Thermal transformation of hydrated ferric oxide gel and preparation of ultrafine oxide

Hydrated ferric oxide gel has been prepared by addition of a solution of ferric ammonium sulphate to that of sodium hydroxide kept at room temperature. Thermal analysis of the gel shows an endothermic peak at 130 C and three exothermic peaks at 210, 315 and 430 C. The sequence of transformation has also been investigated by thermogravimetry, X-ray diffraction, infra-red spectroscopy and surface-area measurement. The gel is found to consist of -FeOOH·nH₂O as the primary particle, which crystallizes at around 210 C and subsequently transforms to -Fe₂O₃ at around 315 C. The initial crystallite size of the oxide formed, is about 700 nm. However, it increases significantly ( 3000 nm) accompanied by an exotherm when the oxide is heated beyond 400 C.     

Observations on the mechanical properties of nickel oxide scales

The mechanical properties of NiO scales produced by the complete oxidation of high-purity (grade-1) Ni and commercial-purity (grade-A) Ni have been investigated at 700 to 1000 C. The modulus of elasticity of both grades of oxide decreased with increasing temperature, whereas the modulus of rupture for grade-A oxide exhibited a maximum at 850 C and that for grade-1 oxide decreased with increasing temperature. At 700 C, elastic deformation to fracture occurred with both oxides, whereas, at temperatures 850 C, plasticity was also observed. The plasticity of grade-1 oxide was 3 times greater than that of grade-A oxide.Creep behaviour of the oxides was studied at 900 and 1000 C. Primary and secondary creep was observed and, in both oxides, the creep rates increased with increasing temperature and load. The creep rate of grade-1 oxide was 10 to 20 times greater than that for grade-A oxide.     

Study of Na2O-SiO2-Fe2O2-Y2O3 glass by Mössbauer and EPR spectroscopy

Mössbauer, EPR and magnetization experiments have been carried out on the glass composition Na₂O-SiO₂-Fe₂O₂-Y₂O₃ in which yttrium iron garnet (YIG) can be precipitated by suitable heat-treatment. The measurements have been carried out on the as-quenched sample as well as samples heat-treated for 4 h at 400, 500, 600, 650, 700, 750, 810 and 850 C. Mössbauer spectra from the as-quenched sample as well as the first six samples showed a quadrupole splitting while the last two samples, as well as the sample heat-treated (i) by a two-stage process at 600 C and then at 750 C for 4 h each, and (ii) at 700 C for 40 h, showed a hyperfine as well as quadrupole splitting. The behaviour of the isomer shift (IS) and quadrupole splitting (E) with the heat-treatment temperature show significant changes at the glass transition and crystallization temperatures. The Mössbauer data have been found consistent with optical and electron micrographs which show a large variation in particle size of the precipitated magnetic phase. This has been further correlated with EPR and magnetization data.     

Direct current electrical conductivity of gamma ferric oxide

The study of the direct current electrical conductivity, , of freshly prepared -Fe₂O₃ and that of a sample stored for seven days in static air suggests that -Fe₂O₃ adsorbs oxygen and water from the atmosphere. From infra-red spectra it is deduced that the absorbed water in -Fe₂O₃ is present as the physically adsorbed water and as lattice water. The adsorbed oxygen and physically adsorbed water are removed by heating to 100 C, while the lattice water remains in -Fe₂O₃ even up to 280 C. The removal of lattice water is associated with a decomposition during which some of the hydrogen formed occupies the vacancy sites. This suggested formation of the hydrogen ferrite phase is based on the kink in the log against T ^–1 curve observed at 177 C. This kink is very well resolved for a sample equilibrated at 100 C in normal atmosphere, and the measurements of above 100 C of this sample are done in an N₂ atmosphere. The suggestion that the hydrogen ferrite phase is formed has been substantiated by comparison of the X-ray diffraction patterns of -Fe₂O₃ heated under the different atmospheres. From the log against T ^–1 plot for a sample heated under a nitrogen atmosphere the activation energy is small (< 0.05 eV) up to 215 C, and it is comparatively large (0.95 eV) above 215 C. These results suggest a hopping mechanism for the direct current electrical conductivity of -Fe₂O₃. This suggestion has been substantiated by data of the temperature variation of Seebeck voltage.     

