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.     

Study of surface-bulk mass transport and phase transformation in nano-TiO2 using hyperfine interaction technique

Phase transition from anatase to rutile for the 70 nm TiO₂ crystallite has been investigated by the time differential perturbed angular correlation (TDPAC) technique. The study involved the annealing of the TiO₂ nanocrystals, adsorbed with the nuclear probe (¹⁸¹Hf/¹⁸¹Ta) at trace level, at different temperatures for different durations. The TDPAC measurement was also supported by XRD measurement where the width of the peaks increases with the increase in annealing temperature indicating a crystal growth. The samples annealed up to 823 K for 4 h showed no phase transition, except for the growth of the crystallites. However, it showed phase transition at the same temperature (823 K), when annealed for longer duration, indicating the slower kinetics of the phase transition process. Further the sample, when annealed at 1123 K for 4 h, showed phase transition. It has also been observed that the ¹⁸¹Hf tracer, adsorbed on 70 nm anatase TiO₂, diffuses from surface to bulk during the phase transition process and the extent of diffusion in anatase differs from that in rutile phase. However, surface to bulk mass-transfer is found to play a significant role in the phase transition process.     

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.     

Nanocrystals magnetic contribution to FINEMET-type soft magnetic materials with Ge addition

Over the last years several works have been published in which magnetic and structural properties of soft magnetic nanocrystalline alloys were reported. Among these, there are a series of articles where the nanocrystals composition of FINEMET-type alloys with Ge addition was obtained by Mössbauer spectroscopy (MS) and X-ray diffraction (XRD). By considering a linear relationship between the magnetic moments of the nanocrystals and the composition of various elements in these crystallites, the magnetic moment of the nanocrystals was calculated. This paper reviews results obtained by different authors since 1980 and they are compared with ours. In turn, we revised some elements not previously considered for the calculus of the nanocrystals composition that allowed us to obtain the magnetic moment of the crystallites in the alloy. In particular, we analyzed FINEMET-type alloys with replacement of B for Ge: Fe_73.5Si_13.5Ge₂B₇Nb₃Cu₁ and Fe_73.5Si_13.5Ge₄B₅Nb₃Cu₁. The nanocrystalline structure was obtained by isothermal annealing of melt-spun ribbons at 823 K for 1 h. From MS and XRD we obtained the atomic composition of the nanocrystals in the magnetic material. The magnetic contribution of the nanocrystals to the alloy was calculated using a linear model and the results were compared with experimental measurements of the samples.     

Influence of Ge on magnetic and structural properties of Joule-heated Co-based ribbons: Giant magnetoimpedance response

Studies of magnetic and structural properties of Fe_3.5Co_66.5Si_12−xGe_xB₁₈ (x=0, 3, and 6) soft magnetic ribbons obtained by melt-spinning were performed. The samples were submitted to Joule-heating treatments with different maximum current values (0.01, 0.05, 0.1, 0.2, and 0.8 A, respectively) with steps of 0.01 A and times by step of 1, 2, and 10 s). X-ray diffraction, temperature dependence of magnetization (for the as-quenched samples), coercivity and giant magnetoimpedance (GMI), measured at different frequencies (100, 500, and 900 kHz, respectively) were performed. All the samples crystallized at annealing currents higher than 0.4 A, which was consistent with the magnetic hardening of the material. Coercivities less than 1 A/m were obtained for the three samples between 0.1 and 0.2 A. Maximum value of GMI response was observed for the sample without Ge in the as-quenched state.     

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 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.     

Critical phenomena in FINEMET alloy

The Fe_73.5Cu₁Nb₃Si_13.5B₉ FINEMET alloy has been prepared by the rapid solidification technique. The critical behaviour of this alloy in the amorphous as well as in its nanocrystalline states has been studied near their respective Curie temperatures. From the values of the critical exponents one can conclude that the alloy behaves like a 3D Heisenberg ferromagnet in the amorphous and nanocrystalline states. But there exists a slight increase in the value of β for the alloy annealed at 823 K (the nanocrystalline state) as observed in most of the amorphous alloys.     

Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

Structural and magnetic properties of SmCo5.6Ti0.4 alloy

Three series of SmCo_5.6Ti_0.4 samples were prepared by quenching, melt spinning, and ball milling, respectively. Annealing at different temperatures was carried out for the three series. The influence of the processing routes on the structural and magnetic properties was systematically investigated for this alloy. The as-quenched bulk sample consisted of three phases with a rather coarse grain microstructure. Low intrinsic coercivity (_iH_c) of 0.12 T was obtained in this sample. While the as-spun ribbons and as-milled/annealed powders showed the CaCu₅-type phase (1:5) plus Th₂Zn₁₇-type phase (2:17), and the 1:5 phase plus TbCu₇-type phase (1:7), respectively, with nanograin microstructure. The _iH_c of as-spun ribbons and as-milled/annealed (700 °C for 2 h) powders was found to be 0.59 and 2.23 T, respectively. Coercivity mechanism of these as-spun ribbons is mainly of nucleation type. In the as-milled/annealed powders, the network of the nanograin boundaries is believed to provide strong pinning sites for the domain wall movement.     

