The effects of some factors on the rheological properties of the lyotropic liquid crystals formed in Brij97/NaDC/IPM/water system: compositions,temperature and polyphenols

In this paper, interaction between Brij97 and NaDC in mixed micelles was studied by surface tension method. Phase behavior for Brij97/NaDC/IPM/H₂O system was investigated at the desire molar ratio of α_NaDC?=?0.42 and the human body temperature of 37?°C. Hexagonal and cubic liquid crystal were found in this system analyzed by small angle x-ray scattering (SAXS). some factors were changed to affect the rheological properties of liquid crystal. Rheological investigations showed: The higher content of water and lower experimental temperature favored the greater values of shear viscosity and viscoelastic modulus; The sample was closer to the plastic fluid and was more likely to recover from disturbed state to equilibrium state at lower ratio of NaDC; The curcumin and TP can influence the shear viscosity, viscoelastic properties and phase transition temperature, even change the structure of liquid crystal. This supplies a way to adjust rheological properties, structure and even phase transition by altering those factors.     

Solubilization of oils or addition of monoglycerides drives the formation of wormlike micelles with an elliptical cross-section in cholesterol-based surfactants: a study by rheology, SANS, and cryo-TEM

We report the formation of wormlike micelles (WLM) in poly(oxyethylene) cholesteryl ether (ChEO(10)) aqueous solutions by the addition of lipophilic monoglycerides at room temperature (monolaurin (ML), monocaprin (MC), and monocaprylin (MCL)) bearing 12-, 10-, and 8-carbon alkyl chains, respectively. A combination of rheology, small-angle neutron scattering (SANS), and cryo-TEM was used to study their viscoelastic properties and structure. With the successive addition of cosurfactant, a significant increase in viscosity and a clear solidlike behavior is obtained, suggesting the formation of a viscoelastic network of wormlike micelles. Only for MCL is typical Maxwellian behavior obtained. The onset of micellar growth, as detected by the occurrence of solidlike behavior and a significant increase in viscosity, is obtained for 0.30 (1 wt%), 0.34 (1 wt%), and 0.60 (1.5 wt%) cosurfactant/ChEO(10) molar ratios with ML, MC, and MCL, respectively. With ML and MC, extremely long relaxation times (exceeding 20 s) compared to those of MCL are obtained, and zero-shear viscosity values are more than 1 order of magnitude higher than with MCL. These results show that cosurfactants with longer alkyl chain lengths (ML and MC) induce the formation of longer wormlike micelles and do so at lower concentrations. SANS measurements on dilute solutions confirm that the viscoelastic behavior correlates with an increase in contour length and reveals an elliptical cross-section with an axial ratio of around 2. Cryo-TEM images provide visual evidence of the wormlike micelles and confirm the elliptical shape of the cross-section. The addition of small amounts of aliphatic oils (ethyl butyrate, EB, and ethyl caprylate, EC) and cyclic oils (peppermint, PP, and tea tree, TT, oils) to ChEO(10) solutions induces wormlike micelle formation at a lower cosurfactant concentration or even in its absence (for PP, TT, and EC) because of their probable localization in the palisade layer. The viscosity peak and height of the plateau modulus occur at increasing monoglyceride concentration following the order PP ≈ TT > EC > EB > no oil.     

Weak transverse magnetic field effect on the viscosity of Mn(NO3)2H2O solution at several temperature

Experiments show that transversally applied magnetic field H of strength 12 kG at 10, 15, 20, 25, 30, 40 and 60°C and the ambient pressure decreases the viscosity of high concentration Mn(NO₃)₂H₂O solution. The largest value of this decrease occurs at the temperature range of 20–25°C. On the other hand, at low paramagnetic ion concentrations, the applied magnetic field increases the viscosity of Mn(NO₃)₂H₂O solution in such a way that the observed effect value in the limit seems to approach the already measured viscosity increase of the pure water. However, the temperature dependence of the observed viscosity increase of the given dilute paramagnetic Mn(NO₃)₂H₂O solution appears to be more complex and at some temperature even opposite to that already shown viscosity—temperature behavior of the diamagnetic pure water.     

