Role of Interfacial Interactions in the Deposition of Colloidal Clay Particles in Porous Media

Colloidal clay particle transport under saturated conditions is believed to be controlled by its interactions with the surrounding environment. The dominating forces among these interactions are electrostatic forces that are determined by colloidal clay particle and porous medium surface charge density and Lifshitz–van der Waals forces that are determined by colloidal clay particle and porous medium surface thermodynamic properties. Electrostatic forces are greatly affected by solution chemistry in terms of solution ionic strength and pH. In this research, electrostatic and Lifshitz–van der Waals forces of natural colloidal clay particles with a model porous medium of silica sand were quantified at different ionic strength and pH conditions. At the same time, colloidal clay particle transport in the model medium of silica sand was conducted in a laboratory column. The maximum electrostatic forces, F ^EL (max), which occurred when the separation distance between colloidal clay particles and the porous medium was in the range of the sum of the double layer thicknesses of the colloidal clay particles and the porous medium, was found to be the determinant factor for colloidal clay particle deposition in the porous medium. Colloidal clay particle desorption in the porous media was related to the net effect of attractive Lifshitz–van der Waals forces and repulsive electrostatic forces, evaluated at the equilibrium distance where physical contact between the colloidal clay particle and silica sand actually occurred (i.e., affix force). Higher colloidal clay particle desorption was found to coincide with smaller affix force values.     

Pore Structure Tailoring of Pillared Clays with Cation Doping Techniques

Techniques and mechanism of doping controlled amounts of various cations into pillared clays without causing precipitation or damages to the pillared layered structures are reviewed and discussed. Transition metals of great interest in catalysis can be doped in the micropores of pillared clay in ionic forms by a two-step process. The micropore structures and surface nature of pillared clays are altered by the introduced cations, and this results in a significant improvement in adsorption properties of the clays. Adsorption of water, air components and organic vapors on cation-doped pillared clays were studied. The effects of the amount and species of cations on the pore structure and adsorption behavior are discussed. It is demonstrated that the presence of doped Ca²⁺ ions can effectively aides the control of modification of the pillared clays of large pore openings. Controlled cation doping is a simple and powerful tool for improving the adsorption properties of pillared clay.     

Evaluation of the role of an ionic liquid as organophilization agent into montmorillonite for NBR rubber nanocomposite production

In this work we have shown the preparation of montmorillonite (Na + Mt) co-intercalated with a quaternary ammonium salt (hexadecyltrimethylammonium — HDTMA) and an ionic liquid (IL) (1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)imide — OMImTf₂N) using a mechanochemical process. Changes in the structure of the organophilized montmorillonite were characterized using X-ray diffraction (XRD), thermal gravimetry (TG), Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The presence of both cations (HDTMA and OMIm) into the clay mineral layers was confirmed by FTIR. XRD studies support that the co-intercalation process of the IL cation is more easily established in phases in which the interlayer space is not totally packed with HDTMA and an additional order in ionic liquid phase was observed when the IL amount exceeds 15 mass%. The addition of IL induced a thermal stability gain of 90 °C in comparison with the ammonium treated montmorillonite. The incorporation of IL in the ammonium based organoclays also displayed their better compatibility with the elastomeric matrix (NBR). Morphology studies by SEM of cryofractured surfaces evidence an improved interface interaction between the clay mineral and elastomer, indicating that ionic liquid has a direct and pronounced effect on the final clay polymer nanocomposites. This result can be assigned to the covered clay mineral particles mainly for higher IL content.     

Bioleaching of iron from highly contaminated Kaolin clay by Aspergillus niger

Kaolin is a clay mineral that has a wide application in the industry specially, in paper, ceramic, and porcelain manufacturing. One of the most important factors that affects the value of this raw material is its brightness. Unfortunately, with the iron oxides deposit on mineral particles during kaolin formation, much of this clay has become unusable for industries. So, several chemical methods have been applied in mineral processing plants to reduce these contaminants, but finding a more sustainable approach like biological methods have always attracted a great attention. In this work bioleaching of iron from a highly contaminated kaolin sample was carried out using two different strains of Aspergillus niger, and the effects of strain type, pulp density, and time of clay addition on the iron removal were investigated by employing a 2³ full factorial design. Finally, it is concluded that strain type has the most significant effect on the response; also, the highest removal extent was 42.8% that was obtained by using the strain isolated from pistachio shell, and at the pulp density of 20 g/l when the clay was added at the beginning of the experiments.     

