XRD, DTA and IR patterns showed clay veins filling fissures in a granite of the Bayerischer Wald (eastern Bavaria) to consist mainly of hydrated halloysite of low crystallinity with traces of gibbsite, 2:1 (mixed layer) clay minerals and iron oxides. The halloysite forms thin plates which exhibit varying degrees and types of enrolment, resulting in platy, tubular and spheroidal crystals within the same sample. Concentrations of the trace elements Rb, Sr, Ba, Zr, Y, Ce, Pb, Zn and Cu indicate halloysite formation to have taken place via an aqueous phase under the influence of vadose waters circulating in fissures.

La mise en contact d'un minéral interstrafié mica-vermiculite, en paillettes de 1 à 4 mm2, avec une solution concentrée d'halogénure de métal alcalin conduit à un échange d'ions ainsi qu'à une adsorption de sel. L'échange d'ions n'est que partiel et l'adsorption de sel a lieu dans les interfeuillets vermiculite. La teneur du minéral en sel adsorbé dépend de la nature du cation et de l'anion du sel ainsi que de la température de la solution. Les complexes salins obtenus possèdent la propriété de gonfler macroscopiquement dans l'eau avec désorption du sel. Dans les cas des chlorures de lithium, de potassium et d'ammonium, les complexes salins tendent vers des compositions définies.

This paper describes reactions occurring between the 25.5 Å ammonium propionate (AP) intercalate of a well-crystallized Georgia kaolinite with ethylene glycol, 1-6-diaminohexane and a quaternary amine (QA), namely

An ethylene glycol kaolinite complex is obtained with a strong d001 reflection at 10.9 Å. Seven 00l orders are observed easily. The IR spectrum shows bands at 3697, 3654 (weak shoulder) 3644 and 3622 cm−1, assigned to OH stretching of kaolinite and a strong OH band of E.G. at 3300 cm−1. No absorption band of AP is observed.

The 1.6-diaminohexane product is characterized by two broad reflections at 16.6 and 7.4 Å. Distinct Amide I and Amide II IR bands imply that the carboxyl group of the propionic acid has reacted with the amino group. By treating the AP complex with QA a very stable kaolinite-QA complex suspension in benzene was obtained. On drying an X-ray amorphous solid with no reflection at spacing & 20 Å was obtained. The hydroxyl stretching bands of the original kaolinite are drastically modified, a very strong band at 3560 cm−1, a strong doublet at 3620 and 3605 cm−1 were observed. A weak singlet is obtained at 3695 cm−1. The two OH bending bands are replaced by a single band at 912 cm−1. A complicated set of interactions results in the loss of stacking order about the C-axis, accompanied by some curling of layer packets. A prolonged treatment with water restores the X-ray and IR spectra of the original kaolinite.

Une vermiculite-M (M = Na,K) sous la forme de macrocristaux gonflés à l'eau, de 1 à 4 mm2, adsorbe par échange d'ions des colorants cationiques en solution aqueuse. La sélectivité de cette vermiculite-M pour ces cations est très faible et sa teneur ne dépasse pas 7% de la capacité d'échange de cations.

Les spectres d'absorption visible des vermiculite-(M,colorant) obtenues, comparés à ceux des cations colorant en solution aqueuse, montrent dans le cas des cations bleu de méthylène, bleu de Nil A et vert brillant un déplacement de l'ordre de 25 nm de l'une des bandes. Du fait de l'adsorption, la charge des cations colorant adsorbés est plus localisée, soit sur leurs hétéroatomes centraux (bleu de méthylène), soit sur leurs hétéroatomes périphériques (vert brillant). La spectrométrie infrarouge ne contredit pas ces résultats.

Les vermiculite-(M,colorant) ne sont pas des pigments colorés et l'utilisation de la vermiculite comme support de colorants est très limitée.

Les auteurs étudient les produits de l'altération fumerollienne et météorique de Vulcano, Iles Eoliennes, Italie. Ces produits sont étudiés par diffraction des rayons X, analyse chimique classique, microscopie électronique et microsonde.

A comprehensive study of weathering in plagioclase-hornblende rock (amphibolite) from La Roche-l'Abeille, Massif Central, using optical and classical methods of clay mineralogy and electron microprobe determinations demonstrates the mineral reactions which can occur as amphibole and plagioclase weather. Both minerals decompose ultimately into beidellitic smectites but of different lattice compositions. It appears, depending on the host mineral, that an aluminous ‘intergrade’ mineral, similar to a hydroxy-complexed vermiculite, forms first, recrystallizing into the beidellites. Exchangeable ion composition of the beidellites suggests that all smectites were in equilibrium with waters of similar chemical activity for Ca and Mg ions at equivalent depths in the profile. The activities of the exchangeable interlayer ions of the newly-formed smectites are similar, regardless of the host mineral. Very local chemical potentials evidently dictate the lattice composition of the phases, ferribeidellite formed from amphiboles, aluminous beidellite formed from plagioclases, but longer range equilibria (centimetric) dictate the type of phase which will crystallize, i.e. smectite.

