Properties of Mg-based materials for hydrogen storage

In the presented paper, microstructures of as-cast MgNi_14.0 and MgNi_27.8 alloys are described. The alloys are composed of α(Mg) phase and Mg₂Ni intermetallic (space group P6₂22) of primary and/or eutectic nature. The α(Mg)+Mg₂Ni eutectic is characterized by an asymmetric zone of coupled growth. Primary Mg₂Ni phase shows a branched dendritic morphology and eutectic Mg₂Ni phase forms narrow and interconnected lamellae. The MgNi_27.8 alloy was electrochemically hydrided in 6 M KOH. XRD proved that the hydriding led to a transformation of the Mg₂Ni phase into Mg₂NiH_x (x=0–0.3) solid solution. It was shown that the hydriding rate increased with bath temperature and that the optimum voltage between cathode and anode was 1.5 V. Higher voltages resulted in H₂ evolution which reduced hydriding efficiency. An 1 h hydriding at 90 °C and 1.5 V was able to produce almost 20 μm layer of the Mg₂NiH_0.3 phase. Further hydriding probably led to a formation of Mg₂NiH₄ hydride which retarded the inward diffusion of H.     

Intermetallic compounds as negative electrodes of Ni/MH batteries

This review is devoted to the main families of thermodynamically stable intermetallic compounds (AB₅-, AB₂- and AB-type alloys) that have been researched in the last thirty years as materials for negative electrodes in nickel–metal hydride batteries. The crystal structure of these compounds and their hydrides is widely described. Their solid–gas hydrogenation properties and, particularly, the related desorption isotherm curves are examined as a useful criterion for the selection of suitable battery materials. The electrochemical performances obtained with these alloys are reported and the given solutions to common problems such as corrosion, passivation, decrepitation and short cycle life are discussed. Only AB₅-based compounds have achieved, up to now, enough development for being widely present on the market, and exhibit improved battery performances in comparison with the polluting Ni/Cd batteries. The high capacity of AB₂-based compounds and the remarkable electrochemical activity of some AB-based alloys make, however, further research on all the reviewed families still valuable. Received: 16 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

A method to pattern Pd over-layers on GdMg films and its application to increase the transmittance of metal hydride optical switches

A process to pattern Pd over-layers on reactive metal films was developed using ion milling through a tungsten trioxide mask patterned by photolithography and wet etching. The WO₃ mask exhibited a low Ar⁺ sputter yield and, unlike conventional mask materials (SiO₂, Si₃N₄), was easily etched in a mild alkaline solution. This procedure was applied to convert a 20-nm Pd cap over a 160-nm GdMg film to a Pd grid with ≈9-μm-diameter openings covering ≈40% of the surface. The Pd grid proved sufficient to catalyze the (de)hydriding reactions required to reversibly switch the GdMg film from reflecting to transparent. The maximum transmittance of the patterned Pd/GdMg hydride bi-layer was twice that of an otherwise identical sample with a continuous Pd cap, with similar hydriding kinetics. Received: 2 May 2000 / Accepted: 9 May 2000 / Published online: 13 September 2000     

Catalytic generation of hydrogen by applying fluorinated-metal hydrides as catalysts

Metal–hydrogen complexes such as NaAlH₄, KBH₄, and NaBH₄ are known as high H-content materials. The highly reactive natures of these materials against moist air and water can be easily stabilized in aqueous KOH and NaOH solutions. Accordingly, it is required to develop catalysts suitable for generating hydrogen from the stabilized metal–hydrogen complexes in alkaline solutions. This work is aimed at developing catalysts that can generate hydrogen from such solutions with considerably high kinetics under moderate temperature and pressure conditions. We have found that Mg₂Ni, a typical high-temperature hydriding alloy, exhibits excellent functions as a catalyst for the hydrolysis of BH₄ ^--ion-containing solutions. The fluorination-treatment (F-treatment) effects on granular particles of Mg₂Ni and Mg₂NiH₄ are reported in this paper. Received: 13 November 2000 / Accepted: 14 November 2000 / Published online: 9 February 2001     

