Nonlinear rheology for threadlike micelles of tetraethylammonium perfluorooctyl sulfonate

Nonlinear rheological features were investigated for an aqueous solution of tetraethylammonium perfluorooctyl sulfonate (C₈F₁₇SO₃ ^–N⁺(C₂H₅)₄; abbreviated as FOSTEA). In the solution (c=0.045 mol/l; 28.3 g/l), spherical micelles of FOSTEA were connected with each other to form threads of pearl-necklace shape. These threads were further organized into a transient network to exhibit linear relaxation characteristic of living polymers, single-mode terminal relaxation widely separated from faster relaxation processes. Nonlinear relaxation experiments against large step-strains γ(≤8) revealed that the terminal relaxation mode had a γ-insensitive relaxation time but its relaxation intensity exhibited significant damping (much stronger than that for entangled polymers). In contrast, the relaxation time and intensity for the fast relaxation modes first increased and then decreased with increasing γ. Under shear flow, the FOSTEA threads exhibited strong thinning of the viscosity. These nonlinear features of the FOSTEA threads were compared with those of other threadlike micelles, analyzed on the basis of an empirically introduced constitutive equation, and discussed in relation to strain/low-induced scission of the living threads. Received: 20 February 1998 Accepted: 30 July 1998     

Influence of molecular parameters on the stress dependence of viscous and elastic properties of polypropylene melts in shear

The stress dependencies of the steady-state viscosity η and, particularly, that of the steady-state elastic compliance J _e of various linear isotactic polypropylenes (PP) and one long-chain branched PP are investigated using creep-recovery tests. The creep stresses applied range from 2 to 10,000 Pa. In order to discuss the stress-dependent viscosity η and elastic compliance J _e with respect to the influence of the weight average molar mass M _w and the polydispersity factor M _w/M _n the PP are characterized by SEC–MALLS. For the linear PP, linear steady-state elastic compliances J_e⁰J_{\rm e}^0 in the range of 10^− 5–10^− 3 Pa^− 1 are obtained depending on the molar mass distribution. J_e⁰J_{\rm e}^0 of the LCB-PP is distinctly higher and comes to lie at around 10^− 2 Pa^− 1. J_e⁰J_{\rm e}^0 is found to be independent of M _w but strongly dependent on polydispersity. η and J _e decrease with increasing stress. For the linear PP, J _e as a function of the stress τ is temperature independent. The higher M _w/M _n the stronger is the shear thinning of η and the more pronounced is the stress dependence of J _e. For the LCB-PP, the strongest stress dependence of η and J _e is observed. Furthermore, for all PP J _e reacts more sensitively to an increasing stress than η. A qualitative explanation for the stronger stress dependence of J _e compared to η is given by analyzing the contribution of long relaxation times to the viscosity and elasticity.     

Vortex ring generation due to the coalescence of a water drop at a free surface

 Results are presented of an experimental investigation of vortex ring formation by a fluid drop contacting a free surface with negligible velocity. The pool fluid is mixed with fluorescein dye, and a laser sheet is used to illuminate a plane of the flow. A series of representative images is recorded by a CCD camera and speculation is made regarding specific sources of vorticity flux through the free surface. Two scaling analyses previously presented by other investigators are demonstrated to be equivalent under the assumptions of this experiment, and they provide the motivation for a series of test runs in which the duration of the coalescence process, τ_*, is related to variations in drop diameter L and fluid surface tension σ. Experimental results are in agreement with the analyses, showing τ_*∼σ^-1/2 and τ_*∼L ^3/2. Received: 22 December 1995 / Accepted: 15 October 1996     

Rheological behavior of dilute solutions of a side-chain liquid-crystalline polysiloxane in 4,4′-n-octylcyanobiphenyl

The electrorheological (ER) behavior and stress transient response of dilute solutions of a side-chain liquid-crystalline polysiloxane (LCP) in 4,4′-n-octylcyanobiphenyl (8CB) is studied. In the flow-tumbling regime of 8CB, i.e. from T = 34–38 °C, the stress transients of both 8CB and LCP/8CB solutions show oscillatory responses, but with shorter oscillation periodicities for the solution. In the flow-aligning regime of 8CB, i.e. at 39 and 40 °C, a transformation to flow-tumbling is observed in the stress transients of the LCP/8CB solution. In both cases, analysis of the transient responses indicates that the change in Leslie viscosity coefficients on dissolving the LCP are δα₂ < 0 and δα₃ > 0. The amplitude of the ER response, defined as the viscosity difference between the on and off states, Δη = η_on − η_off, is only weakly affected by the dissolution of LCP. These rheological results can be interpreted consistently using a modified version of a hydrodynamic theory by Brochard, provided an additional dissipation mechanism is included, which derives from the presence of an elastic torque between director rotation and LCP orientation. Received: 8 September 1999/Accepted: 13 December 1999     

