Inviscid melt-spun high-temperature alumina-magnesia fibres

Al₂O₃-MgO (AM) fibres containing 98.16 wt% Al₂O₃ and 1.84 wt% MgO, were produced via inviscid melt spinning. By using scanning electron microscopy it was found that the as-spun AM fibres were hollow and their surfaces were very rough. The X-ray diffraction pattern of the as-spun AM fibre showed -Al₂O₃ as a major phase and -Al₂O₃ as a minor phase. The DTA curve of the as-spun AM fibre showed a single endothermic peak representing the phase transformation of -Al₂O₃ to -Al₂O₃. This phase transformation was readily confirmed by analysing the X-ray diffraction pattern of heat-treated AM fibres.     

Phase transformation of inviscid melt spun (IMS) alumina-zirconia eutectic fibres

Al₂O₃-ZrO₂ (AZ) eutectic fibres containing 41.05 wt% ZrO₂ and 2.03 wt% Y₂O₃ were produced via inviscid melt spinning (IMS). Scanning electron microscopy (SEM) was used to examine the morphology of the as-spun AZ fibre. Differential thermal analysis (DTA) and X-ray diffraction (XRD) were used to investigate the phase transformations in this fibre. The XRD pattern of the as-spun AZ fibre showed tetragonal ZrO₂, -Al₂O₃, and non-equilibrium -Al₂O₃ phase formation. The DTA curve of the as-spun AZ fibre showed only one endothermic peak representing the phase transformation of -Al₂O₃ to -Al₂O₃. This phase transformation was confirmed by analysing the XRD pattern of heat-treated AZ fibre.     

The hydrolysis product of ferric nitrate in sodium hydroxide

The hydrolysis product of ferric nitrate is obtained by adding ferric nitrate solution to a boiling solution of 2.5 N sodium hydroxide. The sample is amorphous to X-rays when heated below 600° C, but it shows X-ray lines of -Fe₂O₃ at 650° C. Thermal analysis of the sample gives an endothermic peak at 80° C and two small exothermic peaks at 280° C and 700° C. Transmission electron microscopy and infrared spectroscopy confirm the primary particles as a defect form of FeOOH · H₂O. The defect FeOOH form of the sample converts to the disordered form of Fe₂O₃ on further heating around 700° C. The drastic fall in the surface area of the sample beyond 600° C suggests sudden growth of particle size, which is confirmed by a small endothermic peak at 700° C.     

Intermediate Si-Al spinel phase formation in phase transformation of diphasic mullite gel

Al₂O₃-SiO₂ diphasic mullite gel (Si/Al=1/3) has been synthesized by using Al(NO₃)₃·9H₂O and Ludox in basic conditions. Its phase transformation behaviour has been studied by qualitative and quantitative X-ray diffraction techniques. The results indicate that a noncrystalline alumino-silicate phase forms together with the slow crystallization of Si-Al spinel phase of a mullite-like composition up to 1250 °C. Thereafter, it transforms suddenly to orthorhombic mullite around 1325 °C. Earlier studies, e.g. alkali leaching, and measurement of co-ordination number of aluminium in 1000 °C heated diphasic gel, confirm Si-Al spinel formation as an intermediary phase.     

Preparation and study of YSTZ-Al2O3 nanocomposites

Yttria stabilized zirconia-alumina (YSTZ-Al₂O₃) nanocomposite system with various Al₂O₃ concentrations has been synthesized by sol-gel route. The experimental techniques XRD, DTA, TGA, FT-Raman, FT-IR, SEM, Vickers hardness measurements, density measurements and Impedance spectroscopy were used to characterize the synthesized specimens. DTA result shows two exothermic reactions: one around 760°C and another around 960°C. XRD results confirm that the specimen starts to crystallize on heating above 750°C. Well resolved XRD reflections corresponding to tetragonal (t) ZrO₂ were obtained after the specimens were heated at 1000°C. FT-Raman results confirmed that the crystallites developed above 750°C was t-ZrO₂. It was observed from the XRD and DTA results that the bulk and grain boundary region crystallize independently in two different temperatures with a difference in temperature of about 200°C. The crystallization temperatures increase with Al₂O₃ contents. At 1300°C, the pure YSTZ and 5 and 10 wt % Al₂O₃ added YSTZ specimens underwent structural transformation from tetragonal to monoclinic ZrO₂. But, the tetragonal symmetry remains stable at 1300°C with an addition of 15 wt % Al₂O₃. The system which retain its tetragonal symmetry at its processing temperature (1300°C) gives high hardness and maximum density values. Almost 100% theoretical density value was obtained at 1300°C with an addition of 15 wt % of Al₂O₃.     

