Physical properties of slip casting of high pure Al2O3 slurry using porous Al2O3-glass mold

Physical properties of advanced ceramics are influenced by impurities produced in the forming process. The forming compacts produced by slip casting using gypsum molds contain calcium and sulfur in green bodies. Therefore, a porous Al₂O₃-glass mold was produced and slip casting was performed in the present study. Porous Al₂O₃ ceramics as casting molds were examined in comparison with gypsum mold from viewpoints of free energy for wettability and rate of filter cake buildup. The sintered compact of Al₂O₃ produced by slip casting using the porous Al₂O₃-glass mold was compared with those using the gypsum mold. Transmittance of the sintered Al₂O₃ compacts using the porous Al₂O₃-glass molds was increased in comparison with that using the gypsum mold.     

In situ reacted TiB2-reinforced alumina

In situ formation of TiB₂ in Al₂O₃ matrix through the reaction of TiO₂, boron and carbon has been studied. In hot-pressed samples, in addition to TiB₂, TiC and Al₂TiO₅ were also found to be dispersed phases in Al₂O₃ matrix. However, in the case of pressureless-sintered samples, pure Al₂O₃/TiB₂ composite with > 99% relative density can be obtained through a preheating step held at 1300°C for longer than 30 min and then sintering at a temperature above 1500°C. Pressureless-sintered composite containing 20vol% TiB₂ gives a flexural strength of 580 MPa and a fracture toughness of 7.2 MPa m^1/2.     

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.     

Al2TiO5–Al2O3–TiO2 nanocomposite: Structure,mechanical property and bioactivity studies

Novel biomaterials are of prime importance in tissue engineering. Here, we developed novel nanostructured Al₂TiO₅–Al₂O₃–TiO₂ composite as a biomaterial for bone repair. Initially, nanocrystalline Al₂O₃–TiO₂ composite powder was synthesized by a sol–gel process. The powder was cold compacted and sintered at 1300–1500 °C to develop nanostructured Al₂TiO₅–Al₂O₃–TiO₂ composite. Nano features were retained in the sintered structures while the grains showed irregular morphology. The grain-growth and microcracking were prominent at higher sintering temperatures. X-ray diffraction peak intensity of β-Al₂TiO₅ increased with increasing temperature. β-Al₂TiO₅ content increased from 91.67% at 1300 °C to 98.83% at 1500 °C, according to Rietveld refinement. The density of β-Al₂TiO₅ sintered at 1300 °C, 1400 °C and 1500 °C were computed to be 3.668 g cm^?3, 3.685 g cm^?3 and 3.664 g cm^?3, respectively.Nanocrystalline grains enhanced the flexural strength. The highest flexural strength of 43.2 MPa was achieved. Bioactivity and biomechanical properties were assessed in simulated body fluid. Electron microscopy confirmed the formation of apatite crystals on the surface of the nanocomposite. Spectroscopic analysis established the presence of Ca and P ions in the crystals. Results throw light on biocompatibility and bioactivity of β-Al₂TiO₅ phase, which has not been reported previously.     

In situ synthesis and characterization of a hierarchically structured Al2O3/Al3Ti composite

A hierarchically structured α-Al₂O₃/Al₃Ti composite was fabricated by an in situ process called exothermic dispersive synthesis from a powder blend of Al and TiO₂. The microstructure of the composite was investigated by X-ray diffraction, scanning electron microscopy, and X-ray energy dispersive spectroscopy. Three transitional phases, specifically TiO, Ti₂O₃, and γ-Al₂O₃, were found to form during the reactive process. Using differential scanning calorimetry, it was found that the reaction between the Al and TiO₂ occurred through three intermediate steps and their corresponding activation energies were 390, 205, and 197 kJ/mol, respectively. Moreover, the reaction rate of the third step was found to be much higher than that of the second step, and the time taken by each reaction step decreased with the increase of the heating rate. The findings are critical to understanding the microstructural development in the synthesis of strong and tough Al₂O₃/Al₃Ti composites.     

Preparation of ZrO2-Al2O3 powder by thermal decomposition of gels produced from an aluminium chelate compound and zirconium butoxide

Organic precursors containing Al and Zr atoms were synthesized from an aluminium chelate compound and zirconium n-butoxide. A ZrO₂-Al₂O₃ composite powder was prepared by the thermal decomposition of these precursors. An amorphous phase exists to higher temperatures for this ZrO₂-Al₂O₃ powder than for a comparable powder prepared from aluminium sec-butoxide and zirconium n-butoxide. In addition the tetragonal ZrO₂ phase was stabler in this ZrO₂-Al₂O₃ powder than in a comparison powder. The ZrO₂ grains were 50–500 nm in diameter and were homogeneously dispersed in the Al₂O₃ matrix after heating at 1400 °C.     

