Unexpected nanoscale phase separation in sputterdeposited Ni-25 at.%Al thin films

Thin films of nominal composition Ni-25at.%Al, sputter deposited from a target of the intermetallic compound Ni 3 Al on unheated substrates, exhibit an unexpected phase separation, in contrast with other intermetallic-forming systems such as Ti-Al which are deposited as compositionally homogeneous amorphous films under similar conditions. Precipitates of a novel tetragonal phase, a few nanometres in size, were formed in the matrix consisting of a fcc Ni-rich Ni(Al) phase and a hcp Ni-rich Ni(Al) phase. Ni-Al films of the same composition deposited on heated substrates exhibited the formation of a single, chemically long-range-ordered Ni 3 Al phase with the L1 2 structure, the thermodynamically stable phase for this composition.     

Pattern evolution of crystalline Ge aggregates during annealing of an Al/Ge bilayer film deposited on a SiO2 substrate

When an Al/Ge bilayer film deposited on a SiO2 substrate is annealed at 373- 398 K, Ge atoms diffuse out from the inner amorphous Ge layer and spread over the free surface of the outer Al layer to form crystalline Ge aggregates exhibiting complex substructures. Scanning electron microscopy observations indicate that the activation energy for the pattern evolution of Ge aggregates on the free surface because of annealing is 1.56 eV which is about half the activation energy for crystallization of amorphous Ge.     

Reaction of a Ni-coated Al nanoparticle to form B2-NiAl: A molecular dynamics study

The kinetic reaction in a Ni-coated Al nanoparticle with equi-atomic fractions and diameter of approximately 4.5 nm is studied by means of molecular dynamics simulation, using a potential of the embedded atom type to model the interatomic interactions. First, the large driving force for the alloying of Ni and Al initiates solid state amorphization of the nanoparticle with the formation of Ni₅₀Al₅₀ amorphous alloy. Amorphization makes intermixing of the components much easier compared to the crystalline state. The average rate of penetration of Ni atoms can be estimated to be about two times higher than Al atoms, whilst the total rate of inter-penetration can be estimated to be of the order of 10^?2 m/s. The heat of the intermixing with the formation of Ni₅₀Al₅₀ amorphous alloy can be estimated at approximately ?0.34 eV/at. Next, the crystallization of the Ni₅₀Al₅₀ amorphous alloy into B2-NiAl ordered crystal structure is observed. The heat of the crystallization can be estimated as approximately ?0.08 eV/at. Then, the B2-NiAl ordered nanoparticle melts at a temperature of approximately 1500 K. It is shown that, for the alloying reaction in the initial Ni-coated Al nanoparticle, the ignition temperature can be as low as approximately 200 K, while the adiabatic temperature for the reaction is below the melting temperature of the nanoparticle with the B2-NiAl ordered structure.     

Relations between quasicrystals and crystalline phases in Al─Li─Cu─Mg alloys: A new class of approximant structures

Abstract

From an electron-diffraction study the crystalline c-phase, observed together with the quasicrystals in an Al─Li─Cu─Mg alloy, has been analysed as exhibiting an almost perfect icosahedral symmetry. Orientation relationships with quasicrystals are determined and serve to define a new class of approximant structures, including, beyond the c-phase, the Ti₂ Ni and Ti₂ Fe structures.     

Crystallization behaviour of Al-based amorphous alloy and nanocomposites by rapid quenching

The microstructure and crystallization behaviour of melt-spun Al₈₈Ni₉Ce₂Fe₁ amorphous alloy and nanophase composites have been studied by means of X-ray diffraction, transmission electron microscopy and scanning and isothermal calorimetry. The diffraction patterns from Al₈₈Ni₉Ce₂Fe₁ amorphous alloys are diffuse, indicating a basically amorphous structure but contain two rings presumed to be associated with quenched-in nuclei. In the cases of Al₈₈Ni₉Ce₂Fe₁ nanophase composites, nanoscale precipitated particles are homogeneously dispersed in an amorphous matrix, and the crystallite diameter and volume fraction are sensitive to quenching conditions. During thermal crystallization, a two-step phase transformation occurs in the amorphous alloy and nanocomposites, which is characterized by a diffusion-controlled precipitation of nanoscale Al particles and the growth of a Al₃(Ni, Fe) nanophase prior to a Al₁₁Ce₃ nanophase. This study gives insight into structure-control for obtaining nanophases dispersed in an amorphous matrix by rapid quenching.     

