This thesis deals with the diffusion of ions in compactedbentonite clay. Laboratory experiments were performed toexamine in detail different processes that affect thediffusion. To demonstrate that the results obtained from thelaboratory investigations are valid under in situ conditions,two different kinds of in situ experiments were performed. Laboratory experiments were performed to better understandthe impact of ionic strength on the diffusion of Sr2+ and Cs+ions, which sorb to mineral surfaces primarily by ion exchange.Furthermore, surface related diffusion was examined anddemonstrated to take place for Sr2+ and Cs+ but not for Co2+,which sorbs on mineral surfaces by complexation. The diffusion of anions in bentonite clay compacted todifferent dry densities was also investigated. The resultsindicate that anion diffusion in bentonite clay consists of twoprocesses, one fast and another slower. We ascribe the fastdiffusive process to intralayer diffusion and the slow processto diffusion in interparticle water, where anions are to someextent sorbed to edge sites of the montmorillonite. Two different types of in situ experiments were performed,CHEMLAB and LOT. CHEMLAB is a borehole laboratory, where cation(Cs+, Sr2+ and Co2+) and anion (I- and TcO4-) diffusionexperiments were performed using groundwater from a fracture inthe borehole. In the LOT experiments cylindrical bentoniteblocks surrounding a central copper rod were placed in a 4 mdeep vertical borehole. The borehole was then sealed and theblocks are left for 1, 5 or>>5 years. When the bentonitewas water saturated the central copper rod is heated tosimulate the temperature increase due to radioactive decay ofthe spent fuel. Bentonite doped with radioactive Cs and Co wasplaced in one of the lower blocks. Interestingly, the redox-sensitive pertechnetate ion (TcO4-)which thermodynamically should be reduced and precipitate asTcO2·nH2O, travelled unreduced through the bentonite.However, at some spots in the clay, the Tc activity wasconsiderably higher. We ascribe these activity peaks toiron-containing minerals in the bentonite, by which Tc(VII) hasbeen reduced to Tc(IV) and precipitated. The cations Sr2+, Cs+and Co2+, as well as the anion I-, behaved in the CHEMLABexperiments as expected from laboratory studies. Three experiments in the LOT series are completed. The firsttwo diffusion experiments in LOT were less successful, thefirst due to the fact that saturation of the bentonite was notobtained during the experimental period and the radionuclidesdid not move at all. In the second, the uptake of the bentoniteparcel was less successful. Water from the drilling flushedaway large pieces of the top part of the bentonite and thelower part of the test parcel was super-saturated with waterand expanded when released from the rock. The activity distribution in the second experiment wasanalysed. The Co2+ profile looked as we had expected, while Cs+had spread more than our calculations indicated. However, thethird experiment was successful from emplacement, watersaturation and heating to uptake. The activity distribution forboth cations was as expected from laboratory studies. Altogether the three different types of experiments give auniform picture of radionuclide diffusion in bentonite clay forthe ions investigated. / QC 20100621

