Thermal evolution of thin boehmite films

Using transmission electron microscopy, electron diffraction and resistance change measurements, we studied the process of thermal evolution of thin boehmite (-Al₂O₃·H₂O) films. It has been shown that the crystal lattice of boehmite decomposes at a temperature of 670 K, with simultaneous partial dehydration. Above 875 K crystallization of - Al₂O₃ occurs and the morphology of the film changes from fibrous to granular. Annealing of - Al₂O₃ at 1300 K results in its transformation into - Al₂O₃. At temperatures of 1475 to 1575 K the transformation of -Al₂O₃ into - Al₂O₃ was observed. Depending on the temperature of annealing, thin -Al₂O₃ films were composed of fine crystals or of large (micrometre) corundum crystals. The method of producing of the various aluminas in the form of thin films presented in this report makes investigation of the structure transitions in aluminium oxides by means of transmission electron microscopy possible, and such films can be also used as supports for transmission electron microscopy studies of the model metal-oxide supported catalysts.     

Direct synthesis and characterization of the Fe3+ analogue of Naβ″-alumina

A new isomorphic analogue of-alumina, a potassium-free Na-ferrite (Na₂O · 5 (Al_0.10Fe_1.90)O₃, referred to as Na-ferrite), has been synthesized and is characterized using X-ray powder and single crystal diffraction, wet chemical analysis, and transmission electron microscopy (TEM). In addition, Na-aluminate-gallate-ferrate phases were also successfully synthesized, but were not characterized in detail. Na-ferrite grew in a slowly cooling melt or partial melt from 1250° C in air using Na₂CO₃ and Fe₃O₄ (magnetite) as starting materials. The compound was also synthesized using-Fe₂O₃ instead of Fe₃O₄ under the same conditions, but its abundance was much less and-Fe₂O₃ and NaFeO₂ were the dominant phases. The new material (cell dimensionsa = 0.5955,c = 3.5623 nm) is reversibly hygroscopic, andc increases 2% after hydration. TEM images dearly show the 1.19 nm lattice spacing corresponding to the ionic conduction planes, and these planes are observed to be both straight and curled. The origin of the curled lattice planes, the existence of which is also evident in the single crystal precession photographs, is not clear, although we believe it may involve a structural misfit between the ferric oxide spineI block and soda layer.     

Interface characterization of a β-SiC whisker-Al composite

The nature of the interface, the orientation relationship of -SiC whisker (-SiC_w)-Al combination, and the misfit dislocation structures at the -SiC_w-Al interfaces in a -SiC_w-Al composite have been observed by a high-resolution transmission electron microscopy (HRTEM). It was shown that quite a good bonding between the whisker and the aluminium was achieved due largely to the lattice match between SiC and aluminium at the interfaces. The orientation relationship between the whisker and the aluminium was {002}_SiC{111}_Al; 110_SiC110_Al. The interface was clean, faceted and semicoherent. The misfit dislocation cores were located in the whisker side away from the -SiC_w-Al interfaces.     

Large magnetoresistivity of sputtered Al-(O or N)-Bi alloys

Application of the sputtering technique to (Al₂O₃)_xBi_100–x and (AIN)_x Bi_100–x (x = 0 to 100%) has been found to result in the formation of a duplex material consisting of hexagonal bismuth particles dispersed finely and homogeneously in amorphous Al_xO_y and Al_xN_y matrices. The particle size and interparticle distance of the bismuth phase were about 5 to 140nm and 5 to 35 nm. The duplex alloys have high electrical resistivities ranging from 1.82 × 10³ to 3.16 × 10⁵ cm combined with a negative temperature-dependent resistivity of 148 to 342% of ₂₇₃. Furthermore, all the Al-O-Bi and Al-N-Bi alloys have been found to exhibit a positive magnetoresistive change and the maximum value, (H), at 4.2 K and 7.5T reaches 5.85 × 10⁴ cm for (Al-O)_65.7Bi_34.3 and 1.99 × 10⁵ cm for (Al-N)_69.7 Bi_30.3. The large magnetoresistivities are probably due to the unique sputtered structure consisting of metallic bismuth particles with a long mean free path of electrons embedded finely and homogeneously in amorphous Al_xO_y or Al_xN_y matrix, resulting in the large difference of the relaxation times (different mobilities) of electron carriers. It has thus been demonstrated that the oxide- or nitride-based composite materials exhibiting large magnetoresistivities, which cannot be achieved in metallic composite materials, are obtained by sputtering simultaneously Al₂O₃ or AIN and bismuth which is immiscible to aluminium.     