Hydrostatic pressure-enhanced solid-phase epitaxy

Abstract

A large enhancement of solid-phase epitaxial growth (SPEG) due to hydrostatic pressure is explained by stress-enhanced self-diffusivity in the amorphous solid. The crystallization is by the adjustment of atomic positions in the vicinity of the crystalline/amorphous (c-a) interface due to self-diffusion in the amorphous phase, assisted by a free-energy decrease equal to the difference in free energies between the amorphous and crystalline phases. Owing to a mismatch in the bulk moduli between the amorphous and crystalline phases, non-hydrostatic stresses are developed near the c-a interface under hydrostatic pressure. Non-hydrostatic stresses in the amorphous layer enhance the mobility of point defects in the amorphous layer. This leads to an increased self-diffusivity in the amorphous layer and, therefore, an enhancement of the SPEG rate.     

The orientation and temperature dependences of dislocation velocity in Ni 3 Al single crystals

The average velocities of screw dislocations in Ni 3 Al single crystals have been directly measured as a function of resolved shear stress (RSS) and orientation in the temperature domain of the flow stress anomaly using the etch-pit technique. The velocity was found to be extremely sensitive to the RSS in all cases. In contrast with ordinary metals, the screw dislocation velocities in Ni 3 Al show anomalous behaviour; under a constant RSS, the velocities decrease dramatically with increasing temperature. Furthermore, the velocities and the tension-compression asymmetry of the velocities depend on the orientation of applied stress.     

Nanocrystallization in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass

The first stages of thermal relaxation towards equilibrium in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass have been studied by differential scanning calorimetry, X-ray diffraction, transmission electron microscopy and high-resolution electron microscopy. These coupled experiments rule out for this glass the existence of a phase separation on the nanometric scale preceding the onset of crystallization. The first step of crystallization is of the primary type, that is it consists of the nucleation of nanocrystallites in the amorphous matrix with which they coexist in metastable equilibrium. The very high nucleation rate leads to a nanometric composite structure with a number density of about 7 2 10 24 m -3 of 3-4nm crystallites, occupying a volume fraction of about 15%. These features, as well as the crystallization kinetics observed during isochronal or isothermal heating, are discussed.     

Ion-irradiation-induced solid-phase epitaxial growth

Abstract

A model is proposed to explain ion-induced solid phase epitaxial growth (SPEG). The crystallization is by the adjustment of atomic positions in the vicinity of the crystalline/amorphous interface due to self-diffusion in the amorphous solid. The driving energy of SPEG is the difference in free energies between the amorphous and crystalline solids. Irradiation increases the self diffusivity of the amorphous solid by generating point defects in the amorphous solid and thus enhances the crystallization. An expression for the velocity of epitaxial growth is derived. The model explains numerous experimental facts and, at the limit of no irradiation, also gives a correct model of thermal solid-phase epitaxial growth.     

Formation of ductile Al-based metallic glasses without rare-earth elements

Al₇₅Cu₁₇Mg₈ is a eutectic composition according to the ternary phase diagram, which can be quenched into a fully amorphous phase by adding 2-8at.% Ni, but the addition of a similar percentage of Gd failed to form the amorphous phase. The amorphous alloys obtained exhibit two broad diffuse peaks in the X-ray diffraction curves and, correspondingly, two halo rings in the electron diffraction patterns, implying that two types of local atom configuration exist. Thermal analysis of the amorphous alloys indicates that the primary crystallization peak shifts to higher temperatures with increasing Ni content. The occurrence of a nucleation and crystal growth peak during isothermal crystallization reveals the amorphous nature of the quenched ribbon alloys. The quenched amorphous ribbons do not break after bending by 180°. Mechanical testing yielded a tensile strength of 810MPa for (Al₇₅Cu₁₇Mg₈)₉₅Ni₅, and a vein structure, characteristic of amorphous fracture, is apparent in scanning electron micrographs. The different effects of Ni and Gd on the glass formation indicate that the large atomic size of Gd is not critical to the glass formation.     

