Phase diagram of the CuGaSe2–SiSe2 and CuInSe2–SiSe2 systems

The phase diagrams of the CuGaSe₂–SiSe₂ and CuInSe₂–SiSe₂ systems were constructed using the results of differential thermal and X-ray phase analysis. Both systems are of the eutectic type with the eutectic point coordinates 75 mol% SiSe₂, 1042 K (CuGaSe₂–SiSe₂); 67 mol% SiSe₂, 1083 K (CuInSe₂–SiSe₂). Solid solutions based on CuGaSe₂ and CuInSe₂ were discovered in these systems; their extent at 670 K being 24 and 25 mol% SiSe₂, respectively. The crystal structure of the limiting compositions of these solid solutions was refined.     

Subsolidus phase relations in the ZnO–MoO3–B2O3, ZnO–MoO3–WO3 and ZnO–WO3–B2O3 ternary systems

The subsolidus phase relations in the ZnO–MoO₃–B₂O₃, ZnO–MoO₃–WO₃ and ZnO–WO₃–B₂O₃ ternary systems have been investigated by the means of X-ray powder diffraction (XRD). There is no ternary compound in all the systems. There are five binary compounds and five tie lines in the ZnO–MoO₃–B₂O₃ system. This system can be divided into six 3-phase regions. There are three binary compounds and three tie lines in the ZnO–MoO₃–WO₃ system. This system can be divided into four 3-phase regions. There are four binary compounds and four tie lines in the ZnO–WO₃–B₂O₃ system. This system can be divided into five 3-phase regions. The possible component regions for ZnO single crystal flux growth were discussed. The phase diagram of Zn₃B₂O₆–ZnWO₄ pseudo-binary system has been constructed, and the result reveals this system is eutectic system. The eutectic temperature is 1007 °C and eutectic point component is 70 mol% Zn₃B₂O₆.     

Oxygen release behaviour of Ce(1−x)ZrxO2 powders and appearance of Ce(8−4y)Zr4yO(14−δ) solid solution in the ZrO2–CeO2–CeO1.5 system

To clarify the existence of metastable phases in the ZrO₂–CeO₂–CeO_1.5 system, evolved-oxygen gas analyses, (EGA), by heating a single phase of t′ and t″ (Ce_(1−x)Zr_xO₂) with various compositions, x, in a reducing gas and successive oxidation were carried out repeatedly. The oxygen release behaviour of the t′ and t″ phases was very complicated. The single κ phases, (Ce_(1−x)Zr_xO₂) with the composition, x=0.5 and 0.6, which were obtained by oxidizing the resulting pyrochlore as a precursor in O₂ gas at 873 K, exhibited a sharp oxygen release at the lowest temperature; the composition range of κ phase may be x=0.450.65. A new tetragonal phase t*, (Ce_(1−x)Zr_xO₂), which was attained by cyclic redox process together with annealing in O₂ gas at 1323 or 1423 K, exhibited a sharp oxygen release at the highest temperature; the composition range of t* phase may be as wide as x=0.200.65. A metastable solid solution expressed by a chemical formula of Ce_(8−4y)Zr_4yO_(14−δ) (y=01) possessing a CaF₂-related structure appeared on deoxidation of the t* phase. A ternary phase diagram containing the t* and Ce_(8−4y)Zr_4yO_(14−δ) solid solution was proposed.     

ZrO2–SiO2 gradient multilayer oxidation protective coating for SiC coated carbon/carbon composites

In order to eliminate the mismatch of thermal expansion coefficient between the ZrO₂ outer layer and the internal bonding SiC layer, ZrO₂–SiO₂ composition-gradient transition layers were prepared by a sol–gel technique using tetraethoxysilane (TEOS) and zirconyl chloride as source materials. Energy dispersive spectroscopy (EDS) analysis displays that the gradient composition ZrO₂–SiO₂ outer coating could be obtained by immersing the SiC precoated carbon/carbon (C/C) composites into the gradient composition zirconia-silica sols (ZS sol) in turn. Oxidation test shows that, after 10 h oxidation in air at 1773 K, the weight loss of the gradient ZrO₂–SiO₂ coating coated SiC-C/C is only 1.97%.     

Phase diagram and electrical conductivity of the CeBr3–RbBr binary system

Phase equilibrium in the CeBr₃–RbBr binary system was established from differential scanning calorimetry (DSC). This system has three compounds Rb₃CeBr₆, Rb₂CeBr₅ and RbCe₂Br₇ and two eutectics located at (x = 0.141; 858 K) and (x = 0.528; 762 K), respectively. Rb₃CeBr₆ forms at 614 K, undergoes a solid–solid phase transition at 695 K and melts congruently at 966 K. Rb₂CeBr₅ melts incongruently at 830 K and RbCe₂Br₇ at 741 K. The electrical conductivity of CeBr₃–RbBr liquid mixtures was measured down to temperatures below solidification over the whole composition range. Results obtained are discussed in term of possible complex formation.     

