Dehydration and rehydration of a phlogopitic Ca-vermiculite were studied by thermoanalysis (TG, DSC) and by in situ X-ray powder diffractometry. A detailed analysis of the relationship between temperature and state of hydration of the vermiculite close to equilibrium at atmospheric pressure was rendered possible by use of low heating rates in combination with a fast recording position-sensitive detector. The results reveal the existence of a number of distinct states of hydration characterized by basal spacings of 1.515, 1.493, 1.473, 1.188, 1.176 and 0.95 nm. In confirmation of results obtained earlier with Mg-vermiculite, regular interstratification occurred at dehydration during the transition between two- to one- and between one- to zero-layer hydrates showing integral series of 00l reflections with basal spacings of 2.67 and 2.11 nm, respectively.

Caesium aluminium silicates, caesium aluminium fluoride and aluminium fluoride were identified in a mixture obtained through the evaporation of kaolinite aqueous suspension with CsF. The mixture was studied by X-ray powder diffraction and IR spectroscopy. Two types of intercalation complexes of kaolinite were identified (A and B) which were characterized by c-spacings of ∼0.99 and 0.83 nm, respectively. Complex A seems to be an hydrated CsF intercalation complex, whereas complex B is a water intercalation complex, probably containing H3O+ and F−. It showed an IR absorption band at 3518 cm−1. The c-spacings of similar CsCl and CsBr complexes depend on the ionic radii. The intercalated ions are keyed into the ditrigonal cavities of the oxygen plane. A straight line plot of the keying values versus the ionic size indicates that keying is high for F−and decreases with increasing ionic size.

Une nacrite est intercalée par deux composés organiques polaires: le diméthylsulfoxide (DMSO) et le n-méthylacétamide (NMA). Les deux solvants ont des moments dipolaires très voisins (4 debyes) mais des constantes diélectriques différentes (49 pour le DMSO et 179 pour le NMA). L'intercalation du NMA est plus rapide que celle du DMSO. Les deux complexes homogènes obtenus sont étudiés par diffraction des rayons X, spectroscopie infrarouge et ATD. L'étude par spectroscopie IR a montré que la nacrite expansée par du DMSO se comporte comme la kaolinite expansée par le même solvant. Dans le cas de la nacrite intercalée par du NMA, trois nouvelles bandes d'absorption dues aux vibrations de valence des OH liés par pont hydrogène avec le groupement C=O et situées respectivement à 3500, 3543 et 3589 cm−1 apparaissent. La fréquence v(N-H) du NMA est intermédiaire entre celles du liquide et d'une solution diluée, indiquant une liaison par pont hydrogène probablement avec les oxygènes de la couche tétraédrique du silicate. La diffraction des rayons X sur des échantillons orientés nous a permis d'obtenir 13 réflexions 00l pour chaque complexe. Une étude quantitative, par transformée de Fourier monodimensionnelle dans la direction perpendiculaire au plan du feuillet, a permis de déterminer le nombre de molécules organiques intercalées (une molécule par Si2Al2O5(OH)4) et leur orientation dans l'espace interlamellaire. L'ATD a montré par ailleurs que le complexe Nac.DMSO est plus stable que le complexe Nac.NMA.

The development of the infrared (IR) absorption band at 1640 cm−1 (δH2O) is employed to monitor the gain in molecular water of progressively mortar-ground kaolinite. The planimetred area of this band shows a linear correlation with weight loss at 105°C (free moisture) between 2 and 18 h grinding, indicating a steady increase of molecular water in this range. Heating of ground products to 105°C causes a decrease of about ⅓ in the 1640 cm−1 peak area for all ground samples. This area decrease corresponds to a 34% (average) loss of free moisture as determined by gravimetry. The remaining water is held up to 280°C and is more tightly held in the kaolinite ground for shorter (2–5 h) intervals than in further ground kaolinites. The 1640 cm−1 peak is not detected in any ground kaolinite after heating to 600°C the temperature at which kaolinite dehydroxylates completely. The differentiation of the energetically different OH groups present in ground kaolinite and the mechanism of water gain are compared and discussed from IR spectroscopy and weight loss results.

