The interaction of the surface of a pure metal or an alloy with the surrounding atmosphere occurs in a highly complex interfacial regime. During atmospheric corrosion this interfacial regime involves the metal surface, often covered by a naturally formed oxide layer of a few nanometers thickness; an aqueous adlayer, typically with a thickness of a few to a few tens of nanometers, and the atmosphere from which airborne particles, oxygen, and gaseous pollutants dissolve into the adlayer and influence the atmospheric corrosion process. This thesis work is mainly concerned with the initial atmospheric corrosion of zinc and brass induced by carboxylic acids (120 parts per billion of formic, acetic, or propionic acid) in laboratory air with 90% relative humidity. This model system has been chosen to mimic indoor corrosion with carboxylic acids as major corrosion stimulators. The study forms part of a broader research program with the ultimate goal to provide a computer model of the early stages of atmospheric corrosion of copper, zinc and copper-zinc alloys, induced by carboxylic acids. Particular emphasis has been given to identify and quantify the corrosion products formed and to determine their lateral distribution over the corroding surface. This has been accomplished through a multi-analytical approach in which two main techniques are infrared reflection absorption spectroscopy (IRAS) which can identify and quantify corrosion products with a relative accuracy of about 10%, and confocal Raman microspectroscopy (CRM) which can identify and resolve corrosion products with a surface lateral resolution of better than one micrometer. The corrosion products identified on pure zinc are zinc oxide (ZnO) and various forms of Zn-carboxylates. On brass, the main corrosion products identified are a cuprite (Cu2O)-like phase and various forms of Zn-carboxylates. For pure zinc and brass the formation rates of corrosion products in presence of the investigated acids depend, among others, on their deposition velocity and acid strength. The interaction of pure zinc and brass with humidified air containing carboxylic acids follows two spatially separated main pathways: a proton-induced dissolution of metal ions followed by the formation of oxides, and a carboxylate-induced dissolution followed by the deposition of metal carboxylates. When applying this multi-analytical approach, it has been possible to distinguish between anodically and cathodically active areas for brass, but not for pure zinc. Galvanic effects have been shown to play a significant role during the initial corrosion of brass.  Further evidence of the selective formation of corrosion products has been found when exploring the more complex heterogeneous surface of Galvalume, a commercial aluminum-zinc alloy coating. This material has been exposed to humidified laboratory air with additions of carbon dioxide (CO2) and sodium chloride (NaCl) and to a marine atmospheric environment. Initiated in the interdendritic zinc-rich areas, a uniform aluminum oxide (Al2O3) layer is formed. This oxide exhibits an inhibiting effect on the subsequent formation of other corrosion products, including aluminum oxyhydroxide (AlOOH), aluminum hydroxide (Al(OH)3), ZnO, zinc hydroxycarbonate and zinc hydroxychloride. / QC 20110607

Aços carbono trefilados possuem como características excelentes propriedades mecânicas, estabilidade dimensional e bom acabamento superficial. Porém, para fornecimento deste material, um dos cuidados necessários é a proteção temporária contra a corrosão atmosférica, que pode ser definida como um processo resultante de reações químicas e/ou eletroquímicas, pelas quais metais e ligas se deterioram quando submetidos à ação climática. Para evitar / retardar este processo, usualmente é utilizada a aplicação de uma película de óleos formadores de barreira, protegendo o material base. Buscando avaliar a capacidade protetiva de óleos utilizados em materiais trefilados, foram selecionados 3 tipos de produtos usados no polimento e 3 tipos aplicados como proteção final. Diferentes combinações dos produtos foram avaliadas em amostras numa câmara úmida, mostrando que a capacidade protetiva dos óleos de proteção final está diretamente relacionada à sua densidade, diferentemente dos óleos de polimento que não apresentam uma relação direta com as propriedades avaliadas. Com base nestes resultados, pode-se prever a capacidade protetiva de óleos de proteção final utilizando sua densidade como referência, devido a esta relação ser linear, tendo outros fatores, como o tipo de óleo de polimento, afetando a constante da equação da curva. / Drawn carbon steel has excellent mechanical proprieties, dimensional stability and good surface quality as characteristics. But, to supply this material, a necessary care is the temporary protection against atmospheric corrosion, which can be defined as a process resulting from chemical and / or electrochemical reactions, in which metals and alloys deteriorate when subjected to climate action. To avoid / retard this process, usually it’s used an application of an oil coat that protects the base material. Trying to understand the protective capacity of oils used in drawn materials, 3 products used in polishing process and 3 applied as final protection were selected. Samples tested in humid chamber with different combinations of products were evaluated, showing that the protective capacity of oils used as final protection is directly related with their density, a relation that is not presented in polishing oils. With these results we can forecast the protective capacity of oils used as final protection employing its density as reference, because of the linear relation, having another factors, like the type of polishing oil, affecting the curve equation constant.

