Ruthenium, proposed as a new candidate of diffusion barrier, has three different kinds of oxides, which are native oxide, electrochemical reversible oxide and electrochemical irreversible oxide. Native oxide was formed by naturally exposed to air. Electrochemical reversible oxide was formed at lower anodic potential region, and irreversible oxides were formed at higher anodic potential region. In this study, we were focusing on the effect of copper electrodeposition on each type of oxides. From decreased charge of anodic stripping peaks and underpotential deposition (UPD) waves in cyclic voltammetry (CV), efficiency of Cu deposition dropped off indicating that interfacial binding strength between Cu and Ru oxides was weakened when the Ru surface was covered with irreversible oxide and native oxide. Also, Cu UPD was hindered by both O2 and H2 plasma modified Ru surfaces because the binding strength between Cu and Ru was weakened by O2 and H2 plasma treatment. Cu/Ru and Cu/Ta bimetallic corrosion was studied for understanding the corrosion behavior between diffusion barrier (Ta and Ru) and Cu interconnects under the post chemical mechanical planarization (CMP) process in semiconductor fabrication. Gallic acid is used in post CMP slurry solution and is known well as antioxidant which is supposed to oxidize itself to prevent other species from oxidizing. However, in this study under the observation of Cu microdot corrosion test, copper was corroded only in gallic acid at specific pH region of alkaline condition which is close to the pH region for post CMP solution formula. With different pH alkaline condition, gallic acid formed different oxidized products which are characterized by cyclic voltammetry and UV-Vis spectroscopy. Therefore, the specific oxidized product from particular pH region condition caused the Cu corrosion. Also, the corrosion rate of Cu microdots was influenced by substrate effect (Cu/Ru and Cu/Ta) and ambient control, which was included in this study.

Steven Michael Ford, do hereby declare that this thesis is my own unaided work. This thesis has not been submitted in part or in full at this or any other university. This report is submitted in fulfilment of the degree of Master of Science in Engineering at the University of the Witwatersrand. / Aluminium, although often possessing adequate strength and toughness for a specific application, may be deemed unsuitable due to a less than satisfactory corrosion resistance. This unacceptable behaviour is especially prominent in the local mining industry where aluminium alloys corrode severely in the high chloride and sulphate containing waters. Of notable importance and the major motivating force for this research was the historically poor perfomance of aluminium alloy mine cages, which are suited to the task excepting for their unsatisfactory corrosion resistance. Of general importance however, is that the mining sector in South Africa represents a sizeable portion of the economy and could thus become a much greater consumer of aluminium if the metal's corrosion resistance could be improving Apart from varying the composition of the alloy, the other basic technique of increasing a metal's resistance to an environment is by applying a coating of some sort. This research looks into the use of aluminium-based metal sprayed coatings as a form of protection for various aluminium and steel substrate alloys. The purpose of a metal sprayed layer is not merely to isolate the substrate from the environment, hut also to act as a sacrificial anode at regions where the substrate is exposed. Previous work suggested that alloys of aluminium/zinc/indium produced excellent sacrificial anodes and were thus selected for this research. The zinc and indium were always alloyed with pure aluminium, with the percentage zinc varying between 0 and 12%. All the coating alloys were sprayed on a AA6261 and AA5083 aluminium alloys, a metal matrix composite and a mild steel alloy, Various electrochemical and immersion trials were then carried out in several synthetic mine waters and other corrosive media. The basic conclusion to be drawn from the results achieved is that the optimum coating for a particular substrate alloy is the one that provides the greatest potential difference between it and the substrate, while still lasting the required lifetime of the component. The reason for this is that the greater the potential difference, the better the sacrificial protection and hence the better the protection offered to any exposed areas on the surface. The fact that the coating corrodes away with time means that a balance must be found between sacrificial behaviour and required lifetime. / Andrew Chakane 2018

