Nonisothermal Crystallization Kinetics of BixY3−xFe5O12 (0.25≤x≤1.00) Prepared from Coprecipitation Process

The nonisothermal crystallization kinetic of Bi _x Y_{3− x} Fe₅O₁₂ (0.25≤ x ≤1.00) powders prepared by coprecipitation process has been investigated. The activation energy of crystallization was calculated by differential scanning calorimetry at different heating rates. The activation energies of crystallization of Bi _x Y_{3− x} Fe₅O₁₂ system are 492, 447, 377, and 353 kJ/mol and the Avrami constant n are 3.49, 2.25, 2.48, and 2.33 for x =0.25, 0.50, 0.75, and 1.00, respectively. The Avrami exponent values (1< n <3) were consistent with surface and internal crystallizations occurring simultaneously for 0.50≤ x ≤1.00, the value ( n >3) for the Avrami exponent was consistent with bulk crystallization domination in Bi _x Y_{3− x} Fe₅O₁₂ system. The results reveal that increasing the substitution amount of bismuth for yttrium would significantly decrease activation energy in Bi _x Y_{3− x} Fe₅O₁₂ system.     

Low Thermal Conductivity in Garnets

The thermal conductivity of dense, polycrystalline garnet ceramics with compositions of Y₃Al_xFe_(5−x)O₁₂(x = 0.0, 0.7, 1.4, and 5.0) was measured in the temperature range 23° to 1000°C. The high-temperature thermal conductivity of some of these garnets was found to be as low as 2.4 W·m^-1K^-1. The effects of temperature and composition on the observed thermal conductivity are discussed with reference to established theories of thermal conduction. The potential use of yttrium aluminum garnet or YAG (Y₃Al₅O₁₂), in particular, for a specific application of advanced thermal barrier coatings (TBCs) with improved durability is considered.     

Growth of Single Crystals of Incongruently Melting Yttrium Iron Garnet by Flame Fusion Process

Single crystals of yttrium iron garnet (Y₃Fe₅O₁₂) have been grown using the flame fusion process, even though the compound is reported to melt incongruently. The growth of these single crystals involves a mechanism different from that which has been proposed for the growth of single crystals of incongruently melting mullite. Crystal boules were grown at varying linear growth rates and analyzed with chemical, X-ray, and metallographic techniques. With high linear growth rates, the samples are uniformly polycrystalline and three-phase, containing Fe₂O₃, YFeO₃, and Y₃Fe₅O₁₂. When slow linear growth rates are used, single-crystal Y₃Fe₅O₁₂ can be grown. The mechanism is as follows: At the beginning of growth the first phase to precipitate is YFeO₃, and during this stage in growth the molten cap becomes enriched in Fe₂O₃, compared with the Y₃Fe₅O₁₂ composition. The liquid cap composition thus changes to the limit of the peritectic on the Fe₂O₃-rich side, and Y₃Fe₆O₁₂ then crystallizes from the bottom of the melt as Y₃Fe₅O₁₂ powder is added to the top of the molten cap. The central sections of these boules are single-crystal yttrium iron garnet.     

Formation of Metastable Rare-Earth Iron Garnet by Splat Quenching

The droplet with Nd _x Sm_{3− x} Fe₅O₁₂ composition was undercooled in an aerodynamic levitator and splat quenched by copper anvils in order to obtain a metastable garnet with a solubility limit larger than the phase equilibrium solubility limit, x =0.375, for the Nd _x Sm_{3− x} Fe₅O₁₂ system. The peaks of the garnet were identified with the peaks of the perovskite by powder X-ray diffraction (XRD), although the peak intensity for the garnet decreased with increasing the Nd substitution from x =0.43 to 0.2, and finally disappeared at x =2.2. When the garnet was annealed at 1570 K for 24 h in air, it transformed into a mixture of perovskite and hematite, which indicates that the garnet obtained was the metastable phase. Moreover, the amorphous phase was found in the central part of all the samples even at x =2.2, which was confirmed by micro-focus XRD. The formation of the constituent phases in the as-quenched sample was discussed using a continuous cooling transformation diagram.     

Phase Relations In The Pseudo-Ternary System La2O3–SrO–Fe2O3

The phase relations in the pseudo-ternary system La₂O₃–SrO–Fe₂O₃ have been investigated in air. Isothermal sections at 1100° and 1300°C are presented based on X-ray diffraction and thermal analysis of annealed samples. Extended solid solubility was observed for the compounds Sr _{n +1− v} La _v Fe _n O_{3 n +1−δ} ( n =1, 2, 3, and ∞) and Sr_{1− x} La _x Fe₁₂O₁₉, while only limited solubility of La in Sr_{4− z} La _z Fe₆O_13±δ was observed. At high Fe₂O₃ content, a liquid with low La₂O₃ content was stable at 1300°C.     

