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Many experiments demonstrate that the effects of hydrogen solutes decrease macroscopic fracture stresses and strains in ductile materials. Hydrogen-related failures have occurred in nearly all industries involving hydrogen-producing environments. The financial losses incurred from those failures reaches millions if not billions of dollars annually. With the ever-urgent needs for alternative energy sources, there is a strong push for a hydrogen economy from government and private sectors. Safe storage and transportation of hydrogen increases the momentum for studying hydrogen-related failures, especially in ductile materials. To quantify ductile material damage with the effects of hydrogen embrittlement, it is necessary to add hydrogen effects into the void nucleation, void growth, and void coalescence equations. In this research, hydrogen-enhanced void nucleation is our focus, with hydrogen-enhanced void growth and void coalescence t be studied in the future. Molecular Dynamic (MD) and Monte Carlo (MC) simulations with Embedded Atom Method (EAM) potentials were performed to study how hydrogen affects dislocation nucleation, dislocation structure formation and nanovoid nucleation at nickel grain boundaries. The results were inserted into the continuum void nucleation model by Horstemeyer and Gokhale, and the relationships between stress triaxiality-driven void nucleation, grain boundary hydrogen concentrations and local grain geometries were extracted. MD and MC simulations with EAM potentials were also performed to study how hydrogen interstitials affect the dislocation nucleation, dislocation structure formation and subsequent anovoid nucleation of single crystal nickel in different hydrogen-charging conditions. Evolutions of dislocation structures of nickel single crystal with different hydrogen concentrations were compared. The effects of nanovoid nucleation stress and strain at different hydrogen concentrations were quantified. The results were also inserted into the Horstemeyer and Gokhale model and the relationship between stress triaxiality-driven void nucleation and hydrogen concentration caused by stress gradient, which showed similar trends as the grain boundary studies. From nanoscale studies and existing experimental observations, a continuum void nucleation model with hydrogen effects was proposed and used in a continuum damage model based upon Bammann and coworkers. The damage model was implemented into user material code in FEA code ABAQUS. Finite element analyses were performed and the results were compared to the experimental data by Kwon and Asaro.

A series of experiments was performed in an attempt to measure the effects of surface residual stresses on the stress corrosion cracking/hydrogen embrittlement (SCC/HE) behavior of AISI 4340 steel. Stress corrosion tests were performed under load control on cylindrical and notched tensile specimens in acidified 3.5% NaCl solution. The electrochemical potential of the specimens was maintained at -0.7 V versus a saturated calomel reference electrode. Time to failure for specimens tested at various applied and residual stress levels was measured. Stress relieved specimens as well as specimens containing mechanically induced residual stresses were tested. Residual stresses were estimated using Neuber's rule and were measured using an x-ray diffraction technique. In all cases, the sum of the applied and residual stresses was greater than zero. Test results showed the initiation of SCC/HE cracks to be insensitive to the effects of surface residual stresses under the conditions evaluated. This is probably a result of the total time to failure criterion used to evaluate the SCC/HE tests. The extremely aggressive environment used in these experiments apparently led to rapid crack initiation, even in specimens containing compressive residual stresses. Another possible explanation of the insensitivity of this series of tests is crack initiation in the interior of the specimens below the depth of the mechanically induced residual stresses. / Master of Science

Gelöster Wasserstoff in Metallen führt in vielen Fällen zu einer Reduzierung der Güte von mechanischen Eigenschaften. Dies äußert sich auf vielfältige Weise und wird unter dem Begriff Wasserstoffversprödung zusammengefasst. Für ein grundlegendes Verständnis dieses Phänomens müssen die Vorgänge im Metall auf mikroskopischer Skala ergründet werden. Im Rahmen dieser Arbeit wurde daher ein Aspekt der Wasserstoffversprödung, die Interaktion von Wasserstoff mit Versetzungen, näher untersucht. Zur Untersuchung des Einflusses von Wasserstoff auf die Versetzungsbildung wurden verschiedene Verformungsexperimente an Palladium und Vanadium durchgeführt. Prinzipielle Vorgänge der Defektbildung wurden durch Versuche an einzelnen Versetzungen unter Verwendung von Nanoindentation und Zugexperimenten im ETEM durchgeführt, um einen breiten Überblick zu erlangen. Zusätzlich wurden zum besseren Verständnis der Vorgänge Molekulardynamiksimulationen von derartigen Versuchen ausgeführt. Zur Untersuchung der Interaktion von Versetzungen miteinander wurden Säulen im Mikrometerbereich verformt und Blech durch Kaltwalzen verformt. Des Weiteren wurde durch Hochdruck-Torsion maximale Verformungen realisiert. Die verwendeten Modellmaterialien erlauben es verschiedene prinzipielle Vorgänge der Defektbildung zu untersuchen und so einen breiten Überblick über prinzipielle Vorgänge im kfz Gitter (Palladium) bzw. krz Gitter (Vanadium) zu erhalten.

