Abstract der Posterpräsentation: Ebenso wie Geschirrspülmaschinen in deutschen Haushalten mit ca. 68 % eine weite Verbreitung finden, treten unästhetische Korrosionsproduktablagerungen und Lochkorrosion auf Besteckteilen auf [1]. Zur Vermeidung von Korrosionsschäden an metallischen Werkstoffen unter Bedingungen der maschinellen Geschirrreinigung liegt es nahe, eine Schutzanode in den Besteckkorb einzubringen. Der kathodische Korrosionsschutz mit Hilfe von Schutzanoden wird bekanntermaßen bei Schiffen, Pipelines und Bohrinseln genutzt. Der stabile metallische Kontakt durch das Verschrauben der Anode an das Schutzobjekt kann für Besteck im Geschirrspüler jedoch nicht gewährleistet werden, sodass das Aufstellen der Besteckteile auf die Anode zu wechselnden Widerstandsverhältnissen im Kontaktbereich führt. Zudem liegen während eines Spülganges sehr unterschiedliche Bedingungen (Reiniger: pH > 9,5; Klarspüler: pH < 3,5; Essensreste) vor, und es kommt auf Grund der dünnen Elektrolytfilme zu einer graduellen Änderung der lokalen Elektrodenpotentiale längs des Besteckteils. Elektrochemische Untersuchungen an Aluminiumwerkstoffen unterschiedlicher Zusammensetzung sowie an diversen Besteckstählen bestätigen ebenso wie Messungen an beiden Komponenten in galvanischem Kontakt, dass eine kathodische Polarisation des Stahls um mehrere 100 mV zustande kommt. Experimente im Geschirrspüler zeigten jedoch, dass unter verschiedenen Bedingungen eine dünne Ablagerung von Korrosionsprodukten auftrat, so dass die Eingangshypothese anodischer Korrosionsprozesse am Stahl offenbar revidiert werden muss. Ursachen hierfür werden analysiert, indem eine Dünnfilmströmungszelle, die pH-Wert-Messung bei Stahl-Anoden-Kontakt mit geringer Elektrolytmenge und Temperaturanstieg sowie das instrumentierte maschinelle Geschirrspülen (In-situ-Temperatur- und Potentialmessung des Stahles im direkten Kontaktbereich zur Anode) genutzt werden. Die Ursache der Korrosion des Stahles bei Kontakt mit der Anode konnte bisher nicht hinreichend geklärt werden.

In a variety of engineering applications, components are subjected to corrosive environment. Protective coatings are essential to improve the functional performances and/or extend the lifetime of the components. Thermal sprayingas a cost-effective coating deposition technique offers high flexibility in coatings' chemistry/morphology/microstructure design. However, the inherent pores formed during spraying limit the use of coatings for corrosion protection. The recently developed supersonic spray method, High-Velocity-Air-Fuel (HVAF), brings significant advantages in terms of cost and coating properties. Although severely reduced, the pores are not completely eliminated even with the HVAF process. In view of the above gap to have a high quality coating, bi-layer coatings have been developed to improve the corrosion resistance of the coatings. In a bi-layer coating, an intermediate layer is deposited on the substrate before spraying the coating. The electrochemical behavior of each layer is important to ensure a good corrosion protection. The corrosion behavior of the layers strongly depends on coating composition and microstructure, which are affected by feedstock material and spraying process. Therefore, the objective of the researchis to explore the relationships between feedstock material, spraying process, microstructure and corrosion behavior of bi-layer coatings. A specific motivationis to understand the corrosion mechanisms of the intermediate layer which forms the basis for developing superior protective coatings. Cr3C2-NiCr top layer and intermediate layers (Fe-, Co- and Ni-based) were sprayed by different thermal spraying processes. Microstructure analysis, as well as various corrosion tests, e.g., electrochemical, salt spray and immersion tests were performed. The results showed a direct link between the corrosion potential (Ecorr) of the intermediate layer and the corrosion mechanisms. It was found that the higher corrosion resistance of Ni-based coatings than Fe- and Co-based coatings was due to higher Ecorr of the coating in the galvanic couple with top layers. Inter-lamellar boundaries and interconnected pores reduced the corrosion resistance of intermediate layers, however a sufficient reservoir of protective scale-forming elements (such as Cr or Al) improved the corrosion behavior.

