Effect of the high‐density polyethylene melt index on the microcellular foaming of high‐density polyethylene/polypropylene blends

The effect of high‐density polyethylene (HDPE)/polypropylene (PP) blending on the crystallinity as a function of the HDPE melt index was studied. The melting temperature and total amount of crystallinity in the HDPE/PP blends were lower than those of the pure polymers, regardless of the blend composition and melt index. The effects of the melt index, blending, and foaming conditions (foaming temperature and foaming time) on the void fractions of HDPEs of various melt indices and HDPE/PP blends were also investigated. The void fraction was strongly dependent on the foaming time, foaming temperature, and blend composition as well as the melt index of HDPE. The void fraction of the foamed 30:70 HDPE/PP blend was always higher than that of the foamed 50:50 HDPE/PP blend, regardless of the melt index. The microcellular structure could be greatly improved with a suitable ratio of HDPE to PP and with foaming above the melting temperature for long enough; however, using high‐melt‐index HDPE in the HDPE/PP blends had a deleterious effect on both the void fraction and cell morphology of the blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 364–371, 2004     

Effect of vibration extrusion on the structure and properties of high‐density polyethylene pipes

BACKGROUND: The axial strength of a plastic pipe is much higher than its circumferential strength due to the macromolecular orientation during extrusion. In this work, a custom‐made electromagnetic dynamic plasticating extruder was adopted to extrude high‐density polyethylene (HDPE) pipes. A vibration force field was introduced into the whole plasticating and extrusion process by axial vibration of the screw. The aim of superimposing a vibration force field was to change the crystalline structure of HDPE and improve the molecular orientation in the circumferential direction to obtain high‐circumferential‐strength pipes. RESULTS: Through vibration extrusion, the circumferential strength of HDPE pipes increased significantly, and biaxial self‐reinforcement pipes could be obtained. The maximum increase of bursting pressure and tensile yield strength was 34.2 and 5.3%, respectively. According to differential scanning calorimetry and wide‐angle X‐ray diffraction measurements, the HDPE pipes prepared by vibration extrusion had higher crystallinity, higher melting temperature, larger crystal sizes and more perfect crystals. CONCLUSION: Vibration extrusion can effectively enhance the mechanical properties of HDPE pipes, especially the circumferential strength. The improvement of mechanical properties of HDPE pipes obtained by vibration extrusion can be attributed to the higher degree of crystallinity and the improvement of the molecular orientation and of the crystalline morphology. Copyright © 2008 Society of Chemical Industry     

Degradation of polyethylene during extrusion. II. Degradation of low‐density polyethylene,linear low‐density polyethylene,and high‐density polyethylene in film extrusion

The degradation of different polyethylenes—low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and high‐density polyethylene (HDPE)—with and without antioxidants and at different oxygen concentrations in the polymer granulates, have been studied in extrusion coating processing. The degradation was followed by online rheometry, size exclusion chromatography, surface oxidation index measurements, and gas chromatography–mass spectrometry. The degradations start in the extruder where primary radicals are formed, which are subject to the auto‐oxidation when oxygen is present. In the extruder, crosslinking or chain scissions reactions are dominating at low and high melt temperatures, respectively, for LDPE, and chain scission is overall dominating for the more linear LLDPE and HDPE resins. Additives such as antioxidants react with primary radicals formed in the melt. Degradation taking place in the film between the die orifice, and the quenching point is mainly related to the exposure time to air oxygen. Melt temperatures above 280°C give a dominating surface oxidation, which increases with the exposure time to air between die orifice and quenching too. A number of degradation products were identified—for example, aldehydes and organic acids—which were present in homologous series. The total amount of aldehydes and acids for each number of chain carbon atoms were appeared in the order of C5>C4>C6>C7?C2 for LDPE, C5>C6>C4>C7?C2 for LLDPE, and C5>C6>C7>C4?C2 for HDPE. The total amounts of oxidized compounds presented in the films were related to the processing conditions. Polymer melts exposed to oxygen at the highest temperatures and longest times showed the presence dialdehydes, in addition to the aldehydes and acids. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1525–1537, 2004     

Theoretical and experimental study on three-layered polymeric balloon catheter processing

