Reactive compatibilization of polymer blends by γ‐irradiation: Influence of the order of processing steps

Results concerning γ‐irradiation of polymer blends such as HDPE/ground tire rubber (GTR) and PP/HDPE are reported in this article with a special emphasis on the order of processing steps. Irradiation dose varied in the range 0–100 kGy. The two first polymers (HDPE and rubber) are preferentially crosslinked under γ irradiation while PP undergoes chain scission. Mechanical tests and differential scanning calorimetry (DSC) analysis show that the efficiency of the reactive compatibilization by γ irradiation depends greatly on the chronology of γ‐irradiation and injection‐molding steps. Electron spin resonance (ESR) results reveal that numerous radicals remain trapped in the materials after γ‐irradiation even after a long time. Then the effect of irradiation on material properties is different if polymers are melted after irradiation or not. Crosslinking and chain scission are not affected in an equivalent way by the order of processing steps. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Anisotropic multilayer conductive networks in carbon nanotubes filled polyethylene/polypropylene blends obtained through high speed thin wall injection molding

To prepare composites with anisotropic conductive networks, electrical conductive polymer composites (CPCs) consisting of polypropylene (PP) and carbon nanotubes (CNTs) filled polyethylene (PE) are fabricated through high speed thin-wall injection molding. Morphological study demonstrates that CNTs are localized in PE phase while the alternating multilayer structure with different polymer phases elongated as well as conductive network oriented parallel to flow direction is observed. To form such alternating layered structure, the dispersed phases are firstly deformed into discontinuous layers, and finally further deformed into wide and regular continuous alternating layers. In term of the mechanism behind this, the good viscosity match, low interfacial tension between different polymer components, short relaxation time and high shear rate are thought as important issues. The anisotropic conductive behavior of these CPCs, i.e. conductive in longitudinal (parallel to flow direction) and transverse (perpendicular to flow direction) direction but non-conductive in thickness direction, is contributed by the insulating PP layer which cuts off the conductive networks in the core layer. More importantly, much better electromagnetic interference (EMI) shielding ability is obtained for these CPCs with alternating multilayer conductive networks comparing with the same polymer blends with isotropic conductive networks, despite of the fact that much lower resistivity is obtained for the later. This indicates great potential of these anisotropic CPCs for electronic applications. Moreover, this study has shed some light on the potential use of such alternating multi-layered structure to prepare a range of multi-functional materials.     

Morphology and electrical properties of short carbon fiber-filled polymer blends: High-density polyethylene/poly(methyl methacrylate)

Morphology and electrical properties of short carbon fiber-filled high-density polyethylene (HDPE)/poly(methyl methacrylate)(PMMA) polymer blends have been studied. The percolation threshold of HDPE50/PMMA50 blends filled with vapor-grown carbon fiber (VGCF), 1.25 phr VGCF content, is much lower than those of the individual polymers. The SEM micrographs verified that the enhancement of conductivity could be attributed to the selective location of VGCF in the HDPE phase. A double percolation is the basic requirement for the conductivity of the composites, i.e., the percolation of carbon fibers in the HDPE phase and the continuity of this phase in the blends, which hereby are defined as the first percolation and the second percolation, respectively. The SEM micrographs also showed that the short carbon fibers could affect the morphology of the blends. With the increase of VGCF content, the HDPE domains are elongated from spherical into strip shape, finally develop to a continuous structure. As a result, the second percolation threshold of the blends filled with 2.5 phr VGCF, 20 wt % HDPE, is lower than that of the blends filled with 1.5 phr VGCF, 30 wt % HDPE. The influence of molding temperature and time on the second percolation threshold has also been investigated. For the composites molded at a lower temperature, the second percolation threshold is shifted to a higher VGCF content, but there is little influence of molding time on the second percolation threshold. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1813–1819, 1998     

聚烯烃改性PET的研究

通过PET与PP、HDPE、EPDM挤出共混，注射模塑制得试样。经DTA、SEM和力学性能测试，表征了共混体系的热行为、结构形态和力学性能。结果表明，在PET/PP(EPDM、HDPE)共混体系中，加入少量的PP-g-MI(EPDM-g-MAH、PE-g-MI)，可较好地改善PEt与PP(EPDM、HDPE)之间的相容性，使分散相在PET基体连续相中分散均匀，分散相尺寸减小，增加了两相间界面的粘结力；同时对PET的结晶有较强的促进作用，使其冷结晶温度降低，改善了PET的加工性能；并且能大幅度提高共混物的冲击强度。     

Study on morphology of ternary polymer blends. I. Effects of melt viscosity and interfacial interaction

