Rheological properties of molten polymers. II. Two-phase systems

A study is carried out for characterizing two-phase systems of molten polymers by their viscous and elastic properties. The two-phase systems chosen for study are blends of polystyrene and polypropylene, and blends of polystyrene and high-density polyethylene. For the study, measurements of wall normal stresses are made by use of a capillary melt rheometer described in part I of this series. The concept of the “exit pressure” is used to determine the elastic properties of the two-phase polymer systems. The present study shows anomalous viscous and elastic properties of two-phase systems, which are difficult to predict from knowing the viscous and elastic properties of their individual components. A detailed discussion is given on the state of dispersion of two incompatible polymer systems in the molten state, by presenting pictures of the microstructure of the extrudate samples. The state of dispersion appears to vary depending on the blending ratio, extrusion temperature, melt viscosities of individual components, and blending method.     

Experimental and theoretical study of the extrusion of two-phase molten polymer systems

An experimental and theoretical study of two-phase flow of molten polymers has been carried out. The theoretical analyses apply the theory of nonlinear viscoelastic fluids to consider stress and velocity profiles and interface shape in stratified flow between parallel plates and in a tube. The second normal stress difference is predicted to influence interface shape. Experimental studies have been made of stratified two-phase flow of a low viscosity but elastic low-density polyethylene and a high-viscosity polystyrene in a capillary rheometer. In the stratified flow experiment, velocity fields and interface shape in the reservoir approaching capillary die and the emerging extrudate were investigated, the former being observed through visual experiments. The emerging extrudates possessed convex polystyrene surfaces at the interface. A strong tendency toward the collection of bubbles near the capillary entry was found. We have made an experimental study of the extrusion of disperse mixtures of polystyrene and different polyolefins. The morphology of the disperse two-phase emerging extrudates has been investigated.     

A study of coextrusion in a circular die

An experimental study has been carried out of concentric and eccentric two-phase flow of polymer melts in a circular die. For the study, a special die was constructed such that two separate streams of molten polymer could be supplied to the die inlet. Materials used for study were low-density polyethylene, high-density polyethylene, and polystyrene. In the experiment, two different capillary length-to-diameter (L/D) ratios were employed: 4 and 18. For a die having an L/D ratio of 18, wall normal stresses were measured, permitting the determination of the pressure gradient and hence the viscous property. For each set of extrusion conditions (L/D ratio, flow rate, component ratio), extrudate samples were collected. These were later carefully cross sectioned and photographed in order to examine the shape of the interface between the two components. It has been found that the lower-viscosity components tends to wrap around the higher-viscosity component, which is consistent with the previous observations reported in the literature.     

Influence of elasticity on dispersed‐phase droplet size in immiscible polymer blends in simple shearing flow

The influence of elasticity of the blend constituent components on the size and size distribution of dispersed‐phase droplets is investigated for blends of polystyrene and high density polyethylene in a simple shearing flow. The elasticities of the blend components are characterized by their first normal stress differences. The role played by the ratio of drop to matrix elasticity at fixed viscosity ratio was examined by using high molecular weight polymer melts, high density polyethylene and polystyrene, at temperatures at which the viscosity ratios roughly equaled each of three different values: 0.5, 1, and 2. The experiments were conducted by using a cone‐and‐plate rheometer, and the steady‐state number and volume‐mean averages of droplet diameters were determined by optical microscopy. After steady‐state shearing, the viscoelastic drops were larger than the Newtonian drops at the same shearing stress. From the steady‐state dispersed‐phase droplet diameters, the steady‐state capillary number, Ca, defined as the ratio of the viscous shearing stress over the interfacial tension stress, was calculated as a function of the ratio of the first normal stress differences in the droplet and matrix phases. For the blend systems with viscosity ratio 0.5, 1 and 2, the values of steady‐state capillary number were found to increase with the first normal stress difference ratio and followed a power law with scaling exponents between 1.7 and 1.9.     

