Dissertations / Theses on the topic 'Organoclay'

This thesis looks at the study of nanocomposites of Poly(ethylene terephthalate) and organoclays. Two methods of materials blending are investigated for the production of the nanocomposites: solvent blending and melt blending. The main objectives were the investigation of the influence of organoclays and processing conditions on morphological, rheological, mechanical properties, crystal structure and isothermal crystallization kinetics of the nanocomposite and a comparison with unfilled PET. In solvent blending, the use of long sonication time and epoxy led to the formation of a two-dimensional network structure of long, thin particles in a solvent blended PET nanocomposite at low clay loading. The clay network structure seemed not to affect the tensile properties. The long, thin particles were able to be separated and dispersed further by high shear in a twin screw extruder, resulting in a high level of separation and dispersion. The crystallization of the solvent blended nanocomposite was not only influenced by the nanoclay but also by the residual solvent. The extent of clay dispersion did not affect the crystallization of the solvent blended sample. Both solvent blended and melt blended nanocomposites showed that increasing the amount of surfactant improved the degree of nanoclay dispersion in the PET that led to an enhancement in the tensile properties of the nanocomposite compared to the unfilled polymer. The degradation of the organoclay during melt blending did not limit the nanoclay dispersion in the PET. The low thermal stability of the organoclay reduced the strength of the crystalline nanocomposite but it did not affect the strength of the amorphous nanocomposite. In contrast to the solvent blended sample, the extent of clay dispersion influenced the crystallization of the melt blended sample. The poorly dispersed particles were more efficient in nucleating PET crystallization than the well dispersed particles. The crystallization rate of PET increased as the surfactant concentration decreased.

Natural rubber (NR)/organoclay nanocomposites were prepared using organomontmorillonite (OMMT) and organo-sepiolite (OSEP). Both were found to improve modulus significantly more than equivalent amounts of conventional fillers such as carbon black for strains up to 100%. OSEP was found to increase modulus more than OMMT for a given filler content, and NR/OSEP nanocomposites also had potentially anisotropic physical properties. OMMT had more effect on vulcanisation than OSEP, although both produced considerable acceleration. The tensile stress-strain behaviour of NR/OMMT and NR/OSEP nanocomposites were studied using a number of different micromechanical models. Some models were found to give a good empirical fit with experimental data, with the best results given by the Halpin-Tsai model. Furthermore, by analysis of the vulcanisation behaviour using rheometry, and particle morphology using transmission electron microscopy (TEM), it was possible to accurately estimate the Young's modulus of a nanocomposite from knowledge of the cure onset time and the shape factor of the particles. It was discovered that unmodified montmorillonite and sepiolite clays could undergo organic modi cation in situ during mixing into NR following the addition of a suitable modifier. This resulted in vulcanisates with very similar physical properties to those found when using pre-modified OMMT or OSEP. TEM and X-ray diffraction showed that the exfoliation state of the clay modified in situ was also similar to that of pre-modified organoclay. Silane coupling agents were also used with NR/OMMT and NR/OSEP nanocomposites, producing significant increases in modulus. However, the increased modulus was only observed above 40% strain for OMMT and above 25% for OSEP. The coupling agents strengthens the rubber- ller interface preventing interfacial slippage and cavitation in the nanocomposite, and these mechanisms only begin to operate when the interfacial stress reaches a significant level. The most effective coupling agent used was bis[triethoxysilylpropyl] tetrasulfide due to its relatively high reactivity.

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®
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®
15A remained unchanged
however it increased for the organoclays Cloisite®
25A and Cloisite®
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&
#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®
15A containing ternary nanocomposites have higher tensile, flexural and impact strength and Young&
#8217
s and flexural modulus than the ternary nanocomposites prepared with Cloisite®
25A and Cloisite®
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.

A series of polyurethane (PU)-organoclay nanocompositcs were synthcsised by swelling organically-modified layered silicate (organoclay) in a polyol with subsequent polymerisation. The techniques of wide-angle x-ray diffraction (WAXD), small-angle x-ray scattering (SAXS), transmission electronic microscopy (TEM), scanning electronic microscopy (SEM), Fourier transform infer-red spectroscopy (FTIR), modulated differential scanning calorimetry (MDSQ, contact angle measurement and tensile test were used to investigate the effect of addition of organoclay on curing dynamics, phase structure, tensile properties, dynamical mechanical thermal analysis (DMTA), fatigue durability and surface properties of PUs. FTIR and MDSC revealed that the addition of organoclay has an important influence on curing process of PUs. With increasing organoclay, the reaction between -OH group in polyol and- NCO in isocyanate became fast. WAXD and TEM results showed that PU-organoclay nanocomposites prepared in this research were intercalated materials ones. The addition of organoclay has significant influences on the phase structure of PUs. SAXS results revealed that the long period (average thickness of soft and hard segment) decreased with increasing organoclay. Contact angle measurements showed that the organoclay can affect the surface properties of PU nanocomposites. The addition of organoclay resulted in the decrease in surface energy. AFM results revealed that the adhesion force of the surface of PU nanocomposites decreased with increasing organoclay. Tensile strength and elongation of PUs at break were improved significantly by incorporating organoclay. The tensile strength increased up to 100%, and elongation increased up to 120%. At high soft segment content, with increasing organoclay, the modulus decreased slightly, and at low soft segment content, the modulus increased with increasing organoclay. The addition of organoclay improved significantly thermal stability of PUs. Fatigue measurements uggestedt hat the fatigue durability can significantly be improved by incorporating organoclay. A nanospring concept for understanding the enhancemenht as been proposed.

PA 66 nanocomposites and PA 66 blends were prepared using Cloisite 15A, Cloisite 25A and Cloisite 30B as organoclays and Lotader 2210 (E-BA-MAH), Lotader AX8840 (E-GMA) and Lotader AX8900 (E-MA-GMA) as impact modifiers. The effects of the composition, types of the components and the addition order of the nanocomposites on the morphology, mechanical, flow and thermal properties were investigated. Melt compounding step was carried out twice in a co-rotating twin-screw extruder. This was called as All-S mixing sequence when all the components were melt mixed, simultaneously. The concentration of the elastomer was determined as 5 wt% and the organoclay as 2 wt% to minimize agglomeration of the organoclay and decrease in the mechanical properties. The components which exhibited the best mechanical results and organoclay delamination in All-S mixing sequences were compounded by using different addition orders. Substantial increases were not observed in the tensile, impact, flexural and hardness test results of the nanocomposites compared to the polymer matrix that was twice extruded. Addition order of the components affected the properties of the nanocomposites and dispersion of the elastomeric domains and the organoclay. The best mechanical test results were obtained for All-S mixing sequence of (PA 66-15A-2210). The degree of organoclay dispersion is better in Cloisite 15A and Cloisite 25A containing nanocomposites than the ones which have Cloisite 30B. Low melt flow index values aided dispersion of the organoclay whereas the slight changes in the crystallinity did not significantly contribute to the changes in the mechanical properties of the nanocomposites or the blends.

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'
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.

Polypropylene, PP, based nanocomposites were produced via melt blending method by using twin-screw extrusion in this study. The effects of organoclay type, compatibilizer type, and mixing order of components on the morphology, thermal, mechanical and flow properties of ternary nanocomposites were investigated. Terpolymer of ethylene/butyl acrylate/maleic anhydride, ethylene/methyl acrylate/glycidyl methacrylate, and copolymer of ethylene/glycidyl methacrylate elastomers were used as compatibilizer, whereas Cloisite®
30B, Cloisite®
15A, and Cloisite®
25A were used as organoclay. iv In order to determine the optimum amount of compatibilizer, PP/compatibilizer blends were produced with different compositions. The content of compatibilizer was determined as 5 wt % based on the mechanical tests. Then, ternary nanocomposites were prepared with 5 wt % compatibilizer and 2 wt % organoclay contents. In addition, neat PP and PP/organoclay composites were prepared in order to make comparison. After that, the samples were characterized. According to the XRD analysis, the highest increase in the interlayer spacings of organoclays were observed in the PP/E-MA-GMA/Cloisite®
15A (23%) and PP/E-MA-GMA/ Cloisite®
25A (88.3%) ternary systems. SEM micrograms revealed that compatibilizer E-MA-GMA is the most compatible elastomer with PP. Thus, it was decided to investigate the effect of mixing order on the properties of these nanocomposites with E-MA-GMA. DSC analysis showed that the melting behavior of the nanocomposites does not change significantly with the presence of organoclay and compatibilizer. In addition, compatibilizers and organoclays have no significant nucleation activity in PP. The systems PP/E-MA-GMA/Cloisite®
15A and PP/E-MA-GMA/Cloisite®
25A have the highest improvements according to the results of mechanical tests. The results of mechanical tests showed that the mixing sequence (PEC), in which PP, organoclay and compatibilizer were compounded simultaneously in the first extrusion run, is the best sequence.

The purpose of this research was to prepare nanocomposite materials comprised of exfoliated clay particles in a polyimide matrix. Poly(amide acid)/organoclay solutions and polyimide/organoclay films were prepared and the clay dispersion was characterized by visual inspection, XRD, and TEM. Mechanical measurements and certain thermal characterization measurements were also obtained. The research began by attempting to repeat the procedures set forth in the literature. Most of the polyimide/organoclay nanocomposites were being prepared by mixing prepared poly(amide acid) solutions with organoclay solutions. This simple mixing technology was used in the preparation of various polyimide/organoclay hybrid formulations. In-situ polymerization, which involved performing the polymer synthesis in the presence of the organoclay, replaced simple mixing with increased success. Although the in-situ polymerization technique was successful at exfoliating clay particles in certain polyimides, the organoclay degraded at the polyimide cure temperature. In order to raise the use temperature, the aliphatic surfactants found in commonly used organoclays were replaced with aromatic surfactants. The dispersion of the clay was more difficult with the aromatic surfactants. It was facilitated by reducing the charge on the clay surface. This was achieved by replacing some of the cations that reside on the surface of the clay particles with lithium ions in the interior of the particles. The in-situ polymerization of APB-BPDA poly(amide acid) in the presence of an aromatic organoclay with a cation exchange capacity (CEC) of 0.57 meq/g and subsequent cure to the polyimide yielded a film with a high level of clay dispersion.

