Temperature effect on the microstructure and viscoelastic properties of aqueous micellar systems of sodium <Emphasis Type="Italic">N</Emphasis>-methyl-<Emphasis Type="Italic">N</Emphasis>-oleyl taurate

The quantitative characteristics of the temperature effect on the rheological properties of aqueous solutions of the anionic surfactant sodium methyl oleyl taurate (SMOT) are presented. An increase in the intensity of thermal motion of surfactant molecules on heating from 25 to 45 °С was shown to decrease the average contour length of SMOT micelles from 2 μm to 700 nm. The decrease in the length of cylindrical micelles is probably one of the main reasons for a substantial decrease in the viscosity of micellar solutions of the surfactant with temperature.     

Rheology of wormlike micelles in aqueous systems of a mixed amino acid-based anionic surfactant and cationic surfactant

Amino acid-based anionic surfactant, N-dodecanoylglutamic acid, after neutralizing by 2, 2′, 2″-nitrilotriethanol forms micellar solution at 25 °C. Addition of cationic cosurfactants hexadecyltrimethylammonium chloride (CTAC), hexadecylpyridinium chloride (CPC), and hexadecylpyridinium bromide (CPB) to the semi-dilute solution of anionic surfactant micellar solutions favor the micellar growth and after a certain concentration, entangled rigid network of wormlike micelles are formed. Viscosity increases enormously ～4th order of magnitude compared with water. With further addition of the cosurfactants, viscosity declines and phase separation to liquid crystal occurs. The wormlike micelles showed a viscoelastic behavior and described by Maxwell model with a single stress-relaxation mode. The position of viscosity maximum in the zero-shear viscosity curve shifts towards lower concentration upon changing cosurfactant from CPB to CTAC via CPC; however, the maximum viscosity is highest in the CPB system showing the formation of highly rigid network structure of wormlike micelles. In all the systems, viscosity decays exponentially with temperature following Arrhenius type behavior.     

Rheology of viscoelastic solutions of cationic surfactant. Effect of added associating polymer

Rheological studies were performed with aqueous salt solutions of viscoelastic cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride (EHAC) and its mixtures with hydrophobically modified polyacrylamide. The solutions of surfactant itself above the concentration of crossover of wormlike micelles exhibit two regions of rheological response. In the first region, they behave like polymer solutions in semidilute regime characterized by viscoelastic behavior with a spectrum of relaxation times. In the second region, unlike polymer solutions their relaxation after shear is dominated by a single relaxation time. Being composed of "living" micelles, the EHAC solutions easily lose their viscosity at the variation of the external conditions. For instance, heating from 20 to 60 degrees C reduces viscosity by up to 2 orders of magnitude, while added hydrocarbons induce a sudden drop of viscosity by 3-6 orders of magnitude. Polymer profoundly affects the rheological properties of EHAC solutions. The polymer/surfactant system demonstrates a 10,000-fold increase in viscosity as compared to pure-component solutions, the effect being more pronounced for polymer with less blocky distribution of hydrophobic units. A synergistic enhancement of viscosity was attributed to the formation of common network, in which some subchains are made up of elongated surfactant micelles, while others are composed of polymer. At cross-links the hydrophobic side groups of polymer anchor EHAC micelles. In contrast to surfactant itself, the polymer/surfactant system retains high viscosity at elevated temperature; at the same time it keeps a high responsiveness to hydrocarbon medium inherent to EHAC.     

Viscoelastic micellar solutions in a mixed nonionic fluorinated surfactants system and the effect of oils

Formation and rheological behavior of viscoelastic wormlike micelles in aqueous solution of a mixed system of nonionic fluorinated surfactants, perfluoroalkyl sulfonamide ethoxylate, C8F17SO2N(C3H7)(CH2CH2O)nH (abbreviated as C8F17EOn) was studied. In the water-surfactant binary system C8F17EO20 forms an isotropic micellar solution over wide concentration range (>85 wt %) at 25 degrees C. With successive addition of C8F17EO1 to the aqueous C8F17EO20 solution, viscosity of the solution increases swiftly, and a viscoelastic solution is formed. The oscillatory rheological behavior of the viscoelastic solution can be described by Maxwell model at low-frequency region, which is typical of wormlike micelles. With further addition of C8F17EO1, the viscosity decreases after a maximum and phase separation occurs. Addition of a small amount of fluorinated oils to the wormlike micellar solution disrupts the network structure and decreases the viscosity sharply. It is found that polymeric oil, PFP (F-(C3F6O)nCF2CF2COOH), decreases the viscosity more effectively than the perfluorodecalin (PFD). The difference in the effect of oil on rheological properties is explained in terms of the solubilization site of the oils in the hydrophobic interior of the cylindrical aggregates, and their ability to induce rod-sphere transition.     

