Prediction of high density polyethylene processing behavior from rheological measurements

In order to predict the processing behavior of a high density polyethylene resin one must know the resin flow behavior over a wide range of shear rates. Low shear properties are important in applications where melt strength, sagging, etc. are critical. On the other hand, high shear flow properties are a determining factor in applications where melt instability, melt fracture and heat generation are important. The flow behavior of a resin can be established by measuring the zero shear viscosity, η₀, the maximum relaxation time, τ₀, and the shape of the flow curve. We have measured these basic rheological parameters on a large number of high density polyethylene resins. A shear sensitivity parameter which is independent of molecular weight was derived from a correlation between η₀ and τ₀. This parameter, together with η₀, provide the vital information needed in order to predict the processing behavior of the resin. This method is applicable to other polymer systems provided that the rheological parameters η₀ and τ₀ can be experimentally obtained.     

Morphology and rheological properties of polypropylene-linear low density polyethylene blends

The dynamic shear viscosity and the morphology of polypropylene homopolymer and copolymer blended with linear low density polyethylene are studied. A maximum in the dynamic shear viscosity vs. blend composition is reported for the polypropylene copolymer, linear low density polyethylene system. The increasing dynamic shear viscosity is in accordance with the occurrence of a morphology of polyethylene inclusions in rubber surrounded by a polypropylene matrix. Comparing calculations of the dynamic shear viscosities—based on a shell model with interlayer—and experimental results supports this view.     

Ultrasonic oscillations effect on rheological and processing properties of metallocene‐catalyzed linear low density polyethylene

The effects of ultrasonic oscillations and die materials on die pressure, productivity of extrusion, melt viscosity of metallocene‐catalyzed linear low density polyethylene (mLLDPE), as well as their mechanism were studied in a special ultrasonic oscillations extrusion system developed in our lab. Die materials used in our experiment included steel, brass, and polytetrafluoroethylene (PTFE)_. The experimental results showed that ultrasonic oscillations as well as die materials have great influence on the rheological and processing behavior of mLLDPE. Ultrasonic oscillations can greatly increase the productivity of mLLDPE melt extruded through different dies, and can decrease the die pressure and the melt viscosity of mLLDPE. Compared with steel or brass die, mLLDPE melt extruded through PTFE die is more sensitive to ultrasonic oscillations. A possible mechanism for the improved processability of mLLDPE is proposed in this article. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1873–1878, 2003     

加工助剂对HDPE流变性能的影响

采用熔体流动速率仪、毛细管流变仪和Haake流变仪研究了极性低聚物、含氟聚合物、有机硅化合物3种加工助剂对高密度聚乙烯(HDPE)流变性能的影响,并对其作用机理进行了探讨。研究发现:熔体流动速率仪和毛细管流变仪无法表征这三种加工助剂对HDPE的降黏作用;用Haake流变仪测试表明,加入1 000μg/g加工助剂就能明显降低HDPE在挤出过程中的加工扭矩,进而降低能耗,提高机器寿命和生产效率;极性低聚物和有机硅化合物降低HDPE扭矩的机理和含氟聚合物不同,是内外润滑作用相结合的复合效果。     

The effect of processing on rheological and molecular characteristics of a low density polyethylene

The viscoelastic responses of some molten polymers, and particularly of low density polyethylene (LDPE), are known to vary with processing history. Reasons for the variations include the effects of shear history on morphological states of the polymer, or on its molecular weight parameters. A typical low density polyethylene has been used to test the shear-history dependence concept following a variety of processing steps. The polymer was sheared in single-screw and twin-screw extruders, and in a high speed melter / mixer (Gelimat). Samples also were precipitated from very dilute solutions in trichlorobenzene and in p-xylene. GPC analyses showed that, in general, these procedures did not affect the various moments of molecular weight. An exception was the Gelimat-mixed sample, for which mild reductions in M_n and M_w were noted. In contrast, melt viscosity and elasticity readings, the former from low shear evaluations and the latter from extrudate swelling, were affected by the various procedures. A drop in melt viscosity and in elasticity was observed, being most pronounced for precipitated and twin-screw extruded versions of the LDPE. Reductions also were observed in the specimen sheared in the Gelimat instrument. Following conditioning at the test extrusion temperature (170°C), viscous and elastic responses tended to revert to those of the unsheared control sample, the exception again being the sample sheared in the Gelimat melter / mixer. Of the various mechanisms proposed in the literature to account for transient property changes such as those reported, temporary changes in the degree of chain entanglement appear the most satisfactory explanation. Irreversible alterations in viscoelastic properties may be associated with changes in molecular weights due to processing at high shear.     

