Steel corrosion in reinforced concrete is a major concern to transportation agencies nationwide because of the expenses incurred for repair and ultimate shortening of bridge life. Cathodic protection (CP), as a remedy, has been applied to reinforced bridges in the US since 1974. However, application of this technique is largely empirical, lacking fundamental understanding. In order to optimize the performance of a CP system, it is important to monitor the rebar potential with respect to a reliable reference electrode. Moreover, because of potential variation in the concrete, reference cell placement is fundamental to ensure effective protection. The work plan was divided into two parts: laboratory scale experimentation and computer simulation. In the experimentation section, the response of graphite probes was compared to that of an Orion silver-silver chloride electrode. Graphite probes behaved as well as the standard electrode. Furthermore, the home-made graphite probes behaved the same as the commercial ones. This will allow much greater experimental latitude since the home-made probes are much more economical than the commercial ones. A finite difference code was developed to assess the performance of cathodic protection. The potential distribution in a two dimensional geometry of a concrete block with a sprayed zinc anode at one boundary and an iron cathode at the other side was calculated under cathodic protection. The equations were solved by means of a Gauss-Seidel iterative method with the help of an overrelaxation factor. An interval halving method was used to solve for nonlinear boundary condition at the iron. The effects of concrete pore saturation, concrete cover, and applied potential were studied to determine the degree of protection and proper placement of the reference electrode in concrete. Furthermore, a sensitivity analysis was performed versus input parameters: concrete conductivity, oxygen mass transfer coefficient, and oxygen reduction polarization parameters. The results of the simulation showed that the center of the rebar is less protected than the other locations. Therefore, the reference electrode should be located as close to the center as possible. / Graduation date: 1995

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.

M. Tech. Chemical Engineering. / Discusses the effect of ferrous gluconate (FG) and zinc gluconate (ZG) as novel corrosion inhibitors on the corrosion rate of mild steel and aluminium alloy in 3.5% NaCl and 0.5 M H2SO4 media was investigated by electrochemical and weight loss techniques. The effect of inhibitor concentration was investigated. The concentration of these inhibitor ranges from 0.5 to 2.0% g/v at a temperature of 28OC. The synergetic effect of these inhibitors was also studied. High resolution scanning electron microscopy equipped with energy dispersive spectroscopy (HR-SEM/EDS) and Raman spectroscopy was used to characterize the surface morphology of the metals before and after corrosion. Experimental results revealed that ferrous gluconate and zinc gluconate in 3.5% NaCl and 0.5 M H2SO4 solution decreased the corrosion rate at the different concentrations studied. Maximum inhibition efficiency of 100% was achieved for mild steel at 0.5% g/v concentration of FG, 0.5% g/v concentration of ZG and 1.5% g/v synergetic of FG + ZG in 3.5% NaCl solution. Similarly, 100% inhibition efficiency was obtained for aluminium alloy at different media studied (3.5% NaCl and 0.5 M H2SO4). The experimental results obtained from potentiodynamic polarization method showed that the presence of FG and ZG in 3.5% NaCl and 0.5 M H2SO4 solutions decreases the corrosion current densities (icorr) and corrosion rates (CR), and increases the polarization resistance (Rp). It was observed that the inhibitor efficiency depends on the corrosive media, concentration of the inhibitor and the substrate material. The adsorption characteristics of FG and ZG were best described by the Langmuir and Freundlich isotherms. Good correlation exists between the results obtained from both polarization and weight loss methods.

M. Tech. Engineering Metallurgy. / Aims to improve the mechanical and chemical properties of mild steel, by developing highly corrosion resistant surface coatings of zinc-aluminum using the electro-deposition techniques. Properties that are targeted are specifically hardness, wear and corrosion resistances.

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.

