Influence of stabilizers on Na-β′′-Al2O3 phase formation in Li2O(MgO)-Na2O-Al2O3 ternary systems

The influences of stabilizers on - and -Al2O3 phase formations in Li2O(MgO)-Na2O-Al2O3 systems were investigated. When stabilized with 4MgCO3Mg(OH)25H2O, most of the -Al2O3 phase formed below 1200°C and further - to -Al2O3 transformation with an increase of temperature was not observed. On the other hand, when stabilized with Li2CO3,-Al2O3 formation occurred by two steps. First, -Al2O3 was partly formed below 1200°C, and, second, noticeable transformation from -Al2O3 to -Al2O3 occurred at higher temperature ranges. It was shown that transient eutectic liquid in the Li2O-Na2O-Al2O3 system promoted the - to -Al2O3 transformation at higher temperatures. Uniform distribution of both Mg2+ and Li+ stabilizing ions enhanced -Al2O3 formation at low temperatures. In the Li-stabilized systems, however, homogeneous distribution of Li+ ions hindered both the formation of transient eutectic liquid and the second - to -Al2O3 phase transformation at high temperatures.     

Fabrication of β- and β′′-Al2O3 tubes by pressureless powder packing forming and salt infiltration

A new forming method, pressureless powder packing (PLPP), was studied to fabricate the - and -Al2O3 tubes. Alkali sources were infiltrated into the pores of -Al2O3 tube preforms that had been prepared by the PLPP forming method. The composition for the synthesis of -Al2O3 phase was Na2O · 0. 138Li2 · 4.4Al2O3. The -Al2O3 fraction of calcined and sintered bodies was increased with the increase of calcination temperature, and phase formation was largely affected by the type of starting -Al2O3. Large particle size and narrow size distribution of fused -Al2O3 resulted in uniform green microstructure that enhanced the homogeneity of alkali salts after infiltration, which was very important for the -Al2O3 formation. Sintered microstructure was uniform in all specimens but further development was required for density improvement.     

Amorphous phase formation of the pseudo-binary Al2O3–ZrO2 alloy during plasma spray processing

Thick deposits of the Al2O3–ZrO2 with near eutectic compositions were prepared by plasma-spray deposition and subjected to heat treatment to investigate the crystallization and phase transformation behaviors. The structures of as-sprayed deposits are mostly amorphous and a small amount of t-ZrO2 and -Al2O3 particles with a diameter of approximately 20 nm are also present. Simultaneous crystallization of t-ZrO2 and -Al2O3 from the glass occurs at 945 °C, followed by - and -Al2O3 above 1000 °C, and only -Al2O3 are observed above 1200 °C. Phase transformation of t-ZrO2 to m-ZrO2 occurs at 1213 °C. There is no appreciable difference in amorphous formation and subsequent crystallization and phase transformation behaviors with two different feedstock powder sizes. It is shown that it is feasible to produce the thick amorphous Al2O3–ZrO2 materials with proper control of plasma spraying process parameters.     

Formation of catalytic CuLaAl11O19/Al2O3composite powder

The solid-state reaction and hydrocarbon-removal activities of composite powders in the system of CuO and La-modified Al2O3 were studied for the purpose of their application to heat-stable catalyst in exhaust-treatment. X-ray diffraction revealed the formation of catalytic nanocomposite-powder of CuLaAl11O19 and -Al2O3 at 1100 °C from the solid-state reaction between -Al2O3, CuO and La2O3. The La-modification of -Al2O3 was effective to maintain the large surface areas of these composite powders. The C6H6 removal activities were compared with practical automotive catalyst in the system of Pt–Ce and -Al2O3. The composite-powder of CuLaAl11O19 and -Al2O3 is active for complete oxidation of benzene and the microstructure is favourable as a powder for catalytic coat-layer.     

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.     

