Corrosion is the most important mechanical integrity issues the petrochemical industry has to deal with. While significant research has been dedicated to studying corrosion, it is still the leading cause of pipeline failure in the oil and gas industry. Not only is it the main contributor to maintenance costs, but also it accounts for about 15-20% of releases from the petrochemical industry and 80% of pipeline leaks. Enormous costs are directed towards fixing corrosion in facilities across the globe every year. Corrosion has caused some of the worst incidents in the history of the industry and is still causing more incidents every year. This shows that the problem is still not clearly understood, and that the methods that are being used to control it are not sufficient. A number of methods to detect corrosion exist; however, each one of them has shortcomings that make them inapplicable in some conditions, or generally, not accurate enough. This work focuses on studying a new method to detect corrosion under insulation. This method needs to overcome at least some of the shortcomings shown by the commercial methods currently used. The main method considered in this project is X-ray computed tomography. The results from this work show that X-ray computed tomography is a promising technique for corrosion under insulation detection. Not only does it detect corrosion with high resolution, but it also does not require the insulation to be removed. It also detects both internal and external corrosion simultaneously. The second part of this research is focused on studying the behavior of erosion/corrosion through CFD. This would allow for determining the erosion/corrosion rate and when it would take place before it starts happening. Here, the operating conditions that led to erosion/corrosion (from the literature) are used on FLUENT to predict the flow hydrodynamic factors. The relationship between these factors and the rate of erosion/corrosion is studied. The results from this work show that along with the turbulence and wall shear stress, the dynamic pressure imposed by the flow on the walls also has a great effect on the erosion/corrosion rate.

This thesis is a contribution to research into erosion-corrosion investigating the rapid wastage of in-bed heat exchanger tubing in fluidized bed combustors. Two main new areas of research were investigated; erosion-corrosion of mild steel in a temperature gradient and erosion-corrosion modelling. It has been suggested that differences between the wastage behaviour measured in fluidized bed combustors and laboratory studies is due to laboratory tests being carried out isothermally (specimen and fluidized bed at the same temperature) whereas, in a FBC boiler, the fluidized bed is considerably hotter than the metal heat exchanger tubing. The fluidized bed test rig was modified to increase the temperature gradient between the specimen and the fluidized bed from initial tests conducted by Rogers (1992b). Tests were carried out over a range of bed temperatures (300-500° C) and cooled specimen surface temperatures (175-500° C) with a maximum temperature difference between the two of 250° C. It was discovered that the temperature of the wear scar during a test was up to 200° C hotter than the temperature at the back of the specimen where the specimen temperature was initially measured in tests by Rogers (1992b). After temperature calibration tests the wastage of the specimens in a temperature gradient were very similar to the wastage of specimens exposed isothermally at the same metal temperature. Short term oxidation experiments were conducted on mild steel to obtain oxidation kinetics for erosion-corrosion modelling. It was found that the initial apparent parabolic rate constant was an order of magnitude larger than at longer time. Erosion studies were conducted with the aim to obtain quantitative data on the particle flux and the erosive behaviour of the bed with temperature. Results were not accurate enough to yield quantitative data but provided an estimate of the particle flux in the fluidized bed test rig. Results obtained from the short term oxidation and erosion studies were used in simple erosion-oxidation models to construct erosion-corrosion regime maps which tended to predict metal erosion to higher temperatures than observed experimentally. Predictions of material wear from the combination of an oxide removal and spalling mechanism predicted sensible wastage rates which agreed with experimental results.

