CoAl2O4–mullite composites prepared by sol–gel processes

The formation of CoAl₂O₄–mullite composites from diphasic sol–gel precursors with 3:2 mullite composition doped with 1, 2 and 3 at.% Co²⁺ was studied by differential scanning calorimetry (DSC), X-ray diffraction and Rietveld structure refinement. The course of thermal reactions is dominated by the intermediate formation of two faint crystallized phases having different composition and activation energies. The former phase with smaller activation energy (822 kJ mol⁻¹) is attributed to cobalt-containing spinel structure and the latter with larger activation energy (about 1200 kJ mol⁻¹) to Al–Si spinel. With temperature increase Co-containing spinel transforms progressively in CoAl₂O₄, while Al–Si spinel forms mullite above 1100 °C. Mullite lattice parameters, Rietveld refinement data and the CoAl₂O₄/Co²⁺ ratio in annealed samples points out that the majority of cobalt is incorporated in CoAl₂O₄ and only about 0.6 at.% enters mullite structure or the glassy phase, or both.     

Diphasic aluminosilicate gels with two stage mullitization in temperature range of 1200–1300 °C

The crystallization of mullite in amorphous diphasic gel aged for 6 months has been studied using non-isothermal differential scanning calorimetry (DSC) and powder X-ray diffraction with Rietveld structure refinement analysis. The diphasic premullite gels undergo structural changes by aging even when they are calcined at 700 °C. These changes imply segregation of the sample to Al₂O₃-rich and SiO₂-rich regions. From the Al₂O₃-rich region crystallizes poorly defined AlSi spinel at 977 °C followed by two-step mullite crystallization in the temperature interval of 1200–1300 °C. Two overlapped exothermic peaks on DSC scan of aged gel were observed; the first at 1233 °C and the second at 1261 °C. The former is attributed to mullite crystallization by transformation of AlSi spinel, by which excess alumina occurs, which in the second step of mullitization reacts with amorphous SiO₂-rich phase. The activation energy for mullite crystallization in the first step was E_a=935±14 kJ mol⁻¹ and the Avrami exponent n=2.5. The values E_a=1119±25 kJ mol⁻¹ and n=1.2 were obtained for mullite formation in the second step. If amorphous SiO₂-rich phase is extracted from the sample, the value E_a=805±26 kJ mol⁻¹ is obtained. Mullite crystallizing from AlSi spinel (when SiO₂-rich phase has been extracted) differentiates compositionally from that formed by both reactions. Smaller unit cell parameters and higher amount of oxygen vacancies are incorporated into tetrahedral positions of mullite structure, as was determined by Rietveld structure refinement method.     

Glass-ceramic glazes for future generation floor tiles

Glaze in the CaO–MgO–Al₂O₃–SiO₂ system was heated at 950–1190 °C for 2 h and characterized. X-ray diffraction showed that only trace amount of mullite was formed in the glass-ceramic glaze heated at 950 °C. Both mullite and α-cordierite were formed in the glass-ceramic glaze heated at 1050 °C as primary and secondary phases. Glass-ceramic glazes heated at 1120 °C and 1190 °C contained α-cordierite and mullite as major and minor phases. Rietveld analysis revealed that the amount of α-cordierite increased and mullite decreased with increasing heating temperature. Field emission scanning electron microscopy showed presence of mullite crystals dispersed within residual glassy phase in the glass-ceramic glazes heated at 950 °C and 1050 °C. In the microstructures of glass-ceramic glazes heated at 1120 °C and 1190 °C α-cordierite crystals were mainly appeared. Energy Dispersive X-ray analysis corroborated X-ray diffraction results. Vickers microhardness measurement demonstrated highest hardness (8.38 ± 0.07 GPa) of the glass-ceramic glaze heated at 1190 °C.     

