Polypropylene-polyethylene blends

Summary Die swell behaviour and morphology of melt blends of isotactic polypropylene (PP) and high density polyethylene for pure polymers and blends with 25, 50 and 75 weight % PP are described in the present study. A light interference contrast microscopy technique was used for the morphological characterization of melt blends and extrudate samples of the blends obtained with an Instron capillary rheometer. The results indicate that the domains from blends where the dispersed phase has higher viscosity than the continuous phase remain as continuous domains in the extrudate whereas domain destruction takes place when blends where the continuous phase has the higher viscosity are extruded.The die swell behaviour as well as the fiber forming properties of extrudates of melts having unstable domains extruded at high shear stresses resemble the behaviour of homopolymers, whereas samples with stable domains are significantly different, die swell increases with temperature at constant shear stress and stable fibers cannot be obtained after necking.With 10 figures and 1 table     

Numerical study of the combined effects of inertia,slip, and compressibility in extrusion of yield stress fluids

The axisymmetric extrudate swell flow of a compressible Herschel–Bulkley fluid with wall slip is solved numerically. The Papanastasiou-regularized version of the constitutive equation is employed, together with a linear equation of state relating the density of the fluid to the pressure. Wall slip is assumed to obey Navier’s slip law. The combined effects of yield stress, inertia, slip, and compressibility on the extrudate shape and the extrudate swell ratio are analyzed for representative values of the power-law exponent. When the Reynolds number is zero or low, swelling is reduced with the yield stress and eventually the extrudate contracts so that the extrudate swell ratio reaches a minimum beyond which it starts increasing asymptotically to unity. Slip suppresses both swelling and contraction in this regime. For moderate Reynolds numbers, the extrudate may exhibit necking and the extrudate swell ratio initially increases with yield stress reaching a maximum; then, it decreases till a minimum corresponding to contraction, and finally, it converges asymptotically to unity. In this regime, slip tends to eliminate necking and may initially cause further swelling of the extrudate, which is suppressed if slip becomes stronger. Compressibility was found to slightly increase swelling, this effect being more pronounced for moderate yield stress values and wall slip.     

液晶高分子-各向异性流体挤出拉伸分岔研究

应用共转导数型本构方程研究了液晶高分子纺丝挤出过程的拉伸黏度,应用计算机符号运算软件 Maple得出解析表达式,拉伸黏度与拉伸率之间关系(随剪切速率变化)表明存在分岔现象,得出拉伸黏度显著高于相应的剪切黏度,解释了液晶高分子熔体挤出时不发生挤出胀大的物理机制．     

Annular extrudate swell of pseudoplastic and viscoplastic fluids

Numerical simulations have been undertaken for the benchmark problem of annular extrudate swell present in pipe extrusion and parison formation in blow molding. The finite element method (FEM) is used to provide numerical results for different inner/outer diameter ratios κ under steady-state conditions. The Herschel-Bulkley model of viscoplasticity is used with the Papanastasiou regularization, which reduces with appropriate parameter choices to the Bingham–Papanastasiou, power-law and Newtonian models. The present results provide the shape of the extrudate, and in particular the thickness and diameter swells, as a function of the dimensionless power-law index (in the case of pseudoplasticity) and the dimensionless yield stress (in the case of viscoplasticity). The pressures from the simulations have been used to compute the excess pressure losses in the system (exit correction). While shear-thinning leads to reduced swelling relative to the Newtonian values for all κ-values, the opposite is true for shear-thickening fluids, which exhibit considerable swelling. Viscoplasticity leads to decreased extrudate swell as the dimensionless yield stress goes from zero (Newtonian behaviour) to an asymptotic value of fully plastic behaviour. The exit correction decreases to zero with a decrease in the power-law index to zero and an increase in the dimensionless yield stress to its asymptotic limit. However, the decrease is not monotonic: for power-law fluids it has maxima in the range of power-law indices between 0.8 and 0.6, while for viscoplastic fluids it has maxima around Bingham number values of 5.     

