Electronically reconfigurable metal-on-silicon metamaterial

This work was supported by Toyota Motor Engineering and Manufacturing North America and partially supported by the Air Force Office of Scientific Research (Grant No. FA9550-09-1-0562).

Modelling the metal arc weldpool

Traditionally, before flip chips can be assembled the dies have to be attached with solder bumps. This process involves the deposition of metal layers on the Al pads on the dies and this is called the under bump metallurgy (UBM). In an alternative process, however, Copper (Cu) columns can be used to replace solder bumps and the UBM process may be omitted altogether. After the bumping process, the bumped dies can be assembled on to the printed circuit board (PCB) by using either solder or conductive adhesives. In this work, the reliability issues of flip chips with Cu column bumped dies have been studied. The flip chip lifetime associated with the solder fatigue failure has been modeled for a range of geometric parameters. The relative importance of these parameters is given and solder volume has been identified as the most important design parameter for long-term reliability. Another important problem that has been studied in this work is the dissolution of protection metals on the pad and Cu column in the reflow process. For small solder joints the amount of Cu which dissolves into the molten solder after the protection layers have worn out may significantly affect solder joint properties.

An architectural approach to autonomics and self-management of automotive embedded electronic systems

Embedded electronic systems in vehicles are of rapidly increasing commercial importance for the automotive industry. While current vehicular embedded systems are extremely limited and static, a more dynamic configurable system would greatly simplify the integration work and increase quality of vehicular systems. This brings in features like separation of concerns, customised software configuration for individual vehicles, seamless connectivity, and plug-and-play capability. Furthermore, such a system can also contribute to increased dependability and resource optimization due to its inherent ability to adjust itself dynamically to changes in software, hardware resources, and environment condition. This paper describes the architectural approach to achieving the goals of dynamically self-configuring automotive embedded electronic systems by the EU research project DySCAS. The architecture solution outlined in this paper captures the application and operational contexts, expected features, middleware services, functions and behaviours, as well as the basic mechanisms and technologies. The paper also covers the architecture conceptualization by presenting the rationale, concerning the architecture structuring, control principles, and deployment concept. In this paper, we also present the adopted architecture V&V strategy and discuss some open issues in regards to the industrial acceptance.

Modelling metal powder production by the gas atomisation process

Metal powder in the range of 10-100 microns is widely employed in the production of Raney nickel type catalysts for hydrogenation reactions and hydrogen fuel cell manufacture. In this presentation we examine the modelling of powder production in a gas atomisation vessel using CFD techniques. In a fully coupled Lagrangian-Eulerian two phase scheme, liquid meal particles are tracked through the vessel following atomisation of a liquid nickel-aluminium stream. There is full momentum, heat and turbulence transport between particles and surrounding argon gas and the model predicts the position of solidification depending on particle size and undercooled condition. Maps of collision probability of particles at different stages of solidification are computed, to predict the creation of satellite defects, or to initiate solidification of undercooled droplets. The model is used to support experimental work conducted under the ESA/EU project IMPRESS.

Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO2 as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity - sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1: 1. The concentrations of mercury and other heavy metals in the leachates were below 0.10 mg/L and 5 mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na2CO3 and CO2 may practically apply to cement-based s/s of heavy metal-bearing sediment. (C) 2008 Elsevier B.V. All rights reserved.

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition Of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of Si-29 solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research oil the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique. (C) 2008 Elsevier Ltd. All rights reserved.

