Rheological properties of branched polystyrenes: linear viscoelastic behavior

Oscillatory shear measurements on a series of branched graft polystyrenes (PS) synthesized by the macromonomer technique are presented. The graft PS have similar molar masses (M _w between 1.3×10⁵ g/mol and 2.4×10⁵ g/mol) and a polydispersity M _w /M _n around 2. The molar masses of the grafted side chains M _w,br range from 6.8×10³ g/mol to 5.8×10⁴ g/mol, which are well below and above the critical entanglement molar mass M _c of linear polystyrene. The average number of side chains per molecule ranges from 0.6 to 6.7. The oscillatory measurements follow the time–temperature superposition principle. The shift factors do not depend on the number of branches. The zero-shear viscosities of all graft PS are lower than those of linear PS with the same molar mass, which can be attributed to the smaller coil size of the branched molecules. It is shown that the influence of branching on the frequency dependence of the dynamic moduli is weak for all graft PS that were investigated, which can be explained by the low entanglement density.Electronic Supplementary Material Supplementary material is available for this article at This article has already been published online first (DOI: ). Due to an oversight at the publisher's, this version contained several mistakes. The article is herewith republished in its entirety as a "publisher's erratum".     

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.     

The role of short chain molecules for the rheology of polystyrene melts.

Atactic polystyrenes of narrow molar mass distribution with average molar masses larger than the critical molar massM _c were mixed with similar polystyrenes of molecular masses lower thanM _c . Linear viscoelastic melt properties of these binary blends were measured with a dynamic viscometer of the concentric cylinder type. One of the experimental findings is that the time-temperature shift factorsa _T are dependent on the composition of the samples. This can be understood, if free volume due to chain-ends is taken into account. A computer-fitted WLF-equation being modified in a proper way leads to the following results: At the glass-transition-temperature the fraction of free volume in polystyrene of infinite molar mass is only 0.015. At a temperature of 180 °C the mean value of the free volume at a chain end is 0.029 nm³ for the polystyrene investigated.     

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.     

Evaluation of calculated entanglement spacings for undiluted linear amorphous polymers

Conclusions In reality, entanglements based on rheological measurements have been essentially defined operationally as a kinetic or time delay effect present in concentrated polymer systems. This is where intuitively molecular loops or overlap and entanglements of polymer chains are most likely to occur. The evaluation in fig. 2 suggests that the theory of rubber elasticity, even discounting the inherent imprecision of measurements, gives anM _e which is not relatable to polymer composition 1and chain structure. Conversely reliable and internally consistent values ofM _c can come from the molecular weight dependence of: 1.Newtonian viscosities, 2.NMR relaxation times, and 3 the shear dependence of viscosities, see fig. 1. However, entanglement spacings calculated in this way lack adequate theoretical substantiation particularly as to the mechanism of flow. Nonetheless, the correlation ofM _c with composition and structure is convincing and provides a sound empirical correlation and the basis for a renaissance in theoretical interpretation of viscoelastic behavior of linear amorphous polymers. Further theory must rationalize the fact that the shear compliance, which is proportional toM _e , depends on a combination of molecular weight averages involvingZ andZ+1. Yet the break in viscosity-molecular weight curves yieldingM _c has been generally confirmed to depend on only weight average molecular weight. The values ofM _c appear worthy of further experimental and theoretical evaluation. The values ofM _e appear to be based on experimental techniques that at present do not provide sufficient precision to warrant citation of such values molekular weight distribution is thought to have an important yet ill-defined influence on calculated values of M _e .     

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.

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.     

