Phase Transition of Rare-Earth Aluminates (RE4Al2O9) and Rare-Earth Gallates (RE4Ga2O9)

Lattice parameters of RE₄Al₂O₉ (RE = Y, Sin, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb) prepared at 1600–1800°C and those of RE₄Ga₂O₉ (RE = La, Pr, Nd, Sm, Eu, and Gd) prepared at 1400–1600°C were refined by Rietveld analysis for the X-ray powder diffraction patterns. The parameters increased linearly with the ionic radius of the trivalent rare-earth elements ( r _RE). High-temperature differential calorimetry and dilatometry revealed that both RE₄Al₂O, and RE₄Ga₂O, have reversible phase transitions with volume shrinkages of 0.5–0.7% on heating and thermal hystereses. The transition temperatures (7_tr) decreased from 1300°C (Yb) to 1044°C (Sm) for RE₄A1₂O₉, except for Y₄Al₂O₉ ( T_tr = 1377°C), and from 1417°C (Gd) to 1271°C (La) for RE₄Ga₂O, with increasing ionic radius of the rare-earth elements. These transition temperatures were plotted on a curve against the ionic radius ratio of Al³⁺ or Gd³⁺ and RE³⁺ ( r _A1Ga/r_RE) except for Y₄Al₂O₉.     

Hydrolysis of Pure and Sodium Substituted Calcium Aluminates and Cement Clinker Components Investigated by in Situ Synchrotron X-ray Powder Diffraction

The hydrolysis of pure and sodium-substituted calcium aluminates and cement clinker phases was investigated in situ in the temperature range 25°–170°C, using the angle dispersive powder synchrotron powder X-ray diffraction technique. The final hydrolysis product in all cases was Ca₃Al₂(OH)₁₂. The intermediate phase Ca₄Al₂O₇·19H₂O was formed from the pure calcium aluminates, and the intermediate phases Ca₄Al₂O₇· x H₂O, x = 11, 13, or 19, were formed from the cement clinker phases.     

Uniformly Porous Al2O3/LaPO4 and Al2O3/CePO4 Composites with Narrow Pore-Size Distribution

Porous Al₂O₃/20 vol% LaPO₄ and Al₂O₃/20 vol% CePO₄ composites with very narrow pore-size distribution at around 200 nm have been successfully synthesized by reactive sintering at 1100°C for 2 h from RE₂(CO₃)₃· x H₂O (RE = La or Ce), Al(H₂PO₄)₃ and Al₂O₃ with LiF additive. Similar to the previously reported UPC-3Ds (uniformly porous composites with a three-dimensional network structure, e.g. CaZrO₃/MgO system), decomposed gases in the starting materials formed a homogeneous open porous structure with a porosity of ∼40%. X-ray diffraction, ³¹P magic-angle spinning nuclear magnetic resonance, scanning electron microscopy, and mercury porosimetry revealed the structure of the porous composites.     

Low-Temperature Synthesis of Calcium Hexa-Aluminate

Calcium hexa-aluminate (CaO·6Al₂O₃) has been prepared from calcium nitrate and aluminum sulfate solutions in the temperature range of 1000°–1400°C. A 0.3 mol/L solution of aluminum sulfate was prepared, and calcium nitrate was dissolved in it in a ratio that produced 6 mol of Al₂(SO₄)₃·16H₂O for each mole of Ca(NO₃)₂·4H₂O. It was dried over a hot magnetic stirrer at ∼70°C and fired at 1000°–1400°C for 30–360 min. The phases formed were determined by XRD. It was observed that CaO·Al₂O₃ and CaO·2Al₂O₃ were also formed as reaction intermediates in the reaction mix of CaO·6Al₂O₃. The kinetics of the formation of CaO·6Al₂O₃ have been studied using the phase-boundary-controlled equation 1 − (1 − x )^1/3= K log t and the Arrhenius plot. The activation energy for the low-temperature synthesis of CaO·6Al₂O₃ was 40 kJ/mol.     

Synthesis of Titanate Derivatives Using Ion-Exchange Reaction

Two types of titanate derivatives, layered hydrous titanium dioxide (H₂Ti₄O₉· n H₂O) and potassium octatitanate (K₂Ti₈O₁₇) with a tunnellike structure, were synthesized using an ion-exchange reaction. Fibrous potassium tetratitanate (K₂Ti₄O₉· n H₂O) was prepared by calcination of a mixture of K₂CO₃ and TiO₂ with a molar ratio of 2.8 at 1050°C for 3 h, followed by boiling-water treatment of the calcined products for 10 h. The material then was transformed to layered H₂Ti₄O₉· n H₂O through an exchange of K⁺ ions with H⁺ ions using HCl. K₂Ti₈O₁₇ was formed by a thermal treatment of KHTi₄O₉· n H₂O. Pure KHTi₄O₉· n H₂O phase was effectively produced by a treatment of K₂Ti₄O₉ with 0.005 M HCl solution for 30 min. Thermal treatment at 250°–500°C for 3 h resulted in formation of only K₂Ti₈O₁₇.     

