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.     

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.     

Extensional viscosity in uniaxial extension and contraction flow—Comparison of experimental methods and application of the molecular stress function model

Extensional viscosity of a low-density polyethylene was measured at three temperatures in uniaxial extension by Sentmanat Extension Rheometer, and in contraction flow using the Cogswell analysis. The molecular stress function model was applied to describe the experimental results. The achieved maximum values from uniaxial transient tests were in accordance with the ones obtained by Cogswell method at similar strain level, and the molecular stress function model was able to describe the experimental transient uniaxial extensional data. The steady-state extensional viscosity was not reached in the experiments.     

Strain hardening behavior of polymer blends with fibril morphology

We investigate the rheological behavior of the polymer blends with fibril morphology, with special focus on the effect of fibril morphology on the extensional properties under uniaxial extension. We add a small amount of the dispersed phase to the matrix, and control the blend morphology by changing the viscosity ratio. When the fibril morphology is maintained, the blend shows not only a significant increase of the extensional viscosity but the strain hardening behavior. The extensional viscosity increases depending on the aspect ratio of the fibers, while the strain hardening behavior originates from the restricted stretching of deformable fibers, which has been confirmed theoretically by introducing the concept of rigidity of the fiber. It suggests a way to induce the strain hardening behavior by introducing deformable fibrils into the matrix, that is, by the design of polymer blends with a small amount of dispersed phase such that the fibril structure is maintained.     

Step planar extension of polymer melts using a lubricated channel

A technique to do step planar extension on polymer melts has been developed using a rectangular channel with lubricated walls and the linear motor of the Rheometrics System Four rheometer. Using this method we probe the stress relaxation of two polymer melts, a linear low density polyethylene (LLDPE) and a highly branched low density polyethylene (IUPAC X), and compare the step planar extensional data to step shear data. Since a step planar deformation is theoretically equivalent to a step shear in a rotating frame of reference, we expect that the nonlinear modulus for step planar extension should be equivalent to that for step shear. Although we find the time dependence of the stress relaxation modulus to be the same in both shear and planar extension, the strain dependence is surprisingly different for the two experiments.     

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.     

Numerical simulation studies of the planar entry flow of polymer melts

This paper is concerned with the numerical simulation of planar entry flow using a penalty finite element method and the comparison of predictions with flow visualization and birefringence data for two polymer melts. The Phan-Thien Tanner (PTT) model was fit to the steady state shear and extensional viscosity data and the transient extensional viscosity data of both polystyrene and low-density polyethylene (LDPE) melts to obtain the parameters λ, ξ, and ϵ in this model. Agreement was found between the flow visualization and birefringence data and the predictions of streamlines and stress. With some modification of the constitutive equation, the vortex growth and intensity observed for LDPE could be predicted by the use of the PTT model and the material parameters fit to the rheological properties. Likewise, the flow behavior of polystyrene, in which only small vortices with no growth were observed, was also predicted. Furthermore, it was found that the size and intensity of the vortex could be affected by the parameter ϵ in the PTT model which controls the predictions of the extensional viscosity. Based on these results it seems that accurate simulation of entry flow behavior requires the use of a constitutive equation which is capable of giving realistic preciction's of a fluid's extentional flow properties.     

Rheological properties of long glass fiber filled polypropylene

Long glass fiber-filled polypropylene (PP) composites are produced by pultrusion, and the extrudate is cut at different lengths producing composites containing long fibers of controlled length. The rheological properties of such composites in the molten state have been studied using different rheometers. A capillary rheometer has been constructed and mounted on a molding-injection machine. The shear viscosity of filled PP determined from the capillary rheometer, after corrections for entrance effects, was found to be very close to that of unfilled PP. However, large excess pressure losses at the capillary entrance were observed and these data have been used to obtain an apparent elongational viscosity. The apparent elongational viscosity was shown to be considerably larger than the shear viscosity for PP and filled PP, and it increased markedly with fiber length and fiber content. Rotational rheometers with a parallel-plate geometry were used to investigate the viscoelastic properties of these composites and their behavior was found to be non-linear, exhibiting a yield stress. A model is proposed to describe the shear viscosity from a solid-like behavior at low stresses to fluid-like behavior at high shear stresses taking into account fiber content and orientation. A modified model, proposed for elongational flow, describes relatively well the apparent elongational data.     

