Melt elongation flow behaviour of LDPE/LLDPE blends

The extensional rheological properties of low density polyethylene (LDPE)/linear low density polyethylene (LLDPE) blend melts were measured using a melt spinning technique under temperatures ranging from 160 to 200 °C and die extrusion velocities varying from 9 to 36 mm/s. The results showed that the melt elongation stress decreased with a rise of temperature while it increased with increasing extensional strain rate and the LDPE weight fraction. The dependence of the melt elongation viscosity on temperature roughly obeyed the Arrhenius equation, it increased with increasing extensional strain rate and the LDPE weight fraction when the extensional strain rate was lower than 0.5 s⁻¹, and it reached a maximum when the extensional strain rate was about 0.5 s⁻¹, which can be attributed to the stress hardening effect.     

Experimental study on viscosity properties of cyclic olefin copolymer (COC) flowing through micro capillary dies

As an emerging polymer, COC has been commonly used to make microfluidic chips by microinjection molding; and in this process, COC melt flows in a trans-scale cavity in which macro and micro scales coexist. Thus, in such a circumstance, understanding viscosity property of COC melt would be helpful to mold design, parameter determination of injection molding and prediction of molding quality. In this paper, viscosity properties of COC melt flowing in three dies with different diameters (500 μm, 200 μm, 100 μm) were investigated at three different temperatures (240 °C, 260 °C, 280 °C) by a capillary rheometer. The results showed that viscosity of COC melt flowing in different micro dies can be reduced significantly by increasing temperature, and visco-temperature property of COC melt could be described by Vogel equation in a considerable accuracy. It was found that temperature sensitivity of viscosity of COC melt varies with shear rate. Besides, as die diameter decreased, viscosity of COC melt was also reduced greatly. Moreover, in 500 μm die, viscosity of COC decreased constantly with shear rate; however, in 200 μm and 100 μm dies, viscosity witnessed an increase within a certain shear rate range. It implies that behavior of COC molecular chains might varies in different micro-scales.     

熔体黏度对黏土在聚丙烯/聚苯乙烯共混物中优先插层行为的影响

通过熔融共混法在160℃加工条件下制备了聚丙烯/聚苯乙烯/黏土(PP/PS/clay)复合材料.X射线衍射分析(XRD)和透射电镜分析(TEM)的结果表明,黏土在共混物中存在着优先插层现象.黏土优先被PS分子链所插层,且不受PS组分含量和加料方式的影响.基于复合材料中PP和PS组分的熔体黏度对温度敏感性的差别,通过改变加工温度的方法,研究组分的黏度差别对黏土优先插层行为的影响.随共混加工温度的升高,黏土在共混物中的分布位置逐渐从PS相向PP相迁移.TEM和动态黏弹行为测试(ARES)的结果表明,组分间黏度的差别能控制黏土的优先插层行为.组分黏度越高,加工过程中所能传递的剪切应力就越大,插层能力也就越强.     

Melt flow behavior of polypropylene composites filled with multi-walled carbon nanotubes during extrusion

Polypropylene (PP) composites filled with multi-walled carbon nanotubes (MWCNTs) were prepared using a twin-screw extruder. The melt flow properties of the composites were measured with a capillary rheometer in a temperature range from 180 to 230 °C and at various apparent shear rates varying from 100 to 4000 s⁻¹. The results showed that the melt shear stress increased almost linearly while the melt shear viscosity decreased almost linearly with increasing shear rates in a bi-logarithmic coordinate system. The melt shear flow followed the power law relationship and the dependence of the melt shear viscosity on temperature obeyed the Arrhenius equation. The relationship between the melt shear viscosity and the MWCNT weight fraction was roughly linear under the investigated range of temperature or shear rate.     

