Effects of the viscosity ratio on polyolefin ternary blends

Polyolefin binary and ternary blends were prepared from polypropylene (PP), an ethylene–α‐olefin copolymer (mPE), and high‐density polyethylene (HDPE) on the basis of the viscosity ratio of the dispersed phase to the continuous phase. In PP/mPE/HDPE blends, fibrils were observed when the dispersed‐phase (mPE/HDPE) viscosity was less than that of PP, or when the viscosity of mPE was less than that of PP, although the viscosity of mPE/HDPE was greater than that of PP. The notched impact strength and mechanical properties such as the yield strength, flexural modulus, and hardness of PP/mPE binary blends further increased with the addition of HDPE according to the type of HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4027–4036, 2004     

Effects of dispersed phase composition on thermoplastic polyolefins

Ternary blends of polypropylene (PP), ethylene–octene copolymer (mPE), and high‐density polyethylene (HDPE) were prepared based on the phase behavior and physical properties of mPE/HDPE binary blends, and the results were interpreted in terms of morphology and both rheological and mechanical properties of the ternary blends as well as the binary blends. It was found that when mPE encapsulates HDPE in the PP matrix, compared to the encapsulation of mPE by HDPE, better blend properties were obtained, presumably because of the compatibilizing effect of mPE between PP and HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 179–188, 2004     

Thermal properties and crystallization behavior of polyolefin ternary blends

Crystallization behaviors, spherulite growth and structure, and the crystallization kinetics of polypropylene (PP)/ethylene‐α‐olefln copolymer (mPE)/high‐density polyethylene (HDPE) ternary blends and of mPE/HDPE binary blends have been studied using polarizing optical micrography (POM) and differential scanning calorimetry (DSC). In mPE/HDPE blends, large pendant groups of mPE disturbed spherulite growth of HDPE, leading to a different crystallite morphology and isothermal kinetics. Non‐isothermal properties, morphology, and isothermal crystallization kinetics of PP in ternary blends were significantly influenced by the composition and crystallization behavior of the mPE/HDPE binary blends as well as the crystallization condition. Polym. Eng. Sci. 44:1858–1865, 2004. © 2004 Society of Plastics Engineers.     

茂金属聚乙烯的共混改性研究

对三种茂金属聚乙烯 (mPE)做了DSC研究。将茂金属聚乙烯同传统聚烯烃 (HDPE ,PP ,LDPE)进行了共混研究 ,结果表明mPE的加入提高了LDPE的拉伸性能 ,使HDPE和PP的拉伸强度下降 ,但mPE含量在 2 0 %～2 5 %的范围内 ,拉伸强度和断裂伸长率下降很小。mPE的加入大大提高了PP和HDPE的冲击性能。对mPE/LDPE共混物吹膜进行了研究 ,测定了共混物的熔体流动速率 ,探索了吹膜的工艺条件 ,以及薄膜的拉伸性能、撕裂性能与共混组成比的关系。     

Nonisothermal crystallization,melting behavior,and morphology of polypropylene/metallocene‐catalyzed polyethylene blends

The nonisothermal crystallization, melting behavior, and morphology of blends of polypropylene (PP) and a metallocene‐catalyzed polyethylene (mPE) elastomer were studied with differential scanning calorimetry, scanning electron microscopy, polarized optical microscopy, and X‐ray diffraction. The results showed that PP and mPE were partially miscible and could form some cocrystallization, although the extent was very small. A modified Avrami analysis and the Mo method were used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was homogeneous, the growth of the spherulites was three‐dimensional, and the crystallization mechanism of PP was not affected by mPE. The crystallization activation energy was estimated with the Kissinger method. Interesting results were obtained with the modified Avrami analysis and Mo and Kissinger methods, and the conclusions were in good agreement. The addition of less mPE increased the overall crystallization rate of PP. The relationship between the composition and morphology of the blends was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1203–1210, 2004     

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     

Morphology and electrical conductivity of polyethylene/polypropylene blend filled with thermally reduced graphene oxide and surfactant exfoliated graphene

