Microstructure investigations and magnetic after-effect in amorphous and nanocrystalline Fe–Zr–Ti–B–Cu alloy

The microstructure evolution and low field magnetic properties i.e. initial magnetic susceptibility, stabilization field and magnetic after-effect as disaccommodation of the amorphous and nanocrystalline Fe₈₀Zr₄Ti₃B₁₂Cu₁ alloy were investigated. The heat treatment of the as-quenched Fe₈₀Zr₄Ti₃B₁₂Cu₁ alloy at 773 K for 1 h leads to its nanocrystallization. It was stated that initial magnetic susceptibility increases and intensity of disaccommodation decreases with increasing of annealing temperature. The magnetic after-effect of the investigated nanocrystalline samples is connected with relaxation processes that occur in the amorphous matrix.     

Effect of annealing on magnetoimpedance of Co68Fe4Zr10Cu2B16 ribbons

Magnetoimpedance (MI) in Co₆₈Fe₄Zr₁₀Cu₂B₁₆ alloy has been investigated in the frequency range 500 kHz–5 MHz and with the application of external steady magnetic field in the longitudinal direction, up to 100 Oe. MI measurements were carried out on as-cast ribbons and also on conventionally annealed and Joule-annealed ribbons. In as cast ribbons, the maximum MI observed is 13% at a frequency of 500 kHz and it decreases to 5% and 4% with conventional annealing at 100 °C and 150 °C, respectively. On the other hand, MI decreases to 8% and 6% with Joule annealing employing currents of 100 mA and 200 mA, respectively. However, Joule annealing with the application of a magnetic field of 5–10 Oe in the transverse direction causes the MI to decrease to 12% and 11% for currents of 100 mA and 200 mA, respectively. In the as-cast ribbons, double peak behavior is observed in all the frequencies whereas, in the annealed ribbons, double peak behavior in general is observed only at high frequencies.     

Grain growth process of two-phase nanocrystalline soft magnetic materials

In order to clarify the origin of the high thermal stability of the microstructure in bcc-Fe/amorphous two-phase nanocrystalline soft magnetic materials, we have investigated the changes in the magnetic and microstructural properties upon isothermal annealing at 898 K for an Fe₈₉Zr₇B₃Cu₁ alloy by means of transmission electron microscopy, Mössbauer spectroscopy and DC magnetometry. The mean grain size was found to remain almost unchanged at the early stage of annealing. However, rapid grain coarsening was evident at an annealing time of 7.2 ks where the intergranular amorphous phase begins to crystallize into Fe₂₃Zr₆. The grain growth process with a kinetic exponent of 1.6 is observed for the growth process beyond this annealing time, reflecting the disappearance of the intergranular amorphous phase. Our results confirm that the thermal stability of the bcc-Fe/amorphous two-phase nanocrystalline soft magnetic alloys is governed by the residual amorphous phase.     

Structural,microstructural and magnetic properties of nanocomposite isotropic Sm(CobalFe0.1MyZr0.04B0.04)7.5 ribbons with M=Ni,Cu and y=0.09 and 0.12

In boron-substituted melt-spun Sm(Co,Fe,Cu,Zr)_7.5-type alloys a nanocomposite microstructure and high coercivities in both as-spun and short-time annealed ribbons can be obtained. In the present study three different compositions, namely Sm(Co_0.73Fe_0.1Cu_0.09Zr_0.04B_0.04)_7.5, Sm(Co_0.70Fe_0.1Cu_0.12Zr_0.04B_0.04)_7.5 and Sm(Co_0.70Fe_0.1Ni_0.12Zr_0.04B_0.04)_7.5 have been examined in order to investigate the influence of composition on the magnetic properties and the microstructure. Melt-spun ribbons have been obtained and annealing has been followed under argon atmosphere for 30–75 min at 600–870 °C. For the as-spun ribbons the TbCu₇-type of structure and fcc-Co as a secondary phase have been identified in the X-ray diffraction patterns. For the annealed ribbons above 700 °C the 1:7 phase transforms into 2:17 and 1:5 phases. The TEM studies have shown a homogeneous nanocrystalline microstructure with average grain size of 30–80 nm. Coercivity values of 15–27 kOe have been obtained from hysteresis loops traced in non-saturating fields. The coercivity decreases with temperature, but it is sufficiently large to maintain values higher than 5 kOe at 380 °C.     

