Fretting, which can occur when two bodies in contact undergo a low amplitude relative slip, can drastically reduce the fatigue performance of a material. The extent of fretting damage is dependent on the material combination and is affected by many parameters, making it difficult to design against fretting. Some of these parameters include contact force, displacement amplitude, and contacting materials. This work develops a method for quantifying the extent of damage from fretting as a function of these parameters for a thin sheet of AISI 301 stainless steel in the full hard condition in contact with both ANSI A356 aluminum and AISI 52100 steel contacting bodies. Fretting experiments were conducted on a Phoenix Tribology DN55 Fretting Machine using a fixture which was developed for holding thin specimens. The displacement amplitude and normal force were systematically varied in order to cover a range that could typically be experienced during service. The tribological behavior was studied by analyzing friction force during cycling and inspecting the resulting surface characteristics. Fretting damaged specimens were cycled in tension in a servohydraulic test system to failure. The decrease in fatigue life caused by fretting damage was determined by comparing the stress-life (S-N) response of the fretted specimens to the S-N response of the virgin material, thus characterizing the severity of the fretting damage. The conditions that lead to the greatest reduction in life were identified in this way. Using the fracture mechanics based NASGRO model, an Equivalent Initial Flaw Size (EIFS) was used to quantify the level of fretting damage, thus separating the life of the component into crack nucleation and subsequent propagation. This method and data will allow engineers to design more robust components that resist fretting damage, thus increasing the safety and reliability of the system.

The effect of a specific type of pre-exposure heat treatment on the susceptibility of AlSI type 304 stainless steel to stress corrosion cracking was studied in terms of time for crack nucleation and rate of crack propagation. U-bend specimens were exposed to 42 weight percent magnesium chloride aqueous solution after pre-exposure heat treatments at 140°C and 154°C. The straight-line relationship between maximum crack depth and the logarithm of exposure time expressed by the empirical equation log t = log t_o + D/M was obtained. The stress corrosion constants derived from the empirical equation indicate that this type of pre-exposure heat treatment promotes crack nucleation because of the formation of less protective surface films, and retards the rate of crack propagation because of effects on internal structural changes within the alloy. / Master of Science

L’état de surface des vis de liaison des internes de cuve du circuit primaire des REP (Réacteurs à Eau Pressurisée) en 316L en service correspond à une finition d’usinage par rectification. Ces vis sont affectées par l’IASCC (Corrosion Sous contrainte Assistée par l’Irradiation). Le processus d’amorçage de la fissuration est fonction de l’oxydation externe, de l’état de surface et des interactions de la couche d’oxyde avec la localisation de la plasticité. Un des objectifs de cette étude est déterminer l’influence de la préparation de surface sur la cinétique de croissance des couches d’oxyde et la réactivité de surface en général des nuances de type 304, 316 exposées en milieu primaire des REP à 340°C. Le second objectif est de déterminer l’influence de la localisation de la déformation sur la CSC (Corrosion Sous Contraintes) des aciers inoxydables austénitiques en milieu primaire des REP. En effet, la microstructure représentative de ces nuances irradiées correspond à une microstructure à déformation localisée dans des bandes de déformation dépourvues de défauts d’irradiation. Afin de reproduire cette microstructure représentative sur le matériau modèle de l’étude (l’acier austénitique inoxydable A286 durci par la précipitation de la phase γ’ Ni3(Ti,Al)) sans avoir recours à l’irradiation, des essais de fatigue oligocyclique à Δε/2 imposée sont réalisés. Durant le cyclage mécanique (après les premiers cycles de durcissement), les précipités sont dissouts dans des bandes de glissement menant à la localisation de la déformation. Une fois les conditions expérimentales en fatigue oligocyclique permettant d’obtenir la microstructure de déformation désirée déterminées, les interactions bandes de déformation / oxyde de surface sont étudiées en oxydant des coupons pré déformés contenant des bandes de déformation et des coupons non déformés. La préparation de surface des coupons est identique. Les essais de traction lente à une vitesse de déformation de 8 x 10-8/s sont également réalisés sur des éprouvettes pré déformées et non déformées. Les résultats ont montré que la préparation de surface modifie la microstructure du métal sous la couche d’oxyde, conduisant à un ralentissement de la cinétique de croissance de la