Ag(I)/Ag electrode reaction in amide-type room-temperature ionic liquids

Ag(I)/Ag electrode reaction was investigated in some amide-type room-temperature ionic liquids composed of different cations. The morphology of silver deposits and the electrochemical behavior were not sensitive to the difference in the cations of ionic liquids. On the other hand, it was suggested that the adsorption of bis(trifluoromethylsulfonyl)amide (TFSA⁻) is more important for electrodeposition of silver in both ionic liquids and aqueous solutions. The diffusion coefficients of silver cation in the ionic liquids indicated the silver cation is surrounded by TFSA⁻ to form a bulky species. The rate of crystal growth of silver particles in the ionic liquids by electrochemical Ostwald ripening was much slower than that in a nitrate aqueous solution, suggesting the charge transfer in the ionic liquids is slower than that in the aqueous solution.     

Removal of fulvic acid from aqueous media by adsorption onto modified vermiculite

Clay minerals are low cost materials that can be structurally modified and exploited for removal of natural organic matter from freshwaters. The present study shows that vermiculites modified by ion exchange with hexadecyltrimethylammonium or intercalation with poly(hydroxy iron) cations are potential adsorbents for removal of fulvic acid, whereas the adsorption on the raw clay mineral is negligible. The efficiency of the modified vermiculite was evaluated by measuring adsorption isotherms by the batch technique using initial fulvic acid concentrations between 2.5 and 50.0 mg L^− 1, with one hour of contact time. At least 94% of the fulvic acid initially present in a 20 mg L^− 1 solution was sorbed onto either the intercalated poly(hydroxy iron) cations or the organically modified vermiculite. Up to an initial concentration of 5.0 mg L^− 1 the adsorption is irreversible, and no quantifiable fulvic acid was measured in the desorption experiments. For initial fulvic acid concentrations between 10.0 and 50.0 mg L^− 1, desorption was between 2.3% and 4.9% for Fe(III) intercalated vermiculite, and between 1.4% and 9.2% for the organoclay. The adsorption percentages on intercalated poly(hydroxy iron) cations increased upon lowering pH and increasing the ionic strength, indicating the occurrence of strong binding mechanisms such as ligand exchange. Adsorption percentage of fulvic acid onto the organoclay also increased with lowering of pH, but in this case the adsorption percentages showed a small decrease at high ionic strength, suggesting that electrostatic attraction plays an important role in the adsorption process.     

Colloidal flocculation of micellar solutions of anionic surfactants

Micellar solutions of anionic surfactants usually precipitate in the presence of cations, following a mechanism by which initially cations bind themselves to the micellar surface until saturation is achieved. At higher cation concentrations, unbound cations precipitate with surfactant monomers. In a few cases cations, and especially Al³⁺, cause surfactant micelles to flocculate. These flocs have properties as adsorbents of acidic organic compounds, which might be used in water treatment processes. Both α-olefinsulfonates C₁₄−C₁₆, and laurylsulfate micellar solutions are fast flocculation colloidal systems in the presence of Al³⁺.     

Ionic conductivity enhancement of the plasticized PMMA/LiClO4 polymer nanocomposite electrolyte containing clay

This work has demonstrated that the addition of an optimum content of dimethyldioctadecylammonium chloride (DDAC)-modified montmorillonite clay (Dclay) enhances the ionic conductivity of the plasticized poly(methyl methacrylate)-based electrolyte by nearly 40 times higher than the plain system. Specific interactions among silicate layer, carbonyl group (CO) and lithium cation have been investigated using Fourier-transform infrared (FTIR), solid-state NMR, alternating current impedance. The FTIR characterization confirms that both of the relative fractions of ‘complexed’ CO sites and ‘free’ anions increase with the increase of the Dclay content, indicating that strong interaction exists between the CO group and the lithium salt. In addition, the solid-state NMR demonstrates that the interaction between the PMMA and the clay mineral is insignificant. The addition of clay mineral promotes the dissociation of the lithium salt and thus, the specific interaction can be enhanced between the CO and the free lithium cation. However, the balanced attractive forces among silicate layers, CO groups, lithium cations and anions is critical to result in the higher ionic conductivity.     

