Experimental study of elongational flow and failure of polymer melts

A new and simple instrument for measurement of elongational flow response of polymer melts in constant uniaxial extension rate experiments is described. Quantitative stress development data are presented for a series of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polystyrene (PS), polypropylene (PP), and poly(methyl methacrylate) (PMMA) melts. For small elongation rate E, linear viscoelastic behavior was observed; while for large E, LDPE and PS showed exponential stress growth, while HDPE and PP showed only linear stress growth. Stress relaxation experiments were carried out for several of the same melts in the instrument. Elongation to break and mechanisms of filament failure were studied. HDPE and PP have a tendency to neck and exhibit ductile failure, while at high E, LDPE and PS seem to show cohesive fracture. The elongational flow stress response data were compared to predictions of nonlinear viscoelastic fluid theory, specifically the Bogue-White formulation. The qualitative differences in responses of the melts studied were explained in terms of different dependences of the effective relaxation times on deformation rate and, more specifically, on values of the a parameter in the theory.     

Elongation properties of polyethylene melts

The extensional rheological properties of three grades of polyethylene melts, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE) were measured using a melt spinning technique under the test conditions with temperature ranging from 150 to 210°C and extrusion rate varying from 11.25 to 22.50 mm s^?1. The results showed that the melt strength decreased with a rise of temperature while increased with an increase of extensional rate. With the rise of extensional strain rate and temperature, the melt extensional viscosity decreased. The extensional stress and viscosity reduced with increasing extrusion velocity when the temperature and extensional rate were constant. Moreover, the melt strength and extensional viscosity of the LDPE resin was the highest and the LLDPE was the lowest under the same experimental conditions. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Dichotomous behavior of polymer melts in isothermal melt spinning

Isothermal melt spinning experiments have been conducted using two polyethylene melts of low density (LDPE) and high density (HDPE) to produce steady state spinline profiles. The data revealed the threadline extensional viscosity exhibiting a contrasting picture : extension thickening behavior for LDPE and extension thinning one for HDPE. A White-Metzner model having a strain rate-dependent relaxation time was then found to be able to simulate this dichotomy in melt spinning fairly well: the fluids whose relaxation times have smaller strain rate-dependence can fit LDPE data with extension thickening extensional viscosity whereas the fluids whose relaxation times have larger strain rate-dependence can fit HDPE data with extension thinning extensional viscosity. This dichotomous nature of viscoelastic fluids is also believed to be able to explain other similar contrasting phenomena exhibited by polymer melts, such as vortex/no vortex in entry flows, cohesive/ductile fracture modes in extension, and more/less stable draw resonance than Newtonian fluids.     

Self‐reinforcement of high‐density polyethylene/low‐density polyethylene prepared by oscillating packing injection molding under low pressure

This article reports the toughness improvement of high‐density polyethylene (HDPE) by low‐density polyethylene (LDPE) in oscillating packing injection molding, whereas tensile strength and modulus are greatly enhanced by oscillating packing at the same time. Compared with self‐reinforced pure HDPE, the tensile strength of HDPE/LDPE (80/20 wt %) keeps at the same level, and toughness increases. Multilayer structure on the fracture surface of self‐reinforced HDPE/LDPE specimens can be observed by scanning electron microscope. The central layer of the fracture surface breaks in a ductile manner, whereas the break of shear layer is somewhat brittle. The strength and modulus increase is due to the high orientation of macromolecules along the flow direction, refined crystallization, and shish‐kebab crystals. Differential scanning calorimetry and wide‐angle X‐ray diffraction find cocrystallization occurs between HDPE and LDPE. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 799–804, 1999     

The flow of polymer melts through the clearance over a barrier flight in extruders