couche d’oxyde. La préparation de surface induit cependant une accélération du développement de pénétrations d’oxydes dans le métal sous la couche d’oxyde. Ainsi, sur les échantillons rectifiés, la zone recristallisée sous la couche d’oxyde est plus profonde que sur les échantillons polis (jusqu’à 1,5μm contre 500nm au maximum sur les échantillons polis) et la couche d’oxyde est plus fine que sur les échantillons polis, tandis que les pénétrations d’oxyde sont présentes sur près de 1μm de profondeur en sous couche (contre 300nm sur les échantillons polis). Nous montrons que la zone de recristallisation induite par la préparation de surface ne permet pas l’observation des interactions entre les bandes de déformation générées dans le volume par la fatigue oligocyclique et la couche d’oxyde en surface. De fait, la réactivité de surface est très importante pour l’étude de la CSC des aciers inoxydables en milieu primaire des REP. Nous avons également démontré que cette nuance était très sensible à la corrosion intergranulaire en milieu REP à 340°C. Enfin, la localisation de la déformation plastique ne semble pas favoriser la CSC sur cette nuance à cette vitesse de déformation. / The surface conditions of the 316L screw connecting vessel internals of the primary circuit of PWR (pressurized water reactor) corresponds to a grinding condition. These screws are affected by the IASCC (Irradiation Assisted Stress Corrosion Cracking). Initiation of cracking depends on the surface condition but also on the external oxidation and interactions of oxide layer with the deformation bands. The first objective of this study is to point the influence of surface condition on the growth kinetic of oxide layer, and the surface reactivity of 304, 316 stainless steel grade exposed to PWR primary water at 340 ° C. The second objective is to determine influence of strain localization on the SCC of austenitic stainless steels in PWR primary water. Indeed, the microstructure of irradiated 304, 316 grades correspond to a localized deformation in deformation bands free of radiation defects. In order to reproduce that microstructure without conducting irradiations, low cycle fatigue tests at controlled stain amplitude are implemented for the model material of the study (A286 austenitic stainless steel hardened by the precipitation of phase γ ‘Ni 3 (Ti, Al)). During the mechanical cycling (after the first hardening cycles), the precipitates are dissolved in slip bands leading to the localization of the deformation. Once the right experimental conditions in low cycle fatigue obtained (for localized microstructure), interactions oxidation / deformation bands are studied by oxidizing pre deformed samples containing deformation bands and non deformed samples. The tensile tests at a slow strain rate of 8 x 10-8 /s are also carried out on pre deformed samples and undeformed samples. The results showed that surface treatment induces microstructural modifications of the metal just under the oxide layer, leading to slower growth kinetics of the oxide layer. However, surface treatment accelerates development of oxides penetrations in metal under the oxide layer. As example, for grinded samples, the recrystallized area under the oxide layer, induced by surface treatment, is deeper than for polished sample (up to 1.5 microns vs 500 nm for the polished samples) and the oxide layer is thinner than on the polished samples, while the penetrations oxide are expands on nearly 1μm under the oxide layer (against 300nm for the polished samples). We also show that the area recrystallization resulting from surface treatment, does not allow observing the interactions between the deformation bands in the bulk generated by LCF and the oxide layer at surface. Actually, surface reactivity is strongly important for SCC study of stainless steels in PWR primary water. We also demonstrated that this grade was very sensitive to intergranular corrosion in PWR environment at 340 ° C. Finally, localization of plastic deformation does not seem to favor SCC in our A-286 grade, at that strain rate level

A thesis submitted to the Faculty of Engineering and the Built Environment, University of Witwatersrand, Johannesburg in fulfilment of the requirements for the degree of Doctor of Philosophy (Engineering), 2017 / Chromium oxide provides an inexpensive and practical means of increasing the corrosion resistance of austenitic stainless steel in most environments. However, the oxide is prone to dissolve in reducing acids and in chloride containing solutions, which compromises the durability and effective operation of structures made of austenitic stainless steel. This research project explored the use of thin ruthenium surface alloys produced by ion implantation, RF sputtering and pulsed electrodeposition (PED) to improve the corrosion resistance of AISI 304L austenitic stainless steel in reducing acids and chloride solutions via a technique known as cathodic modification. The properties of the alloyed 304L stainless steel