Rheo-optical measurements of the first and third normal stresses of homopolymer poly(vinyl methyl ether) melt

Normal stresses play a key role in polymer processing, yet accurate measurements are still challenging. Simultaneous rheo-optical measurements are conducted on a poly(vinyl methyl ether) homopolymer melt over a wide range of temperatures and oscillatory shear frequencies, in an effort to measure the normal stresses, by using quantitative flow birefringence measurements. The stress optical rule holds well for this polymer as expected, with the value of the stress optic coefficient of (6.38±0.19)×10⁻¹¹ cm²/dyn at 30°C. The first and third normal stress difference coefficients, calculated using a single memory constitutive equation applied to the stress and birefringence data, are in excellent agreement. The ratio of the measured third and first normal stress difference coefficients, (1−β)=0.71±0.05, agrees well with the result of the Doi–Edwards model with independent alignment approximation (β=0.28). The measurement of normal stress difference coefficients with such small deviations proves the robust nature of the improved rheo-optical instrument and its ability to measure complete stress tensor.     

Stress optical measurement of the third normal stress difference in polymer melts under oscillatory shear

Results are reported for the dynamic moduli,G andG, measured mechanically, and the dynamic third normal stress difference, measured optically, of a series bidisperse linear polymer melts under oscillatory shear. Nearly monodisperse hydrogenated polyisoprenes of molecular weights 53000 and 370000 were used to prepare blends with a volume fraction of long polymer, _L, of 0.10, 0.20, 0.30, 0.50, and 0.75. The results demonstrate the applicability of birefringence measurements to solve the longstanding problem of measuring the third normal stress difference in oscillatory flow. The relationship between the third normal stress difference and the shear stress observed for these entangled polymer melts is in agreement with a widely predicted constitutive relationship: the relationship between the first normal stress difference and the shear stress is that of a simple fluid, and the second normal stress difference is proportional to the first. These results demonstrate the potential use of 1,3-birefringence to measure the third normal stress difference in oscillatory flow. Further, the general constitutive equation supported by the present results may be used to determine the dynamic moduli from the measured third normal stress difference in small amplitude oscillatory shear. Directions for future research, including the use of birefringence measurements to determineN ₂/N ₁ in oscillatory shear, are described.     

Comparison of optical and mechanical measurements of second normal stress difference relaxation following step strain

Relaxation of the second normal stress difference (N ₂) following step strain of a concentrated monodisperse polystyrene solution has been studied using mechanical and optical rheometry. Measurements of normal thrust in a parallel plate geometry are corrected for strain inhomogeneity and combined with independent measurements of the first normal stress difference (N ₁) to determine N ₂. Optical experiments were performed using a novel configuration where flow birefringence data collected using multiple light paths within the shear plane are combined with the stress-optical law to determine all three independent stress components for shearing deformations. This technique eliminates end effects, and provides an opportunity to oversample the stress tensor and develop consistency checks of experimental data. N ₂ is found to be nonzero at all accessible times, and relaxes in roughly constant proportion to N ₁. This reflects nonaffine distribution of chain segments, even well within the regime of chain retraction at short times. Data collected with the two techniques are reasonably consistent with each other, and with results of previous studies, generally lying between the predictions of the Doi-Edwards model with and without the independent alignment approximation. The normal stress ratio –N ₂/N ₁ shows pronounced strain thinning in the nonlinear regime.     

Characterization of micellar structure dynamics for a drag-reducing surfactant solution under shear: normal stress studies and flow geometry effects

