Formation of metastable solid solutions of boron in nickel under mechanochemical synthesis from Ni-B and Ni-Nb-B mixtures

Using high-energy ball milling of Ni₈₇B₁₃ and Ni_{87 ? x} Nb _x B₁₃ component mixtures (x = 7, 10, 12, 14) for 2 h, nanocrystalline alloys containing fcc solid solutions of Ni〈B〉 and Ni〈Nb,B〉 were obtained. According to the results of X-ray analysis, oversaturated solid solutions of Ni〈B〉 are interstitial solutions; those of Ni〈Nb,B〉 are substitutional solutions or mixed substitutional-interstitial solutions. Upon heating of the alloys, exothermal effects appear on differential scanning calorimetry (DSC) curves; they are attributed to decomposition of metastable solid solutions and to crystallization of the amorphous phase appearing in mechanical alloying. After heating to 720°C, the Ni₈₇B₁₃ alloy contained stable phases of Ni and Ni₃B; the Ni₇₅Nb₁₂B₁₃ alloy contained a τ phase (Ni₂₁Nb₂B₆) and a metastable solid solution of Ni〈Nb〉.     

Metastable phase accompanying crystallisation of amorphous Al85Ni10Ce5 alloy

Abstract

Isochronal annealing and isothermal annealing of melt spun amorphous Al₈₅Ni₁₀Ce₅ alloy were carried out to investigate the crystallisation behaviour. It has been found that a metastable phase occurring in the crystallisation process, may exist for a certain time but in due course disappears either acting as a nucleus of another phase or transforming into another stable phase with an increase in either annealing temperature or annealing time. Transmission electron microscopy results reveal that Al₃Ce may be one of the metastable phases during the isochronal annealing process. Furthermore, microhardness measurements reveal that the specimens containing metastable phases exhibit higher microhardness than the as quenched and as crystallised alloy.     

Structure, mechanical properties and electrical resistivity of rapidly solidified Pb-Sn-Cd and Pb-Bi-Sn-Cd alloys

A series of Pb-Sn-Cd alloys containing up to 60 wt % Bi were quenched from the melt to room temperature by melt spinning. The structure of rapidly solidified (melt spun), Pb-30 wt % Sn-10 wt % Cd, Pb-30 wt % Bi-20 wt % Sn-10 wt % Cd, and Pb-60 wt % Bi-10 wt % Sn-10 wt % Cd have been investigated by means of an X-ray diffraction technique. From X-ray analysis a crystalline metastable phase, designated (Pb-Bi) is detected. The formation of a metastable crystalline phase in the range of composition investigated causes a pronounced increase in the electrical resistivity. Desirable values of hardness and elastic constants are critically evaluated. It is also observed that the values of the Fermi energy are a few electron volts. Calculated values for the concentration of the conduction electrons, N, m_-3 of Pb -60 wt % Bi-10 wt % Sn-10 wt % Cd rapidly solidified is found to be 0.985×10₂₈ m_-3.     

Metastable phases in the Ni<Subscript>75</Subscript>Nb<Subscript>12</Subscript>B<Subscript>13</Subscript> alloy prepared under nonequilibrium conditions

The structure of Ni₇₅Nb₁₂B₁₃ alloys prepared by liquid quenching (LQ) and mechanical alloying (MA) has been studied by x-ray diffraction. The alloy prepared by LQ at a cooling rate of ～10⁶ K/s is shown to be fully amorphous, while MA yields an amorphous-crystalline material in which the predominant phase is an fcc Ni〈Nb,B〉 solid solution. The thermal stability of the alloys and their structural transformations on heating have been studied by differential scanning calorimetry. The amorphous phase obtained by LQ is shown to crystallize at 490°C. After heating to 720°C, the alloy consists of two equilibrium phases: Ni₂₁Nb₂B₆ (τ) and Ni₅Nb₃B₂ (z). Heating the MA alloy to 720°C leads to the formation of a stable τ-phase, while the Ni-based fcc solid solution remains supersaturated and, hence, metastable. Increasing the milling time leads to the formation of nanocrystalline τ and Ni₃B phases, in addition to the Ni-based fcc solid solution, which corresponds to the equilibrium phase composition of the Ni₇₅Nb₁₂B₁₃ alloy in the Ni-Nb-B phase diagram. The effect of high-energy milling on the phase composition of the alloy is similar to that of heat treatment.     