were evaluated using a number of tools including X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), potentiodynamic polarisation, and electrochemical impedance spectroscopy (EIS). Preliminary tests in 1 M sulphuric acid showed that the ruthenium surface alloys sufficiently raised the corrosion potential of 304L stainless steel to ranges where the stability of chromium oxide is guaranteed. Surface alloys produced by RF sputtering and PED were associated with the best corrosion resistance, and protection efficiencies of at least 85%, but they spalled during corrosion exposure rendering them unsuitable for corrosion application. The corrosion of the ruthenium implanted surface alloys exhibited a strong dependence on the surface roughness of the stainless steel, with the least corrosion rates achieved on rough 304L stainless steel samples implanted with 1016 Ru/cm2 at 50 keV. Corrosion characterisation of these ruthenium implanted surface alloys was studied in various corrosive media including sulphuric acid, sodium chloride, magnesium chloride and simulated fuel cell solutions. Their corrosion rates in sulphuric acid decreased with increase in acid concentration, and exhibited non-Arrhenius behaviour in the acid solutions; corrosion rates were unaffected by increasing exposure temperature from 25 to 50°C. In 3.5 wt% sodium chloride, addition of ruthenium via ion implantation changed pit morphology from elongated to circular, indicating a diminished tendency for pits to initiate at manganese sulphide stringers. Corrosion rates of the ruthenium implanted stainless steels in the simulated fuel cell solutions were at least 69% lower than the target corrosion rate for use in polymer electrode membrane fuel cells (PEMFCs), thus presenting a possible practical application of ruthenium surface alloyed austenitic stainless steel. / CK2018

Student Number : 9904952F - MSc Dissertation - School of Chemical and Metallurgical Engineering - Faculty of Engineering and the Built Environment / This dissertation is a study of the effect of manganese, nitrogen and molybdenum on the corrosion behaviour of a low nickel, austenitic stainless steel. The trademarked steel, HerculesTM, has a composition of 10 wt% Mn, 0.05 wt% C, 2 wt% Ni, 0.25 wt% N and 16.5 wt% Cr. Eighteen alloys with a HerculesTM base composition were made with varying manganese, molybdenum and nitrogen contents, to establish the effect of these elements on the corrosion behaviour of the steel, and to determine a composition that would ensure increased corrosion resistance in very corrosive applications. The manganese was varied in three levels (5, 10 and 15 wt%), the molybdenum in three levels (0.5, 1 and 2 wt%) while the nitrogen was varied only in two levels (0.15 and 0.3 wt%). The dissertation details the manufacturing and electrochemical corrosion testing of these alloys. Preliminary tests were done on 50g buttons, and full-scale tests on 5 kg ingots. The buttons had a composition that was not on target, this was however rectified in the making of the ingots. Potentiodynamic tests were done in a 5 wt% sulphuric acid solution and the corrosion rate (mm/y) was determined directly from the scans. From the corrosion test results, it was clear that an increase in manganese decreases the corrosion rate, since the 5 wt% Mn alloys had the highest corrosion rate, whereas the 15 wt% Mn alloys, the lowest. The addition of molybdenum at 5 wt% Mn decreased the corrosion rate such that a trend of decreasing corrosion rate with increasing molybdenum was observed. At 10 and 15 wt% Mn molybdenum again decreased the corrosion rate significantly, but the corrosion rate value remained more or less constant irrespective of the increasing molybdenum content. At nitrogen levels lower than those of HerculesTM (less than 0.25 wt%) there was no change in corrosion rate as nitrogen was increased to levels closer to 0.25 wt%. For nitrogen levels higher than 0.25 wt%, corrosion rates decreased as nitrogen levels were increased further from 0.25 wt% but only at Mo contents lower than 1.5 wt%. The HerculesTM composition was developed for its mechanical properties. Microstructural analyses revealed that the 5 wt% Mn alloys were not fully austenitic and since the 15 wt% Mn alloys behave similarly to the 10 wt% Mn alloys, it was concluded that 10 wt% Mn was optimum for HerculesTM. All the alloys tested had a much lower corrosion rate than HerculesTM. Any addition of molybdenum thus improved the corrosion rate of this alloy. An alloy with a HerculesTM base composition, 10 wt% Mn, 0.15 wt% N and a minimum addition of 0.5 wt% Mo would be a more corrosion resistant version of HerculesTM. Pitting tests were done on the 10 wt% Mn ingots in a 3.56 wt% sodium chloride solution. The results showed that an increase in molybdenum increased the pitting resistance of the ingots. Immersion tests in a 5 wt% sulphuric acid solution at room temeperature on the 10 wt% Mn ingots confirmed that the ingots corroded by means of general corrosion.

