Molecular weight polydispersity effects on the melt viscoelasticity of styrene-acrylonitrile random copolymers

A series of polydisperse SAN (styrene-co-acrylonitrile) random copolymers was studied by means of oscillatory rheometry in the rubbery plateau zone and in the terminal zone. The plateau modulus, the Newtonian viscosity, and the critical frequencies for the onset of non-Newtonian behavior were extracted from the experimental data. All these viscoelastic quantities consistently indicate that the tail of molecular weights below approximately M _e (the entanglement spacing) acts as a solvent for the rest of the polymer with M>M _e .     

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.     

Mesophase formation in high molecular-weight xanthan solutions

After a short review of theoretical background on mesophase formation in polymer solutions, this paper describes the liquid crystal phase transition and the corresponding rheological properties for aqueous solutions of a high-molecularweight xanthan sample (M _w 1.8 10⁶). The formation of mesophases has been studied using polarizing microscopy and viscometry. The effects of the presence of salts, bacteria cells and proteins have been investigated. The variations in the viscosity, due to mesophase formation, are in qualitative agreement with the predictions of Matheson's theory, but the onset of the ordered phase occurs at very low polymer concentrations and the diphasic domain is much broader than predicted by thermodynamic models. These characteristics of the phase transition are related to the very high molecular weight of the sample studied and can be explained mainly by the effects of cooperative interactions between xanthan chains and of chain flexibility reducing translational entropy.     

The molecular theory of viscoelasticity for thermoplastic elastomer SBS (SIS) at large deformations

A microstructure model for SBS and SIS triblock copolymers with hard domains as multifunctional reinforcing fillers is proposed. Based on this model and proposed mechanism of large deformations, the probability distribution function of the end-to-end vector for each constituent chain and the free energy of deformation for the total networks was calculated by the combination of statistical thermodynamics and kinetics. A new molecular theory of non-linear visco-elasticity for SBS and SIS at large deformations is presented. It is successful in relating the viscoelastic state to molecular constitution by three important parameters (C ₁₀₀,C ₀₂₀, andC ₂₀₀) of the networks. The relations of stress to strain for four types of deformation, the elastic modulus and the constitutive equation for the stress relaxation were derived from this theory. It provides a theoretical foundation for studying the relationships of multiphase network structures and mechanical properties at large deformations. An excellent agreement between the theoretical relationships and experimental data from the experiments and the reference was obtained.Project supported by the National Natural Foundation of China     