O processo de proteção catódica é amplamente utilizada na indústria do petróleo e gás para a prevenção contra a corrosão. Entretanto, devido às reações catódicas induzidas pelo potencial catódico aplicado pode ocorrer a formação de depósito calcário na superfície de componentes protegidos catodicamente em água do mar. Existe certa incerteza na literatura sobre o papel do depósito calcário na absorção de hidrogênio e consequentemente na fragilização pelo hidrogênio. Assim, o presente trabalho visa investigar sua influência a fim de contribuir para o melhor entendimento da participação dessa camada nesse fenômeno. Para isso, foram realizados testes de permeação eletroquímica de hidrogênio, de tração de baixa taxa de deformação (BTD) e de cronoamperometria no aço API 5CT P110 em três soluções diferentes: água do mar sintética (AMS), água do mar sintética sem Ca2+ e Mg2+ e NaCl 3,5%. Além disso, foram aplicados dois potenciais catódicos: -1000 mVECS e -1500 mVECS. Após o ensaio de tração de BTD e de cronoamperometria as amostras foram analisadas em MEV/EDS. A partir dos resultados obtidos verificou-se que o depósito calcário formado em AMS em -1000 mVECS é formado por uma fina camada inicial rica em Mg seguida de cristais de aragonita. A formação dessa camada aparentemente diminuiu o fluxo de hidrogênio no estado estacionário em comparação com as demais soluções avaliadas nesse mesmo potencial. Todavia, essa diminuição não resultou em uma mudança significativa na fragilização do material. O depósito calcário formado em AMS em -1500 mVECS mostrou-se poroso e pulverulento, apresentando principalmente Mg em sua composição. O fluxo de hidrogênio no estado estacionário e a fragilização do material em AMS em -1500 mVECS foi maior do que nas demais soluções nesse potencial. Um possível mecanismo para explicar o efeito do depósito calcário na absorção e na fragilização pelo hidrogênio foi proposto e indica a competição entre o fator superficial ocasionado pela formação do depósito calcário e a sobretensão em hidrogênio. / The process of cathodic protection is widely used in oil & gas industry to corrosion prevention. However, the cathodic reactions induced by the applied cathodic potential can lead to the calcareous deposit formation on the cathodically protected structure surface in sea water. There is uncertainty about the role of calcareous deposit on hydrogen uptake and consequently on hydrogen embrittlement. Hydrogen electrochemical permeations, slow strain rate and chronoamperometric tests were carried out in three different solutions: artificial sea water, artificial sea water without Ca2+ and Mg2+ and 3.5% NaCl solution. Besides that, two cathodic potentials were applied: -1000 mVSCE e -1500 mVSCE. After slow strain rate and chronoamperometric tests the samples were analyzed in SEM/EDS. According to the obtained results it was observed that calcareous deposits formed in artificial sea water at -1000 mVSCE consists on a thin Mg-rich inner layer and an outer layer of aragonite crystals. The deposit formation apparently decreased hydrogen flux at steady state in comparison with other solutions evaluated at the same potential. The calcareous deposit formed in artificial sea water at -1500 mVSCE was porous, powdery and mainly composed by Mg. The hydrogen flux at steady state and the embrittlement of the material were higher in artificial sea water at -1500 mVSCE than in other solutions at the same potential. A possible mechanism to explain the calcareous deposit effect on hydrogen uptake and on hydrogen embrittlement was proposed and it indicates the competition between the surface effect induced by calcareous deposit formation and the hydrogen overpotential.

