This thesis addresses the systematic modification of poly(tetramethylene oxide) (PTMO), polyether based segmented thermoplastic polyurethane with a secondary aminoalkyl functional polydimethylsiloxane (PDMS), which was intended to improve the fire resistance of polyurethane systems. The PDMS oligomer was successfully incorporated into the polyurethane backbone via one step solution polymerization. The effect of PDMS content on thermal stability, morphology, surface composition, mechanical properties, and fire resistance of polyurethane was investigated. These polymers displayed a complex two phase morphology and composition-dependant mechanical properties. The PDMS segment microphase separated from other polyurethane segments and varying microphase separation morphologies were observed with differing PDMS content. Spherical dispersed complex phases and co-continuous phases occurred when the PDMS content was 15wt% and 55wt%, respectively. Similar thermal stability was observed for both the polyurethane control and the PDMS modified polyurethanes, but the later displayed increased char yield in air with increased PDMS concentration. Quantitative measurements of the fire resistance of the modified polyurethanes by cone calorimetry showed that the peak heat release rate of the 15wt% siloxane modified samples dropped 67wt%, compared with the polyurethane control. However, the peak heat release rate did not further change with increasing siloxane content. Excellent mechanical properties, in terms of tensile strength and elongation, were found for the modified polyurethane with 15wt% of PDMS. Higher PDMS levels did reduce tensile strength, probably because of the reduction in strain crystallizing PTMO content. The PDMS modification, which resulted in improved fire resistance and excellent mechanical properties, is attributed to the low surface energy of the PDMS segment that tended to migrate to the surface of the polymer. It could be oxidized into a partially silicate-like material upon heating in air. In addition, the syntheses of primary and secondary aminoalkyl functional PDMS based segmented polyureas are described herein. Two-phase morphology was observed for all the polyurea samples, even when the hard segment concentration was as low as 6wt%. All these polyureas formed clear transparent films that exhibited good mechanical properties even with very high PDMS content, up to 94wt%. They also demonstrated similar thermal stability, independent of the PDMS end group. However, the nature of the end group, i.e. primary or secondary aminoalkyl, had a dramatic effect on mechanical and morphological properties of these PDMS based polyureas, which was interpreted in terms of the level of hydrogen bonding. / Ph. D.

Clinical studies suggest radiation dose and dose rate cause increased failure of medical implants however, little evidence supports this claim and due to the complexity of an in vivo environment, separating variable implants is difficult. Before beginning to understand material changes in vivo, a systematic study of silicone and polyurethane exposed to radiation is needed to verify whether radiation is a major variable contributing to material changes. This research fills a gap within the current literature by investigating low dose therapeutic radiation and varying dose rates at sterilization dose and answers questions on whether radiation in an aqueous environment alone is enough to significantly alter material properties. This is the first research to apply a water environment to therapeutic doses and the first to investigate a range of dose rates for clinical applications. Biomedical grade silicone and polyurethane films will be exposed to both types of radiation in an aqueous environment separately and analyzed for changes. The limited current literature combined with standards for biomedical devices will be used to characterize changes seen in materials. The first strategy used to explore the compliance of biomedical grade polymers employs low doses of therapeutic radiation ranging between 0 Gy and 80 Gy. Analysis of these low doses results in confirming cellular, mechanical and chemical stability of silicone and polyurethane. The second strategy used to investigate silicone and polyurethane exposed materials to 25 kGy (sterilization dose) of gamma irradiation at varying dose rates (3.2 - 833 Gy/min). Results from these studies conclude that varying the dose rate causes slight changes in both materials but not significant enough to alter bulk material properties. In conclusion, the results from this research reveal that both silicone and polyurethane maintain their stability at low doses and varying dose rates of irradiation while in an aqueous environment. This indicates that increased failure rates seen in silicone and polyurethane materials in vivo when exposed to radiation cannot be contributed to radiation alone. With the highly complex environment medical devices are exposed to in vivo, each variable that may contribute to failure should be investigated individually before combining to fully understand the mechanisms of material failure. This study indicates that the environment may play a larger role in material change and there is a need for updates to medical device standards. / PHD / Clinical studies suggest radiation dose and dose rate cause increased failure of medical implants however, little evidence supports this claim and due to the complexity of a human environment, separating factors contributing to failure is difficult. Before beginning to understand material changes, a study of silicone and polyurethane exposed to radiation is needed to verify whether radiation is a major variable contributing to material changes. The results from this research reveal that both silicone and polyurethane maintain their stability at low doses and varying dose rates of irradiation while in water environment. This indicates that increased failure rates seen in silicone and polyurethane materials in clinical settings when exposed to radiation cannot be contributed to radiation alone. With the highly complex environment medical devices are exposed, each factor that may contribute to failure should be investigated individually before combining to fully understand the mechanisms of material failure. This study indicates that the environment may play a larger role in material change and there is a need for updates to medical device standards.

