Growth of Single-Crystal and Polycrystalline Thin Films of MgAl2O4 and MgFe2O4

Single-crystal and polycrystalline films of Mg-Al₂O₄ and MgFe₂O₄ were formed by two methods on cleavage surfaces of MgO single crystals. In one procedure, aluminum was deposited on MgO by vacuum evaporation. Subsequent heating in air at about 510°C formed a polycrystalline γ-Al₂O₈ film. Above 540°C, the γ-Al₂O, and MgO reacted to form a single-crystal MgAl₂O₄ film with {001} MgAl₂O₄‖{001} MgO. Above 590°C, an additional layer of MgAl₂O₄, which is polycrystalline, formed between the γ-Al₂O₃ and the single-crystal spinel. Polycrystalline Mg-Al₂O₄ formed only when diffusion of Mg²⁺ ions proceeded into the polycrystalline γ-Al₂O₃ region. Corresponding results were obtained for Mg-Fe₂O₄. MgAl₂O₄ films were also formed on cleaved MgO single-crystal substrates by direct evaporation, using an Al₂O₃ crucible as a source. Very slow deposition rates were used with source temperatures of ∼1350°C and substrate temperatures of ∼800°C. Departures from single-crystal character in the films may arise through temperature gradients in the substrate.     

Electrochemical Determination of the Gibbs Energy of Formation of MgAl2O4

The standard Gibbs energy of formation of the spinel MgAl₂O₄ from component oxides, MgO and α-Al₂O₃, has been determined in the temperature range 900 to 1250 K using a solid-state cell incorporating single-crystal CaF₂ as the solid electrolyte. The cell can be represented as—Pt,O₂,MgO+MgF₂|CaF₂|MgF₂+MgAl₂O₄+α-Al₂O₃,O₂,Pt—The standard Gibbs energy of formation from binary oxides, computed from the reversible emf, can be represented by the expression—capdelta G °_f,ox=−23600 − 5.91 T (±150) J/mol—The 'second-law' enthalpy of formation of MgAl₂O₄ obtained in this study is in good agreement with high-temperature solution calorimetric studies reported in the literature.     

Quaternary System Al2O3–CaO–MgO–SiO2: II Study of the Crystallization Volume of MgAl2O4

Solid-state compatibility and melting relations of MgAl₂O₄ in the quaternary system Al₂O₃–CaO–MgO–SiO₂ were studied by firing and quenching selected samples located in the 65 wt% MgAl₂O₄, plane followed by microstructural and energy dispersive X-ray analysis. A projection of the liquidus surface of the primary crystallization volume of MgAl₂O₄ was constructed from CaO, SiO₂ and exceeding Al₂O₃, not involved in stoichiometric MgAl₂O₄ formation; those three amounts were recalculated to 100 wt%. The temperature and character of six invariant points, where four solids co-exist with a liquid phase, were defined. One maximum point was localized and the positions of the isotherms were tentatively established. The effect of CaO, SiO₂, and Al₂O₃ impurities on the high temperature behavior of spinel materials was also discussed.     

High-Strain-Rate Superplasticity in Y2O3-Stabilized Tetragonal ZrO2 Dispersed with 30 vol% MgAl2O4 Spinel

High-strain-rate superplasticity is attained in a 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ polycrystal (3Y-TZP) dispersed with 30 vol% MgAl₂O₄ spinel: tensile elongation at 1823 K reached >300% at strain rates of 1.7 × 10⁻²– 3.3 × 10⁻¹ s⁻¹. The flow behavior and the microstructure of this material indicate that the MgAl₂O₄ dispersion should enhance accommodation processes necessary for grain boundary sliding. Such an effect is assumed to arise from an enhancement of the cation diffusion by the dissolution of Al and Mg ions into the ZrO₂ matrix and from stress relaxation due to the dispersed MgAl₂O₄ grains.     

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.     

