Formation and Densification Behavior of MgAl2O4 Spinel: The Influence of Processing Parameters

Different types of dense stoichiometric and nonstoichiometric magnesium aluminate (MgAl₂O₄) spinel (MAS) ceramics were prepared following a conventional double-stage firing process using different commercially available alumina and magnesia raw materials. Stoichiometric, magnesia-rich, and alumina-rich spinels were sintered at 1500°–1800°C for 1–2.5 h. The influence of the different processing parameters (average particle size, degree of spinel phase, green density, mass of the powder compact, sintering temperature, holding time at the peak temperature, and starting composition) on the densification behavior of MAS was assessed by measuring the bulk density, apparent porosity, and water absorption capacity, and microstructural observations. Most of the MAS compositions tested exhibited excellent sintering properties.     

Grain-Boundary Migration in Nonstoichiometric Solid Solutions of Magnesium Aluminate Spinel: I, Grain Growth Studies

The grain-boundary mobility in magnesium aluminate spinel (MgO · nAl₂O₃) of magnesia-rich ( n < 1) and alumina-rich ( n > 1) compositions has been measured from normal grain growth in dense, hot-pressed samples. Over the temperature range 1200° to 1800°C, the mobility in magnesia-rich compositions is found to be greater than that in alumina-rich compositions by a factor of 10² to 10³. Within the alumina-rich field, the mobility varies by less than a factor of 10 over the composition range 1 > n > 1.56. Nearly stoichiometric spinels (1 < n < 1.07) form a variety of sources and starting materials exhibit boundary mobilities within a factor of 5 at fixed temperature, showing an impurity tolerance which has not been found in other ionic solids.     

Translucent Sintered MgAl2O4

A translucent polycrystalline MgAl₂O₄ ceramic was prepared from finely divided coprecipitated spinel in which a small amount of CaO added as a sintering aid was uniformly distributed. The CaO promotes densification through the formation of a liquid phase at the sintering temperatures. Depending on the sintering treatment, the relative density of the sintered spinel was 99.7 to ∼100% of theoretical. The in-line optical transmission was > 10% from 0.3 to 6.5 μm. Total transmission in the visible region was between 67 and 78%.     

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.     

Grain-Boundary Migration in Nonstoichiometric Solid Solutions of Magnesium Aluminate Spinel: II, Effects of Grain-Boundary Nonstoichiometry

The grain-boundary chemistry of magnesium aluminate spinel solid solutions MgO· n Al₂O₃ in which grain growth measurements were reported in part I has been investigated in order to understand the mechanism of grain-boundary migration. It is found that although segregation of impurity Ca and Si is common, much larger deviations in grain-boundary stoichiometry are present. There is an excess of Al and O relative to Mg at grain boundaries in all compositions. Grain-boundary migration appears to be rate-limited by solute drag from intrinsic defects accommodating lattice nonstoichiometry, rather than by extrinsic solutes, consistent with the observed impurity tolerance of grain-boundary mobility. Different rate-limiting defects are proposed for magnesia-rich and alumina-rich spinels.     

Reactive Synthesis of a Porous Calcium Zirconate/Spinel Composite with Idiomorphic Spinel Grains

Porous CaZrO₃/MgAl₂O₄ composites were synthesized in air by pressureless reactive sintering of an equimolar mixture of dolomite (CaMg(CO₃)₂), monoclinic zirconia ( m -ZrO₂), and α-alumina powders, with a 0.5 wt% lithium fluoride additive. The reaction behavior of the mixed powders (with/without LiF additive) was studied using high-temperature X-ray diffraction. A bulk porous composite resulted from sintering at 1300°C for 2 h (in a nearly closed container, so as to increase the LiF-doping effect), which consisted of fine grains (CaZrO₃ and MgAl₂O₄, ∼0.5–1 μm) and well-grown idiomorphic ones (MgAl₂O₄ octahedra ∼ 2–4 μm). The idiomorphic spinel grains were located around the inner walls of relatively large pores. The composite showed appreciably high bending strength (σ_f= 110 ± 8 MPa for a porosity of 31%). The porous CaZrO₃/MgAl₂O₄ composites can be applied as high-temperature filters and lightweight structural components.     

