M. S.

Com a descoberta de novas fontes de petróleo e gás, em regiões remotas e de difícil acesso, tem-se a necessidade do desenvolvimento de novas tecnologias para garantir a eficácia da exploração destes recursos. Essa exploração e extração muitas vezes se dão em ambientes altamente corrosivos e os equipamentos devem apresentar propriedades que garantam um fator de segurança em serviço. Os aços de alta resistência e baixa liga (ARBL) são utilizados em tubulações para o transporte de gás natural e petróleo. Estes estão constantemente expostos a ambientes ácidos os quais são compostos de umidade e sulfeto de hidrogênio (H2S), podendo causar falha induzida pela presença de hidrogênio (Hydrogen Induced Cracking HIC). Este tipo de falha é normalmente abordado na literatura através de ensaios em solução contendo ácido acético e/ou sais (cloreto de sódio, entre outros), sempre com a injeção de H2S. Há vários mecanismos propostos, no entanto, o assunto não está totalmente resolvido. As alterações de composição química dos aços, processos de refino do aço e processos de conformação mecânica são responsáveis pela microestrutura final e determinantes da resistência à fragilização por hidrogênio. O objetivo deste trabalho é analisar e comparar o comportamento quanto à resistência à corrosão e resistência à HIC de quatro materiais: tubo X65 sour, sua região de solda, tubo X65 não-sour e uma chapa destinada a confecção de tubo X65. Os eletrólitos empregados foram: solução A (ácido acético contendo cloreto de sódio) e a solução B (água do mar sintética), os quais correspondem às soluções recomendadas pela norma NACE TM0284-2003. Os materiais foram submetidos a: ensaios de polarização (Polarização Linear para determinação da Resistência de Polarização - Rp) e ensaios de resistência a HIC segundo a norma NACE TM0284-2003; exames em microscópio óptico e eletrônico de varredura para caracterização da morfologia da corrosão e do trincamento. Os ensaios de Rp revelaram que a solução A é mais agressiva do que a solução B, sendo isso explicado pela diferença de pH entre estas duas soluções. Os resultados mostraram ainda que a máxima resistência à corrosão sempre é obtida para o tubo sour, enquanto a mínima ocorreu para o tubo não-sour. Após o ensaio de resistência a HIC os exames em microscópio óptico revelaram que, em ambas as soluções, o tubo de X65 sour, e a sua solda não apresentaram trincas, bem como a chapa destinada a tubo X65; já o tubo de X65 não-sour apresentou trincamento principalmente na região central. Os exames das trincas revelaram que a presença de cementita intergranular e a estrutura bandeada foram as causas do trincamento. No caso do tubo sour, o bom desempenho foi discutido em termos da microestrutura de ferrita poligonal, acicular e microconstituinte M/A. Já o comportamento distinto encontrado para a chapa (para tubo X65), foi discutido levando-se em conta que esta chapa apresentou menor quantidade de cementita intergranular, uma vez que, sua microestrutura é bandeada e não foi encontrado trincamento. Os resultados também revelaram que a solução B, como no caso da resistência à corrosão, é uma solução menos agressiva, pois o trincamento obtido foi muito menor. / The discovery of new oil and gas reserves, at remote and hard to reach locations, makes imperative the development of new technologies to ensure effective exploitation of these resources. This exploitation is often performed at highly corrosive environments and equipment such as pipelines should have special mechanical and corrosion properties to guarantee safety levels in service. High-Strength Low Alloy (HSLA) steels are used in pipelines for transporting gas and oil. These steels are in constant exposure to acid environments containing hydrogen sulfide (H2S) and water, that can cause pipeline failures due to Hydrogen-Induced Cracking - HIC. The literature reports that Hydrogen-Induced Cracking in steels is normally tested in solutions containing acetic acid and/or, salts (sodium chloride and others) with addition of H2S. Chemical composition, steel refining processes and metal forming processes are responsible for the final microstructure of the steel and have effect on the hydrogen embrittlement resistance. The purpose of this work is to analyze and compare the corrosion resistance and HIC