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Ionomers are valued for their exceptional physical properties, antimicrobial activity and superior adhesion to high surface energy solids and polymer blend components. Carboxylate, or sulfonate derivatives, of ethylene-rich thermoplastics are the most commercially available ionomers. Elastomeric ionomers bearing quaternary ammonium and phosphonium halide functionality have a literary standing in both scientific and patent-based publications. Currently cationic ionomers have shown great prominence in their inactivity to a wide range of bacteria and fungi. The specific focus of this research is in the derivatives of isobutylene-rich elastomers due to their exceptional impermeability, oxidative stability and vibration dampening characteristics. Imidazole-derived ionomers support a wider range of ionomer chemistry compared to ammonium and phosphonium analogues. N alkylation of nucleophiles including butyl imidazole, vinyl imidazole and 1,1’(1,4-butanediyl)bis(imidazole) by brominated poly(isobutylene-co-isoprene) yield thermally stable imidazolium bromide salts capable of supporting free radical cures and/or siliceous filler dispersions through further chemical modifications. The versatility of imidazole chemistry extends to the synthesis of isobutylene rich thermoset ionomers. This derives material properties from both a network of covalent crosslinks and a network of ion pair aggregates. Un-crosslinked elastomers are prone to creep and stress relaxation, hence a need for thermoset ionomer chemistry. Ion pairs are poorly solvated by the low dielectric constant of the polymer backbone and favoured thermodynamically by way of self assembly of the ionic functionality. The aggregation of ion pairs establishes a non covalent network of polymer chains whose dynamic mechanical properties approach those of conventional covalent thermosets comprised of carbon-carbon and/or sulfide crosslinks. However, the lability of this ionic network leads to a poor response to static loads leaving the thermoformable ionomers unqualified for engineering applications. A direct route is a more desirable method in preparing thermoset ionomers comprised of covalent crosslink networks and ionic functionality. In all, these reactive imidazolium ionomers look promising in supporting new value added applications for isobutylene rich derivatives, which include yet are not limited to elastomer thermosets, emulsions, filler composites and clay nanocomposites. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2013-12-11 15:34:32.691

The aim of this research was to investigate the potential use of recycled glass fibre composite materials as a replacement for virgin reinforcing materials in new thermoset composites. Specifically the closed-loop mechanical recycling of composites used heavily in the automotive sector known as dough and sheet moulding composites, DMC and SMC respectively, are investigated. The recycling of glass reinforced thermoset polymer composite materials has been an area of investigation for many years and composites used in the automotive industry are of particular interest due to legislative and social pressures on the industry. The mechanical recycling process and then collection of useful fibrous grades of recycled materials, recyclate, by a novel air separation technique were investigated first. The properties of these recyclate fibres were characterised and compared directly with the properties of virgin glass fibres they were to be used to replace. Single fibre tensile tests were employed to compare the strengths of the fibres and single fibre pull-out tests were used to investigate the strength of the interface between the fibres and a polyester matrix. These tests showed the recyclate fibres to be weaker and have a poorer interface with the polyester matrix than the virgin glass fibres. Understanding the properties of the recyclate materials meant their reformulation into new composites could be carefully considered for the production of new high performance materials. Two grades of the collected recyclate materials were then reformulated in to new DMC and SMC composites, replacing percentages of the virgin glass fibre reinforcement. The mechanical properties of the resulting manufactured composites were characterised throughout for direct comparison against one another and an unmodified control material, using both three-point flexural tests and Charpy impact tests. Through the modification of existing manufacturing techniques and the development of novel production equipment it has been possible to successfully manufacture both DMC and SMC composites with the recyclate materials used to replace virgin glass fibres. Virgin glass fibres have successfully been replaced by recyclate materials without disrupting standard production techniques and with minimal reduction of the mechanical properties of the resulting composites. As the loadings of recyclate materials used were greatly increased both the flexural and impact strengths were significantly degraded and it was found that chemical modification of the composite could be used to improve these formulations. It has been shown that the recyclate materials should be considered and treated as a distinct reinforcing ingredient, separately from the remaining virgin glass fibres.

