Flux-driven nucleation at interfaces during reactive diffusion

Nucleation of intermetallic compounds and of voids at interfaces during reactive diffusion is treated with account of influence of the flux divergence in the nucleation regions of the real space as an additional term for drift in the size space (in Fokker–Planck equation for nucleation). Such approach enables the construction of effective Gibbs nucleation barrier which may (in the broad region of parameters) increase to infinity meaning the full suppression of nucleation, or, by the contrast, decrease assisting the nucleation. The introduced effective nucleation barriers depend on kinetic factors – on the ratio of diffusivities in nucleating and in neighboring phases. Thus, the competition of stable and metastable phases is reconsidered, as well as nucleation of Kirkendall/Frenkel voids at the interfaces.     

Comments on Monte Carlo simulations of void-lattice formation

We study the coalescence of neighbouring voids along close-packed directions in recent computer simulation studies of void-lattice formation. The stability against coalescence of a developing void lattice is found to depend very much on the detailed geometry of the local void distribution. The possibility of void coalescence as an artifact, caused by the incorrect assumption of homogeneous void nucleation in these simulations, is suggested and discussed.     

First-principles investigation of bowing parameter in zinc-blende ScxGa1−xN

Helium generated in materials by the nuclear reaction (n,?α) is generally considered to be harmful. It is well-known that helium prompts not only the nucleation of interstitial-type dislocation loops, but also the nucleation of voids in metals and alloys irradiated with high-energy particles, which degrades their mechanical properties. In this study, however, we find that helium trapped by dislocations in Ni increases both the ultimate tensile strength and total elongation.     

Nucleation of recrystallization in fine-grained materials: an extension of the Bailey–Hirsch criterion

Abstract

A new criterion for nucleation in the case of dynamic recrystallization is proposed in order to include the contribution of the grain boundary energy stored in the microstructure in the energy balance. Due to the nucleation events, the total surface area of pre-existing grain boundaries decreases, leading to a nucleus size smaller than expected by conventional nucleation criteria. The new model provides a better prediction of the nucleus size during recrystallization of pure copper compared with the conventional nucleation criterion.     

Reactive solid-state dewetting

High-temperature annealing in air of thick crystalline silver films deposited on high-purity nickel foils promotes solid-state dewetting, whereas no hole through the film is produced when annealing under high purity argon. Scanning electron microscopy observations of the film surface and of cross-sections reveal that dewetting occurs only if a nickel oxide layer forms at the silver-nickel interface, as a result of oxygen diffusion through the silver film. The main dewetting mechanism over short times (1h 1120K in air) is observed to be the condensation, at the silver-nickel oxide interface, of vacancies into voids which grow towards the free surface of the silver film.     

Secondary defects induced by ion and electron irradiation of GaSb

Secondary defects induced by ion and electron irradiation up to 6?dpa (displacements per atom) at liquid-nitrogen temperature in GaSb thin films are compared. For Sn ion (60?keV) irradiation, voids were observed. However, for high-energy electron (2?MeV) irradiation, interstitial-type dislocation loops were produced. The densities of voids and interstitial-type dislocation loops were almost equivalent (8?×?10¹⁴?voids/m² and 3?×?10¹⁴?loops/m²) after irradiations at the same damage level of 6?dpa. It is concluded that the formation of voids by ion irradiation follows the creation of localised vacancy defects in cascade damage.     

Shuffle-set dislocation nucleation in semiconductor silicon device

We have found that a shuffle-set dislocation is nucleated in a semiconductor silicon device subjected to severe thermal processing. The dislocation transforms into a dissociated glide-set dislocation after annealing at 500°C. A possible mechanism for the nucleation of a perfect shuffle-set dislocation during thermal processing is that the dislocation nucleus was nucleated at a low temperature during prior ion-implantation processing.     