Microbiologically Influenced Corrosion (MIC) is a process influenced by microbial presence and their metabolic activities. This study examined the microbial effects on metal corrosion under different environmental conditions with nutrient supplements. Experiments were conducted by inserting stainless steel 304 and mild steel coupons (2.5 x 2.5 cm²) into loam soil and a simulated seawater/sediment system with various nutrient conditions (sterilized, without supplement, 5 mM NaNO₃ or NH₄NO₃). Two mild and stainless steel coupons were removed monthly and the corrosion rate was evaluated based on the weight loss. Bacterial populations were enumerated using the most probable number (MPN) technique. The presence and adhesion of microbes on mild steel coupons were examined using Scanning Electron Microscopy (SEM). The extent of the corrosion process on the surface of the metal coupons were visualized by using the Stereo Microscope. The elemental composition of the corrosion products formed on the coupon surface were determined by Energy Dispersive X-Ray analyses. Isolation and identification of aerobic microorganisms were conducted and examined for its potential in either accelerating or inhibiting corrosion. The bacterial populations present on the mild steel surface were analyzed by fluorescent in situ hybridization. Denaturing gradient gel electrophoresis (DGGE) analyses of PCR-amplified 16S rDNA fragments were conducted to determine the microbial community complexity of the biofilm. Greater weight losses of mild steel in loam soil and the seawater/sediment system with NaNO₃ (48.86 mg/g and 19.96 mg/g of weight loss, respectively after 20 weeks) were observed with total heterotrophic bacterial population presented (106.695 MPN/ml and 0.11187 MPN/ml respectively) compared to the autoclaved control (7.17845 mg/g and 0.12082 mg/g of weight loss respectively). Supplementation of 5 mM NH₄NO₃ increased the total heterotrophic bacterial population and resulted in a decrease in weight loss measurements on the stainless steel coupons (211.4 MPN/ml with a 0.01 mg/g weight loss) after 20 weeks compared to the non-autoclaved loam soil and loam soil supplemented with NaNO₃ (139.2 MPN/ml and 134.9 MPN/ml respectively with no weight loss). SEM images of the mild steel coupons confirmed the presence and adherence of bacteria on the metal surface. Stereo microscopic images displayed reddish-brown deposits and pitting on the coupon surface. Isolation, identification and sequence analysis revealed that most microorganisms were the Bacillus species. This group of microorganisms are iron-oxidizing bacteria that could also promote the corrosion process. After 20 weeks of incubation, the total SRB cell counts were lower in samples supplemented with NaNO₃ in both loam soil and the seawater/sediment system. This study also indicated that the isolated aerobic microorganisms do play a role in the corrosion process in both stainless and mild steel. DGGE analysis revealed microbial diversity in the corrosion products especially those affiliated to the bacterial phyla Firmicutes and Gamma-Proteobacteria. Fluorescent in situ hybridization analysis allowed for an overall estimation of Eubacteria and sulphate-reducing bacteria present in the biofilm formed on the surface of mild steel. The current study indicates that the addition of nitrates did not significantly reduce the rates of corrosion of both mild and stainless steel. However, it does seem that environmental conditions did pose as an important factor in the corrosion process. Therefore, further studies need to be implemented to analyze the environmental type, microbial composition and optimization of the concentration of nitrates for possible mitigation of metal corrosion. To optimize MIC prevention and control, collaboration between engineers and microbiologists proves advantageous to develop an environmentally sound and potentially cost-effective approach to control corrosion. / Thesis (Ph.D.)-University of KwaZulu-Natal, Westville, 2012.

Note: / as hip and knee prosthesis, orthopaedic fixations and coronary stents. The definition of a material's biocompatibility necessitates meeting a number of criteria, including high corrosion resistance and desirable interactions of the material's surface with biological species, such as cells, platelets, and serum proteins. SSs offer acceptable resistance to uniform (general) corrosion when used as materials of construction in sorne industrial applications, which is due to the formation of a thin passive oxide film on their surface. [...] / Les aciers inoxydables (AI) 316-L sont fréquemment utilisés dans le domaine biomédical. Par exemple, nous les retrouvons dans les prothèses de hanche et de genou, dans les fixatures orthopédiques et dans les prothèse vasculaires. Pour qu'un matériel soit biocompatible, il doit avoir une résistence élevée à la corrosion. De plus, la surface du matériel doit avoir des intéractions favorables avec les différentes espèces biologiques c'est-à-dire les cellules.[...]

Thesis (M.S.)--Brigham Young University. Dept. of Mechanical Engineering, 2005. / Includes bibliographical references (leaves 65-67).

