Rheological behaviour and shear thickening exhibited by aqueous CTAB micellar solutions

In this experimental work we carefully investigate the rheological behaviour and in particular the shear thickening exhibited by aqueous micellar solutions of CTAB with NaSal as added counterion. We are particularly interested in the evolution of the critical shear rate (at which shear thickening occurs) versus C _D , the surfactant concentration. We show that , at fixed salt concentration C _S , increases with C _D following a power law evolution with a positive exponent of + 5.8. On the other hand we show that if the ratio C _D / C _S is fixed, decreases with C _D with a negative exponent of -2.0. Nevertheless investigations of the zero shear viscosity indicate that in all situations (implying variation of the surfactant concentration C _D , or the salt concentration C _S or the temperature) is a decreasing function of the length of the micelles. All these evolutions are compatible with a gelation mechanism which could possibly be associated with entanglement effects of large interacting flowing structures. Received: 3 March 1998 / Revised: 16 June 1998 / Accepted: 3 July 1998     

Flow birefringence,stress optical rule and rheology of four micellar solutions with the same low shear viscosity

The flow birefringence and the rheological properties of four viscoelastic solutions having nearly the same zero shear viscosity and subjected to shear flows are investigated in the linear and non-linear domains. The surfactant used for the samples is the cetyltrimethylammonium chloride in water at the concentration of 100 mmol/l with an organic salt, the sodium salicylate. The low shear viscosity curve versus the salt concentration is non-monotonic and has two maxima separated by a minimum forming four domains in which the salt concentration is chosen. For the two solutions belonging to the inner branch, i.e. between the two maxima, a simple Maxwellian behaviour is observed and shear banding occurs as confirmed by the flow birefringence pictures. Contrary to the results of P. Fisher (1996) where the unstable flow regime is restricted to the first decreasing part of the low shear viscosity curve of a cetylpyridinium chloride solution, we show that shear banding exits in a wider domain of the salt concentration. Received 18 November 2002 / Published online: 1 April 2003 RID="a" ID="a"e-mail: Decruppe@lpli.sciences.univ-metz.fr     

Structure and rheology of concentrated wormlike micelles [4]at the shear-induced isotropic-to-nematic transition

We have investigated the simple shear flow behavior of wormlike micelles using small-angle neutron scattering and mechanical measurements. Ternary surfactant solutions made of cetylpyridinium chloride, hexanol and brine (0.2 M NaCl) and hereafter abbreviated as CPCl-Hex were studied in the concentrated regime, . In a preliminary report (Berret et al. [#!ref16!#]), the discontinuity of slope observed in the shear stress versus shear rate curve was interpreted in terms of first-order phase transition between an isotropic state and a shear-induced nematic state ( transition). At the transition rate, , the solution exhibits a macroscopic phase separation into viscous and fluid layers (inhomogeneous shear flow). Above a second characteristic shear rate, the flow becomes homogeneous again, the sheared solution being nematic only. The neutron patterns obtained in the two-state inhomogeneous region have been re-examined. Based on a consistent analysis of both orientational and translational degrees of freedom related to the wormlike micelles, we emphasize new features for the transition. In the present paper, the shear rate variations of the relative proportions of each phase in the two-state region, as well as the viscosity ratio between isotropic and nematic phases are derived. We demonstrate in addition that slightly above the transition rate, the shear induced nematic phase is already strongly oriented, with an order parameter P ₂ = 0.65. The orientational state is that of a nematic flow-oriented monodomain. Finally, from the locations of the neutron scattering maxima for each isotropic and nematic contributions, we evaluate the concentrations for each phase and and derived a dynamical phase diagram of CPCl-Hex, in terms of the stress versus and . According to the classification by Schmitt et al. [#!ref22!#], the transition observed in CPCl-Hex micellar solutions could result from a positive flow-concentration coupling, in agreement with the observed monotonically increasing shear stress in the two-phase region. Received: 16 February 1998 / Revised: 18 February 1998 / Accepted: 24 May 1998     

Synergistic effects in mixed wormlike micelles of dimeric and single-chain cationic surfactants at high ionic strength

