Low-temperature Ti-containing 3:2 and 2:1 mullite nanocrystals from single-phase gels

TiO₂-containig single-phase gels with (Al₂O₃ + TiO₂)/(SiO₂) molar ratios 3/2 and 2/1 were prepared by gelling mixtures of aluminium nitrate, tetraethylorthosilicate and titanium isopropoxide. Gels were fast heated at several temperatures up to 1100 °C. Dried and heated gels were characterized by differential thermal analysis (DTA), magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray powder diffraction (XRD), and scanning and transmission electron microscopies (SEM and TEM). Coupled DTA and XRD results of gels fast heated at 900 °C showed the crystallisation of two mullites as well as a small amount of alumina-silica spinel. ²⁷Al NMR spectra showed the formation of pentacoordinated aluminium before mullite crystallization. The increase of lattice parameters of single-phase mullites heated at 1100 °C indicated that the amount of TiO₂ incorporated into the mullite structure increased on raising the amount of nominal TiO₂ in both series. SEM and TEM images of heated gels at 1100 °C displayed the formation of well-shaped parallelepiped of titanium-doped mullite nanocrystals with crystalline anisotropy.     

Boron-doped mullite derived from single-phase gels

Mullite with low dielectric constant and high transparency in infrared and microwave range has potential applications in communication industry. To improve the above properties of mullite, boron-doped mullite single-phase gels with a constant molar ratio of Al/Si = 3/1 and various B/Al ratios (B/Al = 0–0.4/3) were prepared in this study by slow hydrolysis of aluminum nitrate, boric acid and tetraethoxysilane. It was found that boron reduces the mullite formation temperature and suppresses spinel formation. The cell unit lattice parameters and cell volume in boron-doped mullite generally decrease with the increase of boron amount. The SEM observation shows that a small amount of boron reduces the grain sizes of mullite sintered bodies while a large amount of boron facilitates the formation of elongated grains and the amorphous glass phase. Boron decreases the transmittance of mullite ceramic and produces additional intensive absorption bond at 3.9 μm and also reduces the dielectric constants in the frequent range of 1 M–1 GHz.     

Characterisation of monophasic and diphasic mullite precursors by solid state reaction study

Abstract

The characterisation by various spectroscopic techniques of amorphous mullite precursors formed from monophasic (SH) and diphasic (DG) gels is reviewed. In a new approach, both types of precursor have been heated with CaCO₃ and the crystalline phases formed during solid state reaction monitored using an X-ray powder diffraction technique. The formation of a calcium aluminosilicate phase (gehlenite) rather than calcium aluminate suggests that both precursors consist of an amorphous aluminosilicate phase of composition close to that of 3:2 mullite.     

Comparative study of conventional and microwave sintered mullite fibres: structural study

Mullite fibres were synthesised from a mixture of aluminium, aluminium chloride and acidic silica solutions as monophasic salts using a sol–gel technique. The viscosity and rheological behaviour of the mullite precursor sol were examined. Mullite fibres were synthesised using both conventional and microwave sintering techniques. The samples were characterised by X-ray diffraction and scanning electron microscopy. Pure mullite fibres were synthesised by microwave sintering at a relatively low temperature of 1200°C. The grain size of the fibre samples sintered using the microwave technique was finer than that produced by conventional sintering. These results show that microwave sintering is a promising technique for processing mullite fibres.     

Mechanical,morphological and dielectric properties of sintered mullite ceramics at two different heating rates prepared from alkaline monophasic salts

The sintering behavior of nanocrystalline orthorhombic mullite powders was investigated. The changes in microstructure, mechanical and dielectric properties with two different heating rates were explained. Microstructural characteristics depending on heating rate were explained at different sintering temperatures. Dielectric properties of prepared mullite nanocomposites were studied to examine the synthesized mullite ceramics as high permittivity materials in the microwave range. It was indicated that a sharp decrease in bulk density was observed at 1600 °C due to the exaggerated growth of mullite grains. Moreover, a maximum hardness value of 4.97 GPa was obtained at 1600 °C with slow heating rate (5 °min^?1). The DC electrical resistivity with a slow heating rate at 1300 °C was approximately three times the value of the mullite sample sintered with a fast heating rate (30 °min^?1). The minimum dielectric loss of about 0.017 at 1.5 GHz was achieved at a sintering temperature of 1500 °C with a slow heating rate.     

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.     

Thermal conductivity in mullite/ZrO2 composite coatings

Mullite-based multilayered structures have been suggested as promising environmental barrier coatings for Si₃N₄ and SiC ceramics. Mullite has been used as bottom layer because its thermal expansion coefficient closely matches those of the Si-based substrates, whereas Y–ZrO₂ has been tried as top layer due to its stability in combustion environments. In addition, mullite/ZrO₂ compositions may work as middle layers to reduce the thermal expansion coefficient mismatch between the ZrO₂ and mullite layers. Present work studies the thermal behaviour of a flame sprayed mullite/ZrO₂ (75/25, v/v) composite coating. The changes in crystallinity, microstructure and thermal conductivity of free-standing coatings heat treated at two different temperatures (1000 and 1300 °C) are comparatively discussed. The as-sprayed and 1000 °C treated coatings showed an almost constant thermal conductivity (K) of 1.5 W m⁻¹ K⁻¹. The K of the 1300 °C treated specimen increased up to twice due to the extensive mullite crystallization without any cracking.     

