As ligas à base de níquel de alta resistência são utilizadas em uma infinidade de sistemas avançados, onde baixo peso e sistemas de transmissão mecânica de alta densidade de energia são necessários. Componentes, tais como, engrenagens, rolamentos e eixos poderiam ser consideravelmente menor e mais durável se uma grande melhoria em propriedades mecânicas de ligas à base de níquel for alcançada. Um refinamento significativo no tamanho de grão (incluindo nível nano) é um método promissor para a obtenção de melhorias fundamentais nas propriedades mecânicas. O tamanho de grão é conhecido por ter um efeito significativo sobre o comportamento mecânico dos materiais. Um dos métodos mais favoráveis de alcançar refinamento de grão extremo é submetendo os materiais à deformação plástica intensa. As principais variáveis microestruturais nas superligas são a quantidade de precipitados e sua morfologia, o tamanho e a forma do grão e a distribuição de carbonetos (Cr7C3 e Cr23C6) que poderão reduzir propriedades mecânicas da liga. Neste trabalho é apresentada análise por microscopia óptica e eletrônica de transmissão e também os dados de dureza após deformação plástica intensa (tensão de cisalhamento puro) e alguns tratamentos térmicos. / High strength nickel based alloys are used in a multitude of advanced systems where lightweight, high power density mechanical power transmission systems are required. Components such as gears, bearings and shafts could be made significantly smaller and more durable if a major improvement in nickel based alloy mechanical properties could be achieved. A significant refinement in grain size (includes nano level) is thought to be a promising method for achieving fundamental improvements in mechanical properties. Grain size is known to have a significant effect on the mechanical behavior of materials. One of the most favorable methods of achieving extreme grain refinement is by subjecting the materials to severe plastic deformation. The principal microstructural variations in superalloys are the precipitation amount and morphology, grain size and the distribution of carbide precipitation (Cr7C3 and Cr23C6) that could reduce the mechanical properties of the alloys. This work shows optical and transmission electron microscopy analysis and also hardness data after severe plastic deformation (pure shear stress) and some thermal treatments.

Este trabalho avaliou o comportamento eletroquímico do metal de base (MB) de uma liga a base de níquel-cromo em relação a juntas soldadas desta liga obtidas pelos processos de brasagem (BRA) e Tungsten Inert Gas (TIG), imersos em saliva artificial com pH 2,5 e 5,5. Foram também realizados ensaios de microdureza e caracterização microestrutural, por meio de microscopia óptica e eletrônica de varredura e análise química semi-quantitativa por EDS, nos grupos MB, TIG, BRA e no cordão de solda a laser (LAS). O MB apresentou uma matriz rica em níquel e cromo, distribuída em um arranjo dendrítico típico, apresentando inclusões metálicas de silício e titânio, além de porosidades. As soldas TIG e LAS revelaram uma microestrutura mais refinada que o MB, mostrando, entretanto, uma mesma composição química e distribuição de seus elementos. A solda BRA apresentou diferenças marcantes em sua microestrutura, composição química e distribuição de seus elementos em relação ao MB. Os dados de microdureza Vickers (HV), potencial de corrosão (Ecorr) e densidade de corrente de corrosão (jcorr) foram analisados com ANOVA e teste de Tukey (p<0,05). Para determinação da influência do pH quanto a resistência à corrosão dos grupos MB, TIG e BRA, empregou-se o teste t de Student (p<0,05). O MB apresentou menor média de microdureza (256,13 9,39 HV), seguido pelos grupos TIG (271,53 8,07 HV), LAS (303,73 13,93 HV) e BRA (551,99 37,73 HV). Em pH 2,5 as médias do Ecorr (mV) para o MB, TIG e BRA foram, respectivamente, -67,9 8,43, -52,78 16,74, e -284,33 19,04; e em pH 5,5, médias de -54,03 21,15, -62,08 20,16 e -278,8 28,96. Os valores médios de jcorr (A.cm-2) para o MB, TIG e BRA em pH 2,5 foram, respectivamente, 2,49 0,95, 5,584 1,64 e 27,45 4,9; e em pH 5,5, médias de 1,929 0,83, 4,267 1,51 e 54,2 11,96. Os grupos MB e TIG apresentaram boa resistência à corrosão, com maior módulo de impedância em relação ao grupo BRA. As diferenças no pH da saliva artificial não alteraram o comportamento corrosivo dos grupos MB e TIG. Entretanto, observou-se uma redução marcante na jcorr e no módulo de impedância nas soldas obtidas pelo processo de brasagem. O grupo BRA apresentou corrosão galvânica ao ser analisado formando par com o MB, mostrando uma jcorr de 5,3 A.cm-2. Entretanto, o mesmo não foi observado quando o MB foi associado à solda TIG, onde a jcorr foi cerca de 150 vezes menor. O grupo BRA, além de apresentar um comportamento eletroquímico muito diferente do MB, revelou diferenças marcantes quanto a composição química, aspecto microestrutural e microdureza. As juntas TIG e LAS mostraram semelhanças químicas e microestruturais em relação ao MB, sendo que na solda TIG esta semelhança foi ainda mais evidente. Além disto, a solda TIG apresentou um comportamento eletroquímico muito semelhante ao MB e, portanto, parecendo ser mais recomendável para soldar ligas odontológicas de níquel-cromo em relação aos demais processos de soldagem aqui avaliados. / This study evaluated and compared the electrochemical behavior of the base metal (BM) of a nickel-chromium dental alloy with welded joints obtained by brazing processes (BRA) and Tungsten Inert Gas (TIG), when immersed in artificial saliva at pH 2.5 and 5.5. Microhardness, microstructural characterization by means