In Situ Diffraction Study of Self-Recovery in Aluminum Titanate

Aluminum titanate (Al₂TiO₅) is an excellent refractory and thermal shock resistant material due to its relatively low-thermal expansion coefficient and high melting point. However, Al₂TiO₅ is only thermodynamically stable above 1280°C and undergoes a eutectoid decomposition to α-Al₂O₃ and TiO₂ (rutile) in the temperature range of 900°–1280°C. In this paper, we describe the use of high-temperature neutron diffraction to study the properties of self-recovery in Al₂TiO₅ when it is annealed at ≥1300°C in air. It is shown that the process of decomposition in Al₂TiO₅ is reversible and that self-recovery occurs readily when decomposed Al₂TiO₅ is reheated above 1300°C. It is further shown that the existence of a temperature range (900°–1280°C) in which Al₂TiO₅ is prone to decomposition can be explained by the competing dominance of self-recovery at ≥1280°C and decomposition at ≤1280°C.     

Synthesis, Densification, and Phase Evolution Studies of Al2O3–Al2TiO5–TiO2 Nanocomposites and Measurement of Their Electrical Properties

Alumina–aluminum titanate–titania (Al₂O₃–Al₂TiO₅–TiO₂) nanocomposites were synthesized using alkoxide precursor solutions. Thermal analysis provided information on phase evolution from the as-synthesized gel with an increase in temperature. Calcination at 700°C led to the formation of an Al₂O₃–TiO₂ nanocomposite, while at a higher temperature (1300°C) an Al₂O₃–Al₂TiO₅–TiO₂ nanocomposite was formed. The nanocomposites were uniaxially compacted and sintered in a pressureless environment in air to study the densification behavior, grain growth, and phase evolution. The effects of nanosize particles on the crystal structure and densification of the nanocomposite have been discussed. The sintered nanocomposite structures were also characterized for dielectric properties.     

Al2TiO5 Formation in Alumina/Titania Multilayer Composites

Al₂TiO₅ formation in Al₂O₃/TiO₂ multilayer composites obtained by slip casting has been studied in the temperature interval ranging from 1200° to 1450°C. It has been found that nucleation plays a fundamental role in Al₂TiO₅ formation. Furthermore, it has been observed that initial growth of Al₂TiO₅ is substantially enhanced when in contact with TiO₂.     

Synthesis and Thermal Stability of Aluminum Titanate Solid Solutions

Aluminum titanate solid solutions with empirical formulas of Al₂Ti_1-xZr_xO₅, Al_6(2-x)(6+x)Si_6x/(6+x)□_6x/(6+x)TiO₅, and Al_2(1-x)Mg_xTi_1+xO₅ were synthesized by reaction sintering and annealed at 900° to 1300°C in air to evaluate the thermal stability. Substitution of Al in Al₂TiO₅ by Si and 2Al by Mg and Ti ions to form solid solutions such as AI_{6(2-x)/(6+x)l-Si}6x/(6+x)□_6x/(6+x)TiO₅, and Al_2(1-x)Mg_xTi_1+xO₅ was effective in controlling the thermal decomposition, but substitution of Ti by Zr had little effect.     

Factors Controlling the Thermal Stability of Aluminum Titanate Ceramics in Vacuum

Aluminum titanate (Al₂TiO₅) is a promising engineering material because of its low thermal expansion coefficient, excellent thermal shock resistance, good refractoriness, and nonwetting with most metals. However, it is susceptible to thermal dissociation in the temperature range of 800°–1280°C, which degrades its desirable properties. In this work, the various factors controlling the thermal instability of Al₂TiO₅ in the temperature range of 20°–1100°C have been characterized by neutron diffraction to study the temperature- and time-dependence structural changes in real time during the process of thermal decomposition. Results show that the thermal stability of Al₂TiO₅ is strongly influenced by temperature, dwell time, heating rate, phase purity, grain size, atmosphere, and additives. Possible mechanisms of structure stabilization and instability in Al₂TiO₅ under different conditions are discussed.     

Zirconium Aluminum Carbides: New Precursors for Synthesizing ZrO2–Al2O3 Composites

ZrO₂–Al₂O₃ nanocrystalline powders have been synthesized by oxidizing ternary Zr₂Al₃C₄ powders. The simultaneous oxidation of Al and Zr in Zr₂Al₃C₄ results in homogeneous mixture of ZrO₂ and Al₂O₃ at nanoscale. Bulk nano- and submicro-composites were prepared by hot-pressing as-oxidized powders at 1100°–1500°C. The composition and microstructure evolution during sintering was investigated by XRD, Raman spectroscopy, SEM, and TEM. The crystallite size of ZrO₂ in the composites increased from 7.5 nm for as-oxidized powders to about 0.5 μm at 1500°C, while the tetragonal polymorph gradually converted to monolithic one with increasing crystallite size. The Al₂O₃ in the composites transformed from an amorphous phase in as oxidized powders to θ phase at 1100°C and α phase at higher temperatures. The hardness of the composite increased from 2.0 GPa at 1100°C to 13.5 GPa at 1400°C due to the increase of density.     

