Rozprawy doktorskie na temat „Sulphide corrosion”

[Truncated abstract] Corrosion of steel structures caused by sulphide is a common engineering problem encountered by many industries, such as the petroleum, chemical processing, mining and mineral processing industries. The control of sulphide corrosion is still a controversial topic among corrosion engineers. There is an absence of guideline for a reliable acceptable limit of sulphide level in service and each processing industry has its own empirical values. Selection of inhibitors in the sulphide environment depends on laboratory testing before its actual application in pipelines and reaction vessels. Many investigators have postulated the corrosion mechanisms due to sulphide based on operating envelopes such as pH, chloride, manganese, hydrogen sulphide, sulphate reducing bacteria levels and inhibitor concentration. It is recommended in the literature that the batch dosing of inhibitor and biocide needs to be evaluated in regards to sulphide reducing bacteria (SRB) level, which may produce sulphide concentrations up to 2000 ppm. Although sulphide scale formation may protect the base metal by providing a physical barrier, the detrimental effects of sulphide are often inevitable, such as stress corrosion cracking, hydrogen embrittlement, etc. Currently, there are many chemicals that are used as inhibitors to prevent corrosion by scavenging the sulphide from the environment. Cerium, a rare-earth element, is not used as inhibitor in the sulphide environment. Also, there are no previous research findings on the effects of compounds of rare-earth metals, such as cerium chloride (CeCl3), in sulphide environment. This research examines the corrosion behaviour of 0.4Mo-0.8Cr steel, a High Strength Low Alloy (HSLA) steel, in sulphide-polluted artificial seawater with the addition of CeCl3 and glutaraldehyde. ... It is postulated that the moderate inhibiting effect of CeCl3 is due to the scavenging effect thereby forming Ce2S3 complex. Further reaction of sulphide with steel resulted in ferrous sulphide, leading to an increased corrosion rate. It is also concluded that the CeCl3 interferes with both anodic and cathodic reactions in deaerated conditions. Addition of glutaraldehyde in the sulphide-polluted seawater was found to decrease the corrosion rate. According to the electrochemical measurements conducted, the concurrent addition of glutaraldehyde and CeCl3 appeared to have an added effect on reducing the corrosion of the steel, as evidenced by the increase of the open circuit potential during the short-term testing. From the weight loss measurements after 60 days, sulphide pollution in deaerated seawater was found to increase corrosion rate. This is attributed to the increase of sulphide activity whereby continual dissolution of steel was encountered. From the weight loss tests, it was found that the addition of CeCl3 and glutaraldehyde reduced the corrosion rate of the steel in the solutions containing 0-10 ppm sulphide. There is no noticeable corrosion rate decrease for the solution containing 100 ppm sulphide. The added effect of CeCl3 and glutaraldehyde to the SRB medium has resulted in lower corrosion rates. Further detailed experimentation is required to elucidate the corrosion reduction mechanism in glutaraldehyde-containing environments.

Pits have been observed to initiate at certain inclusions in stainless steel, which affect the composition and properties of the passive film in that region. In this thesis, the VG MA500 high resolution scanning Auger microscope associated with Link EDX is used to investigate the surface chemistry of inclusion groups in stainless steel 316 relative to the bulk composition, before and after exposure to sodium chloride solution. The work demonstrates that careful control of experimental conditions allows the progress of initiation of pits to be observed systematically. The role of inclusions as initiators of pitting corrosion has been studied from the very inception of attack. Detailed observation have been taken from separate manganese sulphide as well as mixture of manganese sulphide and multi-element oxide at various pH values of solutions to trace the behaviour of these inclusions during exposures. It is suggested from this investigation that corrosive attack starts on MnS inclusion proper. The dissolution of MnS takes place in sodium chloride solution followed by the acidification in the microarea and dissolution of metal in the region adjacent to the inclusion. The mechanism for the crevice corrosion is of importance after the microcrevice forms. The observations showed that sulphur precipitated on the area surrounding the inclusion group in acidic sodium chloride solution. This is in contrast to the finding in prior studies by electron probe or EDX analyses in which sulphur precipitation was only observed on the inclusion. Because pitting normally occurs on surfacesthat are initially exposed to air before being immersed in the corrosive solution, an understanding of the change of surface film associated with the change of medium is very important. XPS was used in this work to study the air formed and aqueous films, the transformation when the specimens were immersed in solutions. The study of the energy-loss structure of photoelectron peaks has lead to a better understanding of these various films. It has been used to study in greater detail the composition and properties of the films formed on Fe-Cr alloys during oxidation, vacuum annealing, and to find the relationship between the depth distribution of the components in the films and energy loss background of photoelectron peaks. Three features are of particular importance: the background loss tail height, the baseline slope and the post-peak loss structure. These features have been related quantitatively to the relative amounts of the element and the surrounding matrix in the layers which contribute the greatest signal at any given take-off angle. The present work illustrates that the additional depth information available from closer inspection of the inelastic loss background feature may aid an understanding of the change from the air-formed film to the aqueous film as well its effect on the initiation of pits in stainless steel 316. The combination of AES and EDX with high spatial resolution gave an opportunity to re-investigate the initiation of pits at the site of inclusion on stainless steel by offering both bulk and surface information. The use of AES and XPS associated with the energy loss structure of photoelectron peaks facilitates a comprehensive understanding for the whole surface of various films and the local areas which are involved in the formation of pits.

