The effect of hydrogen charging current density and tensile strain rate on the mechanical properties of X80 pipeline steel were investigated by slow strain rate test (SSRT), Charpy impact test, and scanning electron microscopy (SEM) in this thesis. The results show that both the ultimate tensile strength and elongation to failure of X80 steel were deteriorated significantly after charging with hydrogen. With a strain rate of 5 x 10-5 s-1, the relative tensile strength and plasticity loss of X80 steel had no significant change within the range of assumed hydrogen partial pressures at room temperature. At room temperature, X80 steel had no apparent variation in ultimate tensile strength and elongation, except at the strain rate of 10-6 s-1. Specimens obtained the greatest relative tensile strength loss and plasticity loss when strained at 10-6 s-1 with a current density of 4.6 mA/cm2. The fracture morphology of two test groups of X80 steel exhibited significant brittle rupture when tested with dynamic hydrogen charging. The impact energy of X80 was not affected by hydrogen charging. Different current density also had no influence on the results of the impact test.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-16T14:17:49Z No. of bitstreams: 1 DANIELLE FREIRE DE ARAÚJO - TESE (PPGEQ) 2017.pdf: 4185527 bytes, checksum: e932aa4fa6aa33e42656b4c6d33e01b5 (MD5) / Made available in DSpace on 2018-08-16T14:17:49Z (GMT). No. of bitstreams: 1 DANIELLE FREIRE DE ARAÚJO - TESE (PPGEQ) 2017.pdf: 4185527 bytes, checksum: e932aa4fa6aa33e42656b4c6d33e01b5 (MD5) Previous issue date: 2017-08 / Capes / O presente trabalho teve como objetivo o estudo do aprisionamento de hidrogênio em aços da classe API 5L X60, X65 e X70, classificados como aços de alta resistência e baixa liga (ARBL). A respectiva implicação da difusão do hidrogênio, isto é, adsorvido e dissolvido na matriz metálica dos aços, o aprisionamento em defeitos microestruturais, foram abordados através do estudo da cinética de aprisionamento, com a determinação das taxas de liberação (k) e captura (p), da da obtenção da energia de aprisionamento (EA) e da densidade de sítios aprisionadores (N). Através da energia de aprisionamento, determinada via eletroquímica, foi possível fazer a caracterização dos típos de sítios aprisionadores, presentes nos materiais estudados, no qual se configurou a presença de sítios reversíveis e cuja característica microestrutural mostra a existência de contornos de grãos com fases de ferrita e perlita, identificadas após ataque químico com nital à 2% e pela microscopia óptica. Os resultados obtidos para os parâmetros cinéticos de aprisionamento são condizentes com os resultados encontrados na literatura e por análises de dessorção térmica para esses tipos de aços. / The objective of the present work was to study the hydrogen trapping in steel class API 5L X60, X65 and X70, classified as High-strength low-alloy (HSLA). The respective implication of the diffusion of hydrogen, i.e., adsorbed and dissolved in the metallic matrix of the steels, the trapping in microstructural defects, were approached through the study of the trapping kinetics, with the determination of the release (k) and capture (p ), The trapping energy (EA) and the density of trap sites (N). Through the trapping energy, determined by electrochemistry, it was possible to characterize the types of trap sites, present in the studied materials, in which the presence of reversible sites was configured and whose microstructural characteristic it shows the existence of grain boundaries, with phases of ferrite and perlite, identified after chemical attack with 2% nital and by optical microscopy. The results obtained for the kinetic entrapment parameters are consistent with the results found in the literature and by thermal desorption analysis for these types of steels.