The join calcium monoaluminate-calcium fluoride

The system CaO-Al₂O₃-CaF₂ is important in cement and slag technology and in metallurgy. A section of this system, the pseudo-binary join CaO·Al₂O₃-CaF₂, has been studied and the phase diagram established. This join is of particular interest since CaO·Al₂O₃ is one of the main constituents of high alumina cement.Quenching in sealed platinum capsules followed by microscopic and X-ray examination was the principal method used. The only compound on the join is 3CaO·3Al₂O₃·CaF₂ which melts congruently at 1507±1.5° C and forms one eutectic with CaO·Al₂O₃ at 11% CaF₂ and 1498±5° C and another with CaF₂ at 97.5% CaF₂ and 1405±10° C. There is a wide zone of liquid immiscibility. The m.p. of CaF₂ was determined to be 1422±1° C.Attempts to use high temperature microscopy to study this system are described.     

The crystallization of Gd2 3 -Al2O3 glasses

Glasses of Gd₂O₃ · x Al₂O₃ compositions where x represents 5/3, 4 and 6, were prepared using a rapid quenching apparatus and a laser beam. The crystallization process of the glasses was studied by means of differential thermal analysis (DTA), X-ray diffraction analysis and electron microscopy. The crystallizations of Gd₂O₃ · 5/3Al₂O₃, Gd₂O₃ · 4Al₂O₃ and Gd₂O₃ · 6Al₂O₃ are complex and exhibit one, two and three exothermic peaks in DTA measurement with increasing Al₂O₃ concentration, respectively. The crystallization process of Gd₂O₃ · 5/3Al₂O₃ glass involved the direct formation of the gadolinium aluminium garnet, 3Gd₂O₃ · 5l_{2 3} (GdAG), which is not obtained by the ordinary solid phase reaction. After crystallization of Gd₂O₃ · 4Al₂O₃ and Gd₂O₃ · l_{2 3} glass, both phases become a mixture of Gd₂O₃ · Al₂O₃ (perovskite type) and -Al₂O₃.     

Preparation, sintering and fracture behavior of Al2O3/LaAl11O18 ceramic composites

Al₂O₃/25 vol% LaAl₁₁O₁₈ composites were prepared by pressureless sintering at 1550°C with composite powders obtained by copercipiated method using La(NO₃) · 6H₂O and Al(NO₃)₃ · 9H₂O as starting materials. The enhanced reactive activity of Al₂O₃ and chemically homogeneous mixing of the constituents made LaAl₁₁O₁₈ phase to be formed at low temperature in composite powders. AlF₃ additive was used to reduce the transformation temperature of transition alumina. The LaAl₁₁O₁₈ grains in the composite powder obtained at 1500°C showed rodlike morphology distributed homogeneously in Al₂O₃ powder. The samples sintered at 1550°C for 4 h with CAS (CaO-Al₂O₃-SiO₂) sintering aid can obtain a high relative density. The effects of the sintering time on the grain growth of Al₂O₃ and the fracture toughness of the composites were studied and the results showed that LaAl₁₁O₁₈ grains reduced the growth of Al₂O₃ grains and the rodlike grains increased the fracture toughness. The improvement in fracture toughness of the composites was mainly attributed to the mechanism of crack deflection.     

