O objetivo desta pesquisa foi desenvolver e aperfeiçoar uma formulação com fase gel lamelar contendo óleo de Calendula officinalis e avaliar seu potencial na atividade cicatrizante de úlceras em ratos. A formulação estudada possui valor de EHL 6,0, constituída por óleo de calêndula e sistema tensoativo formado por derivados etoxilados dos alcoóis cetílico e estearílico (Ceteth 2/Steareth 20). Primeiramente, determinou-se a região do diagrama ternário de fases em que se encontravam as emulsões com fase gel lamelares (EFGL), macroscopicamente estáveis. Em seguida foi avaliada a estabilidade do sistema e parâmetros que poderiam influenciar na formação das estruturas anisotrópicas. Avaliou-se o comportamento das emulsões utilizando o teste de perda de massa por evaporação. Na avaliação in vitro, foram realizados testes de citotoxidade do óleo de calêndula frente às células de fibroblastos da linhagem L929 através do ensaio de apoptose e necrose. O teste in vivo foi realizado através do Índice de Cicatrização de Úlceras (ICU) no modelo em dorso de ratos (úlcera excisional contrátil) a fim de avaliar o potencial cicatrizante da emulsão proposta comparando com o sham (grupo controle). As úlceras foram avaliadas mediante análise de imagem nos tempos de 0, 2, 7, 14 e 21 dias após o procedimento cirúrgico. A EFGL demonstrou maior estabilidade frente aos testes de estabilidade preliminar e acelerada em relação as demais formulações. Além disso, esta formulação demonstrou menor área de histerese (tixotropia), portanto menor grau de espalhabilidade e com maior tempo de contato com a úlcera. Durante a evaporação das emulsões houve manutenção das estruturas anisotrópicas O óleo bruto da Calendula officinalis não apresentou interferência na via da apoptose e necrose na concentração de até 1000 ?g/mL em fibroblastos L929. A formulação proposta promoveu melhor cicatrização no modelo de úlcera cutânea (ICU) na região dorsal de ratos, supondo- se modular a fase inflamatória do processo de cicatrização, pois o maior recrutamento de células inflamatórias bem como a colagênese, diminuída no grupo EFGL, foram fatores essenciais que permitiram a total reepitelização das úlceras cutâneas. Portanto, pode-se concluir que a metodologia utilizada nesta pesquisa foi útil para a obtenção de emulsões com fase gel lamelar, sendo que a formação dessa estrutura é importante para a estabilidade do sistema, podendo ser utilizada como uma formulação viável e eficaz no processo cicatricial de feridas. / The aim of this research was to improve a lamellar gel phase emulsion containing Calendula officinalis oil and to investigate its potential as a modern wound dressing. First, we determined the region of the ternary phase diagram in which the emulsions were stable and we also evaluated the intrinsic stability of the system and the action of some parameters which may influence the formation of lamellar gel phase. In addition, we analyzed the samples\' behavior during the evaporation process. Moreover, an in vitro cytotoxicity assay of the calendula oil was performed in order to evaluate apoptosis and necrosis in fibroblast cell line L929. Then, an in vivo test was carried out by the wound healing rate (WHR), using a specific model of ulcer in rats (excisional contractile ulcer), in order to assess potential healing of the proposed emulsion (LGP) by comparing with the sham group. The ulcers were evaluated by image analysis at 0, 2, 7, 14 and 21 days after surgery. The emulsion 6 \'showed greater stability in the preliminary and accelerated stability tests in relation to the previous studied formulation. Moreover, this formulation presented more compatible characteristics, because it showed smaller hysteresis area of ? (thixotropy), therefore a lower degree of spreadability and, accordingly, the formulation may increase contact span with ulcer, which is a desirable characteristic. During evaporation of the emulsions, the anisotropic structures were maintained, but their type varied depending on the decreased amount of water in the system. The crude oil of Calendula officinalis showed no interference with the pathway of apoptosis and necrosis in the concentration of 1000 mg / mL in L929 fibroblasts. The proposed model has promoted better wound healing rate in the ulcers in the dorsal region of rats. It seemed to modulate the inflammatory phase of the healing process, because of the increased recruitment of inflammatory cells as well as collagenesis, once LGP emulsion decreased in the group, were factors essential that allowed total reepithelialization of skin ulcers in rats treated with LGP emulsion. In conclusion, this study produced an enhanced and useful LGP which can be used as a new approach to stimulate the healing process and treat wounds efficiently.