Turbulent fluid flow at high Reynolds numbers presents significant degradation risks to active-passive metals due to enhanced localized degradation phenomena. A multidisciplinary experiment was proposed to study the relationship between hydrodynamics in fully-developed pipe flow and both the growth and performance characteristics of passive films. Preliminary work was performed to set up (i) an environmental chamber for the experiment, (ii) design a custom wall shear stress sensor and constant temperature anemometer traverse system to monitor hydrodynamic conditions in-situ, (iii) monitor in-situ degradation through an array of ultrasonic thickness transducers, and (iv) acquire data and control the environment via a LabVIEW routine. A validation experiment was conducted on a 1220 mm long experimental section of 45.7 mm inner diameter AA2024-T3 tubing in simulated seawater. Extensive degradation was observed in-situ and confirmed with ex-situ techniques after sequential exposure to fully-developed turbulent flow at an expected wall shear stress of 10 Pa for 180ks (Reynolds number of 122,000) and then at 40 Pa for 630ks (Reynolds number of 262,000). No typical erosion-corrosion hydrological features were observed, however significant pitting and intergranular corrosion were observed with corrosion product caps covering 47% of the total ultrasonic transducers' measurement area. Passive film and pit growth were recorded via ultrasonic thickness measurements with an observed simultaneous decrease in dissolved oxygen content. The validation experiment successfully demonstrated the capability of the designed and constructed sensors for the proposed experiment. Numerous areas of suggested development and research were identified to ensure accuracy and improve interpretation of future experiments. / Master of Science

Nickel aluminum bronze (NAB) alloys are used in naval and maritime applications for their excellent corrosion resistance under the influence of seawater. One application involves the use of a NAB butterfly valve within a NAB fluid line to control fluid flow of seawater. Due to the chaotic environment, the corrosion rate of the NAB tubing downstream from the valve increases significantly. The disc angle at which the valve alters fluid flow causes an increase in the fluid velocity and an increase in the turbulence produced on the downstream side of the valve. These fluid conditions contribute to the increase in the corrosion rate of the NAB piping downstream from the valve. This thesis aims to characterize how the change in the disc angle of the butterfly valve causes a change in the erosion-corrosion rate of NAB downstream from the valve. A butterfly valve is simulated using orifice plates of varying diameters to mimic flow conditions at different disc angles. An orifice plate is a simple device with a hole in its center that is designed to restrict fluid flow across a fluid line. Under the same hydrodynamic conditions, the orifice produces nearly the exact same flow coefficients as the valve. At a volumetric flowrate of 0.00757 m^3/s a total of eight locations found along the liquid/metal interface produced pitting sites. The average passivation layer thickness is also measured. / Master of Science

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No description available.

Excessive water flow velocities can contribute to rapid failures of copper premise plumbing systems. This is the first fundamental study to scientifically isolate mechanistic impacts from distinct flow induced failure mechanisms that include concentration cell corrosion, cavitation, particle/bubble impingement and high velocity impingement. Concentration cell effects resulting from exposing different copper surfaces to different flow regimes created a strong electrochemical cell that caused rapid corrosion that persisted for periods lasting from hours to days in certain waters. Free chlorine appeared to inhibit this effect in a range of waters. Under typical water chemistries the resulting non-uniform attack diminished, presumably due to formation of a protective scale or rust layer. Consequently, concentration cell corrosion would not be a major contributor to damage from high flow rates in the range of fresh waters investigated. In experiments using an ultrasonic processor, implosion of vaporous cavitation bubbles against a copper surface caused dramatic pitting, considerable copper weight loss, and, in some cases, the development of pinhole leaks. Changes in water chemistry and the existence of a pre-existing protective scale layer had nearly no mitigating