No description available.

Polymers films and membranes with immobile and irreversible reactive sites can provide significant barrier properties for packaging materials. There is a need to develop mathematical models to understand the behavior of these reactive materials and to confidently extrapolate experimental data. Due to mechanical and optical requirements, barrier films may consist of composites, such as polymer blends and multilayer films with alternating reactive and inert layers. The reactive term that consumes the mobile species in the governing transport equations for such materials is a function of both the mobile species and the immobilized reactive sites, leading to non-linear partial differential equations that typically have to be solved numerically. Composite structures add to the complexity of the model. For the polymer blend, a multiscale model was developed, incorporating the reactive details within the particle into the bulk transport equation. For the multilayer film, initial conditions and diffusion coefficients were assigned independently for reactive or inert layers. The models developed for the three configurations were solved numerically over a wide parameter space. Three regimes were identified, namely early times characterized by an initial flux plateau, and intermediate regime, and long times, characterized by the time lag. Asymptotic analysis of the homogeneous model was used to develop analytical predictions for the three regimes, obviating the need to numerically solve the model’s non-linear equations. These predictions were generalized to polymer blends. For multilayer films, predictions for early and long times were developed. Results for polymer blends and multilayer composites were compared and discussions of the most suitable configuration for different scenarios were presented. The reactive barrier configurations studied require the knowledge of parameters such as reaction rates and coefficients of diffusion and solubility of the reactive polymer. Model and predictive equations have been developed to describe the transient mass uptake in reactive homogeneous films, enabling the extraction of these parameters from sorption experiments. / text

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-24T11:22:53Z No. of bitstreams: 1 MIRTES AILA RODRIGUES DE CARVALHO - DISSERTAÇÃO (PPGECA) 2018.pdf: 2832182 bytes, checksum: eb9e4bf2802a12b8ca3371f98de48cbb (MD5) / Made available in DSpace on 2018-08-24T11:22:53Z (GMT). No. of bitstreams: 1 MIRTES AILA RODRIGUES DE CARVALHO - DISSERTAÇÃO (PPGECA) 2018.pdf: 2832182 bytes, checksum: eb9e4bf2802a12b8ca3371f98de48cbb (MD5) Previous issue date: 2018-04-12 / Capes / As misturas asfálticas com ligantes modificados por polímeros são cada vez mais utilizadas para satisfazer as necessidades crescentes do tráfego rodoviário, melhorando as condições de resistência, de durabilidade dos revestimentos asfálticos sob a ação de cargas pesadas. Os polímeros reativos/não-reativos e o ácido polifosfórico, em separado, são opções utilizadas como modificadores dos ligantes cujo o objetivo é melhorar as propriedades mecânicas da mistura asfáltica. No entanto, o uso combinado dos modificadores pode proporcionar melhores resultados que o uso individual. O objetivo desta pesquisa foi de avaliar o comportamento mecânico de misturas asfálticas quando modificadas por polímero reativo/não-reativo associados ao ácido polifosfórico como catalizador em diferentes teores. Para isso foram realizados ensaios físicos e mecânicos nos ligantes 50/70 com adição de Etileno Acrilato de Metila e Metacrilato de Glicidila (EMA-GMA) comercialmente conhecido por S74, Terpolímero de Alta densidade (SX500) e Ácido Polifosfórico (PPA116%), antes e após envelhecimento a curto prazo (RTFO) e nos ligantes 50/70, 55/75 sem a modificação. Foram dosadas misturas asfálticas com 1,8%S74, 0,3%SX500 associadas a teores variados de 0,15; 0,3 e 0,5% PPA116% e analisado o comportamento mecânico das misturas asfálticas por meio de ensaios de Resistência a Tração, Módulo de Resiliência, Módulo Dinâmico, Flow Number, Lotman Modificado e Desgaste Cântabro. Os resultados indicam que as misturas asfálticas com os ligantes modificados com polímero reativo/não-reativo associados ao ácido polifosfórico nos teores de 0,3 e 0,5%PPA se classificam como ligantes elastoméricos 60/85-E e suas respectivas misturas asfálticas possuem maior resistência a deformação permanente quando submetidos a altas temperaturas, maior resistência ao desgaste e menor susceptibilidade a umidade, indicando que tais misturas podem ser usadas como alternativa a misturas asfálticas convencionais, principalmente para regiões de clima tropical. / The polymer modified asphalt mixtures are increasingly being used to satisfy the growing road traffic needs, improving their resistance conditions and the asphalt coating durability under the action of heavy loads. The reactive/non-reactive polymers and the polyphosphoric acid, separated, are largely used as modifiers for the asphalt binders whose objective is to improve its mechanical properties. However, the combined use of them can provide better results that individually. This researches objective was to evaluate the mechanical behavior of the asphalt mixtures when modified with reactive/non-reactive polymer associated with the polyphosphoric acid as a catalyst in different contents. There were performed physical and mechanical tests on the 50/70 binder with the addition of ethylene methyl acrylate and glycidyl methacrylate (EMA-GMA) commercially known as S74, high density thermo-polymer (SX500) and polyphosphoric acid (PPA 116%), before and after the short term aging process (RTFO). The same procedures were performed on the 50/70 and 55/75 non modified binders. Asphalt mixtures were designed with 1,8%S74, 0,3SX500 associated with varied contents of 0,15; 0,30 and 0,50% PPA 116% and analyzed in relation to its mechanical behavior by means of traction resistance, resilience module, dynamic module, flow number, modified lotman and cântabro wear tests. The results indicate that the asphalt mixtures modified with reactive/non-reactive polymer associated with the polyphosphofic acid in the contents of 0,3 and 0,5%PPA are classified as 60/85-E elastomeric binders and have a higher permanent deformation resistance when subjected to high temperatures, greater wear resistance and lower susceptibility to humidity, indicating that this mixtures can be used as an alternative to conventional asphalt mixtures, mainly in tropical climate regions.

