An anomalous behaviour in the phase stability of the system Fe2O3 and NiO

Iron-nickel mixed oxides containing up to 50 mol% of NiO were prepared by firing the corresponding co-precipitated hydrous oxides; characterization was performed by X-ray diffraction, infrared spectroscopy, magnetic susceptibility, electrical conductivity and thermoelectric power measurements. A non-stoichiometric ferrite phase was formed when a sample containing 20 mol% NiO was sintered at 1050°C. This phase had two- to three-fold higher conductivity than either Fe₂O₃ or the stoichiometric ferrite (NiFe₂O₄). The thermoelectric power of this phase indicated a sharp change of charge carriers from n- to p-type near 350°C. This non-stoichiometric ferrite phase was stable only in a small temperature range and dissociated into -Fe₂O₃ and stoichiometric ferrite above 1200°C. Samples containing 5 and 10 mol% NiO also had small fractions of this non-stoichiometric ferrite phase when sintered at 1050°C.     

A Mössbauer study of the oxidation of Fe-Ni alloys at 535 and 635°C

Fe⁵⁷ transmission Mössbauer spectroscopy, supported by metallography, SEM and X-ray diffraction analysis, has been employed to study the oxidation of Fe-Ni alloys at 535 and 635° C in 1 atm. of air. With increasing Ni content of the alloy, the composition of the scale changed and the oxidation rate decreased. For an alloy containing 0.9% Ni, the oxide scale produced at 535° C was Fe₃O₄ covered by a thin outer layer of-Fe₂O₃, while at 635° C FeO was additionally present as a major phase. The scale formed on a 10% Ni alloy at both 535 and 635° C was similar to that observed for the 0.9% Ni alloy oxidized at 535° C (i.e. of Fe₃O₄ and-Fe₂O₃), although the-Fe₂O₃ layer tended to be relatively thicker. For a 49% Ni alloy, the scale at both 535 and 635° C comprised an inner layer of Ni _x Fe_3–x O₄ (withx0.5, on average) and an outer layer of-Fe₂O₃, of similar thickness. Finally, on an 83% Ni alloy oxidized at 635° C, the scale consisted of roughly equally thick layers of NiO (next to the metal) and NiFe₂O₄, and a thin outer covering of-Fe₂O₃. The decrease in oxidation rate with increasing Ni content of the alloy is discussed briefly in relation to the changing composition of the scale and diffusion in the alloy.     

Chemical and structural properties of the system Fe2O3-Cr2O3

Chemical and structural properties of the mixed metal oxides (1–x)Fe₂O₃+xCr₂O₃ were studied by different techniques. X-ray powder diffraction showed the existence of solid solutions, (Fe_1–x Cr _x )₂O₃, over the whole concentration region, 0x1. The gradual replacement of Fe³⁺ with Cr³⁺ ions in samples prepared at 900°C caused changes in unit-cell parameters; most of these changes took place in the region fromx0.3–0.9. The samples having the fraction of Cr₂O₃ in the region from 0.7–0.8, contained two closely related phases, with slightly different compositions. After an additional heat treatment at 1100°C, these samples contained only one phase.⁵⁷Fe Mössbauer spectroscopy showed a gradual decrease of hyperfine magnetic field with increasing Cr₂O₃ content. The sample having the fraction of Cr₂O₃ of 0.7, and prepared at 900°C, exhibited two separated sextets at room temperature, in comparison with other compositions showing one sextet. It was shown that Fourier transform infrared (FT-IR) spectroscopy is a powerful method for the investigation of structural changes in these solid solutions. The increase in the Cr₂O₃ content resulted in shifts of the corresponding infrared bands. In addition, a gradual transition of the spectrum typical for -Fe₂O₃ to the spectrum typical for Cr₂O₃ was shown. The transition effects observed in the FT-IR spectra were correlated with the X-ray powder diffraction and⁵⁷Fe Mössbauer spectroscopic results.     

