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     

Evaluation of the dynamic-mechanical properties of solids from a cooperative model for stress relaxation

For many solid materials the stress relaxation process obeys the universal relationF = – (d/d lnt)_max = (0.1 ± 0.01) ( ₀ — _i ), regardless of the structure of the material. Here denotes the stress,t the time, ₀ the initial stress of the experiment and _i the internal stress. A cooperative model accounting for the similarity in relaxation behaviour between different materials was developed earlier. Since this model has a spectral character, the concepts of linear viscoelasticity are used here to evaluate the corresponding prediction of the dynamic mechanical properties, i.e. the frequency dependence of the storageE () and lossE () moduli. Useful numerical approximations ofE () andE () are also evaluated. It is noted that the universal relation in stress relaxation had a counterpart in the frequency dependence ofE (). The theoretical prediction of the loss factor for high-density polyethylene is compared with experimental results. The agreement is good.     

Pulsatile blood flow through arterioles

An analytical study was made to examine the effect of vascular deformability on the pulsatile blood flow in arterioles through the use of a suitable mathematical model. The blood in arterioles is assumed to consist of two layers — both Newtonian but with differing coefficients of viscosity. The flow characteristics of blood as well as the resistance to flow have been determined using the numerical computations of the resulting expressions. The applicability of the model is illustrated using numerical results based on the existing experimental data. r, z coordinate system - u, axial/longitudinal velocity component of blood - p pressure exerted by blood - _b density of blood - µ viscosity of blood - t time - , displacement components of the vessel wall - T _t0,T ₀ known initial stresses - density of the wall material - h thickness of the vessel wall - T _t,T stress components of the vessel - K _l,K _r components of the spring coefficient - C _l,C _r components of the friction coefficient - M _a additional mass of the mechanical model - r ₁ outer radius of the vessel - thickness of the plasma layer - r ₁ inner radius of the vessel - circular frequency of the forced oscillation - k wave number - E ₀,E _t, , _t material parameters for the arterial segment - µ _p viscosity of the plasma layer - Q total flux - Q _p flux across the plasma zone - Q _h flux across the core region - Q mean flow rate - resistance to flow - P pressure difference - l length of the segment of the vessel     

On some nearly viscometric flows of viscoelastic liquids

Superposition of oscillatory shear imposed from the boundary and through pressure gradient oscillations and simple shear is investigated. The integral fluid with fading memory shows flow enhancement effects due to the nonlinear structure. Closed-form expressions for the change in the mass transport rate are given at the lowest significant order in the perturbation algorithm. The elasticity of the liquid plays as important a role in determining the enhancement as does the shear dependent viscosity. Coupling of shear thinning and elasticity may produce sharp increases in the flow rate. The interaction of oscillatory shear components may generate a steady flow, either longitudinal or orthogonal, resulting in increases in flow rates akin to resonance, and due to frequency cancellation, even in the absence of a mean gradient. An algorithm to determine the constitutive functions of the integral fluid of order three is outlined.Nomenclature A _n Rivlin-Ericksen tensor of order . - A _k Non-oscillatory component of the first order linear viscoelastic oscillatory velocity field induced by the kth wave in the pressure gradient - d Half the gap between the plates - e _x, e _z Unit vectors in the longitudinal and orthogonal directions, respectively - G(s) Relaxation modulus - G History of the deformation - Stress response functional - I() Enhancement defined as the ratio of the frequency dependent part of the discharge to the frequencyindependent part of it at the third order - I ^*() Enhancement defined as the ratio of the increase in discharge due to oscillations to the total discharge without the oscillations - k Power index in the relaxation modulus G(s) - k _i ^–1 Relaxation times in the Maxwell representation of the quadratic shear relaxation modulus (s ₁, s ₂) - m _i ^–1, n _i ^–1 Relaxation times in the Maxwell representations of the constitutive functions ₁(s ₁,s ₂,s ₃) and ₄ (s ₁, s ₂,s ₃), respectively - P Constant longitudinal pressure gradient - p Pressure field - _mx ,⁽³⁾ _nz ,⁽³⁾ Mean volume transport rates at the third order in the longitudinal and orthogonal directions, respectively - ₀,⁽³⁾, ₁,⁽³⁾ Frequency independent and dependent volume transport rates, respectively, at the third order - s = t- Difference between present and past times t and      

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     

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].     

