An attempt has been made to assemble the best thermodynamic information currently available for soil minerals in the Al2O3-SiO2-H2O system at 25°C and 1 atm. Montmorillonite is included by considering its aluminum silicate phase. Diagrams are presented so that the stability of the minerals can be visualized in relation to the ionic environment. Although the Al2O3-SiO2-H2O system is a very simple one compared to soils and sediments, the stability diagrams depict a mineral stability sequence and mineral pair associations that are in good agreement with natural relations.

According to the stability diagram, mineral pairs that can form in intimate association are gibbsite-kaolinite, kaolinite-montmorillonite, and montmorillonite-amorphous silica. Forbidden pairs are amorphous silica-kaolinite, amorphous silica-gibbsite, and montmorillonite-gibbsite. The formation of intimate mixtures of three or more of these minerals is also forbidden. The stability diagrams predict ion activity relationships that are in reasonable agreement with those obtained from soils and sediments.

Amorphous silica probably limits high silica levels, with montmorillonite also forming at high silica levels. Kaolinite forms at intermediate and gibbsite at low silica levels. These minerals in turn probably control the activity of aluminum ions at a level appropriate to the pH. The formation of gibbsite, kaolinite, montmorillonite and amorphous silica appears to be controlled by a combination of kinetics and equilibria. That is, the kinetic dissolution of unstable silicates appears to control the H4SiO4 level. The new mineral(s) most stable at that H4SiO4 level appear to precipitate in response to solution equilibria.

The electrical conductivity of saturated kaolinite clay-water-electrolyte systems of different particle size distributions and of illite and montmorillonite clays were determined over the frequency range of 50–108 c/s. The conductivity increases as the frequency increases, and the experimental values show two distinct dispersions, one in the low frequency range and the other in the high frequency range. The frequency range over which the first dispersion occurs is experimentally shown to be dependent on particle size. The average particle size is uniquely related to the frequency at which half the dispersion occurs. The magnitude of conductivity variation, the high frequency conductivity and the streaming potential values are related to the microscopic permeability coefficient. This microscopic permeability coefficient, evaluated from a knowledge of the above electrical properties, is shown to be uniquely related to the Darcy permeability coefficient at various consolidation states of the kaolinite clays. Similar unique relationships have been observed in illitic clays.

Weathering products formed on surfaces of both potassium and plagioclase feldspar (An70), which were continuously leached in a Soxhlet extraction apparatus for 140 days with 7·21 of distilled water per day at a temperature of approximately 78°C, are morphologically identical to natural products developed on potassium feldspars weathered under conditions of good drainage in the humid tropics. The new products, which first appear as tiny bumps on the feldspar surface, start to develop mainly at exposed edges but also at apparently random sites on flat cleavage surfaces. As weathering continues, the bumps grow outward from the feldspar surface to form tapered projections, which then develop into wide-based thin films or sheets. The thin sheets of many projections merge laterally to form one continuous flame-shaped sheet. The sheets formed on potassium feldspars may then roll to form tubes that are inclined at a high angle to the feldspar surface. Etch pits of triangular outline on the artificially weathered potassium feldspars serve as sites for development of continuous, non-rolled, hollow tubes. It is inferred from its morphology that this weathering product is halloysite or its primitive form. The product of naturally weathered potassium feldspars is halloysite · 4H2O.

The flame-shaped films or sheets formed on artificially weathered plagioclase feldspar do not develop into hollow tubes, but instead give rise to a platy mineral that is most probably boehmite. These plates form within the flame-shaped films, and with continued weathering are released as the film deteriorates. There is no indication from this experiment that platy pseudohexagonal kaolinite forms from any of these minerals under the initial stage of weathering.

This investigation was designed to integrate the quick-freeze technique for ion diffusion with two computer programs to permit the simultaneous measurement and calculation of the diffus-ivity of a variable number of ions in heteroionic soil system. Kaolinite clay was prepared so as to have the following percentage saturations of the CEC, Sr2+65, Mg2+15, Rb+10, Na+5 and H+5. A quadruplicate radioisotope tag consisting of 85Sr, 28Mg, 86Rb, and 22Na was used to measure the diffusivity of each ion. The complex spectra were resolved by use of Schonfeld’s revised Alpha-M computer program. A probit-transformation procedure was formulated into a computer program to enable the calculation of each diffusion coefficient. These programs are described and illustrated with the diffusivity of 86Rb in kaolinite clay.