Aços carbono trefilados possuem como características excelentes propriedades mecânicas, estabilidade dimensional e bom acabamento superficial. Porém, para fornecimento deste material, um dos cuidados necessários é a proteção temporária contra a corrosão atmosférica, que pode ser definida como um processo resultante de reações químicas e/ou eletroquímicas, pelas quais metais e ligas se deterioram quando submetidos à ação climática. Para evitar / retardar este processo, usualmente é utilizada a aplicação de uma película de óleos formadores de barreira, protegendo o material base. Buscando avaliar a capacidade protetiva de óleos utilizados em materiais trefilados, foram selecionados 3 tipos de produtos usados no polimento e 3 tipos aplicados como proteção final. Diferentes combinações dos produtos foram avaliadas em amostras numa câmara úmida, mostrando que a capacidade protetiva dos óleos de proteção final está diretamente relacionada à sua densidade, diferentemente dos óleos de polimento que não apresentam uma relação direta com as propriedades avaliadas. Com base nestes resultados, pode-se prever a capacidade protetiva de óleos de proteção final utilizando sua densidade como referência, devido a esta relação ser linear, tendo outros fatores, como o tipo de óleo de polimento, afetando a constante da equação da curva. / Drawn carbon steel has excellent mechanical proprieties, dimensional stability and good surface quality as characteristics. But, to supply this material, a necessary care is the temporary protection against atmospheric corrosion, which can be defined as a process resulting from chemical and / or electrochemical reactions, in which metals and alloys deteriorate when subjected to climate action. To avoid / retard this process, usually it’s used an application of an oil coat that protects the base material. Trying to understand the protective capacity of oils used in drawn materials, 3 products used in polishing process and 3 applied as final protection were selected. Samples tested in humid chamber with different combinations of products were evaluated, showing that the protective capacity of oils used as final protection is directly related with their density, a relation that is not presented in polishing oils. With these results we can forecast the protective capacity of oils used as final protection employing its density as reference, because of the linear relation, having another factors, like the type of polishing oil, affecting the curve equation constant.

