On the formation of thermally sprayed alumina coatings

A model for the fomation of thermally sprayed alumina coatings is proposed. The spreading and crystallization of liquid droplets on impact with the substrate are analysed and the thermal history of individual particles related to the kinetics of nucleation of -Al₂O₃ to other forms. The results suggest that under the usual spraying conditions undercooling of the liquid droplets is such that -Al₂O₃ nucleates in preference to -Al₂O₃ and the cooling rate after solidification is sufficiently rapid to prevent transformation to -Al₂O₃ or -Al₂O₃. Transformation of initially formed -Al₂O₃ to -Al₂O₃ appears to be possible only if the lamellae formed on impact are thicker than about 10 m if the substrate is heated to about 1000° C, or if the thickness is greater than about 20 m on an unheated substrate. The -Al₂O₃ generally observed in thermally sprayed coatings is the result of crystallization from pre-existing nuclei arising from incomplete melting of the feed material.     

Sintering of pseudo-boehmite and γ-Al2O3

Sintering of pseudo-boehmite, acicular-Al₂O₃ produced by dehydration of pseudo-boehmite, and-Al₂O₃ ex alum was investigated. The sintering process was studied by X-ray diffraction, transmission electron microscopy with selected area electron diffraction and BET surface area measurements. The solid state reaction to-Al₂O₃ causes a steep drop of the surface area to less than 10 m²g^–1. The acicular pseudo-boehmite and-Al₂O₃ supports exhibit an intermediate state where the acicular particles assume a rod-like shape and the surface area falls from about 300 to 100 m²g^–1. It was established that reaction to -Al₂O₃ and, hence, sintering proceeds via a nucleation and growth mechanism. The rate-limiting step is nucleation of -Al₂O₃. Consequently, the contacts between the elementary alumina particles dominate the sinter process. The contact between the acicular elementary particles of pseudoboehmite and-Al₂O₃ studied leads to the reaction to -Al₂O₃ to be almost complete after keeping samples for 145 h at 1050 °C. Decomposition of alum produces very small particles showing negligible mutual contacts. Consequently an elevated thermal stability is exhibited. Treatment of the alumina ex alum with water and drying results in a xerogel in which contact between elementary particles is much more intimate. Accordingly, treatment at 1050 °C causes a sharp drop in surface area.     

Phase and microstructural development in alumina sol–gel coatings on CoCr alloy

Phase transformation of -Al₂O₃ to -Al₂O₃ in alumina sol gel coatings on biomedical CoCr alloy was studied as function of heat treatment temperature and time. Transformation in unseeded coatings was significant only above 1200 °C. Addition of -Al₂O₃ seed particles having an average size of approximately 40 nm lowered the phase transformation temperature to around 800 °C. These particles were considered to act as heterogeneous nucleation sites for epitaxial growth of the -Al₂O₃ phase. The kinetics and activation energy (420 kJ/mol) for the phase transformation in the seeded coatings were similar to those reported for seeded monolithic alumina gels indicating that the transformation mechanism is the same in the two material configurations. Avrami growth parameters indicated that the mechanism was diffusion controlled and invariant over the temperature range studied but that growth was possibly constrained by the finite size of the seed particles and/or coating thickness. The phase transformation occurred by the growth of -Al₂O₃ grains at the expense of the precursor fine-grained -Al₂O₃ matrix and near-complete transformation coincided with physical impingement of the growing grains. The grain size at impingement was 100 nm which agreed well with that predicted from the theoretical linear spacing of seed particles in the initial sol.     

Distribution characteristics of mechanical properties and correlation between the respective properties on S35C carbon steel

Mechanical properties of tensile strength, , upper yield stress, _SU, lower yield stress, _SL elongation, , area reduction, , Vickers hardness, H _v, and impact absorbed energy, E, were examined using 50 specimens of S35C carbon steel, which were machined from two bars supplied from the same charged and heat-treated material. Distribution characteristics of these properties are discussed, and the correlation between each pair of them is investigated from a statistical viewpoint. The main conclusions obtained are summarized as follows; distribution characteristics of _B, _SL, , , H _v and E are well approximated by a normal distribution, but those of asu are not approximated as well by this type of distribution. In the latter case, a Weibull distribution is preferable to represent the distribution pattern. No significant correlation was observed between each pair of the above mechanical properties. Consequently, individual properties have the inherent distribution characteristics independent of the other properties.     