The flow of polymer melts through the clearance over a barrier flight in extruders involves high, rapidly changing shear rates. Polymer melts, being viscoelastic, are expected to exhibit a high elasticity when they flow through the clearance, so the flow through the clearance may not be predictable or stable. The flow through the clearance over a barrier flight was investigated using a shear refining (SR) module connected to an extruder. Three polymers with different melt properties were tested: branched low density polyethylene (BLDPE), high‐density polyethylene (HDPE), and polystyrene (PS). The measured drag flow rate through the clearance was found to be equal to the prediction for a purely viscous fluid, which gives a linear velocity profile in the clearance. At the threshold rotor speed of the SR module whereupon the predicted drag flow rate through the clearance is the same as the extruder output rate, the melt pressures at the inlet and the outlet of the SR module were nearly equal and stable. Below the threshold rotor speed, the inlet pressure was higher than the outlet pressure. Above the threshold rotor speed, the inlet pressure was nearly zero and the outlet pressure fluctuated. The magnitude of the pressure fluctuation increased with increasing rotor speed and decreased with increasing melt temperature. HDPE, which had a higher melt elasticity, showed more pressure fluctuation than BLDPE and PS. The pressure fluctuation probably results from the flow instability through the clearance caused by the melt elasticity.     

Thermal characteristics and temperature profile changes of structurally different polyethylenes with peroxide modifications

Crosslinking and processing characteristics of polyethylenes (PEs) with different molecular architectures, namely high‐density polyethylene (HDPE), linear low‐density polyethylene (LLDPE), and low‐density polyethylene (LDPE), were studied with regard to the effects of peroxide modifications and coolant flow rates. Dicumyl peroxide (DCP) and di‐tert‐butyl peroxide (DTBP) were used as free‐radical inducers for crosslinking the PEs. The characteristics of interest included normalized gel content, real‐time temperature profiles and their cooling rates, exothermic period, crystallinity level, crystallization temperature, and heat distortion temperature. The experiments showed that LDPE exhibited the highest normalized gel content. The real‐time cooling rates, taken from the temperature profiles for all PEs before the crystallization region, were greater than those after the crystallization region. The cooling rate of the PEs increased with the presence of DCP, whereas the crystallization temperature of the PEs was lowered. The HDPE appeared to show the longest exothermic period as compared with those of the LLDPE and LDPE. The exothermic period showed an increase with increasing coolant flow rate, but it was decreased by the use of DCP. As for the effect of peroxide type, the gel content and cooling rate of the PE crosslinked by DCP were higher than those for the PE crosslinked by DTBP. The DTBP was the more effective peroxide for introducing crosslinks and simultaneously maintaining the crystallization behavior of the PE. J. VINYL ADDIT. TECHNOL., 20:80‐90, 2014. © 2014 Society of Plastics Engineers     

Improvement of the polarity of polyethylene with oxidized Fischer–Tropsch paraffin wax and its influence on the final mechanical properties

The easy, low‐cost modification of the polarity of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) through blending with oxidized Fischer–Tropsch wax was investigated. A 10 wt % concentration of the wax increased the polar component of the total surface free energy 10 times for LDPE and 4.5 times for HDPE. Modified LDPE also had significantly higher adhesion to the polar substrate, which was represented by a crosslinked epoxy‐based resin. This behavior was not observed for HDPE. The conservation of the good mechanical properties of polyethylene was observed. The wax content had only a moderate influence on the mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1164–1168, 2005     

Formation and characterization of polyethylene blends for autoclave‐based expanded‐bead foams

Blends of linear‐low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and high‐ density polyethylene (HDPE) were foamed and characterized in this research. The goal was to generate clear dual peaks from the expanded polyethylene (EPE) foam beads made from these blends in autoclave processing. Three blends were prepared in a twin‐screw mixing extruder at two rotational speeds of 5 and 50 rpm: Blend1 (LLDPE with 20 wt% HDPE), Blend 2 (LLDPE with 20 wt% LDPE), and Blend 3 (LLDPE with 10 wt% HDPE and 10 wt% LDPE). The differential scanning calorimetric (DSC) measurement was taken at two cooling rates: 5 and 50°C/min. Although no dual peaks were present, the results showed that blending with HDPE has a more noticeable effect on the DSC curve of LLDPE than blending with LDPE. Also, the rotational speed and cooling rate affected the shape of the DSC curves and the percentage area below the onset point. The DSC characterization of the batch foamed blends revealed multiple peaks at certain temperatures, which may be mainly due to the annealing effect during the gas saturation process. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

