Varieties of kaolin, a rock, may be classified geologically, mineralogically, crystallographically, genetically, texturally, morphologically, by industrial use, and in other ways which are desired. In this paper, the first-order of classification used is geological, i.e., transported and residual, after which other categories are used as subdivisions.

Scan electron micrographs, SEM, of the textures of kaolin show that distinctive textures characterize the several categories of classification. Varieties in texture of kaolin include similarities to those typical of sedimentary, igneous and metamorphic rocks. Because word descriptions of the textures are inadequate in comparison to pictures of them, the reader is referred to the micrographs.

SEM's illustrate differences between kaolins which were transported, formed, or deposited from solution, a colloidal phase, or as orthodox clastic particles. The parent source of kaolin deposited, or “grown,” from solution may be difficult to ascertain. It is suggested that the total role of solution work in kaolin petrology can be more important than has ordinarily been credited.

By using a transmission electron microscope equipped with an energy dispersive spectrometer, it was possible to detect the morphological, structural, and chemical characteristics of individual asbestos fibers and clay minerals without any realignment of the equipment. A rapid and convenient procedure for semiquantitative analysis is proposed. Analyses are given for 21 hydrous silicates, asbestos and clay minerals, by both ordinary chemical and energy dispersive methods. The energy dispersive results were comparable to those obtained by chemical analysis. Application of this procedure to asbestos fibers proved this method to be practical and valid for characterization of asbestos in environmental and tissue samples.

The adsorption of butanol, hexanol, and octanol on alkylammonium clays of different chain length is studied. The adsorption at infinite dilution compares to the distribution of alcohol between alkane and water in bulk solution. The interlamellar phase of the montmorillonite acts as a solvent even more reactive than carbon tetrachloride. Hydrogen bonds probably occur between the OH group of the alcohol and the NH3+ group. The exchange of water by alcohol on the interlamellar alkylammonium ion is the major factor in the transfer process.

Sixty-five bauxite samples of different ages and origins were studied by scanning electron microscopy. Only broken surfaces of the specimens were investigated. Size and form of individual crystals and of grain aggregates were studied as were different types of microtextures and space-fillers.

Grain size varies from 0.05 μm to 1 mm. Smallest is the grain size of young karstic bauxite deposits that is explained by a physicochemical retardation effect of the carbonate environment. Significant differences were found by comparing the space-filling of karstic and lateritic bauxite deposits. High-level and low-level lateritic deposits show differences as well.

A combined use of macroscopic observations, petrographie microscopy, electron microprobe, SEM, and TЕM furnishes the best clues for any genetic interpretation of bauxites. SEM studies are useful in solving technological problems of bauxite processing.

The influence of Al on the products formed by aerial oxidation at pH 5.5-7 and 20°C of Fe(II) chloride, sulfate and carbonate solutions, was examined. In all cases Al at levels Al/Al + Fe = 0.09−0.30 inhibited the formation of y phases (lepidocrocite and maghemite) in favor of goethite under conditions where, in the absence of Al, these y phases formed. The influence of Al in these laboratory studies was supported by field observations.

At higher levels of Al, ferrihydrite formation was favored. This effect of Al was seen to be the result of a slowing down in the hydrolysis/oxidation rate of the Fe(II) system.

The presence of Al not only changed the direction of mineral formation, but also caused the formation of Al substitued goethites which resembled in particle size and morphology the natural aluminiferous goethite extracted from a soil.

Kaolinites of all kinds (fine, ‘fireclay,’ ‘type IV,’ etc.), some of which do not expand or expand incompletely with the usual intercalation methods used for comparison, are expanded completely by treatment of dry (110°C) clay with dry CsCl salt, followed by contact with hydrazine for 1 day at 65°C and then with DMSO overnight at 90°C. Comparison treatments were grinding in KOAc, soaking in hydrazine, and Li-DMSO, as well as combination of these. Following the Cs-hydrazine-DMSO treatment, the 7.2 Å spacing of 1:1 dioctahedral layer silicates shifts to 11.2 Å and the 11.2 Å/(7.2 + 11.2 Å) ratio ≃1.0. The trioctahedral 1:1 layer silicates and chlorite are not expanded by the Cs-hydrazine-DMSO procedure.

