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     

Oscillatory measurements of silicone oils —Loss and storage modulus master curves

The work describes a way to obtain loss modulus and storage modulus master curves from oscillatory measurements of silicone oils.The loss modulus master curve represents the dependence of the viscous flow behavior on · ₀ ^* and the storage modulus master curve — the dependence of the elastic flow behavior on · ₀ ^* .The relation between the values of the loss modulus and storage modulus master curves (at a certain frequency) is a measurement of the viscoelastic behavior of a system. The G/G-ratio depends on · ₀ ^* which leads to a viscoelastic master curve. The viscoelastic master curve represents the relation between the elastic and viscous oscillatory flow behavior.     

The dynamic performance of the Weissenberg rheogoniometer III. Large amplitude oscillatory shearing — harmonic analysis

The harmonic content of the nonlinear dynamic behaviour of 1% polyacrylamide in 50% glycerol/water was studied using a standard Model R 18 Weissenberg Rheogoniometer. The Fourier analysis of the Oscillation Input and Torsion Head motions was performed using a Digital Transfer Function Analyser.In the absence of fluid inertia effects and when the amplitude of the (fundamental) Oscillation Input motion _I is much greater than the amplitudes of the Fourier components of the Torsion Head motion _Tn empirical nonlinear dynamic rheological propertiesG _n (, ⁰),G _n (, ⁰) and/or _n (, ⁰), _n (, ⁰) may be evaluated without a-priori-knowledge of a rheological constitutive equation. A detailed derivation of the basic equations involved is presented.Cone and plate data for the third harmonic storage modulus (dynamic rigidity)G ₃ (, ⁰), loss modulusG ₃ (, ⁰) and loss angle ₃ (, ⁰) are presented for the frequency range 3.14 × 10^–2 1.25 × 10² rad/s at two strain amplitudes, _CP ⁰ = 2.27 and 4.03. Composite cone and plate and parallel plates data for both the third and fifth harmonic dynamic viscosities ₃ (, ⁰), _S (, ⁰) and dynamic rigiditiesG ₃ (, ⁰),G ₅ (, ⁰) are presented for strain amplitudes in the ranges 1.10 _CP ⁰ 4.03 and 1.80 _PP ⁰ 36 for a single frequency, = 3.14 × 10^–1 rad/s. Good agreement was obtained between the results from both geometries and the absence of significant fluid inertia effects was confirmed by the superposition of the data for different gap widths.     

Flow in porous media II: The governing equations for immiscible,two-phase flow

The Stokes flow of two immiscible fluids through a rigid porous medium is analyzed using the method of volume averaging. The volume-averaged momentum equations, in terms of averaged quantities and spatial deviations, are identical in form to that obtained for single phase flow; however, the solution of the closure problem gives rise to additional terms not found in the traditional treatment of two-phase flow. Qualitative arguments suggest that the nontraditional terms may be important when / is of order one, and order of magnitude analysis indicates that they may be significant in terms of the motion of a fluid at very low volume fractions. The theory contains features that could give rise to hysteresis effects, but in the present form it is restricted to static contact line phenomena.Roman Letters (, = , , and ) A interfacial area of the- interface contained within the macroscopic system, m² - A _e area of entrances and exits for the -phase contained within the macroscopic system, m² - A interfacial area of the- interface contained within the averaging volume, m² - A ^* interfacial area of the- interface contained within a unit cell, m² - A _e ^* area of entrances and exits for the-phase contained within a unit cell, m² - g gravity vector, m²/s - H mean curvature of the- interface, m^–1 - H area average of the mean curvature, m^–1 - H – H , deviation of the mean curvature, m^–1 - I unit tensor - K Darcy's law permeability tensor, m² - K permeability tensor for the-phase, m² - K viscous drag tensor for the-phase equation of motion - K viscous drag tensor for the-phase equation of motion - L characteristic length scale for volume averaged quantities, m - characteristic length scale for the-phase, m - n unit normal vector pointing from the-phase toward the-phase (n = –n ) - p _c p – P , capillary pressure, N/m² - p pressure in the-phase, N/m² - p intrinsic phase average pressure for the-phase, N/m² - p – p , spatial deviation of the pressure in the-phase, N/m² - r ₀ radius of the averaging volume, m - t time, s - v velocity vector for the-phase, m/s - v phase average velocity vector for the-phase, m/s - v intrinsic phase average velocity vector for the-phase, m/s - v – v , spatial deviation of the velocity vector for the-phase, m/s - V averaging volume, m³ - V volume of the-phase contained within the averaging volume, m³ Greek Letters V /V, volume fraction of the-phase - mass density of the-phase, kg/m³ - viscosity of the-phase, Nt/m² - surface tension of the- interface, N/m - viscous stress tensor for the-phase, N/m² - / kinematic viscosity, m²/s     

