The time,temperature and shear dependence of the viscosity of polypropylene and its influence upon the extrusion process

The polypropylene melt viscosity dependence upon temperature, shear and molecular weight, and the molecular weight dependence upon temperature and time were measured and mathematically described. For the dependence of the melt viscosity upon temperature, shear and molecular weight (melt index), a master curve has been found. The influence of the progressive degradation of polypropylene during the extrusion upon the temperature, pressure and dissipated energy down-channel profiles is given.     

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     

Viscometric properties of viscous theta solutions of monodisperse polystyrene

Theta solvents for polystyrene are prepared from high-viscosity blends of styrene and low-molecular-weight polystyrene, and then used to make dilute solutions with monodisperse polystyrene solutes of high-M = 2.3, 6.0, 9.0, 18.0 · 10⁵. A Weissenberg rheogoniometer is used to measure the non-Newtonian viscosity as a function of shear stress, for low values, and also the complex viscosity components and as functions of frequency. A capillary viscometer is used for high- measurements of(). Viscometric properties, at room temperature, are analyzed as functions of high-molecular-weight solute concentrationc with parameters of constant or to obtain [()], [ ()], and [ ()]. Such a collection of data has apparently not previously been available for polymers in theta solvents (in which Gaussian chain statistics prevail). Also unique is the achievement of high stress ( = 2 10⁴ Pa) at low shear rate, by virtue of high solvent viscosity which is not characteristic of other known theta solvents.     

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.     

Internal viscosity in polymer kinetic theory: shear flows

The Gaussian closure method and Brownian dynamics simulations have been used to calculate the shear material properties of a dilute solution of Hookean dumbbells with internal viscosity. Results for the zero-shear-rate material properties and small amplitude oscillatory shear material properties have been found analytically, and numerical results for the steady state shear material properties are also presented. Two interpretations of the stress tensor are investigated and results are compared. Brownian dynamics simulations are used to obtain material properties of the Hookean dumbbell with internal viscosity without approximations. These simulation results are compared with the perturbation solution of Booij and van Wiechen as well as with a new Gaussian closure solution. Also presented are the contracted distribution functions as derived from the Gaussian closure method and from Brownian dynamics simulations.     

Semi-empirical theory of the viscosity of moderately dilute polymer solutions

The viscosity of moderately dilute polymer solutions is formulated on the postulates that in this concentration region is governed by the domain volume per polymer segment and the noddle effect due to entangling chains. The former is treated semi-molecular theoretically, and the latter entirely phenomenologically. All the parameters involved in the theory can be estimated from appropriate dilute solution data as well as the asymptotic molecular-weight dependence of at different concentrations. It is shown that the theory describes almost quantitatively the experimental data obtained by Hamada and Adam and Delsanti for polystyrene in benzene and cyclohexane. Part of these data reveals the breakdown of the semidilute solution approximation used in the theory.     

A three-parameter model describing the experimental relation between shear stress and shear rate for laminar flow of aqueous polymer solutions

Summary A three-parameter model is introduced to describe the shear rate — shear stress relation for dilute aqueous solutions of polyacrylamide (Separan AP-30) or polyethylenoxide (Polyox WSR-301) in the concentration range 50 wppm – 10,000 wppm. Solutions of both polymers show for a similar rheological behaviour. This behaviour can be described by an equation having three parameters i.e. zero-shear viscosity ₀, infinite-shear viscosity , and yield stress ₀, each depending on the polymer concentration. A good agreement is found between the values calculated with this three-parameter model and the experimental results obtained with a cone-and-plate rheogoniometer and those determined with a capillary-tube rheometer.

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Zusammenfassung Der Zusammenhang zwischen Schubspannung und Schergeschwindigkeit von strukturviskosen Flüssigkeiten wird durch ein Modell mit drei Parametern beschrieben. Mit verdünnten wäßrigen Polyacrylamid-(Separan AP-30) sowie Polyäthylenoxidlösungen (Polyox WSR-301) wird das Modell experimentell geprüft. Beide Polymerlösungen zeigen im untersuchten Schergeschwindigkeitsbereich von ein ähnliches rheologisches Verhalten. Dieses Verhalten kann mit drei konzentrationsabhängigen Größen, nämlich einer Null-Viskosität ₀, einer Grenz-Viskosität und einer Fließgrenze ₀ beschrieben werden. Die Ergebnisse von Experimenten mit einem Kegel-Platte-Rheogoniometer sowie einem Kapillarviskosimeter sind in guter Übereinstimmung mit den Werten, die mit dem Drei-Parameter-Modell berechnet worden sind.