“Kaolinites” from classic, large deposits of kaolin are shown commonly in scanning electron micrographs to be mixtures, at least in part, in microdimensions, of kaolin-mineral polymorphs.

Artificial mixtures of selected kaolin polymorphs simulating the natural mixtures, also micrographed, show crystallinities intermediate between the crystallinities of the end members in X-ray powder diffractograms. Thus, apparent crystallinity interpreted from diffractograms of a kaolin specimen may be a product of kaolin-mineral mixture in microdimensions as well as from ordering in the crystals. Evaluation of the crystallinity of a kaolin from powder diffraction may be suspect if independent means, such as SEM, are not used to assess the monomineralic character of that kaolin specimen.

Analogous to the apparent crystallinity of a “kaolinite” being the product of a mixture, so may other widely ranging properties of “kaolinite” be products of kaolin-mineral mixtures in microdimensions. These properties include DTA, IR, chemical composition, free energies of formation, and industrial applications.

Specifications for a monomineralic, nearly ideal kaolinite are considered—the Keokuk geode variety possesses desired crystallographic and chemical properties.

The binding of tris-bipyridyl metal complexes of the type M(bp)32+ (M = Fe2+, Cu2+, Ru2+) to hectorite surfaces is shown to occur by two mechanisms. (1) replacement of Na+ ions in the native mineral by cation exchange up to its cation exchange capacity and (2) intersalation of excess salt beyond the exchange capacity. In the cation exchange mechanism, the binding of metal complex is strongly favored over Na+. The intersalation reactions are dependent on the nature of the counter-anion: SO42-, Br- > CIO4−, Cl−. The homoionic M(bp)32+-hectorites, which exhibit rational 18 Å X-ray reflections, have been characterized with regard to their BET surface areas, water adsorption isotherms, types of water present, selected reactions in the intercalated state, and orientation of the complex ions in the interlayer regions. Mixed Fe(bp)32+, Na+-hectorites have also been examined and the results suggest segregation of the two ions between interlayers or within interlayers. Solid state intersalated phases have been isolated with 18 Å and 29.5 Å spacings. In general, surface areas of the intersalated phases are low, but the 18 Å phase derived from [Fe(bp)3]SO4 adsorption shows a high surface area, which even exceeds the surface area of homoionic Fe(bp)32+-hectorite.

Structural Fe2+ in montmorillonite is readily oxidized by contact with water, salt solutions or on mild heating. This is shown clearly by the Mössbauer spectra and is associated with a sharpening of the infrared absorption near 880 cm−1. It was inferred that this band comprises the Fe2+—OH—Al and Fe3+—OH—Al deformations. The rate at which oxidation occurs depends on the exchangeable cations. High acidity of the interlayers is conducive to oxidation, as is contact with Cu2+-containing solutions or concentrated H2O2 solutions.

The results show clearly that any chemical treatment of montmorillonite causes changes in the oxidation state of structural iron.

The different types of iron oxide phases associated with the surfaces of two suites of kaolins from Georgia, U.S.A., and from the Southwest Peninsula of England, have been identified using electron spin resonance (ESR) spectroscopy combined with magnetic-filtration, thermal, and chemical treatments. It has been shown that the English kaolins are coated with a lepidocrocitelike phase, which is readily removed by de Endredy's method of deferrification, while the Georgia kaolins are coated with a hematite- or goethitelike phase, which is not removed by this treatment. Throughout the course of this study, the effects of the various physical and chemical treatments on the brightness values of the kaolins were examined.

Nickel nitrate solution is potentiometrically titrated (a) with montmorillonite, (b) without montmorillonite, in the nitrate solution. X-ray powder diffraction and chemical analyses are made of the products formed by the clay at various stages of titration. The pH values of the titration curve (a) are lower than those of curve (b) until the brucite-like hydroxynickel interlayer is more or less complete. The resulting product then closely resembles a chlorite. The preferential precipitation of hydroxide in the interlayer region is explained in terms of the acidic character of montmorillonite interlayers.

A series of mixed iron and titanium oxide coprecipitates ranging in composition between 0 < Ti/Ti + Fe < 1 was synthesized and aged under varying conditions of pH, temperature and time in order to establish a working model for pedogenic titanium and titano-ferric oxides. X-ray powder diffraction (XRD), selective chemical dissolution, magnetic susceptibility, charge distribution and electron optical data indicate that the freshly prepared Fe-Ti oxides consist of an Fe-rich (Ti-ferrihydrite) phase (Ti/Ti + Fe ⩽ 0.70) having pH-dependent positive charge and a Ti-rich phase (Ti/Ti + Fe ⩾ 0.7) with permanent and pH dependent negative charge.

