Relationships between linear and nonlinear shear response of polymer nano-composites

Rheological analysis was used to understand the structure?Cproperty relations of polymer nano-composites based on ethylene vinyl acetate. Two geometrically different nano-particles (sphere of CaCO₃ and platelet of montmorillonite) having the same energetic attractions with ethylene vinyl acetate were studied for concentrations between 2.5 and 15 wt%. Three phenomena were studied: the appearance of a solid-like behavior in the linear viscoelastic domain, the limits of linear viscoelasticity, and the presence of stress overshoot in step shear tests. In particular, stress overshoot was investigated based on the tube concept of polymeric chains. Also, differences related to nano-particle geometry (platelet vs. spherical) were investigated based on a filler-network mechanism. Due to higher physical contacting probability, platelet particles can better interact and create a network structure, which dominates the rheological response. On the other hand, although spherical particles can limit the motion of polymeric chains under flow, a strong physical network was not formed. For platelets, scaling behavior was well described by fractal model which considers direct aggregation, and such scaling was not observed for spherical particles. The filler-network mechanism was validated by image analysis.     

The effect of step-stretch parameters on capillary breakup extensional rheology (CaBER) measurements

Extensional rheometry has only recently been developed into a commercially available tool with the introduction of the capillary breakup extensional rheometer (CaBER). CaBER is currently being used to measure the transient extensional viscosity evolution of mid to low-viscosity viscoelastic fluids. The elegance of capillary breakup extensional experiments lies in the simplicity of the procedure. An initial step-stretch is applied to generate a fluid filament. What follows is a self-driven uniaxial extensional flow in which surface tension is balanced by the extensional stresses resulting from the capillary thinning of the liquid bridge. In this paper, we describe the results from a series of experiments in which the step-stretch parameters of final length, and the extension rate of the stretch were varied and their effects on the measured extensional viscosity and extensional relaxation time were recorded. To focus on the parameter effects, well-characterized surfactant wormlike micelle solutions, polymer solutions, and immiscible polymer blends were used to include a range of characteristic relaxation times and morphologies. Our experimental results demonstrate a strong dependence of extensional rheology on step-stretch conditions for both wormlike micelle solutions and immiscible polymer blends. Both the extensional viscosity and extensional relaxation time of the wormlike micelle solutions were found to decrease with increasing extension rate and strain of the step-stretch. For the case of the immiscible polymer blends, fast step-stretches were found to result in droplet deformation and an overshoot in the extensional viscosity which increased with increasing strain rates. Conversely, the polymer solutions tested were found to be insensitive to step-stretch parameters. In addition, numerical simulations were performed using the appropriate constitutive models to assist in both the interpretation of the CaBER results and the optimization of the experimental protocol. From our results, it is clear that any rheological results obtained using the CaBER technique must be properly considered in the context of the stretch parameters and the effects that preconditioning has on viscoelastic fluids.     

A rheological criterion to determine the percolation threshold in polymer nano-composites

In this work, the effect of multi-walled carbon nanotube (CNT) and montmorillonite nanoclay on polymer chain dynamics is investigated around the percolation concentration for systems based on ethylene vinyl acetate (EVA) copolymer. Then, the results obtained are compared with literature data to determine if, regardless of particle characteristics, a universal rheological behavior can be detected at percolation. To do so, rheological analyses are performed under small amplitude oscillatory shear (SAOS), large amplitude oscillatory shear (LAOS), and transient shear step. SAOS data showed that, while the dynamics related to the Rouse relaxation time (τ _R) were not significantly influenced, the reptation relaxation time (τ _D) was strongly increased by the presence of nanoparticles. In step shear transient tests, the critical shear rate \( \left({\dot{\upgamma}}_{\mathrm{cr}}\right) \) for overshoot appearance was decreased due to chain confinement, and the formation of particle network strongly increased the level of stress overshoot. Particle networks increased significantly the nonlinear parameters (I ₃/I ₁ and Q ₀) obtained under LAOS and quantified by FT-rheology. In all measurements, due to the higher surface area associated to its size and density as well as hollow structure, CNT showed stronger effects compared to clay. Moreover, while the percolation concentration was different for CNT and clay, both systems showed similar behavior at percolation: a 0.5 scaling for G′ indicating a Rouse-dominated behavior.     