Formation of Al3Ni2-type nanocrystalline τ 3 phases in the Al–Cu–Ni system by mechanical alloying

An elemental powder mixture of Al (70 at.%), Ni (15 at.%) and Cu (15 at.%) was milled in a high-energy ball mill for various times ranging from 10 to 100?h to form ternary intermetallic alloys. X-ray diffraction and transmission electron microscopy techniques were employed for characterization of the samples. The dissolution of the individual elements into an alloy led to the formation of a τ₃ vacancy-ordered phase after 100?h of milling. This phase was found to be quite stable against milling, and no other crystalline and amorphous phases could be detected. The powder after 100?h of milling was found to contain mostly τ₃ nanophases with partial ordering, and with crystallite sizes in the range 10–20?nm along with a lattice strain of ～0.675%. The milled powder, after annealing at 700°C for 20, 40 and 60?h, revealed the formation of a strain-free and ordered τ₃ phase with a crystallite size of 80?nm, indicating grain coarsening. It is interesting to note that the mechanical energy imparted during milling could not completely destroy the vacancy ordering in the τ₃ phase, unlike other stoichiometric Al–Cu–transition metal (TM) systems, where the disordered B2 (bcc) phase is commonly observed instead of any vacancy-ordered phases.     

Reflectance of multilayer amorphous semiconductor films with random thickness layers

Abstract

Reflectance and transmittance spectra of amorphous semiconductor multilayer films were computed for layers of random thickness. This choice was prompted by the experimental results recently reported on hydrogenated amorphous silicon/silicon-nitride films in which the thickness of the lower bandgap material layers is randomly chosen. The calculation clearly elucidates the origin of a peculiar behaviour of the reflectivity observed in the spectral region of strong absorption.     

Microstructural characterization and high-temperature strength of hot-pressed silicon nitride ceramics with Lu2O3 additives

The microstructures of two hot-pressed Si₃N₄ ceramics, with 3.33 and 12.51 wt% Lu₂O₃ additive, have been characterized using transmission electron microscopy. The microstructures of both samples consisted of elongated β-Si₃N₄ grains and a secondary phase, contained in pockets surrounded by the grains, with a crystalline or amorphous form. In the 3.33 wt% Lu₂O₃-containing Si₃N₄ ceramic, all the multiple-grain junctions were completely crystalline while, in the 12.51 wt% Lu₂O₃-containing Si₃N₄ ceramic, approximately half the junctions were devitrified. A thin intergranular amorphous film present between the two-grain boundary was common; however, a film-free grain boundary was observed in the 12.51 wt% Lu₂O₃ sample. The film-free grain boundary was determined to be approximately 35%. Both ceramics fractured in four-point flexure between 1200 and 1600°C. Their high-temperature strength is closely associated with the nature of the grain-boundary phase formed during the sintering process.     

Stability and strain of decagonal Al-Ni-Co quasicrystal under high pressure up to 70GPa

The stability of high-quality decagonal Al72Ni20Co8 single quasicrystals has been investigated under high pressure up to 67 GPa by means of an in situ angular-dispersive X-ray powder diffraction method using synchrotron radiation and a diamond anvil cell. It is found that the compression behaviour is almost isotropic. On the other hand, the strain behaviour on compression is found to be fairly anisotropic. This means that the quasiperiodic structure in the decagonal Al72Ni20Co8 quasicrystal is much more easily distorted than is the periodic structure.     

Chemical ordering of Co and Ni in a W-(AlCoNi) crystalline approximant related to Al–Co–Ni decagonal quasicrystals studied by atomic resolution energy-dispersive X-ray spectroscopy

A W-(AlCoNi) crystalline approximant, which is closely related to Al–Co–Ni decagonal quasicrystals, in an Al_72.5Co₂₀Ni_7.5 alloy has been studied by atomic resolution energy-dispersive X-ray spectroscopy (EDS), in an instrument attached to a spherical aberration (Cs)-corrected scanning transmission electron microscope. On high-resolution EDS maps of Co and Ni elements, obtained by integrating many sets of EDS data taken from undamaged areas, chemical ordering of Co and Ni is clearly detected. In the structure of the W-(AlCoNi) phase, consisting of arrangements of transition-metal (TM) atoms located at vertices of pentagonal tilings and pentagonal arrangements of mixed sites (MSs) of TM and Al atoms, Co atoms occupy the TM atom positions with the pentagonal tiling and Ni is enriched in part of the pentagonal arrangements of MSs.     