[pt] Na indústria do petróleo, as tubulações de aço que conduzem hidrocarbonetos estão constantemente submetidas à ação do gás sulfídrico (H2S).Na condição de veículo do átomo de hidrogênio, este gás pode ensejar sua difusão no aço, provocando a fragilização do mesmo. O tratamento térmico pós-soldagem,previsto nos procedimentos de soldagem convencionais qualificados pela Petrobras, atua no sentido de atenuar os efeitos danosos do hidrogênio, na medida em que reduz o nível de tensões presentes na junta soldada, quando em contato com o H2S. O presente trabalho conduz um estudo a respeito do comportamento de juntas de topo de tubulações em aço-carbono microligado, soldadas conforme o procedimento conhecido como Dupla-Camada, comparando-o ao de juntas obtidas pelo procedimento de soldagem dito Convencional. O procedimento Dupla-Camada não contempla tratamento térmico pós-soldagem de revenimento, pois as tensões internas remanescentes na zona de solda são aliviadas pelo passe de soldagem subseqüente, agregando, portanto, redução do custo de manutenção e acréscimo da disponibilidade de tubos condutores de derivados do petróleo. Outrossim, este procedimento eleva a vida-útil da junta, pela melhoria da sua tenacidade, em função da redução do tamanho de grão obtida nas zonas termicamente afetadas (ZTA s). A medição das tensões residuais provenientes da soldagem (oriundas de contração, transformação de fases, gradiente de resfriamento e difusão do átomo de hidrogênio inerente ao processo) e da exposição do material ao H2S (provocadas por difusão do H), através do método de difração de raios-X, avaliou a efetividade do alívio de tensões alcançado em juntas idênticas soldadas pelos dois procedimentos citados. Foi, também, investigada a ocorrência de microtrincas inter e/ou transgranulares, bem como foram observadas as microestruturas resultantes, através de metalografias óptica e eletrônica de varredura, medidas as microdurezas das juntas, assim como os tamanhos de grão na zona de ligação das ZTA s, e comparados os resultados obtidos segundo os dois procedimentos de soldagem. A seguir, as amostras foram submetidas a análise em microscópio eletrônico de transmissão, visando a observação das discordâncias existentes, mecanismos que contribuem para o alcance do nível de tensões residuais reinante, que não puderam ser avaliados pelo método de medição empregado. Os resultados obtidos indicaram, em média, um estado de tensões mais relaxado, com evidência de microestrutura de granulação ligeiramente mais fina, após a soldagem pelo procedimento Convencional. Não foram encontradas microtrincas, nem constatada uma substancial existência de discordâncias, e constatou-se uma microdureza maior nas regiões de granulação refinada nas ZTA s. Torna-se necessária a realização de mais medições de tensões residuais, que forneçam suporte estatístico à tomada de decisão na escolha do procedimento de soldagem mais adequado. Do ponto-de-vista operacional, os resultados obtidos indicam a demanda por um controle mais apurado na velocidade de avanço da deposição do eletrodo (metal de adição) por parte do soldador executante do procedimento de soldagem Dupla-Camada, suficiente à garantia da elevação do aporte térmico exigida ao recozimento da microestrutura de granulação grosseira das ZTA s, visando a garantia do alcance das propriedades requeridas à junta soldada. / [en] In petroleum industry, steel pipes that conduct products are frequently submitted to the H2S action, that produces steel atomic hydrogen diffusion and embrittlement. The post- welding heat treatment, predicted in welding procedures qualified by Petrobras, reduce the dangerous hydrogen effect when joint is in contact with H2S, by reducing existing residual internal stresses level. This thesis studies a top joint performance when welded by two different techniques:Conventional, with tempering after welding, and Two-Layer Deposition, without post-welding heat treatment to internal stresses relief. In the last case, the residual stresses produced during welding deposition are reduced by action of second layer, what reduces maintenance costs and increase the equipments availability. This welding procedure increase the welded joint life too, by reducing grain size and increasing toughness of thermal affected zone. By X-ray diffraction methode, were measured internal stresses deriving from welding process and H2S exposition, to detect the efficacy of stress relief made on identical joints welded by the two refered procedures. They were also investigated existing microcracks, observed resultant microstructures by optical and scanning electron microscopy, measured microhardnesses and compared grain sizes in joints regions welded by both procedures. Then, samples were analysed by transmission electron microscopy to evaluate itself existing dislocations level, responsible by internal tension level existing at regions from welded zone that were inable to be measured by X-ray methode. Results obtained showed a major stress relief state and a relatively lowest grain size in joints welded by Conventional welding process. There was detected neither microcracks nor an important dislocations level and the microhardnesses showed higher values on the biggest grains at the thermal affected zones. It´s necessary to make more residual stresses measures to give a statistical support to decision about what is the most adequate welding procedure. From the operational point-of- view, these results suggest the necessity of a better parameters control process by the welder, in the case of alternative welding procedure proposed, the Two-Layer Deposition Technique.

