Phases and reactive-diffusion kinetics for mixed Al-Ni powders

Reactive diffusion has been examined for mixtures of nickel and aluminum powders and also Ni-Al bimetal. An intermediate layer is formed at the boundary between particles, and the phase sequence in this in the direction from nickel to aluminum is NiAl-Ni₂Al₃-NiAl₃. The growth of this intermediate layer under isothermal conditions obeys the law xⁿ=gk(t–t₀), with n=3 for a mixture of the powders and n=2 for the bimetal. The energies of formation for the compounds NiAl, Ni₂Al₃, NiAl₃ are large, so the reactive diffusion in the powder mixtures is accompanied by considerable exothermic effects.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 34–40, November, 1973.     

A phase-field study of the aluminizing of nickel

A quantitative phase-field approach for multiphase systems that is based upon CALPHAD free energies is used to model the aluminization of nickel wires, wherein vapour-phase alloying is used to deposit Al on the surface of the Ni wire and then the wire is annealed so that to remove all Al gradients and achieve a homogenous Ni-Al alloy. Both processes are modelled and numerical results are compared with experiments. It is found that the kinetics of both processes is controlled by bulk diffusion. During aluminization at 1273 K, formation and growth of intermetallics, Ni₂Al₃ NiAl and Ni₃Al, are strongly dependent on the Al content in the vapour phase. Ni₂Al₃ growth is very fast compared with NiAl and Ni₃Al. It is also found that an intermediate Al content in the vapour phase is preferable for aluminization, since the Ni₂Al₃ coating thickness is difficult to control. Ni₂Al₃ is found to disappear in a few minutes during homogenization at 1373 K. Thereafter, the NiAl phase, in which the composition is highly non-uniform after aluminization, continues growing until the supersaturation in this phase vanishes. Then, NiAl coating disappears concomitantly with the growth of Ni₃Al, which disappears thereafter. Finally, the Al concentration profile in Ni(Al) homogenizes.     

Structural evolution of electroless Ni-P coating on Al-12 wt.% Si alloy during heat treatment at high temperatures

The work is concerned with the high-temperature heat treatment of an Al-12 wt.% Si alloy coated by an electroless Ni-P layer. The electroless deposition took place on a pre-treated substrate in a bath containing nickel hypophosphite, nickel lactate and lactic acid. Resulting Ni-P deposit showed a thickness of about 8 μm. The coated samples were heat-treated at 200-550 °C/1-24 h. LM, SEM, EDS and XRD were used to investigate phase transformations. Adherence to the substrate was estimated from the scratch test and microhardness of the heat-treated layers was also measured. It is found that various phase transformations occur, as both temperature and annealing time increase. These include (1) amorphous Ni-P → Ni + Ni₃P, (2) Al + Ni → Al₃Ni, (3) Ni₃P → Ni₁₂P₅ + Ni, (4) Ni₁₂P₅ → Ni₂P + Ni, and (5) Al₃Ni + Ni → Al₃Ni₂. The formation of intermetallic phases, particularly Al₃Ni₂, leads to significant surface hardening, however, too thick layers of intermetallics reduce the adherence to the substrate. Based on the growth kinetics of the intermetallic phases, diffusion coefficients of Ni in Al₃Ni and Al₃Ni₂ at 450-550 °C are estimated as follows: D(Al₃Ni, 450 °C) ≈ 6 × 10⁻¹² cm² s⁻¹, D(Al₃Ni, 550 °C) ≈ 4 × 10⁻¹¹ cm² s⁻¹, D(Al₃Ni₂, 450 °C) ≈ 1 × 10⁻¹² cm² s⁻¹ and D(Al₃Ni₂, 550 °C) ≈ 1 × 10⁻¹¹ cm² s⁻¹. Mechanisms of phase transformations are discussed in relation to the elemental diffusion.     

Segregation of Solutes in Two-Phase Mixtures

Fractions of indium solutes in each phase of a mixture of two binary phases were measured using perturbed angular correlation of gamma rays. Measurements of phase fractions were made on Pd₃Ga₇–PdGa, PdGa–Pd₅Ga₃, and FeAl₂–FeAl mixtures as a function of composition. The phase fractions were analyzed using a thermodynamic model that takes into account differences between energies of solute atoms in the two phases. From the model, segregation coefficients were obtained for the systems studied. Also, earlier measurements on Ni₂Al₃–NiAl were reanalyzed. Large differences are found among the segregation coefficients. This revised version was published online in September 2006 with corrections to the Cover Date.     

