Orientador: Amauri Garcia / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-09T07:59:55Z (GMT). No. of bitstreams: 1 Rosa_DanielMonteiro_D.pdf: 8184541 bytes, checksum: 0b8d932ad9a1091a507ea6b10e4185f8 (MD5) Previous issue date: 2007 / Resumo: As morfologias das estruturas de solidificação, caracterizadas principalmente por arranjos celulares e dendríticos, e suas grandezas representadas por espaçamentos celulares e dendríticos primários, secundários e terciários, controlam os perfis de segregação e a formação de segundas fases dentro das regiões intercelulares ou interdendríticas, que determinam as propriedades finais das estruturas fundidas. O presente trabalho pretende contribuir para o entendimento do desenvolvimento microestrutural de ligas binárias através da análise de dois sistemas binários que possuem elevada importância para a indústria na fabricação de peças fundidas automotivas e grades de baterias: Al-Si e Pb-Sb, respectivamente. Os experimentos realizados utilizaram dois diferentes dispositivos em que o calor é extraído somente pelo sistema de resfriamento a água, localizado no fundo (solidificação ascendente) e no topo (solidificação descendente) da lingoteira. As variáveis térmicas de solidificação foram determinadas pela leitura de temperaturas a partir de termopares posicionados dentro da lingoteira em diferentes posições em relação à superfície refrigerada. Estas variáveis térmicas foram confrontadas com as previsões teóricas de um modelo numérico de solidificação. Os aspectos macroestruturais e microestruturais foram caracterizados ao longo dos lingotes através de microscopia óptica. Para as ligas Al-Si foi realizada uma análise complementar do efeito da convecção térmica e constitucional nos espaçamentos dendríticos terciários na solidificação unidirecional transitória descendente. Ligas hipoeutéticas Pb-Sb foram utilizadas para analisar as influências das variáveis térmicas de solidificação e da concentração de soluto nas estruturas celulares, na transição celular/dendrítica e nas estruturas dendríticas. Os espaçamentos celulares e dendríticos foram comparados com as previsões teóricas fornecidas pelos principais modelos de crescimento estacionário e transitório da literatura. Foram também examinados os efeitos da taxa de resfriamento no crescimento celular da liga Pb 0,85%Sb e a influência do tamanho celular e do perfil de macrossegregação correspondente na resistência à corrosão / Abstract: The morphologies of as-cast microstructures, characterized mainly by cellular and dendritic patterns, and their scales represented by primary, secondary and tertiary arm spacings, control the segregation profiles and the formation of secondary phases within intercellular and interdendritic regions, which determine the final properties of castings. The present work aims to contribute to the understanding of microstructural development of binary alloys by analyzing two binary systems, which possess high industrial importance in the manufacture of as-cast automotive components and battery grids: Al-Si and Pb-Sb, respectively. Experiments have been carried out by using two castings assemblies, which were designed in such way that heat was extracted only through the water-cooled system, located at the bottom (upward solidification) and at the top (downward solidification) of the casting. The solidification thermal variables have been determined from thermal readings acquired by thermocouples located inside of the casting in different positions from the cooled surface. Such experimental thermal variables have been compared with theoretical predictions of a numerical model of solidification. Macrostructural and microstructural aspects along the casting were characterized by optical microscopy. For Al-Si alloys a complementary analysis of the influence of thermosolutal convection on the tertiary dendrite arm spacing during the downward unsteady-state directional solidification has been carried out. Hypoeutectic Pb-Sb alloys have been used to analyze the influences of solute concentrations and solidification thermal variables in the development of cellular structures, the cellular/dendritic transition and dendritic structures. Experimental cellular and dendritic spacings have been compared with the theoretical predictions furnished by the main steady-state and unsteady-state growth models from the literature. The effect of cooling rate on the cellular growth of a Pb 0.85wt%Sb alloy and the influences of cell size and of the corresponding macrosegregation profile on the resultant corrosion behavior have also been examined. / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Com a descoberta de novas fontes de petróleo e gás, em regiões remotas e de difícil acesso, tem-se a necessidade do desenvolvimento de novas tecnologias para garantir a eficácia da exploração destes recursos. Essa exploração e extração muitas vezes se dão em ambientes altamente corrosivos e os equipamentos devem apresentar propriedades que garantam um fator de segurança em serviço. Os aços de alta resistência e baixa liga (ARBL) são utilizados em tubulações para o transporte de gás natural e petróleo. Estes estão constantemente expostos a ambientes ácidos os quais são compostos de umidade e sulfeto de hidrogênio (H2S), podendo causar falha induzida pela presença de hidrogênio (Hydrogen Induced Cracking HIC). Este tipo de falha é normalmente abordado na literatura através de ensaios em solução contendo