Effect of a controlled pre-deformation history on extensional viscosity of dilute polymer solutions

We use a modified filament stretching rheometer to quantify the influence of a known controlled pre-shear history on the transient extensional viscosity of a dilute polymer solution. Two different types of pre-deformation are explored; both influence the subsequent stretching significantly, albeit in opposite ways. Small-amplitude oscillatory straining parallel to the direction of stretching enhances strain hardening and accelerates the tensile stress growth toward the steady-state value. Conversely, steady torsional shearing orthogonal to the direction of stretching retards strain hardening and results in a delayed approach to steady-state elongational flow. In both cases, the final steady-state extensional viscosity is the same as that observed with no pre-shearing. Calculations using a finitely extensible nonlinear elastic Peterlin dumbbell model qualitatively capture the trends observed in experiments, enabling interpretation of these observations in terms of the degree of polymer chain stretching imposed by the flow before extensional stretching.     

Measurement of relaxation times in extensional flow of weakly viscoelastic polymer solutions

The characterization of the extensional rheology of polymeric solutions is important in several applications and industrial processes. Filament stretching and capillary breakup rheometers have been developed to characterize the extensional properties of polymeric solutions, mostly for high-viscosity fluids. However, for low concentration polymer solutions, the measurements are difficult using available devices, in terms of the minimum viscosity and relaxation times that can be measured accurately. In addition, when the slow retraction method is used, solvent evaporation can affect the measurements for volatile solvents. In this work, a new setup was tested for filament breakup experiments using the slow retraction method, high-speed imaging techniques, and an immiscible oil bath to reduce solvent evaporation and facilitate particle tracking in the thinning filament. Extensional relaxation times above around 100 μs were measured with the device for dilute and semi-dilute polymer solutions. Particle tracking velocimetry was also used to measure the velocity in the filament and the corresponding elongation rate, and to compare with the values obtained from the measured exponential decay of the filament diameter.     

Extensional rheology of concentrated poly(ethylene oxide) solutions

The shear and extensional rheology of three concentrated poly(ethylene oxide) solutions is examined. Shear theology including steady shear viscosity, normal stress difference and linear viscoelastic material functions all collapse onto master curves independent of concentration and temperature. Extensional flow experiments are performed in fiber spinning and opposed nozzles geometries. The concentration dependence of extensional behavior measured using both techniques is presented. The zero-shear viscosity and apparent extensional viscosities measured with both extensional rheometers exhibit a power law dependence with polymer concentration. Strain hardening in the fiber spinning device is found to be of similar magnitude for all test fluids, irrespective of strain rate. The opposed nozzle device measures an apparent extensional viscosity which is one order of magnitude smaller than the value determined with the fiber spinline device. This could be attributed to errors caused by shear, dynamic pressure, and the relatively small strains developed in the opposed nozzle device. This instrument cannot measure local kinematics or stresses, but averages these values over the non-homogenous flow field. These results show that it is not possible to measure the extensional viscosity of non-Newtonian and shear thinning fluids with this device. Fiber spin-line experiments are coupled with a momentum balance and constitutive model to predict stress growth and diameter profiles. A one-mode Giesekus model accurately captures the plateau values of steady and dynamic shear properties, but fails to capture the gradual shear thinning of viscosity. Giesekus model parameters determined from shear rheology are not capable of quantitatively predicting fiber spinline kinematics. However, model parameters fit to a single spinline experiment accurately predict stress growth behavior for different applied spinline tensions.     