Eco-friendly combustion-based synthesis of metal aluminates MAl<Subscript>2</Subscript>O<Subscript>4</Subscript> (M = Ni,Co)

Nanosized metal aluminates, MAl₂O₄ (M = Ni, Co), have been prepared following a nonpolluting, low temperature, and self-sustaining starch single-fuel combustion synthesis. The mixed fuel-coordinating actions of starch have given rise to an intermediary precursor which afforded monodisperse metal aluminate nanoparticles. The thermal analysis of the [M(II), Al(III)]-starch precursors indicates a similar thermochemical reactivity for the two compounds, displaying a sequence of well-defined decomposition stages associated with three endothermic effects and three/four (nickel/cobalt) exothermic ones. The XRD data confirm the formation of spinelic phase and a continuous growth of particle sizes with the increase of calcination temperatures. The mechanisms proposed for the formation of metal aluminates essentially consist in a combination of solid-state reactions of amorphous NiO/Co₃O₄ and Al₂O₃ simple oxides. The evaluation criterion of Ni(II) cations into the spinelic lattice is original and is based on the distinct occupancy degree of tetrahedral and octahedral sites in NiAl₂O₄ and γ-Al₂O₃. TEM/HRTEM investigations performed on the cobalt(II) and nickel(II) aluminate oxide powders resulted after calcination at 800 and 900 °C, respectively, for 1 h show the formation of irregular and isolated plate-like particles for Co(II)-based spinelic oxides (the average particle size is 16.6 nm) and submicron aggregates of small, bimodal, and almost uniform (as shape and size) of NiAl₂O₄ mixed oxide (the mean particle size is 33.6 nm). The NIR–UV–Vis spectra for the resulted MAl₂O₄ (M = Co, Ni) mixed oxides reveal a massive presence of tetrahedral divalent cations both for short- and long-time calcined samples. NiO impurities are detected using FTIR and electronic spectra for all NiAl₂O₄ samples.     

Effects of Interface Structures on the Application Properties of Ni/Al Clad Composite

The Ni/Al clad metal composite can be applied for the ultrasonic welding of nickel and aluminum structures for lithium-ion cell packaging. The roll bonding Ni/Al clad sheets with 0.15 mm thickness were produced and the effects of interface microstructures and phase transformation on the application properties of such composites are studied in this investigation. The results show that the interface of Ni and Al forms a jagged, interlocking pattern at the rolling state but not a metallurgical bonding. During the annealing process, the first formed Al₃Ni phase in the interface of Ni and Al is beneficial to their bonding together but the sequently formed Al₃Ni₂ phase results in the formation of cracks and the separation of the Ni/Al layers. The bonding mechanism changes to metallurgical bonding with the formation of such phases. The Ni/Al clad sheet acquires good bending endurance, stable welding strength and suitable electrical resistivity with annealing from 425 to 475°C for 1 h.     

Structural Phase Transformations in Al/Pt Bilayer Thin Films during the Solid-State Reaction

A sequence of phases forming during the solid-phase reaction in Al/Pt bilayer thin films has been investigated by in situ electron diffraction. It is shown that the amorphous PtAl₂ phase forms first during the solid-phase reaction initiated by heating. Upon further heating, PtAl₂, Pt₂Al₃, PtAl, and Pt₃Al crystalline phases sequentially form, which is qualitatively consistent with an effective formation heat model. The content of phases forming during the reaction has been quantitatively analyzed and the structural phase transformations have been examined.

     

X-ray photoelectron spectroscopic studies on oxidation behavior of nickel and iron aluminides under oxygen atmosphere at low pressures

Oxidation behaviors of NiAl, Ni₃Al, and FeAl under oxygen atmosphere at low pressures were studied by X-ray photoelectron spectroscopy (XPS). Clean surfaces of these aluminides were prepared by fracturing in an ultra high vacuum, and then the fractured surfaces were oxidized by exposing to high-purity oxygen at pressures up to 1.3 Pa without exposing to air. The oxides formed on NiAl and FeAl surfaces were Al₂O₃, whereas the oxide on Ni₃Al was NiAl₂O₄. Aluminum, nickel, and iron on clean surfaces were oxidized even at a pressure of 1.3 × 10⁻⁶ Pa. The oxidation evolves with an increase in the pressure of oxygen, and further oxidation of aluminum occurs prior to that of nickel or iron. The oxidation behaviors under such oxygen atmosphere were similar to those of the aluminides oxidized in air, and these behaviors could be predicted from thermodynamic consideration.     

Structural state and phase composition of nickel surface layers modified by high-intensity implantation of titanium ions

This paper reports on the results of experimental investigations into the microstructure and the elemental and phase compositions of ion-alloyed nickel surface layers modified by high-intensity implantation of titanium ions. It is established that the implantation of titanium ions into nickel surface layers up to 1600 nm thick leads to the formation of intermetallic phases (namely, NiTi, Ni₃Ti, and NiTi₂), a solid solution of titanium in nickel, titanium oxides of different stoichiometries, and titanium carbide TiC. It is demonstrated that the phases formed in the ion-alloyed nickel surface layers have a nanocrystalline structure. The average size of the nanocrystal grains is equal to 40 nm.     

