An examination of the ordering process of block copolymer microstructure with respect to concentration was performed. Specifically, the process of solution casting block copolymer films was studied using small-angle X-ray scattering (SAXS). A method for determining the volume fraction of ordered phase in solution as the system dried was developed and used to analyze the solution casting process in several different block copolymer films in the neutral solvent toluene; these polymers include poly(styrene-b-butadiene), poly(styrene-b-isoprene-b-styrene), poly(styrene-b-butadiene-b-styrene), and several poly(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) polymers with different block fractions. A method was also developed for studying different drying rates of these films at a constant temperature. Temperature quenches of poly(styrene-b-isoprene-b-styrene) were performed to evaluate the effect of concentration on ordering rate. In all cases studied, an ordering layer was observed where self-assembly was thermodynamically favorable. This layer steadily grew until it reached the bottom substrate, resulting in a two-step ordering process. In the case of the styrene/diene copolymers, a constant polymer concentration was observed in the ordering layer as it grew to encompass the entire film. Kinetic entrapment was observed in the case of the diblock copolymer, as the system with a medium drying rate with respect to the other two experienced faster kinetics than the other two systems. For the two triblock copolymers, it was found that similar kinetics were observed with respect to the ordering layer concentration, largely due to skinning on the surface allowing time for lower sections of the film to order more completely. In the acrylate copolymers studied, the kinetics were not able to be evaluated with respect to drying rate. This was due to domain compression that cause a disordering of ordered microstructure as solvent was removed. This disordering was attributed to interfacial disruption caused by the compression in the film. In addition, a significant decrease in domain spacing was observed to occur in the vertical direction as a result of compression in that direction and pinning of the film to the substrate in the horizontal direction. Finally, the Avrami kinetic model was fit to several concentration of styrene/isoprene triblock copolymers as they ordered after a temperature quench. A U-shaped curve was observed in the system, as a result of competition between chain mobility effects and thermodynamic effects that occur as polymer concentration increases away from the CODT. It was found that the Avrami exponent remained constant over all concentrations, and an empirical model was fit to find the various rate constants at each polymer concentration. / Ph. D. / Block copolymers are polymers consisting of two or more separate regions made up of different types of polymer chains. Under favorable conditions, these chains will phase separate into ordered structures, with different components being made up of each block. Because they are attached to each other, these structures are in the size range of 10-100nm. For example, a phase separated styrene/butadiene block copolymer of a particular composition can form cylindrical structures where the cylinders are made up of polystyrene, and the surrounding matrix is made up of polybutadiene. These structures can greatly influence the properties of block copolymers, allowing them to be used for everything from lithography to fuel cell membranes. A common method for the production of block copolymer films for applications such as fuel cell membranes is solution casting, where a polymer in a solvent is spread on a surface and the solvent is allowed to dry. The rate of this drying is a parameter that is not often taken into account when designing a process, despite the fact that it can have an effect on the resulting structure. Thus, insight into how the ordering of structures in a film during film drying can be used to improve processing of these materials. Using a computer model to determine the concentration profile of solvent throughout the film, and combining this with x-ray scattering data taken during drying at different rates, it was determined that there was a layer in which ordering could proceed, or ordering layer, that steadily grew as the film dried. This ordering layer continued to grow until it encompassed the entire film. In the diblock (styrene/butadiene) copolymer that was studied, it was found that a medium drying rate produced the fastest ordering. This drying condition balanced the driving force for ordering created by the increased drying rate and the ability of the chains to arrange, which would have been reduced upon faster drying. This effect was not seen in the two triblock copolymers (styrene/butadiene/styrene and styrene/isoprene/styrene). In the triblock copolymers, the ordering rate only depended on bulk ordering layer concentration. This was attributed to the presence of a skin on the surface, which slowed ordering throughout the films. In the case of the acrylate triblocks that were studied, the ordering rate trend could not be determined, as compression in the film due to the removal of solvent caused ordered structures to disorder after they formed. Finally, a model was fit to the styrene/isoprene/styrene at different solvent concentrations. The different concentrations produced a U-shaped curve with respect to ordering time, resulting again from competition between driving force and the ability of the chains to rearrange.

No description available.

<p>Polysaccharides constitute an important source of raw materials for the packaging industry today. Polysaccharides have good natural barrier properties which are necessary for packaging films. Cellulose is the forerunner among renewable polymers for such applications. Hemicelluloses represent a new interesting breed of barrier materials. We have chosen to work with the hemicellulose O-acetyl-galactoglucomannan (AcGGM). The high water solubility of this particular hemicellulose extracted from process waters is both an advantage and a limiting factor. However, through the right modification, the water sensitivity of AcGGM can be regulated.</p><p>This thesis presents four ways to modify AcGGM: (i) benzylation, (ii) plasma surface treatment followed by styrene addition, (iii) vapor-phase (VP) surface grafting with styrene, and (iv) lamination of an unmodified film with a benzylated material. The most important methods of analysis of the films produced include contact angle measurement, dynamic mechanical analysis under moisture scan, and oxygen gas permeability measurement.</p><p>It was found that unmodified AcGGM films have low oxygen permeability at intermediate relative humidity (50 % RH) and good dynamic mechanical properties over a wider humidity range. Films of benzylated material (BnGGM) exhibited a decrease in oxygen permeability at lower humidity but showed better tolerance to higher humidities and indicated better dynamic mechanical behavior than AcGGM films. Lamination proved to be the most promising technique of modification, combining the good gas barrier properties of AcGGM films with the moisture-insensitivity of the BnGGM films.</p>

