Shear and thermal history effects in polypropylene melts

Fiber grade polypropylenes with melt flow indices of 3 and 12 were studied in the aspolymerized (powder) state and after pelletization. Pelletizing operations caused very little change in the molecular weight distributions of these polymers. The lower melt flow index material exhibited much greater apparent viscosity and melt elasticity in the powder than in the pellet from during screw extrusion at 190°C. These results are consistent with the existence of a higher entanglement density in the powder version. Instron rheometer data showed no difference between the two polymer forms because of the possibility for entanglement in the rheometer reservoir during rheological experiments. The effects of sample history noted with the 3 melt flow polymer were less pronounced with the lower molecular weight 12 melt flow material. The differences in flow curves of powder and pelletized forms of the latter polymer were negligible at 175 and 190°C. Differences in die swell were more noticeable, however. The effects observed are attributable to reversible shear-induced decreases in entanglement density. Similar phenomena have been reported for other polymers. The results reported here have implications in quality control procedures for thermoplastics and in the production of polymers with desired property balances.     

Effect of combining boron nitride with fluoroelastomer on the melt fracture of HDPE in extrusion blow molding

Boron nitride (BN) is a new polymer processing aid which not only eliminates surface melt fracture in the extrusion of molten polymers, but also postpones the critical shear rate for the onset of gross melt fracture to significantly higher values that depend on resin type and additive concentration. In this work, the influence of BN as a polymer processing additive is first examined in the extrusion blow molding of high‐density polyethylene (HDPE) resins in order to evaluate its usefulness and performance in operations other than continuous extrusion. The equipment used includes both a Battenfeld/Fisher 50‐mm extrusion blow molding machine and a parallel‐plate rheometer. Two types of HDPE, which are blended with boron nitride at various concentration levels, are tested accordingly. It is found that the degree of BN dispersion, characteristics of the HDPE resins, extrusion temperature, and induction time play an important role in eliminating melt fracture. Finally, the influence of combining BN with fluoroelastomer, as an enhanced and potentially better processing aid on the melt fracture of a third HDPE is examined. It is found that such a combination is a superior processing aid that allows extrusion blow molding at very high shear rates.     

Fluorine-containing arborescent polystyrene-graft-polyisoprene copolymers as polymer processing additives

Linear low density polyethylene (LLDPE) can suffer from melt extrusion defects including sharkskin, cyclic melt fracture, and gross melt fracture during processing. Arborescent polymers are dendritic macromolecules with characteristics, such as a compact structure and a rigid spherical topology, making them potentially useful as polymer processing additives (PPA) to alleviate melt extrusion defects. Arborescent polystyrene-graft-polyisoprene copolymer samples were synthesized from polystyrene substrates of linear and branched architectures functionalized with acetyl groups, and coupled with polyisoprene macroanions. A linear polyisoprene sample was also investigated for comparison. The polymers were hydrosilylated with (tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylsilane on 17-52% of the isoprene units and blended with LLDPE at 0.1 and 0.5% w/w to evaluate their performance as PPA by extrusion at different shear rates. All the samples led to some degree of improvement in the extrusion of LLDPE, albeit the performance of the branched additives was inferior to a commercial fluoroelastomer PPA. The lower molecular weight and more compact (G0 or comb-branched) PPA generally performed better than those with a high molecular weight. Several PPA samples induced the early onset of cyclic melt fracture but glossy, defect-free surfaces were obtained at higher shear rates. This suggests that a minimum shear rate is required for these additives to coat the extrusion die under the experimental conditions used.     

Study on viscosity of polymer melt flowing through microchannels considering the wall‐slip effect

For polymers with long, complicated, branched chains, it is difficult to measure the real shear viscosity and slip velocity, using the capillary rheometer based on the adsorption–desorption mechanism. In this study, a double‐barrel capillary rheometer was used to investigate the viscosities of four polymers including polypropylene, high‐density polyethylene, polystyrene, and polymethylmethacrylate in a microchannel. A general model of polymer viscosity based on the entanglement–disentanglement was presented. The proposed model is important in understanding the mechanism of wall slip. This general model can be transferred to the other different models when changing the parameters. Actually, the entanglement–disentanglement model can also be transformed to the adsorption–desorption model. Using the model, it was found that the viscosities of polystyrene and polymethylmethacrylate were reduced with decreasing die diameter, and the slip velocities were increased with the increase of shear stress which agrees well with polymer microrheology based on the microscale effect. For polymers with long, complicated, branched chains, the proposed model improves the accuracy of the calculated viscosity and gains the real slip velocity when polymer melt flows through a microchannel. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Experimental study of the melt fracture behavior of filled high‐density polyethylene melts

