Complexes are formed between a Ca-saturated fluorhectorite and organic molecules derived from propane by substituting benzene, pyridine, and piperidine rings in the 1,3 positions. The complexes are mainly of the A- and B-types described earlier by Greene-Kelly. Only one of the substances studied forms long-spacing complexes; in this case, the organic molecule is terminated at one end by a benzene ring and at the other by an active =NH group. Neutral forms of this molecule develop double-layer complexes, cationic forms develop single-layer complexes. The results are consistent with data for alcohols, alkyl chlorides and bromides, and alkyl amines.

The results of EPR, UV-VIS and IR spectral studies show that benzimidazole forms various complexes with Cu(II) exchanged in the interlayer space of montmorillonite, depending on the acidity of the reaction medium during synthesis. In a nearly neutral solution a bis(benzimidazole)bis(aqua) Cu(II) cationic complex is formed. In a strongly basic solution, benzimidazole is bound to Cu(II) in the form of an anionic bifunctional ligand and a planar intercalated bis(benzimidazolate) Cu(II) complex is formed, where the benzimidazolate anion acts as a bridging ligand in the polymeric complex. The treatment in basic solution leads to partial illitization of the smectite. In a strongly acid solution, a nearly stoichiometric ionic exchange of benzimidazolium ion for Cu(II) ions takes place in the interlayer space of montmorillonite.

In this study, poly(methyl methacrylate-maleic anhydride) (P(MMA-MAh)) was synthesized in toluene from methyl methacrylate (MMA) and maleic anhydride (MAh) monomers via free radical polymerization, in the presence of 2,2′-Azo-bis-isobutyronitrile (AIBN), as initiator at 80ºC for 8 h. The molar ratio of monomers was found to be 1 MAh:8 MMA using hydrolysis and titration. The molecular weight of co-polymer was determined to be of the order of 104 (g/mol) by gel permeation chromatography. The co-polymer was characterized using Fourier transform infrared and nuclear magnetic resonance spectroscopy. Thermogravimetric analysis indicated the initial decomposition temperature was ~270ºC. Differential scanning calorimetry indicated that the glass transition temperature was near 126ºC.

Rectorite modified with benzyldimethyldodecylammonium chloride (OREC) was used as an additive to modify gel polymer electrolytes (GPEs) which consisted of P(MMA-MAh) used as a polymer matrix, propylene carbonate (PC) as a plasticizer and LiClO4 as the lithium ion source. X-ray diffraction analysis indicates that OREC can exfoliate well in GPEs when the amount of clay is suitable. The temperature dependence of the ionic conductivity of the resulting GPEs agreed well with the VTF (Vogel-Tamman-Fulcher) relation. OREC doses of 5 phr resulted in the greatest ionic conductivity. This OREC addition considerably improved the plasticized retention levels. As a consequence of OREC occupying the free volume space in the polymer matrix of GPEs, the bulk resistance of the GPEs was reduced and the glass transition temperature (Tg) increased.

The arrangement of water molecules in the vicinity of clay mineral surfaces has been the subject of much speculation. Vermiculite offers a promising line of approach to this problem since, in addition to its occurrence in soil-clays, it is available as relatively large flakes which can be studied by single-crystal X-ray diffraction methods. This note reports an as yet incomplete structure analysis of vermiculite. A two-dimensional Fourier synthesis has been carried out and a determination of atomic parameters in the third dimension is in progress. The results obtained so far would appear to justify a preliminary statement.

The (h0l) set of reflexions for a natural Mg-saturated vermiculiet were recorded on two multiple-film packs exposed to MoKα radiation in a Weissenberg camera for 100 hours and 5 hours respectively. Intensities were estimated visually by comparison with a set of standards obtained from the (00·10) reflexion.

Los rasgos característicos geológicos (relieve bajo o medio, clima árido-semiárido, contrastado) y mineralógicos (asociación ópalo-alunita-caolinita) de niveles continentales Prelutecienses apoyan una hipótesis genética no hidrotermal. La evaporación de aguas portadoras de sílice disuelta, procedente de una meteorización del basamento, durante una estación seca, en depresiones, conduce a una precipitación de ópalo. Por otra parte, la desecación de áreas cubiertas por vegetaciones implica una descomposición bacteriana anaeróbica de materia orgánica y génesis de sulfuros; posteriormente, la aireación oxida a estos sulfuros y se generan aguas sulfatadas ácidas. Estas se mezclan con las que contienen silice, precipitando entonces conjuntamente ópalo, alunita y, si el Al3+ está en exceso, tambien caolinita.

