Electrophoretic mobility of imogolite has been reported as positive (migration toward the negative electrode) below pH 9, and zero above pH 9. However, when mobility of dilute imogolite suspensions (5 × 10−3 kg/m3) was measured, it was found to be negative above pH 9. The reason that imogolite does not behave as a negative colloid when the clay concentration is not very dilute is because the imogolite forms floccules large enough to prevent migration. Imogolite has a PZNC at about pH 6, and has a PZC at pH 8.5–9.0 showing a relatively low absolute mobility under alkaline conditions compared to that under acid conditions. The fact that imogolite behaves like this is understandable given the location of negative charge appearing on the inside surface of the thin fibrous tube, according to the structural model of imogolite.

Zinc silicates were synthesized under conditions analogous to surficial weathering environments. The main product, regardless of conditions of precipitation or ageing, was shown by X-ray, i.r., electron microscopic and chemical evidence to be a 2:1 layered zinc silicate equivalent of stevensite. In the presence of aluminium, a 1:1 layered zinc silicate was formed as well, in confirmation of published work. The stability of the zinc silicate, in relation to carbonate, was favoured by the presence of aluminium in the lattice and silicic acid in the equilibrium solution. Zinc layer silicates were formed under conditions that generated orthorhombic zinc hydroxides and/or basic salts in the absence of silicon; the involvement of the brucitic zinc hydroxide (α-form), as proposed by earlier workers, could not be supported. Crystalline zinc layer silicates were formed by the slow evolution of the initial gels. Such layer silicates, but not willemite or hemimorphite, could have an important role in the control of chemical reactions of zinc in soils.

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.

Ionic liquids intercalated in kaolinite constitute a novel class of nanostructured material. Kaolinite-pyrrolidinium halide intercalates have been prepared successfully by reacting the pyrrolidinium salts with kaolinite which was preintercalated with dimethyl sulfoxide (DMSO) using the melt condition under N2. X-ray diffraction, 13C magic angle spinning nuclear magnetic resonance, differential thermal analysis (DTA)-thermal gravimetric analysis, and Fourier transform infrared spectroscopy confirm the displacement of DMSO during the intercalation process. Based on results from the various characterization techniques, a structural model is proposed in which one mole of the pyrrolidinium salt covers two or three structural units of kaolinite, depending on the structure and size of the salt. The thermal stability was improved remarkably after intercalation of the pyrrolidinium salts, compared to the pre-intercalate. The DTA-TGA data show that the largest number of organic units released and decomposed, occurs under N2 flow, at temperatures ranging from 260 to 340°C, depending on the nature of the intercalated organic salts.

The island of Lipari (Italy) is characterized by calc-alkaline to potassic volcanism and a Mediterranean-type climate. The mineralogical and chemical features of two different soil profiles with ages of 92,000 and 10,000–40,000 y, respectively, have been investigated. There were no Andisols, but Vitric and Vertic Cambisols have developed at both sites. Although the morphology of the soils was similar, remarkable differences in the clay mineralogy between the two sites were observed. The site with the Vitric Cambisol was associated with the weathering sequence: glass → halloysite → kaolinite or interstratified kaolinite-2:1 clay minerals. Both sites had smectite in the clay fraction and, to a large extent, this smectite had a low charge and could be characterized as a dioctahedral montmorillonite. At the site with a Vertic Cambisol, smectite was the predominant mineral phase in the clay fraction. The smectites (predominantly montmorillonite) found in this soil were probably not of pedogenetic origin and are, therefore, inherited from the parent material. Their formation is due to hydrothermal alteration of glass particles during or immediately after the emplacement of the pyroclastic flow. The octahedral character of the smectites did not change from the C to the A horizon indicating that they are resistant to weathering processes. A high-charge expandable mineral was detected in small concentrations in the Vertic Cambisol and had a dioctahedral structure. In this case also, no signs of significant weathering or transformation could be detected in the soil profile. In contrast to many other investigations, no active smectite formation within the soil profiles could be measured. The subtropical and rather dry climate in Lipari might, therefore, favor the persistence of dioctahedral low-charge montmorillonites that are associated with a small amount of a high-charge expandable mineral in the soil.