Metastable immiscibility and microstructural development during sintering of a SiO2-Al2O3 plasma prepared powder

The sintering characteristics of SiO₂-36.6 wt % Al₂O₃ powder, prepared by condensation from high frequency plasma, have been studied and microstructural changes occurring during sintering followed by transmission electron microscopy The as-prepared amorphous powder showed evidence of spinodal decomposition into an Al₂O₃-rich and SiO₂-rich glass consistent with the position of a previously reported metastable miscibility gap in the SiO₂-Al₂O₃ system. Mullite crystallized on an extremely fine scale at 1000° C and gradually coarsened at higher temperatures. Sintering occurred above 1100° C by a viscous flow mechanism with activation energy 87 kcal mol^–1 which corresponds to the activation energy for viscous flow of SiO₂-Al₂O₃ glass containing approximately 17 wt % Al₂O₃.     

The structure of plasma-prepared Al2O3-TiO2 powders

The morphology and phase constitution of sub-micron Al₂O₃-TiO₂ powders prepared by oxidation of mixtures of Al₂Br₆ and TiCl₄ in an oxygen-argon high-frequency plasma have been studied. The particle size and distribution were consistent with formation of liquid particles by rapid nucleation and surface reaction followed by growth by coalescence of droplets. The particle size of the powders is related to the concentration of reactants in the gas stream and the temperature difference between condensation and solidification. A metastable solution of TiO₂ in -Al₂O₃ was formed in the range 0 to 7 wt% TiO₂, at higher TiO₂ concentrations particles consisted of a dispersion of rutile particles (~ 10 nm) within single crystals of -Al₂O₃. A metastable phase identified as 3Al₂O₃·TiO₂ was also formed in powder with compositions in the range 14 to 40 wt% TiO₂. Over the composition range 40 to 80 wt% TiO₂ the powder consisted predominantly of crystals with a two-phase Al₂TiO₅-rutile structure. Pure TiO₂ consisted largely of anatase and the addition of Al₂O₃ resulted in the formation of rutile as the major phase. The phase constitution of the powders is interpreted in terms of the nucleation kinetics of the various phases.     

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.     

Reaction sintering fabrication of (AlN, TiN)-Al2O3 composite

The (AlN, TiN)-Al₂O₃ composites were fabricated by reaction sintering powder mixtures containing 10-30 wt.% (Al, Ti)-Al₂O₃ at 1420-1520°C in nitrogen. It was found that the densification and mechanical properties of the sintered composites depended strongly on the Al, Ti contents of the starting powder and hot pressing parameters. Reaction sintering 20 wt.% (Al, Ti)-Al₂O₃ powder in nitrogen in 1520°C for 30 min yields (AlN, TiN)-Al₂O₃ composites with the best mechanical properties, with a hardness HRA of 94.1, bending strength of 687 MPa, and fracture toughness of 6.5 MPa m^1/2. Microstructure analysis indicated that TiN is present as well dispersed particulates within a matrix of Al₂O₃. The AlN identified by XRD was not directly observed, but probably resides at the Al₂O₃ grain boundary. The fracture mode of these composites was observed to be transgranular.     

Laser processing of ceramics of the SiO2-Al2O3 system

An investigation has been made of the constitution of laser-processed ceramics from the SiO₂-Al₂O₃ system. Samples were produced in the form of pellets a few millimetres in diameter by pulsed laser melting of mixtures of silica and alumina powders containing 40, 60 and 70 mol % Al₂O₃. X-ray diffraction identified the main crystalline phases as Al₂O₃ in the pellets produced from the 70 mol % Al₂O₃ mixture and mullite from the 60 and 40 mol % Al₂O₃ mixtures. The proportion of glassy phase present increased with increasing SiO₂ content. Microstructural observations on the 60 mol % Al₂O₃ pellet showed primary mullite crystals and a lamellar structure interpreted as a eutectic of Al₂O₃ and mullite. Pellets prepared by melting kaolin powder consisted essentially of a glassy phase and much porosity. Cladding of an alumina substrate, carried out using a continuous powder feed into a laser-generated melt pool, was carried out using the same silica-alumina mixtures as those employed for pellet production. A clad layer was also produced by preplacing a kaolin coat on the alumina substrate prior to laser processing. The effects of traverse speed over the range 3.7 to 7.4 mm s^?1 inclusive, power density (44.4 and 111 W mm^?2) and powder flow rate (0.13 to 0.47 g s^?1 inclusive) were investigated. It was found that the phases present in the clad layer depended on the composition of the precursor powder and the processing conditions. Microstructural examination of the clad layers produced from SiO₂-60 mol % Al₂O₃ and kaolin that had completely melted during processing exhibited various growth morphologies.     

