Predictions of linear viscoelastic properties for polydisperse entangled polymers

Different blending laws have been proposed in the literature to describe the polydispersity effect on the rheological behavior of polymer melts. In this paper predictions of linear viscoelastic properties of entangled polydisperse polymers have been derived from the double reptation mixing rule. The results in terms of the relaxation modulus, the zero shear-rate viscosity, η₀, and the steady-state compliance, J _e ⁰, have been obtained using three different relaxation functions for the monodisperse fractions, namely the Tuminello step function, the single exponential function and the BSW function. Both discrete and continuous molecular weight distributions (MWDs) have been investigated. The Generalized Exponential Function (GEX) has been considered in the continuous case. The results showed that, in systems with a large number of components, the predictions of linear viscoelastic properties mainly depend on the double reptation mixing rule assumption, while the choice of the relaxation function is not crucial. In particular, the mathematical simplicity of the Tuminello step relaxation function has allowed analytical computation of the linear viscoelastic properties in closed form. Indeed, the analytical results indicated a dependence of η₀ on the MWD that could be expressed in terms of (M _z/M _w)^0.8, in agreement with experimental results reported in the literature. In the case of J _e ⁰, the analytical model defines a dependence on (M _z/M _w)^5.5, i.e. as expected a strong dependence on the MWD is predicted for the steady-state compliance. Finally, dynamic moduli have been computed from the relaxation modulus and their predictions have been favorably compared with experimental results from the literature. Received: 19 July 1999/Accepted: 24 November 1999     

Influence of molecular parameters on the stress dependence of viscous and elastic properties of polypropylene melts in shear

The stress dependencies of the steady-state viscosity η and, particularly, that of the steady-state elastic compliance J _e of various linear isotactic polypropylenes (PP) and one long-chain branched PP are investigated using creep-recovery tests. The creep stresses applied range from 2 to 10,000 Pa. In order to discuss the stress-dependent viscosity η and elastic compliance J _e with respect to the influence of the weight average molar mass M _w and the polydispersity factor M _w/M _n the PP are characterized by SEC–MALLS. For the linear PP, linear steady-state elastic compliances J_e⁰J_{\rm e}^0 in the range of 10^− 5–10^− 3 Pa^− 1 are obtained depending on the molar mass distribution. J_e⁰J_{\rm e}^0 of the LCB-PP is distinctly higher and comes to lie at around 10^− 2 Pa^− 1. J_e⁰J_{\rm e}^0 is found to be independent of M _w but strongly dependent on polydispersity. η and J _e decrease with increasing stress. For the linear PP, J _e as a function of the stress τ is temperature independent. The higher M _w/M _n the stronger is the shear thinning of η and the more pronounced is the stress dependence of J _e. For the LCB-PP, the strongest stress dependence of η and J _e is observed. Furthermore, for all PP J _e reacts more sensitively to an increasing stress than η. A qualitative explanation for the stronger stress dependence of J _e compared to η is given by analyzing the contribution of long relaxation times to the viscosity and elasticity.     

Dependence of the zero shear-rate viscosity and the viscosity function of linear high-density polyethylenes on the mass-average molar mass and polydispersity

Linear high-density polyethylenes with molar masses M _w between 240 and 1,000,000 g/mol, obtained by metallocene catalysts, were characterized in shear using oscillatory and creep tests. The polydispersities of the molar mass distributions (MMDs) lay between 1 and 16. The resulting zero shear-rate viscosities η₀ covered a range from 2.5×10⁻³ to around 10⁸ Pas. Above a critical molar mass of M _c≈2,900 g/mol, the experimental results can be described by the relation η₀ ∼ M _w^3.6, independently of the MMD. The oscillatory data were fitted with a Carreau–Yasuda equation. The resulting parameters were correlated to molecular structure. The parameter a, being a quantity for the width of the transition between the Newtonian and the non-Newtonian regime, showed a dependence on the molar mass M _w but not on M _w/M _n. The parameter λ of the Carreau-Yasuda equation was found to be the reciprocal crossover frequency for all samples with a log-Gaussian MMD. λ depends on the molar mass M _w and also on M _w/M _n.