of optical microscopy, scanning electron microscopy (SEM) and semi-quantitative chemical analysis by Energy Dispersive Spectroscopy (EDS), were performed in the groups BM, TIG, BRA and in joints weld by laser (LAS). The BM showed a matrix rich in nickel and chromium, distributed in a typical dendritic arrangement, with inclusions of silicon and titanium, and porosities. LAS and TIG welds reveled a microstructure more refined than the BM, however, the same chemical composition and distribution of its elements. BRA showed marked differences in their microstructure, chemical composition and distribution of the elements in relation to BM. Vickers microhardness (HV), corrosion potential (Ecorr) and corrosion current density (jcorr) were statistically analyzed with ANOVA and Tukey test (p <0.05). In order to determine the influence of pH and corrosion resistance in groups BM, TIG and BRA, Student t test, with significance level of 95% was used. BM had the lowest average microhardness (HV 256.13 9.39), followed by groups TIG (271.53 8.07 HV), LAS (303.73 13.93 HV) and BRA (551, HV 99 37.73). At pH 2.5 the average Ecorr (mV) for the MB and TIG were respectively -67.9 8.43 and -52.78 16.74, and at pH 5.5, averaging -54, 03 21.15 and -62.08 20.16. LAS group showed averages of Ecorr (mV) at pH 2.5 and 5.5, respectively, -284.33 19.04 and 28.96 -278.8. The average values of jcorr (&#956;A.cm-2) to BM and TIG at pH 2.5 were respectively 2.49 0.95 and 5.584 1.64, and at pH 5.5, 1.929 0.83 and 4.267 1.51. Average jcorr for LAS group (&#956;A.cm-2) at pH 2.5 and 5.5 were respectively 27.45 4.9 and 11.96 54.2. BM and TIG groups showed a good corrosion resistance, with a higher impedance modulus compared to LAS group. Differences in pH of artificial saliva did not affect the corrosion behavior of BM and TIG groups. However, there was a marked reduction in jcorr and modulus of impedance obtained by soldering brazing process. BRA group presented galvanic corrosion when it was analyzed forming pair with BM group, showing a jcorr of 5.3 &#956;A.cm-2. However, this was not observed when the BM was associated with TIG welding, where jcorr was about 150 times lower. BRA group, besides presenting a very different electrochemical behavior of MB revealed marked differences in chemical composition, microstructure and microhardness aspect. TIG and LAS joints showed chemical and microstructural similarities compared to BM, and this similarity was even more evident in the TIG welding. In addition, TIG showed an electrochemical behavior very similar to BM, and therefore seems to be more advisable to solder nickel-chrome based alloys for use in dentistry compared to other welding processes evaluated here.

Made available in DSpace on 2014-12-17T14:07:04Z (GMT). No. of bitstreams: 1 JulianaPN_DISSERT.pdf: 2953662 bytes, checksum: 47355bc7fed206f60c6c6b5d8565099b (MD5) Previous issue date: 2012-06-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 &#956;m and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 &#956;m. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 &#956;m, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 &#956;m, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ? C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ? C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 ?C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 &#956;m active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy / Ligas de N?quel s?o freq?entemente utilizadas em aplica??es que requerem resist?ncia mec?nica a elevadas temperaturas associada ? resist?ncia ? corros?o. Ligas de Ni-Si-C podem ser obtidas por meio de metalurgia do p? em que s?o realizadas misturas de p?s de n?quel met?lico com adi??es de p?s de diferentes portadores de liga, para tal foram utilizados neste trabalho SiC, Si3N4 ou Si met?lico com grafita. P?s de Ni carbonila com tamanho m?dio de part?culas de 11 &#956;m foram misturados a 3% em massa de p?s de SiC com tamanho m?dio de part?culas de 15, 30 e 50 &#956;m e foram obtidas ainda amostras contendo 4 e 5% em massa de SiC com tamanho m?dio de part?culas de 15 &#956;m. Tamb?m foram obtidas amostras variando-se o portador de liga, sendo estes p?s de Si3N4 com grafita, com tamanho m?dio de part?culas de 1,5 e 5 &#956;m, respectivamente. Assim como Si met?lico com grafita, com tamanho m?dio de part?culas de 12,5 e 5 &#956;m, respectivamente. O material de refer?ncia adotado foi n?quel carbonila sinterizado sem adi??o de portadores. A caracteriza??o microestrutural das ligas foi feita por microscopia ?ptica e eletr?nica de varredura com an?lise qu?mica semi-quantitativa. Foram determinadas as densidades das amostras e obtidas medidas de microdureza Vickers. Foi estudada a dissocia??o dos portadores de liga ap?s sinteriza??o em 1200 ?C durante 60 minutos. Foi avaliada, ainda, para as mesmas condi??es de sinteriza??o, a influencia da varia??o do tamanho m?dio de part?culas do portador SiC, para a propor??o de 3% em massa. Por fim, foi estudo a influencia da varia??o das temperaturas de sinteriza??o em 950, 1080 e 1200 ?C sem patamar e, ainda, com patamares de 30, 60, 120 e 240 minutos para sinteriza??o cuja temperatura foi de 950 ?C. As curvas de dilatometria mostraram que o SiC favorece a sinteriza??o do Ni de forma mais eficaz que os demais portadores de liga analisados. O SiC com tamanho m?dio de part?culas de 15 &#956;m ativa a sinteriza??o da liga de forma mais eficaz que os demais SiC utilizados. Por?m, com as an?lises qu?mica e morfol?gica para todas as ligas, foi poss?vel observar que houve dissocia??o do SiC e do Si3N4, assim como difus?o do Si na matriz de Ni e carbono aglomerado e disperso na matriz, o que tamb?m ocorreu para as ligas com portadores Si met?lico e grafita. Portanto, a liga que apresentou melhores resultados foi de Ni contendo Si met?lico com grafita como portadores de liga, j? que esta apresentou grafita melhor dispersa na liga, atingindo o modelo microestrutural proposto, do qual ? necess?rio para material com caracter?stica de lubrificante s?lido, assim como obteve os melhores resultados quando a densidade e dureza da liga

