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.

The exchange of various alkylammonium cations from aqueous solution by sodium laponite has been studied. The affinity of the clay for these organic cations was linearly related to the molecular weight, molecular size or chain length of the alkylammonium ions. The affinity for the clay increases regularly with increasing chain length of the primary amines. A comparison of primary, secondary, and tertiary amines, containing the same alkylgroups shows that the affinity increases in the order R1NH3+ < R2NH2+ < R3NH+. These affinity sequences were attributed to important van der Waals contributions and changes in ion hydration states. The thermodynamic excess function, ΔGmE, was calculated and indicated that with respect to the pure homoionic forms the heterogeneous Na+-alkylammonium surface phases were more stable than they would be if the mixing were ideal.

The broad charge heterogeneity typical of nearly all smectites is not necessarily characteristic of vermiculites. In addition to vermiculites with pronounced heterogeneity, minerals with no or only limited charge heterogeneities are known. Layer charge and charge heterogeneity of 25 vermiculites were determined by alkylammonium ion exchange. The comparison of experimental basal spacings with dL/n-plots provided a simple determination of the average charge density. The spacings of high-charged vermiculites (≥0.8 eq/(Si,Al)4O10) with paraffin-type interlayers follow a straight line in the dL/n-plots. Lower-charged vermiculites were recognized by stepwise increasing spacings due to mono-, two-, or three-layer chain packings. Charge heterogeneity produced a superposition of the dL/n-curves for different charges, and the basal reflections of some of the alkylammonium derivatives became nonintegral.

The layer charge of five smectites, one vermiculitic material, and five reduced-charge clays was determined by the alkylammonium and structural formula methods. The two sets of results were found to be linearly correlated (r =.961); however, the values that were determined by the alkylammonium method were 20 to 30% lower than those determined by the structural formula method, and the regression slope for their linear relationship was 1.67. The fact that the structural formula method includes the effects of cations on the lateral edges of the clay particles probably accounted for some of the differences in the magnitude of the results but should not have caused the regression slope to deviate substantially from 1.00. Therefore, inaccurate estimates of the packing density of alkylammonium cations in the interlayer space of 2:1 phyllosilicates were deemed responsible for the systematic divergence of the results of the two methods. To satisfy the need for a relationship between the two methods of determining layer charge, an empirical means of adjusting the alkylammonium values has been proposed and shown to yield values of layer charge that are comparable to those determined by the structural formula method.

Layer charge and cation-exchange characteristics of weathered biotite isolated from a Gray Luvisol in Saskatchewan showed that this product was a high-charge vermiculite. Cation-exchange capacity (CEC) of the sand-size (100–250 μm) weathered biotite particles from different horizons, as determined by a 30-min Ca/Mg exchange, was low (23–71 meq/100 g). Increasing the exchange period to 24 hr increased the CEC to 33–95 meq/100 g for samples from the solum horizons and to 155–163 meq/100 g for samples from C horizons. The free oxide coatings on the mineral particles in the solum horizon samples apparently prevented the exchange cations from entering the interlayers. Removal of free oxides followed by 24-hr exchange sharply increased the CEC of these samples to 105–155 meq/100 g. Oxidation and loss of structural iron resulted in lower octahedral-cation occupancy (2.4–2.6 per half unit cell), suggesting a transition of the trioctahedral biotite to dioctahedral vermiculite. X-ray powder diffraction and high-resolution transmission electron microscopic analyses of alkylammonium-exchanged samples from the sand fractions of all horizons and magnetic separates of the coarse clays showed a linear increase in the d-value of the vermiculite with increasing chain length of the cations. The linear relationships suggest a paraffin-type arrangement having a uniform and high layer charge (0.70–0.76 per half unit cell in the sand-size particles; 0.80–0.84 in the clay fraction). The empirical relationship between tilt angle (α) and the layer charge density for paraffin-type structures, as suggested by Lagaly and Weiss, cannot be used for accurate layer-charge determination. Based on experimental evidence, a straight line relationship between the tilt angle and layer charge is suggested. The layer charge values show no marked variation within the profile and agree well with those calculated from the chemical composition. The repotassified layers of vermiculite in the sand-size weathered biotite particles did not respond to the Ca/Mg exchange, but were expanded by the alkylammonium cations; in contrast, a pure biotite standard (Bancroft, Ontario) of same particle size was unaffected by either treatment.

