Indirect Dissolution of (Al, Cr)2O3 in CaO—MgO—Al2O3—SiO2 (CMAS) Melts

The dissolution of (Al, Cr)₂O₃ into CaO—MgO—Al₂O₃—SiO₂ melts, under static and forced-convective conditions was investigated at 1550°C in air. With sufficient MgO in the melt, or sufficient Cr₂O₃ in (Al, Cr)₂O₃, a layer consisting of a spinel solid solution, Mg(Al, Cr)₂O₄, formed at the (Al, Cr)₂O₃/melt interface. The dissolution kinetics of 1.5 and 10 wt% Cr₂O₃ specimens were determined as a function of immersion time, specimen rotation rate, and magnesia content of the melt. Electron microprobe analysis was used to characterize concentration gradients in the (Al, Cr)₂O₃ sample, the Mg(Al, Cr)₂O₄ spinel, or in the melt after immersion of specimens containing 1.5 to 78 mol% Cr₂O₃. The dissolution kinetics and microprobe analyses indicated that a steady-state condition was reached during forced-convective, indirect (Al, Cr)₂O₃ dissolution such that spinel layer formation was rate limited by solid-state diffusion through the spinel layer and/or through the specimen, and spinel layer dissolution was rate limited by liquid-phase diffusion through a boundary layer in the melt. This is consistent with a model previously developed for the indirect dissolution of sapphire in CMAS melts.     

Phase Relations in the Garnet Region of the System Y2O3–Fe2O3–FeO–Al2O3

Liquidus equilibrium relations for the air isobaric section of the system Y₂O₃–Fe₂O₃–FeO–Al₂O₃ are presented. A Complete solid-solution series is found between yttrium iron garnet and yttrium aluminum garnet as well as extensive solid solutions in the spinel, hematite, orthoferrite, and corundum phases. Minimum melting temperatures are raised progressively with the addition of alumina from 1469°C in the system Y–Fe–O to a quaternary isobaric peritectic at 1547°C and composition Y _0.22 Fe _1.08 Al _0.70 O _2.83* Liquidus temperatures increase rapidly with alumina substitutions beyond this point. The thermal stability of the garnet phase is increased with alumina substitution to the extent that above composition Y _0.75 Fe _0.65 Al _0.60 O ₃ garnet melts directly to oxide liquid without the intrusion of the orthoferrite phase. Garnet solid solutions between Y _0.75 Fe _1.25 O ₃ and Y _0.75 Fe _0.32- Al _0.93 O ₃ can be crystallized from oxide liquids at minimum temperatures ranging from 1469° to 1547°C, respectively. During equilibrium crystallization of the garnet phase, large changes in composition occur through reaction with the liquid. Unless care is taken to minimize temperature fluctuations and unless growth proceeds very slowly, the crystals may show extensive compositional variation from core to exterior.     

Mechanical Activation of Heterogeneous Sol–Gel Precursors for Synthesis of MgAl2O4 Spinel

MgAl₂O₄ spinel precursor was prepared using a heterogeneous sol–gel process. The effect of high-energy milling on the precursor decomposition and spinel formation was investigated. The milling decreased the Al(OH)₃ dehydroxylation temperature from 190° to about 130°C. The activation energy for spinel formation decreased from 688 kJ/mol for the as-prepared precursors to 468 kJ/mol for the precursors milled for 5 h. Milling of the precursor lowered the incipient temperature of spinel formation from 900° to 800°C, and the temperature of complete MgAl₂O₄ spinel formation from >1280° to ∼900°C.     

