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Waxy crude oils (1/3 of oil produced worldwide), pumping through pipelines considered risky operation due to the crude wax content (15-40 wt.%) and to the temperature at which wax supersaturates and precipitates, leading to the danger of pipe blockage, eventually resulting, in multimillion dollars loss in production and maintenance. This research undertaken to develop operational strategy of waxy crude pipelines, considering the crude and crude gel properties and flow conditions. The research problem was approached by characterizing the crude gel with and without additives using chromatography (GC), differential scanning calorimetry (DSC), cross polarised microscopy (CPM), controlled stress and oscillatory shear rheology (CSR and OSR), the principal parameters being the crude temperature and the rate at which the crude was cooled. GC and DSC were useful in establishing wax composition, content and wax appearance temperature (WAT). Control stress rheometer proved to be the most appropriate as it measured the reduction in apparent viscosity at full production (10-50 s-1 shear rate), near shutdown (1 s-1 ) and yielding when the oil was statically cooled. On this basis, it was established that the wax inhibitor was the most effective. CPM revealed that only the wax inhibitor changed the structure of the gel, disrupting its otherwise knitted crystal network. Dilution with the light crude oil merely reduced the wax content and the pour point depressant reduced the gelling temperature. OSR provided a check on CSR and confirmed the gelation temperature measured. CSR provided the yield stress measured, it also provided comprehensive data that can be used for theoretical modelling of this complex flow. / Libyan Petroleum Institute, Libya

Chromonic liquid crystals are a relatively new class of lyotropic liquid crystals. In an effort to understand this lyotropic phase better, studies on the phase behavior, defects formed in these systems and characterization of the order were performed. We studied three chromonic liquid crystal materials in nematic and biphasic regions: Sunset Yellow FCF (SSY, a food dye), a cationic perylene diimide derivative (PDI, a conducting dye) and cromolyn sodium (DSCG, a drug). For SSY chromonics in the nematic region, order parameters ( and ) were obtained by polarized Raman measurements. Using the order parameters the flow behavior was predicted and was found to be non-flow aligning. A comprehensive viscoelastic property set of SSY chromonics was obtained by studying the statics and dynamics of defects during the formation of planar aligned monodomain. Applications of PDI thin films as vapor sensors were explored; anisotropic electronic properties of oriented PDI films show good conductivity along the columns presumably arising from the overlap between the ? systems. In the biphasic region, growth and fluctuation of SSY tactoids and interesting patterns of biphasic DSCG under capillary geometry were observed; elastic properties and surface tension were estimated based on the shape of DSCG tactoids. Polymer dispersed lyotropic chromonic liquid crystals with different drop shapes and director configurations were also fabricated using various water-soluble polymers.

Le sujet de cette thèse concerne le développement et la caractérisation de résines photosensibles pour le prototypage rapide. L'étude a tout d'abord consisté à optimiser des systèmes photoréticulables commerciaux : systèmes hybrides acrylates/époxydes. La réactivité des différentes formulations préparées ainsi que leurs propriétés thermomécaniques ont pu être évaluées grâce à la spectroscopie infrarouge à transformée de Fourier résolue dans le temps (RT-FTIR) et par analyse mécanique dynamique (DMA). En parallèle, une étude plus fondamentale visant à mieux comprendre et à contrôler la formation de réseaux polymères interpénétrés simultanés méthacrylate/époxyde a été menée. L'influence de paramètres physico-chimiques tels que l'intensité lumineuse, la concentration en photoamorceur sur les propriétés finales du matériau a notamment été abordée. Ensuite, des résines dont la chimie est moins conventionnelle ont été considérées. Comme très peu de ces monomères sont disponibles commercialement, certains d'entre eux ont dû être synthétisés. Certaines formulations ont démontré non seulement une bonne réactivité mais aussi d'intéressantes propriétés thermomécaniques et une limitation du retrait de polymérisation. Finalement, une méthode de mesure du retrait linéaire simple et facile à mettre en œuvre a été mise en place afin de comparer les différents systèmes chimiques proposés au cours de la thèse. L'utilisation de cet outil est très appréciable car il pourrait permettre de choisir le type de formulations induisant le moins de retrait possible lors de la réalisation d'un objet couche par couche. / The aim of this thesis is to develop and characterize UV curable resins for rapid prototyping application. The study started with the optimization of commercially available hybrid acrylate/epoxide systems (IPNs) commonly used in this industrial field. The reactivity of the different tested formulations in conjunction with their thermomechanical properties have been assessed by means of Real time Fourier transform infrared spectroscopy (RT FTIR) and Dynamic mechanical analysis (DMA). In the meantime, a more academic study has been performed on an epoxide/methacrylate mixture in order to get a better understanding and a control of the IPN formation. The influence of the light intensity and the photoinitiator concentration on the final properties has been examined. Then, UV curable resins whose chemistry is less conventional have been considered. Owing to the lack of commercial availability of some monomers, time has been spent to synthesize them. Some formulations display promising features especially in terms of reactivity, thermomechanical properties and linear shrinkage. Finally, a simple method to measure linear shrinkage has been set up to compare the different systems proposed during the thesis and thus evidences the less shrinkable UV curable system.