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO
COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
FUNDAÇÃO DE APOIO À PESQUISA DO ESTADO DO RIO DE JANEIRO
PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO
BOLSA NOTA 10
A susceptibilidade à corrosão sob tensão em aços para dutos é dependente de uma série de eventos que vão desde a manufatura do aço, fabricação do tubo, montagem dos dutos e tipo de substância transportada pelo duto. O procedimento de soldagem envolvido na montagem dos dutos pode modificar as propriedades mecânicas do metal de base na região da zona termicamente afetada (ZTA), assim como as propriedades metalúrgicas e de resistência à corrosão, tornando potencialmente a região da junta soldada com maior probabilidade de incidência de corrosão sob tensão.Este trabalho tem como objetivo estudar a resistência à corrosão sob tensão em presença de sulfeto e fragilização pelo hidrogênio, em soldas circunferenciais de tubo API 5L X80. Foram realizados: -Ensaios de acordo com norma NACE TM0177/96, Método A -Ensaios de Baixa Taxa de Deformação (BTD) de acordo com a norma ASTM G129-00/2006, em solução contendo Tiossulfato de Sódio. Os resultados mostraram que o metal base foi considerado aprovado segundo os requisitos dos testes NACE TM0177/96. Porém as juntas soldadas originadas nos diferentes processos de soldagem estudados apresentaram susceptibilidade à corrosão sob tensão em presença de sulfeto e fragilização pelo hidrogênio, segundo o mesmo critério, fraturando em um período inferior a 720h. Esta susceptibilidade foi comprovada com os resultados dos ensaios de tração BTD, tendo sido constatada uma queda significativa no limite de resistência, alongamento e tempo de ruptura, em comparação aos ensaios realizados ao ar na mesma taxa de deformação. O mecanismo de fratura predominante nos ensaios foi fratura transgranular.
The susceptibility of pipeline steels to stress corrosion cracking (SCC) depends on a series of factors ranging from the manufacture of the steel, the pipe fabrication, the assembly of the pipeline and the type of substances to be transported. Additionally, the welding procedures adopted during the production of the tubes and for construction of the pipelines (field welding), can modify the properties of the base metal in the heat affected zone (HAZ), potentially rendering this region susceptible to sulphide stress corrosion cracking and hydrogen embrittlement.This study evaluates the resistance of girth welds in API 5LX80 pipes to hydrogen embrittlement and also to stress corrosion cracking in the presence of sulphides. The evaluation was performed according to NACE TM0177/96, Method A, applying the criterion of fracture/no fracture, and slow strain rate tensile tests (SSRT) were undertaken using a sodium thiosulphate solution according to the ASTM G29 standard. According to the requirements of the NACE TM0177/96 test, the base metal was considered approved. The weld metal exhibited susceptibility to SCC in the presence of sulphides, failling in a period of less than 720h. The susceptibility of the welded joint to SCC in the presence of sulphides was confirmed by the results obtained with SSRT tensile tests, where a significant decrease in the ultimate tensile strength, elongation and time to fracture were observed. The mechanism of fracture for the tests was predominantly transgranular.

