A study on microstructure,magnetic properties and kinetics of the nanocrystallization of Fe40Ni38B18Mo4 metglass

This study has investigated the microstructure and magnetic properties of Fe₄₀Ni₃₈B₁₈Mo₄ at various degrees of crystallization from the amorphous state. TEM and XRD studies confirmed that phases forming after crystallization at temperatures around 414 and 522 °C were cubic (Fe, Ni, Mo)₂₃B₆ phase and FCC (Fe, Ni) solid solution. The growth behavior and morphology of the nanocrystalline phases have been studied as a function of time and temperature. Nanoparticles were lying in the size range of 10–20 nm and they were stable below 522 °C. Kissinger approach, Ozawa method and Yi Qun Gao method were employed to determine and compare the kinetic parameters of the crystallization processes. A growth mechanism of crystallizing phases was proposed on the basis of these results. Magnetic properties mainly coercivity and saturation magnetization of as-received and heat-treated samples were evaluated.     

Stability of bulk metastable Fe<Subscript>83</Subscript>B<Subscript>17</Subscript> eutectic alloy prepared by hypercooling method

The bulk metastable Fe₈₃B₁₇ eutectic alloy has been successfully prepared using hypercooling solidification. The bulk alloy consists of αFe and metastable Fe₃B phases, without the stable Fe₂B phase. Upon isothermal annealing, decomposition of the metastable Fe₃B phase (prepared by hypercooling) was investigated, as compared to the corresponding behaviour from amorphous Fe-B alloy. PACS 61.82.Bg; 64.60.-i; 64.60.My; 64.70.Kb; 68.60.Dv     

The evolution of electronic configuration and magnetic characterization of Fe<Subscript>9</Subscript>Ni<Subscript>1</Subscript>, Fe<Subscript>8</Subscript>Ni<Subscript>2</Subscript> alloy in theoretical calculation

To analyze the origin of the magnetic enhancement of Fe-Ni alloy, the electronicconfigurations and magnetic properties were investigated using density functional theorybased on the first-principle. The supercell (5 × 1 × 1) of Fe,Fe₉Ni₁ and Fe₈Ni₂ were constructed. Thedefect formation energy, band structure, density of states and electron density differencewere calculated. The results showed that Ni doping changed the electronic configuration ofFe atoms, resulting in the enhancement of spin polarization of Fe and the larger Bohrmagnetic moment in Fe-Ni alloys (Fe₉Ni₁). The results showed thatthe charge transfer and the atomic spacing between Fe atoms and the dopant Ni atoms playedan important role in determination of magnetic moment. The value of Fe supercell(5 × 1 × 1), Fe₉Ni₁ and Fe₈Ni₂ were 23.14,23.34 and 22.61μ _B, respectively.     

Effect of temperature on the magnetoimpedance of an elastically deformed Fe<Subscript>4</Subscript>CO<Subscript>67</Subscript>Mo<Subscript>1.5</Subscript>Si<Subscript>16.5</Subscript>B<Subscript>11</Subscript> foil

The effect of temperature and elastic tensile stresses on the magnetoimpedance of an amorphous Vitrovac 6025Z (Fe₄CO₆₇Mo_1.5Si_16.5B₁₁) foil is studied. Two temperature ranges (20–70 and 70–220°C) in which the effect of elastic tensile stresses on the magnetoimpedance has different characters are detected. The existence of these two temperature ranges is shown to be caused by a change in the sign of a magnetostriction constant at 70°C.     

Genesis,structural, and transport properties of La<Subscript>2</Subscript>Mo<Subscript>2-x</Subscript>W<Subscript>x</Subscript>O<Subscript>9</Subscript> prepared via mechanochemical activation

Fast oxide-ion conductors La₂Mo_2-xW_xO₉ (x = 0–1) have been prepared using mechanochemical activation (MA) of starting oxides in a high-power planetary ball mill. Studies of La₂Mo_2-xW_xO₉ genesis and structural properties using thermal analysis, XRD, SEM, IR, and Raman spectroscopy have revealed that MA results in the formation of an amorphous precursor, while the cubic β-phase is formed after calcination at 700–900 °C. Due to a high dispersion of powders, high-density pellets of W-LAMOX ceramics have been obtained already after sintering at 950 °C. Their electrical conductivity measured by the impedance spectroscopy depends on the W concentration being sufficiently high (up to 5.6?10^?3 S/cm at 630 °C) at temperatures below 650 °C.     

