Thesis (Ph.D.) -- McMaster University, 1998. / Includes bibliographical references (leaves 149-158). Also available via World Wide Web.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1968. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Aniline oligomers have become a very interesting topic for research because of their potential application not only in organic electronics but also in smart coatings for corrosion treatment of iron and steel. A majority of the studies in the literature are focussed on the bulk or direct interaction between the organic molecules with metal substrates, without considering the native oxide film. In order to develop smart coatings (has redox activity and self-healing ability) for iron and steel, one must first understand how these oligomers interact with the native iron oxide film. In this thesis, we develop new knowledge from our fundamental understanding of the interactions of redox-active aniline oligomers with the iron oxide surface. Phenyl capped aniline dimer with two oxidation states [fully reduced (DPPD) and fully oxidized (B2Q1)] and phenyl-capped aniline tetramer (PCAT) with three oxidation states [fully reduced (B5), half-oxidized (B4Q1), fully oxidized (B3Q2)] were chosen for investigation. The former is the smallest redox active aniline oligomer but with one fewer oxidation states than polyaniline whereas the latter mimics the redox system as well as corrosion inhibition properties of polyaniline. Moreover, the phenyl-caps help both of these molecules to resist polymerization on the surface. Raman spectroscopy, mid-IR spectroscopy, atomic force microscopy (AFM), temperature programmed desorption (TPD) and electrochemical impedance spectroscopy (EIS) were used to study interactions. We demonstrate that charge transfer and interconversion to different oxidation states take place during interactions between each of these molecules with iron (III) oxides surfaces. During interaction with the surface, all three tetramer molecules and DPPD prefer standing on their edge orientation, whereas B2Q1 molecules tend to orient in lying down direction on the same surface. Having amino groups in the chain helps reduced and half oxidized molecules to strongly hydrogen bond with the surface and make them static on the surface. On the other hand, a lack of amino groups makes oxidized molecules mobile and loosely bound to the surface. Interactions and change of oxidation states impact the corrosion inhibition properties of PCAT. Strong ability of sticking to the surface and not fully oxidizing (B3Q2) during interactions makes B5 molecules superior corrosion inhibitors than B4Q1 and B3Q2 molecules. Transformation into B3Q2 form at the beginning of interaction allows B4Q1 to moderately inhibit corrosion but as it transforms back to its original form with time it becomes the 2nd best corrosion protector of iron oxide surface after B5. The study of all oxidation states and their surface interactions with iron oxide surface will open up pathways towards of designing smart coatings using aniline oligomers and other redox-active molecules. / Thesis / Doctor of Philosophy (PhD) / Aniline oligomers have become a very interesting topic for research because of their potential application not only in organic electronics but also in smart coatings for corrosion treatment of iron and steel. A majority of the studies in the literature are focussed on the bulk or direct interaction between the organic molecules with metal substrates, without considering the native oxide film. In order to develop smart coatings (has redox activity and self-healing ability) for iron and steel, one must first understand how these oligomers interact with the native iron oxide film. In this thesis, we develop new knowledge from our fundamental understanding of the interactions of redox-active aniline oligomers with the iron oxide surface. Phenyl capped aniline dimer with two oxidation states [fully reduced (DPPD) and fully oxidized (B2Q1)] and phenyl-capped aniline tetramer (PCAT) with three oxidation states [fully reduced (B5), half-oxidized (B4Q1), fully oxidized (B3Q2)] were chosen for investigation. The former is the smallest redox active aniline oligomer but with one fewer oxidation states than polyaniline whereas the latter mimics the redox system as well as corrosion inhibition properties of polyaniline. Moreover, the phenyl-caps help both of these molecules to resist polymerization on the surface. Raman spectroscopy, mid-IR spectroscopy, atomic force microscopy (AFM), temperature programmed desorption (TPD) and electrochemical impedance spectroscopy (EIS) were used to study interactions. We demonstrate that charge transfer and interconversion to different oxidation states take place during interactions between each of these molecules with iron (III) oxides surfaces. During interaction with the surface, all three tetramer molecules and DPPD prefer standing on their edge orientation, whereas B2Q1 molecules tend to orient in lying down direction on the same surface. Having amino groups in the chain helps reduced and half oxidized molecules to strongly hydrogen bond with the surface and make them static on the surface. On the other hand, a lack of amino groups makes oxidized molecules mobile and loosely bound to the surface. Interactions and change of oxidation states impact the corrosion inhibition properties of PCAT. Strong ability of sticking to the surface and not fully oxidizing (B3Q2) during interactions makes B5 molecules superior corrosion inhibitors than B4Q1 and B3Q2 molecules. Transformation into B3Q2 form at the beginning of interaction allows B4Q1 to moderately inhibit corrosion but as it transforms back to its original form with time it becomes the 2nd best corrosion protector of iron oxide surface after B5. The study of all oxidation states and their surface interactions with iron oxide surface will open up pathways towards of designing smart coatings using aniline oligomers and other redox-active molecules.