The mixed micellization between the cationic gemini surfactant [ C₁₂H₂₅( CH₃)₂N⁺( C₂H₄) N⁺( CH₃)₂ C₁₂H₂₅•2Br^-] and the cationic cetyltrimethylammonium bromide (CTAB) in 150 mM KBr solutions has been investigated. The variation of the cmc of the mixtures, measured by surface tension experiments, with composition revealed synergism in micelle formation. T-Jump and light scattering experiments performed in the vicinity of the crossover volume fraction showed the existence of two micellar populations, possibly linear and toroidal micelles. Rheological and dynamic light scattering experiments allowed to fully characterize the linear viscoelasticity of the mixtures. These measurements revealed synergistic gains in viscoelastic properties with a maximum of the stress-relaxation time around the equimolar composition. These effects are ascribed to a progressive intermicellar crosslinking resulting from a continuous increase of the end-cap energy with the 12-2-12 content in the mixture. Received: 18 November 2002 / Accepted: 8 April 2003 / Published online: 27 May 2003 RID="a" ID="a"e-mail: candau@fresnel.u-strasbg.fr     

Electron detachment and fragmentation in collisions between 1.25 keV/carbon and clusters and

The destruction cross-section for 22.5 and 50 keV C^1- , for 10 and 50 keV C₈ ^1- and for 50 and 75 keV C₆₀ ^1- clusters in collisions with H₂ has been measured by an attenuation method. The destruction of the cluster anions is dominated by electron detachment rather than fragmentation and is of the order of the geometric cross-section. The cross-sections vary little with bombarding energy. Received: 16 September 1998 / Received in final form: 23 February 1999     

Role of cationic gemini surfactants toward enhanced ninhydrin–tryptophan reaction

In this paper we report the effect of dicationic ‘gemini’ surfactants (CH₃)₂C₁₆H₃₃N⁺? (CH₂)_m? N⁺C₁₆H₃₃(CH₃)₂, 2Br^? (where m = 4, 5, 6) on the reaction of ninhydrin with DL ‐tryptophan. The gemini surfactant micellar media are comparatively more effective than their conventional monomeric counterpart cetyltrimethylammonium bromide (CTAB) micelles. Also, whereas typical rate constant (k_ψ) increase and leveling‐off regions, just like CTAB, are observed with geminis, the latter produce a third region of increasing k_ψ at higher concentrations. These subsequent increases are ascribed to changes in micellar morphologies, consistent with changes in ¹H NMR line widths. Quantitative kinetic analysis of the rate constant–[surfactant] data has been performed on the basis of modified pseudophase model. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,physicochemical, and biological activities of novel N‐acyl tyrosine monomeric and Gemini surfactants in single and SDS/CTAB–mixed micellar system

A series of single‐chained N‐acyl tyrosine surfactants with varying chain lengths (C₁₀‐C₁₈) and degree of unsaturation, as well as an N‐acyl Gemini tyrosine surfactant with chain length C₁₂, were synthesized, and the structures were confirmed using spectral analysis. The effect of chain length and level of unsaturation on the physicochemical and antibacterial properties of the N‐acyl tyrosine surfactants was evaluated. The C₁₂ derivative displayed the optimum antibacterial activity among the single chain surfactants, and the presence of double bond in the oleoyl derivative enhanced the antibacterial activity over its saturated analogue. The N‐acyl Gemini surfactant displayed the highest antibacterial activity among the series and also showed greater micelle forming ability than its single chain analogue. Mixed micellar behavior of the N‐acyl Gemini surfactant with conventional cationic (CTAB) and anionic (SDS) surfactants in aqueous solution was studied. The negative value of the interaction parameter β₁₂ observed for the N‐acyl Gemini in binary mixture with CTAB surfactant indicated a synergistic interaction within the mixed micellar system. However, the binary mixture with SDS displayed antagonistic behavior. The binary mixture of N‐acyl Gemini surfactant with CTAB displayed better antibacterial activity and foaming properties than with SDS mixtures. Optimum antibacterial activity was observed for N‐acyl Gemini surfactant with mole ratio 0.4 to 0.6 in the CTAB binary mixture, at which the lowest ocular irritation index was observed. Overall, the study showed that the Gemini surfactant in combination with the conventional surfactant CTAB can be used as potential ingredients in detergent and pharmaceutical formulations.     

