Phase Relations in the System Lead—Oxygen

Most of the known oxides of lead including the intermediate oxides Pb₁₂O₁₉ and Pb₂O₃ have been prepared under equilibrium conditions. Precise X-ray powder data have been obtained for the intermediate oxide phases. Solid-vapor equilibrium data have been obtained for reactions in the system lead-oxygen over the range 200° to 900° C and 3 to 1400 bars Po₂. Pressure-temperature univariant equilibrium curves are presented for the reactions PbO₂⇋ Pb₁₂O₁₉+ oxygen, Pb₁₂O₁₉⇋ Pb₃O₄+ oxygen, and Pb₃O₄⇋ PbO + oxygen. The enthalpies of reaction are, respectively, 26.8, 34.6, and 33.7 kcal per mole. Eutectic melting between PbO and Pb₃O₄ occurs at 875° C and 124 bars. A stability field for Pb₂O₃ exists above 1000 bars PO₂ at 600° C. Approximate resistivity data are presented.     

High-Pressure-High-Temperature Polymorphism of the Oxides of Lead

The common oxides of lead, PbO, PbO₂, and Pb₃O₄, were examined at pressures of 0 to 60,000 atmospheres and temperatures of 100° to 600° C. The pressure-temperature curve for the litharge-massicot transition was measured, giving a ΔH of transition of 57 cal. per mole. Unusual meta-stability and inversion characteristics of the massicot phase were examined in detail. PbO₂ (rutile) transformed at pressures in excess of 13,000 atmospheres at 300°C. to an ortho-rhombic form. The univariant equilibrium curve for the transition gave a Δ H of 11 cal. per mole. Pb₃O₄ underwent a disproportionation reaction yielding PbO and "Pb₂O₃." The equilibrium curve for this reaction was measured, and Δ H was determined to be 4500 cal. per mole.     

The System PbO-Chromium Oxide in Air

Phase relations in the system PbO-chromium oxide were determined in air at high temperatures and are considered in terms of the PbO-Cr₂O₃−O₂ ternary because of reactions with atmospheric oxygen. Although not necessarily binary at all temperatures, four established subsystems characterize the air equilibria and indicate oxidation-reduction of chromium. The PbO-PbCrO₄ join contains the compounds Pb₅CrO₃ and Pb₅CrO₈ and consists of two portions, PbO-Pb₂CrO₆ and Pb₂CrO₅−PbCrO₄ The former is binary at all temperatures studied, while the latter exists only below 753° C because of the decomposition of PbCrO₄ at 753°C to Pb₂CrO₅ and Cr₂O₃ with oxygen evolution. Similarly, the join PbCrO₄−Cr₂O₃ exists only below 753°C yielding to Pb₂CrO₃−Cr₂O₃ equilibria above this temperature.     

A Soft Chemistry Route for the Synthesis of Nanostructured Pb2Ru2O6.5 with a Controlled Stoichiometry

A new chemical route to synthesize nanostructured lead ruthenium pyrochlore (Pb₂Ru₂O_6.5) powders was developed. The synthesis was performed starting from a metal nitrate aqueous solution and N , N , N ', N ' tetramethylethylendiamine (TMEDA). The amine, which is a mild basic chelating agent, was able to control the simultaneous precipitation of lead and ruthenium oxo/hydroxides. For the sake of comparison, Pb₂Ru₂O_6.5 powders were prepared using the more conventional polymeric precursor method. The new method was effective for the synthesis of nanostructured Pb₂Ru₂O_6.5 powders already stable at 400°C and up to 1000°C.     

Synthesis of Pb(Mg1/3Nb2/3)O3 in Excess Lead Oxide by Mechanical Activation

Twenty hours of mechanical activation of mixed oxides at room temperature led to the formation of Pb(Mg_1/3Nb_2/3)O₃ (PMN) in excess PbO. The crystallinity of the activation-derived perovskite PMN phase was further established when the activated PMN–PbO phase mixture was subjected to calcination at 800°C. Pyrochlores, such as Pb₃Nb₄O₁₃ and Pb₂Nb₂O₇, were not observed as transitional phases on mechanical activation and subsequent calcination, although 50% excess PbO was deliberately added. The perovskite PMN phase was recovered by washing off excess PbO using acetic acid solution at room temperature. It was sintered to a relative density of 98.9% of theoretical at 1200°C for 1 h and the sintered PMN exhibited a dielectric constant of ∼14 000 at 100 Hz and a Curie temperature of −11°C.     