Stability of Si3N4-Al2O3-ZrO2 composites in oxygen environments

Oxidation of dense Si₃N₄-Al₂O₃-ZrO₂ and Si₃N₄-Al₂O₃ compacts, at 873–1773 K and 98 KPa air atmosphere, results in two different parabolic oxidation regimes. Oxygen diffusion is likely to be the governing step at low temperature (T<1623 K (H= 100kJ mol^–1)), whereas at T> 1623 K (H = 800kJ mol^–1) metal cation diffusion through the grain boundary phase appears limiting. The excellent stability in oxygen environments of the Si₃N₄-Al₂O₃-ZrO₂ composites compared to other ZrO₂-Si₃N₄ materials derives from (i) absence of easy-to-oxidize Zr-O-N phases; (ii) reduced amount of grain boundary phase, and possibly (iii) decreased solubilization rate of the nitride phases in the high viscous oxide film.     

The effect of a Cr2O3-addition on the phase transformation and catalytic properties of γ-Al2O3 in treatment of lean-burn exhausts

The solid-state thermal behaviour of -Al₂O₃ doped with 10 mol% Cr (oxide) was studied with respect to phase-transition behaviour and the co-ordination of the dopant Cr cations. A series of transformations: -Al₂O₃ -Al₂O₃ -Al₂O₃ -Al₂O₃ was observed for Cr₂O₃-doped alumina samples between 500 °C and 1100 °C. Rapid grain growth occurred at temperatures close to 1100 °C. The electron spin resonance (ESR) spectra for the sample heat-treated at 500 °C corresponded to the resonance of -Cr³⁺ in an amorphous Cr oxide impregnated onto the - and -alumina support. The change of ESR spectrum indicated the existence of Cr³⁺, suggesting the formation of a solid solution with the same structures as -Al₂O₃ and/or -Al₂O₃ at 800–1000 °C. The evaluation of catalytic activities for model exhaust was performed under lean-burn (an excess of oxygen) condition of air/fuel ratio A/F = 18 and space velocity SV = 100 000 h^–1 . The modified Al₂O₃ catalyst heat-treated at 1000 °C in air showed removal conversion of 100% for hydrocarbon (C₃H₆), 92% for CO and 5% for NO at 550 °C. Present results suggest that Cr-modification to Al₂O₃ leads to catalytic improvement with good thermal durability.     

Low-temperature synthesis,pyrolysis and crystallization of tantalum oxide gels

Tantalum oxide gels in the form of transparent monoliths and powders have been prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC₂H₅)₅C₂H₅OHH₂OHCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide water HCl ratio, the time of gel formation increased with the alcohol to alkoxide molar ratio. Thermal evolution of the physical and structural changes in the gel has been monitored by differential thermal analysis, thermogravimetric analysis, X-ray diffraction, and infrared spectroscopy. On heating to 400 °C, the amorphous gel crystallized into the low-temperature orthorhombic phase -Ta₂O₅, which transformed into the high-temperature tetragonal phase -Ta₂O₅ when further heated to 1450 °C. The volume fraction of the crystalline phase increased with the firing temperature. The -Ta₂O₅ converted back into the low-temperature phase, -Ta₂O₅, on slow cooling through the transformation temperature of 1360 °C, indicating a slow but reversible transformation.     

Preparation of tricalcium phosphate/alumina composite nanoparticles and self-reinforcing composites by simultaneous precipitation

The composite nanoparticles and corresponding self-reinforcing composites comprising tricalcium phosphate (TCP) and alumina (Al₂O₃) were synthesized by simultaneous precipitation from the CaCl₂, AlCl₃ and (NH₄)₂HPO₄ aqueous solutions, using aqueous NH₄OH as precipitant. Influences of the precipitating media pH and the Ca/P atomic ratios on phase composition and morphology of the composites were investigated. Results showed that except for the major phases -TCP and -Al₂O₃, there was always a third minor phase in the calcined composites coprecipitated either in neutral or alkaline condition. Formation of -TCP is, however, favored at pH 9.2, whereas more of the third phase, mainly AlPO₄, is formed under neutral condition. High Ca/P ratios suppress the formation of -Al₂O₃ phase under alkaline precipitating condition, but the effect is less significant in neutral condition. TEM observation showed that the as prepared composite particles are nano-sized but interconnected to form a network-like morphology. They were changed to a core-shell-like structure after calcination, while their nano-scale dimension was retained. FEGSEM analysis revealed that the -Al₂O₃ phase in the sintered composite compacts was in the form of fibrils dispersed in the phosphate phases. These in situ formed fibrils impart a unique role in self-reinforcement of the sintered composites. Mechanical measurements showed that the incorporation of alumina reinforced -TCP effectively: the flexural strength increased from 15 MPa of the pure -TCP to 84 MPa of the composite with 40 wt% of -Al₂O₃.     