The influence of composition and field annealing on magnetic properties of FeCo-based amorphous and nanocrystalline alloys

We report the influence of composition and very high transverse field annealing on the magnetic properties and structure of four FeCo-based amorphous and nanocrystalline alloys. The compositions (Fe₅₀Co₅₀)₈₉Zr₇B₄ and (Fe₆₅Co₃₅)₈₉Zr₇B₄ were investigated changing the Fe:Co ratio from 50:50 to 65:35. (Fe₅₀Co₅₀)₈₅Zr₂Nb₄B_8.5 was chosen to investigate Nb substitution for Zr in an FeCo-based alloy. This substitution is shown to increase the magnetostrictive constant, _λS${\lambda }_{\mathrm{S}}$, of the nanocrystalline alloy from 36×10⁻⁶ to 54×10⁻⁶. The composition (Fe₆₅Co₃₅)₈₄Cr₅Zr₇B₄ was studied to investigate the influence of Cr on intergranular coupling across the amorphous matrix. Samples of each composition were annealed in the amorphous state at 300 °C and in the nanocrystalline state at 600 °C. Field annealing was performed in 17 T transverse field in an inert atmosphere. Frequency-dependent magnetic properties were measured with an automatic recording hysteresisgraph. Static magnetic properties were measured with a vibrating sample magnetometer. The mass-specific power loss of the alloys decreased with field annealing in both the nanocrystalline and amorphous states for some frequency and induction combinations. Furthermore, the hysteresis loops are sheared after field annealing, indicating a transverse magnetic anisotropy. The nanocrystalline (Fe₅₀Co₅₀)₈₅Zr₂Nb₄B_8.5 composition has a lower relative permeability than the other compositions.     

Long-term stability of soft magnetic properties of amorphous and nanocrystalline alloys based on iron

In the present paper long-term stability of magnetic properties of different amorphous and nanocrystalline alloys was studied. Magnetic properties were measured for annealed samples (300<Ta<900 K) directly after annealing and after long-term aging at room temperature. It was shown that for the Fe_75.3Cu₁Zr_1.7Si₁₃B₉ alloy magnetic permeability of the optimized samples is stable during 8 years aging. For Fe_86−xNb_xB₁₄ alloys the observed long-term instability (3 years aging) is due to annealing out of free volume leading to formations of small iron clusters coherent with the amorphous surroundings.     

Magnetization behavior and magnetocaloric effect in bulk amorphous Fe60Co5Zr8Mo5W2B20 alloy

Microstructure by X-ray diffraction and Mössbauer spectroscopy, and isothermal magnetic entropy changes in the bulk amorphous Fe₆₀Co₅Zr₈Mo₅W₂B₂₀ alloy in the as-quenched state and after annealing at 720 K for 15 min are studied. The as-cast and heat treated alloy is paramagnetic at room temperature. The quadrupole splitting distribution is unimodal after annealing indicating the more homogenous structure in comparison with that for the as-cast alloy. Curie temperature slightly increases after annealing from 265±2 K in the as-quenched state to 272±2 K and the alloy exhibits the second order magnetic phase transition. The maximum of isothermal magnetic entropy changes appears at the Curie points and is equal to 0.30 and 0.42 J/(kg·K) for the alloy in the as-quenched state and after annealing, respectively. In the paramagnetic region the material behaves as a Curie-Weiss paramagnet.     

Annealing effect on soft magnetic properties and magnetoimpedance of Finemet Fe73.5Si13.5B9Nb3Au1 alloy

Effect of annealing on the soft magnetic properties of Fe_73.5Si_13.5B₉Nb₃Au₁ amorphous ribbon has been investigated by means of structure examination, magnetoimpedance ratio (MIR) and incremental permeability ratio (PR) spectra measured in the frequency range of 1–10 MHz at a fixed current of 10 mA X-ray diffraction analysis showed that the as-cast sample was amorphous and it became nanocrystalline under a proper heat treatment. When annealing amorphous alloy at 530 °C for 30, 60, 90 min, soft magnetic properties have been improved drastically. Among the samples investigated, the sample annealed at 530 °C for 90 min showed the softest magnetic behavior. The MIR and PR curves revealed the desirable changes in anisotropy field depending upon annealing.     

High Bs nanocrystalline Fe84−x−yCuxNbySi4B12 alloys (x=0.0-1.4, y=0.0-2.5)

In this study, Cu and Nb content dependences of magnetic properties for annealed Fe_84−x−yCu_xNb_ySi₄B₁₂ alloy ribbons fabricated by melt spinning were investigated. In Fe_83−xCu_xNb₁Si₄B₁₂ alloy systems, the coercivity H_c markedly decreases with increasing x and exhibits a minimum at around x=1.0-1.2, while the saturation magnetic flux density B_s shows a slight variation. In Fe_83−yCu₁Nb_ySi₄B₁₂ alloy systems, H_c markedly decreases at around y=0.5, while B_s shows a monotonic decrease. Fe₈₂Cu₁Nb₁Si₄B₁₂ nanocrystalline alloy ribbons exhibit a high B_s of 1.78 T and a low H_c of 3.2 A/m. The core losses of the present alloys at 1.0 T at 400 Hz, P_10/400, and at 1.0 T at 1 kHz, P_10/1k, are 1.3 and 4.4 W/kg, respectively.     

