Rheotens-mastercurves and elongational viscosity of polymer melts

In a Rheotens experiment, the tensile force needed for elongation of an extruded filament is measured as a function of the draw ratio. For thermo-rheologically simple polymer melts, the existence of Rheotens-mastercurves was proved by Wagner, Schulze, and Göttfert (1995). Rheotens-mastercurves are invariant with respect to changes in melt temperature and changes in the average molar mass. By use of purely viscous models, we convert Rheotens-mastercurves of a branched and a linear polyethylene melt to elongational viscosity as a function of strain rate. The resulting elongational viscosity from constant force extension experiments is found to be in general agreement with what is expected as steady-state viscosity of polyethylene melts measured in either constant strain-rate or constant stress mode.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     

Elongational viscosity by fiber spinning

Isothermal melt, fiber-spinning was recently analyzed by means of a nonlinear, integral, constitutive equation that incorporates shear history effects, spectrum of relaxation times, shear-thinning, and extension thinning or thickening when either the drawing force or the draw ratio is specified. The predictions agreed with experimental data on spinning of polystyrene, low-density polyethylene, and polypropylene melts. The predicted apparent elongational viscosity along the threadline (which, as shown in this work, must be identical to that measured experimentally by fiber spinning type of elongational rheometers) is compared with the true elongational viscosity predicted by the same constitutive equation under well-defined experimental conditions of constant extension rate, independent of any strain history. It is concluded that the apparent elongational viscosity, as measured by fiber-spinning, approaches the true elongational viscosity at low Weissenberg numbers (defined as the product of the liquid's relaxation time multiplied by the extension rate). At moderate Weissenberg numbers, the two viscosities may differ by an order of magnitude and their difference grows even larger at high Weissenberg numbers.     

Rheological behaviour of nano-composites based on polyamide 6 under shear and elongational flow at high strain rates

In this work, the rheological behaviour of high molecular mass polyamide 6 (PA6)/organo-montmorillonite nano-composites, obtained via melt blending, was investigated under shear and extensional flow. Capillary rheometry was used for the measurement of high shear rate steady state shear viscosity and die entrance pressure losses; further, by the application of a converging flow method (Cogswell model) to these experimental results, elongational viscosity data were indirectly calculated. The extensional behaviour was directly investigated by means of melt spinning experiments, and data of apparent elongational viscosity were determined. The results evidenced that the presence of the organo-clay in filled PA6 melts modifies the rheological behaviour of the material, with respect to the unfilled polymer, in dependence on the type of flow experienced by the fluid. In shear flow, the nano-composites showed a slightly lower viscosity than neat PA6, whereas in elongation, they appeared much more viscous, in dependence on the organo-clay content.     

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.     

Elongational flow and rheology of monodisperse polymers in solution

We describe the utilization of idealized stagnation point extensional flows, produced by opposed jets, for birefringence visualization of induced molecular strain and flow resistance measurements. We identify rheological changes associated with the coil---stretch transition which occurs beyond a critical strain-rate in elongational flow-fields. In dilute solutions of monodisperse atactic polystyrene, increases in extensional viscosity are observed as isolated molecules become stretched. The largest increases in extensional viscosity, however, are found only beyond a critical concentration and strain rate, and are associated with the stretching of transient networks of interacting molecules. These results parallel similar effects seen in porous media flow and capillary entrance experiments. We determine the molecular weight dependence of the critical concentration which scales as M^−0.55 in agreement with pairwise interaction of coils, but is much lower than conventional values of the critical polymer concentration, c^*. We believed that polydispersity may play an important role in the development of such transient networks, and in controlling the degradation behaviour during flow.     

Isothermal elongational behavior of liquid-crystalline polymers and LCPs based blends

