Annealing behaviour of amorphous Fe80B20 on continuous heating

Resistance measurements during direct heating of Fe₈₀B₂₀ amorphous alloys indicate phase changes occur at 395, 500, 720 and 840° C. Samples heated to these temperatures, and maintained for five minutes in a neutral atmosphere, show that a hardness maximum occurs at the crystallization temperature of 395° C and that annealing at 500° C produces a material with the same hardness. Above 500° C the microhardness is seen to drop below that of the amorphous alloy. Saturation magnetization measurements show a steady increase following each anneal, up to a temperature of 720° C, and the rate of increase is seen to drop in the range of 720 to 840° C. X-ray diffraction studies show that only a small fraction of the matrix is crystallized following the anneal at 395° C and the transformed phases are -Fe and Fe₃B. Following annealing at 500° C, an increased proportion of -Fe and Fe₃B are observed with complete crystallinity while samples heattreated at 720° C are seen to consist of a three-phase mixture of -Fe, Fe₂₃B₆ and Fe₂B. Annealing at 840° C is seen to produce an equilibrium phase mixture of -Fe and Fe₂B phases. Only in the sample annealed at 395° C is a fraction of the amorphous phase seen to persist, indicating that a 5 min anneal is not sufficient, at this temperature, to induce complete crystallization. These structural features are corroborated by field ion microscope analyses, made at liquid nitrogen temperature in a medium of pure neon, and scanning electron microscopy, and are also consistent with our earlier study involving the isothermal annealing, for various times, of Fe₈₀B₂₀ alloy at 780° C.     

Formation of ternary carbide Fe3Mo3C by mechanical activation and subsequent heat treatment

Ternary carbide, Fe₃Mo₃C was prepared from the powder mixture of Fe/Mo/C = 1/1/1 which was ground for 3 h in a planetary ball mill and subsequently heated at a temperature as low as 700°C, its amount increased with heating temperature. In contrast, when the 1 h-ground and unground samples were heated at 700–1000°C, Mo₂C formed. From the results obtained about the effect of mixing ratio, grinding time and heating temperature of Fe/Mo/C samples on the formation of Fe₃Mo₃C, it was found that the formation of Fe₃Mo₃C strongly depends on the mixing homogeneity and the activated state of the particles of Fe, Mo and C components induced by mechanical grinding. Fe₃Mo₃C obtained belongs to a hard magnet, having saturation magnetization of 0.4 emu g^–1, remanence of 0.13 emu g^–1 and coercivity of 200 Oe.     

Hydrogen absorption and desorption in Nd2Fe17 and Sm2Fe17

The uptake of hydrogen by Nd₂ Fe₁₇ and Sm₂Fe₁₇ has been monitored in a thermopiezic analyser as a function of temperature at an initial pressure of 1 bar (10⁵ Pa). The first stage of hydrogen absorption around 250° C yields R₂Fe₁₇H _y (R = Nd, Sm) withy 2.2; this compound retains the Th₂Zn₁₇ structure of the starting alloy but the cell volume is increased by about 3%. The Curie temperature increases from 57 to 175° C for R = Nd and from 115 to 253° C for R = Sm. A second stage of hydrogen absorption at about 600° C corresponds to disproportionation of the alloy into -Fe + RH_2–.     

High-temperature crystallization behaviour of amorphous Fe80B20

Samples of 0.003 in. round Fe₈₀B₂₀ amorphous wires were annealed in vacuo for 1 sec to 8 h periods at 780° C and the crystallinity induced in these wires from this heat treatment was studied through X-ray diffraction and field-ion microscopy. X-ray diffraction studies indicate that complete crystallinity is produced following 1 sec anneal at 780° C. However, the initial product is a primitive-tetragonal Fe₃B phase unlike the body-centred tetragonal Fe₃B observed in low-temperature isothermal transformation studies with this alloy. The Fe₃B phase is seen to persist in the diffraction patterns for annealing durations of up to 15 min. Upon annealing for periods of up to 1 h, an intermediate three-phase structure consisting of -Fe, Fe₃B, and Fe₂B is seen to result with a gradual decrease in the Fe₃B phase corresponding to longer annealing durations. Anneals of more than 1 h at 780° C are seen to result in the disappearance of the Fe₃B phase producing a two-phase microstructure consisting of -Fe(b c c) and Fe₂B (b c t). Field-ion-microscopy with a pure neon imaging gas at 78 K likewise indicates that existence of a three-stage phase structural change during the isothermal anneals, and the atomic arrangement of the various species are quite readily discernible because of the different symmetries contained in the three distinct phases.     