An experimental study on effects of solid concentration and ζ-potential on pseudoplastic flow of suspensions

The pseudoplastic flow of suspensions, alumina or styrene-acrylamide copolymer particles in water or an aqueous solution of glycerin has been studied by the step-shear-rate method. The relation between the shear rate,D, and the shear stress,, in the step-shear-rate measurements, where the state of dispersion was considered to be constant, was expressed as = AD ^1/2 +CD. The effective solid volume fraction,ø _F, andA were dependent on the shear rate and expressed byø _F =aD ^b andA = D . Combining the above relations, the steady flow curve was expressed by = D ^{1/2 +} + ₀ (1 – a D ^b/0.74)^–1.85 D, where ₀ is the viscosity of the medium.With an increase in solid volume fraction and a decreases in the absolute value of the-potential, the flow behavior of the suspensions changed from Newtonian ( = = b = 0), slightly pseudoplastic ( = b = 0), pseudoplastic ( = 0) to a Bingham-like behavior.The change in viscosity of the medium had an effect on the change in the effective volume fraction.     

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     

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.     

Measurements of slip at the wall during flow of high-density polyethylene through a rectangular conduit

A hot-film probe has been used to measure slip of high-density polyethylene flowing through a conduit with a rectangular cross section. A transition from no slip to a stick-slip condition has been observed and associated with irregular extrudate shape. Appreciable extrudate roughness was initiated at the same flow rate as that at which the relationship between Nusselt number and Péclet number for heat transfer from the probe departed from the behavior expected for a no-slip condition at the conduit wall. A ₁ constant defined by eq. (A3) - C dimensionless group used in eq. (7) - C _p heat capacity - D constant in eq. (13) - f u _s/u - f _lin defined by eq. (A6) - G storage modulus - G loss modulus - k thermal conductivity - L length of hot film in thex-direction - L _eff effective length of large probe found from eq. (A3) - Nu _L Nusselt number, defined for a lengthL by eq. (2) - (Nu _L)₀ value ofNu _L atPe = 0 (eq. (A 1)) - Pe Péclet number,uL/ - Pe ₀ Péclet number in slip flow, eq. (6) - Pe ₁ Péclet number in shear flow, eq. (4) - q _L average heat flux over hot film of lengthL - R _i resistances defined by figure 8 - R _AB correlation coefficient defined by eq. (14) for signalsA andB - T temperature - T _s temperature of probe surface - T ambient temperature - T T _s –T - u average velocity - u _s slip velocity - V _b voltage indicated in figure 8 - W probe dimension (figure 6) - x distance in flow direction (figure 1) - y distance perpendicular to flow direction (figure 1) - thermal diffusivity,k/C _p - wall shear rate - _5% thickness of lubricating layer during probe calibration for introduction of an error no greater than 5%; see Appendix I - ^* complex viscosity - density - time - _c critical shear stress, eq. (13) - _w wall shear stress - frequency characterizing extrudate distortion (figures 12 and 13), or frequency of oscillation during rheometric characterization (figures 18–20) - * quantity obtained from normalized Nusselt number, eq. (A1), or complex viscosity ^* - A actual (small) probe (see Appendix I) - M model (large) probe (see Appendix I)     

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     

Viscoelastic swirling flow with free surface in cylindrical chambers

The flow of a viscoelastic liquid driven by the steadily rotating bottom cover of a cylindrical cup is investigated. The flow field and the shape of the free surface are determined at the lowest significant orders of the regular domain perturbation in terms of the angular velocity of the bottom cap. The meridional field superposed on a primary azimuthal field shows a structure of multiple cells. The velocity field and the shape of the free surface are strongly effected by the cylinder aspect ratio and the elasticity of the liquid. The use of this flow configuration as a free surface rheometer to determine the first two Rivlin-Ericksen constants is shown to be promising.Nomenclature R, ,Z Coordinates in the physical domain D - , , Coordinates in the rest stateD ₀ - r, ,z Dimensionless coordinates in the rest stateD ₀ - Angular velocity - Zero shear viscosity - Surface tension coefficient - Density - Dimensionless surface tension parameter - ₁, ₂ The first two Rivlin-Ericksen constants - Stream function - Dimensionless second order meridional stream function - ^* Dimensionless second normal stress function - 2 Dimensionless sum of the first and second normal stress functions - N ₁,N ₂ The first and second normal stress functions - n Unit normal vector - D Stretching tensor - A _n nth order Rivlin-Ericksen tensor - S Extra-stress - u Velocity field - U Dimensionless second order meridional velocity field - V Dimensionless first order azimuthal velocity field - p Pressure - Modified pressure field - P Dimensionless second order pressure field - J Mean curvature - a Cylinder radius - d Liquid depth at rest - D Dimensionless liquid depth at rest - h Free surface height - H Dimensionless free surface height at the second order     

