High-Pressure Phase Transitions of M2O5(M = V, Nb, Ta) and Thermal Stability of New Polymorphs

The stability regions of various M₂O₅(M = V, Nb, Ta) polymorphs were studied by quenching samples from 600–1300°C at pressures in the range 5.0–8.0 GPa. Above 7.0 GPa, Nb₂O₅and Ta₂O₅were found to have a new polymorph (Zphase) in which the metal atoms are in sevenfold coordination. In addition, the samples contained the high-pressure polymorph B-M₂O₅ with the rutile-related structure. Differential thermal analysis at atmospheric pressure showed a weak, broad exotherm, indicating that the transformation of Z-M₂O₅into other phases begins at 100–150°C and reaches completion at 400°C in Nb₂O₅and 550°C in Ta₂O₅. At p 8.0 GPa and t> 750°C, a new high-pressure phase B-V₂O₅, isostructural with B-Nb₂O₅, was identified (a= 11.9640(6) Å, b= 4.6986(3) Å, c= 5.3249(3) Å, = 104.338(4)°, V= 290.01 ų, Z= 4, sp. gr. C2/c). At atmospheric pressure, B-V₂O₅transforms into -V₂O₅, with two strong exothermic peaks at 230 and 270°C. Experiments in the pressure range 5.0–8.0 GPa confirmed that the high-pressure phase -V₂O₅has a broad stability region.     

Microstructure and mechanical properties of B6O-B4C sintered composites prepared under high pressure

Sintered composites in the B₆O-xB₄C (x = 0–40 vol%) system were prepared under high pressure and high temperature conditions (3–5 GPa, 1500–1800°C) from the mixture of in-laboratory synthesized B₆O powder and commercially available B₄C powder. Relationship among the formed phases, microstructures and mechanical properties of the sintered composites was investigated as a function of sintering conditions and added B₄C content. Microhardness of the sintered composite was found to increase with treatment temperature up to 1800°C, while fracture toughness decreased slightly. Maximum microhardness of Hv 46 GPa was obtained from B₆O-30vol%B₄C sintered composite under the sintering conditions of 4 GPa, 1700°C and 20 min.     

New Cubic Phases in the Li–Na–Sb–Bi System

New compounds with the general formula A _x A"_3-x B _y B"_1-y (A, A" = Li, Na; B, B" = Sb, Bi) were prepared in the system Li–Na–Sb–Bi. Na₃Sb_0.5Bi_0.5has a hexagonal structure (Na₃As type, a= 5.415 Å, c= 9.595 Å), and Li₃Sb_0.5Bi_0.5and Li₂NaSb_0.5Bi_0.5have a cubic structure (BiF₃type, a= 6.645 and 6.772 Å, respectively). The phase transitions of alkali-metal pnictides were studied by in situ x-ray diffraction at room temperature and pressures from 10⁵Pa to 9.0 GPa. Li₃Sb and Na₃Sb were each shown to exist in two polymorphs with hexagonal (Na₃As type) and cubic (BiF₃type) structures. At atmospheric pressure, Li₃Sb undergoes an irreversible – phase transition at 650°C, while Na₃Sb undergoes a reversible transformation into a cubic phase at 2.3 GPa and room temperature.     

High thermal expansion KAlSiO4 ceramic

Orthorhombic kalsilite (KAlSiO₄) was prepared by solid-state reaction from K₂CO₃, Al₂O₃, and SiO₂. The axial thermal expansion coefficients of the orthorhombic kalsilite were 1.6×10^–5°C^–1 for the a-axis, 1.6×10^–5°C^–1 for the b-axis, 2.8×10^–5°C^–1 for the c-axis, and 2.0×10^–5°C^–1 for the average from room temperature to 1000°C. A high thermal expansion ceramic consisting of the orthorhombic kalsilite was prepared by sintering. The densification was promoted by adding Li₂CO₃. The KAlSiO₄ ceramic sintered at 1200°C for 2 h with 5 wt% Li₂CO₃ had a bending strength of 65 MPa and linear thermal expansion coefficient of 2.2×10^–5 °C^–1 from room temperature to 600°C.     

