Shear modification of polyethylene

Polymers like LDPE can be modified by applying a shearing process for an extended period. As a result the melt elasticity is reduced, as evidenced by the decrease in extrudate (die) swell at the exit of a capillary and onset of melt fracture. Melt viscosity was also slightly reduced; melt flow index (measured in short capillary) is highly increased. At the same time, melt density rises. All these parameters vary mostly for LDPE grades that exhibit the highest degree of long-chain branching. It was confirmed that the intrinsic viscosisty of the polymer samples was essentially unaffected, so that chain scission may be ruled out. Moreover, the process itself is shown to be reversible as the initial parameters were recovered by special treatment, due to heating or solvation. The mechanism of shear modification is believed to consist of disentanglement of temporary couplings betwen long branches. The practical utilization of this process will be pursued, as well as the scientific understanding of structuring entangled branched chains.     

Extrudate swell and texture of PS,LDPE, ABS,PVC melts and their blends in extrusion capillary flow using a magnetic die

The extrudate swell behavior and extrudate texture of various thermoplastic melts, namely, polystyrene (PS), low‐density polyethylene (LDPE), acrylonitrile‐butadiene styrene (ABS) copolymer, poly(vinyl chloride) (PVC), and their blends, were examined weith a magnetic die system in a constant‐shear‐rate capillary rheometer at a shear rate range 5–28 s^?1 and a temperature range 170–230 °C. The extrudate swell results obtained from the magnetic die were then compared with those produced by a nonmagnetic die. The results showed that the extrudate swell increased with shear rate, but decreased with temperature. In a pure polymer system, up to 25% increase in the extrudate swell was observed with the application of the magnetic field to the PS melt, and the effect decreased in the order ABS > LDPE > PVC. The extrudate swell changes were associated with the changes in rheological properties of the melts. The extrudate textures of the ABS and PVC melts were improved by the magnetic field. In PS/LDPE or PS/ABS blend, it was found that the magnetic die resulted in higher values of the extrudate swell than the nonmagnetic die for all blends, the magnetic effect being less as the LDPE or ABS content was increased. For PS/LDPE system, the extrudate swell of the PS melt did not change much with addition of 20% LDPE, but slightly decreased at the LDPE loading of 40%. At higher LDPE loadings, the extrudate swell increased towards the value of the pure LDPE melt. For PS/ABS system, the extrudate swell ratio progressively decreased with increasing ABS content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 509–517, 2002     

Effect of shear modification on the rheological behavior of two low-density polyethylene (LDPE) grades

Shear modification treatment represents a special shearing history affecting mainly the elastic behavior of polymer melts. This process has been attributed to reversible physical changes in the entanglement structure of the polymer chain network. Shear modification studies were performed for two well-characterized low-density polyethylene (LDPE) grades differing in molecular weight distribution and degree of long chain branching. The shear working of the material was carried out using a specially designed shearing unit producing definable amounts of pure shear in a continuous process. Measurements of the dynamic storage modulus, G′, steady-state shear compliance; J_e, extrudate swell, melt flow index, and the extensional behavior (Rheotens test) indicate that primarily properties associated with the elasticity of the melt are reduced in value. The observed reduction is found to correlate with the mean specific energy dissipated during sample preparation. Comparing the two LDPE grades showed that higher degrees of modification can be obtained at lower energy input levels for the more highly branched grade. Reversibility tests were performed and complete recovery of the initial material behavior was observed. Comparison of measurement results for samples prepared using the shearing unit presented here and a Brabender Plasticorder indicates that the degree of modification depends not only on the molecular structure of the polymer but also on the manner in which the shearing history is imposed upon the material.     