Increasing concern about the pollution of environment by inorganic and organic chemicals arising from naturally occurring ecological events and industrial processes has created a need for the search of new techniques in the removal of these contaminants. One of the natural material that can be used in such processes is clay. Clay minerals have large surface areas and high cation exchange capacities which enables them to be modified by cationic surfactants. The material prepared, often called as &
#8216
organoclay&
#8217
, can be used to remove hydrophobic organic and anionic contaminants from polluted water. Among the anionic contaminants, oxyanions such as nitrate, chromate are detrimental to human life and environment even at µ
g/L- mg/L levels. Application of organoclays for their removal from polluted water appears as one of the practical and rather cheap solution. In this study, a local clay from Ankara-Kalecik (Hanç
ili Bentonite) was modified by hexadecyltrimethylammonium bromide (HDTMA-Br) to a level of twice of its cation exchange capacity. This process alters the negatively charged surface of the clay into a positively charged one, providing sites for the removal of anionic contaminants. In this study, the degree of HDTMA+ uptake by the clay within a period of eight hours is found to be 97% of the initial amount added. In desorption studies it was revealed that only about 1% of the sorbed HTDMA+ was leached in a seven days of water-organoclay interaction revealing a rather stable organoclay structure in aqeous media. Sorption experiments with nitrate, borate, and chromate solutions were performed in order to determine the anion sorption capacity of the organoclays prepared. It turns out that while untreated clay has insignificant capacity, the modified clay can remove considerable amount of nitrate and chromate ions from aqeous solutions. While the nitrate sorption was increased about eleven fold, change in chromate sorption was reached to a level of twenty fold compared to that of the untreated clay. Sorption data for nitrate and chromate are both well described by the Langmuir isotherms. No significant change was observed in case of borate-organoclay interaction. Desorption of nitrate and chromate ions from organoclay surface were also investigated. Sorption of these oxyanions were found to be almost irreversible in aqeous media. The results imply that a properly prepared organoclay can be used for the removal of oxyanions, such as nitrate and chromate from polluted water systems.

Five series of PT-30/organoclay (Cloisite 10A, Cloisite 30B, Nanomer I.28E, Nanomer I.30E and Nanomer I.44PA) composites were prepared and characterized. The dispersion of clay tactoids in PT-30 resin was studied by XRD and TEM. XRD analyses determined that the d-spacings of each nanoclays of these were expanded upon dispersing in the PT-30 matrix versus the as-received clay. TEM micrographs further demonstrated that the intercalation of clay layers by PT-30 occurred during the curing process. Histograms of clay tactoids distributions were generated based on the combination of XRD and TEM results. The glass transition temperatures (Tg) of selected PT-30/clay composites were measured by DSC and compared. Partial clay exfoliation with some resin intercalation was demonstrated. The average flexural strengths and flexural moduli of all composites were obtained using three-point bending tests.

A number of polyurethane (PU) I poly(ethyl methacrylate) (PEMA) interpenetrating polymer network nanocomposites were investigated with regard to morphology and energy absorbing ability. The nanoclays used were umnodified sodium montmorillonite clay and three different types of organically-modified clays: C15A, C20A and C30B. The nanoclays were incorporated into the IPNs by using an in-situ polymerisation method. The clay dispersions were characterised by wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). The morphologies of the IPNs were determined with dynamic mechanical thermal analysis (DMTA), TEM and modulated-temperature differential scanning calorimetry (M-TDSC), while the mechanical properties were investigated using tensile testing and hardness measurements. Firstly, the original synthesis procedure and formulation was adjusted by varying the nanoclay C20A content, IPN composition ratio, nanoclay mixing time and PU catalyst, including a study of the PU and PEMA homopolymer composites. All IPN composites showed only partially intercalated nanocomposites as revealed by WAXD and TEM results. 70PU/30PEMA (70:30 composition ratio) IPN nanocomposites exhibited potential as materials for damping applications as it had a broad loss factor ≥ 0.3 spanning a wide temperature range. Secondly, the synthesis procedure was modified by changing the order of nanoclay mixing with homopolymer components. All lPN composites were based on a composition ratio of 70PU/30PEMA, 5 wt% C20A content, 1.2 wt% of PU catalyst and 30 min mixing time. High intensity ultrasonic waves were also introduced in the nanoclay mixing step for one hour. However, the ultrasonication showed only a marginal change in damping properties. Finally, a number of other nanoclays were incorporated into the 70PU/30PEMA IPN. All IPN composites achieved only a partial intercalation, except for the C30B-filled lPN where no changes were revealed by W AXD. All nanoclays caused a decrease in the glass transition of both homopolymers. IPN nanocomposites tended to reveal a higher extent of phase separation with increased clay content, but only the Na clay-filled lPN still showed a broad loss factor value, even at higher clay content. Improved modulus of elasticity was shown by all nanoclays, with increased clay loading. Whereas a moderate increase in the tensile strength was only shown at 1 wt% clay content.

Produced water, a byproduct of oil and gas production, includes almost 98% of all waste generated by oil and gas exploration and their production activities. This oil contaminated waste water has a great impact on our environment and is considered to be a high-cost liability. The Department of Energy’s Oil and Gas Environmental Program is concerned with the development of new and affordable technology to clean this produced water. Organically modified clays are proposed as a good option for removal of oil from produced water. Organoclay, incorporated into a treatment process shows promise of being a cost effective method of treatment to remove crude oil from brine either as a final treatment prior to brine disposal at sea or as a precursor to desalination. Organoclay also pre-polishes the waste water before further treatment. This research studies the efficacy of using organoclay to remove oil by measuring its adsorption capacity to remove the oil from a SAE 30 (Golden West Superior) motor oil-water emulsion. A kinetic model was developed to examine the time dependent behavior of the oil adsorbing characteristics of the organoclay and to investigate how closely the experimentally obtained data matches the kinetic model. It was found that organoclay is effective in removing various percentages of oil depending on the concentrations of a SAE 30 (Golden West Superior) motor oil-water emulsion. Moreover, it was found that the experimental data closely follow the kinetic behavior of the organoclay as shown by the kinetic model. Since this research is specific to a particular type of oil, SAE 30, further research is required for verifying the adsorption capacity of organoclay in other types of oils. Moreover, it is also recommended that the adsorption capacity of the organoclay, together with conventional adsorbent such as GAC (Granular Activated Carbon), be investigated to determine if there is any further improvement in the adsorption capacity. Lastly, a detailed investigation using the actual produced water from the oil field should be conducted to determine the efficacy of the organoclay system in removing oil from water produced in the field.

Pyrolytic lignin has negative effect on the quality of bio-oil in the application as fuel and energy source. On the other hand, pyrolytic lignin is also a potential alternative precursor for the manufacturing of general performance grade carbon fibre. Since clay or layered silicate reinforcement has been demonstrated to enhance the mechanical properties of many polymers, improvement of mechanical properties of carbon fibre fabricated in this work is expected. This thesis focuses on the proof-of-concept study of pyrolytic-lignin-based carbon fibres and investigates the potential of organoclay reinforcement in improving the mechanical properties of the resultant carbon fibres. In the process of carbon fibre preparation, the pretreatment (thermal treatment under reduced pressure) was found to be a critical step in the successful preparation of carbon fibres from pyrolytic lignin. Without pretreatment, the pyrolytic lignin tended to develop hollow structures during spinning and the spun fibres fuse when thermostabilized. In the pretreatment, higher temperatures and longer time (170-180oC and 4-6 hrs) led to poor fibre spinning of pyrolytic lignin, whereas lower temperature and shorter time (150oC and 0.5-2 hrs) resulted in lignin fibres fusing in the thermostabilization process. Only a narrow window between these two extremes is suitable for carbon fibre production. By choosing the treatment condition (160°C, 30KPa for 1h) that gives the best fibre spinning, pyrolytic-lignin-based carbon fibres were fabricated, with mechanical properties and yield comparable to those based on technical lignins. Two organoclays were employed containing modifiers with different hydrophobicity. The tensile strength of carbon fibres were improved by 12% to ~440 MPa at a 1 wt% organoclay Cloisite 30B loading. Increasing the organoclay content above 1 wt% resulted in a drop in tensile strength. The Young's modulus of pyrolytic-lignin-based carbon fibres dropped slightly upon addition of both types of organoclays (~32 GPa) and decreased as organoclay content increases. The addition of organoclay only slightly increased the overall yield of carbon fibre production from 45 wt% to 46-47%, which was independent of organoclay type and loading.

This thesis describes a programme of work whose aim was to develop and characterise a novel organoclay derived from montmorillonite clay and the amphoteric surfactant cocamidopropylbetaine (CAB), a plant oil derivative, and to test its compatibility with poly(lactic acid) (PLA). Clay minerals such as montmorillonite increase the mechanical and physical properties of polymers when well dispersed within the polymer matrix, a condition that is more easily achieved when the clay layers are coated with a surfactant such as a quaternary alkyl ammonium compound (QAC). In the first part of the thesis the structure, purity and thermal behaviour of the CAB were characterised and the solubility parameter of the molecule was calculated and compared with that of a surfactant used in a commercial organoclay. The effects of concentration and pH on the uptake of the surfactant by montmorillonite were characterised by analytical and spectroscopic methods including X-ray diffraction analysis. The effect of surfactant loading on the thermal stability of the organoclay was studied using thermogravimetric analysis (TGA). The possibility of a reaction between CAB and PLA was also investigated by thermal and spectral methods. In the second part of the thesis, composites of the novel organoclay and PLA were manufactured by solution casting from chloroform, and melt compounding using a torque rheometer. It was found that intercalated/exfoliated nanocomposites could be made by either method. The biodegradability of the nanocomposites in composting conditions was also investigated. The study showed that CAB can be used to manufacture organoclays that confer useful improvements in the properties of PLA in terms of thermal stability and mechanical strength and on this basis merits further study. It also showed that organoclays based on CAB are a useful addition to the range of tallow-derived organoclays currently available.