The third-normal stress difference in entangled melts: Quantitative stress-optical measurements in oscillatory shear

Stress-optical measurements are used to quantitatively determine the third-normal stress difference (N ₃ = N ₁ + N ₂) in three entangled polymer melts during small amplitude (<15%) oscillatory shear over a wide dynamic range. The results are presented in terms of the three material functions that describe N ₃ in oscillatory shear: the real and imaginary parts of its complex amplitude ₃ ^* = ₃ - i ₃ , and its displacement ₃ ^d . The results confirm that these functions are related to the dynamic modulus by ² ₃ ^* ()=(1-)[G ^*())– G ^*(2)] and ² ₃ ^d ()=(1- )G() as predicted by many constitutive equations, where = –N ₂/N ₁. The value of (1-) is found to be 0.69±0.07 for poly(ethylene-propylene) and 0.76±0.07 for polyisoprene. This corresponds to –N ₂/N ₁ = 0.31 and 0.24±0.07, close to the prediction of the reptation model when the independent alignment approximation is used, i.e., –N ₂/N ₁ = 2/7 – 0.28.     

The wedge subjected to tractions: a paradox resolved

The classical two-dimensional solution provided by Lévy for the stress distribution in an elastic wedge, loaded by a uniform pressure on one face, becomes infinite when the opening angle 2 of the wedge satisfies the equation tan 2 = 2. Such pathological behavior prompted the investigation in this paper of the stresses and displacements that are induced by tractions of O(r ^–) as r0. The key point is to choose an Airy stress function which generates stresses capable of accommodating unrestricted loading. Fortunately conditions can be derived which pre-determine the form of the necessary Airy stress function. The results show that inhomogeneous boundary conditions can induce stresses of O(r ^–), O(r ^– ln r), or O(r ^– ln² r) as r0, depending on which conditions are satisfied. The stress function used by Williams is sufficient only if the induced stress and displacement behavior is of the power type. The wedge loaded by uniform antisymmetric shear tractions is shown in this paper to exhibit stresses of O(ln r) as r0 for the half-plane or crack geometry. At the critical opening angle 2, uniform antisymmetric normal and symmetric shear tractions also induce the above type of stress singularity. No anticipating such stresses, Lévy used an insufficiently general Airy stress function that led to the observed pathological behavior at 2.     

Impacts of local dispersion and first-order decay on solute transport in randomly heterogeneous porous media

Stochastic subsurface transport theories either disregard local dispersion or take it to be constant. We offer an alternative Eulerian-Lagrangian formalism to account for both local dispersion and first-order mass removal (due to radioactive decay or biodegradation). It rests on a decomposition of the velocityv into a field-scale componentv , which is defined on the scale of measurement support, and a zero mean sub-field-scale componentv _s , which fluctuates randomly on scales smaller than. Without loss of generality, we work formally with unconditional statistics ofv _s and conditional statistics ofv . We then require that, within this (or other selected) working framework,v _s andv be mutually uncorrelated. This holds whenever the correlation scale ofv is large in comparison to that ofv _s . The formalism leads to an integro-differential equation for the conditional mean total concentration c which includes two dispersion terms, one field-scale and one sub-field-scale. It also leads to explicit expressions for conditional second moments of concentration cc. We solve the former, and evaluate the latter, for mildly fluctuatingv by means of an analytical-numerical method developed earlier by Zhang and Neuman. We present results in two-dimensional flow fields of unconditional (prior) mean uniformv . These show that the relative effect of local dispersion on first and second moments of concentration dies out locally as the corresponding dispersion tensor tends to zero. The effect also diminishes with time and source size. Our results thus do not support claims in the literature that local dispersion must always be accounted for, no matter how small it is. First-order decay reduces dispersion. This effect increases with time. However, these concentration moments c and cc of total concentrationc, which are associated with the scale below, cannot be used to estimate the field-scale concentrationc directly. To do so, a spatial average over the field measurement scale is needed. Nevertheless, our numerical results show that differences between the ensemble moments ofc and those ofc are negligible, especially for nonpoint sources, because the ensemble moments ofc are already smooth enough.     

