Rheological properties of long glass fiber filled polypropylene

Long glass fiber-filled polypropylene (PP) composites are produced by pultrusion, and the extrudate is cut at different lengths producing composites containing long fibers of controlled length. The rheological properties of such composites in the molten state have been studied using different rheometers. A capillary rheometer has been constructed and mounted on a molding-injection machine. The shear viscosity of filled PP determined from the capillary rheometer, after corrections for entrance effects, was found to be very close to that of unfilled PP. However, large excess pressure losses at the capillary entrance were observed and these data have been used to obtain an apparent elongational viscosity. The apparent elongational viscosity was shown to be considerably larger than the shear viscosity for PP and filled PP, and it increased markedly with fiber length and fiber content. Rotational rheometers with a parallel-plate geometry were used to investigate the viscoelastic properties of these composites and their behavior was found to be non-linear, exhibiting a yield stress. A model is proposed to describe the shear viscosity from a solid-like behavior at low stresses to fluid-like behavior at high shear stresses taking into account fiber content and orientation. A modified model, proposed for elongational flow, describes relatively well the apparent elongational data.     

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.     

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.     

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.     

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.     

Sliding plate rheometry of planar oriented concentrated fiber suspension

The rheology of concentrated planar fiber suspensions is investigated. A new experimental technique for fiber suspensions based on a sliding plate rheometer incorporating a shear stress transducer is developed. It is shown that this instrument works well for the tested material systems. The rheological behavior in steady shear is subsequently investigated. The results can be largely explained by a combination of frictional and hydrodynamic interaction. Despite this evidence of friction no yield stress could be detected for the investigated shear rates. It was also found that the fiber aspect ratio did not influence the steady shear viscosity.     

Exponential shear flow of branched polyethylenes in rotational parallel-plate geometry

Exponential shear flow, as a strong flow with the potential to generate a high degree of molecular stretching, has attracted considerable interest in recent years. So far, exponential shear flow has been realized by either sliding-plate or cone-and-plate (CP) geometry. Both geometries guarantee homogeneous shear flow. Here, we present experimental data on exponential shear flow of several long-chain branched polyethylene melts with different degrees of strain hardening obtained by using parallel-plate (PP) geometry in a rotational rheometer. This type of geometry, which is standard in linear-viscoelastic characterization of polymer materials, produces inhomogeneous shear flow. A comparison of exponential shear flow data obtained by PP and CP geometry is made. Additionally, the experimental data are compared to predictions of the rubber-like liquid (RLL) and the molecular stress function (MSF) theories. For this purpose, the relaxation spectra of the polymer melts considered were obtained by standard linear-viscoelastic characterization. In addition, two irrotational parameters and one rotational parameter are required by the MSF theory. While the irrotational parameters were obtained from fitting to elongational viscosity data, the value of the rotational parameter was used as given in the literature. It can be concluded that viable experimental data in exponential shear flow can be obtained by PP geometry. For finite linear-viscoelasticity (RLL theory), predictions of reduced shear stress for CP and PP geometry coincide, but nonlinear material behavior (as modeled by the MSF theory) leads to small differences between both geometries. Furthermore, it is shown that the MSF predictions are in excellent agreement with the experimental data in exponential shear flow and that this type of flow leads to much less chain stretching than elongational flow.Dedicated to the memory of Prof. Arthur S. Lodge (1922–2005).     

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.     

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     

The effect of viscoelasticity on the extrusion drawing in film-casting process

The governing rheological property for extrusion drawing in film-casting process is proposed in this study. The experiment of film-casting process using the high-pressure process low-density polyethylene (LDPE) was performed. The non-isothermal viscoelastic simulation of the film casting experiment was also carried out to explain the experimental results. Film width reduction phenomenon in an air gap, so-called neck-in behavior, was investigated by using the simulation of the LDPE and the model fluids exhibiting specific viscoelasticity. The neck-in phenomenon was also examined using theoretical model based on force balance and deformation type of a film. As a result, the neck-in normalized by the air gap was in good correlation with the ratio of planar to uniaxial elongational viscosity rather than the strain hardening nature of uniaxial elongational viscosity.     

Determination of elongational viscosity of polymer melts by RME and Rheotens experiments

Several linear (LLDPE, HDPE, PS) and long-chain-branched (LDPE, PP) polymer melts were investigated by an elongational rheometer (RME Rheometrics) and by Rheotens (Göttfert). The Molecular Stress Function (MSF) theory is briefly reviewed and used to extrapolate the steady-state elongational viscosity. To evaluate Rheotens experiments, a new process model is introduced which assumes that the elongational viscosity in the Rheotens test is a function of the draw ratio only. The apparent elongational viscosities extracted from Rheotens curves are found to lie in between the steady-state elongational viscosity and three times the shear viscosity.     

Determination of the elongational viscosity of polymer melts by melt spinning experiments. A comparison with different experimental techniques

In this work, melt spinning experiments were tentatively used for the determination of the elongational viscosity of polymer melts at different levels of tensile strain and strain rate. The materials examined were two high-density polyethylene grades for blow moulding with similar number-average molecular mass but different polydispersity index. The data from melt spinning tests were compared with transient extensional viscosity data obtained by uniform isothermal tensile tests, performed by means of an extensional rheometer, as well as with those produced by converging flow tests (Cogswell model). The results showed that for high strain and strain rate levels, the melt spinning experiments provide elongational viscosity data quite close to the transient extensional viscosity values obtained from the tensile tests.     

