Effect of the vinyl concentration on the structural and rheological characteristics of peroxide‐modified high‐density polyethylenes

The effect of the hydrogenation of the terminal vinyl groups on the peroxide modification and rheological properties of high‐density polyethylene (HDPE) was investigated. The aim of the study was to determine exclusively the effect of the terminal vinyl groups on the peroxide crosslinking and rheological properties of HDPE with one polymer type. This was achieved by hydrogenation of the terminal vinyl groups of a commercial HDPE to obtain an identical material from a structural point of view, which differed only in the nature of the terminal unsaturations, and the comparison of its level of peroxide crosslinking with that of the original polymer. Hydrogenated and unhydrogenated polymer samples were modified at 170°C with different amounts of organic peroxide ranging from 125 to 5000 ppm. Changes in the molecular structure were determined by Fourier transform infrared spectroscopy, size exclusion chromatography, and rheological measurements. Hydrogenation of the terminal groups of the original polymer significantly reduced the rate of modification or crosslinking. The dynamic viscosity and elasticity increased with the level of peroxide modification. Unhydrogenated samples exhibited rapid increases in viscosity and elastic modulus, whereas their hydrogenated counterparts required about 500% of the amount of peroxide needed for the unhydrogenated sample to attain similar structural changes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological and morphological properties of high‐density polyethylene and poly(ethylene–octene) blends

The rheological and morphological properties of blends based on high‐density polyethylene (HDPE) and a commercial ethylene–octene copolymer (EOC) produced by metallocene technology were investigated. The rheological properties were evaluated in steady and dynamic shear experiments at 190°C in shear rates ranging from 90 s^?1 to 1500 s^?1 and frequency range between 10^?1 rad/s and 10² rad/s, respectively. These blends presented a high level of homogeneity in the molten state and rheological behavior was generally intermediate to those of the pure components. Scanning electron microscopy (SEM) showed that the blends exhibit dispersed morphologies with EOC domains distributed homogeneously and with particle size inferior to 2 μm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2240–2246, 2002     

Blend of high‐density polyethylene and a linear low‐density polyethylene with compositional‐invariant mechanical properties

This article presents the tensile properties and morphological characteristics of binary blends of the high‐density polyethylene (HDPE) and a linear low‐density polyethylene (LLDPE). Two constituents were melt blended in a single‐screw extruder. Injection‐molded specimens were evaluated for their mechanical properties by employing a Universal tensile tester and the morphological characteristics evaluated by using a differential scanning calorimeter and X‐ray diffractometer. It is interesting to observe that the mechanical properties remained invariant in the 10–90% LLDPE content. More specifically, the yield and breaking stresses of these blends are around 80% of the corresponding values of HDPE. The yield elongation and elongation‐at‐break are around 65% to corresponding values of HDPE and the modulus is 50% away. Furthermore, the melting endotherms and the crystallization exotherms of these blends are singlet in nature. They cluster around the corresponding thermal traces of HDPE. This singlet characteristic in thermal traces entails cocrystallization between these two constituting components. The clustering of thermal traces of blends near HDPE meant HDPE‐type of crystallites were formed. Being nearly similar crystallites of blends to that of HDPE indicates nearness in mechanical properties are observed. The X‐ray diffraction data also corroborate these observations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2604–2608, 2002     

Rheological behavior and mechanical properties of high‐density polyethylene blends with different molecular weights

The dynamic rheological and mechanical properties of the binary blends of two conventional high‐density polyethylenes [HDPEs; low molecular weight (LMW) and high molecular weight (HMW)] with distinct different weight‐average molecular weights were studied. The rheological results show that the rheological behavior of the blends departed from classical linear viscoelastic theory because of the polydispersity of the HDPEs that we used. Plots of the logarithm of the zero shear viscosity fitted by the Cross model versus the blend composition, Cole–Cole plots, Han curves, and master curves of the storage and loss moduli indicated the LMW/HMW blends of different compositions were miscible in the melt state. The tensile yield strength of the blends generally followed the linear additivity rule, whereas the elongation at break and impact strength were lower than those predicted by linear additivity; this suggested the incompatibility of the blends in solid state. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultrasonic improvement of the compatibility and rheological behavior of high‐density polyethylene/polystyrene blends

The effects of ultrasonic oscillations on the rheological behavior, mechanical properties, and morphology of high‐density polyethylene (HDPE)/polystyrene (PS) blends were studied. The experimental results show that the die pressure and apparent viscosity of HDPE/PS blends are remarkably reduced in the presence of ultrasonic oscillations and that mechanical properties of the blends are improved. The particle size of the dispersed phase in HDPE/PS blends becomes smaller, its distribution becomes narrower, and the interfacial interaction of the blends becomes stronger if the blends are extruded in the presence of ultrasonic oscillations. Ultraviolet spectra and Soxhlet extraction results show the formation of a polyethylene‐PS copolymer during extrusion in the presence of ultrasonic oscillations, which improves the compatibility of HDPE/PS blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 23–32, 2002     

