Experimental study on the capillary thinning of entangled polymer solutions

The transient elongation behavior of entangled polymer and wormlike micelles (WLM) solutions has been investigated using capillary breakup extensional rheometry (CaBER). The transient force ratio X = 0.713 reveals the existence of an intermediate Newtonian thinning region for polystyrene and WLM solutions prior to the viscoelastic thinning. The exponential decay of X(t) in the first period of thinning defines an elongational relaxation time λ _x which is equal to elongational relaxation time λ _e obtained from exponential diameter decay D(t) indicating that the initial stress decay is controlled by the same molecular relaxation process as the strain hardening observed in the terminal regime of filament thinning. Deviations in true and apparent elongational viscosity are discussed in terms of X(t). A minimum Trouton ratio is observed which decreases exponentially with increasing polymer concentration leveling off at Tr_min = 3 for the solutions exhibiting intermediate Newtonian thinning and Tr_min ≈ 10 otherwise. The relaxation time ratio λ _e/ λ _s, where λ _s is the terminal shear relaxation time, decreases exponentially with increasing polymer concentration and the data for all investigated solutions collapse onto a master curve irrespective of polymer molecular weight or solvent viscosity when plotted versus the reduced concentration c[ η], with [ η] being the intrinsic viscosity. This confirms the strong effect of the nonlinear deformation in CaBER experiments on entangled polymer solutions as suggested earlier. On the other hand, λ _e ≈λ _s is found for all WLM solutions clearly indicating that these nonlinear deformations do not affect the capillary thinning process of these living polymer systems.     

Capillary breakup extensional rheometry (CaBER) on semi-dilute and concentrated polyethyleneoxide (PEO) solutions

Semi-dilute ( $c^\ast < c < c_{\rm e}$ ) as well as concentrated, entangled (c?>?c _e) solutions of PEO yield uniformly thinning, cylindrical filaments in capillary breakup extensional rheometry (CaBER) experiments. Up to c?≈ c _e thinning can be characterized by a single elongational relaxation time λ _E. Comparison with the longest shear relaxation time, λ _S reveals that λ _E/λ _S decreases with increasing concentration or molecular weight according to (c[η])^???4/3. This is attributed to the large deformation the solutions experience during filament thinning. A factorable integral model including a single relaxation time and a Soskey or Wagner damping function accounting for the large deformation in CaBER experiments is used to calculate λ _E/λ _S and provides good agreement with experimental results. Irrespective of concentration or molecular weight a beads-on-a-string structure occurs prior to filament breakup at a diameter ratio D/D ₀?≈ 0.01. This instability is supposed to be closely related to a flow-induced phase separation.     

Shear and elongational flow behavior of acrylic thickener solutions

We investigate the effect of hydrophobic aggregation in alkali-swellable acrylic thickener solutions on shear and extensional flow properties at technically relevant polymer concentrations using the commercial thickener Sterocoll FD as model system. Apparent molecular weight of aggregates in water is M _w  ≈ 10⁸ g/mol and decreases by more than an order of magnitude in ethanol. Zero shear viscosity η ₀ is low and shear thinning is weak compared to the high molecular weight of the aggregates. Linear viscoelastic relaxation is described by the Zimm theory up to frequencies of 10⁴ rad/s, demonstrating that no entanglements are present in these solutions. This is further supported by the concentration dependence of η ₀ and is attributed to strong association within the aggregates. Extensional flow behavior is characterized using the capillary break-up extensional rheometry technique including high-speed imaging. Solutions with ϕ ≥ 1% undergo uniform deformation and show pronounced strain hardening up to large Hencky strains. Elongational relaxation times are more than one order of magnitude lower than the longest shear relaxation times, suggesting that aggregates cannot withstand strong flows and do not contribute to the elongational viscosity.

Time periodic electroosmotic flow of the generalized Maxwell fluids between two micro-parallel plates