Microstructure and mechanical properties of silicon carbide fibre-reinforced aluminium nitride composite

SiC continuous fibre (15 vol%)/AlN composite was fabricated using a sintering additive of 4Ca(OH)₂ · Al₂O₃ by hot-pressing at 1650 °C and 17.6 MPa in vacuum. Analytical transmission electron microscopy and scanning electron microscopy were used to investigate the microstructure of as-fabricated and crept SiC fibre/AlN composites. The room-temperature mechanical and high-temperature creep properties of the composite were investigated by four-point bending. The incorporation of SiC fibre into AlN matrix improved significantly the room-temperature mechanical properties. This improvement could result from the crack deflections around the SiC fibres. However, the incorporation degraded severely the high-temperature creep properties under oxidizing atmosphere. This could be attributed to the development of the pores and various oxides at the matrix grain boundary and matrix/fibre interface during creep test.     

In situ fabrication of (α-Al2O3 + Al3Zr)/Al composites in an Al–ZrO2 system

Synthesis of a (α-Al₂O₃ + Al₃Zr)/Al in situ composite via exothermic dispersion synthesis (XD) process in an Al–ZrO₂ system has been investigated. Thermodynamic analysis indicates that the reaction between Al and ZrO₂ can spontaneously occur due to its negative Gibbs free energy of the Al–ZrO₂ system. When the reinforcement volume fraction is 30 vol.%, there is only one exothermic peak observed in the DSC curve. The final combustion products are α-Al₂O₃ particles and Al₃Zr blocks, which distribute uniformly in the aluminum matrix. The tensile strength, elongation rate and micro-hardness are 215.2 MPa, 3.0% and 304 MPa, respectively. However, if the reinforcement volume fraction increases to 100 vol.%, two exothermic peaks are observed in its corresponding DSC curve and the peak intensities are significantly increased. When the heating rates are 10 °C/min, 20 °C/min and 30 °C/min, the initiation temperatures are 744 °C, 776 °C and 782 °C, respectively. The reactions occurred in the Al–ZrO₂ system have two steps: the first is that the Al atom reacts with ZrO₂ to produce the α-Al₂O₃ and active Zr atoms, and the second is that the active Zr atoms disperse into the matrix and react with Al to form Al₃Zr. The values of activation energy of the two reactions are around 315.8 kJ/mol and 191.1 kJ/mol, respectively.     

Vinylphosphonic acid-modified calcium aluminate and calcium silicate cements

Cementitious materials in terms of calcium phosphate cements (CPC) were prepared through the acid-base reaction between vinylphosphonic acid (VPA) and calcium aluminate cement (CAC) reactants or calcium silicate cement (CSC) reactants at 25 °C. Using CAC, two factors were responsible for the development of strength in the cements: one is the formation of an amorphous calcium-complexed vinylphosphonate (CCVP) salt phase as the reaction product, and the other was the high exothermic reaction energy. Because the formation of CCVP depletes the calcium in the CAC reactants, Al₂O₃·xH₂O gel was precipitated as a by-product. CCVP amorphous calcium pyrophosphate hydrate (CPPH) and Al₂O₃·xH₂O -AlOOH phase transitions occurred in the CPC body autoclaved at 100 °C. Increasing the temperature to 200 °C promoted the transformation of CPPH into crystalline hydroxyapatite (HOAp). In the VPA-CSC system, the strong alkalinity of CSC reactant with its high CaO content served in forming the CPPH reaction product which led to a quick setting of the CPC at 25 °C. Hydrothermal treatment at 100 °C resulted in the CPPH HOAp phase transition, which was completed at 300 °C for both the VPA-CAC and VPA-CSC systems, and also precipitated the silica gel as by-product. Although the porosity of the specimens was one of the important factors governing the improvement of strength, a moderately mixed phase of amorphous CPPH and crystalline HOAp as the matrix layers contributed significantly to strengthening of the CPC specimens.     