Lithium nickel oxide Li(Ni0.75Al0.17Co0.08)O2 as cathode material for lithium ion batteries

Al- and Co-substituted lithium nickel oxide of the nominal composition Li(Ni_0.75Al_0.17Co_0.08)O₂ was synthesised by a coprecipitation technique and by several solid state routes. Rietveld analysis of XRD profiles and galvanostatic cycling in glass cells were performed for structural and electrochemical characterisation. Depending on the reactivity of the respective precursor, there is in each case a minimal synthesis temperature, at which a single phase of the R layered structure could be obtained. The coprecipitation technique and solid state routes using pre-substituted nickel hydroxide are suitable for the synthesis of single phase Al- and Co-substituted lithium nickel oxide, even at rather low synthesis temperatures. The electrochemical performance of lithium nickel oxide Li(Ni_0.75Al_0.17Co_0.08)O₂ synthesised in air is poor due to an enhanced lithium nickel disorder. Synthesis in oxygen atmosphere seems to be required. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Behaviour and phase transformations of nickel sulphide inclusions in glass melts

Nickel sulphide inclusions with the NiS composition can cause spontaneous failure of thermally toughened glass. During annealing a phase transformation from high to low-temperature phase takes place, which has a higher volume. This phase transformation, which is very slow at room temperature, generates internal stress in the glass, and after some months up to several years spontaneous fracture can occur. To obtain more information about the nickel sulphide behaviour, NiS and Ni₃S₂ were prepared and investigated in melts of different glass types at various temperatures and melting times. Analysis of the nickel sulphides was done before and after treatment in the melts. Knowing that additives modify the thermodynamics and kinetics of dissolution behaviour, experiments were carried out with 5 mol% Fe or 5 mol% Sn added to Ni₃S₂. The oxidation of the intermediate phases (Ni,Fe)₉S₈ and Ni₃Sn₂S₂ was preferred over the oxidation of the pure nickel sulphides. Additionally, the possible forming process of nickel sulphide in glass was tested. The normally formed phase was Ni₃S₂, but some additional complex metallic phases were also found, depending on the glass type.     

Effects of laser power density on the microstructure and microhardness of Ni–Al alloyed layer by pulsed laser irradiation

Laser alloying of Ni–P electroless deposited layer with aluminum substrate was carried out by Nd–YAG pulsed laser. The phase composition and microstructure of the alloyed layers produced by different laser power densities were identified by X-ray diffractionary (XRD), scanning electron microscope (SEM) accompanied by energy dispersion X-ray analysis (EDS) and transmission electron microscope (TEM). Furthermore, the surface roughness of the alloyed layers was characterised by confocal laser scanning microscope (CLSM). The results showed that the characteristic dendritic or lamellar microstructures were observed in the alloyed layers. The phase constituents of the alloyed zones were intermetallic compounds of nickel–aluminum NiAl, Al₃Ni and Al₃Ni₂, as well as some non-equilibrium phases and amorphous phases depending on the employed laser power density. As a result, the microhardness of the alloyed layer with Ni–P amorphous phases formed at laser power density 5.36×10⁹ W/m² reached to HV_0.1 390.     

Local melting/solidification during peritectic solidification in a steep temperature gradient: analysis of a directionally solidified Al–25at%Ni

Melting of primary Al₃Ni₂ phase and solidification of Al₃Ni peritectic phase during directional solidification of an Al–25at%Ni peritectic alloy have been investigated. In a steep temperature gradient of up to 50 K/mm and at a pulling rate of 20 μm/s, an incomplete coverage of peritectic Al₃Ni phase on the surface of the primary Al₃Ni₂ phase has been observed. Below the peritectic temperature in the presence of the incomplete coverage, melting of primary Al₃Ni₂ on the one side and solidification to the Al₃Ni peritectic phase on the other side proceed swiftly via diffusion through the interphase liquid layer. Theoretical calculations based on an incomplete-coverage-related melting/solidification model are in close agreement with the experimental measurements.     

Crystallization kinetics of Al<Subscript>86</Subscript>Ni<Subscript>8</Subscript>Ho<Subscript>6</Subscript> amorphous alloy

We investigate the processes of crystallization and determined the structure and thermal properties of Al₈₆Ni₈Ho₆ amorphous alloy in a wide temperature range. A three-stage nature of the crystallization process upon heating to a temperature of 700 K is found. According to data of high-temperature X-ray diffraction analysis, the crystallization of an Al₈₆Ni₈Ho₆ amorphous ribbon is rather complex: aluminum crystallites grow in the amorphous phase to a temperature of 470 K, a Ho₃Ni₅Al₁₉ phase is formed above 563 K, and a HoAl₃ phase appears above 598 K. The phases of Ho₃Ni₅Al₁₉ and HoAl₃ are retained up to a temperature of 723 K. A three-stage kinetic model of the crystallization process with the reaction sequence is proposed based on calculations by multivariate nonlinear regression. The values of the total activation energy for each crystallization stage reach 239, 378, and 247 kJ/mol.     