Thermodynamic properties and phase diagrams of the binary systems B2O3–Ga2O3, B2O3–Al2O3 and B2O3–In2O3

We calculated the binary phase diagrams B₂O₃–Ga₂O₃, B₂O₃–In₂O₃ and B₂O₃–Al₂O₃, and the Gibbs energy of formation of the binary compounds, using experimental liquidus data. The B₂O₃–Ga₂O₃ system is of industrial importance, because liquid B₂O₃, in which Ga₂O₃ is not very soluble, is used to protect GaAs during growth of single crystals of GaAs. During recovery of noble metals B₂O₃ is added to slags containing Al₂O₃ to lower the melting point and the viscosity. The B₂O₃–In₂O₃ system is of much less importance to industry. In all three systems we have a liquid miscibility gap, and also solid binary compounds, none of which melt congruently. The miscibility gaps are not surprising, because even in the B₂O₃–Bi₂O₃ system where four congruently melting compounds are present, a liquid miscibility gap exists close to B₂O₃.     

Thermal and conductometric studies of the CeBr3–MBr binary systems (M = Li, Na)

DSC was used to investigate phase equilibrium in the CeBr₃–MBr (M = Li, Na) systems. They represent typical examples of simple eutectic systems. The eutectic composition and eutectic temperature, x(CeBr₃) = 0.249, T_eut = 709 K and x(CeBr₃) = 0.372, T_eut = 692 K, were found for CeBr₃–LiBr and CeBr₃–NaBr systems, respectively.

The electrical conductivity of CeBr₃–MBr liquid mixtures, together with that of pure components was measured down to temperatures below solidification. Results obtained are discussed in term of possible complex formation.     

Spectroscopic and dielectric studies on MnO doped PbO–Nb2O5–P2O5 glass system

PbO–Nb₂O₅–P₂O₅ glasses containing different concentrations of MnO ranging from 0 to 2.5 mol% were prepared. A number of studies viz., differential thermal analysis, infrared, optical absorption, luminescence, Raman and ESR spectra, magnetic susceptibility and dielectric properties (constant ′, loss tan δ, ac conductivity σ_ac over a range of frequency and temperature) of these glasses have been carried out. The results have been analyzed in the light of different oxidation states of manganese ions. The analysis indicates that when the concentration of MnO is around 1.0 mol%, manganese ions mostly exist in Mn²⁺ state, occupy network forming positions with MnO₄ structural units and increase the rigidity of the glass network. When MnO is present in higher concentrations, these ions seem to exist mostly in Mn³⁺ state and occupy modifying positions.     

Pore morphology in sintered ZrO2–8 mol% Y2O3 ceramic: a small-angle neutron scattering investigation

Pore morphology and pore size distribution in yttria-stabilized zirconia (ZrO₂–8 mol% Y₂O₃) have been investigated, for two sintering temperatures, namely 1200 and 1270 °C, using small-angle neutron scattering. The results show that the reduction in the porosity, at 1270 °C compared to that at 1200 °C, occurs by the elimination of the pores at the lower end of the pore size distribution. In addition, the polydispersity is also lower at 1270 °C and the nature of the distribution is altered significantly near the smaller radius range. The average pore size shifts towards the higher radius range. The specific surface area of the pores is also diminished at 1270 °C because of the elimination of the finer pores.     

Spark plasma sintering and in vitro study of ultra-fine HA and ZrO2–HA powders

Spark plasma sintering (SPS) was employed to sinter RF suspension plasma sprayed HA ultra-fine powders and ZrO₂–HA nano-composite powders. The powders were sintered at 1000 °C for 5 min at 11.1 MPa and 1100 °C for 5 min at 11.1 MPa, respectively. After sintering, the samples were ground and polished for subsequent indentation and microscopy studies. The as-sintered compacts of the HA–CaP powders were studied in vitro by immersion in simulated body fluid (SBF). The in vitro studies indicated that a bio-active apatitic layer was formed as early as 1 week after immersion. Optical microscopy and SEM investigation revealed negligible porosity and dense microstructure suggesting liquid phase sintering to have taken place. Phase composition was calculated with the aid of XRD and the Rietveld method. The results indicated that the mechanical properties of the as-sintered compacts were improved in the presence of nano-ZrO₂. The Young’s modulus increased to 130 MPa and the fracture toughness was 1.6 MPa m^1/2 for ZrO₂ loading lower than 3 vol.% indicating greater enhancement of properties than that suggested by the rule of mixtures.     

