Alloying and Phase Transformation of Fe/FeNi Core/Alloy Nanoparticles at High Temperatures

This work explores how to form and tailor the alloy composition of Fe/FexNi1-x core/alloy nanoparticles by annealing a pre-formed particle at elevated temperatures between 180 – 325 oC. This annealing allowed for a systematic FeNi alloying at a nanoparticle whose compositions and structure began as a alpha-Fe rich core, and a thin gamma-Ni rich shell, into mixed phases resembling gamma-FeNi3 and gamma-Fe3Ni2. This was possible in part by controlling surface diffusion via annealing temperature, and the enhanced diffusion at the many grain boundaries of the nanoparticle. Lattice expansion and phase change was characterized by powder X-ray diffraction (XRD), and composition was monitored by X-ray photoelectron spectroscopy (XPS). Of interest is that no phase precipitation was observed (i.e., heterostructure formation) in this system and the XRD results suggest that alloying composition or alloy gradient is uniform. This uniform alloying was considered using calculations of bulk diffusion and grain boundary diffusion for Fe and Ni self-diffusion, as well as Fe-Ni impurity diffusion is provided. In addition, alloying was further considered by calculations for Fe-Ni mixing enthalpy (Hmix) and phase segregation enthalpy (HSeg) using the Miedema model, which allowed for the consideration of alloying favorability or core-shell segregation in the alloying, respectively. Of particular interest is the formation of stable metal carbides compositions, which suggest that the typically inert organic self-assembled monolayer encapsulation can also be internalized.

Effect of natural and artificial ageing on steel mechanical properties and fracture toughness

The operating conditions of welded structures of shipbuilding steels, including operation at northern latitudes, determine high requirements for their quality. Materials used for such structures should guarantee stable mechanical properties, good processability during hull fabrication and serviceability at subzero temperatures. Strain aging is due to the thermodynamic non-equilibrium of steel structure in its initial state and gradual transition to the equilibrium state provided the diffusion mobility of interstitial atoms is sufficient. In unfavorable conditions, this can lead to the degradation of properties during processing (cold straightening, bending, welding), operation or long-term storage. The paper studies the probability of natural and artificial ageing processes in steels of different chemical compositions due to bulk diffusion and carbon dislocation core diffusion (dislocation pipe diffusion). The effect of strain ageing on mechanical properties and the CTOD parameter value has been examined.

Galvanostatic Intermittent Titration Technique Reinvented: Part I. A Critical Review

The galvanostatic intermittent titration technique (GITT), introduced in 1977 by Weppner and Huggins, provided a readily accessible means to measuring the chemical diffusion coefficient of electrochemical electrode materials. The method continues to be widely used today, but the reported diffusivity values are highly inconsistent, ranging as much as four orders of magnitude for some Li layered oxide compositions. Even qualitative trends of diffusivity are inconsistent, suggesting significant flaws in the implementation of the method. Other variants of the GITT method also suffer from similar inconsistency problems. Here we identify numerous sources of significant error including composition-dependent reaction overpotentials, mathematical flaws in the relaxation analysis methods, finite-size and non-planar geometry effects, inter-particle inhomogeneity issues, early transient effects, and surface area uncertainties. We propose a simple relaxation analysis scheme using the time variable t relax + τ − t relax , where t relax is relaxation time and τ is the galvanostatic pulse duration. We also propose to use dense diffusion-limited samples to isolate the bulk-diffusion process in the time domain. Chemical diffusivity can be extracted much more reliably with this improved implementation of the GITT method.

Effect of SiO2 nanoparticle addition on growth of interfacial Ag3Sn intermetallic compound layers between lead-free solder and silver conductor

This study investigated the effects of silver powder modification on intermetallic compound (IMC) formation and silver leaching during soldering at high temperatures. Silica nanoparticles (NPs) were deposited onto a silver powder surface to inhibit silver leaching, which can lead to soldering joint failure during high-temperature soldering. The NPs were deposited through hydrolysis and a condensation reaction of tetraethyl orthosilicate (TEOS) based on the Stöber method. Fourier transform infrared spectroscopy and scanning electron microscopy were used to observe the microstructures of silver powders after the deposition of silica NPs with various TEOS concentrations and various deposition times. As the deposition time increased, the amount of silica NPs on the surface of the silver powder increased. The transmission electron microscopy results show that silica NPs were located at the IMC grain boundaries, which can hinder the dissolution of IMCs by lead-free solder melt along grain boundaries during soldering, retarding silver leaching. The growth kinetics and mechanism of IMCs during soldering were investigated. The results show that the growth of IMCs is mainly dominated by bulk diffusion. The activation energy for IMC growth increased and the growth rate decreased with increasing silica NP addition and deposition time.

