Constitutive equation for dilute polymer solutions in strong elongational flow

A constitutive equation is proposed, which is constructed using both phenomenological and structural ideas. In this formulation, the kinematics of the fluid is characterized by the deformation rate and a structural vector. The vector follows an evolutionary law which is inspired by known molecular models. The expression for the stress is given by introducing a dissipative term related to the strong hydrodynamic interaction of the distorted molecules and a deformation term for the molecules, as well as by using the second law of thermodynamics.A study of the general properties of the evolutionary equation and its response in a homogeneous two-dimensional flow provides evidence of the performance of the proposed model.     

Characteristics of HPAM dilute polymer solutions in three elongational flow situations

Previous work has shown that anomalous pressure behaviour occurs when dilute polymer solutions are subjected to elongational flows such as those existing upstream of a capillary tube entrance, of an orifice and of the stagnation point of a Pilot tube probe. Tests have been conducted with aqueous solutions of HPAM at various concentrations using the above three flow geometries. It is shown that pressure anomalies occured when critical values of the ratio between a velocity and length scale, representative of the strain rate, are exceeded. They are proportional to the power of the strain rate with an exponent larger than one. Based on previous and present results, it appears that the polymer solutions' behaviour may be characterized by three parameters: an anomalous stress magnitude, a relaxation time (inverse of the critical strain rate) and the exponent of the power law. The first two parameters depend on the polymer type, concentration and molecular weight, while the third depends only on the polymer type. The anomalous pressure is also affected by the conformation of the molecules as shown by results obtained with HPAM solutions containing varied amounts of NaCl.     

A new elongational rheometer for polymer solutions

Design and operation of a new elongational rheometer for low elastic polymer solutions are described. The free jet elongational rheometer is easy to operate and for suitable operating conditions a transient elongational flow with an approximately constant rate of strain can be realized. In any case, convenient comparative parameters can be obtained. The method of rheological curve fitting leads to a deformation dependent ralaxation time parameter of a modified upper convected Jeffreys-law.     

Stress and neutron scattering measurements on linear polymer melts undergoing steady elongational flow

We use small-angle neutron scattering to measure the molecular stretching in polystyrene melts undergoing steady elongational flow at large stretch rates. The radius of gyration of the central segment of a partly deuterated polystyrene molecule is, in the stretching direction, increasing with the steady stretch rate to a power of about 0.25. This value is about half of the exponent observed for the increase in stress value σ, in agreement with Gaussian behavior. Thus, finite chain extensibility does not seem to play an important role in the strongly non-linear extensional stress behavior exhibited by the linear polystyrene melt.     

Experiments on elongational flow of dilute polymer solutions: Part II: velocity field for the flow through small apertures

Following Part I which reported on the jet reaction and the excess pressure drop, this paper describes the results of flow velocities measured upstream of small apertures for dilute polymer solutions. The results suggest the existence of the two flow regimes reorted by Boger and Cable: the vortex growth regime and the divergent flow regime. The former corresponds to the regime of zero jet reaction and the latter to the regime of positive jet reaction. The axial velocity development for PEO solutions along the center line upstream of the aperture is found to yield an extremely high velocity rise at the onset of the vortex region and to give a nearly constant elongational rate within the vortex region. The constant elongational rate takes values such that the product with the relaxation time is about 0.5. Separan solutions do not provide so high a velocity rise at the onset of the vortex region but show an exponential rate of elongation in the vortex region.It is shown, by using the upper convected Maxwell model, that the steep velocity rise at the onset of the vortex region is given in the simplified flow model and the constant elongational rate within the vortex region holds the elongational stress nearly constant.     

Investigation of failure during elongational flow of polymer melts

A basic study of the mechanisms of necking and ductile failure of polymer melts in uniaxial elongational flow has been carried out. A linear stability analysis was carried out using a White—Metzner convected Maxwell model with a deformation-rate-dependent relaxation time, which varies according to τ = τ_o/(1 + aτ_o[2trd²]^{$\text{1}\text{2}$}). It was shown that filament stability and elongation to break depend upon τ_oE, where E is the elongation rate, and a. At fixed τ_oE, filament stability decreases with increasing a. At small a, stability increases with increasing τ_oE while for a > $\text{1}\text{√3}$, stability decreases with increasing τ_oE. For a material with small a, ductile failure can occur for small τ_oE, but cohesive fracture should be the cause of failure at larger τ_oE. For a material with large a, however, ductile failure always dominates the failure mode. These results are used to interpret failure in elongational flow of low density and high density polyethylene and polypropylene melts and describe how the latter two melts exhibit ductile failure.     