The rotation of a suspended axisymmetric ellipsoid in a magnetic field

Under the influence of a uniform and parallel magnetic field, a ferromagnetic fiber suspended in a Newtonian fluid rotates to align with the field direction. This study examines the field-induced rotation process for an individual non-Brownian axisymmetric ellipsoid suspended in a stagnant Newtonian fluid. Theoretical predictions are derived by a perturbation analysis for the limiting case where the strength of the applied magnetic field far exceeds the saturation magnetization of the ellipsoid. Numerical calculations are performed for the more general problem of an ellipsoid with known isotropic, non-hysteretic magnetic properties, using nickel and a stainless steel as examples. The analysis encompasses materials with field-induced, nonlinear magnetic properties, distinguishing these results from the simpler cases where the particle magnetization is either independent of, or linearly dependent on, the strength of the applied external field. In this study, predictions indicate that when the ellipsoid is magnetically saturated, the particle rotation is governed by the magnetoviscous time constant, _MV = _s/₀ M _s ² . It is found that the rotation rate depends strongly on the aspect ratio,a/b, of the ellipsoid, but only weakly on the dimensionless magnetization,M _s/H ₀. A geometric parameter for an ellipsoid, defined in eq. (2.5) - a, b major, minor semi-axes of an axisymmetric ellipsoid - D demagnetization tensor for an ellipsoid - D ^M magnetometric demagnetization tensor, the volume-average ofD ^P (r) - D ^P (r) position dependent demagnetization tensor, implicitly defined in eq. (2.12) - D _xx,D _yy,D _zz demagnetization factors, the diagonal elements ofD. Values for ellipsoids are defined in eq. (2.15) - F ^(m) magnetic force exerted on a body in a magnetic field - H _i ;H _i magnetic field inside a ferromagnetic body; magnitude ofH _i - H ₀;H ₀ magnetic field applied by external sources; magnitude ofH ₀ - h _i ;h _ix,h _iy Cartesian components of dimensionless internal magnetic field,h _i =H _i /H ₀ - I moment of inertia tensor - k geometric parameter for hydrodynamic resistance of a body rotating in a Newtonian fluid given in eq. (2.3) - L ^(h);L _z ^(h) hydrodynamic torque exerted on a rotating body; thez-component of the hydrodynamic torque - L ^(m);L _z ^(m) magnetic torque exerted on a magnetic body in a magnetic field, eq. (2.10); thez-component of the magnetic torque - M;M the magnetization, or dipole moment density, of a magnetic material; the magnitude ofM - M _s the saturation value ofM, approached by all ferromagnetic materials asH _i becomes large (figure 3) - m _s the dimensionless saturation magnetization,M _s/H ₀ - r position vector of a point within a ferromagnetic body - s dummy integration variable in eq. (2.5) - t time - U magnetoquasistatic potential energy of a magnetic body in a magnetic field, given in eq. (2.8) - u curve-fitting variable in eq. (4.1);u = logH _i - V volume of a magnetic particle; for an axisymmetric ellipsoid,V = (4/3) ab ² - x, y, z rectangular coordinate axes fixed in the ellipsoid (figure 1) - angle of inclination of the major axis of the ellipsoid with respect toH ₀ - _s viscosity of the Newtonian suspending medium - µ ₀ the magnetic permeability of free space,µ ₀ =4 · 10^–7H/m - _MV the magnetoviscous time constant, a characteristic time for a process involving a competition of viscous and magnetic stresses - the magnetic susceptibility of a magnetic material, = M/H _i - ; _z angular velocity of a rotating body; angular velocity about thez-axis of an ellipsoid, _z=–d/dt     

Viscous heating correction for thermally developing flows in slit die viscometry

In the thermally developing region, d _yy /dx| _y=h varies along the flow direction x, where _yy denotes the component of stress normal to the y-plane; y = ±h at the die walls. A finite element method for two-dimensional Newtonian flow in a parallel slit was used to obtain an equation relating d _yy /dx/ _y=h and the wall shear stress ₀ at the inlet; isothermal slit walls were used for the calculation and the inlet liquid temperature T₀ was assumed to be equal to the wall temperature. For a temperature-viscosity relation /₀ = [1+(T–T₀]^–1, a simple expression [(hd _yy /dx/ _y=h )/ _w0] = 1–[1-F _c(Na)] [M()+P(Pr) ·Q(Gz ^–1)] was found to hold over the practical range of parameters involved, where Na, Gz, and Pr denote the Nahme-Griffith number, Graetz number, and Prandtl number; is a dimensionless variable which depends on Na and Gz. An order-of-magnitude analysis for momentum and energy equations supports the validity of this expression. The function F _c(Na) was obtained from an analytical solution for thermally developed flow; F _c(Na) = 1 for isothermal flow. M(), P(Pr), and Q(Gz) were obtained by fitting numerical results with simple equations. The wall shear rate at the inlet can be calculated from the flow rate Q using the isothermal equation.Notation x,y Cartesian coordinates (Fig. 2) - , dimensionless spatial variables [Eq. (16)] - dimensionless variable, : = Gz(x)^–1 - dimensionless variable [Eq. (28)] - t,t ^* time, dimensionless time [Eq. (16)] - , velocity vector, dimensionless velocity vector - _x , velocity in x-direction, dimensionless velocity - _y , velocity in y-direction, dimensionless velocity - V average velocity in x-direction - _yy , ^* normal stress on y-planes, dimensionless normal stress - shear stress on y-planes acting in x-direction - _w , _w ^* value of shear stress stress at the wall, dimensionless wall shear stress - _w0, _w0 ^* wall shear stress at the inlet, dimensionless variable - , ^* rate-of-strain tensor, dimensionless tensor - wall shear rate, wall shear rate at the inlet - Q flow rate - T, T ₀, temperature, temperature at the wall and at the inlet, dimensionless temperature - h, w half the die height, width of the die - l,L the distance between the inlet and the slot region, total die length - T ₂, T ₃, T ₄ pressure transducers in the High Shear Rate Viscometer (HSRV) (Fig. 1) - P, P2, P3 pressure, liquid pressures applied to T ₂ and T ₃ - , ₀, ^* viscosity, viscosity at T = T ₀, dimensionless viscosity - viscosity-temperature coefficient [Eq. (8)] - k thermal conductivity - C _p specific heat at constant pressure - Re Reynolds number - Na Nahme-Griffith number - Gz Graetz number - Pr Prandtl number     

