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.     

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.     

Magnetic properties and low frequency magnetoimpedance of novel amorphous CoFeTaBCr ribbons

In this report, we study the effect of Cr addition on the dc an ac magnetic properties of novel melt spun amorphous Co_43−x/2Fe_20−x/2Cr_xB_31.5Ta_5.5 (x = 0, 1, 2, 4) alloy series. The saturation magnetization decreases with increasing Cr content as well as the ac relative initial permeability, which showed a high relaxation frequency of 3 MHz. In addition, the magnetoimpedance effect was detected in this alloy series, with a maximum variation ratio of 3% at x = 0.     

Nd5Fe64B23Mo4Y4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The glass forming ability and magnetic properties of Nd₅Fe_68 ? xB₂₃Mo₄Y_x (x = 0, 2, 4, 6) alloys prepared by copper mold casting technique have been studied. Amorphous rods with a diameter of 2 mm were obtained in the Nd₅Fe₆₄B₂₃Mo₄Y₄ alloy. After annealing for 10 min at 1013 K, the Nd₅Fe₆₄B₂₃Mo₄Y₄ alloy showed optimal hard magnetic properties with the coercivity of 764.2 kA/m, remanence of 0.6 T and maximum energy product of 57.3 kJ/m³, respectively. The enhanced magnetic properties can be ascribed to the strong exchange coupling among the magnetically soft α-Fe (25–30 nm), Fe₃B (30–35 nm) and hard Nd₂Fe₁₄B (40–50 nm) grains present in the magnet microstructure. Large size bulk nanocomposite magnets with sound magnetic properties make the Nd–Fe–B–Mo–Y alloy system a promising candidate for industrial applications.     

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.     

Formation and mechanical behavior of (Fe0.5Ni0.5)80−xMoxB20 (x = 0–8) amorphous alloys

Glass forming ability, thermal stability and mechanical behavior of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ (x = 0, 2, 4, 6, 8) amorphous alloys were studied by XRD, TEM, SEM, DSC, tensile test, microhardness test and tearing test. The effects of Mo addition on glass formation, strength and ductility of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ amorphous alloys were discussed. The substitution of Mo for Fe and Ni simultaneously causes improvement in glass forming ability and thermal stability, and changes the crystallization process. The tensile fracture strength of amorphous alloy depends on both hardness and ductility; the alloy with high hardness and good ductility simultaneously also has a high tensile fracture strength. The (Fe_0.5Ni_0.5)₇₈Mo₂B₂₀ amorphous alloy exhibits good glass forming ability and the highest tensile fracture strength among (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ alloys. Micro-plastic deformation occurred in ductile and brittle amorphous alloys that both show viscous flow characteristics. The mechanical behavior of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ amorphous alloys is related to the average outer shell electron concentration of metal atoms.     

Square-wave voltammetry and impedance spectroscopy in iron-doped melts of the system Li2O/Al2O3/SiO2

Glass melts with the basic compositions xLi₂O · 15Al₂O₃ · (85 − x)SiO₂ (x = 8.5, 11, 13.5, 16 and 18.5) doped with 0.25 mol% Fe₂O₃ were studied by square-wave voltammetry and impedance spectroscopy at temperatures in the range from 1100 to 1600 °C. The square-wave voltammograms show a pronounced peak attributed to the reduction of Fe³⁺ to Fe²⁺. The attributed peak potentials which are equal to the standard potentials of the redox pair decrease linearly with the temperature. Impedance spectra measured could be simulated using an equivalent circuit attributed to a simple electron transfer reaction controlled by diffusion.     

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.     

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.     

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.     

Structural and dynamical properties of Fe78Si9B13 alloy during rapid quenching by first principles molecular dynamic simulation

Structural evolution of the Fe₇₈Si₉B₁₃ alloy during rapid quenching was investigated by ab initio molecular dynamics simulation. The second peak splitting has been perceived even at 1473 K in the partial pair correlation functions though not in the total pair correlation function. The (0, 3, 6, 0) polyhedra are abundant in the liquid state while the distorted (0, 3, 6, 0) polyhedra are the featured local structure around B atoms in the amorphous state. The diffusion coefficients of the three elements are evaluated to understand the dynamics of quenching. From 1173 to 873 K the three coefficients are coherent. We think this temperature range corresponds to the supercooled liquid region, and 873 K serves as the glass transition temperature.     

