Morphologies of polyethylene–ethylene/propylene/diene monomer particles in polypropylene‐rich polyolefin blends: Flake structure

Morphologies of polyethylene–ethylene/propylene/diene monomer (PE/EPDM) particles in 93/7 polypropylene (PP)/PE blends were investigated. SEM micrographs of KMnO₄‐etched cut surfaces and fracture surfaces of the blends revealed the existence of the “flake” structure. In the particles, crystalline PE formations with flake shape, which remain after etching, are called flakes. In addition to the PE‐crystalline flakes, amorphous PE, located between PE crystalline lamellae and EPDM rubber, complement the flake structure. The flakes are usually linked with the PP matrix, as seen in the heptane‐treated cut surfaces. These links, although observed with compatibilized samples, originate from the crystalline nature of PE particles, if no compatibilizer is added. Separately, the morphology of Royalene (consisting of high‐density PE and EPDM rubber, used as a PP/PE compatibilizer) was investigated by low‐voltage scanning TEM. The interaction of the components in the PE/EPDM blends can explain the formation of the flakes and toughening of the PP/PE blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3087–3092, 2003     

Miscibility and crystallization of metallocene polyethylene blends with polypropylene

The crystallization and morphology of very‐low‐density polyethylene (VLDPE) and ultra‐low‐density polyethylene (ULDPE) blends with isotactic polypropylene (PP) were studied by differential scanning calorimetry (DSC) and hot‐stage optical microscopy (HSOM) with polarized light. In particular, the isothermal crystallization of PP in molten PE was investigated. A polypropylene homopolymer was melt‐blended with six types of VLDPEs and ULDPEs, with variations in branch content and length and in molecular weight. All the blends contained 20% PP by mass. It was found that the crystallization temperatures of PP and PE changed in the blends, and the crystallization of PP was affected by branch length and content and by the molecular weight of the PE, indicating a certain degree of miscibility between PP and PE. The isothermal crystallization rate of PP decreased in the blends; in particular, the crystallization rate of PP was slower in the ULDPE with lower MFI, suggesting that crystallization of PP was hindered by PE and that its rate was regulated by the viscosity of ULDPE. HSOM images showed that a portion of the PP crystallized from molten PE, although phase separation was obvious, providing additional information on the miscible behavior between PP and VLDPEs (or ULDPEs). Furthermore, the miscible level between the PP and the ULDPEs was higher than that between the PP and the VLDPEs because the degree of change in the crystallization behavior of the PP and PE was greater in the PP–ULDPE blends. This was possibly a result of the higher branch content in the ULDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1179–1189, 2003     

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     

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene (hiPP) were studied by solvent extraction fractionation, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nuclear magnetic resonance (¹³C‐NMR), and selected reblending of different fractions of hiPP. The results indicate that hiPP contains, in addition to polypropylene (PP) and amorphous ethylene‐propylene random copolymer (EPR) as well as a small amount of polyethylene (PE), a series of crystallizable ethylene‐propylene copolymers. The crystallizable ethylene‐propylene copolymers can be further divided into ethylene‐propylene segmented copolymer (PE‐s‐PP) with a short sequence length of PE and PP segments, and ethylene‐propylene block copolymer (PE‐b‐PP) with a long sequence length of PE and PP blocks. PE‐s‐PP and PE‐b‐PP participate differently in the formation of multilayered core‐shell structure of the dispersed phase in hiPP. PE‐s‐PP (like PE) constructs inner core, PE‐b‐PP forms outer shell, while intermediate layer is resulted from EPR. The main reason of the different functions of the crystallizable ethylene‐propylene copolymers is due to their different compatibility with the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Tensile properties and morphology of blends of polyethylene and polypropylene

The tensile behavior of blends of linear polyethylene (PE) and isotactic polypropylene (PP) was examined in relation to their morphology. Yield stress increases monotonically with increasing PP content, while true ultimate strength is much lower in all blends than in the pure polymers as a result of early fracture. The blends fail at low elongation because of their two-phase structure, consisting of interpenetrating networks or of islands of PE in a PP matrix, as shown by scanning electron microscopy of fracture surfaces and transmission electron microscopy of thin films. While spherulites in PP are very large (～100 μm in diameter), addition of 10% or more of PE drastically reduces their average size. This, together with the profusion of intercrystalline links introduced by PE, may be associated with maximization of tensile modulus in blends containing ～80% PP. Introduction of special nucleating agents to PP reduces average spherulite size and is accompanied by slight improvements in modulus. Thin films of blends strained in the electron microscope neck and fibrillate in their PE regions, but fracture cleanly with little fibrillation in areas of PP.     