Stratified two-phase flow of molten polymers

A study has been made of stratified two-phase flow of molten polymers in a slit die. For the experimental study, measurements were taken of wall normal stresses along the longitudinal axis of a rectangular duct which had an aspect ratio of 10. Three pressure transducers were flush-mounted on each of the rectangle's long sides, directly opposite from each other. The measurements permitted one to determine the pressure gradients of each component (their viscous properties) and the exit pressures of each component (their elastic properties). For the theoretical study, the fully developed velocity distributions of two-phase flow were determined by solving the equations of motion by use of a power law model. The volumetric flow rates, calculated theoretically by use of a power law model, are compared with experimentally observed ones. Experimental evidence is presented which clearly shows that polystyrene and polypropylene form two incompatible phases in the molten state.     

A study of bicomponent coextrusion of molten polymers

An experimental study has been carried out of coextruding polystyrene with lowdensity polyethylene and polystyrene with high-density polyethylene, using both slit and circular dies. Two melt streams were separately fed to the die entrance and forced to flow side by side through a die. When using the slit die, wall normal stresses were measured with three melt pressure transducers flush-mounted on each of the rectangle's long sides, directly opposite each other. When using the capillary die, three different capillary length-to-diameter (L/D) ratios were employed: 4, 11, and 18. Wall normal stresses were measured for dies having L/D ratioes of 11 and 18 only. The measurements of wall normal stresses permitted one to determine the pressure gradient, and hence the viscous property. For each set of extrusion conditions (L/D ratio, flow rate, and component ratio), extrudate samples were collected. These were later carefully cross sectioned and photographed in order to examine the shape of the interface between the two components. At the phase interface of the polystyrene/low-density polyethylene system, it has been observed that the polystyrene, which is more viscous and yet less elastic than the low-density polyethylene, has a convex surface. However, at the phase interface of the polystyrene/high-density polyethylene system, the high-density polyethylene, which is more viscous and also more elastic than polystyrene, is seen to be convex. This then appears to indicate that the viscosity ratio of two components is primarily responsible for the final shape of the interface.     

Measurement of the rheological properties of polymer melts with slit rheometer. I. Homopolymer systems

Two slit dies have been designed, having aspect ratios of 10 and 20. Three melt pressure transducers were flush-mounted on the long side of the rectangular slot, along the longitudinal centerline of each die. The dies were then used to measure wall normal stresses along the longitudinal direction of polymer melts flowing through the thin slit. The polymeric materials investigated were high-density polyethylene, low-density polyethylene, polypropylene, and polystyrene. The measurement of wall normal stresses were used to determine the rheological properties of melts, namely, the melt viscosity from the slope of axial pressure profiles and the melt elasticity from exit pressures. The present study shows that the rheological properties determined from the slit rheometer are in good agreement with those from the capillary rheometer reported in the author's earlier papers. Therefore it may be concluded that a slit die also may be used as a means of characterizing polymeric materials by their viscous and elastic properties in the molten state.     

Effect of Rheological Properties of Compounds on Fiber Formation in Mixtures of Incompatible Polymers

Abstract

Mixtures of linear polyethylene with polystyrene were used in studying the fiber formation pattern of mixtures of incompatible polymers whose melts were forced through dies. Variables included the viscosity of the components, mixture preparation conditions, and shear stress. It has been established that the process of fiber formation occurs within a definite range of shear stresses, dependent on the viscosity ratio of the fiber-forming polymer and the polymer serving as the dispersion medium. When this ratio is equal to or less than unity, mixtures containing the fiber-forming component in the form of a finely dispersed phase yields continuous fibers several micrometers in diameter within a broad range of shear stresses. At greater values of the component viscosity ratio (tens of units), no fiber formation takes place in the mixtures.     

