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.     

Morphology,crystallization and melting behaviour of films of isotactic polypropylene blended with ethylene-propylene copolymers and polyisobutylene

The crystallization, the morphology and the thermal behaviour of thin films of isotactic polypropylene (iPP) blended with elastomers such as random ethylene-propylene copolymers (EPM) with different ethylene content and polyisobutylene (PiB) were investigated by means of optical microscopy, differential scanning calorimetry and wide angle X-ray diffractometry. During crystallization EPM copolymers are ejected on the surface of the film forming droplet-like domains. A different morphology is observed in iPP/PiB blends. For these mixtures the elastomers separate from the iPP phase forming spherical domains that are incorporated in the iPP intraspherulitic regions. Both EPM and PiB elastomers act as nucleant agents for iPP spherulites. This nucleation efficiency is strongly dependent on the chemical structure and molecular mass of the elastomers. The addition of EPM causes an elevation of the observed and equilibrium melting temperature of iPP. This unusual effect may be accounted for by assuming that the elastomers are able to extract selectively the more defective molecules of iPP. The depression of the growth rate of spherulites and the observed and equilibrium melting temperature of iPP, noted in iPP/PiB blends, suggests that these two polymers have a certain degree of compatibility in the melt.     

Structure and Properties of PPO/PP Blends Compatibilized by Triblock Copolymer SEBS and SEPS

Morphology, mechanical behavior and other properties of isotactic polypropylene (iPP) and poly(phenylene oxide) (PPO) blends were studied. Large PPO particle sizes or delamination were found in binary iPP/PPO blends when no compatibilizers were added, while fracture toughness of the binary alloy was higher than that of both pure iPP and PPO. The addition of compatibilizers, triblock copolymers SEBS and SEPS, tremendously improved PPO particle dispersion and particle-matrix interfacial adhesion in iPP. The results of mechanical properties of the ternary iPP/PPO/compatibilizer blends showed that the compatiblization of SEPS is better than that of SEBS.     

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.     

Primary nucleation behaviour in isotactic polypropylene/ethylene-propylene random copolymer blends

Primary nucleation of spherulites in blends of isotactic polypropylene (iPP) with ethylene-propylene random copolymer (EPM) has been investigated using optical microscopy. The number of spherulites generally increases with increasing EPM content. It is shown that this increase is caused by migration of heterogeneous nuclei across interface boundaries from EPM to iPP during melt-mixing. The migration was observed in the blends with the nucleating agent initially added to EPM before blending with iPP. It is suggested that the interfacial free energy difference between nuclei and the molten components of the blend is responsible for the migration of nuclei. It is also shown that self-seeded nucleation becomes damped in the blends due to partial solubility of the components and that the degradation of the blends during melt-annealing depresses the primary nucleation.     

Effect of the molecular structure of ethene–propene and styrene–butadiene copolymers on their compatibilization efficiency in low‐density polyethylene/polystyrene blends

The effect of the molecular structure of styrene–butadiene (SB) block copolymers and ethene–propene (EPM) random copolymers on the morphology and tensile impact strength of low‐density polyethylene (LDPE)/polystyrene (PS) (75/25) blends has been studied. The molecular characteristics of SB block copolymers markedly influence their distribution in LDPE/PS blends. In all cases, an SB copolymer is present not only at the interface but also in the bulk phases; this depends on its molecular structure. In blends compatibilized with diblock copolymers, compartmentalized PS particles can also be observed. The highest toughness values have been achieved for blends compatibilized with triblock SB copolymers. A study of the compatibilization efficiency of SB copolymers with the same number of blocks has shown that copolymers with shorter PS blocks are more efficient. A comparison of the obtained results with previous results indicates that the compatibilization efficiency of a copolymer strongly depends both on the blend composition and on the properties of the components. The compatibilization efficiency of an EPM/SB mixture is markedly affected by the rheological properties of the copolymers. The addition of an EPM/SB mixture containing EPM with a higher viscosity leads to a higher improvement or at least the same improvement in the tensile impact strength of a compatibilized blend as the same amount of neat SB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Origin of various lamellar orientations in high-density polyethylene/isotactic polypropylene blends achieved via dynamic packing injection molding: bulk crystallization vs. epitaxy

Epitaxial growth of high-density polyethylene (HDPE) onto lamellae of isotactic polypropylene (iPP), with HDPE chains inclined about 50° to that of iPP, has been achieved for the first time in their blends via dynamic packing injection molding. Even more, the epitaxial growth was found to be dependent on composition of the blends. The sequence of crystallization is not the dominant factor, but the fact that iPP crystallizes before HDPE is prerequisite for epitaxial growth of PE. Various lamellar orientations with composition can be explained by the competition between bulk crystallization and epitaxy at interfaces (i.e. iPP lamellae). In 20PP (20 wt% iPP by weight in blends), HDPE can readily crystallize in the bulk as a result of shear, and no epitaxial growth of PE is observed. For 80PP, however, bulk crystallization of HDPE can be depressed due to lack of nuclei in its bulk, resulting from a much finer droplets dispersed in the iPP matrix, and then epitaxial growth prevails.     

