Polypropylene/polyethylene blends as models for high‐impact propylene–ethylene copolymers,part 1: Interaction between rheology and morphology

In this work, composition effects on interfacial tension and morphology of binary polyolefin blends were studied using rheology and electron microscopy. The amount of dispersed phase (5–30 wt %) and its type [ethylene–octene copolymer, linear low‐density polyethylene (LLDPE), and high‐density polyethylene] was varied, and the influence of different matrix materials was also studied by using a polypropylene homopolymer and a ethylene–propylene (EP) random copolymer. The particle size distribution of the blends was determined using micrographs from transmission electron microscopy (TEM). A clear matrix effect on the flow behavior could be found from the viscosity curves of the blends. Analyzing the viscosity of the blends applying the logarithmic mixing rule indicated a partial miscibility of the EP random copolymer with low amounts of the LLDPE in the melt. Micrographs from TEM also showed a clear difference in morphology if the base polymer is changed, with PE lamellae growing out of the inclusions or being present directly embedded in the matrix. To verify these findings, the interfacial tension was determined. The applicability of Palierne's emulsion model was found to be limited for such complex systems, whereas Gramespacher–Meissner analysis led to interfacial tensions comparable with those already reported in the literature. The improved compatibility when changing the matrix polymer from the homopolymer to the random copolymer allows the development of multiphase materials with finer phase structure, which will also result in improved mechanical and optical performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of copolymer fraction composition in ultrahigh molecular weight polyethylene blends with ethylene/1‐hexene copolymers on material physical and tensile properties

The reactor blends (RBs) with bimodal molecular weight distribution on the base of ultrahigh molecular weight polyethylene (UHMWPE) and low molecular weight random ethylene/1‐hexene copolymers (CEH) were synthesized by two‐step processes including ethylene polymerization followed by ethylene/1‐hexene copolymerization over rac‐(CH₃)₂Si(Ind)₂ZrCl₂/methylaluminoxane catalyst. The four series of blends differed in a composition of copolymer fraction that was varied in a wide range (from 3.0 to 37.0 mol % of 1‐hexene). The differential scanning calorimetric study shows the double melting behavior of the net semicrystalline CEHs, which can be attributed to intramolecular heterogeneity in chain branch distribution. The introduction of CEHs leads to the modification of nascent RB crystalline and amorphous phases. Physical and tensile properties as well as melting indexes of the materials depend not only on the percentage of copolymer fraction that varied from 6.9 to 35.8 wt % but also on its composition. The increase of copolymer fraction with high content of 1‐hexene (≥11.0 mol %) in the blends leads to the change of the character of stress–strain curves; the materials behave as elastomers. Controlled regulation of copolymer fraction characteristics in the synthesis yields RBs combining the enough high strength, good plastic properties with enhanced melting indexes as compared with the net UHMWPE. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40151.     

Structure and properties of polypropylene/high‐density polyethylene blends by solid equal channel angular extrusion

The solid equal channel angular extrusion (ECAE) process on polypropylene (PP)/high‐density polyethylene (HDPE) blends was carried out. Scanning electron microscopy (SEM) was used to observe the sample structures. Results showed that ECAE process could make PP/HDPE blends to produce orientation structure. Impact performance of ECAE‐PP/HDPE samples after ECAE process improved remarkably, especially for ECAE‐PP/HDPE (90/10)‐O whose impact strength reached 91.91 kJ/m², 18.1 times higher than that of pure PP and 11.2 times higher than that of PP/HDPE (90/10). The mechanism of enhancing between HDPE and PP was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39759.     

Dynamic mechanical properties and morphology of high‐density polyethylene/CaCO3 blends with and without an impact modifier

Dynamic mechanical analysis and differential scanning calorimetry were used to investigate the relaxations and crystallization of high‐density polyethylene (HDPE) reinforced with calcium carbonate (CaCO₃) particles and an elastomer. Five series of blends were designed and manufactured, including one series of binary blends composed of HDPE and amino acid treated CaCO₃ and four series of ternary blends composed of HDPE, treated or untreated CaCO₃, and a polyolefin elastomer [poly(ethylene‐co‐octene) (POE)] grafted with maleic anhydride. The analysis of the tan δ diagrams indicated that the ternary blends exhibited phase separation. The modulus increased significantly with the CaCO₃ content, and the glass‐transition temperature of POE was the leading parameter that controlled the mechanical properties of the ternary blends. The dynamic mechanical properties and crystallization of the blends were controlled by the synergistic effect of CaCO₃ and maleic anhydride grafted POE, which was favored by the core–shell structure of the inclusions. The treatment of the CaCO₃ filler had little influence on the mechanical properties and morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3907–3914, 2007     