Investigations of Bi substitution in NdBa2Cu3Oy

Attempts to substitute Bi for Nd in orthorhombic NdBa₂Cu₃O _y , prepared in air or oxygen at about 950°C led instead to formation of Ba₂NdBiO₆, a new cubic compound witha=0.8703 nm. The possibility was then explored of preparing superconducting (Nd_1–x Bi _x )Ba₂Cu₃O _y , by first forming the tetragonal phase at 880–950°C in nitrogen or argon followed by reheating in oxygen or air at 250–500°C in order to insert the additional oxygen required to yield the orthorhombic form while avoiding oxidation of Bi³⁺ to Bi⁵⁺. X-ray diffraction studies, electrical conductivity measurements, and thermogravimetric analysis of products indicate that Bi does not enter the NdBa₂Cu₃O _y , lattice in either the tetragonal or the orthorhombic phase. Ba₂NdBiO₆ clearly forms on reheating in oxygen or air even at low temperatures, and evidence is presented that a poorly crystallized oxygen-deficient form of this compound is already present prior to the reheating.     

The high-temperature thermal expansion of BiPbSrCaCuO superconductor and the oxide components (Bi2O3, PbO,CaO, CuO)

The thermal expansion of superconducting Bi_1.6Pb_0.4Sr₂Ca₂Cu₃Ox (BiPbSrCaCuO) and its oxide components Bi₂O₃, PbO, CaO and CuO have been studied by high-temperature dilatometric measurements (30–800°C). The thermal expansion coefficient for the BiPbSrCaCuO superconductor in the range 150–830°C is =6.4×10^–6K^–1. The temperature dependences of L/L of pressed Bi₂O₃ reveals sharp changes of length on heating (T ₁=712°C), and on cooling (T ₂=637°C and T ₃=577°C), caused by the phase transition monoclinic-cubic (T ₁) and by reverse transitions via a metastable phase (T ₂ and T ₃). By thermal expansion measurements of melted Bi₂O₃ it is shown that hysteresis in the forward and the reverse phase transitions may be partly caused by grain boundary effect in pressed Bi₂O₃. The thermal expansion of red PbO reveals a sharp decrease in L/L, on heating (T ₁=490°C), related with the phase transition of tetragonal (red, a=0.3962 nm, c=0.5025 nm)-orthorhombic (yellow, a=0.5489 nm, b=0.4756 nm, c=0.5895 nm). The possible causes of irreversibility of the phase transition in PbO are discussed. In the range 50–740°C the coefficient of thermal expansion of pressed Bi₂O₃ (_m=3.6 × 10^–6 and _c=16.6×10^–6K^–1 for monoclinic and cubic Bi₂O₃ respectively), the melted Bi₂O₃ (_m=7.6×10^–6 and _c=11.5×10^–6K^–1), PbO (_t=9.4×10⁶ and _or=3.3×10^–6K^–1 for tetragonal and orthorhombic PbO respectively), CaO (=6.1×10^–6K^–1) and CuO (=4.3×10^–6K^–1) are presented.     

Structural and electrical studies on thin films of solid electrolyte Ag6I4WO4

An electrolytic method of preparation of thin films of solid electrolyte Ag₆I₄WO₄ on a silver substrate is described. Films of different quality were obtained when the electrolysis was carried out at different temperatures and current densities. X-ray diffraction studies were carried out to confirm the compound formation. Scanning electron micrographs were taken in order to study the surface characteristics of these films. Investigations on the a.c. electrical conductivity of films prepared at different electrolysis temperatures (10 to 80° C) and two current densities (2 and 10 mA cm^–2) are also reported in the temperature range 30 to 130° C. The films deposited at 65° C gave values of room temperature conductivity and the activation energy for Ag⁺ ion conduction as 0.04 ^–1 cm^–1 and 0.132 eV, respectively.     