Multilayered polymeric balloon catheters, one of the most important components during interventional treatment, are drawing more attention recently due to the microscale cross section, excellent mechanical properties, and high accuracy. During multilayered polymeric balloon catheter processing, many operating conditions can affect the size and shape of cross sections. In this study, polymer melt flow behavior inside extrusion die is theoretically analyzed first. Then, ethylene vinyl acetate (EVA) and polypropylene (PP) are selected as the build materials to produce the middle and inner layers of three-layered polymeric balloon catheters, while polyamide (PA) and thermoplastic elastomer (TPE) are used to make the outer layer of two types of catheters, respectively. Based on the material selection, a three-layered coaxial die is designed and manufactured to coextrude three different polymer melts to form corresponding catheters. In addition, the effects of operating conditions including outer layer materials, pulling speed, gas flow rate, and screw rotation speeds on the diameters and wall thicknesses as well as the concentricity and ovality of the extrudates are investigated. Finally, the PA-EVA-PP and TPE-EVA-PP three-layered catheters are successfully fabricated, which have well-defined geometries and high shape accuracy.     

Statistical and kinetic approaches for linear low‐density polyethylene melting modeling

The aim of this study was to compare different models, either originating from literature or originally proposed in this study, for the interpretation of the melting behavior of polymers. In particular, these models, tested with a linear low‐density polyethylene widely used in rotational molding, are suitable for coupling with energy balances in the study of polymer processing. We obtained the experimental data from differential scanning calorimetry (DSC) dynamic scans, assuming that the endothermic flux was related to the rate of melting of the polymer. The studied models were able to predict the broad melting temperature range typically observed during polymer melting with either a statistical or a kinetic approach. The two different approaches were compared with experimental DSC data. The analysis of model performances with complex thermal programs showed that the statistical approach could provide a more realistic representation of polymer melting. These models were particularly suitable in rotational molding, where the lack of any flow and, hence, of any crystalline orientation leads to a degree of melting determined by the actual temperature of the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 289–295, 2003     

Mechanical properties and structure of high‐density polyethylene samples prepared by injection molding with low‐frequency vibration

To better understand the formation of different crystal structures and improve the mechanical properties of high‐density polyethylene samples, melt vibration technology, which generally includes shear vibration and hydrostatic pressure vibration, was used to prepare injection samples. Through melt vibration, the crystal structure changed from typical spherulites of the traditional injection sample to obviously orientated lamellae of vibration samples. Sizes and orientation degrees of lamellae were different according to different vibration conditions. Crystallinity degrees of vibration samples increased notably. Therefore, the tensile strength of vibration samples increased with increasing vibration frequency and vibration pressure, whereas elongation of vibration samples decreased during the first stage and then continued to increase as the vibration frequency increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 818–823, 2005     

Impact of organoclay and maleated polyethylene on the rheology and instabilities in the extrusion of high density polyethylene

The impact of organoclay on the rheology and extrusion of high density polyethylene (HDPE) was studied. Organoclay effect was studied at very low clay loading (≤0.1 wt %) while serving as a processing aid. A special design slit die with three transducers was used in the study of the extrusion melt instabilities. The rheological results showed that normal stress difference of HDPE was reduced during steady shear rate and stress growth tests when organoclay (≤0.1 wt %) was added. The extensional strain and stress growth of HDPE reduced with the addition of organoclay. So, organoclay (≤0.1 wt %) has an effect on the shear and extensional rheology of HDPE. The intensity of the melt instability was characterized with both a moment analysis and distortion factor (DF) from an advanced Fourier transform analysis. Both showed the same trends in the characterization of the pressure fluctuations in the die. Generally, addition of organoclay (≤0.1 wt %) to HDPE led to the reduction in DF. The ratio of first and second moment analyses became reduced as well. The results quantified the extent of elimination of gross melt fracture in HDPE by organoclay. Also, the extrusion pressure was reduced with organoclay (≤0.1 wt %) inclusion hence more throughput. There was a good correlation between rheology and extrusion. Both showed that the platy‐like organoclay streamlined the melt flow. However, the maleated polyethylene added as a compatibilizer did not give substantial synergistic effect. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ultrasonic decrosslinking of crosslinked high‐density polyethylene: Effect of screw design