ácido acético e/ou sais (cloreto de sódio, entre outros), sempre com a injeção de H2S. Há vários mecanismos propostos, no entanto, o assunto não está totalmente resolvido. As alterações de composição química dos aços, processos de refino do aço e processos de conformação mecânica são responsáveis pela microestrutura final e determinantes da resistência à fragilização por hidrogênio. O objetivo deste trabalho é analisar e comparar o comportamento quanto à resistência à corrosão e resistência à HIC de quatro materiais: tubo X65 sour, sua região de solda, tubo X65 não-sour e uma chapa destinada a confecção de tubo X65. Os eletrólitos empregados foram: solução A (ácido acético contendo cloreto de sódio) e a solução B (água do mar sintética), os quais correspondem às soluções recomendadas pela norma NACE TM0284-2003. Os materiais foram submetidos a: ensaios de polarização (Polarização Linear para determinação da Resistência de Polarização - Rp) e ensaios de resistência a HIC segundo a norma NACE TM0284-2003; exames em microscópio óptico e eletrônico de varredura para caracterização da morfologia da corrosão e do trincamento. Os ensaios de Rp revelaram que a solução A é mais agressiva do que a solução B, sendo isso explicado pela diferença de pH entre estas duas soluções. Os resultados mostraram ainda que a máxima resistência à corrosão sempre é obtida para o tubo sour, enquanto a mínima ocorreu para o tubo não-sour. Após o ensaio de resistência a HIC os exames em microscópio óptico revelaram que, em ambas as soluções, o tubo de X65 sour, e a sua solda não apresentaram trincas, bem como a chapa destinada a tubo X65; já o tubo de X65 não-sour apresentou trincamento principalmente na região central. Os exames das trincas revelaram que a presença de cementita intergranular e a estrutura bandeada foram as causas do trincamento. No caso do tubo sour, o bom desempenho foi discutido em termos da microestrutura de ferrita poligonal, acicular e microconstituinte M/A. Já o comportamento distinto encontrado para a chapa (para tubo X65), foi discutido levando-se em conta que esta chapa apresentou menor quantidade de cementita intergranular, uma vez que, sua microestrutura é bandeada e não foi encontrado trincamento. Os resultados também revelaram que a solução B, como no caso da resistência à corrosão, é uma solução menos agressiva, pois o trincamento obtido foi muito menor. / The discovery of new oil and gas reserves, at remote and hard to reach locations, makes imperative the development of new technologies to ensure effective exploitation of these resources. This exploitation is often performed at highly corrosive environments and equipment such as pipelines should have special mechanical and corrosion properties to guarantee safety levels in service. High-Strength Low Alloy (HSLA) steels are used in pipelines for transporting gas and oil. These steels are in constant exposure to acid environments containing hydrogen sulfide (H2S) and water, that can cause pipeline failures due to Hydrogen-Induced Cracking - HIC. The literature reports that Hydrogen-Induced Cracking in steels is normally tested in solutions containing acetic acid and/or, salts (sodium chloride and others) with addition of H2S. Chemical composition, steel refining processes and metal forming processes are responsible for the final microstructure of the steel and have effect on the hydrogen embrittlement resistance. The purpose of this work is to analyze and compare the corrosion resistance and HIC resistance, and compare of four materials: pipeline steel API 5L X65 for sour service, its welded junctions, pipeline steel API 5L X65 for non-sour service and pipeline steel plate API 5L X65. The materials were submitted to linear polarization test (Rp) and HIC resistance test according to NACE TM0284-2003 standard. Both tests were carried out with two different electrolytes: the solution A (acetic acid and sodium chloride) and solution B (synthetic seawater). Subsequently; the surface of the steels were evaluated by optical microscope and scanning electron microscopy in order to characterize the cracking modes and corrosion morphology. The Rp tests showed that the solution A is more aggressive than solution B, behavior attributed to the pH difference between solutions. Steel API 5L X65 for sour service had the highest corrosion resistance and pipeline steel API 5L X65 for non-sour service had the lowest. The HIC test and the surface examination revealed that in both solutions, pipeline steel API 5L X65 for sour service, the welded junctions and the pipeline steel plate API 5L X65 showed no cracks. On the other hand, pipeline steel API 5L X65 for non-sour service presented cracking mainly in the central region. The tests revealed that the cracks nucleated at the intergranular cementite in the banded structure. The good performance of the pipeline steel API 5L X65 for sour service was discussed in terms of the microstructure, formed by polygonal ferrite, acicular ferrite and M/A microconstituent. The performance of steel plate (for pipeline API 5L X65) was different. This material did not exhibit cracks in the matrix in spite of its banded microstructure. This result was discussed taking into account that the plate studied had a small amount of intergranular cementite. The results also showed that the solution B, as in the case of corrosion resistance tests, was less aggressive than solution A, because the cracks produced were smaller.