Phase transformation in the Al2O3–ZrO2 system

Co-precipitation methods have been used to produce 20 mol% Al2O3–80 mol% ZrO2 mixed oxides, from aqueous solutions of zirconium oxychloride and aluminium chloride, followed by precipitation with ammonia. The resulting gel was calcined at increasing temperatures, and X-ray diffraction confirmed that the structure remained amorphous up to 750°C and then crystallized as a single-phase cubic zirconia solid solution, but with a reduced unit-cell dimension. At higher temperatures, the unit-cell dimension increased and, above 950°C, this phase started to transform to a tetragonal zirconia (t-ZrO2) phase, again of reduced cell dimensions compared with t-ZrO2, with simultaneous appearance of small amounts of -Al2O3. Above 1100°C, the tetragonal phase transformed to monoclinic zirconia on cooling, and the amount of -Al2O3 increased. Above 1200°C, the -Al2O3 transformed to the stable -Al2O3. These results confirm that aluminium acts as a stabilizing cation for zirconia up to temperatures of about 1100°C. © 1998 Chapman & Hall     

Sol-emulsion-gel synthesis of hollow mullite microspheres

Hollow mullite microspheres were obtained from emulsified diphasic sols by an ion extraction method. The surfactant concentration and viscosity of the sols were found to affect the characteristics of the derived microspheres. The gel and calcined microspheres were investigated by using thermogravimetry analysis (TGA), differential thermal analysis (DTA), Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), optical and scanning electron microscopy (SEM) and particle size analysis. TGA indicated the removal of most of the volatiles, i.e. 30.77 wt% up to about 500°C. Crystallization of the Si-Al spinel at 900°–970°C in gel microspheres was confirmed by DTA and XRD. XRD results also showed the formation of orthorhombic mullite at 1200°C. FTIR indicated the sequence of transformations taking place during heat-treatment of gel microspheres at different temperatures. The optical and scanning electron microscopy confirmed the spherical morphology of the gel and calcined particles. Formation of hollow microspheres with a single cavity was identified by SEM. The particle size distribution of the mullite microspheres calcined at 1300°C/1h exhibited a size range of 6–100 m with an average particle size (d ₅₀) of 22.5 m.     

Sol gel preparation,structure and thermal stability of crystalline zirconium titanate microspheres

Very pure and crystalline ZrTiO₄ microspheres (15–50 m) were prepared by two sol gel methods using a zirconia sol and two types of titania sols and characterized by scanning electron microscopy, X-ray diffraction and simultaneous differential thermal and thermogravimetric analysis. On gelation of the mixed sols, microspheres of an amorphous material with Zr/Ti ratio of 1.0 were obtained by each route. The amorphous materials obtained by the two routes transformed to fully crystalline ZrTiO₄ at 500 and 600 °C, respectively. The high temperature thermal stabilities of these materials were also studied.     

Influence of the silica matrix on the formation of α-alumina in a mullite–alumina composite from a diphasic precursor

In mullite–alumina composite precursors, interaction between the silica matrix and the fine -alumina texture strongly influences the precursor phase transformation, the nucleation and the crystal geometry both of the mullite and of the -alumina. The mullite–alumina composite precursor calcined at 1000 °C has a layered structure probably derived from the layered texture of the -alumina. The phase transition of this layered texture is retarded by the presence of the silica matrix and a metastable mullite phase is formed before nucleation of -alumina. By leaching away the silica matrix, the remaining layered texture is readily transformed into very fine, thin -alumina platelets by calcination at 1000 °C. This seems to be one reason for the appearance of elongated mullite grains in a pure mullite matrix and the platelet shaped -alumina grains in the mullite–alumina composite prepared from diphasic precursors. © 1998 Chapman & Hall     

Spray atomization of two Al–Fe binary alloys: solidification and microstructure characterization

The effect of solidification history on the resultant microstructures in atomized Al–3Fe and Al–7Fe powders is studied, with particular emphasis on the relationships between droplet size, undercooling and phase stability. The atomized Al–Fe powders exhibit four microstructural features, i.e. Al3Fe phase, Al + Al6Fe eutectic, -Al dendrite and a predendritic structure. The presence of these is noted to depend on a kinetic phase competitive growth mechanism, which was determined by the initial undercooling experienced by the powders. The results of scanning electron microscope analysis demonstrate that the content of Fe in the -Al phase increases with decreasing powder particle size, i.e. for Al–3 wt% Fe powders, the content of Fe in the -Al phase is 2.21 and 2.56 wt% corresponding to powder particle sizes of 90 and 33 m, respectively; for Al–7 wt% Fe powders, the content of Fe in the -Al phase is 5.51 and 5.98 wt% corresponding to powder sizes of 90 and 33 m, respectively. In the present study, homogeneous nucleation undercooling, corresponding to the -Al phases, is also estimated using an existing correlation.     

