Anauxite crystals are reported to contain a higher SiO2:Al2O3 ratio than the 2:1 ratio found in kaolinite. A structure proposed for anauxite places the excess silica in double silica sheets, but an exact structure for anauxite has never specifically been determined. Many workers believe that anauxite is kaolinite associated with some extremely fine-grained excess silica which is not a part of the structure. Eight specimens studied in this work included portions of type materials from Bilin, Czechoslovakia, and the lone formation in California.

Amorphous silica and alumina are readily soluble in boiling (N/2)NaOH. Kaolinite is only slowly soluble in this reagent, but becomes readily soluble after dehydroxylation. Weight loss, differential solution rate, kinetic and X-ray diffraction studies were used to establish that the kaolinite clay fraction in the anauxite specimens had the composition of:

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Some of the anauxite grains are single crystals, while others are aggregates. The latter appear to be bound together by an amorphous silica phase. Hot caustic leaching extracts the amorphous silica and breaks up the aggregates producing “fines.” Improved characterizations of minor impurities were obtained when the residues from hot caustic treatments were studied with X-ray diffraction techniques.

Vermiculites and smectites in soils and sediments are frequently partially interlayered or “chloritized”. Dioctahedral expansible layer silicates are those most frequently interlayered, and hydroxy-Al appears to be the principal component of the non-exchangeable interlayer material.

The most favorable soil conditions for interlayer formation appear to be: moderate pH (4·6–5·8), frequent wetting and drying cycles, and low organic matter content.

In marine sediments, hydroxy-Mg interlayering may be significant. Soil-derived clays containing partially filled hydroxy-Al “brucite” sheets may be filled out with hydroxy-Mg. Under reducing conditions, hydroxy-Fe interlayers may be important.

Depending on the OH/Al ratio and Al content of hydroxy-Al interlayers, expansible layer silicate may either promote or retard the formation of gibbsite. Interlayered expansible layer silicates also may be precursors to kaolinite.

The effect of varying concentrations of Al3+ and H+ upon the simultaneous diffusion of 85Sr and 86Rb was measured in salt-free aliquots of clay having different Al:H ratios. The Sr and Rb saturation of the CEC was held constant while the exchangeable Al and H were varied from Al52:H1 to Al12:H34. Aliquots of each clay-treatment were dually tagged with 85Sr and 86Rb. Self-diffusion of Sr and Rb was measured at 4, 24, 48, and 75°C. Radioassay of 85Sr and 86Rb was made with an automatic gamma-detection system equipped with a 400 channel analyzer and card punch unit. The selfdiffusion equation was programmed for the 7040 computer to permit the simultaneous calculation of 85Sr and 86Rb self-diffusion coefficients. Rb diffusion was not significantly altered as the Al3+ concentration was increased from 12 to 52 per cent. The diffusion of Sr was significantly increased as Al3+ increased from 12 to 52 per cent. The faster diffusing Rb ion had a greater energy of activation than Sr (4·8 to 3·6 kcal/mole), however the Arrhenius frequency factor for Rb (a measure of the probability of ion exchange) was much greater for Rb than Sr (28·8 and 0·4 × 10−4, respectively). Altering the Rb and Sr saturation and the complementary ions resulted in changes in the diffusivity, the energy of activation, and the frequency factor for these ions, but not always in the same direction or to the same degree.

A Georgia kaolinite, at water contents from 55 to 95 per cent, was tested by means of a Weissenberg Rheogoniometer under conditions of pure shear with sinusoidally varying deformation over a frequency range of 3 decades. The results, including time-dependent effects, are expressed in terms of the magnitude of the complex modulus and the phase angle, as developed in the theory of linear viscoelasticity, and stress-strain hysteresis curves. The complex modulus is a two-component quantity, which has a real part associated with the elastic or energy storage characteristics of the material and an imaginary part associated with its viscous or energy dissipation characteristics. Although the complex modulus interpretation is very good for linearly viscoelastic materials, its applicability and usefulness diminishes as the material departs from linear viscoelastic behavior. On the other hand, the determination of energy dissipation from stress-strain hysteresis curves does not depend on any assumption concerning material behavior, because the area enclosed by the curve gives a direct measure of the energy dissipated in a single cycle of deformation. The dissipation characteristics obtained by the two methods are compared and used to illustrate the degree of validity and some limitations of linear viscoelasticity theory.