Porous mullite ceramics through diphasic gels of large boehmite and small silica particles

Mullite formation process has been studied in stoichiometric mullite (3Al₂O₃·2SiO₂) diphasic gel containing large boehmite (1 m) and small silica (10 nm) particles. It has been found that initial mullitization did not take place inside the silica phase (cristobalite), but took place in the defect -alumina phase. -alumina was stabilized by silica when the temperature was below 1350°C. At temperatures above 1350°C, mullite crystallized directly. It was suggested that silica diffused into the pores (<1.8 nm) of -alumina and prevented the collapse of -alumina pore structure. On the other hand, when silica was not present, the pore structure of -alumina collapsed and -alumina crystallized at 1100°C. Porous mullite ceramics were obtained by using special diphasic gels containing large boehmite and small silica particles.     

Thermal stability of expanded perlite modified by mullite

Results of the thermal stability of expanded perlite modified by mullite are presented. Mullite was formed from alumino-silicate gel by sol–gel method. This method allowed us to obtain very homogenous and reactive gel and phase formation of mullite took place at relatively low temperatures. Expanded perlite modified with alumino-silicate gel after firing above the temperature of mullite formation had better thermal stability and durability during heating. The thermal stability of this material was examined up to 1400 °C.     

A structural study of polyelectrolyte gels in a unidirectionally swollen state

We investigated the structures of polyelectrolyte gels, poly(N-isopropylacrylamide-co-2-acrylamido-2-methylpropane sulfonic acid) (NIPA/AMPS) hydrogels in a unidirectionally swollen state by using small-angle X-ray scattering (SAXS). The SAXS results show that the structure of the NIPA/AMPS gels strongly depends upon the composition of NIPA/AMPS. Increase in composition of AMPS causes suppression of concentration fluctuations in the long wavelength. As a consequence, a NIPA/AMPS hydrogel with a low composition of AMPS macroscopically phase-separated at high temperatures, while microphase separation occurred for a NIPA/AMPS gel with a higher composition of AMPS. The instability in the microphase separation initially occurred in the direction perpendicular to the swelling for the latter gel. In the disordered state near the microphase separation region, an elliptic scattering pattern was observed, and the scattering intensity around the peak position in the direction perpendicular to the unidirectionally swelling was larger than that in the direction parallel to it. The behavior became more remarkable, as the interaction parameter χ became larger. These behaviors are consistent with the prediction from the Rabin-Panukov theory. The scattering vector at the scattering maximum in the perpendicular direction q_m,⊥ significantly shifted to smaller q, where q represents the magnitude of the scattering vector, when the microphase separation occurred. It is shown that the periodicity of the microphase-separated structure ranged from 300 to 400 Å.     

Preparation and properties of hierarchical structural alumina/mullite composites

Hierarchical structural alumina/mullite composites constructed by alumina platelets inter-locked porous matrices and mullite whiskers secondary structures had been designed and prepared based on the fluorine-catalyzed gas-phase process. In the composites, mullite whiskers grew on the alumina platelets of the matrices to form cactus-like structures, before that, topaz rods as transitional secondary structures formed at lower temperature. The fluorine-etching effects on secondary structures’ nucleation were discussed. The alumina/mullite composites (1300 °C) had low bulk density (1.10 g/cm³), high porosity (71.4%), and proper compression strength (～14.2 MPa), meanwhile, the average filtration efficiencies of PM2.5 and PM10 during the filtration tests were 78% and 76%, respectively. The introduced mullite whiskers with length of ～1 µm had not induced obvious changes on the structural parameters, hence, the alumina/mullite composites (1300 °C) possessed similar particle filtration performances compared with the alumina porous matrices, and both of the two species materials could be applied for hot gas filtration.     

Thermal insulation and anti-vibration properties of MoSi2-based coating on mullite fiber insulation tiles

Thermal protection materials with excellent thermal insulation properties and high reliability are crucial for aerospace vehicle. Mullite fiber insulation tiles coated with MoSi₂-borosilicate glass (MFIT@MoSi₂) were prepared by a simple slurry method. Results shown that the surface temperature rapidly reached 1043.1 °C under the heat flux of 450 kW/m², while the cold-surface remained at room temperature. The adjusting effects of MoSi₂-based coating on the thermal response and transfer properties of MFIT were investigated systematically. Compared with MFIT, the surface and internal temperatures of MFIT@MoSi₂ were obviously suppressed, due to the existence of MoSi₂-based coating with high emissivity, which effectively enhanced the thermal radiation of the surfaces. Finally, the structural reliability under coupled environment of heating (q₀ = 450 kW/m²) and random vibration with high magnitude (20–2000 Hz, Grms = 20 g) was also investigated. Destructive cracking and peeling of the coating were not observed, due to the excellent bonding strength between the coating and the substrate. The results provided an important basis for the potential application of insulation tiles with mullite fibers in aerospace vehicles and the design of lightweight thermal protection systems.     

