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.     

Melt rheology and morphology of LLDPE/EVA blends: Effect of blend ratio,compatibilization, and dynamic crosslinking

The melt rheological properties of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were investigated with special reference to the effect of blend ratio, temperature, shear rate, compatibilization, and dynamic vulcanization. The melt viscosity of the blends determined with a capillary rheometer is found to decrease with an increase of shear rate, which is an indication of pseudoplastic behavior. The viscosity of the blend was found to be a nonadditive function of the viscosities of the component polymers. A negative deviation was observed because of the interlayer slip between the polar EVA and the nonpolar LLDPE phases. The melt viscosity of these blends decreases with the increased concentration of EVA. The morphology of the extrudate of the blends at different shear rates and blend ratios was studied and the size and distribution of the domains were examined by scanning electron microscopy. The morphology was found to depend on shear rate and blend ratio. Compatibilization of the blends with phenolic‐ and maleic‐modified LLDPE increased the melt viscosity at lower wt % of compatibilizer and then leveled off. Dynamic vulcanization is found to increase the melt viscosity at a lower concentration of DCP. The effect of temperature on melt viscosity of the blends was also studied. Finally, attempts were made to correlate the experimental data on melt viscosity and cocontinuity region with different theoretical models. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3210–3225, 2002     

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     

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     

Ultralow density polyethylene blends with polypropylene

Two types of ultralow density polyethylene (ULDPE) of different melt viscosities were blended with a polypropylene (PP) in a twin screw extruder. Morphology, thermal, rheological, and mechanical properties of the blends were determined. Morphological observation from SEM showed a clean phase separation of PP/ULDPE blends. However, depending on the viscosity ratio, a significant difference in the extent of phase separation, as well as in the phase inversion composition, was demonstrated. The melting temperature of PP and ULDPE were respectively increased and decreased in the blend. Crystallization rate and the, crystallinity of PP and ULDPE were first increased and then decreased as the other component was increased. Yield at low frequencies was observed with 30 wt% ULDPE in PP. In ULDPE-rich compositions, complex viscosities of the blends gave negative deviation from the additive rule of mixing. Mechanical properties such as flexural modulus, elongation at break and Vicat softening point were closely relatable to the morphology. The impact strength of PP is significantly improved by ULDPE addition.     

PP/LLDPE共混体系的研究

研究了聚丙烯(PP)／线性低密度聚乙烯(LLDPE)共混体系的形态结构与宏观性能之间的关系。对共混用的PP和LLDPE品种以及共混的工艺路线进行了选择；采用扫描电子显微镜(SEM)和偏光显微镜(PLY)观察了PP／LLDPE微观形态结构，并测试了力学性能和热性能。结果表明：屈服强度、拉伸模量、维卡软化点降低；当LLDPE用量增大时，随着LLDPE用量增加，材料的冲击强度增加，而拉伸共混体系形成互穿网络结构，具有良好的综合性能。     

黏度比对PP/POE共混物性能与结构的影响

研究了黏度比对聚丙烯(PP)/乙烯-辛烯共聚物(POE)共混物力学性能、形态结构以及结晶性能的影响。结果表明,黏度比对弯曲性能以及抗冲击性能有很大的影响,黏度比从0.55升至4.22时,弯曲模量从752.5MPa提高至875.3MPa,弯曲强度从20.5MPa提高至23.4MPa,低温冲击强度从347.8J/m提高至600.2J/m。当黏度比接近2.00时,冲击断面较光滑,说明PP和POE的黏度越接近,分散相的颗粒越小。共混物的熔融温度以及结晶温度均随着黏度比的降低而升高。     

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.     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

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     

Adhesion between individual components and mechanical properties of natural rubber-polypropylene thermoplastic elastomeric blends

Adhesion between individual components and the mechanical properties of natural rubber (NR)-polypropylene (PP) thermoplastic elastomeric blends with reference to adhesion have been studied. The adhesion strength between the component phases was varied by incorporating a third component, namely ethylene propylene diene rubber (EPDM) or chlorinated polyethylene (CPE), and their effects on the mechanical properties were also studied. It was observed that the level of adhesion between NR and PP is improved by incorporating 20 parts of EPDM or CPE in NR. The mechanical properties of the blends are also improved for a particular composition. The enhancement in the strength properties and modulus of an NR:X:PP (where X is the third component) (70:10:30 or 70:20:30) blend is apparent when a correction due to the hard-phase contribution of the blend is made by taking the ratio of the strength of the composite to the strength of the hard phase or modulus of the blends. When the three-component blends were compared with a 90:30 blend of NR-PP, the role of adhesion played by EPDM or CPE in improving the strength and modulus could be demonstrated. In fact, there is a direct qualitative relationship between the adhesion and the mechanical properties in such composites. The stronger the adhesion, the greater the tensile strength and modulus. The higher adhesion strength is further reflected from the morphology of various blends. Separation of the phases during swelling and subsequent drying is restricted in the systems exhibiting higher adhesion strength between the components.     

