The overall objective of this work was to develop processing, structure, and property relationships in graphene/polymer nanocomposites. To this end, different types of graphene platelets were produced from graphite oxide, dispersed into various thermoplastics and elastomers, and the morphology and properties of the resulting nanocomposites were evaluated. A range of tests were carried out on the nanocomposites to assess property improvements, including stress-strain testing, dynamic mechanical analysis, and thermal and electrical conductivity testing. Extensive morphological characterization, primarily through transmission electron microscopy (TEM) analysis, was performed to gain insight into the mechanisms behind the observed property improvements. The processing method used to disperse graphene platelets into a given polymer was found to exert significant influence over the nanocomposite morphology and properties. In both thermoplastics and elastomers, liquid-based dispersion methods were typically found to yield a better dispersion of graphene platelets compared with melt processing; the effectiveness of melt processing appeared to depend in part upon the method used to produce the graphene platelets. Latex compounding of graphene platelets and natural rubber generated nanocomposites with a network morphology with properties that were sensitive to further processing. The effect of graphene platelet intrinsic structure on nanocomposite properties was studied and property improvements with other nanofillers were compared to graphene platelets. The impact of platelet oxidation on nanocomposite properties was explored in two different systems and produced varying results depending on the polarity of the polymer matrix. An increased average aspect ratio of graphene platelets was not found to improve mechanical properties or a lower percolation threshold when dispersed in natural rubber. Graphene platelets produced superior reinforcement to multi-walled carbon nanotubes and exfoliated montmorillonite when dispersed in natural rubber; however, the carbon nanotubes produced the largest thermal and electrical conductivity enhancements. Qualitative observation of platelet dispersion by TEM was found to provide excellent correlation with nanocomposite properties when comparing different processing methods or filler materials. The average platelet aspect ratio of three different nanocomposite systems was determined by quantitative TEM analysis and used as a parameter in composite models to generate modulus predictions. Good agreement was found between model predictions and the experimental data. / text

Single walled carbon nanotube (SWNT)-based polymer nanocomposites have generated a lot of interest as potential multifunctional materials due to the exceptional physical properties of SWNTs. To date, investigations into the electromechanical response of these materials are limited. Previous studies have shown marginal improvements in the electromechanical response of already electroactive polymers (EAPs) with addition of SWNTs. However, in general, disadvantages of EAPs such as high actuation electric field, low blocked stress and low work capacity remain unaddressed. This dissertation targets a comprehensive investigation of the electromechanical response of SWNT-based polymer nanocomposites. Specifically, the study focuses on incorporating SWNTs in three polymeric matrices: a non-polar amorphous polyimide (CP2), a polar amorphous polyimide ((-CN) APB-ODPA), and a highly polar semicrystalline polymer (PVDF). In the first step, emergence of an electrostrictive response is discovered in the non-polar polyimide CP2 in the presence of SWNTs. Transverse and longitudinal electrostrictive coefficients are measured to be six orders of magnitude higher than those of known electrostrictive polymers like polyurethane and P(VDF-TrFE) at less than 1/100th of the actuation electric fields. Next, the effect of the polymer matrix on the electrostrictive response is studied by focusing on the polar (-CN) APB-ODPA. A transverse electrostriction coefficient of 1.5 m2/MV2 is measured for 1 vol percent SWNT- (-CN) APB-ODPA, about twice the value found for 1 vol percent SWNT-CP2. The high value is attributed to higher dipole moment of the (-CN) APB-ODPA molecule and strong non-covalent interaction between the SWNTs and (-CN) APB-ODPA matrix. Finally, polyvinylidene fluoride (PVDF) matrix is selected as a means to optimize the electrostrictive response, since PVDF demonstrates both a high dipole moment and a strong non-covalent interaction with the SWNTs. SWNT-PVDF nanocomposites fared better than SWNT-CP2 nanocomposites but had comparable response to SWNT-(-CN) APB-ODPA nanocomposites. This was attributed to comparable polarization in both the polar nanocomposite systems. To maximize the SWNT-PVDF response, SWNT-PVDF samples were stretched leading to increase in the total polarization of the nanocomposite samples and decrease in the conductive losses. However, the dielectric constant also decreased after stretching due to disruption of the SWNT network, resulting in a decrease of the electrostrictive response.

