Time-resolved powder neutron diffraction study of the phase transformation sequence of kaolinite to mullite

Mullite formation from kaolinite was studied by means of high-temperature in situ powder neutron diffraction by heating from room temperature up to 1370 °C. Neutron diffractometry under this non-isothermal conditions is suitable for studying high-temperature reaction kinetics and to identify short-lived species which otherwise might escape detection. Data collected from dynamic techniques (neutron diffraction, DTA, TGA and constant-heating rate sintering) were consistent with data gathered in static mode (conventional X-ray diffraction and TEM). The full process occurs in successive stages: (a) kaolinite dehydroxylation yielding metakaolinite in the ∼400–650 °C temperature range, (b) nucleation of mullite in the temperature range ∼980–992 to ∼1121 °C (primary mullite) side by side with a crystalline cubic phase (Si-Al spinel) detected in the ∼983–1030 °C temperature interval; (c) growth of mullite crystals from ∼1136 °C, (d) high (or β) cristobalite crystallization at T > ∼1200 °C and (e) secondary mullite crystallization at T > ∼1300 °C. The calculated activation energy for the kaolinite dehydration was 115 kJ/mol; for the mullite nucleation was 278 kJ/mol and for the growth of mullite process was 87 kJ/mol; finally for cristobalite nucleation the calculated apparent activation energy was 481 kJ/mol.     

Preparation of mullite by the reaction sintering of kaolinite and alumina

In the present study, mullite specimens and mullite/alumina composites are prepared by reaction sintering kaolinite and alumina at a temperature above 1000°C. The phase and microstructural evolution of the specimens and their mechanical properties are investigated. Primary mullite appears at a temperature around 1200°C. The alumina particles are inert to the formation of primary mullite. Alumina starts to react with the silica in glassy phase to form secondary mullite above 1300°C. The formation of secondary mullite decreases the amount of glassy phase. Furthermore, the addition of alumina reduces the size of mullite grains and their aspect ratio. The strength and toughness of the resulting mullite increase with the increase of alumina content; however, the mechanical properties of the mullite and mullite/alumina composites are lower than those of alumina for their relatively low density.     

Recycling photovoltaic silicon waste for fabricating porous mullite ceramics by low-temperature reaction sintering

In this study, porous mullite ceramics with coral-like structures were fabricated at a low temperature of 900 °C by using photovoltaic silicon waste (PSW) as the silicon source directly. The effects of additive content and sintering temperature on the mullitization reaction of green bodies were studied. The results showed that ammonium molybdate tetrahydrate molybdenum (H₂₄Mo₇N₆O₂₄·4H₂O) as an additive could reduce the reaction temperature for mullitization from 1100 °C to 900 °C. The research on the influence of catalyst on material properties showed that porous mullite ceramics with a flexural strength of 52.83 MPa, a 41.78 % porosity, a sintering expansion rate of 0.49 % and an average pore size of 0.23 μm could be fabricated by introducing 7.5 % H₂₄Mo₇N₆O₂₄·4H₂O at the sintering temperature of 1000 °C. This study develops an environment-friendly recycling method of PSW and provides a new idea for the low-cost preparation of porous mullite ceramics with high purity.     

Anisotropic grain growth in boria-doped diphasic mullite gels

Densification and anisotropic grain growth were investigated in sol-gel derived, boria-doped diphasic mullite. Boria enhanced viscous flow densification by reducing the viscosity and also produced a fine grain microstructure. Whisker-like mullite grains evolved from the dense, equiaxed microstructure. The onset temperature was ∼1500°C. Chemical leaching was employed to characterize the anisotropic grains. Growth kinetics showed that anisotropic grains followed the empirical equation Gⁿ-G_oⁿ=Kt with n=3 and n=4 for the length and thickness directions, respectively. The activation energies for grain growth were 660 kJ mol⁻¹ for elongation and 800 kJ mol⁻¹ for thickening.     