A thesis submitted to the Faculty of Engineering and the Built Environment, University of Witwatersrand, Johannesburg in fulfilment of the requirements for the degree of Doctor of Philosophy (Engineering), 2017 / Chromium oxide provides an inexpensive and practical means of increasing the corrosion resistance of austenitic stainless steel in most environments. However, the oxide is prone to dissolve in reducing acids and in chloride containing solutions, which compromises the durability and effective operation of structures made of austenitic stainless steel. This research project explored the use of thin ruthenium surface alloys produced by ion implantation, RF sputtering and pulsed electrodeposition (PED) to improve the corrosion resistance of AISI 304L austenitic stainless steel in reducing acids and chloride solutions via a technique known as cathodic modification. The properties of the alloyed 304L stainless steel were evaluated using a number of tools including X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), potentiodynamic polarisation, and electrochemical impedance spectroscopy (EIS). Preliminary tests in 1 M sulphuric acid showed that the ruthenium surface alloys sufficiently raised the corrosion potential of 304L stainless steel to ranges where the stability of chromium oxide is guaranteed. Surface alloys produced by RF sputtering and PED were associated with the best corrosion resistance, and protection efficiencies of at least 85%, but they spalled during corrosion exposure rendering them unsuitable for corrosion application. The corrosion of the ruthenium implanted surface alloys exhibited a strong dependence on the surface roughness of the stainless steel, with the least corrosion rates achieved on rough 304L stainless steel samples implanted with 1016 Ru/cm2 at 50 keV. Corrosion characterisation of these ruthenium implanted surface alloys was studied in various corrosive media including sulphuric acid, sodium chloride, magnesium chloride and simulated fuel cell solutions. Their corrosion rates in sulphuric acid decreased with increase in acid concentration, and exhibited non-Arrhenius behaviour in the acid solutions; corrosion rates were unaffected by increasing exposure temperature from 25 to 50°C. In 3.5 wt% sodium chloride, addition of ruthenium via ion implantation changed pit morphology from elongated to circular, indicating a diminished tendency for pits to initiate at manganese sulphide stringers. Corrosion rates of the ruthenium implanted stainless steels in the simulated fuel cell solutions were at least 69% lower than the target corrosion rate for use in polymer electrode membrane fuel cells (PEMFCs), thus presenting a possible practical application of ruthenium surface alloyed austenitic stainless steel. / CK2018

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of requirements for the degree of Master of Science. Johannesburg, 2016. / Metal dusting (MD) is a severe type of corrosion that occurs mainly in petrochemical industries. The occurrence of MD is mainly due to syngas attacking Fe-, Ni- and Co-based alloys at elevated temperatures. More recently, literature has shown that apart from syngas, liquid hydrocarbon sources have been causing problems on platformer units in refineries. In the first part of this study a highly corrosion resistant Ni-based alloy (Hastelloy C276), in its polished form, was subjected to MD conditions at 800 °C using a liquid hydrocarbon (toluene) and helium (carrier gas) for 1 h. Exposure to these conditions revealed the formation of carbon nanofilaments and graphite layers which were confirmed by laser Raman spectroscopy, scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). Burning off the carbon nanofilaments and the graphite layers in laboratory air for 1 h at 800 °C revealed that pits were formed on the Hastelloy C276. These same pits were not evident when Hastelloy C276 was exposed to either the carrier gas (helium) or laboratory air alone. Besides MD being a continuous problem in industry, this mechanism has been shown to be beneficial in the synthesis of carbon nanofilaments viz., carbon nanofibers (CNTs) and nanotubes (CNFs). In the second part of this study, unpolished Hastelloy C276 blocks (as opposed to polished blocks) were used to synthesize carbon nanofilaments. This was done as prior studies had shown that carbon nanofilaments were produced with better quality and greater yields this way. Here the flow rate (80, 160 and 240 mL/min) and reaction duration (10, 15, 30, 45, 60, 120 and 240 min) were studied using toluene (a liquid hydrocarbon). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the quality and quantity of the carbon nanofilaments synthesized. Besides the formation of carbon nanofilaments, a less important material known as graphite particle structures (GPSs) were also synthesized. These studies collectively showed that MD had taken place on the surface of Hastelloy C276 when exposed to toluene at 800 °C. / TG2016