Viscosity effect in polyolefin ternary blends and composites

Ternary blends of PP (80) /rubber (EPM, EPDM) (10) / PE (10) and PP (80) / rubber (10) / CaCO₃ (10) composites were prepared in a twin-screw extruder. With polyethylene (PE) viscosity comparable to, or higher than that of rubber, the dispersed phase formed a reticulate structure with reduced size. On the contrary, when the viscosity of PE was significantly lower than that of rubber, the dispersed phase formed almost homogeneous morphology. With reticulate morphology, PE crystallinity content, hardness, modulus, and elongation at break of the ternary blend increased. In polypropylene (PP) / rubber / CaCO₃ composites, better dispersion of CaCO₃ in the PP matrix was obtained when the viscosity of rubber was significantly higher than that of matrix. With better dispersion, hardness and tensile properties were improved, but the impact strength more or less decreased. © 1993 John Wiley & Sons, Inc.     

Toughening of polypropylene by combined rubber system of ultrafine full-vulcanized powdered rubber and SBS

A combined rubber system of ultrafine full-vulcanized powdered rubber (UFPR) and SBS was used for polypropylene toughening. The PP toughened with the combined rubber system shows not only higher impact strength as compared to each rubber component used alone but also good stiffness and heat resistance. Crystallization study shows that the UFPR is more efficient in promoting the crystallization of PP than SBS, leading to a higher crystallinity and an enhancement of stiffness and heat resistance of PP. The combined rubber system containing UFPR and a small amount of SBS still possesses a good nucleating ability. Transmission electron microscopy results indicate that the combined rubber system mostly forms an encapsulation structure of UFPR particles encapsulated by SBS phase. This morphology was also confirmed by scanning electron microscopy results through observing the fracture surfaces of toughened samples. A small amount of SBS was found to be helpful for a better dispersion of UFPR in PP matrix. The causes for the encapsulation morphology and the synergistic toughening effect were discussed. A tentative explanation was given by comparison of the solubility parameter of each component in the toughened samples.     

Rubber-toughening in polypropylene

To deformation and fracture behavior of several polypropylene (PP) and rubber-modified PP materials have been investigated. Plastic deformation mechanisms of these systems depend upon the test rate and temperature with high rates and low temperatures being in favor of crazing. The ductility and toughness of these materials are explained in light of the competition between crack formation and the degree of plastic deformation through crazing and shear yielding. The second phase morphology with smaller average rubber particle diameter D appears to be more efficient than that with larger D in toughening PP. Theoretical calculations indicate that the stresses imposed upon the rubber particles due to volume shrinkage of PP during crystallization are sufficient to compensate for the stresses due to differential thermal contraction in cooling from solidification temperature to end-use temperature. The difference between these two is small, and therefore they provide very little contribution to interfacial adhesion between rubber particle and PP matrix, the adhesion being insufficient for the rubber particles to be effective in controlling craze propagation. The rubber particles, in addition to promoting crazing and shear yielding, can also improve the fracture resistance of PP by varying the crystalline structure of PP (e.g., reducing the spherulite dimensions).     

Fracture toughness of rotationally molded polyethylene and polypropylene

In this work, the fracture toughness of rotationally molded polyethylene (PE) and polypropylene (PP) was measured using J integral methods at static loading rates and at room temperature. Two different commercially available rotational molding grades PE and PP were tested in this study which have been used in various rotationally molded products such as small leisure craft, water storage tanks, and so on. Scanning electron microscope (SEM), optical microscope, differential scanning calorimetry (DSC), solid‐state nuclear magnetic resonance (solid‐state NMR), and X‐ray scattering were used to investigate the microstructure, fracture surfaces, and compare toughness properties of these materials. In PE, higher molecular weight and broader molecular weight distribution, larger amorphous and crystal region thicknesses are found to be related to higher toughness values. High molecular weight favors higher number of entanglements that improve fracture energy and broader distribution increases long chain branching of higher molecular weight fractions which creates higher entanglements at the branch sites. Larger amorphous regions promote microvoiding more easily compared to thinner amorphous regions, leading to greater plastic deformation and energy absorption. Higher crystal thickness also contributes to microvoiding in the amorphous region. For PP, greater plastic deformation observed in the fracture surfaces is related to higher fracture toughness values. POLYM. ENG. SCI., 58:63–73, 2018. © 2017 Society of Plastics Engineers     

