Plastic deformation of low‐density polyethylene reinforced with biodegradable polylactide,Part 2: Creep characterization and modeling

The behavior of low‐density polyethylene (LDPE) and two blends prepared with polylactide (PLA) was determined by means of a novel video‐controlled testing method under stretching at constant true strain rate, under creep at constant true stress, and under creep at constant nominal stress. Most tests were performed at 23°C and 50°C. In this second part, the experimental data are modeled with the G'Sell‐Jonas phenomenological law expressing the axial true stress versus axial true strain and axial true strain rate. This model describes correctly the various deformation stages: (i) initial viscoelasticity, (ii) plastic yielding, and (iii) strain hardening up to rupture. It shows clearly the reinforcing effect of the PLA particles that increases the yield stress in stretching experiments and slows down the deformation kinetics under creep. It is shown how the local stress/strain behavior is related to the standard force/extension curves. Consequently, it is proposed that tensile tests at constant true strain rates should be systematically preferred to creep tests for the characterization of constitutive relations because they take much less time to be performed. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

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     

Binary mixtures of polyethylene and oxidized wax: Dependency of thermal and mechanical properties upon mixing procedure

The influence of the preparation procedure on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)– and LDPE–oxidized wax blends was investigated. It was found that mechanically mixed blends show reduced thermal stability as well as ultimate mechanical properties (stress and strain at break) compared to that of extrusion mixed blends. However, the structure of the blend and consequently its thermal and mechanical behavior also depend on the initial morphology of polyethylene. DSC measurements show miscibility up to high wax contents in both blend types, but increasing the amount of wax in LDPE blends induces increasing crystallinity. As a result, the LDPE/wax blends show improved thermal stability of between 20 and 50°C at low wax concentrations. Although the elasticity modulus of the blends increases, increasing the amount of wax generally degrades the mechanical properties. The main reason for this is the reduced number of tie chains. Changes in the average concentration of tie chains with increasing wax content were calculated and a correlation was made with the ultimate properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2446–2456, 2003     

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     

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.     

Properties of mLLDPE/LDPE blends in film blowing

We evaluated the inline birefringence of two blend systems in film blowing. The first system consisted of a metallocene catalyzed linear low density polyethylene (mLLDPE‐1) and a low density polyethylene (LDPE‐1); the second one was made of a metallocene catalyzed polyethylene containing sparse long chain branches (mLLDPE‐2) and another low density polyethylene (LDPE‐2). Experimental data show that before the crystallization starts, the birefringence of the mLLDPE‐2/LDPE‐2 blends is a linear function of blend composition, suggesting miscibility of the mLLDPE‐2/LDPE‐2 blends. However, the birefringence of the mLLDPE‐1/LDPE‐1 blends shows positive deviations with respect to a linear function of blend composition. This is caused by the existence of form birefringence, suggesting immiscibility of the mLLDPE‐1/LDPE‐1 blends. The nonuniform biaxial elongational viscosity (NUBEV) at the reference temperature of 175°C for LDPE‐1 was evaluated for different operating conditions. The results show that NUBEV is approximately a unique function of the deformation rate, confirming the validity of the assumptions and technique used for the NUBEV calculation. The NUBEV and the nonuniform biaxial Trouton ratio (NUTR) of the mLLDPE‐2/LDPE‐2 blends was also evaluated using the same technique. The NUBEV of all mLLDPE‐2/LDPE‐2 blends shows a strain‐thinning behavior within the deformation rates investigated. Furthermore, the NUTR results show that LDPE‐2 deviates largely from the Newtonian fluid behavior, whereas mLLDPE‐2 is quite close to the Newtonian behavior. Nevertheless, the NUTR of the mLLDPE‐2/LDPE‐2 blends is almost a linear function of blend composition. POLYM. ENG. Sci., 45:343–353, 2005. © 2005 Society of Plastics Engineers     

Improving viscoelasticity and rebound resilience of crosslinked low‐density polyethylene foam by blending with ethylene vinyl acetate and polyethylene‐octene elastomer

To obtain high‐rebound resilience of crosslinking low‐density polyethylene (LDPE) foam and decrease the foam density at the same content of foaming agent, the melt viscoelasticity of LDPE with different compositions (ethylene vinyl acetate [EVA], polyethylene‐octene elastomer, and crosslinking agent) was investigated by dynamic rheology test. Then, LDPE/EVA/(polyethylene‐octene elastomer) foams with different composition ratios were produced by a continuous foaming process and investigated by the rebound resilience test. The results show that the melt viscoelasticity behavior of LDPE and its blends in the molten state possessed more melt elasticity behavior after the crosslinking was introduced. Meanwhile, the rebound resilience of LDPE foam was increased 54% at the lower foam density (0.031 g/cm³). It could meet the requirements of sports mats for high‐rebound resilience (>50%) and decrease the material cost when EVA was introduced into the foaming system. J. VINYL ADDIT. TECHNOL., 22:61–71, 2016. © 2014 Society of Plastics Engineers     

