On the predictive/fitting capabilities of the advanced differential constitutive equations for linear polyethylene melts

This contribution examines the capabilities of three differential constitutive models (XPP, PTT-XPP, and modified Leonov) in predicting rheological properties of two virtually linear polyethylene materials (HDPE Tipelin FS 450-26, mLLDPE Exact 0201) with specific attention to both steady as well as transient shear and uniaxial elongational flow situations. For each situation the (dis)advantages of the individual models are discussed and both, qualitative and quantitative model efficiency evaluation has been carried out.     

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     

Transient shear and elongational behavior of blends of PET with a LCP

Blends of polyethylene terephthalate (PET) with a liquid crystalline polymer (LCP) and a compatibilizer were produced by twin screw extrusion and injection molding. Transesterification and compatibilization studies were made in a torque rheometer. The morphology of the injection-molded plaques was studied by scanning electron microscopy. The blends shear growth function was measured in a cone and plate rheometer. The elongational growth function was measured in a modified rotational rheometer. Transesterification was observed in the PET/LCP/compatibilizer 95/5/0 blend. The injection-molded plaques displayed the usual “skin-core” morphology. All the blends were highly shear-thinning, even at low shear rates; thus, a zero-shear viscosity could not be calculated. The compatibilized blend had the highest shear viscosity of all the blends, confirming the strong PET/LCP interphase and the effectiveness of the compatibilizing agent. On the other hand, the 90/10/0 blend had the lowest shear viscosity. All the blends showed strain softening behavior, similar to the PET. The 90/10/0 blend had the highest elongational growth function, while the 95/5/0 had the lowest. The compatibilized blend had an intermediate behavior between both blends.     

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.     

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.     

The BKZ as an alternative to the Wagner model for fitting shear and elongational flow data of an LDPE melt

For the low density polyethylene Melt I, which is the melt for which the most complete set of shear and elongational data exists, the semi-empirical single integral Wagner model gives an excellent data-fit, but suffers the drawback of having no entropic constitutive equation, that is a relationship between strain history and elastic free energy from which viscous heating and cohesive failure can be predicted. We show here that the BKZ model, which does possess an entropic constitutive equation, gives as good a fit as does the Wagner model to both the shear and elongational data.     

Rheological properties of branched polystyrenes: nonlinear shear and extensional behavior

Nonlinear shear and uniaxial extensional measurements on a series of graft-polystyrenes with varying average numbers and molar masses of grafted side chains are presented. Step-strain measurements are performed to evaluate the damping functions of the melts in shear. The damping functions show a decreasing dependence on strain with an increase in mass fraction of grafted side chains. Extensional viscosities of the melts of graft-polystyrenes exhibit a growing strain hardening with increasing average number of grafted side chains as long as the side branches have a sufficient molar mass to be entangled. Graft-polystyrenes with side arms below the critical molar mass M _c for entanglements of linear polystyrene but above the entanglement molar mass M _e of linear polystyrene (M _e < M _w,br < M _c) still show a distinct strain hardening. With decreasing molar mass of the grafted side chains (M _w,br < M _e) the nonlinear-viscoelastic properties of the graft-polystyrene melts approach the behavior for a linear polystyrene with comparable polydispersity.Electronic Supplementary Material Supplementary material is available for this article at     

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.     

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.     

Coarse-grained model of entangled polymer melts in non-equilibrium

A coarse-grained model developed for entangled polymeric systems and calibrated to represent melts in equilibrium (Rakshit, Picu, J Chem Phys 125:164907(1)–(10), 2006) is used to model shear flows. The model is a hybrid between multimode and mean-field representations: chain inner blobs are constrained to move along the chain backbone and the end blobs are free to move in 3D and continuously redefine the diffusion path for the inner blobs. Therefore, contour length fluctuations and reptation are captured. Constraint release is implemented by tracing the position of chain ends and performing a local relaxation of the chain backbones once end retraction is detected. This algorithm takes advantage of the multi-body nature of the model and requires no phenomenological parameters other than the length of an entanglement segment. The model is used to study start-up and step strain shear flows and reproduces features observed experimentally such as the overshoot during start-up shear flow, the Lodge–Meissner law, the monotonicity of the steady state shear stress with the strain rate, and shear thinning at large . These simulations are performed in conditions in which using a fully refined model of the same system would have been extremely computationally demanding or simply impossible with the current methods.     