The effect of screw design on decrosslinking of the crosslinked high‐density polyethylene (XHDPE) by means of ultrasonic twin‐screw extruder with two screw configurations is investigated. Die pressure and ultrasonic power consumption during extrusion are recorded. Swelling characteristics, rheological properties, thermal analysis, scanning electron microscopy, and tensile properties are used to investigate the structure–property relationship of decrosslinked XHDPE. It is found that the screw configuration with conveying elements and reverse conveying elements (decrosslinking screws) is an effective means to reduce the gel fraction and crosslink density of decrosslinked XHDPE and significantly improve its processibility. Rheological properties of decrosslinked XHDPE are correlated with structural changes occurring during ultrasonic decrosslinking. The presence of the highly branched sol in decrosslinked XHDPE is revealed through measurements of the activation energy for flow. Comparison of morphologies of the lamellar structure of HDPE, XHDPE, and decrosslinked XHDPE reveals that the presence of the crosslink network inhibits the lamella growth. Significant improvements in the mechanical performance of decrosslinked XHDPE are obtained by using decrosslinking screws. The molecular structure and morphology of the lamellar structure of decrosslinked XHDPE are used to explain the processing–solid‐state property relationship. The measured results on the gel fraction and crosslink density are compared with those of numerical simulations. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40680.     

Effect of styrene‐butadiene‐styrene addition on polystyrene/high‐density polyethylene blends

In order to prepare an ideal mixture, the physical and chemical properties of the constituent polymers must be known in detail. Thus, selection of the polymers that will constitute the mixture and a thorough study of the mixing methods and the economic factors become important. A rigid plastic is toughened by dispersing a small amount of rubbery material (generally 5–20%) in the rigid plastic matrix. Such a mixture of plastics is characterized by its impact resistance. Among thermoplastics toughened in this way are polystyrene (PS), poly(vinyl chloride), poly(methyl methacrylate), polypropylene, polycarbonate, and nylons, and recently thermoset resins such as epoxies, unsaturated polyester resins, and polyamids. In this study PS and high‐density polyethylene polymers were mixed in various ratios. In order to increase the compatibility of the mixtures, 5, 7.5, and 10% SBS copolymer was also added. The mixing operation was conducted by using a twin‐screw extruder. The morphology and the compatibility of the mixtures were examined by using SEM and DSC techniques. Furthermore, the elastic modulus, yield and tensile strengths, percent elongation, Izod impact resistance, hardness, and melt flow index values of the polymer alloys of various ratios were determined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2967–2975, 2002; DOI 10.1002/app.2325     

Interfacial tension measurements and evidence of order in high‐density polyethylene melts

Polyethylene (PE) is a widely used product commercially. However, our knowledge is incomplete about the properties of high‐density polyethylene (HDPE) at temperatures above its melting point, where solid crystals disappear. Recently, there has been increasing evidence from rheological, differential scanning calorimetry, and NMR studies that suggests the presence of microstructural order in the bulk of PE melts. In this study, the interfacial tension of HDPE melts in contact with silicone oil was measured with a spinning drop tensiometer in the same temperature range in which phase transitions have been observed in the bulk HDPE. Anomalous temperature dependence of interfacial tension was found between 200 and 230°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4061–4067, 2003     

Processability‐enhanced bimodal high‐density polyethylene with comb‐branched high‐density polyethylene

Two solution reactors in series were utilized to synthesize comb‐branched high‐density polyethylene (HDPE), cbHDPE, where the first reactor prepares vinyl‐terminated HDPE macromers catalyzed by an organometallic catalyst favoring beta hydride transfer and the second reactor copolymerizes HDPE macromers with ethylene using a different organometallic catalyst capable of incorporating macromers. A bimodal HDPE, biHDPE with bimodalities in molecular weight, and hexene content of the desired composition distribution was also prepared in a gas phase reactor using silica supported dual organometallic catalysts. By blending 3% solution‐made cbHDPE into the gas‐phase biHDPE, the resulting trimodal HDPE preserves the excellent stiffness and toughness of the bimodal HDPE while having exceptional melt strength and processability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45755.     

