用凝胶法制备片状莫来石粉及其应用

用拟薄水铝石和非晶态ＳｉＯ_２微粉为原料，用溶胶－凝胶工艺制取了莫来石凝胶。通过干燥、煅烧，制得片状结晶莫来石粉．初步研究了凝胶法莫来石粉在钛酸铝陶瓷和烧结刚玉砖中的应用。实验结果表明，片状莫来石起了促进烧结、降低烧成温度的作用，并使钛酸铝－莫来石复相陶瓷和刚玉砖的强度得到显著提高．     

Effect of Y2O3 additive on conventional and microwave sintering of mullite

Mullite has become a strong candidate material for advanced structural and functional ceramics. Much interest has recently focused on sintering aids for mullite. The aim of this study was to evaluate the effect of Y₂O₃ as a sintering aid in the conventional and microwave sintering of mullite. To accomplish this study, a highly pure industrial mullite was used. Mullite with and without Y₂O₃ was pressed under a cold isostatic pressure of 200 MPa. Samples were sintered conventionally at 1400, 1450, 1500, 1550 and 1600 °C for 2 h and microwave-sintered for up to 40 min using a large range of power. The microstructure and physical properties of the microwave-sintered samples were compared to those of the conventionally sintered samples. The results showed that Y₂O₃ improved the densification of mullite bodies in the conventional and microwave sintering processes, but high densifications were achieved in just a few minutes when Y₂O₃ was used with microwave processing.     

溶胶—凝胶法制备莫来石粉末

以硝酸和正硅酸乙酯为主要原料，采用溶胶－凝胶法制备莫来石粉末，并利用DSC技术和XRD技术研究了莫来石的形成过程、物相组成，制定出合理的煅烧温度。     

Impact of microwave processing on porcelain microstructure

Microstructural evolution on sintering of porcelain powder compacts using microwave radiation was compared with that in conventionally sintered samples. Using microwaves sintering temperature was reduced by ~ 75 °C and dwell time from 15 min to 5 min while retaining comparable physical properties i.e. apparent bulk density, water absorption to conventionally sintered porcelain. Porcelain powder absorbed microwave energy above 600 °C due to a rapid increase in its loss tangent. Mullite and glass were used as indicators of the microwave effect: mullite produced using microwaves had a nanofibre morphology with high aspect ratio (~ 32 ± 3:1) believed associated with a vapour-liquid-solid (VLS) formation mechanism not previously reported. Microwaves also produced mullite with different chemistry having ~ 63 mol% alumina content compared to ~ 60 mol% alumina in conventional sintered porcelain. This was likely due to accelerated Al⁺³ diffusion in mullite under microwave radiation. Liquid glass was observed to form at relatively low temperature (~ 900–1000 °C) using microwaves when compared to conventional sintering which promoted the porcelains ability to absorb them.     

Mullite fibres prepared by sol–gel method using polyvinyl butyral

Mullite fibres with uniform diameter and smooth surface have been synthesized using commercial grade polyvinyl butyral (PVB) as binder. The sol with good spinnablity was obtained at reaction temperature of 60 °C for 1 h. The results of X-ray diffraction indicated that the Al–Si spinel was obtained before complete mullization, which implied the addition of PVB retarded the phase transformation of mullite. The fibres showed a rough surface and lateral cracks at 800 °C. Smooth and dense surface was observed when fibres were sintered at 1200 °C and completed transformation to mullite was achieved. This technique offered the possibility of synthesizing mullite fibres at considerably lower cost than at present.     

Fabrication of mullite ceramics by rotary forging and pressureless sintering

Mullite ceramics were fabricated from boehmite/silica diphasic gels using a rotary forging compaction technique and pressureless sintering. Almost fully dense mullite samples were obtained after sintering at 1350°C for 2 h. The microstructure of sintered samples comprised fine (average size <1 μm), equiaxed grains. The samples showed superior sintering behaviour in comparison to those fabricated using conventional uniaxial and isostatic pressing. Powder compaction by rotary forging is thought to generate viscous deformation of the contact points increasing the interparticle contact area as well as increasing the packing density by breaking down hard agglomerates more effectively with concomitant rearrangement of the primary powder particles, thus promoting greater densification at relatively low temperatures. ©     

Influence of zircon particle size on conventional and microwave assisted reaction sintering of in-situ mullite–zirconia composites

Mullite–zirconia composites were fabricated by reaction sintering of ZrSiO₄ and α-Al₂O₃ using conventional heating and microwave processing. The powder mixtures were prepared from sub-micron zircon powders with three different particle sizes and CIPed as coin shaped samples. The samples sintered both in a muffle furnace and microwave furnace. The open porosities, bulk and true densities were measured. Phase transformations were characterized by X-ray diffraction and microstructures were evaluated by scanning electron microscopy. The effects of zircon particle size on the in-situ transformation system and mullitization was evaluated for both methods. As a result, decreasing zircon particle size decreases the in-situ transformation temperature for 25 °C (1575 °C) in conventional heating. Microwave assisted sintering (MAS) lowers the transformation temperature at least 50 °C by lowering the activation energy more efficiently and gives better densification than conventional sintering. Furthermore, milling also produces structures having finer mullite grains.     

