The work is concerned with the development of a multi-stage corrosion fatigue lifetime model, with emphasis on pitting as a precursor to cracking. The model is based upon the quantitative evaluation of damage during the overall corrosion fatigue process. The fatigue response of as-received API 5L X65 linepipe steel has been investigated in terms of the evolution of damage during pit development, pit-to-crack transition and crack propagation. Micro-potentiostatic polarisation was conducted to evaluate role of stress on pit development. Crack growth rate measurements were conducted on pre-pitted specimens, which were tested in air and brine, to evaluate the initiation and propagation behaviour of cracks emanating from artificial pits. Finite element analysis was undertaken to evaluate the stress and strain distribution associated with the pits. A cellular automata finite element model was also developed for predicting corrosion fatigue damage. Pit growth rate was enhanced under stress. It was considered that the strain localisation effect of the pit facilitated strain-assisted dissolution. In air, cracks initiated predominantly from the pit mouth. FEA results indicated that this was due to localisation of strain towards the pit mouth. In corrosion fatigue, cracks tended to initiate at the pit base at low stress and at the pit mouth at higher stresses. Crack initiation lifetimes were shorter in the aggressive environment compared to air and the effect of the environment on crack initiation lifetime was lower at higher stress levels. Crack initiation lifetime for double pits generally decreased with decreasing pit-to-pit separation distance. The microstructure was observed to influence crack growth behaviour in air particularly in the early stages when cracks were short. The acceleration and retardation in crack growth were attributed to the resistance of grain boundaries to crack advance. Cracks sometimes arrested at these barriers and became non-propagating. Introduction of the environment for a short period appear to eliminate the resistance of the microstructural barriers thus promoting re-propagation of the previously arrested crack. The continued crack propagation after the removal of the environment suggests that the influence of the environment is more important in the early stages of crack growth. Crack growth rates were higher in the aggressive environment than in air. The degree of environmental enhancement of crack growth was found to be greater at lower stress levels and at short crack lengths. Oxide-induced crack closure and crack coalescence were two mechanisms that also affected crack growth behaviour.2-D cellular automata finite element simulation results, with and without stress, show good agreement agreed with experiments i.e. pit depth and pit aspect ratio increase with time. Results from 3-D cellular automata simulations of pits are also consistent with experiments. Fatigue lifetimes were significantly shorter (i) in the brine environment than in air and (ii) for specimens with double pits compared to single pits of similar depth. Fatigue strength in air was found to decrease with increasing pit depth. Corrosion fatigue lifetimes predicted based upon the developed model showed good agreement with the experimental lifetimes.

In dieser Arbeit wurde das elektrochemische Korrosionsverhalten von zwei Nietverbindungen in Hybridbauweise untersucht. Auf der Grundlage von elektrochemischen Polarisationsversuchen der Nietkomponenten sowie durch Simulation mit der Methode der Finiten Elemente konnte das Korrosionsverhalten für den gefügten Zustand abgeleitet werden. Das Korrosionsverhalten für den gefügten Zustand wurde aus der grafischen Analyse der erhaltenen Stromdichte-Potential-Kurven abgeleitet. Zudem wurde in der Simulation ein kritischer Abstand für galvanisch induzierte Lochkorrosion auf der Aluminiumlegierung berechnet. Das grafisch abgeleitete sowie das berechnete Korrosionsverhalten wurden für beide Nietverbindungen im Experiment bestätigt. Weiterhin wurde ein systemspezifischer Werkstoffparameter mit einer neuentwickelten Analysemethode extrahiert und dessen Abhängigkeit von der Expositionszeit der Nietverbindungen in dem Klimawechseltest nach VDA 621-415 und dem VDA 621-414 Freibewitterungstest untersucht.

