Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1993. / Vita. Abstract. Includes bibliographical references (leaves 134-141). Also available via the Internet.

Water diffusion is widely believed to be a driving factor in the breakdown of corrosion protection by polymer coatings. However, in the epoxy-phenolic system examined, water absorption into more cured, electrically resistive coatings is shown to increase, contradicting the common perception that hydrophobic coatings yield improvements in corrosion protection. Water uptake into epoxy-phenolic coatings was estimated as a function of time using the dielectric and resistive properties of the coating measured using electrochemical impedance spectroscopy (EIS). Bulk water uptake through the coating surface and the localised nature of corrosive failure was then confirmed using localised electrochemical impedance (LEIS). This technique also allowed comparison of resistance for coatings with different curing degrees. The greater degree of water absorption into highly cured coatings was attributed to diffusion into the polymer free volume, which increases with prolonged crosslinking. Evidence for this mechanism was found in the decreasing density of epoxy-phenolic coatings as a function of cure time. The effect of coating volume was therefore evaluated with respect to the dry coating dielectric properties. Cathodic delamination of the epoxy-phenolic coatings was achieved on tinplated steel substrates, whereas this was not possible from tin-free steel (ECCS). The electrochemical behaviour of these two substrates was examined under the same NaCl concentration, their surfaces were analysed by XPS prior to immersion, and XRD after potentiostatic polarisations. The electrochemical behaviour of the bare substrates was found to be unchanged by heating to the coating cure temperature (within the accuracy of polarisation tests carried out). Nonetheless, the delamination rate of epoxy-phenolic coatings deposited on them was dependent on the coating crosslinking (cure time). The reason coating adhesion selectively failed on tinplate substrates is believed to be the lower concentration of hydroxides on its relatively flat surface, allowing less bonding to take place at the interface with the coating. The impact of the substrate on coating resistivity was further investigated by volume resistivity measurements in the presence and absence of a metallic substrate. The resistivity of free standing films was tested in permeation cells, and showed a direct correlation between the polymer resistivity and the resistivity of the solution in which it was immersed. In comparison, attached films remained highly resistive at all examined concentrations. To conclude, the results presented here demonstrate that water uptake is not as critical to the breakdown in the protection offered by epoxy-phenolics as bonding at the metal-polymer interface. These results suggest that the complex interaction between these two dissimilar materials determines the overall coating electrochemical behaviour.

No description available.

Filmes inorgânicos de ZrO2 e filmes híbridos orgânico-inorgânicos de ZrO2-PMMA, preparados pelo método sol-gel, foram estudados como protetores contra a corrosão de aço inoxidável em meio ácido. Os sóis foram preparados a partir de uma solução submetida à irradiação de ultra-som e contendo o alcóxito metálico correspondente como precursor, álcool como solvente e ácido acético glacial como agente quelante para modificar a reatividade do alcóxito metálico. Várias concentrações de PMMA foram adicionadas aos sóis e estes foram caracterizados através de reometria, espectroscopia na região do infravermelho (FTIR), calorimetria explanatória diferencial (DSC) visando estudar a evolução de suas características morfológicas durante o envelhecimento. Os filmes de ZrO2 e ZrO2-PMMA foram depositados, utilizando-se a técnica de imersão, sobre lâminas de aço inoxidável 316L (AISI 316L), densificados a 200&#176C e o tempo de tratamento térmico foi variado de 5 a 180 minutos. Os filmes foram caracterizados por espectroscopia de reflexão especular na região do infravermelho; a morfologia, composição e textura superficiais foram determinadas por microscopia eletrônica de varredura (MEV), dispersão de energia de raios X (EDS) e perfilometria, respectivamente. curvas de polarização potenciodinâmica a 1 mVs-1 foram usadas para estudar a eficiência dos diferentes recobrimentos na proteção do AISI 316L contra a corrosão em soluções de H2SO4 0,5 mol.L-1. Os resultados mostram que os filmes híbridos ZrO2-PMMA aumentam em média 30 vezes o tempo de vida do substrato em relação aos filmes puramente inorgânicos. / ZrO2 inorganic and ZrO2-PMMA hybrids organic-inorganic films, obtained by the sol-gel method, were studied in order to determine their properties as protective layers against corrosion of stainless steel in acid media. The sol was prepared from a sonocatalyzed solution containing the appropriate metal alkoxide as precursor, alcohol as solvent, and glacial acid acetic as chelant agent to modify the reactivity of the metal alkoxide and PMMA was added into these sols. Reology, infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were employed to determine the evolution of structural changes during aging time. The ZrO2 and ZrO2-PMMA films were deposited on stainless steel by dip-coating technique and heat treated at 200&#176C at times of heating ranging from 5 to 180 minutes. The films were characterized by FTIR reflection spectroscopy, scanning electronic microscopy, X-ray dispersive energy and profilometry to determine the surface morphology, composition and texture, respectively. Potentiodynamic polarization curves (PPC) at 1 mVs-1 were used to study the efficiency on the protection of AISI 316L against corrosion in H2SO4 0,5 mol.L-1, showing that ZrO2-PMMA increase in a factor up 30 the life time of substrate.