Durante a exploração de petróleo offshore (fora da costa), a injeção de água do mar no processo de recuperação secundária de petróleo, ocasiona a produção de sulfeto de hidrogênio (H2S) pela presença das bactérias redutoras de sulfato (BRS), que reduzem o sulfato presente na água em sulfeto. A produção intensiva de H2S tem sido um dos maiores problemas das indústrias petrolíferas, pois constitui-se uma das principais causas de corrosão em linhas de produção (tubulações), equipamentos e tanques metálicos. Os principais micro-organismos presentes em amostras salinas provenientes de tanques de armazenamento de água e óleo da indústria do petróleo são as bactérias anaeróbias heterotróficas totais (BANHT) e as bactérias redutoras de sulfato (BRS). Atualmente, a quantificação desses grupos microbianos é realizada através da técnica do Número Mais Provável (NMP) que estima o resultado em aproximadamente 28 dias. Neste trabalho foi utilizada a metodologia de produção semi-contínua de sulfetos biogênicos por 15 dias, numa tentativa de correlacionar com os resultados de quantificação de BANHT e BRS através da técnica convencional do NMP. Nesse caso, avaliou-se as condições mais adequadas para a produção biogênica de sulfetos em tanques, alterando-se parâmetros tais como salinidade, temperatura e composição do meio de cultura. Verificou-se que os aumentos da salinidade e da temperatura do meio implicaram na diminuição da atividade biogênica semi-contínua de geração de sulfetos. E conforme dilui-se o meio de cultura, o crescimento de bactérias foi reduzido, assim como a geração de sulfetos. A quantificação de BRS e BANHT foi avaliada pela técnica do NMP de acordo com o método do FDA em 2011 e de Harrigan em 1998. Este último subestima a população microbiana, desconsiderando os limites e erros provenientes da técnica
During off-shore oil recovery, seawater injection for secondary oil recovery, produces hydrogen sulphide (H2S), due to the presence of sulphate reducing bacteria (SRB), that reduces sulphate from seawater to sulphide. The massive production of H2S is presently one of the main problems in the petroleum industries, constituting one of the main causes of corrosion in production lines (dutes), equipments and tanks. The main microbial species found in this type of saline samples comes from water and oil storage tanks in the petroleum industry, being general anaerobic heterotrophic bacteria (GAHB) and sulphate reducing bacteria (SRB). Presently, the quantification of those microbial groups is made through a technique known as Most Probable Number (MPN). This quantification is obtained in around 28 days. In the present work a methodology based on the semi-continuous production of sulphide during 15 days was conducted, in an attempt to correlate these results with the quantification of GAHB and SRB cells through conventional MPN technique. In this case, the most suitable conditions for biogenic sulphide production in tanks, was studied through the evaluation of environmental parameters such as salinity, temperature and culture medium composition. It could be observed that an increase in salinity and temperature of the medium produced a marked decrease in the semi-continuous biogenic production of sulphide. In relation to the culture medium, its dilution promoted a decreased in cell growth, consequently in the production of sulphides. The quantification of SRB and GAHB was evaluated through the MPN technique, according to procedures suggested by FDA in 2011 and Harrigan in 1998. It was observed that this last procedure underestimated the microbial population, due to the lack of information about limits and standard deviations