No description available.

Acid oxidation of multi-walled carbon nanotubes (MWCNTs) introduced carboxylic acid sites onto the MWCNT surface, which permitted further functionalization. Derivatization of carboxylic acid sites yielded amide-amine and amide-urea functionalized MWCNTs from oxidized precursors. Conventional MWCNT characterization techniques including X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Raman spectroscopy supported successful MWCNT functionalization. Incorporation of MWCNTs functionalized with hydrogen bonding groups into a segmented polyurethane matrix led to an increase in mechanical properties at optimized MWCNT loadings, in contrast with non-functionalized MWCNTs that resulted in mechanical property decreases across all loadings. Dynamic mechanical analysis (DMA) demonstrated an increase in the polyurethane-MWCNT composite flow temperature with increasing hydrogen bonding MWCNT incorporation, as opposed to non-functionalized MWCNT composites which displayed no significant change in flow temperature. Variable temperature Fourier transform infrared spectroscopy (VT FT-IR) probed temperature-dependent hydrogen bonding in the polyurethane-MWCNT composites and revealed a significant impact on composite hydrogen bonding interactions upon MWCNT incorporation, which was amplified in composites formed using hydrogen bonding functionalized MWCNTs. Acid oxidation of carbon nanohorns (CNHs) yielded carboxylic acid functionalized CNHs, providing sites for further reaction with histamine to afford histamine-functionalized CNHs (His-CNHs). Raman spectroscopy, XPS and TGA confirmed successful functionalization. Transmission electron microscopy (TEM) demonstrated that His-CNHs efficiently complex quantum dots (QDs) through imidazole-Zn interactions. Combination of His-CNHs, QDs, and a poly(oligo-(ethylene glycol9) methyl ether methacrylate)-block-poly(4-vinyl imidazole) copolymer using an interfacial complexation technique afforded stable ternary nanocomplexes with average hydrodynamic diameters under 100 nm. These ternary nanocomplexes represent promising materials for photothermal cancer theranostics due to their size and stability. The efficient reaction of 2-isocyanatoethyl methacrylate with amines afforded urea-containing methacrylic monomers, where the amine-derived pendant groups determined the polymer Tg. Reversible addition-fragmentation chain-transfer (RAFT) polymerization enabled the synthesis of ABA triblock copolymers with urea-containing methacrylic outer blocks and poly(2-ethylhexyl methacrylate) inner blocks. These ABA triblocks copolymers displayed composition dependent phase-separated morphologies and desirable mechanical properties. The urea-containing polymers efficiently complexed gold nanoparticles through urea-gold interactions. Furthermore, urea-containing methacrylic polymers served as a useful matrix for incorporation of silica-coated upconverting nanoparticles, affording upconverting nanoparticle composite films.The novel ionene monomer N1,N2-bis(3-(dimethylamino)propyl)oxalamide permitted synthesis of novel oxalamide-containing ammonium ionenes. The hydrogen bonding, charge density, and counter anion tuned the ionene mechanical properties. The ionene structure also influenced water uptake and conductivity. The differences in physical properties correlated well with the morphology observed in small-angle X-ray scattering. The oxalamide-containing ionenes greatly enhance mechanical properties compared to typical ammonium ionenes, and further expand the library of ionene polymers. / Ph. D.