Measurement of the rheological properties of polymer melts with slit rheometer. II. Blend systems

A slit rheometer described in part I of this series was used for characterizing two blend systems by their viscous and elastic properties in the molten state. The blend systems chosen for study were blends of two high-density polyethylenes having widely different molecular weight distributions and blends of polystyrene and polypropylene which are incompatible in the molten state. The present study shows that blends of two high-density polyethylenes and blends of polystyrene with polypropylene exhibit a minimum in melt viscosity and a maximum and minimum in melt elasticity (in terms of “exit pressure”) at certain blending ratios. These results confirm the author's earlier findings, which were obtained with a capillary rheometer.     

Measurement of the rheological properties of polymer melts with annular rheometer

An annular die has been designed having a very thin gap distance between two coaxial cylinders. The die was then used to measure wall normal stresses along the longitudinal direction of polymer melts flowing through the thin annulus. The materials investigated were high-density polyethylene, low-density polyethylene, polypropylene, and polystyrene. Also investigated were blends of polystyrene and polypropylene, and blends of polystyrene and high-density polyethylene The measurements of wall normal stresses were used to determine the rheological properties of the melts, namely, the melt viscosity from the slope of axial wall normal stress profiles and the melt elasticity from exit pressures. The interpretation of the experimental data was made possible by the fact that the narrow-gap annular die can be considered as a substitute for a thin slit die. It has been found that the results obtained in the present study are consistent with those reported earlier by the author, who at that time used both capillary and slit dies.     

Rheological and extrusion behavior of dispersed multiphase polymeric systems

An experimental study of temperature effect and composition effect on the rheological and extrusion properties of several dispersed multiphase polymer melts were investigated, using a cone-and-plate rheometer and a capillary rheometer. The polymeric systems studied included three homopolymers (two polystyrenes and one poly(methyl methacrylate) (PMMA)), a mechanically blended copolymer of polystyrene and PMMA, two graft copolymers (rubber-modified polystyrene and PMMA), and three particulate-filled polystyrene (CaCO₃, milled glass fiber, and glass flake). It was found that the principal normal stress difference plotted against shear stress gives rise to a temperature independence for all dispersed multiphase polymeric systems. Composition independent correlations, however, do not exist for the principal normal stress difference. The extrudate swell plotted against shear stress becomes independent of temperature only for the homopolymers and graft copolymers. For the mechanically blended polymers and particulate-filled polymers, the temperature independent correlation does not exist. The reduction in viscosity of the glass fiber- and glass flake-filled polystyrenes is found due to the degradation of the base polymer during mixing.     

Melt flow instabilities in capillary flow of two-phase polymer systems

An experimental study was made of melt flow instabilities in extrusion of two-phase polymer systems. For the study, blends were prepared from two polymers: polystyrene (Dow Chemical STYRON 686) and high density polyethylene (Union Carbide DMDJ 4309). The experimental technique used in the present study was the same as that described in a previous paper by the authors. The study shows that there are abrupt increases both in exit pressure and in the recoverable shear strain (defined as the ratio of the exit pressure to shear stress) at the critical flow conditions. It has also been found that an addition of a small amount of high density polythylene (2.5 wt-% and 5.0 wt-%) increases the critical shear rate of polystyrene and hence results in a higher throughput rate before extrudate distortion is actually observed. This result is explained in terms of the independently determined melt elasticity of the two-phase systems investigated.     

Efficient mixing of polymer blends of extreme viscosity ratio: Elimination of phase inversion via solid‐state shear pulverization

A novel, continuous process, solid‐state shear pulverization (S³P), efficiently mixes blends with different component viscosities. Melt mixing immiscible polymers or like polymers of different molecular weight often requires long processing times. With a batch, intensive melt mixer, a polyethylene (PE)/polystyrene (PS) blend with a viscosity ratio (low to high) of 0.019 required up to 35 min to undergo phase inversion. Phase inversion is associated with a morphological change in which the majority component, the high‐viscosity material in these blends, transforms from the dispersed to the matrix phase, and may be quantified by a change from low to high mixing torque. In contrast, such blends subjected to short‐residence‐time (～3 min) S³P yielded a morphology with a PS matrix and a PE dispersed phase with phase diameters ≤ 1 μm. Thus, S³P directly produces matrix and dispersed phases like those obtained after phase inversion during a melt‐mixing process. This assertion is supported by the similarity in the near‐plateaus in torque obtained in the melt mixer at short times with the pulverized blend and at long times with the non‐pulverized blend. The utility of S³P to overcome problems associated with melt mixing like polymers of extreme viscosity ratio is also shown.     

