This thesis investigates how to improve transparent flexible water vapour barriers by understanding how water permeates through them. The barriers consisted of a reactively sputtered aluminium oxide coating on an industrial-grade polypropylene substrate. Some also incorporated a di-acrylate smoothing layer. Key deposition conditions were studied and optimised for permeation and visible-light transparency: sputtering power, thickness & sequential deposition rate. One of the main deposition conditions corresponded to increasing coating nitrogen content in order to induce barrier-water interaction. The final investigation consisted of including acrylate layers in different barrier stacking combinations. It was found that thin, high sputter power coatings formed the best barriers to permeation. This was due to denser packing of the oxide and the inclusion of fewer macro-defects (large defects allowing unhindered permeation) and nano-defects (defects small enough to cause the permeant to interact with the coating). No clear benefit to permeation was found from the inclusion of nitrogen, but refractive index was seen to increase and the oxynitride coatings mechanically failed at a greater force than the oxides. This case illustrated the importance of considering the role of permeation through nano-defects: although a high activation energy was achieved for the nitrogen containing films, possibly suggesting greater interaction between the water vapour and the barrier, the amount of permeation was not reduced as the nitrogen gave rise to increased permeation due to nano-defects, thus changing the processing and chemistry can affect both the macro-defect and nano-defect permeation. Smoothing layers were found to reduce the permeation rate by covering large substrate features, thus allowing rough substrates to be used even for high barriers. Although a coating of acrylate on top of a barrier oxide showed no improvement, a 1-2-1-2 stack of smoothing layer (1) and oxide (2) was found to exhibit a large delay in the onset of permeation.

Increased understanding of plasma-polymer interactions is required to further the technological use of such processes, and elucidates heterogeneous physico-chemical reactions which occur under bombardment by complex combinations of energetic species. This thesis presents a systematic investigation into the effect of exposing organic and inorganic polymeric surfaces to controlled non-isothermal plasmas. Concurrently, a novel process is presented by which metal oxide gas barrier coatings are synthesized on polymer substrates by non- isothermal plasma treatment. Organic polymers exhibiting a range of structures were modified using non-isothermal plasmas at atmospheric and low pressure. The extent of atmospheric discharge oxygenation, measured by X-ray photoelectron spectroscopy (XPS), correlated with the polymers' ozonolysis rate constants. Surface physical disruption, studied using atomic force microscopy (AFM), after atmospheric discharge treatment was more pronounced than after low pressure plasma treatment. During low pressure oxygen plasma treatment, polymers containing phenyl groups were oxygenated to an extent which varied with the strength of π-π* valence band excitation in XPS C(1s) spectra of the untreated polymers, suggesting a dominance of reaction of plasma atomic oxygen at polymer radical sites excited by plasma vacuum ultraviolet radiation. The size of globules, observed by AFM, on the plasma modified surfaces correlated with the extent of surface chemical modification, inkeeping with a mechanism of chemically driven agglomeration of plasma oxidized low molecular weight polymer material. Oxygen plasma was more effective than water plasma in chemically modifying the surface of films of zirconium-normal-butoxide spin coated on polyester substrates, and the resulting optimized treatment produced a significant reduction in gas permeation of the substrate. XPS studies showed that oxygen plasma treatment of a polyphenylsilsesquioxane film on polyester film created a SiO(_2) layer less than 8 nm thin, which reduced O(_2) and Ar permeation of the coated film by 37.5 % and 31.6% respectively.

No description available.