The relative stability ofβ andβ″-phases in Na2O-Al2O3 beta alumina

To reveal the relative stability of and -phases in beta alumina, effects of Na₂0 content and calcination and annealing history on the relative content of and -phases have been studied for compositions ranging from Na₂O-5Al₂O₃ to Na₂O-9.5Al₂O₃. The relative stability appears to be dependent on the calcination or annealing history, except holding time such as annealing or re-annealing time, but independent of the Na₂O content and the holding time. From these results it can be demonstrated that the relative stability of and -phases is sensitive to the heat treatment path, except the holding time. The two stage model on the /. polytypic transition in silicon carbide has been quoted to explain the heat treatment pathdependent characteristics.     

Ageing studies of discontinuous copper and silver thin films

The results of experiments carried out on the post-deposition resistance changes in discontinuous films of copper and silver with and without overlayers of SiO and Al₂O₃ are presented. The changes in the sheet resistance of the films with time and pressure were studied for the above combinations. Mobility coalescence is assumed to be responsible for the resistance increase of an uncovered copper film of initial resistance 1.9 M/. On exposure to the atmosphere, it was found that an Ag/SiO combination of initial resistance of 0.1 M/ achieved stability in the sheet resistance much quicker than a Cu/Al₂O₃ combination of initial resistance 20 M/. The fall in resistance of the Cu/Al₂O₃ composite is attributed to the formation of Al₂(OH)₆ due to the interaction of Al₂O₃ with the water vapour in atmosphere. Copper films with and without overlayers of Al₂O₃ show an abrupt increase in the sheet resistance as a function of pressure at a pressure of about 5 × 10^–2 torr with the maximum rate of change of resistance occurring at higher pressure for the higher resistance film. This indicates that the overlayer of Al₂O₃ is very porous in nature. Field effect studies were carried out on an uncovered copper film of initial resistance 10 M/ and the behaviour was found to be ohmic up to a field of 800 V cm^–1.     

Effect of AlN and Al2O3 additions on the phase relationships and morphology of SiC Part II: Microstructural observations

Additions of AlN and Al₂O₃ to -SiC hot pressed at 2100°C strongly effect the - to -SiC phase transformation and the resultant -SiC polytypes which are formed. Scanning and transmission electron microscopy were utilized to investigate the microstructural changes occurring in SiC due to these additions and to correlate these observations to their mechanical properties. The results suggest that Al₂O₃ additions stabilize the formation of the 6H-polytype of -SiC which grows rapidly into an elongated plate-like morphology, while AlN additions stabilize the 2H-polytype of -SiC resulting in fine equiaxed 2H-SiC: AlN solid solution grains. It is speculated that the elongated growth of 6H-SiC with Al₂O₃ additions can be controlled through the simultaneous addition of AlN. The formation of 2H-SiC : AlN solid solution grains inhibits the growth of the 6H-SiC grains since AlN(2H) will not go into solid solution in the SiC(6H) structure, effectively pinning the growth of the 6H-SiC grains.     

Ion transport studies in PEO∶NH4I polymer electrolytes with dispersed Al2O3

Ion conducting polymer electrolyte films having high salt concentrations have been studied. The system studied is PEONH₄I, dispersed with -Al₂O₃. Mechanically stable films with NH ₄ ⁺ /EO ratio 0.13 have been obtained by dispersal of Al₂O₃. The films have been characterized using various techniques such as X-ray diffraction (XRD), differential thermal analysis (DTA), polarization and complex impedance spectroscopy. Intercorrelation between polymer matrix crystallite size, conductivity, and -Al₂O₃ particle size is established.     

Hydrothermal synthesis of barium titanate fine particles from amorphous and crystalline titania

Barium titanate fine particles of cubic system were synthesized hydrothermally from aqueous barium hydroxide solutions with fine particles of either amorphous or crystalline (rutile) titania in suspension. The mean size of barium titanate particles prepared from amorphous titania ranged from 0.03 m to 0.11 m, depending on hydrothermal conditions. The particle size approximately agreed with the crystallite size (0.04–0.09 m). On the other hand, the mean size of barium titanate particles prepared from rutile titania ranged from 0.2 to 0.7 m, which was about six times as large as the crystallite size. The difference of sizes of barium titanate particles prepared might be ascribed to the difference in dissolution rates of amorphous or crystalline titania particles.Nomenclature mean particle size, m - BT barium to titanium molar ratio - d crystallite size, m - K shape factor appearing in Equation 3 - half value breadth of diffraction peak - lattice strain - Bragg diffraction angle, degree - wave length of X-ray, urn - _g geometric standard deviation defined by 84.1%-size/50%-size in a log normal size distribution     

Transport property and battery discharge characteristic studies on 1−x(0.75Agl∶0.25AgCl)∶ xAl2O3 composite electrolyte system

Various experimental studies on a new fast Ag⁺ ion-conducting composite electrolyte system: (1–x) (0.75Agl0.25AgCl)xAl₂O₃ are reported. Undried Al₂O₃ particles of size <10 m were used. The conventional matrix material Agl has been replaced by a new mixed 0.75Agl0.25AgCl quenched and/or annealed host compound. Conductivity enhancements 10 from the annealed host and 3 times from the quenched host obtained for the composition 0.7(0.75Agl0.25AgCl)0.3Al₂O₃, can be explained on the basis of the space charge interface mechanism. Direct measurements of ionic mobility as function of temperature together with the conductivity were carried out for the best composition. Subsequently, the mobile ion concentration n values were calculated from and a data. The value of heat of ion transport q* obtained from the plot of thermoelectric power versus 1/T supports Rice and Roth's free ion theory for superionic conductors. Using the best composition as an electrolyte various solid state batteries were fabricated and studied at room temperature with different cathode preparations and load conditions.     