Investigation of polypropylene degradation during melt processing using a profluorescent nitroxide probe: A laboratory-scale study

Degradation of polypropylene (PP) during melt processing was studied using a novel profluorescence technique. The profluorescent nitroxide probe, 1,1,3,3-tetramethyldibenzo[e,g]isoindolin-2-yloxyl (TMDBIO) was added to PP during melt processing to act as a sensor for carbon-centred radicals. Trapping of carbon-centred radicals, formed during degradation of PP, led to an increase in fluorescence emission from TMDBIO adducts. Through analysis of viscosity changes during processing cumulative chain scission degradation was estimated. At processing temperatures of 210 °C or below, fluorescence emission from TMDBIO adducts could be correlated with cumulative chain scissions when the number of chain scissions was small. At higher temperatures, a correlation was not observed most probably due to radical-trap instability rather than decomposition of the TMDBIO. Thus, TMDBIO may be used as a profluorescent sensor for degradation of PP during melt processing when the processing temperature is 210 °C or below.     

Capillary extrusion of polypropylene/high-density polyethylene immiscible blends as studied by rheo-particle image velocimetry

The capillary extrusion of polypropylene (PP) and high-density polyethylene (HDPE) immiscible blends was studied in this work by rheo-particle image velocimetry (Rheo-PIV). The PP/HDPE blends were prepared by single screw extrusion and extruded through a transparent capillary die at a temperature of 200 °C and concentrations of 80/20, 60/40, 40/60 and 20/80 wt%, respectively. PIV measurements described accurately the flow behavior of PP/HDPE blends and revealed continuous velocity profiles in the die, without macroscopic phase separation, for all the blends in the resolution range of the PIV technique. The flow behavior of all the blends was shear-thinning (power-law) type and their viscosities laid in between the values corresponding to the neat polymers and increased in an exponential way along with the concentration of the highest viscosity component in the blend (HDPE). Also, it was found that the extruded blends acquired a stratified morphology and that HDPE mitigates extrudate distortions in PP, meanwhile PP eliminates slip and flow instabilities in HDPE by migrating to the region of highest shear stresses in the die. Migration of PP to the capillary wall was corroborated by Raman spectroscopy measurements on the periphery of solid extrudates. Finally, via calculations of the density of the molten blends under flow using the velocity profiles in the die, we show that the homopolymers are compatible in the molten state and follow a simple inverse relation for their density, and an exponential one for their viscosity.     

Rheological characterization of the die swell phenomenon of rubber compounds

The die swell phenomenon of rubber compounds in capillary experiments with various ratios of length to diameter of capillaries is investigated. This knowledge is important for the design of injection heads for the extrusion of rubber profiles. The die swell of viscoelastic rubber compounds depends on the geometry of the capillary dies, on the melt temperature and on the shear strain rate. One empirical relationship will consider all these dependencies. Usage of this equation and identification of only one new material parameter enables the comparison and assessment of the die swell of different materials, independently of the corresponding geometry of the capillary die used. Furthermore, the influence of melt temperature, molecular structure and extrusion process on the die swell can be identified. The investigation was performed with various rubber compounds as well as rubber blends used in industry, mainly EPDM and carbon black in different compositions.     

Detecting extensional viscosity of polypropylene melt using the Rheotens test: A comparison between standard and steady state test modes

The Rheotens test was used to determine the extensional viscosity of a polypropylene (PP) melt at three different extrusion velocities and using two capillaries with different length-to-diameter ratios. Results showed that, in the standard Rheotens test, the extensional viscosity curves determined under different testing conditions exhibit an obvious difference, especially under low extensional strain rates. This is attributed to the pre-orientation of macromolecular chains taking place in the capillary. Hence, a steady state Rheotens test was tentatively proposed. It was demonstrated that the extensional viscosity curves determined under most of the testing conditions by this test mode almost overlap, which is attributed to the fact that the pre-orientation of chains relaxes sufficiently near the capillary exit. This implies that equivalent extensional viscosities can be obtained under a wider range of extrusion velocities and capillary length-to-diameter ratios. Moreover, the equivalent extensional viscosities determined in the steady state Rheotens test exhibit good agreement with the extrapolated extensional viscosity curve determined using the Cogswell convergent flow method.     