Dip coated 12CaO·7Al2O3 thin films through sol-gel process using metal alkoxide

Transparent nanostructured 12CaO·7Al₂O₃ thin films with cubic structure have been prepared on soda lime glass substrates via the sol-gel dip coating using the precursor sol solution at low temperature. The structural, compositional, morphological and optical properties of the 12CaO·7Al₂O₃ films and powder were studied using X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy. Optical properties of 12CaO·7Al₂O₃ films have been investigated using UV-visible spectroscopy. Two different precursor sols were prepared using calcium-2-ethyl hexonate and aluminium isopropoxide as precursor materials in isopropanol and ethylene glycol monomethyl ether solvents. Dip coated gel like films were dried at 120 °C for 15 min and subsequently heat-treated at 450 °C for 1 h in air atmosphere. The influence of films thickness and optical transparency with use of different solvent and sol concentration on microstructure of the films were established. In addition, XRD patterns revealed that 12CaO·7Al₂O₃ films have been composed of cubic phase. SEM observations exhibited that the films structure becomes more homogeneous using isopropanol as compared to ethylene glycol monomethyl ether solvent. The 12CaO·7Al₂O₃ films prepared using 2 (wt.%) sol in isopropanol had high transparency nearly 88% in wide visible range with maximum of 90% at 600 nm wavelength.     

Sintering and crystallization of (SrO·SiO2)-(SrO·Al2O3·2SiO2) glass-ceramics

In the ternary SrO-Al₂O₃-SiO₂ system the pseudobinary join composition of 50 wt % SrO·SiO₂–50 wt % SrO·Al₂O₃·2SiO₂ (SS-SA2S) showed a glass melting temperature of 1500 °C and a crystallization peak temperature of 1100 °C. The (SS-SA2S) glass-ceramic pellets prepared by cold pressing and pressureless sintering, showed very low porosity. The (SS-SA2S) glass-ceramics containing B₂O₃ and those containing B₂O₃ and TiO₂ revealed crystallization peak temperatures of 1000 °C and unexpectedly high porosity. By applying Kissinger analyses to the DTA data the activation energy values for crystallization of the three glass-ceramics were determined to range from 196 to 255 kJ/mol. The Ozawa analyses on the DTA data gave the Avrami parameter values at 3.69 to 3.95. The X-ray diffraction (XRD) patterns from the three glass-ceramics revealed formation of the equilibrium crystalline phases of SrO·SiO₂ and SrO·Al₂O₃·2SiO₂ (monocelsian).     

Solid state reactions in the ZrO2 · SiO2 - αAl2O3 system

Solid state reactions between ZrO₂· SiO₂ and Al₂O₃ in mixed powders were studied by quantitative X-ray diffraction, density measurements and qualitative EDAX. Data were obtained at temperatures ranging from 1400 to 1600° C for 5 h; the initial molar ratios of the reactants (Al₂O₃/ZrO₂ · SiO₂) varying from 0 to 5. The results indicate that: (1) ZrO₂· SiO₂ and Al₂O₃ react and form ZrO₂, crystalline 3Al₂O₃ · 2SiO₂ and a noncrystalline mullite phase; (2) the non-crystalline mullite phase is an important transitional phase towards equilibrium under subsolidus conditions. In the experimental conditions used the amount of the non-crystalline phase varies by as much as about 15%. This phase is of great importance in the mechanisms of reaction sintering between ZrO₂ · SiO₂ and Al₂O₃.     

Economical synthesis of Al2O3 nanopowder using a precipitation method

Al₂O₃ nanopowder was synthesized by the precipitation method using inexpensive AlCl₃·6H₂O and Al powder as raw materials. The dried precipitate was heat treated in the range of 60-1200 °C. The influence of heat treatment on crystallization and phase transformation of the precipitate was investigated using X-ray diffractometry (XRD), thermogravimetry and differential thermal analysis (TG-DTA) and Fourier transform infrared spectroscopy (FTIR). Scanning electron microscopy (SEM) reveals that the particle size of the powders lies between 30 and 95 nm.     

High-temperature glass-ceramics of the BaO-Al2O3-SiO2-Ta2O5 system and molybdenum metal composites

Glass-ceramics which consist of tantalum pentoxide (Ta₂O₅), hexacelsian (BaO·Al₂O₃· 2SiO₂), and aluminium tantalate (Al₂O₃·Ta₂O₃) are described. These glass-ceramics can form refractory composites up to 1400° C with molybdenum metal. The glass-ceramics and metal have compatible physical and chemical properties which allow close thermal expansion and excellent bonding.     