The origins of mullite formation

The evolution of mullite formation has been studied from Al₂O₃-SiO₂ gels. The studies have established (a) the identity of the controversial cubic phase, (b) the chemical, structural and compositional continuity in the evolution of mullite formation, (c) the existence of solid solutions between (32) and (21) mullites, (d) the origins of the exotherms, and (e) the origins of mullite formation. The Al-Si spinel has a composition and structure similar to that of the (21) mullite, i.e. _x Al_16-x ^vi[Al _x Si_4-x ]^ivO₃₂.     

Effect of small amount of alumina doping on superplastic behavior of tetragonal zirconia

The effect of Al₂O₃ doping of around 0.1 wt% on superplastic behavior was studied in 3 mol% yttria-stabilized tetragonal zirconia polycrystal (TZP) which was free from SiO₂ contamination and had a grain size of 0.4 m. Compression creep tests revealed that high-purity TZP with less than 0.07 wt% Al₂O₃ had two deformation regions: the low stress region had a stress exponent of three and an apparent activation energy of 640 kJ/mol, and the high stress region had two and 460 kJ/mol. On the other hand, TZP containing more than 0.12 wt% Al₂O₃ had only one region which had a stress exponent of two and an activation energy of 480 kJ/mol. The region of diffusion control with a stress exponent of one was not observed in any samples. High resolution transmission electron microscopy revealed that no amorphous grain boundary phase was produced even with 0.18 wt% Al₂O₃ doping. Energy dispersive X-ray spectroscopy near grain boundaries revealed that yttrium was segregating at the grain boundaries with denuded zones of 30 nm width, which were created during slow cooling from the sintering temperature.     

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.     

Effect of AlN and Al2O3 additions on the phase relationships and morphology of SiC Part I Compositions and properties

X-ray diffraction was utilized to follow the transformation from -SiC (3C) to the various -SiC polytypes in the presence of AlN and Al₂O₃ additives after hot pressing from 1700 to 2100°C. The 2H- and 6H-polytypes of -SiC were the predominate polytypes with additions of only AlN or Al₂O₃, respectively. The amount of 2H- and 6H-polytypes, and subsequently the microstructural morphology of the SiC materials, were found to be controlled by varying the amount of AlN and Al₂O₃. Improvements in fracture toughness to 9 MPa-m were achieved with flexural strengths ranging from 600 to 900 MPa. These results suggest that accurate control of the polytypic make-up of SiC-based materials, along with their mechanical properties, can be achieved through AlN and Al₂O₃ additions.     

Sintering mechanisms and microstructural development of coprecipitated mullite

Coprecipitated mullite precursor powders of the bulk compositions 78 wt% Al₂O₃+22 wt% SiO₂ (high-Al₂O₃ material) and 72 wt% Al₂O₃+28 wt% SiO₂ (low-Al₂O₃ material) have been used as starting materials. The precursor powders were calcined at 600, 950, 1000, 1250, and 1650 C, and test sintering runs were performed at 1550, 1600, 1650, 1700, and 1750 C. Homogeneous and dense ceramics were obtained from cold isostatically pressed (CIPed) powders sintered in air at 1700 C. Therefore, all further sintering experiments were carried out at 1700 C. After pressureless sintering, sample specimens were hot isostatically pressed (HIPed) at 1600 C and 200 bar argon gas pressure. Sintering densifications of low Al₂O₃ materials ranged between 94% and 95.5%. There was no clear dependency between densification and calcination temperature of the starting powders. High-Al₂O₃ compositions displayed sintering densities which increased from 97% at 600 C calcination temperature to 99% at 950 C calcination temperature. Higher calcination temperatures first caused slight lowering of the sintering density to 95.5% (calcination temperature 1250 C) but later the density strongly decreased to a value of 85% (calcination temperature 1650 C). HIPing of pressureless sintered specimens prepared from powders calcined between 600 and 1100 C yielded 100% density. At the given sintering temperature of 1700 C, the microstructure of sample specimens was influenced by Al₂O₃/SiO₂ ratios and by calcination temperatures of the starting powders. Homogeneous and dense microstructures consisting of equiaxed mullite plus some minor amount of -Al₂O₃ were produced from high-Al₂O₃ powders calcined between 600 and 1100 C. Low-Al₂O₃ sample specimens sintered from precursor powders calcined between 600 and 1100 C were less dense than high-Al₂O₃ materials. Their microstructure consisted of relatively large and elongated mullite crystals which were embedded in a fine-grained matrix of mullite plus a coexisting glass phase. The different microstructural developments of high- and low-Al₂O₃ compositions may be explained by solid-state and liquid-phase sintering, respectively. The microstructure of HIPed samples was very similar to that of pressureless sintered materials, but without any pores occurring at grain boundaries.     