Electrospun mullite nanofibers derived from diphasic mullite sol

Fine‐grained mullite nanofibers derived from the diphasic mullite sol were successfully fabricated by electrospinning and subsequent pyrolysis at 1500°C. Polymethylsiloxane and aluminum tri‐sec‐butoxide were selected as the silicon and aluminum source to synthesize the diphasic sol. Results show that the weight loss of mullite precursor fibers in our work was about 60 wt.%, which is similar with that of fibers fabricated using the monophasic sol. This low weight loss was mainly attributed to the high ceramic yield of polymethylsiloxane and low introduced polyvinylpyrrolidone content, which ensures the integrity of fiber morphology during the sintering process. Mullite fibers with 216 nm average diameter were fabricated after sintered at 1500°C and the corresponding grain size was only ~100 nm, much smaller than that in mullite fibers derived from monophasic sols. Therefore, it can be predicated that mullite fibers in this work should possess a higher mechanical strength than those derived from monophasic sols when the sintering temperature was higher than 1400°C and therefore was an ideal starting materials for the fabrication of mullite nanofibrous ceramics used as the high‐temperature thermal insulation materials.     

In situ mullite foam fabrication using microwave energy

In situ mullite ceramic foams were fabricated using polymeric sponge replication method from ceramic slurry containing alpha alumina and kaolin mixtures. Ceramic preforms were processed using microwave energy and conventional heating. The sintered foam samples were characterized by SEM and XRD observations, density measurements and compression tests in order to observe the effect of two different sintering techniques on the structure and properties. It was found that the microwave processing was completed in a shorter burning out and sintering cycle and produced structures having higher mullite transformation ratio and fine grains.     

Rapid densification of SiC ceramic rollers by microwave sintering

Ultralarge silicon carbide (SiC) ceramic rollers are successfully prepared in a microwave multimode cavity at 2·45 GHz. The length of the rollers is 1220 mm with outer diameter of 62 mm and thickness of 7 mm. The optimised sintering temperature of microwave sintering is ～980°C, which is ～400°C lower than that of conventional sintering. Mullite was detected within microwave sintered samples, rather than conventional sintered ones, which preferentially appeared around SiC as well as inside the residual pores. This might be attributed to the unique features of microwave sintering of ‘hot spot effect’, plasma behaviour and high frequency electromagnetic fields.     

Spark plasma sintering to restrict sintering reactions and enhance properties of hydroxyapatite–mullite biocomposites

Herein, we demonstrate how spark plasma sintering (SPS) can be useful in restricting the sintering reactions and faster densification in Hydroxyapatite–Mullite system, which otherwise shows extensive sintering reactions during conventional pressureless sintering, as reported in a recent study [Nath et al. J. Am. Ceram. Soc. 93 (2010) 1639–1649]. The microstructure of SPSed Hydroxyapatite (HAp)-20 wt% mullite composites was characterized by submicron sized HAp and equiaxed mullite grains. Another important result has been the achievement of higher hardness of 7 GPa, which is much higher than pressureless sintered composites. The cell culture study including cellular viability using MTT analysis establishes good cytocompatibility of SPSed composites.     

Effect of viscosity of polyvinyl alcohol solution on morphology of the electrospun mullite nanofibres

Mullite nanofibres with diameters of 85–110 nm were obtained by electrospinning of solutions containing different amounts of polyvinyl alcohol (PVA, as the template) ranging from 0 wt% to 10 wt%, which were added to the sol, and sintered at different temperatures. The sol was prepared by the sol–gel method, using aluminium isopropoxide (AIP), hydrated aluminium nitrate (AN) and tetraethylorthosilicate (TEOS) as the precursors. The details of crystal development, microstructure and thermal decomposition behaviour of the electrospun nanofibres were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and simultaneous thermal analysis (STA). The optimal content of 6 wt% of PVA in the electrospinning polymeric solutions was found to be the suitable viscosity for the electrospinning and ultimately resulted in the formation of the most pure and uniform mullite nanofibres.     

Mining tailings as raw materials for reaction-sintered aluminosilicate ceramics: Effect of mineralogical composition on microstructure and properties

This paper presents studies on the utilization of aluminosilicate-based mining tailings as raw materials for mullite-based ceramics. Based on the 3:2 stoichiometric composition, mullite was synthesised by reactive sintering with a series of powder mixtures with alumina additions. X-ray diffractometry and scanning electron microscopy analyses revealed that, at the specific mineralogical composition, mullite structure formed surrounded by an amorphous glass phase in reaction-sintered powder mixtures. Results demonstrated that the chemical and mineralogical composition of mining tailings do have an effect on mullite formation possibilities and, only with the particular mineralogical composition, the mullite formation is possible regardless of the correct Al:Si ratio in tailings. Physical and mechanical properties of the formed ceramics were defined, showing comparable values to 3:2 mullite reference. Mullite structure formation enables a better thermal resistance up to above 1450?°C of the formed tailings-based ceramics compared to other aluminosilicates, reflecting their utilization potential for refractory ceramic applications.     