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.     

Suspensions of monodisperse spheres in polymer melts: particle size effects in extensional flow

Suspensions in polymeric, viscoelastic liquids have been studied in uniaxial extensional flow. The fibre wind-up technique has been used for this purpose. The effects of particle size and particle volume fraction have been investigated, using monodisperse, spherical particles. The results have been compared with shear flow data on the same materials. The values of the relative extensional viscosities at low stretching rates are in agreement with the relative shear viscosities and relative moduli. This indicates that hydrodynamic forces are stronger than the particle interaction forces. At larger strain rates strain hardening occurs; it is suppressed when particles are added. Small aggregating particles reduce the strain hardening more strongly than larger particles; strain hardening can even be totally eliminated. When further increasing the stretching rate, hydrodynamic effects dominate again and the effect of particle size effect on strain hardening disappears.     

Effect of vinyl acetate content and silicate loading on EVA nanocomposites under shear and extensional flow

In this study, three EVAs (ethylene-vinyl acetate co-polymers) with different vinyl contents (VA) ranging from 9 wt% to 28 wt% (EVA9, EVA18 and EVA28) were melt blended with organo-clay to obtain polymer layered silicate nanocomposites. Filler intercalation and exfoliation were evidenced by X-ray diffraction. The melt state viscoelastic properties of EVA nanocomposites were studied to examine the influence of clay in altering the flow properties of these polymeric nanocomposites. The EVA18 and EVA28 nanocomposites exhibited remarkable difference in dynamic and steady shear properties compared to neat polymers. On the other hand, EVA9-5% nanocomposite did not exfoliate and exhibited rheological behaviour very similar to that of the neat polymer. Furthermore, the first normal stress difference was found to be dependent on the silicate loadings when measured at low shear stresses. The uniaxial extensional viscosity measurement indicated that the strain hardening was weaker in EVA nanocomposites compared to neat polymers. Environmental scanning electron (ESE)-microscopy elucidated a possible reason for reduced strain hardening in these systems.     

Rheological predictions of a transversely isotropic fluid model with extensible microstructure

A continuum extensible director theory was formulated to describe the isothermal, incompressible flow of uniaxial rodlike semiflexible liquid crystalline polymers. The model is strictly restricted to material that flow-align in shear, and that, in the absence of flow, are sufficiently far from the nematic-isotropic phase transition. The microstructure of the continuum is described by a variable length director, but the extensibility is finite. The model is an extension of the TIF (Transversely Isotropic Fluid) model of Ericksen (1960). The thermodynamic restrictions on the model parameters are found using the non-negative definiteness of the entropy production. The rheological material functions predicted by the model are calculated for steady simple shear and steady uniaxial extensional flows. In the rigid rod limit the model predictions agree with those of the TIF model, and for the finite extensibility case the model predictions are in agreement with those associated with flexible isotropic polymers: strong non-Newtonian shear viscosity, positive first normal stress differences, recoverable shear of order one, negative second normal stress differences, and a maximum in the steady uniaxial extensional viscosity.     

Smoothed particle hydrodynamics techniques for the solution of kinetic theory problems: Part 2. The effect of flow perturbations on the simple shear behavior of LCPs

The effect of slight perturbations to simple shear flow of liquid-crystalline polymers (LCPs) is explored by using the SPH technique to solve the unapproximated orientation distribution function equation arising from the Doi Theory. First, the case of simple shear flow is outlined, and it is shown that skewed distributions play an important role in the transition from periodic to steady behavior as the shear rate is increased. Next, we consider perturbations to flows that are slightly more extensional than simple shear, parametrized by the flow type parameter α. They are shown to eliminate all periodic director behavior (tumbling and wagging), even when the relative increment in flow type is small. At lower shear rates (or more properly, lower Peclet number Pe based upon the rotational diffusivity), the elimination occurs through a homoclinic bifurcation, the transition being rather abrupt as the flow type is changed. At higher Pe, periodic behavior is suppressed more gradually through a Hopf bifurcation, with tumbling being replaced by wagging and negative θ flow-aligning, where θ is the angle of the director in the shear plane. The effect of these perturbations on rheological behavior is also explored. As the flow is made slightly more extensional, the zero-shear rate limiting value of the generalized viscosity η decreases dramatically, due to the slowing down of tumbling as the system approaches a homoclinic orbit; as Pe is increased, the viscosity rises again before falling, due to the induction of wagging behavior where tumbling would normally prevail in simple shear. Finally, it is found when the flow type is changed sufficiently, the interesting, non-monotonic behavior of rheological functions seen in simple shear of LCPs is replaced by monotonic behavior, even though the flow is still relatively close to simple shear.     

