Influence of the modification, induced by zirconia nanoparticles, on the structure and properties of polycarbonate

Melt compounding was used to prepare polycarbonate (PC)-zirconia nanocomposites with different amounts of zirconia. The effect of the zirconia loading, in the range of 1-5 wt.%, on the structure, mechanical properties and thermal degradation kinetics was investigated. The zirconia nanoparticle aggregates were well dispersed in the PC matrix and induced the appearance of a local lamellar order in the polycarbonate as inferred by SAXS findings. This order could be a consequence of the intermolecular interactions between zirconia and the polymer, in particular with the quaternary carbon bonded to the methyl groups and the methyl carbon as inferred from the NMR results. The presence of zirconia caused a decrease in the storage and loss moduli below the glass transition temperature. However, the highest amount of zirconia increased the modulus. The presence of zirconia in PC slightly increased the thermal stability, except for the highest zirconia content which showed a decrease. The activation energies of thermal degradation for the nanocomposites were significantly lower than that for pure PC at all degrees of conversion

Development of Dual-Cure Hybrid Polybenzoxazine Thermosets

Polybenzoxazines are potential high performance thermoset replacements for traditional phenolic resins that can undergo an autocatalytic, thermally initiated ring - opening polymerization, and possess superior processing advantages including excellent shelf-life stability, zero volatile loss and limited volumetric shrinkage. The simplistic monomer synthesis and availability of a wide variety of inexpensive starting materials allows enormous molecular design flexibility for accessing a wide range of tailorable material properties for targeted applications. Despite the fact, once fully cured, benzoxazines are difficult to handle due to their inherent brittleness, leaving a very little scope for any modifications. The motivation of this dissertation is directed towards addressing the common limitations of polybenzoxazines and to enable tailor made material properties for expanding the scope of future applications. In this work, a unique approach has been demonstrated incorporating a dually polymerizable bifunctional benzoxazine based monomer; designed to form a sequentially addressable intermediate B-staged network, followed by the formation of a final hybrid network via thermal curing of benzoxazines. This strategy offers a systematic route to study the formation of glassy polymeric materials in discrete, orthogonal steps, and a handle to access a broad range of material properties within the same system. The dissertation study is focused on manipulating the monomer design, to study different cure chemistries, in conjunction with benzoxazines. These cure chemistries included - rapid UV curable thiol-ene click chemistry, thermally curable ring-opening metathesis polymerization of norbornene, and free radical photo-polymerization of meth(acrylate) functionalities. A strong fundamental understanding of structure-property relationships with respect to network structure, kinetics, processing control and material properties of the hybrid networks was established

The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of polycarbonate

Polycarbonate/silica nanocomposites with different silica quantities were prepared by a melt compounding method. The effect of silica amount, in the range 1\u20135 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of polycarbonate (PC) was investigated. Clusters of silica nanoparticles were well dispersed in the polycarbonate whose structure remained amorphous. NMR results showed intermolecular interactions involving the carbonyl groups of different polymeric chains which did not affect the intramolecular rotational motions. The presence of the lowest silica content showed a decrease in the storage and loss moduli below the glass transition temperature, probably due to a plasticization effect. However, an increase in the amount of silica increased the moduli. The presence of silica in PC slightly increased the thermal stability, except for the highest silica content which showed a decrease. The activation energies of thermal degradation for the nanocomposites depended on the amount of silica and on the degree of conversion

Photoresponsive supramolecular polymer films : comparison of the hydrogen and ionic bonding strategies