Structures, magnetic properties, and magnetocaloric effect in MnCo1−xGe (0.02?x?0.2) compounds

The crystalline structures, magnetic properties and magnetocaloric effect (MCE) of MnCo_1−xGe alloys (0.02?x?0.2) have been reported. The crystalline structures of MnCo_1−xGe (x?0.06) alloys are mainly of TiNiSi-type phase, and Ni₂In-type structure dominates for x>0.06. With decreasing Co concentrations the saturated magnetization of these compounds decreases. Large low-field magnetic entropy change −ΔS_M of about 2.3 J/kg K in MnCo_0.94Ge alloy has been obtained for a magnetic field change of 1 T. Moreover, it is found that TiNiSi-type phase exhibits larger −ΔS_M than Ni₂In-type one. For MnCo_0.94Ge alloy, considerable low-field refrigerant capacity (RC) (∼460 mJ/cm³), low coercivity and easy synthesis make these alloys potential candidates for near-room temperature magnetic refrigerants.     

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.     

Interactions of germanium atoms with silica surfaces

GeH₄ is thermally cracked over a hot filament depositing 0.7-15 ML Ge onto 2-7 nm SiO₂/Si(1 0 0) at substrate temperatures of 300-970 K. Ge bonding changes are analyzed during annealing with X-ray photoelectron spectroscopy. Ge, GeH_x, GeO, and GeO₂ desorption is monitored through temperature programmed desorption in the temperature range 300-1000 K. Low temperature desorption features are attributed to GeO and GeH₄. No GeO₂ desorption is observed, but GeO₂ decomposition to Ge through high temperature pathways is seen above 750 K. Germanium oxidization results from Ge etching of the oxide substrate. With these results, explanations for the failure of conventional chemical vapor deposition to produce Ge nanocrystals on SiO₂ surfaces are proposed.     

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.     

Exchange bias behavior in Ni50.0Mn35.5 In14.5 ribbons annealed at different temperatures

Heusler alloy Ni_50.0Mn_35.5In_14.5 ribbons were prepared by melt-spinning technique. Several short time annealings were carried out in order to enhance the exchange bias effect in this alloy ribbon. The magnetic transition temperature increases with the annealing, compared to the as-spun sample, however no significant differences in respective Curie temperatures were observed for austenite and martensite phases in such annealed samples. Exchange bias effect is observed at low temperatures for all samples and practically vanishes at 60 K for the as-spun sample, whereas for the annealed ribbons it vanishes at 100 K.     

The magnetic and magnetocaloric effect of (Mn0.5Co0.5)65Ge35 alloy in low magnetic field

The crystal structure and magnetocaloric effect (MCE) of water-quenched and annealed (Mn_0.5Co_0.5)₆₅Ge₃₅ alloys were studied in this paper. A CoMnGe-single phase was formed in the water-quenched alloy, and mixture phases of CoMnGe and Mn+2O in the annealed alloy. The annealed alloy has a smaller crystal parameter than the water-quenched alloy. The Curie temperature is 275 and 298 K for the water-quenched and annealed alloys, respectively, which means that the magnetic-transition temperature in this material can be controlled by anneal. In addition, the same magnetic entropy change was found in these two alloys, even though their Curie temperatures have a significant difference.     

Nonmagnetic heavy-fermion superconductor, CePt3Si

We have studied the effect of heat treatment and the Ge substitution in place of Si in the recently discovered heavy-fermion superconductor CePt₃Si. The annealed CePt₃Si exhibited nonmagnetic heavy-fermion behavior instead of the antiferromagnetism (AF) found in quenched samples. The AF state was destroyed by only about 1 at.% of Ge-substitution and may not be a stable phase. Specific-heat measurements on the annealed CePt₃Si and the Ge-substituted samples revealed a large hump around 2.2 K, originally claimed as Néel temperature. Its true nature is not clarified yet but conjectured at present as a sort of quadrupolar transition rather than AF long-range order. The superconducting transition around 0.75 K was equally sharp with ΔC_p/γT_c=0.7 for clean quenched and annealed samples. The interplay between the 2.2 K-anomaly and the superconductivity is discussed.     

