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     

Relationship between processing history and rheological properties during postprocessing annealing for anomalous polyethylene blends

The effect of applied processing history and postprocessing annealing treatment on the rheological properties has been studied for a binary blend composed of linear low‐density polyethylene (LLDPE) and low‐density polyethylene produced by radical polymerization (LDPE). It has been found that intensive processing in an internal mixer depresses oscillatory modulus, especially storage modulus, at lower frequency region for LDPE and the blends with LLDPE, whereas the rheological properties of LLDPE are independent of both processing and annealing procedures. Further, the depression of the modulus is found to be more prominent for the blends with 20–40 wt % of LLDPE than that for the pure LDPE, although the phenomenon is ascribed to conformation change of long‐chain branches. Moreover, the blends show slower recovery of the modulus during the postprocessing annealing than do LDPE. The results demonstrate that processing and mixing conditions have to be considered seriously for LDPE/LLDPE blends showing enhanced melt elasticity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1078–1083, 2006     

Co‐crystallization in ternary polyethylene blends: tie crystal formation and mechanical properties improvement

Understanding the co‐crystallization behavior of ternary polyethylene (PE) blends is a challenging task. Herein, in addition to co‐crystallization behavior, the rheological and mechanical properties of melt compounded high density polyethylene (HDPE)/low density polyethylene (LDPE)/Zeigler ? Natta linear low density polyethylene (ZN‐LLDPE) blends have been studied in detail. The HDPE content of the blends was kept constant at 40 wt% and the LDPE/ZN‐LLDPE ratio was varied from 0.5 to 2. Rheological measurements confirmed the melt miscibility of the entire blends. Study of the crystalline structure of the blends using DSC, wide angle X‐ray scattering, small angle X‐ray scattering and field emission SEM techniques revealed the formation of two distinct co‐crystals in the blends. Fine LDPE/ZN‐LLDPE co‐crystals, named tie crystals, dispersed within the amorphous gallery between the coarse HDPE/ZN‐LLDPE co‐crystals were characterized for the first time in this study. It is shown that the tie crystals strengthen the amorphous gallery and play a major role in the mechanical performance of the blend.© 2016 Society of Chemical Industry     

Modification of recycled high‐density polyethylene by low‐density and linear‐low‐density polyethylenes

The present study investigated mixed polyolefin compositions with the major component being a post‐consumer, milk bottle grade high‐density polyethylene (HDPE) for use in large‐scale injection moldings. Both rheological and mechanical properties of the developed blends are benchmarked against those shown by a currently used HDPE injection molding grade, in order to find a potential composition for its replacement. Possibility of such replacement via modification of recycled high‐density polyethylene (reHDPE) by low‐density polyethylene (LDPE) and linear‐low‐density polyethylene (LLDPE) is discussed. Overall, mechanical and rheological data showed that LDPE is a better modifier for reHDPE than LLDPE. Mechanical properties of reHDPE/LLDPE blends were lower than additive, thus demonstrating the lack of compatibility between the blend components in the solid state. Mechanical properties of reHDPE/LDPE blends were either equal to or higher than calculated from linear additivity. Capillary rheological measurements showed that values of apparent viscosity for LLDPE blends were very similar to those of the more viscous parent in the blend, whereas apparent viscosities of reHDPE/LDPE blends depended neither on concentration nor on type (viscosity) of LDPE. Further rheological and thermal studies on reHDPE/LDPE blends indicated that the blend constituents were partially miscible in the melt and cocrystallized in the solid state.     