Montmorillonites saturated with small quaternary alkylammonium ions such as tetramethyl-ammonium (TMA) or trimethylphenylammonium (TMPA) are excellent sorbents for aromatic pollutants. In some cases, water inhibits arene sorption, but the inhibition mechanism is not understood completely. The objectives of this study were to determine whether arenes interact with adsorbed TMA and TMPA ions and/or with siloxane surfaces, and how water affects these interactions. We reacted benzene and ethylbenzene vapors with normal- and reduced-charge TMA- and TMPA-montmorillonite films at several relative humidities, and obtained infrared spectra of the resulting sorbate-clay complexes. Arene sorption caused the methyl asymmetric deformation vibrations adsorbed TMA and TMPA to shift to lower wave-number, whereas water sorption caused shifts to higher wavenumber. In the absence of water, benzene and ethylbenzene adsorbed on the siloxane surface as well as interacted directly with TMA and TMPA ions. The proportion of TMA and TMPA ions that interacted with benzene and ethylbenzene was greater for reduced-charge than normal-charge montmorillonite. Comparison of the HOH deformation and cation methyl asymmetric deformation vibrations indicated that both benzene and ethylbenzene inhibited water sorption substantially, and that water more readily displaced benzene and ethylbenzene from TMA and TMPA ions than from siloxane surfaces. Water inhibited arene sorption mainly by hydrating exchangeable cations, thereby obscuring siloxane surfaces adjacent to adsorbed TMA and TMPA ions and decreasing the average pore dimensions. These results indicate that in the presence of bulk water, arene adsorption likely occurs primarily on the siloxane surface.

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.

—The charge of the expandable interlayers in a series of fourteen diagenetic illite/smectites (I/S) from lower Paleozoic K-bentonites was determined by the alkylammonium ion exchange method. The magnitude (<0.50 equivalents per half formula unit) and characteristic heterogeneous distribution of interlayer charges in eight samples with expandabilities from 70% to about 15% confirm the smectitic character of the expandable interlayers in this range. This result coupled with the lack of a correlation between expandability and interlayer charge is consistent with the hypothesis of a layer-by-layer transformation from a precursor smectite to highly illitic I/S clays during K-bentonite diagenesis. The charge of the expandable interlayers in I/S samples with about 10% or less expandabilities have been inferred to be vermiculitic rather than smectitic. The K-fixed interlayers and expandable interlayers in these samples appear to be similar in charge. The significantly higher charges inferred for the highly illitic samples can be consistent both with a layer-by-layer transformation and the neoformation mechanisms proposed in the literature for the formation of illite.

High resolution transmission electron microscopy (HRTEM) have been performed on dispersed portions of one R > 1 and two R3 illite/smectite (I/S) samples from Silurian K-bentonites. R > 1 sample was studied by HRTEM before and after alkylammonium ion treatment and R3 samples were studied only after alkylammonium ion treatment. The HRTEM images of the chemically untreated R > 1 sample were predominated by lattice fringe contrast with 20–40 Å periods, interpreted to represent various ordered I/S units. HRTEM images of the three alkylammonium-treated samples displayed very small, dispersed particles composed of illite packets separated by alkylammonium expanded interlayers. In the R > 1 sample, illite packets were mostly 20 Å to 40 Å thick whereas in R3 samples they were predominantly over 40 Å. Although a good degree of dispersion of the bulk samples was achieved, dispersed particles recorded on images were thicker than the fundamental particles postulated by Nadeau and coworkers. Alkylammonium ion-expanded interlayer thicknesses point out a trend toward a higher charge in the expandable interlayers (i.e., illite particle surfaces) with increasing illite content from the R > 1 sample to the R3 samples. In the R3 samples, the interlayer charge is sufficiently high to be vermiculitic.

