Influence of atmospheric and chemical environments on metal products leads usually to the corrosion damage. This master´s thesis deals with way to protect metals from corrosion, especially by polysiloxane coatings in combination with coatings containing zinc. Corrosion resistance of created coatings systems is tested by laboratory accelerated tests in corrosion chamber, where the natural atmospheric conditions are simulated. Chemical resistance in selected environments is verified by drop test. Quality characteristics coatings – thickness, adhesion to the underlying material, hardness and stability of the coating colour and gloss are evaluated too.

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[pt] Atualmente, pesquisas envolvendo metais e suas ligas têm como um de seus objetivos o controle microestrutural, como forma de aprimorar as propriedades de interesse, para as aplicações desejadas. Um fator importante que possui influência nas propriedades dos materiais policristalinos são os tipos, e distribuições de contornos de grãos e/ou de fase. A aplicação de processos que envolvam altas temperaturas, como tratamentos térmicos ou processos de soldagem, podem levar a transformações de fase, as quais modificam a cristalografia, composição química, distribuição e tamanho dos grãos. Os aços inoxidáveis duplex são ligas bifásicas constituídas de proporções aproximadamente iguais de ferrita e austenita pertencentes ao sistema Fe-Cr-Ni. Essa estrutura bifásica combina elevada resistência, boa tenacidade e excelente resistência à corrosão. Devido à essas excelentes propriedades são utilizadas em vários setores industriais como: indústrias químicas, petroquímicas, de petróleo e gás, e de construção naval. Incrementos na concentração de Cr e Ni nestes aços levam a formação de duas novas classes, os aços super e hiper duplex, cujas propriedades são semelhantes aos aços duplex, porém superiores. Neste caso, devido ao aumento no teor dos elementos de liga os processos de soldagem podem levar a formação de fases intermetálicas e/ou precipitados, as quais são deletérias as propriedades dos aços, facilitando o processo de corrosão. Muitas das transformações no estado sólido que ocorrem nos aços, seguem determinadas relações de orientação cristalográfica. Essas relações descrevem as interfaces de baixa energia que determinam os processos de nucleação e crescimento de novas fases. Portanto a determinação das relações de orientação presente nos aços duplex, super-duplex e hiper-duplex, a partir de transformações de fase obtidas em condições de equilíbrio e paraequilíbrio foram estudadas com a intenção de correlacionar com a susceptibilidade à corrosão por pites. Foram estudados os aços UNS S32205, UNS S32750 e UNS S33207, respectivamente pertencendo as classes duplex, super e hiperduplex A determinação das relações de orientação e fração de fases foi obtida por difração de elétrons retroespalhados (Electron Backscattering Diffraction - EBSD). A composição química das fases foi obtida por Espectroscopia de Energia Dispersiva (Energy Dispersion Spectroscopy - EDS). Estes dados foram correlacionados com os resultados obtidos após testes de corrosão ASTM G-48. Para todos os aços se observa a tendência do aumento da relação de orientação KS após submissão aos ciclos térmicos. No entanto, para as condições estudadas não foi encontrada uma correlação clara entre a presença da orientação KS com a formação de pites na ferrita. / [en] Currently, research involving metals and their alloys has microstructural control as one of its objectives, to improve the properties of interest, for the desired applications. An important factor that influences the properties of polycrystalline materials are the types and distributions of grain and/or phase boundaries. The application of processes involving high temperatures, such as heat treatments or welding processes, can lead to phase transformations, which modify the crystallography, chemical composition, distribution and size of the grains. Duplex stainless steels are biphasic alloys made up of approximately equal proportions of ferrite and austenite belonging to the Fe-Cr-Ni system. This two-phase structure combines high strength, good toughness and excellent corrosion resistance. Due to these excellent properties, they are used in various industrial sectors such as: chemical, petrochemical, oil and gas, and shipbuilding industries. Increases in the concentration of Cr and Ni in these steels lead to the formation of two new classes, super and hyper duplex steels, whose properties are like duplex steels, but superior. In this case, due to the increase in the content of alloying elements, the welding processes can lead to the formation of intermetallic phases and/or precipitates, which are deleterious to the properties of the steels, facilitating the corrosion process. Many of the solid-state transformations that occur in steels follow certain crystallographic orientation relationships. These relationships describe the lowenergy interfaces that determine the processes of nucleation and growth of new phases. Therefore, the determination of orientation relationships presents in duplex, super-duplex and hyper-duplex steels, from phase transformations obtained under equilibrium and paraequilibrium conditions, were studied with the intention of correlating with the susceptibility to pitting corrosion. The UNS S32205, UNS S32750 and UNS S33207 steels were studied, respectively belonging to the duplex, super and hyperduplex classes. of the phases was obtained by Energy Dispersion Spectroscopy (EDS). These data were correlated with the results obtained after ASTM G-48 corrosion tests. For all steels, there is a trend towards an increase in the KS orientation ratio after submission to thermal cycles, however no clear correlation between the presence of the KS orientation and the formation of pits in the ferrite was found.

