Spanish montmorillonites from Frente Archidona were used to demonstrate the determination of charge density, CEC and, in mixtures, the montmorillonite content by the aikylammonium method. Special attention is directed to heterogeneous montmorillonites and the determination of the charge density distribution. Some problems which arise by application of the method are discussed: relations between layer charge and cation densities, particle size corrections, microstructures and unsymmetric charge distributions in the interlayer spaces.

Progress in science is not a linear function of time but resembles more closely a sigmoidal process in which new trends depend on the nucleation of new ideas and the re-activation of older studies. New and improved instruments, particularly electron microscopes and microprobes, infrared spectrometers and atomic absorption analysers have been the nucleating agents for many new lines of investigation. The interdisciplinary nature of clay mineralogy makes communication between different areas of study very important and the clay mineral societies have an important part to play in this respect.

In the future, renewed efforts to obtain a convenient and reliable method of quantitative mineral analysis are likely to be made. Crystal structure analysis will be directed increasingly towards the study of order and disorder in cation distributions, layer charges, and layer stacking arrangements. Studies of domain structures in layer silicates will continue, and further refinements in mixed-layer structure analysis can be expected. Infrared spectroscopic analysis will increasingly become a major tool. The study of clay mineral synthesis and alteration in nature and in the laboratory shows signs of important re-activation. Clay-organic studies are developing in many directions.

Par l'étude de la variation de la charge réticulaire relative et de la surface spécifique relative, accessible à l'eau, de smectites ayant subì l'effet Hofmann-Klemen à différents degrés, on montre que celles caractérisées par des substitutions tétraédriques (Beidellite B de Rupsroth et Ascan-gel) se différencient clairement de l'Ascan-argile qui ne contient que des substitutions en couche octaédrique. Dans la beidellite, la démixtion des cations Li, Na est totale pour toutes les compositions de la garniture cationique tandis que la démixtion n'apparaìt dans le cas de la montmorillonite que si (Na+/Li+) < 0·75. L'Ascan-gel occupe une position intermédiaire. Ces observations sont interprétées comme une indication que les substitutions tétraédriques empèchent l'expansion des feuillets en suspension.

Separation of the clay fraction from a calcareous soil usually involves chemical pretreatments which could affect the separated clays. A technique based on separating the flocculated particles (flocs) of a sonified soil-water suspension was used on highly calcareous samples and a highly gypseous one collected from a limestone ridge in Egypt. The relative abundance of the clay minerals in flocs (identified by XRD and electron microscopy) was found to be identical to that of < 1 μm clay separated by sedimentation. The suspensions were prepared by washing the soils repeatedly with distilled water (about 2 1/g) until spontaneous peptization.

Washing removed both 'amorphous' silica and alumina as detected in the flocs. The composition of poorly-ordered aluminosilicates (SiO2/Al2O3) of the 1μm clays was heterogeneous whereas in the flocs it was homogeneous.

Fluoride reactivity of both clay separates and prepared mixtures of CaCO3 with palygorskite (the dominant clay mineral present) was also studied.

Lepidocrocite was synthesized from the oxidation of FeCl2 solutions with and without soluble Si and at various Fe(II) concentrations and pH. Pure well crystallized lepidocrocite was only obtained if CO2 was excluded (to prevent goethite formation) and if pH was kept between 5 and 7 (to prevent maghemite and ferrihydrite formation). Si in solution prevented crystallization of lepidocrocite with increasing Si/Fe atomic ratio (varied between 0 and 0·156) and at the same ratio with decreasing pH. Most of the Si added is probably included in the lepidocrocite and ferrihydrite structure (up to 4·4% Si) and these Si contents are linearly correlated with the initial Si/Fe ratio. No indication from XRD and i.r. spectroscopy was found for changes in the lepidocrocite structure due to Si uptake. The ferrihydrite containing 4·35% Si showed a broad Si-O-stretching vibration which in contrast to pure silica (1080 cm−1) is shifted to lower frequencies (940 cm−1) indicating some Si-O-Fe bonds.

Electron microscopic examination of montmorillonite from the deposit near Redhill shows that the particles of the so-called blue clay are predominantly lathshaped with an average length: width ratio of 5. The so-called yellow clay from Redhill also contains a high proportion of similar lath-shaped particles, but many smaller lamellar particles are present which appear to be the results of lateral fracture of the laths. The majority of particles of montmorillonite in the fullers' earth deposit near Bath, Somerset, are platy with a similar shape distribution to Wyoming Bentonite, although smaller in size.

The electron microscopic technique used is based on a positively charged supporting film which, immersed in a clay suspension, preferentially selects negatively charged montmorillonite from the predominantly uncharged impurities. A conventional replica technique also showed lath-shaped particles in the blue clay.

The possible practical consequences of the different particle shapes are discussed.

The evolution of clay minerals in a Navarre Andosol (Spain) is investigated. The results indicate formation of allophane, evolution of trioctahedral mica to dioctahedral illite and the appearance of 10:14 A interstratified mineral in the lower layer. In the top horizons the interstratified mineral changes into vermiculite. The mineral distribution in the profile is indicated.

