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.     

Extrudate swell of Boger fluids

Boger fluids are dilute polymer solutions exhibiting high elasticity at low apparent shear rates, which leads to high extrudate swell. Numerical simulations have been undertaken for the flow of three Boger fluids (including benchmark Fluid M1), obeying an integral constitutive equation of the K-BKZ type, capable of describing the behavior of dilute polymer solutions. Their rheology is well captured by the integral model. The flow simulations are performed for planar and axisymmetric geometries without or with gravity. The results provide the extrudate swell and the excess pressure losses (exit correction), as well as the shape and extent of the free surface. All these quantities increase rapidly and monotonically with increasing elasticity level measured by the stress ratio, S_R. It was found that the main reason for the high extrudate swelling is high normal stresses exhibited in shear flow (namely, the first normal-stress difference, N₁). Surprisingly, the elongational parameter of the model or a second normal-stress difference N₂ do not affect the results appreciably. Gravity serves to lower the swelling considerably, and makes the simulations easier and in overall agreement with previous experiments.     

The rheology of suspensions of vinylon fibers in polymer liquids. II. Suspensions in polymer solutions

Summary The rheological properties of vinylon fiber suspensions in polymer solutions were studied in steady shear flow. Shear viscosity, first normal-stress difference, yield stress, relative viscosity, and other properties were discussed. Three kinds of flexible vinylon fibers of uniform length and three kinds of polymer solutions as mediums which exhibited remarkable non-Newtonian behaviors were employed. The shear viscosity and relative viscosity ( _r ) increased with the fiber content and the aspect ratio, and depended upon the shear rate. Shear rate dependence of _r was found only in the low shear rate region. This result was different from that of vinylon fiber suspensions in Newtonian fluids. The first normal-stress difference increased at first slightly with increasing fiber content but rather decreased and showed lower values for high content suspensions than that of the medium. A yield stress could be determined by using a modified equation of Casson type. The flow properties of the fiber suspensions depended on the viscosity of the medium in the suspensions under consideration.With 16 figures and 1 table     

Dynamic flow properties of vinylon fibre and glass fiber reinforced polyethylene melts

An experimental study of the dynamic shear flow properties of polyethylene melts filled with glass fibers and vinylon fibers was carried out and comparison with the steady shear flow properties was made. The effects of loading level and the characteristics of the fibers on the rheological properties of the fiber-filled systems is discussed. The rigidity and complex viscosity of the fiber-filled systems is sensitive not only to the quantity of fibers but also to their length, distribution and properties. The Cox-Merz empirical law for complex viscosity and steady shear viscosity, and Roscoe's empirical relation for estimating the normal-stress coefficients are both able to be applied to pure polymer melts but not to fiber-filled systems.     

Constitutive relationships for polymeric materials with power-law distributions of relaxation times

The linear relaxation modulus of polydisperse polymer melts and solutions can often be approximated by a power law,ct ^–m over some range of time,t. If, in addition, the nonlinear rheology is given by a separable integral equation, with a strain-dependent factor typical of those observed experimentally, then some commonly observed empirical rules and equations can be readily derived as approximations, namely the Cox-Merz relationship between complex viscosity and steady-state shear viscosity, Bersted's predictions of steady shear stress and first normal-stress difference from a truncated spectrum of linear relaxation times, and the observation of Koyama and coworkers that the ratio of the nonlinear to the linear time-dependent elongational viscosity is independent of strain rate, over a range of strain rates outside the linear regime.     

Elongational flow behavior of polymeric fluids according to the Leonov model

The viscoelastic behavior of polymeric systems based upon the Leonov model has been examined for (i) the stress growth at constant strain rate, (ii) the stress growth at constant speed and (iii) the elastic recovery in elongational flow. The model parameters have been determined from the available rheological data obtained either in steady shear flow (shear viscosity and first normal-stress difference as a function of shear rate) or oscillatory flow (storage and loss moduli as a function of frequency in the linear region) or from extensional flow at very small strain rates (time-dependent elongation viscosity in the linear viscoelastic limit). In addition, the effect of the parameter characterizing the strain-hardening of the material during elongation has also been studied. The estimation of this parameter has been based upon the structural characteristics of the polymer chain which include the critical molecular weight and molecular weight of an independent segment. Five different polymer melts have been considered with varying number of modes (maximum four modes). Resulting predictions are in fair agreement with corresponding experimental data in the literature.     

The relationship between simple shear and pure shear for a simple fluid without coupling effects

Similarities between simple shear and pure shear or planar extension are exploited to derive equations relating stress in pure shear at constant extension rate to the stress in simple shear at constant shear rate. For the class of materials considered it follows that there are only two independent material functions required to describe simple shear. The relationships derived may also be used to estimate the ratio of first to second normal-stress differences in simple shear using experimental results from pure shear experiments.     

Viscosity,first and second normal-stress coefficients,and molecular stretching in concentrated solutions and melts

A numerical method to solve the diffusion equation for the encapsulated FENE-dumbbell model is presented. Viscosity, first and second normal-stress coefficients, and molecular stretching for steady state shear flow are calculated. From the graphs of these quantities one can see the effect of anisotropy of Stokes' resistance and the Brownian force on rheological properties. The accuracy of the approximate method used by Bird and DeAguiar is assessed.     

