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.     

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.     

Flow of wormlike micelle solutions past a confined circular cylinder

In this paper, we present the results of an investigation into the flow of a series of viscoelastic wormlike micelle solutions past a confined circular cylinder. Although this benchmark flow has been studied in great detail for polymer solutions, this paper reports the first experiments to use a viscoelastic wormlike micelle solution as the test fluid. The flow kinematics, stability and pressure drop were examined for two different wormlike micelle solutions over a wide range of Deborah numbers and cylinder to channel aspect ratios. A combination of particle image velocimetry and pressure drop measurements were used to characterize the flow kinematics, while flow-induced birefringence measurements were used to measure the micelle deformation and alignment in the flow. The pressure drop was found to decrease initially due to the shear thinning of the test fluid before increasing at higher flow rates as elastic effects begin to dominate the flow. Above a critical Deborah number, an elastic instability was observed for just one of the test fluids studied, the other remained stable for all Deborah number tested. Flow-induced birefringence and velocimetry measurements showed that observed instability originates in the extensional flow in the wake of the cylinder and appears not as periodic counter-rotating vortices as has been observed in the flow of polymer solutions past circular cylinders, but as a chaotic rupture event in the wake of the cylinder that propagates axially along the cylinder. Reducing the cylinder to channel aspect ratio and the degree of shearing introduced by the channel walls had a weak impact on the stability of the flow. These measurements, when taken in conjunction with previous work on flow of wormlike micelle solutions through a periodic array of cylinders, definitively show that the instability can be attributed to a breakdown of the wormlike micelle solutions in the extensional flow in the wake of the cylinder.     

Impact dynamics of drops on thin films of viscoelastic wormlike micelle solutions

The impact dynamics of water drops on thin films of viscoelastic wormlike micelle solutions is experimentally studied using a high-speed digital video camera at frame rates up to 4000 frame/s. The composition and thickness of the thin film is modified to investigate the effect of fluid rheology on the evolution of crown growth, the formation of satellite droplets and the formation of the Worthington jet. The experiments are performed using a series of wormlike micelle solutions composed of a surfactant, cetyltrimethylammonium bromide (CTAB), and a salt, sodium salicylate (NaSal), in deionized water. The linear viscoelastic shear rheology of the wormlike micelle solutions is well described by a Maxwell model with a single relaxation time while the steady shear rheology is found to shear thin quite heavily. In transient homogeneous uniaxial extension, the wormlike micelle solutions demonstrate significant strain hardening. The size and velocity of the impacting drop is varied to study the relative importance of Weber, Ohnesorge, and Deborah numbers on the impact dynamics. The addition of elasticity to the thin film fluid is found to suppress the crown growth and the formation of satellite drops with the largest effects observed at small film thicknesses. A new form of the splashing threshold is postulated which accounts for the effects of viscoelasticity and collapses the satellite droplet data onto a single master curve dependent only on dimensionless film thickness and the underlying surface roughness. Additionally, a plateau is observed in the growth of the maximum height of the Worthington jet height with increasing impact velocity. It is postulated that the complex behavior of the Worthington jet growth is the result of a dissipative mechanism stemming from the scission of wormlike micelles.     

A simple extensional viscometer

An extensional viscometer is described in which the liquid filament leaving a capillary is subjected to a stretching deformation. In order to keep the flow rate through the capillary unaltered upon inception of stretching, the pressure head at the capillary entrance has to be reduced by an amount equal to the extensional viscoelastic stress at the capillary exit. This affords a simple means of measuring small fluid forces such as those that occur in the stretching of dilute polymer solutions. Since stretch rates can be obtained from a knowledge of the mass flow rate and the filament diameter profile, extensional viscosities can be computed. The efficacy of the technique is demonstrated by obtaining the anticipated results for Newtonian liquids.     

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 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.     

Experimental study on the capillary thinning of entangled polymer solutions

The transient elongation behavior of entangled polymer and wormlike micelles (WLM) solutions has been investigated using capillary breakup extensional rheometry (CaBER). The transient force ratio X = 0.713 reveals the existence of an intermediate Newtonian thinning region for polystyrene and WLM solutions prior to the viscoelastic thinning. The exponential decay of X(t) in the first period of thinning defines an elongational relaxation time λ _x which is equal to elongational relaxation time λ _e obtained from exponential diameter decay D(t) indicating that the initial stress decay is controlled by the same molecular relaxation process as the strain hardening observed in the terminal regime of filament thinning. Deviations in true and apparent elongational viscosity are discussed in terms of X(t). A minimum Trouton ratio is observed which decreases exponentially with increasing polymer concentration leveling off at Tr_min = 3 for the solutions exhibiting intermediate Newtonian thinning and Tr_min ≈ 10 otherwise. The relaxation time ratio λ _e/ λ _s, where λ _s is the terminal shear relaxation time, decreases exponentially with increasing polymer concentration and the data for all investigated solutions collapse onto a master curve irrespective of polymer molecular weight or solvent viscosity when plotted versus the reduced concentration c[ η], with [ η] being the intrinsic viscosity. This confirms the strong effect of the nonlinear deformation in CaBER experiments on entangled polymer solutions as suggested earlier. On the other hand, λ _e ≈λ _s is found for all WLM solutions clearly indicating that these nonlinear deformations do not affect the capillary thinning process of these living polymer systems.     