The surface conductivity of salt free montmorillonite clay gels saturated with lithium, sodium, potassium and cesium has been studied. The theory of the behavior of heterogeneous dielectrics adapted to systems having a surface charge density has been applied to the clay gels. From numerical calculations it became evident that the value of the depolarization factor may be extrapolated to 1 in the direction of the small axis of the platelet, meaning that the field action is zero in this direction. Along the long axis, however, the action is complete and the motion of the charge carriers is essentially tangential to the platelet. The values of the surface conductance are of an order of magnitude of 10−9 Mho.

The investigation of the behavior of the water molecules has been carried out over a wide temperature range (145–320°K). At temperatures below 273°K, the conduction appears to be predominantly protonic; the counterions are considered to be disturbing elements in the water layer structures, thus creating a number of lattice defects able to transport the current. Above 273°K, the conduction is essentially due to the adsorbed cations, their contribution starts during the phase change.

Certain clay minerals have the ability to catalyze the polymerization of some unsaturated organic Compounds (styrene, hydroxyethyl methacrylate) and yet to inhibit polymer formation from other closely related monomers (e.g. methyl methacrylate). This apparently contradictory behaviour of the clay minerals can be rationalized in terms of electron accepting and electron donating sites in the silicate layers. The electron acceptor sites are aluminium at crystal edges and transition metals in the higher valency state in the silicate layers; the electron donor sites are transition metals in the lower valency state.

The catalyzed polymerizations involve the conversion of the organic molecule to a reactive intermediate; thus where the clay mineral accepts an electron from the vinyl monomer a radical-cation is formed, where the organic compound gains an electron it forms a radical-anion. Examples of these reactions are discussed.

The inhibition of polymerization processes involves the conversion of reactive organic intermediates, such as free radicals, which have been formed by heat or radical initiators, to non-reactive entities. For example, loss of an electron from the free radical gives a carbonium ion; in some cases this will not undergo polymerization. An example of this type is the thermal polymerization of methyl methacrylate.

The color reactions on clay minerals are useful in predicting the electron accepting or electron donating behaviour of the clay minerals because they proceed by similar mechanisms to the polymerization reactions. For example, the benzidine blue reaction is a one electron transfer from the organic molecule to the electron accepting sites in the mineral (aluminium edges, transition metals in higher valency state).

Masking of the crystal edge with a polyphosphate destroys the electron accepting properties of the crystal edge; this technique can be used to control the reactivity of the mineral and to distinguish between the crystal edge and transition metal sites as electron-acceptor sites in the clay minerals.

A detailed study of sediments from the Triassic of the French Jura shows that clay minerals vary continuously with the facies. Near the coasts of the Jura Sea, sediments consisted of sandy, continental detritus and the minerals are poorly crystallized. At the center of the basin, in what was a cation-rich chemical environment, they are well crystallized. A progressive mineralogical variation can be observed from degraded illite to well-crystallized chlorites passing through the intermediate stages of more-or-less regular mixed-layer structures. This variation is due to a true crystalline transformation.

Similarly, chemical variations in clay minerals and whole-rock samples are related to the paleogeography of the basin. The distribution of major and trace elements is a function of distance from the Jura Sea coastline and also a function of the mineralogical composition of the fine fraction. The most obvious relationships are: (1) An increase in the concentration of MgO and the percentage of ignition-loss water from the coast toward the deep sea; (2) A decrease in the concentration of SiO2, Al2O3, and TiO2 as well as that of trace elements such as vanadium, gallium, and cobalt from the coastal regions to the center of the basin; (3) A lack of statistically significant variations in the concentration of Fe2O3, Mn3O4, B, and Ni throughout the basin.

The authors conclude that: ( 1 ) Transformations (aggradations) observed by means of X-ray diffraction methods are in agreement with the chemical analyses; (2) Transformations are contemporaneous with the sedimentation; they are not diagenetic; (3) Clay minerals play an important role in the geochemical balance of sedimentary basins.

Samples of smectites and vermiculites were evaluated to (1) determine the effects of source and amount of charge, (2) determine if a continuum of properties exists, and (3) improve the basis for differentiating criteria for identification.