Molten Salt Synthesis of Magnesium Aluminate (MgAl2O4) Spinel on Ti3AlC2 Substrate

A MgAl₂O₄ (MA) spinel layer was synthesized on Ti₃AlC₂ substrate through the molten salt synthesis (MSS) method. The Ti₃AlC₂ substrate was immersed in MgCl₂·6H₂O powders and treated at 800°, 850°, and 900°C for 4 h in air. A continuous and 10-μm-thick MgAl₂O₄ layer was obtained at 900°C, by which the surface hardness of Ti₃AlC₂ can be effectively improved. The combined scanning electron microscopy observations and crystal morphology simulation further revealed that the as-formed MgAl₂O₄ presents tetragonal bipyramids morphology with (400)-orientation.     

Interdiffusion in the System MgO-MgAl2O4

Interdiffusion coefficients in single-crystal MgO were determined using an MgO-MgAl₂O₄ diffusion couple. For a concentration of 1 mol% Al₂O₃ in MgO, the interdiffusion coefficient can be expressed as D =2.0±0.2 exp (−76,000±3,000/ RT ) for the MgO-MgAl₂O₄ couple. This relation compares well with previous measurements in the MgO-Al₂O₃ system. The interdiffusion coefficients, which increased with the mol fraction of cation vacancies, were in the range of 10⁻⁸ to 10⁻¹⁰ cm²s⁻¹ for the concentrations and temperatures studied. Diffusion was enhanced below 1640°C if powdered MgAl₂O₄ was used. Self-diffusion coefficients for Al³⁺ ions in MgO were calculated; Al³⁺ diffuses faster than Cr³⁺ in MgO.     

Electrical Conductivity of MgAl2O4 and Y3A15O12

The electrical conductivities of single crystal and polycrystalline MgAl₂O₄ and Y₃Al₅O₁₂ were measured to 1260 K using a three-contact, guard-ring technique. The electrical conduction mechanisms change with temperature, with anomalous oxygen pressure and time-dependent inflections in log σ versus T⁻¹ curves between 900 to 1000 K. The conduction processes of Y₃Al₅O₁₂ and MgAl₂O₄ appear to be similar and possibly related to A1³⁺ ion diffusion.     

Oxidation Protection of MgO–C Refractories by Means of Al8B4C7

The effect of Al₈B₄C₇ used as an antioxidant in MgO–C refractories and the behavior of Al₈B₄C₇ in CO gas were investigated in the present study. Al₈B₄C₇ was found to react with CO gas, to form Al₂O₃( s ), B₂O₃( l ), and C( s ), at temperatures >1100°C. The Al₂O₃ reacts with MgO to form MgAl₂O₄ near the surface of the material. At the same time, B₂O₃( l ) evaporates and reacts with MgO, to form a liquid phase, at >1333°C, the eutectic point between 3MgO·B₂O₃ and MgO. The coexistence of the liquid and MgAl₂O₄ makes the protective layer more dense, thus inhibiting oxidation of the refractory. At >1333°C, the process apparently is controlled by oxygen diffusion, whereas it is controlled by chemical reaction when the temperature is <1333°C.     

Elastic Modulus and Fracture Toughness of Ternary PbO-ZnO-B2O3 Glasses

The elastic moduli and fracture toughnesses of a series of PbO-ZnO-B₂O₃ glasses were measured for different PbO/ZnO ratios and for B₂O₃ contents from 30 to 70 mol%. Substituting ZnO for PbO increased both the elastic modulus and fracture toughness at all B₂O₃ levels with the fracture toughness being related to the elastic modulus. Structural effects on these properties are discussed.     