Vorticity characteristics of the turbulent intermediate wake

Measurements of the lateral components _j (j=2 and 3) of the vorticity fluctuation vector have been made, using a vorticity probe consisting of two X-wires, in the intermediate wake of a circular cylinder. The effect of the spatial resolution of the probe on the measurement of _j has been studied. As the spatial resolution impairs, the variance and flatness factor of _j decrease whereas the skewness of _j increases. Reasonably accurate values of _j ² can be obtained by applying spectral corrections for the spatial resolution effect.Near the beginning of the intermediate wake, the variance of ₂ is larger than that of ₃ due to the significant contribution from ribs which connect consecutive spanwise roll vortices. This difference decreases with downstream distance. Also, the presence of the rolls is reflected by a local extremum in the skewness of ₃ on each side of the wake centerline. The magnitude of the extremum decreases with downstream distance.The support of the Australian Research Council is gratefully acknowledged.     

Normal forms for random diffeomorphisms

Given a dynamical system (,, ,) and a random diffeomorphism (): ^{d d} with fixed point at x=0. The normal form problem is to construct a smooth near-identity nonlinear random coordinate transformation h() to make the random diffeomorphism ()=h()^–1() h() as simple as possible, preferably linear. The linearization D(, 0)=:A() generates a matrix cocycle for which the multiplicative ergodic theorem holds, providing us with stochastic analogues of eigenvalues (Lyapunov exponents) and eigenspaces. Now the development runs pretty much parallel to the deterministic one, the difference being that the appearance of turns all problems into infinite-dimensional ones. In particular, the range of the homological operator is in general not closed, making the conceptof-normal form necessary. The stochastic versions of resonance and averaging are developed. The case of simple Lyapunov spectrum is treated in detail.     

Rheology of polydisperse polymers: relationship between intermolecular interactions and molecular weight distribution

An expression of the relaxation function of linear polydisperse polymers is proposed in terms of intermolecular couplings of reptative chains. The relaxation times of each molecular weight are assumed to be shifted according to a tube renewal mechanism accounting for the diffusion of the surrounding chains. The subsequent shift is applied to the relaxation function of each molecular weight obtained from an analytical expression of the complex compliance J ^*(). Therefore the complex shear modulus G ^*() is derived from the overall relaxation function using the probability density accounting for the molecular weight distribution and four species-dependent parameters: a front factor A for zero-shear viscosity, plateau modulus G _N ⁰ , activation energy E and characteristic temperature T . All the main features of the theology of polydisperse polymers are described by the proposed model.     

Hausdorff Dimension of Invariant Sets for Random Dynamical Systems

Suppose X() is a compact random set, invariant with respect to a continuously differentiable random dynamical system (RDS) on a separable Hilbert space. It is shown that the Hausdorff dimension dim _H (X()) is an invariant random variable, and it is bounded by d, provided the RDS contracts d-dimensional volumes exponentially fast. Both exponential decrease of d-volumes as well as the approximation of the RDS by its linearization are assumed to hold uniformly in . The results are applied to reaction diffusion equations with additive noise and to two-dimensional Navier–Stokes equations with bounded real noise.     