Methanation reactivity of carbon deposited directly from CO2 on to the oxygen-deficient magnetite

The methanation reactivity of surface carbon deposited from CO₂ on the oxygen-deficient magnetite was studied by the isothermal methanation reaction and the temperature programmed surface reaction (TPSR). In the methanation reaction with H₂ gas, in a closed system at 150–200C, active carbon, which was not observed by the TPSR measurements, was found. About 20% out of the deposited carbon was in the form of atomic carbon and readily converted into CH₄ (5 min) above 150C with H₂, and about 80% at 300C. At 350C these atomic carbons were transformed into polymerized carbons, which was less reactive for methanation.     

Grain boundary sensitization and desensitization during the ageing of 316L(N) austenitic stainless steels

Two casts of type 316L(N) austenitic stainless steel have been solution treated for 1 h at 1070 C, air-cooled, then aged for up to 20 000 h at temperatures between 550 C and 750 C. Grain boundary precipitation of the M₂₃C₆ phase occurs, and the Cr composition profile normal to the grain boundaries has been determined at high resolution by an analytical electron microscope. The data have been fitted firstly to collector plate models, which indicated that some of the material was in the process of desensitization, or healing, indicated by a rise in the boundary Cr content. The data were then fitted to a model of the Cr profile as a function of ageing treatment in the healing regime, and a good correlation was obtained.     

Synthesis and characterization of a high-temperature oxide lubricant

PbMoO₄ is a potential solid lubricant for use at elevated temperatures in oxidizing environments. Pulsed laser deposition (PLD) was utilized to grow thin films of this material because it allows good control over film chemistry and crystallinity. Films were grown at different substrate temperatures in vacuum and in partial pressures of oxygen. The chemistry and crystallinity of the films were evaluated using X-ray photoelectron spectroscopy, Raman spectroscopy, and glancing angle X-ray diffraction. Friction coefficients and wear lives were measured using a ball-on-flat tribometer at room temperature and 700C. Films deposited in vacuum, at room temperature and at 300C, were oxygen deficient. To adjust chemistry and crystallinity, films were grown in a partial pressure of oxygen (i.e. 6.7×10^–1 Pa). Stoichiometric, crystalline films of PbMoO₄ were produced when films were grown at 300C in this environment. PbMoO₄ films were lubricious ( = 0.35) and long lived at 700C, but at room temperature had high friction and failed quickly. The properties of the films grown at the different conditions are discussed.     

Particle generation and film formation in an atmospheric-pressure chemical vapour deposition process using tetraethylorthosilicate

Effects of an oxygen flow rate on film formation and nanometre-sized particle generation in the gas phase were examined simultaneously in an atmospheric-pressure chemical vapour deposition reactor using tetraethylorthosilicate (TEOS). The critical temperature for particle generation decreased rapidly to 340C from 740C with increasing oxygen flow rate, but it decreased slightly to 600C from 700C for film formation. There were no conditions where film was deposited without particle generation in a TEOS/O₂ system. The nanometre-sized particles generated in the systems were amorphous and non-spherical, and their size distributions were polydisperse. The Fourier transform infrared (FT-IR) and thermal desorption (TDS) spectra of the particles were not affected by oxygen flow rate, and showed that the particles contained a small amount of an ethoxy group and a relatively large amount of a hydroxyl group. It was found from comparisons between FT-IR and TDS spectra of particles and films that the SiO₂ films were formed by -elimination reactions, where C₂H₄ and H₂O are released from the ethoxy group.     

Phase transformations in the thermotropic liquid crystal polymer: 60/40 PABA/PET

Microstructures observed in 60/40 PABA/PET co-polyester in transmitted polarized light are reported. The microstructure changes as a function of temperature. Between 190 and 340 C the optical textures are similar to those seen in small molecule liquid crystals in the smectic C modification; above 340 C the textures are typical of nematic structures. At 420 C the specimen is totally isotropic and begins to degrade. Rapid cooling to below 190 C can quench in the high temperature phases, including the isotropic one. DSC traces show endotherms identifiable with the onset of mobility at 190 C, the transition from smectic C to nematic-like textures at 340 C and the development of the isotropic phase in the range 350 to 420 C. The smectic C to nematic transition in texture is associated with the appearance of a transient microstructure, known as a myelin texture, and reported here for the first time in a liquid crystal polymer.     

