Epoxy coatings are currently the most popular corrosion protection mechanism for steel reinforcement in structural concrete. However, these coatings are easily damaged on worksites, negating their intended purpose. This study investigates self-healing coatings for steel reinforcement to introduce an autonomous healing mechanism for damaged coatings. Coatings were applied to steel coupons, intentionally damaged, and introduced to a corrosive environment via aerated salt-water tanks. Performance of the experimental coatings was evaluated qualitatively and quantitatively. Adhesion strength and effects of coating thickness were also studied. Results from coated steel coupons subjected to damage and submerged in salt-water aeration tanks exhibited improved corrosion resistance performance with self-healing coatings. However, self-healing coatings have comparable poor adhesion to the substrate as do conventional coatings. This paper shows preliminary results demonstrating the potential benefits of self-healing coatings for steel reinforcement and identifies numerous avenues for future research.

A corrosão nos materiais metálicos causa sérias perdas financeiras e impactos ambientais. Apesar de eficientes, os revestimentos orgânicos podem gerar fissuras com o tempo, propiciando locais favoráveis à corrosão. Diante disso, o conceito de autorreparação em revestimentos tem sido estudado, para que este tipo de dano seja minimizado, sem necessitar da intervenção humana. O método de encapsulamento de formadores de filme em microcápsulas poliméricas é bastante utilizado nos sistemas de autorregeneração. Neste trabalho, estudou-se o processo de emulsificação do óleo de linhaça, etapa determinante para a obtenção das microcápsulas, que serão posteriormente aditivadas em um primer de epóxi base água. Inicialmente, foi necessário aperfeiçoar o preparo da emulsão, analisando-se para isso três tipos diferentes de tensoativos em termos de propriedades e composições. Foi feito um planejamento estatístico no qual se adotou o modelo de projeto fatorial completo para cada um dos tensoativos, onde os fatores analisados foram a variação da fração mássica do tensoativo, a aplicabilidade do ultrassom ou dispersor Ultra-Turrax® e a adição ou não de cloreto de sódio. O pequeno número de ensaios envolvidos e a simplicidade para se analisar e interpretar os dados justificam a escolha deste modelo. As variáveis resposta foram a determinação do diâmetro médio volumétrico das gotículas e a medida do potencial zeta das emulsões para analisar a estabilidade das mesmas. Além disso, observou-se a forma, tamanho e característica das gotículas com o auxílio de um microscópio óptico. A estabilidade da emulsão também foi avaliada pela observação e registro fotográfico da separação de fases, depois de certo tempo em repouso, em um tubo de ensaio. Após a determinação do melhor tensoativo e condições de preparo da emulsão na obtenção das microcápsulas, estas foram obtidas e adicionadas no primer e o mesmo foi aplicado sobre corpos de prova de aço carbono. O efeito de autorreparação proporcionado pela ruptura das microcápsulas ao se provocar um defeito foi avaliado pelas técnicas de espectroscopia de impedância eletroquímica (EIS), técnica de varredura com eletrodo vibratório (SVET) e pelo ensaio acelerado de corrosão em câmara de névoa salina (SSC). As microcápsulas foram caracterizadas por microscopia óptica e microscopia eletrônica de varredura (SEM). / The corrosion of metallic materials causes serious financial losses and environmental impacts. Although efficient, organic coatings may generate cracks over time, generating potential sites for corrosion. Hence, the self-healing concept on coatings has been studied in order to minimize this type of damage, without requiring human intervention. The encapsulation method of film formers in polymeric microcapsules is widely used in self-healing systems. In this study, the emulsification process of linseed oil was investigated, since it is a determining step to obtain the microcapsules that will later be doped in a water based epoxy primer. Initially, it was necessary to improve the emulsion preparation, by analyzing three types of surfactants with different properties and compositions. A statistical planning adopting the full factorial design model was conducted for each of the surfactants, in which the factors considered were the variation of the weight fraction of surfactant, and the use or not of ultrasound, Ultra-Turrax® disperser and sodium chloride. The small number of trials involved and the simplicity to analyze and interpret the data justify the choice of this statistical model. The response variables were the determination of the droplet volumetric mean diameter and the measurement of the zeta potential of the emulsions to assess its stability. Moreover, the shape and characteristics of the droplets were observed with the aid of an optical microscope. The emulsion stability was also evaluated by observation and photographic register of phase separation after some rest time in a test tube. After determining the best surfactant and conditions for the emulsification to obtain the microcapsules, they were produced and added to the primer, which was applied on carbon steel specimens. The self-healing effect provided by the rupture of the microcapsules after an intentional defect was evaluated by electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) and accelerated corrosion tests in a salt spray chamber (SSC). The microcapsules were characterized by optical and scanning electron microscopes (SEM).

