Structure and dynamics of surfactant interfaces in organically modified clays

Organic modification of clays with surfactants is required for the preparation of polymer-clay nanocomposites for a variety of applications. We have studied the structure and dynamics of interfaces in synthetic clays modified with phosphonium surfactants. The chemical shifts, line widths, and relaxation times measured by 31P, 13C, and 1H NMR and the relaxation times measured by impedance spectroscopy allow us to monitor the dynamics over a wide range of time scales. The results show that the phosphonium headgroup is most restricted and that the mobility increases with increasing separation from the clay surface. The carbon chemical shifts show that the 16-carbon and 12-carbon surfactant tails of hexadecyltributyl phosphonium and dodecytriphenyl phosphonium are disordered at the interface and experience mobility over a range of time scales. The dynamics depend most strongly on the structure of the surfactant headgroup, and tributylphosphoniums are more mobile than the triphenylphosphoniums. Two dimensional chemical shift anisotropy spin exchange experiments show that the phosphorus atoms in the triphenylphosphonium surfactant are immobile on the clay surface on a 1 s time scale. The dynamics measured by impedance spectroscopy show a similar dependence on headgroup structure, even though the processes occur on very different time scales and length scales. The relationship between the structure and dynamics of the interface and the properties of composites are considered.     

Dispersion and distribution of organically modified montmorillonite in nylon‐66 matrix

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with an alkyl ammonium surfactant pretreated montmorillonite (MMT). The thermal stability of the organic MMT powders was measured by thermogravimetric analysis. The decomposition of the surfactant on the MMT occurred from 200 to 500 °C. The low onset decomposition temperature of the organic MMT is one shortcoming when it is used to prepare polymer nanocomposites at high melt‐compounding temperatures. To provide greater property enhancement and better thermal stability of the polymer/MMT nanocomposites, it is necessary to develop MMT modified with more thermally stable surfactants. The dispersion and spatial distribution of the organic MMT layers in the nylon‐66 matrix were characterized by X‐ray diffraction. The organic MMT layers were exfoliated but not randomly dispersed in the nylon‐66 matrix. A model was proposed to describe the spatial distribution of the organic MMT layers in an injection‐molded rectangular bar of nylon‐66/organic MMT nanocomposites. Most organic MMT layers were oriented in the injection‐molding direction. Layers near the four surfaces of the bar were parallel to their corresponding surfaces; whereas those in the bulk differed from the near‐surface layers and rotated themselves about the injection‐molding direction. The influence of the spatial distribution of the organic MMT on crystallization of nylon‐66 was also investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1234–1243, 2003     

Effect of surfactant and solvent properties on the stacking behavior of non-aqueous suspensions of organically modified clays

Montmorillonite clay was treated with quaternary ammonium surfactants with 1-3 long chains of 10-18 carbons to form organoclays which can be suspended in non-aqueous solvents. The effects of surfactant chain length, number of long chains, and the properties of the solvent on the colloidal behavior of the surfactant coated clay plates were studied using small-angle X-ray scattering. The scattering data were modeled using a one-dimensional aggregation theory to describe the stacking of the clay plates. The plates self-organize into stacks with a reproducible basal spacing in the range of 30-50 A, and for each surfactant, the basal spacing falls into one of two preferred distances. We interpret this by considering that the surfactant layer on the clay has two strata, one being the polar near-clay headgroup region and the other the nonpolar alkane chain region. Polar solvents will swell the polar stratum preferentially while nonpolar solvents will swell the nonpolar stratum of the surfactant. As the nonpolar stratum is larger than the polar one, the nonpolar solvents increase the basal spacing between the clay plates more than the polar solvents. The number of long chains on the surfactant does not have an effect on the basal spacing, as the density of surfactant molecules on the surface is low enough to allow the unimpeded swelling of the chains. The one-dimensional aggregation theory can be used to determine the number of plates in a stack, but the effect of changing clay particle size or concentration is not as great as would be expected from this theory. This may be due to the formation of large-scale structures in the suspensions which prevent a true equilibrium stack size being attained.     