Aggregation behavior of morpholinium surfactants in the presence of organic electrolytes

It was shown that the addition of organic electrolytes to aqueous solutions of morpholinium surfactants facilitates micellization, reduces the micellar surface potential, increases the hydrodynamic diameter of micelles and favors the formation of cylindrical micelles which behave as pseudoplastic fluids. At low shear rates, the viscosity is extremely large and changes insignificantly, and it decreases sharply with increase in shear rate. Significant decrease in viscosity upon the increase in shear deformations indicates the orientation of cylindrical micelles along the direction of the flow with the increase in shear rate.     

Are large micelles rigid or flexible? A reinterpretation of viscosity data for micellar solutions

Surfactant solutions in which large cylindrical micelles form are characterized by two essential features, namely, they are polydisperse and the average micelle size is proportional to the square root of the micelle concentration. These features of the cylindrical micelles imply that the intrinsic viscosities of these micellar solutions should also depend on the concentration of micelles. This fact has been ignored in all past treatments of micellar viscosity data. Here, viscosity data available in literature were reexamined in terms of concentration-dependent intrinsic viscosity so as to evaluate the rigidity or the flexibility of the large micelles. It is found that the interpretation of viscosity data assuming that the large micelles are rigid rods is in very good agreement with the theoretically anticipated essential features of large micelles. It is concluded that large micelles can be satisfactorily represented by rigid rods rather than by flexible rods or coils.     

Wormlike micelles in mixed amino acid-based anionic/nonionic surfactant systems

We present the formation of viscoelastic wormlike micelles in mixed amino acid-based anionic and nonionic surfactants in aqueous systems in the absence of salt. N-Dodecylglutamic acid (designated as LAD) has a higher Krafft temperature; however, on neutralization with alkaline amino acid l-lysine, it forms micelles and the solution behaves like a Newtonian fluid at 25 degrees C. Addition of tri(oxyethylene) monododecyl ether (C(12)EO(3)) and tri(oxyethylene) monotetradecyl ether (C(14)EO(3)) to the dilute aqueous solution of the LAD-lysine induces one-dimensional micellar growth. With increasing C(12)EO(3) or C(14)EO(3) concentration, the solution viscosity increases gradually, but after a certain concentration, the elongated micelles entangle forming a rigid network of wormlike micelles and the solution viscosity increases tremendously. Thus formed wormlike micelles show a viscoelastic character and follow the Maxwell model. Tri(oxyethylene) monohexadecyl ether (C(16)EO(3)), on the other hand, could not form wormlike micelles, although the solution viscosity increases too. The micelles become elongated; however, they do not appear to form a rigid network of wormlike micelles in the case of C(16)EO(3). Rheological measurements have shown that zero shear viscosity (eta(0)) increases with the C(12)EO(3) concentration gradually at first and then sharply, and finally decreases before phase separation. However, no such maximum in the eta(0) plot is observed with the C(14)EO(3). The eta(0) increases monotonously with the C(14)EO(3) concentration till phase separation. In studies of the effect of temperature on the wormlike micellar behavior it has been found that the eta(0) decays exponentially with temperature, following an Arrehenius behavior and at sufficiently higher temperatures the solutions follow a Newtonian behavior. The flow activation energy calculated from the slope of log eta(0) versus 1/T plot is very close to the value reported for typical wormlike micelles. Finally, we also present the effect of neutralization degree of lysine on the rheology and phase behavior. The formation of wormlike micelles is confirmed by the Maxwell model fit to the experimental rheological data and by Cole-Cole plots.     