Diffusion behavior of univalent cations during cation interchange across an ion-exchange membrane

Measurements have been made of two-cationic cell potentials and cation interchange fluxes for the exchange between K⁺, Na⁺, Li⁺ and H⁺ across a polystyrenesulfonic acid ion-exchange membrane separating solutions of hydrochloric acid and the univalent chloride salts of varied composition. The experimental data have been used to estimate the magnitudes of ionic mobility ratios, membrane ionic concentrations, “effective” single-ion diffusion and interdiffusion coefficients of the interchanging cations in the membrane corresponding to various time intervals during a normal integral cation interchange process. The results indicate that during cation interchange the “effective” single-ion diffusion coefficients of the counterdiffusing cations in the membrane vary markedly over ranges of up to 80% of equilibrium of the interchange processes investigated.     

A Striking Effect of Ionic‐Liquid Anions in the Extraction of Sr2+ and Cs+ by Dicyclohexano‐18‐Crown‐6

Abstract

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr²⁺ and Cs⁺ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr²⁺ over Na⁺, K⁺, and Cs⁺ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazolium cations.     

Influence of pore water chemistry on the swelling behavior of compacted clays

The influences of the exchange complex and pH of the solution used for cation saturation on Atterberg limits, compaction, and swelling potential of a compacted clay were investigated. The study involved transforming the exchange complex from a heterogeneous to a homogeneous one so that a frame of reference can be set for the clay behavior under such an ideal condition. The employed method for altering the exchange complex successfully yielded homo-ionic clay. The introduction of different species of cations gave rise to different particles associations. When introduced to the tested clay, potassium cations bond its particles with a rather strong bond (K-linkage), causing a drastic decrease in the specific area of the clay (about one-fourth of its untreated specific area), a decrease in the CEC, as well as a drastic decrease in the swell potential. For example, the swell pressure decreased from 1.87 kg/cm² for the untreated samples to 0.4 kg/cm² for the K-treated samples (under the same conditions). Also, the swell potential vs. time relationships can be modeled accurately using a rectangular hyperbola.     

The Effect of Lithium on the Cation Exchange Behaviour of Crystalline and Amorphous Clays

The amount of cations displaced by LiCl—LiOAc from standard clay minerals and soil clays was dependent on the concentration and pH of the replacing solution. Lithium was more effective in replacing monovalent ions than ammonium. Appreciable quantities of Li were adsorbed by replacement on the broken bonds of the clay surfaces, especially in the amorphous clays. Certain montmorillonite clays fixed some of the sorbed Li. In general, the cation exchange behaviour was highly dependent on the structure of the clay mineral and the nature of its surface. The sum of displaced cations can be taken as representing the exchange capacity of the clay at the experimental conditions, while the amount of retained Li provides supplemental information on the nature of the bonds.     

Differences in the rheology and surface chemistry of kaolin clay slurries: The source of the variations

Kaolinite clays from two sources were found to display different rheological and electrokinetic behaviour despite having similar mineral composition. This difference is mainly due to the surface chemistry at the edges of the clay particles. Making the edge surface chemistry similar with an adsorbed small anionic additive such as citrate, produced a similar yield stress-pH behaviour for the different kaolin clay slurries. Heterogeneous attraction between positively charged edges and negatively charged faces of the clay particles is responsible for the yield stress behaviour of the clay slurry. However, the different points of zero charge of the edge caused the clay slurries to display different yield stress-pH behaviour. Adsorption of anionic citrate on negatively charged kaolin clay particles is reflected in a significant increase in the magnitude of the negative zeta potential. The adsorption is likely to be on the edge of the clay particles. Adsorbed citrate generally reduces or eliminates heterogeneous charge attraction leading to a much denser sediment being formed in the kaolin slurries with a coarser particle size distribution.     

