The effect of MgAl2O4 on the formation kinetics of Al2TiO5 from Al2O3 and TiO2 fine powders

The formation of Al_2(1–x)Mg _x Ti_(1+x)O₅ solid solutions from Al₂O₃-TiO₂-MgAl₂O₄ powder mixtures of 1 m particle size and moderate purity has been studied at 1300°C for different final composition values: x=0 (pure Al₂TiO₅), 10^–3, 10^–2 and 10^–1. Analysis of the kinetic data and microstructural observation indicates that MgAl₂O₄ affects the mechanism of Al₂TiO₅ formation by providing active nuclei for the growth of the new phase. These nuclei are probably constituted by Mg_0.5AlTi_1.5O₅, i.e. the equimolar Al₂TiO₅-MgTi₂O₅ solid solution, and are formed by reaction between MgAl₂O₄ and TiO₂ at temperatures above 1150 °C. As the value of x increases, the number of titanate particles per unit volume accordingly increases and the conversion of the original oxides is faster. At values of x10^–2, the prevailing mechanism is the nucleation and growth of Al₂TiO₅ nodules for fractional conversion up to 0.8. Further conversion of the residual Al₂O₃ and TiO₂ particles dispersed into the titanate nodules is slower and controlled by solid-state diffusion through Al₂TiO₅. At x=0.1, a large number of nucleation sites is present, and solid-state diffusion through Al₂TiO₅ becomes important even in the initial stage of reaction, as the diffusion distances are strongly reduced. The study of Al₂TiO₅ formation under non-isothermal conditions in the temperature range 1250–1550°C shows that reaction proceeds between 1300 and 1350 °C for x=0.01 and between 1250 and 1300 °C for x=0.1. Densification of the titanate becomes important at temperatures above 1300°C for x=0.1, but only above 1450 °C for x=0.01.     

Decomposition of Al2TiO5-MgTi2O5 solid solutions: a thermodynamic approach

The decomposition of Al_1–x Mg _x Ti_1+x O₅ solid solutions with x=0.0, 0.1, 0.2, 0.4, 0.5 and 0.6 was studied in the temperature range 900–1175 °C using a 250 h annealing test. As x increases from 0–0.2 there is a strong stabilizing effect and the decomposition temperature decreases from 1280 °C (Al₂TiO₅) down to 1125 °C. For 0.2x0.5 the decomposition temperature does not decrease further. For x=0.6 no decomposition was observed. For x0.5 decomposition is complete or almost complete at 1000 °C; at 900 °C transformation is kinetically hindered and solid solutions with x=0.2 and 0.4 are unaffected by the thermal treatment. A relationship between the decomposition temperature and the parameter x has been derived using the regular solution model to describe the Al_2(1–x)Mg _x Ti_(1+x)O₅ solid solution.     

Thermal stabilization of aluminium titanate and properties of aluminium titanate solid solutions

Aluminium titanate has a near zero thermal expansion coefficient (=0.8×10^–6 °C^–1) in the range 20 to 1000 °C, nevertheless it decomposes below 1200 °C.The thermal stabilization of Al₂TiO₅ without altering its thermal expansion has been considered by partial substitution in the structure compound of Al³⁺ ions by Fe³⁺ ions.The solid solutions prepared by solid state reaction are in agreement with the general formula Al(1–x)₂Fe_2x TiO₅(0<x<0.2)The iron ions present in the crystal structure of Al₂TiO₅ act on its lattice parameters and bring about a catalytic effect in the formation of materials.Solid solutions show a strong thermal stability and a thermal expansion coefficient specially for the solid solution (x=0.1) which is not far from the Al₂TiO₅ value even after annealing for 300 h at 1000 °C.The mechanical properties of such materials corresponding to that solid solution present strength values lower than Al₂TiO₅ ones. After annealing, however, these are improved later due to a microcrystallization.     