Two‐step degradation of high‐density polyethylene during multiple extrusion

Ensuing our recent studies on polyethylene stabilization,^1,2 further multiple extrusion experiments were carried out with a high‐density polyethylene (HDPE) polymer containing various amounts of a sterically hindered phenolic antioxidant. Discoloration, thermoxidative stability, and melt flow index (MFI) retention were measured by standard techniques; the functional group content of the polymer was determined by Fourier transform infrared (FTIR) spectroscopy, and rheological, as well as mechanical properties, were also measured. The results indicated that degradation and stabilization reactions take place according to two different mechanisms in the first and subsequent processing steps, respectively. Color development could be described well by the simple first‐order overall reaction kinetics proposed earlier, and color change could be related to the stability of the polymer. The existence of general correlations among the properties proved that all chemical reactions are interrelated. The reactions of the stabilizer lead to color development, while those of the polymer to a modification of its molecular architecture, which determines the rheological and mechanical characteristics of the product. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1596–1605, 1999     

Electrical resistivity of carbon black filled high‐density polyethylene composites

The electrical resistivity of high‐density polyethylene (HDPE) loaded with carbon black (CB) blends was evaluated as a function of the blending time and the melt index of HDPE. The relationship between the positive temperature coefficient effect and the room temperature volume resistivity was investigated. The positive temperature coefficient effect and reproducibility were improved significantly when the blending time of HDPE and CB was comparatively long. The effects of ⁶⁰Co γ‐ray and electron beam irradiation on the positive and negative temperature coefficient behavior of the blends were studied. The effect of thermal aging on the volume resistivity was studied to ascertain the structural stability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2440–2446, 2002     

Ultraviolet preirradiation of high‐density polyethylene for the grafting of maleic anhydride during reactive extrusion

High‐density polyethylene was irradiated with ultraviolet light for various exposure times, as a prestep for hydroperoxide production, before a bulk grafting reaction with maleic anhydride in the melt phase by reactive extrusion. This method was compared with a traditional grafting procedure using peroxides optimized by an evaluation of the grafting level versus the screw speed; the highest speed showed the greatest grafting value. The reaction was followed by Fourier transform infrared, the gel percentage, and the grafting degree, which was evaluated by titration. The effect of grafting for both methods under the established processing conditions on the thermal properties was observed with differential scanning calorimetry via their heating and cooling thermograms; there were notorious changes in the fusion peak temperatures, indicating differences in the crystallization process after the grafting reaction. The latter was confirmed by NMR spectroscopy, which showed succinic anhydride rings attached to the polyethylene chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2882–2888, 2006     

Melt flow indexer evidence of high‐temperature transitions in molten high‐density polyethylenes

A melt flow indexer (MFI) was used to investigate high‐temperature transitions in melts of high‐density polyethylene (HDPE). The MFI data were obtained in the range 190–230°C. These transitions were found in the MFI at about 210 and 225°C and reproduced in a Haake melt blender. Polystyrene was used in the blender experiment to demonstrate typical amorphous behavior. For HDPE melts, the MFI–temperature behavior and the torque–temperature data of the blender were found to be alternative images of the same anomalous temperature dependency in the range 210–225°C. Also, the Haake melt blender was able to reproduce the 150°C transition observed by Kolnaar and Keller in the extrusion of HDPE. Regardless of the simplicity of the MFI device, results are in agreement with our previous DSC findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1309–1313, 2004     

Effects of chemical modification of wood flour on the rheological properties of high‐density polyethylene blends

Chemical modification of lignocellulosic fibers can improve interfacial adhesion and dimensionally stabilize the resulting plastic composites. This study examined the rheological properties of wood flour/high density polyethylene (HDPE) melts after poplar wood flour was modified with glutaraldehyde (GA, mainly cell wall cross‐linking) and 1,3‐dimethylol‐4,5‐dihydroxyethyleneurea (DMDHEU, mainly poly‐condensation). Results show improvement in both the dispersibility of treated wood flour in the HDPE and its interfacial compatibility. Treatment with GA decreased melt viscosity, moduli, and shear stress as evidenced by rheometry. However, the modifying effects of DMDHEU were not observed, which was mainly due to reduced HDPE content. This study indicates that chemical modification of wood flour is a promising approach to improve the processability of highly filled wood thermoplastic composites via extrusion/injection molding processing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41200.     