The use of waste (or recycled) wood as a fuel in heat and power stations is becoming more widespread in Sweden (and Europe), because it is CO2 neutral with a lower cost than forest fuel. However, it is a heterogeneous fuel with a high amount of chlorine, alkali and heavy metals which causes more corrosion than fossil fuels or forest fuel. A part of the boiler which is subjected to a high corrosion risk is the furnace wall (or waterwall) which is formed of tubes welded together. Waterwalls are made of ferritic low-alloyed steels, due to their low price, low stress corrosion cracking risk, high heat transfer properties and low thermal expansion. However, ferritic low alloy steels corrode quickly when burning waste wood in a low NOx environment (i.e. an environment with low oxygen levels to limit the formation of NOx). Apart from pure oxidation two important forms of corrosion mechanisms are thought to occur in waste environments: chlorine corrosion and alkali corrosion. Although there is a great interest from plant owners to reduce the costs associated with furnace wall corrosion very little has been reported on wall corrosion in biomass boilers. Also corrosion mechanisms on furnace walls are usually investigated in laboratories, where interpretation of the results is easier. In power plants the interpretation is more complicated. Difficulties in the study of corrosion mechanisms are caused by several factors such as deposit composition, flue gas flow, boiler design, combustion characteristics and flue gas composition. Therefore, the corrosion varies from plant to plant and the laboratory experiments should be complemented with field tests. The present project may thus contribute to fill the power plant corrosion research gap. In this work, different kinds of samples (wall deposits, test panel tubes and corrosion probes) from Vattenfall’s Heat and Power plant in Nyköping were analysed. Coated and uncoated samples with different alloys and different times of exposure were studied by scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDX), X-ray diffraction (XRD) and light optical microscopy (LOM). The corrosive environment was also simulated by Thermo-Calc software. The results showed that a nickel alloy coating can dramatically reduce the corrosion rate. The corrosion rate of the low alloy steel tubes, steel 16Mo3, was linear and the oxide scale non-protective, but the corrosion rate of the nickel-based alloy was probably parabolic and the oxide much more protective. The nickel alloy and stainless steels showed good corrosion protection behavior in the boiler. This indicates that stainless steels could be a good (and less expensive) alternative to nickel-based alloys for protecting furnace walls. The nickel alloy coated tubes (and probe samples) were attacked by a potassium-lead combination leading to the formation of non-protective potassium lead chromate. The low alloy steel tubes corroded by chloride attack. Stainless steels were attacked by a combination of chlorides and potassium-lead. The Thermo-Calc modelling showed chlorine gas exists at extremely low levels (less than 0.1 ppm) at the tube surface; instead the hydrated form is thermodynamically favoured, i.e. gaseous hydrogen chloride. Consequently chlorine can attack low alloy steels by gaseous hydrogen chloride rather than chlorine gas as previously proposed. This is a smaller molecule than chlorine which could easily diffuse through a defect oxide of the type formed on the steel. / <p>QC 20130423</p>

Under våren 2021 upptäcktes förhöjda halter av polyaromatiska kolväten (PAH) i Björklinges dricksvattennät. Då ett vattenprov taget hos användare påvisade halter som låg över Livsmedelsverkets gränsvärden och källan till föroreningen inte identifierats, rekommenderades hushållen i Björklinge att inte använda kranvattnet till mat och dryck under en period. Efter sektionering av nätet och provtagning identifierades en äldre, nyligen reparerad, ledningssträcka av gjutjärn som trolig föroreningskälla. Denna typ av ledning är relativt vanligt förekommande i delar av Uppsala Vattens nät. Syftet med denna studie var att få en djupare förståelse för orsakerna till PAH-föroreningen i Björklinge och bedöma risken för att liknande föroreningar ska hända igen, samt att tillhandahålla ett beslutsunderlag för Uppsala Vattens hantering av äldre