This project investigates the moisture barrier properties of bio-based polymers and ways of improving them. The first section addresses the effect of crystallinity on the water permeability of poly(lactic acid) (PLA). The second section investigates PLA/talc composites and PLA/ montmorillonite nanocomposites. The third section is focused on a new polymer, polybutylene succinate (PBS), and its nanocomposites with montmorillonite. In the first section, the water vapour transmission rates (WVTR) through samples of polylactic acid of different crystallinities have been measured. Three different grades of commercial PLA were used with different ratios of L-lactide and D-lactide to give a range of crystallinities from 0 to 50%. Sheets of PLA were prepared by melt compounding followed by compression moulding and annealing at different temperatures and for different times to give the range of crystallinities required. Crystallinity was measured by differential scanning calorimetry (DSC) and the morphology of the samples was observed under crossed polars in a transmitted light microscope. Water vapour transmission rates through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased linearly with increasing crystallinity of the PLA from 0 to 50%. The results are discussed in terms of the effect of crystallinity on solubility and shown to fit the tortuous path model. The model was also successfully used to explain published data on water permeability of polyethylene terephthalate. In the second section, a series of PLA/talc composites and PLA/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The morphologies of the composites were investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was found that the fillers were well dispersed in the polymer matrix. The average aspect ratio of the compounded talc was found to be 8, and that of the nanoclay was found to be 50. Water vapour transmission rates (WVTR) through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased with increasing filler content and the results gave good agreement with predictions from the Nielsen tortuous path model. In the third section, PBS/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The melting and crystallisation behaviour of the pure PBS samples were investigated using differential scanning calorimetry (DSC) and cross polarised optical microscopy. A slight decrease of the degree of crystallinity was found in PBS containing 5% nanoclay. The morphology of the composites was investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was confirmed that that composite structures were intercalated. Water vapour transmission rates (WVTR) through the PBS sheets were measured using a MOCON Permatran-W®398. The measured values of WVTR decreased with increasing nanoclay content. However, the experimental values were all higher than the values predicted by the Nielsen tortuosity model. This result shows that in the case of PBS, which is a highly crystalline polymer, the nanoclay is not as well dispersed and is not as effective in reducing water vapour permeability as in the case of PLA.

Dans le contexte actuel d'une prise de conscience environnementale générale, concernant plus particulièrement la gestion des polymères en fin vie, la thèse se propose d'étudier la substitution d'une matrice non biodégradable (Polyéthylène) par une matrice biodégradable (Polybutylene Succinate) dans le cadre de la propriété singulière de thermorétraction mise à profit dans le secteur de l'emballage.Ce travail de thèse, cofinancé par un industriel du secteur de l'emballe et par l'Agence de l'Environnement et de la Maitrise de l'Energie (ADEME) a donc consisté à :- Mettre en évidence l'influence des branchements longs contenus dans certains polymères, ainsi que leurs mélanges avec des polymères linéaires sur le comportement rhéologique en cisaillement et en élongation,- Proposer une modélisation de la contrainte interne stockée lors de l'étape de mise en forme par extrusion de film à plat (extrusion dite « cast ») en vue de prédire la contrainte de thermorétraction,- Etablir le lien entre la structure des matériaux, ses conditions de mise en œuvre et la morphologie du film final afin d'établir une corrélation avec le taux de rétraction.Dans un premier temps, cette étude a été réalisée sur des matrices modèles de polyéthylènes et ensuite transposée à une matrice biodégradable de Polybutylène Succinate. / Due to environmental concerns growth including the management of the end of life of polymer wastes, the present work proposes to study the feasibility of a substitution of conventional non-biodegradable polyethylene by a biodegradable matrix of Polybutylene Succinate in order to produce heat shrinkable films with equivalent properties. This property is mostly used in the packaging industry to wrap product such as six packs bottles, cans or other food products together.This work half-financed by a packaging company based in France and by the French environment and energy management agency consisted on:- Highlight the impact of the macromolecular architectures of the polymers and their blends on the rheological behavior under shear and elongational flow,- Developing a modeling approach of the stress stored in the molten polymer during the cast film extrusion process in order to predict the shrinkage stress,- Correlate the structure of the materials with their processing conditions and the morphology(ies) of the final film in order to correlate them with the shrinkage rate.The first part of this work was dedicated to the understanding of the shrinkage mechanism and to develop an approach on polyethylenes matrices used as models and then to transpose this approach to a biodegradable matrices of Polybutylene Succinate and therefore conclude on the feasibility of the use of such a matrices for heat shrinkable films for packaging application.