Preparation and bactericidal property of MgO nanoparticles on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

After being impregnated in the solution containing Mg(NO₃)₂·6H₂O, -Al₂O₃ was dried and calcined at 500°C which results in the production of a bactericide, highly dispersed MgO loaded on the surface of -Al₂O₃. The threshold value of the monolayer dispersion of MgO on -Al₂O₃ is 14.97%, and MgO crystal formed when the load amount beyond this value. The samples with different load amount were characterized by X-ray Diffraction (XRD), Low-temperature N₂ adsorption-desorption, Inductively Coupled Plasma (ICP) and High Resolution Scan Electronic Microscope (SEM). The results showed that these MgO microcrystals are highly dispersed and have regular size in the range of 4 to 10.8 nm. The specific surface, pore volume and pore size of the sample decreases with the increase of load amount. It is demonstrated that -Al₂O₃ with highly dispersed MgO on the surface is efficient bactericide, and the one with 20% load amount of MgO can kill more than 99% bacteria and spore cells.     

Reactions between mercury-wetted aluminium and liquid water

The reaction of solid aluminium with liquid water has been studied by several investigators. In this paper, the reaction between mercury-wetted aluminium and liquid water is described. At 25 and 90 °C, the reaction products were identified by X-ray diffraction analysis as bayerite,-Al₂O₃.3H₂O, and boehmite,-Al₂O₃.H₂O, respectively. The transitions of these hydrates to-Al₂O₃ upon heating were indicated by endothermic peaks on DTA thermograms and weight-loss measurements by TGA.The wetting mercury film acts as a medium for rapid transport of aluminium in solution from the solid-liquid interface to the liquid-vapour or liquid-liquid interface. This unique condition produces readily identifiable materials since it avoids some of the difficulties encountered by other investigators in their attempts to study the reactions of air and liquid water directly with aluminium foil or bulk samples.     

Sol-gel prepared Ni-alumina composite materials

The sol-gel method has been utilized for the preparation of dense, homogeneous ceramic-metal composites with up to 50% Ni in Al₂O₂. Examination by SEM and TEM shows that the materials consist of micrometre-size Al₂O₃ with metallic Ni in isolated regions from 50 m down to nanometre size. The density ranges from 97% (10% Ni) to 74% (50% Ni) of the theoretical number. The hardness decreases from 18 GPa for pure alumina to 10 GPa for alumina containing 50% Ni. The fracture toughness increases significantly from K _1c=3–4 MPa m^1/2 to K _1c=8.5 MPa m^1/2. The elastic and shear moduli decrease from E=400 GPa and G=160 GPa for pure alumina to E=320 GPa and G=135 GPa when containing 50% Ni. The electrical resistivity is 10⁶m with 10 to 40% Ni but decreases drastically at 50% Ni content.     

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.     

Mullite formation from xerogels of (0.84–2.2) Al2O3·1SiO2

Xerogels of (0.84–2.2) Al₂O₃·1SiO₂ prepared by chemical coprecipitation of Al(NO₃)₃·9H₂O and Si(OC₂H₅)₄ experience three thermal reaction paths for mullite formation. Those with pseudoboehmite are found to form mullite via the paths of either Al-Si spinel mullite transformation or -Al₂O₃ -Al₂O₃ + amorphous SiO₂ mullite, depending upon the ratios of Al₂O₃/SiO₂. Higher SiO₂ content may prefer the former reaction. Xerogels composed of bayerite form mullite via the route -Al₂O₃ -Al₂O₃ + amorphous SiO₂ mullite. Mullite thus formed exhibits a different crystal size, being 20–25 nm for that obtained from pseudoboehmite and around 37 nm for bayerite. The highest yield of mullite formation may be achieved with xerogels of pseudoboehmite with the stoichiometric mullite compositions, 3Al₂O₃·SiO₂.     

The critical curve in an antiferromagnetic superconductor with nonmagnetic impurities

The critical curve of a transition of the second kind in an antiferromagnetic superconductor (AFS) with nonmagnetic impurities has been studied. The AFS is described by using the mean-field model given by Nass, Levin, and Grest and assuming a one-dimensional electron band. We find that the points on the critical curve satisfy the thermodynamic stability condition for 0₁/₀5.04 and 0.49H_Q/₀1.64.Here ₁ is the inverse lifetime of a conduction electron for nonmagnetic impurity scattering,H _Q is the antiferromagnetic molecular field, ₀ is the zero-temperature order parameter of a superconductor in the absence ofH _Q and impurities. Further, ₁ and H_Q denote the values of these quantities for points on the critical curve. For ₁/₀>5.04 and H_Q/₀>1.64, the phase transition from the superconducting to the normal state is always of the second kind. Some thermal properties of the system near the critical curve have also been investigated and we find that these depends dramatically on the impurity concentration.     

