Effect of pH on 980 °C spinel phase-mullite formation of Al2O3-SiO2 gels

Different reaction paths of mullite formation via sol-gel processing techniques are reviewed. These variations are due to differences in hydrolysis/gelation behaviours of the silica and alumina components used. Variations of pH during processing without altering other variables follow three different routes of mullite formation. In the highly acidic region(pH 1), the gel does not exhibit a 980 °C exotherm but forms -Al₂O₃. Mullite forms at high temperature by diminution of -Al₂O₃ and -cristobalite, respectively. In the pH range of 3–4.5, gels exhibit a 980 °C exotherm and develop only mullite. In the highly alkaline region (pH 14), the gel produces a Si-Al spinel phase at the 980 °C exotherm and mullite formation at the 1330 °C exotherm takes place from the intermediate Si-Al spinel phase.     

On the formation of mullite from kandites

Data are presented that support the explanation of the 980° C differential thermal analysis (DTA) exotherm of kandites in terms of transitional mullite (premullite) formation. The evolution of this material towards final 32 mullite takes place with change in the tetrahedral aluminium/octahedral aluminium ratio, as evidenced by IR spectroscopy. The so-called mullite peak at 1250° C is shown to disappear when soaking experiments are carried out at lower temperatures, indicating that it is an effect of the dynamical character of DTA techniques.     

Gel formation in mullite precursors obtained via tetraethylorthosilicate (TEOS) pre-hydrolysis

Tetraethylorthosilicate (TEOS) and aluminium chloride were taken as sources of SiO2 and Al2O3 to prepare precursors of mullite by pre-hydrolysis of TEOS under refluxing conditions. Gelation was carried out at different pH values and the effect of the pH of gelation on the subsequent temperature-induced phase transformations was characterized by differential thermal analysis, powder X-ray diffraction and 29Si and 27Al solid-state nuclear magnetic resonance spectroscopy. A pH-dependent exothermic peak was observed at 980°C. Strong acidic conditions (pH=1.5) were found to be beneficial for improving the mixing scale of the Al–Si components, leading to a mullitization temperature of 1200° and a sharp 980°C exothermic peak. In strong basic conditions (pH=11.5), no evident 980°C exothermic peak was detected, and the mullitization temperature was as high as 1350°C, probably due to heterogeneity in the mixing scale of the Al–Si components in the precursor system. A gel formation process has been proposed.     

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al₂O₃-2SiO₂). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminium nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment in these two types of sol-gel-derived mullite precursor powders, have been characterized by differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and infrared spectroscopy (IRS). Monophasic xerogel transforms to an aluminium-silicon spinel from an amorphous structure at 980 ° C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at 1360 ° C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (-Al₂O₃, cristobalite) even after heating at high temperatures for long periods (1600 ° C, 6 h). The diphasic powder could be sintered to high density but not the monophasic powder, in spite of its molecular-level homogeneity.     

Characterization of the spinel phase in a diphasic mullite gel using dynamic X-ray diffraction

Dynamic X-ray diffraction (DXRD) has been used in an effort to identify the specific phase changes which are responsible for observed thermal events at 980 °C in mullite gel precursors. Specifically, changes in the evolution of the common and strongest diffraction peak (d = 0.139 nm) corresponding to both transient alumina phases and the Al-Si spinel were followed in order to descriminate between these two phases. Results which compare the DXRD results for a diphasic mullite gel and a boehmite gel are presented and suggest that the Al-Si spinel phase forms at 980 °C in diphasic gels along with - and/or -Al₂O₃. These results are corroborated by separate TEM measurements which indicate the presence of both phases in samples quenched from 1000 °C.     

A thermogravimetric study of the oxidation of CuFeO2

The oxidation kinetics of CuFeO₂ have been studied between 500 and 1000° C under various oxygen partial pressures using thermogravimetric analysis (TGA). The oxidation rate was found to increase as the oxygen partial pressure was increased, and for a given partial pressure of oxygen it was found to be maximum at 700° C. The enthalpy and activation energy for the oxidation of CuFeO₂ were calculated to be 26.6±2 and 18±2 kcal mol^–1 respectively. The oxidation of CuFeO₂ resulted in the formation of CuFe₂O₄ and CuO, and the rate of reaction followed an S-type curve as found in the pearlitic transformation in steels.     