Rheological behavior of viscoelastic wormlike micelles in mixed sodium dodecyl trioxyethylene sulfate–monolaurin aqueous system

Rheological behavior of viscoelastic wormlike micelles in an aqueous system of mixed sodium dodecyl trioxyethylene sulfate (SDES)–monolaurin (ML) is presented. Dilute aqueous solution of SDES has a high fluidity and follows Newtonian liquid-like behavior due to formation of small globular type of micellar structure. Addition of lipophilic nonionic cosurfactant ML to dilute or semidilute solution of SDES decreases the interfacial curvature of the aggregates favoring one dimensional micellar growth, and hence, viscosity increases. After a certain concentration of ML, the elongated micelles get entangled with each other leading to the formation of viscoelastic wormlike micelles. The viscoelastic solution follows Maxwell model of a single stress relaxation mode at low-frequency region. Further addition of ML decreases the viscosity of the solution due to formation of micellar joints in the network structure. The viscosity of the viscoelastic wormlike micelles decreases upon heating, and the system with poor viscoelastic character is observed at higher temperatures.     

Rheological behavior of PAA–C n TAB complex: influence of PAA charge density and surfactant tail length in PAA semidilute aqueous solution

Interactions between anionic polyelectrolyte, poly(acrylic acid) (PAA), and cationic surfactant, alkyltrimethylammonium bromide (C _n TAB), were investigated by rheological measurements in semidilute PAA solution. The dependences of the rheological behavior on the chain length of the surfactant, PAA neutralization degree, and temperature were discussed. The results revealed that both dodecyl and cetyltrimethylammonium bromides (C₁₂TAB and C₁₆TAB) could increase the viscosity of PAA solution when the surfactant amounts surpassed a critical surfactant concentration (C _c), and C _c of C₁₆TAB was lower than that of C₁₂TAB at same PAA neutralization degree. The increase of viscosity is attributed to the surfactant micelles bridging of the polymer chains and confine the mobility PAA chain. On the other hand, it is found that the hydrogen bonding also played an important role in the PAA–C _n TAB system, especially in lower neutralization degree PAA solution, which results in the viscosity increase rapidly with the added surfactant into lower neutralization degree PAA solution.     

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.     

Linear viscoelastic characteristics of in situ compatiblized binary polymer blends with viscoelastic properties of components variable

By Friedel‐Crafts alkylation reaction, catalyzed by a Lewis acid of anhydrous aluminum chloride (AlCl₃), binary polymer blends of polypropylene (PP)/polystyrene (PS) with volume proportion of 80/20 were in situ compatiblized and prepared in an XSS‐30 melt mixer at 210 °C. The linear viscoelastic characteristics of the blends were investigated by checking the variations of storage modulus, loss modulus, complex modulus, and complex viscosity of the in situ compatiblized blends, which were dependent on AlCl₃ content. In addition, Han plots of the in situ compatiblized blends with different AlCl₃ content were also used to characterize the linear viscoelastic properties of the blends. The results showed that both the dynamic rheological parameters and the Han plots were obviously influenced by the rheological properties of the matrix and slightly influenced by the rheological properties of the dispersed phase. Further investigations revealed that phase geometry contributions to the dynamic rheological parameters of the blends could be ignored in comparison with the contributions of the components and the interfacial modification, which were defined and obtained according to log‐linear‐additivity rule. The linear viscoelastic characteristics of the blends were mainly controlled by the combination of the effects of interfacial modification between phases and the rheological properties of the matrix. Storage modulus is the most sensitive dynamic rheological parameter to characterize the interfacial compatiblization effects in the in situ compatiblized binary polymer blends with rheological properties of components variable. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1349–1362, 2010     

Effect of Potassium Oleate on Rheological Behavior of Cationic Guar in Aqueous Solution with Varying Temperatures

The rheology of the cationic guar (CG) solution was measured and the effects of potassium oleate (KOA) upon the rheological properties of CG solution were studied. The steady shear viscosity measurement has shown that the viscosity of CG solution increased dramatically in the presence of KOA. The viscosity enhancement of KOA upon CG solution can be approximate three orders in magnitude. The gel-like formation of CG solution is observed at the high concentration of KOA. The excess addition of KOA results in the phase separation of CG solution. The oscillatory rheological measurement has shown that the crossover modulus Gc (corresponding to either storage modulus G′ or loss modulus G″ at the frequency w_c where G′ equals G″) for CG solution, decreases with the increasing the concentration of KOA in solution. On the other hand, the apparent relaxation time τ_app (=1/w_c) increases with increasing the concentration of KOA in solution. Our experimental results suggest that for surfactant such as KOA which has a stronger tendency to form micelles in solution, the cooperative hydrophobic interaction of polymer bound to surfactants is less necessary to the formation of aggregates in solution, especially at the high concentration of surfactants. In fact, with the increase of the concentration of KOA, the number of the aggregates which associate polymer together decreases whereas the intensity of these aggregates increases. The effect of temperature upon the aggregation is also significant. With the increase of temperature, the number of the aggregates increases whereas the intensity of these aggregates decreases, probably because the ionization of KOA increases at high temperature.     