Structure and morphology of polyethylene/polypropylene in‐reactor alloys synthesized by spherical high‐yield Ziegler–Natta catalyst

A series of spherical polyethylene/polypropylene (PE/PP) in‐reactor alloys were synthesized with spherical high‐yield Ziegler–Natta catalyst by sequential multistage polymerization in slurry. The morphology of PE/PP alloy granule was evaluated by optical microscopy, scanning electron microscopy, and transmission electron microscopy. The results show PE/PP in‐reactor alloy with excellent morphology, high porosity, and narrow distribution of the particle size. The PE/PP in‐reactor alloys show excellent mechanical properties with good balance between toughness and rigidity. It was fractionated into five fractions by temperature‐gradient extraction fractionation, and every fractionation was analyzed by FTIR, ¹³C‐NMR, DSC, and WAXD. The PE/PP in‐reactor alloy was found to contain mainly five portions: PP, PE, segmented copolymer with PP and PE segment of different length, ethylene‐b‐propylene copolymer, and an ethylene–propylene random copolymer. The characteristic chain structure leads to good compatibility between the fractions of the alloy that shows a multiphase structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2075–2085, 2007     

Grafting of polystyrene branches to polyethylene and polypropylene

Polyethylene (PE) and polypropylene (PP) were reacted with benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) to prepare PE‐TEMPO and PP‐TEMPO macroinitiators, respectively. Molecular weight of PP decreased, whereas that of PE increased during the reaction with the BPO/TEMPO system. Polystyrene (PS) branches were grafted to PE and PP backbone chains as a result of bulk polymerization of styrene with the PE‐TEMPO and PP‐TEMPO macroinitiators. A significant amount of PS homopolymer was produced as a byproduct. Weight of the resulting PE‐g‐PS and PP‐g‐PS increased with the polymerization time up to 20 h and then leveled off. Melting point of PE and PP domains in PE‐g‐PS and PP‐g‐PS, respectively, lowered as the content of PS in the copolymers increased. However, glass transition of the copolymers was almost identical with that of PS homopolymer, indicating that the constituents in the copolymers were all phase‐separated from each other. In scanning electron microscopy of the incompatible PE/PS, PP/PS, and PE/PP/PS compounded with PE‐g‐PS and PP‐g‐PS, any clear indication of enhanced adhesion between the phases was not observed. However, phase domains in the blends were, nevertheless, reduced significantly to raise mechanical properties such as maximum stress and elongation at break by 20–75%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1103–1111, 2002     

Morphology and properties of blends of polypropylene with ethylene-propylene rubber

Great attention has been paid to the toughening of isotactic polypropylene (PP) in recent years in order to make full use of this plastic. This paper presents the results of our study on the compatibility of PP with ethylene-propylene-diene rubber (EPT), polybutadiene rubber (PB) or styrene-butadiene rubber (SBR) through characterization of the blends' morphology, and on. the morphology and properties of binary blends of PP with EPT (EPT/PP) and ternary blends of PP, EPT, and polyethylene (PE) (EPT/PE/PP). Morphological structure of solution blends and the great improvement in low-temperature impact strength and other properties of the mechanical blends have shown the difference among EPT, PB, and SBR in compatibility with PP, the effectiveness of using EPT as PP's toughening agent, and the effect of EPT on EPT/PP blend as both toughening agent and compatibilizer. Addition of EPT to EPT/PP made interesting changes in morphology but no effect on properties was observed.     

Sequences of fracture toughness micromechanisms in PP/CaCO3 nanocomposites

Mechanical properties and fracture toughness micromechanisms of copolypropylene filled with different amount of nanometric CaCO₃ (5–15 wt %) were studied. J‐integral fracture toughness was incorporated to measure the effect of incorporation of nanoparticle into PP matrix. Crack‐tip damage zones and fracture surfaces were studied to investigate the effect of nanofiller content on fracture toughness micromechanisms. It was found that nanofiller acted as a nucleating agent and decreased the spherulite size of polypropylene significantly. J‐integral fracture toughness (J_c) of nanocomposites was improved dramatically. The J_c value increased up to approximately two times that of pure PP at 5 wt % of nano‐CaCO₃. The fracture micromechanisms varied from rubber particles cavitation and shear yielding in pure PP to simultaneous existence of rubber particles cavitation, shear yielding, filler particles debonding, and crazing in PP/CaCO₃ nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PE100管及其热熔接头的蠕变裂纹扩展行为