As chapas de ligas de alumínio trabalháveis são produzidas atualmente por dois processos, o método de vazamento contínuo conhecido TRC (Twin Roll Continous Casting) ou pelo método tradicional de vazamento de placas DC (Direct Chill). A fabricação de ligas de alumínio pelos dois processos confere características microestruturais diferentes quando comparadas entre si, o que se reflete em suas propriedades. Além disto, ocorrem variações microestruturais ao longo da espessura, especialmente nas chapas produzidas pelo processo TRC. Neste sentido, é importante estudar a evolução microestrutural que ocorre durante o seu processamento e sua influência com relação à resistência à corrosão. Dessa forma foi realizado neste trabalho um estudo comparativo do comportamento de corrosão, bem como das microestruturas do alumínio de alta pureza AA1199 (99,995% Al) e das ligas de alumínio AA1050 (Fe+Si0,5%) e AA4006 (Fe+Si1,8%) produzidas pelos processos industriais de lingotamento contínuo e semi-contínuo. Os resultados obtidos evidenciaram que as microestruturas das ligas AA4006 DC e AA4006 TRC são distintas, sendo observada maior fração volumétrica dos precipitados na liga fabricada pelo processo TRC comparativamente ao DC. Para caracterizar o comportamento de corrosão foram realizados ensaios de Espectroscopia de Impedância Eletroquímica e Polarização Potenciodinâmica, que mostraram a maior resistência à corrosão localizada para a liga fabricada pelo processo TRC em comparação ao processo DC. Além disso, foi verificada, em ordem decrescente, uma maior resistência à corrosão do alumínio AA1050, seguida pela superfície da liga AA4006 e por fim, pelo centro da chapa desta última. Os resultados obtidos por espectroscopia de impedância eletroquímica para as ligas AA4006 fabricadas pelo processo TRC apresentaram melhor desempenho que o processo DC, principalmente em intervalos de 2 a 12 horas de imersão na solução de sulfato de sódio contaminada com íons cloreto. Para tempos de imersão acima de 4 horas foi observado comportamento indutivo em baixas frequências para os dois tipos de processamento investigados, o que foi associado à adsorção de espécies químicas, principalmente íons sulfato e oxigênio, na interface metal/óxido. As curvas de polarização anódica mostraram maior resistência à corrosão localizada para a liga fabricada pelo processo viii TRC em comparação ao processo DC. Este comportamento foi associado às diferentes características microestruturais, observadas para liga AA4006 obtida pelos dois processos. / Currently, wrought aluminum alloys are manufactured by two different processes: the twin roll continuous casting (TRC) or the more conventional method of Direct Chill (DC). The production method of the aluminum alloys through both processes results in different microstructures when compared to each other, which has a direct influence on their final properties. Besides this, there are also microstructural variations across sheet thickness, especially in alloys obtained by the TRC casting mode. Therefore, it is important to study the microstructural evolution that occurs during the casting process and its influence regarding corrosion resistance. In the present work both the microstructural characteristics and the corrosion behavior of the AA4006 (Fe + Si 1.8%) aluminum alloys sheets produced by both TRC and semi-continuous DC industrial processes were studied and compared to the commercial AA1050 aluminum (Fe + Si 0.5%) and to the high purity aluminum AA1199 (99,995% Al). The results demonstrate that size and distribution of intermetallic compounds are quite distinct in DC and TRC alloys, resulting in higher volumetric fractions of the precipitates in TRC, when compared to the DC process. Electrochemical Impedance Spectroscopy and Potentiodynamic Polarization tests were carried out to establish the corrosion behavior of aluminum alloys, and in both tests a higher resistance to localized corrosion in the alloy produced by TRC, when compared to the DC process was verified.The results have also showed, in decreasing order, a higher corrosion resistance of AA1050 TRC followed by the surface of AA4006 TRC, and finally by the center of AA4006 TRC sheet. The electrochemical impedance spectroscopy results showed better performance in the center of the AA4006 TRC than in the its surface, when submitted to low aggressive media for periods of immersion higher than 24 hours. The AA4006 DC in sulfate solution containing chloride ions presented worse performance, mainly in immersion periods from 2 to 12 hours, when compared to the corrosion behavior in the AA4006 TRC process. After 4 hours of immersion, the impedance results presented inductive behavior in low frequencies for both manufacture processes. This behavior was attributed to the adsorption of intermediates, mainly sulfate and oxygen ions on metal/oxide interface. The anodic polarization curves showed higher localized corrosion resistance (Pit Corrosion) for the alloy manufactured by the TRC process in comparison to the DC process. This behavior was associated with different microstructural characteristics observed in AA4006 obtained by these two processes.

