A scheme is presented for the semi-micro analysis for the major elements in clay minerals, based mainly on improvements to conventional colorimetric methods. Silica and alumina are determined after fusing a 50-mg sample with sodium hydroxide. Titanium, total iron, calcium, magnesium, phosphorus and manganese are determined colorimetrically on a hydrofluoric-sulphuric acid digest of a 50-mg sample; sodium and potassium are determined flame photometrically on the same digest. Ferrous iron is determined separately. Additional methods for the determination of total water, total sulphur and fluorine are indicated.

A naturally occurring macroscopic sodium vermiculite from Unst, Shetland is described. It is similar in many respects to synthetic materials recently prepared from phlogopite by potassium replacement. In other respects, however, it is more akin to macroscopic Mg-vermiculites.

Water released by dehydroxylation was trapped in clay compacts during reactive hot pressing. The dynamic conditions of water pressure and temperature produced in the compacts modified the high temperature reactions of kaolinite. Kaolinite was converted to pyrophyllite or mullite in the temperature range 600-700°C depending on the applied pressure. Oriented aggregates of clay were used to determine orientational relationships between kaolinite and the high temperature phases. Structural continuity was observed in the reactions through the basal planes of kaolinite and pyrophyllite to the (130) plane of mullite.

X-ray analyses of argillaceous rocks from the Skipton anticline show that their average composition is quartz 30%, calcite 27%, feldspar 5%, illite 15%, kaolin 17%. Pyrite and other constituents account for the remaining 6 %. The quartz, calcite and feldspar are considered to be detrital, the variations in their quantity and size reflecting changes in the source of the sediments. The evidence indicates the general predominance of kaolin over illite, which is contrary to other published results on Carboniferous marine shales. A kaolin-rich source is necessary to account for the composition of the sediments. An occurrence of unusually pure and well-crystalline melanterite is recorded from the Draughton Limestone.

A 14 Å swelling mineral, interlayered with what is probably an organometallic complex, occurs in the surface horizon of a gleyed soil near Gartly, Aberdeenshire. The interlayer material is thermally stable at 300°C and is easily removed by oxidation with H2O2 and NaOCl. Treatment with HCl and Na2EDTA destroys the ability of the mineral to expand with glycerol, although not if the clay is H2O2 treated beforehand. The Gartly clay mineral is also unusual in that Mg-saturation, using magnesium acetate at pH 7, leads to the rapid formation of brucite-like interlayers. It is concluded that in the investigation of soil clays it is best to avoid all pretreatments.

A method is outlined and apparatus described to prepare rapidly and conveniently a reproduceable linear density gradient of any low-to-high value. The apparatus consists of two prismatic connected vessels of triangular shape one of which is inverted and tilted to a pre-calculated degree to account for the density difference of the liquids in the vessels. The liquids emerge, by gravitational levelling, from a common efflux tube connecting the vessels. 30 ml of density gradient can be withdrawn in 5 min. The linearity of the etflux is theoretically derived and shown experimentally using a number of organic liquids.

Because of increased interest in mineralogical analysis of soils a rapid, generally applicable method to separate clay minerals is needed, and such a method is described here. The technique is a modification of the heavy liquid density gradient centrifugation method which is commonly applied in mineralogical practice. Modifications are:

1. (1) The use of suitable surface active agents to overcome the flocculation problem.

2. (2) The use of the ultra centrifuge at about 33,000 g to hasten sedimentation.

3. (3) The use of a linear density gradient which supplies in addition a quick identification of the mineral composition.

Preliminary experiments, evaluating different variables (e.g. cation form, ultrasonic treatment, influence of surfactant), reveal the scope and limitations of the procedure presented.

Clay minerals of different density can be separated. However, if the clay minerals of a mixture have overlapping densities, or if they contain a series of mixed-layer minerals, only a broad fractionation is possible. This is shown by X-ray diffraction and electron microscope studies of isolated zones (or parts of them) which develop in the centrifuged density gradient columns containing various pre-treated natural clays or clay mixtures.

The electrical conductivity of synthetic zeolites, types X and Y has been studied to give information about the distribution and possibility of migration of the exchangeable cations, located at various sites. The Na+ samples were exchanged with K+, Cs+, Ag+, Li+, and NH4+. The various cationic forms were pressed into pellets and treated at 430°C under high vacuum for 24 hours. After cooling, the electrical conductivity and capacity was measured as a function of frequency (500–20,000 c/s) at various temperatures from −20°C up to 500°C. For each sample the reversibility was investigated. The experimental results allow the calculation of the specific conductivity, the real (ε′) and imaginary (ε″) part of the complex dielectric constant (ε*) and the loss factor tgδ.

The results show an ionic conductivity: the specific conductivity depends on the nature of the exchangeable cations as follows: Cs+ > K+ > Ag+ > Na+ > Li+. There is a different conductivity mechanism in the high temperature region compared with the low temperature region. At high temperatures (T > 400°K) the activation energy is independent of frequency. At low temperatures, a dielectuc absorption phenomenon occurs. The activation energy, calculated for this process was somewhat higher, but of the same order of magnitude as that of the high temperature region. It is suggested that the migration of the exchangeable cations in the supercage to interstitial positions gives rise to this dipole absorption phenomenon.

A comparison of the decationated Y zeolites with Na+Y and Na+X made it possible to attribute the conductivity to the cations in the supercage only. The exchangeable cations in the cubo-octahedra and in the hexagonal prisms lower the activation energy of the moving cations. Thus the energy of activation of X zeolites is lower than of Y zeolites.

The fibrous aluminosilicate imogolite has been studied by electronoptical and infrared absorption methods. Electron diffraction patterns are interpreted in terms of repeat units of 8·4 Å parallel and 23 Å perpendicular to the fibre axis. These spacings can not be reconciled with a continuous silicate chain structure and this conclusion is supported by an Si-O vibration near 930 cm−1. A structure is postulated in which distorted chains of Al-O octahedra are cross-linked through isolated Si2O7 groups.

Multiple OH stretching vibrations indicate different types of OH group in the imogolite structure. Absorption bands near 1000, 700 and 600 cm−1 are sensitive to sample orientation. This is attributed to the morphology and dimensions of the imogolite fibres.