Influence of branching characteristics on thermal and mechanical properties of Ziegler–Natta and metallocene hexene linear low‐density polyethylene blends with low‐density polyethylene

The effect of the branch content (BC) and composition distribution (CD) of linear low‐density polyethylene (LLDPE) on the thermal and mechanical properties of its blends with LDPE were studied. All blends and pure resins were conditioned in a Haake PolyDrive blender at 190°C and in the presence of adequate amounts of antioxidant. Two metallocene LLDPEs (m‐LLDPE) and one Ziegler–Natta (ZN) hexene LLDPE were melt blended with the same LDPE. The effect of the BC was investigated by blending two hexene m‐LLDPEs of similar weight‐average molecular weights and molecular weight distributions but different BCs with the same LDPE. The effect of the CD was studied by using a ZN and an m‐LLDPE with similar weight‐average molecular weights, BCs, and comonomer type. Low‐BC m‐LLDPE blends showed separate crystallization whereas cocrystallization was observed in the high‐BC m‐LLDPE‐rich blends. However, ZN‐LLDPE/LDPE blends showed separate crystallization together with a third population of cocrystals. The influence of the crystallization behavior was reflected in the mechanical properties. The BC influenced the modulus, ultimate tensile strength, and toughness. The addition of a small amount of LDPE to a low‐BC m‐LLDPE resulted in a major improvement in the toughness, whereas the results for the high‐BC pair followed the additivity rule. ZN‐LLDPE blends with LDPE blends were found to be more compatible and exhibited superior mechanical properties compared to m‐LLDPE counterparts with the same weight‐average molecular weight and BC. All mechanical properties of ZN‐LLDPE blends follow the linear rule of mixtures. However, the CD had a stronger influence on the mechanical properties in comparison to the BC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2488–2498, 2005     

Rheology of LLDPE,LDPE and LLDPE/LDPE blends and its relevance to the film blowing process

The relevance of polymer melt rheology in film blowing process for linear low‐density polyethylene (LLDPE) and its blends with three different low‐density polyethylenes (LDPEs) has been discussed. The effect of different LDPE components as well as their concentration on shear and elongational viscosity has been investigated. A good correlation has been observed between the extensional rheological parameters of LDPEs measured by different experimental techniques. The molecular structure of parent polymers as well as blend composition play an important role in the rheology of these blends and consequently their performance in the film blowing process. © 2000 Society of Chemical Industry     

Development of polybutadiene (BR)–polyethylene (LDPE) blend based microcellular soles for low‐temperature applications

Microcellular (MC) soles based on polybutadiene (BR) and low‐density polyethylene (LDPE) blends for low‐temperature applications were developed. A part of BR in BR–LDPE blend was replaced by natural rubber (NR) for property improvement. The BR–NR–LDPE blend‐based MC sole shows good technical properties. Sulphur curing and DCP curing were tried in BR–LDPE and NR–BR–LDPE blends. Study shows that sulphur‐cured MC sheets possess better technical properties than DCP‐cured MC sheets. 90/10 BR–LDPE and 60/30/10 BR–NR–LDPE blend combinations are found to be suitable for low‐temperature applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 277–281, 2000     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

Melt rheology of compatibilized polystyrene/low density polyethylene blends

Investigations have been made on the melt rheological behaviors of compatibilized blends composed of polystyrene, low density polyethylene and hydrogenated (styrene‐butadiene‐styrene) triblock copolymer used as a compatibilizer. The experiments were carried out on a capillary rheometer. The effects of shear stress, temperature and blending ratio on the activation energy for viscous flow and melt viscosity of the blends are described. The study shows that the viscosity of the blends exhibits a maximum or minimum value at a certain blending ratio. The activation energy for viscous flow decreases with increasing LDPE content. Furthermore, the concept of equal‐viscosity temperature is presented and its role in the processing of the blend is discussed. In addition, the morphology of the extrudate sample of the blends was observed by scanning electron microscopy and the correlation between the morphology and the rheological properties is explored. © 1999 Society of Chemical Industry     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

Rheological,thermal, and morphological properties of low‐density polyethylene/ultra‐high‐molecular‐weight polyethylene and linear low‐density polyethylene/ultra‐high‐molecular‐weight polyethylene blends