Effects Of Low Metal Levels On A Clonal Hydroid

We frequently require sensitive bioassay techniques with which to study the effects of marine contaminants at environmentally realistic concentrations. Unfortunately, it is difficult to achieve sensitivity and precision in an organism amenable to indefinite periods of laboratory culture. Results from different laboratories are often extremely variable: LC50 values for the same substance, using the same organism, may differ by two or even three orders of magnitude (Wilson, Cowell & Beynon, 1975). Moreover, some of the most sensitive bioassay organisms require nutrient media, which may alter the availability and toxicity of metals by complexing them (Jones, 1964; Kamp-Nielsen, 1971; Hannan & Patouillet, 1972) and often contain metal impurities at significant levels (Albert, 1968; Steeman Nielsen & Wium Anderson, 1970). The object of the work reported here has been to develop a technique by which these problems might be minimized or avoided. Hydroids were chosen as bioassay organisms for a variety of reasons. They are tolerant but sensitive to small variations in their chemical environment. Techniques for growing hydroids are simple and they can be cultured under conditions of near optimal temperature, salinity and food supply, thus minimizing the errors frequent in bioassay work arising from variations in the history of the test organisms, their size, sex or physiological state. An important source of variability in all work with organisms is that inherent in the genetic material, but with hydroids this can be avoided by the use of a single clone.

Xanthoria parietina as a biomonitor of airborne heavy metal pollution in forest sites in the North East of Morocco

Xanthoria parietina, common foliose lichen, growing in its natural habitat, was analysed for the concentration of five heavy metals (Fe, Cr, Zn, Pb and Cu) from different forest sites of North East of Morocco (Kenitra, Sidi Boughaba, Mkhinza, Ceinture Verte near Temara city, Skhirate, Bouznika and Mohammedia). The quantification was carried out by inductively coupled plasma - atomic emission spectrometry (ICP-AES). Results were highly significant p<0,001. The concentration of metals is correlated with the vehicular activity and urbanization. The total metal concentration is highest at the Kenitra area, followed by Ceinture Verte site near Temara city, which experience heavy traffic throughout the year. Scanning electron microscopy (SEM) of particulate matter on lichen of Xanthoria parietina was assessed as a complementary technique to wet chemical analysis for source apportionment of airborne contaminant. Analysis revealed high level of Cu, Cr, Zn and Pb in samples near roads.  

Giovanni Battista Montano as Architectural Draughtsman: Recording the Past and Designing the Future

Giovanni Battista Montano (1534-1621), who was born in Milan and trained as a woodcarver, relocated permanently to Rome in the early 1570s where his interest in sculpting was replaced by intense study of the city’s antique monuments and ruins. Although Montano carried out several sculptural and architectural projects during his time in Rome, it is his surviving corpus of drawings that testifies to his passion of exploring ancient architecture through the medium of drawing. While Montano was not famous during his lifetime, a large body of his intriguing designs became celebrated and widely circulated after his death thanks to the 1624 publication of Montano’s designs by his loyal pupil, Giovanni Battista Soria. Montano’s lifelong work differs from virtually all of his predecessors and contemporaries in its “fantastical” and ornamental nature. This thesis explores Montano’s artistic training as it relates to his later interest in imaginatively reconstructing antique buildings, along with his disregard for archaeological or historical accuracy. The subject matter upon which Montano focused is discussed, along with his objective in creating a large corpus of half-historical, half-invented drawings. His drawing techniques are explored with specific reference to the largest group of extant Montano drawings, today housed in Sir John Soane’s Museum, London, England, and also in reference to three original Montano drawings in the Centre Canadien d’Architecture/Canadian Centre for Architecture, Montréal. Also explored is the legacy and impact of Montano’s drawings and the later publications of his designs on the works of Roman Baroque architects, specifically Borromini and Bernini. This thesis ultimately attempts to understand the impact of the intellectual and artistic environment surrounding Montano in late sixteenth and early seventeenth century Rome, his drawing techniques, his choice of subject matter, and the reception that his unique works received from contemporary artists and intellectuals, along with those of the following generation.

