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.     

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 of stable and metastable eutectics in FeSiB metallic glasses

Two iron-based metallic glasses, Fe₇₈Si₉B₁₃ and Fe₇₈Si₁₀B₁₂, have been examined after isothermal annealing at different temperatures and it has been found that both stable and metastable eutectics can crystallize simultaneously during the annealing process. At low temperatures, the majority of the eutectic cells in the structure consist of -iron and the stable Fe₂B phase with a lesser amount of the -iron and metastable Fe₃B eutectic, whereas at higher temperatures the metastable eutectic predominates. It is suggested that these observations may be explained in terms of the presence of overlapping coupled zones of both the stable and metastable eutectics in the phase diagram.     

Crystallization of the metallic glass Fe78B13Si9

The microstructures and kinetics with heating for an amorphous Fe₇₈B₁₃Si₉ alloy were studied by X-ray diffraction, transmission electron microscopy, differential thermal analysis and differential scanning calorimetry. The first crystallization takes place by the simultaneous formation of -(Fe,Si) and Fe₃B having the shapes of dendrite and spherulite, respectively. Metastable Fe₃B then transformed into a stable phase of Fe₂B at a higher temperature. The activation energy for crystallization and the Avrami exponent were determined. It was found that crystallization behaviour in Fe₇₈B₁₃Si₉ is controlled by nucleation rather than growth.     

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.     

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.     

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.     

Mössbauer spectroscopic studies of the crystallization of amorphous Fe80B20−x Si x (x=0, 2, and 8) alloys

The crystallization process of amorphous Fe₈₀B_20–x Si _x (x=0, 2, and 8) ferromagnetic alloys has been studied by using ⁵⁷Fe Mössbauer spectroscopy and X-ray diffraction studies. Results for samples heat treated at different temperatures for different times show that the crystallization of Fe₈₀B_20–x Si _x samples having x=0 and 2 leads to -Fe and t-Fe₃B, while for x=8, it leads to -Fe, t-Fe₂B, and perhaps Fe-Si. It is further observed that the addition of silicon to the Fe-B system improves the thermal stability of the system.     

Crystallization of Fe-Si-B metallic glasses studied by X-ray synchrotron radiation

We have studied the crystallization kinetics of Fe_90-x Si _x B₁₀ amorphous alloys withx ranging from 7 to 21, by synchrotron X-ray radiation. Using energy- dispersive X-ray diffraction, the kinetics of the different crystalline phases evolving during isothermal annealing were followed. These crystalline phases were identified as precipitation of-Fe(Si) and/or Fe₃Si in the amorphous matrix. At a later time or at a higher temperature, Fe₂B starts to crystallize (x < 21 ). Only at low iron concentration (x = 21) was the second phase different, namely Fe₅SiB₂ The hypo- and hyper-eutectic Fe-Si-B glasses were found to crystallize differently. The crystallization processes are discussed in some detail.     

Distribution of α-AlFeSi and β-AlFeSi particles in surface layer of AA6063 alloy billets after heat treatment

We developed the EPMA mapping method of small -AlFeSi(Al_8.3Fe₂Si) and -AlFeSi(Al_8.9Fe₂Si₂) particles in the billets of Al-Mg-Si alloys such as AA6063 alloys. To discriminate between -AlFeSi and -AlFeSi particles we used the relative X-ray intensities of Fe/Si ratio, the I _Fe/I _Si ratio, instead of the Fe/Si mass ratio. To obtain the I _Fe/I _Si ratio, we used a Monte Carlo method. In this study, using this method the mapping of -AlFeSi and -AlFeSi particles in the surface layer of AA6063 billets after the heat treatment (for 2 h at 580°C) was done. Namely, the distribution of -AlFeSi and -AlFeSi particles of zones from the billet surface to a depth of 800 m was measured. Results showed the zone from the surface to a depth of 200 m was occupied mainly by -AlFeSi particles and the zone from a depth of 200 m toward the center was occupied mainly by -AlFeSi particles. From these results, it was found that if we remove zones from the surface to a depth of 200 m, we can remove the majority of the -AlFeSi particles, and thus improve the quality of anodizing performance of Al-Mg-Si alloys extrusions.     

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 mechanism of Fe80Si8B12 metallic glass

In order to gain an understanding of the glass-forming mechanism during the rapid quenching of a metallic alloy, the nucleation and growth process of the crystalline phase which competes with the metallic glass must be investigated. The microstructures of melt-spun Fe₈₀Si₈B₁₂ alloy ribbons with different thicknesses were examined using optical and electron microscopy. The phase competing with the metallic glass is-(Fe, Si) ferrite, nucleated by the homogeneous nucleation. The growth process of-(Fe, Si) dendrites was explained well by Liptonet al.'s theory of dendritic growth in an undercooled alloy melt. It was concluded that the easy glass-forming ability during rapid quenching of the Fe₈₀Si₈B₁₂ alloy is due to (i) the slow growth rate of-(Fe, Si) dendrite, and (ii) the wide gap between the temperatures of the maximum nucleation rate and the maximum growth velocity.     

