Hydrothermal Synthesis of Manganese Zinc Ferrite Powders from Oxides

Manganese zinc (MnZn) ferrite powders were prepared via the hydrothermal treatment of a homogeneous mixture of the raw oxides (i.e., Fe₂O₃, ZnO, and Mn₃O₄ or MnO) at temperatures of 220°-320°C in air or an inert atmosphere. The final results of the hydrothermal reactions between the raw oxides were fine powders with a heterogeneous phase composition. In addition to lower concentrations of the residual reactants (Fe₂O₃, Mn₃O₄), two types of spinel-structure-based reaction products-ferrite ((Mn²⁺,Zn)Fe₂O₄) and manganate ((Zn,Mn²⁺)Mn₂³⁺O₄)-were detected after the synthesis. The composition of the ferrite products, as well as the ratio of ferrite products to manganate products, were mainly functions of the oxidation state of the manganese that was present during treatment. The oxidation state of manganese during reaction was dependent on the valence of the manganese in the starting manganese oxide and on the atmosphere in the autoclave during reaction. When the hydrothermal reaction was conducted in air, almost-pure zinc ferrite was identified, whereas during reaction in an inert atmosphere, MnZn ferrite was formed. The kinetics of the hydrothermal reactions also were dependent on the oxidation state of manganese, as well as the temperature and specific surface area of the starting Fe₂O₃.     

Preparation of Crystalline Aluminum Phosphate by the Reaction Using Boron Phosphate

The use of BPO₄ in the synthesis of crystalline AlPO⁴ has been investigated. The best results are obtained if BPO₄ and hydrated alumina are heated in molten KCl: at 1050°C the conversion degree of BPO₄ into AlPO⁴ is >90% (in 4 h). The product consists of the tridymite AlPO⁴ form.     

Synthesis and Electrical Properties of Stabilized Manganese Dioxide (α-MnO2) Thin-Film Electrodes

Manganese dioxide (α-MnO₂) thin films have been explored as a cathode material for reliable glass capacitors. Conducting α-MnO₂ thin films were deposited on a borosilicate glass substrate by a chemical solution deposition technique. High carbon activities originated from manganese acetate precursor, (Mn(C₂H₃O₂)₂·4H₂O) and acetic acid solvent (C₂H₄O₂), which substantially reduced MnO₂ phase stability, and resulted in Mn₂O₃ formation at pyrolysis temperature in air. The α-MnO₂ structure was stabilized by Ba²⁺ insertion into a (2 × 2) oxygen tunnel frame to form a hollandite structure. With 15–20 mol% Ba addition, a conducting α-MnO₂ thin film was obtained after annealing at 600–650°C, exhibiting low electrical resistivity (∼1 Ω·cm), which enables application as a cathode material for capacitors. The hollandite α-MnO₂ phase was stable at 850°C, and thermally reduced to the insulating bixbyte (Mn₂O₃) phase after annealing at 900°C. The phase transition temperature of Ba containing α-MnO₂ was substantially higher than the reported transition temperature for pure MnO₂ (∼500°C).     

Effect of Additives on the Electromechanical Properties of Pb(Zr,Ti)O3–Pb(Y2/3W1/3)O3 Ceramics

Dielectric and piezoelectric properties of 0.02Pb(Y_2/3W_1/3)O₃ 0.98Pb(Zr0.52Ti0.48)O3 ceramics doped with additives (Nb₂O₅, La₂O₃, MnO₂, and Fe₂O₃) were investigated. The grain sizes of these ceramics decreased with increasing amounts of additives. For additions of MnO₂ and Fe₂O₃, dielectric losses decreased, while for Nb₂O₅ and La₂O₃, these values increased. The maximum values of the mechanical quality factor Q_m were found to be 956 and 975 for additions of 0.9 wt% Fe₂O₃ and 0.7 wt% MnO₂, respectively, but donor dopants (Nb₂O₅ and La₂O₃) did not change the values of Q_m . On the other hand, the piezoelectric constant d₃₃ and the electromechanical coupling factor k_p decreased with additions of MnO₂ and Fe₂O₃, but improved with additions of Nb₂O₅ and La₂O₃.     

The System Manganese Oxide–Cr2O3 in Air

The quenching technique has been used to determine equilibrium relations in the system manganese oxide-Cr₂O₃ in air in the temperature range 600° to 1980°C. The following isobaric invariant situations have been determined: At 910°± 5°C tetragonal Mn₃O₄ solid solution, cubic Mn₃O₄ solid solution (=spinel), Mn₂O₃ solid solution, and gas coexist in equilibrium. Cubic Mn₃O₄ solid solution, Cr₂O₃ solid solution, liquid, and gas are present together in equilibrium at 1970°± 20°C. The invariant situation at which cubic Mn₃O₄ solid solution, Mn₂O₃ solid solution, Cr₂O₃ solid solution, and gas exist together in equilibrium is below 600°C.     