Pipeline steels that carry oil and natural gas in severe environments suffer from two important modes of failure: stress corrosion cracking (SCC) and hydrogen-induced cracking (HIC). The SCC has been studied extensively in the literature; however, HIC phenomenon in pipeline steels is less investigated by researchers. Nevertheless, HIC is recognized as the most important damage mode in sour environment. Hydrogen atoms produced due to surface corrosion of the steel diffuse into it through microstructural defects. When a critical amount of hydrogen is accumulated in such defects, HIC cracks initiate and propagate. The main objectives of this thesis are to find the HIC crack nucleation and propagation sites, evaluate a role of texture and grain boundary character distribution in crack growth and finally establish the effect of different microstructural parameters contributing to the HIC related failure in pipeline steel. In this thesis, HIC standard test and electrochemical hydrogen-charging experiments were used to induce HIC cracks in pipeline steels. HIC cracks at the cross section of tested samples were observed using scanning electron microscope (SEM). The SEM observations clearly indicate that the investigated X60 and X70 steels are susceptible to HIC while the X60SS steel showed a higher resistance to HIC. This experiment also proved that the X70 steel has higher susceptibility to HIC than the other investigated steel. Energy dispersive spectroscopic (EDS) analyses indicated that two types of inclusion namely manganese sulfide and carbonitiride precipitates serve as crack nucleation sites. HIC cracks were observed to propagate at the center of cross section where the segregation of some elements such as carbon and manganese occurred. Moreover, two other experiments were carried out in order to evaluate the capability of pipeline steels for hydrogen-trapping. The first test, hydrogen-permeation experiment, showed that all pipeline steel specimens, such as X70, X60 and X60SS steels, contain both reversible and irreversible hydrogen traps. However, the density of traps at the center of cross section was higher than other regions in all tested specimens. The hydrogen-discharging experiments also showed that all specimens keep a considerable amount of hydrogen inside their traps. The hydrogen traps, based on their binding energy with the metal matrix, are categorized as reversible (weak) and irreversible (strong) traps and the roles of each type of traps are explained. Electron backscatter diffraction (EBSD) measurements were done along the HIC crack in X70 steel after standard HIC test. The results showed that the {100} texture was strong while the {111} texture was weak. Some special texture components, such as the {110}, {332} and {112}, were observed after the HIC crack-stoppage. EBSD results also documented that fine grain colonies were prone to intergranular HIC crack propagation and IPF and PF, calculated in both sides of HIC cracks, showed the preferences of ND||<100> orientation. Both susceptible X60 and non-susceptible X60SS steel to HIC were compared based on the EBSD results. It was observed that the high amount of recrystallization fraction with no stored energy is one of the main reasons for a higher HIC resistance of X60SS steel to HIC. Moreover, Kernel Average Misorientation (KAM) data showed that the deformation is more concentrated in the as-received and HIC tested X60 specimens. The effect of hydrogen-charging during tensile/fatigue loading of X60SS steel was studied and it was observed that some HIC cracks at the cross section of X60SS steel were appeared after hydrogen-charging at stresses below the yield stress. Experiments were carried out to understand the effect of cold-rolling and annealing on HIC susceptibility in pipeline steels. The results documented that the {100} dominant texture is more pronounced in 50% and 90% cold-rolled and annealed specimens. The effect of different factors such as KAM degree and recrystallized fraction affecting HIC susceptibility on cold-rolled and annealed specimens was investigated. The obtained results showed that the cold-rolling and annealing process may not be considered as an effective method to increase HIC resistance in pipeline steels.