This study was conducted to investigate the effects of component concentrations and addition order of the components, on the final properties of ternary nanocomposites composed of poly(ethylene terephthalate), organoclay, and an ethylene/methyl acrylate/glycidyl methacrylate (E-MA-GMA) terpolymer acting as an impact modifier for PET. In this context, first, the optimum amount of the impact modifier was determined by melt compounding binary PET-terpolymer blends in a corotating twin-screw extruder. The amount of the impact modifier (5 wt. %) resulting in the highest Young&rsquo / s modulus and reasonable elongation at break was selected owing to its balanced mechanical properties. Thereafter, by using 5 wt. % terpolymer content, the effects of organically modified clay concentration and addition order of the components on ternary nanocomposites were systematically investigated. Mechanical testing revealed that different addition orders of the materials significantly affected mechanical properties. Among the investigated addition orders, the best sequence of component addition (PI-C) was the one in which poly(ethylene terephthalate) was first compounded with E-MA-GMA. Later, this mixture was compounded with the organoclay in the subsequent run. Young&#039 / s modulus of not extruded pure PET increased by 67% in samples with 5 wt. % E-MA-GMA plus 5 wt. % clay loading. The highest percent elongation at break was obtained as 300%, for the addition order of PI-C, with 1 wt. % clay content, which is nearly 50 fold higher than that obtained for pure PET. In X-ray diffraction analysis, extensive layer separation associated with delamination of the original clay structure occurred in PI-C and CI-P sequences with both 1 and 3 wt. % clay contents. X-ray diffraction patterns showed that, at these conditions exfoliated structures resulted as indicated by the disappearence of any peaks due to the diffraction within the consecutive clay layers.

This study was conducted to investigate the effects of organoclay type and concentration on the nanocomposites synthesized by &ldquo / In-Situ Polymerization&rdquo / and &ldquo / Prepolymerization&rdquo / methods. In-Situ Polymerization Method was in fact a new route which consisted of dispersing the monomers / propylene glycol, maleic anhydride and o-phthalic anhydride into the galleries of montmorillonite followed by subsequent polymerization. The Prepolymerization Method involved the addition of montmorillonite to the previously synthesized unsaturated polyester. As the first step, all the compositions were prepared by Cloisite 30B, and then for comparison of clay type, nanocomposites containing 3 wt.% of Cloisite 15A and Cloisite 25A were also synthesized. The efficiency of the two methods were compared with regards to their structural, thermal and mechanical properties. According to the results of XRD analysis, in both methods, maximum intercalation was observed when Cloisite 30B was used. An exfoliated structure was obtained in the Prepolymerization Method at 3 wt. % Cloisite 30B content. In all clay types, the increase in the d-spacings of the organoclays was higher when the Prepolymerization Method was applied. With Cloisite 30B, maximum improvement in the impact strength was obtained at 3 wt. % organoclay loading and the In-Situ Method yielded better results leading to a 77% increase in the impact strength at this organoclay loading. Among the organoclay types, Cloisite 15A was found to give rise to maximum increase in the impact strength. With the Prepolymerization Method higher improvement in flexural strength and flexural modulus was obtained owing to the lower styrene content in the crosslinking medium. The elongation at break values followed a decreasing trend with increasing clay content but did not show any significant difference when the clay types were compared.

In this study, the effects of glycol type, organoclay type and concentration on the final properties of nanocomposites based on recycled poly(ethylene terephthalate) was investigated. For this purpose, first recycled PET was glycolysed and after that unsaturated polyester-montmorillonite nanocomposites were synthesized by using three different types of glycols (i.e. ethylene glycol (EG), propylene glycol (PG) and diethylene glycol (DEG)). As the first step, all the compositions were prepared by Cloisite 30B type of clay, and then for comparison of clay type, nanocomposites containing 1 wt. % of Cloisite 15A and Cloisite 25A type of clay were also synthesized. Morphological and mechanical analyses were performed for the characterization of the nanocomposites. According to the results of XRD analysis, for all glycol types maximum intercalation was observed in Cloisite 30B containing samples. Exfoliated structures were obtained in the samples containing EG at 1 wt. % Cloisite 30B content and DEG at 3 wt. % Cloisite 30B content. Mechanical tests showed that, for all properties, glycol type is the most effective experimental parameter. DEG based samples are the most flexible whereas PG based samples are the least flexible. EG and DEG based samples give maximum tensile strength and tensile modulus values at 1 wt. % clay loading. Samples prepared by DEG exhibited maxima in both flexural strength and modulus at 1 wt. % clay content. With respect to the organoclay type, Cloisite 30B containing samples gave the highest compatibility with the unsaturated polyester matrix as indicated by the tensile test results. Organoclay type and content had no positive effect on the impact strength. Clay particles acted as stress concentrators and lowered the impact strength.

