Sorption of Bisphenol A as Model for Sorption Ability of Organoclays

The arrangement of bisphenol A molecules into organoclays and their interactions with the intercalated surfactant were studied. The organoclays were prepared via solid-state intercalation of four cationic surfactants, such as dodecyltrimethyl-, tetradecyltrimethyl-, hexadecyltrimethyl-, and didodecyldimethyl-ammonium, as bromide salts, at different loading levels into the interlayers of two natural clays. The natural clays, the prepared organoclays, and the spent organoclays were characterized by X-ray powder diffraction, infrared spectroscopy, and scanning electron microscopy. X-ray powder diffraction measurements showed successive interlayer expansions of the d₀₀₁ basal spacing due to the intercalation of the cationic surfactants and the bisphenol A sorption. The increased d₀₀₁ basal spacing of the organoclays after bisphenol A sorption indicates that the molecules are integrated between the alkyl chains of the surfactant in the organoclays interlayers. Infrared spectroscopy was employed to probe the intercalation of the cationic surfactants and the sorbed bisphenol A. New characteristic bands attributed to the bisphenol A phenol rings appear in the range 1518–1613 cm⁻¹ on the infrared spectra of the spent organoclays, proving the presence of bisphenol A in the hydrophobic interlayers. Scanning electron microscopy of the organoclays before and after BPA sorption shows that their morphology becomes fluffy and that the presence of the organic molecules expands the clay structure.     

Intercalation of a nonionic surfactant (C10E3) bilayer into a Na-montmorillonite clay

A nonionic surfactant, triethylene glycol mono-n-decyl ether (C(10)E(3)), characterized by its lamellar phase state, was introduced in the interlayer of a Na-montmorillonite clay at several concentrations. The synthesized organoclays were characterized by small-angle X-ray scattering in conjunction with Fourier transform infrared spectroscopy and adsorption isotherms. Experiments showed that a bilayer of C(10)E(3) was intercalated into the interlayer space of the naturally exchanged Na-montmorillonite, resulting in the aggregation of the lyotropic liquid crystal state in the lamellar phase. This behavior strongly differs from previous observations of confinement of nonionic surfactants in clays where the expansion of the interlayer space was limited to two monolayers parallel to the silicate surface and cationic surfactants in clays where the intercalation of organic compounds is introduced into the clay galleries through ion exchange. The confinement of a bilayer of C(10)E(3) nonionic surfactant in clays offers new perspectives for the realization of hybrid nanomaterials, since the synthesized organoclays preserve the electrostatic characteristics of the clays, thus allowing further ion exchange while presenting at the same time a hydrophobic surface and a maximum opening of the interlayer space for the adsorption of neutral organic molecules of important size with functional properties.     

Stabilization of hydroxyl-group-terminated SERS-marker molecules on microAg particles by silanization

Surfactant modified montmorillonitic clays synthesized by ion exchange using the hydrothermal reaction method have been compared using XRD and thermal analysis. X-ray diffraction (XRD) shows the changes in the surface properties of organoclays through expansion with surfactant loading. A polynomial relationship exists between the basal spacing and the CEC loading described by the equation y=0.3232x(2) + 0.2052x+1.2834 with R(2)=0.9955. Different arrangements of the surfactant molecules in the organoclays are inferred from the changes in basal spacings. para-Nitrophenol also causes the expansion of the montmorillonite clay and affects the arrangements of the surfactant molecules within the clay layers. Changes in the surfactant molecular arrangements were analyzed by thermogravimetry. Additional thermal decomposition steps were observed when para-nitrophenol is adsorbed on the organoclay.     

Adsorption of p-nitrophenol on organoclays

In this study, organoclays were prepared through ion exchange of a single cationic surfactant, hexadecyltrimethylammonium bromide and characterised by a range of methods including X-ray diffraction (XRD) and thermogravimetric analysis. Changes in the surface properties of montmorillonite and the organoclays were observed and the basal spacings of organoclays with and without p-nitrophenol were determined using XRD. The thermal stability of both organoclays were measured using thermogravimetry. As the surfactant loading increased, the expanded basal spacings were observed, and different molecular configurations of surfactant were identified. When the surfactant loading exceeded 1.0 CEC, surfactant molecules tend to adsorb strongly on the clay surface and this resulted in increased affinity to organic compounds. The adsorbed p-nitrophenol and the surfactant decomposed simultaneously. Hence, the surfactant molecules and adsorbed p-nitrophenol are important in determining the thermal stabilities of organoclays. This study enhances the understanding of the structure and adsorption properties of organoclays and has further implications for the application of organoclays as filter materials for the removal of organic pollutants in aqueous solutions.     