Investigation of the rheological properties of short glass fiber-filled polypropylene in extensional flow

The behavior of short glass fiber–polypropylene suspensions in extensional flow was investigated using three different commercial instruments: the SER wind-up drums geometry (Extensional Rheology System) with a strain-controlled rotational rheometer, a Meissner-type rheometer (RME), and the Rheotens. Results from uniaxial tensile testing have been compared with data previously obtained using a planar slit die with a hyperbolic entrance. The effect of three initial fiber orientations was investigated: planar random, fully aligned in the stretching flow direction and perpendicular to it. The elongational viscosity increased with fiber content and was larger for fibers initially oriented in the stretching direction. The behavior at low elongational rates showed differences among the various experimental setups, which are partly explained by preshearing history and nonhomogenous strain rates. However, at moderate and high rates, the results are comparable, and the behavior is strain thinning. Finally, a new constitutive equation for fibers suspended into a fluid obeying the Carreau model is used to predict the elongational viscosity, and the predictions are in good agreement with the experimental data.     

Filament stretching of carbon nanotube suspensions

This paper reports the application of a recently developed filament stretching protocol for the study of the extensional rheology of both treated and untreated carbon nanotubes (CNT) suspended within an epoxy resin. It was experimentally observed that filaments formed by treated and untreated CNT suspensions behaved differently after initial stretching. The filament thinning process of the base epoxy was consistent with a simple Newtonian fluid, whilst the filament of treated CNT suspensions also thinned in a Newtonian way but with an enhanced extensional viscosity. Filaments formed with untreated CNT suspensions behaved in a non-uniform way with local fluctuation in filament diameter, and it was not possible to obtain reliable extensional viscosity data. Irregularity of the untreated CNT filaments was consistent with coupled optical images, where spatial variation in CNT aggregate concentration was observed. In the case of treated CNT suspensions, the enhanced extensional viscosity was modelled in terms of the alignment of CNTs in the stretching direction, and the degree of alignment was subsequently estimated using a simple orientation model.     

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.     

Measurements and model predictions of transient elongational rheology of polymeric nanocomposites

Transient elongational rheology of two commercial-grade polypropylene (PP) and the organoclay thermoplastic nanocomposites is investigated. A specifically designed fixture consisting of two drums (SER Universal Testing Platform) mounted on a TA Instruments ARES rotational rheometer was used to measure the transient uniaxial extensional viscosity of both polypropylene and nanoclay/PP melts. The Hencky strain rate was varied from 0.001 to 2 s^− 1, and the temperature was fixed at 180°C. The measurements show that the steady-state elongational viscosity was reached at the measured Hencky strains for the polymer and for the nanocomposites. The addition of nanoclay particles to the polymer melt was found to increase the elongation viscosity principally at low strain rates. For example, at a deformation rate of 0.3 s^− 1, the steady-state elongation viscosity for polypropylene was 1.4 × 10⁴ Pa s which was raised to 2.8 × 10⁴ and 4.5 × 10⁴ Pa s after addition of 0.5 and 1.5 vol.% nanoclay, respectively. A mesoscopic rheological model originally developed to predict the motion of ellipsoid particles in viscoelastic media was modified based on the recent developments by Eslami and Grmela (Rheol Acta 47:399–415, 2008) to take into account the polymer chain reptation. We show that the orientation states of the particles and the rheological behavior of the layered particles/thermoplastic hybrids can be quantitatively explained by the proposed model.     

The effect of pre-shear on the extensional rheology of wormlike micelle solutions

The effect of initial microstructural deformation, alignment, and morphology on the response of wormlike micelle solutions in transient uniaxial extensional flows is investigated using a pre-shear device attached to a filament stretching rheometer. In filament stretching experiments, increasing the strength and the duration of the pre-shear just before stretch is found to delay the onset of strain hardening. In these experiments, the wormlike micelle solution filaments fail through a rupture near the axial midplane. The value of the elastic tensile stress at rupture is found to decrease with increasing pre-shear rate and duration. The most dramatic effects are observed at shear rates for which shear banding has been independently observed. The reduction in the strain hardening suggests that pre-shear before filament stretching might break down the wormlike micelles reducing their size before stretch. Strain hardening is also observed in capillary breakup rheometry experiments; however, the pre-sheared wormlike micelle solutions strain harden faster, achieve larger steady-state extensional viscosities and an increase in the extensional relaxation time with increasing shear rate and duration. The difference between the response of the wormlike micelles in filament stretching and capillary breakup experiments demonstrates the sensitivity of these self-assembling micelle networks to pre-conditioning.     