Selon l'American Lung Association, dans les dernières années, les maladies pulmonaires sont devenues la troisième cause mondiale de décès après les maladies cardiovasculaires et le cancer. Et il est prévu que la position augmente dans ce classement au cours des dix prochaines années. Les maladies pulmonaires telles que la broncho-pneumopathie chronique obstructive (BPCO) et la fibrose interstitielle affectent des millions de personnes dans le monde, tuant des milliers d'entre eux chaque année tandis que de nouveaux cas sont signalés. Aujourd'hui, il n'y a pas de diagnostic précoce des maladies pulmonaires. Celles-ci se manifestent essentiellement par une modification des propriétés viscoélastiques du parenchyme pulmonaire qui ne peut être détectée par les techniques usuelles appliquées généralement sur les autres organes. La tomodensitométrie par rayons X et la biopsie pulmonaire chirurgicale peuvent indiquer la maladie. Cependant, il n'est pas encore possible de prédire la progression de cette dernière ni de déterminer la durée optimale de la thérapie, ni encore d'explorer l'administration d'autres agents potentiellement moins toxiques que ceux utilisés de nos jours. Les causes et les mécanismes de la maladie ainsi que les facteurs génétiques associés ne sont pas encore déterminés. Les enjeux sociétal et médical sont énormes. Les propriétés viscoélastiques des tissus pulmonaires jouent un rôle clé dans la fonction-même de l'organe. Elles pourraient être des biomarqueurs pulmonaires très sensibles puisqu'elles dépendent de la structure des tissus, des conditions biologiques, et qu'elles sont considérablement altérées par la plupart des maladies pulmonaires comme le cancer, l'emphysème, l'asthme ou la fibrose interstitielle. Toutefois, l’auscultation et l’exploration tactile couramment utilisées ne peuvent pas localement les sonder in vivo. Dans ce travail de thèse, une nouvelle modalité a été développée pour cartographier les propriétés viscoélastiques du parenchyme pulmonaire afin de détecter, quantifier et classer les maladies qui les modifient. Cette nouvelle méthode d'imagerie, l’élastographie par résonance magnétique de l'hélium-3 hyperpolarisé, bénéficie de l'innocuité et de la sensibilité de la technique ainsi que de l'importance du signal d'hélium-3 hyperpolarisé dans les poumons.Tout d'abord, la technique a été validée sur des fantômes de poumons préservés de cochon. D'une part, les hypothèses de confinement du gaz et de l'indépendance à la composition du gaz qui sous-tendent l'élastographie IRM quantitative de l'hélium-3 ont été confirmées. D'autre part, la sensibilité de la technique a été éprouvée par rapport à l'inflation des poumons et à leur dépendance à la gravité. Puis, un mode d'excitation original a été développé et les protocoles d'acquisition IRM ont été optimisés pour réaliser l'élastographie IRM de l'hélium-3 in vivo. Les premières mesures de propagation d'ondes de cisaillement ont été obtenues à la fois dans des poumons de rat et d'humain. Les modules d'élasticité de cisaillement obtenus s'accordent assez bien avec les valeurs de rigidité obtenues ex vivo par les techniques alternatives. Ce travail ouvre une voie unique d'exploration in vivo de la physiopathologie pulmonaire. / According to the American Lung Association, for the last few years, lung diseases have become the third most common cause of death worldwide after cardiovascular disease and tumors, and it is expected to rise up the ranking position in the next ten years. Lung diseases such as Chronic Obstructive Pulmonary Disease and interstitial fibrosis affect millions of people worldwide, killing thousands of them every year while new cases are reported. Today, there is no early diagnosis of these pulmonary diseases. They effectively manifest by a modification of the viscoelastic properties of the lung parenchyma which cannot be detected by usual techniques that are applied to other organs. X-ray computer tomography and surgical lung biopsy can state the disease. However, it is not yet possible to predict its progression, to determine the optimal length of the therapy, or to explore the administration of other agents potentially less toxic than those used nowadays. Causes and mechanisms