Theoretical study of hydrogen dissociation and diffusion on Nb and Ni co-doped Mg(0001): A synergistic effect

The interaction of H₂ with clean, Ni and Nb doped Mg(0001) surface are investigated by first-principles calculations. Individual Ni and Nb atoms within the outermost surface can reduce the dissociation barrier of the hydrogen molecule. They, however, prefers to substitute for the Mg atoms within the second layer, leading to a weaker catalytic effect for the dissociation of H₂, a bottleneck for the hydriding of MgH₂. Interestingly, co-doping of Ni and Nb stabilizes Ni at the first layer, and results in a significant reduction of the dissociation barrier of H₂ on the Mg surface, coupled with an increase of the diffusion barrier of H. Although codoped Ni and Nb shows no remarkable advantage over single Nb here, it implies that the catalytic effect could be optimized by co-doping of “modest” transition metals with balanced barriers for dissociation of H₂ and diffusion of H on Mg surfaces.     

Electrochemical properties of modified negative electrode for Ni-MH cell

This study discusses the influence of different composition of negative electrode material on the performance of Ni-MH cells. Two major groups of multicomponent alloys were used during the experiments: AB₅ and AB₂ types. The best capacity was observed for the AB₅-type alloy with the highest content of Co in its structure. The presence of Co in the alloy increased the capacity of the negative electrode most likely as a result of hydriding/dehydriding processes or Faradaic reaction following the dissolution-precipitation mechanism. The influence of different amounts of nickel (0–20 wt%) was determined. The presence of nickel in the electrode materials increased the current density as well as the diffusion of hydrogen into the bulk of alloys. Moreover, the carbon materials have been used as an additive for negative electrode grains in order to increase the conductivity and hydrogen sorption properties.     

Role of buried ultra thin interlayer silicide on the growth of Ni film on Si(100) substrate

The presence of a buried, ultra-thin amorphous interlayer in the interface of room temperature deposited Ni film with a crystalline Si(100) substrate has been observed using cross sectional transmission electron microscopy (XTEM). The electron density of the interlayer silicide is found to be 2.02 e/?³ by specular X-ray reflectivity (XRR) measurements. X-ray diffraction (XRD) is used to investigate the growth of deposited Ni film on the buried ultra-thin silicide layer. The Ni film is found to be highly textured in an Ni(111) plane. The enthalpy of formation of the Ni/Si system is calculated using Miedema’s model to explain the role of amorphous interlayer silicide on the growth of textured Ni film. The local temperature of the interlayer silicide is calculated using enthalpy of formation and the average heat capacity of Ni and Si. The local temperature is around 1042 K if the interlayer compound is Ni₃Si and the local temperature is 1389 K if the interlayer compound is Ni₂Si. The surface mobility of the further deposited Ni atoms is enhanced due to the local temperature rise of the amorphous interlayer and produced highly textured Ni film. Received: 2 March 2000 / Accepted: 28 March 2000 / Published online: 11 May 2000     

Study of cohesive,electronic and magnetic properties of the Ni–In intermetallic system

Cohesive, electronic and magnetic properties of the intermetallic system Ni–In, specifically the stable phases Ni₃In-hP8, Ni₂In-hP6, NiIn-hP6 and Ni₂In₃-hP5, have been investigated. At present, these materials are of great interest in connection to the application of the In–Sn alloys as lead-free micro-soldering alloys, and considering Ni as the contact material. In spite of this, scarce literature regarding basic thermodynamic properties of the Ni–In intermetallic phases has been found. Full-Potential Linear Augmented Plane Wave method (FP-LAPW) within the framework of the Density Functional Theory (DFT) with exchange and correlation effects in the Generalized Gradient (GGA) and Local Density (LDA) approximations is used. All the calculations include spin polarization. Structural parameters, formation energies and cohesive properties of the different phases are studied through minimization of internal parameters. The electronic density of states (DOS) is analyzed for each optimized structure. We found that the NiIn-hP6 phase is the most stable one and only the Ni₃In-hP8 phase exhibits magnetic properties.     

