The mineralogical and chemical changes of sheridanite were followed in different alteration horizons as weathering of its host amphibolite increased. Microscopic and microprobe analyses of phases produced in or around the chlorite allowed a classification of the different alteration stages relative to their position in the profile. In the unweathered rock, prehnite and a sericite—kaolinite assemblage appear to have formed at grain boundaries between chlorites and plagioclases. These represent low-pressure (PH2O < 2.5 ± 1 Kb) and low-temperature (320–360°C) metamorphic phases. In the saprock, where initial rock structure is still preserved, chlorites weather to a more or less regular mixed-layer chlorite-vermiculite. In the saprolite, large-grain (20 µm) vermiculite forms in the clayey zones (plasma) when rock structure is destroyed. The chemical composition of these newly-formed minerals is influenced by the original chlorites and mixed-layer minerals.

Des lizardites substituées (Mg,Fe,Ni)3Si2O5(OH)4 ont été étudiées par spectrométrie en réflectance diffuse de 340 à 2500 nm, de manière à déterminer l'environnement de Mg2+, Ni2+ et Fe2+, en particulier la symétrie des sites et les distances métal-ligands. L'examen de la structure de la lizardite sensu stricto ayant conduit à définir pour Mg2+ deux sites hexacoordonnés M1 et M2 non équivalents dans la couche octaédrique du feuillet serpentineux, l'interprétation, à l'aide de la théorie du champ cristallin, des spectres d'absorption de lizardites de compositions chimiques variées a fourni les résultats suivants: 1. Le site M1 a la symétrie C2v: octaèdre orthorhombique. 2. Le site M2 a la symérie C3v: octaèdre rhomboédrique. 3. Fe2+ est hexacoordonné, et occupe les deux sites M1 et M2 si sa teneur est supérieure à environ 2%. Pour une teneur inférieure, Fe2+ n'occupe que M1. 4. Dans une lizardite Mg + Fe + Ni, Ni2+ est hexacoordonné et occupe le site M2. Ce site du nickel est plus grand en présence de Fe2+, que lorsque le nickel y est seul (népouite). Ni2+ y occupe une position plus rapprochée du centre de la couche octaédrique que Mg2+, ce qui contribue à réduire la flexion du plan des cations dans cette couche. 5. Dans une lizardite proche du pôle nickelifère (népouite), il y a réorganisation de la structure autour d'un site hexacoordonné unique de symétrie C3v. Ce site est déformé, et plus petit: distance moyenne métal-ligand r = 2·06 Å dans la népouite, r = 2·11 Å dans la lizardite magnésienne sensu stricto. Cette réduction de la taille du site ne peut se concevoir que par la réduction de l'épaisseur de la couche octaédrique: 2·20 Å (pôle Mg) à 2·16 Å (pôle Ni).

Interactions of ammonium sulphates and various silicate and oxide minerals have been studied by X-ray heating methods and simultaneous TG-DTA. Kaolinite and other clay minerals were found to be very susceptible to these sulphating treatments, (NH4)3Al(SO4)3, (NH4)Al(SO4)2 and Al2(SO4)3 being formed successively with increasing temperature from 350 to ∼550°C. The same reaction products were obtained on heating mixtures of (NH4)2SO4 and γ-Al2O3, Al(OH)3 and bauxite. Fe-, Mg- and Ti-silicates and oxides gave NH4-double sulphates below 400°C and the corresponding metal sulphates above this temperature.

Quantitative estimates were made by visually matching computer-simulated with experimental X-ray powder diffractometer patterns for two samples. One was a natural mixture of dickite and nacrite in about equal proportions. The second sample contained mostly quartz with corundum and mullite in small (0.5–1%) amounts. Percentages deduced from pattern matching agreed to within ±10% of the weight fractions of the components determined by an alternative method of analysis.

X-ray diffraction, optical and microprobe studies of a kaolinized oligoclase—orthoclase—two-mica—granite (Southern Armorican Massif) indicated that low-temperature metasomatism had produced three series of minerals. 1. Partial alteration of muscovite resulted in the formation of ferrous-magnesium-phengite. Biotite was destabilized to a kaolinite-titanium oxide assemblage. 2. Phengite, unreacted muscovite and feldspars recrystallized to an aluminous, magnesian 1M sericite mineral ranging in composition from mica to illite. 3. Feldspars were entirely destabilized to produce the assemblage potassic-beidellite-kaolinite—Al-illite. Kaolinite was the predominant mineral in the most altered rock. A fourth stage of mineral equilibrium was also observed; this occurred after material from stage 3 had been reworked. In this environment, the potassic-beidellite was replaced by a calcic-montmorillonite. Potassic-beidellite was not stable under weathering conditions.