Sintering and crystallization of off-stoichiometric BaO·Al2O3·2SiO2 glasses

Glass-ceramics with off-stoichiometric celsian composition of 50 wt% BaO·2SiO₂ – 50 wt% BaO·Al₂O₃·2SiO₂, (B2S-BA2S) were fabricated and investigated for their sintering and crystallization characteristics. (B2S-BA2S) glass powder showed a melting temperature much lowered compared to that of stoichiometric BaO·Al₂O₃·2SiO₂ (BA2S) glass powder and high sintering ability. (B2S-BA2S) glass powder containing B₂O₃, (B2S-BA2S)B and that containing B₂O₃ and TiO₂, (B2S-BA2S)BT revealed much lowered crystallization peak temperatures, but rather low sintered density. By applying Kissiger analysis to differential thermal analysis (DTA) data activation energy values for crystallization were determined as 265, 195 and 242 kJ/mol, respectively for (B2S-BA2S), (B2S-BA2S)B and (B2S-BA2S)BT glasses. X-ray diffraction (XRD) patterns from all the glass-ceramics crystallized at 1100°C for 4 h revealed formation of crystalline phases of -BaO·2SiO₂, monocelsian and hexacelsian. (B2S-BA2S) glass-ceramics crystallized at 1400°C for 4 h showed formation of -BaO·2SiO₂ and monocelsian phases with only trace of metastable hexacelsian phase.     

Low-temperature mechanochemical–thermal synthesis of α-Al2O3 nanocrystals

The great capability of high-energy ball milled basic polyaluminium chloride gel (PACl) which consisted of the monomeric Al³⁺ ions and polymerized Al³⁺ species such as [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ with a Keggin like structure to enhance the phase transformation into α-Al₂O₃ nanocrystals at low temperature was verified. PACl gel 10 min milled and annealed at 400 °C, partially transformed to nanocrystalline α-Al₂O₃ with the mean XRD crystallite size in the range of 15–17 nm, embedded in an amorphous or transition alumina matrix. Further crystal growth up to ∼50 nm and phase pure α-Al₂O₃ powder was obtained when heat-treated at 1000 °C. In contrast to this, the non-milled PACl gel transforms to the transition θ-Al₂O₃ phase at 1000 °C. The evolution of α-Al₂O₃ nanocrystals was studied by XRD, TEM, selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM) methods.     

The effect of carbon coating of AIN powder on sintering behavior and thermal conductivity

High thermal conductive AlN ceramics doped with Y₂O₃ were produced by sintering the powders obtained after applying a carbon coating to the surface of AlN powder grains. During sintering at 1800°C for 1 hour, the carbon reacts with the surface of the AlN grains by carbothermal-reduction of Al₂O₃, and also with the Al₂Y₄O₉ intermediate phase to form AlN, Y₂O₃ and CO. By adding 0.56 mass% of carbon, almost all the Al₂Y₄O₉ is reacted and the thermal conductivity increases from 184 W/(m · K) to 224 W/(m · K). Further carbon addition decreases the thermal conductivity and also the final sintered density.     

The phase equilibrium diagram of the ternary subsystem CaO-CaO·Al2O3-11 CaO·7 Al2O3·CaF2

On the basis of the experimental results obtained from the study of high-temperature equilibrium relations of seven pertinent joins the phase diagram of the subsystem CaO-CaO·Al₂O₃-11 CaO·7 Al₂O₃·CaF₂ has been constructed. In this diagram the delineation of the boundary curves of the primary fields of CaO, 3 CaO·Al₂O₃, CaO·Al₂O₃ and the 11 CaO·7 Al₂O₃·CaF₂ solid solution has been improved over our previously published phase diagram of the system CaO-Al₂O₃-CaF₂ [1]. The isotherms have also been drawn more precisely to give a better idea about the topography of the portion investigated.