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.     

Preparation of Metal Ruthenates by Spray Pyrolysis

Submicrometer crystalline metal ruthenate powders with perovskite structure, MRuO₃ (M = Sr, La), and pyrochlore structure, M₂Ru₂O_{7- x} (0.5 < x < 1; M = Bi, Pb, Y, Eu, Gd, Tb, Dy, Ho, Er, Tm), were prepared by spray pyrolysis using metal nitrates and glycolates under an oxygen-gas atmosphere at temperatures up to 1100°C. Submicrometer-sized solid single crystals (SrRuO₃), submicrometer-sized hollow spheres consisting of nanocrystallites (pyrochlore rare-earth ruthenates, Bi₂Ru₂O₇, and Pb₂Ru₂O_6.5 below 1000°C), and nanometer-sized particles (Pb_2.31Ru_1.69O_6.5 and Bi-Pb-O above 1000°C) were observed. Particle formation proceeded by intraparticle reaction and intraparticle reaction followed by evaporation of volatile metal oxides to form metal oxide vapors followed by condensation and reaction to form particles. The former was observed for systems where no volatile metal oxides were formed, whereas the latter occurred for the Pb-Ru-O and Bi-Ru-O systems, where volatile metal oxides, such as Bi₂O, PbO, and RuO _x could occur. Particle morphology depended strongly on precursor properties. Submicrometer-sized single-crystal SrRuO₃ particles could be formed from the metal nitrates but not from Sr(NO₃)₂ and ruthenium glycolate, which gave hollow polycrystalline particles. In general, crystallite size could be controlled by varying precursor properties and reactor temperature, with higher temperatures giving larger crystallite sizes.     

Strength and Creep Behavior of Rare-Earth Disilicate–Silicon Nitride Ceramics

The flexural strength and creep behavior of RE₂Si₂O₇–Si₃N₄ materials were examined. The retention in room-temperature strengths displayed by these ceramics at 1300°C was 80–91%, with no evidence of inelastic deformation preceding failure. The steady-state creep rates, at 1400°C in flexural mode, displayed by the most refractory materials are among the lowest reported for sintered Si₃N₄. The creep behavior was found to be strongly dependent on residual amorphous phase viscosity as well as on the oxidation behavior of these materials. All of the rare-earth oxide sintered materials, with the exception of Sm₂Si₂O₇–Si₃N₄, had lower creep strains than the Y₂Si₂O₇–Si₃N₄ material.     

Phase Equilibria in the Spinel Region of the System FeO-Fe2O3-Al2O3

Phase relations in the spinel region of the system FeO-Fe₂O₃-Al₂O₃ were determined in CO₂ at 1300°, 1400°, and 15000°C and for partial oxygen pressures of 4 × 10⁻⁷ and 7 × 10⁻¹⁰ atmospheres at 15OO°C. The spinel field extends continuously from Fe₃O_4-x to FeAl₂O_4+z.     

Ceramic Properties of Samarium Oxide and Gadolinium Oxide; X-Ray Studies of Other Rare-Earth Oxides and Some Compounds

Samarium oxide forms a ceramic of medium strength and density (6.0) when it is fired at 1300°C. When it is fired at 1500°C., its density is increased to 7.4 but it loses its stability toward boiling water. X-ray data are given concerning the structure of the oxide as received and at 1300°C. and of the reaction product of Sm203 with water. Gadolinium oxide forms a ceramic of somewhat higher density (7.0) at 1300° than does Sm₂O₃; at 1500°C. its density is slightly higher (7.6) whereas its stability toward water is unchanged. Data concerning both oxides include density, shrinkage, moduli of elasticity and of rupture, linear thermal expansion, differential thermal analysis, and specific heat as well as X-ray data. Results are given of a brief survey of the reaction products obtained when Sm₂O₃ and Gd₂O₃ are heated at 1500°C. in equimolecular quantities with Al₂O₃, BaO, CaO, CdO, Fe₂O₃, HfO₂, MgO, SO₂, SrO, ThO₂, and ZrO₂. X-ray data for the following rare-earth oxides as received and after calcination at 1400°C. are given: ceria, praseodymia, neodymia, europia, dysprosia, holmia, erbia, thulia, and ytterbia.     