The nickel arsenate KNiAsO4 has a mica-like layer structure with surface charge densities similar to brittle micas. In contrast to micas it easily exchanges alkylammonium ions. The interlayers have paraffin-type chain arrangements, as in alkylammonium vermiculites and alkylamine smectites and vermiculites, but the very regular chain packing causes a marked odd/even alternation of the basal spacings. The reactions of KNiAsO4 throw light on the exchange behaviour of micas.

La determinación del orden o desorden en la dirección perpendicular a las láminas en una nontronita anhidra ha sido efectuada a partir de las reflexiones 001 y 003 y de una parte de la difusión a pequeños ángulos. Mediante la comparación de diagramas experimentales y curvas calculadas a partir de modelos, se pretende poner en evidencia si el sistema es ordenado o desordenado y en el segundo caso la manera de establecer un modelo que traduzca el desorden del sistema. Se llega a la conclusión de que la nontronita potásica anhidra es un sistema desordenado en la dirección perpendicular a las láminas en el que aparecen espaciados correspondientes a varias distancias discretas afectadas por proporciones determinadas.

La composition minéralogique de la phase <2 µm de la croûte d'altération de teinte pâele et de quelques millimétres d'épaisseur, développée sur les faces des prismes basaltiques de Roudadou, près d'Aurillac, Cantal, a été étudiée par plusieurs techniques: RX, analyse thermique différentielle, thermogravimétrie, spectroscopie infra-rouge entre 600 et 200 cm−1, mesure des surfaces totales. Cette phase fine est constituée d'une fraction non cristalline relativement réduite et surtout de minéraux argileux cristallisés, parmi lesquels l'imogolite est largement dominante (50%), accompagnée de l'halloysite (30%). Parfois une smectite compléte ce cortège argileux. A notre connaissance, l'imogolite n'avait jamais été identifiée parmi les produits d'altération superficielle des roches volcaniques du Massif Central.

The method described uses external standard mixtures, both natural and artificial. Variations in degree of structural order between standard and analyte mineral are taken into account. ‘Amorphous’ materials in standard mixtures are simulated by alkali-boron-silicon glasses. Variations in response of the X-ray equipment with time are assessed by running a standard multiphase mixture. Strict control is exercised on particle orientation, and thermal treatments are used to separate overlapping reflections in the low-2θ region.

Porewater composition is the main control on diagenetic reactions in sandstones. Porewater has two possible contrasting primary sources: (i) fresh meteoric water, which is dilute and acidic, (ii) sea-water, which is alkaline and more concentrated than meteoric water. During burial, unstable minerals equilibrate with these porewaters, thus increasing the concentrations of dissolved species. A simple manometer model is used to describe the diagenesis of interconnected (fluvial or deltaic) sandstones. This model illustrates the following geological relationships: (a) a hydraulic head causes meteoric waters to penetrate deep into sedimentary basins, typically generating authigenic kaolinite; (b) decrease of the hydraulic head (by lowering the land level or by raising sea level) causes concentrated brines to rise within the basin, typically forming illitic cements; (c) enclosed sandstones (marine facies) are isolated from meteoric water flux and only receive fluxes when fault-induced or when uplifted. Kaolinite morphology and distribution are identified as being flux- or diffusion-controlled.

Scanning electron microscopy revealed that the organization of the interstitial micaceous mineral in the title sandstones depended on the manner of drying of the specimen. After air- and freeze-drying, the lath-like mineral tended to occur as mats densely packed against the pore walls, whereas after critical-point drying an open tangled web of very long, thin ribbons virtually filling the pore space was observed (this arrangement is the one most likely to occur in situ). The ends of these filamentous ribbons often appear to be bedded in authigenic quartz overgrowths on sand grains, thus anchoring them firmly in the pores. From transmission electron microscope observations, the individual laths were frequently only 2–3 nm thick and, from electron diffraction patterns, elongated along the a-axis: the stacking modification is 1M. X-ray diffraction patterns are those that would be expected from a fully-ordered interstratified mica-smectite containing ∼20% smectite layers. It is difficult to reconcile this with the thickness as observed under the transmission electron microscope, but a possible explanation is that the ‘smectite’ interlayers in reality represent spaces between individual crystals which formed when they sedimented into an oriented aggregate.

Under the influence of a pulsed field, dilute clay sols become birefringent as the particles undergo orientational order. The rate of decay of the birefringence on removal of the field is characteristic of the particle geometry. Measurement of the decay rates under two specific experimental conditions provides sufficient information from which the particle-size distribution can be evaluated in terms of a two-parameter function. Experimental data are reported and analysed in terms of a log-normal distribution of particle sizes for attapulgite (rods), kaolinite (discs) and halloysite (ellipsoids) sols and compared with success to electron microscopic data. The ability of the method to determine size distributions in terms of the major dimensions of the clay particles, rather than those of the often used equivalent sphere, is highlighted.