First Z-scan n2 measurements on crystal hosts for ultraviolet laser systems

We report the results of the first measurements of the non-linear Kerr refractive index, n₂, for LiBaF₃ and LiLuF₄ crystal hosts, known as prospective UV-emitting tunable laser media when doped with Ce³⁺ ions. These n₂ values (2.7×10^-16 and 1.5×10^-16 cm²/W at 532 nm, respectively), obtained using the well-established Z-scan technique, are important for the characterization of new optical materials particularly in relation to their potential ultrafast applications. Received: 6 June 2000 / Published online: 5 October 2000     

Mg3MNi2 (M=A1, Ti) 的晶体结构与电子性能原子模拟研究

利用元素取代Mg2Ni合金的部分Mg后得到Mg3MNi2(M=Al,Ti)合金。计算得到的Mg2Ni和Mg3MNi2(M=Al,Ti)的晶格常数和实验一致,研究了Mg3MNi2(M=A1,Ti)的电子性能和储氢性能的关系,结果表明：Mg2Ni合金中Al和Ti部分取代Mg形成新的合金Mg3MNi2(M=A1,Ti)后,Mg和Al、Ti之间形成共价键。从晶体结构特征和电子性能等方面分析预测了Mg3MNi2 (M=A1,Ti) 合金比Mg2Ni合金具有较低的吸、放氢温度。     

Acid-base properties of Ni-MgO-Al2O3 materials

Ni-MgO-Al₂O₃ materials of different Ni/Mg ratios were prepared by the co-precipitation method. Acid-base properties of the samples after calcination and reduction were examined by the temperature programmed desorption of ammonia and carbon dioxide. Thermal treatment of the materials in air at 400 °C led to the formation of hydrotalcite-like phases. The increase of Ni/Mg ratio decreased the stability of the hydrotalcite structure. The number and the strength of acid and base sites were related to the Ni/Mg ratio and thermal treatment conditions of materials. It was found that the replacement of Ni with Mg decreased the acidity and increased basicity of the surface of oxide materials. Thermal treatment of the samples in hydrogen led to the structural changes. The presence of magnesia improved thermal stability. The ratio of the number of acid to base sites in the reduced samples gradually increased with the increase of magnesia content.     

Unique magnetism observed in single-wall carbon nanohorns

The magnetic properties of single-wall carbon nanohorns (SWNH) were studied by electron spin resonance (ESR) and static magnetic susceptibility measurements. The SWNHs were ESR active with linewidth (ΔH) of ∼6 G in vacuo at room temperature. ΔH was susceptible to the partial pressure of O₂ and became 53 G at 1 atmospheric pressure of O₂, while the integrated ESR intensity was independent on O₂ pressure and behaved as Curie-like, suggesting an intrinsic ESR origin with localized electron spin character. The diamagnetic susceptibility for SWNHs indicated a value smaller than that of randomly oriented graphite by an order of magnitude, but showing a magnitude comparable to those of C₆₀ and C₇₀. It is suggested that the large diamagnetism expecting for sp² networked carbon materials will be canceled by the Van Vleck constant paramagnetism. Received: 20 November 2000 / Accepted: 21 November 2000 / Published online: 25 July 2001     

Ab-initio investigation of electronic properties and magnetism of half-Heusler alloys XCrAl (X=Fe, Co, Ni) and NiCrZ (Z=Al, Ga, In)

The electronic structures and magnetism of the half-Heusler alloys XCrAl (X=Fe, Co, Ni) and NiCrZ (Z=Al, Ga, In) have been investigated to search for new candidate half-metallic materials. Here, we predict that NiCrAl, and NiCrGa and NiCrIn are possible half-metals with an energy gap in the minority spin and a completely spin polarization at the Fermi level. The energy gap can be attributed to the covalent hybridization between the d states of the Ni and Cr atoms, which leads to the formation of bonding and antibonding peaks with a gap in between them. Their total magnetic moments are 1μ_B per unit cell; agree with the Slater-Pauling rule. The partial moment of Cr is largest in NiCrZ alloys and moments of Ni and Al are in antiferromagnetic alignment with Cr. Meanwhile, it is also found that FeCrAl is a normal ferromagnetic metal with a magnetic moment of 0.25μ_B per unit cell and CoCrAl is a semi-metal and non-magnetic.     

