Effect of the addition of EPM copolymers on the properties of high density polyethylene/isotactic polypropylene blends: II. Morphology and mechanical properties of extruded samples

The influence of the addition of two ethylene-propylene random copolymers (EPM) with different composition on the mechanical properties, thermal behavior and overall morphology of high density polyethylene (HDPE)/isotactic polypropylene (iPP) blends, was investigated on extruded samples. The experimental data showed that the morphology of binary HDPE/iPP blends is drastically modified by these additives and that the ultimate mechanical properties of these mixtures are greatly improved. A reasonable explanation of these results can be ascribed to the fact that these copolymers can act as “compatibilizing agents” in the amorphous regions of the two semicrystalline homopolymers. The extent of such effects is dependent on the chemical structure and/or on the molecular mass of the added copolymer as well as on the HDPE/iPP blend compositions.     

The cocrystallization behavior of binary blends of isotactic polypropylene and propylene-ethylene random copolymers

Rapidly crystallized blends of metallocene isotactic polypropylene and propylene-ethylene random copolymers with an ethylene content varying from 0.76 to 7 mol% were found to cocrystallize to different degrees depending on the composition of the comonomer and content of copolymer in the blend. The degree of molecular mixing was studied using differential scanning calorimetry and solvent extraction techniques. A high extent of cocrystallization is obtained in the whole composition range of blends with a copolymer having up to ～ 2 mol% of ethylene. The degree of cocrystallization decreases gradually with increasing ethylene content or with increasing copolymer content in the blend. It is found that for ethylene contents as high as 5–7 mol% the copolymer rich blends show partial separate crystallization of the propylene ethylene copolymer. Thus, these crystals were selectively extracted at temperatures just above the dissolution temperature of the pure copolymer. In these blends, the fractional content of segments from the copolymer molecules incorporated in the cocrystal is low, yet it prevents extraction of these molecules at temperatures above the dissolution temperature of the copolymer. The degree of cocrystallization is explained by differences in crystallization kinetics of the pure components. The percentage of extracted material was found to be directly related to the dissolution temperature of the cocrystal which was also found to be a linear function of the inverse of the crystallite thickness. The high extent of cocrystallization observed for these polypropylene blends contrasts with comparable blends of polyethylenes. The blends of linear PE with a copolymer of 4 mol% branch units and higher, form separate crystals even after rapid crystallization.     

Shear-induced epitaxial crystallization in injection-molded bars of high-density polyethylene/isotactic polypropylene blends

As a continuation of our previous works on exploring shear-induced epitaxial crystallization of polyolefin blends during practical molding processing [Na et al. Polymer 2005; 46, 819 and 5258], the present study focused on the importance of molecular weight on the formation of epitaxial structure in injection-molded bars of high-density polyethylene (HDPE)/isotactic polypropylene (iPP) blends. By choosing two kinds of HDPE and two kinds of iPP with high molecular weight or low molecular weight, four blends with different molecular weight combinations can be designed. After making the blends via melt mixing, the injection-molded bars were prepared in a so-called dynamic packing injection molding equipment where repeated shearing was imposed on the melts during the solidification stage. Crystal structure and orientation were estimated mainly through 2D-WAXD. Our results indicated that an appropriate matching of low molecular weight HDPE and high molecular weight iPP was more favorable for epitaxial crystallization than other component matches. The effects of orientation and epitaxy on the re-crystallization behaviors of polyolefin blends have been elucidated in detail through PLM experiments. Moreover, epitaxy has been proved to play a positive effect in determining the ultimate mechanical properties of injection-molded bars.     

Morphology and mechanical properties in the binary blends of isotactic polypropylene and novel propylene-co-olefin random copolymers with isotactic propylene sequence 1. Ethylene-propylene copolymers

The additive effects of the novel ethylene-propylene random (EP) copolymers with high isotacticity in propylene sequence on the morphology and mechanical properties of isotactic polypropylene (iPP) were investigated using polarized optical microscopy, transmission electron microscopy, dynamic mechanical analysis and tensile behavior. According to these results, the EP copolymers with a propylene content of more than 84 mol% were miscible with iPP, in which the crystallizable PP sequences in these EP copolymers were incorporated in crystal lattice of iPP and the other portions in the EP chains were excluded to the amorphous phases. Consequently, they act as tie molecules linking between adjacent lamellae, leading to enhancement of yield toughness of iPP. On the other hand, the EP copolymers with a propylene-unit content of less than 77 mol% were incompatible with iPP. The iPP/EP blends showed the phase-separated morphology.     

