The langevin approach to the dumbbell kinetic problem in rheology

An alternative formalism to the dumbbell kinetic problem is proposed which is believed to be more fundamental than the classical Liouville one. The new formulation provides a logical approach to non-conservative systems and systems with varying frictional coefficients. A non-linear dumbbell with internal viscosity and varying frictional factor for the beads is examined. It is proved that the centre of gravity of the dumbbell must move affinely with the solvent continuum. A useful class of approximation is suggested to reduce the constitutive equation to an explicit form. The response of the model is computed for a number of flow fields. For shear flows, the introduction of the internal viscosity results in a shear-thinning phenomenon. The onset of non-Newtonian behaviour occurs at the correct order of magnitude of the dimensionless shear rate. Also, a negative second normal stress difference is found which varies with shear rate. In an oscillatory shear flow, the internal viscosity leads to a finite limiting value of the dynamic viscosity at high frequencies. In elongational flow the effects of the varying frictional coefficient dominate that of the internal viscosity. Interesting phenomena include the presence of a hysteresis loop and the ability of the dumbbell to maintain an extended configuration at moderate elongational rates. Clearly, these are relevant in turbulent drag reduction applications. The model has sufficient merits to deserve more investigation.     

Dilute solution rheology: experimental results and finitely extensible nonlinear elastic dumbbell theory

Experimental results for intrinsic viscosity and for intrinsic complex viscosity of polymer solutions were compared with the rheological predictions of the finitely extensible, nonlinear elastic (FENE) dumbbell theory of a dilute suspension. The FENE dumbbell adequately models the intrinsic viscosity of flexible polymers, but less successfully portrays the behavior in small amplitude oscillatory motion. Expressions for the high frequency asymptotic limit of the intrinsic complex viscosity of a FENE dumbbell suspension, and the mean-square end-to-end distance of FENE dumbbells in steady shear flow are given.     

The effect of the hydrodynamic interaction on the rheological properties of Hookean dumbbell suspensions in steady state shear flow

The diffusion equation for the configurational distribution function of Hookean dumbbell suspensions with the hydrodynamic interaction (HI) was solved, in terms of Galerkin’s method, in steady state shear flow; and viscosity,first and second normal-stress coefficients and molecular stretching were then calculated. The results indicate that the HI included in a microscopic model of molecules gives rise to a significant effect on the macroscopic properties of Hookean dumbbell suspensions. For example, the viscosity and the first normal stress coefficient, decreasing as shear rate increases, are no longer constant; the second normal-stress coefficient, being negative with small absolute value and shear-rate dependent, is no longer zero; and an additional stretching of dumbbells is yielded by the HI. The viscosity function and the first normal-stress coefficient calculated from this method are in agreement with those predicted from the self-consistent average method qualitatively, while the negative second normal-stress coefficient from the former seems to be more reasonable than the positive one from the latter.     

A constitutive equation derived from Lodge's network theory

A constitutive equation is presented, derived from Lodge's molecular network theory. The equation is of a form similar to the one presented previously by Carreau. The rate of creation of junctions and the probability of loss of junctions depend here also on the second invariant of the rate-of-strain tensor. The dependence, however, is through simple exponential functions, resulting in easy-to-use equations.Material functions are presented for the viscosity, the primary normal stress coefficient, the complex viscosity, the stress relaxation after cessation of steady simple shear, the stress growth after onset of steady simple shear and for elongational flow. The usefulness of the simplified (series truncated) equations is discussed and the model is evaluated with typical viscoelastic data.     

A constitutive equation for a dilute solution of Hookean dumbbells with approximate hydrodynamic interaction

In a recent series of papers, Öttinger's consistently averaged hydrodynamic interaction has been shown to yield shear-rate dependent viscosity and normal stress coefficients in steady shear flow for dilute solutions of elastic dumbbells and chains. Even more recently, Fan has numerically solved the diffusion equation for the Hookean dumbbell with complete hydrodynamic interaction and he has compared his results with those of the Öttinger model.In this paper, a new approximation¹ for the Oseen—Burgers tensor is proposed where the configuration-dependent terms are replaced by appropriate averages rather than averaging the Oseen—Burgers tensor as a whole as in the Öttinger model. The proposed model leads to a differential constitutive equation which at low shear rates is similar to the Giesekus constitutive equation for a Hookean dumbbell with anistropic drag and anisotropic Brownian motion. The steady shear viscosity and normal stress coefficients for the proposed model are shear-rate dependent and are in close agreement with Fan's numerical calculations. Elongational viscosity for both positive and negative elongation rates are calculated.     