聚乙烯(PE)管性能优异,广泛应用于城市水及燃气供应系统。PE管的主要破坏形式是长期静压载荷下的慢速裂纹扩展失效。在蠕变条件下,采用光滑试样和裂纹圆棒试样对PE100管及其热熔接头进行了测试,得到了基于蠕变断裂参数C*的蠕变裂纹扩展动力学关系式。利用扫描电子显微镜(SEM)分析了裂纹圆棒试样的断面形貌,对比分析结果发现,蠕变裂纹扩展失效模式对应的最大应力为15.05 MPa,热熔接头熔合面分布有约11个/mm^2、直径范围为1~5μm的微气孔,热熔接头断裂微纤平均长度比母材约小20%~45%。当热熔对接时,熔合面存在的微气孔以及系带分子的浅渗透是导致PE100热熔接头蠕变裂纹扩展抗力降低的主要原因。     

Processing of polyolefin blends

The morphology of binary and ternary polyolefin blends of polypropylene (PP), ethylene-propylene-diene terpolymer (EPDM) and polyethylene (PE) following processing by injection and compression molding has been examined by optical and scanning electron microscopy. Internal surfaces were generated by low temperature fracture and etching with cyclohexane. In binary blends, droplets of EPDM are elongated in the flow direction within 400μm of the mold surface in injection molding, yielding a skin region which is distinct from an isotropic core containing spherical EPDM inclusions. Spherical droplets of EPDM or PE in binary blends with PP increase in size with increasing compression molding time. In ternary blends, spherical inclusions containing both EPDM and PE are dispersed in PP. With increasing compression molding time, EPDM separates from PE and concentrates at the outer edges of the PE inclusion, effectively isolating PE from the PP matrix.     

Fracture toughness of modified polypropylene/poly(styrene‐ran‐butadiene) blends

Fracture toughness of polypropylene (PP)/poly(styrene‐ran‐butadiene) rubber (SBR) blends as a function of concentration of maleic anhydride (MA) in the maleated polypropylene (MAPP) compatibilizer was investigated under uniaxial static and impact loading conditions. The addition of MAPP to the unmodified PP/rubber blend enhanced the tensile modulus and yield stress as well as the Charpy impact strength. The maximum values were recorded at 1.0 wt% grafted MA in the compatibilizer. V‐shaped blunt‐notched specimens exhibited typical ductile behavior and no breakage of the specimens occurred during the impact fracture tests. Sharp‐notched specimens of uncompatibilized and low‐content MA blends broke in a semibrittle manner, supported by a rapid crack propagation process. Increasing MA content in the blends led to semibrittle‐to‐ductile transition characterized by stable crack propagation. Fracture mechanics experiments, supplemented by scanning electron microscopy (SEM), were also employed to obtain a better understanding of the fracture and deformation behavior. Copyright © 2005 Society of Chemical Industry     

Dynamic mechanical properties and morphology of polypropylene block copolymers and polypropylene/elastomer blends

The relation between the dynamic mechanical properties and the morphology of polypropylene (PP) block copolymers and polypropylene/elastomer blends was studied by dynamic mechanical analysis (DMA), light- and electron microscopy. The latter techniques contributed to an improvement in assignments of relaxation transitions in the DMA spectra. It was established that PP block copolymers had multiphase structure since the ethylene/propylene rubber phase (EPR) formed in the copolymerization contained polyethylene (PE) domains. An identical morphology was found in the case of PP/polyolefin thermoplastic rubber (TPO) blends. Impact modification of PP by styrene/butadiene block copolymers led to a multiphase structure, too, due to the polystyrene (PS) domains aggregated in the soft rubbery polybutadiene phase. In the semicrystalline polyolefinic and in the amorphous styrene/butadienebased thermoplastic rubbers, PE crystallites and PS do mains acted as nodes of the physical network structure, respectively. PP/EPDM/TPO ternary blends developed for replacing high-density PE showed very high dispersion of the modifiers as compared to that of PP block copolymers. This fine dispersion of the impact modifier is a basic regulating factor of impact energy dissipation in the form of shear yielding and crazing.     