The first occurrence of Ni-rich stevensite found in the ophiolite complex of Othrys, Central Greece is described. The stevensite, which develops in cracks in a host serpentinite, formed at the expense of serpentine. Two varieties of stevensite have been described: a Mg-rich, Ni-poorer variety with 0.4–1.2 octahedral Ni atoms per half formula unit (p.h.f.u.) and a Ni-rich variety with >2 Ni atoms p.h.f.u. The layer charge in both varieties is −0.24 p.h.f.u.. Stevensite layers are completely separated when dispersed in dilute polyvinylpyrrolidone (PVP) solutions and begin to convert to talc after heating at 250°C for 90 min. Total conversion to talc is observed at 550°C. Formation of Ni-rich stevensite took place at ambient temperature during supergene processes. The scarcity of Ni-rich stevensite occurrences in nature is attributed to the metastability of smectite and to the analytical procedures used in previous studies. Stevensite is considered a phase containing domains with variable numbers of octahedral vacancies. A new experimental protocol is proposed for the determination of Ni-rich stevensite, based on a combination of XRD after solvation with various organic liquids and subsequent heating at 750°C.

This paper presents thermal conductivity data for highly compacted Ca-smectite, Na-smectite, illite, and palygorskite as a function of density (i.e., compaction pressure), water content, and temperature. All the clays behaved similarly: thermal conductivity increased directly with density and water content. Specifically, the thermal conductivity increased from 0.63 to 1.32 W/m·K as the dry density increased from 1.2 to 1.8 g/cm3 (for a water content of 17%). An increase of water content from 6 to 17% resulted in an increase in thermal conductivity from 0.63 to 1.22 W/m·K (for a dry density of 1.6 g/cm3). Differences from one clay to the other were less important. The thermal conductivity (in W/m·K) for constant conditions of 12% of water and a dry density of 1.6 g/cm3 were: Ca-smectite 0.80, Na-smectite 0.74, palygorskite 0.71, and illite 0.69. Heating to 188°C produced only a 10% increase in the thermal conductivity.

Bentonite, biotite, illite, kaolin, muscovite, vermiculite and zeolite were acidified or alkalized with HCl orNaOH of concentrations 0.0, 0.1, 1.0 and 5.0 mole dm−3 at room temperature for 2 weeks and converted into Ca homoionic forms. Low-temperature nitrogen and room-temperature water-vapor adsorption-desorption isotherms were used to characterize the mineral pores of radii between 1 and 30 nm. Nanopore volumes, size distributions, average radii and fractal dimensions were calculated. Values calculated from the nitrogen isotherms differed from those derived from water-vapor data. With an increase of the acid-treatment concentration, the pore volumes measured using both adsorption techniques increased markedly for all minerals. The pore radii measured from nitrogen isotherms appeared to decrease for all minerals except zeolite, while the pore radius calculated from water-vapor data increased in most cases. The fractal dimension measured from water vapor isotherms decreased in all cases indicating smoothing of the mineral surfaces and decrease in pore complexity. No well defined trends in any of the pore parameters listed above were noted under alkaline treatment. In the reaction of each mineral with acid and alkali treatments, the individual character of the mineral and the presence of impurities seems important.

Montmorillonite-based catalysts were compared with an acidic ion-exchange resin of the type used industrially for the production of methyl t-butyl ether (MTBE) from methanol and isobutene or t-butanol. When 1,4-dioxan was used as solvent, Al3+-exchanged montmorillonites had about half the efficiency of the resin Amberlyst 15 at 60°C; they were, however, about twice as efficient at this temperature at Ti3+-montmorillonite or K10, a commercially available acid-treated bentonite. Montmorillonite exchanged with Chlorhydrol solutions to give interlayer [Al13O4(OH)2(H2O)12]7+ ions and pillared clays derived from such materials were poor catalysts, as was K306, a more drastically acid-treated bentonite- based commercial catalyst. Freeze-drying of the Al3+-clay before reaction to produce a more open, porous structure had no effect on its catalytic efficiency. The activation energy for the reaction of isobutene and methanol in dioxan was 44 kj/mole for an Al3+-clay catalyst compared with 25 kJ/mole for reactions catalyzed by Amberlyst 15. With no solvent (as in industrial processes), the rates of reaction were considerably slower for both the clay- and resin-catalyzed reactions. As has been found previously for resin-catalyzed reactions using stoichiometric amounts or an excess of methanol, the rate was proportional to the isobutene concentration, and the rate-determining step appeared to be protonation of the alkene. The performance of the Al3+-clay catalyst was increased by reducing the water content of the clay. In most reactions the clay catalysts were equilibrated at 12% relative humidity. Exposure of the clay to a low vacuum (10−1 torr) before use increased its catalytic activity from 50 to 60% of that of Amberlyst 15.

