Phase relations in the system Ca-Ta-O and thermodynamics of calcium tantalates in relation to calciothermic reduction of Ta2O5

Phase equilibria of the system Ca-Ta-O is established by equilibrating eleven samples at 1200 K for prolonged periods and phase identification in quenched samples by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Four ternary oxides are identified: CaTa4O11, CaTa2O6, Ca2Ta2O7 and Ca4Ta2O9. Isothermal section of the phase diagram is composed using the results. Thermodynamic properties of the ternary oxides are measured in the temperature range from 975 to 1275 K employing solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells essentially measure the chemical potentials of CaO in two-phase fields (Ta2O5 + CaTa4O11), (CaTa4O11 + CaTa2O6), (CaTa2O6 + Ca2Ta2O7), and (Ca2Ta2O7 + Ca4Ta2O9) of the pseudo-binary system CaO-Ta2O5. The standard Gibbs energies of formation of the four ternary oxides from their component binary oxides Ta2O5 and CaO are given by: Delta G(f)((ox))(o) (CaTa4O11) (+/- 482)/J mol(-1) = -58644+21.497 (T/K) Delta G(f)((ox))(o) (CaTa2O6) (+/- 618)/J mol(-1) = -55122+21.893 (T/K) Delta G(f)((ox))(o) (Ca2Ta2O7) (+/- 729)/J mol(-1) = -82562+31.843 (T/K) Delta G(f)((ox))(o) (Ca4Ta2O9) (+/- 955)/J mol(-1) = -126598+48.859 (T/K) The Gibbs energy of formation of the four ternary compounds obtained in this study differs significantly from that reported in the literature. The thermodynamic data and phase diagram are used for understanding the mechanism and kinetics of calciothermic and electrochemical reduction of Ta2O5 to metal. (C) 2014 Elsevier B.V. All rights reserved.

Phase evolutions, growth kinetics and diffusion parameters in the Co-Ni-Ta system

Diffusion couple experiments are conducted to study phase evolutions in the Co-rich part of the Co-Ni-Ta phase diagram. This helps to examine the available phase diagram and propose a correction on the stability of the Co2Ta phase based on the compositional measurements and X-ray analysis. The growth rate of this phase decreases with an increase in Ni content. The same is reflected on the estimated integrated interdiffusion coefficients of the components in this phase. The possible reasons for this change are discussed based on the discussions of defects, crystal structure and the driving forces for diffusion. Diffusion rate of Co in the Co2Ta phase at the Co-rich composition is higher because of more number of Co-Co bonds present compared to that of Ta-Ta bonds and the presence of Co antisites for the deviation from the stoichiometry. The decrease in the diffusion coefficients because of Ni addition indicates that Ni preferably replaces Co antisites to decrease the diffusion rate. (C) 2014 Elsevier B.V. All rights reserved.

Oxygen potentials and phase equilibria in the system Ca-Co-O and thermodynamic properties of Ca3Co2O6 and Ca3Co4O9.163

Oxygen potentials established by the equilibrium between three condensed phases, CaOss+CoOss+ Ca3Co2O6 and CoOss+Ca3Co2O6+Ca3CO3.93+O-alpha(9.36-delta), are measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen as the reference electrode. Cation non-stoichiometry and oxygen non-stoichiometry in Ca3Co3.93+alpha O9.36-delta are determined using different techniques under defined conditions. Decomposition temperatures and thermodynamic properties of Ca3Co2O6 and Ca3Co4O9.163 are calculated from the results. The standard entropy and enthalpy of formation of Ca3Co2O6 at 298.15 K are evaluated. Using thermodynamic data from this study and auxiliary information from the literature, phase diagram for the ternary system Ca-Co-O is computed. Isothermal sections at representative temperatures are displayed to demonstrate the evolution of phase relations with temperature. (C) 2014 Elsevier Inc. All rights reserved.

Selective growth of single phase VO2(A, B, and M) polymorph thin films

We demonstrate the growth of high quality single phase films of VO2(A, B, and M) on SrTiO3 substrate by controlling the vanadium arrival rate (laser frequency) and oxidation of the V atoms. A phase diagram has been developed (oxygen pressure versus laser frequency) for various phases of VO2 and their electronic properties are investigated. VO2(A) phase is insulating VO2(B) phase is semi-metallic, and VO2(M) phase exhibits a metal-insulator transition, corroborated by photoelectron spectroscopic studies. The ability to control the growth of various polymorphs opens up the possibility for novel (hetero) structures promising new device functionalities. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Pattern-Formation During Self-organization in Three-Phase Eutectic Solidification

Eutectic growth is an interesting example for exploring the topic of pattern-formation in multi-phase systems, where the growth of the phases is coupled with the diffusive transport of one or more components in the melt. While in the case of binary alloys, the number of possibilities are limited (lamellae, rods, labyrinth etc.), their number rapidly increases with the number of components and phases. In this paper, we will investigate pattern formation during three-phase eutectic solidification using a state-of-the art phase-field method based on the grand-canonical density formulation. The major aim of the study is to highlight the role of two properties, which are the volume fraction of the solid phases and the solid-liquid interfacial energies, in the self-organization of the solid phases during directional growth. Thereafter, we will show representative phase-field simulations of a micro-structure in a real alloy (Ag-Al-Cu) using an asymmetric phase diagram as well as interfacial properties.