PP/LLDPE交联共混物的力学性能研究

采用两步交联加工法制备出具有优良力学性能的PP／LLDPE共混物。实验表明：当m(PP)／m(LLDPE)／m(SBS)／m(交联剂)为80／20／10／3时，交联共混物的冲击强度、拉伸强度和断裂伸长率分别达到466．3J／m、27．1MPa和715．1％，比未交联的共混物分别提高262％、8．28％和115％；交联作用的存在使共混物的脆韧转变点明显提前；随交联剂用量的增加，共混物的力学性能不断提高，但增大趋势逐渐变小。     

Morphology and properties of blends with different thermoplastic polyurethanes and polyolefines

Unmodified blends of two thermoplastic polyurethanes (TPU) and six polyolefines were used to study the influence of the component viscosities on the blend morphology and mechanical properties. Blends were produced by melt mixing using a twin screw extruder. Interactions between the blend components could not be detected by DSC, DMA, selective extraction, and SEM micrographs of cryofractures. The variation in tensile strength with blend composition produce a U-shaped curve with the minimum between 40 and 60 wt % of polyolefine. At similar viscosity ratios (η_d/η_m), blends with polyether based TPU (TPU-eth) have a finer morphology than blends with polyester based TPU (TPU-est). This is due to the lower surface free energy of the polyether soft segments compared to the polyester soft segments. Different morphologies also lead to changes in mechanical behavior. Blends with TPU-eth show a lower decrease in tensile strength with blend composition than blends with TPU-est. The viscosity ratio between TPU and polyolefines can be directly correlated to the blend morphology obtained under similar blending conditions. TPU/PE blends show a lower dispersity than TPU/PP blends, due to the higher viscosity ratios of TPU/PE blends. This results in a greater reduction in tensile strength with the disperse phase content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 749–762, 1997     

BHDPE/HDPE/LLDPE共混体系的研究

采用线性低密度聚乙烯(LLDPE)对双峰高密度聚乙烯(BHDPE)和高密度聚乙烯(HDPE)进行共混,测定共混物的力学性能和DSC曲线。结果显示共混物均可以产生共晶,LLDPE对BHDPE力学性能影响较大;在LLDPE/HDPE中添加BHDPE,三者共混物具有更好的力学性能,流变性能显示三者共混物体系黏度变化不大,为制备性能最优、成本最低的三者共混物提供了依据。     

Comprehensively improved mechanical properties of silane crosslinked polypropylene/ethylene propylene diene monomer elastomer blends

The properties and structure of silane crosslinked polypropylene (PP)/ethylene propylene diene monomer (EPDM) elastomer blends had been carried out. Fourier transform infrared spectroscopy and gel content tests were employed to evaluate the crosslinking reaction of PP/EPDM blends. Crosslinking efficiency of PP/EPDM blends was investigated using thermogravimetric analysis, differential scanning calorimeter, dynamic mechanical analysis, dynamic rheology, and tensile testing. Tanδ curves of silane crosslinked PP/EPDM blends exhibited an obvious “gel point” originated from the formation of dynamic crosslinking network. The blend corresponding to the “gel point” presented comprehensively improved mechanical properties. These results demonstrated that characteristic rheological parameters showed close correlations with key mechanical properties of silane crosslinked PP/EPDM blends. Scanning electron microscopy images illustrated that crosslinking had remarkably changed the morphologies of PP/EPDM blends. The large deformation mechanism of these blends had been suggested.     