resistance, and compare of four materials: pipeline steel API 5L X65 for sour service, its welded junctions, pipeline steel API 5L X65 for non-sour service and pipeline steel plate API 5L X65. The materials were submitted to linear polarization test (Rp) and HIC resistance test according to NACE TM0284-2003 standard. Both tests were carried out with two different electrolytes: the solution A (acetic acid and sodium chloride) and solution B (synthetic seawater). Subsequently; the surface of the steels were evaluated by optical microscope and scanning electron microscopy in order to characterize the cracking modes and corrosion morphology. The Rp tests showed that the solution A is more aggressive than solution B, behavior attributed to the pH difference between solutions. Steel API 5L X65 for sour service had the highest corrosion resistance and pipeline steel API 5L X65 for non-sour service had the lowest. The HIC test and the surface examination revealed that in both solutions, pipeline steel API 5L X65 for sour service, the welded junctions and the pipeline steel plate API 5L X65 showed no cracks. On the other hand, pipeline steel API 5L X65 for non-sour service presented cracking mainly in the central region. The tests revealed that the cracks nucleated at the intergranular cementite in the banded structure. The good performance of the pipeline steel API 5L X65 for sour service was discussed in terms of the microstructure, formed by polygonal ferrite, acicular ferrite and M/A microconstituent. The performance of steel plate (for pipeline API 5L X65) was different. This material did not exhibit cracks in the matrix in spite of its banded microstructure. This result was discussed taking into account that the plate studied had a small amount of intergranular cementite. The results also showed that the solution B, as in the case of corrosion resistance tests, was less aggressive than solution A, because the cracks produced were smaller.

Com o decorrer dos anos o consumo de petróleo e seus derivados aumentou significativamente e com isso houve a necessidade de se investir em pesquisas para descobertas de novas jazidas de petróleo como o pré-sal. Porém, não apenas a localização dessas jazidas deve ser estudada, mas, também, sua forma de exploração. Essa exploração e extração, na maioria das vezes, se dão em ambientes altamente corrosivos e o transporte do produto extraído é realizado através de tubulações de aço de alta resistência e baixa liga (ARBL). Aços ARBL expostos a ambientes contendo H2S e CO2 (sour gas) sofrem corrosão generalizada que promovem a entrada de hidrogênio atômico no metal, podendo diminuir sua tenacidade e causar falha induzida pela presença de hidrogênio (Hydrogen Induced Cracking HIC), gerando falhas graves no material. Tais falhas podem ser desastrosas para o meio ambiente e para a sociedade. O objetivo deste trabalho é estudar a tenacidade, utilizando ensaio Charpy, de um tubo API 5L X65 sour após diferentes tempos de imersão em uma solução saturada com H2S. O eletrólito empregado foi a solução A (ácido acético contendo cloreto de sódio) da norma NACE TM0284 (2011), fazendo-se desaeração com injeção de N2, seguida de injeções de H2S. Os materiais foram submetidos a: ensaios de resistência a HIC segundo a norma NACE TM0284 (2011) e exames em microscópio óptico e eletrônico de varredura para caracterização microestrutural, de inclusões e trincas. As amostras foram submetidas a imersão em solução A durante 96h e 360h, sendo que, após doze dias do término da imersão, foram realizados os ensaios Charpy e exames fractográficos. Foram aplicados dois métodos: o de energia absorvida e o da expansão lateral, conforme recomendações da norma ASTM E23 (2012). As curvas obtidas, em função da temperatura de impacto, foram ajustadas pelo método da tangente hiperbólica. Esses procedimentos foram realizados nas duas seções do tubo (transversal e longitudinal) e permitiram a obtenção dos seguintes parâmetros: energias absorvidas e expansão lateral nos patamares superior e inferior e temperaturas de transição dúctil-frágil (TTDF) em suas diferentes definições, ou seja, TTDFEA, TTDFEA-DN, TTDFEA-FN, TTDFEL, TTDFEL-DN e TTDFEL-FN (identificação no item Lista de Abreviaturas e Siglas). No exame fractográfico observou-se que o material comportou-se