Preparation of macroporous cordierite monoliths via the sol–gel process accompanied by phase separation

Monolithic cordierite with a cocontinuous macroporous structure has been successfully prepared by the sol–gel process accompanied by phase separation in the presence of poly(acrylamide) (PAAm). Propylene oxide (PO) acts as an acid scavenger to mediate the gelation of MgO–Al₂O₃–SiO₂ ternary system, while PAAm works as a phase-separation inducer as well as a network former. The dried gel and that heat-treated at 800 °C are amorphous, and the sapphirine begins to precipitate at 900 °C, then transforming to orthorhombic β-cordierite at 1100 °C. After heat-treated at and above 1200 °C, the resultant β-cordierite further transforms to stable hexagonal α-cordierite. Heat-treatment changes the macroporous structure of cordierite monoliths such as macropore size and its distribution. The macroporous cordierite monolith after heat-treated at 1200 °C is found to possess a total porosity of 54%, interconnected macropores and dense solid skeletons.     

Effect of composition on sinter-crystallization and properties of low temperature co-fired α-cordierite glass–ceramics

This article investigates effect of composition, including SiO₂ and impurity defined to contain K₂O, Na₂O, Fe₂O₃, etc., from K-feldspar, on sinter-crystallization and properties of the low temperature co-fired α-cordierite glass–ceramics. Increasing impurity content from 5.72 wt% to 9.16 wt% leads to enhanced crystallinity, formation of leucite and more pores but the crystallinity and porosity decreased with a further increase to 10.8 wt%. The main impurity K₂O is critical for formation of α-cordierite and leucite. Only α-cordierite was precipitated from the glasses with different SiO₂ contents but an increase of SiO₂ content slightly improves their densification. The impurity and SiO₂ contents greatly affect the properties of glass–ceramics. Notably, some glass–ceramics from K-feldspar show high densification at low temperature, low dielectric constant (6–8), low loss (about 0.005), appropriate linear CTEs (4.32–5.87 × 10⁻⁶ K⁻¹) and flexural strength (above 100 MPa), all of which meet the requirements of LTCC substrates.     

Crystallisation of amorphous spray-dried precursors in the Al2O3–SiO2 system

The crystallisation of amorphous precursors has been studied in the whole range of composition in the Al₂O₃–SiO₂ system. The amorphous precursors have been obtained by hydrolysing TEOS directly in a diluted aqueous solution of aluminium nitrate, spray drying the clear solution and heating the resulting powder. Up to 70 mol % Al₂O₃, only mullite crystallises around 980–1000 °C; between 70 and 80 mol % Al₂O₃ mullite and spinel crystallise together; and for more than 80 mol % Al₂O₃ only spinel is formed. In the 70–80 mol % Al₂O₃ range of composition, when both mullite and spinel crystallise, low heating favours the crystallisation of mullite and it is nearly possible to crystallise only mullite from a 75 mol % Al₂O₃ sample. By rapid heating it is also possible to crystallise only spinel from the same 75 mol % Al₂O₃ precursor. The enthalpy and the activation energy for crystallisation are maximum for 60–80 mol % Al₂O₃. Heating the samples up to 1700 °C for 1 h, the phase equilibrium is not reached, particularly when both mullite and spinel crystallise together, and θ-Al₂O₃ is still present.     

Effect of SiC whiskers on the anti-oxidation properties of Yb2Si2O7/mullite/SiC tri-layer environmental barrier coating for CMCs