Functionalization of high‐density polyethylene in the molten state by glycidyl methacrylate grafting

:This study concerns the melt‐free radical grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE). We studied the effect of two initiators (tert‐butyl cumyl peroxide and di‐tert‐butyl peroxide) onto HDPE. Crosslinking of polymer was observed in the presence of 0.3 wt % tert‐butyl cumyl peroxide but not with 0.3 wt % di‐tert‐butyl peroxide. The grafting was carried out in a Brabender batch mixer at 190 °C. The grafting yield of GMA onto HDPE (determined by infrared spectrometry) is weak (<1 wt % for an initial concentration in monomer of 6 wt %). Moreover, it was noted that the degree of grafting did not vary with the concentration and the nature of peroxide used. To increase the grafting yield of GMA, we added to the HDPE/peroxide/GMA system an electron‐donating monomer, such as styrene. Adding this comonomer multiplied the rate of grafted GMA 3‐ or 4‐fold, resulting in a ratio [styrene]_i/[GMA]_i = 1 mol/mol with [GMA]_i = 6 wt %. So, the copolymerization is favored compared with the homopolymerization. This kind of copolymer presenting reactive functions is very attractive in the field of compatibilizing immiscible polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 581–590, 2001     

Melt strength of linear low‐density polyethylene/low‐density polyethylene blends

Linear low‐density polyethylenes and low‐density polyethylenes of various compositions were melt‐blended with a batch mixer. The blends were characterized by their melt strengths and other rheological properties. A simple method for measuring melt strength is presented. The melt strength of a blend may vary according to the additive rule or deviate from the additive rule by showing a synergistic or antagonistic effect. This article reports our investigation of the parameters controlling variations of the melt strength of a blend. The reciprocal of the melt strength of a blend correlates well with the reciprocal of the zero‐shear viscosity and the reciprocal of the relaxation time of the melt. An empirical equation relating the maximum increment (or decrement) of the melt strength to the melt indices of the blend components is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1408–1418, 2002     

Preparation and characterization of isotactic polypropylene/high‐density polyethylene/carbon black conductive films with strain‐sensing behavior

Novel conductive films with a unique strain (ε)‐sensing behavior and based on a blend of isotactic polypropylene (iPP), high‐density polyethylene (HDPE), and carbon black (CB) were fabricated by an extrusion casting method. The morphology and ε‐sensing behavior of the films were investigated. Scanning electron microscope images showed that the oriented lamellae with a growing direction perpendicular to the extrusion direction were obtained in the HDPE phase and were accompanied by a cocontinuous structure of the iPP phase and HDPE/CB phase. The conductive percolation threshold (m_c) and resistivity–ε behavior of the thin films are affected by the drawing ratio during the process of film preparation. The m_c and electrical resistance of the iPP/HDPE/CB composite films increased with the drawing ratio. The gauge factor of the films within the elastic region decreased with increasing drawing ratio. Furthermore, the result of iPP/(HDPE/CB) 40/60 with a high drawing ratio shows that a reversible conductivity was obtained during the cyclic tensile testing (ε = 10%), but an irreversible conductivity makes the film fail during use at the applied ε values of up to 15%. This makes them good piezoresistive candidates for ε‐sensing materials. Moreover, a simple structural model was proposed to describe the reversible and irreversible phenomena in the electrical resistance behavior of the iPP/HDPE/CB films under tensile loading. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40686.     

Contribution of the melting stage to the evolution of the morphology and chemical conversion of immiscible polyamide/polyethylene blends in twin‐screw extruders

This study investigates the effects of processing conditions (the screw speed, throughput, barrel temperature, and screw configuration) on the chemical conversion and morphology evolution of polyamide/polyolefin blends along a twin‐screw extruder. Polymer samples were collected rapidly at specific barrel locations with a special sampling device for subsequent chemical and morphological characterization. Increasing the screw speed or using more restrictive screw modules at the beginning of the melting zone promoted a faster reaction and better dispersion along the extruder. Increasing the throughput or decreasing the barrel temperature slowed the evolution of the morphology and chemical conversion along the extruder because of the lower melting rate. As soon as melting started, the chemical reaction took place. However, high chemical conversion rates required extensive melting, that is, significant interface generation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009