Thermodynamic Properties of Manganese Oxides

Transposed temperature drop calorimetry and hightemperature drop solution calorimetry in molten 2PbO·B₂O₃ at 977 K were used to study the energetics of some manganese oxides, namely pyrolusite (MnO₂), bixbyite (Mn₂O₃), hausmannite (Mn₃O₄), and manganosite (MnO). The enthalpies of oxidation at 298 K in the manganeseoxygen system, which were determined by appropriate thermodynamic cycles, were (in kJ/mol of oxygen): –441.4 ± 5.8 for the reaction 6MnO + O₂→ 2Mn₃O₄, –201.8 ± 8.7 for the reaction 4Mn₃O₄+ O₂→ 6Mn₂O₃, and –162.1 + 7.2 for the reaction 2Mn₂O₃+ O₂→ 4MnO₂. These values agreed very well with previous data that were obtained using equilibrium measurements that were reported in the literature. Thus, direct calorimetric measurements were well suited to obtain reliable enthalpy of formation data for oxides that contain manganese in the 2+, 3+, and 4+ states. Using these new values of enthalpies and reliable standard entropies, the phase-stability diagram of the manganeseoxygen system was constructed.     

Equilibrium Studies of Fe in Alkali Phosphate Glasses

The Fe²⁺-Fe³⁺ equilibrium in binary Na₂O-P₂O₅, glasses was studied by equilibrating glass melts at different temperatures in air. The enthalpy change (δH) of the reaction 1/2Fe₂O₃⇌FeO+1/4O₂ was calculated for 4 glasses. The results indicate that (1) the equilibrium shifts toward the oxidized state as the Na₂O content of the glass increases (plots of log ([Fe²⁺]/[Fe³⁺]) vs mol% alkali were linear) and (2) Δ H values for glasses of different composition are nearly equal but differ from the standard (calculated) value for the reaction. The experimental ΔH values were nearly equal to that for the reaction FePO₄→1/3 Fe₃(PO₄)²+ 1/6P₂O₅+1/4O₂, indicating that Fe forms phosphate or polyphosphate configurations in the Na₂O-P₂O₅ glasses. In certain of the glasses studied a faint-pink solid precipitated; its X-ray diffraction pattern indicated that its principal component is crystalline Na₂Fe¹¹¹P₃O₁₀.     

Effect of Metal Oxide Additions on the High-Temperature Electrical Conductivity of Alumina

Several metal oxide additions were made to typical 99 and 96% alumina compositions to study their effect on the electrical conductivity of alumina from 500° to 1400°C. The metal oxide additions investigated were CO₂O₃, Cr₂O₃, CuO, Fe₂O₃, MnO₂, NiO, and TiO₂. Using a guarded two-probe technique, dc resistivities were measured on nonporous ceramic specimens. Additions of 0.5 to 2 mole % Co₂O₃, 2 mole % CuO, 1 mole % Fe₂O₃, or 2 mole % NiO to either a 96 or a 99% alumina composition increased the electrical resistivity. The addition of 1 mole % Cr₂O₃ to either a 96 or a 99% alumina showed practically no change in the resistivity. All changes in resistivity seemed to be structure dependent.     

Electrical Properties and Cation Valencies in Mn3O4

The electrical conductivity and thermopower of Mn₃O₄ were measured in the temperature range 920° to 1530°C. Electrical conduction in cubic Mn₃O₄ is explained by the small polaron hopping of electron holes between Mn⁴⁺ and Mn³⁺ on octahedral sites. The concentrations of Mn⁴⁺ and Mn³⁺ are governed by the disproportionation equilibrium 2Mn _oct ³⁺⇄Mn _oct ⁴⁺+ Mn _oct ²⁺. This model also explains the electrical behavior of NiMn₂O₄ and CuMn₂O₄.     

Chemical Reactions of Ultraphosphate Glasses with Water at Various Temperatures

The chemical reactions between P₂O₅-ZnO-H₂O ultraphosphate glasses and water were characterized between room temperature and 500°C, using thermogravimetry, differential scanning calorimetry, X-ray diffraction, and ³¹P nuclear magnetic resonance. Water adsorption and hydrolysis reactions of the glass leads to the formation of H₃PO₄ and crystalline ZnH₂P₂O₇ below 200°C. The rate of water adsorption increases, owing to the hygroscopicity of the hydrolysis products of the glass. Devitrification occurs at 250°C via surface reactions. The microstructure of the devitrified glass consists of crystalline Zn₂P₄O₁₂ and a liquid phase containing hydrolysis products of P₂O₅ like metaphosphoric acid (HPO₃) _n. Devitrification is finally followed by water desorption at higher temperatures.     