Inspiré par la technique couche par couche traditionnelle (LBL), Ce travail de thèse démontre le premier effort pour développer une nouvelle méthodologie pour l’auto-assemblage des multicouches sur la base des interactions hydrophobes et d'adsorption physique pour fabriquer des films composites stratifié en Polyéthylène (LLDPE) - organoargile (OMMT). Contrairement à la technique LbL électrostatique, ici, les films multicouches ont été synthétisés en partant d'un substrat de polymère non polaire/non chargé et successivement le dépôt de couches d’organo-argile apolaire et de couches de PE non polaires/non chargés avec des dépôts répétitifs qui se suivent. La variation alternative de l'angle de contact (85° en moyenne pour l’organo-argile et 107° pour les couches de PE) a confirmé la profilométrie et les résultats de la microscopie électronique à balayage, ainsi que le modèle de croissance linéaire, la formation très stratifiée réussie de bicouches répétitives composées de 450 nm couches d’organo-argiles et 2,25 µm couches de PE. Ultérieurs essais de caractérisation ont été effectués pour évaluer l'effet de la variation des principaux paramètres de processus identifiés (concentration, température, les étapes de rinçage et de séchage, et le type de solvant), sur la formation et la croissance d'épaisseur des films. En conséquence, la forte dépendance de l'auto-assemblage aux paramètres du procédé testés a été montrée par les résultats expérimentaux obtenus. Les propriétés de barrière des films multicouches ont également été évaluées par la caractérisation de la perméabilité à la vapeur d'eau, à l'oxygène (O2) et au dioxyde de carbone (CO2), ainsi que la sorption de la vapeur d'eau. Un revêtement de 5 bicouches (OMMT/PE) (~ 14 µm d'épaisseur) a réduit la perméabilité à l'O2 d'un film de PE de 160 µm d'épaisseur de 84,4% et la perméabilité au CO2 de 70%, tandis que la perméabilité a la vapeur d’eau a été réduite de 45%. Ces réductions de perméabilité obtenues par seulement l’ajout de 2,4% (v/v) de nano-argile se sont révélés être significativement plus élevée par rapport aux valeurs de réduction rapportées dans la littérature pour les nanocomposites dispersés préparés à base de PE/organo-argile. Cette connaissance peut être utilisée dans la mise en place d'une approche pour produire des micro/nanostructures stratifiés ayant des propriétés de barrière sur mesure pour l'application dans l'emballage alimentaire
Inspired by the traditional Layer-by-Layer (LbL) assembly technique, this PhD study demonstrates the first effort to develop a novel methodology for multilayer self-assembly on the basis of hydrophobic interactions and further physical adsorption to fabricate stratified Polyethylene(LLDPE)-organoclay(OMMT) nano-enabled composite film. In contrary to the electrostatic LbL technique, here, the multilayer films were synthesized by starting from an uncharged apolar polymer substrate and successively depositing apolar organoclay and uncharged apolar PE layers with subsequent repeating depositions. The alternate variation of contact angle (85° average for organoclay and 107° for PE layers) confirmed the profilometry and the scanning electron microscopy results as well as the linear growth pattern, i.e. the successful highly stratified assembly of repetitive bilayers comprised of 450 nm organoclays and 2.25 µm PE layers. Further characterization tests were performed to evaluate the effect of the main identified process parameters (concentration, temperature, rinsing and drying steps, and solvent type) variation on the formation and thickness growth of the films. As a consequence, the high dependence of the self-assembly’s growth to the tested process parameters was showed by the obtained experimental results. The barrier properties of the multilayer films were also evaluated by characterizing the Water vapour, Oxygen (O2), and Carbon dioxide (CO2) permeability as well as the water vapour sorption. A 5-bilayer (OMMT/PE) coating (∼14 µm thick) reduced the O2 permeability of a 160 µm-thick PE film by 84.4% and the CO2 permeability by 70%, while the WVP was reduced by 45%. These permeability reductions obtained by only 2.4 v/v % of nanoclay addition level were found to be significantly greater compared to the reduction values reported in the literature for prepared blend PE/organoclay nanocomposites. This knowledge can be used in the establishment of an approach to produce stratified micro/nanostructures with tailored barrier properties for food packaging application

Elastomer nanocomposites based on NR/EPDM/organoclay were prepared by two-roll mill to investi-gate the effect of different percentages of nanoclay (0, 1, 3, 5 & 7 Wt%) and different matrix compositions (100/0, 75/25, 50/50, 25/75 & 0/100) on the microstructure, mechanical properties and best applicability of the mathematical models. Results of X-ray diffraction showed that enlargement of the silicate layers, pene-tration of polymer chains into layers and formation of an intercalated and exfoliated structure which was confirmed by TEM analysis. Mechanical properties as well as heat build up of the samples improved by addition of nanoclay. Addition the compounds with EPDM leads to an increase in compression strength, modulus and compressin set and decrease in tensile and tear strength. The prepared samples receive more aging resistance by addition of more clay and EPDM. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35610

Novel solutions to offset thermal degradation of polyamide-6 (PA-6) and organoclay (organically modified layered silicates) nanocomposites during melt compounding have been investigated. In this research, a novel chain extender (Joncryl ADR 3400) has been used to improve thermal stability of PA-6 and PA- 6/organoclay nanocomposites during melt compounding. The materials were compounded using a linear twin extruder and various laboratory scale mixers. The effects of organoclay and chain extender were studied using both processing methods. In order to replicate large scale production used in industry, a comprehensive plan of experimental work was carried out under different processing conditions (extrusion temperature and screw speed), organoclay and chain extender loading using a linear twin screw extruder. Rheology, mechanical and thermal properties were analysed and selected samples were also characterised by TEM and FTIR. Process induced degradation of PA-6 during the melt compounding was found to have significant influence on the rheological and mechanical properties. Rheological and mechanical characterisation clearly showed showed that incorporation of the chain extender minimised thermal degradation of PA-6 and nanocomposites during melt processing. Visual analysis of selected nanocomposites using TEM confirmed that chain extender increased the dispersion of nanoclays in the PA- 6 matrix. The crystallinity of the PA-6 was slightly affected by addition of organoclay and chain extender. The samples obtained by linear twin screw extrusion showed higher rheological properties than the samples from laboratory scale mixers suggesting better mixing and less thermal degradation during extrusion.

The objective of this work was the development of an efficient adsorbent for irreversible immobilization of heavy metals in contaminated soils. The adsorbent was prepared by pillaring montmorillonite with silica followed by the grafting of a chelate ligand onto its surface. Its structure was studied by the Brunauer, Emmett, and Teller Method adsorption of N2, Dynamic Light Scattering, and Scanning Electron Microscopy. The adsorption capacity of the organoclay was measured by its mixing with contaminated kaolin soil samples and by analysis of heavy metal contents in leachate. The adsorbent was efficient in immobilization of heavy metals in both neutral aqueous and acidic media. In addition, the adsorbent was efficient in environmental samples reducing the concentration of iron in all samples in aqueous and acidic media. As a result, the adsorbent can be used for reduction of heavy metal leaching from contaminated sites.

Presence of a chelating ligand in the clay structure significantly improves its ability to immobilize heavy metals from contaminated sludge or wastewater. Two-step modification procedure comprising sequential pillaring and grafting of chelating agent to the modified clay is involved. Montmorillonite and kaolin were chosen as typical examples of expandable and non-expandable clays, correspondingly. Modifications with silica and ferric oxide were targeted on development of mesoporous structure. Laboratory tests of the organoclay efficiency for purification of wastewater were conducted with the most promising sample, i.e. organoclay with the highest specific loading of chelating agent. Experiments were conducted with model wastewater containing either individual or mixed cations of heavy metals. The modified organoclay displayed a high adsorption capacity on heavy metal cations even in acidic media. The method of modification presented in this work can be used for synthesis of efficient adsorbents for applications in contaminated areas.

Malaria is still the most important parasitic disease in humans with most cases occurring in Sub-Saharan Africa (90% cases). It is transmitted via anopheles mosquitoes. Several vector control methods are available, e.g. long lasting insecticidal mosquito nets (LLINs), insecticide-treated nets (ITNs) and indoor residual spraying (IRS). However, they are effective only when a person is in-doors. Outdoor protection can be obtained for short periods (48-72 hours) using topical repellents. This preliminary study investigated the possibility to develop longer acting delivery forms based on polymer technology. The viability of two different approaches were considered for the controlled release of the natural repellent 3,7-dimethyloct-6-en-1-al (citronellal). The first idea was to dissolve the repellent in the polymer while controlling the rate of release by clay nanoplatelets dispersed in the matrix. Towards this, ethylene vinyl acetate (EVA) copolymer (18% VA) was modified with organically modified nanoclay. Release tests showed that this approach was not viable as only a small amount of repellent could be incorporated and it was lost within a day or two from thin polymer strands. The second approach targeted the use of a polymer in which the repellent is not soluble at ordinary temperature but where solubility is achieved at high temperatures. In this case polyethylene was used as host polymer. It was shown that large quantities of repellent can be trapped inside the polymer matrix using the temperature induced phase separation method (TIPS). Scanning electron microscopy revealed that a microporous co-continuous phase structure was obtained by shock cooling homogeneous mixtures to temperatures well below the spinodal phase boundary curve. The phase behaviour of the LLDPE-citronellal system was studied using cloud point determinations in a microscope fitted with a hot stage and by differential scanning calorimetry. The experimental data points on the bimodal phase envelope were used to fix parameter values of the Flory-Huggins equation. The latter was then used to predict the location of the spinodal lines. At 40 wt.% polymer the spinodal boundary is located at 96 C. However, experiments showed that quenching temperature of 5°C (i.e. the temperature of typical cooling baths used during filament extrusion) is sufficient to generate the desired microporous structure.
Dissertation (MSc)--University of Pretoria, 2014.
tm2015
Chemical Engineering
MSc
Unrestricted

The aim of this study was to improve the mechanical properties &ldquo
Moplen&rdquo
EP300L which is a heterophase copolymer. Polymer blends and nanocomposites were prepared by melt compounding method in a twin screw extruder. Nanofil®
5 (N5) and Nanofil®
8(N8) were used as the organoclays, and maleic anhydride grafted polypropylene (M) was used as the compatibilizer. The effects of additive concentrations and types of organoclays on the morphology, mechanical and thermal properties were investigated. Organoclay loading over 2 wt% prevented the intercalation mechanism resulting in large aggregates of clay, thus the material properties became poor even in the presence of compatibilizer. Compatibilizer addition improved the intercalation ability of the polymer, however a substantial increase in mechanical properties was not obtained up to 6 wt % loading of the compatibilizer. XRD analysis revealed that intercalated structures were formed with the addition of compatibilizer and organoclay. The nanocomposites that were prepared with N5 type organoclay showed delaminated structures at 6 wt % compatibilizer loading. v Nanofill ®
5 exhibited the highest improvements in mechanical properties, since the degree of organoclay dispersion was better in Nanofill ®
5 containing nanocomposites in comparison to Nanofill ®
8 containing ones. The DSC analysis indicated a insignificant reduction in the melting temperature of the ternary nanocomposites.

According to the Texas Railroad Commission (TRC), ????over 250 billion gallons of produced water is taken out of Texas Soil every year, and more than 35% of this water is not currently fit to use.?? Therefore, it can be assumed that domestically and globally, the petroleum industries challenge has been to develop a high-tech and cost effective method to purify the large volumes of oilfield brines and produced water. Currently, most of the produced water requires several pre- and post- treatment methods to aide in reducing fouling of membranes, separation of components, increasing influent and effluent quality, and preventing unwanted work stoppage during the desalination process. As a result, the pre- and post- treatment conditioning of the produced water affects the economics and scale-up (i.e. residence times, absorption capacity, etc??) of the varying processes parameters. Therefore, this research focuses on developing an economic analysis and determining the adsorption capacity of an organoclay system to remove oil.