Microstructure and Electrical Properties of MgAl2O4 Thin Films for Humidity Sensing

Active elements for humidity sensors based upon MgAl₂O₄ thin films or sintered pellets were investigated. Thin films were deposited on Si/SiO₂ substrates by radiofrequency (rf) sputtering. Sintered MgAl₂O₄ pellets were prepared by traditional ceramic processing. Scanning electron microscopy (SEM) analysis showed that the thin films were rather dense and homogeneous, made up of clustered particles of about 20–30 nm, while the pellets showed a wide pore-size distribution. X-ray photoelectron spectroscopy (XPS) demonstrated that the thin films have a stoichiometry close to that of MgAl₂O₄. Sintered MgAl₂O₄ is crystalline, while it is disordered in thin-film form. The presence of two different components of the Al 2 p peaks was correlated with the structural difference between pellets and thin films. The relationship between good film–substrate adhesive properties and the chemical composition at the interface was studied. The electrical properties of the sensing elements were studied at 40°C in environments at different relative humidity (RH) values between 2% and 95%, using ac impedance spectroscopy. MgAl₂O₄ thin films showed interesting characteristics in terms of their use in humidity-measurement devices. Resistance versus RH sensitivity values showed variations as high as 4 orders of magnitude in the RH range tested for thin films, and 5 orders of magnitude for pellets. The differences in the electrical behavior of MgAl₂O₄ pellets and thin films were correlated with their different microstructures.     

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.     

Thermochemistry of MgAl2O4-Al8/3O4 Defect Spinels

Solution calorimetry of MgAl₂O₄-Al_8/3O₄ solid solutions was performed in a molten 2PbO · B₂O₃ solvent at 975 K. The results indicate small negative heats of mixing, relative to spinel standard states for both end-members. These data were combined with information on the energetics of the α-γ transition in Al₂O₃ and on the MgAl₂O₄-Al_8/3O₄ (MgO-Al₂O₃) subsolidus phase relations to estimate the partial molar entropy of mixing of γ-Al_8/3O₄ in the solid solution. This entropy is much less positive than that calculated from several models for the configurational entropy of mixing of magnesium, aluminum, and vacancies on octahedral and/or tetrahedral sites. The data suggest a good deal of local order to be present in the solid solutions, consistent with negative enthalpies of mixing and entropies of mixing far less than ideal configurational values.     

Modification of MgAl2O4 Microwave Dielectric Ceramics by Zn Substitution

MgAl₂O₄ microwave dielectric ceramics were modified by Zn substitution for Mg, and their dielectric characteristics were evaluated, along with their structures. Dense (Mg_{1− x} Zn _x )Al₂O₄ ceramics were obtained by sintering at 1550°–1650°C in air for 3 h, and the (Mg_{1− x} Zn _x )Al₂O₄ solid solution was determined in the entire composition range. With Zn substitution for Mg, the dielectric constant ɛ of MgAl₂O₄ just varied from 7.90 to 8.56, while the Q × f value had significantly improved up to a maximal value of 106 000 GHz at x =1.0. Moreover, the τ_f of MgAl₂O₄ ceramics had declined from −73 to −63 ppm/°C.     

Exsolution of β-Ga2O3 Crystalline Solutions in the System MgAl2O3-Ga2O3

The subsolidus phase equilibrium diagram for the pseudobinary join MgAl₂O₄-Ga₂O₃ was determined. The shape of the exsolution boundary was obtained by heat-treating samples pre- equilibrated at 1600°C. Crystalline solubility of Ga₂O₃ in MgAl₂O₄ decreased from 73 mole % at 1600°C to 55 mole % at 1200°C. The crystalline solution was formed by the replacement of Mg²⁺ions by Ga³⁺ ions to produce a cation defect spinel. The phase precipitated was the mono-clinic δ-Ga₂O₃ (=δ-Al₂O₃ structure). Changes in the ratios of relative X-ray diffraction intensities indicated that the crystalline solutions also disorder with temperature.     

Chemical Interaction Between LiF and MgAl2O4 Spinel During Sintering

Reactions between LiF and MgAl₂O₄ at temperatures up to 1500°C are examined with a variety of tools, including differential scanning calorimetry, thermo-gravimetric analysis, X-ray diffraction, and scanning electron microscopy. LiAlO₂ and MgF₂ are found to be the active reaction products at these temperatures. A transient liquid phase comprising MgF₂ and LiF forms at intermediate temperatures, but then is consumed at higher temperatures during the reformation of MgAl₂O₄. If processed as an uncompacted powder mixture, all of the initial LiF in the system eventually vaporizes at temperatures exceeding 1300°C. A new reaction sequence relevant to the densification of LiF-doped MgAl₂O₄ spinel is proposed.     