Sintering and dielectric properties of 0.88Al2O3-0.12TiO2 microwave ceramics by glass addition

The microwave characteristics and the microstructures of 0.88Al₂O₃-0.12TiO₂ with various amounts of MgO-CaO-SiO₂-Al₂O₃ (MCAS) glass sintered at different temperatures have been investigated. The sintering temperature can be lowered to 1300 °C by the addition of MCAS glass. The densities, dielectric constants (ε_r) and quality values (Q×f) of the MCAS-added 0.88Al₂O₃-0.12TiO₂ ceramics decrease with the increase of MCAS glass content. The temperature coefficients of the resonant frequency (τ_f) are shifted to more negative values as the MCAS content or the sintering temperatures increase. The change of the crystalline phases of Al₂TiO₅ phase and rutile-TiO₂ phase has profound effects on the microwave dielectric properties of the MCAS-added Al₂O₃-TiO₂ ceramics. As sintered at 1250 °C, 0.88Al₂O₃-0.12TiO₂ ceramics with 2 wt.% MCAS glass addition exists a ε_r value of 8.63, a Q×f value of 9578 and a τ_f value of +5 ppm/°C.     

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.     

Effect of calcination on characteristics and sintering behaviour of Al2O3-ZrO2 composite powders

The effect of calcination on the characteristics and sintering behaviour of zirconia-toughened alumina (ZTA) composite powders has been investigated. TiO₂ was selected as an additive to promote the sinterability of ZTA powders. The starting materials were Al₂O₃ powder, Zr(OC₃H₇)₄ and Ti(OC₃H₇)₄, and homogeneous ZTA powder containing Zr-O-Ti bonding was prepared. Calcination affected the tetragonalmonoclinic phase transformation temperature of ZrO₂ crystallizing from the gels. Calcination improved the densification rate of ZTA powder compact during sintering, which was attributed to the optimal ZrO₂ particle size and distribution on the surface of alumina. A ZTA specimen with high bulk density and high tetragonal ZrO₂ content was obtained under the conditions of 850°C/1 h calcination and 1500°C/1 h sintering.     

Effects of TiO2 doping on microstructure and properties of directed laser deposition alumina/aluminum titanate composites

ABSTRACT

Al₂O₃-based composite ceramics have excellent high temperature performance and are ideal materials for preparing hot end components. However, poor fracture toughness and thermal shock resistance limit its applications. Based on the excellent low thermal expansion characteristics and thermal shock resistance of Al₂TiO₅ ceramic, different composition ratios of Al₂O₃/Al₂TiO₅ composite ceramics were prepared by directed laser deposition (DLD) technology. Effects of TiO₂ doping amount on microstructure and properties of the composite ceramics were investigated. Results show that α-Al₂O₃ phase is discretely distributed in the continuous aluminum titanate matrix when TiO₂ doping amount between 2 and 30?mol%. With the increase of TiO₂ doping amount, content of Al₂O₃ gradually decreases and its morphology changes from cellular to dendritic. When TiO₂ doping amount reaches 43.9?mol%, the microstructure transforms into fine Al₂TiO₅/Al₆Ti₂O₁₃ eutectic structure. Property test results show that Al₂O₃/Al₂TiO₅ composite ceramics have good comprehensive mechanical properties when TiO₂ doping amount between 2 and 6?mol%.     