No description available.

La contamination microbienne des surfaces est l’une des préoccupations majeures des secteurs d’activités comme l’industrie agro-alimentaire, la santé publique et les milieux hospitaliers. Face aux problèmes de santé publique liés à contamination bactérienne sur les surfaces, la préparation de surfaces aux propriétés antibactériennes est devenue un intérêt de recherche majeur pour de nombreux scientifiques et ce, dans de nombreux domaines de recherches. Du point de vue de la chimie, des matériaux et de la microbiologie, la fonctionnalisation des surfaces de matériaux polymères préexistants sans altérer leur propriété initiale est une solution séduisante. Pour cela, développer des nouveaux matériaux antibactériens/antifouling où la surface serait fonctionnalisée par des polymères antimicrobiens, greffés de manière robuste i.e. de façon covalente représente une solution idéale. Afin de faciliter et d’accélérer le processus de criblage, il est proposé dans ce travail une nouvelle approche pour obtenir des polymères ayant des propriétés antimicrobiennes à la fois en solution et à partir de la surface. Ce travail comprend une étude de (co)-polymérisations contrôlées d'esters actifs servant d’intermédiaires pouvant être post-modifiés pour synthétiser des polymères d'intérêts présentant les caractéristiques antimicrobiennes attendues.Ce travail démontre que la polymérisation radicalaire contrôlée en présence de Cu(0)/Cu(II) est une technique appropriée qui permet de préparer facilement des (co)-polymères réactifs, en solution mais aussi à partir de surface de poly (téréphtalate d’éthylène), communément appelé PET. Dans un premier temps, nous aborderons l'étude de la polymérisation contrôlée du méthacrylate de pentafluorophényle (PFPMA), avec son optimisation en solution, puis à partir de surface du PET porteuse de groupement d’amorçage. De plus, la polymérisation du méthacrylate de p-nitrophényle (NPMA) sera également examinée, ainsi que la copolymérisation des deux esters actifs là-encore par polymérisation de type contrôlée en présence de Cu(0)/Cu(II). La post-modification des polymères activés est ensuite présentée. La post-modification s’est révélée efficace et facile à mettre en œuvre. La structure et les caractéristiques des polymères obtenus ont été analysées et confirmées. Il est à noter que la post-modification a pu être effectuée par un processus séquentiel avec une fonctionnalisation simple ou avec plusieurs huiles essentielles, qui possèdent des propriétés naturelles antibactériennes ou antioxydantes. Différents films de PET ont été modifiés, des polymères aux propriétés anti-adhérentes ont été greffés par cette même méthodologie. Ces surfaces modifiées ont été testées contre deux bactéries modèles telles que Staphylococcus aureus et Pseudomonas aeruginosa afin de déterminer si les modifications de surface ont conféré au film de PET les propriétés biologiques attendues. / Microbial contamination on surfaces has become major concern in various areas including industrial process as well as public health and hospitalization. Being aware of several problems causing by adherence and attachment of bacteria on a surface, preparation of antibacterial surface has become a global research interest for researchers in many domains. From the chemistry integrated with material science and microbiology point of view, functionalization of existing polymeric material surfaces is an attractive solution. In this domain, the surface functionalized with covalently grafted antimicrobial polymers represents an ideal solution. In order to facilitate the screening process, it is proposed in this particular research a new approach to obtain polymers with antimicrobial properties both in solution and from surface. The present approach includes a study in controlled (co)polymerization of active ester(s) serving as intermediate templates that can be eventually modified by polymer post-modification process to fabricate polymer of interest with expected antimicrobial characteristics.In general, it is demonstrated herein that the use of Cu(0)-mediated reversible deactivation radical polymerization (RDRP) is a suitable technique that allows facile preparation of reactive (co)polymers in solution and from surface of poly(ethylene terephthalate). First of all, this thesis focused on the study of controlled polymerization of pentafluorophenyl methacrylate (PFPMA) which appeared to be challenging. Furthermore, along with the optimization of