Chiroptical aggregates from block copolymer bearing amino acid moieties in aqueous solution

Optically active poly(ethylene glycol) monomethyl ether‐b‐poly(methacryloyl‐L ‐leucine methyl ester) (denoted as MPEG‐b‐PMALM) copolymers were prepared via atom transfer radical polymerization (ATRP), using bromine (Br) end‐capped poly(ethylene glycol) monomethyl ether (denoted as MPEG‐Br) as macroinitiator in the presence of CuBr/tris(2‐dimethylaminoethy1)amine (Me₆TREN) as catalytic system. Broad range of morphologies, such as spherical, cylindrical, and vesicular micelles, which were prepared by initially dissolving prepared polymer in organic solvent at different concentration followed by addition various amount of water before dialysis against water to remove any added solvent, was observed by transmission electron microscope (TEM). More detailed chiroptical properties of the micelles/aggregates in aqueous solution were evaluated by circular dichroism (CD) spectroscopy as a function of micelles morphologies, polymer concentration, solvents employed, temperature, etc. The micellar solutions exhibit almost the same CD spectra regardless of its morphologies. The intensity of the CD spectra of the cylindrical micelles decreased in the molar ellipticities as the micellar concentration in water was increased. The Cotton effect was markedly changed when the solvent hydrophobicity was changed by addition of trifluoromethyl ethanol (TFME) to water. The intensity of the CD spectra decreased not too much within the temperature range from 20 °C to 90 °C, indicating good stability of the micelles upon temperature variation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1345–1355, 2009     

The spinnability of viscoelastic solutions of tetradecyl- and hexadecyl-trimethylammonium salicylates

The spinnability was measured for aqueous viscoelastic solutions of tetradecyl- and hexadecyltrimethylammonium salicylates (C₁₄TASal, C₁₆TASal) in the absence and presence of sodium salicylate (NaSal) and sodium bromide (NaBr). The spinnability is classified into two types, D and C. While the intrinsic drawing length in type D is proportional to the drawing velocity, the drawing intrinsic length in type C decreases with the drawing velocity or is independent of it. The spinnability changes from type D to C, as the drawing velocity and the surfactant concentration increase, and the temperature lowers. The effect of salt is different between NaSal and NaBr. It can be assumed that a pseudo-network structure composed of rod-like micelles is formed in viscoelastic and spinnable surfactant solutions. Then, the spinnability depends on the balance between the elasticity and the viscosity in which the structure results.     

Phase behavior and rheological properties of enzymatically synthesized trehalose decanoate aqueous solutions

Surface tension properties of an enzymatically synthesized equimolar mixture of trehalose mono- and didecanoate in aqueous solutions have been determined. At 20 degrees C a critical micellar concentration (CMC) of 50 micromol/l and a minimal surface tension of 28 mN/m have been obtained. Above the CMC, it has been shown that up to a concentration of 42 wt%, and in a 20-60 degrees C temperature range the sugar ester aqueous solutions do not form any crystalline structure, nor present any phase transition, and the trehalose decanoate molecules form an isotropic worm-like micellar phase. The rheological properties indicate however a more complicated picture in the same concentration and temperature ranges. In steady shear, the viscosity of the trehalose decanoate solutions do not exhibit any shear rate dependence from 1 to 100 s(-1) for concentrations up to 42 wt%. Below 0.8 wt%, the viscosity remains constant and close to that of water; then, between 0.8 and 23 wt%, the viscosity shows a quadratic increase with surfactant concentration. For higher concentrations, up to 42 wt%, no further significant increase in viscosity is observed. In oscillatory shear experiments, the solutions exhibit viscoelastic properties. The observed rheological behavior as a function of concentration and temperature may be due to a progressive evolution of the trehalose decanoate molecular associations: as the concentration increases, the system evolves towards an entangled and/or partially branched or cross-linked micellar network, and eventually a multiconnected network of cross-linked micelles.     

Application of the theory of dilute polymer solutions to the assessment of the structure and properties of styrene-acrylic acid copolymers

Properties of dilute solutions of polystyrene and styrene-acrylic acid copolymers in DMF and ethyl acetate were studied in the temperature range 20–35°C. It was shown that the dependences of the intrinsic viscosity and Huggins constants on temperature for the copolymers differ from that for polystyrene. Comparison of the “quality” of the solvents was carried out.     