The Effective Continuum Micromechanics Analysis Code (EC-MAC) was developed for predicting effective properties of composites containing multiple distinct nanoheterogeneities (fibers, spheres, platelets, voids, etc.) each with an arbitrary number of coating layers based upon either the modified Mori-Tanaka method (MTM) and self consistent method (SCM). This code was used to investigate the effect of carbon nanofiber morphology (i.e., hollow versus solid cross-section), nanofiber waviness, and both nanofiber-resin interphase properties and dimensions on bulk nanocomposite elastic moduli. For a given nanofiber axial force-displacement relationship, the elastic modulus for hollow nanofibers can significantly exceed that for solid nanofibers resulting in notable differences in bulk nanocomposite properties. The development of a nanofiber-resin interphase had a notable effect on the bulk elastic moduli. Consistent with results from the literature, small degrees of nanofiber waviness resulted in a significant decrease in effective composite properties. Key aspects of nanofiber morphology were characterized using transmission electron microscopy (TEM) images for VGCNF/vinyl ester (VE) nanocomposites. Three-parameter Weibull probability density functions were generated to describe the statistical variation in nanofiber outer diameters, wall thicknesses, relative wall thicknesses, visible aspect ratios, and visible waviness ratios. Such information could be used to establish more realistic nanofiber moduli and strengths obtained from nanofiber tensile tests, as well as to develop physically motivated computational models for predicting nanocomposite behavior. This study represents one of the first attempts to characterize the distribution of VGCNF features in real thermoset nanocomposites. In addition, the influence of realistic nanoreinforcement geometries, distinct elastic properties, and orientations on the effective elastic moduli was addressed. The effect of multiple distinct heterogeneities, including voids, on the effective elastic moduli was investigated. For the composites containing randomly oriented wavy vapor grown carbon nanofibers (VGCNFs) and voids, the predicted moduli captured the essential character of the experimental data, where the volume fraction of voids was approximated as a nonlinear function of the volume fraction of reinforcements. This study should facilitate the development of multiscale materials design by providing insight into the relationships between nanomaterial morphology and properties across multiple spatial scales that lead to improved macroscale performance.

Doctor of Philosophy / The drastic improvements in stiffness and strength even with the addition of small percentage of clay to a polymer are commonly traded-off with significant reductions in fracture toughness. It is believed that the presence of a stiff nano-filler will restrict the mobility of the surrounding matrix chains, and thus limit its ability to undergo plastic deformation, thereby decreasing their fracture toughness. To understand the role of rigid nano-fillers, like clay and their constraint effect on the surrounding polymer matrix, the effects of preferentially organized polyamide 6 lamellae in the vicinity of organoclay layers on the toughening processes are studied and compared with polyamide 6 filled with an elastomeric additive (POE-g-MA). It is suggested that to impart high toughness to polymer/organoclay nanocomposites, full debonding at the polymer-organoclay interface is necessary so that shear yielding of large volumes of matrix material can be enhanced. However, due to the strong tethering junctions between the individual organoclay layers and the matrix, full-scale debonding at the polymer-organoclay interface is rarely observed under stress conditions indicating that the constraint on the polymer adjacent to the clay is not relieved. Therefore, this has led to the development of ternary nanocomposites by adding a soft elastomeric dispersed phase to polymer/clay systems to obtain well-balanced mechanical properties. Polyamide 66/SEBS-g-MA/organoclay nanocomposites are prepared with four different blending protocols to understand the effect of blending protocol on the microstructure, mechanical properties and fracture mechanisms of the ternary nanocomposites so as to obtain new insights for producing better toughened polymer nanocomposites. In general, it is found that the level of enhancement of fracture toughness of ternary nanocomposites depends on: (i) the location and extent of dispersion of organoclay and (ii) the internal cavitation of rubber particles leading to effective relief of crack-tip tri-axial constraint and thus activating the matrix plastic deformation. Based on the wear/scratch damage studies on different polymer nanocomposite systems, it is suggested that elastic modulus and toughness of polymer nanocomposites are not the predominant factors controlling the material removal or friction coefficient and cannot be the sole indicators to compare and rank candidate materials. It is also found that nano-fillers by themselves, even if uniformly dispersed with good interfacial interaction with the matrix, do not irrevocably improve the wear (and friction) properties. Although it is important to consider these factors, it is necessary to thoroughly understand all microstructural parameters and their response to wear/scratch damage. Other important factors that should be considered are the formation of a uniform and stable transfer film on the counterface slider and the role of excessive organic surfactants or other modifiers added to disperse nanoparticles in a polymer matrix. It is also emphasized that the mechanisms of removal of materials during the wearing/scratching process should be studied meticulously with the use of high resolution microscopic and other analytical tools as this knowledge is critical to understand the surface integrity of polymer nanocomposites.