Powder processing and densification behaviour of alumina–high zirconia nanocomposites using chloride precursors

Al₂O₃–ZrO₂ composites having nominal equal volume fraction of Al₂O₃ and ZrO₂ were prepared from gel-precipitated powder, precipitated powder and washed precipitated powder. These different processing routes affected the crystallization temperature of the amorphous powder as well as the phase evolution of Al₂O₃ and ZrO₂ during calcination. The agglomerate size was largest for gel-precipitated powder (30 μm) and it was smallest for washed precipitated powder (19 μm). While gel-precipitated powder produce hard agglomerated powder (P_j = 110 MPa), washed precipitated powder produce soft agglomerates with low agglomeration strength (P_j = 70 MPa). Thus, washed precipitated powder could sinter to a high density at lower sintering temperature. The bending strength exhibits a semi logarithmic relationship with porosity. The hardness shows an increasing trend with sintering temperature.     

Hydriding kinetics of the La1.5Ni0.5Mg17–H system prepared by hydriding combustion synthesis

An experimental investigation of the hydrogen absorption rate in the two-phase (–β) region of La_1.5Ni_0.5Mg₁₇ powder under the condition of various pressures and temperatures is presented. The results are well interpreted using the Jander diffusion model, [1−(1−ξ)^1/3]²=k(T,P)t, which suggests that the rate-controlling step of hydrogen absorption in La_1.5Ni_0.5Mg₁₇ is three-dimensional diffusion. An apparent activation energy for such diffusion process of 90±1 kJ/mol H₂ has been obtained from the absorption data.     

Properties of ZrO2–Al2O3 composite as a function of isothermal holding time

Zirconia and alumina based ceramics present interesting properties for their application as implants, such as biocompatibility, good fracture resistance, as well as high fracture toughness and hardness. In this work the influence of sintering time on the properties of a ZrO₂–Al₂O₃ composite material, containing 20 wt% of Al₂O₃, has been investigated. The ceramic composites were obtained by sintering, in air, at 1600 °C for sintering times between 0 and 1440 min. Sintered samples were characterized by microstructure and crystalline phases, as well as by mechanical properties. The grain growth exponents, n, for the ZrO₂ and Al₂O₃ were 2.8 and 4.1, respectively, indicating that different mechanisms are responsible for grain growth of each phase. After sintering at 1600 °C, the material exhibited a dependency of hardness as function of sintering time, with hardness values between 1500 HV (120 min) and 1310 HV (1440 min) and a fracture toughness of 8 MPa m^1/2, which makes it suitable for bioapplications, such as dental implants.     

Phase relations in the SrO–Ga2O3–B2O3 system

The subsolidus phase relations in the SrO–Ga₂O₃–B₂O₃ system were investigated. The system contains 10 binary compounds and two ternary compounds, and can be divided into 15 three-phase regions. The new ternary compound SrGaBO₄ has two modifications (- and β-phases), both of which crystallize in the orthorhombic system but with different space groups.     

Influence of Al- and Cu-doping on the thermodynamic properties of the LaNiIn–H system

The Pressure–Composition–Temperature (P–C–T) relations for the LaNiIn, LaNi_0.95Cu_0.05In and LaNiIn_0.98Al_0.02–H systems were measured by a volumetric Sieverts’ method at 398–423 K. All isotherms show plateau pressure regions indicating equilibria between two hydride phases. The replacements of Ni by Cu and In by Al affect the P–C–T diagrams, stability of the hydrides, homogeneity regions of the hydrides formed, slope of the isotherms and critical temperatures of the β–γ transition. In addition, the Cu-doping induces a significant hysteresis between the hydrogen absorption and desorption processes. The relative partial molar thermodynamic properties for the studied systems are: ΔH_H = −34.6 ± 2.1 kJ (mol_H)⁻¹, ΔS_H = −70.7 ± 3.6 J (K·mol_H)⁻¹ for LaNiIn–H; ΔH_H = −34.1 ± 0.5 kJ (mol_H)⁻¹, ΔS_H = −74.9 ± 1.0 J (K·mol_H)⁻¹ for LaNi_0.95Cu_0.05In–H; ΔH_H = −33.2 ± 0.8 kJ (mol_H)⁻¹, ΔS_H = −68.3 ± 1.2 J(K·mol_H)⁻¹ for LaNiIn_0.98Al_0.02–H.     

Effect of atomic order on the martensitic transformation of Ni–Fe–Ga alloys

The effect of atomic order on martensitic transformation (MT) temperatures has been studied by differential scanning calorimetry in three polycrystalline alloys with compositions Ni_53.5+x–Fe_19.5−x–Ga_27.0 (x = 0, 0.5 and 1.5). Samples water quenched from different temperatures (470–1070 K) exhibit higher MT temperatures than ones slow cooled from the same temperature. This effect has been ascribed to a decrease of the L2₁ degree of order of the austenitic phase, which promotes an increase in the MT temperatures in these Ni–Fe–Ga alloys. The differences in ordering with cooling rate have been qualitative confirmed by electron diffraction patterns.     