Este trabalho tem por objetivo estudar a eficiência dos oxiânions molibdato (MoO4 2-) e tungstato (WO4 2-) na inibição da corrosão localizada em aços inoxidáveis austeníticos (347 e 304L) em sistemas de água com alto grau de pureza na presença de íons cloreto (Cl-). Para avaliar a ação dos oxiânions estudados foram empregadas técnicas eletroquímicas de monitoramento do potencial de circuito aberto (Eoc), espectroscopia de impedância eletroquímica (EIS), polarização cíclica (PC) e cronoamperometria (CA). Para caracterização superficial foram utilizadas microscopia óptica (MO) e microscopia eletrônica de varredura (SEM). Os ensaios foram realizados em meios contendo somente água pura desoxigenada e água pura desoxigenada contendo íons cloreto (50, 100, 200, 300 e 500 ppm) variando a concentração (0, 10-4, 10-3 e 10-2 M) dos inibidores molibdato e tungstato de sódio. Todos os experimentos foram realizados à temperatura ambiente e em condições hidrodinâmicas controladas, empregando o sistema de eletrodo de disco rotativo (RDE) com velocidade constante de1200 rpm. Os resultados mostraram que os aços inoxidáveis 347 e 304L permanecem passivos em água pura, uma vez que o meio não é agressivo. Entretanto, a adição de íons cloreto tornou-os susceptíveis à corrosão por pites, pois os cloretos atuam como desapassivadores, fragilizando o filme passivo que fornece proteção aos aços inoxidáveis. O aumento da concentração dos íons cloreto no eletrólito aumentou a sua agressividade para os dois aços estudados, sendo observado o precoce aparecimento da corrosão. No entanto, a adição dos inibidores molibdato e tungstato de sódio melhorou a qualidade da camada passiva, aumentando os valores de potencial de pite (Ep) e de módulo de impedância, mantendo a passividade dos aços num amplo intervalo de potenciais. Ensaios cronoamperométricos mostraram que na presença dos oxiânions os valores medidos de densidade de corrente de resposta para os aços inoxidáveis 347 e 304L foram acentuadamente menores em relação aos valores obtidos na ausência dos mesmos, confirmando que os inibidores utilizados atuam na melhora da camada passiva, diminuindo a sensibilidade aos cloretos e conseqüentemente aumentando a resistência contra a corrosão por pites dos aços. O estudo mostrou que os melhores resultados para ambos os aços foram obtidos na presença de 10-2 M de inibidor, tanto para o tungstato quanto para o molibdato, sendo este com eficiência levemente melhor. Além disso, o aço 304L sem partículas incrustadas de alumina mostrou-se menos susceptível aos ataques dos cloretos do que o aço 347. Nas amostras que tiveram a superfície tratada com lixas de abrasivo de alumina, essas partículas foram incrustadas nos aços e isso levou ao desaparecimento de um potencial de pite bem definido. Na presença de alta concentração de cloretos, essas partículas foram arrancadas pelo ataque às regiões deformadas mecanicamente, localizadas ao redor das partículas incrustadas e as propriedades do aço em si puderam ser verificadas. / The aim of this work is to study the efficiency of molibdate (MoO4 2-) and tungstate (WO4 2-) oxianions in the inhibition of the localized corrosion in austenitic stainless steels (347 and 304L) in high purity water systems in the presence of chloride ions (Cl-). In order to evaluate the action of the oxianions electrochemical techniques as open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), cyclic polarization (CP) and chronoamperometry (CA) were accomplished. For surface characterization optical microscopy (OM) and scanning electron microscopy (SEM) were used. The experiments were carried out in deoxygenated pure water and deoxygenated pure water containing chloride ions (50, 100, 200, 300 and 500 ppm) adding different concentrations (0, 10-4, 10-3 and 10-2 M) of molibdate and tungstate ions. All the experiments were performed at room temperature under controlled hydrodynamic conditions using a rotating disk electrode (RDE) at constant rotation speed of 1200 rpm. The results showed that 347 and 304L stainless steels remain passive in pure water, since the environment is not aggressive. However, in the presence of chloride ions they become susceptive to pitting corrosion, with chloride ions acting depassivity agents weakening the passive film that supplies protection to the stainless steels. The increase of chloride ions concentration in the electrolyte enhanced the aggressiveness for both steels evidenced by a precocious accurance of pitting corrosion. On the other hand, the addition of sodium molibdate and tungstate inhibitors improved the quality of the passive layer, increasing the pitting potentials (Ep) and the impedance modulus, improving the the passivity of steels a large of potential range. Chronoamperometric measurements showed that in the presence of oxianions response current density for 347 and 304L stainless steels was