Polymeric composites are any of the combinations or compositions that comprise two or more materials as separate phases, at least one of which is a polymer. By mixing a polymer with another material, such as glass, carbon, or another polymer, it is often possible to improve the desired properties of the polymer. In this study, ternary composites were prepared by using recycled poly(ethylene terephthalate), PET as the matrix material, short glass fiber (SGF) as the reinforcing filler and thermoplastic elastomer as the impact modifier. Bottle grade recycled PET was mixed in a twin screw extruder with a thermoplastic elastomer which is a terpolymer of ethylene/methyl acrylate/glycidyl methacrylate (E-MA-GMA), and E type short glass fiber is fed to the extruder from a side feeder. During this study, recycled PET was mixed with from 10 to 50 wt. % elastomer, and SGF was added to the system in the range from 10 to 40 % by weight. Processing parameters were kept constant during extrusion. The composites were then compression molded for characterization experiments. The produced composites were characterized in terms of their mechanical and thermal properties and morphologies. Melt behavior and fiber length distribution of the composites were also determined for selected composites. In ternary systems with 10 % elastomer, highest tensile strength values were observed. High tensile and flexural moduli values were obtained for the composites containing 20 % elastomer. Results of impact tests designated that impact strength increased significantly after 30 % elastomer content. Thermal analyses of the composites were done by using a DSC (Differential Scanning Calorimeter). Degree of crystallinity of ternary system decreased with increasing elastomer content, but melting points of the composites were not affected significantly. SEM micrographs showed that the adhesion between the matrix and fiber increased considerably with elastomer addition.

In this study, the thermal and mechanical properties of poly(ethylenetheraphthalate) (PET)-thermotropic liquid crystal polyester (TLCP), mixtures and poly(methyl methacrylate) (PMMA)-TLCP mixtures were studied. The curing of PMMA-TLCP mixtures was done by heat, gamma radiation and microwave. The amount of TLCP in mixtures was % 0.5, 2 and 5 TLCP by weight. TLCP was synthesized by melt-acidolysis system, and PET-TLCP mixtures were prepared by using lab scale batch mixer. PMMA samples were prepared according to denture manufacturer&rsquo / s procedure. The characterization of polymer samples and mixtures were carried by FT-IR, NMR, DSC, DMA, tensile, impact, three point bending tests and light microscopy. The mixing of TLCP with PMMA yielded heterogeneous dispersions. This was observed from light micrographs. The mechanical and rheological properties of all polymers were not positively affected by inclusion of TLCP. It is also worthwhile to note that weakening of PET-TLCP mixtures were due to the thermal degradation as the thermal age of the mixtures is much higher.

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 organoclay loading, compatibilizer loading and polyethylene type on the morphology, rheology, thermal properties and mechanical properties of polyethylene/compatibilizer/organoclay nanocomposites were investigated. As compatibilizer, terpolymer of ethylene-methacrylate-glycidyl methacrylate (Lotader&reg / AX8900), as organoclay Cloisite&reg / 15A were used. All samples were prepared by a co-rotating twin screw extruder, followed by injection molding. Considering ternary nanocomposites, highest impact strength results were obtained with 10% compatibilizer plus 2% organoclay / highest yield stress, elastic modulus, flexural strength, flexural modulus were obtained with 5% compatibilizer plus 4-6% organoclay. DSC data indicated that addition of organoclay and compatibilizer did not change the melting point remarkably / on the other hand it affected the crystallinity. The organoclay used had no nucleation effect on polyethylene, and the compatibilizer decreased the crystallinity of the matrix. X-ray diffraction showed that in all ternary nanocomposites and in binary nanocomposite of high density polyethylene with organoclay, layer separation associated with intercalation of the clay structure occurred,. The highest increase of interlayer gallery spacing was obtained with 10% compatibilizer plus 2% organoclay, which were 25%, 28% and 27% for HDPE, LLDPE and LDPE matrices respectively.

The thermal conductivities of foamed polymer based materials are much lower thermal conductivity values than unfoamed polymeric materials. Especially, thermal conductivity values of foamed polymers with closed-cell structure decreases to 0.03 W/m.K. The reinforcement of foamed polymeric materials by mixing with bitumen lowers the raw material cost. The main objective of this study is to make a new thermal insulation material with low thermal conductance. In this study, the effects of concentration of calcium carbonate as inorganic filler and the effects of cross-linking on the properties foamed and unfoamed ethylene-vinyl acetate (EVA) copolymer based bituminous blends and composites were investigated. Applications such as thermal, mechanical characteristics of foamed and unfoamed EVA based bituminous composites were investigated. Foamed EVA based bituminous composites were prepared by using Brabender Plastic Coder, PLV 151. Mixing was made at 120 &ordm / C at 60 rpm for 15 minutes. The prepared blends were molded by a technique called Hand Lay-up Self-expanding Batch Molding (HLUSEBM) which was firstly applied by our group. The molding temperature was 170 &ordm / C at which chemical blowing agent and cross-linking agent decomposes. According to test results, at moderate chemical blowing agent and EVA content, the best closed-cell structure with high porosity and low thermal conductivity values were obtained. The compressive properties of foamed polymer based bituminous composites (FPBBCs) increase with increasing CBA and EVA content. With increasing calcium carbonate and EVA concentration, the porosity of FPBBCs increases but thermal conductivity of them decreases. On the other hand, with increasing filler content but with decreasing EVA concentration elastic modulus of FPBBCs increases but elastic recovery decreases.