Linear low-density polyethylene addition to polypropylene/elastomer blends: Phase structure and impact properties

Morphology features and effects of particle size and composition of the disperse phase on the impact properties have been studied for the blends of isotactic polypropylene (PP)/ethylene-propylene-diene terpolymer and (EPDM)/linear low-density polyethylene (LLDPE). The blend components were mixed in a twin-screw extruder, press molded, and analyzed by scanning electron microscopy, SEM (fractured and toluene etched samples), and by transmission electron microscopy, TEM (RuO₄ stained samples). TEM was most effective for the identification of component distribution and particle size measurement. An increasing degree of LLDPE and EPDM interpenetration was observed with the PE content. Not one case of a neat component separation was detected. LLDPE addition improves the EPDM dispersability, affecting mainly the larger particles. The impact properties at room temperature were especially dependent on the rubber content, whereas at low temperature the particle diameter appears to be the controlling parameter. The affect of LLDPE on blend toughness is more evident in the latter case.     

Melting,nonisothermal crystallization behavior and morphology of polypropylene/random ethylene—propylene copolymer blends

The melting, nonisothermal crystallization behavior and morphology of blends of polypropylene (PP) with random ethylene–propylene copolymer (PP‐R) were studied by differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and X‐ray diffraction. The results showed that PP and PP‐R were very miscible and cocrystallizable. Modified Avrami analysis was 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 heterogeneous, the growth of the spherulites was tridimensional, and the crystallization mechanism of PP was not affected by PP‐R. The crystallization activation energy was estimated using the Kissinger method. An interesting result was obtained with the modified Avrami analysis and the Kissinger method, whose conclusions were in good agreement. The addition of a minor PP‐R phase favored an increase in the overall crystallization rate of PP. Maximum enhancing effect wass found to occur with a PP‐R content of 20 wt %. The relationship between the composition and the morphology of the blends is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 670–678, 2006     

Effect of addition of polyethylene on properties of polypropylene/ethylene–propylene rubber blends

Toughening of polypropylene was carried out by adding two types of ethylene-propylene rubber (EPR) having different ethylene content, and three commercial types of EPR containing high density polyethylene (PE). The concentration of EPR was varied from 0–30%. Globular morphology of the dispersed phase was observed at all concentrations. Average particle size of the dispersed phase (EPR) was about 2–4 μm with about 10% within the 0.5–1 μm range. Although most of the properties were not affected by the presence of polyethylene, high notched Izod impact strength was achieved only with samples containing PE. Melt flow rate, yield strength and modulus were found to decrease almost linearly with increasing elastomer concentration in the blend. Elongation at break was enhanced by the addition of EPR, particularly those containing PE. The contribution of PE to the properties was explained by the specific EPR/PE particle morphology (core-shell or interpenetrating) but the exact mechanism of toughening of PP with EPR in the presence of PE is not clear. © 1996 John Wiley & Sons, Inc.     

Tensile properties in the oriented blends of high-density polyethylene and isotactic polypropylene obtained by dynamic packing injection molding

In this article, tensile properties have been discussed in terms of phase morphology, crystallinity and molecular orientation in the HDPE/iPP blends, prepared via dynamic packing injection molding, with aid of scanning electron microscopy (SEM), differential scanning calorimetry (DSC) as well as two dimensional X-ray scattering (2D WAXS). For the un-oriented blends, the tensile properties (tensile strength and modulus) are mainly dominated by the phase morphology and interfacial adhesion related to the influenced crystallization between HDPE and iPP component. A maximum in tensile strength and modulus is found at iPP content in the range of 70-80 v/v%. As for the oriented blends, however, the presence of dispersed phase in the blends, independent of phase morphology and crystallinity, always makes tensile properties to be deteriorated through reducing molecular orientation of matrix. It is molecular orientation of matrix that determines the tensile properties of oriented blends. In the blends with HDPE as matrix, steep decreasing of tensile properties is related to the rapid reducing of molecular orientation of HDPE, whereas in the blends with iPP as a major component, slight decreasing of molecular orientation of iPP results in slight reducing of tensile properties. Other factors, such as interfacial properties and phase morphology, seem to be little contribution to the modulus and tensile strength.     

Rheological and mechanical properties of ternary blends of linear-low-density polyethylene/polypropylene/ethylene-propylene block polymers

The effect of addition of an ethylene-propylene block polymer on rheological and mechanical properties of a linear-low-density polyethylene/polypropylene blend was examined. The samples were prepared by melt blending in a twin-screw extruder followed by injection molding. The single-, two- and three-component systems were treated the same way. The mechanical behavior of the blends was evaluated by means of tensile, and flexural, tests at 23 and ?40°C. The capillary, elongational, and dynamic-flow measurements were performed at 190°C.     