The Center for Ocean Energy Technology at Florida Atlantic University is developing an ocean energy turbine system to investigate the feasibility of harnessing Florida's Gulf Stream current kinetic energy and transforming it into a usable form. The turbine system has components which are prone to marine corrosion given the materials they are made of and to the harsh environment they will be exposed to. This study assumes a two-part system composed of a coating system acting as a barrier and sacrificial anode cathodic protection which polarizes the metal structures to a potential value where corrosion is significantly reduced. Several configurations (varying in anode quantity, size and location) were considered in order to cathodically protect the structures with various coating qualities (poor, good and excellent). These cases were modeled and simulated via Boundary Element Method software and analyzed so as to assess the most appropriate design. / by Nicolas Gantiva. / Thesis (M.S.C.S.)--Florida Atlantic University, 2010. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.

This study investigates corrosion initiation and propagation in instrumented specimens obtained from segments of dry-cast reinforced concrete pipes. Potential, LPR and EIS measurements were carried out. During the propagation stage in different exposures, reinforcement eventually reached negative potentials values, which suggest mass transfer limitations. So far these specimens show no visual signs of corrosion such as cracks or corrosion products with one exception; where corrosion products have reached the surface. Moreover, the apparent corrosion rate values obtained suggest high corrosion rate. No crack appearance so far, could be explained by the high porosity of the specimens; the corrosion products are filling these pores. It is speculated that although, there might be mass transfer limitations present, the current demanded by the anode is being balanced by a larger cathode area due to macrocell effects, since the high moisture conditions likely reduced the concrete resistivity and increased the throwing power. / by Hariharan Balasubramanian. / Thesis (M.S.C.S.)--Florida Atlantic University, 2013. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

Instrumented dry-cast reinforced concrete pipe (DC-RCP) specimens in which corrosion of the reinforcing steel had initiated were selected to accelerate the corrosion. Type C and type F DC-RCP were used. An anodic current density of various magnitudes (0.5 μA/cm2, 1 μA/cm2 and 2.5 μA/cm2) was applied during the corrosion propagation stage. The specimens were placed in high humidity and selected specimens were later covered with wet sand. Selected specimens were terminated for visual examination and gravimetric analysis. Typically, the reinforcement potentials during the accelerated corrosion period were more negative for F specimens compared to C specimens. The C specimens experienced ~2× more corrosion than the F specimens. The accumulated corrosion products did not cause cracks. A method was developed that allows for modest corrosion acceleration during the corrosion propagation stage of DC-RCP. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2014. / FAU Electronic Theses and Dissertations Collection

The corrosion propagation stage of D-CRP (types F and C) was tested under immersion in water, high humidity, and covered with wet sand. The half-cell potential, linear polarization test, and electrochemical impedance spectroscopy measurements were performed. Selected specimens were terminated after 300 days of exposure and visually inspected. Based on corrosion potential measurements obtained during the corrosion propagation observation, and calculated corrosion rate based on LPR measurements: all specimens were actively corroding. Additionally, EIS-Rc values were calculated for FS, CS and CH specimens. The Rc_EIS were generally greater than Rc_LPR values. EIS spectra for CI and FI specimens usually included mass transport limitations, as these specimens were immersed. Both type of specimens immersed in water (FI and CI), appeared to have higher corrosion rate based on LPR-Rc. However, upon autopsy it was revealed that a more modest amount of corrosion occurred on the reinforcing steel of FI and CI terminated specimens. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2014. / FAU Electronic Theses and Dissertations Collection