Completeness of exchange of K from muscovite by Ba2+ ions decreased with particle size below 20 μ. Accompanying K exchange at 120°C, using a repeated batch technique, was a marked loss of Si and the formation of boehmite in the finer fractions. Several possible explanations for the unexpected high K retention of fine mica fractions are discussed. The formation of a diffusion-inhibiting surface “skin” is discounted, because equilibrium was obtained more rapidly with the fine fractions than with coarser fractions. The average degree of bending of unit mica layers due to peripheral expansion is probably greater in large particles. With bending, rotation of tetrahedra and shifting of adjacent layers with respect to each other may induce greater release of K and a lower selectivity for this ion. Fault planes may induce preferential expansion of individual layers and initiate interstratification and splitting of particles. Splitting of particles may reduce bending and increase K selectivity.

A structure model for amorphous hydrated or dehydrated silico-aluminas with composition varying between 0 < Al: Al + Si < 1 is presented. A central core made from a tetrahedral network in which silicon is partially substituted by aluminium carries a net negative electrical charge. This charge is balanced by more or less polymerized hydroxyaluminium cations forming a coating around the core.

As Al: Al + Si increases, the number of substitutions in the core increases as well as the complexity of the hydroxyaluminium cations in the coating.

For Al: Al + Si ≳ 0·8, a demixing is observed, leading to the formation of a crystalline pseudo-boehmite and bayerite.

Upon heating, the coating as well as the demixed phases are transformed into a spinel structure containing tetrahedral aluminium, while the core structure remains unaffected.

This model could explain the solubility features, the phosphate reaction and the catalytic properties of amorphous silico-aluminas.

The small angle X-ray scattering data obtained in an earlier investigation of a series of Na-montmorillonite clay samples containing varying concentrations of sodium metaphosphate have been used to calculate the potential energy φ(x) of the interaction between two isolated parallel clay platelets separated by a distance x. All φ(x) curves have the form expected for Na-montmorillonite. In each curve there is a potential well for a platelet separation approximately equal to the most probable separation distance determined in the earlier study. Because the depth of the potential well is of the order of 0·01 eV for all samples, the attractive forces are relatively weak. While the calculated φ(x) functions are not highly accurate, in future investigations precautions can be taken to increase the reliability of the computed potential energy functions. This preliminary study suggests that determination of φ(x) from small angle X-ray scattering data can be a useful method for quantitative study of interparticle forces in Na-montmorillonite clays.

Palygorskite and sepiolite were digested with large excesses of hydrochloric acid at constant temperature for various periods of time. The reaction was found to be of first order with respect to the magnesium, aluminum and iron components in the clay and also with respect to hydrochloric acid concentration.

The reaction rate constant for Mg is larger than for Fe, which is larger than for Al. Approximately one-third of the octahedral-type cations are extraneous, suggesting that only three of the five octahedral positions are filled. The reaction rate constant of Mg in sepiolite is about 240 times that for palygorskite. This may be an indication that sepiolite is less stable to chemical weathering than palygorskite.

The activation energies for Mg, Al and Fe in palygorskite were found to be the same and equal to about 18·4 kcal per mole.

Treatment of partially acid-digested palygorskite with magnesium ions under alkaline conditions resulted in an increase in the X-ray intensity of the 10·5 Å spacing, suggesting some of the palygorskite was reconstituted.

Polytypism in trioctahedral 1 : 1 phyllosilicates results from two variable features in the structure. (1) The octabedral cations may occupy the same set of three positions throughout or may alternate regularly between two different sets of positions in successive layers. (2) Hydrogen bonding between adjacent oxygen and hydroxyl surfaces of successive layers can be obtained by three different relative positions of layers: (a) direct superposition of layers, (b) shift of the second layer by a/3 along any of the three hexagonal X-axes of the initial layer, with a positive or negative sense of shift determined uniquely by the octahedral cation set occupied in the lower layer, and (c) shift of the second layer by ± b/3 along Y1 (normal to X1) of the initial layer regardless of octahedral cation sets occupied. Assuming ideal hexagonal geometry, no cation ordering, and no intermixing in the same crystal of the three possible types of layer superpositions, then twelve standard polytypes (plus four enantiomorphs) with periodicities between one and six layers may be derived. Relative shifts along the three X-axes lead to the same layer sequences derived for the micas, namely 1M, 2M1, 3T, 2M2, 2Or, and 6H. Polytypes 1T and 2H1 result from direct superposition of layers. Layer shifts of b/3 lead to polytypes designated 2T, 3R, 2H2, and 6R. The twelve standard 1 : 1 structures can be divided into four groups (A = 1M, 2M1, 3T; B = 2M2, 2Or, 6H; C = 1T, 2T, 3R; D = 2H1, 2H2, 6R) for identification purposes. The strong X-ray reflections serve to identify each group and the weaker reflections differentiate the three structures within each group. Examples of all four groups and of 9 of the 12 individual structures have been identified in natural specimens. Consideration of the relative amounts of attraction and repulsion between the ions in the structures leads to the predicted stability sequence group C > group D > group A > group B, in moderately good agreement with observed abundances of these structural groups.