Piezoelectric Properties of Pb(Mg1/3Nb2/3)O3 PbTiO3 -PbZrO3 Ceramics Modified with Certain Additives

Effects of additives on the piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-PbZrO₃ ceramics in a perovskite-type structure are described. The tetragonality of Pb(Mg_1/3Nb_2/3)_0.375-Ti_0.375Zr_0.25O₃ ceramics increased with the addition of NiO, Cr₂O₃, or Fe₂O₃ but decreased with the addition of MnO₂ or CoO. The dielectric and piezoelectric properties of the base composition were improved markedly through selection of additives in proper amounts. Addition of NiO yielded a high dielectric constant and planar coupling coefficient for compositions at the morphotropic transition boundary. High mechanical Q -factors and low electrical dissipation factors were obtained by addition of MnO₂. Addition of both NiO and MnO₂ produced a mechanical Q -factor of 2051 and a planar coupling coefficient of 0.553. The resonant frequency of Pb(Mg_1/2Nb_2/3)_0.4375Ti_0.4375 zr_0.125O₃ containing MnO₂ had very low temperature and time dependence. The microstructure indicated that ceramics with a high mechanical Q -factor had a fine, uniform grain structure. Addition of Cr₂O₃ retarded grain growth and addition of MnO₂, NiO, CoO, or Fe₂O₃ promoted grain growth in the ternary system.     

Oxidation of Manganese Ferrite

The oxidation of manganese ferrite (MnFe₂O₄) in air has been studied in the temperature range 750° to 1150°C. Between 1050° and 1150° a homogeneous oxidation takes place, resulting in a spinel phase of a defect type containing up to 10% of the manganese in the trivalent state. At 1050° and below, bixbyite (Mn₂O₃) and hematite (Fe₂O₃) are precipitated. The kinetics indicate that initially a diffusion-limited homogeneous reaction takes place, followed by precipitation and grain growth. At lower temperatures, well-defined Widmanstätten precipitates are formed; at higher temperatures, recrystallization alters these precipitates. The oxidation of manganese ferrite can be strongly retarded by a ceramic glaze, offering a practical method of preparing the material by air firing.     

Reaction Kinetics of Polycrystalline Yttrium Iron Garnet

The formation of yttrium iron garnet, Y₃Fe₂-(FeO₄)₃, starting with (1) Fe₂O₃ and Y₂O₃ and (2) Fe₃O₄ and Y₂O₃, was studied as a function of temperature and time by means of magnetic moment and X-ray measurements. The reaction began at 600°C. and was completed at 1200°C. The perovskite phase appeared only between 600° and 800°C. Above 1200°C. only the garnet phase was present. The microwave line width and g -factor at 9303 mc. per second were also measured and related to the preparation variables.     

Kinetics of Solid-State Reaction of Bi2O3 and Fe2O3

Solid-state reactions of equimolar mixtures of Bi₂O₃ and Fe₂O₃ from 625° to 830°C and their kinetics were investigated. The reaction rates were determined from the integrated X-ray diffraction intensities of the strongest peaks of the reactants and products. The activation energy for the formation of BiFeO₃ was 96.6±9.0 kcal/mol; that for a second-phase compound, Bi₂Fe₄O₉, which formed above 675°C, was 99.4±9.0 kcal/mol. Specific rate constants for these simultaneous reactions were obtained. The preparation of single-phase BiFeO₃ from the stoichiometric mixture of Bi₂O₃ and Fe₂O₃ is discussed.     

Spray Pyrolysis of Fe3O4–BaTiO3 Composite Particles

Fe₃O₄–BaTiO₃ composite particles were successfully prepared by ultrasonic spray pyrolysis. A mixture of iron(III) nitrate, barium acetate and titanium tetrachloride aqueous solution were atomized into the mist, and the mist was dried and pyrolyzed in N₂ (90%) and H₂ (10%) atmosphere. Fe₃O₄–BaTiO₃ composite particle was obtained between 900° and 950°C while the coexistence of FeO was detected at 1000°C. Transmission electron microscope observation revealed that the composite particle is consisted of nanocrystalline having primary particle size of 35 nm. Lattice parameter of the Fe₃O₄–BaTiO₃ nanocomposite particle was 0.8404 nm that is larger than that of pure Fe₃O₄. Coercivity of the nanocomposite particle (390 Oe) was much larger than that of pure Fe₃O₄ (140 Oe). These results suggest that slight diffusion of Ba into Fe₃O₄ occurred.     