TG characterization of organically modified montmorillonite

Montmorillonite was modified with octadecyltrimethylammonium chloride, under different reaction conditions, as evidenced by TG and XRD. TG curves presented two degradation peaks (295 and 395°C). At low salt concentrations, only the 395°C-degradation appeared, which increased with reaction time to the limit of 9 g of salt/100 g of clay. The second peak presented a limit at 17/100 m/m of salt/clay ratio. XRD analysis confirmed clay organic modification as the basal distance increased, showing greater reaction time effect than the salt mass effect, and with only one d-spacing. This suggested that an intercalation complex was formed but also that octadecyltrimethylammonium was adsorbed on the external surfaces of clay particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Analytical applications of organically modified silicates

Inorganic-organic hybrid materials prepared by the sol-gel process have become an attractive field of study due to the immense versatility associated with this method of composite material preparation. The blending of inorganic precursors with organosilicon reagents enables unique materials to be fabricated with the desired chemical and physical characteristics. The ability to control the interfacial polarity, the degree of porosity, and the chemical functionality in the matrix has been shown to be a powerful tool in the design of materials for sensor, optical, chromatographic, and catalytic applications. In this review, the preparation of the organically modified silicates (ORMOSILs) where the individual precursors are covalently bound to each other is discussed and selected examples of their potential usefulness in analytical applications is presented.     

Ferricyanide immobilized within organically modified MCM-41; application for electrocatalytic reduction of hydrogen peroxide

Carbon paste electrode modified with aminated Mobil Catalytic Material Number 41 (MCM-41) was prepared and used for immobilization of K₃[Fe(CN)₆] in acidic medium, and then electrochemical behavior of modified electrode containing ferricyanide was studied in detail, including pH-dependence and scan rate effect. Cyclic voltammetry studies showed that the electrode reaction is a surface-controlled process at the scan rate range from 5 to 60 mV s⁻¹. Also, the electrocatalytic behavior of modified electrode toward the reduction of H₂O₂ is reported and the effect of pH on catalytic peak current was discussed. According to experimental results, with increasing solution pH, the catalytic effect of this modified electrode is decreased. Catalytic reduction current of H₂O₂ increases linearly with its concentration. It has been demonstrated that ferricyanide immobilized on the aminated MCM-41 is a stable catalyst for the electrocatalytic reduction of H₂O₂.     

Dynamics of alkyl ammonium intercalants within organically modified montmorillonite: Dielectric relaxation and ionic conductivity

The low-frequency (0.01 Hz-10 MHz) dynamic characteristics of alkyl quaternary ammonium exchanged montmorillonite (SC20A) were investigated to determine the correlation between temperature-dependent changes in the interlayer structure and collective mobility of the surfactant. From 25 to 165 degrees C, SC20A exhibits two interlayer transitions, one ascribed to the melting of the intercalated alkyl chains of the surfactant (20-40 degrees C) and another associated with an abrupt decrease in the interlayer's coefficient of thermal expansion (100 degrees C). For this temperature range, the excess surfactant and residual electrolytes present in commercially manufactured SC20A enhance the direct current conductivity and increase low-frequency space-charge polarization, which is believed to occur across percolation paths established by the surfaces of the SC20A crystallites. In contrast, a higher-frequency relaxation, which was less sensitive to process history and impurity content, is ascribed to relaxation within the interlayer at the surfactant-aluminosilicate interface electrostatic couple. The temperature dependence of these dielectric relaxations indicated a drastic increase in mobility as the interlayer organic phase transitions from static and glasslike into molten and mobile. Overall, SC20A displayed features of alternating current universality, including time-temperature superposition, common in other types of disordered ion-conducting media. The presence of long-range transport and its sensitivity to low amounts of impurities imply that from a dynamic perspective the local environment of the surfactants are substantially diverse and a minority fraction, such as at the edge of the crystallite (gallery and aluminosilicate layer), may dominate the lower-frequency dielectric response.     