Synthetic Ti-ferrihydrite and amorphous TiO2 were completely soluble in acid ammonium oxalate (2 hr extraction in the dark) whereas poorly crystalline anatase (width at half height, WHH > 2.0°2θ) was partly oxalate soluble. NH4-oxalate soluble Ti was particularly high in soils developed under a cool montane climate (afro-alpine) and lower in soils of warmer subtropical climate, which contain anatase and rutile.

Several mixed Fe-Ti crystalline phases were identified after aging NH3 coprecipitates of Fe and Ti nitrate at 70°C and pH 5.5 for 70 days:

1. (1) goethite and hematite in the composition range 0 < Ti/Ti + Fe ⩽ 0.20; at low Ti concentrations (<5 mole %) goethite was favored and/or hematite inhibited

2. (2) microcrystalline pseudorutile in the composition range 0.20 ⩽ Ti/Ti + Fe ⩽ 0.70

3. (3) anatase and ferriferous anatase in the range 0.70 ⩽ Ti/Ti + Fe < 1.0; with decreasing proportion of Ti the crystal-Unity of anatase decreased.

The results suggest that secondary or pedogenic Ti-Fe oxides can form by coprecipitation and crystallization in the weathering solution, and emphasize the essential role of water (as opposed to dry oxidation) in the alteration of primary titaniferous minerals.

A unique vanadium-titanium-bearing mixed-layered clay is currently being mined as an ore of vanadium at Potash Sulphur Springs, AR. The clay contains 80% expandable portion and has both a 14.22 and 18.24 Å hydration state in addition to the 9.49 Å dehydrated state; ethylene glycol expands this material to 16.69 Å. The 060 reflection for all hydration states is between 1.50 and 1.51 Å indicating the material is dioctahedral. The “mean chemical formula” calculates as(Ca0.08 K0.02 Na0.03)0.13 (Al0.11 V0.90 Ti0.19 Fe0.64 Mg0.14)1.98 (Si3.79 Al0.21)4 O10 (OH)2·nH2O.

The equilibrium diagrams developed for Al-hydroxide and for kaolinite by Garrels and Christ (1965) have been modified by taking into account the existence of gels. From the stability zones obtained, the “appropriate” concentrations can be deduced and utilized for synthesizing these species, provided the requirements to insure good crystal growth are observed. Among procedures to promote these crystallizations, homogeneous precipitation processes (La Iglesia et al., 1974, 1976) appear to be particularly adequate.

The theoretical considerations provide an explanation for most of the processes observed until now, both successful and unsuccessful syntheses, and also give an explanation for many field observations. The crystallizations, however, remain poorly reproducible, indicating that many factors are still poorly known. Some points requiring further investigation include (i) better values for ΔGr0, (ii) the influence of organic complexes, (iii) the effect of preexisting crystalline phases, (iv) those involving dehydration processes in these systems.

The hydrated form of tubular halloysite [halloysite (10 Å)] was observed by a conventional electron microscope equipped with an environmental cell (E.C.), by which the “natural” form was revealed without dehydration of the interlayer water. This study mainly reports the selected area electron diffraction (SAED) analysis of the halloysite (10 Å) and its morphological changes by dehydration. The SAED pattern showed halloysite (10 Å) has two-layer periodicity in a monoclinic structure with the unit cell parameters of a = 5.14 Å, b = 8.90 Å, c = 20.7 Å, β = 99.7°, in space group Cc, and almost the same structure as the dehydrated form of halloysite [halloysite (7 Å)]. This means that the dehydration of the interlayer water did not greatly change or affect the structure of halloysite (10 Å). Accompanying the dehydration of the interlayer water, there appeared along the halloysite tube axis clear stripes that were about 50–100 Å in width. The diameters of the tubular particles also increased about 10%. From the results of various experiments, such as a focussing series, observation of the surface structure by the replica method, observation of end-views of the tubular particles, and others, these two phenomena were explained as follows: Halloysite crystals have “domains” along the c-axis direction, the thicknesses of the “domains” vary ca. 50–100 Å. They are tightly connected with each other when the halloysite is hydrated, but are separated from each other by the dehydration of the interlayer water, whereupon the stripes come into existence along the tube axis. Taking these considerations into account, a model of dehydration is proposed. Moreover, a new method of calculating the β-angle is proposed in the Appendix.

