of the B2 phase is observed in the temperature range of 200-500 K for nanowires of cross-sectional dimensions in the range of 17.22-28.712 angstrom, whereas the elastic modulus of the BCT phase shows a decreasing trend with an increase in the temperature.

Thermoelectric Properties of Co4Sb12 Skutterudite Materials with Partial In Filling and Excess In Additions

The properties of Co4Sb12 with various In additions were studied. X-ray diffraction revealed the presence of the pure δ-phase of In0.16Co4Sb12, whereas impurity phases (γ-CoSb2 and InSb) appeared for x = 0.25, 0.40, 0.80, and 1.20. The homogeneity and morphology of the samples were observed by Seebeck microprobe and scanning electron microscopy, respectively. All the quenched ingots from which the studied samples were cut were inhomogeneous in the axial direction. The temperature dependence of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) was measured from room temperature up to 673 K. The Seebeck coefficient of all In-added Co4Sb12 materials was negative. When the filler concentration increases, the Seebeck coefficient decreases. The samples with In additions above the filling limit (x = 0.22) show an even lower Seebeck coefficient due to the formation of secondary phases: InSb and CoSb2. The temperature variation of the electrical conductivity is semiconductor-like. The thermal conductivity of all the samples decreases with temperature. The central region of the In0.4Co4Sb12 ingot shows the lowest thermal conductivity, probably due to the combined effect of (a) rattling due to maximum filling and (b) the presence of a small amount of fine-dispersed secondary phases at the grain boundaries. Thus, regardless of the non-single-phase morphology, a promising ZT (S 2 σT/κ) value of 0.96 at 673 K has been obtained with an In addition above the filling limit.

Phase separation versus spin glass behavior in La0.85Sr0.15CoO3

We present comprehensive studies of dc magnetization, ac susceptibility, and magnetotransport of two sets of La0.85Sr0.15CoO3 samples, one exhibits phase separation and the other exhibits spin glass behavior. Our study reveals that the phase separation in La0.85Sr0.15CoO3 is neither inherent nor ubiquitous; rather, it is a consequence of preparation condition. It is realized that the low temperature annealed sample exhibits phase separation while the high temperature annealed one shows the characteristic of spin glass behavior. This study shows that the most probable magnetic state of La0.85Sr0.15CoO3 is spin glass.

Thermodynamic properties of Pb2PtO4 and PbPt2O4 and phase equilibria in the system Pb–Pt–O

The compounds Pb2PtO4 and PbPt2O4 were synthesized from an intimate mixture of yellow PbO and Pt metal powders by heating under pure oxygen gas at 973 K for periods up to 600 ks with intermediate grinding and recompacting. Both compounds were found to decompose on heating in pure oxygen to PbO and Pt, apparently in conflict with the requirements for equilibrium phase relations in the ternary system Pb–Pt–O. The oxygen chemical potential corresponding to the three-phase mixtures, Pb2PtO4 + PbO + Pt and PbPt2O4 + PbO + Pt were measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas at 0.1 MPa pressure as the reference electrode. The standard Gibbs free energies of formation of the ternary oxides were derived from the measurements. Analysis of the results indicated that the equilibrium involving three condensed phases Pb2PtO4 + PbO + Pt is metastable. Under equilibrium conditions, Pb2PtO4 should have decomposed to a mixture of PbO and PbPt2O4. Measurement of the oxygen potential corresponding to this equilibrium decomposition as a function of temperature indicated that decomposition temperature in pure oxygen is 1014(±2) K. This was further confirmed by direct determination of phase relations in the ternary Pb–Pt–O by equilibrating several compositions at 1023 K for periods up to 850 ks and phase identification of quenched samples using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Only one ternary oxide PbPt2O4 was stable at 1023 K under equilibrium conditions. Alloys and intermetallic compounds along the Pb–Pt binary were in equilibrium with PbO.

Phase field study of precipitate growth: Effect of misfit strain and interface curvature

We have used phase field simulations to study the effect of misfit and interfacial curvature on diffusion-controlled growth of an isolated precipitate in a supersaturated matrix. Treating our simulations as computer experiments, we compare our simulation results with those based on the Zener–Frank and Laraia–Johnson–Voorhees theories for the growth of non-misfitting and misfitting precipitates, respectively. The agreement between simulations and the Zener–Frank theory is very good in one-dimensional systems. In two-dimensional systems with interfacial curvature (with and without misfit), we find good agreement between theory and simulations, but only at large supersaturations, where we find that the Gibbs–Thomson effect is less completely realized. At small supersaturations, the convergence of instantaneous growth coefficient in simulations towards its theoretical value could not be tracked to completion, because the diffusional field reached the system boundary. Also at small supersaturations, the elevation in precipitate composition matches well with the theoretically predicted Gibbs–Thomson effect in both misfitting and non-misfitting systems.

Interdiffusion and activation energy in Ti3Au phase with A15 crystal structure

The knowledge of diffusion parameters, such as integrated diffusion coefficient and the activation energy for diffusion is important to understand the growth rate of the product phase and the atomic mechanism of diffusion. These parameters are determined in Ti3Au phase with A15 crystal structure. The calculated diffusion parameters will help in validating the theoretical analysis on defect structure of the phase.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems for Tm, Yb and Lu

Phase diagrams for Tm2O3-H2O-CO2. Yb2O3-H2O-CO2 and Lu2O3-H2O-CO2 systems at 650 and 1300 bars have been investigated in the temperature range of 100–800°C. The phase diagrams are far more complex than those for the lighter lanthanides. The stable phases are Ln(OH)3, Ln2(CO3)3.3H2O (tengerite phase), orthorhombic-LnOHCO3, hexagonal-Ln2O2CO3. LnOOH and cubic-Ln2O3. Ln(OH)3 is stable only at very low partial pressures of CO2. Additional phases stabilised are Ln2O(OH)2CO3and Ln6(OH)4(CO3)7 which are absent in lighter lanthanide systems. Other phases, isolated in the presence of minor alkali impurities, are Ln6O2(OH)8(CO3)3. Ln4(OH)6(CO3)3 and Ln12O7(OH)10,(CO3)6. The chemical equilibria prevailing in these hydrothermal systems may be best explained on the basis of the four-fold classification of lanthanides.