Conventional- versus microwave-hydrothermal leaching of glass from sintered kaolinite to make porous mullite

A microwave-hydrothermal treatment with 1 and 5N-NaOH solution was used at 150°C and 190°C to dissolve excess silica glass and thus make porous mullite ceramics from a fired New Zealand kaolin honeycomb. The effect of microwave-hydrothermal (M-H) treatment time on the dissolution of the glass was examined and compared to the result of conventional-hydrothermal (C-H) treatment. As expected, the rate of the dissolution of glass was faster with M-H treatment compared to C-H treatment. The dissolution of 40–43% glass was almost complete after M-H treatment in 1N-NaOH for 6 hrs at 150°C, in¹N-NaOH for 3 hrs at 190°C, in⁵N-NaOH for 1.5 hrs at 150°C, and in 5N-NaOH for 35 minutes at 190°C. When the M-H treatment in 5N-NaOH solution at 190°C was more than 45 minutes, nonporous prismatic crystals were formed on the honeycomb and these crystals decreased the specific surface area. There were no changes in the morphology of mullite whiskers or in the structure of porous mullite body after M-H treatments in NaOH solutions compared to that of C-H treatment. The M-H treatment has been shown to be a rapid technique to prepare porous mullite ceramics from fired kaolin honey comb.     

Influences of quartz and muscovite on the formation of mullite from kaolinite

A kaolin containing muscovite and quartz (K-SZ) and a pure kaolin (K-SX) with the addition of potassium feldspar, K₂SO₄ and quartz, respectively, were used to investigate the influences of muscovite and quartz on the formation of mullite from kaolinite in the temperature range 1000–1500 °C. In K-SZ formation of mullite began at 1100 °C, and in K-SX at 1000 °C. In K-SZ quartz accelerated the formation of cristobalite and restrained the reaction of mullite and silica. Muscovite in K-SZ acted as a fluxing agent for silica and mullite before 1400 °C and accelerated the formation of cristobalite. The FTIR band at 896.8 cm^− 1 was used to monitor the formation of orthorhombic mullite.     

Effect of topaz on the synthesis of mullite in mixtures of kaolinite and alumina

The synthesis of mullite in mixtures of kaolinite and alumina in the presence of small amounts of topaz is studied. Topaz is shown to activate the synthesis of both the primary (from kaolinite) and secondary mullite (through binding silica produced by thermal degradation of kaolinite), decrease the temperature of synthesis by 100°C, and increase the total yield of mullite. Products of the thermal degradation of topaz — mullite and gaseous chemically active fluoride compounds — are shown to play the role of mineralizing agents.Translated from Novye Ogneupory, No. 8, pp. 49 – 53, August, 2004.For previous communication, see Novye Ogneupory, No. 7, 41 – 46 (2004).     

Preparation of elongated mullite self-reinforced porous ceramics

Elongated mullite was synthesized using mullite powder as a raw material and AlF₃·3H₂O as an additive, and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The effects of AlF₃·3H₂O content and reaction temperature on the formation of elongated mullite were investigated, and the relevant growth mechanism was discussed based on the experimental results and density functional theory (DFT) calculations. When the optimal amount of AlF₃·3H₂O (4?wt% in the present work) was used, the length and diameter of elongated mullite increased with increasing the reaction temperature, and elongated mullite of 22.3?µm in average length and 4.6?µm in average diameter was formed after 5?h at 1873?K. Based on the results, elongated mullite self-reinforced porous ceramics were prepared by a combined foam-gelcasting and solid-reaction method, and their mechanical properties were examined. Elongated mullite in-situ formed in the porous samples evidently enhanced their mechanical strength. The flexural strength of the elongated mullite self-reinforced porous sample with 67.0% porosity (prepared using 6?wt% AlF₃·3H₂O) was as high as 13.9?MPa, which was about 26.4% higher than that of a porous sample (11.0?MPa) prepared without AlF₃·3H₂O.     