Dynamic mechanical behavior of high‐density polyethylene/ethylene vinyl acetate copolymer blends: The effects of the blend ratio,reactive compatibilization,and dynamic vulcanization

The effects of the blend ratio, reactive compatibilization, and dynamic vulcanization on the dynamic mechanical properties of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends have been analyzed at different temperatures. The storage modulus of the blend decreases with an increase in the EVA content. The loss factor curve shows two peaks, corresponding to the transitions of HDPE and EVA, indicating the incompatibility of the blend system. Attempts have been made to correlate the observed viscoelastic properties of the blends with the blend morphology. Various composite models have been used to predict the dynamic mechanical data. The experimental values are close to those of the Halpin–Tsai model above 50 wt % EVA and close to those of the Coran model up to 50 wt % EVA in the blend. For the Takayanagi model, the theoretical value is in good agreement with the experimental value for a 70/30 HDPE/EVA blend. The area under the loss modulus/temperature curve (LA) has been analyzed with the integration method from the experimental curve and has been compared with that obtained from group contribution analysis. The LA values calculated with group contribution analysis are lower than those calculated with the integration method. The addition of a maleic‐modified polyethylene compatibilizer increases the storage modulus, loss modulus, and loss factor values of the system, and this is due to the finer dispersion of the EVA domains in the HDPE matrix upon compatibilization. For 70/30 and 50/50 blends, the addition of a maleic‐modified polyethylene compatibilizer shifts the relaxation temperature of both HDPE and EVA to a lower temperature, and this indicates increased interdiffusion of the two phases at the interface upon compatibilization. However, for a 30/70 HDPE/EVA blend, the addition of a compatibilizer does not change the relaxation temperature, and this may be due to the cocontinuous morphology of the blends. The dynamic vulcanization of the EVA phase with dicumyl peroxide results in an increase in both the storage and loss moduli of the blends. A significant increase in the relaxation temperature of EVA and a broadening of the relaxation peaks occur during dynamic vulcanization, and this indicates the increased interaction between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2083–2099, 2003     

Novel polyethylene‐b‐polyurethane‐b‐polyethylene triblock copolymers: Facile synthesis and application

A series of novel polyethylene‐b‐polyurethane‐b‐polyethylene (EUE) triblock copolymers is successfully prepared through a facile route combining the thiol‐ene chemistry, addition polymerization, and coupling reaction. The resulting EUE triblock copolymers are characterized by Nuclear magnetic resonance (¹H NMR), Fourier transform‐infrared spectra (FT‐IR), High temperature gel permeation chromatography (HT‐GPC), Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA), and Transmission electron microscopy (TEM). In addition, the EUE triblock copolymers have been evaluated as compatibilizers in the polymer blends of thermoplastic polyurethane elastomer (TPU) and high‐density polyethylene (HDPE). The SEM results show that the compatibility of immiscible blends is enhanced greatly after the addition of EUE triblock copolymers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42967.     

Photodegradation of thermodegraded polypropylene/high‐impact polystyrene blends: Mechanical properties

The influence of the addition of high‐impact polystyrene (HIPS) on polypropylene (PP) photodegradation was studied with blends obtained by extrusion with and without styrene–butadiene–styrene (SBS) copolymer (10 wt % with respect to the dispersed phase). The concentrations of HIPS ranged from 10 to 30 wt %. The blends and pure materials were exposed for periods of up to 15 weeks of UV irradiation; their mechanical properties (tensile and impact), fracture surface, and melt flow indices were monitored. After 3 weeks of UV exposure, all of the materials presented mechanical properties of the same order of magnitude. However, for times of exposure greater than 3 weeks, an increasing concentration of HIPS resulted in a better photostability of PP. These results were explained in light of morphological observations. This increase of photostability was even greater when SBS was added to the blends. It was more difficult to measure the melt flow index of the binary PP/HIPS blends than that of PP for low concentrations of HIPS; this was most likely due to energy transfer between the blend domains during photodegradation. This phenomenon was not observed for the ternary blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization and fracture behaviors of high‐density polyethylene/linear low‐density polyethylene blends: The influence of short‐chain branching

