In the oil and gas industry, high corrosion resistance and hardness are needed to extend the lifetime of the coatings due to exposure to high stress and salt environments. Electrodeposition has become a favorable technique in synthesizing coatings because of low cost, convenience, and the ability to work at low temperatures. Electrodeposition of metal matrix composites has become popular for enhanced corrosion resistance and hardness in the oil and gas industry because of the major problems that persist with corrosion. Two major alloys of copper-nickel, 90-10 and 70-30, were evaluated for microbial corrosion protection in marine environments on a stainless steel substrate. Copper and copper alloys are commonly used in marine environments to resist biofouling of materials by inhibiting microbial growth. Literature surveying the electrodeposition of Cu-Ni incorporated with nano- to micro- particles to produce metal matrix composites has been reviewed. Also, a novel flow cell design for the enhanced deposition of metal matrix composites was examined to obtain the optimal oriented structure of the layered silicates in the metal matrix. With the addition of montmorillonite into the Ni and Cu-Ni matrix, an increase in strength, adhesion, wear and fracture toughness of the coating occurs, which leads to an increase corrosion resistance and longevity of the coating. These coatings were evaluated for composition and corrosion using many different types of instrumental and electrochemical techniques. The overall corrosion resistance and mechanical properties were improved with the composite films in comparison to the pure metals, which proves to be advantageous for many economic sectors including the oil and gas industry.

The new nickel/layered silicate nanocomposites were electrodeposited from different pHs to study the influence on the metal ions/layered silicate plating solution and on the properties of the deposited films. Nickel/layered silicate nanocomposites were fabricated from citrate bath atacidic pHs (1.6−3.0), from Watts’ type solution (pH ~4-5), and from citrate bath at basic pH (~9). Additionally, the new nickel/molybdenum/layered silicate nanocomposites were electrodeposited from citrate bath at pH 9.5. The silicate, montmorillonite (MMT), was exfoliated by stirring in aqueous solution over 24 hours. The plating solutions were analyzed for zeta potential, particle size, viscosity, and conductivity to investigate the effects of the composition at various pHs. The preferred crystalline orientation and the crystalline size of nickel, nickel/layered silicate, nickel/molybdenum, and nickel/molybdenum/layered silicate films were examined by X-ray diffraction. The microstructure of the coatings and the surface roughness was investigated by scanning electron microscopy and atomic force microscopy. Nickel/molybdenum/layered silicate nanocomposites containing low content of layered silicate (1.0 g/L) had increase 32 % hardness and 22 % Young’s modulus values over the pure nickel/molybdenum alloy films. The potentiodynamic polarization and electrochemical impedance measurements showed that the nickel/molybdenum/layered silicate nanocomposite layers have higher corrosion resistance in 3.5% NaCl compared to the pure alloy films. The corrosion current density of the nickel/molybdenum/layered silicate nanocomposite composed of 0.5 g/L MMT is 0.63 µA·cm-2 as compare to a nickel/molybdenum alloy which is 2.00 µA·cm-2.