OBJETIVO: Comparar a viscosidade dinâmica da camada superficial da fáscia temporal com a de outros tecidos biológicos tradicionalmente utilizados em implantes de pregas vocais para o tratamento de rigidez de pregas vocais. DESENHO DO ESTUDO: Experimental. MÉTODO: Amostras de camada superficial da fáscia temporal, camada profunda da fáscia temporal e gordura abdominal de 12 cadáveres são submetidas a medição de viscosidade dinâmica. RESUTADOS: A viscosidade dinâmica das diferentes amostras apresenta-se na seguinte ordem crescente: camada superficial da fáscia temporal, camada profunda da fáscia temporal e gordura abdominal. Observa-se diferença estatística na comparação entre todas as amostras. DISCUSSÃO: Quanto maior for a viscosidade da mucosa da prega vocal, maior é a pressão subglótica necessária para se iniciar a fonação. Dessa maneira, um bom material implantável em lâmina própria de prega vocal deve ter baixa viscosidade. Por esse parâmetro, a camada superficial da fáscia temporal é um material promissor para implantação em pregas vocais. CONCLUSÃO: A viscosidade dinâmica da camada superficial da fáscia temporal é menor que a da camada profunda da fáscia temporal e que a da gordura abdominal. / OBJECTIVE: To compare the dynamic viscosity of superficial layer of temporalis fascia with that of other biological tissues traditionally used for vocal fold implants to treat vocal fold rigidity. STUDY DESIGN: Experimental. METHOD: Measurement of dynamic viscosity of samples of superficial layer of temporalis fascia, deep layer of temporalis fascia and abdominal fat of 12 cadavers are performed. RESULTS: Dynamic viscosity values of the different samples are presented in the following increasing order: superficial layer of temporalis fascia, deep layer of temporalis fascia and abdominal fat. There is statistical difference among all the samples. CONCLUSION: Dynamic viscosity of superficial layer of temporalis fascia is lower than the ones of deep layer of temporalis fascia and abdominal fat.

Orientadores: Edvaldo Sabadini, Rosângela Barros Zanoni Lopes Moreno / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T12:17:08Z (GMT). No. of bitstreams: 1 Rodrigues_RobertaKamei_D.pdf: 3168201 bytes, checksum: 311be9e2895bc6d972563662136638fa (MD5) Previous issue date: 2013 / Resumo: O presente trabalho descreve o potencial das micelas gigantes como aditivos para facilitar operações de gravel-pack. O objetivo da operação de completação gravel-pack é obtenção de um filtro de areia ou cerâmica (gravel) capaz de conter areia da formação durante a produção de um poço de petróleo. As micelas gigantes podem ser utilizadas na fase de preenchimento do gravel-pack, com a finalidade de produzir um sistema capaz de reduzir as perdas de carga geradas pelo fluxo turbulento do fluido (por redução de atrito hidrodinâmico), melhorar a homogeneidade da distribuição de areia na dispersão e, consequentemente, viabilizar a operação em cenários de janela operacional estreita. O fênomeno de redução de atrito hidrodinâmico está relacionado com a menor energia requerida para o escoamento de líquidos em regime turbulento, quando certas macromoléculas estão dissolvidas. Estudos indicam que a redução de atrito hidrodinâmico pode estar diretamente relacionada à flexibilidade e ao tamanho de macromoléculas, que podem interagir com os vórtices e evitar a dissipação da energia. Soluções de alguns surfactantes, em determinadas condições, podem formar micelas alongadas (gigantes). O sistema resultante possui algumas características de soluções poliméricas, sendo capaz de produzir o mesmo efeito, sem, no entanto, sofrer degradação mecânica devido ao bombeamento ou cisalhamento prolongado. Foram desenvolvidos estudos fundamentais a partir de medidas reológicas, calorimétricas e de espalhamento dinâmico de luz para investigar a estabilidade térmica e mecânica de micelas gigantes formadas por surfactantes catiônicos e ânions aromáticos. Em seguida, foram avaliadas as melhores composições, nas quais se obtiveram significativos níveis de redução de atrito hidrodinâmico em condições de temperaturas de fundo de poço, em soluções de alta salinidade e usando-se micelas gigantes formadas por surfactantes comerciais. Os resultados desses estudos fundamentais foram utilizados para avaliar o desempenho das micelas gigantes em circuitos de escoamento. Também foi verificado o efeito da presença das micelas gigantes no arraste do grão de areia, em condições próximas às das operações de gravel-pack / Abstract: This thesis describes the potential of wormlike micelles as additives to improve gravel-pack operations. The aim of the completion operation of grave-pack is to create a sand or ceramic filter able to contain the sand formation during the gravel-pack operation in order to produce a system capable of reducing friction losses on a fluid in turbulent flow (by drag reduction), to improve the homogeneity of the distribution of sand dispersion and thus facilitate the operation in case of narrow window scenarios. The phenomenon of drag reduction is related to the lower energy required for liquid transports in turbulent flow when certain macromolecules are dissolved. Studies indicate that drag reduction can be directly related to the flexibility and size of the