Extensional rheology of a shear-thickening cornstarch and water suspension

A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.     

Transient filament stretching rheometer

The Lagrangian specification is used to simulate the transient filament stretching rheometer. Simulations are performed for a dilute PIB-solution modeled as a four mode Oldroyd-B fluid and a semidilute PIB-solution modeled as a non-linear single integral equation. The simulations are used to investigate a sequence of filament stretching rheometers. The questions of special and temporal homogeneity of the experiment are investigated. The simulations are compared with data from a specific rheometer by Tirtaadmadja and Sridhar.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Numerical modelling of step–strain for stretched filaments

This article addresses the modelling of filament-stretching/step–strain deformation under viscoelastic capillary break-up configurations of the CaBER-type. Start-up, prior to step–strain, is conducted under constant stretch-rate synchronous plate retraction with impulsive sessation of plate motion. The study encompasses variation in material rheology, appealing to Oldroyd, Geisekus and Phan-Thien/Tanner-type models, which display differences in shear and extensional viscosity properties (shear thinning/extension hardening). Two different viscosity ratio settings are considered to reflect high- and low-solvent viscosity constituent components; the former representing typical Boger fluids, the latter high-polymer concentration fluids. We compare and contrast results for three alternative filament aspect ratios at the onset of step–strain. Throughout the step–strain period, we have been able to successfully capture such physical features as drainage to the filament feet, necking at the filament centre, and periods with travelling waves through the axial filament length. In addition, we have identified the suppressive influence that larger capillary forces have upon radial fluctuations, and the minor impact that gravitational forces have upon the ensuing deformation. From this study, estimates for rheometrical data have been derived in terms of characteristic material relaxation time and apparent extensional viscosity. The computational techniques employed include a compressed-mesh (CM) procedure, an Arbitrary Lagrangian–Eulerian scheme (ALE) and a free-surface particle tracking technique. Spatial discretisation of the problem is accomplished through a hybrid finite element/finite volume algorithm implemented in the form of a time-stepping incremental pressure-correction formulation.     

Rheological characterization of commercial highly viscous alginate solutions in shear and extensional flows

The rheological properties of sodium alginate in salt-free solutions were studied by steady shear, dynamic oscillatory and extensional measurements. This biopolymer consists of mannuronic and guluronic acid residues that give a polyelectrolyte character. We applied the scaling theories and checked their accordance with polyelectrolyte behaviour for low concentrations with a shift to neutral polymer behaviour at larger concentrations. This nature was supported by the effect of the concentration on the specific viscosity, the relaxation times from steady shear and the longest relaxation times from small amplitude oscillatory shear (SAOS) measurements. To analyze the extensional behaviour of the samples, we conducted a study of dimensionless numbers and time scales where filament thinning driven by viscous, capillary or elastic forces is at play. We conclude that an exponential filament thinning followed by breakup results in the best regimes that describe the experimental data. Besides, the data pointed out that alginate in salt-free concentrated solutions shows strain thinning of the extensional viscosity and chain rigidity, behaviours that cannot be inferred from the shear rheometry.     