Some surfactant solutions have been observed to exhibit a strong drag reduction behavior in turbulent flow. This effect is generally believed to result from the formation of large cylindrical micelles or micellar structures. To characterize and understand better these fluids, we have studied the transient rheological properties of an efficient drag-reducing aqueous solution: tris (2-hydroxyethyl) tallowalkyl ammonium acetate (TTAA) with added sodium salicylate (NaSal) as counter ion. For a 5/5 mM equimolar TTAA/NaSal solution, there is no measurable first normal stress difference (N ₁) immediately after the inception of shear, but N ₁ begins to increase after a well-defined induction time — presumably as shear-induced structures (SIS) are formed — and it finally reaches a fluctuating plateau region where its average value is two orders of magnitude larger than that of the shear stress. The SIS buildup times obtained by first normal stress measurements were approximately inversely proportional to the shear rate, which is consistent with a kinetic process during which individual micelles are incorporated through shear into large micellar structures. The SIS buildup after a strong preshear and the relaxation processes after flow cessation were also studied and quantified with first normal stress difference measurements. The SIS buildup times and final state were also found to be highly dependent on flow geometry. With an increase in gap between parallel plates, for example, the SIS buildup times decreased, whereas the plateau viscosity increased.     

Molecular theory for moderately concentrated polymer solutions in shear flow

A molecular theory for the rheological properties of moderately concentrated polymer solutions is developed on the basis of a model of interacting dumbbells. The interaction is treated in a mean field approximation, leading to an effective one-particle potential and a Gaussian stationary distribution function. Various rheological functions such as birefringence, shear viscosity and first normal-stress coefficient for simple shear flow and the Trouton viscosity for simple extensional flow are calculated. Good qualitative agreement with experimental observations is found, especially at intermediate flow rates. It is predicted, for example, that the birefringence increases approximately linearly with shear rate at intermediate shear rates and that the concentration dependence of the gradient varies asc ^1/2. The typical non-Newtonian behaviour is obtained for the shear viscosity. For small concentrations the onset of shear rate dependence decreases asc ^–1/2. At intermediate shear rates an apparent power law is obtained with an exponent between – 0.5 and – 1.0, decreasing with concentration.     

Theoretical and experimental investigation of the flow of a viscoelastic fluid in the gap between two rotating disks

A theory of the nonlinear viscoelastic behavior of polymer fluids has been constructed in [1]. The theory was used in [2] to investigate the motion of a nonlinear viscoelastic medium under steady and unsteady deformation rates in simple shear flow, and a comparison was made with experiment. The experiments in [2], which were performed on a cone-plate Weissenberg rheogoniometer, indicate that this arrangement is unsuitable for measurements of normal stresses under unsteady conditions in fluids with a fairly high viscosity. Below, we will show the suitability of using a disk-disk Weissenberg rheogoniometer to measure normal stresses in this case for unsteady conditions (transition to steady flow and stress relaxation). In this regard, a theoretical study of the flow of a viscoelastic fluid in the gap between rotating disks is needed. Note that in this case new information will be obtained from a comparison with simple uniform shear flow, since in the flow of a polymer between two disks all three normal stress components contribute to the axial force, while in the gap between a cone and a plate only the first normal stress difference contributes to the normal force.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 2, pp. 25–30, March–April, 1976.     

New laboratory tests to measure rheological properties of paper coatings in transient and steady-state flows

The paper describes pertinent laboratory tests to characterize the rheological properties of paper coatings with regard to blade coating over a very wide range of shear rates in both transient and steady-state shear flows. Shear rates as high as 10⁶ s^–1 can be reached by means of a gas-driven capillary rheometer. Examples for the evaluation of end effects, wall effects, and coating thixotropy are given. A stiff and fast Couette rheometer is used to determine flow curves and the shear stress overshoot in step shear rate tests. The primary normal stress difference can be measured up to 10⁴ s^–1 by means of a high shear cone-plate rheometer with piezo transducer. A correct evaluation of the measurements has to take into account inertia contributions to the normal force. First results using a sinusoidal modulation of the shear rate are presented.Paper presented at: International Symposium on Pigment Coating Structure and Rheology, Helsinki, Febr. 8–9, 1989     

