Decomposition of Mullite by Silica Volatilization

Thermal decomposition of mullite into corundum was investigated using a high-temperature X-ray single-crystal camera equipped with a gas-flame furnace and by scanning electron microscopy and electron probe microanalysis (EPMA). When heated to ∼1750°C, mullite decomposed to corundum by the liberation of the SiO₂ component with topotaxial relations of:

• (1) 

  (310)_mull∥(001)_cor; [001]_mull∥[110]_cor
• (2) 

  (130)_mull∥(001)_cor; [001]_mull∥[110]_cor
• (3) 

  (110)_mull∥(001)_cor; [001]_mull∥[110]_cor

Thus, it was considered that, when mullite decomposed into corundum, their oxygen close-packed planes were almost preserved. The SEM photographs showed that the crystals of the developed corundum are prismatic and ∼5 μm wide. The EPMA showed that the phase boundary between mullite and developed corundum is discontinuous.     

Synthesis of Submicrometer Mullite Powder via High-Temperature Aerosol Decomposition

High-purity mullite powders (3Al₂O₃.2SiO₂) have been prepared using a high-temperature aerosol decomposition technique yielding submicrometer (0.6 μm average) particles of spherical morphology with no hard agglomerates using aluminum nitrate and fumed silica as precursors. Depending upon the reaction conditions used, the powders range from amorphous to crystalline with no evidence of secondary-phase formation. This mullite synthesis approach has the advantages of not requiring postsynthesis milling, the ability to use a wide range of precursor systems, and enhanced control over chemical homogeneity and particle size/shape.     

高岭土热分解期间莫来石形成的两个阶段

采用X射线技术研究了英国高岭土在加热时的结构变化，用计算机Rietveld程序计算了莫来石和方石英的晶格参数、应变值以及晶体尺寸的变化。这些结果表明了高岭土反应期间莫来石形成的两个独立阶段。讨论了在莫来石形成过程中其成分的变化。     

莫来石—钛酸铝复相陶瓷的高温强度与热分解

本文介绍了莫来石－钛酸铝复相陶瓷的制备工艺及其主要性能，重点对它的高温强度、热分解及抗热震性等进行了讨论并提出了我们的见解。     

高铝粉煤灰中莫来石及硅酸盐玻璃相的热分解过程

研究了高铝粉煤灰-Na2CO3体系中莫来石(3Al2O3·2SiO2)和硅酸盐玻璃相在焙烧过程中可能发生的化学反应,并以热力学计算为指导,研究了物料配比、焙烧温度、焙烧时间对反应的影响.实验结果表明:在Na2CO3与粉煤灰的质量比为1.0、焙烧温度为880℃、恒温1h时,粉煤灰中莫来石(3Al2O3·2SiO2)和硅酸盐玻璃相的分解率可达到98%以上.对粉煤灰中莫来石及硅酸盐玻璃相的热分解过程的动力学研究结果表明,该过程符合CrankGinstling-Braunshtein方程,由实验结果计算,其表观活化能为149.19kJ·mol-1.     

莫来石晶须前驱体原位增强海胆状莫来石材料的性能研究

为了提高粉煤灰的高附加值利用,分别以氢氧化铝和粉煤灰漂珠作为海胆状莫来石前驱体的铝源和硅源,氢氧化铝和粉煤灰为莫来石晶须前驱体增强剂的铝源和硅源,AlF3和V2 O5为晶须促进剂和烧结助剂,采用固相法原位制备了莫来石陶瓷材料.主要研究了增强剂与海胆状莫来石前驱体的配比(质量比分别为3:7、4:6、5:5、6:4、7:3...     

Mullite Decomposition Kinetics and Melt Stabilization in the Temperature Range 1900—2000°C

An investigation of the mullite decomposition mechanism and kinetics in the temperature range 1900—2000°C was conducted. SEM-EDS and XRD analysis showed that the decomposition of mullite in this temperature range was primarily caused by the presence of carbon from furnace components. A reaction mechanism, in which gas-phase SiO₂ reacts with carbon to form SiO and CO, is proposed; both IR analysis and kinetic studies support the proposed mechanism. The decomposition was completely suppressed by the introduction of a modified crucible assembly and the addition of excess SiO₂ to the reaction system. A mullite melt of stable composition was thus obtained, setting the groundwork for inviscid melt spinning mullite fiber making process development.     

Tape Casting and Properties of Mullite and Zirconia–Mullite Ceramics

Mullite and ZrO₂-mullite ceramics have been prepared by tape casting mixtures of Al₂O₃, quartz, and ZrO₂ powders and subsequent reaction sintering. Tape casting leads to homogeneous, high-density green materials with good sinterability. The design of a thermal cycle which favors densification with respect to mullitization allows the preparation of nearly dense, nearly fully reacted materials at sintering temperatures below 1600°C. ZrO₂ additions limit grain growth, but the ZrO₂ content must not be too high when a high tetragonal:monoclinic ratio is required.     

Structural Parameters of Mullite Formed During Heating of Diphasic Mullite Gels

Diphasic gels of four different compositions were synthesized. Lattice parameters, crystallite size, and strain values of mullite formed at different stages of annealing of diphasic gels have been calculated by quantitative standard less analysis using X-ray diffraction. Results show that all three parameters change on progressive heating. Changes in the microstrain of mullite show a reciprocal relationship with crystallite size. Silica-rich gel shows that the relative changes in the calculated values of three structural parameters of mullite formed during its formation process are because of an increase in its crystallinity rather than changes in composition. However, gels of composition in the solid solution range show that the relationship between lattice constants and chemical composition of mullite formed at high temperature agrees with Cameron data.     