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-06-26T12:59:39Z No. of bitstreams: 1 VALMIR RODRIGUES BATISTA - TESE (PPGCEMat) 2016.pdf: 18369155 bytes, checksum: 4dd7420f9b0bf191a2596450d01bfaa6 (MD5) / Made available in DSpace on 2018-06-26T12:59:39Z (GMT). No. of bitstreams: 1 VALMIR RODRIGUES BATISTA - TESE (PPGCEMat) 2016.pdf: 18369155 bytes, checksum: 4dd7420f9b0bf191a2596450d01bfaa6 (MD5) Previous issue date: 2016-02-22 / CNPq / Neste trabalho é apresentado um estudo sobre a susceptibilidade à fragilização por hidrogênio de juntas soldadas de metais dissimilares presentes em equipamentos submarinos da indústria do petróleo, as quais ficam submetidas a condições de uso que envolvem esforços mecânicos severos, em ambientes corrosivos, proveniente da água do mar e do fluido petrolífero. O objetivo dessa pesquisa foi avaliar o efeito da utilização dos processos Plasma Pó (PTA-P) e MIG para a aplicação de "amanteigamentos" com Liga de Ni sobre a susceptibilidade à fragilização por hidrogênio de juntas soldadas de aços dissimilares utilizadas em aplicação offshore utilizando diferentes temperaturas de preaquecimento e interpasse e também comparar os resultados para dois aços para válvula, o AISI 8630M e AISI 4130. O processo de soldagem utilizado para a união das juntas foi o processo MIG utilizando-se como metal de adição o arame eletrodo, Inconel-625 (ER NiCrMo-3) de 1,2 mm de diâmetro. Os dois aços foram submetidos a três diferentes combinações de temperaturas de preaquecimento e interpasse antes dos amanteigados pelos processos PTA-P e MIG. Após a etapa de amanteigamento foram realizadas análises de composição química por EDS, microestruturais por MO e MEV, e de microdureza antes e depois do TTAT. Em seguida foram executadas as soldagens de união pelo processo MIG. As amostras de tração foram previamente hidrogenadas simulando as condições existentes de proteção catódica em ambiente submarino. O aumento das temperaturas de preaquecimento e interpasse resultou em maior refino dos grãos da ZTA, entretanto proporcionou aumento da média de sua microdureza e de sua extensão, e em maior migração de Fe do MB para o MS, resultando em maior fragilização por hidrogênio. Pelo processo PTA-P houve uma menor diversidade e frequência de incidência de zonas parcialmente diluídas (ZPD), sendo encontradas apenas ZPD do tipo contínua, enquanto que pelo processo MIG foram encontradas ZPD do tipo descontínua, com diferentes morfologias. O TTAT proporcionou uma significativa redução de 20% a 44% nos valores da microdureza da ZTA. Com base nos níveis de deformação e Índice de Fragilização (IF), o aço AISI 4130 apresentou os melhores resultados com relação à fragilização por hidrogênio. / This Thesis presents a study about hydrogen embrittlement susceptibility of dissimilar metals welded joints present in oil industry equipment, specifically in valves connections with pipes for the oil transport, which are subject to use conditions involving severe mechanical stresses in corrosive environments, from the seawater and the oil fluid. As the valves steel are martensitic its heat affected zone (HAZ) may be susceptible to hydrogen embrittlement not only from cathodic protection but also from the seawater and H2S. Therefore, to prevent this potential embrittlement and consequently crack formation in these regions of the welded joint, is used as nickel alloy filler metal. Therefore, the part of martensitic steel previously undergoes a "buttering" process which consists of applying layers of Ni deposited by welding. The welding process used for the union of the joints was the MIG process using as filler metal the Inconel-625 (ER NiCrMo-3) wire electrode 1.2 mm in diameter. Two steels were buttering, AISI 8630M and AISI 4130. Both were subjected at the three different combinations of preheat and interpass temperatures. For the buttering realization, the same alloy, in powder form, was used by Plasma powder process (PTA-P). To evaluate the efficiency of the PTA-P process in buttering operation it was compared with other buttering performed by MIG process with the same filler metal of the weld joint. After buttering the samples were subjected to post welding heat treatment (PWHT). Chemical composition analyses were performed by Energy Dispersive Spectroscopy (EDS), microstructure by Optical Microscopy (OM) and Scanning Electron Microscopy (SEM), and microhardness. After the welding the samples were machined and hydrogened using a process similar to those used for cathodic protection and submitted to tension tests. The Increase in the preheat and interpass temperature resulted in higher refining the grains of the HAZ however it, increased its average microhardness and extension, promoted greater Fe migration from MB to the buttering, increasing the hydrogen embrittlement. The use of PTA-P process promoted a very lower incidence and diversity of partially diluted zone (PDZ), being found only continuous PDZ. The PWHT promoted a reduction from 20% to 44% of hardness values. Based on the deformation levels and Embrittlement Index (EI), the AISI 4130 steel showed the best results with respect to hydrogen embrittlement.