The location of iron in five deferrated soil kaolinites and several reference samples has been investigated using chemical analyses, acid dissolution and electron paramagnetic resonance spectroscopy.

The iron of most of the kaolinites can be divided into a 'structural iron' content, measured by the amount of iron, dissolved at the same rate as aluminium by acid attack, and a 'resistant iron' content, which is concentrated with the residues.

Integration of the geff~4 resonance bands of the electron paramagnetic resonance (EPR) spectra allows a semiquantitative estimate of the 'structural iron' in the samples. A multiple relationship seems to exist between the crystallinity index, the 'structural iron' content and the shape and intensity of both geff~4 and geff~2 EPR signals. The tropical soil kaolinites are a peculiar category with a high content of iron (>2% structural Fe2O3) fire-clay kaolinite, low crystallinity and a specific EPR spectrum exhibiting strong geff~4 resonance bands and no or weak geff~2 sharp doublet.

Dans ce travail, nous avons determine les caractéristiques des états d'équilibre de la montmorillonite calcique placée dans la phase vapeur délivrée par des solutions aqueuses d'éthane 1·2 diol, de propane 1·2 diol, de propane 1·3 diol, de butane 1·3 diol, de butane 1·4 diol et de butane 2-3 diol.

Les diagrammes de sélectivité, calculés à partir des isothermes d'adsorption, la diffraction des rayons X et la spectroscopic infrarouge mettent en evidence l'existence de deux phases adsorbées ayant des caractéristiques très différentes.

1. (1) Une phase interagrégat dont la composition est égale à celle de la solution d'équilibre.

2. (2) Une phase interfoliaire dont les caractéristiques sont étroitement liées à la stéréochimie de la molécule organique.

Les différents états stables mis en evidence s'expliquent par les energies mises en jeu par les interactions cations dipoles et les liaisons hydrogène intermoléculaires.

L'action catalytique des argiles sur la polymérisation des acides aminés en solution aqueuse a été étudiée. Les résultats rapportés par Katchalsky et coll. dans le cas de la polymérisation de l'analyl adenylate en presence de montmorillonite n'ont pu ètre reproduits. D'autres types d'activation des acides aminés ont été examines.

Glaukonitglimmer von 10 kretazischen Gesteinen werden mineralogisch und chemisch untersucht. Die von den Glaukonitkòrnern und Glimmern der Kolloidtonfraktion errechneten Strukturformeln der Glaukonitglimmer bestàtigen die Glaukonitglimmer als exakt dioktaedrische Minerale. Die Strukturformeln geben nur Mittelwerte der Verteilung der chemischen Hauptbestandteile und der Kationenladung der Glaukonitstruktur an. Innerhalb des Konzentrationsdreieckes Muskowit-Seladonit-Pyrophyllit deckt sich das Areal der Glaukonite mit dem der Illite, wenn auf den Seiten des Dreieckdiagrammes die Kationenladungen der Tetraeder-, Oktaeder- und Zwischenschichten aufgetragen werden. Entsprechend der iibereinstimmenden Verteilung der Kationenladungen in der Glaukonit- und Illitstruktur kònnen die Glaukonite als die eisenreichen Àquivalente der Illite angesehen werden. Der Gehalt an Spurenelementen in Glaukoniten ist, abgesehen vom Bor, deutlich geringer als in Biotiten und Muskowiten. Die chemische und strukturelle Inhomogenitat der Glaukonite in den Gesteinen wird am besten durch eine Entstehung der Glaukonite aus Gelen im Sediment erklàrt.

Bei der Untersuchung von 6 Glaukonitproben mit Hilfe der ‘H-Kernresonanz-Spektroskopie zeigen sich deutlich zwei verschieden gebundene OH-Gruppierungen. Wàhrend die relativ scharfen Signale A auf die in der Oktaederschicht flxierten zwei OH-Gruppen zuriickzufuhren sind, muB fiir die anderen OH-Gruppen des breiteren Signals B eine andere Bindungsnatur gefordert werden. Es ist móglich, dafl es sich bei den OH-Gruppen des Signals B ebenfalls um verschieden gebundene OH-Gruppen handelt und zwar um solche, die an Eisenhydroxid- Verunreinigungen gebunden sind und solche, die zwischenschichtlich in Form von Eisen-Hydroxo-Komplexen gebunden sind. Eine Unterscheidung zwischen letzteren beiden Mòglichkeiten ist aber nicht mòglich.