Aluminium och aluminiumlegeringar har ganska bra korrosionsbeständighet, men dessa material kan fortfarande korrodera. Metallkorrosion är aldrig önskvärt och det kan leda till katastrofala resultat i olika branscher och applikationer. Det finns olika metoder för att skydda aluminium och dess legeringar från korrosion, såsom anodisering och användning av olika beläggningstekniker. Inte mycket forskning har gjorts på aluminium belagd med en organisk beläggning innehållande ledande polymer. Ännu mindre är känt om aluminium belagt med en vattenbaserad polymer matris innehållande ledande polymer.  Tre system undersöktes i mitt examensarbete om deras korrosionsskyddande egenskaper. För detta ändamål användes elektrokemisk impedansspektroskopi, öppen kretspotential och potentiodynamisk polarisering, samt gjordes även en del atomkraftsmikroskopi, AFM, mätningar. Aluminium belagt med en vattenbaserad polymer matris i frånvaro av PANI hade ett bra korrosionsskydd först men reducerade barriäregenskaper över tiden i 1 M NaCl. Hållbarheten för den vattenbaserade polymer matrisen i frånvaro av PANI undersöktes också kort. Det visades att en nygjord vattenbaserad polymer matris uppvisade bättre korrosionsskydd än en 2 år gammal vattenbaserad polymer matris lagrad vid rumstemperatur.  Aluminium belagt med den vattenbaserade polymer matrisen i närvaro av PANI visade initialt tecken på aktivt korrosionsskydd men övergick till passivt korrosionsskydd med tiden. Atomkraftmikroskop användes i olika lägen för att få insikt om den vattenbaserade polymer matrisen i närvaro av PANI. Ett ledande nätverk observerades i AFM-mätningarna och konfokalt ljusmikroskop antydde verkligen att detta skulle vara fallet. Det ledande nätverket i den vattenbaserade polymer matrisen kan förklara det aktiva korrosionsskyddet som observerades initialt. Fler studier behövs för att få insikt om de kemiska processerna vid gränssnittet mellan aluminiumlegeringen och den vattenbaserade polymer matrisen i närvaro av PANI. / Aluminum and aluminum alloys have rather good corrosion resistance, but these materials can still corrode. Metal corrosion is never wanted, and it can lead to disastrous outcomes in various industries and applications. There are different methods to protects aluminum and its alloys from corrosion, such as anodization and the use of various coatings techniques. Not a lot of research have been done on aluminum coated with an organic coating containing conductive polymer. Even less is known about aluminum coated with a waterborne polymer matrix containing conductive polymer.  Three systems were investigated in my diploma thesis work regarding their anti-corrosion properties. To this end electrochemical impedance spectroscopy, open circuit potential and potentiodynamic polarization were utilized, and also some atomic force microscopy, AFM, measurements were done. Aluminum coated with a waterborne polymer matrix in the absence of PANI had a good corrosion protection at first but reduced barrier properties over time in 1 M NaCl. The shelf-life of the waterborne polymer matrix in the absence of PANI was also briefly investigated. It was shown that a freshly made waterborne polymer matrix exhibited better corrosion protection than a 2 years old waterborne polymer matrix stored at room temperature.  Aluminum coated with the waterborne polymer matrix in the presence of PANI showed signs of active corrosion protection initially, but it transitioned to passive corrosion protection with time. Atomic force microscopy was used in various modes to gain insight on the waterborne polymer matrix in the presence of PANI. A conducting network was observed in the AFM measurements and confocal light optical microscopy indeed suggested that this would be the case. The conducting network in the waterborne polymer matrix could explain the active corrosion protection observed initially. More studies are needed to gain insight on the chemical processes at the interface of the aluminum alloy and the waterborne polymer matrix in presence of PANI.