The rheological behavior of two flexible thermoplastics, Nylon-6 (Ny) and bisphenol-A polysulfone (PSu), and two wholly aromatic liquid crystalline polymers, Vectra-A900 (VA) and Vectra-B950 (VB), as well as that of Ny/VB and PSu/VA blends with 10% LCP, has been investigated by the use of capillary viscometers equipped with cylindrical dies having different length-to-diameter ratios. The elongational viscosity of all materials was calculated, from the results of isothermal measurements carried out at 290°C, by means of the Cogswell's analysis, based on the estimation of the pressure drop due to the converging flow at the die inlet. The behavior in elongational flow was compared with the rheological behavior in shear flow conditions. It was found that the elongational viscosities of VA and VB are very large and account for a fairly marked pressure drop at the die entrance, due to the orientation of the LCP domains taking place in the converging flow zone. For these materials, the ratio of the elongational viscosity to the Newtonian shear viscosity is up to two orders of magnitude higher than the value expected on the basis of the Trouton rule. For the flexible resins, the Trouton ratio is 3 and ca. 3–10, are common values for high molar mass linear polymers. The addition of 10% LCP into the flexible resins strongly increases their elongational viscosity and makes the blends resemble neat LCPs in their extensional flow behavior. In shear flow, on the contrary, the addition of LCP was shown to induce a marked reduction of the melt viscosity, even when, as for the Ny/VB blend, the LCP is more viscous than the matrix.     

Numerical simulation of entry flow of the IUPAC-LDPE melt

Numerical simulations have been undertaken for the creeping entry flow of a well-characterized polymer melt (IUPAC-LDPE) in a 4:1 axisymmetric and a 14:1 planar contraction. The fluid has been modeled using an integral constitutive equation of the K-BKZ type with a spectrum of relaxation times (Papanastasiou–Scriven–Macosko or PSM model). Numerical values for the constants appearing in the equation have been obtained from fitting shear viscosity and normal stress data as measured in shear and elongational data from uniaxial elongation experiments. The numerical solutions show that in the axisymmetric contraction the vortex in the reservoir first increases with increasing flow rate (or apparent shear rate), goes through a maximum and then decreases following the behavior of the uniaxial elongational viscosity. For the planar contraction, the vortex diminishes monotonically with increasing flow rate following the planar extensional viscosity. This kinematic behavior is not in agreement with recent experiments. The PSM strain-memory function of the model is then modified to account for strain-hardening in planar extension. Then the vortex pattern shows an increase in both axisymmetric and planar flows. The results for planar flow are compared with recent experiments showing the correct trend.     

Experimental estimation of elongational stresses of dilute polymer solutions and a related examination of some constitutive equations

Elongational stresses of dilute polymer solutions have been estimated by utilizing the flow through small orifices under the condition of no vortex upstream of the orifice plane. The flow was approximated with a linearly converging flow towards an apex of a cone, its validity being partially confirmed by the measured center velocities, and the elongational stresses are determined from the measured thrusts of dilute polymer solutions. On the other hand, elongational stresses were theoretically obtained with the modified Maxwell model and the second order fluid. A comparison was made between the experimental and the theoretical results and the following points were clarified; below an elongational rate of 2 × 10⁴ s⁻¹ the modified Maxwell model gives elongational stresses close to the experimentally determined ones, but above that elongational rate it deviates from the experimental results. The second order fluid is not sufficient to describe the stresses in this kind of elongational flow and an acceleration term such as δ²e^ij/δt² may be necessary in this case.     

Rheo-optical measurements of the elongational flow of aqueous polymer solutions

An opposed jets rheometer was used to investigate the elongational viscosity as a function of the strain rate for dilute aqueous solutions of polyvinylformamide and polyacrylamide. Critical strain rates at which the enhancement in elongational viscosity occurs were determined for both systems. The influence of the polymer concentration on the elongational viscosity was investigated. The measurements were performed with polymer concentrations less than the critical polymer concentration c_p^* c_p^* . In order to assess the deformation and orientation of the macromolecules, flow-induced birefringence was measured simultaneously.     

液晶高分子-各向异性流体挤出拉伸分岔研究

应用共转导数型本构方程研究了液晶高分子纺丝挤出过程的拉伸黏度,应用计算机符号运算软件 Maple得出解析表达式,拉伸黏度与拉伸率之间关系(随剪切速率变化)表明存在分岔现象,得出拉伸黏度显著高于相应的剪切黏度,解释了液晶高分子熔体挤出时不发生挤出胀大的物理机制．     

Rubber-like behaviour of poly(ethylene oxide) solution in elongational flow

The behaviour of an aqueous poly(ethylene oxide) sucrose solution and of a suspension of glass beads in a similar solution has been examined in elongational flow using a spinline rheometer. Over the accessible strain-rate range of ca. 1 to 10 s^?1 these fluids behaved essentially as elastic materials whereas, at similar strain rates in shear, they show shear-thinning behaviour.     

