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].     

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      

Rheological characteristics of glass-fibre-filled polypropylene melts

The rheological properties of glass fibre-filled polypropylene melts have been investigated. A high pressure capillary rheometer has been used for the experimental study. The effect of shear rate, temperature, and fibre concentration on the melt viscosity and viscoelastic properties have been studied. An equation has been proposed to correlate the melt viscosity with shear rate, temperature and fibre content. A master curve relation on this basis has been brought out using the shift factora _T . a _T shift factor (=/ _r ) - A _i coefficients of the polynomical of eq. (1) (i = 0, 1, 2, ,n) - B constant in the AFE equation (eq. (2)) (Pa s) - B constant in eq. (3) - D extrudate diameter - d capillary diameter - activation energy at constant shear rate (kcal/mole) - E activation energy at constant shear stress (kcal/mole) - T melt temperature (K) - X fraction glass fibre by weight - shear rate (s^–1) - shear viscosity (Pa s) - normal stress coefficient (Pa s²) - ₁ – ₂ first normal-stress difference (Pa) - shear stress (Pa) - r at reference temperature     

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     

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     

Measurement of the first normal-stress difference at high shear rates for a polyisobutylene/decalin solution “D2”

Reasonable agreement is found between values of the first normal-stress differenceN ₁ for samples of D2, a polyisobutylene/decalin solution, measured in steady shear flow using three different instruments: a Weissenberg Rheogoniometer (a cone-plate rotational rheometer), a Torsional Balance (plate-plate rotational) Rheometer, and a Stressmeter (a transverse-slot slit-die rheometer). Viscosity values are also in reasonable agreement. Ranges of variables common to at least two rheometers include values of shear stress up to 3,700 Pa and shear rate up to 20,700 s^–1 near 25 °C. The agreement supports the approximate validity of the semi-empirical HPBL equation used to calculateN ₁ from Stressmeter data over a range of shear rates up to 20,700 s^–1 near 25 °C. Time-temperature superposition behavior exhibited by Stressmeter data at temperatures in the range 21 °C to 111 °C suggest that the range of validity of the Stressmeter method for determiningN ₁ approximately may extend up to shear rates of 290,000 s^–1 at 111 °C.     

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     

Slit die viscometry at shear rates up to 5 × 106s−1: An analytical correction for small viscous heating errors

If the viscosity can be expressed in the form = (T)f(), the walls are at a constant temperatureT ₀, and the extra stress, velocity and temperature fields are fully developed, then the wall shear rate can be calculated by applying the Weissenberg-Rabinowitsch operator toF _c Q instead of to the flow rateQ, whereF _c is a correction factor which differs from 1 when the temperature field is non-uniform; the isothermal equation relating the wall shear stress and pressure gradient is still valid. For the case in whcih = ₀|| ⁿ /(1 +(T–T ₀)), wheren, ₀, and are independent of shear stress and temperatureT, an exact analytical expression forF _c in terms of the Nahme-Griffith numberNa andn is obtained. Use of this expression gives agreement with data obtained for degassed decalin ( = 2.5 mPa s) from a new miniature slit-die viscometer at shear rates up to 5 × 10⁶s^–1; here, the correction is only 7%,Na is 1.3, andGz, the Graetz number at the die exit, is 119. For a Cannon standard liquidS6 ( = 9 mPa s), agreement extends up to 5 × 10⁵s^–1; at 2×10⁶s^–1 (whereNa = 7.2 andGz = 231), the corrections are 11% (measured) and 36% (calculated).Notation x, y Cartesian coordinates - v _x ,v velocity inx-direction, dimensionless velocity - p _xx ,p _yy normal stress onx- andy-planes - N ₁ first normal stress difference - shear stress ony-planes acting inx-direction - _w value of shear stress at the wall - shear rate, shear rate at the wall - Q, Q flow rate (Eqs. (2.13), (2.15)) - T, T ₀ temperature, temperature at the wall - ø, dimensionless temperature (Eqs. (2.24), (2.25)) - h, w half of die height, width of die - R diameter of a tube - , ₀ viscosity, viscosity atT = T ₀ - viscosity-temperature coefficient - k thermal conductivity - c _p specific heat at constant pressure - n, m dimensionless parameters characterizing shear stress dependence of viscosity - Na Nahme Griffith number (Eq. (2.21)) - Gz Graetz number (Eq. (5.1)) - F _c viscous heating correction factor (Eq. (2.18)) - ( ) a function characterizing temperature dependence of viscosity (Eq. (2.8)) - J _k ( ) Bessel function of the first kind This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Rheological models for gypsum plaster pastes