Nanocrystal formation in gas-atomized amorphous Al85Ni10La5 alloy

An Al₈₅Ni₁₀La₅ amorphous alloy, produced via gas atomization, was selected to study the mechanisms of nanocrystallization induced by thermal exposure. High resolution transmission electron microscopy results indicated the presence of quenched-in Al nuclei in the amorphous matrix of the atomized powder. However, a eutectic-like reaction, which involved the formation of the Al, Al₁₁La₃, and Al₃Ni phases, was recorded in the first crystallization event (263°C) during differential scanning calorimetry continuous heating. Isothermal annealing experiments conducted below 263°C revealed that the formation of single fcc-Al phase occurred at 235°C. At higher temperatures, growth of the Al crystals occurred with formation of intermetallic phases, leading to a eutectic-like transformation behaviour at 263°C. During the first crystallization stage, nanocrystals were developed in the size range of 5 ～ 30 nm. During the second crystallization event (283°C), a bimodal size distribution of nanocrystals was formed with the smaller size in the range of around 10 ～ 30 nm and the larger size around 100 nm. The influence of pre-existing quenched-in Al nuclei on the microstructural evolution in the amorphous Al₈₅Ni₁₀La₅ alloy is discussed and the effect of the microstructural evolution on the hardening behaviour is described in detail.     

Investigation of the thermoelastic phase transformation in a NiAl alloy by molecular dynamics simulation

The Ni_xAl_1−x alloys exhibit shape memory effect, for which thermoelastic phase transformations are essential, in the composition range of 60<x<65. The analytical studies are very difficult on the thermoelastic phase transformations because these types of transformations exhibit anharmonic behaviour. In order to overcome this difficulty, it is possible to benefit from the molecular dynamics (MD) calculations based on interatomic interaction potentials. In the present study, the interatomic interactions of Ni_62.5Al_37.5 alloy have been modelled by means of Lennard-Jones potential energy function. A MD cell of 1024 atoms in B2 super lattice has been chosen and the structural changes were investigated on this system with changing temperature. It has been observed that the model alloy exhibits the thermoelastic phase transformation with thermal cycling. A hysteresis has been determined between forward and backward transformation temperatures. The structural analysis is also done before and after the transformation.     

High-temperature superelasticity in CoNiGa,CoNiAl, NiFeGa,and TiNi monocrystals

The influence of the crystal orientation on the thermoelastic martensitic transformations developing under load was investigated for Co₄₉Ni₂₁Ga₃₀, Co₄₀Ni₃₃Al₂₇, Co₃₅Ni₃₅Al₃₀, Ni₅₄Fe₁₉Ga₂₇, and Ti_49.4Ni_50.6 (аt. %) monocrystals. It has been shown that the superelastic temperature range depends on the crystal orientation and reaches a maximum for [001]-oriented crystals. In monophase crystals of Co₄₉Ni₂₁Ga₃₀, Co₄₀Ni₃₃Al₂₇, Co₃₅Ni₃₅Al₃₀, and Ni₅₄Fe₁₉Ga₂₇ (at. %), segregation of dispersion particles takes place at test temperatures T > 623 K. A criterion for high-temperature superelasticity has been proposed which implies the attainment of high strength of the high-temperature phase due to a proper choice of the crystal orientation, deviation from stoichiometry, and segregation of dispersion particles. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10. pp. 19–37. October, 2008.     

MICROSTRUCTURE AT THE INTERFACE OF TITANIUM CARBIDE AND NICKEL ALUMINIDES

Microstructure at the interface of titanium carbide and nickel aluminides in the samples obtained by infiltration of molten Ni₃Al alloy has studied by a scanning electron microscopy (SEM) and an analytical transmission electron microscopy (ATEM) with an energy dispersive spectrometer (EDS). It is found that the morphology at the interfaces between hard phase skeleton of TiC_0.7 and metallic phases depends on the ratio of Ti/C in carbide. Some periodic zigzag fringes are observed at a smooth interface between metallic phase and carbides in the sample of Ni₃Al/TiC_0.7. The results of analysis using EDS show that Ti in TiC_0.7 carbide is easier than that in TiC_0.7 to dissolve into the molten alloy during solid-liquid reaction. The formation of this periodic zigzag fringe,which may be a growth zone of a new Ti-Ni-Al phase,in the interface of TiC_0.7/Ni₃Al would occur during the initial stage of solidification.