Submitted by Haroudo Xavier Filho (haroudo.xavierfo@ufpe.br) on 2016-04-01T18:23:34Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese Juliana Carvalho da Silva UFPE.pdf: 7095359 bytes, checksum: d445a956305aec4d1e8bc5f1753f949b (MD5) / Made available in DSpace on 2016-04-01T18:23:34Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Tese Juliana Carvalho da Silva UFPE.pdf: 7095359 bytes, checksum: d445a956305aec4d1e8bc5f1753f949b (MD5) Previous issue date: 2015-07-31 / CAPES / O petróleo, por sua relevância na economia global, demanda um volume crescente de pesquisas no setor e com isso a necessidade do uso de materiais resistentes à ambientes agressivos como é o caso do petróleo cru, gerando procedimentos eficazes e seguros que minimizem impactos ao meio ambiente. Revestimento termicamente aspergido tem sido intensamente utilizado na indústria de petróleo, aeroespacial, elétrica entre outros. Os revestimentos podem ser feitos de metal, cerâmica, vidros e a maioria dos plásticos, e o uso de um compósito adequado pode melhorar a resistência à corrosão em altas temperaturas. As cerâmicas apresentam alto ponto de fusão e são bons isolantes térmicos, porém apresentam baixa tenacidade e fragilidade. Estudos mostram que o uso de óxidos como ZrO2, TiO2 como reforços e de aditivos como óxidos de elementos de terras raras Y2O3, La2O3 podem melhorar a tenacidade da cerâmica à base de alumina. A primeira etapa desta pesquisa teve como objetivo a produção de compósitos cerâmicos à base de alumina, reforçados com 5%, 10%, 15%, 20% e 30% em peso de zircônia estabilizada com óxidos de terras raras La2O3 e Y2O3 variando entre 1 e 7%. A metodologia experimental utilizada consistiu da preparação do compósito cerâmico através da moagem em moinho de bolas, confecção de pastilhas por prensagem uniaxial em prensa hidráulica, e sinterização das amostras que foi realizada nas temperaturas de 13000C, 1350 0C e 14000C por 48h, com posteriores análises de absorção, dureza vickers, microscopia ótica, DRX e MEV. De posse dos resultados, numa segunda etapa a pesquisa foi direcionada à aplicação do compósito cerâmico Al2O3 – ZrO2 reforçado com óxido de ítrio em revestimento de chapas metálicas usadas na fabricação de tanques de armazenamento e transporte de petróleo depositado pelo processo de aspersão térmica a plasma – Atmospheric Plasma Spray, com e sem Bond coat (método de aspersão HVOF – High Velocity Oxi-Fuel), seguidos de ensaios para caracterização e pré-qualificação dos revestimentos como ensaios de adesão, riscamento e MEV. De um modo geral, os valores obtidos nos ensaios de adesão e as imagens de MEV indicam que o compósito estudado é adequado para revestimentos tipo barreira térmica para aplicação em ambientes corrosivos ao petróleo cru. / Oil, for its relevance in the global economy requires a growing body of research in the industry as well as need for the use of materials resistant to harsh environments such as crude oil, generating effective and safe procedures that minimize impacts on the environment . Thermally sprayed coating has been intensively used in the oil industry, aerospace, electrical and more. The coatings may be made of metal, ceramic, glass and most plastics, and the use of an appropriate composite can improve the corrosion resistance at high temperatures. Ceramics have a high melting point and are good insulators, but have low toughness and fragility. Studies show that the use of oxides such as ZrO2, TiO2 as fillers and additives such as oxides of rare earth elements Y2O3, La2O3 can improve the toughness of alumina based ceramic. The first step of this research was aimed at the production of ceramic composites based on alumina reinforced with 5%, 10%, 15%, 20% and 30% zirconia weight stabilized with rare earth La2O3 and Y2O3 oxides ranging from 1 and 7%. The used experimental methodology consisted of the preparation of ceramic composite by grinding in ball mill, preparation of pellets by uniaxial pressing in a hydraulic press, and sintering of the samples was performed at temperatures of 13000C, 13500C and 14000C for 48 hours with subsequent analysis absorption, Vickers hardness, optical microscopy, XRD and SEM. With the results in a second step the research was directed to the application of the ceramic composite Al2O3 - ZrO2 reinforced with yttrium oxide coating of sheet metal used in the manufacture of storage tanks and transport of oil deposited by thermal spray process the plasma - Atmospheric Plasma Spray, with and without bond coat (HVOF spraying method - High Velocity Oxy-Fuel), followed by assays for characterization and classification of pre-testing coatings such as adhesion, scratching and SEM. In general, the values obtained in the adhesion tests and SEM images indicate that the composite studied is suitable for thermal barrier-type coatings in corrosive environments for application to the crude oil.

