Effect of Si addition on the glass-forming ability of a NiTiZrAlCu alloy

The effect of Si addition on the glass-forming ability (GFA) of a NiTiZrAlCu alloy was investigated by using differential scanning calorimetry (DSC), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The maximum diameter of glassy rods increased from 0.5 mm for the Ni₄₂Ti₂₀Zr₂₅Al₈Cu₅ alloy (the base alloy) to 2.5 mm for the Ni₄₂Ti₂₀Zr_21.5Al₈Cu₅Si_3.5 alloy and to 3 mm for the Ni₄₂Ti₁₉Zr_22.5Al₈Cu₅Si_3.5 alloy, when prepared by using the copper mould casting. The GFA of the alloys can be assessed by the reduced glass transition temperature T_rg(=T_g/T_l) and a newly proposed parameter, δ(=T_x/T_l − T_g). An addition of a proper amount of Si and a minor substitution of Ti with Zr can enhance the GFA of the base alloy by suppressing the formation of primary Ni(TiZr) and (TiZr)(CuAl)₂ phases and inducing the composition close to eutectic.     

Preparation, thermal stability, and magnetic properties of Fe---Co---Zr---Mo---W---B bulk metallic glass

A bulk metallic glass (BMG) cylinder of Fe₆₀Co₈Zr₁₀Mo₅W₂B₁₅ with a diameter of 1.5 mm was prepared by copper mould casting of industrial raw materials. The amorphous state and the crystallization behavior were investigated by X-ray diffraction (XRD). The thermal stability parameters, such as glass transition temperature (T_g), crystallization temperature (T_x), supercooled liquid region (ΔT_x) between T_g and T_x, and reduced glass transition temperature T_rg (T_g/T_m) were measured by differential scanning calorimetry (DSC) to be 891, 950, 59 K, and 0.62, respectively. The crystallization process took place through a single stage, and involved crystallization of the phases -Fe, ZrFe₂, Fe₃B, MoB₂, Mo₂FeB₂, and an unknown phase, as determined by X-ray analysis of the sample annealed for 1.5 ks at 1023 K, 50 K above the DSC peak temperature of crystallization. Mössbauer spectroscopy was studied for this alloy. The spectra exhibit a broadened and asymmetric doublet-like structure that indicated paramagnetic behavior and a fully amorphous structure. -Fe was found in the amorphous matrix for a cylinder with a diameter of 2.5 mm. The success of synthesis of the Fe-based bulk metallic glass from industrial materials is important for the future progress in research and practical application of new bulk metallic glasses.     

Boron content dependence of crystallization, glass forming ability and magnetic properties in amorphous Fe-Zr-B-Nb alloys

The glass forming ability (GFA) was investigated in Fe_91−xZr₅B_xNb₄ alloys with B contents of 0–36 at.%. The GFA changes with B content, and fully amorphous alloys were prepared by melt spinning for B contents between 5 and 30 at.%. The amorphous alloys crystallize with a primary crystallization mode in the low B content range of 5≤x≤20 at.%, but in the eutectic mode in the high B content range of 20<x<30 at.%. A single new metastable Fe-Zr-B-Nb cubic phase with a lattice constant of 1.0704 nm, a saturation magnetization of 137 emu/g and a coercivity of 7.3 Oe at room temperature is formed when crystallizing in a polymorphous mode at x=30 at.%. The glass transition temperature (T_g), crystallization temperature (T_x), Curie temperature (T_c) and saturation magnetizations (M_s) of the amorphous alloys increase with increasing B content, but the coercivity (H_c) decreases. As the B content exceeds 20 at.%, not only increase the T_g, T_x and GFA sharply, due to the change of crystallization mode, but also the concentration dependence of the T_c and M_s changes. It is concluded that the amorphous alloys have better GFA, thermal stability and soft magnetic properties for the high B contents of 25–30 at.% than for the low B contents of 5–20 at.%.     

