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.     

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.     

Measurement of extensional viscosity of polymer solutions

A filament stretching technique for measuring the extensional viscosity of polymer solutions at constant stretch rate is presented. The liquid sample is held between two coaxial discs and stretched by moving the bottom disc downwards with a speed that increases exponentially with time. This is illustrated using a constant viscosity, elastic fluid consisting of 0.185% polyisobutylene in a solvent of kerosene and polybutene. For the case of this particular fluid, two distinct stretch rate regions are found to arise. The stretch rate in the first region is much higher than in the second, which is, in most cases, close to the overall stretch rate imposed on the sample. Nonetheless, all the results of any given run can be represented using an average extensional rate. The extensional stress growth data, plotted as the Trouton ratio against time, show an initial linear viscoelastic region where T_R rises to a value of 3, independent of extensional rate. Beyond this region, T_R depends on the stretch rate and rises dramatically to values in excess of 10³; the higher the extensional rate, the faster is the increase in T_R. These data do not seem to reach a steady state and appear to be similar to polymer melt data obtained by others in the past. The reproducibility of the results is very good and all this suggests that it is now possible to obtain unambiguous constant-stretch-rate stress-growth data for polymer solutions stretched from a state of rest.     

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.     

Experimental investigations into an isothermal spinning threadline: Extensional rheology of a Separan AP 30 solution in glycerol and water

Summary Experimental observations on a steady isothermally extending filament of a water/glycerol solution of Separan AP 30 are presented. Photographic records were analysed to give filament diameter (and hence filament speed) as a function of distance below the extrusion die (a glass capillary). Measurements of inline tension were also made. When effects of weight, surface tension and air drag were accounted for, the extensional stress at every point along the filament could be calculated. Results for stress versus extension rate are presented for various flow situations.Independent rheogoniometric measurements of simple shear viscosity, first and second normal stress differences, and of a crude relaxation time were also made at comparable rates of deformation.Comparison shows that apparent extensional viscosities are several orders of magnitude larger than corresponding simple shear viscosities. After discussion, no conclusion can be drawn about what constitutive equation is most suitable to describe the results.An analysis to predict air drag is given.With 18 figures     

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.     

An innovative extensional viscometer for low-viscosity and low-elasticity liquids

A spinline-type extensional viscometer is described in which an innovative method of tensile stress measurement is employed. A limited amount of liquid flows through a vertical capillary at a constant flow rate under the influence of a constant pressure head. The drainage time decreases when the liquid stream leaving the capillary is stretched by the application of vacuum. These drainage times are measured in a manner similar to that used for intrinsic viscosity measurements. The measured difference in drainage times, with and without stretching, is trivially related to the extensional stress at the capillary exit, and this provides a very simple method of accurately determining fluid stretching forces having a magnitude as low as 10^-4 N; stresses at other axial locations in the stretched liquid jet are obtained by means of a force balance in the usual manner. The validity of the proposed technique is demonstrated by obtaining the expected results for a Newtonian oil having a shear viscosity of 56.2 mPa-s. Also presented are preliminary data on polyethylene oxide-in-water solutions having an even lower shear viscosity.     

扰动本构方程及粘弹流体拉伸流动不稳定性

提出“准衰退记忆”新概念,发展了非牛顿流体扰动本构理论,并研究了粘弹流体拉伸流动的不稳定性规律     

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.     

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.     

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.     

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.     

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     

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.     

Measuring uniaxial extensional viscosity using a modified rotational rheometer

Knowledge of the extensional behaviour of polymer melts is extremely important due to the industrial relevance of extensional flows in common processing techniques and sequences such as blow moulding, film blowing, fibre spinning, melt flow through extrusion dies and injection mould filling. One of the main problems both researchers and industrialists come across is the fact that, unlike shear flows, steady-state extensional flows are not easy to generate and maintain experimentally. This fact limits the extent to which one can characterise the materials and, therefore, the degree of optimisation of the productive process. In this paper, a modification to a commercially available controlled rate rotational rheometer is proposed in order to produce a cheap, easy to set-up, flexible extensional rheometer. This is based on the well-known Meissner-type extensional rheometer and makes use of the accurate velocity control and torque measurement possibilities of the rotational apparatus. In this case, the adaptation was performed on a TA Instruments Weissenberg Rheogoniometer, but the idea is applicable to most other similar devices. The feasibility of the modification will be discussed and confirmed, results being presented for two materials at different temperatures. These include the calculation of transient uniaxial extensional viscosity and a study of rupture conditions.     