Melt flow behavior in capillary extrusion of nanometer calcium carbonate filled PCL bio-composites

Nanosized calcium carbonate (nano-CaCO₃) filled polycaprolactone (PCL) bio-composites were prepared by using a twin-screw extruder. The melt flow behavior of the composites, including the entry pressure drop, melt shear flow curves and melt shear viscosity, were measured through a capillary rheometer operated in a temperature range of 170∼200 °C and shear rates varying from 50 to 10³ s⁻¹. The entry pressure drop showed a non-linear increase with increasing shear stress when the filler weight fraction was less than 3%, while it decreased slightly with an increase of shear stress at a filler weight fraction of 4%. The melt shear flow roughly followed a power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Moreover, the influence of the nano-CaCO₃ on the melt shear viscosity of the PCL composite was not significant at low filler levels.     

超高分子量聚苯乙烯的流变性能

以毛细管流变仪和Hakke转矩流变仪对稀土催化合成的超高分子量聚苯乙烯 (UHMWPS)的流变与加工性能进行了研究 .结果表明 ,UHMWPS最显著的流变特征为超高的熔体粘度和低剪切速率下出现不稳定流动 .不稳定流动与超高分子量聚合物长的松弛时间有关 ,并提出了临界剪切速率与分子量和温度的定量关系式 .较低的分子量和较高的温度有利于提高临界剪切速率 ,改善挤出物外观质量和降低熔体粘度 .分子链极度缠结不仅导致超高的熔体粘度 ,也使UHMWPS链解缠加快 ,导致更高的剪切速率敏感性 .UHMWPS塑化时熔体粘度高 ,转矩大 ,加工性能劣于通用聚苯乙烯 (GPPS)     

热致性液晶共聚酯的拉伸流动行为

采用入口收缩流动的实验方法研究了改性PET/ 80PHB液晶共聚酯LCP80的拉伸流动行为 ,考察了拉伸速率、温度等对其拉伸粘度、Trouton比的影响 .实验结果表明 ,LCP80的入口压降值很大 ,其中由拉伸引起的入口压降是主要的 .在该文实验条件下LCP80均表现出拉伸稀化现象 ,并且Trouton比值都远大于 3 .根据流动中液晶织态结构的变化解释了实验现象 ,并对入口收缩流动的实验数据处理方法作了改进 ,比Beery的方法更为合理 ,也具有更广的适用性 .     

Characterization of elongation viscosity for polyethylene melts

Elongation viscosity is an important characterization of flow properties for polymer melts. In the present article, a new extensional viscosity equation for polymer melts was established by introducing a relaxation time equation based on the Cross model. The elongation viscosities of a low-density polyethylene (LDPE) melt at 200 °C and a metallocene linear low-density polyethylene (mLLDPE) melt at 130 °C were estimated using this equation; then, the calculations of the melt elongation viscosity were compared with the measured data from the extension experiments of the LDPE melt and the mLLDPE melt reported in the reference. Good agreement was found between the predictions and the measured data from the LDPE and mLLDPE melts. In addition, this equation is easy to use for characterization of elongation viscosity during single shaft elongation flow for polymer melts.     

Characteristics and design procedure of hyperbolic dies

Nozzle profiles capable of generating constant extensional strain rates are termed hyperbolic dies. When used in polymer extrusion, they exhibit greater potential in inducing and retaining polymer molecular orientation than conventional capillary dies. Most mathematical expressions found in the literature involve several processing variables in describing and designing such nozzle profiles. This report reveals that a hyperbolic die profile, although rather complicated, can be expressed with equations in terms of two ordinary geometrical parameters—the exit diameter and the hyperbolic length. This finding greatly simplifies the design procedure of hyperbolic dies. The extensional strain rate of a hyperbolic die can be related to the length-to-diameter ratio for any given exit diameter. Examples of various types of die profiles are presented and their constant extensional strain-rate characteristics are discussed.     

