Melt miscibility and mechanical properties of metallocene linear low‐density polyethylene blends with high‐density polyethylene: influence of comonomer type

In this paper, the implications of melt miscibility on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)/high‐density polyethylene (HDPE) blends were assessed with respect to the influence of the comonomer type. The influence of the latter was examined by selecting one butene LLDPE and one octene LLDPE of very similar weight‐average molecular weight (M_w), molecular‐weight distribution (MWD) and branch content, keeping the comonomer type as the only primary molecular variable. Each of the two metallocene LLDPEs was melt‐blended with the same HDPE at 190 °C in a Haake melt‐blender. The rheological, thermal and mechanical properties were measured by the use of an ARES rheometer, differential scanning calorimeter and Instron machine, respectively. The rheological measurements, made over the linear viscoelastic range, suggested no significant influence of the branch type on the melt miscibility. The rheology results are in agreement with those obtained from previous transmission electron microscopy (TEM) and small‐angle neutron scattering (SANS) studies. The dynamic shear viscosity and total crystallinity of the metallocene (m)‐LLDPE blends with HDPE followed linear additivity. At small strains, the branch type has little or no influence on the melt miscibility and solid‐state properties of the blends. Even the large‐strain mechanical properties, such as tensile strength and elongation at break, were not influenced by the comonomer type. However, the ultimate tensile properties of the HDPE‐rich blends were poor. Incompatibility of the HDPE‐rich blends, as a result of the weak interfaces between the blend components, is suggested to develop at large strains. Copyright © 2005 Society of Chemical Industry     

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     

Polyphosphazene/low‐density polyethylene blends: Miscibility and flame‐retardance studies

The effect of poly(dianilinephosphazene) (PDAP) on the processability, thermal behavior, crystallinity, morphology, mechanical properties, and flammability behavior of low‐density polyethylene (LDPE) was studied. Plasticorder traces of PDAP/LDPE blends implied good processability and miscibility. Thermogravimetric analysis showed that PDAP improved the thermal stability of LDPE. X‐ray diffraction results indicated that PDAP was a semicrystalline polymer, and the crystallinity of the blends decreased with increasing PDAP content. A new reflection at 2θ = 23.15° was found in wide‐angle X‐ray diffraction spectra of the blends, indicating that these two components interacted with one another. The scanning electron microscopy microstructures of the blends also supported these findings. Moreover, PDAP substantially enhanced the limited oxygen index and elongation at break of LDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 709–714, 2002     

Influence of maleic anhydride on the compatibility of thermal plasticized starch and linear low‐density polyethylene

In the presence of dicumyl peroxide, the compatibility of thermal plasticized starch/linear low‐density polyethylene (TPS/LLDPE) blends using maleic anhydride (MAH) as compatibilizer was investigated. The thermal plasticization of starch and its compatibilizing modification with LLDPE was accomplished in a single‐screw extruder at the same time. We prepared three types of blends containing different percentages of TPS and MAH. The content of MAH based on LLDPE was 0, 1, and 2 wt %, respectively. The morphology of the blends was studied by SEM. It was found that, with the addition of MAH, the blends have good interfacial adhesion and finely dispersed TPS and LLDPE phases, which is reflected in the mechanical and thermal properties of the blends. The blends containing MAH showed higher tensile strength, elongation at break, and thermal stability than those of blends without MAH. The rheologic properties of the blends demonstrated the existence of processing. Finally, the dynamic thermal mechanical analysis results indicated that, with the addition of MAH, the compatibility between TPS and LLDPE in the blends was substantially improved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 686–695, 2004     

Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Blends of high‐density polyethylene with solid silicone additive

