No description available.

Un matériau est dit « barrière » quand il induit un retard à la diffusion de la molécule « pénétrante ». Il existe peu de possibilités pour moduler les propriétés barrière d'un matériau donné (ex. emballage). La possibilité technologique la plus utilisée consiste à augmenter la tortuosité du chemin du pénétrant par l'addition d'obstacles. Ces obstacles peuvent être obtenus par la création d'une morphologie cristalline particulière ou par l'addition de nano-charges. L'efficacité ainsi obtenue dépend du facteur de forme des obstacles, de leur densité et orientation par rapport à la direction principale des transferts. Les travaux de thèse ont exploré une voie différente, dont les principes ont été formalisés précédemment à partir de considérations théoriques de la diffusion sur des surfaces d'énergie hétérogènes ou d'une description de la réactivité en catalyse hétérogène. L'idée directrice repose sur une augmentation du temps de parcours en lieu et place d'une augmentation du chemin de diffusion en incorporant dans le matériau de nano-adsorbants (obstacles actifs). Dans ce cas, le matériau devient une barrière spécifique à un ou une famille de solutés. En particulier, une théorie étendue des volumes libres a été développée pour séparer les interactions avec la surface active (montmorillonites dans cette étude) des effets des volumes-libres dans le polymère. Les propriétés de sorption des argiles pures et modifiées ont été caractérisées expérimentalement et par modélisation moléculaire pour déterminer les conditions pour lesquelles le coefficient de partage Kcontrast entre la surface des argiles et les polymères testés (polycaprolactone=PCL, alcool polyvinylique=PVA) seraient plus grand que l'unité. Les systèmes PVA+argiles natives ont présenté les meilleures propriétés barrières aux solutés modèles étudiés, avec une activation par les températures basses et une sélectivité modulable par l'humidité relative. Les effets bloquants ont été en bon accord avec la description du piégeage des solutés organiques dans entre les claies empilées des argiles sous contrôle à la fois entropique et enthalpique. / A material is defined as “barrier” when it is able to delay the diffusion of a penetrant. There are few possibilities to modulate the barrier properties of a prescribed material (e.g. packaging material). Most of conventional technological strategies aim at increasing the tortuosity path of the penetrant by adding obstacles. Such obstacles could be obtained either by creating a crystalline morphology or by adding of nano-fillers. The gain in diffusion barrier depends on the shape factor of obstacles, their concentration and orientation according to the main direction of transfer. In this PhD work, a novel direction to improve the barrier property has been studied; its principles have been early formalized independently from theoretical considerations on random walk on heterogeneous energy surfaces and from modeling of reactivity in heterogeneous catalysis. The central idea relies on increasing retention times instead of diffusion path lengths by incorporating nano-adsorbents (i.e. active obstacles) in the material. In this case, the considered material becomes a barrier specific to one or a family of solutes. This new concept has been tested on organic solutes to develop new barrier materials (e.g. biobased food packaging, materials for fuel tank…). The results brought out the engineering principles of such materials and experimental evidences to support the concepts. In particular, an extended free-volume theory has been developed to separate interactions with active surfaces (i.e. montmorillonites (MMT) in this work) from free-volume related effects in the polymer. Sorption properties of pristine MMT and organo-modified ones have been characterized experimentally and by molecular simulation to derive conditions where the partition coefficient Kcontrast between the surface of MMT and tested polymers (i.e. polycaprolactone (PCL), polyvinyl alcohol (PVA)) could be much greater than unity. PVA materials containing pristine MMT exhibited the most promising barrier properties to studied model solutes, which can be activated by decreasing temperature and whose selectivity can be controlled by varying the relative humidity. The blocking effects were in good agreement with the proposed description of “trapping” of organic solutes by intercalation in MMT galleries and on its enthalpic and entropic control.

No description available.

Poly(lactic acid) is biodegradable polymer derived from renewable resources and non-toxic, which has become most interested polymer to substitute petroleum-based polymer. However, it has low glass transition temperature and poor gas barrier properties to restrict the application on hot contents packaging and long-term food packaging. The objectives of this research are: (a) to reduce coagulation of graphene oxide/single-walled carbon nanotube (GOCNT) nanocomposite in poly(lactic acid) matrix and (b) to improve mechanical strength and oxygen barrier property, which extend the application of poly(lactic acid). Graphene oxide has been found to have relatively even dispersion in poly(lactic acid) matrix while its own coagulation has become significant draw back for properties of nanocomposite such as gas barrier, mechanical properties and thermo stability as well as crystallinity. Here, single-walled carbon nanotube was hybrid with graphene oxide to reduce irreversible coagulation by preventing van der Waals of graphene oxide. Mass ratio of graphene oxide and carbon nanotube was determined as 3:1 at presenting greatest performance of preventing coagulation. Four different weight percentage of GOCNT nanocomposite, which are 0.05, 0.2, 0.3 and 0.4 weight percent, were composited with poly(lactic acid) by solution blending method. FESEM morphology determined minor coagulation of GOCNT nanocomopsite for different weight percentage composites. Insignificant crystallinity change was observed in DSC and XRD data. At 0.4 weight percent, it prevented most of UV-B light but was least transparent. GOCNT nanocomposite weight percent was linearly related to ultimate tensile strength of nanocomposite film. The greatest ultimate tensile strength was found at 0.4 weight percent which is 175% stronger than neat poly(lactic acid) film. Oxygen barrier property was improved as GOCNT weight percent increased. 66.57% of oxygen transmission rate was reduced at 0.4 weight percent compared to neat poly(lactic acid). The enhanced oxygen barrier property was ascribed to the outstanding impermeability of hybrid structure GOCNT as well as the strong interfacial adhesion of GOCNT and poly(lactic acid) rather than change of crystallinity. Such a small amount of GOCNT nanocomposite improved mechanical strength and oxygen barrier property while there were no significant change of crystallinity and thermal behavior found. / Master of Science