Evaluation of molecular weight distribution from dynamic moduli

A method to evaluate molecular weight distribution (MWD) from dynamic moduli is presented here. It relies on the least-square fitting of the dynamic data to a model whose parameters depend on the MWD. In particular, the analytical solution for the relaxation modulus previously obtained from the double reptation model, with the Tuminello step relaxation function and the Generalized Exponential Function (GEX) describing the MWD (Nobile and Cocchini 2000), has been used. A Finite Element Approximation (FEA) has been applied to calculate dynamic moduli from the relaxation modulus as a function of MWD. The sensitiveness of the GEX-double reptation dynamic moduli on the model parameters has also been investigated and the results show that large changes of the M_w/M_n ratio weakly affect the dynamic moduli, while small changes of the M_z/M_w ratio significantly deform the dynamic moduli curves. The use of rheological data to obtain MWD, by the model used in this paper, will, therefore, be able to give rather well defined M_z/M_w ratios, while more uncertainty will be presented in the M_w/M_n results. The so-called GEX-rheological model for the dynamic moduli was applied to fit the experimental data of different polymers in order to obtain the best-fit parameters of the MWD of these polymers, without the need for the inversion of the double reptation integral equation. The stability of the results has been confirmed through the evaluation of the 90% confidence intervals for the first molecular weight averages. Finally, concerning the M_w and M_z values, the predictions obtained from the dynamic moduli measurements differ by less than 10% from those obtained from GPC measurements while, as expected, more uncertainty is present in the M_n predictions. Received: 6 February 2000 Accepted: 22 August 2000     

An experimental evaluation of the behaviour of mono and polydisperse polystyrenes in Cross-Slot flow

The behaviour of a number of mono and polydisperse polystyrenes are probed experimentally in complex extensional flow within a Cross-Slot geometry using flow-induced birefringence. Polystyrenes with similar molecular weight (M _w) and increasing polydispersity (PD) illustrated the effect of PD on the principal stress difference (PSD) pattern in extensional flow. Monodisperse materials exhibited only slight asymmetry at moderate flowrates, although increased asymmetry and cusping was observed at high flowrates. The response of monodisperse materials of different M _w at various flowrates is presented and characterised by Weissenberg numbers for both chain stretch and orientation using a theory for linear entangled polymers. The comparison of stress profiles against Weissenberg number for each process is used to determine whether the PSD pattern observed is independent of M _w and elucidate which relaxation mechanism is dominant in the flow regimes probed. For monodisperse materials, at equivalent chain orientation Weissenberg number (We _τd), different molecular weight materials were seen to exhibit similar steady state PSD patterns independent of We _τR (chain stretch We). Whilst no obvious critical Weissenberg number (We) was found for the onset of increased asymmetry and cusping, it was found to occur in the “orientating flow without chain stretch” regime.     

Viscosity and compliance from molar mass distributions using double reptation models

Various empirical correlations between linear viscoelastic properties and molar mass distribution of linear polymers have been proposed. Many of these summarize the distribution in terms of the first few moments. This is sufficient when studying samples of limited variability. In parallel, various fundamental models that enable calculation of these rheological characteristics from the full distribution have been proposed. The advantage of the modeling approach is the ease of creating distributions, thus enabling independent control of moments up to any desired order. It is the goal of this contribution to explore this advantage and compare the findings of the single exponential (DRSE) and modified time-dependent diffusion (DRmTDD) double reptation models with the empirical relations. The models predict that η ₀ is primarily a function of the weight-average molar mass M _w, with subtle dependence on polydispersity. Furthermore, the model depends mainly on a combination of the second (M _z/M _w) and third (M _z+1/M _z) polydispersity index. The DRmTDD model shows that conventional moment-based fit equations are only valid for limited distribution parameter ranges. General fit equations are proposed based on genetic programming. The details of the predictions are sensitive to the precise physical model formulation and need to be validated from experiments.     

