Effects of Lithium and Oxygen Losses on Magnetic and Crystallographic Properties of Spinel Lithium Ferrite

The effects of sintering temperature and cooling rate on the magnetic and crystallographic properties of lithium ferrite were studied. The magnetic moments and lattice parameters increased with increasing sintering temperature; these increases result from correlated oxygen and lithium oxide losses. Either annealing at lower temperatures or slow cooling under O₂ causes reoxidation of the Fe²⁺ formed at higher temperatures with attendant decreases in moment and lattice parameter and gradual precipitation of α-Fe₂O₃ as a second phase. The products formed on rapid cooling are equivalent to solid solutions of spinel lithium ferrite with Fe₃O₄, and those formed on slow cooling, to solid solutions of lithium ferrite and γ-Fe₂O₃ with precipitation of α-Fe₂O₃. Lithium losses and α-Fe₂O₃ precipitate amounts are calculated. The magnetic moment of stoichiometric lithium ferrite at 25°C is 3736±20 G; the lattice parameter at 28°C is 8.3296±0.0005 Å.     

Synthesis of Magnesium Aluminate Spinel Platelets from α-Alumina Platelet and Magnesium Sulfate Precursors

Spinel platelets were formed from a powder mixture of 3–5 μm wide and 0.2–0.5 μm thick α-Al₂O₃ and 1–8 μm (average 3 μm) MgSO₄ heated 2 h at 1200°C. The hexagonal platelet shape of the original α-Al₂O₃ platelet was maintained in the spinel, although their size was slightly increased and their surface roughened. When a mixture of α-Al₂O₃ platelets and MgO powder was heated 3 h at 1400°C, the spinel formed lost the platelet morphology of the alumina.     

Stabilization of Ordered Zirconium Titanates through the Chemical Substitution of Ti4+by Al3+/Ta5+

We have investigated the ZrO₂–AITaO₄ system to understand how selected chemical substitutions can be used to control cation-ordering transformations in zirconium titanate based dielectric ceramics. The complete replacement of the Ti content of Zr _x Ti_2–xO₄ by a coupled Al³⁺/Ta⁵⁺ substitution permits the synthesis of a wide range of isostructural Zr _x (Al_0.5Ta_0.5)_2–xO₄ solid solutions. At high temperatures a disordered α-PbO₂ type of structure is formed for 0.375 ≤ x ≤ 1.03. Samples with 0.67 ≤ x ≤ 1.03 undergo a cation-ordering reaction to a structure in which the a and b axes of the parent disordered Cell are doubled. The stabilities of these cation-ordered derivative structures are significantly greater than those of the ordered zirconium titanates. The ordering temperatures are composition dependent with a maximum of 1393°C occurring for Zr_0.86(Al_0.5TaO_0.5)_1.14O₄. The higher transition temperatures also enhance the kinetics of the ordering transition; whereas the pure zirconium titanates require extended annealing to produce complete cation order, fully ordered Zr_χ(Al_0.5Ta_0.5)_2–χO₄ solid solutions are produced during a normal furnace cool.     

Formation of Alumina/Zirconia (3 mol% Yttria) Composite Powders Prepared by the Hydrazine Methods

Alumina/3 mol% yttria-doped zirconia composite powders have been prepared by the hydrazine method. As-prepared powders are AlO(OH) gel solid solutions and the mixtures of this and amorphous ZrO₂ below and above 10 mol% ZrO₂, respectively. The formation process leading to α–Al₂O₃– t -ZrO₂ composite powders is examined.     

Internal Reactions in Oxide Solid Solutions

Oxidation of wustite-type solid solutions (A, B)0 and reduction of sesquioxide solid solutions (A, B)₂0₃ can lead to the precipitation of a spinel phase (A, B)₃0₄ at an inner reaction front. A representation of the reaction scheme and kinetics for each of the two cases will be given. Observations on the macroscopic morphology of the spinel precipitates and on the structure of the precipitate/matrix interphase boundary are discussed.     

