A series of experiments were performed to study the sorption of humic acid and Eu3+ ion (at trace concentrations) on the minerals: montmorillonite, bentonite, diatomite and kaolinite in ternary systems. Humic acid and europium sorption were investigated as a function of humic acid concentration, ionic strength and pH. There was a strong uptake of humic acid on to the minerals with sorption increasing as humic acid concentration decreases. For montmorillonite, the uptake of discrete size fractions was also studied. It was found that the larger fractions were more strongly sorbing and were better able to retain Eu in solution.The ionic strength has an impact on Eu behaviour: in the absence of humic acid, sorption strength decreases, whilst in the presence of high concentrations of humic it increases. The sorption of Eu3+ increases from pH 2 to 5 in both the presence and absence of humic acid. Above pH 5, the Eu3+ showed different behaviour with and without humic acid, and as humic concentration became high (100 ppm), the Eu behaves in the same way as the humic. Bentonite is able to sorb humic acid and Eu3+ at any concentration expected in the environment, and shows the strongest sorption of any of the materials tested. Experiments confirmed that Eu is an excellent analogue for Am in these systems.The sorption of selected divalent and trivalent metal ions: Ni2+, Co2+, Zn2+, Cd2+, Eu3+ and Cr3+ on montmorillonite has been investigated in the micro-molar concentration range. In all cases, sorption strength increased with pH, and was consistently stronger for the tri-valent ions. In the presence of humic acid, there was some evidence for the enhancement of sorption. Uptake of metal ions (Co2+, Ni2+, Cd2+, Cr3+, Eu3+ and La3+) by natural and modified kaolinite was studied, and for all except Cr3+, it was found that kaolinite modified by manganese hydrothermal treatment gave the strongest sorption.A simple kinetic model was developed to simulate the experimental data for the sorption of humic acid and Eu3+ on the minerals. The model allows two humic binding sites on the mineral surface and two types of humic in solution, which can have different Eu3+ binding strengths. Metal ion surface complexation is modelled with a single kinetic equation. Ternary complexes are included in the model. The interaction of humic acid on the minerals can be fitted reasonably well. However, for the Eu3+ ion behaviour, although the model was able to give a reasonable fit to data for montmorillonite and bentonite, it could not reproduce the behaviour for kaolinite and diatomite.

Les nanocomposites à matrice polymère et à renforts d’argile ont pris une grande importance au cours de ces deux dernières décennies. Ceci trouve son explication d’une part, dans la grande disponibilité et le faible coût de production de la phase renforçante, et d’autre part dans les remarquables améliorations de propriétés physiques et mécaniques. Ces améliorations sont observées même à de très faibles quantités de renforts comparées à celles de leurs homologues microcomposites. Le développement de ces nouveaux matériaux suscite un fort engouement tant au niveau de la recherche académique qu’industrielle. Cependant, les mécanismes responsables de ces améliorations de propriétés demeurent mal compris et restent l’une des principales préoccupations des chercheurs. Il s’agit dans ce travail de thèse, d’apporter une contribution à la compréhension et à la mise au point d’outils prédictifs du comportement mécanique de nanocomposites polymères à renforts d’argile de type montmorillonite. Pour y parvenir, deux approches de modélisation sont utilisées : la micromécanique des matériaux hétérogènes et la simulation de dynamique moléculaire. Du point de vue analytique, un modèle micromécanique basé sur l’approche auto-cohérente est développé. Le modèle proposé est validé par nos données expérimentales et celles issues de la littérature. Un protocole de simulation de dynamique moléculaire est proposé pour la modélisation à l’échelle atomique de ces nanomatériaux. Cette approche nous a permis, entre autres, de faire la lumière sur les interactions moléculaires entre les différents constituants, et de déterminer les propriétés élastiques effectives du nanocomposite. / Polymer nanocomposites reinforced with clay minerals have attracted a great consideration during the last two decades. That can be explained, firstly, by the availability and the reduced production cost of the reinforcing phase, and secondly, by the remarkable improvements in physical and mechanical properties. These improvements are observed even at very low amounts of reinforcements compared to their microcomposite counterparts. The development of these new materials creates a keen interest both in academic and industrial research. However, the mechanisms responsible of these property improvements are still poorly understood and remain a major concern of researchers. This work contributes to the understanding and to the development of predictive tools of the mechanical behavior of polymer nanocomposites reinforced with montmorillonite clay using two modeling approaches: the micromechanics of heterogeneous materials and the molecular dynamics simulation. An analytical micromechanical model based on the self-consistent approach is developed. The proposed model is validated by our experimental data and those from the literature. A new molecular dynamics simulation protocol is proposed for the modeling of these nanomaterials at the nanometric scale. This approach has allowed us, inter alia, to get insight into the molecular interactions between the different components and to determine the effective elastic properties of the nanocomposite.