As nanocomposites provide considerable improvements in material properties, scientists and engineers are focussing on biodegradable nanocomposites having superior material properties as well as degradability. This thesis has investigated the properties of biodegradable nanocomposites of the aliphatic thermoplastic polyester, poly (lactide acid) (PLA) and the synthetic biodegradable polyester, poly (butylene succinate) (PBS). To enhance the properties of this blend, nanometer-sized clay particles, have been added to produce tertiary nanocomposite. High aspect ratio and surface area of clay provide significant improvement in structural, mechanical, thermal and barrier properties in comparison to the base polymer. In this study, a series of PLA/PBS/layered silicate nanocomposites were produced by using a simple twin-screw extruder. PLA/PBS/Cloisite 30BX nanocomposites were prepared containing 1, 3, 5, 7 and 10 wt% of C30BX clay, while PLA and PBS polymers compositions were fixed at a ratio of 80 to 20. This study also included the validation of a gas barrier model for these biodegradable nanocomposites. WAXD indicated an exfoliated structure for nanocomposites having 1 and 3 wt% of clay, while predominantly development of intercalated structures was noticed for nanocomposites higher than 5 wt% of clay. However, TEM images confirmed a mixed morphology of intercalated and exfoliated structure for nanocomposite having 1 wt% of clay, while some clusters or agglomerated tactoids were detected for nanocomposites having more than 3 wt% of clay contents. The percolation threshold region for these nanocomposites lied between 3-5 wt% of clay loadings. Liquid-like behaviour of PLA/PBS blends gradually changed to solid-like behaviour with the increase in concentration of clay. Shear viscosity for the nanocomposites decreased as shear rate increased, exhibiting shear thinning non-Newtonian behaviour. Tensile strength and Young's modulus initially increased for nanocomposites of up to 3 wt% of clay but then decreased with the introduction of more clay. At high clay content (more than 3 wt%), clay particles tend to aggregate which causes microcracks at the interface of clay-polymer by lowering the polymer-clay interaction. Percentage elongation at break did not show any improvement with the addition of clay. PLA/PBS blends were considered as immiscible with each other as two separate glass transition and melting temperatures were observed in modulated differential scanning calorimetry (MDSC) thermograms. MDSC showed that crystallinity of the nanocomposites was not much affected by the addition of clay and hence some compatibilizer is required. Thermogravimetric analysis showed that the nanocomposite containing 3 wt% of clay demonstrated highest thermal stability compared to other nanocomposites. Decrease in thermal stability was noticed above 3 wt% clay; however the initial degradation temperature of nanocomposites with 5, 7 and 10 wt% of clay was higher than that of PLA/PBS blend alone. Gas barrier property measurements were undertaken to investigate the transmission of oxygen gas and water vapours. Oxygen barrier properties showed significant improvement with these nanocomposites, while that for water vapour modest improvement was observed. By comparing the relative permeabilities obtained from the experiments and the model, it was concluded that PLA/PBS/clay nanocomposites validated the Bharadwaj model for up to 3 wt% of clay concentration.

Greaseproof paper has a dense structure and therefore provides a natural barrier against materials like fat and oils. The barrier is obtained by extensive refining of the pulp. This refining is however a costly operation, not only in terms of direct costs for the refining but also in terms of indirect costs because the energy consumption for the drying of the paper is affected by the refining. A full-scale trial was performed to investigate the role of the pulp with respect to the energy demand and the barrier properties of the final papers. Paper made of 100% sulphite pulp with a low degree of refining exhibited the lowest energy consumption at a given level of air permeance. In addition, the effect of refining on the air permeance was compared with that of calendering. The calendering affected the air permeance less than the refining. The papers produced in the full-scale trial were later used as substrates for coatings and for detailed studies of the paper structure. Coating with chitosan was examined on a bench-scale and on a pilot scale. The studies showed that greaseproof paper can be upgraded with an oxygen barrier, but also that suitable coating techniques are lacking for the application of the coating in a sufficient amount. The influence of the base paper on the barrier properties of chitosan-coated paper was investigated in another study, in which it was found that greaseproof paper possesses a unique coating hold-out which cannot be met by other types of paper with a more open structure. It was also found that the coated paper had a lower oxygen permeability than the chitosan coating itself, and this indicates that the dense surface layer of greaseproof paper contributed to the oxygen permeability of the coated paper. The pore volume fraction of the greaseproof paper was found to be approximately 40% and it is therefore surprising that its air permeance is so low. To bring understanding to this question, the structure of greaseproof paper was studied using several methods. It was found that the structure was dominated by very small pores with a median diameter of <0.3 µm. The fraction of closed pores was also substantial. A porosity gradient was also found, indicating that the papers used in the study had a closed surface. The hypothesis that the surface layer of the paper contributed to the oxygen barrier was tested in an experiment in which greaseproof paper was extrusion-coated with polyethylene. The oxygen permeability was measured at 0%, 50% and 90% relative humidity, and the permeability was found to increase with increasing moisture content. Because only the cellulose layer in the paper and not the polyethylene layer in the coating is affected by moisture, this result supports the hypothesis that the surface layer of the paper contributed to the oxygen barrier properties of the coated paper.