Silica-Free Phases with Mullite-Type Structures

Silica-free phases which have a structure similar to that of mullite can be crystallized from gels in the Na₂O-Al₂O₃ and (Na,K)₂O-BaO-Al₂O₃ systems. A gelation step appears to be necessary, since a solid-state reaction between Na₂CO₃ and Al(OH)₃ does not give the mullite-type phase. Crystallization of this phase requires a high alkali content during formation of the gel. A well-crystallized phase is formed at 950°C and is stable to at least 1000°C; at higher temperatures (i.e. 1200°C), β-Al₂O₃ and corundum are formed. The mullite-type phase appears to crystallize with an increase in temperature at the expense of a γ-Al₂O₃ phase, indicating adsorption of Na on the defect spinel structure, which is then rearranged to give the mullite-type phases.     

Crystalline Solution in the System MgO-Mg,SiO4,-MgAl2,O4,

Crystalline solubility relations in the system MgO-Mg₂SiO₄MgAl₂O₄ (periclase-forsterite-spinel) were studied using coprecipitated gels as starting materials. The substitution 2Al = Mg + Si was investigated along the join Mg₂SiO₄-Mg-Al₂O₄,. At 1720°C the maximum crystalline solution in forsterite is about 0.5 mole % MgAI₂O₄, and in spinel it is slightly more than 5.0 mole % Mg₂SiO₄. The solubility of MgO in forsterite was 0.5 mole % at 1860°C, whereas more than 11 mole % Mg₂SiO₄ can be dissolved in the periclase structure at this temperature. Ternary crystalline solution exists in the periclase structure to a composition of Mg_0.853Al_0.063Si_0.026O at 1710°C.     

TEM Characterization of Nanostructured MgAl2O4 Synthesized by a Direct Conversion Process from γ-Al2O3

Nanostructured MgAl₂O₄ spinel was synthesized by a direct conversion process from cubic γ-Al₂O₃. The effect of post-annealing temperature (300°, 500°, and 800°C) on MgAl₂O₄ phase formation was investigated using transmission electron microscopy, selected area electron diffraction (SAED), electron energy loss spectroscopy (EELS), and energy-dispersive spectroscopy (EDS). Relative diffraction intensities as well as lattice parameter measurements from SAED revealed that MgAl₂O₄ spinel structure starts forming at temperatures as low as 300°C. EELS and EDS spectrum images also revealed an increase in elemental homogeneity with increasing annealing temperature. The degree of ordering of Mg and Al between octahedral and tetrahedral sites has been determined from relative diffraction intensities. Results show that annealing to 800°C leads to a spinel phase with an order parameter of 0.78.     

Coherent Precipitation in the System MgO-Al2O3-Cr2O3

An isothermal section of the ternary system MgO–Al₂O₃-Cr₂O₃ was determined at 1700°± 15°C to delineate the stability field for spinel crystalline solutions (cs). Crystalline solutions were found between the pseudobinary joins MgAl₂O₄–Cr₂O₃ and MgCr₂O₄-Al₂O₃, and the binary join MgAl₂O₄-MgO. The first two crystalline solutions exhibit cation vacancy models while the latter can probably be designated as a cation interstitial model. Precipitation from spinel cs may proceed directly to an equilibrium phase, (Al_1-xCr_x)₂O₃, with the corundum structure or through a metastable phase of the probable composition Mg(Al_1-xC_r)₂₆O₄₀. The composition and temperature limits were defined where the precipitation occurs via metastable monoclinic phases. The coherency of the metastable monoclinic phase with the spinel cs matrix can be understood by considering volume changes with equivalent numbers of oxygens and known crystallographic orientation relations. Electron probe and metallographic microscope investigations showed no preferential grain boundary precipitation.     

