A dissertation submitted to the University of the Witwatersrand in fulfilment of the requirements for the degree of Master of Science in Engineering (Metallurgy & Materials) 2016 / The surfaces of AISI 316L stainless steel plate were laser alloyed with ruthenium powder as well as a mixture of ruthenium and nickel powders using a Nd:YAG laser set at fixed operating parameters. The microstructure, elemental composition, and corrosion characteristics of the alloyed zone were analysed using optical and scanning electron microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and corrosion potential measurements. EDS analysis of the alloyed specimen showed that through the laser surface alloying, 2 mm surface layers with 12.5wt % Ru and 5.2wt% Ru were produced on an AISI 316L stainless steel. Similar microstructures which were dendritic and columnar grains, typical of weld beads under non-equilibrium cooling conditions were observed for all samples. Hardness profile measurements showed a significant increase from 160 HV for the substrate to a maximum of 247 HV for the alloyed layer. Using an Autolab potentiostat, the corrosion behaviour and resistance of the laser alloyed layers, substrate AISI 316L, and Hastelloy© C-276 were evaluated and compared in sulphuric acid solution of different concentration and temperatures. The Hastelloy© C-276, followed by the 12.5wt% Ru presented the most noble corrosion potential (Ecorr) and the lowest corrosion current density (icorr). However, in 60wt% H2SO4 and 40oC, the 5.22 wt% Ru alloys exhibited slightly better anticorrosive properties than 12.5wt% Ru. The observed corrosion potential, Ecorr, for untreated AISI 316L stainless steel sample in 40wt% sulphuric acid solution at 40oC was -277 mV. The 5.22 wt% Ru and 12.5wt% Ru alloyed stainless steel samples presented -240 mV, and 61 mV respectively in the same solution. Besides showing comparable performance to 5.2wt%Ru sample within specific short potential ranges, Hastelloy© C-276 was generally superior in all solutions. In addition it was found that the stability of the passive layer was improved with additions of Ru. Based on the developed costing equation the cost of 5 mm AISI 316L stainless steel plate with surface area (A = 1 m2) surface alloyed with 5.2wt% Ru to a depth of 2 mm using Nd: YAG laser is estimated at R15 989, and it is less than the cost of a Hastelloy© C-276 plate of similar size which is estimated at R19 900. As the material thickness increases, the cost benefit of laser surface treatment increases and vice versa. Reduction of the Ru additions to levels below 5.2wt% would improve cost competition without detracting from performance. / MT2017

Thesis. 1977. Ph.D.--Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / Ph.D.

No description available.

Thesis (M.S.)--University of Michigan, 1973.

Thesis (M.S.)--University of Michigan, 1973.

The master’s thesis deals with corrosion resistance of cast duplex steels. In the first part the corrosion mechanisms and their individual types are described, the second part characterizes the types of stainless steels in terms of their properties, use, structural components, and their impact on mechanical and corrosion properties of steels. Individual chapter is dedicated to duplex steels. In the experimental part the resistance of 1.4517 steel against pitting corrosion depending on the alloy contents and the PREN value was investigated. Four specimens graded according to PREN were cast. Supplemented with sample stirrer blade which was affected by corrosion during service they were subjected to corrosion test according to ASTM G48-11 standard in 6% FeCl3 solution. Cast specimens were subjected to tensile test and impact test.