The temperature dependence of the magnetoelastic characteristics of cores for force sensors utilizing Fe<Subscript>70</Subscript>Ni<Subscript>8</Subscript>Si<Subscript>10</Subscript>B<Subscript>12</Subscript> amorphous alloy

This paper presents the results of investigation on the influence of temperature on magnetoelastic characteristics of the two ring-shaped cores, made of Fe₇₀Ni₈Si₁₀B₁₂ amorphous alloy. The cores were annealed for 1 h at 350 and 400°C, respectively. The compressive force F was applied perpendicular to the direction of the magnetizing field H in the sample. Special cylindrical backing enables application of the uniform compressive stress σ to the wound ring sample. A resistive furnace heated the experimental set-up. Results presented in the paper indicate a significant influence of the temperature on the magnetoelastic characteristics of Fe₇₀Ni₈Si₁₀B₁₂ amorphous alloy. Information about the magnetoelastic characteristics of this material may be useful in the magnetoelastic sensor development. Also this will create new possibilities in the development of physical model of magnetoelastic effect.      

Mechanochemical reactions in Co<Subscript>80</Subscript>B<Subscript>20</Subscript> and Co<Subscript>60</Subscript>B<Subscript>40</Subscript> mixtures during ball milling and postannealing

The solid-phase interaction of cobalt with boron during high-energy ball milling of Co₈₀B₂₀ and Co₆₀B₄₀ mixtures was studied. It was found that Co₃B boride forms during the mechanical alloying of components in the presence of both modifications of Co with a reduction in the size of blocks of up to 7–15 nm. The transformation of the metastable Co₃B phase into stable Co₂B and CoB borides is observed in the temperature range of 590–700°C.     

A metastable phase forming during crystallization of an amorphous Ni70Mo10P20 alloy

The evolution of the structure of an amorphous Ni₇₀Mo₁₀P₂₀ alloy during annealing in the temperature range from 673 to 873 K is studied using x-ray diffraction and transmission electron microscopy. It is found that a previously unknown metastable phase forms during crystallization of the amorphous Ni₇₀Mo₁₀P₂₀ alloy. The morphology of the newly formed crystals is studied, the space group and the lattice constant are determined, and the atom positions for the phase that forms are proposed. It is found that the metastable phase is a phosphide whose composition is close to (Ni(Mo))₃P. We established that, as the temperature or the duration of annealing is increased further, the metastable phase turns into the equilibrium Ni₃P phase. The orientation relations between the metastable and equilibrium phases are determined.     

Effect of Al-Mo codoping on the structure and ionic conductivity of sol-gel derived Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript> ceramics

Al-Mo codoped Li₇La₃Zr₂O₁₂ ceramics with fine grain were prepared by sol-gel method. The influences of Al-Mo codoping on the structure, microstructure, and conductivity of Li₇La₃Zr₂O₁₂ were investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and impedance spectroscopy. The cubic phase Li₇La₃Zr₂O₁₂ has been stabilized by partial substitution of Al for Li and Mo for Zr. Li_6.6-3yAl_yLa₃Zr_1.8Mo_0.2O₁₂ (0?≤?y?≤?0.1) has been sintered at 1040–1060 °C for 3 h. The liquid sintering facilitated its densification. The relative density of the composition with x?=?0.075 was approximately 96.4%. Results indicated that the Al-Mo codoped LLZO synthesized by sol-gel method effectively lowered its sintering temperature, accelerated densification, and improved the ionic conductivity.     

Improvement in rate capability of lithium-rich cathode material Li[Li<Subscript>0.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>]O<Subscript>2</Subscript> by Mo substitution

Lithium-rich cathode material Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D _Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g^?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g^?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.     

Magnetic and Mössbauer Studies of Fe<Subscript>76</Subscript>Mo<Subscript>8</Subscript>Cu<Subscript>1</Subscript>B<Subscript>15</Subscript> Amorphous Alloy

“Zero field”-Mössbauer and magnetization measurements have been performed on an amorphous Fe₇₆Mo₈Cu₁B₁₅ alloy in the temperature range of (10-340) K. The room-temperature Mössbauer spectrum exhibits magnetic dipole and electric quadrupole interactions. At approximately 306 K, the magnetic interactions vanish and the alloy shows fully paramagnetic behavior. On the other hand, the relative representation of paramagnetic component becomes weak with decreasing temperature and below 220 K the magnetic dipole interactions prevail. Below this temperature an anomaly in the low-temperature dependencies of ac susceptibility and of magnetization, measured during cooling the specimen from 340 K down to 20 K is observed. The anomaly on the magnetization curve vanishes in the field of 200 Oe.     