Tomorrow’s lightweight, high-performance composite systems will be made of structures built with materials that have unprecedented intrinsic properties for performing a wide range of functions, such as EMI shielding, thermal management, flame resistance, lightning strike protection, acoustic damping, and health-monitoring. Current structures require parasitic components, e.g., metal strips, copper wire meshes, strain gauges, and heat sinks to provide these functions. By eliminating parasitic components, future high-performance multifunctional systems can achieve the intended objectives, while maintaining optimum weight, reliability, cost, and fuel efficiency. With the continuing growth of polymer composites in industries, such as aerospace, automotive, and wind energy, research and development on lightweight, high-performance composites that possess extraordinary properties for future multifunctional systems has generated considerable interest and excitement. Recent advances in nanomaterial synthesis and functionalization have shown that tailored property combinations are possible with reduced parasitic content to achieve multifunctionality. Cyanate ester (CE), a class of high-performance thermosetting resins (high T [subscript g], >250°C), has received considerable attention due to its good mechanical properties, thermal stability, flammability properties, ease of process, and volatile-free curing process. Multiwall carbon nanotubes were selected due to their unique combination of excellent mechanical, electrical, and thermal properties. The principal objective of this work is to determine the extent to which several different processing techniques will affect the MWNT dispersion and corresponding nanocomposite properties, such as thermal, flammability, mechanical, and electrical properties. A processing-structure-property relationship, as well as performance of this class of carbon-based CE nanocomposite, will be established. Therefore, a major scientific contribution of this study will be the development and characterization of a novel, multifunctional CE nanocomposite. Different mixing instruments, such as high shear mixer, ultrasonicator, planetary centrifugal mixer, etc. were used to disperse the nanotubes in the cyanate ester resin matrix. Microstructural morphology characterizations by SEM, STEM, and TEM show that various degrees of dispersions of MWNTs were obtained by the different mixing techniques. An attempt to quantify the MWNT dispersion was made. Electrical resistivity of samples processed by both stand mixer and three-roll mill passes the ESD requirement; however, the MWNT percolation thresholds by the two techniques are different. Thermal analysis shows that the addition of the Fe³+ catalyst or the coupling agent lowers the glass transition temperature and degrades the mechanical properties (e.g., storage modulus, tangent of phase angle delta) of the CE resin. On the other hand, processing techniques only affect the mechanical properties of the resin. Thermal stability of CE is only slightly affected by different processing techniques, as well as the addition of MWNTs. Much more significantly, flammability characterization shows that the incorporation of either the Fe³+ catalyst or the coupling agent substantially increases the peak heat release rate (PHRR) relative to the neat CE resin value. / text

