Development of nanofibrous morphology in LDPE/LLDPE/PP blends and its effect on mechanical properties of blend films

Nanofibrous morphology has been observed in ternary blends of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and isotactic polypropylene (PP) when these were melt‐extruded via slit die followed by hot stretching. The morphology was dependent on the concentration of the component polymers in ternary blend LDPE/LLDPE/PP. The films were characterized by wide angle X‐ray diffraction (XRD), scanning electron microscopy (SEM), and testing of mechanical properties. The XRD patterns reveal that the β phase of PP is obtained in the as‐stretched nanofibrillar composites, whose concentration decreases with the increase of LLDPE concentration. The presence of PP nanofibrils shows significant nucleation ability for crystallization of LDPE/LLDPE blend. The SEM observations of etched samples show an isotropic blend of LDPE and LLDPE reinforced with more or less randomly distributed and well‐defined nanofibrils of PP, which were generated in situ. The tensile modulus and strength of LDPE/LLDPE/PP blends were significantly enhanced in the machine direction than in the transverse direction with increasing LLDPE concentration. The ultimate elongation increased with increasing LLDPE concentration, and there was a critical LLDPE concentration above which it increased considerably. There was a dramatic increase in the falling dart impact strength for films obtained by blow extrusion of these blends. These impressive mechanical properties of extruded samples can be explained on the basis of the formation of PP nanofibrils with high aspect ratio (at least 10), which imparted reinforcement to the LDPE/LLDPE blend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of blends of linear low density polyethylene and poly(ethene‐propene‐1‐butene)

Blends of linear low density polyethylene (LLDPE) and ethene‐propene‐1‐butene copolymer (t‐PP) were obtained through mechanical mixing using a single‐screw extruder with different compositions: 20, 40, 50, 60, and 80 wt % of t‐PP. For this, two types of polyethylene were used: 1‐hexene comonomer and 1‐octene comonomer based. The same blends were prepared in a batch mixer and the torque and temperature were analyzed. The torque showed a decrease with increasing t‐PP content, indicating better processability of the mixture in comparison with LLDPE. The morphology of the blends was analyzed by SEM and showed a composition dependence. The mechanical properties of the blends were evaluated by tensile tests. The results revealed that the best properties were obtained in a 20% t‐PP blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1255–1261, 2006     

Isothermal crystallization and spherulite nucleation in blends of polypropylene with metallocene‐prepared polyethylene

The isothermal crystallization behavior and morphology of a polypropylene (PP)‐based copolymer, a metallocene‐prepared linear low‐density polyethylene (M‐LLDPE) and their three 10/90, 30/70 and 50/50 M‐LLDPE/PP blends have been investigated. The PP and M‐LLDPE contained 5 ethylene and 3.3 mol% hexene‐1 as a comonomer, respectively. Isothermal crystallization studies revealed a different temperature‐dependence on crystallization for M‐LLDPE, PP and their blends and the crystallization half‐life for the M‐LLDPE was higher than either PP or the blends at a certain temperature. The PP‐rich blends also showed a quite similar crystallization rate to that of PP. Investigations on the variation of spherulite growth rate of PP in the blends at different temperatures revealed no significant change and was quite independent of the amount of M‐LLDPE being employed. The morphology studies revealed that the nucleation densities of the PP spherulites decreased by introducing M‐LLDPE into PP and the M‐LLDPE remained as discrete droplets dispersed throughout the PP spherulites. The results obtained were consistent with no miscibility between the two components. Copyright © 2005 Society of Chemical Industry     

Microhardness of ternary blends of polyolefins with recycled polymer components

Microhardness tests, Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) measurements were performed on melt‐pressed films of multicomponent blends based on low‐density polyethylene (LDPE), linear LDPE (LLDPE), high‐density polyethylene (HDPE), and polypropylene (PP), and their recycled homologues. Some of the PE blends also contained ethylene‐propylene‐diene monomer (EPDM) as compatibilizer. In all cases, the variation of microhardness as a function of content of the recycled component follows the additivity law of components. Thus, the range of hardness values of polyolefin blends can be controlled by choice of both components and their relative content in the blend. The hardness of the components increases from LDPE, to LLDPE, to HDPE, to PP and increases from 20 to 84 MPa. For recycled components, the hardness values are reduced by ～15%. According to DSC results, all the blends are immiscible. Results are discussed in terms of the levels of crystallinity reached for the different blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2046–2050, 2003     

