In non-aqueous systems, kaolinite can show, in addition to the physical interactions, considerable chemical activity. This study considers the chemical reactions that can occur at the kaolinite surface and explains these reactions in terms of acid-base interactions. In certain applications the chemical activity must be controlled if satisfactory products are to be obtained; for example, when kaolinite is used as a filler in rubber or as a diluent for insecticide powders. The concept of acid-base interactions is used to explain rheological and film properties in kaolinite-organic systems. The strength of the surface acid sites of kaolinite varies with the moisture content. At 1% moisture the surface is equivalent to 48% sulphuric acid whereas at 0% it is equivalent to 90% sulphuric acid. Therefore, the moisture level is extremely important and dry kaolinite will promote or catalyze many chemical reactions and where acid-base interactions are involved the presence of even small amounts of water usually retards or inhibits the reaction. Several examples explaining these interactions are given in the paper.

Extinction bend contours, observed in Cs-treated mica-vermiculites by transmission electron microscopy, give information on the morphology and crystal orientation and continuity in individual particles of clay size. Interlayer Cs apparently stretches that part of the silicate sheet in closest proximity and when exchange by Cs is incomplete, warping of the particle occurs. Warping favors the appearance of bend contours in transmission electron microscopic images of the particles. These contours terminate at crystal boundaries within a particle. A specimen tilting stage is useful in bringing the contours into view and in “exploring” individual particles.

The results of X-ray diffraction, DTA, i.r. spectroscopy, and chemical tests are presented for some chlorites typical of the Flagstaff Hill area. The area is notable for the large variety of chlorite types occurring in considerable quantities. Chlorite, in this area, is found as veins, as pseudomorphs, and as individual crystals. Textures vary from massive, fine-grained aggregates to books which are more than 20 mm in width. Crystals more than 5 mm in size occur in parallel groupings at rock interfaces. Judging from 45 chlorite samples studied, sheridanite is most abundant; clinochlore and ripidolite are common. Penninite and its Cr-chlorite equivalent are less abundant. The parent rock is an irregularly shaped ultramafic body surrounded by low-grade schists and located very close to a granodiorite stock. The original ultramafic rocks have been highly altered by metamorphism and metosomatism into assemblages comprised mainly of serpentine, talc, hornblende, and chlorite with relics of olivine, pyroxene, and other less abundant original minerals. Much of the exposed rock is essentially monomineralic, mostly consisting of various polytypes of serpentine. Preliminary investigation indicates that the area merits much more study because of the opportunity for readily observing the various chlorite types and determining their genesis, alteration sequences and weathering characteristics. The area, being easily accessible, could also serve as an adequate source for samples to be used as reference standards.

An experimentally determined Ca-Mg exchange isotherm of montmorillonite is reported. The selectivity coefficient of this exchange over a wide range of Mg saturation was calculated and found constant.

Standard free energies of exchange, thermodynamic equilibrium constants and activity coefficients of the exchangeable Ca and Mg ions in vermiculite and montmorillonite, were predicted from knowledge of the microstructure of these two clays, assuming that coulombic forces are the main ones playing a role in the interaction between the counterions and the charged clay surface. The standard free energies of exchange (ΔGCa°Mg = 238 cal/mole) predicted a preference for Ca in montmorillonite and a preference for Mg in vermiculite (ΔGCa°Mg = - 1665 cal/mole). The predicted thermodynamic equilibrium constants were compatible with the experimentally determined selectivity coefficients KsCaMg = 0·67 as compared with KsCaMg = 0·68 in montmorillonite, which remains constant over all the range of Mg saturation, and KCaMg = 16·7 as compared with KsCaMg = 13·9 in vermiculite at 95% Mg saturation. The activity coefficients of Ca and Mg counterions in montmorillonite were found to be and , respectively, and to remain constant. The activity coefficients of exchangeable Ca and Mg in vermiculite were found to be and , respectively, at an equivalent fraction of unity. The activity coefficient of exchangeable Mg increased as the saturation with Mg decreased, and was found to be 1·7 × 10-3 in the range of the low Mg saturation.

The microstructure, the isomorphic substitution and the surface charge density provided an understanding of the changes taking place in the activity coefficients of the counterions.

Inorganic gel and allophane collected from basaltic saprolite on Maui, Hawaii, and studied by Patterson in 1964 were reexamined. The main constituent of the gel is imogolite, and gibbsite and allophane are the minor constituents. Electron and X-ray diffraction patterns, DTA curve, and an infrared spectrum of the gel are characteristic of imogolite. The allophane is virtually noncrystalline to X-rays but contains a small amount of imogolite in relatively short threads. High-resolution electron micrographs indicate differences in structural organization between allophane and imogolite and suggest crystallization of imogolite from allophane.