Current technology of polymer nanocomposites (PNC) emphasizes the need for fundamental understanding of the links between manufacturing method and macro-scale properties in order to engineer processing and performance of PNCs. The manufacturing method is one key variable that dramatically defines interfacial interactions on the nano-scale and thus the properties of polymer near the interface of nanomaterial/polymer or interphase, level of dispersion and the crystallization behavior of semi-crystalline PNCs. These factors in particular govern reinforcing mechanisms at the interface and consequently impart important properties to PNCs. The current approach to manufacturing PNCs involves trial and error with elaborate, costly and time consuming experimental characterization of PNCs. Therefore, a deep insight into the links among manufacturing method, interfacial interactions and bulk properties is essential in order to design and fabricate PNCs with engineered performance. The main goal of this study was to provide a better understanding of the effect of manufacturing methods on the macro-scale properties of PNCs, with a focus on the role of interfacial interactions, that can lead to fabrication of PNCs with multifunctional performance. The objectives of this research were to: i) determine the detail correlations among manufacturing method, nano- and microstructure and macro-scale properties of multifunctional exfoliated graphite nanoplatelets/polyamide 12 polymer nanocomposites with enhanced mechanical and electrical performance through systematic manufacturing and experimental methodologies, ii) understand correlations among nano-scale interfacial interactions, physical and structural properties of the polymer at the interface and macro-scale behavior of PNCs, and iii) evaluate effect of manufacturing method on electrical behavior of PNCs with directionally dependent performance. This study demonstrated key correlations among manufacturing techniques, interfacial interactions and macro-scale properties of PNCs. A methodology was introduced to understand and determine the characteristics of a complex constrained region produced at the interface of nanomaterials and polymer in semi-crystalline PNCs. Finally, the study illustrated superior electrical and morphological properties of selective laser sintering (SLS) processed parts over injection molded PNCs and thus confirmed the capability of SLS in the development of electrically conductive PNCs that exhibit multifunctional performance. In conclusion, the study provided an insight into the links among process, nano-scale interfacial interactions and microstructure to better understand effects of manufacturing technique on macro-scale properties of PNCs, which enables fabrication of conductive PNCs with multifunctional performance.

Doctor of Philosophy / The drastic improvements in stiffness and strength even with the addition of small percentage of clay to a polymer are commonly traded-off with significant reductions in fracture toughness. It is believed that the presence of a stiff nano-filler will restrict the mobility of the surrounding matrix chains, and thus limit its ability to undergo plastic deformation, thereby decreasing their fracture toughness. To understand the role of rigid nano-fillers, like clay and their constraint effect on the surrounding polymer matrix, the effects of preferentially organized polyamide 6 lamellae in the vicinity of organoclay layers on the toughening processes are studied and compared with polyamide 6 filled with an elastomeric additive (POE-g-MA). It is suggested that to impart high toughness to polymer/organoclay nanocomposites, full debonding at the polymer-organoclay interface is necessary so that shear yielding of large volumes of matrix material can be enhanced. However, due to the strong tethering junctions between the individual organoclay layers and the matrix, full-scale debonding at the polymer-organoclay interface is rarely observed under stress conditions indicating that the constraint on the polymer adjacent to the clay is not relieved. Therefore, this has led to the development of ternary nanocomposites by adding a soft elastomeric dispersed phase to polymer/clay systems to obtain well-balanced mechanical properties. Polyamide 66/SEBS-g-MA/organoclay nanocomposites are prepared with four different blending protocols to understand the effect of blending protocol on the microstructure, mechanical properties and fracture mechanisms of the ternary nanocomposites so as to obtain new insights for producing better toughened polymer nanocomposites. In general, it is found that the level of enhancement of fracture toughness of ternary nanocomposites depends on: (i) the location and extent of dispersion of organoclay and (ii) the internal cavitation of rubber particles leading to effective relief of crack-tip tri-axial constraint and thus activating the matrix plastic deformation. Based on the wear/scratch damage studies on different polymer nanocomposite systems, it is suggested that elastic modulus and toughness of polymer nanocomposites are not the predominant factors controlling the material removal or friction coefficient and cannot be the sole indicators to compare and rank candidate materials. It is also found that nano-fillers by themselves, even if uniformly dispersed with good interfacial interaction with the matrix, do not irrevocably improve the wear (and friction) properties. Although it is important to consider these factors, it is necessary to thoroughly understand all microstructural parameters and their response to wear/scratch damage. Other important factors that should be considered are the formation of a uniform and stable transfer film on the counterface slider and the role of excessive organic surfactants or other modifiers added to disperse nanoparticles in a polymer matrix. It is also emphasized that the mechanisms of removal of materials during the wearing/scratching process should be studied meticulously with the use of high resolution microscopic and other analytical tools as this knowledge is critical to understand the surface integrity of polymer nanocomposites.

No description available.