effects on copper cavitation damage. An exponential relationship was found between the initial copper pipe wall thickness and the time necessary to cause a leak via vaporous cavitation. On the basis of this relationship, a Type M tube would be expected to last 23 and 3000 times less than a Type K and L tube, respectively, when facing continual cavitation attack. However, it was not possible to re-create cavitation damage in any practical circumstance that was tested in copper pipes, even though it is strongly believed that cavitation can play a practical role in service failures. On the basis of the above results, it was hypothesized that brief intervals of cavitation could remove protective scale from portions of the copper pipe surface exposed to high turbulence. In this case, even if minimal damage from cavitation occurred directly, it could allow concentration cell corrosion to become a significant contributor to non-uniform corrosion damage. On the basis of preliminary testing, it appears that this idea has considerable merit. A combination of brief cavitation and waters that create strong concentration cell effects is expected to cause serious damage to copper pipe. These potential synergies are deserving of additional research. In experiments testing the effect of high velocity jets (17.5 ft/sec) impinging against submerged copper plates perpendicularly and longitudinally, plates in heated sea water were aggressively gouged and penetrated. It is believed that the copper plate damage resulted from a combination of mechanisms including concentration cell corrosion, cavitation implosion, and high velocity impingement. Impingement of sand on the surface of copper tube created very little damage. This was surprising given prior reports in the literature. / Master of Science

Amostras de um aço inoxidável martensítico AISI 410 temperado e revenido foram nitretadas a plasma em baixa temperatura usando o tratamento de nitretação plasma DC e a nitretação a plasma com tela ativa. Ambos os tratamentos foram realizados a 400 °C, utilizando mistura gasosa de 75 % de nitrogênio e 25 % de hidrogênio durante 20 horas e 400 Pa de pressão. As amostras de aço AISI 410 temperado e revenido foram caracterizadas antes e depois dos tratamentos termoquímicos, usando as técnicas de microscopia óptica, microscopia eletrônica de varredura, medidas de microdureza, difração de raios X e medidas de teor de nitrogênio em função da distância à superfície por espectrometria WDSX de raios X. A resistência à erosão por cavitação do aço AISI 410 nitretado DC e com tela ativa foi avaliada segundo a norma ASTM G32 (1998). Os ensaios de erosão, de erosão - corrosão e de esclerometria linear instrumentada segundo norma ASTM C1624 (2005) somente foram realizados no aço AISI 410 nitretado com tela ativa. Ensaios de nanoindentação instrumentada forma utilizados para medir a dureza (H) e o módulo de elasticidade reduzido (E*) e calcular as relações H/E* e H3/E*2 e a recuperação elástica (We), utilizando o método proposto por Oliver e Pharr. Ambos os tratamentos produziram camadas nitretadas de espessura homogênea constituídas por martensita expandida supersaturada em nitrogênio e nitretos de ferro com durezas superiores a 1200 HV, porém, a nitretação DC produziu maior quantidade de nitretos de ferro do que o tratamento de tela ativa. Os resultados de erosão por cavitação do aço nitretado DC mostraram que a precipitação de nitretos de ferro é prejudicial para a resistência à cavitação já que reduziu drasticamente o período de incubação e aumentou a taxa de perda de massa nos estágios iniciais do ensaio; entretanto, depois da remoção desses nitretos de ferro, a camada nitretada formada somente por martensita expandida resistiu bem ao dano por cavitação. Já no caso do aço nitretado com tela ativa, a resistência à erosão por cavitação aumentou 27 vezes quando comparada com o aço AISI 410 sem nitretar, fato atribuído à pequena fração volumétrica e ao menor tamanho dos nitretos de ferro presente na camada nitretada, às maiores relações H/E* e H3/E*2 e à alta recuperação elástica da martensita expandida. A remoção de massa ocorreu, principalmente, pela formação de crateras e de destacamento de material da superfície dos grãos por fratura frágil sem evidente deformação plástica. As perdas de massa acumulada mostradas pelo aço nitretado foram menores do que aquelas do aço AISI 410 nos ensaios de erosão e de erosão corrosão. O aço nitretado apresentou uma diminuição nas taxas de desgaste em ambos os ensaios de aproximadamente 50 % quando comparadas com o aço AISI 410. O mecanismo