No description available.

The voltammetric behavior of selected nitrophenols (2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol and 2,4,6-trinitrophenol) was investigated by differential pulse voltammetry (DPV) and by adsorptive stripping voltammetry (AdSV) at an unmodified electrode (CPE) and a clay-modified carbon paste electrodes modified by montmorillonite (MMT-CPE) and sepiolite (SEP-CPE) using electrochemical reduction and oxidation in Britton-Robinson buffer. For reduction, optimum conditions have been found at pH 2 for 2-NP and 4-NP, at pH 3 for 2,4-DNP and at pH 4 for 2,4,6-TNP. For oxidation, optimum conditions have been found at pH 2 for 2-NP and 4-NP and at pH 5 for 2,4-DNP. Voltammetric determination using electrochemical oxidation is not a suitable method for 2,4,6-TNP. The lowest detection limits were obtained for 2-NP using cathodic AdSV on SEP-CPE with 2,9·10-7 mol.dm-3 , for 4-NP using cathodic DPV on MMT-CPE with 2·10-6 mol.dm-3 , for 2,4-DNP using cathodic AdSV on SEP-CPE with 2,7·10-7 mol.dm-3 and for 2,4,6-TNP using cathodic DPV on unmodified electrode with 4,8·10-7 mol.dm-3 . Determination of mixture 2-NP and 4-NP and the possibility of the selective determination using open circuit sorption with DPV detection was further studied.

The objective of this work is development of a new adsorbent on the base of an organoclay with a chelating ligand covalently attached to the clay mineral surface. The presence of a chelating ligand in the clay structure significantly improves its ability to immobilize heavy metal ions from contaminated sludge of wastewater. Montmorillonite and kaolinite were chosen as typical examples of expandable and non-expandable clay minerals. A two-step modification procedure comprised of sequential modification with oxides and grafting of a chelating agent to the modified clay minerals was used. Modifications with silica and ferric oxide were conducted by reacting the dispersed raw clay minerals with tetraethoxysilane and ferric nitrate solution. A chelating ligand, N-[3-(trimethoxysilyl)propyl]ethylenediamine triacetic acid trisodium salt, was introduced into interlayer space of raw and modified clay minerals in aqueous solutions. 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 heavy metal ions. The modified organoclay displayed high adsorption capacity for 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.

To extend the time of service of asphalt roads modified montmorillonite nanoparticles were incorporated into bitumen with the aim of creating a gas barrier inside the bitumen which slows down the diffusion of oxygen through the bitumen. For this purpose [montmorillonite/alkyl-quat-primer] adducts ([MMT/PEI(nkD)xQyR]) were fabricated in which single-montmorillonite platelets were coated by a ultrathin polymer film by reacting montmorillonite particles with poly(ethylenimine) based polycations. The alkyl-quat-primer polymers were synthesised by adding ammonium groups and alkyl chains to hyperbranched poly(ethylenimine)s in a solvent-free reaction. Adducts with fully intercalated polymers were obtained when the polymers were reacted with an aqueous solution of [MMT/CTAB] or by mixing the polymers with montmorillonite and CTAB in an aqueous solution. The polymers replaced the CTAB in an intermediate formed [MMT/CTAB] adduct and adhered strongly to the montmorillonite due to a cooperative electrostatic interaction between the positively charged ammonium moieties of the macromolecules and the negatively charged montmorillonite surface. [MMT/alkyl-quat-primer] and [MMT/CTAB] adducts were incorporated via a single screw extruder into polymer- and non-polymer-modified bitumina to create bitumen-nanocomposites. Composites prepared under optimised conditions exhibited an adduct network inside the bitumen at adduct concentrations larger 5 wt.% and when non-polymer modified bitumina were modified. The aspect ratio of the incorporated montmorillonite platelets depended strongly on the adduct composition and the used bitumen, and was with [MMT/PEI(10kD)10Q80R10] adducts were very high (~ 300 - 1000) but with [MMT/PEI(10kD)10Q60R14] and [MMT/CTAB] adducts considerably lower (~ 30 - 90).