M. Tech. (Department of Metallurgical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / Pure Ti, Nb, Zr, Al and V powders were used as starting materials. Ti, Ti-6Al-4V and Ti-34Nb-25Zr materials produced by SPS were compared on the basis of density, microstructure, biocompatibility, tensile strength and corrosion resistance. In this study, powder metallurgy (PM) processing route was used to fabricate the alloys. The processing route was mechanical alloying (MA) and spark plasma sintering (SPS). Commercially pure metallic powders (Ti, Nb, Zr, V and Al) of different morphological features and different formulations were prepared. Powder mixing for ternary alloys with Ti as the matrix were conducted in a turbula mixer at a speed of 49 rpm. Followed by mechanical alloying of Ti, Ti-6Al-4V and Ti-34Nb-25Zr in a high energy ball mill for 5h at 500rpm, with a ball to powder ratio of 10:1. Spark plasma sintering of Ti, Ti-6Al-4V and Ti-34Nb-25Zr biomedical alloys was conducted using a hybrid spark plasma sintering furnace at a sintering temperature, heating rate, holding time and pressure of 1200°C, 100°C/min, 10min and 50MPa, respectively. Ti-34Nb-25Zr was fabricated in two ways, fully densified and porous samples. The fully densified sample was fabricated at a sintering temperature, heating rate and holding time and pressure of 1200°C, 100°C/min, 10min and 50MPa, respectively. Whereas, porous Ti-34Nb-25Zr was fabricated using NaCl space holder at a sintering temperature, heating rate, holding time and pressure of 750°C, 50°C/min, 5min and 50MPa, respectively. This was done to compare the solid and porous alloy biocompatibility behaviour. Microstructures, elemental compositions. Phase constitution of the sintered specimens were examined using a field emission scanning electron microscope (FE-SEM) equipped with energy dispersive x-ray spectrometer (EDS) and an x-ray diffractometer (XRD). The microstructure of Ti-34Nb-25Zr had pores and precipitates of niobium. Relative density, micro-hardness, biocompatibility and corrosion test was also conducted on the metallographically polished cross sections of sintered specimens. Ti, Ti-6Al-4V and Ti-34Nb-25Zr alloys made from the irregularly shaped Ti powders and sintered on the hybrid sintering machine yielded higher densifications reaching up to 100 % relative densities. Hardness values ranging from 300-600Hv at a load of 0.5kg. The corrosion resistance of the alloys was higher in the range of 2-4 nA/cm2 exhibiting a passive behaviour in simulated body fluids, such as Hank’s, 0.9wt.% NaCl and eagles minimum essential + 10% fetal bovine serum (E-MEM+ 10% FBS). Biocompatibility tests were conducted (cytotoxicity by WST-1 with SaOS-2 human osteosarcoma cells, protein adsorption and surface wettability). Fibronectin adsorption was less for solid Ti and Ti-34Nb-25Zr (<2ng/mm) compared to Ti-34Nb-25Zr porous and Ti-6Al-4V (4 ng/mm). Albumin adsorption was the highest on Ti substrate (3 ng/mm) than on the fully densified and porous Ti-34Nb-25Zr surfaces followed by less adsorption on Ti-6Al-4V. Surface wettability of Ti and Ti-6Al-4V showed a high contact angle of between 93-98° compared to 86° for the Ti-34Nb-25Zr solid alloy, indicating that Ti-34Nb-Zr alloys exhibited hydrophilic behaviour. The surface wettability results correlated well to less fibronectin adsorption on Ti-34Nb-25Zr solid alloy and excellent adsorption for Ti-6Al-4V. Solid and porous Ti-34Nb-25Zr showed less cell proliferation (0.06 and 0.02% cell viability) which was possibly linked to fibronectin adsorption results. Biocompatibility behaviour of Ti-34Nb-25Zr solid and porous alloys was poorer than Ti (0.20% cell viability) and Ti-6Al-4V (0.23% cell viability). There was poor protein adsorption and cell proliferation on all the alloy substrates.

Superhydrophobic coatings (SHC) with excellent self-cleaning and corrosion resistance property is developed on magnetite coated AISI SAE 1020 steel by using a simple immersion method. Roughness measurement, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), contact angle measurement (CAM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS), and qualitative characterization of self-cleaning behavior, antifouling property and durability of the coatings are assessed. A water contact angle as high as 152o on the coated surface with excellent self-cleaning and resistivity to corrosion and good longevity in atmospheric air is obtained. Self-cleaning test results prove that these surfaces can find applications in large scale production of engineering materials. Potentiodynamic polarization tests and EIS tests confirm that the superhydrophobic low carbon steel surfaces have better resistance to corrosion compared to bare steel and magnetite coated steel in 3.5% NaCl solution. But the longevity of the coated steel surfaces in 3.5% salt solution is limited, which is revealed by the immersion durability test. However, hydrophobic coatings (HC) have better stability in normal tap water, and it can stay unharmed up to 15 days. Finally, hydrophobic coatings on low carbon steel surface retains hydrophobic in open atmosphere for more than two months. Results of this investigation show surface roughness is a critical factor in manufacturing hydrophobic steel surfaces. Higher contact angles are obtained for rougher and more uniform surfaces. A linear mathematical relationship (y =6x+104; R2 = 0.93) is obtained between contact angle (y) and surface roughness (x).