Effects of plasticizer on shear modification of polystyrene

The elastic and viscous properties of polymer melts may be affected by the shear history of the polymer. The extrudate swell of a polymer melt is primarily a manifestation of the elasticity of the polymer melt. In this study, a single screw extruder was used to impose different shear histories on a polystyrene polymer which was processed with and without added plasticizer. The extrudate swell and apparent viscosity of these melts were measured with a capillary rheometer. These characteristics of unplasticized polystyrene are almost not affected by the various preshearing processes. However, the extrudate swell and viscosity of polystyrene containing plasticizer are affected by plasticizer level, shear history and thermal history. After most of the plasticizer in the presheared plasticized polystyrene was extracted, the extrudate swell was still lower than that of the parent sheared polystyrene with the same shear history and the same plasticizer content. These results were obtained without significant changes in molecular weight. Shear modification by conventional process equipment may become impractical if the shear field intensity or dwell time of the material in the apparatus is limited. In such cases, shear refinability by standard process equipment may be observed if the coupling density in the polymer is reduced by some additional means, such as blending with a plasticizer.     

Measurement of melt viscoelastic properties of polyethylenes and their blends—a comparison of experimental techniques

Two polyethylene resins (LDPE and HDPE) and their blends were characterized for dynamic shear rheology, extrudate swell in a capillary rheometer, and recoverable strain as measured by the Melt Elasticity Indexer in attempts to compare parameters related to the so-called “melt elasticity” as obtained by different experimental techniques. Such parameters may be useful in screening materials for their melt processability. Data were obtained at equivalent shear rates/frequencies and different temperatures. With respect to the individual blend components, the LDPE resin with the lower Melt Index (MI) had higher storage modulus and Weissenberg number than the HDPE resin. However, by using criteria based on “recoil” and strain recovery, ranking was different with the LDPE resin shown to exhibit lower “melt elasticity.” In this case, extrudate swell data were found to correlate reasonably well with equilibrium recoverable strain data. With respect to blends, complex viscosity and storage modulus versus composition curves showed positive deviations from linearity, similar to those observed in melt heterogeneous blends. Similarities between the short time recoverable strain vs. composition and the storage modulus vs. composition curves suggest that similar morphological states may exist in the melt over the experimental times and conditions applicable to these different experimental techniques.     

Influence of shearing history on polymer properties. III

As a continuation of the investigation of the effects of shearing history on the subsequent properties of polypropylene, the changes of crystalline structure induced by differences in shearing history were examined. It was found that even extremely high shear in a capillary does not increase the crystal orientation in the extrudate. Such orientation is increased by either extremely high rates of extension of the molten extrudate or by slight plastic deformation occurring in the solidified extrudate as a result of imposed stress. The size of crystallites was found to decrease with increasing shear rate experienced by the polymer prior to the crystallization process. A possible explanation for these changes in polymer properties related to shearing history is proposed as an extension of the cluster flow theory of Busse. This explanation takes into account the size of the ball-like clusters, their internal structure, as well as the type, number, and length of the intercluster connections. The changes induced in a polymer by shearing are of technologic importance in connection with both melt flow characteristics and solid-state properties subsequently developed.     

Melt rheology of compatibilized polystyrene/low density polyethylene blends

Investigations have been made on the melt rheological behaviors of compatibilized blends composed of polystyrene, low density polyethylene and hydrogenated (styrene‐butadiene‐styrene) triblock copolymer used as a compatibilizer. The experiments were carried out on a capillary rheometer. The effects of shear stress, temperature and blending ratio on the activation energy for viscous flow and melt viscosity of the blends are described. The study shows that the viscosity of the blends exhibits a maximum or minimum value at a certain blending ratio. The activation energy for viscous flow decreases with increasing LDPE content. Furthermore, the concept of equal‐viscosity temperature is presented and its role in the processing of the blend is discussed. In addition, the morphology of the extrudate sample of the blends was observed by scanning electron microscopy and the correlation between the morphology and the rheological properties is explored. © 1999 Society of Chemical Industry     

