Many problems—from soil research to ceramics—require a reliable characterization of the clay minerals involved. This can be done using four clay-organic reactions: (i) staining tests and dye adsorption; (ii) glycerol and glycol adsorption; (iii) intercalation; (iv) alkylammonium ion exchange. Dye adsorption (staining tests) and glycerol adsorption allow a preliminary identification of the clay mineral groups. Intercalation reactions indicate minute differences between kaolins which cannot be detected by XRD and DTA. Alkylammonium ion exchange provides the best method for characterizing smectites and is sensitive to changes in the layer charge.

Nous proposons l'étude du mècanisme de gonflement d'une smectite, basée sur l'exploitation des diagrammes de diffusion aux petits angles obtenus avec la source de rayons X synchrotron de Lure (Orsay). Cette technique a permis d'étudier le gonflement, en fonction de la température, d'une montmorillonite Na, en suspension dans l'eau et concentrée à 20%.

L'analyse des diagrammes est éffectuée par une méhode basée sur la comparaison des courbes expérimentales à des courbes théoriques. Les modèles de structure permettant le calcul des diagrammes théoriques fait appel à la notion de particule (définie comme un empilement de feuillets parallèles) et de structure interne de la particule (définie par un ensemble de translations di affectées des probabilités pi qui déterminent la position mutuelle des feuillets).

Les résultats montrent qu'à basse température, les particules de très grande taille sont constituées par la superposition de sous empilements, comportant 4 à 5 feuillets, hydratés d'une manière homogène et se désorientant mutuellement pour former la structure du gel. On explique ainsi que la structure du gel formé est correlée avec celle du solide initial et que le phénomène de gonflement est quasi réversible.

Analysis of the distribution of gibbsite in soils and saprolites of Galicia, NW Spain, leads to the conclusion that this mineral is mostly formed by inorganic mechanisms in open, well-drained and desaturated systems in the initial stages of weathering of various aluminosilicates, especially plagioclases. No evidence has been found to support the hypothesis that it is a feature inherited from hotter climates, as it has not been identified to date either in ancient sediments or in the most evolved and weathered soils. The role of organic matter and the possibility ofa biogeochemical origin is also discussed: it is considered that this mechanism is only important during podsolic soil development.

Neuf saponites synthétiques ont été utilisées pour étudier l'influence des substitutions Si-Al sur le paramètre b et la distance basale d001 des phyllosilicates 2/1 trioctaèdriques. Dans les saponites hydratées à deux couches, le paramètre best le résultat des interactions entre couches octaèdrique et tétraèdriques. Dans les saponites hydratées à une couche, il dépend non seulement des paramètres des couches octaèdrique et tétraèdriques mais encore de la nature de la couche interfoliaire. L'effet du cation interfoliaire varie avec sa taille et sa localisation dans l'espace interfoliaire.

The structure of kaolin has been examined together with aspects of dosimetry and energy loss mechanisms of radiation to explain the formation of g = 2 EPR centres. The analysis points to the formation of a trapped hole on the ‘inner layer’ oxygen atoms of kaolin located at the boundaries between divalent ion and trivalent ion ‘cells’, in particular at the boundaries with excess negative charge. Direct interaction of X-rays with atoms and the possibility of proton recoil are eliminated. The means of production appears to be by transfer of charge following ionization of atoms by secondary electrons, with transfer of vacancies ultimately to the oxygen ions. Mechanisms which result in a decrease in signal strength with increase in concentration are examined. It is concluded that the cell mechanisms discussed are consistent with the rates of production and that at 20 Mrad (air) the number of centres should be reaching saturation.

Statistical (Q-mode) analysis of the chemical compositions of 122 dioctahedral smectites obtained from the literature have enabled the main solid solution ranges (montmorillonite, beidellite and nontronite) to be distinguished on a triangular diagram. In the montmorillonite area, the Wyoming, Tatatilla, Otay, Chambers and Non-Ideal montmorillonite compositional ranges are identified. Certain crystallochemical features of the smectites may be correlated with different genetic environments.

XRD, DTA, IR, chemical and electron microscopic data are presented for three specimens of regularly interstratified 25 Å minerals from Roseki deposits in Japan. The layer charges of these dioctahedral mica-smectites originate mainly from tetrahedral Al-for-Si substitution. The non-expandable interlayers are occupied by relatively large amounts of Ca and K as well as Na. The expansion characteristics of the expandable interlayers are montmorillonitic in spite of the beidellitic composition of the 2:1 layers.

Una sepiolita procedente de Toledo (España) se ha activado por tratamiento con disoluciones 0·25, 0·50 y 0·75 n de NO3H, seguido de calentamiento durante 10 h a 110, 200, 300, 400 y 500°C. Para cualquier concentración ácida, un calentamiento de 110, 200 y, a veces, 300°C, produce un aumento del número de poros mientras que las temperaturas superiores significan un cierre de los mismos tanto mayor cuanto más elevada es la temperatura de tratamiento. El máximo desarrollo de la superficie accesible al N2 tiene lugar con una disolución 0·50 n de NO3Hy 200°C (449 m2/g, método de BET); la superficie específica de la sepiolita natural es de 321 m2/g.

In the three previous papers of this series the role played by the exchangeable cations in the adsorption of methanol by homoionic montmorillonites has been investigated by different techniques, namely desorption isotherms, X-ray determination of the basal spacings and IR spectroscopy. In this last paper, models based on the previous discussions are presented. In the adsorbed state, methanol shows a strong tendency to form on the clay surface, hydrogen-bonded zig-zag chains analogous to those in crystalline CH3OH. The exchangeable cations perturb this arrangement to different extents. For Li+ the perturbation is negligible, for Ca2+ a complete rearrangement is observed and for Na+ and Ba2+ the chains are broken into smaller fragments.