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     

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     

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     

Rheological and thermal properties of single‐site polyethylene blends

Branched polyethylenes, low‐density polyethylenes (LDPE1 and LDPE2) or long‐chain‐branched very low density polyethylenes (VLDPE2), were blended with very low density polyethylenes containing short branches (VLDPE1 and VLDPE3). The rheological and thermal measurements of the pure copolymers and their blends (VLDPE1–LDPE1, VLDPE1–LDPE2, VLDPE1–VLDPE2, and VLDPE2–VLDPE3) were taken by controlled stress rheometry and differential scanning calorimetry, respectively. The shear‐thinning effect became stronger with increasing long‐chain‐branched polymer compositions when it was correlated with the flow behavior index, and the extent of shear thinning was different for each blend set. Stronger shear thinning and a linear composition dependence of the zero‐shear viscosity were observed for the VLDPE1–LDPE1 and VLDPE1–LDPE2 blends. These blends followed the log additivity rule, and this indicated that they were miscible in the melt at all compositions. In contrast, a deviation from the log additivity rule was observed for the VLDPE1–VLDPE2 blend compositions with 50% or less VLDPE2 and for the VLDPE3–VLDPE2 blends with 50% or more VLDPE2. The thermal properties of the blends were consistent with the rheological properties. VLDPE1–LDPE1 and VLDPE1–LDPE2 showed that these blends were characteristic of a single‐component system at all compositions, whereas the phase separation (immiscibility) was detected only for VLDPE1–VLDPE2 blends with 50% or less VLDPE2 and for VLDPE3–VLDPE2 blends with 50% or more VLDPE2. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1549–1557, 2005     

Effects of glycerol and PE‐g‐MA on morphology,thermal and tensile properties of LDPE and rice starch blends

The effects of glycerol and polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the morphology, thermal properties, and tensile properties of low‐density polyethylene (LDPE) and rice starch blends were studied by scanning electron microscopy (SEM), differential scanning calorimetry, and the Instron Universal Testing Machine, respectively. Blends of LDPE/rice starch, LDPE/rice starch/glycerol, and LDPE/rice starch/glycerol/PE‐g‐MA with different starch contents were prepared by using a laboratory scale twin‐screw extruder. The distribution of rice starch in LDPE matrix became homogenous after the addition of glycerol. The interfacial adhesion between rice starch and LDPE was improved by the addition of PE‐g‐MA as demonstrated by SEM. The crystallization temperatures of LDPE/rice starch/glycerol blends and LDPE/rice starch/glycerol/PE‐g‐MA blends were similar to that of pure LDPE but higher than that of LDPE/rice starch blends. Both the tensile strength and the elongation at break followed the order of rice starch/LDPE/glycerol/PE‐g‐MA blends > rice starch/LDPE/glycerol > LDPE/rice starch blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 344–350, 2004     

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     

Effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on thermal properties,morphology, and tensile properties of low‐density polyethylene (LDPE) and corn starch blends

The effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the thermal properties, morphology, and tensile properties of blends of low‐density polyethylene (LDPE) and corn starch were studied with a differential scanning calorimeter (DSC), scanning electron microscope (SEM), and Instron Universal Testing Machine, respectively. Corn starch–LDPE blends with different starch content and with or without the addition of PE‐g‐MA were prepared with a lab‐scale twin‐screw extruder. The crystallization temperature of LDPE–corn starch–PE‐g‐MA blends was similar to that of pure LDPE but higher than that of LDPE–corn starch blends. The interfacial properties between corn starch and LDPE were improved after PE‐g‐MA addition, as evidenced by the structure morphology revealed by SEM. The tensile strength and elongation at break of corn starch–LDPE–PE‐g‐MA blends were greater than those of LDPE–corn starch blends, and their differences became more pronounced at higher starch contents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2904–2911, 2003     

Modification of low‐density polyethylene by graft copolymerization with maleic anhydride and blends with polyamide 6

Modification of low‐density polyethylene (LDPE) hyperbranched grafting with a maleic anhydride (MAH) was carried out using corotating twin screw extruder in the presence of benzoyl peroxide. The LDPE/polyamide 6 (PA6) and LDPE‐g‐MAH/PA6 blends were obtained with a corotating twin screw extruder. The melt viscosity of the grafted LDPE was measured by a capillary rheometer. The grafted copolymer was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy The effects of variations in temperature, PA6 loading, and benzoyl peroxide and MAH concentration were investigated. The results show that most MAH monomers were grafted onto the LDPE at a lower MAH concentration. With the proper selection of the reaction parameters, we obtained a grafting degree higher than 4.9%. Mechanical test results indicate that the blends had good interfacial adhesion and good stability of the phase structure during heating, which was reflected in the mechanical properties. Furthermore, the results reveal that the tensile strength of the blends increased continuously with increasing PA6 content. Moreover, the home‐synthesized maleated LDPE could be used for the compatibilization of LDPE/PA 6 blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological and mechanical characteristics of low density polyethylene/ethylene‐vinyl acetate/organoclay nanocomposites