Effect of the components' molar mass and of the mixing conditions on the compatibilization of PE–LCP blends by PE‐g‐LCP copolymers

The rheology, morphology, and mechanical properties of blends of high‐density polyethylene (HDPE) with a semiflexible liquid crystalline copolyester (SBH) were studied in order to assess the compatibilizing ability of added PE‐g‐SBH copolymers, and its dependence on the molar mass of the PE matrix, and on the technique used for blend preparation. The PE‐g‐SBH copolymers were synthesized as described in previous articles, either by the polycondensation of the SBH monomers in the presence of a functionalized PE sample containing free carboxyl groups, or by reactive blending of the latter polymer with preformed SBH. Two samples of HDPE having different molar masses, and two samples of SBH with different melt viscosity and different microstructure, were used for preparing the blends. The two components and the compatibilizer were either blended in a single batch or used to prepare binary master blends to which the third component was added at a later stage. The results indicate that the PE‐g‐SBH copolymers do, in fact, compatibilize the PE–SBH blends and that the effect is more pronounced with the lower molar mass PE matrix and with the SBH sample having lower viscosity. The experiments carried out on blends prepared with different techniques show that the compatibilizing ability of the graft copolymer is improved if the latter is first blended with either of the two main components. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 603–613, 1999     

Processing and characterization of microcellular foamed high-density polythylene/isotactic polypropylene blends

In this paper, a study on the batch processing and characterization of microcellular foamed high-density polyethylene (HDPE/iPP) blends is reported. A microcellular plastic is a foamed polymer with a cell density greater than 10⁹ cells/cm³ and fully grown cells smaller than 10 µm. Recent studies have shown that the morphology and crystallinity of semicrystalline polymers have a great influence on the solubility and diffusivity of the blowing agent and on the cellular structure of the resulting foam in microcellular batch processing. In this research, blends of HDPE and iPP were used to produce materials with variety of crystalline and phase morphologies to enhance the subsequent microcellular foaming. It was possible to produce much finer and more uniform foams with the blends than with neat HDPE and iPP. Moreover, the mechanical properties and in particular the impact strength of the blends were significantly improved by foaming.     

The influence of HOCP oligomer on the crystallization and morphology of iPP/HDPE blends

Summary Ternary mixtures of isotactic polypropylene (iPP), high density polyethylene (HDPE) and hydrogenated oligo(cyclopentadiene) (HOCP) commercial products were prepared by melt mixing. The crystallization behaviour of iPP/HDPE and (iPP/HDPE)/HOCP systems were compared. It was shown that the ternary system separated in two binary systems. The presence of HOCP modified the morphology of iPP and HDPE phases. The polyolefins nucleation and crystal growth rates decreased due to the diluent effect of the oligomer. HDPE showed higher compatibility with HOCP than iPP.     

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.     

高密度聚乙烯／尼龙1010共混体系的研究

采用接枝共聚方法,合成了高密度聚乙烯与马来酸酐,甲基丙烯酸和丙烯酸丁酯的接枝共聚物增容剂,研究了增容剂中接枝单体的种类及含量和增容剂用量等因素对高密度聚乙烯／尼龙1010共混体系力学性能的影响,结果表明在不同类型的接枝共聚物中以聚乙烯马来酸酐接枝共聚物对HDPE／PA1010共混体系的增容效果最好,在接枝单体含量和增容剂用量分别为4％－6％和5％左右时,共混体系的力学性能最好。     

Blends of high density polyethylene and ethylene/1‐octene copolymers: Structure and properties

The morphology formation in the blends comprising a high density polyethylene (HDPE) and selected ethylene/1‐octene copolymers (EOCs) was studied with variation of blend compositions using atomic force microscopy (AFM). The binary HDPE/EOC blends studied showed well phase‐separated structures (macrophase separation) in consistence with individual melting and crystallization behavior of the blend components. For the blends comprising low 1‐octene content copolymers, the lamellar stacks of one of the phases were found to exist side by side with that of the another phase giving rise to leaflet vein‐like appearance. The formation of large HDPE lamellae particularly longer than in the pure state has been explained by considering the different melting points of the blend components. The study of strain induced structural changes in an HDPE/EOC blend revealed that at large strains, the extensive stretching of the soft EOC phase is accompanied by buckling of HDPE lamellar stack along the strain axis and subsequent microfibrils formation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1887–1893, 2007     

