Numerical simulation of elongational flow behaviour in the cross cell experiments

In this work, numerical simulation of an elongational flow of polymer solutions is tried. The flow field is computed in a cell of simple geometry for newtonian, non-newtonian inelastic and non-newtonian elastic fluids. For the latter, an Oldroyd four-constant-model was adopted. The results are qualitatively in good agreement with the experimental results.     

The influence of blending polystyrenes of narrow molecular weight distribution on melt creep flow and creep recovery in elongation

Creep and creep recovery experiments in elongation were performed with melts of anionically polymerized polystyrenes (PS) and with their blends at a temperature of 150 °C. For stresses ₀ < 10 000 N/m² the samples with narrow molecular weight distribution show linear viscoelastic behavior up to the maximum Hencky strain = 3.5, achievable in a newly developed elongational rheometer for polymer melts. The compliances,D (t), of the blends are linear-viscoelastic only up to a strain limit _L . For strains beyond _L the compliance of each blend depends on the stress ₀. For a series of binary blends, prepared from the same components of narrow MWD, the linear-viscoelastic limit _L seems to be independent of the mixing ratio and stress. _L seems to be a function only of the molecular weights of the original components, the blends investigated were made from.Paper presented at the Annual Conference of the German Society of Rheology at Ulm, March 7–10, 1983.     

Metastable flow in capillary tubes: An experimental evaluation

This work presents the results of an experimental study with pure refrigerants R-134a and R-600a and refrigerant–oil mixtures flowing through capillary tubes in order to analyse the metastable flow. A large number of experiments were carried out to verify the influence of several variables on the underpressure of vaporization, mainly the inlet subcooling, internal diameter and inlet pressure. Capillary tubes with internal diameter of 0.69 mm and 0.82 mm were tested for condensation temperatures between 40 °C and 50 °C and subcooling degrees between 3 °C and 12 °C. Measurements for oil concentrations of 1% and 3% were conducted and compared with those for pure refrigerant R-134a. The oil influence on the metastable flow was tested and the effect on the underpressure of vaporization is addressed for lower oil concentrations.     

Shear flow properties of concentrated solutions of linear and star branched polystyrenes

Summary The linear viscoelastic and viscometric functions have been determined for solutions of wellcharacterized monodisperse linear and star-branched polystyrenes and for commercial, polydisperse polystyrene. The value of the product c for these solutions was large and was obtained by using both high and low The effect of structure on the rheological properties was determined by examining how parameters in a modified Carreau viscosity equation (used to fit the data) varied with c, , and branching. No enhancement effects on the rheological properties were observed because of branching.The Cox-Merz rule was observed to describe the similarities between the viscosity and complex viscosity for most of the monodisperse samples studied. The broad molecular weight distribution polystyrene solutions did not follow this empiricism.With 17 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.

Extensional flow of HDPE/LDPE blends

Elongational viscosity data, obtained through the converging flow analysis by Cogswell, are presented for two types of HDPE/LDPE blends at various compositions and different temperatures. The results relative to the homopolymer parents compare favourably with literature data obtained also with different and more sophisticated techniques. Those relative to blends show peculiar features for the two cases: when the newtonian viscosity of the LDPE is higher all the blends show a behaviour typical of the LDPE with a maximum in _el / ₀ enhanced at small percentage of HDPE; when the newtonian viscosity of the LDPE is similar to that of the HDPE there is only a gradual change in the properties.     

Linear stability of homogeneous elongational flow of the upper convected Maxwell fluid

We prove that planar elongational flow of the upper convected Maxwell fluid is linearly stable and analyze the associated spectral problem.     

Analysis of entry flow to determine elongation flow properties revisited

The minimisation technique proposed by Binding (J. Non-Newtonian Fluid Mech., 27 (1988) 173) was used in our Generalised Engineering Bernoulli Equation framework to relate the entry pressure and stress power. We arrived at a final result similar to Binding's using assumed kinematics. Through subsequent assumptions to the kinematics we finally arrive at a result exactly equivalent to Cogswell's technique (Trans. Soc. Rheol., 16 (1972) 383). Thus, these two techniques are related in this general framework. The techniques were used to predict elongation flow properties of a polymer melt and polymer solution. The results for the polymer melt clearly show Cogswell's technique is adequate at high elongation rates. All these techniques require minimisation of the stress power with respect to the flow volume and discussion is given as to the validity of this minimisation technique. In addition, the approximate variational technique we propose gives clears limits as to when a technique, such as Cogswell's, can be applied.     

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.