Magnetic and magnetoimpedance properties of Mn-doped FINEMET

In this study, the effect of substituting Mn for Fe on the magnetic and magnetoimpedance (MI) properties of amorphous and nanocrystalline Fe_73.5?xMn_xCu₁Nb₃Si_13.5B₉ (x = 1, 3, 5, 7) alloys has been investigated. A higher Mn content causes a decrease in the saturation magnetization and Curie temperature. For as-received Fe_73.5?xMn_xCu₁Nb₃Si_13.5B₉ (x = 0, 1, 3, 5, 7) ribbons, the measured values of the MI are 11%, 12%, 16%, 12% and 15% for x = 0, 1, 3, 5, 7, respectively. The magnitude of the MI ratio increases in annealed samples, indicating that they are magnetically softened by nanocrystallisation. The change in MI is found to be ～70% for the x = 3 sample annealed at 550 °C. It is also found that replacing a small amount of Fe by Mn improves the magnetic softness of Fe_73.5?xMn_xCu₁Nb₃Si_13.5B₉ alloys.     

Glassy state and structure of Sn–Sb–Se chalcogenide alloy

The effect of Sn addition on the glass transition and structure of c-Sb₂₀Se₈₀ chalcogenide alloy have been studied by X-ray diffraction and differential scanning calorimetric studies. The increase in the glass forming region and the glass transition temperature with the addition of Sn is discussed by considering the formation of [SnSe₄] tetrahedra, another type of network former, which inhibits the crystallization. The differential scanning calorimetric studies on Sn_xSb₂₀Se_80−x (8 ⩽ x ⩽ 18) glassy samples reveal a single glass transition temperature for all values of x while a single crystallization peak was obtained only for 10 ⩽ x < 12. The X-ray diffraction studies reveal that the glass crystallizes to Sb₂Se₃ and SnSe₂ phases upon annealing. The glass formation and composition dependence of glass transition temperature in the Sn–Sb–Se chalcogenide alloy could be understood by considering the topological phase transitions and a chemically ordered network model.     

X-ray diffraction measurements for liquid Ge–Si alloys using synchrotron radiation

Energy dispersive X-ray diffraction measurements have been carried out for liquid Ge_1−xSi_x alloys (x = 0.0, 0.3, 0.5, 1.0) using synchrotron radiation at SPring-8. We measured the X-ray diffraction spectra of liquid Ge and Si up to a high temperature range, (liquid Ge from 1270 to1870 K and liquid Si from 1680 to 2020 K), liquid Ge_0.7Si_0.3 at 1620 K, and liquid Ge_0.5Si_0.5 at 1540, 1590, 1670 and 1720 K. The total structure factors of the liquid Ge–Si alloys have a characteristic shoulder on the high-wave-vector side of the first peak. We deduced a pair distribution function from the Fourier transform of the observed structure factor, which was weakly dependent on the temperature. The nearest-neighbor coordination number of liquid Ge–Si alloys is close to that of pure liquid Ge and Si. The first peak of the pair distribution function moved to a shorter distance with increasing Si concentration. These results may indicate that the atomic radii of the Si and Ge atoms in the pure liquid are preserved in the liquid alloys.     

A molecular dynamics study of the role of the cation in modifying the structure of alkali borate glasses

The structures of the full series of alkali borate glasses (M₂O)_x(B₂O₃)_1?x (M = Li, Na, K, Rb and Cs) at two different concentrations, x = 0.14 and x = 0.30, have been investigated by means of molecular dynamics simulations. Additional compositions have also been investigated for the lithium and caesium borate glasses (x = 0.10, 0.20, 0.25, and 0.40). The main experimental trends are well reproduced by the simulations, even if the agreement is not quantitative. Our results indicate that lithium atoms can enter into the matrix of pure vitreous B₂O₃ without inducing large modifications in the B–O network, even at large concentrations. However when the other alkali ions are added to the initial structure, the network opens to accommodate the larger size of the cation. These modifications induce the appearance of a low-Q shoulder or pre-peak, whose intensity increases with increasing alkali concentration as well as with increasing alkali size.     