The morphology of α-Fe crystals which grow in the amorphous Fe80(C1−xBx)20 alloys

Crystallization behaviour of amorphous Fe₈₀(C_1–x B _x )₂₀ alloys, obtained by splat-cooling technique, for x values ranging from zero to unity has been investigated mainly by transmission electron microscopy. The crystalline phase which first appeared in the amorphous matrix was -Fe for all alloys studied. However, the morphology of -Fe phase changed from a spherical shape for low x values to a watch-glass shape for intermediate x values and to dendritic for large x values. The nucleation of -Fe crystals was homogeneous for low x samples while preferred nucleation on edges and surfaces was noted for samples with higher x values. The final volume fraction of -Fe phase before the appearance of the second crystalline phase increased with the increase in x.     

Preparation of ultrafine Fe-Si-C powders in a radio-frequency thermal plasma and their catalytic properties

Ultrafine Fe-Si-C powders were prepared from mixed gases of SiH₄-CH₄-Fe(CO)₅ using a newly developed thermal-plasma apparatus with a dual-radio-frequency-coupled-plasma-torch system. The phases of the powders prepared were classified into two groups; one composed of -FeSi₂ which was prepared by rapid quenching, while the other was composed of -Fe, Fe₃Si, Fe₅Si₃, FeSi, -SiC and amorphous Si, which were prepared by slow quenching. The diameters of these powders were in the range 5–50 nm. The catalytic activities of these powders for Fischer-Tropsch synthesis were examined. The ultrafine -FeSi₂ powder was very active for the selective formation of olefin. On the other hand, powders of -Fe, Fe₃Si and Fe₅Si₃ were low in their selectivity but gave high CO conversion. Relations between the plasma conditions for the preparation of ultrafine Fe-Si-C powders and their catalytic properties are discussed.     

EPMA mapping of small particles of α-AlFeSi and β-AlFeSi in AA6063 alloy billets

It is well known that the spatial distribution and the spatial density of the particles o-AlFeSi and -AlFeSi in the billets of Al-Mg-Si alloys, such as AA6063 alloys affect the quality of anodizing performance of their extrusions. For this reason it is very important to control the spatial distribution and the spatial density of both AlFeSi particles at extrusion plants. The X-ray diffraction method (XRD) has been used for discrimination between -AlFeSi and -ALFeSi particles. However it is not an appropriate method for determining the spatial distributions of particles in the alloys. As an alternative method an electron probe microanalyzer (EPMA) has been used for determining the spatial distributions of each element in the microstructures. However, unfortunately it is difficult to discriminate between the particles composed of the same elements like -AlFeSi and -AlFeSi particles. Thus, we tried to develop a convenient method to discriminate between -AlFeSi and -AlFeSi particles in the microstructure of AA6063 alloys and developed the EPMA mapping of -AlFeSi and -AlFeSi particles. First, in order to discriminate between the two particles, we tried to use the relative X-ray intensity ratio, the I _Fe/I _Si ratio instead of the Fe/Si mass ratio. Then, we calculated the value of the I _Fe/I _Si ratio from -AlFeSi and -AlFeSi by using Monte Carlo calculations and obtained the critical value of the I _Fe/I _Si ratio, to distinguish between -AlFeSi and -AlFeSi. After that, using the discrimination value, we developed the EPMA mapping program (EPMA method) to observe the distributions of -AlFeSi and -AlFeSi, and to calculate the areas (%) of -AlFeSi and -AlFeSi. Finally, we checked the correlation between the EPMA and the XRD methods. Consequently, the two methods were in good agreement. Today, this EPMA method instead of the XRD method is successfully used in the quality control of 6063 aluminum alloy billets after heat treatment at our aluminum extrusion works.     