Filmes inorgânicos de ZrO2 e filmes híbridos orgânico-inorgânicos de ZrO2-PMMA, preparados pelo método sol-gel, foram estudados como protetores contra a corrosão de aço inoxidável em meio ácido. Os sóis foram preparados a partir de uma solução submetida à irradiação de ultra-som e contendo o alcóxito metálico correspondente como precursor, álcool como solvente e ácido acético glacial como agente quelante para modificar a reatividade do alcóxito metálico. Várias concentrações de PMMA foram adicionadas aos sóis e estes foram caracterizados através de reometria, espectroscopia na região do infravermelho (FTIR), calorimetria explanatória diferencial (DSC) visando estudar a evolução de suas características morfológicas durante o envelhecimento. Os filmes de ZrO2 e ZrO2-PMMA foram depositados, utilizando-se a técnica de imersão, sobre lâminas de aço inoxidável 316L (AISI 316L), densificados a 200&#176C e o tempo de tratamento térmico foi variado de 5 a 180 minutos. Os filmes foram caracterizados por espectroscopia de reflexão especular na região do infravermelho; a morfologia, composição e textura superficiais foram determinadas por microscopia eletrônica de varredura (MEV), dispersão de energia de raios X (EDS) e perfilometria, respectivamente. curvas de polarização potenciodinâmica a 1 mVs-1 foram usadas para estudar a eficiência dos diferentes recobrimentos na proteção do AISI 316L contra a corrosão em soluções de H2SO4 0,5 mol.L-1. Os resultados mostram que os filmes híbridos ZrO2-PMMA aumentam em média 30 vezes o tempo de vida do substrato em relação aos filmes puramente inorgânicos. / ZrO2 inorganic and ZrO2-PMMA hybrids organic-inorganic films, obtained by the sol-gel method, were studied in order to determine their properties as protective layers against corrosion of stainless steel in acid media. The sol was prepared from a sonocatalyzed solution containing the appropriate metal alkoxide as precursor, alcohol as solvent, and glacial acid acetic as chelant agent to modify the reactivity of the metal alkoxide and PMMA was added into these sols. Reology, infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were employed to determine the evolution of structural changes during aging time. The ZrO2 and ZrO2-PMMA films were deposited on stainless steel by dip-coating technique and heat treated at 200&#176C at times of heating ranging from 5 to 180 minutes. The films were characterized by FTIR reflection spectroscopy, scanning electronic microscopy, X-ray dispersive energy and profilometry to determine the surface morphology, composition and texture, respectively. Potentiodynamic polarization curves (PPC) at 1 mVs-1 were used to study the efficiency on the protection of AISI 316L against corrosion in H2SO4 0,5 mol.L-1, showing that ZrO2-PMMA increase in a factor up 30 the life time of substrate.