Das Ziel der Arbeit bestand darin, die aus der Literatur bekannten Zusammenhänge zwischen Korrosionsaktivität von Stahl im Beton und einer galvanostatischen Pulsmessung, welche unter Laborbedingungen gute Ergebnisse liefern, auf Messungen an realen Bauwerken anzuwenden. Dazu wurden zunächst Untersuchungen an 13 Jahre alten Prüfkörpern durchgeführt und ausgewertet. Die abgeleiteten Zusammenhänge konnten anschließend an realen Bauteilen verifiziert werden. Somit stellt die galvanostatische Pulsmessung eine hilfreiche zerstörungsfreie Prüfmethode zur Interpretation des Korrosionszustandes dar. Die neuen Erkenntnisse lassen eine bessere Einschätzung des Korrosionsverhaltens in Stahlbetonbauwerken zu, als es die Potentialmessung erlaubt.

Early developed non-bulk Fe-based glasses, e.g. Fe-Cr(-Mo)-metalloid(s), exhibit extraordinary corrosion resistance, but low glass formation ability (GFA). Newly developed bulk glass-forming Fe-based alloys have on the contrary high GFA, but also very different compositions and therefore their corrosion behaviour is expectedly not similar. Fundamental investigations regarding corrosion behaviour were performed for one of the most prominent bulk glassy alloy, namely (Fe44.3Cr5Co5Mo12.8Mn11.2C15.8B5.9)98.5Y1.5. Particularly, the free corrosion and the anodic polarization behaviour, the passivation ability and the pitting susceptibility have been assessed in electrolytes with varying pH values and anion species concentrations. Due to its monolithic single phase microstructure this alloy has a much lower corrosion rate in acids than a two-phase conventional steel (DIN X210Cr12) with much higher content of passivating Cr, i.e. 11.4 at. %. However, the high concentration of electrochemically active Mn and B as well as the unfavourably high Mo to Cr concentration ratio determine a higher corrosion rate of this bulk glassy alloy in strong alkalis and also a very poor passivation ability in acids. On the contrary, the high content of Mo has a positive influence on the pitting resistance by inhibiting very effectively the propagation of pits occurring at Y2O3 inclusions. Detailed microscopic analysis investigations by HRSEM and in-situ AFM revealed the formation of characteristic morphological features at the micro- and nanometre scale on the surface of samples exposed to acidic solutions. These were explained by selective dissolution of active elements, e.g. Mn, B. This study demonstrated the necessity to investigate the corrosion properties of newly developed bulk glass-forming Fe-based alloys – they are not per-se highly corrosion resistant, but their corrosion behaviour depends on their particular chemical composition. / Früh entwickelte, nicht-massive amorphe Eisenbasislegierungen, z.B. Fe-Cr(-Mo)-Metalloid(e), zeigen bemerkenswerte Korrosionsbeständigkeit, aber niedrige Glasbildungsfähigkeit (englisch: glass-forming ability, GFA). Neu entwickelte massiv-glasbildende Eisenbasislegierungen haben im Gegenteil eine höhere GFA, aber auch sehr unterschiedliche Zusammensetzungen und deshalb ist ihr Korrosionverhalten ist wie zu erwarten nicht änlich. Grundlegende Untersuchungen des Korrosionsverhaltens einer der bekanntesten massiven amophen Legierung, nämlich (Fe44.3Cr5Co5Mo12.8Mn11.2C15.8B5.9)98.5Y1.5, wurden vorgenommen. Insbesondere wurde das Augenmerk auf das freie Korrosions- und das anodische Polarisationsverhalten, die Passivierungseigenschaften und die Anfälligkeit gegenüber Lochfraß in Elektrolyten mit verschiedenen pH-Werten und Anionenkonzentrationen gerichtet. Aufgrund ihres einphasig monolitischen Gefüges zeigt diese Legierung in Säuren eine viel niedrigere Korrosionsgeschwindigkeit als die eines zweiphasigen herkömmlichen Stahls (DIN X210Cr12) mit viel höherem Gehalt an passivierendem Cr, d.h. 11.4 at.%. Der höhere Gehalt an electrochemisch aktivem Mn und B sowie das nachteilige Verhältnis von Mo zu Cr Konzentration sind für eine höhere Korrosionsgeschwindigkeit dieser massiven amorphen Legierung in konzentrierten Alkalien sowie eine geringere Passivierungsfähigkeit in Säuren verantwortlich. Der hohe Gehalt an Mo hat jedoch einen positiven Einfluss auf die Lochfraßbeständigkeit – er hindert sehr wirksam das Wachstum der an Y2O3-Einschlüssen gebildeten Löcher. Detaillierte mikroskopische Untersuchungen durch HRSEM und in-situ AFM zeigten die Bildung charakteristischer Morphologien im Mikrometer- und Nanometerbereich auf der Oberfläche von Proben, die starken Säure ausgesetzt waren. Dieses wurde durch selektive Auflösung aktiver Elemente, z.B. Mn, B, erklärt. Diese Arbeit unterstreicht die Notwendigkeit, die Korrosionseigenschaften der neu entwickelten, massivglasbildenden Eisenbasislegierungen zu untersuchen – diese sind nicht per-se „hochkorrosionsbeständig“, stattdessen hängt ihr Korrosionsverhalten vielmehr von ihrer besonderen chemischen Zusammensetzung ab.