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     

Neck propagation as a shock wave

Neck propagation in the stretching of elastic solid filaments having a yield point was analyzed using the space one-dimensional thin filament governing equations developed previously by the authors and other researchers. Constitutive model for the filament was assumed to be expressible as engineering tensile stress(X) (tensile force) given as a function of elongational strain with the(X) curve having a yield point maxima followed by a minima and a breaking point greater than the yield point maxima. Also incorporated into the model is the hysteresis of irreversible plastic deformation. When inertia is taken into consideration, the thin filament equations were found to reduce to the nonlinear wave equation ² (X)/ ² =C ₁ ² X/ ² where is Lagrangean space coordinate, is time, andC ₁ is inertia coefficient. The above nonlinear wave equation yields a solutionX(, ) having a stepwise discontinuity inX which propagates along the axis. The zero speed limit of the step wave solution was found to describe the above neck propagation occurring in solid filaments. Furthermore, it was recognized that the nonlinear wave equation was known for many years to also govern the plastic shock wave which propagates axially within a metal rod subjected to a very strong impact on its end. The one-dimensional atmospheric shock wave also was known to be governed by the nonlinear wave equation upon making certain simplifying assumptions. The above and other evidences lead to the conclusion that neck propagation occurring in the extension of solid filament obeying the above(X) function can be formally described as a shock wave.     

Temperature and concentration dependent viscosity and gelation temperature of ABA triblock copolymer solutions

In solutions of ABA-triblock copolymers in a poor solvent for A thermoreversible gelation can occur. A three-dimensional dynamic network may form and, given the polymer and the solvent, its structure will depend on temperature and polymer mass fraction. The zero-shear rate viscosity of solutions of the triblock-copolymer polystyrene-polyisoprene-polystyrene in n-tetradecane was measured as a function of temperature and polymer mass fraction, and analyzed; the polystyrene blocks contained about 100 monomers, the polyisoprene blocks about 2000 monomers. Empirically, in the viscosity at constant mass fraction plotted versus inverse temperature, two contributions could be discerned; one contribution dominating at high and the other one dominating at low temperatures. In a comparison with theory, the contribution dominating at low temperatures was identified with the Lodge transient network viscosity; some questions remain to be answered, however. An earlier proposal for defining the gelation temperature T _gel is specified for the systems considered, and leads to a gelation curve; T _gel as a function of polymer mass fraction.Mathematical symbols {} functional dependence; e.g., f{x} means f is a function of x - p _log logarithm to the base number p; e.g., ¹⁰log is the common logarithm - exp exponential function with base number e - sin trigonometric sine function - lim limit operation - – in integral sign: Cauchy Principal Value of integral, e.g., - derivative to x - partial derivative to x Latin symbols dimensionless constant - b constant with dimension of absolute temperature - constant with dimension of absolute temperature - B dimensionless constant - c mass fraction - dimensionless constant - constant with dimension of absolute temperature - d ^* dimensionless constant - D{0} constant with dimension of absolute temperature - e base number of natural (or Naperian) logarithm - g distribution function of inverse relaxation times - G relaxation strength relaxation function - h distribution function of relaxation times reaction constant enthalpy of a molecule - H Heaviside unit step function - i complex number defined by i ² = –1 - j{0} constant with dimension of viscosity - j index number - k Boltzmann's constant - k _H Huggins' coefficient - m mass of a molecule - n number - N number - p index number - s entropy of a molecule - t time - T absolute temperature Greek symbols as index: type of polymer molecule - as index: type of polymer molecule - shear as index: type of polymer molecule - shear rate - small variation; e.g. T is a small variation in T relative deviation Dirac delta distribution as index: type of polymer molecule - difference; e.g. is a difference in chemical potential - constant with dimension of absolute temperature - (complex) viscosity - constant with dimension of viscosity - [] intrinsic viscosity number - inverse of relaxation time - chemical potential - number pi; circle circumference divided by its diameter - mass per unit volume - relaxation time shear stress - angular frequency     

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     

Zum Mischen rheologisch inhomogener Stoffsysteme auf Einschneckenmaschinen

Zusammenfassung Das Mischen von Stoffen mit unterschiedlichen rheologischen Eigenschaften in Schneckenmaschinen ist in der Kunststoffauf- und -verarbeitung eine Standardaufgabe. Trotzdem gibt es hierfür kein zufriedenstellendes mathematisch-physikalisches Modell. Daher werden zunächst einfache Mischmodelle diskutiert. Auf der Basis dieser Modelle wird dann unter Berücksichtigung der Besonderheiten des Plastifizierextruderprozesses eine Mischgütebeziehung mathematisch formuliert. Die experimentelle Überprüfung erfolgt mit Hilfe der Grauwertanalyse extrudierter Zweistoffsysteme, bei denen ein Stoff mit Ruß eingefärbt war. Da der Mischprozeß hochgradig stochastisch ist, streuen die Meßergebnisse. Unter Berücksichtigung dieses Tatbestandes ist der theoretische Ansatz zufriedenstellend.

