Anisotropic conduction of heat caused by molecular orientation in a flowing polymeric liquid

To demonstrate the influence of molecular orientation on the heat conduction in a flowing polymeric liquid, we consider a variant of the Graetz-Nusselt problem. A polymeric liquid is flowing between two flat, parallel plates with a sudden change in the wall temperature. The temperature distribution in the entrance region is calculated numerically taking viscous dissipation into account. It is assumed that the material properties are independent of the temperature. It is shown that the change in the temperature distribution in the fluid caused by molecular orientation is large enough to affect polymer processing significantly.     

A network theory for the thermal conductivity of an amorphous polymeric material

A model to relate the thermal conductivity tensor to the deformation of an amorphous polymeric material above the glass transition temperature is presented. The basis of the model is formed by the transient network theory for polymer melts. With this theory it is possible to calculate the average orientation of the macromolecular segments as a function of the history of the deformation. Combined with an expression which relates the thermal conductivity to the orientation of the molecules, this provides us with the information needed to calculate the heat conduction tensor. Despite the fact that the simplest possible network model is chosen, there is good agreement with the sparse, experimental results.     

Viscometric flows of polymeric melts treated according to the rational theory of Eckart's continuum. I. General theory

The purely rational theory of Eckart continua (i.e. elastic bodies with a variable relaxed state) is applied to viscometric flows of polymeric melts. The main assumptions are thermodynamic non-interaction of inelastic behaviour and of non-elastic stress, as well as elastic isotropy. After establishing the time-dependent differential equations of viscometric flow, these equations are simplified to a set of algebraic equations describing steady-state flow. From this we deduce two general equations connecting the three elastic steady-state viscometric functions which do not depend upon the elastic behaviour. The law of rubber elasticity used in this paper is described in the Appendix.     

Fractal-time stochastic processes and dynamic functions of polymeric systems

Dynamic material functions of polymeric systems are calculated via a defect-diffusion model. The random motion of defects is modelled by a fractaltime stochastic process. It is shown that the dynamic functions of polymeric solutions can be approximated by the defect-diffusion process of the mixed type. The relaxation modulus of Kohlrausch type is obtained for a fractal-time defect-diffusion process, and it is shown that this modulus is capable of portraying the dynamic behavior of typical viscoelastic solutions.The Fourier transforms of the Kohlrausch function are calculated to obtain and. A three-parameter model for and is compared with the previous calculations. Experimental measurements for five polymer solutions are compared with model predictions. D rate of deformation tensor - G(t) mechanical relaxation modulus - H relaxation spectrum - I(t) flux of defects - P _n (s) probability of finding a walker ats aftern-steps - P generating function ofP _n (s) - s(t) fraction of surviving defects - , () gamma function (incomplete) - ₀ zero shear viscosity - ^* () complex viscosity - frequency - t _n n-th moment - F[] Fourier transform - f ^* (u) Laplace transform off(t) - , components of ^* - G _f, _f ^* fractional model - G ₃, ₃ ^* three parameter model - complex conjugate ofz - material time derivative ofD     

Driven torsion pendulum for measuring the complex shear modulus in a steady shear flow

