Prediction of multiple overshoots in shear stress during fast flows of bidisperse polymer melts

We present a differential constitutive model of stress relaxation in polydisperse linear polymer melts and solutions that contains contributions from reptation, contour-length fluctuations, and chain stretching. The predictions of the model during fast start-up and steady shear flows of polymer melts are in accord with experimental observations. Moreover, in accordance with reported experimental literature (Osaki et al. in J Polym Sci B Polym Phys 38:2043–2050, 2000), the model predicts, for a range of shear rates, two overshoots in shear stress during start-up of steady shear flows of bidisperse polymer melts having components with widely separated molar masses. Two overshoots result only when the stretch or Rouse relaxation time of the higher molar mass component is longer than the terminal relaxation time of the lower molar mass component. The “first overshoot” is the first to appear with increasing shear rate and occurs as a result of the stretching of longer chains. Transient stretching of the short chains is responsible for the early time second overshoot. The model predictions in steady and transitional extensional flows are also remarkable for both monodisperse and bidisperse polymer solutions. The computationally efficient differential model can be used to predict rheology of commercial polydisperse polymer melts and solutions.     

Constant interchain pressure effect in extensional flows of oligomer diluted polystyrene and poly(methyl methacrylate) melts

The constant ‘interchain pressure’ idea has been addressed, to evaluate if it is an adequate quantitative assumption to describe the fluid mechanics of oligomer diluted entangled NMMD polymer systems. The molecular stress function constitutive framework has been used with the constant interchain pressure assumption. Furthermore, the maximal extensibility based on the number of Kuhn steps in an entanglement has been used based on the relative Padé inverse Langevin function. The model predictions agree with the extensional measurements on all previously published poly(methyl methacrylate)s and almost all published oligomer diluted NMMD polystyrenes. The only deviation is on the most diluted and largest molecular weight case of an 18% 1880 kg/mol polystyrene in oligomer diluent. In this case, the maximal extensibility is not needed.     

Linear rheology of diluted linear, star and model long chain branched polymer melts

We present experiments and theory on the diluted melt dynamics of monodisperse entangled polymers of linear, star and H-shaped architecture. Frequency-dependent rheological data on a series of progressively diluted linear, star and H-polymers are in good agreement with a refined tube-model theory that, for H-polymers, combines star polymer melt behaviour at high frequency, with linear polymer reptation behaviour at low frequencies. Taking into account the effect of dilution via some simple scaling relations, mild polydispersity and by incorporating the high frequency Rouse modes, we are able to model quantitatively the entire frequency range. This work suggests a novel rheological route to analysing long chain branching in polymer melts. Received: 6 April 2000/Accepted: 21 December 2000     

Nonequilibrium stretching dynamics of dilute and entangled linear polymers in extensional flow

We propose an extension of the FENE-CR model for dilute polymer solutions [M.D. Chilcott, J.M. Rallison, Creeping flow of dilute polymer solutions past cylinders and spheres, J. Non-Newtonian Fluid Mech. 29 (1988) 382–432] and the Rouse-CCR tube model for linear entangled polymers [A.E. Likhtman, R.S. Graham, Simple constitutive equation for linear polymer melts derived from molecular theory: Rolie–Poly equation, J. Non-Newtonian Fluid Mech. 114 (2003) 1–12], to describe the nonequilibrium stretching dynamics of polymer chains in strong extensional flows. The resulting models, designed to capture the progressive changes in the average internal structure (kinked state) of the polymer chain, include an ‘effective’ maximum contour length that depends on local flow dynamics. The rheological behavior of the modified models is compared with various results already published in the literature for entangled polystyrene solutions, and for the Kramers chain model (dilute polymer solutions). It is shown that the FENE-CR model with an ‘effective’ maximum contour length is able to describe correctly the hysteretic behavior in stress versus birefringence in start-up of uniaxial extensional flow and subsequent relaxation also observed and computed by Doyle et al. [P.S. Doyle, E.S.G. Shaqfeh, G.H. McKinley, S.H. Spiegelberg, Relaxation of dilute polymer solutions following extensional flow, J. Non-Newtonian Fluid Mech. 76 (1998) 79–110] and Li and Larson [L. Li, R.G. Larson, Excluded volume effects on the birefringence and stress of dilute polymer solutions in extensional flow, Rheol. Acta 39 (2000) 419–427] using Brownian dynamics simulations of bead–spring model. The Rolie–Poly model with an ‘effective’ maximum contour length exhibits a less pronounced hysteretic behavior in stress versus birefringence in start-up of uniaxial extensional flow and subsequent relaxation.     