Densification, Structure, and Thermophysical Properties of Ytterbium–Gadolinium Zirconate Ceramics

(Yb _x Gd_{1− x} )₂Zr₂O₇ (0≤ x ≤1.0) ceramic powders synthesized with the chemical-coprecipitation and calcination method were pressureless-sintered at 1550–1700°C to develop new thermal barrier oxides with a lower thermal conductivity than yttria-stabilized zirconia ceramics. (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics exhibit a defective fluorite-type structure. The linear thermal expansion coefficients of (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics increase with increasing temperature from room temperature to 1400°C. The measured thermal conductivity of (Yb _x Gd_{1− x} )₂Zr₂O₇ ceramics first gradually decrease with increasing temperature and then slightly increase above 800°C because of the increased radiation contribution. YbGdZr₂O₇ ceramics have the lowest thermal conductivity among all the composition combinations studied.     

A Novel Way to Synthesize Yttrium Aluminum Garnet from Metal–Inorganic Precursors

Yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) was synthesized by sol–gel processing from the stoichiometric amounts of aluminum pellets, Y(NO₃)₃·6H₂O, and Al(NO₃)₃·9H₂O or AlCl₃·6H₂O, with suitable kinds of acid (citric acid, acetic acid, etc.) as catalysts. Polycrystalline YAG powder was obtained by drying the YAG precursor followed by calcination at temperatures above 900°C. Thermogravimetry/differential thermal analysis and Fourier transform infrared specotrscopic analyses in air showed an exothermic peak at ∼900°C, attributed to the formation of a polycrystalline YAG phase and weight loss of 60% at 1000°C, caused by the decomposition of hydroxyl and NO₃⁻, etc. X-ray diffraction analysis showed that YAG can be formed at 900°C, and no other intermediate was observed. In particular, the YAG sol can be used for dry-spinning fibers with the aid of some organic polymer.     

Synthesis of Phase-Pure Pb(ZnxMg1–x)1/3Nb2/3O3 up to x= 0.7 from a Single Mixture via a Soft-Mechanochemical Route

Phase-pure perovskite Pb(Zn _x Mg_{1– x} )_1/3Nb_2/3O₃ solid solution (PZ _x M_{1– x} N) is obtained for x ≦ 0.7 by heating a milled stoichiometric mixture of PbO, Mg(OH)₂, Nb₂O₅, and 2ZnCO₃·3Zn(OH)₂·H₂O at 1100°C for 1 h. Percent perovskite ( f _P) with respect to total crystalline phase decreases with increasing temperature of subsequent heating then increases to 900°C for the mixtures where x ≦ 0.8 and milled for 3 h. For mixtures with x = 0.9 and x = 1, f _P decreases monotonically. Curie temperature increases almost linearly with increasing x up to x = 0.7. The maximum dielectric constant at 1 kHz is 2×10⁴ and 1.7×10⁴ for the mixture with x = 0.4 and x = 0.7, respectively. The stabilization mechanism of strained perovskite is discussed.     

The System MgO─P2O5─H2O at 25°C

The phase diagram for the ternary system MgO─P₂O₅─H₂O at 25°C has been constructed. The magnesium phosphates represented are Mg(H₂PO₄)₂· n H₂O ( n = 4, 2, 0), MgHPO₄·3H₂O, and Mg₃(PO₄)₂· m H₂O ( m = 8, 22). Because of the large differences in the solubilities of these compounds, the technique which involves plotting the mole fractions of MgO and P₂O₅ as their 10th roots has been employed. With the exception of MgHPO₄·3H₂O, the magnesium phosphates are incongruently soluble. Because incongruency is associated with a peritectic-like reaction, the phase Mg₂(PO₄)₃· 8H₂O persists metastably for an extended period.     

Preparation of BaTi4O9 from Oxalates

A barium titanate precursor with a barium:titanium ratio of 1:4 was prepared by controlled coprecipitation of mixed barium and titanium species with an ammonium oxalate aqueous solution at pH 7. The results of thermal analysis and IR measurement show that the obtained precursor is a mixture of BaC₂O₄·0.5H₂O and TiO(OH)₂·1.5H₂O in a molar ratio of 1:4. Crystallized BaTi₄O₉ was obtained by the thermal decomposition of a precipitate precursor at 1300°C for 2 h in air. The dimensions of the powder calcined at 1000°C are between 100 and 300 nm. The grain dimensions of the sintered sample for 2 h at 1300°C are of the order of 10 to 30 μm. Dielectric properties of disk-shaped sintered specimens in the microwave frequency region were measured using the TE₀₁₁ mode. Excellent microwave characteristics for BaTi₄O₉—ɛ= 38 ± 0.5, Q = 3800–4000 at 6–7 GHz and τ _f = 11 ± 0.7 ppm/°C—were found.     

