Organic coatings are frequently applied to metals, often in circumstances where there is a need to protect the substrate from corrosion or to improve the aesthetic quality of a product. Increasingly, coatings are also expected to provide additional functionality, such as anti-bacterial properties. Concurrent with the need to satisfy ever more demanding specifications, coating formulators are being obliged to comply with stringent environmental legislation. A research area which may benefit the development of coating formulations is that of nanocomposite synthesis, in which the composite additives have at least one dimension in the nanometre size range. The current research has sought to modify a waterborne organic coating primer with two types of nano-sized additives: layered clays and titanium dioxide nanoparticles. Dispersion of the particles at loadings up to 5% w/w was achieved by ball milling and the modified coatings were subjected to numerous tests to ascertain the effect of the additives. Titanium dioxide was found to improve the tribological properties and corrosion resistance of the coatings, while the addition of magnesium aluminium hydroxycarbonate (hydrotalcite) layered clay had a deleterious effect. Some coatings exhibited a cracked morphology, although no correlation between particle loading and the presence of cracks could be determined. A preliminary investigation into substrate preparation was also conducted. This ensured that the degree of cleanliness of the hot-dip galvanized substrates was both satisfactory and consistent.

Zinc and its alloys are among the most widely utilised metallic coatings for the sacrificial protection of steel. Although excellent in this mode of protection, these coatings are often less durable when subjected to environments of combined wear and corrosion due to their intrinsic relative softness and ductility. A possible and fast growing way of improving the durability of these coating is by the codeposition of inert particles into the zinc and zinc-alloy matrix. The main aim of this research was therefore to improve the durability of zinc and zinc-nickel coatings by the incorporation of inert particles via electrolytic codeposition methods. The first five chapters of this thesis comprise literature review on the electrodeposition of zinc, its alloys and composite electrodeposition in general. A major part of which was dedicated to the review of various conventional methods and parameters such as current density, agitation, temperature, solution composition, bath additives and pH usually investigated in electrodeposition. The experimental work was principally based on DC electrodeposition and was aimed at understanding the deposition behaviour of zinc and zinc-nickel electrodeposition baths, conditions which influence them and solution compatibility to the introduction of silica particles. A systematic study on the deposition behaviour of both zinc/silica and zinc-nickel/silica composite baths was carried out with particular interest on the rate of particle incorporation and the influence of particles on zinc-nickel alloy deposition. The complimentary codeposition behaviour of the nickel and silica particles was observed. The influence of bath additives such as N,N Dimethyldodecylamine (NND) and sodium nitrate on the rate of silica incorporation was also studied. Both additives were found to improve the rate of particle incorporation for the zinc/silica. The morphologies and compositions of the coatings were analysed with the use of SEM and FEGSEM. Corrosion performance studies were carried out in a neutral salt spray chamber and linear polarisation resistance methods used to determine barrier corrosion properties of the coatings. Anodic polarisation studies were also carried out. The results show an improvement in the corrosion performance of these coatings with the addition of silica particles Reciprocating wear tests were used to determine the wear behaviour of the coatings in terms of weight loss. Improvement in wear resistance was not observed in the zinc/silica coatings probably due to the high content of silica in the coatings. Lower silica contents may be required for the desired improvements. However, there were obvious improvements in the wear behaviour of the zinc-nickel/silica coatings due to the presence of the silica particles.

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.

