Rheological behavior and mechanical properties of high‐density polyethylene blends with different molecular weights

The dynamic rheological and mechanical properties of the binary blends of two conventional high‐density polyethylenes [HDPEs; low molecular weight (LMW) and high molecular weight (HMW)] with distinct different weight‐average molecular weights were studied. The rheological results show that the rheological behavior of the blends departed from classical linear viscoelastic theory because of the polydispersity of the HDPEs that we used. Plots of the logarithm of the zero shear viscosity fitted by the Cross model versus the blend composition, Cole–Cole plots, Han curves, and master curves of the storage and loss moduli indicated the LMW/HMW blends of different compositions were miscible in the melt state. The tensile yield strength of the blends generally followed the linear additivity rule, whereas the elongation at break and impact strength were lower than those predicted by linear additivity; this suggested the incompatibility of the blends in solid state. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

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     

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     

Melt strength of linear low‐density polyethylene/low‐density polyethylene blends

Linear low‐density polyethylenes and low‐density polyethylenes of various compositions were melt‐blended with a batch mixer. The blends were characterized by their melt strengths and other rheological properties. A simple method for measuring melt strength is presented. The melt strength of a blend may vary according to the additive rule or deviate from the additive rule by showing a synergistic or antagonistic effect. This article reports our investigation of the parameters controlling variations of the melt strength of a blend. The reciprocal of the melt strength of a blend correlates well with the reciprocal of the zero‐shear viscosity and the reciprocal of the relaxation time of the melt. An empirical equation relating the maximum increment (or decrement) of the melt strength to the melt indices of the blend components is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1408–1418, 2002     

Influence of side‐chain structures on the viscoelasticity and elongation viscosity of polyethylene melts

Metallocene‐catalyzed, low‐density and linear low‐density polyethylenes with similar melt indexes were used to investigate how side‐chain structures influence the elongation viscosity and viscoelastic properties. The viscoelastic properties were determined with a rotation rheometer, while the elongation viscosities were acquired by using isothermal fiber spinning. The Phan‐Thien‐Tanner (PTT) model was also used to understand how the side‐chain structure affects the elongation behavior. Experimental results demonstrate that the log G′ vs. log G″ plot can qualitatively describe the effects of the side chain branch on the rheological properties of polyethylene melts. According to the results determined by the PTT model, low‐density polyethylene (LDPE) has low elongation viscosities at high strain rates. This low elongation viscosity can be attributed to the fact that LDPE has high shear thinning behavior. The long‐chain branching tends to increase entanglements, thereby enhancing the storage modulus, elongation viscosity and shear‐thinning behaviors. Uniform side‐chain distribution lowers the entanglements, which results in a low storage modulus, elongation viscosity and shear‐thinning behavior.     

Linear low density polyethylenes and their blends: Part 4 shear flow of LLDPE blends with LLDPE and LDPE

The steady state and dynamic shear behavior of linear low density polyethylenes (LLDPE) blended with low density polyethylene (LDPE) and with another LLDPE resin were measured in capillary and parallel plate geometries at T = 150, 190, and 230°C. The extrudate swell and the Bagley correction were determined. It was observed that the pressure correction plays a significant role in capillary flow of LLDPE/LDPE blends–an indication of immiscibility. Several other rheological functions also suggested a phase separation for the system. Nevertheless, the blend behaved as a “compatible” mixture of emulsion type. By contrast, blends of two LLDPE resins show expected miscibility. However, even in this case additivity was not always observed. A new simple method of calculating the relaxation spectrum was developed. The method is analytical and its accuracy depends on adequacy of the semiempirical relation (proposed previously) to describe dynamic viscosity dependence on the test frequency. For all samples the spectrum allowed computation of storage modulus in good agreement with experimental findings.     

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     

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     

Study of mechanical and rheological behaviors of linear and branched polycarbonates blends

A study of the mechanical and rheological properties of linear and branched polycarbonates blends is presented. Phase separations of the blends were checked through DSC and SEM, and, subsequently, mechanical and rheological properties were investigated. Phase separations were not observed in the blends. The mechanical properties were examined through tensile, flexural, and impact tests. All the mechanical properties of the blends were relatively independent of the compositions. For study of the rheological properties, melt viscosity, storage and loss moduli, and melt tension of the blends with various compositions were examined at various temperatures. The dependence of the viscosity on the molecular weight was also studied. As the content of branched polycarbonate increases, the dependence of the viscosity on the molecular weight and the shear thinning behavior became more marked. Melt tensions were also increased as the branched polycarbonate content increased in the blends for all tested temperatures. In this study, the blend systems which have same mechanical properties but different rheological properties can be obtained through blending of linear and branched polycarbonates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1814–1824, 2001     