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     

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     

The relaxation of concentrated polymer solutions

The focus of this paper is on the viscoelastic properties of concentrated polymer solutions and polymer melts. Dynamic mechanical measurements were performed on various polystyrene/ethylbenzene solutions with polymer concentrations ranging from 40% up to 100% and temperatures from Tg+30°C up to 70°C (230°C for polymer melts). The basis polymers are two commerical grade polystyrenes (BASF) with M _W = 247 kg/mol and 374 kg/mol, respectively. To avoid solvent loss due to evaporating during the measurements, a special sealing technique was used.A phenomenological model which describes quantitatively the relaxation spectrum of concentrated polymer solutions from the flow regime up to the glass transition regime is developed. The relaxation data of the respective polymer melt and the glass transition temperature of the solution are the only input parameters needed. The temperature dependence is described by a universal, concentration invariant WLF-equation. The relaxation spectra are divided into two parts accounting for the entanglement and the segmental relaxation modes, respectively. The relaxation strength related to the flow and entanglement regime scale with c ^2.3, whereas the segmental relaxation strength does not alter with concentration. All relaxation times change with concentration proportional to c ^3.5. Flow curves can be calculated from these relaxation spectra and thus, our results are useful for engineering applications.Roman Symbols a _T Time temperature superposition shift - factor - a _c Time concentration superposition - shift factor in the flow regime - a _c Time concentration superposition - shift factor in the glassy regime - b _T Modulus temperature superposition - shift factor - b _c Modulus concentration shift factor - in the flow regime - b _c Modulus concentration shift factor - in the glassy regime - B Virial coefficients - c Polymer mass fraction kg/kg - c ₁ WLF-parameter - c2 WLF-parameter K - g Relaxation strength of a relaxation Pa mode - G(t) Relaxation modulus Pa - G Storage modulus Pa - G Loss modulus Pa - GN Plateau modulus of linear flexible Pa polymers - (x) Delta function: (0) = 1, - (x<>0)=0 - h() Damping function - H() Relaxation spectrum Pa - J ₀ ^N Recoverable compliance Pa^–1 - m Mass kg - M _c Critical molecular weight kg/mol - M _e Entanglement molecular weight kg/mol - M _w Weight average molecular weight kg/mol - M Number of datapoints - n Scaling exponent - N Number of discrete relaxation modes - T Temperature °C - T _g Glass transition temperature °C - V Volume 1 Greek Symbols Scaling exponent - _f Thermal expansion coefficient K^–1 - Scaling exponent - Shear deformation - Shear rate s^t–1 - Relaxation time s - _c Characteristic relaxation time of thes Cross model - _e Entanglement relaxation time s - Viscosity Pa s - ₀ Zero shear viscosity Pa s - ₀ First normal stress coefficientPa s2 - Segmental friction coefficient - Frequency rad/s Indices f Flow and entanglement regime - g Glass transition regime - i Count parameter - p Polymer - ref Reference state - s Solvent 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     

A comparison of extensional viscosity measurements from various RME rheometers

The transient uniaxial extensional viscosity η _e of linear low density polyethylene (LLDPE) has been measured using the commercial Rheometric Scientific RME and the Münstedt Tensile Rheometer in an effort to compare the performance of available extensional rheometers. The RME indicated a significant strain hardening of the LLDPE, especially at a strain rate of 1 s⁻¹. In contrast, the Münstedt rheometer showed the LLDPE to be only slightly strain hardening. This artificial strain hardening effect in the RME resulted from the strain rate applied to the sample, determined from the sample deformation, being up to 20% less than the set strain rate. These results initiated a round-robin experiment in which the same LLDPE was tested on several RMEs in various locations around the world. All but one of the RMEs indicated a deviation between set and applied strain rates of at least 10%, especially at strain rates above 0.1 s⁻¹. The strain rate deviation was found to depend strongly on the value of the basis length L ₀ , and may result from the upper pair of belts not properly gripping the sample during extension. Thus visual inspection of the sample deformation is necessary to determine the applied strain rate. The most accurate measurements of η _e with respect to the strain rate deviation were obtained when the correct L ₀ value and belt arrangement were used. A list of recommendations for running an RME test is provided. Future work focusing on the fluid mechanics during the test may identify fully the cause of the strain rate deviation, but from a practical point of view the problem can be corrected for in the determination of η _e . Received: 27 September 2000/Accepted: 5 February 2001     

Grafting of polyamide 6 on a styrene–acrylonitrile maleic anhydride terpolymer: melt rheology at the critical gel state