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T21:32:45Z No. of bitstreams: 1 JOÃO PAULO DANTAS DE CARVALHO - DISSERTAÇÃO PPGEQ 2015..pdf: 1534561 bytes, checksum: 93959f6eca85fa51565d250b6a984284 (MD5) / Made available in DSpace on 2018-03-23T21:32:45Z (GMT). No. of bitstreams: 1 JOÃO PAULO DANTAS DE CARVALHO - DISSERTAÇÃO PPGEQ 2015..pdf: 1534561 bytes, checksum: 93959f6eca85fa51565d250b6a984284 (MD5) Previous issue date: 2015-11-11 / CNPq / Desde a sua descoberta, em 1864 por Cailletet, a fragilização de metais por hidrogênio, foi sujeito a inúmeras investigações, sendo primeiramente estudado com a injeção de hidrogênio gasoso em metais e ligas. Devanathan e Stachurski (1962) desenvolveram a técnica eletroquímica de permeação de hidrogênio em metais e ligas, tornando o estudo mais prático, esta metodologia se baseia em uma dupla célula eletroquímica dispostas simetricamente onde o metal a ser estudado é inserido entre elas. Uma delas conhecida como célula de carga irá gerar o H2 a ser permeado através do corpo de prova e na outra, conhecida como célula de detecção, o mesmo será oxidado e quantificado seu fluxo. Toda a detecção é realizada potenciostaticamente, mas a geração pode ser realizada por meio galvanostático (método galvanostático-potenciostático), potenciostacamente (método duplo-potenciostático) ou por permeação em circuito aberto em meio ácido, chamado de „PCAA‟. As normas ASTM 148-97 (2003) e ISO 17081 (2004) padronizam os experimentos de permeação eletroquímica de hidrogênio. Como os diferentes métodos são baseados em soluções de contorno diferenciados para solução da segunda lei de Fick, tais normas não levam isto em consideração adotando o cálculo da difusividade do hidrogênio apenas pelo método duplo potenciostático, mesmo para aqueles que estudam o fenômeno, diga-se de passagem, em sua grande maioria, utilizando a metodologia galvanostático-potenciostático. Autores como McBreen et al (1966) e Boes & Zuchner (1972) descrevem o fenômeno de permeação de hidrogênio em metais de forma matemática, a partir da solução da segunda de lei de Fick, estes trabalhos atestam a diferença entre os métodos duplo-potenciostatico e galvanostático-potenciostático, porém nunca foi proposto um modelo que descreva o comportamento do método PCAA. Com isso, o trabalho tem como objetivo elucidar o emprego dos modelos matemáticos para determinação do coeficiente de difusão do hidrogênio em metais através das distintas técnicas eletroquímicas de permeação, utilizando os aços API 5L X70 e X65, além disto procurou-se um modelo matemático para o caso em que a geração de hidrogênio seja realizada pelo método PCAA. Neste trabalho atesta-se que que o uso das equações proposta pela norma, a princípio, subestimam o valor da difusividade. A equação proposta para o método PCAA, apresentou um perfeito ajuste de dados experimentais de permeação. A correlação proposta para o cálculo da difusividade mostrou-se coerente para estimar este parâmetro, não só para o caso PCAA, como também para todos os casos. / Since its discovery in 1864 by Cailletet, hydrogen embrittlement of metals, was subjected to numerous investigations, first being studied with the injection of gaseous hydrogen in metals and alloys. Devanathan and Stachurski (1962) developed the electrochemical technique of hydrogen permeation in metals and alloys, making it the study more practical this methodology is based on a dual symmetrically arranged electrochemical cell where the metal to be studied is inserted between them. One known as load cell will generate H2 to be permeated through the specimen and the other, known as the detection cell, it will be oxidized and its flow quantified. All detection is performed potentiostaticly, but the generation can be performed by galvanostatic (galvanostaticpotentiostatic method), potentiostaticly (double- potentiostatic method), or by hydrogen permeation on acid environment method known as a PCAA. The regulations ASTM 148-97 (2003) and ISO 17081 (2004) standardize the electrochemical hydrogen permeation experiments. How different methods are based on different workarounds for solution of the second Fick's law, such rules do not take this into account by adopting the calculation of the hydrogen diffusivity only by the dual voltage method, even for those who study the phenomenon, say passing for the most part, using the galvanostatic-potentiostatic methodology. Authors such as McBreen et al (1966) and Boes & Züchner (1972) describe the hydrogen permeation phenomenon in mathematical form of metal from the solution of the second Fick law, these works attest to the difference between the double-potentiostatic methods and galvanostatic-potentiostatic, but has never proposed a model that describes the behavior of the PCAA method. Thus, the study aims to elucidate the use of mathematical models to determine the hydrogen diffusion coefficient in metals through the different electrochemical techniques permeation using the API 5L steels X70 and X65, in addition sought a mathematical model for the case where the hydrogen generation is performed by the PCAA method. This work testifies that the use of the equations proposed by the standard at first underestimate the value of diffusivity. The equation proposed for the PCAA method, presented a perfect fit experimental permeation data. The proposed correlations for calculating the diffusivity was found to be consistent to estimate this parameter not only to the case PCAA, but also for all cases.