High‐density polyethylene (HDPE)/polypropylene (PP) composites with graphenes were prepared by melt‐compounding method. Graphene sheets were prepared through thermally reduced graphene oxide (TRG) and surfactant exfoliated graphene (SEG), respectively. Structural characterization showed that the TRG sheets exhibited a few‐layers composition with more defects compared to the SEG sheets. Morphological observations of the composites demonstrated that the graphene was preferentially dispersed in the HDPE phase and the addition of graphene (TRG and SEG) influenced the phase structure of the HDPE/PP composites. The distribution of the TRG sheets in the HDPE phase was better than the SEG sheets, and the obtained HDPE/PP composites exhibited a low electrical percolation threshold with the highly dispersed graphene. The TRG/HDPE/PP composite showed a low electrical percolation threshold of 3 wt% (1.25 vol%). For the SEG/HDPE/PP system, the percolation threshold was 7 wt% (2.98 vol%). Differences in the behavior of the two graphene components (TRG and SEG) in the HDPE/PP composites influenced the formation of percolation networks and electrical properties. POLYM. COMPOS., 38:2098–2105, 2017. © 2015 Society of Plastics Engineers     

Melting behavior and isothermal crystallization kinetics of polypropylene/metallocene‐catalyzed polyethylene elastomer blends

Polypropylene (PP)/metallocene‐catalyzed polyethylene elastomer (mPE) blends were prepared in a twin‐screw extruder. The melting behavior, crystallization behavior, and isothermal crystallization kinetics of the blends were studied with differential scanning calorimetry. The results showed that PP and mPE were partially miscible and that the addition of mPE shifted the melting peak of PP to a lower temperature but the crystallization temperature to a higher temperature, demonstrating a dilution effect of mPE on PP. The isothermal crystallization kinetics of the blends were described with the Avrami equation. The values of the Avrami exponent indicated that the nucleation mechanism of the blends was heterogeneous, the growth of spherulites was almost three‐dimensional, and the crystallization mechanism of PP was not affected much by mPE. At the same time, the Avrami exponents of the blends were higher than that of pure PP, and this showed that the addition of mPE helped PP to form more perfect spherulites. The crystallization rate of PP was increased by mPE because the dilution effect of mPE on PP increased the mobility of PP chains. The crystallization activation energy was estimated with the Arrhenius equation, and the nucleation constant was determined by the Hoffman–Lauritzen theory. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced toughening of poly(propylene) with reclaimed‐tire rubber

The dynamic vulcanization of reclaimed‐tire rubber (RTR) and homopolypropylene (PP) was performed by melt‐mixing using either a sulfur crosslinking agent, maleic anhydride (MA), dicumyl peroxide (DCP), or the combination of MA and DCP, in two consecutive machines, first a two‐roll mill and then a counterrotating twin‐screw extruder. In the case of applying a sulfur crosslinking agent, it was demonstrated that the RTR/PP blend at the ratio of 30/70 had the highest impact strength. This could be attributed to the limitation of carbon black in the blend. When the combination of MA and DCP was applied, the result was higher impact strength of the blend at the same ratio. This could be attributed to not only the cohesion between the polymer chains in each phase, PP phase and rubber phase, but also the interfacial adhesion between PP and RTR chains in these two phases. For comparison, the GRT/PP blends with and without sulfur crosslinking agent were prepared as well. All these blends showed low impact strength, which was nearly the same as that of PP. The effects of different crosslinking agents on dispersion and distribution of rubber domain size, viscosity, and percentage crystallinity were also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 510–515, 2004     

Electrical and mechanical properties of expanded graphite‐reinforced high‐density polyethylene

High‐density polyethylene (HDPE) was reinforced with expanded and untreated graphite in a melt‐compounding process. Viscosity increased upon addition of graphite phase, with the expanded graphite (EG) showing more dramatic rise than the untreated graphite (UG) in viscosity. The increase in viscosity was attributed to the increased surface‐to‐volume ratio for the EG filler after acid treatment. Electrical conductivity also increased from that pertaining to an insulator to one characteristic of a semiconductor. The EG system showed a lower percolation threshold for transition in conductivity compared to that in the UG system. DSC results indicated that the fillers acted as a nucleating agent in inducing the crystallization of HDPE in the composites. However, the overall degree of crystallinity and melting temperature of HDPE decreased with the addition of EG and UG. Mechanical properties improved as a function of filler content but the overall enhancement was not impressive. It was conjectured that the filler–matrix interface was not optimized in the melt‐mixing process. However, the role of EG as a reinforcement phase for both electrical and mechanical properties was unambiguously established. The EG composites demonstrated potentially useful attributes for antistatic, barrier, mechanical, electrical, and cost‐effective applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:2781–2788, 2004     

Rheological properties and crystalline structure of the dynamically cured EPDM and PP/HDPE ternary blends