This research introduces and applies the concept of digital state models for civil infrastructure condition assessment and structural testing. Digital state models are defined herein as any transient or permanent 3D model of an object (e.g. textured meshes and point clouds) combined with any electromagnetic radiation (e.g., visible light, infrared, X-ray) or other two-dimensional image-like representation. In this study, digital state models are built using visible light and used to document the transient state of a wide variety of structures (ranging from concrete elements to cold-formed steel columns and hot-rolled steel shear-walls) and civil infrastructures (bridges). The accuracy of digital state models was validated in comparison to traditional sensors (e.g., digital caliper, crack microscope, wire potentiometer). Overall, features measured from the 3D point clouds data presented a maximum error of ±0.10 in. (±2.5 mm); and surface features (i.e., crack widths) measured from the texture information in textured polygon meshes had a maximum error of ±0.010 in. (±0.25 mm). Results showed that digital state models have a similar performance between all specimen surface types and between laboratory and field experiments. Also, it is shown that digital state models have great potential for structural assessment by significantly improving data collection, automation, change detection, visualization, and augmented reality, with significant opportunities for commercial development. Algorithms to analyze and extract information from digital state models such as cracks, displacement, and buckling deformation are developed and tested. Finally, the extensive data sets collected in this effort are shared for research development in computer vision-based infrastructure condition assessment, eliminating the major obstacle for advancing in this field, the absence of publicly available data sets. / Ph. D.

Aluminium smelting is a high temperature electrometallurgical process, which suffers considerable inefficiencies in power utilization and equipment maintenance. Aluminium smelting cell works in the extreme environments that contain extraordinarily aggressive gases, such as HF, CO and SO2. Mild steel used as a structural material in the aluminium industry, can be catastrophically corroded or oxidized in these conditions. This project was mainly concerned with extending the lifetime of metal structures installed immediately above the aluminium smelting cells. An aluminium-rich coating was developed on low carbon steel A06 using pack cementation technique. Yttria (Y2O3) was also used to improve the corrosion resistance of coating. Kinetics of the coating formation were studied. XRD, FESEM and FIB were employed to investigate the phase constitution and the surface morphology. Together with other potentially competitive materials, aluminium-rich coating was evaluated in simulated plant environments. Results from the long time (up to 2500h) isothermal oxidation of materials at high temperature (800??C) in air showed that the oxidation resistance of coated A06 is close to that of stainless steel 304 and even better than SS304 in cyclic oxidation tests. Coated A06 was also found to have the best sulfidation resistance among the materials tested in the gas mixture contains SO2 at 800??C. Related kinetics and mechanisms were also studied. The superior corrosion resistance of the coated A06 is attributed to the slow growing alpha-Al2O3 formed. Low temperature corrosion tests were undertaken in the gas mixtures containing air, H2O, HCl and SO2 at 400??C. Together with SS304 and 253MA, coated A06 showed excellent corrosion resistance in all the conditions. The ranking of the top three materials for corrosion resistance is: 253MA, coated A06 and SS304. It is believed that aluminised A06 is an ideal and economical replacement material in the severe corrosive aluminium smelting cell environment.

Ph.D. / Electrical Engineering / A novel combinatory on-line technique coupling Electrochemistry (EC) with Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) for in-situ quantitative determination of the corrosion mechanism in magnetic thin film structures has been developed in this research. Detailed construction of a system and a comprehensive methodology was described in this dissertation. Uniformly coated multi-layer magnetic thin film samples with multi-elemental alloys containing CoCrPtB and CrMo/Cr on the Ni/P substrate were used in this research for demonstrations. In-situ quantifications conducted in a series of experiments revealed that elemental dissolution was a predominant mechanism during corrosion courses of metallic thin film materials. At the microscopic scale, using results from depletion rate determination as well as cross-sectional analyses of microstructures and magnetic features, elemental passivity was observed to occur, depending on corrosion conditions. Without external influences, surface topographic measurements indicated that passive film could be produced at the macro-scale. The dependence of the dissolution rate of each metallic ion of alloys on electrolyte concentration, potential bias, scanning rate, and corrosion duration suggested that the most critical influential factor in corrosion mechanisms was epitaxial microstructures with strongly-oriented arrangements of grains and grain boundaries. Through the use of cross-sectional microstructural analysis, including high resolution TEM micrography, electron FFT diffraction, and nano-probe with EDS profiling, variations of elemental spatial distributions at grains and grain boundaries due to the corrosion phenomena were discovered, which provided a comprehensive understanding of occurrences of micro-corrosion in thin film structures. Because of the unique magnetic property of magnetic thin films, extensive studies of field strengths from the surface were also performed in this research. Important magnetization variations were noticed when cross-sectional images were obtained. Finally, models of corrosion kinetics in the multiple layers of magnetic thin film structures were proposed.