Preparation and Properties of Spinel Made by Vapor Transport and Diffusion in the System MgO-Al2O3

In a hydrogen atmosphere, MgO was vaporized by heating MgO (periclase) in the range 1500° to 1900° C, and the vapor products diffused into Al₂O₃ (sapphire) to form a uniform outer layer of spinel on all surfaces. At 1900°C. a spinel layer 48 mils thick could be obtained in 16 hours. The rates of spinel formation were determined and the activation energy was calculated to be about 100 kcal. per mole. In the spinel layer, the lattice constant, Vickers hardness, and the refractive index varied from the outer surface to the inner boundary in a fairly uniform manner, indicating a continuous change in composition from 1MgO: 1Al₂O₃ to 1MgO: 2–3Al₂O₃. In conversion to spinel a volume increase of 47% over that of the original sapphire took place. Transparent clear shapes of spinel such as disks and rods were obtained from clear sapphire and from translucent polycrystalline alumina. Clear rods of spinel with polished ends acted as thin lenses, round rods as convex lenses, and flat rods as planocylindrical lenses owing to the increase in refractive index from the outer surface to the inner central portion. Objects made of opaque polycrystalline alumina were also converted to spinel. The MgO periclase blocks were etched in the hydrogen atmosphere, and the vapor products of Al₂O₃ entered the MgO to form tiny spinel droplets in an opalescent border. In an oxidizing atmosphere, spinel was formed only on the surface of the sapphire directly in contact with periclase, in the range 1500° to 1900°C.     

Crystal Chemistry and Phase Relations in the System Li2O-Fe2O3-TiO2

Above 755°C, compounds along the spinel join LiFe₅O₈-Li₄Ti₅O₁₂ form a complete solid solution and below that temperature a two-phase region separates the ordered LiFe₅O₈ and the disordered spinel phase. At 800° and 900°C, cubic LiFeO₂ ( ss ) and monoclinic Li_zTi0₃ ( ss ) exist on the monoxide join LiFeO₂-Li₂TiO₃. The distributions of cations in both the spinel and monoxide structures were calculated as a function of equilibrium temperature and composition. Sub-solidus equilibria in the system Li₂O-Fe₂O₃-TiO₂ at 800° and 900°C were determined for compositions containing ∼50 mol% Li₂O.     

Microstructure of (Fe0.2Co0.8)0.8(Fe2.38Co0.62O4): A Magnetic Oxidation Resistant Composite Formed by Coprecipitation

The metal–ferrite composite (Fe_0.2Co_0.8)_0.8(Fe_2.38Co_0.62O₄) has been studied by X-ray diffractometry measurements and high-resolution transmission electron microscopy. Spinel ferrite occurs in highly crystalline domains 100–150 nm in size, and the iron–cobalt alloy occurs in smaller and less-crystalline domains (10–20 nm). Both phases are heterogeneous in composition. The metal is embedded in the spinel phase, located near the edges, and overlaid by a poorly crystallized layer or misshapen regions containing small spinel crystals and amorphous phases. By annealing under vacuum up to 800°C, the misshapen regions disappear and the size of the metallic regions increases. The concentration of iron in the metallic regions decreases and their structure changes to face-centered cubic, while the spinel becomes enriched in iron.     

Interpretation of the Kaolinite-Mullite Reaction Sequence from Infrared Absorption Spectra

The phases in the kaolinite-mullite reaction sequence were reexamined by ir absorption spectrophotometry. Particular attention was paid to the controversial intermediate Al-containing phases. Amorphous materials were leached from fired kaolinite samples with NaOH to help identify crystalline phases. Metakaolinite partially decomposes, releasing amorphous γ-Al₂O₃ and SiO₂, before the "950°C" exothermic reaction in which metakaolinite is completely decomposed. The resulting spinel-type phase, which is associated with amorphous SiO₂ and some poorly crystalline "primary" mullite, is γ-Al₂0₃ (crystalline) rather than an Al-Si spinel. There is some evidence, however, that a fraction of the γ-Al₂O₃, may be an Al-Si spinel. At ≥1100°C secondary mullite therefore forms primarily from the γ-Al₂O₃/amorphous SiO₂ reaction and the recrystallization of primary mullite, whereas excess amorphous SiO₂ eventually crystallizes as cristobalite.     