In situ conversion electron Mössbauer spectrometry (CEMS) studies on α- and γ-Fe2O3 gas sensors

Clarification of the sensing mechanism of-Fe₂O₃ and -Fe₂O₃ gas sensors was attempted. The information on the surface states of iron oxides at working temperature (400° C for-Fe₂O₃ and 250° C for-Fe₂O₃) was obtainedin situ by applying thein situ CEMS. The-Fe₂O₃ gas sensor, prepared by the precipitation of Fe(OH)₃ from a solution of iron (III) sulphate and tin (IV) chloride, was composed of fine particles (–15 nm) and was superior in sensitivity to other-Fe₂O₃. The gas sensitivity was found to depend on the amounts of remaining sulphate ion, the microstructure and a small amount of iron (II) species generated through the reduction of-Fe₂O₃. The sensing mechanism of-Fe₂O₃ gas sensor was confirmed to be due to the reduction of-Fe₂O₃ to the low resistive Fe_3-x O₄ by combustible gas and to depend on the crystal structure.     

Electrical conductivity study of oxidation process in manganese-substituted magnetites

During oxidation in air of finely-grained manganese-substituted magnetites (Mn _0.8x ²⁺ Fe _1–0.8x ³⁺ )_A– (Fe _1+0.6x ³⁺ Fe _1–0.8x ²⁺ Mn _0.2x ³⁺ )_BO ₄ ^2– (A=tetrahedral, B=octahedral) the temperature dependence of the electrical conductivity over a temperature range of 100 to 700° C was investigated. Below 500° C the evolution of electrical conductivity might be closely associated with the position and nature of cations in the spinel lattice. The profile of the =f(t) curves show that the mechanism of electrical conduction in the temperature range 150 to 300° C can be explained in terms of the oxidation of Fe²⁺ to Fe³⁺ ions at octahedral sites. For the temperature range 300 to 400° C the conductivity involves the hopping of electrons from tetrahedral-site Mn²⁺ ions to tetrahedral-site Mn³⁺ ions. Above 500° C the oxidation of Mn²⁺ ions leads to an increase in conductivity with the generation of new phases of -Fe₂O₃, Mn₂O₃ and -(MnFe)₂O₃.     

Oxidation behavior of FeAl alloys with and without titanium

The influence of Ti addition on the high temperature oxidation behavior of FeAl intermetallic alloys in air at 1000°C and 1100°C has been investigated. The oxidation kinetics of FeAl alloys was examined by the weight gain method and oxide products were examined by XRD, SEM, EDS and EPMA. The results showed that the oxidation kinetic curves of both Ti-doped and binary Fe-36.5Al alloys could be described as different parabolas that followed the formula: (W/S)² = K _p t + C. The parabolic rate constant, K _p values are approximately 2.4 and 3.3 mg² cm^–4 h^–1 for Fe-36.5Al alloy and about 1.3 and 2.0 mg² cm^–4 h^–1 for Fe-36.5Al-2Ti alloy when oxidizing at 1000°C and 1100°C respectively. The difference between Fe-36.5Al and Fe-36.5Al-2Ti alloy is not only in the surface morphology but also in the phase components. In the surface there is only -Al₂O₃ oxide for Fe-36.5Al alloy while there are -Al₂O₃ and TiO oxides for Fe-36.5Al-2Ti alloy. The effects of Ti addition on the oxidation resistance of FeAl alloy were addressed based on the microstructural evidence.     

Formation of NiFe2O4 nanoparticles by mechanochemical reaction

Preparation of nanosized NiFe₂O₄ particles by mechanochemical reaction(NiO+α-Fe₂O₃) and subsequent thermal treatment was investigated using X-ray diffraction (XRD). Thermal treatment of the as-milled powder at 700 °C for 1 h led to the formation of NiFe₂O₄ nanoparticles with an average crystal size of about 23 nm. Effect of thermal treatment temperature on the crystal size of the nanoparticles was studied. The mechanism of nanoparticles growth was primarily discussed. The activation energy of NiFe₂O₄ nanoparticle formation during calcination was calculated to be 16.6 kJ/mol.     