To investigate the viscoelastic behavior of fluid dispersions under steady shear flow conditions, an apparatus for parallel superimposed oscillations has been constructed which consists of a rotating cup containing the liquid under investigation in which a torsional pendulum is immersed. By measuring the resonance frequency and bandwidth of the resonator in both liquid and in air, the frequency and steady-shear-rate-dependent complex shear modulus can be obtained. By exchange of the resonator lumps it is possible to use the instrument at four different frequencies: 85, 284, 740, and 2440 Hz while the steady shear rate can be varied from 1 to 55 s^–1. After treatment of the theoretical background, design, and measuring procedure, the calibration with a number of Newtonian liquids is described and the accuracy of the instrument is discussed.Notation a radius of the lump - A geometrical constant - b inner radius of the sample holder - c constant - C ₁, C ₂ apparatus constants - D damping of the pendulum - e _x , e _y , e _z Cartesian basis - e _r , e , e _z orthonormal cylindrical basis - E geometrical constant - E _t , ⁰ E _t , _t relative strain tensor - f function of shear rate - F _t relative deformation tensor - G (t) memory function - G ^* complex shear modulus - G Re(G ^* ) - G Im(G ^* ) - h distance between plates - H ^* transfer function - , functional - i imaginary unit: i ²= – 1 - I moment of inertia - J _exc excitation current - J ₀ amplitude of J _exc - k ^* = k – ik complex wave number - K torsional constant - K fourth order tensor - l length of the lump - L mutual inductance - M _dr driving torque - M _liq torque exerted by the liquid - ⁰ M _liq, _liq steady state and dynamic part of Mliq - n power of the shear rate - p isotropic pressure - Q quality factor - r radial position - R,R ₀, R _c Re(Z ^*, Z ₀ ^* , Z _c ^* ) - s time - t, t time - T temperature - T, ⁰ T, stress tensor - u velocity - U lock-in output - ₀ velocity - V _det detector output voltage - V _sig, V _cr signal and cross-talk part of V _det - x Cartesian coordinate - X , X ₀, X _c Im(Z ^*, Z ₀ ^* , Z _c ^* ) - y Cartesian coordinate - z Cartesian coordinate, axial position     

A note on the coefficient of viscosity of pure molten 2,4,6-trinitrotoluene (TNT)

The viscosity of pure molten TNT has been investigated over the temperature range 82.0°–95.4°C. The temperature dependence of viscosity was found to be best represented by a relation of the type = A e ^B/T whereA = 0.000541,B = 3570, is the viscosity in mPa s andT is the temperature in Kelvin. Earlier work, which suggests an inverse temperature dependence of the flow activation energy, is shown to include an error in the published equation for the temperature dependence of the viscosity of molten TNT.     

The steady shear viscosity of filled polymeric liquids described by a linear superposition of two relaxation mechanisms

Filled polymeric liquids often exhibit apparent yielding and shear thinning in steady shear flow. Yielding results from non-hydrodynamic particle—particle interactions, while shear thinning results from the non-Newtonian behavior of the polymer melt. A simple equation, based on the linear superposition of two relaxation mechanisms, is proposed to describe the viscosity of filled polymer melts over a wide range of shear rates and filler volume fraction.The viscosity is written as the sum of two generalized Newtonian liquid models. The resulting equation can describe a wide range of shear-thinning viscosity curves, and a hierarchy of equations is obtained by simplifying the general case. Some of the parameters in the equation can be related to the properties of the unfilled liquid and the solid volume fraction. One adjustable parameter, a yield stress, is necessary to describe the viscosity at low rates where non-hydrodynamic particle—particle interaction dominate. At high shear rates, where particle—particle interactions are dominated by interparticle hydrodynamics, no adjustable parameters are necessary. A single equation describes both the high and low shear rate regimes. Predictions of the equation closely fit published viscosity data of filled polymer melts. n power-law index - n ₁,n ₂ power-law index of first (second) term - shear rate - steady shear viscosity - ₀ zero-shear rate viscosity - _{0, 1}, _{0, 2} zero-shear rate viscosity of first (second) term - time constant - ₁, ₂ time constant of first (second) term - µ _r relative viscosity of filled Newtonian liquid - ₀ yield stress - ø solid volume fraction - ø _m maximum solid volume fraction     

Bildung orientierter Randschichten in Spritzgußplatten aus Polypropylen

Zusammenfassung An 2 mm dicken unter verschiedenen Bedingungen spritzgegossenen Platten aus zwei Polypropylentypen mit unterschiedlicher Molmassenverteilung wird durch Messung der optischen Doppelbrechung die Dicke der hochorientierten Randschichten bestimmt. Durch solche Messungen an Platten, die mit und ohne Nachdruck gespritzt wurden, lassen sich die während der Füllphase von den während der Nachdruckphase entstandenen Orientierungsanteilen trennen. Möglichkeiten der theoretischen Berechnung der Randschichtdicke werden diskutiert.Hieraus ergibt sich, daß die hochorientierten Randschichten bereits während des Füllvorganges entstehen und deren Dicke vermutlich durch die Konkurrenz zwischen scherinduzierter Kristallisation und Relaxation bestimmt wird. Beim Spritzen ohne Nachdruck kann die Schmelze in der Mitte der Platte zwischen den Randschichten relaxieren und stark unterkühlt werden, bevor sie kristalliert, wie durch zusätzliche Messungen nachgewiesen wurde.

