Influence of shearing history on the rheological properties and processability of branched polymers. II. Optical properties of low-density polyethylene blown films

An investigation was performed to determine how optical properties of LDPE blown films changed when the material was subjected to extrusion shearing. In this study, shearing histories were given to the materials by designed extrusion shearing. Recognizable variations take place in haze and gloss of the blown film during the extrusion shearing. Such variations were expressed as a function of the processing index (PI), which was introduced in a preceding paper as a measure of the memory effect of shearing histories of LDPE. This means that the variations originate in a certain change in the cohesive state of the polymer molecules attributable to the shearing.     

Influence of shearing history on the rheological properties and processability of branched polymers. I

The influence of shearing history on the viscoelastic properties of low-density polyethylene (LDPE) is investigated. Swelling of extrudates from a melt indexer is measured for monitoring the variation in viscoelasticity. Continuous shearing of molten LDPE reduces the swelling ratio. The reduction is not due to molecular degradation, as evidenced by constancy of intrinsic viscosity. The rate of the reduction in the swelling ratio depends on the shearing conditions and characteristics of LDPE, but the swelling ratio finally attain a steady value. The swelling ratio reduced by the continuous shearing is completely recovered by solvent or heat treatment. The ratio of the completely reduced swelling ratio to the completely recovered one is defined as a new index representing the viscoelastic variation, the processing index (PI), and the relationship between PI and the primary molecular parameters of LDPE is investigated. It is concluded that the variation in the viscoelastic properties becomes more remarkable with increase in the weight-average molecular weight. The cause of the viscoelastic variation is also discussed from the rheological and thermodynamic points of view.     

Influence of shearing history on the rheological properties and processability of branched polymers. III. An amorphous long-chain branched polymer

Viscoelastic properties of branched polymers vary with their shearing history; notwithstanding, their primary molecular parameters do not change. According to a recent study, such viscoelastic variation was believed to be observed only with crystalline long-chain branched polymers such as low-density polyethylene or polyacetal. That is, the origin of the viscoelastic variation was attributed to the presence of specific entanglements at the branching points, which was formed during the crystallization process. However, the viscoelastic variation of the long-chain branched polymers is the phenomenon at temperatures well above their melting points, namely, it is considered that whether the long-chain branched polymers are crystalline or not is not essential for the occurrence of the viscoelastic variation. Thus, the influence of the shearing history on the rheological properties of an amorphous long-chain branched polymer was investigated in this paper, and it was found that, irrespective of their crystallinity, the viscoelastic properties of long-chain branched polymers vary according to their shearing history.     

Linear low-density polyethylene/high-density polyethylene blends: Effect of high-density polyethylene content on die swell and flow instability

This work aimed to evaluate the effect of high-density polyethylene (HDPE) content and of shear rate on the die swell and flow instability of linear low-density polyethylene (LLDPE)/HDPE blends. The results showed that the die swell of the LLDPE/HDPE blends increased with the increase in the shear rate. At high shear rates, the increase in the HDPE content led to an increase in the die swell of LLDPE/HDPE blends. The surface morphology analysis of the extrudates by optical and scanning electron microscopy revealed the presence of sharkskin and stick–slip flow instabilities in LLDPE and LLDPE/HDPE blends at the shear rates investigated. These instabilities were attenuated with the addition of HDPE and almost disappeared in the LLDPE/HDPE blend containing 50 wt% of HDPE.     

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.     

Effects of additions of high-density polyethylene on the processability of linear low-density polyethylene

In considering the processing characteristics of typical linear low-density polyethylenes, it is very likely that the nature and amount of the “high-density” portion of the short chain branching distribution has a strong effect on rheological behavior. In this study, highdensity resins of varying molecular weight were blended into a linear low-density polyethylene base resin to determine the effect on viscosity, elasticity, and onset of haze. It was determined that it is not only the high-molecular-weight characteristics of the high-density portion but also the linear nature of the molecules that has a negative effect on processability. © 1993 John Wiley & Sons, Inc.     

Impact of processing history on rheological properties for branched polypropylene

The impact of applied processing history and the post-processing annealing procedure on the rheological properties of long-chain branched polypropylene (B-PP) have been studied intensively as compared with conventional linear polypropylene (L-PP) and low-density polyethylene (LDPE) produced by autoclave process. It was found that drawdown force, as a measure of melt elasticity for B-PP, is greatly depressed even by the short-time processing in an internal batch mixer, whereas the rheological properties of L-PP are unchanged by the processing history. Considering that the drawdown force is recovered to the original value during the post-processing annealing, the phenomenon is ascribed to the conformation change related to the branch structure, i.e. the alignment of long branches to a backbone chain, which is known as ‘shear modification’. Further, it is demonstrated that the depression of the drawdown force for B-PP is more significant than that for LDPE. Moreover, it is also clarified that B-PP needs a longer post-processing annealing time to recover the drawdown force than LDPE. The difference in the recovery curves during the annealing suggests that B-PP has less relatively ‘short’ long branches.     