A new elongational rheometer for polymer melts and other highly viscoelastic liquids

In polymer melt elongational rheometry only by the rotary clamp technique large elongations can be obtained homogeneously. However, as described in this paper, there still remain disadvantages that led to the development of a new rheometer with the following main features: The dimensions of the required sample are small (60 × 7 × 2 nun³), the sample is supported by a cushion of inert gas and, after having reached the test temperature of up to well above 300°C, it can be extended by a new type of clamps that make use of metal conveyor belts. The resulting tensile force is measured with a resolution of better than 100 mgf (0.001 N). The strain rate range is 0.001-1 s^–1, and the maximum Hencky strain is 7, corresponding to a maximum stretch ratio of 1100. Within the sample, the temperature variation in time and space is less than 0.1°C. For the evaluation and documentation of the test performance, a video camera records the top and side views of the sample that carries a marking powder to permit the evaluation of the true strain rate. The operation of the instrument is easy, and so is the sample preparation, but care must be taken concerning the necessary isotropy and internal homogeneity. Examples of test results are given for several polymer melts at various temperatures: (1) Polystyrene up to a total Hencky strain larger than 7 at 170°C, (2) several types of polyethylene (LDPE, LLDPE, HDPE) at 150°C, (3) poly(amide) at 250°C, and (4) poly(ethersulfone) at 350°C. The wide applicability of the new rheometer is demonstrated by adding results obtained from samples of bread dough. The surface tension has no influence on the results if an error of 3% can be tolerated. From the results it follows that by means of the newly developed rheometer many problems in polymer melt elongation have been solved.Dedicated to Professor Dr. Hermann Janeschitz-Kriegl on the occasion of his 70th birthday.Extended version of a paper presented at the XIth International Congress on Rheology, Brussels, Belgium, August 17–21, 1992.     

Shear and elongational flow behavior of acrylic thickener solutions

We investigate the effect of hydrophobic aggregation in alkali-swellable acrylic thickener solutions on shear and extensional flow properties at technically relevant polymer concentrations using the commercial thickener Sterocoll FD as model system. Apparent molecular weight of aggregates in water is M _w  ≈ 10⁸ g/mol and decreases by more than an order of magnitude in ethanol. Zero shear viscosity η ₀ is low and shear thinning is weak compared to the high molecular weight of the aggregates. Linear viscoelastic relaxation is described by the Zimm theory up to frequencies of 10⁴ rad/s, demonstrating that no entanglements are present in these solutions. This is further supported by the concentration dependence of η ₀ and is attributed to strong association within the aggregates. Extensional flow behavior is characterized using the capillary break-up extensional rheometry technique including high-speed imaging. Solutions with ϕ ≥ 1% undergo uniform deformation and show pronounced strain hardening up to large Hencky strains. Elongational relaxation times are more than one order of magnitude lower than the longest shear relaxation times, suggesting that aggregates cannot withstand strong flows and do not contribute to the elongational viscosity.

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     

Simultaneous stress and birefringence measurements during uniaxial elongation of polystyrene melts with narrow molecular weight distribution

Tensile stress and flow-induced birefringence have been measured during uniaxial elongation at a constant strain rate of two polystyrene melts with narrow molecular weight distribution. For both melts, the stress- optical rule (SOR) is found to be fulfilled upto a critical stress of 2.7 MPa, independent of strain rate and temperature. Estimation of the Rouse times of the melts, from both the zero-shear viscosity and the dynamic-shear moduli at high frequency, shows that the violation of the SOR occurs when the strain rate multiplied by the Rouse time of the melt exceeds by approximately 3. The presented results indicate that in contrast to current predictions of molecular theories, the regime of extensional thinning observed by Bach et al. (2003) extends well beyond the onset of failure of the SOR, and therefore the onset of chain stretch in the non-Gaussian regime.

