Rheological studies of aqueous alkylpolyglucoside surfactant solutions

Alkylpolyglucosides (C _Y G _X ) are industrial products of mixtures consisting of a hydrocarbon chain with Y carbon atoms linked to X sugar residues. Based on detailed analytical investigation of technical grade alkylpolyglucosides (C_8–10G _X , C_12–14G _X and C_8–16G _X )/water systems using high-performance liquid chromatography in combination with a special kind of mass spectroscopy their rheological behaviour is discussed and compared to the rheological behaviour of pure alkyl monoglycosides (C₈G₁ and C₁₀G₁) in water. The rheological properties that exhibit a dependence on the alkyl chain length, Y, and the degree of polymerisation, X, are investigated by rotation and oscillation experiments over an extended concentration range. The Maxwell model fits the frequency dependence of the dynamic functions fairly well. The viscosity shows an Arrhenius-like dependence on temperature. A comparison is drawn between the monoglucosides and the polyglucosides, which shows that the rheological properties are more sensitive to the a change in chain length than in the degree of polymerisation. Phase transitions, especially liquid-crystalline to isotropic solutions, phase split into two coexisting liquid phases, and could be followed using visual observation and rheology. Depending on the difference in the rheological properties of the corresponding phases, viscoelastic measurements showed these transitions clearly. Additionally, the changes in viscosities were measured after addition of a second surfactant. Received: 4 January 1999 Accepted in revised form: 12 April 1999     

Mg-Fe-HTlc对黄原胶流变性的影响

研究了荷负电高分子物质黄原胶(XG)及类水滑石HTlc/XG复合悬浮体系的流体类型及触变性. 结果发现, 供试体系流变曲线都符合Herschel-Bulkley模型. 在0.05～0.20 wt%范围内, 随XG含量增加, XG溶液表现出由假塑性流体到塑性流体的转变, 没有触变性|1.5 wt%纯HTlc悬浮体系为牛顿流体, 无触变性. 当HTlc/XG质量比为29.0～6.5时(复合悬浮体系固含量保持为1.5%), 体系均表现为假塑性流体|除HTlc/XG质量比为29.0体系无触变性外, 其它复合悬浮体系均表现为正触变性.     

Experimental Study and Numerical Modeling of Rheological and Flow Behavior of Xanthan Gum Solutions Using Artificial Neural Network

This study investigated effect of temperature, concentration, and shear rate on rheological properties of xanthan gum aqueous solutions using a Couette viscometer at temperatures between 25°C and 55°C and concentrations of 0.25 wt% to 1.0 wt%. The Herschel–Bulkley model described very well the non-Newtonian behavior of xanthan gum solutions. Shear rate, temperature, and concentration affected apparent viscosity and an equation was proposed for the temperature and concentration effect valid for each shear rate. This article also presents an artificial neural network (ANN) model to predict apparent viscosity. Based on statistical analysis, the ANN method estimated viscosity with high accuracy and low error.     

Viscoelastic behaviors and molecular motions of highly syndiotactic poly(vinyl alcohol) fibers

The viscoelastic behavior and molecular motion of highly syndiotactic poly(vinyl alcohol) (S‐PVA) fibers with a dyad syndiotacticity (r) of 69% were studied by dynamic mechanical thermal analysis and wide‐angle X‐ray diffraction and compared with those of atactic poly(vinyl alcohol) (A‐PVA) fibers with r = 54%. The β_c dispersion, based on the molecular motion of the chain molecules in the crystalline regions, was observed for A‐PVA around 120–140 °C, and the only primary (α_c) dispersion was observed for S‐PVA around 180 °C. The thermal expansion coefficients for the a and c axes of the A‐PVA crystal changed discontinuously around 120 °C, which corresponded to the β_c dispersion. For S‐PVA, the coefficient for the (002) plane changed discontinuously around 100 °C, similarly to A‐PVA, but that for the (100) plane remained unchanged between 20 and 220 °C. These results showed that the intermolecular hydrogen bonding of S‐PVA was stronger in the direction of the a axis than in the other directions, suppressing the β_c dispersion. The storage modulus and thermal expansion coefficient of the (020) plane (molecular axis) of S‐PVA decreased markedly around 180 °C, and this indicated that the α_c dispersion was due to the torsional motion of the molecular chains in the crystalline regions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 800–808, 2004     

Phase behaviors of polymer solutions using molecular simulation technique

Phase behaviors of polymer solutions are estimated using a combination of thermodynamic models and molecular simulation technique. In general, many parameters of binary systems are determined by fitting a thermodynamic model with experimental data. In this study, we obtained all parameters using molecular simulation. To take the specific interaction into account, we assume that it only occurs between a solvent molecule and a specific group. Our results show that the theoretical treatment accounting for the specific interaction gives more accurate predictions than those without consideration of specific interaction. Also, our approach describes the phase equilibria of various polymer solutions over the entire concentration remarkably well.     