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.     

Suspensions of monodisperse spheres in polymer melts: particle size effects in extensional flow

Suspensions in polymeric, viscoelastic liquids have been studied in uniaxial extensional flow. The fibre wind-up technique has been used for this purpose. The effects of particle size and particle volume fraction have been investigated, using monodisperse, spherical particles. The results have been compared with shear flow data on the same materials. The values of the relative extensional viscosities at low stretching rates are in agreement with the relative shear viscosities and relative moduli. This indicates that hydrodynamic forces are stronger than the particle interaction forces. At larger strain rates strain hardening occurs; it is suppressed when particles are added. Small aggregating particles reduce the strain hardening more strongly than larger particles; strain hardening can even be totally eliminated. When further increasing the stretching rate, hydrodynamic effects dominate again and the effect of particle size effect on strain hardening disappears.     

A new look at extensional rheology of low-density polyethylene

The nonlinear rheology of three selected commercial low-density polyethylenes (LDPE) is measured in uniaxial extensional flow. The measurements are performed using three different devices including an extensional viscosity fixture (EVF), a homemade filament stretching rheometer (DTU-FSR) and a commercial filament stretching rheometer (VADER-1000). We show that the measurements from the EVF are limited by a maximum Hencky strain of 4, while the two filament stretching rheometers are able to probe the nonlinear behavior at larger Hencky strain values where the steady state is reached. With the capability of the filament stretching rheometers, we show that LDPEs with quite different linear viscoelastic properties can have very similar steady extensional viscosity. This points to the potential for independently controlling shear and extensional rheology in certain rate ranges.     

Structure and rheology of wormlike micelles

In a semi-dilute aqueous solution under certain conditions, surfactant molecules will self assemble to form wormlike micelles. The micelles are dynamic in structure since they can break and reform, providing an additional mode of relaxation. The viscoelastic properties of the wormlike micelles can be predicted using simple theological models. For many surfactant solutions the mechanical data can be related to the optical data by the stress-optical rule. From the viscoelastic data it is possible to estimate the breaking time of the micelle. The techniques of birefringence and small angle light scattering are used to study the microstructure of a surfactant solution under simple shear and extensional flow. The sample under investigation is a solution of cetyltrimethylammonium bromide and sodium salicylate in water, with a salt to surfactant ratio of 7.7. Below a critical shear rate, the birefringence increases linearly with shear rate and the stress-optical rule is valid. The SALS patterns reveal distinctive butterfly patterns indicating that scattering is a result of concentration fluctuations that moderately couple to the flow. However, above a critical shear rate the birefringence plateaus and the stress-optical rule is no longer valid. SALS patterns show both a bright streak and a butterfly pattern. The bright streak is caused by elongated structures aligned in the direction of the flow. The oriented structures occur when the characteristic time of flow is faster than the breaking time of the micelles.Dedicated to Prof. Dr. J. Meissner on the occasion of his retirement from the chair of Polymer Physics at the Eidgenössische Technische Hochschule (ETH) Zürich, Switzerland     

Generation of inkjet droplet of non-Newtonian fluid

In this study, the generation of inkjet droplets of xanthan gum solutions in water–glycerin mixtures was investigated experimentally to understand the jetting and drop generation mechanisms of rheologically complex fluids using a drop-on-demand inkjet system based on a piezoelectric nozzle head. The ejected volume and velocity of droplet were measured while varying the wave form of bipolar shape to the piezoelectric inkjet head, and the effects of the rheological properties were examined. The shear properties of xanthan gum solutions were characterized for wide ranges of shear rate and frequency by using the diffusive wave spectroscopy microrheological method as well as the conventional rotational rheometry. The extensional properties were measured with the capillary breakup method. The result shows that drop generation process consists of two independent processes of ejection and detachment. The ejection process is found to be controlled primarily by high or infinite shear viscosity. Elasticity can affect the flow through the converging section of inkjet nozzle even though the effect may not be strong. The detachment process is controlled by extensional viscosity. Due to the strain hardening of polymers, the extensional viscosity becomes orders of magnitude larger than the Trouton viscosities based on the zero and infinite shear viscosities. The large extensional stress retards the extension of ligament, and hence the stress lowers the flight speed of the ligament head. The viscoelastic properties at the high-frequency regime do not appear to be directly related to the drop generation process even though it can affect the extensional properties.     