polymerization in solution was the investigation of surface-initiated polymerization of this monomer from PET surface. Besides, polymerization of p-nitrophenyl methacrylate (NPMA) and copolymerization of the two active esters by Cu(0)-mediated RDRP were also examined. In addition, polymer post-modification of obtained (co)polymers with various compounds had been proven to be efficient, easy to perform. The structure and characteristics of obtained products were confirmed to match with expectations. It is remarkable that the post-modification can be done as sequential process, single or dual functionalization with several different essential oils, which are natural antibacterial or antioxidant compounds. On the other hand, the success in polymerization and post-modification of polymer of active esters in solution allowed the fabrication of different PET film grafted with polymers that are envisaged to have antiadhesion properties. Attempts to test such properties were also done against two model bacteria including Staphylococcus aureus and Pseudomonas aeruginosa to investigate if expectations are valid.

Le mélange de polymères est une méthode répandue pour élaborer des matériaux polymères. Cependant, la plupart des polymères sont thermodynamiquement immiscibles entre eux, engendrant une séparation de phase des mélanges et une détérioration de leurs propriétés. Afin de palier ces problèmes, la méthode dite compatibilisation réactive est souvent employée. Elle est basée sur la formation in-situ de copolymères à bloc ou greffés par l’intermédiaire de réactions interfaciales entre polymères réactifs. Cette thèse a pour objet de développer un concept dit agent compatibilisant-traceur réactif qui permettra d’utiliser de faibles quantités d’agents compatibilisants réactifs pour évaluer leurs efficacités de compatibilisation directement sur des extrudeuses bi-vis industrielles, d’une part ; et de caractériser la performance du mélange d’une extrudeuse bi-vis en fonction des conditions opératoires et/ou du profil de vis employé. Ses principales contributions se résument ci-après. L’anthracène de 9-méthylaminométhyle (MAMA), une molécule fluorescente, est incorporée dans un copolymère statistique de styrène (St) et d’isocyanate de 3-isopropenyle-?, ?’-diméthylebenzène (TMI), noté PS-TMI, pour former un agent compatibilisant-traceur réactif, noté PS-TMI-MAMA. Ce dernier sert à la fois comme agent compatibilisant réactif grâce aux groupements isocyanate et traceur grâce aux groupements fluorescents. Il est utilisé pour les mélanges à base de polystyrène (PS) et de polyamide 6 (PA6) afin d’évaluer son efficacité de compatibilisation. Les mélanges PS/PA6 sont élaborés dans un mélangeur discontinu et une extrudeuse bi-vis, respectivement. Dans le cas du mélangeur discontinu, la quantité du copolymère greffé formé in-situ, noté PS-g-PA6-MAMA, augmente alors que le diamètre des domaines de la phase dispersée (DDD) diminue considérablement au début du mélange. Lorsque le mélange se poursuit, le nombre de greffons en PA6 du PS-g-PA6-MAMA augmente, engendrant une composition très asymétrique du PS-g-PA6-MAMA qui est thermodynamiquement instable aux interfaces. De ce fait, il peut être arraché des interfaces vers la phase PA6 et peut y former des micelles. Lorsqu’il est arraché des interfaces, il perdra son efficacité de compatibilisation et le DDD augmentera. L’action du mélange a un double effet sur le procédé de compatibilisation réactive. Il promeut la réaction interfaciale entre le PS-TMI-MAMA et le PA6, d’une part ; et aggrave l’arrachage du PS-g-PA6-MAMA de l’interface, d’autre part. L’utilisation de faibles quantités de l’agent compatibilisant-traceur réactif permet de mesurer les évolutions de la teneur en agent compatibilisant-traceur réactif, du DDD et de la teneur en agent compatibilisant-traceur réactif ayant réagi en fonction du temps de séjour dans une extrudeuse bi-vis. Pour une masse molaire donnée, l’efficacité de compatibilisation d’un agent compatibilisant-traceur réactif augmente avec l’augmentation de la teneur en TMI dans une certaine limite. Pour une teneur en TMI donnée, la réaction interfaciale est plus rapide avec la diminution de la masse molaire dans une certaine limite et le DDD devient plus petit en un temps plus court. L’influence du taux de remplissage de la vis est plus significative que celle du temps de séjour. Lorsque le taux de remplissage de la vis augmente, le taux de la réaction interfaciale augmente et le DDD diminue. Lorsque