Quantitative evaluation of extrudate swell from viscoelastic properties of polystyrene

A theory of extrudate swell for short, intermediate or long dies is presented. In our experiment, we consider that the swelling phenomenon is mainly due to the recoverable elongational strain induced by the converging flow at the die entrance, as well as by recoverable shear strain originating within the die. From these concepts, an equation has been derived for the quantitative prediction of extrudate swell from the elastic material properties such as the entrance pressure drop, the relaxation modulus and the recoverable shear strain. Excellent agreement is found between predicted and measured values of extrudate swell obtained on commercial polystyrene melt, using capillaries of length-to-diameter ratios ranging from 1 to 20 and in a wide range of shear rates.     

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.     

Prediction of extrudate swell in polymer melt extrusion using an Arbitrary Lagrangian Eulerian (ALE) based finite element method

Accurate prediction of extrudate (die) swell in polymer melt extrusion is important as this helps in appropriate die design for profile extrusion applications. Extrudate swell prediction has shown significant difficulties due to two key reasons. The first is the appropriate representation of the constitutive behavior of the polymer melt. The second is regarding the simulation of the free surface, which requires special techniques in the traditionally used Eulerian framework. In this paper we propose a method for simulation of extrudate swell using an Arbitrary Lagrangian Eulerian (ALE) technique based finite element formulation. The ALE technique provides advantages of both Lagrangian and Eulerian frameworks by allowing the computational mesh to move in an arbitrary manner, independent of the material motion. In the present method, a fractional-step ALE technique is employed in which the Lagrangian phase of material motion and convection arising out of mesh motion are decoupled. In the first step, the relevant flow and constitutive equations are solved in Lagrangian framework. The simpler representation of polymer constitutive equations in a Lagrangian framework avoids the difficulties associated with convective terms thereby resulting in a robust numerical formulation besides allowing for natural evolution of the free surface with the flow. In the second step, mesh is moved in ALE mode and the associated convection of the variables due to relative motion of the mesh is performed using a Godunov type scheme. While the mesh is fixed in space in the die region, the nodal points of the mesh on the extrudate free surface are allowed to move normal to flow direction with special rules to facilitate the simulation of swell. A differential exponential Phan Thien Tanner (PTT) model is used to represent the constitutive behavior of the melt. Using this method we simulate extrudate swell in planar and axisymmetric extrusion with abrupt contraction ahead of the die exit. This geometry allows the extrudate to have significant memory for shorter die lengths and acts as a good test for swell predictions. We demonstrate that our predictions of extrudate swell match well with reported experimental and numerical simulations.     

Melt shear rheology of carbon nanofiber/polystyrene composites

The rheological behavior and morphology of carbon nanofiber/polystyrene (CNF/PS) composites in their melt phase have been characterized both through experimental measurements and modeling. Composites prepared in the two different processes of solvent casting and melt blending are contrasted; melt-blended and solvent-cast composites were each prepared with CNF loadings of 2, 5, and 10 wt%. A morphological study revealed that the melt blending process results in composites with shorter CNFs than in the solvent-cast composites, due to damage caused by the higher stresses the CNFs encounter in melt blending, and that both processes retain the diameter of the as-received CNFs. The addition of carbon nanofiber to the polystyrene through either melt blending or solvent casting increases the linear viscoelastic moduli, G′ and G″, and steady-state viscosity, η, in the melt phase monotonically with CNF concentration, more so in solvent cast composites with their longer CNFs. The melt phase of solvent-cast composites with higher CNF concentrations exhibit a plateau of the elastic modulus, G′, at low frequencies, an apparent yield stress, and large first normal stress difference, N ₁, at low strain rates, which can be attributed to contact-based network nanostructure formed by the long CNFs. A nanostructurally-based model for CNF/PS composites in their melt phase is presented which considers the composite system as rigid rods in a viscoelastic fluid matrix. Except for two coupling parameters, all material constants in the model for the composite systems are deduced from morphological and shear flow measurements of its separate nanofiber and polymer melt constituents of the composite. These two coupling parameters are polymer–fiber interaction parameter, σ, and interfiber interaction parameter, C _I. Through comparison with our experimental measurements of the composite systems, we deduce that σ is effectively 1 (corresponding to no polymer–fiber interaction) for all CNF/PS nanocomposites studied. The dependence of CNF orientation on strain rate which we observe in our experiments is captured in the model by considering the interfiber interaction parameter, C _I, as a function of strain rate. Applied to shear flows, the model predicts the melt-phase, steady-state viscosities, and normal stress differences of the CNF/PS composites as functions of shear rate, polymer matrix properties, fiber length, and mass concentration consistent with our experimental measurements.     