With growing environmental concerns, efforts are made to replace petroleum based products with renewable alternatives. This is particularly evident in the packaging industry, where replacing synthetic polymers with renewable materials is of considerable interest. Materials for food packaging need to give protection, acting as a barrier against substances that can adversely affect the food quality such as water and oxygen. In this work, barrier dispersion coatings based on starch were used to produce coated papers which act as barrier against water and oxygen. However, since starch is both a hydrophilic and hygroscopic material, this barrier material becomes problematic to use at high relative humidity. In order to reduce this problem and improve the barrier properties enabling starch based barrier materials to be used in food packaging applications, two approaches were studied. Citric acid was utilized as a cross-linker of the starch and it was found to reduce the moisture sorption, the molecular movement and swelling at high relative humidity. It was seen that cross-linking and hydrolysis due to the low pH both affected the barrier properties significantly, but in opposing directions. By controlling these two reactions it was seen that this could lead to reduced gas permeability. It was also seen that cross-linking of starch by citric acid occurs at low temperatures, 70 °C at pH as high as 6.5. Starch nano-composites were produced by incorporating montmorillonite, to the barrier dispersion to improve the barrier properties. It was seen that the suspension viscosity was reduced by poly(ethylene glycol) and citric acid adsorption on the montmorillonite particles. Also, a tendency for improved barrier properties with reduced aggregate volume fraction and reduced swelling was observed. It was also seen that up scaling this formulation to pilot scale was possible and that promising results were achieved. / Baksidestext With growing environmental concerns, efforts are made to replace petroleum based materials with renewable alternatives such as starch. In this work, dispersions based on starch were used to produce coated papers which act as barrier against substances that can adversely affect the food quality such as water and oxygen. However, since starch is both a hydrophilic and hygroscopic material, this barrier material becomes problematic to use at high relative humidity. Citric acid was utilized as cross-linker for starch and it was found to reduce the moisture sorption, diffusion and swelling at high relative humidity. Both cross-linking and hydrolysis due to the low pH affected the barrier properties significantly, but in opposing directions. By controlling these two reactions it was possible to achieve reduced gas permeability. Starch nano-composites were produced by incorporating montmorillonite clay, to the barrier dispersion. It was seen that the suspension viscosity was reduced by poly(ethylene glycol) and citric acid adsorption on the clay. Also, a tendency for improved barrier properties with reduced aggregate volume fraction and reduced swelling was observed. It was also seen that up scaling this formulation to pilot scale was possible and promising results were achieved. / Renewable Functional Barriers

In this study, polythiophene(PTP)/montmorillonite(MMT) nanocomposites were synthesized by in situ intercalative polymerization and chemical oxidative polymerization. In in situ intercalative polymerization method, composites containing 90 and 95% MMT were prepared. In chemical oxidative polymerization method, a series of composites ranging from 1 to 15% by weight MMT were synthesized. Thermal and morphological properties of samples were investigated by Differential Scanning Calorimeter (DSC), Thermal Gravimetric Analysis (TGA), X-ray Diffraction (XRD) and Scanning Electron Microscope (SEM) / electrical conductivities were measured by four probe technique. Since PTP/MMT composites are unprocessable PTP/polypropylene(PP) composites were prepared. Amounts of PTP were changed in the range 2-30 % by weight in the composites. Mechanical properties were investigated by tensile tests. Four probe technique was used for measurement of electrical conductivities. Morphological characterizations were made by SEM. Formation of PTP and its incorporation in PTP/MMT composite were confirmed by FTIR analysis. DSC results showed that PTP does not have any thermal transition in the range 25-300 0C. TGA results showed that PTP/MMT composites have outstanding stability compared to that of PTP. XRD analysis revealed the formation of nanocomposites resulting from intercalation of thiophene in MMT at high MMT contents. Composites were observed as globular particles and clusters in SEM studies. Conductivity values of PTP/MMT composites were in the order of 10-3 S/cm. It is observed that tensile modulus of PTP/PP composites increases by the addition of PTP, but percentage strain at break does not appreciably change. Increasing PTP content increased electrical conductivity.

The effects of melt state compounding and addition order of ethylene-butyl acrylate-maleic anhydride (E-BA-MAH), ethylene-glycidyl methacrylate (E-GMA), ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and/or three types of organoclays (Cloisite&reg / 15A, 25A and 30B) on morphology, thermal, mechanical and dynamic mechanical properties of polyamide-6 are investigated. XRD patterns show that the interlayer spacing for Cloisite&reg / 15A remained unchanged / however it increased for the organoclays Cloisite&reg / 25A and Cloisite&reg / 30B in both polyamide-6/organoclay binary nanocomposites and in polyamide-6/organoclay/impact modifier ternary systems. TEM analyses indicate that exfoliated-intercalated nanocomposites are formed. Sizes of elastomeric domains in nanocomposites are larger than the domains in their corresponding blends. The MFI results show that incorporation of elastomer reduces the MFI, due to the formation of graft copolymer. Both storage and loss moduli and complex viscosity of polyamide-6 increase with organoclay addition. In DMA measurements, in rubbery region, all nanocomposites show higher storage modulus than the unfilled counterparts. In general, the organoclays increase tensile and flexural strength, Young&amp / #8217 / s and flexural modulus and elongation at break, but decrease the impact strength, on the contrary, the addition of elastomer has the opposite effect. Generally, Cloisite&reg / 15A containing ternary nanocomposites have higher tensile, flexural and impact strength and Young&amp / #8217 / s and flexural modulus than the ternary nanocomposites prepared with Cloisite&reg / 25A and Cloisite&reg / 30B. In general, nanocomposites processed by adding all the ingredients simultaneously give higher tensile and flexural strength and modulus than the nanocomposites produced by other mixing sequences.