Thickening behaviour of dilute polymer solutions in non-inertial elongational flows

A molecular interpretation is proposed to interpret the thickening behaviour of dilute solutions of high molecular weight flexible polymers in non-intertial flows having an elongational character. A set of new results has been gathered showing that the onset of very high end-pressure losses at high deformation rates in capillary flow can be explained by a flow-induced coil-stretch transition of macromolecules in solution. When a high degree of elongation is achieved a marked increase in viscous dissipation occurs in elongational flows.     

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.

PIV measurements of flow in drying polymer solutions during solvent casting

An experimental method based on confocal microscopy and particle image velocimetry (PIV) is used to characterize the flow in a polymer solution during solvent casting. The flow inside a 200-μm-thick film of a poly(vinyl alcohol) (PVA) solution is visualized near a vertical wall of a mold using confocal microscopy of seed particles during solvent evaporation at 25, 35, and 45°C, and the corresponding velocity vector fields are determined from projections of the confocal images. Flow toward the vertical wall is observed inside the film as well as a slower Marangoni-type counter flow at the film surface during the initial phase of solvent evaporation, resulting from a polymer concentration gradient along the film due to a local variation in evaporation rate. Total volume of the polymer solution in the observation volume as well as solvent evaporation rate are determined as a function of time, both revealing close correlation to average horizontal velocity data from PIV. The PIV measurements show significant differences in the flow velocity fields at different temperatures. The PIV measurements correlate with the solvent evaporation rates as well as the final polymer thicknesses on the vertical wall of the mold. Surface tension and viscosity measurements are taken for different concentrations of PVA solution.     

Experiments on elongational flow of dilute polymer solutions Part I: Jet reaction and excess pressure drop for the flow through small apertures

Experiments have been made with dilute polymer solutions on the reaction of jets issuing from small orifices and the excess pressure drop for orifice and capillary flows.Under the flow conditions with vortices occurring upstream of the aperture, the jet reaction is nearly zero below some mean velocity for PEO solutions and similarly zero below some generalized Reynolds number for Separan solutions. The normalized jet reactions, when they possess positive values, are correlated with the generalized Reynolds number irrespective of the aperture diameters for both kinds of solution.In most cases, the pressure is higher than in the corresponding water flow, but for some flows with no vortex it is lower. For the vortex flow of PEO solutions the normalized excess pressure drop is inversely proportional to the Reynolds number for both orifices and capillaries, while for Separan solutions this quantity is not correlated with the generalized Reynolds number for orifice flow but is correlated with it for capillary flow.     

Branched viscoelastic surfactant solutions and their response to elongational flow

Several years ago, Münstedt and Laun reported on the influence of branching on the elongational flow properties of polymer chains (Münstedt and Laun, 1981). They concluded that, in addition to the molecular weight distribution, the degree of branching strongly affects the degree of strain thickening of the elongational viscosity in such a way that the maximum in this material function increases with branching. In a recent paper by Lin, a ternary system of dodecyldimethylamine oxide-sodium laureth sulphate-sodium chloride surfactant solutions was investigated by CryoTEM and rheology (Lin, 1996). He reported a linear relation between the added sodium chloride and the branching of the wormlike micelles. In this paper we present an investigation of these surfactant solutions in elongational flow. Our results indicate that for branched micellar systems the presence of branching enhances the maximum of the elongational viscosity in the same manner as in the case of polymer melts.     

Transient elongational viscosities of aqueous polyacrylamide solutions measured with an optical rheometer

An anionic polyacrylamide solution was characterized in elongational flow by combining laser-Doppler velocimetry to determine the strain rate in the flow direction and the two-color flow-induced birefringence method to measure the first normal stress difference along the axial centerline of a hyperbolic die. The elongational rate was constant along the axial centerline of the planar hyperbolic die as long as vortices at the die entrance did not occur. The transient elongational viscosity μ ⁺ was determined as a function of the elongational rate. The parameters varied are the Hencky strain rate and the polymer concentration. μ ⁺ showed a pronounced increase over the linear viscoelastic behavior above critical Hencky strains of 1.2 to 1.5; that is, a significant strain hardening could be observed for polyacrylamide solutions. This strain hardening is stronger the higher the elongational rate. A slight enhancement of strain hardening was found by increasing the concentration from 0.5 to 1 g/l. The stress optical coefficient was determined as 1.8 × 10⁻⁷ Pa⁻¹ (0.5 g/l) and 1.2 × 10⁻⁷ Pa⁻¹ (1 g/l).