Large-deformation properties of wheat dough in uni- and biaxial extension. Part I. Flour dough

Rheological and fracture properties of optimally mixed flour doughs from three wheat cultivars which perform differently in cereal products were studied in uniaxial and biaxial extension. Doughs were also tested in small angle sinusoidal oscillation. In accordance with previously published results the linear region was found to be very small. The rheological properties at small deformations hardly depended on the cultivar. A higher water content of the dough resulted in a lower value for the storage modulus and a slightly higher value for tan . For both uniaxial and biaxial extension a more than proportional increase in stress was found with increasing strain, a phenomenon called strain hardening. In uniaxial extension (i) stresses at a certain strain were higher and (ii) the stress was less dependent on the strain rate than in biaxial extension. This indicates that in elongational flow orientational effects are of large importance for the mechanical properties of flour dough. This conclusion is consistent with published data on birefringence of stretched gluten. Fracture stress and strain increased with increasing deformation rate. The observed time-dependency of fracture properties can best be explained by inefficient transport of energy to the crack tip. Presumably, this is caused by energy dissipation due to inhomogeneous deformation because of friction between structural elements, e.g. between dispersed particles and the network. Differences in the rheological properties at large deformations between the cultivars were observed with respect to (i) stress, (ii) strain hardening, (iii) strain rate dependency of the stress, (iv) fracture properties and (v) the stress difference between uniaxial and biaxial extension.     

The effect of pre-shear on the extensional rheology of wormlike micelle solutions

The effect of initial microstructural deformation, alignment, and morphology on the response of wormlike micelle solutions in transient uniaxial extensional flows is investigated using a pre-shear device attached to a filament stretching rheometer. In filament stretching experiments, increasing the strength and the duration of the pre-shear just before stretch is found to delay the onset of strain hardening. In these experiments, the wormlike micelle solution filaments fail through a rupture near the axial midplane. The value of the elastic tensile stress at rupture is found to decrease with increasing pre-shear rate and duration. The most dramatic effects are observed at shear rates for which shear banding has been independently observed. The reduction in the strain hardening suggests that pre-shear before filament stretching might break down the wormlike micelles reducing their size before stretch. Strain hardening is also observed in capillary breakup rheometry experiments; however, the pre-sheared wormlike micelle solutions strain harden faster, achieve larger steady-state extensional viscosities and an increase in the extensional relaxation time with increasing shear rate and duration. The difference between the response of the wormlike micelles in filament stretching and capillary breakup experiments demonstrates the sensitivity of these self-assembling micelle networks to pre-conditioning.     

Constitutive equations for polymer fluids based on the concept of configuration-dependent molecular mobility: a generalized mean-configuration model

After a brief outline of the concept of configuration-dependent molecular mobility for the particular case of the one-mode mean-configuration theory, a generalized model is introduced in which the dependence of the mobility tensor on the configuration tensor is given by a relaxation-type functional. This model is analysed for steady and transient extensional and shear flows. In extensional flow it predicts a maximum in the steady-state uniaxial viscosity curves and stress overshoot in the stressing curves, and in shear flow it predicts even larger stress overshoot in the stressing curves. This model bridges the gap between the current molecular models and the most elaborate network models. In an appendix it is shown that for the relaxation-type dependence of the mobility it is only by using the upper Oldroyd derivative that physically acceptable results are predicted.     