Epitaxy growth and directed crystallization of high-density polyethylene in the oriented blends with isotactic polypropylene

Various lamellar orientations of high-density polyethylene (HDPE), due to competition between bulk nucleation and interfacial nucleation, have been realized in its melt drawn blends with isotactic polypropylene (iPP) upon cooling after subjected to 160 °C for 30 min. Directed crystallization, with heterogeneous nucleation in the bulk (within domains), is defined as lamellar growth along boundary of anisotropic domains and is favored in larger domains at higher temperature (slow cooling), since overgrowth of lamellae can feel the interface rather than impingement with neighbor ones as a result of scare nuclei at higher temperature. Moreover, lamellar growth caused by directed crystallization is dependent of dimension of confinement. Due to 2D confinement of cylindrical domains, lamellae can only grow along the axis of cylinder and thus b-axis orientation is formed. While in the layered domains with 1D confinement, however, lamellae grow with the normal of (110) plane along the melt drawn direction. On the other hand, epitaxial growth of HDPE chains onto iPP lamellae is related to the surface-induced crystallization and dominated by the interfacial nucleation. Only interfacial nucleation is preferred can epitaxial growth occur. Therefore, retarded crystallization, realized by either strong confinement in finer domains or rapid cooling or both, is favorable for it.     

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.     

Shear‐induced fibrillation and resultant mechanical properties of injection‐molded polyamide 1010/isotactic polypropylene blends

It is feasible to control the phase morphology and orientation for immiscible polymer blends to manipulate their properties. In this paper, the blend of polyamide 1010 (PA1010) and isotactic polypropylene (iPP) (mainly at a fixed ratio of PA1010/iPP = 80/20) was used as an example to demonstrate the effect of shear on the morphology and resultant mechanical properties. After being melt blended, the injection‐molded bars were prepared via a dynamic packing equipment to impose a prolonged shearing on the melts during the solidification stage. By controlling the shear time, the structure evolution and morphological development of the blends can be well controlled. Mechanical measurement of the molded bar showed a dramatically improved tensile property and impact strength with increasing shear time. Morphological examination revealed that the iPP droplets are elongated and become thin fibrils along the shear direction with increasing shear time. The shear‐induced fibrillation, instead of orientation, is believed to be responsible for the largely improved properties of the blend, particularly for the impact strength. The toughening mechanism is discussed based on the combined effect of hindrance of crack propagation and the transferring and bearing of the load due to the existence of the fibrils. This was further proved by changing the blending ratio and using low molecular weight iPP. Finally, we propose a concept for designing blending materials with good comprehensive properties. Copyright © 2011 Society of Chemical Industry     

Rheological properties of linear low density polyethylene/polypropylene blends. Part 2: Solid state behavior

This second paper of a series continues the examination of the tensile properties of two series of linear low density polyethylene/polypropylene, (LLDPE/PP) blends. The blends were prepared using a twin-screw extruder and cover the whole concentration range, An Instron Universal Tensile Tester was used to measure the tensile properties of the blends between 10 and 70°C, and the temperature and composition dependences of the modulus were examined. A comparison is established between the solid state and melt properties to underline the behavior in the PP rich region. Results of dynamic mechanical experiments and differential scanning calorimetry on the same materials are also given, and the mechanical behavior is discussed in terms of the variation of the system's crystallinity.     

Mechanical properties of injection‐molded isotactic polypropylene/roselle fiber composites

Natural fiber‐thermoplastic composite materials, based on their cost‐effectiveness and environmental friendliness, have attracted much interest both scientifically and technologically in recent years. Other advantages of natural fibers are good specific strength, less abrasion, and less irritation upon inhalation (in comparison with some common inorganic fillers). In the present contribution, roselle (Hibiscus sabdariffa L.) fibers were chosen and used as reinforcing fillers for isotactic polypropylene (iPP) for the first time, due mainly to the cost‐effectiveness and natural abundance on Thai soil. Processibility and mechanical properties of the resulting composites were investigated against the type and the mean size of the fibers. The results showed that the highest mechanical properties were observed when roselle bast fibers were incorporated. When whole‐stalk (WS) fibers (i.e., the weight ratio of bast and core fibers was 40 : 60 w/w) were used, moderate mechanical properties of the resulting composites were realized. The optimal contents of the WS fibers and the maleic anhydride‐grafted iPP compatibilizer that resulted in an improvement in some of the mechanical properties of the resulting composites were 40 and 7 wt %, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3291–3300, 2006     

Influence of comonomer incorporation on morphology and thermal and mechanical properties of blends based upon isotactic metallocene–polypropene and random ethene/1‐butene copolymers

Blends of isotactic polypropene (i‐PP) with random ethene/1‐butene (EB) copolymers containing 10, 24, 48, 58, 62, 82, and 90 wt % 1‐butene were prepared in order to examine the influence of the EB molecular architecture on the morphology development as well as on the thermal and mechanical properties. Compatibility between i‐PP and EB increased with increasing 1‐butene content in EB to afford single‐phase blends at a 1‐butene content exceeding 82 wt %. The morphology was investigated using AFM and TEM. Improved compatibility accounted for enhanced EB dispersion and interfacial adhesion. Highly flexible as well as stiff blends with improved toughness were obtained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 838–848, 1999     