RESUM Les reïnes epoxi constitueixen un dels polímers més emprats en el món de la industria, si bé presenten una sèrie d’inconvenients, els més importants dels quals són: la seva inherent fragilitat, la seva excessiva resistència tèrmica que en dificulta l’eliminació d’un substrat un cop finalitzada la seva vida útil i l’encongiment que experimenten durant el procés de curat. Per tal de reduir o eliminar aquests problemes aquesta tesi proposa l’ús de polímers hiperramificats així com polímers estrella i copolímers lineal-hiperramificat de bloc com a modificants químics de reïnes comercials. Amb aquesta estratègia s’han aconseguit millorar la tenacitat degut a efectes flexibilitzants o a separacions de fase del modificant en la matriu epoxídica, així com reduir l’encongiment en el curat o la degradabilitat de les reïnes, sense afectar altres propietats de la reïna com la seva Tg o la seva duresa. / ABSTRACT Epoxy resins are one of the most used polymers in the field of technological applications. However, they present some drawbacks being the most important the following: they are inherently brittle materials; they present excessive thermal resistance that limits their reworkability; and the shrinkage they experiment during curing. To overcome these problems this thesis proposes the use of hyperbranched polymers, as well as star polymers and lineal-hyperbranched block copolymers as chemical modifiers of commercially available epoxy resins. With this strategy tougher materials have been obtained due to either a flexibilizing effect or a phase separation of the modifier within the epoxy matrix. Moreover, the shrinkage on curing and the degradability of the thermosets have been improved without compromising other properties of the resin such as its Tg or its hardness.

Lactic acid based thermoset were synthesised by reacting lactic acid with glycerol andfunctionalizing lactic acid branches by methacrylic anhydride. Resins with different chainlength were prepared and their thermo mechanical properties were examined through DMAanalysis and their molecular structures were analyzed by NMR method and their viscositywere investigated through rheometry analysis and three monomers were selected as the bestchain length. Degree of reaction in different reaction times was evaluated by a modifiedtitration method and bulk preparation of resin was performed by optimal process condition.DSC analysis was conducted in order to evaluate curing behaviour of resin with benzoylperoxide as cross-linking initiator. TGA analysis was performed to check thermo stability ofthe resin. Bio composites by viscose unidirectional and bidirectional knitted fabrics and alsonon woven viscose fiber with different fiber loads were prepared by ordinary hand layupimpregnation followed by compress moulding and their mechanical and thermo mechanicalproperties were characterized by tensile, flexural, charpy and DMA analysis and optimumfiber loads were identified for each fiber type. Ageing properties of prepared composites wereexamined by placing samples in climate chamber to simulate long time ageing and ageingexperiment was followed by tensile and flexural test to evaluate mechanical properties afterageing simulation. Composite`s swelling properties for water and some other solvents wereinvestigated and also their chemical resistance were evaluated by immersing them in 1M HCland KOH. The resin was also compared with a commercial oil based thermoset by preparingglass fiber reinforced composites and also effect of adding styrene to the resin were evaluated.Results of this work demonstrated that the novel synthesised have very high mechanical andthermo mechanical properties surpassing commercial oil based poly esters but ageingbehaviour is not very good however adding styrene can improve ageing properties. Also theresin is compatible with cellulosic natural fibers and forms strong composites. / Program: Masterutbildning i energi- och material

Chancen und Möglichkeiten des Duroplast für MID-Anwendungen

This study describes the mechanical response of thermoset polymers under high compressive loads. The study is divided into two parts. The first part focuses on the behaviour of a powder coating when used in a clamping force joint and how the properties vary when the chemical and physical structure of the coating is changed. The second part discusses the fundamental understanding of the behaviour of thermoset polymers with small thickness-to-width ratio subjected to compressive stresses, the aim being to develop mathematical material models for viscoelastic materials under high compressive loads. In the first part polyester powder coatings were used with variations in molecular weight, number of functional groups of the resin, amount and type of filler and thickness of the coating. The coatings were subjected to conventional tests for coatings and polymers and also to specially designed tests developed to study the behaviour of powder coatings in clamping force joints. The high compressive loads in a clamping force joint put high demands on the relaxation and creep resistance of the coating and the study shows the importance of crosslink density, filler content, and also coating thickness in order to achieve the desired mechanical properties of a coating. A high reactivity of the resin, facilitating a high crosslink density and hence a high Tg, is the most important property of the coating. A film with high crosslink density shows increase in relaxation time and in apparent yield strength under compression, and also an increase in relaxation modulus and storage modulus in tension at temperatures above Tg. Addition of fillers reduces the deformation during compression and tension, but also induces a lower strain at break and hence a more brittle coating. The reinforcing effect of the fillers is pronounced when increasing the crosslink density of the coating, especially in the compression tests. The effect is evident in compression even at low amounts of fillers, where the relaxation time and resistance to deformation are strongly increased. The combination of high crosslink density and addition of fillers is therefore desirable since fillers then can be used moderately in order to achieve a reinforcing effect in compression while minimising embrittlement. The study also showed that increased coating thickness will give rise to defects in the coating, especially voids and blisters due to evaporation of water formed during the curing of the polyester powder coating. These defects will give rise to stress concentrations and increased plastic deformations in the coating, impairing the properties of the clamping force joint. The results from relaxation tests in tension were used to create a micromechanical model. This model was used in finite element modelling to estimate the loss of clamping force in a screw joint and to correlate with the experimental results of the powder coatings. In the second part of the study a well-defined free radically cured vinyl ester resin was used and studied in six different geometries in order to determine the dependence of apparent mechanical properties on the particular size and shape of a sample when it is subjected to high compressive loads. Variation of the specimen thickness, boundary conditions and loading conditions reveals that the geometry of the sample has a significant effect on the mechanical performance of the polymer. The apparent modulus and the yield strength increase dramatically when the thickness-to-width ratio of the sample is reduced, whereas they decrease when the friction between the sample and the compression plate is reduced. The creep strain rate decreases when the thickness of the material is reduced and it decreases even more when the amount of material surrounding the compressed part of the sample is increased. Creep and strain recovery tests on large specimens were used to develop a mathematical model including non-linear viscoelastic and viscoplastic response of a thermoset vinyl ester. The model was used in FEM calculations where the experimental results were compared with the calculated results in order to model the trends of the material response when varying the sample geometry. / QC 20100921