This Thesis is about the aging of FECRAL surface coatings. In this thesis various substrates have been investigated such as 16 Mo3, 304, 347, Sanicro 31, 800HT, Nikrothal 80 and Kanthal APMT. These substrates have been coated with different FeCrAl alloys, using two different coating methods spraying with (High Velocity Air Force) and welding with (Metal Inert Gas). The purpose of coating is to achieve specific properties of the layer without affecting the original properties of the substrate. Therefore, it is important to investigate the boundary layer between these two different materials to observe how the interdiffusion of different substances such as Cr, Al, Fe and C is affected, which is the purpose of this project. The method used to investigate this purpose was to expose these combinations in different temperatures and in different environments for different time intervals. Then, using LOM, SEM and EDS analysis, the change that the boundary layers have undergone is examined. Some calculations in DICTRA have also been performed to see if it was possible to find any connection between experimental data and simulation results. The result showed carburization of FeCrAl-coatings on 16Mo3 substrates which can lead to deterioration of mechanical properties in the substrates but also decreased corrosion resistance for the coated layers. The result has also shown that it is difficult to perform spraying for small cylindrical products. The reason for this may be the high powder dispersion and the expansion of certain products when spraying, which causes the layer to loosen due to the shrinkage followed by cooling. APMT sprayed with Nikrothal 80 has shown high porosity in the substrates and high interdiffusion of Fe and Ni. High Ni diffusion in low Al alloys such as K 198 may be a reason why the coated layer cannot optimally form the protective oxide. / Detta projekt handlar om åldring av FECRAL ytbeläggningar. I den här avhandlingen så har olika substrat blivit undersökta såsom 16Mo3, 304, 347, Sanicro 31, 800HT, Nikrothal 80 och Kanthal APMT. Dessa substrat har blivit belagda med olika FeCrAl legeringar, med hjälp av två olika beläggningsmetoder, påsprutning (High Velocity Air Force) och påsvetsning (Metal Inert Gas). Syftet med att materialet beläggs är att uppnå specifika egenskaper utan att påverka substratens ursprungliga egenskaper. Det är därför viktigt att undersöka gränsskiktet mellan dessa två olika material för att se hur interdiffusionen av olika element såsom Cr, Al, Fe och C påverkas av värmebehandling. Metoden som användes för att undersöka detta var att exponera dessa kombinationer i olika temperaturer och i olika miljöer för olika tidsintervall. Därefter med hjälp av LOM, SEM och EDS analys undersöktes förändringen som gränsskikten har genomgått. Några beräkningar i DICTRA har även utförts för att se om det var möjligt att hitta någon koppling mellan experimentella data och simuleringsresultatet. Resultaten visade att 16Mo3 kombinationer fått en tydlig hög uppkolning i skiktet vilket kan påverka mekaniska egenskaperna och korrosionbeständigheten under användning vid höga temperaturer. Resultatet har även visat att det är svårt att utföra påsprutning för små cylindriska produkter. Anledningen till detta kan vara hög pulverspridningen samt den termiska expansionen av vissa produkter vid påsprutning som leder till att skiktet kan lossna på grund av krympningen vid svalning. APMT påsprutad med Nikrothal 80 har visat hög porositet i substraten och hög interdiffusion av Fe, Al och Ni under exponering vid 1200°C. Hög uppblandning och diffusion av nickel för det FECRAL belagda skiktet med relativt låg halt av aluminium K 198 kan vara en anledning till att belagda skiktet inte kan forma en skyddande oxid på ett optimalt sätt.