gjutjärnsledningar.En litteraturstudie genomfördes och data från Björklinge analyserades. Resultaten av litteraturstudien visade att frisättning av PAH från äldre gjutjärnsrör med korrosionsskydd innehållande stenkolstjära eller bitumen är ett välkänt fenomen. Biofilmen har en skyddande effekt och graden av frisättning kan därför påverkas av faktorer som klorering eller syrehalt i vattnet. Även mekaniskt slitage i form av reparationsarbete och tryckvågor kan leda till förhöjda nivåer av PAH. Korrosion av ledningarna är troligen också en viktig faktor.Utifrån litteraturstudien och resultaten från användarprover tagna i Björklinge respektive Skuttunge kunde det konstateras att problemen i Björklinge hade ett samband med frisättning av PAH från gjutjärnsrör. Vid tidpunkten för studien kunde ökande PAH-halter observeras på vissa platser i ledningsnätet även efter ledningsbytet i Björklinge våren 2021, vilket tydde på fortsatt kontaminering. Inga uppmätta halter i användarprover låg dock över något av Livsmedelsverkets gränsvärden och PAH i dricksvattnet anses inte vara ett stort hälsomässigt problem i dagsläget. Det är däremot viktigt att fortsätta monitorera halterna av PAH i Uppsala Vattens nät då denna typ av problem kan uppstå igen. Man bör också vara försiktig med åtgärder som kan påverka biofilmen samt vara återhållsam med spoling av denna typ av ledningar. De ledningar som identifierats som föroreningskällor bör åtgärdas. Med tanke på ledningarnas stigande ålder, begränsad kunskap om PAH och dess hälsoeffekter, samt WHOs rekommendationer bör man dock initiera ett långsiktigt arbete med att byta ut eller renovera denna typ av ledningar i Uppsala Vattens nät. / During the spring of 2021 elevated levels of polyaromatic hydrocarbons (PAH) were discovered in the drinking water supply network of Björklinge. Levels above the limit set by the Swedish Food Agency were observed in one user sample, which led to the inhabitants of Björklinge being recommended not to use the tap water for drinking or cooking while the source of the contamination was being identified. After sectioning and sampling the network, an older, recently repaired cast iron pipe was identified as the probable source of the contamination. This type of pipe is not uncommon in the drinking water network of Uppsala Vatten. The purpose of this study was to gain a deeper understanding of the causes of the PAH contamination in Björklinge and to determine the risk of similar contaminations happening again. Further, it aimed to provide a basis for future decisions regarding the handling of older cast iron pipes in the drinking water network of Uppsala Vatten.A literature study was done and data from Björklinge was analysed. The results of the literature study showed that the release of PAH from older cast iron pipes with coal tar or bitumen coating is a well-known phenomenon. The biofilm has protective properties, and the degree of PAH release can hence be affected by factors such as chlorination or oxygen concentration of the water. Mechanical wear in the form of repair work or pressure waves can also cause increased levels of PAH in the water.Based on the literature study as well as the results from the user samples of Björklinge and Skuttunge, it could be determined that the PAH contamination in Björklinge was related to the release of PAH from old cast iron pipes. At the time of this study, increasing levels of PAH could be observed in some parts of the drinking water network even after the suspected pipes had been replaced during the spring of 2021. This might indicate that the contamination was still ongoing. However, no samples were above the limits set by the Swedish Food Agency and PAH is currently not considered a major health problem. Despite this, it is important to keep monitoring the levels of PAH in the drinking water since the PAH levels might increase again. It is also important to be careful with measures that might affect the biofilm and when flushing cast iron pipes. The pipes that have already been identified as sources of contamination should be replaced. Given the increasing age of the cast iron pipes, the limited knowledge of PAH and its health effects, as well as the recommendations from the WHO, a long-term plan for how to remove or renovate this type of pipes from the drinking water network of Uppsala Vatten should be initiated.