Impact of spark plasma sintering (SPS) on mullite formation in porcelains

The effect of the spark plasma sintering (SPS) process on mullite formation in porcelains was studied using X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. SPS affected the kinetics and morphology of formed mullite. After sintering at 1100°C, unlike conventional sintering, SPS promoted the formation of mullite due to the combination of vacuum and applied pressure. Mullite crystal growth was altered by the atmosphere (vacuum), dwell time (0‐15 minutes), and temperature (1000‐1200°C). The applied pressure caused the mullite needles to orient perpendicular to the direction of the applied load. Depending on SPS dwell time, the mullite formed after sintering at 1100°C also had different crystal structure (tetragonal for short dwell time of 0‐5 minutes and orthorhombic for a long dwell time of 10‐15 minutes). Dissolution of mullite was observed at 1100°C by extending the dwell time by up to 15 minutes and the dissolved mullite reprecipitated on the small needles (~40 nm) and coarsened via Oswald ripening resulting in larger mullite needles (~60 nm).     

Synthesis of mullite nanofibres by electrospinning of solutions containing different proportions of polyvinyl butyral

In this paper, the synthesis of continuous mullite (3Al₂O₃·2SiO₂) nanofibres by combination of the sol–gel and electrospinning technique is reported. To find out the optimum viscosity of the electrospinning solution for obtaining the high quality mullite nanofibers, solutions containing different amounts of polyvinyl butyral (PVB, 0–8 wt%) and the precursor sol were prepared for the electrospinning process. The precursor sol was made by using proper amounts of aluminium isopropoxide (AIP), hydrated aluminium nitrate (AN) and tetraethylorthosilicate (TEOS). Crystal phase, microstructure and thermal decomposition behaviour of the electrospun mullite nanofibres were investigated by conventional methods of analysis. The optimal amount of PVB in the electrospinning polymeric solutions was found to be between 4 and 6 wt% and the mullite nanofibres obtained as such were pure, smooth and uniform with diameter sizes of 85–130 nm after calcination at 1200 °C.     

Synthesis and two-step sintering behavior of sol–gel derived nanocrystalline corundum abrasives

Nanocrystalline corundum abrasive with mean crystal size of less than 100 nm was synthesized by two-step sintering method using sol–gel process. A remarkable suppression of grain growth was achieved by controlling sintering temperature and taking advantage of sintering aids during the final stage of a two-step sintering process. The grain size of the high densification samples (>99% theoretical density) produced by two-step sintering method was about 10 times less than the samples made by the conventional sintering technique. The microstructure of the samples was homogeneous without abnormal grain growth and the sol–gel derived corundum abrasive with two-step sintering technique exhibited excellent mechanical properties and wear resistance compared to those sol–gel derived corundum abrasive with conventional sintering methods and fused corundum abrasive.     

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.     

凝胶法片状莫来石粉的制备及应用

采用拟薄水铝石和非晶态超细SiO_2微粉为原料。以溶胶-凝胶工艺制取莫来石凝胶,通过干燥、煅烧研制得片状结晶莫来石粉。初步研究了凝胶法莫来石粉在钛酸铝陶瓷和烧结刚玉砖中的应用。实验结果表明:凝胶粉起到了促进烧结、降低烧成温度的作用,并使钛酸铝——莫来石复相陶瓷和刚玉砖的强度得到了显著提高。     

Mechanical Properties of Mullite–Corundum Composites Prepared from Bauxite

Mullite–corundum composites have been prepared by reaction sintering of Indian bauxite having considerable amount of impurities and silica sol. The effect of changing mullite phase proportion on the mechanical properties (i.e., flexural strength, elastic modulus, hot modulus of rupture, thermal shock resistance) of prepared composites has been studied. Flexural strength and elastic modulus increase with increasing free corundum phase content in the composites. Hot modulus of rupture for the sample containing only mullite phase increases with increasing test temperature over entire temperature range. Theoretical thermal shock resistance parameters R and R? are well supported by experimental thermal shock data.     

Sintering and microstructural study of mullite prepared from kaolinite and reactive alumina: Effect of MgO and TiO2

Mullite ceramic was prepared using kaolinite and synthesized alumina (combustion route) by solid-state interaction process. The influence of TiO₂ and MgO additives in phase formation, microstructural evolution, densification, and mechanical strengthening was evaluated in this work. TiO₂ and MgO were used as sintering additives. According to the stoichiometric composition of mullite (3Al₂O₃·2SiO₂), the raw materials, ie kaolinite, synthesized alumina, and different wt% of additives were wet mixed, dried, and uniaxially pressed followed by sintering at different temperature. 1600°C sintered samples from each batch exhibit enhanced properties. The 1 wt% TiO₂ addition shows bulk density up to 2.96 g/cm³ with a maximum strength of 156.3 MPa. The addition of MgO up to 1 wt% favored the growth of mullite by obtaining a density and strength matching with the batch containing 1 wt% TiO₂. These additives have shown a positive effect on mullite phase formation by reducing the temperature for complete mullitization by 100°C. Both additives promote sintering by liquid phase formation. However, the grain growth, compact microstructure, and larger elongated mullite crystals in MgO containing batch enhance its hardness properties.