Microwave-Hydrothermal Synthesis of Monodispersed Nanophase α-Fe2O3

Synthesis of monodispersed nanophase α-Fe₂O₃ (hematite) powder to be used as a red pigment in porcelains was investigated using microwave-hydrothermal and conventional-hydrothermal reactions using 0.018 M FeCl₃·6H₂O and 0.01 M HCl solutions at 100°–160°C. Acicular and yellow β-FeOOH (akaganite) particles 300 nm in length and 40 nm in thickness were dominantly formed at 100°C after 2–3 h, while spherical α-Fe₂O₃ particles 100–180 nm in diameter were preferentially formed after 13 h using a conventional-hydrothermal reaction. However, a microwave-hydrothermal reaction at 100°C led to monodispersed and red α-Fe₂O₃ particles 30–66 nm in diameter after 2 h without the formation of β-FeOOH particles. In this paper, the effect of microwave radiation during hydrothermal treatment at 100°–160°C on the formation yield, kinetics, morphology, phase type, and color of α-Fe₂O₃ was investigated.     

Role of the Initial Degree of Ionization of Polyethylenimine in the Dispersion of Silicon Carbide Nanoparticles

The role of the initial degree of ionization (α_i) of polyethylenimine (PEI) in the dispersion of SiC nanopartilces in water was investigated by sedimentation and rheological measurements. The ionization of PEI was characterized by potentiometric titration, which indicated a pH-dependent conformational transition. The dispersion of SiC particles in the presence of PEI was found to strongly depend on the α_i. In the presence of 0.4% by weight PEI, the 23.8% SiC by volume (Φ_SiC= 23.8) slurries showed a Newtonian behavior for α_i= 0.12–0.4 values, whereas a shear-thinning behavior was observed for α_i > 0.4 in the optimal pH range of around pH 4. The rheological behavior of the slurries exhibited a strong dependence on the concentration of PEI of α_i= 0.12–0.4 and the slurry showed a Newtonian behavior at an optimal concentration of 0.4% by weight. The stabilization may be dominated by an electrosteric effect arising from the adsorbed PEI of α_i= 0.12–0.4. The flocculation mechanism of the slurries with PEI of α_i > 0.4 is also discussed.     

Formation of Zirconia Solid Solutions Containing Alumina Prepared by New Preparation Method

In the system ZrO₂–Al₂O₃, a new method for preparing ZrO₂ solid solutions from ZrCl₄ and AlCl₃ using hydrazine monohydrate is investigated. c -ZrO₂ solid solutions containing up to ∼40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials. The formation mechanism is discussed from IR spectral data. The values of the lattice parameter α increase linearly from 0.5072 to 0.5105 nm with increasing Al₂O₃ content. At higher temperatures, transformation of the solid solutions proceeds as follows: c ( SS ) → t ( ss ) → t ( ss ) +α-Al₂O₃→ m +α-Al₂O₃. m -ZrO₂–α-Al₂O₃ composite ceramics are fabricated by hot isostatic pressing for 2 h at 1250°C and 196 MPa. Microstructures and mechanical properties are examined, in connection with increasing Al₂O₃ content.     

The α–β Transformation in Silicon Nitride Single Crystals

Single crystals of α-Si₃N₄ were annealed at 2000°–2150°C. The β phase was detected after annealing at 2150°C only when the crystals were surrounded by MgO·3Al₂O₃ or Y₂O₃ powders. On the other hand, no evidence of the α–β transformation was found when the crystals were annealed without additives. The solution–precipitation mechanism was concluded to be the dominant factor in the α–β transformation of Si₃N₄.     

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.     

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.     

Hydrothermal Synthesis and Low-Temperature Sintering of Zinc Gallate Spinel Fine Particles

Nanosized powders of single-phase zinc gallate (ZnGa₂O₄) spinel were hydrothermally synthesized from solutions in the presence of NaOH over the pH range of 1.9 to 7.0 and from solutions above pH 7.0, i.e., the very basic medium (pH of 13.85), by removing the residual ZnO phase by washing with aqueous H₂SO₄ from the precipitate mixtures of zinc gallate spinel particles and ZnO. A very wide compositional range (Zn/2Ga = 0.705–1.157) of zinc gallate spinel solid solutions could be hydrothermally synthesized in the form of nanosized particles from acid and very basic mediums (pH of 2.4–13.85) in the presence of NaOH. These hydrothermally synthesized spinel powders showed good sinterability and almost full densification at 1100°C for 1 h. Dense sintered bodies consisting of single-phase zinc gallate spinel were fabricated at 1100°C using zinc gallate spinel powders having almost stoichiometric composition formed from the solution at pH 9.95 in the presence of aqueous ammonia.     