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 &
#506
to about 28-34 &
#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.

The objective of this study is to process and characterize the compatibilized blends of acrylonitrile-butadiene-styrene (ABS) and polyamide-6 (PA6) using olefin based reactive copolymers and subsequently to utilize this blend as a matrix material in short glass fiber (SGF) reinforced composites and organoclay based nanocomposites by applying melt processing technique. In this context, commercially available epoxydized and maleated olefinic copolymers, ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) and ethylene-n butyl acrylate-carbon monoxide-maleic anhydride (EnBACO-MAH) were used as compatibilizers at different ratios. Compatibilizing performance of these two olefinic polymers was investigated through blend morphologies, thermal and mechanical properties as a function of blend composition and compatibilizer loading level. Incorporation of compatibilizer resulted in a fine morphology with reduced dispersed particle size. At 5 % EnBACO-MAH, the toughness was observed to be the highest among the blends produced. SGF reinforced ABS and ABS/PA6 blends were prepared with twin screw extrusion. The effects of SGF concentration and extrusion process conditions on the fiber length distribution, mechanical properties and morphologies of the composites were examined. The most compatible organosilane type was designated from interfacial tension and short beam flexural tests, to promote adhesion of SGF to both ABS and PA6. Increasing amount of PA6 in the polymer matrix improved the strength, stiffness and also toughness of the composites. Effects of compatibilizer content and ABS/PA6 ratio on the morphology and mechanical properties of 30% SGF reinforced ABS/PA6 blends were investigated. The most striking result of the study was the improvement in the impact strength of the SGF/ABS/PA6 composite with the additions of compatibilizer. Melt intercalation method was applied to produce ABS/PA6 blends based organoclay nanocomposites. The effects of process conditions and material parameters on the morphology of blends, dispersibility of nanoparticles and mechanical properties were investigated. To improve mixing, the screws of the extruder were modified. Processing with co-rotation yielded finer blend morphology than processing with counter-rotation. Clays were selectively exfoliated in PA6 phase and agglomerated at the interface of ABS/PA6. High level of exfoliation was obtained with increasing PA6 content and with screw speed in co-rotation mode. Screw modification improved the dispersion of clay platelets in the matrix.

Adsorption kinetics and adsorption-desorption of atrazine on organoclay composites prepared with the surfactant 6-piperazin-1-yl-N,N'-bis-(1,1,3,3-tetramethyl-butyl)-(1,3,5)triazine-2,4-diamine and Houston Black clay were studied using the indirect batch equilibration procedure. The organoclay composites sorbed significantly more atrazine than the Houston Black clay. Adsorption equilibrium was reached after 72 h for the organoclay composites. Atrazine adsorption isotherms were described by linear partitioning. The Koc values ranged from 605 to 5271 L kg-1 for the organoclay composites compared to a value of 41 L kg-1 for the Houston Black clay. The organoclay composite containing 20% surfactant on a total weight basis provided the most efficient adsorption of atrazine, although organoclay composites containing much lower amounts of surfactant also adsorbed significant amounts of atrazine. An average of 11% of sorbed atrazine was released during desorption. Characterization of desorption products showed only atrazine molecules being released from the organoclay composites.

Orientadores: Meuris Gurgel Carlos da Silva, Onelia Aparecida Andreo dos Santos
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
Made available in DSpace on 2018-08-24T22:59:54Z (GMT). No. of bitstreams: 1 Bedin_Sidmara_M.pdf: 4205652 bytes, checksum: d622e46268c9acb2352410201461233c (MD5) Previous issue date: 2014
Resumo: Diariamente, uma grande quantidade de fluxos de água sofre contaminação por compostos orgânicos como, por exemplo, o benzeno, tolueno e xileno (BTX), os quais são compostos tóxicos e nocivos ao meio ambiente e aos seres humanos. Sendo assim, o estudo de técnicas de remoção e tratamento desses poluentes vem se tornando tema de muitas pesquisas. A adsorção tem se mostrado uma técnica bastante eficiente, pois atende aos limites da legislação, apresenta baixo consumo energético e custo de processo, ainda mais quando se faz uso de um adsorvente alternativo, como é o caso da argila organofílica. Nesse trabalho foi proposto avaliar a argila esmectítica sódica nacional Fluidgel, na forma natural e organofilizada, como materiais adsorventes alternativos na remoção dos compostos orgânicos BTX de soluções aquosas, em ensaios em sistema batelada e em sistema dinâmico. A argila organofílica foi preparada a partir da argila comercial e do sal quaternário de amônia HDTMA e se verificou a capacidade de troca catiônicas dos adsorventes. Foram realizadas técnicas de caracterização com a finalidade de determinar a área superficial do material, estrutura de poros, estrutura cristalina, morfologia de superfície, composição química, perda de massa e água e identificação de grupos funcionais de superfície. Testes preliminares comprovaram o caráter hidrofóbico da argila organofílica e sua afinidade por compostos orgânicos, bem como o caráter hidrofílico da argila comercial. Ensaios cinéticos de pH mostraram que o mesmo não afeta de maneira significativa o processo de adsorção. Os ensaios cinéticos de adsorção realizados em sistema batelada alcançaram o equilíbrio em 3h e apresentaram porcentagens de remoção de poluente superiores a 90%, com concentração inicial de 1,09 mmol/L. Os modelos cinéticos analisados foram o de pseudoprimeira ordem, pseudossegunda ordem e o de difusão intrapartícula, sendo que o modelo de pseudossegunda ordem melhor descreveu os dados experimentais. Para as isotermas de equilíbrios, testou-se as temperaturas de 35, 25 e 15 oC, sendo a maior capacidade de remoção com a maior temperatura, indicando que a adsorção nesse caso é de natureza endotérmica. Os modelos de isotermas avaliados foram Langmuir, Freundlich, Sips, DSL, MSAM e D-R, porém apenas o modelo de D-R descreveu de maneira satisfatória os dados experimentais. Pela análise dos parâmetros termodinâmicos, verificou-se que o processo de adsorção em estudo é espontâneo, favorecido a altas temperaturas e que possivelmente ocorre fisissorção. Devido à alta volatilidade dos compostos BTX, foi feita uma adaptação na adsorção em sistema dinâmico através de coluna de leito fixo e se realizou um ensaio cinético em leito de adsorção. A ordem de remoção dos compostos orgânicos, para ambas as argilas, foi xileno > tolueno > benzeno
Abstract: Daily a large amount of water flows suffers contamination by organic compounds as, for example, benzene, toluene and xylene (BTX), which are toxic compounds and harmful to the environment and to humans. Thus, the study of techniques for removal and treatment of these pollutants has become the subject of much research. The adsorption has proven to be a very effective technique because it meets the limits of the law, has low energy consumption and process cost, further when it makes use of an alternative adsorbent, as is the case with organoclay. In this study, it was proposed evaluate the national sodium smectite clay Fluidgel , in the natural and organophilizated form, as an alternative adsorbent material to the removal of organic compounds BTX from aqueous solutions in batch and dynamic system essays. The organoclay was prepared from the commercial clay and the quaternary ammonium salt HDTMA and it was verified the cationic exchange capacity of the adsorbents. Were performed characterization techniques in order to determine the surface area of the material, pore structure, crystal structure, surface morphology, chemical composition, mass and water loss and identification of surface functional groups. Preliminary tests confirmed the hydrophobic character of the organoclay and their affinity for organic compounds and the hydrophilic character of the commercial clay. pH kinetic experiments showed that the same does not affect significantly the adsorption process. Kinetic assays of adsorption performed in batch system reached equilibrium in 3 hours and showed pollutant removal percentages greater than 90%, with an initial concentration of 1.09 mmol/L. The kinetic models analyzed were the pseudo first order, pseudo second order and the intraparticle diffusion, being that the pseudo second order model best described the experimental data. For the equilibrium isotherm, was tested at temperatures of 35, 25 and 15 °C, being the largest removal capacity with the greatest temperature, indicating that the adsorption of this case is endothermic in nature. The isotherm models evaluated were Langmuir, Freundlich, Sips, DSL, MSAM and D-R, but only the D-R model described satisfactorily the experimental data. By the analysis of the thermodynamic parameters, it was found that the adsorption in study is spontaneous and favorable at high temperatures and that possibly occurs physisorption. Due to the high volatility of BTX compounds, it was made an adaptation to dynamic adsorption system through fixed bed column and a kinetic assay was carried out in adsorption bed. The order of removal of organic compounds for both clays was xylene > toluene > benzene
Mestrado
Engenharia Química
Mestra em Engenharia Química