A novel organoclay with antibacterial activity prepared from montmorillonite and Chlorhexidini Acetas

A series of novel organoclays with antibacterial activity were synthesized using Ca-montmorillonite and Chlorhexidini Acetas (CA) by ion-exchange. The resultant organoclays were characterized using X-ray diffraction (XRD), high-resolution thermogravimetric analysis (HRTG) and Fourier transform infrared spectroscopy (FTIR). Their antibacterial activity was assayed by so-called halo method. In the organoclays prepared at low CA concentration, CA ions within the clay interlayer adopt a lateral monolayer while a 'kink' state or a special state with partial overlapping of the intercalated CA in the organoclays prepared at 1.0-4.0 CEC. HRTG analysis demonstrates that CA located outside the clay interlayer exists in all synthesized organoclays, resulting from the complex molecular configuration of CA. The dramatic decrease of the surface adsorbed water and interlayer water is caused by the surface property transformation and the replacement of hydrated cations by cationic surfactant. These observations are supported by the results of FTIR. Antibacterial activity test against E. coli demonstrates that the antibacterial activity of the resultant organoclays strongly depends on the content of CA. Meanwhile, the resultant organoclay shows a long-term antibacterial activity that can last for at least one year. These novel organoclays are of potential use in synthesis of organoclay-based materials with antibacterial activity.     

Insertion of fluorophore dyes between Cloisite Na+ layered for preparation of novel organoclays

The aim of this study was to obtain novel photo-functional organomontmorillonites from the intercalation reaction of Cloisite Na⁺ and fluorescent dyes of auramine O, and safranin T in an aqueous solution. The insertion of surfactants in the interlamellar space of nanoclay was followed by Fourier transform infrared spectroscopy and X-ray measurements. An X-ray diffraction analysis established that incorporation of the organic dye cations into the Cloisite Na⁺ expands remarkably the mineral interplanar distances from 1.17 to 1.83–1.97 nm. Field emission scanning electron microscopy was used to study the morphology of the synthesized organoclays. The thermal behavior of the novel hybrid materials was investigated by thermogravimetric analysis and the results show that the organo modified clays verify stepwise decomposition corresponding to initial weight loss from residual water desorption, followed by decomposition of the fluorescent dyes and the dehydroxylation of structural water of the clay layers. Fluorescence properties of the cationic dyes, auramine O, and safranin T incorporated in the clay have significant differences from their behavior in organic solvents and water and the results show that both dyes exhibit a significant fluorescence emission at room temperature when adsorbed in clay.     

Thermal stability of organoclays with mono- and di-alkyl cationic surfactants

In this study, mono- and di-alkyl cationic surfactants were used to prepare organoclays through ion exchange and the prepared organoclays were characterised by X-ray diffraction (XRD) and thermogravimetric analysis (TG). Larger basal spacings were observed in the interlayer of the organoclays intercalated with DDDMA than organoclays intercalated with DDTMA. The DTG curves identify the thermal stability of organoclays intercalated with two different types of surfactants (DDTMA and DDDMA) and the different arrangements of the surfactant molecules intercalated in the montmorillonite. Both organoclays intercalated with organic surfactant molecules proved to be thermally stable at high temperature. This study provides an understanding of the structure and properties of organoclays, which will enhance the potential applications of organoclays in environmental remediation.     

Effect of surfactant agent upon the structure of montmorillonite

The modification of sodium montmorillonite (MMT) through the incorporation of amphiphilic octadecylammonium cations in various concentrations (10–200% CEC) into the clay’s interlayer spaces has been studied. High resolution thermogravimetric analysis shows that the thermal decomposition of modified montmorillonite occurs in three steps. The first step of mass loss is related to dehydration of adsorbed water and water hydrating metal cations such as Na⁺. The second step of mass loss is attributed to the decomposition of surfactant. The third step is due to the loss of OH units during the dehydroxylation of the montmorillonite. The conformation of the surfactant cations in the confined space of the silicate galleries is investigated by X-ray diffraction analysis. These analyses are very important for any attempt to incorporate the organomodified MMT particles into different media for various applications such as polymer nanocomposite preparation.     