Synthesis and Characterization of Ce3+:YAG Phosphors by Heterogeneous Precipitation Using Different Alumina Sources

Ce³⁺-doped yttrium aluminum garnet (Ce:YAG) phosphor powders were synthesized by heterogeneous precipitation process using three different aluminum sources: α-phase, θ-phase, and boehmite (AlOOH). Mixtures of yttrium and cerium nitrate solutions containing various aluminum sources were precipitated by ammonia solution in normal and reverse strike methods. The influence of pH was studied in the normal strike method by maintaining the solutions at pH 7, 9, and 11 during precipitation. Dried precipitates were double calcined at 1300°C/16 h and 1300–1500°C/24 h, at a ramping rate of 10°C/min, with an intermittent wet ball milling in water. Structural evolution of the resultant phosphors was studied by powder XRD. In the normal strike method, a highly pure YAG phase was formed by α- alumina (pH 7, 11) and θ-alumina (pH 11) while boehmite source ended up with mixed phases of YAlO₃ (YAP) and Y₄Al₂O₉ (YAM) along with YAG phase at all pH values of precipitation. However, in the reverse strike process, the θ-phase of alumina gave an extremely pure Ce:YAG phase at a relatively lower calcination temperature (1400°C/24 h) compared with the α-phase and also showed more intense emission of yellowish-green light under blue (λ=469 nm) excitation. Scanning electron microscopy revealed 1–2 μm sized particles with least agglomeration in the reverse strike method.     

Hydrothermal Precipitation of Lead Zirconate Titanate Solid Solutions: Thermodynamic Modeling and Experimental Synthesis

A previously developed thermodynamic model of hydro-thermal synthesis of ceramic powders has been extended to include cases when solid solutions are formed. The model has been applied to the synthesis of a series of lead titanate zirconate solid solutions PbZr _x Ti_{1– x} O₃ (PZT, 0.46 < x ≤ 0.75). It predicts the optimum conditions (i.e., reagent, concentration, pH, and temperature) for the precipitation of phase-pure homogeneous PZT, provided that the reactants are well mixed. The predictions have been experimentally corroborated using coprecipitated hydrous oxide Zr _x Ti_{1– x} C₂ n H₂O (0.46 < x ≤ 0.75), as a precursor for Ti and Zr and water-soluble lead acetate or nitrate salts as a source for Pb. When mixtures of hydrous oxides ZrO₂· n H₂O and TiO₂· n H₂O were employed as Ti and Zr precursors, independent PbTiO₃ and PbZrO₃ precipitates rather than the PZT solid solutions formed. These results can be rationalized on the basis of reaction kinetics where thermodynamic modeling includes or excludes the possibility of solid-solution formation.     

Electronic Structures of Ln3+α-SiAIONs with Correlations to Solubility and Solution Effects

First-principles molecular-orbital calculations using the discrete-variational Xα method have been made on model clusters of α-Si₃N₄ and its solid solutions with lanthanide elements, which occupy interstitial sites in the structure. The formula is Ln_χSi_12–4.5χAl_4.5χO_1.5χN16–1.5χ (Ln = La, Nd, Gd, Dy, Ho, Er, Tm, Yb), i.e., a Ln-α-SiAION solid solution. Covalent bond strength between Si and N, evaluated by overlap population, increases because of the presence of trivalent charges at the interstitial sites. When a Ln³⁺ ion is present, antibondings occur between Ln orbitals and N/Si orbitals, and they depend significantly on the ionic radius of Ln³⁺. The total overlap population for the whole cluster is determined by the balance of Si-N bond reinforcement and Ln-N/Si antibonding. Although no lattice relaxation around the Ln³⁺ ion is included in the present calculation, good correlation between maximum solubility and the total overlap population for the whole cluster is demonstrated for the first time.     