Use of Mixed-Rare-Earth Oxide in the Preparation of Reaction-Bonded Mullite at ≤1300°C

A process for production of near-net-shape mullite-matrix ceramic composites at ≤1300°C has been achieved by reaction-bonding Al₂O₃, silicon, mullite seeds, and eutectics of Al₂O₃–SiO₂–mixed-rare-earth oxide. The fusion temperature of the eutectic composition utilized is 1175°C. This liquid phase facilitates silicon oxidation, mullitization, and sintering. Mullite phase develops with low residual Al₂O₃ when 7.5 wt% mixed-rare-earth oxide and 5 wt% mullite seeds are used. The final sinter is >90% of theoretical density, >90% mullite (by quantitative XRD), and suffers 2.2% sintering shrinkage.     

Microcavity Formation in Alumina Using Ti Templates II: Mechanism and Kinetics

In part I of this work, it was found that titanium (Ti) wire encapsulated within mechanically milled alumina powder and sintered at 1350°C forms potentially useful microcavities due to the consolidation of Kirkendall porosity. Here a series of samples sintered at 1350°C in the range 0–24 h has shown the remarkable way in which these cavities form. The cavity has already started in samples quenched from the top of the heating ramp (0 min at 1350°C). It is surrounded by a diffusion zone ∼300 μm in diameter, which does not change size throughout the firing process although the contents change markedly. The diffusion zone microstructure is initially complex with phase sequence TiO₂/Al₂O₃/TiO₂+Al₂O₃/Al₂TiO₅. Microstructure evolution may be summarized as outward growth of the cavity accompanied by inward growth of the Al₂TiO₅ resulting in a ∼190-μm-diameter cavity surrounded by a 50-μm-thick layer of Al₂TiO₅. The formation of the cavity and surrounding microstructure is discussed although some features, such as the nucleation of Al₂TiO₅ in the part of the diffusion zone furthest from the Ti source and the ring of Al₂O₃, which persists in between Ti-rich parts of the diffusion zone are still poorly understood.     

Aluminum Titanate Formation by Solid-State Reaction of Fine Al2O3 and TiO2 Powders

The formation of Al₂TiO₅ has been studied in equimolar Al₂O₃-TiO₂ powder mixtures of ∼1μm particle sizes and moderate purity (∼99.8 wt%) at temperatures around 1300°C, where the free energy of formation is very small. Micro-structural development and reaction kinetics indicate that different mechanisms operate depending on the advancement of the reaction. The rapid initial reaction stage is interpreted as the nucleation-growth of Al₂TiO₅ cells in a virtually non-reacting matrix. The final reaction stage corresponds to the slow diffusion-controlled elimination of Al₂O₃ and TiO₂ dispersoids trapped during the growth of the initial Al₂TiO₅ cells.     

Microwave Dielectric Properties of Li2TiO3 Ceramics Doped with ZnO–B2O3 Frit

A type of new low sintering temperature ceramic, Li₂TiO₃ ceramic, has been found. Although it is difficult for the Li₂TiO₃ compound to be sintered compactly at temperatures above 1000°C for the volatilization of Li₂O, dense Li₂TiO₃ ceramics were obtained by conventional solid-state reaction method at the sintering temperature of 900°C with the addition of ZnO–B₂O₃ frit. The sintering behavior and microwave dielectric properties of Li₂TiO₃ ceramics with less ZnO–B₂O₃ frit (≤3.0 wt%) doping were investigated. The addition of ZnO–B₂O₃ frit can lower the sintering temperature of the Li₂TiO₃ ceramics, but it does not apparently degrade the microwave dielectric properties of the Li₂TiO₃ ceramics. Typically, the good microwave dielectric properties of ɛ_r=23.06, Q × f =32 275 GHz, τ_f = 35.79 ppm/°C were obtained for 2.5 wt% ZnO–B₂O₃ frit-doped Li₂TiO₃ ceramics sintered at 900°C for 2 h. The porosity was 0.08%. The Li₂TiO₃ ceramic system may be a promising candidate for low-temperature cofired ceramics applications.     