No description available.

[pt] Atualmente, pesquisas envolvendo metais e suas ligas têm como um de seus objetivos o controle microestrutural, como forma de aprimorar as propriedades de interesse, para as aplicações desejadas. Um fator importante que possui influência nas propriedades dos materiais policristalinos são os tipos, e distribuições de contornos de grãos e/ou de fase. A aplicação de processos que envolvam altas temperaturas, como tratamentos térmicos ou processos de soldagem, podem levar a transformações de fase, as quais modificam a cristalografia, composição química, distribuição e tamanho dos grãos. Os aços inoxidáveis duplex são ligas bifásicas constituídas de proporções aproximadamente iguais de ferrita e austenita pertencentes ao sistema Fe-Cr-Ni. Essa estrutura bifásica combina elevada resistência, boa tenacidade e excelente resistência à corrosão. Devido à essas excelentes propriedades são utilizadas em vários setores industriais como: indústrias químicas, petroquímicas, de petróleo e gás, e de construção naval. Incrementos na concentração de Cr e Ni nestes aços levam a formação de duas novas classes, os aços super e hiper duplex, cujas propriedades são semelhantes aos aços duplex, porém superiores. Neste caso, devido ao aumento no teor dos elementos de liga os processos de soldagem podem levar a formação de fases intermetálicas e/ou precipitados, as quais são deletérias as propriedades dos aços, facilitando o processo de corrosão. Muitas das transformações no estado sólido que ocorrem nos aços, seguem determinadas relações de orientação cristalográfica. Essas relações descrevem as interfaces de baixa energia que determinam os processos de nucleação e crescimento de novas fases. Portanto a determinação das relações de orientação presente nos aços duplex, super-duplex e hiper-duplex, a partir de transformações de fase obtidas em condições de equilíbrio e paraequilíbrio foram estudadas com a intenção de correlacionar com a susceptibilidade à corrosão por pites. Foram estudados os aços UNS S32205, UNS S32750 e UNS S33207, respectivamente pertencendo as classes duplex, super e hiperduplex A determinação das relações de orientação e fração de fases foi obtida por difração de elétrons retroespalhados (Electron Backscattering Diffraction - EBSD). A composição química das fases foi obtida por Espectroscopia de Energia Dispersiva (Energy Dispersion Spectroscopy - EDS). Estes dados foram correlacionados com os resultados obtidos após testes de corrosão ASTM G-48. Para todos os aços se observa a tendência do aumento da relação de orientação KS após submissão aos ciclos térmicos. No entanto, para as condições estudadas não foi encontrada uma correlação clara entre a presença da orientação KS com a formação de pites na ferrita. / [en] Currently, research involving metals and their alloys has microstructural control as one of its objectives, to improve the properties of interest, for the desired applications. An important factor that influences the properties of polycrystalline materials are the types and distributions of grain and/or phase boundaries. The application of processes involving high temperatures, such as heat treatments or welding processes, can lead to phase transformations, which modify the crystallography, chemical composition, distribution and size of the grains. Duplex stainless steels are biphasic alloys made up of approximately equal proportions of ferrite and austenite belonging to the Fe-Cr-Ni system. This two-phase structure combines high strength, good toughness and excellent corrosion resistance. Due to these excellent properties, they are used in various industrial sectors such as: chemical, petrochemical, oil and gas, and shipbuilding industries. Increases in the concentration of Cr and Ni in these steels lead to the formation of two new classes, super and hyper duplex steels, whose properties are like duplex steels, but superior. In this case, due to the increase in the content of alloying elements, the welding processes can lead to the formation of intermetallic phases and/or