Octapod-shaped,nanosized, amorphous precipitates in a crystalline ferrite matrix

The development of uniquely octapod-shaped nanosized amorphous silicon–nitride precipitates in a ferrite matrix was observed upon nitriding of Fe–4.5at.%Si alloy. The legs of the amorphous precipitate are oriented along ?1?1?1?-directions of the ferrite. The occurrence of such peculiarly shaped amorphous silicon–nitride precipitates, which experience a volume misfit of more than 100% with the surrounding ferrite, was attributed to precipitate growth influenced by long-range diffusion within the evolving highly anisotropic stress field around the developing precipitates after nucleation.     

Enhancement of hardening and thermal resistance of Mg–Sn-based alloys by addition of Cu and Al

Mg–Sn-based alloys are considered as a promising precipitation-hardening system for applications at elevated temperatures, but the hardening effect is not satisfactory owing to sluggish nucleation and rapid coarsening of the major Mg₂Sn lath precipitates. In this study, Cu and Al are added to a Mg–6Sn–1Mn base alloy. The age-hardening response and the microstructures of these modified alloys have been investigated and are compared to that of the base alloy. The additional elements are found to bring several beneficial effects to the alloys for applications at elevated temperatures. Firstly, a eutectic structure consisting of strong intermetallic phases, i.e. Mg₂Cu in the Mg–6Sn–1Mn–2Cu alloy and Al_0.93Cu_1.07Mg in the Mg–6Sn–1Mn–2Cu–2Al alloy, remains stable along the grain boundaries after solution and ageing heat treatments. Secondly, the precipitate density has been increased significantly and the precipitate size has been refined remarkably during ageing at 200?°C. Moreover, the growth of the precipitates is inhibited remarkably during the over-ageing period. Therefore, the age-hardening response and over-ageing resistance are notably improved.     

3D atom probe study of solute atoms clustering during natural ageing and pre-ageing of an Al-Mg-Si alloy

The pair-correlation function applied to 3D Atom Probe reconstructed volumes has been used to study the influence of a pre-ageing treatment (363?K) on the early stages of precipitation at 458?K in an Al-Mg-Si 6016 alloy. Mg-Si short-range positive pair correlation (clustering) is shown to form after a pre-ageing treatment. The hetero-atomic clusters are thought to act as preferential nucleation sites and lead to a finer dispersion of precipitates after ageing.     

Formation of Cu precipitates and vacancy clusters in neutron-irradiated Fe–Cu alloys

Two Fe–Cu binary model alloys, Fe–0.3Cu and Fe–0.6Cu, were irradiated with fission neutrons at doses ranging from 4?×?10^?6 to 0.16 dpa (displacements per atom) at ～573 K to investigate the formation of Cu precipitates and microstructural evolution. The Cu content only affected the formation of Cu precipitates and microvoids at low doses. In Fe–0.3Cu, the formation of microvoids and Cu precipitates initiated at doses of 1.2?×?10^?4 and 4?×?10^?5 dpa, respectively. On the other hand, the formation of microvoids started at a dose of 4?×?10^?4 dpa in Fe–0.6Cu, and Cu precipitates were formed even after irradiation to 4?×?10^?6 dpa. On further irradiation, the difference in the formation of Cu precipitates and microvoids was small. Microvoids grew with increasing irradiation dose up to 3?×?10^?3 dpa in both alloys. Prominent aggregation of Cu atoms occurred upon irradiation from 3?×?10^?3 to 1.6?×?10^?2 dpa and the microvoids shrank. The Cu precipitates no longer grew, and microvoids nucleated and grew in the matrix above a dose of 1.6?×?10^?2 dpa in both alloys. The present studies clearly reveal the relationships between the formation and growth of Cu precipitates and microvoids with irradiation dose.     

Segregation of copper in an Fe–Cu alloy under pulsed electric current

Effect of electric current on the segregation of copper precipitates in the Fe–13.6Cu alloy is evaluated. Results of this approach present two stages of segregation, namely, grain-boundary segregation during the solidification and interphase-boundary segregation during the decomposition of a solid solution. The segregation becomes apparent not only because the thermodynamic barrier for segregation is decreased, but also because the diffusion is greatly enhanced. Based on the thermodynamic and kinetic aspects, the segregation process under electric current would be of great interest and of physical importance because this kind of electric current-induced segregation was much stronger than the thermal diffusion segregation.     