Relaxation phenomena in concentrated polyelectrolyte solution. II

Dynamic viscoelastic properties of 10 and 20% aqueous solutions of sodium polyacrylate were studied by the electromagnetic transducer method at 500 cps in the temperature range of 0–50°C. These solutions distinctly showed a relaxation phenomenon in this temperature range which was also affected by addition of such compounds as sodium chloride, urea, and dioxane. An anomalous behavior that cannot be explained as due to the relaxation phenomenon was observed on the addition of small amounts of these agents. One of the causes of this behavior is ascribed to the ion association in the solution. The static viscosity of the solution was also measured by using a rotating cylinder viscometer and the results compared with the dynamic data.     

Micelles of SDS Surfactants in Concentrated NaCl Solutions

We investigated the aggregation behavior of rod-like micelles of sodium dodecyl sulfate (SDS) in concentrated NaCl solution by quasi-elastic light scattering (QLS) and viscosity measurement over a range of temperature (25 °C to 50 °C) and NaCl concentration. The reduced viscosity of aqueous SDS in the presence of NaCl has been measured by an Ubbelohde-type capillary viscometer. We show mean hydrodynamic radius of micelles can be determined from viscosity data. We also determined mean hydrodynamic radius using quasi-elastic light scattering. Micellar size decreases with increasing temperature, whereas it increases with increasing ionic strength. The results of viscosity and dynamic light-scattering measurements are interpreted as the extension of length of rod-like micelles. We compare viscosity and light scattering experimental results.     

季铵盐Gemini表面活性剂胶团水溶液的流变性质

用毛细管振荡剪切流动法研究联接基团为聚亚甲基链的季铵盐型Gemini表面活性剂C_12-s-C₁₂·2Br(s=2,4,8)的流变性质,并用动态光散射技术测定胶团生长过程中的胶团形状和大小的变化规律,探索联接基团长度对胶团形状、大小以及溶液流变性质的影响.实验结果表明,胶团形状和大小与联接基团长度有关,而溶液的流变性质主要由胶团的大小和形状所决定,球形和棒状(长椭球体)胶团溶液的流变性质以纯粘度为主,而线性胶团溶液则显示粘弹性质.此外,增加电解质浓度和降低温度均使溶液的粘度增大.     

Wormlike micelles of a C22-tailed zwitterionic betaine surfactant: from viscoelastic solutions to elastic gels

The 22-carbon-tailed zwitterionic surfactant erucyl dimethyl amidopropyl betaine (EDAB) forms highly viscoelastic fluids in water at low concentrations and without the need for salt or other additives. Here, semidilute aqueous solutions of EDAB are studied by using a combination of rheological techniques, small-angle neutron scattering (SANS) and cryo-transmission electron microscopy (cryo-TEM). EDAB samples show interesting rheology as a function of temperature. At low temperatures (approximately 25 degrees C), a 50 mM EDAB sample behaves like an elastic gel with an infinite relaxation time and viscosity. Upon heating to approximately 60 degrees C, however, the sample begins to respond like a viscoelastic solution; that is, the relaxation time and zero-shear viscosity become finite, and the rheology approaches that of a Maxwell fluid. The same pattern of behavior is repeated at higher EDAB concentrations. Cryo-TEM and SANS reveal the presence of giant wormlike micelles in all EDAB samples at room temperature. The results imply that, depending on temperature, EDAB wormlike micelles can exhibit either a gel-like response or the classical viscoelastic ("Maxwellian") response. The unusual gel-like behavior of EDAB micelles at low temperatures is postulated to be the result of very long micellar breaking times, which, in turn, may be due to the long hydrophobic tails of the surfactant.     

Rheology of the Melt of Acrylonitrile–Styrene Copolymer Modified with Montmorillonite

The rheological properties of the acrylonitrile–styrene copolymer modified with hydrophobized montmorillonite Cloisite 30B and composites are studied in a wide range of shear rates and shear frequencies at a temperature of 230°C. It is shown that the filler insignificantly affects the viscoelastic properties of the compositions, but the viscosity of composite melts considerably increases at low shear rates and monotonically grows with increasing concentration, whereas at high shear rates the effective viscosity declines appreciably in the concentration range of about 0.3 vol %.     