Este trabalho avaliou o comportamento eletroquímico do metal de base (MB) de uma liga a base de níquel-cromo em relação a juntas soldadas desta liga obtidas pelos processos de brasagem (BRA) e Tungsten Inert Gas (TIG), imersos em saliva artificial com pH 2,5 e 5,5. Foram também realizados ensaios de microdureza e caracterização microestrutural, por meio de microscopia óptica e eletrônica de varredura e análise química semi-quantitativa por EDS, nos grupos MB, TIG, BRA e no cordão de solda a laser (LAS). O MB apresentou uma matriz rica em níquel e cromo, distribuída em um arranjo dendrítico típico, apresentando inclusões metálicas de silício e titânio, além de porosidades. As soldas TIG e LAS revelaram uma microestrutura mais refinada que o MB, mostrando, entretanto, uma mesma composição química e distribuição de seus elementos. A solda BRA apresentou diferenças marcantes em sua microestrutura, composição química e distribuição de seus elementos em relação ao MB. Os dados de microdureza Vickers (HV), potencial de corrosão (Ecorr) e densidade de corrente de corrosão (jcorr) foram analisados com ANOVA e teste de Tukey (p<0,05). Para determinação da influência do pH quanto a resistência à corrosão dos grupos MB, TIG e BRA, empregou-se o teste t de Student (p<0,05). O MB apresentou menor média de microdureza (256,13 9,39 HV), seguido pelos grupos TIG (271,53 8,07 HV), LAS (303,73 13,93 HV) e BRA (551,99 37,73 HV). Em pH 2,5 as médias do Ecorr (mV) para o MB, TIG e BRA foram, respectivamente, -67,9 8,43, -52,78 16,74, e -284,33 19,04; e em pH 5,5, médias de -54,03 21,15, -62,08 20,16 e -278,8 28,96. Os valores médios de jcorr (A.cm-2) para o MB, TIG e BRA em pH 2,5 foram, respectivamente, 2,49 0,95, 5,584 1,64 e 27,45 4,9; e em pH 5,5, médias de 1,929 0,83, 4,267 1,51 e 54,2 11,96. Os grupos MB e TIG apresentaram boa resistência à corrosão, com maior módulo de impedância em relação ao grupo BRA. As diferenças no pH da saliva artificial não alteraram o comportamento corrosivo dos grupos MB e TIG. Entretanto, observou-se uma redução marcante na jcorr e no módulo de impedância nas soldas obtidas pelo processo de brasagem. O grupo BRA apresentou corrosão galvânica ao ser analisado formando par com o MB, mostrando uma jcorr de 5,3 A.cm-2. Entretanto, o mesmo não foi observado quando o MB foi associado à solda TIG, onde a jcorr foi cerca de 150 vezes menor. O grupo BRA, além de apresentar um comportamento eletroquímico muito diferente do MB, revelou diferenças marcantes quanto a composição química, aspecto microestrutural e microdureza. As juntas TIG e LAS mostraram semelhanças químicas e microestruturais em relação ao MB, sendo que na solda TIG esta semelhança foi ainda mais evidente. Além disto, a solda TIG apresentou um comportamento eletroquímico muito semelhante ao MB e, portanto, parecendo ser mais recomendável para soldar ligas odontológicas de níquel-cromo em relação aos demais processos de soldagem aqui avaliados. / This study evaluated and compared the electrochemical behavior of the base metal (BM) of a nickel-chromium dental alloy with welded joints obtained by brazing processes (BRA) and Tungsten Inert Gas (TIG), when immersed in artificial saliva at pH 2.5 and 5.5. Microhardness, microstructural characterization by means of optical microscopy, scanning electron microscopy (SEM) and semi-quantitative chemical analysis by Energy Dispersive Spectroscopy (EDS), were performed in the groups BM, TIG, BRA and in joints weld by laser (LAS). The BM showed a matrix rich in nickel and chromium, distributed in a typical dendritic arrangement, with inclusions of silicon and titanium, and porosities. LAS and TIG welds reveled a microstructure more refined than the BM, however, the same chemical composition and distribution of its elements. BRA showed marked differences in their microstructure, chemical composition and distribution of the elements in relation to BM. Vickers microhardness (HV), corrosion potential (Ecorr) and corrosion current density (jcorr) were statistically analyzed with ANOVA and Tukey test (p <0.05). In order to determine the influence of pH and corrosion resistance in groups BM, TIG and BRA, Student t test, with significance level of 95% was used. BM had the lowest average microhardness (HV 256.13 9.39), followed by groups TIG (271.53 8.07 HV), LAS (303.73 13.93 HV) and BRA (551, HV 99 37.73). At pH 2.5 the average Ecorr (mV) for the MB and TIG were respectively -67.9 8.43 and -52.78 16.74, and at pH 5.5, averaging -54, 03 21.15 and -62.08 20.16. LAS group showed averages of Ecorr (mV) at pH 2.5 and 5.5, respectively, -284.33 19.04 and 28.96 -278.8. The average values of jcorr (&#956;A.cm-2) to BM and TIG at pH 2.5 were respectively 2.49 0.95 and 5.584 1.64, and at pH 5.5, 1.929 0.83 and 4.267 1.51. Average jcorr for LAS group (&#956;A.cm-2) at pH 2.5 and 5.5 were respectively 27.45 4.9 and 11.96 54.2. BM and TIG groups showed a good corrosion resistance, with a higher impedance modulus compared to LAS group. Differences in pH of artificial saliva did not affect the corrosion behavior of BM and TIG groups. However, there was a marked reduction in jcorr and modulus of impedance obtained by soldering brazing process. BRA group presented galvanic corrosion when it was analyzed forming pair with BM group, showing a jcorr of 5.3 &#956;A.cm-2. However, this was not observed when the BM was associated with TIG welding, where jcorr was about 150 times lower. BRA group, besides presenting a very different electrochemical behavior of MB revealed marked differences in chemical composition, microstructure and microhardness aspect. TIG and LAS joints showed chemical and microstructural similarities compared to BM, and this similarity was even more evident in the TIG welding. In addition, TIG showed an electrochemical behavior very similar to BM, and therefore seems to be more advisable to solder nickel-chrome based alloys for use in dentistry compared to other welding processes evaluated here.

Um dos principais mecanismos de falha que causam riscos de fratura a reatores de água pressurizada é a corrosão sob tensão de ligas metálicas em água do circuito primário (CSTAP). É causada por uma combinação das tensões de tração, meio ambiente em temperatura e microestruturas metalúrgicas susceptíveis. Ela pode ocorrer, dentre outros locais, nos bocais do mecanismo de acionamento das barras de controle. Essa fratura pode causar acidentes que comprometem a segurança nuclear através do bloqueio das barras de controle e vazamentos de água do circuito primário reduzindo a confiabilidade e a vida útil do reator. O objetivo desta Tese de Doutorado é o estudo de modelos e uma proposta de modelagem para fraturas por corrosão sob tensão em liga 75Ni15Cr9Fe (liga 600), em água de circuito primário de reator de água pressurizada nesses bocais. São superpostos modelos eletroquímicos e de mecânica da fratura e validados com dados obtidos em experimentos e na literatura. Na parte experimental foram utilizados resultados obtidos pelo CDTN no equipamento recém-instalado de ensaio por taxa de deformação lenta. Na literatura está proposto um diagrama que exprime a condição termodinâmica de ocorrerem diversos modos de CSTAP na liga 600: partiu-se de diagramas de potencial x pH (diagramas de Pourbaix), para a liga 600 imersa em água primária à alta temperatura (3000C a 3500C). Sobre ele, determinaram-se os submodos de corrosão, a partir de dados experimentais. Em seguida acrescentou-se uma dimensão adicional ao diagrama, correlacionando uma variável a que se denominou fração de resistência à corrosão sob tensão. No entanto, é possível acrescentar-se outras variáveis que exprimem a cinética de iniciação e/ou crescimento de trinca, provenientes de outras modelagens de CSTAP. A contribuição original deste trabalho se insere nessa fase: partindo-se de uma condição de ensaio de potencial versus pH, foram iniciadas as modelagens de um modelo empírico-comparativo, um semi-empírico-probabilístico, um de tempo de iniciação e um de taxa de deformação, a partir dos ensaios experimentais e superpostas a essa condição. Esses exprimem respectivamente a susceptibilidade à CSTAP, o tempo de falha, e nos dois últimos o tempo de iniciação de falha por corrosão sob tensão. Os resultados foram comparados com os da literatura e se mostraram coerentes. Através desse trabalho, obteve-se uma metodologia de modelagem a partir de dados experimentais. / One of the main failure mechanisms that cause risks to pressurized water reactors is the primary water stress corrosion cracking (PWSCC) occurring in alloys. It can occurs, besides another places, at the control reactor displacement mechanism nozzles. It is caused by the joint effect of tensile stress, temperature, susceptible metallurgical microstructure and environmental conditions of the primary water. These cracks can cause accidents that reduce nuclear safety by blocking the