Shear stress and shear rate data obtained for gypsum plaster pastes were correlated by means of different rheological models. The pastes were prepared from a commercial calcium sulfate hemihydrate at various water/plaster ratios ranging from 100/150 to 100/190. The tests were performed at 25°C using a rotating coaxial cylinder viscosimeter. The measurements were accomplished by applying a step-wise decreasing shear rate sequence. Discrimination among the models was made: (1) on the basis of the fitting goodness; (2) by checking the physical meaning of the calculated parameters; (3) on the basis of the stability of the parameters and of their prediction capacity beyond the limits of the experimental data. In the light of above, the Casson model seemed to be most effective for application to gypsum plaster pastes. K Consistency - n Power-law index - N Number of experimental data - P Number of parameters - Shear rate (s^–1) - ₀ Viscosity (Pa · s) - _d Dispersing medium viscosity (Pa · s) - _p Plastic viscosity (Pa · s) - Viscosity at zero shear rate (Pa · s) - Viscosity at infinite shear rate (Pa · s) - [] Intrinsic viscosity - ² Variance - Shear stress (Pa) - ₀ Yield stress (Pa) - Solid volume fraction - _m Maximum solid volume fraction     

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     

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     

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     

Representation of the rheological properties of polymer melts in terms of complex fluidity

In dynamic rheological experiments melt behavior is usually expressed in terms of complex viscosity ^* () or complex modulusG ^* (). In contrast, we attempted to use the complex fluidity ^* () = 1/µ ^* () to represent this behavior. The main interest is to simplify the complex-plane diagram and to simplify the determination of fundamental parameters such as the Newtonian viscosity or the parameter of relaxation-time distribution when a Cole-Cole type distribution can be applied. ^* () complex shear viscosity - () real part of the complex viscosity - () imaginary part of the complex viscosity - G ^* () complex shear modulus - G() storage modulus in shear - G() loss modulus in shear - J ^* () complex shear compliance - J() storage compliance in shear - J() loss compliance in shear - shear strain - rate of strain - angular frequency (rad/s) - shear stress - loss angle - ^* () complex shear fluidity - () real part of the complex fluidity - () imaginary part of the complex fluidity - ₀ zero-viscosity - ₀ average relaxation time - h parameter of relaxation-time distribution     

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     

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     

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     

Transient stress responses predicted by the internal viscosity model in elongational flow

Predictions are made for the elongational-flow transient rheological properties of the dilute-solution internal viscosity (IV) model developed earlier by Bazua and Williams. Specifically, the elongational viscosity growth function _e ⁺ (t) is presented for abrupt changes in the elongational strain rate . For calculating _e ⁺, a novel treatment of the initial rotation of chain submolecules is required; such rotation occurs in response to the macroscopic step change of at t = 0. Representative are results presented for N = 100 (N = number of submolecules) and = 1000 f and 10000 f (where is the IV coefficient and f is the bead friction coefficient), using h ^* = 0 (as in the original Rouse model) for the hydrodynamic interaction. The major role of IV is to cause the following changes relative to the Rouse model: 1) abrupt stress jump at t = 0 for _e ⁺; 2) general time-retardance of response. There is no qualitative change from the Rouse-model prediction of unbounded il growth when exceeds a critical value ( ), and calculations of submolecule strains at various show that the unbounded- _e ^– behavior arises from unlimited submolecule strains when . However, the time-retardance could delay such growth beyond the timescale of most experiments and spinning processes, so that the instability might not be detected. Finally, _e ⁺ (t) and _e ( ) in the limit are presented for N = 1 and compared with exact predictions for the analogous rigid-rod molecule; close agreement lends support for the new physical approximation introduced for solving the transient dynamics for any N.     

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.     

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.     

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)