Dicyclopentadiene (DCPD), a tricyclic olefin, is available from the C5 fraction of petroleum feedstocks. Owing to its high reactivity (due to the presence of a strained alkene), low cost, and lack of other commercial uses, DCPD has been extensively pursued as a monomer for use in ring-opening metathesis polymerization processes. The olefin metathesis reaction, for which Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock received the 2005 Nobel prize, is among the most attractive approaches to polymerize olefins, allowing production of high-molecular weight polymers including linear macromolecules, block copolymers, and crosslinked materials. Polydicyclopentadiene (PDCPD), which can be produced using a variety of early- and late-transition metal catalysts, is a thermoset polymer with a highly crosslinked structure. PDCPD has excellent impact strength, high storage modulus, good chemical resistance, wide service temperature range, and low density. As a result, it has found broad commercial utility in industrial manufacturing. Additionally, the reaction injecting molding (RIM) process used for DCPD polymerization makes it possible to precisely control the shape and dimensions of PDCPD products. Owing to its lack of chemical functionality, however, polydicyclopentadiene has many limitations. Previously, our research group developed a modified dicyclopentadiene monomer by adding an electron withdrawing group – a methyl ester functional group – on the pendent cyclopentene ring of the monomer. Polymerization of this functionalized monomer led to a novel thermoset material – methyl ester functionalized polydicyclopentadiene (fPDCPD) – that exhibits tunable surface hydrophobicity. In experiments described in this dissertation, my collaborators and I confirmed the thermal crosslinking mechanism of fPDCPD using a combination of solution-state and solid-state NMR, FTIR, and Raman spectroscopy. We also explored the surface chemistry of our novel material, by harnessing the embedded functional group in order to exert finer control over hydrophobicity, and to control interactions with biological organisms through the conjugation of biologically relevant functional groups. To further extend the utility of our functionalized dicyclopentadiene monomer, we synthesized a series of statistical polymers: fPDCPD-stat-PDCPD. Once again, we used a wide range of characterization methods, and showed that we can both tune the surface hydrophobicity of the copolymers and manipulate the mechanical properties by adjusting the molar fractions of functionalized and non-functionalized monomers. Chemical structures of these copolymers were interrogated by NMR, FTIR, and Raman spectroscopy. Frontal ring-opening metathesis polymerization was applied in an effort to study the kinetics of (co)polymerization. Finally, to lay the groundwork for future fPDCPD manufacturing, we successfully optimized the production of fDCPD monomers to half-kilo scale and fPDCPD polymers at 20-gram scale, while developing a reaction-injection molding process that permitted the production of dimensionally controlled fPDCPD objects. This in turn allowed us to conduct a rigorous assessment of the mechanical properties of our fDCPD through dynamic mechanical analysis (DMA), which established for the first time that our functionalized material has a comparable storage modulus to that of the parent (unmodified) PDCPD. The development of fPDCPD is approaching a new stage where it is ready to be commercialized and mass produced. We hope that our novel fPDCPD material will soon play a crucial role in replacing traditional metallic components in vehicle design and engineering material manufacturing. / Graduate / 2021-12-14