Anisotropy of optical and mechanical properties of stretched low density polyethylene

Summary Parallel measurements of IR dichroism, birefringence and microhardness anisotropy of drawn low density polyethylene films have been carried out. The angle α between the dipole moment vector of the IR band at 1367 cm⁻¹ and the chain axis has a value of 50°. The longitudinal and transverse moduli of the drawn samples, measured by microhardness indentations, increase as the draw ratio increases after passing through a minimum for a draw ratio of around 1.5. Received: 27 April 1998/Revised version: 22 July 1998/Accepted: 22 July 1998     

Blends of high‐density polyethylene with chlorinated polyethylene: Morphology,thermal, rheological,and mechanical properties

Blends of high‐density polyethylene (HDPE) with chlorinated polyethylene (CPE) were generated using melt mixing. CPE of two different chlorination contents was used and its amount in the blends was varied from 1% till 30%. The rheological, thermal, mechanical, and morphological properties of the blends were characterized along with miscibility analysis. In general, better mixing of the CPE polymer in HDPE was observed at lower CPE concentration and reduced mixing or immiscibility occurred at higher concentration of CPE. However, the extent of immiscibility was different in both CPE25 and CPE35 systems. The rheological analysis of the data using Cole‐Cole, Han‐Chuang and van Gurp plots confirmed the miscibility of CPE25 blends (except for 30% CPE25 blend at lower frequency) whereas CPE35 blends with 10–30% CPE content were immiscible. Highest increase in the rheological properties (complex moduli) was observed at 2% CPE content. The mechanical properties of the CPE25 blends were superior than the corresponding CPE35 blends especially at higher CPE concentration where effects of immiscibility as well as matrix plasticization played a role. The morphology characterization using TEM indicated change in the crystalline features of the polymer in the case of CPE35 blends. The optical microscopy also confirmed the better mixing of CPE25 polymers in HDPE than CPE35. The CPE25 blends exhibited uniformly dispersed CPE phase which was also confirmed by the rheological analysis. However, the blends of CPE35 with 10% CPE content onwards had significant phase immiscibility. POLYM. ENG. SCI., 54:85–95, 2014. © 2013 Society of Plastics Engineers     

LDPE分子结构对流变行为的影响

采用流动双折射和动态流变实验方法研究了低密度聚乙烯(LDPE)分子结构对其流变行为的影响.熔体在突变收缩口模中流动时的等差线图显示,两种LDPE的流动特性明显不同.由动态流变实验可知,LDPE 1810D在低频剪切时复数黏度比LDPE 2426K大,拟合得到的离散松弛时间谱范围较窄,表明两者的相对分子质量及其分布差别较...     

The effect of processing conditions on the rheological properties of blends of ultra high molecular weight polyethylene with high‐density polyethylene

Blends of high‐density polyethylene (HDPE) with small amounts of ultra‐high molecular weight polyethylene (UHMWPE) were prepared by melt mixing in a twin‐screw microcompounder. Two types of UHMWPE differing in their states of chain entanglement were used. The blend composition, time of mixing, and rotation speed of the screws were varied. Rheological properties of the blends were studied in oscillatory shear and uniaxial elongational tests. Reduction in phase angle measured in dynamic shear rheology and increase in extensional strain hardening were found to be useful indicators for quantifying the extent of mixing of the two components. Although the disentangled UHMWPE showed reasonable mixing with HDPE during typical residence times of melt compounding operations, the entangled UHMWPE remained essentially undissolved. The extent of mixing increased with mixing time and screw speed. POLYM. ENG. SCI., 59:821–829, 2019. © 2018 Society of Plastics Engineers     

Electrical properties of natural-fiber-reinforced low density polyethylene composites: A comparison with carbon black and glass-fiber-filled low density polyethylene composites

The electrical properties of sisal fiber-low density polyethylene (LDPE) and coir fiber-LDPE composites have been studied. The dielectric constant progressively increases with increase of fiber loading and decreases with increase of frequency in the case of all composites. The dielectric constant of sisal-LDPE composites has been studied as a function of fiber length. Volume resistivity values decrease with fiber content. The increase of dielectric constant with fiber loading is more predominant at low frequencies in both the sisal fiber-LDPE and coir fiber-LDPE composites. The results of the natural-fiber-filled composites were compared to those of the carbon and glass-fiber-filled LDPE composites. The dielectric constant of carbon-black-loaded LDPE composites increases with carbon content, and the increase is sharper at high carbon content. This is associated with the network formation of carbon black in LDPE matrix. © 1997 John Wiley & Sons, Inc.     