Preparation and properties of a γ-Al2O3 washcoat deposited on a ceramic honeycomb

Washcoat deposited on ceramic honeycomb was prepared using pseudoboehmite, the CeO₂–ZrO₂–La₂O₃ solid solution, pore enlarger and other additives. The microstructures and surface performances of washcoat/honeycomb were investigated by SEM, BET surface area, XRD, ultrasonic vibration and hot shock simulation. The results show that the performance and loading of washcoat are affected obviously by the properties of slurry gel, such as the apparent viscosity, solid content, particle size and its distribution. When the apparent viscosity of slurry is lower, the gel with a narrow particle size distribution and finer particles can be obtained, with which the coating having an excellent performance can be prepared. Adding a small quantity of the CeO₂–ZrO₂–La₂O₃ solid solution can promote the thermal stability of washcoat, such as, after calcined at 1000 °C for 5 h the sample exhibits mainly the γ-Al₂O₃ phases and the θ-Al₂O₃ -Al₂O₃ and κ-Al₂O₃ phases have not been detected in the XRD spectra. It is found also that the washcoat prepared has excellent properties of the vibration-resistant, heat-resistant and its BET surface area reaches 50 m²/g.     

Effect of ZnO additive on sintering behavior and microwave dielectric properties of 0.95MgTiO3–0.05CaTiO3 ceramics

The effects of ZnO additive on the microstructures, the phase formation and the microwave dielectric properties of MgTiO₃–CaTiO₃ ceramics were investigated. The sintering temperature of ZnO-doped 0.95MgTiO₃–0.05CaTiO₃ ceramics can be lowered to 1300 °C due to the liquid phase effect. Formation of second phase MgTi₂O₅ can be effectively restrained through the addition of ZnO. The microwave dielectric properties are found strongly correlated with the sintering temperature as well as the amount of ZnO addition. At 1300 °C, 0.95MgTiO₃–0.05CaTiO₃ ceramics with 1 wt% ZnO addition possesses a dielectric constant _r of 20, a Q × f value of 65,000 (at 7 GHz) and a τ_f value of −5.8 ppm/°C. In comparison with pure 0.95MgTiO₃–0.05CaTiO₃ ceramics, the doped sample shows not only a 16% loss reduction but also a lower sintering temperature. That makes it a very promising material to replace the present one for GPS patch antennas.     

Microstructural, Raman and dielectric properties of (1−x)NaNbO3–xBiCrO3 biphase ceramics

The phase, microstructural and dielectric properties of (1−x)NaNbO₃–xBiCrO₃ (x = 0.1, 0.2, 0.3, 0.4 and 0.5) ceramics with perovskite–pyrochlore mixed-phase were investigated. A single-phase solid solution in the sintered specimens was identified as observed perovskite phase for x = 0.1 and pyrochlore for x = 0.5. The results indicate that the microstructure has mixed large and small grains. Dielectric constants and dielectric loss were measured as functions of temperatures (−15 to 200 °C) at 1 kHz. Complex impedance spectroscopy shows the presence of barrier layers in biphase ceramics. The Raman spectra and porosity percentage in the biphase system were also measured.     

Spectroscopic and 1.06 μm laser properties of Nd-doped K–Sr–Al phosphate and fluorophosphate glasses

Optical absorption, fluorescence and decay curves for the ⁴F_3/2 level of Nd³⁺ ions in phosphate (P₂O₅–K₂O–SrO–Al₂O₃) and fluorophosphate (P₂O₅–K₂O–SrO–Al₂O₃–AlF₃ and P₂O₅–K₂O–SrO–Al₂O₃–BaF₂) glasses doped with three concentrations (0.1, 1.0 and 2.0 mol%) of Nd³⁺ ions have been investigated. The Judd–Ofelt (JO) theory has been applied to the absorption spectra of 1.0 mol% Nd³⁺-doped glasses to derive JO intensity parameters which are in turn used to calculate the radiative properties of the Nd³⁺ ion fluorescent levels. The assigned energy level data of Nd³⁺ (4f³) ions are analysed in terms of a parametrized free-ion Hamiltonian model that consists of 20 interaction parameters of atomic nature. The stimulated emission cross section and branching ratios have been calculated using the emission spectra. The relatively higher branching ratio for ⁴F_3/2 → ⁴I_11/2 transition shows the suitability of these glasses for laser application. It is interesting to note that the measured decay curves of the ⁴F_3/2 level remain nearly single exponential even for higher Nd³⁺ ion concentration but with shortening of lifetime.