Analytical solutions are presented using method of separation of variables for the time periodic EOF flow of linear viscoelastic fluids between micro-parallel plates. The linear viscoelastic fluids used here are described by the general Maxwell model. The solution involves analytically solving the linearized Poisson–Boltzmann equation, together with the Cauchy momentum equation and the general Maxwell constitutive equation. By numerical computations, the influences of the electrokinetic width K denoting the characteristic scale of half channel width to Debye length, the periodic EOF electric oscillating Reynolds number Re and normalized relaxation time λ₁ω on velocity profiles and volumetric flow rates are presented. Results show that for prescribed electrokinetic width K, lower oscillating Reynolds number Re and shorter relaxation time λ₁ω reduces the plug-like EOF velocity profile of Newtonian fluids. For given Reynolds number Re and electrokinetic width K, longer relaxation time λ₁ω leads to rapid oscillating EOF velocity profiles with increased amplitude. With the increase of the K, the velocity variations are restricted to a very narrow region close to the EDL for small relaxation time. However, with the increase of the relaxation time, the elasticity of the fluid becomes conspicuous and the velocity variations can be expanded to the whole flow field. As far as volume flow rates are concerned, for given electrodynamic width K, larger oscillating Reynolds number Re results in a smaller volume flow rates. For prescribed oscillating Reynolds number Re, with the changes of relaxation time λ₁ω, volume flow rates will produce some peaks no matter how the electrodynamic width K varies. Moreover, the time periodic evolution of the velocity profiles provides a detail insight of the flow characteristic of this flow configuration.     

Unsteady flows of Oldroyd-B fluids in a channel of rectangular cross-section

The aim of this note is to present the exact solutions corresponding to two types of unsteady flows of an Oldroyd-B fluid in a channel of rectangular cross-section. The solutions that have been obtained satisfy both the associate partial differential equations and all imposed initial and boundary conditions. For λ_r or λ→0 they tend toward similar solutions for a Maxwell or second-grade fluid. If both λ_r and λ→0, the solutions for Navier-Stokes fluids are recovered.     

Some exact solutions for rotating flows of a generalized Burgers’ fluid in cylindrical domains

The velocity field and the adequate shear stress corresponding to the flow of a generalized Burgers’ fluid model, between two infinite co-axial cylinders, are determined by means of Laplace and finite Hankel transforms. The motion is due to the inner cylinder that applies a time dependent torsional shear to the fluid. The solutions that have been obtained, presented in series form in terms of usual Bessel functions J₁( ? ), J₂( ? ), Y₁( ? ) and Y₂( ? ), satisfy all imposed initial and boundary conditions. Moreover, the corresponding solutions for Burgers’, Oldroyd-B, Maxwell, second grade, Newtonian fluids and large-time transient solutions for generalized Burgers’ fluid are also obtained as special cases of the present general solutions. The effect of various parameters on large-time and transient solutions of generalized Burgers’ fluid is also discussed. Furthermore, for small values of the material parameters, λ₂ and λ₄ or λ₁, λ₂, λ₃ and λ₄, the general solutions corresponding to generalized Burgers’ fluids are going to those for Oldroyd-B and Newtonian fluids, respectively. Finally, the influence of the pertinent parameters on the fluid motion, as well as a comparison between models, is shown by graphical illustrations.     

Boundary layer development on a continuous moving surface with a parallel free stream due to impulsive motion

The development of the momentum and thermal boundary layers over a semi-infinite flat plate has been studied when the external stream as well as the plate are impulsively moved with constant velocities. At the same time the temperature of the wall is suddenly raised from T_∞, the temperature of the surrounding fluid, toT _w and maintained at this temperature. The problem has been formulated in a new system of scaled coordinates such that fort?=0 it reduces to Rayleigh type of equation and fort? → ∞ it reduces to Blasius or Sakiadis type of equation. A new scale of time has been used which reduces the region of integration from an infinite region to a finite region which reduces the computational time considerably. The governing singular parabolic partial differential equations have been solved numerically using an implicit finite difference scheme. For some particular cases, analytical solutions have been obtained. The results show that there is a smooth transition from Rayleigh solution to Blasius or Sakiadis solution as the dimensionless timeξ increases from zero to one. The shear stress at the wall is negative for the friction parameterλ<0.5, positive forλ>0.5 and zero forλ=0.5. The zero shear stress at the wall does not imply separation but corresponds to the parallel flow. The surface heat transfer is strongly dependent on the Prandtl numberPr and increases with it. Also forPr<Pr ₀, the surface heat transfer is enhanced as the friction parameterλ increases, but forPr>Pr ₀ it get reduced.     