A technique was developed for forming clay beds of uniform porosity between 48 and 62 per cent. The surface conductance and streaming potential of sodium kaolinite were determined over a range of values. Zeta potential as calculated from the classical formula was about - 30 mV at neutral pH and changed sign at pH 4. The surface conductivity of the sodium clay at various pH values was directly proportional to the zeta potential and from 12 to more than 30 times as large as the calculated electrokinetic surface conductivity. Similar measurements were made on kaolinite in the acid (hydrogen-aluminum) and calcium forms. The acid clay fitted the experimental correlation found for the sodium series, but the calcium clay, with less than one-tenth of the zeta potential of the sodium clay at neutral pH, had half its surface conductance. The results are interpreted as showing that exchangeable ions on kaolinite are mostly in a condensed layer on the surface where the mobility determines surface conductance. The surface mobilities for Na, Ca and H-Al are 20, 8 and 0 per cent of normal, respectively. Apparently hydrogen ion from the solution is very effective in replacing sodium, which exhibits its electrokinetic and conductive properties in proportion to its concentration on the surface.

Tosudite from the Takatama mine is found as an alteration mineral of the wall rocks (tuff and tuffaceous sediments of Tertiary age) of gold-silver-quartz veins. A specimen free from impurities was obtained by the sedimentation method. Chemical composition: SiO2 42·14%; Al2O3 37·38%; Fe2O3 0·30%; MgO 0·08%; CaO 1·65%; Na2O 0·15%; K2O 1·40%; H2O+ 11·22%; H2O− 6·16%; total 100·48%. A negligible amount of MgO indicates that both octahedral sheets of the chlorite structure are dioctahedral. Structural formula is given as (K0.58 Na0.09 Ca0.57)(Mg0.04 Fe3+0.07 Al12.05) (Al2.28 Si13.72) O40.00(OH)20.008.88H2O.

A reflection at 30 Å with its higher order reflections and another reflection at 1·493 Å are observed. After heating at 300°C, a 27 Å phase has appeared, in which a single plane of water molecules was confirmed as the interlayer water of montmorillonite. The structures in air-dried state and in dehydrated steps were proved by comparing the calculated and observed F-values, and by Fourier synthesis. The DTA and TG curves and the i.r. absorption spectrum are reported in this paper.

Crystallites of the finest fraction of a clay mineral from Rosamund, California, which account for over 50 per cent of the total weight, are identified as wairakite single crystals of 0·1–1 μ size. High-magnification electron microscopy revealed flat, almost perfectly square-shaped lamellae, which consist of superimposed layers of approximately < 50 Å thickness. Electron diffraction patterns from a selected single crystal proved that the basal plane of the crystallite aligned perpendicular to the electron beam is the (111) plane. It is suggested on the basis of the present study and the report of previous investigators that the pseudocubic wairakite crystals cleave along their (111) and ($\bar 1$11) planes. The indices of high order reflections, unpublished or previously reported as uncertain, are determined.

The process of deformation in clays is visualized as the combination of recoverable deformation resulting from bending and rotation of individual particles and irrecoverable deformation due to relative movement between adjacent particles at their points of contact. The relative movement between particles is treated as a rate process in which interparticle bonds are continually broken and reformed as the deformation proceeds. Accordingly, the rate of deformation is governed by the activation energy associated with the rupture of interparticle bonds. Thus, in terms of a rheological model, the fundamental element consists of a spring, representing the recoverable deformation, in series with a rate process dashpot representing the irrecoverable deformation.

Owing to the heterogeneous nature of the fabric of clay soils, i.e. varying particle size, shape, orientation, surface characteristics, etc., a wide range of activation energies, elastic stiffness, and other material properties is anticipated. This is accounted for by assuming a Gaussian distribution for the model properties. Thus, the complete rheological model postulated in this study consists of a combination of spring and dashpot elements covering the complete spectrum of model properties.

The response of the rheological model is analyzed for creep and constant strain-rate loading. The analysis is accomplished numerically using a digital computer since no closed form solution exists for the non-linear systems of equations that result from this model. Experimental data for a number of triaxial tests on clays under various conditions of loading are presented for comparison with the model behavior.