Sintering and crystallization of mullite in diphasic gels

Diphasic monolithic mullite gel of stoichiometric composition shows a multiple aggregation of colloidal SiO₂ ( 12 nm) and AlOOH (10 nm) particles. The identity of the colloidal particles is retained up to the crystallization of mullite at a temperature of 1240°C in unpressed or 1220°C in gels cold-isostatically pressed at 1.5 GPa. Intensive sintering is closely followed by crystallization of mullite. Both sintering and crystallization are apparently related with the formation of a silica continuum. Nucleation of mullite appears to occur at points of contact (interface) of SiO₂/-Al₂O₃ particles.     

Characterization of pyrolysed silacyclobutasilazane

Silacyclobutasilazane (SCBZ) is a candidate organosilicon polymer suited to many hightemperature applications. Pyrolysis of SCBZ occurs over two distinct temperature ranges 400–800 and 1400–1800 °C. X-ray diffraction analysis showed that amorphous SCBZ transforms to crystalline SiC above 1400 °C. Thin foils of the pyrolysed (1800 °C) SCBZ were prepared and examined using the analytical electron microscope. The material was found to contain 200 nm-SiC particles scattered through a matrix consisting of 50 nm radiating clusters of pyrolytic graphite crystals and a highly carbonaceous amorphous background. It is suggested that during 1400–1800 °C pyrolysis two major reactions occurred. Initially, SCBZ through nitrogen loss, decomposed to crystalline SiC and amorphous carbon. Subsequent graphitization then produced the radiating crystal clusters.     

Some properties of mullite powders prepared by chemical vapour deposition

The sinterability of mullite (3Al₂O₃·2SiO₂) powder prepared by chemical vapour deposition was examined to improve the conditions for fabricating dense mullite ceramics. The starting powder contained not only mullite, but also a small amount of -Al₂O₃ (Al-Si spinel) and amorphous material. Although the compressed powder was fired at a temperature between 1550 and 1700 °C for 1, 3 and 5 h, the relative densities of the sintered compacts were limited to 90%: (i) due to the creation of pores/microcracks during the solid state reaction (1100–1350 °C), and (ii) due to restriction on the rearrangement of grains because the amount of liquid phase (1550–1700 °C) was insufficient. Calcination of the starting powder was effective for preparation of easily sinterable powder with homogeneous composition. When the compact formed by compressing the calcined powder at 1400 °C for 1 h was fired at 1650 °C for 3 h, the relative density was raised up to 97.2%; moreover, mullite was the only phase detected from the sintered compact. The sintered compact was composed of polyhedral grains with sizes of 1–2 m and elongated grains with long axes of 6 m.     

Spherical particle preparation of Na+-ion conductive Na4Zr2Si3O12 by mist pyrolysis

Spherical polycrystalline particles of Na₄Zr₂Si₃O₁₂ (NZS) have been prepared by a mist pyrolysis technique with alkoxide ethanol solution. Firing the precursor particles, obtained by pyrolysing at 550 °C, yielded the NZS with the highest S/N ratio and the least second phase at 1000 °C. Each spherical particle with an average size of 0.5 m was composed of primary particles of 0.1 m diameter after firing. Comparing the particle formation process with the sol-gel, alkoxide pyrolysis and the aqueous solution processes, it would appear that the primary particle size of the mist-pyrolysed NZS depends on the size and residual alkyl group content of the precursor polymers.     

Change of mechanical properties of rigid poly(vinylchloride) during photochemical ageing

Thermally stabilised, unpigmented, rigid PVC samples, were exposed to accelerated photoageing at 40°C, 55°C and 70°C. The concentration profiles of photoproducts were determined on microtome slices ( 20 m) parallel to the irradiated surface using IR (carbonyls) and UV (polyenic double bonds) spectrophotometry and by steric exclusion chromatography (Mn and Mw). They indicate that carbonyls and chain scissions predominate only in a thin superficial layer whereas polyconjugated double bonds and crosslinks predominate in a subcutaneous layer (300–400 m). Tensile measurements show that the ultimate elongation decreases after an induction period whose duration is a decreasing function of temperature. The change of mechanical behaviour can be described in terms of a ductile-brittle transition shift mechanism in which crosslinking plays an important role. A tentative explanation of a such crosslinking induced transition is proposed in the discussion.     