ABSTRACT PRODUCTION AND CHARACTERIZATION OF RESOL TYPE PHENOLIC RESIN / LAYERED SILICATE NANOCOMPOSITES TaSan, Cemal Cem M.S., Department of Metallurgical and Materials Engineering Supervisor: Assoc.Prof. Cevdet Kaynak April 2005 133 Pages Polymer / layered silicate (P/LS) nanocomposites belong to one of the most promising group of materials of the past few decades and most probably for the near future. Combining two of the most widely studied topics of material science: composite materials and nanotechnology / P/LS research have drawn great attention starting with the pioneering works of Toyota Research Group in 1980&rsquo / s. The research is now being carried out world wide / since the excellent properties of these new materials, which is achieved by using very low amounts of a cheap reinforcement material (clay), increases the interest on these materials everyday after. In this present study, the object was to investigate the production parameters of phenol formaldehyde based layered silicate nanocomposites. For this purpose, 14 different specimen groups were produced / using two different resol type phenolic resins (PF76 and PF76TD) as the matrix / and 9 different montmorillonite clays (Rheospan, Resadiye, Cloisite Na+, 10A, 15A, 20A, 25A, 30B, 94A) as the reinforcement phase. Initially the curing schedules for the available resins were experimentally determined. Then, a short and effective mixing procedure for the thermosetting resin and the montmorillonite clay was developed. The effects of several processing parameters / such as clay type, clay source, clay content, clay modification, resin type, resin cure type, cure cycle and mixing cycle were determined by X-ray Diffraction, Scanning Electron Microscopy and Mechanical Tests. Then, Transmission Electron Microscopy was used to investigate the level of intercalation and/or exfoliation of the layered silicates. Finally, Differential Scanning Calorimetry was also carried out to analyse thermal properties of the specimens. It was concluded that, a partially intercalated and/or exfoliated structure could be obtained in resol type phenolic resin based systems at very low clay contents (such as 0,5%) leading to remarkable increases in mechanical properties (e.g. 66% increase in fracture toughness).

In this study the effects of compatibilizer type, organoclay type, and the addition order of components on the morphological, thermal, mechanical and flow properties of ternary nanocomposites based on low density polyethylene, LDPE were investigated. As compatibilizer, ethylene/methyl acrylate/glycidyl methacrylate, ethylene/glycidyl methacrylate, and ethylene/butyl acrylate/maleic anhydride / as organoclay Cloisite&amp / #61666 / 15A, Cloisite&amp / #61666 / 25A and Cloisite&amp / #61666 / 30B were used. All samples were prepared by a co-rotating twin screw extruder, followed by injection molding. Before producing the ternary nanocomposites, in order to determine the optimum amount of the organoclay and compatibilizer, binary mixtures of LDPE/organoclay and LDPE/compatibilizer blends with different compositions were prepared. Based on the results of the mechanical tests, compatibilizer and organoclay contents were determined as 5 wt. % and 2 wt % respectively. After that, ternary nanocomposites were prepared with each compatibilizer/organoclay system and characterization of these nanocomposites was performed. Among the investigated addition orders, mechanical test results showed that the best sequence of component addition was (PCoC), in which LDPE, compatibilizer and organoclay were simultaneously compounded in the first run of the extrusion. Considering the ternary nanocomposites, compositions of LDPE/E-MA-GMA/15A, LDPE/E-GMA/15A and LDPE/E-nBA-MAH/30B showed the highest improvement in mechanical properties. According to the DSC analysis, addition of organoclay and compatibilizer does not influence the melting behavior of the compositions and both compatibilizers and organoclay types have no nucleation activity in LDPE. In the X-Ray analysis, the highest increase of the basal spacing for ternary nanocomposites obtained for LDPE/E-BA-MAH/organoclay nanocomposites. This increase was 83 %, 198 %, and 206 % for samples containing 15A, 25A and 30B respectively.