Ferromagnetism in MnxGe1−x films prepared by magnetron sputtering

Mn_xGe_1−x thin films were prepared by magnetron sputtering with a substrate temperature of 673 K and subsequently annealed at 873 K. The X-ray diffraction (XRD) measurements showed that all samples had a single Ge cubic structure. No films showed clear magnetic domain structure under a magnetic force microscope (MFM). Atom force microscope (AFM) measurements showed that the films had an uniform particle size distribution, and a columnar growth pattern. X-ray photoelectron spectroscopy (XPS) measurements indicated that the valences of both Mn and Ge atoms increase with the Mn concentration. The resistance decreased with increasing temperature, suggesting that the films were typical semiconductors. Magnetic measurements carried out using a Physical Property Measurement System (PPMS) showed that all samples exhibited ferromagnetism at room temperature. There was a small concentration of Mn₁₁Ge₈ in the films, but the ferromagnetism was mainly induced by Mn substitution for Ge site.     

Structural transformations and magnetic properties of Fe60Pt15B25 and Fe60Pt25B15 nanocomposite alloys

Structural and magnetic properties of two rapidly solidified and post-annealed Fe₆₀Pt₁₅B₂₅ and Fe₆₀Pt₂₅B₁₅ alloys are compared. The as-quenched Fe₆₀Pt₁₅B₂₅ ribbon was fully amorphous whereas in the Fe₆₀Pt₂₅B₁₅ alloy the amorphous phase coexists with an fcc FePt disordered solid solution. Differential scanning calorimetry curves of both alloys reveal a single exothermal peak with onset temperatures of 873 and 847 K for Fe₆₀Pt₁₅B₂₅ and Fe₆₀Pt₂₅B₁₅, respectively. Magnetically hard, tetragonal ordered L1₀ FePt and magnetically soft Fe₂B nanocrystalline phases were formed due to the annealing of the alloys, as indicated by X-ray diffraction and Mössbauer spectroscopy measurements. Two-phase behavior was detected in the temperature dependence of magnetization of the annealed samples. A magnetic hardening was observed for all annealed ribbons. Magnetic properties of the annealed alloys, studied by hysteresis loop measurements, were related to the differences in the relative fractions of the hard and soft magnetic phases calculated from Mössbauer spectra. The alloy with 25 at% Pt exhibits better hard magnetic properties (H_c=437 kA/m, M_r/M_s=0.74) than the alloy with smaller Pt content (H_c=270 kA/m, M_r/M_s=0.73) mainly due to the larger abundance of the ordered tetragonal FePt phase.     

The effect of different temperature annealing on phase relation of LaFe11.5Si1.5 and the magnetocaloric effects of La0.8Ce0.2Fe11.5−xCoxSi1.5 alloys

The phase relation of LaFe_11.5Si_1.5 alloys annealed at different high-temperature from 1223 K (5 h) to 1673 K (0.5 h) has been studied. The powder X-ray diffraction (XRD) patterns show that large amount of 1:13 phase begins to form in the matrix alloy consisting of α-Fe and LaFeSi phases when the annealing temperature is 1423 K. In the temperature range from 1423  to 1523 K, α-Fe and LaFeSi phases rapidly decrease to form 1:13 phase, and LaFeSi phase is rarely observed in the XRD pattern of LaFe_11.5Si_1.5 alloy annealed at 1523 K. With annealing temperature increasing from 1573  to 1673 K, the LaFeSi phase is detected again in the LaFe_11.5Si_1.5 alloy, and there is La₅Si₃ phase when the annealing temperature reaches 1673 K. There almost is no change in the XRD patterns of LaFe_11.5Si_1.5 alloys annealed at 1523 K for 3-5 h. According to this result, the La_0.8Ce_0.2Fe_11.5−xCo_xSi_1.5 (0≤×≤0.7) alloys are annealed at 1523 K (3 h). The analysis of XRD patterns shows that La_0.8Ce_0.2Fe_11.5xCo_xSi_1.5 alloys consist of the NaZn₁₃-type main phase and α-Fe impurity phase. With the increase of Co content from x=0 to 0.7, the Curie temperature T_C increases from 180 to 266 K. Because the increase of Co content can weaken the itinerant electron metamagnetic transition, the order of the magnetic transition at T_C changes from first to second-order between x=0.3 and 0.5. Although the magnetic entropy change decreases from 34.9 to 6.8 J/kg K with increasing Co concentration at a low magnetic field of 0-2 T, the thermal and magnetic hysteresis loss reduces remarkably, which is very important for the magnetic refrigerant near room temperature.