Extensional flow behavior of polymer solutions and particle suspensions in a spinning motion

Mechanical spinning of fluid filaments was used to generate an extensional flow, in which rheological measurements were obtained for a Newtonian fluid, two aqueous polymer solutions, and two fluid suspensions of rod-shaped particles. The tensile stress was determined by measuring the tensile force of the fluid filament while the kinematics were determined from photographic measurement of the filament profile and the assumption of a flat velocity profile. The measured tensile stresses for the Newtonian fluid matched predicted stresses, thereby confirming the validity of the experimental technique.The spinning behavior of each polymer solution could be correlated as stress versus extension rate. The apparent “spinning viscosity” increased with increasing rate of extension, in contrast to shear-thinning behavior in viscometric flow. For the fluid suspensions, the presence of rod-shaped particles increased the apparent viscosity far more in extensional flow than in shear. Tensile stresses calculated from a theoretical formula for suspensions proposed by Batchelor agreed rather well with experiment. Some general criteria for the interpretation of the spinning experiment are proposed, and some microrheological implications of the present findings are discussed.     

The relevance of entry flow measurements for the estimation of extensional viscosity of polymer melts

The extensional viscosity of some flexible chain polymers and a thermotropic liquid crystalline polymer was measured in uniaxial extensional flow at constant extension rate. Power law functions were found for the dependence of the extensional viscosity at constant accumulated strain on strain rate. The stress growth curves were compared with measurements in axisymmetric entry flow, where both elongation and shear occur. The comparison showed that the values of the extensional viscosity calculated from the measurements in the entry flow correspond to the ones calculated from the viscosity growth measured in uniaxial elongation and averaged over extensional strain equal to what is accumulated on the fluid as it flows from the barrel into the capillary.     

Dehnviskosität von Kautschukmischungen

It is shown that the extensional viscosity measured by uniaxial stretch may give useful information as to the processability of rubber compounds. A simple apparatus was constructed to measure this rheological property at constant rate of strain. The influence of rubber type, filler, aging, mastication and degree of crosslinking on the reduced stress is represented by diagrams. No steady-state extensional viscosity was obtained for highly filled rubber compounds. It was found that the flow behaviour of rubber compounds can be better characterized with an extensional rheometer than with a high-pressure capillary rheometer.

     

On the “viscosity overshoot” during the uniaxial extension of a low density polyethylene

An experimental investigation of the viscosity overshoot phenomenon observed during uniaxial extension of a low density polyethylene is presented. For this purpose, traditional integral viscosity measurements on a Münstedt-type extensional rheometer are combined with local measurements based on the in-situ visualization of the sample under extension. For elongational experiments at constant strain rates within a wide range of Weissenberg numbers (Wi), three distinct deformation regimes are identified. Corresponding to low values of Wi (regime I), the tensile stress displays a broad maximum, but such maximum is observed with various polymeric materials deformed at low rates and it should not be confused with the “viscosity overshoot” phenomenon. Corresponding to intermediate values of Wi (regime II), a local maximum of the integral extensional viscosity is systematically observed. Moreover, within this regime, a strong discrepancy between integral measurements and the space average of the local elongational viscosity is observed which indicates large deviations from an ideal uniaxial deformation process. Images of samples within this regime reinforce this finding by showing that, corresponding to the maximum of the integral viscosity, secondary necks develop along the sample. The emergence of a maximum of the integral elongational viscosity is, thus, related to the distinct inhomogeneity of deformation states and most probably not to the rheological properties of the material. In the fast stretching limit (high Wi, regime III), the overall geometric uniformity of the sample is well preserved, no secondary necks are observed and both the integral and the space averaged transient elongational viscosity show no maximum. A detailed but yet incomplete comparison of the experimental findings with results from the literature is presented and several open questions are stated.     

Uniaxial extensional flow behavior of immiscible and compatibilized polypropylene/liquid crystalline polymer blends

In this work liquid crystalline polymer (LCP) and thermoplastic (TP) blends with and without compatibilizer were studied with respect to their elongational flow behavior, under uniaxial extensional flow. This knowledge is important because in processes involving dominantly extensional deformations, like the case of the formation of the LCP fibrillation, transient extensional flow properties become more important than transient or steady-shear properties. In systems characterized by disperse phase morphologies (10 and 20 wt%) the LCP acts as a plasticizer, decreasing the viscosity of the system and increasing its durability with respect to that of the matrix. On the other hand, for a system in which a co-continuous morphology is present (40 wt% LCP) fibrils and droplets deformation occurs simultaneously, leading to a much higher strain hardening and durability. Moreover, the addition of compatibilizers to the blends gives rise to an increase of the strain hardening and to a decrease of the durability, which is in accordance with the mechanical properties, namely a higher Young’s modulus and lower elongation at break, in comparison with noncompatibilized systems.     