In this work, we studied the melt rheology of multigraft copolymers with a styrene–acrylonitrile maleic anhydride (SANMA) terpolymer backbone and randomly grafted polyamide 6 (PA 6) chains. The multi-grafted chains were formed by interfacial reactions between the maleic anhydride groups of SANMA and the amino end groups of PA 6 during melt blending. Because of the phase separation of SANMA and PA 6, the grafted SANMA backbones formed nearly circular domains which were embedded in the PA 6 melt with a diameter in the order of 20 to 40 nm. The linear viscoelastic behaviour of PA 6/SANMA blends at a sufficiently large SANMA concentration displayed the characteristics of the critical gel state, i.e. the power relations G′ ∝ G′′ ∝ ω ^0.5. In elongation, the PA 6/SANMA blend at the critical gel state showed a non-linear strain hardening behaviour already at a very small Hencky strain. In contrast to neat PA 6, the elasticity of the PA 6/SANMA blends was strongly pronounced, which was demonstrated by recovery experiments. Rheotens tests agreed with the linear viscoelastic shear oscillations and the measurements using the elongational rheometer RME. Increasing the SANMA concentration led to a larger melt strength and a reduced drawability. The occurrence of the critical gel state can be interpreted by the cooperative motion of molecules which develops between the grafted PA 6 chains of neighbouring micelle-like SANMA domains.     

Some correlations involving the shear viscosity of polystyrene melts

Based upon a compilation of steady-shear and dynamic-shear viscosity data from the literature for polystyrene melts, an assessment has been made concerning the relative merits of the Cross and Carreau models in describing the shear-rate dependence of such viscosities. It is shown that the Cross model is decidedly more appropriate for PS of BMWD. Based upon master plots, it is demonstrated that the Cox-Merz relation applies to PS of both BMWD and NMWD. It is also shown that the Cox-Merz relation applies even into the second-Newtonian regime, with being independent ofM _w and MWD. In addition, the applicability of the Prest-Porter-O'Reilly relationship between shear viscosity and recoverable shear compliance is corroborated in the case of PS of NMWD.     

A simple method of evaluating the complex moduli of polystyrene blends

In the search for a workable mixing rule, use was made of experimental data for complex moduli of melts of narrow molar mass distribution polystyrenes and their homogeneous blends. In the course of this work two basic observations were made as to the nature of the relaxation time spectra of these blends:

1. The relaxation strength (a product of the weight fraction and the plateau modulus) of a component of large molecules is reduced by the presence of shorter molecules, the latter molecules acting like ordinary diluent molecules even if their molar masses are larger thenM _c .
2. The relaxation time of a molecule (known from measurements on the respective monodisperse component) is considerably changed by the blending. The width of the distribution of relaxation times, as expected from the known composition of the blend, is significantly reduced.

For both processes approximate empirical equations could be found. It turned out that, after the application of the required modifications, the complex moduli of the components could successfully be added in order to obtain the complex moduli of the blend at circular frequencies characteristic for the flow and rubber transition regions. On the basis of these results one may expect that for the melt of any linear polymer the linear viscoelastic properties can be evaluated with reasonable accuracy from the knowledge of the molar mass distribution.     

Finite element analysis of mode III steady crack growth in anisotropic hardening materials

In this paper, the steady crack growth of mode III under small scale yielding conditions is investigated for anisotropic hardening materials by the finite element method. The elastic-plastic stiffness matrix for anisotropic materials is given. The results show the significant influences of anisotropic hardening behaviour on the shape and size of plastic zone and deformation field near the crack tip. With a COD fracture criterion, the ratio of stress intensity factorsk _ss/k_c varies appreciably with the anisotropic hardening parameterM and the hardening exponentN.     

Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow

Zero shear viscosities, ₀, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in ₀ (T) and in M _c , the critical molecular weight determined in plots of log ₀ vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M _c declines considerably. The former observation is explained by analogy to the transition from fragile to hard glasses resulting from increased crosslinking. The latter effect can also be rationalized in terms of a physical network reducing the molecular weight that is required for the formation of entanglements.     

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     

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.