Réalisé dans le cadrr du pôle de compétitivité Véhicule du Futur » de la région ,11k.c Franche Comté_ cc uas_ul de thèse porta sur la hmblcmatsque du remplacement des étoffes complexes textiles utilisées dans les applications d'habillage intérieur automobile. La législation sur les véhicules hors d'usage impose des produits automobiles a 1 $ "), rccyclablcs et t 95' réutilisables dl ici janvier 2015. Alin de rebondie u la problématique posée ainsi qua la législation Europécnnc, des industriels et des acteurs de la recherche de la regain mulhousienne ont lias aillé ensemble dans le cadre du poilez VERTILAP" sur le développement d'un nouveau textile non-tissé 3D. Ce travail de thèse a eu pour objectif de développer le proucde de ! abris ation de ces nouveaux matériaux ainsi que les produits non-tisses 3D obtenus. La démarche de développements procédé produits a consisté Ii faire évoluer le prototype expérimental VERTILAP' au travers de la caractérisation physique et mécanique en compression des produits obtenus. Des méthodes ci dcsj outils de caractérisations adaptés a ces nouveaux produits ont etc mis au point. L'analyse de résultats obtenus s'est appuyée sur les outils statistiques i abn de valider ces résultats. Une étude comparative avec les produits contenant de la mousse polyuréthane (PU) a permis de montrer que ces nouveaux non-tissés 3D pouvaient être utilisés en remplacement des mousses PU. La réalisation de prototypes pour des applications d'habitacle autinnobilu a été faite et a prouvé la faisabilité industrielle d'un tel remplacement. Les résultats de ce travail ont été utilisés pour [élaboration du cahier des charges d'ur prototype semi industriel VERTILAP". / The question of the recycling of the laminated textile fabrics especially in the automotive indusuy represents one of the main requests and challenge of the car manufactures and the OEM's sine 2000. indced, it is nowadays impérative l'or car industry to promote ecological methods of developinent in regard to new consumer sensibility. Rcgarding the Europcan directives 2000 CE53, the automotive products should be at 85% recyclable and at 95% reusable by January 2015. In order to answer this issue, sonie textile industrialists and researchers are working together, through the VERTILAP projet to develop a new material as a 3D nonwoven which will be used to substitute polyuréthane (PU) foam. This work aims to develop the VERTILAP experimental prototype through the physical and mechanical characterizations in compression of thosc new 3D nonwovens. Methods and tools have been canied out to reach Chat goal. Statistical analyses have been used to validate the obtained experimental data. A comparative study between the VERTILAP" products, issued from the VERTILAP" process, and the automotive PU foams bas shows that the new 3D nonwovens can be used to substitute the PU foams. VERTILAP" experimental prototypes such as headrest upholstery and door panel have been developed and have proved the feasibility of the foam exchange. The already obtained results of this work have been taking alto accourt in the spécifications of the new VERTILAP" serai industrial prototype.