Deformation Mechanism of Fine-Grained Magnesium Aluminate Spinel Prepared Using an Alkoxide Precursor

Polycrystalline MgAl₂O₄ spinel with high purity and stoichiometric composition was prepared using alkoxide precursors. The average grain size of the polycrystal was fine (1.7 μm). The deformation mechanism of the polycrystal was investigated in air at temperatures of 1300°–1400°C. At 1300°C, oxygen lattice diffusion controlled the deformation, despite the fine grain size; however, increases in the temperature and applied stress caused cavities to nucleate and grow. Spinel possessed better creep resistance than alumina of comparative grain size. The effective diffusion coefficient was determined as follows: [formula omitted]     

Oxygen Diffusion in Magnesium Aluminate Spinel

Oxygen self-diffusion in MgAl₂O₄ single crystals was investigated by annealing the samples in ¹⁸O enriched gas at 98 kPa (1 atm) and measuring the tracer concentration profiles using a proton activation technique. The diffusion coefficients in the range 1625 to 1925 K for stoichiometric crystals are represented by:    
Oxygen diffusivity in alumina-rich nonstoichiometric samples is higher than in stoichiometric samples.     

Reducing the Sintering Temperature for MgO–Al2O3Mixtures by Addition of Cryolite (Na3AlF6)

The preparation of near stoichiometric spinel and alumina-rich spinel composites from Al₂O₃and MgO powders with the addition of Na₃AlF₆up to 4 wt% in the temperature range 700°–1600°C was studied; 98 wt% spinel containing 72 wt% Al₂O₃can be produced from the mixture of 72 wt% (50 at.%) Al₂O₃+ 28 wt% (50 at.%) MgO powders with the addition of 1 wt% Na₃AlF₆fired at 1300°C for 1 h. Spinels containing 81–85 wt% Al₂O₃can be produced from either the mixture of 90 wt% (78 at.%) Al₂O₃+ 10 wt% (22 at.%) MgO or the mixture of 95 wt% (88 at.%) Al₂O₃+ 5 wt% (12 at.%) MgO powders with the addition of 4 wt% Na₃AlF₆in the temperature range 1300°–1600°C by using a torch-flame firing for 3 min, followed by quenching in water, while the same system under slow cooling in a furnace results in spinel containing 74–76 wt% Al₂O₃. Microscopic studies indicate that the alumina-rich spinel composites consist of a continuous majority spinel phase and an isolated minority corundum phase, regardless of slow cooling in a furnace or quenching in water.     

Structure of Spinel

This paper reviews the crystal structure of compounds with the general formula AB₂X₄, which crystallize with the same atomic structure as the mineral spinel, MgAl₂O₄. Three degrees of freedom associated with the detailed atomic arrangements of spinels are considered here: (i) the lattice parameter, a ; (ii) the anion parameter, u ; and (iii) the cation inversion parameter, i. Oxide spinels are used as examples to explore the interrelationships between these parameters.     

Mineralizing Magnesium Aluminate Spinel Formation With B2O3

B₂O₃ mineralizes spinel formation from stoichiometric (1:1 mole ratio) calcined magnesia and alumina. After 3 h at 1100°C, X-ray diffraction (XRD) shows the mineralization effect of B₂O₃ is limited to 1.5 wt% additions with higher B₂O₃ contents leading to Mg₃B₂O₆ formation and reduced spinel content. Boron nuclear magnetic resonance, electron probe microanalysis (EPMA), scanning electron microscopy, transmission electron microscopy (TEM) and XRD reveal formation of a boron-containing liquid. Energy dispersive spectroscopy in the TEM and EPMA of the glassy phases formed from solidification of the liquid reveal that initially it is Mg borate, later becoming a magnesia-modified boroaluminate, composition suggesting dissolution–precipitation as opposed to templated growth as the mechanism of this liquid phase mediated mineralization.     

Sequential Precipitation of MgAl2O4 on Mg1-x CaxAl2O4 in Hot-Pressed MgO Single Crystals

In a hot-pressed and deformed MgO single crystal, precipitates of Mg_1-xCa_xAl₂O₄ spinel upon which MgAl₂O₄ spinel subsequently precipitated were observed and analyzed using transmission electron microscopy and scanning electron microscopy. This behavior is related to the respective solubility limits of CaO and Al₂O₃ in MgO at the hot-pressing temperature and may be aided by impurity segregation to the dislocations. The spinel selectively precipitated at the nodes of a dislocation network which was formed during [001] hot-pressing deformation, as a result of the reaction b₃= b₁+ b₂= (1/2) [011] + (1/2)     = [001]. The dislocation is sessile, and the precipitates have a <100>_matrix≨ <100>_spinel coherent relationship.     