<div>Magnesium alloys are regarded as the most promising structure materials in transportation and aerospace fields because of their low densities and high specific strengths. However, the unsatisfactory mechanical performance and corrosion resistance restrict their applications. Grain refinement is an effective way to improve the mechanical properties and widen the applications. Among which, ultrasonic shot peening shows a great potential in producing refined grains or even nanocrystalline. A nanocrystalline forms at the surface after ultrasonic shot peening treatment. The formed nanocrystalline has been proved to dramatically affect the mechanical properties, such as hardness, mechanical stress, wear resistance and fatigue life. </div><div><br></div><div> </div><div>In this dissertation, the microstructure evolution of AZ31 Mg alloy after the ultrasonic shot peening as well as its effect on the mechanical properties are investigated. The grain size, the twin structure, the surface roughness and the residual stress distribution after ultrasonic shot peening are characterized. A gradient nanostructure is achieved through ultrasonic shot peening and the thickness of this gradient nanostructure increases with prolonging the treated time. The grains at the top surface after 5 min treatment is refined to 45 nm and further refined to 42 nm for 10 min and 37nm for 15 min treatment from the XRD result. A lamellar nanocrystaline is below the top surface and a lot of tensile twins are found at the heavily deformed grains below the nanocrystalline layer. Below the twinned layer, a residual stress is distributed as deep as 400 $\mu$m in the matrix. A rough surface is obtained and the surface roughness of the 5 min treated sample was 5.934 $\mu$m, increased to 6.161 $\mu$m for10 min and 6.236 $\mu$m for 15 min. The nanocrystalline leads to the improvement of the microhardness, from 65 HV of the as-received to 123 HV, 127 HV and 145 HV for 5 min, 10 min and 15 min treatment, respectively. The tensile stress and compression stress are also improved remarkably. The yield stress is increased from 127.7 MPa of as-received to 198 MPa of 10 min treated sample and the compression stress is improved from 73 MPa to 100 MPa. The improved yield stress is attributed to the grain refinement and the work hardening of the nanocrystalline. </div><div><br></div><div> </div><div> </div><div>The wear resistance of AZ31 Mg alloy is improved greatly after ultrasonic shot peening process. The coefficient of friction and the wear rate of the ultrasonic shot peening treated sample are both lower than that of as-received. The width of the wear track of ultrasonic shot peening treated is also narrower than that of as-received, and the worn surface has a lower surface roughness. In as-received samples, abrasion and oxidation dominate the wear mechanism at low sliding speed and low applied load. The increase of sliding speed or applied load resulted in the delamination. Severe wear such as thermal softening happens with the further increase of load value or sliding speed. In ultrasonic shot peening treated samples, oxidation, the abrasion and delamination are also existing while no severe wear is found. The improved wear resistance of the ultrasonic shot peened sample is due to the improved hardness and a higher activity of oxidation during wear process. The nanocrystalline on the top surface leads to the the transition boundary between the mild wear and severe wear to a higher sliding speed and higher applied load. </div><div><br></div><div><br></div><div>The corrosion resistance of AZ31 Mg alloy before and after ultrasonic shot peening is tested in 3.5 $\%$ NaCl solution. The corrosion resistance after ultrasonic shot peening is reduced greatly because of the Fe particles at the top surface, which was exfoliated from the shot during the treating process. After a 40 $\mu$m thick polishing, Fe particles are removed totally and the corrosion resistance is improved, compared with that of as-received. The anodic current density of the nanocrystallized surface after polishing is reduced because of the compression residual stress and a rapid formation of protective layer. Meanwhile, the grain boundary acts as a physical barrier for corrosion and reduces the corrosion rate. </div><div><br></div><div><br></div><div>The bending behavior of AZ31 Mg alloy before and after ultrasonic shot peening is studied by a V-bending test. The ultrasonic shot peening treated sample has a similar bending performance even though the ductility has been reduced after ultrasonic shot peening. A single side ultrasonic shot peening (either at the inner side or the outer side) changed the bending behavior because of its asymmetric structure. The ultrasonic shot peening at the inner side for 5 min improves the bendability and longer treated, such as 10 min and 15 min degenerates the bendability to as-received. The improved bendability of 5 min treated sample is due to the drawing back of the neutral layer. The ultrasonic shot peening at the outer side for 5 min also improves the bending performance and a longer treatment of 15 min further enhanced the bendability. The improved bendability after outer side treatment is due to the high yield stress of nanocrystalline at the convex, resulting in the smaller strain here. </div>