Steady and transient shear flows of polystyrene solutions I: Concentration and molecular weight dependence of non-dimensional viscometric functions

Start up from rest and relaxation from steady shear flow experiments have been performed on monodisperse polystyrene solutions with molecular weight ranging from 1.3 × 10⁵ to 1.6 × 10⁶ and concentration c ranging from 5% to 40%. A method of reduced variables based on the use of a characteristic time τ_w is proposed. τ_w is defined as the product of zero shear viscosity with the steady state elastic compliance.Reduced steady and transient viscometric functions so obtained depend on the ratio M/M_e (where M_e is the entanglement molecular weight). Limiting forms are obtained when M/M_e ? 18. In steady flow, a simple correlation is found between shear and normal stresses.In stress relaxation experiments, independent of shear rate, the long-time behaviour can be characterised by a single relaxation time τ₁, which is identical for shear and normal stresses. τ₁ can be simply related to the zero shear rate viscosity and the limiting elastic compliance.     

Measurement of extensional viscosity of polymer solutions

A filament stretching technique for measuring the extensional viscosity of polymer solutions at constant stretch rate is presented. The liquid sample is held between two coaxial discs and stretched by moving the bottom disc downwards with a speed that increases exponentially with time. This is illustrated using a constant viscosity, elastic fluid consisting of 0.185% polyisobutylene in a solvent of kerosene and polybutene. For the case of this particular fluid, two distinct stretch rate regions are found to arise. The stretch rate in the first region is much higher than in the second, which is, in most cases, close to the overall stretch rate imposed on the sample. Nonetheless, all the results of any given run can be represented using an average extensional rate. The extensional stress growth data, plotted as the Trouton ratio against time, show an initial linear viscoelastic region where T_R rises to a value of 3, independent of extensional rate. Beyond this region, T_R depends on the stretch rate and rises dramatically to values in excess of 10³; the higher the extensional rate, the faster is the increase in T_R. These data do not seem to reach a steady state and appear to be similar to polymer melt data obtained by others in the past. The reproducibility of the results is very good and all this suggests that it is now possible to obtain unambiguous constant-stretch-rate stress-growth data for polymer solutions stretched from a state of rest.     

Terminal velocities of clean and fully-contaminated drops in vertical pipes

Terminal velocities and shapes of drops rising through vertical pipes in clean and fully-contaminated systems are measured by using a high-speed video camera and an image processing method. Silicon oils and glycerol water solutions are used for the dispersed and continuous phases, respectively. Triton X-100 is used for surfactant. Clean and contaminated drops take either spherical, spheroidal or deformed spheroidal shapes when the diameter ratio λ is less than a critical value, λ_C, whereas they take bullet shapes for λ > λ_C (Taylor drops). The applicability of available drag and Froude number correlations is examined through comparisons with the measured data. Effects of surfactant on the shape and terminal velocity of a Taylor drop are also discussed based on the experimental data and interface tracking simulations. The conclusions obtained are as follows: (1) drag and Froude number correlations proposed so far give reasonable estimations of the terminal velocities of clean drops at any λ, (2) the terminal velocities of contaminated drops are well evaluated by making the viscosity ratio μ^* infinity in the drag correlation for clean drops in the viscous force dominant regime, (3) the effects of surfactant on the shape and terminal velocity of a Taylor drop become significant as the Eötvös number, Eo_D, decreases and μ^* increases, and (4) the reduction in surface tension due to the addition of surfactant would be the cause of the increase in the terminal velocity and elongation of a contaminated Taylor drop.     

Kinetic modeling of particles in stratified flow – Evaluation of dispersion tensors in inhomogeneous turbulence

The continuum equations for a dilute particle distribution in inhomogeneous turbulence are tested against results from a Langevin particle tracking simulation. Reeks’ version of the kinetic theory is used to generate the mass, momentum and kinetic stress equations for the particle distribution. The particle tracking data are used to directly evaluate the dispersion tensors λ and μ which serve as closure relations for the continuum equations. These exact forms are compared to approximate, local forms. Even for low Stokes numbers (corresponding to low particle inertia defined by τ/τ_p ? 1), the tensor λ is strongly affected by the inhomogeneity and depends on turbulence parameters in the volume corresponding to the particle path dispersion over the particle Lagrangian integral timescale τ. In contrast, the locally homogeneous form of the velocity dispersion tensor μ is a sufficient approximation, since it depends on the dispersion volume over the much smaller particle relaxation time τ_p. It is demonstrated that the body force due to the dispersion vector γ cannot be neglected. In the limit of passive tracers (zero stopping distance), γ is equal to the gradient of λ, if the physical setting is such that we can invoke constant tracer density in this limit.     