A study of molecular reorientation in a series of liquid n-alkanes using light-scattering spectroscopy

The spectra of the depolarized (VH) light scattered from the n-alkanes C₆H₁₄, C₈H₁₈, C₁₀H₂₂, C₁₂H₂₆, C₁₄H₃₀, C₁₅H₃₂ and C₁₆H₃₄ have been measured using a high resolution piezo-electrically scanned Fabry-Perot interferometer. The values of the molecular relaxation times τ _s derived from the spectra are compared with relaxation times τ _f derived from flow birefringence. The experimental results are discussed in terms of a phenomenological activation energy and also in terms of the coupling between the molecular reorientation and the hydrodynamic shear modes, allowing estimates of the strength of the coupling between these modes to be made.     

SANS structural determination of a nonionic surfactant layer adsorbed on clay particles

We study adsorption of two nonionic surfactants (C₁₂E₅ and C₁₂E₈) on a dispersed suspension of negatively charged laponite particles. First, we quantify adsorption, i.e. the amount of adsorbed molecules per gram of dried solid. Then, we show that contrast variation experiments under controlled conditions along the adsorption isotherm of the surfactant on dispersed laponite particles allow to determine the average thickness of a nonionic surfactant layer adsorbed on a solid anisotropic particle. Received 4 August 1998     

Dispersion of the birefringence in (CH12H25NH3)2ZnCl4 and (C12H25NH3)2ZnCl4: Co around their isotropic points

The optical dispersion of (C₁₂H₂₅NH₃)₂ZnCl₄ and (C₁₂H₂₅NH₃)₂ZnCl₄: Co is investigated by means of birefringence and optical absorption measurements in the temperature region around their isotropic points. The birefringence dispersion is analyzed in terms of a simple oscillator model based on the absorption band structure of both materials. A fairly good agreement is found between the thermal behaviour of the adjustable parameters of the oscillator model and the temperature dependence of the absorption spectra. The results suggest the existence of a structural phase transition at 315 K.     

Synthesis and room temperature photoluminescence of ZnO/CTAB ordered layered nanocomposite with flake-like architecture

Flake-like ZnO/surfactant ordered layered nanocomposite has been synthesized by self-assembly at room temperature with the presence of cetyltrimethylammonium bromide (CTAB, CH₃(CH₂)₁₅N⁺(CH₃)₃Br⁻) surfactant. The procedure described in this study is attractive since it gives high yields of ordered layered nanocomposite with flake-like architecture. XRD results showed the formation of a layered structure with two layered spacings ca. 18.56 Å. SEM and FT-IR spectroscopy were used to further characterize ZnO/CTAB nanolayered composite. The ZnO/CTAB-ordered layered nanocomposite exhibits the room temperature photoluminescence (RTPL) characteristics. It is inferred that the RTPL of ZnO/CTAB-layered nanocomposite might be induced by the interfacial effect between the ZnO and the surfactant.     

Microphase separation in weakly charged hydrophobic polyelectrolytes

Aqueous solutions of a well-defined poly(N-isopropylacrylamide-co-sodium 2-acrylamido-methylpropanesulfonate) (NIPAM/NaAMPS in a 95/5 molar ratio) have been investigated by means of small-angle neutron scattering (SANS) and rheological experiments as a function of temperature ( 25^° C T 60^° C) and polymer concentration ( 0.5wt% C 12wt%). The solutions remain optically transparent and isotropic over the whole temperature range, in contrast with the homopolyNIPAM which precipitates above its lower critical solution temperature (LCST = 32^° C). Upon addition of salt, the systems undergo a micro-macrophase separation. At temperatures above 45^° C, the SANS spectra exhibit a sharp peak at a scattering wave vector, q _max, which increases slightly with temperature. At high temperature ( T∼ 60^° C), the scattered intensity follows a power law I(q) ∼q ^-4 in the asymptotic regime, characteristic of two-density media with sharp interfaces, and q _max is found to vary with polymer concentration as q _max∼C ^0.22. Estimates of the typical sizes give values between 40 ? and 200 ?. These results provide a strong evidence of a thermally induced microphase separation, which is corroborated by the very sharp increases of the viscosity (over 2 decades) and of the stress relaxation time of the solutions, occurring in the temperature range where the scattering peak is observed. The results are discussed and compared with the theoretical models proposed for weakly charged polyelectrolytes in a poor solvent. Received 1 October 2001     