The mullite and ytterbium disilicate (β-Yb₂Si₂O₇) powders as starting materials for the Yb₂Si₂O₇/mullite/SiC tri-layer coating are synthesized by a sol–gel method. The effect of SiC whiskers on the anti-oxidation properties of Yb₂Si₂O₇/mullite/SiC tri-layer coating for C/SiC composites in the air environment is deeply studied. Results show that the formation temperature and complete transition temperature of mullite were 800–1000 and 1300°C, respectively. Yb₂SiO₅, α-Yb₂Si₂O₇, and β-Yb₂Si₂O₇ were gradually formed between 800 and 1000°C, and Yb₂SiO₅ and α-Yb₂Si₂O₇ were completely transformed into β-Yb₂Si₂O₇ at a temperature above 1200°C. The weight loss of Yb₂Si₂O₇/(SiC_w–mullite)/SiC tri-layer coating coated specimens was 0.15 × 10⁻³ g cm⁻² after 200 h oxidation at 1400°C, which is lower than that of Yb₂Si₂O₇/mullite/SiC tri-layer coating (2.84 × 10⁻³ g cm⁻²). The SiC whiskers in mullite middle coating can not only alleviate the coefficient of thermal expansion difference between mullite middle coating and β-Yb₂Si₂O₇ outer coating, but also improve the self-healing performance of the mullite middle coating owing to the self-healing aluminosilicate glass phase formed by the reaction between SiO₂ (oxidation of SiC whiskers) and mullite particles.     

Thermo-mechanical and high-temperature dielectric properties of cordierite-mullite-alumina ceramics

Heterogeneous ceramics made of cordierite (55–56 wt%), mullite (22–33 wt%) and alumina (23–11 wt%) were prepared by sintering non-standard raw materials containing corundum, talc, α-quartz, K-feldspar, kaolinite and mullite with small amounts of calcite, cristobalite and glass phases. The green specimens prepared by PVA assisted dry-pressing were sintered within the temperature range of 950–1500 °C for different dwelling times (2–8 h). The effects of sintering schedule on crystalline phase assemblage and thermomechanical properties were investigated. The sintered ceramics exhibited low coefficients of thermal expansion (CTE) (3.2–4.2×10⁻⁶ °C⁻¹), high flexural strength (90−120 MPa and high Young modulus (100 GPa). The specimens sintered at 1250 °C exhibited the best thermal shock resistance (∆T~350 °C). The thermal expansion coefficients and thermal shock resistance were studied using Schapery model, the modelling results implying the occurrence of non-negligible mechanical interactions between the phases in bulk. The dielectric properties characterized from room to high temperature (RT– HT, up to 600 °C) revealed: (i) noticeable effects of sintering schedule on dielectric constant (5–10) and dielectric loss factor (~0.02–0.04); (ii) stable dielectric properties until the failure of the electrode material. The thermomechanical properties coupled with desirable dielectric properties make the materials suitable for high density integrated circuitry or high temperature low-dielectric materials engineering.     

Electrical properties of cordierite obtained by non-hydrolytic sol–gel method

Cordierite ceramic material, due to its properties such as low thermal expansion coefficient, low dielectric constant and high specific resistivity, could be used as an insulating material in high-frequency electronics, as well as a substrate for integrated circuits and electronic modules. In this paper, cordierite (2MgO·2Al₂O₃·5SiO₂) was synthesized by the non-hydrolytic sol–gel process combined with solvothermal treatment starting from aluminium chloride, TEOS and magnesium chloride dissolved in absolute ethanol. Crystallization of μ-cordierite from gel occurred at temperatures between 900 and 1000 °C and a higher calcination temperature resulted in the transformation of μ-cordierite to α-cordierite. Cordierite material obtained by sintering of powder in the temperature range from 1400 to 1450 °C showed values of the dielectric constants from 7.93 to 3.78 and values of dielectric loss tangents from 0.049 to 0.001.     

Formation,conversion, and elimination of intermediate spinel phase in MgO/kaolin mixture firing for cordierite

