Influence of nickel content on the electrochemical behavior of Finemet type amorphous and nanocrystalline alloys

The aim of this work has been the systematic study of the influence of partial substitution of Fe by Ni in the Ni_xFe_73.5−xSi_13.5B₉Nb₃Cu₁ alloy within the range 0 ⩽ x ⩽ 10% atom (x = 0, 2, 4, 6, 8, 10) on electrochemical behavior, corrosion rate and the structural changes in amorphous and nanocrystalline alloys. The amorphous nature of the alloys was confirmed by X-ray diffraction and the chemical compositions were determined by ICP. The glass transition and kinetic crystallization of amorphous alloys were studied by DSC. The technique of XPS was used for evaluating the chemical states of elements present in native oxide films. The electrochemical behavior of amorphous and nanocrystalline alloys have been investigated in 0.5 M KOH using cyclic voltammetry. The experimental results show that the formation of different nanocrystalline phases is not excessively transformed by the addition of small amount of nickel and the electrochemical behavior is improved as nickel content increased.     

XAS and XMCD studies of amorphous FeCo-based ribbons

This paper reports x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) studies at Fe L_3,2 and Co L_3,2-edges to investigate the electronic structure of (Fe_100 ? xCo_x)₇₈Si₉Nb₃B₉Cu₁ (0 < x < 95) alloys. The influence of controlled Co addition on electronic structural and magnetic properties of (Fe_100 ? xCo_x)₇₈Si₉Nb₃B₉Cu₁ (x = 0, 20, 40, and 60) alloys has been investigated and it has been observed that Co exists as Co²⁺/Co³⁺, while Fe exists as a mixture of Fe⁰ (metallic) and Fe²⁺. The XMCD studies confirm these results and reveal that Co-ions are responsible for the room temperature ferromagnetism (RTFM) in the system, while at Fe L_3,2-edge it shows a diamagnetic behavior.     

Magnetoimpedance effect in surface pinned nanostructured Fe-based alloys

Amorphous Fe-based ribbons of the composition Fe_73.5Si_13.5B₉Nb₃Cu₁ have been nanocrystallized using conventional heat treatment at 550 °C for 60 min. Nanostructured ribbons have been irradiated using pulsed Nd:YAG laser (1064 nm). To investigate the pinning effect, different energies have been used to illuminate the ribbons. Pinning behavior has been studied using magnetoimpedance data. It has been shown that an increase in laser beam energy makes the pinning centers more effective.     

Influence of Cr additions on corrosion resistance of Fe- and Co-based metallic glasses and nanocrystals in H2SO4

The influence of Cr concentration on the corrosion resistance of Fe_73.5Si_13.5B₉Nb₃Cu₁ and Co_73.5Si_13.5B₉Nb₃Cu₁ metallic glasses was studied by DC electrochemical methods in different concentrations of H₂SO₄ (1, 3 and 5 M) at room temperature. Gravimetric tests were performed to establish the reliability of the data obtained electrochemically. Every test was determined with the same material in different states: amorphous, nanocrystalline and crystalline. In all cases metallic glasses and nanocrystals showed better resistance to corrosion in the tested conditions with increasing chromium concentration. However, in test conditions, the Fe-based materials maintained a high corrosion rate. The corrosion resistance of Co-based materials was slightly greater than that of Fe-based materials.     

In-situ crystallization of amorphous Fe73−xNbxAl4Si3B20 alloys through synchrotron radiation

In the present work Fe_73−xNb_xAl₄Si₃B₂₀ (x = 5, 10) alloys have been processed by melt-spinning with the aim of studying the crystallization sequence through annealing in suitable temperatures. Melt-spun ribbons were characterized by differential scanning calorimetry (DSC), X-ray diffractometry (XRD) through Cu-Kα (λ = 1.54 Å) and synchrotron radiation (λ = 1.77 Å) and transmission electron microscopy (TEM). Soft magnetic properties were measured through the hysteresis loop tracer. In-situ XRD through synchrotron radiation was very accurate in phase identification. Fe_73−xNb_xAl₄Si₃B₂₀ (x = 5, 10) alloys showed the possibility of forming ferromagnetic amorphous alloys composed of commercial Fe-based master alloys with fine nanocrystalline structure and good soft magnetic properties.     