Neoarchean arc magmatism followed by high-temperature, high-pressure metamorphism in the Nilgiri Block, southern India

The Nilgiri Block, southern India is an exhumed lower crust formed through arc magmatic processes in the Neoarchean. The main lithologies in this terrane include charnockites, gneisses, volcanic tuff, metasediments, banded iron formation and mafic-ultramafic bodies. Mafic-ultramafic rocks are present towards the northern and central part of the Nilgiri Block. We examine the evolution of these mafic granulites/metagabbros by phase diagram modeling and U-Pb sensitive high resolution ion microprobe (SHRIMP) dating. They consist of a garnet-clinopyroxene-plagioclase-hornblende-ilmenite +/- orthopyroxene +/- rutile assemblage. Garnet and clinopyroxene form major constituents with labradorite and orthopyroxene as the main mineral inclusions. Labradorite, identified using Raman analysis, shows typical peaks at 508 cm(-1), 479 cm(-1), 287 cm(-1) and 177 cm(-1). It is stable along with orthopyroxene towards the low-pressure high-temperature region of the granulite fades (M1 stage). Subsequently, orthopyroxene reacted with plagioclase to form the peak garnet + clinopyroxene + rutile assemblage (M2 stage). The final stage is represented by amphibolite facies-hornblende and plagioclase-rim around the garnet-clinopyroxene assemblage (M3 stage). Phase diagram modeling shows that these mafic granulites followed an anticlockwise P-T-t path during their evolution. The initial high-temperature metamorphism (M1 stage) was at 850-900 degrees C and similar to 9 kbar followed by high-pressure granulite fades metamorphism (M2 stage) at 850-900 degrees C and 14-15 kbar. U-Pb isotope studies of zircons using SHRIMP revealed late Neoarchean to early paleoproterozoic ages of crystallization and metamorphism respectively. The age data shows that these mafic granulites have undergone arc magmatism at ca. 25392 +/- 3 Ma and high-temperature, high-pressure metamorphism at ca. 2458.9 +/- 8.6 Ma. Thus our results suggests a late Neoarchean arc magmatism followed by early paleoproterozoic high-temperature, high-pressure granulite facies metamorphism due to the crustal thickening and suturing of the Nilgiri Block onto the Dharwar Craton. (C) 2015 Elsevier B.V. All rights reserved.

Evolution of high-pressure mafic granulites and pelitic gneisses from NE Madagascar: Tectonic implications

The occurrence of high-pressure mafic-ultramafic bodies within major shear zones is one of the indicators of paleo-subduction. In mafic granulites of the Andriamena complex (north-eastern Madagascar) we document unusual textures including garnet-clinopyroxene-quartz coronas that formed after the breakdown of orthopyroxene-plagioclase-ilmenite. Textural evidence and isochemical phase diagram calculations in the Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O-TiO2 system indicate a pressure-temperature (P-T) evolution from an isothermal (780 degrees C) pressure up to c. 24 kbar to decompression and cooling. Such a P-T trajectory is typically attained in a subduction zone setting where a gabbroic/ultramafic complex is subducted and later exhumed to the present crustal level during oceanic closure and final continental collision. The present results suggest that the presence of such deeply subducted rocks of the Andriamena complex is related to formation of the Betsimisaraka suture. LA-ICPMS U-Pb zircon dating of pelitic gneisses from the Betsimisaraka suture yields low Th/U ratios and protolith ages ranging from 2535 to 2625 Ma. A granitic gneiss from the Alaotra complex yields a zircon crystallization age of ca. 818 Ma and Th/U ratios vary from 1.08 to 2.09. K-Ar dating of muscovite and biotite from biotite-kyanite-sillimanite gneiss and garnet-biotite gneiss yields age of 486 +/- 9 Ma and 459 +/- 9 Ma respectively. We have estimated regional crustal thicknesses in NE Madagascar using a flexural inversion technique, which indicates the presence of an anomalously thick crust (c. 43 km) beneath the Antananarivo block. This result is consistent with the present concept that subduction beneath the Antananarivo block resulted in a more competent and thicker crust. The textural data, thermodynamic model, and geophysical evidence together provide a new insight to the subduction history, crustal thickening and evolution of the high-pressure Andriamena complex and its link to the terminal formation of the Betsimisaraka suture in north-eastern Madagascar. (C) 2015 Elsevier B.V. All rights reserved.