Celsian formation from barium-exchanged geopolymer precursor: Thermal evolution

In this paper, thermal evolution, including element & phase composition and microstructure, of Ba²⁺ exchanged K-based geopolymer precursor (BaGP) were systematically investigated during high-temperature treatment. The results proved that celsian precursor with lower residual alkaline cation content were obtained through amorphous geopolymer than traditional ion-exchanged celsian through crystallized zeolite. With the increase in temperature, weight loss of BaGP was due to evaporation of OH groups and decomposition of BaCO₃. Similar to K-based geopolymer, BaGP showed amorphous structure, and nanometer-sized celsian nucleuses first crystallized from the amorphous BaGP matrix after it was treated at 900 °C. In the treatment temperature range from 1000 to 1400 °C, hexagonal celsian became the main phase. After being treated at 1400 °C, hexagonal celsian grains were clearly noticeable with extra SiO₂ locating between celsian grains. It was therefore concluded that geopolymer precursor technique provides an alternative route for the preparation of celsian ceramics.     

Thermal behavior of mullite between 4 K and 1320 K

The evolution of metric parameters of 2:1 and 3:2 mullites have been measured between 4 K and 1320 K using neutron and X‐ray powder diffraction. Negative thermal expansion was observed at low temperature for the a‐cell parameter and consequently for the cell‐volume, which is more pronounced for 2:1 mullite than those for 3:2 mullite. Each parameter is simulated using Grüneisen first‐order approximation for the zero pressure equation of state at 0 K, where the vibrational energy was calculated using microscopic approach. While the b‐ and c‐cell parameters require only one Debye term, a second Debye spectrum with negative Grüneisen parameter was required to fit the a‐cell parameter as well as the cell volume. At 4 K, 300 K and 1320 K the model, respectively, calculates the volume thermal expansion coefficients of 0.09x10^?6 K^?1, 9x10^?6 K^?1, and 17.3x10^?6 K^?1 for 2:1 mullite, and 0.09x10^?6 K^?1, 8.7x10^?6 K^?1, and 17.3x10^?6 K^?1 for 3:2 mullite. Temperature‐dependent Raman spectra and phonon density of states hint for the possible microscopic sources of the cell contraction at low temperature. A simple polynomial approach is presented to calculate the elastic stiffness coefficients of the 3:2 mullite, which are not available from experiments.     

Thermal and mechanical properties of functionalized mullite reinforced unsaturated polyester composites

This work studies the development of varying weight percentages (0.5, 1.0, and 1.5 wt%) of surface functionalized mullite reinforced unsaturated polyester (UP) composites and their thermal, dielectric, water absorption, and mechanical properties. The synthesized mullite was functionalized with vinyltriethoxysilane (VTES). The introduction of vinyl groups on the surface of mullite was confirmed by FT‐IR, TGA, and X‐ray diffraction (XRD) analyses. Varying weight percentages (0.5, 1.0 and 1.5 wt%) of vinyl functionalized mullite (VFM) were incorporated into UP resin with a benzoyl peroxide initiator to obtain composites. The resultant data obtained from thermal, mechanical, dielectric, and water absorption studies, indicate that incorporation of VFM, leads to a significant improvement in the thermo mechanical, dielectric, and moisture resistant properties of the UP composites, compared with those of neat UP matrices. The molecular dispersion of VFM fiber in reinforced UP matrix composites was confirmed by SEM analysis. POLYM. COMPOS., 35:1663–1670, 2014. © 2013 Society of Plastics Engineers     

Small angle neutron scattering studies on structural inhomogeneities in polymer gels: irradiation cross-linked gels vs chemically cross-linked gels

A comparison of network structure in a solvent was made for two types of poly(N-isopropylacrylamide) gels cross-linked by chemical reaction with N,N′-methylenebisacrylamide (BIS) (chemical gels) and by γ-ray irradiation (γ-ray gels). The cross-linking density dependence for these gels was examined by small angle neutron scattering (SANS). The SANS results indicated an increase of frozen inhomogeneities with an introduction of cross-links for both chemical and γ-ray gels. However, it was found that the effect of cross-linking is much stronger in the chemical gels than in the γ-ray gels. The differences in the structure were successfully interpreted by a statistical-mechanical theory of gels proposed by Panyukov-Rabin (Phys. Rep. 269 (1996) 1). The degree of polymerization between cross-links, N, was a decreasing function of cross-linking content for both types of gels, while that for the γ-ray gels was a weak function of irradiation dose. Quantitative analyses on BIS concentration and γ-ray dose dependence led to an experimental evidence of the existence of cross-linking saturation threshold.     

Thermal and related studies of some zirconia gels

The thermal properties of a number of zirconia gels, prepared with various precipitants, have been studied by thermogravimetry, differential thermal analysis and evolved gas analysis. The results obtained show that ligands derived from the various precipitants are incorporated in these gels and strongly influence their high temperature behaviour. The observed properties are interpreted on the basis of a defect structure involving O^2- vacancies generated through the removal of these ligands at higher temperatures.