Defect Structure and Electrical Properties of La1−ySryFe1−xAlxO3−δ

La_{1− y} Sr _y Fe_{1− x} Al _x O_3−δ perovskites were studied as potential materials for solid-oxide fuel cell (SOFC) cathodes. The phase relations in the LaFeO₃–SrFeO_3−δ–LaAlO₃ system were investigated by X-ray powder diffraction analysis. The defect structure of the La_{1− y} Sr _y Fe_{1− x} Al _x O_3−δ perovskites was investigated by Mössbauer spectroscopy and weight-loss analysis. Relations between the nonstoichiometry and the conductivity of the La_{1− y} Sr _y Fe_{1− x} Al _x O_3−δ perovskites were investigated. The incorporation of aluminum ( x ) into LaFe_{1− x} Al_xO₃ was found to have no influence on the defect structure but to decrease the conductivity. The incorporation of strontium ( y ) into La_{1− y} Sr _y Fe_{1− x} Al _x O_3−δ promotes the formation of anion vacancies and Fe⁴⁺ that lead to higher conductivity.     

Novel Synthesis of Silica-Coated Ferrite Nanoparticles Prepared Using Water-in-Oil Microemulsion

Ferrite nanoparticles (magnetite (Fe₃O₄) and cobalt-ferrite (Co _x Fe_{3− x} O₄)) coated with silica (SiO₂) were prepared using water-in-oil microemulsion of a polyoxyethylen(15)cetylether/cyclohexene system. Observation via transmission electron microscopy revealed that the ferrite nanoparticles were located nearly at the center of spherical SiO₂ particles. The sizes of Fe₃O₄ and Co _x Fe_{3− x} O₄ nanoparticles were in the range of 8–12 nm and 10–14 nm, respectively, and the thickness of the SiO₂ layer was ∼14.0 nm. The solid solution of cobalt ions into Fe₃O₄ to form Co _x Fe_{3− x} O₄ nanoparticles led to an increase in the coercivity of the SiO₂-coated ferrite nanoparticles. The coercivity increased with increasing amounts of added cobalt, obtaining a maximum value of 780 Oe around a Co/Fe ratio of 0.3–0.4.     

Effect of La Doping on the Phase Conversion, Microstructure Change, and Electrical Properties of Bi2Fe4O9 Ceramics

Undoped and La-doped Bi₂Fe₄O₉ ceramics were synthesized using a soft chemical method. It is observed that in calcining La-doped Bi₂Fe₄O₉, Bi(La)FeO₃ phase rather than Bi_{2− x} La _x Fe₄O₉ gradually increases with increasing La doping content. The phase conversion from mullite-type structure of Bi₂Fe₄O₉ to rhombohedrally distorted perovskite one of Bi(La)FeO₃ with increasing La doping content indicates that La doping can stabilize the structure of BiFeO₃. This is further evidenced that Bi₂Fe₄O₉ can be directly converted to Bi(La)FeO₃ by heating the mixtures of nominal composition of Bi₂Fe₄O₉/ x La₂O₃. Furthermore, the microstructure changes and the room temperature hysteresis loops and leakage current for Bi_{2− x} La _x Fe₄O₉ with x =0 and 0.02 were characterized.     

Quaternary Compounds Prepared in a CaO–Y2O3–SnO2 System

Compounds in a CaO–Y₂O₃–SnO₂ system were prepared by a solid-state reaction at 1673 K. The phase relation in this system was investigated by powder X-ray diffraction. Besides the previously reported ternary compounds, CaSnO₃, Ca₂SnO₄, Y₂Sn₂O₇, and a quaternary compound Ca_0.4Y_1.2Sn_0.4O₃, solid-solution series of Ca_{2− x} Y_{2 x} Sn_{1− x} O₄ with 0≤ x ≤0.5, and Ca_{1− y} Y_{2 y} Sn_{1− y} O₃ with 0≤ y ≤0.2 and 0.95≤ y ≤1.0 were found. The cell parameters of these solid-solution series were refined. The changes of rhombohedral cell parameters in the samples prepared in the range 0.565< y <0.714 of Ca_{1− y} Y_{2 y} Sn_{1− y} O₃ suggested the existence of solid solutions of Ca_0.4Y_1.2Sn_0.4O₃, although their single phases could not be prepared, except at y =0.6.     