Effect of cross‐linked LLDPE/PP blend (LLDPE‐PP) as compatibilizer on morphology,crystallization behavior and mechanical property of LLDPE/PP blends

Moderate cross‐linked blend (LLDPE‐PP) of linear low‐density polyethylene (LLDPE) and polypropylene (PP) with benzoyl peroxide (BPO) were prepared by the reactive melt mixing in HAAKE mixer. Effect of LLDPE‐PP as compatibilizer on the morphology, crystallization behavior and mechanical properties of LLDPE/PP (87/13) blends were studied using scanning electron microscopy (SEM), polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and mechanical testing machines. The results showed that LLDPE‐PP not only improved the interfacial adhesion between the LLDPE and PP but also acted as selective nucleating agent for crystal modification of PP. In the blends, the sizes of LLDPE and PP spherulites became smaller, and their melting enthalpies reduced in the presence of LLDPE‐PP. Furthermore, the mechanical properties of LLDPE/PP blends were improved with the addition of LLDPE‐PP, and when the concentration of LLDPE‐PP was 2 phr, the ternary blend had the best mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical Properties and Morphology of Ternary PP/EPDM/PE Blends

The ternary blends of high‐density polyethylene (PE), EPDM terpolymer and polypropylene (PP) have been used as a model low interfacial tension system to study encapsulation dynamics in ternary blends and their relation to the blends' mechanical properties. It was found that the modulus, tensile strength and impact resistance can be improved by PE addition if the PE is localized within the EPDM phase. A range of blend morphology was found depending on the PE viscosity and polymer incorporation sequence in the twin‐screw extruder. In the most favorable sequence, PE and EPDM were mixed together prior to their dispersion in the PP matrix. This practice resulted in a 50% increase in impact resistance when compared to mixing the three components in a single‐step.     

Effect of molecular structure in branched polyethylene on adhesion properties with polypropylene

Adhesion properties between branched polyethylene (PE) and isotactic polypropylene (PP) were studied by a peel test and scanning electron microscopy. In this study, two types of branched PEs were used; one is a linear low density polyethylene (LLDPE) and the other is a high pressure low density polyethylene (LDPE). The adhesive strength of the LLDPE/PP is much higher than that of LDPE/PP. Furthermore, the formation of PE influxes between PP spherulites has a small effect on the adhesion. The dynamic viscoelastic measurements for the binary blends composed of branched PE and PP were also carried out to estimate the interfacial tension by using a rheological emulsion model proposed by Palierne. The interfacial tension is 1.0 mN for LLDPE/PP and 2.1 mN for LDPE/PP, suggesting that the interfacial thickness of LLDPE/PP is about twice that of LDPE/PP. The adhesive strength between branched PE and PP will be determined by the interfacial thickness, which represents the entanglements between two polymers. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 457–463, 1998     

Properties of uncompatibilized and compatibilized poly(butylene terephthalate)–LLDPE blends

In this work, blends of poly(butylene terephthalate) (PBT) and linear low‐density polyethylene (LLDPE) were prepared. LLDPE was used as an impact modifier. Since the system was found to be incompatible, compatibilization was sought for by the addition of the following two types of functionalized polyethylene: ethylene vinylacetate copolymer (EVA) and maleic anhydride‐grafted EVA copolymer (EVA‐g‐MAH). The effects of the compatibilizers on the rheological and mechanical properties of the blends have been also quantitatively investigated. The impact strength of the PBT–LLDPE binary blends slightly increased at a lower concentration of LLDPE but increased remarkably above a concentration of 60 wt % of LLDPE. The morphology of the blends showed that the LLDPE particles had dispersed in the PBT matrix below 40 wt % of LLDPE, while, at 60 wt % of LLDPE, a co‐continuous morphology was obtained, which could explain the increase of the impact strength of the blend. Generally, the mechanical strength was decreased by adding LLDPE to PBT. Addition of EVA or EVA‐g‐MAH as a compatibilizer to PBT–LLDPE (70/30) blend considerably improved the impact strength of the blend without significantly sacrificing the tensile and the flexural strength. More improvement in those mechanical properties was observed in the case of the EVA‐g‐MAH system than for the EVA system. A larger viscosity increase was also observed in the case of the EVA‐g‐MAH than EVA. This may be due to interaction of the EVA‐g‐MAH with PBT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 989–997, 1999     