conforme o previsto, ou seja, em temperaturas mais altas ocorreu fratura dúctil, em temperaturas próximas a TTDF obteve-se fratura mista e nas temperaturas mais baixas observou-se o aparecimento de fratura frágil. Os resultados mostraram que quanto maior o tempo de imersão na solução A, menor é a energia absorvida e a expansão lateral no patamar superior, o que pode ser explicado pelo (esperado) aumento do teor de hidrogênio em solução sólida com o tempo de imersão. Por sua vez, os resultados mostraram que há tendência à diminuição da temperatura de transição dúctil-frágil com o aumento do tempo de imersão, particularmente, as TTDFEA-DN e TTDFEL-DN das duas seções do tubo (longitudinal e transversal). Esse comportamento controverso, que pode ser denominado de tenacificação com o decorrer do tempo de imersão na solução A, foi explicado pelo aparecimento de trincas secundárias durante o impacto (Charpy). Isso indica uma limitação do ensaio Charpy para a avaliação precisa de materiais hidrogenados. / Over the years the consumption of crude oil and its derivatives increased significantly, creating the necessity to invest in research to discover new sources of pre-salt crude oil. However, not only the location of these deposits should be studied, but also its extraction. This exploration and extraction, in most cases, occur in highly corrosive environments and the transport of the extracted product is performed by high strength low alloy steel pipes (HSLA). HSLA steels exposed to environments containing CO2 and H2S (sour gas) suffer general corrosion that promotes the diffusion of atomic hydrogen into the metal structure, which may decrease its toughness and induce cracks by the presence of hydrogen (Hydrogen Induced Cracking - HIC), leading the material to severe failures. Such events can be disastrous for the environment and the society. The objective of this work is to study the toughness using Charpy Impact Tests on an API 5L X65 sour service steel pipe, submitted to different immersion times in a H2S saturated solution. The used electrolyte was the NACE TM0284 (2011) solution A (acetic acid containing sodium chloride), with deaeration by N2 injection followed by H2S injection. The materials were submitted to HIC resistance tests according to NACE TM0284 (2011) standard and examination by optical microscopy and scanning electron microscopy for microstructural inclusions and cracks characterization. The samples were immersed in the solution for 96h and 360h and after twelve days of immersion, Charpy tests and fracture analysis were performed. Two analytical methods were applied to Charpy tests results: the energy absorbed and lateral expansion, as recommended by the ASTM E23 (2012). The obtained curves, that are a function of impact temperature, were adjusted by the hyperbolic tangent method. This procedure was performed in two different orientations in the pipe (transverse and longitudinal) and allowed the determination of the following parameters: energy absorbed and lateral expansion in the upper and lower levels and ductile-to-brittle transition temperatures (DBTT) in its different definitions: DBTTAE, DBTTAE-DN, DBTTAE-FN, DBTTLE, DBTTLE-DN e DBTTLE-FN. Fracture analysis revealed that the material behaved as expected, meaning that at higher temperatures ductile fracture occurred, at temperatures near DBTT it was obtained a mixed fracture and at lower temperatures it was observed the presence of brittle fracture. Results showed that when the immersion time in the solution was higher, the energy absorbed in upper shelf decreases, and also lateral expansion in upper shelf decreases, which may be explained by the (expected) increase of hydrogen level in solid solution, induced by the immersion time. It was found that there is a tendency of the ductile-to-brittle transition temperature to be lower with the increase of immersion time, particularly the DBTTAE-DN and DBTTLE-DN of the two pipe sections (longitudinal and transversal). This controversial behavior, which may be defined as the toughening by the increase of immersion time in the solution A, was explained by the appearance of secondary cracks during impact test (Charpy). This indicates a limitation of the Charpy test for the accurate characterization of hydrogenated materials, concerning toughness.