A simple method of evaluating the complex moduli of polystyrene blends

In the search for a workable mixing rule, use was made of experimental data for complex moduli of melts of narrow molar mass distribution polystyrenes and their homogeneous blends. In the course of this work two basic observations were made as to the nature of the relaxation time spectra of these blends:

1. The relaxation strength (a product of the weight fraction and the plateau modulus) of a component of large molecules is reduced by the presence of shorter molecules, the latter molecules acting like ordinary diluent molecules even if their molar masses are larger thenM _c .
2. The relaxation time of a molecule (known from measurements on the respective monodisperse component) is considerably changed by the blending. The width of the distribution of relaxation times, as expected from the known composition of the blend, is significantly reduced.

For both processes approximate empirical equations could be found. It turned out that, after the application of the required modifications, the complex moduli of the components could successfully be added in order to obtain the complex moduli of the blend at circular frequencies characteristic for the flow and rubber transition regions. On the basis of these results one may expect that for the melt of any linear polymer the linear viscoelastic properties can be evaluated with reasonable accuracy from the knowledge of the molar mass distribution.     

Exact solutions for the flow of a generalized Oldroyd-B fluid induced by a constantly accelerating plate between two side walls perpendicular to the plate

The unsteady flow of an incompressible generalized Oldroyd-B fluid induced by a constantly accelerating plate between two side walls perpendicular to the plate has been studied using Fourier sine and Laplace transforms. The obtained solutions for the velocity field and shear stresses, written in terms of the generalized G and R functions, are presented as sum of the similar Newtonian solutions and the corresponding non-Newtonian contributions. For α = β = 1 and λ_r → λ these solutions are going to the corresponding Newtonian solutions. Furthermore, the solutions for generalized Maxwell fluids as well as those for ordinary Oldroyd-B and Maxwell fluids, performing the same motion, are also obtained as limiting cases of our general solutions. In the absence of the side walls, namely when the distance between the two walls tends to infinity, the solutions corresponding to the motion over an infinite constantly accelerating plate are recovered. For λ_r → 0 and β → 1, these solutions reduce to the known solutions from the literature. Finally, the effect of the material parameters on the velocity profile is spotlighted by means of the graphical illustrations.     

Numerical simulation of entry flow of the IUPAC-LDPE melt

Numerical simulations have been undertaken for the creeping entry flow of a well-characterized polymer melt (IUPAC-LDPE) in a 4:1 axisymmetric and a 14:1 planar contraction. The fluid has been modeled using an integral constitutive equation of the K-BKZ type with a spectrum of relaxation times (Papanastasiou–Scriven–Macosko or PSM model). Numerical values for the constants appearing in the equation have been obtained from fitting shear viscosity and normal stress data as measured in shear and elongational data from uniaxial elongation experiments. The numerical solutions show that in the axisymmetric contraction the vortex in the reservoir first increases with increasing flow rate (or apparent shear rate), goes through a maximum and then decreases following the behavior of the uniaxial elongational viscosity. For the planar contraction, the vortex diminishes monotonically with increasing flow rate following the planar extensional viscosity. This kinematic behavior is not in agreement with recent experiments. The PSM strain-memory function of the model is then modified to account for strain-hardening in planar extension. Then the vortex pattern shows an increase in both axisymmetric and planar flows. The results for planar flow are compared with recent experiments showing the correct trend.     

Mixed convection boundary layer flow past a wedge with permeable walls

The effects of suction/injection on steady laminar mixed convection boundary layer flow over a permeable horizontal surface of a wedge in a viscous and incompressible fluid is considered in this paper. The similarity solutions of the governing boundary layer equations are obtained for some values of the suction/injection parameter f ₀, the constant exponent m of the wall temperature as well as the mixed convection parameter λ. The resulting system of nonlinear ordinary differential equations is solved numerically for both assisting and opposing flow regimes using an implicit finite-difference scheme known as the Keller-box method. Numerical results for the reduced skin friction coefficient, the local Nusselt number, and the velocity and temperature profiles are obtained for various values of parameters considered. Dual solutions are found to exist for the case of opposing flow.     

Rheological characterization of commercial highly viscous alginate solutions in shear and extensional flows

The rheological properties of sodium alginate in salt-free solutions were studied by steady shear, dynamic oscillatory and extensional measurements. This biopolymer consists of mannuronic and guluronic acid residues that give a polyelectrolyte character. We applied the scaling theories and checked their accordance with polyelectrolyte behaviour for low concentrations with a shift to neutral polymer behaviour at larger concentrations. This nature was supported by the effect of the concentration on the specific viscosity, the relaxation times from steady shear and the longest relaxation times from small amplitude oscillatory shear (SAOS) measurements. To analyze the extensional behaviour of the samples, we conducted a study of dimensionless numbers and time scales where filament thinning driven by viscous, capillary or elastic forces is at play. We conclude that an exponential filament thinning followed by breakup results in the best regimes that describe the experimental data. Besides, the data pointed out that alginate in salt-free concentrated solutions shows strain thinning of the extensional viscosity and chain rigidity, behaviours that cannot be inferred from the shear rheometry.     