Stability of nickel coated sapphire whiskers

The effect of high temperature annealing (1100 to 1300° C) on the stability of nickel coated purified sapphire whiskers has been investigated. It was found that the initially coherent coating spheroidized to form a series of partially adherent nickel particles, which increased in size with continued time at temperature. The time for complete adhesion of the particles, which was established from the product of the number and volume of particles per unit area of surface, decreased from 72 h at 1100° C to 3 h at 1300° C, giving an activation energy of 70 kcal/mol. In addition at 1300° C, after 8 h, there was evidence for whisker breakdown from a sapphire-nickel reaction.     

Sintering and crystallization of mullite powder prepared by sol-gel processing

Mullite powder with the stoichiometric composition (3Al₂O₃.2SiO₂) was synthesized by a sol-gel process, followed by hypercritical drying with CO₂. Within the limits of detection by X-ray diffraction, the powder was amorphous. Crystallization of the powder commenced at 1200 °C and was completed after 1 h at 1350 °C. In situ X-ray analysis showed no intermediate crystalline phases prior to the onset of mullite crystallization and the pattern of the fully crystallized powder was almost identical to that of stoichiometric mullite. The synthesized powder was compacted and sintered to nearly theoretical density below 1250 °C. The microstructure of the sintered sample consisted of nearly equiaxial grains with an average size of 0.2 m. The effect of heating rate (1–15 °C min^–1) on the sintering of the compacted powder was investigated. The sintering rate increased with increasing heating rate, and the maximum in the sintering curve shifted to higher temperatures. The sintering kinetics below 1150 °C can be described by available models for viscous sintering.     

Effects of aluminium on the electrical and mechanical properties of PTCR BaTiO3 ceramics as a function of the sintering temperature

The effect of AI additions on the electrical behaviour of positive temperature coefficient of resistance (PTCR) BaTiO₃ ceramic sintered in air at temperatures ranging between 1220 and 1400° C have been investigated. Two batches of material, both showing a PTCR effect, were prepared identically except that additions of AI₂O₃ (0.55 mol %) were made to one of them. It has been confirmed that the presence of aluminium results in an increase in the temperature at which the maximum resistivity, _max, occurs as well as reducing the sintering temperature, in the presence of silicon, to 1240° C. Additionally, direct comparisons between the two materials have demonstrated that such additions result in an increase of 100% in the minimum resistivity, _min, at sintering temperatures beyond 1280° C. A similar increase in _max for sintering temperatures below 1360° C and a five-fold reduction in the ratio of _max/_min in samples sintered above 1320° C have also been attributed to the presence of aluminium. It was further found that aluminium increases the average grain size by 30% and promotes the formation of a liquid phase.     

Carbothermal reduction synthesis of nanocrystalline zirconium carbide and hafnium carbide powders using solution-derived precursors

Zirconium carbide (ZrC) and hafnium carbide (HfC) powders were produced by the carbothermal reduction reaction of carbon and the corresponding metal oxide (ZrO₂ and HfO₂, respectively). Solution-based processing was used to achieve a fine-scale (i.e., nanometer-level) mixing of the reactants. The reactions were substantially completed at relatively low temperatures (<1500°C) and the resulting products had small average crystallite sizes (50–130 nm). However, these products contained some dissolved oxygen in the metal carbide lattice and higher temperatures were required to complete the carbothermal reduction reactions. Dry-pressed compacts prepared using ZrC-based powders with 100 nm crystallite size could be pressurelessly sintered to 99% relative density at 1950°C.     

Hydrothermal precipitation and characterization of nanocrystalline BaTiO3 particles

Crystalline BaTiO₃ powders were precipitated by reacting fine TiO₂ particles with a strongly alkaline solution of Ba(OH)₂ under hydrothermal conditions at 80°C to 240°C. The characteristics of the powders were investigated by X-ray diffraction, transmission electron microscopy, thermal analysis and atomic emission spectroscopy. For a fixed reaction time of 24 hours, the average particle size of BaTiO₃ increased from 50 nm at 90°C to 100 nm at 240°C. At synthesis temperatures below 150°C, the BaTiO₃ particles had a narrow size distribution and were predominantly cubic in structure. Higher synthesis temperatures produced a mixture of the cubic and tetragonal phases in which the concentration of the tetragonal phase increased with increasing temperature. A bimodal distribution of sizes developed for long reaction times (96 h) at the highest synthesis temperature (240°C). Thermal analysis revealed little weight loss on heating the powders to temperatures up to 700°C. The influence of particle size and processing-related hydroxyl defects on the crystal structure of the BaTiO₃ powder is discussed.     

