L'objectif de ces travaux est d'étudier les effets d'une irradiation ultrasonore haute fréquence (500 kHz) sur la synthèse électrochimique de polymères conducteurs en milieu aqueux. Les ultrasons favorisent la réaction de polymérisation électrochimique en augmentant le transport des espèces électroactives vers l'électrode. Ils engendrent des films plus compacts, présentant une topographie plus fine et plus homogène. Les effets chimiques engendrés par la propagation de l'onde acoustique permettent un meilleur taux de dopage des films. Néanmoins, leur conductivité électrique se trouve légèrement diminuée, dû à une dégradation des chaînes polymères par l'activité cavitationelle. La possibilité de contrôler les propriétés de morphologie fut mise à profit dans différentes applications comme celles des capteurs pH potentiométriques ou des revêtements anti-corrosion. Pour de telles applications, utilisant ces films en tant que couche fonctionnelle, les surfaces obtenues en présence d'irradiation ultrasonore mènent à de meilleurs résultats. Une technique de masquage sélectif à base d'ultrasons focalisés a également été développée afin d'élaborer un substrat biphasique laissant présager d'intéressantes applications biologiques

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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.

Les composés hybrides organiques-inorganiques représentent une classe intéressante de matériaux dotés d'un très large éventail d'applications potentielles dans les revêtements protecteurs, les micro-optiques, conducteurs ioniques, membrane échangeuse de protons etc. Depuis le début des années 1990, le développement de la chimie sol-gel, dite «Chimie Douce», a donné naissance à une nouvelle ère de matériaux hybrides, où des conditions douces de synthèse ont permis un accès simplifié aux matériaux nanocomposites. Parmi les divers précurseurs sol-gel, des organoalkoxysilanes sont très attractifs en raison de leur stabilité, leur faible toxicité et de leur accessibilité. Mais l'insolubilité de ces précurseurs a jusqu'à présent limité leur utilisation dans un procédé sol-gel conventionnel.L'essentiel de la chimie détaillée dans cette thèse porte sur la formation de films hybrides à partir de n-alkylsilanes. Tout d'abord, la partie linéaire et alkyle hydrophobe peut fournir des propriétés barrières à la pénétration de l'eau et des ions, ce qui est un élément clé dans la protection contre la corrosion de substrats métalliques. Deuxièmement, les alkylsilanes possèdent la géométrie et la composition appropriée à un auto-assemblage pour générer des nanostructures périodiquement ordonnées. Récemment, la recherche menée dans le LPIM à Mulhouse démontré le potentiel d’une photopolymérisation inorganique sans solvant. Basée sur la photogénération de superacides par photolyse de sels d'onium qui sont photoamorceurs cationiques classiques, cette voie offre une chance pour étudier l’aptitude de film à base d’alkylsilanes pour la protection des métaux (Partie I) et l'assemblage supramoléculaire (Partie II). / Hybrid organic-inorganic materials have attracted tremendous attention due to their wide range of potential applications in protective coatings, micro-optics, ionic conductors, proton-exchange membrane and so on. Since the early 1990s, the development of sol-gel chemistry (“Chimie Douce”) has given birth to a new age of hybrid materials, where mild synthetic conditions allowed a simplified access to well dispersed and chemically designed nanocomposite materials. Among various sol-gel precursors, organo alkoxysilanes are very attractive because of their superior stability compared to other hybrid precursors, low toxicity and accessibility. However, their insolubility in polar solvents and water has so far limited their use in conventional classic hydrolytic sol-gel procedure.In this thesis, the combination of a UV-driven solvent-free sol-gel process simultaneously to organic photopolymerization has been introduced to form hybrid films based on simple n-alkylsilane building blocks. Based on the photogeneration of superacids under photolysis of onium salts that are conventional photoinitiators, this pathway offers a new chance to investigate alkylsilanes in metal corrosion protection (Part I) and supramolecular assembly (Part II). As the linear and hydrophobic alkyl moiety can provide barrier-properties to the penetration of water and ions, which is a key feature in the corrosion protection of metallic substrates, in part I, the effect of alkyl chain structure of the alkylsilanes as well as their proportions on the corrosion resistance properties has been studied by Salt spray tests and Electron impendence spectroscopy. Furthermore, an effort to correlate the corrosion resistance and coating structure was made as a range of characterization techniques have been implemented (Real time FTIR, 29Si solid state NMR and contact angle measurement). Secondly, alkylsilanes have the proper geometry and composition to self-assemble and generate periodically ordered nanostructures. In part II, the influence on the mesostructure, alkyl chain packing arrangement and its conformational order, which come from alkyl chain length of the silane precursors and the experimental conditions (light intensity, temperature and humidity), has been investigated depending on various characterization techniques (X ray diffraction, microscope, solid state NMR, RT-FTIR). As an application example, a patterned 3D multilayer crystalline organosilica film has been amplified via a facile photopattrerning pathway.

