Modeling strain hardening of polydisperse polystyrene melts by molecular stress function theory

The strain hardening of blends of polystyrene (PS) and ultra-high molecular weight polystyrene (UHMW-PS) in elongational flow is modeled by the molecular stress function (MSF) theory. Assuming that the ratios of strain energies stored in polydisperse and monodisperse polymers are identical for linear and nonlinear deformations, the value of the only non-linear parameter of the theory in extensional flows, the maximum molecular stress f_max, can be determined and is shown to be related to steady-state compliance J_e0. Using only linear-viscoelastic data, the elongational viscosity of PS/UHMW-PS blends is consistently predicted by the MSF theory.     

Large amplitude oscillatory elongation flow

A filament stretching rheometer (FSR) was used for measuring the elongation flow with a large amplitude oscillative elongation imposed upon the flow. The large amplitude oscillation imposed upon the elongational flow as a function of the time t was defined as where ε is the Hencky strain, is a constant elongational rate for the base elongational flow, Λ the strain amplitude (Λ ≥ 0), and Ω the strain frequency. A narrow molecular mass distribution linear polystyrene with a molecular weight of 145 kg/mol was subjected to the oscillative flow. The onset of the steady periodic regime is reached at the same Hencky strain as the onset of the steady elongational viscosity ( Λ = 0). The integral molecular stress function formulation within the ‘interchain pressure’ concept agrees qualitatively with the experiments.     

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.     

Morphology development in polystyrene/polyethylene blends during uniaxial elongational flow

The deformation of linear low-density and low-density polyethylene particles dispersed in a polystyrene matrix was studied during defined uniaxial elongational flow conditions for different capillarity numbers and different temperatures. The morphology of the elongated samples was analysed by quenching the specimens in liquid nitrogen directly after the deformation. Furthermore, morphology development after recovery was investigated. By measuring the transient elongational viscosity of the blend matrix the true hydrodynamic stress during the flow process was calculated. Using a modified critical capillarity number, the fibril formation of the dispersed phase could be described at all test conditions. Virtually no break-up processes were observed. This finding could be explained by calculating the characteristic time of fibril break-up due to Rayleigh instabilities. By annealing the elongated samples a spherical shape of the dispersed droplets was regained. Compared with the initial sample morphology a pronounced increase of the particle sizes due to coalescence processes during elongation was observed.     

Birefringence measurements on polymer melts in an axisymmetric flow cell

 The stress-optical rule relates birefringence to stress. Consequently, measurement of flow birefringence provides a non-intrusive technique of measuring stresses in complex flows. In this investigation we explore the use of an axisymmetric geometry to create a uniaxial elongational flow in polymer melts. In axisymmetric flows both birefringence and orientation angle change continuously along the path of the propagating light. The cumulative influence of the material's optical properties along the light's integrated path makes determination of local birefringence in the melt impossible. One can nevertheless use birefringence measurements to compare with predictions from computer simulations as a means of evaluating the constitutive equations for the stress. More specifically, in this investigation we compare the light intensity transmitted through the experimental set-up vs entry position, with the theoretically calculated transmitted intensity distribution as a means of comparing experiment and simulation. The main complication in our experiments is the use of a flow cell that necessarily consists of materials of different refractive indices. This introduces refraction and reflection effects that must be modeled before experimental results can be correctly interpreted. We describe how these effects are taken into account and test the accuracy of predictions against experiments. In addition, the high temperatures required to investigate polymer melts mean that a further complication is introduced by thermal stresses present in the flow cell glass. We describe how these thermal-stresses are also incorporated in the simulations. Finally, we present some preliminary results and evaluate the success of the overall method. Received: 2 April 2001 Accepted: 27 August 2001     

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     

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 measurements of velocity and stress distributions in polyisobutylenes using laser-Doppler velocimetry and flow induced birefringence

An experimental device was set up for the synchronous measurement of velocities and stresses in polyisobutylenes using laser-Doppler velocimetry (LDV) and the two-colour flow-induced birefringence method (FIB). The materials investigated are three low molecular polyisobutylenes. Velocity (LDV) and stress (FIB) measurements are performed in the flow entrance region and inside a slit die with a contraction ratio of 1:10. The behaviour of the polyisobutylenes is Newtonian under the flow conditions applied. Therefore, the stresses inside the fluids can be calculated and compared to the stresses experimentally determined. A good agreement in shear and elongational flows was found between the calculated (LDV) and directly measured stresses (FIB). This result demonstrates the applicability of the experimental setup as an optical rheometer that can preferentially be used to measure elongational properties of low viscous fluids.