Adding layered double hydroxides (LDHs) to polymer compounds has been shown to make them more resistant to corrosion and improve their physical and chemical properties. However, the main challenge lies in the compatibility between inorganic LDH fillers and organic polymer matrices. The incompatibility between these two is due to differences in polarity and surface properties, which makes dispersion of LDHs within the polymer very difficult, negatively affecting the final material's performance and characteristics. In this work, Zn-Al-NO3 LDH particles were synthesized through co-precipitation method and then modified by decavanadate via the anion exchange process. Then, a silane coupling agent was used to functionalize intercalated LDH particles to make them more hydrophobic; this helped the particles to disperse well inside epoxy coating, which ultimately resulted in better corrosion inhibition performance for the coating. The concentration effect of silane coupling agent on LDHs' surface grafting was also studied using various concentrations of 3-aminopropyltriethoxy silane (APTES). Compositional and structural characterization study on revealed more insight into how the surface treatments worked. Finally, to modify LDHs, sodium dodecyl sulfate was inserted in LDH structure, then APTES molecules were grafted on the dodecyl sulfate intercalated LDHs' surface. These organic intercalation and grafting steps made LDHs more suitable with acrylic resin to form uniform composite mixture through solvent solution mixing. The thermal stability of acrylic coating improved by adding modified hybrid LDH fillers and elevation in decomposition temperature was confirmed using thermogravimetric analysis.

Le Cold spray est une technique de réalisation de dépôts épais par projection à haute vitesse de particules. Pour cette technologie, la température du gaz vecteur reste inférieure au point de fusion de poudres projetées. Dans ce cas, les mécanismes d’adhésion sont liés aux hautes déformations plastiques que subissent les particules lors de leur impact avec le substrat. Parmi la grande variété de poudres disponibles, trois compositions ont été retenues pour ce travail. Elles autorisent l’élaboration (i) d’alliage d’aluminium, (ii) d’acier inoxydable et (iii) de magnésium. L’ajout de particules de SiC (en fonction de leur quantité ou taille) aux poudres d’aluminium a également permis de modifier les propriétés mécaniques (telle que la dureté) des couches produites. En formant des couches denses et très peu poreuses, les revêtements cold spray présentent tous les atouts des revêtements anti-corrosion. Ce travail de thèse s’est attaché à comprendre les relations existantes entre les paramètres de projection de poudres (température et pression du gaz vecteur, concentration et tailles des particules de SiC) et la qualité du revêtement obtenu, de définir les interfaces substrat / revêtement en fonction de leur composition chimique et leurs influences sur les propriétés de protection vis-à-vis de la corrosion du substrat. D’un point de vu microstructural, les résultats obtenus montrent que l’augmentation de température du gaz améliore la densité des revêtements. En diminuant le nombre de défauts mais également en optimisant la qualité de l’interface substrat/revêtement, la résistance à la corrosion se trouve également améliorée. Sur la base des différences de potentiel entre le revêtement et le substrat, il est possible de classer la nature des couches selon (i) les revêtements sacrificiels et (ii) les revêtements cathodiques. Quel que soit leur nature, les revêtements obtenus par cold spray présentent tous de bonnes propriétés barrières. Toute fois le mode de dégradation des revêtements sacrificielles a pu être assimilé à de la corrosion intergranulaire en lien avec la morphologie du dépôt mais également la distribution et la taille de particule SiC (cas particulier du revêtement d’aluminium). Si les essais de corrosion longue durée ne permettent pas d’amorcer la corrosion du substrat après dissolution du revêtement (pour les couches sacrifielles), des essais de corrosion galvanique autorisent une discrimination rapide de l’efficacité de la couche barrière. Ces tests électrochimiques sont également l’occasion de discuter des effets de la rupture d’un revêtement sur les cinétiques de corrosion des matériaux qu’ils protègent. L’ensemble des caractérisations métallurgiques ainsi que les tests électrochimiques menés sur les différents assemblages substrat/revêtements indiquent que la technique de cold spray est une méthode de choix pour la protection des matériaux de structures vis-à-vis de la corrosion. / Cold spray is a relatively new coating technology in which coatings are produced by powders projected at high velocity. A significant feature of cold spray is that bonding is generated through severe plastic deformation at temperatures well below melting point of feedstock powders. In the present study, kinds of metallic coatings were produced by cold spray, including aluminum alloy coating, pure magnesium coating, magnesium alloy coating, stainless steel coating and SiC reinforced composite coatings. According to the manner in which the coating protects its substrate against corrosion, these cold sprayed coatings can be divided into two types, i.e. sacrificial anodic coating and noble barrier coating. The objective of this thesis is to verify the feasibility of producing both sacrificial anodic coating and noble barrier coating with high corrosion performance by cold spray, and meanwhile demonstrate the usefulness of electrochemical measurements for the characterization of corrosion protection properties of cold sprayed coatings. Besides material system, process parameters which influence corrosion performance of cold sprayed coatings were studied. Two factors, i.e. process gas temperature and process gas pressure were chosen. Results showed that higher process gas temperature leads to denser aluminum coating. Likely, higher process gas pressure improves denseness and corrosion resistance of stainless steel 316L coating. SiC reinforced aluminum based composite coatings were deposited on aluminum, stainless steel and magnesium substrate. Compared with aluminum coating, the addition of hard ceramic particle affects microstructure of coatings, and improves corrosion resistance by increasing denseness. Ceramic particle fraction and size affect coating microstructure in different ways and also influence corrosion behavior. In view of corrosion process, results indicate that corrosion protection of cold sprayed coating could be divided into two steps. In the first step, substrate is completely shielded by dense coating, no corrosion reaction occurs on substrate. In the second step, two types of coatings show totally different behavior. In the case of sacrificial anodic coating, substrate is under cathodic protection in galvanic couple; hence no corrosion (or weakened corrosion) happens on substrate. In contrast, when the coating is noble than substrate, the protection effect would be immediately interrupted once corrosive electrolyte penetrates through coating to interface. The overall results indicate that cold spray is a highly reliable alternative for production of coatings in anti-corrosion applications. Electrochemical measurements are useful tools for quality evaluation of corrosion behavior of cold sprayed coatings.