Rheological properties and interfacial slip of a multilayer structure under dynamic shear

Interfacial slip between polymer melt under steady shear has been studied using a simplified multilayer structure. In this investigation, interfacial slip under dynamic shear was studied by calculating the angular displacements of the multilayer structure and its component layers. On the basis of the angular displacements, a slip index was defined to quantify the degree of interfacial slip. A relationship governing the rheological behavior of the multilayer structure under slip and nonslip condition was established. These results were correlated with equations derived from consideration of energy equilibrium in the multilayer structure. Polymer multilayer structures of high‐density polyethylene/polystyrene and liquid crystal polymer(LCP)/poly ethylene naphthalate(PEN) were investigated. Of all the polymers investigated, large interfacial slip was found at LCP/PEN interface under dynamic shear. The high rigidity and alignment along the interface of LCP molecules was believed to prevent chain entanglement in the interfacial layer and therefore promote interfacial slip at the interface. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2683–2693, 2005     

Rheological and structural studies of linear polyethylene melts under planar elongational flow using nonequilibrium molecular dynamics simulations

We present various rheological and structural properties of three polyethylene liquids, C50H102, C78H158, and C128H258, using nonequilibrium molecular dynamics simulations of planar elongational flow. All three melts display tension-thinning behavior of both elongational viscosities, eta1 and eta2. This tension thinning appears to follow the power law with respect to the elongation rate, i.e., eta approximately epsilon(b), where the exponent b is shown to be approximately -0.4 for eta1 and eta2. More specifically, b of eta1 is shown to be slightly larger than that of eta2 and to increase in magnitude with the chain length, while b of eta2 appeared to be independent of the chain length. We also investigated separately the contribution of each mode to the two elongational viscosities. For all three liquids, the intermolecular Lennard-Jones (LJ), intramolecular LJ, and bond-stretching modes make positive contributions to both eta1 and eta2, while the bond-torsional and bond-bending modes make negative contributions to both eta1 and eta2. The contribution of each of the five modes decreases in magnitude with increasing elongation rate. The hydrostatic pressure shows a clear minimum at a certain elongation rate for each liquid, and the elongation rate at which the minimum occurs appears to increase with the chain length. The behavior of the hydrostatic pressure with respect to the elongation rate is shown to correlate with the intermolecular LJ energy from a microscopic viewpoint. On the other hand, R(ete)2 and R(g)2 appear to be correlated with the intramolecular LJ energy. The study of the effect of the elongational field on the conformation tensor c shows that the degree of increase of tr(c)-3 with the elongation rate becomes stronger as the chain length increases. Also, the well-known linear reaction between sigma and c does not seem to be satisfactory. It seems that a simple relation between sigma and c would not be valid, in general, for arbitrary flows.     

Rheological properties of immiscible polymer blends under parallel superposition shear flow

The small amplitude oscillations can be superimposed parallelly on steady shear flows. The resulting moduli provide information about time‐ and shear‐dependent microstructure. For this purpose, model blends composed of polydimethylsiloxane and polyisobutylene with the viscosity ratio of 7.9 and 0.25 are investigated. The resulting moduli are compared with the results derived from numerical calculation as well as analytical solutions, developed here by introducing the conditions under parallel superposition flow field into MM model. Good agreement is found in the interfacial contribution of the storage moduli for blend with low volume fraction. Moreover, detailed analysis on hydrodynamic interaction between droplets is given to explain the discrepancies. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 431–440, 2008     

Determination of molecular parameters from polymer solutions in shear flow

A light scattering photometer with a double cylinder shear cell has been developed which allows detection not only in one plane as usual, but in a half-spherical range around the scattering volume. The anisotropic scattering behavior of oriented and deformed polymer molecules in dilute solution was investigated. All measurements were performed on polystyrene in several viscous solvents. From measurements in the plane of flow the average orientation angle was determined. By variation of detector position and wavelength of the primary beam, the determination of all three axes of the molecular gyration space of polymer coils was possible. Compared to predictions of the well-known dynamic theories by Kuhn, Rouse and Zimm, corresponding orientation data were found while the molecular deformation ratio shows much lower values than expected.     