Surface and bulk magnetic properties of amorphous and nanocrystalline Ni-substituted FINEMET samples

The effect of partial substitution of Fe by Ni on the bulk and surface magnetic properties in as-quenched and nanocrystalline Fe_73.5?xNi_xCu₁Nb₃Si_13.5 (x = 0, 8, 10 and 20) alloys has been investigated. A study of the variation of the surface magnetic properties with oxidation in these alloys is also presented. The surface hysteresis loops were obtained by the transverse magneto-optical Kerr effect. The experimental results show that the as-quenched and annealed samples with lower surface coercive field values are those with lower Fe/Si ratio in the sample surfaces. No significant changes between the values of surface H_c for the oxidized and non-oxidized annealed samples with the same Ni content have been observed.     

Bulk glassy (Fe0.474Co0.474Nb0.052)100 − x(B0.8Si0.2)x alloys prepared using commercial raw materials

The alloy compositions have been optimized by modifying the B and Si contents in (Fe_0.474Co_0.474Nb_0.052)_100 ? x(B_0.8Si_0.2)_x alloy system with commercial materials. The thermal stability of the supercooled liquid improves with the increased B and Si contents from x = 22 to 28. The composition of the alloy with x = 26 is close to a eutectic point. By copper mold casting, (Fe_0.474Co_0.474Nb_0.052)_100 ? x(B_0.8Si_0.2)_x bulk glassy alloys with diameters up to 5 mm were synthesized for the composition range of x from 22 to 28. In addition to high glass-forming ability (GFA), the (Fe_0.474Co_0.474Nb_0.052)_100 ? x(B_0.8Si_0.2)_x glassy alloys exhibit good soft magnetic properties as well, i.e., rather high saturation magnetization of 0.84–1.07 T, low coercive field of 1.8–3.2 A/m, high initial permeability of 10100–24100 at 1 kHz under a field of 1 A/m and Curie temperature of 620–730 K.     

Optimization of the microstructure and corrosion resistance of Finemet type alloys in KOH solutions

The effect of Cr replacement for Fe on the kinetics of Cu clustering and on the electrochemical behavior of Fe_73.5−XCu₁Nb₃Si_13.5B₉Cr_X amorphous alloys has been studied for improving the corrosion resistance of Fe–Si–B–Nb–Cu Finemet type alloys. The corrosion testing of these materials was performed in 0.5 M KOH solutions using AC impedance measurements. These experimental results are discussed from the thermodynamical point of view, and the optimized microstructure to achieve a high corrosion resistance has been found.     

Structural and magnetic properties of nanocrystalline particles in an amorphous Fe73.5Nb3CuSi13.5B9 matrix

We report structural and magnetic properties of fine particles embedded in an amorphous magnetic matrix. As-quenched amorphous Fe_73.5Nb₃CuSi_13.5B₉ ribbons (FINEMET) were submitted to the thermal treatments of several times (1 ? t ? 240 min) at 570 °C using a conventional furnace. The analyses of the X-ray diffraction patterns at room temperature reveal that our samples consist of single phase Fe₃Si nanocrystals embedded in a residual amorphous phase. Magnetic measurements show that the saturation moment at T = 450 °C increases as a function of annealing time. This behavior is attributed to an increase of the fraction of nanocrystallites in the residual amorphous phase.     

Preparation of thin ribbon and bulk glassy alloys in CoFeBSiNb(Ga) using planar flow casting and suction casting methods