Sepiolite from Vallecas (Spain) was treated with HCl solutions (1.25; 2.5; 5.0; 10.0 and 20.0 wt%) at 25°C for 2, 6, 24 and 48 h. The solutions obtained after washing the acid treated samples were analysed and a kinetic model was applied to the cation dissolution data. The development of porosity and number of acid centres was studied. The experimental conditions which yield products with the highest surface activity were established. The size of the silica fibres, obtained after the treatment, decreases when the intensity of the treatments is increased. These characteristics are important for the adsorptive properties and the catalytic potential of a solid.

Proteins (catalase, albumin, pepsin and lysozyme with different molecular weights and isoelectric points) were differently adsorbed at pH 7.0 on the clay fraction of three raw Na-saturated smectites (Crook and Uri montmorillonites and one hectorite). The adsorption isotherms of proteins on clay minerals showed typical Langmuir characteristics. Lysozyme was adsorbed under the effect of electrostatic interactions between the opposite charges of clay surfaces and protein molecules, whereas catalase and albumin were adsorbed under the effect of non-electrostatic forces. Pepsin was held in relatively high amounts only on the surfaces of hectorite. Proteins were intercalated in the interlayers spaces of smectites, usually undergoing extensive unfolding. Protein-smectite complexes showed different behaviour to heating treatment. Some complexes remained practically unchanged after heating at 200°C. Presence of ‘wrecks’ of interlayered materials was found after heating at 500°C for two hours. The amounts of proteins adsorbed on the external and interlamellar surfaces of clay minerals, partially coated with OH-Al species, were much lower than those fixed on the clean clays. Only lysozyme was intercalated in chlorite-like complexes.

L'arrangement des cations décylammonium échangés entre les feuillets de la vermiculite et de l'hectorite a été précisé à l'aide des spectrométries infrarouge (IR) et Raman. Les expériences de deutération et de dichroïsme faites par spectrométrie IR montrent que l'axe C3 du groupe NH3+ est confondu avec l'axe de la cavité hexagonale sous-jacente, dans le cas de la vermiculite comme dans celui de l'hectorite, et que dans la vermiculite, les groupes NH sont engagés dans des liaisons hydrogène avec les atomes d'oxygène des tétraèdres substitués. La spectrométrie Raman permet de comparer l'arrangement des chaînes alkyles dans les deux phyllosilicates. En effet, cette technique donne accès à des modes de vibration très sensibles à la conformation des chaînes carbonées, en particulier grâce à la décomposition des bandes de vibration de valence des groupements CH2 et CH3. Ainsi, dans la vermiculite, on montre que les chaînes sont linéaires, et que leur arrangement interdigité est proche de celui du chlorure de décylammonium cristallisé. Les spectres Raman obtenus pour l'hectorite mettent en évidence l'existence de conformations gauches dans les chaînes alkyles, qui caractérisent une rotation de la chaîne autour de la liaison C-C voisine du groupe NH3+ terminal. Les résultats obtenus en Raman montrent par ailleurs que les interactions entre les chaînes alkyles sont beaucoup plus faibles que dans le cas de la vermiculite et confortent le modèle proposé ici pour le complexe hectorite-décylammonium, pour lequel les chaînes sont parallèle aux surfaces des feuillets.

Samples from deep wells of the Palaeozoic Illinois Basin show the evolution of the illite-smectite (I-S) mineral transformation under low temperatures for very long periods of time. Curve decomposition of the XRD traces was used to identify and follow the evolution of the different clay minerals. All samples showed the presence of a large amount of illite (fine and coarse grained micaceous material) and a much smaller quantity of I-S. In a vertical section the R=1, I-S diffraction peak initially changes with depth indicating change from 80 to 95% illite content but it changes little with further depth. The I-S intensity decreases with depth compared with the illite peaks. These relations indicate that the clays in the Palaeozoic sequence of the Illinois Basin evolve continuously in the deep well, It appears that the final stages of I-S mineral transformation can reach a compositional stagnation (smectite content) as the I-S phase is dissolved to produce illite.

Using a kinetic model to describe the smectite to illite clay transformation, it is deduced that the Illinois basin had a longer period of deposition than indicated by present stratigraphy and that almost 1.5 km of sediments deposited in the Mesozoic were eroded in later Tertiary times. These conclusions are confirmed by published data on the maturation of organic matter.