Nano-ball allophane is a hydrous Al silicate with a hollow-sphere morphology that contains some defects or pores along the spherule walls. Enlargement of the pore openings by dilute alkali treatment was confirmed by cation exchange capacity determinations using various alkylammonium cations as replacement cations. An allophane sample with a low Si/Al ratio (0.67) was equilibrated with 10 mM CaCl2 (pH = 6.0) and the Ca2+ retained was extracted using aqueous 1 M NH4C1 or alkylammonium chloride salts. The Ca2+ extracted by ${\text{NH}}_4^{+}$ was 15.1 cmolc kg−1, but ${\text{CH}}_3{\text{NH}}_3^{+}$${\rm{C}}{{\rm{H}}_3}{\rm{NH}}_3^ + $ (mean diameter = 0.38 nm) only extracted 7.9 cmolc kg−1 of Ca2+. After 10 mM NaOH treatment (0.25 g:100 mL) of the allophane, the Ca2+ extracted by ${\text{NH}}_4^{+}$${\rm{NH}}_4^ + $ was 29.7 cmolc kg−1, 29.6 cmolc kg−1 by ${\text{CH}}_3{\text{NH}}_3^{+}$${\rm{C}}{{\rm{H}}_3}{\rm{NH}}_3^ + $, and 29.4 cmolc kg−1 by ${{\text{(CH}}_3\text{)}}_2{\text{NH}}_2^{+}$${{\rm{(C}}{{\rm{H}}_3}{\rm{)}}_2}{\rm{NH}}_2^ + $. The extraction of Ca2+ by the large ${\text{C}}_2{\text{H}}_5{\text{NH}}_3^{+}$${{\rm{C}}_2}{{\rm{H}}_5}{\rm{NH}}_3^ + $ cation (mean diameter = 0.46 nm) only decreased to 26.1 cmolc kg−1, indicating that pore diameters were enlarged from ∼0.35 to 0.45 nm. The significant increase in Ca2+ retention after NaOH treatment was attributed to the dissociation of increased numbers of newly exposed silanol groups in the enlarged pores. The low Si/Al ratio of the NaOH-dissolved material (0.35) and the decreased intensity of the 348 cm−1 IR band also suggested selective dissolution of the pore region. For allophane with a high Si/Al ratio (0.99) and much accessory polymeric Si, dissolution of polymeric Si and of the pore region occurred simultaneously. Alkali treatment produced a smaller increase in pore size and Ca2+ retention for allophanes with large Si/Al ratios than for allophanes with small Si/Al ratios. It was concluded that by altering the dilute alkali treatment conditions and varying the Si/Al ratio of allophane, the extent of structural modification or pore enlargement of the hollow spheres might be controlled.

In order to understand the microscopic properties of alkylammonium-intercalated vermiculites, molecular dynamics simulations employing the clayff-CVFF force field were performed to obtain the interlayer structures and dynamics. The layering behavior of alkyl chains was uncovered. With the model used in the present study (1.2 e per unit cell), the alkyl chains formed monolayers with carbon-chain lengths of C6, bilayers from C7 to C10, and pseudo-trimolecular layers from C15 to C18. Intermediate states also existed between bilayer and pseudo-trimolecular layer states from C11 to C14. The ammonium groups had two locations: most ammonium groups were located over the six-member rings (~90%), and the rest above the substitution sites (~10%). The ammonium groups interacted with the vermiculite surface through H bonds between ammonium H atoms and surface O atoms. The ammonium groups were fixed firmly on surfaces and, therefore, had very low mobility. The alkyl chains were slightly more mobile. The similarities and differences between alkylammonium-intercalated vermiculites and smectites were revealed. The layering behaviors of alkyl chains were similar in alkylammonium-intercalated vermiculites and smectites: the alkyl chain behavior was controlled by both the amount of layer charge and the carbon chain length. The distributions of ammonium groups, however, were different, caused by the layer-charge distribution in vermiculites being different from that in smectites. The atomic-level results derived in the present study will be useful for future research into and the applications of organo-vermiculites.