Die design for rigid PVC—the effect of die land length on extrudate swell

PVC profile extrusion compounds have a unique morphology. While other polymers gradually decrease in extrusion die swell with increasing length/thickness (L/D) ratio, PVC profile extrusion compounds have a low die swell, quite independent of the die's L/D ratio in the range of 5 to 20. The fact that the die land length can be changed without changing the extrudate swell is an important consideration, which makes die design and balancing dies simpler and easier for PVC profile extrusion compounds. While other polymers substantially increase extrudate swell with increased shear rate, the swell of the PVC profile compounds is not much affected by shear or extrusion rate. This unique behavior allows wider processing latitude in profile extrusion and faster extrusion rates than with other polymers. Another unique factor in the rheology of PVC profile extrusion compounds is that extrusion die swell increases with increasing melt temperature, while other polymers have decreasing die swell with increasing melt temperature. The unusual rheology of PVC profile extrusion compounds is attributed to its unique melt morphology, where the melt flow units are 1 um bundles and molecules that have low surface to surface interaction and entanglement at low processing temperatures but increased melting and increased entanglement at higher processing temperatures. Other polymers, unlike PVC, have melt flow at the molecular level.     

LLDPE／LDPE共混物熔体挤出胀大行为的研究

应用毛细管流变仪，考察了实验条件下线性低密度聚乙烯与低密度聚乙烯共混物（ＬＬＤＰＥ／ＬＤＰＥ）熔体挤出胀大行为及其影响因素。结果表明，挤出胀大比Ｂ与剪切应力近似呈幂律关系，而随口型长径比的增加呈指数衰减，当共混比为５０／５０时，Ｂ产生局部极涉值现象。     

Experimental studies on radial extrudate swell and velocity profiles of flowing PS melt in an electro‐magnetized die of an extrusion rheometer

This article investigates the radial extrudate swell and velocity profiles of polystyrene melt in a capillary die of a constant shear‐rate extrusion rheometer, using a parallel coextrusion technique. An electro‐magnetized capillary die was used to monitor the changes in the radial extrudate swell profiles of the melt, which is relatively novel in polymer processing. The magnetic flux density applied to the capillary die was varied in a parallel direction to the melt flow, and all tests were performed under the critical condition at which sharkskin and melt fracture did not occur in the normal die. The experimental results suggest that the overall extrudate swell for all shear rates increased with increasing magnetic flux density to a maximum value and then decreased at higher densities. The maximum swelling peak of the melt appeared to shift to higher magnetic flux density, and the value of the maximum swell decreased with increasing wall shear rate and die temperature. The effect of magnetic torque on the extrudate swell ratio of PS melt was more pronounced when extruding the melt at low shear rates and low die temperatures. For radial extrudate swell and velocity profiles, the radial swell ratio for a given shear rate decreased with increasing r/R position. There were two regions where the changes in the extrudate swell ratio across the die diameter were obvious with changing magnetic torque and shear rate, one around the duct center and the other around r/R of 0.65–0.85. The changes in the extrudate swell profiles across the die diameter were associated with, and can be explained using, the melt velocity profiles generated during the flow. In summary, the changes in the overall extrudate swell ratio of PS melt in a capillary die were influenced more by the swelling of the melt around the center of the die. Polym. Eng. Sci. 44:2298–2307, 2004. © 2004 Society of Plastics Engineers.     

高分子材料动态成型过程中熔体非线性行为的研究

借助流变测量和连续介质理论,不依赖已有的本构关系,对平行叠加正弦振动条件下高分子熔体经毛细管的动态挤出过程进行了理论分析。以低密度聚乙烯(LDPE)为原材料,实验测量LDPE熔体在一定振动频率和振幅下毛细管入口压力、体积流量和挤出胀大的瞬态值,即可得到动态成型过程中高分子熔体剪切应力、剪切速率和表观粘度的变化规律:随振幅和频率的变化,LDPE熔体的表观粘度呈非线性变化趋势;在不同的振幅和频率下动态挤出LDPE熔体,跟稳态挤出时一样,壁面剪切应力与壁面剪切速率也成非线性比例关系。     

Basic study of extrusion of polyethylene and polystyrene foams

A fundamental study of bubble morphology development and apparent rheological properties in foam extrusion is reported. The influence of melt temperature, die length/diameter ratio, and blowing agent level on the morphology are considered. Measurements of the influence of blowing agent on viscosity, extrudate swell, and end-pressure losses are described. The viscosity is reduced, but extrudate swell is increased. End-pressure losses were found to become very large relative to the die wall shear stress at low extrusion rates. These results were interpreted in terms of bubble development. The filling of molds by foaming melts was observed and is described.     

