ODTMA+ and HDTMA+ organo-montmorillonites characterization: New insight by WAXS,SAXS and surface charge

In this work we investigate the microstructure and properties of organo-montmorillonites (OMts) synthesized by intercalation of a Patagonian Mt with different surfactant/CEC ratios (0.5, 1 and 2) of octadecyl trimethylammonium (ODTMA⁺) and hexadecyl trimethylammonium (HDTMA⁺) cations. X-ray diffraction (XRD) patterns showed that in all OMt samples d₀₀₁ value increases with respect to raw Mt (1.258 nm). Small angle and wide angle X-ray scattering (SAXS and WAXS) curves, particle apparent diameters (determined by laser), zeta potential values and scanning electron microscopy (SEM) images, showed the presence of assorted d₀₀₁ values (which depend on storage conditions), aggregate formation and charge reversal (which varied with loading and cation length) for samples obtained with 1 and 2 CEC. However, for samples intercalated with 0.5 CEC, we found evidence of smaller aggregate formation, no charge reversal, and similar d₀₀₁ and zeta potential values (both higher than those of Mt). Findings reported here will help attain better conditions to functionalize highly charged Mt making them suitable to be used as nanocomposite precursors for different applications.     

Inverse gas chromatographic characterization of polystyrene and organo-montmorillonite/polystyrene nanocomposites

Polymer nanocomposites of a polystyrene (PS) matrix containing 2% and 5% organo-montmorillonite (OMt) by mass were prepared using the solution blending method with sonication. Hexadecyl trimethyl ammonium bromide was used to modify the montmorillonite after its surface was saturated with Na⁺ ions. X-ray diffraction and transmission electron microscopy revealed the mixed nanomorphology of nanocomposites. The majority of OMt is dispersed in the polymer matrix in the form of an ordered tactoid (multilayer particles) structure consisting of few silicate layers and a small amount of exfoliation was achieved. The synthesized nanocomposites showed a higher decomposition temperature in comparison with pure PS according to the thermogravimetric analysis. Inverse gas chromatography under infinite dilution conditions was applied to evaluate the surface properties of the PS and OMt/PS nanocomposites. The IGC results were in agreement with conceptual and theoretical expectations. The dispersive component of the free energy of adsorption and specific interactions (acid–base properties) were determined using polar and non-polar adsorbates (probes) of known properties in the temperature range 40–70 °C. The IGC data showed that the introduction of a very small amount of OMt into the polymer matrix significantly changed the surface characteristics of the final material.     

The influence of surfactant loading level in a montmorillonite on the thermal,mechanical and rheological properties of EVA nanocomposites

In this work, montmorillonite (Mt) has been organically modified with ethyl hexadecyl dimethyl ammonium (EHDDMA) in 20, 50, 80 and 100% of the nominal exchange capacity (CEC) of the Mt. A full characterization of the organo-montmorillonite (OMt) obtained has been made, including thermal analysis, X-Ray Diffraction, elemental analysis CHN and nitrogen adsorption. According to the results, 12% in mass of the surfactant added is strongly retained by the Mt. When the mass percentage of EHDDMA exchanged in the OMt is increased up to this level, the interactions OMt–EHDDMA are steeply reduced depending on the EHDDMA content.Clay polymer nanocomposites (CPN) were prepared by melt mixing of EVA and different loads of OMt. The CPN were compress molded to obtain 1 mm thick sheets, which have been characterized according to their mechanical, thermal and rheological behaviors. The major changes in the structure of the OMt are obtained for low contents of EHDDMA. Nevertheless, the CPN containing OMt exchanged at 20 and 50% of the CEC show relatively low effect of the EHDDMA while the mechanical response and rheological behavior of CPN with OMt modified at 80 and 100% of the CEC are much more pronounced.     

Some Surface Properties of Polysorbates and Cetyl Trimethyl Ammonium Bromine Mixed Systems

Mixed surfactant solutions consisting of cationic/nonionic surfactants were prepared in different compositions of the components in aqueous solution in order to determine the surface properties. The critical micelle concentration (CMC) of aqueous solutions of the individual surfactants cetyl trimethyl ammonium bromide (CTAB) and polysorbate nonionics, and their mixtures are determined at different proportions. The results show that there is synergistic behavior in mixtures at higher mole fraction of nonionic surfactant. The effect of the alkyl chain on the CMC is also determined.     