The dynamic rheological behavior of low‐density polyethylene (LDPE)/ultra‐high‐molecular‐weight polyethylene (UHMWPE) blends and linear low‐density polyethylene (LLDPE)/UHMWPE blends was measured in a parallel‐plate rheometer at 180, 190, and 200°C. Analysis of the log–additivity rule, Cole–Cole plots, Han curves, and Van Gurp curves of the LDPE/UHMWPE blends indicated that the blends were miscible in the melt. In contrast, the rheological properties of LLDPE/UHMWPE showed that the miscibility of the blends was decided by the composition of LLDPE. The differential scanning calorimetry results and scanning electron microscopy photos of the LLDPE/UHMWPE blends were consistent with the rheological properties, whereas with regard to the thermal and morphological properties of LDPE/UHMWPE blends, the results reveal three endothermic peaks and phase separation, which indicated a liquid–solid phase separation in the LDPE/UHMWPE blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

BMDPE／LDPE／LLDPE共混熔体的流变行为与力学性能

研究了双峰中密度聚乙烯（BMDPE），低密度聚乙烯（LDPE）与线型低密度聚乙烯（LLDPE）共混熔体的流变行为和力学性能，讨论了共混物的组成，剪切应力和剪切速率以及温度对熔体流变行为，熔体粘度和膨胀比的影响，测定了不同配比熔体的非牛顿指数，熔体流动速率，粘流活性能及屈服应力，断裂应力和断裂伸长率，为BMDPE的加工和使用以及开发高性能价格比的PE材料提供了依据。     

Melt strength and film bubble instability of LLDPE/LDPE blends

The relevance of measuring the melt strength of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blends to their performance in terms of bubble stability in the film blowing process has been investigated. A good correlation between the melt strength values for two series of LLDPE/LDPE blends and the size of the operating window for stable film bubble formation has been established. Both the macromolecular structure of the parent polymers, and melt morphology play an important role in the performance of these blends in the film blowing process. © 1999 Society of Chemical Industry     

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

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

The role of the interface in melt linear viscoelastic properties of LLDPE/LDPE blends: Effect of the molecular architecture of the matrix

The rheological properties of blends consisting of a long chain branched low‐density polyethylene (LDPE) and two linear low‐density polyethylenes (LLDPE) are studied in detail. The weight fractions of the LDPE used in the blends are 5 and 15%. The linear viscoelastic characterization is performed at different temperatures for all the blends to check thermorheological behavior and miscibility in the melt state. Blends containing metallocene LLDPE as the matrix display thermorheologically complex behavior and show evidences of immiscibility in the melt state. The linear viscoelastic response exhibits the typical additional relaxation ascribed to the form deformation mechanism of dispersed phase droplets (LDPE). The Palierne model satisfactorily describes the behavior of these blends in the whole frequency range explored. However, those blends with Ziegler‐Natta LLDPE as the matrix fulfill the time‐temperature superposition, but exhibit a broad linear viscoelastic response, further than the expected for an immiscible system with a sharp interface. The rheological analysis reveals that, in addition to the droplets form relaxation, another mechanism at lower frequencies exists. The broad linear response of the blends with the Ziegler‐Natta LLDPE can be explained by hypothesizing a strong interaction between the high molecular weight linear fraction of the LLDPE and the low molecular weight (almost linear) chains of the LDPE phase, forming a thick interface with its own viscoelastic properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compatibility of HDPE/postconsumer HDPE blends using compatibilizing agents