Rheology and flow-birefringence from viscoelastic polymer-clay solutions

 The shear orientation of viscoelastic clay-polymer solutions was investigated by means of rheology and flow birefringence (Δn). The polymer chains are in dynamic adsorption/desorption equilibrium with the clay particles to form a “network”. The elastic behavior of the network was characterized by constant stress, oscillatory shear, and stress relaxation experiments. Constant stress experiments indicated a yield stress upon which shear flow started and no strain recovery could be observed. Oscillatory shear experiments showed a broad elastic region followed by flow when a critical strain was reached. Stress relaxation experiments showed several relaxation times when the same critical strain was reached. Experiments under steady flow characterized the transient behavior of the network. With increasing steady shear rate a pronounced minimum in birefringence was observed at a critical shear rate. The shear rate dependent viscosity showed near power law behavior and no corresponding critical feature. While birefringence detects orientational effects on a microscopic length scale, rheology averages over macroscopic changes in the sample. The same degree of orientation could be achieved under constant shear rate or constant stress conditions. Received: 25 January 2001 Accepted: 22 May 2001     

The transmission of turbulent boundary layer unsteady pressure and shear stress through a viscoelastic layer

The transmission of unsteady pressure and shear stress, generated by a turbulent boundary layer in water, through a viscoelastic layer backed by a rigid plate is investigated. Analytical models are used to estimate the unsteady pressure and shear stress from 10 to 1000 Hz for a flat plate boundary layer with zero pressure gradient. Additionally, models for the transfer of the unsteady pressures and shear stress through the viscoelastic layer are developed. The models are used to predict the unsteady pressure fluctuations, or flow noise, which would be seen by a finite size sensor embedded under the elastomer layer. The unsteady pressure levels are found to be 20 dB greater than the unsteady shear stress levels across all frequency ranges computed, in agreement with recent measurements. The unsteady pressure transfer functions have a peak at the shear wavenumber and are larger than the shear stress transfer magnitudes from 10 to 50 Hz. The unsteady shear stress transfer functions have a peak at the acoustic wavenumber and are larger than the pressure transfer magnitudes from 50 to 1000 Hz. Over the frequency range examined, the unsteady pressures were found to be the dominant contributor to the sensor flow noise due to the considerably larger magnitude of the unsteady pressures on the top of the viscoelastic layer.     

Rheo-PIV of a shear-banding wormlike micellar solution under large amplitude oscillatory shear

We explore the behavior of a wormlike micellar solution under both steady and large amplitude oscillatory shear (LAOS) in a cone–plate geometry through simultaneous bulk rheometry and localized velocimetric measurements. First, particle image velocimetry is used to show that the shear-banded profiles observed in steady shear are in qualitative agreement with previous results for flow in the cone–plate geometry. Then under LAOS, we observe the onset of shear-banded flow in the fluid as it is progressively deformed into the non-linear regime—this onset closely coincides with the appearance of higher harmonics in the periodic stress signal measured by the rheometer. These harmonics are quantified using the higher-order elastic and viscous Chebyshev coefficients e _n and v _n , which are shown to grow as the banding behavior becomes more pronounced. The high resolution of the velocimetric imaging system enables spatiotemporal variations in the structure of the banded flow to be observed in great detail. Specifically, we observe that at large strain amplitudes (γ ₀ ≥ 1), the fluid exhibits a three-banded velocity profile with a high shear rate band located in-between two lower shear rate bands adjacent to each wall. This band persists over the full cycle of the oscillation, resulting in no phase lag being observed between the appearance of the band and the driving strain amplitude. In addition to the kinematic measurements of shear banding, the methods used to prevent wall slip and edge irregularities are discussed in detail, and these methods are shown to have a measurable effect on the stability boundaries of the shear-banded flow.     

The peculiar rheo-optical behavior of bisphenol A-polycarbonate and polymethylmethacrylate

The rheological and stress-optical behavior of the melts of several grades ob bisphenol-A-polycarbonate (PC) and polymethylmethacrylate (PMMA) is investigated. Pertinent flow birefringence measurements are carried out in a remodelled cone-plate apparatus [1]. The shear stress in the polymer melt is calculated from the dynamic moduli, which are determined separately. It is shown that the linear stress optical rule is obeyed. In this way, the stress-optical coefficient C of the melt can be determined. The low-Mw polycarbonates all behave as Maxwellian fluids. The main stress direction does not deviate significantly from 45°. In the temperature range from 160° to 260°C the stress-optical coefficients of the different grades lie between 3 and 4×10^–9 Pa^–1 and show a weak temperature dependence. The stress-optical coefficient of PMMA is about a factor of 100 lower and shows a peculiar temperature-dependence, changing its sign at 144°C. The results are discussed in terms of the anisotropy of the polarizability of the polymer chain.     

