Weathered perthite and mixed muscovite-kaolinite from a kaolinitic granite at Trial Hill in east Queensland and kaolinized sericitic alteration from a granite from the Ardlethan Tin Mine of New South Wales were examined by optical, scanning electron (SEM), and transmission electron microscopy (TEM) to determine the alteration process of muscovite to kaolinite and kaolinite to halloysite (7Å). Muscovite was found intimately interleaved with kaolinite in a variety of proportions on a sub-micrometer scale. The contact was generally parallel to the (001) layers of both minerals, and the thickness of the contact layer alternated between 10 and 7 Å over short distances. Where the kaolinite to muscovite contact was at an acute angle to the muscovite layers, a small angle existed between the layering of the two phases, consistent with a topotactic alteration of muscovite to kaolinite. One tetrahedral sheet in the muscovite appeared to have been removed over 50–100 Å, converting a 10-Å layer to a 7-Å layer. The mica near the contact with kaolinite was easily damaged in the electron beam and showed Al loss during analytical transmission electron microscopy; thus, H3O+ probably substituted for K+ in this transitional phase.

An SEM examination of completely weathered plagioclase showed kaolinite plates having attached, parallel, polygonal rods of halloysite (7Å), which had planar sides and a central void, partly fused with the surfaces of the kaolinite crystals. TEM study showed that the kaolinite altered to halloysite, and that, where the kaolinite was partly altered to halloysite, a series of sharp kinks were present in the kaolinite plate in which alteration had occurred. These kinks were interspersed with linear kaolinite relics, 0.1–0.2 μm long, which appear to have provided local rigidity to the clay packet. Apparently, the altered clay first curled into loosely wound spirals, which ranged in cross-section from triangles to irregular octagons, with pentagons and hexagons being most common. The tendency to pentagons and hexagons compares well with a statistical study of the angles, which were most commonly grouped around 120°. As alteration of the kaolinite relics progressed, the linear parts of the spiral lost their rigidity and became circular or oval shaped. The long axis of the halloysite spirals was parallel to the X axis of the kaolinite. Halloysite spirals formed most readily if they had space to curl; if space was not available, the halloysite formed sheaves. Rare, thin layers of muscovite were present projecting through kaolinite into halloysite. Where muscovite relics reached open spaces, the 10-Å structure expanded to 14 Å.

The dehydration reaction of kerolite was investigated using high-pressure differential thermal analysis at pressures as high as 600 bars. The peak associated with the dehydration is broad, suggesting the presence of a series of overlapping reactions ranging from the release of adsorbed water to interlayer water. The peak temperature is 136°C at 1.8 bars and increases to 516°C at 586 bars. The primary reaction represents loss of adsorbed water having a bond energy of 1.5 ± 1 kJ/mole. A small amount of water may be present as interlayer water and has a bond energy of 7.5 ± 3 kJ/mole.

Mixtures of kaolinite clay and quartz sand were packed in columns and leached with NaCl-CaCl2 solutions of different concentrations (ranging from 0.5 M to distilled water) having sodium adsorption ratios (SAR) of 5, 10 and 20. Sodium hexametaphosphate (NaHMP) (10 g/m3) was added to each solution. Changes in the hydraulic conductivity (HC) and clay concentration in the effluent were measured, and the dispersion of the clay was evaluated. In the absence of NaHMP, using distilled water instead of 0.01 M solutions caused some reduction in the HC; the reduction became more severe as the SAR increased. At SAR 20 the HC dropped to 73% of that obtained when the 0.5 M salt solution was used. This reduction in HC was related to increases in the pH of the effluent and partial dispersion of the clay. On adding the NaHMP to the leaching solutions, a marked decrease in the HC and severe clay dispersion were observed at all SAR levels, if the kaolinite-sand mixtures were leached with dilute solutions and distilled water. The HC dropped to 40% of that obtained when leaching with 0.5 M salt solution, and dispersed clay in the effluent peaked at about 1% in the SAR 20 treatment following leaching with distilled water. The observed reduction in the HC of the kaolinite-sand mixture when NaHMP was added to the leaching solutions was due to the dispersive effect of NaHMP and sodium on the kaolinite. The polyanion NaHMP reduced the edge-to-face particle interactions, thereby enabling the dimise double-layer repulsion forces to predominate. Following addition of the polyphosphate, the response of kaolinite to sodium and electrolyte concentration was similar to that reported in the literature for smectite.