No description available.

The economic impact of metallic corrosion on global infrastructure, spanning pipeline networks, bridges, refineries, and automobiles, is considerable. In 2013, it accounted for 3.4% of the global GDP, totaling US$ 2.5 trillion. Organic coatings have gained significance as a prominent strategy to address this widespread issue. Polyaniline (PANI), a conducting polymer, has long been recognized as an effective anti-corrosion coating. This study explores the potential of polyaniline analogs and their nanocomposites as candidates for protective organic coatings in corrosion control applications. Initially, the investigation focuses on conducting polymers with side chains comprising long, branched alkyl groups as potential corrosion suppression coatings. These polymers, containing carbazole, phenothiazine, and phenoxazine cores, serve as analogs to polyaniline. Prepared through the Buchwald/Hartwig coupling reaction, these polymers demonstrated promising corrosion suppression capabilities, as tested by potentiodynamic polarization studies and electrochemical impedance spectroscopy (EIS). Morphological characterization using scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed that phenothiazine- and carbazole-containing polymers exhibit excellent corrosion resistance, with phenothiazine displaying a protection efficiency (PE) of 95.9% and 89.0% respectively, outperforming polyaniline coating. Further exploration involved the derivatives of phenothiazine-based PANI analogs, specifically poly(heterocyclic diphenylamine) (poly-HDA), prepared through the Buchwald/Hartwig coupling reaction. Evaluation through weight loss, potentiodynamic polarization, and EIS in a 3.5 wt.% NaCl solution showcased the reduced corrosion current density on surfaces coated with long-branched alkyl-substituted phenothiazine-based PANI analogs. Moreover, the reinforcement of the phenothiazine-based PANI analog polymer was achieved by creating an epoxy-based nanocomposite with 2,5-dimethyl-1,4-phenylenediamine functionalized graphene oxide (PT/DPPD-fGO) at varying concentrations into an epoxy anticorrosive coating for AISI 4130 steel from corrosion. Results from immersion in 5 % sodium chloride solution, coupled with standard electrochemical measurements, demonstrate that PT/DPPD-fGO effectively protects AISI 4130 steel from corrosion, with coatings containing 5 % PT/DPPD-fGO exhibiting the best corrosion performance among the tested specimens. The results indicate the potential of phenothiazine- and carbazole-based PANI analogs, along with their nanocomposites, as candidates for protective organic coatings in transportation, aviation, marine, and oil and gas industrial applications.

Th.--Sci.--Bordeaux 1, 1981. N°: 716.