O uso de ligas metálicas na odontologia continua tendo aplicação em grande número de situações clínicas de próteses convencionais ou sobre implantes. O objetivo deste estudo foi avaliar a corrosão superficial do Ti cp, submetido a processo de escovação. Foram confeccionados espécimes, com 15,0 mm de diâmetro e 2,5 mm de espessura, obtidos pelo método de fundição por cera perdida. Em seguida, divididos em 4 grupos (n=6). Ensaios eletroquímicos e escovação mecânica (abrasão) foram realizados. Para a análise de Potencial em Circuito Aberto (OCP), o período de mensuração foi de 1 hora, com leitura do potencial da amostra a cada 0,6 segundos. No Grupo G1 foi realizada a análise de Pontecial em Circuito Aberto (OCP), em seguida, aplicado um Potencial Anódico a -250 mV por 1 hora e logo após, realizada a Espectroscopia de Impedância Eletroquímica (EIS) à -250mV. Para o Grupo G2 foi realizada a análise de OCP, em seguida, aplicado um Potencial Catódico a +1000 mV por 1 hora e logo após, realizada a EIS à +1000 mV. Os Grupos G1 e G2 não foram submetidos ao teste de escovação mecânica. O Grupo G3 foi submetido, primeiramente, ao ensaio de escovação mecânica, sendo a máquina acionada até atingir 14.600 ciclos, que representa 1 ano de escovação por um indivíduo saudável52 e corresponde a 41 minutos de funcionamento do equipamento. Posteriormente, foi realizada a mesma sequência do ensaio corrosivo do Grupo G1, ou seja: OCP + Aplicação de Potencial anódico à -250mV + EIS à -250 mV. Para o Grupo G4 primeiro foi realizado o ensaio de escovação mecânica, (14.600 ciclos). Em seguida, foi realizado a mesma sequência do ensaio corrosivo do Grupo G2 , ou seja: OCP + Aplicação de Potencial Catódico à +1000 mV + EIS a +1000 mV. Os resultados obtidos mostram não haver alteração estatisticamente significante na rugosidade superficial dos corpos-de-prova entre os grupos testados. No entanto, as imagens obtidas através dos testes de Interferometria Digital 3D e Microscopia eletrônica de varredura, sugerem a formação de superfícies com menos irregularidades, para os grupos 3 e 4, os quais foram submetidos a escovação mecânica antes dos ensaios eletroquímicos. Os valores da resistência do óxido (Róxido) observada após a EIS á -250 mV (grupos 1 e 3) e á + 1000 mV (grupos 2 e 4) foram estaticamente diferentes entre si (p&le;0,05), sendo que os grupos 1 e 2 , submetidos somente ao teste eletroquímico, demonstraram menor resistência do óxido, quando comparados com os grupos 3 e 4, escovados mecanicamente antes do teste eletroquímico. Concluiu-se que a escovação interfere positivamente na resistência a corrosão do Ti cp. / The use of metal alloys in dentistry continues to have application in many clinical situations of conventional prosthesis and implants. The aim of this study was to evaluate the effect of brushing and corrosion on the cp Ti surface. Specimens were prepared with 15.0 mm diameter and 2.5 mm thickness, obtained by the method of lost wax casting. Then divided into 4 groups (n=6). Electrochemical tests and mechanical brushing (abrasion) were performed. For the analysis of Open Circuit Potential (OCP), the measurement period was 1 hour, with the potential of sample reading every 0.6 seconds. For Group G1 Pontecial Open Circuit (OCP) analysis was performed, then applying a Anode potential at -250 mV for 1 hour and soon after, performed the Electrochemical Impedance Spectroscopy (EIS) at -250mV. For the Group G2 OCP analysis was performed, then applying a Cathodic Potential at +1000 mV for 1 hour and soon after, performed the EIS at +1000 mV. The Groups G1 and G2 were not subjected to mechanical brushing test. The Group G3was submitted, first, the mechanical brushing, and the machine was thrown up to 14,600 cycles, which represents 1 year of brushing for a healthy individual [52] and corresponds to 41 minutes of operation of the equipment. Subsequently, the same sequence of G1 Group corrosive test was performed (OCP + Potential Application of anodic at - 250mV + EIS at -250 mV). For the group G4, first mechanical brushing (14,600 cycles) was performed. Then was performed the same sequence of Group G2 corrosive test, (OCP + Application of Cathodic Potential at +1000 mV + EIS at +1000 mV). The results showed no statistical significance change of surface roughness between the tested groups. However, the images obtained through the 3D Digital interferometry and scanning electron microscopy tests , suggest the formation of surfaces with less irregularities, for groups 3 and 4, which were subjected to mechanical brushing before the electrochemical tests. The oxide resistance values (Róxido) observed after the EIS at -250 mV (groups 1 and 3) and at +1000 mV (groups 2 and 4) were statistically different ( p &le; 0.05 ), and the groups 1 and 2 ,subjected only to the electrochemical test showed less oxide resistance when compared with groups 3 and 4, mechanically brushed before the electrochemical testing. It was concluded that brushing positively interferes at the corrosion resistance of cp Ti.