This diploma thesis is focused on the evaluation of changes in non-freezing heat transfer liquid composed of mixture of polyols and water, used in the real solar thermic system. On the base of the research a new heat transfer liquid is proposed on the platform of 1,3-polyols. The emphasis is put on the non-toxic properties of such system revealing the two chemical candidates for a new heat transfer liquid: 1,3-propanediol and glycerol. These chemicals are mixed together with water using different volume concentrations and properties of such liquids are evaluated.

This thesis deals with the evaluation of changes in properties of an antifreeze heat transfer fluid based on polyols used in real solar thermal system. Emphasis is placed on the use of substances with low impact on the environment.

[pt] Corrosão é um fenômeno natural que afeta basicamente todo tipo de material, consome bilhões de dólares anualmente em todo o mundo e pode ter resultados catastróficos. Revestimentos são a técnica de prevenção de corrosão mais utilizada de todas. Nesse sentido, resinas epóxi são amplamente utilizadas em todos os setores da indústria. Apesar de serem polímeros de alta performance, resinas epóxi apresentam problemas, como a necessidade do uso de endurecedores normalmente tóxicos e longos tempos de cura. Benzoxazinas são uma classe emergente de monômeros termofixos de alta performance e auto-cura. Enquanto monômeros mono- e bifuncionais são tipicamente explorados, benzoxazinas de funcionalidade mais alta e sintetizados em procedimento sem solvente e purificados por solventes mais seguros, são um caminho mais desejável em direção à síntese de PBZ para aplicações de alta performance. Nesse trabalho nós descrevemos uma abordagem sustentável para a síntese de benzoxazina trifuncional a partir de melamina, fenol e paraformaldeído. A estrutura química do monômero sintetizado foi confirmada por análises espectroscópicas, enquanto o processo de polimerização foi monitorado por análise calorimétrica. O monômero de benzoxazina foi, então, copolimerizado com uma resina epóxi bifuncional comercial. Nós investimgamos o efeito sinergístico no aumento das propriedades térmicas por meio de DSC e TGA. Resultados revelaram temperatura de transição vítrea de até 268 Graus C. Alta estabilidade térmica também foi obtida, com início de degradação próximo a 400 Graus C e rendimento residual de 22 wt (porcentagem) a 800 Graus C. Posteriormente, o copolímero foi combinado com sílica para produzir revestimentos anti-corrosão. Resultados revelaram superfícies superhidrofóbicas com ótimas resistência a risco e adesão ao substrato de aço. Teste eletroquímico provou alta efetividade dos revestimentos como barreira anti-corrosão, com performance aumentada pela incorporação de sílica. / [en] Corrosion is a natural phenomenon that affects virtually every material, consumes billions of dollars annually worldwide and may result in catastrophic events. Coating is the most utilized technique to prevent corrosion. In this sense, epoxies are widely applied in all sectors of industry. Despite being high performance polymers, epoxies present issues, such as the use of toxic crosslinkers and long curing time. Benzoxazines are an emerging class of high performance self-curing thermosets. While typical monomers are based on mono- and difunctional derivatives, higher functional benzoxazines, prepared without using solvents, but purified with nontoxic solvents, are more desirable towards a greener synthesis of PBZ for high performance applications. Herein, we describe an environment-friendly approach to synthesizing a trifunctional benzoxazine from melamine, phenol, and paraformaldehyde. The chemical structure of the synthesized benzoxazine was confirmed by spectroscopic analyses, while the polymerization was monitored by thermal analysis. The synthesized benzoxazine monomer is, then, copolymerized with a commercial difunctional epoxy resin. We investigate the synergistic effect on improved thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Results showed that a glass transition temperature of up to 268 Degrees C was obtained. A higher thermal stability was also achieved with an onset degradation of nearly 400 Degrees C and char yield of 22 wt (percentage) at 800 degrees C. Later, the copolymer was combined with silica to produce anticorrosion coatings. Results revealed superhydrophobic surfaces with great scratch resistance and adhesion to steel substrate. Electrochemical test proved high effectiveness of the coatings as anti-corrosion barrier, with increasing performance with the incorporation of silica.