Attempts were made to trace the effect of organoclay (OC) on the rheological and mechanical behaviors of the low density polyethylene (LDPE)/ethylene‐vinyl acetate (EVA) blends. To do this effectively, in addition to LDPE/EVA/OC system, pure LDPE and LDPE/EVA blends were also examined as model systems. The rheological behavior was determined by the capillary rheometer. Morphological characterization was also carried out using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and theoretical approach based on interfacial energies. Shear viscosity, tensile strength and elastic modulus of LDPE/EVA were found to decrease by increasing the EVA content, while for LDPE/EVA/OC ternary nanocomposites, such properties showed an increase by increasing the content of EVA. Such behavior was explained by the morphological characteristic of the system in which OC was mainly intercalated/exfoliated in the EVA phase. This morphological characteristic was corroborated by the XRD, TEM and interfacial energies data. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Compatibilization of low‐density polyethylene/plasticized starch blends by reactive compounds and electron beam irradiation

Blends based on various compositions of low‐density polyethylene (LDPE) and plasticized starch (PLST) were prepared by melt extrusion and molding in the form of sheets under hot press. The rheology properties during mixing were studied in terms of torque and temperature against mixing time. The structural properties of LDPE/PLST blends before and after electron beam irradiation was characterized by IR spectroscopy, tensile mechanical testing, and scanning electron microscopy (SEM). The torque‐time curves during the mixing process showed that the values of torque in the first region of mixing for pure LDPE or LDPE/PLST blends are higher in the presence of the compatibilizer PEMA than that in the presence of EVA. In addition, the stability of mixing was attained after a short time in the presence of PEMA. The IR spectroscopy suggests that the compatibilization by EVA and PEMA compounds proceeds through the formation of hydrogen bonding during mixing and this compatibility was improved after electron beam irradiation. The stress–strain curves of pure LDPE and its blends with PLST showed the behavior of tough polymers with yielding properties. The SEM micrographs of the fracture surfaces give supports to the effect of EVA and PEMA as compatibilizers and the effect of electron beam irradiation. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Elongational rheology of LLDPE / LDPE blends

The objective of this study is to investigate the effect of low density polyethylene (LDPE) content in linear low density polyethylene (LLDPE) on the crystallinity and strain hardening of LDPE / LLDPE blends. Three different linear low density polyethylenes (LL‐1, LL‐2 and LL‐3) and low density polyethylenes (LD‐1, LD‐2 and LD‐3) were investigated. Eight blends of LL‐1 with 10, 20, 30 and 70 wt % of LD‐1 and LD‐3, respectively, were prepared using a single screw extruder. The elongational behavior of the blends and their constituents were measured at 150°C using an RME rheometer. For the blends of LL‐1 with LD‐1, the low shear rate viscosity indicated a synergistic effect over the whole range of concentrations, whereas for the blends of LL‐1 with LD‐3, a different behavior was observed. For the elongational viscosity behavior, no significant differences were observed for the strain hardening of the 10–30% LDPE blends. Thermal analysis indicated that at concentrations up to 20%, LDPE does not significantly affect the melting and crystallization temperatures of LLDPE blends. In conclusion, the crystallinity and rheological results indicate that 10–20% LDPE is sufficient to provide improved strain hardening in LLDPE. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3070–3077, 2003     

Oxidative degradations of oxodegradable LDPE enhanced with thermoplastic pea starch: Thermo‐mechanical properties,morphology, and UV‐ageing studies

The abiotic UV‐degradation behavior of oxodegradable LDPE was investigated in the presence of thermoplastic pea starch (TPPS) in this study. Oxodegradable LDPE was first melt‐blended with thermoplastic pea starch (TPPS) using an internal mixing chamber to enhance the abiotic oxidative degradation of oxodegradable LDPE. Because of their different affinity, maleated polyethylene was added as compatibilizer. Tensile properties, thermal properties, and morphology of resulting melt‐blends were determined at different content in TPPS. High content in TPPS (40 wt %) could be readily added to oxodegradable LDPE without affecting the tensile properties of resulting melt‐blends. UV‐ageing studies on compatibilized TPPS/oxodegradable LDPE melt‐blends were carried out by Attenuated Total Reflectance infrared spectroscopy (ATR‐FTIR), Dynamic Thermomechanical Analyses (DMTA) and Differential Scanning Calorimetry (DSC) under abiotic conditions. These results suggested a synergistic effect on the UV‐ageing of TPPS‐based melt‐blends provided by both components during the first stage of UV‐irradiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Positive temperature coefficient effect and interaction based on low‐density polyethylene/graphite powder composites

In this article, the positive temperature coefficient (PTC) and interaction based on low‐density polyethylene (LDPE) filled with the loading of graphite (G) powder have been investigated. The dependence of the room temperature resistivity on filler content showed the significant decrease. The PTC behavior enhanced with increasing graphite content but this was not always the case. The maximum PTC effect was observed in LDPE/G composites (G, 45 wt %) with the relatively low room temperature resistivity. The thermal behavior was measured by differential scanning calorimetry (DSC). The structure characteristic for LDPE/G composites was examined by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (SEM), and stress–strain test. The fact was revealed that the slight interaction between LDPE matrix and graphite may lead to change the thermal‐electric properties of the PTC materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012