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.     

Fracture toughness of concretes at high temperature

The fracture toughness of ordinary and refractory concretes in the range of 20–1300C was investigated, and the stress intensity factor, K _Ic, on three-point bent specimens (according to ASTM E-399 recommendation) determined. With an increase in testing temperature, the stress intensity factor decreases for both concretes. The values of K _Ic at 20C for both concretes are comparable, being equal to 0.64 MNm^–3/2 for ordinary concrete, and 0.72 MNm^–3/2 for refractory concrete, respectively. At 1100C, K _Ic has a value of 0.043 MNm^–3/2 for ordinary concrete, and for the refractory concrete at 1300C, K _Ic=0.34 MNm^–3/2. The method presented for predicting the behaviour of concrete at high temperature may be used in engineering practice.     

Temperature-dependent change of Cu-O bond in La2CuO4 and YBa2Cu3O7

Valence-band spectra of La₂CuO₄ and YBa₂Cu₃O₇ were obtained by using X-ray photoemission varying the temperature of the measurement (35, 260, 300, and 500 C). In La₂CuO₄ the broad band centred around 4eV splits into two peaks at 260 C. At both 35 and 500 C the spectra show almost similar shape. In YBa₂Cu₃O₇ the broad peak centred around 4eV splits into two peaks at 500 C. Below 300 C the spectra show almost similar shape. These splittings of the valence-band spectra may be due to the rearrangement of the crystal structure accompanying the phase transition from the orthorhombic to tetragonal symmetry.     

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.     

Surface and grain boundary analysis of doped zirconia ceramics studied by AES and XPS

The surface- and grain boundary composition of Y, Ce and Ti doped zirconia were studied by X-ray Photoelectron Spectroscopy and Auger Electron Spectroscopy/Scanning Auger Microscopy. The grain boundaries and free surfaces showed the same enrichment levels. After heat treatment 1000 C all yttria doped samples showed yttrium enrichment. In the ZrO₂-Y₂O₃ system the yttrium enrichment did not depend on the bulk concentration and amounted 30–34 mol% YO_1.5 in all cases. As a consequence the segregation factor increases with decreasing solute concentration in the bulk. The thickness of the segregation layer was about 2–4 nm. In the ternary Y doped systems yttrium is the main segregant. In ceria-doped tetragonal zirconia polycrystals (Ce-TZP) systems significant segregation of cerium starts atT1300C and is mainly attributed to Ce³⁺. In Y,Ti-TZP systems also strong segregation of Ti⁴⁺ occurs. The absolute value of the increase of the surface concentration in fine grained material is smaller than in coarse grained material. This is mainly due to depletion of the bulk.     

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.     

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.     

Thermomechanical correction to the drag force on a sphere and a cylinder moving in HeII

The drag force on a sphere and a cylinder moving in HeII is considered on the basis of the full system of the two-fluid dissipative hydro-dynamical equations. It is shown, that due to the thermomechanical effect in superfluid there exists a specific correction to the drag force on a body. The value of this thermomechanical correction F has the order of the ratio1 _T/R or1 _T ² /R² (R is the size of the body, and1 _T is the length of the formation of the convective heat flow). The value of F grows at low temperatures, where1 _T is proportional to the characteristic time of the phonon-roton scattering process, and in the region near the -point, where1 _T has the same temperature dependence as the order parameter correlation length 1_T (T–T)^–2/3. The effects under discussion can be investigated experimentally by measurements of the mobility of small objects. A comparison is given with the data of the mobility of positive and negative ions in HeII near the -point.     

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.     

Microstructural,electrical and magnetic properties of NdBa2Cu3O7−δ prepared from BaO2

NdBa₂Cu₃O_7– was synthesized in oxygen from a stoichiometric mixture of Nd₂O₃, BaO₂ and CuO between 890 and 1070 C. The resulting material was composed of small crystals of NdBa₂Cu₃O_7– (2 to 10 m) and of BaCuO₂ as a secondary phase. The effect of the synthesis temperature on the normal-state resistivity, the critical current density and the magnetic susceptibility was investigated. The highestJ _c values (175 A cm^–2) were measured in samples treated between 1010 and 1050 C.     

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.     

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.     

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.     

Superfluid density near the lambda point of4He under pressure

The superfluid density in ⁴ He was determined near T from the second-sound velocity as a function of T–T and pressure. The critical exponent of the superfluid density was found to depend, even slightly, on the pressure. Furthermore, the fundamental length ₀ in the coherence length = ₀ [1–(T/T)]^–' seemed to be proportional to the mean interatomic distance. The implications of the results are also discussed.This work was partly supported by The Ito Science Foundation and by The Nishina Memorial Foundation.     