Cordierite ceramic is usually used for diesel particulate filter owing to its excellent low thermal expansion coefficient and high thermal shock resistance properties. However, the co-exited intermediate spinel phase can deteriorate the thermal and mechanical performances of cordierite ceramic product, because the spinel phase has much higher thermal expansion coefficient comparing to that of cordierite. In this study, two methods are utilized to reduce the spinel impurity in the cordierite ceramic. On the one hand, rational reaction resources were introduced to decrease spinel production. The formation of intermediate spinel phase is systematically researched by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman characterizations and the results clarified the preference of path “Enstatite + Mullite → Cordierite” for less spinel production in comparison to path “Enstatite + Al₂O₃ → Cordierite + Spinel.” Additionally, MgO was introduced as fluxing agent to promote liquid-phase sintering, thus facilitating the conversion of spinel. On the other hand, the sintering schedule was improved by introducing a holding temperature gradient to promote the diffusion of Si⁴⁺ and further promote the conversion of spinel into cordierite. With these methods, the residual spinel phase is minimized, the resulting high-purity cordierite has a 47% reduction in the thermal expansion coefficient from 3.07 × 10⁻⁶/K to 1.63 × 10⁻⁶/K compared to the original cordierite sample.     

Preparation of refractory cordierite using amorphous rice husk silica for thermal insulation purposes

This study aims to investigate the effect of sintering temperatures on the phase formation and physical characteristics of refractory cordierite prepared from rice husk silica, Al₂O₃, and MgO powders. The samples were subjected to sintering temperatures of 1050–1350 °C, and development of structures was characterized using Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD) coupled with Rietveld analysis, scanning electron microscopy (SEM) and dilatometry. The results obtained indicated the significant role of sintering temperatures on phase transformation of spinel and cristobalite into cordierite, in which at sintering temperatures of 1230–1350 °C the cordierite emerges as a dominant phase, while spinel and cristobalite are practically undetected. Formation of cordierite was followed by decrease in density, porosity, and thermal expansion coefficient, while for hardness and bending strength the opposite was true. Thermal expansion coefficient of the sintered sample at 1350 °C is 3.3×10⁻⁶/°C and the XRD analysis demonstrated that the main crystalline phase is cordierite. Based on these characteristics, the samples are considered as insulator, suggesting their potential use in refractory devices.     

Preparation of α-cordierite through mechanochemical activation of MgO–Al2O3–SiO2 ternary system

Samples of the ternary system MgO–Al₂O₃–SiO₂ with stoichiometric composition in relation to α-cordierite (Mg₂A_l4Si₅O₁₈), consisting of 22.2 mol% MgO, 22.2 mol% Al₂O₃, and 55.6 mol% SiO₂, were activated in a low energy mill with a constant speed of 100 rpm, in an aqueous medium. The precursors used were corundum (Al₂O₃), silica gel HF254 type 60 (SiO₂), and periclase (MgO). The objective of the present study was to evaluate the effect of mechanochemical activation on the solid-state synthesis of α-cordierite, using a low energy ball mill. Another objective was to shed light on the effect of mechanochemical activation on the steps of α-cordierite formation. For this end several grinding conditions were evaluated, varying the time and mass ratio of precursors/grinding elements, as well as calcination at different temperatures between 950 °C and 1350 °C for 2 h. The samples were analyzed for the determination of the formed phases by Infrared (IR) and X-ray Diffraction (XRD). The phases identified in uncalcined samples were brucite (Mg(OH)₂), forsterite (Mg₂SiO₄), enstatite (MgSiO₃), spinel (MgAl₂O₃), amorphous silica (SiO₂), corundum (α-Al₂O₃), and zirconia (monoclinic and tetragonal ZrO₂). The lowest temperature corresponding to the formation of α-cordierite (α-Mg₂Al₄Si₅O₁₈) was 1150 °C and a considerable amount of this phase (16.2%) was observed at this temperature, for the sample with the higher mechanochemical activation. In a solid-state reaction, α-cordierite is normally obtained at around 1400 °C, therefore, the formation of this phase at 1150 °C confirms that the mechanochemical activation method, using a low-cost ball mill, is efficient in reducing the solid-state reaction temperature.     