As ligas a base de Níquel são frequentemente utilizadas na indústria do petróleo devido à elevada resistência mecânica e excelente resistência à corrosão. Neste cenário, a utilização da soldagem como etapa na fabricação de dutos rígidos de grande comprimento é inevitável. Assim, chapas da liga Inconel 625® foram unidas através do processo Friction Stir Welding (FSW). A soldagem foi executada com uma ferramenta de nitreto cúbico de boro policristalino e o inerente desta ferramenta foi analisado. Em um primeiro momento, na seleção de parâmetros de processo, diversas condições de processo foram analisadas para escolha da melhor solda. Após esta etapa, novas juntas soldadas foram produzidas com o parâmetro de processo adequado (velocidade de rotação da ferramenta de 200 rpm e velocidade de avanço de 1 mm/s). A caracterização da superfície de topo da solda foi realizada através da microscopia ótica, microscopia eletrônica de varredura, microdureza e ensaios de dobramento. Defeitos superficiais foram inspecionados com líquidos penetrantes. Além disso, os estados de tensões residuais foram obtidos com a difração de raios-X. Ainda, a resistência à corrosão localizada foi estudada com o ensaio de imersão em cloreto férrico e a determinação da temperatura crítica de pite (conhecida como CPT) Por fim, a susceptibilidade à corrosão intergranular foi avaliada com o ensaio Streicher Test. O processo de soldagem promoveu o refino de grão e o aumento de dureza na solda. As micrografias do metal de base (MB) mostraram carbonetos do tipo MC, M6C, M23C6. Por outro lado, a melhor junta soldada apresentou uma microestrutura livre de defeitos, homogênea, onde não foram percebidos carbonetos do tipo M6C, M23C6 nos contornos de grão, foi aprovada nos ensaios de dobramento, líquidos penetrantes e imersão em FeCl3. Entretanto, ocorreu o um desgaste da ferramenta, mas reduzido e aceitável para esta solda. Tensões residuais longitudinais trativas da ordem de 50 MPa foram observadas na zona de mistura. Considerando o valor médio, o MB alcançou uma CPT de 77 °C, enquanto no centro da solda a CPT foi de 86°C. A taxa de corrosão média alcançada após o ensaio de corrosão intergranular foi de 0,4406 mm/ano, valor que sugere uma boa qualidade da solda. / Nickel based alloys are often used in the oil and gas industry due to their great mechanical strenght as well as excelent corrosion resistance. In this scenario, welding as manufacturing step for long lenght rigid tubes is inevitable. Therefore, Inconel 625® sheets were joined by Friction Stir Welding (FSW). The welding was performed with a Polycrystalline Cubic Boron Nitride (pcBN) tool and the unavoidable tool wear was verified. At first, in the process parameter development step, different process conditions were analyzed for choosing the best welded joint. Afterwards, new welded joints were produced with the suitable process parameter (tool rotational speed of 200 rpm and welding speed of 1 mm/s). Top surface characterization of friction-stir-welded Inconel 625 was carried out by optical microscopy, scanning electron microscopy, microhardness and bending tests. Surface defects were verified by dye penetrant inspection (DPI). In addition, residual stress states were obtained by X-ray diffraction. Furthermore, localized corrosion resistance was studied by the immersion test in FeCl3 and the critical pitting temperature (CPT) determination. Finally, the susceptibility to intergranular corrosion was evaluated by Streicher Test. FSW process promoted grain refining as well as increased microhardness in the joint Base material micrographs showed different carbides as MC, M6C, M23C6. On the other hand, the best joint presented a sounds weld without defetcs, homogeneous microstructure, grain boundaries free of M6C, M23C6 carbides, approved in bending tests, DPI and the immersion test. However, a tool wear was also noted, but reduced and acceptable for this weld. Tensile longitudinal residual stresses of 50 MPa were observed in the stir zone. As an avarage, the base material CPT was 77 °C, while the CPT was 86 °C at the weld center. The mean corrosion rate after intergranular corrosion test was 0.4406 mm/year, a value which suggests a good weld quality.