NMR Studies on 3He-3He and 3He-4He tunneling motions in solid 3He-4He mixtures

Helium-3 nuclear spin relaxation times T ₁, T ₂, and T ₁have been measured for ³He-⁴He solid mixtures at the exchange plateau region (~0.5K). The ³He concentrations X ₃of the samples were 7.2, 2.9, 1.8, 1.4, 0.67, 0.65, and 0.22%, and their molar volumes varied between 19.9 and 20.9cm³/mole in hcp phase. The spectral density function J() for dipolar field fluctuations was determined in the low-frequency branch from T ₁measurements and in the high-frequency branch from conventional T ₁measurements. It was found that J() is given by J() = cJ()|_3–4 + (1–c)J()|_3–3, where J()|_3–4 is the spectral density function due to the ³He-⁴He tunneling motions, and J()|_3–3 is that due to the ³He-³He tunneling motions. Using the Torrey theory, the correlation frequency of the ³He-⁴He tunneling motions was evaluated from T ₁data, and was found to be in good agreement with Landesman 's theory.Supported in part by the Japan Society for the Promotion of Science through a grant to Y.H.     

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.     

Preparation of ceramic coatings from pre-ceramic precursors

SiC-coatings derived from pyrolysis of polycarbosilane layers on stainless steel and mild steel substrates have been studied using a combination of scanning electron microscopy (SEM), energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and ultramicrohardness techniques. The coatings on mild steel plates at firing temperatures of 700C are cracked but uncracked SiC coatings can be formed on stainless steel substrates at 700–800C. X-ray photoelectron studies show that these coatings are covered with a layer of SiO₂ and contain graphitic carbon, while Rutherford backscattering studies indicate inhomogeneities in the coating layer due to mixing of substrate and coating components at the interface between the two. Ultramicrohardness results indicate the SiC/stainless steel coatings formed at 800C are softer than the equivalent SiC coatings formed on alumina substrates at 1100C. Above 800C, a possible combination of both thermal expansion mismatch and CrN formation, which causes the growth of chromium-rich nodules in the stainless steel, serve to disrupt and ultimately destroy the coherence of the SiC coatings. The use of sol-gel-derived SiO₂ coatings as a barrier does not prevent the destruction of the SiC coating by this mechanism.     

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.     

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.     

Phase stability and oxygen transport characteristics of yttria- and niobia-stabilized bismuth oxide

As a part of an overall study to explore the potential application of stabilized Bi₂O₃ as oxygen separator in various electrochemical systems, an investigation of the stability and transport characteristics of yttria- and niobia-stabilized bismuth oxide was undertaken. Polycrystalline Bi₂O₃ samples containing 25mol % Y₂O₃ were fabricated by pressureless sintering powder compacts at 1000 C in air. Samples containing 15mol % Nb₂O₅ were also fabricated by pressureless sintering at 900 C in air. The resulting samples were dense and of an equiaxed microstructure with grain size in the range from 28m for the yttria-stabilized and 42m for the niobia-stabilized materials, respectively. X-ray diffraction of the as-sintered specimens showed them to be single phase with CaF₂-type structure. Ionic conductivity was measured by an a.c. technique over a wide range of temperatures. It was observed that the ionic conductivity of the yttria-stabilized bismuth oxide was greater than that of the niobia-stabilized one.The specimens subsequently were annealed over a range of temperatures between 600 C and 700 C for up to several days. X-ray diffraction traces taken on the Y₂O₃-stabilized samples indicated that the original cubic solid solution had decomposed. The decomposition of the yttria-stabilized samples was also accompanied by the occurrence of exaggerated grain growth. The observed decomposition is not in agreement with the phase diagram available in the literature, according to which the cubic phase should be stable over the range of temperatures the samples were annealed in the present study. By contrast, Nb₂O₅-stabilized Bi₂O₃ remained cubic, although it appeared to have dissociated into two cubic solid solutions of slightly differing lattice parameters. There was no perceptible change in the grain size of the niobia-stabilized samples.Several electrolyte tubes made of the yttria- and niobia-stabilized bismuth oxide were electrolytically tested under a d.c. mode with silver electrodes. In tubes made of the yttriastabilized material, the current density decreased with time (under a constant applied voltage) at 650 C and at 700C but did not at 700C consistent with the observation that the material did not decompose at 700 C but did at 650 C. At 600 C, the rate of decrease was slower than at 650 C indicating that the kinetics of phase decomposition is probably slower at 600 C. In the niobia-stabilized tubes the decrease in the current density was lower. This decrease is probably related to the apparent formation of two cubic solid solutions of slightly differing compositions.The present work shows that the published phase diagram of the Y₂O₃-Bi₂O₃ system is incorrect. The present results also suggest that for application to temperatures as low as 650 C (and possibly lower), electrolytes made with Nb₂O₅ as the stabilizer are preferable.