Crystallization behavior and microstructure of Fe75Co6Zr9B10 alloy

Fe₇₅Co₆Zr₉B₁₀ amorphous alloy prepared by melt-spinning was annealed at various temperatures. The crystallization behavior and microstructure were investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The three exothermal peaks in the DTA curve of Fe₇₅Co₆Zr₉B₁₀ amorphous alloy correspond to the formations of α-Fe and α-Mn type phases, the growth of BCC-Fe volume fraction at the expense of α-Mn and residual amorphous phase and the precipitations of Fe₃Zr, etc. intermetallic compounds, respectively. The second exothermic peak is not influenced by heating rate, but it shifts to a higher temperature region with increasing preannealing temperature of Fe₇₅Co₆Zr₉B₁₀ alloy. The α-Mn type phase is metastable and its lattice parameter determined by TEM is 0.8830 nm. AFM images show the development of surface morphology of alloy after annealing. The particle size increases with increasing annealing temperature.     

Effect of the addition of Ge to the FINEMET alloy

The results obtained by partially substituting Ge for B and Si in the FINEMET alloy for the purpose of improving its magnetic properties at high temperatures are presented in this work. Nanocrystalline ribbons were obtained from controlled crystallization of amorphous material made employing the melt spinning technique. The studied compositions were: Fe_73.5Si_13.5Ge₂Nb₃B₇Cu₁ and Fe_73.5Si_13.5Ge₄Nb₃B₅Cu₁. The structural evolution of these alloys was studied using X-ray diffraction (XRD) and differential scanning calorimetry (DSC) and these results were correlated with their magnetic properties at different annealing temperatures. The coercivity obtained for both alloys was below 1 A/m at anneling temperatures between 773 and 823 K. The amorphous saturation magnetization was satisfactory, almost 137 emu/g, comparable with that obtained for FINEMET alloys. The nanocrystallization and the Curie temperatures are dependent on Ge concentration.     

Structural relaxation,crystallization and improvement of magnetic properties in FeXSiB (X=Cr,Nb)-type amorphous alloys

In the present paper, the influence of Nb and Cr on intensity of structural relaxation, crystallization processes, electric and magnetic properties in the Fe₇₆Nb₂Si₁₃B₉, Fe₇₆Cr₂Si₁₃B₉ and Fe₇₆Nb₁Cr₁Si₁₃B₉ alloys were investigated. It was shown that the improvement of magnetic permeability caused by a suitable annealing is a thermally activated process. Activation energy of this process is found to be of the order of 1 eV. Cr as an alloying addition to the Fe–Si–B alloy does not change the 1 h optimization annealing temperature and causes an increase of its efficiency. Nb as an alloying addition causes an increase of the 1 h optimization annealing temperature, and also the temperature of the first step of crystallization.     

Recoilless fraction, structural, magnetic and thermal properties of Fe73.5Cu1Nb3Si13.5B9 alloy

Differential scanning calorimetry, X-ray diffraction and room temperature Mössbauer spectrum measurements of Fe_73.5Cu₁Nb₃Si_13.5B₉ (Finemet) alloy have been carried out in order to study its structural and magnetic properties as a function of annealing temperature. The DSC profile of as-quenched Finemet showed two exothermic peaks at 530 and 702 °C, corresponding to two crystallization processes. The Finemet alloy remains amorphous at 450 °C with one broad peak in XRD pattern and one broad sextet in Mössbauer spectrum. When the Finemet alloy was annealed at 550 °C, only well indexed body-center-cubic phase was detected. After being annealed at 650 and 750 °C, the XRD patterns showed the coexistence of α-Fe(Si) and Fe-B intermetallic phases with the increase in XRD peak intensities, indicating the growth of crystallites and the decomposition of Fe_73.5Cu₁Nb₃Si_13.5B₉ alloy at elevated temperatures. The Mössbauer spectra of annealed Finemet alloy could be fitted with 4 or 5 sextets and one doublet at higher annealing temperatures, revealing the appearance of different crystalline phases corresponding to the different Fe sites above the crystallization temperature. The appearance of the nanocrystalline phases at different annealing temperatures was further confirmed by the recoilless fraction measurements.     