macromolecules, which can interact with the vortices and prevent dissipation of energy. Solutions of some surfactants, under certain conditions, can form long micelles (wormlike micelles). The resulting system has some characteristics of polymer solutions, being able to produce the same effect, however without suffering degradation due to pumping or high shear. Fundamental studies were conducted using rheological, calorimetric and dynamic light scattering measurements in order to investigate the thermal and mechanical stability of wormlike micelles formed by cationic surfactants and aromatic anions. Then, the best compositions were evaluated, which were obtained significant levels of drag reduction under bottom hole temperature, in solutions of high salinity and using wormlike micelles formed by commercial surfactants. The results of these fundamental studies were used to evaluate the performance of wormlike micelles in flow loops. We also checked the effect of the presence / Doutorado / Físico-Química / Doutora em Ciências

Orientadores: Flavio Luis Schmidt, Alessandro Nogueira / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-20T07:43:19Z (GMT). No. of bitstreams: 1 Quast_Ernesto_D.pdf: 3408175 bytes, checksum: 2c21225123069a5fa9cfeb4921650aca (MD5) Previous issue date: 2012 / Resumo: O umê (Prunus mume) é um fruto de caroço que apresenta alta rusticidade e adaptabilidade agrícola, sendo muito estudado como porta-enxerto de pêssegos, nectarinas e ameixas. Embora no Brasil não existam estudos visando o processamento dos frutos, o umê é muito consumido e apreciado em países asiáticos devido às propriedades nutracêuticas relacionadas ao consumo de concentrados de frutos verdes ou flores, por isso, o objetivo do presente trabalho é possibilitar o aproveitamento desta matéria prima pela elaboração de um produto apreciado pelo consumidor brasileiro, com apelo saudável. Foram utilizados frutos de diferentes localidades do Estado de São Paulo, caracterizados segundo suas dimensões, massa e rendimento no despolpamento, bem como seus aspectos botânicos. Os frutos tiveram a sua maturação acompanhada pela cor e após maduros, foram branqueados termicamente, despolpados, desaerados e envasados a quente na planta piloto de Frutas e Hortaliças da Faculdade de Engenharia de Alimentos da UNICAMP. Foram realizadas análises de textura instrumental em frutos verdes e maduros. Na Universidade Estadual de Ponta Grossa (UEPG) foram realizadas análises químicas de compostos fenólicos e da atividade antioxidante dos frutos colhidos em cinco diferentes localidades do Estado de São Paulo e em diferentes graus de maturação, bem como as análises reológicas. As dimensões dos frutos (2,0 a 3,6 cm de diâmetro) e suas massas foram significativamente inferiores (6 a 16 gramas) aos valores relatados em trabalhos científicos de autores asiáticos. Os frutos não apresentaram variação significativa do teor de compostos fenólicos e da atividade antioxidante durante a maturação, a partir de sua completa maturação fisiológica (88 dias após a floração), cujos valores foram de 147 a 226 mg catequina/ g base seca e 21 a 34 µMol Trolox/ g base seca, respectivamente. A reologia foi realizada para polpa de umê nas concentrações de 6 a 9 ºBrix, nas temperaturas de 15 a 75 ºC. O comportamento reológico da polpa de umê se mostrou independente do tempo, com comportamento não-Newtoniano e pseudoplástico (Herschel-Bulkley). Apresentou bom ajuste aos modelos reológicos de Herschel-Bulkley, Casson, Bingham e Lei da Potência. A equação de Arrhenius possibilitou o cálculo da energia de ativação para diferentes concentrações de polpa. A consistência da polpa de umê é altamente influenciada pela concentração dos sólidos solúveis do produto. A micro estruturação da polpa com alginato, para adição ao suco clarificado de umê mostrou-se estável com a elevação do pH para valores superiores a 3,5 / Abstract: Prunus mume is a stone fruit that exhibits high robustness and agriculture adaptability. Its use is being extensively studied as rootstocks for peaches, nectarines and plums. Although in Brazil there are no studies for mume fruit processing, in Asian countries this fruit is widely consumed and appreciated due to the nutraceutical properties related to the consumption of concentrated or processed green-stage fruits or flowers. The present work aim is to produce a highly acceptable product with health appeal. Fruits from different locations in São Paulo State were characterized according to their size, weight and yield pulping, as well as its botanical characteristics. Fruits were evaluated during maturation by color and after fully-ripe they were thermally blanched, pulped, deaerated and hot filled in the pilot plant of Fruits and Vegetables of the Faculty of Food Engineering at UNICAMP. Instrumental texture analyses of green and ripe fruits were performed. At the State University of Ponta Grossa (UEPG) were done chemical analysis of total phenolic compounds and antioxidant activity of fruits collected in 5 different locations in the State of São Paulo and at different stages of maturity, as well as rheological analyses. The fruit dimensions (2.0-3.6 cm diameter) and their mass were significantly lower (6-16 g) than values reported in scientific studies done in Asian countries. Total