A numerical study of various rheological polydispersity measures

Model calculations were performed in order to investigate the sensitivity of various rheological polydispersity parameters for variations in the moments of the molar mass distribution (MMD) of linear polymers. Molar mass distributions were generated with the Gaussian and the Generalised exponential distribution functions, using a fixed weight average molar mass M _w and variable M _w /M _n and M _z /M _n . Assuming linear entangled polymeric chains, the linear viscoelastic properties were predicted by calculating the stress relaxation modulus of the consecutive monodisperse fractions with the BSW relaxation time spectrum and blending these curves with the double reptation blending rule. BSW relaxation parameters appropriate for polypropylene were used.  It was found that both the zero-shear viscosity and the so-called cross-over frequency, at which and are equal, depend mostly on M _w but also significantly on both M _w /M _n and M _z /M _w . By contrast, the steady-state compliance depends mainly on M _z /M _w , its functional dependence on moments of the MMD being best described by the Ferry equation.  None of the polydispersity parameters PI (from the modulus cross-over), MODSEP (the modulus separation) or PDR (from the shape of the flow curve), as introduced in literature depends solely on the polydispersity M _w /M _n . PI is the most sensitive indicator for this purpose. Finally, the parameters ER ( at a fixed low value of , MODSEP en DRI (from the shape of the flow curve) are shown to be good indicators for the weight (M _z /M _w ) of the high molar mass tail of the molar mass distribution. Received: 5 May 1998 Accepted: 30 July 1998     

Steady and transient shear flows of polystyrene solutions I: Concentration and molecular weight dependence of non-dimensional viscometric functions

Start up from rest and relaxation from steady shear flow experiments have been performed on monodisperse polystyrene solutions with molecular weight ranging from 1.3 × 10⁵ to 1.6 × 10⁶ and concentration c ranging from 5% to 40%. A method of reduced variables based on the use of a characteristic time τ_w is proposed. τ_w is defined as the product of zero shear viscosity with the steady state elastic compliance.Reduced steady and transient viscometric functions so obtained depend on the ratio M/M_e (where M_e is the entanglement molecular weight). Limiting forms are obtained when M/M_e ? 18. In steady flow, a simple correlation is found between shear and normal stresses.In stress relaxation experiments, independent of shear rate, the long-time behaviour can be characterised by a single relaxation time τ₁, which is identical for shear and normal stresses. τ₁ can be simply related to the zero shear rate viscosity and the limiting elastic compliance.     

Recoverable strains and retardation times of monodisperse suspensions of silicon dioxide spheres in poly(dimethylsiloxane)

Steady-state viscosities η, steady-state recoverable strains γ _rs and characteristic retardation time τ _1/2 were measured for suspensions of monodisperse silicon dioxide (SiO₂) spheres in poly(dimethylsiloxane) (PDMS) with various volume fractions Φ of the suspended spheres at various creep stresses σ ₀. Two different regions are found in plots of η/η _m vs γ _rs, where η/η _m denotes the relative viscosity of the suspensions. In one region, η/η _m is proportional to γ _rs, while γ _rs is independent of η/η _m in the other region. In both regions, τ _1/2 is the functions of the shear strain rate in the steady-state of creep test independently of Φ. The origin of the elasticity is related to the ‘maximally distorted’ cages recovered owing to the repulsive interaction between the SiO₂ spheres and recovery of the cages in the shear-induced clusters of the suspended spheres.     

Quantitative predictions of linear viscoelastic rheological properties of entangled polymers

The “dual constraint” model developed by Mead, Van Dyke et al. is here extended by inclusion of “early-time” contour-length fluctuations and constraint-release Rouse relaxation, and then evaluated by comparing its predictions with literature data for over 50 different linear and star polymers. By combining the reptation model of Doi and Edwards with contour-length fluctuations and constraint release, the model provides a systematic approach to prediction of the rheological properties of polymers. The parameters are taken from the literature and used consistently for linear polymers, star polymers, and their mixtures having the same chemical compositions. In most cases, the predictions of the model appears to agree well with data for monodisperse, bidisperse, and polydisperse linear and star polymers, except at low molecular weights. Received: 23 December 1999 Accepted: 28 March 2000     