precipitates, which are deleterious to the properties of the steels, facilitating the corrosion process. Many of the solid-state transformations that occur in steels follow certain crystallographic orientation relationships. These relationships describe the lowenergy interfaces that determine the processes of nucleation and growth of new phases. Therefore, the determination of orientation relationships presents in duplex, super-duplex and hyper-duplex steels, from phase transformations obtained under equilibrium and paraequilibrium conditions, were studied with the intention of correlating with the susceptibility to pitting corrosion. The UNS S32205, UNS S32750 and UNS S33207 steels were studied, respectively belonging to the duplex, super and hyperduplex classes. of the phases was obtained by Energy Dispersion Spectroscopy (EDS). These data were correlated with the results obtained after ASTM G-48 corrosion tests. For all steels, there is a trend towards an increase in the KS orientation ratio after submission to thermal cycles, however no clear correlation between the presence of the KS orientation and the formation of pits in the ferrite was found.

This research extended the knowledge of the solid phase transformation and the resulting influence on impact toughness and pitting corrosion resistance in super austenitic stainless steel (SASS) SANICRO® 35. A time-temperature-transformation diagram (TTT diagram) was assembled by performing isothermal heat treatments in the temperature range of 650-1050 °C for different periods of time, ranging from 5 min to 500 min. Microstructural analysis via LOM-DIC, SEM-EDS shows that the nose temperature of dominating σ phase is located in between 900-950 °C. Minor nitrides including π phase and Cr2N with the nose temperature of 900 °C and 850 °C, respectively, were detected after prolonged heat treatment times. Area fraction of precipitates was calculated by analyzing micrographic images in the software ImageJ. Charpy impact tests indicate that the impact toughness degrades with increasing area fraction of precipitates but at a higher rate at the early stage of precipitation. Despite a much-lessened area fraction, fine precipitates decorating the grain boundaries in a continuous pattern impose significant negative effect on impact toughness. Pitting corrosion resistance was indicated by critical pitting temperature (CPT) as per ASTM G150mod (3M MgCl2). Pitting corrosion resistance deteriorated with increasing amount of σ phase due to the Cr- and Mo-depleted surrounding area, but it is more dependent on the distribution pattern of precipitates, as well as the secondary phase type. The lowest CPTs were measured after heat treatment for 500 min at 800 °C and 850 °C where nitrides including Cr2N and π phase were formed and the small precipitates were distributed on grain boundaries continuously. Auxiliary simulation of TTT diagram via TC PRISMA shows drastic variation from experimental results in regard of time scale. The enhancement pre-factor for the interfacial mobility and interfacial energy can be modified to approach the experimental results. / Detta arbete utfördes för att undersöka fasomvandlingar och dess inflytande på slagsegheten och gropfrätningsmotståndet för det superaustenitiska rostfria stålet (SASS) SANICRO® 35. Ett tid-temperatur-transformationsdiagram (TTT-diagram) har tagits fram genom att utföra isotermiska värmebehandlingar mellan 650-1050 °C med olika hålltider från 5-500 minuter. Mikrostrukturanalys genom LOM-DIC, SEM-EDS undersökning visar att nosen för den dominerande σ-fasen ligger mellan 900-950 °C. Mindre nitrider, som π-fas och Cr2N, med nosarna vid 900 °C respektive 850 °C observerades vid längre hålltider. Areafraktionen av utskiljningar beräknades genom analys av mikrobilder med programmet ImageJ. Slagprovning visade att slagsegheten minskar med ökande fraktion utskiljningar men med en tydligare försämring i början av fastransformationen. Trots att de utgör en betydligt mindre areafraktion så kan mindre utskiljningar som följer korngränserna