of the disease, associated genetic factors are not determined yet. The social and medical issues are huge. The viscoelastic properties of lung tissue play a key role in the basic function of the organ. They could be very sensitive pulmonary biomarkers as they depend on the tissue structure, the biological conditions, and they are dramatically altered by most lung diseases like cancer, emphysema, asthma, or interstitial fibrosis. However, current auscultation and tactual explorations fail to regionally probe them in vivo.In this PhD work, a new modality was developed to regionally measure the viscoelastic properties of the lung parenchyma in order to detect, quantify, and classify diseases that modify them. This new imaging approach, hyperpolarized helium-3 Magnetic Resonance Elastography (MRE), benefit from the innocuity and the sensitivity of the technique as well as from the huge hyperpolarized helium-3 signal in the lung. First, the technique was validated on preserved pig lung phantoms. On the one hand, the assumptions of gas confinement and gas content independence that support quantitative helium-3 MRE were assessed. On the other hand, the sensitivity of the technique was challenged with respect to lung inflation and gravity dependence. Second, original means of mechanical excitation were developed and MR acquisition protocols were optimized to perform helium-3 MRE in vivo. First measurements of shear wave propagation were achieved in both rat and human lungs. Resulting shear elasticity agrees fairly well with stiffness values found ex vivo by alternative measurement techniques. This work opens up promising insights into lung pathophysiology in vivo.

L’étude de la durabilité des élastomères des stators des pompes Moineau a été menée en utilisant à la fois des simulations numériques, des essais thermomécaniques et des analyses physico-chimiques. Les simulations numériques ont eu pour principal objectif de permettre de déterminer la localisation et le niveau des maximums des champs mécaniques dans le stator. Les essais ont permis quant à eux de caractériser le comportement mécanique du matériau élastomère sous sollicitations mécaniques cycliques à différentes températures. Une première étude a permis d’analyser l’évolution de l’effet Payne en fatigue. Une seconde s’est concentrée sur l’analyse de l’effet de l’application d’un chargement thermomécanique sur l’évolution de la microstructure du matériau élastomère. / The study of the sustainability of the rubber, which is the main constitutive material of the Moineau pump stator, was carried out using finite element analyses, thermomechanical experiments and physic-chemical analysis. The numerical simulations were performed to identify the range and location of the maximal stress and strain within the pump stator. The experimental tests allowed to characterize the mechanical behaviour of rubber under cyclic solicitation at several temperatures. The first part of the study focused on the Payne effect during fatigue loading while the second dealt with the effect of a thermomechanical loading on the rubber microstructure evolution.

This master thesis deals with the optimization of the procedure of modification of hyaluronic acid structure for the use in the artificial synovial liquids. Based on the literature research, the amino acid alanine was used for the modification of carboxylic group in the glucuronic acid. The main subject of study is the improvement of the stability and mechanical properties of synovial liquid. DLS microrheology, macrorheology, thermogravimetric analysis (TGA), multi-angle light scattering with flow-field flow fractionation (AF4-MALS) and infrared spectroscopy (FTIR) were used for characterization. The theoretical part of this theses submits review of the musculoskeletal system, role of hyaluronic acid in metabolism and summary of synovial liquid. The experimental part focuses on the measurement of the stability and mechanical properties of three artificial samples (first with no modification, second with modified hyaluronic acid and third with modified hyaluronic acid and chondroitin sulphate). These samples were compared with real horse synovial fluid and artificial viscosupplement Orthovisc®.