Fermionic quantum systems. Part I: Phase transitions in quantum dots. Part II: Nuclear matter on a lattice

In the first part I perform Hartree-Fock calculations to show that quantum dots (i.e., two-dimensional systems of up to twenty interacting electrons in an external parabolic potential) undergo a gradual transition to a spin-polarized Wigner crystal with increasing magnetic field strength. The phase diagram and ground state energies have been determined. I tried to improve the ground state of the Wigner crystal by introducing a Jastrow ansatz for the wave function and performing a variational Monte Carlo calculation. The existence of so called magic numbers was also investigated. Finally, I also calculated the heat capacity associated with the rotational degree of freedom of deformed many-body states and suggest an experimental method to detect Wigner crystals.

The second part of the thesis investigates infinite nuclear matter on a cubic lattice. The exact thermal formalism describes nucleons with a Hamiltonian that accommodates on-site and next-neighbor parts of the central, spin-exchange and isospin-exchange interaction. Using auxiliary field Monte Carlo methods, I show that energy and basic saturation properties of nuclear matter can be reproduced. A first order phase transition from an uncorrelated Fermi gas to a clustered system is observed by computing mechanical and thermodynamical quantities such as compressibility, heat capacity, entropy and grand potential. The structure of the clusters is investigated with the help two-body correlations. I compare symmetry energy and first sound velocities with literature and find reasonable agreement. I also calculate the energy of pure neutron matter and search for a similar phase transition, but the survey is restricted by the infamous Monte Carlo sign problem. Also, a regularization scheme to extract potential parameters from scattering lengths and effective ranges is investigated.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Electric field driven quantum phase transition between band insulator and topological insulator

We demonstrate theoretically that electric field can drive a quantum phase transition between band insulator to topological insulator in CdTe/HgCdTe/CdTe quantum wells. The numerical results suggest that the electric field could be used as a switch to turn on or off the topological insulator phase, and temperature can affect significantly the phase diagram for different gate voltage and compositions. Our theoretical results provide us an efficient way to manipulate the quantum phase of HgTe quantum wells.

GROWTH OF GASB AND GAASSB IN THE SINGLE-PHASE REGION BY MOVPE

GaSb layers are grown on GaSb substrates; the effects of input partial pressure of trimethylantimony and the V/III ratio are studied. A model of the MOVPE phase diagram for the growth of GaSb and GaAsxSb1-x is developed which assumes thermodynamic equilibrium to be established at the solid-vapor interface.

以金属为缓冲层在Si（111）上分子束外延GaN及其表征

用电子束蒸发方法在Si（111）衬底上蒸发了Au/Cr和Au/Ti/Al/Ti两种金属缓冲层,然后在金属缓冲层上用气源分子束外延（GSMBE）生长GaN.两种缓冲层的表面都比较平整和均匀,都是具有Au（111）面择优取向的立方相Au层.在Au/Cr/Si（111）上MBE生长的GaN,生长结束后出现剥离.在Au/Ti/Al/Ti/Si（111）上无AlN缓冲层直接生长GaN,得到的是多晶GaN;先在800℃生长一层AlN缓冲层,然后在710℃生长GaN,得到的是沿GaN（0001）面择优取向的六方相GaN.将Au/Ti/Al/Ti/Si（111）在800℃下退火20min,金属层收缩为网状结构,并且成为多晶,不再具有Au（111）方向择优取向.

Ti/莫来石陶瓷界面反应的俄歇电子能谱研究

结果表明，在淀积过程中，最初淀积的Ti与衬底表面的氧形成Ti-O键，界面区很窄；450℃退火1h后，有少量元素态Al、Si原子析出，界面区有所展宽，但变化不大；650℃退火1h后，界面发生强烈反应，有TiO和Ti-Al、Ti-Si化合物生成。850℃退火1h后，除上述反应产物外又生成了Ti_2O。

Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.

Monte Carlo simulation of phase behavior of polymer blends with special interactions

Full Paper: The phase, behavior of A-B-random copolymer/C-homopolymer, blends with special interaction was studied by a. Monte, Carlo simulation in two dimensions. The interaction between I segment A and segment C was repulsive, whereas it was attractive between segment B and segment C. The simulation results showed that the blend became two large co-continuous phase domains at lower segment-B component compositions, indicating that the blend showed spinodal decomposition. With an increase of the segment-B component, the miscibility between the copolymer,and the polymer was gradually improved up to being miscible. In addition, it was found that segment B tended to move to the surface of the copolymer phase in the case of a lower component of segment B. On the other hand, if was observed that the average, end-to-end distances ((h) over bar) for both copolymer and polymer changed slowly with increasing segment-B component of the copolymer up to 40%, thereafter they increased considerably with increasing segment B component. Moreover, it was found that the (h) over bar of the copolymer was obviously shorter than that of the homopolymer for the segment-B composition, region from 0% to 80%. Finally, a, phase diagram showing I phase and - II phase regions under the condition of constant-temperature is presented.