Isotactic polypropylene/polymethylmethacrylate blends: Effects of addition of propylene-graft-methylmethacrylate copolymer

A novel graft copolymer of unsaturated propylene with methyl methacrylate (uPP-g-PMMA) was added to binary blends of isotactic polypropylene (iPP) and atactic poly(methyl methacrylate) (aPMMA) with a view to using such a copolymer as a compatibilizer for iPP/aPMMA materials. Optical microscopy (OM), scanning electron microscopy, wide angle X-ray scattering (WAXS), and small angle X-ray scattering (SAXS) techniques showed that, contrary to expectation, the uPP-g-PMMA addition does not provide iPP/aPMMA compatibilized materials, irrespective of composition. As a matter of fact the degree of dispersion of the minor component achieved following the addition of uPP-g-PMMA copolymer remained quite comparable to that exhibited by binary blends of iPP and aPMMA with no relevant evidence of adhesion or interconnection between the phases. On the other hand the crystalline texture was deeply modified by the copolymer presence. With increasing uPP-g-PMMA content (w/w) the iPP spherulites were found to become more open and coarse and the dimensions and number per unit area of the amorphous interspherulitic contact regions were found to increase. According to such OM results the copolymer uncrystallizable sequences were assumed to be mainly located in interfibrillar and interspherulitic amorphous contact regions. SAXS analysis demonstrated that the phase structure developed in the iPP/aPMMA/uPP-g-PMMA blends is characterized by values of the long period increasing linearly with increasing copolymer content (w/w). Assuming a two phase model for the iPP spherulite fibrillae, constituted of alternating parallel crystalline lamellae and amorphous layers, the lamellar structure of the iPP phase in the ternary blends is characterized by crystalline lamellar thickness (L_c) and an interlamellar amorphous layer (L_a) higher than that shown by plain iPP and L_c and L_a values both increased with increasing uPP-g-PMMA content (w/w). Such SAXS results have been accounted for by assuming that a cocrystallization phenomenon between propylenic sequences of the uPP-g-PMMA copolymer and iPP occurs. The development of the iPP lamellar structure in the iPP/aPMMA/uPP-g-PMMA blends was thus modeled hypothesizing that during such a cocrystallization process copolymer PMMA chains with comparatively lower molecular mass remain entrapped into the iPP interlamellar amorphous layer forming their own domains. Moreover, evidence of strong correlations between the crystallization process of the uPP-g-PMMA copolymer and the iPP crystallization process was shown also by differential scanning calorimetry and WAXS experiments. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2377–2393, 1997     

Isotactic polypropylene/polystyrene blends: Effects of the addition of a graft copolymer of propylene with styrene

A novel graft copolymer of unsaturated propylene with styrene (uPP-g-PS) was added to binary blends of isotactic polypropylene (iPP) and atactic polystyrene (aPS) with a view to using such a copolymer as compatibilizer for iPP/aPS materials. Differential scanning calorimetry, optical microscopy, scanning electron microscopy (SEM), wide angle X-ray scattering, and small angle X-ray scattering (SAXS) techniques have been carried out to investigate the phase morphology and structure developed in solution-cast samples of iPP/aPS/uPP-g-PS ternary blends. It was found that the uPP-g-PS addition can provide iPP/aPS-compatibilized materials and that the extent of the achieved compatibilization is composition-dependent. Blends of iPP and aPS exhibited a coarse domain morphology that is characteristic of immiscible polymer systems. By adding 2% (wt/wt) of uPP-g-PS copolymer a very broad particle-size distribution was obtained, even though the particles appeared coated by a smooth interfacial layer, as expected according to a core–shell interfacial model. With increasing uPP-g-PS content (5% wt/wt), a finer dispersion degree of particles, together with morphological evidence of interfacial adhesion, was found. With further increase of uPP-g-PS amount (10% wt/wt) the material showed such a homogeneous texture that neither domains of dispersed phase nor holes could be clearly detected by SEM. The type of interface developed in such iPP/aPS/uPP-g-PS blends was accounted for by an interfacial interpenetration model. The iPP crystalline texture, size, neatness, and regularity of iPP spherulites crystallized from iPP/aPS/uPP-g-PS blends were found to decrease when the copolymer content was slightly increased. Assuming, for the iPP spherulite fibrillae, a two-phase model constituted by alternating parallel crystalline lamellae and amorphous layers, it was shown by SAXS that the phase structure generated in iPP/aPS/uPP-g-PS blends is characterized by crystalline lamellar thickness (L_c) and interlamellar amorphous layer thickness (L_a) higher than that shown by plain iPP; the higher the copolymer content, the higher the L_c and L_a. It should be remarked that considerably larger increases have been found in L_a values. Such SAXS results have been accounted for by assuming that a cocrystallization phenomenon between propylenic sequences of the uPP-g-PS copolymer and iPP occurs and that during such a process PS chains grafted into copolymer sequences remain entrapped in iPP interlamellar amorphous layers, where they form their own separate domains. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1539–1553, 1997     