Synergism on tensile properties of injection molded polybutene-1 /polypropylene blends

Blends of polybutene- 1 (PB-1) and polypropylene (PP) have been injection and compression molded. A synergism appears in the ultimate elongation and the tensile strength for the injection moldings. The maximum point of the synergism at the composition of 25 wt% PB-1 shifts to 50 wt% PB-1 after annealing at 145° C for 1 h. A linear relation and negative deviation from the additivity rule for these two properties are observed for the compression moldings with quick cooling and slow cooling, respectively. Thermal analysis, polarized optical microscopy, and scanning electron microscopy (SEM) are used to study the occurrence of the synergism. The mutual interference between the two components on the crystal formation and the plasticization effect of PB- 1 on PP result in the synergism. An increased phase separation probably occurs during the compression molding with slow cooling. So, the blends compression-molded with slow cooling having a higher amount of PP have brittle breaks, similar to pure PP.     

Effect of melt flow on morphology and linear thermal expansion of injection‐molded ethylene–propylene–diene terpolymer/isotactic polypropylene blends

An ethylene–propylene–diene terpolymer/isotactic polypropylene blend with a structure of co‐continuous microlayers was fabricated by injection molding and was then investigated. The blend exhibited an extremely low coefficient of linear thermal expansion (CLTE) in the directions of the length and the width. As the thickness of the oriented portion increased, the CLTE was further reduced. The morphology of the co‐continuous microlayers and the thermal expansion behavior varied with the sampling positions on the injection‐molded sheets. To study the relationship between the morphology and the melt flow, the melt flow behavior during injection molding was simulated using Moldflow. Orientation of the microlayers was determined using shear flow. When the shear rate increased, the orientation state increased and the CLTE decreased. © 2015 Society of Chemical Industry     

Extrusion of polyethylene/polypropylene blends with microfibrillar‐phase morphology

Extrusion of immiscible polymers under special conditions can lead to creation of microfibrillar‐phase morphology, ensuring significant increase of mechanical properties of polymer profiles. Polyethylene/polypropylene blend extrudates with microfibrillar‐phase morphology (polypropylene microfibrils reinforcing polyethylene matrix phase) were prepared through continuous extrusion with semihyperbolic‐converging die enabling elongation and orientation of microfibrils in flow direction. Structure of extruded profiles was examined using electron microscopy and wide‐angle X‐ray scattering. Tensile tests proved that extrudates with microfibrillar‐phase morphology show significantly higher mechanical properties than the conventional extrudates. The presented concept offers possibility of replacing the existing expensive multi‐component medical devices with fully polymeric tools. POLYM. COMPOS., 31:1427–1433, 2010. © 2009 Society of Plastics Engineers     

Effect of the elastomer viscosity on the morphology and impact behavior of injection molded foams based on blends of polypropylene and polyolefin elastomers

The impact resistance of injection-molded polypropylene (PP) parts is severely reduced when they are foamed. It is necessary to implement strategies, such as elastomer toughening, to increase the impact behavior of foamed parts. However, the knowledge on the effect of elastomer addition on the morphology, cellular structure, and impact of injection-molded cellular parts is very limited. In this work, foamed parts based on blends of PP and polyolefin elastomers have been produced and characterized. A high and a low viscosity octene-ethylene copolymer (EOC) and a high viscosity butene-ethylene copolymer (EBC) were employed. The blends have been thermally and rheological characterized. Solids materials and foams (relative density 0.76) were injection-molded. The solid phase and cellular structure morphologies were studied using scanning electron microscopy. The results showed that elastomer toughening has been successful to obtain an improvement of the impact behavior in solid and cellular polymers. In this case, EOC materials provide an appropriate interfacial adhesion and optimized cellular structure which results in high impact resistance. The optimum elastomer to improve the properties is the EOC with a higher viscosity which provides impact resistance with n values below 3 due to the toughening of polymer matrix, thick skin thickness, and low cell size.     

Unusual crystallization behavior of isotactic polypropylene and propene/1-alkene copolymers at large undercoolings

During the investigation of the crystallization of metallocene isotactic polypropylene and copolymers with low amount of 1-butene and 1-hexene at large undercoolings, an unexpected behavior has been found. Random copolymers crystallize faster than the homopolymer between 80 and 40 °C, while at high temperatures the overall crystallization rates follow the expected trend. On the basis of structural and morphological evidences we suggest that the overall structuring kinetics of the homopolymer is slowed down by the concomitant formation of mesophase and monoclinic structures. This effect is absent in the copolymers because the branched counits retard the development of mesophase.