In this work, the melt fracture behavior of microfilled polymer melts based on a high‐density polyethylene (HDPE) was investigated by means of a capillary rheometer, which operated at constant piston velocity. The microfilled melts examined had the same filler content (10 vol%), but differed for the type of filler (glass beads, discontinuous glass fibers, and talc). The results demonstrated that the presence of rigid fillers influences the melt fracture behavior of the filled melts in a way that is dependent on the type of filler dispersed in the HDPE melt. Opposite effects were induced by lamellar particles of talc and by glass fillers (either beads or fibers): the former promoted flow stability, whereas the latter fostered the occurrence of instabilities of “stick‐slip” type. The effects induced by the presence of the glass fillers on the oscillating flow that takes place when “stick‐slip” instabilities occur were also analyzed and discussed. POLYM. ENG. SCI., 54:364–377, 2014. © 2013 Society of Plastics Engineers     

一种阻燃抗静电聚丙烯的流变性能

采用毛细管流变仪和旋转流变仪分别研究了溴系阻燃剂、炭黑填充对聚丙烯熔体高剪切挤出畸变和动态黏弹特性的影响。发现低含量下随填充量的提高,发生挤出畸变的临界剪切速率提高,扩大了加工窗口。动态流变试验表明树脂中添加更多炭黑后剪切变稀时的复数黏度、储能模量和损耗模量都增大,但损耗因子下降。进一步用缠结模型和Cross模型定量分析表明,填料吸附高分子链段而减少其壁面吸附,减轻挤出畸变,进而提高临界剪切速率;粒子分布网络提高了平台模量和缠结密度,缩短了松弛时间,恢复更快而减小挤出胀大比。复合材料中添加3.5%（质量）炭黑后形成逾渗网络,表现为高零切黏度和长松弛时间,发生“类液-类固”转变;同时材料表面电阻下降明显,此时黏弹逾渗点与导电逾渗点基本一致。     

Effects of Extrusion Rate,Temperature, and Die Diameter on Melt Flow Properties During Capillary Flow of Low-Density-Polyethylene

The melt flow properties of a low-density polyethylene were measured at test temperatures varying from 140 to 170°C and in a wide range of extrusion rates by means of a capillary rheometer, to identify the influence of extrusion conditions (such as temperature, shear rate, and die diameter) on the melt flow behavior in the present paper. The results showed that the entry pressure drop increased nonlinearly with an increase of the piston speeds, and it decreased with an addition of the die diameter. The melt shear flow obeyed roughly the power law and the melt shear viscosity decreased approximately linearly with an increase of the true shear rates in a bi-logarithmic coordinate system. The dependence of the melt shear viscosity on temperature accorded approximately the Arrhenius expression. Under these experimental conditions, the entrance pressure drop increases as an exponential function with an addition of the channel contraction ratio.     

Capillary extrusion of composite materials

Investigations on the extrusion characteristics of composite systems were performed on the Sieglaff-McKelvey capillary rheometer, with particular emphasis on the characterization of flow instability and “melt fracture” phenomena. The mechanisms of melt fracture appear to be identical for both the filled and unfilled polymers (1. Polyethylene with glass beads; 2. Ethylene-propylene copolymer with graphitized carbon black). In all cases, the flow curves exhibit a plateau at some value of the shear stress. Above this shear stress plateau, melt fracture occurs. Although slip flow is the dominant mode of transport during melt fracture, the slippage in the tube may not be a necessary condition for the subsequent severe melt fracture.     