Microstructure and Physicochemical Studies of Pure and Zinc-Substituted Lithium Ferrites Sintered above 1000°C

The effects of sintering temperature above 1000°C and of cooling rate on the microstructual development of pure and Zn-substituted spinel lithium ferrites are discussed. The strong dependence of microstructural features on cooling rate can be explained on the basis of the precipitation of α-Fe₂O₃ or the formation of a solid solution of ferrite phase with Fe₃O₄ occurring during sintering above 1000°C. These two phenomena are studied by detailed characterization analyses: SEM, XRD, magnetization, and ac electrical resistivity measurements.     

Numerical Data for Some Commonly Used Solid State Reaction Equations

Many solid state reactions can be represented by equations of the type F (α) = kt , where α is the fraction of material reacted in time, t. These equations can be expressed in the form F (α) = A ( t/t _0.5) where t _0.5 is the time for 50% reaction and A is a calculable constant depending on the form of F (α). Numerical tables are given of F (α) in relation to α, and to ( t/t _0.5), for nine equations corresponding to reactions which are diffusion controlled, or are reaction-rate controlled, or obey first order kinetics, or follow the equations of Avrami and Erofe'ev. The application of the tables to the analysis of experimental data is described.     

Spinel-Corundum Phase Equilibria in the Systems Mn-Cr-Al-O and Co-Cr-Al-O at 1373 K

The tie lines delineating ion-exchange equilibria between MCr₂O₄-MAl₂O₄ spinel solid solution, where M is either Mn or Co, and Cr₂O₃-Al₂O₃ solid solution with the corundum structure were determined at 1373 K by electron microprobe and E0AX point count analysis of the oxide phases equilibrated with metallic Co and Au-5% Mn. The component activities in the spinel solid solutions are derived from the tie lines and the thernodynamic data for Cr₂O₃-Al₂O₃ soiid solutions available hi the literature. The Gibbs free energies of mixing calculated from the experimental data are discussed in relation to the values derived from the cation distribution a.odel based on the site preference energies and assuming random mixing on both tetrahedral and octahedral sites. Positive deviations from ideality observed in this study suggest a miscibility gap for both series of spinel solid solutions at low temperatures in the absence of oxidation.     

Optical Spectra of Synthetic Spinels in the System MgAl2O4–MgCr2O4

Unpolarized optical spectra were measured in the wavelength range 322–1666 nm by the diffuse reflection technique from spinel powders synthesized in the system MgAl₂O₄–MgCr₂O₄. The spectra were interpreted by the crystal-field theory on the basis of trigonally distorted spinel octahedra with D_3d symmetry. For chromium-rich solid solutions, including the MgCr₂O₄ end-member, results after peak fittings showed octahedral D_3d local symmetry around Cr³⁺ ions, identical to the crystallographic site symmetry. For chromium-poor solid solutions, however, octahedral C_3v local symmetry was suggested around Cr³⁺ ions, different from the D_3d crystallographically expected.     

Reactions in the System Li2O–MgO–Al2O3–SiO2: I, The Cordierite-Spodumene Join

Phase equilibria along the nonbinary join between cordierite (2MgO · 2Al₂O₃· 5SiO₂) and spodumene (Li₂O · Al₂O₃· 4SiO₂) were investigated in the temperature range 800° to 1550°C. using the quench technique on fourteen compositions. The phase diagram at high temperatures is characterized by a very small region of solid solution on the cordierite side, appreciable solid solution on the spodumene side, and regions of three and four phases toward the center of the system, including liquid, α-cordierite, mullite, spinel, corundum, and β-spodumene and its solid solutions. The liquidus has a flat minimum between 40 and 50% cordierite at 1347°, and rises on one side to the congruent melting point of β-spodumene (1421°) and on the other side to the temperature of complete melting of cordierite (1530°). The lowest temperature at which liquid appears is 1325°. At low temperatures a complete series of metastable solid solutions exists between μ-cordierite and β-spodumene. The significance of the data in the preparation of thermal-shock-resisting bodies is discussed.