Extensional flow of a viscoelastic filament governed by the FENE-CR model

A thin filament model is used to analyze the extensional flow of a viscoelastic thread governed by the FENE-CR model. The problem is solved numerically by finite differences using a third-order upwind scheme in space and a second order Runge-Kutta scheme in time. The behavior of the filament is controlled by the competing effects of surface tension and axial normal stresses which are characterized in terms of three-dimensional groups, the Deborah number De, the extensibility parameter L and the capillary number Ca. Surface tension has a destabilizing effect causing the filament to thin in the mid-section leading to a rupture. On the other hand normal stresses tend to stabilize the filament. If axial normal stresses are sufficiently large the filament deforms almost uniaxially due to strain hardening.     

The triple jet: influence of shear history on the stretching of polymer solutions

A kerosene-based aircraft safety fuel and aqueous solutions of poly (ethylene oxide) and polyacrylamide are examined using the “triple jet” system. This device allows the solution to be stretched as it flows from a capillary tube and the axial stress, strain and strain rate in the liquid are measured.The shear history of the solution is altered by placing cylindrical inserts in the capillary tube. This is shown to have a large effect on the extensional behaviour of aircraft safety fuel, a moderate effect on the extensional behaviour of poly (ethylene oxide) solution and little effect on the behaviour of polyacrylamide solution. The extensional viscosity of the aircraft fuel is raised by an order of magnitude when a long period of high shear is used; the effects last for periods of up to one second, though traditional methods suggest a relaxation time of the order of 10^?3 seconds. A liquid of shear viscosity 4 centipoise may have an extensional viscosity of over 100 poise.Plots of the extensional modulus of the jet as a function of distance along the jet emphasize the importance of shear history for the first two types of solution and suggest that the latter stages of the stretching process are elastic in character. Typical extensional moduli for the solutions tested are in the range 1.3–5.0 × 10⁴ dyn.cm^?2.The relevance of the interplay between shearing and stretching flow to the phenomena of lubrication and turbulence suppression is mentioned.     

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.     

Dynamics of worm-like micelles: the Cox–Merz rule

The viscoelastic behaviour of worm-like micelles in small-amplitude oscillatory, steady simple shear and uniaxial extensional flows are analyzed with a model that couples the Oldroyd-B constitutive equation with a kinetic equation that accounts for the structural changes induced by the flow. In some cases, the constitutive equation predicts a viscoelastic behaviour that is consistent with the Cox–Merz rule. Departures from this rule are also predicted. Experimental data obtained for two worm-like micellar systems indicate that in these solutions, the Cox–Merz rule is not usually followed, in agreement with the predictions of our model. In uniaxial extensional flow, the model predicts a strain hardening in the extensional viscosity at low extensional rates and a strain-thinning at high extensional rates.     

The effects of chain conformation in the microfluidic entry flow of polymer–surfactant systems

An associative polymer–surfactant system has been used to observe the effects of chain conformation in the entry flow through a microfabricated planar 16:1:16 contraction–expansion geometry. The well-studied system of the flexible polymer poly(ethylene oxide) (PEO) and anionic surfactant sodium dodecyl sulfate (SDS) was used. Dilute polymer solutions with increasing SDS concentration were characterized in steady and dynamic shear, as well as capillary breakup extensional rheology. Based on this characterization, the primary quantitative difference is an increase in zero-shear viscosity as a result of the PEO chain expansion brought on by association of SDS surfactant micelles. However, these quantitatively similar solutions were observed to exhibit much more qualitatively different flow patterns via fluorescent streak imaging in the entry flow. In contrast to previous work on PEO solutions, the PEO–SDS systems were observed to transition to a steady viscoelastic flow regime characterized by stable lip vortices at much lower elasticity and Weissenberg numbers. The resulting insight gained regarding the utility of microfluidic flows in elucidating effects of subtle conformational changes further illustrates the potential for using microfabricated devices as rheometric tools for measuring the properties of dilute and weakly viscoelastic fluids.     

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.     

Breakup of liquid threads in linear flows

We study, theoretically, the surface-tension-driven breakup of a long filament of fluid in a general linear flow, v = L·x. By analyzing the problem in a moving frame and assuming a circular cross section we find that the flow around the filament is an axisymmetric extensional flow with a time-dependent strength, which can be calculated from the rate of rotation of the filament and a contribution to the axial velocity which varies with the azimuthal angle. The analysis of the axisymmetric time-dependent case does not appear to be overly restrictive: the asymmetric variation may be small even in the case of a simple shear flow, in which the asymmetry is the greatest among all possible linear flows, depending on the initial orientation of the filament. We present calculations for two special cases: hyperbolic extensional flow and simple shear flow. The results indicate that under similar conditions, the drop fragments produced on breakup in simple shear flow are larger than those in hyperbolic extensional flow. The predictions of the theory also compare reasonably well with some previous experimental data in hyperbolic extensional flow and simple shear flow.