The morphology of some ternary blends was investigated. In all of the blends polypropylene, as the major phase, was blended with two different minor phases, ethylene–propylene–diene terpolymer (EPDM) or ethylene–propylene–rubber (EPR) as the first minor phase and high‐density polyethylene (HDPE) or polystyrene (PS) as the second minor phase. All the blends were investigated in a constant composition of 70/15/15 wt %. Theoretical models predict that the dispersed phase of a multiphase polymer blend will either form an encapsulation‐type phase morphology or phases will remain separately dispersed, depending on which morphology has the lower free energy or positive spreading coefficient. Interfacial interaction between phases was found to play a significant role in determining the type of morphology of these blend systems. A core–shell‐type morphology for HDPE encapsulated by rubber was obtained for PP/rubber/PE ternary blends, whereas PP/rubber/PS blends showed a separately dispersed type of morphology. These results were found to be in good agreement with the theoretical predictions. Steady‐state torque for each component was used to study the effect of melt viscosity ratio on the morphology of the blends. It was found that the torque ratios affect only the size of the dispersed phases and have no appreciable influence on the type of morphology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1129–1137, 2001     

Deformation and fracture of Mg(OH)2‐filled polyolefin composites under tensile stress

The tensile behavior of high‐density polyethylene (HDPE), polypropylene (PP), and linear low‐density polyethylene composites containing a titanate coupling agent and silicone‐oil‐treated magnesium hydroxide [Mg(OH)₂] was studied. The increase in the extent of the ultimate elongation of the composites was affected by the yield stress and the strain‐hardening tendency of the polymer matrix in the composites. Ethylene–propylene–diene rubber and octane–ethylene copolymer were introduced to adjust the yield stress of PP and HDPE. Although the ultimate elongation of PP/elastomer and HDPE/elastomer blends was higher than that of virgin PP or HDPE, the ultimate elongation of the filled composites dropped at a high content of Mg(OH)₂. Scanning electron microscopy showed that the difference in the uniformity of the interface exfoliation decreased with the yield stress of the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3248–3255, 2003     

Partial replacement of EPR by GTR in highly flowable PP/EPR blends: Effects on morphology and mechanical properties

This research analyzes the effect of ground tire rubber (GTR) and a novel metallocene‐based ethylene–propylene copolymer (EPR), with high propylene content, on the morphology and mechanical behavior of ternary polymer blends based on a highly flowable polypropylene homopolymer (PP). The PP/EPR blends morphology, with very small domains of EPR dispersed in the PP matrix, indicates a good compatibility among these materials, which leads to a significant improvement on elongation at break and impact strength. The incorporation of EPR on the rubber phase of thermoplastic elastomeric blends (TPE) based on GTR and PP (TPE^GTR) has a positive effect on their mechanical performance, attributed to the toughness enhancement of the PP matrix and to the establishment of shell‐core morphology between the rubber phases. The mechanical properties of the ternary blends reveal that TPE^GTR blends allow the upcycling of this GTR material by injection molding technologies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42011.     

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     

Effect of microfiber reinforcement on the morphology,electrical, and mechanical properties of the polyethylene/poly(ethylene terephthalate)/carbon nanotube composites

In situ microfiber reinforced conductive polymer composites consisting of high‐density polyethylene (HDPE), poly(ethylene terephthalate) (PET), and multiwalled carbon nanotube (CNT) were prepared in a twin screw extruder followed by hot stretching of PET/CNT phase in HDPE matrix. For comparison purposes, the HDPE/PET blends and HDPE/PET/CNT composites were also produced without hot stretching. Extrusion process parameters, hot‐stretching speed, and CNT amount in the composites were kept constant during the experiments. Effects of PET content and molding temperature on the morphology, electrical, and mechanical properties of the composites were investigated. Morphological observations showed that PET/CNT microfibers were successfully formed in HDPE phase. Electrical conductivities of the microfibrillar composites were in semi‐conductor range at 0.5 wt% CNT content. Microfiber reinforcement improved the tensile strength of the microfibrillar HDPE/PET/CNT composites in comparison to that of HDPE/PET blends and HDPE/PET/CNT composites prepared without hot stretching. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Effect of morphology on the electric conductivity of binary polymer blends filled with carbon black