The rheological properties and crystalline structure of the polyolefin ternary blends of EPDM/polypropylene/high density polyethylene were studied. Blends were prepared in a laboratory internal mixer by two different methods. In blend–cure process, blending and curing were performed simultaneously and EPDM was cured by dicumyl peroxide (DCP) in the presence of PP/HDPE under shear. The cure–blend was to cure EPDM alone first under shear (dynamic curing) and then mix the cured EPDM with PP and HDPE. The effect of DCP concentration, intensity of the shear mixing, and the rubber/plastic composition were studied using capillary rheometer and X-ray diffractometer. The PP-rich ternary blends showed the effect of the mechanooxidative degradation of PP by shear and peroxide. The melt viscosity increased with increasing DCP concentration in blends of EPDM-rich compositions. X-ray diffraction studies revealed that the inclusion of 25 wt % of linear EPDM in the PP/HDPE mixture for the PP-rich ternary blends changed the crystal structure of polypropylene component in the ternary blends. However, the dynamic curing did not alter the crystal structure of PP or HDPE in the blends.     

Developing laminar morphology in higher‐viscosity‐ratio polyblends by controlling flow fields in a single‐screw extruder

The morphology of high‐density polyethylene (HDPE)/polyamide‐6 (PA‐6) blends with different melt‐shear‐viscosity ratios (VRs), prepared by combining a single‐screw extruder with a convergent die was studied. Two different screw geometries, metering and mixing screws, and three screw speeds, 20, 40 and 60 rpm, were evaluated to investigate their effects on the morphology of extruded ribbons. Two mixing screws with low and high shear intensity, respectively, were used. Both the geometry and speed of screw were found to have an important role in the morphological changes of the blends. In contrast to previous studies, the results shown in this work reveal that it is possible to develop a laminar structure of PA‐6 in an HDPE matrix with a VR larger than one by controlling the flow fields, through appropriately combining the type and shear intensity of the screw with its speed. A well‐developed laminar PA‐6 phase with an aspect ratio of about 100 was obtained under the optimum combination. Copyright © 2004 Society of Chemical Industry     

Shear flow behavior and oil distribution between phases in thermoplastic vulcanizates

The high rate shear flow behavior and the morphology of five different oil‐extended polypropylene (PP)/ethylene‐propylene‐diene monomer (EPDM) thermoplastic vulcanizate blends were investigated with the melt flow rate (MFR) of the PP varying from 0.7 to 20. The ratio of rubber to PP is 70 : 30 in three of the thermoplastic vulcanizates (TPVs) and 50 : 50 in the other two TPVs. The distribution of the high‐temperature oil between the PP melt and the rubber is a key parameter because this will affect the viscosity of the PP/oil medium. The object of this study was to estimate the matrix composition in each of the TPVs at processing temperatures and to compare the shear viscosity of the effective matrix with that of the TPV. To this end, several PP/oil mixtures were prepared and their viscosity curves were correlated with the neat PP melt viscosity curves by means of shift factors varying with oil concentration. The oil distribution between the PP and rubber phases was estimated from TEM micrographs of the TPV blends. The results show that the PPs are mixed with oil to different proportions in the different TPVs and the viscosity curves of these mixtures exhibit the same trends in magnitude as the corresponding TPV viscosity curves. Hence, the shear flow of TPVs can be understood more readily in terms of the effective PP/oil medium flow behavior than in terms of the neat PP melt flow. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 113–121, 2004     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Melt compounding of polypropylene‐based clay nanocomposites

Polypropylene (PP)‐based nanocomposites containing 4 wt% maleic anhydride grafted PP (PP‐g‐MA) and 2 wt% Cloisite 20A (C20A) were prepared using various processing devices, viz., twin‐screw extruder (TSE), single‐screw extruder (SSE), and SSE with an extensional flow mixer (EFM). Two processing methods were employed: (I) masterbatch (MB) preparation in a TSE (with 10 wt% C20A and clay/compatibilizer ratio of 1:2), followed by dilution in TSE, SSE, or SSE + EFM, to 2 wt% clay loading; (II) single pass, i.e., directly compounding of dry‐blended PP‐g‐MA/clay in TSE, SSE, or SSE + EFM. It has been indicated that the quality of clay dispersion, both at micro‐ and nanolevel, of the nanocomposites depends very much on the operating conditions during processing, such as mixing intensity and residence time, thus affecting the mechanical performance. Besides that the degradation of the organoclay and the matrix is also very sensitive to these parameters. According to results of X‐ray diffraction, field emission gun scanning electron microscopy, transmission electron microscopy, and mechanical tests, the samples prepared with MB had better overall clay dispersion, which resulted in better mechanical properties. The processing equipment used for diluting MB had a marginal influence on clay dispersion and nanocomposite performance. POLYM. ENG. SCI., 47:1447–1458, 2007. © 2007 Society of Plastics Engineers     

