No description available.

Despite the high demand for press-hardenable steel (PHS) with coatings that provide sacrificial cathodic protection, Zn-based coatings have experienced limited use due to the significant challenges associated with avoiding liquid metal embrittlement (LME) while maintaining robust cathodic protection when using conventional PHS materials and processing techniques. The present research addresses these challenges by reducing the conventional direct hot press forming (DHPF) temperature to between 600–700 °C, such that forming and quenching occurs well below the Zn(Fe)liq → Г-Fe3Zn10 peritectic temperature of 782 °C, thereby removing the conditions necessary for LME to occur while allowing for formation of the cathodically-protective Г-Fe3Zn10 phase. The objective of this work was to define a process window for two galvanized prototype PHS alloys with compositions of 0.20C-2.01Mn-0.26Si-0.005B and 0.19C-2.5Mn-0.26Si-0.005B (wt%) that would result in fully martensitic microstructures, tensile strengths (TS) ≥ 1500 MPa, and robust cathodic protection, defined as attaining ≥ 15 vol% Г-Fe3Zn10 in the coating microstructure, while avoiding LME. Accomplishing this task involved characterizing both grades as a function of austenization time, stamping temperature, and strain imposed by the forming process in order to define process windows that resulted in parts that met the aforementioned property requirements. It was found that the approach of increasing the Mn content relative to conventional PHS grades was successful in improving the hardenability sufficiently to enable the formation of fully martensitic microstructures despite the lower effective cooling rates associated with the reduced DPHF temperatures. Microstructural imaging and tensile testing demonstrated that, for both prototype PHS grades, a process window exists for the production of parts that satisfy the targets of the formation of fully martensitic microstructures and TS ≥ 1500 MPa while exhibiting uniform elongation of about 0.05 followed by significant post-uniform elongation. The effect of DHPF temperature and strain imposed by the forming process on mechanical properties was found to be negligible. Tensile tests and fractography revealed that reducing the DHPF temperature to between 600–700 °C was successful in preventing LME, thereby allowing samples to fracture in a ductile manner. Micro-cracking in the coating of the DHPF part was observed; however, these cracks were arrested at the coating-substrate interface. For all tested conditions, the coating met the target of ≥ 15 vol% Г-Fe3Zn10, implying that robust cathodic protection is expected. Based on the results of these experiments, it was concluded that DHPF process windows that meet all of the property targets include austenization times and DHPF temperatures of 120–180 s and 600–700 °C, respectively, for the 2Mn grade, and 60–180 s and 600–700 °C, respectively, for the 2.5Mn grade. / Thesis / Master of Science (MSc)

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

Gegenstand des Vorhabens im Rahmen der WTZ mit Russland ist die Versprödung des Reaktordruckbehälters infolge der Strahlenbelastung mit schnellen Neutronen im kernnahen Bereich. Um den Einfluss von bestrahlungsinduzierten Gitterdefekten auf die mechanischen Eigenschaften zu ermitteln, wurden analytische Berechnungen zum Einfluss von Hindernissen auf die Beweglichkeit von Versetzungen und damit auf die Ausbildung einer plastischen Zone an der Rissspitze durchgeführt. Es wird demonstriert, dass sich die an der Rissspitze entstehenden Versetzungen an dem Hindernis (bestrahlungsinduzierte Punktdefekte) aufstauen. In Abhängigkeit der Rissbelastung KI und der Entfernung des Hindernisses von der Rissspitze werden die Versetzungsdichte und das durch den Versetzungsstau verursachte Spannungsfeld berechnet. Mit Hilfe von Experimenten zur Neutronenkleinwinkelstreuung (SANS - small angle neutron scattering) an verschiedenen WWER-Stählen und Modelllegierungen wurden Größenverteilungen und die Volumenanteile der strahleninduzierten Defekte für verschiedene Bestrahlungszustände (Fluenzen, Bestrahlungstemperaturen) ermittelt. Es wurde gezeigt, dass sich die strahleninduzierte Werkstoffschädigung durch Wärmebehandlung weitgehend wieder ausheilen lässt. Nach der thermischen Ausheilung ist der Werkstoff bei erneuter Bestrahlung weniger anfällig für strahleninduzierte Defekte. Die Ergebnisse der SANS-Untersuchungen wurden mit der Änderung der mechanischen Eigenschaften (Härte, Streckgrenze und Sprödbruchübergangstemperatur) korreliert. Mit der kinetischen Gitter-Monte-Carlo-Methode wurden numerische Sensitivitätsstudien zum Einfluss des Cu-Gehalts auf die Stabilität von Defekt-Clustern durchgeführt. Die Berechnungen zeigen, dass die Anwesenheit von Cu-Atomen zur Bildung von langlebigen Defekten führt. Dabei werden Leerstellen in Cu/Leerstellen-Cluster eingefangen. Leerstellen in reinem Eisen sind bei Bestrahlungstemperaturen von 270 °C dagegen nicht stabil, die Lebensdauer liegt zwischen 0.01 s und 1 s. Die kritische Cu-Konzentration, ab welcher stabile Defekte entstehen, beträgt ca. 0.1 Masseprozent.