Further EPR studies of molecular motions in polymer/plasticizer mixtures

Molecular motions in mixtures of the side chain polymer—poly(vinyl acetate) and dibuthyl phthalate were studied as a functionof polymer concentration and temperature using the technique of paramagnetic resonance (EPR). When the small spherical probe tempol (TPL) was used, we were able to approximate the observed EPR spectrum with a simulation using a single rotational correlation time τ. The peviously developed Grest–Cohen all-temperature model matched the Arrhenius polts. The EPR spectra from a cigar-shaped cholestane (COL) probe could not be adequately matched by single τ simulation when the polymer was at temperatures somewhat above the glass to rubber transition temperature (T_g). Points corresponding to these temperatures were left of the Arrhenius plot and a discontinuity was observed where the gap in the data occurred. As the concentration of plasticizer was increased, we found that the discontinuity became less steep, but the τ at which the gap occurs was always ≈ 10^?8. The spectra observed at the temperature region of the gap were approximately 50–50 composites of experimental spectra observed at ± K. In both the TPL and COL cases, there was evidence of the existence of multiple correlation times. Preliminary studies of other polymers, both with and without side chains, also indicated the existence of the gap when COL is used as the probe. © 1993 John Wiley & Sons, Inc.     

Rheological properties of aqueous solutions of polyethylene glycols with various molecular weights

The dependences of the kinematic viscosity of dilute aqueous solutions of polyethylene glycols (PEGs) with various molecular weights in the temperature range of 293.15–323.15 K were investigated. The intrinsic viscosity, the Huggins constant, and the activation energy of a viscous flow were calculated for these solutions. Proposals regarding the structure of polymer macromolecules in solution are made. The constants of the Mark-Kuhn-Hauvink equation required to estimate the polymer molecular weights were determined for PEG-water systems at various temperatures.     

Association under shear flow in aqueous solutions of pectin

Effects of oscillatory and steady shear flows on intermolecular associations in dilute and semidilute aqueous solutions of pectin in the absence and presence of the hydrogen bond breaking agent urea are reported. A weak oscillatory shear perturbation builds up, depending on polymer concentration, multichain aggregates or networks in the course of time and these association structures are mainly stabilized through hydrogen bonds. The association effect is more pronounced at higher concentrations, and the growth of intermolecular interactions is inhibited by the addition of urea. Steady shear measurements on the pectin-water solutions reveal shear thickening at low shear rates for all the concentrations, except the lowest one, and disruption of intermolecular junctions at high shear rates. In the presence of urea, no shear thickening is detected. The polymer concentration dependence of the viscosity at a low shear rate can be described by a power law η ∼ c^x, with x = 1.9 and 1.4 without and with urea, respectively. When a low constant shear rate is applied to pectin solutions and this monitoring shear rate is interrupted periodically by transitory high shear rates perturbations during a short time, prominent association structures evolve upon return to the monitoring shear rate. This effect is more evident at a lower polymer concentration, and in the presence of urea, the growth of the association complexes is damped. The shear-induced alignment and stretching of polymer chains and the formation of hydrogen-bonded structures are analyzed in the framework of a model, where cooperative zipping of stretched chains play an important role. Viscosity enhancement is found for a semidilute pectin-water solution in the presence of moderate levels of salt addition (NaCl), suggesting that partial screening of electrostatic interactions promotes growth of energetic cross-links.     

Rheological measurements and light-scattering experiments of dilute solutions of high molecular polystyrene. Light-scattering of flowing polymer solutions

We describe the behavior of dilute polymer solutions by means of light-scattering under shear flow. Solution properties of polystyrene in benzene over a wide range of molecular weight has been studied to determine the coefficientsa andK of the Mark-Houwink relationship and to estimate the rheological conditions with regard to light-scattering experiments of flowing polymer solutions. The investigations were carried out to measure the shear-rate dependence of macromolecules in solution, e.g., to observe an orientation and changing of the mean-square radius of gyration.     

Gelation in solutions of high-molecular-mass polyacrylonitrile under shear deformation

The effect of shear fields on the rate of physical gelation in semidilute solutions of ultra-high-molecular-weight polyacrylonitrile in propylene carbonate and on the structural features of the resulting gels has been studied. At 30–70°C in the uniform shear field, the induction period of gelation decreases from several hours to several seconds with an increase in the shear stress. The patterns of these dependences are rather close at shear stresses above 20 Pa, while significant differences are observed at these temperatures only at low shear stresses (below 15 Pa). Depending on the shear stress, two types of gelation can be distinguished at 70°C. At stresses below 15 Pa, the polymer phase emerging in the course of shear deformation is aligned along shear lines and the sample is macroscopically nonuniform. At higher shear stresses, the structure of the sample is uniform throughout its bulk.     