A new Cu–Hf–Al ternary bulk metallic glass with high glass forming ability and ductility

We have discovered a new Cu-based bulk metallic glass (BMG). Although of a simple Cu₄₉Hf₄₂Al₉ ternary composition, the as-cast alloy is a monolithic, uniform BMG with a critical diameter as large as 10 mm. The width of the supercooled liquid region ΔT_x and the reduced glass transition temperature T_rg for this glass are 85 K and 0.62, respectively. In addition to its high glass-forming ability and high density of 11 g/cc, this BMG exhibits high ductility with a compressive plastic strain of 11–13%, making it a good candidate for applications as well as for studies of deformation behavior of Cu-based BMGs.     

Thermal stability and magnetic properties of Gd–Fe–Al bulk amorphous alloys

Gd₆₅Fe₂₀Al₁₅, Gd₆₅Fe₁₅Al₂₀ and Gd₇₀Fe₁₅Al₁₅ bulk amorphous alloys were produced by copper mold casting method with the maximum diameters of 2, 1 and 1 mm, respectively. The crystallization temperature (T_x) and melting temperature (T_m) of the Gd₆₅Fe₂₀Al₁₅ bulk amorphous alloy are 808 and 943 K, respectively. Accordingly, the temperature interval of T_m and T_x, ΔT_m (=T_m − T_x), is as small as 135 K and the reduced crystallization temperature (T_x/T_m) is as high as 0.86. The small ΔT_m and high T_x/T_m values are presumed to be the origin for the achievement of the high amorphous-forming ability of the Gd–Fe–Al bulk amorphous alloy. The Gd₆₅Fe₂₀Al₁₅, Gd₆₅Fe₁₅Al₂₀ and Gd₇₀Fe₁₅Al₁₅ bulk amorphous cylinders with a diameter of 1 mm exhibit superparamagnetism at room temperature, while the amorphous ribbon shows the paramagnetism at room temperature. Finally, the mechanical properties of Gd₆₅Fe₂₀Al₁₅ bulk amorphous alloys are investigated.     

Thermal stability and mechanical properties of Gd-Co-A1 bulk glass alloys

The glass forming ability of Gd-Co-A1 ternary alloy systems with a composition ranging from 50% to 70% （molar fraction） for Gd and from 5% to 40% （molar fraction） for AI were investigated by copper mold casting and Gd60Co25Al15 bulk glass alloy cylinders with the maximum diameter of 5 mm were obtained. The reduced glass transformation temperature （TG/Tm） and the distance of supercooling region ATx are 0.616 and 45 K, respectively for this Gd-Co-A1 alloy. The compressive fracture strength （σf） and elastic modulus （E） of Gd-Co-A1 glassy alloys are 1 170-1 380 MPa and 59-70 GPa, respectively. The Gd-AI-Co bulk glassy alloys with high glass forming ability and good mechanical properties are promising for the future development as a new type function materials.     

Formation and Structural Evolution of Fe_(72.5)B_(15.6)Si_(7.8)Nb_(1.7)Zr_(1.7)Cu_(0.7) Nanocrystalline Alloy

A 2.5-mm Fe_(72.5)B_(15.6)Si_(7.8)Nb_(1.7)Zr_(1.7)Cu_(0.7) glassy rod was successfully fabricated using copper mold casting.The introduction of Cu resulted in the formation of large quantities of a-Fe nanoparticles embedded in the glassy matrix after isothermal annealing.The Fe_(72.5)B_(15.6)Si_(7.8)Nb_(1.7)Zr_(1.7)Cu_(0.7) nanocrystalline alloy exhibited high saturation magnetization(～1.26 T) and a low coercive force(～0.8 A/m) after annealing at 833 K for 15 min due to the precipitation of ～15-nm-sized a-Fe nanoparticles in the glassy matrix.The structural evolution of the FeBSiNbZrCu amorphous alloy during the annealing process was discussed using a dual-cluster model.     