Direct measurements of local bed shear stress in the presence of pressure gradients

This paper describes the development of a shear plate sensor capable of directly measuring the local mean bed shear stress in small-scale and large-scale laboratory flumes. The sensor is capable of measuring bed shear stress in the range \(\pm\) 200 Pa with an accuracy up to \(\pm\) 1 %. Its size, 43 mm in the flow direction, is designed to be small enough to give spatially local measurements, and its bandwidth, 75 Hz, is high enough to resolve time-varying forcing. Typically, shear plate sensors are restricted to use in zero pressure gradient flows because secondary forces on the edge of the shear plate caused by pressure gradients can introduce large errors. However, by analysis of the pressure distribution at the edges of the shear plate in mild pressure gradients, we introduce a new methodology for correcting for the pressure gradient force. The developed sensor includes pressure tappings to measure the pressure gradient in the flow, and the methodology for correction is applied to obtain accurate measurements of bed shear stress under solitary waves in a small-scale wave flume. The sensor is also validated by measurements in a turbulent flat plate boundary layer in open channel flow.     

Normal stress measurements

An apparatus designed to measure the dynamic viscoelastic response of polymer melts is described. Dynamic elasticity (G) and viscosity () can be measured over a frequency range 10^–2-10^–3 Hz and at temperatures up to 350 °C. The sample under test is held in a cone and plate assembly. A small strain is introduced by driving the plate with a variable speed synchronous motor and off-centre cam at low frequencies and by an electromagnetic vibrator at high frequencies. The amplitudes of the cone and plate are detected using the optical lever principle and photocell strips. The phase difference between the cone and plate is measured from a recorder trace at low frequencies and by direct reading on a meter at high frequencies.Results are described of measurements on silicone fluids, and on commercial grades of polyethylene with different molecular weight distributions and degrees of branching.A discussion is given of the correlation between the dynamic viscosity measurements and those taken under steady-flow conditions.Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968. — Original paper published in J. Sci. Instruments Series 2,1, 1102–1112 (1968).     

Compliance effects on the torsional flow of a viscoelastic fluid

The effects of transducer compliance on transient stress measurements in torsional flows of a viscoelastic fluid are investigated theoretically. The analysis is based on the torsional flow of an upper-convected Maxwell fluid between a rotating and ‘stationary’ disk, which is allowed to twist and displace axially as a result of the stresses exerted on the disk by the fluid. An approximate analytical solution to the governing equations is obtained using a standard perturbation method. Results of the analysis are used to examine how the fluid velocity is altered by the motion of the stationary disk and to gain insight on how transient stress measurements are affected by transducer compliance. The analysis shows that compliance effects increase with applied shear rate and that the effects of torsional and axial compliance are coupled in measurements of the shear stress and first normal stress difference.     

Rheo-optical investigations of lyotropic mesophases of polymeric surfactants

The shear orientation of hexagonal and lamellar liquid crystalline phases of polymeric surfactants was investigated by rheo-optical techniques (flow birefringence (Δn), small-angle light scattering) as well as by nuclear magnetic resonance and optical microscopy. The evolution of birefringence in the hexagonal phase is discussed for simple and oscillatory shear, and an alignment of rodlike micelles along the flow direction was found. A shear induced formation of vesicles (“onions”) is observed with the lamellar phase. They displayed a characteristic four-lobe pattern in depolarized light scattering. Above a critical shear stress vesicles were degraded and perpendicularly aligned lamellae (i.e. with their normal along the vorticity direction) were obtained. A comparison of experiments performed at constant stress and constant rate revealed that the vesicle to planar lamellae transition occurred above a critical shear stress. The behavior of the polysoap lyotropic mesophases under shear, i.e. the strain dependent alignment in the hexagonal phase, the shear induced formation of vesicles, and a transition to planar lamellae in the lamellar phase, is very similar to the behavior of lyotropic mesophases formed by low molar mass surfactants or amphiphilic block copolymers. The geometrical constraints that are introduced when amphiphilic side groups are fixed to a polymer backbone do not significantly alter the response of the mesophase to a shear deformation. Received: 4 May 1999 /Accepted: 19 July 1999     