Two commercial polyethylene samples, linear high‐density polyethylene (HDPE) and branched linear low‐density polyethylene with almost the same molecular weight distribution but different contents of short‐chain branching (SCB) were melt blended based on the consideration of practical application. Dynamic rheology analysis indicated good compatibility of all the blends with different compositions. Common differential scanning calorimeter (DSC) tests and successive self‐nucleation and annealing (SSA) treatment showed several interesting phenomena. First, without consideration of the effect of molecular weight and molecular weight distribution impact, co‐crystallization occurred at all ratios even the two components had a considerable difference in SCB distribution. Second, in SSA curves the area of the first two melting peaks, i.e., the amount of the thick lamellas of the two components showed an obvious positive deviation with the increase of HDPE content owing to the crystal perfection improved by the co‐crystallization. Essential Work of Fracture tests proved the co‐crystallization effects had a positive effect on the improvement of the resistance to crack propagation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flow‐induced solidification of high‐impact polypropylene copolymer compositions: Morphological and mechanical effects

Polypropylene‐based impact copolymers are a complex composition of matrix material, a dispersed phase and many optional modifiers. The final heterophasic morphology of such systems is influenced significantly by the processing step, adding an additional level of complexity to understanding the structure‐property relation. This topic has hardly been studied so far. The effect of thermal history and shear flow on the solidification process of three different compositions of a polypropylene‐based impact copolymer, i.e., one base material and two compounds with either high density polyethylene or ethylene‐co‐octene added, is investigated. Samples are examined using differential scanning calorimetry, extended dilatometry, transmissions electron microscopy, and finally, tensile testing. With flow, the materials show pronounced flow‐enhanced crystallization of the matrix material and deformed filler content. Compared to the base polymer, the stress–strain response of the compounded samples shows a lower yield stress and more pronounced influence of shear, reflected in the increasing strain hardening modulus. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42040.     

Correlation between the fracture toughness and β‐crystal fraction in a β‐nucleated propylene‐based propylene–ethylene random copolymer

Propylene‐based propylene–ethylene random copolymer (PPR) has been widely used in the production of hot‐water pipes. To further improve its toughness and thermal resistance, β‐nucleating agents (β‐NAs) are frequently incorporated. In this study, PPR containing 5.6 mol % ethylene units was modified by two kinds of β‐NAs, that is, calcium pimelate and N,N′‐dicyclohexylterephthalamide. The notched Izod impact strength of PPR increased with the addition of the β‐NAs. Drastically different toughening effects were found between the two β‐NAs. The structure of PPR with and without a β‐NA was investigated by calorimetry, X‐ray diffraction, and thermomechanical analysis. The results indicated that the relative fraction of β crystals (k_β) in the injection‐molded specimens was determined by the type and content of β‐NA. The relationship between k_β and the impact toughness was summarized. A critical value for k_β (0.68) was identified for the brittle–ductile transition of PPR. PPR with β‐NA having a k_β greater than 0.68 displayed a higher impact strength than the other mixtures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42930.     

Rice husk/poly(propylene‐co‐ethylene) composites: Effect of different coupling agents on mechanical,thermal, and morphological properties

Poly(propylene‐co‐ethylene) composites with rice husk were prepared in a corotating intermeshing twin‐screw extruder using four different coupling agents. While modified maleic anhydrides such as maleated polypropylene (MAPP) and maleated polyethylene (MAPE) are commonly used as compatibilizers to improve interfacial adhesion between lignocellulosic filler and matrix, in this study, polypropylene grafted with acid comonomer (CAPP) and high‐density polyethylene grafted with acid comonomer (CAPE) were also used. The morphologies and the thermal and mechanical properties of the composites were characterized using scanning electron microscopy, thermogravimetric analysis, differential scanning analysis, tensile and impact tests. The results indicate that the base resin of the compatibilizer is an important factor in determining the effectiveness of compatibilizers for composites. Composites with PP‐based compatibilizers are more effective than PE‐based compatibilizers due to the improved wetting of the former compatibilizer in the matrix polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and mechanical properties of linear low‐density polyethylene/low‐density polyethylene/wax ternary blends

