No description available.

The aim of this study was to compare the barrier properties of organic coatings with the same polymer matrix but different types of iron oxide particles, commercial and recycled. The work was carried out for the company SSAB with the aim of investigating whether the pigment Merox ferric oxide, which is produced in-house at the company during the pickling process, can be used and replace commercial iron oxide pigment. Evaluation of the barrier properties was done using electrochemical impedance spectroscopy where the capacitance of the coatings is calculated and reflects the water absorption of the coating over a period of exposure to the electrolyte. By comparing the capacitance of the different coatings, an estimation of the water transport through the different coatings was made. Complementary methods used were digital optical microscopy and scanning electron microscopy.  In this project, 6 lab samples were evaluated. In common, the samples consisted of the same metal substrate, hot-dip galvanized steel, and the binder in the coatings was polyester-melamine. Sample 1 consisted of the binder only, sample 2 contained the commercial iron oxide pigment, samples 3 and 4 consisted of Merox pigments but different levels of chlorine in the pigment. The thickness of the coatings of the 4 samples was 6 m. Sample 5 had a thicker coating of 20 m and contained Merox pigment. The last sample evaluated was a reference sample with anti-corrosive pigment with a thickness of 20 m. Furthermore, exposure tests were carried out with sample 5 to test how different electrolyte solutions affected the samples. The electrolytes tested were 1 M Na2SO4 (for reference), 1 M NaNO3 and 0.1 M NaCl.  The impedance measurements were performed in 3 parallel measurements on the samples with thinner coating (6 m) and an average of the capacitance was used to analyze how the capacitance changes over time. The results showed that sample 1 had much better barrier properties than the samples containing iron oxide pigments, although the exposure time to electrolyte was longer for this sample, the capacitance was lower. Both samples 2 and 4 increased rapidly in capacitance over a short period of time. Sample 3 had a rapid increase at the beginning which later decreased, the sample showed better barrier properties compared to samples 2 and 4. Cross-sectional studies carried out by scanning electron microscopy detected corrosion formation between the zinc and the coating on all samples with thinner coatings. Only one impedance measurement was made on samples 5 and 6, hence multiple measurements need to be performed to calculate the capacitance over time and provide complete and reliable results for these samples.  The results of the exposure tests indicated that the electrolyte used for the electrochemical impedance measurements, 1 M Na2SO4 is more corrosive than the other electrolytes tested, 1 M NaNO3 and 0.1 M NaCl. / Syftet med denna studie var att jämföra barriärsegenskaper hos organiska beläggningar med samma polymer matris men olika typer av järnoxidpartiklar, kommersiella och återvunna. Arbetet utfördes åt företaget SSAB med målet att undersöka om pigmentet Merox ferric oxide, vilket produceras internt på företaget under betningsprocessen, kan användas och ersätta kommersiellt järnoxidpigment. Utvärdering av barriärsegenskaperna gjordes med elektrokemisk impedansspektroskopi där beläggningarnas kapacitans beräknas och avspeglar vattenabsorption av beläggningen över en tidsperiod av exponering till elektrolyt. Genom att jämföra kapacitansen för de olika beläggningarna, har en estimering av vattentransporten genom de olika beläggningarna gjorts. Kompletterande metoder som användes var digitalt optiskt mikroskop och svepelektronmikroskopi.  I detta projekt utvärderades 6 labb-prover. Gemensamt bestod proverna av samma metallsubstrat, varmförzinkat stål och bindaren i beläggningarna var polyester-melamine. Prov 1 bestod endast av bindaren, prov 2 innehöll kommersiellt järnoxidpigmentet. Prov 3 och 4 bestod av Merox pigment men olika halter av klor i pigmentet. Tjockleken på beläggningarna hos de 4 proverna var 6 m. Prov 5 hade en tjockare beläggning på 20 m och innehöll Merox pigment. Det sista provet som utvärderades var ett referensprov med anti-korrosivt pigment med en tjocklek på 20 m. Vidare gjordes exponeringstester med prov 5 för att testa hur olika elektrolytlösningar påverkade proverna. Elektrolyterna som testades var 1 M Na2SO4 (som referens), 1 M NaNO3 och 0,1 M NaCl.  Impendansmätningarna utfördes i 3 parallella mätningar på proverna med tunnare beläggning (6 m) och ett medelvärde av kapacitansen användes för att analysera hur kapacitansen förändras över tiden. Resultatet visade att prov 1 hade mycket bättre barriärsegenskaper än proverna som innehöll järnoxid pigment, även fast exponeringstiden gentemot elektrolyt var längre för detta prov så var kapacitansen lägre. Både prov 2 och 4 ökade snabbt i kapacitans under en kort tidsperiod. Prov 3 hade en snabb ökning i början som senare avtog, provet visade bättre barriärsegenskaper jämfört med prov 2 och 4. Tvärsnittsstudier som genomfördes med svepelektronmikroskopi detekterade korrosionsbildning mellan zink och beläggningen på alla prover med tunnare beläggning. Endast en impedansmätning på prov 5 och 6 utfördes, därav behövs flera mätningar genomföras för att kunna beräkna kapacitansen över tid och ge fullständiga och pålitliga resultat för dessa prover.  Resultaten från exponeringstesterna visade på att elektrolyten som använts för elektrokemiska impedansmätningarna, 1 M Na2SO4 är mer korrosiv än de andra elektrolyterna som testades, 1 M NaNO3 och 0,1 M NaCl.