Neste trabalho, visando-se melhorar o desempenho ao desgaste e/ou à corrosão de revestimentos de ligas auto-fluxantes, amostras de aço SAE 1020 foram revestidas pelo processo de aspersão térmica, sendo que uma delas foi revestida apenas com uma liga auto-fluxante a base de níquel (\'NI\"CR\"B\"SI\"C\') e outras duas, às quais aplicou-se essa liga com adições de carboneto de boro ou carboneto de silício. As camadas foram caracterizadas por meio de ensaios micrográficos ópticos e eletrônicos, microdurezas, corrosão e de microdesgaste. A camada adicionada com carboneto de boro apresentou o maior nível de dureza e melhor desempenho ao desgaste, seguida pela camada com carboneto de silício e a liga auto-fluxante pura. As amostras adicionadas de carboneto de boro e silício apresentaram comportamentos similares à corrosão, com potenciais de corrosão superiores ao da amostra sem adição. / In this work, aiming to improve the wear and/or corrosion performance of self-fluxing alloys coatings, samples SAE 1020 steel were coated by thermal spray process, one of then was coated only with a self-fluxing nickel-based (\'NI\"CR\"B\"SI\"C\') alloy and two others, in which was applied this alloy with additions of boron carbide or silicon carbide. The coatings were characterized by means of optical and electronic micrography, microhardness, corrosion and microwear tests. The coating added with boron carbide showed the highest level of hardness and the better wear performance, followed by the coating with silicon carbide and the pure self-fluxing alloy. The samples added with boron or silicon carbide showed similar corrosion performance, with higher corrosion potential in comparison to that presented by the sample without addition.

Neste trabalho, visando-se melhorar o desempenho ao desgaste e/ou à corrosão de revestimentos de ligas auto-fluxantes, amostras de aço SAE 1020 foram revestidas pelo processo de aspersão térmica, sendo que uma delas foi revestida apenas com uma liga auto-fluxante a base de níquel (\'NI\"CR\"B\"SI\"C\') e outras duas, às quais aplicou-se essa liga com adições de carboneto de boro ou carboneto de silício. As camadas foram caracterizadas por meio de ensaios micrográficos ópticos e eletrônicos, microdurezas, corrosão e de microdesgaste. A camada adicionada com carboneto de boro apresentou o maior nível de dureza e melhor desempenho ao desgaste, seguida pela camada com carboneto de silício e a liga auto-fluxante pura. As amostras adicionadas de carboneto de boro e silício apresentaram comportamentos similares à corrosão, com potenciais de corrosão superiores ao da amostra sem adição. / In this work, aiming to improve the wear and/or corrosion performance of self-fluxing alloys coatings, samples SAE 1020 steel were coated by thermal spray process, one of then was coated only with a self-fluxing nickel-based (\'NI\"CR\"B\"SI\"C\') alloy and two others, in which was applied this alloy with additions of boron carbide or silicon carbide. The coatings were characterized by means of optical and electronic micrography, microhardness, corrosion and microwear tests. The coating added with boron carbide showed the highest level of hardness and the better wear performance, followed by the coating with silicon carbide and the pure self-fluxing alloy. The samples added with boron or silicon carbide showed similar corrosion performance, with higher corrosion potential in comparison to that presented by the sample without addition.

The proposed dissertation thesis deals with the characterization of HVOF and APS-thermally sprayed coatings prepared on the AZ31 and AZ91 magnesium substrates. The theoretical part of the thesis describes in-detail Mg substrates used in the experimental part of the thesis. There are also characterized materials and coatings based on NiCrAlY and FeCrNiMoSiC metals, WC-CoCr cermets, and YSZ ceramic materials. At the end of the theoretical part, the literary research summarizing the characterization and analysis performed on thermally sprayed coatings on Mg alloys. Based on the theoretical knowledge, the characterization of Mg substrates and deposited coatings was performed in terms of the surface morphology, microstructure, and the chemical composition using the light microscopy (LM) and scanning electron microscopy with energy-dispersive spectroscopy (SEM+EDS). The phase composition of the coatings was analyzed using the X-ray diffraction (XRD). The diffractions corresponding to the sprayed coatings were compared with the feedstock powders, i.e. materials used for the spraying of the coatings. The characterization of the prepared coatings in terms of the mechanical and tribological properties was performed. The hardness and microhardness of the coatings as well as the coefficient of friction, and the wear rate were measured. The last chapter of the experimental part deals with the evaluation of the electrochemical corrosion properties by the potentiodynamic measurements in a 3.5% NaCl solution. In the case of exposed samples, the evaluation of the surface and coating/substrate interface was performed using LM and SEM with EDS. The mechanism of the corrosion attack and degradation was determined from the acquired knowledge and base on the results of the short-term measurements. Based on the measured results, it can be stated that the deposited coatings were successfully applied on the surface of both Mg alloys. All the coatings increase the surface hardness of the Mg alloys and significantly improve their tribological properties. However, except for FeCrNiMoSiC coatings, the corrosion properties of Mg alloys deteriorate due to the fact that the corrosion environment can pass through the coating to the less noble Mg substrate and the corrosion microcells are created.