The thermal and mechanical properties of uncrosslinked three‐component blends of linear low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and a hard, paraffinic Fischer–Tropsch wax were investigated. A decrease in the total crystallinity with an increase in both LDPE and wax contents was observed. It was also observed that experimental enthalpy values of LLDPE in the blends were generally higher than the theoretically expected values, whereas in the case of LDPE the theoretically expected values were higher than the experimental values. In the presence of higher wax content there was a good correlation between experimental and theoretically expected enthalpy values. The DSC results showed changes in peak temperature of melting, as well as peak width, with changing blend composition. Most of these changes are explained in terms of the preferred cocrystallization of wax with LLDPE. Young's modulus, yield stress, and stress at break decreased with increasing LDPE content, whereas elongation at yield increased. This is in line with the decreasing crystallinity and increasing amorphous content expected with increasing LDPE content. Deviations from this behavior for samples containing 10% wax and relatively low LDPE contents are explained in terms of lower tie chain fractions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1748–1755, 2005     

Morphology and mechanical properties of binary blends of polypropylene with statistical and block ethylene‐octene copolymers

In the present work, statistical (EOCs) and block (OBCs) ethylene‐octene copolymers, with similar densities and crystallinities, were used as impact modifiers of isotactic polypropylene (iPP), and the toughening effects of these two types of elastomers were compared. The viscosity curves of EOCs were similar to those of OBCs with equivalent melt flow rate (MFR), enabling a comparison of the viscosity ratio and elastomer type as independent variables. No distinct differences on the crystal forms and crystal perfection of iPP matrix in various blends were observed by thermal analysis. Morphological examination showed that OBCs form smaller dispersed domains than EOCs with similar MFRs. The flexural modulus, yield stress, stress and strain at break showed the same variation tendency for all the investigated polypropylene/elastomer blends. However, the room temperature Izod impact toughness of iPP/OBC blend was higher than that of iPP/EOC blend containing elastomer with the similar MFRs. The experimental results indicated that the compatibility of iPP/OBCs was much higher than that of iPP/EOCs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and mechanical properties of silicon rubber/cis‐polybutadiene rubber/ethylene–propylene–diene monomer blends

Considering the properties of silicon rubber, ethylene–propylene–diene monomer (EPDM), and cis‐polybutadiene rubber (BR), a blend made by a new method was proposed in this article; this blend had thermal resistance and good mechanical properties. The morphology of the blend was studied by SEM, and it was found that the adhesion between the phases of BR, EPDM, and polysiloxanes (silicon rubber) could be enhanced, and the compatibility and covulcanization were good. The influence of the mass ratio of peroxide and silica on the mechanical properties and thermal resistance of the blend was studied. The results showed that the mechanical properties and thermal resistance of the blend were improved when silicon rubber/BR/EPDM was 20/30/50, dicumyl peroxide/sulfur was 2.5/2.5, and the amount of silica was 80 phr. The integral properties of rubber blend had more advantages than did the three rubbers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4462–4467, 2006     

Photochemical aging and processability of life‐time‐controlled polystyrene/high‐impact polystyrene blends

This work investigated the influence of the addition of acetophenone and benzophenone (2.5 and 5%) on the photodegradability of polystyrene/high‐impact polystyrene blends (50/50 w/w) prepared by sheet extrusion, aiming to improve their decomposition during exposure to a natural environment. The modified materials were submitted to photodegradation under controlled conditions, and the extent of degradation was monitored by suitable characterization techniques, such as infrared and ultraviolet–visible spectroscopy, viscosimetry, and measurements of the mechanical properties. The processability of the modified blends was also studied by capillary and oscillatory rheometry. Evidence for the formation of hydroperoxides and carbonyl groups, the occurrence of chain scission, and the loss of mechanical properties was achieved, being greater for samples with benzophenone. It was also observed that for the same ketone level, benzophenone caused greater changes in the mechanical properties, and this was in agreement with the decrease in the molecular weight observed. Thus, the addition of this type of chemical compound could enhance the photodegradability of polystyrene/high‐impact polystyrene blends without a significant effect on their processability and mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Rheological and mechanical properties of compatibilized polystyrene/ethylene vinyl acetate blends