Ce travail de doctorat concerne le stockage des déchets radioactifs à vie longue et haute activité en site géologique profond. Dans le concept actuellement retenu par l’Andra (Agence nationale pour la gestion des déchets radioactifs), c’est une enveloppe en acier non allié, appelée « surconteneur », qui sera au contact de l’environnement. Dans les conditions anoxiques où se retrouvera l’acier après une période initiale relativement courte, des vitesses de corrosion très faibles sont attendues, ce qui garantirait l’intégrité du surconteneur pour des millénaires. Cependant, il n’est pas exclu que des bactéries sulfurogènes puissent se développer à proximité ou au contact du surconteneur et modifier localement la cinétique de la corrosion via les espèces sulfures produites par leur métabolisme. L’objectif de cette thèse consistait à améliorer notre compréhension du système de corrosion constitué de l’acier, de sa couche de rouille essentiellement composée de sidérite FeCO3 et d’un électrolyte sulfuré.Pour ce faire, il a été nécessaire dans un premier temps de caractériser par microspectroscopie Raman les sulfures de fer impliqués dans les processus de corrosion et d’étudier les mécanismes de leur formation et de leur transformation dans différentes conditions de concentration en Fe(II) et S(-II), de pH, de température et d’oxygénation. Il a pu être démontré que le spectre Raman de la mackinawite FeS, composé qui précipite à partir de Fe(II) et S(-II) dissous dans toutes les conditions considérées ici, évoluait avec la cristallinité et l’oxydation du composé. Par ailleurs, les mécanismes de l’oxydation à 80°C en milieu acide anoxique de la mackinawite en greigite Fe3S4 ont pu être décrits. Cette étude a permis de démontrer que les sulfures de fer souvent présents sur les objets archéologiques ferreuxissus de milieux anoxiques sont soit de la mackinawite, soit étroitement apparentés à la mackinawite.Dans un deuxième temps, nous avons étudié la formation de produits de corrosion carbonatés par polarisation anodique d’électrodes d’acier à température ambiante dans des électrolytes désaérés à base de NaHCO3. Les conditions expérimentales permettant d’obtenir la sidérite ont été re précisées et utilisées pour synthétiser des couches modèles de FeCO3 sur acier. Par ailleurs, il a été observé que la rouille verte carbonatée était le principal produit se formant aux faibles concentrations en espèces carbonates (0,003 et 0,1 mol L-1 par exemple),la sidérite se formant aux fortes concentrations (0,5 et 1 mol L-1). Les conditions permettant la formation de la chukanovite, l’hydroxycarbonate de Fe(II) de formule Fe2(OH)2CO3, n’ont pas pu être explicitées, même si cette phase a été obtenue dans un électrolyte contenant à la fois des ions SO42- et HCO3- à la concentration de 0,03 mol L-1.Enfin, les interactions entre sulfures et produits de corrosion ont été étudiées. La sidérite, la lépidocrocite et la goethite sont toutes réactives vis-à-vis des sulfures. Ainsi, il apparaît clairement que les espèces sulfures produites par les BSR devraient interagir avec la couche de produits de corrosion avant d’interagir avec le métal sous-jacent. Les tests effectués sur des analogues archéologiques du 16ème siècle, immergés deux mois dans des solutions sulfurées en conditions anoxiques ont permis de le démontrer. Le principal effet de cette immersion a été la formation de sulfures de fer à l’interface entre la couche dense de produits de corrosion, essentiellement constituée de sidérite, et le milieu transformé, zone où s’entremêlent les minéraux propres au sol et ceux produits par la corrosion du fer. Les espèces sulfures n’ont pas été détectées au voisinage immédiat de la surface du métal
This PhD work deals with the nuclear waste disposal. In France, it is envisaged byAndra (French national radioactive waste management agency) that high-level radioactivewastes will be confined in a glass matrix, stored in a stainless steel canister, it self placed in a carbon steel overpack. The wastes will then be stored at a depth of ~500 m in a deep geological repositery, drilled in a very stiff (indurated) clay (argillite) formation. The kineticsof corrosion expected for the overpack in this disposal concept are low and will stay low if the somehow protective rust layer that will develop initially on the steel surface remains undamaged. Local changes of the physico-chemical conditions may however degrade this layer and induce accelerated kinetics of corrosion. In particular, the growth of sulphate reducing bacteria (SRB) close to the steel overpack cannot be excluded and the sulphid especies these micro-organisms produce may modify the corrosion process. The aim of this work was then to achieve a better understanding of the corrosion system constituted with steel, its rust layer mainly made of siderite FeCO3, and a sulphide-containing electrolyte.First, it proved necessary to characterise the iron sulphides involved in the corrosion processes by Raman micro-spectroscopy so as to study their formation and transformation mechanisms in various conditions of Fe(II) and S(-II) concentration, pH, temperature andaeration. It could be demonstrated that the Raman spectrum of mackinawite FeS, thecompound that precipitated in any case from dissolved Fe(II) and S(-II) species with the experimental conditions considered here, depended on the crystallinity and oxidation state.Moreover, the mechanisms of the oxidation of mackinawite into greigite Fe3S4 in acidicanoxic solutions at 80°C could be described. Finally, iron sulphides, often present on archaeological artefacts, could be identified using Raman micro-spectroscopy. The compounds present were mainly mackinawite and greigite.Secondly, to investigate the nature and properties of carbonated rust layers, carbonsteel electrodes were polarised anodically in NaHCO3 electrolytes continuously de-aerated byan argon flow. The experiments were performed at room temperature. The carbonated greenrust was observed to form at 0.003 and 0.1 mol L-1 NaHCO3 whereas FeCO3 was obtained atthe largest concentrations (0.5 and 1 mol L-1). Additional experiments were performed similarly in solutions of NaHCO3 and Na2SO4. Chukanovite, the Fe(II) hydroxycarbonate with formula Fe2(OH)2CO3, could be obtained in solutions containing 0.03 mol L-1 of eachsalt.Finally, interactions between sulphide species and corrosion products were studied.Siderite, goethite and lepidocrocite proved to be reactive towards sulphide. So, it seems clear that sulphide species produced by SRB should interact with the rust layer before to reach the metal underneath. Tests were performed with ferrous archaeological artefacts immersed 2months in anoxic sulphide-containing electrolytes to demonstrate it. The main effect of theimmersion was the formation of iron sulphide at the interface between the dense corrosion products layer, mainly constitute of siderite, and the transformed medium, where minerals ofthe soil are mixed with corrosion products. Sulphide species were not detected at the vicinityof the iron surface

In the petrochemical industry, carbon steels exposed to H2S environments may be susceptible to stress-corrosion cracking. A tensile residual stress and high hardness increases the risk of cracking in H2S environments. NACE SP 0472 limits weld metal hardness to 210 HV10 (200 HB) and heat-affected zone hardness to 250 HV10 to prevent stress-corrosion cracking of carbon steel welds in H2S. The hardness is controlled by the weld thermal cycle or by a post-weld heat treatment. In this project, the effect of hardness on the susceptibility to stress-corrosion cracking was investigated by increasing electrode strength systematically and measuring residual stress in the weld metal in the as-welded state. Samples were manufactured from SA 516 Gr 70, a carbon steel used extensively in the petrochemical industry. Heavily clamped plates were welded to minimise distortion and to maximise residual stress. The weld metal hardness was increased by using E6013, E7018-1, E8018-B2 and E9018-B3 electrodes without a post-weld heat treatment. Mechanical tests included all-weld and transverse tensile tests, impact strength and hardness testing. As the nominal strength of the weld metal increased, the all-weld tensile strength increased from 512 to 829 MPa, while the yield strength increased from 443 to 659 MPa. The average weld metal hardness increased from 177 to 317 HV10. The transverse tensile strength was between 511-517 MPa, while the yield strength (in the transverse direction) was between 360 and 382 MPa. Residual stresses of the welded joint were measured by neutron diffraction in the through-thickness, longitudinal and transverse direction. The Von Mises theorem evaluated the principle residual stress. Results indicate that the residual stress in the weld metal may be up to 99% of the yield strength. For stress-corrosion cracking, the samples were submerged in the standard TM0177-2005 test solution for 30 days. The only sample to crack was the E9018, with an average weld metal hardness of 317 HV10. The study results were consistent with the NACE SP0472 specification and earlier publications.
Dissertation (MEng)--University of Pretoria, 2017.
TM2019
Materials Science and Metallurgical Engineering
MEng
Unrestricted