Crystallization and morphology of metallocene polyethylenes with well‐controlled molecular weight and branching content

The crystallization and morphology of some metallocene polyethylenes with well‐controlled molecular weight and branching content were investigated by DSC, WAXD, PLM and SALS. The banded spherulites observed in linear PE are not seen in crystallization of branched PEs. The small spherulites with small lamellae or fringed micelle crystals are formed when branching content is higher, as suggested by PLM and SALS. The expansion of the unit cell was observed by WAXD as the molecular weight and branching content increased. At even higher branching content (more than 7 mol%), a shrinkage of the unit cell was seen, probably due to a change of crystal morphology from lamellar‐like crystals to fringed micelle‐like crystals. Crystallization temperature, melting point and crystallinity are greatly decreased for branched PEs compared with linear PEs. The equilibrium melting temperature cannot be determined via the Hoffman–Weeks approach for branched PEs since T_m is always 5–6 °C higher than T_c and there is no intercept with the T_m = T_c line. Our results show a predominant role of branches in the crystallization of polyethylene. © 2003 Society of Chemical Industry     

Melt miscibility and mechanical properties of metallocene linear low‐density polyethylene blends with high‐density polyethylene: influence of comonomer type

In this paper, the implications of melt miscibility on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)/high‐density polyethylene (HDPE) blends were assessed with respect to the influence of the comonomer type. The influence of the latter was examined by selecting one butene LLDPE and one octene LLDPE of very similar weight‐average molecular weight (M_w), molecular‐weight distribution (MWD) and branch content, keeping the comonomer type as the only primary molecular variable. Each of the two metallocene LLDPEs was melt‐blended with the same HDPE at 190 °C in a Haake melt‐blender. The rheological, thermal and mechanical properties were measured by the use of an ARES rheometer, differential scanning calorimeter and Instron machine, respectively. The rheological measurements, made over the linear viscoelastic range, suggested no significant influence of the branch type on the melt miscibility. The rheology results are in agreement with those obtained from previous transmission electron microscopy (TEM) and small‐angle neutron scattering (SANS) studies. The dynamic shear viscosity and total crystallinity of the metallocene (m)‐LLDPE blends with HDPE followed linear additivity. At small strains, the branch type has little or no influence on the melt miscibility and solid‐state properties of the blends. Even the large‐strain mechanical properties, such as tensile strength and elongation at break, were not influenced by the comonomer type. However, the ultimate tensile properties of the HDPE‐rich blends were poor. Incompatibility of the HDPE‐rich blends, as a result of the weak interfaces between the blend components, is suggested to develop at large strains. Copyright © 2005 Society of Chemical Industry     

Effects of filler–filler and polymer–filler interactions on rheological and mechanical properties of HDPE–wood composites

High‐density polyethylene (HDPE)–wood composite samples were prepared using a twin‐screw extruder. Improved filler–filler interaction was achieved by increasing the wood content, whereas improved polymer–filler interaction was obtained by adding the compatibilizer and increasing the melt index of HDPE, respectively. Then, effects of filler–filler and polymer–filler interactions on dynamic rheological and mechanical properties of the composites were investigated. The results demonstrated that enhanced filler–filler interaction induced the agglomeration of wood particles, which increased the storage modulus and complex viscosity of composites and decreased their tensile strength, elongation at break, and notched impact strength because of the stress concentration. Stronger polymer–filler interaction resulted in higher storage modulus and complex viscosity and increased the tensile and impact strengths due to good stress transfer. The main reasons for the results were analyzed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Chemical and thermal characterization of high‐ and low‐density irradiated polyethylenes

A comparative study of the dynamic mechanical relaxation spectra of high‐ and low‐density polyethylenes irradiated with γ‐radiation from a Co⁶⁰ source was performed. The irradiation doses ranged from 0 to 100 Mrad. All the samples were previously characterized by determination of the molecular weight distribution, the number of functional groups, and the crystalline fraction. All the relaxation zones between ?145°C and the melt were studied in the frequency range from 0.3 to 30 Hz. The changes observed in the mechanical relaxation spectra were related to modifications in the chemical structure and morphological parameters attributed to the exposure of the samples to the γ‐radiation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1953–1958, 2002     

Dynamic rheological properties of high‐density polyethylene/polystyrene blends extruded in the presence of ultrasonic oscillations