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The thickness of highly oriented skin layers is determined on 2-mm-thick plates injected under different processing conditions by birefringence measurements. Two technical polypropylene types of different molar mass distributions are used. Measurements on samples injected with and without pressure hold after filling make it possible to decide between chain orientation caused during injection and chain orientation caused by the pressure hold after filling. Different models for the calculation of the oriented layer thickness are discussed.The results reveal that the highly oriented skin layers are already formed during the filling phase and that thickness is probably determined through the opposing development of stress-induced crystallization and relaxation. Further measurements indicate that at the injection molding without pressure hold after filling, the melt can relax between the skin layers and can be strongly supercooled before it crystallizes.

Erweiterte Fassung eines Vortrages anläßlich des Hamburger Symposiums Rheologie makromolekularer Stoffe, 18.–22. 9. 1986     

Effect of processing and particulate fillers on the rheology of a nematic polymer melt

Processing of a nematic HBA/HNA polymer melt increases the capillary diameter dependence of the viscosity and induces structural changes which are evident in oscillatory shear, but cannot be characterized by DSC. The effect of 6-m calcium carbonate particulate fillers is to increase the viscosity uniformly. Low concentrations of sub-micron carbon black particles cause an unexplained viscosity minimum in a large (30-mil) capillary.     

Messung der dynamischen Eigenschaften verdünnter Polymerlösungen

Zusammenfassung Ein neuartiges Rheometer zur Ermittlung der rheologischen Eigenschaften von Polymerlösungen im linear-viskoelastischen Bereich wird vorgestellt. Durch Anwendung der Laser-Doppler-Anemometrie, die eine im hydro-dynamischen Sinn störungsfreie Meßmethode darstellt, ist es möglich, niedrig-viskose bis hin zu wasserähnlichen Proben zu vermessen.Zur Bewältigung der in großer Zahl anfallenden Daten und Rechenoperationen findet ein Mikrocomputer-System Verwendung. Es erledigt im einzelnen die Aufgaben Versuchsablauf-Steuerung, Meßwerterfassung, Auswertung, Dokumentation und graphische Darstellung der Ergebnisse.Anhand von Messungen an newtonschen Flüssigkeiten werden der Funktionsnachweis erbracht und die Betriebsbereiche der Ringspaltsysteme unterschiedlichen Durchmessers ermittelt.Die viskoelastischen Eigenschaften von wäßrigen Polyethylenoxid- und Polyacrylamid-Lösungen niedriger Viskosität lassen sich über einen Frequenzbereich von 0,1 bis 100 Hz messen. Die Ergebnisse werden mit Hilfe der komplexen Viskositätsfunktion dargestellt. Daraus läßt sich als gleichwertige Darstellung das diskrete Relaxationsspektrum eines konkreten Stoffgesetzes gewinnen.

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A novel rheometer for determining the elastic characteristics of polymeric solutions in the linear-viscoelastic region is described. Laser-Doppler anemometry, which does not introduce hydrodynamic disturbances, is used to enable low viscosity liquids including water-like samples to be measured.A microcomputer system is utilized to control the experiments, store and analyse the measured data, and provide graphical representations of the results. Measurements on Newtonian liquids verified the validity of the method and allowed the operational regions of the annulus systems with different diameters to be determined.The elastic characteristics of low viscosity aqueous solutions of polyethyleneoxide and polyacrylamide can be measured at frequencies from 0.1 to 100 Hz. The results are presented using the complex viscosity function. As a result the discrete relaxation spectrum of a special material law can be obtained as an equivalent representation.