Neste trabalho, materiais nanocompósitos de poli(imida) (PI) derivada de BTDA-pFDA-Mel e argila do tipo montmorilonita, organicamente modificada (O-MMT), foram sintetizados usando a metodologia de two-steps. O componente inorgânico do nanocompósito foi adicionado nas concentrações de 3,3, 5,3 e 8,3% em massa. As membranas sintetizadas foram caracterizadas por Espectroscopia de Absorção na Região do Infravermelho com Transformada de Fourrier (FTIR), Difração de Raio X (DRX), Termogravimetria (TG), Espectroscopia de Fotoelétrons Excitados por Raio X (XPS) e Microscopias Ótica (MO), Eletrônica de Varredura (MEV) e de Transmissão (MET). Os resultados comprovam a formação de PI e uma estrutura de nanocompósito do tipo intercalado, onde a cadeia polimérica expulsa o surfactante do espaço interlamelar; além de apresentar estruturas de argila parcialmente esfoliadas. Os materiais sintetizados foram avaliados como polieletrólito em célula a combustível alcalina (Alkaline Fuel Cell - AFC), obtendo condutividades iônicas em torno de 0,032 S cm-1 e de 0,017 S cm-1 para as membranas de PI pura e de nanocompósito com 3,3% de argila em massa, respectivamente, ambas a 60 °C, as quais são na ordem ou até mesmo superior que os polieletrólitos comercias (Tokuyama®, 0,014 S cm-1) para eletrólito alcalino. Apesar de condutividades razoáveis, a performance obtida para as AFCs em operação não foram satisfatórias, desta forma, membranas de nanocompósitos com PI de cadeia principal de maior mobilidade foram sintetizadas, caracterizadas e avaliadas nas AFCs. Ademais, neste segundo nanocompósito, a adição de grupamentos amino na cadeia principal foram realizados para aumentar a condutividade iônica. Assim, este segundo material apresentou uma maior performance nas AFCs quando comparado com o nanocompósito de PI de cadeia mais rígida e com a membrana comercial Tokuyama® nas mesmas condições. Além disso, a carbonização superficial das amostras foi realizada por meio de tratamento térmico. A formação de estruturas grafitizadas nos materiais de PI pura e dos nanocompósitos foram investigadas por FTIR, DRX, TG, XPS e EPR. Foi encontrado que a formação de estruturas do tipo grafite nas amostras ocorrem principalmente nas primeiras camadas (grafitização superficial), preservando a estrutura interna da poli(imida). Com isso, estruturas poliméricas ou nanocompósitos com superfícies grafitizadas podem atuar tanto como polieletrólitos e ser um caminho promissor para o desenvolvimento de arranjos eletrodo-membrana (Membrane Electrode Assembly - MEA) mais eficientes para células a combustíveis alcalinas, como em processos de catálise heterogênea e processos de separação com membranas.
In this work, Poli(imide)/clay (PI/clay) nanocomposite membranes were synthesized by employing a two-steps method using organically modified montmorillonite clay (O-MMT) with different amounts of O-MMT loading (3.3, 5.3 and 8.3 wt.%). Fourier transform infrared spectroscopy (FTIR), X-ray power diffraction (XRD), thermogravimetric analysis (TG), X-ray photoelectron spectroscopy (XPS), optical microscopy (OM), scanning electron microscope (SEM) and transmission electron microscopy (TEM) measurements, confirmed the formation of pure PI and intercalated-nanocomposite structures. The results revealed parallel clay layers with interlamellar PI and some organoclay partially exfoliated. In addition, the polyelectrolyte membranes of PI and PI/O-MMT (3.3 wt.%) showed that the ionic conductivity were 2- and 1-fold, respectively, higher than that of commercial membrane (Tokuyama®, 0.014 S cm-1), in alkaline fuel cells (AFC) at 60 °C. Despite the fact that the membranes of pure PI and PI/O-MMT demonstrated a good degree of ionic conductivity, rapid fuel cell performance deactivation occurred for the temperature higher than 75 °C. Furthermore, the lack of prepared polyelectrolyte ionic groups, led us to consider alternative synthesis of PI/clay nanocomposite membranes. Thus, the performance for second polyelectrolyte was superior when compared to pure PI, PI/O-MMT and commercial Tokuyama® membranes at same conditions. Moreover, the samples were also surface carbonized by thermal treatment. Combining FTIR, XRD, TG, XPS and electron paramagnetic resonance (ESR) analysis, the results suggested that graphitized nanostructures formation occurred mainly on the surface, maintaining the PI bulk structure. Therefore, graphitized PI/clay membranes may act as one promising way for enhancing both membrane electrode assembly in alkaline fuel cells and gas separation or catalysis.

Sais quaternários de amônio são amplamente usados como agentes antissépticos, desinfetantes, detergentes e preservantes. Além disso, sais quaternários de amônio são frequentemente utilizados como algicidas, sendo o cloreto de dodecil dimetil benzil amônio (Cloreto de benzalcônio) o mais efetivo contra estes microorganismos. No entanto sua aplicação como algicida de superfícies é limitada, devido a sua alta hidrofilicidade, ocasionando uma alta lixiviação deste composto quando a superfície é exposta à alta umidade e intempéries de clima tropical. Atualmente compostos como Diuron e S-Triazina são empregados como algicidas, considerados de baixa lixiviação. No entanto, altos níveis de concentração destes biocidas foram detectados em regiões costeiras evidenciando a lixiviação destes biocidas, quando utilizados em tintas para casco de navio. Assim surge a necessidade do desenvolvimento de um algicida para suprir as deficiências de lixiviação dos compostos empregados atualmente. Materiais como as argilas organofílicas são uma excelente alternativa, pois são altamente hidrofóbicas. Portanto sintetizou-se neste trabalho uma argila organofílica utilizando-se cloreto de benzalcônio, a qual foi utilizada em uma formulação de tinta imobiliária. O material foi caracterizado pelas técnicas de difração de Raios X e análise termogravimétrica. Um filme de tinta foi submetido a uma câmara de lixiviação, simulando a ação da chuva. Após a lixiviação o filme de tinta seguiu para testes microbiológicos, para verificar se a superfície ainda possui proteção microbiana. As algas testadas foram das espécies Phormidium cebenense, Trentepohlia odorata, Chlorella sp e Scenedesmus quadricauda colocadas num pool de algas. Através das análises de Difração de Raios X e termogravimétrica é possível determinar a estrutura e quantificar o teor cloreto de benzalcônio no material, respectivamente. Os testes microbiológicos e de lixiviação avaliaram a capacidade biocida assim como a resistência à intempérie do material. O novo composto sintetizado neste trabalho apresentou um alto potencial para uso como agente microbiano em tintas.
Quaternary ammonium compounds are widely used as antiseptic agents, disinfectants, detergents and preservatives. In addition, quaternary ammonium compounds are often used as algaecides, and dodecyl dimethyl benzyl ammonium chloride (benzalkonium chloride) is the most effective against these microorganisms. However benzalkonium chloride is not used as surface algaecide compound due its high hydrophilic, bring on high leaching of this compound when the surface is exposed to high humidity and severe weather from tropical climate. Currently, compounds such as diuron and s-triazine are used as microbial agent, considered low leaching. However diuron and s-triazine were detected in coastal regions in high levels concentration showing the leaching of these biocides when used in antifouling paints in ships. Considering these, it can be observed the necessity to develop a new algaecide to overcome the failings of leaching of the compounds used nowadays. Material as organoclay is an excellent alternative because they are highly hydrophobic. Therefore in this work was synthesized a new nanomaterial using benzalkonium chloride, which was applied in a house paint formulation. The material was characterized by the techniques of X-ray diffraction and thermogravimetric analysis. A film coating was placed in a leaching chamber, simulating the action of rain. After leaching the coating film was applied to microbiological tests to check if the surface still had microbial protection against the following algae species: Phormidium cebenense, Trentepohlia odorata, Chlorella sp and Scenedesmus quadricauda; placed in a pool of algae. It was possible to determine the structure and quantify the amount of benzalkonium chloride in the material through X-ray Diffraction and Thermogravimetric analysis, respectively. The biocide capabilities as well as the resistance to weathering of coating with the material were analyzed by microbiological and leaching test, respectively. The new compound developed in this study has a high potential to be used as microbial agent in paints.

Neste trabalho foram investigados a obtenção de argilas organofílicas e nanocompósitos de Poliestireno com estas argilas. A primeira parte deste trabalho teve como objetivo a modificação de argilas esmectíticas naturais brasileiras, tornando-as organofílicas e adequadas à aplicação em nanocompósitos de matriz poliméricas. Para modificação foram utilizados sais quaternários e foi avaliado quais parâmetros do processo de obtenção mais influenciam nas propriedades das argilas organofílicas. Para tanto foi utilizada a argila Brasgel (fornecida pela BUN, e naturalmente cálcica), e foram propostos diferentes métodos de preparo de argilas, onde quatro parâmetros foram avaliados: os sais quaternários amônio; a granulometria da argila (#400 e coloidal), a temperatura de processamento (ambiente e a 70oC) e os tempos utilizados durante o processo de incorporação dos sais quaternários na estrutura dos materiais argilosos. Os materiais obtidos foram caracterizados por difração de raios-X (DRX), ensaios de inchamento de Foster e analise térmica diferencial (DTA). Obteve-se incremento do espaçamento basal com todas as argilas utilizadas. Mostrou-se que os dois principais parâmetros determinantes na incorporação das argilas são o tempo de mistura e a temperatura (de 70oC) empregada. A segunda parte do trabalho teve como objetivo obter nanocompósitos de PS com argilas organofílicas (sendo uma argila obtida na primeira parte e uma comercial, Cloisite 20A) via intercalação no polímero fundido. Os nanocompósitos foram preparados em extrusora de rosca dupla e em misturador interno. As argilas foram adicionadas ao polímero fundido na forma de um pó e em suspensão de etanol. Os nanocompósitos obtidos foram moldados por compressão e injeção (com variações nas condições de injeção para avaliar a influencia na estrutura final), para realização da caracterização. A principal técnica de caracterização utilizada foi a caracterização reológica com ensaios de cisalhamento de pequenas amplitudes (COPA) e de varredura de tempo. Os materiais foram caracterizados também por técnicas auxiliares como DRX, microscopia eletrônica de transmissão (MET), analises térmicas diferenciais (DTA) e ensaios mecânicos. Obteve-se nanocompósitos de estrutura intercalada. Os materiais obtidos no misturadores mostraram as melhores dispersões de argila. . Verificou-se que o tempo de residência dos materiais é um dos fatores mais importantes na obtenção dos nanocompósitos. Os ensaios mecânicos não mostraram alteração significativa.
In this work, the obtention of organoclays and nanocomposites of polystyrene (PS) using these modified clays was studied. In a first part Brazilian smectites clays were modified to be used in clay containing polymer nanocomposites. Several quaternary ammonium salts and experimental methods to modify the clays were used. In particular four parameters were evaluated: the type of ammonium salt, the particle clay size, the temperature and time used during the process of modification. The samples obtained were characterized by X-ray diffraction (XRD), Foster swelling test and differential thermal analysis (DTG). The results indicated that the most two important parameters in the process of modification are the time and the temperature used. In a second part nanocomposites of PS with organoclays (one obtained in the first part, and commercial clay, named cloisite 20A) were obtained by melt intercalation method using a twin screw extruder and an internal mixer. The clays were incorporated to the polymer as a fine dried powder and as a suspension of ethanol. Nanocomposites were molded by compression and injection. The injection conditions were modified to evaluate their influence on the morphology of the samples. The nanocomposites samples were characterized by XRD, transmission electronic microscopy (TEM), DTG and mechanical tests. Small amplitude oscillatory shear (SAOS) and time sweep tests were carried out. Nanocomposites of intercalated structure were obtained. The ones obtained using the internal mixer were shown to present a finer microstructure. The experimental results revealed that the residence time was showed the most important parameter in obtention of nanocomposites.