For the aim of production of poly(ethylene terephthalate), PET based flame retardant composites / boron based flame retardant additives, 3.5 mole hydrated zinc borate and boron phosphate were synthesized. Zinc borate was synthesized with the reaction of boric acid and zinc oxide in both laboratory and pilot scale reactors. Effects of reaction parameters on kinetics of reaction and final product particle size were evaluated. Boron phosphate was synthesized via dry, wet and microwave methods. In addition to the synthesized flame retardant additives, several non-halogenated flame retardant additives, which were commercially available, were also used. Composites were prepared using twin screw extruder and molded by injection molding, followed by characterization in terms of flame retardancy behavior, mechanical and thermal properties, and morphologies. Based on the results of first stage experiments, aiming to determine effective additives, different amounts and combinations of triphenyl phosphate, triphenyl phosphine oxide, zinc borate and microwave produced boron phosphate were chosen and used in PET matrix. Flame retardancy of the composites were determined by conducting horizontal burning rate and limiting oxygen index (LOI) tests. Smoke emissions during fire were also measured. According to the LOI test results, LOI of neat PET was determined as 21%, and with the addition of 5% boron phosphate and 5% triphenyl phosphate together, LOI was increased up to 36%. The smoke density analysis results implied that, boron phosphate was a successful smoke suppressant for PET matrix. In addition to flammability properties, tensile and impact properties of the composites were also improved with flame retardant additives and expecially with the addition of triphenyl phosphate.

The impact strength of Nylon 6 was improved by adding Ethylene- n-Butyl acrylate- maleic anhydride (E-nBA-MAH) terpolymer with various concentrations from 0% (w/w) to 15% (w/w). The bare interaction energy between two polymers was investigated by using melting point depression approach utilizing both the Flory-Huggins (FH) theory and the Sanchez-Lacombe Equation of State (SL EOS). The solution of the mixture was electrospun, and the effects of process parameters on the expected radii of nanofibers were investigated. The effects of process parameters such as polymer concentration in solution, electrical field, diameter of syringe needle, feed rate, and collector geometry on nanofibers were studied. The statistical analysis to relate these parameters on the diameter of nanofibers was carried out by using Johnson SB distribution. The ratio of elastic modulus to viscosity coefficient of nanofibers was worked out by using AFM and combined viscoelastic models. The experiments were carried out on single fiber. The ratio came out to be a function of nanofiber diameter and terpolymer concentration. Isothermal crystallization kinetics and WAXS diffraction patterns of blends revealed and also SEM images supported that after 5% addition of elastomeric terpolymer, the interaction between the components of the blend gets weaker. The elastic modulus of the blend with 5% of terpoymer was greater than that of the neat Nylon 6, but the elastic modulus decreased for the blends containing more than 5% terpolymer.