The role of solution structure in apparent thickening behavior of dilute peo/water systems

An experimental investigation was undertaken to determine the role of solution structure on the apparent thickening exhibited by “dilute” polyethylene oxide/water solutions in extensional flow. Measurements of apparent relative viscosity were obtained as a function of wall shear rate for solutions flowing from a reservoir through a 0.1 mm internal diameter tube. As the wall shear rate was increased, slightly shear thinning behavior was observed up until a critical wall shear rate was exceeded at which point a large increase in relative viscosity was seen. Other researchers have observed these apparent thickening effects and have interpreted them in terms of individual polymer molecules undergoing coil-stretch transitions. However, in the systems used in this study, the critical wall shear rate and the degree to which relative viscosity increased wer both seen to be strong functions of solution aging time and concentration. These results are inconsistent with the simple picture of individual polymer coils undergoing a coil-stretch transition and instead are consistent with the picture of aggregated systems or micronetworks being stretched from their equilibrium configurations.     

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.     

Formation of fibrous crystals in flowing blends of polyethylene melts

Flow induced crystallization of high density polyethylene has been studied in a two-phase flow system using low density polyethylene as the carrier phase. Extensional stresses were generated under slow flow conditions by either of two methods: one involving flow past a stationary seed, the other involving a droplet deformation and bursting mechanism. In both cases, oriented, fibrillar crystallization of the high density phase was observed optically and correlated with calculations indicating the presence of flow-induced extensional gradients. Morphological, thermal, and birefringence data indicate that the crystalline fibers produced are oriented and superheatable, and consist of a multifibrillar substructure. For fibers produced by the droplet bursting process a semi-quantitative agreement was found between fiber melting point and birefringence based on a simplified analysis for the bursting induced extensional flow. These results demonstrate that two-phase flows of crystallizable systems are a convenient means for studying the phenomenon of flow induced crystallization in polymer melts.     

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.     

Viscosity enhancement in the flow of hydrolysed poly(acrylamide) saline solutions around spheres: implications for enhanced oil recovery

We have studied dilute aqueous solutions of hydrolysed poly(acrylamide), in various ionic environments, in flow around single spheres and around two spheres aligned on the axis of flow. The spheres are held on flexible cantilevers, while the polymer solutions, or solvent, are drawn past at controlled flow rates. We estimate the specific viscosities of the various solutions as a function of the strain rate over strain rates encompassing both the shear thinning and extension thickening regimes. For flow of solutions without added salts around a single sphere, we observe shear thinning followed by a significant increase in the non-Newtonian viscosity with increasing strain rate. The shear thinning reduces the maximal extensional viscosities of the solutions, which has important implications regarding the effectiveness of hydrolysed poly(acrylamide) in oil field applications. For flow of polymer solutions around two axially aligned spheres, we observe a significant reduction in the non-Newtonian forces experienced by the downstream sphere in comparison to the upstream sphere. We consider that this is salient to the understanding of non-Newtonian viscosification in porous media flow.     

Elongational viscosity by fiber spinning

Isothermal melt, fiber-spinning was recently analyzed by means of a nonlinear, integral, constitutive equation that incorporates shear history effects, spectrum of relaxation times, shear-thinning, and extension thinning or thickening when either the drawing force or the draw ratio is specified. The predictions agreed with experimental data on spinning of polystyrene, low-density polyethylene, and polypropylene melts. The predicted apparent elongational viscosity along the threadline (which, as shown in this work, must be identical to that measured experimentally by fiber spinning type of elongational rheometers) is compared with the true elongational viscosity predicted by the same constitutive equation under well-defined experimental conditions of constant extension rate, independent of any strain history. It is concluded that the apparent elongational viscosity, as measured by fiber-spinning, approaches the true elongational viscosity at low Weissenberg numbers (defined as the product of the liquid's relaxation time multiplied by the extension rate). At moderate Weissenberg numbers, the two viscosities may differ by an order of magnitude and their difference grows even larger at high Weissenberg numbers.     