Mechanically alloyed metal hydride systems

Mechanosynthesis of metal hydrides is a new field in which important progress has been reported. In this paper, we present recent developments in mechanosynthesis of magnesium-based hydrides for storage applications. The effect of intense milling on magnesium and magnesium hydrides is presented. The influence of various additives on hydrogen-sorption properties is discussed with special emphasis on nanocomposite MgH₂+5 at. % V, where hydrogen-storage characteristics, cycling properties and the mechanism of hydrogen desorption are presented. The production of novel nanocrystalline porous structures by mechanical alloying followed by a leaching technique is discussed. Hot ball-milling, as a new method for rapid synthesis of alloys, is also presented. Finally, two other methods of production of metal hydrides are discussed. One is reactive milling where metal hydrides are synthesized by mechanical alloying under hydrogen pressure, while the other is milling elemental hydrides to produce complex hydrides. Received: 15 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Soft magnetic properties of NiFe compacted powder alloys

It is known that Ni–Fe based alloys (permalloys) are important soft magnetic materials, which have been widely applied in the field of electronic devices and industry. The most suitable permalloys for application exhibit low value of coercivity and magnetostriction (for about 80 at% Ni), high saturation magnetic induction (for about 50 at% Ni), higher electrical resistivity (for about 35 at% Ni). The aim of this work was to investigate the structure and magnetic properties of _Ni81Fe19${\mathrm{Ni}}_{81}{\mathrm{Fe}}_{19}$ (wt%) compacted powder material in the form of small cylinders.     

Dielectric and acoustic properties of the family of new lead-free materials with the general formula BiMe 2/3Sb1/3O3 (Me = Mg, Ni, Co, Zn)

A family of new lead-free materials with the general formula BiMe _2/3Sb_1/3O₃ (Me = Mg, Ni, Co, Zn) have been synthesized using the standard ceramic technology. The temperature dependences of the permittivity ??? have been studied at frequencies from 0.5 to 1000 kHz in the temperature range from 300 to 800 K. At high temperatures, the permittivity ??? of the Ni-, Mg-, Co-, and Zn-containing materials has been found to exhibit maxima (at 765, 768, 748, and 780 K, respectively) related to structural phase transitions, which has been confirmed by the measurements of the elastic, inelastic, and thermal properties.     

Deposition of duplex Al2O3/aluminum coatings on steel using a combined technique of arc spraying and plasma electrolytic oxidation

Plasma electrolytic oxidation (PEO) is a cost-effective technique that can be used to prepare ceramic coatings on metals such as Ti, Al, Mg, Nb, etc., and their alloys, but this promising technique cannot be used to modify the surface properties of steels, which are the most widely used materials in engineering. In order to prepare metallurgically bonded ceramic coatings on steels, a combined technique of arc spraying and plasma electrolytic oxidation (PEO) was adopted. In this work, metallurgically bonded ceramic coatings on steels were obtained using this method. We firstly prepared aluminum coatings on steels by arc spraying, and then obtained the metallurgically bonded ceramic coatings on aluminum coatings by PEO. The characteristics of duplex coatings were analyzed by X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The corrosion and wear resistance of the ceramic coatings were also studied. The results show that, duplex Al₂O₃/aluminum coatings have been deposited on steel substrate after the combined treatment. The ceramic coatings are mainly composed of α-Al₂O₃, γ-Al₂O₃, θ-Al₂O₃ and some amorphous phase. The duplex coatings show favorable corrosion and wear resistance properties. The investigations indicate that the combination of arc spraying and plasma electrolytic oxidation proves a promising technique for surface modification of steels for protective purposes.     