Structural evolution and magnetic properties of mechanically alloyed metastable Fe–Ni–Zr–B system

Present investigation focuses on synthesizing metastable Fe₅₂Ni₂₆B₁₈Zr₄ (at.%) soft magnetic material through mechanical alloying. Mechanical alloying was employed to achieve nanocrystalline phase under optimized milling parameters such as milling speed, milling time, composition, etc. The effects of milling time on structural evolution and magnetic properties of Fe₅₂Ni₂₆B₁₈Zr₄ powders were analyzed using x-ray diffraction (XRD), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). Nano crystallization was achieved during the early stages of milling. The crystallite size of Fe₅₂Ni₂₆B₁₈Zr₄ was decreased with increasing milling time. The minimum grain size was found to be about 6 nm. The appreciable magnetic softening, in terms of coercivity values, observed as the milling progresses in amorphous phase at 25 h milling.     

Decomposition behaviour of rapidly quenched Al–Nb alloys– TEM study

Abstract

Two binary Al-rich Al–Nb alloys containing 4·5 and 7·7 wt-%Nb have been rapidly quenched from the liquid state using the ‘gun’ technique. Transmission electron microscopy and diffraction techniques have been extensively employed to characterize the as quenched as well as externally heat treated alloy foils. Each alloy in the as-quenched state shows only a supersaturated solid solution, indicating a substantial increase in the solid solubility limit of Nb in Al by rapid quenching. Elongated solid solution grains and defect structures have also been observed in the as-quenched foils. While no precipitation was found to occur on annealing the quenched dilute alloy (Al–4·5Nb) foils for 1 h at 673 K, precipitation along grain boundaries was observed in the concentrated alloy (Al–7·7Nb). Higher temperature annealing (≥773 K) resulted in the formation of a new metastable phase having an ordered fcc GeCa₇ type structure with a lattice parameter a ~ 0·8 nm. This phase forms predominantly with a rodlike morphology and is arranged in a Widmanstätten pattern inside the grains, although fine precipitate particles have also been observed. On prolonged annealing at or above 773 K, the metastable phase transforms with the formation of the equilibrium tetragonal Al₃Nb phase.

MST/391     

Metastable phase formation in rapidly solidified Al–Mo alloys

Abstract

In Al-Mo alloys, rapidly quenched from the melt at rates of approximately 10⁶ KS^?1, it has been demonstrated that single phase solid solution alloys can be obtained in materials with up to 1·3 at.-%Mo. Above this concentration, two new metastable phases are observed in the form of small precipitates within the matrix of aluminium-rich solid solution. These have been identified as a diamond cubic phase, space group Fd3m, a =1·4–1·5 nm and a hexagonal phase, space group P6/mmm or P6/mmc, a = 0·45 nm, c = 0·27 nm. The maximum supersaturation of the solid solution matrix, obtained in alloys containing such precipitates, was found to be 2·45 at.-%Mo. Upon annealing, both the solid solutions and the metastable intermediate phases decompose directly to the equilibrium structure of aluminium-rich solid solution and Al₁₂Mo. The Al₁₂Mo forms either as precipitates on the grain boundaries or as a layer around the metastable intermediate phases. From a good correlation between the maximum supersaturation obtained and that predicted by consideration of thermodynamic and kinetic factors it is suggested that a similar theoretical treatment may be used to provide an indication of the maximum supersaturation achievable in other systems.

MST/824     

Role of aluminium addition on structure of Fe substituted Fe73·5 − x Si13·5B9Nb3Cu1Al x alloy ribbons

The investigation has dealt with the structure and magnetic properties of rapidly solidified and annealed Fe_73·5???x Si_13·5B₉Nb₃Cu₁Al _x (x?=?0, 2, 4, 6 at%) ribbons prepared by melt spinning. Complete amorphous structure was obtained in as-spun ribbons of x?=?0 and 2 at% compositions, whereas structure of ribbons containing higher Al was found to be partially crystalline. Detailed thermal analyses of the alloys and the melt spun ribbons revealed that the glass forming ability in the form of ${{ \textit{T}}}_{\mathbf{x}}{/}{{ \textit{T}}}_{\mathbf{l}}$ (ratio between crystallization and liquidus temperature) is the highest for 2 at% Al alloys and decreases with further addition of Al. Annealing of all as spun ribbons resulted in the precipitation of nanocrystalline phase embedded in amorphous matrix in the form of either ${ \textit{DO}}_{{ 3}}$ phase or bcc ${\upalpha}$ -Fe(Si/Al) solid solution depending on the initial composition of the alloy. Only bcc ${\upalpha}$ -Fe(Si/Al) solid solution was formed in 2 at% Al ribbons whereas ordered DO₃ structure was found to be stabilized in other ribbons including 0 at% Al. A detailed study on determination of precision lattice parameter of nanocrystalline phase revealed that the lattice parameter increases with the addition of Al indicating the partitioning behaviour of Al in nanocrystalline phase.     