The montmorillonites expanded to the equivalent two-layer complex upon solvation by condensation of ethylene glycol or glycerol vapor. Beidellite exhibited the one-layer complex with glycerol vapor and the two-layer complex with ethylene glycol. The vermiculite samples did not yield regular two-layer complexes regardless of saturating cation, prior moisture or solvating agent. A number of different complexes of vermiculite were obtained depending on conditions of solvation. These corresponded to spacings of approx 13·6, 14·0, 14·3, 15·0, and 15·3 Å. Two or more of the complexes may be present in the same sample.

Potassium-saturated vermiculites and smectites both exhibited collapsed layers in a dry atmosphere. Hydration of smectites occurred at humidities above 20 per cent and resulted in poorly ordered diffraction maxima of 11–12 Å. The K-saturated vermiculites tended to retain the collapsed lattice and exhibited diffraction maxima of 10–10·6 Å with integral higher orders. Some hydration occurred as evidenced by peak asymmetry or the appearance of a small 14·3 Å line at higher humidities, although the collapsed spacing predominated. The tendency of vermiculite to hydrate decreased as the exchange capacity increased.

Differences in properties can be related to both source and amount of charge. Nevertheless, a continuum in the properties of expansion and collapse between the smectites and vermiculites was not observed. The data indicate two discrete populations. These properties may be used as differentiating criteria for identification.

Absorptions of purine and pyrimidine derivatives by Co- and Ni- montmorillonite at pH < 6 and by Cu-montmorillonite at pH < 3 are similar to their absorption by Ca-montmorillonite and take place primarily by a cation exchange process. In the weakly acidic to weakly alkaline range, absorption is due to complex formation with the inorganic cations, and decrease in the order Cu ≫ Ni > Co ≫ Ca. Adenine, 7-methyladenine, hypoxanthine, and purine are strongly absorbed, 9-methyladenine, 6-chloropurine, and cytosine are weakly absorbed, and thymine and uracil are not absorbed. At pH < 5, the nucleosides are absorbed by Co-, Ni-, and Cu-montmorillonite in approximately the same manner as by Ca-montmorillonite, but at pH > 6 their absorptions decrease in the order Cu ≫ Ni > Co > Ca. Fe(III)-montmorillonite behaves quite differently from the other mont-morillonites studied. With purines and pyrimidines, there is strong absorption from pH 3 to pH 7–8; with the nucleosides, the absorption varies considerably with the compounds considered decreasing in the order adenosine > cytidine ≫ guanosine ≫ inosine.

Hydroxy-Al and -Fe interlayers were prepared in “mono-mineralic” fine and coarse clay montmorillonite and coarse clay and silt vermiculite at 3°C and 21°C. The formation of hydroxy interlayers was evaluated by X-ray diffraction, cation exchange capacity, and chemical analyses.

At comparable particle size and regardless of temperature, the amounts of hydroxy-Al and -Fe interlayers in montmorillonite exceeded by far those formed in vermiculite. Likewise, the aluminum systems exhibited a higher degree of interlayering than iron systems.

Within montmorillonite, the amount of hydroxy-Al and -Fe interlayers increased as the particle size decreased, regardless of temperature. The aluminum interlayered montmorillonite equilibrated at 3°C was characterized by basal spacings of about 17 Å after Ca-saturation plus 54 per cent relative humidity. These spacings are larger than those normally observed for smectites.

Within vermiculite systems equilibrated at 3°C, more hydroxy-Al interlayers were recorded in coarse clay than in silt fraction, whereas at 21°C about equal amounts of interlayers were formed. By contrast, hydroxy-Fe interlayer was favored by the silt fraction at both temperature levels.

The formation of aluminum interlayers in both minerals increased with increasing temperature. The formation of hydroxy-Fe interlayers in montmorillonite was generally not temperature dependent, whereas the formation of such interlayers in vermiculite increased slightly with increasing temperature.

These data may partially explain the formation of chloritic intergrades in soils as a function of type of minerals, kind of ions, and thermal variations.