Modification of Wyoming montmorillonite surfaces using a cationic surfactant

Surfaces of Wyoming SWy-2-Na-montmorillonite were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Changes in the surfaces and structure were characterized using X-ray diffraction (XRD), thermal analysis (TG), and electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Three different molecular environments for surfactants within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Both XRD patterns and TEM images demonstrate that SWy-2-Na-montmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant reduces the clay particle size and aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic impurities from aqueous media.     

非离子表面活性剂对多壁碳纳米管在乙醇中高浓度分散的作用

如果能在无需聚合物或共价官能团辅助的条件下, 将多壁碳纳米管(MWNTs)高浓度地分散在乙醇中, 那么向各种复合材料引入MWNTs的过程就会更加便捷. 为此, 制备了多种含有表面活性剂的多壁碳纳米管乙醇悬浮液并对比考查了它们的稳定性. 非离子表面活性剂Triton X-100 和Tween 65显示出了在乙醇中分散悬浮高浓度MWNTs的能力, 能够使1.0 g·L-1 MWNTs乙醇悬浮液的上层清液经240 h后浓度仍分别在0.50和0.35 g·L-1以上. 这样长时间稳定的、没有聚合物或共价官能团辅助的MWNTs乙醇悬浮液, 其浓度比文献报道的值高. 进一步探讨了这些非离子表面活性剂分子结构对于分散MWNTs的优势, 并直观给出了其吸附于碳纳米管表面的可能形式. X射线光电子能谱和透射电子显微镜的表征结果都证实了表面活性剂分子吸附于碳纳米管表面.     

Structure of organoclays--an X-ray diffraction and thermogravimetric analysis study

X-ray diffraction has been used to study the changes in the surface properties of a montmorillonitic clay through the changes in the basal spacings of montmorillonite (SWy-2) and surfactant-intercalated organoclays. Variation in the d-spacing was found to be a step function of the surfactant concentration. High-resolution thermogravimetric analysis (HRTG) shows that the thermal decomposition of SWy-2-MMTs modified with the surfactant octadecyltrimethylammonium bromide takes place in four steps. A mass-loss step is observed at room temperature and is attributed to dehydration of adsorption water. A second mass-loss step is observed over the temperature range 87.9 to 135.5 degrees C and is also attributed to dehydration of water hydrating metal cations such as Na+. The third mass loss occurs from 178.9 to 384.5 degrees C and is assigned to a loss of surfactant. The fourth mass-loss step is ascribed to the loss of OH units through dehydroxylation over the temperature range 556.0 to 636.4 degrees C. A model is proposed in which, up to 0.4 CEC, a surfactant monolayer is formed between the montmorillonitic clay layers; up to 0.8 CEC, a lateral-bilayer arrangement is formed; and above 1.5 CEC, a pseudotrimolecular layer is formed, with excess surfactant adsorbed on the clay surface.     

Investigation of structure and thermal stability of surfactant-modified Al-pillared montmorillonite

For combining the properties of organoclays and pillared clays, inorganic–organic clays have attracted much attention in recent years. In this study, Al Keggin cation pillared montmorillonites (Al-Mts) were first prepared and parts of Al-Mts were calcined at different temperatures (C-Al-Mts). The inorganic–organic montmorillonites were synthesized by intercalating Al-Mts and C-Al-Mts with the cationic surfactant, hexadecyltrimethyl ammonium bromide (HDTMAB). The products were characterized by X-ray diffraction, X-ray fluorescence, and simultaneous thermogravimetric analysis. For HDTMAB-modified uncalcined Al Keggin cation pillared montmorillonites (H-Al-Mts), the basal spacing increased with the increment of surfactant loading level, but the Al content of H-Al-Mts decreased simultaneously, indicating that the intercalated surfactant replaced some Al Keggin cations in the interlayer space. However, in the case of C-Al-Mts, the interlayer spaces could not be further expanded after surfactant modification, implying that the neighboring montmorillonite layers were “locked” by the aluminum pillars which were formed by dehydroxylation of Al Keggin cation pillars during thermal treatment. The thermal stability of HDTMAB-modified C-Al-Mts (H-C-Al-Mts) was much better than that of H-Al-Mts. The major mass loss of H-C-Al-Mts occurred at ca. 410 °C, corresponding to decomposition of intercalated surfactant cations. In contrast, H-Al-Mts displayed two mass loss temperatures at ca. 270 and 410 °C, corresponding to the evaporation of surfactant molecules and the decomposition of surfactant cations in the interlayer space, respectively.     

