Several clay organic complexes were prepared by placing organic cations on the exchange sites of smectite clays and studied as sorbents for pentachlorophenol (PCP). The organic cations used ranged from very hydrophobic in nature (e.g., dioctadecyldimethyl+ (DODMA+)- and hexadecyltrimethyl+ (HDTMA+)-ammonium) to those having minimal hydrophobic properties, such as tetramethylammonium+ (TMA+). In general, the more hydrophobic the cation on the smectite the greater the uptake of PCP from water. For the very hydrophobic clays (DODMA+- and HDTMA+-smectite) the uptake of PCP was via non-polar interactions between the alkyl (e.g., -C18) groups on the organic cation and PCP. In a mechanistic sense, this interaction appeared to be similar to a partitioning process between water and the organic phase of the clay-organic complex. The organic phases of DODMA+-smectite were about 10 times more effective than the organic matter of natural sediments for removing PCP from water. For those organo-clays containing small organic cations (e.g., TMA+), the organic phase consisted of separate small organic moieties, such as the methyl group. This phase did not act as an effective partitioning medium despite a significant carbon content, and very little PCP was taken up. Results from this study suggest the possibility of treating soils and subsurface materials with large hydrophobic organic cations to enhance the sorptive properties of these natural materials.

A stable 8.4 Å hydrate of kaolinite was prepared by exchanging ethylene glycol for water in the 10.8 Å intercalate of ethylene glycol in kaolinite. The hydrate of kaolinite was characterized by XRD, FTIR and TGA/DSC. From the TGA data, one can estimate that there is 0.60 water molecule per Al2Si2O5(OH)4 units. The IR data suggest a similarity of the local environment of the intercalated water in this 8.4 Å hydrate of kaolinite and the 8.4 Å hydrate of nacrite previously described by Wada (1965).

The surface thermodynamic properties of a series of n-alkylammonium and quaternary ammonium treated clay films were determined by contact angle measurement of drops of test liquids using the Young equation for polar materials. The two clays were a Wyoming montmorillonite (SWy-1) and Laponite RD. For a series of primary n-alkyl (6 ≤ n ≤ 15) and several quaternary organic cations, the organo-clay (both SWy-1 and Laponite RD) showed very little change in the value of γLW compared to the equivalent ammonium-saturated clay. Also, γ⊕ remained small or increased slightly compared to the ammonium-saturated clay. For SWy-1 exchanged by both quaternary ammonium and primary n-alkylammonium cations, the value of γ⊖ was smaller (0.1 ≤ γ⊖ ≤ 15.8 mJ/m2) than for the ammonium-saturated clay (γ⊖ = 36.2 mJ/m2) and decreased linearly with the number of carbon atoms. The γ⊖ values for the organic cation-exchanged Laponite RD samples (24.2 ≤ γ⊖ ≤ 31.2 mJ/m2) were smaller than or comparable to the ammonium saturated clay (γ⊖ = 30.7 mJ/m2), and were relatively insensitive to the number of carbon atoms in the organic cation. Thus, for both clays the increased adsorption of organic molecules resulting from replacement of inorganic cations by organic cations is due primarily to the decrease in the value of the Lewis base parameter, γ⊖.

Enhancement of the physico-chemical properties of elastomers can be achieved by the addition of fillers, such as silica, but the search for less expensive alternative materials continues. The objective of this study was to investigate natural or organically modified clay minerals as such an alternative. Organo-clays modified by quaternary ammonium cations with three methyl groups and longest alkyl chains of different lengths were prepared by ion-exchange reaction of the commercial product JP A030 (Envigeo, Slovakia) based on Jelšový Potok bentonite with organic salts: tetramethylammonium (TMA) chloride, octyltrimethylammonium (OTMA) bromide, and octadecyltrimethylammonium (ODTMA) bromide. Physico-chemical characterizations of the organo-clays used as fillers in rubber nanocomposites and their mechanical properties were measured using Fourier transform infrared (IR) spectroscopy, which provided information on the chemical composition of the mineral and on the amount of organic moieties adsorbed. X-ray diffraction analysis (XRD) was used to monitor the arrangement of organic chains in galleries of montmorillonite and showed that the longest-chain alkylammonium ODTMA+ ions were intercalated between layers, adopting a pseudotrimolecular conformation, while OTMA+ and TMA+ were in monomolecular arrangement. Surface areas were measured by sorption of N2 and ethylene glycol monoethyl ether. Natural rubber-clay nanocomposites were prepared by melt intercalation, in some cases also with addition of silica, a conventional reinforcing filler. The microstructure of montmorillonite in these composites was characterized by XRD analysis. The effect of clay and organo-clays loading from 1 to 10 phr (parts by weight per hundred parts of rubber) on stress at break, strain at break, and Modulus 100 (M100) was investigated by tensile tests. Filler ODTMA-JP A030 appears to be the most effective among the organoclays; surprisingly similar values of composite elongation and strength were obtained with unmodified bentonite JP A030.