方柱绕流中聚乙烯熔体流变行为的数值模拟

采用了DCPP和S-MDCPP两种模型分别描述低密度聚乙烯熔体的本构行为。在迭代分步算法中引入了改进的有限增量微积分(FIC)法,并采用离散的弹性黏性应力分裂技术(DEVSS)/迎风流线(SU)法解决黏弹性流动分析中的对流占优问题。讨论了S-MDCPP模型预测的速度、压力及主链拉伸分布随Weissenberg(Wi)数的变化。结果表明,两种模型预测的速度、主应力差等色条纹和主链拉伸分布吻合较好;随Wi的增大,速度及压力均增大。     

Numerical simulation of polymer foaming process in extrusion flow

Computer simulations of polymer foaming processes in extrusion flow have been carried out in order to improve current understanding of viscoelasticity and bubble growth effects on die-swelling in the production of polymer foam. The linear and non-linear viscoelastic materials functions of a commercial low density polyethylene (LDPE) melt have been extracted by fitting its rheometric data with constitutive models including a simple viscoelastic model (SVM), the exponential Phan-Thien–Tanner (EPTT) model and the double convected pom–pom (DCPP) model. Simulations of LDPE melt under extrusion flow without foaming show that the predictions of the die-swell by the SVM are in reasonably good agreement with the results obtained from the EPTT and DCPP models. By comparison of the simulation results of LDPE foaming in extrusion flow using the Bird–Carreau model and the SVM, a cooperative effect of polymer viscoelasticity and bubble growth on the die-swell has been quantified. The numerical results also show that the density of polymeric foam decreases significantly with the increasing concentration of foaming agent, and that the combination of the SVM and bubble growth model can account for some essential physics of polymer foaming process in extrusion flow.     

A theoretical analysis of non-isothermal flow in wire-coating co-extrusion dies

A theoretical study of non-isothermal superimposed flow of two polymer melts in wire coating co-extrusion dies has been carried out. Numerical methods have been employed to solve the coupled momentum- and energy-balance equations. Various combinations of three polymers—namely, high density polyethylene (HDPE), polystyrene (PS) and low density polyethylene (LDPE) have been studied and least squares curve fitted quadratic polynomials have been used for constitutive equations for all three polymers in non-Newtonian high shear rate regions. A multitude of thermal and mechanical boundary conditions can be treated by this algorithm. It was found that temperature and velocity profiles in the die depend significantly on the arrangement of the polymers. Maximum temperature rise has been noted to increase sharply with wire velocity but it can be reduced by increasing the die radius. When the thickness of the outer layer is increased from zero, the shear stress at the wall undergoes a dramatic change (if the viscosities of the polymers are different) at small values of the flow rate ratio and it reaches an asymptotic value at large values of flow rate ratio. It was also found that viscosity ratio at the interface can be reduced by changing the initial temperatures of the liquids. It was observed in some cases that large errors in the calculation of rheological and thermal variables for this problem can be made if temperature rise due to viscous dissipation is not considered.     

Melt spinning flow behaviour of high-density polyethylene blended with low-density polyethylene

ABSTRACT

The melt spinning flow behaviour of a high-density polyethylene (HDPE) blended with a low-density polyethylene (LDPE) was studied using a melt spinning technique in temperature ranging from 160 to 200°C and die extrusion velocity varying from 9 to 36?mm?s^?1. The results showed that the melt apparent extension viscosity of the blends was higher than those of the LDPE and HDPE; the melt apparent extension viscosity decreased with increasing temperature; while the melt apparent extension viscosity increased with increasing extension strain rate when the extension strain rate was lower than 0.2?s^?1, and then decreased; the melt apparent extension viscosity reached up to a maximum value when extension strain rate was about 0.2?s^?1; the relationship between the melt apparent extension viscosity and the LDPE weight fraction did not follow the mixing rule.     