phenolic content and antioxidant activity did not vary during maturation of the fruit, from its full physiological maturity (88 days after flowering), with values of 148-226 mg catechin/ g dy basis and 21- 34 mMol Trolox/ g dry basis, respectively. Pulp concentrations at 6-9 °Brix were used to study the rheological properties from 15 to 75 °C. The rheological behavior of mume pulp is non-Newtonian pseudoplastic (Herschel-Bulkley). Herschel-Bulkley, Casson, Bingham and Power Law rheological models described well the mume pulp behavior. The Arrhenius equation was used to calculate the activation energy for different concentrations of pulp and was shown that consistency is highly influenced by soluble solids concentration. Micro structured particles of pulp with alginate for adding into clarified mume juice just showed stability with pH increase over 3.5 / Doutorado / Tecnologia de Alimentos / Doutor em Tecnologia de Alimentos

Abstract Doppler optical coherence tomography (DOCT) provides a non-disruptive, high resolution and real-time method for imaging flow velocity profiles inside small channels and capillaries. DOCT has been mostly used in the biomedical field to image blood flow. However, applications in the field of rheology have been rare. In this thesis, the time domain DOCT (TD-DOCT) was utilized to measure flow velocity profiles inside capillaries with high resolution. Time domain configuration was chosen due to the ability to implement dynamic focusing and, in addition, to have sufficient velocity range, especially at high speeds. The accuracy and reliability of the laboratory-built DOCT device was verified with Newtonian suspension and, further, the performance was compared to the commercial DOCT. In vivo measurements with slime mould Physarum polycephalum showed the versatility of DOCT to measure the flow velocity profile of a different kind of scattering suspension even with very low flow rates. The effects of multiple scattering on the accuracy of the measured flow velocity profiles were experimentally studied with two phantom configurations. The first case consisted of the static superficial layer, where the plain glass capillary with flowing Intralipid suspension was embedded into a cuvette. In the second case the moving superficial layer was made by introducing a second glass capillary in front of the studied flow. The results showed that multiple scattering has noticeable effect on the accuracy of the measured flow velocity profiles, especially at the deeper regions. Novel application of the DOCT technique is presented by implementing it to a capillary viscometer. As a result, the absolute viscosity of the Newtonian suspension is derived with high precision directly from the measured flow velocity profile and pressure drop without making any assumption of the flow under study. The results are consistent with the reference values measured with the commercial viscometer. / Tiivistelmä Doppler optinen koherenssitomografia (DOCT) on tekniikka, jolla on mahdollista mitata suspensioiden virtausnopeusprofiili virtausta häiritsemättömästi, reaaliaikaisesti ja tarkalla resoluutiolla ohuista kapillaareista. DOCT-tekniikkaa on hyödynnetty erityisesti lääketieteen alueella silmän rakenteen kuvantamisessa ja veren virtausmittauksissa. Tekniikan sovellukset nesteiden reologian tutkimuksessa ovat olleet harvinaisia. Tämän työn tarkoituksena on kehittää DOCT-tekniikkaa ja soveltaa sitä kapillaariviskometrissä viskositeetin määritykseen suoraan mitatusta virtausnopeusprofiilista. Tässä työssä hyödynnettiin laboratoriossa rakennettua aikatason DOCT-laitetta (TD-DOCT), jolla mitattiin virtausnopeusprofiili kapillaarin sisältä mikrometrien resoluutiolla. TD-DOCT valittiin, koska siinä voitiin käyttää dynaamista fokusointia parantamaan sivusuuntaista resoluutiota ja signaali-kohinasuhdetta. Tämän lisäksi se soveltuu laaja-alaisesti eri virtausnopeuksille, erityisesti nopeille virtauksille. Rakennetun DOCT-laitteen tarkkuus ja luotettavuus todennettiin mittaamalla Newtonista suspensiota ja vertaamalla mittaustuloksia kaupallisella DOCT:lla tehtyihin mittauksiin. Mittaukset elävässä organismissa, Physarum polycephalum -limasienessä, osoittavat laitteen soveltuvuuden erilaisten suspensioiden virtausnopeusprofiilin mittaukseen myös hyvin hitaissa virtauksissa. Moninkertaisen sironnan vaikutusta mitattujen profiilien tarkkuuteen tutkittiin kahdella eri konfiguraatiolla. Ensimmäisessä asetelmassa virtausnopeusprofiili mitattiin kapillaarista, joka oli upotettu valoa sirottavaan Intralipid-suspensioon, ja jonka upotussyvyyttä voitiin säätää. Toisessa asetelmassa muodostettiin dynaaminen valoa sirottava kerros asettamalla toinen Intralipidiä sisältävä kapillaari mitattavan kapillaarin eteen. Tulokset osoittavat, että monikertainen sironta vaikuttaa mitatun virtausnopeusprofiilin tarkkuuteen erityisesti kun valoa sirottava kerroksen paksuus kasvaa. Tässä työssä DOCT -tekniikkaa käytetään ensimmäistä kertaa kapillaariviskometrin yhteydessä. Newtonisen suspension absoluuttinen viskositeetti määritetään hyvin tarkasti suoraan mitatusta virtausnopeusprofiilista ja painehäviöstä ilman oletuksia virtaavasta nesteestä. Mitatut viskositeettiarvot vastaavat vertailumittauksia, jotka tehtiin kaupallisella rotaatioviskosimetrilla.