Formation of oxide phases in the system Fe2O3-NiO

Mixed metal oxides in the system Fe₂O₃-NiO were prepared by coprecipitation of Fe(OH)₃/Ni(OH)₂ and the thermal treatment of hydroxide coprecipitates up to 800 or 1100°C. X-ray diffraction showed the presence of -Fe₂O₃, NiO and NiFe₂O₄ in samples prepared at 800°C. The oxide phases -Fe₂O₃, NiO, NiFe₂O₄ and a phase with structure similar to NiFe₂O₄ were found in samples prepared at 1100°C. Fourier transform-infrared spectra of oxide phases formed in the system Fe₂O₃-NiO are discussed. Two very strong infrared bands at 553 and 475 cm^–1, a weak intensity infrared band at 383 cm^–1 and two shoulders at 626 and 441 cm^–1 were observed for -Fe₂O₃ prepared at 1100°C. NiFe₂O₄, prepared at the same temperature, showed two broad and very strong infrared bands at 602 and 411 cm^–1, while NiO showed a broad infrared band at 466 cm^–1. Fourier transform infrared spectroscopic results were in agreement with X-ray diffraction.     

Corrosion Behavior of α-Fe and 20kh13 Steel in Contact with Oxygen-Containing Lead Melts

We study the structure and chemical composition of the reaction products formed in the process of contact of -Fe and 20Kh13 steel with oxygen-containing stagnant lead melts (600–700°C, 3000 h, C _O[Pb] (1–4) · 10^–5 wt.%). It is shown that a heterogeneous structure is formed in the interaction zone. This structure consists of an external intermediate layer (with low hardness, the same composition as the matrix, and lead accumulated on the grain boundaries) and a thin oxide film (Fe₃O₄ for -Fe and FeCr₂O₄ and Cr₂O₃ for 20Kh13 steel), which separates the intermediate layer from the internal porous suboxide layer of the matrix and blocks the process of penetration of lead into the matrix.     

In situ X-ray diffraction of the early stages of the crystallization of Fe80B20

A new technique has been used for the early stages of crystallization of amorphous materials, like metallic alloys. In situ X-ray diffraction has been performed during the early stages of crystallization of Fe₈₀B₂₀. The samples are resistively heated to 600°C in a customized vacuum chamber. A programmable charge-coupled device detector records simultaneously the evolution of the three phases: -Fe, Fe₃B and Fe₂B in the minute scale. This is the first in situ X-ray diffraction study of this system in these temperature and time scales. Interesting behaviours have been seen: appearance and disappearance of phases, -Fe supersaturation solution in boron (found for the first time in this compound), and migration of B out of the -Fe matrix. The two-dimensional diffraction pictures show topography irregularities indicating crystallite inhomogeneties.     

Mössbauer study on the magnetic state of iron particles in Fe-N and Fe-Zr-N soft magnetic thin films

The magnetic state of -Fe particles and the behaviour of nitrogen and zirconium during annealing in Fe₉₆N₄ and Fe_85.6Zr_7.6N_6.8 magnetic thin films have been studied by conversion electron Mössbauer spectroscopy for ⁵⁷Fe. The crystalline phases present in the Fe-N annealed films were -Fe and -Fe₄N, and those in the Fe-Zr-N annealed films were -Fe and ZrN. In the Fe-N films annealed below 300°C, about 60% nitrogen is incorporated interstitially into -Fe and the rest is used for the formation of -Fe₄N. In the Fe-N film annealed at 500°C, almost all nitrogen participates in the formation of -Fe₄N, leading to the grain growth of -Fe particles and an increase in coercive force. The values (291–325 kOe) of internal magnetic field of iron sites in -Fe in the Fe-Zr-N films are much smaller than that (333 kOe) of the iron site in pure -Fe. Even if the Fe-Zr-N films were annealed at 500–700°C, some zirconium and nitrogen is still incorporated substitutionally and interstitially into -Fe, respectively. In particular, the substitutional zirconium depresses the grain growth of -Fe particles, perhaps due to a chemical interaction between zirconium and iron.     