Plant derived oils bear intrinsic double-bond functionality that can be utilized directly for the thiol–ene reaction. Although terminal unsaturations are far more reactive than internal ones, studies on the reversible addition of thiyl radicals to 1,2-disubstituted alkenes show that this is an important reaction. To investigate the thiol–ene coupling reaction involving these enes, stoichiometric mixtures of a trifunctional propionate thiol with monounsaturated fatty acid methyl esters (methyl oleate or methyl elaidate) supplemented with 2.0 wt.% Irgacure 184 were subjected to 365-nm UV-irradiation and the chemical changes monitored. Continuous (RT– FTIR) and discontinuous (NMR and FT–Raman) techniques were used to follow the progress of the reaction and reveal details of the products formed. Experimental results supported by numerical kinetic simulations of the system confirm the reaction mechanism showing a very fast cis/trans-isomerization of the alkene monomers (<1.0 min) when compared to the total disappearance of double-bonds, indicating that the rate-limiting step controlling the overall reaction is the hydrogen transfer from the thiol involved in the formation of final product. The loss of total unsaturations equals thiol consumption throughout the entire reaction; although product formation is strongly favoured directly from the trans-ene. This indicates that initial cis/trans-isomer structures affect the kinetics. High thiol–ene conversions could be easily obtained at reasonable rates without major influence of side-reactions demonstrating the suitability of this reaction for network forming purposes from 1,2-disubstituted alkenes. To further illustrate the validity of this concept in the formation of cross-linked thiol–ene films a series of globalide/caprolactone based copolyesters differing in degree of unsaturations along the backbone were photopolymerized in the melt with the same trithiol giving amorphous elastomeric materials with different thermal and viscoelastic properties. High thiol–ene conversions (>80%) were easily attained for all cases at reasonable reaction rates, while maintaining the cure behaviour and independent of functionality. Parallel chain-growth ene homopolymerization was considered negligible when compared with the main coupling route. However, the comonomer feed ratio had impact on the thermoset properties with high ene-density copolymers giving networks with higher glass transition temperature values (Tg) and a narrower distribution of cross-links than films with lower ene composition. The thiol–ene systems evaluated in this study serve as model example for the sustainable use of naturally-occurring 1,2-disubstituted alkenes at making semi-synthetic polymeric materials in high conversions with a range of properties in an environment-friendly way. / Vegetabiliska oljor som innehåller dubbelbindningar kan användas direkt för thiolene reaktioner. Trots att terminala dubbelbindningar är mycket mer reaktiva än interna visar dessa studier att den reversibla additionen av thiyl radikaler till 1,2-disubstituerade alkener är en viktig reaktion. För att undersöka tiol–ene reaktionerna, som ivolverar dessa alkener förbereddes stökiometriska blandningar av en trifunktionell propionat tiol och enkelomättade fettsyrametylestrar (metyloleat eller metyl elaidat) samt 2.0 vikt.% Irgacure 184. Dessa blandningar utsattes för 365-nm UV strålning och de kemiska förändringarna studerades. De kemiska förändringarna analyserades med olika kemiska analysmetoder; realtid RT–FTIR, NMR och FT–Raman. Dessa användes för att analysera de kemiska reaktionerna i realtid och följa bildandet av produkterna. Reaktionsmekanismen bekräftades med hjälp av experimentella data och beräkningar av numeriska och kinetiska simuleringar för systemet. Resultaten visar en mycket snabb cis/trans-isomerisering av alkenmonomeren (<1.0 min) jämfört med den totala förbrukningen av dubbelbindningarna, vilket indikerar att det hastighetsbegränsande steget kontrolleras av väteförflyttningen från tiolen till slutprodukten. Förbrukningen av den totala omättade kolkedjan är lika med tiolförbrukningen under hela reaktionen, även om bildandet av produkten gynnas från trans-enen. Detta indikerar att den första cis/trans-isomerstrukturen påverkar kinetiken. Höga tiol-ene utbyten kan enkelt erhållas relativt snabbt utan inverkan av sidoreaktioner. Detta innebär att denna reaktion kan användas som nätverksbildande reaktion för flerfunktionella 1,2-disubstituted alkenmonomerer. Vidare användes fotopolymerisation i smälta på en serie globalid/kaprolaktonbaserade sampolyestrar med varierad grad av omättnad med samma tritiol vilket resulterade i bildandet av amorfa elastomeriska material med olika termiska och viskoelastiska egenskaper. Hög omsättning (>80%) uppnåddes relativt enkelt för samtliga blandningar oberoende av den initiala funktionaliteten. Homopolymerisation av alkenen var försumbar i jämförelse med den tiol–en-reaktionen. Mängden alkengrupper har inverkan på härdplastsegenskaperna där en hög andel alken ger en nätstruktur med högre glastransitionstemperatur (Tg). Tiol–ene reaktionen utvärderades i modellsystem baserade på naturlig förekommande 1,2-disubstituterade alkener för att demonstrera konceptet med tiol-förnätade halvsyntetiska material. / QC 20110915

