Analysis of Local Cation Arrangement in Mullite Using 29Si Magic-Angle Spinning Nuclear Magnetic Resonance Spectra

Local cation arrangements for mullites with various chemical compositions were examined using ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra and the X-ray Rietveld method. The structure of mullite was refined using the Rietveld method, and the relations between chemical composition and lattice constants were revised. ²⁹Si NMR spectra of mullites showed a main resonance at −86 ppm accompanied by weak resonances at −94, −90, and −81 to −82 ppm. These resonances were assigned to each local cation arrangement of TO₄ tetrahedra in mullite by calculating the chemical shift according to Sherriff and Grundy's method. The resonances at −81 to −82 ppm were assigned to the arrangement of the T(Si),T(Al)–O^*_c–T^* (Al) cluster, which has been considered to be rather unusual, and their population was found to increase with increase in the Al₂O₃ content in mullite.     

Cell Dimensions, Solid Solution, Polymorphism, and Identification of Mullite and Sillimanite

X-ray, optical, and chemical data are presented for sillimanites and for a wide range of natural and synthetic mullites. Single-crystal X-ray studies have revealed a new type of mullite (called S mullite) characterized by subsidiary sharp reflections in distinction to the extra diffuse reflections of common mullite (called D mullite). Atomic substitution of aluminum in D mullite leads to expansion of a and c but not of b, whereas substitution of iron and titanium in natural mullites gives a slight initial decrease in a and b followed by a subsequent increase; c increases uniformly for all concentrations. The data are consistent with solid solution ranging between the extremes 3Al₂O₃.2SiO₂, 2Al₂O₃.-SiO₂, and 3(Al_0.9Fe_0.1)₂O₃.2SiO₂. Cell dimensions of sillimanite vary only slightly. Consideration of the various methods of distinguishing mullite and sillimanite shows that the measurement of cell dimensions is the most reliable and for mullite has the added advantage that the S and D polymorphs may be distinguished and an estimate of the composition obtained for D mullite.     

Mullite Crystallization from SiO2-Al2O3 Melts

SiO₂-Al₂O₃ melts containing 42 and 60 wt% A1₂O₃ were homogenized at 2090°C (∼10°) and crystallized by various heat treatment schedules in sealed molybdenum crucibles. Mullite containing ∼78 wt% A1₂O₃ precipitated from the 60 wt% A1₂O₃ melts at ∼1325°± 20°C, which is the boundary of a previously calculated liquid miscibility gap. When the homogenized melts were heat-treated within this gap, the A1₂O₃ in the mullite decreased with a corresponding increase in the Al₂O₃ content of the glass. A similar decrease of Al₂O₃ in mullite was observed when crystallized melts were reheated at 1725°± 10°C; the lowest A1₂O₃ content (∼73.5 wt%) was in melts that were reheated for 110 h. All melts indicated that the composition of the precipitating mullite was sensitive to the heat treatment of the melts.     

High-Temperature Hydroxylation of Mullite

A plane-parallel, polished, 0.9 mm thick, single-crystal (001) plate of 2:1 mullite was treated for 6 h at 1600°C in an Ar/H₂O (90/10) gas mixture at 100 kPa. Optical microscopy studies and infrared (IR) reflection spectroscopy studies of the lattice vibrations yielded no evidence for change with respect to the untreated reference crystal. However, IR absorption spectroscopy showed that structurally bound OH groups were formed by the heat treatment in the Ar/H₂O gas mixture. IR absorption depth profile analysis showed a rather homogeneous OH distribution through the crystal. Five different hydroxyl groups were separated according to dipole orientations and peak positions: E ‖ a , ω _{a 1}= 3447 cm⁻¹, ω _{a 2}= 3579 cm⁻¹; E ‖ b , ω _{b 1}= 3456 cm⁻¹, ω _{b 2}= 3544 cm⁻¹; and E ‖ c , ω _{c 1}= 3498 cm⁻¹. All IR peaks were strongly broadened (between 90 and 150 cm⁻¹) because of a distribution in O-H binding distances caused by the real structure of mullite.     

Quantitative Analysis of High-Alumina Refractories Using X-ray Powder Diffraction Data and the Rietveld Method

Quantitative determination of phase abundance in high-alumina refractories has been performed using the Rietveld refinement method applied to X-ray powder diffraction data. The use of a "whole-pattern" method for analysis has allowed the simultaneous determination of accurate unitcell parameters and the phase abundance of major (mullite and cristobalite) and minor (quartz, corundum, and andalusite) phases. A comparison of the accurate unit-cell parameters, produced during refinement, with published data has allowed the composition of mullite to be estimated at 3:2 Al₂O₃:SiO₂. Cristobalite has been shown to be present in two distinct forms, both of which have been quantified in spite of severe overlap in their diffraction patterns. There is excellent agreement between SiO₂ and Al₂O₃ contents calculated from the measured phase contents and those measured by X-ray fluorescence spectrometry. The addition of fluorite in a known amount as an internal standard has allowed the estimation of the amount of amorphous material present.     