Processability and mechanical properties for binary blends of PP and LLDPE produced by metallocene catalyst

Processability at extrusion coating and mechanical properties of the films obtained are investigated by means of linear and nonlinear rheological measurements and tensile tests for blends of polypropylene (PP) and linear low‐density polyethylene (LLDPE). Both materials are produced by metallocene catalyst. The processability of PP is found to be improved by the addition of LLDPE; the blend shows low level of motor torque and head pressure in an extruder and small level of neck‐in as compared with pure PP. Further, the anisotropy of ultimate tensile strength, which is prominent for PP, is reduced by blending with LLDPE. As a result, the blend having 20 wt % of LLDPE shows appropriate properties in the molten state for extrusion coating and in the solid state as a film. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermostimulative shape memory effect of linear low‐density polyethylene/polypropylene (LLDPE/PP) blends compatibilized by crosslinked LLDPE/PP blend (LLDPE–PP)

A novel linear low‐density polyethylene (LLDPE)/polypropylene (PP) thermostimulative shape memory blends were prepared by melt blending with moderate crosslinked LLDPE/PP blend (LLDPE–PP) as compatibilizer. In this shape memory polymer (SMP) blends, dispersed PP acted as fixed phase whereas continuous LLDPE phase acted as reversible or switch phase. LLDPE–PP improved the compatibility of LLDPE/PP blends as shown in scanning electron microscopic photos. Dynamic mechanical analysis test showed that the melt strengths of the blends were enhanced with increasing LLDPE–PP content. A shape memory mechanism for this type of SMP system was then concluded. It was found that when the blend ratio of LLDPE/PP/LLDPE–PP was 87/13/6, the blend exhibited the best shape memory effect at stretch ratio of 80%, stretch rate of 25 mm/min, and recovery temperature of 135°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

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     

Mechanical properties and morphology of polylactide,linear low‐density polyethylene,and their blends

Melt blending of linear low density polyethylene (LLDPE) and polylactide (PLA) was performed in an extrusion mixer with post extrusion blown film attachment with and without compatibilizer‐grafted low density polyethylene maleic anhydride. The blend compositions were optimized for tensile properties as per ASTM D 882‐91. On the basis of this, LLDPE 80 [80 wt % LLDPE and 20 wt % poly(L ‐lactic acid) (PLLA)] and MA‐g‐low‐density polyethylene 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) were found to be an optimum composition. The blends were characterized according to their mechanical, thermal, and morphological behavior. Fourier transform infrared spectroscopy revealed that the presence of compatibilizer enhanced the blend compatibility to some extent. The morphological characteristics of the blends with and without compatibilizer were examined by scanning electron microscopy. The dispersion of PLLA in the LLDPE matrix increased with the addition of compatibilizer. This blend may be used for packaging applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dynamic mechanical, thermal, physico-mechanical and morphological properties of LLDPE/EMA blends

The effect of blend composition on the morphology, dynamic mechanical properties, thermal and physico-mechanical properties of linear low density polyethylene (LLDPE)/ ethylene-co-methyl acrylate (EMA) blends were studied. The blend showed both dispersed and continuous phase morphology that depends on the blend composition. A co-continuous structure is formed for blends containing 50 wt% of EMA. Dynamic mechanical studies showed that flexibility of the blend enhanced with the expansion of the amorphous region as EMA content increased. However, two separate melting temperature peak observed in differential scanning calorimetry (DSC) analysis indicate that the blends are immiscible in crystalline region of the two polymers. X-ray diffraction (XRD) studies showed that crystallinity of blends decreases with increase in EMA content and negative deviation of tensile strength from the mixing rule indicates the poor interfacial adhesion between the two components. FTIR spectroscopy established the lack of chemical interaction between LLDPE and EMA, which support the SEM, DSC, DMA and XRD observations. Parallel-Voids model has been applied to characterize phase morphology of these blends.     