strongly diminished in relation to the values obtained in the absence of the inhibitors, confirming that the inhibitors act in the improvement of the passive layer, decreasing its sensitivity to chlorides and consequently increasing the steels resistance against pitting corrosion. Results showed that the best results for both steels were obtained in the presence of 10- 2 M tungstate or molibdate, being this latter with efficiency lightly better. Moreover, the 304L stainless steel showed to be less susceptive to pitting corrosion compared to 347 stainless steel. For stainless steel specimens previously treated with Al2O3 emery papers, Al2O3 particles become embedded in the steel surface and led to the indefinition of the pitting potential values. In the presence of high chloride concentrations, the mechanically affected region of steel in the surrounding of Al2O3 particles was attacked and Al2O3 particles were removed reveling the stainless steel own resistance to chlorides.

Chapas laminadas a quente com 6 mm de espessura dos aços AISI 304L e 316L apresentaram na condição inicial uma microestrutura composta por grãos recristalizados equiaxiais de austenita e ilhas de ferrita δ, em maior quantidade no centro da chapa. A austenita apresentou textura cristalográfica fraca, com um gradiente de textura ao longo da espessura. Os tratamentos térmicos de solubilização causaram a eliminação da ferrita, mas não causaram modificação substancial na textura. Os fenômenos de encruamento, recuperação e recristalização foram então estudados após solubilização, seguida de deformação por laminação em diferentes temperaturas e posterior recozimento das amostras deformadas. O endurecimento por deformação e a porcentagem de martensita α’ formada mostraram forte dependência com a composição química da austenita e com a temperatura de deformação. A textura de deformação encontrada nos aços inoxidáveis austeníticos 304L e 316L é característica dos materiais CFC com baixa e média energia de empilhamento laminados a frio. A temperatura de reversão da martensita α’ foi próxima de 550°C, praticamente não depende da quantidade presente e é praticamente idêntica nos dois aços. O aço 316L apresentou maior resistência à recristalização, pois tem maior EDE e apresenta menor endurecimento por deformação em relação ao 304L. A temperatura de recristalização situouse aproximadamente 150°C acima da temperatura de reversão da martensita α’. A temperatura de laminação não influenciou significativamente a temperatura de recristalização. A textura de recristalização nos dois aços continuou sendo semelhante à textura de deformação. As propriedades mecânicas de tração dos dois aços mostraram-se muito sensíveis à temperatura do ensaio. Tratamentos mecânicos e térmicos adequados produziram combinações interessantes de propriedades mecânicas nos dois aços, tais como limite de escoamento por volta de 1000 MPa com alongamento da ordem de 10%. Os resultados do presente trabalho sugerem que para se obter nos aços inoxidáveis austeníticos combinações atrativas de alta resistência mecânica com ductilidade razoável, por meio de tratamentos mecanotérmicos ou termomecânicos, duas diretrizes devem ser observadas: i) durante a deformação grandes quantidades de martensita devem ser produzidas e as principais variáveis neste aspecto são a EDE do aço e a quantidade e a temperatura de deformação; ii) durante o recozimento do material encruado deve ocorrer reversão da martensita, mas a recristalização completa deve ser evitada, por meio do controle rigoroso da temperatura e do tempo de recozimento, obtendo-se uma microestrutura muito fina de grãos e sub-grãos. A possibilidade de tratamentos sucessivos de deformação/recozimento é promissora e deve ser explorada em trabalhos futuros. A caracterização microestrutural foi realizada com auxílio de várias técnicas complementares de análise microestrutural, tais como microscopia óptica, microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (MET), medidas magnéticas, difração de raios X (análise de fases e determinação de textura) e microdureza Vickers. A caracterização mecânica envolveu a realização de ensaio de tração em várias temperaturas, com a determinação de limite de escoamento, limite de resistência, alongamento total e coeficiente de encruamento n. / Hot rolled AISI 304L and 316L austenitic stainless steel sheets, 6mm thick, presented recrystallized equiaxial grains with austenite and islands of delta ferrite, in larger quantities mainly in the center of both steel sheets. The austenite had a weak texture, with a gradient through the thickness. The solution annealing eliminated delta ferrite, however it did not change the texture. Phenomena such as work hardening and strain induced α’ martensite formation showed strong dependency on the chemistry composition and rolling temperature. The rolling texture observed in AISI 304L