Rheology of poly(methyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-styrene) particles suspended in water: effects of electrostatic surface layer

 Linear and nonlinear viscoelastic properties were examined for aqueous suspensions of monodisperse poly(methyl methacrylate-co-styrene) (MS) particles having the radius a ₀ =45 nm and the volume fractions φ=0.428−0.448. These particles had surface charges and the resulting electrostatic surface layer (electric double layer) had a thickness of t_s=5.7 nm. At low frequencies in the linear viscoelastic regime, the MS particles behaved approximately as the Brownian hard particles having an effective radius a _eff=a ₀ + t_s, and the dependence of their zero-shear viscosity η₀ on an effective volume fraction φ_eff (={a _eff/a ₀}³φ) agreed with the φ dependence of η₀ of ideal hard-core silica suspensions. In a range of φ_eff < 0.63, this φ_eff dependence was well described by the Brady theory. However, the φ_eff dependence of the high-frequency plateau modulus was weaker and the terminal relaxation mode distribution was narrower for the MS suspensions than for the hard-core suspensions. This result suggested that the electrostatic surface layer of the MS particles was soft and penetrable (at high frequencies). In fact, this “softness” was more clearly observed in the nonlinear regime: the nonlinear damping against step strain was weaker and the thinning under steady shear was less significant for the MS suspension than for the hard-core silica suspensions having the same φ_eff. These weaker nonlinearities of the concentrated MS particles with φ_eff∼ 0.63 (maximum volume fraction for random packing) suggested that the surface layers of those particles were mutually penetrating to provide the particles with a rather large mobility. Received: 10 July 2001 Accepted: 2 November 2001     

Non-linear rheology and flow-induced transition of a lamellar-to-vesicle phase in ternary systems of alkyldimethyl oxide/alcohol/water

 The time-dependent transformation of an ionically charged lamellar phase (L _α-phase) into a vesicle phase under the influence of shear is investigated using rheological and conductivity measurements. The L _α-phase consists of the zwitterionic surfactant tetradecyldimethylaminoxide (C₁₄DMAO), hexanol, oxalic acid and water. The experiments were carried out on the L _α-phase in a well defined state. It was prepared by a special route from the neighbouring L ₃-phase that consists of 100 mM C₁₄DMAO, 250 mM hexanol and 5 mM oxalicdiethylester (OEE). The OEE hydrolyses in the L ₃ -phase to oxalic acid and ethanol. The result is a virgin L _α-phase which consists of stacked bilayers and which has not been exposed to shear. When this low-viscous phase is subjected to shear it is transformed into a highly viscous vesicle phase. The transformation of the L _α-phase into vesicles under constant shear was monitored by recording the viscosity and conductivity with time. It is observed that at least three different time constants can be distinguished in the transformation process. The conductivity passes through a minimum (τ₁) in the direction of shear. The viscosity first passes through a minimum (τ₂) and then over a maximum (τ₃). It is concluded that τ₁ belongs to the complete alignment of the bilayer parallel to the wall, τ₂ to the beginning of the break-up of the bilayers to the vesicles and τ₃ to the complete transformation of the L _α- to the vesicle phase. When the shear rate was varied, it was noted that the product of the time constants and shear is constant. Received: 30 June 1999/Accepted: 30 August 1999     

Influence of NaClO3 on the rheological behaviour of a micellar solution of CPCl

It is now well know that a small addition of salt to a micellar solution often increases the zero-shear viscosity η₀ of the solution, the understanding of the behaviour at high salt content is more questionable. In this situation, addition of more salt induces a decrease of η₀. In this experimental work we investigate the linear and non-linear rheological behaviour of a new micellar system: CPCl (surfactant)/NaClO₃ (salt). Studies of the evolution of η₀ as well as G₀ (the elastic modulus) or τ_R (the relaxation time) are in agreement with the hypothesis of a diminution of the mean micellar length when, after the maximum η₀, the salt content increases. In the non-linear behaviour (non-Newtonian viscosity) the evolution of γ˙ _c, (which defines the occurrence of the shear thinning) with salt concentration C_S is also in agreement with such a hypothesis. Received: 29 March 1999/Accepted: 20 March 2000     