Made available in DSpace on 2014-12-17T15:42:01Z (GMT). No. of bitstreams: 1 IedaNSM.pdf: 5948604 bytes, checksum: dbf245a349dd04cff535e8ba2e89601d (MD5) Previous issue date: 2007-07-06 / The aim of this work was to study a series of 11 different compositions of Ti-Zr binary alloys resistance to aggressive environment, i. e., their ability to keep their surface properties and mass when exposed to them as a way to evaluate their performance as biomaterials. The first stage was devoted to the fabrication of tablets from these alloys by Plasma-Skull casting method using a Discovery Plasma machine from EDG Equipamentos, Brazil. In a second stage, the chemical composition of each produced tablet was verified. In a third stage, the specimen were submitted to: as-cast microstructure analysis via optical and scanning electron microscopy (OM and SEM), x-ray dispersive system (EDS) chemical analysis via SEM, Vickers hardness tests for mechanical evaluation and corrosion resistence tests in a 0.9% NaCl solution to simulate exposition to human saliva monitored by open circuit potential and polarization curves. From the obtained results, it was possible to infer that specimens A1 (94,07 wt% Ti and 5,93% wt% Zr), A4 (77,81 wt % Ti and 22,19 wt % Zr) and A8 (27,83 wt% Ti and 72,17 wt% Zr), presented best performance regarding to corrosion resistance, homogeneity and hardness which are necessary issues for biomaterials to be applied as orthopedic and odontological prosthesis / Este trabalho teve como finalidade estudar uma s?rie de onze ligas met?licas bin?rias, tit?nio zirc?nio, quanto ? capacidade de resistirem ?s deteriora??es sem sofrerem modifica??es de suas propriedades iniciais de massa e superf?cie quando expostas a meios agressivos, como condi??o fundamental para que as mesmas sejam aplicadas como biomateriais. A primeira etapa tratou da confec??o das amostras das ligas em forma de pastilhas, empregando-se o processo de fundi??o Plasma Skull realizado na m?quina Discovery Plasma, produzida no Brasil pela EDG Equipamentos. Na segunda etapa, as amostras confeccionadas foram submetidas aos ensaios para a determina??o da composi??o qu?mica resultante de cada liga da s?rie ap?s a fus?o. E durante a terceira etapa foram feitos os procedimentos de avalia??es das amostras quanto ? homogeneidade e apresenta??o da microestrutura de cada uma das ligas no estado bruto de fus?o, como resultados dos ensaios metalogr?ficos por microscopia ?ptica e microscopia eletr?nica de varredura acoplada a espectroscopia por energia dispersiva de raios-x; quanto ? propriedade mec?nica de dureza medida em escala Vickers (HV); e quanto ?s propriedades qu?micas de resist?ncia ? corros?o, quando expostas em solu??o de cloreto de s?dio 0,9 %, para simular a saliva, empregando-se o monitoramento do potencial de circuito aberto e as curvas de polariza??o. A partir dos resultados obtidos foi poss?vel identificar as pastilhas de composi??es qu?micas A1 (94,07% de Ti e 5,93% de Zr), A4 (77,81% de Ti e 22,19% de Zr) e A8 (27,83% de Ti e 72,17% de Zr) que resultaram como maiores detentoras do conjunto de propriedades de resist?ncia ? corros?o, homogeneidade e dureza, as quais s?o mais necess?rias em biomateriais tipo pr?teses ortop?dicas ou odontol?gicas

Duplex stainless steels can be very attractive alternatives to austenitic grades due to their almost double strength at equal pitting corrosion resistance. When welding, the duplex alloys normally require addition of filler metal, while the commodity austenitic grades can often be welded autogenously. Over-alloyed consumables are used to counteract segregation of important alloying elements and to balance the two phases, ferrite and austenite, in the duplex weld metal. This work focuses on the weldability of the recently-developed lean duplex stainless steel LDX 2101® (EN 1.4162, UNS S32101). The pitting corrosion resistance of this grade is better than that of austenitic AISI 304 (EN 1.4307) and can reach the level of AISI 316L (EN 1.4404). The austenite formation is rapid in LDX 2101 compared to older duplex grades. Pitting resistance tests performed show that 1-2.5 mm thick laser and gas tungsten arc (GTA) welded LDX 2101 can have good corrosion properties even when welding autogenously. Additions of filler metal, nitrogen in the shielding gas, nitrogen-based backing gas and use of laser hybrid welding methods, however, increase the austenite formation. The pitting resistance may also be increased by suppressing formation of chromium nitrides in the weld metal and heat affected zone (HAZ). After thorough post-weld cleaning (pickling), pitting primarily occurred 1-3 mm from the fusion line, in the parent metal rather than in the HAZ. Neither the chromium nitride precipitates found in the HAZ, nor the element depletion along the fusion line that was revealed by electron probe microanalysis (EPMA) were