Photocatalytic activity of nanostructured γ-Al2O3/TiO2 composite powder formed via a polyelectrolyte-multilayer-assisted sol–gel reaction

Nanostructured, γ-Al₂O₃/TiO₂ composite powder was fabricated via an in situ, sol–gel reaction of titanium iso-propoxide in a self-assembled, polyelectrolyte multilayer (PEM) formed on the surface of high-specific-area, polycrystalline, γ-Al₂O₃ lamellas. The infiltration of the titanium precursor into the PEM, followed by the hydrolysis and condensation reactions with the water absorbed in the PEM after annealing, resulted in the formation of a nanostructured TiO₂ layer on the surface of the γ-Al₂O₃ lamellas. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were employed to evaluate the morphology, the chemical composition and the crystallinity of the γ-Al₂O₃/TiO₂ particles of the composite powder. The as-formed, nanostructured, γ-Al₂O₃/TiO₂ composite powder exhibited a 2.7-times-higher photo-activity in the near-UV region compared to commercially available TiO₂ (Degusa P25), as monitored by the photo-decomposition of a methylene blue (MB) dye.     

Effects of copper and Al2O3 particles on characteristics of Cu–Al2O3 composites

High-energy milling was used for production of Cu–Al₂O₃ composites. The inert gas-atomized prealloyed copper powder containing 2 wt.%Al and the mixture of the different sized electrolytic copper powders with 4 wt.% commercial Al₂O₃ powders served as starting materials. Milling of prealloyed copper powders promotes formation of nano-sized Al₂O₃ particles by internal oxidation with oxygen from air. Hot-pressed compacts of composites obtained from 5 and 20 h milled powders were additionally subjected to the high-temperature exposure in argon at 800 °C for 1 and 5 h. Characterization of processed material was performed by optical and scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), microhardness, as well as density and electrical conductivity measurements. Due to nano-sized Al₂O₃ particles microhardness and thermal stability of composite processed from milled prealloyed powders are higher than corresponding properties of composites processed from the milled powder mixtures. The results were discussed in terms of the effects of different size of starting copper powders and Al₂O₃ particles on the structure, strengthening of copper matrix, thermal stability and electrical conductivity of Cu–Al₂O₃ composites.     

Preparation of SiO2-Al2O3 glass powders by the sol-gel process for dental applications

SiO₂-Al₂O₃ binary glass powders with Al₂O₃ contents up to 50 wt% have been synthesized by the sol-gel process. The starting solution (sol) consisted of 1 mole of tetraethoxysilane, 50 moles of water containing aluminum nitrate, 10 moles of ethyl alcohol and 0.02 moles of HCl catalyst. The sol was converted into gel by heating at 85°C and suction by running water. The sintering process was analysed by DTG thermal analysis. The fired powders were examined by XRD. It was confirmed that the gels were converted into the glass structure without crystallization. The measurements of refractive index and powder size of fired powders revealed that these powders could be used as refractive-index-adjustable fillers for dental composite resins. The other potential usage of the SiO₂-Al₂O₃ powders obtained might be in the production of powders for dental cements.To whom correspondence should be addressed at Osaka University, Faculty of Dentistry, Department of Dental Technology, 1-8 Yamadaoka, Suita, Osaka 565, Japan.     

Effect of preparative parameters on the electrical conductivity of Li2SO4-Al2O3 composites

The effect of various preparative parameters, such as the size and form of alumina and also the time of sintering, on the electrical conductivity of the Li₂SO₄-Al₂O₃ composite system has been investigated. The sintering time appears to be an insignificant preparative parameter. The role of different phases of Al₂O₃ on the electrical conductivity of the composite clearly establishes that the maximum enhancement is achieved for γ-Al₂O₃. The 50 m/o Al₂O₃ composition was found to exhibit the highest conductivity, an enhancement of three orders of magnitude at 500°C. The experimental data indicates higher conduction in the space charge layer near the surface to be the possible mechanism of conductivity enhancement.     

A new method for surface modification of TiO2/Al2O3 nanocomposites with enhanced anti-friction properties

In this paper, the TiO₂/Al₂O₃ composite nanoparticles were prepared by a hydrothermal method and in situ modified with acrylic acid. It was found that the mean particle size of modified TiO₂/Al₂O₃ composite nanoparticles was about 80 nm with a uniform distribution by the particle size analysis. The modified TiO₂/Al₂O₃ composite nanoparticles can disperse in lubricating oil homogenously for several weeks. The dispersion stabilization of modified TiO₂/Al₂O₃ composite nanoparticles in lubricating oil was significantly improved in comparison with the as-prepared nanoparticles, which was due to the introduction of grafted polymers by surface modification. The formation of covalent bands was identified by Fourier transform infrared spectrum. Under an optimized concentration of 0.1 wt%, the averaged friction coefficient was reduced by 14.75%, when the modified TiO₂/Al₂O₃ composite nanoparticles were used as lubricating oil additivities.