A dissertation submitted in fulfilment of the requirement for the degree of Master of Science in Engineering, to the Faculty of Engineering and the Built Environment, School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, 2018 / The two hydrofluoric acid (HF) storage tanks used for holding 70% technical grade HF product at the HF plant at Necsa started leaking in March 2012. An evaluation of the failure was conducted in the form of a corrosion failure analysis. It was confirmed that a higher than usual nitric acid (HNO3) content in the technical grade HF stream changed the corrosion mechanisms typically experienced within the HF storage vessels, which then caused the tanks to fail. Immersion type corrosion experiments were done to safely simulate the corrosive environment experienced by the mild steel, stainless steel and nickel alloys used on site, and to predict the change in corrosion rates and characteristics associated with the HNO3 contamination in the HF production plant circuit. Since the corrosion resistance of mild steel in HF is heavily dependent on the thickness of the protective scale on the steel, a series of planned interval corrosion tests (PICTs) was done to reproduce and then examine the oxidefluoride barrier on mild steel coupons in pure 70% HF prior to corrosion tests. These shorter PICTs were also done on the stainless steel and nickel alloys and showed that the prepassivation step had a surface cleaning effect when exposed for only 24 h. Eleven day corrosion tests were conducted to establish the effect of HNO3 concentration and temperature on mild steel corrosion in 70% HF, and to determine the change in corrosion rates and mechanisms associated with HNO3 contamination (0.1-1% HNO3) of the downstream HF products. The corrosion was characterized by analysing the corroded coupons for mass loss, apparent corrosion rates, acid consumptions, visual observations of scale formation and pits, as well as depth profiles from scanning electron microscopy and energy dispersive spectroscopy analyses. Linear relationships were frequently observed when analysing mass losses for the coupons over time, making it possible to define corrosion rates in terms of first order reaction kinetics. The harshest corrosive condition for mild steel in HF was determined to be 1% HNO3 in 70% HF at a constant temperature of 25ºC. The corrosion characteristics of alloys used in the HF plant, as affected by HNO3 impurities (in the range 50–10000 ppm) in the final HF acid product (70% Technical grade) were successfully established. Normalized SA516 Grade 70 mild steel and Monel 400 were found not adequate for use as construction materials in a plant where HNO3 contamination was >100 ppm. However, the corrosion resistance of SS 904 L was suitable under these conditions and was recommended for applications in HF solutions where the presence of an oxygen-containing acid (e.g. HNO3) is consistent. It was recommended that Alloy 31, Alloy 33 or Nirosta 4565S, with higher chromium content (>20 wt% Cr), should be considered for construction material of the HF plant when HNO3 contamination becomes unavoidable. However, if the continued use of mild steel at the plant cannot be avoided, other inhibition strategies tailored to the selective consumption of HNO3 in the HF product stream need to be investigated. / XL2019

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

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.

Tribocorrosion is a term used to describe the material degradation due to the combination of electrochemical and tribological processes. Due to a synergetic effect, the material loss can be larger than the sum of the losses due to wear and corrosion acting separately. In this thesis, the synergy of wear and corrosion was investigated for different types of material, namely the Ti-6Al-4V alloy, the SS316L stainless steel coated with a thin film of Diamond Like Carbon (DLC), and the SS301 stainless steel coated with a thin film of chromium silicon nitride (CrSiN). / A tribocorrosion apparatus was designed and constructed to conduct wear experiments in corrosive media. Sliding ball-on-plate configuration was used in this design, where the contact between the ball and the specimen is totally immersed in the test electrolyte. The specimen was connected to a potentiostat to control its electrochemical parameters, namely the potential and the current. Electrochemical techniques were used to control the kinetics of corrosion reactions, and therefore it was possible to assess separately the role of corrosion and wear in the total degradation of material, and to evaluate the synergy between them. / For Ti-6Al-4V, it was found that the corrosion and tribocorrosion depend strongly on the structure of the material. The alpha-equiaxed microstructure with fine dispersed beta-phase exhibited the best corrosion resistance. The corrosion resistance was found to decrease when the basal plane was preferentially aligned parallel to the surface, which is attributed to a low resistance to charge transfer in the oxide films formed on this plane. On the other hand, when wear and corrosion were involved simultaneously, the oxide layer protecting the substrate against dissolution was mechanically destroyed leading to a high corrosion rate. It was found that the hardness was the most important factor determining the tribocorrosion behavior of the Ti-6Al-4V alloy; samples with high hardness exhibited less mechanical wear, less wear-enhanced corrosion, and less corrosion-enhanced wear. / For DLC coatings, it was found that interface engineering plays a crucial role in the tribocorrosion behavior of DLC films. DLC films with nitrided interface layer (SS\N3h\DLC) were shown to have very poor tribocorrosion resistance; the DLC film delaminated from the substrate after 50 cycles of sliding wear at 9 N load in Ringer's solution. It should be mentioned that a previous study performed at Ecole Polytechnique de Montreal [4] has shown that the same coating resisted 1800 cycles of dry wear at 22 N without delamination. This demonstrates clearly the effect of corrosion on the wear resistance of DLC films. The use of a-SiN:H bond layer between the SS316L substrate and the DLC film improved significantly the tribocorrosion behavior of the coating. This layer acts as a barrier against corrosion reaction; the polarization resistance was 5.76 GO.cm2 compared to 27.5 MO.cm2 and 1.81 MO.cm2 for the DLC-coated SS316L with nitrided interface layer and the bare substrate, respectively. / For CrSiN coatings, it was also shown that nitriding treatment of the substrate prior to deposition reduces significantly the tribocorosion resistance of the CrSiN-coated SS301 substrates. This is attributed to the peculiar morphology of the nitrided surface prior to deposition. The high relives at the grain boundaries of the substrate may be the reason for the generation, during sliding wear, of defects in the film, which makes the infiltration of the liquid easier, and consequently leads to the destruction of the CrSiN film.