Thermochemische Randschichthärteverfahren ermöglichen eine ausscheidungsfreie Einlagerung von Kohlenstoff bzw. Stickstoff innerhalb des austenitischen Mischkristalls. Im Zusammenhang mit einer Randschichtbehandlung thermisch gespritzter Schichtsysteme stellen die charakteristischen Strukturmerkmale eine bislang weitgehend unerforschte Einflussgröße für die Beurteilung von Diffusionsprozessen dar. Bei der Verarbeitung von randschichtgehärtetem Pulver durch Verfahren des thermischen Spritzens ist die Phasenstabilität des Spritzzusatzwerkstoffs von übergeordneter Bedeutung. Die beiden Möglichkeiten einer Verfahrenskombination werden für hochgeschwindigkeitsflamm- und atmosphärisch plasmagespritzte Schichtsysteme des Werkstoffs EN 1.4404 durch systematische Prozess- und Parametervariation eingehend betrachtet. Für die einzelnen Schichtsysteme werden Einflussfaktoren struktur- und prozessspezifisch sowie in Abhängigkeit vom Anreicherungsmedium erfasst und im Kontext der Massivwerkstoffreferenz eingeordnet. Die daraus abgeleiteten allgemeingültigen Aussagen zu verfahrenstechnischen Wechselwirkungseffekten ermöglichen eine anwendungsorientierte Verfahrensauswahl bzw. Entwicklungsstrategie. / Thermochemical surface hardening enables a precipitation-free solvation of carbon or nitrogen on interstices of the austenitic crystal lattice. However, the interplay of the diffusion mechanisms with the structural properties of thermal spray coatings has not yet been understood. Thermal spraying of surface-hardened powders is a further opportunity, where the phase stability of the feedstock material is of crucial importance. A process and parameter study is conducted on high velocity oxy-fuel and atmospheric plasma spraying of AISI 316L considering both basic concepts. Structural and process-specific influence factors are examined for the different coating systems in comparison to the bulk material reference. Correlation effects are determined allowing for an application-oriented process selection or development strategy.

A solution-hardening of AISI 316L stainless-steel powder was conducted. The expansion of the crystal lattice and a strong increase in the nanoindentation hardness confirm the successful diffusion of carbon and nitrogen in the interstices. A multiphase state of the powder feedstock with phase fractions of the metastable S-phase (expanded austenite) mainly at the particle’s edge, and the initial austenitic phase within the core was found. Thermal spraying using high velocity oxy-fuel (HVOF) and atmospheric plasma spraying (APS) prove the sufficient thermal stability of the Sphase. Microstructural investigations of the HVOF coating reveal the ductility of the S-phase layer, while the higher heat load within the APS cause diffusion processes with the initial austenitic phase. The lattice expansion and the nanoindentation hardness decrease during thermal spraying. However, the absence of precipitates ensures the sufficient heat stability of the metastable S-phase. Even though further efforts are required for the thermochemical treatment of powder feedstock, the results confirm the feasibility of the novel powder treatment approach.

Gas nitriding is known as a convenient process to improve the wear resistance of steel components. A precipitation-free hardening by low-temperature processes is established to retain the good corrosion resistance of stainless steel. In cases of thermal spray coatings, the interstitial solvation is achieved without an additional surface activation step. The open porosity permits the penetration of the donator media and leads to a structural diffusion. An inhomogeneous diffusion enrichment occurs at the single spray particle edges within the coating’s microstructure. A decreasing diffusion depth is found with increasing surface distance. The present study investigates an adjusted process management for low-temperature gas nitriding of high velocity oxy-fuel-sprayed AISI 316L coatings. To maintain a homogeneous diffusion depth within the coating, a pressure modulation during the process is studied. Additionally, the use of cracked gas as donator is examined. The process management is designed without an additional surface activation step. Regardless of surface distance, microstructural investigations reveal a homogeneous diffusion depth by a reduced processing time. The constant hardening depth allows a reliable prediction of the coatings’ properties. An enhanced hardness and improved wear resistance is found in comparison with the as-sprayed coating condition.