Thermochemistry of Evaporation and Sublimation of 2,4,6‐Triazido‐1,3,5‐triazine

Saturated vapor pressure over cyanuric triazide melt was measured in the temperature range 393.15–453.15 K using glass membrane Bourdon pressure gauges. Measured evaporation heat and evaporation entropy are equal to 61.1±3.3 kJ mol^–1 and 111.3±6.1 J mol^–1 K^–1, respectively. According to DSC data, melting heat and melting entropy of cyanuric triazide are 22.2±1.3 kJ mol^–1 and 60.5±3.5 J mol^–1 K^–1, respectively. Based on the results obtained, the following dependence was found for the saturated vapor pressure over solid cyanuric triazide: P _s [Pa]=10^14.0 ⋅ exp[(–83300±3300)/RT ]. Concequently, sublimation heat and sublimation entropy of cyanuric triazide are equal to 83.3±3.3 kJ mol^–1 and 171.8±9.6 J mol^–1 K^–1, respectively. Saturated vapor pressure over solid cyanuric triazide at room temperature is equal to 0.25 Pa (1.9×10⁻³ Torr). It is concluded that high volatility of cyanuric triazide is caused by its low sublimation heat.     

Crystallization behavior and sintering of cordierite synthesized by an aqueous sol–gel route

The purpose of the research was to investigate crystallization behavior and sintering of cordierite synthesized by a low-price aqueous sol–gel route starting from silicic acid and magnesium and aluminum salts. Viscous sintering of the gel occurred in the temperature range of 800–850 °C, followed by μ-cordierite crystallization at about 900 °C, which proves the homogeneity of the gel. Decreasing of μ-cordierite crystallinity in a wide temperature range prior to commencing of α-cordierite crystallization at about 1200 °C indicates reconstructive type of μ- → α-cordierite transformation. The transformation was fully completed at 1350 °C. The value of the Avrami parameter indicates that μ-cordierite crystallization was controlled by surface or interface nucleation, which implies that viscous sintering occurred in the primary gel particles, which leads to shrinkage, and thereafter nucleation occurred on the surface or interface of the particles. The overall activation energy of μ-cordierite crystallization was 382.0 kJ/mol. The sinterability of the powder obtained by calcination at 1300 °C, where well-crystallized α-cordierite was formed, was better than that of the powder obtained by calcination at 850 °C, where the most intensive shrinkage occurred before the onset of crystallization of μ-cordierite.     

Low temperature synthesis of highly pure cordierite materials by spark plasma sintering nano-oxide powders

The development of cordierite ceramics, using traditional materials and conventional methods, remains a key challenge because of the high and narrow sintering temperature range. In this work, single-phase cordierite ceramics were produced by spark plasma sintering nano-oxide powders, at low temperatures. A starting mixture of Al₂O₃, SiO₂, and MgO nano-powders with the composition of stoichiometric cordierite was first sonicated, then, sintered in the temperature range 900–1200 °C. The raw powders, sonicated powder mixture, phase transformations, and fracture surface of sintered specimens were characterized by using an x-ray diffractometer and a field emission scanning electron microscope (FE-SEM). The hardness and fracture toughness were measured using the indentation technique. The influence of testing conditions, process parameters, characterization technique, and calculation method on hardness and fracture toughness was investigated. The FE-SEM images, x-ray maps, and EDS results revealed the homogeneity and stoichiometry of the sonicated powder and sintered samples. Highly pure α-cordierite was formed at 1150 °C. Samples that were sintered at 1150 and 1200 °C had bulk density of 2.58 g/cm³ (relative density of 100%), and maintained low average grain sizes of 28.68 and 34.95 nm, respectively. With the decrease in the temperature from 1200 to 1150 °C, the hardness of cordierite was slightly increased from 8.25 ± 0.158 to 8.46 ± 0.188 GPa, the fracture toughness was marginally improved from 2.2 ± 0.158 to 2.25 ± 0.238 MPa mm^1/2, and the critical strain energy release rate was raised from 32.46 to 33.95 J/m².     