l’angle d’un élément de mélange augmente, les efficacités du mélange distributif et du mélange dispersif augmentent, ce qui se traduit par une augmentation de la quantité du PS-g-PA6-MAMA formée et une diminution du DDD par rapport à la même quantité de PS-g-PA6-MAMA produite. Lorsque la largeur d’un élément de mélange augmente, l’efficacité du mélange distributive augmente alors que celle du mélange dispersif demeure inchangée. La substitution d’éléments de mélange par des éléments inverses améliore l’efficacité du mélange distributif et celle du mélange dispersif / Polymer blending is a common method to prepare high-performance polymer materials. However, most polymer pairs are thermodynamically immiscible, leading to phase separation and deterioration in material properties. To overcome such problems, the most common method is reactive compatibilization which is based on the in-situ formation of a graft or block copolymer by interfacial reaction between reactive polymers. This thesis aims at developing a concept of reactive compatibilizer-tracer which will allow using small amounts of reactive compatibilizers to evaluate their compatibilizing efficiency in industrial scale twin screw extruders, on the one hand; and to characterize the mixing performance of a twin screw extruder as a function of process conditions and/or screw profile. Its main contributions are summarized below. 9-(methylaminomethyl) anthracene (MAMA), a fluorescent molecule, is incorporated into a random copolymer of styrene (St) and 3-isopropenyl-?, ?’-dimethylbenzene isocyanate (TMI), denoted as PS-TMI, to form a reactive compatibilizer-tracer, denoted as PS- TMI-MAMA. The latter serves both as a reactive compatibilizer due to its isocyanate moieties and a tracer due to its fluorescent moieites. It is used for polystyrene (PS)/polyamide 6 (PA6) blends to evaluate its compatibilizing efficiency. Compatibilized PS/PA6 blends are processed in a batch mixer and in a twin screw extruder, respectively. In the case of the batch mixer, the amount of the in-situ formed graft copolymer denoted as PS-g-PA6-MAMA increases and the dispersed phase domain diameter (DDD) decreases drastically in the initial period of mixing. As the mixing further proceeds, the number of PA6 grafts of the PS-g-PA6-MAMA increases, resulting in a highly asymmetrical composition of the PS-g-PA6-MAMA which causes thermodynamic instablility at the interface. As a result, it could be pulled out of the interface to the PA6 phase and form micelles. Once it is pulled out of the interface, it will lose its compatibilizing efficiency and the dispersed phase domain diameter increases sharply. Mixing has a dual effect on the reactive compatibilization process. On the one hand, it promotes the interfacial reaction between the PS-TMI-MAMA and PA6. On the other hand, it aggravates the pull out of the resulting PS-g-PA6-MAMA from the interface. The use of small amounts of the reactive compatibilizer-tracer together with transient experiments for RTD allows assessing the evolutions of the reactive compatibilizer-tracer content (CC), the dispersed phase domain diameter (DDD), and the reacted reactive compatibilizer-tracer content (RCC) as a function of residence time in a twin-screw extruder. Based on the above results, the emulsification curve (DDD vs. CC), the RCC vs. CC curve and effective emulsification curve (DDD vs. RCC) are obtained. When the molar mass of the reactive compatibilizer-tracer is fixed, its compatibilizing efficiency increases with increasing TMI content within an appropriate range. When its TMI content is fixed, the interfacial reaction goes faster as the molar mass of the reactive compatibilizer-tracer decreases within a certain range, and the DDD becomes smaller in a shorter time. The effect of degree of fill fixed by the throughput Q/screw speed N ratio is more dominant than that of residence time. As the degree of fill increases, the interfacial reaction increases and the DDD decreases. As the angle of adjacent the kneading block increases, its distributive and dispersive mixing efficiencies increase, resulting in an increase in interfacial area generation and a decrease in DDD on the basis of the same amount of PS-g-PA6-MAMA. On the other hand, as the width of the kneading block increases, the distributive mixing efficiency increases and the dispersive mixing efficiency remains unchanged. Substitution of kneading blocks by reverse ones increase both the distributive and dispersive mixing efficiencies