Predicting the linear viscoelastic properties of monodisperse and polydisperse polystyrenes and polyethylenes

 For linear homopolymers the linear viscoelastic predictions of the double reptation model are compared to those of a recent, more detailed model, the “dual constraint model” and to experimental data for monodisperse, bidisperse, and polydisperse polystyrene melts from several laboratories. A mapping procedure is developed that links the empirical parameter K of the double reptation model to the molecular parameter τ_e of the dual constraint model, thereby allowing the parameter K to be related to molecular characteristics such as the monomeric friction coefficient ζ. Once K (or τ_e) are determined from data for monodisperse polymers, the double reptation model predicts that for fixed weight-average molecular weight M_w, the zero-shear viscosity η₀ increases slightly with increasing polydispersity M_w/M_n for log normal distributions, while for the dual constraint model η₀ is almost independent of M_w/M_n. Experimental data for polystyrenes show no increase (or even a slight decrease) in η₀ with increasing M_w/M_n at fixed M_w, indicating a deficiency in the double reptation model. The dual constraint theory is also applied to hydrogenated polybutadienes and commercial high-density polyethylenes, where we believe it can be used to indicate the presence of long side branches, which are difficult to detect by other analytic methods. Received: 11 October 2000 Accepted: 17 May 2001     

Uniaxial deformation and relaxation of polymer blends: relationship between flow and morphology development

Uniaxial elongational flow followed by stress relaxation of a dilute mixture of polystyrene/polymethylmethacrylate) PS/PMMA with PS (5 wt%) as a dispersed phase was investigated. The behavior of the blend was found to be dominated by the PMMA matrix during elongation and by the interface during the relaxation at long time. Such a behavior was related to drop deformation and shape recovery during the relaxation process as was confirmed by morphological analyses on samples quenched within the rheometer just after elongation and at various times during the relaxation process. The morphology and the rheological material functions variation were compared to the Yu model (Yu W, Bousmina M, Grmela M, Palierne JF, Zhou C (2002) Quantitative relationship between rheology and morphology in emulsions. J Rheol 46(6):1381–1399).     

Excluded volume effects on the birefringence and stress of dilute polymer solutions in extensional flow

An algorithm is derived for calculating flow-induced birefringence using a bead-spring model with and without excluded volume effects. The simulation results for the bead-spring model compare well with experimental results for stress and birefringence in extensional flows of dilute solutions of polystyrene molecular weight 2 million in a filament-stretching device in both “theta” and “good” solvents (Orr and Sridhar 1999; Sridhar et al. 2000). In a “good” solvent, both stress and birefringence rise much more rapidly with strain than in a “theta” solvent, making extensional rheology a very sensitive indicator of solvent quality. Received: 7 December 1999 Accepted: 23 May 2000     

An experimental study of diabatic spiral vortex flow

In spiral vortex flow, between concentric cylinders with the inner cylinder rotating and the outer stationary, the addition of a thermal gradient across the gap is a known complicating factor. The present diabatic study for narrow and wide gaps (radius ratios N=0.955 and N=0.8), with a heated outer and adiabatic inner cylinder, was undertaken to investigate this problem. The heat transfer characteristics and the modes of transition have been investigated together with the relationship between them. Using standard on-line digital computer techniques, the onset of vortex flow and its higher transitions have been shown to cause a sharp increase in Nusselt number. At higher Taylor numbers, of the order of 10⁶, a marked change in the Nusselt number occurs with the onset of the transition to periodic turbulent vortex flow. Outer wall heating is seen to affect the modes of transition. Diabatic critical Taylor numbers are much higher than those for adiabatic conditions and are found to depend on the close approach of the vortices to the outer wall     

Squeezing flow of a highly viscous incompressible liquid pressed between slightly inclined lubricated wide plates

The theoretical force-height relationships of Newtonian and pseudo plastic liquids compressed between slightly tilted frictionless plates are compared with those produced when the plates are perfectly parallel. It is shown that a very small inclination angle can distort the flow curve to such an extent that a Newtonian liquid will appear as a pseudo plastic fluid, and a pseudo plastic liquid as having a flow index considerably smaller than its true one. The shape of the biaxial elongational viscosity vs biaxial strain rate relationship is also highly sensitive to the plates' inclination angle. Thus, if an experimental force-height relationship is used to determine a material's biaxial elongational viscosity, an unsuspected slight tilt will result in a considerable underestimate of the viscosity. A slight tilt will also produce an apparent strain rate dependency in a Newtonian liquid, which obviously does not exist. The mathematical model developed to reach these conclusions was tested with commercial mayonnaise, a self-lubricating fluid. A reasonable agreement was found between the predicted force-height relationships and those experimentally determined at tilts of 1°, 3°, and 5°. Received: 4 August 2000 Accepted: 21 August 2000     

An experimental study of planar entry flow of rubber compound

An automated rheometer based on an injection molding machine is developed for the evaluation of entry flow problems. Several entry flow geometries having different contraction and expansion angles and different channel lengths are tested. Two pressure transducers are flushmounted along the die length and a displacement transducer is installed to measure the screw motion. Signals generated by the pressure transducers and displacement transducer are supplied to an A/D converter and an IBM PC/AT computer. The pressure losses for a rubber compound are measured between two cross-sections along the flow direction. The time evolution of pressure with overshoot during flow before and after the entry region is observed. At low flow rates the pressure drops of the expansion flow are larger than those of the contraction flow. At high flow rates the pressure drops of the contraction flow become higher than those of the expansion flow. A ratio of the pressure drop to absolute pressure before the entry is found to be almost independent of flow rate.     

