Decoration of active sites to create bimetallic surfaces and its implication for electrochemical processes

The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity.

Recent innovations in cold-formed tubular sections

Cold-formed tubular sections are widely used in many modern steel structures. Two innovative cold-formed sections have been introduced to the Australian building industry. They are the 'in-line' galvanized rectangular hollow section (RHS) tubes and the hollow flange beams (HFB). They offer significant advantages but at the same time provide challenges to designers because of their special characteristics. The application, manufacturing, advantages and characteristics of these two sections are described.

Review of continuum, finite element and hybrid techniques in the analysis of stress concentrations in structures

When a uniform flow of any nature is interrupted, the readjustment of the flow results in concentrations and rare-factions, so that the peak value of the flow parameter will be higher than that which an elementary computation would suggest. When stress flow in a structure is interrupted, there are stress concentrations. These are generally localized and often large, in relation to the values indicated by simple equilibrium calculations. With the advent of the industrial revolution, dynamic and repeated loading of materials had become commonplace in engine parts and fast moving vehicles of locomotion. This led to serious fatigue failures arising from stress concentrations. Also, many metal forming processes, fabrication techniques and weak-link type safety systems benefit substantially from the intelligent use or avoidance, as appropriate, of stress concentrations. As a result, in the last 80 years, the study and and evaluation of stress concentrations has been a primary objective in the study of solid mechanics. Exact mathematical analysis of stress concentrations in finite bodies presents considerable difficulty for all but a few problems of infinite fields, concentric annuli and the like, treated under the presumption of small deformation, linear elasticity. A whole series of techniques have been developed to deal with different classes of shapes and domains, causes and sources of concentration, material behaviour, phenomenological formulation, etc. These include real and complex functions, conformal mapping, transform techniques, integral equations, finite differences and relaxation, and, more recently, the finite element methods. With the advent of large high speed computers, development of finite element concepts and a good understanding of functional analysis, it is now, in principle, possible to obtain with economy satisfactory solutions to a whole range of concentration problems by intelligently combining theory and computer application. An example is the hybridization of continuum concepts with computer based finite element formulations. This new situation also makes possible a more direct approach to the problem of design which is the primary purpose of most engineering analyses. The trend would appear to be clear: the computer will shape the theory, analysis and design.

An investigation of well-characterized small gold clusters by photoelectron spectroscopy, tunneling spectroscopy, and cognate techniques

After microscopic characterization of the size distributions of gold clusters, deposited on carbon substrates by vacuum evaporation or by soft landing, Au(4f') binding energy of the clusters has been measured as a function of the mean cluster size. Similar measurements have been carried out on Au clusters prepared from sols by chemical means and high-nuclearity cluster compounds. In general, small clusters with a mean diameter of $2 nm show significantly larger binding energies than the bulk metal value, due to the onset of nonmetallicity. Nonmetallicity manifests itself in terms of a tunneling conductance gap only in clusters of diameter ;5 1 nm containing 40 atoms or fewer.

Effect of Micro-Structured Copper as Cathode Material for P3HT-Based Diode

Here, the effect of micro-structured cathode material on the device performance of indium tin oxide/poly(3hexylethiophene)/copper diode (ITO/P3HT/Cu) is investigated. Two different forms of copper namely bulk metal (Cu{B}) and nanoparticle (Cu{N}) were used as top electrode to probe its effect on device performance. Crystallographic structure and nanoscale morphology of top Cu electrodes were characterized using X-ray diffraction and scanning electronmicroscopy. Electrode formed by evaporation of copper nanoparticle showed enhancement in current density. From capacitance based spectroscopy we observed that density of trap states in ITO/P3HT/copper larger size grain (Cu-LG) are one order greater than that in ITO/P3HT/copper smaller size grain (Cu-SG) device.