Flow of branched polymer melts in a lubricated cross-slot channel: a combined computational and experimental study

Numerical simulations have been performed to evaluate the accuracy of the multimode Giesekus model in predicting the flow behavior of a rheologically well characterized low-density polyethylene melt in a lubricated cross-slot channel. Specifically, the fidelity of the numerical results is established by detailed comparison with flow-induced birefringence measurements in a new optical rheometer with lubricated side walls that allows the creation of ideal two-dimensional flow kinematics that lead to the elimination of end effects commonly encountered in flow birefringence measurements. Based on these comparisons, the ability of the multimode Giesekus model to capture the flow characteristics with reasonable accuracy in the experimentally available Wi range of 21 to 29 has been established. However, it should be noted that the model predictions are, at best, qualitative in the vicinity of the stagnation point. The discrepancy between numerically predicted and experimentally observed stresses in this region is mainly attributed to the inaccuracy of the experimental data that stem from the occurrence of multiple orders of retardation within the measurement volume. Overall, these studies have paved the way for the development of a hi-fidelity lubricated cross-slot channel rheometer.     

Modelling elongational and shear rheology of two LDPE melts

Experimental data of two low-density polyethylene (LDPE) melts at 200°C for both shear flow (transient and steady shear viscosity as well as transient and steady first normal stress coefficient) and elongational flow (transient and steady-state elongational viscosity) as published by Pivokonsky et al. (J Non-Newtonian Fluid Mech 135:58–67, 2006) were analysed using the molecular stress function model for broadly distributed, randomly branched molecular structures. For quantitative modelling of melt rheology in both types of flow and in a very wide range of deformation rates, only three nonlinear viscoelastic material parameters are needed: Whilst the rotational parameter, a ₂, and the structural parameter, β, are found to be equal for the two melts considered, the melts differ in the parameter describing maximum stretch of the polymer chains.     

Simultaneous measurement of transient stress and flow birefringence in one-sided compression (biaxial extension) of a polymer melt

Summary Investigation of time dependent behaviour of a polystyrene melt is carried out with the aid of a new apparatus for biaxial extension. Use is made of the method of two impinging fluid streams guided by lubricated trumpet shaped metal walls. The flow birefringence is measured in the plane of symmetry and, at the same time, the force is measured which tends to separate the trumpets. The linear stress-optical relation turns out to be valid in this new flow geometry. An accurate value for the stress-optical coefficient can be determined from the relaxation experiments. The stress build-up as calculated from the optical measurements, is compared with the pertinent result of the theory of linear viscoelasticity. For the desired interconversion of dynamic moduli use is made of the approximation by Schwarzl and Struik. The steady state measurements are checked by the results of the non-linear model of Acierno et al.With 16 figures and 2 tables     

