Preparation of NiAl2O4/SiO2 and Co2+-Doped NiAl2O4/SiO2 Nanocomposites by the Sol–Gel Route

NiAl₂O₄/SiO₂ and Co²⁺-doped NiAl₂O₄/SiO₂ nanocomposite materials of compositions 5% NiO – 6% Al₂O₃– 89% SiO₂ and 0.2% CoO – 4.8% NiO – 6% Al₂O₃– 89% SiO₂, respectively, were prepared by a sol–gel process. NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals were grown in a SiO₂ amorphous matrix at around 1073 K by heating the dried gels from 333 to 1173 K at the rate of 1 K/min. The formations of NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals in SiO₂ amorphous matrix were confirmed through X-ray powder diffraction, Fourier transform infrared spectroscopy, differential scanning calorimeter, transmission electron microscopy (TEM), and optical absorption spectroscopy techniques. The TEM images revealed the uniform distribution of NiAl₂O₄ and cobalt-doped NiAl₂O₄ nanocrystals in the amorphous SiO₂ matrix and the size was found to be ∼5–8 nm.     

Effect of Additives on the Electromechanical Properties of Pb(Zr,Ti)O3–Pb(Y2/3W1/3)O3 Ceramics

Dielectric and piezoelectric properties of 0.02Pb(Y_2/3W_1/3)O₃ 0.98Pb(Zr0.52Ti0.48)O3 ceramics doped with additives (Nb₂O₅, La₂O₃, MnO₂, and Fe₂O₃) were investigated. The grain sizes of these ceramics decreased with increasing amounts of additives. For additions of MnO₂ and Fe₂O₃, dielectric losses decreased, while for Nb₂O₅ and La₂O₃, these values increased. The maximum values of the mechanical quality factor Q_m were found to be 956 and 975 for additions of 0.9 wt% Fe₂O₃ and 0.7 wt% MnO₂, respectively, but donor dopants (Nb₂O₅ and La₂O₃) did not change the values of Q_m . On the other hand, the piezoelectric constant d₃₃ and the electromechanical coupling factor k_p decreased with additions of MnO₂ and Fe₂O₃, but improved with additions of Nb₂O₅ and La₂O₃.     

The System Si3N4-SiO2-Y2O3

Subsolidus phase relations were established in the system Si₃N₄-SiO₂-Y₂O₃. Four ternary compounds were confirmed, with compositions of Y₄Si₂O₇N₂, Y₂Si₃O₃N₄, YSiO₂N, and Y₁₀(SiO₄)₆N₂. The eutectic in the triangle Si₃N₄-Y₂Si₂O₇-Y₁₀(SiO₄)₆N₂ melts at 1500°C and that in the triangle Si₂N₂O-SiO₂-Y₂Si₂O₇ at 1550°C. The eutectic temperature of the Si₃N₄-Y₂Si₂O₇ join was ∼ 1520°C.     

Phase Relations in the Pseudobinary System Na2TiSi4O11-Na2Ti2Si2O9

The quenching technique was used to study subliquidus and subsolidus phase relations in the pseudobinary system Na₂ Ti₂Si₂ O₁₁-Na₂ Ti₂ Si₂ O₉. Both narsarukite (Na₂TiSi₄O₁₁) and lorenzenite (Na₂Ti₂Si₂O₉) melt incongruently. Narsarsukite melts at 911°±°C to SiO₂+liquid, with the liquidus at 1016°C. Lorenzenite melts at 910°±5°C to Na₂ Ti₆ O₁₃+liquid; Na₂ Ti₆ O₁₃ reacts with liquid to form TiO₂ and is thus consumed by 985°±5°C. The liquidus occurs at 1252°C.     

Phase Relations in the System Bi2O3-WO3

Phase relations in the system Bi₂O₃-WO₃ were studied from 500° to 1100°C. Four intermediate phases, 7Bi₂O₃· WO₃, 7Bi₂O₃· 2WO₃, Bi₂O₃· WO₃, and Bi₂O₃· 2WO₃, were found. The 7B₂O · WO₃ phase is tetragonal with a ₀= 5.52 Å and c ₀= 17.39 Å and transforms to the fcc structure at 784°C; 7Bi₂O₃· 2WO₃ has the fcc structure and forms an extensive range of solid solutions in the system. Both Bi₂O₃· WO₃ and Bi₂O₃· 2WO₃ are orthorhombic with (in Å) a ₀= 5.45, b ₀=5.46, c ₀= 16.42 and a ₀= 5.42, b ₀= 5.41, c ₀= 23.7, respectively. Two eutectic points and one peritectic exist in the system at, respectively, 905°± 3°C and 64 mol% WO₃, 907°± 3°C and 70 mol% WO₃, and 965°± 5°C and 10 mol% WO₃.     