A corrosão nos materiais metálicos causa sérias perdas financeiras e impactos ambientais. Apesar de eficientes, os revestimentos orgânicos podem gerar fissuras com o tempo, propiciando locais favoráveis à corrosão. Diante disso, o conceito de autorreparação em revestimentos tem sido estudado, para que este tipo de dano seja minimizado, sem necessitar da intervenção humana. O método de encapsulamento de formadores de filme em microcápsulas poliméricas é bastante utilizado nos sistemas de autorregeneração. Neste trabalho, estudou-se o processo de emulsificação do óleo de linhaça, etapa determinante para a obtenção das microcápsulas, que serão posteriormente aditivadas em um primer de epóxi base água. Inicialmente, foi necessário aperfeiçoar o preparo da emulsão, analisando-se para isso três tipos diferentes de tensoativos em termos de propriedades e composições. Foi feito um planejamento estatístico no qual se adotou o modelo de projeto fatorial completo para cada um dos tensoativos, onde os fatores analisados foram a variação da fração mássica do tensoativo, a aplicabilidade do ultrassom ou dispersor Ultra-Turrax® e a adição ou não de cloreto de sódio. O pequeno número de ensaios envolvidos e a simplicidade para se analisar e interpretar os dados justificam a escolha deste modelo. As variáveis resposta foram a determinação do diâmetro médio volumétrico das gotículas e a medida do potencial zeta das emulsões para analisar a estabilidade das mesmas. Além disso, observou-se a forma, tamanho e característica das gotículas com o auxílio de um microscópio óptico. A estabilidade da emulsão também foi avaliada pela observação e registro fotográfico da separação de fases, depois de certo tempo em repouso, em um tubo de ensaio. Após a determinação do melhor tensoativo e condições de preparo da emulsão na obtenção das microcápsulas, estas foram obtidas e adicionadas no primer e o mesmo foi aplicado sobre corpos de prova de aço carbono. O efeito de autorreparação proporcionado pela ruptura das microcápsulas ao se provocar um defeito foi avaliado pelas técnicas de espectroscopia de impedância eletroquímica (EIS), técnica de varredura com eletrodo vibratório (SVET) e pelo ensaio acelerado de corrosão em câmara de névoa salina (SSC). As microcápsulas foram caracterizadas por microscopia óptica e microscopia eletrônica de varredura (SEM). / The corrosion of metallic materials causes serious financial losses and environmental impacts. Although efficient, organic coatings may generate cracks over time, generating potential sites for corrosion. Hence, the self-healing concept on coatings has been studied in order to minimize this type of damage, without requiring human intervention. The encapsulation method of film formers in polymeric microcapsules is widely used in self-healing systems. In this study, the emulsification process of linseed oil was investigated, since it is a determining step to obtain the microcapsules that will later be doped in a water based epoxy primer. Initially, it was necessary to improve the emulsion preparation, by analyzing three types of surfactants with different properties and compositions. A statistical planning adopting the full factorial design model was conducted for each of the surfactants, in which the factors considered were the variation of the weight fraction of surfactant, and the use or not of ultrasound, Ultra-Turrax® disperser and sodium chloride. The small number of trials involved and the simplicity to analyze and interpret the data justify the choice of this statistical model. The response variables were the determination of the droplet volumetric mean diameter and the measurement of the zeta potential of the emulsions to assess its stability. Moreover, the shape and characteristics of the droplets were observed with the aid of an optical microscope. The emulsion stability was also evaluated by observation and photographic register of phase separation after some rest time in a test tube. After determining the best surfactant and conditions for the emulsification to obtain the microcapsules, they were produced and added to the primer, which was applied on carbon steel specimens. The self-healing effect provided by the rupture of the microcapsules after an intentional defect was evaluated by electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) and accelerated corrosion tests in a salt spray chamber (SSC). The microcapsules were characterized by optical and scanning electron microscopes (SEM).