Effect of applied stress on precipitation of Guinier–Preston zones in a Cu–0.9 wt.% Be single crystal

A stress-oriented formation of plate-shaped Guinier–Preston (GP) zones in single crystals of a Cu–0.9?wt.%?Be alloy aged at 200°C has been found. A compressive stress applied in the [001] direction assists the formation of the GP zones perpendicular to the [001] axis, while a tensile stress results in the preferential formation of the GP zones parallel to the stress axis. The applied stress strongly affects the nucleation of the GP zones. Free ageing at 275°C after compressive-stress ageing at 200°C produces plate-shaped γ′′ precipitates perpendicular to the stress axis, indicating a continuous change in the structure of the GP zones into that of the γ′′ phase. From length-change measurements during ageing, the misfit strains of the GP zone or γ′′ precipitate in directions parallel and perpendicular to the plate plane are estimated, respectively, as ?0.01 and ?0.10 for the GP zone and ?0.01 and ?0.11 for the γ′′ precipitate.     

Compositions of different phases appearing during devitrification of Zr46.75Ti8.25Cu7.5Ni10Be27.5 bulk metallic glass

The devitrification process of Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 metallic glass during annealing in the supercooled liquid region has been studied by conventional, high-resolution and analytical transmission electron microscopy (TEM). Two kinds of particle appear during devitrification: quasicrystals and crystalline precipitates. Nanoanalysis with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy reveal that quasicrystals are Be free, while the crystallites have the ZrBe₂ hexagonal structure. These experiments confirm the key role of Be during devitrification. They also indicate that quasicrystals can form in the system Zr–Ti–Cu–Ni (without Be), as further evidenced by direct synthesis and an in situ neutron diffraction investigation, according to the chemical composition deduced from the TEM analysis.     

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.     

Design considerations for achieving simultaneously high-strength and highly ductile magnesium alloys

A comprehensive scheme of phase configuration optimization in the Mg–Zn–Ca(–Zr) system by thermodynamic simulations and microstructural analyses is presented. A composition window of 0.2–0.4?wt% Ca and 5–6?wt% Zn is defined as optimal for establishing a complex heterogeneous microstructure allowing for enhanced ductility and simultaneously high strength of the material. Literature data analysis and our own results confirm the enhanced performance of alloys from this composition window.     

Mathematical modelling of nucleation and growth of crystals with buoyancy effects

A complete analytical solution of the integro-differential model describing the nucleation of crystals and their subsequent growth in a binary system with allowance for buoyancy forces is constructed. An exact analytical solution of the Fokker-Planck-type equation for the three-parameter density distribution function is found for arbitrary nucleation kinetics. Two important cases of the Weber–Volmer–Frenkel–Zel’dovich and Meirs kinetics are considered in some detail. It is shown that the solute concentration decreases and the distribution function increases with increasing the melt supercooling (with increasing the depth of a metastable system). It is demonstrated that the distribution function attains its minimum at a certain size of crystals owing to buoyancy forces.     

Solutal gradients in strained equilibrium

Abstract

We demonstrate that the distortion of a crystal, caused by secondary phase precipitates, can stabilize a solutal gradient around the precipitate. The gradient persists in the quasi-static state stabilized by the gradient of the elastic energy around the precipitate. The peak concentration at the interface between precipitate and matrix hereby is independent of the radius of the precipitate and no mechanism of ripening is active in an arrangement of precipitates of different size. The model offers an explanation of experimental observations of the anomalous stability of nano-precipitates in Al–Cu.     

Characteristics of the interaction of Cu-rich precipitates with irradiation-produced defects in α-Fe

The interaction between copper-rich precipitates in α-iron and either vacancies or self-interstitial atoms and their clusters is studied by atomic-scale modelling. Results are compared with predictions of elasticity theory and interpreted in terms of size misfit of precipitates and defects, and the modulus and cohesive energy differences between iron and copper. Interstitial defects are repelled by precipitates at large distance but, like vacancies, attracted at small distance. Hence, copper precipitates in iron can be sinks for both vacancy and interstitial defects, and can act as strong recombination centres under irradiation conditions. This leads to a tentative explanation for the mixed Cu–Fe structure of precipitates and the absence of precipitate growth under neutron irradiation conditions. More generally, both vacancy and interstitial defects may be strongly bound to precipitates with weaker cohesion than the matrix.     

Composition and magnetic character of nanometre-size Cu precipitates in reactor pressure vessel steels: Implications for nuclear power plant lifetime extension

The sensitivity of positrons to nanometre-size Cu precipitates in Fe alloys has enabled us to apply a novel spin-polarized element-specific method to probe the composition and magnetic character of the precipitates responsible for reactor pressure vessel (RPV) steel embrittlement. The results clearly show that the precipitates are non-magnetic and place an upper limit of about 10at% on their Fe content. The practical implication of this result is that the Cu precipitate contribution to RPV steel embrittlement saturates is not expected to contribute further during lifetime extension. Our study demonstrates that polarized positrons can be used as a powerful probe of the magnetic character of nanoscale materials, even those embedded in a strongly magnetic host.     