Electron microscopy of particles in size fractions (0·5–1·0 μ, 0·1–0·5 μ, 0·05–0·1 μ and < 0·05 μ e.s.d.) obtained by centrifugation of Na-saturated montmorillonites from Wyoming (two samples); Chambers, Arizona; and Fayette County, Texas, has shown details of particle morphology. The finest fraction of each montmorillonite consists predominantly of very thin, separate flakes whereas all coarser fractions, totalling 80 per cent or more by weight of the samples studied, are composed of microaggregates. For all the samples, preferred orientation is best developed in specimens formed from flakes of the finest fractions. Microaggregates are stable in dilute suspension although they swell to give large interlayer spacings, but can be disrupted into smaller, thinner flakes by ultrasonic vibration. Differences in dispersion behavior between separate flakes and microaggregates are not due to differences in interlayer charge or chemical composition, which are very small between fractions of each sample, but are thought to be due to the interlocking of flakes in microaggregates during crystal growth, which prevents their complete separation in dilute suspension.

A specimen montmorillonite (Arizona bentonite) was treated with hydroxy-aluminum solutions of various basicity. The cation exchange sites of this clay were found not to be homogeneous in their strength of retaining hydroxy-aluminum polymers; this strength varied from very weak, with which the Al polymers were only loosely held, to very strong, with which stable interlayer Al-clay complexes were formed. When a large amount of clay was treated with a small amount of solution, the polymers were held only in positions of strong affinity; the polymers were difficult to extract with neutral salt solutions and did not change to crystalline Al(OH)3 during prolonged aging. When a small amount of clay was treated with a large amount of solution, the exchange sites were completely occupied by polymers; a portion of these polymers was easily extractable with neutral salt solutions and, during aging, changed to Al(OH)3. This contrast is significant in any attempt to compare results obtained under different experimental conditions and to correlate laboratory experimentation with the occurrence of gibbsite and interlayer Al-clay complexes in nature.

Dickite and kaolinite are polymorphs of Al4(Si4O10)(OH)8. Dickite traditionally is regarded as hydrothermal, based on field and laboratory evidence. Dickite and kaolinite occur in cavities in phylloid algal limestones, in interstices of biocalcarenites and sandstones, and along joints, fractures, and stylolites, in Pennsylvanian rocks exposed throughout 9600 square miles of southeastern Kansas. The stratigraphic interval of approximately 1100 ft extends from the Fort Scott Limestone (Desmoinesian) through the Lecompton Limestone (Virgilian). The best crystallized dickites are found in porous algal limestones as pockets of glistening white powder composed of well developed pseudohexagonal plates up to 40 μ across. Very well crystallized kaolinites occur similarly, except the crystals are much smaller. Less well crystallized dickites and b-axis disordered kaolinites occur in less porous rocks. Variations in crystal size and morphological development are genetically significant.

Dickite-kaolinite distribution is related to: (1) stratigraphic alternation of limestones and impervious shales; (2) gentle, westward regional dip; (3) thick, mound-like buildups of highly porous algal limestones, miles in length and width; (4) igneous intrusions (early Tertiary?) in Woodson and Wilson counties. Dickite is confined to an elliptical area 125 miles long northeast-southwest, extending 60 miles eastward from the intrusions. Dickite is associated preferentially with porous algal mounds. Kaolinite occurs in less porous rocks within the dickite area, and also is abundant well beyond. Heated groundwaters, possibly mixed with magmatic waters, moved readily up-dip and along strike outward from the intrusions through the conduit-like algal mounds; dickite was deposited from such solutions. Where water movement was restricted or where water had travelled tens of miles from the intrusions, water temperature fell below the limit for dickite crystallization, and kaolinite precipitated instead. Kansas dickite, unlike most other reported dickites, formed in rocks that were neither deeply buried nor extensively altered hydrothermally.

Aluminum interlayers were synthesized under the same experimental conditions in a number of vermiculites and montmorillonites from different sources to determine the effects of the degree of neutralization of Al solutions, the time of reaction, and the type of structure.

Vermiculite fixed Al as well as hydroxy-Al ions in its interlayers, producing a stable 14 Å spacing and decreasing its cation exchange capacity considerably. Heating the Al-interlayered vermiculite at 300°C produced an interstratified mixture, indicating that some interlayers collapsed while others did not. The different collapse was attributed to different charge on vermiculite layers.

Neither the aging of vermiculite in Al solutions nor their OH/A1 ratios changed the stability of the interlayers appreciably.