Formation of high-temperature crystalline phases in ceramic from illite clay and dolomite

The formation of ceramic with the prevailing cordierite/mullite in the crystalline phase is greatly dependent on the raw materials used. In the present work the cordierite and mullite (or their solid—solutions accordingly with spinels and corundum) formation processes from compositions of natural raw materials (illite clay, dolomite) with synthetic additives (MgO, Al(OH)₃, K₂CO₃) are studied. It is shown that the illite clay acts as a low viscosity liquid medium as well as a precursor for cordierite and mullite crystallisation in ceramics.The phase development using XRD—analysis and the SEM is studied. Particles size distribution of staiting powder and some properties of ceramic obtained are also demonstrated. It is shown that formation of the above mentioned phases starts at temperatures 1050–1080 °C and remarkably increases at 1200 °C for mullite and at 1300 °C for cordierite.     

Low-temperature sintering and microstructure control of mullite–Mo composites

Dense mullite–Mo (45 vol%) composites with homogeneous microstructure have been obtained by plasma activated sintering of a mixture of Mo and mullite precursors at a relatively low temperature (1350 °C) and a pressure of 30 MPa. The mullite precursor was synthesized by a sol–gel process followed by a heat-treatment at 1000 °C. The influence of different mullite precursors on the densification behavior and the microstructure of mullite–Mo composites has been studied. The precursor powder heat-treated at 1000 °C with only Si–Al spinel but no mullite phase shows an excellent sintering activity. Following the sintering shrinkage curves, a two-stage sintering process is designed to enhance the composite densification for further reducing the sintering temperature. The study reveals that viscous flow sintering of amorphous SiO₂ at low temperatures effectively enhances the densification. Moreover, microstructure of these composites can be controlled by selecting different precursors and sintering temperatures.     

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.     

Synthesis,sintering, and grain growth kinetics of Hf6Ta2O17

A systematic study of the solid-state synthesis, pressureless sintering, and grain growth kinetics of Hf₆Ta₂O₁₇ is presented. The ideal conditions for solids-state synthesis of Hf₆Ta₂O₁₇ powder with minimal particle necking was 1250 °C for 2 h in air. The resultant powder has an average particle size of 210 ± 70 nm. The combined synthesis and ball-milling procedure produces highly sinterable Hf₆Ta₂O₁₇ powder, achieving > 97 % of theoretical density after pressureless sintering at 1600 °C for 2 h in air. The grain growth mechanism was sensitive to processing conditions, appearing to be primarily driven by surface diffusion below 1600 °C and grain boundary diffusion above 1650 °C. The respective activation energies for grain growth were found to be Q_S = 659 ± 79 kJ mol⁻¹ and Q_GB = 478 ± 63 kJ mol⁻¹.     

Novel cordierite-acicular mullite composite for diesel particulate filters

Cordierite-acicular mullite composites containing 0, 25, 50, 75 and 100 wt% of mullite were fabricated from waste MoSi₂ and commercial powders of Al₂O₃ and spinel (MgAl₂O₄). Careful oxidation of pulverised waste MoSi₂ rendered a precursor mixture of MoO₃ and amorphous SiO₂, which served as pore forming agent and SiO₂ source, respectively. Evaporation of MoO₃ at ～750 °C allowed production of highly porous cordierite-mullite ceramic composite after sintering in air at 1350 °C for 4 h. The combination of equiaxed cordierite grains and elongated (prism-like) mullite grains, resulted in unique microstructure with open porosity between 53.3 and 55.6 vol% which makes the obtained composite convenient for application as diesel particulate filter material. The presence of mullite affected four key thermo-mechanical properties which determine the thermal shock resistance of cordierite-mullite composite. The best thermal shock resistance was measured in composite containing 75 wt% of mullite. It was a result of improved thermal conductivity (1.081 W/mK) and bending strength (3.62 MPa) and relatively low values of coefficient of thermal expansion (3.8 × 10^?6 K^?1) and elastic modulus (2.27 GPa).