Formation and characterization of the solid solutions (CrxFe1−x)2O3, 0⩽x⩽1

The solid solutions (Cr_xFe_1–x)₂O₃, 0 x 1, were prepared by traditional ceramic procedures. The samples were characterized using X-ray diffraction, Mössbauer, Fourier transform infra-red (FT-IR) and optical spectroscopic measurements. In the whole concentration range two phases exist phase F, -(Cr_xFe_1–x)₂O₃, which is isostructural with -Fe₂O₃ and phase C, which is closely related to Cr₂O₃. Phase F exists in samples heated up to 900°C, for 0 x 0.95. Phase C exists from x0.27 to x=1 for samples heated up to 900°C and from x0.65 to x=1 for samples heated up to 1200 °C. For samples heated up to 900 °C, the solubility limits were 27.5 ± 0.5 mol% of Cr₂O₃ in -Fe₂O₃ and 4.0 ± 0.5 mol % of -Fe₂O₃ in Cr₂O₃. For the samples heated at 1200 °C the diffraction peaks for the F and C phases in the two phase region were severely overlapped and thus the solubility limits could not be determined accurately as for previous samples. ⁵⁷Fe Mössbauer spectra of the samples heated up to 1200 °C showed significant broadening of spectral lines and a gradual decrease of the hyperfine magnetic field with increase of x up to 0.50. For x0.7, a paramagnetic doublet with collapsing sextet was observed. The spectra were interpreted in terms of an electronic relaxation effect; however, an agglomeration of iron ions which would contribute to the superparamagnetic effect could not be excluded. The FT-IR spectra showed transition effects in accordance with the X-ray diffraction results. The most intense absorption bands, observed for the samples heated up to 1200 °C, were located at 460 and 370 nm (22 000 and 27 000cm^–1) for x 0.5, 500 and 360 nm for x < 0.3, and might be correlated with the strong enhancement of the pair transitions through antiferromagnetic interactions. The intensification of the ⁶A₁ 4T₁ Fe³⁺ ions in all spectra and the development of the absorption at 13000 cm^–1 due to a metal-metal charge transfer (Cr³⁺ Fe³⁺) transition, might be explained by exchange coupling which has been observed in some spinel compounds.     

Hydrazine method of synthesis of γ-Fe2O3 useful in ferrites preparation. Part IV – preparation and characterization of magnesium ferrite, MgFe2O4 from γ-Fe2O3 obtained from hydrazinated iron oxyhydroxides and iron (II) carboxylato-hydrazinates

Electro-magnetic properties and microstructural characterization of MgFe₂O₄ synthesized by a ceramic technique at 1000°C from iron oxides, consisting of mainly -Fe₂O₃ and traces of alpha-Fe₂O₃, prepared from iron ore rejects, are compared with the ferrite obtained from commercial alpha-Fe₂O₃. The sources of -Fe₂O₃ are hydrazinated iron (II) carboxylates and iron oxyhydroxides which autocatalytically decompose giving mainly -Fe₂O₃ of uniform particles of 10–30 nm (by scanning electron microscopy (SEM) studies) having high surface area. The ferrite synthesized from such nanoparticle size -Fe₂O₃ gave a porosity of 25% with grains ranging from 0–3 m. On the other hand, MgFe₂O₄ obtained from commercial alpha-Fe₂O₃ grains (of 1–2 m size) gave particles of 0–6 m with a porosity 42%. Saturation magnetization values 922–1168 G are found for MgFe₂O₄ from -Fe₂O₃ source while the alpha-Fe₂O₃ source gave the lowest value, 609. The Curie temperature, T_c, from magnetic susceptibility, initial permeability and resistivity measurements indicated a highest T_c of 737 K for MgFe₂O₄ from alpha-Fe₂O₃, while lower values are found for the ferrite prepared from -Fe₂O₃.     

Chemical vapour growth of HfC whiskers and their morphology

HfC whiskers were prepared from a gas mixture of HfCl₄ + CH₄ + H₂ + Ar in the presence of metal impurities, and the growth conditions and morphology were examined. The HfC whiskers preferentially grew at an H/Cl ratio of above 8, an HfCl₄ gas flow rate of 10–20 standard cm³ min^–1, a CH₄ flow rate of 10–20 standard cm³ min^–1, and at temperatures above 1050 °C. HfC whiskers, 60–170 m long, with a ball-like tip and periodically varying diameters, were obtained at 1250 °C using a cobalt impurity.     

The solid state bonding of nickel,chromium and nichrome sheets to α-Al2O3

This paper describes experiments to measure the interfacial shear strengths of bonds formed between nickel, chromium and nichrome sheets hot pressed on to -Al₂O₃ single crystal plaques. Nickel developed bonds of 8×10³ psi (56 MN. m^–2) in shear when pressing was carried out under non-reducing conditions at 1100° C, 1 tsi (15 MN. m^–2) for 2 h: in the case of chromium, the effect of pressing temperature (1000 to 1300° C) pressing pressure (1/2 to 3 tsi [7.7 to 45 MN. m^–2]) and pressing time (1/2 to 7 h) on the bond was investigated. Nickel-chrome alloys produced from alternate nickel and chromium strips showed bond strengths up to 20×10³ psi (140 MN. m^–2) whilst commercial nickel-chrome (containing a silicon impurity) was not as effective in bonding to alumina. In material prepared from alternate strips of nickel and chromium, the degree of alloy homogenisation was investigated using microprobe analysis and suggestions made as to the mechanism of the interfacial reactions with alumina.     