Preparation of superconducting YBa2Cu3O7−x powders by a solution technique

Bulk superconducting YBa₂Cu₃O_7–x powder has been synthesized by a solution technique using a mixture of Ba-ethylenediaminetetra-acetic acid (EDTA) and [Y, Cu]-citric acid complexes. A light-blue, molecular-level, homogeneously mixed precursor was prepared, and transferred to powder form through vacuum drying. The vacuum-dried powder was decomposed at 800 °C for 4 h under flowing oxygen, then heat treated at high temperature from 850 to 950 °C for 6–12 h. The results ofT _c measurements and X-ray analysis show that the orthorhombic, superconducting phase can be formed at temperatures above 850 °C following low-temperature annealing. A sharp transition (T2 K) and high density can be achieved after 930 °C heat treatment. The 930 °C heat treated sample shows aJ _c value of 510 A cm^–2. It is concluded that this solution technique provides better stoichiometric control and lower reaction temperature than the conventional solid-state sintering process.     

Growth and Properties of K2TiNb2P2O13Crystals

K₂TiNb₂P₂O₁₃single crystals (monoclinic structure, a= 13.788 Å, b= 6.418 Å, c= 16.927 Å, = 97°) were grown from off-stoichiometric K₂O–TiO₂–Nb₂O₅–P₂O₅melts, and their habit was described. The 300°C electrical conductivity of the crystals was determined to be 5 × 10^–4S/cm.     

Crystallization characteristics of an amorphous Nb81Si19 alloy under high pressure and formation of the A15 phase

Amorphous Nb-19 at% Si alloy, prepared by rapid quenching from the molten state, was annealed while being subjected to a pressure of 10 GPA. X-ray diffraction investigations on the alloy specimens quenched to ambient conditions have shown that pressure greatly alters the crystallization characteristics and the cubic A15 (Nb₃Si)-phase forms in preference to the tetragonal Nb₃Si-phase at temperatures in the range from 710° C to 800° C. Up to 680° C, the component atoms do not show any tendency towards ordering upon crystallization and the body-centred tetragonal solid solution forms; while, at 830° C, niobium atoms diffuse to form the body-centred cubic Nb precipitates. Superconducting properties have been measured for the single-phase A15 structure with the lattice parametera=0.5155 nm with the results that the transition temperature,T _C, is 3.4 K and the temperature coefficient of the upper critical field,H _C2, is 1.2 MA m^–1 K^–1 (15 kOe K^–1).     

Mechanical behaviour of polycrystalline BeO,Al2O3 and AlN at high pressure

The mechanical behaviour of various types of BeO, Al₂O₃, and AlN have been investigated at confining pressures up to 1.25 GPa, at 25° C, and at strain rates of 3 to 7×10^–5 sec^–1. The stress-strain data taken in uniaxial compressive-stress loading indicate the BeO aggregates undergo a transition from brittle fracture at low pressures to plastic flow at high pressures. Depending on the fabrication process, this transition pressure in BeO occurs at 0.4 to 0.7 GPa. Concurrently, the ultimate compressive strength of BeO increases from 1.0 to 1.9 GPa at 0.1 MPa pressure to over 4.0 GPa at 1.O GPa. Alumina remains brittle at all pressures up to 1.25 GPa; its strength increases from 4.5 GPa at 0.1 MPa pressure to over 6.0 GPa at 1.25 GPa. Aluminium nitride behaves similarly to BeO, having a brittle-ductile transition at 0.55 GPa. Its ultimate strength increases from 3.2 GPa at 0.1 MPa pressure to 4.7 GPa at 0.8 GPa. The distortional strain energy (proportional to the area under the stress-strain curve) absorbed by each material during compression at pressure was calculated and compared to available data from the literature. Alumina shows a degraded energy absorption with pressure, but both BeO and AlN yield a strongly enhanced performance at moderate pressures. Beryllium oxide and AlN thus appear to be promising structural materials for certain applications where high strengths and ductilities are required at moderate pressures.     

High pressure consolidation of B6O-diamond mixtures

Sintered composites in the B₆O-xdiamond (x= 0–80 vol%) system were prepared under high pressure and high temperature conditions (3–5 GPa, 1400–1800°C) from the mixture of in-laboratory synthesized B₆O powder and commercially available diamond powder with various grain sizes (<0.25, 0.5–3, and 5–10 m). Relationship among the formed phases, microstructures, and mechanical properties of the sintered composites was investigated as a function of sintering conditions, added diamond content, and grain size of diamond. Sintered composites were obtained as the B₆O-diamond mixed phases when using diamond with grain sizes greater than 0.5 m, while the partial formation of the diamond-like carbon was observed when using diamond grain sizes less than 0.25 m. Microhardness of the sintered composite was found to increase with treatment temperature and pressure, and the fracture toughness slightly decreased. A maximum microhardness of H _v57 GPa was measured in the B₆O-60 vol% diamond (grain size < 0.25 m) sintered composite under the sintering conditions of 5 GPa, 1700°C and 20 min.     