Experimental studies of suspended ferromagnetic fibers in a magnetic field

The analysis of the rotation of a ferromagnetic ellipsoid suspended in a Newtonian fluid and subjected to a uniform magnetic field is extended to include a long, slender cylindrical fiber which is magnetically saturated. Experimental observations of rotating nickel cylinders with aspect ratiosL/D ranging from 5 to 40 agree with the theoretical predictions that: (1) the proper magnetoviscous time constant for the motion is _MV = _s/µ ₀ M _s ² , (2) larger fiber aspect ratios result in considerably longer orientation times; and (3) the strength of the applied external field has only a slight effect on the overall fiber rotation, and has no effect on the maximum angular velocity achieved. Quantitative agreement of theory and experiments is obtained for fibers withL/D 20; for the shorter fibers, the theory tends to overpredict the fiber rotation rate by as much as 30%. D diameter of the cylinder - D ^P (r) position-dependent demagnetization tensor, implicitly defined in eq. (2.5) - D _xx,D _yy,D _zz volume-averaged demagnetizing factors for an ellipsoid equivalent to a uniformly magnetized cylinder, defined in eq. (2.6) - H _i ;H _i magnetic field inside a ferromagnetic body; magnitude ofH _i - H ₀;H ₀ magnetic field applied by external sources; magnitude ofH ₀ - k geometric parameter in the hydrodynamic resistance of a body rotating in a Newtonian fluid, eq. (2.2) - L length of the cylinder - L ^(h);L _z ^(h) hydrodynamic torque exerted on a rotating body; thez-component ofL ^(h) on the cylinder - L ^(m);L _z ^(m) magnetic torque exerted on a magnetic body in a magnetic field, eq. (2.4); thez-component ofL ^(m) on the cylinder - M the magnetization of a magnetic material - M _s the saturation magnitude ofM, approached by all ferromagnetic materials asH _i becomes large - r position vector of a point within a ferromagnetic body - V volume of a magnetic particle - x, y, z rectangular coordinate axes fixed in the cylinder according to figure 1 - angle of inclination of the axis of the cylinder with respect toH ₀ - shear rate - small parameter of slender body theory,=1/ln (2L/D) - _s constant viscosity of the suspending fluid - µ ₀ the magnetic permeability of free space,µ ₀=4 · 10^–7 H/m - _MV the magnetoviscous time constant, a characteristic time for a process involving a competition of viscous and magnetic stresses - ₁ the first normal-stress coefficient - ; _z angular velocity of a rotating body; angular velocity of a cylinder about thez-axis, _z =– d/dt     

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     

Stress optical measurement of the third normal stress difference in polymer melts under oscillatory shear