Low-temperature sintering of zinc oxide varistors

High-field varistors in the system ZnO-CoO-MnO-Bi₂O₃ were fabricated using powders prepared by a previously developed coprecipitation process. Following calcination, the powders were compacted and densified by conventional pressureless sintering at temperatures below 750° C in air, The effects of sample green density, sintering temperature, and grain-growth inhibitor on densification and microstructure development were investigated. Addition of aluminium at the 125 p.p.m level was used to inhibit grain growth. Samples with densities >0.98 theoretical and grain sizes <1m were fabricated by high-pressure cold-isostatic pressing followed by sintering at 730° C. For comparison, typical commercial varistor devices have grain sizes of about 20 m and switching fields of approximately 2 kV cm^–1 after sintering at 1200 to 1400° C. As a result of the fine grain size, our high-field varistors had switching fields of 45 kV cm^–1 at a current density of 10 A cm^–2. Consistent with earlier work on extremely high-density varistors (>0.98 theoretical) prepared from similar powders, nonlinearity coefficients of about 10 were measured for current densities between 2.5 and 10 A cm^–2.     

Formation of iron oxides by the oxidation of iron in Fe-MOH-H2O and Fe-MOH-H2O-O2 systems (M = Li,Na, K)

The oxidation behaviours of iron powders, ca. 100 m in diameter, in 5–50 m NaOH, 5–40 m KOH and 5–40 m LiOH solutions at 373–573 K were investigated in the absence and presence of oxygen, where m is molality. The oxidation of iron proceeded noticeably above 423 K to form Fe₃O₄, -Fe₂O₃, -NaFeO₂, -Fe₂O₃, Li _x Fe_3–xO₄ and -LiFeO₂ depending on the reaction conditions. The rate of oxidation in LiOH solutions was much slowerthan those in NaOH and KOH solutions.     

Mechanism of Ferrite Spinel Formation Revisited

Data on the volume changes of the starting reagents and reaction products were used to analyze the reactions taking place in the ferrite-forming systems MgO–Fe₂O₃, Mn_0.75Mg_0.25O–Fe₂O₃, and NiO–Fe₂O₃ in the temperature range 1255–1315°C. It was shown that, under these conditions, there is no oxygen transport through the gas phase. The possible formation of Fe²⁺ ions is attributed to partial electron compensation for the charge on the M²⁺ cations as a result of counterdiffusion. The presence of excess Fe in the spinel phase at the intermediate stages of ferrite formation is due to the transformation of -Fe₂O₃ into -Fe₂O₃ at a certain M²⁺ concentration.     

An electron microscope study of thin ferrite films prepared by the oxidation of high purity vacuum-evaporated metal thin films

The oxidation of thin films of nickel, cobalt, iron, NiFe₂ and CoFe₂ has been investigated between 200 and 1200° C. The oxidation products for the elemental metals differ from the oxidation products observed in previous work upon bulk material. The oxidation mechanism proposed for bulk material is in general still valid in the thin film situation. Above oxidation temperatures of approximately 850° C both NiFe₂ and CoFe₂ form the respective ferrites, although in the case of nickel ferrite, traces of the -Fe₂O₃ tetragonal superstructure can still be detected at oxidation temperatures of 1200° C. Films of nickel ferrite and cobalt ferrite upon single-crystal magnesium oxide substrates, produced by oxidation of vacuum-deposited NiFe₂ and CoFe₂ thin films, have been investigated by transmission and scanning electron microscopy. It has been found that (100) nickel ferrite prepared by this technique grows epitaxially upon (100) magnesium oxide.     

Formation of cadmium-containing W-type hexagonal ferrite

The main steps of the phase formation processes which take place in samples of W-type hexaferrites containing cadmium, prepared by chemical coprecipitation, have been analysed. The processes were followed by Mössbauer spectroscopy, powder X-ray diffraction, thermomagnetic analysis and magnetic measurements. For samples heated in the temperature range 1000–1100°C, the phase formation processes are the same as those verified for the other zinc, nickel, cobalt W-type compounds: forT _h=1000°C the only phases present are SrFe₁₂O₁₉ (M-type ferrite) and CdFe₂O₄ (spinel ferrite); in contrast, forT _h>1100°C, the solid state reaction between the M-type and the spinel phases does not take place and the spinel phase decomposes, leading to the formation of -Fe₂O₃.     

