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.

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.

Submitted by Rafael Santana (rafael.silvasantana@ufpe.br) on 2017-04-19T19:20:06Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação completa (FINAL).pdf: 5768431 bytes, checksum: 342e336553ff7aabb5d24cb8e9437063 (MD5) / Made available in DSpace on 2017-04-19T19:20:06Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação completa (FINAL).pdf: 5768431 bytes, checksum: 342e336553ff7aabb5d24cb8e9437063 (MD5) Previous issue date: 2016-11-17 / CAPES / Nas diversas etapas processuais da indústria de petróleo – extração, recuperação, armazenamento, transporte e refino, os materiais metálicos são expostos a fluidos corrosivos e solicitações mecânicas. Na etapa de armazenamento, em tanques de petróleo, é possível evidenciar a presença de duas fases, uma oleosa e outra aquosa, que de forma isolada ou associada podem influenciar no processo corrosivo. No transporte de petróleo, apresenta-se o efeito de corrosão-erosão (C-E) gerado pela presença de sais, gases e partículas sólidas que prejudicam a integridade dos equipamentos. Este trabalho teve como objetivo avaliar o comportamento do aço ASTM 572 Gr50 exposto a óleo cru, água do mar e misturas desses fluidos em diferentes proporções; sob condições estáticas simulando tanques de armazenamento e dinâmicas, visando simular transporte dos fluidos. Foram realizados testes de imersão do aço em diferentes fluidos corrosivos (óleo cru, água do mar, misturas de óleo e água do mar nas proporções de 20 e 50 % em volume de água do mar), ao longo de 60 dias em condições estáticas e dinâmicas. O processo corrosivo do material exposto aos diferentes meios foi analisado através de ensaios de perda de massa, análises eletroquímicas de potencial de circuito aberto (PCA), polarização potenciodinâmica e espectroscopia de impedância eletroquímica (EIE). A morfologia da corrosão foi avaliada através de microscopia eletrônica de microscopia óptica (MO) e varredura (MEV). Testes de microdureza Vickers e análises microestruturais foram realizados para analisar a ocorrência de mudanças nas propriedades mecânicas dos aços. Os resultados evidenciaram a influência do teor de água do mar no processo corrosivo, onde foram observados maiores valores de taxa de corrosão para os sistemas contendo maior proporção de água do mar. O mecanismo de C-E, observado nos sistemas dinâmicos mostrou ser mais agressivo que o processo de corrosão isoladamente (sistemas estáticos) o que foi observado por meio dos maiores valores de taxa de corrosão e também pelas morfologias de processo de deterioração da superfície vista por MO e MEV, onde cavidades de maior longitude e pites internos foram observados para os sistema sujeitos ao processo de C-E. Não foram observadas mudanças significativas na microestrutura do material após exposição às condições de fluido estudadas. Os resultados de MEV mostraram a presença de corrosão localizada em todos os sistemas, inclusive para os sistemas contendo apenas óleo cru, que apresentou baixa taxa de corrosão. Os ensaios eletroquímicos de PCA, polarização e EIE realizados com os eletrólitos advindos dos ensaios de imersão (fase aquosa) mostraram que o contato entre fluidos distintos (óleo e água do mar) sob condições de agitação, promove uma intensa troca composicional entre os meios, aumentando a agressividade e modificando a interação metal/meio. O eletrólito proveniente do sistema dinâmico contendo mistura de óleo e água do mar (50%) foi o que se mostrou mais agressivo, visto que no ensaio de polarização linear apresentou o maior valor de densidade de corrente anódica. / In the various procedural stages of the oil industry - extraction, recovery, storage, transportation and refining, metal materials are exposed to corrosive fluids and mechanical stresses. In oil tanks of the storage step, it is possible to demonstrate the presence of two phases, an oily and other aqueous, which isolated or associated, can influence the corrosion process. In the oil transport the corrosion-erosion (C-E) effect is present and it is generated by the presence of salts, gases and solid particles that can influence the integrity of the equipment. This study aimed to evaluate the behavior of ASTM 572 GR50 steel exposed to crude oil, sea water and mixtures of these fluids in different proportions; under static conditions simulating storage tanks and dynamic conditions, aiming to simulate fluid transport. Immersion tests were performed in different corrosive fluids (crude oil, seawater, oil mixtures and sea water in the proportions of 20 to 50% by seawater volume) for 60 days, under static conditions and dynamics. The corrosive process of material exposed to different media was analyzed by mass loss tests and electrochemical analysis of open circuit potential (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The morphology of corrosion was assessed by microscopy optical (OM) and scanning electron microscopy (SEM). Vickers microhardness testing and microstructure analysis were performed to examine the changes occurring in the mechanical properties of steels. The results showed the influence of the seawater content in the corrosion process, in which were observed higher corrosion rate values for the systems containing higher proportion of seawater. The C-E mechanism, seen in dynamical systems proved to be more aggressive than corrosion process isolated (static systems) which was observed by means of higher corrosion rate values and also by the morphologies of the surface deterioration process seen by OM and SEM, where the greater length and internal cavities pits were observed for the system subject to the C-E process; There were not significant changes in the microstructure of the material after exposure to conditions fluid studied. SEM results showed the presence of localized corrosion on all systems, including systems containing only crude oil, which showed low corrosion rate. Electrochemical test OCP, polarization and EIS conducted with electrolytes arising from immersion tests (aqueous phase), showed that the contact between different fluids (oil and seawater) under agitation conditions, promotes an intense exchange compositional between the fluids, increasing the aggressiveness and modifying the metal/media interaction. The electrolyte from the dynamic system containing a mixture of oil and seawater (50%) was the more aggressive electrolyte, as can be seen in the linear polarization that showed the highest value of anodic current density.