Aged suspensions of microspheres and two kaolinites exhibit several horizontal layers. Particle concentration is greater at the top of a layer; lower layer tops have increasing particle concentrations. Lower layers also settle more rapidly than upper layers; however, an increase in original suspension concentration results in a proportional increase in the particle concentration of comparable layers and causes comparable layers to settle at a slower rate. The average equivalent diameter of particles within and between kaolinite layers is identical. The maximum measured diameters are also identical. Microsphere layers show similar uniformity of average and maximum diameters. Ultimate settling of layers in suspension does not result in observable layers in the sediment. Data are interpreted as indicating that, in a colloidal suspension, particles interact to become observable as definite horizontal layers. A sequence of mechanisms is proposed for layer formation.

Nickel-chlorite has been obtained by the co-precipitation of nickelous hydrous oxide and montmorillonite at an OH/Ni ratio of 2.0. Chemical analysis shows that 16 me of Ni is fixed per gram of clay. System without any free nickelous hydrous oxide is quite stable up to an investigated period of 6 months, shows impedence to collapse on heating to 550°C, and no expansion of 001 spacing on glycerol treatment.

Different properties studied (X-ray diffraction analysis, thermal [D.T.A. and T.G.A.] data, i.r. absorption analysis, Polarographic reduction behavior and cation exchange capacity measurements) confirm the complete transformation of montmorillonite to nickel-chlorite.

“Seeding” of the hydroxide out of the “fixed” interlayer positions takes place on ageing the sample with free nickelous hydrous oxide. No montmorillonite could be detected by X-ray diffraction analysis in spite of this backward reaction.

Single crystal X-ray diffraction patterns reveal that the structure of selected anauxite crystals is the same as the structure of macroscopic kaolinite crystals. Anauxite and kaolinite crystals are intergrowths on a domain scale of units in pseudotwin orientations. Individual domains in anauxite have the triclinic geometry of kaolinite, and give X-ray reflections that compare closely in intensity with those calculated from the atomic parameters of kaolinite. Large crushed crystals of anauxite give powder patterns identical with that of kaolinite. Because it has been shown recently that the chemical composition of anauxite is also identical with that of kaolinite, it is recommended that the term “anauxite” no longer be used.

The co-absorptions of various purines and pyrimidines from aqueous solutions by Na- and Ca-montmorillonite are studied in the range of pH 1–6. The pyrimidines, thymine and uracil, which are not absorbed from solutions of these Compounds alone, are appreciably absorbed from solutions containing also adenine or 2,6-diaminopurine, are weakly absorbed from solutions containing hypo-xanthine, and are not absorbed from solutions containing purine, cytosine, and caffeine. The specific co-absorption is tentatively attributed to hydrogen-bond formation between the molecules in solution rather than to an overlapping of the molecular configurations (vertical stacking). The montmorillonite-organic associations have a basal spacing of about 12-5 Å which permits only a single molecular layer between successive silicate layers.

The crystal structure of nacrite from Pike’s Peak district, Colorado, has been refined by least squares and electron density difference maps utilizing ten levels of data. Complete refinement was inhibited by thick domains involving a/3 interlayer shifts in the “wrong direction”. The ideal structure is based on a 6R stacking sequence of kaolin layers, in which each successive layer is shifted relative to the layer below by −1/3 of the 8·9 Å lateral repeat. This direction is X in nacrite, contrary to the usual convention for layer silicates, because of the positioning of the (010) symmetry planes normal to the 5·1 Å repeat direction. Alternate layers are also rotated by 180°. The pattern of vacant octahedral sites reduces the symmetry to Cc and permits description of the structure as a 2-layer form with an inclined Z axis.

Adjacent tetrahedra are twisted by 7·3° in opposite directions so that the basal oxygens approach more closely both the Al cations in the same layer and the surface hydroxyls of the layer below. Interlocking corrugations in the oxygen and hydroxyl surfaces of adjacent layers run alternately parallel to the [110] and [11̄0] zones in successive layers. The upper and lower anion triads in each Al-octahedron are rotated by 5·4° and 7·0° in opposite directions as a result of shared edge shortening. Nacrite has a greater interlayer separation and smaller lateral dimensions than dickite and kaolinite, and the observed β angle deviates by 1½° from the ideal value. These features, as well as its overall lesser stability, are believed due to the less favorable positioning in nacrite of the basal oxygens relative to the directed interlayer hydrogen bonds.