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Mixing of polymer resins with different rheological properties is a usual demand in plastics processing using screw extruders. A mathematical model describing this processing problem sufficiently is not known, however. Therefore, simple mixing models will be discussed. Based on these, a concept for the calculation of mixing homogeneity will be presented, including the particular requirement of the plasticating screw process. An experimental investigation utilizes the grey-value analysis of extruded two-component materials, which in one phase is carbon-black filled. Considering the fact that the mixing process is highly random, the theoretical model leads to a good level of aggreement with the scattering measurement data.

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b Schneckenkanalbreite - B Bandbreite der Grauwerte - c Konstante - mittlere Konzentration, bezogen auf die Grauwertbandbreite - h Höhe, Gangtiefe, Schneckenkanalhöhe - h ₀ Gangtiefe der Einzugszone - h ₁ Gangtiefe der Ausstoßzone - L Länge - gemittelte Schmelzebettlänge - n Exponent des Potenzfließgesetzes - s Standardabweichung der Grauwerte bezogen auf die Grauwertbandbreite - S Standardabweichung der Grauwerte - t Verweilzeit - t ₁ kürzeste Verweilzeit - mittlere Verweilzeit - ₀ Umfangsgeschwindigkeit - mittlere Geschwindigkeit - V Volumenstrom - w Dicke eines Kontrollelements - w Ausstreichdicke eines Kontrollelements - x Koordinate - Mittelwert der Grauwerte - y Koordinate - Scherdeformationswinkel - Scherdeformation - mittlere Scherdeformation - Schergeschwindigkeit - Viskosität - ₁ dimensionslose kürzeste Verweilzeit - dimensionsloser Volumenstrom - _LSM laminarer Schermischgrad - _{LSM, the} theoretischer laminarer Schermischgrad - _{LSM, exp} experimenteller laminarer Schermischgrad - ² Varianz der Verweilzeit im Schmelzebett - Schubspannung - Gangsteigungswinkel der Schnecke - ø Volumenanteil - dimensionslose Kennzahl     

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     

On the relationship between swelling of myofibrils and their suspension rheology

The swelling of myofibrils extracted from white bovine muscle was followed by measuring their suspension rheology. Swelling of the myofibril with increasing pH and ionic strength was accompanied by an increase in both the steady shear viscosity of the suspension and the dynamic viscoelastic properties. Swelling was continuously monitored by measuringG while the ionic strength of the suspension was being changed by dialysis. The relationship between the degree of swelling and the rheological parameters is complicated because myofibrils are rodshaped and swell radially and therefore swelling results in a change in shape. To allow for this an attempt was made to generalize the data by plotting viscosity andG againstcS/ø _m , wherec is the protein concentration in the suspension,S is the swollen volume of the myofibrils per weight of protein, and ø _m is the maximum packing fraction.The best fit to the data was represented by the equations _sp = 1.05 (cS/ _m – 0.84)^1.23 Pa · sG = 8.78 (cS/ _m – 0.67)^2.22 N m^–2. The scatter was greatest forG, possibly because at low degrees of shear the myofibrils were associated and this was confirmed by optical microscopy. Pronounced non-Newtonian behavior was observed and it was suggested that this was due to the disruption of aggregate structures, although at low concentration, orientation of the rods in the shear field may also be important.     

A model for the effect of physical ageing on the stress relaxation behavior of high density polyethylene

The stress relaxation behavior of high density polyethylene (HDPE) can be affected by ageing processes; e.g., with increasing storage time at a low temperature following a quench from a high temperature (close to the melting point) the relaxation curves change shape. More specifically, the stress level approached after very long loading times in a stress relaxation experiment increases with the ageing time. Here this stress level is denoted the internal stress _i. Struik has pointed out that physical ageing may also occur in semicrystalline polymers like HDPE. The physical ageing should then be associated with that part of the amorphous phase which is closest to the surfaces of the crystallites. This part of the amorphous phase of HDPE can be assumed to have a restricted mobility at room temperature and may have a partially glassy character. In this paper a model for explaining the increase in _i for HDPE with increasing ageing time is proposed and discussed. It is based on the separation of the amorphous phase into two parts as suggested by Struik. The glassy part of the amorphous phase ages in a way similar to that of an entirely amorphous polymer quenched to a temperature below its glass transition, while the more rubbery phase is assumed not to undergo any physical ageing.