Structural phase transition study of the morphotropic phase boundary compositions of Na0.5Bi0.5TiO3-PbTiO3

Neutron, synchrotron x-ray powder diffraction and dielectric studies have been performed for morphotropic phase boundary (MPB) compositions of the (1 - x )Na1/2Bi1/2TiO3-xPbTiO(3) system. At room temperature, the MPB compositions (0.10 < x <= 0.15) consist of a mixture of rhombohedral (space group R3c) and tetragonal ( space group P4mm) structures with the fraction of tetragonal phase increasing with increasing PbTiO3 content. On heating, while the rhombohedral phase just outside the MPB region, i.e. x = 0.10, transforms directly to a cubic phase, the rhombohedral phase of the MPB compositions transforms gradually to a tetragonal phase, until interrupted by a rhombohedral-cubic phase transition. The correspondence of the dielectric anomalies with the structural transitions of the different compositions has been examined and compared with earlier reports.

Barium hexaferrite (M-phase) exhibiting superstructure

Barium hexaferrite (M-phase) prepared by the flux method is found to exhibit \checkmark 3 \ut \times \checkmark 3 \ut superstructure similar to barium hexaaluminate.

Synthesis of wurtzite-phase ZnS nanocrystal and its optical properties

The wurtzite phase of ZnS nanocrystal has been prepared by annealing in 200-600 degrees C temperature range, its cubic phase of 2-3 nm size. prepared through soft chemical method. Results of isochronal experiments of 2 h at different temperatures indicate that visible transformation to wurtzite from cubic ZnS appears at a temperature of 400 degrees C, which is about three times smaller than that of bulk ZnS phase transition temperature. The phases, nanostructures, and optical absorption characteristics are obtained through X-ray diffraction. transmission electron microscopy, and UV-visible absorption spectroscopy. A stable and green photoluminescence emission peaked at 518 nm is observed from the 600 degrees C annealed samples, under ultraviolet light excitation.

Fabrication and Phase Transformation in Crystalline Nanoparticles of PbZrO3 Derived By Sol-Gel

In this research fabrication of crystalline PbZrO3 (PZ) nanoparticles and their phase transformation behavior is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PZ, which was dried at 150 degrees C and then calcined at 300-700 degrees C for 1 h. The morphology, crystallinity and phase formation of as synthesized nanoparticles were studied by the selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermal gravimetric analysis/differential scanning calorimetry (TGA-DSC), and high resolution transmission electron microscope (HRTEM). The XRD, SAED, and TGA-DSC analyses confirmed the tetragonal lead rich zirconia phase (t-Z phase) and monoclinic zirconia phase (m-Z phase) as the intermediate phases during the calcinations process followed by crystallization of single orthorhombic PZ phase at about 700 degrees C. The average PZ particle size was observed about 20 nm as confirmed by TEM study. Energy-dispersive X-ray spectroscopy (EDX) analysis demonstrated that stoichiometric PbZrO3 was formed.

Structure and phase transition of the (1-x)PbTiO3-(x)BiAlO3 system

The system (1 - x)PbTiO3 - (x)BiAlO3 has been studied with regard to its structure and phase transition behaviour using x-ray, neutron and dielectric measurements. The structure is tetragonal within the solid solubility limit (x < 0.25). Interatomic distance analysis revealed that the Pb-O bond lengths remain unaffected and the only the Ti-O lengths are altered by BiAlO3 substitution. The results are suggestive of a crossover from and A-site & B site driven ferroelectric system for x = 0 to a dominant A-site driven ferroelectric system for higher x. This cross-over is brought about by (i) a reduction in the contribution to the ferroelectric stability from B-site cations due to dilution of the Ti-sublattice by Al and (ii) a reinforcement to the stability of the ferroelectric state by the A-site cations by the Bi+3 cations..

Topological close packed mu phase formation and the determination of diffusion parameters in the Co-Mo system

The study on the formation and growth of topological close packed (TCP) compounds is important to understand the performance of turbine blades in jet engine applications. These deleterious phases grow mainly by diffusion process in the superalloy substrate. Significant volume change was found because of growth of the p phase in Co-Mo system. Growth kinetics of this phase and different diffusion parameters, like interdiffusion, intrinsic and tracer diffusion coefficients are calculated. Further the activation energy, which provides an idea about the mechanism, is determined. Moreover, the interdiffusion coefficient in Co(Mo) solid solution and impurity diffusion coefficient of Mo in Co are determined.

Precipitate growth with composition-dependent diffusivity: Comparison between theory and phase field simulations

We consider the growth of an isolated precipitate when the matrix diffusivity depends on the composition. We have simulated precipitate growth using the Cahn-Hilliard model, and find good agreement between our results and those from a sharp interface theory for systems with and without a dilatational misfit. With misfit, we report (and rationalize) an interesting difference between systems with a constant diffusivity and those with a variable diffusivity in the matrix.