General rules for predicting where a catalytic reaction should occur on metal surfaces: A density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces

To predict where a catalytic reaction should occur is a fundamental issue scientifically. Technologically, it is also important because it can facilitate the catalyst's design. However, to date, the understanding of this issue is rather limited. In this work, two types of reactions, CH4 CH3 + H and CO C + 0 on two transition metal surfaces, were chosen as model systems aiming to address in general where a catalytic reaction should occur. The dissociations of CH4 - CH3 + H and CO --> C + O and their reverse reactions on flat, stepped, and kinked Rh and Pd surfaces were studied in detail. We find the following: First, for the CH4 Ch(3) + H reaction, the dissociation barrier is reduced by similar to0.3 eV on steps and kinks as compared to that on flat surfaces. On the other hand, there is essentially no difference in barrier for the association reaction of CH3 + H on the flat surfaces and the defects. Second, for the CO C + 0 reaction, the dissociation barrier decreases dramatically (more than 0.8 eV on Rh and Pd) on steps and kinks as compared to that on flat surfaces. In contrast to the CH3 + H reaction, the C + 0 association reaction also preferentially occurs on steps and kinks. We also present a detailed analysis of the reaction barriers in which each barrier is decomposed quantitatively into a local electronic effect and a geometrical effect. Our DFT calculations show that surface defects such as steps and kinks can largely facilitate bond breaking, while whether the surface defects could promote bond formation depends on the individual reaction as well as the particular metal. The physical origin of these trends is identified and discussed. On the basis of our results, we arrive at some simple rules with respect to where a reaction should occur: (i) defects such as steps are always favored for dissociation reactions as compared to flat surfaces; and (ii) the reaction site of the association reactions is largely related to the magnitude of the bonding competition effect, which is determined by the reactant and metal valency. Reactions with high valency reactants are more likely to occur on defects (more structure-sensitive), as compared to reactions with low valency reactants. Moreover, the reactions on late transition metals are more likely to proceed on defects than those on the early transition metals.

On the generation of metal clusters with the electrochemical scanning tunneling microscope

In the present work we consider two aspects of the deposition of metal clusters on an electrode surface. The formation of such clusters with the tip of a scanning tunneling microscope is simulated by atom dynamics. Subsequently the stability of these clusters is investigated by Monte Carlo simulations in a grand-canonical ensemble. In particular, the following systems were considered explicitly: Pd clusters on Au(111), Cu on Au(111), Ag on Au(111), Pb on Au(111) and Cu on Ag(111). The analysis of the results obtained for the different systems leads to the conclusion that optimal systems for nanostructuring are those where the metals participating have similar cohesive energies and negative heats of alloy formation. In this respect, the system Cu-Pd(111) is predicted as a good candidate for the formation of stable clusters. (c) 2005 Elsevier B.V. All rights reserved.

C-H bond activation over metal oxides: A new insight into the dissociation kinetics from density functional theory

The C-H activation on metal oxides is a fundamental process in chemistry. In this paper, we report a density functional theory study on the process of the C-H activation of CH4 on Pd(111), Pt(111), Ru(0001), Tc(0001), Cu(111), PdO(001), PdO(110), and PdO(100). A linear relationship between the C-H activation barrier and the chemisorption in the dissociation final state on the metal surfaces is obtained, which is consistent with the work in the literature. However, the relationship is poor on the metal oxide surfaces. Instead, a strong linear correlation between the barrier and the lattice O-H bond strength is found on the oxides. The new linear relationship is analyzed and the physical origin is identified. (c) 2008 American Institute of Physics.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N-2+3H(2)-->2NH(3)). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H-->NH, NH+H-->NH2 and NH2+H-->NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H-->CH and O+H-->OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors. (C) 2003 American Institute of Physics.

Resolution of an ancient surface science anomaly: Work function change induced by N adsorption on W{100}

For many decades it has been assumed that an adsorbate centered above a metal surface and with a net negative charge should increase the work function of the surface. However, despite their electronegativity, N adatoms on W{100} cause a significant work function decrease. Here we present a resolution of this anomaly. Using density functional theory, we demonstrate that while the N atom carries a negative charge, of overriding importance is a reduction in the surface overspill electron density into the vacuum, when that charge is engaged in bonding to the adatom. This novel interpretation is fundamentally important in the general understanding of work function changes induced by atomic adsorbates.