Structural-chemical evolution within exfoliated clays

The exfoliated (delaminated) structures of lamellar clays offer potential as precursors for the formation of various nanostructured materials. In this article, Lucentite and Laponite phyllosilicate clays, which both have empirical formulas of Na(0.33)[Mg(2.67)Li(0.33)Si4O10(OH)2] but differ in nanodimensions, have been exfoliated. Experiments were carried out for mixtures containing approximately 1 wt % phyllosilicate in a 5% aqueous solution of poly(acrylic acid) at different temperatures. X-ray diffraction and photoemission spectroscopy measurements for the solid products recovered after stirring the mixtures at 20 degrees C showed that the fully extended chains of poly(acrylic acid) were intercalated within the interlayer spaces between the silicate plates of the clays. At 85 degrees C, however, the clays were exfoliated and/or partially exfoliated. Photoemission spectroscopy also indicated that the exfoliated structures primarily consisted of silica nanoplates. 29Si nuclear magnetic resonance and oxygen K-edge near-edge X-ray absorption fine structure indicated that the surfaces of the plates were terminated by high concentrations of the silanol (-SiOH) groups, which created structural branches during intercalation. A model was developed in which intercalation and the removal of ions from the clays after the poly(acrylic acid) interactions reduced the electrostatic van der Waals forces between the plates. It was also shown that the formation of branches created a steric effect that inhibited the stacking of the plates. Together these resulted in exfoliation.     

Removal of boron from aqueous solution by clays and modified clays

In order to increase the adsorption capacities of bentonite, sepiolite, and illite for the removal of boron form aqueous solution, the clay samples were modified by nonylammonium chloride. Specific surface areas of the samples were determined as a result of N2 adsorption-desorption at 77 K using the BET method. X-ray powder diffraction analysis of the clays and modified clays was used to determine the effects of modifying agents on the layer structure of the clays. The surface characterization of clays and modified clay samples was conducted using the FTIR technique before and after the boron adsorption. For the optimization of the adsorption of boron on clays and modified clays, the effect of pH and ionic strength was examined. The results indicate that adsorption of boron can be achieved by regulating pH values in the range of 8-10 and high ionic strength. In order to find the adsorption characteristics, Langmuir, Freundlich, and Dubinin-Radushkevich adsorption isotherms were applied to the adsorption data. The data were well described by Freundlich and Dubinin-Radushkevich adsorption isotherms while the fit of Langmuir equation to adsorption data was poor. It was reached that modification of bentonite and illite with nonylammonium chloride increased the adsorption capacity for boron sorption from aqueous solution.     

Thermal analysis of organically modified siloxane melting gels

Hybrid melting gels were prepared by a sol–gel process, starting with a mono-substituted siloxane and a di-substituted siloxane, methyltrimethoxysilane (MTES) together with dimethyldimethoxysilane (DMDES). Five gel compositions were prepared with concentrations between 50% MTES–50% DMDES and 75% MTES–25% DMDES (in mol.%). The consolidation temperature, the treatment temperature after which the melting gel no longer softens, increased from 135 to 160 °C with a decrease in the amount of the mono-substituted siloxane. The glass transition temperature, recorded with differential scanning calorimetry, decreased from −0.3 to −56.7 °C with a decrease in the amount of the mono-substituted siloxane. When a sample was heat treated isothermally for 2 h at the consolidation temperature, the glass transition temperature increased by about 15°, indicating further crosslinking of the siloxane network.     

Electrospinning of polyurethane/organically modified montmorillonite nanocomposites

Polyurethane/organically modified montmorillonite (PU/O‐MMT) nanocomposites were electrospun and the effect of O‐MMT on the morphology and physical properties of the PU/O‐MMT nanofiber mats were investigated for the first time. The average diameters of the PU/O‐MMT nanofibers were ranged from 150 to 410 nm. The conductivities of the PU/O‐MMT solutions were linearly increased with increasing the content of O‐MMT, which caused a decrease in the average diameters of the PU/O‐MMT nanofibers. The as‐electrospun PU and PU/O‐MMT nanofibers were not microphase separated. The exfoliated MMT layers were well distributed within the PU/O‐MMT nanofibers and oriented along the fiber axis. When the PU/O‐MMT nanofibers were annealed, the exfoliated MMT layers hindered the microphase separation of the PU. The electrospinning of PU/O‐MMT nanocomposites resulted in PU nanofiber mats with improved Young's modulus and tensile strength. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3171–3177, 2005     

