Metal deposition using Ionic liquids

There is an interest to create zinc/tin alloys to replace cadmium as a corrosion protective coating material. Existing aqueous electroplating systems for these alloys are commercially available but have several limitations. Dangerous and highly toxic complexing agents are uses e.g. cyanides. To overcome these problems, ionic liquids could provide a solution to obtain an alloy containing 20 to 30% of zinc. Ionic liquids (IL’s) often have wider electrochemical windows which allow the deposition of e.g. refractive metals that can not be deposited from aqueous solutions. In IL’s it is often not necessary to add complexing agents. The Zn/Sn alloy deposition from IL’s is therefore a promising application for the plating industry. Nevertheless, there are some issues with this alternative for aqueous systems. The degradation of the organic components, the control of the concentration of two metals and the risk of a two phase deposition instead of an alloy had to be overcome first. It is the main purpose of this thesis to obtain a Zn/Sn alloy with 20% zinc using IL’s as an electrolyte. First a separate study was performed on both the zinc and the tin deposition. Afterwards, an attempt to deposit a Zn/Sn alloy was made. An introduction to a study about the electrodeposition of refractive metals concludes this work. It initiated the research for oxygen-free IL’s to deposit molybdenum or tungsten. Several parameters (temperature, metal source and concentration, organic complexing agents,…) were optimized for both the zinc, tin and zinc/tin deposition. Experiments were performed both in a parallel plate cell and a Hull cell, so as to investigate the effect of current density as well. Ethaline200 was selected as electrolyte. As substrate, brass and iron were selected, while as anode a plate of the metal to deposit was chosen, tin for the alloy. The best efficiencies were always obtained on brass; however the iron substrate resulted in the best depositions. A concentration of 0.27M ZnCl2, 0.07M SnCl2 with 0.015M of K3-HEDTA as complexant resulted in a deposition containing the desired alloy with the amount of 20% zinc and 80% tin with good appearance. Refractory metals as molybdenum and tungsten cannot be electrodeposited from aqueous solutions without forming a co-deposition with Ni, Co or Fe. Here, IL’s could again provide a solution. A first requirement is the dissolution of a metal source. MoO3 could be suitable, however there are doubts about using oxides. Oxygen-free IL’s were sought for. A first attempt was the combination of ZnCl2 with chlormequat (CCC), which gave liquids below 150°C in molar ratios of 2 : 1 and 3 : 1. Unfortuna tely, MoO3 didn’t dissolve in these IL’s. Another route to design oxygen-free IL’s was the synthesis of quaternary ammonium salts. None of the methods used, proved viable as reaction time was long and resulted in very low yields. Therefore, no sufficient quantities were obtained to perform the possible electrochemical behavior of refractive metals.

Single-metal deposition: optimization of this fingermark enhancement technique

Following the introduction of single-metal deposition (SMD), a simplified fingermark detection technique based on multimetal deposition, optimization studies were conducted. The different parameters of the original formula were tested and the results were evaluated based on the contrast and overall aspect of the enhanced fingermarks. The new formula for SMD was found based on the most optimized parameters. Interestingly, it was found that important variations from the base parameters did not significantly affect the outcome of the enhancement, thus demonstrating that SMD is a very robust technique. Finally, a comparison of the optimized SMD with multi-metal deposition (MMD) was carried out on different surfaces. It was demonstrated that SMD produces comparable results to MMD, thus validating the technique.

Why silver deposition is so fast: Solving the enigma of metal deposition

A perfect match: Silver deposition is one of the fastest electrochemical reactions, even though the Ag+ ion loses more than 5 eV solvation energy in the process. This phenomenon, an example of the enigma of metal deposition, was investigated by a combination of MD simulations, DFT, and specially developed theory. At the surface, the Ag+ ion experiences a strong interaction with the sp band of silver, which catalyzes the reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the Electrochemical Deposition and Dissolution of Divalent Metal Ions

The deposition of Cu2+ and Zn2+ from aqueous solution has been investigated by a combination of classical molecular dynamics, density functional theory, and a theory developed by the authors. For both cases, the reaction proceeds through two one-electron steps. The monovalent ions can get close to the electrode surface without losing hydration energy, while the divalent ions, which have a stronger solvation sheath, cannot. The 4s orbital of Cu interacts strongly with the sp band and more weakly with the d band of the copper surface, while the Zn4s orbital couples only to the sp band of Zn. At the equilibrium potential for the overall reaction, the energy of the intermediate Cu+ ion is only a little higher than that of the divalent ion, so that the first electron transfer can occur in an outer-sphere mode. In contrast, the energy of the Zn+ ion lies too high for a simple outer-sphere reaction to be favorable; in accord with experimental data this suggests that this step is affected by anions.