Structural Analysis of Orthorhombic Hafnia by Neutron Powder Diffraction

The crystal structure of orthorhombic HfO₂ synthesized at 600°C and 6 GPa was investigated by a time-of-flight neutron powder diffraction experiment. Rietveld analysis of these data revealed that the space group of this phase is Pbca. The refined lattice parameters are a ₀= 1.00177, b ₀= 0.52276, and c ₀= 0.50599 nm. The structure is derived from a distorted fluorite (CaF₂) structure by a b -glide parallel to the a -axis. The hafnium atom is in seven-fold coordination. The structure of orthorhombic HfO₂ is found to be the same as that of an orthorhombic ZrO₂, which occurs under high pressure above 3 GPa.     

Solid Solution Range and Microstructures of Melt-Grown Mullite

The solid solution range of melt-grown mullite was examined by crystal-chemical methods. The maximum Al₂O₃ content as determined by EDX was ∼83.6 wt%, 75 mol%, or the nominal composition 3Al₂O₃.SiO₂. For samples of overall composition 81 to 83 wt% Al₂O₃, extra lines indicating crystallographic superstructure appeared in Guinier X-ray patterns. The corresponding TEM microstructure consisted of a mullite matrix finely twinned on (001), the twins being 0.02 to 0.10 μm wide, with oriented exsolution of α-A1₂O₃, often twinned, also being present. The analogy between mullite superstructure and that of plagioclase feldspars, as well as the relevance of these findings to the SiO₂-Al₂O₃ metastable phase equilibria are discussed.     

Metastable Crystal Structure of Strontium- and Magnesium-Substituted LaGaO3

The metastable crystal structure of strontium- and magnesium-substituted LaGaO₃ (LSGM) was studied at room and intermediate temperatures using powder X-ray diffractometry and Rietveld refinement analysis. With increased strontium and magnesium content, phase transitions were found to occur from orthorhombic (space group Pbnm ) to rhombohedral (space group R [Threemacr] c ) at the composition La_0.825Sr_0.175Ga_0.825Mg_0.175O_2.825 and, eventually, to cubic (space group Pm [Threemacr] m ) at the composition La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8. At 500°C in air and at constant strontium and magnesium content, a phase transformation from orthorhombic (space group Pbnm ) to cubic (space group Pm [Threemacr] m ) was observed. For the orthorhombic modification, thermal expansion coefficients were determined to be α _a ,ortho = 10.81 × 10⁻⁶ K⁻¹, α _b ,ortho = 9.77 × 10⁻⁶ K⁻¹, and α _c ,ortho = 9.83 × 10⁻⁶ K⁻¹ (25°–400°C), and for the cubic modification to be α_cubic= 13.67 × 10⁻⁶ K⁻¹ (500°–1000°C).     

Revised Phase Diagram for the System Al2O3—SiO2

On the basis of 190 runs made up to 1860°C in sealed noble-metal containers the following revisions have been made in the equilibrium diagram for the system A1₂O₃–SiO₂. Mullite melts congruently at 1850°C. The extent of equilibrium solid solution in mullite at solidus temperature is from approximately 60 mole % Al₂O₃ (3/2 ratio) to 63 mole % A1₂O₃. Metastable solid solutions can be prepared up to about 67 mole % Al₂O₃. There is no evidence for stable solubility of excess SiO₂ beyond the 3/2 composition at pressures below 3 kbars. Refractive indices are presented for glasses containing up to 60 mole % Al₂O₃ and from them the composition of the eutectic is confirmed at 5 mole % SiO₂. The variation in lattice constants of the mullite solid solution is not an unequivocal guide to composition since mullites at one composition produced at different temperatures show differences in spacing, no doubt reflecting Al-Si ordering phenomena. The possibility of quartz and corundum being the stable assemblage at some low temperatures and pressures cannot be ruled out. A new anhydrous phase in the system is described, which was previously thought to be synthetic andalusite; it is probably a new polymorph of the Al₂SiO₅ composition with ortho-rhombic unit-cell dimensions a =7.55 A, b =8.27 A, and c = 5.66 A.     