Incommensurate Dynamical Properties of Optimally Doped YBa2Cu3O6.9

The resonance and incommensurate peaks in optimally doped high-T _c superconductor YBa₂Cu₃O_6.9 are observed by means of TOF neutron scattering technique. Obtained overall dynamical properties in a wide Q-E space show distinct incommensurate structure around antiferromagnetic (AF) zone center (, ). The incommensurability of =0.1 at 36 meV corresponds to the previous triple-axis neutron measurement. Variation of temperature dependence suggests the spectral weight of antiferromagnetic fluctuation observed around 25 meV at (, ) shifts to resonance peak position below T _c. Moreover obtained results with E _i=80 meV neutron energy indicate new feature of dynamical incommensurate structure at higher frequency region up to 53 meV.     

The formation of α-Al2O3 from θ-Al2O3: The relevance of a “critical size” and: Diffusional nucleation or “synchro-shear”?

The coarsening of -Al₂O₃ crystals to a 'critical size' is often interpreted as the first step in the shear nucleation of -Al₂O₃. The existence of this so-called critical size has also been used to explain the observation that -Al₂O₃ nuclei are generally twice as large as the crystals in the -Al₂O₃ matrix. This paper discusses the important issues in the nucleation of -Al₂O₃ from -Al₂O₃. A few key experiments are also presented to clarify the nucleation process. It is concluded that a critical -Al₂O₃ crystal size is not a prerequisite for -Al₂O₃ nucleation, but is primarily a result of the incubation time required to produce -Al₂O₃ nuclei by diffusional nucleation. It is proposed that the large observed -Al₂O₃ crystal size also does not result from a shear nucleation event in a 'critical size' -Al₂O₃ crystal, but is due to the intrinsically low -Al₂O₃ nucleation density, together with rapid growth of -Al₂O₃ after nucleation.w     

Characterization of metal films on corundum substrates

Gold layers on corundum, -Al₂O₃, substrates, with intermediate sputtered copper and chromium layers, are used for microwave integrated circuit applications. The existance of islands of monocrystalline Au and Cu in otherwise polycrystalline material has been verified using X-ray and electron diffraction techniques. In these monocrystalline regions, a discrete Cr layer, under the Au and Cu layers, is no longer present. Investigations on specially prepared samples established the monocrystalline Cu to be a twinned epitaxic layer with (111)Cu//(0001)-Al₂O₃; [¯1¯12] Cu//[2¯1¯10]-Al₂O₃. In a sample consisting of a single Cr layer on -Al₂O₃, the Cr was found to be epitaxic with (110) Cr//(0001)-Al₂O₃. Epitaxic islands are detrimental to device performance, and their formation has been suppressed by reducing the sputtering power density.     

Physicochemical properties of rare earth perovskite oxides used as gas sensor material

The change of the conductivity in the rare earth perovskite oxide took place after the chemisorption of flammable gases. The sensitivity for methanol was highest. From the conductivity change of these perovskite oxides after the injection of methanol, the energy needed to promote an electron from a conducting to a nonconducting state, E=E _c-E _t, could be derived from the equation=A ₀ exp (–E/kT). LnCoO₃ had the smallest E and H (metal-O), which is the binding energy of oxygen coordinating to the metal ions, but exhibited the highest activity for gas sensing. The gas sensing mechanism was also considered.     

Thermal stabilization of an active alumina and effect of dopants on the surface area

The -AI₂O₃ transformation of a monolithic active alumina has been increased from 1200 to 1380 C through structural incorporation of silica. This shift is significant since -Al₂O₃ transformation determines the limits of the usefulness of these materials as catalysts and catalyst carriers. The thermal stabilization effect is optimized at around 6% silica doping. At elevated temperatures, the material containing no silica rapidly loses surface area, primarily by -Al₂O₃ transformation, whereas the material containing excess silica loses surface area by classical sintering.     

Microstructural development of a ZrO2 Naβ″-Al2O3 composite

Microstructural development in Na-Al₂O₃ containing 15 vol% ZrO₂ particles is described. Intergranular ZrO₂ particles inhibit abnormal grain growth of the Na-Al₂O₃. The growth of the Na-Al₂O₃ grains and the intergranular ZrO₂ followed a cubic time law. Direct particle coalescence consisting of encounter and spheroidizing processes was found to be the basic growth mechanism for the intergranular ZrO₂