Dans le but de développer des matériaux à partir d’une ressource renouvelable de moindre coût que l’amidon, des matériaux à base de farine de maïs ont été élaborés par extrusion-injection. La caractérisation des propriétés physico-chimiques de ces matériaux a révélé que le taux de glycérol (ajouté à la farine de maïs en tant que plastifiant) et le profil des zones de cisaillement employé lors de l’extrusion influencent significativement le taux de déstructuration de l’amidon et des protéines de la farine de maïs. Ceci a pu être établi en croisant notamment les résultats de l’analyse par diffraction aux rayons X, par spectroscopie infra-rouge à transformée de Fourier, de l’analyse calorimétrique différentielle à balayage à des observations par microscopie confocale à balayage laser des matériaux. De plus, le suivi des cinétiques d’hydrolyse en sucres réducteurs de l’amidon par des enzymes amylolytiques en présence et en absence d’enzymes protéolytiques a pu être relié à la déstructuration des protéines. Les matériaux obtenus présentent cependant des inconvénients rédhibitoires pour certaines applications comme l’hygroscopie élevée et le vieillissement rapide dans le temps. L’ajout de polybutylène succinate (PBS) au mélange farine-glycérol a cependant permis de conduire à une amélioration des propriétés mécaniques et à une réduction de l’hygroscopie de ces matériaux. Les observations de la morphologie de ces matériaux par microscopie électronique à balayage ont montré que la farine de maïs et le PBS sont incompatibles et présentent une morphologie qui varie selon le taux de PBS dans le mélange (30, 50 ou 70%). L’étude de la cinétique d’hydrolyse de l’amidon de la farine de maïs par des enzymes amylolytiques a permis de mettre en évidence l’influence de plusieurs facteurs : (i) la cristallinité de l’amidon, (ii) l’aire spécifique, (iii) la porosité et (iv) la morphologie des matériaux. De plus, l’évaluation de la biodégradation par voie microbienne en milieu liquide et solide par voie aérobie ou anaérobie a montré les mêmes tendances globales que les résultats obtenus par voie enzymatique. Ainsi, les matériaux élaborés à partir des formulations présentant des proportions de PBS excédant 50 % ne sont pas biodégradables au sens de la norme ISO 14855/1999 et sont également faiblement hydrolysés par les enzymes amylolytiques. / In order to develop materials from a cheaper renewable resource than starch, materials based on corn flour were prepared by extrusion and injection. The physicochemical characterization of these materials revealed that the glycerol content (used as plasticizer) and the profiles of shear zones used during extrusion significantly influence the destructuration intensity of starch and proteins of that composed corn flour. This could be established by combining the results of X-ray diffraction analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, and laser scanning confocal microscopy observations. In addition, the kinetics of the hydrolysis of starch into reducing sugars by amylolytic enzymes in the presence and absence of proteolytic enzymes significantly differed only when the initial structuration of proteins in corn flour was preserved. The materials obtained presented limitations for some applications namely due to their high hygroscopicity and rapid aging over time. The addition of polybutylene succinate (PBS) to flour-glycerol mixture improved mechanical properties and reduced hygroscopicity of the materials. The observation of these materials by scanning electron microscopy showed that corn flour and PBS are incompatible and have a morphology that varies according to the PBS content in the mixture (30, 50 or 70%). The study of the hydrolysis kinetics of starch corn flour by amylolytic enzymes contributed to highlight the influence of several parameters : (i) starch crystallinity, (ii) specific area, (iii) porosity, and (iv) material morphology. In addition, the evaluation of the microbial biodegradation in liquid and solid media aerobically or anaerobically showed the same overall trends as the results obtained by enzymatic hydrolysis. Thus, materials produced from formulations having PBS ratios exceeding 50% are not biodegradable according to the ISO 14855/1999 and are weakly hydrolyzed by amylolytic enzymes.

The master's thesis focuses on preparation of blown films from polylactid acid (PLA) which was blended with selected polyesteres – poly(butylene adipate-co-terephtalate) (PBAT), polycaprolactone (PCL) and polybutylene succinate (PBS) – and thermoplastic starch (TPS) in amount of 30% in order to soften PLA films. The influence of the aditives on static and mechanical tensile properties, on structure, morphology and thermal properties of the films was determined and the obtained parameters were compared to properties of films prepared from neat PLA and high density polyethylene (HDPE). The results showed that the additives increased crystalinity of PLA and thus significantly influenced the properties of the films. In contrast to the film from neat PLA, softening in terms of lowering glass transition temperature occured only by adding PBS and TPS, in terms of increasing ductility only by adding PBAT. All PLA films showed nearly constant elastic modulus up to the beginning of glass transition enabling their potential application till 50 °C. Preparation of the film with TPS was problematic and the film showed the worst mechanical properties. Preparation of other films was without any problems. The most promising additive from the tested ones was PBAT which showed comparable mechanical properties as the film from HDPE.