Phase-Pure Mullite from Kaolinite

Sintering of kaolinite in the presence of certain carbonate mineralizers, viz., CaCO₃, Na₂CO₃, and K₂CO₃, has been conducted at 950°–1350°C. The influence of these mineralizers at the above temperatures is evaluated using XRD and SEM techniques. A comparative study of phase formation of the above compositions shows that the sodium- and calcium-fluxed samples give rise to multiphase systems, while K₂CO₃-incorporated samples give phase-pure mullite. The observation that kaolinite in the presence of K₂CO₃ can act as a precursor material for phase-pure mullite is of great industrial significance.     

Preparation of Mullite Ceramics from Coprecipitated Aluminum Hydroxide and Kaolinite Using Hexamethylenediamine

Mullite ceramics have been prepared from an aqueous suspension of kaolinite (raw or ground) and aluminum hydroxide. The precursor was coprecipitated in the mixture using hexamethylenediamine (HMDA) or ammonium hydroxide, and a solution of aluminum chloride from acid dissolution of wastes of aluminum metal. The precursor and the resulting materials were characterized and studied by X-ray diffraction, thermal methods, and mechanical strength and porosity measurements. The feasibility of the proposed chemical processing route for mullite preparation was demonstrated, in particular using HMDA as a precipitating agent for aluminum hydroxide instead of ammonium hydroxide, which adversely affects the system reactivity. The use of HMDA, as compared with ammonium hydroxide, and ground kaolinite produces single-phase mullite and enhances the flexural strength (maximum of 49 MPa) of the resultant ceramic porous bodies (porosity ca. 52–45 vol%) fired at 1550–1600°C for 30 min.     

Formation of Mullite from Pyrophyllite by Mechanical and Thermal Treatments

When pyrophyllite is submitted to mechanical and thermal treatments, significant changes take place, according to XRD and DTA results. With grinding, the DTA endothermic peak is shifted to 540°C and becomes sharper and similar to kaolinite. A sharp exothermic peak is also produced at 1000°C, which is not present in the unground material. Increasing the mullite is associated with the formation of the latter peak. Thermal treatment causes the formation of mullite at higher temperatures.     

Electron-Beam-Induced Phase Transformations from Metakaolinite to Mullite Investigated by EF-TEM and HRTEM

Both energy-filtered electron diffraction and EDS data clearly indicate extraction of amorphous silica from the parent metakaolinite by electron beam heating. Compared with the extracted silica through furnace heating, a larger population with inhomogeneous distribution and higher structural disorder of extracted silica by beam heating was noticed. There is a possibility that the spinel-type phase has lower symmetry than the suggested cubic symmetry, while the 〈111〉 orientation of the spinel-type phase is not perpendicular to the (001) plane of metakaolinite. HRTEM images of mullite crystals apparently demonstrate their random orientations with respect to the parent metakaolinite.     

Acicular Mullite Crystals in Vitrified Kaolin

The microstructure of vitrified kaolin ceramic tapes has been studied via scanning and transmission electron microscopy (SEM and TEM). The sintered samples contained crystalline phase of predominantly stoichiometric mullite (3Al₂O₃·2SiO₂), which consisted of high aspect ratio, acicular crystals that are often referred to as secondary mullite. These crystals were interlocked and embedded in an aluminosilicate glass matrix of inhomogeneous composition. The glass matrix contained an average of ∼3.63 wt% K as determined by energy-dispersive X-ray analysis (EDS), whose composition could be approximated to 5Al₂O₃·16SiO₂·0.1MgO·0.3K₂O·0.15TiO₂·0.12Fe₂O₃. The acicular crystals have approximately the stoichiometric composition of Al₂O₃:SiO₂= 3:2. They have grown along a specific crystallographic orientation along the [001] axis. The crystal growth front exhibited facetting on the {110) planes with microfacetting on both the {100) and {010) planes.     