Influence of intercalated montmorillonite/polyethylene glycol binary processing aids on the rheological and mechanical properties of metallocene linear low-density polyethylene

Summary Organomodified Na⁺-montmorillonite/polyethylene glycol (PEG) processing aids were prepared. Melt compounding was used to prepare nanocomposites of exfoliated montmorillonite platelets dispersing in a metallocene linear low-density polyethylene (mLLDPE) matrix. The extent of intercalation of PEG into montmorillonite layers and clay platelet exfoliation in the mLLDPE matrix was studied by X-ray diffraction. The influence of montmorillonite/PEG binary processing aids on the rheological properties and sharkskin melt fracture of mLLDPE was studied using a capillary rheometer and scanning electron microscope (SEM). The crystallization and melting characters were also studied by differential scanning calorimetry (DSC) and X-ray diffraction. The montmorillonite/PEG binary processing aids could reduce the viscosity of mLLDPE. Meanwhile, the critical apparent shear rate of the onset of sharkskin melt fracture of mLLDPE was increased by adding the aids. Also the nanocomposite prepared with the montmorillonite/PEG processing aids had better mechanical properties than pure mLLDPE. And the crystallinity, crystallization temperature, crystallization rate and melting temperature of mLLDPE/BPA nanocomposites were increased by adding the binary processing aids, and crystallization of mLLDPE became more complete.     

Influence of shearing history on the properties of polymer melt. II

The flow pattern of molten polymer through capillaries was studied by using a tracing method. An incompatible polymer was added to polypropylene as a tracer, and the influence of shear in a capillary rheometer on the tracer particle size as well as on the distribution of the particles in the extrudate in relation to flow was studied. It was found that the particle size varied inversely with shear rate of extrusion, capillary aspect ratio, polymer viscosity, and extrusion temperature. The flow was found to be of the telescopic type, and the tracer particle size was independent of position along the radius of the cylindrical extrudate. It is assumed that the supermolecular structure of a polymer melt is of the cluster type suggested by Busse, and it is postulated that spherical clusters of molecules in the melt are modified by shear analogously to the spherical particles of the incompatible tracer polymer. The large spectrum of melt properties obtainable, by various shearing treatments, from a polymer of constant molecular structure suggests that a wide range of supermolecular structures must be possible in the polymer melt.     

Influence of shearing history on the properties of polymer melt. I.

Melt flow behavior was examined using “as polymerized,” mechanically intact polypropylene, and the same polymer after pelletization in a screw extruder. In addition, the polymers were extruded through different capillaries and subsequently tested for melt flow characteristics. Significant differences in shear stress at a given shear rate and shear rate critical to the onset of extrudate roughness were found and compared with the previous shearing history. Both shearing intensity and mode of flow were found to impart long-lasting and short-term effects to the melt flow properties of the polymer. These differences were not explainable on the basis of changed molecular weights, since no significant differences were observed in the molecular weights as a result of the shearing treatments used in this study.     

Mechanical and flow properties of high-density polyethylene/low-density polyethylene blends

The recycling of plastic waste is of particular interest in large urban areas where municipal waste represents a large ecological problem. To achieve their objective (consumer products from plastic waste), formulators of a recycling program have to understand the implications of working with mixtures of different resins. Furthermore, in a multiphase system, the thermomechanical history experienced by the resins during processing represents an important link between operating conditions, resin properties, and final product performance. High-density polyethylene/low-density polyethylene (HDPE/LDPE) blends (10, 20, 35, 50, 65, 80, and 90 percent by weight HDPE) were melt blended in an internal mixer. A complete rheological characterization was performed on each blend. The resulting blends were extruded under different processing conditions. The extruded sheets were further characterized to determine their mechanical properties, The experimental results show important differences in the mechanical properties (transverse and longitudinal) of the sheets obtained from the blends. These differences are explained on the basis of the processing conditions (thermomechanical history) and the rheological properties of the molten blends.     

Steady flow and dynamic viscoelastic properties of branched polyethylene

The presentation of viscoelastic properties of molten high polymers in a complex plane makes three characteristic rheologic parameters appear. These are examined for a series of commercial samples of low density polyethylene. For instance, it enables products to be recognized which are very similar as far as the melt index is concerned but have different molecular weight distribution, different long chain branching index and consequently different processing properties.     