Structural analysis of amorphous (Fe1-x Mn x )78B22 alloys by X-ray diffraction and electrical resistance

The structure of amorphous (Fe_1–x Mn _x ) alloys prepared by a single roller technique has been investigated in terms of X-ray diffraction and electrical resistance. The lattice parameter of the crystalline precipitates, which were-Fe and b c t (FeMn)₃B, was determined under different heat treatments. On heating up to 440° C where a mixture of amorphous and crystalline phases exists and up to 550° C corresponding to the completion of crystallization, the lattice parameter of the-Fe phase rises to that of pure-Fe with increasing manganese concentration. In samples annealed at 660° C for 5 h, the opposite behaviour is observed. These results can be explained on the basis of the position of the boron atom occupying the-Fe lattice, the pressure effect exerted by the environment, and the enhancement of the chemical short-range ordering between manganese and boron atoms with manganese concentration. In the b c t phase, which shows a reduction in lattice parameter with manganese concentration independent of heat treatment, the effect of redistribution of the atoms in the unit cell should be also taken into account.     

Structural properties of precipitates formed by hydrolysis of Fe3+ ions in Fe2(SO4)3 solutions

The structural properties of the solid phase, formed by the hydrolysis of Fe³⁺ ions in Fe₂(SO₄)₃ solutions at 90 or 120 °C, were investigated using X-ray diffraction,⁵⁷Fe Mössbauer spectroscopy, Fourier transform-infrared spectroscopy (FT—IR) and transmission electron microscopy. The concentration regions of Fe₂(SO₄)₃ were determined for the precipitation of goethite, -FeOOH, or hydronium jarosite, H₃OFe₃(OH)₆(SO₄)₂ as a single phase. Superparamagnetic behaviour of -FeOOH particles was observed. Hydrolysis of Fe³⁺ ions in 0.1 M Fe₂(SO₄)₃ solutions at 120 °C produced H₃OFe₃(OH)₆(SO₄)₂ and basic sulphate, Fe₄(OH)₁₀SO₄. The interpretation of⁵⁷Fe Mössbauer and FT—IR spectra is given.     

Solid state reactions in the Fe2O3-CaCO3-In2O3 system

The kinetics of solid-state reactions of powdered reactants were investigated by X-ray and by differential thermogravimetry in a magnetic field. Measurements revealed mutual diffusion of the Fe³⁺ and In³⁺ ions in the Fe₂O₃-In₂O₃ system heat treated for 3 h at 700 to 1400° C. Diffusion of indium into the Fe₂O₃ lattice caused a shift of the Curie temperature of the antiferromagnetic iron oxide towards lower temperatures. Only Caln₂O₄ was found between CaCO₃ and In₂O₃ up to 1400° C. Also, in the Fe₂O₃-CaCO₃-In₂O₃in system, the reaction started with the mutual diffusion of iron and indium and the forming of CaFe₂O₄. End-products were the magnetic -Ca₄Fe₁₄O₂₅ and CaFe₄O₇, and the non-magnetic CaFe₅O₇, depending on the In³⁺ concentration. Indium stabilized the magnetic calcium-iron oxide structures, shifting their Curie temperatures towards lower values.     

Effect of high pressure on the crystallization of an amorphous Fe83 B17 alloy

Amorphous Fe-17 at %B alloy prepared by a splat-quenching technique was annealed at temperatures ranging from 250 to 500° C for different periods. A time-temperature transformation diagram has been constructed from X-ray diffraction examination of annealed samples. On annealing the alloy at a pressure of 50 kbar, an appreciable retardation of crystallization was observed. The crystalline phase precipitated first from the amorphous matrix at 1 bar. This was -Fe containing a small amount of boron, but at 50 kbar this was a mixture of -Fe(B) and intermetallic phase Fe₃B. Under the increased pressure of 100 kbar the mode of the crystallization was further changed and Fe₃B became the first precipitating phase. Preferential formation of Fe₃B under pressure can be explained assuming a modified dense-random packing model for the amorphous structure.On leave from Institute of Physics, Academia Sinica, Beijing, China.     