Several carbon black (CB)‐filled binary polymer blends were prepared in Haake rheometer. Distribution states of CB and effect of morphology on the electric conductivity of different ternary composites were investigated. Under our experimental condition CB particles located preferentially at the interface between polymethyl methacrylate (PMMA) and polypropylene (PP) in PMMA/PP/CB composites, in high‐density polyethylene (HDPE) phase in PP/HDPE/CB composites, and in Nylon6 (PA6) phase in polystyrene (PS)/PA6/CB, PP/PA6/CB, PMMA/PA6/CB, and polyacrylonitrile (PAN)/PA6/CB composites; the ternary composites in which CB particles locate at the interface of two polymer components have the highest electric conductivity when the mass ratio of the two polymers is near to 1 : 1. The ternary composites in which CB particles located preferentially in one polymer have the highest electric conductivity usually when the amount of the polymer component having CB particles is comparatively less than the amount of the polymer component not having CB particles; if the formulations of PS/PA6/CB, PP/PA6/CB, and PMMA/PA6/CB composites equaled and PA6/CB in them is in dispersed phase, PS/PA6/CB composites have the highest electric conductivity and PP/PA6/CB composites have the lowest electric conductivity; suitable amount of PS or PAN in PA6/CB composites increase the electric conductivity due in the formation of a parallel electrocircuit for electrons to transmit. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Behavior of polyolefin blends with acetylated sisal fibers

The influence of acetylation on the mechanical, thermal and thermodegradative behavior of sisal fiber‐reinforced PP, PP/HDPE and PP/HDPE with functionalized and non‐functionalized EPR composites was studied. Acetylation of the fiber improves adhesion of the fiber to the polyolefin matrix. In general, acetylation of the sisal fiber was found to enhance the tensile strength and modulus of the resulting composites, except in some cases. Thermal properties suggest that the mixing and molding temperatures are between 160 and 230 °C and that when acetylated fiber is mixed with polyolefins, greater polymer‐fiber interactions takes place, which slightly favor stability of these composite materials. The results allow us to suggest that a satisfactory profit/cost relation justifies the addition of acetylated fiber to PP, PP/HDPE, and PP/HDPE/EPR. © 2000 Society of Chemical Industry     

Effect of ethylene-propylene copolymer with residual PE crystallinity on mechanical properties and morphology of PP/HDPE blends

Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispresed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. © 1995 John Wiley & Sons, Inc.     

Rheological properties of polypropylene/high-density polyethylene blend melts. I. Capillary flow properties

Three kinds of isotactic polypropylenes (PP) with different melt flow indexes (MFIs) were melt-blended with three kinds of high-density polyethylenes (HDPE) with different MFI using a screw extruder, and the morphologies and capillary flow properties such as flow curve, entrance effect, Barus effect, and melt fracture were studied. When HDPE contents were 70 wt % or above and PP particles formed the disperse phase, the size of the particles decreased with decreasing viscosity of PP. When HDPE contents were 30 wt % or below and HDPE particles formed the disperse phase, the size of the particles was minimum when the viscosities of PP and HDPE were similar. The die swell ratios of the blends were higher than those of the components. On the other hand, the entrance correction coefficients of the blends were intermediate between those of the components. There was no correlation between the die swell ratio and the entrance corretion coefficient. Therefore, it is not always appropriate to regard the entrance correction coefficient as a measure of melt elasticity in the case of inhomogeneous polymer systems such as PP/HDPE blend.     

Ultrasonic measurement of orientation in HDPE/iPP blends obtained by dynamic packing injection molding

The orientation of polymer chain has a great effect on its mechanical properties, therefore, it is always an important issue on how to characterize, accurately and quickly, the orientation of polymer chain during processing. In this article, according to the property that ultrasound travels in different velocities in anisotropic media, normal incident shear wave was utilized to explore the orientation structure of HDPE/iPP blends obtained by dynamic packing injection molding. The ultrasonic technique is consistent with the 2D-WAXS in charactering the orientation degree of polymer chains, although ultrasonic technique focuses on the overall orientation of polymer blends while the 2D-WAXS reveals the crystalline orientation of each component. Our work demonstrates that ultrasonic technique might be a reliable, fast and easy way to characterize the orientation structure of crystalline polymer blends. The ultrasonic measurements were performed off-line, but the achievement provides the possibility for on-line detection of orientation structure in injection molding by using ultrasonic technique.     

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.     

Effect of molding temperature on crystalline and phase morphologies of HDPE composites containing PP nano-fibers

A high-density polyethylene (HDPE)/isotactic polypropylene (PP) (75/25) blend containing 25 wt% of PP was fibrillated by roller drawing at 138 °C. The fibrillated blend was processed again at temperatures ranging from 155 to 200 °C by compression molding or extrusion. The effects of molding temperature on the morphology and mechanical properties of the blend were investigated. Wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) were used to study the morphology of the samples. The roller-drawn blend exhibited a fibrous structure with the chain direction aligned parallel to the drawing direction. After molding at 155 °C, the HDPE formed parallel-stacked lamellae retaining the parallel orientation after the melting of the PE crystals. As the molding temperature increased the parallel orientation gradually vanished and some of the parallel-stacked lamellae changed into twisted lamellae. The PP phase existed as fibrils in the PE matrix and the crystals stayed with their molecular chain aligned parallel to the fibrillation direction even when the molding temperature was far above the melting temperature of PP. Nevertheless, the orientation of the crystals did not change as the molding temperature increased from 155 to 165 °C. The internal structure of the PP fibrils changed from a needle structure to a parallel-stacked one. The PP fibrils induced the crystallization of the PE melt, leading to the formation of a trans-crystalline layer at their surface. As the molding temperature increased, more PE lamellae protruded into the PP fibrils and the interface between the PP fibrils and the PE matrix became diffuse.     