Silicotungstic acid/organically modified silane proton-conducting membranes

Proton-conducting gels and membranes were made from an organically modified silane incorporating a heteropoly acid, i.e. silicotungstic acid. The ORMOSIL host was generated from a bis end-capped triethoxysilane chemically bonded via the urea bridges to (1) a long poly(propylene glycol) chain or (2) a long poly(dimethylsiloxane) chain. The heteropolyacid acted simultaneously as a source of mobile protons and as a catalyst, initiating the hydrolysis/condensation reactions of the sol–gel composite. In addition to the bis end-capped triethoxysilane network former, different alkoxysilanes were tested as network modifiers to optimize the gelation time, mechanical properties, ionic conductivity and the retention of the heteropolyacid during soaking of the membranes in water. Among alkoxysilane modifiers the most promising results were given by perfluorooctyltriethoxysilane and phenyltriethoxysilane. The conductivity of the membranes was up to 10^–2–10^–1 S cm^–1 at elevated temperatures and saturated humidity conditions. Fourier transform IR attenuated total reflection spectroscopy was used to follow the gelation of the samples and, in parallel to thermogravimetric/differential scanning calorimetry measurements, also the thermal stability of the membranes.     

New nanocomposites constituted of polyethylene and organically modified ZnAl-hydrotalcites

The thermal properties and combustion behaviour of new PE–hydrotalcites nanocomposites are described. Hydrotalcites were synthesized and then intercalated with stearate anion, because of the compatibility of long alkyl chain with polyethylene chains. The presence of inorganic filler shields PE from thermal oxidation, shifting the temperature range of volatilisation towards that of thermal degradation in nitrogen, and brings to a reduction of 55% in heat release rate during combustion.     

有机改性膨润土对水中钙黄绿素的吸附性能

在微波作用下用十六烷基溴化吡啶(CPB)、十六烷基三甲基溴化铵(CTMAB)和盐酸萘乙二胺(NETH)对天然膨润土进行改性,制得了CPB-膨润土(CPB-Bt)、CTMAB-膨润土(CTMAB-Bt)和NETH-膨润土(NETH-Bt),并比较了它们对水中钙黄绿素的吸附性能.结果表明,在钙黄绿素浓度25 mg·L-1、...     

Adsorption of benzoic acid and hydroquinone by organically modified bentonites

Two organobentonites (ODTMA-B, HDTMA-B) were synthesized using hexadecyltrimethyle ammonium bromide (HDTMAB) and octadecyltrimethyle ammonium bromide (ODTMAB). Synthesized organobentonites were characterized by X-ray diffraction particle size, and surface area analysis. Particle size analyses of the original bentonite and organobentonites showed that the organobentonites contained a greater number of coarse particles than present in the original bentonite. While the basal spacings of the organobentonites increased organic cation, the surface area decreased.

To evaluate the potential use of two modified bentonites in removing organic pollutants such as benzoic acid and hydroquinone from water, adsorption experiments were performed under conditions of varied pH (3, 6 and 11) and temperatures(298 and 313 K). Experimental results showed that the sorption capacities increase with decreasing pH value and increasing temperature. The adsorption equilibrium of benzoic acid and hydroquinone on organobentonites was described by the Langmuir and Dubinin–Radushkevich (D–R) models. It was concluded that the isotherm shapes were not affected by pH and temperature. Adsorption capacity of ODTMA-B for benzoic acid was higher compared to that of HDTMA-B at various pH and temperatures.     