Montmorillonites, on the other hand, did not fix Al ions but fixed appreciable amounts of hydroxy-Al ions. In addition, the stability of the interlayers in montmorillonite increased on aging in hydroxy-Al solutions and exceeded the stability of the interlayers produced in vermiculite. To explain the greater stability of montmorillonite interlayers, it was postulated that the more expanded interlayer space in montmorillonite provides a favorable locale for the organization of hydroxy-Al ions into gibbsite structure while the restricted expansion in vermiculite prevents it.

An X-ray spectrochemical method is compared with the flame photometer determination of potassium in a series of sixty-five soil clay fractions. Two methods of preparing the clay samples for the X-ray determination were used. In one case a 20 mg sample of clay in suspension was dried onto a plastic disc as a thin film. Potassium was determined by comparing the fluorescence intensity of the unknown with a sample of known composition which was prepared for analysis by the same technique. For the second method a 100 mg sample of dried clay was pressed into a pellet using methyl cellulose as a backing. In this case a National Bureau of Standards sample (NBS-98) was prepared in an identical manner and used as a standard for determining the potassium in the unknown. The results for both techniques were highly significantly correlated with the values as determined by flame photometric analysis. The pellet technique gave a more accurate measure of the potassium content. With the thin films the same sample may be used for X-ray diffraction analysis. In either case the X-ray spectrochemical technique provides a fairly rapid and simple procedure that can be useful for handling large numbers of samples.

A ternary plot of the tetrahedral R3+ and octahedral R3+ populations for the dioctahedral 2:1 clay minerals shows a broad range of compositional variation within each of the major clay minerals. The clay minerals can be subdivided on the basis of total charge, location of the charge, and the relative amounts of Al and Fe3+ in the octahedral sheet. The division is natural and is controlled by the misfit between the tetrahedral and octahedral sheets and the need for tetrahedral rotation. The compositions of the tetrahedral and octahedral sheets are interdependent. Whereas muscovite has a lower limit of 1·7 Al octahedral occupancy, illite and montmorillonite have a lower limit of 1·3 Al; lower Al values result in the formation of a chain structure.

Various fractions, ranging in size from 5 to 0·05 μ of natural clays from Mexico and Wyoming, occurring as heterogeneous or multicomponent cationic systems, were studied under specific equilibrium conditions of salt concentrations in the range found in many drilling fluids and formation waters.

Glass electrodes were utilized in this study. A Tektite electrode was found to have specific sensitivity to divalent cations.

High swelling bentonites cannot be analyzed for exchangeable cations with exactly the same technique as most soils. To resolve varied techniques used in the past and to establish a reliable procedure, the effects of sample size, the number of saturations, washes and extractions, and the volume of extracting solutions were determined on three high-swelling bentonites.

Small samples must be used to insure complete extraction of exchangeable cations, and the 0·5 g weight was the best size of those tested. Most exchangeable cations were removed in three extractions with 25 or 33 ml volumes of ammonium acetate. More extractions could result in excessive solubilization of minerals. Centrifugal force must be sufficient to prevent loss of sample during decantation. This varied from 4500 to 7500 g for 10–20 min, depending on particle size and sample dispersion.

The proposed CEC method requires little time, but still compared closely with Frink’s more extensive method and showed no significant difference between treatment means. The procedure was used to analyze high-swelling bentonites from fourteen locations in six Western States. Chemical properties changed within each deposit and with geographical location, but in general the bentonites contained high amounts of exchangeable Na, moderate amounts of exchangeable Ca and Mg, and low amounts of exchangeable K. Total exchangeable reliability of the proposed method.

The mechanism of boron uptake by clays, especially illitic clays, and the factors which control such uptake have long been debated issues. In an attempt to answer some of the questions of the controversy, three illites were treated in solutions containing boron. In the study, boron concentration, salinity, temperature, and time were varied independently over rather wide ranges.

For the illites studied, irreversible uptake of boron was increased by increasing boron concentration, salt concentration, temperature, and time of treatment. The amount of boron which was fixed also varied with the type of illite treated. The amount of fixation was controlled primarily by the specific surface area of the clay and also by the crystallinity, K content, and/or amount of mixed-layer material (“frayed-edge” development?), and apparently was independent of the original boron content of the clay.

A two-step mechanism is proposed for boron fixation by illite, consisting of rapid chemical adsorption of the tetrahedral B(OH)4− anion at the “frayed-edge” of the illite flake followed by much slower diffusion of boron into the tetrahedral part of the structure.