An infrared method has been developed for estimating kaolinite in sediments. Hydroxyl stretching bands of kaolinite in sediments can be recorded by using a differential technique which eliminates the overlapping owing to other mineralic constituents present. By adding known amounts of an appropriate standard to the sample and by measuring intensities of the OH bands before and after the addition it is possible to calculate the proportion of kaolinite in the test sample. The choice of the added standard is made from characteristic features of the hydroxyl stretching bands.

The i.r. spectra (4000-1200 cm-1) are obtained for several homoionic montmorillonite films on which various amounts of dimethyl sulfoxide (DMSO) were adsorbed. Analyses of these spectra indicate that H- and natural-montmorillonite-DMSO complexes contain an intercalated layer of physisorbed DMSO while transition metal cation substituted-montmorillonite-DMSO complexes possess both physi- and chemisorbed DMSO in their interlamellar spaces. The latter species involve coordination of DMSO molecules with the exchangeable cations by their oxygen atoms. Most of the interlamellar water is replaced by DMSO as the latter molecules penetrate the interlamellar spaces. Heat-treating transition metal cation substituted-montmorillonite-DMSO complexes at 120°C for 48 hr results in both the desorption of physisorbed DMSO and the retention of intercalated monolayers involving DMSO-transition metal cation coordination. A water-sensitive, reversible color change (tan to light purple) is produced by either desiccating over P2O5 or heat-treating at 120°C the cobalt-montmorillonite-DMSO complex. Interpretation of the visible spectra suggests that Co2+-cations undergo changes from octahedral to tetrahedral coordination during desiccation or heating. Band assignments are made for the clay complexes using the assignments for related gases, liquids, and crystals.

Several dioctahedral clay minerals are related through reaction series. These series can be produced hydro-thermally from beidellite gel and montmorillonite by making simple changes in interlayer and solution chemistry. The series are:

• gel-K-beidellite-random illite/smectite-K-rectorite-illite

• K-montmorillonite-K-rectorite-illite

• Na-montmorillonite or beidellite-Na-rectorite-paragonite

• Li-montmorillonite-Li-tosudite-Li-rectorite-cookeite(?)

• Mg-montmorillonite-Mg-rectorite-tosudite-sudoite(?)

• Ca-montmorillonite-Ca-rectorite-margarite(?)

• Al-Ca-montmorillonite-kaolinite/smectite-kaolinite (150°C)

• Al-Ca-montmorillonite-pyrophyllite/smectite-pyrophyllite (320°C).

Assuming stability for the mixed-layer phases, paragenesis is a function of P, T, and X conditions. If the phases are considered to be metastable, paragenesis is a function of the speed and path of reaction.

A correlation was made of crystallochemical data from 15 smectites with the half time of dissolution (t05) in 6 N hydrochloric acid at 96°C. From this the relation

ln t05 = 3.95 - 1.96 FeVI - 2.30 MgVI

was developed. It shows a remarkable dependence of the apparent dissolution rate of the octahedral layer of the smectites on the substitution of Fe3+ and Mg2+ for Al+3 in the octahedral position.

A laboratory study of cadmium exchangeability revealed large differences in extractable cadmium which are dependent on the exchange solution being utilized. The standard exchange solutions employed in this study were: N NaNO3, N NaOAc, N NH4OAc, NCaCl2, and 2N CaCl2, in order of increasing Cd removal. An interpretation of the chemical behavior of Cd and an experiment with mixed sodium nitrate and acetate solutions suggest that cadmium carbonate, octavite, was precipitated when the sediments were saturated with Cd prior to the exchange experiments and that the quantities of Cd recovered in the acetate solutions were erroneously high because of the dissolution of the carbonate material. Dissolution of solid phases, the lack of pH buffering, and the possible formation of a complex hydroxyl chloride salt also made the Cd values obtained with the chloride solutions too high. Sodium nitrate exchange solutions minimize these problems and are thought to best represent the exchangeable cadmium in the sediment.