The environmentally-assisted fatigue crack growth behaviour of austenitic stainless steels in deoxygenated high temperature water at low strain rates has been reported to be greatly affected by the sulphur (S) content of the specimen, with high S specimens exhibiting significant reduced crack growth rates (retardation) when compared to low S specimens. To further the understanding of the mechanistic behaviour, fatigue crack growth experiments have been performed on high and low sulphur Type 316 austenitic stainless steel specimens tested in high temperature water and evaluated via microstructural characterisation techniques. At high strain rates the enhanced crack growth for both specimens appeared to be crystallographic and associated with slip localization. Furthermore, matching fracture surface analysis indicated discrepancy of the slip steps and micro-cleavage cracks between the matching surfaces, suggesting that slip steps and micro-cleavage cracking occurred after the crack-tip had advanced. It was also postulated that their formation may involve cathodically-produced hydrogen and shear deformation on the fracture surface. However, when the loading frequency was decreased, the high S specimens retarded the crack growth and the path was no longer crystallographic. Significant differences in the crack-tip opening displacements were observed in both materials, with blunt crack-tips in the high sulphur specimen and sharp tips in the low sulphur specimen when the strain rate was low. EBSD analysis at the crack-tips of both specimens showed that the strain was more localised at the crack-tip of the low sulphur specimen whist the strain ahead of the high sulphur specimen was more homogenous. It is thus postulated that retardation occurs when slip localisation is no longer the dominant factor. The localised deformation during enhancement is believed to have been caused by hydrogen enhanced localised plasticity (HELP) which causes the crack-tip to sharpen. The diffused strain distribution during crack growth retardation is believed to have been caused by hydrogen enhanced creep (HEC) which causes the crack-tip to blunt. It is also believed that both enhancement and retardation mechanisms are associated with contrasting effects deriving from hydrogen enhanced plasticity. Oxide induced crack closure was excluded as a mechanism responsible for retardation of fatigue crack growth when the stress ratio is high. Effects of hydrogen induced alpha' and ε martensite phases on oxidation behaviour of austenitic stainless steels in deoxygenated high temperature water have also been studied. Microstructural characterisation shows that hydrogen induced alpha' martensite enhances oxidation of austenitic stainless steels in deoxygenated high temperature water. The implications of this finding on environmentally assisted cracking of austenitic stainless steels in deoxygenated high temperature water is discussed.

Este trabalho tem por objetivo avaliar os efeitos do hidrogênio em três diferentes tipos de aços de alta resistência mecânica. São descritos os fenômenos de introdução, difusão e aprisionamento de hidrogênio (H) dentro dos metais, em conjunto com os diferentes tipos de danos provocados devido à presença do hidrogênio. Os materiais de estudo são aços da família Advanced High Strength Steels (AHSS): aços Dual Phase (DP 1000 e DP 1200) e aço Martensítico (M 190). A introdução de hidrogênio nos materiais foi realizada através de carregamento catódico, o qual é representativo para as condições industriais a que se destinam. De modo a avaliar a influência do H nas propriedades mecânicas dos aços, os seguintes ensaios foram propostos: ensaio de carregamento com H, para determinar o conteúdo total de H (saturação) e conteúdo de H difusível (suscetibilidade a fragilização); ensaio de tração ao ar, para determinar a tensão no final da região elástica e resistência à tração na região do entalhe e ensaio de tração com carga constante em ambiente hidrogenado, para avaliar os efeitos provocados pela presença do H e determinar o patamar abaixo do qual o H não apresenta efeito crítico sobre o material. Os efeitos provocados pela aplicação de diferentes densidades de correntes (0,2 – 1,0 mA/cm²) foram avaliados nos ensaios de quantificação de H difusível. Conforme os resultados obtidos todos os aços apresentaram perdas na resistência mecânica à tração quando em ambiente hidrogenado, ou seja, sofreram fragilização por H. Os aços DP 1200 e M 190 (de microestrutura predominantemente martensítica) foram fortemente afetados, conforme evidenciado pela notável queda nos valores de tensão necessários para provocar a falha. Por outro lado, o aço DP 1000, de menor resistência mecânica, demonstrou menor suscetibilidade à fragilização, o que é atribuído a menor permeabilidade do H na microestrutura austenítica. / This work aims to evaluate the effects of hydrogen in three high- strength steel grades. The phenomena of hydrogen (H) entry, transport and trapping inside the metals, together with the different types of damages due to the presence of hydrogen are presented. The study materials are a range of AHSS steel grades: Dual Phase Steel (DP 1000 and DP 1200) and Martensitic Steel (M 190). The hydrogen entry was performed by cathodic charging, which is suitable for industrial applications. In order to evaluate the influence of H on the steel mechanical properties, the following tests were done: H charging, to measure total H content (saturation point) and diffusible H content (embrittlement susceptibility); uniaxial tensile test of uncharged samples to determine notched tensile strength values and the strength levels at the end of elastic region and constant load tensile testing carried out in hydrogen environment, to determine the threshold values where hydrogen has an effect on the material. DP 1200 and M 190 were strongly affected by H pre-charging, as shown by the significant drop in stress required to break them. On the other hand, DP 1000 showed a lower embrittlement susceptibility, which is attributed to its lower mechanical strength. The current densities effects (0.2 up to 1.0 mA/cm²) were evaluated during H charging to measure diffusible H content. All steels showed a drop in the tensile strength i.e. experienced hydrogen embrittlement. Steels with higher tensile strength, as DP 1200 and M 190, showed a much bigger drop that is related to the favorable characteristics of martensitic microstructure regarding to the hydrogen permeability and diffusivity.