A produção de H2S (sulfeto de hidrogênio) é um dos principais problemas na indústria do petróleo, sendo esta uma das causas da corrosão de tanques de estocagem e tubulações. Essa produção é possibilitada devido à injeção de água do mar durante o processo de recuperação secundária do petróleo, onde alguns micro-organismos presentes nessa água, tais como as bactérias anaeróbias heterotróficas totais (BANHT) e as bactérias redutoras de sulfato (BRS), que promovem a redução do sulfato a sulfeto. Atualmente, o método de quantificação destes micro-organismos é a técnica do Número Mais Provável (NMP) que estima o resultado em aproximadamente 28 dias. No presente trabalho foi utilizada a metodologia da produção semi-contínua de sulfeto biogênico pelo período de 15 dias, com o intuito de correlacionar com os resultados das quantificações de BANHT e BRS através da técnica convencional do NMP. Foram analisadas amostras de diferentes procedências da indústria do petróleo, apresentando variação na salinidade de 0 a 16 g.L-1. O objetivo deste procedimento foi avaliar as velocidades específicas e instantâneas de produção de H2S, sugerindo, desta forma, quais amostras apresentam maior potencial para a produção biogênica de sulfeto e em quais condições essa produção se dá. Observou-se que em todas as amostras a geração do H2S se dá de forma crescente até a estabilização desta produção, sendo esta obtida quase sempre em seis dias (144h) do crescimento microbiano. A produção do sulfeto biogênico se deu de forma mais intensa nas amostras do fundo de tanque de estocagem de óleo e da água de formação. A quantificação das BANHT e das BRS foram avaliadas pelo método do NMP de acordo com a tabela de Harrigan, a qual subestima a população microbiana, desconsiderando erros provenientes da técnica
The production of H2S (hydrogen sulfide) is a major problem in the oil industry, which is a cause of corrosion of pipes and storage tanks. This production is made possible due to seawater injection during the secondary oil recovery process where some microorganisms present in this water, such as total heterotrophic anaerobic bacteria (THAB) and sulphate-reducing bacteria (SRB) that promote reduction of sulfate to sulfide. Currently, the method of quantification of these microorganisms is the technique of the Most Probable Number (MPN) which estimates the results in about 28 days. The present study used the methodology of semi-continuous production of biogenic sulfide by 15 days period, in order to correlate with the measurements results of BANHT and BRS through the conventional technique of MPN. There were several samples analyzed from different origins in the oil industry, with variations in salinity from 0 to 16 g.L-1. The purpose of this procedure was to evaluate the specific speeds and instantaneous H2S production, suggesting thereby that samples had increased biogenic sulfide production and this production conditions which occurs. It was observed that all samples in the generation of H2S occurs incrementally until stabilization of this production, these being almost always obtained in six days (144h) of microbial growth. The production of biogenic sulfide occurred more intensely in the samples of oil storage tank bottom and formation water. The quantification of SRB and THAB were evaluated by the MPN method according to Harrigan table, which underestimates the microbial population, disregarding errors arising in the art

Sulphate-reducing bacteria are known to play an important role in anaerobic corrosion processes. They are often found associated with metal surfaces and their activities can be of particular economic significance in many industrial areas. The aim of this thesis was to investigate anaerobic corrosion of metals by the sulphate-reducing bacteria in the presence of mixed microbial consortia in various heterogeneous marine environments. A laboratory model system was designed, based on part of an offshore oil storage system. An extensive bacteriological analysis and comprehensive study of the consequent physicochemical parameters involved in the microbial corrosion process was carried out. Particular attention was paid to the activity of the sulphate-reducing bacteria on metal surfaces. A method was developed to measure both acid-volatile and non-acid-volatile sulphur formation, produced by the activity of the sulphate-reducing bacteria on mild steel coupons. The importance of this method is firmly stressed. Previous results involving rates of sulphate reduction estimated without considering non-acid-volatile sulphur product formation, must be interpreted with caution. A study of non-biological methods of analysing corrosion and their various limitations was carried out to assess their usefulness in determining the effect of microbial corrosion in various environments. It must be stated that no single technique can be used to study anaerobic microbial corrosion. Therefore, it is recommended that a series of tests should be utilised. These should include microbiological, chemical and metallurgical methods.