Coil coatings are durable  organic coatings used to protect metal sheets from corrosion and improve their aesthetic properties. Because of their extensive use, coil coatings have long been of interest for industrial and academic researchers. This interest has recently been furthered by a societal push towards the replacement of fossil-based raw materials with alternatives that are biobased and renewable. The aim of this licentiate thesis is to demonstrate how analyses on the macro-, micro-, and nanoscale can be used to better understand the degradation process of polyester-based coil coatings. The included manuscripts showcase methods for evaluating and comparing different coil coating formulations and for verifying accelerated weathering techniques. Multiple techniques, focusing on infrared (IR) spectroscopy and atomic force microscopy (AFM), were used to analyze coating systems before and after different types of weathering. IR data acquired from techniques without spatial resolution, such as attenuated total reflection (ATR) and photoacoustic spectroscopy (PAS) have been expanded upon with spatially resolved focal plane array (FPA) and s-SNOM  (scattering-type scanning near-field optical microscopy) measurements. Spatially resolved chemical data of coating cross sections were acquired and used to assess how the degradation at the surface and in the bulk was related. Additionally, differences between the degradation behavior of a standard fossil-based coating and a similar coating with biobased components as well as differences between the degradation caused by artificial and natural weathering was discussed. Nanoscale mechanical measurements of simplified coating surfaces showed that weathering increased nanomechanical stiffness and led to homogenization of mechanical properties on the local level. In addition, measurements with nanoscale FTIR correlated with macroscale FTIR. Even relatively minor changes in band intensities could be tracked on a local scale. Although the simplified samples were chemically homogeneous, nanoscale FTIR shows great promise for the assessment of local degradation of full systems. / Bandlackering är en process för att applicera stabila organiska beläggningar på metallytor för att skydda från korrosion och förbättra deras utseende. På grund av beläggningarnas omfattande användning så har utvärdering och analys av dem varit av intresse för både akademi och industri i flera årtionden. Detta långvariga intresse har ytterligare främjats av en ökade miljömedvetenhet och ett tryck att ersätta miljöfarliga och fossila råmaterial mot biobaserade och förnyelsebara alternativ. Målet med denna licentiatavhandling är att visa hur analysmetoder på makro-, mikro-, och nanonivå kan användas för att bättre förstå nedbrytning av bandlackerade beläggningar. Denna förståelse kan användas både för att utvärdera prestandan hos både nya redan befintliga system, men också för att kunna verifiera accelererade testmetoder vars mål är att minska tiden som krävs för utvärdering. Flera tekniker, med fokus på infraröd (IR) spektroskopi och atomkrafts-mikroskopi  (AFM) använts för att analysera beläggningar före och efter att de blivit utsatta för olika typer av aggressiva miljöer. Spektroskopiska data utan spatial upplösning som attenuerad totalreflektions FTIR (ATR) och fotoakustisk spektroskopi (PAS) har kompletterats med spatialt upplösta fokalplans array (FPA) och s-SNOM mätningar. Kemisk information med spatial upplösning har använts för att utvärdera hur nedbrytningen nära ytan relaterade till nedbrytningen längre ner i beläggningen. Likheter och skillnader i nedbrytningen som skedde i en standardbeläggning och ett system med biobaserade additiv jämfördes efter både väderbestendighets-testning som skedde utomhus och i labb. Skillnader mellan dessa exponeringsmetoder diskuterades också. Nanomekanisk analys med hjälp av atomkraftsmikroskopi användes för att bestämma lokala förändringar av mekaniska egenskaper i förenklade klarlacker. Mätningarna visade att exponeringar i aggressiva miljöer leder till en lokal homogenisering av mekaniska egenskaper och ökad styvhet. Utöver detta så utvärderades likheter och skillnader mellan FTIR spektra som tagits på makro- och nanonivå. Dessa mätningar gav lovande resultat för fortsatta ytanalyser. / <p>QC 2023-05-15</p>

Объектом исследования является идея осуществления производства антикоррозийных продуктов. Целью работы является обоснование экономической целесообразности реализации проекта по производству антикоррозийных продуктов. В процессе выполнения работы были получены следующие результаты. В рамках изучения методических подходов к оценке экономических перспектив были даны определения экономического и маркетингового анализа, определены их основные методы и задачи. А также составлена авторская классификация антикоррозионных продуктов, учитывающая их ключевые признаки. Результаты анализа рыночных и перспектив позволили выявить основных потребителей и конкурентов интересующего отраслевого рынка, а также позволили определить оптимальный объем выпуска антикоррозийного продукта и его среднерыночную стоимость. Таким образом, оптимальный объем выпуска, не нарушающий сложившегося рыночного равновесия, составляет порядка 30 тонн, а среднерыночная стоимость 1 тонны продукта составляет 100-110 тыс. рублей. Результаты патентного исследования, проведенного в рамках оценки научно-технических перспектив, позволили определить динамику патентования и выявить аналогичные технические решения. На основе результатов проведенного патентного исследования пределен средний срок жизни проекта по производству железооксидного пигмента с противокоррозионными свойствами – 4 года. Научно-практическим результатом, полученным автором в процессе выполнения работы, является создание модели производства, учитывающей более эффективные инструменты реализации идеи по производству антикоррозийных продуктов. В рамках этой модели, с учетом выводов, сделанных в аналитической части работы, рассчитаны показатели экономической эффективности трех вариантов трансфера технологии. / The object of the study is the idea of the production of anti-corrosion products. The purpose of the work is to justify the economic feasibility of the project for the production of anti-corrosion products. The following results were obtained in the course of the work. As part of the study of methodological approaches to the assessment of economic prospects, the definitions of economic and marketing analysis were given, their main methods and tasks were determined. And also the author's classification of anticorrosion products, taking into account their key features. The results of market and prospects analysis allowed to identify the main consumers and competitors of the industry market of interest, as well as to determine the optimal volume of production of anti-corrosion product and its average market value. Thus, the optimal volume of output that does not violate the existing market balance is about 30 tons, and the average market value of 1 ton of product is 100-110 thousand rubles. The results of the patent research conducted in the framework of the assessment of scientific and technical prospects allowed to determine the dynamics of patenting and to identify similar technical solutions. Based on the results of the patent research, the average life of the project for the production of iron oxide pigment with anti – corrosive properties is limited to 4 years. The scientific and practical result obtained by the author in the process of the work is the creation of a production model that takes into account more effective tools for the implementation of the idea for the production of anti-corrosion products. Within the framework of this model, taking into account the conclusions made in the analytical part of the work, the indicators of economic efficiency of the three options for technology transfer are calculated.