Shear stress and normal stress measurements of aqueous polymer solutions in a cone-and-plate rheogoniometer

Summary The rheological behaviour of aqueous solutions of Separan AP-30 and Polyox WSR-301 in a concentration range of 10–10000 wppm is investigated by means of a cone-and-plate rheogoniometer. The relation between the shear stress and the shear rate is for lower shear rates characterized by a timet ₀, which is concentration dependent. Both polymers show for 4000 s^–1 < < 10000 s^–1 a behaviour similar to that of a Bingham material, characterized by a dynamic viscosity ₀ and an apparent yield stress ₀, which also depend on the concentration. The inertial forces are measured for water and some other Newtonian liquids. An explanation is given why the theoretical model developed for these forces does not match the experimental values; the shape of the liquid surface is shear rate dependent. To obtain the first normal stress difference, we have to correct for these inertial forces, the surface tension and the buoyancy. The normal forces, measured for Separan AP-30, appear to be a linear function of the shear rate for 350 s^–1 < < 3300 s^–1.

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Zusammenfassung Das rheologische Verhalten wäßriger Polymerlösungen von Separan AP-30 und Polyox WSR-301 wird in einem Konzentrationsgebiet von 10–10000 wppm in einem Kegel-Platte-Rheogoniometer untersucht. Der Zusammenhang zwischen Schubspannung und Schergeschwindigkeit wird für niedrige Schergeschwindigkeiten durch eine konzentrationsabhängige Zeitt ₀ gekennzeichnet. Für Schergeschwindigkeiten 4000 s^–1 < < 10000 s^–1 zeigen beide Polymere ein genähert binghamsches Verhalten, gekennzeichnet durch eine dynamische Viskosität ₀ und eine scheinbare Fließgrenze ₀, welche ebenfalls konzentrationsabhängig sind. Die Trägheitskräfte werden für Wasser und einige newtonsche Öle bestimmt. Die Abweichung der experimentellen Ergebnisse vom theoretischen Modell wird durch die Abhängigkeit der Gestalt der Flüssigkeitsoberfläche von der Schergeschwindigkeit erklärt. Um die Werte der ersten Normalspannungsdifferenz zu erhalten, muß man bezüglich der Trägheitskräfte, der Oberflächenspannung und der Auftriebskräfte korrigieren. Die Normalspannungen für Separan AP-30, gemessen für 350 s^–1 < < 3300 s^–1, zeigen eine lineare Abhängigkeit von der Schergeschwindigkeit.

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c concentration (wppm) - g acceleration of gravity (ms^–2) - K force (N) - K _b buoyant force (N) - K _c force, acting on the cone (N) - K ₀ dimensional constant def. by eq. [24] (N) - K _s force, def. by eq. [22] (N) - M dimensional constant def. by eq. [24] (Ns) - P _s pressure def. by eq. [17] (Nm^–2) - P ₀ average pressure in the liquid atr = 0 (Nm^–2) - P _R average pressure in the liquid atr = R (Nm^–2) - r ₁,r ₂ radii of curved liquid surface (m) - R platen radius (m) - R _w radius of wetted platen area (m) - S _x standard deviation ofx - t ₀ characteristic time def. by eq. [1] (s) - T temperature (°C) - V volume of the submerged part of the cone (m³) - v tangential velocity of liquid (ms^–1) - x distance (m) - angle (rad) - ₀ cone angle (rad) - calibration constant (Nm^–3) - shear rate (s^–1) - dynamic viscosity (mPa · s) - ₀ viscosity def. by eq. [1] (mPa · s) - contact angle (rad) - density (kgm^–3) - static surface tension (Nm^–1) - shear stress (Nm^–2) - ₀ yield stress def. by eq. [1] (Nm^–2) - _c, _p angular velocity (c = cone,p = plate) (s^–1) With 8 figures and 3 tables     

Surface tension measurement of aqueous polymer solutions

The surface tension of aqueous polymer solutions of polyacrylamide (PAM), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), and hydroxyethyl cellulose (HEC) was studied over a range of polymer concentrations by using the maximum bubble pressure method at temperatures ranging from 20 to 65°C. The surface tension of water was also measured by the maximum bubble pressure method as well as by the DuNoüy ring method over the same temperature range. The experimental water data are in excellent agreement with the well-established tabulated data in the literature.