Hydrogen is the smallest element in the periodical table. It has been shown in several studies that hydrogen has a large influence on the corrosion and cracking behaviour of stainless steels. Hydrogen is involved in several of the most common cathode reactions during corrosion and can also cause embrittlement in many stainless steels. Some aspects of the effect of hydrogen on corrosion and hydrogen-induced stress cracking, HISC, of stainless steels were studied in this work. These aspects relate to activation of test specimens for uniform corrosion testing, modification of a test cell for dewpoint corrosion testing and the mechanism of hydrogen-induced stress cracking. The results from uniform corrosion testing of superduplex stainless steels indicated that there is a large difference between passive and activated surfaces in hydrochloric acid and in lower concentrations of sulphuric acid. Hence, initial activation of the test specimen until hydrogen evolution can have a large influence on the results. This may provide another explanation for the differences in iso-corrosion curves for superduplex stainless steels that have previously been attributed to alloying with copper and/or tungsten. In concentrated sulphuric acid, potential oscillations were observed; these oscillations activated the specimen spontaneously. Due to these potential oscillations the influence of activation was negligible in this acid. An experimental set-up was developed for testing dewpoint corrosion of stainless steels in a condensate containing 1 % hydrochloric acid. There was an existing experimental set-up that had to be modified in order to avoid azeotroping of the water and hydrogen chloride system. A separate flask with hydro chloric acid was included in the experimental set-up. The final set-up provided reasonably good agreement with field exposures in contrary to much higher corrosion rates in the original set-up. Relaxation and low temperature creep experiments have been performed with several stainless steels in this work. The aim was to understand how creep and relaxation relates to material properties and the relative ranking between the tested materials. For low temperature creep with a load generating stresses below the yield strength, as well relaxation at stress levels above and below the yield strength, the same ranking with respect to changes in mechanical properties of the steel grades was found. For low temperature creep with a load level above the yield strength, the same ranking was not obtained. This effect can most probably be explained by annihilation and generation of dislocations. During low temperature creep above the yield strength, dislocations were generated. In addition, low temperature creep experiments were performed forone superduplex stainless steel in two different product forms with differentaustenite spacing in the microstructure. The superduplex material experienced low temperature creep at a lower load level for the material with large austenite spacing compared to the one with smaller austenite spacing. Also this differenceis influenced by dislocations. In a material with small austenite spacing the dislocations have more obstacles that they can be locked up against. Studies of the fracture surfaces of hydrogen induced stress cracking, HISC, tested duplex stainless steels showed that HISC is a hydrogen-enhanced localised plasticity, HELP, mechanism. Here a mechanism that takes into account the inhomogeneous deformation of duplex stainless