酸碱条件下莫来石形成机理研究

以正硅酸乙酯(C8H20O4Si),硝酸铝(Al(NO3)3·9H2O)为主要原料,氨水调节pH值,通过溶胶凝胶法制备出酸碱条件下纯相莫来石粉体.通过热分析得知粉体在升温过程中吸热、放热和晶相转换过程;通过XRD研究了凝胶在热处理过程中的结晶变化;通过红外吸收光谱测定了粉体中Si-O-Al键的存在和变化;通过环境扫描电子显微镜测定研究了莫来石粉末的表面特性.最终得出凝胶转变至莫来石的相变过程:酸碱条件下莫来石的生成过程都经历了由无定形铝和无定形硅转变为硅铝尖晶石再到莫来石的过程;在碱性条件下,莫来石开始转变温度低于酸性;同时生成的莫来石中,碱性条件比酸性条件粒度小.     

Mullite Formation from Nonstoichiometric Diphasic Precursors

Diphasic gels with Al/Si atomic ratios of 6/1, 3.1/1, 3/1, 2/1, and 1/1 were used to study the effect of precursor composition on mullite formation process and the resulting microstructure. Mullite formation initiated at about 1300°C for all samples, with only some slight differences in temperatures. The mullite formation temperature was a minimum for an Al/Si ratio of 3.1/1 and increased as the Al/Si ratio of the gels increased or decreased. For the 6/1 gel, dissolution of alumina into mullite solid solution was observed after the initial mullite formation. The dissolution process was reversed above 1450°C with the formation of θ-Al₂O₃ and then α-Al₂O₃. Change of microstructures from equiaxed to elongated mullite grain structures was found within a narrow range of composition near the nominal Al/Si ratio of 3/1.     

Evolution of Mullite Texture on Firing Tape-Cast Kaolin Bodies

Kaolin undergoes a series of phase changes on heating to elevated temperature, proceeding through kaolin, metakaolin, γ-Al₂O₃ spinel, and mullite. The morphologic evolution of the kaolin–mullite reaction series was investigated in the present study. A highly textured kaolin green body was prepared by a tape-casting technique, and the morphology evolution from kaolin flakes to mullite aciculars on firing from 450° to 1600°C was then monitored using X-ray diffractometry and scanning electron microscopy. Equiaxed mullite nuclei first appeared at 1000°C; the aspect ratio of the mullite grains then increased with increased firing temperature. The mullite aciculars rearranged their orientation in a glassy phase until they impinged on each other. A highly textured mullite specimen was prepared by firing the kaolin tape at a temperature >1500°C.     

用Sol－Gel法合成莫来石超细粉机理及过程的研究

以正硅酸乙酯（ＴＥＯＳ）和硝酸铝为原料，用Ｓｏｌ－Ｇｅｌ法合成了莫来石超细粉。探讨了ＴＥＯＳ在硝酸铝存在下的水解缩聚机理。并用差热一逸气、Ｘ一射线衍射、红外光谱及透射电镜等对莫来石的形成过程、结构及颗粒大小进行了研究。结果表明，参与了Ｓｏｌ－Ｇｅｌ过程，并起酸的催化作用，Ａｌ￣（３＋）也参与了网络结构。莫来石相是经过铝硅尖晶石转化成的，在１１５０℃明显生成。１２００℃尖晶石相消失，全部为莫来石，平均粒径为０．０５μｍ。     

Kaolinite–Mullite Reaction Series: The Development and Significance of a Binary Aluminosilicate Phase