Morphology and Properties of Polypropylene Foaming Sheet with Alternating Multilayered Structure

In this work, the foaming sheet was designed as alternating multilayered foam/film structure of foaming layers and film layers. The foaming layer contained polypropylene (PP)/high density polyethylene (HDPE)/Talc ternary composites. The film layer contained PP only. The rheological data showed that the melt elasticity of PP was obviously improved by the addition of HDPE and talc. The results exhibited that the alternating multilayered structure was well kept and hardly influenced by the foaming layers, and then the mechanical properties were obviously improved. The cell in the alternating multilayered sheet with 16 layers was smaller and more homogenous than that in pure PP foaming sheet.     

Mechanical and fracture characterization of 50:50 HDPE/PET blends presenting different phase morphologies

Uncompatibilized and compatibilized blends of poly(ethylene terephthalate) (PET) and high‐density polyethylene (HDPE) (50:50 PET/HDPE) have been prepared and characterized. A commercial grade of ethylene/methacrylic acid copolymer was used as compatibilizing agent and added to the blends in two different proportions, 1% and 7%. Compounded blends were processed following three different procedures: compression molding, extrusion, and extrusion followed by annealing. In every case, there is evidence that suggests that HDPE constitutes the matrix and PET is the dispersed phase. The PET phase shape was related to the processing procedure of the blends. PET adopted a globular morphology in the compression molded samples but it took the form of microfibers (microfibrillar‐like reinforced composites) in extruded samples, which were flattened during the postextrusion annealing process. According to the results obtained in tensile and fracture tests, extruded blends having 7% of ethylene/methacrylic acid copolymer appeared as the optimum combination of processing method and compatibilizer content. POLYM. ENG. Sci., 45:354–363, 2005. © 2005 Society of Plastics Engineers     

Development of isotropic compatible HDPE/PP blends for structural applications

In an attempt to provide superior products for the structural applications, this study aimed at preparing isotropic compatible high density polyethylene (HDPE)/ polypropylene (PP) blends without the use of the expensive compatibilization technique. Morphological and structural characterizations of the homopolymers and blends were carried out. In addition, some of the structurally important mechanical and thermal properties were characterized. Such characterizations were performed to investigate whether or not the blends are compatible and therefore acceptable for the structural applications. Scanning electron microscope (SEM) micrographs of the blend samples indicate that the interfacial adhesion between HDPE and PP phases is intimate in the 5/95 HDPE‐PP, good in the 85/15 HDPE‐PP and 95/5 HDPE‐PP, fair in the 30/70 HDPE‐PP and very poor in the 50/50 HDPE‐PP. Similarly, mechanical and thermal responses of the first three blends are remarkable. The 30/70 HDPE‐PP blend displays a fairly good performance. Whereas, the properties of the 50/50 HDPE‐PP blend are very poor. This decides that the first three blends are compatible and, therefore, structurally attractive materials. The fourth is partially compatible and, as a consequence, can be rather acceptable for the structural applications. However, the fifth is incompatible and, of course, is not acceptable for such applications. On the other hand, SEM micrographs and differential scanning calorimetry results indicate that the crystalline structures of individual polymers are appreciably affected by blending. Additionally, the study reveals that the end use performance of blends is strongly dependent on the crystalline structure changes occurring in each component due to blending as well as the compatibility between the blend components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and properties of rubber-modified polypropylene impact blends

The state of dispersion of poly(ethylene-co-propylene) (PEP) rubber and high-density polyethylene (HDPE) in polypropylene (PP) blends was investigated using scanning electron microscopy to examine solvent-etched microtomed surfaces cut at low temperatures. The validity of the method was established by comparing the areal fraction of dispersed particles in micrographs with the volume fraction of PEP and HDPE in PP-rich blends. When small amounts of PEP and HDPE were added to PP, they combined to form composite PEP–HDPE particles with characteristic internal structures in a PP matrix. Changes in impact strength and flexural modulus with changes in mixing conditions and blend composition were determined and interpreted in terms of the size, composition, and internal structure of the dispersed particles. Particle growth in the melt limited the impact strength level achieved in molded articles. A simple model proposed for screening rubbers for toughening of brittle plastics successfully predicts that PEP rubber should be an excellent impact modifier for PP.