Thin films with the ability to impart oxygen and other types of gas barrier are crucial to commercial packaging applications. Commodity polymers, such as polyethylene (PE), polycarbonate (PC) and polyethylene terephthalate (PET), have insufficient barrier for goods requiring long shelf life. Current gas barrier technologies like plasma-enhanced vapor deposition (PECVD) often create high barrier metal oxide films, which are prone to cracking when flexed. Bulk composites composed of polymer and impermeable nanoparticles show improved barrier, but particle aggregation limits their practical utility for applications requiring high barrier and transparency. Layer-by-layer (LbL) assemblies allow polymers and nanoparticles to be mixed with high particle loadings, creating super gas barrier thin films on substrates normally exhibiting high gas permeability. Branched polyethylenimine (PEI) and poly (acrylic acid) (PAA) were deposited using LbL to create gas barrier films with varying pH combinations. Film thickness and mass fraction of each component was controlled by their combined charge. With lower charge density (PEI at pH 10 and PAA at pH 4), PEI/PAA assemblies exhibit the best oxygen barrier relative to other pH combinations. An 8 BL PEI/PAA film, with a thickness of 451 nm, has an oxygen permeability lower than 4.8 x 10^-21 cm^3 * cm/cm^2 * s * Pa, which is comparable to a 100 nm SiOx nanocoating. Crosslinking these films with glutaraldehyde (GA), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (EDC) or heating forms covalent bonds between PEI and/or PAA. Oxygen transmission rates (OTR) of 8 BL films crosslinked with 0.1M GA or 0.01M EDC show the best oxygen barrier at 100% RH. Graphene oxide (GO) sheets and PEI were deposited via LbL with varying GO concentration. The resulting thin films have an average bilayer thickness from 4.3 to 5.0 nm and a GO mass fraction from 88 to 91wt%. Transmission electron microscopy and atomic force microscopy images reveal a highly-oriented nanobrick wall structure. A 10 BL PEI/GO film that is 91 nm thick, made with a 0.2 wt% GO suspension, exhibits an oxygen permeability of 2.5 x 10^-20 cm^3 * cm/cm^2 * s * Pa. Finally, the influence of deposition time on thin film assembly was examined by depositing montmorillonite (MMT) or laponite (LAP) clays paired with PEI. Film growth and microstructure suggests that smaller aspect ratio LAP clay is more dip-time dependent than MMT and larger aspect ratio MMT has better oxygen barrier. A 30 BL PEI/MMT film made with 10 second dips in PEI has the same undetectable OTR as a film with 5 minute dips (with dips in MMT held at 5 minutes in both cases), indicating LbL gas barrier can be made more quickly than initially thought. These high barrier recipes, with simple and efficient processing conditions, are good candidates for a variety of packaging applications.