The increasing demands for oil and gas and associated difficult drilling operations require oil-based drilling fluids that possess excellent rheological properties and thermal stability. The objective of the present work was to investigate the rheological properties and thermal stability of organo-montmorillonite (OMnt) modified with various surfactants and under various loading levels in oil-based drilling fluids, as revealed by the interaction between organic surfactants and montmorillonite. The influence of the structural arrangement of surfactants on the thermal stability of organo-montmorillonite (OMnt) in oil-based drilling fluids was also addressed. OMnt samples were prepared in aqueous solution using surfactants possessing either a single long alkyl chain two long alkyl chains. OMnt samples were characterized by X-ray diffraction, high-resolution transmission electron microscopy, thermal analysis, and X-ray photoelectron spectroscopy. Organic surfactants interacted with montmorillonite by electrostatic attraction. The arrangements of organic surfactants depended on the number of long alkyl chains and the geometrical shape of organic cations. In addition to the thermal stability of surfactants, intermolecular interaction also improved the thermal stability of OMnt/oil fluids. A tight paraffin-type bilayer arrangement contributed to the excellent rheological properties and thermal stability of OMnt/oil fluids. The deterioration of rheological properties of OMnt/oil fluids at temperatures up to 200°C was due mainly to the release of interlayer surfactants into the oil.

Reflectance spectroscopy is a rapid and non-destructive method that can be used to detect organic compounds in geologic samples over a wide range of spatial scales that includes outcrops, hand samples, drill cores, and planetary surfaces. In order to assess the viability of this technique for quantification of organics and aliphatic compounds in particular, the present study examines how clay mineralogy, water content, and albedo influence the strength of organic absorptions in near-infrared (NIR) reflectance spectra. The effects of clay structure and water content are evaluated using kaolinite, smectite (montmorillonite), and a mixed-layer illite-smectite as starting materials. Absorption strengths for C—H absorptions are compared to known total organic carbon (TOC) values using both reflectance spectra and single scattering albedo (SSA) spectra derived from a Hapke radiative transfer model. A linear relationship was observed between band depth and TOC for each sample suite, but strong albedo variation led to non-unique trends when band depths were calculated from reflectance spectra. These effects were minimized by conversion to SSA, for which band depth-TOC trends were similar for all mixture suites regardless of albedo or hydration level, indicating that this approach may be more broadly applicable for clay and organic-bearing samples. Extrapolation of band depth-TOC trends for the synthetic mixtures suggested a very conservative lower limit of detection of <1 wt.% TOC, but preliminary results for natural organic-bearing shales indicated that detection limits may be an order of magnitude lower.