The purpose of this research work was to develop a nozzle capable of depositing dense CoNiCrAlY coatings via cold gas dynamic spray (CGDS) as well as compare the oxidation performance of bond coats manufactured by CGDS, high-velocity oxy-fuel (HVOF) and air plasma spray (APS) at temperatures of 1000°C and 1100°C. The work was divided in two sections, the design and manufacturing of a CGDS nozzle with an optimal profile for the deposition of CoNiCrAlY powders and the comparison of the oxidation performance of CoNiCrAlY bond coats. Throughout this work, it was shown that the quality of coatings deposited via CGDS can be increased by the use of a nozzle of optimal profile and that early formation of protective α-Al2O3 due to an oxidation temperature of 1100°C as opposed to 1000°C is beneficial to the overall oxidation performance of CoNiCrAlY coatings.

The purpose of this research work was to develop a nozzle capable of depositing dense CoNiCrAlY coatings via cold gas dynamic spray (CGDS) as well as compare the oxidation performance of bond coats manufactured by CGDS, high-velocity oxy-fuel (HVOF) and air plasma spray (APS) at temperatures of 1000°C and 1100°C. The work was divided in two sections, the design and manufacturing of a CGDS nozzle with an optimal profile for the deposition of CoNiCrAlY powders and the comparison of the oxidation performance of CoNiCrAlY bond coats. Throughout this work, it was shown that the quality of coatings deposited via CGDS can be increased by the use of a nozzle of optimal profile and that early formation of protective α-Al2O3 due to an oxidation temperature of 1100°C as opposed to 1000°C is beneficial to the overall oxidation performance of CoNiCrAlY coatings.

Corrosion protection performance of a completely soluble polyaniline-dodecylbenzenesulfonic acid salt (PANI-DBSA) on C45 steel has been studied with electrochemical impedance and potentiodynamic measurements. Chloroform is the most suitable solvent to process the pristine PANI-DBSA because of negligible interaction of the solvent with the polyaniline (PANI) backbone. An anodic shift in the corrosion potential (<img src="http://scitation.aip.org/stockgif3/Dgr.gif" alt="Delta" align="bottom" border="0"><i>E</i>=~70&nbsp;&nbsp;mV), a decrease in the corrosion current and a significant increase in the charge transfer resistance indicate a significant anti-corrosion performance of the soluble PANI deposited on the protected steel surface. Corrosion protection follows the mechanism of formation of a passive oxide layer on the surface of C45 steel. In situ UV-Vis spectroscopy was used to investigate the differences in permeability of aqueous anions into PANI-DBSA. Preliminary results of electron diffraction studies show that PANI-DBSA possesses an orthorhombic type of crystal structure. An increase in the feed ratio of DBSA to aniline increases the tendency of aggregation of spherical particles of PANI obvious in transmission electron microscopy. PANI-DBSA slowly loses its electrochemical activity in acid free electrolyte without undergoing degradation.