också påverka materialet signifikant negativt. Gropfrätningsmotståndet testades genom att mäta Critical Pitting Temperature (CPT) enligt ASTM G150mod (3M MgCl2). CPT minskade med ökande andel σ-fas p.g.a. den Cr- och Mo-utarmade zon som omger de utskilda partiklarna. Det finns även en stark koppling mellan lägre CPT och distributionen av utskiljningarna samt andra typer av faser. Lägst CPT uppmättes efter 500 minuter vid 800 °C och 850 °C då små nitrider inklusive Cr2N och π-fas bildats längs med stora delar av korngränserna. Simulering av TTT-diagram i TC PRISMA visade en drastisk skillnad i tiden till utskiljning/mängden utskiljningar jämfört med de experimentella resultaten. Diffusionförstärkningsfaktorn (eng. “mobility enhancement pre-factor”) och ytenergin kan minskas för att bättre överensstämma med de experimentella resultaten.

Additive manufacturing (AM) has the potential to overtake the conventional production of pipe systems of stainless steel grade 316L intended for bioprocessing applications by utilising powder bed fusion laser beam (PBF-LB) technologies. However, challenges such as high surface roughness need to be overcome and corrosion properties improved to meet industry standards. This can be done by applying surface post-treatments to the printed parts. Therefore, the first aim of this thesis was to investigate the ability of different post-treatments of PBF-LB 316L samples, including tumbling, electropolishing, chemical milling, Hirtisation®, and DryLyte®, to reduce the surface roughness. One set of samples was left untreated, as-built set, and used as reference. The second aim was to try to correlate the surface roughness with the corrosion properties of the various post-treated samples. Analytical techniques used included needle profilometry, light optical microscopy (LOM), critical pitting temperature (CPT), cyclic potentiodynamic polarisation (CPDP) and immersion in 1M NaCl and 1M NaOH for two different durations for each solution. While some results were expected, others were surprising. Even though tumbled samples resulted in the lowest surface roughness, the results for immersion and CPDP curves tests indicated the lowest corrosion resistance compared to the other post-treatments. On the other hand, electropolishing resulted in the lowest surface roughness reduction among the post-treated samples. However, these samples had comparatively high corrosion resistance in the CPT and CPDP tests. The DryLyte® samples were tested using two DryLyte® medias where one of them resulted in the second lowest surface roughness and showed highest corrosion resistance in all three corrosion tests even though the process parameters are still to be developed. The results for samples post-treated by Hirtisation® and chemical milling were inconsistent and need further investigations. The reference as-built set showed high corrosion resistance in its untreated state, indicating post-treatments having minor impact on its performance from a corrosion perspective. / Additiv tillverkning (AM) har möjlighet att konkurrera ut konventionell produktion av rörsystem i rostfritt stål typ 316L avsett för bioprocessapplikationer genom att använda pulverbäddsinfusionslaserstråleteknik (PBF-LB). För tekniken kvarstår dock utmaningar för att uppfylla branschstandarder då tillverkningen medför material med hög ytråhet och sämre korrosionsegenskaper än traditionella metoder. Detta kan åstadkommas genom olika typer av efterbearbetning av de printade ytorna. Ett syfte med denna studie var att utvärdera hur olika typer av efterbehandling av PBF-LB 316L (trumling, elektropolering, kemisk etsning, Hirtisation® och DryLyte®) påverkar ytråheten. Som referensmaterial användes obearbetade printade ytor. Studiens andra huvudmål var att undersöka möjligheten för korrelation mellan ytråhet efter behandling och korrosionsegenskaperna. Analyser gjordes med hjälp av nålprofilometri, ljusoptisk mikroskopi (LOM), bestämning av kritisk gropfrätningstemperatur (CPT), framtagning av cykliska potentiodynamiska polarisationskurvor (CPDP) samt