A comprehensive study of the intercalation of organo-phosphonium salts into Thai bentonite (Mt) was conducted to investigate the influence of the molecular structures of organic moieties, including chain types (alkyl vs. aryl), chain length, and structural symmetry, on their intercalation. A series of quaternary phosphonium salts with systematically varied molecular structures (tetraphenyl phosphonium, TPP-Br; tetrabutyl phosphonium, TBP-Br; tetraoctyl phosphonium, TOP-Br; methyl triphenyl phosphonium, MTPP-Br; and butyl triphenyl phosphonium, BTPP-Br) was intercalated into Mt via an ion-exchange reaction. From thermogravimetric analysis results, tetrabutyl phosphonium-modified Mt (TBP) with shorter alkyl chain length began to decompose at a slightly lower temperature (263 vs. 351°C), yet showed comparable thermal stability (i.e. maximum decomposition temperature) at 470°C, compared to tetraoctyl phosphonium-modified Mt (TOP). Aryl phosphonium-modified Mt (TPP) showed a higher thermal decomposition temperature (576 vs. 470°C) than those of alkyl phosphonium-modified Mts (TBP and TOP). Introducing short alkyl chains into the aryl phosphonium moiety (MTPP, BTPP) caused a slight decrease in thermal decomposition temperature, but an increase in cation loadings of their modified Mts (71 and 73%, respectively). X-ray diffraction analysis showed that the flexibility of alkyl chains in TBP yielded smaller increases in basal spacing, i.e. lower degree of intercalation, compared to the rigid aryl structure in TPP. Increasing chain length resulted in greater basal spacing in alkyl phosphonium-modified Mts (1.67 nm. in TBP vs. 2.46 nm. in TOP). Such an effect, however, was less significant in aryl phosphonium-modified Mt.

The transformation of clay minerals into organo-clays by surfactant intercalation is of great environmental and industrial importance because it causes the clay to attract hydrophobic contaminants and other non-polar organic compounds, but a better understanding is needed of the mechanisms by which different classes of surfactants are intercalated. The purpose of this study was to synthesize and characterize an organo-clay comprising triethylene glycol monodecyl ether (C10E3) non-ionic surfactant, which has a lamellar phase at room temperature, intercalated into Ca-montmorillonite from Wyoming (SWy-2). The C10E3 non-ionic surfactant differed from previous non-ionic surfactants used in the formation of a lamellar phase in that it consisted of the stacking of molecules by hydrophobic interaction. C10E3-clay composites were characterized by complementary techniques (adsorption isotherms, X-ray diffraction, and infrared spectroscopy) and were compared to benzyldimethyltetradecyl ammonium chloride (BDTAC) cationic surfactant-clay composites for different loadings of the surfactant. For large loadings, the amount of C10E3 adsorbed, which can be described by the Langmuir equation, seemed to reach a steady state close to that of the cationic surfactant. The adsorption processes of the two surfactants were different. For the cationic surfactant, the adsorption, as described in the literature, was due to ion exchange between organic cations and Ca2+ counterions. The adsorption of C10E3 did not depend on electrostatic interaction but rather was due to several interaction mechanisms (H-bonding, ion-dipole, and hydrophobic interaction). For both surfactants, the expansion was limited to two adsorbed monolayers parallel to the clay surface. The expansion of the basal spacing to 17 Å suggested a complete dissociation of the C10E3 lamellar phase when adsorbed on the Ca-smectite. Organo-clays made using the non-ionic surfactant were stable, changing the chemical nature of clay to hydrophobic, and allowing for other cations to be exchanged, which has importance in the manufacture of new nanocomposites or geochemical barriers.

Non-ionic surfactants Brij 56 and Igepal CO 720, containing hydrophilic poly(ethylene oxide) (PEO) segments, expanded smectite from 1.5 nm to 1.7 nm at room temperature. The surfactant-smectite composites had larger layer spacings than Ca-smectite after heat treatment. The surfactant-smectite composites were solvated and expanded to 1.8–1.9 nm by polar solvents, glycerol and water, but were not affected by the non-polar or weakly polar solvents, toluene, hexane or octanol. The hydrophilic PEO segments of non-ionic surfactants would logically access the interlayer spaces of smectite whereas the hydrophobic segments extend away from the mineral. The molecular structure and solvation properties suggest that the surfactant molecules are probably concentrated in the margin area of the interlayer galleries forming an annular ring structure between two neighboring silicate sheets. Only two layers or less of the surfactants could access the interlayer galleries of smectite and layer spacings did not exceed 1.8 nm even where excess surfactant was introduced into the composites. The layer spacings of the surfactant-smectite composites were well preserved during water or electrolyte solution washings, indicating stability of most non-ionic surfactant molecules in the interlayer galleries even though ∼30% of the adsorbed Igepal CO 720 was desorbed by exhaustive washing. The non-ionic surfactant treatment preserved >80% of the CEC of the smectite. The interlayer cations of the resulting surfactant-smectite were exchangeable as in the untreated smectite. Therefore, the non-ionic surfactant-smectite was much more efficient at removing heavy metal ions than activated carbon or cationic surfactant-treated smectite. The surfactant-smectite composites effectively removed aromatic chlorophenols from a pH 4.9 acetate buffer solution while untreated smectite did not adsorb these molecules. The enhanced adsorption of the aromatic compounds is attributed to the aliphatic segments of the two surfactants.