This thesis describes technical and scientific aspects of new types of composite films/coatings for corrosion protection of carbon steel, composite films with nanometer thickness consisting of mussel adhesive protein (Mefp‐1) and ceria nanoparticles, and polymeric composite coatings with micrometre thickness consisting of conducting polymer and ceria nanoparticles in a UV‐curing polyester acrylate (PEA) resin. The influence of microstructure on corrosion behaviour was studied for a Fe‐Cr‐V‐N alloy containing micro‐sized nitrides with different chemical composition spread in martensitic alloy matrix. The Volta potential mapping suggested higher relative nobility for the nitride particles than the alloy matrix, and the nitrides with higher amounts of nitrogen and vanadium exhibited higher nobility. Potentiodynamic polarization measurements in a 0.1 M NaCl solution at neutral pH and ambient temperature showed passivity breakdown with initiation of localized corrosion which started in the boundary region surrounding the nitride particles, especially the ones enriched in Cr and Mo. Mefp‐1/ceria nanocomposite films were formed on silica and metal substrates by layer‐by‐layer immersion deposition. The film formation process was studied in situ using a Quartz Crystal Microbalance with Dissipation (QCM‐D). The film grows linearly with increasing number of immersions. Increasing Mefp‐1 concentration or using Mefp‐1 with larger size leads to more Mefp‐1 being deposited. Peak Force Quantitative Nanomechanical Mapping (Peak Force QNM) of the composite films in air indicated that the elastic modulus of the film increased when the film deposited had a higher Mefp‐1 concentration. It was also noted that the nature of the outermost layer can affect bulk morphology and surface mechanical properties of the film. The QCM‐D study of Mefp‐1 on an iron substrate showed that Mefp‐1 adsorbs at a high rate and changes its conformation with increasing adsorption time. The QCM‐D and in situ Peak Force QNM measurements showed that the addition of Fe3+ ions causes a transition in the single Mefp‐1 layer from an extended and soft layer to a denser and stiffer layer. In situ ATR‐FTIR and Confocal Raman Microscopy (CRM) analyses revealed complex formation between Fe3+ and catechol groups in Mefp‐1. Moreover, optical microscopy, SEM and AFM characterization of the Mefp‐1/ceria composite film formed on carbon steel showed micron‐size aggregates rich in Mefp‐1 and ceria, and a nanostructure of well dispersed ceria particles in the film. The CRM analysis confirmed the presence of Mefp‐1/Fe complexes in the film. Electrochemical impedance microscopy and potentiodynamic polarization measurements showed that the Mefp‐1/ceria composite film can provide corrosion protection for carbon steel, and that the protection efficiency increases with exposure time. Composite coatings of 10 μm thickness composed of a UV‐curing PEA resin and a small amount of conductive polymer and ceria nanoparticles were coated on carbon steel. The conductive polymer (PAni) was synthesized with phosphoric acid (PA) as the dopant by chemical oxidative polymerization. The ATR‐FTIR and SEM analyses confirmed that the added particles were well dispersed in the coatings. Electrochemical measurements during long exposure in 0.1 M NaCl solution, including open circuit potential (OCP) and EIS, were performed to investigate the protective performance of the coatings. The results showed that adding ceria nanoparticles can improve the barrier properties of the coating, and adding PAni‐PA can lead to active protection of the coating. Adding PAni‐PA and ceria nanoparticles simultaneously in the coating can improve the protection and stability of the composite coating, providing excellent corrosion protection for carbon steel. / <p>QC 20131024</p>

The purpose of this research work was to develop a nozzle capable of depositing dense CoNiCrAlY coatings via cold gas dynamic spray (CGDS) as well as compare the oxidation performance of bond coats manufactured by CGDS, high-velocity oxy-fuel (HVOF) and air plasma spray (APS) at temperatures of 1000°C and 1100°C. The work was divided in two sections, the design and manufacturing of a CGDS nozzle with an optimal profile for the deposition of CoNiCrAlY powders and the comparison of the oxidation performance of CoNiCrAlY bond coats. Throughout this work, it was shown that the quality of coatings deposited via CGDS can be increased by the use of a nozzle of optimal profile and that early formation of protective α-Al2O3 due to an oxidation temperature of 1100°C as opposed to 1000°C is beneficial to the overall oxidation performance of CoNiCrAlY coatings.