Facile monomer synthesis provided routes towards novel step-growth polymers for emerging applications. Adjustment of reaction conditions enabled green synthetic strategies, and promising scalability studies offered impetus for industrial funding. Engineering thermoplastics, such as linear polyetherimides (PEIs), had carefully targeted molecular weights for analysis of the effect of molecular weight and regiochemistry on the thermomechanical and rheological properties of PEIs. The design of linear, high performance PEIs comprising 3,3'- and 4,4'-bisphenol-A dianhydride (bis-DA) and m-phenylene diamine (mPD) provided an opportunity to elucidate the influence of dianhydride regiochemistry on thermomechanical and rheological properties. This unique pair of regioisomers allowed the tuning of the thermal and rheological properties for high glass transition temperature polyimides for engineering applications. The selection of the dianhydride regioisomer influenced the weight loss profile, entanglement molecular weight, glass transition temperature (Tg), tensile strain-at-break, zero-shear melt viscosity, average hole-size free volume, and the plateau modulus prior to viscous flow during dynamic mechanical analysis (DMA). The 3,3'-PEI composition interestingly exhibited a ~20 °C higher Tg than the corresponding 4,4'-PEI analog. Moreover, melt rheological analysis revealed a two-fold increase in Me for 3,3'-PEI, which pointed to the origin of the differences in mechanical and rheological properties as a function of PEI backbone geometry. The frequently studied 4,4'-PEI exhibited exceptional thermal, mechanical, and rheological properties, yet the 3,3'-PEI regioisomer lacked significant study in the industrial and academic sectors due to its 'inferior' properties, namely poor mechanical properties. Introduction of long-chain branching (LCB) into PEIs provided a unique comparison between a commercially relevant PEI (Ultem® 1000) and a regioisomer infrequently found in the literature. Thermal stability remained consistent for each regioisomer, and Tgs for the 3,3'- and 4,4'-LCB-PEIs agreed well with prior literature. Rheological analysis demonstrated typical shear thinning and low-shear viscosity trends for LCB systems. The targeted molecular weights for the 3,3'-LCB-PEIs were well below the Me cutoff for "high molecular weight," and for this reason the rheological properties demonstrated inconsistent trends. Further study of PEIs led to the incorporation of ionic endgroups. These provided physical crosslinks, which enhanced mechanical and rheological properties of branched PEIs compared to their non-ionic analogs. The Tgs decreased with an increase in branching concentration for the phenyl-terminated PEI, while it remained unchanged for the ionically-endcapped PEIs. The divalent salts demonstrated higher mechanical strength and melt viscosities compared to the monovalent salt and the non-ionic PEIs. Interestingly, the zinc-endcapped PEI series exhibited decreased high-shear viscosities compared to the other PEIs, lending to promising industrial applications for the zinc-endcapped branched and linear PEIs for high temperature applications. Additional engineering thermoplastics in the form of bio-based polyureas exhibited mechanical properties similar to those of non-bio-based polyureas. The isocyanate-free synthetic route incorporated an essential urea degradation mechanism at elevated temperatures to produce isocyanic acid, which then reacted with amines to produce linear polyurea thermoplastics. Urea provided a sustainable and bio-friendly reagent for high molecular weight, isocyanate-free polyureas. Poly(propylene glycol) triamine enabled the long-chain branching of thermoplastic polyureas. Differential scanning calorimetry (DSC) showed no change in Tg for the series; however, melting peaks decreased in intensity as the branching concentration increased, indicating a reduction in crystallinity. Tensile testing eluded to a decrease in ultimate stress values for higher branching concentrations, while melt rheology showed significant differences in melt viscosities. Viscosities increased markedly with an increase in branching concentration, signifying greater entanglement and stronger physical crosslinks for the branched polyureas. Further analysis of possible isocyanate-free routes led to the use of 1,1'-carbonyldiimidazole (CDI) to generate polyureas and polyurethanes. CDI, known in the literature for its use in amidation and functionalization reactions, enabled the production of well-defined and stable polyurethane monomers. The functionalization of butanediol with CDI yielded an electrophilic