     

Measurement of the shear viscosity using a newly developed GRLDA-viscometer

A two-point laser-Doppler anemometer is used to determine velocity gradients. Measuring additionally the pressure drop in channel flow allows one to use this instrument as a viscometer. This is demonstrated by measuring two polymer solutions as well as water. Besides the velocity gradient, the system also furnishes the velocity as well as velocity fluctuations. For surfactant solutions the sudden increase in these fluctuations go hand-in-hand with the sudden shear thickening reported. This behavior thus seems to be caused by a change in type of flow field (structural turbulence) rather than a change in the rheology of the surfactant solutions.This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Apparent thickening behavior of dilute polystyrene solutions in extensional flows

An experimental investigation was undertaken to study the apparent thickening behavior of dilute polystyrene solutions in extensional flow. Among the parameters investigated were molecular weight, molecular weight distribution, concentration, thermodynamic solvent quality, and solvent viscosity. Apparent relative viscosity was measured as a function of wall shear rate for solutions flowing from a reservoir through a 0.1 mm I.D. tube. As increased, slight shear thinning behavior was observed up until a critical wall shear rate was exceeded, whereupon either a large increase in or small-scale thickening was observed depending on the particular solution under study. As molecular weight or concentration increased, decreased and, the jump in above , increased. increased as thermodynamic solvent quality improved. These results have been interpreted in terms of the polymer chains undergoing a coil-stretch transition at . The observation of a drop-off in at high (above ) was shown to be associated with inertial effects and not with chain fracture due to high extensional rates.     

The stability of the helical flow of pseudoplastic liquids in a narrow annular gap with a rotating inner cylinder

The stability of a laminar helical flow of pseudoplastic liquids in an annular gap with a rotating inner cylinder is investigated theoretically. The analysis is carried out under the assumption of a torroidal form of the secondary flow (torroidal Taylor vortices) for the narrow gap geometry. The power law model has been applied to describe the pseudoplasticity of liquids. The problem of the stability has been formulated with the aid of the method of small disturbances, and solved using the Galerkin method. In order to describe the stability limit the Reynolds and Taylor numbers defined with the aid of the mean viscosity value have been introduced. It has been found that pseudoplasticity has a considerably destabilizing influence on the Couette motion as well as on the helical flow in the initial range of the Reynolds number values (Re<30). A decrease of the flow index value,n, is accompanied by a decrease of the critical value of the Taylor number. This destabilizing effect of pseudoplasticity vanishes in the range of the larger values of the Reynolds number. In the rangeRe>30, the stability limit of the flow of pseudoplastic liquids can be described by a general dependence of the critical valueTa _c onRe, which is consistent with results obtained for the case of Newtonian fluids. a frequency number (Eq. (27)), 1/s - b wave number (Eq. (27)), 1/m - B = M/N parameter - d = R ₂ –R ₁ gap width, m - f(y, B, k) function of viscosity distribution (Eq. (7)) - f ₀ (x) function of viscosity distribution (narrow gap Eq. (35)) - F(x) = V(x)/V _m dimensionless distribution of axial flow velocity - G(x) = U(x) _i dimensionless distribution of angular flow velocity - K consistency coefficient, N sⁿ/m² - M = (P/L)R ₂ parameter of the stress field (Eq. (1)), N/m² - M ₀ torque per unit length, N - n flow index - N = M ₀/(2R ₂ ² ) parameter of the stress field (Eq. (1)), N/m² - p = 1/2n–1/2 parameter - pressure disturbance amplitude, N/m² - p pressure disturbance, N/m² - (P/L) pressure drop per unit length of the gap, N/m² - r radial coordinate, m - r _m location of the maximum value of the axial velocity, m - R ₁,R ₂ inner, outer radius of the annulus, m - Re = V _m 2d/ _m Reynolds number - S = (P/L · d/N) parameteer of the stress field (narrow gap) - t time, s - Ta = _i d ^3/2 R ₁ ^1/2 / _m Taylor number - U tangential velocity, m/s - U _i tangential velocity at the surface of the inner cylinder, m/s - V axial velocity, m/s - V _m mean axial velocity, m/s - V disturbance vector of velocity field, m/s - amplitude of theV _k -disturbance, m/s - X, Y, Z functions in Eqs. (36–38) - y = r/R ₂ dimensionless radial coordinate - x = (r—(R ₁+R ₂)/2)d radial coordinate (narrow gap) - L ₁ L ₄ linear operators in Eqs. (36–38) - = ad/V _m dimensionless frequency number - = b·d dimensionless wave number - component of the rate of strain tensor, 1/s - component of the rate of strain tensor corresponding to the disturbance, 1/s - = R ₁/R ₂ radius ratio - apparent viscosity, Ns/m² - ₀ apparent viscosity in the main flow, Ns/m² - µ disturbance of the apparent viscosity, Ns/m² - µ _m mean apparent viscosity, Ns/m² - density, kg/m³ - _ij component of the stress tensor, N/m² - angular velocity, rad/s - _i angular velocity of the inner cylinder, rad/s     