O cobre e suas ligas constitui um dois metais mais amplamente utilizados para a produção de peças com interesse histórico. Isto se deve a sua grande capacidade de combinar com outros compostos, formando pátinas das mais diversas colorações. As peças metálicas do patrimônio histórico se encontram submetidas a condições de exposição atmosférica cada vez mais agressiva, porém frente à necessidade de preservação de nossas memórias históricas este patrimônio deve ser submetido a intervenções de natureza preventiva. O presente trabalho tem por objetivo investigar o comportamento de cobre em águas de chuva sintéticas de São Paulo e de Rio de Janeiro e em solução de NaCl 0,1 M. Investiga-se também o processo de consolidação destas patinas e a ação anticorrosiva das camadas de verniz geralmente utilizado para a proteção do patrimônio histórico (Paraloide B-72) nas soluções e águas de chuva sintéticas. As técnicas eletroquímicas empregadas foram o acompanhamento do potencial de circuito aberto, curvas de polarização anódica e catódica e a espectroscopia de impedância eletroquímica. Como técnicas de caracterização microestrutural e química foram empregadas a microscopia eletrônica de varredura, a difração de raios X e a espectroscopia de fotoelétrons de raios X. Os resultados mostraram que, entre os vernizes empregados para a proteção do patrimônio histórico, os do tipo paralóide são menos suscetíveis à umidade que a cera microcristalina. Para avaliar a resposta do sistema cobre + pátina é importante compreender como o substrato não-tratado responde eletroquimicamente quando é exposto às águas de chuva sintéticas. Os resultados mostraram que na água de chuva sintética do Rio de Janeiro, com baixa concentração de amônio, o ataque prosseguia nas regiões defeituosas da camada de cuprita. Na água de chuva de São Paulo, onde os íons de amônio são abundantes, a regeneração parcial da cuprita ocorre de maneira uniforme melhorando o comportamento eletroquímico. Por sua vez, as pátinas artificiais sobre o substrato de cobre apresentaram uma melhor consolidação quando expostas à atmosfera aberta (Laboratório de Eletroquímica e Corrosão) do que quando expostas a um ambiente com completa ausência de umidade (dessecador). Nos ensaios intermitentes, as pátinas desenvolveram respostas de impedância típica de eletrodo poroso com comprimento de poro semi-infinito seguindo um modelo clássico (DE LEVIE, 1964). Por outro lado, nas amostras de cobre revestidas com paralóide B-72, o grau de diminuição da capacidade protetora após períodos longos de exposição à luz foi atribuída a degradação foto-oxidativa do verniz. A associação do cobre com pátina, sobre a qual se aplicava o verniz Paralóide B-72, mostrou que o sistema de revestimento aumenta a proteção contra a corrosão em ensaios intermitentes. Nos ensaios de imersão contínua, nem as pátinas sozinhas nem quando protegidas com o verniz polaróide, suportaram esses ensaios sem apresentar destacamento. / Copper is one of the metals most widely used to produce metallic artifacts of the artistic and cultural heritage. This is partially due to its great ability to combine with other compounds, forming patinas of different colors. Many of such artifacts are permanently exposed to open air, being thus subjected to the action of atmospheric agents such as rain and pollutants. Thus, these cultural heritage monuments must be submitted to interventions of preventive nature. This work is devoted to investigate the electrochemical behavior of pure copper, with and without an artificial patina layer, in contact with São Paulo and Rio de Janeiro synthetic rainwater and in NaCl 0,1M solution. The consolidation process of these patinas and the anticorrosive action of varnishes generally used for the protection of the cultural heritage were also investigated. The electrochemical techniques used in this work were: cathodic and anodic potentiodynamic polarization curves and electrochemical impedance spectroscopy. Microstructural and chemical characterizations were performed by means of Scanning Electronic Microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results had shown that the varnishes of Paraloid type used for the protection of the historic monuments are less susceptible to the humidity than the microcrystalline wax. The experiments performed with copper in the synthetic rainwater evidenced an important role for the ammonium ions in the corrosion process. Although with a high complexation power towards copper, accelerating its dissolution rate, these ions participate in the partial regeneration of cuprite. Therefore, in the Rio de Janeiro synthetic rainwater, with low ammonium concentration, once the corrosive attack has started it proceeds in the defective regions of the cuprite layer. On the other hand, in the São Paulo synthetic rainwater, where ammonium ions are more abundant, partial regeneration of cuprite occurs and the electrochemical behavior of copper remains stable with time. The experiments performed with copper coated with an artificial patina layer showed better consolidation of these latter when exposed to the open atmosphere (Electrochemistry and Corrosion Laboratory) when compared to samples stored in a dissecator, where humidity is absent. In the intermittent tests patinated samples developed an impedance response which was typical from porous electrode with semi-infinite porous length, in accordance with the classical model proposed by de Levie (DE LEVIE, 1964). On the other hand, Paraloid B-72 coated samples presented a strong degradation when exposed to sunlight for long exposure periods, which was ascribed to the photooxidative degradation of the coating. The system copper plus patina with a Paraloid B-72 layer showed a good protection towards corrosion, as long as photooxidative degradation had not begun. On the other hand, in the continuous immersion tests, neither the patinas nor the Paraloid varnish exhibited a good performance and were detached after relatively short testing period.

Aços carbono trefilados possuem como características excelentes propriedades mecânicas, estabilidade dimensional e bom acabamento superficial. Porém, para fornecimento deste material, um dos cuidados necessários é a proteção temporária contra a corrosão atmosférica, que pode ser definida como um processo resultante de reações químicas e/ou eletroquímicas, pelas quais metais e ligas se deterioram quando submetidos à ação climática. Para evitar / retardar este processo, usualmente é utilizada a aplicação de uma película de óleos formadores de barreira, protegendo o material base. Buscando avaliar a capacidade protetiva de óleos utilizados em materiais trefilados, foram selecionados 3 tipos de produtos usados no polimento e 3 tipos aplicados como proteção final. Diferentes combinações dos produtos foram avaliadas em amostras numa câmara úmida, mostrando que a capacidade protetiva dos óleos de proteção final está diretamente relacionada à sua densidade, diferentemente dos óleos de polimento que não apresentam uma relação direta com as propriedades avaliadas. Com base nestes resultados, pode-se prever a capacidade protetiva de óleos de proteção final utilizando sua densidade como referência, devido a esta relação ser linear, tendo outros fatores, como o tipo de óleo de polimento, afetando a constante da equação da curva. / Drawn carbon steel has excellent mechanical proprieties, dimensional stability and good surface quality as characteristics. But, to supply this material, a necessary care is the temporary protection against atmospheric corrosion, which can be defined as a process resulting from chemical and / or electrochemical reactions, in which metals and alloys deteriorate when subjected to climate action. To avoid / retard this process, usually it’s used an application of an oil coat that protects the base material. Trying to understand the protective capacity of oils used in drawn materials, 3 products used in polishing process and 3 applied as final protection were selected. Samples tested in humid chamber with different combinations of products were evaluated, showing that the protective capacity of oils used as final protection is directly related with their density, a relation that is not presented in polishing oils. With these results we can forecast the protective capacity of oils used as final protection employing its density as reference, because of the linear relation, having another factors, like the type of polishing oil, affecting the curve equation constant.