利用废弃陶瓷材料制备莫来石轻质材料

为了回收利用废弃陶瓷材料,节约资源,以废弃陶瓷材料为主要原料,加入不同量的黏土(质量分数分别为15%、25%、35%),外加锯末和结合剂,经混料、成型、烘干后,1 200、1 250、1 300、1 350、1 400℃保温3 h热处理,然后检测试样的物理性能,并进行了物相和显微结构分析。结果表明,当废弃陶瓷材料与黏土的质量比为85 15,烧成温度为1 400℃时,试样的综合性能最优;由于热处理过程中发生了莫来石化,试样中的主要物相为莫来石;1 400℃热处理后试样的孔隙直径比1 200℃的大,基质结构也更加致密,由K2O、SiO2、Al2O3组成的液相也较多,因而使材料的强度增大。     

Characterization of textured ceramics containing mullite from phyllosilicates

Organized ceramics are obtained from kaolinite and muscovite suspensions and shaped by aqueous tape casting or centrifugation. These processes favor the preferential orientation of particles in the powder compact. After sintering at 1400 °C, this study analyzed sample microstructures using QTA to determine the degree of the mullite orientation. The analyses revealed two main texture components, a planar texture along the c-axis of the mullite and a preferred orientation along the a-axis, which were aligned parallel and perpendicular to the casting plane, respectively. The important role of processing parameters in the organization degree of the mullite was apparent during the study. The elastic properties at different measurement scales were obtained using US echography and nanoindentation and were closely related to the organization degree of the mullite crystals obtained from the QTA analyses that were consistent with the development of an interconnected mullite network. The Young's moduli due to the nanoindentations were also determined parallel and perpendicular to the layers, and indicated the samples' anisotropic behavior. Both the Young's modulus and the anisotropy of the Young's modulus were correlated with the texture index. In particular, the anisotropy of the Young's moduli was linearly related to the overall texture index, highlighting the microstructures' anisotropic nature.     

Thermo-mechanical properties of mullite ceramics: New data

Coefficients of elastic stiffnesses and thermal expansion of hot isostatically pressed, reaction-sintered and technical fused-mullite ceramics were measured between 100 and 1673 K in comparison with single crystal mullite employing resonant ultrasound spectroscopy and dilatometry, respectively. Additionally, chemical and phase compositions and the microstructure of the ceramics were studied using X-ray diffraction techniques and scanning electron microscopy. Our studies revealed that despite polycrystallinity and slight porosity of up to 1.6%, the elastic behavior of the hot isostatically pressed ceramics is near to ideal aggregate elastic properties of mullite single crystal, for example, their bulk moduli fit within 0.7% to B = 170.0 GPa of single crystal mullite. On the other hand, with B = 155 GPa, the reaction-sintered mullite behaves significantly softer. The difference can be explained with more tight grain to grain contacts in hot isostatically pressed ceramics as compared to reaction-sintered materials. The thermal expansion of both types of ceramics almost coincides with the corresponding averaged behavior of single crystal mullite. For example, between 573 and 1273 K, the volume expansion coefficients of all these materials are (18.0 ± 0.3)·10⁻⁶ K⁻¹. Obviously, the microstructural features are less important for the macroscopic thermal expansion. Due to heterogeneous microstructure and high α-alumina and zirconia contents, the corresponding properties of fused-mullite refractory deviate strongly from those of the other mullite materials.     