Phase Equilibria in the System Si3N4-SiO2-BeO-Be3N2

The 1780°C isothermal section of the reciprocal quasiternary system Si₃N₄-SiO₂-BeO-Be₃N₂ was investigated by the X-ray analysis of hot-pressed samples. The equilibrium relations shown involve previously known compounds and 8 newly found compounds: Be₆Si³N₈, Be₁₁Si₅N₁₄, Be₅Si²N₆, Be₉Si₃N₁₀, Be₈SiO₄N₄, Be₆O₃N₂, Be₈O₅N₂, and Be₉O₆N₂. Large solid solubility occurs in β-Si₃N₄, BeSiN₂, Be₉Si₃N₁₀, Be₄SiN₄, and β-Be₃N₂. Solid solubility in β-Si₃N₄ extends toward Be₂SiO₄ and decreases with increasing temperature from 19 mol% at 1770°C to 11.5 mol% Be₂SiO₄ at 1880°C. A 4-phase isotherm, liquid +β-Si₃N₄ ( ss )Si₂ON₂+ BeO, exists at 1770°C.     

Studies in Lithium Oxide Systems: XI, Li2O–B2O3–P2O5

The glassforming region in the system was roughly outlined and liquidus data were obtained for the three joins LiPO₃-BPO₄, Li₄P₂O₇-BPO₄, and Li₃PO₄-Li₂B₄O₇. Compatibility relations for the ternary subsystems Li₄P₂O₇-BPO₄-P₂O₅ and Li₂O-Li₃PO₄-Li₂B₈O₁₃ were established. Two ternary compounds with the probable compositions 22Li₂O - 11B₂O₃ - 13P₂O₅ and 2Li₂O 3B₂O₃ P₂O₅ were detected.     

Na2SO4-lnduced Corrosion of Si3N4 Coated with Chemically Vapor Deposited Ta2O5

Hot isostatically pressed Si₃N₄ was coated with chemically vapor-deposited Ta₂O₅, and subjected to oxidative and corrosive environments to determine the feasibility of using a Ta₂O₅ coating for protecting Si₃N₄ from hot corrosion. The coated structure was relatively stable at 1000^deg;C in pure O₂. However, the Ta₂O₅-Si₃N₄ system became unstable in an environment containing Na₂SO₄ and O₂ at 1000^deg;C because (1) Ta₂O₅ and Na₂SO₄ reacted rapidly to form NaTaO₃ and (2) subsequently NaTaO₃ interacted destructively with the underlying Si₃N₄ substrate to form a molten phase.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

125Te, 27Al, and 71Ga NMR Study of M2O3–TeO2 (M = Al and Ga) Glasses

The structures of M₂O₃–TeO₂ (M = Al and Ga) glasses have been investigated by means of ¹²⁵Te, ²⁷Al, and ⁷¹Ga NMR spectroscopies. The structural units of respective cations in M₂O₃–TeO₂ glasses were quantitatively analyzed. The fractions of TeO₄ trigonal bipyramid, AlO₆ and GaO₆ octahedra decreased and those of TeO₃ trigonal pyramid, AlO₄, AlO₅, and GaO₄ polyhedra increased with increasing M₂O₃ content. Based on the local structures around Te, Al, and Ga atoms, the structure models of M₂O₃–TeO₂ glasses were proposed.     

Crystal Structure and Microwave dielectric Properties of Ba(Zn1/3Ta2/3)O3–(Sr,Ba)(Ga1/2Ta1/2)O3 Ceramics

The microwave dielectric properties and crystal structure of Ba(Zn_1/3Ta_2/3)O₃– (Sr,Ba)(Ga_1/2Ta_1/2)O₃ ceramics were investigated in the present study. The Q value of Ba(Zn_1/3Ta_2/3)O₃ was improved by adding 5 mol% Sr(Ga_1/2Ta_1/2)O₃. The maximum Q value of Q × f = 162000 GHz was obtained at 0.95Ba(Zn_1/3Ta_2/3)O₃. 0.05Sr(Ga_1/2Ta_1/2)O₃. For this composition, a lattice super structure caused by hexagonal ordering was observed. A further improvement in the Q value was attained when some Sr was replaced with Ba, and 0.95Ba(Zn_1/3Ta_2/3)O₃· 0.05(Sr_0.25Ba_0.75)(Ga_1/2Ta_1/2)O₃ exhibited a maximum Q value such that Q × f = 210000 GHz. Despite the increased Q value with the replacement of Sr by Ba, the c/a value, which indicates the degree of lattice distortion, remained constant near 3/2. The Q value thus improved without lattice distortion in the system Ba(Zn_1/3Ta_2/3)O₃-(Sr,Ba)(Ga_1/2Ta_1/2)O₃, whereas the improvement of Q value increased with lattice distortion in the solid solution system with Ba(Zn_1/3Ta_2/3)O₃ as an end member.     