Deformation in spinel

Stoichiometric MgAl₂O₄ spinel was deformed in compression at temperatures from 1790 to 1895 C and the dislocation structures analysed by transmission electron microscopy. {1 1 1}1 1 0 slip was observed on both the primary and cross-slip systems, and there was much secondary slip as well; all six 1 1 0 Burgers vectors were present in electron micrographs. This secondary slip leads to very high work-hardening rates, approximately/70 at 1790 C, where is the shear modulus. Since it is known that deformation in nonstoichiometric (alumina-rich) spinel crystals occurs by {1 1 0}1 1 0 slip, the electrostatic and geometric aspects of 1/4 110 dislocations moving on {1 1 1} and {1 1 0} planes are considered in some detail. It is porposed that the octahedral cation vacancies present in non-stoichiometric spinel diffuse to dislocations during deformation and thus favour {1 1 0} slip.     

Oxidation behaviour of Β-sialon fabricated from α-Si3N4 and aluminium iso-propoxide

-sialon with z=0.5 was fabricated by hot pressing of a spray-dried mixture of -Si₃N₄ and aluminium iso-propoxide solution. The oxidation behaviour of this -sialon was investigated, comparing it with commercial -sialon containing Y₂O₃ as a sintering aid. Oxidation tests were carried out at 1200 and 1400C for 25 to 200 h in air. The oxide layer of aluminium isopropoxide-derived -sialon was thin, dense, smooth and homogeneous without bubbles and cracks. The strength after oxidation at 1400C for 200 h was about 800 MN m^–2, almost the same value as before oxidation. The oxide layer of Y₂O₃-doped -sialon was thick and inhomogeneous, containing many bubbles, cracks and grown needle-like crystallites (Y₂Si₂O₇). The strength after oxidation at 1200C for 200 h fell to 1/2(440 MN m^–2) because of pit formation in the oxide layer, and at 1400C for 200 h fell to 1/4(200 MN m^–2) because of severe swelling and flaking of the oxide layer. The high oxidation resistance of aluminium iso-propoxide derived -sialon was mainly due to its homogeneous microstructure and freedom from foreign constituents such as Y₂O₃.     

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.     

Wetting of nickel by silver

Sessile drop experiments of molten silver and nickel were performed in air and helium at 970 C. A NiO layer formed at the interface in air; silver formed a 90 contact angle. In helium silver formed a 9 contact angle on nickel. The role of solution reactions in forming these angles is discussed.     

Antimicrobial and antifungal agents derived from clay minerals

Montmorillonite supported by Ag⁺-chelate of hypoxanthine was synthesized and heat-treated at 200 C intervals below 800 C under nitrogen. These samples were subjected to examinations of the structure and properties including antimicrobial activity. Hypoxanthine itself did not possess antimicrobial activity to bothStaphylococcus aureus andEscherichia coli, but montmorillonites supported by the Ag⁺-chelate exhibited activity. Hypoxanthine in montmorillonite decomposed at 400–600 C; and Ag metal particles deposited after heating to 600 C and grew with raising heating temperature. The Ag⁺-chelate montmorillonite showed clear antimicrobial activity even after heating to 800 C.     

Time-dependent structural modifications in tin oxide thin films under environmental conditions

Time-dependent crystalline structure and surface morphology of transparent conducting thin films of undoped tin oxide have been studied under environmental conditions by X-ray diffractometry and scanning electron microscopy. Tin oxide thin films were produced, via chemical vapour deposition, in three batches; two batches with single deposition at substrate temperatures of 400 C and 560 C, respectively, and the third batch produced by double deposition firstly at 560 C and then at 400 C substrate temperature. It is found that the crystallinity of the as-grown tin oxide thin films produced by single deposition degrades with shelf-life period and an amorphous phase is developed under environmental conditions. In the tin oxide films produced by double deposition there was no degradation in the crystallinity of the films, but a change in the preferential crystallite orientation was observed. The implications are discussed.     