Mechanical properties, molecular weight, X‐ray diffraction, and differential scanning calorimetry (DSC) characterization of blends of virgin high‐density polyethylene (HDPE) with two types of recycled material were investigated. The recycled came from urban plastic waste; one kind was only washed and grounded and the other was extruded and pelletized to remove most of contaminant particles. Starting with the 30/70 virgin/grounded recycled and 50/50 virgin/pelletized recycled blends the recycled content was increased in both blends and compatibilizing agents were used to increase the blend performance. A mixture of phenolic antioxidants and phosphite costabilizers under the name of Recycloblend?, ethylene vinyl acetate (EVA) copolymer, low‐density polyethylene (LDPE), and linear low density polyethylene (LLDPE) were used as compatibilizers. The effect of these additives and the recycled content on the performance of extrusion blow‐molded bottles was determined. The results suggest that blends of virgin/grounded recycled and virgin/pelletized recycled HDPE, in general, were not significantly different among each other and both had a quite similar behavior than the virgin HDPE when compatibilizing agents were used. The addition of compatibilizing agents yielded a material with properties similar to those for the virgin HDPE, helping to reduce the effect of polymers degradation on the rheological and mechanical behavior, with Recycloblend and LLDPE being the most effective for the blends with grounded recycled material, and LLDPE y EVA, for the blends with pelletized recycled. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3696–3706, 2006     

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     

Morphology and rheological properties of compatibilized low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch blends

Morphology and rheological properties of low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch (LDPE/LLDPE/TPS) blends are experimentally investigated and theoretically analyzed using rheological models. Blending of LDPE/LLDPE (70/30 wt/wt) with 5–20 wt % of TPS and 3 wt % of PE‐grafted maleic anhydride (PE‐g‐MA) as a compatibilizer is performed in a twin‐screw extruder. Scanning electron micrographs show a fairly good dispersion of TPS in PE matrices in the presence of PE‐g‐MA. However, as the TPS content increases, the starch particle size increases. X‐ray diffraction patterns exhibit that with increase in TPS content, the intensity of the crystallization peaks slightly decreases and consequently crystal sizes of the blends decrease. The rheological analyses indicate that TPS can increase the elasticity and viscosity of the blends. With increasing the amount of TPS, starch particles interactions intensify and as a result the blend interface become weaker which are confirmed by relaxation time spectra and the prediction results of emulsion Palierne and Gramespacher‐Meissner models. It is demonstrated that there is a better agreement between experimental rheological data and Coran model than the emulsion models. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44719.     

Crystallization of low‐density polyethylene‐ and linear low‐density polyethylene‐rich blends

The crystallization of a series of low‐density polyethylene (LDPE)‐ and linear low‐density polyethylene (LLDPE)‐rich blends was examined using differential scanning calorimetry (DSC). DSC analysis after continuous slow cooling showed a broadening of the LLDPE melt peak and subsequent increase in the area of a second lower‐temperature peak with increasing concentration of LDPE. Melt endotherms following stepwise crystallization (thermal fractionation) detailed the effect of the addition of LDPE to LLDPE, showing a nonlinear broadening in the melting distribution of lamellae, across the temperature range 80–140°C, with increasing concentration of LDPE. An increase in the population of crystallites melting in the region between 110 and 120°C, a region where as a pure component LDPE does not melt, was observed. A decrease in the crystallite population over the temperature range where LDPE exhibits its primary melting peaks (90–110°C) was noted, indicating that a proportion of the lamellae in this temperature range (attributed to either LDPE or LLDPE) were shifted to a higher melt temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1009–1016, 2000     

Effects of ultrasonic oscillations on processing behavior and mechanical properties of metallocene‐catalyzed linear low‐density polyethylene/low‐density polyethylene blends

The influences of ultrasonic oscillations on rheological behavior and mechanical properties of metallocene‐catalyzed linear low‐density polyethylene (mLLDPE)/low‐density polyethylene (LDPE) blends were investigated. The experimental results showed that the presence of ultrasonic oscillations can increase the extrusion productivity of mLLDPE/LDPE blends and decrease their die pressure and melt viscosity during extrusion. Incorporation of LDPE increases the critical shear rate for sharkskin formation of extrudate, crystallinity, and mechanical properties of mLLDPE. The processing behavior and mechanical properties of mLLDPE/LDPE blends were further improved in the presence of ultrasonic oscillations during extrusion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2522–2527, 2004