Constructing Gemini‐Like Surfactants with Single‐Chain Surfactant and Dicarboxylic Acid Sodium Salts

Construction of gemini‐like surfactants using the cationic single‐chain surfactant cetyltrimethylammonium bromide C₁₆H₃₃N(CH₃)₃Br₂ (CTAB) and the anionic dicarboxylic acid sodium salt NaOOC(CH₂)_n‐2COONa (C_nNa₂, n = 4, 6, 8, 10, 12) by way of non‐covalent interactions has been investigated by surface tension measurements, hydrogen‐1 nuclear magnetic resonance (¹H NMR) spectroscopy and isothermal titration microcalorimetry (ITC). The critical micelle concentrations (cmc) of the CTAB/C_nNa₂ mixtures are obviously lower than that of CTAB and strongly depend on the mixing ratio. Moreover, the cmc values of the CTAB/C_nNa₂ mixtures decrease gradually with an increasing methylene chain length of C_nNa₂, indicating hydrophobic interaction between the hydrocarbon chains of CTAB and C_nNa₂ facilitates micellization of the mixtures. In particular, the ITC curves and ¹H NMR spectra indicate that the binding ratio of CTAB to C_nNa₂, except C₄Na₂, is around 2:1, i.e., (CTAB)₂C_nNa₂. Additionally, CTAB/C_nNa₂ mixtures are soluble in a whole molar ratio and concentration ranges have been studied, even at the electrical neutralization point. Therefore, these results reveal that highly soluble gemini‐like surfactants are conveniently constructed with oppositely‐charged cationic single‐chain surfactants and dicarboxylic acid sodiums. In an attempt at improving the performance of surfactants this work provides guidance for choosing additives that form gemini‐like surfactants via an uncomplicated synthesis.     

Abrasivity by bentonite dispersions

Bentonites are used for various industrial applications. Their physicochemical properties depend on the mineralogical and chemical composition, the type of smectite, the grain size distribution, the cation exchange capacity (CEC), the dominant interlayer cation (Na⁺, Ca²⁺, Mg²⁺), and the layer charge density. All these parameters can be measured with acceptable precision. Nevertheless, the performance of a bentonite in a given application is often unpredictable. An additional relevant parameter is the “microfabric” describing the arrangement of minerals and/or the intergrowth of the minerals with glass. The microfabric is supposed to affect different bentonite properties such as swelling capacity and rheology. The present study focuses on the influence of different microfabrics on the abrasivity by bentonite dispersions.The abrasivity of bentonite dispersions mainly depended on two factors: 1) on the amount of hard and sharp accessory minerals and volcanic glass and 2) the grain size distribution, which was produced by different grinding techniques. The abrasivity increased with decreasing grain size, which was caused by breaking the hard components (minerals and glass) leading to an increased number of sharp edges.In addition, there was evidence for a subordinate influence of the type of exchangeable cations. This influence is explained by the different relative arrangements of smectite particles towards the surfaces of hard and sharp minerals. Na⁺ exchanged glass rich samples showed higher abrasion values than the Ca²⁺ exchanged samples.     

Oil swollen surfactant gel based synthesis of metal oxides nanoparticles: An attractive alternative for the conventional sol gel synthesis

Metals (Zr, Zn and Cu) containing oil swollen surfactant gels have been utilized as precursors for the preparation of metal oxides (ZrO₂, ZnO and CuO) nanoparticles. No metal alkoxide, external gelating agent or any other intricate molecule have been utilized to reinforce gelation; gel stage has been achieved simply through judicial adjustment of water to surfactant ratio and salinity of the reaction mixture. Unlike, several previously published reports, in this approach surfactant has been added not to just increase the viscosity of solution but it has also formed rod shaped gelatinous micelles in response to the variation in water to surfactant ratio, which endowed mechanical strength to the gel. The effect of nature of metal salt on mechanical properties of gel has also been investigated. Zn and Cu containing cetyltrimethylammonium bromide (CTAB) gels have been found to be strongest and weakest, respectively. Metal containing CTAB gels were heat treated at various temperatures (600, 700 and 800 °C) in order to obtain metal oxides nanoparticles. The effect of calcination temperature on crystallinity, particle size and morphology of the metal oxides nanoparticles has also been investigated. A comparison between ZrO₂ nanoparticles prepared using conventional sol gel and oil swollen surfactant gel method has also been carried out in terms of crystallinity, particle size and optical property.     