The rheology of suspensions of vinylon fibers in polymer liquids. I. Suspensions in silicone oil

Summary The steady shear flow properties of suspensions of vinylon fibers in silicone oil were measured by means of a cone-plate type rheometer. Three kinds of vinylon fibers used had no distributions of length and were more flexible than glass fibers and the like. The content of the fibers ranged from 0 to 7 wt.%. Shear viscosity, the first normal-stress difference, yield stress, and relative viscosity were discussed. Shear viscosity and relative viscosity increased with the fiber concentration and the aspect ratio, and depended upon the shear rate. The applicability of Ziegel's equation of viscosity for fiber suspensions was investigated. The first normal-stress difference increased with the fiber concentration, aspect ratio, and shear rate and its relative increase was much larger than for shear stress and viscosity depending on the properties of the characteristic time, The yield stress could be determined by Casson plots for large aspect ratio fiber suspensions even in low concentration comparing with the suspensions of spherical particles or powder. The influence of the flexibility of the fibers for the rheological properties of the fiber suspensions can not be ignored.With 12 figures and 2 tables     

A new eccentric-cylinder rheometer

A new eccentric-cylinder rheometer with guard-ring equipment was constructed as an auxiliary set-up to a Rheometrics Mechanical Spectrometer, type 7200, which enables measurements with the eccentric disk technique. Experimental tests with Newtonian fluids and polymer solutions of relatively low viscosity show that this instrument yields reliable plots of shear viscosity and first normal-stress coefficient over several decades of the effective average shear rate. These coincide very well with plots from a commercial cone-and-plate rheometer even for higher relative eccentricities (up to 0.75). However, no systematic effects of eccentricity, to be expected for higher shear rates, could be observed with these fluids, so that supplementary tests applying fluids with more pronounced viscoelastic properties are to be carried out.     

Shear flow rheological properties of vinylon- and glass-fiber reinforced polyethylene melts

Shear viscosity, shear stress and first normal-stress difference have been investigated for glass- and vinylon-fiber filled polyethylene melts over a wide range of shear rate by means of three kinds of instruments. The influence of fiber content and fiber properties on the rheological properties is discussed. The viscosity increases with increasing aspect ratio and fiber content, and the influence of these parameters on the flow properties is evident at low shear rates. The first normalstress difference increases more rapidly with increasing glass fiber content, especially at low shear stresses. The influence of vinylon fibers on the first normal stress-difference vs. shear-stress relationship is different from that of glass fibers.     

Drag reduction in the turbulent pipe flow of polymers

The paper concerns an experimental study of the fully developed turbulent pipe flow of several different aqueous polymer solutions: 0.25%, 0.3% and 0.4% carboxymethylcellulose (CMC), 0.2% xanthan gum (XG), a 0.09%/0.09% CMC/XG blend, 0.125% and 0.2% polyacrylamide (PAA). The flow data include friction factor vs. Reynolds number, mean velocity and near-wall shear rate distributions, and axial velocity fluctuation intensity u′ at a fixed radial location as a laminar/turbulent transition indicator. For each fluid we also include measurements of shear viscosity, first normal-stress difference and extensional viscosity. At high shear rates we find that the degree of viscoelasticity increases with concentration (0.3% CMC is an exception) for a given polymer, and in the sequence XG, CMC/XG, CMC, PAA, whilst at low shear rates the ranking changes to CMC, CMC/XG, XG, PAA. The extensional viscosity ranking is XG/CMC, XG, CMC, PAA at high strain rates and the same as that for the viscoelasticity at low shear rates. We find that the observed drag-reduction behaviour is consistent for most part with the viscoelastic and extensional-viscosity behaviour at the low shear and strain rates typical of those occurring in the outer zone of the buffer region.Although laminar/turbulent transition is practically indiscernible from the friction factor vs. Reynolds number plots, particularly for PAA and XG, the u′ level provides a very clear indicator and it is found that the transition delay follows much the same trend with elasticity/extensional viscosity as the drag reduction.     

Natural convection of a viscoelastic fluid

The influence of elasticity and shear thinning viscosity on the temperature distribution and heat transfer in natural thermal convection is discussed. The numerical investigations are based on a four-parameter Oldroyd constitutive equation, which represents the typical fluid response of dilute solutions and melts. It was found that especially the second normal-stress difference affects the heat transfer mechanism.     

On the relaxation of shear and normal stresses of viscoelastic fluids following constant shear rate experiments

By means of a cone and plate rheometer the relaxation of the shear stress and the first normal stress difference in polymer liquids upon cessation of a constant shear rate were examined. The experiments were conducted mostly in a high shear rate region of relevance for the processing of these materials. The relaxation behavior at these shear rates can only be measured accurately under extremely precise specifications of the rheometer. To determine under which conditions the integral normal thrust is a convenient measure for the relaxing local first normal stress difference the radial distribution of the pressure in the shear gap was measured. The shape of relaxation of both the shear stress and the first normal stress difference could be closely approximated for the entire measured shear rate and time range by a two parameter statistical function. In the range of measured shear rates, one of the parameters, the standard deviationS, is equal for the shear and the normal stress, and is independent of the shear rate within the limit of experimental error. The second parameter, the mean relaxation timet _50, of the shear stress andt _50, of the first normal stress difference, can be calculated approximately from the viscosity function and only a single relaxation experiment.     