Growth and Characterization of PrBa2Cu3O7?x Thin Film Used as Template Layer on SrTiO3 Substrate

We have grown PrBa₂Cu³O_7–x (PBCO) thin films on (100) SrTiO₃ substrates using pulsed laser deposition (PLD). X-ray diffraction (XRD) studies indicate that the orientation of PBCO films varied with increasing deposition temperature: b axis oriented films can be grown at 680°C, and a axis oriented films at the temperature between 692°C and 705°C. Atomic force microscopy (AFM) reveals that a good flatness of the films was obtained with surface mean roughness of less than 24 Å, indicating that it is suitable for use as template layers in a axis oriented epitaxial YBa₂Cu₃O_7–y /PBCO and YBCO/tetragonal–YBCO/PBCO multilayer structures.     

Thermal expansion of the cubic (3C) polytype of SiC

Thermal expansion of the cubic beta or (3C) polytype of SiC was measured from 20 to 1000° C by the X-ray diffraction technique. Over that temperature range, the coefficient of thermal expansion can be expressed as the second order polynominal: ₁₁=3.19×10^–6+ 3.60×10^–9 T–1.68×10^–12 T ² (1/° C). It increases continuously from about 3.2×10^–6/° C at room temperature to 5.1×10^–6/° C at 1000° C, with an average value of 4.45 × 10^–6/° C between room temperature and 1000° C. This trend is compared with other published results and is discussed in terms of structural contributions to the thermal expansion.     

Processing and characterization of an amorphous Si–N–(O) fibre

Si–N–(O) fibres were grown according to a high temperature vapour–solid process involving the reaction between SiO and NH₃ on a substrate. The oxygen concentration of the fibres is related to the partial pressures of SiO and NH₃ during fibre growth, depending respectively, on the processing temperature and the ammonia flow rate. The fibres consist of amorphous silicon oxynitride of composition Si0_2x N_4(1–x)/3 (0.1 < x < 0.2). They exhibit a large spread in tensile strength. The lowest values (about 1 GPa) correspond to large surface defects caused by intergrowth while the highest values reach 5 GPa for perfect fibres. The fibres are stable in nitrogen up to 1450 °C (10 h) in terms of composition, structure and mechanical behaviour owing to their high processing temperature (1450 °C) and the nitrogen pressure preventing decomposition. A superficial crystallization into Si₃N₄ is only observed at 1500 °C inducing a moderate decrease of strength. In argon, decomposition starts at 1400 °C yielding gaseous species (SiO and N₂), crystalline Si₃N₄ and free silicon beyond 1400 °C and induce a catastrophic drop of strength. Annealing in oxygen results in a growth of a protective SiO₂ scale, amorphous or partially crystalline at 1400 °C.     

Tungsten-oxide thin films as novel materials with high sensitivity and selectivity to NO2, O3, and H2S. Part II: Application as gas sensors

The electrical response of tungsten-oxide thin films as-deposited by electron-beam deposition and annealed (at 350–800 °C for 1–3 h in O₂) to NO₂, O₃ and H₂S was studied both experimentally and theoretically. In order to interpret the kinetic characteristics of tungsten-oxide thin films on exposure to different gases, a model based on surface adsorption/desorption processes coupled with bulk diffusion was used. A link between the geometrical and chemical heterogeneities of the tungsten-oxide film surfaces and their performance characteristics as gas sensors was established. It was shown that the nature and amount of surface-adsorption sites in the different nonstoichiometric phases (W _n O_3n–2 or W _n O_3n–1) and WO₃ as well as their conduction mechanisms are defined from the phase composition of the film, the crystallographic and electronic structures of the phases, the orientation of the crystallites within the film and the geometrical shape and dimensions of the crystallites. All tungsten-oxide thin films investigated in this work are suitable for detection of very low concentrations of NO₂ (0.05–0.5 ppm in N₂ and synthetic air), ozone (25–90 ppb) and H₂S (3–15 ppm in N₂ and synthetic air) at very low working temperatures (80–160 °C). The films annealed at 400 °C for 1–2 h are very selective to ozone at 120–160 °C; the films annealed at 400 °C for 1–3 h and at 800 °C for 1 h are very sensitive to NO₂ (in N₂).     