A corrosão é um processo resultante da ação do meio sobre um determinado material, causando sua deterioração. Em geral, essa deterioração causa prejuízos incalculáveis, fazendo com que o material se torne inadequado ao uso. Os heterocíclicos apresentam inúmeras aplicações tecnológicas e em alguns casos médico-farmacológicas. Mais recentemente, esses compostos têm sido utilizados como eficientes inibidores de corrosão para a proteção de metais em meio ácido ou salino. Nesta Dissertação realizou-se a modificação química da poliacrilonitrila com a incorporação de grupos tetrazol em diferentes teores (8%, 15%, 30% e 30%). Os copolímeros de acrilonitrila e 5-vinil-tetrazol obtidos foram caracterizados por espectroscopia na região do infravermelho e foram quantificados os respectivos teores de incorporação por meio de titulação ácido-base e análise elementar. A poliacrilonitrila e os copolímeros heterocíclicos foram avaliados como inibidores de corrosão para aço-carbono, alumínio e latão em solução aquosa de HCl 2 mol/L e HNO3 2 mol/L, alcançando, em alguns casos, uma eficiência de inibição superior a 75%, com diferença estatisticamente significativa (P < 0,05, ANOVA) para a poliacrilonitrila não modificada / Corrosion is a process resulting from the action of environment on a given material, causing its deterioration. In general, these deteriorations cause incalculable damage, making the material unsuitable for use. The heterocycles have numerous technological applications and in some cases medical and pharmacological. More recently, these compounds have been used as efficient corrosion inhibitors to protect metals in acidic or saline environments. This Dissertation was conducted on the chemical modification of polyacrylonitrile with the incorporation of tetrazole at different contents (8%, 15%, 30% and 30%). Copolymers of acrylonitrile and 5-vinyl-tetrazole were characterized by infrared spectroscopy and were quantified the respective contents of incorporation by acid-base titration and elemental analysis. The polyacrylonitrile and heterocyclic copolymers were evaluated as corrosion inhibitors for carbon steel, aluminum and brass in aqueous 2 mol/L HCl and 2 mol/L HNO3, resulting in some cases, an efficiency of greater than 75% inhibition, which was statistically significant (P<0.05, ANOVA) for the unmodified polyacrylonitrile

A corrosão é um processo resultante da ação do meio sobre um determinado material, causando sua deterioração. Em geral, essa deterioração causa prejuízos incalculáveis, fazendo com que o material se torne inadequado ao uso. Os heterocíclicos apresentam inúmeras aplicações tecnológicas e em alguns casos médico-farmacológicas. Mais recentemente, esses compostos têm sido utilizados como eficientes inibidores de corrosão para a proteção de metais em meio ácido ou salino. Nesta Dissertação realizou-se a modificação química da poliacrilonitrila com a incorporação de grupos tetrazol em diferentes teores (8%, 15%, 30% e 30%). Os copolímeros de acrilonitrila e 5-vinil-tetrazol obtidos foram caracterizados por espectroscopia na região do infravermelho e foram quantificados os respectivos teores de incorporação por meio de titulação ácido-base e análise elementar. A poliacrilonitrila e os copolímeros heterocíclicos foram avaliados como inibidores de corrosão para aço-carbono, alumínio e latão em solução aquosa de HCl 2 mol/L e HNO3 2 mol/L, alcançando, em alguns casos, uma eficiência de inibição superior a 75%, com diferença estatisticamente significativa (P < 0,05, ANOVA) para a poliacrilonitrila não modificada / Corrosion is a process resulting from the action of environment on a given material, causing its deterioration. In general, these deteriorations cause incalculable damage, making the material unsuitable for use. The heterocycles have numerous technological applications and in some cases medical and pharmacological. More recently, these compounds have been used as efficient corrosion inhibitors to protect metals in acidic or saline environments. This Dissertation was conducted on the chemical modification of polyacrylonitrile with the incorporation of tetrazole at different contents (8%, 15%, 30% and 30%). Copolymers of acrylonitrile and 5-vinyl-tetrazole were characterized by infrared spectroscopy and were quantified the respective contents of incorporation by acid-base titration and elemental analysis. The polyacrylonitrile and heterocyclic copolymers were evaluated as corrosion inhibitors for carbon steel, aluminum and brass in aqueous 2 mol/L HCl and 2 mol/L HNO3, resulting in some cases, an efficiency of greater than 75% inhibition, which was statistically significant (P<0.05, ANOVA) for the unmodified polyacrylonitrile