Some properties of the solutions of wave equations

Some properties of solutions of initial value problems and mixed initial-boundary value problems of a class of wave equations are discussed. Wave modes are defined and it is shown that for the given class of wave equations there is a one to one correspondence with the roots _i (k) or k _j () of the dispersion relation W(, k)=0. It is shown that solutions of initial value problems cannot consist of single wave modes if the initial values belong to W ₂ ¹ (–, ); generally such solutions must contain all possible modes. Similar results hold for solutions of mixed initial-boundary value problems. It is found that such solutions are stable, even if some of the singularities of the functions k _j () lie in the upper half of the plane. The implications of this result for the Kramers-Kronig relations are discussed.     

Concentration dependence of the critical viscoelastic properties of gelatin at the gel point

Gelatin gel properties have been studied through the evolution of the storage [G()] and the loss [G()] moduli during gelation or melting near the gel point at several concentrations. The linear viscoelastic properties at the percolation threshold follow a power-law G()G() and correspond to the behavior described by a rheological constitutive equation known as the Gel Equation. The critical point is characterized by the relation: tan = G/G = cst = tan ( · /2) and it may be precisely located using the variations of tan versus the gelation or melting parameter (time or temperature) at several frequencies. The effect of concentration and of time-temperature gel history on its variations has been studied. On gelation, critical temperatures at each concentration were extrapolated to infinite gel times. On melting, critical temperatures were determined by heating step by step after a controlled period of aging. Phase diagrams [T = f(C)] were obtained for gelation and melting and the corresponding enthalpies were calculated using the Ferry-Eldridge relation. A detailed study of the variations of A with concentration and with gel history was carried out. The values of which were generally in the 0.60–0.72 range but could be as low as 0.20–0.30 in some experimental conditions, were compared with published and theoretical values.     

Dynamic melt viscoelastic behavior of random copolymers

Summary The viscoelastic properties of 65/35 styrenen-butyl methacrylate random copolymers were determined using the Eccentric Rotating Disks device of the Rheometrics Mechanical Spectrometer. Similar to the behavior observed in homopolymers, an increase in the molecular weight of the copolymer resulted in extension of the rubbery plateau and in a reduction in the terminal region. The dynamic complex viscosity showed onset of non-Newtonian flow at higher frequencies, with the non-Newtonian region increasing with increasing molecular weight.The elastic modulus,G, was dependent upon the frequency,, asG ^1.5 in the terminal region, rather than asG ² observed for polystyrene. The viscous modulus,G, was proportional to the frequency,, asG , similar to what is observed for polystyrene. The dynamic viscosity | ^*| at high frequencies showed a region independent of molecular weight where a power law of | ^*| ^0.9 is applicable, consistent with entanglement models. Thy dynamic viscosity at low frequencies in the Newtonian region is related to molecular weight as |^*| . Using WLF equations, the coefficient of expansion, _f , was obtained that, together with glass transition, showed a negative deviation from the Fox-Flory relationship.

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Zusammenfassung Die viskoelastischen Eigenschaften von statistischen 65/35-Styrol/n-Butyl-Methacrylat-Kopolymeren wurden mit Hilfe einer Maxwell-Rheometer-Anordnung in Verbindung mit dem Mechanischen Spektrometer der Fa. Rheometrics bestimmt. Ähnlich dem bei Homopolymeren beobachteten Verhalten ergab sich auch hier mit wachsendem Molekulargewicht eine Verbreiterung des Kautschuk-Plateaus und eine Verkleinerung des Endbereichs. Die komplexe Viskosität zeigte erst bei höheren Frequenzen das Einsetzen nicht-newtonschen Fließens an, wobei der nichtnewtonsche Bereich mit steigendem Molekulargewicht größer wurde.Der SpeichermodulG ergab sich im Endbereich als proportional zu ^1,5, im Unterschied zu der bei Polystyrol beobachteten Proportionalität mit ². Dagegen war der VerlustmodulG der Frequenz direkt proportional, ähnlich wie es auch bei Polystyrol beobachtet worden war. Die dynamische Viskosität | ^*| zeigte unabhängig vom Molekulargewicht bei hohen Frequenzen einen Bereich, in dem eine Potenz-Beziehung | ^*| ~ ^0,9 herrschte, was auf die Wirkung von Verzweigungen hindeutet. Dagegen galt bei den niedrigen Frequenzen des newtonschen Bereichs|^*| ~ . Mit Hilfe der WLF-Gleichung wurde der Ausdehnungskoeffizient _f bestimmt, der ebenso wie der Glasübergang eine negative Abweichung von der Fox-Flory-Beziehung zeigte.

