The use of compliant coatings, in particular polyurea, for improved blast protection of structures has been reported recently in the literature. The goal of this research is to develop a comprehensive understanding of the reasons for improved performance of coated structures through experimentation and correlation with simulation. The different factors influencing the response of an elastomer coated ductile metal subjected to a blast load have been examined and quantified. First, dynamic strain localization in the metal is a precursor to ductile failure; this was characterized for the metal of interest with and without the polymer coating. Experiments with the expanding ring/tube and experiments have demonstrated that for Al 6061-O and Al 3003-H14, the localization strain is unaffected by both deformation rate and the polymer coating; however, two important effects of the coating have been explored. First the additional mass of the coating provides an inertial resistance. Second, the flow resistance of the polymer provides continued dissipation of energy even after the metal has yielded potentially preventing failure in the metal, or at least containing fragments. These effects were examined for two different types of polymers – polyurea, an elastomer and polycarbonate, a thermoplastic shear yielding polymer. It is shown that these two effects can be used to tailor the coating to optimize blast protection of the bilayer system. In order to take advantage of this optimization, the constitutive behavior of the elastomer coating must be determined at strain rates and loading conditions that are experienced in the blast loading; these strain rates are in the range of 1000 to 10,000 per second. This has been accomplished through a hybrid method that combines measurements with numerical simulations to extract the constitutive response of the material. The strain rate dependent behavior of polyurea for rates in the range of 800-8000 per second has been determined by measuring the spatio-temporal evolution of the particle velocity and strain in a thin strip subjected to high speed impact loading that generates uniaxial stress conditions and comparing this with numerical simulations of the one-dimensional problem using the method of characteristics. A similar scheme to track the particle velocity and strain during the axisymmetric deformation of a membrane subjected to high speed loading has also been developed; this requires two projections of the deformation to be obtained in order to facilitate the measurement of axial and kink waves in the membrane. The finite volume method is adapted for simulations of these dynamic uniaxial and axisymmetric problems with a view towards simulating shock waves that are expected to form in some loading conditions. The hybrid method is used once again to characterize the constitutive response. The axisymmetric experiments have demonstrated the inability of the uniaxial models for both polyisoprene rubber and polyurea to completely capture their behavior during a more complex loading, and left a need for further work on characterizing the dynamic constitutive response of these polymers. / text

An estimated 200,000 injuries to the anterior cruciate ligament (ACL) occur annually in the United States, with approximately 100,000 total ACL reconstructions performed each year. Due to inherent limitations with existing ACL reconstruction strategies, the development of tissue engineered ligaments is a key area of musculoskeletal research. Although great strides have been made in the scaffold design, current strategies are limited by the inability to replicate the mechanical behavior of native ligament tissue with synthetic polyesters or natural polymers. Poly(ester urethane)s have recently been investigated as possible scaffold materials because of their established biocompatibility, excellent mechanical properties, and exceptionally tunable structure. However, non-specific degradation makes it difficult to tailor polyurethane structure to complement ligament regeneration. In contrast, a biomaterial that features system-responsive degradation would integrate with native ligament remodeling and thus provide effective load transfer to newly formed tissue that is necessary to restore mechanical integrity. In this study, enzyme-labile peptide sequences were conjugated to ether-based polyols to form collagen-mimetic soft segments that feature cell-responsive degradation. Synthetic routes were first developed to functionalize these polyols with favorable end groups for peptide coupling. Upon successful conjugation, biodegradable soft segments were then incorporated into the structure of linear polyurea elastomers. By varying soft segment chemistry, soft segment molecular weight, and the hard to soft segment ratio, a library of cell-responsive, biodegradable polyureas was developed. This library can then be used to elucidate key structure-property relationships necessary to complement neotissue formation. Overall, synthesis of a novel biomaterial that combines the strength and tunability of synthetic elastomers with cell-responsive degradation will assist in the development of an improved tissue engineered graft for ACL reconstruction.

A new design of dual-functional polyurea microcapsules was proposed for chronic wound dressings to provide both non-leaching infection control and sustained topical drug delivery functionalities. Quaternary ammonium functionalized polyurea microcapsules (MCQs) were synthesized under mild conditions through an interfacial crosslinking reaction between branched polyethylenimine (PEI) and 2,4-toluene diisocyanate (TDI) in a dimethylformamide/cyclohexane emulsion. An in-situ modification method was developed to endow non-leaching surface antimicrobial properties to MCQs via bonding antimicrobial surfactants to surface isocyanate residues on the polyurea shells. The resultant robust MCQs with both non-leaching antimicrobial properties and sustained drug releasing properties have potential applications in medical textiles, such as chronic wound dressings, for infection control and drug delivery.