Slat-band chains are used as conveyors by the food industry, breweries and bottling plants. The operating conditions require abrasion resistance and strength which are at the limit of the capabilities of the current material of choice, cold worked type 430. In an unconventional way of strengthening this material, Mintek developed a process in which the cold worked material is aged between 450°C and 500°C. The present work aims to elucidate the strengthening mechanism, using type 430 stainless steel containing 16.42% Cr and 0.036% C, in the cold-rolled condition (38% reduction in area), with and without prior solution heat treatment. The Cr-rich precipitate α" may form in the 450°C to 500°C range (due to the miscibility gap in the Fe-Cr system), resulting in the increased hardness and lowered ductility. Mossbauer studies confirmed that the α", at this composition and temperature, forms through the process of nucleation and growth. Hardening due to α" precipitation was only observed after aging for 64 hours or more, however. After increasing the dissolved interstitial content by solution heat treatments (in the vicinity of 900°C), increases in Vickers hardness of 30-50 kg/mm2 could be obtained after only 8 minutes at 475°C. This hardness increase corresponds to an increase in tensile strength of more than 100 MPa. The increased hardness does not appear to be caused by strain aging, and presumably results from fine carbide or nitride precipitation. Solution treatment at 930°C also introduced some martensite (α') into the microstructure, which raised the hardness of the unaged cold worked material. Overaging of the carbide and nitride precipitates was observed at 475°C, but not at 450°C, probably due to the lower diffusion rates at the lower temperature. No averaging of the α" precipitates occurred, for aging times up to 2072 hours. Samples aged for selected periods of time at 475°C had low impact strengths - even well before the formation of α" - and revealed predominantly cleavage fracture with some ductile fracture areas, mostly at grain boundaries. Both impact strength and lateral expansion indicated that embrittlement accompanies the increased hardness obtained by aging. Calculation of critical crack lengths from the impact data, however, revealed that a maximum flaw length of 0.8 mm, for specimens solution treated at 880°C, could be tolerated before catastrophic failure. Since it is not expected that flaws of that size would exist in the as manufactured links, fatigue will probably determine the lifetime of the chains, although the lower K1c values indicate that less crack propagation will be tolerated before brittle fracture. During the aging treatment, the strength may be lowered by recrystallisation of the coldworked material. Transmission electron microscopy (TEM) revealed the start of recovery, but no recrystallisation. Some large precipitates (around lμm in diameter) were present. These were identified, through their diffraction patterns, as M23C6; these carbides were present in both aged and unaged material and hence represent precipitates which had not dissolved during the initial solution treatments. The α" precipitates- and the presumed newly formed nitride and carbide precipitates - were too fine for detection by TEM. Potentiodynamic testing of the treated material in a 0.5M H2SO4 solution indicated that, although the probable hardening mechanisms imply localised Cr depletion of the matrix, the general corrosion resistance and passivation behaviour were not affected. It is concluded that the strength of the chain may be increased markedly by short-term heat treatments at 475°C, with lowered toughness, but with no decrease in corrosion resistance. Martensite, work hardening, and precipitation of carbides and nitrides all contribute to the final strength, with α" formation only becoming significant after longer aging times. / Dissertation (MEng)--University of Pretoria, 2013. / Materials Science and Metallurgical Engineering / unrestricted

The purpose of the thesis was to study chemical and corrosion resistance of selected conversion coatings. The corrosion and the possibilities of corrosion protection with focus on conversion coatings on aluminum and steel surface were described in the theoretical part. In the experimental part corrosion and chemical resistance of samples without the next treatment and samples with polyester powder coating and synthetic coating were tested.

The glass-forming Ti75Zr10Si15 alloy is regarded as a potential new material for implant applications due to its composition of non-toxic, biocompatible elements and many interesting mechanical properties. The effects of partial substitution of 15 at.-% Ti by Nb on the microstructure and mechanical behavior of the alloy have been investigated. The limited glass-forming ability (GFA) of the Ti75Zr10Si15 alloy results for melt-spun ribbons mainly in nanocomposite structures with β-type nanocrystals being embedded in a glassy matrix. Addition of Nb increases the glass-forming ability. Raising the overheating temperature of the melt prior to melt-spinning from 1923 K to 2053 K yields a higher amorphous phase fraction for both alloys. A decrease of hardness (H), ultimate stress and reduced Young’s modulus (Er) is observed for Ti60Zr10Nb15Si15 rods as compared to Ti75Zr10Si15 ones. This is attributed to an increase of the fraction of the β-type phase. The melt-spun ribbons show an interesting combination of very high hardness values (H) and moderate reduced elastic modulus values (Er). This results in comparatively very high H/Er ratios of >0.075 which suggests these new materials for applications demanding high wear resistance. The corrosion and passivation behavior of these alloys in their homogenized melt-spun states have been investigated in Ringer solution at 37°C in comparison to their cast multiphase crystalline counterparts and to cp-Ti and β-type Ti-40Nb. All tested materials showed very low corrosion rates. Electrochemical and surface analytical studies revealed a high stability of their passive states in a wide