Direct measurement of static yield properties of cohesive suspensions

A technique of yield stress investigation based upon the combined use of two devices (an applied stress rheometer and an instrument for measuring the propagation velocity of small amplitude, torsional shear waves) is described. Investigations into the low shear rate rheological properties of illitic suspensions are reported for shear rates, typically, in the range 10^–4— 10^–1 s^–1 under applied stresses in the range 0.01 — 10 Nm^–2 and involving shear strains between 10^–1 and 10^–4. Results are presented which demonstrate that the technique does not invoke the excessive structural disruption of material associated with applied shear rate based methods (direct and otherwise) and the widely encountered problem of wall slip at the surface of rotational measuring devices is avoided using miniature vane geometries. Results are compared with those obtained using smooth-walled cyclindrical measuring devices in both applied stress and applied shear rate instruments.Yield measurements are considered in relation to the structural properties of the undisturbed material state and shear moduli obtained by studying the propagation of small amplitude (10^–5 rad), high frequency (~ 300 Hz) torsional shear waves through the test materials are reported. Experimental techniques and instrument modifications to permit these measurements are described.     

The measurement of normal stresses by means of liquid-filled holes in a surface

Summary This paper concerns the systematic errors that may arise when using pressure measurements, made by means of holes in the surfaces of a viscometer, to estimate the normal stresses in steady shear flows. The work is closely related to some recent measurements ofBroadbent et al. (1968) and ofKaye, Lodge &Vale (1968) who first proposed that such errors may be important in determining the normal-stress differences of fluids in steady shear flows. Some dimensional arguments are presented to show how our estimate of the normal stress at the surface may be affected by the measuring technique and by the particular kind of curvilinear shear flow in which the measurements are being made. An experimental investigation of the influence of some of the dimensionless parameters has been made in a cone-and-plate viscometer, the results of which suggest that the estimate of the normal stress at the surface is not greatly affected by geometric changes of the hole. On the other hand, some measurements made by Dr.J. M. Broadbent for shear flows generated between concentric cylinders suggest that the experimental estimate of the normal stresses on the walls of the cylinders are dependent upon the parameterR/d whereR is the radius of the cylinder andd is the diameter of the hole used to make the measurement. From the results of a calculation byTanner &Pipkin (1969) of the error that arises from this measuring technique when a second-order fluid flows past a two-dimensional slot in a plane wall, and with the possible extension to more complicated fluids it appears that this source of error could account for the inconsistencies in the measurements ofKaye, Lodge &Vale (1968).

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Zusammenfassung Diese Arbeit behandelt die möglichen systematischen Fehler bei der Bestimmung der Normalspannungen in stationären Scherströmungen, wenn dazu Druckmessungen mittels Bohrungen in den Oberflächen eines Viskosimeters herangezogen werden. Sie schließt an einige neuere Messungen vonBroadbent und Mitarb. (1968) und vonKaye, Lodge, undVale (1968) an. Letztere wiesen erstmals darauf hin, daß solche Fehler bei der Ermittlung von Normalspannungs-Differenzen in stationären Scherströmungen bedeutsam sein können. Anhand einer Dimensionsbetrachtung wird gezeigt, inwieweit die Meßtechnik selbst und die besondere Art der Scherströmung mit gekrümmten Stromlinien einen Einfluß auf die Bestimmung der Normalspannung an der Oberfläche haben.Der Einfluß einiger dimensionsloser Parameter wurde in einem Platte-Kegel-Viskosimeter experimentell untersucht. Die gewonnenen Ergebnisse deuten darauf hin, daß Veränderungen in der Geometrie der Meßbohrungen die Bestimmung der Normalspannungen nur wenig beeinflussen. Andererseits lassenBroadbents Messungen in Scherströmungen zwischen zwei konzentrischen Zylindern erkennen, daß die experimentellen Werte der Normalspannungen in der Zylinderoberfläche vom ParameterR/d abhängen (R — Zylinderradius,d — Durchmesser der Meßbohrung).Aufgrund einer Fehlerberechnung für diese Meßtechnik, wobei eine Flüssigkeit 2. Ordnung entlang einer ebenen Wand mit zweidimensionaler Nut angenommen wurde (Tanner undPipkin, 1969), aufgrund der möglichen Erweiterung dieser Berechnung auf kompliziertere Flüssigkeiten, erscheint es möglich, daß die oben erwähnte Fehlerquelle der Grund für die Widersprüche in den Messungen vonKaye, Lodge undVale sind.