Rheology and high-temperature stability of novel viscoelastic gemini micelle solutions

To broaden the application of clean fracturing fluid based on surfactant, a gemini cationic C₂₅-tailed surfactant, called FL-25, was synthesized. FL-25 can form a wormlike viscoelastic fluid in aqueous solution without adding any organic or inorganic salts. The rheological properties and thermal stability of the novel gemini micelle solutions were further investigated. The results show that the gemini micelle solution possesses viscoelasticity, thixotropy, and shear-thinning properties. The apparent viscosity of the viscoelastic gemini micelle solution at a shear rate of 170?s^?1 remains approximately 69?mPa?·?s at 110°C for 90 minutes, showing good high-temperature-resistance property. FL-25 may be a novel gemini surfactant applied in clean viscoelastic surfactant fracturing fluids in the oil and gas field.     

Rheology Behaviors of C22-Tailed Carboxylbetaine in High-Salinity Solution

Viscoelastic wormlike micelles have attracted special interests over the past decade due to their unique rheological response. Few efforts were however devoted to the rheological properties of worms in high-salinity solution. Here, worm-containing viscoelastic fluid is designed from single N-erucamidopropyl-N,N-dimethyl carboxybetaine (EMAB), using brine water (total dissolved solids: 32,868 mg L^?1; [Ca²⁺] + [Mg²⁺]: 873 mg L^?1) as solvent. Upon increasing concentration, EMAB brine solution shows remarkable macroscopic viscoelasticity above a low overlapping concentration (0.04 wt%) without adding special hydrotropes, implying a giant 3D network-like entanglement formation. Such a viscoelastic network aggregates exhibit thermo-induced thickening behavior in a comparable temperature range due to the hydrogen bond interaction, and excellent thermal stability. The apparent viscosity at 170 s^?1 can keep above 50 mPa · s at 130°C for 2 hours. These preliminary results will give EMAB a rich prospective for use as rheological modifier, especially for using in some extremely environment such high temperature, high salinity, and high shear.     

Melt rheology of ion-containing polymers. I. Effect of ionic content in a model polyesterionomer

The effects of copolymerizing small amounts of an ionic moiety (0–7 mol %) into the backbone of a polycondensation polymer have been investigated by a combination of linear viscoelastic, steady-shear, and extensional testing. At a constant viscosity in dilute solution, both the zero-shear-rate viscosity and the maximum relaxation time in the melt increase monotonically with an increase in the ionic character. These effects are present after the data are normalized to remove the increase in the glass transition temperature T_g with increased ionic content. Large-strain, steady-shear flow experiments showed that the viscoelastic memory of the melt is affected by ionic content. An increase in ion content causes a decrease in the effect of strain on the memory function. This effect is not apparent in extensional flow experiments, which indicate that the ionic content does not affect the response if the tests are conducted at a constant temperature above T_g.     

Weak transverse magnetic field effect on the viscosity of Ni(NO3)2H2O solution

Experiments performed at 25°C show that transversally applied magnetic field H of strength of 12 kG; at high concentrations decreases the viscosity of Ni(NO₃)₂H₂O solution. At low concentrations, however, the applied magnetic field increases the viscosity of Ni(NO₃)₂H₂O solution in such a way as the observed effect value approaches the already measured viscosity increase of the pure water at the same magnetic field and temperature conditions.     

Viscoelasticity and rheology in the regimes from dilute to concentrated in cellulose 1-ethyl-3-methylimidazolium acetate solutions

Dynamic rheological behaviors of α-cellulose 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) solutions were investigated in a large range of concentrations (0.1–10 wt %) at 25 °C. On the basis of data from the dynamic viscoelastic test, the exponents of the specific viscosity η _sp versus concentration c were determined as 1.0, 2.0 and 4.7 for dilute, semidilute unentangled and entangled regimes respectively, which were in accordance with the scaling prediction for neutral polymer in θ solvent. The intrinsic viscosity [η] of the solution was determined to be 253 mL/g at 25 °C. The linear viscoelastic response of the dilute and semidilute unentangled solutions could be described successfully by the Zimm and Rouse model (ν = 0.5 for θ solution) respectively, suggesting that the motion of cellulose chain in [Emim]Ac changed from Zimm to Rouse model with increasing concentration. At low concentrations, failure of the Cox–Merz rule with steady shear viscosity larger than complex viscosity was observed. While as the concentration increased, the deviation from the Cox–Merz rule disappeared due to the formation of homogeneous entanglement structure in cellulose solution.     