Studies on structural foam processing I. The rheology of foam extrusion

An experimental study was carried out to investigate the flow behavior of gas-charged molten polymers in foam extrusion. For the study, a rectangular slit die with glass windows was constructed to permit visual observations, from the direction perpendicular to flow, of the dynamic behavior of gas bubbles when a gas-charged molten polymer flows between two parallel planes. Pictures were taken of gas bubbles in the flow channel with the aid of a camera attached to a microscope, and these were later used to determine the position at which gas bubbles start to grow. Using three melt pressure transducers mounted on the short side of the rectangular slot, pressure distributions were measured along the longitudinal centerline of the die. The polymeric materials used were high-density polyethylene and polystyrene, and the chemical blowing agents used were a proprietary hydrazide which generates nitrogen, and sodium bicarbonate which generates carbon dioxide. It was observed that the gas-charged molten polymer shows a curved pressure profile as the melt approaches the die exit, whereas the polymer without a blowing agent shows a linear pressure profile. The visual observations of the bubble growth in the flow channel, together with the pressure measurements, permitted us to determine the bubble inflation pressure, often referred to as the critical pressure for bubble inflation. It was found that the critical pressure decreases with increasing melt extrusion temperature, and increases with increasing blowing agent concentration. It was also found that the bulk viscosity of gas-charged molten polymers decreases with increasing blowing agent concentration and with increasing melt temperature. A general remark is made concerning the precaution one should take when an Instron rheometer is used for determining the bulk viscosity of gas-charged molten polymers.     

The phenomenon of draw resonance in polmeric melts. Part II—correlation to molecular parameters

The Phenomenon of draw resonance and the cyclic size fluctuation of an extruded shpae are related to basic changes in the “melt strength” (force per average cross-sectional area required to draw the molten fiber down under fixed conditions). Melt strength values are obtained by a modified rheometer which consists of a vertical chamber to melt and hold the polymers at 190–250°C, a piston for extrusion, a take-up system, a strain gauge to measure the drawdown force and a recorder for continuous force-time plots. Melt strength increases with take-off speed but not proportionally. At higher velocities, draw resonance is apparent through a sinusoidal-like variation in fiber diameter. The amplitudes of melt strength and diameter waves are correlated with molecular weight, melt viscosity, swell, melt temperature and take-off speeds.     

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.     

Correlation between entry pressure losses and elongation viscosity of polyethylene melts

The correlation between the entry pressure drop and elongation viscosity during entry converging flow of polymer melts was discussed in this article. The entry pressure drop during extrusion of a low density polyethylene (LDPE) melt and a linear low density polyethylene (LLDPE) melt was measured by means of a capillary rheometer under test conditions with temperature of 170 °C and shear rate varying from 10 to 300 s⁻¹. The results showed that the entry pressure drop increased nonlinearly with an increase of the shear stain rate, and the variation of entry pressure drop of the two melts was close to each other. The melt elongation viscosity of the two resins was estimated using Cogswell equation from the measured entry pressure drop data, and the predictions were compared with the melt extension viscosity measured by using a melt spinning technique published in literature. It was found that the melt extension viscosity from entry converging flow was slightly lower than that from melt spinning technique under the same temperature and extension strain rate.     

Relationship between shear stress and shear strain of polymer melt under vibrating force field

Abstract

When a sinusoidal vibration was superimposed in parallel on the flow direction of a polymer melt being extruded through a capillary, the shear stress and shear rate of the polymer melt were analysed with a constant velocity type dynamic rheometer of capillary (CVDRC) devised by the authors. By measuring the instantaneous data of capillary entry pressure, capillary volume flux (or absolute velocity of piston rod) and their phase difference in a vibrating force field, it was found that the relationship between the pulsating amplitude value coefficient of entry pressure and that of volumetric flowrate was an approximate power series; the wall shear stress and wall shear rate of low density polyethylene (LDPE) melt extruded dynamically under various amplitudes and frequencies also exhibited a non-linear proportional relationship.     

Solid state extrusion of semicrystalline polymers

The dynamics of solid state extrusion of polypropylene, high density polyethylene, and poly(tetrafluorethylene) have been investigated at various extrusion temperatures and piston velocities. A model of solid state extrusion of semicrystalline polymers is proposed. The formulae are obtained relating the value of the extrusion pressure with the parameters of the process and polymer properties. It has been found that for certain values of the parameters, defects of two main types emerge. A mechanism of defect formation is suggested.     

