XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy

We present a novel method for preparing an ultra-uniform Raney-Ni catalyst, which includes melt-quenching, hydrogen treatment and leaching in an alkali solution. The resultant catalyst shows superior activity in the reaction of cyclohexanone hydrogenation. X-ray diffraction (XRD) and XPS have been employed to characterize the catalysts. As demonstrated, the pretreatment with hydrogen caused a distinct phase transfer of the Ni-Al alloys, forming more of the Ni2Al3 component. In the subsequent leaching process, the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores. Moreover, metallic Al in the hydrogen-pretreated alloy appeared to be leached more easily and thus the aluminium species remaining on the catalyst surface is aluminium oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface. Copyright (C) 2001 John Wiley & Sons, Ltd.

Structure and properties of samarium overlayer and Sm/Rh surface alloy on Rh(100)

The structure and properties of Sm overlayer and Sm/Rh surface alloy have been investigated with Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption spectroscopy (TDS). The growth of Sm on Rh(100) at room temperature (RT) appears following the Stranski-Krastanov growth mode and only the trivalent state Sm is observed from XPS results. Thermal treatment of the Sm film at 900 K leads to the formation of ordered surface alloy which shows the c(5 root2 x root2)R45 degrees and c(2 x 2) LEED patterns. Annealing the Sm film at temperature above 400 K makes the binding energy (B.E.) of Sm 3d(5/2) shift to higher energy by 0.7 eV, which indicates charge transfer from Sm to Rh(100) substrate, causing the increase of CO desorption temperature.

Lightweight Modeling of Java Virtual Machine Security Constraints using Alloy

The Java programming language has been widely described as secure by design. Nevertheless, a number of serious security vulnerabilities have been discovered in Java, particularly in the component known as the Bytecode Verifier. This paper describes a method for representing Java security constraints using the Alloy modeling language. It further describes a system for performing a security analysis on any block of Java bytecodes by converting the bytes into relation initializers in Alloy. Any counterexamples found by the Alloy analyzer correspond directly to insecure code. Analysis of a real-world malicious applet is given to demonstrate the efficacy of the approach.

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

Galvanic replacement is a versatile synthetic strategy for the synthesis of alloy and hollow nanostructures. The structural evolution of single crystalline and multiply twinned nanoparticles <20 nm in diameter and capped with oleylamine is systematically studied. Changes in chemical composition are dependent on the size and crystallinity of the parent nanoparticle. The effects of reaction temperature and rate of precursor addition are also investigated. Galvanic replacement of single crystal spherical and truncated cubic nanoparticles follows the same mechanism to form hollow octahedral nanoparticles, a mechanism which is not observed for galvanic replacement of Ag templates in aqueous systems. Multiply twinned nanoparticles can form nanorings or solid alloys by manipulating the reaction conditions. Oleylamine-capped Ag nanoparticles are highly adaptable templates to synthesize a range of hollow and alloy nanostructures with tuneable localised surface plasmon resonance.

Comprehensive search for new phases and compounds in binary alloy systems based on platinum-group metals, using a computational first-principles approach

We report a comprehensive study of the binary systems of the platinum-group metals with the transition metals, using high-throughput first-principles calculations. These computations predict stability of new compounds in 28 binary systems where no compounds have been reported in the literature experimentally and a few dozen of as-yet unreported compounds in additional systems. Our calculations also identify stable structures at compound compositions that have been previously reported without detailed structural data and indicate that some experimentally reported compounds may actually be unstable at low temperatures. With these results, we construct enhanced structure maps for the binary alloys of platinum-group metals. These maps are much more complete, systematic, and predictive than those based on empirical results alone.

Magneto-hydro-dynamic analysis of an electrolysis cell for aluminum production

An electrolytic cell for Aluminum production contains molten metal subject to high currents and magnetic flux density. The interaction between these two fields creates electromagnetic forces within the liquid metal and can generate oscillations of the fluid similar to the waves at the free surface of oceans and rivers. The study of this phenomenon requires the simulation of the current density field, of the magnetic flux density field and the solution of the equations of motion of the liquid mass. An attempt to analyze the dynamical behavior of this problem is made by coupling different codes, based on different numerical techniques, in a single tool. The simulations are presented and discussed.