The present work is devoted to establishing of a new generation of self-healing anti-corrosion coatings for protection of metals. The concept of self-healing anticorrosion coatings is based on the combination of the passive part, represented by the matrix of conventional coating, and the active part, represented by micron-sized capsules loaded with corrosion inhibitor. Polymers were chosen as the class of compounds most suitable for the capsule preparation. The morphology of capsules made of crosslinked polymers, however, was found to be dependent on the nature of the encapsulated liquid. Therefore, a systematic analysis of the morphology of capsules consisting of a crosslinked polymer and a solvent was performed. Three classes of polymers such as polyurethane, polyurea and polyamide were chosen. Capsules made of these polymers and eight solvents of different polarity were synthesized via interfacial polymerization. It was shown that the morphology of the resulting capsules is specific for every polymer-solvent pair. Formation of capsules with three general types of morphology, such as core-shell, compact and multicompartment, was demonstrated by means of Scanning Electron Microscopy. Compact morphology was assumed to be a result of the specific polymer-solvent interactions and be analogues to the process of swelling. In order to verify the hypothesis, pure polyurethane, polyurea and polyamide were synthesized; their swelling behavior in the solvents used as the encapsulated material was investigated. It was shown that the swelling behavior of the polymers in most cases correlates with the capsules morphology. Different morphologies (compact, core-shell and multicompartment) were therefore attributed to the specific polymer-solvent interactions and discussed in terms of “good” and “poor” solvent. Capsules with core-shell morphology are formed when the encapsulated liquid is a “poor” solvent for the chosen polymer while compact morphologies are formed when the solvent is “good”. Multicompartment morphology is explained by the formation of infinite networks or gelation of crosslinked polymers. If gelation occurs after the phase separation in the system is achieved, core-shell morphology is present. If gelation of the polymer occurs far before crosslinking is accomplished, further condensation of the polymer due to the crosslinking may lead to the formation of porous or multicompartment morphologies. It was concluded that in general, the morphology of capsules consisting of certain polymer-solvent pairs can be predicted on the basis of polymer-solvent behavior. In some cases, the swelling behavior and morphology may not match. The reasons for that are discussed in detail in the thesis. The discussed approach is only capable of predicting capsule morphology for certain polymer-solvent pairs. In practice, the design of the capsules assumes the trial of a great number of polymer-solvent combinations; more complex systems consisting of three, four or even more components are often used. Evaluation of the swelling behavior of each component pair of such systems becomes unreasonable. Therefore, exploitation of the solubility parameter approach was found to be more useful. The latter allows consideration of the properties of each single component instead of the pair of components. In such a manner, the Hansen Solubility Parameter (HSP) approach was used for further analysis. Solubility spheres were constructed for polyurethane, polyurea and polyamide. For this a three-dimensional graph is plotted with dispersion, polar and hydrogen bonding components of solubility parameter, obtained from literature, as the orthogonal axes. The HSP of the solvents are used as the coordinates for the points on the HSP graph. Then a sphere with a certain radius is located on a graph, and the “good” solvents would be located inside the sphere, while the “poor” ones are located outside. Both the location of the sphere center and the sphere radius should be fitted according to the information on polymer swelling behavior in a number of solvents. According to the existing correlation between the capsule morphology and swelling behavior of polymers, the solvents located inside the solubility sphere of a polymer give capsules with compact morphologies. The solvents located outside the solubility sphere of the solvent give either core-shell or multicompartment capsules in combination with the chosen polymer. Once the solubility sphere of a polymer is found, the solubility/swelling behavior is approximated to all possible substances. HSP theory allows therefore prediction of polymer solubility/swelling behavior and consequently the capsule morphology for any given substance with known HSP parameters on the basis of limited data. The latter makes the theory so attractive for application in chemistry and technology, since the choice of the system components is