The corrosion performance of Al-Cu and Al-Mg alloys with and without Li additions have been investigated. These include; AA2024-T3, AA2099-T8E77 (coarse and fine grain structure), AA5083-T351, spray formed Al-Mg-Li and spray formed Al-Mg-Li-Cu-Zn alloy. Atmospheric corrosion was investigated for up to 12 months of exposure in a rural-urban environment, prolonged immersion testing in 3.5 wt.% NaCl for up to 96 hr s and potentiodynamic polarisation in 3.5 wt.% NaCl were examined. This was to answer whether Li additions, spray forming and grain size impacted on the corrosion resistance. Atmospheric exposure showed Al2(CO3)3, NOx, SOx and NaCl compounds being deposited. Cathodic intermetallic compounds (Fe, Si, Mn and Cu rich) were shown to be associated with pitting corrosion, whereas anodic intermetallic compounds (Mg rich) offered sacrificial protection to the matrix. The Al-Cu alloys showed more corrosion compared to the Al-Mg alloys in all three corrosion investigations. The Al-Cu alloys showed pitting corrosion and intergranular corrosion, compared to primarily pitting corrosion on the Al-Mg alloys. AA2024-T3 developed a weakened, friable layer on the surface, consisting of a network of intergranular corrosion and numerous shallow pits. The Al-Cu-Li alloys also showed intergranular corrosion and pitting corrosion, but also developed selective grain dissolution, leading to extensive sub-surface cavities. This showed that Li additions in the Al-Cu alloys was detrimental and was primarily associated with the T type phases likely to be; T1 phase (Al2CuLi). Li additions in the Al-Mg alloys did not show any measurable improvement or reduction in corrosion resistance. Spray forming also did not appear to improve the corrosion resistance. Grain size in turn was shown to impact on corrosion resistance, with the general consensus being that finer grains offer increased corrosion resistances. Al-Cu alloys showed fine grain structures developed easy path propagation for intergranular corrosion, whereas fine grain structures on Al-Mg alloys promoted increased corrosion resistance.

Proprietary mixtures of amines and carboxylic acids are used as volatile corrosion inhibitors (VCIs) for the protection of steel and iron components against atmospheric corrosion during storage and transportation. Interactions between amines and carboxylic acids have been comprehensively reported in the literature. However, little is known about the nature of the vapours these mixtures emit. The present study focused on the development of the evolved gas analysis method which will help in the characterisation of the vapours released by VCIs. In the method, the evaporation of various amine-carboxylic acid binary mixtures was monitored by thermogravimetric analysis (TGA). The nature and the composition of the released vapours was followed by Fourier transform infrared (FTIR) spectroscopy. Mixtures consisting of triethylamine (TEA) and acetic acid were studied as a model compound using TGA-FTIR at 50 °C to validate the TGA-FTIR method. As vaporisation progressed, the composition of the remaining liquid and the emitted vapour converged to a fixed amine content of ca. 27 mol %. This is just above the composition expected for the 1:3 amine: carboxylic acid complex. Mixtures close to this composition also featured the lowest volatility. TGA-FTIR proved to be a convenient method for studying the evaporation of TEA-acetic acid mixtures, and the nature and composition of the released vapours. Amine addition leads to the dissociation of carboxylic acid dimers in favour salt formation. The formation of an ion pair between the amine and carboxylic acid was confirmed by the FTIR spectra of the liquid phase. The resulting amine-carboxylic acid mixtures showed a slow mass loss rate on TGA when compared with the pure amines and pure carboxylic acids. This indicated that the mixtures have low volatility, hence low vapour pressure compared with the pure components. The low vapour pressure of the mixtures was confirmed by the calculated gas permeability values. These values were much higher for the pure amines and the pure carboxylic acids. However, they dropped significantly on amine addition. The strong amine-carboxylic acid interaction is responsible for the suppressed volatility of the mixtures. No interaction is observed between amine and carboxylic acid molecules in the vapour phase at 230 °C. The method developed was applied to characterise the model compounds simulating the amine-carboxylic acid-based volatile corrosion inhibitors. These model systems contained the primary, secondary and tertiary amines (hexylamine, morpholine and triethylamine), as well as carboxylic acids with different chain lengths (acetic, propanoic, hexanoic and octanoic). These systems are usually employed as equimolar mixtures to protect ferrous metals against atmospheric corrosion. The key finding of the study was that the vapours released by such equimolar mixtures initially contain almost exclusively free amine. After prolonged vaporisation, a steady-state “azeotrope”-like composition is approached. It contains excess acid and features impaired corrosion-inhibition efficiencies according to the Skinner test. In part, this behaviour can be attributed to the mismatch between the volatilities of the amine and carboxylic acid constituents. / Thesis (PhD)--University of Pretoria, 2013. / gm2013 / Chemical Engineering / unrestricted