Damage Tolerance of Silicon Carbide- and Alumina-Matrix Surface Composites

A method for the fabrication of a ceramic-matrix composite (CMC) layer on the surface of a monolithic substrate via chemical vapor infiltration (CVI) is described. Preforms consisted of tows of fibers wound onto the surface of monolithic cylindrical tubes. Nicalon fibers were wound onto mullite substrates and infiltrated with β-SiC from CH₃SiCl₃/H₂ gas mixtures in a cylindrical cold-wall reactor. Similarly, Nextel fibers were wound onto A1₂O₃ substrates and infiltrated with α-Al₂O₃ from AlCl₃/H₂/CO₂/N₂ gas mixtures. Composites with densities as high as 88% of the theoretical value were fabricated in 8 h. The effective fracture strength of the SiC- and Al₂O₃-matrix surface composites, as determined from diametral compression tests of C-ring specimens, was found to be insensitive to damage caused to the outer diameter by a Vickers indentation. The tolerance of the SiC-matrix surface composites to surface damage was retained in specimens subjected to oxidation at 1000°C for 6 h.     

Anisotropic Thermal Expansion of Tetragonal Zirconia Polycrystals

Thermal expansion coefficients (α _a and α _c ) in two crystallographic axes ( a and c ) of the tetragonal phase are measured at 25°–1200°C in ZrO₂–M₂O₃ (M = Sc, In, Yb) and in ZrO₂–YTaO₄. The difference between these two thermal expansion coefficients, α _c –α _a , decreases with M₂O₃ or YTaO₄ composition even though the tetragonality ( c/a ) behaves differently in these two systems. The locus of α _c =α _a represents a maximum tetragonality for the tetragonal phase, but not the phase boundary for the cubic phase. The relationships among thermal expansion, temperature, and composition are discussed.     

Cation Ordering and Domain Boundaries in Ca[(Mg1/3Ta2/3)1−xTix]O3 Microwave Dielectric Ceramics

Cation ordering and domain boundaries in perovskite Ca[(Mg_1/3Ta_2/3)_{1− x} Ti _x ]O₃ ( x =0.1, 0.2, 0.3) microwave dielectric ceramics were investigated by high-resolution transmission electron microscopy (HRTEM) and Rietveld analysis. The variation of ordering structure with Ti substitution was revealed together with the formation mechanism of ordering domains. When x =0.1, the ceramics were composed of 1:2 and 1:1 ordered domains and a disordered matrix. The 1:2 cation ordering could still exist until x =0.2 but the 1:1 ordering disappeared. Neither 1:2 nor 1:1 cation ordering could exist at x =0.3. The space charge model was used to explain the cation ordering change from 1:2 to 1:1 and then to disorder. A comparison between the space charge model and random layer model was also conducted. HRTEM observations showed an antiphase boundary inclined to the (111) _c plane with a projected displacement vector in the 〈001〉 _c direction and ferroelastic domain boundaries parallel to the 〈100〉 _c direction.     

Stoichiometry of Fluorotopaz and of Mullite Made from Fluorotopaz

Mixtures of alumina and silica containing 68–78 wt% alumina react above 600°C with 0.5 mol of SiF₄ per mole of alumina to form fluorotopaz. High-resolution X-ray powder diffraction data were used to determine very accurate cell parameters of fluorotopaz as a function of 1 wt% compositional increments. The samples containing 69–76 wt% A1₂O₃ were found to have a linear cell parameter relationship. Compositions outside that range show discontinuities in the cell parameters, indicating solid solution behavior between 69 and 76 wt% alumina. Within this range the composition of fluorotopaz may be written 2A1₂O₃·_xSiO₂· SiF₄ where 1.07 x 1.53. Pyrolysis of all compositions of fluorotopaz solid solution yields mullite whiskers containing 76.1 wt% alumina (65.2 mol%).     

Change in Chemical Composition of Mullite Formed from 2SiO2°3Al2O3 Xerogel During the Formation Process

The chemical composition of mullite which was termed from 2SiO₂3Al₂O₃ xerogel by firing was examined by analytical TEM. Mullite formed at 950°C firing showed around 66 mol% Al₂O₃, which was fairly Al₂O₃ rich compared with the bulk composition. The chemical composition of mullite gradually approached the bulk composition as the firing temperature increased to 1400°C and slightly departed again above that firing temperature.     