Foam-gelcasting preparation of high-strength self-reinforced porous mullite ceramics

High-strength self-reinforced porous mullite ceramics were prepared via foam-gelcasting using mullite powder as a main raw material, AlF₃·3H₂O (0–8 wt%) as an additive, Isobam-104 as a dispersing and gelling agent, sodium carboxymethyl cellulose as a foam stabilizing agent, and triethanolamine lauryl sulfate as a foaming agent. The effects of AlF₃·3H₂O content on rheological and gelling behaviors of the slurries, and porosity and mechanical properties of self-reinforced porous mullite samples were examined. Addition of AlF₃·3H₂O promoted the in-situ formation of elongated mullite in the fired porous samples, which improved considerably their mechanical properties. Compressive strength and flexural strength of 67.0% porous mullite ceramics prepared with addition of 6 wt% AlF₃·3H₂O was as high as 41.3 and 13.9 MPa, respectively. Its hot modulus rupture (HMOR) increased initially with the testing temperature, and peaked (with a maximum value of 16.6 MPa) at 800 °C above which it started to decrease with the testing temperature. Nevertheless, it was still retained as high as 6.7 and 2.8 MPa at 1200 and 1400 °C, respectively.     

Properties and mechanism of mullite whisker toughened ceramics

High-strength ceramics were prepared from high alumina fly ash (HAFA) and activated alumina as raw materials with magnesia as a sintering additive. The growth kinetics and influence mechanism of secondary mullite whiskers were investigated. Meanwhile, the effects of the Al₂O₃/SiO₂ mass ratio (A/S) and the amount of magnesia on the content and morphology of mullite in the green body were investigated, so as to emphasize the effect of the liquid phase in the sintering process on the growth of secondary mullite whiskers. The results showed that the aspect ratio of secondary mullite whiskers increased significantly after adding activated alumina to increase the A/S ratio of raw materials. When 30 wt% activated alumina was added, the mullite content increased by 5.39%, and the whisker length increased from 1.36 μm to 4.18 μm. The addition of magnesia improved the liquid phase formed during the sintering process and the K value method was used to determine the sintering liquid phase content under various conditions. It was observed that increasing the magnesia level by 1 wt% could raise the liquid phase content by 5–7%. When the total liquid content of the system was 30–40%, the growth activation energy in the diameter direction of the whisker reduced significantly, promoting the growth of secondary mullite whiskers along the C axis. The morphology of mullite gradually developed from fibrous to long columnar crystal, making it combine more densely with the green body matrix. Furthermore, the staggered long columnar mullite crystal structure changes the fracture mode of ceramics from intergranular to transgranular fracture, which fully uses the high mechanical strength of mullite. As a result, the fracture energy and strength of ceramics are significantly improved.     

Preparation of self-reinforcement of porous mullite ceramics through in situ synthesis of mullite whisker in flyash body

Self-reinforced porous mullite ceramics were fabricated by a starch consolidation method with flyash, different aluminium sources (Al(OH)₃ and Al₂O₃) and the additive AlF₃ as raw materials. The reinforcement mechanism of needle-like mullite whiskers through in situ synthesis in ceramic body was investigated. The bulk density, apparent porosity and bending strength of the samples were tested. Phase compositions and microstructures of the sintered samples were measured by XRD and SEM, respectively. It showed that AlF₃ as additive was helpful to the formation of mullite whiskers at a low temperature. As the aluminium sources, Al(OH)₃ was more suitable for the preparation of mullite whiskers than Al₂O₃. The in situ synthesized mullite whiskers formed an interlocking structure, which enhanced the mechanical strength of the porous mullite ceramics. Porous mullite ceramics with bending strength of about 100 MPa and apparent porosity of about 55% were made at 1550 °C.     

Near-net-size preparation of porous mullite matrix ceramics with in situ formed 3D mullite whisker network

Porous mullite matrix ceramics have excellent thermal and mechanical properties suitable for applications such as in thermal insulation. However, their applications are limited by processing defects from nonuniform sintering shrinkage and the trade-off between high porosity (preferred for low thermal conductivity) and high mechanical strength. Herein, we seek to minimize the sintering shrinkage by near-net-size preparation and improve the strength by in situ formed whisker network structure. Gelcasting forming technology and pressureless sintering were used to prepare porous mullite matrix ceramics using kyanite and α-Al₂O₃ powders as the starting materials and using MoO₃ to promote the growth of mullite whiskers. The results showed that the sintering shrinkage could be compensated by the volume expansion from solid-state reaction during reaction sintering. The in situ formed three-dimensional (3D) whisker network further reduced sintering shrinkage and effectively improved the strength of the ceramics. An ultralow sintering shrinkage of .78% was achieved. The near-net-shape porous mullite matrix ceramics strengthened by 3D whisker network had a high porosity of 63.9%, a high compressive strength of 83.8 MPa and a high flexural strength of 53.5 MPa.     