Photo-curable organically modified silicate-phosphate alternating copolymer for photonics applications

Photo-curable vinyl modified silicate-phosphate alternating copolymers were prepared by a direct condensation of organochlorosilane and organophosphoric acid in a solvent-free condition. The obtained copolymers have complete alternating copolymer structure of silicate and phosphate unit, where the main oxo chain consist of –(Si–O–P–O) _n -network. They exhibited an excellent solubility of ionic species such as ionic organic dyes. It was also demonstrated the photo-reduction of Au⁺ ions to form Au nano particles for plasmonics applications. Micro patterns were also fabricated by soft lithographic processes. These results indicate that the photo-curable alternating copolymers are one of promising materials for advanced optical information processing devices.     

Synthesis and characterization of polydimethylsiloxane-cured organically modified silicate hybrid coatings

Hybrid coatings based on polydimethylsiloxane-cured organically modified silicate were synthesized through a sol-gel technique. Amino-terminated siloxane, 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane were used as precursors for the hybrid coatings. These hybrid films were deposited via spin coating onto an aluminum alloy to improve the corrosion protection. The effects induced by the different chain lengths of siloxane on the chain dynamics, thermal stability and corrosion performance of the coated samples were investigated. The rotating-frame spin-lattice relaxation times and scale of the spin-diffusion path length indicated that the configuration of the hybrid films was highly crosslinked, dense and adhered to the aluminum alloy substrates. The thermal stability and the apparent activation energy, evaluated by van Krevelen's method, of the hybrid coatings depended on the siloxane chain length. Potentiodynamic analysis revealed that the hybrid films provided exceptional barrier and corrosion protection in comparison with untreated aluminum alloy substrates.     

Investigation of the properties of organically modified ordered mesoporous silica films

Organically modified, ordered mesoporous silica films, which can provide hydrophobicity and low polarizability to the framework, were prepared using Brij-76 block copolymer as a template. Due to a fast condensation reaction of the silica precursor, mesostructured silica films were not properly synthesized. To circumvent this problem, a synthesis procedure was modified to provide an enhancement of pore periodicity through the incorporation of methyl ligands on the framework. The micropore volume was reduced, and the pore size was enlarged, as the concentration of the methyl ligands on the framework was increased. A mesophase transition from a two-dimensional hexagonal structure to a body-centered cubic (BCC) structure was observed according to the concentration of incorporated methyl ligands. The mechanical properties of the fabricated films were investigated according to the pore ordering and film density. The mechanical properties of the films with random pore geometry show a positive correlation between film density and elastic modulus. Meanwhile, the mechanical behavior of organically modified mesoporous silica films with periodic pore distribution represents a negative correlation within a certain density range, which is advantageous to the low-k materials. Especially, film with a low micropore volume fraction and BCC pore ordering is more applicable to a low-k material due to low dielectric constant and high mechanical strength.     

Synthesis of organically modified layered magnesium silicate by the sol-gel method

Organically modified layered magnesium silicate was for the first time synthesized by thermal treatment of a sol of silicon dioxide, magnesium hydroxide, and hexadecyl trimethylammonium bromide, with reflux of the liquid phase. The material obtained can be used as an ultradispersed component in polymer-inorganic composites.     

DC electrorheological response of polyethylene/organically modified layered silicate nanocomposites

The present work reports the electrorheological (ER) response of high‐density polyethylene (HDPE)/organically modified silicate layers nanocomposites based on four commercially available HDPE matrices. Two single‐site catalyzed bimodal resins, one single‐site catalyzed unimodal resin and one Ziegler–Natta catalyzed unimodal resin are studied. It is revealed that the distinct separation of the two modes of the bimodal HDPE resins significantly enhances the ER response. It is proposed that the slower structural relaxation modes introduced by higher molecular weight species in the bimodal HDPE matrices enhance the ER response of the nanocomposites. This is ascribed to the longer induction time for leaking current density, which is an indicator of mobility and release of immobilized cationic surfactants at the silicate layers surface induced by field exposure. It is found that the screening effect of prematurely released cationic surfactants leads to a weaker ER response in nanocomposites whose matrices have faster relaxation modes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1298–1309