The semiquantitative estimations of 980°C exothermic reaction products of kaolinite by quantitative X-ray diffraction (QXRD) and chemical leaching techniques show the formation of a significant amount of amorphous aluminosilicate phase (∼ 30 to 40 wt%). The theoretically expected AlO₄/AlO₆ ratio in the 980°C reaction is in close agreement with the value measured by the X-ray fluorescence (XRF) technique and the experimental radial electron distribution (RED) profile agrees with the suggested 980°C formation of Si-Al spinel with mullite-like composition. Mullitization of kaolinite has been compared with a synthetic Al₂O₃—SiO₂ mixture. In synthetic mixtures development of an intermediate amorphous aluminosilicate phase is an essential step prior to mullitization. Kaolinite forms mullite in two ways: (i) by polymorphic transformation of cubic mullite at 1150° to 1250°C and (ii) by nucleation of mullite in the amorphous aluminosilicate phase and its subsequent growth above 1250°C. Thus chemical continuity is maintained throughout the reaction series and the intermediate spinel phase is silicon bearing and its subsequent transformation to mullite confirms the topotactic concept in the kaolinite transformation.     

Resolution of Thermal Peaks of Kaolinite in Thermomechanical Analysis and Differential Thermal Analysis Studies

The recent findings for the kaolinite metakaolinite, cubic-mullite, and orthorhombic-mullite reaction series have been thoroughly examined by differential thermomechanical analysis (DTMA) and differential thermal analysis (DTA). Metakaolinite shows two differential contraction peaks in the vicinity of 980°C caused by final dehydroxylation at the endothermic dip just before 980°C in DTA with expulsion of 35–37 wt% SiO₂, formation of a defect aluminosilicate phase and simultaneous contraction of the latter phase, and crystallization of cubic mullite at the 980°C exotherm in DTA. Mullitization takes place in two simultaneous reaction steps: (i) polymorphic transformation of cubic mullite to orthorhombic mullite during the ∼1250°C exotherm shown by DTA which coincides with the differential expansion peak in DTMA and (ii) nucleation followed by crystallization of orthorhombic mullite from the residual aluminosilicate compact phase during the ∼1330°C exotherm shown by DTA. The aluminosilicate formed during the large differential contraction at 1100°–1400°C as shown by DTMA. These results, obtained by the two physical techniques, corroborate earlier findings of the kaolinite transformation series.     

Mullite Formation Kinetics of a Single-Phase Gel

A reaction kinetic study of the formation of mullite from single-phase aluminosilicate gels has been performed using dynamic X-ray diffraction. In situ measurements of conversion and separate infrared spectra data indicate that the amorphous single-phase precursors form crystalline mullite at temperatures as low as 1213 K. All of the data are consistent with a nucleation rate-controlled mechanism, unlike previous work with diffusion-limited powders and diphasic gels. At temperatures below 1400 K, the conversion data are adequately fit with a binary model that can approximate a uniform distribution of activation energies. At higher temperatures, evidence indicates that diffusion mechanisms become the rate-limiting step.     

Preparation of Mullite Cordierite Composite Powders by the Sol-Gel Method: Its Characteristics and Sintering

Mullite/cordierite composite powders containing different proportions of cordierite were prepared by the sol-gel method using boehmite, colloidal silica, and Mg(NO₃)₂·6H₂O. Mullite and cordierite sols were prepared separately and mixed to form the composite sol. Mullitization temperature depends on the cordierite content in the composite. Also, α-cordierite crystallizes at a lower temperature in a mullite-rich (MC20) composite. The XRD patterns of the powders calcined at 1450°C for 12 h showed that mullite and cordierite exist as two different phases, and no additional phases were observed. The IR absorbance spectra of composites showed characteristic peak corresponding to both mullite and cordierite. The sintered density of the powders increases with temperature up to 1450°C and decreases beyound the melting point of cordierite (1455°C). The microstructure of MC30 sintered at 1440°C for 3 h consisted of acicular grains, whereas in MC40 and MC50 equiaxed grain morphology was observed under similar sintering conditions. The flexural strength and Vickers hardness decreases with the increase of cordierite content in the composite. Dielectric constant and thermal expansion showed a similar behavior.     

