L'analyse par diffraction des rayons X, résonance paramagnétique électronique et par spectrométrie infra-rouge des constituants minéraux du profil des Canonnettes (Sud-Est de la France) permet de montrer que les kaolinites sont ferrifères. De plus, au fur et à mesure du développement et de l'accumulation des oxy-hydroxydes de fer et d'alumine dans le profil, on note l'enrichissement progressif des kaolinites en fer en même temps qu'augmente leur désordre et que les taux de substitution en moles % d'AlOOH des goethites alumineuses devient plus important. Finalement, les kaolinites disparaissent remplacées par les oxy-hydroxydes de fer et d'aluminium, là ou leur accumulation est maximum.

The adsorption of cerium(IV) by both natural and Na-exchanged kaolinite from aqueous solutions of ceric ammonium nitrate was studied in equilibrium systems. Cerium may be adsorbed either as a monomeric species or as a polymeric hydroxy cation. The species adsorbed depends on the concentration of cerium in the stock solution, the age of this solution prior to the preparation of the equilibrium system and on the equilibration period. Adsorbed cations undergo polymerization on the surface of the kaolinite; the resulting polymeric species forms strong bonds with the clay surface—it is not desorbed by sulphuric acid—and may be considered fixed. Adsorption of cerium reaches a maximum in solutions containing 0·15 M sulphuric acid.

L' étude de la structure d' une argile sensible du Québec est abordée en porosimétrie au mercure après lyophilisation et en microscopie électronique à balayage sur une surface obtenue par fracture de l' échantillon congelé (système Cryoscan). On observe une structure en agrégats définissant deux classes de pores. A grande vitesse de congélation, la cristallisation de la glace semble surtout affecter les points faibles de la structure, qui sont les ponts de plaquettes reliant les agrégats les uns aux autres.

Complex formation between halloysites, from soil and geological sources, and a series of amides has been investigated. All the amides used can be intercalated to give single-layer complexes with basal spacings between 10·4 Å (for formamide) and 12·4 Å (for N,N-dimethylacetamide). When the interlayer space of halloysite has already been expanded by water, as is the case with fully hydrated samples, the rate and extent of intercalation depend more on the properties of the organic species than on the mineralogy of the clay. With partially and completely dehydrated halloysite, however, complex formation is influenced by the particle size, crystallinity, and iron content of the mineral. A large particle size, a high degree of crystallinity, and a low iron content are all conducive to complex formation. The iron content of halloysite also appears to affect particle shape. Low structural iron contents are associated with long tubular particles, intermediate contents with short and/or wide tubes, and high contents with spheroidal and other non-tubular forms. Halloysites containing high amounts of extractable (non-structural) iron generally show a low intercalating ability.

Olique-texture electron diffraction examination of K-saturated dioctahedral smectites after 70–100 wetting-drying cycles allows the determination of cation distribution between trans and cis octahedra of the 2:1 layers. Studies of smectites with different compositions has revealed a wide variety of occupancies of the available octahedral sites.

La relation entre la surface développée par les particules d'une poudre et leur paramètre de taille et de morphologie est abordée de façon théorique, rigoureuse et générale. A l'aide d'un nouveau choix des grandeurs mesurées, il est possible de ne prendre en compte qu'une seule distribution statistique, de l'un des paramètres, les autres paramètres n'apparaissant dans la formulation qu'à travers leurs moyennes arithmétiques. Dans le cas de plaquettes, le problème est analysé de façon théorique et expérimentale. La formulation est encore simplifiée et on voit que la formule la plus simple consistant à négliger surfaces latérales et distribution de taille est finalement parmi les meilleures, les deux approximations se compensant.

Bulk mineralogy, clay fraction mineralogy and layer ratio in interstratified illite-smectite were studied in three Upper Miocene profiles, up to 200 m deep and representing very low sedimentation rates (∼80 mm/103 yr) with environments of sedimentation ranging from hypersaline (gypsum deposits) to brackish. No correlation was found between mineralogy and depth, or between mineralogy and chemical environment of deposition, despite the use of precise identification techniques. It is concluded that smectites and interstratified illite-smectites are stable in marine sediments until the elevated temperatures of deep diagenesis are reached.

Les vermiculites magnésiennes chauffées durant plus de 24 h à une température de 700°C dans l'air, donnent une phase non gonflante qui est un biopyribole. Les diagrammes de diffraction X obtenus avec un monocristal montrent que ce matériau est constitué de deux phases: une enstatite en épitaxie sur le plan (010) d'un phyllosilicate. Le phyllosilicate a un empilement des feuillets semi-ordonné. Les rangées du plan (h0l) éant entièrement discrètes, la projection x0z a été étudiée par une analyse de Fourier classique à deux dimensions. Les autres rangéés du réseau réciproque sont plus ou moins diffuses dans la direction c*. Le désordre est creéé par une distribution aléatoire de trois translations entre les feuillets adjacents. Les relations structurales existant entre le phyllosilicate et l'enstatite expliquent l'absence de propriétés de gonflement de la phase phyllosilicate du biopyribole.