Yield stress of structured fluids measured by squeeze flow

Various structured fluids were placed between the parallel circular plates of a squeeze-flow rheometer and squeezed by a force F until the fluid thickness h was stationary. Fluid thickness down to a few microns could be measured. Most fluids showed two kinds of dependence of f on h according to an experimentally-determined thickness h ^*. If h > h ^* then F varied in proportion to h ⁻¹ as predicted by Scott (1931) for a fluid with a shear yield stress τ₀. The magnitude of τ₀ from squeeze-flow data in this region was compared with the yield stress measured by the vane method. For some fluids τ₀ measured by squeeze flow was less than the vane yield stress, suggesting that the yield stress of fluid in contact with the plates was less than the bulk yield stress. If h < h ^* then F varied approximately as h ^−5/2 and the squeeze-flow data in this region analysed with Scott's relationship gave a yield stress which increased as the fluid thickness decreased. This previously unreported effect may result from unconnected regions of large yield stress in the fluid of size similar to h ^* which are not sensed by the vane and which become effective in squeeze flow only when h < h ^*. Received: 13 December 1999/Accepted: 4 January 2000     

Free volume dependence of polymer viscosity

The Simha–Somcynsky (S–S) equation of state (eos) was used to compute the free volume parameter, h, from the pressure–volume–temperature (PVT) dependencies of eight molten polymers. The predicted by eos variation of h with T and P was confirmed by the positron annihilation lifetime spectroscopy; good agreement was found for h(P = constant) = h(T) as well as for h(T = constant) = h(P). Capillary shear viscosity (η) data of the same polymers (measured at three temperatures and six pressures up to 700 bars), were plotted as logη vs 1/h, the latter computed for T and P at which η was measured. In previous works, such a plot for solvents and silicone oils resulted in a “master curve” for the liquid, in a wide range of T and P. However, for molten polymers, no superposition of data onto a “master curve” could be found. The superposition could be obtained allowing the characteristic pressure reducing parameter, P*, to vary. The necessity for using a “rheological” characteristic pressure reducing parameter, P*_R = κP*, with κ = 1 to 2.1 indicates that the free volume parameter extracted from the thermodynamic equilibrium data may not fully describe the dynamic behavior. After eliminating possibility of other sources for the deviation, the most likely culprit seems to be the presence of structures in polymer melts at temperatures above the glass transition, T _g. For example, it was observed that for amorphous polymers at T ≅ 1.52T _g the factor κ = 1, and the deviation vanish.     

Recoverable strains and retardation times of monodisperse suspensions of silicon dioxide spheres in poly(dimethylsiloxane)

Steady-state viscosities η, steady-state recoverable strains γ _rs and characteristic retardation time τ _1/2 were measured for suspensions of monodisperse silicon dioxide (SiO₂) spheres in poly(dimethylsiloxane) (PDMS) with various volume fractions Φ of the suspended spheres at various creep stresses σ ₀. Two different regions are found in plots of η/η _m vs γ _rs, where η/η _m denotes the relative viscosity of the suspensions. In one region, η/η _m is proportional to γ _rs, while γ _rs is independent of η/η _m in the other region. In both regions, τ _1/2 is the functions of the shear strain rate in the steady-state of creep test independently of Φ. The origin of the elasticity is related to the ‘maximally distorted’ cages recovered owing to the repulsive interaction between the SiO₂ spheres and recovery of the cages in the shear-induced clusters of the suspended spheres.     

Shear and elongational flow behavior of acrylic thickener solutions

We investigate the effect of hydrophobic aggregation in alkali-swellable acrylic thickener solutions on shear and extensional flow properties at technically relevant polymer concentrations using the commercial thickener Sterocoll FD as model system. Apparent molecular weight of aggregates in water is M _w  ≈ 10⁸ g/mol and decreases by more than an order of magnitude in ethanol. Zero shear viscosity η ₀ is low and shear thinning is weak compared to the high molecular weight of the aggregates. Linear viscoelastic relaxation is described by the Zimm theory up to frequencies of 10⁴ rad/s, demonstrating that no entanglements are present in these solutions. This is further supported by the concentration dependence of η ₀ and is attributed to strong association within the aggregates. Extensional flow behavior is characterized using the capillary break-up extensional rheometry technique including high-speed imaging. Solutions with ϕ ≥ 1% undergo uniform deformation and show pronounced strain hardening up to large Hencky strains. Elongational relaxation times are more than one order of magnitude lower than the longest shear relaxation times, suggesting that aggregates cannot withstand strong flows and do not contribute to the elongational viscosity.