Oxidation of monolithic TiB2 and of Al2O3-TiB2 composite

In view of the susceptibility of TiB₂ to oxidation, the thermal stability of monolithic TiB₂ and Al₂O₃-TiB₂ composite was investigated. The temperature at which TiB₂ ceramic starts to oxidize is about 400°C, oxidation kinetic being controlled by diffusion up toT900°C and in the first stage of the oxidation at 1000 and 1100°C (up to 800 and 500 min, respectively), and by a linear law at higher temperatures and longer periods. Weight gains of Al₂O₃-TiB₂ composite can be detected only at temperatures above 700°C and the rate-governing step of the oxidation reaction is characterized by a one-dimensional diffusion mechanism atT=700 and 800°C and by two-dimensional diffusion at higher temperatures. The composition and morphology of the oxidized surfaces were analysed.     

Preparation of composite Al2O3-TiO2 particles from organometallic precursors and transformations during heating

Equimolar Al₂O₃-TiO₂ composite powders were prepared via controlled hydrolysis of organometallic precursors, sometimes in the presence of submicrometre commercial-Al₂O₃ or anatase-TiO₂ particles. Variations in the chemical procedures were used aimed at different submicrostructures within the resulting powders. Heating such powders in air shows that structural behaviour is influenced by the micromorphology of the composite particle. Transformation temperatures of the titania phases seem to depend upon some size parameter which would represent their morphology within the powders. Studies performed on a series of non-equimolar Al₂O₃-TiO₂ composite powders showed that the temperature of -Al₂O₃ formation may be decreased by 210° C possibly due to a seeding effect of rutile. Pseudobrookite Al₂TiO₅ was never detected at 1300° C in air.     

Mechanical and magnetic properties of the rapidly quenched Cu2MnAl

Rapidly solidified Cu₂MnAl ribbons were fabricated by the chill-block melt-spinning technique as a function of rotation speed of an iron roller. The rapidly quenched ribbons were relatively ductile, and the total strain at failure for the bend test increased with increasing rotation speed of the roller. The effect of rapid quenching on long-range ordering in Cu₂MnAl alloy was studied by X-ray diffraction. The decomposition characteristics during isothermal ageing at temperatures between 350 and 600° C were also examined by X-ray diffraction, magnetization and Vickers hardness measurements. The decomposition reaction at temperatures below 400° C was Cu₂MnAl-Cu₉Al₄+T-Cu₃Mn₂Al+-Mn. However, at temperatures between 500 and 600° C, Cu₂MnAl decomposed into a new L2₁ type Cu₂MnAl and-Mn, and further annealing caused the appearance of-Cu₉Al₄. The decomposition rate of the rapidly quenched ribbons was faster than that of the water-quenched alloy.     

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.     

Effect of ZrSiO2 and MgO additions on reaction sintering and properties of Al2TiO5-based materials

Two sets of Al₂TiO₅-based composites were prepared by reaction sintering of (a) Al₂O₃/TiO₂/ZrSiO₄ and (b)Al₂O₃/TiO₂/ZrSiO₄/MgO powder mixtures. The influence of the variation of ZrSiO₄ content (0 to 10wt%) and the addition of 2 wt% MgO on the reaction-sintering process, microstructure, mechanical and thermal properties, were evaluated. ZrSiO₄ addition shifted the Al₂TiO₅ formation to higher temperatures, whereas MgO accelerated both Al₂TiO₅ formation and ZrSiO₄ decomposition. The presence of ZrSiO₄ and an excess of Al₂O₃ generated a dispersion of ZrO₂ and mullite particles in the grain boundaries and enhanced simultaneously the densification process. After sintering in the temperature range 1350 to 1500 ° C, the obtained composites exhibited significantly higher bending strength than the monophasic aluminium titanate (up to 80 M Pa). Al₂TiO₅ (80wt%)-mullite-ZrO₂ composites which combined good mechanical strength (55MPa), low thermal expansion (_20–1000C < 1 × 10^–6 K^–1) and excellent thermal stability were obtained by reaction and sintering of powder mixtures containing both ZrSiO₄ and MgO.     