Rapid conical flows of viscoelastic solutions

Several examples of conical, stretching flows of viscoelastic solutions are described. Two cases are then examined in more detail, the rapidly stretching free jet and an internally pressurised sheet of liquid in which extension takes place in a circumferential direction.It is shown that both the stress and strain rate may readily be calculated at different positions, provided certain assumptions are made. The changes of extensional viscosity necessary to produce the specified flow geometries are then shown to be anomalous and inconsistent. If, however, a solid-like model based on the Green measure of strain is used, a more satisfactory interpretation of the behaviour is achieved.It is emphasised that these are high-speed, high Deborah number flows and that such a flow pattern is not a general one.An example is also given in which the stretching of rubber is shown to be consistent with the same solid-like model, and values of the extensional moduli of elasticity are quoted for both liquids and rubber.     

On the interpretation of data from Converging Flow Rheometers

A reappraisal of data obtained from a Converging Flow Rheometer (CFR) is presented, together with new results for a specific polymer solution.Particular emphasis is placed on the interpretation of the experimental pressure data in terms of a planar extensional viscosity. It is suggested that previous interpretations, while yielding viscosity levels that appear reasonable, nevertheless fail to give the qualitative behaviour that might be expected on the basis of predictions from well accepted constitutive models. This, in the authors' opinions, arises because certain fluids, i.e. those that are highly tension-thickening, cease to flow in accordance with the assumed kinematics at high flow rates.By adapting a recently proposed approximate analysis for flow through a contraction it is shown that better qualitative behaviour, for the planar extensional viscosity, can be obtained from the Converging Flow Rheometer.     

Dehnviskosität von Kautschukmischungen

It is shown that the extensional viscosity measured by uniaxial stretch may give useful information as to the processability of rubber compounds. A simple apparatus was constructed to measure this rheological property at constant rate of strain. The influence of rubber type, filler, aging, mastication and degree of crosslinking on the reduced stress is represented by diagrams. No steady-state extensional viscosity was obtained for highly filled rubber compounds. It was found that the flow behaviour of rubber compounds can be better characterized with an extensional rheometer than with a high-pressure capillary rheometer.

     

The relevance of entry flow measurements for the estimation of extensional viscosity of polymer melts

The extensional viscosity of some flexible chain polymers and a thermotropic liquid crystalline polymer was measured in uniaxial extensional flow at constant extension rate. Power law functions were found for the dependence of the extensional viscosity at constant accumulated strain on strain rate. The stress growth curves were compared with measurements in axisymmetric entry flow, where both elongation and shear occur. The comparison showed that the values of the extensional viscosity calculated from the measurements in the entry flow correspond to the ones calculated from the viscosity growth measured in uniaxial elongation and averaged over extensional strain equal to what is accumulated on the fluid as it flows from the barrel into the capillary.     

Effect of a spectrum of relaxation times on the capillary thinning of a filament of elastic liquid

The capillary thinning of a filament of viscoelastic liquid, which is the basis of a microrheometer, is analyzed in terms of a multi-mode FENE fluid. After a short time of viscous adjustment, the stress becomes dominated by the elastic contribution and the strain-rate takes on a value equal to two-thirds the rate at which the stress would relax at fixed strain. This strain-rate decreases as the dominant mode changes. At late times, modes reach their finite extension limit. The fluid then behaves like a suspension of rigid rods with a large extensional viscosity, and the liquid filament breaks. Predictions are compared with the experiments of Liang and Mackley (1994).