"February, 2004." / Bibliography: leaves 231-249. / xxvii, 261 leaves : ill. (some col.), plates, photos (col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Examines ways of reducing the risk of hydrogen assisted cold cracking in pipeline construction by modifying the construction procedure to reduce residual stress and hydrogen concentration. A numerical model of the pipeline construction procedure capable of modelling the process in a transient sense was created. Experimental validation of the model involved using the "blind hole drilling" strain gauge method of residual stress measurement. The diffusion of hydrogen during welding was modelled using a scheme based on Fick's Second Law of Diffusion, finding that the parameters which dominate the rate of diffusion are the timing of the weldment process, joint geometry, pre-heating and post-heating. / Thesis (Ph.D.)--University of Adelaide, School of Mechanical Engineering, 2004

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O processo de proteção catódica é amplamente utilizada na indústria do petróleo e gás para a prevenção contra a corrosão. Entretanto, devido às reações catódicas induzidas pelo potencial catódico aplicado pode ocorrer a formação de depósito calcário na superfície de componentes protegidos catodicamente em água do mar. Existe certa incerteza na literatura sobre o papel do depósito calcário na absorção de hidrogênio e consequentemente na fragilização pelo hidrogênio. Assim, o presente trabalho visa investigar sua influência a fim de contribuir para o melhor entendimento da participação dessa camada nesse fenômeno. Para isso, foram realizados testes de permeação eletroquímica de hidrogênio, de tração de baixa taxa de deformação (BTD) e de cronoamperometria no aço API 5CT P110 em três soluções diferentes: água do mar sintética (AMS), água do mar sintética sem Ca2+ e Mg2+ e NaCl 3,5%. Além disso, foram aplicados dois potenciais catódicos: -1000 mVECS e -1500 mVECS. Após o ensaio de tração de BTD e de cronoamperometria as amostras foram analisadas em MEV/EDS. A partir dos resultados obtidos verificou-se que o depósito calcário formado em AMS em -1000 mVECS é formado por uma fina camada inicial rica em Mg seguida de cristais de aragonita. A formação dessa camada aparentemente diminuiu o fluxo de hidrogênio no estado estacionário em comparação com as demais soluções avaliadas nesse mesmo potencial. Todavia, essa diminuição não resultou em uma mudança significativa na fragilização do material. O depósito calcário formado em AMS em -1500 mVECS mostrou-se poroso e pulverulento, apresentando principalmente Mg em sua composição. O fluxo de hidrogênio no estado estacionário e a fragilização do material em AMS em -1500 mVECS foi maior do que nas demais soluções nesse potencial. Um possível mecanismo para explicar o efeito do depósito calcário na absorção e na fragilização pelo hidrogênio foi proposto e indica a competição entre o fator superficial ocasionado pela formação do depósito calcário e a sobretensão em hidrogênio. / The process of cathodic protection is widely used in oil & gas industry to corrosion prevention. However, the cathodic reactions induced by the applied cathodic potential can lead to the calcareous deposit formation on the cathodically protected structure surface in sea water. There is uncertainty about the role of calcareous deposit on hydrogen uptake and consequently on hydrogen embrittlement. Hydrogen electrochemical permeations, slow strain rate and chronoamperometric tests were carried out in three different solutions: artificial sea water, artificial sea water without Ca2+ and Mg2+ and 3.5% NaCl solution. Besides that, two cathodic potentials were applied: -1000 mVSCE e -1500 mVSCE. After slow strain rate and chronoamperometric tests the samples were analyzed in SEM/EDS. According to the obtained results it was observed that calcareous deposits formed in artificial