potential range. The addition of Nb does not only improve the glass-forming ability and the mechanical properties but also supports a high pitting resistance even at extreme anodic polarization. With regard to the corrosion properties, the Nb-containing nearly single-phase glassy alloy can compete with the β-type Ti-40Nb alloy. In addition, it has been demonstrated that thermal oxidation could be well applied to Ti75Zr10Si15 and Ti60Zr10Nb15Si15 melt-spun ribbons. Thermal oxidation treatment is one of the simple and cost-effective surface modification methods to improve the surface characteristics of these alloys. In the first tests, ribbon samples of the ternary and the quaternary alloy which were oxidized at 550°C in synthetic air showed suitable fundamental properties for implant applications, i.e. high hardness, good wettability and hydroxyapatite-forming ability after 10 days. All these properties recommend the new glass-forming alloys for application as wear- and corrosion-resistant coating materials for implants. / Die glasbildende Legierung Ti75Zr10Si15 wird wegen ihrer biokompatiblen Zusammensetzung ohne toxische Elemente und auf Grund interessanter mechanischer Eigenschaften als potentielles neues Implantatmaterial betrachtet. Es wurden 15 at.-% Ti durch Nb partiell substituiert und die Effekte auf die Mikrostruktur und die mechanischen Eigenschaften der Legierung untersucht. Auf Grund der eingeschränkten Glasbildungsfähigkeit von Ti75Zr10Si15 bestehen die schmelzgeschleuderten Bänder dieser Legierung hauptsächlich aus Nanokomposit-Strukturen mit β-phasigen Nanokristallen in einer glasartigen Matrix. Die Zugabe von Nb steigert die Glasbildungsfähigkeit. Das Anheben der Überhitzungstemperatur der Schmelze vor dem Schmelzschleudern von 1923 auf 2053 K führt für beide Legierungen zu einem höheren Anteil amorpher Phase. Es wird bei der Legierung Ti60Zr10Nb15Si15 im Vergleich zur Ti75Zr10Si15-Legierung eine Abnahme der Härte (H), Bruchfestigkeit und ein reduzierter E-Modul (Er) beobachtet. Dies wird mit dem Anstieg des beta-Phasenanteils erklärt. Die schmelzgeschleuderten Bänder zeigen eine interessante Kombination aus sehr hoher Härte und moderaten E-Modul Werten (Er). Dies führt zu vergleichsweise sehr hohen H/Er-Verhältnissen von >0,075, wodurch diese Materialien für Anwendungen mit hohen Verschleißanforderungen geeignet sind. Das Korrosions- und Passivierungsverhalten dieser Legierungen in ihrem homogenisierten schmelzgeschleuderten Zustand wurde in Ringer-Lösung bei 37°C untersucht und mit dem gegossenen vielphasigen kristallinen Zustand dieser Legierungen sowie mit cpTi und beta-Typ Ti-40Nb verglichen. Alle untersuchten Materialien zeigten sehr niedrige Korrosionsraten. Elektrochemische Studien und Oberflächenanalysen belegen eine hohe Stabilität der Passivfilme in einem weiten Potentialbereich. Die Zugabe von Niob verbessert nicht nur die Glasbildungsfähigkeit und die mechanischen Eigenschaften, sondern erhöht weiterhin die Lochfraßbeständigkeit, selbst bei stark anodischer Polarisation. Bezüglich der Korrosionseigenschaften konkurriert die Nb-haltige fast einphasige glasartige Legierung mit β-phasigem Ti-40Nb. Weiterhin wurde gezeigt, dass an schmelzgeschleuderten Bändern der Legierung Ti75Zr10Si15 und Ti60Zr10Nb15Si15 eine thermische Oxidation erfolgreich durchgeführt werden konnte. Die thermische Oxidation ist eine der einfachsten und kosteneffektivsten Möglichkeiten der Oberflächenmodifikation um die Eigenschaften der Oberflächen dieser Legierungen zu verbessern. In den ersten Tests zeigten die Bänder-Proben der ternären und der quaternären Legierung, die bei 550°C in synthetischer Luft oxidiert wurden, entsprechende Eigenschaften für Implantat-Anwendungen, d.h. hohe Härte, gute Benetzbarkeit und die Fähigkeit nach 10 Tagen Hydroxylapatit auf der Oberfläche zu bilden. Alle zuvor genannten Eigenschaften machen diese neuen glasbildenden Legierungen zu geeigneten Materialien für die Anwendung als verschleiß- und korrosionsbeständige Beschichtung für Implantate.

[ES] En los últimos años, se han desarrollado numerosos tipos de recubrimientos superficiales frente a la corrosión basados especialmente en aleaciones de cinc-aluminio-magnesio (conocidas como aleaciones "ZM"), como alternativas a los recubrimientos tradicionales basados en cinc (conocidos como "Z"), con el fin de mejorar sus características técnicas y reducir su coste. Los fabricantes de estos nuevos tratamientos reivindican una mayor resistencia a la corrosión, basándose en ensayos de corrosión acelerada y ensayos de campo, estos últimos de muy pocos años de duración. La presente tesis, tiene como principal objetivo la estructuración y análisis de toda la información existente en el actual estado de la técnica, y en particular, el estudio de los ensayos de campo existentes para corroborar su resistencia a la corrosión en distintos tipos de ambientes y a partir de ello, proponer un modelo matemático que facilite su cálculo a largo plazo. Se presenta una revisión del estado de la técnica de recubrimientos metálicos basados en aleaciones ZM, que cubre su evolución en el tiempo, las diferentes calidades y designaciones existentes en el mercado, su estructura y composición, normas internacionales que los regulan y una detallada investigación sobre ensayos de campo en localizaciones de todo el mundo, habiéndose encontrado ensayos de una duración máxima de 6 años. A partir del análisis de estos ensayos de campo, se propone una Metodología para verificar el rendimiento y la evolución de la función corrosión-tiempo, en los diferentes ambientes de exposición, categorizados a través de la norma internacional ISO 9223 (ISO, 2012), que los denomina "categorías de corrosividad", y que abarcan desde C1 (muy bajo) hasta CX (extremo). Este análisis ha clasificado todos los resultados de los ensayos por material, categoría de corrosividad y evolución a lo largo del tiempo. De esta forma, cada categoría de corrosividad ha sido investigada en profundidad, mediante un análisis estadístico, poniendo especial énfasis en la corrosión anual, medida como