Synthesis and electrochemical properties of Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> cathode material for lithium-ion battery

The layered Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ lithium-rich manganese-based solid solution cathode material has been synthesized by a simple solid-state method. The as-prepared material has a typical layered structure with R-3m and C2/m space group. The synthesized Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ has an irregular shape with the size range from 200 to 500 nm, and the primary particle of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ has regular sphere morphology with a diameter of 320 nm. Electrochemical performances also have been investigated. The results show that the cathode material Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ prepared at 900 °C for 12 h has a good electrochemical performance, which can deliver a high initial discharge capacity of 233.5, 214.2, 199.3, and 168.1 mAh g^?1 at 0.1, 0.2, 0.5, and 1 C, respectively. After 50 cycles, the capacity retains 178.0, 166.3, 162.1, and 155.9 mAh g^?1 at 0.1, 0.2, 0.5, and 1 C, respectively. The results indicate that the simple method has a great potential in synthesizing manganese-based cathode materials for Li-ion batteries.     

Temperature dependence of the magnetic properties and magnetoimpedance of nanocrystalline Fe<Subscript>73.5</Subscript>Si<Subscript>16.5</Subscript>B<Subscript>6</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript> ribbons

The temperature dependences of the magnetic properties and the magnetoimpedance effect of soft magnetic nanocrystalline Fe_73.5Si_16.5B₆Nb₃Cu₁ alloy ribbons are studied in the temperature range 24–160°C. A high temperature sensitivity of the impedance and the magnetoimpedance effect of the ribbons are detected in the ac frequency range 0.1–50 MHz. At an ac frequency of 50 MHz, the change in the impedance reaches 0.2 Ω/°C (0.5%/°C) in the temperature range 85–160°C. When the temperature increases, a monotonically decreasing character of the dependence of the magnetoimpedance effect on the applied magnetic field changes into a dependence having an increasing initial segment. The effect of temperature on the magnetoimpedance properties of the soft magnetic nanocrystalline ribbons is shown to result from temperature-induced changes in their electrical conductivity, magnetization, and effective magnetic anisotropy.     

An experimental and theoretical study of Ni impurity centers in Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript>

The local environment and the charge state of a nickel impurity in cubic Ba_0.8Sr_0.2TiO₃ are studied by XAFS spectroscopy. According to the XANES data, the mean Ni charge state is ~2.5+. An analysis of the EXAFS spectra and their comparison with the results of first-principle calculations of the defect geometry suggest that Ni²⁺ ions are in a high-spin state at the B sites of the perovskite structure and the difference of charges of Ni²⁺ and Ti⁴⁺ is mainly compensated by distant oxygen vacancies. In addition, a considerable amount of nickel in the sample is in a second phase BaNiO_{3 ? δ}. The measurements of the lattice parameter show a decrease in the unit cell volume upon doping, which can indicate the existence of a small amount of Ni⁴⁺ ions at the B site.     

Nanocrystallization of an amorphous Fe<Subscript>80</Subscript>B<Subscript>20</Subscript> alloy during severe plastic deformation

The structural evolution of an amorphous Fe₈₀B₂₀ alloy subjected to severe plastic deformation at room temperature or at 200°C was studied. Deformation leads to the formation of α-Fe nanocrystals in an amorphous phase. After room-temperature deformation, nanocrystals are localized in shear bands. After deformation at 200°C, the nanocrystal distribution over the alloy is more uniform. Possible causes of the crystallization of the amorphous phase during severe plastic deformation are discussed.     

Synthesis and electrochemical properties of P2-Na<Subscript>2/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>2/3</Subscript>O<Subscript>2</Subscript>

The pure phase P2-Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g^?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g^?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na_2/3Ni_1/3Mn_2/3O₂ is a potential cathode material for sodium-ion batteries.     