Nanocrystalline microstructures in Fe93 − x Zr7B x alloys

The crystallization behaviour of amorphous Fe_{93 – x} Zr₇B _x (x = 3, 6, 12 at.%) alloys, the microstructures of the primary crystallization products of stable and metastable phases and the subsequent transformations, have been studied using a combination of differential scanning calorimetry, differential thermal analysis, X-ray diffraction and transmission electron microscopy, including microdiffraction. It has been found that, for x = 3 and 6 at.%, the sole product of primary crystallization is the bcc -Fe phase and the average grain sizes of the crystalline phase were 14 nm and 12 nm for the two alloys, respectively. However, when x = 12 at.%, primary crystallization results in more than one crystalline phase, and a metastable phase with the cubic Fe₁₂Si₂ZrB structure is the major crystallization product after the primary crystallization reaction, accompanied by the -Fe phase. The average grain size of this metastable phase was 35 nm for the alloy heated to 883 K at 20 K/min. Isothermal heat treatments at 873 K and 973 K confirm that after being heated for 240 h, this metastable phase transforms into equilibrium phases: bcc -Fe, hcp ZrB₂ and probably hcp Fe₂Zr. The apparent activation energies for the primary crystallization reaction during continuous heating for these three alloys are 4.4 ± 0.2 eV, 3.5 ± 0.2 eV and 6.9 ± 0.3 eV, respectively.     

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.     

Crystallization process and magnetic properties of Fe100−x,B x (10 ≦ × ≦ 35) amorphous alloys and supersaturated state of boron inα-Fe

Amorphous specimens of Fe_100–x B _x were prepared in the range 10 × 35 at % B by a single-roller method. The crystallization process and the boron concentration dependence of the Curie temperature were examined by differential scanning calorimetry, X-ray diffraction, Mössbauer spectroscopy and magnetic measurements. Two-step crystallization was observed in specimens with× < 17: amorphous amorphous + boron-supersaturated b c c phase (-Fe(B)) t-Fe₃B +-Fe. A single-Fe(B) phase was not observed. The transition temperature from t-Fe₃B to stable (-Fe + t-Fe₂B) sensitively depends on the boron content in the alloys. The crystallization temperature (T _x) of the amorphous alloys was almost unchanged for 17 × 31, but increased remarkably at high boron concentrations of× 33, where the decomposition products consisted of t-Fe₂B and o-FeB. The Curie temperature (T _c) of the amorphous phase was as low as 480 K at× = 10, increased with increasing boron content up to 820 K and then decreased in the high boron concentration alloys of× > 28. A single-Fe(B) phase was not detected in the as-quenched specimens of× = 8 and 10. The phase coexisted with the o-Fe₃B and amorphous phases. The lattice parameter of the phase was 0.2861₀ nm which was smaller than that of pure iron by 2/1000, indicating the substitutional occupation of boron atoms in the b c c lattice.     

Magnetic properties and surface crystallization induced by selective oxidation in Fe-B-Si amorphous alloy

The relationship between the annealing atmosphere and the magnetic properties of Fe_78.5B₁₃Si_8.5 amorphous alloy has been studied, showing that annealing in nitrogen, argon, hydrogen and air significantly improved the iron loss of the amorphous ribbon, giving much better results than annealing in an H₂ + H₂O atmosphere. A boron-depletion zone with the alloy composition O to 3 mol % B and 9 to 11 mol% Si was detected by Auger electron spectroscopy under the oxide film formed during annealing in H₂ + H₂O. The iron crystalline phase is formed only on the ribbon surface after annealing in H₂ + H₂O. A mechanism is proposed explaining the deleterious effect of annealing in the H₂ + H₂O, whereby the H₂O in this atmosphere selectively oxides boron in the amorphous alloy to form a B₂O₃ film and the boron-depletion zone, and the alloy in this zone is then crystallized into -Fe. This surface crystalline layer induces out-of-plane magnetic anisotropy in the amorphous alloy ribbon (which was observed by transmission Mössbauer spectroscopy) and thus deterioration of the iron loss.     

The magnetic properties of the glassy ferromagnets Fe81.5B14.5Si4 and Fe40Ni40B20

The galssy ferromagnets Fe_81.5B_14.5Si₄ and Fe₄₀Ni₄₀B₂₀ have been studied by Mössbauer spectroucopy from 77.5 up to 650 and 680K, respectively, In the glassy state, the average magnetic hyperfine field decreases with increasing temperature due to a distribution of exchange inter-actions. At low temperatureH(T)/H(0) has a temperature dependence (1 -BT ^/32 -CT ^/52) whereB andC are constants, indicative of spin-wave excitations in glassy ferromagnets. The value of B_/32) = 0.40 = 0.05 is almost four times larger than those of crystalline iron and nickel. On the other hand, fluctuations of the exchange interaction constant are found to decrease with increasing temperature. The Curie temperaturesT _c - 608 K for the glassy Fe_81.5B_14.5Si₄ andT _c = 583K for the glassy Fe₄₀Ni₄₀B₂₀ are found to be well defined. AtT close toT _c H(T) behaves as a power law with critical exponent = 0.3. The crystallizationT _cr glassy Fe_81.5B_14.5Si₄ was found to be 645K. The crystalline material obtained contains three different phases, namely -Fe, Fe₂B and Fe-8% Si.