Identification of industrial sources of airborne heavy metal pollution in urban areas

The research examines the deposition of airborne particles which contain heavy metals and investigates the methods that can be used to identify their sources. The research focuses on lead and cadmium because these two metals are of growing public and scientific concern on environmental health grounds. The research consists of three distinct parts. The first is the development and evaluation of a new deposition measurement instrument - the deposit cannister - designed specifically for large-scale surveys in urban areas. The deposit cannister is specifically designed to be cheap, robust, and versatile and therefore to permit comprehensive high-density urban surveys. The siting policy reduces contamination from locally resuspended surface-dust. The second part of the research has involved detailed surveys of heavy metal deposition in Walsall, West Midlands, using the new high-density measurement method. The main survey, conducted over a six-week period in November - December 1982, provided 30-day samples of deposition at 250 different sites. The results have been used to examine the magnitude and spatial variability of deposition rates in the case-study area, and to evaluate the performance of the measurement method. The third part of the research has been to conduct a 'source-identification' exercise. The methods used have been Receptor Models - Factor Analysis and Cluster Analysis - and a predictive source-based deposition model. The results indicate that there are six main source processes contributing to deposition of metals in the Walsall area: coal combustion, vehicle emissions, ironfounding, copper refining and two general industrial/urban processes. |A source-based deposition model has been calibrated using facctorscores for one source factor as the dependent variable, rather than metal deposition rates, thus avoiding problems traditionally encountered in calibrating models in complex multi-source areas. Empirical evidence supports the hypothesised associatlon of this factor with emissions of metals from the ironfoundry industry.

Carbon nanotube-supported metal catalysts for NOx reduction using hydrocarbon reductants. Part 1:catalyst preparation, characterization and NOx reduction characteristics

A dual catalyst system for the Selective Catalytic Reduction of NOx with hydrocarbons (HC-SCR), including distinct low and high temperature formulations, is proposed as a means to abate NOx emissions from diesel engines. Given that satisfactory high temperature HC-SCR catalysts are already available, this work focuses on the development of an improved low temperature formulation. Pt supported on multiwalled carbon nantubes (MWCNTs) was found to exhibit superior NOx reduction activity in comparison with Pt/Al2O3, while the MWCNT support displayed a higher resistance to oxidation than activated carbon. Refluxing the MWCNT support in a 1:1 mixture of H2SO4 and HNO3 prior to the metal deposition step proved to be beneficial for the metal dispersion and the NOx reduction performance of the resulting catalysts. This support effect is ascribed to the increased Brønsted acidity of the acid-treated MWCNTs, which in turn enhances the partial oxidation of the hydrocarbon reductant. Further improvements in the HC-SCR performance of MWCNT-based formulations were achieved using a 3:1 Pt–Rh alloy as the supported phase.

Atomistic molecular dynamics study of interface formation: Al on poly(p-phenylene vinylene)

We model interface formation by metal deposition on the conjugated polymer poly-para-phenylene vinylene, studying direct aluminum and layered aluminum-calcium structures Al/PPV and Al/Ca/PPV. To do that we use classical molecular dynamics simulations, checked by ab initio density-functional theory calculations, for selected relevant configurations. We find that Al not only migrates easily into the film, with a strong charge transfer to the neighboring chains, but also promotes rearrangement of the polymer in the interfacial region to the hexagonal structure. On the other hand, our results indicate that a thin Ca layer is sufficient to protect the film and maintain a well-defined metal/polymer interface, and that also a thin Al capping layer may protect the whole from environmental degradation.

Spatio-temporal modelling of environmental data

Programa Doutoral em Matemática e Aplicações.

Detection of fingermarks by colloidal gold (MMD/SMD): beyond the pH 3 limit

This work is part of a continuing goal to improve the multimetal deposition technique (MMD), as well as the single-metal deposition (SMD), to make them more robust, more user-friendly, and less labour-intensive. Indeed, two major limitations of the MMD/SMD were identified: (1) the synthesis of colloidal gold, which is quite labour-intensive, and (2) the sharp decrease in efficiency observed when the pH of the working solution is increased above pH 3. About the synthesis protocol, it has been simplified so that there is no more need to monitor the temperature during the synthesis. The efficiency has also been improved by adding aspartic acid, conjointly with sodium citrate, during the synthesis of colloidal gold. This extends the range of pH for which it is possible to detect fingermarks in the frame of the MMD/SMD. The operational range is now extended from 2 to 6.7, compared to 2-3 for the previous formulations. The increased robustness of the working solution may improve the ability of the technique to process substrates that tend to increase the pH of the solution after their immersion.