Layered clay/epoxy nanocomposites: Thermomechanical,flame retardancy,and optical properties

In this study, layered clay/polymer nanocomposites were developed based on epoxy resins and montmorillonite as the nanoplatelet reinforcement. Clay particles were treated with hexadecyltrimethylammonium chloride (HTCA) through an ion exchange reaction. In this way, Na⁺ interlayer cations of the clay is exchanged with onium cation of the surfactant that turns the hydrophilic clays (MMT) to organophilic (OMMT) characteristics. Thermal analysis results revealed that the glass transition temperature (T_g) and the dynamic mechanical properties including the storage and loss modulus of the neat epoxy resin increases by the incorporation of clay particles. It was also found that flame resistance of the polymer is improved by the addition of the clay particles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structural Rearrangement of Dps-DNA Complex Caused by Divalent Mg and Fe Cations

Two independent, complementary methods of structural analysis were used to elucidate the effect of divalent magnesium and iron cations on the structure of the protective Dps-DNA complex. Small-angle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-EM) demonstrate that Mg²⁺ ions block the N-terminals of the Dps protein preventing its interaction with DNA. Non-interacting macromolecules of Dps and DNA remain in the solution in this case. The subsequent addition of the chelating agent (EDTA) leads to a complete restoration of the structure of the complex. Different effect was observed when Fe cations were added to the Dps-DNA complex; the presence of Fe²⁺ in solution leads to the total complex destruction and aggregation without possibility of the complex restoration with the chelating agent. Here, we discuss these different responses of the Dps-DNA complex on the presence of additional free metal cations, investigating the structure of the Dps protein with and without cations using SAXS and cryo-EM. Additionally, the single particle analysis of Dps with accumulated iron performed by cryo-EM shows localization of iron nanoparticles inside the Dps cavity next to the acidic (hydrophobic) pore, near three glutamate residues.     

Dielectric behaviour and relaxation processes of montmorillonite clay nano‐platelet colloidal suspensions in poly(vinyl pyrrolidone)–ethylene glycol oligomer blends

BACKGROUND: Intercalated and exfoliated montmorillonite (MMT) clay structures in polymer matrices improve the thermal, mechanical, electrical and pharmaceutical properties of organic–inorganic materials. Poly(vinyl pyrrolidone) (PVP)–ethylene glycol oligomer (EGO) blends are biocompatible and non‐toxic materials. The dielectric characterization of MMT clay nano‐platelet colloidal suspensions in PVP–EGO blends is important in understanding the ionic conduction behaviour in many complex phenomena occurring in biological systems, and in selective membranes and their use in controlled drug release systems and in liquid electrolytes. RESULTS: An investigation using dielectric spectroscopy in the 20 Hz to 1 MHz frequency range of MMT clay nano‐platelet colloidal suspensions in PVP–EGO blends confirmed that the PVP segmental motion, ionic conduction relaxation time, electric double layer relaxation time and direct current electrical conductivity are significantly influenced by the clay concentration and EGO chain length. In these materials, ionic motion and PVP segmental dynamics are strongly coupled. Intercalation of EGO structures in clay galleries and exfoliation of clay platelets by adsorption of PVP–EGO structures on clay surfaces are governed by hydrogen bonding interactions between the carbonyl groups of PVP monomer units, the hydroxyl groups of EGOs and the hydroxylated aluminate surfaces of the MMT clay. CONCLUSION: The dielectric behaviour of intercalated and exfoliated structures of MMT clay nano‐platelet colloidal suspensions in PVP–EGO blends provides a convenient way to obtain liquid organic‐inorganic polymeric nanocomposite electrolytes with tailored ionic conduction properties. Copyright © 2009 Society of Chemical Industry     

Improved efficiency of a divalent herbicide in the presence of clay, by addition of monovalent organocations