Adsorption of fluorescent R6G dye into organophilic C12TMA laponite films

The absorption and fluorescence properties of rhodamine 6G (R6G) in organophilic laponite (Lap) clay films are studied. For this purpose, organo-Lap clays are synthesized by the incorporation of dodecyltrimethylammonium (C12TMA) as surfactant into the interlayer space of Lap clays. Two organo-Lap clays are prepared: one with moderate surfactant content (around 70% of the total cation-exchange capacity (CEC) of the clay) and a second with a high surfactant loading (about 130% CEC). Supported films are elaborated by the spin-coating technique and characterized by several techniques such as atomic force microscopy, elemental CHN analysis, X-ray diffraction, and thermogravimetry. IR spectroscopy reveals that the intercalation of R6G into organo-Lap films takes place at the detriment of the adsorbed C12TMA molecules. The photophysical properties of R6G monomers in the interlayer space of Lap films are improved by the presence of surfactant molecules. Moreover, organophilic environments can reduce the dye aggregation and favor the formation of fluorescent J-type aggregates, enhancing the fluorescence ability of dye/clay films with high dye contents. This improvement depends on the surfactant content.     

Effect of polymerically‐modified clay structure on the morphology and properties of UV‐cured polyurethane acrylate/clay nanocomposites

Polyurethane acrylate (PUA)/clay nanocomposites were prepared by UV‐curing from a series of styrene‐based polymerically‐modified clays and PUA resin. Effect of the chemical structure of the polymeric surfactants on the morphology and tensile properties of nanocomposites has been explored. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) experimental results indicated that surfactants having hydroxyl or amino groups show better dispersion and some of the clay platelets were fully exfoliated. However, the composites formed from pristine clay and other polymerically‐modified clays without hydroxyl or amino groups typically contained both tactoids and intercalated structure. The mechanical properties of PUA composites were greatly improved where the organoclays dispersed well. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were carried out to examine the thermal properties of the composites. The results showed that the loading of polymerically‐modified clays do not effect the thermal stability, but increased the Tgs of PUA/clay composites. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis, characterization of mono, di and tri alkyl surfactant intercalated Wyoming montmorillonite for the removal of phenol from aqueous systems

Organoclays were synthesized by the ion exchange of cationic surfactants containing single, double and triple alkyl chains for sodium ions in an aqueous suspension of Wyoming Na-montmorillonite. The characterization of organoclays with and without adsorbed phenol was determined by X-ray diffraction, TEM and thermal analysis. Differences in the surfaces and in the interlayer of the mono, di and tri alkyl chain organoclays resulted in differences in the adsorption efficiency for phenol with tri > di > mono > Na-Mt. The results prove that organoclays can be effective for the removal of phenol from an aqueous solution and this removal is a function of the surfactant molecule and its concentration. In general, the higher the concentration as measured by the CEC value and the greater the number of alkyl chains in the surfactant molecule, the greater the percentage of the phenol that is removed.     

Preparation and characterization of zwitterionic surfactant-modified montmorillonites

A series of zwitterionic surfactant-modified montmorillonites (ZSMMs) were synthesized using montmorillonite and three zwitterionic surfactants with different alkyl chain lengths at different concentrations [0.2-4.0 cation exchange capacity (CEC)]. These ZSMMs were characterized by X-ray diffraction (XRD), thermo-gravimetric analysis and differential thermo-gravimetric (TG/DTG) analyses. The zwitterionic surfactant could be intercalated into the interlayer spaces of montmorillonites and causing interlayer space-swelling. From XRD measurements, the amount of the surfactants loaded and the basal spacing increased with surfactant concentration and alkyl chain length. One endothermic DTG peak occurred at ~390 °C, which was assigned to the decomposition of the zwitterionic surfactant on the organo-montmorillonites from 0.2 to 0.6 CEC. When the surfactant loading was increased, a new endothermic peak appeared at ~340 °C. From the microstructures of these ZSMMs, the mechanism of zwitterionic surfactant adsorption was proposed. At relatively low loadings of the zwitterionic surfactant, most of surfactants enter the spacing by an ion-exchange mechanism and are adsorbed onto the interlayer cation sites. When the concentration of the zwitterionic surfactant exceeds the CEC of montmorillonite, the surfactant molecules then adhere to the surface-adsorbed surfactant. Some surfactants enter the interlayers, whereas the others are attached to the clay surface. When the concentration of surfactant increases further beyond 2.0 CEC, the surfactants may occupy the inter-particle space within the house-of-cards aggregate structure.     