Synthesis and Processing of Barium Hexaaluminogallates

Barium hexaaluminogallate was synthesized by the mixed-oxide method and the coprecipitation method. Barium hexaaluminate and barium hexagallate were found to form barium hexaaluminogallate, Ba(Al,Ga)₁₂O₁₉, at 1400°C. BaCo(Al,Ga)₁₁O₁₉ of magnetoplumbite structure was formed from a mixture of metal oxides at 1200°C for 6 h. Co was successfully introduced to barium hexaaluminogallate, although the synthesis of BaCoAl₁₁O₁₉ is quite difficult via solid-state reaction of oxide powders. Anisotropic BaCo(Al,Ga)₁₁O₁₉ particles crystallized at 1100°C for 2 h through the coprecipitation method using metal nitrates and ammonium carbonate. BaCo(Al,Ga)₁₁O₁₉ supported on a cordierite honeycomb had the ability to reduce NO _x with methane over 500°C in the presence of excess oxygen.     

Alumina Dissolution into Silicate Slag

Dissolution of commercial white fused and tabular Al₂O₃ grains into a model silicate slag was investigated after 1 h at 1450° and 1600°C. Formation of CA₆ and hercynitic spinel layers was observed at all Al₂O₃/slag interfaces. The spinel layer was not always continuous, and so, compared with the CA₆ layer, it had a less-significant effect on the dissolution process. The CA₆ layer that formed adjacent to the tabular Al₂O₃ was incomplete at both temperatures, so that its dissolution was not a totally indirect process. These incomplete CA₆ and spinel layers meant that slag penetrated into the tabular Al₂O₃ grains, which, thus, were corroded and disintegrated by the penetrating slag. There was evidence of liquid in the CA₆ layer adjacent to the fused Al₂O₃ after 1 h at 1450°C, which also enabled direct dissolution. After 1 h at 1600°C, fused Al₂O₃ revealed a thick (∼60 μm), continuous and unpene-trated CA₆ layer, indicating fully indirect dissolution at this temperature.     

Preparation of Larnthanum β-Alumina with High Surface Area by Coprecipitation

Mixtures of La₂O₃ and Al₂O₃ with various La contents were prepared by co-precipitation from La(NO₃)₃ and Al(NO₃)₃ solutions and calcined at 800° to 1400°C. The addition of small amounts of La₂O₃ (2 to 10 mol%) to Al₂O₃ gives rise to the formation of lanthanum β-alumina (La 2 O₃·11–14Al₂O₃) upon heating to above 1000°C and retards the transformation of γ-Al₂O₃ to α-Al₂O₃ and associated sintering.     

Li-(Mg,Zn,Ni) Vanadates

Phase relations were determined in the systems of Li-(Mg,Zn,Ni) vanadates in the temperature range between 500° and 800°C. Each of the ternary systems Li₂O-(Mg, Zn, or Ni)O-V₂O₅ is characterized by an orthovanadate: olivine-type LiMgVO₄, phenakite-type LiZnVO₄, and spinel-type LiNiVO₄. Mutual solid solutions form between them. Two solid solutions, a large region of the NiV₂O₆ type and a complete series between MgV₂O₆ and ZnV₂O₆, exist in the system (Mg,Zn,Ni)V₂O₆. The system (Mg,Zn,Ni)₂V₂O₇ has an extensive solid-solution region based on Ni₂V₂O₇, whereas the system (Mg,Zn,Ni)₃V₂O₈ is characterized by a complete series.     

Formation of NiAl2O4 by Solid State Reaction

The growth of nickel-aluminum spinel, NiAl₂O₄, in diffusion couples of polycrystalline Al₂O₃ and NiO was investigated between 1200° and 1500°C. The growth kinetics for the spinel layer obeyed a parabolic rate law in this temperature range. Marker experiments showed that the spinel layer formed by counterdiffusion of nickel and aluminum ions. Comparison of experimental and theoretical values of the parabolic rate constants suggests that the diffusion of aluminum ions through the spinel layer is rate controlling.     