Rheological studies of the gelation kinetics of Cr+3-polyacrylamide solutions

A new rheological approach for the study of the gelation kinetics of aqueous Cr⁺³ polyacrylamide solutions has been investigated which relies on the assumption that at the gel point, GP, a constant amount of Cr⁺³ will have reacted, independent of the initial Cr⁺³ concentration. From this, a kinetic expression relating GP to the initial concentrations of Cr⁺³ and reactive groups on the polymer has been derived for the case of a crosslinking reaction first order in Cr⁺³ and polymer. Experimental evidence that the amount of Cr⁺³ reacted at the GP is constant for a given polymer and solution pH has been obtained. The good fit of the kinetic expression to the rheological data provides new evidence that the gelation reaction is first order in Cr⁺³ rather than second order as claimed previously.     

Structural studies of lamellar surfactant systems under shear

Recent experimental studies on concentrated surfactant systems are reviewed. Particular attention is focused on the transformation from planar lamellar sheets to multilamellar vesicles. It is discussed whether both of these states are thermodynamic stable, or if the MLV is an artifact of shear induced factors. Recent studies includes the dependence on shear, and dependence on salt and cosurfactants, and thereby related lamellar defects. The review include moreover the demonstration that polymeric amphiphiles dramatically enhance the quality of classical surfactants.     

Grafted polymers under strong shear: Scaling and non-equilibrium Monte Carlo studies

End-grafted polymer chains exposed to strong shear solvent flow in the x-direction are investigated by a non-equilibrium Monte Carlo method using the bond-fluctuating model. The solvent flow is modelled by an enhanced jump rate of monomers in the flow direction. Under strong enough shear flow, the shear force is non-linear with the blob size ζ depending on the shear force and not on the monomer volume fraction ϕ. For the case of a grafted single chain, our data on the end-to-end distance of the polymer for a wide range of shear rate γ agree well with the proposed scaling form and compare reasonably well with the Langevin force law in the extreme strong shear case. Also the scaling for the blob size is derived with ζ = aN^vK(γN^2+v) for some scaling function K, and verified by our simulation data. For the case of a polymer brush, we derive the crossover force scale F^* separating the weak and strong shear regime with F^*a/(kT) = ϕ^v/(3v−1) where v is the usual self-avoiding walk exponent. For the case of a polymer brush under strong shear, the velocity profile, v(z), inside and above the brush is calculated analytically by treating the flow as in a porous medium and solving the Brinkman equation. The solution of the velocity profile is then combined with non-equilibrium Monte Carlo simulation data which allow a self-consistent determination of the chain end-to-end length and the incline angle of the chain. Also we derive the scaling form for the positions x(n) of the nth monomer and verify it by our simulation data. We further obtain an analytical expression for x(n) in terms of the effective viscosity η of the model, given by F = ηav(z). The effective viscosity is also found from our simulation to be ηa²/(kT) ≃ 0.02 ± 0.005.     

Transport properties of acetone aqueous solutions: molecular dynamics simulation and NMR studies

Two quantities η_rel and are applied to study the nonideal acetone–water association mixture. An all-atom acetone model and a TIP5P water model have been adopted for molecular dynamics simulation. We study the transport properties of the system comparing the 's of strong hydrogen bond and weak contact based on transport properties, MD simulations together with NMR experimental data and find good agreement of concentration dependence, which exhibits the cooperation effect.     

Rheological and phase behavior of polyamidobenzimidazole solutions under the effect of temperature and deformation

The viscosities and phase stabilities of solutions of rigid-chain polyamidobenzimidazole and its copolymer with poly(p-phenylene terephthalamide) in dimethylacetamide are investigated during their flow within wide temperature and shear-rate ranges. These systems are characterized by amorphous separation with the lower critical temperature of mixing. In the range of the phase-separation temperature, viscosity passes through a minimum owing to the formation of a microemulsion followed by gelation of the reversible system accompanied by its blurring due to uncompleted phase separation. The temperatures of phase separation and the temperatures of minimum viscosity for the investigated solutions decline with an increase in the polymer concentration and increase with an increase in the shear rate.