Corrosion Protection and Microstructure of Dissimilar Materials. A thesis submitted to The University of Manchester for the degree of Doctor of Philosophy by Uyime, Donatus on the 30th of July, 2015.Investigations on the micro- and macro-galvanic corrosion mechanisms in un-coupled AA2024-T3 alloys, AA2024-T3 coupled with mild steel (with and without the influence of cadmium and under varying solution temperatures), dissimilar friction stir welds of AA5083-O and AA6082-T6 alloys and a friction stir welded AA7018 alloy have been carried out. Selected methods of preventing and / or minimising the investigated corrosion phenomena were also investigated. The investigation of the corrosion behaviour of the uncoupled AA2024-T3 alloy revealed that there are two distinct stages of polarization during the galvanostatic polarization of AA2024T3 alloy in de-aerated 3.5% NaCl solution. From the first stage, the relationships between the pitting incubation time, pitting potential and applied current density for AA2024T3 alloy in the de-aerated condition were established. Whilst studying the in situ corrosion phenomena on the uncoupled AA2024-T3 alloy using the scanning vibrating electrode technique (SVET),three distinct stages in the variation of the recorded current density values with time were revealed. Attempts were made to correlate these stages with the corrosion behaviour of the alloy. The study of the galvanic interactions between AA2024-T3 and mild steel revealed that AA2024-T3 is anodic to mild steel at room temperature, but polarity reversal of the couple starts (from a temperature as low as 35 oC upwards) when the couple is introduced into the solution above ambient temperature. Importantly, AA2024-T3 is clearly cathodic to mild steel at 60 oC, although with very low measured galvanic current values. Cadmium coating (at ambient temperature) on the mild steel reduced the galvanic corrosion of the couple by as much as 20 µA/cm2 because of the formation of a CdO/Cd(OH)2 layer on mild steel. In the study of the dissimilar friction stir welds of AA5083-O and AA6082-T6 alloys, it was observed that material flows (pushes but does not mix) more from the advancing side into the retreating side and that the mixture of materials is far from complete. Two welding speeds were compared; the welding speeds have no clear influence on the microhardness, but affected the mixing proportions in the flow arm and in the nugget stem. The faster welding speed resulted in increased susceptibility to corrosion because of the reduced tool rotation per weld length for heat generation and the mixing of materials. The heat affected zones of both alloys and the transition regions between the AA5083-O alloy and the AA6082-T6 alloy rich zones have been identified to be the regions that are most susceptible to corrosion. Anodizing the weld in order to minimise corrosion showed that the AA5083-O alloy rich zones materials, in the weld, oxidizes more during anodizing compared with the AA6082-T6 alloy rich zones. Sputtering deposition prior to anodizing, promotes the formation of a uniform oxide film across the entire weld zones and prevents the boundary dissolution that occurs when the dissimilar weld of AA5083-O and AA6082-T6 alloys is anodized in 4 M H2SO4 solution at 15 V at ambient temperature. The investigation of the corrosion susceptible regions in friction stir welded AA7018 alloy, which was based on the use of ISO 11846 immersion test and the potentiodynamic polarization technique in naturally aerated 3.5 % NaCl solution, revealed intergranular, crystallographic and second phase particle influenced mode of attack. The heat affected zone was found to be the most susceptible to corrosion.

This master´s thesis is focused on classification of corrosion resistivity magnesium alloy type AZ91 in environment of salt vapour testing in corrosion chambers. For tests were used samples of magnesium alloy manufactured by three different methods of casting: cast-iron mold, die vacuum casting, die casting without vacuum and method of die casting with additional pressure (squeeze casting). In this work was accomplished metallographic evaluation of corrosion attack and detailed analysis of corrosion products. Conclusions of exposits tests are assembled of analysis of influence of corrosion environment on structure of alloy. On the basis of these conclusions of corrosion tests were evaluated influences of corrosion speed [mm/year] on time [hours] for individual states of magnesium alloy.