Microstructure of Varistors Prepared with Zinc Oxide Nanoparticles Coated with Bi2O3

Zinc oxide (ZnO) nanoparticles coated with 1–5 wt% Bi₂O₃ were prepared by precipitating a Bi(NO₃)₃ solution onto a ZnO precursor. Transmission electron microscopy showed that a homogeneous Bi₂O₃ layer coated the surface of the ZnO nanoparticles and that the ZnO particle size was ∼30–50 nm. Scanning electron microscopy showed that ZnO grains sintered at 1150°C were homogeneous in size and surrounded by a uniform Bi₂O₃ layer. When the ZnO grains were surrounded fully by Bi₂O₃ liquid phases, further increases in the ZnO grain size were not affected by the Bi₂O₃ content. This predesigned ZnO nanoparticle structure was shown to promote homogeneous ZnO grains with perfect crystal growth.     

The System MgO-Cr2O3−Fe2O3 at 1300°c in Air

Phase relations in air at 1300°C were determined for the system MgO-Cr₂O₃−Fe₂O₃ by conventional quenching techniques. Details of the phase equilibria were established for: (1) the sesquioxide solid solution between Cr₂O₃ and Fe₂O₃, (2) the spinel solid solution field between MgCr₂O₄ and MgFe₂O₄, and (3) the periclase solid solution field for MgO. Selected tie lines connecting coexisting compositions were established with X-ray diffractometer data. Diffuse reflectance spectra, diffractometer intensity ratios, and lattice parameter measurements were obtained for quenched samples to study the structural inversion in the spinel series MgCr₂O4-MgFe₂O₄.     

Elastic Moduli of Refractory Spinels

Elastic moduli of spinel phases in the system Mg(Al, Cr, Fe)₂O₁ were determined from sonic analyses of porous, polycrystalline specimens prepared by hot-pressing. A special iterative least-squares technique (ILS) and standard curve-fitting techniques were used to obtain moduli at zero porosity by extrapolation. A minimal standard error of estimate was achieved in all cases by using an exponential form for the porosity dependence and the ILS technique. Moduli were checked for self-consistency. Extrapolated moduli for MgAl₂O₁ agreed well with respective moduli calculated from single-crystal elastic constants and Birch's law. Longitudinal and shear sound velocities decreased with increasing phase density in the solid-solution systems and systematics indicate that elastic moduli of arbitrary solid solutions can be estimated to lt; ± 10% from the phase density.     

Single-Calcination Synthesis of Pyrochlore-Free 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 and Pb(Mg1/3Nb2/3)O3 Ceramics Using a Coating Method

A coating approach for synthesizing 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃ (0.9PMN–0.1PT) and PMN using a single calcination step was demonstrated. The pyrochlore phase was prevented by coating Mg(OH)₂ on Nb₂O₅ particles. Coating of Mg(OH)₂ on Nb₂O₅ was done by precipitating Mg(OH)₂ in an aqueous Nb₂O₅ suspension at pH 10. The coating was confirmed using optical micrographs and zeta-potential measurements. A single calcination treatment of the Mg(OH)₂-coated Nb₂O₅ particles mixed with appropriate amounts of PbO and PbTiO₃ powders at 900°C for 2 h produced pyrochlore-free perovskite 0.9PMN–0.1PT and PMN powders. The elimination of the pyrochlore phase was attributed to the separation of PbO and Nb₂O₅ by the Mg(OH)₂ coating. The Mg(OH)₂ coating on the Nb₂O₅ improved the mixing of Mg(OH)₂ and Nb₂O₅ and decreased the temperature for complete columbite conversion to ∼850°C. The pyrochlore-free perovskite 0.9PMN–0.1PT powders were sintered to 97% density at 1150°C. The sintered 0.9PMN–0.1PT ceramics exhibited a dielectric constant maximum of ∼24 660 at 45°C at a frequency of 1 kHz.