L'intérêt porté à la synthèse de la kaolinite a été suscité par des préoccupations d'ordre pédologique, qui nous ont amenés à comparer les expériences réalisées en laboratoire aux situations naturelles considérées comme propices à la formation de la phyllite 1/1. Il apparaît essentiel, pour le succès des synthèses, de privilégier la formation d'ions hydroxylés monomères de Al, pouvant réagir avec l'acide orthosilicique. La neutralisation lente et partielle de solutions très diluées semble garantir ces conditions. Deux séries d'essais ont été entrepris. Les résultats expérimentaux tendent à démontrer la possibilité d'obtenir une précipitation de kaolinite à partir des ions en solution et par simple neutralisation. Le mécanisme proposé par Siffert (1962), mettant en jeu la formation d'éléments T-O, semble le plus probable. Ces éléments prendraient naissance par réaction de l'acide orthosilicique et de l'ion Al(OH)2+. Le rapprochement entre l'importance du rôle joué ici par ce monomère hydroxylé et la place qu'il occupe dans le schéma de dissolution établi par Sarazin (1979) peut permettre de comprendre que les néoformations de kaolinite correspondent à des sols relativement bien drainés.

Plans to close a German radioactive waste repository in rock salt include as one alternative the construction of a ‘Cross Section Closure (CSC)’ sealing barrier. The proposed material for the sealing barrier is highly compacted bentonite. To investigate the swelling behaviour of a highly compacted bentonite, a large number of laboratory tests were performed. In addition, large scale model tests were carried out to demonstrate the development of a nearly homogeneous and isotropic swelling pressure. The results of the large scale model tests were interpreted numerically based on the models for stress-strain behaviour and water uptake which are implemented in the finite element computer codes FEST03 and HYDOPO. The investigations show good agreement between the results of the model tests and the corresponding analyses and show that the theoretical models are capable of describing the behaviour of sealing structures based on highly compacted bentonite.

A grafted polymer (P(MMA-MAh)-PEGME)) was synthesized by reacting poly(ethylene glycol) monomethyl ether (PEGME) with copolymer of poly(methyl methacrylate-maleic anhydride) (P(MMA-MAh)and end-capping the residual carboxylic acid with methanol. Natural rectorite (REC) was made organophilic by modification with the surfactant dodecyl benzyl dimethyl ammonium chloride. The organoclay was termed OREC and was used as a filler additive to modify gel polymer electrolytes (GPEs) which consisted of the grafted polymer (used as a polymer matrix), propylene carbonate (PC) as a plasticizer and LiClO4 as a lithium ion producer.

The temperature dependence of the ionic conductivity of the GPEs agreed well with the VTF (Vogel-Tamman-Fulcher) relation. 5 phr doses of OREC resulted in the highest ionic conductivity. Using OREC also considerably improved the plasticizer retention levels. As a consequence of OREC occupation of the free volume space in the polymer matrix of GPEs, the bulk resistance of the GPEs was reduced and the glass transition temperature (Tg) increased. From the present research, it can be concluded that the incorporation of PEGME into the copolymer of P(MMA-MAh) produced a great improvement in ionic conductivity, plasticizer retention capability and movement of carrier charge of Li+.

The relationship between the K-Ar dates of mixed natural clays and the ratios of detrital and diagenetic components follows in most cases a linear trend, which agrees with the theory when the K2O contents of the end-members are similar. However, significant deviations from a linear trend may occur and take the form of poorly-defined concave curves. The absence of a linear trend is less likely to be due to the imprecise determination of the ratio between the two end-members than to heterogeneities of the natural samples which may arise from complex K-Ar evolutions of the detrital and diagenetic end-members. The straight-line approach is of limited use in the definition of diagenetic ages in shales by extrapolating linear trends to diagenetic end-members.

The composition of fluvial waters can be used to predict the processes of formation and evolution of secondary minerals in Galician soils. These processes are similar in areas with different rocks, from acid to basic, the only exception being strongly serpentinized materials. In general, the nature of the rock has less influence than the characteristics of the alteration system, which is always open, acid and freely draining. Mineral neoformation is always of the monosialitic type, having different degrees of evolution. The incipient phases tend to form gibbsite as a more stable mineral, and halloysite, allophanes and imogolite as metastable forms. With time, a crystalline kaolinite would be the only stable species. These results agree with the mineralogy and the andic or ferralic properties of the soils.