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.     

Influence of wall slip on extrudate swell: a boundary element investigation

This paper reports a numerical study of the extrudate swell by a transient Boundary Element Method (BEM). Furthermore the fluid, which is modeled by a differential constitutive equation, is allowed to slip at the wall, where the slip velocity is a prescribed function of the wall shear stress. This function is a curve fit of the extensive data of Ramamurthy on linear low density polyethylene which incorporates two parameters: a critical wall shear stress above which slip occurs, and another parameter which governs the shape of the slip velocity versus shear stress curve. The results show that wall slip reduces both the amount of extrudate swell and the critical Weissenberg number above which our numerical scheme no longer converges.     

Rheology and birefringence of Fomblin YR at very high shear rates

The rheological and structural properties of perfluoropolyether (PFPE) lubricant films including viscosity, shear stress, and birefringence were measured at relatively low to extremely high shear rates using a rotational optical rheometer. The viscosity of various films with different thicknesses exhibit Newtonian behavior up to a shear rate 1 × 10⁴ s⁻¹, with a transition to shear-thinning behavior obvious at higher shear rates. Birefringence of these films was also measured for the first time, and these results indicate chain alignment with shear in the shear-thinning regime. The shear rate at which alignment occurs is similar to that of the onset of shear thinning. This correlation between chain alignment and shear thinning provides direct evidence that the ability of PFPEs to lubricate hard drives at high shear rates is a direct consequence of the ability of the applied shear field to align the molecules on a molecular level.     

Extrudate swell of linear and branched polyethylenes: ALE simulations and comparison with experiments

Extrudate swell is a common phenomenon observed in the polymer extrusion industry. Accurate prediction of the dimensions of an extrudate is important for appropriate design of dies for profile extrusion applications. Prediction of extrudate swell has been challenging due to (i) difficulties associated with accurate representation of the constitutive behavior of polymer melts, and (ii) difficulties associated with the simulation of free surfaces, which requires special techniques in the traditionally used Eulerian framework. In a previous work we had argued that an Arbitrary Lagrangian Eulerian (ALE) based finite element formulation may have advantages in simulating free surface deformations such as in extrudate swell. In the present work we reinforce this argument by comparing our ALE simulations with experimental data on the extrudate swell of commercial grades of linear polyethylene (LLDPE) and branched polyethylene (LDPE). Rheological behavior of the polymers was characterized in shear and uniaxial extensional deformations, and the data was modeled using either the Phan–Thien Tanner (PTT) model or the eXtended Pom–Pom (XPP) model. Additionally, flow birefringence and pressure drop measurements were done using a 10:1 contraction–expansion (CE) slit geometry in a MultiPass Rheometer. Simulated pressure drop and contours of the principal stress difference were compared with experimental data and were found to match well. This provided an independent test for the accuracy of the ALE code and the constitutive equations for simulating a processing-like flow. The polymers were extruded from long (L/D = 30) and short (L/D = 10) capillaries dies at 190 °C. ALE simulations were performed for the same extrusion conditions and the simulated extrudate swell showed good agreement with the experimental data.     

On the time-dependency of the flow-induced dynamic moduli of a liquid crystalline hydroxypropylcellulose solution

Some unusual rheological features of a liquid crystalline solution of hydroxypropylcellulose (HPC) in water have been investigated. Measurements have been performed by using a variety of different apparatuses with cone and plate geometries. Particular attention has been devoted to the experimental procedures, including the use of different sealing techniques, which are necessary to avoid solvent evaporation during the very long transients. Shear fracture effects, and their dependence on the type of sealing agents have also been studied. In steady shear, the HPC solution shows some rheological features which are common to other lyotropic systems, such as a three-region viscosity curve, and a double sign change in the first normal stress difference vs shear rate curve. The structural changes which take place after cessation of shear flow have been investigated by following the evolution of the dynamic moduli as a function of the time elapsed after the shear flow is stopped. It was found that the rate of the previously applied shear strongly affects both the kinetics and the asymptotic, long time values of the dynamic properties. Possible explanations for such behavior in terms of microstructure evolution are presented and discussed.     