Shrinking and swelling in Yazoo Clay is a cause of concern for construction projects in Mississippi. This thesis investigated the effects of adding lime and Douglas Fir biochar on the shrinking and swelling capabilities of Yazoo Clay. Samples of Yazoo Clay were mixed with the additives in defined ratios and subjected to the free swell test and the COLE(rod) test. Biochar addition reduced the COLE(rod) of the samples a large amount, while increasing the swelling potential of the clay samples. The addition of lime slightly reduced both the shrinking and swelling potentials of the samples. The mineralogical variability of Yazoo Clay vertically and horizontally could limit the applicability of these results across the formation and is important to be considered before further application. While constrained to one location, this study showed the influence of biochar and lime on the shrinking and swelling capabilities of Yazoo Clay.

Hybrid organic-inorganic nanocomposites have received considerable attention during the last five years due to their unexpected properties. This work incorporated nanodispersed organically modified montmorillonite clay into polydicyclopentadiene resin matrices. Montmorillonite consists of 1 nm platelet sheets with a 2:1 structure, consisting of an alumina octahedral layer sandwiched between two silica tetrahedral layers. The relative weak forces between platelets allow small molecules like water, solvents and monomers as well as polymers, to enter into the interlayer spacings between the platelet sheets. In-situ polymerization of highly delaminated clay/dicyclopentadiene(DCPD) dispersions was used to prepare clay/polydicyclopentadiene (polyDCPD) nanocomposites. Highly delaminated composites were characterized using X-ray diffraction, X-ray scattering and high resolution TEM. Composites with 0.5-1 weight percent of clay had higher Tg values and flexural moduli. The flow properties of the organically-modified montmorillonite/DCPD liquid dispersions were examined using a co-rotating viscometer. The dispersions with clay concentrations higher than 0.5wt% clay in DCPD showed thixotropic flow behavior. Small angle neutron scattering (SANS) experiments were performed to obtain anisotropic scattering of highly delaminated clay in DCPD due to the orientation of clay platelets and tactoids in the shear field. No anisotropic scattering was observed. The reason for this unexpected result is not yet understood. Highly delaminated organically-modified clay composites were examined using small angle neutron scattering (SANS) and ultra small angle neutron scattering (USANS). The SANS data from 0.5, 1 and 2wt% clay/polyDCPD composites with 2 different types of clay were fitted to the stacked disk model. The average number of clay layers per tactoid was predicted by fitting the experimental data to the stacked disk model. Extensive high-resolution TEM analyses were performed on the same samples to obtain the average numbers of clay layers per tactoid. Two finite element models, one for the intercalated clay/polyDCPD nanocomposite and one for the exfoliated clay/polyDCPD nanocomposite, were developed. The effects of these different dispersion geometries for seven platelets in the polyDCPD matrix on the stress distributions were examined. The exfoliated platelet model showed reduced deformations and uniform stress distributions. The highest stress concentrations were found on the platelets? surfaces and where platelets were in close proximity.

No description available.

Free-swelling properties of montmorillonites in water systems were studied using X-ray diffraction techniques. Four specimen type montmorillonites (Wyoming bentonite, Otay bentonite, hectorite and nontronite) and several soil clays were selected. In Phase I of the study the differential swelling properties were related to the type of cation on the exchange complex and to variations in the mineralogical properties of the montmorillonites. / Ph. D.