Characterization of surface-modified montmorillonite nanocomposites

Montmorillonite K-10 clay was surface-modified using the cationic surfactants viz., butyltriphenylphosphonium bromide (BTPB), cetyltrimethylammonium bromide (CTAB), and tributylhexadecylphosphonium (TBHPB) bromide. Of these, CTAB and TBHPB modified clays were chosen for surface grafting with 3-aminopropyltrimethoxy silane (APTMS) coupling agent. The nanocomposites were fully characterized by powder X-ray diffraction (XRD), solid state ²⁹Si NMR, Fourier transform infrared spectroscopy (FTIR) and thermogravimetry (TGA). The XRD and FTIR confirmed the increase in basal plane spacing and intercalation of long chain surfactant molecules into the clay gallery, while TGA indicated the onset degradation and 10% weight loss temperature (T_10%) in case of quaternary phosphonium modified clay that was higher than the corresponding ammonium counterpart; these values increased further after the grafting with APTMS. The ²⁹Si NMR peak deconvolution study suggested that the molar % of T units and total degree of silica condensation for different APTMS grafted clay samples were more than 20% and 80%, respectively.     

二聚阳离子表面活性剂改性蒙脱土的制备和表征

合成了二聚阳离子表面活性剂GeminiC12,用核磁共振氢谱(1HNMR)表征了它的结构,并用它作为有机插层剂应用于蒙脱土的改性处理。红外光谱(FTIR)、热重分析(TGA)表明,GeminiC12已插层到蒙脱土片层间。X射线粉末衍射(XRD)表明,插层后蒙脱土层间距从1 19nm增加到3 8nm,是十六烷基三甲基溴化铵(CTAB)处理效果的两倍。沉降实验表明,改性后蒙脱土在苯乙烯和石蜡中形成凝胶体系,表现出很好的相容性和分散性,这种改性效果优于目前常用的CTAB处理效果,更有利于聚合物或其单体进入蒙脱土层间形成纳米复合材料。     

A Comparative Study on the Aggregation and Thermodynamic Properties of Anionic Sodium Dodecylsulphate and Cationic Cetyltrimethylammonium Bromide in Aqueous Medium: Effect of the Co-solvent N-Methylacetamide

The effect of co‐solvent N‐methylacetamide (NMA) (0.035, 0.046, 0.127, and 0.258 mol kg^?1) on the micellization behaviour of anionic surfactant sodium dodecylsulphate (SDS) (3.21–10.35 mmol kg^?1) and cationic surfactant cetyltrimethylammonium bromide (CTAB) (0.19–3.72 mmol kg^?1) in aqueous solution was explored by employing conductivity measurements at different temperatures (298.15–313.15 K). The critical micelle concentration (CMC) values for SDS and CTAB in aqueous solutions of NMA were determined from the conductivity versus surfactant concentration plots. The variations in the CMC values of SDS with NMA concentration are in striking contrast to those observed in the case of CTAB. The various relevant thermodynamic parameters of micellization, viz. standard enthalpy change, ΔH_m^o, standard entropy change, ΔS_m^o, and standard Gibbs free energy change, ΔG_m^o, were determined using the temperature variation of the CMC values and counterion binding. The results not only relate these thermodynamic parameters to the consequences of intermolecular interactions but are also able to differentiate between SDS–water–NMA and CTAB–water–NMA systems in terms of contributions from head groups as well as alkyl chains of surfactants.     

Modification of montmorillonite with cationic surfactants. Thermal and chemical analysis including CEC determination

The thermal stability of synthesized and commercial organically modified montmorillonites has been investigated using thermogravimetric analysis (TGA). Four organo-montmorillonites have been prepared by replacing the inorganic cations of a commercial montmorillonite with aliphatic and aromatic ammonium bromide or chloride salts. The modification has been carried out by cation exchange to obtain a high level of intercalation in the montmorillonite. Conformations of the intercalated surfactants have been characterized using Fourier transform infrared spectroscopy (FTIR). Besides fixed organic surfactant, some surfactant in excess still remained in the montmorillonite after repeated washing with water or ethanol/water. The use of a suitable eluent for the surfactants in the washing step was the key issue as shown by the changes of the first degradation peak of Cloisite-Na⁺-hexadecyl benzyl dimethylammonium (CLO-BDHA), Cloisite-Na⁺-benzyl triethylammonium (CLO-BTA) and Cloisite-Na⁺-hexadecyl trimethylammonium (CLO-HTA). Hexadecyl trimethylammonium (HTA) was more sensitive to water and ethanol/water as eluents. Sonication and the use of a polar activator during the modification of montmorillonite increased the amount of surfactant adsorbed by cation exchange. Ammonium acetate method has been revealed as an adequate chemical method to measure the cation exchange capacity (CEC) of inorganic and organic montmorillonites. This method has the advantage with respect to TGA that it does not measure the unfixed surfactant.     