X-Ray Study of the Solid Solution of TiO, Fe2O3, and G, O3 in Mullite (3A12O3a2Si02)

A study of the solid solution of TiO₂, Fe₂O₃, and Cr₂0₃ in mullite was made by measuring the changes in lattice parameters and unit-cell volume. Synthetic mullite (3O₃-2SiO₂) was reacted with up to 12 weight % of the oxides at temperatures ranging from 1000° to 17000C. The approximate minimum temperature required for the formation of solid solution was 12000C. for Fe₂0₃ and 1400°C. for Cr₂O₃ and TiO₃. The maximum amount of solid solution found was 2 to 4% TiO₂ at 1600°C., 10 to 12% Fe₂O_s at 1300°C., and 8 to 10% Cr_ZO₃ at 1600OC. Lattice parameters and unit-cell volumes for each solid solution series increased with increasing amounts of foreign oxide. There was good agreement between the calculated and observed increase in cell dimensions for the iron oxide series. Except in the case of titania, there was good agreement between X-ray data and petrographic observations.     

Reaction-Forming of Mullite Ceramics Using an Aqueous Milling Medium

Mullite and mullite/ZrO₂ ceramics were fabricated starting from Si/Al₂O₃ and Si/Al₂O₃/ZrO₂ powder mixtures, which were mixed and attrition milled with TZP balls in water. Isopressed powder compacts were subjected to a heat treatment in air, during which the Si was oxidized to SiO₂. At } 1410°C, reaction between Al₂O₃ and SiO₂ occurred, resulting in mullite (3Al₂O₃·2SiO₂). Depending on the composition of the starting powders, the end product was either single-phase mullite or a mullite composite. The reaction process was monitored by thermogravimetry and dilatometry. It was found that the microstructure and mechanical properties of the reaction-formed mullite ceramics were significantly improved by ZrO₂ additions.     

High-Temperature Mechanical Properties of Ceramic Materials: IV, Sintered Mullite Bodies

An attempt was made to sinter relatively pure 3A1₂O₃-2SiO₂ and 2A1₂O₃-SiO₂ compositions to low porosities at 1710° and 1650°C, respectively, using an addition of 1% MgO to each body to facilitate the reaction. The 3A1₂O₃-2SiO₂ body sintered to a porosity of 7.1% and was practically all mullite. The 2Al₂O₃SiO₂ body sintered to a porosity of 10.9% and was composed of mullite and corundum. Strength and elastic modulus measurements were made at several temperatures up to 1200°C, and some observations of the load-bearing properties were made.     

Tetragonal-to-Cubic Structural Phase Transition in Pollucite by Low-Temperature X-ray Powder Diffraction

The tetragonal-to-cubic structural phase transition in pollucite (CsAlSi₂O₆) was investigated using low-temperature X-ray powder diffraction in the temperature range of 93 to 298 K, and the lattice constants were refined with Rietveld analysis. It was found that CsAlSi₂O₆ had a tetragonal phase with a space group of I 4₁/acd in the temperature range of 93 to 248 K, a = 1.36337(4) nm, c = 1.36988(6) nm at 248 K, and underwent a phase transition from tetragonal to cubic with a space group of Ia-3 in the temperature range of 248 to 273 K, a = 1.36645(3) nm at 273 K.     

Processing and Microstructure of Mullite-Zirconia Composites Prepared from Sol-Gel Powders

A high-purity stoichiometric mullite precursor was obtained by hydrolysis of the alkoxides Al(OC₃H₇)₃ and Si(OC₂H₂)₄. Fully sintered mullite ceramics can be prepared from sol-gel powders by sintering them at 1600°C for 4 h in air with the addition of 15 to 20 Vol% ZrO₂ or 1 to 3 mol% Y₂O₃ or both. Introduction of 1 to 3 mol% Y₂O₃ aids the retention of tetragonal ZrO₂; the volume fraction of t -ZrO₂ retained increases with increasing Y₂O₃ content. The maximum t -ZrO₂ retained reaches 34% in a matrix of synthetic mullite with 3 mol% Y₂O₃, but most of this t -ZrO₂ does not undergo stress-induced transformation during grinding.     

Thermal Behavior of Alumina—Silica Xerogels During Calcination

Xerogels of 3Al₂O₃·2SiO₂ mullite were prepared by hydrolyzing Al(NO₃)₃·9H₂O and Si(OC₂H₅)₄ solutions with pH values of 8.3, 9.4, 10.1, and 10.4; the xerogels were composed of a combination of singlephase and diphasic materials. A strong alkaline solution enhanced bayerite formation in the gels. Mullite from the diphasic xerogels was produced by reacting θ-Al₂O₃ with amorphous SiO₂, whereas mullite from the single-phase xerogels was transformed from Al-Si spinel. For the single-phase xerogel, the DTA curve closely resembled the kaolinite-to- mullite reaction. For the diphasic xerogels, the Al³⁺ -containing solution gelled to pseudoboehmite, which transformed to bayerite in solution. The bayerite then decomposed to η-Al₂O₃ and to θ-Al₂O₃ sequentially on heating.