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     

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 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     

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.     

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     

Viscoelastic,thermal and environmental characteristics of poly(lactic acid), linear low-density polyethylene and low-density polyethylene ternary blends and composites

Poly(lactic acid) (PLA)/(linear low-density polyethylene (LLDPE)–low-density polyethylene (LDPE)) PLA/(LLDPE-LDPE) ternary blends were prepared and characterized as function of the PLA content. (50/50) PLA/(LLDPE–LDPE) blend was also compatibilized using maleic anhydride grafted low-density polyethylene (PE-g-MA) incorporated with a concentration of 5 wt.%. PLA/(LLDPE–LDPE) blend composites have been prepared by dispersing 5 wt.% of an organophilic montmorillonite (Org-MMT), added according to two different mixing methods. These materials were subjected to several investigations such as X-rays diffraction (XRD), dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry, and environmental tests. In the PLA glassy region, DMTA results showed that the storage modulus of PLA/(LLDPE–LDPE) blends decreases upon decreasing the PLA content. When PE-g-MA and Org-MMT were added, PLA exhibited a noticeable increase in the storage modulus across the glass transition region due the interface reinforcement and the enhancement of the blends stiffness. The decrease in the magnitude of the PLA tan δ peak was attributed to the decrease in the molecular mobility that could result from the increase in the interfacial resistance. XRD analysis showed that the method of dispersion of the nanoclay controls the final structural properties of the composites. (50/50) PLA/(LLDPE-LDPE) blend and composites revealed a satisfactory aptitude to biodegradation.     

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     

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     

Correlations between processing parameters,morphology, and properties of blown films of LLDPE/LDPE blends,part 2: Crystalline and amorphous biaxial orientation by WAXD pole figures

The biaxial molecular orientation of blown films made of blends of linear low density polyethylene (LLDPE) with low density polyethylene (LDPE) was characterized by two different methods: complete pole figures obtained by wide angle X‐rays diffraction (WAXD) and polarized infrared spectroscopy (IR) using the Krishnaswamy approach. The molecular orientation of the blends amorphous phase was also evaluated by polarized IR. The crystallinity of the blown films was determined by WAXD. A good correlation between the X‐ray pole figures and the polarized IR results was obtained. At all blends compositions, it was shown that the a‐axis of the polyethylene orthorhombic cell was preferentially oriented along the machine direction, the orientation degree along this direction increasing with the increase of the LDPE amount in the blends. The b‐axis changed its preferential orientation from film thickness in the 100/0 LLDPE/LDPE film to along the transverse direction with increasing LDPE in the blends. The c‐axis changed its orientation from orthogonal to normal direction in the 100/0 LLDPE/LDPE film to along the film thickness with increasing LDPE in the blends. Polarized IR characterization showed a negligible orientation of the amorphous phase. The amount of crystallinity was dependent on blend composition decreasing with the increase of LDPE content in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2760–2767, 2006     

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     

Effect of Polyethylene Molecular Architecture on the Dynamic Viscoelastic Behavior of Polyethylene/Polyhexene-1 Blends and Its Correlation with Morphology

In the present work, the rheology, morphology, and interfacial interaction of polyethylene/polyhexane-1 (PE/PH-1) blends with various polyethylene types with different molecular architectures are investigated. The scanning electron microscopy (SEM) images showed a droplet-matrix morphology in all percentage of PH-1 for all blend systems and the size of droplets increased proportionally with PH-1 content. The minimum droplet size is observed for high-density polyethylene (HDPE)/PH-1 blends. The homogeneity of the blends at various compositions is assessed by using viscoelastic parameters determined by dynamic oscillation rheometry in the linear viscoelastic region. A distinct Newtonian plateau at low frequencies is perceived and the variations of complex viscosity (η*) versus angular frequency (ω) for all blend systems are in good agreement with Carreau-Yasuda model. The complex viscosity of samples at various percentages of PH-1 showed the negative deviation from mixing rule in low and high frequencies for all blend systems. The Cole-Cole plots deviated from semi-circular shape at higher percentages of PH-1 than 10wt% in the blends of low-density polyethylene (LDPE)/PH-1 and linear low-density polyethylene (LLDPE)/PH-1. By using emulsion theoretical model, the lowest interfacial tension is found for HDPE/PH-1 blends comparing with its counterparts based on LDPE and LLDPE and the best fitting with experimental data was observed for this blends system.     

Morphology and deformation of compatibilized polystyrene low density polyethylene blends

This investigation deals with the morphology and tensile behavior of polystyrene/low density polyethylene blends compatibilized by hydrogenated styrene‐b‐butadiene‐b‐styrene triblock copolymer. The stress‐strain measurements indicate that blends with excellent toughness were achieved, due to the compatibilizing role of the triblock copolymer in the system. The morphology of the blends was observed by scanning electron microscopy (SEM), and the results show that the state of polystyrene changes from continuous phase to dispersed phase with increasing LDPE content. The correlation between mechanical properties and morphology is discussed. The morphologies of the tensile bars were also examined by SEM, and the deformation mechanisms of the blend were further analysed according to fractography. © 1999 Society of Chemical Industry     

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。     

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     

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     

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     

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.     

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     

Water crosslinking reactions of silane‐grafted polyolefin blends

Water crosslinking reactions of LDPE, PP, LLDPE, and the LDPE/PP and LDPE/LLDPE blends are investigated. Degrees of crosslinking of these samples are quantitatively compared and discussed in detail in terms of crosslinking ability, phase‐separation behavior, molecular weight (or viscosity), morphology of the constituents in blends, or in the pure state. It is found that PP gives negligible crosslinking reactions in the pure state and in blends with LDPE. LDPE and LLDPE are both capable of giving considerable degrees of crosslinking, with LLDPE giving a higher degree of crosslinking than LDPE at all conditions studied. Degrees of crosslinking of the LDPE/LLDPE blends are not linearly but are zigzagly related to the compositions of the blends with the LDPE/LLDPE = 50/50 blend giving a relatively high degree of crosslinking at 100, 120, and 140°C for a certain time except the condition at 140°C for 12 h compared with the LDPE/LLDPE = 75/25 and 25/75 blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1799–1807, 2001     

LLDPE/LDPE/TiO2复合膜的分散及光学性能

讨论了纳米TiO2在线型低密度聚乙烯（LLDPE），低密度聚乙烯（LDPE）复合体系中的分散和体系流变行为，研究了复合薄膜的光学性能。结果表明，以高流动性LDPE为基体的纳米TiO2母料，加入LLDPE，LDPE体系中后。复合体系的表观粘度有所提高。但拉伸粘度显著下降。纳米TiO2母料在LLDPE／LDPE复合体系中具有良好的分散性，复合薄膜中的纳米TiO2为一次粒子。纳米TiO2起到了异相成核剂的作用。球晶的粒子得到细化。在本研究的纳米填充范围内（质量分数不大于1.0％），复合薄膜的透光度基本不变。雾度发生了较大幅度上升，复合薄膜在紫外光区域的吸收显著增强。