Structures and Electrochemical Performances of As-spun RE-Mg-Ni-Mn-based Alloys Applied to Ni-MH Battery

The La-Mg-Ni-Mn-based AB₂-type La_1-xCe_xMgNi_3.5Mn_0.5 (x = 0, 0.1, 0.2, 0.3, and 0.4) alloys were fabricated by melt spinning technology. The effects of Ce content on the structures and electrochemical hydrogen storage performances of the alloys were studied systematically. The XRD and SEM analyses proved that the experimental alloys consist of a major phase LaMgNi₄ and a secondary phase LaNi₅. The variation of Ce content causes an obvious change in the phase abundance of the alloys without changing the phase composition. Namely, with the increase of Ce content, the LaMgNi₄ phase augments and the LaNi₅ phase declines. The lattice constants and cell volumes of the alloys clearly shrink with increasing Ce content. Moreover, the Ce substitution for La results in the grains of the alloys clearly refined. The electrochemical tests showed that the substitution of Ce for La obviously improves the cycle stability of the as-spun alloys. The analyses on the capacity degradation mechanism demonstrate that the improvement can be attributed to the ameliorated anti-corrosion and anti-oxidation ability originating from substituting partial La with Ce. The as-spun alloys exhibit excellent activation capability, reaching the maximum discharge capacities just at the first cycling without any activation treatment. The substitution of Ce for La evidently improves the discharge potential characteristics of the as-spun alloys. The discharge capacity of the alloys first increases and then decreases with growing Ce content. Furthermore, a similar trend also exists in the electrochemical kinetics of the alloys, including the high rate discharge ability (HRD), hydrogen diffusion coefficient (D), limiting current density (I_L) and charge transfer rate.     

A study of the crystallization kinetics of Ge-Te amorphous systems

The glass-forming ability of binary Ge_xTe_100-x (x=15, 20, 30) alloys was investigated. The crystallization mechanism of these amorphous bulks was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and differential scanning calo-rimetry (DSC). The temperature of glass transition, the temperature of crystallization, the activation energy for glass transition and crystallization, and the order of the crystallization mechanism were calculated from the different heating-rates.     

Preparation and mechanical behavior of Mg-based bulk metallic glasses and their matrix composite

Mg87-xCuxDy13(x=22,27,32) bulk metallic glasses (BGMs) with a diameter of 6-8 mm and in-situ Mg phase reinforced Mg70Cu17Dy13 BMG matrix composite with a diameter of 3 mm have been prepared by copper mould casting. The glass forming ability (GFA) of Mg-Cu-Dy alloys have been investigated by differential scanning calorimetry (DSC) and X-Ray diffraction (XRD) and tne mechanical properties have been measured. Results show that Mg87-xCuxDy13(x=22,27,32) alloys in the Mg-Cu-Dy alloy system exhibit excellent GFA, and Mg60Cu27Dy13 alloy has the largest GFA among these alloys. And In-situ Mg phase reinforced Mg70Cu17Dy13 BMG matrix composite exhibits some work hardening and a high fracture compressive strength of 702.38 MPa and some plastic strain of 0.81%. The improvement of the mechanical properties is attributed to the fact that the Mg phase distributed in the amorphous matrix of the alloy has some effective load bearing and plastic deformation ability to restrict the expanding of shear bands and cracks and produce its own plastic deformation.     

Formation and thermal stability of Cu-Zr-Al-Er bulk metallic glasses with high glass-forming ability

The formation and thermal stabilities of Cu_46.25Zr_46.25-xAl_7.5Er_x, (x=0 to 8) bulk metallic glasses (BMGs) were investigated. The addition of a small amount of Er (2at%) for replacing Zr effectively improves the glass-forming ability of Cu_46.25Zr_46.25Al_7.5 alloy, and the glassy rod with a diameter of at least 12 mm can be formed. The glass transition temperature (T_g), temperature interval of supercooled liquid region ΔT_x (= T_x − T_g, and reduced glass transition temperature T_rg (=T_g/T₁) of Cu_46.25Zr_44.25Al_7.5Er₂ glassy alloy are 699 K, 62 K and 0.607, respectively.     