Solid-state 29Si and 27Al NMR spectroscopy with magic-angle spinning was used to study two smectites, two illites and a vermiculite. 27Al NMR was able to directly observe the coordination of aluminium. 29Si NMR was sensitive to both the chemical nature of the interlayer species and the presence of aluminium in the tetrahedral sheet. Well-resolved resonances in the vermiculite at δ = −84·6, −88·7 and −92·9 (ppm relative to TMS) were assigned to Q3(2Al), Q3(1Al) and Q3(0Al) respectively. The smectites exhibited single resonances centred at δ = −93 (Q3(0Al)). The illites displayed broad resonances between δ = −80 and −105. The 29Si spectrum of a smectite complexed with alkylammonium cations showed a shielding of up to 1 ppm relative to the untreated sample.

Rodrique et al. (1972) reported that kaolinite was formed at 200°C from gels with an A12O3/(A12O3 + SiO2) weight ratio ⩽0·315 and pH values ranging from 4·8 to 5·8. At this temperature and using a gel with an A12O3/(A12O3 + SiO2) weight ratio >0.315, boehmite and pseudoboehmite, were obtained at pH values of up to 5·8. The latter minerals were also observed in the products formed under similar conditions at 175°C.

Unlike the situation under acidic conditions, where gel composition is important, the gel/solution ratio becomes critical under alkaline conditions. When the gel/solution ratio is low, zeolites are produced from a gel with a weight ratio between 0·3 and 0·5 in the presence of NaOH at 130-170°C (De Kimpe, 1976). When the gel/solution ratio is high, kaolinite instead of zeolites is formed under similar conditions (De Kimpe, 1969, 1976). For an intermediate gel/solution ratio, smectite is produced from a gel with a weight ratio of 0.4 in the presence of NaOH at 175°C In the presence of KOH, however, kaolinite is the only crystalline product formed under similar pH and temperature conditions (De Kimpe et al., 1981).

The electron microprobe has been used in petrographic research for almost 20 years and more recently as a tool for investigations of clay minerals. However, to the author's knowledge no information has been published concerning the reliability of such analyses―especially those of the alkali elements. Since the alkali contents of clays are often critical, e.g. in determining the smectite content of mixed-layered minerals, it is important to have some idea of the reliability of an analysis made using an electron microprobe.

Three variables can be controlled in electron microprobe analysis—time, beam-current intensity and beam size (the diameter of the beam which excites the sample). Exaggerated conditions of any one of these variables tend to diminish the signal received by the detectors for the alkali elements, especially sodium. As an example, the effect of varying two of these parameters on the intensity of sodium radiation for sodium-aluminumsilicon glass is shown in Fig. 1. The signal decreases (% loss Na) over a 200 s counting time. Beam intensity and beam diameter were varied in this example.

Much interest has been shown in IR cells capable of maintaining one or more samples at constant temperature, constant water vapour or gas pressure, or under vacuum conditions (Farmer, 1974). This note describes a cell capable of maintaining a vacuum between 10-3 torr and 10-4 tort from room temperature to 1000°C whilst the spectrum is being recorded; such cells have been constructed previously but for less severe conditions.

The cell and associated vacuum system are shown schematically in Fig. 1. The vacuum in the cell body is produced by an Edwards rotary pump and a normal mercury diffusion pump. To obtain a vacuum of 10-3 to 10-4 torr, a liquid nitrogen trap and foreline trap are used. The trap is filled with activated alumina. The O-ring seals in the cell are made of Viton. The constant vacuum control is obtained with Pirani and Penning gauges.

It is well established that palygorskite has an amphibole-like, double-chain structure. The linked tetrahedral groups forming continuous sheets are divided into ribbons of various widths due to alternation of the direction of tetrahedra which run parallel to the fibre axis (Brindley, 1980). This alternation of the chains leaves a series of holes of well-defined size which are filled with water molecules (channel water). Based on microscopic observations of cleavage surfaces (Bailey, 1980), the mineral appears to be built up of regular stacking of planes parallel to (h00) and (hk0) which form predominantly the surface of the laths parallel to the c-axis. This is further supported by the enhanced X-ray reflections from these planes. Some degree of structural disorder might be expected to result from the progressive elimination of the channel water on heating. In addition, the weak interchain bonding in palygorskite is likely to result in a shift of the layers parallel to the fibre axis.

Lors de l'étude du gonflement des smectites par analyse de la diffusion des rayons X aux petits angles, Pons et al. (1981) et Ben Rhaiem (1983) ont obtenu des diagrammes de diffusion caractérisés dans le domaine étudié par des modulations plus ou moins prononcées de la courbe d'intensité.

L'analyse quantitative des courbes de diffusion, et en particulier de ces modulations, permet alors de remonter à une description de la structure du gel ou de la pâte et aux relations existant entre texture et structure (Pons et al., 1981; Pons et al., 1982). La méthode générale d'interprétation proposée par Pons et al. (1981) repose sur une comparaison entre intensité expérimentale et intensité théorique calculée à partir de modèles.