Unmodified and surfactant-modified clinoptilolite-rich tuff (referred to here as “clinoptilolite”) and muscovite mica were examined with tapping-mode atomic force microscopy (TMAFM) and high-resolution thermogravimetric analysis (HR-TGA) in order to elucidate patterns of hexadecyltrimethylammonium bromide (HDTMA) sorption on the treated surface and to understand the mechanisms of this sorption. TMAFM images were obtained to a scale of 50 nm by 50 nm. The images of unmodified clinoptilolite showed a framework pattern on the ac plane, comparable to previously reported images. Images of modified clinoptilolite at 12.5% and 25% of external cation exchange capacity (ECEC) coverage by HDTMA showed evidence of the HDTMA molecules arranged as elongated, topographically raised features on the ac plane. At 50% HDTMA coverage, the images contained what appeared to be agglomerations of surfactant tail groups. The z-directionthickness of the raised features on the 12.5% coverage sample corresponded to the thickness of the carbon chain of the surfactant tail-group (0.4 nm), whereas the z-thicknesson the 25% coverage sample was between 0.4 and 0.8 nm, indicating crossing or doubling of tail groups. Repulsive forces between the modified clinoptilolite and the silicon TMAFM probe increased with increasing HDTMA coverage. HR-TGA showed a 100 °C increase in HDTMA pyrolysis temperatures at coverages of less than 50%, probably due to an increased stabilization of the HDTMA due to direct tail interactions with the clinoptilolite surface at lower coverages versus smaller stabilization due to surfactant tail-tail interactions at higher coverages. Our results indicate that buildup of HDTMA admicelles or some form of a bilayer begins before full monolayer coverage is complete.

The adsorption of hexadecyltrimethylammonium (HDTMA) in smectite was studied by adsorption isotherms, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Smectites that had reacted for 48 h with HDTMA cations equivalent to 0.2–3.0 times the cation exchange capacity (CEC) were converted to HDTMA-exchanged smectites with various d-spacings. Study of HDTMA-smectites by HRTEM suggests that the HDTMA adsorption results in interlayer expansion with various d-spacings and irregular wavy layer structures. We believe that HDTMA loading beyond the CEC of smectite affects the structure of clay by the additional adsorption of HDTMA-Br− via hydrophobic bonding. Surfactant orientation probably depends on the quantity of surfactant in the interlayer. Our TEM study shows that the structure of the adsorbed HDTMA layer in the interlayers of smectite depends on the charge distribution and chemical composition of smectite.

In this study, the feasibility of using surfactant-modified palygorskite (PFl-1) and sepiolite (SepSp-1) for removal of anionic contaminants from water was evaluated from batch experiments. The results showed that both minerals had strong affinity for hexadecyltrimethylammonium (HDTMA), a cationic surfactant used for surface modification. The HDTMA sorption capacities were 520 and 260 mmol/kg for PFl-1 and SepSp-1, respectively. Accompanying HDTMA sorption, the sorption of counterion bromide reached 380, and 210 mmol/kg, for PFl-1 and SepSp-1, respectively, indicating that the sorbed surfactant molecules form admicelles on the minerals’ surfaces. After modification by HDTMA to sorption maxima, these clays showed strong affinity for anionic contaminants such as chromate and nitrate. The chromate sorption capacities were 42 and 34 mmol/kg for HDTMA-modified PFl-1 and SepSp-1, respectively. Desorption of counterion bromide due to sorption of chromate followed a straight-line relationship, suggesting that the sorption of chromate on surfactant-modified palygorskite and sepiolite was also due to anion exchange as with other surfactant-modified clay minerals and zeolites.

The adsorption behaviour of the herbicide clomazone on inorganic and organically modified montmorillonite from the Bogovina deposit in Serbia was investigated. Montmorillonite was modified first with NaCl and then with organic complexes such as hexadecyltrimethylammonium bromide (HDTMA) and phenyltrimethylammonium chloride (PTMA). Changes in the surface properties and morphology of the montmorillonite before and after the modification with various concentrations of organic complexes were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Adsorption of clomazone on all examined samples was investigated using the batch adsorption method. Montmorillonite modified with HDTMA-bromide displayed greater uptake of the clomazone compared to the PTMA-montmorillonite, and both organically modified montmorillonites displayed greater uptake of the herbicide compared to the inorganic montmorillonite. Comparing the Freundlich coefficient and maximum adsorbed clomazone quantity values obtained by Langmuir model, the levels of adsorption of clomazone decreased in the following order: HDTMA-montmorillonite with 1.00 cation-exchange capacity (CEC) saturation > HDTMA-montmorillonite with 0.75 CEC saturation > PTMA-montmorillonite with 1.00 CEC saturation > PTMA-montmorillonite with 0.75 CEC saturation > HDTMA-montmorillonite with 0.50 CEC saturation > HDTMA-montmorillonite with 0.25 CEC saturation > PTMA-montmorillonite with 0.50 CEC saturation > PTMA-montmorillonite with 0.25 CEC saturation > Na-montmorillonite > raw sample. The type and content of an organic cation plays an important role in the behaviour of clomazone in a solid/liquid system. It is concluded that organically modified montmorillonite from Bogovina might be used as an effective adsorbent for clomazone.

The dehydration of hexadecyltrimethylammonium (HDTMA)-exchanged smectites has been studied using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC). The basal spacing of hydrated HDTMA-smectites changed with temperature. The 2.5 HDTMA-smectite (i.e. smectite treated with HDTMA equivalent to 2.5 times the CEC) showed a continuous increase in its basal spacing during dehydration up to 200ºC, while the 1.2 HDTMA-smectite showed a significant decrease in basal spacing. It is assumed that the less ordered alkyl chains in the wet state in the interlayer region may be rearranged to ordered chains (e.g. all-trans conformation) during sequential dehydration. This results in a decrease in interlayer spacing in the phase with low organic packing density and a flat-lying array (i.e. 1.2 HDTMA-smectite), and a gradual increase in the basal spacing when the chains have a vertical configuration (2.5 HDTMA-smectite).

The morphological and structural changes in smectite caused by hexadecyltrimethylammonium (HDTMA) treatment were studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The HDTMA-exchanged smectite shows not only morphological features such as irregular, wavy surface with curled edges, but also structural features such as large d-spacings (20 – 26 Å ) and lattice distortions. The surface morphological heterogeneity is assumed to be related to the inhomogeneous intercalation of HDTMA cations into the interlayer of smectite.