Microstructure, Piezoelectric, and Ferroelectric Properties of Bi2O3-Added (K0.5Na0.5)NbO3 Lead-Free Ceramics

Lead-free piezoelectric (K_0.5Na_0.5)NbO₃– x wt% Bi₂O₃ ceramics have been synthesized by an ordinary sintering technique. The addition of Bi₂O₃ increases the melting point of the system and improves the sintering temperature of (K_0.5Na_0.5)NbO₃ ceramics. All samples show a pure perovskite phase with a typical orthorhombic symmetry when the Bi₂O₃ content <0.7 wt%. The phase transition temperature of orthorhombic–tetragonal ( T _{O − T} ) and tetragonal–cubic ( T _C) slightly decreased when a small amount of Bi₂O₃ was added. The remnant polarization P _r increased and the coercive field E _c decreased with increasing addition of Bi₂O₃. The piezoelectric properties of (K_0.5Na_0.5)NbO₃ ceramics increased when a small amount of Bi₂O₃ was added. The optimum piezoelectric properties are d ₃₃=140 pC/N, k _p=0.46, Q _m=167, and T _C=410°C for (K_0.5Na_0.5)NbO₃–0.5 wt% Bi₂O₃ ceramics.     

Piezoelectric Properties of Pb(Mg1/3Nb2/3)O3 PbTiO3 -PbZrO3 Ceramics Modified with Certain Additives

Effects of additives on the piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-PbZrO₃ ceramics in a perovskite-type structure are described. The tetragonality of Pb(Mg_1/3Nb_2/3)_0.375-Ti_0.375Zr_0.25O₃ ceramics increased with the addition of NiO, Cr₂O₃, or Fe₂O₃ but decreased with the addition of MnO₂ or CoO. The dielectric and piezoelectric properties of the base composition were improved markedly through selection of additives in proper amounts. Addition of NiO yielded a high dielectric constant and planar coupling coefficient for compositions at the morphotropic transition boundary. High mechanical Q -factors and low electrical dissipation factors were obtained by addition of MnO₂. Addition of both NiO and MnO₂ produced a mechanical Q -factor of 2051 and a planar coupling coefficient of 0.553. The resonant frequency of Pb(Mg_1/2Nb_2/3)_0.4375Ti_0.4375 zr_0.125O₃ containing MnO₂ had very low temperature and time dependence. The microstructure indicated that ceramics with a high mechanical Q -factor had a fine, uniform grain structure. Addition of Cr₂O₃ retarded grain growth and addition of MnO₂, NiO, CoO, or Fe₂O₃ promoted grain growth in the ternary system.     

Phase Equilibria in the System CaF2-AlF3-Na3AlF6 and Part of the System CaF2-AlF3-Na3AlF6-Al2O3

The complete phase-equilibrium diagram of the system CaF₂-AlF₃-Na₃AlF₆ and the subsolidus portion of the system CaF₂-AlF₃-Na₃AlF₆-Al₂O₃ were established from microscopic, powder X-ray diffraction, quench, and DTA data obtained from samples encapsulated in sealed tubes and either reacted in the solid state or melted and recrystallized. The system Na₃AlF₆-CaF₂ contains a simple eutectic with no compound formation or solid solution. The system CaF₂-AlF₃-Na₃AlF₆ contains two ternary compounds, NaCaAlF₆ and NaCaAl₂F₉, which melt incongruently at 735° and 712°C, respectively; NaCaAlF₆ exists in three polymorphic forms with transitions at 610° and 722°C and NaCaAl₂F₉ is body-centered cubic with a₀= 10.765 Å. The three binary and two ternary compounds divide the system into eight compatibility triangles. Along the NaCaAlF₆-Na₃AlF₆ join, 7 mol% NaCaAlF₆ is soluble in α-cryolite at 525° and 42% in β-cryolite at 731°C. The quaternary system Na₃AlF₆-AlF₃-CaF₂-Al₂O₃ contains eight compatibility tetrahedra.     

Phase Equilibria in the Pseudoternary System ZrO2−Y2O3−Cr2O3 at 1600°C in Air

The pseudoternary system ZrO₂-Y₂O₃-Cr₂O₃ was studied at 1600°C in air by the quenching method. Only one intermediate compound, YCrO₃, was observed on the Y₂O₃−Cr₂O₃ join. ZrO₂ and Y₂O₃ formed solid solutions with solubility limits of 47 and 38 mol%, respectively. The apex of the compatibility triangle for the cubic ZrO₂, Cr₂O₃, and YCrO₃ three-phase region was located at =17 mol% Y₂O₃ (83 mol% ZrO₂). Below 17 mol% Y₂O₃, ZrO₂ solid solution coexisted with Cr₂O₃. Cr₂O₃ appears to be slightly soluble in ZrO₂(ss).     