Rheological properties of associates of ionic monomers with micelles of oppositely charged surfactants

Rheological properties of associates formed by interaction of trimethyl[methacryl-oxyethyl]ammonium methyl sulfate with sodium octyl- and dodecyl sulfate micelles, as well as associates of sodium 4-styrenesulfonate with dodecyltrimethylammonium bromide micelles in aqueous solutions were studied by steady shear and oscillatory (dynamic) shear measurements with Fourier transform. It was shown that viscosity depends on the composition and achieves maximum value at equimolar ratio of components for two of studied systems. The extremal dependence of the viscosity vs. composition is not observed for systems with sodium octyl sulfate due to weak interactions between the components. The systems exhibiting the anomalous dependencies of concentration to viscosity are viscoelastic fluids due to the physical entanglements between the associates.     

Self-assembled networks highly responsive to hydrocarbons

Rheological studies were performed with aqueous salt solutions of anionic surfactant potassium oleate and its mixtures with hydrophobically modified polyacrylamide. Semidilute solutions of the surfactant in the presence of salt (KCl) demonstrate viscoelastic properties due to the formation of a transient network of entangled wormlike micelles. These systems are highly responsive to hydrocarbons: the addition of n-heptane or n-dodecane reduces the viscosity of solutions by up to 4 to 5 orders of magnitude, thus inducing the transition of a gellike system to a fluid one. It is the transformation of cylindrical surfactant micelles into spherical ones upon absorption of hydrocarbon that disrupts the network. The addition of a small amount (0.5 wt %) of associating polymer leads to up to a 5000-fold increase in the zero-shear viscosity and enhances the susceptibility to hydrocarbons. SANS data show that independently of the presence of polymer the radius of wormlike micelles is roughly equal to the length of a surfactant molecule, whereas the radius of spheres formed upon the absorption of hydrocarbon is 2-2.5-fold higher. A possible structure of the spherical micelles is discussed.     

Temperature structural transformations of reverse micelles of oxyethylated surfactants

The dependence of the hydrodynamic radius of reverse micelles of Tergitol NP-4 on temperature (20–50°C), solubilization capacity (0–7 vol %), electrolyte composition (NH₄NO₃, KNO₃, HNO₃, NH₄OH, and KOH), and electrolyte concentration (0–8 mol/l) in an aqueous pseudophase was studied by photon-correlation spectroscopy. The hydrodynamic radius of micelles was shown to decrease with increasing temperature regardless of the concentration and type of electrolyte, and spherical micelles were formed in the process. It was ascertained that temperature aligns the features of interaction between solubilisate and micelles due to dehydration of the surfactant molecules: the radius of spherical micelles at 50°C depended only on solubilization capacity.     

Effect of temperature on the rheology of wormlike micelles in a mixed surfactant system

The formation and rheological behavior of a viscoelastic wormlike micellar solution in an aqueous solution of a mixed surfactant system of alkyl ethoxylate sulfate (AES), C(12)H(25)(OCH(2)CH(2))(3)OSO(-)(3)Na(+), and polyoxyethylene dodecyl ether, C(12)EO(3), and the unusual effect of temperature on the rheological behavior have been studied. Upon successive addition of C(12)EO(3) to the dilute micellar solution of AES, viscosity increases swiftly and reaches its peak where a viscoelastic solution with nearly Maxwellian behavior is formed. With the further addition of C(12)EO(3), viscosity decreases sharply, which is attributed to the formation of micellar joints. With increasing temperature, the extent of micellar growth increases and the viscosity maximum is achieved at a lower mixing fraction of C(12)EO(3), but the maximum viscosity attained by the system decreases. The evolution of relaxation time and network density of the viscoelastic network also suggests that with increasing temperature, enhanced micellar growth takes place, but an additional, faster relaxation mechanism becomes increasingly favorable at high concentrations of C(12)EO(3). These results can be explained in terms of the increase in free energy of hemispherical end-caps (end-cap energy) of the micelles with increasing temperature.