The sorption of Sr2+ ions by natural clinoptilolite was investigated using the batch method. The effects of pH, contact time and strontium concentrations were tested and the optimal conditions for sorption were determined. The process was very fast initially and equilibrium was reached within 24 h. Kinetic sorption data were fitted to pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The simple pseudo-second-order rate model provides good agreement with the experimental data for Sr2+ uptake. The respective rate constants, k2, calculated at different initial Sr2+ concentrations, were obtained. The equilibrium data were analysed by applying the Langmuir, Freundlich and Dubinin–Raduchkevich isotherm models. The Langmuir model describes the observed Sr2+ uptake most accurately and the value of the monolayer sorption capacity is 32.81 mg Sr2+/g. The effect of Na+ ions and the effectiveness of uptake from low saline groundwater simulated solutions were also studied and discussed.

The Neogene marls from the lower Kert area (northeast Morocco) were characterized to evaluate their suitability for the ceramics industry. Two cross-sections involving all of the Neogene facies were studied on both banks of the Kert River. Grey and green marls occurring between sandstone and tuffs were characterized by mineralogical (X-ray diffraction) and physicochemical (grain size, Atterberg limits, X-ray fluorescence and specific surface area) analyses. The Neogene clays studied are mainly calcareous silty marls containing 13–20 wt.% calcite. They consist of quartz, calcite, feldspars, dolomite, illite, kaolinite, chlorite and 10–14 Å illite-vermiculite mixed layers. Cristobalite was detected only in the uppermost level of the green marls, and it originates from a volcanic ash of Messinian age. Trace amounts of siderite and rhodochrosite indicate reducing or locally oxidizing conditions during sedimentation or shortly thereafter. The marls have medium to high plasticity, making them optimal for extrusion. Raw Neogene marls are suitable for manufacturing structural clay products. More specific uses, such as hollow products, roofing tiles and masonry bricks, were supported by the geochemical results and grain-size distribution.

X-ray photoelectron spectroscopy (XPS) was used to determine the surface-charge magnitude and distribution for some micas and high-illite I-S clays. Based on predictable layer by layer atomic ratios for margarite, muscovite and sericite it was possible to establish an escape depth of ∼15 Å for photoelectrons. After the replacement of surface ions by Ba2+, interlayer ion (Ca, K, Na)/Ba ratios are a measure of the relative layer charges on external surfaces and the first internal interlayer. These ratios can be used to assign charge magnitudes and ascertain layer charge asymmetry when it occurs. The O/Ba ratios determined by XPS serve the same purpose. Diagenetic I-S from the Vienna Basin gives an XPS-determined symmetrical layer charge of 0.41; in a similar clay from the Gulf Coast sequence, the outer surface is smectitic, with an external charge of 0.21, in contrast to an opposing silica layer with a charge of 0.31.

The behaviour of iron in the natural weathering of hornblende in a sedentary soil profile has been investigated using the Mòssbauer effect. The spectra from samples at different stages of weathering show appreciable differences which can be accounted for if ferrous iron is lost preferentially from M(3) sites where it is coordinated to hydroxyl groups in a trans arrangement. Unlike biotite the proportion of ferric iron does not increase during weathering and this illustrates the difficulty with which the ferrous iron is oxidized in the amphibole structure.

Cretaceous and Eocene bentonites from Azerbaijan have been studied from the standpoint of their occurrence, mode of formation, and mineralogy. The bentonites are shown to be derived from the vitroclastic products of volcanic eruption by transformation in a marine environment.

Montmorillonites ion-exchanged with Li+, Na+, K+ Ca2+, Mg2+ and Ni2+ and acidic clay were used as catalysts for the polymerization of a cyclic siloxane monomer, 2,4,6,8- tetramethylcyclotetrasiloxane. Montmorillonites with Ni2+ and Mg2+ in the interlayer, and acidic clay exhibit a greater ability for siloxane polymerization in both yield and mean molecular weight of products than those containing Li+, Na+ and K+. The difference in catalytic ability of the ionexchanged montmorillonites is caused by the number of Brmasted acid sites due to the polarization of H2O. This was confirmed experimentally by FTIR analysis of pyridine-treated samples. Therefore, it may be possible to design a catalyst for controlling siloxane polymerization (i.e. mean molecular weight of product) by changing the number of Bronsted acid sites through exchange of the interlayer cations of montmorillonites.

It is nearly a year now since we commenced the systematic investigation of our local soil clays in the North-East of Scotland by the powder method of X-ray analysis. In Aberdeenshire, one of the most wide-spread Soil Associations is the Insch Association, and this is the one I want particularly to talk about to-day. An association consists of soils derived from similar parent material, and the parent material of the Insch Association is till derived from basic igneous rock—mainly hypersthene gabbro, but sometimes with olivine also present.