Total cross-sections for positron scattering by a series of molecules

The additivity rule is employed to obtain the total (elastic+inelastic) cross-sections for positron scattering from molecules including a number of diatomic, polyatomic molecules (H₂, N₂, HCl, CO₂, NH₃, SF₆, CH₄, C₂H₄ and C₃H₈) over an incident energy range of 10-1000 eV. The total cross-sections (TCS) of the constituent atoms of molecules are obtained by employing a complex optical model potential (composed of static, polarization and absorption potential). The present results are compared with experimental data and other theoretical calculations, good agreement is obtained in intermediate- and high-energy region. Received: 11 November 1997 / Revised: 23 March 1998 / Accepted: 16 June 1998     

Alternating magneto-birefringence of ionic ferrofluids in crossed fields

A dynamic probing of magnetic liquids is performed experimentally, using a static magnetic field modulated by another smaller field, normal and alternating. The optical magneto-birefringence under these crossed magnetic fields is recorded as a function of the frequency for different field intensities and different sizes of the magnetic nanoparticles. A general reduced behavior is found for the in-phase and the out-of-phase optical response which is well-described by a simple mechanical model. Depending on the value H _ani of the anisotropy field of the nanoparticles, we can distinguish two different high magnetic field regimes: - a rigid dipole regime (large anisotropy energy with respect to k _B T) for cobalt ferrite nanoparticles with a relaxation time inversely proportional to the field intensity H _C(H _C < H _ani), - a soft dipole regime (anisotropy energy of the order of k _B T) for maghemite nanoparticles with a relaxation time independent of the field intensity H _C(H _C > H _ani). Received 5 June 2000 and Received in final form 8 January 2001     

Synthesis and characterization of hexagonal nano-sized nickel selenide by simple hydrothermal method assisted by CTAB

Nano-sized nickel selenide powders have been successfully synthesized via an improved hydrothermal route based on the reaction between NiCl₂·6H₂O, SeCl₄ and hydrazine (N₂H₄·H₂O) in water, in present of cetyltrimethyl ammonium bromide (CTAB) as surfactant, at various conditions. The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray energy dispersive spectroscopy analysis. Effects of temperature, reaction time and reductant agent on the morphology, the particle sizes and the phase of the final products have been investigated. It was found that the phase and morphology of the products could be greatly influenced by these parameters. The synthesis procedure is simple and uses less toxic reagents than the previously reported methods. Photoluminescence (PL) was used to study the optical properties of NiSe samples.     

Synthesis and luminescence properties of lead-halide based organic–inorganic layered perovskite compounds (CnH2n+1NH3)2PbI4 (n=4, 5, 7, 8 and 9)

This paper describes the synthesis and characterization of organic–inorganic layered perovskite compounds, (C_nH_2n+1NH₃)₂PbI₄ (n=4, 5, 7, 8 and 9). The effect of the number of carbon atoms on luminescence properties has been examined. Thin films of microcrystalline (C_nH_2n+1NH₃)₂PbI₄ fabricated by spin-coating are highly oriented, with the c-axis perpendicular to the substrate surface. Temperature-dependent optical absorption spectra reveal that (C_nH_2n+1NH₃)₂PbI₄ films (n=4, 7, 8 and 9) show the structural phase transitions. The excitonic structures of (C_nH_2n+1NH₃)₂PbI₄ vary with the number of carbon atoms of the alkyl chain length. At low temperatures below 100 K, the lowest-energy free-exciton band of (C_nH_2n+1NH₃)₂PbI₄ (n=7, 8 and 9) split into three fine-structure levels. In contrast to (C_nH_2n+1NH₃)₂PbBr₄ films, (C_nH_2n+1NH₃)₂PbI₄ (n=7, 8 and 9) shows no triplet exciton emission, but it shows the Stokes-shifted emission from bound excitons.     