Co-based ferromagnetic bulk glassy alloy (BGA) system is promising for future applications as new structural and functional materials. In the present paper as-cast Co₄₇Fe_20.9B_21.2Si_4.6Nb_6.3 bilayer, ribbon, rods with diameter up to 5 mm and [Co₄₇Fe_20.9B_21.2Si_4.6Nb_6.3]₉₈Ga₂ as-cast ribbon as well as rod with 4 mm diameter were investigated. Co based master ingots with the composition Co₄₇Fe_20.9B_21.2Si_4.6Nb_6.3 have been prepared in a vacuum furnace. The as-prepared master ingots were then purified by fluxing. Small amount of gallium (2 at.%) was added into one part of the purified master alloy. Ribbons, bilayer and bulk samples in form of rods were prepared by subsequent planar flow casting and suction casting method, respectively. Glassy structure of as-cast samples was examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal stability associated with glass transition temperature (T_g), crystallization temperature (T_x) and supercooled liquid region (?T_x = T_x – T_g) were examined by differential scanning calorimetry (DSC). The Curie temperature of the investigated ribbons and rods was determined by magnetic thermogravimetry analysis (TGA). Using special disc-shaped samples field dependencies of magnetostriction in parallel and perpendicular directions of the applied magnetic field were obtained by direct measurement.     

Corrosion behavior of Fe-based ferromagnetic (Fe,Ni)–B–Si–Nb bulk glassy alloys in aqueous electrolytes

Fe-based ferromagnetic [(Fe_1?xNi_x)_0.75B_0.2Si_0.05]₉₆Nb₄ (x = 0, 0.2 and 0.4) bulk glassy alloys (BGAs) with a diameter of 2 mm were prepared by copper mold casting. The corrosion behavior of glassy alloy rods obtained was investigated in 0.5 M NaCl, 0.5 M NaOH and 0.5 M H₂SO₄ aqueous electrolytes, respectively, using weight loss and electrochemical polarization measurements. It was found that the corrosion rates significantly decrease with an increase in Ni content in all examined solutions. The Ni-containing BGAs are spontaneously passivated with wide passive regions and low passive current densities in NaCl and NaOH solutions, but exhibit the active–passive–transpassive behavior in H₂SO₄ solution. The partial substitution of Ni for Fe results in a considerable improvement on the corrosion resistance of [(Fe_1?xNi_x)_0.75B_0.2Si_0.05]₉₆Nb₄ BGAs, because of the structural and chemical homogeneousness of the amorphous phase and the effect of Ni on promoting the formation of a passive film. Besides their high glass-forming ability (GFA), excellent soft-magnetic properties and good mechanical performance, which have been reported before, these FeNi-based BGAs also feature rather high corrosion resistance.     

Crystallization kinetics and magnetic properties of Fe63.5Co10Si13.5B9Cu1Nb3 nanocrystalline powder cores

Amorphous ribbons of the alloy Fe_63.5Co₁₀Si_13.5B₉Cu₁Nb₃ were prepared by the standard single copper wheel melt spinning technique in air and their crystallization kinetics was analyzed by non-isothermal differential scanning calorimetry (DSC) measurements. The crystallization activation energies (E_x, E_a1 and E_a2) of amorphous ribbons calculated from Kissinger model were 448, 385 and 396 kJ/mol for the first and the second crystallizations, respectively. The Avrami exponent n was calculated from the Johnson–Mehl–Avrami (JMA) equation and was used to identify the crystallization mechanism for the amorphous ribbons. The ribbons were milled into different sized flakes, which were molded subsequently to cores using 3 wt.% epoxy as a binder. The effective permeability of the cores showed high frequency stability and increased with the size of the flakes. For the cores made from small sized flakes (? 75 μm), the quality factor was increased at high frequencies, which was attributed to the reduction in the eddy current loss.     

Influence of composition in the crystallization process of Fe75−xNb10B15+x metallic glasses

The devitrification process of Fe_75−xNb₁₀B_15+x (x = 0, 5, 10) metallic glasses produced by melt-spinning has been analyzed by calorimetric, microstructural and magnetic measurements. The experimental results show large differences in the behavior of these alloys as a function of composition. The alloy x = 0 undergoes a primary crystallization process separated in two stages while only one is observed for alloys with x = 5 and x = 10. This difference, observed by DSC, is correlated with a microstructural change in the phases that precipitate. For alloys x = 5 and 10, Fe₂₃B₆ and bcc-Fe are identified after the first calorimetric peak. In the sample x = 0, bcc-Fe and an unidentified phase precipitate in the first peak but massive crystallization of bcc-Fe is observed after the second stage. Finally the thermal dependence of magnetization has been measured and the Curie temperatures for the metallic glasses are determined. The change of these quantities with heat treatment and composition is discussed.     