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.

Intercalation of a wide variety of alkylammonium cations into the interlayer spaces of swelling clay minerals leads to many different applications, ranging from surface-charge measurements to rendering the clay compatible for the preparation of clay nanocomposites, but knowledge of the exact conformation of the intercalated organic species is still incomplete, thus preventing a full understanding of this process. The purpose of this study was to investigate the interlayer conformation of dodecyltrimethylammonium (DDTMA) bromide in rectorite as affected by the amounts of DDTMA intercalated, using a battery of physical and spectroscopic methods. The capacity of rectorite to intercalate DDTMA was equivalent to 1.67 times the cation exchange capacity (1.67 CEC) of the mineral even though the initial input was as much as 5.00 CEC. When the DDTMA intercalated was <0.50 CEC of the mineral, minimal counterion sorption was associated with DDTMA intercalation. Derivative thermogravimetric (DTG) analyses revealed a single-peak decomposition temperature (Tpeak) at 430°C. X-ray diffraction (XRD) analyses indicated a flat-lying monolayer of the intercalated molecules, while shifts in Fourier Transform infrared (FTIR) bands confirmed gauche conformation. These results suggested that cation exchange was the dominant mechanism. At the maximum intercalation, the DDTMA adopted a horizontal trilayer arrangement with mainly gauche conformation as determined by FTIR and XRD. Meanwhile a second Tpeak appeared at 255°C, similar to the Tpeak of solid DDTMA. Counterion bromide sorption accompanying DDTMA intercalation reached a capacity of 310 mmol/kg. The results indicated that van der Waals interaction was responsible for the DDTMA uptake at the amount beyond 0.50 CEC. When the amount of DDTMA intercalated was between 0.5 and 1.67 CEC, the XRD patterns showed non-integrality, i.e. the 002 reflection was split into two non-integral peaks with 2 × d002 < d001 and 3 × d003 > d001. They became integral at 1.67 CEC. The results suggest that the mineral might be composed of mixed layers of a monolayer intercalated rectorite and a trilayer intercalated rectorite, without a bilayer as intermediate, when the amount of DDTMA intercalated was between 0.5 and 1.67 CEC.

The flavonoid naringin is the main source of the undesirable bitter taste in some citrus juices. In commercial debittering processes, the naringin is adsorbed on non-ionic polymeric resins. Organo-clays (OCs), which have been used as sorbents for organic pollutants, could also have affinity for the naringin molecule, and thus potentially could serve as a debittering agent. The objective of the present study was to characterize the sorption capacity of a prepared OC to evaluate its ability to remove naringin from aqueous solutions, investigating the effect of adsorbent dose, initial concentration of naringin, temperature, contact time, and pH. The OC was prepared by the intercalation of cationic surfactant hexadecyltrimethylammonium bromide in a Mexican bentonite. The host clay and the OC were characterized by X-ray diffraction, Fourier-transform infrared, and nitrogen gas adsorption. The OC showed a surface area of 9.3 m2 g-1, 11.35 nm average pore diameter, and a basal spacing, d001, of 2.01 nm. The adsorbent removed naringin at the rate of 60-72% at 25°C and pH 3. The sorption capacity increased with pH and temperature. Experimental data were well fitted by both Langmuir and Freundlich adsorption models. Most of the sorption took place during the first 10 min and the equilibrium time was reached within 720 min. The rate of sorption was adjusted to pseudo second-order kinetics.