Precipitate characteristics and selected area diffraction patterns of the β′ and Q′ precipitates in Al–Mg–Si–Cu alloys

In this study, the precipitate characteristics and selected area diffraction patterns (SADP) of the β?′ and Q?′ precipitates formed at the over-aged state of Al–Mg–Si–Cu alloys are systematically investigated by means of high-resolution transmission electron microscopy and transition matrix. The β?′ precipitates have two cross-sections, rectangle-shaped and round-shaped aligned with [0?0?1]_Al direction, but only rectangle-shaped cross-section exists for Q?′ precipitates. And, both of them have 12 variants and orientations with Al matrix. However, there are only three different zone axes, [0?0?0?1]_β?′, [1?4?5?0]_β?′, and [5?4?1?0]_β?′ for β?′ precipitates, and [0?0?0?1]_Q?′, [1?4?5?0]_Q?′, and [3?2 1?0]_Q?′ for Q?′ precipitates, parallel to the [0?0?1]_Al direction when they are precipitated from the Al matrix, respectively. Then, a new [0?0?1]_Al SADP model, which superposes diffraction patterns of the β?′ and Q?′ precipitates, is established. Furthermore, some “cross-shaped” diffraction streaks appeared at over-aged state can be explained reasonably by this model, which is good in agreement with the experimental data.     

Influence of heat treatment on the microstructural evolution of Al–3 wt.% Cu during high-pressure torsion

Solution-treated, peak-aged and overaged samples of the model alloy Al–3?wt.% Cu, obtained by selective heat treatments of the pre-material, have been subjected to high-pressure torsion at room temperature and at 200?°C. The mechanical behaviour of the samples was investigated with torque measurements during deformation and microhardness measurements after deformation. Irrespective of the initial material condition, in the saturation regime a comparable equilibrium microstructure was found consisting of ultrafine aluminium grains stabilized by precipitates formed at grain boundaries.     

Partitioning and segregation of trace element Sn in a low-alloy steel

The partitioning of the trace element Sn into Cu-rich precipitates in a low-alloy pressure-vessel steel has been characterized using the three-dimensional atom probe (3DAP) technique. This investigation has revealed for the first time that the trace element Sn, present at only 0.007?at.% in the steel, partitions strongly to both small spherical precipitates (<4?nm in diameter) and to large non-spherical precipitates (largest dimension 10–50?nm) during thermal ageing. Sn was also seen to segregate strongly to the precipitate/matrix interface of a large Cu precipitate and particularly in the region where a dislocation appears to intersect the precipitate. The strong attraction of large solute atoms to special sites probably drives the interfacial segregation of Sn. This is consistent with the observation of stronger segregation of Sn to the interface of large precipitates than to the coherent interface of smaller precipitates.     

Chemistry and morphology of β′ precipitates in an aged Mg-Nd-Y-Zr alloy

While the Mg–Y–Nd system is used for industrial applications, the details of the precipitation sequence and exact role of each alloying element during ageing have not been fully quantified. Focusing on WE43, a Mg–Y–Nd alloy containing Zr, the chemistry of β′ precipitates and matrix during isothermal ageing at 250 °C is investigated using atom probe tomography. Precipitate morphologies and compositions are compared with previous electron microscopy observations, and the roles of the alloying elements are discussed.     

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.     

Electron back-scatter diffraction study of inoculation of Al

The microstructure of cast commercial-purity aluminium inoculated by addition of an Al-Ti-C grain refiner has been studied by scanning electron microscopy and electron back-scatter diffraction (EBSD). It is found that a small fraction of the TiC particles present in the melt act as nucleation centres for grains. EBSD shows that the aluminium grains have a crystallographic cube-cube orientation relationship with the particles on which they nucleate. Nucleation occurs only on the largest particles, consistent with model predictions. Despite potential thermodynamic instability, TiC particles are effective nucleating agents.     

Variational solution of the one-dimensional t–J model

A new variational scheme based on a modified Bethe–Peierls method is used to study the ground state properties of the one-dimensional t–J model. Expectation values are evaluated by cutting out a four-site cluster from a correlated Fermi sea, the ground state of which is described by a variational trial wave function. We study a generalized Gutzwiller state where nearest-neighbour hole–hole correlations are controlled variationally. From the electron concentration dependence of the ground state energy, we determine the true thermodynamic boundary where segregation into an electron-rich, and purely hole phase sets in. We also determine the spinodal line and pair susceptibilities. The variational method is applied also to an extended t–J–V model, where V is the coupling constant of the charge interaction term.