Synthesis of an Al/MgAl2O4In situ Metal Matrix Composite from Silica Gel

An aluminum/MgAl₂O₄ in situ metal matrix composite has been synthesized using silica gel containing ∼98% SiO₂ in an Al–5Mg alloy. The thermodynamics and kinetics of MgAl₂O₄ formation have been discussed in detail. A transition phase of composition between MgO and MgAl₂O₄ has been detected in the SEM-EDS analysis of the particles extracted from the composite by a 25% NaOH solution. This confirms the gradual transformation of MgO to MgAl₂O₄ by the reaction 3SiO₂( s )+2MgO( s )+4Al( l )→2MgAl₂O₄( s )+3Si( l ). The stoichiometry, n , of MgAl₂O₄ has been found to sustain close to 1 and the crystallite growth of MgAl₂O₄ has been stopped at D ∼30 nm in the composites held at 750°C up to 10 h.     

Ternary System Al2O3-MgO-CaO: I, Primary Phase Field of Crystallization of Spinel in the Subsystem MgAl2O4-CaAl4O7-CaO-MgO

Using a novel experimental procedure in the field of ceramics/materials science that is based on the precise microanalysis (scanning electron microscopy, coupled with wavelength-dispersive spectroscopy) of the phases that are present in equilibrated specimens, the solid-state compatibility relations in the subsystem MgAl₂O₄-CaAl₄O₇-CaO-MgO and the melting relationships in the subsystems MgAl₂O₄-CaAl₂O₄-MgO and MgAl₂O₄-CaAl₂O₄-CaAl₄O₇ were established. The primary phase field of crystallization of spinel in the above-mentioned subsystem, MgAl₂O₄-CaAl₄O₇-CaO-MgO, was determined subsequently. The temperature, composition, and character of the ternary invariant points of the subsystem were established, and the ranges of the solid solutions in periclase, spinel, monocalcium aluminate, and dicalcium aluminate also were studied and determined, up to 1725°C.     

Ternary System Al2O3—MgO—CaO: Part II, Phase Relationships in the Subsystem Al2O3—MgAl2O4—CaAl4O7

Solid-state compatibility and melting relationships in the subsystem Al₂O₃—MgAl₂O₄—CaAl₄O₇ were studied by firing and quenching selected samples located in the isopletal section (CaO·MgO)—Al₂O₃. The samples then were examined using X-ray diffractomtery, optical microscopy, and scanning and transmission electron microscopies with wavelength- and energy-dispersive spectroscopies, respectively. The temperature, composition, and character of the ternary invariant points of the subsystem were established. The existence of two new ternary phases (Ca₂Mg₂Al₂₈O₄₆ and CaMg₂Al₁₆O₂₇) was confirmed, and the composition, temperature, and peritectic character of their melting points were determined. The isothermal sections at 1650°, 1750°, and 1840°C of this subsystem were plotted, and the solid-solution ranges of CaAl₄O₇, CaAl₁₂O₁₉, MgAl₂O₄, Ca₂Mg₂Al₂₈O₄₆, and CaMg₂Al₁₆O₂₇ were determined at various temperatures. The experimental data obtained in this investigation, those reported in Part I of this work, and those found in the literature were used to establish the projection of the liquidus surface of the ternary system Al₂O₃—MgO—CaO.     

Formation of N-phase and Phase Relationships in MgO–Si2N2O–Al2O3 System

Formation of N-phase in the system Mg,Si,Al/N,O was studied. Its composition was confirmed to be MgAl₂Si₄O₆N₄ (2Si₂N₂OMgAl₂O₄). Subsolidus phase relationships in the MgO–Si₂N₂O-Al₂O₃ system were determined. The results are discussed by comparing with two similar systems, CaO-and Y₂O₃–Si₂N₂O–Al₂O₃.