Shear banding during nonlinear creep with a solution of monodisperse polystyrene

Creep experiments with a solution of polystyrene (M _w = 2.6 MDa, 16 vol.%, 25 °C) in diethyl phthalate are reported for stresses between 100 and 2,500 Pa (≈ 3G _N ⁰/4). The aim was to look for a flow transition as reported for strongly entangled poly(isobutylene) solutions. The experiments with the polystyrene solution were repeated for cone angles of 2, 4, and 6° (radius 15 mm) and showed no dependence on cone angle. The Cox–Merz rule was not fulfilled for stresses beyond about 800 Pa. The tangential observation with a CCD camera showed that the edge took a concave shape because of the second normal stress difference. Beyond 1,000 Pa, the concave edge develops into a crevice, thus substantially reducing the effective cross-section. This leads to runaway in a constant torque experiment. At p ₂₁ = 800 Pa, head-on particle tracking confirms that the originally linear velocity profile takes a gooseneck shape, thus revealing shear banding. When the creep stress is stepped down to 100 Pa, this velocity profile evolves back to a linear one. The conclusion from this work is that even if nonlinear creep experiments are reproducible and a steady state is reached, this does not mean that the flow field is homogeneous. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Direct comparison of equibiaxial elongational viscosity measurements from lubricated squeezing flow and the MultiAxiales Dehnrheometer

We present the first direct comparisons of rheological data from the lubricated squeezing flow (LSF) technique and the MultiAxiales Dehnrheometer (MAD) instrument developed by Meissner and coworkers (J Rheol 47:989–1010, 2003). Comparisons of transient equibiaxial elongational viscosity are carried out at strain rates well into the nonlinear regime on low-density polyethylene and polystyrene melts. We find data obtained using LSF deviate from the MAD data when the Hencky strain reaches a value of approximately 1, which we interpret as a failure of the LSF technique. The strain at which the LSF technique fails is relatively insensitive to experimental parameters including strain rate. For Hencky strains larger than 1, LSF data display behavior that could easily be mistaken for the phenomenon of strain hardening.     

The shear viscosity dependence on concentration,molecular weight,and shear rate of polystyrene solutions

The solution viscosity of narrow molecular weight distribution polystyrene samples dissolved in toluene and trans-decalin was investigated. The effect of polymer concentration, molecular weight and shear rate on viscosity was determined. The molecular weights lay between 5 10⁴ and 24 10⁶ and the concentrations covered a range of values below and above the critical valuec ^*, at which the macromolecular coils begin to overlap. Flow curves were generated for the solutions studied by plotting log versus log . Different molecular weights were found to have the same viscosity in the non-Newtonian region of the flow curves and follow a straight line with a slope of – 0.83. A plot of log ₀ versus logM _w for 3 wt-% polystyrene in toluene showed a slope of approximately 3.4 in the high molecular weight regime. Increasing the shear rate resulted in a viscosity that was independent of molecular weight. The sloped (log)/d (logM _w ) was found to be zero for molecular weights at which the corresponding viscosities lay on the straight line in the power-law region.On the basis of a relation between _sp and the dimensionless productc · [], simple three-term equations were developed for polystyrene in toluene andt-decalin to correlate the zero-shear viscosity with the concentration and molecular weight. These are valid over a wide concentration range, but they are restricted to molar masses greater than approximately 20000. In the limit of high molecular weights the exponent ofM _w in the dominant term in the equations for both solvents is close to the value 3.4. That is, the correlation between _sp andc · [] results in a sloped(log _sp)/d(logc · []) of approximately 3.4/a at high values ofc · [] wherea is the Mark-Houwink constant. This slope of 3.4/a is also the power ofc in the plot of ₀ versusc at high concentrations. a Mark-Houwink constant - B ₁,B ₂,B _n constants - c concentration (g · cm^–3) - c ^* critical concentration (g · cm^–3) - K, K constants - K _H Huggins constant - M molecular weight - M _c critical molecular weight - M _n number-average molecular weight - M _w weight-average molecular weight - n sloped(log _sp)/d (logc · []) at highc · [] - PS polystyrene - T temperature (K) - shear rate (s^–1) - critical shear rate (s^–1) - viscosity (Pa · s) - ₀ zero-shear viscosity (Pa · s) - _s solvent viscosity (Pa · s) - _sp specific viscosity - [] intrinsic viscosity (cm³ · g^–1) - dynamic viscosity (Pa · s) - | ^*| complex dynamic viscosity (Pa · s) - angular frequency (rad/s) - density of polymer solution (g · cm^–3) - ₁₂ shear stress (Pa) Dedicated to Prof. Dr. J. Schurz on the occasion of his 60^th birthday.Excerpt from the dissertation of Reinhard Kniewske: Bedeutung der molekularen Parameter von Polymeren auf die viskoelastischen Eigenschaften in wäßrigen und nichtwäßrigen Medien, Technische Universität Braunschweig 1983.     