Wood is a widely used construction material that has many advantageous properties, and some drawbacks. These drawbacks are mainly associated with the porous vascular structure of wood that makes it a high water-absorbent material. In addition, wood’s properties alter substantially with respect to the moisture content. Amongst the treatment techniques that limit the water uptake capacity of wood, vacuum-aided impregnation has exhibited promising results. However, little research has explored the effect of key parameters (such as the vacuum pressure) on the effectiveness of the impregnation. This study aims to optimize the performance of SiO2 impregnation of spruce wood under vacuum pressures. The main objective of this research is to overcome wood’s weakness by reducing its water uptake capacity through a vacuum-aided impregnation technique and study its effect on the physico-mechanical properties of wood under dry and saturated conditions. The study was conducted in two parts. In the first part, wood samples underwent impregnation under atmospheric and three vacuum pressures. Density measurements, water uptake tests, microscopy examination, thermogravimetric analysis, and dynamic mechanical analysis were conducted on non-treated and SiO2-treated samples. Quantitative and qualitative analyses demonstrated that SiO2 impregnation performed under -90 kPa was able to effectively enhance the wood’s properties compared to the other conditions. The SiO2 impregnation under high vacuum pressure demonstrated an effective increase in the density of the wood and achieved a significant reduction in the water uptake capacity. The analysis of the wood’s viscoelastic properties revealed that SiO2 impregnation under atmospheric and vacuum conditions triggered two different reinforcing mechanisms: a solid film, causing stick-slip oscillation, and particle diffusion, causing particle-particle and particle-lumen wall friction, respectively. For the second part, characterization methods such as Impact test, DMA, SEM, EDS, Porosity, and SAXS tests were conducted on non-treated and -90 kPa treated spruce wood samples in dry, saturated, and submerged states in order to reveal the synergistic effect of the SiO2 impregnation pressure and water uptake on the wood’s properties. The results showed that high vacuum impregnation pressure has a significant positive reinforcing effect on the wood’s properties. It increased the impact resistance of wood in dry and saturated conditions. A high vacuum impregnation was able to overcome the softening effect of water and caused a significant increase in the Storage modulus by strengthening the wood’s vascular structure, which accordingly increased the wood’s capacity to absorb energy. High vacuum impregnation was also able to counteract the plasticizing effect of water and significantly increased the Loss modulus by increasing the internal friction in the wood with the diffusion of the nanoparticles in the wood’s cell walls and vascular structure. This phenomenon increased the wood's capacity to absorb and dissipate energy under dry and submerged conditions.

Wood is a viscoelastic composite material that has been historically prominent in the construction of buildings and continues to see widespread use. When used for exterior applications, wood is exposed to dynamic environmental conditions and can degrade if left untreated. Previous research by Lemaire-Paul et al. (2022) has proven that vacuum impregnation of the wood cell structure with a silica (SiO₂) nanoparticle colloid under a vacuum pressure of -90 kPa can enhance the viscoelastic properties, increase the density, and reduce the water uptake of white spruce wood. However, the behaviour of SiO₂-treated wood under different environmental conditions over time has yet to be fully explored. This research aims to examine the durability and performance of SiO₂-treated spruce wood samples subjected to accelerated aging conditions under high temperature and humidity as well as freeze-thaw cycling. Spruce wood samples were treated with 40% SiO₂ nanoparticle colloid under a vacuum pressure of -90 kPa. One set was placed in a hydrolytic aging chamber at 90°C and 80% RH. Another set was placed in a freeze-thaw cycling chamber that cycled from 25°C to -18°C and back at a rate of 6 cycles per day. The samples were removed at regular intervals and thermogravimetric analysis, dynamic mechanical analysis, tensiometry, X-Ray diffraction, and scanning electron microscopy were performed. When compared to the results obtained from a set of non-treated samples, it was found that the SiO₂-treated samples exhibited lower water uptake values that stabilized over time, as well as a lower rate of decrease in peak cellulose degradation temperatures under hydrolytic aging and a slight increase in peak cellulose degradation temperature over time under freeze-thaw aging. The effects of both aging conditions on the viscoelastic properties of the samples were also found to be insignificant. Both types of samples under both types of aging also exhibited an increase in crystallinity over time. These results indicate that the durability and properties of wood can be improved through nano-SiO₂ impregnation as the material remains relatively stable when subjected to high temperature and humidity conditions as well as freeze-thaw cycling over time.