A unified approach to closed-form solutions of moving heat-source problems

A closed-form model for the computation of temperature distribution in an infinitely extended isotropic body with a time-dependent moving-heat sources is discussed. The temperature solutions are presented for the sources of the forms: (i) ₀₁(t)=₀ exp(−λt), (ii) ₀₂(t) =₀(t/t ^*)exp(−λt), and ₀₃(t)=₀[1+a cos(ωt)], where λ and ω are real parameters and t ^* characterizes the limiting time. The reduced (or dimensionless) temperature solutions are presented in terms of the generalized representation of an incomplete gamma function Γ(α,x;b) and its decomposition C _Γ and S _Γ. The solutions are presented for moving, -point, -line, and -plane heat sources. It is also demonstrated that the present analysis covers the classical temperature solutions of a constant strength source under quasi-steady state situations. Received on 13 June 1997     

Nonlinear rheology of concentrated spherical silica suspensions: 3. Concentration dependence

Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically dispersed in the media in the quiescent state, and their effective volume fraction φ_eff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σ_B due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced anisotropy in the particle distribution that resulted in decreases of σ_B/γ. The damping became stronger for larger φ_eff. This φ_eff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φ_eff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σ_B/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η₊ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γ_d and γ_s for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φ_eff. This φ_eff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φ_eff. Received: 26 June 1998 Accepted: 9 December 1998     

Testing viscometric predictions of the internal viscosity model,using dilute viscous theta solutions

A stress-symmetrized internal viscosity (I.V.) model for flexible polymer chains, proposed by Bazua and Williams, is scrutinized for its theoretical predictions of complex viscosity ^* () = – i and non-Newtonian viscosity (), where is frequency and is shear stress. Parameters varied are the number of submolecules,N (i.e., molecular weightM = NM _s ); the hydrodynamic interaction,h ^*; and/f, where andf are the I.V. and friction coefficients of the submolecule. Detailed examination is made of the eigenvalues _p (N, h ^*) and how they can be estimated by various approximations, and property predictions are made for these approximations.Comparisons are made with data from our preceding companion paper, representing intrinsic properties [], [], [] in very viscous theta solutions, so that theoretical foundations of the model are fulfilled. It is found that [ ()] data can be predicted well, but that [ ()] data cannot be matched at high. The latter deficiency is attributed in part to unrealistic predictions of coil deformation in shear.     

The role of the mathematical mean value theorem (MVT) in rheometry: an easy way to convert apparent flow curves into correct ones

The mean value theorem of integral calculus guarantees that the apparent viscosity η _a can easily be converted into the correct viscosity η. For ordinary liquids there is a direct identity between η _a and η but the apparent shear rate (or apparent shear stress) has to be shifted to the representative shear rate γ˙^ (or representative shear stress τ^). A model free approximation scheme is introduced which implies a constant shift factor. The corresponding approximation for η is acceptable for liquids most commonly encountered. For plastic fluids the relation between η and η _a is more complex since it involves a function depending upon α; the yield stress relative to the maximum stress within the viscometer. Using the same approximation scheme as before the shift factor will involve α as well. The corresponding approximation of η is shown to be acceptable for the whole range of α. Received: 7 February 2000/Accepted: 15 February 2000     

Viscoelastic properties of ultra-high viscosity alginates

Ultra-high viscosity alginates were extracted from the brown seaweeds Lessonia nigrescens (UHV_N, containing 61% mannuronate (M) and 2% guluronate (G)) and Lessonia trabeculata (UHV_T, containing 22% M and 78% G). The viscoelastic behavior of the aqueous solutions of these alginates was determined in shear flow in terms of the shear stress σ ₂₁, the first normal stress difference N ₁, and the shear viscosity η in isotonic NaCl solutions (0.154 mol/L) at T = 298 K in dependence of the shear rate [(g)\dot]\dot{\gamma} for solutions of varying concentrations and molar masses (3–10 × 10⁵ g/mol, homologous series was prepared by ultrasonic degradation). Data obtained in small-amplitude oscillatory shear (SAOS) experiments obey the Cox–Merz rule. For comparison, a commercial alginate with intermediate chemical composition was additionally characterized. Particulate substances which are omnipresent in most alginates influenced the determination of the material functions at low shear rates. We have calculated structure–property relationships for the prediction of the viscosity yield, e.g., η–M _w–c–[(g)\dot]\dot{\gamma} for the Newtonian and non-Newtonian region. For the highest molar masses and concentrations, the elasticity yield in terms of N ₁ could be determined. In addition, the extensional flow behavior of the alginates was measured using capillary breakup extensional rheometry. The results demonstrate that even samples with the same average molar mass but different molar mass distributions can be differentiated in contrast to shear flow or SAOS experiments.     