According to XRD, DTA, geochemistry and electron microscopy data of a few selected samples, three categories of smectitic clay minerals occur in the Cenomanian and Turonian chalks sampled in several sections of northern France. The first one corresponds to detrital illitesmectite mixed-layers reworked from pedogenic blankets. The second category, characterized by crystalline overgrowths around detrital particles, is especially well-developed in slowly deposited sediments. The third category, located in thin marly horizons, corresponds to Cheto-montmorillonite derived from the submarine alteration of volcanic glass. Smectitic minerals having distinct origins may therefore occur at different levels of a given formation. From these examples, the smectite-rich clay sedimentation of the Late Cretaceous is tentatively explained by the combination of favourable factors induced mainly by highstand of the sea-level. The climatic conditions, the reduction of continental areas, the development of carbonate platforms and the decrease in sedimentation rates constitute the most relevant of these factors.

Two profiles in Devonian marine deposits have been studied, consisting of pelites, subgreywackes, greywackes and quartzites. Quartz and clay minerals are major components and feldspar and calcite are minor ones. Phyllosilicates in the fine fractions are kaolinite and illite; kaolinite has a high degree of ordering; illite is predominantly of a 1Md polytype, with low Na content and poor crystallinity and has a phengitic composition in greywackes, whereas in pelites it is muscovitic in composition. Both phyllosilicates may be inherited from a source area with intensive weathering processes, although illite may also be a diagenetic phase. These mineral characteristics indicate that the Devonian rocks did not reach the anchizone boundary in their post-depositional evolution.

The chemical composition of pelites and subgreywackes reveals a high degree of chemical maturity. Chondrite-normalized REE patterns indicate a higher degree of weathering of these Devonian sediments than of Post-Archaean Australian Shales (PAAS), possibly as a consequence of sedimentary recycling processes. The REE patterns of the Devonian rocks in addition to the high Th/Sc, La/Sc and Th/Co ratios suggest a felsic composition of the primitive source area, probably a K-rich granite.

The Tertiary sediments of the southern part of Almazán basin (Province of Soria) exhibit two different facies with a sharp transition between them: (1) a coarse detrital facies; and (2) a lutite and carbonate facies. The vertical evolution of these facies in the different sections and boreholes is made up of several retrograde depositional sequences which evolve from proximal alluvial fans to carbonate lacustrine systems associated with the most distal fan sediments.

The variation of the mineralogical association (carbonates, quartz, detrital clay minerals, palygorskite and, occasionally, sepiolite and smectites) allows four ‘mineralogical facies’ to be established. Each facies has a distinctive mineralogy related to the main genetic processes: (1) detrital facies; (2) transitional facies; (3) ‘chemical dolomite-palygorskite’ facies and (4) ‘chemical calcite’ facies. Although the carbonates (calcite and dolomite) are always the most abundant minerals, fibrous clay minerals are also important. The main mechanism of mineral authigenesis in this basin is chemical precipitation; the presence and distribution of carbonates and fibrous clay minerals is controlled by the relative concentrations of [Mg2+], [Ca2+], pCO2, pH and [SiO4H4]. Palygorskite occurrences, in these conditions, are related to dissolution-precipitation mechanisms of pre-existing detrital material.

The transition between very low-grade and low-grade metamorphism has been studied in the Urbión and Enciso Groups of the Late Jurassic-Early Cretaceous Cameros basin (NE Spain). The ‘illite crystallinity’ (IC) values do not appear to be controlled by burial depth but rather by: (1) XRD overlap with other phases (e.g. paragonite and mixed-layered muscovite-paragonite) in the siliciclastic samples; (2) the presence of carbonates, which delay illitization, resulting in an increase in the IC values, that becomes more pronounced as the P-T conditions decrease towards the diagenesis zone; and (3) the permeability of the sediments, which controls the circulation of metamorphic fluids and therefore the distribution of ‘crystallinities’ and mineral assemblages within the basin.

The anchizone is represented by a narrow range of ‘chlorite crystallinity’ (ChC) values. Therefore, ChC is a less sensitive parameter than IC for estimating changes from diagenetic to low-grade metamorphic conditions. However, ChC can be a useful tool when there is a great heterogeneity of facies types, as it is not affected by the presence of carbonates.