Thermal,dynamic mechanical,and rheological behavior of linear low-density polyethylene/poly(octadecene-co-maleic anhydride) blends

Blends of linear low-density polyethylene (LLDPE) and a 50:50 copolymer of octadecene and maleic anhydride (C₁₈-MAH) were characterized by calorimetry, dynamic mechanical testing, and rheometry. In the solid state, the blends are essentially immiscible. No evidence was obtained for cocrystallization of the LLDPE with the paraf-finic side-chains of the C₁₈-MAH. Interactions between the blend components were observed in three ways. First, presence of the C₁₈-MAH in the LLDPE melt increases the nucleation rate for LLDPE crystallization. Second, side-chain crystallization in a portion of the C₁₈-MAH component equivalent to approximately 15% of the total blend is apparently suppressed in the blends. Third, although the mechanical loss of the blends is essentially a sum of the pure components, the β relaxation of the LLDPE is absent in blends containing more than 20% C₁₈-MAH. The blends are also immiscible in the melt. The steady and dynamic shear rheology is dominated by the immiscibility and mismatch in viscosity, η, between the two polymers. A linear dependence on blend composition was found for log η in dynamic (small strain) tests. Nonlinear behavior with positive and negative deviations from linearity was found for log η in steady shear (large strain) tests.     

Dynamic rheological,morphology and mechanical properties of compatibilized LLDPE/EMA blends

Blends of linear low density polyethylene (LLDPE) and ethylene-co-methyl acrylate (EMA) having 60/40 composition was studied with and without compatibilizing agent. The compatibilizing agent used was maleic anhydride grafted linear low density polyethylene (LLDPE-g-MA). The LLDPE backbones of the compatibilizer are compatible with LLDPE blend component, whereas the maleic anhydride is affinated with carbonyl groups of EMA. The effectiveness of the compatibilizing agent was evaluated using different techniques like mechanical, thermal, scanning electron microscopy and rheological studies. Best compatibilization effect was found in the blend at a loading of 3 wt% of compatibilizer since at this level of compatibilizer complex viscosity, tensile strength, modulus, elongation at break, impact strength was found to be higher. The increase in the melt viscosity, storage modulus and thermal stability of the compatibilized blends indicated enhanced interactions between the discrete LLDPE and EMA phases induced by the functional compatibilizer.     

不同促进剂对PP/PP-g-MAH/脱硫胶粉共混物性能影响

选用促进剂N-环己基-2-苯并噻唑次磺酰胺(CZ)、四甲基秋兰姆(TMTD)和N-叔丁基-2-苯并噻唑次磺酰胺(NZ)作为脱硫再生剂,分别对废旧胶粉进行改性,制备脱硫再生胶粉,然后制备聚丙烯(PP)/马来酸酐接枝PP(PP-g-MAH)/脱硫胶粉共混物,研究共混物力学性能、流动性能、断面形貌、流变性能和热性能的影响.结...     

Rheological Properties of Thermoplastic Polyvinyl Alcohol and Polypropylene Blend Melts in Capillary Extrusions

A single screw extruder with a static mixer was used to prepare molten blends of thermoplastic polyvinyl alcohol (TPVA) and polypropylene (PP). The effects of shear rate, blending ratio and temperature on rheological properties for the blends in capillary extrusions were investigated, and ends correction was also carried out. Rheological parameters such as non-Newtonian index and activation energy were also calculated and evaluated. It was found that the viscosities of the blends were lower than those of TPVA and PP; moreover, the non-Newtonian indices and the activation energies of the blend melts were higher than those of the homopolymers. In particular, the blend with 60 wt% TPVA had the highest non-Newtonian indices and activation energies among blend melts. These results indicate that TPVA and PP blends are negative deviation blends. Furthermore, at a blending ratio of 60 wt% of TPVA, the shear-sensitivity of the viscosity was the lowest and the temperature dependence of the viscosity was the highest. In addition, an increase in temperature led to an increase in non-Newtonian index, therefore the shear-rate dependence of the blend viscosities decreased with a rise in temperature. As the shear rate was increased, the variation of the viscosity over blending ratios decreased while the activation energy of the blends decreased. Thus the effects of temperature and blending proportion on flow behavior were diminished by increasing shear rate.     

PP/UHMWPE共混物力学性能的研究

采用不同结构的聚丙烯(PP)分别与不同流动性能的超高摩尔质量聚乙烯(UHMWPE)进行共混，对共混物的力学性能进行了研究。发现PP和UHMWPE类型的适当匹配对共混物性能的提高非常重要。流动性较好的UHMWPE对熔体质量流动速率较小的嵌段共聚型PP(PPB)增韧增强效果突出，常温缺口冲击强度可达74．2kJ／m^2，断裂伸长率大于700％；同时共混物的强度和刚性也有一定程度的提高。在PPB／UHMWPE二元共混物中加入适当线性低密度聚乙烯(LLDPE)，能够起到“减粘”和“增容”作用，有利于共混物性能，尤其是抗冲性能的进一步提高。