茂金属线型低密度聚乙烯的结构与性能

利用傅里叶变换红外光谱、凝胶渗透色谱、差式扫描量热法和力学性能测量等手段表征了茂金属线型低密度聚乙烯(mLLDPE)和传统线型低密度聚乙烯(LLDPE)的结构及性能,用热分级法表征了LLDPE的片晶厚度多散性,测试了mLDPE薄膜的相关性能。结果发现,mLLDPE的片晶厚度分布指数为1.1347,小于传统LLDPE,表明其具有更好的支化均匀性,但其相对分子质量分布窄;mLLDPE薄膜具有较高的落镖冲击强度、撕裂强度、热封强度和突出的光学性能。     

Molecular,rheological, and crystalline properties of low‐density polyethylene in blown film extrusion

The molecular weight and its distribution, degree of long chain branching and cooling rate strongly influence crystallinity during processing, which in turn determines the processability and the ultimate properties of the blown film. Generally a decrease in the number of branches and molecular weight of the polymer and the cooling rate results in an increase of the crystallinity. Length of the main chain and extent of branching in low‐density polyethylene (LDPE) are also factors that affect melt rheology and film crystallinity. Long chain branched polyethylene is suitable in the blown film process due to its better melt strength for bubble stability. The objective of this article is to describe the effect of molecular properties (e.g. molecular weight and its distribution, degree of long chain branching etc) of LDPE on film crystallinity at different cooling rates of blown film extrusion. Two different grades of LDPE were selected to investigate molecular characteristics, crystallinity, and rheology. The resins were processed in a blown film extrusion pilot plant using four different cooling rates. Molecular, rheological, and crystalline properties of the resins were key parameters considered in this study. POLYM. ENG. SCI., 47:1983–1991, 2007. © 2007 Society of Plastics Engineers     

茂金属线性低密度聚乙烯树脂的结构与性能

对国产和进口茂金属线性低密度聚乙烯树脂(mLLDPE)的分子量及分布、支化程度、基本性能与流变行为进行了对比分析,研究表明国产mLLDPE与进口同类产品相比,分子量分布宽,支化程度高,加工性能更好,可以通过流变测试的各种参数如黏流活化能、剪切变稀指数、松弛谱分布宽度对其结构进行剖析。同时对两者薄膜制品的性能进行了研究,结果表明,国产mLLDPE树脂生产的薄膜力学性能更为优异,但鱼眼稍多,外观略差。     

Mechanical properties of polystyrene/low density polyethylene blends

Some mechanical properties of blends of polystyrene and low density polyethylene have been derived from stress-strain and impact measurements. The strength and impact properties are improved by adding a graft copolymer of polystyrene and low density polyethylene to the blends. It is assumed that the copolymer acts as an adhesive at the interface of the homopolymers thus decreasing the stress concentrations around the dispersed polymer particles at yield. The impact strength and modulus of polystyrene-graft copolymer blends could be made comparable to those of commercial rubber-modified impact polystyrenes by adjusting the fraction of copolymer in the blend.     

Morphology,thermomechanical properties,and biodegradability of low density polyethylene/starch blends

The biodegradability of low density polyethylene (LDPE)/starch and LDPE/starch/starch acetate (STAc) blends was tested and observed to be dependent on STAc content. The binary and ternary blends containing up to a maximum concentration of 30% starch were examined for their thermal, mechanical, and morphological properties. The blends with no STAc or 2.5% STAc show almost no adherence of two phases. With 10% STAc, dispersion of starch was observed to increase with some adherence to LDPE. Tensile strength, elongation at break, and Izod impact strength of the blends decreased with increased starch content. However, incorporation of STAc along with starch improved all these properties, particularly elongation at break and toughness. The melt flow index was also improved on partial substitution of starch by STAc. Maximum biodegradability was observed for the blends containing 30% (starch + STAc). Cell growth was observed to increase with increasing concentration of (starch + STAc) in the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2791–2802, 1999     

High density polyethylene/polystyrene blends: Phase distribution morphology,rheological measurements,extrusion, and melt spinning behavior