Formation and Transformation of Cubic Lead Niobate Pyrochlore Solid Solutions

Formation of lead niobate pyrochlores by the reaction of PbO with Nb₂O₅ in various molar ratios and at various temperatures has been investigated. It has been shown that for a PbO/Nb₂O₅ molar ratio between 1.5 and 3.0, a pyrochlore solid solution having cubic symmetry is formed at low temperatures (∼500-600°C). X-ray diffraction data show evidence for the existence of compositional inhomogeneity for this phase which contains part of the Pb in the Nb site leading to the formula Pb_{1.5+ x} (Nb_{2- y} Pb _y )O_7-delta (0.0 < x < 0.5; 0.0 < y < 0.5). A phase-pure Pb-deficient pyrochlore (Pb_1.5Nb₂O_6.5) and Pb-excess pyrochlores (Pb_2.5Nb₂-O₈, Pb₃Nb₂O₈) are formed by the decomposition of this cubic solid solution and subsequent reaction at high temperatures. These results indicate that the mechanism of the structural transformation from the low-temperature (LT) cubic solid solution to the corresponding high-temperature (HT) phases is reconstructive.     

Mineralizing Effect of Li2B4O7 and Na2B4O7 on Magnesium Aluminate Spinel Formation

Lithium borate (Li₂B₄O₇) and sodium borate (Na₂B₄O₇) mineralize spinel formation from stoichiometric MgO and Al₂O₃ between 1000° and 1100°C. Mineralization with both compounds is shown to be mediated by B-containing liquids which form glass on cooling. However, the liquid compositions depend on the type of mineralizer and temperature, suggesting that templated grain growth or dissolution–precipitation mechanisms are operating, one dominating over the other under certain conditions. Na₂B₄O₇-mineralized compositions show predominantly templated grain growth at 1000°C, which changes to dissolution–precipitation at 1100°C, whereas Li₂B₄O₇-mineralized compositions show dissolution–precipitation from 1000°C. Li₂B₄O₇ is a stronger mineralizer as spinel formation is complete with 3 wt% Li₂B₄O₇ at 1000°C and with ≥1.5 wt% addition at 1100°C, whereas Na₂B₄O₇-mineralized compositions are found to retain some unreacted corundum even at 1100°C.     

Solubility Limit of La in the Lead Zirconate-Titanate System

The disappearing-phase method was used to determine the extent of the solid-solution region of the PLZT system for conventionally sintered ceramics prepared at 1100° and 1300°C in a PbO atmosphere provided by pbZrO₃. A decrease in the firing temperature from 1300° to 1100°C lowers the solubility limit by 5 to 8 at.% La. Beyond the limits of solubility, additional La forms La₂Zr₂O₇ and/or La₂Ti₂O₇. The limit determined by the disappearing-phase method (1300°C firing) is compared to values determined by the parametric method. The Curie temperature is stabilized at 5 at.% La for modified PbZrO₃ (1300°C firing).     

Sintering of Si3N4 with the Addition of Rare-Earth Oxides

The effect of rare-earth oxide additives on the densification of silicon nitride by pressureless sintering at 1600° to 1700°C and by gas pressure sintering under 10 MPa of N₂ at 1800° to 2000°C was studied. When a single-component oxide, such as CeO₂, Nd₂O₃, La₂O₃, Sm₂O₃, or Y₂O₃, was used as an additive, the sintering temperature required to reach approximate theoretical density became higher as the melting temperature of the oxide increased. When a mixed oxide additive, such as Y₂O₃–Ln₂O₃ (Ln=Ce, Nd, La, Sm), was used, higher densification was achieved below 2000°C because of a lower liquid formation temperature. The sinterability of silicon nitride ceramics with the addition of rare-earth oxides is discussed in relation to the additive compositions.     