Results are reported for the dynamic moduli,G andG, measured mechanically, and the dynamic third normal stress difference, measured optically, of a series bidisperse linear polymer melts under oscillatory shear. Nearly monodisperse hydrogenated polyisoprenes of molecular weights 53000 and 370000 were used to prepare blends with a volume fraction of long polymer, _L, of 0.10, 0.20, 0.30, 0.50, and 0.75. The results demonstrate the applicability of birefringence measurements to solve the longstanding problem of measuring the third normal stress difference in oscillatory flow. The relationship between the third normal stress difference and the shear stress observed for these entangled polymer melts is in agreement with a widely predicted constitutive relationship: the relationship between the first normal stress difference and the shear stress is that of a simple fluid, and the second normal stress difference is proportional to the first. These results demonstrate the potential use of 1,3-birefringence to measure the third normal stress difference in oscillatory flow. Further, the general constitutive equation supported by the present results may be used to determine the dynamic moduli from the measured third normal stress difference in small amplitude oscillatory shear. Directions for future research, including the use of birefringence measurements to determineN ₂/N ₁ in oscillatory shear, are described.     

Finite shear strain behavior of a crosslinking polydimethylsiloxane near its gel point

A power law distribution of relaxation times, large normal stress differences, and physical rupture of molecular network strands dominate the shear behavior of polymers at the gel point (critical gels). This is shown in a series of well-defined experiments with increasing magnitude of shear on a model-network polymer system consisting of a linear, telechelic, vinyl-terminated poly-dimethylsiloxane (PDMS) and a four-functional siloxane crosslinker. Stable samples were prepared by stopping the crosslinking reaction at different extents of reaction in the vicinity of the gel point (GP). The Gel Equation has been shown to be valid up to strains of about 2 when using a finite strain tensor. Larger strains have been found to disrupt the network structure of the crosslinking polymer, and introduce a mechanical delay to the gel point. A sample that was crosslinked beyond the gel point (p>p _c ) can be reduced from the solid state to a critical gel, or even to a viscoelastic liquid, depending on the magnitude of shear strain. As a consequence, the relaxation exponent of a critical gel created under the influence of shear is less than that of a quiescently crosslinked critical gel.     

A method for correction of the wall-slip effect in a Couette rheometer

A simple method for correction of the wall-slip effect in a Couette rheometer was derived. The method requires only two series of measurements (two flow curves) performed in two measuring sets of any dimensions, and therefore it may be applied for the results obtained in each rheometer with a standard cup and bob set. The method was checked for experimental data and also verified theoretically for a hypothetical liquid. H height of cylinder - M torque - r distance from axis - R _i ,R ₀ radius of inner and outer cylinder - R _m average radius defined by Eq. (7) - u slip velocity - shear rate - shear rate for no-slip conditions - Newtonian viscosity - angular speed - angular speed of the rotating cylinder     

Fragile networks and rheology of concentrated suspensions

Suspensions consisting of particles of colloidal dimensions have been reported to form connected structures. When attractive forces act between particles in suspension they may flocculate and, depending on particle concentration, shear history and other parameters, flocs may build-up in a three-dimensional network which spans the suspension sample. In this paper a floc network model is introduced to interpret the elastic behavior of flocculated suspensions at small deformations. Elastic percolation concepts are used to explain the variation of the elastic modulus with concentration. Data taken from the suspension rheology literature, and new results with suspensions of magnetic -Fe₂O₃ and non-magnetic -Fe₂O₃ particles in mineral oil are interpreted with the model proposed.Non-zero elastic modulus appeared at threshold particle concentrations of about 0.7 vol.% and 0.4 vol.% of the magnetic and non-magnetic suspensions, respectively. The difference is attributed to the denser flocs formed by magnetic suspensions. The volume fraction of particles in the flocs was estimated from the threshold particle concentration by transforming this concentration into a critical volume concentration of flocs, and identifying this critical concentration with the theoretical percolation threshold of three-dimensional networks of different coordination numbers. The results obtained indicate that the flocs are low-density structures, in agreement with cryo-scanning electron micrographs. Above the critical concentration the dynamic elastic modulus G was found to follow a scaling law of the type G ( _f - _f ^c ) ^f , where _f is the volume fraction of flocs in suspension, and _f ^c is its threshold value. For magnetic suspensions the exponent f was found to rise from a low value of about 1.0 to a value of 2.26 as particle concentration was increased. For the non-magnetic a similar change in f was observed; f changed from 0.95 to 3.6. Two other flocculated suspension systems taken from the literature showed a similar change in exponent. This suggests the possibility of a change in the mechanism of stress transport in the suspension as concentration increases, i.e., from a floc-floc bond-bending force mechanism to a rigidity percolation mechanism.     