Dissimilar metal joining was performed with the main goal being maximization of the strength of the joined samples, but because of some potential applications of the dissimilar joints, analyzing their corrosion behavior also becomes crucial. Starting with materials that initially have suitable corrosion resistance, ensuring that the laser processing does not diminish this property is necessary. Conversely, the laser shock peening processing was implemented with a complete focus on improving the corrosion behavior of the workpiece. Thus, many commonalities occur between these two manufacturing processes, and this thesis goes on to analyze the thermal and mechanical influence of laser processing on materials’ corrosion resistances. Brittle intermetallic phases can form at the interfaces of dissimilar metal joints. A process called autogenous laser brazing has been explored as a method to minimize the brittle intermetallic formation and therefore increase the fracture strength of joints. In particular, joining of nickel titanium to stainless steel wires is performed with a cup/cone interfacial geometry. This geometry provides beneficial mechanical effects at the interface to increase the fracture strength and also enables high-speed rotation of the wires during irradiation, providing temperature uniformity throughout the depth of the wires. Energy dispersive X-ray spectroscopy, tensile testing, and a numerical thermal modelling are used for the analysis. The material pair of nickel titanium and stainless steel have many applications in implantable medical devices, owing to nickel titanium’s special properties of shape memory and superelasticity. In order for an implantable medical device to be used in the body, it must be ensured that upon exposure to body fluid it does not corrode in harmful ways. The effect that laser autogenous brazing has on the biocompatibility of dissimilar joined nickel titanium to stainless steel samples is thus explored. While initially both of these materials are considered to be biocompatible on their own, the laser treatment may change much of the behavior. Thermally induced changes in the oxide layers, grain refinement, and galvanic effects all influence the biocompatibility. Nickel release rate, polarization, hemolysis, and cytotoxicity tests are used to help quantify the changes and ascertain the biocompatibility of the joints. To directly exert a beneficial influence on materials’ corrosion properties laser shock peening (LSP) is performed, with a particular focus on the stress corrosion cracking (SCC) behavior. Resulting from the combination of an applied load on a susceptible material exposed to a corrosive environment, SCC can cause sudden material failure. Stainless steel, high strength steel, and brass are subjected to LSP and their differing corrosion responses are determined via cathodic charging, hardness, mechanical U-bend, Kelvin Probe Force Microscopy, and SEM imaging. A description accounting for the differing behavior of each material is provided as well as considerations for improving the effectiveness of the process. SCC can occur by several different physical processes, and to fully encapsulate the ways in which LSP provides mitigation, the interaction of microstructure changes induced by LSP on SCC mechanisms is determined. Hydrogen absorbed from the corrosive environment can cause phase changes to the material. Cathodic charging and subsequent X-ray diffraction is used to analyze the phase change of sample with and without LSP processing. Lattice dislocations play an important role, and transmission electron microscopy helps to aid in the analysis. A finite element model providing spatially resolved dislocation densities from LSP processing is performed.

Corrosion and stress corrosion cracking of structural components cost an estimated $300 billion annually in the United States alone and are a safety concern for a number of industries using hot alkaline environments. These process environments may contain different amounts of sulfide and chloride; however, the combined role of these ions on the stress corrosion cracking of duplex stainless steels, which are widely used because of their generally reliable performance, had never been studied. This study shows that chlorides in sulfide-containing caustic environments actually have a significant influence on the performance of these alloys. A mechanism for stress corrosion cracking of duplex stainless steels in hot alkaline environments in the presence of sulfide and/or chloride was proposed. Microstructural and environmental aspects were studied using mechanical, electrochemical, and film characterization techniques. The results showed that selective corrosion of the austenite phase depended on percent sulfidity, alkalinity, and chloride content. Chlorides enhanced crack initiation and coalescence along the austenite/ferrite phase boundaries. Unstable passivity of duplex stainless steels in hot alkaline-sulfide environments was due to anion adsorption on the surface leading to defective film formation. Chlorides and sulfide available at the electrolyte/film surface reduced the charge transfer resistance and shifted the response of the films to lower frequencies indicating the films became more defective. The surface films consisted of an outer, discontinuous layer, and an inner, barrier layer. Fe, Mo, and Mn were selectively dissolved in alkaline and alkaline-sulfide environments. The onset of stress corrosion cracking was related to the extent of selective dissolution and was consistent with a film breakdown and repair mechanism similar to slip-step dissolution. Recommendations for reducing the susceptibility of duplex stainless steels to stress corrosion cracking in sulfide-containing caustic environments include reducing the chloride to hydroxide ratio and alloying with less Mo and Mn. The results will impact the petrochemical, pulp and paper, and other process industries as new duplex grades can be developed with optimal compositions and environments can be controlled to extend equipment life.