Determination of the elongational viscosity of polymer melts by melt spinning experiments. A comparison with different experimental techniques

In this work, melt spinning experiments were tentatively used for the determination of the elongational viscosity of polymer melts at different levels of tensile strain and strain rate. The materials examined were two high-density polyethylene grades for blow moulding with similar number-average molecular mass but different polydispersity index. The data from melt spinning tests were compared with transient extensional viscosity data obtained by uniform isothermal tensile tests, performed by means of an extensional rheometer, as well as with those produced by converging flow tests (Cogswell model). The results showed that for high strain and strain rate levels, the melt spinning experiments provide elongational viscosity data quite close to the transient extensional viscosity values obtained from the tensile tests.     

Investigation of the rheological properties of short glass fiber-filled polypropylene in extensional flow

The behavior of short glass fiber–polypropylene suspensions in extensional flow was investigated using three different commercial instruments: the SER wind-up drums geometry (Extensional Rheology System) with a strain-controlled rotational rheometer, a Meissner-type rheometer (RME), and the Rheotens. Results from uniaxial tensile testing have been compared with data previously obtained using a planar slit die with a hyperbolic entrance. The effect of three initial fiber orientations was investigated: planar random, fully aligned in the stretching flow direction and perpendicular to it. The elongational viscosity increased with fiber content and was larger for fibers initially oriented in the stretching direction. The behavior at low elongational rates showed differences among the various experimental setups, which are partly explained by preshearing history and nonhomogenous strain rates. However, at moderate and high rates, the results are comparable, and the behavior is strain thinning. Finally, a new constitutive equation for fibers suspended into a fluid obeying the Carreau model is used to predict the elongational viscosity, and the predictions are in good agreement with the experimental data.     

Extensional rheology of a shear-thickening cornstarch and water suspension

A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.     

Design of new HDPE/silica nanocomposite and its enhanced melt strength

Linear polymers are restricted to use in processes that involve severe extensional deformation, such as fiber spinning, film blowing, and thermoforming. To extend their applicability, the extensional properties of polymer melts should be enhanced such that strain hardening, which is defined as an increase in extensional viscosity under a large strain that deviates from the linear viscoelastic curve, is pronounced. In this study, a novel preparation method of linear polymer/inorganic nanocomposites was proposed with a main focus on enhanced melt strength. The design of molecular structure consists of three components—linear polymer, compatibilizer, and surface-modified particles. High-density polyethylene was used as a linear polymer while polyethylene grafted with maleic anhydride was used as a compatibilizer. Silica particles were synthesized and modified on their surfaces by 3-aminopropyltriethoxysilane. The strain hardening behavior of the surface-modified silica composites was pronounced. However, such a result was not observed for the composites of the same composition with pure-silica. In addition, the dispersion of the modified silica was much better than that of pure-silica.     

An unsymmetric constitutive equation for anisotropic viscoelastic fluid

A continuum constitutive theory of corotational derivative type is developed for the anisotropic viscoelastic fluid–liquid crystalline (LC) polymers. A concept of anisotropic viscoelastic simple fluid is introduced. The stress tensor instead of the velocity gradient tensor D in the classic Leslie–Ericksen theory is described by the first Rivlin–Ericksen tensor A and a spin tensor W measured with respect to a co-rotational coordinate system. A model LCP-H on this theory is proposed and the characteristic unsymmetric behaviour of the shear stress is predicted for LC polymer liquids. Two shear stresses thereby in shear flow of LC polymer liquids lead to internal vortex flow and rotational flow. The conclusion could be of theoretical meaning for the modern liquid crystalline display technology. By using the equation, extrusion–extensional flows of the fluid are studied for fiber spinning of LC polymer melts, the elongational viscosity vs. extension rate with variation of shear rate is given in figures. A considerable increase of elongational viscosity and bifurcation behaviour are observed when the orientational motion of the director vector is considered. The contraction of extrudate of LC polymer melts is caused by the high elongational viscosity. For anisotropic viscoelastic fluids, an important advance has been made in the investigation on the constitutive equation on the basis of which a series of new anisotropic non-Newtonian fluid problems can be addressed. The project supported by the National Natural Science Foundation of China (10372100, 19832050) (Key project). The English text was polished by Yunming Chen.