Extensional rheology of concentrated poly(ethylene oxide) solutions

The shear and extensional rheology of three concentrated poly(ethylene oxide) solutions is examined. Shear theology including steady shear viscosity, normal stress difference and linear viscoelastic material functions all collapse onto master curves independent of concentration and temperature. Extensional flow experiments are performed in fiber spinning and opposed nozzles geometries. The concentration dependence of extensional behavior measured using both techniques is presented. The zero-shear viscosity and apparent extensional viscosities measured with both extensional rheometers exhibit a power law dependence with polymer concentration. Strain hardening in the fiber spinning device is found to be of similar magnitude for all test fluids, irrespective of strain rate. The opposed nozzle device measures an apparent extensional viscosity which is one order of magnitude smaller than the value determined with the fiber spinline device. This could be attributed to errors caused by shear, dynamic pressure, and the relatively small strains developed in the opposed nozzle device. This instrument cannot measure local kinematics or stresses, but averages these values over the non-homogenous flow field. These results show that it is not possible to measure the extensional viscosity of non-Newtonian and shear thinning fluids with this device. Fiber spin-line experiments are coupled with a momentum balance and constitutive model to predict stress growth and diameter profiles. A one-mode Giesekus model accurately captures the plateau values of steady and dynamic shear properties, but fails to capture the gradual shear thinning of viscosity. Giesekus model parameters determined from shear rheology are not capable of quantitatively predicting fiber spinline kinematics. However, model parameters fit to a single spinline experiment accurately predict stress growth behavior for different applied spinline tensions.     

Shear viscosity of slightly-elastic concentrated suspensions at low and high shear rates

A quasi-static asymptotic analysis is employed to investigate the elastic effects of fluids on the shear viscosity of highly concentrated suspensions at low and high shear rates. First a brief discussion is presented on the difference between a quasi-static analysis and the periodic-dynamic approach. The critical point is based on the different order-of-contact time between particles. By considering the motions between a particle withN near contact point particles in a two-dimensional “cell” structure and incorporating the concept of shear-dependent maximum packing fraction reveals the structural evolution of the suspension under shear and a newly asymptotic framework is devised. In order to separate the influence of different elastic mechanisms, the second-order Rivlin-Ericksen fluid assumption for describing normal-stress coefficients at low shear rates and Harnoy's constitutive equation for accounting for the stress relaxation mechanism at high shear rates are employed. The derived formulation shows that the relative shear viscosity is characterized by a recoverable shear strain,S _R at low shear rates if the second normal-stress difference can be neglected, and Deborah number,De, at high shear rates. The predicted values of the viscosities increase withS _R , but decrease withDe. The role ofS _R in the matrix is more pronounced than that ofDe. These tendencies are significant when the maximum packing fraction is considered to be shear-dependent. The results are consistent with that of Frankel and Acrivos in the case of a Newtonian suspension, except for when the different divergent threshhold is given as [1 ? (Φ/Φ _m )^1/2] ? 1.     

Selection of kernel functions used in a new constitutive equation for viscoelastic fluids

A selection of kernel functions is given to be used in a new integral constitutive equation proposed by Piau whereby the deviatoric stress is calculated from the integral of the history of the past intrinsic rate of rotation and rate of deformation tensors through a representation theorem. Piau has demonstrated the objectivity of a frame moving with a given particle whose axis are directed along the eigenvectors of the rate of deformation tensor. The use of such a framework provides a new approach in the attempt to reduce the computational difficulties associated with conventional constitutive equations written in co-deformational or co-rotational reference frames.The shear and primary normal-stress material functions and the extensional (elongational) stress growth function are defined for the proposed integral constitutive equation. These material functions are used to calculate the kernel functions using steady state, stress relaxation and stress growth data of Attané in simple shear flow for monodisperse polystyrene solutions. The shear and extensional stress growth data of Meissner for a polyethylene melt are also used to show the flexibility of the rheological model.The material functions are first written in terms of five monotonically decreasing functions of the time lag between the past and the present time. Then kernel functions are chosen such that when substituted in the new integral constitutive equation they yield the functions used to describe the data. A further condition imposed on the normalized kernel functions is that they be decreasing functions of time lag.     

Thermodynamic admissibility of the pompon model for branched polymers

The pompon model for branched polymers is re-formulated within a general framework of nonequilibrium thermodynamics. While the original model of McLeish and Larson is found to be thermodynamically admissible, nonequilibrium thermodynamics strongly suggests several model modifications. As an immediate consequence, a nonzero second normal-stress coefficient in shear flow is predicted by the modified pompon model. Received: 12 April 2000 Accepted: 11 September 2000