An experimental study of the development of phase morphology, rheological properties, and processing behavior of mechanical blends of a polystyrene (PS) and a high density polyethylene (PE) is presented. Phase morphologies were determined by scanning electron microscopy for (i) products prepared in a screw extruder/static mixer system, (ii) samples removed from a cone-plate viscometer, (iii) extrudates, and (iv) melt spun fibers. Disperse phase dimensions were measured. The values varied from 1–5 μm in the products from static mixers. The dimensions of the dispersed phase in the blend products from the cone plate and capillary die were of the same order. The melt-spun fibers exhibited disperse phase dimensions as low as 0.35 μm. Polystyrene was extracted from the blend fibers producing small diameter, PE fibrils, or minifibers. Both the initial melts and the blends were rheologically characterized. The shear viscosity and principal normal stress difference N₁ exhibit maxima and minima when plotted as a function of composition. The characteristics of extrudates and melt spinning behavior of the blends were investigated. The shrinkage of extrudates of PE is much greater than PS. Additional small amounts of PE to PS greatly increase its shrinkage. Addition of PE to PS initially increases extrudate swell, though the swell shows maxima and minima when considered as a function of composition. The positions of the maxima and minima correspond to those of N₁. The onset of draw resonance has been investigated in isothermal melt spinning. Wide angle X-ray diffraction studies have been carried out on blend fibers and the orientation of the crystalline polyethylene regions has been determined as a function of process conditions. This orientation decreases rapidly with the addition of polystyrene when the melt-spun filaments are compared at the same spinline stress or drawdown ratio.     

Effect of compatibiliser on rheological behaviour of straw fibre/low density polyethylene composites

Abstract

Rheological behaviour of suspensions of straw fibre in low density polyethylene (LDPE) melts was investigated at a certain temperature over a wide range of frequencies using a plate rheometer operated in dynamic mode. The viscoelastic of composite melt changed gradually with the straw fibre content increasing, for example at the low frequency region the slope of the G′ decreased from 1.67 of the plain LDPE to 0.889 of 50?wt-% straw fibre plastic composite. The addition of compatibiliser doubled the tensile strength, and the relaxation time reduced from 405 to 214?s. It was observed that the presence of compatibiliser may be attributed to improve interaction between the polymer and filler, which reduces the resistance of the agglomeration of straw fibres, lessening the relaxation time. Consequently, the straw fibre plastic composite is easier to produce.     

Mechanical and rheological properties of reinforced polyethylene

The rheological and mechanical properties of a high density polyethylene (HDPE) filled with surface-treated mica flakes are reported. Young's modulus decreases with different treatments, whereas break elongation and maximum strength slightly increase. Young's modulus increases with the addi ion of mica flakes, but the decrease in elongation is also quite significant. For 20% mica composites, hardly any change was observed in the properties. The high shear viscosity does not show any significant effect as a result of the surface treatment. Viscosity of composites increases with silane treatment and decreases with titanate treatment. It is suggested that the coupling agent, depending on its chemical structure and nature of the filler, may act as an adhesion promoter or as a lubricating agent.     

Origin of the molecular structure and properties of low density polyethylene

It is generally accepted that the origin of the structural features of low density polyethylene (branching, unsaturation, molar mass and its distribution) can be explained by various isomerisation and decomposition reactions of the macroradicals and by various chain transfer processes. On the other hand, it is known that ethylene molecules under high pressure are organised in various supermolecular particles. There are several phases in compressed ethylene (α, β and γ) depending on the pressure and temperature. The purpose of the present work was to determine the effects of the phase state of ethylene on the structure and properties of polyethylene. The authors have compiled published data about the effects of the synthesis pressure and temperature on the structure and properties of polyethylene. The entropy of ethylene under sythesis conditions for those published experiments was determined from the available information on pressure and temperature. The effects of ethylene entropy on the number and type of short chain branches, long chain branches, unsaturated bonds, molar mass and its distribution, chain flexibility, density and the melting point of polyethylene are demonstrated. It was found that under given ethylene entropy conditions, the same structure and properties of polyethylene are obtained.     

Orientation and mechanical properties of polycarbonate- linear low density polyethylene blends

Five blends of polycarbonate (PC) with linear low density polyethylene (LLDPE) were studied. Characterization of the blends was made by means of rheological measurements and domain morphology determined by SEM microscopy. A fine dispersion was obtained for the 25/75 PC/LLDPE. The blends were then oriented, LLDPE and 25/75 PC/LLDPE at room temperature, and the others at 165°C. For the hot drawn blends (50/50 and 75/25 PC/LLDPE), a significant increase in tensile strength and elongation at break is observed. For the room temperature drawn samples, modulus and tensile strength values increase whereas elongation at break decreases. This is explained in terms of morphological and molecular orientation effects. Comparison of the experiments to the predictions of different models for the modulus shows a good agreement for unoriented blends. However, for oriented samples, important discrepancies are observed, suggesting that the morphology and orientation are important factors in predicting the modulus of these blends. A model which takes into account these factors is proposed and a good fit of the modulus is obtained.