Synthesis of carbon nanotube films by thermal CVD in the presence of supported catalyst particles. Part I: The silicon substrate/nanotube film interface

The interface between the silicon substrate and a carbon nanotube film grown by thermal CVD with acetylene (C₂H₂) and hydrogen at 750 or 900 °C has been characterized by high resolution and analytical transmission electron microscopy, including electron spectroscopic imaging. Silicon (0 0 2) substrates coated with a thin (2.8 nm) iron film were heat treated in the CVD furnace at the deposition temperature in a mixture of flowing argon and hydrogen whereby nanosized particles of (Fe,Si)₃O₄ formed. These particles were reduced to catalytic iron silicides with the –(Fe, Si), ₂–Fe₂Si and ₁–Fe₂Si structures during CVD at 900 °C, and multi-wall carbon nanotubes grew from supported particles via a base-growth mechanism. A limited number of intermediate iron carbides, hexagonal and orthorhombic Fe₇C₃, were also present on the substrate surface after CVD at 900 °C. The reduction of the preformed (Fe, Si)₃O₄ particles during thermal CVD at 750 °C was accompanied by disintegration leading to the formation of a number of smaller (<5 and up to 10 nm) iron and silicon containing particles. It is believed that the formation of these small particles is a prerequisite for the growth of aligned multi-wall carbon nanotube films.     

Crystallization of amorphous Fe78B13Si9

Crystallization of amorphous Fe₇₈B₁₃Si₉ has been investigated using a combination of differential scanning calorimetry (DSC) and conventional and high-resolution transmission electron microscopy. The crystallization mechanisms and crystalline products are sensitive to the annealing temperature. At 450C, crystallization takes place by the growth of b c c -Fe (Si) dendrites, while at 510 and 515C there are three simultaneous reactions to form dendritic b c c -Fe (Si), elliptical crystals of b c t Fe₃B and lamellar eutectic spherulites of b c c -Fe (Si) and b c t Fe₃B. Quantitative TEM shows that the b c c -Fe (Si) dendrites and b c c -Fe (Si)-b c t Fe₃B spherulites both form with constant nucleation and growth rates, in agreement with previous. DSC measurements of an Avrami exponent of 4.     

Crystallization and structure of high boron content iron-boron ultrafine amorphous alloy particles

Amorphous to crystalline transformation of chemically prepared Fe₆₄B₃₆ ultrafine amorphous alloy particles has been investigated by Mössbauer spectroscopy, Brunauer-Emmett-Teller surface area measurements and transmission electron microscopy. Structural relaxation was observed below 350°C, which resulted in narrowing the full width at half maximum for the hyperfine field distribution from 13.0 to 10.6 T, while the average hyperfine field kept unchanged, to be about 20.3 T. Crystallization started on the surface at about 300°C and proceeded into the bulk at about 400°C. Partial crystallization between 400 and 450°C resulted in increasing the average hyperfine field for the remaining Fe-B amorphous matrix to 21.6 T. -Fe and Fe₂B were the only iron containing phases related to bulk crystallization, with the latter as a predominant component, accompanied by the segregation of about 19% boron atoms. Above 500°C, sintering of the particles became very remarkable and a solid state reaction between diffusing iron and boron atoms to form Fe₂B took place making the spectral area ratio for Fe₂B to -Fe components increase accordingly. A locally distorted non-stoichiometric Fe₂B quausicrystalline structure for the high boron content sample was proposed.     