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO4

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO₂ gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO₄), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO_2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO₄ was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO₄+WO_2.72/CaO-ZrO₂/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO₃(s)NiWO₄(s) G°=–10500–0.708 T (±250) cal mol^–1.     

Synthesis of cubic boron nitride with boron nitride powder formed from triammoniadecaborane

Cubic BN was synthesized under high temperature and pressure conditions from BN powder formed by reaction of triammoniadecaborane (TAD) with ammonia. The BN powder formed from TAD and ammonia had a low degree of ordering. The crystal lattice of the BN powder increased in regularity with increasing synthesis temperature and time for the reaction of TAD with ammonia. The conversion yield of cubic BN at 1300 °C and 6.5 GPa in the presence of AIN increased with decreasing of reaction temperature of TAD and ammonia from 1000–700 °C. Cubic BN decreased in yield with increasing reaction time of TAD and ammonia at 800 °C. BN powder pre-heat treated at 1550 °C had a crystallite size,L _c, of 22 nm, and was converted to cubic BN in a 43% yield at 1300 °C and 6.5 GPa for 10 min. The activation energy for cubic BN synthesis from BN powder-20 mol% AIN was 97 kJ mol^–1, when the starting BN was synthesized at 800 °C. The conversion yield of cubic BN from the disordered BN-20 mol% AIN was 100% after heat treatment at 1300 °C and 6.5 GPa for 20 min.     

D. C. electrical properties of hot-pressed nitrogen ceramics

The d.c. electrical properties of some hot-pressed polycrystalline nitrogen ceramics have been measured between 18 and 500° C in applied electric fields up to 1.1×10⁴ Vcm^–1. The materials examined were Si₃N₄, 5wt%, MgO/Si₃N₄ and two sialons havingz=3.2 andz=4.0. The conduction in all the materials showed similar general features. The time dependent charging (I _c) and discharging currents (I _D) were observed which followed a I(t)t_–n law at room temperature withn=0.7 to 0.8. The exponentn forI _c decreased with increasing temperature. The current density-field (J _s-E) characteristics were ohmic in applied fields of less than 3×10³ Vcm^–1; conductivity increased with electric field above that range. Above about 280° C, a was independent ofE, its temperature dependence following log T ^–1. Below about 230° C conductivity fitted a exp (–B/T _1/4) law in both low and high fields. There is a good correlation between the temperature and field variations of time dependent current and the steady current. The conductivities were in the range of 10^–15 to 10^–16–1 cm^–1 at 18° C and rose to 4×10^–10 to 2×10^{–12 –1} cm^–1 at 500° C. The activation energies were in the range of 1.45 to 1.80 eV and 0.05 to 0.15 eV at above 300° C and near room temperature respectively. Various models to explain the data are considered.     

Synthesis, Crystal Structure, and Ionic Conductivity of Tl2Ta2(PO4)2(HP5O16)

Tl₂Ta₂(PO₄)₂(HP₅O₁₆) is synthesized at 400°C in molten polyphosphoric acids containing Tl, Ta, and P in the ratio 4 : 1 : 15, and its crystal structure is determined: monoclinic cell, a = 5.1469 Å, b= 18.451 Å, c = 10.793 Å, = 95.65°, Z = 2, sp. gr. P2₁/m. The framework of the structure is made up of monophosphate and hydrogen pentaphosphate groups which share corners with TaO₆ octahedra. The Tl atoms reside in infinite channels. Neighboring pentaphosphate groups are hydrogen-bonded. In the range 60–350°C, the compound has a rather high ionic conductivity, which is tentatively attributed to proton transport. The activation energy of conduction is 48 ± 1 kJ/mol.