<p>Cellulose nanocrystals (CNCs) and its composite coatings may impart many benefits in packaging, electronic, optical, etc. applications; however, large-scale coating production is a major engineering challenge. To fill this knowledge gap, a potential large-scale manufacturing technique, roll-to-roll reverse gravure processing, has been described in this work for the manufacture of CNC and CNC-poly(vinyl alcohol) (PVA) coatings on a flexible polymer substrate. Various processing parameters which control the coating structure and properties were examined. The most important parameters in controlling liquid transfers were gravure roll, gravure speed, substrate speed, and ink viscosity. After successful fabrication, coating adhesion was investigated with a crosshatch adhesion test. The surface roughness and morphology of the coating samples were characterized by atomic force microscopy and optical profilometer. The Hermans order parameter (S) and coating transparency were measured by UV–Vis spectroscopy. The effect of viscosity on CNC alignment was explained by the variation of shear rate, which was controlled by the micro-gravure rotation. Finally, the CNC alignment effect was investigated for gas barrier and thermal management applications.</p> <p>In packaging applications, cellulose nanomaterials may impart enhanced gas barrier performance due to their high crystallinity and polarity. In this work, low to superior gas barrier pristine nanocellulose films were produced using a shear-coating technique to obtain a range of anisotropic films. Induction of anisotropy in a nanocellulose film can control the overall free volume of the system which effectively controls the gas diffusion path and hence, controlled anisotropy results in tunable barrier properties. The highest anisotropy materials showed a maximum of 900-fold oxygen barrier improvement compared to the isotropic arrangement of nanocellulose film. The Bharadwaj model of nanocomposite permeability was modified for pure nanoparticles, and the CNC data were fitted with good agreement. Overall, the oxygen barrier performance of anisotropic nanocellulose films was 97 and 27 times better than traditional barrier materials such as biaxially oriented poly(ethylene terephthalate) (BoPET) and ethylene vinyl alcohol copolymer (EVOH), respectively, and thus could be utilized for oxygen-sensitive packaging applications. </p> The in-plane thermal conductivity of CNC - PVA composite films containing different PVA molecular weights, CNC loadings and varying order parameters (S) were investigated for potential application in thermal management of flexible electronics. Isotropic CNC - PVA bulk films with 10-50 wt% PVA solid loading showed significant improvement in thermal conductivity compared to either one component system (PVA or CNC). Furthermore, anisotropic composite films exhibited in-plane thermal conductivity as high as ~ 3.45 W m-1 K-1 in the chain direction, which is higher than most polymeric materials used as substrates for flexible electronics. Such an improvement can be attributed to the inclusion of PVA as well as to a high degree of CNC orientation. The theoretical model was used to study the effect of CNC arrangement (both isotropic and anisotropic configurations) and interfacial thermal resistance on the in-plane thermal conductivity of the CNC-PVA composite films. To demonstrate an application for flexible electronics, thermal images of a concentrated heat source on both neat PVA and CNC-PVA composite films were taken that showed the temperature of the resulting hot spot was lower for the composite films at the same power dissipation.

Le manuscrit porte sur l'élaboration de couches minces ayant des propriétés barrières aux liquides, aux gaz et aux ultra-violets. Pour réaliser nos différents systèmes, la technologie plasma à décharge à barrière diélectrique à la pression atmosphérique (DBD) a été utilisée. Dans la première partie, des films polymère plasma à base de 1H, 1H, 2H, 2H, Perfluorodecyl acrylate ont été développé. En fonction des paramètres plasma une surface dîtes superhydrophobe en une étape a été obtenue grâce à l'obtention d'un film composé de nanoparticules fluorés. La seconde partie des travaux a consisté à développer des films barrières aux gaz à partir de l'hexamethyldisiloxane. Ainsi, des films minces SiOx et multicouches SiOxHyCz/SiOx ont pu être obtenue afin d'améliorer les performances barrières de substrat PET et PEN. Enfin, l'obtention de film barrière aux UV a consisté à une croissance in-situ de nanoparticules de dioxyde de titane (TiO2) à partir du film polymère plasma. La matrice polymère constitué d'une structure siloxane et aminée plasma joue le rôle de nano-réacteur pour la croissance de cristaux de TiO2. / This works presents the development of plasma-polymrized surfaces for superhydrophobic, gas