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.     

Comparison of the elongational behaviour of a polyethylene melt at constant stress and constant strain rate

Summary Two different apparatuses for measuring the elongational behaviour of polymer melts at constant tensile stress and constant elongational strain rate are described. Measurements on a low density polyethylene were carried out up to stretching ratios of 400. The homogeneity of sample deformation in both test methods was sufficient to reach a steady-state of elongational flow where the tensile stress and the strain rate as functions of time are constant. By unloading the molten rod the recoverable strain can be determined at any state of deformation. The recoverable strain increases with growing deformation and reaches a constant value in the steady-state. The elongational viscosity calculated from the rate of viscous flow agrees with the Trouton viscosity in the case of very small deformations only. With growing deformation the elongational viscosity increases up to a constant value in the steady-state which is greater than the Trouton viscosity by about a factor of six at measured strain rates of 0.03 s^–1 and 0.1 s^–1, respectively. The elongational viscosity and the recoverable strain in the steady-state measured with the two different test methods under the same experimental conditions are in good agreement.

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Zusammenfassung Zwei verschiedene Apparaturen zur Untersuchung des Dehnverhaltens von Polymerschmelzen unter konstanter Zugspannung und konstanter Dehngeschwindigkeit werden beschrieben. An einem Polyäthylen niedriger Dichte wurden Messungen bis zu Verstreckgraden von 400 durchgeführt. Die ausreichend homogene Probenverformung erlaubt in beiden Versuchsführungen das Erreichen eines stationären Dehnfließens mit zeitlich konstanter Zugspannung und Dehngeschwindigkeit. Durch Entlasten des Schmelzestranges ist der reversible Dehnungsanteil für jeden Verformungszustand direkt zu messen. Die reversible Dehnung steigt mit wachsender Dehnverformung an, bis sich im stationären Bereich ein konstanter Wert einstellt. Die aus der Geschwindigkeit des viskosen Dehnfließens berechnete Dehnviskosität stimmt nur für den Grenzfall kleiner Deformationen mit der Trouton-Viskosität überein. Mit wachsender Dehndeformation steigt die Dehnviskosität bis zu einem Gleichgewichtswert an, der bei den gemessenen Dehngeschwindigkeiten von 0,03 s^–1 und 0,1 s^–1 um etwa einen Faktor 6 über dem Wert der Trouton-Viskosität liegt. Die unter gleichen Versuchsbedingungen mit beiden Apparaturen bestimmten Dehnviskositäten und reversiblen Dehnungen im stationären Bereich stimmen überein.

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Parts of this paper were presented at the VII^th Internat. Congress on Rheology, Gothenburg, Sweden.

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With 10 figures and 2 tables     

Elongational properties and molecular structure of polyethylene melts

Summary The viscosity and the recoverable strain in the steady state of elongation have been measured on several polyethylenes of different molecular structures. The elongational viscosity as a function of tensile stress runs through a more or less pronounced maximum in the nonlinear range whereas in the linear range the Trouton viscosity is reached. For low density polyethylenes it could be demonstrated that the maximum of the steady-state elongational viscosity and the elasticity expressed by the steady-state compliances in shear and tension sensitively increase if the molecular weight distribution is broadened by the addition of high molecular weight components. A variation of the weight average molecular weight does only shift the elongational viscosity curve but leaves its shape unchanged. Two of the four high density polyethylenes investigated do not show a maximum of the steady-state elongational viscosity, for the others it is less pronounced than in the case of low density polyethylenes. The influence of branching on the elongational behaviour of polyethylene melts in the steady-state and the transient region is qualitatively discussed.With 11 figures and 4 tables     

Time-dependent non-linear dynamics of polymer solutions in microfluidic contraction flow—a numerical study on the role of elongational viscosity

A generalised form of the finitely extensible non-linear elastic (FENE) model for modelling non-linear flow of semi-dilute polymer solutions is proposed. It accounts for conformation-dependent polymer elasticity and predicts shear-thinning shear viscosity, non-linear elongational viscosity and first and second normal stress differences. The rheometric material functions predicted by the model are critically compared with the results of the linear Phan–Thien–Tanner model. The predictabilities of these constitutive models under benchmark flow problems are evaluated by time-dependent simulations, using finite volume method based on a CFD simulation toolbox. The effects of the model parameters, the inertia and the contraction ratio are numerically studied. The modified FENE model qualitatively captures the non-linear flow phenomena of polymer solution in the high elasticity number ( $\mathrm {El}$ ) flow regime observed in experiments. The results show that an accurate growth function of the elongational viscosity is the key to the prediction of the time-dependent highly asymmetric flow patterns.     