Polymerization of vinyl acetate in microemulsions stabilized with dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide

The polymerization of vinyl acetate in microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) or mixture of these surfactants is examined. The polymerization rate diminishes as the surfactant mixture becomes richer in DTAB. Also, particles grow with conversion and become increasingly larger as the DTAB content in the mixture increases. Our results indicate that chain transfer reactions to monomer are more important than chain transfer reactions to polymer even at high conversions with CTAB. However, as the content of DTAB increases, bimolecular termination induced by coagulation, terminal double bond polymerization and chain transfer reactions to polymer become increasingly more important.     

Influence of sodium dodecyl sulfate and cetyl trimethylammonium bromide upon calcium carbonate precipitation on bacterial cellulose

Calcium carbonate was deposed on bacterial cellulose (BC) never-dried membranes in the presence of different concentrations of sodium dodecyl sulfate (SDS) and cetyl trimethylammonium bromide (CTAB) by a precipitation reaction between aqueous solutions of calcium chloride (CaCl₂) and sodium carbonate (Na₂CO₃) containing, or not, surfactant in their composition. Different shapes of crystals were obtained from rhombohedral ones to flowerlike, depending on surfactant type and concentration. From the two surfactants tested, SDS has a greater influence on calcium carbonate morphology than CTAB. The only polymorph obtained in all studied cases was calcite. The composite films BC-calcite were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and color measurements. The obtained BC-calcium carbonate composites could be used in paper manufacturing.     

Effect of different surfactants on methane hydrate formation rate, stability and storage capacity

The effects of anionic surfactants sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), cationic surfactant cetyl trimethyl ammonium bromide (CTAB) and non-ionic surfactant ethoxylated nonylphenol (ENP) on the formation, dissociation and storage capacity of methane hydrate have been investigated. Each surfactant was tested with 3 concentrations 300, 500 and 1000 ppm and it has been found that SDS, when prepared with these three concentrations speeds up the hydrate formation rate effectively. LABS increases the hydrate formation rate at 500 and 1000 ppm but decreases it at 300 ppm. CTAB and ENP have promotion effect on hydrate formation rate at 1000 ppm but decrease it at 300 and 500 ppm. Hydrate stability tests have been performed at three temperatures 268.2, 270.2 and 272.2 K with and without surfactant promoters. The results show that all tested additives increase the dissociation rate of methane hydrate below the ice point. CTAB has the minimum and LABS the maximum effect on the methane hydrate dissociation rate. Experimental results on hydrate gas content revealed that maximum storage capacity of 165 V/V is obtained with 1000 ppm of CTAB in water.     

微乳法合成磷酸钙纳米纤维及其机理探讨

分别以非离子表面活性剂（C₁₂E₈）和阳离子表面活性剂（CTAB）为模板剂,在反微乳体系中制备了磷酸钙纳米纤维.在水/C₁₂E₈/环己烷体系中纤维长约为325 nm,宽约为13 nm,为无定形态;在水/CTAB/环己烷体系中纳米纤维的长度>500 nm,宽度约为14 nm,结晶较完全.两种表面活性剂的作用机理完全不同：在非离子表面活性剂体系中,表面活性剂主要起到“微反应器”的作用;而在阳离子表面活性剂中,表面活性剂主要起到“生长引导剂”作用.     