On a Crystalline Variational Problem, Part II:¶BV Regularity and Structure of Minimizers on Facets

For a nonsmooth positively one-homogeneous convex function φ:ℝ ⁿ → [0,+∞[, it is possible to introduce the class ?_φ (ℝ ⁿ ) of smooth boundaries with respect to φ, to define their φ-mean curvature κ_φ, and to prove that, for E∈?_φ (ℝ ⁿ ), κ_φ∈L ^∞(δE) [9]. Based on these results, we continue the analysis on the structure of δE and on the regularity properties of κ_φ. We prove that a facet F of δE is Lipschitz (up to negligible sets) and that κ_φ has bounded variation on F. Further properties of the jump set of κ_φ are inspected: in particular, in three space dimensions, we relate the sublevel sets of κ_φ on F to the geometry of the Wulff shape ?_φ≔{φ≤ 1 }. Accepted October 11, 2000?Published online 14 February, 2001     

On a Crystalline Variational Problem, Part I:¶First Variation and Global L∞ Regularity

Let φ:ℝ ⁿ → [0,+∞[ be a given positively one-homogeneous convex function, and let ?_φ≔{φ≤ 1 }. Pursuing our interest in motion by crystalline mean curvature in three dimensions, we introduce and study the class ?_φ (ℝ ⁿ ) of “smooth” boundaries in the relative geometry induced by the ambient Banach space (ℝ ⁿ , φ). It can be seen that, even when ?_φ is a polytope, ?_φ(ℝ ⁿ ) cannot be reduced to the class of polyhedral boundaries (locally resembling ∂?_φ). Curved portions must be necessarily included and this fact (as well as the nonsmoothness of ∂?_φ) is the source of several technical difficulties related to the geometry of Lipschitz manifolds. Given a boundary δE in the class ?_φ(ℝ ⁿ ), we rigorously compute the first variation of the corresponding anisotropic perimeter, which leads to a variational problem on vector fields defined on δE. It turns out that the minimizers have a uniquely determined (intrinsic) tangential divergence on δE. We define such a divergence to be the φ-mean curvature κ_φ of δE; the function κ_φ is expected to be the initial velocity of δE, whenever δE is considered as the initial datum for the corresponding anisotropic mean curvature flow. We prove that κ_φ is bounded on δE and that its sublevel sets are characterized through a variational inequality.     

Experimental studies on drag reduction and rheology of mixed cationic surfactants with different alkyl chain lengths

Experimental studies of the effects of mixtures of cationic surfactants on their drag reduction and rheological behaviors are reported. Cationic alkyl trimethyl quaternary ammonium surfactants with alkyl chain lengths of C₁₂ and C₂₂ were mixed at different molar ratios (total surfactant concentrations were kept at 5 mM with 12.5 mM sodium salicylate (NaSal) as counterion). Drag reduction tests showed that by adding 10% (mol) of C₁₂, the effective drag reduction range expanded to 4–120 °C, compared with 80–130 °C with only the C₂₂ surfactant. Thus mixing cationic surfactants with different alkyl chain lengths is an effective way of tuning the drag reduction temperature range. Cryo-TEM micrographs revealed thread-like micellar networks for surfactant solutions in the drag reducing temperature range, while vesicles were the dominant microstructures at non-drag reducing temperatures. High extensional viscosity was the main rheological feature for all solutions except 50% C₁₂ (mol) solution, which also does not show strong viscoelasticity. It is not clear why this low extensional viscosity solution with relatively weak viscoelasticity is a good drag reducer. Received: 3 November 1999/Accepted: 5 January 2000     

Three views of viscoelasticity for Cox–Merz materials

A slight rearrangement of the classical Cox and Merz rule suggests that the shear stress value of steady shear flow, , and complex modulus value of small amplitude oscillatory shear, G^∗(ω) = (G^′2 + G^″2)^1/2, are equivalent in many respects. Small changes of material structure, which express themselves most sensitively in the steady shear stress, τ, show equally pronounced in linear viscoelastic data when plotting these with G^∗ as one of the variables. An example is given to demonstrate this phenomenon: viscosity data that cover about three decades in frequency get stretched out over about nine decades in G^∗ while maintaining steep gradients in a transition region. This suggests a more effective way of exploiting the Cox–Merz rule when it is valid and exploring reasons for lack of validity when it is not. The τ −G^∗ equivalence could also further the understanding of the steady shear normal stress function as proposed by Laun.