No description available.

No description available.

Organic coatings are widely used to lower the corrosion rate of metallic structures. However, penetration of water, oxygen and corrosive ions through pores present in the coating results in corrosion initiation and propagation once these species reach the metal substrate. Considering the need for systems that offer active protection with self-healing functionality, composite coatings containing polyaniline (PANI) conducting polymer are proposed in this study. In the first phase of my work, PANI was synthesized by various methods and characterized. The rapid mixing synthesis method was chosen for the rest of this study, providing PANI with high electrical conductivity, molecular structure of emeraldine salt, and morphology of spherical nanoparticles. PANIs doped with phosphoric and methane sulfonic acid revealed hydrophilic nature, and I showed that by incorporating a long-chain alkylphosphonic acid a hydrophobic PANI could be prepared. The second phase of my project was dedicated to making homogenous dispersions of PANI in a UV-curable resin based on polyester acrylate (PEA). Interfacial energy studies revealed the highest affinity of PEA to PANI doped with phosphoric acid (PANI-PA), and no attractive or long-range repulsive forces were measured between the PANI-PA surfaces in PEA.This is ideal for making conductive composites as, along withno aggregation tendency, the PANI-PA particles might come close enough to form an electrically connected network. Highly stable PEA/PANI-PA dispersions were prepared by pretreatment of PANI-PA in acetone followed by mixing in PEA in small portions under pearl-milling. The third phase of my project dealt with kinetics of the free radical polymerization that was utilized to cure the PEA/PANI-PA mixture. UV-vis absorption studies suggested a maximum allowed PANI-PA content of around 4 wt.% in order not to affect the UV curing behavior in the UV-C region. Real-time FTIR spectroscopy studies, using a laboratory UV source, revealed longer initial retardation of the photocuring and lower rates of crosslinking reactions for dispersions containing PANI-PA of higher than 3 wt.%. The presence of PANI-PA also made the formulations more sensitive to changes in UV light intensity and oxygen inhibition during UV curing. Nevertheless, curing of the dispersions with high PANI-PA content, of up to 10 wt.%, was demonstrated to be possible at either low UV light intensities provided the oxygen replenishment into the system was prevented, or by increasing the UV light intensity to very high levels. In the last phase of my project, the PEA and PEA/PANI-PA coatings, cured under high intensity UV lamps, were characterized. SEM analysis showed small PANI-PA particles to be closely packed within the matrix, and the electrical conductivity of the composite films was measured to be in the range of semiconductors. This suggested the presence of a connected network of PANI-PA, as confirmed by investigations of mechanical and electrical variations at the nanoscale by PeakForce TUNA AFM. The data revealed the presence of a PEA-rich layer at the composite-air interface, and a much higher population of the conductive network within the polymer matrix. High current signal was correlated with a high elastic modulus, consistent with the level measured for PANI-PA, and current-voltage studies on the conductive network showed non-Ohmic characteristics. Finally, the long-term protective property of the coatings was characterized by OCP and impedance measurements. Short-term barrier-type corrosion protection provided by the insulating PEA coating was turned into a long-term and active protection by addition of as little as 1 wt.% PANI-PA. A large and stable ennoblement was induced by the coatings containing PANI-PA of up to 3 wt.%. Higher content of PANI-PA led to poorer protection, probably due to the hydrophilicity of PANI-PA facilitating water transport in the coating and the presence of potentially weaker spots in the film. An iron oxide layer was found to fully cover the metal surface beneath the coatings containing PANI-PA after final failure observed by electrochemical testing. / <p>QC 20141103</p>

No description available.