Chemical Interactions between La-Sr-Mn-Fe-O-Based Perovskites and Yttria-Stabilized Zirconia

Orthoferrite-based perovskites are of interest as materials for the cathode in solid oxide fuel cells (SOFCs). Therefore, the chemical compatibility between perovskites of the composition (La_1−xSr_x)_zFe_1−yMn_yO_3−δ (0 # x # 0.3; 0.2 # y # 1; z = 0.90, 0.95, 1.00) and the solid electrolyte zirconia (ZrO₂) doped with 8 mol% yttria (Y₂O₃) (8YSZ) has been investigated. Powder mixtures of the two materials have been annealed at different temperatures. The formation of monoclinic ZrO₂ at 1000°C, as well as of La₂Zr₂O₇ and SrZrO₃ at 1400°C, has been determined in some samples. The reactions that are observed are discussed, with respect to the thermodynamic activities, tolerance factor, and oxygen-ion migration energies. Some perovskite compositions seem to be compatible with Y₂O₃-stabilized ZrO₂ (YSZ), thereby offering the possibility to use orthoferrite-based perovskites in SOFCs with a solid electrolyte made of YSZ.     

Phase Diagram and Oxygen-Ion Conductivity in the Y2O3-Nb2O5 System

The phase equilibria in the Y₂O₃-Nb₂O₅ system have been studied at temperatures of 1500° and 1700°C in the compositional region of 0-50 mol% Nb₂O₅. The solubility limits of the C-type Y₂O₃ cubic phase and the YNbO₄ monoclinic phase are 2.5 (±1.0) mol% Nb₂O₅ and 0.2 (±0.4) mol% Y₂O₃, respectively, at 1700°C. The fluorite (F) single phase exists in the region of 20.1-27.7 mol% Nb₂O₅ at 1700°C, and in the region of 21.1-27.0 mol% Nb₂O₅ at 1500°C, respectively. Conductivity of the Y₂O₃- x mol% Nb₂O₅ system increases as the value of x increases, to a maximum at x = 20 in the compositional region of 0 ≤ x ≤ 20, as a result of the increase in the fraction of F phase. In the F single-phase region, the conductivity decreases in the region of 20-25 mol% Nb₂O₅, because of the decrease in the content of oxygen vacancies, whereas the conductivity at x = 27 is larger than that at x = 25. The conductivity decreases as the value of x increases in the region of 27.5 ≤ x ≤ 50, because of the decrease in the fraction of F. The 20 mol% Nb₂O₅ sample exhibits the highest conductivity and a very wide range of ionic domain, at least up to log p _O2=−20 (where p _O2 is given in units of atm), which indicates practical usefulness as an ionic conductor.     

Synthesis of New Nanocrystalline Titanium–Niobium Oxynitride Powders

New titanium–niobium oxynitride (Ti_{1− z} Nb _z O _x N _y ) powders were synthesized by ammonolysis of nanosized TiO₂/Nb₂O₅ composite powders at 700°–900°C for 5 h. The products were characterized by X-ray diffraction (XRD), chemical analysis, and transmission electron microscopy. The results indicated that the as-synthesized powders were pure cubic structures with sizes of 30–60 nm. With increasing value of z , XRD peaks of Ti_{1− z} Nb _z O _x N _y powders tended to shift toward low 2θ angle and the cell parameter showed a linear increase.     

Microwave Synthesis of Yttrium Iron Garnet Powder

A 28 GHz microwave heating method was used to react an Fe₂O₃+ Y₂O₃ powder mixture to form yttrium iron garnet (YIG, Y₃Fe₅O₁₂) powder. The minimum temperature to form YIG was lower than the conventional (external) heating method. YIG began to form after only 70 s of irradiation, which means that the solid-state reaction proceeded very rapidly. The amounts of byproducts were controlled by the starting composition and by the Y₂O₃ particle size. The resultant YIG particle size also was controlled by the Y₂O₃ particle size.     

Hydrothermal Preparation of Ultrafine Ferrites and Their Sintering

Ultrafine and nearly spherical ferrites such as NiFe₂O₄, ZnFe₂O₄, Ni_xZn_1−xFe₂O₄, Mn_0.5Zn_0.5Fe₂O₄, and CoFe₂O₄ were prepared under mild hydrothermal conditions by precipitating from metal nitrates with aqueous ammonia. These hydrothermal ferrite powders were shown to sinter to almost theoretical density at 1000°C without any sintering aids.     