Pure liquids described as concentrated cluster dispersions

The Fulcher-Tammann-Hesse-Vogel equation, ln = A + B/(T – T ₀ ), is shown to be equivalent to the general viscosity-composition relationship, ln _r =k f /(1 – f ), for binary mixtures. The Cailletet-Mathias law of the Rectilinear Diameter is rearranged to represent a density mixture formula for two components. Temperature-independent viscosities and densities can then be calculated for dense, solid cluster fractions, dispersed in a low-density, low-viscosity non-clustered continuous phase. The cluster fraction decreases with temperature. The value ofT ₀ is shown to be related to the liquid- or solid-like behavior of the clusters. For liquids with a vapor pressure < 1 mm Hg at the melting point, the calculated cluster volume fraction suggests close packing of clusters, ranging in shape from monodisperse spheres to polydisperse non-spherical particles. Examples are given for molecular liquids, molten metals, and molten salts. The size of the clusters is estimated from the heat of evaporation.     

Evaluating Herschel-Bulkley fluids with the back extrusion (annular pumping) technique

A mathematical model was developed to describe the behavior of Herschel-Bulkley fluids in a back extrusion (annular pumping) device. A technique was also developed to determine the rheological properties (yield stress, flow behavior index, and consistency coefficient) of these fluids. Mathematical terms were expressed in four dimensionless terms, and graphical aids and tables were prepared to facilitate the handling of the expressions.Nomenclature a radius of the plunger, m - dv/dr shear rate, s^–1 - F force applied to the plunger, N - F _b buoyancy force, N - F _cb force corrected for buoyancy, N - F _T recorded force just before the plunger is stopped, N - F _Te recorded force after the plunger is stopped, N - g acceleration due to gravity, m/s² - H(t) momentary height between plunger and container bottom, m - K a/R, dimensionless - L length of annular region, m - L(t) depth of plunger penetration, m - n flow behavior index, dimensionless - p static pressure, Pa - P _L pressure in excess of hydrostatic pressure at the plunger base, Pa - p ₀ pressure at entrance to annulus, Pa - P pressure drop per unit of length, Pa/m - Q total volumetric flow rate through the annulus, m³/s - r radial coordinate, measured from common axis of cylinder forming annulus, m - R radius of outer cylinder of annulus, m - s reciprocal of n, dimensionless - t time, s - T dimensionless shear stress, defined in Eq. (3) - T ₀ dimensionless yield stress, defined in Eq. (4) - T _w dimensionless shear stress at the plunger wall - _p velocity of plunger, m/s - velocity, m/s - mass density of fluid, kg/m³ - Newtonian viscosity, Pa s - P p ₀ –p _L , Pa - consistency coefficient, Pa sⁿ - value of where shear stress is zero - _–, ₊ limits of the plug flow region (Fig. 1) - r/R - shear stress, Pa - _y yield stress, Pa - _w shear stress at the plunger wall, Pa - dimensionless flow rate defined in Eq. (24) - dimensionless velocity defined by Eq. (5) - _–, ₊ dimensionless velocity outside the plug flow region - _max dimensionless maximum velocity in the plug flow region - _p dimensionless velocity at the plunger wall     

Rheological properties of skim milk gels at various temperatures; interrelation between the dynamic moduli and the relaxation modulus