Formation and thermal stability of Pd-based bulk metallic glasses

The glass-forming ability and thermal stability of bulk glassy Pd₇₉Cu₆Si₁₀P₅ alloy were studied by substitution of Cu with Ag and with Au + Ag from 0 to 6 at.%. The results indicated that the small addition of Ag strongly affects the thermal stability and glass-forming ability of the Pd₇₉Cu₆Si₁₀P₅ alloy. The alloy doped with 4 at.% Ag (Pd₇₉Cu₂Ag₄Si₁₀P₅) exhibits the largest glass-forming ability among the Pd₇₉Cu_6−xAg_xSi₁₀P₅ (x = 0–6 at.%) alloys. The critical diameter for glass formation of this alloy reaches as large as 7 mm by copper mold casting. On the other hand, the multi-addition of Au + Ag does not increase the glass forming ability though the Ag and Au are similar in atomic size. The largest glass forming ability is obtained at 1 at.% Au + 2 at.% Ag among the Pd₇₉Cu_6−x−yAu_xAg_ySi₁₀P₅ (x = 1–4 at.%, y = 1–3 at.%) alloys. The critical diameter of this alloy is 5 mm by copper mold casting.     

Crystallization kinetics of Fe73.5−xMnxCu1Nb3Si13.5B9 (x = 0, 1, 3, 5, 7) amorphous alloys

In this study, we have investigated the effect of substituting Mn for Fe on the crystallization kinetics of amorphous Fe_73.5−xMn_xCu₁Nb₃Si_13.5B₉ (x = 1, 3, 5, 7) alloys. The samples were annealed at 550 °C and 600 °C for 1 h under an argon atmosphere. The X-ray diffraction analyses showed only a crystalline peak belonging to the α-Fe(Si) phase, with the grain size ranging from 12.2 nm for x = 0 to 16.7 nm for x = 7. The activation energies of the alloys were calculated using Kissinger, Ozawa and Augis-Bennett models based on differential thermal analysis data. The Avrami exponent n was calculated from the Johnson-Mehl-Avrami equation. The activation energy increased up to x = 3, then decreased with increasing Mn content. The values of the Avrami exponent showed that the crystallization is typical diffusion-controlled three-dimensional growth at a constant nucleation rate.     

Mixed transition-ion effect in the glass system: Fe2O3-MnO-TeO2

In earlier studies on phosphate and tellurite glasses containing vanadium and iron oxides, non-linear variation of physical properties as functions of the ratios of the transition ions (V/V + Fe) were observed. The most striking effect was observed with electrical conductivity, where a 3 orders of magnitude reduction in conductivity was observed at a V/V + Fe ratio of ~ 0.4. The effect was termed Mixed Transition-ion Effect or MTE. In phosphate glasses, however, MTE was not observed when one of the transition ions was manganese. It was concluded that Mn does not contribute to conduction in these glasses. In the present study, we demonstrate a mixed transition ion effect in tellurite glasses containing MnO and Fe₂O₃ (xFe₂O₃(0.2 ? x) MnO0.8TeO₂ with x varying from 0 to 0.2). A maximum in the property at an intermediate composition (x = 8.5 mol%), was observed in DC resistivity, activation energy, molar volume etc. Mossbauer and optical absorption (UV–VIS–NIR) measurements were performed on these glasses and the transport mechanism has been identified to be hopping of small polarons between Fe^3 + (Mn^3 +) and Fe^2 + (Mn^2 +) sites.     

Electrical properties of liquid 3d transition metal–Si alloys

The electrical resistivity, R, and the thermoelectric power, S, have been measured for liquid transition metal–Si alloys (TM_cSi_1−c, TM = Ni, Fe, Mn), and liquid Cr_0.1Si_0.9 and Co_0.1Si_0.9 alloys as a function of temperature. The electrical resistivity increases rapidly with the addition of Fe, Mn and Cr to liquid Si and the liquid Mn_cSi_1−c alloys with 1 ⩾ c ⩾ 0.6 have an electrical resistivity of approximately 200 μΩ cm. The composition dependence of the electrical resistivity for liquid Fe_cSi_1−c and Ni_cSi_1−c systems exhibits a maximum at the composition c = 0.5 and c = 0.6, respectively. Liquid TM–Si alloys have a negative value of thermoelectric power over the wide composition range. The variation of R and S by the addition of Fe, Co and Ni solutes to liquid Si is in good agreement with that estimated from the 3d resonant scattering theory. The composition dependence of R and S of liquid Ni–Si can be qualitatively explained by the extended Ziman’s formula.     