Ionic Conductivity Enhancement of La2Mo2−xWxO9 Nanocrystalline Films Deposited on Alumina Substrates by the Sol–Gel Method

Dense, crack-free, and uniform La₂Mo_{2− x} W _x O₉ ( x =0, 0.1, and 0.2) nanocrystalline films were successfully synthesized on poly-alumina substrates via a modified sol–gel method, with inorganic salt of La(NO₃)₃·6H₂O, (NH₄)₆Mo₇O₂₄·4H₂O, and (NH₄)₆H₂W₁₂O₂₄ as precursors. Pure La₂Mo₂O₉ phase was confirmed by X-ray diffractometer when the annealing temperature was >500°C. The average grain size of the La₂Mo_{2− x} W _x O₉ films is in the range of 90–400 nm, depending upon the conditions of thermal treatment, and the thickness of films can reach 1 μm by repetitive spin-coating. The electrical conductivity increases with decreasing grain size and reaches 0.074 S/cm at 600°C in the film with a grain size of 90 nm, which is one order of magnitude higher than that in the corresponding bulk materials. W-doping can suppress the phase transition that occurs at 580°C in pure La₂Mo₂O₉ and enhance the low-temperature ionic conductivity. Furthermore, the activation energy of conductivity in the nanocrystalline La₂Mo₂O₉ films decreases to about 0.6 eV in comparison with 1.0 eV in the bulk ones, which implies that the grain resistance prevails in the total resistance, when grain size reduces to nanometer domain.     

Synthesis and Characterization of (Ce0.67Tb0.33)MnxMg1−xAl11O19 Phosphors Derived by Sol–Gel Processing

A (Ce_0.67Tb_0.33)Mn _x Mg_{1− x} Al₁₁O₁₉ phosphor powder was synthesized, using a simple sol–gel process, by mixing citric acid with CeO₂, Tb₄O₇, Al(NO₃)₃·9H₂O, Mg(OH)₂·4MgCO₃·6H₂O, and Mn(CH₃COO)₂. The phosphor crystallized completely at 1200°C, and the phosphor particle size was between 1 and 5 μm. The excitation spectrum was characteristic of Ce³⁺, while the emission spectrum was composed of lines from Tb³⁺ and Mn²⁺. The Mn²⁺ gave a green fluorescence band, and concentration quenching occurred when x > 0.10. The luminescent properties of the phosphor were explained by a configurational coordinate model.     

Spectroscopic Properties of Er3+-Doped Na2O–La2O3–Al2O3–SiO2 Glasses

Er³⁺-doped sodium lanthanum aluminosilicate glasses with compositions of (90− x )(0.7SiO₂·0.3Al₂O₃)· x Na₂O·8.2La₂O₃· 0.6Er₂O₃·0.2Yb₂O₃·1Sb₂O₃ (in mol%) ( x = 12, 20, 24, 40, 60 mol%) were prepared and their spectroscopic properties were investigated. Judd–Ofelt analysis was used to calculate spectroscopic properties of all glasses. The Judd–Ofelt intensity parameter Ω _t ( t = 2, 4, 6) decreases with increasing Na₂O. Ω₂ decreases rapidly with increasing Na₂O while Ω₄ and Ω₆ decrease slowly. Both the fluorescent lifetime and the radiative transition rate increase with increasing Na₂O. Fluorescence spectra of the ⁴ I _13/2 to ⁴ I _15/2 transition have been measured and the change with Na₂O content is discussed. It is found that the full width at half-maximum decreases with increasing Na₂O.     

Mechanochemical Changes of Weinschenkite-Type RPO4·2H2O (R = Dy, Y, Er, or Yb) by Grinding and Thermal Reactions of the Ground Specimens

It is reported that, on mechanochemical treatment, weinschenkite-type RPO₄·2H₂O (R = Dy, Y, or Er) gradually transforms into rhabdophane-type RPO₄· nH₂O (n = 0.5 to 1) and weinschenkite-type YbPO₄·2H₂O into xenotime-type YbPO₄, at room temperature in air. Rhabdophane-type YPO₄·0.8H₂O and ErPO₄·0.9H₂O obtained by grinding weinschenkite-type RPO₄·2H₂O (R=Y or Er) are new. The new rhabdophane-type YPO₄·0.8H₂O and ErPO₄·0.9H₂O gradually transform to xenotime-type YPO₄ and ErPO₄ when heated above 900°C (R = Y) and 700°C (R = Er) in air.     