A study on age hardening in cast Fe-Mn-Al-Si-C alloys

Phase transformations in a group of cast and solution treated (at 1100° C) Fe-Mn-Al-Si-C alloys during isothermal ageing have been investigated as a function of (a) ageing temperature (500 to 800° C), (b) aluminium (5 to 10%) and carbon (0.27 to 0.9%) contents for fixed manganese ( 30%) and silicon ( 1.5%) levels. Irrespective of the ageing temperature and carbon content, 5% Al alloys do not undergo appreciable ageing. Ageing tendency increases with increase in aluminium and carbon contents. Hardening is caused by the precipitation of Al(Fe, Mn)C _x phase inside the austenite grain and Mn₁₂Si₇Al₅ phase at the grain boundaries. The sequence of precipitation of the phases depends on the ageing temperature and composition. Cold working by rolling, after homogenization at 1100° C, accelerates ageing.     

The modulated structure formed by isothermal ageing in ZrO2-5.2 mol % Y2O3 alloy

The modulated structure produced by isothermal ageing of ZrO₂-5.2 mol % Y₂O₃ alloy was examined mainly by electron microscopy. It was found that the modulated structure was formed at ageing temperatures between 1400 and 1600° C, but not at 1700° C. The structure is developed by spinodal decomposition, which produces compositional fluctuation in the elastically soft 111 direction in cubic zirconia. The hardness increase caused by the development of modulated structure during ageing is larger than the hardening by precipitation of tetragonal phase in the cubic matrix.Graduate Student, Tohoku Univerisy, Sendai, Japan.     

Preparation and sintering of narrow-sized Al2O3-TiO2 composite powders

Narrow size distribution Al₂O₃-TiO₂ composite powders containing nominally 10 to 60 mol % TiO₂ were prepared by the stepwise hydrolysis of titanium alkoxide in an Al₂O₃ dispersion. Particle size was controlled by selecting the particle size of the starting Al₂O₃ powder. The TiO₂ content was determined by the amount of alkoxide hydrolysed. Composite powder compacts were prepared by filter casting or centrifugal casting the composite powder dispersions. All compacts had similar shrinkage behaviour during sintering. When fired above 1300° C, the compacts containing less than 50 mol % TiO₂ became Al₂TiO₅-Al₂O₃ composite bodies with high densities, the compact containing 50 mol % TiO₂ became an Al₂TiO₅ body with domain structure, and the compact containing 60 mol % TiO₂ formed a TiO₂-Al₂TiO₅ composite structure. When these composite bodies were annealed below 1300° C, they showed different decomposition behaviour and microstructures.     

Effect of TiO2 addition on oxidation behavior of sintered bodies composed of Si3N4-Y2O3-Al2O3-AlN

The effect of TiO₂ content on the oxidation of sintered bodies from the conventional Si₃N₄-Y₂O₃-Al₂O₃-AlN system was investigated. Sintered specimens composed of Si₃N₄, Y₂O₃, Al₂O₃, and AlN, with a ratio of 100 : 5 : 3 : 3 wt% and containing TiO₂ in the range of 0 to 5 wt% to Si₃N₄, were fabricated at 1775 °C for 4 h at 0.5 MPa of N₂. Oxidation at 1200 to 1400 °C for a maximum of 100 h was performed in atmospheres of dry and wet air flows. The relation between weight gain and oxidation time was confirmed to obey the parabolic law. The activation energies decreased with TiO₂ content. In the phases present in the specimens oxidized at 1300 °C for 100 h in dry air, Y₃Al₅O₁₂ and TiN, which had existed before oxidation, disappeared. Alpha-cristobalite and Y₂O₃·2TiO₂ (Y2T) appeared in their place and increased with increasing TiO₂ content. In those oxidized at 1400 °C, -cristobalite was dominant and very small amounts of Y₂O₃·2SiO₂ and Y2T were contained. There was a tendency for more -cristobalite to form in oxidation in wet air than in dry air. Therefore, moisture was confirmed to affect the crystallization of SiO₂ formed during oxidation. Judging from the lower activation energy, the crystallization, and the pores formation, we concluded that the addition of TiO₂ decreases oxidation resistance.     