biscarbamate monomer, bis-carbonylimidazolide (BCI), suitable for further step-growth polymerization in the presence of amines. The reaction of this novel monomer with aliphatic diamines produced thermoplastic polyurethanes with high thermal stability, tunable glass transition temperatures based on incorporation of flexible polyether segments, and creasable thin films. It is envisioned that CDI functionalized diols will afford access to various polymeric backbones without the use of toxic isocyanate-containing strategies. Additionally, non-isocyanate polyurethane (NIPU) foams were produced from BCI monomers without the need of blowing agents, catalysts, or solvents. These materials offered an alternative to existing foaming technology, which typically employed isocyanates. Polyurethanes were foamed through a CO2 thermal decomposition mechanism involving the BCI monomers. We investigated two series of polyurethane foams with a tunable Tg range from ~0 °C to ~110 °C. We found that the incorporation of aromatic amines vastly altered the foam thermomechanical properties, and the resulting foams were closed-cell in nature. / Doctor of Philosophy / Step-growth polymers play a significant role in commercial and industrial applications. On-going work in this field focuses on sustainability, biodegradability, and improved processability. This dissertation encompasses the improvement and innovation of current and novel engineering thermoplastics and foams. The careful purification and step-growth synthetic strategies herein, afforded targeted molecular weights for analysis of linear and long-chain branched (LCB) polyetherimides (PEIs). Further analysis of LCB-PEIs, with monovalent and divalent ionic endgroups, provided an opportunity to study the effect of ionic interactions and physical crosslinks at high temperatures (>300 °C). The long branches improved the melt processability compared to linear analogues at equivalent molecular weights. The challenge to investigate polyurethanes using non-isocyanate methodologies offered an opportunity to apply fundamental small-molecule, organic synthesis to macromolecular science. 1,1'-Carbonyldiimidazole (CDI) provided a platform to generate polymeric chains from industrially relevant monomers. Additional testing serendipitously discovered the generation of CO2 upon thermal degradation of the novel monomers. Harnessing the release of CO2, during the gelation of polyurethanes, provided an isocyanate-, catalyst-, and solvent-free synthetic route towards polyurethane foams that boasts scalability and industrial relevance.

Die Arbeit beschreibt die Synthese und Charakterisierung von amphiphilen Polyurethanen mit Emulgatoreigenschaften für die Polymerisation hydrophober Monomere in wässriger Phase. Der Emulgator wurde mit kolloid- und polymerchemischen Methoden hinsichtlich seiner grenzflächenaktiven Eigenschaften sowie einer Strukturbildung in wässriger Phase charakterisiert. Die Emulsionspolymerisation mit dem polymeren PU-Emulgator am Beispiel von Styrol ist untersucht worden. Dabei sind die Partikelgrössen und deren Verteilung in Abhängigkeit von Reaktionsparametern mittels Photonen-Korrelations-Spektroskopie und durch Fluss-Feldfluss-Fraktionierung (F-FFF) bestimmt worden. Weiterhin wurde mittels Dilatometrie und Reaktionskalometrie die Polymerisationskinetik untersucht. Die Partikelmorphologie konnte durch Festkörper-NMR modelliert werden. Durch Atomic Force Microscopy (AFM) im Tapping mode konnte die Oberfläche und die Phasenseparation der polymeren Phasen charakterisiert werden. / This paper describes the synthesis of a reactive amphiphilic polyurethane, and its use as an emulsifier for the emulsion polymerization of styrene. The colloid properties and the structure of the emulsifier in the aqueous phase have been investigated. When the acrylic polymerization is carried out with hydrophobic monomers, we obtain a composite particle structure. The variation of particle size and particle size distribution as a function of the reaction parameters was measured by light scattering methods and Flow-fieldflow-fractionation (F-FFF) . Through investigation by dilatometry and reaction calorimetry it was possible to compare the polymerization process with that of common emulsion polymerization. Solid State NMR analysis allowed us to develop a core-shell model for the composite particle structure, and to determine the presence of an interphase layer between core and shell. Atomic Force Microscopy (AFM) methods were used to characterize the surface of the films, and tapping mode AFM was used to characterize the polymer phase separation on the micro scale.