The rheological properties of rennet-induced skim milk gels were determined by two methods, i.e., via stress relaxation and dynamic tests. The stress relaxation modulusG _c (t) was calculated from the dynamic moduliG andG by using a simple approximation formula and by means of a more complex procedure, via calculation of the relaxation spectrum. Either calculation method gave the same results forG _c (t). The magnitude of the relaxation modulus obtained from the stress relaxation experiments was 10% to 20% lower than that calculated from the dynamic tests.Rennet-induced skim milk gels did not show an equilibrium modulus. An increase in temperature in the range from 20° to 35 °C resulted in lower moduli at a given time scale and faster relaxation. Dynamic measurements were also performed on acid-induced skim milk gels at various temperatures andG _c (t) was calculated. The moduli of the acid-induced gels were higher than those of the rennet-induced gels and a kind of permanent network seemed to exist, also at higher temperatures. G storage shear modulus,N·m^–2; - G loss shear modulus,N·m^–2; - G _c calculated storage shear modulus,N·m^–2; - G _c calculated loss shear modulus,N·m^–2; - G _e equilibrium shear modulus,N·m^–2; - G _ec calculated equilibrium shear modulus,N·m^–2; - G(t) relaxation shear modulus,N·m^–2; - G _c (t) calculated relaxation shear modulus,N·m^–2; - G ^*(t) pseudo relaxation shear modulus,N·m^–2; - H relaxation spectrum,N·m^–2; - t time,s; - relaxation time,s; - angular frequency, rad·s^–1. Partly presented at the Conference on Rheology of Food, Pharmaceutical and Biological Materials, Warwick, UK, September 13–15, 1989 [33].     

Einfluß nichtnewtonscher Stoffeigenschaften auf die Taylor-Wirbelströmung

Zusammenfassung Nach einer kurzen Beschreibung über die Anwendung der Taylor-Wirbelströmung bei der Filtration von nichtnewtonschen Flüssigkeiten werden polymere Modellflüssigkeiten charakterisiert, die als Partikel- und Netzwerklösungen in einer Wirbelströmungsapparatur eingesetzt wurden. Die Fließkurven der Polymerlösungen zeigen aufgrund der extrem hochmolekularen Polymerproben neben strukturviskosen Erscheinungen auch dilatantes Fließverhalten mit besonderer Wirkung auf die Taylor-Wirbelströmung.Die Versuchsflüssigkeiten offenbaren vier verschiedene Typen von Strömungsinstabilitäten: spiralförmige, schwingende und stationäre Instabilitäten sowie gedämpfte Turbulenz. Während die stark strukturviskosen Netzwerklösungen alle genannten Formen aufweisen, fehlt bei den Partikellösungen die spiralförmige Instabilität.Unter Zuhilfenahme des Hantelmolekülmodells zur Beschreibung viskoelastischer Strömungsphänomene gelingt es, durch Einführung einer kritischen Deborahzahl den Einsatzpunkt nichtnewtonscher Taylorströmungseffekte vorauszusagen. Die gefundene Beziehung steht in engem Zusammenhang mit dehnviskositätserhöhenden Polymerwirkungen in Porenströmungen und mit reibungsmindernden Polymereffekten in turbulenten Rohrströmungen.

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Experimental investigations dealing with dilute polymer solutions are described after a short review of the application of Taylor-vortex flow in the filtration processes of non-Newtonian fluids. The test fluids represent both viscoelastic solutions with isolated macromolecules and network solutions with power law fluid behaviour.These solutions show four different types of flow instabilities: spiral-shaped, oscillatory, steady and turbulent phenomena. The Taylor-numbers which depend upon the polymer concentration are determined for the onset of these instability types. For isolated macromolecule solutions, the Deborah-number concept for dilute dumbbell solutions can be applied to describe the first appearance of irregular nonstationary Taylor vortices.The present data are compared to literature values. This fluid behaviour is related to extensional viscosity increases which are also observed in porous media flow and turbulent pipe flow of dilute macromolecular solutions.