FINEMET type alloy without Si: Structural and magnetic properties

Magnetic and structural properties of a Finemet type alloy (Fe_73.5Ge_15.5Nb₃B₇Cu₁) without Si and high Ge content were studied. Amorphous material was obtained by the melt spinning technique and was heat treated at different temperatures for 1 h under high vacuum to induce the nanocrystallization of the sample. The softest magnetic properties were obtained between 673 and 873 K. The role of Ge on the ferromagnetic paramagnetic transition of the as-quenched alloys and its influence on the crystallization process were studied using a calorimetric technique. Mössbauer spectroscopy was employed in the nanocrystallized alloy annealed at 823 K to obtain the composition of the nanocrystals and the amorphous phase fraction. Using this data and magnetic measurements of the as-quenched alloy, the magnetic contribution of nanocrystals to the alloy annealed at 823 K was estimated via a linear model.     

Microstructure and magnetic properties of bulk amorphous and nanocrystalline Fe61Co10Zr2.5Hf2.5Nb2W2B20 alloy

The microstructure and magnetic properties, i.e. the initial magnetic susceptibility, its disaccommodation, core losses and approach to ferromagnetic saturation of the bulk amorphous and partially crystallized Fe₆₁Co₁₀Zr_2.5Hf_2.5Nb₂W₂B₂₀ alloy are studied. From X-ray, Mössbauer spectroscopy and electron microscopy studies we have stated that all samples in the as-quenched state are fully amorphous. However, after annealing the samples at 850 K for 30 min the crystalline α-FeCo grains embedded in the amorphous matrix are found. Moreover, from Mössbauer spectra analysis we have stated that the crystalline phase in those samples exhibits the long-range order. The alloy in the as-quenched state shows good thermal stability of the initial magnetic susceptibility. Furthermore, the intensity of the magnetic susceptibility disaccommodation in the rod is lower than in the ribbon. It is due to low quenching rate during the rod preparation which involves the reduction of free volumes. From the analysis of the isochronal disaccommodation curves, assuming the Gaussian distribution of relaxation times, we have found that activation energies of the elementary processes responsible for this phenomenon range from 1.2 to 1.4 eV. After the annealing of the samples the initial susceptibility slightly enhances and disaccommodation drastically decreases. From high-field magnetization studies we have learned that the size of structural defects depends on the quenching rate (the shape of the samples) and changes after annealing.     

Effect of Cu and Ga additions on the anisotropy of R2Fe14B/α-Fe nanocomposite die-upset magnets (R=Pr,Nd)

Fully dense nanocomposite magnets containing hard R₂Fe₁₄B and soft α-Fe phases were produced from both melt-spun and mechanically milled alloys by hot pressing and subsequent die upsetting. Although R-lean R–Fe–B alloys that do not contain the grain-boundary R-rich phase are known not to be susceptible to texture development by means of die upsetting, we found that small additions of Cu make the texturing possible. The resulting microstructure of oriented platelet grains is similar to that of the R-rich die-upset magnets. Properties of the Cu-containing R₂Fe₁₄B/α-Fe die-upset magnets can be further improved by adding Ga. The anisotropic Pr₁₂Fe₈₀Cu₁Ga₁B₆ magnet made from mechanically milled alloy and containing 17.2 wt% α-Fe had a remanence of 13 kG and a maximum energy product of 23.4 MG Oe. The Pr_11.25Fe_80.75Cu₁Ga₁B₆ magnet made from melt-spun alloy and containing 16.2 wt% α-Fe had a maximum energy product of 19.9 MG Oe. The low coercivity of 3–4 kOe typical for the Cu-containing R₂Fe₁₄B/α-Fe die-upset magnets is due to the relatively coarse α-Fe grains. The latter grains are too large for intergranular exchange interaction, but, nevertheless, they are well coupled with the R₂Fe₁₄B grains by a long-range magnetostatic interaction.     