A new design of dual-functional polyurea microcapsules was proposed for chronic wound dressings to provide both non-leaching infection control and sustained topical drug delivery functionalities. Quaternary ammonium functionalized polyurea microcapsules (MCQs) were synthesized under mild conditions through an interfacial crosslinking reaction between branched polyethylenimine (PEI) and 2,4-toluene diisocyanate (TDI) in a dimethylformamide/cyclohexane emulsion. An in-situ modification method was developed to endow non-leaching surface antimicrobial properties to MCQs via bonding antimicrobial surfactants to surface isocyanate residues on the polyurea shells. The resultant robust MCQs with both non-leaching antimicrobial properties and sustained drug releasing properties have potential applications in medical textiles, such as chronic wound dressings, for infection control and drug delivery.

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.

abstract: Improved knowledge connecting the chemistry, structure, and properties of polymers is necessary to develop advanced materials in a materials-by-design approach. Molecular dynamics (MD) simulations can provide tremendous insight into how the fine details of chemistry, molecular architecture, and microstructure affect many physical properties; however, they face well-known restrictions in their applicable temporal and spatial scales. These limitations have motivated the development of computationally-efficient, coarse-grained methods to investigate how microstructural details affect thermophysical properties. In this dissertation, I summarize my research work in structure-based coarse-graining methods to establish the link between molecular-scale structure and macroscopic properties of two different polymers. Systematically coarse-grained models were developed to study the viscoelastic stress response of polyurea, a copolymer that segregates into rigid and viscous phases, at time scales characteristic of blast and impact loading. With the application of appropriate scaling parameters, the coarse-grained models can predict viscoelastic properties with a speed up of 5-6 orders of magnitude relative to the atomistic MD models. Coarse-grained models of polyethylene were also created to investigate the thermomechanical material response under shock loading. As structure-based coarse-grained methods are generally not transferable to states different from which they were calibrated at, their applicability for modeling non-equilibrium processes such as shock and impact is highly limited. To address this problem, a new model is developed that incorporates many-body interactions and is calibrated across a range of different thermodynamic states using a least square minimization scheme. The new model is validated by comparing shock Hugoniot properties with atomistic and experimental data for polyethylene. Lastly, a high fidelity coarse-grained model of polyethylene was constructed that reproduces the joint-probability distributions of structural variables such as the distributions of bond lengths and bond angles between sequential coarse-grained sites along polymer chains. This new model accurately represents the structure of both the amorphous and crystal phases of polyethylene and enabling investigation of how polymer processing such as cold-drawing and bulk crystallization affect material structure at significantly larger time and length scales than traditional molecular simulations. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2016

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<p> Polyurea microcapsules are micron-scale, hollow polymer spheres commonly used in agriculture to encapsulate pesticides for controlled diffusive release onto target crops. Diffusion of these active materials through a protective polymer wall offers a safer and more effective method of delivery compared to the direct spraying of crops with toxicants. The approach we are taking to control the release rate is to coat pre-formed porous polyurea capsules with a separate release-controlling outer layer. This allows us to separately optimize the load-bearing capsule wall and the release control layer, an approach commonly used in other membrane diffusion systems.</p> <p> Montmorillonite clay incorporation into polymer matrices can reduce membrane permeability by forcing diffusants to take a tortuous path around the stacked silicate sheets. Effective formation of clay-polyurea composites requires the delamination of clay particles into thin sheets with high aspect ratios, and their incorporation into polyurea microcapsules either during interfacial polymerization, or post-polymerization. The net negative surface charge of the silicate sheets should facilitate their initial binding to the cationic polyurea surfaces, as well as subsequent binding of polycations to the clay-coated polyurea capsules to create layer-by-layer (LbL) capsule assemblies with decreasing release rates of internal materials.</p> <p> The main focus of this project is to gain a fundamental understanding of montmorillonite clay and polyurea microcapsules, and the development of a model polyurea composite capsule for release rate analysis. Emphasis will be placed on the reduced permeability of microcapsules coated with clay by LbL assembly post-polymerization, followed by an exploration of further layering with polycations.</p> / Thesis / Master of Science (MSc)