Analysis of entrance pressure drop techniques for extensional viscosity determination

In this work, a novel (patent pending) orifice die design for precise extensional viscosity data determination from entrance pressure drop measurements has been developed and tested both theoretically (through Finite Element Analysis) and experimentally. It has been demonstrated that the proposed novel orifice die allows much more precise extensional viscosity measurements for polymer melts in comparison with conventional orifice dies. Moreover, it has been found that, for extensional strain hardening and extensional strain thinning polymer melts, the corrected Cogswell model and Binding/Gibson model should be preferred, respectively. Otherwise, the extensional viscosity determination can be rather erroneous.     

Die swell ratio of polystyrene melt from an electro‐magnetized capillary die in an extrusion rheometer: effects of barrel diameter,shear rate and die temperature

A constant shear‐rate extrusion rheometer with an electro‐magnetized capillary die was utilized to investigate die swell behavior and flow properties of a polystyrene melt as the application of an electro‐magnetic field to the capillary die was relatively novel in polymer processing. The test conditions such as magnetic flux density, barrel diameter, extrusion rate and die temperature were studied. The results suggest that the maximum swelling of the polystyrene melt with application of the electro‐magnetic field could be enhanced up to 2.6 times (260%) whereas that without the electro‐magnetic field was 1.9 times (190%). The barrel diameter of 30 mm was found to be a critical value in the case of the die swell ratio and flow properties of the polystyrene melt were significantly affected by the magnetic flux density. This involved the number and angle of magnetic flux lines around the barrel part. Under the electro‐magnetic field, there were two mechanical forces influencing the die swell ratio and the flow properties; magnetic torque and shearing force. The die swell at wall shear rates less than 11.2 sec^?1 was caused by the magnetic torque, whereas at higher wall shear rates it was dependent on the shearing force. For a given magnetic flux density, the maximum increase in the die swell ratio as a result of the magnetic torque was calculated to be approximately 20%. Increasing the die temperature from 180 to 200°C reduced the overall die swell ratio and suppressed the effect of the magnetic flux density. Copyright © 2004 John Wiley & Sons, Ltd.     

Rheological,morphological, thermal,and mechanical properties of blends of vectra A950 and poly(trimethylene terephthalate): A study on a high-viscosity-ratio system

Poly(trimethylene terephthalate) (PTT) and a liquid crystalline polymer, Vectra A950 (VA), were melt-blended and subjected to capillary rheometry. Effects of VA content, shear rate and temperature on viscosity and flow activation energy (E_a) were investigated. Partial fibrillation was found even though the viscosity ratio was greater than one, leading to the formation of in-situ composites. Thermal and thermogravimetric analysis of the blends suggested that they were immiscible and their thermal stabilities were enhanced. From tensile tests, the incorporation of VA improved tensile modulus, slightly decreased tensile strength, and drastically lowered elongation at break, compared to neat PTT. It was found that the blend with the best VA dispersion can be achieved at the minimum VA content (10 wt%) and lowest processing temperature (250 °C). Not only did this blend exhibit improved mechanical properties comparable to those of blends processed at temperatures closer to the crystalline-to-nematic transition of VA (～280 °C), it also shows enhanced processibility through the reduction of both melt viscosity and E_a.     

Studies on melt flow properties during capillary extrusion of PP/Al(OH)3/Mg(OH)2 flame retardant composites

The apparent melt shear viscosity of polypropylene (PP) composites filled with aluminium hydroxide (Al(OH)₃) and magnesium hydroxide (Mg(OH)₂) was measured by means of a melt flow rate instrument under experimental conditions of temperature ranging from 170 to 195 °C and load varying from 2.16 to 12.5 kg, to identify the effects of particle size and content. The results showed that the melt shear flow of the composites obeyed the power law under the experimental conditions, the dependence of the melt apparent shear viscosity (η_a) on temperature was consistent with the Arrhenius equation, and the sensitivity of the η_a for the composite melts to temperature increased with addition of flame retardant. The η_a of the composites decreased with increasing apparent shear rate. The η_a increased with an increase of the content of flame retardant, but this rate of increase decreased with a rise of temperature or load. When the particle size of flame retardant was smaller than 5 μm, the η_a of the composites increased with increase of particle size of flame retardant, and then reduced with a further increase of particle size of flame retardant.     

Effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene compatibilizer on the recycled polypropylene and recycled high‐impact polystyrene blends

The recycled polypropylene/recycled high‐impact polystyrene (R‐PP/R‐HIPS) blends were melt extruded by twin‐screw extruder and produced by injection molding machine. The effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene copolymer (SEPS) used as compatibilizer on the mechanical properties, morphology, melt flow index, equilibrium torque, and glass transition temperature (T_g) of the blends were investigated. It was found that the notch impact strength and the elongation at break of the R‐PP/R‐HIPS blends with the addition of 10 wt% SEPS were 6.46 kJ/m² and 31.96%, which were significantly improved by 162.46% and 57.06%, respectively, than that of the uncompatibilized blends. Moreover, the addition of SEPS had a negligible effect on the tensile strength of the R‐PP/R‐HIPS blends. Additionally, the morphology of the blends demonstrated improved distribution and decreased size of the dispersed R‐HIPS phase with increasing the SEPS content. The increase of the melt flow index and the equilibrium torque indicated that the viscosity of the blends increased when the SEPS was incorporated into the R‐PP/R‐HIPS blends. The dynamic mechanical properties test showed that when the content of SEPS was 10 wt%, the difference of T_g decreased from 91.72°C to 81.51°C. The results obtained by differential scanning calorimetry were similar to those measured by dynamic mechanical properties, indicating an improved compatibility of the blends with the addition of SEPS.     

Rheological behavior of POM polymer melt flowing through micro-channels

Determination of the rheological behavior of the polymer melt within micro-structured geometry is vital for accurate simulation modeling of micro-molding. The lack of commercial equipment is one of main hurdles in the investigation of micro-melt rheology. In this study, a melt viscosity measurement system for POM melt flowing through micro-channels was established. For measured pressure drop and volumetric flow rate, both capillary and slit flow models were used for the calculation of viscosity. The calculated results were also compared with those of PS resin to discuss the effect of morphology structure on the viscosity characteristics of polymer within micro-channels. It was found that the measured POM viscosity values in the test ranges are significantly lower (about 29-35% for a channel size of 150 μm) than those obtained with a traditional capillary rheometer. Meanwhile, the percentage reduction in the viscosity value and the ratio of slip velocity relative to mean velocity all increase with decreasing micro-channel size, but less significantly when compared with PS resin. In the present study we emphasize that the rheological behavior of the POM resin in microscopic scale is also different from that of macroscopic scale as PS resin but displays a less significant lower. It also revealed that the wall slip occurs more easily for the PS resin within micro-channels than POM resin due to enlarge the effect of molecular weight.     

Melt extrudate swell behavior of graphene nano-platelets filled-polypropylene composites

The extrudate swell ratios of polypropylene (PP) composite melts filled with graphene nano-platelets (GNPs) were measured using a capillary rheometer within a temperature range of 180–230 °C and apparent shear rate varying from 100 to 4000 s⁻¹ in order to identify the effects of the filler content and test conditions on the melt die-swell behavior. It was found that the values of the extrudate swell ratio of the composites increased with increasing apparent shear rate, with the correlation between them obeying a power law relationship, while the values of the extrudate swell ratio decreased almost linearly with rise in temperature. The values of the melt extrudate swell ratio increased approximately linearly with increasing shear stress, and decreased roughly linearly with an increase of the GNP weight fraction. In addition, the extrudate swell mechanisms are discussed from the observation of the fracture surface of the extrudate using scanning electronic microscopy. This study provides a basis for further development of graphene reinforced polymer composites with desirable mechanical performance and good damage resistance.