Mesoscopic dynamics of polymer chains in high strain rate extensional flows

We take a step towards accessing the physics of viscoelastic liquid breakup in high speed, high strain rate flows by performing Brownian dynamics computations of dilute uniaxial, equibiaxial, and ellipsoidal polymeric extensional flows. Our computational implementation of the bead-spring model, when tailored to the DNA molecule, consistently with recent works of Larson and co-workers, is shown: (a) to predict a coil-stretch transition at Deborah number De≈0.5, and (b) to reproduce the experimental longest relaxation time. Furthermore, after adapting the model parameters to represent the polyethylene oxide (PEO) chain (for M=10⁶ Da), we find it possible to reproduce our own experimental data of the longest relaxation time, the transient extensional viscosity of dilute solutions at small Deborah numbers, and a coil-stretch transition at Deborah number De≈0.5. Extended to large Deborah numbers, the model predicts that polymer stretching is controlled by: (a) the randomness of the initial conditions that, in combination with rapid kinematically imposed compression, lead to the formation of initially frozen chain-folds, and (b) the speed with which thermo-kinematic processes relax these folds. The slowest fold relaxation occurs during uniaxial extension. As expected, the introduction of stretching along a second direction enhances the efficiency of fold relaxation mechanisms. Even for Deborah numbers (based on the chain longest relaxation time) of the order of one thousand, there is a large variation in the time a polymer needs in order to extend fully, and the effects of Brownian motion cannot be ignored. The computed Trouton ratios and polymer contributions to the total stress as functions of Hencky strain provide information about the relative importance of elastic effects during polymeric liquid stretching. At high strain rates, the steady state elastic stresses increase linearly with the Deborah number, resembling at that stage an anisotropic Newtonian fluid (constant extensional viscosity).     

Improved modal truncation method for eigensensitivity analysis of asymmetric matrix with repeated eigenvalues

An improved modal truncation method with arbitrarily high order accuracy is developed for calculating the second- and third-order eigenvalue derivatives and the first- and second-order eigenvector derivatives of an asymmetric and non-defective matrix with repeated eigenvalues. If the different eigenvalues λ1, λ2,, λrof the matrix satisfy |λ1| |λr| and |λs| |λs+1|(s r-1), then associated with any eigenvalue λi(i s), the errors of the eigenvalue and eigenvector derivatives obtained by the qth-order approximate method are proportional to |λi/λs+1|q+1, where the approximate method only uses the eigenpairs corresponding to λ1, λ2,, λs. A numerical example shows the validity of the approximate method. The numerical example also shows that in order to get the approximate solutions with the same order accuracy, a higher order method should be used for higher order eigenvalue and eigenvector derivatives.     

Temperature solutions due to time-dependent moving-line-heat sources

A closed-form model for the computation of temperature distribution in an infinitely extended isotropic body with a time-dependent moving-line-heat sources is discussed. The temperature solutions are presented for the sources of the forms: (i) $\dot Q_1 (t) = \dot Q_0 \exp ( - \lambda t)$ , (ii) $\dot Q_2 (t) = \dot Q_0 (t/t^ \star )\exp ( - \lambda t)$ , and $\dot Q_3 (t) = \dot Q_0 [1 + a\cos (\omega t)]$ , whereλ andω are real parameters andt? characterizes the limiting time. The reduced (or dimensionless) temperature solutions are presented in terms of the generalized representation of an incomplete gamma function Γ (α,x;b) and its decompositionsC _Γ andS _Γ. It is also demonstrated that the present analysis covers the classical temperature solution of a constant strength source under quasi-steady-state situations.     

Solution bounds of a new complex PMSM system

This paper has investigated the boundedness of solutions of a complex permanent magnet synchronous motor system. We have obtained the globally exponentially attractive set Ψ _λ,m and the ultimate bound Ω _λ,m for this system. Furthermore, we can conclude that the rate of the trajectories of the system going from the exterior of the set Ψ _λ,m to the interior of the set Ψ _λ,m is exponential. The estimate of the trajectories rate is also obtained. Numerical simulations are presented to show the effectiveness of the proposed scheme.