Nanogranular Phase Formation During Devitrification of Fe(NiCo)ZrB Amorphous Alloys

A comprehensive review of our recent experimental and theoretical developments in the processing of nanocrystalline soft magnetic materials made by crystallization of amorphous precursors and containing new nanocrystalline phases is given. The relationship between the structures of the metastable and equilibrium phases and their transformations are discussed. Nickel-rich amorphous precursors with stoichiometry Ni₆₄Fe₁₆Zr₇B₁₂Au₁ were produced by melt-spinning technique and then heat-treated at temperatures ranged from 420 °C to 600 °C for one hour to form nanostructured alloy. The transformation from the amorphous state into the nanocrystalline state was investigated by the differential scanning calorimetry (DSC), the x-ray diffraction (XRD), the vibrating sample magnetometry (VSM) and Mössbauer techniques. The annealing favours the emergence of cubic Fe_xNi_23-xB₆ crystalline grains (10-25 nm in diameter). Magnetic measurements made at 4.2-1100 K reveal rather high value of saturation magnetization (nearly 60 and 40 Am²/kg at 4.2 K and room temperature, respectively) in amorphous as well as in nanocrystalline states. These facts are consistent with 300 K ⁵⁷Fe Mössbauer results which are well supported by the calculations of Ni and Fe magnetic moments in Ni₂₃B₆ and Fe₂₃B₆ phases, using the spin polarized tight binding linear muffin-tin orbital (TB-LMTO) method. However, anomalous high magnetic moments of Fe and Co atoms were found in some inequivalent positions in the crystal structure.     

Cluster formation in LiNi<Subscript>0.4</Subscript>Fe<Subscript>0.6</Subscript>O<Subscript>2</Subscript>

The structure of an LiNi_0.4Fe_0.6O₂ cubic solid solution is determined using magnetic measurements and electron diffraction. It is found that this solid solution has a microinhomogeneous structure due to the formation of superparamagnetic clusters. The electron diffraction analysis of LiNi_0.4Fe_0.6O₂ samples has revealed diffuse scattering characteristic of the substitutional short-range order in ordered solid solutions with a B1-type structure. It is shown that the short-range order is associated with the LiNiO₂-type rhombohedral superstructure (space group \(R\bar 3m\)), i.e., with the redistribution of lithium and nickel atoms in the (111)_B1 alternating planes. The short-range order is observed in regions with a nickel content higher than the mean nickel content corresponding to the macroscopic composition.     

Inelastic neutron scattering study and Hubbard model description of the antiferromagnetic tetrahedral molecule Ni<Subscript>4</Subscript>Mo<Subscript>12</Subscript>

The tetrameric Ni(II) spin cluster Ni₄Mo₁₂ has been studied by INS. The data were analyzed extensively in terms of a very general spin Hamiltonian, which includes antiferromagnetic Heisenberg interactions, biquadratic 2-spin and 3-spin interactions, a single-ion magnetic anisotropy, and Dzyaloshinsky-Moriya interactions. Some of the experimentally observed features in the INS spectra could be reproduced, however, one feature at 1.65 meV resisted all efforts. This supports the conclusion that the spin Hamiltonian approach is not adequate to describe the magnetism in Ni₄Mo₁₂. The isotropic terms in the spin Hamiltonian can be obtained in a strong-coupling expansion of the Hubbard model at half-filling. Therefore detailed theoretical studies of the Hubbard model were undertaken, using analytical as well as numerical techniques. We carefully analyzed its abilities and restrictions in applications to molecular spin clusters. As a main result it was found that the Hubbard model is also unable to appropriately explain the magnetism in Ni₄Mo₁₂. Extensions of the model are also discussed.     

Structural evolutions of the mechanically alloyed Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> powders

Elemental mixtures of Al, Cu, Fe powders with the nominal composition of Al₇₀Cu₂₀Fe₁₀ were mechanically alloyed in a planetary ball mill for 80 h. Subsequent annealing of the as-milled powders were performed at 600–800°C temperature range for 4 h. Structural characteristics of the mechanically alloyed Al₇₀Cu₂₀Fe₁₀ powders with the milling time and the heat treatment were investigated by X-ray diffraction (XRD), differential scanning calorimeter (DSC) and differential thermal analysis (DTA). Mechanical alloying of the Al₇₀Cu₂₀Fe₁₀ did not result in the formation of icosahedral quasicrystalline phase (i-phase) and a long time milling resulted in the formation of β-Al(Cu,Fe) solid solution phase (β-phase). The i-phase was observed only for short-time milled powders after heat treatment above 600°C. The β-phase was one of the major phases in the Al₇₀Cu₂₀Fe₁₀ alloy. The w-Al₇Cu₂Fe₁ phase (w-phase) was obtained only after heat treatment of the short-time milled and unmilled samples. The present investigation indicated that a suitable technique to obtain a large amount of quasicrystalline powders is to use a combination of short-time milling and subsequent annealing.