Rheological properties of molten polymers. I. Homopolymer systems

Experimental work has been carried out to investigate the influence of molecular weight distribution and long chain branching on both viscous and elastic properties of molten polymers, using a capillary rheometer, as described in a recent paper by Han. The materials used for the study are three high-density polyethylene samples of widely different molecular weight distributions and a low-density polyethylene containing much long-chain branching. For the analysis of the experimental data, and to obtain the information on the melt elasticity, the concept of the exit pressure recently advanced by Han is used. The study shows that the sample containing long-chain branching is much more elastic than the samples containing little or no long-chain branching, and that the broader the molecular weight distribution of the material, the more elastic the material is. These findings are in conformity with those reported in the literature. Also studied were blends of two high-density polyethylenes having widely different molecular weight distributions. The results of the blends systems show a maximum in melt viscosity as well as in elasticity for a certain blending ratio. The results of the present study may be of considerable interest to those who are concerned with modifying the structure of polymer and also with determining optimum processing conditions.     

Transient and steady-state deformations and breakup of dispersed-phase droplets of immiscible polymer blends in steady shear flow

Transient and steady-state deformations and breakup of viscoelastic polystyrene droplets dispersed in viscoelastic high-density polyethylene matrices were observed in a simple steady shear flow between two transparent parallel disks. By separately varying the elasticities of the individual blend components, the matrix shear viscosity, and the viscosity ratio, their effects on the transient deformation, steady-state droplet size, and the breakup sequence were determined. After the startup of a steady shear flow, the viscoelastic droplet initially exhibits oscillations of its length in the flow direction, but eventually stretches preferentially in the vorticity direction. We find that at fixed capillary number, the oscillation amplitude decreases with increasing droplet elasticity, while the oscillation period depends primarily on, and increases with, the viscosity ratio. At steady-state, the droplet length along the vorticity direction increases with increasing capillary number, viscosity ratio, and droplet elasticity. Remarkably, at a viscosity ratio of unity, the droplets remain in a nearly undeformed state as the capillary number is varied between 2 and 8, apparently because under these conditions a tendency for the droplets to widen in the vorticity direction counteracts their tendency to stretch in the flow direction. When a critical capillary number, Ca_c, is exceeded, the droplet finally stretches in the vorticity direction and forms a string which becomes thinner and finally breaks up, provided that the droplet elasticity is sufficiently high. For a fixed matrix shear stress and droplet elasticity, the steady-state deformation along the vorticity direction and the critical capillary number for breakup both increase with increasing viscosity ratio.     

十字聚焦型微通道内弹状液滴在黏弹性流体中的生成与尺寸预测

利用高速摄像仪对十字聚焦微通道内液滴在黏弹性流体中的生成过程进行了实验研究。微通道截面为600μm×600 μm 的正方形结构,采用硅油作为分散相,含0.3%表面活性剂十二烷基硫酸钠(SDS)的聚环氧乙烷(PEO)水溶液(质量分数分别为0.1%,0.3%,0.6%)为连续相。实验观察到了弹状流、滴状流和喷射流3 种流型。对弹状流型下液滴生成过程的颈部动力学进行了研究,考察了两相流率、连续相毛细数及弹性数对液滴尺寸的影响。结果表明:弹状液滴尺寸随连续相流率、毛细数及弹性数的增加而减小,随分散相流率的增加而增加,连续相弹性对液滴尺寸的影响相对较小。以油水两相流率比和连续相的毛细数及Reynolds 数为变量建立了弹状液滴尺寸的预测关联式,预测值与实验值吻合良好。     