rods displacement and may cause leakage of primary water, reducing the reactors life. In this work it is proposed a study of the existing models and a modeling proposal to primary water stress corrosion cracking in these nozzles in a nickelbased Alloy 600. It is been superposed electrochemical and fracture mechanics models, and validated using experimental and literature data. The experimental data were obtained at CDTN-Brazilian Nuclear Technology Development Center, in a recent installed slow strain rate testing equipment. In the literature it is found a diagram that indicates a thermodynamic condition for the occurrence of some PWSCC submodes in Alloy 600: it was used potential x pH diagrams (Pourbaix diagrams), for Alloy 600 in high temperature primary water (3000C till 3500C). Over it, were located the PWSCC submodes, using experimental data. It was added a third parameter called stress corrosion strength fraction. However, it is possible to superpose to this diagram, other parameters expressing PWSCC initiation or growth kinetics from other models. Here is the proposition of the original contribution of this work: from an original experimental condition of potencial versus pH, it was superposed, an empiric-comparative, a semi-empiric-probabilistic, an initiation time, and a strain rate damage models, to quantify respectively the PWSCC susceptibility, the failure time, and in the two lasts, the initiation time of stress corrosion cracking. It was modeling from our experimental data. The results were compared with the literature and it showed to be coherent. From this work was obtained a modeling methodology from experimental data.

Mechanical properties of structural materials are highly correlated to their microstructure. The relationship between microstructure and mechanical properties can be established experimentally. The growing need for structural materials in industry promotes the study of microstructural evolution of materials by design using computational approaches. This thesis presents the microstructural evolution of two different structural materials. The first uses a genetic algorithm approach to study the microstructural evolution of a high-temperature nickel-based oxide-dispersion-strengthened (ODS) alloy. The chosen Ni-20Cr ODS system has nano Y2O3 particles for dispersion strengthening and submicron Al2O3 for composite strengthening. Synergistic effects through the interaction of small dispersoids and large reinforcements improved high-temperature strength. Optimization considered different weight factors on low temperature strength, ductility, and high temperature strength. Simulation revealed optimal size and volume fraction of dispersoids and reinforced particles. Ni-20Cr-based alloys were developed via mechanical alloying for computational optimization and validation. The Ni-20Cr-1.2Y2O3-5Al2O3 alloy exhibited significant reduction in the minimum creep rate (on the order of 10-9 s-1) at 800oC and 100 MPa. The second considers the microstructural evolution of AA 7050 alloy during friction stir welding (FSW). Modeling the FSW process includes thermal, material flow, microstructural and strength modeling. Three-dimensional material flow and heat transfer model was developed for friction stir welding process of AA 7050 alloy to predict thermal histories and extent of deformation. Peak temperature decreases with the decrease in traverse speed at constant advance per revolution, while the increase in tool rotation rate enhances peak temperature. Shear strain is higher than the longitudinal and transverse strain for lower traverse speed and tool rotation rate; whereas for higher traverse speed and tool rotation rate, shear and normal strain acquire similar values. Precipitation distribution simulation using TC-PRISMA predicts the presence of η' and η in the as-received AA 7050-T7451 alloy and mostly η in the friction stir welded AA7050 alloy, which results in the lower predicted strength of friction stir welded alloy. Further, development of modeling assists in process optimization and innovation, and enhances the progression rate. Accelerating the development process requires coupling experimental methods with predictive modeling. The overall purpose of this work was to develop an integrated computational model with predictive capabilities. In the present work, an application tool to predict thermal histories during FSW of AA7050 was developed using COMSOL software.