添加微量稀土钇对铜基合金非晶形成能力的影响

针对铜基非晶合金玻璃形成能力问题,分析了添加微量稀土元素Y对合金的玻璃形成能力、热稳定性的影响,利用铜模吸铸法制备出Cu-Zr-Al-Y9mm非晶合金.研究结果表明：制备的9mm铜基非晶合金试样（Cu45Zr47Al8）97Y3,在过冷液相区ΔT和约化玻璃转变温度Trg分别是79.42K和0.775 3.随着稀土元素Y含量的增加Trg值变小,合金的非晶形成能力降低,通过Trg值变化可以判别该合金的非晶形成能力.     

Glass formation of ternary Sin-based Sm-AI-Co bulk metallic glasses

Ternary Sm-based Sm-AI-Co alloys at specific compositions designed using an e/a- and cluster-related criteria exhibit high glass forming abilities and form bulk glassy rods of 3 mm in diameter by a copper mold suction-casting method. Four compositions of bulk metallic glasses (BMGs) are Sm₅₀Al₂₅Co₂₅, Sm₅₂Al₂₄Co₂₄, Sm₅₄Al₂₃Co₂₃ and Sm₅₆Al₂₂Co₂₂, which all satisfy a constant conduction electron concentration of 1.5. Among them, the BMG exhibiting the largest reduced glass transition temperature (T_rg) is Sm₅₀Al₂₅Co₂₅, which reaches 0.648. The glass transition temperature T_g and the onset crystallization temperature T_x of this alloy are respectively 579 and 640 K at a heating rate of 20 K/min.     

Bulk glass formation in ternary Cu-Zr-Ti system

The formation of bulk metallic glasses (BMGs) in ternary Cu-Zr-Ti system was investigated by a copper mold casting method. The nature of the amorphous phase was verified by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). It was demonstrated that the BMGs could be formed in a broad composition range in this system. Cu₅₀Zr_42.5Ti_7.5, Cu₆₀Zr_27.5Ti_12.5, CU₆₀Zr₃₀Ti₁₀, and Cu₆₀Zr_32.5Ti_7.5 alloys exhibit strong glass-forming ability (GFA), and fully glassy rods of 5 mm in diameter can be obtained. In the center region of the ternary diagram, however, the GFA of the alloys was degraded due to the presence of Laves phase. The degradation of the GFA results from easy nucleation of the Laves phase in the undercooled liquid.     

A cluster line approach to finding new Fe-B-Y-Nb-Zr bulk metallic glasses

The glass forming ability of the [(Fe_12/13Y_1/13)_100-xB_x]₉₆Nb₂Zr₂ (x=9–26) system was investigated using a series of cluster lines. Three types of clusters, an icosahedron (Fe₁₂Y), a capped Archimedes anti-prism (Fe₈B₃) and a capped trigonal prism (Fe₉B), as well as a binary eutectic (Fe₈₃B₁₇) were considered. Bulk glassy alloy rods of 3 mm in diameter were synthesized using a copper mold suction-casting method. The glass transition temperature was observed for all samples in the boron range of 15.9at%-25.7at%, with the alloy at 15.9at% of boron having the best thermal properties. The ferrous-based bulk metallic glasses (BMG) obtained have high reduced glass transition temperatures with the maximum reaching 0.63 and large supercooled liquid regions with the maximum reaching 111 K. Magnetic testing revealed a large value of coercive force and remanent magnetization, being 11 kA/m and 0.1 T, respectively.     

Effects of Si and Ce on the microstructure and hydrogen storage property of Ti<Subscript>26.5</Subscript>Cr<Subscript>20</Subscript>V<Subscript>45</Subscript>Fe<Subscript>8.5</Subscript>Ce<Subscript>0.5</Subscript> alloy

In this paper, the effects of Si and Ce on the microstructure and hydrogen storage property of Ti_26.5Cr₂₀V₄₅Fe_8.5Ce_0.5 alloy were studied, respectively. First of all, effects of Si on the microstructure and hydrogen storage properties of Ti_26.5Cr₂₀(V₄₅Fe_8.5)_1−x Si _x Ce_0.5 (x = 0, 0.5, 1.0, 1.5 and 2.0 at%) alloys were studied by X-ray diffraction, scanning electron microscopy and P-C isotherm measurements. As the Si addition increases, the hydrogen absorption capacities of alloys decrease but the equilibrium pressure increases, due to the formation of Laves phase. Secondly, the effect of Ce on Ti_26.5Cr₂₀ (V₄₅Fe_8.5)_0.98Si₂ alloy was studied. It was found that Ce addition is an effective way to eliminate the effect of Si on the hydrogen storage properties of the alloy. Supported by the National Hi-Tech Research and Development Program of China (“863” Project) (Grant No. 2006AA05Z144)     