Capillary extrusion behavior of phenolphthalein poly(ether-ether-sulphone) (PES-C)

The capillary extrusion flow properties of novel engineering thermoplastic phenolphthalein poly(ether-ether-sulphone) (PES-C) have been investigated using capillary rheometer. The dependence of viscosity on the wall shear rate and temperatures were obtained. The flow activation energy was found to decrease with shear rate but to be constant with shear stress. The entrance effect was calculated and from which the extensional behavior was estimated using Cogswell's method. From the extrudate swell ratio the principal normal stress was evaluated and a temperature-independent correlation was observed when they were plotted against shear stress. The melt fracture phenomena were checked and discussed also. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:951–958, 1997     

Effect of molecular structure on extrudate swell behavior for different thermoplastic melts in an electro‐magnetized die

The extrudate swell ratio of five different thermoplastic melts flowing in a constant shear rate rheometer having a capillary die with and without application of magnetic field was studied. The effects of the magnetic flux direction and density, die temperature, and wall shear rate on the extrudate swell and flow properties were investigated. The experimental results suggested that an increasing wall shear rate increased the swelling ratio for the polystyrene (PS), LLDPE, and PVC melts, but the opposite effect was observed for the ABS and PC melts. The extrudate swell ratio for the PS, ABS, PC, and LLDPE melts decreased with increasing die temperature, the effect being reversed for the PVC melt. Thermoplastic melts having high benzene content in the side‐chain and exhibiting anisotropic character were apparently affected by the magnetic field, the extrudate swell ratio increasing with magnetic flux density. The effect of the magnetic field on the extrudate swell ratio decreased in the order of PS → ABS → PC. The extrudate swell ratio for the co‐parallel magnetic field system was slightly higher than that for the counter‐parallel magnetic field system at a high magnetic flux density. POLYM. ENG. SCI., 47:270–280, 2007. © 2007 Society of Plastics Engineers.     

Experimental studies on extrudate swell behavior of PS and LLDPE melts in single and dual capillary dies

Extrudate swell behavior of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts was investigated using a constant shear rate capillary rheometer. Two capillary dies with different design configurations were used, one being a single flow channel and the other being a dual flow channel. A number of extrudate swell related parameters were examined, and used to explain the discrepancies in the extrudate swell results obtained from the single and dual flow channel dies, the parameters including output rate and output rate ratio, power law index, wall shear rate, wall shear stress, melt residence time, pressure drop induced temperature rise, flow channel position relative to the barrel centerline, and the flow patterns. It was found in this work that the power law index (n value) was the main parameter to determine the output rate ratio and the extrudate swell between the large and small holes for the dual flow channel die: the greater the n value the lower the output rate ratio and thus decreased extrudate swell ratio. The differences in the extrudate swell ratio and flow properties for PS and LLDPE melts resulted from the output rate ratio and the molecular chain structure, respectively. The extrudate swell was observed to increase with wall shear rate. The discrepancies in the extrudate swell results from single and dual dies for a given shear rate were caused by differences in the flow patterns in the barrel and die, and the change in the melt velocities flowing from the barrel and in the die to the die exit. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1713–1722, 2003     

Evaluation of melt flow as a measure of low density polyethylene processability into blown films

Melt capillary flow and extrudate swelling for low density polyethylenes (LDPE), differing in ease of heavy-duty, blownfilm extrusion, have been employed as processability criteria. LDPE of good processability is characterized by a unique combination of melt fluidity, temperature, shear rate dependence and melt elasticity. These characteristics of flow are correlated with LDPE film blowing process variables such as maximum take-up speed, film thickness scatter, and extruder temperatures profile. Intuitively, these melt flow criteria should be extended to Trouton's viscosity and the tensile strength of the melt. The limited development of the elongation viscometry techniques, however, has limited their application.     