La maintenance des ouvrages en matériaux cimentaires fissurés a un coût économique et environnemental considérable, les méthodes de traitement actuelles étant polluantes et d’une efficacité limitée à long terme. La biocicatrisation, reposant sur la formation d’un dépôt de carbonate de calcium d’origine bactérienne au sein des fissures du matériau, est une alternative durable et écologique aux résines synthétiques. Cette thèse a pour objectif de créer une méthode de biocicatrisation de fissures d’ouvertures comprises entre 150 et 500 μm, en optimisant sa mise en oeuvre pour une utilisation commerciale. Cette méthode repose sur l’injection de bactéries dans les fissures, par le biais d’un milieu épaissi favorisant la précipitation de CaCO3 biosourcé. Pour ce faire, ce travail de thèse repose sur trois axes. Dans un premier temps, le milieu épaissi est créé puis ses propriétés rhéologiques sont optimisées à l’aide de mesures rhéologiques et d’essais d’injection dans des éprouvettes de mortier fissurées. Dans un deuxième temps, l’effet de l’épaississement du milieu sur la croissance de B. pseudofirmus et sur la bioproduction de carbonate de calcium est évalué. Enfin, des essais de biocicatrisation sont conduits en conditions contrôlées et en milieu extérieur sur des matériaux fissurés afin de vérifier le potentiel de cette méthode à différentes échelles allant de l'éprouvette de mortier à la dalle de béton. Les essais réalisés ont permis de formuler une suspension thixotropique et rhéofluidifiante en combinant deux épaississants, le Welan et l’Attagel. Cette suspension peut être injectée efficacement et sans drainage dans des fissures de 150 à 800 μm d’ouverture. L’ajout d’épaississants n’a pas d’impact sur la croissance de B. pseudofirmus et augmente la production de carbonate de calcium par les bactéries. Les essais de biocicatrisation ont démontré que l’utilisation de milieu épaissi contribue durablement au colmatage des fissures en formant un film solide lors de son séchage, et constitue un support au sein duquel les bactéries peuvent réaliser le processus de biocicatrisation malgré les fortes contraintes imposées par une utilisation in situ. A l’issue du traitement de biocicatrisation, la production de CaCO3 au sein des fissures par la souche bactérienne d’étude, B. pseudofirmus, a pu être démontrée par des observations microscopiques (MEB). Les essais menés au cours de ce projet ont permis de mettre au point une méthode de biocicatrisation ayant un potentiel pour une utilisation commerciale, se démarquant par sa facilité d’emploi et le cumul entre colmatage abiotique et biologique. / Abstract : Maintenance of cracked cementitious materials comes at a high environmental and economic cost, as current reparation technologies are polluting and lack long-term durability. Bio-healing, which relies on the clogging of cracks with bacterial calcium carbonate, is a durable and environmentfriendly alternative to synthetic resins. Indeed, calcium carbonate, calcite in particular, is a long-lasting material, and bacterial activity does not require the use of any toxic chemicals. Based on a previous study proving the bio-healing potential of the bacteria Bacillus pseudofirmus under controlled conditions, this project aims to design a bio-healing method allowing to repair cracks from 150 to 500 µm wide and fitting commercial use. This method relies on the injection of bacteria in cracks, using a thickened medium which enhances CaCO3 bioproduction. To achieve this goal, the work was organized according to three phases. The first phase is to create and characterize the thickened medium through rheological measurements and injection tests in cracked mortars. For the second phase, the effect of the thickened medium on bacterial growth and bioproduction of CaCO3 is assessed through growth experiments. For the third phase, bio-healing tests are performed in a controlled environment and outdoors on cracked materials in order to confirm the potential of this method for commercial use, for lab and pilot scales. During the rheological experiments, we created a thixotropic and shear-thinning suspension using two thickeners in combination, Welan and Attagel. This suspension can be efficiently injected into 150 and 800 µm wide cracks without post-injection drainage. Adding thickeners does not alter bacterial growth, and increases CaCO3 bioproduction. Biocicatrisation tests revealed that the use of a thickened suspension contributes to sealing of cracks as it dries to form a solid film inside the cracks, and embed the bacteria so they could precipitate significant amounts of CaCO3 despite the constraints of in situ conditions. At the end of the bio-healing treatment, the strain B. pseudofirmus has been proven to precipitate CaCO3 through SEM observations. The experiments which have been performed during this PhD led to the creation of a bio-healing method which holds a true potential for commercial use, as it is particularly easy to use and combines biotic and abiotic sealing of the cracks.