Die Wechselwirkung von Tensiden mit Textilien unter besonderer Berücksichtigung von Baumwolle und Nylon

Interaction between Surfactants and Textiles under Special Consideration of Cotton and Nylon The adsorptions of Ca²⁺ ions as well as anion active Na-dodecylsulfate (NaDS) and cation active surfactant cetyltrimethyl monium bromide (CTAB) on Avicel (cellulose) and Nylon various pH-values were investigated in model experiments. In the presence of Ca²⁺ ions NaDS is strongly adsorbed on cellulose and Ca-dodecyl sulfate, which might possibly be precipitated is partly taken up by the substrate. In the case of CTAB, the Ca^2--ions instead of the surfactant were selectively adsorbed on cellulose, however, at higher pH-values more surfactant is adsorbed Both NaDS and CTAB were adsorbed on Nylon, whereby with increasing pH-values the adsorption in the system Nylon NaDS decreases and that in Nylon/CTAB increases. The Ca²⁺ ions have only a small influence on CTAB. Experiments with cotton and Nylon-6 fabrics have shown that the results of model experiments also hold good for the said fabrics.     

Synthesis and characterization of nanosized polypyrrole–polystyrene composite particles

Nanosized polypyrrole–polystyrene (PPy–PS) composite particles were synthesized by the polymerization of pyrrole on PS nanoparticles in the presence of FeCl₃. The PS nanoparticles were prepared from microemulsion polymerizations using the cationic nonpolymerizable surfactant cetyltrimethylammonium bromide (CTAB), the nonionic polymerizable surfactant ω‐methoxy[poly(ethylene oxide)₄₀]undecyl α‐methacrylate (PEO–R–MA‐40), or the cationic polymerizable surfactant ω‐acryloyloxyundecyltrimethylammonium bromide (AUTMAB). For the latexes stabilized by CTAB, the resulting PPy–PS composite particles exhibited relatively poor colloidal stability and the pressed pellets exhibited relatively low electrical conductivities (～10^?7–10^?3 S cm^?1). However, for the latexes stabilized by polymerizable surfactants, the resulting PPy–PS composite particles exhibited relatively good colloidal stability and relatively high conductivities (～10^?5–10^?1 S cm^?1). The effect of polymerizable surfactants on the colloidal stability of composite particles and the conducting mechanism of the composites are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1360–1367, 2004     

Nucleophilic substitution sulfonation in emulsions: Formation of sodium benzyl sulfonate

Benzyl bromide was sulfonated at 298 K in emulsions formed with dioctyldimethylammonium bromide, or chloride. If mixing was sufficient, the emulsion was maintained throughout the reaction period. Lower conversions were obtained whenever benzyl bromide phase separated from the mixture. Chloride as surfactant counterion gave higher reaction rate, but decreased the conversion to C₇H₇SO₃^?Na⁺due to formation of benzyl chloride. The conversion to C₇H₇SO₃^?Na⁺ displayed a broad maximum as R₂(Me)₂^?N⁺Br concentration increased. Except at low concentration, the reaction rate increased with the concentration of Na₂SO₃ in accord with the S_N2 mechanism. The reaction rate increased with the reactant concentrations until interface saturation was achieved, suggesting that product formation did not interfere with the access of the reactants to the interface.     

Radiation-induced admicellar polymerization of isoprene on silica: Effects of surfactant's chain length

This research compared radiation-induced admicellar polymerization with the traditional thermal process and studied the influence of the hydrocarbon chain length of different surfactants on film formation. Three types of surfactants were used in this study: dodecyl trimethyl ammonium bromide (DTAB), tetradecyl trimethyl ammonium bromide (TTAB) and cetyl trimethyl ammonium bromide (CTAB). Isoprene was used as a monomer for the formation of thin film inside the surfactant bilayers, called admicelle, adsorbed on silica surface. The results showed that an optimum dose can lead to a better film formation on silica, compared with the thermal method. However, when the dose was over the optimum value, the formation of polyisoprene film was diminished. The formation of polyisoprene film was found to depend not only on the hydrocarbon chain length of the surfactant, but also on the density of adsorbed surfactant on silica surface.     

Surfactant concentration effects on the microemulsion polymerization of vinyl acetate

The polymerization of vinyl acetate in oil-in-water microemulsions stabilized with cetyltrimethylammonium bromide (CTAB) is reported here as a function of surfactant concentration. Reaction rate decreases as the CTAB/water ratio is increased in the parent microemulsions. Polymer particles in the latexes grow with conversion; they also become bigger as the initial surfactant content is increased. Number-average molar masses are smaller than those expected by termination by chain transfer to monomer, but weight-average molar masses increased as the surfactant concentration in the parent microemulsion is raised. However, the latter are much smaller than those obtained by polymerization in an emulsion stabilized with the same surfactant. Possible explanations to this unusual behavior are provided here.