Substantial environmental contamination has occurred from coal tar creosote and pentachlorophenol (C5P) in wood preserving solutions. The present studies focused on the characterization and remediation of these contaminants. The first objective was to delineate a sequence of biological changes caused by chlorinated phenol (CP) exposure. In Clone 9 cells, short-term exposure to 10 ?M C5P decreased pH, GJIC, and GSH, and increased ROS generation. Long-term exposure caused mitochondrial membrane depolarization (25 ?M), increased intracellular Ca2+ (50 ?M), and plasma membrane depolarization (100 ?M). Cells were affected similarly by C5P or 2,3,4,5-C4P, and similarly by 2,3,5-C3P or 3,5-C2P. Endpoints were affected by dose, time, and the number of chlorine substituents on specific congeners. Thus, this information may be used to identify and quantify unknown CPs in a mixture to be remediated. Due to the toxic effects observed due to CP exposure in vitro, the objective of the second study was to develop multi-functional sorbents to remediate CPs and other components of wood preserving waste from groundwater. Cetylpyridinium-exchanged low pH montmorillonite clay (CP-LPHM) was bonded to either sand (CP-LPHM/sand) or granular activated carbon (CP-LPHM/GAC). Laboratory studies utilizing aqueous solution derived from wood preserving waste indicated that 3:2 CP-LPHM/GAC and CP-LPHM/sand were the most effective formulations. In situ elution of oil-water separator effluent indicated that both organoclay-containing composites have a high capacity for contaminants identified in wood preserving waste, in particular high molecular weight and carcinogenic PAHs. Further, GAC did not add substantial sorptive capacity to the composite formulation. Following water remediation, the final aim of this work was to explore the safety of the parent clay minerals as potential enterosorbents for contaminants ingested in water and food. Calcium montmorillonite and sodium montmorillonite clays were added to the balanced diet of Sprague-Dawley rats throughout pregnancy. Based on evaluations of toxicity and neutron activation analysis of tissues, no significant differences were observed between animals receiving clay supplements and control animals, with the exception of slightly decreased brain Rb in animals ingesting clay. Overall, the results suggest that neither clay mineral, at relatively high dietary concentrations, influences mineral uptake or utilization in the pregnant rat.

L’adsorption sur un substrat représente un moyen simple, efficace et peu couteux pour remédier aux polluants inorganiques et organiques. Les minéraux argileux ont montré par le passé des propriétés d’adsorption exceptionnelles pour de nombreux composés organiques. La modification chimique de leur surface via l’intercalation de surfactant, pour la préparation d’organoclays, permet d’améliorer leurs capacités d’adsorption, en particulier vis-à-vis des composés organiques hydrophobes tels que les produits pharmaceutiques (PPs) qui sont de plus en plus fréquemment retrouvés dans les réseaux d’eaux usées ainsi que les eaux de surface de par leurs fortes consommations et excrétions par la population associées à une inefficacité des systèmes épuratoires conventionnels pour éliminer ces composés. Dans ces travaux, l’adsorption de PPs d’actions thérapeutiques différentes et aux propriétés physico-chimiques variées sur une smectite de référence et des organoclays préparés au moyen de différents surfactants (cationiques et nonioniques) a été étudiée avec une attention particulière sur la détermination des mécanismes d’interactions entre PPs et adsorbants selon diverses conditions expérimentales afin (i) d’évaluer la stabilité des matériaux pour une application en contexte épuratoire et (ii) appréhender le rôle des phases minérales dans le devenir des micropolluants organiques dans le milieu naturel. Les données expérimentales obtenues par un jeu de techniques complémentaire révèlent que les organoclays de manière générale et plus particulièrement ceux préparés avec des surfactants nonioniques semblent être les matériaux les plus polyvalents pour l’adsorption des PPs. Les résultats soulignent également l’importance du milieu hydrophobe généré par l’intercalation de surfactants qui offrent de nouveaux sites d’interaction pour l’adsorption des PPs. Ceci permet de statuer de l’efficacité et du caractère prometteur des organoclays quant à leurs capacités de remédiation des effluents en station d’épuration
Adsorption represents an easy, simple and low-cost way to remove both organic and inorganic pollutants in water. Clay minerals are well known for their outstanding adsorption properties for numerous products. The chemical modification of its surface through the intercalation of surfactants for the preparation of organoclays considerably improves the adsorption properties, in particular for hydrophobic organic compounds such as pharmaceutical products (PPs) which are more and more commonly found in sewage and surface water. In the present contribution, the adsorption PPs with different therapeutic actions and varied physicochemical properties onto clay mineral and organoclay derivatives prepared with different surfactants (cationic and nonionic) has been studied with a particular understanding of the interactional mechanisms of PP with the adsorbents in order to (i) evaluate the stability of materials for an application in purifying context and (ii) to apprehend the role of the mineral phases in the fate of organic micropollutants in the natural environment. The experimental data obtained by a set of complementary techniques reveal that organoclays prepared with nonionic surfactants show a versatility for numerous PPs while the hydrophobic environment generated by the grafting of surfactants with alkyl-chains particularly enhances the adsorption of the organic compounds. The study confirmed the efficiency and the promising remediation behavior of organoclays for wastewater treatment

The synthesis, characterization and application of dendrimers on solid supports are described. Melamine-based dendrimers are incorporated on clay minerals and silica gel. The hybrid materials are characterized using a variety of analytical techniques including thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). The first chapter gives an overview of the two main methods, convergent and divergent, for the synthesis of dendrimers. It also describes the synthesis of melamine-based dendrimers and their advantages over conventional dendrimers. Synthetic strategies and applications of dendrimers at surfaces are discussed. The preparation of organoclay materials containing dendritic surfactants is presented in the second chapter. The morphology of these organoclays is studied by X-ray powder diffraction (XPD). A new type of morphology is observed when large dendritic surfactants are incorporated onto the clay. This new morphology is described as frustrated intercalation. The ability of the dendritic organoclay composites to recognize small organic molecules in water is presented in the third chapter. Atrazine, a commonly used herbicide, is used as a model compound. Structure-activity relationship studies were conducted in order to gain some insight on the recognition and sequestration mechanisms. In the fourth chapter, reactive resins are evaluated for the covalent sequestration of monochlorotriazines from organic and aqueous solutions. The sequestration is monitored spectrophotometrically and using liquid chromatography coupled to a mass spectrometer (LC-MS). 1H NMR spectroscopy and MS are used to identify the covalent adducts formed between the monochlorotriazines and the resins. The efficiency of the resin is compared to several types of charcoal using aqueous solutions of atrazine. The final chapter describes the attachment of melamine-based dendrimers onto silica gels. Dendrimers are incorporated to the silica gel surface using two synthetic strategies, the stepwise growth strategy (SGS) and the "attach-to" strategy (ATS). These composites are also evaluated for their ability to remove atrazine from aqueous solutions.

The aim of this study was to improve the mechanical properties of a recycled grade polypropylene. Polymer blends and nanocomposites were prepared by melt compounding method in a twin screw extruder. Cloisite®
15A, Cloisite®
25A and Cloisite®
30B were used as organoclays, and ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) and maleic anhydride grafted polypropylene (PP-MAH) were used as compatibilizers. The effects of additive concentrations, types of organoclays and compatibilizers, processing conditions, and the compatibilizer to organoclay ratio on the morphology and mechanical, thermal and flow properties were investigated. Organoclay loading over 2 wt% prevented the intercalation mechanism and material properties, even in the presence of compatibilizer, as a consequence of large clay agglomerate formation. E-MA-GMA compatibilizer improved the intercalation ability of the polymer
however a substantial increase in mechanical properties was not obtained. PP-MAH is found to be a better compatibilizer. Processing conditions significantly affected both mechanical properties and morphology. When the processing temperature was decreased and screw speed was increased simultaneously, tensile and impact properties were improved owing to enhanced shear and dispersive forces. TEM analysis revealed that intercalated and delaminated structures were formed with the addition of PP-MAH compatibilizer. In addition to that, as the ratio of PP-MAH to organoclay was increased, more effective dispersion of organoclay was observed and hence resultant improvements in both tensile and impact properties were greater at compatibilizer to organoclay ratio of three. Cloisite®
15A exhibited the highest improvements in mechanical properties, although the degree of organoclay dispersion was better for Cloisite®
25A and particularly for Cloisite®
30B. Melt flow index values were lower compared to pure recycled polypropylene in the presence of organoclay and compatibilizers. DSC analysis indicated no significant change in the melting behavior of the matrix materials.

Polystyrene, PS, is a preferable polymer in industry, but, its brittle characteristic restricts its utilization. The aim of this study is to improve the impact strength of PS by the help of elastomeric materials SEBS-g-MA and E-BA-GMA. In order to prevent the reduction in the tensile strength of the materials, three different types of organic montmorillonites, MMT, (Cloisite®
30B, 25A and 15A) were used as fillers. Nanocomposite preparation was performed in a co-rotating twin screw extruder. Initially elastomer and organoclay contents were kept at 5wt% and 1-2wt% respectively. Well dispersed silicate layers were obtained for the nanocomposite containing SEBS-g-MA and Cloisite®
25A owing to the high viscosity of SEBS-g-MA and the solubility of polystyrene end block of SEBS with PS matrix. Owing to higher hydrophobicity of Cloisite®
15A a better dispersion was expected compared to Cloisite®
25A, but, it was concluded that two long aliphatic tails of Cloisite®
15A limited the access of polymer chains to the clay surface. The desired impact strength values could not be achieved by using 5wt% elastomeric materials
therefore, it was decided to increase the SEBS-g-MA content up to 15, 20, 30 and 40wt%. With increasing elastomer content, increasing average elastomer domain size was obtained. Also, it was observed that with the addition of organoclay, the elastomeric domain size increases since the clay particles reside in the elastomer phase and at the interphase between elastomer and PS. The mechanical test results showed that the nanocomposites containing 15 and 20wt% SEBS-g-MA have the optimum average domain size that results in better impact strength values without deteriorating tensile properties.