Orientador: Anselmo Eduardo Diniz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-22T09:27:39Z (GMT). No. of bitstreams: 1 OliveiraJunior_CarlosAncelmo_M.pdf: 7354499 bytes, checksum: 05a6c099baa7c4f194f916c8e418d4db (MD5) Previous issue date: 2013 / Resumo: Os aços inoxidáveis super duplex são ligas extremamente resistentes à corrosão, desenvolvidas para aplicações com altos níveis de exigência, em que as peças terão contato com ambientes corrosivos como a água do mar, por exemplo. Devido à sua composição química e microestrutura, que proporcionam alta resistência mecânica, alta resistência ao calor e também alta ductilidade, que são fatores positivos para a aplicação, a usinabilidade dessas ligas é geralmente muito baixa o que resulta em longos ciclos de produção e alto custo de ferramental. Este trabalho trata do torneamento da liga UNS 32750 comercialmente conhecida como SAF2507 e sua consequente influência na resistência à corrosão apresentada ao longo da aplicação. Durante os ensaios, houve variação de velocidade de corte, classe e cobertura da ferramenta, além da condição de refrigeração com alternativas de alta e baixa pressão. Os resultados indicam que as pastilhas com cobertura PVD são mais resistentes ao desgaste e, combinadas ao uso de refrigeração de alta pressão, podem melhorar o seu desempenho em relação à vida útil e rugosidade bem como à posterior resistência à corrosão do material. Desgaste de entalhe e aderência encontrados na usinagem com pastilhas PVD, juntamente com lascamentos e quebras que ocorreram nas pastilhas CVD, foram os tipos e mecanismos de desgaste/avaria da ferramenta mais encontrados durante os ensaios / Abstract: Super duplex stainless steels are extremely corrosion-resistant alloys that were developed to work in very demanding applications, in which the workpieces are exposed to corrosive environments like sea water, for example. Due to their chemical composition and microstructure, that provide high mechanical and heat resistance besides high ductility, which are favorable factors for the application, the machinability of these alloys is generally poor and results in long production cycles and high tool costs. The goal of this research is to study turning operation of the UNS 32750 alloy, commercially called SAF2507, and its consequent influence in the corrosion resistance for application situations. During the tests, the input variables were cutting speed, grade and coating of the inserts, besides the cooling conditions with low and high pressure options. The results indicate that the PVD coated inserts are more wear-resistant than the CVD inserts and when they are combined with high pressure cooling, their performance related to tool life and workpiece roughness as well as the corrosion resistance of the material after machining is improved. Notch wear and attrition found in machining with PVD inserts, together with chipping and tool breakage that occurred in machining with CVD inserts, were the most frequent types of wear/damage and wear mechanism found during the tests / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Biomining technologies have been developed to use acidophilic microorganisms and the reactions that they catalyze to extract metals from ores in the mining industry. This biological processing through hydrometallurgy is responsible for the production of a significant portion of the world’s copper and gold supplies. Acidithiobacillus ferrooxidans is one of the better-studied and important chemolithotrophic bacterial species that is a part of the natural consortia found in mines across the world. This acidophile is unique in the array of redox reactions it participates in as it is capable of oxidizing both iron and reduced inorganic sulfur species, enabling dissolution of metal from minerals. As the transition to renewable energy continues and the demand for electronic devices grows, more copper and other valuable metals will need to be extracted from increasingly low-grade ores, such as chalcopyrite. Additionally, there has been a growing interest in further developing this biotechnology for the leaching and the recovery of valuable metals from scrap alloys and electronic waste as these feedstock streams can contain rare metals at concentrations above those found in the earth. However, the challenge in deploying biomining to these applications involves understanding the interactions that can potentially inhibit the extraction of these metals. In this dissertation, we expanded the genetic toolbox for A. ferrooxidans by using a transposition technique for the chromosomal integration of exogenous genes. The ability to permanently modify the genome enables engineering of strains that can be used in industry without the need of maintaining selective pressure for plasmid-based expression. Next, we investigated the potential role of A. ferrooxidans in microbially influenced corrosion. We focused on finding conditions that would enable the corrosion of stainless steel, which is resistant to the medium typically used for the growth of the bacterium. Additionally, the further optimization of the corrosive environment and the introduction of genetically engineered cells led to additional corrosion of a higher-grade stainless steel. Then, we explored how altering the bioavailability of sulfur in different formulations could shift the population phenotypes in A. ferrooxidans. We found that a unified description with a few parameters could describe the wide range of behaviors observed in the presence of iron and sulfur. Thus, using this improved understanding of A. ferrooxidans, we are able to engineer phenotypes of interest to generate robust strains that can modulate leaching conditions.