Les phénomènes de mouillage et la rhéologie des fluides à seuil sont deux domaines de la physique des matériaux mous dans lesquels de grandes avancées ont été faites lors des derniers siècles. De plus ces questions sont d'une grande importance au niveau des applications industrielles, ce qui contribue à leur dynamisme. En revanche, le mouillage des fluides à seuil a été peu étudié, alors que c'est une situation fréquente. En effet, presque tous les fluides rencontrés dans l'industrie et la vie quotidienne sont des fluides à seuil. D'autre part, la connaissance des propriétés de mouillage est cruciale lors de leur manipulation car la plupart des processus font intervenir des interfaces.Dans ma thèse, je m'intéresse aux questions suivantes : comment la tension de surface apparente est-elle affectée par le seuil ? Comment le seuil influence-t-il la dynamique du mouillage, habituellement décrite par la loi de Tanner ? Pourquoi l'angle de contact d'une goutte de fluide à seuil n'est-il pas prédit par la loi d'Young-Dupré ?J'ai réalisé des expériences sur un fluide à seuil modèle appelé carbopol. La première expérience a consisté à mesurer la force d'adhésion d'un pont capillaire, qui a été comparée au cas des fluides simples. Les résultats ont montré l'importance de l'histoire de la déformation et de l'élasticité du fluide. La seconde expérience a porté sur l'étalement de gouttes sur une surface hydrophile. J'ai étudié la dynamique d'étalement, ainsi que l'angle de contact final. Alors que la dynamique est contrôlée par la viscoélasticité, l'état final est déterminé par le seuil / Wetting phenomena and yield-stress fluids rheology are subfields of soft matter physics where big understanding steps have been made during the last centuries. In addition, these two fields have very important potential implications for industry, which contributes to their dynamism. But their combination, the wetting of yield-stress fluids, has received little interest until the very last years, although it is a situation that happens all the time. Indeed, yield-stress fluids gather nearly all the fluids encountered in food industry, cosmetics, building industry, oil and gas industry… and wetting properties are crucial when processing or using the fluids, as many processes involve interfaces with air or a solid surface.In this thesis, I consider the following questions: how is the apparent surface tension affected by yield stress? How does the yield stress influence the wetting dynamics, classically described by Tanner’s law? Why can the final contact angle of a sessile drop of yield-stress fluid not be predicted by Young-Dupré’s theory?I performed experiments with a model yield-stress fluid called carbopol. The first experiment consisted in measuring the adhesion force of a capillary bridge and comparing it to the case of simple fluids. The main results show the importance of the deformation history and of the fluid elasticity. The second main experiment concerned spreading of drops on a hydrophilic surface. I studied the short-time dynamics and the long-time dynamics, as well as the final contact angle. The first regime is controlled by viscoelasticity, whereas the final state is determined by the yield stress

Le développement de lubrifiants à haute valeur ajoutée subissant des conditions opératoires de plus en plus draconiennes, économes en carburant et performants pendant une longue durée reste un défi considérable pour les fabricants d’huiles. Cette thèse concerne l’étude du rôle et des actions des améliorants d’indice de viscosité (ou Viscosity Index Improvers (VII)) dans les lubrifiants moteurs. Le premier objectif visé dans ce travail est la caractérisation des comportements rhéologiques et la modélisation de la viscosité en fonction de conditions réelles de température, pression et contrainte de cisaillement pour des solutions d’huile de base et de polymère sans additifs fonctionnels. Plusieurs polymères (PAMA, OCP et PISH) de masses moléculaires et conformations (peigne, linéaire et étoile) différentes sont utilisés à 1,2% en masse dans une huile de base minérale hydrocraquée. L’originalité de la thèse réside dans l’utilisation de rhéomètres non-commerciaux à haute pression (jusqu’à 800 MPa). Un deuxième défi réside dans la compréhension de la relation entre la réponse rhéologique des lubrifiants automobiles simplifiés et les mécanismes présents à l’échelle moléculaire en explorant les notions de conformation, de solubilité et de rayon hydrodynamique grâce à l’extension de la loi d’Einstein à haute pression. Enfin, l’étude se concentre sur le lien entre rhéologie et tribologie et par extension, entre la composition chimique du lubrifiant et la tribologie. Les épaisseurs de