Molecular approach in linear polymer dynamics: Theory and numerical experiment

A constitutive equation for polymer solutions and melts is obtained on the basis of the dynamics of noninteracting dumbbells moving in a nonlinear anisotropic fluid. The equation obtained is used to describe nonlinear effects under conditions of simple shear and steady-state flow in a circular tube and for the numerical investigation of a flow in a finite cylinder with a rotating end face. Barnaul. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 1, pp. 3–13, January–February, 2000.     

Flow-induced nucleation in polymer melts: a study of the GO model for pure and bimodal blends, under shear and extensional flow

We present a rapid rescaling algorithm that enables a systematic comparison between the Graham and Olmsted (GO) model for flow-induced nucleation of polymer melts (Graham and Olmsted, Phys Rev Lett 103(11): 115702, 2009) and direct nucleation rate measurements from a flowing polymer melt. We consider polymer melts consisting of pure long chains and bimodal blends of long and short chains. We simulate the nucleation rate for a wide range of free energy barriers under a wide range of applied shear and extensional flows by using an accelerated nucleation algorithm. We then develop a semi-analytical technique to compute efficiently the nucleation rate under flow for monodisperse melts. We extend our approach to bimodal blends using a method to rescale reference data. This allows us to compare the GO model to experimentally measured nucleation rates at several different temperatures. The GO model is able to consistently account for the effect of temperature on flow-induced nucleation. Our modelling will also contribute to the derivation of computationally inexpensive molecular models of flow-induced nucleation in polymers.     

The role of convective constraint release in parallel superposition flows of nearly monodisperse entangled polymer solutions

Recent experiments by Li and Wang (Macromolecules 43:5904–5908, 2010) on parallel superposition flows of nearly monodisperse entangled polymer solutions revealing a flow-induced acceleration of the relaxation dynamics are here analyzed by using a simple differential constitutive equation based on the tube model to examine the role of convective constraint release (CCR) in these situations. Contrary to the expectations of Wang and coworkers, we find that such a flow-induced acceleration is not a CCR effect. Rather, our results suggest that the acceleration is simply due to convection per se (not to be confused with CCR) and to nonlinear orientation effects.     

A generalized relation between MWD and relaxation time spectrum

An inversion procedure for converting linear viscoelastic properties of polymer melts into molecular weight distribution (MWD) described by the generalized exponential function (GEX) has been implemented and applied in a previous work (Cocchini F, Nobile MR. Rheol Acta 42:232–242, 2003). It is based on the elegant relationship between the relaxation spectrum and the MWD function proposed by Thimm W, Friedrich C, Marth M. J Rheol 43:1663–1672 (1999). In the present paper, such a methodology has been generalized to properly account for sharp MWDs, in particular, nearly monodisperse or blends of nearly monodisperse polymer samples. The generalized relationship has been verified and calibrated using the BSW kernel (Baumgaertel M, Schausberger A, Winter HH. Rheol Acta 29:400–408, 1990) to describe the rheological behavior of some Polystyrene samples from the literature, in terms of the known MWD. Then, it has been successfully applied to the inversion problem for a wider set of samples, with both broad and sharp distributions. The Rouse contribution at high frequencies and the accelerating effect on the relaxation times due to polydispersion have been also addressed.     

Theoretical analysis of non-uniform extensional flows in relation to processing rheology and predictions of some constitutive equations

In this paper, a characteristic equation involving the stream function, already given by one of the authors in a previous work for classifying axisymmetric incompressible flows, is re-considered. Non-uniform nearly extensional flows are derived as particular solutions from this equation. Using experimental data in the literature for polymer solutions and melts, it is proved that particular solutions of the characteristic equation lead to kinematics very close to those encountered in the fiber-spinning process. The kinematic equations satisfactorily correlating the fiber-spinning data are used in order to determine the ability of constitutive equations to predict realistic stresses in the flow domain. The rheological parameters of the fluids, obtained from experiments, are used for computation of differential and integral constitutive equations in the spinning conditions. Comparisons with the stress response of adequate constitutive equations are given and discussed.Also affiliated to: Université Joseph Fourier Grenoble I and Institut National Polytechnique de Grenoble, Associé au CNRS (URA 1510)     

On the burst of branched polymer melts during inflation

Two molten low-density polyethylene melts, shaped as plates, have been inflated into a circular cylinder during isothermal conditions. Lowering the inflation rates allow the plates to be inflated into a larger volume of the cylinder before bursting. Numerical simulations of the inflations have been performed, using a time-strain separable constitutive K-BKZ equation based on the potential function from the Doi–Edwards theory. The material parameters in the constitutive model are based on liner viscoelastic and time dependent uniaxial elongational viscosities. The numerical calculations show quantitative agreement with the experiments, including the appearance of the burst, for a wide range of experimental conditions. This strongly suggests that the initiation of the burst in the polymer melts is a hydrodynamic phenomenon.     