Influence of Cd and Ge on the kinetics of Guinier–Preston zone formation in Cu–Be alloys

The influence of Cd and Ge on the kinetics of Guinier–Preston zone formation has been studied for Cu–2?wt%?Be–0.3?wt%?Cd and Cu–2?wt% Be–0.3wt%?Ge solid solutions. The relative volume fractions of these Guinier–Preston (GP) zones are determined for different times of ageing at 473?K by a method based on microhardness measurements. Cd atoms in Cu–Be–Cd accelerate GP zone formation. This is due to the supersaturation of Cd atoms in Cu and their strong binding energy with vacancies. In contrast, the Ge atoms do not influence GP zone formation in Cu–Be–Ge. The binding energies between the two solute atoms and a vacancy, and the concentration of the quenched-in vacancies bound to the solute atoms, are calculated using the Hasiguti formula and the Kimura equation.     

Voids formed from solidifying tin particles in solid aluminium

In this study, voids commonly associated with tin particles in two aluminium alloys containing microalloying additions (0.01 at.%) of tin have been observed by transmission electron microscopy. The voids were generated by quenching the alloys at moderate rates (10²–10³ K s^?1) from a temperature (718 K) in excess of the melting temperature (501 K) of elemental tin in tin–microalloyed aluminium. Estimates of the void volume as a function of the volume of the associated tin particle reveal a linear relationship consistent with the excess volume resulting from the solidification of the tin particle. The formation and stabilisation of shrinkage voids in metallic alloys are suggested to arise from a combination of high vacancy supersaturation, the large volumetric misfit strain of the solidifying tin particle and a reduction in void surface energy associated with segregation of alloying elements.     

Criteria of kinetic suppression of lateral growth of intermediate phases

In many cases, the formation of intermediate phases in solid-state reaction starts from nucleation, proceeds at first by lateral spreading along interface in the form of narrow layer and after that continues slow growth in normal direction. So far, the lateral growth stage was considered as something almost instant. Yet, if the emerging phase is not the first one and the already growing phase layer has high diffusivity, the lateral growth can be also kinetically suppressed due to ‘sucking out’ of atoms from the moving interface into the growing first phase layer. Criteria of such suppression are formulated and examples of real systems are discussed.     

A new counter-example to Kelvin's conjecture on minimal surfaces

A survey of the published literature on undercooled metallic and oxide melts suggests that phase selection during solidification can be categorized as nucleation controlled or growth controlled. Common characteristics governing the phase-selection pathway have been identified for various alloy systems. It is recognized that when competing stable and metastable phases share the same crystalline characteristics and have comparable interface kinetic coefficients, the principle of nucleation control applies for primary phase formation in a deeply undercooled melt. However, there can be a difference of two or three orders of magnitude in the interface kinetic coefficients for competing phases, either between an ordered intermetallic compound and a disordered solid solution, or between a crystalline phase with a high level of complexity and a simple crystal. In such cases, the principle of growth control will apply; more specifically, the phase with the faster growth kinetics should be favoured and the competing counterpart with sluggish interface kinetics should be suppressed at high undercoolings. Some simple predictions are suggested on the basis of this principle when considering stable and metastable phase diagrams. The specific conditions under which the present categorization is applicable are outlined. Future work is required to elucidate phase competition under conditions of very rapid solidification.     

Dislocation nucleation and vacancy formation during high-speed deformation of fcc metals

Recently, a dislocation-free deformation mechanism was proposed by Kiritani et al. on the basis of a series of experiments where thin foils of fcc metals were deformed at very high strain rates. In the experimental study, they observed a large density of stacking fault tetrahedra but very low dislocation densities in the foils after deformation. This was interpreted as evidence for a new dislocation-free deformation mechanism, resulting in a very high vacancy production rate. In this paper we investigate this proposition using large-scale computer simulations of bulk and thin films of copper. To favour such a dislocation-free deformation mechanism, we have made dislocation nucleation very difficult by not introducing any potential dislocation sources in the initial configuration. Nevertheless, we observe the nucleation of dislocation loops, and the deformation is carried by dislocations. The dislocations are nucleated as single Shockley partials. The large stresses required before dislocations are nucleated result in a very high dislocation density, and therefore in many inelastic interactions between the dislocations. These interactions create vacancies and a very large vacancy concentration is quickly reached.     