Defect-driven transport of impurities plays a key role in the microstructure evolution of alloys, and has a great impact on the mechanical properties at the macroscopic scale. This phenomenon is greatly enhanced in irradiated materials because of the large amount of radiation-induced crystal defects (vacancies and interstitials). For instance, the formation of nanosized solute clusters in neutron-irradiated reactor pressure vessel (RPV) ferritic steels has been shown to hinder dislocation motion and induce hardening and embrittlement. In Swedish RPV steels, this mechanical-property degradation is enhanced by the high content of manganese and nickel impurities. It has been suggested that the formation of Mn-Ni-rich clusters (which contain also Cu, Si, and P) might be the outcome of a dynamic process, where crystal defects act both as nucleation sites and solute carriers. Solute transport by point defects is therefore a crucial mechanism to understand the origin and the dynamics of the clustering process. The first part of this work aims at modeling solute transport by point defects in dilute iron alloys, to identify the intrinsic diffusion mechanisms for a wide range of impurities. Transport and diffusion coefficients are obtained by combining accurate ab initio calculations of defect transition rates with an exact mean-field model. The results show that solute drag by single vacancies is a common phenomenon occurring at RPV temperature (about 300 °C) for all impurities found in the solute clusters, and that transport of phosphorus and manganese atoms is dominated by interstitial-type defects. These transport tendencies confirm that point defects can indeed carry impurities towards nucleated solute clusters. Moreover, the obtained flux-coupling tendencies can also explain the observed radiation-induced solute enrichment on grain boundaries and dislocations. In the second part of this work, the acquired knowledge about solute-transport mechanisms is transferred to kinetic Monte Carlo (KMC) models, with the aim of simulating the RPV microstructure evolution. Firstly, the needed parameters in terms of solute-defect cluster stability and mobility are calculated by means of dedicated KMC simulations. Secondly, an innovative approach to the prediction of transition rates in complex multicomponent alloys is introduced. This approach relies on a neural network based on ab initio-computed migration barriers. Finally, the evolution of the Swedish RPV steels is simulated in a "gray-alloy" fashion, where impurities are introduced indirectly as a modification of the defect-cluster mobilities. The latter simulations are compared to the experimental characterization of the Swedish RPV surveillance samples, and confirm the possibility that solute clusters might form on small interstitial clusters. In conclusion, this work identifies from a solid theoretical perspective the atomic-transport phenomena underlying the formation of embrittling nanofeatures in RPV steels. In addition, it prepares the ground for the development of predictive KMC tools that can simulate the microstructure evolution of a wide variety of irradiated alloys. This is of great interest not only for reactor pressure vessels, but also for many other materials in extreme environments. / <p>QC 20151123</p>

No description available.