barrier and UV attenuation properties. These functional coatings have been deposited by means of atmospheric pressure dielectric barrier discharge (DBD). The first part deals on the plasma polymerization of the de 1H, 1H, 2H, 2H, Perfluorodecyl acrylate. According to the plasma parameters, surperhydrophobic coatings have obtained on several substrates. Morphologies analysis have shown the formation of fluorinate nanoparticles. The second part of the work was to develop gas barrier films from hexamethyldisiloxane. Thus, SiOx thin films and SiOxHyCz / SiOx multilayers have been obtained in order to improve the barrier performance of PET and PEN substrate. Finally, obtaining UV barrier film was to an in-situ growth of nanoparticles of titanium (TiO2) dioxide from the plasma polymer filin. The plasma polymer acts as a nano-reactor for the growth of TiO2 nanoparticles

Les panneaux d'isolation sous vide (PIV) sont constitués d'un matériau de coeur nanoporeux en dépression, et d'une enveloppe barrière aux gaz atmosphériques. Leur conductivité thermique initiale est de l'ordre de 5 mW/(m.K), cinq à huit fois inférieure à celle des isolants conventionnels. Au regard des isolants classiques, le questionnement le plus important concerne le couple performance / durabilité. La réponse passe par la compréhension et la modélisation des transferts thermiques et massiques dans les PIV. De nombreuses études expérimentales et numériques ont conduit à un modèle semi-empirique pour la conductivité thermique apparente d'un PIV, prenant en compte les différents modes de transfert dans le panneau. Ce modèle met en lumière le principal mécanisme de vieillissement : du fait de la perméation gazeuse à travers l'enveloppe, pression et humidité dans le panneau remontent au cours du temps, ce qui engendre une augmentation de la conductivité thermique. L'étude des transferts massiques à travers l'enveloppe est particulièrement délicate. Premièrement, la modélisation de la perméabilité des enveloppes utilisées (membranes multicouches de films polymères métallisés) repose sur la prise en compte des micro-défauts dans les couches métallisées, qui gouvernent le débit total de perméation. Deuxièmement, les valeurs des perméabilités à mesurer sont trop basses pour beaucoup de techniques conventionnelles. Troisièmement, une analyse de la littérature montre une lacune de taille en ce qui concerne la prise en compte de l'influence conjointe de la température et de l'humidité relative dans le modèle classique de perméation gazeuse. En se basant sur des données expérimentales existantes, le rôle de l'humidité relative sur les propriétés barrières des enveloppes des PIV est mis en lumière. L'existence d'un couplage entre les flux des différents gaz est posé comme hypothèse de départ à la mise en place d'un nouveau modèle de perméation gazeuse, prenant en compte pression partielle et pression totale, et donc la concentration molaire de chaque gaz dans le mélange. Les prédictions de ce modèle sont comparées à celles issues du modèle classique de perméation gazeuse, et les différences de comportement entre les deux modèles sont mises en avant. Deux séries de mesure de perméance sont ensuite mises en place, par vieillissement de PIV en enceintes climatiques et par mesure directe de perméance sur échantillons de membrane (méthode manométrique). Ces mesures sont menées à température et humidité relative fixées (T = 48 °C, φ = 65 % HR), mais avec une pression totale variant de 80 mbar à 1 bar. Cette campagne de mesure exploratoire ne montre pas d'influence notable de la pression totale sur la perméabilité à la vapeur d'eau. Ces résultats permettent de dresser les premières conclusions sur le rôle respectif de la pression partielle et de la pression totale, et de proposer une suite à la démarche expérimentale initiée dans cette étude. / Vacuum insulation panels (VIPs) are composed of an evacuated nanoporous core material, and a barrier envelope to atmospheric gases. Their apparent thermal conductivity after manufacturing is approximately 5 mW/(m.K), five to eight times lower than that of conventional insulation materials. Compared to conventional insulation materials, the most important issue remains in the duality performance / durability. The answer lies in the understanding and modeling of heat and mass transfer in VIPs. Many experimental and numerical studies about heat transfer led to a semi-empirical model for the apparent thermal conductivity of a VIP, taking into account the different transfer modes in the panel. This model highlights the main mechanism of VIPs aging: due to gas permeation through the envelope, pressure and humidity in the panel increase gradually over time, which causes an increase of the apparent thermal conductivity. The study of mass transfer through the gas barrier envelope is particularly