Functional coatings produced using scalable and cost-effective processes such as electrodeposition and etching lead to the creation of random roughness at multiple length scales on the surface. The first part of thesis work aims at developing a fundamental mathematical understanding of multiscale coatings by presenting a fractal model to describe wettability on such surfaces. These surfaces are described with a fractal asperity model based on the Weierstrass-Mandelbrot function. Using this description, a model is presented to evaluate the apparent contact angle in different wetting regimes. Experimental validation of the model predictions is presented on various hydrophobic and superhydrophobic surfaces generated on several materials under different processing conditions. Superhydrophobic surfaces have myriad industrial applications, yet their practical utilization has been severely limited by their poor mechanical durability and longevity. Toward addressing this gap, the second and third parts of this thesis work present low cost, facile processes to fabricate superhydrophobic copper and zinc-based coatings via electrodeposition. Additionally, systematic studies are presented on coatings fabricated under different processing conditions to demonstrate excellent durability, mechanical and underwater stability, and corrosion resistance. The presented processes can be scaled to larger, durable coatings with controllable wettability for diverse applications. Apart from their use as superhydrophobic surfaces, the application of multiscale coatings in photo-thermal conversion systems as solar selective coatings is explored in the final part of this thesis. The effects of scale-independent fractal parameters of the coating surfaces and heat treatment are systematically explored with respect to their optical properties of absorptance, emittance, and figure of merit (FOM). / Master of Science / Coatings are extensively used through various industries and serve a range of purposes such as providing protection, changing the physical and chemical properties, decoration, and adding other new properties to the base surface. Coatings produced using scalable and cost-effective processes such as electrodeposition and etching are inherently rough and have features ranging from micro- to nano-scale, leading to their multiscale nature. The first part of thesis work aims at developing a fundamental mathematical understanding of these rough coatings by presenting a model to describe and predict the wettability on such surfaces. Wettability of a surface is its ability to maintain contact with a liquid, resulting from intermolecular interactions when the two are brought together. Wettability for a solid surface is generally quantified by the contact angle, measured through the liquid, where a liquid-vapor interface meets the solid surface. A mathematical model is presented to evaluate the apparent contact angle on such multiscale rough surfaces. Experimental validation of the model predictions is presented on various hydrophobic and superhydrophobic surfaces generated on several materials under different processing conditions. Superhydrophobic surfaces do not get wet by water and water droplet contact angle on these surfaces exceed 150°. Such surfaces have extensive industrial applications, yet their practical utilization has been severely limited by their poor mechanical durability and longevity. Toward addressing this gap, the second and third parts of this thesis work present low cost, facile processes to fabricate superhydrophobic copper and zinc-based coatings via electrodeposition. Additionally, systematic studies are presented on coatings fabricated under different processing conditions to demonstrate excellent durability, mechanical and underwater stability, and corrosion resistance. The presented processes can be scaled to larger, durable coatings with controllable wettability for diverse applications. Apart from their use as superhydrophobic surfaces, the application of multiscale coatings in photo-thermal conversion systems as solar selective coatings is explored in the final part of this iv thesis. Solar selective coatings aim to improve photo-thermal conversion efficiency by providing a high solar absorptance and low thermal emittance. Solar selective coatings ensure that maximum incoming solar radiation is absorbed into the surface and radiative losses due to emissions at high temperatures are minimized. The effects of scale-independent mathematical parameters of the coating surfaces and heat treatment are systematically explored with respect to their optical properties of absorptance, emittance, and figure of merit (FOM).

La fluorescence en temps résolu est une méthode d'analyse spectrophotométrique avancée permettant la sélection des photons émis par luminescence sur un critère temporel. Il est ainsi possible, et cela même dans des milieux complexes et pollués issu de l'industrie, de faire émerger sélectivement le signal d'espèces luminescentes présentant des durées de vie de luminescence relativement grandes.Ce type d'analyse spectrale est particulièrement adapté à la détection de trace d'éléments lanthanides. Chacun des éléments de la série présente en effet des propriétés luminescentes uniques bien que largement fonction de la nature des ligands qui les entourent. Les travaux de thèse présentés dans ce manuscrit utilisent avantageusement la constatation précédente. Deux technologies ont étés mise sur pied et/ou optimisées pour permettre un transfert vers des domaines industriels aux cahiers des charges bien définis.Ainsi dans le domaine de la lutte anti-contrefaçon l'ajout de marqueurs luminescents à temps résolu à base de lanthanide rend possible la surveillance de l'origine et du devenir de divers produits industriels.Dans le domaine pétrolier l'analyse des effluents à l'aide de sondes luminescentes à base de lanthanide permet de quantifier le taux résiduel de plusieurs classes d'additifs chimiques et permet d'optimiser la sécurité, la rentabilité et l'impact écologique du processus d'extraction.Dernièrement un prototype de spectrofluorimètre résolu en temps adapté à un usage industriel a été mis au point pour permettre un transfert technologique du laboratoire vers le milieu industriel / Time-resolved fluorescence is an advanced spectrophotometric analysis method which allows the selection of emitted luminescent photons on a time-based parameters. It is possible to extract the signal of long-lived luminescent species even in complex and polluted matrix from the industry. This type of analysis is especially fitted for the detection of lanthanide ions. During this thesis two technologies based on time-resolved analysis were designed to answer specific industrial problematics. The first one yields the residual concentration of chemical additives used during oil and gas extraction. The second one aims at protecting crude oils and refined fuels from counterfeiting. They both rely on the use of lanthanide complex and the measurement of their luminescent properties. A prototype of time-resolved spectrofluorimeter was also built to transfer the technologies from the laboratory to the industrial world

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>