pérdida de masa (µm / año), la función corrosión-tiempo y su ajuste a un determinado comportamiento. Se han analizado asimismo los recubrimientos Z con el fin de poder comparar ambas alternativas y corroborar la hipótesis de partida, cuyo supuesto principal es la mayor resistencia a la corrosión de las aleaciones ZM frente a los recubrimientos Z. Este análisis ha sido el punto de entrada, para establecer un modelo matemático que determine el rendimiento de la corrosión a largo plazo, con el fin de proporcionar a los profesionales de proyectos en la ingeniería, una herramienta que permita estimar la resistencia a la corrosión y la optimización del coste de una instalación cuando se utilizan diferentes tipos de materiales. El compendio de todo este análisis se ha reflejado en el apartado de Resultados y comentarios. La referida metodología, se ha aplicado a un caso de estudio para mostrar cómo seleccionar la calidad del recubrimiento y su espesor óptimo, así como un cálculo de costes, con el objetivo de garantizar los requisitos de un determinado proyecto, en términos de resistencia a la corrosión y coste. Las conclusiones finales ponen de manifiesto que existen algunas ventajas de las aleaciones ZM frente a recubrimientos Z, principalmente en lo que respecta a la resistencia a la corrosión, al haber encontrado relaciones que pueden duplicar y triplicar su rendimiento, en los períodos para los que hay datos disponibles. Del mismo modo, se han encontrado algunas desventajas, que deben investigarse más a fondo en futuros trabajos de investigación, para dar continuidad a esta tesis. Por ejemplo, la limitación de estos recubrimientos para lograr grandes espesores, la limitada duración de los ensayos de campo, el rendimiento en partes específicas de los componentes (cortes, embuticiones, doblados, soldaduras...), etc. / [CA] En els últims anys, s'han desenvolupat nombrosos tipus de recobriments superficials enfront de la corrosió basats especialment en aliatges de zinc-alumini-magnesi (conegudes com a aliatges "ZM"), com a alternatives als recobriments tradicionals basats en zinc (coneguts com a "Z"), amb la finalitat de millorar les seues característiques tècniques i reduir el seu cost. Els fabricants d'aquests nous tractaments reivindiquen una major resistència a la corrosió, basant-se en assajos de corrosió accelerada i assajos de camp, aquests últims de molt pocs anys de duració. La present tesi, té com a principal objectiu l'estructuració i anàlisi de tota la informació existent en l'actual estat de la tècnica, i en particular, l'estudi dels assajos de camp existents per a corroborar la seua resistència a la corrosió en diferents tipus d'ambients i a partir d'això, proposar un model matemàtic que facilite el seu càlcul a llarg termini. Es presenta una revisió de l'estat de la tècnica de recobriments metàl·lics basats en aliatges ZM, que cobreix la seua evolució en el temps, les diferents qualitats i designacions existents en el mercat, la seua estructura i composició, normes internacionals que els regulen i una detallada investigació sobre assajos de camp en localitzacions de tot el món, havent-se trobat assajos d'una duració màxima de 6 anys. A partir de l'anàlisi d'aquests assajos de camp, es proposa una metodologia per a verificar el rendiment i l'evolució de la funció corrosió-temps, en els diferents ambients d'exposició, categoritzats a través de la norma internacional ISO 9223 (ISO, 2012), que els denomina "categories de corrosivitat", i que abasten des de C1 (molt baix) fins a CX (extrem). Aquesta anàlisi ha classificat tots els resultats dels assajos per material, categoria de corrosivitat i evolució al llarg del temps. D'aquesta manera, cada categoria de corrosivitat ha sigut investigada en profunditat, mitjançant una anàlisi estadística, posant especial èmfasi en la corrosió anual, mesura com a pèrdua de massa (µm / any), la funció corrosió-temps i el seu ajust a un determinat comportament. S'han analitzat així mateix els recobriments Z amb la finalitat de poder comparar totes dues alternatives i corroborar la hipòtesi de partida, el supòsit principal de la qual és la major resistència a la corrosió dels aliatges ZM enfront dels recobriments Z. Aquesta anàlisi ha sigut el punt d'entrada, per a establir un model matemàtic que determine el rendiment de la corrosió a llarg termini, amb la finalitat de proporcionar als professionals de projectes en l'enginyeria, una eina que permeta estimar la resistència a la corrosió i l'optimització del cost d'una instal·lació quan s'utilitzen diferents tipus de materials. El compendi de tota aquesta anàlisi s'ha reflectit en l'apartat de Resultats i comentaris. La referida metodologia, s'ha aplicat a un cas d'estudi per a mostrar com seleccionar la qualitat del recobriment i la seua grossària òptima, així com un càlcul de costos, amb l'objectiu de garantir els requisits d'un determinat projecte, en termes de resistència a la corrosió i cost. Les conclusions finals posen de manifest que existeixen alguns avantatges dels aliatges ZM enfront de recobriments Z, principalment pel que fa a la resistència a la corrosió, en haver trobat relacions que poden duplicar i triplicar el seu rendiment, en els períodes per als quals hi ha dades disponibles. De la mateixa manera, s'han trobat alguns desavantatges, que han d'investigar-se més a fons en futurs treballs de recerca, per a donar continuïtat a aquesta tesi. Per exemple, la limitació d'aquests recobriments per a aconseguir grans grossàries, la limitada duració dels assajos de camp, el rendiment en parts específiques dels components (talls, embuticions, doblegats, soldadures...), etc. / [EN] In recent years, numerous types of surface corrosion coatings, based especially on zinc-aluminium-magnesium alloys (known as "ZM" alloys), have been developed as alternatives to traditional zinc-based coatings (known as "Z"), to improve its technical characteristics and reduce its cost. The manufacturers of these new treatments claim greater resistance to corrosion, based on accelerated corrosion tests and field tests, the latter