film sont mesurées et comparées avec les prédictions analytiques de Hamrock-Dowson et avec les simulations numériques basées sur l’équation de Reynolds généralisée en incluant les modèles rhéologiques. Les données expérimentales et numériques sont en adéquation. / The development of high value-added lubricants overcoming more and more drastic operating conditions, fuel-efficient and providing excellent performance during a long time remains a huge challenge for oil makers. This thesis is dedicated to the study of the role and the actions of Viscosity Index Improvers (VII) in engine lubricants. The first objective targeted in this work is the characterization of the rheological behaviors and the modeling of viscosity in function of realistic conditions of temperature, pressure and shear stress for polymer-thickened base oil solutions without functional additives. Several polymers (PAMA, OCP and PISH) with different molecular weights and conformations (comb, linear and star) are used with a concentration of 1.2% (w/w) in a hydrocracked mineral base oil. The originality of the thesis lies in the use of non-commercial rheometers under high pressure (up to 800 MPa). A second challenge is the understanding of the relationship between the rheological response of simplified engine lubricants and the mechanisms occurring at the molecular scale by exploring the notions of conformation, solubility and hydrodynamic radius by the extension of the Einstein’s law at high pressure. Finally, the study focuses on the link between rheology and tribology and by extrapolation, between the chemical composition of the lubricant and tribology. The film thickness is measured and compared with the Hamrock-Dowson analytical predictions and with the numerical simulations based on the generalized Reynolds’ equation including the rheological models. Both experimental and numerical data are in good agreement.

Les matériaux d’oxyde de silice et de titane sont présents dans de nombreux domaines (chimie, environnemental, médical, pharmaceutique, etc.). Le principal problème de ces matériaux concerne les forts coûts financier et environnemental de leur synthèse. Dans ce travail de recherche, l’objectif fut de résoudre cette problématique. Ainsi, une nouvelle synthèse d’oxyde de silice a été élaborée. Ces nanostructures ont été analysées par les méthodes de caractérisation classique en sciences des matériaux (Adsorption volumétrique N2, Analyse Thermogravimétrique (ATG), …). Les propriétés viscoélastiques des milieux réactionnels ont été déterminées par micro-rhéologie. Une stratégie d’élimination de certaines familles de surfactant non ioniques (poloxamères et polyéthoxydes) utilisées comme template dans les synthèses de matériaux mésoporeux à base de silice (SBA-n, MSU-X, …) a été également mise en œuvre. Cette procédure a permis à la fois de récupérer les surfactants et d’obtenir des matériaux aux propriétés physicochimiques remarquables, identifiées par les mêmes méthodes d’instrumentation. Après fonctionnalisation de leur surface, les matériaux lavés semblent plus efficaces en termes d’adsorption de composés organiques que leurs homologues calcinés. Etendu aux oxydes de titane, tout aussi efficace pour éliminer les composés tensio-actifs, le procédé de lavage semble produire à partir d’un pourcentage de TiO2 (> 70 %) des matériaux hautement réactifs en photocatalyse et au pouvoir antibactérien assez élevé. / Silica and titanium oxides are present in many fields (chemistry, environmental, medical, pharmaceutical, etc…). The main problem of these materials concerns the synthesis financial and environmental costs. In this work, the aim was to solve this problem. A new greener silica oxide nanoparticles synthesis was prepared. These nanomaterials have been analyzed by the conventional characterization methods in material sciences (N2 volumetric adsorption, Thermogravitometric Analysis (TGA),...). The viscoelastic properties of the reaction media were determined by micro-rheology. A strategy for the elimination of non-ionic surfactant families (poloxamers and polyethylene oxide) ) used as template in the synthesis of mesoporous materials based on silica (SBA-n, MSU-X, ....) was also implemented. This procedure allowed to recover the surfactants and to obtain materials with remarkable physicochemical properties identified by the same methods instrumentation. After functionalization of the surface, the washed materials appear to be more efficient in terms of adsorption of organic compounds as their calcined counterparts. Extended to titanium oxide, the washing process seems to produce from a percentage of TiO2 (> 70%) highly reactive materials in photocatalysis and with a high antibacterial power.