Steel and aluminium in a low carbon future

Production of steel and aluminium creates 10% of global carbon emissions from energy and processes. Demand is likely to double by 2050, but climate scientists are recommending absolute reductions of at least 50% and these are Increasingly entering law. How can reductions of this order happen? Only 10-20% savings can be expected in liquid metal production, so the primary industry is pursuing carbon sequestration as the main solution. However, this Is as yet unproven at scale, and as well as carrying some risk, the capital and operating costs are likely to be high, but are as yet unknown. In parallel with these strategies we can also examine whether we can reduce demand for liquid metal. 'Material efficiency' may allow delivery of existing services with less requirement for metal, for instance through designing products that use less metal, reducing process scrap, diverting scrap for other use, re-using components or delaying end of life. Overall demand reduction could occur if goods were used more intensely, alternative means were used to deliver the same services, or total demand were constrained. The paper analyses all possible options, to define and evaluate scenarios that meet the 2050 target, and discuss the steps required to bring them about. The paper concludes with suggestions for key areas where future research In metal forming can support a future low carbon economy. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Weinheim.

Surface Plasmon Resonances of Cu Nanowire Arrays

Surface plasmon resonances of arrays of parallel copper nanowires, embedded in ion track-etched polycarbonate membranes, were investigated by systematic changes of nanowires’ topology and arrays area density. The extinction spectra exhibit two peaks which are attributed to interband transitions of Cu bulk metal and to a dipolar surface plasmon resonance, respectively. The resonances were investigated as a function of wire diameter and length, mean distance between adjacent wires, and angle of incidence of the light field with respect to the long wire axis. The dipolar peak shifts to larger wavelengths with increasing diameter and length, and diminishing mean distance between adjacent wires. Additionally, the shape effect on the dipolar peak is investigated.

One-step synthesis and characterization of polyelectrolyte-protected gold nanoparticles through a thermal process

Polyelectrolyte-protected gold nanoparticles have been facilely obtained by heating an amine-containing polyelectrolyte/HAuCl4 aqueous solution without the additional step of introducing other reducing agents. All experimental data indicate that different initial molar ratio of polyelectrolyte to gold can lead to the formation of dispersed nanoparticles, quasi one-dimensional aggregates of nanoparticles or bulk metal deposits. More importantly, the growth kinetics of gold particles thus formed can be tuned by changing the initial molar ratio of polyelectrolyte to gold.

A generic time and space accurate numerical approach to closely coupled fluid-structure interaction problems

Fluid structure interaction, as applied to flexible structures, has wide application in diverse areas such as flutter in aircraft, flow in elastic pipes and blood vessels and extrusion of metals through dies. However a comprehensive computational model of these multi-physics phenomena is a considerable challenge. Until recently work in this area focused on one phenomenon and represented the behaviour of the other more simply even to the extent in metal forming, for example, that the deformation of the die is totally ignored. More recently, strategies for solving the full coupling between the fluid and soild mechanics behaviour have developed. Conventionally, the computational modelling of fluid structure interaction is problematical since computational fluid dynamics (CFD) is solved using finite volume (FV) methods and computational structural mechanics (CSM) is based entirely on finite element (FE) methods. In the past the concurrent, but rather disparate, development paths for the finite element and finite volume methods have resulted in numerical software tools for CFD and CSM that are different in almost every respect. Hence, progress is frustrated in modelling the emerging multi-physics problem of fluid structure interaction in a consistent manner. Unless the fluid-structure coupling is either one way, very weak or both, transferring and filtering data from one mesh and solution procedure to another may lead to significant problems in computational convergence. Using a novel three phase technique the full interaction between the fluid and the dynamic structural response are represented. The procedure is demonstrated on some challenging applications in complex three dimensional geometries involving aircraft flutter, metal forming and blood flow in arteries.

Multi-scale rheological model for discontinuous phenomena in materials under deformation conditions

A study of possibilities given by the developed Cellular Automata–Finite Element (CAFE) multi-scale model for prediction of the initiation and propagation of micro-shear bands and shear bands in metallic materials subjected to plastic deformation is described in the paper. Particular emphasis in defining the criterion for initiation of micro-shear and shear bands, as well as in defining the transition rules for the cellular automata, is put on accounting for the physical aspects of those phenomena occurring in two different scales in the material. The proposed approach led to the creation of the real multi-scale model of strain localization. This model predicts material behavior in various thermo-mechanical processes. Selected examples of applications of the developed model to simulations of metal forming processes, which involve strain localization, are presented in the paper. An approach based on the Smoothed Particle Hydrodynamic, which allows to overcome difficulties with remeshing in the traditional CAFE method, is presented in the paper as well. In this approach remeshing becomes possible and mesh distortion, which limits application of the CAFE method to simple deformation processes, is eliminated.