Thermal Decomposition of Alkoxides in an Inert Organic Solvent: Novel Method for the Synthesis of Homogeneous Mullite Precursor

Thermal decomposition of a mixture of aluminum iso-propoxide and tetraethoxysilane (Al/Si = 3) in toluene at 300°C was examined. The reaction completely proceeded and yielded an amorphous product. The DTA profile of the product showed a sharp peak at ∼1000°C which was associated with crystallization of mullite and a small amount of the spinel phase. The mullite prepared by calcination of the product at 1300°C was composed of micro-crystals having an average diameter of 30 nm and had a large surface area of 41 m²g.     

Infrared-Transparent Mullite Ceramic

Mullite ceramic, transparent in the infrared, was prepared by hot-pressing and hot-isostatically pressing starting materials derived from alkyloxides. A composition with 72.3 wt% Al₂O₃ yielded transparent, submicrometer grain size bodies at 1630°C, whereas higher temperatures produced glass-containing microstructures. A composition with 76 wt% A1₂O₃ formed precipitates of α-Al₂O₃ at the consolidation temperature, which could be removed by subsequent annealing between 1800° and 1850°C. Spectral transmittance and absorption coefficients of the bodies are reported. The formation of the second phases was linked to phase equilibria and grain growth that promoted compositional equilibration of the mullite phase. The results suggest adjustments to phase boundaries in the high-temperature segment of the SiO₂-Al₂O₃ phase diagram.     

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.     

Mechanical Properties of Mullite

The mechanical properties of alkoxy-derived, high-purity, translucent, theoretically dense mullite (3AI₂O₃.2SiO₂) were investigated over the temperature range room temperature to 1500°C. Large agglomerates were found to contribute to the formation of porosity nests which act as strength-controlling flaws at room temperature as well as at high temperatures. Despite the slow crack growth above 1300°C, a slight increase in fracture stress and a large increase in K_Ic were observed up to 1500°C. These increases are explained by the dominance of energy dissipation through plastic relaxation in the plastic zone over grain-boundary sliding due to the presence of the glassy phase.     

Synthesis of Mullite Whiskers

Mullite whiskers were synthesized by heating a mixture of SiO₂ and silicon in an alumina tube reactor under a flow of H₂ and CF₄. The length and diameter of the whiskers were several hundred micrometers and >15 μm, respectively. It was postulated that a vapor phase reaction between SiF₄ and AlF₃ made possible the synthesis of the large mullite whiskers.     

Elastic Properties of Mullite

Using ultrasonic methods, we determined the ambient-temperature elastic constants of dense (99.7%) hot-pressed polycrystalline 3:2 mullite (3Al₂O₃2SiO₂). We report the usual polycrystal elastic constants: Young's, shear, and bulk moduli, and the Poisson's ratio (nu). The Poisson's ratio (nu = 0.280) suggests interatomic bonding that is very different from that of either alumina or silica. Temperature dependences of the elastic constants show a strong irregularity; for example, nu decreases as the temperature increases. This irregularity suggests an internal-state change that is perhaps related to the incommensurate structural modulation.     

Desiliconization of Mullite Felt

High-temperature evaporation from 80% porous, rigid mullite (3Al₂O₃·2SiO₂) whisker felt was studied under vacuum and at various helium pressures using gravimetry, X-ray diffractometry, SEM, and EDS. Heat treatments at 1350° to 1550°C resulted in evaporation of SiO₂ from mullite with a rate strongly dependent on temperature and pressure. A concentration gradient of SiO₂ was observed through the cross section of samples after heating under vacuum, indicating that SiO₂ preferentially evaporated from whiskers on the periphery of the samples. The SiO₂ concentration gradient was accompanied by sharp microstructural changes across the specimens. The gradient was decreased by raising the ambient helium pressure during heat treatment. A mathematical model was developed to predict the SiO₂ concentration profile. The model agrees well with experimental results and demonstrates that the diffusivity of SiO₂ in the vapor phase controls the gradient of SiO₂ through the cross section of mullite felt.     

Occurrence of Pseudotetragonal Mullite

Mullite-type phases with about 74 wt% Al₂O₃ and 26 wt% SiO₂ were prepared from tetraethyl orthosilicate and aluminum butylate between 950° and 1000°C. The lack of 120/210, 240/420, 041/401, and 250/520 reflection pair splitting on the X-ray diffractograms indicates tetragonal symmetry, whereas normal mullite is orthorhombic. We believe that the tetragonal character of the phase is due to twinning and/or domain formation of orthorhombic structural units in an elementary cell scale. Therefore, the mullite-type phase should be designated as pseudotetragonal rather than tetragonal. According to our present knowledge, pseudotetragonal mullite is formed from highly reactive metal organic compounds only. The phase is metastable and transforms gradually to orthorhombic mullite at temperatures above 1000°C.     

Preparation of Mullite Fiber

Transparent mullite fibers have been prepared using aluminum carboxylates (ACs) and tetraethyl orthosilicate (TEOS) as starting materials. The ACs are derived from the catalyzed dissolution of elemental aluminum in a mixture of formic acid and acetic acid. The solubility of aluminum in the acids is influenced by the concentrations of the acids, water, and additives and the preparation temperature. A 1:4:3:24 molar ratio of aluminum, formic acid, acetic acid, and water dissolves the aluminum completely to give a colorless, clear solution suitable for fiber synthesis. The mixture of the ACs and TEOS, in the presence of ethyl alcohol as a mutual solvent at 50°–60°C, is concentrated to give a spinnable dope, from which mullite precursor fibers can be drawn. Heat treatment of the precursor at 1250°C yields crystallized and transparent mullite fibers.