The structure and dynamics of alkylammonium-intercalated smectites were simulated using molecular dynamics employing the clayff-CVFF force field, the reliability of which was firstly validated for these systems. The layering behaviors of alkyl chains confirm the scenarios of the monolayer, transition and bilayer configurations for short, medium-length and long carbon tails, respectively. In the systems without water, the alkylammonium groups are all anchored firmly above the surface six-member rings through H bonds between ammonium hydrogen and surface oxygen, and the alkyl tails are a little more mobile. With water involved, some ammoniums are dragged out of the potential barriers of the six-member rings by water molecules through the strong H bonds between water oxygen and ammonium hydrogen. The intercalated water scarcely affects the basal spacing, alkyl chain layering or alkylammonium dynamics. It is also found that the systems with alkyl chains of 11 to 14 exhibit the greatest density, resulting in the extremely limited mobility of the intercalated species.

The objective of this study was to design new, functional, nanostructured materials from the abundant clay mineral kaolinite, in spite of development problems with the interlayer chemistry of kaolinite because of its non-swelling properties. A particular goal of this work was to graft, in a controlled way, alkylammonium groups onto the aluminol interlayer surfaces of kaolinite. This was successfully achieved by soft-chemical approaches, more specifically by the melting intercalation process of alkylammonium ionic liquids which were synthesized for this purpose. The resulting nanohybrid materials were characterized chemically and structurally by X-ray diffraction analysis, thermal analysis (TG/DTA), 13C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy, and Fourier-transform infrared spectroscopy. The amount of grafted organic material was quantified from TGA results. Alkylammonium salts with a short alkyl chain were grafted directly using a melting reaction at 180°C under N2 involving the in situ displacement of dimethylsulfoxide (DMSO) from a DMSO-kaolinite pre-intercalate; for longer alkyl chains, the grafting was done in two steps. In the first step, the corresponding amino-alcohol was grafted into the kaolinite by displacement of DMSO from the interlayer space. The second step consisted of quaternarization of the grafted material by reaction with iodomethane or iodoethane.

The kinetics of cation exchange in phlogopite have been studied in situ by hydrothermal atomic force microscopy (HAFM). The exchange of interlayer K by octylammonium ions caused an increase in the interlayer distance and the formation of reaction fronts which can be locally resolved by AFM. The observed reaction fronts revealed substantial variations in their propagation rates — even within single interlayers. This observed variability in interlayer reactivity could mainly be attributed to chemical and structural inhomogeneities of the samples. A quantitative evaluation of the front propagation at representative sites yielded a diffusion coefficient of the K+ exchange by octylammonium of 1.2±0.6 × 10−11 cm2/s assuming negligible transport normal to the layers. The reverse reaction, i.e. the exchange of organic ions by K+, resulted in a retreat of the reaction fronts and a general restoration of the original morphological state. However, indications of structural alterations and areas with trapped octylammonium ions were found.

Inceptisols are the major forest soils in northern Taiwan. Some chemical, physical and morphological properties have been documented for these soils, yet there is little information on the mineralogy and the charge characteristics of their constituent 2:1 clay minerals. In this study we conducted a detailed characterization of the clay mineralogy of two Inceptisols. Two pedons were sampled at diagnostic horizons and the clay mineralogy was examined by X-ray diffraction. The magnitude of the layer charge of the 2:1 phyllosilicates was estimated using the alkylammonium exchange method (nC = 12). The clay mineralogy of both soils was dominated by vermiculite and mica with small amounts of kaolinite. The surface horizon contained more mica and kaolinite than the lower horizons. The mean layer charge of vermiculite ranged between 0.60 and 0.86 cmolc/(O10(OH)2). The distribution of clay layer charge decreased with increasing soil depth in two pedons. Differences in layer charge between samples are due to differences in weathering processes. The difference in the extent of clay mineral weathering in the A and Bsm horizons could be partly because the mineral surfaces in the Bsm horizon were coated with organo-Fe complexes which protected them from weathering.