Effects of process conditions and mixing protocols on structure of extruded polypropylene nanocomposites

Polymer melt‐direct intercalation or exfoliation is a promising approach for the preparation of nanocomposites. The structure of nanoclay platelets in the nanocomposites depends not only on the properties of polymer matrix and nanoclay, but also on the operating conditions during processing. The objective of the present work is to investigate the effects of clay chemical modifiers, mixing protocols, and operating conditions upon the clay structure in nanocomposites prepared with a corotating twin‐screw extruder. Two mixing methods were used for the nanocomposite preparation: two‐step mixing and one‐step mixing. Experimental results obtained from melt flow index and complex viscosity measurements suggest that nanoclay C15A is more exfoliated than C30B in a polypropylene homopolymer containing a maleic anhydride grafted PP (PB) as compatibilizer. The two‐step mixing method results in better exfoliation for the nanofillers than the one‐step mixing method. A numerical simulation has been carried out to evaluate the mean residence time and shear rate in different screw configurations under various process conditions. X‐ray diffraction experiments indicate that the residence time is a dominant factor in producing satisfactory nanocomposites in extruders. However, high shear rate coupled with long residence time might result in poor exfoliation of clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1891–1899, 2004     

Mechanical properties and morphologies of PP/mPE/filler composites

Because of the poor impact behavior of polypropylene (PP) at low temperatures, the blending of PP with metallocene‐polymerized polyethylene (mPE) elastomers was investigated in this study. However, a reduced modulus of the overall blend was inevitable because of the addition to elastomers. To obtain a balance of the properties, we introduced rigid inorganic fillers to PP/mPE blends. The performance of the composites was characterized with tensile and Charpy notched impact tests, and the fracture morphology was examined with scanning electron microscopy. The results showed that the effects of fillers in a brittle matrix and in a ductile matrix were quantitatively different. For PP/mPE/filler ternary composites, the dependence of Young's modulus and yield strength on CaCO₃ content was not significant compared with that of PP/filler binary composites, whereas the elongation at break and tensile toughness at room temperature for PP/mPE/filler systems were more improved. The impact strength of the PP/mPE blends filled with untreated glass beads and CaCO₃ at a low temperature was lowered because of the weak interfacial bond. However, the values of the impact strength of the PP/mPE/filler composites at a low temperature remained at a high level compared with that of pure PP. In particular, a PP/mPE blend filled with surface‐treated kaolin had a higher low‐temperature impact toughness than the unfilled blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3029–3035, 2002; DOI 10.1002/app.2333     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of compatibilizers and reactive blending

Epoxidized natural rubber (ENR) was prepared using the performic epoxidation method. TPVs based on ENR/PP blends were later prepared by melt‐mixing processes via dynamic vulcanization. The effects of blend ratios of ENR/PP, types of compatibilizers, and reactive blending were investigated. Phenolic modified polypropylene (Ph‐PP) and graft copolymer of maleic anhydride on polypropylene molecules (PP‐g‐MA) were prepared and used as blend compatibilizers and reactive blending components of ENR/Ph‐PP and ENR/PP‐g‐MA blends. It was found that the mixing torque, apparent shear stress and apparent shear viscosity increased with increasing levels of ENR. This is attributed to the higher viscosity of the pure ENR than that of the pure PP. Furthermore, there was a higher compatibilizing effect because of the chemical interaction between the polar groups in ENR and PP‐g‐MA or Ph‐PP. Mixing torque, shear flow properties (i.e., shear stress and shear viscosity) and mechanical properties (i.e., tensile strength, elongation at break, and hardness) of the TPVs prepared by reactive blending of ENR/Ph‐PP and ENR/PP‐g‐MA were lower than that of the samples without a compatibilizer. However, the TPVs prepared using Ph‐PP and PP‐g‐MA as compatibilizers exhibited higher values. We observed that the TPVs prepared from ENR/PP with Ph‐PP as a compatibilizer gave the highest rheological and mechanical properties, while the reactive blending of ENR/PP exhibited the lowest values. Trend of the properties corresponds to the morphology of the TPVs. That is, the TPV with Ph‐PP as a blend compatibilizer showed the smallest rubber particles dispersed in the PP matrix, while the reactive blending of ENR/PP‐g‐MA showed the largest particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4729–4740, 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