The present study was aimed at exploring the purification and modification of montmorillonite rich Turkish bentonites by organic salts and their subsequent effects on the morphology (X-diffractometry, transmission electron microscopy, scanning electron microscopy), melt flow index, mechanical (Tensile, Impact) and especially thermal stability (thermal gravimetric analysis, differential scanning calorimetry) properties of polymer/organoclay nanocomposites with and without an elastomeric compatibilizer. The bentonite clay mined from Resadiye (Tokat/Turkey) was purified by sedimentation, resulting in higher cation exchange capacity and thermal stability in comparison to unpurified clay, and then used in the synthesis of six thermally stable organoclays by replacing the interlayer inorganic sodium cations with two (alkyl, aryl) phosphonium and four di-(alkyl, aryl) imidazolium surfactant cations in an attempt to overcome the problem of early decomposition of alkyl ammonium organoclays usually used in polymer nanocomposites. An optimum amount of these organoclays (wt %2) was then used in the production of Polyamide 66 and Poly(ethylene terephthalate) based nanocomposites by melt blending with the help of an optimum amount of elastomeric compatibilizer (wt %5) which also acted as impact modifier. Phosphonium organoclays were used in the production of nanocomposites for both polymers, whereas imidazolium organoclays were used with PET only. The importance of clay purification was revealed in the removal of non-clay minerals available in the raw bentonite clay as confirmed by XRF and XRD, the significant increase in cation exchange capacity and the improved thermal stability of the purified clays as proven by TGA. The interlayer spacing of the phosphonium organoclays ranged from 1.78 to 2.52 nm indicating arrangement between pseudo-trilayers and paraffin-type chains, while the interlayer spacing of imidazolium organoclays ranged between 1.35 nm and 1.45 nm indicating a monolayer arrangement. The effects of chemical structure (chain type), counter ion and alkyl chain length on the thermal stability of the imidazolium salts were investigated. TGA analysis showed that the thermal stability of (alkyl, aryl) phosphonium and di-(alkyl, aryl) imidazolium organoclays proved to be superior to conventionally used quaternary alkyl ammonium organoclays. Not only the thermal stability of the organoclays prevented the nanocomposite from early decomposition, but these organoclays also improved the onset decomposition temperatures of PA66 and PET nanocomposites compared to the pure polymer owing to the dominant barrier effect of the silicate layers as a result of the formation of carbonaceous-silicate char. The reinforcement of PA66 with surface modified phosphonium organoclays and PET with surface modified phosphonium and imidazolium organoclays enhanced the mechanical and thermal properties of the binary and ternary nanocomposites. The mechanical properties were in good agreement with DSC analysis for all the PA66 and PET compositions. The presence of elastomer and organoclays promoted the nucleation process in PA66 blend, binary and ternary nanocomposites. However, the presence of elastomer and organoclay retarded the nucleation in most of the PET composites.

The objectives of this study are to synthesize poly(dimethylsilane) (PDMS) preceramic polymer and to investigate its effect on morphology, flame retardant and mechanical properties of polypropylene (PP) based composites. There are mainly two parts in this thesis. In the first part, PDMS was synthesized by electrochemical polymerization of dichlorodimethylsilane, which was dissolved in 1,2 dimethoxyethane (DME) solvent consisting of tetrabutyl ammonium perchlorate (TBAP), as supporting electrolyte. PDMS was obtained in powder form and characterized with Fourier transform infrared, ultraviolet-visible and proton nuclear magnetic resonance spectroscopic analyses, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Since PDMS has some impurities coming from TBAP and DME, alternatively, the PDMS synthesis was done by electrochemical reduction of dichlorodimethylsilane without using solvent and/or supporting electrolyte for seven days. PDMS was produced as pure and characterized with the same methods used for previous synthesis. In the second part of this thesis, PP based composites with additives were prepared by using a twin-screw extruder and injection molding machine and were characterized with limiting oxygen index (LOI), horizontal burning, TGA, differential scanning calorimetry (DSC), tensile and impact tests and SEM analysis. Triphenyl phosphate, boron phosphate, magnesium hydroxide, intumescent flame retardants (IFR) (melamine phosphate (MP) and pentaerythritol (PER)), antimony trioxide and poly(methylsilsesquioxane) were additives used in this study other than PDMS. According to LOI test results, the highest LOI value among the PDMS composites was obtained in 1% PDMS, 14.25% MP and 4.75% PER (w/w) containing composite as 24%, whereas the LOI value of neat PP was measured as 17.5%. It was determined that elastic moduli of all the composites studied were higher than neat PP.

Glass fiber reinforced poly(ethylene terephthalate), GF/PET has excellent potential for future structural applications of composite materials. PET as a semi-crystalline thermoplastic polyester has high wear resistance, low coefficient of friction, high flexural modulus and superior dimensional stability make it a versatile material for designing mechanical and electromechanical parts. Glass fibers are currently used as strength giving material in structural composites because of their high strength and high performance capabilities. In order to obtain high interfacial adhesion between glass fiber and polymer, glass fibers are treated with silane coupling agents. The objective of this study is to produce GF/PET composites with varying glass fiber concentration at constant process parameters in a twin screw extruder. Also, by keeping GF content constant, it is aimed to observe the effects of process parameters such as screw speed and feed rate on structural properties of the composites. Another objective of the study is to investigate the influence of different coupling agents on the morphological, thermal and mechanical properties and on fiber length distributions of the composites. Tensile strength and tensile moduli of the GF/PET composites increased with increasing GF loading. There was not a direct relation between strain at break values and GF content. The interfacial adhesion between glass fiber received from the manufacturer and PET was good as observed in the SEM photograps. Degree of crystallinity values increased with the addition of GF. Increasing the screw speed did not affect the tensile strength of the material significantly. While increasing the feed rate the tensile strength decreased. The coupling agent, 3-APME which has less effective functional groups than the others showed poor adhesion between glass fiber and PET. Therefore, lower tensile properties were obtained for the composite with 3-APME than those of other silane coupling agents treated composites. Number average fiber length values were reduced to approximately 300&amp / #61549 / m for almost all composites prepared in this study.