<p>For patients suffering bradycardia, i.e., too slow heart rhythm, the common treatment is having a pacemaker implanted. The pacemaker system consists of the pacemaker and a pacing lead. The pacing lead is connected to the pacemaker and at the other end there is a stimulation electrode. The most common conductor material is a cobalt-based super alloy (MP35N^® or 35N LT^®), with the main constituents Ni, Co, Cr and Mo. The pacemaker electrode is often made of a substrate material with a rough surface coating. The substrate materials are predominantly platinum/iridium alloy and titanium. The material choice is of great importance for the performance and stability during long-term service. Excellent corrosion resistance is required to minimize elution of metal ions in the human body.</p><p>In this thesis, the electrochemical behaviour and corrosion resistance of the Co-based alloys and Ta (as electrode substrate), in a phosphate buffer saline (PBS) solution with and without addition of H₂O₂, was investigated by means of potentiodynamic polarization, cyclic voltammetry, electrochemical impedance spectroscopy and simulated pacemaker pulsing. The metal release from the Co-based alloy during the passivation treatment and exposure in the synthetic biological media was measured by using inductive coupled plasma - atomic emission spectroscopy (ICP-AES). Moreover, surface composition was analyzed by using x-ray photoelectron spectroscopy.</p><p>The results show that the chemical passivation of Co-based alloy 35N LT^® increased the corrosion resistance and reduced Co release significantly, even in more hostile environment, i.e. PBS with addition of H₂O₂. The increased corrosion resistance is due to the Cr enrichment in the surface layer. The reduced Co release is due to a preferential dissolution of Co from the surface oxide layer during the chemical passivation. The electrochemical investigation of uncoated and rough TiN coated Ta show that uncoated Ta is not suitable electrode material due to formation of a highly resistive surface oxide film. Whereas the rough TiN coated Ta exhibits desirable electrochemical performance for pacemaker electrodes. The addition of H₂O₂in the PBS has a large influence on the electrochemical behaviour of Ta, but the influence is small on the rough TiN coated Ta. </p>

O uso de ligas metálicas na odontologia continua tendo aplicação em grande número de situações clínicas de próteses convencionais ou sobre implantes. O objetivo deste estudo foi avaliar a corrosão superficial do Ti cp, submetido a processo de escovação. Foram confeccionados espécimes, com 15,0 mm de diâmetro e 2,5 mm de espessura, obtidos pelo método de fundição por cera perdida. Em seguida, divididos em 4 grupos (n=6). Ensaios eletroquímicos e escovação mecânica (abrasão) foram realizados. Para a análise de Potencial em Circuito Aberto (OCP), o período de mensuração foi de 1 hora, com leitura do potencial da amostra a cada 0,6 segundos. No Grupo G1 foi realizada a análise de Pontecial em Circuito Aberto (OCP), em seguida, aplicado um Potencial Anódico a -250 mV por 1 hora e logo após, realizada a Espectroscopia de Impedância Eletroquímica (EIS) à -250mV. Para o Grupo G2 foi realizada a análise de OCP, em seguida, aplicado um Potencial Catódico a +1000 mV por 1 hora e logo após, realizada a EIS à +1000 mV. Os Grupos G1 e G2 não foram submetidos ao teste de escovação mecânica. O Grupo G3 foi submetido, primeiramente, ao ensaio de escovação mecânica, sendo a máquina acionada até atingir 14.600 ciclos, que representa 1 ano de escovação por um indivíduo saudável52 e corresponde a 41 minutos de funcionamento do equipamento. Posteriormente, foi