Cette étude fondamentale est dédiée à la compréhension de l’influence de la composition chimique, notamment la teneur en chrome, des alliages base de nickel sur leur mécanismes de corrosion et d’oxydation. La corrosion sous contrainte intergranular (CSCIG) est un mode de dégradation qui affecte de nombreux alliages au sein des réacteurs à eau pressurisé. En particulier, les alliages base nickel tubes des générateur de vapeur (GV). La sensibilité à la CSC est désormais dépend de la teneur en chrome, ce qui a conduit au remplacement de l’alliage 600 (Ni-16Cr-9Fe) par l’alliage 690 (Ni-30Cr-9Fe). Cependant le bon comportement de l’alliage 690 en termes de résistance à la corrosion restes mal défini. L’objective de cette thèse est double : i) déterminer l’effet de la teneur en chrome, ii) contribuer à la compréhension de l’effet de fer étant un élément d’addition sur la résistance à la corrosion et l’oxydation généralisée des alliages base nickel en milieu primaire assimilé et en vapeur surchauffée à 700°C. Par ailleurs, des analyses électrochimiques pertinentes dans la température ambiante ont été mené afin d’établir une corrélation entre les propriétés physiques de film passive susceptible de protéger le matériau et de la teneur en chrome. Des alliages modèles binaires Ni-Cr, à teneur de chrome varie entre 14 et 30 % en poids, des alliages ternaires Ni-Cr-8Fe et l’alliage 600 ont été étudies. L’aspect expérimental de cette étude repose sur des techniques conventionnelles: SEM, STEM, EDX, Potentiodynamique, EIS, Chronoamperometrie, Mott-Schottky. La cinétique d’oxydation en vapeur surchauffée a été déterminée en mesurant l’apport de masse. L’impact de l’état de surface sur le processus de la corrosion et l’oxydation a été mis en évidence. Les polissages miroir et électrochimique ont été réalisés afin de découpler l’effet de l’écrouissage développé en subsurface, induit par la préparation de surface, et la composition chimique de l’alliage. La teneur en chrome limite à partir de laquelle l’alliage a un comportement satisfaisant en corrosion a été déterminé à 20% dans le milieu primaire. Cependant les analyses électrochimiques ont décelé l’existence d’une teneur en chrome optimal à 26%. La cinétique d’oxydation des alliages modèles ainsi que la morphologie des oxydes formés sur ces matériaux dans le milieu vapeur surchauffée ont indiqué l’existence d’une teneur en chrome optimal à 24%. Une dégradation des propriétés des films d’oxydes a été observée en augmentant la teneur en chrome au-dessus de l’optimum. En résumé, ce travail se préoccupe de l’optimisation de la teneur en chrome, méthode plus adéquate, pour l’amélioration de la résistance à la corrosion et l’oxydation des alliages base nickel. / This fundamental study is focused on the understanding of the influence of the chemical composition of Ni-based alloys on their corrosion and oxidation mechanisms. This work is not dedicated for a particular application. It is well known for instance that Ni-based alloys are susceptible to intergranular stress corrosion cracking (IGSCC) in primary water. Thus, Alloy600 (Ni-16Cr-9Fe), used in steam generator (SG) tubing, was replaced by higher chromium content material Alloy690 (Ni-30Cr-9Fe). This later shows a better resistance to IGSCC which may be linked to the growth of more protective oxide layer as chromium content is increased to 30 wt.%. The main goal of this study is to investigate: i) the influence of chromium content, ii) impact of iron addition on the corrosion and oxidation resistance of Ni-based alloys in primary water and superheated steam at 700°C. Furthermore, analytical approach in acidic solution is conducted at room temperature. This allowed to establish a relationship between alloying elements and physical properties of the oxide layers. For this purpose, Ni-xCr (14 ≤ x≤ 30 wt.%), Ni-xCr-8Fe (x=14,22 and 30 wt.%) model alloys and industrial material Alloy600 have been studied. To characterize the oxide scales, conventional technics were used: SEM, STEM, EDX, Potentiodynamic, EIS, Chronoamperometry, Mott-Schottky. Furthermore, steam oxidation kinetics was evaluated by means of weight gain measurements. To uncouple the effect of surface cold-work and the chemical composition of the base metal, mirror and electro polishing were carried out. In primary water, critical chromium content (20 wt.%), which corresponds to the minimum amount of chromium required to the transition from non-protective to protective and compact Cr-oxide layer, is determined. However, the analytical approach, using electrochemical technics, at room temperature elucidated the existence of optimum chromium content (26 wt.%) in terms of corrosion resistance. In superheat steam, oxidation kinetics and oxide scale characteristics showed the existence of optimum chromium content (24 wt.%) in terms of oxidation resistance. The corrosion and oxidation resistance is degraded as chromium content was increased more than optimal amount. Iron addition (8 wt.%) had a detrimental effect on the protectivess of the resulting oxide scales. Finally, this study showed that optimizing of chromium content is more appropriate method for enhancing corrosion and oxidation resistance, that increasing chromium content to high level is not necessary beneficial to those parameters. This work provides a useful knowledge to design new alternative materials. For this purpose, more investigations should be conducted to test other parameters such as: weldability, fabricability, thermal conductivity,etc.