Fe和Co元素在铁磁性形状记忆合金Mn50Ni25－xFe(Co)xGa25中的作用

为了进一步改善材料的性能和探索新的材料，将Mn₂NiGa合金中的Ni元素分别用Fe和Co替代，制备了Mn₅₀Ni_25-xFe(Co)_xGa₂₅系列合金. 研究了Fe和Co元素对Mn₂NiGa合金的结构、马氏体相变行为、磁性和机械性能等方面的影响. 关键词： 铁磁形状记忆合金 Heusler合金 50Ni_25-xFe(Co)_xGa₂₅')" href="#">Mn₅₀Ni_25-xFe(Co)_xGa₂₅     

Solid-state synthesis and phase transformations in Ni/Fe films: Structural and magnetic studies

We have used X-ray diffraction, volume magnetocrystalline anisotropy constant and resistance measurements to study solid-state synthesis in Ni(0 0 1)/Fe(0 0 1), Ni/Fe(0 0 1) and Ni/Fe thin films with the atomic ratio between Fe and Ni of 1:1 (1Fe:1Ni), and 3:1 (3Fe:1Ni). We have found that the formation of Ni₃Fe and NiFe phases in the 1Fe:1Ni films takes place at temperatures ∼620 and ∼720 K, correspondingly. In the case of the 3Fe:1Ni films the solid-state synthesis starts with Ni₃Fe and NiFe phase formation at the same temperatures as for the 1Fe:1Ni films. The increasing of annealing temperature above 820 K leads to the nucleation of a paramagnetic γ_par phase at the FeNi/Fe interface. The final products of solid-state synthesis in the Ni(0 0 1)/Fe(0 0 1) thin films are crystallites which consist of the epitaxially intergrown NiFe and γ_par phases according to the [1 0 0](0 0 1)NiFe||[1 0 0](0 0 1)γ_par orientation relationship. The crystalline perfection and epitaxial growth of the (NiFe+γ_par) crystallites on the MgO(0 0 1) surface allow to distinguish (0 0 2)γ_par and (0 0 2)NiFe X-ray peaks (the cell parameters are: a(γ_par)=0.3600±0.0005 nm and a(NiFe)=0.3578±0.0005 nm, correspondingly). At low temperatures the paramagnetic γ_par phase undergoes the martensite _γpar→α^′${\gamma }_{\mathrm{par}}\to {\alpha }^{\prime }$ phase transition which can be hindered by thermal and epitaxial strains and epitaxial clamping with a MgO substrate. On the basis of the studies of the thin-film solid-state synthesis we predict the existence of two novel structural phase transformations at the temperatures of about 720 and 820 K for alloys of the invar region of the Fe–Ni system.     

Influence of Al3Ni crystallisation origin particles on hot deformation behaviour of aluminium based alloys

Abstract

Binary Al–Ni, Al–Mg and ternary Al–Mg–Ni alloys containing various dispersions and volume fraction of second-phase particles of crystallisation origin were compressed in a temperature range of 200–500 °C and at strain rates of 0.1, 1, 10, 30 s^?1 using the Gleeble 3800 thermomechanical simulator. Verification of axisymmetric compression tests was made by finite-element modelling. Constitutive models of hot deformation were constructed and effective activation energy of hot deformation was determined. It was found that the flow stress is lowered by decreasing the Al₃Ni particle size in case of a low 0.03 volume fraction of particles in binary Al–Ni alloys. Intensive softening at large strains was achieved in the alloy with a 0.1 volume fraction of fine Al₃Ni particles. Microstructure investigations confirmed that softening is a result of the dynamic restoration processes which were accelerated by fine particles. In contrast, the size of the particles had no influence on the flow stress of ternary Al–Mg–Ni alloy due to significant work hardening of the aluminium solid solution. Atoms of Mg in the aluminium solid solution significantly affect the deformation process and lead to the growth of the effective activation energy from 130–150 kJ/mol in the binary Al–Ni alloys to 170–190 kJ/mol in the ternary Al–Mg–Ni alloy.