Preparation and characterization of mullite microspheres based porous ceramics with enhancement of in-situ mullite whiskers

High-strength insulating ceramic materials were prepared using lightweight mullite microspheres with dense surfaces and high internal porosity as the main raw material and silica sol as a binder. The effects of AlF₃·3H₂O content on the in situ formation and growth of mullite whiskers were analyzed by X-ray diffraction and scanning electron microscopy. The obtained results showed that mullite whiskers were formed in large quantities at 1200 °C using AlF₃·3H₂O and V₂O₅ as additives; their optimal growth was observed at 4 wt% AlF₃·3H₂O and 1 wt% V₂O₅. The apparent porosity of the produced specimens was 39%; the MOR and CCS of the specimens were 31 and 152 MPa, respectively; the HMOR at 1300 °C was 11.32 MPa; and the thermal conductivity at 900 °C was 0.783 W m⁻¹ K⁻¹. The staggered whisker network structure formed between mullite microspheres not only improved the mechanical properties of the material, but also refined its pore size, reduced the thermal conductivity, and enhanced the thermal insulation properties.     

Effects of different potassium salts on the formation of mullite as the only crystal phase in kaolinite

The phase transition in kaolinite from 1050 °C to 1600 °C without and with different potassium salts (KF, KNO₃ and K₂SO₄) as mineralizers and the changes of the composition and morphologies of mullite formed in kaolinite have been investigated. The adding of enough potassium has been found to inhibit the formation of cristobalite in kaolinite. The fluorine is found to be beneficial to increase the reaction activity of aluminium from metakaolinite and so the potassium fluoride has promoted more pseudotetragonal mullite formed at 1100 °C than the other two mineralizers. The influence of potassium salts on the composition and microstructure of mullite formed from kaolinite with increasing the heating temperature has been scrutinized in detail. The formation condition for the only crystal phase of mullite from kaolinite has been shown.     

Effect of mullite phase formed in situ on pore structure and properties of high-purity mullite fibrous ceramics

Porous mullite ceramics are potential advanced thermal insulating materials. Pore structure and purity are the main factors that affect properties of these ceramics. In this study, high performance porous mullite ceramics were prepared via aqueous gel-casting using mullite fibers and kaolin as the raw materials and ρ-Al₂O₃ as the gelling agent. Effects of addition of mullite fibers on the pore structure and properties were examined. The results indicated that mullite phase in situ formed by kaolin, and ρ-Al₂O₃ ensured the purity of mullite samples and mullite fibers bonded together to form a nest-like structure, greatly improving the properties of ceramic samples. In particular, the apparent porosity of mullite samples reached 73.6%. In the presence of 75% of mullite fibers, the thermal conductivity was only 0.289 W/m K at room temperature. Moreover, the mullite samples possessed relatively high cold compressive strength in the range of 4.9–9.6 MPa. Therefore, porous mullite ceramics prepared via aqueous gel-casting could be used for wide applications in thermal insulation materials, attributing to the excellent properties such as high cold compressive strength and low thermal conductivity.     

Anisotropic sintering shrinkage in injection-moulded composite ceramics

The sintering shrinkage of injection-moulded silicon nitride bars reinforced with 0–30 vol.% silicon carbide platelets or whiskers was measured in three orthogonal directions. The extent of shrinkage anisotropy is discussed in relation to inclusion aspect ratio, volume fraction and orientation.