Effects of the viscosity ratio on polyolefin ternary blends

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

Ternary nylon-6/rubber/modified rubber blends: Effect of the mixing procedure on morphology, mechanical and impact properties

Ternary polyamide-based blends have been prepared by adding to nylon-6 (PA6) an ethylene-propylene random copolymer (EPM) and the same EPM functionalized by inserting onto its backbone maleic anhydride groups (EPM-g-SA). Two kinds of processing have been used: (a) one-step mixing in which the three components were simultaneously introduced in the mixer; (b) two-step mixing in which the two rubbers EPM and EPM-g-SA were separately premixed before the final mixing with PA6. Also binary PA6/EPM-g-SA blends have been prepared to compare their properties with those of the ternary one.

Mechanical tensile characterization at room temperature and impact Izod tests at different temperatures as well as a morphological analysis of smoothed samples have been performed on all the blends. It has been shown by a model reaction that both in binary and ternary blends an EPM-g-PA6 graft copolymer is formed, which acts as an interfacial agent between the rubbery dispersed phase and the polyamide matrix. The blends obtained by the one-step mixing showed a gross morphology and a very poor impact resistance, whereas the ones prepared by the two-step mixing exhibited very fine morphologies and excellent impact performances. In addition, as shown at least in the case of one ternary blend, there seems to be good morphological stability of these materials after a second processing. This has been attributed to the influence of the interfacial agent formed during the melt mixing of the two premixed rubbers with PA6.     

Thermal properties and crystallization behavior of polyolefin ternary blends

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

The supermolecular structure of isotactic polypropylene/atactic polystyrene blends

The supermolecular structure of binary isotactic polypropylene/atactic polystyrene (iPP/PS) injection‐molded blends were studied by wide‐angle X‐ray diffraction, differential scanning calorimetry, and optical microscopy. The combination of different methods gives a possibility of analysis of relation between the phase transformation in polypropylene and crystallization parameters. Effect of compatibilization of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) grafted with maleic anhydride (SEBS‐g‐MA) block copolymers in the iPP/PS blends on the structure, nucleation, crystal growth, solidification, and the phase morphology was analyzed. We found that the β‐crystallization tendency of polypropylene matrix can be enhanced by adding atactic polystyrene. However, the incorporation of SEBS‐g‐MA into iPP/PS blends resulted in an important decrease in β‐content of iPP. It is evident that the presence of compatibilizing agent caused a very significant reduction of the α‐spherulite growth rates and the crystal conversion as well as increases of half‐time crystallization in comparison with the iPP/PS systems. The relation between kinetic parameters of crystallization process and polymorphic structure of iPP in blend systems has been satisfactorily explained. Moreover, a strong effect of processing parameters on the β‐phase formation was observed. The results clearly show that at a higher temperature of mold and lower injection speed, the amount of β‐phase of iPP matrix slightly decreases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Morphology—properties relationships in binary polyamide 6/rubber blends: Influence of the addition of a functionalized rubber

The modification of an amorphous random ethylene-propylene rubbery copolymer (EPM) has been accomplished by solution grafting of maleic anhydride molecules promoted by radical initiators, The resulting EPM-g-succinic anhydride (EPM-g-SA) and EPM have been used to obtain binary polyamide 6/EPM or polyamide 6/EPM-g-SA and ternary polyamide 6/EPM/EPM-g-SA blends by melt mixing. The formation of an EPM-g-PA6 graft copolymer during the blend preparation has been assumed. Different blend morphologies were observed by scanning electron microscopy (SEM) according to the nature and content of the rubber used. The tensile mechanical properties and the impact behavior of the prepared blends were investigated and correlated with the SEM analysis of the fracture surfaces. Binary and ternary blends containing 20 percent by weight of total rubber show a significant improvement of the impact properties at low temperature (?20°C) when the rubber is partly or entirely EPM-g-SA. In the case of PA6/EPM-g-SA (80/20) blend these results are related to the presence of rubbery domains of very small size strongly adherent to the PA6 matrix. In the case of 80/10/10 ternary blends, a much more complicated overall morphology is observed. Such morphology is characterized by the presence of large EPM domains, likely containing some EPM-g-PA6 graft molecules acting as an interfacial agent, and domains of EPM-g-PA6 of smaller size strongly adherent to the matrix as in the previous case.