Due to brittleness of polystyrene, PS, its usage area is restricted. To solve this problem and expand the usage area of PS, it can be blended and impact modified with an elastomeric material. In this study, the decrease in the modulus and tensile strength imparted by impact modification was overcome by reinforcing this mixture by incorporating organoclays and producing nanocomposites. This study consists of two parts. In the first part of this study three different types of aliphatic elastomeric materials and three different types of organoclays were used and their effects on the morphology, mechanical, thermal, and rheological properties of PS were investigated. Lotader AX8900, Lotader AX8840 and Lotader 2210 were chosen as the aliphatic elastomeric compatibilizers
and Cloisite

Orientador: Melissa Gurgel Adeodato Vieira
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
Made available in DSpace on 2018-08-24T22:58:23Z (GMT). No. of bitstreams: 1 Stofela_SaraKarolineFigueiredo_M.pdf: 3437110 bytes, checksum: 75c3b9d81bd674bc6b2d46a4347ba152 (MD5) Previous issue date: 2014
Resumo: Resíduos contaminados com compostos orgânicos, sendo grande parte formados por hidrocarbonetos aromáticos, como o benzeno, tolueno e xileno, vem sendo gerados em grandes quantidades nas indústrias e em derramamentos de postos de estocagem de combustíveis. Sendo assim, surge espaço para novas pesquisas de tratamento desses efluentes, como a adsorção em argilas organofílicas. Portanto, o objetivo deste trabalho é avaliar o potencial da argila organofílica Spectrogel na adsorção dos compostos BTX. Para este estudo foram realizados teste de hidratação e expansão em meio orgânico, estudo do efeito do pH, avaliação do potencial de remoção e estudo cinético, por meio de ensaios cinéticos de adsorção monocomposto, bicompostos e tricompostos, estudo de equilíbrio, atráves de ensaios de equilíbrio monocomposto, bicompostos e tricompostos, nas temperaturas de 15, 25 e 35 oC, estudo termodinâmico, caracterização do material adsorvente antes e após os ensaios de adsorção, estudo de regeneração do adsorvente, e análise estatística do processo de adsorção. A argila apresentou uma eficiência de remoção de 95%, 89% e 96% para o benzeno, tolueno e xileno, respectivamente e mostrou que o processo é rápido com no máximo 120 min para atingir o equilíbrio. No estudo cinético, tanto o modelo pseudoprimeira-ordem, quanto o pseudossegunda ordem apresentaram boas correlações. O modelo de difusão intrapartícula e modelo de Boyd indicaram que a adsorção é controlada tanto pela difusão intrapartícula, como pela difusão externa. O estudo de equilíbrio indicou que o xileno é o contaminante com maior afinidade pelo meios adsorvente. Entre os modelos de isotermas utilizados nos ajustes dos dados experimentais, o modelo de Dubinin-Radushkevitch foi o que apresentou melhor correlação para todas as isotermas monocomposto. Para as isotermas bicompostos, o modelo de Freundlich foi o que melhor se ajustou. Os parâmetros termodinâmicos mostraram que o processo de adsorção de BTX em argila Spectrogel é espontâneo e endotérmico. A caracterização do adsorvente após a adsorção dos BTX mostrou que o mesmo é pouco poroso e possui a superfície heterogênea, evidenciando a presença dos compostos BTX e algumas mudanças estruturais no material adsorvente. Por fim, os ensaios de regeneração indicaram a regeneração do adsorvente por meio do eluente etanol
Abstract: Contaminated waste with organic compounds, being largely composed of aromatic hydrocarbons such as benzene, toluene and xylene, has being generated in large quantities in industries and spills fuel storage stations. Thus, it arises space for further research about treatment of these effluents, such as adsorption on organoclay. Therefore, the aim of this study is to evaluate the adsorption of BTX compounds into organoclay Spectrogel. For this study tests of hydration and expansion in organic media and tests of the effect of pH were conducted. Equilibrium study was also performed by tests of mono-component, bi-component and multicomponent solutions at temperatures of 15, 25 and 35 oC. The adsorbent was characterized before and after the adsorption experiments. Finally, the regeneration of the adsorbent through eluents and a statistical study of the adsorption process were also performed. The evaluation of the potential removal provided a removal efficiency of 95%, 89% and 96% for benzene, toluene and xylene, respectively and showed that the process is fast taking a maximum of 120 min to reach equilibrium. In the kinetic study, both the pseudo first order model, as well as pseudo second order model showed a good correlation. The intraparticle diffusion model and Boyd model indicated that adsorption is controlled by both intraparticle diffusion and external diffusion. The equilibrium study indicated that xylene is the most competitive contaminant by active adsorption site. Among the isotherm models used, only the Dubinin-Radushkevitch showed a good correlation for all mono-component isotherms. For bi-component isotherms, the Freundlich model showed the best fit. The thermodynamic parameters indicated that the adsorption process of BTX into clay is spontaneous and endothermic. The characterization of the study showed that the this adsorbent is porous and presents a heterogeneous surface after adsorption and the presence of BTX compounds and structural changes were observed in the adsorbent material after process. The dessorption tests indicated a possible regeneration of the adsorbent using ethanol as eluent.z
Mestrado
Desenvolvimento de Processos Químicos
Mestra em Engenharia Química

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&
#61666
15A, Cloisite&
#61666
25A and Cloisite&
#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.

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.

In this thesis study, the use of clay-polymer nanocomposites for their applicability in landfill sites as a product of retardation of waste water infiltration was evaluated. For this purpose, organophilic clays from HDTMA+ organic cation and nanocomposites of montmorillonite were prepared. The bentonite samples B1, B2 and B3 dominantly contain 2:1 layer montmorillonite and 1:1 interstratification of illite/smectite mixed layer as clay minerals. B1 is an unmodified yellow bentonite and B2 is a grey bentonite modified from B1, by the addition of Na2CO3 (Soda Ash). They were obtained from Hanç
ili (Kalecik-Ankara) bentonite deposit which belongs to the Hancili Formation of Early Pliocene age. B3 is a standard Wyoming (SWy-1) white bentonite and belongs to the Newcastle formation of Cretaceous age. Their cation exchange and swelling capacity values were determined and the values increase from B1, B2 to B3. In order to produce clay-polymer nanocomposites, firstly organoclays were produced in bentonite samples. Claypolymer nanocomposite production was achieved by in situ intercalative polymerization successfully with intercalation and partly exfoliation of clay minerals with polyacrylamide (PAM). The samples of sand (S1), sand+bentonite (S2) and sand+nanocomposite (S3) mixtures were prepared and their permeability was determined. As a result of these values, the permeability of samples decrease from S1, S2 to S3. The results imply that the permeability of sample decreases as the claypolymer nanocomposite content increases resulting in a retardation of water penetration throughout the sample. The product has a potential to be used as a retardant for waste water infiltration in landfill sites.

Apesar dos vários avanços que levaram à expansão do uso de compósitos dentários, ainda há deficiências que limitam suas aplicações. A resistência inadequada ao desgaste mastigatório é constantemente citada como problema das resinas e que acaba tornando-se responsável parcialmente pela redução de sua vida útil. O desgaste do material ocorre pela perda ou degradação da matriz orgânica permitindo a exposição da matriz inorgânica e consequentemente levando a perda desta. Sendo assim, o presente trabalho tem como objetivo principal avaliar o efeito das diferentes concentrações de argila organofílica nas propriedades de uma resina dentária modelo. Primeiramente, foi realizada a purificação da argila e sua posterior troca iônica, o preparo das resinas experimentais e posterior adição de argila em diferentes concentrações, e finalmente a confecção dos corpos de prova. Então, as resinas foram avaliadas através de técnicas como o DMA, TGA, PCA, FTIR, DRX e por testes de inchamento para avaliar a absorção de água. Por FTIR e por PCA foi possível realizar o acompanhamento da cinética de reação das resinas preparadas, obtendo-se assim o seu grau de conversão e também uma análise da sua cinética de polimerização, sendo observado que em concentrações maiores de argila, o grau de conversão e a taxa de polimerização diminuíram. Por TGA foi possível observar dois picos no segundo processo de degradação térmica da amostra sem adição de argila, indicando uma polimerização não homogênea; conforme aumenta-se a quantidade de argila presente na mistura, os picos duplos tornam-se um. DMA mostrou discreto aumento da Tg e aumento de E\' e E\", indicando um reforço destes compósitos. DRX mostrou que não houve exfoliação da argila no polímero, podendo ter a formação de um compósito convencional ou de um compósito intercalado sem expansão do espaço interlamelar. Já os testes de inchamento mostraram que quanto maior o teor de argila maior a absorção de água das resinas.
In spite of the developments that led to the use of dental composites, there are still some shortcomings that limit their use. Inadequate resistance due to the mastigatory wearing is often cited as an issue in resins, which is partially responsible for reducing its lifetime. Wearing out of the material occurs by the loss or degradation of the organic matrix, thus allowing the inorganic matrix to become exposed and consequently leading to its loss. Therefore, the present work has as main goal the evaluation of the effect of different organoclay filler content in the properties of a experimental dental resin. For such, the clay was first purified and then underwent through cationic exchange, following preparation of the resins and later addition of the organoclay obtained and preparing the specimens. The, the resins were evaluated by techniques such as DMA, TGA, PCA, DRX and swelling tests to observe water sorption. By FTIR and PCA it was possible to follow the reaction kinectics of the prepared resins, thus obtaining the degree of convertion and polymerization rate, allowing to observe that the higher the organoclay loadings the lower was both the polymerization rate and the degree of convertion. TGA allowed us to observe two peaks on the second process of thermal degradation on the sample with no clay, thus indicating a non-homogeneous polymerization; and with higher clay loadings the double peaks become one single peak. DMA showed a slight increase of Tg and also an increase in E\' and E\", indicating a reinforcement of the obtained composites. DRX showed no exfoliation of the polymer, thus forming either a conventional composite or maybe a interlacated composite with no expansion of the interlamelar space. Swelling tests showed that the higher the amount of organoclay added the higher was the amount of water absorbed by the specimens.