de remoção de material foi predominantemente dúctil, mesmo com o grande aumento na dureza. Os resultados de esclerometria linear instrumentada mostraram que a formação de martensita expandida possibilitou uma diminuição considerável do coeficiente de atrito em relação ao observado no caso do aço AISI 410 sem nitretar. O valor de carga crítica de falha foi de 14 N. O mecanismo de falha operante no aço nitretado foi trincamento por tensão. / Specimens of a quenched and tempered AISI 410 martensitic stainless were low temperature plasma nitrided using DC pulsed plasma treatment and the pulsed plasma active screen technic. Both treatments were carried out at 400 °C in a mixture of 75 % of nitrogen and 25 % of hydrogen during 20 hours and 400 Pa of pressure. Nitrided and non-nitrided AISI 410 specimens were characterized by optical and scanning electron microscopy, micro and nanohardness measurements, X ray diffraction and determination of the nitrogen content as a function of the depth using wavelength dispersive spectroscopy WDSX. Cavitation erosion tests were carried out according to ASTM G32 (1998) standard for both DC nitrided steel and active screen nitrided steel, whereas, the erosion, erosion - corrosion tests and scratch tests according to ASTM C1624 (2005) were conducted only for active screen nitrided steel. Nanoindentation tests were carried out in order to assess the hardness (H), the reduced elastic modulus (E*) the H/E* and H3/E*2 ratios and the elastic recovery (We) of the active screen nitrided steel according to the procedure proposed by Oliver and Pharr. Both nitrided treatments produced thick nitrided cases composed of nitrogen supersaturaded expanded martensite and iron nitrides, however, the DC treatment promoted the precipitation of large quantities of iron nitrides in comparison to the active screen technic. The cavitation erosion results of the DC nitrided steel showed that iron nitrides precipitation is harmful for the cavitation resistance as it drastically reduced the incubation period, despites this, after the removal of those iron nitrides, the nitrided case composed solely of expanded martensite resisted the cavitation damage. On the other hand, the active screen technic increased 27 times the cavitation erosion resistance of the AISI 410 steel. The increase in cavitation erosion resistance was attributed to minor quantities of smaller size iron nitrides, the higher H/E* and H3/E*2 ratios and to the higher elastic response of the expanded martensite. The material removal mainly comes from the formation of craters and from debris detachment from the grain surfaces due to brittle fracture, without plastic deformation. The active screen nitrided steel showed the lower cumulative mass losses in erosion and erosion - corrosion tests. The nitrogen addition decreased around 50 % the erosion rate in both tests. The active screen nitrided steel showed a ductile behavior despite the intense increase in hardness. The scratch tests showed that expanded martensite formation led to a significant decrease of the friction coefficient. The critical load was 14 N and the failure mechanism acting in the nitrided case was tensile cracking.

Amostras de um aço inoxidável martensítico AISI 410 temperado e revenido foram nitretadas a plasma em baixa temperatura usando o tratamento de nitretação plasma DC e a nitretação a plasma com tela ativa. Ambos os tratamentos foram realizados a 400 °C, utilizando mistura gasosa de 75 % de nitrogênio e 25 % de hidrogênio durante 20 horas e 400 Pa de pressão. As amostras de aço AISI 410 temperado e revenido foram caracterizadas antes e depois dos tratamentos termoquímicos, usando as técnicas de microscopia óptica, microscopia eletrônica de varredura, medidas de microdureza, difração de raios X e medidas de teor de nitrogênio em função da distância à superfície por espectrometria WDSX de raios X. A resistência à erosão por cavitação do aço AISI 410 nitretado DC e com tela ativa foi avaliada segundo a norma ASTM G32 (1998). Os ensaios de erosão, de erosão - corrosão e de esclerometria linear instrumentada segundo norma ASTM C1624 (2005) somente foram realizados no aço AISI 410 nitretado com tela ativa. Ensaios de nanoindentação instrumentada forma utilizados para medir a dureza (H) e o módulo de elasticidade reduzido (E*) e calcular as relações H/E* e H3/E*2 e a recuperação elástica (We), utilizando o método proposto por Oliver e Pharr. Ambos os tratamentos produziram camadas nitretadas de espessura homogênea constituídas por martensita expandida supersaturada em nitrogênio e nitretos de ferro com