Sinter forging of zirconia toughened alumina

Sinter forging experiments have been carried out on powder compacts of zirconia toughened alumina (ZTA) Ceramics Alumina-15 wt% zirconia was prepared by a gel precipitation method and calcined at temperatures of 900 or 1100°C. Full densification of ZTA ceramics was obtained within 15 min at 1400°C and 40 MPa. A homogeneous microstructure can be observed with an alumina grain size of 0.7 m and a zirconia grain size of 0.2 m. Almost no textural evolution occurred in the microstructure. During sinter forging the densification behaviour of the compacts was improved by an effective shear strain, for which values of more than 100% could be obtained. As a result of the shear deformation the densification of ZTA in the alumina phase stage shifted to lower temperature. During pressureless sintering the to alumina transformation temperature was dependent of the preceding calcination temperature, while during sinter forging this phase transformation was independent of calcination temperature and took place at a lower temperature.     

New high permittivity and low loss ceramics in the BaO–TiO2–Nb2O5 composition

New dielectric ceramics with formula BaTi3Nb4O17 and Ba6Ti14Nb2O39 have been prepared and characterized. BaTi3Nb4O17 was densified to 92% of TD after firing at 1310 °C for 4 h. However, Ba6Ti14Nb2O39 fired under optimized conditions (1260 °C for 4 h) showed only 85% TD together with secondary phase. The crystal system of both of the compositions is orthorhombic. The BaTi3Nb4O17 has r56, Qu2100 (at 4.402 GHz), f+86 p.p.m. K-1 and Ba6Ti14Nb2O39 as r50, Qu650 (4.359 GHz) and f+165 p.p.m. K-1. © 1998 Kluwer Academic Publishers     

Chemical Transformations of γ-Al(OH)3during Closed-System Heat Treatment

The chemical transformations of -Al(OH)₃during closed-system heat treatment in a self-generated gaseous atmosphere (water vapor) were studied. At t 200°C, -Al(OH)₃was found to convert into -AlOOH, which, in turn, converts into the equilibrium phase -Al₂O₃at t 400°C. The processes underlying the effect of water vapor on the kinetics and mechanisms of the chemical transformations of -Al(OH)₃and -AlOOH in a closed system are discussed.     

Electron diffraction study of superlattices and orientation variants in Ca3SrAl6SO16

Samples having the nominal composition of Ca₃SrAl₆SO₁₆ were sintered at 1380 °C and analysed by electron diffraction. The frequent appearances of forbidden and satellite reflections in this compound imply the presence of a number of basal and nonbasal superlattices so that the microstructure of this cement clinker was characterized by various superstructures including one-, two- and even three-dimensional superstructures along the 0 0 1, 1 1 0, 1 1 2, 1 1 4 or 2 2 1, 0 1 3 and 1 2 3 directions with repeat periods of two or three times of that of basic one, respectively, and intergrowth of these. Various domain structures with 90°, 120° and 48.2°, etc., orientation relationships were also detected in these superstructures and the total number of these orientation variants related to the symmetry elements lost in the process of phase transformation, can be predicted according to the conclusions of Van Tendeloo and Amerlinckx, or they are equal to the number of those unique planes in the matrix.     

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.     

A high-temperature solid-state potentiometric sensor for nitrogen based on ceramic LaAl12O18N

The nitrogen-sensing properties of LaAl12O18N are described for the first time. Positive e.m.f. measurements at high temperature across the cells -Nb (N), -Nb2N, -Al2O3, LaAl12O18NLaAl11O18 (or LaAl12O18N)LaAl12O18N, -Al2O3, -Nb2N, -Nb4N3, were in agreement with PN2(-Nb2N, -Nb4N3)>PN2(-Nb(N), -Nb2N) for the idealized stoichiometric cell reaction -Nb4N3+2-Nb(N)3-Nb2N, thus demonstrating the nitrogen-sensing property of these cells. The e.m.f. for a variety of cells with electrodes containing -V2N, -Nb2N, -Ta2N and Ti2N, were consistent with the predicted equilibrium nitrogen partial pressures.     