Structural properties of precipitates formed by hydrolysis of Fe3+ ions in aqueous solutions containing NO 3 − and Cl− ions

The structural properties of precipitates formed by hydrolysis of Fe³⁺ ions in aqueous solutions, containing N0 ₃ ^– and Cl^– ions, were investigated. The reactions of hydrolysis were performed in glass autoclaves at 120 °C. X-ray diffraction showed that -FeOOH and -Fe₂O₃ were present in hydrolytical products formed in solutions containing N0 ₃ ^– ions, while -FeOOH and -Fe₂O₃ were typical hydrolytical products in solutions containing Cl^– ions. In the mixed Fe(N0₃)₃+FeCl₃ solutions, the phase composition of the hydrolytical products was determined by the concentration of the dominant Fe(III)-salt. Fourier transform infrared spectroscopy and Mössbauer spectroscopy were also used for the structural characterizations of the hydrolytical products. Transmission electron microscopy showed a diversity of shapes of the particles, which depended strongly on the experimental conditions. All types of particle, observed by transmission electron microscopy, were interpreted.     

Infrared and Structural Properties of Y1?xNdxBa2Cu3O7?δ (0 ≤ x ≤ 1)

Infrared and structural properties of Y_1–x Nd _x Ba₂Cu₃O_7– (0 x 1) were investigated using infrared absorption spectroscopy and X-ray powder diffraction. The unit cell parameters of the samples were defined using X-ray diffraction data. The resistance measurements showed that the samples revealed superconductivity in the temperature range of 80–100 K. It was observed that by the substitution of Nd to Y in YBa₂Cu₃O_{7 –} IR band at 573 cm^–1 that is assigned as Cu–O axial antisymmetric stretching mode shifts to 533 cm^–1 while the band at 620 cm^–1 that is due to Cu–O symmetric stretching mode in YBa₂Cu₃O_7– shifts to 588 cm^–1.     

Preparation of fatigue-free SrBi2Ta2O9 thin films by r.f. magnetron sputtering and their ferroelectric properties

Fatigue-free bismuth-layered SrBi₂Ta₂O₉ (SBT) films were deposited on Pt/Ti/SiO₂/Si substrates by r.f. magnetron sputtering at room temperature. The variation of structure and electrical properties were studied as a function of annealing temperatures from 750–850 °C. The films annealed at 800 °C had a composition ratio of Sr:Br:Ta = 0.7:2.0:2.0. X-ray photoelectron spectroscopy signals of bismuth show an oxygen-deficient state within the SBT films. The films annealed at 800 °C have a thickness of 200 nm and a relatively dense microstructure. The remanent polarization (2P _r), and the coercive field (2E _c), obtained for the SIBT films, were 9.1 C cm^–2 and 85 kV cm^–1 at an applied voltage of 3 V, respectively. The films showed fatigue-free characteristics up to 10¹⁰ cycles under 5 V bipolar square pulses. The leakage current density was about 7 × 10^–7 A cm^–2 at 150 kV cm^–1. The SBT films prepared by r.f. magnetron sputtering were attractive for application to non-volatile memories.     

Formation region of monophase with cubic spinel-type oxides in Mn–Co–Ni ternary system

This study was performed to find the composition area of cubic spinel-type monophase oxides composed of the Mn–Co–Ni ternary system. Starting materials were prepared by mixing Mn, Co, and Ni nitrates then evaporating to dryness. Each starting oxide was fired at 700, 800, 900, 1000, and 1100 °C in air. The regions of cubic spinel monophase (CSM) were confirmed to spread with decreasing firing temperatures. The region of CSM at 1000 °C was seen near the line connecting the points of Mn : Co : Ni = 2 : 4 : 0 and 4.5 : 0 : 1.5. The area at 800 °C spread toward Co and Ni, as compared to the results at 1000 °C. In the region containing more Mn above the area of CSM at 800 °C, the phase had tetragonal spinel or -Mn₂O₃ besides cubic spinel structure. Below this area, the phase contained rock-salt-type crystal besides cubic spinel structure. This tendency at 1000 °C was the same as that at 800 °C.