Mullite/Alumina Mixtures for Use as Porous Matrices in Oxide Fiber Composites

Weakly bonded particle mixtures of mullite and alumina are assessed as candidate matrixes for use in porous matrix ceramic composites. Conditions for the deflection of a matrix crack at a fiber-matrix interface are used to identify the combinations of modulus and toughness of the fibers and the matrix for which damage-tolerant behavior is expected to occur in the composite. Accordingly, the present study focuses on the modulus and toughness of the particle mixtures, as well as the changes in these properties following aging at elevated temperature comparable to the targeted upper-use temperature for oxide composites. Models based on bonded particle aggregates are presented, assessed, and calibrated. The experimental and modeling results are combined to predict the critical aging times at which damage tolerance is lost because of sintering at the particle junctions and the associated changes in mechanical properties. For an aging temperature of 1200°C, the critical time exceeds 10 000 h for the mullite-rich mixtures.     

Role of Iron in Mullite Formation from Kaolins by Mössbauer Spectroscopy and Rietveld Refinement

This paper examines the role of iron in mullite nucleation and growth from kaolins. We chose two typical raw kaolins containing a reduced impurity level and characterized by very different degrees of crystallinity of the kaolinite phase. Both the structural iron in kaolinite and also some iron deposited onto phyllosilicate layers by a chemical route were considered. After firing in the 900–1100°C temperature range, the Fe environment was determined by Mössbauer spectroscopy. From X-ray spectra of samples fired at 1250°C, mullite stoichiometries were obtained by Rietveld refinements. It was shown that iron contributes to the structural reorganization stage of the material, when mullite is nucleated. Fe atoms are essentially in octahedral sites, which favors an increase of the c parameter of the orthorhombic cell. The iron quantity attains a saturation level for an Fe-to-Al ratio between 0.3 and 0.4, depending on the raw kaolinite crystallinity. Besides mullite, the excess iron associates with titanium to form a pseudobrookite phase and hematite.     

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.     

Formation of Zeolite During Caustic Dissolution of Fiberglass: Implications for Studies of the Kaolinite-to-Mullite Transformation

Insoluble zeolitic reaction products are formed during the caustic dissolution of fiberglass filters. The zeolite that forms is Linde B₁, the higher temperature form of the zeolite identified during caustic dissolution of free SiO₂ in kaolinite-to-mullite transformations. The Linde B₁ is a sodium aluminosilicate hydrate that preferentially incorporates Ca²⁺ and Mg²⁺. Formation of the Linde B₁ zeolite from fiberglass dissolution in NaOH indicates that caustic dissolution of kaolinite does not preferentially dissolve free amorphous SiO₂, but dissolves any multicomponent amorphous phase present.     

Mullite Whiskers from Precursor Gel Powders

A mullite precursor sol was prepared by mixing boehmite and silica sols. On addition of 3.5 wt% F⁻ ion as a 47% solution of HF, the mullite sol was gelled. The dried gel was ball-milled and calcined at 1400°C for 1 h in an airtight container. Mullite whiskers grew on the (111) plane along the 〈001〉 direction.     

Preparation of Porous Silica from Mechanically Activated Kaolinite

Mesoporous silica has been prepared by leaching of the Al₂O₃ component from mechanically amorphized kaolinite. The kaolinite was amorphized by grinding in a planetary ball mill for 1 h. After grinding the amorphized kaolinite was chemically treated with dilute sulfuric acid at 90°C for varying times. The influence of the leaching time on the porous properties and structure of the silica was studied by XRD, XRF, FTIR and BET adsorption methods. The specific surface areas of the leached samples were found to vary from 312 m²/g to 284 m²/g. The pore size distribution, calculated by the BJH method based on N₂ gas isotherms, showed a unimodal pore size distribution with an average pore size of about 3.8 nm. The total pore volume of the porous silica varied from 0.28 ml/g to 0.312 ml/g, with a uniform pore size distribution in the mesopore regions. New applications exploiting the characteristic pore size of this material are to be expected.     

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.