An intriguing empirical rule for computing the first normal stress difference from steady shear viscosity data for concentrated polymer solutions and melts

The Cox–Merz rule and Laun’s rule are two empirical relations that allow the estimation of steady shear viscosity and first normal stress difference, respectively, using small amplitude oscillatory shear measurements. The validity of the Cox–Merz rule and Laun’s rule imply an agreement between the linear viscoelastic response measured in small amplitude oscillatory shear and the nonlinear response measured in steady shear flow measurements. We show that by using a lesser-known relationship also proposed by Cox and Merz, in conjunction with Laun’s rule, a relationship between the rate-dependent steady shear viscosity and the first normal stress difference can be deduced. The new empirical relation enables a priori estimation of the first normal stress difference using only the steady flow curve (i.e., viscosity vs shear rate data). Comparison of the estimated first normal stress difference with the measured values for six different polymer solutions and melts show that the empirical rule provides values that are in reasonable agreement with measurements over a wide range of shear rates, thus deepening the intriguing connection between linear and nonlinear viscoelastic response of entangled polymeric materials.     

Dynamics of rigid and flexible polymer chains in confined geometries. part I: steady simple shear flow

This paper describes exact solutions to the response of both the elastic and rigid dumbbell models to a steady simple shear flow in a channel having a length scale comparable to the dumbbells themselves. Results are given for rheological properties over the entire range of the ratio of the channel width to the length of the dumbbell. It is found that both models lead to a decrease in viscosity as the channel is reduced in size with the elastic dumbbell predicting a stronger dependence on that parameter compared with the rigid dumbbell. The elastic dumbbell predicts shear independent rheological properties whereas the rigid dumbell predicts shear thinning as in the case of unbounded flows. The rate of shear thinning, however, decreases with decreasing channel width.     

Possibility of a master plot for material functions of high-polymer solutions

A new systematic method has been developed for estimating rheological properties (such as relaxation time, viscosity, primary normal stress difference) for various polymer solutions form the zero-shear-rate specific viscosity and a dimensionless shear rate.A linear relation has been found between the relaxation time and the zero-shear-rate specific viscosity on a double-logarithmic plot, and a new master plot for the primary normal stress difference has been established. In addition the applicability of the FENE-P dumbbell model to high-polymer solutions is discussed.     

Monte Carlo simulation of self-avoiding lattice chains subject to oscillatory shear flow in polymer solution

 This paper has introduced a pseudo-potential in bond-fluctuation model to simulate oscillatory shear flow of multiple self-avoiding chains in three dimensions following our previous work under simple shear flow. The oscillatory flow field was reasonably reproduced by lattice Monte Carlo simulation using this pseudo-potential neglecting hydrodynamic interaction. By sampling the configuration distribution functions, the macroscopic viscoelasticity of semi-concentrated polymer solution was determined. Both Newtonian and non-Newtonian regimes were studied. The complex modulus and dynamic viscosity exhibit a reasonable power relation with oscillatory frequency, which is consistent with present theories and experiments. Consequently, lattice Monte Carlo simulation has been extended to model free-draining self-avoiding multi chains subject to oscillatory shear flow and to investigate associated viscoelasticity on the molecular level. Received: 1 October 1999 Accepted: 19 October 1999     

Internal viscosity in polymer kinetic theory: shear flows

The Gaussian closure method and Brownian dynamics simulations have been used to calculate the shear material properties of a dilute solution of Hookean dumbbells with internal viscosity. Results for the zero-shear-rate material properties and small amplitude oscillatory shear material properties have been found analytically, and numerical results for the steady state shear material properties are also presented. Two interpretations of the stress tensor are investigated and results are compared. Brownian dynamics simulations are used to obtain material properties of the Hookean dumbbell with internal viscosity without approximations. These simulation results are compared with the perturbation solution of Booij and van Wiechen as well as with a new Gaussian closure solution. Also presented are the contracted distribution functions as derived from the Gaussian closure method and from Brownian dynamics simulations.     