Numerical simulation of vacuum dezincing of lead alloy

Removing zinc by distillation can leave the lead bullion virtually free of zinc and also produces pure zinc crystals. Batch distillation is considered in a hemispherical kettle with water-cooled lid, under high vacuum (50 Pa or less). Sufficient zinc concentration at the evaporating surface is achieved by means of a mechanical stirrer. The numerical model is based on the multiphysics simulation package PHYSICA. The fluid flow module of the code is used to simulate the action of the stirring impeller and to determine the temperature and concentration fields throughout the liquid volume including the evaporating surface. The rate of zinc evaporation and condensation is then modelled using Langmuir’s equations. Diffusion of the zinc vapour through the residual air in the vacuum gap is also taken into account. Computed results show that the mixing is sufficient and the rate-limiting step of the process is the surface evaporation driven by the difference of the equilibrium vapour pressure and the actual partial pressure of zinc vapour. However, at higher zinc concentrations, the heat transfer through the growing zinc crystal crust towards the cold steel lid may become the limiting factor because the crystallization front may reach the melting point. The computational model can be very useful in optimising the process within its safe limits.

Reliability study of the electroless Ni–P layer against solder alloy

Copper (Cu) has been widely used in the under bump metallurgy of chip and substrate metallization for chip packaging. However, due to the rapid formation of Cu–Sn intermetallic compound (IMC) at the tin-based solder/Cu interface during solder reaction, the reliability of this type of solder joint is a serious concern. In this work, electroless nickel–phosphorous (Ni–P) layer was deposited on the Cu pad of the flexible substrate as a diffusion barrier between Cu and the solder materials. The deposition was carried out in a commercial acidic sodium hypophosphite bath at 85 °C for different pH values. It was found that for the same deposition time period, higher pH bath composition (mild acidic) yields thicker Ni–P layer with lower phosphorous content. Solder balls having composition 62%Sn–36%Pb–2%Ag were reflowed at 240 °C for 1 to 180 min on three types of electroless Ni–P layers deposited at the pH value of 4, 4.8 and 6, respectively. Thermal stability of the electroless Ni–P barrier layer against the Sn–36%Pb–2%Ag solder reflowed for different time periods was examined by scanning electron microscopy equipped with energy dispersed X-ray. Solder ball shear test was performed in order to find out the relationship between the mechanical strength of solder joints and the characteristics of the electroless Ni–P layer deposited. The layer deposited in the pH 4 acidic bath showed the weak barrier against reflow soldering whereas layer deposited in pH 6 acidic bath showed better barrier against reflow soldering. Mechanical strength of the joints were deteriorated quickly in the layer deposited at pH 4 acidic bath, which was found to be thin and has a high phosphorous content. From the cross-sectional studies and fracture surface analyses, it was found that the appearance of the dark crystalline phosphorous-rich Ni layer weakened the interface and hence lower solder ball shear strength. Ni–Sn IMC formed at the interfaces was found to be more stable at the low phosphorous content (∼14 at.%) layer. Electroless Ni–P deposited at mild acidic bath resulting phosphorous content of around 14 at.% is suggested as the best barrier layer for Sn–36%Pb–2%Ag solder.

The effects of thermo-electrically induced convection in alloy solidification

The effects of a constant uniform magnetic field on thermoelectric currents during dendritic solidification were investigated using a 2-dimensional enthalpy based numerical model. Using an approximation of the dendrite growing in free space it was found that the resulting Lorentz force generates a circulating flow influencing the solidification pattern. As the magnetic field strength increases it was found that secondary growth on the clockwise side of the primary arm of the dendrite was encouraged, while the anticlockwise side is suppressed due to a reduction in local free energy. The preferred direction of growth rotated in the clockwise sense under an anti-clockwise flow for both the binary alloy and pure material. The tip velociy is significantly increased compared to growth in stagnant flow. This is due to a small recirculation that follows the tip of the dendrite; bringing in colder liquid and lower concentrations of solute. The recirculation being not normally incident on the tip is most likely the cause for the rotation. Grain growth consisting of multiple seeds with the same anisotropy growing in the same plane, gives a competition to release latent heat resulting in stunted growth. The initial growth for each dendrite is very similar to the single seed cases indicating that dendrites must become before the thermoelectric interactions are significant.

Thermoelectric effects on alloy solidification microstructure

Thermoelectric currents in the presence of a magnetic field generate Lorentz forces which can drive fluid flow. In the case of dendritic growth a naturally occurring thermoelectric current exists and in the presence of a high magnetic field micro convections are generated. Experimental evidence has attributed changes in microstructure to this effect. A numerical model has been developed to study the flow field around an unconstricted equiaxed dendrite growing under these conditions. The growth is modeled in 2D and 3D by an enthalpy based method and a complex flow structure has been predicted. Using a pseudo-3D approximation for economy, realistic 2D simulations are obtained where a fully coupled transient scheme reveals significant changes to the dendrite morphology reflecting experimental evidence. There is a rotation of the preferred direction of growth and increased secondary branching.