Material functions for constant-strain-rate elongational flows

The problem of determination of invariant material functions for elongational flows in which two components of the constant strain-rate tensor are equal is briefly discussed, and a method of its solution described. The method is based on simultaneous modeling of the elongational viscosity as measured in uniform uniaxial elongational flow, and the shear viscosity as measured in steady viscometric flow. A single integral model with a strain-rate dependent memory is used to correlate both viscosities over a given experimental range of strain rates. The procedure has been applied to a set of experimental data obtained for a low-density polyethylene melt by Laun and Münstedt.     

Shear rheometry and visualization of glass fiber suspensions

The nonlinear rheological behavior of short glass fiber suspensions has been investigated in this work by rotational rheometry and flow visualization. A Newtonian and a Boger fluid (BF) were used as suspending media. The suspensions exhibited shear thinning in the semidilute regime and weaker shear thinning in the transition to the concentrated one. Normal stresses and relative viscosity were higher for the BF suspensions than for the Newtonian ones presumably due to enhanced hydrodynamic interactions resulting from BF elasticity. In addition, relative viscosity of the suspensions increased rapidly with fiber content, suggesting that the rheological behavior in the concentrated regime is dominated by mechanical contacts between fibers. Visualization of individual fibers and their interactions under flow allowed the detection of aggregates, which arise from adhesive contacts. The orientation states of the fibers were quantified by a second order tensor and fast Fourier transforms of the flow field images. Fully oriented states occurred for shear rates around 20 s^− 1. Finally, the energy required to orient the fibers was higher in step forward than in reversal flow experiments due to a change in the spatial distribution of fibers, from isotropic to planar oriented, during the forward experiments.     

Measurement of planar elongation stress and viscosity in step planar elongation flow for mobile viscoelastic fluids

We propose a new technique which can treat low viscous viscoelastic fluids and which can measure the start-up and relaxation behavior of elongational stress in step elongation rate flow. This new device consists of two parts: the squeeze cell and the optical analyzer. The squeeze cell generates the planar squeeze flow and causes the step planar elongational flow at the stagnation point. The optical system measures the transient behavior of both birefringence and orientation angle in the start-up and relaxation region at the stagnation point. In this paper, we demonstrate the two-dimensionality of the flow in the planar squeeze cell. Next, we evaluated the planar elongational stress and viscosity from optical results for Maxwell fluid. These results show good agreement with Maxwell model. Finally, we clarify the measurement accuracy from the measurement results in channels of various sizes.     

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.     

Influence of molecular structure on secondary flow of polyolefin melts as investigated by laser-Doppler velocimetry

Laser-Doppler velocimetry (LDV) is applied to investigate velocity profiles in the entrance region of a slit die. Due to the high spatial resolution of the device and the accuracy of the velocity measurements the secondary flow patterns of different polyolefins have quantitatively been analyzed for the first time. A linear polyethylene is compared with two long-chain branched polyethylenes and a conventional linear polypropylene with a long-chain branched one. All materials are rheologically characterized with respect to their viscosity functions, elasticity, and elongational properties. For the two linear materials no indication of secondary flow is found, but the three long-chain branched polymers (two polyethylenes and one polypropylene) exhibit pronounced vortices. Neither viscosity nor elasticity seem to be decisive for the occurrence of secondary flow. The viscosity has an influence, however, on the size of the vortices and the velocities within them. All of the three long-chain branched polymers are strongly strain hardening which gives rise to the conclusion that this behavior may be a necessary condition for the formation of vortices. The linear polypropylene does not show any indication of strain hardening. The linear polyethylene, surprisingly, is significantly strain hardening, but it becomes less pronounced with higher strain rates. As most of the deformation in the entrance region takes place at elongational rates at which the strain hardening of the linear polyethylene is not significant, the findings on the linear polyethylene do not contradict the hypothesis that strain hardening and vortex formation in entrance flow may be related to each other. Received: 27 April 2000 Accepted: 30 November 2000     

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.     

Transient shear flow behavior of concentrated long glass fiber suspensions in a sliding plate rheometer

In order to eventually predict the behavior of long fiber suspensions in complex flows commonly found in processing operations, it is necessary to understand their rheology and its connection to the evolution of fiber orientation and configuration in well defined flows. In this paper we report the transient behavior at the startup of shear flow of a polymer melt containing long glass fibers with a length (L) >1 mm, using a sliding plate rheometer (SPR). The operation of the SPR was confirmed by comparing the transient shear viscosity (η⁺) for a polymer melt and a melt containing short glass fibers (L < 1 mm) with measurements obtained from a cone-and-plate device, using a modified sample geometry that was designed to avoid wall effects. For the long fiber systems, measurements could only be obtained in the SPR because these systems would not stay within the gap of the rotational rheometer. Transient stress growth behavior of the long fiber systems was obtained as a function of shear rate and fiber concentration for samples prepared with three different initial orientations. Results showed that, unlike short fiber systems (with a random planar initial orientation) that usually exhibit a single overshoot peak followed by a steady state, η⁺ of the long fiber suspensions often passed through multiple transient regions, depending on the fiber concentration and applied shear rate. Additionally, η⁺ of the long fiber suspensions was found to be highly dependent on the initial orientation of the sheared samples. Finally, the initial and final fiber orientations of the long glass fiber samples were measured and used to initiate an explanation of the viscosity behavior. The results obtained in this research will be useful for future assessment of a quantitative correlation between transient rheology and the evolution of fiber orientation.