difficult for three main reasons. First, the permeation modeling of VIPs envelopes (multilayer membranes with metalized polymer films) has to take into account micro-defects in the metallic layers, which play a key role in the total permeation rate. Second, the permeances to be measured are too low for many conventional methods, especially for dry air. Third, a literature analysis shows that the classical model for mass transfer through barrier envelopes does not take into account the combined influence of temperature and relative humidity, which is a great lacuna. From experimental data available in the literature, the role of relative humidity on the barrier properties of the VIPs envelopes is highlighted. The existence of a coupling phenomenon between the mass flows of the various gases is hypothesized to start the establishment of a new gas permeation model, which takes into account partial pressure and total pressure, and thus the molar concentration of each gas in the mixture. The predictions of this model are compared with predictions based on the classical model for gas permeation, and the differences between the two models are analyzed. Two experimental campaign are then implemented to measure envelope permeance, through whole VIPs aging in climatic boxes and through direct measurement of the permeance on membrane samples (manometric method). These measurements are carried out at fixed temperature and relative humidity (T = 48 °C, φ = 65 % HR), but with a total pressure ranging from 80 mbar to 1 bar. This exploratory measurement campaign shows no significant influence of the total pressure on the apparent permeability to water vapor. These results are used to draw first conclusions on the respective roles of the partial pressure and the total pressure, and suggest some outlooks to the experimental approach initiated in this study.

Ce travail concerne l'étude des modifications de nanocharges lamellaires synthétiques (α-ZrP) et de leur influence sur les propriétés mécaniques et barrière aux gaz de nanocomposites à matrice élastomère (SBR). Cette étude s'inscrit dans le cadre de l'amélioration de l'étanchéité des pneumatiques. L'une des originalités de ce travail a résidé dans l'introduction des nanocharges hydrophiles par le biais d'une dispersion aqueuse (slurry), dans la matrice SBR hydrophobe. La première phase de ce travail a consisté à entreprendre plusieurs types de modification des nanocharges afin d'étudier les mécanismes d'intercalation et/ou d'exfoliation des ces dernières dans le slurry. Ces différentes familles de charges modifiées ont été utilisées pour réaliser des nanocomposites selon différentes voies de mise en oeuvre : principalement solvant et latex. Nous avons ensuite étudié l'influence, (i) de la nature des intercalants, (ii) des distances interfoliaires initiales des nanocharges et (iii) des procédés de mise en oeuvre des nanocomposites, sur la morphologie et les propriétés finales des matériaux. Cette étude a montré la synergie de ces trois paramètres et mis en évidence l'importance du contrôle des interactions charges modifiées/matrice sur les propriétés de transport de gaz. Parmi l'ensemble des matériaux synthétisés, nous avons pu mettre en avant une formulation, permettant d'atteindre des propriétés mécaniques et barrière intéressantes. Cette formulation, en voie latex, est basée sur l'utilisation de la charge modifiée aminosilane et de l'agent de couplage Si69 / This work concerns the study of the modification of synthetic lamellar nanofillers (α-ZrP) and their influence on mechanical and gas barrier properties of elastomeric nanocomposites (SBR). This study is part of improving the tire tightness. One of the originalities of this work is the introduction of hydrophilic nanofillers through an aqueous dispersion (slurry) in the hydrophobic SBR matrix. The first step of this work was to undertake several types of nanofiller modifications state in order to study their intercalation/exfoliation mechanisms in a slurry. These different families of modified fillers were then used to make nanocomposites with different ways of implementations: mainly solvent and latex ones. The influence of, (i) the nature of the intercalating agent, (ii) the initial nanofiller interlayer distance and (iii) the nanocomposite implementation processes, on the morphology and final properties of materials were studied. The synergy of these three parameters was demonstrated and the importance of controlling the modified filler/matrix interactions on the gas transport and mechanical properties was also proved. Among all the synthesized materials, a formulation was put forward which allowed to achieve interesting mechanical and barrier properties. This formulation, processed by the latex route, is based on the use of aminosilane modified nanofillers and the Si69 coupling agent