L'étude expérimentale de l'adsorption d'ions La3+ sur une smectite, successivement saturée en ions K+, Na+ puis Ca2+, montre que la stoechiomérie de l'échange s'effectue dans le rapport des charges des cations participant à la réaction. Dans un domaine de force ionique suffisamment restreint, l'échange a lieu dans les rapports suivants: 1 La3+ pour 3 Na+ ou 3 K+, et 1 La3+ pour 1·4 Ca2+. L'adsorption de toutes les terres rares sur la smectite et une illite s'effectue sans ségrégation notable dans cette famille d'éléments, les terres rares les plus lourdes étant un peu plus adsorbées que les terres rares légères. La désorption des terres rares est plus difficile, leur charge trivalente devant les stabiliser en position interfoliaire dans les minéraux argileux.

The technique of neutron inelastic scattering has demonstrated the presence of longitudinal acoustic phonons in two layer-silicate minerals. Values of the elastic constants determined from the dispersion curves have established the validity of the technique for this class of materials.

On étudie les équilibres de distribution de deux éléments de transition divalents A,B, entre gels silicatés inorganiques de formule SiO2-(A,B)O-nH2O et solutions aqueuses A2+,B2+ (A.B = Mg, Mn, Ni, Co, Cu, Zn). On montre que l'enthalpie libre molaire standard d'échange de deux éléments A,B entre gel et solution est une fonction linéaire de l'enthalpie libre d'échange calculée en considérant un échange théorique entre hydroxyde et solution. Les relations obtenues permettent de prévoir le comportement d'autres éléments divalents.

Sorption interlayer complexes of n-butylamine, sec-butylamine, iso-butylamine and diethylamine with homoionic Ln-montmorillonites (Ln = La, Sm, Gd, Er, Y) have been prepared. Compositions of the complexes are of the type: [Ln(butylamine)4]3+ and [Ln-(diethylamine)2]3+. The disposition of amine molecules surrounding the ion, the interaction between the amine group and the Ln3+ ion, and the strength of the ion-dipole bond have been studied by X-ray diffraction, IR spectroscopy and differential thermal analysis.

The Bridport Sands is a widespread marine sandstone of Lower Jurassic age found in much of southern England. It is a very fine grained, moderately sorted quartz-arenite and is characterized by the alternation of friable and hard calcareous-cemented layers. The sands form the upper reservoir in the Wytch Farm Field, Dorset, which is currently producing at the rate of around 4000 barrels per day. Investigation of core material to assess the suitability of water injection for gas/oil recovery has shown that significant reductions of liquid permeability compared to air permeability occur. These reductions vary from 30% or less in the best quality reservoir to more than 70% in low-permeability sandstones. Clay minerals in the Bridport Sands comprise mainly kaolinite and mixed-layer clays of both the illite-chlorite and illite-smectite types. Small amounts of vermiculite and chlorite also occur. The kaolinite is found as loosely-attached, discrete particles, whilst the mixed-layer clays form patchy pore linings. The permeability reductions may be explained by: (i) the adsorption of water and expansion of poorly-crystalline mixed-layer illite-smectites causing blockage of pore space (this reduction is largely reversible) and (ii) the physical movement of authigenic kaolinite crystal aggregates blocking pore-throats (this reduction is largely non-reversible). The pore-size distribution, clay particle sizes, the distribution of the clays within the pore space, and the composition of the clays are all important factors in controlling porosity/permeability relationships and permeability reductions in the friable reservoir intervals in the Bridport Sands.

Le mécanisme de dispersion dans l'eau d'une smectite a été étudié en fonction de 2 paramètres: la nature du cation interlamellaire, la nature du feuillet de smectite. Pour cela, on a observé l'évolution du diagramme de diffusion aux petits angles en fonction de la température (entre −15°C et la température ambiante) d'une série de dispersions contenant 20 g d'argile dans 100 g d'eau. La méhode d'interprétation des diagrammes est basée sur la comparaison entre courbes expérimentales et calculées. Les résultats obtenus montrent le rôle, dans l'aptitude au gonflement de la smectite, du cation interlamellaire, de la charge cu feuillet et de sa localisation. Ils montrent également quelles caractéristiques de la structure sont conservées entre la dispersion finale et le solide initial, ce qui permet d'en déduire le mécanisme de dispersion pour chaque smectite.