A metastable phase Al3Cu2

A new metastable intermediate phase having a trigonal unit cell belonging to the space groupP¯3ml has been detected in a rapidly solidified aluminium-45 at. % copper alloy. The unit cell dimensions area=4.106 andc=5.094 å. With five atoms per unit cell, the observed structure can be regarded as an isotype of Al₃Ni₂.     

Characterization of Al-Si-alloys rapidly quenched from the melt

Aluminium-silicon alloys with compositions in the range 0 at% to 33.9 at % Si were rapidly quenched from the melt at cooling rates between 10⁶ and 10⁷ K sec^–1 using the melt-spinning technique. The resulting ribbons were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and X-ray diffraction methods. Metastable solid solubilities of silicon in aluminium were determined from lattice parameter and DSC data. The values found were strongly dependent on specimen thickness and a maximum of about 5 at % Si was reached for an alloy composition of 15 at % Sl (maximal equilibrium solid solubility of silicon in aluminium is 1.58 at % Si). Discrepancies between published values of metastable silicon solid solubities were related to the interpretation of the lattice parameter data. Alloy composition was shown to determine the lattice parameter of the silicon-rich phase. The crystallite sizes and the lattice distortions in the aluminium-rich and silicon-rich phases were determined by X-ray diffraction line profile analysis. From the aluminiumrich phase only strain broadening was observed whereas the silicon-rich phase gave rise to both size and strain broadening. The origin of the lattice strains was discussed. Changes in solidification behaviour are reflected in the structure parameters measured.     

Microstructures and crystallization of electroless Ni-P deposits

A study has been made of microstructures and crystallization of the electroless Ni-P deposits containing 11.3 to 23.0 at% P obtained from acidic nickel sulphate baths with sodium hypophosphite as a reducing agent by means of differential scanning calorimetry, X-ray diffractometry and hot stage transmission electron microscopy. The deposits containing low phosphorus content of 11.3 at% could be represented as an fcc Ni-P solid solution of 5 to 10 nm microcrystallites, whereas the deposits containing high phosphorus content were amorphous. The crystallization process of amorphous Ni-P solution involved more than one intermediate phases; precrystallized nickel or off-stoichiometric Ni₃(P, Ni) or Ni₅(P, Ni)₂ phase in which some phosphorus sites are replaced by nickel atoms. The final equilibrium phases were bct Ni₃P and fcc nickel crystals regardless of phosphorus content. The amorphous phase containing 20 to 22 at% phosphorus was the most stable among the amorphous Ni-P alloys.     

The structural transitions during leaching of Ni2Al3 phase in a Raney Ni-Al alloy

The microstructure transitions during leaching of a rapidly solidified Ni-Al alloy have been investigated by means of X-ray diffraction, transmission electron microscopic (TEM) and high resolution electron microscopic (HREM) techniques. Ni₂Al₃ was the main phase in the starting Ni-Al alloy. The microstructure of the Raney nickel catalyst consists of nano-scale nickel crystallites, residue of source phases surrounded by nano-scale boundary regions. The transformation during leaching of Ni₂Al₃ phase was an advancing interface type process. Clusters of AuCu-structure type face-centrered tetragonal Ni₃Al₂ as an intermediate phase seems to appear in the reaction front. Based on an analysis of the atomic configurations of phases Ni₂Al₃, Ni₃Al₂ and nickel, a reasonable explanation for the transition mechanism during leaching of Ni₂Al₃ phase and the arc characteristic of diffraction spots was proposed. The nickel crystallites generated during leaching obey an orientation relationship with the source Ni₂Al₃ phase, which is consistent with the Delannay's orientation relationship proposed for nickel and NiAl phases. The nano-scale structural characteristic of the Raney nickel catalyst, especially its porous structure at the boundary regions, provides an excellent hydrogenation catalytic activity and selectivity of the catalyst.     