In this study, a blend of polystyrene (PS)/ethylene vinyl acetate (EVA) (PS/EVA, 90 : 10 wt %) was compatibilized with three different block copolymers, in which their end blocks were compatible with either styrene or EVA. The compatibilized blends with different compositions were prepared using a twin‐screw extruder and injection molded into the required test specimens. Mechanical properties of the blends, such as tensile properties and Charpy impact strength, morphology of tensile fractured surfaces, rheological properties, and thermal properties, were investigated. The results show that the interaction between the dispersed and continuous phase can be improved by the addition of a compatibilizer. Appreciable improvement in the impact strength of the blend with 15 wt % of compatibilizer C (polystyrene‐block‐polybutadiene) was observed. Its mechanical properties are comparable to those of the commercial high‐impact polystyrene, STYRON 470. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2071–2082, 2004     

Surface segregation of polyethylene in low‐density polyethylene/ethylene–propylene–diene rubber blends: Aspects of component structure

Aspects of the molecular weight and its distribution, the branching of low‐density polyethylene (LDPE), and the molecular composition of the ethylene–propylene–diene rubber (EPDM) matrix are presented in this article in terms of their influence on the surface segregation of polyethylene (PE) in elastomer/plastomer blends. All of the PEs studied, despite different weight‐average molecular weights and degrees of branching, segregated to the surface of the LDPE/EPDM blends. Atomic force microscopy pictures demonstrated defective crystalline structures on the surface of the blends, which together with a decrease in the degrees of their bulk crystallinity and a simultaneous increase in their melting temperatures, pointed to a low molecular weight and a defective fraction of PE taking part in the surface segregation. The extent of segregation depended on the molecular structure of the EPDM matrix, which determined the miscibility of the components on a segmental level. The higher the ethylene monomer content in EPDM was, the lower was the PE content in the surface layer of the blends. The composition and structure of the surface layer was responsible for its lower hardness in comparison with the bulk of the blends studied. The surface gradient of the mechanical properties depended on the physicochemical characteristics of the components and the blend composition, which created the possibility of tailoring the LDPE/EPDM blends to dedicated applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 625–633, 2006     

Polypropylene/linear low‐density polyethylene blends: Morphology,crystal structure,optical, and mechanical properties

The morphology, crystal structure, crystallization behavior, optical, and mechanical properties of isotactic polypropylene (iPP) blended with metallocene linear low‐density polyethylene (mLLDPE) and Ziegler–Natta linear low‐density polyethylene (zLLDPE), with and without nucleating agents, were investigated. The correlation between the structures and optical properties was investigated. The addition of linear low‐density polyethylenes (LLDPEs), nucleating agents, and poly(ethylene‐co‐octene) (POE) had little influence on the crystal form of the iPP. The growth along the b axis was favorable in the presence of nucleating agents and LLDPEs. The LLDPEs led to much finer crystal morphologies, and the nucleating agents further prohibited spherulite formation; consequently, light scattering from the bulk crystalline structure was reduced. In all blends, biphase morphology was observed, and POE could improve the adhesion between the iPP and mLLDPE. After blending with LLDPEs, the haze and stiffness decreased, and the gloss increased. mLLDPE enhanced the toughness whereas zLLDPE had a slight influence on it. The nucleating agents decreased the haze, increased the gloss more, and ameliorated the stiffness; however, they changed the toughness little. POE increased the toughness of the blend significantly, accompanied by a much lower haze, higher gloss, and almost the same stiffness. When the concentration of 1,3 : 2,4‐bis(3,4‐dimethyl‐benzylidene sorbitol) exceeded 0.25 wt %, the optical properties and mechanical properties leveled off. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Role of crystalline ethylene‐propylene copolymer on mechanical properties of impact polypropylene copolymer

Impact polypropylene copolymer (IPC) has been known as a multiphase material in which an ethylene‐propylene (EP) random copolymer, serves as toughening component, is dispersed in the homo‐polypropylene hPP matrix. The crystalline EP copolymer (cEP) is another component whose role and microstructural effect on the IPC properties has not been well understood. This work reveals the relationship between the microstructure of cEP and the mechanical properties, that is, impact and tensile resistance, of IPC. We clarify that IPC comprising high contents of cEP with long homo‐PP segment can extend the elongation at break while cEP with high content of homo‐PE segment contributes to high impact strength. Mechanisms for both of these processes have been proposed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013