Platinum Electrodeposition in an Ionic Liquid Analogue. Solvent Stability Monitoring

The use of ionic liquid analogues as solvents has increased in order to substitute the aqueous solvents in some applications in which the side reactions are undesirable. However these solvents prepared from the mixture in the eutectic proportion of species establishing hydrogen bonds are susceptible of electrochemical reactions. The study of platinum deposition on vitreous carbon in an ionic liquid analogue (2 urea: choli ne chloride) is presented; the electrochemical study has permitted to interpret the sequence of the metal deposition process and simultaneously to analyze the behavior of the ionic liquid analogue along the process. Reduction reactions of the solvent relat ed both to the electronation of choline and hydrogen formation have been detected. Different substrata have been used in order to test the possibility and the extent of these reactions depending on the nature of material. The results indicate that the feas ible electrochemical window of the substrate/solvent is highly dependent of the kind of substrate; the negative limit is tied by the massive hydrogen reaction, reaction enhanced by the electrocatalytic character of the substrate.

Optimization of electroless copper plating on polyethylene films modified by surface grafting of vinyl ether of monoethanolamine

Metallized plastics have recently received significant interest for their useful applications in electronic devices such as for integrated circuits, packaging, printed circuits and sensor applications. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. There are several techniques for metal deposition on surface of polymers such as evaporation, sputtering, electroless plating and electrolysis. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. Polyethylene films were subjected to gamma-radiation induced surface graft copolymerization with vinyl ether of monoethanolamine. Electroless copper plating was carried out effectively on the modified films. The catalytic processes for the electroless copper plating in the presence and the absence of SnCl2 sensitization were studied and the optimum activation conditions that give the highest plating rate were determined. The effect of grafting degree on the plating rate is studied. Electroless plating conditions (bath additives, pH and temperature) were optimized. Plating rate was determined gravimetrically and spectrophotometrically at different grafting degrees. The results reveal that plating rate is a function of degree of grafting and increases with increasing grafted vinyl ether of monoethanolamine onto polyethylene. It was found that pH 13 of electroless bath and plating temperature 40°C are the optimal conditions for the plating process. The increasing of grafting degree results in faster plating rate at the same pH and temperature. The surface morphology of the metallized films was investigated using scanning electron microscopy (SEM). The adhesion strength between the metallized layer and grafted polymer was studied using tensile machine. SEM photos and adhesion measurements clarified that uniform and adhered deposits were obtained under optimum conditions.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Estudo de tensões residuais em juntas soldadas utilizando o método dos elementos finitos

Pós-graduação em Engenharia Mecânica - FEG

Spontane-Desorption-Massenspektrometrie zur Charakterisierung von gemischten, selbstorganisierten Schichten zur Metallabscheidung und zur Beobachtung von chemischen Reaktionen in dünnsten Filmen

Spontane-Desorption-Massenspektrometrie zur Charakterisierung von gemischten, selbstorganisierten Schichten zur Metallabscheidung und zur Beobachtung von chemischen Reaktionen in dünnsten Filmen Stephan Krämer Ein Ziel dieser Arbeit war es, selbstorganisierte Schichten aus steifen benzolhaltigen Thiolen herzustellen und zu charakterisieren. Diese selbstorganisierten Schichten sollten als optimale Substrate zur Abscheidung von Metallen durch CVD dienen.In einem ersten Schritt wurden Schichten aus Biphenylthiol (BT) und Biphenyldithiol (BDT) auf Edelmetalloberflächen hergestellt. Die Abhängigkeit der Eigenschaften der Schicht von dem verwendeten Substrat und von der Dauer der Selbstorganisation wurde mit der Spontane-Desorption-Massenspektrometrie untersucht. Die Untersuchung der Schichtdicke erfolgte mit Oberflächenplasmonen-Spektroskopie und die Frage der Struktur der Schichten wurde versucht, mit Hilfe der Fourier-Transform-Infrarot-Spektroskopie zu klären. Nach der Charakterisierung der reinen Schichten wurden binäre Mischungen aus BT und BDT hergestellt und auf Goldoberflächen abgeschieden. Die so hergestellten binären Schichten wurden als Substrate zur Abscheidung von Gold benutzt. Dazu wurde mit Hilfe der CVD-Technik Gold auf den Filmen abgeschieden. Im nächsten Schritt wurden die einfacheren Halogen-substituierten Phenylthiole sowohl als reine Schichten als auch als binäre Mischungen untersucht. Ein weiterer Schwerpunkt stellte die Untersuchungen zur Abscheidung von Metallen auf selbstorganisierten Schichten durch CVD dar. Neben der schon vorgestellten Abscheidung von Gold wurde die Abscheidung von Palladium und von Kupfer untersucht. Im letzten Teil dieser Arbeit wurden der Verlauf einer chemischen Reaktion in einem ultradünnen Polymerfilm beobachtet. Dazu wurden die Vernetzungsreaktion und die Hydrolyse des Copolymer P[tBMA1-co-DMIMA0,11] untersucht.