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.     

Rheology for deposition control of polymer-amended oil sands tailings

Mineral slurries may be dewatered to the point that they manifest non-Newtonian behavior. Many such slurries exhibit both thixotropic and hysteric behavior in their rheology, which has important implications for managing their deposition in tailings impoundments. This paper characterizes the rheology of a mineral slurry with relatively high clay content, which is treated with a high molecular weight anionic polymer to induce flocculation. The rheology exhibits viscosity bifurcation behavior similar to pure clay, including shear history-dependent apparent yield stress values. Rheometry results are presented including stress growth, controlled stress tests, and oscillatory rheometry, all using a vane fixture. The measured rheology is modeled using a previously published viscosity bifurcation model that accounts for hysteresis in the apparent yield stress. The rheology results are used semi-quantitatively to explain deposition rate-dependent behavior seen in flume tests. The geometry of tailings in flume tests with relatively slow deposition is affected by the presence of deposited tailings that have come to rest sufficiently to manifest the yield stress of initially fully structured material, rather than the lower value yield stress that characterizes when the material first comes to a stop. This full recovery of the yield stress seems to be particularly important to managing surface deposition, as zones of tailings that have stopped moving substantially steepen the slope of deposits near the deposition point.     

Rheological properties of suspensions of TiO2 particles in polymer solutions. 1. Shear viscosity

This paper presents results on the rheological behaviour of suspensions of two kinds of TiO₂ particles in two different polymer solutions. The particles differ in their hydrophilic or hydrophobic properties. The dispersing media are a solution of high molecular weight polyisobutylene in decalin and a solution of a low molecular weight polybutene in decalin. The concentrations of polymer are adjusted in order to get the same zero shear viscosity. The shear viscosity measurements display an apparent yield stress in some cases. The existence and the values of the yield stress depend on the volume fraction of solid particles and on the type of particles. The evolution of the intrinsic viscosity and of the maximum packing fraction vs the shear rate is interpreted in terms of evolution of the size and of the shape of aggregates of particles under shear. The effect of temperature on the development of the yield stress is also discussed. The results are completed by microscopic observations.     

A simple model to predict extrudate swell of polystyrene and linear polyethylenes

In a previous paper (Guillet and Seriai, 1991) we derived a simple analytical expression which allows the prediction of extrudate swell of polystyrene in a wide range of residence time. This was done using the rubber-like elasticity theory and calculation of the elongational strain recovery of a Lodge fluid. The theoretical extrudate swell ratio mainly depends on the relaxation modulus, the extension ratio and the recoverable shear strain. The main advantage of this model is to provide good accuracy with short dies in a wide range of shear rate. In this paper, we examine the validity of the proposed equation with different contraction ratios at the die entrance (ECR) and its ability to predict extrudate swell of other commodity polymers such as polyethylenes.     

Steady-shear viscosity and transient stress response for elasto-thixotropic fluids

A phenomenological model for dispersed systems which exhibit complex rheological behaviour such as shear and time-dependent viscosity, yield stress, and elasticity is proposed. The model extends the Quemeda model to describe the viscosity function with a structural parameter λ which varies according to different kinetic orders of particle aggregation and segregation. The transient stress response is obtained by solving an instantaneous Maxwell model with an assumed shear modulus functionG of the same form as the viscosity function η. Accuracy of the proposed model is verified experimentally with the results obtained for two oil (creosote)/water emulsions. The model that gives the best fit of experimental data appears to be the one with kinetic ordersn=m=2.     

弹性-触变性流体的定态剪切粘度与瞬态应力响应

用四种不同级数的动力学方程以表示分散物系内结构单元的聚集与解聚速率,并导出相应的定态和瞬态结构参数式。设弹性模量 G 与结构参数的关系具有与粘度函数相同的形式,求解 Maxwell 方程获得瞬态应力响应。 两种乳浊液的实验证明本文提出的流变模型可以表征弹性-触变性流体的流变性。用n=m=2 的模型可对这些乳浊液作出最佳模拟。