Silicone masterbatch (SMB) is a pelletized formulation containing 50% of an ultrahigh molecular‐weight polydimethylsiloxane dispersed in polyethylene. This SMB is designed to be used as an additive in polyethylene‐compatible systems to impart benefits such as processing improvement and modification of surface characteristics. In this work, binary blends of high‐density polyethylene (HDPE) and SMB were prepared by melt‐mixing technique to study the influence of this masterbatch on the processing and mechanical properties of HDPE. Ternary blends were also prepared by the addition of silane‐grafted polyethylene (HDPE‐VTES) as compatibilizer. The blends were analyzed by melting flow rate (MFR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and tensile tests. Data of final torque and MFR showed that SMB improved the processability of pure HDPE. DSC results showed differences in crystalline behavior between binary and ternary blends. In the former, the degree of crystallinity increased up to 10 wt % of SMB content; beyond this concentration, it decreased. In ternary blends, a reverse behavior was observed. The morphologic study showed silicone particles uniformly distributed in HDPE matrix. With high SMB concentration, the addition of HDPE‐VTES significantly reduced the size of silicone particles. In the range of SMB composition studied, the mechanical properties of blends lower slightly compared to pure HDPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2347–2354, 2002     

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     

Implications of melt compatibility/incompatibility on thermal and mechanical properties of metallocene and Ziegler–Natta linear low density polyethylene (LLDPE) blends with high density polyethylene (HDPE): influence of composition distribution and branch content of LLDPE

In this paper, the implications of melt compatibility on thermal and solid‐state properties of linear low density polyethylene/high density polyethylene (LLDPE/HDPE) blends were assessed with respect to the effect of composition distribution (CD) and branch content (BC). The effect of CD was studied by melt blending a metallocene (m‐LLDPE) and a Ziegler‐Natta (ZN) LLDPE with the same HDPE at 190 °C. Similarly, the effect of BC was examined. In both cases, resins were paired to study one molecular variable at a time. Thermal and solid‐state properties were measured in a differential scanning calorimeter and in an Instron mechanical testing instrument, respectively. The low‐BC m‐LLDPE (BC = 14.5 CH₃/1000 C) blends with HDPE were compatible at all compositions: rheological, thermal and some mechanical properties followed additivity rules. For incompatible high‐BC (42.0 CH₃/1000 C) m‐LLDPE‐rich blends, elongation at break and work of rupture showed synergistic effects, while modulus was lower than predictions of linear additivity. The CD of LLDPE showed no significant effect on thermal properties, elongation at break or work of rupture; however, it resulted in low moduli for ZN‐LLDPE blends with HDPE. For miscible blends, no effect for BC or CD of LLDPE was observed. The BC of LLDPE has, in general, a stronger influence on melt and solid‐state properties of blends than the CD. Copyright © 2004 Society of Chemical Industry     

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     

Morphology and mechanical properties of styrene–ethylene/butylene–styrene triblock copolymer/high‐density polyethylene composites

The morphology and mechanical properties of a styrene–ethylene/butylene–styrene triblock copolymer (SEBS) incorporated with high‐density polyethylene (HDPE) particles were investigated. The impact strength and tensile strength of the SEBS matrix obviously increased after the incorporation of the HDPE particles. The microstructure of the SEBS/HDPE blends was observed with scanning electron microscopy and polar optical microscopy, which illustrated that the SEBS/HDPE blends were phase‐separation systems. Dynamic mechanical thermal analysis was also employed to characterize the interaction between SEBS and HDPE. The relationship between the morphology and mechanical properties of the SEBS/HDPE blends was discussed, and the toughening mechanism of rigid organic particles was employed to explain the improvement in the mechanical properties of the SEBS/HDPE blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ultrasonic improvement of the compatibility and rheological behavior of high‐density polyethylene/polystyrene blends

The effects of ultrasonic oscillations on the rheological behavior, mechanical properties, and morphology of high‐density polyethylene (HDPE)/polystyrene (PS) blends were studied. The experimental results show that the die pressure and apparent viscosity of HDPE/PS blends are remarkably reduced in the presence of ultrasonic oscillations and that mechanical properties of the blends are improved. The particle size of the dispersed phase in HDPE/PS blends becomes smaller, its distribution becomes narrower, and the interfacial interaction of the blends becomes stronger if the blends are extruded in the presence of ultrasonic oscillations. Ultraviolet spectra and Soxhlet extraction results show the formation of a polyethylene‐PS copolymer during extrusion in the presence of ultrasonic oscillations, which improves the compatibility of HDPE/PS blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 23–32, 2002     