Organoclays from alkaline-treated acid-activated clays

The cetyltrimethylammonium hydroxide (C16TMAOH) solution was proposed for the preparation of organoclays. Montmorillonite clay was acid activated at different acid/clay (a/c) (in mass) ratios, then treated with alkaline (sodium hydroxide) solution before being reacted with C16TMAOH solution. The acid activation caused a reduction in the number of cation exchange sites, and hence improved the exfoliation of the silicate sheets at higher pH values. The basal spacing increased significantly from 2.20 to 4.01 nm, and depended on the a/c ratios. The acid-activated clays with a/c ratios greater than 0.3 adsorbed significant amounts of C16TMA cations with a basal spacing of 4.01 nm compared with the non-acid-activated montmorillonite (2.51 nm). Meanwhile, the treatment of NaOH solution yielded clays with similar properties to that of the raw used clay. The XRF data, FT-IR, and ²⁹Si MAS-NMR techniques confirmed that the resulting amorphous silica during the acid activation was dissolved, and accompanied by a dramatical reduction in the surface areas. Similar amounts of C16TMA cations were adsorbed, i.e., close to 1 mmol g^?1, with a single basal spacing of 2.52 nm, independently of the treated acid-activated clays. The in-situ powder XRD studies revealed that an increase of the basal spacing to 4.20 nm was observed at intermediate temperatures ranging from 50 to 150 °C for organo-acid-activated clays with basal spacing of 4.01 nm, while a continuous decrease of the basal spacing was observed for organoclays with a basal spacing of 2.52 nm. At higher temperatures greater than 250 °C, the decomposition of the surfactant occurs, and the basal spacing decreases to a value of about 1.4 nm.     

Characterisation of organoclays and adsorption of p-nitrophenol: environmental application

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.     

Influence of organic surfactants on structural stability of mechanochemically treated bentonite

The aim of this work was to compare the influence of organocations with different length of alkylammonium chain on the structural stability of clays towards mechanochemical treatment. An industrial product JP A030 (Envigeo, Inc., Slovakia) based on Jelšovy Potok bentonite (Slovakia) and three organoclays prepared from this material via ion exchange with tetramethylammonium, octyltrimethylammonium and octadecyltrimethylammonium cations (TMA-JP A030, OTMA-JP A030 and ODTMA-JP A030, respectively) were ground for 1–20 min in a high-energy planetary mill. The products were investigated by X-ray diffraction analysis, thermal analysis, scanning electron microscopy and energy dispersive X-ray analysis. The long-chain organic cations apparently enhance the structural stability of bentonite during high-energy grinding.     

Use of a polyhedral oligomeric silsesquioxane (POSS)-imidazolium cation as an organic modifier for montmorillonite

Recent studies on organically modified clays (OMCs) have reported enhanced thermal stabilities when using imidazolium-based surfactants over the typical ammonium-based surfactants. Other studies have shown that polyhedral oligomeric silsesquioxanes (POSS) also improve the thermal properties of composites containing these macromers. In an attempt to utilize the beneficial properties of both imidazolium surfactants and POSS macromers, a dual nanocomposite approach to prepare OMCs was used. In this study, the preparation of a new POSS-imidazolium surfactant and its use as an organic modifier for montmorillonite are reported. The purity, solubility, and thermal characteristics of the POSS-imidazolium chloride were evaluated. In addition, several OMCs were prepared by exchanging the Na+ with POSS imidazolium cations equivalent to 100%, 95%, 40%, 20%, and 5% of the cation exchange capacity of the clay. The subsequent OMCs were characterized using thermal analysis techniques (DSC, SDT, and TGA) as well as 29Si NMR to determine the POSS content in the clay interlayer both before and after thermal oxidation degradation. Results indicate the following: (1) the solvent choice changes the efficiency of the ion-exchange reaction of the clay; (2) self-assembled crystalline POSS domains are present in the clay interlayer; (3) the d-spacing of the exchanged clay is large (3.6 nm), accommodating a bilayer structure of the POSS-imidazolium; and (4) the prepared POSS-imidazolium exchanged clays exhibit higher thermal stabilities than any previously prepared imidazolium or ammonium exchanged montmorillonite.