The linear rheological properties of high‐density polyethylene (HDPE), polystyrene (PS), and HDPE/PS (80/20) blends were used to characterize their structural development during extrusion in the presence of ultrasonic oscillations. The master curves of the storage shear modulus (G′) and loss shear modulus (G″) at 200°C for HDPE, PS, and HDPE/PS (80/20) blends were constructed with time–temperature superposition, and their zero shear viscosity was determined from Cole–Cole plots of the out‐of‐phase viscous component of the dynamic complex viscosity (η″) versus the dynamic shear viscosity. The experimental results showed that ultrasonic oscillations during extrusion reduced G′ and G″ as well as the zero shear viscosity of HDPE and PS because of their mechanochemical degradation in the presence of ultrasonic oscillations; this was confirmed by molecular weight measurements. Ultrasonic oscillations increased the slopes of log G′ versus log G″ for HDPE and PS in the low‐frequency terminal zone because of the increase in their molecular weight distributions. The slopes of log G′ versus log G″ for HDPE/PS (80/20) blends and an emulsion model were used to characterize the ultrasonic enhancement of the compatibility of the blends. The results showed that ultrasonic oscillations could reduce the interfacial tension and enhance the compatibility of the blends, and this was consistent with our previous work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3153–3158, 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.     

Bleached extruder chemi‐mechanical pulp fiber‐PLA composites: Comparison of mechanical,thermal, and rheological properties with those of wood flour‐PLA bio‐composites

An environmentally friendly bleached extruder chemi‐mechanical pulp fiber or wood flour was melt compounded with poly(lactic acid) (PLA) into a biocomposite and hot compression molded. The mechanical, thermal, and rheological properties were determined. The chemical composition, scanning electron microscopy, and Fourier transform infrared spectroscopy results showed that the hemicellulose in the pulp fiber raw material was almost completely removed after the pulp treatment. The mechanical tests indicated that the pulp fiber increased the tensile and flexural moduli and decreased the tensile, flexural, and impact strengths of the biocomposites. However, pulp fiber strongly reinforced the PLA matrix because the mechanical properties of pulp fiber‐PLA composites (especially the tensile and flexural strengths) were better than those of wood flour‐PLA composites. Differential scanning calorimetry analysis confirmed that both pulp fiber and wood flour accelerated the cold crystallization rate and increased the degree of crystallinity of PLA, and that this effect was greater with 40% pulp fiber. The addition of pulp fiber and wood flour modified the rheological behavior because the composite viscosity increased in the presence of fibers and decreased as the test frequency increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44241.     

Morphology and mechanical properties of styrene–ethylene/butylene–styrene triblock copolymer/high‐density polyethylene composites

The morphology and mechanical properties of a styrene–ethylene/butylene–styrene triblock copolymer (SEBS) incorporated with high‐density polyethylene (HDPE) particles were investigated. The impact strength and tensile strength of the SEBS matrix obviously increased after the incorporation of the HDPE particles. The microstructure of the SEBS/HDPE blends was observed with scanning electron microscopy and polar optical microscopy, which illustrated that the SEBS/HDPE blends were phase‐separation systems. Dynamic mechanical thermal analysis was also employed to characterize the interaction between SEBS and HDPE. The relationship between the morphology and mechanical properties of the SEBS/HDPE blends was discussed, and the toughening mechanism of rigid organic particles was employed to explain the improvement in the mechanical properties of the SEBS/HDPE blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ultrahigh molecular weight polyethylene/polypropylene/organo‐montmorillonite nanocomposites: Phase morphology,rheological, and mechanical properties

Phase morphology, rheological, and mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE)/PP/organo‐montmorillonite nanocomposites were investigated in this work. The results of TEM and XRD indicated that the organo‐montmorillonite PMM prepared with the complex intercalator [2‐methacryloyloxyethyldodecyldimethylammonium bromide/poly(ethylene glycol)] were exfoliated and dispersed into UHMWPE matrix, and the synergistic effect of the complex intercalator on the exfoliation and intercalation for montmorillonite occurred. Besides, the presence of PMM in UHMWPE matrix was found able to lead to a significant reduction of melt viscosity and enhancement in tensile strength and elongation at break of UHMWPE, except that izod‐notched impact strength was without much obvious change. The dispersed PMM particles exhibited a comparatively large two‐dimensional aspect ratio (L_clay/d_clay = 35.5), which played an important role in determining the enhancement of mechanical properties of UHMWPE nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of ultrasonic oscillations on the rheological behavior and morphology of Illite‐filled high‐density polyethylene composites

The effects of ultrasonic oscillations on the rheological and viscoelastic properties and morphology of high‐density polyethylene (HDPE)/Illite (70/30) composites were studied. The experimental results showed that the die pressure and apparent viscosity of the HDPE/Illite (70/30) composites were reduced greatly, and so the mass‐flow rate significantly increased in the presence of ultrasonic oscillations during the extrusion. Scanning electron microscopy and linear viscoelasticity tests showed that ultrasonic oscillations improved the dispersion of the Illite particles into the HDPE matrix. The aggregation of the Illite particles disappeared on the fractured surfaces of HDPE/Illite (70/30) composites extruded in the presence of ultrasonic oscillations, and this indicated that ultrasonic oscillations promoted the homogeneous dispersion of Illite particles into the HDPE matrix. Ultrasonic oscillations caused the permanent reduction of the dynamic viscosity and zero‐shear viscosity of HDPE/Illite (70/30) composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 379–384, 2005     