A severe decrease in efficacy of contact herbicides such as diquat (DQ) is caused by dust accumulated on the weeds. Such inactivation was explained by the adsorption of herbicides on dust particles. As a result of this inactivation, the rates of pesticides needed for efficient pest control are usually larger than the recommended rates, which increases the expenses, and pose a real danger to the environment and to the ecological balance of watersheds. We proposed the hypothesis that the addition of a monovalent organic cation to the herbicide formulation might improve the efficacy by lowering the amount of herbicide that is inactivated by the sorption to clay minerals. This hypothesis was tested on lettuce and pepper plants dusted with clay, using the commercial formulation of diquat (“Reglone”) and adding the monovalent organic cations acriflavin (AF) and mepiquat (MQ). We observed that a clay mineral with a high cation exchange capacity (CEC), such as montmorillonite, reduced the herbicidal activity of DQ more than a lower CEC clay as sepiolite. However, addition of 5–20 mM concentrations of AF or MQ may overcome the influences of a clay dust on the activity of a cationic herbicide. Such addition allowed the obtainment of good herbicidal results with less than 1/3 of the normal used amount of herbicide. The results of our research point out to a mechanism that may lower the needed doses of contact herbicides, due to a competitive adsorption on the clay–dust particles between the pesticide and monovalent organic cations that leaves more herbicide available to act on the weed.     

The electrochemical oxidation of phenylenediamines

Five p-phenylenediamines were oxidized electrochemically at a glassy carbon rotating ring-disk-electrode assembly. The overall reaction comprises the transfer of two electrons per molecule. At low to intermediate potentials the rate determining step for all the five compounds is the acid dissociation of the semiquinonediimine radical cation formed in a pre-equilibrium involving the transfer of one electron. Only at higher potentials can the radical cation be oxidized in parallel to the neutral semiquinone radical to form the quinonediimines. In contrast, the neutral semiquinonediimine radicals are oxidized at the same or even a lower potential than the parent phenylenediamines. The dissociation rate constants of the radical cations are in the range of 10-300 s⁻¹. The effect of the substituents on the oxidation potentials is as expected by their property to donate electrons to the mesomeric system. Their effect on the dissociation rates, however, seems to rather correlate with the inductive effect and might influence not only the electronic structure of the molecule itself but also the structure of the ions and the solvent around them. The semiquinonediimine radical cations are found to be slightly more acidic than their protonated parent phenylenediamine cations with pK_a values somewhat below 6.     

Temperature effects on iodine adsorption on organo-clay minerals: I. Influence of pretreatment and adsorption temperature

The sorptive capability of clay minerals for anionic radionuclides can be improved substantially by exchanging the natural inorganic interlayer cations with certain organic cations. After screening a variety of possible candidates, four organic cations were selected and combined with three clay minerals, providing 12 organo-cation/clay mineral combinations. The samples were tested for anion adsorption in batch experiments with radioiodide in a concentration range of 10⁻² to 10⁻⁹ mol l⁻¹ and exhibited high adsorption in bidistilled water as well as in synthetic groundwater. Results for two clay minerals—a smectite and a vermiculite—and four organic cations are given in this paper.Tests were also performed with temperature pretreated material. An increase of the pretreatment temperature from 20 to 40, 60, 80 and 100 °C did not result in a remarkable effect on iodide adsorption, except for the 1,12-dipyridiniododecan/vermiculite combination.In batch experiments with equilibrium temperatures of 20–60 °C, iodide adsorption decreased slightly with increasing temperature. Only 1,12-dipyridiniododecan in combination with smectite and vermiculite showed a somewhat lower iodide adsorption at higher temperatures.     

Highly efficient monovalent ion transport enabled by ionic crosslinking-induced nanochannels

Charge-governed ion transport is of significant importance to industrial development, and advanced membrane materials with fast and selective ionic transport are essential components. In cell membranes, ionic transport is mainly determined by the charge-governed protein channels, representing an architecture with functional differentiation. Inspired by this, a novel class of membranes was developed by ionically crosslinking sulfonated (poly[ether ether ketone]) and quaternized poly(2,6-dimethyl-1,4-phenylene oxide) to construct the cationic conductive biomimetic nanochannels. Ionic crosslinking was tailored to realize nanophase separation and efficient ion transport mainly based on surface chemistry without altering the scaffold feature of polymeric pore channels. The best-performing ionic crosslinking membrane exhibited a high ionic permeation (2.23 mol·m⁻²·h⁻¹ for K⁺) and high cationic selectivity (7.91 for K⁺/Mg²⁺), which were comparable with the commercial monovalent cation permselective CIMS membrane, owing to the negligent surface resistance toward monovalent cations but strong positively charged repulsion against divalent cations.