In this study, organo-montmorillonite (OMMT) nanocomposites containing 1%, 5%, 10% and 15% OMMT were prepared by in situ intercalative oxidative polymerization of pyrrole in the presence of OMMT. Thermal and morphological properties of the Polypyrrole(PPy)/OMMT nanocomposites were investigated by Thermal Gravimetric Analysis (TGA), X-ray Diffraction Analysis (XRD) and Scanning Electron Microscope (SEM). Electrical conductivities of composites were measured by four probe technique. Formation of PPy and its incorporation in PPy/OMMT composites were confirmed by FTIR analysis. TGA results showed that PPy/OMMT composites have outstanding thermal stability compared to that of PPy. XRD analysis revealed intercalation of PPy in the OMMT lamelles. Scanning electron micrographs demonstrated that the morphology of the PPy/OMMT nanocomposites differ slightly from that of the clay, since the modification of PPy was not significant in flaky structure of OMMT nanoparticles. Conductivity values of PPy/OMMT composites were found in the order of 10-3S/cm. Since PPy has poor processibility, Polypropylene(PP)/PPy composites were prepared in the composition range of 2-20 % PPy. Mechanical properties were investigated by tensile tests. Electrical conductivities were measured by four probe technique. Morphological characterizations were made by SEM. Young&amp / #8217 / s Modulus of PPy/PP composites increased with increasing PPy content, and addition of 2 wt % PPy to PP resulted in a dramatic decrease in the tensile strain at break of the material. Also by addition of 2 wt % PPy to PP, the tensile strength of material decreased and further increase in PPy content, tensile strength increased. Furthermore, an increase in the PPy content in PPy/PP composites resulted in an increase in conductivity. SEM micrographs revealed that as the PPy loading increases from 10% to 20% in composite system, adhered PPy particles by PP matrix were driven out of PP matrix while PP matrix oriented along the draw direction during tensile test.

Polymer-clay nanocomposites have received a lot of attention because of outstanding improvements in properties when compared with neat polymeric materials. The aim of this study was to prepare epoxy-clay nanocomposites by mixing organically modified montmorillonite with an epoxy resin and to investigate the effects of clay content on the mechanical, thermal and flammability properties of the resultant nanocomposites. The production of the epoxy-clay nanocomposites was accomplished by in-situ polymerization. In the nanocomposite synthesis, organically modified clay content was varied from 1 wt.% to 9 wt.%. Araldite LY556 epoxy resin, Aradur 918 anhydride hardener, and DY070 imidazole type accelerator were used in the epoxy system. Closite 30B, an organoclay modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH), was used as the clay material. X-ray diffraction results showed that d-spacing between the platelets of organoclay increased from 1.80 nm to 4.4 nm. The microstructures of nanocomposites were investigated by scanning electron microscopy (SEM). The SEM micrographs indicated that at 1 wt.% clay loading, no clay aggregates were observed. On the other hand, beyond 1 wt.% clay loading, formation of clay agglomerations was observed. Tensile strength and tensile strain values of nanocomposites decreased with clay loading. The tensile strength value of neat epoxy resin decreased from 55 MPa to 29 MPa with 9 % clay loading. On the other hand, Young&amp / #8217 / s modulus increased with clay content and a maximum value was obtained at 5 wt. % clay loading. At 9 % clay loading, Young&amp / #8217 / s modulus value was 26 % higher than that of the neat epoxy resin. Impact strength property had a minimum value at 7 wt. % clay content. Flexural strength and flexural strain at break property behaved in a similar trend. They had a minimum value at 5 % clay loading. At this clay loading, flexural strength value became approximately 43 % lower compared to the flexural strength of the neat epoxy resin. On the other hand, at 9 wt.% clay loading flexural modulus value increased approximately 48 % compared to the pure epoxy resin. Up to 7 wt.% clay ratio, initial decomposition temperature of epoxy resin was slightly improved. Also, according to TGA results, amount of char formation increased with clay loading. DSC results indicate that Tg of the cured nanocomposite resins decreased from 147 oC to 129 oC with 9 wt. % clay loading. The flammability of neat epoxy resin was not significantly affected with Cloisite 30B addition.