Co‐crystallization in ternary polyethylene blends: tie crystal formation and mechanical properties improvement

Understanding the co‐crystallization behavior of ternary polyethylene (PE) blends is a challenging task. Herein, in addition to co‐crystallization behavior, the rheological and mechanical properties of melt compounded high density polyethylene (HDPE)/low density polyethylene (LDPE)/Zeigler ? Natta linear low density polyethylene (ZN‐LLDPE) blends have been studied in detail. The HDPE content of the blends was kept constant at 40 wt% and the LDPE/ZN‐LLDPE ratio was varied from 0.5 to 2. Rheological measurements confirmed the melt miscibility of the entire blends. Study of the crystalline structure of the blends using DSC, wide angle X‐ray scattering, small angle X‐ray scattering and field emission SEM techniques revealed the formation of two distinct co‐crystals in the blends. Fine LDPE/ZN‐LLDPE co‐crystals, named tie crystals, dispersed within the amorphous gallery between the coarse HDPE/ZN‐LLDPE co‐crystals were characterized for the first time in this study. It is shown that the tie crystals strengthen the amorphous gallery and play a major role in the mechanical performance of the blend.© 2016 Society of Chemical Industry     

Modification of recycled high‐density polyethylene by low‐density and linear‐low‐density polyethylenes

The present study investigated mixed polyolefin compositions with the major component being a post‐consumer, milk bottle grade high‐density polyethylene (HDPE) for use in large‐scale injection moldings. Both rheological and mechanical properties of the developed blends are benchmarked against those shown by a currently used HDPE injection molding grade, in order to find a potential composition for its replacement. Possibility of such replacement via modification of recycled high‐density polyethylene (reHDPE) by low‐density polyethylene (LDPE) and linear‐low‐density polyethylene (LLDPE) is discussed. Overall, mechanical and rheological data showed that LDPE is a better modifier for reHDPE than LLDPE. Mechanical properties of reHDPE/LLDPE blends were lower than additive, thus demonstrating the lack of compatibility between the blend components in the solid state. Mechanical properties of reHDPE/LDPE blends were either equal to or higher than calculated from linear additivity. Capillary rheological measurements showed that values of apparent viscosity for LLDPE blends were very similar to those of the more viscous parent in the blend, whereas apparent viscosities of reHDPE/LDPE blends depended neither on concentration nor on type (viscosity) of LDPE. Further rheological and thermal studies on reHDPE/LDPE blends indicated that the blend constituents were partially miscible in the melt and cocrystallized in the solid state.     

非牛顿流体自然收敛半角方程的实验验证

引言非牛顿流体从大截面流道进入小截面流道时形成的收敛流动，是工业过程中常见的流型，如石油输运、聚合物加工过程等．流体的自然收敛角定量地描述了流体在流道入口前区的流动形态．在先前的工作中，作者应用最小能原理，导出非牛顿流体自然收敛半角方程式中，e是Bagley校正因子，n是非牛顿指数，是与流体的粘附性能有关的系数．聚合物熔体属于典型的非牛顿流体．本工作中，拟在考察聚乙烯熔体于毛细管挤出过程中流变行为的基础上，对方程（2）作初步验证1实验1.1原材料选用高密度聚乙烯（HDPE）和低密度聚乙烯（LDPE）作为试样材料…     

Comparative ozonization of LDPE and HDPE and grafting of some monomers to elaborate new ion exchange membranes

A comparative study of the ozonization of low density polyethylene (LDPE) and high density polyethylene (HDPE) was carried out. A grafting study of acrylic acid (AA), N,N‐dimethylamino‐2‐ethylmethacrylate (MADAME) and vinyl phosphonic acid (VPA) on LDPE and HDPE was performed in mass and solution. The ozonized polyethylene and the grafting polymers were characterized by IR spectroscopy and elementary analysis. Ion exchange membranes were prepared from grafted copolymers and characterized by the exchange capacity and electrical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4423–4429, 2006     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.