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Nomenklatur A, B Konstanten aus Randbedingungen der Ringspaltströmung - C Polymerkonzentration - D Schergeschwindigkeit - De Deborahzahl - l Länge einer Wirbelzelle - L Zylinderlänge - m Gesamtanzahl der Wirbelpaare zur Bestimmung der Wellenzahl - M Molmasse der Polymere - M _w Gewichtsmittel der Molmasse - M _v Viskositätsmittel der Molmasse - n Drehzahl des Rotors - universelle Gaskonstante - r Radius - R _a Radius des Außenzylinders - R _i Radius des Innenzylinders - s Spaltweite - s ^* dimensionslose Spaltweite - T Temperatur - Ta Taylorzahl - v Umfangsgeschwindigkeit - z Anzahl der Wirbelpaare zur Bestimmung der Wellenzahl Griechische Symbole Deformationskoeffizient von Makromolekülen - Wellenzahl - Dehnrate - dynamische Viskosität - [] Grenzviskositätszahl - Relaxationszeit - Dichte - Schubspannung - Winkelgeschwindigkeit - _a Winkelgeschwindigkeit des Außenzylinders - _i Winkelgeschwindigkeit des Innenzylinders Indices c kritisch (erstmaliges Auftreten von Taylorwirbel) - N newtonsch - o onset, Schwellwert - P polymer - r radial - Sch schwingend - Spir spiralförmig - Stat stationär - Turb turbulent - T Taylorströmung - Umfangsrichtung Herrn Prof. Dr. Heinz Harnisch zum 60. Geburtstag gewidmet     

Experimental investigations of the stability limit of the helical flow of pseudoplastic liquids

The stability of the laminar helical flow of pseudoplastic liquids has been investigated with an indirect method consisting in the measurement of the rate of mass transfer at the surface of the inner rotating cylinder. The experiments have been carried out for different values of the geometric parameter = R ₁/R ₂ (the radius ratio) in the range of small values of the Reynolds number,Re < 200. Water solutions of CMC and MC have been used as pseudoplastic liquids obeying the power law model. The results have been correlated with the Taylor and Reynolds numbers defined with the aid of the mean viscosity value. The stability limit of the Couette flow is described by a functional dependence of the modified critical Taylor number (including geometric factor) on the flow indexn. This dependence, general for pseudoplastic liquids obeying the power law model, is close to the previous theoretical predictions and displays destabilizing influence of pseudoplasticity on the rotational motion. Beyond the initial range of the Reynolds numbers values (Re>20), the stability of the helical flow is not affected considerably by the pseudoplastic properties of liquids. In the range of the monotonic stabilization of the helical flow the stability limit is described by a general dependence of the modified Taylor number on the Reynolds number. The dependence is general for pseudoplastic as well as Newtonian liquids.Nomenclature C _i concentration of reaction ions, kmol/m³ - d = R ₂ –R ₁ gap width, m - F _M () Meksyn's geometric factor (Eq. (1)) - F ₀ Faraday constant, C/kmol - i _l density of limit current, A/m³ - k _c mass transfer coefficient, m/s - n flow index - R ₁,R ₂ inner, outer radius of the gap, m - Re = V _m ·2d·/µ _m Reynolds number - Ta _c = _c ·d^3/2·R ₁ ^1/2 ·/µ _m Taylor number - Z _i number of electrons involved in electrochemical reaction - = R ₁/R ₂ radius ratio - µ apparent viscosity (local), Ns/m² - µ _m mean apparent viscosity value (Eq. (3)), Ns/m² - µ _i apparent viscosity value at a surface of the inner cylinder, Ns/m² - density, kg/m³ - _c angular velocity of the inner cylinder (critical value), 1/s     

Thermal expansivity of particulate composites: Interlayer versus molecular model

We continue the comparison of the results of an interlayer model, based on the theory of elastic continua, and a molecular model, derived from a theory of mixtures, previously presented in terms of bulk moduli K. We now derive expressions for the dependence of the thermal expansivity _c on the volume fraction _f of the filler, at low and elevated values of _f . Correspondencies between the characteristic parameters, viz. adhesion and repulsion ratios on the one hand, and interlayer content and thermal properties of matrix, filler, and layer, on the other, are examined. Since in the molecular theory both andK are derived from an equation of state, the identical set of parameters determines both functions and suggests correlations between them.     