Stress relaxation in zirconium carbide. Report 2. Mechanisms of stress relaxation. The relationship of the processes of creep and relaxation

Mechanisms of stress relaxation in ZrC_1.00 (d=6–35 .m) in the area of the ductile-to-brittle transition temperature (1600–2200C) are considered. It is established that in the 1800–2000C range for ZrC_1.00 with grain sizes of 6 and 14–35 m, respectively, stress relaxation occurs as the result of pure grain boundary slip while at higher temperatures by intragranular cross slip. It is shown that creep in the steady stage and stress relaxation in ZrC_1.00 with grain sizes of 6–35 m are controlled by different physical processes, which makes impossible obtaining for these materials of data on stress relaxation by conversion with use of information on steady creep.Translated from Problemy Prochnosti, No. 2, pp. 55–60, February, 1994.     

p-Version hierarchical three dimensional curved shell element for heat conduction

This paper presents a finite element formulation for a three dimensional nine node p-version hierarchical curved shell element for heat conduction where the element temperature approximation can be of arbitrary order p , p , and p in the , and directions. This is accomplished by first, constructing one dimensional hierarchical approximation functions and the corresponding nodal variable operators for each of the three directions , and using Lagrange interpolating polynomials and then taking their products (sometimes also called tensor products). The element approximation functions as well as the nodal variables are hierarchical and therefore the element matrices and the equivalent heat vectors are hierarchical also i.e. the element properties corresponding to polynomial orders p , p , and p are a subset of those corresponding to (p +1), (p +1), and (p +1). The element formulation ensures C ⁰ continuity. The curved shell geometry is constructed in the usual way by taking the coordinates of the nodes lying on the middle surface of the element (=0) and the nodal thickness vectors. The element properties i.e. element matrices and the equivalent heat vectors are derived using weak formulation (or quadratic functional) of the three dimensional F ourier heat conduction equation and the hierarchical element temperature approximation. The element formulation is equally effective for very thin as well as extremely thick shells. Numerical examples are presented to demonstrate the accuracy, efficiency, modeling convenience, faster rate of convergence and over all superiority of the present formulation. The h-approximation results are presented for comparison purposes.     

Microstructures and subcritical crack growth in oxidized hot-pressed Si3N4

The microstructure of the oxide scales, primarily the size, distribution, and density of the pits, was characterized in hot-pressed Si₃N₄ oxidized at different temperatures from 1300 to 1450 C. These microstructural features and the chemical changes in Si₃N₄ due to oxidation were related to the elevated-temperature subcritical crack-growth (SCG) behaviour. Oxidation at 1375 C for 240h resulted in a measurable improvement in SCG over that in as-hot-pressed and 1300 C-oxidized Si₃N₄.     

Formation and characteristics of lead lanthanum zirconium titanate thin films formed by using the r.f. sputtering method

PLZT (lead lanthanum zirconium titanate) thin films were prepared by using the r.f. magnetron sputtering method and post-annealing for crystallization at 650 C. The films which were annealed at 650 C for 10 min consisted of a metastable phase and a stable phase. However, another film which was annealed at 650 C for 20 min had only stable perfect perovskite phase. The stability of the post-annealed thin film and substrate interfaces was observed by using scanning electron microscopy. The longer the annealing time, the more unstable were the interfaces. By analysing the EDX data, the composition difference between the sputtering target and thin films, and the composition variation between as-deposited and post-annealed PLZT were studied. The films annealed at 650 C for 20 min showed good ferroelectric and electrical properties with a remanent polarization (P _r) of 11.5 C cm^–2, and a coercive field (E _c) of 164 kV cm^–1.     

90‡ domain reversal in Pb(Zr x Ti1−x )O3 ceramics

A simple and direct method has been proposed, which may be used for quantitatively distinguishing the mechanisms of domain reorientation processes in polycrystalline materials. Using this method, the 90 domain reorientation in the Pb(Zr _x Ti_1–x )O₃ ceramic under an electric field was examined through the X-ray diffraction analysis. It was found that polarization switching in the PZT ceramic with a composition near the morphotropic phase boundary, is predominantly controlled by the two successive 90 domain processes rather than only the 180 domain reversal process. Experimental results also indicate that the coercive field of ferroelectric ceramics is related to the cooperative deformation associated with each grain. This cooperative deformation arises from the 90 domain-reversal process.