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.     

Activity–Composition Relations in NiAl2O4─MnAl2O4 Solid Solutions and Stabilities of NiAl2O4 and MnAl2O4 at 1300° and 1400°C

Activities of NiO were measured in the oxide and spinel solutions of the system MnO–NiO–Al₂O₃ at 1300° and 1400° C with the aim of deriving information on the thermodynamic properties of the spinel phases. Synthetic samples in selected phase assemblages of the system were equilibrated with metallic nickel and a gas phase of known oxygen partial pressures at a total pressure of 1 atm. The data on NiO activities and directions of conjugation lines between coexisting oxide and spinel phases were used to establish the activity–composition relations in spinel solid solutions at 1300° and 1400°C. The MnAl₂O₄–NiAl₂O₄ solid solutions exhibit considerable negative deviations from ideality at these temperatures. The free energy of formation of MnAl₂O₄ from its oxide components (MnO + Al₂O₃) at 1300° and 1400°C is calculated to be −24.97 and −26.56 kJ. mol⁻¹, respectively. The activities determined in the stoichiometric spinel solid solutions are more negative as compared with those predicted from cation distribution models.     

Zirconia-Stabilized Cubic Europia

The system Eu₂O₃-ZrO₂ was studied, concentrating attention on the region 0 to 33 mol% ZrO₂, which is of interest for fast-reactor neutron absorber applications. The addition of ∼20% ZrO₂ to Eu₂O₃ resulted in stable cubic phases. Results are compared for coprecipitated powders and pellets prepared from mechanically mixed powders fired at 1300°C and 1S50°C. The thermal stability of cubic structures at 600°C and 800°C for 8000 h was also demonstrated.     

Temperature-Dependent Iron Solubility in Mullite

Sample disks prepared from Al₂O₃ (61 wt%), SiO₂ (28 wt%), and Fe₂O₃(II wt%) powders were sintered at 1270° and 1440°C and then annealed between 1300° and 1670°C. The annealed samples consisted of mullite as the main compound with minor amounts of glass and sometimes magnetite. The iron content of the mullites decreases strongly from ∼ 10.5 wt% Fe₂O₃ at 1300°C to ∼ 2.5 wt% Fe₂O₃ at 1670°C. A complex temperature-controlled exsolution mechanism of iron from mullite is considered.     

Compound Formation and Phase Equilibria in the System PbO-SiO2

Compound formation in the system PbO-SiO₂ was studied; the results are contrasted with those previously reported. Fifteen binary phases, 4 of which had not been reported, were prepared in the present study. The new phases include Pb₅Si₈O₂₁, an orthorhombic polymorph of PbSiO₃, Pb₃SiO₅, and a high-SiO₂ phase containing ∼ 60 mol% SiO₂. It was shown that Pb₃SiO₅ is thermodynamically stable relative to Pb₂SiO₄ and 4PbO.SiO₂ below 640±5°C. A revised phase equilibrium diagram is presented.     

Interface Reactions between Silicon Dioxide-Lead Oxide Glass and Manganese Zinc Ferrite

The interface reations between SiO₂–PbO melt and Mn-Zn ferrite were studied using electron probe microanalysis (EPMA) and X-ray diffraction (XRD). Intermediate layers were formed at the interface between the glass and the Mn-Zn ferrite which were heated at 800° and 900°C, although those layers were not found in specimens heated at 1000°C. Using EPMA and XRD, the intermediate layers were found to be Pb₂(Mn, Fe)₂Si₂O₉ and Pb₈(Mn, Fe)Si₆O₂₁. The mechanisms of interface reactions are discussed, related to glassforming regions. It was concluded that the interface reaactions between SiO₂–PbO melt and Mn-Zn ferrite are controlled by the dissolution of Zn ions and Mn ions from the Mn-Zn ferrite.