Branched viscoelastic surfactant solutions and their response to elongational flow

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

Non-Newtonian viscous oscillating free surface jets, and a new strain-rate dependent viscosity form for flows experiencing low strain rates

A model for oscillating free surface jet flow of a fluid from an elliptical orifice, together with experimental measurements, can be exploited to characterize the elongational viscosity of non-Newtonian inelastic fluids. The oscillating jet flow is predominantly elongational, with a small strain that oscillates rapidly between large and zero strain rates. We find that to reproduce the experimentally observed steady oscillating jet flow in model simulations, the assumed form of the non-Newtonian viscosity as a function of strain rate must have zero gradient, i.e., be Newtonian, at zero strain rate (a behavior exhibited, in general, by real inelastic fluids). We demonstrate that the Cross, Carreau, Prandtl-Eyring, and Powell-Eyring forms, although they have finite viscosity at zero strain rate, have either nonzero or even unbounded gradient at zero, and hence are unable to model oscillating jet behavior. We propose a new non-Newtonian viscous form which has all of the desirable features of existing forms (high and low strain rate plateaus, with adjustable location and steepness of the transition) and the additional feature of Newtonian behavior at low strain rates. Received: 7 February 2000 Accepted: 31 October 2000     

An unsymmetric constitutive equation for anisotropic viscoelastic fluid

A continuum constitutive theory of corotational derivative type is developed for the anisotropic viscoelastic fluid–liquid crystalline (LC) polymers. A concept of anisotropic viscoelastic simple fluid is introduced. The stress tensor instead of the velocity gradient tensor D in the classic Leslie–Ericksen theory is described by the first Rivlin–Ericksen tensor A and a spin tensor W measured with respect to a co-rotational coordinate system. A model LCP-H on this theory is proposed and the characteristic unsymmetric behaviour of the shear stress is predicted for LC polymer liquids. Two shear stresses thereby in shear flow of LC polymer liquids lead to internal vortex flow and rotational flow. The conclusion could be of theoretical meaning for the modern liquid crystalline display technology. By using the equation, extrusion–extensional flows of the fluid are studied for fiber spinning of LC polymer melts, the elongational viscosity vs. extension rate with variation of shear rate is given in figures. A considerable increase of elongational viscosity and bifurcation behaviour are observed when the orientational motion of the director vector is considered. The contraction of extrudate of LC polymer melts is caused by the high elongational viscosity. For anisotropic viscoelastic fluids, an important advance has been made in the investigation on the constitutive equation on the basis of which a series of new anisotropic non-Newtonian fluid problems can be addressed. The project supported by the National Natural Science Foundation of China (10372100, 19832050) (Key project). The English text was polished by Yunming Chen.     

Uniaxial elongational flow effects and morphology development in LDPE/phosphate glass hybrids

Shear and elongational viscosity measurements were performed on low-density polyethylene/phosphate glass (LDPE/Pglass) hybrid materials in the liquid state. Under shear deformation, the hybrids with low concentrations of Pglass showed a Newtonian region at low frequencies, followed by shear-thinning behavior at high frequencies. High Pglass concentrations displayed shear-thinning behavior over the whole range of frequencies studied. Deviations from the log-additivity rule for viscosity were found to be compositionally dependent and generally indicated an immiscible mixture. The elongational viscosity of the hybrids increased at very low Pglass concentrations (1–2 vol.% Pglass) and then was drastically reduced at higher concentrations (i.e., >10 vol.% Pglass). In addition, elongational flow was found to induce the formation of Pglass fibrils in hybrids containing at least 10 vol.% Pglass. This was correlated to the elongational capillary number; the critical elongational capillary number was estimated to be 0.22. The elongational deformation was also found to greatly increase the overall crystallinity of the system due to molecular orientation of the LDPE polymer chains as confirmed by wide angle X-ray diffraction. A critical composition of 5 vol.% Pglass was found to be the point at which LDPE hybrid rheological properties, molecular orientation, and morphology changed drastically.