Structure development and property changes in high‐density polyethylene/calcium carbonate blends during pan‐milling

A new self‐designed mechanochemical reactor, inlaid pan‐mill, was used in studying high density polyethylene (HDPE) and calcium carbonate (CaCO₃) blends. The effects of CaCO₃ on the crushing and structure of HDPE matrix and the properties of HDPE/CaCO₃ blends were investigated. Scanning electron microscopy, Fourier transformed IR spectroscopy, dynamical mechanical testing analysis, capillary rheometer, and Instron material testing system were used to characterize the structure of HDPE and evaluate the properties of HDPE/CaCO₃ blends. The introduction of calcium carbonate during milling improved milling efficiency, and time needed for each cycle was greatly reduced. Oxygen‐containing groups on HDPE chains, which were produced during milling, increased interfacial interactions and improved the dispersion and distribution of calcium carbonate particles in HDPE/CaCO₃ blends. Rheological, thermal, and mechanical properties were also improved. The elongation at break of milled blends with high concentrations of calcium carbonate was significantly higher than that of unmilled blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1459–1464, 1999     

Self‐reinforcement of high‐density polyethylene/low‐density polyethylene prepared by oscillating packing injection molding under low pressure

This article reports the toughness improvement of high‐density polyethylene (HDPE) by low‐density polyethylene (LDPE) in oscillating packing injection molding, whereas tensile strength and modulus are greatly enhanced by oscillating packing at the same time. Compared with self‐reinforced pure HDPE, the tensile strength of HDPE/LDPE (80/20 wt %) keeps at the same level, and toughness increases. Multilayer structure on the fracture surface of self‐reinforced HDPE/LDPE specimens can be observed by scanning electron microscope. The central layer of the fracture surface breaks in a ductile manner, whereas the break of shear layer is somewhat brittle. The strength and modulus increase is due to the high orientation of macromolecules along the flow direction, refined crystallization, and shish‐kebab crystals. Differential scanning calorimetry and wide‐angle X‐ray diffraction find cocrystallization occurs between HDPE and LDPE. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 799–804, 1999     

Mechanical properties of uncrosslinked and crosslinked linear low‐density polyethylene/wax blends

The mechanical properties of uncrosslinked and crosslinked linear low‐density polyethylene (LLDPE)/wax blends were investigated, using differential scanning calorimetry (DSC), tensile testing, and melt flow indexing. A decrease in the degree of crystallinity, as determined from the DSC melting enthalpies, was observed with an increase in the dicumyl peroxide (DCP) concentration. The Young's modulus increased with increased wax portions, and there was a higher increase for crosslinked blends. The yield stress generally decreased with increased peroxide content. Crosslinking caused an increase in elongation at yield, but increased wax content caused a decrease in elongation at yield. The stress at break generally increased with increasing peroxide content, but it decreased with increased wax content. The elongation at break decreased with an increase in the DCP concentration. Melt flow rate measurements indicated a mutual miscibility in LLDPE/wax blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 973–980, 2001     

Degradation behaviors of linear low‐density polyethylene and poly(L‐lactic acid) blends

In this study, the degradability of linear low‐density polyethylene (LLDPE) and poly(L ‐lactic acid) (PLLA) blend films under controlled composting conditions was investigated according to modified ASTM D 5338 (2003). Differential scanning calorimetry, X‐ray diffraction, and Fourier transform infrared spectroscopy were used to determine the thermal and morphological properties of the plastic films. LLDPE 80 (80 wt % LLDPE and 20 wt % PLLA) degraded faster than grafted low‐density polyethylene–maleic anhydride (M‐g‐L) 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) and pure LLDPE (LLDPE 100). The mechanical properties and weight changes were determined after composting. The tensile strength of LLDPE 100, LLDPE 80, and M‐g‐L 80/4 decreased by 20, 54, and 35%, respectively. The films, as a result of degradation, exhibited a decrease in their mass. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