Influence of substituting Ni with Co on hydriding and dehydriding kinetics of melt spun nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1−x Co _x (x=0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg₂Ni but results in the formation of secondary phase MgCo₂. No amorphous phase is detected in the as-spun Co-free alloy, but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However, it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4, the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy, and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).     

Glass-forming ability and chemical stability of magneto-optical glass heavily doped with rare earth oxide

The glass-forming region of B₂O₃-Al₂O₃-SiO₂ (BAS) glass heavily doped with rare earth oxides was investigated by an effective method, and the chemical stability was investigated by powder method. Influences of rare earth oxides on the glass-forming ability and the chemical stability of the BAS glass were also discussed. The experimental results show that the BAS glass-forming region expands firstly with the increase of the Tb₂O₃ content up to 30mol% and then shrinks. The acid-resistant capacity of the BAS glass doped with rare earth oxides is the lowest, the water-resistant capacity is secondary, and the alkali-resistant capacity is the best. Besides, the glass chemical stability can be improved by doping appropriate amount of rare earth oxides. Moreover, the stronger the ionic polarization ability of the rare earth ions is, the better the chemical stability of the BAS glass will be.     

Corrosion Behavior of Mg65Cu25-xZnxGd10 （x=0, 5）Metallic Glass

The effect of substitutional element Zn on corrosion behavior of Mg65Cu25Gd10 glass was investigated. The amorphous structure of Mg65Cu25-xZnxGd10 （x=0,5） alloys were examined by X-ray diffractometry and differential scanning calorimetry （DSC）. The dissolution rates of Mg65Cu25-xZnxGd10 （x=0, 5） metallic glasses in a 5 wt% NaCl solution with pH value of 7 were determined by a hydrogen evolution testing method. The corrosion behavior of these alloys was characterized using dipping tests with 5 wt% NaCl, in combination with electrochemical measurements and scanning electron microscopy （SEM）. Results show that the anti-corrosion ability of Mg65Cu25Gd10 alloy is significantly improved due to the addition of Zn. Possible mechanism responsible for the improvement is discussed.     

Formation and mechanical properties of ductile Fe-based amorphous alloys using a cast iron with minor addition of B and Al

Fe-based amorphous alloys with ductility were synthesized using the commercial cast iron QT50 (denoted as QT) with the combining minor addition of B and Al by single roller melt-spinning. The melt-spun (QT_1-xB_x)₉₉Al₁ (x is from 0.006wt% to 0.01wt%) amorphous alloys exhibit onset crystallization temperatures and Curie temperatures of 759–780 and 629–642 K respectively, and which increase with B content. The amorphous ribbons are ductile and can be bent 180° without breaking. With the increase in B content from 0.006wt% to 0.01wt%, the Vickers microhardness of the amorphous alloys increases from Hv 830 to Hv 1110. The effects of the additional B and Al elements on the glass forming ability and mechanical properties were also discussed.     

Effect of dy on structure and magnetic properties of CoPt alloys

The effects of Dy on the microstructure and magnetic properties of Dy _x Co_50?x Pt₅₀ alloys were investigated. The XRD results indicate that all the alloys homogenized at 1000 °C contain only a single A1 (fcc) phase, while the alloys annealed at 675 °C consist of a hard-magnetic face-centered-tetragonal (fct) phase and a magnetically soft face-centered-cube (fcc) phase. Maximum values for the coercivity H _c and remanence ratio m _r were achieved in Dy_0.4Co_49.6Pt₅₀ alloys annealed at 675 °C for 80 min. For the series of Dy _x Co_50?x Pt₅₀ alloys annealed at 675 °C for 60 min, H _c decreases monotonically with increasing Dy concentration, but m _r is first enhanced and then weakened.     

Compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni bulk metallic glasses

Starting from the quaternary Cu47Ti34Zr11Ni8 alloy, the compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni alloys was systematically investigated. Quaternary Cu-Ti-Zr-Ni alloys can be cast directly from the melt into copper molds to form fully amorphous strips or rods with the thickness of 3-6 mm. The evidence of the amorphous nature of the cast rods was provided by X-ray spectra. The measured glass transition temperature (Tg) and crystallization temperature (Tx) were obtained for the alloys using differential scanning calorimetry (DSC) at the heating rate of 20 K/s. In the results, the differences between the glass temperature and the crystallization tempera-ture (△Tx=Tx-Tg) are measured with values ranging up to 33-55 K. The reduced glass transition temperature (Trg), which is the ratio of the glass temperature to the liquidus temperature (T1), is often used as an indication of the glass-forming ability of metallic alloys. For the present Cu-Ti-Zr-Ni alloys, this ratio is typically in the range of 0.5838-0.5959, characteristic of metallic alloys with good glass-forming ability. The elastic constants for several selected alloys were measured using ultrasonic methods. The values of the elastic shear modulus, bulk modulus, and Poisson's ratio were also given.     

Gaseous and electrochemical hydrogen storage kinetics of as-quenched nanocrystalline and amorphous Mg2Ni-type alloys

The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1?x Co _x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo₂ and Mg instead of altering the major phase Mg₂Ni. No amorphous phase is detected in the as-quenched Cofree alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient (D) along with the limiting current density (I _L ) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg<Subscript>12</Subscript>-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg₁₂-type LaMg₁₁Ni + x wt% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter (DSC) connected with a H₂ detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability (HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.     

Structural evolution and stability of mechanically alloyed Fe-Ni nanocrystalline

The structural evolution and stability of Fe100-xNix(x=10, 20, 35, 50) alloys prepared by mechanical alloying were investigated through X-ray diffraction analysis and transmission electron microscopy. The intrinsic conditions of preparation determining phase stability in nanocrystalline were clarified. After being milled for 120 h, the powders of Fe90Ni10 and Fe80Ni20 consist of a single α(bcc) phase, Fe30Ni30 powders are a single γ(fcc), and for Fe65Ni35 powders there is co-existence of α and γ phases. The as-milled Fe80Ni20 powders annealed at 680 ℃ exhibits the stability of high-temperature γ phase at room temperature, which is consistent with the theoretical prediction.     

Bulk metallic glasses formed by alloying the Cu6Zr5 cluster

The bulk metallic glass formation in the Cu-Zr-M ternary systems by alloying of a binary basic Cu₆Zr₅ cluster was investigated, where M stands for Sn, Mo, Ta, Nb, Ag, Al and Ti. The Cu₆Zr₅ cluster is a capped Archimedean antiprism that characterizes the local structure of the Cu₁₀Zr₇ crystalline phase. This cluster composition almost superposes with Cu-Zr eutectic Cu_0.56Zr_0.44. A series of alloys along the cluster line (Cu₆Zr₅)_1-xM_x were examined for their glass forming abilities. Alloy rods with a diameter of 3 mm were prepared by copper mould suction casting method and analyzed by XRD and thermal analysis. The Cu-Zr based bulk metallic glasses were discovered with minor Nb, Sn, Mo, Ta additions (≤2at%) and Al, Ti, Ag (8at%≤concentration≤9at%). The alloying mechanism was discussed in the light of atomic size, cluster-linking structure and electron concentration factors.     

Crystallization of amorphous Ni-Zr alloys during heating with molecular dynamics simulations

The heating processes of amorphous Ni_xZr_100-x(x=10, 16.7, 33.3) alloys were investigated with molecular dynamics simulations. The simulation results show that the crystallization of amorphous alloys during heating is controlled by the heating rate and the alloy's composition. The slower heating rate depresses the crystallizing temperatures and the melting temperatures of the amorphous alloys. Crystallization can be eliminated at rapid heating rates, the critical value of which decreases with increasing Ni content of the studied amorphous Ni-Zr alloys. Different crystalline structures formed during crystallizing depend on the heating rate, and the transition between crystalline structures was observed in the heating processes.