LLDPE/LDPE blends. I. Rheological,thermal, and mechanical properties

Structure and mechanical properties were studied for the binary blends of a linear low density polyethylene (LLDPE) (ethylene‐1‐hexene copolymer; density = 900 kg m⁻³) with narrow short chain branching distribution and a low density polyethylene (LDPE) which is characterized by the long chain branches. It was found by the rheological measurements that the LLDPE and the LDPE are miscible in the molten state. The steady‐state rheological properties of the blends can be predicted using oscillatory shear moduli. Furthermore, the crystallization temperature of LDPE is higher than that of the LLDPE and is found to act as a nucleating agent for the crystallization of the LLDPE. Consequently, the melting temperature, degree of crystallinity, and hardness of the blend increase rapidly with increases in the LDPE content in the blend, even though the amount of the LDPE in the blend is small. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3153–3159, 1999     

Effect of EVA copolymer on properties of different polyethylenes in silane crosslinking process

Abstract

The effect of molecular structure of polyethylene (PE) [low density PE (LDPE), linear LDPE and high density PE] and silane/peroxide concentration on the grafting level and gel content in silane crosslinking process has been studied. The effect of incorporation of ethylene vinyl acetate (EVA) copolymer on the rate of crosslinking and thermal properties of PEs has been reported. The order of gel content was LDPE>linear LDPE>high density PE. With the incorporation of EVA, the rate of crosslinking increased. The degree of crystallinity did not change with crosslinking significantly. However, the shape of melting and crystallisation peaks changed, and two regions due to gel and sol parts were formed. In EVA/PE blends, two melting points were observed for both crosslinked and uncrosslinked samples. The SEM images showed the droplet matrix morphology with the EVA as the dispersed phase, especially for EVA/LDPE blend. The EVA/PE blends failed in hot set test, while the origin of PEs passed the hot set test successfully.     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Effects of dispersed phase composition on thermoplastic polyolefins

Ternary blends of polypropylene (PP), ethylene–octene copolymer (mPE), and high‐density polyethylene (HDPE) were prepared based on the phase behavior and physical properties of mPE/HDPE binary blends, and the results were interpreted in terms of morphology and both rheological and mechanical properties of the ternary blends as well as the binary blends. It was found that when mPE encapsulates HDPE in the PP matrix, compared to the encapsulation of mPE by HDPE, better blend properties were obtained, presumably because of the compatibilizing effect of mPE between PP and HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 179–188, 2004     

PP-硅橡胶-LLDPE三元共聚物的合成及性能研究

以聚丙烯(PP)为基体树脂,硅橡胶为增韧剂,线性低密度聚乙烯( LLDPE)为辅增韧剂,制备了一系列的PP/硅橡胶LLDPE的三元共聚物,考察了PP填充不同配比的硅橡胶共混物的力学性能.结果表明,随着硅胶含量不断的增加,样条的断裂伸长率,弹性模量,冲击强度逐渐增加,样条的拉伸强度随着硅胶的增加而逐渐减少;LLDPE的加入量为15％时,PP/硅橡胶/LLDPE的三元共混体系力学性能最佳;硅橡胶的加入量为20％时,PP/硅橡胶/LLDPE的三元共混体系具有良好的拉伸性能和冲击强度.     

Toughening of polyamide 11 via addition of crystallizable polyethylene derivatives

BACKGROUND: Conventional rubber‐like toughening modifiers are soft and amorphous, and when used to toughen polyamide 11 (PA11) they commonly induce a decrease in the tensile strength and modulus. In this study, crystallizable polyethylene (PE) derivatives, i.e. linear low‐density polyethylene (LLDPE) and maleic anhydride‐grafted polyethylene (PE‐g‐MA), were adopted to toughen PA11. RESULTS: Compared to pure PA11, a highest improvement by a factor of eight in the impact toughness was achieved; also, the tensile strength and modulus could be maintained at a relatively high level. PE‐g‐MA acted as a compatibilizer for PA11 and LLDPE, bringing strong interfacial adherence, and especially a domain‐in‐domain morphology observed in PA11/PE‐g‐MA/LLDPE (70/10/20 by weight) blends. The observation that PA11 was toughened by the crystallizable PE derivatives is discussed in depth, based on the combined effect of surface crystallization of LLDPE on pre‐formed PA11 crystallites and interfacial compatiblization between PA11 and PE‐g‐MA. CONCLUSION: The crystallizable PE derivatives LLDPE and PE‐g‐MA were shown to be effective toughening modifiers for the proportions PA11/PE‐g‐MA/LLDPE 70/10/20 (by weight), which is considered to be an optimum composition: special domain‐in‐domain morphology was observed indicating a good dispersion of PE in the PA11 matrix and strong interfacial adherence between PE phase and PA11 phase. The reason why strength and modulus were maintained at a high level in the as‐prepared blends was attributed to the existence of rigid crystalline domains in PE. Copyright © 2009 Society of Chemical Industry     

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.