site determination of dilute Cu in beta-phase NiAl by 63Cu nuclear magnetic resonance and X-ray emission channelling patterns

A sharply bimodal lattice site distribution of dilute Cu in both Ni-deficient and Al-deficient beta-phase Ni-Al alloys has been observed in the 63Cu nuclear magnetic resonance (NMR) spectra. These NMR results are correlated with results derived from incoherent channelling patterns (ICPs) formed by variations in characteristic X-ray emission as a function of incident fast electron orientation. Statistical analysis of ICP data, generated near a 210 zone axis, indicates that Cu occupies substitutional sites; Cu is exclusively on the Al sublattice sites in the Al-deficient alloy, whilst the partition ratio of Ni : Al sublattice sites for Cu in the Ni-deficient alloy is about 80 : 20. Comparison of ICP contrast from Cu X-ray emission with ICPs from the host lattice enables the two peaks in the 63Cu NMR spectrum to be individually identified as originating from Cu on Ni sublattice sites, and from Cu on Al sublattice sites. The respective NMR line intensities from the Ni-deficient alloy yields a Ni : Al sublattice site occupancy ratio which is in good agreement with the partitioning ratios derived from channelling patterns     

Synthesis of amorphous and quasicrystal phases by mechanical alloying of Ti 45 Zr 38 Ni 17 powder mixtures,and their hydrogenation

Mechanical alloying of Ti 45 Zr 38 Ni 17 powder mixture forms an amorphous phase, but subsequent annealing causes the formation of an icosahedral ( i ) phase. The maximum hydrogen concentration that can be loaded at 573K at a hydrogen pressure of 3.8MPa is the same (\[H]/\[M] 1.5) for the amorphous and i -phase powders. With hydrogenation, the i -phase is almost stable, forming no hydrides, whereas the amorphous phase transforms to a fcc hydride. The activation energy for hydrogen desorption for the i -phase is about 127kJmol -1, which is lower than that for the amorphous phase, suggesting that the i -phase powder may have better properties for hydrogen-storage applications.     

Structural effects on diffusion in metallic glasses: The pressure dependence of Ni diffusion in as-quenched and relaxed Co42Zr58

In order to clarify the role of thermal defects in diffusion in metallic glasses, we have measured the temperature and pressure dependences of diffusion of Ni, a probe for Co, in relaxed and non-relaxed amorphous Co₄₂Zr₅₈ alloys by means of the tracer technique in combination with secondary-ion mass spectroscopy. For the relaxed state, the activation energy and the pre-factor are Q _{= (}1:65=0:08₎ eV and D _{0 =} 2:4+3:9 10-6m2 s-1 respectively. The pressure - 1:9 dependence yields an activation volume V _{act = (}0:66 0:15₎Omega, with Omega being the average atomic volume of the alloy. This value is similar to activation volumes in crystalline materials and is indicative of diffusion via thermally generated defects. Unlike monovacancies in crystals, these defects appear to be spread out, judging from recent isotope-effect measurements. Comparison with literature data shows that the activation volume and hence the diffusion mechanism in metallic glasses clearly depend on the structure and composition even for the very same component. The activation volume in the as-quenched state was found to be _{( )} ^{0:93 0:25 Omega.}     

High-resolution in situ electron microscopy of a silicon surface modification by molten aluminium at high temperatures

High-resolution in situ heating experiments in a transmission electron microscope have been applied to a study of the surface modification of Si by molten Al in a vacuum of 1 10^-5 Pa. Transformation from an atomically rough to an atomically flat surface was induced by wetting of molten Al atoms. Si {110}, {112}, {115} and {773} surfaces show sawtooth-like structures composed of nanofacets. It is concluded that molten Al atoms remove a native amorphous oxide layer which existed on the original Si surface, making the surface 'clean' even in a non-ultra-high vacuum such as 10^-5Pa.