The motion of long bubbles through viscoelastic fluids in capillary tubes

The penetration of long gas bubble through a viscoelastic fluid in a capillary tube has been studied in order to investigate the influence of viscoelastic material properties on the hydrodynamic coating thickness and local flow kinematics. Experiments are conducted for three tailored ideal elastic (Boger) fluids, designed to exhibit similar steady shear properties but substantially different elastic material functions. This allows for the isolation of elastic and extensional material effects on the bubble penetration process. The shear and extensional rheology of the fluid is characterized using rotational and filament stretching rheometers (FSR). The fluids are designed such that the steady-state extensional viscosity measured by the FSR at a Deborah number (De) greater than 1 differs over three orders of magnitude (Trouton ratio = 10³–10⁶). The experiment set up to measure the hydrodynamic coating thickness is designed to provide accurate data over a wide range of capillary numbers (0.01 < Ca < 100). The results indicate that the coating thickness in this process increases with an increase in the extensionally thickening nature of the fluid. Experiments are also conducted using several different capillary tube diameters (0.1 < D < 1 cm), in order to compare responses at similar Ca but different flow De. Suitable scaling methods and nonlinear viscoelastic constitutive equations are explored to characterize the displacement process for polymeric fluids. Bubble tip shapes at different De are recorded using a CCD camera, and measured using an edge detection algorithm. The influence of the mixed flow field on the bubble tip shape is examined. Particle tracking velocimetry experiments are conducted to compare the influence of viscoelastic properties on the velocity field in the vicinity of the bubble tip. Local shear and extension rates are calculated in the vicinity of the bubble tip from the velocity data. The results provide quantitative information on the influence of elastic and extensional properties on the bubble penetration process in gas-assisted injection molding. The bubble shape and velocity field information provides a basis for evaluating the performance of constitutive equations in mixed flow. Received: 19 January 1999 Accepted: 30 June 1999     

On the “viscosity overshoot” during the uniaxial extension of a low density polyethylene

An experimental investigation of the viscosity overshoot phenomenon observed during uniaxial extension of a low density polyethylene is presented. For this purpose, traditional integral viscosity measurements on a Münstedt-type extensional rheometer are combined with local measurements based on the in-situ visualization of the sample under extension. For elongational experiments at constant strain rates within a wide range of Weissenberg numbers (Wi), three distinct deformation regimes are identified. Corresponding to low values of Wi (regime I), the tensile stress displays a broad maximum, but such maximum is observed with various polymeric materials deformed at low rates and it should not be confused with the “viscosity overshoot” phenomenon. Corresponding to intermediate values of Wi (regime II), a local maximum of the integral extensional viscosity is systematically observed. Moreover, within this regime, a strong discrepancy between integral measurements and the space average of the local elongational viscosity is observed which indicates large deviations from an ideal uniaxial deformation process. Images of samples within this regime reinforce this finding by showing that, corresponding to the maximum of the integral viscosity, secondary necks develop along the sample. The emergence of a maximum of the integral elongational viscosity is, thus, related to the distinct inhomogeneity of deformation states and most probably not to the rheological properties of the material. In the fast stretching limit (high Wi, regime III), the overall geometric uniformity of the sample is well preserved, no secondary necks are observed and both the integral and the space averaged transient elongational viscosity show no maximum. A detailed but yet incomplete comparison of the experimental findings with results from the literature is presented and several open questions are stated.     

Large amplitude oscillatory elongation flow

A filament stretching rheometer (FSR) was used for measuring the elongation flow with a large amplitude oscillative elongation imposed upon the flow. The large amplitude oscillation imposed upon the elongational flow as a function of the time t was defined as where ε is the Hencky strain, is a constant elongational rate for the base elongational flow, Λ the strain amplitude (Λ ≥ 0), and Ω the strain frequency. A narrow molecular mass distribution linear polystyrene with a molecular weight of 145 kg/mol was subjected to the oscillative flow. The onset of the steady periodic regime is reached at the same Hencky strain as the onset of the steady elongational viscosity ( Λ = 0). The integral molecular stress function formulation within the ‘interchain pressure’ concept agrees qualitatively with the experiments.     

