Dissertation (Ph. D.)--University of Akron, Dept. of Polymer Engineering, 2009. / "August, 2009." Title from electronic dissertation title page (viewed 9/23/2009) Advisor, Sadhan C. Jana; Committee members, Avraam I. Isayev, James L. White, George G. Chase, Shing-Chung Josh Wong; Department Chair, Sadhan C. Jana; Dean of the College, Stephen Z. D. Cheng; Dean of the Graduate School, George R. Newkome. Includes bibliographical references.

Yes / Polymer nanocomposites are usually characterized using various methods, such as small angle X-ray diffraction (XRD) or transmission electron microscopy, to gain insights into the morphology of the material. The disadvantages of these common characterization methods are that they are expensive and time consuming in terms of sample preparation and testing. In this work, near infrared spectroscopy (NIR) spectroscopy is used to characterize nanocomposites produced using a unique twin-screw mini-mixer, which is able to replicate, at ~25 g scale, the same mixing quality as in larger scale twin screw extruders. We correlated the results of X-ray diffraction, transmission electron microscopy, G′ and G″ from rotational rheology, Young’s modulus, and tensile strength with those of NIR spectroscopy. Our work has demonstrated that NIR-technology is suitable for quantitative characterization of such properties. Furthermore, the results are very promising regarding the fact that the NIR probe can be installed in a nanocomposite-processing twin screw extruder to measure inline and in real time, and could be used to help optimize the compounding process for increased quality, consistency, and enhanced product properties

Polymer nanocomposites represent a class of advanced, multifunctional materials, combining the attractive features of both nanomaterials and polymers. The level of dispersion of the nanoparticles directly controls the extent to which nanocomposites can maximize the unique attributes of their nano-scale fillers. However, as a consequence of the tendency of nanofillers to agglomerate, the anticipated superior properties of polymer nanocomposites are yet to be realised, and remain merely a theoretical prediction. As a result, the surface chemistry of nanofillers is often tailored to reduce the attractive interparticle interactions that promote agglomeration. This modification can also be used to enhance the interfacial interactions between the nanofiller and polymer matrices to achieve improved filler dispersion. Accordingly, this thesis addresses this challenge in nanocomposite technology by investigating the chemical surface functionalisation of various nanoparticles in order to produce polypropylene (PP) nanocomposites with superior electrical, mechanical and thermal properties. Part I describes covalent modification of nanosilica, microsilica, furnace Carbon Black (CB), acetylene black (ACB) and carbon nanotube (CNT) nanomaterials by carbene insertion and azo-coupling reactions, in a series of studies, in order to tailor their surfaces for application in polypropylene (PP) nanocomposites. The surface characterisation of the modified nanomaterials was assessed in detail using XPS, CHN, SSNMR, BET, ATR-IR and thermal analysis techniques. The surface grafting densities were estimated to be of the order of 10¹³ and 10¹⁴ molecules/cm² and additionally, SSNMR provided direct evidence of the diarylcarbene reaction to the silica surface. Following nanocomposite production with PP by solvent mixing methods, the macroscopic properties were studied demonstrating altered electrical, mechanical and thermal properties following assessment of the DC conductivity, dielectric properties, thermal analysis (TGA, DSC, DMA) and morphological measurements. In particular, the introduction to the CB surface of a diaryl complex with terminal dodecyl hydrocarbon chains demonstrated substantial improvements to the DC electrical and dielectric properties of the PP nanocomposites. Part II explores the non-covalent surface functionalisation of CB and ACB by the physisorption of the non-ionic surfactant Triton-X-100. Various protocols were developed in which an optimal surface loading for CB was determined by treatment at 0.024 mM(aq). In addition, the modification procedure was combined with the granulation protocol of ACB in an effort to evaluate the potential for industrial applications. The degree of surface functionalisation was extensively characterised by BET, XPS, thermal analysis, UV-Vis and ATR-IR analyses. PP nanocomposites produced by solvent and melt mixing methods demonstrated similar conductive properties following the nanoscale modification, however morphological, dielectric and thermal analysis indicated altered interfacial interactions demonstrating improved mechanical properties.

As a preliminary starting point for the present study, physical and mechanical properties of polypropylene nanocomposites (PPNCs) for samples received from Queen's University Belfast have been evaluated. Subsequently, polymer/clay nanocomposite material has been produced at Bradford. Mixing and processing routes have been explored, and mechanical properties for the different compounded samples have been studied. Clay intercalation structure has received particular attention to support the ultimate objective of optimising tensile and fracture behaviour of isotropic and die-drawn PPNCs. Solid-state molecular orientation has been introduced to PPNCs by the die-drawing process. Tensile stress-strain measurements with video-extensometry and tensile fracture of double edge-notched tensile specimens have been used to evaluate the Young's modulus at three different strain rates and the total work of fracture toughness at three different notch lengths. The polymer composite was analyzed by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, wide angle x-ray diffraction, and transmission electron microscopy. 3% and 5% clay systems at various compatibilizer (PPMA) loadings were prepared by three different mixing routes for the isotropic sheets, produced by compression moulding, and tensile bars, produced by injection moulding process. Die-drawn oriented tensile bars were drawn to draw ratio of 2, 3 and 4. The results from the Queen's University Belfast samples showed a decrement in tensile strength at yield. This might be explained by poor bonding, which refers to poor dispersion. Voids that can be supported by intercalated PP/clay phases might be responsible for improvement of elongation at break. The use of PPMA and an intensive mixing regime with a two-step master batch process overcame the compatibility issue and achieved around 40% and 50% increase in modulus for 3% and 5% clay systems respectively. This improvement of the two systems was reduced after drawing to around 15% and 25% compared with drawn PP. The work of fracture is increased either by adding nanoclay or by drawing to low draw ratio, or both. At moderate and high draw ratios, PPNCs may undergo either an increase in the size of microvoids at low clay loading or coalescence of microvoids at high clay loading, eventually leading to an earlier failure than with neat PP. The adoption of PPMA loading using an appropriate mixing route and clay loading can create a balance between the PPMA stiffness effect and the degree of bonding between clay particles and isotropic or oriented polymer molecules. Spherulites size, d-spacing of silicate layers, and nanoparticles distribution of intercalated microtactoids with possible semi-exfoliated particles have been suggested to optimize the final PPNCs property.