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With 10 figures and 1 table     

Free damped oscillations of the linear viscoelastic material

This work shows that the complex dynamic viscosity ^* () can be evaluated from experimental data of free damped oscillations (FDO) when upper and lower angular displacements measured in a plate-plate geometry are analyzed by Fourier series. We deduce the equation required to evaluate experimentally the dynamic functions of linear viscoelastic materials in FDO. Two loss tangents can be defined in FDO, which are not necessarily equal to tan () of the forced oscillation test.     

An analogue study for flame flickering

An analogue experiment is proposed to simulate flame flickering comprising a free ascending column fed on its side with a light gas (helium) emerging from a vertical slot in ambient air. The convective motion of the helium jet is considered to represent the motion of burnt gases of buoyant jet flames. The helium jet is accelerated by buoyancy effects and the flow field is similar to that of burnt gases observed for real buoyant flames. The vertical velocity profile of the steady helium jet is measured at different vertical distances. The unsteady helium jet is also studied by measuring the instability frequency as a function of ambient pressure at different injection flow rates, and by analyzing the tomography images of the helium jet. The instability morphology is the same as that observed on real buoyant flames. We conclude that this type of instability can be approximately characterized by the maximum vertical velocityu _max, and the distance betweenu _max in the helium ascending column andu = o in the ambient air. For this type of instability the local vorticity is proportional to which can be influenced by gravity and ambient pressure. Theoretical prediction of the instability frequency as a function of gravity and ambient pressure has been obtained, and is in good agreement with the experimental results.List of symbols C ₁,C ₂ constants - F instability frequency - F _c critical frequency - F _m the most amplified frequency - F (K, ) function defined in (11) - g gravitational acceleration - g reduced gravity acceleration g(₀-^*)/^* - k real wave number of the disturbance - K reduced wave numberK=2k - K _c reduced wave number of the critical instability mode - K _m nondimensional wavenumber of the most amplified mode - L vertical characteristic length (in x direction) - P ambient pressure - u local vertical buoyant velocity (inx direction) - u _max local maximum vertical velocity - v local velocity component iny direction (horizontal) - V ₀ injection velocity of helium (iny direction) - x vertical distance measured from the leading edge of boundary layer - y horizontal distance measured from the exit plane of the vertical slot - Z(K, ) function defined in equation (11) Greek symbols distance betweenu _max in the helium ascending column andu = o in the ambient air - - wavelength of instability - _c critical wavelength - _m the most amplified wavelength - ^* helium density at slot exit - ₀ ambient air density - ^* helium dynamic viscosity at slot exit - v ^* helium kinematic viscosity at slot exit - complex number presented in disturbancee ^i(kx+t) - _i imaginary part of , representing the amplification rate of disturbance - _r real part of , where ( _r /k) represents the group velocity - reduced complex number of , defined      

Stabilization of the interface instability of moving magnetizable fluids

A study is made of the stabilization of the interface between two moving magnetizable fluids by means of an external magnetic field H={H₀ cos t, H₀ sin t, 0} of circular polarization. The fluids are assumed to be ideal, incompressible, nonconducting, and electrically neutral. An equation of motion is derived for the perturbed interface. The Borg criterion is used to obtain sufficient conditions of stability of small perturbations of the interface; these conditions relate the amplitude H₀ and the frequency of the external magnetic field to the characteristic parameters of the problem and the wave vector k. The dependence of H₀ and on the modulus of the wave vector is investigated. The obtained results are compared with the results of [1].Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 118–122, July–August, 1980.     