High‐density polyethylene/ultrahigh‐molecular‐weight polyethylene blend. I. The processing,thermal, and mechanical properties

Various blend ratios of high‐density polyethylene (HDPE) and ultrahigh‐molecular‐weight polyethylene (UHMWPE) were prepared with the objective of determining their suitability as biomaterials. Although the presence of HDPE in the blends enabled melt processing, the presence of UHMWPE helped to improve the toughness of the resulting blends. The processability of the blends was investigated with the Brabender torque, which was used as an indication of the optimum blend conditions. The blends were characterized with differential scanning calorimetry. The mechanical tests performed on the blends included tensile, flexural, and impact tests. A 50:50 (w/w) blend yielded optimum properties in terms of the processability and mechanical properties. The tensile property of the 50:50 blend was intermediate between those of HDPE and UHMWPE, but the strain at break increased 200% in comparison with that of both neat resins. The energy at break of the 50:50 blend revealed an improvement in the toughness. The fracture mechanism was also investigated with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 413–425, 2005     

Compatibilization of high‐impact polystyrene/high‐density polyethylene blends by styrene/ethylene–butylene/styrene block copolymer

Compatibilization of polymer blends of high‐impact polystyrene (HIPS) and high‐density polyethylene (HDPE) blend by styrene/ethylene–butylene/styrene (SEBS) was elucidated. Polymer blends containing many ratios of HIPS and HDPE with various concentrations of SEBS were prepared. The Izod impact strength and elongation at break of the blends increased with increases in SEBS content. They increased markedly when the HDPE content was higher than 50 wt %. Tensile strength of blends increased when the SEBS concentration was not higher than 5 pphr. Whenever the SEBS loading was higher than 5 pphr, the tensile strength decreased and a greater decrease was found in blends in which the HDPE concentration was more than 50 wt %. The log additivity rule model was applied to these blends, which showed that the blends containing the HIPS‐rich phase gave higher compatibility at the higher shear rates. Surprisingly, the blends containing the HDPE‐rich phase yielded greater compatibility at the lower shear rates. Morphology observations of the blends indicated better compatibility of the blends with increasing SEBS concentration. The relaxation time (T₂) values from the pulsed NMR measurements revealed that both polymer blends became more compatible when the SEBS concentration was increased. When integrating all the investigations of compatibility compared with the mechanical properties, it is possible to conclude that SEBS promotes a certain level of compatibilization for several ratios of HIPS/HDPE blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 742–755, 2004     

Short‐time fabrication of well‐mixed high‐density polyethylene/ultrahigh‐molecular‐weight polyethylene blends under elongational flow: morphology,mechanical properties and mechanism

As linear polyethylenes, ultrahigh‐molecular‐weight polyethylene (UHMWPE) and high‐density polyethylene (HDPE) have the same molecular structure, but the large difference in viscosity between them makes it difficult to obtain well‐mixed blends. An innovative eccentric rotor extruder (ERE) generating an elongational flow was used to prepare HDPE/UHMWPE blends within short processing times. Compared with the obvious two‐phase morphology of a sample from a twin‐screw extruder observed with a scanning electron microscope, few small UHMWPE particles were observed in the HDPE matrix for a sample from the ERE, indicating the good mixing on a molecular level of HDPE/UHMWPE blends achieved by the ERE during short processing times. The morphological changes of blends prepared using the ERE evidenced the good integration of HDPE and UHMWPE even though the UHMWPE content is up to 50 wt% in the blends. Moreover, all blends retained most of the intrinsic molecular weight. The good mixing was further confirmed from the thermal, crystallization and rheological behaviors determined using differential scanning calorimetry and dynamic rheological measurements. Importantly, the 50/50 blend presented improved mechanical properties, especially super‐impact strength of 151.9 kJ m^?2 with incomplete‐break fracture state. The strengthening and great toughening effects of UHMWPE on the blends were attributed to the addition of unwrapped UHMWPE long molecular chains. The effective disentanglement mechanism of UHMWPE chains under elongational flow was explained schematically by a non‐parallel three‐plate model. © 2019 Society of Chemical Industry