Uniaxial elongational viscosity of PS/a small amount of UHMW-PS blends

A series of polystyrene (PS) and a small amount of ultra high molecular weight (UHMW) PS blends have been prepared by using tetrahydrofuran (THF). Matrix PS has an M_w of 423,000 (M_w/M_n= 2.36) and UHMW-PS has either an M_w of 3,220,000 (M_w/M_n= 1.05) or 15,400,000 (M_w/M_n=1.30) in the range of concentration from 0 wt% to 1.5 wt%. The influence of a small amount of UHMW on dynamic viscoelasticity was investigated. At the frequency lower than 0.001 rad/s, the enhancement of G′ was observed by the incorporation of a small amount of UHMW. And the degree of enhancement was in the order of M_w of UHMW and its concentration. The measurement of uniaxial elongational viscosity for the blends was performed and the effects of UHMW on strain-hardening properties were analyzed at equal strain-rate conditions. The concentration of UHMW where the strain-hardening becomes substantially stronger was determined. To get more insight into the cause of enhancement of strain-hardening at a certain concentration, the damping function from step-shear stress relaxation was measured. The influence of a small amount of UHMW on the damping function was found to be small. It was interpreted, from time- and strain-dependency points, that the enhancement of strain-hardening by a small amount of UHMW was governed by the long relaxation time. Received: 6 September 2000 Accepted: 11 January 2001     

Rheological behavior of cellulose/monohydrate of n-methylmorpholine n-oxide solutions Part 1: Liquid state

Steady-state and dynamic experiments have been performed on solutions containing cellulose dissolved in monohydrate of N-methylmorpholine N-oxide (NMMO). The dependence of the zero-shear viscosity η₀, and of the terminal relaxation time τ _c , on concentration, average degree of polymerization (DP) and temperature are discussed. The behavior of this semi-rigid, polymolecular polymer in solution differs from that of flexible monodisperse ones. The slope of the plot of log(η₀) versus, on the one hand, log(c) at fixed molecular weight (DP)=600, and, on the other hand, log(DP) at fixed concentration (c=5%w/w) are equal to 4.6 and 5 respectively, instead of 3.4 in the concentrated region. Experimental data for the shear modulus were fitted using the classical Doi-Edwards equation with a log normal distribution of relaxation time. This distribution is compared to the distribution of DP. Received: 25 February1997 Accepted: 30 December 1997     

Rheologische Messungen an Polypropylenschmelzen

Zusammenfassung Es wurden Fließkurven von Polypropylenschmelzen bei 190 °C in einem Schergefällebereich von etwa 10^–1 bis 10² sec^–1 aufgenommen, wobei drei Serien von Polymerproben herangezogen wurden: eine Serie PP 1–7 von isotaktischen Propylenpolymerisaten mit einer Molekulargewichtsverteilung, die durch¯M _w /¯M _n 4–6 gekennzeichnet war; eine zweite Serie PP 1d–5d von abgebauten Polymerproben mit¯M _w /¯M _n 2–3; eine dritte Serie PP 1m–3m, die aus Mischungen von Polypropylenen bestand und die durch¯M _w /¯M _n >10 gekennzeichnet war. Es wurde der Einfluß des Molekulargewichts und der Molekulargewichtsverteilung auf die Fließkurven untersucht, insbesondere der Einfluß auf den Exponentenn in derOstwald-de Waele-Gleichung=KD ⁿ . Es wurde versucht, die Ergebnisse durch die universaleVinogradov-Viskositätsfunktion darzustellen, wobei sich aber sehr wesentliche Abweichungen infolge Variation des Molekulargewichts und der Molekulargewichtsverteilung ergaben.

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Summary Flow curves of molten polypropylene were determined at 190 °C over a shear gradient range of about l0^–1 to 10² sec^–1. Three series of polymer samples have been used: one series PP 1–7 of isotactic propylene polymerization products with a molecular weight distribution characterized by¯M _w /¯M _n 4–6, another series of degraded polymer samples PP 1d–5d with¯M _w /¯M _n 2–3, and still another series of polymer mixtures PP 1m–3m with¯M _w /¯M _n >10. The influence of molecular weight and molecular weight distribution on the flow curves was investigated, particularly on the exponentn in theOstwald-de Waele-power law=KD ⁿ . An attempt to plot the results by the universalVinogradov-viscosity function produced marked deviations due to variation of molecular weight and molecular weight distribution.

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Vorgetragen auf der Arbeitstagung der Sektion Rheologie des Vereins Österreichischer Chemiker am 17. November 1967 in Graz. Mitteilung I, II: Rheol. Acta5, 89 (1966); ibid. im Druck [Messung und Interpretation von Filmkurven].     