Dynamic viscoelastic properties of spread monostearin monolayer in the presence of glycine

The monostearin monolayer at the air-aqueous interface is more expanded in presence of glycine and at higher temperature from both the surface pressure-area per molecule (pi-A) isotherms and static elasticity-surface pressure (E(s)-pi) curves. The dilational viscoelastic properties of monostearin monolayer spread on the subphase of glycine solution have been determined by the dynamic oscillation method and discussed as a function of surface pressure, temperature, and frequency. At the frequency of 50 mHz, the monostearin monolayer on pure water shows negative dilational viscosity and is viscoelastic at some surface pressures, while the monostearin monolayer in the presence of glycine is nearly elastic over a wide range of surface pressure, especially at 25 degrees C. Both positive and negative loss angle tangent can be deduced as a function of surface pressure. The negative dilational viscosity can be attributed to the phase transitions induced by the propagation of the surface waves during the dynamic oscillation. It can be convinced that the interactions between monostearin and glycine play an important role in the formation and rheological behavior of the monolayer. On the other hand, temperature has effect on the dilational elasticity and the dilational viscosity of the monostearin monolayer in different extents. Furthermore, at the surface pressure of 20 mN/m, the monostearin monolayer on the glycine solution at 18 degrees C is essentially elastic at lower frequency (<100 MHz) and shows viscoelastic behavior at higher frequency. These phenomena should be associated with the complicated monolayer structure and structural reorganization due to the interactions between monostearin and glycine in presence of glycine.     

pH and temperature-responsive wormlike micelles formed by single amine oxide surfactant

In this paper, a novel type of pH- and temperature-responsive smart wormlike micelles based on (Z)-N,N-dimethyl-3-(octadec-9-enamido) propan-1-amine oxide (OAPAO) synthesized was studied. The structure of OAPAO was characterized by ¹H NMR and FTIR. The micellization and aggregation properties of the OAPAO surfactant in aqueous solution at different pH values were studied using equilibrium surface tension. The OAPAO solution exhibited pH-regulated surface activity at the air–water interface by assessing relevant parameters such as cmc, γ_cmc, Г_max, and A_min at pH?=?2.10, 6.80, and 11.90. The viscosity and rheological measurements demonstrated the pH-sensitive flowing behavior and property, which was attributed to the interactions transition between the OAPAO head groups. Moreover, the system could be promptly switched between low viscous fluid and highly viscoelastic fluid by alternatively adjusting the pH between 2.05 and 6.82. Combining the distribution state of OAPAO, a mechanism for the different intermolecular forces at different pH regions was proposed. Furthermore, the OAPAO solution exhibited an evident temperature-responsiveness at pH?=?6.82 and 11.88 in a certain temperature range (25–65°C) resulting from the effect of temperature on the hydrophobic effect and the intermicellar branching junctions.     

Short haired wormlike micelles in mixed nonionic fluorocarbon surfactants

We have studied the rheological behavior of viscoelastic wormlike micellar solution in a mixed system of nonionic fluorinated surfactants, perfluoroalkyl sulfonamide ethoxylate, C(8)F(17)SO(2)N(C(3)H(7))(CH(2)CH(2)O)(n)H abbreviated as C(8)F(17)EO(n) (n=10 and 20). Above critical micelle concentration, the surfactant, C(8)F(17)EO(20) forms small spherical micelles in water and the viscosity of the solution remains constant regardless of the shear rate, i.e., the solutions exhibit Newtonian behavior. However, upon successive addition of the C(8)F(17)EO(10) the viscosity of the solution increases and at certain C(8)F(17)EO(10) concentration, shear-thinning behavior is observed indicating the formation wormlike micelles. Contrary to what is expected, there is a viscosity increase with the addition of the hydrophilic C(8)F(17)EO(20) to C(8)F(17)EO(10) aqueous solutions at certain temperature and concentration, which could be attributed to an increase in rigidity of the surfactant layer and to the shifting of micellar branching to higher temperatures. The oscillatory-shear rheological behavior of the viscoelastic solution can be described by Maxwell model at low frequency. Small-angle X-ray scattering (SAXS) measurements confirmed the formation of small spherical micellar aggregates in the dilute aqueous C(8)F(17)EO(20) solution. The SAXS data shows the one-dimensional growth on the micellar size with increase in the C(8)F(17)EO(10) concentration. Thus, the present SAXS data supports the rheological data.     