realizada a mesma sequência do ensaio corrosivo do Grupo G1, ou seja: OCP + Aplicação de Potencial anódico à -250mV + EIS à -250 mV. Para o Grupo G4 primeiro foi realizado o ensaio de escovação mecânica, (14.600 ciclos). Em seguida, foi realizado a mesma sequência do ensaio corrosivo do Grupo G2 , ou seja: OCP + Aplicação de Potencial Catódico à +1000 mV + EIS a +1000 mV. Os resultados obtidos mostram não haver alteração estatisticamente significante na rugosidade superficial dos corpos-de-prova entre os grupos testados. No entanto, as imagens obtidas através dos testes de Interferometria Digital 3D e Microscopia eletrônica de varredura, sugerem a formação de superfícies com menos irregularidades, para os grupos 3 e 4, os quais foram submetidos a escovação mecânica antes dos ensaios eletroquímicos. Os valores da resistência do óxido (Róxido) observada após a EIS á -250 mV (grupos 1 e 3) e á + 1000 mV (grupos 2 e 4) foram estaticamente diferentes entre si (p&le;0,05), sendo que os grupos 1 e 2 , submetidos somente ao teste eletroquímico, demonstraram menor resistência do óxido, quando comparados com os grupos 3 e 4, escovados mecanicamente antes do teste eletroquímico. Concluiu-se que a escovação interfere positivamente na resistência a corrosão do Ti cp. / The use of metal alloys in dentistry continues to have application in many clinical situations of conventional prosthesis and implants. The aim of this study was to evaluate the effect of brushing and corrosion on the cp Ti surface. Specimens were prepared with 15.0 mm diameter and 2.5 mm thickness, obtained by the method of lost wax casting. Then divided into 4 groups (n=6). Electrochemical tests and mechanical brushing (abrasion) were performed. For the analysis of Open Circuit Potential (OCP), the measurement period was 1 hour, with the potential of sample reading every 0.6 seconds. For Group G1 Pontecial Open Circuit (OCP) analysis was performed, then applying a Anode potential at -250 mV for 1 hour and soon after, performed the Electrochemical Impedance Spectroscopy (EIS) at -250mV. For the Group G2 OCP analysis was performed, then applying a Cathodic Potential at +1000 mV for 1 hour and soon after, performed the EIS at +1000 mV. The Groups G1 and G2 were not subjected to mechanical brushing test. The Group G3was submitted, first, the mechanical brushing, and the machine was thrown up to 14,600 cycles, which represents 1 year of brushing for a healthy individual [52] and corresponds to 41 minutes of operation of the equipment. Subsequently, the same sequence of G1 Group corrosive test was performed (OCP + Potential Application of anodic at - 250mV + EIS at -250 mV). For the group G4, first mechanical brushing (14,600 cycles) was performed. Then was performed the same sequence of Group G2 corrosive test, (OCP + Application of Cathodic Potential at +1000 mV + EIS at +1000 mV). The results showed no statistical significance change of surface roughness between the tested groups. However, the images obtained through the 3D Digital interferometry and scanning electron microscopy tests , suggest the formation of surfaces with less irregularities, for groups 3 and 4, which were subjected to mechanical brushing before the electrochemical tests. The oxide resistance values (Róxido) observed after the EIS at -250 mV (groups 1 and 3) and at +1000 mV (groups 2 and 4) were statistically different ( p &le; 0.05 ), and the groups 1 and 2 ,subjected only to the electrochemical test showed less oxide resistance when compared with groups 3 and 4, mechanically brushed before the electrochemical testing. It was concluded that brushing positively interferes at the corrosion resistance of cp Ti.