Advances in amorphous and nanocrystalline materials

A new amorphous alloy has been recently introduced which shows a saturation magnetic induction B_s of 1.64 T which is compared with B_s=1.57 T for a currently available Fe-based amorphous alloy and decreased magnetic losses. Such a combination is rare but can be explained in terms of induced magnetic anisotropy being reduced by the alloy's chemistry and its heat treatment. It has been found that the region of magnetization rotation in the new alloy is considerably narrowed, resulting in reduced exciting power in the magnetic devices utilizing the material. Efforts to increase B_s also have been made for nanocrystalline alloys. For example, a nanocrystalline alloy having a composition of Fe_80.5Cu_1.5Si₄B₁₄ shows B_s exceeding 1.8 T. The iron loss at 50 Hz and at 1.6 T induction in a toroidal core of this material is 0.46 W/kg which is 2/3 that of a grain-oriented silicon steel. At 20 kHz/0.2 T excitation, the iron loss is about 60% of that in an Fe-based amorphous alloy which is widely used in power electronics. Another example is a Fe₈₅Si₂B₈P₄Cu₁ nanocrystalline alloy with a B_s of 1.8 T, which is reported to exhibit a magnetic core loss of about 0.2 W/kg at 50 Hz and at 1.5 T induction. This article is a review of these new developments and their impacts on energy efficient magnetic devices.     

Fe65B22Nd9Mo4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The Fe₆₅B₂₂Nd₉Mo₄ nanocomposite permanent magnets in the form of a rectangular cross sectioned rod have been prepared by annealing the amorphous precursors. The thermal behavior, structure and magnetic properties of the magnets have been investigated by differential scanning calorimetry, X-ray diffractometry, electron microscopy and magnetometry techniques. The as-cast Fe₆₅B₂₂Nd₉Mo₄ alloy showed soft magnetic properties, which changed into magnetically hard after annealing. Results provoke that the magnetic properties of the alloy are sensitive to thermal processing conditions. The optimum hard magnetic properties with a remanence (B_r) of 0.56 T, coercivity (_iH_c) of 920.7 kA/m and maximum energy product (BH)_max of 50.15 kJ/m³ were achieved after annealing the alloy at 983 K for 10 min. The good magnetic properties of Fe₆₅B₂₂Nd₉Mo₄ magnets are ascribed to the exchange coupling between the nano-scaled soft α-Fe, Fe₃B and hard Nd₂Fe₁₄B magnetic grains.     

Structural characterization and magnetoimpedance effect in amorphous and nanocrystalline AlGe-substituted FeSiBNbCu ribbons

Two series of rapidly solidified FINEMET (Fe_73.5Si_13.5B₉Nb₃Cu₁) alloys with and without partial substitution of Al (1.5 at%)/Ge (1 at%) were prepared by melt-spinning technique. The nanocrystallization process was carried out by the heat treatment of the as-spun ribbons at 560 °C for 1 h in a vacuum furnace. X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimeter (DSC), Mössbauer spectroscopy, and magnetoimpedance (MI) measurements were conducted on the as-quenched and heat-treated alloys to investigate their structural and magnetic properties. The average crystallite sizes obtained for the heat-treated samples were in the range of 10–12 nm as confirmed by our XRD and TEM data. The ultrasoft magnetic behavior observed for the Al/Ge-substituted nanocrystalline alloys was confirmed both by our magnetic data and magnetoimpedance ratio (MIR%) results. A twofold increase in the magnitude of the MIR% (99%) was observed for the Al/Ge-substituted nanocrystalline alloy against that of the pure FINEMET alloy (∼48%) measured at 5.5 MHz. This is believed to be related to the decrease of the magnetocrystalline anisotropy as well as magnetostriction decline due to the Al substitution for Fe atoms in this nanostructured alloy.     

Microstructure and some magnetic properties of bulk amorphous (Fe0.61Co0.10Zr0.025Hf0.025Ti0.02W0.02B0.20)100−xYx (x=0, 2, 3 or 4) alloys

Microstructure, revealed by X-ray diffraction, transmission electron microscopy and Mössbauer spectroscopy, and magnetic properties such as magnetic susceptibility, its disaccommodation, core losses and approach to magnetic saturation in bulk amorphous (Fe_0.61Co_0.10Zr_0.025Hf_0.025Ti_0.02W_0.02B_0.20)_100−xY_x (x=0, 2, 3 or 4) alloys in the as-cast state and after the annealing in vacuum at 720 K for 15 min. are studied. The investigated alloys are ferromagnetic at room temperature. The average hyperfine field induction decreases with Y concentration. Due to annealing out of free volumes its value increases after the heat treatment of the samples. The magnetic susceptibility and core losses point out that the best thermal stability by the amorphous (Fe_0.61Co_0.10Zr_0.025Hf_0.025Ti_0.02W_0.02B_0.20)₉₇Y₃ alloy is exhibited. Moreover, from Mössbauer spectroscopy investigations it is shown that the mentioned above alloy is the most homogeneous. The atom packing density increases with Y concentration, which is proved by the magnetic susceptibility disaccommodation and approach to magnetic saturation studies.