and 316L austenitic stainless steels is characteristic of FCC materials with low and medium stacking fault energy (SFE), after cold rolling. The α’ reversion temperature was around 550°C for both steels and was independent of the volume fraction of α’ martensite. The AISI 316L showed a strong recrystallization resistance as it has higher SFE and smaller work hardening than the AISI 304L. The recrystallization start temperature is approximately 150°C higher than the α’ reversion temperature. The rolling temperature did not influence the recrystallization temperature. Recrystallization texture for both steels remained similar to the rolling texture. Proper thermal and mechanical treatments provided interesting combinations of mechanical properties for both steels, such as yield strength around 1000 MPa with 10% elongation. These results suggest that the obtained austenitic stainless steels provide attractive combinations not only with high mechanical resistance but also with reasonable toughness and ductility. Through thermo-mechanical treatments, two point must be stressed: i) during the deformation great quantities of α’ martensite are being produced due to the SFE of the steel and the degree and the temperature of deformation; ii) during the annealing treatment of the work hardened material the α’martensite reverts to austenite, but complete recrystallization must be avoided, thus strict control of temperature and annealing time must be ensured to obtain a refined microstructure (of grains and subgrains). The possibilities of employing successive deformation / annealing treatments is promising and should be explored in future research. Several microstructural characterization techniques have been employed: optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), magnetic measurements, X-ray diffraction to analyze phases and textures, and Vickers microhardness tests. Mechanical characterization involved tensile testing at different temperatures, with determination of yield strength, tensile strength, total elongation and strain hardening coefficient n.

Os aços inoxidáveis austeníticos são materiais atrativos para serem utilizados em vários setores industriais que operam sob meios corrosivos, como por exemplo: indústria química, alcooleira, petroquímica, de papel e celulose, na prospecção de petróleo e nas indústrias têxtil e farmacêutica. Contudo, apresentam propriedades tribológicas pobres. No sentido de melhorar essas propriedades, como aumentar a dureza superficial, a resistência ao desgaste e a resistência à fadiga, vários métodos de tratamentos superficiais vêm sendo utilizados. Dentre eles, o mais eficiente é a nitretação por plasma. Este processo é realizado em uma câmara de vácuo sob uma mistura gasosa de hidrogênio e nitrogênio. É aplicada uma diferença de potencial entre o cátodo (porta amostras) e o ânodo (paredes da câmara), acelerando os íons contra a superfície da peça, aquecendo-a e arrancando elétrons de sua superfície. Os íons reagem com espécies da superfície do plasma formando compostos instáveis do tipo FeN que se recombinam para formarem nitretos estáveis. O sucesso deste tratamento se deve à baixa temperatura de operação, ao menor tempo efetivo de tratamento e ao controle da uniformidade da espessura da camada. A camada de nitretos formada durante o tratamento possui uma influência positiva na vida em fadiga de um componente, graças a dois motivos principais. O primeiro é o atraso na nucleação da trinca devido ao aumento da resistência mecânica superficial. O segundo motivo está relacionado com a introdução de tensões residuais compressivas durante o processo de endurecimento da superfície, que retarda a iniciação da trinca e diminui o fator de intensidade de tensão. Os corpos de prova foram nitretados a 400ºC durante 6 horas, com uma pressão de 4,5 mbar e utilizando uma mistura gasosa de 80% vol.H2 e 20%vol.N2. Ocorreu um aumento da resistência mecânica próxima á superfície, devido à camada de nitretos, o que ficou evidente com o sensível aumento no valor do limite de fadiga do material nitretado em relação ao não nitretado. O limite de fadiga do aço AISI 316 não tratado foi de 400MPa e do nitretado foi de 510MPa, enquanto que, para o aço AISI 304, o limite de fadiga do material não tratado foi de 380MPa e o limite para material submetido ao tratamento de nitretação foi de 560MPa. / The austenitic stainless steels are attractive materials to many industrial sectors which work on corrosive environments, as chemical industry alcohol, petrochemical, cellulose industries, in the petroleum prospection and pharmaceutical and textiles industries. However, they present poor tribological properties. In order to improve these properties, like increasing superficial hardness, wear and fatigue resistance superficial heat treatment methods have being used. The most efficient is the plasma nitriding