Effect of partial substitution of Co with Fe on the properties of LaNi3.55Mn0.4Al0.3Co0.75−xFex (x=0, 0.15, 0.55) alloys electrodes

The effect of iron substitution on the electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x compounds (x=0, 0.15, 0.55) has been studied by chronopotentiometry and cyclic voltammetry techniques. The maximum capacity decreases linearly from 308 to 239 mAhg⁻¹ when the iron content increases from 0 to 7.3 wt.% (x=0.55). This decrease can be explained by the corrosion of the alloy in the aqueous KOH electrolyte. In spite of this decrease and of the long time needed for the activation, a good stability of discharge capacity was observed in LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x compounds. The reversibility of the electrochemical redox reaction of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x alloy electrodes has been observed in the alloys least rich in iron. The hydrogen diffusivity in LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x alloy electrodes decreases when increasing the iron content. The obtained values of the hydrogen diffusion coefficient D_H, varies between 2.1×10⁻⁷ and 8.2×10⁻⁹ cm² s⁻¹ depending on the iron content of the electrode.     

Cu-based bulk amorphous alloy with larger glass-forming ability and supercooled liquid region

The glassy rod with a maximum sample thickness of 11 mm and larger supercooled liquid region of 108 K was successfully fabricated when substituting Cu with minor amount of Ag in the Cu–Zr–Al–Gd alloy system. The value of γ reaches a maximum of 0.418 for the Cu_45.5Zr₄₅Al₇Gd₂Ag_0.5 bulk metallic glass (BMG) alloy. The high glass-forming ability (GFA) and larger supercooled liquid region are discussed from atomic size, negative mixing heat among constituent elements and thermodynamics.     

Glass-forming ability and magnetic properties of mechanically solid-state reacted Co100−xTix alloy powders

A high-energy ball milling technique using the mechanical alloying method has been employed for fabrication of glassy Co_100−xTi_x (25≤x≤67) alloy powders at room temperature. The fabricated glassy alloys in the Co-rich (33≥x) side exhibit good soft magnetic properties. The binary glassy alloys for which the glass transition temperatures (T_g) have rather high temperatures (above 800 K), show large supercooled liquid regions before crystallization (ΔT_x larger than 50 K). The reduced glass transition temperature (ratio between T_g and liquidus temperatures, T_l (T_g/T_l)) was found to be larger than 0.56. We have also performed post-annealing experiments on the mechanically deformed Co/Ti multilayered composite powders. The results show that annealing of the powders at 710 K leads to the formation of a glassy phase (thermally enhanced glass formation reaction), of which the heat of formation was measured directly. The similarity in the crystallization and magnetization behaviors between the two classes of as-annealed and as-mechanically alloyed glassy powders implies the formation of the same glass state.     

Non-isothermal Crystallization Kinetics and Isothermal Crystallization Kinetics in Supercooled Liquid Region of Cu–Zr–Al–Y Bulk Metallic Glass

The crystallization kinetics of Cu_(43)Zr_(48)Al_9and(Cu_(43)Zr_(48)Al_9)_(98)Y_2bulk metallic glasses in non-isothermal and isothermal conditions was studied by differential scanning calorimetry.In the non-isothermal and isothermal modes,the average activation energy of(Cu_(43)Zr_(48)Al_9)_(98)Y_2is larger than that of Cu_(43)Zr_(48)Al_9,meaning the higher stability against crystallization of(Cu_(43)Zr_(48)Al_9)_(98)Y_2.In addition,the average activation energies for Cu_(43)Zr_(48)Al_9and(Cu_(43)Zr_(48)Al_9)_(98)Y_2calculated using Arrhenius equation in isothermal mode are larger than the values calculated by Kissinger–Akahira–Sunose method in non-isothermal mode,indicating that the energy barrier is higher in isothermal mode.The Johnson–Mehl–Avrami model was used to analyze the crystallization kinetics in the non-isothermal and isothermal modes.The Avrami exponent n for Cu_(43)Zr_(48)Al_9is above 2.5,indicating that the crystallization is mainly determined by a diffusion-controlled three-dimensional growth with an increasing nucleation rate,while the Avrami exponent n for(Cu_(43)Zr_(48)Al_9)_(98)Y_2is in the range of 1.5–2.5 in the non-isothermal mode,implying that the crystallization is mainly governed by diffusion-controlled three-dimensional growth with decreasing nucleation rate.Finally,the Avrami exponents n for Cu_(43)Zr_(48)Al_9and(Cu_(43-)Zr_(48)Al_9)_(98)Y_2are different in the non-isothermal and isothermal conditions,which imply different nucleation and growth behaviors during the crystallization processes.     