Dissolution of Iron in Silicate Melts

The oxidation and dissolution of metallic iron in silicate melts were investigated. The base composition consisted of Idaho soil with quartz and potassium feldspars as primary phases. Iron immersed in melts of unaltered soil and SiO₂-K₂O underwent minimal oxidation at 1400°C. Melts consisting of soil, 10 wt% of added K₂O, and 5-20 wt% of added Fe₂O₃ were capable of dissolving Fe. Progressively greater Fe dissolution occurred with increasing Fe₂O₃ content. A melt containing 20 wt% Fe₂O₃ dissolved 10 wt% Fe within 3 h. Melts containing greater than 10 wt% Fe₂O₃ crystallized almost entirely as magnetite (Fe₃O₄) and augite (Ca(Mg,Fe(2+))(SiO₃)₂). The data obtained also suggest that added Fe₂O₃ contributed to an increased rate of oxygen diffusion in these melts.     

Syntheses and Unit-Cell Determination of Ba3V4O13 and Low-and High-Temperature Ba3P4O13

The syntheses and the results of unit-cell determinations ofBa₃V₄O₁₃ and the two forms (low- and high-temperature) of Ba₃P₄O₁₃ are presented. Ba₃V₄O₁₃ crystallizes in the monoclinic system, space group Cc or C2/c with unit-cell dimensions a=16.087, b=8.948, c=10.159 (x10nm), β=114.52° Low-Ba₃P₄O₁₃ crystallizes in the triclinic system, space group P1 or P1 with unit-cell dimensions a=5.757, b=7.243, c=8.104 (x10 nm) α=82.75°, β=73.94°, γ=70.71°. Low-Ba₃P₄O₁₃ transforms at 870°C into high-Ba₃P₄O₁₃ which crystallizes in the orthorhombic system, space group Pbcm (No. 57) (or Pbc2, No. 29) with unit-cell dimensions a =7.107, b=13.883, c=19.219 (x10 nm). No relations have been found between the structures of the tribarium tetravanadate and the tribarium tetraphosphate.     

Phase Relations in the System Iron Oxide—Cr2O3 in Air

The quenching method has been used to determine approximate phase relations in the system iron oxide-Cr₂O₃ in air. Only two crystalline phases, a sesquioxide solid solution (Fe₂O₃–Cr₂O₃) with corundum structure and a spinel solid solution (approximately FeO ·Fe₂O₃–FeO – Cr₂O₃), occur in this system at conditions of temperature and O₂ partial pressure (0.21 atm.) used in this investigation. Liquidus temperatures increase rapidly as Cr₂O₃ is added to iron oxide, from 1591°C. for the pure iron oxide end member to a maximum of approximately 2265°C. for Cr₂O₃. Spinel(ss) is the primary crystalline phase in iron oxide-rich mixtures and sesquioxide (ss) in Cr₂O₃–rich mixtures. These two crystalline phases are present together in equilibrium with a liquid and gas (po₂= 0.21 atm.) at approximately 2075°C.     

Conversion of Tetranary Borate Glasses to Phosphate Compounds in Aqueous Phosphate Solution

In our earlier work, it was found that particles of a ternary alkali-borate glass, containing either CaO or BaO, converted completely to a crystalline phosphate of calcium or barium when reacted in an aqueous phosphate solution at 37°C. The present work is an extension of our earlier work to investigate the conversion of tetranary borate glass with the composition 10Li₂O·10CaO·10(AeO or T₂O₃)·60B₂O₃ (weight percent), where Ae is the alkai-earth metal Mg or Ba, and T is the transition metal La, Sm, or Dy. In the experiments, particles of each glass (150–300 μm) were reacted in 0.25 M K₂HPO₄ solution with a starting pH of ∼9.0 at 37°C. Weight loss and pH measurements indicated that the reaction was complete after 30–50 h, yielding an amorphous product. X-ray fluorescence showed that the as-formed product consisted of a calcium phosphate phase that contained the alkali-earth metal or transition metal present in the starting glass. Heating the as-formed material for 8 h at 600°–700°C produced a mixture of two crystalline phosphates: calcium phosphate and an alkali-earth or transition metal phosphate. The kinetics and mechanism of converting tetranary borate glass to phosphate materials are discussed and compared with data from earlier work for the conversion of ternary borate glass.     

Oxygen Evolution During MnO-Mn3O4 Dissolution in a Borosilicate Melt

Foam evolution during dissolution of MnO-Mn₃O₄ pellets and powders in borosilicate glass was recorded photographically. The pellets were placed horizontally in transparent crucibles, covered with molten glass, and held at 1150°C. If the Mn₃O₄ content in pellets was more than 31 wt%, they developed foam after an initial foamless period. The length of the foamless period decreased and the duration of foaming increased as the Mn₃O₄ content increased. Batches prepared from MnO-Mn₃O₄ powders and frit, and soaked at 1150°C, foamed without an initial foamless period. The foam developed and collapsed before the set temperature was established within the melt and rose to a higher level than foam produced by pellets. Thermogravimetry of batches heated in 1 atm (∼10⁵ Pa) of O₂ shows oxidation at 400° to 600°C followed by mass loss due to volatilization and oxygen evolution.