Deformation,yield and fracture of elastomer‐modified polypropylene

In recent decades, great attention has been devoted to the toughening of isotactic poly(propylene) (PP) with elastomers such as ethylene–propylene rubber (EPR). The most important reasons for this interest are the moderate cost and favorable properties of PP. This article is focused on the role of EPR in the deformation and fracture mechanism of PP/EPR blends with different volume fractions of elastomer phase. Differential scanning calorimetry (DSC), tensile tests, and microscopy techniques were used in this study. The fracture mechanism of isotactic PP toughened by EPR (PP/EPR) has also been studied by three point bending (3‐PB) and four point bending (4‐PB) tests. Rubber particle cavitation appears to be the main mechanism of microvoid formation, although some matrix/particle debonding was observed. The investigation of the toughening mechanism shows that a wide damage zone spreads in front of the pre‐crack. Optical microscopy (OM) illustrates that, in pure PP, crazing is the only fracture mechanism, and no evidence of shear yielding is found, while in PP blends craze‐like features associated with shear yielding are observed, which have been identified as high shear localized dilatational bands. This type of deformation pattern supports a model previously proposed by Lazzeri 1 to explain the interparticle distance effect on the basis of the stabilization effect on dilatational band propagation exerted by stretched rubber particles. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3767–3779, 2003     

Tensile deformation mechanisms of polypropylene/elastomer blends reinforced with short glass fiber

Polypropylene hybrid composites reinforced with short glass fiber (SGF) and toughened with styrene–ethylene butylenes–styrene (SEBS) elastomer were prepared using extrusion and injection‐molding techniques. Moreover, hybrids compatibilized with SEBS‐grafted maleic anhydride (SEBS‐g‐MA) and hybrid compatibilized with PP grafted with maleic anhydride (PP‐g‐MA) were also fabricated. The matrix of the latter hybrid was designated as mPP and consisted of 95% PP and 5% PP‐g‐MA. Tensile dilatometry was carried out to characterize the fracture mechanisms of hybrid composites. Dilatometric responses showed that the elastic deformation was the dominant deformation mechanism for the SGF/SEBS/PP and SGF/SEBS‐g‐MA/PP hybrids. However, cavitation deformation prevailed over shearing deformation for both hybrids at the higher strain regime. The cavitation strain resulted from the debonding of glass fibers and from the crazing of the matrix in the SGF/SEBS/PP hybrid. In contrast, the cavitation was caused by the debonding of SEBS particles from the matrix of the SGF/SEBS‐g‐MA/PP hybrid. The use of PP‐g‐MA resulting in elastic deformation was the main mode of deformation in the low‐strain region for the SGF/SEBS/mPP and SEBS/SEBS‐g‐MA/mPP hybrids; thereafter, shearing appeared to dominate at the higher strain regime. This was attributed to the MA functional group improving the bonding between the SGF and PP. The correlation between fracture morphology and dilatometric responses also is presented in the article. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 441–451, 2003     

Development and characterization of an all‐olefin thermoplastic sandwich composite system

In this investigation an all‐olefin thermoplastic sandwich system was developed and characterized. Commingled glass fiber polypropylene (PP) composite was used as skin and HDPE (PE) foam with closed cells as core. Infra‐red heating was used for melting the surfaces of the substrates for surface fusion bonding with a cold press. Two tie layer films, viz. ethylene‐propylene copolymer (EPC) and HDPE/elastomer blend, were used as hot melt adhesives for bonding the substrates. Single lap shear joints were prepared from PP composite and PE foam adherends with a bonding area of 25.4 mm × 25.4 mm to determine the interface strength. EPC tie layer provided higher bond strength (27.4 kg/cm²) to the all‐olefin sandwich system than HDPE/elastomer blend based one (19.7 kg/cm²). For EPC tie layer based sandwiches, a mixed mode a failure was observed in the failed lap shear samples; about 40% is cohesive failure through tie layer, and the rest of failure was adhesive either at PP composite or PE surfaces. Environmental scanning electron micrographs (ESEM) reveal that in the process of surface fusion bonding, PE foam cells in the vicinity of 0.80 mm interphase area were coalesced with high temperature and pressure. No macro level penetration of tie layer melt front into foam cells was observed. As the surface morphology of foam was altered on account of IR surface heating and the PP composite bonding side had a resin‐rich layer, the bonding situation was closer to that between two polymer film surface.