The occurrence of imogolite as a weathering product has been reported in many localities from pyroclastic materials but not from massive rocks. Probably the exceptionally high rainfall, excellent subsurface permeability of the weathered material, and the low pH and high organic content of the leaching solution provide favorable conditions for formation of imogolite from basalt on Maui.

Sepiolite and attapulgite have been found to be common, sometimes the major, clay minerals in calcareous lacustrine deposits on the southern High Plains in West Texas and eastern New Mexico. Deflation debris derived from the basins and calcareous soils developed in the debris and in the lacustrine deposits also often contain either or both minerals. Dolomite is the carbonate commonly associated with sepiolite and calcite has a similar relationship to attapulgite in the lacustrine deposits. Pedogenic formation of sepiolite and attapulgite appears unlikely in the area studied since an association with lacustrine materials was made in a very high percentage of the occurrences.

Sepiolite was found to be highly concentrated in the < 0•2μ fraction. A similar, but less pronounced, distribution was noted for attapulgite. The studies suggest that the minerals have developed authigenically in alkaline lacustrine environments during periods of desiccation. Such an environment, interrupted by more humid periods, would have obtained during dry Pleistocene intervals. Volcanic ash is suggested as the source of the essential silica. The Mg concentration would appear to determine whether sepiolite-dolomite or attapulgite-calcite were formed.

A thermodynamic study has been made of the ion exchange equilibria of the n-alkylammonium ions in sodium montmorillonite. Exchange isotherms of ammonium, methylammonium, ethylammonium, propylammonium and butylammonium with sodium montmorillonite were determined at 4°, 25° and 55°C. From these data the changes in free energy, enthalpy and entropy for the exchange reactions were calculated. In the temperature region used in this work, no enthalpy change was observed. Thus the exchange was only controlled by entropy effects. The thermodynamic excess functions were calculated from the surface activity coefficients. The affinity of the organic ions for the clay increases with chain length. It is shown that this increase can not be ascribed to van der Waals forces, but must be due to the combined effect of variations in electrostatic interactions with the clay lattice and of the hydration state.

Sepiolite is seldom reported in playa deposits, even though it is generally believed to form in a highly saline, alkaline environment. Its rareness suggests that unusual conditions are necessary for formation of sepiolite. Sepiolite is a major constituent of a near-surface playa bed 4 ft thick in the Amargosa Desert, southern Nye County, Nevada. Associated materials include dolomite and small to trace amounts of quartz, feldspar, montmorillonite, illite, and volcanic glass. The dolomite, averaging about 2μ in size, makes up about 40% of the bed. The overlying beds and the underlying ones down to a sampled depth of 13½ ft are montmorillonitic (saponite) clays with moderate to trace amounts of sepiolite; dolomite is abundant in all these clays except in the uppermost several feet, where calcite is a major constituent. Ground water in this area contains abundant magnesium compared with that in the rest of the Amargosa Desert. An initial high concentration of magnesium in the playa lake water probably promoted the development of sepiolite and dolomite. Concentration of dissolved salts through evaporation of water is believed to have started chemical precipitation of dolomite, and this precipitation and the continued evaporation later caused deposition of sepiolite.

Sonic anisotropy of clay resulting from particle orientation was studied by means of velocity measurements on anisotropically consolidated kaolinite. Samples were prepared from a kaolin-water slurry under consolidation pressures ranging from 80 to 400 psi, with two distinct stress histories. Directional velocity measurements were made over a wide range of water contents as saturated samples were allowed to dry by evaporation to water contents below the shrinkage limit. Directional variation was most pronounced with partial saturation, when directional velocities differed by as much as a factor of two. The degree of sonic anisotropy is seen to correlate with variation in the shrinkage limit, showing a systematic dependence on particle orientation, but no unique relation to consolidation stress exists because of the overriding influence of stress history.

The i.r. spectra (4000-1200 cm-1) are obtained for several cation-substituted-montmonl-lonite-lysine complexes that were prepared at their natural pH’s. Analyses of the spectra of copper-, cobalt-, nickel- and zinc-montmorillonite films indicate that bidentate chelate complexes which contain protonated ∈-amino-groups are present in the interlamellar spaces. Investigation of the spectra of the hydrogen-, calcium- and natural-montmorillonite films indicates that the dominant adsorbed species for these complexes is a lysine cation in which both the α- and the ɛ-amino-groups are protonated while the carboxyl group is ionized.

The conversion of lepidocrocite (-γFeOOH) to its more stable polymorph, goethite (αFeOOH) was followed by observing changes in crystal morphology, oxalate solubility, surface area and X-ray diffraction. In conjunction, kinetics were measured as functions of surface area, temperature, alkalinity and seeding with goethite crystals.