Fokus ove doktorske disertacije je bilo izučavanje sorpcionog ponašanja tri herbicida koji se nalaze na listi prioritetnih supstanci prema Okvirnoj Direktivi o vodama EU (2000/60/EC) sa generalnim ciljem dobijanja podataka korisnih za prioritizaciju na osnovu novog fundamentalnog znanja o efikasnosti (ad)sorpcije za uklanjanje ovihsupstanci iz  vode u lokalno specifičnim uslovima. Odabrani su ksenobiotici različite rastvorljivosti, hidrofobnosti i donorsko-akceptorskih osobina, koji  pripadaju  različitim klasama  herbicida (dinitroanilinski-trifluralin, hloroacetamidni-alahlor i triazinski-  atrazin). Prva faza je obuhvatala karakterizaciju sorbenata i vodenih matriksa .U sintetičkom matriksu, trifluralin pokazuje veći afinitet na ispitivanim sedimentima u odnosu na alahlor i atrazin. I u slučaju organoglina, sorpcija je najizraženija za trifluralin. Alahlor i atrazin pokazuju slične sorpcione kapacitete na TMA-K, dok je na TMA-B, sorpcija izraženija za alahlor u odnosu na atrazin. U  zavisnosti od prirodnog matriksa, na oba sedimenta, najveće  Kd vrednosti su dobijene za trifluralin, dok su Kd vrednosti za atrazin i alahlor  bile veoma slične ili pak veće za atrazin. U slučaju organoglina, vrednosti  K_d su rasle sa porastom log  K_OW vrednosti herbicida na TMA-K u oba prirodna matriksa. Kada je u pitanju TMA-B, rast K_d vrednosti sa rastom log  K_OW vrednosti uočava se u površinskom matriksu pri C_e  = 0,05 mg/l i 0,5 mg/l, i podzemnom matriksu pri najvećoj ravnotežnoj koncentraciji C_e  = 0,5 mg/l. Kao najefikasniji sorbenti su se pokazali  TMA-B (Kd  = 10,5 -  483 l/kg) i model sediment (Kd = 16,4 -  761 l/kg). Odsustvo jasne linearne korelacije izmeĎu  Kd i  % TOC upućuje na važnost interakcija mineralne faze i herbicida. U slučaju sedimenata nisu utvrđene korelacije K_d sa log  K_OW vrednostima, dok kod organoglina one postoje. K _d  /K_OW odnosi su najveći kod atrazina na svim sorbenti ma pa se pretpostavlja da on najviše učestvuje u  uspostavljanju specifičnih interakcija zbog svojih donorsko-akceptorskih osobina. Što se tiče uticaja DOC,  zaključuje se da poreĎenje efikasnosti sorbenata treba sprovoditi u prirodnim matriksima jer sorpcioni koeficijenti variraju u zavisnosti od koncentracije polutanata, tipa i sadržaja DOC. Kolonskim eksperimentima je pokazano da atrazin i alahlor prolaze kroz kolonu sedimenta, dok je trifluralin skoro u potpunosti adsorbovan i u vrlo maloj koncentraciji detektovan u efluentu što je u saglasnosti sa rezultatima šaržnih eksperimenata na ovom sorbentu. Procenjeni faktor retardacije pomoću modela TransMod za atrazin je veći u prirodnim matriksima (R  _d  = 54 i R_d = 55 u podzemnoj i površinskoj vodi, redom) nego u sintetičkoj vodi (R _d = 40). Kod alahlora nisu uočene značajne promene faktora retardacije meĎu matriksima (R _d = 30-35). Ovi rezultati su suprotni očekivanjima na osnovu hidrofilnosti ksenobiotika i mogu biti  rezultat upravo interakcija sa organskim materijama koje su bile izražene u kolonskim testovima, verovatno i više nego u šaržnim testovima gde se nije pojavilo povećanje R_d vrednosti u prirodnim matriksima u odnosu na sintetički matriks.  Bez obzira što je  alahlor hidrofobniji od atrazina, u uslovima datog matriksa i sorbenta ispoljava slične (šaržni testovi) ilislabije sorpcione karakteristike  (kolonski testovi)  koje upućuju na mobilnost kroz prvi zaštitini sloj.  Treća faza je obuhvatala ispitivanje adsorpcije herbicida na aktivnim ugljevima u prahu. Ispitana je kinetika adsorpcionog procesa određivanjem koeficijenta za unutarčestični prenos mase herbicida u sirovim i ozoniranim prirodnim matriksima. Određena je efikasnost uklanjanja herbicida na razlilčitim ugljevima u prahu. Efikasnost uklanjanja se kretala u različitim opsezima u zavisnosti od odabranog uglja, vodenog matriksa i doze uglja. Na komercijalnim ugljevima najveća postignuta efikasnost (doza uglja od 15 mg/l) za  alahlor iznosi u površinskoj vodi 95%, a u podzemnoj 76%. Za atrazin to je u površinskoj vodi 58% i u podzemoj vodi 56%, a za trifluralin u površinskoj vodi 87%, a u podzemnom matriksu 92%. Na uglju sitnih čestica koji se koristi u kombinaciji sa membranskom filtracijom ovevrednosti su  i veće. Stepen uklanjanja DOC na komercijalnim ugljevima (pri dozi od 15 mg/l) iznosi do 57% za površinski matriks i do  51% za podzemni matriks. Slična efikasnost u uklanjanju DOC je postignuta i na uglju sitnih čestica u oba matriksa. Ozonizacija je ispoljila očekivan negativan uticaj, više ili manje izražen. U slučaju ksenobiotika, uticaji ozonizacije su bili različiti, u zavisnosti od primenjenog uglja, matriksa i supstance. Najizraženiji uticaj je kod alahlora,  i to u negativnom smislu,zbog pada efikasnosti uklanjanja, verovatno zbog kompeticije sa organskom materijom ili efekta solubilizacije. U nekim slučajevima, ali mnogo manje, taj efekat je primećen i kod trifluralina. Na oba komercijalna uglja primećen je pozitivan uticaj ozonizacije na uklanjanje atrazina, ali u različitim matriksima,  pa se može spekulisatipretpostavljanjem da dolazi do favorizovane raspodele u novim oblogama  POM na uglju formiranim nakon ozonizacije koje su i dovoljno adsorbabilne, ali i sa dovoljno reaktivnim osobinama za asociranje sa polarnim supstancama, što je delimično i potvrđeno rezultatima adsorpcione analize.  
The focus of  this doctoral thesis was the study of the sorption behavior of three herbicides which are on the list of priority substances according to Water Framework Directive (2000/60/EC). The aim  was  to obtain the  data useful for prioritization on the basis of the  new fundamental knowledge about (ad) sorption efficiency  for the removal of these substances from the  locally specific water matrices. Selected xenobiotics  were  differing  in  solubility, hydrophobicity, and donor-acceptor properties, which belong to different classes of compounds(trifluralin as herbicide, alachlor as chloracetamide herbicide and atrazine as triazine herbicide).  In the first phase  of the thesis  characterization  of sorbents and water matrices  was performed. The aim of the second phase was the testing  of  the sorption anddesorption of organic xenobiotics in the sediments and organoclays. The equilibrium  sorption parameters and removal efficiencies of herbicides were determined in different water matrices.  In the synthetic matrix, trifluralin showed a higher sorption affinity onto tested sediments in comparison to the alachlor and atrazine. In the case of organoclays, sorption was mostly  pronounced for trifluralin. Alachlor and atrazine have similar sorption capacities onto the TMA-K. For the TMA-B, the sorption was more pronounced for alachlor than atrazine. Depending on the natural water matrices,  the highest  K_d values were obtained for trifluralin onto both sediments. The  K_d values for atrazine and alachlor were very similar or even greater for atrazine. In the case of organoclays, K_d values increased with increasing log  K_OW values of herbicides onto TMA-K in both natural matrices. When it comes to TMA-B,  K_d  valuesincreased with increasing log  K_OW values in  the surface matrix forC_e = 0,05 mg/l and 0,5 mg/l, and in groundwater at the highest equilibrium  concentration  C _e   = 0,5 mg/l. TMA-B (K_d = 10,5  -  483 l/kg) and model  sediment  (kd= 16,4 to 761 l/kg) were the most efficient s orbents. The absence of  the  clear linear correlation between  K_d and % TOC  indicates the importance of the interaction of mineral phases and herbicides. Correlation between K _d  and K_OW values did not existed in the case of sediments,  contrary to the organoclays.  Since K _d  /K_oW ratios were the h  ighest for atrazine onto all sorbents, it  was  assumed that atrazine mostly participate in specific interactions due to its donor-acceptor properties. Regarding the  influence of DOC on sorption, it was concluded that a comparison of sorbents efficiencies should be carried in  native matrices as sorption coefficients vary depending on the concentration of pollutants, the type and content of DOC. Column  experiments showed that atrazine and alachlor passed through the column of the sediment, while the trifluralin almost completely was adsorbed and in very low concentrations detected in the effluent which is in accordance with the results of the  batch experiments.  Estimated retardation factors of atrazine were higher in natural matrices (R _d  = 54 and R_d = 55 in groundwater and surface water, respectively) than in  the synthetic water (R_d = 40_{). I}n the case of alachlor, retardation factors were similar among water matrices (R_d = 30-35). These results are in the opposition  based on the xenobiotic hydrophilicity, and they could be the consequence of interaction with the organic matter  present  in the column tests, probably more than in the batch tests. Estimations of  R_d based on batch tests  did not show an increase of R_d values in natural matrices, in comparison to the synthetic matrix. More hydrophobic alachlor, in the circumstances of the sorbent matrix exerts similar  (batch  tests) or lower sorption (column tests) characteristics that indicate mobility through the first protective layer.  The third phase  included herbicide adsorption tests onto powdered activated carbons. The adsorption kinetics was examined by determining the intraparticle mass transfer coefficients for herbicides in raw and ozonated natural water matrices. The removal efficiencies of herbicides for different powdered activated carbons were determined. Removal efficiencies were in different ranges depending on the selected carbon, water matrix and carbon dose. The highest removal efficiencies  for commercial carbons (for carbon dose of 15  mg/l)  for  alachlor were 95% and 76% in surface and groundwater, respectively. The highest  removal of atrazine was  58% in surface water and 56% in groundwater. In thecase of trifluralin, removal efficiencies were  87% in surface water and 92% in groundwater. The removal efficiencies for the carbon with fine particles  (usually  used in combination with a membrane filtration)  were greater. The removal of DOC    by  commercial carbons (at the dose of 15 mg/l) was less than 57% in the surface water and 47% in groundwater. A similar efficiency in DOC removal was achieved for the carbon with fine particles in both water matrices. Ozonation showed the expected   negative influence on  DOC  removal efficiencies, more or less pronounced. In the case of xenobiotics, ozonation influence was different, depending on the applied carbon and xenobiotic. The most important negative influence was  in the case of alachlor probably due to competition with organic matter or solubilization effect. The  same, but less pronounced effect was observed for trifluralin. The positive influence of ozonation was observed in removal of atrazine  by  both commercial carbons but in   different water matrices.  One can speculate that it comes to the favorable distribution in new NOM coatings on carbons formed upon ozonation, which are sufficiently adsorbable, but with enough reactive qualities for association with polar substances, which is partly confirmed by the results of adsorption analysis.

I materiali (nano)compositi, unendo al loro interno le prestazioni dei loro componenti, che in alcuni casi possono addirittura agire sinergicamente sviluppando nuove proprietà non appartenenti alle singole fasi isolate, appaiono come una risposta ottimale alle nuove esigenze che richiedono materiali performanti dal punto di vista meccanico e sempre più dotati di funzionalità aggiuntive. È noto come l’uso di nanocariche consenta non solo di migliorare le proprietà meccaniche, ma di aggiungere proprietà funzionali di varia natura. In questo lavoro di tesi si sono quindi valutate due tipologie di nanocariche, grafene e organoclay (ritardante di fiamma), come modificatori di una matrice epossidica commerciale. La stessa matrice è stata utilizzata anche per produrre compositi contenenti fibra di carbonio riciclata da pirolisi, con la prospettiva futura di unire i processi e ottenere compositi da fibra di riciclo e matrice multifunzionale.