Reverse Micellar Route to Nanocrystalline Titanates (SrTiO3, Sr2TiO4, and PbTiO3): Structural Aspects and Dielectric Properties

Nanoparticles of strontium titanates (SrTiO₃, Sr₂TiO₄) and lead titanate (PbTiO₃) have been obtained using reverse micelles as nanoreactors. Powder X-ray diffraction studies of the powders after calcining at 800°C show monophasic SrTiO₃, Sr₂TiO₄, and PbTiO₃. X-ray line broadening studies and transmission electron microscopic studies show spherical grains of 30–40 nm size for strontium titanates, while PbTiO₃ is obtained in the form of nanorods. The dielectric constant of SrTiO₃ and Sr₂TiO₄ is found to be 90 and 30, respectively, (at 100 kHz) for samples sintered at 1000°C. PbTiO₃ shows a dielectric constant of 160 (at 100 kHz) after sintering at 900°C. The dielectric constant of Sr₂TiO₄ (with temperature) is highly stable. The temperature variation studies of the dielectric constant of PbTiO₃ show a ferroelectric phase transition at 490°C (1 kHz). The T _c varies with frequency and is found to decrease to 470°C at 100 kHz.     

Preparation of Titanium Nitride/Alumina Laminate Composites

A preparation route for TiN/Al₂O₃ laminate composites has been described. A water-based process using Al₂O₃ and TiN slurries with solids contents of 40 and 35 vol%, respectively, was used to make TiN and Al₂O₃ tapes. The removal of the binder was monitored by weight-loss measurements in a thermogravimetry unit. Bodies composed of Al₂O₃ and TiN tapes were densified at temperatures of 1400° and 1500°C using the Spark Plasma Sintering^® (SPS) technique. Densities of >98% of the theoretical densities were approached. Crack-free and almost fully densified TiN/Al₂O₃ compacts were prepared by heating the burned-out green bodies to the final sintering temperature (1500°C) at a rate of 100°C/min, and with a holding time of 5–10 min, under a pressure of 75 MPa. The microstructures of the obtained compacts were studied using scanning electron microscopy. Grain sizes in the sintered Al₂O₃ and TiN compacts were similar to those of the precursor powders. Hardness and indentation fracture toughness were measured at room temperature, and the monolithic compacts as well as the laminate composites exhibited anisotropic mechanical behavior; i.e., the cracks propagated much more easily in a direction parallel to the laminas than perpendicular to them.     

Sintering of Al2O3–TiC Composite in the Presence of Liquid Phase

The results obtained from the sintering of Al₂O₃–50TiC (in weight percent) composite in the temperature range from 1650° to 1800°C with addition of Y₂O₃ are presented. Densification is accelerated by the formation of liquid at temperatures above 1750°C, and 99% of theoretical density can be achieved by vacuum sintering at 1800°C for 15 min. The liquid presented at the sintering temperature is crystallized to YAG (Y₃Al₅O₁₂) during cooling.     

Subsolidus Phase Relationships in the System Fe2O3–Al2O3–TiO2 between 1000° and 1300°C

Subsolidus phase equilibria in the system Fe₂O₃–Al₂O₃–TiO₂ were investigated between 1000° and 1300°C. Quenched samples were examined using powder X-ray diffraction and electron probe microanalytical methods. The main features of the phase relations were: (a) the presence of an M₃O₅ solid solution series between end members Fe₂TiO₅ and Al₂TiO₅, (b) a miscibility gap along the Fe₂O₃–Al₂O₃ binary, (c) an α-M₂O₃( ss ) ternary solid-solution region based on mutual solubility between Fe₂O₃, Al₂O₃, and TiO₂, and (d) an extensive three-phase region characterized by the assemblage M₃O₅+α-M₂O₃( ss ) + Cor( ss ). A comparison of results with previously established phase relations for the Fe₂O₃–Al₂O₃–TiO₂ system shows considerable discrepancy.     

Calcium Hexaluminate and Its Stability Relations in the System CaO–Al2O3–SiO2

By a combination of solid-state sintering and quenching experiments the validity of calcium hexaluminate as a stable phase and the extent of its primary field in the system CaO–Al₂O₃–SiO₂ have been established. The size of the primary field is considerably reduced from that suggested by earlier work. The anorthite-corundum-calcium hexaluminate invariant point has been relocated at 28.0% CaO, 39.7% Al₂O₂, and 32.3% SiO₂ and at 1405°± 5°C.     