Of the multifarious economic activities of the sulphate-reducing bacteria, the best documented is that of steel corrosion. In the latter part of this century reports of SRB-induced corrosion have come from a variety of industries and much work has been done on practical as well as theoretical aspects of the problem. Despite this the corrosion mechanism has remained indeterminate. The bulk of the argument centres on the role of hydrogenase in the removal of hydrogen from cathodic sites on the steel surface, and whether this is important compared to cathodic depolarisation caused by biogenic ferrous sulphide. A relatively new industry where cognisably the SRB may manifest corrosion is the disposal of radioactive wastes, which concept entails the use of steel canisters. Many concepts for high-level waste disposal do envisage just this with burial in a mined repository, and backfilling with the clay mineral bentonite. For the UK concepts effort has been made to produce a safety assessment giving canister wall thicknesses to provide a steel canister of 500-1000 years integrity. The work effectuated for this thesis is of a dual nature. Firstly, consideration was given to the present theories of SRB-induced corrosion with experimentation aimed at deducing the most important mechanism(s) by a process of elimination. Secondly, and of equal emphasis, experiments were designed to examine what extra effect SRB may have on steel canister integrity under some conditions of high-level radioactive waste disposal, with a view to fitting any such extra effects into the safety analysis. SRB were found to be ubiquitous in proposed nuclear waste disposal sites examined for their presence. Laboratory corrosion studies using pure cultures of SRB (static and continuous culture) showed that corrosion of relevant mild carbon steel will be affected by levels of organic carbon, sulphate and phosphate which are unlikely to be present in significant quantities in a waste vault. Fe2+ availability was also shown to be a prerequisite to high corrosion rates. For high level radioactive waste the use of bentonite, a proposed backfilling material for waste canisters, containing SRB was shown to enhance corrosion of mild carbon steel. A model system to show this was set up using a bentonite clay/granitic groundwater mix in which SRB and steel coupons were present. Corrosion mechanisms which are likely to be involved include cathodic depolarisation and FeS production; it is not envisaged that the volatile phosphorus compound `identified' by Iverson as a corrosion product is involved. Genetic manipulation to produce hydrogenase-less mutants were unsuccessful during this study. It was aimed to produce such mutants to test the roles of the enzyme hydrogenase in rates of corrosion under repository conditions. Other factors (e.g. high pH) affecting the activity and effects of SRB on nuclear waste isolation materials were examined and are discussed for intermediate level radioactive waste disposal.

M.Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology
Corrosion responses of some carbon steels, stainless steel and copper alloys in the presence of a culture of bacteria (referred to as SRB-Sulphate-reducing bacteria) found in industrial heat exchangers, was studied to recommend best alloys under this service condition, with techno-economic consideration. Water from cooling towers in three plants in a petrochemical processing complex were analysed for SRB presence. Two of the water samples showed positive indication of SRB presence. The mixed cultures obtained from plant one were grown in prepared media and incubated at 35 °C for 18 days. Potentiodynamic polarisation studies in anaerobic conditions were done on the selected alloys in aqueous media with and without the grown SRB. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were then used to study the corrosion morphology and corrosion products formation. The voltamograms show higher icorr for alloys under the SRB compared to the control media, indicating the SRB indeed increased the corrosion rates. The surface analysis showed pitting on steel alloy ASTM A106-B. Localised attack to the grain boundaries on a selective area, was seen on ASTM A516-70 dislodging the grains, and intergranular corrosion was seen throughout the exposed area of ASTM A179. Copper alloys showed pitting on ASTM B111 grade C71500 (70-30), and denickelification on ASTM B111 grade C70600 (90-10), and is a good alternative material for use apart from carbon steel alloys, recording a low corrosion rate of 0.05 mm/year. The EDS analysis supported the findings showing higher weight percent of iron and sulphur on surface of the alloys after exposure to the SRB media. This implies that the presence of the sulphur ion indeed increased the corrosion rate. ASTM A516-70 carbon steel was chosen as a suitable alternative material to the stainless steel in this environment. The Tafel plot recorded a corrosion rate of 1.08 mm/year for ASTM A516-70 when exposed to SRB media.

The corrosion characteristics of Alloy 625 (UNS 00625, Ni - 22 Cr - 10 Mo) in oxygenated ammoniacal sulphate environments are determined at room temperature and pressure and up to high temperatures and pressures (673 K, 250 bar) commensurate with the process of supercritical water oxidation (SCWO). Electrochemical methods such as linear polarization, potentiodynamic polarization and impedance spectroscopy are used. It is found that the electrochemical and morphological response is dictated by the alloying element Cr and the formation of a Cr(III) oxide. Mo and, to a lesser extent Ni, are found to dissolve readily. Thermodynamic analysis of the Ni-NH₃-H₂O system, including new Pourbaix diagrams at temperatures as high as 653 K , has shown that Ni - ammine formation is possible at moderate temperatures but that the stability of these complexes decreases substantially with temperature. According to one of the models investigated, which is based on the only available high temperature equilibrium constant data, Ni-ammines become unstable above approximately 473 K . Impedance spectroscopy has shown that transpassive dissolution of the alloy's ptype, cation conducting, Cr(III) oxide occurs at temperatures as low as 373 K and total pressure (oxygen saturated) as low as 40 bar. As temperature and pressure are increased the corrosion process is increasingly diffusion controlled. Transpassive dissolution results in the thinning and eventual total removal of the alloy's protective semiconductor barrier layer. Cation ejection from the barrier layer into the solution and porous outer layer phase results in precipitation of a Cr(III) scale (oxide or hydroxyl-oxide) at the alloy surface which acts as a diffusion barrier. It is hypothesized that the outer layer is either physically removed at supercritical conditions due to rapid dissolution and grain boundary attack of the alloy or chemically removed by solution acidification due to the formation of sulphuric acid at high density supercritical conditions. Alloys 625, 316 L, Ni - 20 Cr and pure Nb are tested at SCWO conditions and it is found that the corrosion resistance increases with Cr content and Nb is found to perform well in sulphate containing SCWO solutions at oxygen concentrations up to 4 m. It is also confirmed in this work that maximum material loss occurs in the high-density supercritical region of the reactor. New Pourbaix diagrams for Nb at elevated temperatures (348 and 368 K) are calculated and compared to electrochemical and weight loss measurements performed in concentrated acids. Through electrochemical experiments in concentrated sulphuric and hydrochloric acids, Nb is found to be an ideal candidate for the high-density supercritical sections of SCWO reactors.
Applied Science, Faculty of
Materials Engineering, Department of
Graduate