The temperature profile needed to complete the reaction between the sodium-diamine complex and the isocyanate terminated prepolymer has been established. The sodium diamine complex has the advantage of blocking the nearly instantaneous reaction between the diamine and isocyanate from taking place until it is released at elevated temperatures. Because of its low melting temperature (~40 °C) and its low molecular weight (low viscosity), this chain extension reaction is not dependent on the participation of the prepolymer. Instead, the rate of reaction is dependent on the dissolution of the 4,4’-methylenedianiline (MDA) complex into the system. The dissolution of the MDA complex has been demonstrated to be strongly dependent on particle size. Both the plasticizer Bis(2-ethylhexyl) adipate and the quaternary ammonium compound found in soy lecithin play crucial roles for this reaction. The quaternary ammonium compound is crucial in the dissolution of the complexes. Although the plasticizer has been shown to dissolve the complex to a small extent, the principal role of the plasticizer is to disperse the complexes and to prevent their agglomeration. Other additives such as Dimethyl Sulfoxide (DMSO) have demonstrated to be highly efficient in dissolving the complex. However its effectiveness limits the mixing window needed before reaction take place, resulting in a disadvantage.

Cellulose nanocrystals (CNCs) are crystalline nanoparticles that are extracted from renewable sources such as trees or bacteria through mechanical or chemical treatments of their source. CNCs are of interest to several research communities concerned with sustainable technologies. Specifically, CNCs have attracted great interest in the polymer composite community given their high theoretical specific strength and modulus. Two key obstacles surround the use of CNCs in polymer composites, namely their comparatively lower thermal stability and hydrophilicity render their dispersion, and therefore mechanical reinforcement, in polymer matrices challenging. This research considered a waterborne epoxy and a polyurethane elastomer for CNC/polymer composites since these composites are seldom reported in literature or often suffer from degraded mechanical properties. In the epoxy/CNC composites, samples were prepared by two methods, first an epoxy emulsion was mixed with an amine crosslinker and an aqueous based CNC suspension (1-step mixing), and second, the epoxy emulsion was premixed with the aqueous based CNCs and the amine crosslinker was added some time later (2-step mixing). Both composites were mixed by magnetic stirring, however the samples prepared by the 2-step mixing method exhibited enhanced dispersion and mechanical properties, specifically the storage modulus (E’), tensile strength, and work of fracture. Zeta potential measurements and chemical analysis by FTIR indicated that the dispersion mechanism was physical in nature, rather than chemical. In the second composite system, CNCs were chemically modified with an isophorone diisocyanate (IPDI) monomer having unequally reactive isocyanate groups. The goal of the modification step was to react only one isocyanate group with the CNC surface and have a free isocyanate group available for further modification. The chemical structure of one linked isocyanate (urethane bond) and one free isocyanate was confirmed by FTIR and 13C NMR. The particles modified by IPDI (m-CNC) and the neat particles (um-CNC) were incorporated into a polyurethane matrix based on IPDI and a triol crosslinker. Upon visual inspection of the cured composites, it was clear that the modification step produced homogeneously dispersed nanoparticles in the polyurethane while the um-CNCs were aggregated. When the mechanical properties were tested by uniaxial tensile testing, it was determined that the m-CNC composites resulted in improvements in the tensile strength and work of fracture without degradation of the elongation of break property when compared to the neat matrix. Overall the findings in this research highlight important considerations for designing CNC/thermoset composites with enhanced dispersion and mechanical performance.

Construction projects involving the installation or repair of subsurface structures or utilities often require dewatering to induce a temporary lowering of the local groundwater elevation to facilitate construction. In the event that a known contaminant plume is present in an adjacent area, this dewatering may inadvertently draw the contaminant into the previously uncontaminated work area. Uretek Holdings, Inc. has developed its Injectable BarrierSM to be installed prior to dewatering exercises to provide a groundwater cut-off by reducing the potential movement of groundwater due to the hydraulic gradient induced by dewatering. A benefit of Injectable BarrierSM as compared to conventional methods of hydraulic control is that excavation is not required prior to its installation and no excess soils are generated through its installation. Injectable BarrierSM is a proprietary process registered with the United States Patent and Trademark Office by Uretek Holdings, Inc. Since methodical in-situ testing of the effectiveness of the Injectable BarrierSM has not been performed to date, it was the focus of this research to test the performance of the barrier under in-situ conditions utilizing a subsurface environment indicative of a West-Central Florida location. A testing plot to perform this research was selected on Hillsborough County property in Tampa, Florida which provided both a relatively shallow groundwater elevation in addition to a clay confining layer at a relatively shallow depth, making this an ideal location for testing the performance of the Injectable BarrierSM. After establishing the native conditions through baseline pump testing and repeating the testing procedure following the installation of the Injectable BarrierSM, a quantification of the reduction in hydraulic conductivity was achieved. Pumping tests were performed on the Injectable BarrierSM at its standard spacing as well as modified versions of the barrier with variation in the lateral spacing to include 6 foot, 4 foot, 3 foot, and 2 foot injection patterns to determine if a modified injection process could improve its performance. The 3 foot lateral spacing corresponding to the standard Injectable BarrierSM process indicated a 20% reduction in the hydraulic conductivity following its installation. By performing a small scale excavation following the completion of all pumping tests, it was discovered that the dispersion of the material in the subsurface appeared insufficient to provide the coverage needed to establish a barrier capable of further reducing the local hydraulic conductivity, especially at the shallowest injection depth of 3 feet below land surface (ft bls). It is concluded that modified amounts of injected material, closer lateral injection spacing, and potentially modified injection temperatures and component ratios could increase the effectiveness of the Injectable BarrierSM.