Beidellite clays near Chang-yuan, 80 km south of Hwalien, form vein-like bodies 5-10 m wide and 20-45 m deep. Andesitic rocks have been fractured by faulting permitting hydrothermal solutions to percolate and produce an altered mineral assemblage in which beidellite is associated with a mixed-layer illite-smectite, kaolinite, dusty pyrite, microquartz, cristobalite, calcite and dolomite, plagioclase, and gypsum. Ca-clay is common on outcrops and subsurface, where the clay is leached, Na-clay is found; some outcrops are partly kaolinized. Chemical analyses of the beidellite show that the structure is charged predominantly in the tetrahedral sheets. Exchange capacities are mainly in the range 120-140 mEq/100 g clay (110°C); exchangeable cations are Na ≫ Ca ≃ Mg > K. After K saturation and heating, ten samples still expand to near 17 A with ethylene glycol, but the two samples with the highest tetrahedral charge expand only to 14·6-15·0 Å although their total charge is similar to the other samples.

Three soil profiles developed on a serpentinite body (La Rochel'Abeille, near Limoges) show three stages of weathering. All soils contain iron-rich smectites and secondary chlorites. The latter are very silica-rich, more so than 14 Å chlorites from crystalline rocks. In the (B)1g horizon of the hydromorphic profile, these minerals seem to give a reaction of the type:

This reaction, typical of a closed system, appears to be operative in a soil profile which is certainly, in part, open to chemical migration. The chemistry of the weathered serpentinite and the chemical composition of newly formed minerals as well as those of the serpentinite are used to indicate the chemiographic relations of clay minerals formed in the weathering profiles.

L'exploitation des diagrammes de sélectivité de la montmorillonite, en equilibra avec la phase vapeur délivrée par des solutions aqueuses d'éthane 1-2 diol, permet de montrer que la quantité de diol interfoliaire est supérieure a 25 % et qu'elle est directement reliée à la chaleur d'hydratation des cations compensateurs.

Les cinétiques de désorption, réalisées à plusieurs températures, permettent de retrouver les mèmes résultats, à savoir que l'encombrement moléculaire depend du cation compensateur.

Ainsi, la mesure des surfaces totales des minéraux argileux avec l'éthane 1·2 diol n'a de sens que si, d'une part, on opere toujours avec le mème cation (σm = cte) et, d'autre part, on determine la quantité de diol en contact avec la surface à partir de plusieurs cinétiques de désorption réalisées à différentes temperatures.

Some parameters of the firing of kaolin around 900°C are examined: (1) firing shrinkage; (2) densification, hardening and textural evolution of kaolin ceramics. Experimental results are accounted for by an empirical formula describing the isotherm firing shrinkage of kaolin ceramics.

Depending on the precursor salt added, the spreading and dispersion of the mineralizer is more or less homogeneous. If, during thermal decomposition, the salt induces much porosity, this effect can counterbalance the shrinkage caused by the mineralizer. The kinetics of shrinkage, and the final density after firing depend both on the latter effects and on the mineralizer cation. A very good correlation is observed between shrinkage, final density (residual pore volume) and the strength of the fired clay product. The introduction of uniformly dispersed mineralizers causes an increase in mechanical resistance (for identical temperatures and firing times) by a factor greater than 3, occasionally 5) and, for equal firing times and mechanical strengths, lowers the firing temperature by 100-200°C.

A semi-quantitative mineralogical analysis of colliery spoil by XRD has been developed and used to compare spoils from eight collieries, in connection with work on the production of synthetic dense aggregates from spoil. Phase analysis of clay, which constitutes over half of all these spoils, is carried out by comparing X-ray peak areas of oriented specimens after heating and treatment with ethylene glycol. Total clay is obtained by difference, after determination of quartz and other minerals by an internal standard technique, allowing calculation of the proportion of each clay mineral. The results are tested against chemical analysis and a semiquantitative X-ray analysis of the chlorite present indicated that it is a highly ferruginous variety. Differences are detected in the mineralogy of all eight spoils but, except for the predominance of kaolinite in the spoils from Scotland, these differences are small.

The amorphous mineral selectively dissolved from the clay (<2 μm) fractions of twenty-six ferruginous soils contains considerable iron in addition to silicon and aluminium. SiO2/Al2O3 and SiO2/R2O3 molar ratios are between 2·03-3·52 and 1·72-2·95 respectively. The model of the amorphous ferri-aluminosilicate (AFAS) consists mainly of negatively charged tetrahedrally coordinated silica-alumina phase Si3AlO6(OH)4 containing domains of neutral FeOOH, with an outer positively charged hydroxyaluminium polymeric component [Al(OH)2.5]n.The calculated hydroxyl water content of the AFAS averages 17·8%; cation exchange capacity varies from 48·6 to 112·0 mEq/100 g and shows a negative correlation with the outer hydroxyaluminium octahedral component and a positive correlation with the ratio of the tetrahedral Si-Al component to the octahedral hydroxyaluminium component. The K-fixation capacity (1·9-6·1 mEq/100 g) of the AFAS does not appear to be related to the chemical composition. The genesis of the amorphous mineral is discussed.

Two outcrops were studied which showed granite in the early stages of weathering. Reactions between specific mineral species were observed, and especially the formation of an illite-like phase which is similar to that of sedimentary illite. This phase has a composition distinct from that of the initial micas in the rocks, notably in its iron and magnesium content. This suggests solution-solid equilibria which involve ionic transfer beyond the grain bondary region where the mineral is found.