Heat transfer characteristics of boundary-layer flows induced by continuous surfaces stretched with prescribed skin friction

A continuous surface stretched with velocity u _w=u _w (x) and having the temperature distribution T _w=T _w (x) interacts with the viscous fluid in which it is immersed both mechanically and thermally. The thermal interaction is characterized by the surface heat flux q _w=q _w (x) and the mechanical one by the skin friction τ _w=τ _w (x). In the whole previous theoretical research concerned with such processes, either (u _w and T _w) or (u _w and q _w) have been prescribed as known boundary conditions. The goal of the present paper is to initiate the investigation of the boundary layer flows induced by stretching processes for which either (τ _w and T _w ) or (τ _w and q _w) are the prescribed quantities. The case of an isothermal surface stretched with constant skin friction, (τ _w=const., T _w=const. ≠ T _∞) is worked out in detail. The corresponding flow and heat transfer characteristics are compared to those obtained for the (well known) case of a uniformly moving isothermal surface (u _w=const., T _w=const. ≠ T _∞).     

Viscosity of concentrated noncolloidal bidisperse suspensions

At the same solid volume fraction (Φ) the relative viscosity (η _r ) of a concentrated noncolloidal bidisperse suspension of hard spherical particles is lower than that of a monodisperse suspension. In this paper a semi-analytical viscosity model of noncolloidal bidisperse suspensions is derived using an integration method. In this model the random loose packing density obtained by computer simulation is taken as the limit of solid volume fraction Φ _m which depends upon both the diameter ratio (λ) of large to small particles and the volume fraction of large particles (ξ=Φ _l /Φ). This model shows that at high solid volume fraction, Φ > 0.40, both λ and ξ significantly influence η _r . For example, at Φ=0.5, it predicts that for monodisperse suspensions η _r =70, while for bidisperse suspensions (λ=2 and ξ=0.7) η _r =40. Comparison shows that, at high solid volume fraction (0.4–0.5), the relative viscosity predicted by this model is in good agreement with that predicted by the work of Shapiro and Probstein (1992) and of Patlazhan (1993), but is higher than that predicted by the work of others. Received: 27 February 2001 Accepted: 25 April 2001     

The effect of entanglements on the rheological behavior of polybutadiene critical gels

We investigated the stress relaxation behavior of critical gels originating from six nearly monodisperse, highly entangled polybutadiene melts of different molecular weight from 18000 to 97 000 g/mole. The polymers were vulcanized by a hydrosilation reaction which takes place nearly exclusively at the pendant 1,2-vinyl sites distributed randomly along the polybutadiene chain. The BSW spectrum represents the relaxation of the initial uncrosslinked precursor. A characteristic parameter is the longest relaxation time of the precursor. Crosslinking increases this longest time even further. Surprisingly, the relaxation spectrum of the precursor is not altered much by the crosslinking except for an additional long time behavior. At the gel point (critical gel), this long time behavior is self-similar. It follows the typical power law as described by the Chambon-Winter gel equation, G(t) = St ^–n , in the terminal zone. The critical relaxation exponent was found to be close to n = 0.5 over a range of stoichiometric ratios and for all precursor molecular weights analyzed. A new scaling relationship was found between the gel stiffness, S, and the precursor molecular weight of the form: S M _w ^zn , where exponent z from the zero shear viscosity-molecular weight relationship, ₀ M _w ^z , is commonly found to be z = 3.3 – 3.6.     

The role of the mathematical mean value theorem (MVT) in rheometry: an easy way to convert apparent flow curves into correct ones

The mean value theorem of integral calculus guarantees that the apparent viscosity η _a can easily be converted into the correct viscosity η. For ordinary liquids there is a direct identity between η _a and η but the apparent shear rate (or apparent shear stress) has to be shifted to the representative shear rate γ˙^ (or representative shear stress τ^). A model free approximation scheme is introduced which implies a constant shift factor. The corresponding approximation for η is acceptable for liquids most commonly encountered. For plastic fluids the relation between η and η _a is more complex since it involves a function depending upon α; the yield stress relative to the maximum stress within the viscometer. Using the same approximation scheme as before the shift factor will involve α as well. The corresponding approximation of η is shown to be acceptable for the whole range of α. Received: 7 February 2000/Accepted: 15 February 2000