Film Synthesis of Y3Al5O12 and Y3Fe5O12 by the Spray–Inductively Coupled Plasma Technique

Thin films of yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) and yttrium iron garnet (YIG, Y₃Fe₅O₁₂) were synthesized on single-crystal Al₂O₃ substrates by a modification of spray pyrolysis using a high-temperature inductively coupled plasma at atmospheric pressure (spray–ICP technique). Using this technique, films could be grown at faster rates (0.12 μm/min for YAG and 0.10 μm/min for YIG) than using chemical vapor deposition (0.005–0.008 μm/min for YAG) or sputtering (0.003–0.005 μm/min for YIG). The films were dense and revealed a preferred orientation of (211). The growth of YIG was accompanied by coprecipitation of α-Fe₂O₃. The coprecipitation, however, could be largely suppressed by preliminary formation of a Y₂O₃ layer on the substrate.     

Magneto-Dielectric Properties of Mg–Cu–Co Ferrite Ceramics: I. Densification Behavior and Microstructure Development

The densification, grain growth, and microstructure development of Mg–Cu–Co ferrite ceramics (MgFe_1.98O₄, Mg_{1− x} Cu _x Fe_1.98O₄, with x =0.10–0.30 and Mg_{0.90− x} Co _x Cu_0.10Fe_1.98O₄, with x =0.05–0.20) were studied. The primary objective was to develop magneto-dielectric materials for miniaturization of high frequency and very-high frequency antennas. It was found that magnesium ferrite (MgFe_1.98O₄) is a promising magneto-dielectric material. However, due to its poor densification, it could not be fully sintered at a temperature below 1200°C. High-temperature sintering resulted in undesirable electrical and dielectric properties, due to the formation of Fe²⁺ ions. The poor densification and slow grain growth rate of MgFe_1.98O₄ can be considerably improved by incorporating Cu, due to the occurrence of liquid-phase sintering at a high temperature. A critical concentration of Cu was observed for Mg_{1− x} Cu _x Fe_1.98O₄, above which both densification and grain growth were maximized or saturated. The presence of Co did not have a significant influence on the densification and grain growth of the Mg-based ferrite ceramics.     

Composition Limits and Magnetic Properties of Sintered Y2.66Gd0.34FexAl0.677Mn0.09O12 Garnets

Single-phase garnet solid solutions can be synthesized between the composition limits of x =4.18 and x =4.22 in Y_2.66Gd_0.34Fe _x Al_0.677Mn_0.09O₁₂ at temperatures between 1340° and 1500°C in O₂. Solid solutions occur only on the Y₂O₃-excess side of the stoichiometric garnet composition. Electromagnetic properties and microstructural features of sintered garnets depend critically on small changes in Fe content in the vicinity of the garnet solid-solution region. An intergranular spinel-type second phase exists for compositions when x >4.22 and has a deleterious effect on remanent induction and magnetic loss at 3 GHz. The relative density of powder compacts sintered for 16 h at 1500°C in O₂ increases with increasing Fe content (i.e. as x increases) in the garnet solid solution.     

Oxygen Ion Diffusion in Single-Crystal and PoIycrystaIIine Yttrium Iron Garnet

The oxygen ion self-diffusion coefficient was determined for single-crystal and polycrystalline yttrium iron garnet (Y₃Fe₅O₁₂). The rate of exchange between oxygen gas enriched with the stable isotope ¹⁸O and solid yttrium iron garnet was measured. Oxygen ion diffusion rates were found to be the same in single-crystal and 8μ polycrystalline Y₃Fe₅O₁₂ between 1100° and 1400°C. This is in contrast to previous measurements of anion diffusion in several alkali halides and in AI₂O₃ where a strong dependence of diffusion rates on the presence of grain boundaries was found. Enhancing oxidation rates in dense, reduced yttrium iron garnet at low temperature by minimizing the final fired grain size in the sintering process does not appear to be possible on the basis of the results obtained in this investigation. The temperature dependence of the diffusion coefficient of oxygen measured at 100 torr can be represented by D = 0.40 exp (-65.4/RT) cm² per second.     

ac Impedance Study of Zirconia Doped with Yttria and Calcia

The ionic conductivity in the system (1 − 0.08 x − 0.12 y )ZrO₂–0.08 x Y₂O₃–0.12 y CaO (where x + y = 1 and y = 0–1) has been investigated using the complex impedance technique at 523–973 K. Doping CaO in the ZrO₂–Y₂O₃ system may result in an increase in the activation energy for lattice conduction and depress the grain-boundary effect on conduction. Analysis of the temperature dependence of the lattice conductivity, according to the familiar Arrhenius equation, predicts that the examined ternary system may exhibit greater lattice conductivity than the ZrO₂–Y₂O₃ binary system at higher temperatures. Preliminary explanations for these experimental phenomena and predictions also have been presented.