lasting only a few years. The main objective of this thesis is the structuring and analysis of all the existing information in the current state of the art, and in particular, the study of the existing field tests to corroborate their resistance to corrosion in different types of environments and based on this, propose a mathematical model that facilitates its long-term calculation. A review of the state of the art of metal coatings based on ZM alloys is presented, which covers their evolution over time, the different qualities and designations existing in the market, their structure and composition, international standards that regulate them and a detailed research on field tests in different locations around the world, having found tests of a maximum duration of 6 years. From the analysis of these field tests, a methodology is proposed to verify the performance and evolution of the corrosion-time function in the different exposure environments, categorized through the international standard ISO 9223 (ISO, 2012), which calls them "corrosivity classes", and which range is from C1 (very low) to CX (extreme). This analysis has classified all the test results by material, corrosivity class and evolution over time. In this way, each corrosivity class has been investigated in depth, through statistical analysis, with special emphasis on annual corrosion, measured as mass loss (µm / year), the corrosion-time function and its adjustment to a certain behaviour. The Z coatings have also been analysed to be able to compare both alternatives and corroborate the main hypothesis, whose main assumption is the greater resistance to corrosion of ZM alloys compared to Z coatings. This analysis has been the entry point to establish a mathematical model that determines the long-term corrosion performance, to provide project engineering professionals, with a tool to estimate the corrosion resistance and optimize the cost of an installation when different types of materials are used. The summary of all this analysis has been reflected in the Results and discussion section. The referred methodology has been applied to a case study to show how to select the quality of the coating and its optimal thickness, as well as a cost calculation, in order to guarantee the requirements of a specific project, in terms of resistance to corrosion and cost. The final conclusions show that there are some advantages of ZM alloys over Z coatings, mainly with regard to corrosion resistance, having found relationships that can double and triple their performance, in the periods for which there are data available. In the same way, some disadvantages have been found, which must be investigated further in future research works, to give continuity to this thesis. For example, the limitation of these coatings to achieve large thicknesses, the limited duration of field tests, the performance of specific parts of the components (cuts, embossments, bends, welds ...), etc. / Chenoll Mora, E. (2021). Analysis of metallic coatings based in zinc-aluminium-magnesium alloys, in terms of performance and long-term corrosion. Case study: Electrical cable trays selection in project design [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/167418

In this work, the mechanism of the corrosion behavior of laser-treated aluminum is studied. Two different laser techniques are used to fabricate the samples, direct laser interference patterning (DLIP) and direct laser writing (DLW), using nanosecond laser sources. The DLIP treatment uses a two-beam optical configuration producing line-like periodic structures. The DLW technique is employed to produce non-periodic structures on the Al-surface with the same cumulated fluences as in DLIP. The surface topography is analyzed by confocal microscopy, and the formation of oxide layers is investigated by scanning electron microscopy of cross-sections produced using a focused ion beam. Wetting measurements performed on the laser-treated samples exhibit a contrasting behavior, leading to either superhydrophobic or superhydrophilic states. In the case of the DLIP treatment, the static water contact angle is increased from 81° up to 158°, while for DLW, it decreases to 3°. Electrochemical tests demonstrate a decreased corrosion rate after laser treatment. Additionally, findings indicate no correlation between wettability and corrosion reduction. Therefore, the improvement in corrosion resistance is mainly attributed to the oxide layer formed by laser treatment. Although similar corrosion rates are achieved for both treatments, surfaces produced with DLIP can be beneficial when additional surface properties are required.

The corrosion resistance under elevated temperature of additively manufactured 316L stainless steel made by directed energy deposition was studied. Test samples were prepared in a hybrid additive manufacturing machine using standard deposition parameters recommended by the manufacturer. Control samples were cut from wrought material to compare the results. The test was performed under a corrosive atmosphere with a solution of water with 3.5 % in weight of salt (NaCl). The total duration of the test was 635 hours, divided in five stages of 12, 24, 48, 226, and 325 hours to analyze the samples between each stage. The samples were analyzed quantitatively measuring weight loss and surface topography, and qualitatively by macroscopic inspection with digital photography, and microscopic inspection with optical and scanning electron microscopy. The results show a higher corrosion rate for the additively manufactured samples compared to the control samples. An evident increase in the size of pits initially present on the samples was observed and quantified on the additively manufactured. Although the additively manufactured samples were more aggressively attacked by corrosion, they still presented a shiny surface finish at the end of the test, reinforcing the idea of the formation of a passive oxide layer and suggesting that the corrosion was focalized in the surface defects by pitting and crevice corrosion mechanisms.