Isochronal crystallization kinetics of Fe40Ni40B20 amorphous alloy

The kinetics of crystallization of amorphous Fe₄₀Ni₄₀B₂₀ alloy upon isochronal annealing was investigated applying power-compensating differential scanning calorimetry with heating rates of (5, 10, 20, 30, 40) K/min. The corresponding microstructural evolution was studied by means of X-ray diffraction, focused ion beam and scanning electron microscopy, and transmission electron microscopy. Crystallization of Fe₄₀Ni₄₀B₂₀ alloy upon isochronal annealing takes place by formation of nano-scaled grains consisting of a face-centered cubic solid solution phase (Fe,Ni) and an orthorhombic compound phase (Fe,Ni)₃B. Kinetic analysis was performed by application of a modular model of phase transformation kinetics, fitted to all experimental transformation-rate curves simultaneously. The crystallization reaction can be described by nucleation with a continuous nucleation rate incorporating a nucleation index a and by growth in three dimensions according to a linear growth law. The kinetics of transformation and the resulting microstructure observed upon isochronal annealing clearly differ from those upon isothermal annealing investigated in a previous study, reflecting different mechanisms operating upon isochronal and isothermal crystallization.     

Tem study of nanocrystalline NdFeB

A detailed study is reported of the microstructure in a nanocrystalline alloy, Nd₄Fe₇₈B₁₈, consisting of a mixture of hard (Nd₂Fe₁₄B) and soft (Fe₃B) magnetic phases, utilizing conventional and analytical transmission electron microscopy (TEM). The nanocrystalline microstructures were fabricated by annealing the melt-spun amorphous Nd₄Fe₇₈B₁₈ ribbons by means of conventional (furnace) annealing techniques and also by the so-called flash-annealing process. Enhanced remanence and coercivity were reported previously for the flash-annealed alloys. Furnace-annealed ribbons contained 20–30 nm equiaxed grains with Fe/Nd = 17–19.6. Also observed were large (50–100 nm) equiaxed grains of α-Fe. For flash-annealed ribbons, significant amounts of Nd₂Fe₂₃B₃, a metastable cubic phase, were observed, as well as a marked difference in the second phase morphology. For the flash-annealed ribbon whose hysteresis loop showed good coupling of the magnetic phases, a refined microstructure was found and the large α-Fe grains were absent.     

Brazing of SiC and SiCf/SiC composites performed with 84Si-16Ti eutectic alloy: microstructure and strength

The microstructure and strength of brazed joints for monolithic SiC and SiC_f/SiC composites are presented and discussed; the brazing technique is based on the use of the 84Si-16Ti (at%) eutectic alloy. The rather low melting point of the used alloy allows to avoid a degradation of the fibre/matrix-interfaces in the composite materials. All the joints did not show any discontinuities and defects at the interface and revealed a fine eutectic structure. Moreover, in the case of composites, the joint layer appeared well adherent both to the matrix and the fibre interphase, and the brazing alloy infiltration looked sufficiently controlled. High resolving electron microscopic investigations of the microstructure and of the nanochemistry (HREM, EELS, esp. ELNES) revealed atomically sharp interfaces without interdiffusion or phase formation at the interlayer leading to the conclusion that direct chemical bonds are responsible for the adhesion. The joints of SiC_f/SiC composites showed 71 ± 10 MPa shear strength at RT and nearly the same values at 600°C.     

Crystallization of amorphous Ni60 Nb40−x Cr x alloys

Crystallization behaviour of amorphous Ni₆₀ Nb_40-x Cr _x (x = 0, 5, 10 and 13 at%) alloys was studied by differential Scanning calorimetry and X-ray diffraction measurements. It is shown that the addition of chromium reduces the crystallization temperature, stages of crystallization and activation energies associated with the crystallization sages of the Ni₆₀Nb₄₀ glass. Crystallization of the Ni₆₀Nb₄₀ glass occurred in three stages; in the initial stage a metastable M-phase formed in the amorphous matrix as reported earlier [1] . However, contrary to earlier observation [1], M -phase was not very stable and transformed together with some amorphous phase to the equilibrium Ni₃Nb phase in the second stage of crystallization. In the third stage, the remaining amorphous matrix transformed to the equilibrium NiNb phase. On addition of chromium the formation/stability of the M-phase was found to be suppressed and equilibrium NbCr₂ phase precipitated preferentially in the first stage. The second stage, corresponding to the formation of Ni₃Nb phase, remained almost unaltered. The third stage corresponding to the crystallization of NiNb phase disappeared completely at 13 at% Cr. In the fully crystallized samples the proportion of the NiNb phase decreased and that of NbCr₂ phase increased continuously with chromium concentration.     