Submitted by RAFAEL PARRA RIBEIRO null (rafa_parra1988@yahoo.com.br) on 2018-01-11T11:50:55Z No. of bitstreams: 1 Dissertação Versão FINAL 3.0.pdf: 3444946 bytes, checksum: 0a56c18e1734b605a90aea40283cc295 (MD5) / Approved for entry into archive by Maria Marlene Zaniboni null (zaniboni@bauru.unesp.br) on 2018-01-11T13:13:15Z (GMT) No. of bitstreams: 1 ribeiro_rp_me_bauru.pdf: 3444946 bytes, checksum: 0a56c18e1734b605a90aea40283cc295 (MD5) / Made available in DSpace on 2018-01-11T13:13:15Z (GMT). No. of bitstreams: 1 ribeiro_rp_me_bauru.pdf: 3444946 bytes, checksum: 0a56c18e1734b605a90aea40283cc295 (MD5) Previous issue date: 2017-08-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Devido às suas propriedades mecânicas, soldabilidade e baixo custo, o aço carbono é um material amplamente utilizado nos mais diversos setores. Entretanto, o aço carbono é facilmente oxidado quando exposto ao ambiente. Para evitar esse problema, alguns trabalhos sugerem o desenvolvimento de revestimentos protetivos utilizando técnicas de deposição a plasma baseadas no composto hexametildisiloxano, HMDSO. A partir deste composto podese obter desde estruturas organosilicones até as inorgânicas pela alteração dos parâmetros de deposição. Revestimentos tipo óxido de silício são mais resistentes à corrosão que os organosilicones, porém sua estabilidade física é menor. Com o objetivo de associar as propriedades favoráveis de ambos os tipos de revestimentos, investigou-se, no presente trabalho, a possibilidade de revestir o aço carbono com sistemas bicamadas SiOx/SiOxCyHz através da combinação de metodologia de deposição e oxidação em plasmas de baixa pressão. Para tanto, filmes do tipo SiOxCyHz foram depositados a plasma de mistura de HMDSO (70%), O2 (20%) e Ar (10%) excitado por radiofrequência (150 W). A pressão total da atmosfera de deposição foi de 20 Pa. Os filmes foram depositados por 30 min e, posteriormente, expostos a plasmas de O2 (3,3 Pa, 10-300 W, 60 min) com o objetivo de criar uma camada superficial inorgânica. Foram investigados os efeitos da potência de excitação do plasma de O2 na espessura de camada, estrutura química e composição elementar das amostras. Avaliou-se também o efeito da potência do plasma de oxidação nas propriedades de barreira do revestimento depositado sobre aço carbono. Filmes como-depositados foram caracterizados como organosilicones. A exposição ao plasma de oxigênio foi observada remover hidrogênio, carbono e grupos metil da estrutura transformando-a em óxido de silício, sendo, todavia, o grau de conversão e a espessura da camada convertida fortemente dependentes da potência do plasma de oxidação. A resistência do sistema preparado sobre o aço carbono à corrosão foi observada depender da espessura final da camada e também da conectividade da estrutura convertida em sílica mais que do grau de conversão. A condição de tratamento eleita como ótima neste trabalho foi a conduzida com 50 W de potência por criar uma camada superficial inorgânica fina, compacta, com uma estrutura superficial similar a da sílica além de preservar a espessura do filme e aumentar as propriedades de barreira do sistema. / Due to its mechanical properties, welding and low cost, carbon steel is a material widely used in several sectors. However, carbon steel is easily oxidized when exposed to the environment. To avoid this problem, some work suggests the development of protective coating using plasma deposition techniques based on the compound hexamethyldisiloxane, HMDSO. From this compound it is possible to obtain from organosilicones structures to inorganic by changing the parameters of deposition. Silicon oxide type coatings are more resistant to corrosion than organosilicones, but their physical stability is lower. With the objective of associating the favorable properties of both types of coatings, the present work investigated the possibility of coating the carbon steel with SiOx/SiOxCyHz bilayer systems through the combination of deposition and oxidation methodology in low pressure plasmas. For that, SiOxCyHz films were deposited in a mixture plasma of HMDSO (70%), O2 (20%) and Ar (10%) excited by radiofrequency (150 W). The total pressure of the atmosphere of deposition was 20 Pa. The films were deposited for 30 min and subsequently exposed to O2 plasmas (3.3 Pa, 10-300 W, 60 min) to create an inorganic surface layer. The effects of the excitation power of the O2 plasma on the layer thickness, chemical structure and elemental composition of the samples were investigated. The effect of the oxidation plasma power was also evaluated in the barrier properties of the coating deposited on carbon steel. As-deposited films were characterized as organosilicones. Exposure to oxygen plasma was observed to remove hydrogen, carbon and methyl groups from the structure transforming it into a silicon oxide, however, the degree of conversion and the thickness of the converted layer is strongly dependent on the power of the oxidation plasma. The corrosion resistance of the system prepared on carbon steel was observed to depend on the final thickness of the layer and also on the connectivity of the structure converted to silica rather than the degree of conversion. The treatment condition chosen as optimal in this work was the one conducted with 50 W of power by creating a thin, compact, inorganic surface layer with a silica-like surface structure in addition to preserving the film thickness and increasing the barrier properties of the system. / 1560670 / 1545023