No presente trabalho quatro ligas Al-Si hipereutéticas, três das quais foram produzidas por conformação por \"spray\" e a outra por fundição, foram caracterizadas quanto a textura, dureza, microestrutura e resistência à corrosão em meio de condensado sintético automotivo (CSA). Duas das ligas conformadas por \"spray\" foram retiradas de camisas de cilindro e a outra de um pré-formado obtido em laboratório. A conformação por \"spray\" envolve a atomização de uma liga e a deposição de gotículas em um substrato, antes mesmo que todas se encontrem no estado sólido. Este processo permite a obtenção de materiais que se caracterizam por uma microestrutura livre de macrossegregações e bastante refinada, implicando melhor trabalhabilidade a quente. A caracterização da microestrutura das quatro ligas hipereutéticas revelou a presença de porosidades na liga obtida em laboratório, e microestrutura com distribuição homogênea de precipitados primários nas três ligas conformadas por \"spray\". A microestrutura de uma das ligas apresentou-se muito diferenciada, com a presença de eutético, sugerindo que esta foi fabricada por fundição. Nas camisas de cilindro foram feitas medidas de rugosidade, e em todas as ligas foram realizados ensaios de microdureza. A liga conformada por \"spray\" e obtida em laboratório foi laminada a quente e a frio. Foram realizados também estudos de textura, para tentar estabelecer uma correlação entre todas as ligas quanto ao processo de fabricação. A avaliação da textura indicou que a presença de fases de silício primário, finamente distribuídas impedem o aparecimento de texturas típicas de deformação de ligas de alumínio, mesmo após severas deformações, como as necessárias para a transformação de pré-formados em tubos que originam as camisas de cilindro. As medidas de rugosidade indicaram características próprias do acabamento superficial usado para a produção das camisas, por brunimento ou por ataque químico. Os ensaios de microdureza apresentaram variações de acordo com as rotas de fabricação sendo que a liga eutética apresentou os maiores valores de microdureza em comparação às ligas conformadas por \"spray\". Todas as ligas foram avaliadas quanto a resistência à corrosão por ensaios de espectroscopia de impedância eletroquímica em dois meios, CSA com pH 3,3 e CSA com pH 11. As quatro ligas hipereutéticas estudadas apresentaram mecanismo de corrosão similar em condensado sintético automotivo (CSA) pH 3,3. Em todas ocorreu o ataque intenso da matriz de alumínio e as partículas de silício primário atuaram como regiões catódicas. A liga 2 apresentou maior resistência à corrosão entre todas as ligas ensaiadas, tanto em CSA pH 3,3 como em pH 11. Neste último meio, uma camada de produtos de corrosão formou-se sobre todas as ligas, e os resultados indicaram mecanismos diferentes para o ataque da matriz de Al e para o crescimento da camada depositada na superfície das ligas estudadas. O ataque da matriz da liga 2 neste meio foi aparentemente mais lento do que sobre as demais ligas, com a formação de uma camada mais compacta de produtos de corrosão, estabelecendo um controle por difusão dos processos interfaciais para maiores períodos de ensaio. A camada formada sobre as demais ligas neste meio apresentou-se mais defeituosa, e nestas ocorreu também menor controle da velocidade das reações interfaciais por processos difusionais. / In the present study four hypereutectic Al-Si alloys, three produced by spray forming and one by casting, were characterized for microhardness, roughness, microstructure, texture and corrosion resistance in a synthetic automotive condensed solution (SACS). Two of the spray formed alloys tested were obtained from cylinder liners and the other was laboratory made. Spray forming involves alloy atomization and droplets deposition on a substrate, previous to the solidification of all of the droplets. This process favours the production of materials with a fine microstructure free of macrosegregation that is related to improved hot workability. The microstructure characterization of the four alloys revealed the presence of porosities in the laboratory made alloy. All the three alloys produced by spray forming showed a homogeneous distribution of primary precipitates. The microstructure of one of the alloys showed eutectic microstructure, indicating that this alloy was fabricated by casting. In the cylinder liners, the surface roughness was measured and the microhardness of all the alloys was also evaluated. Furthermore, the laboratory made alloy was hot and cold rolled. Texture determinations were carried out to investigate the correlation between the alloy type and their fabrication process. The texture investigation indicated that the fine distribution of primary silicon phase in the alloy hindered the development of texture typical of aluminium alloys deformation, even after severe mechanical work, such as those used in the conversion of pre-formed in cylinder liners. The surface roughness results indicated typical characteristics of the surface finishing used, honing or chemical etching. The microhardness results were dependent on the fabrication process used, with higher microhardness associated to the eutectic alloy comparatively to the spray formed ones. All hypereutectic alloys were tested for corrosion resistance using electrochemical impedance spectroscopy in two electrolytes, SACS with pH 3.3 and SACS with pH 11. The four tested alloys showed similar corrosion mechanisms in the acid electrolyte (SACS pH 3.3). The intense attack of the aluminium matrix occurred in ali tested alloys and the primary silicon phase was unattacked and appeared as emerging from the surface after corrosion immersion test. The primary silicon particles acted as cathodic sites. The alloy 2 showed the highest corrosion resistance among the tested alloys in both electrolytes, SACS pH 3.3 and SACS pH 11. In this last medium, a layer of corrosion products formed on all the alloys, and the results indicated different mechanisms for the aluminium matrix corrosive attack and growth of the deposited layer on the alloys surface. The kinetics of aluminium matrix attack was apparently slower in the alloy 2 than for the other alloys, resulting in the formation of a more compact layer of corrosion products, leading to diffusion controlled interfacial processes for longer test periods. The layer of corrosion products on the other three alloys (1, 3, and 4) had more defects and for these alloys diffusional controlled interfacial processes were not as significant as for alloy 2.