The properties of materials, especially of solids, can be attributed mainly to the phenomena occurring at the surface. Surface engineering deals with altering the surface properties of materials to realize useful functionalities like wear and corrosion resistance, biocompatibility, hardening etc. Among the various methods adopted, plasma surface modification stands out, because of the inherent dry processing nature and little amount of left over chemicals. In conventional plasma systems, the process is carried out in a low pressure environment. This restricts its use in treating vacuum incompatible materials including tissues and bio-medical samples. Moreover, the batch processing nature and use of expensive vacuum pumps put a bottle-neck in the throughput of any production line. The subject matter of this thesis is about developing and optimizing an atmospheric pressure (760 torr) plasma system and to use it for surface modification of polymers. The experimental system developed, consists of two parallel electrodes facing each other, each of which is covered with a dielectric plate. A gap of 4mm exists between the dielectric surfaces, through which an axial flow of the working gas is maintained. When a high voltage is applied across the electrodes, the gas breaks down, creating plasma. The surface of the sample kept in this plasma, undergoes various phenomena, depending on the power applied, type of gas used and gas flow rate. To drive the plasma a high voltage power supply, which is able to generate 10 kV at 5.8 kHz, was developed in the laboratory. By varying the process parameters, the inherent filamentary nature of discharge can be converted to a diffuse uniform glow. The purity of plasma was studied and established by analyzing the optical emission from the plasma. After optimizing the system, it was used to modify the surface properties of polyester sheets. The wetting nature was altered using fluorocarbon and oxygen plasmas, realizing hydrophobic and hydrophilic surfaces. The contact angle of a water droplet made with the surface changed from 72° to 84° degree for hydrophobic and to 22° for hydrophilic surfaces respectively. Through this investigation, an insight to the procedure for developing an Atmospheric glow discharge system was developed. The details about system frame work, the power supply, electrical and optical characterization of the plasma, are well studied and recorded. The work establishes the various parameters to be varied to convert the filamentary discharge to a uniform glow. Purity of the plasma has been studied extensively and the system design and process values essential for maintaining the purity have been dealt with. Finally the plasma was put in use for surface modification of polymers, and the surface wetting nature alteration was studied and quantified.

Aluminium smelting is a high temperature electrometallurgical process, which suffers considerable inefficiencies in power utilization and equipment maintenance. Aluminium smelting cell works in the extreme environments that contain extraordinarily aggressive gases, such as HF, CO and SO2. Mild steel used as a structural material in the aluminium industry, can be catastrophically corroded or oxidized in these conditions. This project was mainly concerned with extending the lifetime of metal structures installed immediately above the aluminium smelting cells. An aluminium-rich coating was developed on low carbon steel A06 using pack cementation technique. Yttria (Y2O3) was also used to improve the corrosion resistance of coating. Kinetics of the coating formation were studied. XRD, FESEM and FIB were employed to investigate the phase constitution and the surface morphology. Together with other potentially competitive materials, aluminium-rich coating was evaluated in simulated plant environments. Results from the long time (up to 2500h) isothermal oxidation of materials at high temperature (800??C) in air showed that the oxidation resistance of coated A06 is close to that of stainless steel 304 and even better than SS304 in cyclic oxidation tests. Coated A06 was also found to have the best sulfidation resistance among the materials tested in the gas mixture contains SO2 at 800??C. Related kinetics and mechanisms were also studied. The superior corrosion resistance of the coated A06 is attributed to the slow growing alpha-Al2O3 formed. Low temperature corrosion tests were undertaken in the gas mixtures containing air, H2O, HCl and SO2 at 400??C. Together with SS304 and 253MA, coated A06 showed excellent corrosion resistance in all the conditions. The ranking of the top three materials for corrosion resistance is: 253MA, coated A06 and SS304. It is believed that aluminised A06 is an ideal and economical replacement material in the severe corrosive aluminium smelting cell environment.

Spheroidal graphite cast iron is a material widely used in the industry for the manufacturing of all kind of covers and protective casings thanks to its good combination of mechanical properties, processability and cost. When cast iron components are put into service in corrosive environments the most common approach to protect the components is painting them. The protective painting has been found to flake off with time when aggressive washing procedures, such as the ones used in the Food &amp; Beverage industry, are applied several times. In this project, the coating of cast iron with a corrosion resistant AISI 316L stainless steel by Laser Metal Powder Deposition has been studied as an alternative protection against corrosion. Several samples with different combinations of substrate preparation, number of layers and surface conditions were produced and analysed by optical microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, wash down tests and salt spray chamber corrosion tests. Main results show that the diffusion of carbon from the carbon-rich cast iron to the stainless steel coating, which would have a negative effect on the corrosion resistant properties, was significantly low as a result of the low penetration and dilution achieved during the laser metal powder deposition process. The deposited stainless steel coatings successfully protected the substrate during the corrosion tests and the integrity of the coatings is not expected to fail during the washing producers applied in the industry.