Application of radial return mapping algorithm for finite strain elastoplasticity in a hybrid finite element and particle-in-cell model

The radial return mapping algorithm within the computational context of a hybrid Finite Element and Particle-In-Cell (FE/PIC) method is constructed to allow a fluid flow FE/PIC code to be applied solid mechanic problems with large displacements and large deformations. The FE/PIC method retains the robustness of an Eulerian mesh and enables tracking of material deformation by a set of Lagrangian particles or material points. In the FE/PIC approach the particle velocities are interpolated from nodal velocities and then the particle position is updated using a suitable integration scheme, such as the 4th order Runge-Kutta scheme[1]. The strain increments are obtained from gradients of the nodal velocities at the material point positions, which are then used to evaluate the stress increment and update history variables. To obtain the stress increment from the strain increment, the nonlinear constitutive equations are solved in an incremental iterative integration scheme based on a radial return mapping algorithm[2]. A plane stress extension of a rectangular shape J2 elastoplastic material with isotropic, kinematic and combined hardening is performed as an example and for validation of the enhanced FE/PIC method. It is shown that the method is suitable for analysis of problems in crystal plasticity and metal forming. The method is specifically suitable for simulation of neighbouring microstructural phases with different constitutive equations in a multiscale material modelling framework.

Development of the multi-scale analysis model to simulate strain localization occurring during material processing

Abstract A detailed description of possibilities given by the developed Cellular Automata—Finite Element (CAFE) multi scale model for prediction of the initiation and propagation of micro shear bands and shear bands in metallic materials subjected to plastic deformation is presented in the work. Particular emphasis in defining the criterion for initiation of micro shear and shear bands, as well as in defining the transition rules for the cellular automata, is put on accounting for the physical aspects of these phenomena occurring in two different scales in the material. The proposed approach led to the creation of the real multi scale model of strain localization phenomena. This model predicts material behavior in various thermo-mechanical processes. Selected examples of applications of the developed model to simulations of metal forming processes, which involve strain localization, are presented in the work. An approach based on the Smoothed Particle Hydrodynamic, which allows to overcome difficulties with remeshing in the traditional CAFE method, is a subject of this work as well. In the developed model remeshing becomes possible and difficulties limiting application of the CAFE method to simple deformation processes are solved. Obtained results of numerical simulaA detailed description of possibilities given by the developed Cellular Automata—Finite Element (CAFE) multi scale model for prediction of the initiation and propagation of micro shear bands and shear bands in metallic materials subjected to plastic deformation is presented in the work. Particular emphasis in defining the criterion for initiation of micro shear and shear bands, as well as in defining the transition rules for the cellular automata, is put on accounting for the physical aspects of these phenomena occurring in two different scales in the material. The proposed approach led to the creation of the real multi scale model of strain localization phenomena. This model predicts material behavior in various thermo-mechanical processes. Selected examples of applications of the developed model to simulations of metal forming processes, which involve strain localization, are presented in the work. An approach based on the Smoothed Particle Hydrodynamic, which allows to overcome difficulties with remeshing in the traditional CAFE method, is a subject of this work as well. In the developed model remeshing becomes possible and difficulties limiting application of the CAFE method to simple deformation processes are solved. Obtained results of numerical simulations are compared with the experimental results of cold rolling process to show good predicative capabilities of the developed model.tions are compared with the experimental results of cold rolling process to show good predicative capabilities of the developed model.

Nitrocarburising and low-temperature chromising duplex surface treatment

A new duplex surface engineering process has been developed that involves the deposition of chromium on ferritic nitrocarburised steel surfaces at low temperatures. This process formed a thin and hard chromium carbonitride surface layer and is to be applied to hardened tooling used in metal forming operations for improved wear performance and die life.