Aqueous gels of unaltered (oxidized) and chemically reduced ferruginous smectite (SWa-1 from the Source Clays Repository of The Clay Minerals Society) were characterized by transmission electron microscopy, electron diffraction, and energy-dispersive X-ray fluorescence to establish details regarding their texture, inter-layer and inter-particle arrangements, and chemical composition. Micrographs revealed that the reduction of structural Fe(III) to Fe(II) caused a consolidation of smectite particles from an extensive network of small crystals (1–6 layers thick) to distinct particles of limited size in the a-b direction and about 20–40 layers thick. The interlayer distances in the reduced sample appeared to be more uniform than in the oxidized sample, but both exhibited spacings of about 12.6 A. Chemical analysis showed no qualitative differences as a result of oxidation state. Electron diffraction patterns displayed marked differences. The pattern of the oxidized sample consisted of homogeneous rings, indicating that the stacking order in the a-b plane was turbostratic or disordered, whereas the reduced pattern exhibited much more order as evidenced by distinct spots amid low-intensity rings, suggesting that inter-layer attractive forces were stronger if Fe(II) was present in the clay crystal.

The interaction of Mn and akaganéite in neutral to alkaline media has been investigated using X-ray powder diffraction and transmission electron microscopy. Akaganéite transformed into goethite and/or hematite, whereas Mn precipitated as hausmannite and birnessite at pH > 12 and as manganite at pH 7.5–8.5. Mn influenced the kinetics of the transformation of akaganéite: the rate-determining step, i.e., the dissolution of akaganéite, was retarded by adsorbed Mn species. Hematite formation was not suppressed. By catalyzing the air oxidation of adsorbed Mn(II), akaganéite promoted the formation of birnessite. Akaganéite did not retard recrystallization of the Mn phases. The incorporation of Mn in the structure of goethite formed in this system was negligible, and jacobsite (MnFe2O4) did not form. The formation of mixed Mn-Fe phases appeared to require a ratio of Mn2+: Fetotal > 0.02; this ratio was not achieved due to the oxidation of Mn2+ at the akaganéite surface.

The reaction of gibbsite in various organic solvents at 250°–300°C under spontaneous vapor pressure of the solvents was examined. Glycols and aminoalcohols afforded the organic derivatives of boehmite in which one of the oxygen atoms of the glycol molecule or the alcoholic oxygen atom of aminoalcohol was incorporated into the boehmite layers. By increasing the molecular size of the solvent, the yield of the boehmite derivative decreased, and, at the same time, the basal spacing of the boehmite derivative increased. The product had a honeycomb texture on the surface of the particle, which suggests a dissolution-recrystallization mechanism for the formation of the boehmite derivatives. A hydroxyl group and a functional group, such as hydroxyl, methoxyl, or amino group having the ability to donate its lone pair electrons, were apparently necessary for the organic solvent molecules to form the boehmite derivative by this mechanism.

Hydroxy-Al-montmorillonite was prepared by mixing Na-Wyoming montmorillonite with Al(OH)2.5 polycations and aging the mixture for 10 days. The reactions of this complex with citric acid at millimolar concentrations were investigated at different pHs for a 4-hr reaction time. The citrate sorption data, X-ray powder diffraction patterns of the montmorillonite adsorbent, and solubility products for Al(OH)3, estimated after computer speciation of the aqueous solution phase, suggested two reaction mechanisms, depending on pH. At 4 < pH < 5.5, the complex was stable, and only external hydroxy-Al polycations could react with citrate, yielding a sorption envelope characteristic of an acid having a low pKa. At higher pH, and particularly at pH > 7, the interlayer Al-polymers became accessible to the ligand and desorbed quickly from the montmorillonite basal planes to form a new, external, X-ray-amorphous solid phase with citrate. This reaction produced a large second peak in the sorption envelopes near pH 8, which was controlled by the increasingly negative surface charge at high pH and by the initial concentration of citric acid. This ligand accelerated, i.e., favored kinetically, the dissociation of adsorbed hydroxy-Al polymers from montmorillonite at pH > 7.