Microstructural development and mechanical properties of pressureless-sintered SiC with plate-like grains using Al2O3-Y2O3 additives

Dense SiC ceramics with plate-like grains were obtained by pressureless sintering using -SiC powder with the addition of 6 wt% Al₂O₃ and 4 wt% Y₂O₃. The relationships between sintering conditions, microstructural development, and mechanical properties for the obtained ceramics were established. During sintering of the -SiC powder compact the equiaxed grain structure gradually changed into the plate-like grain structure that is closely entangled and linked together through the grain growth associated with the phase transformation. With increasing holding time, the fraction of phase transformation, the grain size, and the aspect ratio of grains, increased. Fracture toughness increased from 4.5 MPa m^1/2 to 8.3 MPa m^1/2 with increasing size and aspect ratio of the grains. Crack deflection and crack bridging were considered to be the main operative mechanisms that led to improved fracture toughness.     

Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO₂, Y₂Cu₂O₅ and Y₂BaCuO₅ from component oxides have been measured using solid state galvanic cells incorporating CaF₂ as the solid electrolyte under pure oxygen at a pressure of 1.01×10⁵ Pa BaO + CuO BaCuO₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=–63.4–0.0525T(K) Y₂O₃ + 2CuO Y₂Cu₂O₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=18.47–0.0219T(K) Y₂O₃ + BaO + CuO Y₂BaCuO₅ G _f,ox ^o (± 0.7) (kJ mol^–1)=–72.5–0.0793T(K) Because the superconducting compound YBa₂Cu₃O_7– coexists with any two of the phases CuO, BaCuO₂ and Y₂BaCuO₅, the data on BaCuO₂ and Y₂BaCuO₅ obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.     

Phase transformations of δAl2O3 (Saffil) fibres during their interaction with molten MgLi alloys

The phase transformation of Al₂O₃ occurring in Saffil fibres during their infiltration with molten Mg-8 wt% Li alloy was studied by secondary ion mass spectroscopy, X-ray diffraction and infrared spectroscopy methods. It has been shown, that lithium penetrates very quickly into the whole fibre volume, attaining up to Li/Al 0.25–0.30 ion ratio. The metastable spinel-like compound, (Li), was formed by incorporation of Li⁺ ions into the Al₂O₃ lattice in which the basic spinel structure unit has been assigned by the formula Al₈ [Al(_40–x)/3(_8–2x )/3]Li _x ]O₃₂. During long-term annealing, a further transformation (Li) LiAl₅O₈ proceeded, and LiAlO₂ aluminate was also identified in Saffil fibres with high Li/Al concentration ratio values. In parallel with lithium, magnesium also penetrated the Saffil fibres within an infiltration period; however, the incorporation of magnesium into the spinel lattice has not been observed.     

A high-resolution-electron-microscopy study of a γ/γ′-α directionally solidified eutectic alloy

The microstructure of a /- directionally solidified (DS) eutectic alloy with a nominal composition of Ni-30.26Mo-6.08Al-1.43V (wt%) was investigated by means of high-resolution electron microscopy (HREM) and analytical electron microscopy. The -fibres exhibited a typical morphology with a rectangular cross-section and they displayed the Bain orientation relationship (OR) with the / matrix; that is, [001][001] and (110)(010). Misfit dislocations and lattice strain fields existed at the / interface for different habit planes; that is, (110)(010) and (100)(110) were analysed. EDAX (Energy dispersive X-ray) analysis showed that the composition of the -phase was approximately Ni₄(Mo, Al, V); it contained 90° rotational domains of Ni₃(Mo, Al, V) with a DO₂₂ structure and Ni₂(Mo, Al, V) with a Pt₂Mo structure.     

Properties of Multicomponent Solid Solutions Based on Lead Zirconate Titanate near Morphotropic Regions

The structural and dielectric ( ^T ₃₃/₀) properties of Pb(Ti,Zr)O₃–PbB"_1-B"O₃–PbB"_1-B"O₃solid solutions were studied along the morphotropic region. Depending on the nature of the substituent cations, the properties of the solid solutions either vary monotonically with the content of the soft-electric component or exhibit extrema at a certain average electronegativity of the B-site cations.