Phase Relations and Ordering in the Systems MgO-Y2O3-ZrO2 and CaO-MgO-ZrO2

The phase relations in the systems MgO-Y₂O₃-ZrO₂ and CaO-MgO-ZrO₂ were established at 1220° and 1420°C. The system MgO-Y₂O₃-ZrO₂ possesses a much-larger cubic ZrO₂ solid solution phase field than the system CaO-MgO-ZrO₂ at both temperatures. The ordered δ phase (Zr₃Y₄O₁₂) was found to be stable in the system ZrO₂-Y₂O₃ at 1220°C. Two ordered phases φ₁ (CaZr₄O₉) and φ₂ (Ca₆Zr₁₉O₄₄) were stable at 1220°C in the system ZrO₂-CaO. At 1420°C no ordered phase appears in either system, in agreement with the previously determined temperature limits of the stability for the δ, φ₁, and φ₂ phases. The existence of the compound Mg₃Y_zO₆ could not be confirmed.     

Porous Glass-Ceramics with a Skeleton of the Fast-Lithium-Conducting Crystal Li1+xTi2−xAlx(PO4)3

Porous glass-ceramics with a skeleton of the fast-lithium-conducting crystal Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ (where x = 0.3–0.5) were prepared by crystallization of glasses in the Li₂O─CaO─TiO₂─Al₂O₃–P₂O₅ system and subsequent acid leaching of the resulting dense glass-ceramics composed of the interlocking of Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ and β-Ca₃(PO₄)₂ phases. The median pore diameter and surface area of the resulting porous Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ glass-ceramics were approximately 0.2 μm and 50 m²/g, respectively. The electrical conductivity of the porous glass-ceramics after heating in LiNO₃ aqueous solution was 8 × 10⁻⁵ S/cm at 300 K or 2 × 10⁻² S/cm at 600 K.     

The System HfO2-Y2O3-Er2O3

A mathematical model of the liquidus surface based on a reduced polynomial method was proposed for the system HfO₂-Y₂O₃-Er₂O₃. The results of calculations according to this model agree fairly well with the experimental data. Phase equilibria in the system HfO₂-Y₂O₃-Er₂O₃ were studied on melted (as-cast) and annealed samples using X-ray diffraction (at room and high temperatures) and micro-structural and petrographic analyses. The crystallization paths in the system HfO₂-Y₂O₃-Er₂O₃ were established. The system HfO₂-Y₂O₃-Er₂O₃ is characterized by the formation of extended solid solutions based on the fluorite-type (F) form of HfO₂ and cubic (C) and hexagonal (H) forms of Y₂O₃ and Er₂O₃. The boundary curves of these solid solutions have the minima at 2370°C (15. 5 mol% HfO₂, 49. 5 mol% Y₂O₃) and 2360°C (10. 5 mol% HfO₂, 45. 5 mol% Y₂O₃). No compounds were found to exist in the system investigated.     

Effect of Praseodymium on Superconductivity and Magnetism in Y1–xPrxBa2Cu4O8 Prepared by Nitrite Pyrolysis Method

X-ray diffraction patterns show that most samples of Y_1-x Pr_xBa₂Cu₄O₈ examined in the present study contained a single YBa₂ Cu₄O₈ (1-2-4) superconductive phase for x<0.7.Lattice parameters a and b increased with Pr concentration, suggesting that most of the Pr is trivalent in Y_1-x Pr_x-Ba₂Cu₄O₈. The zero-resistance temperature, T _co, decreases monotonically from 80 K at x=0 to 12 K at x=0.65, and superconducting transition widths tend to broaden for x>0. The room-temperature resistivity changes linearly until x=0.7 and increases abruptly at x=-0.75. The critical concentration, x_cr, thus was estimated to be 0.7. The effective magnetic moments of Pr in Y _1-x Pr_xBa₂Cu₄O₈ were 3.63., 3.35, and 3.23, μ_B for x=0.2, 0.4 and 0.6, respectively. In the R_0.8 Pr_0.2Ba₂Cu₄O₈ system, the depression of T_c weakly depends on the ionic radius of rare-earth elements. Similarities and differences between Y _1-x Pr_xBa₂Cu₄O₈ and Y_1-xPr_x-Ba₂Cu₃O_7-y also were noted and are discussed in this paper.