Synthesis and characterization of primary alumina,titania and binary membranes

The synthesis and characterization of supported and non-supported membranes of -Al₂O₃, TiO₂ and their binary combinations are described. Non-supported -Al₂O₃ and TiO₂ membranes were prepared from colloidal dispersions (sols) of boehmite and titania, respectively. Stable binary sols were also prepared by mixing boehmite and titania sols under appropriate pH conditions, and these were used to prepare binary (-Al₂O₃/TiO₂) membranes. Supported -Al₂O₃, TiO₂ and binary membranes were made by the slip-casting process using the same sols. The membrane layers had, after calcination, a thickness of 3–6 m depending on the dipping conditions, and an average pore diameter of -3–4 nm with a narrow pore-size distribution. The structural transformation of titania from the anatase to the rutile phase was retarded by performing the hydrolysis in the presence of sulphate ions. Polyvinyl alcohol was added to the sols to strengthen the gel network during the drying and calcination process. This resulted in a less critical and more controllable membrane formation process. Multiple dipping (e.g. to repeat the dipping, drying and calcination steps) appeared to be a technique by which (i) defected layers could be repaired; (ii) thick membrane layers could be prepared; and (iii) multilayer membranes consisting of layers of different components could be prepared.     

Structural transformation during sintering and annealing of beta alumina

Changes in the phase content, microstructure and lattice parameter are observed in stabilized/ alumina specimens following extended sintering and annealing treatments. The resulting state is dependent on composition of the starting powder and on temperature and duration of heat treatment; the kinetics of transformation between and alumina are generally slow and certain/ ceramics remain in a metastable state even after a prolonged high temperature anneal. Following post-sinter heat treatment, splitting of X-ray diffraction peaks reveals a segregation of the phase into two components of differing lattice parameter. With sintering schedules of a long duration the splitting may even be present in the as-fired condition as recently reported by Harbach [1]. The splitting is attributed to a structural change resulting from the expulsion of Na₂O from supersaturated grains.     

The preparation of alumina fibre by sol-gel processing

Attempts have been made to prepare alumina fibre from the colloidal sol and polymerized alkoxides. The aluminium chloride or aluminium nitrate systems were found to be potential methods for producing continuous alumina fibre: the aluminium nitrate system had a better sintering behaviour than the aluminium chloride system. The aluminium isopropoxide system, however, was unsuitable for preparing alumina fibre but was suitable for the preparation of monoliths, membranes, powders, and multicomponent ceramics. The thermal changes of these precursors were studied by transmission electron microscopy, Fourier-transform infrared spectroscopy and X-ray diffraction. The results demonstrated the different routes of phase transformation as the temperature increases. The aluminium chloride system exhibits two routes for phase transformation: (a) boehmite -Al₂O₃, and (b) gibbsite -Al₂O₃.     

Microstructure and mechanical properties of a Si3N4/Al2O3 nanocomposite

A nanocomposite material fabricated by hot pressing in the form of nanometre-sized Si3N4 particles dispersed in an Al2O3 matrix has been shown to exhibit enhanced mechanical properties compared with monolithic matrix material. It was observed by transmission electron microscopy (TEM) for the first time that the alumina grains were in the shape of elongated columns with aspect ratios in the range 2.5–4. The presence of liquid phase during sintering was found to be responsible for the appearance of columnar grains. Regular hexagon-shaped larger -Sialon grains formed during sintering were mainly situated at grain boundaries of the matrix material while irregular smaller dispersoids were trapped within the alumina grains. The improvement in the mechanical properties of the nanocomposite is attributed to the change in fracture mode from intergranular fracture to transgranular fracture, the self-reinforcement effect arising from the elongated columnar grains of the matrix, as well as the pinning effect due to the existence of intergranular -sialon particles. It was revealed that the trapped particles have an -Al2O3 structure with partial sites of aluminium and oxygen atoms substituted by silicon and nitrogen atoms, which is also likely to lead to the strengthening of the composite.