Mechanically induced crystalline–glassy phase transformations of mechanically alloyed Ta55Zr10Al10Ni10Cu15 multicomponent alloy powders

New multicomponent Ta-based glassy alloy powder was synthesized by mechanical alloying (MA) the elemental powders of Ta₅₅Zr₁₀Ni₁₀Al₁₀Cu₁₅ at room temperature, using a low-energy ball milling technique. During the early stage of milling the agglomerated crystalline powders are mechanically crushed and fresh surfaces are rapidly created. Kneading of such ground powders enhances the atomic diffusion and leads to local alloying. As the MA time increases, the number of vacancies in the Ta lattice (base material) increases so that the atoms of the alloying elements for Zr, Al, Ni and Cu tend to migrate to the open defected lattice of metallic Ta. The number of atoms of the alloying elements that migrate to the bcc lattice of the base material are increasing with increasing MA time and this leads to a monotonic expansion of the Ta lattice. Further milling time (86–130 ks) plays an important role in increasing the rate of diffusion and this leads to an increase in the number of migrated atoms of the alloying elements that pass into the Ta lattice. The a₀ of the yielded solid solution at this stage does not change anymore with increasing MA time and a homogeneous supersaturated bcc-solid solution is obtained after 130 ks of MA time. This solid solution, which is subjected to continuous imperfections, is gradually transformed into a glassy phase upon increasing the MA time. The glassy powders of the final-product (1080 ks) in which its glass transition temperature (T_g) lies at a high temperature (834 K), crystallize through a single sharp exothermic peak at 1004 K (T_x). The total enthalpy change of crystallization (ΔH_x) is −10.32 kJ/mol. The width of the supercooled liquid region before crystallization (ΔT_x) of the synthesized glassy powder shows the largest value (170 K) of any reported metallic glassy system.     

Magnetic properties of nanocrystalline Finemet alloys with Co addition

This report focuses on ac magnetic properties of (Fe_0.5Co_0.5)_73.5Cu₁Nb₃Si_13.5B₉ alloy in the high temperature. The effects of replacing 50% Fe by Co in Fe_73.5Cu₁Nb₃Si_13.5B₉ alloy on the static magnetic properties have also been studied. Addition of Co leads to an increase around 110 K of the Curie temperature of the amorphous phase, much higher than Ge-containing Finemet alloy. The material has much better ac magnetic properties than Hitperm alloy. An excellent stability of initial permeability in high temperature (up to 650 K) and high frequency (up to 5 × 10⁵ Hz) can be observed with respect to the Co-free alloy.     

Electrochemical properties of the MmNi3.55Mn0.4Al0.3Co0.75−xFex (x = 0.55 and 0.75) compounds

The hydrogen storage alloys MmNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x (x = 0.55 and 0.75) were used as negative electrodes in the Ni-MH accumulators. The chronopotentiommetry and the cyclic voltammetry were applied to characterize the electrochemical properties of these alloys. The obtained results showed that the substitution of the cobalt atoms by iron atoms has a good effect on the life cycle of the electrode. For the MmNi_3.55Mn_0.4Al_0.3Co_0.2Fe_0.55 compound, the discharge capacity reaches its maximum of 210 mAh/g after 12 cycles and then decreases to 190 mAh/g after 30 charge–discharge cycles. However, for the MmNi_3.55Mn_0.4Al_0.3Fe_0.75 compound, the discharge capacity reaches its maximum of 200 mAh/g after 10 cycles and then decreases to 160 mAh/g after 30 cycles.