Les complexes supramoléculaires dans lesquels un azobenzène photoactif est lié de manière non-covalente à un polymère représentent des alternatives simples, économiques et flexibles par rapport aux matériaux photosensibles traditionnels de type azopolymères à chaînes latérales. La photoisomérisation rapide et réversible des azobenzènes permet d'exercer un contrôle externe efficace des propriétés du matériau hôte et peut donner lieu à des déplacements moléculaires à grande échelle, tels que le transport de masse macroscopique photoinduit sous illumination par de la lumière polarisée. Les phénomènes induits par la lumière dans les azomatériaux offrent un grand potentiel dans divers domaines d’application allant de la photonique à la biologie. Les matériaux supramoléculaires photosensibles sont souvent basés sur des liaisons hydrogène mais l'utilisation des liaisons ioniques entre des composés de charges opposées est également une approche supramoléculaire intéressante pour concevoir des complexes azopolymères. Dans ce mémoire, les assemblages supramoléculaires du poly(4-vinylpyridine) (P4VP) photopassif et de son dérivé quaternisé (P4VPMe) sont liés par des liaisons hydrogène et ioniques à de petites molécules photoactives analogues, respectivement le 4-hydroxy-4’-diméthylamino- azobenzène (azoOH) et l'orange de méthyle (MO), qui présente un groupement sulfonate à la place de la fonction OH. Ces complexes photoactifs sont étudiés avec les objectifs suivants : 1. Comprendre l'effet du type d'interaction sur les propriétés photoinduites des azocomplexes, en particulier leur orientation moléculaire et l’efficacité de diffraction de leurs réseaux de relief de surface (SRG). 2. Déterminer le rôle de la masse molaire du polymère (5,2 kg/mol, 50 kg/mol et 200 kg/mol) sur la photosensibilité des azocomplexes. La complexation entre les composants est d'abord confirmée par spectroscopie infrarouge statique (IR) et RMN 1H. La spectroscopie UV-visible de film minces irradiés par un faisceau laser à 488 nm polarisé linéairement confirme l'absence de séparation de phases et révèle un pourcentage minimum d'isomères cis à l'état photostationnaire similaire pour les deux séries de complexes (respectivement 14% et 20 % pour azoOH et MO). La spectroscopie IR d'absorption structurale avec modulation de la polarisation (PM-IRSAS) est ensuite utilisée pour étudier l'impact du type d'interaction supramoléculaire et de la masse molaire du polymère sur l'orientation photoinduite des azocomplexes. Leurs mouvements macroscopiques photoinduits par un patron d'interférence de lumière polarisée circulairement à 488 nm sont également étudiés en mesurant in situ l'efficacité de diffraction lors de l'inscription de SRG. Nous avons trouvé que les complexes ioniques répondent à la lumière beaucoup plus fortement que les complexes analogues liés par liaisons H, à la fois en termes d'orientation et d'efficacité de diffraction. Les résultats de PM-IRSAS montrent également une contribution beaucoup plus grande de la redistribution angulaire sur la déplétion angulaire sélective (angular hole burning) pour les complexes de MO. Par contre, la masse molaire du polymère hôte n’a pas d’impact important sur la photo-orientation moléculaire, alors qu’elle a un effet substantiel sur l’efficacité de l’inscription des SRG, le complexe de faible masse molaire présentant une performance supérieure à celle des deux autres complexes. Nous concluons que l'enchevêtrement des chaînes joue un rôle plus important que la température de transition vitreuse pour le phototransport dans ces systèmes. Le mémoire fournit des connaissances fondamentales sur l'effet de la nature et de la force des interactions supramoléculaires sur la photosensibilité des azocomplexes, contribuant ainsi à améliorer la conception de polymères photosensibles supramoléculaires efficaces.Supramolecular non-covalently bonded azobenzene-containing complexes are easy-to-prepare alternatives to covalently bonded azopolymers as photoresponsive materials. The rapid and reversible nanoscale photoisomerization of azobenzenes enables effective external control of the host material's properties and they can give rise to large-scale motions, such as macroscopic mass transport with polarized illumination. The light-induced phenomena in azomaterials offer great potential in various areas ranging from photonics to biology. Photoresponsive supramolecular materials often hydrogen bond between a passive polymer and a photoactive small molecule. However, ionic bonding between oppositely-charged components is also a versatile supramolecular approach to design azobenzene-containing systems. In this M.Sc. thesis, supramolecular assemblies of photopassive poly(4-vinylpyridine) (P4VP) and its quaternized derivative (P4VPMe) are hydrogen-bonded (H-bonded) and ionically bonded (i-bonded), respectively, with analogous photoactive small molecules. The small molecules studied are 4-hydroxy-4-dimethylaminoazobenzene (azoOH) and methyl orange (MO), respectively, where the OH functionality of azoOH is replaced by a sulfonate group in MO. These photoactive complexes are studied with the following objectives: 1. To understand the effect of the bonding type on the photoinduced properties of azocomplexes, in particular their molecular orientation and their surface relief grating (SRG) diffraction efficiency (DE). 2. To determine the role of the polymer molecular weight (5.2, 50, and 200 kg/mol) on the photosensitivity of the azocomplexes. The complexation between components is first confirmed using static infrared (IR) spectroscopy and 1H NMR. UV-visible spectroscopy studies under illumination of linearly polarized 488-nm laser light of spin-coated thin films confirms the absence of phase separation in both series of complexes and reveals a similar minimum percentage of cis isomers (14% vs. 20% for azoOH and MO, respectively). Polarization modulation infrared structural absorbance spectroscopy (PM-IRSAS) is then used to investigate the impact of the supramolecular interaction type and the polymer molecular weight (MW) on the molecular-level photoinduced orientation () of the azocomplexes using linearly polarized 488-nm light. Then, their photoinduced macroscopic-scale motion that produces surface relief gratings (SRG) is investigated using an interference pattern of circularly polarized 488-nm light. We find that i-bonded complexes respond to light more strongly than their analogous H-bonded complexes, both in terms of and DE values. The PM-IRSAS results also show a much larger contribution of angular redistribution over angular hole burning for the MO-based complexes. In addition, the host polymer MW does not impact the molecular photo-orientation, while it does affect the SRG inscription efficiency. The low MW complex shows a higher DE than the two higher MW complexes. We can conclude that chain entanglement plays a more important role than the glass transition temperature for phototransport in these systems. The M.Sc. thesis provides fundamental knowledge of the effect of the supramolecular interaction type and strength on the photosensitivity of azocomplexes. This knowledge contributes to practical guidelines for the design of efficient supramolecular photoresponsive polymers