durezas superiores a 1200 HV, porém, a nitretação DC produziu maior quantidade de nitretos de ferro do que o tratamento de tela ativa. Os resultados de erosão por cavitação do aço nitretado DC mostraram que a precipitação de nitretos de ferro é prejudicial para a resistência à cavitação já que reduziu drasticamente o período de incubação e aumentou a taxa de perda de massa nos estágios iniciais do ensaio; entretanto, depois da remoção desses nitretos de ferro, a camada nitretada formada somente por martensita expandida resistiu bem ao dano por cavitação. Já no caso do aço nitretado com tela ativa, a resistência à erosão por cavitação aumentou 27 vezes quando comparada com o aço AISI 410 sem nitretar, fato atribuído à pequena fração volumétrica e ao menor tamanho dos nitretos de ferro presente na camada nitretada, às maiores relações H/E* e H3/E*2 e à alta recuperação elástica da martensita expandida. A remoção de massa ocorreu, principalmente, pela formação de crateras e de destacamento de material da superfície dos grãos por fratura frágil sem evidente deformação plástica. As perdas de massa acumulada mostradas pelo aço nitretado foram menores do que aquelas do aço AISI 410 nos ensaios de erosão e de erosão corrosão. O aço nitretado apresentou uma diminuição nas taxas de desgaste em ambos os ensaios de aproximadamente 50 % quando comparadas com o aço AISI 410. O mecanismo de remoção de material foi predominantemente dúctil, mesmo com o grande aumento na dureza. Os resultados de esclerometria linear instrumentada mostraram que a formação de martensita expandida possibilitou uma diminuição considerável do coeficiente de atrito em relação ao observado no caso do aço AISI 410 sem nitretar. O valor de carga crítica de falha foi de 14 N. O mecanismo de falha operante no aço nitretado foi trincamento por tensão. / Specimens of a quenched and tempered AISI 410 martensitic stainless were low temperature plasma nitrided using DC pulsed plasma treatment and the pulsed plasma active screen technic. Both treatments were carried out at 400 °C in a mixture of 75 % of nitrogen and 25 % of hydrogen during 20 hours and 400 Pa of pressure. Nitrided and non-nitrided AISI 410 specimens were characterized by optical and scanning electron microscopy, micro and nanohardness measurements, X ray diffraction and determination of the nitrogen content as a function of the depth using wavelength dispersive spectroscopy WDSX. Cavitation erosion tests were carried out according to ASTM G32 (1998) standard for both DC nitrided steel and active screen nitrided steel, whereas, the erosion, erosion - corrosion tests and scratch tests according to ASTM C1624 (2005) were conducted only for active screen nitrided steel. Nanoindentation tests were carried out in order to assess the hardness (H), the reduced elastic modulus (E*) the H/E* and H3/E*2 ratios and the elastic recovery (We) of the active screen nitrided steel according to the procedure proposed by Oliver and Pharr. Both nitrided treatments produced thick nitrided cases composed of nitrogen supersaturaded expanded martensite and iron nitrides, however, the DC treatment promoted the precipitation of large quantities of iron nitrides in comparison to the active screen technic. The cavitation erosion results of the DC nitrided steel showed that iron nitrides precipitation is harmful for the cavitation resistance as it drastically reduced the incubation period, despites this, after the removal of those iron nitrides, the nitrided case composed solely of expanded martensite resisted the cavitation damage. On the other hand, the active screen technic increased 27 times the cavitation erosion resistance of the AISI 410 steel. The increase in cavitation erosion resistance was attributed to minor quantities of smaller size iron nitrides, the higher H/E* and H3/E*2 ratios and to the higher elastic response of the expanded martensite. The material removal mainly comes from the formation of craters and from debris detachment from the grain surfaces due to brittle fracture, without plastic deformation. The active screen nitrided steel showed the lower cumulative mass losses in erosion and erosion - corrosion tests. The nitrogen addition decreased around 50 % the erosion rate in both tests. The active screen nitrided steel showed a ductile behavior despite the intense increase in hardness. The scratch tests showed that expanded martensite formation led to a significant decrease of the friction coefficient. The critical load was 14 N and the failure mechanism acting in the nitrided case was tensile cracking.

No description available.