In situ synthesis of Mo(Si,Al)2-SiC composites

An in situ reaction was proposed and investigated to produce Mo(Si_{1 – x} Al _x )₂-SiC composites. The starting powders were MoSi₂, Al and C. A direct current hot pressing (DCHP) method was used to prepare these composites. When the mixed powder was hot pressed at temperatures lower than 1500°C, the phase composition was Mo(Si,Al)₂ and -SiC. When the hot pressing temperature was higher than 1600°C, however, Nowotny phase Mo₅Si₃C₁ appeared. The chemical stoichiometry of the proposed in situ reaction becomes difficult because of the formation of solid solution among these phases and the appearance of Mo₅Si₃C phase. The in situ formed SiC phase in the x = 0.3 sample was partly in whisker shape. However, the SiC phase in x = 0.15 sample was in particle shape. These in situ formed SiC particles and whiskers acted as crack deflection and bridging elements and improved the fracture toughness. The Vickers hardness and fracture toughness of the x = 0.3 sample hot pressed at 1700°C for 60 min in vacuum were 15.6 GPa and 5.39 MPa · m^1/2, respectively.     

Preparation and photoconduction of rapidly quenched films in the Bi2O3-TiO2 system

The rapidly quenched films in the Bi₂O₃-TiO₂ system (0 to 60% TiO₂) were prepared using a twin-roller type apparatus. The films precipitated Bi₂O₃ solid solutions of different types in the composition ranges, with TiO₂ contents of 0 to 5, 7.5 to 10 and 12.5 to 40%, respectively. The first solid solution had a tetragonal structure of -form. The second, though also crystallized in the tetragonal structure, adopted a disordered modification of the -form. The third solid solution was -form (defect fluorite structure). The formation of amorphous phase commenced in the composition with 30% TiO₂, and the films became completely amorphous beyond 50% TiO₂. The quenched films showed a certain instability to decompose or transform into the different phase assemblage by annealing at higher temperatures (about 400 to 500° C, except 260° C for the pure Bi₂O₃ film). The quenched films were also characterized by a high photoconductivity. The photoconduction mechanism was suggested to be associated with a structural imperfection of Bi₂O₃ accompanied by a certain amount of pentavalent bismuth ion.     

Low-fired microwave dielectrics in ZnO-TiO2 ceramics doped with CuO and B2O3

The microwave dielectric properties and the microstructure of low-firing zinc titanate ceramics have been investigated. The microstructure of these ceramics have been studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and it was found that CuO addition has the important effect of stabilizing the Zn₂TiO₄ phase. When the sintering temperatures are in the range of 870–950 °C, dielectric constant values ( _r ) saturate at 21–25, the Q×f value is 20 000 GHz (at 10 GHz). The temperature coefficient of resonant frequency ( _f ) was 10 ppm °C^–1. Therefore, the 0.5 wt %-CuO and 1.0 wt %-B₂O₃ doped ZnO-TiO₂ ceramics can be used in multi-layer microwave devices requiring low sintering temperature.     

Solid ? liquid phase transformations in hypereutectic P/M Al-Si-Fe-X alloys

In this study, the metastable and stable solid liquid phase transformations of the hypereutectic alloys Al-20Si-5Fe-2Ni (wt%) and Al-17Si-5Fe-3.5Cu-1.1Mg-0.6Zr in as-atomised powder and in as-hot-forged material have been investigated. Differential Scanning Calorimetry (DSC) measurements at high temperatures have been performed. The resultant products have been thoroughly analysed using Light Optical Microscopy (LOM), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) microanalysis. During solidification large Si, (Al₄FeSi₂), FeNiAl₉, Al₇Cu₂Fe and Q(Cu₂Mg₈Si₆Al₅) are formed. A cooling rate of 5 °C/min and 1 °C/min is too high for the formation of the equilibrium phases (Al₅FeSi) and Al₇Cu₂Fe. The understanding of the sequence of transformations is useful in order to define appropriate processing parameters for these alloys produced by powder metallurgy. The temperature at which the first liquid phase appears during heating at 5 °C/min is 559 °C for the Al-Si-Fe-Ni powder and 506 °C for the Al-Si-Fe-Cu-Mg-Zr powder.     