Elongational flow properties of low-density polyethylene and linear low-density polyethylene from nonisothermal melt spinning experiments

Low-density polyethylene (LDPE) and also linear low-density polyethylene (LLDPE) resins can be characterized by the degree of strain hardening and down-gaging during elongation. A new method for the determination of the apparent elongational flow characteristics is presented. In a small scale apparatus, a molten monofilament is stretched under nonisothermal conditions similar to those found in tubular film extrusion. Measurement of resistance to elongational flow and apparent elongational strain rates permit the comparison of the process-ability of different resins under specified conditions. The effect of melt temperature and extension ratio are examined. The importance of the molecular structure of both LDPE and LLDPE resins on these properties is also outlined.     

A study on the rheological properties and processability of polycarbonate

The transport theory for the solids conveying zone in a single‐screw extruder was applied to calculate the pressure distributions along the screw channel for several bisphenol A polycarbonate resins based on the screw revolution speed and the flow rate. The pressure distributions and the flow rates of the resins were related to the structural and rheological properties. When polymers have the same chemical structure and number‐average molecular weight and the same mechanical properties, the polymer having a broader molecular weight distribution showed a lower glass transition temperature. For the polymer with broader MWD a relatively low pressure was developed along the screw channel, and an increased flow rate was observed. A relatively short melting length was also observed for this polymer and, accordingly, it was concluded that the polymer with a broader MWD has a better processability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2921–2929, 2002     

Influence of shearing and time on the rheological properties of milk chocolate during tempering

The quality of chocolate is highly dependent on proper tempering. During tempering, crystals are formed as the chocolate is subjected to shear. The aim of this work was to evaluate the applicability of traditional rheological techniques to gain a better understanding of the relationship between rheological properties and the degree of shearing and time of tempering. Treatments of two shearing rates (15 and 30 s⁻¹) covering four tempering times (0, 400, 600, and 800 s) were investigated. As samples were cooled from a melt temperature of 50°C, the apparent viscosity followed the Arrhenius equation. An induction time, which was affected by shear rate, was observed during tempering, followed by an increase in apparent viscosity, caused by formation of crystalline structures. Various characteristics of the rewarming curve were attributed to polymorphism. Steady-shear constitutive models assessed after rewarming showed that the yield stress was dependent on shear and tempering time. Collectively, findings showed that traditional rheological methods may be used as tools to investigate crystallization and flow properties of molten chocolate indirectly during tempering.     

Influence of soapstone waste on the mechanical and rheological properties of high-density polyethylene

Soapstone is an abundant mineral in Ouro Preto - Minas Gerais, Brazil and its main destination is in the production of craftsmanship. Rock recovery in those activities is low and the waste disposal is done with little control, which can be hazardous to the environment. This work proposes an alternative use of such potentially harmful waste as reinforcement in a novel polymer matrix composite, which can be particularly attractive to the automotive industry and of which very little information is available elsewhere in the literature. Firstly, the characterization of the waste was performed. Particle size and shape parameters were determined by automated image analysis and the mineralogical composition was determined by X-ray diffraction, infrared, and Raman spectroscopy. High-density polyethylene was used as matrix and the composites were made in three matrix/filler ratios: 90/10, 80/20, and 70/30 by weight. Tensile and rheological properties were measured in order to determine the influence of the particles on the polymer mechanical behavior and processing conditions. The materials showed a pseudoplastic behavior and the filler's influence was more pronounced in the 70/30 composites, which showed higher viscosities than the neat polymer. The addition of particles resulted in more brittle and rigid composites, with higher values of tensile strength.     

Rheological properties of polypropylene/high-density polyethylene blend melts. I. Capillary flow properties

Three kinds of isotactic polypropylenes (PP) with different melt flow indexes (MFIs) were melt-blended with three kinds of high-density polyethylenes (HDPE) with different MFI using a screw extruder, and the morphologies and capillary flow properties such as flow curve, entrance effect, Barus effect, and melt fracture were studied. When HDPE contents were 70 wt % or above and PP particles formed the disperse phase, the size of the particles decreased with decreasing viscosity of PP. When HDPE contents were 30 wt % or below and HDPE particles formed the disperse phase, the size of the particles was minimum when the viscosities of PP and HDPE were similar. The die swell ratios of the blends were higher than those of the components. On the other hand, the entrance correction coefficients of the blends were intermediate between those of the components. There was no correlation between the die swell ratio and the entrance corretion coefficient. Therefore, it is not always appropriate to regard the entrance correction coefficient as a measure of melt elasticity in the case of inhomogeneous polymer systems such as PP/HDPE blend.