Réalisé dans le cadrr du pôle de compétitivité Véhicule du Futur » de la région ,11k.c Franche Comté_ cc uas_ul de thèse porta sur la hmblcmatsque du remplacement des étoffes complexes textiles utilisées dans les applications d'habillage intérieur automobile. La législation sur les véhicules hors d'usage impose des produits automobiles a 1$" ), rccyclablcs et t 95' réutilisables dl ici janvier 2015. Alin de rebondie u la problématique posée ainsi qua la législation Europécnnc, des industriels et des acteurs de la recherche de la regain mulhousienne ont lias aillé ensemble dans le cadre du poilez VERTILAP" sur le développement d'un nouveau textile non-tissé 3D. Ce travail de thèse a eu pour objectif de développer le proucde de ! abris ation de ces nouveaux matériaux ainsi que les produits non-tisses 3D obtenus. La démarche de développements procédé produits a consisté Ii faire évoluer le prototype expérimental VERTILAP' au travers de la caractérisation physique et mécanique en compression des produits obtenus. Des méthodes ci dcsj outils de caractérisations adaptés a ces nouveaux produits ont etc mis au point. L'analyse de résultats obtenus s'est appuyée sur les outils statistiques i abn de valider ces résultats. Une étude comparative avec les produits contenant de la mousse polyuréthane (PU) a permis de montrer que ces nouveaux non-tissés 3D pouvaient être utilisés en remplacement des mousses PU. La réalisation de prototypes pour des applications d'habitacle autinnobilu a été faite et a prouvé la faisabilité industrielle d'un tel remplacement. Les résultats de ce travail ont été utilisés pour [élaboration du cahier des charges d'ur prototype semi industriel VERTILAP".

Abdominal aortic aneurysm (AAA) is a prevalent disease in developed countries. While endovascular aneurysm repair is fairly successful, it has shortcomings. Polymeric endoluminal paving and sealing is a method that has previously been developed to treat a range of diseases. Our goal is to further develop this technique to treat AAA, a process we have named polymeric endo-aortic paving (PEAP). We hypothesize that PEAP will overcome many of the limitations associated with EVAR by providing a minimally invasive treatment which can be used on patients with complicated AAA geometries and reducing incidence of migration and endoleak. Additionally, we plan to incorporate drug delivery into PEAP to improve efficacy. The purpose of this work was to evaluate a potential graft material for PEAP and to develop a thrombus mimic which will aid in further PEAP development. Blends of polycaprolactone/polyurethane (PCL/PU) were assessed by characterizing their mechanical, thermoforming, and degradation properties. PCL/PU grafts have a similar stiffness to aortic tissue and can be thermoformed at temperatures approaching 37 degrees C. Blending PCL with PU significantly reduces PCL's degradation. An anisotropic hyperelastic strain energy function was developed for the PCL/PU blends and finite element modeling (FEM) was used to show that stress reduction on the AAA wall that can be achieved by PEAP is similar to current EVAR. Stiffness varies throughout the AAA thrombus, and thrombus mimics were developed that have similar stiffness, components, and structure to native AAA thrombus.