Se estudia el efecto de la deshidratación sobre la superficie especifica y distribución del tamaño de poro en sepiolita y palygorskita. Se emplean las técnicas de A.T.D., A.T.G., adsorción-desorción de nitrógeno y microscopía electrónica.

La eliminación del agua higroscópico-zeolitica incrementa en los dos minerales la superficie especifica y la proporción de microporos accesibles a las moléculas de nitrógeno.

Con la pérdida del agua de cristalización disminuye, en ambos minerales, la superficie especifica y la proporción de los citados microporos, desapareciendo los de anchura inferior a 7 Å en las próximidades de la eliminación completa de esta clase de agua.

La eliminación del agua de constitución origina neuvos descensos de la superficie especifica en la sepiolita de acuerdo con las alteraciones sufridas, puestas de manifesto en al análisis térmico; más acusadas que en la palygorskita.

Les auteurs ont étudié, par la technique de la diffusion brownienne l'interaction existant entre l'acide-L-glutamique et les systèmes eau-kaolinite et eau-montmorillonite, ainsi que l'influence du pH sur les coefficients de diffusion.

Il nous a été possible d'éliminer les facteurs mécaniques d'allongement de parcours en étudiant la diffusion de l'eau dans le système eau-argile.

Les résultats montrent une plus faible diffusion de l'acide glutamique dans le système eau-kaolinite que dans le système eau-montmorillonite.

L'effet du pH est discuté.

The reaction of ammonia with Mg-saturated vermiculite and hydrobiotite was studied by chemical analysis, X-ray diffraction, and differential thermal analysis, and the hydrobiotite also by infrared spectroscopy. The experimental evidence indicates that ammonia is adsorbed mainly as the ammonium ion, formed partly by reaction with interlayer water and partly by reaction with protons dissociated from octahedral layer hydroxyl groups, giving a single sheet of ions and molecules with irregular interlayer spacing. With large flakes (0.5–1.0 mm) the adsorbed ammonia is strongly retained on heating or on rehydration with water vapour: smaller flakes lose ammonia more readily. Ammonia uptake is related quantitatively to cation exchange capacity with two vermiculites and three hydrobiotites, and to the water content prior to adsorption.

Na-saturated vermiculite adsorbs a similar amount of ammonia to the Mg form, but it is mostly desorbed on rehydration. Cu-saturated vermiculite displays intermediate behaviour, with much of the ammonia initially present as a Cu-ammine which slowly reacts to give more ammonium ion.

The diagenesis of illite from smectite was investigated in relation to temperature on marly shale core samples from different Tertiary stages (depths between 200 and 3000 m) by X-ray and chemical analyses. It is concluded that the alteration of smectite to illite primarily depends on the cumulative energy supply (temperature × time). Small grain size and high potassium concentrations in the pore solutions shorten the time necessary to complete the alteration. Potassium is supplied by decomposition of feldspar within the sediment so that the replacement of feldspar by secondary calcite increases the availability of potassium. Supply of potassium by pore solutions from distant sources is very unlikely due to reduced permeability in compacted shales. Illite diagenesis is influenced by the inherited layer charge of the initial smectite.

The chemical composition of nine samples of Lower and Middle Chalk from the Givendale area of Yorkshire was determined; acetic acid residues were mechanically, chemically and mineralogically analysed. All nine chalk samples proved to be exceptionally pure calcium carbonate (96±1·5%), with only small amounts of MgO (1·03±0·53%), Al2O2 (0·33±0·28%) and Fe2O2 (0·20±0·14%). Insoluble residues ranged from 1·07 to 4·46%. Clay formed 56–88% of the insoluble residue. The non-clay fraction consisted of flint, quartz, collophane, limonite, feldspar, tourmaline and zircon. The clay fractions were dominated by montmorillonite (50%) with secondary illite (30%), apatite (3%), and quartz (8–30%). Kaolinite was detected by X-ray diffraction in the Lower Chalk.

On heating at temperatures below 600°C kaolinite reacts with salts of alkali metals according to the equation

2SiO2 · Al2O3 · 2H2O + 2nMX → 2SiO2 · Al2O3 · nM2O + 2nHX + (2−n)H2O

The reaction commences with the dehydroxylation of the clay and is favoured by high solubility of the salt and small size of the alkali ion.

It appears that on dehydroxylation the clay becomes reactive and, concurrently, the water liberated dissolves adjacent salt particles and catalyses the reaction.

Infrared spectra indicate that alkali ions are incorporated directly into the aluminosilicate structure, without the formation of metakaolinite as a detectable intermediate. The initial product is disordered, but as n approaches 1, crystalline phases tend to be formed.

Silicifications and smectite-dominated clay assemblages are associated in the marine Cretaceous sediments of England. Both are neoformed, and have developed at approximately the same time in the host sediment. Two silicification types, opal-CT and α-quartz, have a distribution pattern unrelated to the stratigraphy or lithology of the Lower Greensand, Upper Greensand and Lower Chalk. The petrography of five examples suggest that the two silicification types were both precipitated from the porewaters of their host sediment, and their silica mineralogy and their associated silicate minerals were controlled generally by the silica concentration of the porewaters and more locally by the pH gradients.