The objective of the current research was to contribute to the area of mechanics of composite polymeric materials. This objective was reached by establishing a quantitative assessment of the fatigue strength and evolution of mechanical property changes during fatigue loading of nanocomposite fibers and films. Both experimental testing and mathematical modeling were used to gain a fundamental understanding of the fatigue behavior and material changes that occurred during fatigue loading. In addition, the objective of the study was to gain a qualitative and fundamental understanding of the failure mechanisms that occurred between the nanoagent and matrix in nanocomposite fibers. This objective was accomplished by examining scanning electron microscopy (SEM) fractographs. The results of this research can be used to better understand the behavior of nanocomposite materials in applications where degradation due to fatigue and instability of the composite under loading conditions may be a concern. These applications are typically encountered in automotive, aerospace, and civil engineering applications where fatigue and/or fracture are primary factors that contribute to failure.

This research explored the processing and properties of PNCs using a polyfurfural alcohol (PFA) matrix. The precursor for PFA, furfuryl alcohol (FA) is sourced from feedstocks rich in hemicellulose, such as corn cobs, oat hulls and wood. To exploit FA as a polymerizable solvent, cellulose whiskers (CW) and montmorillonite clay (MMT) were used as the nanoparticle phase. Results from PNC processing show that CW and MMT can be dispersed in the PFA matrix by means of insitu polymerization, without the use of surfactants or dilution in solvents. Both CW and MMT nanoparticles catalyze the polymerization of furfuryl alcohol (FA). Moreover, the insitu intercalative polymerization of FA in the interlayer galleries of MMT leads to the complete exfoliation of the MMT in the PFA matrix. CW and MMT both function as effective matrix modifiers, increasing the thermal stability of PFA nanocomposites compared to pure PFA polymer. The increased thermal stability is seen as significant increases in the onset of degradation and in residual weight at high temperature. This research also explored the surface functionalization of Cu, Ni and Pt substrates by self-assembly of a range of difunctional linker molecules. Characterization by XPS and PM-IRRAS indicate that diisocyanides and dicarboxylic acids both form chemically "sticky" surfaces after self-assembly on Cu and Ni. Sticky surfaces may provide a means of increasing nanoparticle dispersion in metal nanocluster filled PNCs, by increasing their interaction with the matrix polymer. Another potential application for sticky surfaces on Cu is in the ongoing miniaturization of circuit boards. The functionalization of Cu bond pad substrates with linker molecules may provide an alternate means of bonding components to their bond pads, with higher placement accuracy compared to solder bumps.

Driven by ever growing demands of miniaturization, increased functionality, high performance and low cost for microelectronic products and packaging, embedded passives will be one of the key emerging techniques for realizing the system integration which offer various advantages over traditional discrete components. Novel materials for embedded capacitor applications are in great demand, for which a high dielectric constant (k), low dielectric loss and process compatibility with printed circuit boards are the most important prerequisites. To date, no available material satisfies all these prerequisites and research is needed to develop materials for embedded capacitor applications. Conductive filler/polymer composites are likely candidate material because they show a dramatic increase in their dielectric constant close to the percolation threshold. One of the major hurdles for this type of high-k composites is the high dielectric loss inherent in these systems. In this research, material and process innovations were explored to design and develop conductive filler/polymer nanocomposites based on nanoparticles with controlled parameters to fulfill the balance between sufficiently high-k and low dielectric loss, which satisfied the requirements for embedded decoupling capacitor applications. This work involved the synthesis of the metal nanoparticles with different parameters including size, size distribution, aggregation and surface properties, and an investigation on how these varied parameters impact the dielectric properties of the high-k nanocomposites incorporated with these metal nanoparticles. The dielectric behaviors of the nanocomposites were studied systematically over a range of frequencies to determine the dependence of dielectric constant, dielectric loss tangent and dielectric strength on these parameters.