In this Master of Science thesis screws with different coatings were exposed to an accelerated corrosion test in order to investigate the corrosion development. The test matrix constituted of hexagonal and flange screws (fastened on frames) coated with either zinc/iron (ZnFe) or a flake system of aluminum and zinc (GEOMET). The corrosion results were analyzed by means of X-ray diffraction (XRD). In this study the screws were also crosscut and analyzed by means of FEG-SEM in order to determine the thickness and the elemental content of the surface coating. The result of the corrosion test showed that the screws coated with GEOMET showed a very good corrosion resistance whilst the screws coated with ZnFe failed to fulfill the demands on corrosion resistance of Scania.

In a previous project, mobile exposures in road environments have been performed in various areas of the world. A number of materials and coatings have been attached under trailers which travels long distances in different types of road environments. One of the materials, zinc, demonstrated various corrosion rates in different parts of the world. In this investigation two various accelerated corrosion tests have been performed at the laboratory of Swerea Kimab in order to realize parameter influence on zinc. Even though the corrosion rates are known, the relation to formed corrosion products has not been investigated earlier. In the present study, corrosion products on zinc have been analyzed using XRD and FTIR. The results from analyses of formed corrosion products have been evaluated together with measured corrosion rates, both from the mobile exposure and the accelerated tests, in order to try to understand under what conditions certain corrosion products are formed and how it affects the corrosion rate. A cold humid climate was found to be the most corrosive. In these environments, de ‐icing salts are used which promotes formation of Simonkolleite and in a subsequent step; Gordaite (if there is a not negligible deposition rate of SO2/SO42‐) which is often observed as the end product in marine environments.

The interaction of carboxylic acids with copper is a phenomenon found both outdoors and, more commonly, indoors. The influence on copper of some carboxylic acids (formic, acetic, propionic, and butyric) have so far been studied at concentrations levels at least three or four orders of magnitude higher than actual indoor conditions (< 20 ppb, volume parts per billion), and with only limited emphasis on any mechanistic approach. In this licentiate study a unique analytical setup has been successfully applied for in situ characterization and quantification of corrosion products formed during initial atmospheric corrosion of copper in the presence of acetic, formic or propionic acid. The setup is based on monitoring mass changes by the quartz crystal microbalance (QCM) and simultaneously identifying the chemical species by infrared reflection-absorption spectroscopy (IRAS). Post-analysis of corrosion products was performed by coulometric reduction (mass of copper (I) oxide formed), grazing incidence x-ray diffraction (phase identification) and atomic force microscopy (surface topography). The absolute amounts of mass of individual constituents in the corrosion products, mainly copper (I) oxide or cuprite, copper (II) carboxylate and water or hydroxyl groups, have been deduced in situ during exposure in 120 ppb of carboxylic acid concentration, 95% relative humidity and 20ºC. An overall result is the consistency of analytical information obtained. For copper (I) oxide the quantified data estimated from IRAS, QCM or coulomeric reduction agrees with a relative accuracy of 12 % or better. The interaction of copper with the carboxylic acids seems to follow two spatially separated main pathways. A proton-induced dissolution of cuprous ions followed by the formation of copper (I) oxide, and a carboxylate-induced dissolution followed by the formation of copper (II) carboxylate. The first pathway is initially very fast but levels off with a more uniform growth over the surface. This pathway dominates in acetic acid. The second pathway exhibits a more constant growth rate and localized growth, and dominates in formic acid. Propionic acid exhibits low rates for both pathways. The difference between the carboxylic acids with respect to both total corrosion rate and carboxylate-induced dissolution can be attributed to differences in acid dissociation constant and deposition velocity.