Iron dispersed carbon composites formed from iron-polyvinylalcohol complexes

Iron-polyvinylalcohol (Fe-PVA) complexes have been pyrolysed at the temperatures up to 1000 K, and the iron-carbon composites formed have been characterized. The yield of carbon was much higher for the complexes than for PVA alone. The degree of carbon graphitization and the chemical form of iron species were dependent on the pyrolysis temperature. About 30 wt% fine particles of Fe₃O₄ or -Fe were dispersed in the matrix of amorphous carbon at 800 or 900 K, respectively. At 1000 K, -Fe was partly transformed to Fe₃C, and the agglomeration of -Fe was not so significant. At this temperature the carbon was graphitized, which resulted in a lowering of the surface area of the composite. It is suggested that the graphitization proceeds through the mechanism involving the formation and subsequent decomposition of Fe₃C. Thus, the use of Fe-PVA complexes achieves a high yield of carbon and a high dispersion of a large amount of iron species throughout the carbon matrix.     

Ultrafine magnetic metal dispersed carbons prepared from anisotropic pitch and metal acetylacetonate complexes

Transition metal (Fe, Co or Ni) dispersed carbon composites were prepared using the mixtures of metal acetylacetonate complex as a source of metal particles and an anisotropic coal-tar pitch as a carbon matrix precursor by heat treatment at the temperatures up to 1000°C. Mixing of the metal complexes and the pitch by dissolving in quinoline permitted the notable fine dispersion of the complex in the pitch. Then the resulting mixtures were easily converted to the metal dispersed carbons by pyrolysis under an inert atmosphere. The appeared particles were Fe₃O₄/-Fe/Fe₃C, -Co or Ni when using the corresponding metal complex. Besides, their particle diameters were much less than 30 nm and distributed evenly throughout the carbon matrix. The magnetic properties of the metal dispersed carbons were evaluated with a vibrating sample magnetometer, and it was found that saturation magnetization and coercive force ranged from 1.03 × 10^–5 to 5.65 × 10^–5 Wb · m/kg and from 0.21 × 10⁴ to 3.06 × 10⁴ A/m, respectively.     

Phase-precipitation studies of Fe-B-Si metallic glasses using Mössbauer spectroscopy

Phase-precipitation studies have been performed on samples of the metallic glasses Fe₇₉B₁₆Si₅ and Fe₇₈B₁₃Si₉, heated in the range 300–475 °C for various times (1–16 h) using ⁵⁷Fe Mössbauer transmission spectroscopy and X-ray diffraction methods. These measurements have helped in identifying the temperature ranges and annealing durations in which the amorphous structure of these metallic glasses is retained. The results revealed that the thermal stability increases as boron is replaced by silicon in the Fe-B-Si metallic glasses and that these alloys remain amorphous below 450 °C. The various phases precipitated above this temperature were identified as -Fe, -(Fe, Si), Fe₃B, and Fe₂B. The direction of magnetization in the two metallic glasses appears to change upon annealing.     

Phase Composition of the Products of Fe Oxidation in Fe + C + NaCl + H2O + O2 Exothermic Mixtures

Using thermodynamic analysis of the Fe–C–NaCl–H₂O–O₂ system and experimental studies (x-ray diffraction and Mössbauer spectroscopy) of exothermic mixtures containing Fe metal, activated carbon, water, and NaCl, we identified the state of Fe and determined the phase composition of the reaction products at different stages of oxidation with atmospheric oxygen. The calculation and experimental results are in reasonable agreement. Under the conditions of restricted access for air, the main oxidation product is magnetite, Fe₃O₄. Free access for air leads to the formation of hydrous ferric oxide, Fe₂O₃ · nH₂O. The most stable phase under the conditions of interest is goethite, Fe₂O₃ · H₂O (-FeOOH). Storage of incompletely oxidized samples away from air for 7–14 days leads to partial reduction of iron(III) oxide phases to Fe₃O₄ and -Fe.     

The thermal diffusivity of ice and water between −40 and + 60° C

The thermal diffusivity _s of triply-distilled deionised water, and ^L of single-crystal ice along the c-axis, have been measured by Angström's method. The temperature range covered was –40 to +60° C. The results for water compare well with published data for the thermal conductivity, but for ice there are unexplained discrepancies. The linear relationships _s=(8.43–0.101 T) 10^–3 cm²/sec and _L=(1.35+0.002 T) 10^–3 cm²/sec where T° C is the temperature, fit the data obtained.