sea water at -1000 mVSCE consists on a thin Mg-rich inner layer and an outer layer of aragonite crystals. The deposit formation apparently decreased hydrogen flux at steady state in comparison with other solutions evaluated at the same potential. The calcareous deposit formed in artificial sea water at -1500 mVSCE was porous, powdery and mainly composed by Mg. The hydrogen flux at steady state and the embrittlement of the material were higher in artificial sea water at -1500 mVSCE than in other solutions at the same potential. A possible mechanism to explain the calcareous deposit effect on hydrogen uptake and on hydrogen embrittlement was proposed and it indicates the competition between the surface effect induced by calcareous deposit formation and the hydrogen overpotential.

Ce travail de thèse porte sur l’étude de divers mécanismes de fragilisation d’un acier inoxydable supermartensitique 16Cr-4Ni à basse teneur en carbone (Virgo™38) utilisé pour la fabrication des compresseurs centrifuges produits par GE Oil&Gas.Il a été montré que la microstructure fine, polyphasée et morphologiquement très complexe de cet alliage était sensible aux conditions de traitement thermique. Notamment, la proportion et la répartition de l’austénite de réversion, la présence de carbure de chrome et la ségrégation intergranulaire d’éléments fragilisant tel que le phosphore ont été mis en évidence suite à plusieurs traitements thermiques. La ségrégation du phosphore aux joints de grain (SPJG) est l’un des mécanismes entrainant la fragilisation du Virgo™38 sous certaines conditions de traitement thermique.La présence d’austénite de réversion n’entraine pas seulement une amélioration de la ténacité de l’alliage mais également le piégeage de l’hydrogène dans cette phase. Etant donnée la grande instabilité mécanique de l’austénite, sa transformation sous contrainte provoque la libération de cet hydrogène piégé et ainsi une surconcentration locale en hydrogène. La fragilisation par hydrogène est le deuxième mécanisme entrainant la fragilisation du Virgo™38 étudié dans cette thèse.Les mécanismes mis en jeu lors de la formation de l’austénite de réversion conduisent à la répartition hétérogène des éléments d’alliage. L’une des conséquences de cette répartition hétérogène est la corrosion sélective de l’une ou l’autre des phases de l’alliage en fonction du pH de l’environnement et de la charge appliquée. La dissolution préférentielle est le dernier mécanisme abordé. / This PhD thesis is focused on the study of embrittlement mechanisms in a 16Cr-4Ni low carbon supermartensitic stainless steel (Virgo™38) used for the construction of rotating parts of centrifugal compressors produced by GE Oil&Gas.It is shown that the morphologically complex multiphase microstructure of this alloy is very sensitive to the heat treatment conditions. In particular, the fraction and repartition of retained austenite, the presence of chromium carbides and the phosphorous grain boundary segregation (PGBS) are evidenced consecutive to several heat treatments. PGBS is one of the mechanisms leading to brittle failure of Virgo™38 after specific heat treatments.The presence of retained austenite is not only beneficial for toughness but also leads to hydrogen trapping in this phase. Due to the mechanical instability of retained austenite, its transformation under applied stress leads to the release of trapped hydrogen into newly formed martensite and thus to a local overconcentration of hydrogen. Hydrogen embrittlement is the second mechanism studied in this report.Mechanisms involved during the formation of retained austenite lead to the heterogeneous repartition of alloying elements (partitioning). One of the consequences being the selective dissolution of one or the other phase of the alloy as a function of the pH of the environment and of the load applied. Preferential dissolution is the third mechanism studied.