Particle dimensions in polystyrene/polyethylene blends as a function of their melt viscosity and of the concentration of added graft copolymer

Apparent particle dimensions in blends of low density polyethylene (PE) and polystyrene (PS) made by mixing in the molten state have been measured and have been shown to depend on the viscosity of the mixed system. At a certain shearing rate small particles of the dispersed polymer are obtained if the polymer in excess has a high viscosity. At a higher concentration however this effect is counteracted completely if the dispersed phase has a low viscosity and thus lowers the overall viscosity. Coalescence is affected in the same way and the size of the particles increases greatly with increasing concentrations. If a highly viscous polymer is dispersed in a low viscosity polymer matrix relatively large particle sizes will be found at the preset shearing rate mentioned above. With increasing concentration of the highly viscous dispersed phase the particle size decreases due to the increasing viscosity. This effect is counteracted by coalescence leading to a relatively slow increase of particle size with concentration. Addition of surfactants such as graft copolymers based on PS and PE leads to smaller particle sizes as expected.     

Y聚焦型微通道内磁流体液滴的生成与调控

利用高速摄像仪研究了截面为400 μm×400 μm Y聚焦型微通道内磁流体液滴在矿物油中的生成过程。以水基磁流体EMG 807为分散相,含4%表面活性剂Span-20的矿物油为连续相。实验观察到了3种流型：弹状流、滴状流和喷射流。分别考察了两相流量、连续相毛细数及磁感应强度对液滴尺寸及生成过程的影响。结果表明：可通过改变两相流量及磁场调控液滴尺寸。当分散相流量不变时,液滴尺寸随着两相流量比的增加而减小。液滴尺寸随着连续相毛细数及磁感应强度的增加而减小,随着分散相流量的增加而增加。以两相流量比、连续相毛细数和磁Bond数为参数提出了一个液滴尺寸的关联式,预测值与实验值吻合良好。     

A Dielectric Investigation of Miscibility and Morphology in Engineering Thermoplastics

Measurements of complex relative permittivity over extended ranges of frequency and temperature have been obtained for a number of commercially important engineering thermoplastics. The study provides evidence for partial miscibility of the component polymers of impact-modified polycarbonate/polybutylene terephthalate and polycarbonate/polyethylene terephthalate blends and for a two-phase blend morphology with a polyester-rich dispersed phase in a continuous matrix rich in polycarbonate. A second representative conclusion concerns poly(acrylonitrile–butadiene–styrene) where dielectric spectroscopy yields separate absorptions which can be related to the miscibility and morphology of the individual phases. In this case two low-temperature absorptions are attributed respectively to rubber-rich and styrene–acrylonitrile-rich regions in the core and shell of the latex particles which constitute the dispersed phase. © 1997 SCI.     

Dynamic mechanical properties,structure, and composition of impact polystyrene

Two series of impact polystyrene were studied; they had been obtained by grafting and by mechanical mixing, at two different known polybutadiene levels. Their biphasic structure had been characterized by optical microscopy and physicochemical separation. The following factors were investigated: morphology and content of the dispersed phase and continuous phase, composition of the dispersed phase, and molecular weight of the continuous phase. The elastic shear modulus and mechanical damping were measured. It was found that the elastic shear modulus of the two series of materials does not depend on the total polybutadiene content, as is often suggested in the literature, but on the rubbery dispersed phase content. The polybutadiene concentration of this phase, although varying between 100% for the mechanical mixes and 34% for one of the grafted polymers, does not influence the mentioned correlation. The particle size of the dispersed phase and the molecular weight the continuous phase have very little or no influence. The found correlation agrees with the theories for the moduli of models consisting of dispersions of spheres or particles in a matrix, like those of Kerner,¹³ Hashin,^14,15 and Mackenzie.¹⁸