CO/pH2: A Molecular Thermometer

We utilize reversible temperature dependent changes in the IR absorption spectrum of CO molecules isolated in solid parahydrogen (pH₂) to probe bulk temperature changes during rapid vapor deposition. The intensity of a well resolved feature near 2135 cm^–1 increases monotonically with temperature over the 2 to 5 K range. The thermally populated initial state of this transition lies 12 K above the CO/pH₂ ground state. During the deposition of 100 ppm CO/pH₂ samples, we detect temperature gradients 10 K/cm in 0.1 cm-thick samples subjected to heat loads 10 mW/cm². The resulting estimated thermal conductivity (TC) is 3(±2) mW/cm-K, averaged over the 2 to 5 K region. This value is 1000 times lower than the TC of single crystal solid pH₂, and 10 times lower than previously measured for pH₂ solids doped with 100 ppm concentrations of heavy impurities [Manzhelii, Gorodilov, and Krivchikov, Low Temp. Phys. 22, 131 (1996)]. We attribute this abnormally low TC to the known mixed fcc/hcp structure of the rapid vapor deposited solids.     

Hydrothermal Synthesis and Spectroscopic Properties of Crystalline ZnO Powders and Films

Polycrystalline zinc oxide is synthesized under mild hydrothermal conditions (150–250°C). The phase composition, morphology, and pulsed cathodoluminescence (PCL) spectra of ZnO powders, polycrystalline films, and single crystals are studied as a function of synthesis conditions (the nature of the precursor, the type and concentration of the solvent, solution temperature, and the redox potential of the system). The crystallite size in the resultant materials varies from 100 nm to 10 m, depending on the synthesis conditions. The PCL spectra measured under pulsed electron-beam ( 2 ns) or laser (Nd:YAG, fourth harmonic, = 266 nm, 10 ns) excitation show two bands in the UV and visible spectral regions. The intensity ratio between these bands depends on the ZnO preparation conditions. The influence of the precursor and solvent on the PCL spectrum of ZnO is studied. The redox potential of the system is shown to have a strong effect on the luminescent properties of the resultant material.     

Electrical properties of non c-axis oriented SrBi2(Ta0.95V0.05)2O9 thin films

Pulsed laser deposition technique was used to grow off c-axis oriented SrBi₂(Ta_0.95V_0.05)₂O₉ (SBTV) ferroelectric thin films. X-ray diffraction studies revealed the c-axis suppression in the films grown at lower substrate temperature (350°C) followed by annealing at higher temperatures (650°C). In-plane lattice parameters of the films were decreased with increase in annealing temperature. SBTV films annealed at 750°C exhibited enhanced ferroelectric properties with remanent polarization (2P _r) of 31.5 C/cm² and coercive field (E _c) of 157 kV/cm. The dielectric permmitivity of the films increased with increase in annealing temperature and it was attributed to the grain size dependence. The films annealed at 750°C showed maximum value of dielectric permittivity 172 with a tangential loss of 0.1, at 100 kHz. Higher value of dissipation factor at lower annealing temperature is explained in terms of space charge accumulation at grain boundaries. The leakage current densities of the films follow ohmic behavior at low field regime and space charge limited current dominates at higher fields.     

Investigation of superplasticity by the impression creep technique

Impression creep tests have been carried out on a Zn-22% Al eutectoid alloy in two heattreatment conditions, as a function of applied stress and at temperatures of 25 to 270° C. At small grain sizes ( 0.9m) and in the temperature range 180 to 270° C, the observed deformation response conforms to Regions I, II and III typical of superplastic behaviour. Furthermore, strain-rate index values determined for Region II fall in the range 0.44 to 0.51, consistent with superplasticity. It is concluded that the impression creep technique offers considerable potential for characterization of superplastic alloy systems on small specimen volumes.