Differential constitutive equation for entangled polymers with partial strand extension

Beginning with a formal statement of the conservation of probability, we derive a new differential constitutive equation for entangled polymers under flow. The constitutive equation is termed the Partial Strand Extension (PSE) equation because it accounts for partial extension of polymer strands in flow. Partial extensibility is included in the equation by considering the effect of a step strain with amplitude E on the primitive chain contour length. Specifically, by a simple scaling argument we show that the mean primitive chain contour length after retraction is L=L ₀ E ^1/2, not the equilibrium length L ₀ as previously thought. The equilibrium contour length is infact recovered only after a characteristic stretch relaxation time λ _s that is bounded by the reptation time and longest Rouse relaxation time for the primitive chain. The PSE model predictions of polymer rheology in various shear and extensional flows are found to be in good to excellent agreement with experimental results from several groups. Received: 16 July 1997 Accepted: 22 January 1998     

Brownian configuration fields and variance reduced CONNFFESSIT

Stochastic simulation techniques, such as Brownian dynamics, provide us an extremely powerful tool for solving the usually nonlinear equations describing polymer dynamics in solutions and melts [1]. However, the most challenging problems (e.g. the investigation of the universal behaviour of long polymer chains, or the flow calculation based on stochastic simulation techniques) involve a very large number of degrees of freedom and hence require an enomous amount of computer time. In order to solve such problems on currently available computers it is therefore necessary to develop strategies to drastically suppress the level of the fluctuations in the simulations. The purpose of this note is to show that the recently proposed concept of Brownian configuration fields [2] in viscoelastic flow calculations can be regarded as an extremely powerful extension of variance reduction techniques based on parallel process simulation.     

The rational mechanics and thermodynamics of polymeric fluids based upon the concept of a variable relaxed state

The conceptual framework of polymer continuum mechanics based upon Eckart's idea of a variable relaxed state is developed. No constitutive models are explicitly used. The theory admits four constitutive functions only, the scalar specific internal energy, the vectorial heat flux, and two tensorial fluxes representing non-elastic stress and flow (slippage). The non-linearity of the constitutive relations includes self-induced anisotropy (Leonov) with Reiner-Rivlin's equation representing a special example for this. — The effectiveness of this non-linear theory is demonstrated by treating elongational flows of polymer melts.     

An unsymmetric constitutive equation for anisotropic viscoelastic fluid

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

Assessment of nonlinear strain measures for extensional and shearing flows of polymer melts

From stress-strain experiments in extensional and shearing flows, nonlinear strain measures and effective damping functions are derived for a polyisobutylene melt. The strain measures determined in planar extensional flow and in simple shear flow coincide. Experimental results are compared with predictions of two molecular theories, the Doi-Edwards model and the molecular stress function approach of Wagner and Schaeffer. Discrepancies between theories and experiment lead to a reconsideration of the classification of extensional flows. The symmetry of the flow field is identified and quantified as an important parameter influencing the strain measure, and a unifying strain measure for general extensional and shearing flows of polymer melts is presented.     

Suspension-based rheological modeling of crystallizing polymer melts

The applicability of suspension models to polymer crystallization is discussed. Although direct numerical simulations of flowing particle-filled melts are useful for gaining understanding about the rheological phenomena involved, they are computationally expensive. A more coarse-grained suspension model, which can relate the parameters in a constitutive equation for the two-phase material to morphological features, such as the volume fractions of differently shaped crystallites and the rheological properties of both phases, will be more practical in numerical polymer processing simulations. General issues, concerning the modeling of linear and nonlinear viscoelastic phenomena induced by rigid and deformable particles, are discussed. A phenomenological extension of linear viscoelastic suspension models into the nonlinear regime is proposed. A number of linear viscoelastic models for deformable particles are discussed, focusing on their possibilities in the context of polymer crystallization. The predictions of the most suitable model are compared to direct numerical simulation results and experimental data.