The diffusion behavior of hydrogen in the negative electrodes made from these alloys was characterized by cyclic voltammetry after few activation cycles. The values of the hydrogen coefficient in MmNi_3.55Mn_0.4Al_0.3Co_0.2Fe_0.55 and MmNi_3.55Mn_0.4Al_0.3Fe_0.75 are, respectively, equal to 2.96 × 10⁻⁹ and 4.98 × 10⁻¹⁰ cm² s⁻¹. However, the values of the charge transfer coefficients are, respectively, equal to 0.33 and 0.3. These results showed that the substitution of cobalt by iron decreases the reversibility and the kinetic of the electrochemical reaction in these alloys.     

Effect of Mn concentration on the spin glass transition temperature of Fe0.70−xMnxAl0.30 alloys

Magnetization measurements on zero field cooled (ZFC) and field cooled (FC) samples as a function of temperature where made on Fe_0.70−xMn_xAl_0.30 alloys with 0≤x≤0.10. Our data show the existence of two regimes of the spin glass temperature T_f when increasing the concentration x of the Mn atoms. We found that T_f decreases slowly with increasing x up to x=0.06 and then shows a rapid linear decrease above this concentration. The existence of two regimes of T_f behavior with x may be attributed to the disappearance of ferromagnetic clusters which exist for low values of x (x<0.06). Compared to the Mn-free alloy, the relative changes in T_f are bigger and exceed 40% at x=0.10. The second regime (x>0.06) is associated with more influence of x on T_f.     

Electrochemical investigation of the iron-containing and no iron-containing AB5-type negative electrodes

The electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x (x = 0, 0.15, 0.55, 0.75) intermetallic compounds has been studied and presented [C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, Int. J. Hydrogen Energy 29 (2004) 307–311; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 360 (2003) 266–271; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 384 (2004) 249–253]. It has been deduced that the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound has interesting electrochemical properties. In this paper we present the electrochemical study of LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound properties compared with the parent LaNi_3.55Mn_0.4Al_0.3Co_0.75 compound. Several techniques, such as, the chronopotentiometry, the constant potential discharge (CPD), the cyclic voltammetry (CV) and the linear polarization (LP) were applied to characterize these electrochemical properties. The electrochemical discharge capacity of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 alloy increases to reach 294 mAh g⁻¹ after few cycles only (five cycles). However, the activation of the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy takes more than 20 cycles to be achieved and the obtained maximum discharge capacity is 194 mAh g⁻¹. The hydrogen diffusion coefficient D_H was determined by constant potential discharge and cyclic voltammetry techniques. The obtained values of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compounds are 6.29 × 10⁻¹¹ and 7.62 × 10⁻¹¹, and 2 × 10⁻⁸ and 7.5 × 10⁻⁸ cm² s⁻¹ by CPD and CV techniques, respectively. The exchange current density values, determined by a linear polarization technique, are 44 and 27 mA g⁻¹, respectively, for LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloys.     

Glass formation ability, structure and magnetocaloric effect of a heavy rare-earth bulk metallic glassy Gd55Co20Fe5Al20 alloy

The structure and magnetic entropy changes in melt-spun and annealed LaFe_11.8−xCo_xSi_1.2 (x = 0, 0.4 and 0.8) ribbons have been investigated. It is found that the value of T_c can be increased continuously up to 290 K for x = 0.8 and the phase transition, at T_c from paramagnetic to ferromagnetic, is changed from first- to second-order due to Co substitution. Large values of the magnetic entropy change are 31 and 13.5 J/kg K in the magnetic field change from 0 to 5 T at 201 K for the LaFe_11.8Si_1.2 and at 290 K for the LaFe₁₁Co_0.8Si_1.2 ribbons, respectively. The magnetic entropy change in the LaFe₁₁Co_0.8Si_1.2 ribbons is higher than that reported in the bulk counterpart and that of conventional MCE materials, such as pure Gd. The enhanced magnetic entropy change of ribbons compared to bulk counterpart is attributed to a more uniform microstructure and element distribution resulting from the high cooling rate by melt-spinning.     