The effect of step-stretch parameters on capillary breakup extensional rheology (CaBER) measurements

Extensional rheometry has only recently been developed into a commercially available tool with the introduction of the capillary breakup extensional rheometer (CaBER). CaBER is currently being used to measure the transient extensional viscosity evolution of mid to low-viscosity viscoelastic fluids. The elegance of capillary breakup extensional experiments lies in the simplicity of the procedure. An initial step-stretch is applied to generate a fluid filament. What follows is a self-driven uniaxial extensional flow in which surface tension is balanced by the extensional stresses resulting from the capillary thinning of the liquid bridge. In this paper, we describe the results from a series of experiments in which the step-stretch parameters of final length, and the extension rate of the stretch were varied and their effects on the measured extensional viscosity and extensional relaxation time were recorded. To focus on the parameter effects, well-characterized surfactant wormlike micelle solutions, polymer solutions, and immiscible polymer blends were used to include a range of characteristic relaxation times and morphologies. Our experimental results demonstrate a strong dependence of extensional rheology on step-stretch conditions for both wormlike micelle solutions and immiscible polymer blends. Both the extensional viscosity and extensional relaxation time of the wormlike micelle solutions were found to decrease with increasing extension rate and strain of the step-stretch. For the case of the immiscible polymer blends, fast step-stretches were found to result in droplet deformation and an overshoot in the extensional viscosity which increased with increasing strain rates. Conversely, the polymer solutions tested were found to be insensitive to step-stretch parameters. In addition, numerical simulations were performed using the appropriate constitutive models to assist in both the interpretation of the CaBER results and the optimization of the experimental protocol. From our results, it is clear that any rheological results obtained using the CaBER technique must be properly considered in the context of the stretch parameters and the effects that preconditioning has on viscoelastic fluids.     

Is there a relation between the relaxation time measured in CaBER experiments and the first normal stress coefficient?

We investigate a variety of different semidilute polymer solutions in shear and elongational flow. The shear flow is created in the cone-plate-geometry of a commercial rheometer. We use capillary thinning of a filament that is formed by a polymer solution in the Capillary Breakup Extensional Rheometer (CaBER) as an elongational flow. We compare the relaxation time measured in the CaBER with relaxation times based on the first normal stress difference and the zero shear polymer viscosity that we measure in our rheometer. All of these three measurable quantities depend on different fluid parameters—the viscosity of the solvent, the polymer concentration within the solution, and the molecular weight of the polymers—and on the shear rate (in the shear flow measurements). Nevertheless, we find that the first normal stress coefficient depends quadratically on the CaBER relaxation time. Several scaling laws are presented that could help to explain this empirical relation.     

A model long-discontinuous-fiber filled thermoplastic melt in extensional flow

The shear cell model works for dilute fiber filled systems in extensional flow. This research investigates the suitability of the idea for highly aligned fibers in a concentrated suspension. A model fiber-filled polymer system made from nylon fibers in low-density polyethylene provided a means of controlling the material parameters. Two systems, with fiber aspect ratios of 20 and 100, containing 50% 0.5 mm fibers by volume are investigated. The thickness of the polymer layer, i.e. with fibers this size, allows bulk viscosity data to be compared with the data from the filled fluid. A weaving process created the discontinuous fiber/polyethylene preforms with high alignment of the fibers and with control of the fiber to fiber overlap. Testing the polyethylene in simple shear and extending the nylon/polyethylene provided the data needed to check the micro mechanics. A cone and plate rheometer and a capillary instrument produced the viscosity/strain rate data that characterized the specific polyethylene used in the composite. A furnace inset placed in an Instron hydraulic test machine allowed extension of the filled system at strain rates from 0.002 to 0.4 s⁻¹. The shear experiments show that the low-density polyethylene is a simple shear-thinning melt that provides a good model fluid. The extension of the filled systems shows an increase of the apparent extensional viscosity from that of neat polyethylene. Apparent viscosity rises two to three orders of magnitude for the systems investigated. The micromechanics allowed the conversion of the extensional data from the two filled systems to the shear viscosity of the polymer surrounding the fibers. The calculated polyethylene viscosity compares well with the data from the standard rheometers. The shear cell approach may be applied to highly aligned, high fiber-volume-fraction suspensions when the viscosity of the polymer is known at the scale of the film surrounding each fiber.