Asymptotic analysis of wall modes in a flexible tube

The stability of wall modes in a flexible tube of radius R surrounded by a viscoelastic material in the region R < r < H R in the high Reynolds number limit is studied using asymptotic techniques. The fluid is a Newtonian fluid, while the wall material is modeled as an incompressible visco-elastic solid. In the limit of high Reynolds number, the vorticity of the wall modes is confined to a region of thickness in the fluid near the wall of the tube, where the small parameter , and the Reynolds number is , and are the fluid density and viscosity, and V is the maximum fluid velocity. The regime is considered in the asymptotic analysis, where G is the shear modulus of the wall material. In this limit, the ratio of the normal stress and normal displacement in the wall, , is only a function of H and scaled wave number . There are multiple solutions for the growth rate which depend on the parameter .In the limit , which is equivalent to using a zero normal stress boundary condition for the fluid, all the roots have negative real parts, indicating that the wall modes are stable. In the limit , which corresponds to the flow in a rigid tube, the stable roots of previous studies on the flow in a rigid tube are recovered. In addition, there is one root in the limit which does not reduce to any of the rigid tube solutions determined previously. The decay rate of this solution decreases proportional to in the limit , and the frequency increases proportional to . Received: 5 November 1997 / Revised: 10 March 1998 / Accepted: 29 April 1998     

Effect of surfactants on the degradation of perfluorooctanoic acid (PFOA) by ultrasonic (US) treatment

Perfluorooctanoic acid (C₇F₁₅COOH, PFOA) is an aqueous anionic surfactant and a persistent organic pollutant. It can be easily adsorbed onto the bubble-water interface and both mineralized and degraded by ultrasonic (US) cavitation at room temperature. The aim of this study is to investigate whether the effect of US on the degradation of PFOA in solution can be enhanced by the addition of surfactant. To achieve this aim, we first investigated the addition of a cationic (hexadecyl trimethyl ammonium bromide, CTAB), a nonionic (octyl phenol ethoxylate, TritonX-100), and an anionic (sodium dodecyl sulfate, SDS) surfactant. We found the addition of CTAB to have increased the degradation rate the most, followed by TritonX-100. SDS inhibited the degradation rate. We then conducted further experiments characterizing the removal efficiency of CTAB at varying surfactant concentrations and solution pHs. The removal efficiency of PFOA increased with CTAB concentration, with the efficiency reaching 79% after 120 min at 25 °C with a 0.12 mM CTAB dose.     

Synthesis of Novel Fluorescent Cyclohexenone Derivatives and their Partitioning Study in Ionic Micellar Media

An approach is demonstrated toward the synthesis of four novel cyclohexenone derivatives (CDs) via a convenient route of Michael addition of ethyl acetoacetate. The molecular structures of CDs were confirmed by means of FT-IR, ¹H NMR, EIMS, UV and also by X-ray single crystal structure analysis. CDs are strongly fluorescent compounds and their fluorescent spectra exhibits intense violet fluorescence. To model the binding to biological membranes the behavior of CDs in micellar solutions of a cationic surfactant, cetyltrimethylammonium bromide (CTAB) and an anionic surfactant, sodium dodecylsulfate (SDS) has also been examined. The characteristics of partition and binding interactions of CDs with CTAB and SDS were investigated by UV-Visible and fluorescence spectroscopic techniques. Higher values of all mentioned interactions in case of CTAB, compared to SDS, indicate that there are greater interactions between the CDs and CTAB than with SDS.     

阳离子表面活性剂三甲基溴化铵与硝酸铵相互作用的表面和热力学研究

本文系统研究了阳离子表面活性剂三甲基溴化铵和硝酸铵盐的表面现象和自聚集行为. 采用电导法和表面张力法研究在不同温度下阳离子表面活性剂三甲基溴化铵的表面性质和热力学性质. 通过表面张力测定得到临界胶束浓度、吸附自由能、胶束化的自由能、最小分子面积和表面过量浓度. 该研究表明,胶束化过程是自发放热反应. 电导测定结果确定了临界胶束浓度、电离程度和反离子结合度. 加入硝酸铵盐至表面活性剂溶液后,临界胶束浓度降低,电离程度和反离子结合度增加,更加有利于胶束化过程的自发. 该研究对进一步理解电解质和表面活性剂之间相互作用具有重要意义.