Linear and non-linear rheological behaviour of cement and silica suspensions. Effect of polymer addition

Oil well cement pastes and model silica suspensions demonstrate similar rheology: in oscillatory shear, beyond a critical stress, a sharp transition is ob- served between gel and liquid behaviour. In creep tests, an apparent yield stress and shear-thinning are followed by the appearance of shear thickening. The minimum viscosity measured in steady shear is close in value to the complex viscosity obtained from oscillatory measurements. The observations can be explained by the formation of liquid trapping aggregates whose compactness may be estimated by fitting the Tsenoglou model, and whose cohesion is reflected in the rigidity of the gel and in the critical strain (or stress) of gel dissolution. Substituting cement or silica particles by polymer redispersible powder causes a decrease of the storage modulus in the gel state and a lower viscosity, while leaving the general features of the flow curve unchanged. Decrease in material rigidity may be due to a weaker inter-particle attraction generated by the polymer presence. The decrease in viscosity is explained by a lessening of water entrapped within the aggregates, which now contain polymer particles which are less hydrophilic than either cement or silica.     

Is there a relation between the relaxation time measured in CaBER experiments and the first normal stress coefficient?

We investigate a variety of different semidilute polymer solutions in shear and elongational flow. The shear flow is created in the cone-plate-geometry of a commercial rheometer. We use capillary thinning of a filament that is formed by a polymer solution in the Capillary Breakup Extensional Rheometer (CaBER) as an elongational flow. We compare the relaxation time measured in the CaBER with relaxation times based on the first normal stress difference and the zero shear polymer viscosity that we measure in our rheometer. All of these three measurable quantities depend on different fluid parameters—the viscosity of the solvent, the polymer concentration within the solution, and the molecular weight of the polymers—and on the shear rate (in the shear flow measurements). Nevertheless, we find that the first normal stress coefficient depends quadratically on the CaBER relaxation time. Several scaling laws are presented that could help to explain this empirical relation.     

刚性圆管中血液周期振荡流的切应力分布

本文通过求解圆管内血液振荡流的基本方程，求得圆管内血液流的压力梯度与切应力之间的关系式。在此基础上，详细讲座了圆管中轴向流速和切变率谐波的变化规律，指出流速谐波和切变率谐波的幅值都将随着谐波次数的增大而逐渐减小。为了使所得结果便于应用。文章通过管轴向中心线流速与压力梯度之间的关系式，进一步给出一种利用管轴向中心线流速计算管内切应力分布的简便方法。该方法用于检测活体血管内血液振荡流的切应力分布，具有操作简单，精度较高的优点。最后，以人体颈动脉为例，讨论血液周期振荡流的切应力的分布特性。发现在任意时刻，除了邻近管壁处切应力急剧增大到一定数值之外，沿管截面切应力分布相当均匀且接近于零，呈现出与定常流不同的切应力分布特征。     

Orthogonal superposition of small and large amplitude oscillations upon steady shear flow of polymer fluids

The orthogonal superposition of small and large amplitude oscillations upon steady shear flow of elastic fluids has been considered. Theoretical results, obtained by numerical methods, are based on the Leonov viscoelastic constitutive equation. Steady-state components, amplitudes and phase angles of the oscillatory components of the shear stress, the first and second normal stress differences as functions of shear rate, deformation amplitude and frequency have been calculated. These oscillatory components include the first and third harmonic of the shear stresses and the second harmonic of the normal stresses. In the case of small amplitude superposition, the effect of the steady shear flow upon the frequency-dependent storage modulus and dynamic viscosity has been determined and compared with experimental data available in literature for polymeric solutions. The predicted results have been found to be in fair agreement with the experimental data at low shear rates and only in qualitative agreement at high shear rates and low frequencies. A comparison of the present theoretical results has also been made with the predictions of other theories.In the case of large amplitude superposition, the effect of oscillations upon the steady shear flow characteristics has been determined, indicating that the orthogonal superposition has less influence on the steady state shear stresses and the first difference of normal stresses than the parallel superposition. However, in the orthogonal superposition a more pronounced influence has been observed for the second difference of normal stresses.     