found to locally decrease the pitting resistance. The preferential pitting location is suggested to be controlled by the residual weld oxide composition that varies over the surface. The composition and thickness of weld oxide formed on LDX 2101 and 2304 (EN 1.4362, UNS S32304) were determined using X-ray photoelectron spectroscopy (XPS). The heat tint on these lean duplex grades proved to contain significantly more manganese than what has been reported for standard austenitic stainless steels in the AISI 300 series. A new approach to heat tint formation is presented; whereby evaporation of material from the weld metal and subsequent deposition on the already-formed weld oxide are suggested to contribute to weld oxide formation. This is consistent with manganese loss from the weld metal, and nitrogen additions to the GTA shielding gas enhance the evaporation. The segregation of all elements apart from nitrogen is low in autogenously welded LDX 2101. This means that filler wire additions may not be required as for other duplex grades assuming that there is no large nitrogen loss that could cause excessive ferrite contents. As the nitrogen appears to be controlling the austenite formation, it becomes essential to avoid losing nitrogen during welding by choosing nitrogen-containing shielding and backing gas. / QC 20101213

<p>Proučavane su koroziona postojanost i tendencija lepljenja različitih<br />materijala u kontaktu sa tečnom Al&ndash;Si&ndash;Cu legurom. Ispitivanjem su<br />obuhvaćeni čelik za rad na toplo, plazma nitrirani čelik i dupleks<br />slojevi sa CrN, TiAlN, TiAlSiN i CrAlN prevlakama, različitog nivoa<br />površinske hrapavosti. Za ispitivanja pomenutih fenomena<br />primenjena je metoda izvlačenja, koja je unapređena kako bi se povećale<br />njena tačnost i verodostojnost simulacije procesa livenja. Korozioni<br />efekti su pojačani tako što su uzorci osim kratkog kontakta sa odlivkom<br />zadržavani i u dužim periodima u kontaktu sa tečnom legurom (5 i 20<br />min). Uprkos opštim stavovima, za ispitivane materijale je<br />ustanovljeno da su sile izvlačenja uzoraka iz Al&ndash;Si&ndash;Cu odlivaka<br />nezavisne od njihovog hemijskog sastava. Uticaj hrapavosti je izražen<br />kod uzoraka sa prevlakama kod kojih pri smanjenju hrapavosti dolazi do<br />povećanja sile izvlačenja. Sve ispitane prevlake su sklone mehaničkom<br />lepljenju Al&ndash;Si&ndash;Cu legure za svoje površine, ali sa aspekta korozije u<br />tečnom metalu značajno prevazilaze performanse čelika i plazma<br />nitriranog sloja. Duži kontakt livene legure sa površinama prevlaka<br />uzrokovao je niže vrednosti sila izvlačenja, što je posledica<br />oksidacije površina prevlaka. Ustanovljeno je da su ispitivane<br />prevlake inertne ka tečnoj leguri aluminijuma. Međutim, dolazi do<br />oksidacije i korozije materijala podloge kroz greške rasta koje su<br />prisutne u prevlakama. Stečena znanja o identifikovanim<br />mehanizmima habanja i propadanja zaštitnih slojeva prevlaka<br />poslužiće daljem razvoju dupleks slojeva namenjenih za zaštitu alata<br />za livenje pod pritiskom.</p> / <p>Corrosion resistance and soldering tendency of different materials in molten<br />Al&ndash;Si&ndash;Cu alloy were studied. Hot-working tool steel, plasma nitrided steel and<br />duplex layers with CrN, TiAlN, TiAlSiN and CrAlN top coatings, which were<br />produced to various degree of surface roughness, were covered by the study.<br />An ejection test was employed for investigation of the concerned phenomena.<br />The ejection test was improved in order to increase its accuracy and the<br />reliability of process simulation. Samples were examined in both short and<br />extended periods of contact (5 and 20 min) with liquid casting. Casting<br />solidification was extended in order to intensify the corrosion effects. Contrary<br />to common findings, it was found that the ejection force of the investigated<br />materials does not depend on their chemical composition. For the coated<br />samples, a pronounced dependence of the ejection force on the surface<br />roughness was found. The ejection force increases with decrease in surface<br />roughness. All investigated coatings are prone to mechanical soldering by Al&ndash;<br />Si&ndash;Cu alloy. Still, their corrosion resistance substantially exceeds the corrosion<br />resistance of steel and plasma nitrided layer. Longer exposure of coated<br />samples to cast alloy induced lower ejection forces, which is a consequence<br />of coatings oxidation. It was found that the investigated coatings are inert to<br />liquid aluminium. However, the underlying material undergoes oxidation and<br />corrosion through coating growth defects. The findings concerning the wear<br />mechanisms of protective layers support further development of duplex layers<br />intended for die casting tools protection.</p>