The effects of salts on the rheological characteristics of a drag-reducing cationic surfactant solution with shear-induced micellar structures

The effect of the counterion salt sodium salicylate (Nasal) on the transient rheological properties of a drag-reducing surfactant system tris (2-hydroxyethyl) tallowalkyl ammonium acetate (TTAA) has been studied with both rheometric and rheo-optical methods. Three types of transient behavior for N₁ and viscosity were identified in 5 mM TTAA solutions depending on the counterion concentration: induction and growth (below equimolar concentration); overshoot and growth (above equimolar concentration); and overshoot then plateau (at high concentrations of Nasal). The transient flow birefringence and orientation angle show trends similar to those of the viscosity and N₁. The second type of transient behavior suggests a two-stage alignment and shear thickening process. The SIS buildup time from the quiescent state, the rebuilding time after a strong preshear, and the relaxation time were also obtained from N₁ measurements, and show a maximum around equimolar conditions. The initial N₁ and viscosity immediately after the flow startup, on the other hand, show a maximum around a ratio of 2.5 to 3 Nasal/TTAA. For solutions with a Nasal concentration in the ratio 1.5 to 3, the steady state values of N₁ and viscosity do not show much variation with Nasal concentration over the shear rate range covered, however. The effect of an addition of sodium chloride (NaCI) to an equimolar Nasal/TTAA solution on the characteristic times and steady state values was also quantified. These rheological results provide us with tools to determine the optimal concentration ratio for practical drag reduction applications.     

Extensional behavior influence on viscoelastic turbulent channel flow

In this work we use in the simulation of a viscoelastic turbulent channel flow a modification of the finitely extensible of non-linear elastic dumbbells with the Peterlin approximation (FENE-P) constitutive model for dilute polymer solutions, applicable to high extensional deformations. The new feature introduced by this modification is that the free energy of the polymer (since it is assumed to be entirely entropically driven) remains always bounded (FENE-PB). The characteristics of the model under steady shear flow, pure elongational flow and transient extensional behavior are presented. It is found that the FENE-PB model is more shear thinning than FENE-P. Most importantly, it also shows a higher extensional viscosity than the FENE-P model. Although the steady-state Trouton ratio asymptotically reaches at high extensional rates the same limit as the FENE-P model, the transition from the Newtonian value is sharper and faster. We use the FENE-PB model in direct numerical simulations (DNS) of viscoelastic turbulent channel flow using spectral approximations. The results for various statistics of the flow and the polymer conformation, when compared against those obtained with the original FENE-P model and the same rheological parameters, show an enhanced polymer-induced drag reduction effect and enhanced deformation of the polymer molecules. This indicates that it is not only the asymptotic but also details from the extensional rheological behavior that matter in quantitatively specifying turbulent viscoelastic flow behavior.     

Rheological behaviour of nano-composites based on polyamide 6 under shear and elongational flow at high strain rates

In this work, the rheological behaviour of high molecular mass polyamide 6 (PA6)/organo-montmorillonite nano-composites, obtained via melt blending, was investigated under shear and extensional flow. Capillary rheometry was used for the measurement of high shear rate steady state shear viscosity and die entrance pressure losses; further, by the application of a converging flow method (Cogswell model) to these experimental results, elongational viscosity data were indirectly calculated. The extensional behaviour was directly investigated by means of melt spinning experiments, and data of apparent elongational viscosity were determined. The results evidenced that the presence of the organo-clay in filled PA6 melts modifies the rheological behaviour of the material, with respect to the unfilled polymer, in dependence on the type of flow experienced by the fluid. In shear flow, the nano-composites showed a slightly lower viscosity than neat PA6, whereas in elongation, they appeared much more viscous, in dependence on the organo-clay content.