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. 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. IV. Capillary flow and die swell of low-density polyethylene

Low-density polyethylene (LDPE) melts show anomalous rheological behavior; their viscoelastic properties vary with their shearing histories although their molecular structural parameters do not change. Capillary flow and die swell behavior were dependent not only on the experimental conditions such as temperature or shear stress but also on the processing index (PI), which was introduced in a preceding article in order to quantify the anomalous rheological behavior of LDPE melts. In addition, it was found that the flow activation energy at constant shear stress also varied with the shearing histories. The experimental findings are discussed in terms of the rheological flow units of LDPE melts.     

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.     

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.     

Cold rolling of polymers. 1 Influence of rolling on properties of amorphous polymer

Strips of ductile, amorphous thermoplastic polymers such as polycarbonates, acrylonitrile-butadiene-styrenes, polysulfones and polyphenylene oxides have been reduced in thickness by passing them through a metalworking rolling mill at room temperature. Properties of the rolled strips were studied as a function of the thickness reduction. In addition to rolling unidirectionally, cross rolling (biaxial rolling) was also studied using equal thickness reductions in each direction. The maximum thickness reduction (t_o — t_f)100/t_o which could be achieved was approximately 60 per cent regardless of the polymer studied here. Stress-strain curves, density changes, thermal stability, hardness and Izod impact strengths have been determined as a function of thickness reduction and sheet direction.     

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.     

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     

支化结构对树枝状聚合物溶液剪切前后流变性能的影响

采用吴茵混调器模拟聚合物在其配制、输送、注入中的机械剪切作用,研究了不同支化程度对剪切前后的驱油用树枝状聚合物溶液的流变性能的影响。首先制备了3种不同支化程度的树枝状聚合物,研究了剪切前后的树枝状聚合物的分子链粒径分布和分子量大小,然后研究了不同因素对树枝状聚合物流变性能的影响并考察了树枝状聚合物溶液的黏弹性能,最后结合环境扫描电镜分析支化结构对剪切前后树枝状聚合物溶液的流变性能的影响。结果表明：支化程度高的树枝状聚合物具有更大的流体力学半径和分子量,受环境影响较小;树枝状聚合物溶液呈现假塑性流体特征,支化程度越高,剪切前后的聚合物溶液幂律指数n越小、稠度系数K越大;支化程度高的树枝状聚合物溶液支链间越容易发生缠结,形成致密、多层的空间网状结构,致使剪切前后的聚合物溶液的流变性能越好。     

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 nonionic polymers on the rheological and electrical properties of Egyptian bentonite

The rheological properties of Egyptian bentonite suspensions in the presence of nonionic polymers were investigated. Two different types of nonionic polymers were studied: poly(ethylene glycol) (molecular weight = 6000 g/mol) and poly(vinyl pyrrolidone) (molecular weight = 40,000 g/mol). The rheological properties (plastic viscosity, apparent viscosity, and yield point) of concentrated clay suspensions (6–8% w/w) at different temperatures after 24 h were determined. As the nonionic polymer concentrations increased, the rheological properties of the bentonite suspensions showed a slight increase, especially at an 8% clay content. The electrical properties (electrophoretic mobility and ζ potential) of Egyptian bentonite in the presence of different nonionic polymers were measured with a ζ meter. The results showed that the ζ potential of this bentonite was higher with 200 mg/L poly (vinyl pyrrolidone) than with 1000 mg/L poly(ethylene glycol). Potential energy profiles for bentonite suspensions for these nonionic polymers were constructed to show that the net energy barrier for bentonite suspensions followed repulsion or attraction between particles. These profiles showed that the potential energy profile of a bentonite suspension with 200 mg/L poly(vinyl pyrrolidone) produced a high repulsion potential energy between clay surfaces; that is, the suspension stability improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of long-chain branching on the rheological properties of low density poly(ethylene)

The objective of this work was to correlate rheological parameters with basic molecular parameters such as different molecular weights and level of long-chain branching (LCB) in low density polyethylene. LCB is known to exert a considerable influence on resin's melt flow characteristics which have been useful in predicting resin end-use properties (especially processability). In the scope of the work steady flow measurements were done with an Instron Rheometer and dynamic oscillatory measurements using a balance rheometer. The molecular weight data were obtained using gel permeation chromatography, light scattering technique, and solution viscosimetry. A correlation matrix was calculated for 34 measured properties. The results showed that good correlations may be obtained especially between LCB-parameters, die swell and optical properties of the polymer. The LCB properties may also be quite correctly predicted from dynamic viscosity data at low frequencies.     

Studies on the preparation and properties of conductive polymers. III. Metallized polymer films by retroplating out

A novel method to prepare polymer metallized films was found by using polymer metal chelate films treated with wetted metal plates (or metal powders). The polymer metal chelate films were prepared by metal salts mixed with the polymers containing a functional group, such as poly(vinyl alcohol) (PVA), polyamide, polyacrylamide (PAAm), and polyurethane (PU). This novel method is called the retroplating-out method. Polymer metallized films exhibited low surface resistivity around 10^?1 Ω/cm² by using this novel method. The surfaces of these films were shown to be metallized by means of X-ray analysis. The conduction mechanism was verified reasonably well by using scanning electron microscope (SEM) and UV-visible absorption data.     

Effects of coupling agents on the rheological properties,processability, and mechanical properties of filled polypropylene

An experimental study was carried out to investigate the effects of coupling agents on the rheological properties, processability, and mechanical properties of highly filed polypropylenes (PP). Inorganic fillers used were CaCO₃ and glass beads, and coupling agents used were two silane coupling agents, N-octyl triethoxy silane and γ-aminopropyl triethoxy silane, and one titanate coupling agent, isopropyl triisostearoyl titanate. It was found that the addition of the coupling agents to the PP-CaCO₃ (50 wt percent) decreased the melt viscosity and increased the melt elasticity (first normal stress difference). However, the addition of the silane coupling agents to the PP-glass beads (50 wt percent) affected the rheological properties of the melts quite differently. The N-octyl triethoxy silane had relatively little effect on either the melt viscosity or the melt elasticity, whereas the γ-aminopropyl triethoxy silane increased the melt viscosity and decreased the melt elasticity. The CaCO₃- or glass bead-filled polypropylenes, with and without coupling agents, were injection-molded and the mechanical properties of the molded specimens were measured by the use of an Instron testing machine. It was found that the effect on the tensile strength and percent elongation of the filled polypropylenes depended upon the specific coupling agent utilized. A melt-spinning study was also carried out to investigate the effect of coupling agents on the spinnability (defined as the maximum draw-down ratio) of the PP-CaCO₃ system, and on the mechanical properties of the melt-spun fibers. It was found that the spinnability of the PP-CaCO₃ was enhanced considerably by the addition of the coupling agents, and that the tensile strength of the melt-spun fibers was also improved by their addition. Scanning electron micrographs were taken of the fracture surface of injection-molded specimens and an attempt was made, with the aid of photomicrographs, to explain the mechanical properties of molded specimens observed experimentally.