La décrépitation (fracturation) des matériaux actifs de batteries associée à leur variation volumique lors des cycles de charge/décharge a pour effet d'accélérer leur corrosion par l'électrolyte et/ou d'induire une perte de connectivité électronique au sein de l'électrode ce qui réduit notablement leur durée de vie. C’est particulièrement le cas des hydrures métalliques utilisés dans les batteries Ni-MH. À ce jour, l'évaluation de leur fracturation se limite généralement à une observation post mortem des électrodes par microscopie ce qui ne permet pas une analyse détaillée du processus de décrépitation. À ce titre, un de nos principaux objectifs dans le cadre de ce travail de recherche a été de développer une méthode d'analyse novatrice et performante basée sur l'émission acoustique (EA) afin d'étudier in situ la fracturation d'électrodes négatives pour batteries Ni-MH. Dans une première étape, nous avons analysé en détail les signaux acoustiques produits lors de la charge (hydruration) d'un alliage commerciale à base de LaNi5 et d'un alliage MgNi obtenu par broyage mécanique. Nous avons ainsi pu séparer les signaux générés par la fracturation des particules d’hydrures métalliques de ceux associés à la formation de bulles de H2, ce qui a permis d’établir les mécanismes qui régissent leur fracturation. Par la suite, un montage expérimental, constitué d’une cellule électrochimique connectée à un capteur de force en compression et d’un équipement d’EA, a été mis point pour suivre in-situ la fracturation et la force générée par l’expansion/contraction lors du cyclage des électrodes MgNi et LaNi5. Nous avons ainsi pu confirmer que l’expansion/contraction volumique de l’alliage MgNi est plus progressif que pour l’alliage à base de LaNi5. Par la suite, l’étude comparée par EA des alliages MgNi, Mg0.9Ti0.1Ni et Mg0.9Ti0.1NiAl0.05 a permis de mettre en évidence l'influence de leur composition sur leur résistance à la pulvérisation. Finalement, nous avons étudié en détail l’influence de l’addition de palladium dans l’alliage Mg0.9Ti0.1NiAl0.05 sur son comportement électrochimique et sa résistance à la fracturation. / The pulverization (cracking) of active materials in batteries, induced by their volume change during charge/discharge cycles, accentuates their corrosion by the electrolyte and/or leads to a loss of electronic connectivity within the electrode, which notably reduces their cycle life. This particularly occurs for metallic hydrides used in Ni-MH batteries. To date, the evaluation of their cracking is generally limited to post mortem observations of the electrodes by microscopy, which does not allow for a detailed analysis of the decrepitation process. In this respect, one of our main research objectives was to develop an innovative and efficient analysis method based on acoustic emission (AE) for in situ monitoring of the cracking of negative electrodes for Ni-MH batteries. As a first step, a detailed analysis of the acoustic signals generated during the charge (hydriding) of a commercial LaNi5-based alloy and a MgNi alloy obtained by mechanical alloying was performed. This allowed separating the signals generated by the cracking of the metallic hydride particles from those induced by the formation of H2 bubbles. We have shown that the mechanism which governs the pulverization of the MgNi alloy remarkably differs from that of the LaNi5-based alloy. In a second step, an experimental set-up made of an electrochemical cell linked to a compression force cell and an AE equipment was elaborated, in order to monitor concomitantly the cracking and the force generated by the expansion/contraction of the MgNi and LaNi5 during cycling. We have thereby been able to confirm that the volume expansion/contraction of the MgNi alloy is more progressive than that of the LaNi5 alloy. The AE-based comparative study of MgNi, Mg0.9Ti0.1NiAl5 and Mg0.9Ti0.1NiAl0.05 alloys then allowed demonstrating the positive effect of the partial Mg substitution by Ti and adding of Al on the alloy decrepitation resistance. As a final step, we have studied the impact of palladium addition in the Mg0.9Ti0.1NiAl0.05 alloy on its electrochemical behaviour and cracking resistance.

Dans l’industrie nucléaire, différents composants des réacteurs à eau pressurisée sont soudés par le procédé TIG (Tungsten Inert Gas). Pour obtenir une résistance à la corrosion et une tenue en service suffisante, ces pièces sont réalisées en alliage base nickel NY690. La compréhension des phénomènes physiques impliqués durant le soudage est nécessaire afin de connaître l’évolution de la microstructure et leur influence sur le comportement mécanique. Pour améliorer la qualité des produits soudés, il est crucial de déterminer les contraintes résiduelles après soudage ce qui implique de connaître le comportement mécanique de l’alliage NY690. En effet, le soudage de ces pièces massives dont l’épaisseur est comprise entre 50 et 250 mm nécessite un grand nombre de passes et donc grand nombre de cycles thermo-mécaniques. Pour reproduire ces chargements complexes se produisant dans la zone affectée thermiquement, des essais mécaniques ont été réalisés en utilisant la machine Gleeble 3500 et une machine de traction/torsion MTS-809. Des essais de traction et des essais cycliques ont été réalisés pour différents états microstructuraux à température ambiante et à 750°C. Plus précisément, l’influence de la taille de grain et de la présence des carbures de chrome sur le comportement mécanique a été étudiée dans le but de déterminer les paramètres à prendre en compte pour modéliser le comportement mécanique. Le comportement mécanique en chargement monotone a ensuite été modélisé en fonction de la température et de la vitesse de déformation en utilisant le formalisme de Kocks-Mecking-Estrin. Ce modèle ensuite été implémenté sous Sysweld pour simuler des expériences de soudage. / Mechanical behavior of nickel alloy 690 (NY690) is characterized from 25°C to 1100°C and for a strain rate ranging from 10-4 to 5×10-3s-1. The effects of chromium carbides and grain size (50-150 µm) on the tensile properties of NY690, were studied at 25°C and 750°C. Chromium carbides have negligible influence on the yield stress and on the strain hardening whereas the grain size slightly decreases the yield stress and the hardening rate at room temperature. The grain size has little influence on the strain-hardening but increases the steady-state stress. The dislocation density is the major microstructural parameter governing the mechanical behavior of the alloy for the studied experimental conditions. The Kocks-Mecking-Estrin formalism is adapted to a wide range of temperature and strain rate to predict the mechanical behavior.