Wall effects in the flow of flexible polymer solutions through small pores

Effective viscosities of dilute and semidilute flexible solutions flowing through small cylindrical pores were determined in the Newtonian regime for various pore diameters. The low viscosities relative to the bulk were associated with a depletion phenomenon due to a steric exclusion of macromolecules from the pore wall. Using a two-fluid flow model, the depletion layer thickness was determined and discussed as a function of polymer concentration, ionic strength, and molecular weight. This thickness, which was constant and close to the macromolecule gyration radius in dilute regime, was found to decrease rapidly with polymer concentration in the semidilute regime.     

Viscosity of some clay-based coating colors at high shear rates

The shear viscosity of clay-based coating colors containing latex and carboxymethyl cellulose (CMC) has been measured over a relatively large shearrate region. In the shear-rate range of 50–1500 s^–1 the measurements were performed using a rotational viscometer and, at higher shear rates extending into the region 10⁵ – 10⁶ s^–1, a high pressure capillary viscometer was employed. The viscosity of the clay colors increased with increasing CMC-concentration, but the influence of the CMC-content was less pronounced at higher shear rates. The apparent shear-thinning behavior of the investigated colors could, in part, be attributed to the shear-thinning of the corresponding polymer (CMC) solution constituting the liquid phase of the color, but the influence of another factor was also indicated. At low shear rates, the interaction between the color components can produce relatively high viscosity levels, but in the high shear rate region these interactions appear to be less important for the viscosity level. It is also of interest to note that the viscosity dependence on the solids content in the high shear-rate region could be described with reasonable accuracy using an empirical equation neglecting interactions between the color components.     

The non-isothermal elastic dumbbell: A model for the thermal conductivity of a polymer solution

In a flowing polymeric liquid, molecular orientation will give rise to anisotropic conduction of heat. In this paper, a theory is presented relating the thermal conductivity tensor to the deformation history of the fluid. The basis of this theory is formed by the Hookean dumbbell. It is shown that the anisotropy of the thermal conductivity is proportional to the polymer contribution to the extra-stress tensor. This stress-thermal law makes it relatively simple to incorporate anisotropic heat conduction into the numerical simulation of a flowing polymeric liquid.     

Prediction of the non-linear rheological properties of polymer solutions by means of the Rouse-Zimm model with slippage

The non-affine deformation of macromolecules and the slippage function are discussed. In case of polymer solutions with moderate concentration the slippage function is determined by means of the Cox-Merz rule. The non-linear viscoelasticity of these solutions is described with the aid of the Rouse-Zimm model with slippage function. The theoretical predictions show good agreement with published experimental data.     

Compression creep of molten poly (butylene terephthalate)

Viscoelastic parameters of poly(butylene terephthalate) melt in compression creep have been measured in an Instron Capillary Rheometer. Bulk compression creep complianceB(t) shows plateau regions in the molten state and in the melt crystallized state, both decreasing with increasing stress. Shifting ofB(t) curves provides master curves suitable for analyzing the total (superposed elastic and viscous) bulk compression behavior.Volume viscosity decreases with both increasing stresses and compression rates but seems to be independent of temperature. Its values are larger than those from constant compression rate experiments, possibly due to the presence of elastic effects.