Fabrication of Transparent, Sintered Sc2O3 Ceramics

We report here the fabrication of transparent Sc₂O₃ ceramics via vacuum sintering. The starting Sc₂O₃ powders are pyrolyzed from a basic sulfate precursor (Sc(OH)_2.6(SO₄)_0.2·H₂O) precipitated from scandium sulfate solution with hexamethylenetetramine as the precipitant. Thermal decomposition behavior of the precursor is studied via differential thermal analysis/thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffractometry, and elemental analysis. Sinterability of the Sc₂O₃ powders is studied via dilatometry. Microstructure evolution of the ceramic during sintering is investigated via field emission scanning electron microscopy. The best calcination temperature for the precursor is 1100°C, at which the resultant Sc₂O₃ powder is ultrafine (∼85 nm), well dispersed, and almost free from residual sulfur contamination. With this reactive powder, transparent Sc₂O₃ ceramics having an average grain size of ∼9 μm and showing a visible wavelength transmittance of ∼60–62% (∼76% of that of Sc₂O₃ single crystal) have been fabricated via vacuum sintering at a relatively low temperature of 1700°C for 4 h.     

The System CaO-Al2O3-H2O

Phase equilibria have been determined in the system CaO-Al₂O₃-H₂O in the temperature range 100° to 1000°C. under water pressures of up to 3000 atmospheres. Only three hydrated phases are formed stably in the system: Ca(OH)₂, 3CaO·Al₂O₃·6H₂O, and 4CaO·3Al₂O₃-3H₂O. Pressure-temperature curves delineating the equilibrium decomposition of each of these phases have been determined, and some ther-mochemical data have been deduced therefrom. It has been established that both the compounds CaO·Al₂O₃ and 3CaO·Al₂O₃ have a minimum temperature of stability which is above 1000°C. The relevance of the new data to some aspects of cement chemistry is discussed.     

Synthesis and Properties of Dielectric Ceramics from Metallo-Organic Precursors through the Solid-State Reaction of Mixed Gels

A perovskite structure of 0.4Pb(Mg_1/3Nb_2/3)O₃·0.3Pb(Mg_1/2W_1/2)O₃·0.3PbTiO₃ was prepared from metallo-organic precursors through the solid-state reaction of the mixed gels. Three types of mixed gels were crystallized to obtain PbTiO₃, MgNb₂O₆, and MgWO₄ powders. These powders were calcined at 900°C after mixing with a stoichiometric amount of Pb(CH₃COO)₂·3H₂O. The dielectric constant of the ceramic fired at 900°C was improved by adding an excess of 10 mol% Mg(OC₂H₅)₂, and the ceramic achieved X7T specification of the Electric Industries Association standard. The dielectric loss was reduced by adding an excess of 5 mol% Pb(CH₃COO)₂·3H₂O.     

The System CaO-Al2O3-P2O5-H2O at 200°C

The phase relations were established experimentally for the system CaO-Al₂O₃-P₂O₅-H₂O at 200°C and 1710 kPa. The quaternary compound, crandallite, CaAl₃(PO₄)₂(OH)₅· H₂O, was found to be stable. Compatibility joins in the system were determined. The phase relations are presented on the isothermal-isobaric 90 wt% water plane and by projecting the primary fields of the liquidus surface onto the same plane.     

Thermal Decomposition of Some Substituted Barium Titanyl Oxalates and Its Effect on the Semiconducting Properties of the Doped Materials

Thermal analysis has been performed on BaTiO(C₂O₄)₂.4H₂O, Ba_0.6Sr_0.4TiO(C₂O₄)₂.4H₂O, Sr(TiO(C₂O₄)₂.4H₂O, Ba_0.9Pb_0.1TiO(C₂O₄)₂.4H₂O, and BaTi_0.9Zr_0.1O(C₂O₄)₂.4H₂O. It was observed that the strontium compound decomposes differently than the others. Previous investigators have proposed conflicting mechanisms for the pyrolysis of the barium salt and these results are discussed in comparison with this work. The electrical resistivity and temperature coefficient of fired lanthanum-doped materials were found to vary with the calcination temperature. Maximum conductivity was observed in samples calcined at 900°C whereas maximum positive temperature coefficient was observed for materials calcined at 1050°C. Particle sizes of the calcined material were compared with grain sizes in the fired pieces and correlated with the electrical properties. A cursory examination was made on the effects of fabrication pressure, 1.25 to 15 tsi, on the electrical conductivity. Both the conductivity and positive temperature coefficient were found to increase with decreasing fabrication pressure.     

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.