steels was proposed. This mechanism involves an interaction between hydrogen diffusion and plastic straining. Due to the different mechanical properties of the phases in a superduplex stainless steel, plastic straining due to low temperature creep can occur in the softer ferrite phase. A comparison between low temperature creep data showed that for the coarser grained material, HISC occurs at the load levelwhen creep starts. However, in the sample with small austenite spacing, HISC did not occur at this load level. Microhardness measurements indicated that the hydrogen level in the ferrite was not high enough to initiate cracking in the coarser material. The proposed mechanism shows that occurrence of HISC is an interaction between local plasticity and hydrogen diffusion. / QC20100618

Bei dem Prozess einer Wasserstoffinduzierten Spannungsrisskorrosion (H-SpRK) handelt es sich um einen zeitabhängigen Vorgang, der zu einer Reduzierung der Duktilität und Widerstandskraft des Spannstahls führt und daraus resultierend ein sprödes und schlagartiges Versagen eines Spannbetonbauwerkes zur Folge haben kann. Der Prozess selbst und insbesondere auch die ihn beeinflussenden Parameter sind für die im Bauwesen verwendeten hochfesten Spannstähle älterer Produktion weitestgehend unerforscht. Die Relevanz für bestehende Bauwerke ist jedoch nicht zuletzt durch einzelne dokumentierte und untersuchte Schadensfälle nachgewiesen. Ziel der vorliegenden Arbeit war es, die zur Verfügung stehenden Bauwerksuntersuchungen aus den zurückliegenden ca. 10 Jahren statistisch zu analysieren und auszuwerten. Auf dieser Basis war ein Berechnungsmodell wahrscheinlichkeitstheoretischer Basis zu entwickeln, mit dem die Gefahr eines spröden Bauwerksversagens für das Gesamttragwerk beurteilt und hinsichtlich der Auswirkungen auf das einzuhaltende Sicherheitsniveau bewertet werden kann. Es wurden insgesamt 31 Bauwerksuntersuchungen statistisch ausgewertet und beurteilt. Die zur Verfügung stehenden Daten wurden analysiert und hinsichtlich der Prüfqualität sowie der Quantität der Proben bewertet. Dabei war festzustellen, dass aufgrund fehlender konkreter Vorgaben im Regelwerk eine sehr heterogene Datenbasis vorliegt. Nicht alle Untersuchungsergebnisse konnten in die weitere Auswertung einbezogen werden. Die in ausreichender Datenqualität und Datenumfang geeigneten Untersuchungen wurden hinsichtlich ihrer Relevanz für den Prozess einer H-SpRK analysiert und die Auswirkungen einzelner Parameter bewertet. Im Ergebnis der materialtechnischen Untersuchungen und statistischen Auswertung der Bauwerksuntersuchungen wurde ein Berechnungsmodell vorgestellt, das den gleichzeitigen Ausfall von Spannstahl in allen Bereichen des Bauwerkes berücksichtigt. Zusätzlich zum Standardverfahren des beschriebenen Vorgehens wird das Modell um den Ansatz eines korrelierten Spannstahlausfalls erweitert. Außerdem wird für Bauwerke mit einem statisch unbestimmten Anteil der Vorspannung sowie für Konstruktionen mit gestaffelter Spannstahlbewehrung die Anwendung des Verfahrens konkretisiert. Neben der Erstellung des Berechnungsmodells wurden Vorschläge zu Vorgaben für die Bauwerksprüfung vorgestellt. Dazu zählen insbesondere die Festlegung von Prüfintervallen sowie einheitliche Vorgaben zu den verwendeten Prüfmethoden und -verfahren. Bezüglich der Festlegung von Mindestumfängen von Proben wird zwischen bestehenden und auch weiter zu nutzenden Bauwerken einerseits sowie Probennahmen im Rahmen von Rückbaumaßnahmen unterschieden.