Large-pore La-Al-pillared montmorillonite was prepared by reacting montmorillonite with hydrothermally treated mixtures of aluminum chlorohydrate and lanthanum chloride. The large-pore La-Al-pillared montmorillonite is characterized by basal spacings of about 26 Å, surface areas of 300–500 mVg, and pore volumes in the range 0.2–0.3 cm2/g. Large-pore pillared montmorillonite products were obtained from solutions refluxed for >72 hr or treated in autoclaves at 120°–160°C for 12–96 hr. The most favorable pillaring solution for the production of large-pore La-Al-pillared montmorillonite had an OH/Al ratio of 2.5, a La:Al ratio of 1:5, and was 2.5 M with respect to Al. The elemental composition of large pore La-Al-pillared montmorillonite is similar to that of a conventional Al-pillared montmorillonite that has a basal spacing of about 19 Å. The 26-Å spacing is believed to be associated with the formation of large polymeric La-bearing Al-cations upon hydrothermal treatment of the solutions.

The rehydration properties and behavior of interlayer cations of Ca-, Mg-, Na-, and K-saturated homoionic saponite and vermiculite heated at various temperatures were examined and their rehydration mechanisms elucidated. The most notable features of saponite were (1) except for the Mg-saturated specimen, all saponite samples rehydrated until the crystal structure was destroyed by heating; (2) the rehydration rate in air after heating decreased in the order: K+ > Na+ > Ca2+ > Mg2+; (3) the interlayer cations apparently migrated into hexagonal holes of the SiO4 network on thermal dehydration; and (4) the b-parameter expanded on thermal dehydration. The rehydration properties and behavior of interlayer cations of vermiculite were: (1) except for the K-saturated specimen, all vermiculite samples rehydrated until the crystal structure was destroyed by heating; (2) the rehydration rate in air after heating decreased in the order: Mg2+ > Ca2+ > Na+ > K+; (3) the interlayer cations apparently did not migrate into the hexagonal holes, but remained at the center of the interlayer space, even after thermal dehydration; and (4) except for the K-saturated specimen, the 6-parameters of the samples contracted on thermal dehydration. The different rehydration properties of saponite and vermiculite were apparently due to the behavior of the interlayer cations during thermal dehydration. For rehydration to occur, the interlayer cations of saponite had to migrate out of the hexagonal holes. Consequently, saponite saturated with a large cation rehydrated rapidly, whereas saponite saturated with a small cation rehydrated slowly. On the other hand, the interlayer cations of vermiculite remained in the interlayer space; therefore, the rehydration properties of vermiculite were strongly affected by the hydration energies of the interlayer cations. Furthermore, electron diffraction patterns suggested that the saponite and vermiculite consisted of random stacking and ordered stacking of adjacent 2:1 layers, respectively. The nature of the stacking of the minerals seemed to be the most important factor controlling the behavior of interlayer cations in the thermal dehydration process.

Hydrous phyllosilicate minerals exhibit many variations in unit-cell shape and symmetry, distortion due to cation ordering, polytypic repeats along Z, and lateral modulations that can affect the ease of indexing of X-ray powder diffraction patterns. In indexing the patterns of monoclinic and triclinic hydrous phyllosilicates it is important that the indices of all overlapping but nonequivalent lines be listed and used in the indexing program, with weights assigned according to their multiplicities. Deviations from orthogonal unit-cell geometry show up by a broadening or a splitting of nearly superimposed lines, as occurs also if the observed ß angle differs from that produced by a layer shift of ideal magnitude (e.g., a/3). Observed powder intensities should be correlated with those expected from the structure, and an index should not be assigned solely on the basis of the calculated d-value that is closest to that observed. Assigned indices should not violate space group extinctions. Multilayer structures show up in reflections of type k ≠ 3n for C-centered unit cells, not in 00/reflections.