Investigation on the interaction between C16TAB and NaCMC in semidilute aqueous solution based on rheological measurement

The rheological behavior of unentangled and entangled semidilute solution of anionic polyelectrolyte sodium carboxymethyl cellulose (NaCMC) containing cationic surfactant cetyltrimethylammonium bromide (C₁₆TAB) was investigated. The results reveal that the rheological properties of these semidilute NaCMC solutions depend on the amount of C₁₆TAB added. In the unentangled semidilute NaCMC solution (0.5 g/L), the viscosity decreases with the increase of C₁₆TAB amount in the low surfactant concentration region (below the critical aggregation concentration, CAC). However, in high surfactant concentrations (above CAC), the viscosity decreases sharply with the increase in C₁₆TAB amount. It is found that viscosity change of NaCMC solution could be described using Colby’s model when surfactant concentrations are between CAC and saturated concentration (C_s), suggesting that no inter-polymer interaction exists between C₁₆TAB and NaCMC in the unentangled semidilute solution. However, for the entangled semidilute NaCMC solution (5 g/L), the addition of C₁₆TAB leads to an increase in viscosity. Meanwhile, the solution exhibits an enhanced shear thinning behavior due to adding more C₁₆TAB than 1 mM. The viscosity increase is ascribed to the physical cross linking of surfactant micelles with NaCMC chains. Furthermore, it is suggested that the enhanced shear thinning behavior results from weak interaction between NaCMC chains and C₁₆TAB micelles.     

Rheology and microstructure studies of SDS/CTAB/H2O system

Phase behavior of mixed sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) aqueous solution was studied. The rheological properties and microstructure were investigated using a rheostat and freeze-fracture technique and are shown to be closely related to the phase behavior. Experimental investigations reveal two symmetrical aqueous two-phase systems (ATPS) in the ternary phase diagram of SDS/CTAB/H₂O system. In the surfactant rich phase of ATPS or in the adjacent stoichiometric state of ATPS, the system has high viscosity because of its long range ordered structure. Lamellar phase was found in the high viscosity samples in which the cationic and anionic surfactant are in 1: 3 or 3: 1 stoichiometry. In addition, the viscosity has a tendency to increase when salt was added to the solution. The viscosity increase is due to the salt can screen the repulsion between different charged headgroups and thus reduces the effective size of surfactants and facilitates the spherical or rod likes micelles to be transformed to worm-like micelles which can form hexagonal or liquid crystal phases. Large-size salt ions like sodium sulfate (especially organic salt ions) have more significant effect on the surfactant solution viscosity. The text was submitted by the authors in English.     

Rheological evidence for the existence of subphases in the liquid crystalline 4-n-alkoxybenzoic acids

The rheological behaviour of the homologous series, the alkyloxybenzoic acids, has been studied at steady flow and small amplitude oscillatory shear. The temperature dependencies of the viscosity were compared with differential scanning calorimetry data in order to estimate pretransitional phenomena in mesophases. The values of the viscosity and flow activation energy (E) can be indicative of the mesophase state. 4-n-pentyloxybenzoic acid yields a classic nematic (N) phase while the next homologues show a cybotactic nematic phase having a higher E value. The N phase is a Newtonian fluid of lower viscosity than that of the isotropic phase. The cybotactic nematic phase by its rheological properties takes an intermediate position between the N phase and a smectic C (SmC) phase. The SmC phase is a viscoelastic and viscoplastic medium. The SmC phase of 4-n-octyloxy-, 4-n-nonyloxy-, 4-n-decyloxy- and 4-n-dodecyloxybenzoic acid can exist in high- and low-ordered states. The more ordered smectic phase is characterised by higher stiffness, viscosity and yield stress than those of the less ordered. The SmC phase of 4-n-hexadecyloxybenzoic acid is characterised by the only state with unstable value of apparent viscosity. The phase state and the transition temperature can be dependent on the thermal history of the sample and a mechanical shear.     

Phase equilibrium and rheology of poly(1-trimethylsilyl-1-propyne) solutions

The phase equilibrium and rheological properties of poly(1-trimethylsilyl-1-propyne) solutions obtained with tantalum catalysts are studied. For three polymers with different molecular masses, phase diagrams are determined in a number of solvents. From these diagrams, the Hansen solubility parameters of poly(1-trimethylsilyl-1-propyne) are calculated by the method proposed in this work. Dilute solutions of poly(1-trimethylsilyl-1-propyne) behave as Newtonian liquids, whereas the viscosity of viscoelastic concentrated systems decreases as the shear rate grows. The molecular and rheological characteristics of studied poly(1-trimethylsilyl-1-propyne) samples are compared with the samples prepared with NbCl₅ catalysts. Poly(1-trimethylsilyl-1-propyne) obtained with a catalytic system involving tantalum pentachloride is characterized by high intrinsic viscosity and solution viscosity compared to poly(1-trimethylsilyl-1-propyne) prepared with niobium catalyst. The difference in properties is due to the dissimilar ratios of cis and trans units in the samples.