Reducing the Sintering Temperature for MgO–Al2O3Mixtures by Addition of Cryolite (Na3AlF6)

The preparation of near stoichiometric spinel and alumina-rich spinel composites from Al₂O₃and MgO powders with the addition of Na₃AlF₆up to 4 wt% in the temperature range 700°–1600°C was studied; 98 wt% spinel containing 72 wt% Al₂O₃can be produced from the mixture of 72 wt% (50 at.%) Al₂O₃+ 28 wt% (50 at.%) MgO powders with the addition of 1 wt% Na₃AlF₆fired at 1300°C for 1 h. Spinels containing 81–85 wt% Al₂O₃can be produced from either the mixture of 90 wt% (78 at.%) Al₂O₃+ 10 wt% (22 at.%) MgO or the mixture of 95 wt% (88 at.%) Al₂O₃+ 5 wt% (12 at.%) MgO powders with the addition of 4 wt% Na₃AlF₆in the temperature range 1300°–1600°C by using a torch-flame firing for 3 min, followed by quenching in water, while the same system under slow cooling in a furnace results in spinel containing 74–76 wt% Al₂O₃. Microscopic studies indicate that the alumina-rich spinel composites consist of a continuous majority spinel phase and an isolated minority corundum phase, regardless of slow cooling in a furnace or quenching in water.     

Molten-Salt Synthesis of Ba1–xPbxTiO3 in the System BaTiO3–PbCl2

Ba_{1– x} Pb _x TiO₃ powder with a fixed composition was prepared by the reaction of BaTiO₃ powders with molten PbCl₂at various PbCl₂/BaTiO₃ molar ratios at 600° and 800°C in a nitrogen atmosphere. When 0.1 μm powder was used, the reaction was finished when x = 0.9. Two phases of BaTiO₃and a solid solution of Ba_{1– x} Pb _x TiO₃ coexisted, but the final phase gave a solid solution of Ba_{1– x} Pb _x TiO₃ at 800°C. When 0.5 μm powder was used, the two phases coexisted in the products at 600°C at PbCl₂/BaTiO₃= 1.0. A sintered compact of Ba_{1– x} Pb _x TiO₃ powders solid solution was prepared by hot isostatic pressing, and its dielectric constant was measured in the temperature range 20°–550°C.     

Enhanced Thermal Stability of Zinc-Based Titanate (Dielectric) Ceramics Prepared by the Modified Sol–gel Route

A multi-component substitution of Co and Ni was incorporated into ZnTiO₃ to form pure hexagonal Zn_{1− x} (Co_1/2Ni_1/2) _x TiO₃ ( x =0,0.8,0.9,1.0) dielectric ceramic powders by a modified sol–gel route, following heat treatments at 600°C for 3 h and at 800°C for 6 h. Differential scanning calorimetry measurements revealed that the order of increasing thermal stability of solid solution compound Zn_{1− x} (Co_1/2Ni_1/2) _x TiO₃ was ZnTiO₃ (945°C), Zn_0.1Ni_0.9TiO₃ (1346°C), Zn_0.1(Co_1/2Ni_1/2)_0.9TiO₃ (1390°C), and Zn_0.1Co_0.9TiO₃ (>1400°C). Both the dielectric constant and loss tangent reached a maximum at x =0.8 and then decreased with solubility, x , and measurement frequency.     

Characterization and Sintering Behavior of Alkoxide-Derived Aluminosilicate Powders

Submicrometer SiO₂-Al₂O₃ powders with compositions of 46.5 to 76.6 wt% Al₂O₃ were prepared by hydrolysis of mixed alkoxides. Phase change, mullite composition, and particle size of powders with heating were analyzed by DTA, XRD, IR, BET, and TEM. As-produced amorphous powders partially transformed to mullite and Al-Si spinel at around 980°C. The compositions of mullite produced at 1400° and 1550°C were richer in Al₂O₃ than the compositions of stable mullite solid solutions predicted from the phase diagram of the SiO₂-Al₂O₃ system. Particle size decreased with increasing Al₂O₃ content. The sintered densities depended upon the amount of SiO₂-rich glassy phase formed during sintering and the green density expressed as a function of particle size.     

Some Properties of Aluminum Carbide Powder Prepared by the Pyrolysis of Alkylaluminu

Ultrafine aluminum carbide (Al₄C₃) powders with crystallite sizes of <40 nm were prepared by the pyrolyses of alkylaluminums, i.e., trimethylaluminum (Al(CH₃)₃: TMAL), triethylaluminum (Al(C₂H₅)₃: TEAL), triisobutylaluminum (Al(i-C₄H₉)₃: TIBAL) at a temperature between 950° and 1100°C. Although the pyrolysis of TMAL produced Al₄C₃ at 950°C, the pyrolysis temperature of TEAL to produce Al₄C₃ was raised up to 1100°C. The pyrolysis of TIBAL at 1100°C produced not only crystalline Al₄C₃ but also amorphous oxycarbide. The TEAL-derived powder had the highest true density (2.89 g^.cm⁻³ or 97% of the theoretical density) among the three kinds of powders.