The modification of the external surface area and the two types of microporosity of palygorskite (structural and interfiber porosity) were examined as a function of the temperature of a vacuum thermal treatment to 500°C. The methods used included: controlled-transformation-rate thermal analysis, N2 and Ar low-temperature adsorption microcalorimetry, conventional and continuous gas-adsorption volumetry (for N2 and Ar) at 77 K and CO2 at 273 and 293 K, water vapor adsorption gravimetry, and immersion microcalorimetry in water. At temperatures < 100°C only 18% of the structural microporosity was available to N2, 13% to Ar, and 100% to CO2 at 273 K. In both experiments the channels filled at very low relative pressures. At temperatures between 70° and 130°C the structure folded, and the mineral transformed to anhydrous palygorskite, which showed no structural microporosity. The interfiber microporosity was found to be independent of the temperature treatment, and the external surface area decreased slightly from 65 to 54 m2/g. The water adsorption isotherms showed that the folding of the structure was reversible up to final outgassing temperatures >225°C.

The catalytic power of Ca-nontronite (0.2–2 μm) for the polycondensation of phenols and glycine and the associated reactions that involve the ring cleavage of phenols and the decarboxylation and deamination of glycine was studied in systems free of microbial activity. At the end of a 90-hr reaction period, the amount of CO2 released from the Ca-nontronite-glycine-pyrogallol, Ca-nontronite-glycine-eatechol, and Ca-nontronite-glycine-hydroquinone systems were 5.1, 8.7, and 11.6 times higher, respectively, than those from the respective nontronite-free systems, showing the catalytic role of Ca-nontronite in the ring cleavage of phenols and the decarboxylation of glycine. The release of CO2 and NH3 from the Ca-nontronite-glycine system revealed that Ca-nontronite can catalyze decarboxylation and deamination of glycine. The ability of Ca-nontronite to catalyze the deamination of glycine was substantially enhanced by the presence of a phenol. The visible absorbances at both 472 and 664 nm of the supernatants, the total yields of N-containing humic polymers, and the fractions of glycine converted to nitrogenous polymers indicated that polycondensation of glycine and phenol was greatly catalyzed by Ca-nontronite. The total N-containing humic polymers formed in the systems decreased in the order: Ca-nontronite-glycine-pyrogallol > Ca-nontronite-glycine-cateehol > Ca-nontronite-glycine-hydroquinone > glycine-pyrogallol > glycine-hydroquinone > glycine-catechol. The infrared and electron spin resonance spectra of humic acid (HA) and fulvic acid (FA) formed in the supernatants of the reaction systems were quite similar to those of soil HA and FA. The catalytic power of Ca-nontronite in affecting the ring cleavage of phenols, deamination and decarboxylation of amino acids, and formation of humic substances derived from phenols with amino acids in soils and the related environments thus merits attention.

In a study of “rana” soils of central Spain, hydroxy-interlayered 2:1 clay minerals were identified in the upper horizons and high-charge smectite in the lower horizons, with kaolinite the most abundant phyllosilicate. The high-charge smectite showed a basal spacing of 18 Å on Mg-saturation and glycerol solvation and 10 Å on K-saturation and air-drying. It is concentrated in the coarse fractions and appears to be basically a beidellite in the fine-silt fractions and a montmorillonite in the clay fractions. Pre-existing illite was probably transformed into hydroxy-interlayered 2:1 clays in the surface horizons, whereas high-charge smectite formed in the deeper horizons. These minerals, which were apparently not stable in the existing soil conditions, were the first stage in the degradation process of illite. The stable mineral in these soil profiles was kaolinite.