Since metals in general, and steels in particular, are vital construction materials in our modern society, the corrosion protection of said materials is of great importance, both to ensure safety and to reduce costs associated to corrosion. Previously, chromium (VI) and other harmful substances were effectively used to provide corrosion protection to steel, but since their use was heavily regulated around year 2000, no coating has yet been developed that, in a fully satisfactory manner, replaces their corrosion protective properties.In this thesis, the use of hydrophobic and superhydrophobic surface coatings as part of corrosion protective coating systems has been studied. Since the corrosion mechanism relies on the presence of water to take place, the use of a superhydrophobic coating to retard the penetration of water to an underlying metal surface is intuitive. The evaluation of corrosion protective properties of the hydrophobic and superhydrophobic surfaces was performed using mainly contact angle measurements and electrochemical measurements in severely corrosive 3 wt% NaCl water solution.First, the differences in corrosion protection achieved when employing different hydrophobic wetting states were investigated using a model alkyl ketene dimer wax system. It was found that superhydrophobicity in the Lotus state is superior to the other states, when considering fairly short immersion times of less than ten days. This is due to the continuous air film that can form between such a superhydrophobic surface and the electrolyte, which can retard the transport of electrolyte containing corrosive ions to the metal surface to the point where the electrical circuit is broken. Since corrosion cannot occur unless an electrical current is flowing, this is a very efficient way of suppressing corrosion.An air layer on an immersed superhydrophobic surface is, however, not stable over long time, and to investigate long-term corrosion protection using hydrophobic coatings a polydimethylsiloxane formulation containing hydrophobic silica nanoparticles was developed. This system showed enhancement in corrosion protective properties with increasing particles loads, up until the point where the particle load instead causes the coating to crack (at 40 wt%). The conclusion is that the hydrophobicity of the matrix and filler, in combination with the elongatedivdiffusion path supplied by the addition of particles, enhanced the corrosion protection of the underlying substrate.To further understand how hydrophobicity and particle addition affect the corrosion protective properties of a coating a three layer composite coating system was developed. Using this coating system, consisting of a polyester acrylate base coating, covered by TiO2 particles (with diameter &lt; 100 nm) and finally coated with a thin hexamethyl disiloxane coating, it was found that both hydrophobicity and particles are needed to reach a great enhancement in corrosion protective properties also for this system. / Eftersom metaller, och då särskilt stål, är viktigta konstruktionsmaterial i vårt moderna samhälle är korrosionsskydd av stor betydelse, både för att garantera säkerhet och för att minska kostnader som uppkommer i samband med korrosion. Tidigare har sexvärt krom och andra skadliga ämnen använts för att på ett effektivt sätt skydda stål från korrosion, men efter att deras användning kraftigt reglerades runt år 2000 har ännu ingen beläggning utvecklats som helt kan ersätta krombeläggningarna med avseende på funktion.I denna avhandling har hydrofoba och superhydrofoba ytbeläggningar och deras möjliga applikation som en del av ett korrosionsskyddande beläggningssystem studerats. Eftersom korrosionsmekanismen är beroende av närvaron av vatten, är användandet av en superhydrofob beläggning för att fördröja transporten av vatten till den underliggande metallytan intuitiv. De korrosionsskyddande egenskaperna hos superhydrofoba ytbeläggningar utvärderades här främst med hjälp av kontaktvinkelmätningar och elektrokemisk utvärdering i korrosiv lösning bestående av 3 vikts% NaCl i vatten.Först undersöktes skillnaden i korrosionsskydd som uppnås vid användandet av ytbeläggningar med olika hydrofoba vätningsregimer med hjälp av ett modellsystem bestående av ett alkylketendimer vax. Det konstaterades att superhydrofobicitet i Lotusregimen är överlägset bättre än de andra hydrofoba vätningsregimerna, i alla fall när man ser till relativt korta exponeringstider, typiskt mindre än tio dagar. Detta beror på att den kontinuerliga luftfilm som kan bildas på en sådan typ av superhydrofob yta kan minska transporten av elektrolyt (som innehåller korrosiva joner) till metallytan till den grad att den elektriska kretsen bryts. Eftersom korrosion inte kan ske utan en sluten elektrisk krets är detta ett mycket effektivt sätt att förhindra korrosion från att ske.Ett luftskikt på en superhydrofob yta nedsänkt i vatten är dock inte stabilt under lång tid. För att undersöka möjligheten till korrosionsskydd under längre tid med hjälp av hydrofoba beläggningar utvecklades en hydrofob ytbeläggning bestående av polydimetylsiloxan och hydrofoba nanopartiklar av kiseldioxid. Detta system visade en förbättring av korrosionsskyddet vid ökat partikelinnehåll upp till den koncentration (40 wt%) där i stället sprickbildning i ytbeläggningen observerades. Från detta system kunde slutsatsen dras att matrisens och partiklarnasvihydrofobicitet i kombination med den längre diffusionsvägen som partiklarna orsakade förbättrade korrosionsskyddet av den underliggande metallen.För att ytterligare förstå hur hydrofobicitet och partikeltillsatser påverkar en ytbeläggnings korrosionsskyddande egenskaper har dessutom ett treskikts kompositbeläggningssystem utvecklats. Genom att använda detta beläggningssystem, som består av en basbeläggning av polyesterakrylat, ett lager TiO2-partiklar (med en diameter på &lt;100 nm) slutligen belagt med ett tunt ytskikt bestående av hexametyldisiloxan så kunde slutsatsen dras att både en hydrofob matris och partiklar behövs för att nå en markant förbättring av ytbeläggningens korrosionsskyddande egenskaper. / <p>QC 20151015</p>

La prévention contre la corrosion est un facteur déterminant pour la durabilité des matériaux. Historiquement, le développement des applications des matériaux avancés n'est pas envisageable sans une approche scientifique poussée des mécanismes fondamentaux qui conduisent à la dégradation en service. L'histoire humaine a été ponctuée par les progrès technologiques, qui ont tous été permis par les progrès de la science des matériaux, de l'âge du fer à l'âge de silicium. Par exemple, c'est la fusion du minerai qui a fait basculer l'humanité de l'âge de pierre aux premiers alliages (bronze) et la fondation ultérieure d'une société basée sur les métaux. Ces métaux retournent à l'état naturel en suivant des lois thermodynamiques et cinétiques. l'objet de la thèse vise à comprendre le comportement de certains matériaux dits passivables pour tenter de proposer des lois de comportement à partir du modèle du défaut ponctuel. Cette approche s'appuie sur des caractérisations électrochimique et physico-chimique des matériaux métalliques considérés. / Corrosion control is an important facet of durable and responsible engineering. Historically, the development of advanced materials applications stymied without sufficient scientific understanding of the fundamental mechanisms that dominate degradation in the system of application. Human history has been punctuated by advances in technology, all of which were enabled by advances in materials science, from the iron age to the silicon age. For instance, it was the invention of smelting ores that brought humanity out of the stone age, leading to the first alloys (bronze) and the subsequent foundation of a metals based society. During the infancy of the planet earth, around four billion years ago, the first photosynthesizers began converting carbon dioxide into oxygen. However, oxygen gas was not released into the atmosphere in great quantities because it was immediately bound up with dissolved metals in the ocean; mostly iron, forming a large fraction of the iron ores we rely upon. Producing such metals from oxides formed during the previous four billion years involves flying in the face of the thermodynamic desire to return to the oxide state.

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