In 1986, geosynthetic clay liners (GCLs) were invented and successfully used as a replacement for the soil layer in composite lining systems. In some applications an additive (polymer) is mixed with the bentonite to increase performance, especially in those that have low concentrations of sodium bentonite (EPA 2001).Studies showing significant increases in hydraulic conductivity values for bentonite in the presence of high salt concentrations are frequently documented and there is a risk of early breakthrough due to performance failure of the GCL clay component. (Ashmawy et al, 2002). It has also been stated that sodium, potassium, calcium, and magnesium have such a high affinity for the clay's surface other chemical species have little chance of attenuation (EPA 2001). For these reasons, researching sorption in the presence of major salt cations and polymers gains great importance.Distribution coefficients were extrapolated from Linear, Freundlich and Langmuir sorption isotherms for sodium and calcium cations modeled from data collected from batch tests of sodium bentonite and various manufactured and custom mixed polymer modified bentonites. Surface characterization before and after calcium or sodium solution exposure of all tested media was accomplished by use of scanning electron microscopy and energy dispersive x-ray analysis.

Because of its low permeability and high swelling characteristics, bentonite is used in various hydraulic barrier systems and in the manufacturing of Geosynthetic Clay Liners (GCLs). Exposure to inorganic solutions containing elevated concentrations of electrolyte can significantly increase their permeability. To enhance the bentonite's chemical resistance to inorganic solutions, the manufacturers of GCL materials introduced propriety soluble polymeric compounds as an additive to bentonite. The resulting materials are referred to as polymer-treated, chemically-enhanced, or contaminant-resistant clays, and are arguably resistant to a host of inorganic chemicals. In this study, the response of both regular and polymer treated bentonite clays to ordinary tap water and inorganic landfill leachate is evaluated using permeability tests, index tests and x-ray diffraction. The results indicate the high dependence of performance on sample preparation techniques, pre-hydration conditions, and first wetting liquid and, to a lesser extent, polymer treatment. The x-ray diffraction results indicate that the samples reached chemical equilibrium during the permeation process, as demonstrated by a full shift in d-spacing from Na-bentonite to Ca-bentonite. Further, the results show that the cation exchange capacity, the clay plasticity ratio, and the swell index appear to be reliable indicators of the hydraulic compatibility of bentonite permeated with inorganic chemicals

In this study, the effects of chain extension and branching on the properties of nanocomposites produced from recycled poly(ethylene terephthalate) and organically modified clay were investigated. As the chain extension/branching agent, maleic anhydride (MA) and pyromellitic dianhydride (PMDA) were used. The nanocomposites were prepared by twin-screw extrusion, followed by injection molding. Recycled poly(ethylene terephthalate), was mixed with 2, 3 and 4 weight % of organically modified montmorillonite. During the second extrusion step, 0.5, 0.75 or 1 weight % of MA or PMDA was added to the products of the first extrusion. As the second extrusion step is reactive extrusion, the anhydrides were added at three different screw speeds of 75, 150, 350 rpm, in order to observe the change of properties with the screw speed. XRD analysis showed that, the interlayer spacing of Cloisite 25A expanded from 19.21 &amp / #506 / to about 28-34 &amp / #506 / after processing with polymer indicating an intercalated structure. PMDA, MA and organoclay content as well as the screw speed did not have a recognizable effect on interlayer distance. In the first extrusion step, nanocomposites containing 3% organoclay content gave significant increase in Young&rsquo / s modulus and decrease in elongation to break values indicating good interfacial adhesion. After the addition of chain extenders, it was observed that both MA and PMDA gave rise to improved mechanical properties of the nanocomposite owing to the branching and chain extending effects that increase the molecular weight. However, PMDA gave better mechanical properties at lower content which makes it a more effective chain extender. DSC analysis showed that MA was more effective in increasing the glass transition temperature and melting temperature in comparison to PMDA.

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).