Synthesis and characterization of high‐density polypropylene‐grafted polyethylene via a macromolecular reaction and its rheological behavior

High‐density polyethylene grafted isotactic polypropylene (PP‐g‐HDPE) was prepared by the imidization reaction between maleic anhydride grafted polyethylene and amine‐grafted polypropylene in a xylene solution. The branch density was adjusted by changes in the molar ratio between maleic anhydride and primary amine groups. Dynamic rheology tests were conducted to compare the rheological properties of linear polyolefins and long‐chain‐branched polyolefins. The effects of the density of long‐chain branches on the rheological properties were also investigated. It was found that long‐chain‐branched hybrid polyolefins had a higher storage modulus at a low frequency, a higher zero shear viscosity, a reduced phase angle, enhanced shear sensitivities, and a longer relaxation time. As the branch density was increased, the characteristics of the long‐chain‐branched structure became profounder. The flow activation energy of PP‐g‐HDPE was lower than that of neat maleic anhydride grafted polypropylene (PP‐g‐MAH) because of the lower flow activation energy of maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH). However, the flow activation energy of PP‐g‐HDPE was higher than that of PP‐g‐MAH/HDPE‐g‐MAH blends because of the presence of long‐chain branches. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization behavior of glass bead‐filled low‐density polyethylene composites

The effects of the filler content and the filler size on the crystallization and melting behavior of glass bead‐filled low‐density polyethylene (LDPE) composites have been studied by means of a differential scanning calorimeter (DSC). It is found that the values of melting enthalpy (ΔH_c) and degree of crystallinity (x_c) of the composites increase nonlinearly with increasing the volume fraction of glass beads, ϕ_f, when ϕ_f is greater than 5%; the crystallization temperatures (T_c) and the melting temperatures (T_m) of the composites are slightly higher than those of the pure LDPE; the effects of glass bead size on x_c, T_c, and T_m are insignificant at lower filler content; but the x_c for the LDPE filled with smaller glass beads is obviously greater than that of the filled system with bigger ones at higher ϕ_f. It suggests that small particles are more beneficial to increase in crystallinity of the composites than big ones, especially at higher filler content. In addition, the influence of the filler surface pretreated with a silane coupling agent on the crystallization behavior are not too outstanding at lower inclusion concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 687–692, 1999     

Tailoring the crystalline morphologies and mechanical properties of high‐density polyethylene parts by a change in the fluid flow pattern under gas‐assisted injection molding

In this study, an increase in the cooling rate of high‐density polyethylene parts was carried out via a change in the fluid flow pattern to introduce gas cooling under a gas‐assisted injection‐molding process; this was conducive to the retention of orientation chains shaped during the injection stage and further developed into much more oriented crystals. Morphological observation showed that the parts without gas cooling (WOGC) were composed of oriented crystals except the gas channel zone, whereas the parts with gas cooling (WGC) were full of oriented crystals, especially much more interlocking shish‐kebab structures in the subskin zone. The WGC parts had a higher degree of orientation than the corresponding zone of the WOGC parts. Although the lower crystallinity, the wider orientation regions, and much more interlocking shish‐kebab structures led to considerable increases from 32 and 990 MPa in the WOGC parts to 36 and 1150 MPa in the WGC parts for the yield strength and elastic modulus, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40349.     

Time‐dependent rheological behavior of low‐density polyethylene white color masterbatches under dynamic stress field

The time‐dependent behavior of low‐density polyethylene (LDPE) white color masterbatches (WCMBs), which were concentrated suspensions filled with titanium dioxide (TiO₂), was found using dynamic stress rheometer. The viscosity first decreased slightly with time then continuously increased with time, and T_g(δ) (δ was the angle of loss) decreased with time, which meant the time‐dependent behavior of the elastic contribution was more pronounced than that of the viscous contribution. The higher the experimental frequency and temperature, the more pronounced the viscosity increase. However, the higher experimental stress did not lead to pronounced viscosity increase, which was attributed to the existence of small defects at higher stress. The 30 wt % of TiO₂ content was critical to obvious time‐dependent behavior. The viscosity increase with time was related to the formation of a hard shell around the melt sample during the test. It was verified by thermogravimetric analysis that the TiO₂ concentration at the outer surface was higher than that at the core of the sample and, because the outer surface contained more TiO₂, a hard shell was formed, which impeded further deformation of the sample. This was completely different from the other reported systems with time‐dependent behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2793–2799, 2002