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.     

Preparation of MgAl2O4 Spinel Powders via Freeze-Drying of Alkoxide Precursors

High-sinterability MgAl₂O₄ powder has been produced from alkoxide precursors via a freeze-drying method. Clear alumina sol and magnesium methoxide were used as starting materials in the process. The spinel powders were characterized by various techniques, such as thermal analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The tap density and sinterability of the spinel power are affected by the ball-milling techniques. Highly dense, transparent, polycrystalline MgAl₂O₄ has been obtained from these powders by sintering and hot isostatic pressing. Bimodal grain-size microstructure is observed in a HIPed sample.     

Ambient-Temperature Mechanical Response of Alumina–Fluoromica Laminates

Flexural delamination experiments were used to evaluate the mechanical performance of thermochemically stable alumina–fluoromica laminates. Hot-pressed, precracked laminate specimens, in which two MgAl₂O₄-spinel-coated alumina substrates were separated by a thin layer of fluorophlogopite (KMg₃(AlSi₃)O₁₀F₂), were tested in fourpoint flexure at room temperature. Two types of mechanical response were observed: steady-state delamination and brittle failure. Microstructural analysis showed that the delamination response was associated with fine (≤5 μm) grains of the mica; the brittle response occurred when the mica interphase consisted of large (>30 μm) grains that bridged the interphase. The steady-state strain-energy release rate ( G _ss) measured on the graceful, delaminating beams was 9.1 ± 0.4 Jm^–2 for randomly oriented ∼ 5–μm grains but only 2.8 ± 0.2 Jm^–2 for ∼1–μm grains that were aligned with easy-cleavage planes parallel to the laminate interfaces. The results suggested that debonding of the specimens occurred via cleavage of the mica grains. Observation of delamination cracks confirmed this point: propagation occurred within the fluoromica interphase rather than along the spinel/alumina or spinel/fluorophlogopite interfaces. The mechanical feasibility of laminate specimens without the protective spinel coating on the substrate containing the notch was also tested to address an issue related to the preparation of alumina fiber/mica interphase/alumina matrix composites. The delamination response again occurred for the case of a fine-grained mica interphase.     

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.     

Indirect Dissolution of Sapphire into Calcia-Magnesia-Alumina-Silica Melts: Electron Microprobe Analysis of the Dissolution Process

Spinel, MgAl₂O₄, has been observed to form on sapphire during sapphire dissolution into CaO-MgO-Al₂O₃-SiO₂ (CMAS) melts at 1450°. and 1550°C. Electron microprobe analysis was used to characterize the sapphire/melt interface for cases in which spinel did (indirect dissolution) or did not (direct dissolution) form on the sapphire during dissolution into CMAS melts. The concentrations of Al₂O₃, MgO, CaO, and SiO₂ were determined as a function of position within the spinel reaction product and in the adjacent melt. The rate-limiting steps for direct and indirect sapphire dissolution into CMAS melts are discussed.     

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.     

Formation and Densification Behavior of Mullite Aggregates from Beach Sand Sillimanite

Dense mullite aggregates with 60% and 70% Al₂O₃ have been prepared from precursor mixtures consisting of beach sand sillimanite and a high-purity aluminum hydroxide following conventional single- and double-stage firing processes. The bulk density (BD), apparent porosity (AP), and water absorption (WA) capacity of sintered mullite aggregates were found to be strongly influenced by the premullitization step of this precursor mixture. Mullite aggregates formed in a double-stage firing process exhibited higher BD and mullite content and lower AP and WA capacity in comparison with those obtained by the single-stage firing process. The values of coefficient of thermal expansion of sintered mullite aggregates are close to those found in the literature reports for high-purity stoichiometric mullite.     

Mechanochemical Synthesis of Magnesium Aluminate Spinel Powder at Room Temperature

MgAl₂O₄ spinel was successfully synthesized using a mechanochemical route that avoided the formation and calcination of its precursors at high temperatures. The method involved a single step in which γ-Al₂O₃–MgO, AlO(OH)–MgO, and α-Al₂O₃–MgO mixtures were milled at room temperature under air atmosphere. The formation of MgAl₂O₄ occurred faster with γ-Al₂O₃ than with AlO(OH) or α-Al₂O₃. After 140 h, the mechanochemical treatment of the γ-Al₂O₃–MgO mixture yielded 99% of MgAl₂O₄.