Pattern forming systems coupling linear bulk diffusion to dynamically active membranes or cells

Some analytical and numerical results are presented for pattern formation properties associated with novel types of reaction–diffusion (RD) systems that involve the coupling of bulk diffusion in the interior of a multi-dimensional spatial domain to nonlinear processes that occur either on the domain boundary or within localized compartments that are confined within the domain. The class of bulk-membrane system considered herein is derived from an asymptotic analysis in the limit of small thickness of a thin domain that surrounds the bulk medium. When the bulk domain is a two-dimensional disk, a weakly nonlinear analysis is used to characterize Turing and Hopf bifurcations that can arise from the linearization around a radially symmetric, but spatially non-uniform, steady-state of the bulk-membrane system. In a singularly perturbed limit, the existence and linear stability of localized membrane-bound spike patterns is analysed for a Gierer–Meinhardt activator-inhibitor model that includes bulk coupling. Finally, the emergence of collective intracellular oscillations is studied for a class of PDE-ODE bulk-cell model in a bounded two-dimensional domain that contains spatially localized, but dynamically active, circular cells that are coupled through a linear bulk diffusion field. Applications of such coupled bulk-membrane or bulk-cell systems to some biological systems are outlined, and some open problems in this area are discussed. This article is part of the theme issue ‘Recent progress and open frontiers in Turing’s theory of morphogenesis’.

Role of surfactant-induced Marangoni stresses in drop-interface coalescence

We study the effect of surfactants on the dynamics of a drop-interface coalescence using full three-dimensional direct numerical simulations. We employ a hybrid interface-tracking/level-set method, which takes into account Marangoni stresses that arise from surface-tension gradients, interfacial and bulk diffusion and sorption kinetic effects. We validate our predictions against the experimental data of Blanchette and Bigioni (Nat. Phys., vol. 2, issue 4, 2006, pp. 254–257) and perform a parametric study that demonstrates the delicate interplay between the flow fields and those associated with the surfactant bulk and interfacial concentrations. The results of this work unravel the crucial role of the Marangoni stresses in the flow physics of coalescence, with particular attention paid to their influence on the neck reopening dynamics in terms of stagnation-point inhibition, and near-neck vorticity generation. We demonstrate that surfactant-laden cases feature a rigidifying effect on the interface compared with the surfactant-free case, a mechanism that underpins the observed surfactant-induced phenomena.

Alkylimidazolium Ionic Liquids Absorption and Diffusion in Wood

Ionic liquids represent a class of highly tunable organic compounds responsible for many applications in the domain of wood-based materials. It has often been emphasized that the use of ionic liquids derives from their high affinity for lignocellulose and their good penetration ability into wood structures. This paper discusses the sorption ability of different types of 1-alkyl-3-methylimidazolium ionic liquids with lateral alkyl chains, ranging from ethyl to hexyl into spruce and beech wood, as a function of their cation molecular mass, anion type (chloride, tetrafluoroborate, acetate), and intrinsic properties (surface tension and kinematic viscosity) at room temperature. All the studied ionic liquids present high relative uptake values at the equilibrium, ranging from 11.2% to 69.7%. The bulk diffusion coefficients of the ionic liquids into the wood range from 2 × 10−3 to 28 × 10−3 mm2/min, being higher in the longitudinal direction for both types of wood. The value of the diffusion coefficients for 1-ethyl-3-methylimidazolium chloride is only 25% lower than that for water, despite the obvious differences in viscosity and surface tension, demonstrating a good penetration ability and the potential for wood industry-related applications (as impregnation compound carriers and preservatives).

Tailoring atomic diffusion for in situ fabrication of different heterostructures

Atomic diffusion has been recognized as a particularly powerful tool in the synthesis of heterostructures. However, controlled atomic diffusion is very difficult to achieve in the fabrication of individual nanostructures. Here, an electrically driven in situ solid-solid diffusion reaction inside a TEM is reported for the controlled fabrication of two different hetero-nanostructures in the Ag-Te system. Remarkably, the morphology and structure of the as-formed heterostructures are strongly dependent on the path of atomic diffusion. Our experiments revealed that the surface diffusion of Te atoms to Ag nanowires leads to a core-shell structure, while the bulk diffusion of Ag atoms give rise to a Ag2Te-Te segmented heterostructure. Heat released by Joule heating caused the surface diffusion process to be replaced by bulk diffusion and thereby determined the structure of the final product. Our experimental results provide an insight into solid-state diffusion reactions under an electric field and also propose a new process for the fabrication of complex nanostructures.