Effect of substituting Ni with Cu on the cycle stability of La0.7Mg0.3Ni2.55−xCo0.45Cux (x = 0–0.4) electrode alloy prepared by casting and rapid quenching

In order to improve the cycle stability of the La–Mg–Ni system (PuNi₃-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Cu. Hydrogen storage alloys La_0.7Mg_0.3Ni_2.55−xCo_0.45Cu_x (x = 0, 0.1, 0.2, 0.3, 0.4) were prepared by casting and rapid quenching. The effects of substituting Ni with Cu and the quenching rate on the microstructures and the cycle stability of the as-cast and quenched alloys were investigated in detail. The results obtained by X-ray diffraction show that the as-cast and quenched alloys have a multiphase structure, including the (La, Mg)Ni₃ phase, the LaNi₅ phase and the LaNi₂ phase, and the amount of the LaNi₂ phase increased with the increase of the Cu content. The substitution and rapid quenching have an inappreciable influence on the phase compositions of the alloys, but both obviously changed the phase abundances of the alloys. The results derived by transmission electron microscopy confirm that the substitution of Cu for Ni is favourable for the formation of an amorphous phase in the as-quenched alloys. The results obtained by the electrochemical measurement indicate that substituting Ni with Cu improved the cycle stability. When the Cu content increases from 0 to 0.4, the cycle lives of the as-cast and rapidly solidified alloys increased from 72 cycles to 88 cycles and from 100 cycles to 122 cycles, respectively.     

Structure and decomposition behaviour of rapidly solidified Al-Fe alloys

The structure and decomposition behaviour of rapidly solidified Al-5, 10 and 15 at% Fe alloys have been investigated by detailed transmission electron microscopy and differential scanning calorimetry. Rapid solidification produces a variety of metastable phases: microquasicrystalline, decagonal, Al _m Fe, Al₆Fe and Al₁₃Fe₄, in order of increasing thermodynamic stability. The rapidly solidified microstructure depends upon the alloy composition and cooling rate. Primary and cellular particles of the microquasicrystalline phase are preferred at higher cooling rates, and primary or eutectic particles of the Al _m Fe phase are preferred at lower cooling rates. With increasing iron content, the microquasicrystalline phase is replaced with primary particles of the decagonal phase. After annealing at moderate temperatures, the microquasicrystalline phase in Al-5 and 10 at% Fe decomposes into Al _m Fe and Al₆Fe, and the microquasicrystalline phase in Al-15 at% Fe decomposes into Al _m Fe. After annealing at higher temperatures, the Al _m Fe, Al₆Fe and decagonal phases then decompose into stable Al₁₃Fe₄.     

A new metastable phase near 60 at% Zr from amorphous Ni-Zr

Metallic glass alloys of Ni-Zr were prepared by vapour and liquid quenching. For glass compositions at and near 60 at% Zr, crystallization proceeded by the sequence: amorphous metastable crystalline phase NiZr₂ + NiZr. The metastable Ni₄₀Zr₆₀ phase exhibited a very distinctive X-ray diffraction pattern and was present in both liquid- and vapour-quenched samples. Long-term anneals of samples with the metastable structure produced the equilibrium phases NiZr₂ and NiZr. The crystallization of the amorphous structure directly to a single metastable phase shows a correspondence between the compositions of the amorphous and crystalline phases. These results thus suggest a connection between the short-range structure of the glassy phase and the crystalline phases to which they transform. An observation of peaks and valleys in a plot of the X-ray scattering vector,Q _p, against glass composition is noted.     

Transformation studies and mechanical properties of melt-quenched amorphous titanium-silicon alloys

The formation, stability and decomposition characteristics of the amorphous phase in binary titanium-silicon alloys rapidly quenched from the molten state have been investigated. Electron microscopy and diffraction coupled with X-ray diffraction techniques suggested that the amorphous phase could be obtained in alloys containing 15 to 20 at% silicon. The transformation of the amorphous phase to the equilibrium phases took place in two stages. A metastable b c c titanium solid solution, containing silicon in excess of the equilibrium value, formed initially, followed by the precipitation of the Ti₅Si₃ intermetallic compound. Microstructural features at various stages of decomposition have been described and interpreted in terms of the constitution of the alloys. Mechanical properties of the amorphous alloys have also been investigated.