Influence of the formation of associations of macromolecules on the rheo-optical properties of their dilute solutions. I. Theory

Assuming the formation of doublets in the flow according to a mass action law, the shear rate and the concentration dependence of the extinction angle, of the birefringence, and of the average coil expansion are calculated for dilute solutions of flexible macromolecules. It is shown that this reversible association process has a strong influence on the measurable parameters in a flow birefringence experiment. c concentration (g/cm³) - h ² mean square end-to-end distance at shear rate - h ₀ ² mean-square end-to-end distance at zero-shear rate - n refractive index of the solution (not very different from the solvent for a very dilute solution) - E mean coil expansion - K ₀,K constant of the mass action law - M molecular weight - R _G gas constant - T absolute temperature - ₁ – ₂ optical anisotropy of the segment - ₀ Deborah number: - Deborah number: - shear rate - ₀, reduced concentration - _s viscosity of the solvent - [] ₀ intrinsic viscosity at zero-shear rate - [] intrinsic viscosity at shear rate - extinction angle - N _a Avodagro's number - _n magnitude of the birefringence     

Response of an elastic Bingham fluid to oscillatory shear

The response of an elastic Bingham fluid to oscillatory strain has been modeled and compared with experiments on an oil-in-water emulsion. The newly developed model includes elastic solid deformation below the yield stress (or strain), and Newtonian flow above the yield stress. In sinusoidal oscillatory deformations at low strain amplitudes the stress response is sinusoidal and in phase with the strain. At large strain amplitudes, above the yield stress, the stress response is non-linear and is out of phase with strain because of the storage and release of elastic recoverable strain. In oscillatory deformation between parallel disks the non-uniform strain in the radial direction causes the location of the yield surface to move in-and-out during each oscillation. The radial location of the yield surface is calculated and the resulting torque on the stationary disk is determined. Torque waveforms are calculated for various strains and frequencies and compared to experiments on a model oil-in-water emulsion. Model parameters are evaluated independently: the elastic modulus of the emulsion is determined from data at low strains, the yield strain is determined from the phase shift between torque and strain, and the Bingham viscosity is determined from the frequency dependence of the torque at high strains. Using these parameters the torque waveforms are predicted quantitatively for all strains and frequencies. In accord with the model predictions the phase shift is found to depend on strain but to be independent of frequency.Notation A plate strain amplitude (parallel plates) - A _R plate strain amplitude at disk edge (parallel disks) - G elastic modulus - m torque (parallel disks) - M normalized torque (parallel disks) = 2m/R ³₀ - N ratio of viscous to elastic stresses (parallel plates) =µ A/ ₀ ratio of viscous to elastic stresses (parallel disks) =µ A _R/₀ - r normalized radial position (parallel disks) =r/R - r radial position (parallel disks) - R disk radius (parallel disks) - t normalized time = t — /2 - t time - _E elastic strain - _P plate strain (displacement of top plate or disk divided by distance between plates or disks) - _PR plate strain at disk edge (parallel disks) - ₀ yield strain - _E normalized elastic strain = _E/₀ - _P normalized plate strain = _P/₀ - _PR normalized plate strain at disk edge (parallel disks) = _PR/₀ - ₀ normalized plate strain amplitude (parallel plates) =A/ ₀ — normalized plate strain amplitude at disk edge (parallel disks) =A _R/₀ - phase shift between _P andT (parallel plates) — phase shift between _PR andM (parallel disks) - µ Bingham viscosity - stress - ₀ yield stress - T normalized stress =/ ₀ - frequency