Os aços inoxidáveis endurecidos por precipitação vêm sendo largamente empregados na indústria aeronáutica, por combinar resistência mecânica, tenacidade à fratura e resistência à corrosão. E deste modo, são materiais que possibilitam a substituição dos aços carbonos utilizados atualmente, que necessitam de tratamento superficial adicional, como o cádmio, para melhorar a resistência à corrosão. A utilização desses revestimentos traz desvantagens como o custo, a fabricação, a susceptibilidade à fragilização por hidrogênio além dos aspectos ambientais. Neste contexto, o aço endurecido por precipitação UNS S46500, designado como Custom 465® foi avaliado considerando o efeito da temperatura de envelhecimento sobre as propriedades mecânicas e a resistência à corrosão por pite. Amostras tratadas nas condições solubilizada e envelhecida a 510ºC (H950) e 538ºC (H1000) foram submetidas ao ensaio de tração, caracterização microestrutural e ensaios de polarização potenciodinâmica (PP) para determinar a resistência à corrosão por pite. Os exames microestruturais foram realizados com auxílio de microscopia óptica (MO), microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS) e difração de raios X. Também foram realizadas análises utilizando o software Thermo-Calc. A resistência à corrosão por pite foi avaliada em solução 0,6M NaCl com adições crescentes de Na2SO4. Os resultados obtidos nos ensaios de PP nas duas condições de tratamento térmico foram comparados entre si e com resultados disponíveis na literatura (CALDERÓN-HERNANDEZ, 2012) para o aço inoxidável UNS S30403 (304L). Os exames e análises da microestrutura revelaram que o aço Custom 465® envelhecido apresenta uma matriz martensítica, precipitados de fase chi, austenita e precipitados Ni3Ti. O tratamento H950 apresentou maior resistência mecânica e menor alongamento do que o tratamento H1000. Tal comportamento foi devido à produção de maior porcentagem de fase chi e menor porcentagem de austenita nesse tratamento de envelhecimento. Os diferentes tratamentos térmicos, condição solubilizada, H950 e H1000 apresentaram praticamente a mesma resistência à corrosão por pite. Por outro lado, o aço Custom 465® apresentou ótima resposta à inibição da nucleação de pite com adições crescentes de sulfato em meio de 0,6M NaCl, sendo que a condição H1000 se sobressai sobre a H950 nessa questão. Além disso, através da adição de sulfato foi 7 possível obter maior resistência a corrosão por pite do aço Custom 465® comparativamente ao aço 304L. Tal comportamento foi discutido em termos da afinidade química entre níquel, cloreto e sulfato, levando a maior resistência à corrosão por pite quando o aço contém maior teor de níquel (que é o caso do aço Custom 465®). Este trabalho indicou que o critério na escolha do tratamento de envelhecimento do aço Custom 465® deve ser o das propriedades mecânicas almejadas, uma vez que a resistência à corrosão por pite mostrou-se praticamente independente do tratamento térmico.
The precipitation hardened stainless steels have been widely used in the aircraft industry to combine mechanical strength, fracture toughness and corrosion resistance. And therefore, are materials that enable replacement of the carbon steels used today, which require additional surface treatment, such as cadmium plating, to improve the corrosion resistance. The use of such coatings brings disadvantages such as cost, manufacturing, susceptibility to hydrogen embrittlement beyond environmental aspects. In this context, the precipitation hardened steel UNS S46500, known as Custom 465® were evaluated for the effect of aging temperature on the mechanical properties and the resistance to pitting corrosion .Treated samples in solubilized and aged condition at 510°C (H950) and 538ºC (H1000) were subjected to tensile strength test, microstructural characterization and potentiodynamic polarization (PP) tests to determine the pitting corrosion resistance. The microstructural studies were performed with the aid of optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction. Analyzes were also performed using the Thermo -Calc software. The resistance to pitting corrosion was evaluated at 0.6M NaCl solution with increasing additions of Na2SO4. The results obtained from tests of PP in both heat treatment conditions were compared with each other and with results available in the literature (CALDERÓN HERNANDEZ, 2012) to stainless steel UNS S30403 (304L). The analysis of the microstructure revealed that the steel aged Custom 465 ® presents a martensitic matrix, chi precipitates, Ni3Ti precipitates and austenite phase. The H950 age treatment had higher mechanical strength and lower elongation than the treatment H1000. Such behavior was due to the production of higher percentage of chi and a lower percentage of austenite phase in aging treatment. The different heat treatments, solubilized condition, H950 and H1000 showed almost the same pitting corrosion resistance. On the other hand, the Custom 465® showed good response to pitting inhibition with increasing nucleating additions of sulfate in 0.6M NaCl, with enhanced result for H1000 condition. Furthermore, by adding sulfate was possible to obtain greater pitting corrosion resistance of Custom 465® compared to the 304L steel. This behavior has been discussed in terms of the chemical affinity between nickel, chloride and sulphate, leading to higher pitting corrosion resistance when the steel contains a higher nickel 9 content (which is the case of steel Custom 465®). This study indicates that the criterion in selecting the aging heat treatment of Custom 465® steel must be the desired mechanical properties, since the pitting corrosion resistance was found to be substantially independent of heat treatment.