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a Pa^–1 physical quantity defined by:a = {1 – ( / ₀)}/ ₀ - c l concentration (wppm) - D m capillary diameter - L m length of capillary tube - P Pa pressure drop - R m radius of capillary tube - u m s^–1 average velocity - v _r m s^–1 local axial velocity at a distancer from the axis of the tube - shear rate (–dv _r /dr) - local shear rate in capillary flow - s^–1 wall shear rate in capillary flow - Pa s dynamic viscosity - _a Pa s apparent viscosity defined by eq. [2] - ( _a ) Pa s apparent viscosity in capillary tube at a distanceR from the axis - ₀ Pa s zero-shear viscosity defined by eq. [4] - Pa s infinite-shear viscosity defined by eq. [5] - l ratior/R - kg m^– density - Pa shear stress - ₀ Pa yield stress - _r Pa local shear stress in capillary flow - _R Pa wall shear stress in capillary flow _R = (PR/2L) - _v m³ s^–1 volume rate of flow With 8 figures and 1 table     

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.     

Non-linear behaviour of asphalts in steady and transient shear flow

Steady-state and transient shear stress and normal stress data were obtained for four asphalts with a modified Weissenberg Rheogoniometer. Interest was specially related to non-linear behaviour at high shear-rates. The time-temperature superposition principle was found to hold in non-linear behaviour. Moreover, steady-state and transient data could be plotted as master curves irrespective of the nature of the asphalts. In particular, the master curve of steady-state viscosity could be extended to results published in the literature. In the nonlinear region the shear stress relaxation after cessation of a steady shear rate becomes a function of t only and is related to the primary normal-stress coefficient, as predicted by the Yamamoto equation. In the shear stress growth experiment an overshoot is obtained at a constant strain close to 1.5, independent of the rate of strain.     

On the eddy viscosity model of periodic turbulent shear flows

Physical argument shows that eddy viscosity is essentially different from molecular viscosity. By direct numerical simulation, it was shown that for periodic turbulent flows, there is phase difference between Reynolds stress and rate of strain. This finding posed great challenge to turbulence modeling, because most turbulence modeling, which use the idea of eddy viscosity, do not take this effect into account. The project supported by the National Natural Science Foundation of China (19732005) and Liu Hui Center for Applied Mathematics of Nankai & Tianjin University     

Shear dependence of viscosity for perfluoropolyether fluids

The shear dependence of the bulk viscosities of two structurally different types of perfluoropolyether fluids was determined by two different techniques. The first involved direct measurement in a high shear Couette viscometer, the second utilized the time-temperature superposition principle to establish master curves from viscosity determinations at low shear rates and temperature; the results are comparable. Both fluids begin to show non-Newtonian behavior at shear rates above 10,000 s^–1.     

Testing viscometric predictions of the internal viscosity model,using dilute viscous theta solutions

A stress-symmetrized internal viscosity (I.V.) model for flexible polymer chains, proposed by Bazua and Williams, is scrutinized for its theoretical predictions of complex viscosity ^* () = – i and non-Newtonian viscosity (), where is frequency and is shear stress. Parameters varied are the number of submolecules,N (i.e., molecular weightM = NM _s ); the hydrodynamic interaction,h ^*; and/f, where andf are the I.V. and friction coefficients of the submolecule. Detailed examination is made of the eigenvalues _p (N, h ^*) and how they can be estimated by various approximations, and property predictions are made for these approximations.Comparisons are made with data from our preceding companion paper, representing intrinsic properties [], [], [] in very viscous theta solutions, so that theoretical foundations of the model are fulfilled. It is found that [ ()] data can be predicted well, but that [ ()] data cannot be matched at high. The latter deficiency is attributed in part to unrealistic predictions of coil deformation in shear.     