nedsänkning i 1M NaCl och 1M NaOH under två olika tidsperioder per lösning. Resultaten var delvis väntade och delvis överraskande. Trots att de trumlade proverna resulterade i lägst ytråhet, visade de elektrokemiska studierna (CPDP) i de olika lösningarna på att lägre korrosionsbeständighet jämfört med övriga efterbehandlingar. Å andra sidan resulterade elektropolering resulterade i den lägsta minskningen i ytråhet bland de efterbehandlade proverna. Dessa prover visade dock på en jämförelsevis hög korrosionsbeständighet i både CPT och CPDP testerna. DryLyte®-proverna studerades med två olika DryLyte®-medier, varav en av dem gav näst lägst ytråhet samt visade högst korrosionsbeständighet i samtliga korrosionstester trots att processparametrarna inte ännu är optimerade för denna nya teknik. Resultaten för prover som efterbehandlats med Hirtisation® och kemisk etsning var tvetydiga och behöver studeras vidare. De obehandlade referensproverna indikerade hög korrosionsbeständighet, vilket tyder på att efterbehandlingar hade minimal påverkan ur ett korrosionsperspektiv.

No description available.

Duplex stainless steels can be very attractive alternatives to austenitic grades due to their almost double strength at equal pitting corrosion resistance. When welding, the duplex alloys normally require addition of filler metal, while the commodity austenitic grades can often be welded autogenously. Over-alloyed consumables are used to counteract segregation of important alloying elements and to balance the two phases, ferrite and austenite, in the duplex weld metal. This work focuses on the weldability of the recently-developed lean duplex stainless steel LDX 2101® (EN 1.4162, UNS S32101). The pitting corrosion resistance of this grade is better than that of austenitic AISI 304 (EN 1.4307) and can reach the level of AISI 316L (EN 1.4404). The austenite formation is rapid in LDX 2101 compared to older duplex grades. Pitting resistance tests performed show that 1-2.5 mm thick laser and gas tungsten arc (GTA) welded LDX 2101 can have good corrosion properties even when welding autogenously. Additions of filler metal, nitrogen in the shielding gas, nitrogen-based backing gas and use of laser hybrid welding methods, however, increase the austenite formation. The pitting resistance may also be increased by suppressing formation of chromium nitrides in the weld metal and heat affected zone (HAZ). After thorough post-weld cleaning (pickling), pitting primarily occurred 1-3 mm from the fusion line, in the parent metal rather than in the HAZ. Neither the chromium nitride precipitates found in the HAZ, nor the element depletion along the fusion line that was revealed by electron probe microanalysis (EPMA) were found to locally decrease the pitting resistance. The preferential pitting location is suggested to be controlled by the residual weld oxide composition that varies over the surface. The composition and thickness of weld oxide formed on LDX 2101 and 2304 (EN 1.4362, UNS S32304) were determined using X-ray photoelectron spectroscopy (XPS). The heat tint on these lean duplex grades proved to contain significantly more manganese than what has been reported for standard austenitic stainless steels in the AISI 300 series. A new approach to heat tint formation is presented; whereby evaporation of material from the weld metal and subsequent deposition on the already-formed weld oxide are suggested to contribute to weld oxide formation. This is consistent with manganese loss from the weld metal, and nitrogen additions to the GTA shielding gas enhance the evaporation. The segregation of all elements apart from nitrogen is low in autogenously welded LDX 2101. This means that filler wire additions may not be required as for other duplex grades assuming that there is no large nitrogen loss that could cause excessive ferrite contents. As the nitrogen appears to be controlling the austenite formation, it becomes essential to avoid losing nitrogen during welding by choosing nitrogen-containing shielding and backing gas. / QC 20101213