聚合物动态挤出流变行为研究

本文论述聚合物材料毛细管动态流变行为的测量原理,介绍了自行研制成功的用于合物熔体挤出的毛细管动态流变仪。在该仪器上对ＬＤＰＥ进行了实验研究,发现熔体的粘度与振动源的频率、振幅呈非线性关系。在振动必场作用下ＬＤＰＥ熔体的粘度减小,随振动频率的变化有一最小值。这对矣合物动态塑化挤出工艺过程控制具有十分重要意义。     

Characterization of melt flow instabilities in polyethylene/carbon nanotube composites

The effect of single (SWCNT) and multi- (MWCNT) walled carbon nanotubes on the melt flow instabilities of polyethylenes with different topologies was characterized by means of a novel capillary rheometer allowing in-situ measurements of the pressure fluctuations inside the die and by scanning electron microscopy (SEM) analysis. Our results show that carbon nanotubes modify the main characteristics of the spurt instability developed by the linear polyethylene. Furthermore, the sharkskin instability, developed in short chain branched polyethylene, is reduced at low amounts of MWCNT and SWCNT. Noteworthy, the critical shear rate for the on-set of the spurt and the sharkskin instabilities decreases in the nanocomposites due to the physical interactions between the polymer and the nanofiller.At high shear rates, the gross melt fracture instability is completely erased in the nanocomposites based on the linear polymer whereas in short chain branched polyethylene the amplitude of this bulk distortion is rather moderated. These changes were confirmed by on-line pressure measurements using the novel capillary rheometer set-up. Based on our results, it is concluded that carbon nanotubes drastically affect the non-linear molecular dynamic leading to polyethylene melt flow instabilities.     

Polymer blend de‐mixing and morphology development of immiscible polymer blends during tube flow

This work is an investigation of morphology and de‐mixing of polymer blends during melt flow through a tube. Morphology is the relative size, shape and location of each distinguishable phase present in a polymer blend. De‐mixing is the shear‐induced migration of different types of polymers away from each other during the flow. The ability to tailor de‐mixing during extrusion can potentially result in a new family of plastics waste recycling processes with mixed waste entering an extruder and separate streams of different polymer types leaving it. Also, control of morphology development can lead to the formation of layered structures without the need for two or more extruders and co‐extrusion. This work is directed at elucidating morphology development and de‐mixing of polymer blends in the most simple process design: melt flow through a tube. Shear‐induced migration was quantitatively shown in various polyethylene‐polypropylene, polypropylene‐nylon 6 and polyethylene‐nylon 6 blends. The migration observed was in accord with the hypothesis that the system tends to minimize its rate of energy dissipation for a fixed flow rate. The ratio of the viscosity of the dispersed phased to that of the continuous phase greatly influenced the morphology of polypropylene‐nylon 6 and polyethylenenylon 6 blends: a droplet‐dispersed phase structure occurred at a high viscosity ratio, whereas a multi‐layer structure resulted at viscosity ratios near unity. Shear‐induced deformation and coalescence contributed to formation of the multi‐layer structure.     

Dynamic rheological behavior of polypropylene melts with pulsatile pressure flow in a dynamic capillary rheometer

A self‐made dynamic capillary rheometer (DCR) was designed to investigate the dynamic viscoelastic characteristic of polypropylene (PP) melt during the pulsatile pressure extrusion. A vibration force field was parallel superposed upon steady shear flow in this DCR by means of a vibration driven piston. During the pulsatile pressure extruding process in DCR, the PP melt displayed apparent viscoelasticity. The experiment results proved the pressure pulsatile extrusion could reduce the viscosity of polymer melts effectively. The phase difference between the shear stress and the shear rate decreased with the superposed vibration. But, at large amplitude conditions, the viscosity has an increasing tendency. This maybe illuminated that large amplitude could be harmful for the vibration‐assistant polymer processing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1834–1838, 2006     

Abnormal Rheological Behavior of Linear Low Density Polyethylene Melts at High Shear Rate

Abnormal rheological behavior is observed during capillary extrusion with a linear low density polyethylene (LLDPE). The nominal viscosity in the stick-slip flow regime and the gross melt fracture regime increase with a rise in temperature. This is attributed to slippage of the polymer melts. It is generally accepted that the occurrence of slippage can be detected by a Mooney analysis. However, it is found that the Mooney analysis is not applicable to detect the occurrence of slippage in the gross melt fracture regime. This is attributed to the main assumptions in the Mooney analysis being invalid in this regime, mainly due to the presence of a turbulent-like flow pattern. We suggest that failure of the time-temperature superposition principle can be used as an indication of slippage for polymer melts.     

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.