脉冲磁场处理Fe52Co34Hf7B6Cu1非晶的低温真空退火效应

对Fe₅₂Co₃₄Hf₇B₆Cu₁非晶合金进行了低频磁脉冲处理,研究低温真空退火对磁脉冲处理Fe_52Co₃₄Hf₇B₆Cu₁非晶软磁性能的影响.结果表明,磁脉冲处理导致非晶合金发生纳米晶化,析出晶态相α-Fe（Co）,晶粒尺寸为5-10 nm,形成的纳米晶粒弥散分布于非晶基体的双相纳米合金中.对磁脉冲处理的试样进行低温真空退火,可以进一步优化纳米合金的软磁性能,在100℃退火可以得到最佳的软磁性能.     

High permeability nano-crystalline FeSiBTaAg ribbons obtained by direct casting

Nano-crystalline soft magnetic ribbons, being extensively used as magnetic cores for switching power supplies, have been invariantly obtained by melt-spinning followed by post-annealing. Reported herewith are the attainment, by direct-casting without annealing, of nano-crystalline Fe_77.4−xSi_15.5B₇Ta_xAg_0.1 (x = 1, 2) ribbons with superior soft magnetic properties (named TAGMET after the addition of Ta and Ag). The grain size of nano-crystalline -FeSi, from 20 to 30 nm, varies with composition and quenching speeds. As-spun Fe_75.4Si_15.5B₇Ta₂Ag_0.1 ribbons consisting of 25 nm nano-crystals exhibit a saturation magnetization of 157 emu/g (1.45 T), an effective permeability of 56,000 at 1 kHz, and coercivity, 8 A/m. With the combination of easier manufacturing process and excellent soft magnetic properties, this alloy is competitive in industrial applications versus the well-known FINEMET.     

Microstructures and magnetic properties of hydrogenation disproportionation desorption recombination-processed Nd–Fe–B materials with different Nd content of 11.0 and 12.6 at.%

The hydrogenation disproportionation desorption recombination (HDDR) process was performed on the generally used alloy composition of Nd_12.6Fe_63.1Co_17.4Zr_0.1Ga_0.3B_6.5 and a low rare earth content alloy composition of Nd_11.0Fe_65.0Co_17.8Zr_0.1Ga_0.3B_5.8. A detailed evaluation was made of the relationship between the microstructure and magnetic properties of these HDDR-processed magnetic powders with respect to their different rare earth element concentrations. The HDDR-processed powders of both alloy compositions were transformed to the Nd₂Fe₁₄B phase consisting of fine recombined crystal grains of around 400–500 nm in size and maintained the anisotropic magnetic characteristic that was present before HDDR processing. However, reduction of the rare earth content drastically reduced coercivity, and the alloy composition of Nd_11.0Fe_65.0Co_17.8Zr_0.1Ga_0.3B_5.8 did not manifest magnetic properties. From the results of an examination of their microstructures, it was inferred that the coercivity decreased due to a decline in the concentration of the rare earth element at the grain boundaries of the fine Nd₂Fe₁₄B grains with the reduction of the rare earth content of the alloys. Accordingly, in magnetic powders obtained by the HDDR process, the nucleation type of coercivity mechanism predominates, in which rare earth-rich regions present at the grain boundaries of fine Nd₂Fe₁₄B grains play a large role in the manifestation of coercivity.