Au Québec, lors de la période de gel et dégel, l’enrobé bitumineux, constituant le revêtement de la chaussée, est soumis à des conditions sévères qui le dégradent. Ces conditions sont : précipitations de pluie et fontes de neige générant une saturation partielle du matériau, présence de sel déverglaçant, passages de véhicule lourd sollicitant mécaniquement le matériau, variations de températures engendrant la création de déformations et de contraintes au sein du revêtement, et présence de cycles de gel-dégel.A cet effet, la revue de la littérature porte sur l’étude : des conditions sévères (sollicitations mécaniques, climatiques, hydriques et chimiques), et des caractéristiques physiques de l’enrobé qui affectent sa durabilité, ses comportements mécaniques (viscoélastique linéaire et en fatigue) et thermomécaniques (coefficient de dilatation-contraction thermique).Notamment, un programme expérimental de laboratoire a été réalisé en vue de vérifier l’influence de ces conditions sévères sur la dégradation et le comportement de l’enrobé. Premièrement, des essais thermiques, incluant des cycles de gel et dégel, ont été réalisés sur des éprouvettes d’enrobé à l’état sec et partiellement saturé en eau ou en saumures. Les éprouvettes sont instrumentées d’une jauge axiale et de deux thermocouples. L’éprouvette partiellement saturée en eau, comparativement à celles partiellement saturées en saumures, est soumise à des dilatations et des contractions nettement plus importantes lors de la formation et la fonte de la glace. De +10 à +23°C, les coefficients de dilatation linéique des éprouvettes partiellement saturées sont assez similaires, mais supérieurs à celui de l’enrobé à l’état sec, ce qui implique que l’enrobé partiellement saturé se contracte et se dilate un peu plus que celui a l’état sec à ces températures.Deuxièmement, les éprouvettes ont été soumises à des essais mécaniques, de module complexe, afin d’évaluer l’évolution de leur endommagement suite aux cycles de gel et dégel. Les résultats des essais et du modèle rhéologique 2S2P1D ont été utilisés afin de simuler le comportement de l’enrobé selon les divers états. Au fil des cycles de gel et dégel, un endommagement est observable pour l’ensemble des éprouvettes, mais nettement supérieur pour l’éprouvette partiellement saturée en eau. De plus, pour les éprouvettes partiellement saturées, un comportement distinct est observable en dessous et au-dessus de la température de solidification des liquides.Pour terminer, l’étude du comportement à la fatigue de l’enrobé suivant l’état sec et partiellement saturé en eau est réalisée. A +10°C et 10Hz, seules des diminutions légères ont été observées au niveau du module (3%) et de la résistance à la fatigue (ɛ6 de 105 vs 109ƒμdef) pour l’enrobé partiellement saturé en eau. Ces faibles diminutions sont attribuables à la faible période d’immersion des éprouvettes d’enrobé dans l’eau, à la faible température de l’eau et de l’essai, à la faible teneur en vides des éprouvettes, au bitume modifié et aux granulats de qualité utilisés / During winter and spring in the province of Quebec, hot mix asphalt (HMA) pavement could be subjected to sever conditions over their design life. These conditions are: 1) rainfall and snowmelt, which generates the partial saturation of the HMA, 2) winter maintenance requiring the presence of de-icing salt, which acting chemically on HMA, 3) traffic, which acting mechanically on HMA, and 4) temperature changes and presence of freeze-thaw cycles (FTC) creating thermal stress and deformation (thermo-mechanical coupling) within the pavement, and pressure, within the material, generated by freezing water or brines. More specifically, the literature review of this work focuses on the study of: 1) severe conditions such as climatic, chemical and mechanical solicitations, 2) physical characteristics of HMAthat affect its durability, mechanical properties (viscoelastic and fatigue) and thermomechanical properties (coefficient of thermal contraction).An experimental laboratory program was conducted to verify the influence of these severe conditions on the degradation and behavior of HMA. First, thermal testing (-18 to +23°C), including freeze-thaw cycles (FTC, -18 to +10°C) were performed on samples under dry (D)and partially saturated (PS), with water or brine, states. The samples were instrumented with an axial gauge and two thermocouples. During FTC (-18 to +10°C), sample partially saturated with water, compared to those partially saturated with brines, is subject to expansions and contractions significantly greater during formation and melting of ice. In the temperature range from +10 to +23°C, the linear coefficients of thermal contraction of partially saturated samples are quite similar, but higher than that of HMA in dry state. At such temperature range, this implies that the partially saturated HMA contracts and expands a little more than that in dry state. Secondly, the samples were subjected to mechanical testing.The complex modulus test was performed in order to evaluate the damage of samples due to FTC. The test results and rheological model 2S2P1D were used to simulate the behavior of the HMA according to the various states. Over FTC, damage is observed for all samples, butmuch higher for the PS sample with water. Moreover, for PS samples, a distinct behavior is observable below and above the solidification temperature of the liquid. Finally, the study of the fatigue behavior of HMA under PS, with water, and D states is performed. At +10°C and 10Hz, only slight decreases were observed for complex modulus (3%) and fatigue (ε6 = 105 vs 109μstrain) for HMA partially saturated with water. These small decreases are due to the low period of immersion of samples in water, lowers temperatures of water and test, low void content of the samples, modified bitumen and good aggregates used.