Surface and Interfacial Design and Control of High Performing Thermoplastics: Polysulfones and Beyond

The study of a class of materials almost always begins with the development of an understanding of properties in the bulk state. However, it is the study of surface critical phenomena that has led to a number of new important insights into polymer behavior. A systematic understanding of physical properties in the immediate vicinity of surface and interfacial layers, which cannot be deduced by simple extrapolation of bulk properties, is of significant importance for advancements in polymer applications where the interface drives performance, such as in membranes, coatings, drug-delivery systems, medical devices, and composites. First, the surface and interfacial modification and characterization of sulfone polymers will be described (Part I). Much of what exists in molecular modeling and experimental literature explains the behavior of flexible or modified chains. There is still a lack of accepted models that adequately explain chain conformation, structural organization, and dynamics of semi-rigid and rigid rod polymers at surfaces and interfaces. The purpose of this research was to investigate the environmental and structural parameters that determine polymer chain conformation, organization, and dynamics at the polymer-air interface for a series of semi-rigid and rigid rod sulfone polymers cast from solution. Refined models of polysulfones (and by extension semi-rigid/rigid rod polymers) behavior at surfaces and interfaces were developed through combined experimental and simulation analysis. The second section of this work (Part II) will discuss the nanophase manipulation of polyisobutylene (PIB) based thermoplastic elastomers (TPE’s) and polyhedral oligomeric silsesquioxane (POSS) nanocomposites. The phase behavior and permeability of (PS-PIB)2-s-PAA miktoarm star terpolymers with varying volume fractions of PAA was investigated for potential applications as permselective TPE’s. Results of this work present the potential for design of novel microstructures for specific applications through precise control of architecture, composition, and interaction parameters of the components. Lastly, the rheological properties and crystallization kinetics of POSS filled polyphenylenesulfide (PPS) and polyetheretherketone (PEEK) nanocomposites were studied. The findings indicate the potential for improvements in melt viscosity and crystallization of high temperature thermoplastics with tailored POSS/polymer interactions

Polyurethane-polymethyl methacrylate graft copolymers

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Natural Polymers and Biopolymers II

BioPolymers could be either natural polymers – polymer naturally occurring in Nature, such as cellulose or starch…, or biobased polymers that are artificially synthesized from natural resources. Since the late 1990s, the polymer industry has faced two serious problems: global warming and anticipation of limitation to the access to fossil resources. One solution consists in the use of sustainable resources instead of fossil-based resources. Hence, biomass feedstocks are a promising resource and biopolymers are one of the most dynamic polymer area. Additionally, biodegradability is a special functionality conferred to a material, bio-based or not. Very recently, facing the awareness of the volumes of plastic wastes, biodegradable polymers are gaining increasing attention from the market and industrial community. This special issue of Molecules deals with the current scientific and industrial challenges of Natural and Biobased Polymers, through the access of new biobased monomers, improved thermo-mechanical properties, and by substitution of harmful substances. This themed issue can be considered as collection of highlights within the field of Natural Polymers and Biobased Polymers which clearly demonstrate the increased interest in this field. We hope that this will inspire researchers to further develop this area and thus contribute to futures more sustainable society.

Synthesis and Physico-Chemical Investigation of some Thermosets and Their Composites

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Characterization and Tailoring the Properties of Hydrogels Using Spectroscopic Methods

Hydrogels represent heterogeneous systems that consist of a large amount of water retained by a three-dimensional network. The hydrogel network is the result of assembly through physical interactions or chemical cross-linking of polymers or small molecules. The applications of hydrogels (water purification, tissue regeneration, therapeutic delivery, bio-detection or bio-imaging, etc.) depend on their physicochemical properties and structural features. Although electron microscopy and viscoelastic measurements provide general information about a gel material, the spectroscopic methods complement these methods and also afford a deep insight into the gel structure. In this chapter, the applications of several spectroscopic methods for characterizing polymeric or supramolecular hydrogels are discussed. Thus, this review highlights the particular application of vibrational spectroscopy, circular dichroism, fluorescence (these providing information on assembly in the network), interactions that occur between network and solvent (water), pulsed-field gradient NMR (determination of mesh size) and EPR spectroscopy (a method that can provide extensive information regarding the assembly process, diffusion and release)