The present work investigates the effect of carbon nanotube (CNT) inclusions on the electrical and thermal conductivity of a thermoset epoxy resin. The characterization of electrical and thermal conductivity of CNT/epoxy composites is presented. Pristine, oxidized, and fluorine-functionalized unpurified CNT mixtures ("XD grade") were dispersed in an epoxy matrix, and the effect of stirring rate and pre-curing of the epoxy on the dispersion of the CNTs was evaluated. In order to characterize the dispersion of the CNTs at different length scales, Optical Microscopy (OM), Raman Spectroscopy, and Scanning Electron Microscopy (SEM) was performed. Samples of varying CNT weight fractions were fabricated in order to find the effect of CNT weight fraction on thermal and electrical conductivity. Electrical conductivity was measured using a dielectric spectrometer, and thermal conductivity was determined by a transient plane source thermal analyzer. It was found that electrical conductivity increases by orders of magnitude for the pristine and oxidized XD CNT composites relative to the neat epoxy matrix, while fluorinated XD CNT composites remain electrically non-conductive. A small, but significant, increase in thermal conductivity was observed for pristine, oxidized, and fluorinated XD CNT composites, showing a linear increase in thermal conductivity with increasing CNT weight fraction. Pristine XD CNTs were ball-milled for different times in order to reduce the degree of agglomeration and entanglement of CNTs, and composites were fabricated using the same technique as with non-milled XD CNTs. Using ball-milled CNTs shows improved dispersion but results in an electrically non-conductive composite at the CNT weight fractions tested. The thermal conductivity of the ball-milled CNT samples shows an initial increase higher than that of non-milled pristine, oxidized, and fluorinated XD CNTs, but remains constant with increasing CNT weight fraction. A micromechanics model based on the composite cylinders method was implemented to model the electrical and thermal conductivity of the CNT/epoxy composites. Nanoscale effects in electrical and thermal conduction, such as electron hopping and interface thermal resistance, respectively, were incorporated into the model in order to accurately predict the acquired results. Modeling results show good agreement with acquired experimental results.

In 2007 the production of expanded polystyrene (EPS) in the world was over 4 million tonnes and is expected to grow at 6 percent per year. With the increased concern about environmental protection, alternative biodegradable materials from renewable resources are of interest. The present doctoral thesis work successfully demonstrates that starch-based foams with mechanical properties similar to EPS can be obtained by reinforcing the cell-walls in the foams with cellulose nanofibers (MFC). High cellulose nanofiber content nanocomposites with a highly plasticized (50/50) glycerol-amylopectin starch matrix are successfully prepared by solvent-casting due to the high compatibility between starch and MFC. At 70 wt% MFC, the nanocomposites show a remarkable combination of high tensile strength, modulus and strain to failure, and consequently very high work to fracture. The interesting combination of properties are due to good dispersion of nanofibers, the MFC network, nanofiber and matrix properties and favorable nanofiber-matrix interaction. The moisture sorption kinetics (30% RH) in glycerol plasticized and pure amylopectin film reinforced with cellulose nanofibers must be modeled using a moisture concentration-dependent diffusivity in most cases. The presence of cellulose nanofibers has a strong reducing effect on the moisture diffusivity. The decrease in zero-concentration diffusivity with increasing nanofiber content could be due to geometrical impedance, strong starch-MFC molecular interaction and constrained swelling due to the cellulose nanofiber network present. Novel biomimetic starch-based nanocomposite foams with MFC contents up to 40 wt% are successfully prepared by freeze-drying. The hierarchically structured nanocomposite foams show significant increase in mechanical properties in compression compared to neat starch foam. Still, better control of the cell structure could further improve the mechanical properties. The effect of cell wall composition, freeze-drying temperature and freezing temperature on the resulting cell structure are therefore investigated. The freeze-drying temperature is critical in order to avoid cell structure collapse. By changing the starch content, the cell size, anisotropy ratio and ratio between open and closed cells can be altered. A decrease in freezing temperature decreases the cell size and increases the anisotropy ratio. Finally, mechanical properties obtained in compression for a 30 wt% MFC foam prepared by freeze-drying demonstrates comparable properties (Young's modulus and yield strength) to expanded polystyrene at 50% RH and similar relative density. This is due to the reinforcing cellulose nanofiber network within the cell walls. / QC 20100913