A parallel coextrusion technique for simultaneous measurements of radial die swell and velocity profiles of a polymer melt in a capillary rheometer

This article proposes a new experimental technique to simultaneously measure radial die swell and velocity profiles of polystyrene melt flowing in the capillary die of a constant shear rate rheometer. The proposed technique was based on parallel coextrusion of colored melt‐layers into uncolored melt‐stream from the barrel into and out of the capillary die. The size (thickness) ratio of the generated melt layers flowing in and out of the die was monitored to produce the extrudate swell ratio for any given radial position across the die diameter. The radial velocity profiles of the melt were measured by introducing relatively light and small particles into the melt layers, and the times taken for the particles to travel for a given distance were measured. The proposed experimental technique was found to be both very simple and useful for the simultaneous and accurate measurement of radial die swell and velocity profiles of highly viscous fluids in an extrusion process. The variations in radial die swell profiles were explained in terms of changes in melt velocity, shear rate, and residence time at radial positions across the die. The radial die swell and velocity profiles for PS melt determined experimentally in this work were accurate to 92.2% and 90.8%, respectively. The overall die swell ratio of the melt ranged from 1.25 to 1.38. The overall die swell ratio was found to increase with increasing piston speed (shear rate). The radial extrudate swell profiles could not be reasoned by the shear rate change, but were closely linked with the development of the velocity profiles of the melt in the die. The die swell ratio was high at the center (～1.9) and low (～0.9) near the die wall. The die swell ratio at the center of the die reduced slightly as the piston speed was increased. Polym. Eng. Sci. 44:1960–1969, 2004. © 2004 Society of Plastics Engineers.     

Melt extrudate swell behavior of multi‐walled carbon nanotubes filled‐polypropylene composites

The extrudate swell behavior of polypropylene (PP) composite melts filled with multi‐walled carbon nanotubes (MWCNTs) was studied using a capillary rheometer in a temperature range from 190 to 230°C and at various apparent shear rates varying from 50 to 800 s⁻¹. It was found that the values of the extrudate swell ratio of the composites increased nonlinearly with increasing apparent shear rates, while the values of the extrudate swell ratio decreased almost linearly with increasing temperature. The values of the melt extrudate swell ratio increased approximately linearly with increasing shear stress, while decreased approximately nonlinearly with an increase of the MWCNT weight fraction. In addition, the extrudate swell mechanisms were discussed with observation of the fracture surface of the extrudate using a scanning electronic microscopy. This study provides a basis for further development of MWCNTs reinforced polymer composites with desirable mechanical and thermal properties. POLYM. COMPOS., 38:2433–2439, 2017. © 2015 Society of Plastics Engineers     

茂金属聚乙烯（mPE）／高压聚乙烯（LDPE）共混熔体的流变学

研究了不同比例共混的茂金属聚乙烯（mPE)和高压聚乙烯（LDPE）熔体的流变行为,讨论了共混物组成、剪切速率和剪切应力以及温度对熔体流变曲线、熔体粘度和膨胀比的影响,mPE的加工提供了理论依据。不同共混比的熔体均为假塑性流体,且熔体假塑性随LDPE含量增大而增强。熔体流动活化能随LDPE组成的增加逐渐增大,粘度对温度的敏感性增强,共混物的非牛顿指数随LDPE的增加而降低,改善了mPE的加工性能。     

Mechanism of shear modification of low density polyethylene

In this paper we address the aspects associated with shear modification of low density polyethylene by extrusion. By successive passes of the polymer through an extruder it can be shown that both the melt viscosity and melt elasticity are reduced by shear modification. These reversible variations are not accompanied by significant changes in molecular weight distribution. The major effects of extrusion are to decrease the amount of elastically effecitve material. Study of proton relaxation times at 150°C shows that the melt comprises regions of relatively ordered, entangled, and unentangled polymer. Shearing reduces the proportion of more ordered material. The elastically effective anchors that are reduced by shearing are regions with restricted segmental mobility rather than conventional entanglements or intermolecular knots. Successive extrusions produce a relatively small decrease in the number of such constraints to molecular motion. Repeated shearing has a diminishing effect on the proportion of more ordered material in the polyethlene melt. This parallels observations of the effects of repeated shear modification on the properties of polyethylene films and other extrudates.