Identification of crystal nucleation and growth in an amorphous FeZr2 alloy by means of electrical resistance measurements

A polymorphous crystallization process in an amorphous FeZr₂ alloy has been investigated by means of accurate electrical resistance measurements (ERMs) at elevated temperatures. It was found that, upon crystallization of the amorphous alloy, the electrical resistance increased with increasing temperature, exhibiting three distinct stages. Quantitative microscopy observations revealed that the three stages originated from crystal nucleation, from subsequent growth of crystal nuclei and from coarsening of the crystallites respectively. The activation energies for the crystal nucleation and growth determined from the ERM data agree satisfactorily with the data in the literature. The success in identification of the crystal nucleation and growth processes by means of ERMs may originate from differences in electrical resistance changes due to the crystal formation and the crystalline-amorphous interface formation processes from the amorphous phase.     

Secondary ageing in Al-Cu-Mg

Secondary ageing, that is microstructural evolution occurring at room temperature after short heating at temperatures above the metastable phase boundary of Guinier-Preston zones, has been studied for an Al-Cu-Mg alloy with a high Cu-to-Mg ratio. Combined data from positron annihilation spectroscopy, Vickers microhardness measurements and differential scanning calorimetry show that, on secondary ageing after 5 or 7min at 190°C, firstly, hardening takes place at a rate nine to 16 times slower than natural age hardening; secondly, vacancies slowly released by Cu-rich aggregates formed during the heat treatment at 190°C promote further formation of solute aggregates, with a time-dependent chemical composition; thirdly, the thermal stability of the structures formed during secondary ageing increases with increasing dwell time at room temperature; and, fourthly, solute aggregates formed at 190°C undergo a structural reorganization and possibly a change in the composition, leading to species with a different thermal stability. The slow release of vacancies from Cu-rich aggregates is proposed as one of the limiting factors of the hardening rate.     

Kinetic pinning versus capillary pinning of voids at the moving interface during reactive diffusion

Two mechanisms of the Kirkendall voids pinning at the moving interface are discussed. Besides common Zener pinning, voids can be additionally, kinetically pinned to the interface by the additional vacancy concentration gradient, existing due to unideal vacancy sinks/sources at the interface and at the both sides of it. Kinetic pinning may explain the influence of copper substrate defect prehistory on the pinning behaviour. Capillary pinning is difficult to apply for the cases of voids enveloping by the growing phase.     

Structural evolution during crystal nucleation in supercooled liquids with icosahedral short-range order

The structural evolution during crystal nucleation in supercooled Lennard–Jones liquids at a supercooling of 0.3T _m (T _m is the melting temperature) has been studied by molecular dynamic simulations. The icosahedral clusters are observed to compete with crystalline clusters in space, and rearrange before crystal nucleation. Both the stable face-centered-cubic and hexagonal-close-packed (hcp) structures and metastable body-centered-cubic (bcc) structures nucleate simultaneously, resulting in the formation of an incomplete bcc meso-layer in the nuclei. The nuclei form twinned crystal with five-fold axes through a successive twinning process bounded by planes with hcp atoms.     

Reversible plasticity under nanoindentation of atomically flat and stepped surfaces of fcc metals

Using atomistic simulation, the indentation of single-crystalline Cu is investigated for both an ideal and a stepped (111) surface. Both systems exhibit an intermediate regime of reversible plasticity, characterized by the formation of extended stacking faults, which heal entirely upon withdrawal of the indenter. This regime can be employed to clarify the role of pure stacking fault generation and cross-slip in plasticity. Its existence reveals that, on the atomistic scale, plastic deformation is characterized by material transport rather than by the nucleation of stacking faults. Finally, we establish a criterion–based on the total displacement of particles–to determine after which indentation depth plasticity is generated irreversibly in the material.     