Molecular orientation in non-Newtonian flow of dilute polymer solutions around spheres

A novel approach is presented to study the benchmark problem of flow around spheres in model dilute solutions of monodisperse samples of atactic polystyrene in di-octyl phthalate. Spheres are held stationary on flexible cantilevers of known spring-constant, k, while the polymer solutions are pumped past at controlled flow rates, allowing access to a wide range of Deborah number. In this way the non-Newtonian forces experienced by the spheres can be measured as a function of Deborah number, while detailed observations and measurements of birefringence are made, enabling assessment of macromolecular strain and orientation. In addition the flow field around a sphere has been measured in an a-PS solution. Experiments have been performed on a single sphere and on two spheres axially aligned in the direction of flow. The extensional flow around the downstream stagnation point of the single sphere is found to play a pivotal role in the development of molecular strain and stress, resulting in flow modification and subsequent non-Newtonian behaviour. The flow birefringence in the wake is found to modify severely the flow around a second, downstream, sphere, affecting the non-Newtonian forces encountered by the second sphere. This provides an explanation for the time interval dependent terminal velocity often observed when two spheres follow the same path through viscoelastic liquids.     

An experimental investigation of the shear behaviour of polyethylenes with different structures

Rheological properties in shear flow are presented for four different polyethylene samples: a high density, a linear low density and two low density polyethylenes manufactured using different techniques. Tests have been performed with the aid of capillary types of instrument equipped with capillaries of various lengths at three different temperatures. End correction factors have been determined and true flow curves obtained. Swelling ratios for both unannealed and annealed samples have been determined as well as the shear rate and shear stress at which irregularities begin. In some cases generalized plots have been prepared and in all cases the rheological response is discussed in terms of molecular characteristics, in particular the average molecular weight, molecular weight distribution and degree of branching.     

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     

Rheological behaviour and molecular structure of long-chain branched semifluorinated thermoplastics

The long-chain branched thermoplastic tetrafluoroethylene–hexafluoropropylene–vinylidenefluoride terpolymers (LCB THV) investigated in this paper are new polymers with a unique combination of properties like a high stability against aging or weathering and a very good chemical resistance. But not much is known about the rheological behaviour of the LCB THV, yet. In this paper, non-linear rheological properties like shear thinning and strain hardening are studied. Two different types of the THV with different contents of comonomers and, therefore, different melting points are examined. The THV with the higher melting point is insoluble. The other with the lower melting temperature is soluble and, therefore, was characterised by size exclusion chromatography coupled with light scattering with respect to its molecular structure. The results of the rheological measurements show a pronounced shear-thinning and strain-hardening behaviour for the long-chain branched materials. Both properties are of great importance for processing operations governed by shear and elongational flows.

Channel flow of a liquid crystal polymer around an obstacle: Weld line structure and strain field

 We have studied by in situ microscopy the flow of a lyotropic liquid crystal polymer, hydroxypropylcellulose (HPC) in water, around an obstacle placed in a rectangular flow channel. The obstacle separates the flow into two parts which rejoin downstream of the obstacle, resulting in the formation of a `weld-line'. Measuring the velocity field in the vicinity of the weld-line beyond the obstacle, we find as expected a positive elongational strain (acceleration) along the weld (parallel to the flow direction). For an anisotropic (concentrated) HPC solution we observe in addition a significant shear strain in the weld-line region, there being an important velocity gradient perpendicular to the plane of the weld line. Isotropic (lower concentration) solutions of the same polymer demonstrate no visible weld line, a larger elongational strain rate near the obstacle, and no shear component of strain downstream of the obstacle. These results are similar to observations reported for fluids reinforced by macroscopic fibres. Polarised light observations of the anisotropic solution show that the strain field generates a generally increased degree of orientation of the liquid crytalline polymer near the weld (generally reduced crossed-polariser transmitted intensity when the polariser is parallel to the flow direction), however there is also a striking fine birefringent colour variation in the weld-line region, reminiscent of the structure observed at the channel side walls in rectangular channel flow (Haw and Navard 2000). The results show that the simple concept of weld-line structure as confined to an enhanced alignment along the weld due to elongational strain is incomplete; the two-dimensional shear strain field must also be taken into account for the anisotropic fluid. Received: 22 December 1999/Accepted: 4 January 2000