Sepiolite and attapulgite were identified by X-ray diffraction, elemental, and thermal analyses in the calcareous zone of a soil formed on a relict basin-fill plain in Dona Ana County, New Mexico. Sepiolite occurs in the lower part of the zone of calcium carbonate accumulation; attapulgite occurs above, in, and below the sepiolite zone.

The sepiolite was observed as whitish aggregates remaining after the carbonate was dissolved with sodium acetate buffer (pH 5). Extended treatment with this buffer dissolved a significant amount of the sepiolite but did not appear to dissolve much attapulgite. Sepiolite was concentrated for analysis without significant solution by separating the <100 mesh material from the crushed soil, treating it with pH 5 buffer for a short time and separating the carbonate-free clay. The sepiolite is relatively high in aluminum compared to most sepiolites.

The sequence of dominant clay mineral with depth in the profile is montmorillonite, attapulgite, sepiolite, attapulgite, montmorillonite. No sepiolite or attapulgite was found above the calcareous zone; a little attapulgite was found at the base of the profile, which was not totally free of carbonates. Thin sections showed sepiolite and attapulgite occurring as aggregates, as coatings on mineral grains and as small fibers. The distribution of these minerals in the profile and the arrangement of the small fibers in the calcrete suggest that these minerals crystallized during the period of caliche formation.

As will be seen (Table 5) the sepiolite is present mainly in the nodular calcareous zone; the attapulgite, mainly in the blocky calcareous zone and in the transition zone below the calcareous zone (C6).

Using bentonites to adsorb aflatoxin is an effective method of minimizing the toxicity of aflatoxin to animals and humans. Early studies indicated a more than 10-fold difference in aflatoxin adsorption capacity among different bentonites. The determining mineralogical and chemical properties of the clays in aflatoxin adsorption are still poorly understood. The objective of this study was to test the hypothesis that a bentonite’s selectivity and adsorption capacity for aflatoxin is mainly determined by the ‘size matching’ requirement, on a nm scale, between the non-polar interlayer surface domains and the aflatoxin molecules. The non-polar surface domain size of smectites was varied by (1) selecting smectites with different charge densities; and (2) changing the valence and the size of exchange cations to control the amount of water in the hydration shells of the cations. Infrared spectroscopy and X-ray diffraction were also used to characterize the aflatoxin-smectite complexes to investigate if layer-charge density would affect the bonding strength between aflatoxin and the minerals. A large aflatoxin adsorption capacity and high selectivity for aflatoxin were achieved by selecting smectites that had low charge density as represented by their <110 meq/100 g cation exchange capacity. An individual smectite’s selectivity and adsorption capacity for aflatoxin could be enhanced or weakened by replacing the exchange cation. When the smectite was saturated with divalent cations that have smaller hydrated radius (e.g. Ba2+), the smectite’s adsorption capacity and affinity for aflatoxin were enhanced. Aflatoxin entered the interlayer of all six smectites tested. The strength of its bonding to the smectites was not affected by the layer-charge density of the smectites. The results confirmed the importance of nm-scale polarity and size match between aflatoxin molecules and the adsorbing sites on smectite. The high selectivity for aflatoxin can be achieved by selecting a smectite with adequate charge density or by replacing the exchange cations with divalent cations that have low hydration energy.

The characterization of cations associated with clay materials has generally been approached by the sequential use of specific chemical reagents. To avoid the disturbing effect of the chemical reagents on the state and location of compensating cations of clays and to get information in situ, far-infrared spectroscopy was used. The far-infrared vibrational spectra of the potassium cation in muscovite, phlogopite, and biotite were recorded before and after heating at the dehydroxylation temperature. The vibrational frequency of K in micas before dehydroxylation was found to be a function of the di- or trioctahedral character and of the Fe content. After dehydroxylation or deprotonation, shifts of the K absorption band to lower frequencies were observed for the heated muscovite, in which K exchangeability increased, and to higher frequencies for the heated biotite, in which K exchangeability decreased. These results suggest that the vibrational frequency of potassium is characteristic of the state of K in these minerals and of its ability to be exchanged.