Determination of the steady-state shear viscosity from measurements of the apparent viscosity for some common types of viscometers

Considering a number of model fluids, the relation between the (measurable) apparent viscosity _a and the (true) shear viscosity is studied for some commonly used viscometers, like capillary, slit, plate-plate and concentric cylinders (including the influence of the bottom of the cylinder), as well as for one laboratory type of viscometer. As long as is a purely monotonic function, a shift factor < 1 allows one to deduce from _a . Though in general variable, it frequently suffices for practical purposes to use a constant shift factor (the constant being characteristic of the type of viscometer used). This does not apply to dilute solutions or any fluids with two plateau values for . For plastic fluids, it is shown that Casson or Bingham behavior can — if valid at all — only describe the high shear stress limit of _a .     

Phenomena of high polymer solutions while flowing through capillaries at high rates of shear

Generally solutions of high polymers show a shear-rate dependent flow behaviour and so the properties of these fluids have to be measured under conditions of shear corresponding to the practical service. Capillary viscometry is suitable for achieving high rates of shear but relaxation phenomena can effect the results, which is proved experimentally. The flow behaviour of a lubricant blended with a high polymer additive is measured and a graphical representation of the dependence of flow behaviour on temperature and rate of shear is recommended.     

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     

Effect of a controlled pre-deformation history on extensional viscosity of dilute polymer solutions

We use a modified filament stretching rheometer to quantify the influence of a known controlled pre-shear history on the transient extensional viscosity of a dilute polymer solution. Two different types of pre-deformation are explored; both influence the subsequent stretching significantly, albeit in opposite ways. Small-amplitude oscillatory straining parallel to the direction of stretching enhances strain hardening and accelerates the tensile stress growth toward the steady-state value. Conversely, steady torsional shearing orthogonal to the direction of stretching retards strain hardening and results in a delayed approach to steady-state elongational flow. In both cases, the final steady-state extensional viscosity is the same as that observed with no pre-shearing. Calculations using a finitely extensible nonlinear elastic Peterlin dumbbell model qualitatively capture the trends observed in experiments, enabling interpretation of these observations in terms of the degree of polymer chain stretching imposed by the flow before extensional stretching.     

A new semi-empirical spectrum model for complex steady shear viscosity of complex fluids

A semi-empirical spectrum model is proposed to describe the experimental data of the steady shear properties of a Shengli waxy crude oil near its gel point, where sophisticated structural effects become apparent due to the existence of waxy crystals in the crude oil. The model, consisting of a time spectrum, can well fit the steady shear viscosities of the waxy crude oil over the whole experimental shear rate region from 10-4 to 102 s- 1. Two other experiments on complex fluids reported recently in the literature are also well described by this model demonstrating the applicability and accuracy of the model.     

Low frequency/shear rate measurements on polymer melts with a novel rheometer

To obtain the time dependent viscosity function over a wide experimental window, data from two different measuring instruments and methods were combined. The instruments involved were a conventional dynamic rheometer and the magnetoviscometer (MVM), a novel apparatus specially designed for measuring at low shear rates. For most of the investigated materials the MVM-data allow an expansion of the known time-range to higher values, thus giving additional information about the longest relaxation times in the systems, which in turn correspond to the high-molecular tail of the molar mass distribution. Especially in the long time range where it is difficult to get good dynamical data the experimental error of the MVM-data is very small.     

On the extensional viscosity of mobile polymer solutions

We describe experimental results on the extensional viscosity of mobile polymer solutions obtained from two instruments, the first being a commercial Spin Line Rheometer and the second a custom-built lubricated-die Converging Flow Rheometer. The interpretation of data in terms of Trouton ratios is facilitated by a simple analysis for the Generalized Newtonian Fluid model.Agreement between data from the two rheometers is satisfactory and we show that polymer solutions can be either tension stiffening or tension thinning. However, the Trouton ratios in both cases are greater than the Newtonian values and we anticipate that this will always be the case for polymer solutions.Invited paper, presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986