Characterization of shock-hardened Al-8090 alloy

The structure and mechanical properties of Al-Li8090 alloy, that was dynamically deformed and then age hardened, were studied as a function of the changes in the nature and amount of precipitates produced. A comparison was made between two groups of samples, one group that was solution heat treated (SHT) and quenched from 530°C before the dynamic deformation and the other group that was dynamically deformed in the as-received (AR) condition. The higher values for microhardness and ultimate tensile strength observed (138 and 140 VHN, and 405 and 458 MPa, respectively), subsequent to shock treatment (ST), have been attributed to the increase in dislocation density and grain-boundary precipitation produced due to shock deformation. Dislocations and grain boundaries were assumed to act as precipitation sites and an increase in dislocation density, due to ST, was expected to increase precipitation density of (Al₃Li), S(Al₂CuMg), and T₁(Al₂CuLi) phases which, in turn, are expected to increase strength properties of the alloy. Differential scanning calorimetry showed that, for the species that precipitate below 180°C, (Al₃Li) and GP zones, an increase in the amount of deformation increased the precipitation temperatures. However, for the species that precipitate at 197°C, S(Al₂CuMg), an increase in the amount of deformation produced a decrease in its precipitation temperature. These results have been partially confirmed by the activation energy calculations for temperatures below 197 °C, which show a decrease of precipitation energies with an increase in the amount of deformation. Activation energies calculated from ageing curves showed that when ageing at low temperature (165–180 °C range), activation energies for the precipitation process are decreased upon increase in cold work. Shock treatment of SHT samples exhibited decreased activation energy values of precipitation, from 36.14 kcal mol^–1 for the SHT sample to 24.18, 24.08, and 21.00 kcal mol^–1 for SHT + ST samples 1, 2, and 3, respectively (corresponding to 1, 2, and 3 sheets of explosive). Activation energies of precipitation for AR + ST samples showed even lower values; 9.45, 9.95, and 8.21 kcal mol^–1 for samples 4, 5, and 6, respectively. These activation energies strongly corroborate the role of defect substructure on the age-hardening kinetics of this alloy.     

Oxidation protection of carbon-carbon composites by sol-gel ceramic coatings

Carbon-carbon composites were coated with Calcium Magnesium Zirconium Phosphate (CMZP) and Mg-doped Al₂TiO₅ sol-gels in order to form an oxygen barrier at temperatures above 650°C. The coatings were applied using a dipping technique and controlled drying procedures. It was determined that 10 coats of CMZP sol-gel fired every other coat created crack free coatings and oxidation protection. Mg-doped AlTi₂O₅ coatings produced were unsuccessful as oxidation barriers.     

Thermal stability in the Al-Al3Ti system

Directionally solidified samples of an Al-2 wt% Ti alloy were annealed at temperatures between 435° C and 660° C to investigate the thermal stability of phases formed during an incomplete peritectic transformation. The proportion of Al₃Ti present in the assolidified alloy is less than equilibrium up to about 480° C, and more than equilibrium at higher temperatures. Hence, Al₃Ti particles will be stable up to about 500° C and will tend to dissolve at higher temperatures. Diffusion due to non-equilibrium composition of the phase continues at all temperatures but is sluggish up to about 600° C. The diffusion coefficient of Ti in Al at 635° C is estimated to be 2×10^–11 cm² sec^–1.     

Phase Relations in the Systems Al2TiO5–Fe2O3 , Al2O3–TiO2–Fe2O3 , and Al2TiO5–Cr2O3

Phase relations in the systems Al₂TiO₅–Fe₂O₃, Al₂TiO₅–Cr₂O₃, and Al₂O₃–TiO₂–Fe₂O₃ are investigated, and the composition ranges of pseudobrookite Al_{2 – 2x} M_2x TiO₅ (M = Fe, Cr) solid solutions are determined.