Pillared bentonites were found to be efficient catalysts for the O-methyl bond cleavage of anisoles (e.g., m-methylanisole, guaiacol, and creosol) under very mild, static conditions (150°C, a few hours, inert atmosphere). The O-methyl bond cleavage led to phenolic products. Gas chromatographymass spectrometry and solid-state 13C nuclear magnetic resonance (NMR) techniques used to probe 13C-labeled anisoles revealed that dealkylation and transalkylation reactions occurred to a large extent, and that conversion was efficient at >95% after two days. Ortho- and para-isomers were observed exclusively, without any evidence of meta-substitution. Volatile products were determined by mass spectrometry to be 13CH3OH and (13CH3)2O. Magic-angle spinning 13C NMR experiments showed that the molecules were fairly mobile in the clay micropores prior to catalysis. After catalysis, cross-polarization NMR showed that molecular motion had decreased markedly. Ultraviolet-visible spectroscopy of the colored complexes suggested some quinone formation. The trend of clay reactivity was found to be: pillared bentonite ≫ acid-washed montmorillonite > untreated bentonite > pillared fluorhectorite ≃ untreated fluorhectorite.

Reduction of structural Fe in Na-exchanged dioctahedral smectites decreases swellability in water, but because clay interlayers also collapse in the process the concomitant effect on surface hydration energy is uncertain. This study examined the hydration behavior of oxidized and reduced dioctahedral smectite clays exchanged with polar (Na) and weakly-polar (organic) cations to determine the nature of the surface before and after Fe reduction, and to determine if clay surfaces are hydrophilic or hydrophobic. The H2O content in various dioctahedral smectites decreased if Na was replaced by tetramethylammonium (TMA), trimethylphenylammonium (TMPA), or hexadecyltrimethylammonium (HDTMA). Among the organo-clays, H2O adsorption decreased with increasing complexity of the cation. For oxidized smectites, those exchanged with TMPA retained less H2O than those exchanged with Na at all pressures. The extent of this difference depended on the clay and decreased with increasing applied pressure. Reduction of Fe(III) to Fe(II) in the octahedral sheets decreased the swelling of Na-saturated smectites, apparently causing some previously swelling interlayers to collapse. If the Na interlayer cation was exchanged to alkylammonium after reduction, but prior to swelling-pressure measurements, the swelling increased or remained near constant, suggesting that the organo-cation disrupted the collapse process of the interlayers associated with the reduced smectite layers. Reduced TMPA-saturated smectite surfaces are more strongly hydrated if the octahedral sheet is reduced than if oxidized. Thus, reduction of structural Fe increases the hydration energy of smectite basal surfaces, but swellability could decrease or increase depending on the extent of interlayer collapse occurring with different exchangeable cations.

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.

The sorption of nitrate ions on calcined hydrotalcite-type compounds at 550°C (HT550), 650°C (HT650), and 850°C (HT850) from pure water solution at 25°C has been studied. The influence of the temperature was also investigated for the sample calcined at 850°C by studying the sorption process at 10 and 40°C. The experimental sorption data points were fitted to the Langmuir equation in order to calculate the sorption capacities (Xm) of the samples; Xm values range from 61.7 g kg−1 (HT550 at 25°C) to 147.0 g kg−1 (HT850 at 40°C). The values for the removal efficiency (R) obtained ranged from 70.5% for HT550 at 25°C to 99.5% for HT850 at 40°C. The sorption experiments showed that the greater the calcination temperature (850°C), the more effective the removal of nitrate. The increase in the temperature from 10 to 40°C for sample HT850 also tends to increase the sorption of nitrate from 63.3 g kg−1 to 147 g kg−1 and the corresponding removal efficiency from 71.5 to 99.5%.

Expansion of kaolinite with potassium acetate reduces the intensity of the 3695 cm−1 absorption band and causes the appearance of an additional one at 3600 cm−1. Subsequent deuteration with D2O vapor shifts the 3695 cm−1 and 3600 cm−1 absorption bands to 2725 cm−1 and 2650 cm−1 respectively. The hydroxyls absorbing at 3620 cm−1 do not interact with the acetate anion and do not readily exchange with D2O vapor.