As ligas a base de Níquel são frequentemente utilizadas na indústria do petróleo devido à elevada resistência mecânica e excelente resistência à corrosão. Neste cenário, a utilização da soldagem como etapa na fabricação de dutos rígidos de grande comprimento é inevitável. Assim, chapas da liga Inconel 625® foram unidas através do processo Friction Stir Welding (FSW). A soldagem foi executada com uma ferramenta de nitreto cúbico de boro policristalino e o inerente desta ferramenta foi analisado. Em um primeiro momento, na seleção de parâmetros de processo, diversas condições de processo foram analisadas para escolha da melhor solda. Após esta etapa, novas juntas soldadas foram produzidas com o parâmetro de processo adequado (velocidade de rotação da ferramenta de 200 rpm e velocidade de avanço de 1 mm/s). A caracterização da superfície de topo da solda foi realizada através da microscopia ótica, microscopia eletrônica de varredura, microdureza e ensaios de dobramento. Defeitos superficiais foram inspecionados com líquidos penetrantes. Além disso, os estados de tensões residuais foram obtidos com a difração de raios-X. Ainda, a resistência à corrosão localizada foi estudada com o ensaio de imersão em cloreto férrico e a determinação da temperatura crítica de pite (conhecida como CPT) Por fim, a susceptibilidade à corrosão intergranular foi avaliada com o ensaio Streicher Test. O processo de soldagem promoveu o refino de grão e o aumento de dureza na solda. As micrografias do metal de base (MB) mostraram carbonetos do tipo MC, M6C, M23C6. Por outro lado, a melhor junta soldada apresentou uma microestrutura livre de defeitos, homogênea, onde não foram percebidos carbonetos do tipo M6C, M23C6 nos contornos de grão, foi aprovada nos ensaios de dobramento, líquidos penetrantes e imersão em FeCl3. Entretanto, ocorreu o um desgaste da ferramenta, mas reduzido e aceitável para esta solda. Tensões residuais longitudinais trativas da ordem de 50 MPa foram observadas na zona de mistura. Considerando o valor médio, o MB alcançou uma CPT de 77 °C, enquanto no centro da solda a CPT foi de 86°C. A taxa de corrosão média alcançada após o ensaio de corrosão intergranular foi de 0,4406 mm/ano, valor que sugere uma boa qualidade da solda. / Nickel based alloys are often used in the oil and gas industry due to their great mechanical strenght as well as excelent corrosion resistance. In this scenario, welding as manufacturing step for long lenght rigid tubes is inevitable. Therefore, Inconel 625® sheets were joined by Friction Stir Welding (FSW). The welding was performed with a Polycrystalline Cubic Boron Nitride (pcBN) tool and the unavoidable tool wear was verified. At first, in the process parameter development step, different process conditions were analyzed for choosing the best welded joint. Afterwards, new welded joints were produced with the suitable process parameter (tool rotational speed of 200 rpm and welding speed of 1 mm/s). Top surface characterization of friction-stir-welded Inconel 625 was carried out by optical microscopy, scanning electron microscopy, microhardness and bending tests. Surface defects were verified by dye penetrant inspection (DPI). In addition, residual stress states were obtained by X-ray diffraction. Furthermore, localized corrosion resistance was studied by the immersion test in FeCl3 and the critical pitting temperature (CPT) determination. Finally, the susceptibility to intergranular corrosion was evaluated by Streicher Test. FSW process promoted grain refining as well as increased microhardness in the joint Base material micrographs showed different carbides as MC, M6C, M23C6. On the other hand, the best joint presented a sounds weld without defetcs, homogeneous microstructure, grain boundaries free of M6C, M23C6 carbides, approved in bending tests, DPI and the immersion test. However, a tool wear was also noted, but reduced and acceptable for this weld. Tensile longitudinal residual stresses of 50 MPa were observed in the stir zone. As an avarage, the base material CPT was 77 °C, while the CPT was 86 °C at the weld center. The mean corrosion rate after intergranular corrosion test was 0.4406 mm/year, a value which suggests a good weld quality.