Linear viscoelastic behavior of narrow molecular weight distribution 1,4 polybutadiene: Comparison with Doi-Edwards theory of reptation

Linear viscoelastic behavior of narrow molecular weight distribution 1,4 polybutadiene samples with molecular weights between 42500 and 779000 has been correlated with molecular structure using a simple modification of the Doi-Edwards theory of reptation. The entire GPC curve is required for the calculations of viscoelastic behavior.The plateau modulus obtained from the experimental data is comparable to literature values, while the equilibrium compliance (which is indicative of polydispersity) is greater than values reported in the literature for nearly monodisperse polybutadienes. Reasonable agreement between theory and experiment is obtained over the entire molecular weight range. The agreement between theory and experiment using the GPC curve is better than that obtained by assuming the polymer to be monodisperse or by using the Doi fluctuation model. The model appears to break down for a more polydisperse sample . This study indicates that it may be possible to use the Doi-Edwards theory to explain the viscoelastic behavior of narrow MWD polybutadienes without introducing any new concepts into the theory (fluctuations, constraints release, etc.).     

Linear viscoelasticity,simple and planar melt extension of linear polybutadienes with bimodal molar mass distributions

Shear oscillations, simple and planar elongations have been performed with anionically polymerized polybutadienes (PB) and their blends at room temperature. The PB components were of different molar mass averages and of narrow molar mass distributions; the blends had bimodal molar mass distributions and are represented by the weight ratio w of the high molecular component. The crossover G() = G() obtained from oscillatory measurements shows correlations with molecular parameters. For the zero shear viscosity the well-known relation ₀ M _w ^3.4 is found. The recoverable equilibrium shear compliance J _e ⁰ is nearly the same for the components; for the blends it strongly depends on w with a pronounced maximum at small w. In elongation outside the linear region strain hardening is found; its magnitude depends on M _w of the components, the composition w of the blend, the mode of elongation (simple or planar), and the elongational strain rate. The hardening revealed in the increase of the elongational viscosity above the linear viscoelastic limit increases as a function of w up to a maximum similar to J _e ⁰ such that, for both properties, the molecular processes may be the same. The elongational viscosity µ₂ (from the lateral stress in planar elongation) is above the linear viscoelastic limit for bimodal and below this limit for conventional broad molar mass distributions. In general, it can be stated that with a more narrow molar mass distribution of linear polymers the elongational behavior of the melts comes closer to the linear viscoelastic limit.Dedicated to Professor Arthur S. Lodge on the occasion of his 70th birthday and his retirement from the University of Wisconsin.Extended version of a paper presented at the Annual Conf. German Soc. of Rheology, Berlin, May 13–15, 1991.     

Rheology of polymer blends with matrix-phase viscoelasticity and a narrow droplet size distribution

A Hamiltonian framework of non-equilibrium thermodynamics is adopted to construct a set of dynamical continuum equations for a polymer blend with matrix viscoelasticity and a narrow droplet size distribution that is assumed to obey a Weibull distribution function. The microstructure of the matrix is described in terms of a conformation tensor. The variable droplet distribution is described in terms of two thermodynamic variables: the droplet shape tensor and the number density of representative droplets. A Hamiltonian functional in terms of the thermodynamic variables is introduced and a set of time evolution equations for the system variables is derived. Sample calculations for homogenous flows and constant droplet distribution are compared with data of a PIB/PDMS blend and a HPC/PDMS blend with high viscoelastic contrast. For the PIB/PDMS blend, satisfactory predictions of the flow curves are obtained. Sample calculations for a blend with variable droplet distribution are performed and the effect of flow on the rheology, droplet morphology, and on the droplet distribution are discussed. It is found that deformation can increase or decrease the dispersity of the droplet morphology for the flows investigated herein.