The doctoral thesis deals with analysis of the ageing of concrete and reinforced concrete pipes in sewage systems. The ageing of the sewage system is caused by several reasons, for example material abrasion, chemical and biological corrosion and subsequent static overload sewer construction. One of the common causes of degradation of sewage systems made from materials bonded with cement sealant is biogenic sulphate corrosion. Due to the corrosion the degradation of the pipe walls accelerates, particularly in upper part of the pipe and reduces planned lifetime of the sewage system. There is proposed new ageing analysis monitoring method for observation and evaluation of the loss of thickness of concrete and reinforced concrete pipes, which is caused by biogenic sulphate corrosion. Residual lifetime is calculated from the expected corrosion rate, it`s the loss of wall thickness on the monitored section of the sewer system. There is designed the monitoring system of the loss of wall thickness on the sewage system for practical application of the measurement procedure, which is administrated in cooperation with the BVK, a. s. The thesis uses existing knowledge regarding this subject. We use this information for better understanding of the process of the loss of wall thickness in sewage systems in real time and the posibility to correct and in-time implementation of appropriate operational measures. This should cause the limitation of the degradation process of piping material while extended service life and safe operation in sewage systems within the required time period. Based on the methodology is proposed to determine the residual life of the sewage system and maintenance and rehabilitation can be done more effectively. There is needed to be noted that only long-term monitoring period can bring a better overview of the technical condition of sewage systems in time and thus better and more effective maintenance and rehabilitation, which is related to the effective u

碩士
國立海洋大學
材料工程研究所
85
Constant extension rate tensile tests were performed to investigate the fracture characteristics of the A387 steel weldments in H2S charging environment.

The aim of this study was to assess the strength, durability properties and corrosion resistance of concrete samples using supplementary cementitious blended materials. In this investigation, three supplementary concrete materials (SCMs) were used together with ordinary Portland Cement (OPC) to form cementitious blends at different proportions. The supplementary materials are silica fume (SF), ground granulated blast furnace slag (GGBS) and fly ash (FA). Sixteen (16) different proportions of the cementitious blends were produced. Tests carried out on concrete samples include slump test, compressive strength, oxygen permeability, sorptivity, porosity, chloride conductivity test, resistance to chloride and sulphate attack. The electrode potentials of tested samples were also observed using electrochemical measurements. Concrete specimens prepared with 10%, 20%, 30%, 40%, up to 60% of blended cements replacement levels were evaluated for their compressive strength at, 7, 14, 28, 90 and 120 days while the specimens were evaluated for durability tests at 28, and 90 days respectively. The results were compared with ordinary Portland cement concrete without blended cement. Voltage, and temperature measurements were also carried out to understand the quality of concrete. The corrosion performance of steel in reinforced concrete was studied and evaluated by electrochemical half-cell potential technique in both sodium chloride, and magnesium sulphate solutions respectively. The reinforced concrete specimens with centrally embedded 12mm steel bar were exposed to chloride and sulphate solutions with the 0.5 M NaCl and MgSO4 concentrations respectively. An impressed voltage technique was carried out to evaluate the corrosion resistance of the combination of quaternary cementitious blended cement, so as to get the combination with optimum performance. Improvement of strength, durability, and corrosion resistance properties of blended concrete samples are observed at different optimum percentages for binary, ternary and quaternary samples. The effect of cementitious blends is recognized in limiting the corrosion potential of the tested SCM concrete samples. Generally, the cementitious blends with limited quantity of SF to 10% have the potential to produce satisfactory concrete. These should however be used for low cost construction, where high quality concrete is not required.
Civil and Chemical Engineering
M. Tech. (Chemical Engineering)