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.     

Effect of Mo–Fe substitution on glass forming ability and thermal stability of Fe–C–B–Mo–Cr–W bulk amorphous alloys

Amorphous Fe_67?xC₁₀B₉Mo_7+xCr₄W₃ (x = 1–7 at.%) plates with 0.64 mm thickness were prepared by copper mold casting. The thermal properties and microstructural development during heat treatments were investigated by a combination of differential scanning calorimetry, differential thermal analysis, and X-ray diffraction. The glass forming ability (GFA) and activation energy for crystallization have a distinct dependence on Mo content. Fe₆₂C₁₀B₉Mo₁₂Cr₄W₃ was the best glass former in this study, demonstrating a supercooled liquid region, ΔT_x = 51 K, and an activation energy for crystallization, Q = 453 kJ/mol. The GFA of alloys in this system was governed by elastic strain optimization resulting directly from the variation in Mo content. Heat treatments were performed to demonstrate resistance to crystallization under typical processing conditions. Alloys in this system exhibited a three phased evolution during crystallization. A second set of heat treatments was performed to identify each phase. An analysis of phase evolution revealed a distinct dependence of phase evolution with stepwise substitution of Mo for Fe in this system.     

Effect of Mo element on the properties of Fe–Mo–P–C–B bulk metallic glasses

Bulk Fe_80?xMo_xP₁₀C_7.5B_2.5 (x = 5–10 at.%) metallic glasses are synthesized by copper mold casting, which have a critical diameter up to 3 mm, fracture strength over 3000 MPa, plastic strain up to 2.5% and saturation magnetization reaching 1.1 T. Results show that the glass forming ability and strength increase with increasing Mo content, while the plasticity and saturation magnetization do otherwise. These Mo content dependent properties are illuminated with the atomic interactions in the alloys that could be strengthened by suitable addition of Mo element. The effects of Mo on the properties of the alloys imply that proper Mo element should be chosen in designing Fe-based glassy alloys with desired properties.     

Crystallization of NANOPERM-type amorphous alloys

In the present work, we have investigated progress of crystallization in the Fe_91?xMo₈Cu₁B_x (x = 12, 15, 17, 20) alloy as a function of annealing temperature. This material belongs to the family of the Fe–M–B–(Cu) alloys (transition metal M = Zr, Nb, Hf, Mo, …) called also NANOPERM. The alloy was found to contain small amounts (<5%) of bcc Fe(Mo) and Mo₂FeB₂ nanocrystallites (<2 nm) located on the surface of the ribbon-shaped samples already in the as-quenched state. Depending upon composition, the nanocrystallites are formed on the air and/or wheel side of the ribbon. They are characterized by atomic force microscopy, conversion electron Mössbauer spectroscopy, and by X-ray diffraction of synchrotron radiation. Fast detection (every 10 s) of the latter during continuous heating of as-quenched specimens enabled an in situ observation of the evolution of the crystallization. For x = 12, the crystallization starts earlier at the wheel side of the ribbon but its progress is more rapid at the opposite, i.e. air side.     

Calorimetric study and Kissinger analysis of melt-spun DyMn6−xGe6−xFexAlx (1 ⩽ x ⩽ 2.5) alloys

Thermal properties of rapidly quenched alloys from the DyMn_6?xGe_6?xFe_xAl_x (1 ? x ? 2.5) series produced by melt-spinning have been investigated by differential scanning calorimetry (DSC). The DSC curves show two exothermic effects connected with crystallization processes. Crystallization temperatures and enthalpies ΔH have been estimated. The systematic changes in these parameters allow concluding that the crystallization exothermic events are independent. Effective activation energies E have been determined using the Kissinger analysis and relatively high values up to 480 ± 20 kJ/mol for DyMn₄Ge₄Fe₂Al₂ have been found indicating high thermal stability of the amorphous state in this alloy series.