The purpose of this study was to examine the performance of several generic types of organic protective coatings as a corrosion protection method for the interior of subsea pipelines in sour gas media. The sour gas environment was simulated in the laboratory by the use of an Autoclave and the performance of the organic coatings was studied via the use of Electrochemical Impedance Spectroscopy (EIS) and Linear Polarization Resistance (LPR) tests to determine the coatings resistance, capacitance and corrosion behavior before and after the exposure to sour gas environment. The coating degradation and the corrosion products formed were examined by the use of SEM/EDS. The results indicated that both FBE and Novolac Epoxy coatings had excellent adhesion properties and chemical resistance. The Amine-Cured Novolac Epoxy coating exhibited good adhesion properties and chemical resistance. However, the Phenolic Epoxy coating started to degrade over time and corrosion took place under the coating.

No description available.

L’objectif de cette thèse consiste en une étude fondamentale de différentes approches pour la modification de surfaces d’alliages d’aluminium. Elle s’inscrit dans le cadre du projet FLYCOAT, subventionné par la région Wallonne. Ce dernier avait pour objectif le développement d’alternatives au couplage classique d’un procédé d’anodisation utilisant des bains de Cr (VI) aux résines époxy pour la protection des alliages d’aluminium contre la corrosion. Dans un premier temps, la synthèse par plasma atmosphérique dans un réacteur de type décharge à barrière diélectrique (DBD) de films riches en groupements carboxyliques à partir de 8 précurseurs organiques est étudiée. Une attention particulière est portée à la compréhension fondamentale des mécanismes de polymérisation de ces précurseurs. L’influence significative de minimes variations de la structure chimique du précurseur est étudiée. Concrètement, nous démontrons l’impact de la présence et de la position de doubles liaisons ou encore le ratio C/O dans le monomère injecté sur le mécanisme de synthèse des couches déposées. Pour ce faire, une méthodologie combinant des analyses de la phase plasma et des films déposés est proposée. Les propriétés électriques de la DBD d’argon sont évaluées par oscilloscope avant et durant l’injection des différents précurseurs. La quantité d’énergie transférée de la décharge vers le précurseur est évaluée par spectroscopie d’émission optique et corrélée à sa structure. Une fragmentation réduite est mise en évidence par spectrométrie de masse pour les monomères contenant une double liaison. Ces analyses de la phase plasma sont alors corrélées avec les propriétés physiques et chimiques des films synthétisés. Les compositions chimiques de surface et de la matrice des couches minces sont étudiées par spectroscopie à photoélectrons X (XPS) et infrarouge. Le rôle essentiel de la présence et de la position de la double liaison dans la molécule injectée est démontré. Les vitesses de dépôt et la rugosité des films déposés par plasma atmosphérique avec l’injection des 8 précurseurs sont évaluées par profilométrie à stylet. Dans la seconde partie, le couplage de deux méthodes de plasma atmosphérique est proposé pour la synthèse de couches d’alumine aux propriétés adaptables. Le premier traitement consiste en un nombre varié de passages d’une torche plasma opérant dans un régime d’arc. L’effet du nombre de passages sur les propriétés physiques et chimiques du substrat est étudié par XPS, angle de contact, microscopie électronique à balayage et mesures de diffraction à rayons X. Une corrélation est suggérée entre le nombre de passages de la torche et les propriétés électrochimiques du substrat. L’influence de ce premier traitement sur les propriétés de la couche d’oxyde d’aluminium synthétisée par oxydation par plasma électrolytique est mise en évidence. Dans un troisième temps, le plasma pouvant être considéré comme un réservoir d’énergie, une étude de faisabilité est réalisée afin d’évaluer sa potentielle utilisation pour la réticulation d’une résine de type benzoxazine. L’efficacité du traitement par DBD atmosphérique d’argon ou hélium est comparée et discutée. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Reliability analysis plays an important role in keeping manufacturers in a competitive position. It can be applied in many areas such as warranty predictions, maintenance scheduling, spare parts provisioning, and risk assessment. This dissertation focuses on statistical modeling and predictions based on lifetime data, degradation data, and recurrent event data. The datasets used in this dissertation come from the field, and have complicated structures. The dissertation consists of three main chapters, in addition to Chapter 1 which is the introduction chapter, and Chapter 5 which is the general conclusion chapter. Chapter 2 consists of the traditional time-to-failure data analysis. We propose a statistical method to address the failure data from an appliance used at home with the consideration of retirement times and delayed reporting time. We also develop a prediction method based on the proposed model. Using the information of retirement-time distribution and delayed reporting time, the predictions are more accurate and useful in the decision making. In Chapter 3, we introduce a nonlinear mixed-effects general path model to incorporate dynamic covariates into degradation data analysis. Dynamic covariates include time-varying environmental variables and usage condition. The shapes of the effect functions of covariates may be constrained to be, for example, monotonically increasing (i.e., higher temperature is likely to cause more damage). Incorporating dynamic covariates with shape restrictions is challenging. A modified alternative algorithm and the corresponding prediction method are proposed. In Chapter 4, we introduce a multi-level trend-renewal process (MTRP) model to describe component-level events in multi-level repairable systems. In particular, we consider two-level repairable systems in which events can occur at the subsystem level, or the component (within the subsystem) level. The main goal is to develop a method for estimation of model parameters and a procedure for prediction of the future replacement events at component level with the consideration of the effects from the subsystem replacement events. To explain unit-to-unit variability, time-dependent covariates as well as random effects are introduced into the heterogeneous MTRP model (HMTRP). A Metropolis-within-Gibbs algorithm is used to estimate the unknown parameters in the HMTRP model. The proposed method is illustrated by a simulated dataset. / Ph. D.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Organic coatings are extensively used as protective coatings in several industries including the automotive and aircraft industries. The last few years have witnessed an increased interest in improving not only the mechanical properties but also the corrosion protection properties of organic coatings. Among the currently investigated methods of improving the performance of organic coatings is the incorporation of additives in the organic paint matrix. Vapor grown carbon nanofibers (VGCNFs) are a class of carbon fibers that are produced by catalytic dehydrogenation of a hydrocarbon at high temperatures. Depending on the method of synthesis and the post-treatment processes, the diameter of the VGCNFs is normally in the 10-300 nm range. The small size, light weight, high aspect ratio, and unique physical, thermal, mechanical, and electrical properties of VGCNF make it an ideal reinforcing filler in polymer matrix nanocomposites to enhance the mechanical properties of the pure polymeric material in high performance applications in several industries such as the automotive, aircraft, battery, sensors, catalysis, electronics, and sports industries. The main objective of the current investigation was to study the corrosion protection offered by the incorporation of VGCNFs into a commercial alkyd paint matrix applied to the surface of mild steel coupons. The corrosion protection was investigated by immersing samples in air saturated 3% NaCl solution (artificial seawater). The samples were studied by electrochemical impedance spectroscopy (EIS) along with other measurements, including electrochemical (open circuit potential, cyclic voltammetry), chemical (salt spray test), electrical conductivity, and surface analysis (SEM, AFM, optical profilometry, and nanoindentation). The study involved the investigation of the effect of the weight percent (wt %) of the VGCNF as well as the coating film thickness on the corrosion protection performance of the coated steel samples when exposed to the corrosive electrolyte. By way of contrast, the EIS behavior of steel coupons coated with a paint coating incorporating different weight percents of powdered silicon carbide (SiC) particles was also studied. The EIS spectra were used to calculated and graph several corrosion parameters for the investigated systems. At the end, the studied coatings were ranked in order of their anticorrosive properties.