Ultra-high strength steels is known to be susceptible for hydrogen embrittlement at very low concentrations of hydrogen. In this thesis three methods to prevent or reduce the hydrogen embrittlement in martensitic steel, with tensile strength of 1500 MPa, were studied. First, a barrier layer of aluminium designed to prevent hydrogen to enter the steel, which were deposited by vacuum evaporation. Second, a decarburization process of the steels surface designed to mitigate the induced stresses from cutting. Last, a hydrogen relief treatment at 150°C for 11 days and 200°C for 4 days, to reduce the hydrogen concentration in the steel. The effect of the hydrogen embrittlement was analyzed by manual measurements of the elongations after a slow strain rate testing at 5*10-6 mm/s, and the time to fracture in an in-situ constant load test with a current density of 1.92 mA/cm2 in a 0.5 M Na2SO4 solution. The barrier layer showed an increase in time to fracture, but also a decrease in elongations. The decarburized steel had a small increase in the time to fracture, but not enough to make it a feasible process. The hydrogen relief treatment showed a general decrease in hydrogen concentrations, but the elongation measurements was irregular although with a tendency for improvement. The simplicity of the hydrogen relief treatment makes it an interesting process to reduce the influence of hydrogen embrittlement. However, more investigations are necessary.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-06-26T12:59:39Z No. of bitstreams: 1 VALMIR RODRIGUES BATISTA - TESE (PPGCEMat) 2016.pdf: 18369155 bytes, checksum: 4dd7420f9b0bf191a2596450d01bfaa6 (MD5) / Made available in DSpace on 2018-06-26T12:59:39Z (GMT). No. of bitstreams: 1 VALMIR RODRIGUES BATISTA - TESE (PPGCEMat) 2016.pdf: 18369155 bytes, checksum: 4dd7420f9b0bf191a2596450d01bfaa6 (MD5) Previous issue date: 2016-02-22 / CNPq / Neste trabalho é apresentado um estudo sobre a susceptibilidade à fragilização por hidrogênio de juntas soldadas de metais dissimilares presentes em equipamentos submarinos da indústria do petróleo, as quais ficam submetidas a condições de uso que envolvem esforços mecânicos severos, em ambientes corrosivos, proveniente da água do mar e do fluido petrolífero. O objetivo dessa pesquisa foi avaliar o efeito da utilização dos processos Plasma Pó (PTA-P) e MIG para a aplicação de "amanteigamentos" com Liga de Ni sobre a susceptibilidade à fragilização por hidrogênio de juntas soldadas de aços dissimilares utilizadas em aplicação offshore utilizando diferentes temperaturas de preaquecimento e interpasse e também comparar os resultados para dois aços para válvula, o AISI 8630M e AISI 4130. O processo de soldagem utilizado para a união das juntas foi o processo MIG utilizando-se como metal de adição o arame eletrodo, Inconel-625 (ER NiCrMo-3) de 1,2 mm de diâmetro. Os dois aços foram submetidos a três diferentes combinações de temperaturas de preaquecimento e interpasse antes dos amanteigados pelos processos PTA-P e MIG. Após a etapa de amanteigamento foram realizadas análises de composição química por EDS, microestruturais por MO e MEV, e de microdureza antes e depois do TTAT. Em seguida foram executadas as soldagens de união pelo processo MIG. As amostras de tração foram previamente hidrogenadas simulando as condições existentes de proteção catódica em ambiente submarino. O aumento das temperaturas de preaquecimento e interpasse resultou em maior refino dos grãos da ZTA, entretanto proporcionou aumento da média de sua microdureza e de sua extensão, e em maior migração de Fe do MB para o MS, resultando em maior fragilização por hidrogênio. Pelo processo PTA-P houve uma menor diversidade e frequência de incidência de zonas parcialmente diluídas (ZPD), sendo encontradas apenas ZPD do tipo contínua, enquanto que pelo processo MIG foram encontradas ZPD do tipo descontínua, com diferentes morfologias. O TTAT proporcionou uma significativa redução de 20% a 44% nos valores da microdureza da ZTA. Com base nos níveis de deformação e Índice de Fragilização (IF), o aço AISI 4130 apresentou os melhores resultados com relação à fragilização por hidrogênio. / This Thesis presents a study about hydrogen embrittlement susceptibility of dissimilar metals welded joints present in oil industry equipment, specifically in valves connections with pipes for the oil transport, which are subject to use conditions involving severe mechanical stresses in corrosive environments, from the seawater and the oil fluid. As the valves steel are martensitic its heat affected zone (HAZ) may be susceptible to hydrogen embrittlement not only from cathodic protection but also from the seawater and H2S. Therefore, to prevent this potential embrittlement and consequently crack formation in these regions of the welded joint, is used as nickel alloy filler metal. Therefore, the part of martensitic steel previously undergoes a "buttering" process which consists of applying layers of Ni deposited by welding. The welding process used for the union of the joints was the MIG process using as filler metal the Inconel-625 (ER NiCrMo-3) wire electrode 1.2 mm in diameter. Two steels were buttering, AISI 8630M and AISI 4130. Both were subjected at the three different combinations of preheat and interpass temperatures. For the buttering realization, the same alloy, in powder form, was used by Plasma powder process (PTA-P). To evaluate the efficiency of the PTA-P process in buttering operation it was compared with other buttering performed by MIG process with the same filler metal of the weld joint. After buttering the samples were subjected to post welding heat treatment (PWHT). Chemical composition analyses were performed by Energy Dispersive Spectroscopy (EDS), microstructure by Optical Microscopy (OM) and Scanning Electron Microscopy (SEM), and microhardness. After the welding the samples were machined and hydrogened using a process similar to those used for cathodic protection and submitted to tension tests. The Increase in the preheat and interpass temperature resulted in higher refining the grains of the HAZ however it, increased its average microhardness and extension, promoted greater Fe migration from MB to the buttering, increasing the hydrogen embrittlement. The use of PTA-P process promoted a very lower incidence and diversity of partially diluted zone (PDZ), being found only continuous PDZ. The PWHT promoted a reduction from 20% to 44% of hardness values. Based on the deformation levels and Embrittlement Index (EI), the AISI 4130 steel showed the best results with respect to hydrogen embrittlement.