usually performed on the basis of a large number of different parameters that should mutually match. Even slight change of the technology sometimes leads to the necessity to find the analogue of this or that solvent in a sense of solvency but carrying different chemistry. Usage of the HSP approach in this case is indispensable. In the second part of the work examples of the HSP application for the fabrication of capsules with on-demand-morphology are presented. Capsules with compact or core-shell morphology containing corrosion inhibitors were synthesized. Thus, alkoxysilanes possessing long hydrophobic tail, combining passivating and water-repelling properties, were encapsulated in polyurethane shell. The mechanism of action of the active material required core-shell morphology of the capsules. The new hybrid corrosion inhibitor, cerium diethylhexyl phosphate, was encapsulated in polyamide shells in order to facilitate the dispersion of the substance and improve its adhesion to the coating matrix. The encapsulation of commercially available antifouling agents in polyurethane shells was carried out in order to control its release behavior and colloidal stability. Capsules with compact morphology made of polyurea containing the liquid corrosion inhibitor 2-methyl benzothiazole were synthesized in order to improve the colloidal stability of the substance. Capsules with compact morphology allow slower release of the liquid encapsulated material compared to the core-shell ones. If the “in-situ” encapsulation is not possible due to the reaction of the oil-soluble monomer with the encapsulated material, a solution was proposed: loading of the capsules should be performed after monomer deactivation due to the accomplishment of the polymerization reaction. Capsules of desired morphologies should be preformed followed by the loading step. In this way, compact polyurea capsules containing the highly effective but chemically active corrosion inhibitors 8-hydroxyquinoline and benzotriazole were fabricated. All the resulting capsules were successfully introduced into model coatings. The efficiency of the resulting “smart” self-healing anticorrosion coatings on steel and aluminium alloy of the AA-2024 series was evaluated using characterization techniques such as Scanning Vibrating Electron Spectroscopy, Electrochemical Impedance Spectroscopy and salt-spray chamber tests. / In Anlehnung an den Selbstheilungsmechanismus der menschlichen Haut entwickeln wir ein innovatives Verfahren zur Funktionalisierung von Korrosionsschutzbeschichtungen, um auch diese in die Lage zu versetzen Beschädigungen selbstständig „auszuheilen“. Dazu werden winzige Mikro- und Nanobehälter mit aktiven Substanzen (z. B. Korrosionshemmstoffen, Versiegelungsmitteln, Bioziden etc.) befüllt und anschließend in eine Korrosionsschutzbeschichtung eingebettet. Kommt es nun im Zeitablauf zu korrosionsauslösenden Beschädigungen der Schutzbeschichtung (z. B. durch Kratzer oder Risse) werden an der Defektstelle die eingebetteten Behälter zerstört und aktiv wirkende Gegensubstanzen freigesetzt. Dadurch wird die verletzte Stelle sofort wieder verschlossen und die Korrosionsgefahr eliminiert. Der entscheidende Vorteil derart funktionalisierter Schutzbeschichtungen ist ihre aktive Rückkopplung mit dem Korrosionsauslöser: Die aktive Schutzsubstanz wird nur an der Defektstelle und nur in der zur Korrosionsvermeidung erforderlichen Menge freigegeben. Somit werden eine länger anhaltende Wirkdauer sowie eine deutlich höhere Nachhaltigkeit der Beschichtungen ermöglicht. Dieses „intelligente Verhalten“ der neuen aktiven Korrosionsschutzbeschichtungen ist nur dank ihrer innovativen Mikrostruktur möglich. Die winzigen Mikro- und Nanobehälter beinhalten nicht nur aktive Substanzen in ihrem Inneren sondern besitzen auch eine intelligent konstruierte Hüllenstruktur, deren Durchlässigkeit sich je nach Art des Korrosionsauslösers ändert. Wird die eingekapselte aktive Substanz freigesetzt, fängt diese sofort an gegen die korrosionsverursachenden Einflüsse zu wirken. Ist die Gefahr beseitigt verringert sich die Durchlässigkeit der Behälterhülle wieder. Diese bedingte Reversibilität zwischen geschlossenem und geöffnetem Zustand des Behälters sorgt für einen sehr sparsamen Verbrauch der aktiven Substanz und für die stark verbesserte Schutzwirkung darauf basierender Antikorrosionsbeschichtungen. Diese Arbeit befasst sich mit dem Aufbau polymerer Kern-Schale-Mikrokapseln, die entsprechende Korrosionsinhibitoren und Biocide enthalten. Der Morphologie wird für zahlreiche Lösungsmittel und Polymere mit Hilfe der Hansen-Löslichkeitsparameter in guter Übereinstimmung mit elektronenmikroskopischen Experimenten beschrieben. Die Wirkungsweise in technischen Beschichtungen wird quantifiziert anhand von elektrochemischer Impedanzspektroskopie, Rastervibrationssondenmessungen und industrienahen Testverfahren.