Deuteration of expanded hydrazine-kaolinite complex at room temperature shifts the infrared stretching frequencies 3695, 3670, 3650 and 3620 cm−1 to 2725, 2710, 2698 and 2675 cm−1 respectively. The OH-OD exchanges for the hydroxyls absorbing at 3695, 3670 and 3650 cm−1 are 67, 60 and 62 per cent respectively, and for the 3620 cm−1 only 22 per cent. The 3695, 3670 and 3650 cm−1 absorption bands are correlated predominantly to inner-surface hydroxyls and the 3620 cm−1 to inner hydroxyls located below the holes in the silica tetrahedral layer.

The ν(OH) absorption bands at 3695, 3670 and 3650 cm−1, and the ν(OD) at 2725, 2698, and 2675 cm−1 are pleochroic, whereas the 3620 cm−1 absorption band is non-pleochroic. The direction of the dipole moment change of OH groups absorbing at 3695 cm−1 and 3670 cm−1, and of OD groups absorbing at 2725 cm−1 and 2698 cm−1, is nearly at right angles to the basal plane (001); for the 3650 cm−1 and 2675 cm−1 bands, the angle is large, but less than 90°. The inner hydroxyls absorbing at 3620 cm−1 have their dipole moment change inclined at about 15° to the “ab” cleavage plane.

A comparison of the ν(OH) and ν(OD) absorption intensities for the film rotated 45° and normal to the infrared incident radiation shows that the pleochroism is more intense in the ν(OD) region than in the ν(OH) region. This indicates that partial deuteration perturbs the direction of dipole moment change of the “hydrogen bond” with respect to the initial orientation prior to deuteration; the net result is the formation of larger angles between the direction of the OD dipole moment changes and the basal plane (001) than existed for OH prior to deuteration.

To determine the dependency of rheological properties on mineralogical characteristics, eleven organophilic hectorite and nine organophilic saponite samples were prepared from hydrothermally synthesized smectites and a quaternary ammonium salt containing mainly octadecyl groups as alkyl chains and were examined by X-ray powder diffraction (XRD), particle size, chemical, and rheological procedures. The rheological properties of the organophilic products dispersed in toluene were found to depend chiefly on (1) particle size, (2) the expansion behavior of the stacked clay platelets, in which the amount and location of negative charge of the silicate layer affected the expandability, and (3) the amount of methanol added as a polar activator. By the addition of 2–4% methanol, apparent viscosities of the hectorite clays were drastically increased at low shear rate, although even a 10% addition did not significantly affect the saponite clays. Under the most suitable gellation conditions, the saponite clays showed lower apparent viscosity than the hectorite clays. Inasmuch as the former had its negative charge near the surface of the silicate layer and formed strong bonds to the organic ion, the expansion of the platelets was apparently difficult. An optimum layer charge for increasing the viscosity was found; specifically 0.45–0.50 and 0.50–0.55 equivalents per half unit cell for saponite and hectorite clays, respectively. Because the saponite clays contained a denser population of organic ions than the hectorite clays, the ion density in the interlayer of both clays was considered to be the same, i.e., about 0.4 organic ions per unit ab area.

The 1–5 μ size fractions of different ground muscovites were treated for a 30-day period for K+ removal with a pH 7.5 solution containing sodium tetraphenylboron. The initial K+ contents ranged from 211 to 219 me/100 g. After the extraction period, the final K contents ranged from 21 to 37 me/100 g. The apparent structural charge on the expanded material decreased to values ranging from 156 to 184 me/100 g, which are within the charge range for natural vermiculites. The b-dimensions of these laboratory-produced vermiculites were found to vary with the exchange ion and with the hydration state of the ion. For hydrated samples, saturation with Cs+, Li+, and Mg2+ ions increased the observed b-dimension in comparison to that of the corresponding parent mica, whereas saturation with Sr2+ and La3+ ions had little effect on b. After dehydration at 350°C, only Cs+-saturated samples had a b-dimension greater than that of the parent mica. The observed b-dimension for the dehydrated samples was found to be a direct function of the crystal radius of the interlayer ion. Apparently, as the ion dehydrates, the surface oxygen triads rotate until some of the oxygens “lock” onto the ion, limiting the minimum b-dimension. Before dehydration, however, the water of hydration in the interlayer region is evidently held with sufficient energy to limit rotations of the oxygen triads that give rise to a decrease in b. When Li+ and Mg2+ ions occupy the interlayer region, their water network apparently even produces a slight increase in the observed b-dimension.