Small and large strain rheology of wheat gluten

 The rheological properties of wheat gluten were studied under both small and large deformation and compared with those of the parent flours. The limiting strain of linear viscoelastic behaviour of gluten doughs, 3 × 10⁻², was an order of magnitude larger than that of the flour doughs, 10⁻³. The role of starch in the lower limiting strain of flour doughs was indicated by the exponential decrease in the limiting strain of gluten-starch mixtures with greater quantities of starch. Large strain measurements showed gluten doughs possessed greater shear and elongational viscosities than flour doughs and these differences were greatest at lower shear and elongation rates (0.01 and 0.1 s⁻¹). The larger viscosities of flour and gluten doughs at the low strain rates help to stabilise and prevent the collapse of gas bubbles during bread fermentation and baking. Increasing starch levels in gluten-starch mixtures, at either constant or optimal water levels, lowered the elongational viscosity. Dynamic measurements were, however, more sensitive to the level of water added to the gluten-starch mixtures. The storage modulus decreased with increasing starch levels when constant water levels were used to prepare the mixtures, but when optimal water levels were used the storage modulus increased. Gluten and starch are major contributors to the large and small strain rheological properties of flour doughs; however, gluten-starch mixtures were unable to duplicate exactly the rheological properties of flour doughs, indicating that other flour components such as pentosans, lipids and water soluble proteins also influence dough rheology. Received: 20 March 2001 Accepted: 11 July 2001     

Numerical simulation of large amplitude oscillatory shear of a high-density polyethylene melt using the MSF model

We study the flow response in large amplitude oscillatory shear of the molecular stress function (MSF) model that has recently been proposed by Wagner et al. [M.H. Wagner, P. Rubio, H. Bastian, The molecular stress function model for polydisperse polymer melts with dissipative convective constraint release, J. Rheol. 45 (2001) 1387–1412]. The MSF model is derived from molecular theory and has only two parameters to describe the non-linear material response. The model predictions are analysed in both the frequency and time domain. It shows good agreement with experimental data for a linear high-density polyethylene melt. At low and medium strains, MSF model predictions are in excellent agreement with experimental data and predictions of a six-mode Giesekus model which has six parameters to describe the non-linear material response. At medium strains, the basic Doi–Edwards model, which has no non-linear parameters, already underpredicts the data. At high strains, the MSF model predictions agree slightly better with the experimental data than the Giesekus model. Surprisingly, however, it is the Doi–Edwards model that shows excellent agreement with experimental data at high strains. For the linear melt we consider, it outperforms the models that have non-linear parameters, both in the time and frequency domain.     

Rheological characterisation of a high-density polyethylene with a multi-mode differential viscoelastic model and numerical simulation of transient elongational recovery experiments

The rheological characterisation of a high-density polyethylene is performed by means of measurements of the storage and loss moduli, the shear viscosity and the transient uniaxial elongational viscosity, the latter being obtained with the Meissner extensional rheometer. The rheological behaviour of the polymeric material is described by means of a multi-mode Phan Thien-Tanner fluid model, the parameters of which are successively fitted on the basis of the linear and non-linear properties. By using a semi-analytical technique and the finite element method, numerical investigations are performed for the shape recovery of the sample, and the predictions are compared with their experimental counterparts. Surface tension effects are also explored. We discuss the agreement between the experiments and the simulation results. Received: 15 October 1998 Accepted: 22 December 1998     

Inlet instabilities in the capillary flow of polyethylene melts

Inlet instabilities in the capillary flow of polyethylene melts were studied in this work. Extrudate distortions in branched polyethylenes, produced by unstable upstream flow, were found to be accompanied by pressure oscillations that do not have their origin in the slip phenomenon, but on polymer compressibility. The absence of slip was clearly evidenced in the experiments, and the differences between pressure oscillations occurring in linear and branched polymers are shown.Pressure oscillations in the capillary flow of branched polyethylenes were found to be made up of at least two components of different frequency and amplitude. These two components were identified with different bulk defects appearing in the extrudates. Information about the dynamics of vortices upstream of the contraction and extrudate distortions is obtained from the analysis of pressure oscillations.The influence of capillary entrance angle on flow curves was also investigated. From the results, it is concluded that the extensional component of the flow in the contraction is the main factor responsible for the slope change usually found in the log-log flow curves of both linear and branched polyethylenes.     

Molecular mass dependence of the zero shear-rate viscosity of LDPE melts: evidence of an exponential behaviour

The molecular mass dependence of the zero shear-rate viscosity of low-density polyethylene (LDPE) melts is revisited for a series of LDPE samples of different molecular masses and densities. The long-chain branching structure and absolute weight average molecular masses are determined using a state-of-the-art size exclusion chromatography system coupled with multi-angle laser light-scattering. Creep experiments in a stress-controlled rotational rheometer are used to determine the zero shear-rate viscosity. The experimental results give evidence of an exponential molecular mass dependence of zero shear viscosity. It is demonstrated that these results can qualitatively be explained by comparison with recent theoretical predictions of the rheological properties of comb-branched model polymers.