process which occurs in a vacuum container under hydrogen and nitrogen gas mixture. A potential difference is applied between the cathode (samples receptor) and the anode (container walls), accelerating the ions against the piece, heating it and removing electron from the surface of material. These atoms react with the surface plasma species, producing unstable compounds like FeN, which recombine producing stable nitrides. The success of this treatment is due to the low temperature operation, the short effective time of treatment and to the uniformity control of the layer’s thickness. The nitrides layer produced during the treatment have a positive influence in the fatigue life of a component, thanks to two main reasons. The first is the retardation in crack nucleation due to increasing of superficial mechanical strength. The second reason is due to introduction of compressive residual stress during the surface hardening process, which retards de crack initiation process. The specimens were nitriding at 400°C during 6 hours, at a 4,5mbar pressure and using a gas mixture of 80% vol. H2 and 20% vol. N2. The surface mechanical strength increased, due to the nitrides layer, which was evident with the sensitive increase in the fatigue limit of the nitriding specimens, comparing to the untreated ones. The fatigue limit of the AlSl 316 steel in untreated condition was 400 MPa and in nitriding condition was 510 MPa, whereas AlSl 304 steel, the fatigue limit of the untreated condition was 480 MPa and the fatigue limit for the nitrided condition was 560 MPa.

A crescente tendência de utilização de materiais austeníticos soldados e cladeados em componentes críticos em alguns setores industriais, como nas indústrias de óleo&gás e nuclear, leva a um aumento na demanda sobre ensaios não-destrutivos confiáveis na avaliação de sua integridade estrutural. Dentre os métodos utilizados na inspeção de soldas cladeados austeníticos estão os métodos de ultrassom por phased array, que são normalmente utilizados na detecção e localização de defeitos. No entanto, componentes com esse tipo de microestrutura são difíceis de inspecionar por phased array devido a anisotropia e inomogeneidade causadas pela microestrutura de grãos grosseiros que costumam levar ao aumento do nível de ruído, ao deslocamento de indicações e ao surgimento de indicações falsas. Sendo assim, a seleção de um método de phased array apropriado precisa levar em conta a habilidade do método em superar os problemas causados pela anisotropia e inomogeneidade. Esta tese apresenta dois métodos de imagem por phased array ultrassônico não-convencionais pensados como formas de ajudar na determinação da integridade de componentes onde soldas e cladeados austeníticos estão presentes. Ambos os métodos tem como base o método de foco total (TFM), sendo que o primeiro é uma extensão do método de leis de atraso adaptativas chamado Método de Foco Total de Atraso Adaptativo (ADTFM) e o segundo método usa fatores de coerência associado à imagens de TFM. A partir dos métodos de imagem aplicados é possível aumentar significativamente a qualidade das imagens por ultrassom em comparação com as imagens padrão obtidas por TFM, especialmente quando foi possível utilizar ambos os métodos combinados. / The increasing trend to use austenitic welded and cladded materials in critical components employed in some industrial sectors, such as the oil&gas and nuclear industries, leads to an increasing demand for their non-destructive assessment by reliable non-destructive methods. Among the methods used to access the integrity of austenitic welds and claddings are the Ultrasonic Phased Array methods, which are usually used to detect the presence and determine the position of defects. However, austenitic welds and claddings are challenging to inspect with Phased Array methods due to the anisotropy and inhomogeneity caused by their coarse grain microstructure, which is capable of increasing noise levels, misplace indications and create false indications. Therefore, the selection of an appropriate phased array method needs to take into account the method’s ability to overcome the impairment caused by anisotropy and inhomogeneity. This thesis presents two non-conventional methods based on ultrasonic phased array imaging techniques designed to assist the structural integrity assessment of components where austenitic welds and clads are present. Both proposed methods are based on the Total Focusing Method (TFM); the first approach is an expansion of the adaptive delay laws concept named Adaptive Delay Total Focusing Method (ADTFM), while the second method uses the coherence weights combined with the TFM images. From the imaging methods applied it was possible to significantly increase the quality of the ultrasonic images in comparison with the standard TFM, primarily when it was possible to combine both approaches.