A new material for use as a proton exchange membrane in fuel cells has been developed: a blend of a perfluorocyclobutane-based block ionomer (S-PFCB) and Poly (vinylidene-co-hexafluoropropylene) (Kynar Flex, KF). This thesis details the work done thus far to characterize the morphology of this material, using small angle x-ray scattering, differential scanning calorimetry, atomic force micrscopy, and some other techniques to a lesser extent. Small angle x-ray scattering (SAXS) of pure S-PFCB showed a strong block copolymer- associated phase separation, on the order of 25 nm. Differential scanning Calorimetry (DSC) confirmed this finding. SAXS also revealed the presence of a peak representing individual ionic aggregates on the order of 3 nm. Finally, it was shown with DSC that no crystallinity develops in the S-PFCB block copolymer, while one of the blocks, known as 6F, crystallizes extensively. SAXS of incremental blend compositions of KF and S-PFCB revealed a steady increase in size of the block copolymer phase separation peak in SAXS, demonstrative of the miscibility of KF and the non-sulfonated 6F block of S-PFCB. Furthermore, this incremental study determined the scattering vector range relevant for comparing amounts of KF crystallinity. DSC of incremental blend compositions revealed two phases of KF crystallinity develops upon cooling a membrane, independent of cooling rate. Atomic force microscopy (AFM), small angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) corroborate to suggest a nonuniform morphology through the thickness of solution cast membranes. Also, the effect of different casting temperatures and after-casting anneals on morphology was assessed. Future work on this project involves morphological studies at various relative humidities and temperatures, as well as following up on discoveries already made. Finally, transmission electron micrscopy (TEM) should be performed to provide a visual analog, which will greatly help in developing an accurate morphological model. / Master of Science

No description available.

Chitosan, Whey Protein Isolate (WPI) and vital wheat gluten (WG) are three biomaterials that have quite promising properties for packaging purposes. They have good film forming properties and good gas barrier properties in dry conditions. Moreover, because they are produced from industrial waste of food processing, they offer an ecological advantage over polymers made from petroleum. However, their physicochemical characteristics still must be improved for them to be of commercial interest for the food packaging industry. The purpose of this work was to study different strategies aiming to improve the water resistance and aging properties of these polymers, which are some of the key disadvantages of these materials. The produced solution cast chitosan and WPI films were characterised with scanning electron microscopy (SEM), density measurements and thermogravimetry. The water vapour transmission rate was determined at a relative humidity of 11%. In the first part, mechanical properties of solid films and seals were assessed by tensile testing. WG film’s tensile properties and oxygen and water vapour permeabilities were measured as a function of aging time. The changes in the protein structure were determined by infrared spectroscopy and size-exclusion high-performance liquid chromatography and the film structure was revealed by optical and scanning electron microscopy. Gluten-clay nanocomposites were characterised by tensile testing, X-ray diffraction and transmission electron microscopy. The incorporation of a hydrophobic biodegradable polymer, poly ( ε-caprolactone), PCL, in both chitosan and whey protein, yielded a significant decrease in water vapour transmission rate. It was observed that a certain amount of the PCL particles were ellipsoidal in chitosan and fibrous in WPI. The obtained data also indicated that the particle shape had an important influence in the water vapour transmission rate. In the second part, the aging properties of WG films, plasticized with glycerol and cast from water/ethanol solutions with pH=4 or pH=11 were investigated. WG films made from alkaline solutions were mechanically more time-stable than the acidic ones, the latter being initially very ductile but turning brittle towards the end of the aging period. The protein solubility measurements indicated that the protein structure of the acidic films was initially significantly less aggregated than the in basic films. During aging the acidic films lost more mass than the basic films through slow evaporation of volatiles (water/ethanol) and through migration of glycerol to the paper support. The oxygen permeability was also lower for the basic films. In the last part, the properties of new and aged glycerol-plasticized WG films at acidic and basic conditions containing ≤4.5 wt% natural or quaternary-ammonium-salt-modified montmorillonite were studied. Films of WG with montmorillonite were possible to produce by solution casting. The aging rate of acidic and basic films was unaffected by the incorporation of clay. However, the large reduction in water vapour permeability for most systems suggested that the clay sheets were evenly distributed within the films. The film prepared from basic solution and containing natural clay was almost completely exfoliated as revealed by transmission electron microscopy and X-ray diffraction. The best water vapour barrier properties were obtained by using modified clay. / QC 20101013

Polysaccharides constitute an important source of raw materials for the packaging industry today. Polysaccharides have good natural barrier properties which are necessary for packaging films. Cellulose is the forerunner among renewable polymers for such applications. Hemicelluloses represent a new interesting breed of barrier materials. We have chosen to work with the hemicellulose O-acetyl-galactoglucomannan (AcGGM). The high water solubility of this particular hemicellulose extracted from process waters is both an advantage and a limiting factor. However, through the right modification, the water sensitivity of AcGGM can be regulated. This thesis presents four ways to modify AcGGM: (i) benzylation, (ii) plasma surface treatment followed by styrene addition, (iii) vapor-phase (VP) surface grafting with styrene, and (iv) lamination of an unmodified film with a benzylated material. The most important methods of analysis of the films produced include contact angle measurement, dynamic mechanical analysis under moisture scan, and oxygen gas permeability measurement. It was found that unmodified AcGGM films have low oxygen permeability at intermediate relative humidity (50 % RH) and good dynamic mechanical properties over a wider humidity range. Films of benzylated material (BnGGM) exhibited a decrease in oxygen permeability at lower humidity but showed better tolerance to higher humidities and indicated better dynamic mechanical behavior than AcGGM films. Lamination proved to be the most promising technique of modification, combining the good gas barrier properties of AcGGM films with the moisture-insensitivity of the BnGGM films. / QC 20101117

No description available.