Este trabalho tem por objetivo avaliar os efeitos do hidrogênio em três diferentes tipos de aços de alta resistência mecânica. São descritos os fenômenos de introdução, difusão e aprisionamento de hidrogênio (H) dentro dos metais, em conjunto com os diferentes tipos de danos provocados devido à presença do hidrogênio. Os materiais de estudo são aços da família Advanced High Strength Steels (AHSS): aços Dual Phase (DP 1000 e DP 1200) e aço Martensítico (M 190). A introdução de hidrogênio nos materiais foi realizada através de carregamento catódico, o qual é representativo para as condições industriais a que se destinam. De modo a avaliar a influência do H nas propriedades mecânicas dos aços, os seguintes ensaios foram propostos: ensaio de carregamento com H, para determinar o conteúdo total de H (saturação) e conteúdo de H difusível (suscetibilidade a fragilização); ensaio de tração ao ar, para determinar a tensão no final da região elástica e resistência à tração na região do entalhe e ensaio de tração com carga constante em ambiente hidrogenado, para avaliar os efeitos provocados pela presença do H e determinar o patamar abaixo do qual o H não apresenta efeito crítico sobre o material. Os efeitos provocados pela aplicação de diferentes densidades de correntes (0,2 – 1,0 mA/cm²) foram avaliados nos ensaios de quantificação de H difusível. Conforme os resultados obtidos todos os aços apresentaram perdas na resistência mecânica à tração quando em ambiente hidrogenado, ou seja, sofreram fragilização por H. Os aços DP 1200 e M 190 (de microestrutura predominantemente martensítica) foram fortemente afetados, conforme evidenciado pela notável queda nos valores de tensão necessários para provocar a falha. Por outro lado, o aço DP 1000, de menor resistência mecânica, demonstrou menor suscetibilidade à fragilização, o que é atribuído a menor permeabilidade do H na microestrutura austenítica. / This work aims to evaluate the effects of hydrogen in three high- strength steel grades. The phenomena of hydrogen (H) entry, transport and trapping inside the metals, together with the different types of damages due to the presence of hydrogen are presented. The study materials are a range of AHSS steel grades: Dual Phase Steel (DP 1000 and DP 1200) and Martensitic Steel (M 190). The hydrogen entry was performed by cathodic charging, which is suitable for industrial applications. In order to evaluate the influence of H on the steel mechanical properties, the following tests were done: H charging, to measure total H content (saturation point) and diffusible H content (embrittlement susceptibility); uniaxial tensile test of uncharged samples to determine notched tensile strength values and the strength levels at the end of elastic region and constant load tensile testing carried out in hydrogen environment, to determine the threshold values where hydrogen has an effect on the material. DP 1200 and M 190 were strongly affected by H pre-charging, as shown by the significant drop in stress required to break them. On the other hand, DP 1000 showed a lower embrittlement susceptibility, which is attributed to its lower mechanical strength. The current densities effects (0.2 up to 1.0 mA/cm²) were evaluated during H charging to measure diffusible H content. All steels showed a drop in the tensile strength i.e. experienced hydrogen embrittlement. Steels with higher tensile strength, as DP 1200 and M 190, showed a much bigger drop that is related to the favorable characteristics of martensitic microstructure regarding to the hydrogen permeability and diffusivity.