     

Flow birefringence and rheological measurements on shear induced micellar structures

Aqueous solutions of cationic surfactant systems with strongly binding counterions show the striking phenomenon of shear induced phase transitions. At low shear rates or angular frequencies, the solutions exhibit Newtonian flow. At high rates of shear, however, the rheological properties change dramatically. Above a well defined threshold value of the velocity gradient, a supermolecular structure can be formed from micellar aggregates. This shear induced structure (SIS) behaves like a gel and exhibits strong flow birefringence. The formation of the shear induced structure is very complicated and depends on the specific conditions of the surfactant system. In this paper we discuss new results which have been obtained from rheological measurements and from flow birefringence data. We examine the stability of the shear induced state as a function of temperature, surfactant concentration and salt concentration and we analyse the effect of solubilisation of alcohols and hydrocarbons. The results are interpreted in terms of a kinetic model which accounts for the observed behavior.Dedicated to the 60. birthday of Prof. H. Harnisch, Hoechst AGPartly presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986     

Birefringence and stress growth in uniaxial extension of polymer solutions

Simultaneous measurements of extensional stresses and birefringence are rare, especially for polymer solutions. This paper reports such measurements using the filament stretch rheometer and a phase modulated birefringence system. Both the extensional viscosity and the birefringence increase monotonically with strain and reach a plateau. Estimates of this saturation value for birefringence, using Peterlin’s formula for birefringence of a fully extended polymer chain are in agreement with the experimental results. However, estimates of the saturation value of the extensional viscosity using Batchelor’s formula for suspensions of elongated fibres are much higher than observed. Reasons for the inability of the flow field to fully unravel the polymer chain are examined using published Brownian dynamics simulations. It is tentatively concluded that the polymer chain forms a folded structure. Such folded chains can exhibit saturation in birefringence even though the stress is less than that expected for a fully extended molecule.Simultaneous measurements of stress and birefringence during relaxation indicate that the birefringence decays much more slowly than the stress. The stress-birefringence data show a pronounced hysteresis as predicted by bead-rod models. The failure of the stress optic coefficient in strong flows is noted.Experiments were also performed wherein the strain was increased linearly with time, then held constant for a short period before being increased again. The response of the stress and birefringence in such experiments is dramatically different and can be traced to the different configurations obtained during stretching and relaxation. The results cast doubt on the appropriateness of pre-averaging the non-linear terms in constitutive equations.     

The instron rheometer

The rheometer is based on an original design by the Monsanto Chemical Co., for the study of flow properties of polymer melts. Shear rates over the range 10¹ to 10⁶ reciprocal seconds are obtained by driving a plunger at constant rates through a barrel with interchangeable capillary tubes at the exit. The resulting shear stress is measured by the accurate load measuring system of the basic instrument.Errors due to the length to diameter ratio of the capillaries, plunger friction, polymer compressibility, temperature rise due to friction and pressure drop in the barrel, are discussed and correction methods suggested.Standard and special applications of the rheometer are discussed indicating that it can be used to determine factors other than apparent viscosity.Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968. — Original paper published in Instron Application Series SA-3