Os aços inoxidáveis possuem numerosas aplicações devido à boa combinação de propriedades tais como resistência à corrosão e oxidação, ductilidade, tenacidade, soldabilidade e resistência mecânica em temperaturas elevadas. No entanto suas propriedades e desempenho estão fortemente relacionados com a microestrutura que por sua vez, no caso de peças fundidas, dependem principalmente da composição química e da velocidade de solidificação. No presente trabalho o efeito destas duas variáveis foram estudados e os resultados experimentais comparados com as previsões teóricas e modelos disponíveis na literatura. Dezesseis corridas de diferentes aços inoxidáveis austeníticos foram fundidas e suas composições químicas completas (16 elementos analisados) foram determinadas. A maioria das corridas analisadas apresentou modo de solidificação do tipo C. Foram encontrados teores de ferrita (medidos com auxílio de ferritoscopia) na faixa de 0 a 11%. A influência da composição química do aço na quantidade de ferrita delta formada foi marcante, enquanto a influência da espessura foi pouco acentuada. Dentre as numerosas fórmulas testadas para a previsão da quantidade de ferrita delta, as duas que apresentaram melhor resultado foram as fórmulas de Schneider e de Schoefer, sendo que esta última é recomendada pela norma ASTM A800. A amostra contendo cerca de 10% de ferrita apresentou uma rede quase contínua, o que pode comprometer a tenacidade da peça, caso esta ferrita venha a sofrer fragilização. Nas amostras contendo por volta de 5% de ferrita, a rede de ferrita é semi-contínua, enquanto para teores baixos (por volta de 2%), a ferrita apresenta-se como ilhas isoladas. As morfologias encontradas foram classificadas como sendo todas do tipo vermicular. Os estudos de micro-análise química dos elementos Si, Mo, Cr, Fe e Ni, efetuados na ferrita e na austenita revelaram coeficientes de partição de acordo com o previsto pela literatura. O efeito da espessura nas variações de composição foi pequeno e não conclusivo. / Stainless steel has numerous applications due to a good combination of properties such as corrosion and oxidation resistance, toughness, weldability and mechanical strength at high temperatures. However these properties and performance are strongly related to the microstructure and in the case of castings are mainly dependent of chemical composition and cooling rate. In this work the effect of these two factors were studied and the experimental results compared with theoretical models available in the literature. Sixteen heats of different austenitic stainless steel were cast and their complete chemical compositions (16 elements) were determined. Most of analyzed heats showed the solidification mode type C. Ferrite values (measured with ferritoscope) were found in the range from 0 to 11%. The influence of chemical composition on delta ferrite was strong while the influence of thickness was less accentuated. Among numerous tested formulas to estimate the quantity of delta ferrite two that demonstrated better results were the ones of Schneider and Schoefer, where the last one is recommended by ASTM A800 standard. The sample with approximately 10% of ferrite showed an almost continuous ferrite network microstructure that may deteriorate component part toughness if this ferrite comes to suffer embrittlement. On the samples with content ferrite around 5% the ferrite network is semi-continuous while for low values (around 2%) the ferrite showed isolated cores. The morphologies were classified as vermicular. The study of micro chemical analysis of Si, Mo, Cr, Fe and Ni on ferrite and austenite showed partition coefficient in accordance with values defined in literature. The thickness effect on chemical composition was small and not conclusive.