Room temperature ferromagnetism and photoluminescence of nanocrystalline Zn1 − xCoxO thin films prepared by sol–gel MOD

Zn_1???xCo_xO (ZC) [x?=?0, 1, 3, 5, 7 and 9?mol%] thin films were prepared by sol–gel combined metallo-organic decomposition method. The films were deposited on the Si substrate with spin-coating technique and annealed at 600?°C for 3?h. X-ray diffraction pattern shows the formation hexagonal wurtzite phase and distortion (c/a) decreases with increasing Co concentration in ZnO. The average grain size is measured using Scherer relation. Atomic force microscopy is used to confirm the formation of nanograins resulted by the use of polyethylene glycol as surfactant. The photoluminescence was recorded by using He-Cd laser of excitation wavelength 325?nm in wavelength region of 350–650?nm which exhibits some influence of Co doping on the multiplication of defects such as O vacancies, Zn interstitials and grain boundary defects. All thin films show room temperature ferromagnetism except pure ZnO which is diamagnetic and 9?mol% of Co shows paramagnetism. This behaviour is interpreted as due to fluctuations in the magnetic ordering, depending on grain size and site location in grain boundaries or oxygen vacancies.     

Effects of Ag and Pd on the nucleation and growth of the nano-icosahedral phase in Zr65Al7.5Ni10Cu7.5M10 (M = Ag or Pd) metallic glasses

The nucleation and growth of a nano-icosahedral phase from a supercooled liquid region of Zr₆₅Al_7.5Ni₁₀Cu_7.5M₁₀ (M = Ag or Pd) glasses have been examined by differential scanning calorimetry and transmission electron microscopy. The growth rate of the icosahedral phase is nearly constant at the initial stage and much slower than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 metallic glass. The homogeneous nucleation rate has a maximum value of 4.4 x 10²⁰ m^-3 s^-1 at 695 K in the Zr₆₅Al_7.5Ni₁₀Cu_7.5Ag₁₀ glass, which is approximately 10² times higher than that for the formation of quasicrystalline phase in the Zr_69.5Al_7.5Ni₁₁Cu₁₂ glass and 10⁴ times higher than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 glass. With increasing Pd content, the nucleation rate of the primary phase increases significantly and the growth rate decreases at the crystallization temperature. Thus, the addition of Ag and Pd is effective for an increase in the number of nucleation sites and the suppression of grain growth, which is the main reason for the formation of icosahedral nanoparticles. The significant increase in the nucleation rate is due to an increase in the number of nucleation sites resulting from the short-range ordering consisting of Zr-(Ag or Pd) strong pairs. It is implied that the strong pair Zr-(Ag or Pd) also contributes to the restraint of the long-range rearrangements of the constitutional elements. The formation of the nanoicosahedral phase suggests that icosahedral short-range order exists in the glassy state in the present alloys.     

On the role of Ag in enhanced age hardening kinetics of Mg–Gd–Ag–Zr alloys

The addition of Ag to the age hardenable Mg–Gd–Zr alloy system dramatically enhances early stage age hardening kinetics. Using atom probe tomography (APT), Ag-rich clusters were detected in a Ag-containing Mg–Gd–Zr alloy immediately after solution treatment and water quenching. During subsequent isothermal ageing at 200 °C, a high density of basal precipitates was observed during the early stages of ageing. These basal precipitates were enriched with Ag and Gd, as confirmed by APT. It is posited that Ag-rich clusters in the context of quenched-in vacancies can attract Gd atoms, increasing diffusion kinetics to facilitate the formation of the Ag + Gd-rich basal precipitates. The rapid formation of Ag + Gd-rich precipitates was responsible for accelerated ageing.