On the Ellipticity of the Middle Surface of a Shell and its Application to the Asymptotic Analysis of ‘Membrane’ Shells

We consider a surface S = (), where ² is a bounded, connected, open set with a smooth boundary and : ³ is a smooth map; let () denote the components of the two-dimensional linearized strain tensor of S and let 0 with length 0 > 0. We assume the the norm ,|| ()||0, in the space V0() = { H¹() × H¹() × L²(); = 0 on 0 } is equivalent to the usual product norm on this space. We then establish that this assumption implies that the surface S is uniformly elliptic and that we necessarily have 0 = .     

Relations between steady flow and oscillatory shear measurements

Summary Results are given of a comparison between dynamic oscillatory and steady shear flow measurements with some polymer melts. Comparison of the steady shear flow viscosity,, with the absolute value of the dynamic viscosity, ¦¦, at equal values of the shear rate,q, and the circular frequency,, has shown the relation thatCox andHerz had found empirically to be substantially correct.Further, the coefficients of the normal stress differences obtained by streaming birefringence techniques have been compared with 2G () · ^{– 2} in the same range of shear rates as covered by the viscosity measurements (G is the real part of the dynamic shear modulus). Two polystyrenes with narrow molecular weight distribution showed the same shift factor along the orq axis for the normal stress coefficients with respect to 2G () · ^{– 2} and the steady shear flow viscosities with respect to the real part of the dynamic viscosity,. For two polyethylenes the results are not so conclusive owing to the smallness of the shift factor found. An empirical equation is proposed predicting the main normal stress difference from dynamic measurements only.

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Zusammenfassung Die Ergebnisse von Messungen unter erzwungenen Schwingungen und stationärer Scherströmung an einigen Polymerschmelzen werden miteinander verglichen. Der Vergleich der stationären Viskosität mit der absoluten dynamischen Viskosität ¦¦ bei gleichen Werten des Strömungsgradientenq und der Kreisfrequenz zeigt die Gültigkeit der empirischen Beziehung vonCox undHerz.Weiter wurden die Koeffizienten der Normalspannungsdifferenzen, welche durch Messung der Strömungsdoppelbrechung erhalten wurden, mit 2G() · ^–2 verglichen, und zwar wiederum bei gleichen Werten vonq und, wobeiG die Speicherkomponente des dynamischen Schubmoduls ist. Zwei Polystyrole mit enger Molekulargewichtsverteilung zeigen die gleiche Verschiebung entlang der-oderq-Achse für die Normalspannungskoeffizienten in bezug auf2G()· ^–2 und für die stationären Scherviskositäten in bezug auf den Realteil der dynamischen Viskosität. Für zwei Polyäthylene sind die Ergebnisse weniger signifikant, da die entsprechenden Verschiebungen zu klein waren. Eine empirische Beziehung zwischen den Hauptnormalspannungsdifferenzen und den dynamischen Meßwerten wird vorgeschlagen.

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Paper presented at the British Society of Rheology Conference, held at Shrivenham, from 9th–12th September, 1968.     

Comparison of a new internal viscosity model with other constrained-connector theories of dilute polymer solution rheology

Complex viscosity ^* = -i predictions of the Dasbach-Manke-Williams (DMW) internal viscosity (IV) model for dilute polymer solutions, which employs a mathematically rigorous formulation of the IV forces, are examined in the limit of infinite IV over the full range of frequency number of submolecules N, and hydrodynamic interaction h ^*. Although the DMW model employs linear entropic spring forces, infinite IV makes the submolecules rigid by suppressing spring deformations, thereby emulating the dynamics of a freely jointed chain of rigid links. The DMW () and () predictions are in close agreement with results for true freely jointed chain models obtained by Hassager (1974) and Fixman and Kovac (1974 a, b) with far more complicated formalisms. The infinite-frequency dynamic viscosity predicted by the DMW infinite-IV model is also found to be in remarkable agreement with the calculations of Doi et al. (1975). In contrast to the other freely jointed chain models cited above, however, the DMW model yields a simple closed-form solution for complex viscosity expressed in terms of Rouse-Zimm relaxation times.