Magnetic properties of liquid 3d transition metal–Si alloys

The magnetic susceptibility has been measured for liquid transition metal–Si alloys (TM_1−cSi_c, TM = Ni, Co, Fe, Mn) as a function of temperature. The magnetic susceptibilities of liquid Ni_1−cSi_c with c ⩾ 0.3, liquid Co_1−cSi_c with c ⩾ 0.4 and liquid Fe_1−cSi_c with c ⩾ 0.6 were found to be almost independent of temperature, which suggests that the Ni, Co and Fe ions on the Si side are in the non-magnetic state. Liquid Ni_1−cSi_c with c ⩽ 0.2, liquid Co_1−cSi_c with c ⩽ 0.3 and liquid Fe_1−cSi_c with c ⩽ 0.5 show the Curie–Weiss behavior with a reasonable value of effective Bohr magnetic number. Liquid Mn_1−cSi_c with c ⩽ 0.2 and c ⩾ 0.6 were found to be in their non-magnetic state. However, the Curie–Weiss behavior was observed for liquid Mn_1−cSi_c with c = 0.3, 0.4 and 0.5. The magnetic susceptibility of their liquid alloys in the non-magnetic state has been studied by using Anderson model. The density of 3d states at the Fermi level can be estimated from the data of magnetic susceptibility.     

Estimation of diffusivity governing primary nanocrystallisation and its relation to thermal stability of amorphous phases

Thermal stability and changes of both the average size of Al nanocrystals and their crystallised volume fraction formed in a series of the amorphous Al–(Ni,Co,Fe)–(Gd,Y,Tb) alloys as well as of α-Fe(Si) in the Fe_73.5Si_13.5B₉Cu₁Nb₃ alloy under isothermal conditions have been experimentally studied by a combination of X-ray diffraction (XRD) analysis, differential scanning calorimetry (DSC) and electrical resistance measurements. The experimental data have been fitted with the analytical models describing the diffusion-limited growth of nanocrystals and nanocrystallisation kinetics accounting for impingement of diffusion fields and the values of the effective diffusivity governing this process have been estimated. The obtained values of the diffusivity in Al-based amorphous alloys follow the Arrhenius-type dependencies with correlation between the pre-exponential factors and the activation energies somewhat different from that found for impurity diffusion coefficients in amorphous alloys. It has been established that at the onset crystallisation temperatures varying from 453 to 778 K, the values of the effective diffusivity in the investigated amorphous alloys are in the narrow range of 1.7–4.7 × 10^? 20 m² s^? 1, which indicates a crucial role of the effective diffusivity for the thermal stability of nanocrystals forming amorphous alloys and the possible reason for this is discussed.     

Effect of Nb in the nanocrystallization and magnetic properties of FeNbBCu amorphous alloys

The crystallization of melt-spun Fe_79?xNb_5+xB₁₅Cu₁ (x = 0, 2, 4) ribbons has been studied by differential scanning calorimetry and X-ray diffraction. A primary crystallization of bcc-Fe nanoparticles embedded in an amorphous matrix, followed by the precipitation of metastable borides from the residual matrix at higher temperatures is observed. The characteristic temperatures of crystallization events change with Nb concentration. The results obtained from thermal and structural characterization are related to the magnetic properties of the sample. A dependence of the magnetic behavior with the Fe/Nb content in the alloy is also unveiled. The decrease of Nb content in the alloy leads to an enhancement of both the saturation polarization and the Curie temperature due to variations in the exchange coupling between Fe atoms. However, the maximum values of magnetic entropy change do not vary appreciably among the three amorphous alloys. In nanocrystalline samples the amount of the nanocrystalline transformed fraction seems to be the main reason for the change in the saturation polarization of the sample.