For a fixed concentration, all of the polymer solutions exhibited a decrease in surface tension with increasing temperature level. When compared with water at a fixed temperature level, the PAM and CMC solutions showed slightly higher surface tension values, whereas the PAA solutions yielded values equal to those found for water. In the case of the HEC solutions, the measured surface tensions decreased with concentration at a fixed temperature level and were lower than the values found for water. For a concentration of 2000 wppm the surface tension values for the hydroxyethyl cellulose were of the order of 10% lower than those for water at a fixed temperature level.

A comparison of the new measurements with the relatively limited previously published studies showed good agreement.     

On the dynamics of bubbles in polymer aqueous solutions

By analysing experimentally the rheological behaviors of polyethylene oxide solutions, polyacrylamide solutions, carboxymethylcellulose solutions, and hydroxyethylcellulose solution, a rheological model is proposed. The effect of various polymer additives on an air-liquid surface tension is made clear. The equation of motion for a bubble and the pressure equation are derived by using the new rheological expression, and then the effects of a kind of polymer and a polymer concentration on the bubble radius-time history and impulse pressure are numerically examined.     

Direct comparison of equibiaxial elongational viscosity measurements from lubricated squeezing flow and the MultiAxiales Dehnrheometer

We present the first direct comparisons of rheological data from the lubricated squeezing flow (LSF) technique and the MultiAxiales Dehnrheometer (MAD) instrument developed by Meissner and coworkers (J Rheol 47:989–1010, 2003). Comparisons of transient equibiaxial elongational viscosity are carried out at strain rates well into the nonlinear regime on low-density polyethylene and polystyrene melts. We find data obtained using LSF deviate from the MAD data when the Hencky strain reaches a value of approximately 1, which we interpret as a failure of the LSF technique. The strain at which the LSF technique fails is relatively insensitive to experimental parameters including strain rate. For Hencky strains larger than 1, LSF data display behavior that could easily be mistaken for the phenomenon of strain hardening.     

Normal stress measurements on drag-reducing polymer solutions

Summary The elastic properties of very dilute solutions of a number of drag-reducing polymers differing either in chemical nature or molecular weight were investigated over a range of values of shear stress using the jet thrust method. Parallel drag reduction measurements were also made with the solutions. The results indicate a general relationship between the value of the first normal stress difference at the wall, (p ₁₁-p ₂₂, and the dragreducing ability.The data tends to confirm the generality of the correlation between the value of theWeissenberg number and the drag reduction reported byMetzner for a single polymer sample.     

Dynamic measurements on polymer solutions and melts

Summary An apparatus for the measurement of the dynamic viscosity is described. In a coaxial cylinder geometry forced vibrations are executed in the frequency region from 2·10^–4 to 50 cycles/sec. Fluids with a wide range of viscosities (10^–1 to 10⁷ poise) can be measured. A number of experimental results obtained on dilute solutions and melts of polymers are given and compared with results of the molecular theories.

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Zusammenfassung Es wird ein Gerät für die Messung der dynamischen Viskosität beschrieben. Innerhalb eines koaxialen Zylindersystems werden im Frequenzgebiet von 2 · 10^–4 bis 50 Hz erzwungene Schwingungen ausgeführt. Messungen an Flüssigkeiten sind in einem weiten Viskositätsbereich (10^–1 bis 10⁷ Poise) möglich. Einige Messungen an verdünnten Lösungen oder Schmelzen von Hochpolymeren werden mitgeteilt und mit Voraussagen molekularer Theorien verglichen.

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Paper read at the Annual Meeting of the German Rheologits, Berlin-Dahlem, May 20–21, 1968).     

Rheological interpretation of pressure anomalies of aqueous dilute polymer solutions (ADPS) in orifice flow

The response of a considerable number of solutions of several polymers (PEO, HPAM, PAM) with concentrations of less than 100 ppm in orifice flow has been investigated. It is shown that the excess pressure (difference between the ADPS and the solvent total pressure drop) behaves linearly as a function of a superficial strain rate (ratio between a velocity and a length scale). In rheological terms this behaviour is interpreted as the result of a constant elongational viscosity whose values are two to three orders of magnitude larger than the shear viscosity. A formal approach to this phenomenological interpretation is suggested.