Who conceived the “complex viscosity”?

In small amplitude oscillatory shear flow, we now universally represent the response of a viscoelastic fluid as a complex quantity, which we call “complex viscosity.” This short piece deepens our understanding of the origins of the complex viscosity and of the man who coined this term, now widely used in rheology.     

Coupling between flow and diffusion at polymer/polymer interfaces: large amplitude oscillatory shear experiments

 Coupling between flow and diffusion at symmetric polymer/polymer interfaces has been investigated. Polystyrene/polystyrene sandwich assemblies were subjected to large-amplitude oscillatory shear (LAOS) using a sliding-plate rheometer (SPR) and the stress was monitored as a function of time. The results were treated using a new model combining Wagner's model with the theory of Doi and Edwards. The model explicitly expresses the influence of the strain and stress amplitudes frequency and time on the self-diffusion process. The apparent self-diffusion coefficient was found to increase with welding time, in agreement with our previous results obtained using small-amplitude oscillatory shear measurements. However, it was found in the present case that the self-diffusion coefficient depends strongly on the strain and stress amplitudes and frequency, and its steady state value was found to be larger than that determined from small-amplitude oscillatory shear measurements. It appears that the large strain oscillatory shear field continuously increases the density of chain ends at the interface and thus increases the flux of mass transport. Received: 30 January 2001 Accepted: 12 June 2001     

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

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

Analysis of simple shear endochronic equations for finite plastic deformation

IntroductionThestress_strainbehaviorofmaterialswithfiniteplasticdeformationisaninterestingissue ,onwhichsignificantprogresshasbeenmadethroughboththephenomenologicalandphysicalapproaches.Thephenomenologicalapproachisbasedoncontinuummechanicsofplasticity .Ithasitsadvantageinsolvingcomplicatedproblemsbecauseofitssimplicity .Mostofphenomenologicaltheoriesareinvolvedintheconceptofcorotationalrates.Thematerialderivativeofstresswasnotobjectiveunderfinitedeformation .TheJaumannratewasusuallyusedbefo…     

Prediction of normal stresses under large amplitude oscillatory shear flow

The dynamic response of viscoelastic fluids under large amplitude oscillatory shear (LAOS) has been a subject of long history. In the LAOS flow, the analysis has been mostly focused on shear stress, possibly due to the lack of accurate measurement of normal stress. However, the normal stress may become larger than shear stress at high-strain amplitudes, and thus it is important that we have a good understanding of the normal stress behavior. Furthermore, with the advancement in the instrumentation, it has become possible to get more reliable data. The purpose of this paper is to develop a research platform to analyze and to understand the normal stress behavior of complex fluids under LAOS flow. In this study, we utilized the Giesekus model as a representative constitutive model, and investigated its diverse responses. We defined the dynamic properties corresponding to normal stress, in a similar way to define dynamic moduli from shear stress, and examine their behavior with various analyzing tools. Experimental data were also compared with model predictions. Despite the fact that it is not yet possible to compare all of the predictions because of instrumental limitation, the prediction has been found to fit well with the experimental data. This study is expected to provide a useful framework for further understanding the nonlinear behavior of complex fluids at large deformation.     

Structure and dynamics of a polymer solution subject to flow-induced phase separation

Experiments combining mechanical rheometry with polarimetry (birefringence and scattering dichroism) have been conducted on a 6% solution of polystyrene (1.86x10⁶ molecular weight) in dioctyl phthalate. Birefringence is used to measure the extent of segmental orientation, whereas the dichroism is sensitive to orientation and deformation of concentration fluctuations associated with the process of flow-induced phase separation. The results indicate that these fluctuations grow predominately along the neutral (or vorticity axis) of a simple shear flow. At higher rates of shear, orientation in the flow direction is favored. The transition in orientation direction is accompanied by time-dependent behavior in the optical properties of the solution during shear and the onset of shear thickening of the viscosity and the first normal stress difference coefficient.