The results suggest that the transformation is not topochemical, but proceeds through the solution phase. The main steps governing the rate of transformation are, (1) the dissolution of lepidocrocite, and (2) the formation of goethite nuclei and subsequent growth. Either of these processes can be rate-determining under appropriate conditions.

Several illites and a mixed-layer illite-montmorillonite developed fractures in some particles during progressive removal of interlayer potassium by solutions containing sodium tetraphenylboron. The appearance of the splinters in bundles, some connected to incompletely broken plates, suggests the process is related to the differential release of stresses known to exist as a consequence of octahedral-tetrahedral misfit. The formation of splinters produces additional surface area for ion removal and may influence the rate of vermiculite development.

Electron optical observations on Marblehead illite showed the presence of twinned aggregates of lath-shaped crystallites. The selected area diffraction patterns of these aggregates indicate a strict orientational relationship between them.

Original twinned mica flakes display all possible stages of the transformation of these micas into lath-shaped illites, where the a and b dimensions of layers do not show any noticeable changes, but c-dimension becomes shortened in the illites. The transformation seems to involve parting along (110) of the micas, subsequent H2O and OH inclusion in the structure and other possible chemical changes resulting from the hydration. The morphology and the size of lath-shaped crystallites displaying (001) and (110) forms seem to be responsible for the excess of water and K-deficiency in the Marblehead illite compared to the micas.

Individual illite laths commonly have a length 0·1–4 μ, a width of 0·01–0·1 μ and a thickness varying between 10 and 50 Å.

The cell dimensions and compositions of four chlorites whose crystal structures have been determined in detail are used to test existing graphs and regression equations designed to give tetrahedral and octahedral compositions. It is found that the thicknesses of the tetrahedral sheet, the 2:1 octahedral sheet, the interlayer sheet, and the space between the 2:1 layer and the interlayer can vary appreciably from specimen to specimen quite independently of tetrahedral composition. Total octahedral composition, the number of octahedral vacancies, cation ordering, and the distribution of trivalent cations and of charge between the two octahedral sheets must have effects on d(001) that are additional to the effect of tetrahedral composition. Nevertheless, Brindley’s d(001) graph and a regression equation by Kepezhinskas both should give tetrahedral compositions with an average error of 10%, or about 0·1 AlIV, for most trioctahedral chlorites. They are not valid for dioctahedral or di, trioctahedral species. Equations derived from the data of von Engelhardt and of Shirozu relating the b parameter to octahedral Fe, Mn content give results with an average error of 10%, or 0·1 Fe, Mn, for the four test chlorites provided Cr is included with the Fe, Mn, as does a regression equation by Kepezhinskas that contains terms for both the b parameter and d(001). Methods using the (00l) intensities or structure amplitudes give less consistent results for heavy atom contents than the spacing methods, but can be used to give approximate values for the asymmetry in distribution of heavy atoms between the 2:1 octahedral sheet and the interlayer.

A smectite rich in ferrous iron and low in aluminum occurs abundantly in the Red Sea Geothermal Deposits, and appear to be forming at present.

Chemical analyses and Mössbauer spectra indicate the mineral is intermediate in composition between nontronite and the as yet undescribed trioctahedral ferrous iron end member.

Oxidation of octahedral ferrous iron in biotite by saturated bromine water results in a loss of both octahedral and interlayer cations. The hydroxyl adjacent to vacant octahedral cation sites adopt an inclined orientation resulting in a more stable environment for interlayer cations. The only structural change accompanying these processes is a decrease in b-axis dimension which is linearly related to octahedral ferric iron content. These findings are in agreement with observations made on naturally weathered biotites.

Alteration products of volcanic materials from various localities in Wyoming, U.S.A., Italy, Yugoslavia and Mozambique are mainly smectites and cristobalites with small amounts of kaolinite.

Smectite and cristobalite form separate and intergrown aggregates of microcristallinity. X-ray diffraction studies show that the silica is α-cristobalite with a noticeable stacking disorder. Small aggregates of optically pure α-cristobalite, which were separated by an appropriate mixture of bromo-form and carbon tetrachloride, are shown to contain a noticeable amount of smectite on Debye-Scherrer diffraction photographs for the samples from Italy and Wyoming, U.S.A.

Transmission electron micrographs and selected area electron diffraction photographs show, in addition to smectite and α-cristobalite aggregates, the presence of idiomorph single crystals of kaolinite.

Interlayer K was extracted with sodium tetraphenylboron solution from a powdered sericite heated to the temperature of dehydroxylation and quenched to room temperature. By this procedure, sericite of the 2M1 type was changed to an interstratified mineral. The X-ray diffraction properties of this interstratified mineral are similar to “rectorite”.