Rheological and calorimetric evidences of the fractionated crystallization of iPP dispersed in ethylene/α-olefin copolymers

In this work, the melt crystallization of immiscible blends of isotactic polypropylene (iPP) and branched polyethylenes (PE) was followed by oscillatory shear measurements during controlled cooling. All the blends contained 20% iPP finely dispersed in several ethylene/α-olefin copolymer matrices (with and without a nucleating agent) with densities ranging from 0.88 to 0.92 g/cm³ (linear low, very low, and ultra low density polyethylenes: LLDPE, VLDPE, and ULDPE). The rheological results were compared with parallel differential scanning calorimetry (DSC) measurements at the same cooling rate. During preliminary evaluations of the neat resins, no effect was found of the variation of the frequency of oscillation or the applied shear strain on their crystallization (at least in the range explored in this work). In the case of the blends, when the iPP crystallized in a fractionated fashion, only one sudden increase in the storage modulus (G′) was observed during cooling due to the partial coincident crystallization of both iPP and the PE matrix. In the presence of a nucleating agent, an almost complete separation between the crystallization of both components in the blend was achieved and two increases in G′ were clearly observed upon cooling. A close match between the dynamic crystallization kinetics obtained by DSC and torsion rheometry was demonstrated by a direct comparison between calorimetrically measured solid conversion and G′ during cooling from the melt. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2481–2493, 1997     

Shear and elongational rheology of polyethylenes with different molecular characteristics. I. Shear rheology

Four metallocene polyethylenes (PE), one conventional low density polyethylene (LDPE), and one conventional linear low density polyethylene (LLDPE) were characterized in terms of their complex viscosity, storage and loss moduli, and phase angle at different temperatures. The effects of molecular weight, breadth of molecular weight distribution, and long‐chain branching (LCB) on the shear rheological properties of PEs are studied. For the sparsely long‐chain branched metallocene PEs, LCB increases the zero‐shear viscosity. The onsets of shear thinning are shifted to lower shear rates. There is also a plateau in the phase angle, δ, for these materials. Master curves for the complex viscosity and dynamic moduli were generated for all PE samples. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Shear and elongational behavior of linear low-density and low-density polyethylene blends from capillary rheometry

In this work we present an experimental study of shear and apparent elongational behavior of linear low-density (LLDPE) and low-density (LDPE) polyethylene blends by means of capillary rheometry. The characterization of these rheological properties is crucial in the design of a blend that combines the ease of processing of LDPE with the mechanical advantages of the LLDPE. Two different low-density polyethylenes and one common linear low-density polyethylene were used to prepare the blends. The results obtained indicate a strong sensitivity of the rheology of the blend to changes in the molecular weight of the LDPE employed. For the higher molecular weight LDPE, the shear viscosity of the blend was essentially equal to that of the LDPE homopolymer up to a concentration of 25% of LLDPE, whereas the apparent extensional viscosity was appreciably lower. For the lower molecular weight LDPE, the same trend was obtained regarding the shear viscosity, but in this case the apparent extensional viscosity of the blend was somewhat higher than that of the LDPE homopolymer.     

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     

Study of the miscibility and mechanical properties of NBR/HNBR blends

In this study, hydrogenated acrylonitrile butadiene rubber (HNBR, ZETPOL‐2010L) and nitrile butadiene rubber (NBR, NIPOL‐DN4555) were blended at different ratios in a Haake melt blender at 130°C. The HNBR and the NBR were of very similar acrylonitrile content and Mooney viscosity. The melt miscibility and solid‐state properties were investigated by rheological, thermal, and mechanical testing and scanning electron microscopy (SEM) techniques. The dynamic viscosity of the blends followed the log‐additivity rule, while the flow activation energy closely followed the inverse additivity rule. On the other hand, the storage modulus showed synergistic effects at all compositions, suggesting the presence of emulsion morphology at both ends of the composition range. For the 50/50 HNBR/NBR blend, the SEM micrographs suggest a uniform elongated structure. The thermal analysis showed the presence of two glass transitions, representing the pure components, at all blend ratios, suggesting the absence of segmental miscibility of the blends. The small‐strain mechanical properties such as tensile modulus and yield stress followed linear additivity. However, HNBR and HNBR‐rich blends were observed to strain harden at a rate higher than that of NBR. Induced crystallization of HNBR was suggested to be the reason for the strain hardening. The different rheological, thermal, and mechanical testing techniques agree in suggesting that the structurally similar HNBR and NBR are not thermodynamically miscible but mechanically compatible. Polym. Eng. Sci. 44:2346–2352, 2004. © 2004 Society of Plastics Engineers.     

Melt rheology of poly(lactic acid): Consequences of blending chain architectures

The rheology of blends of linear and branched poly(lactic acid) (PLA) architectures is comprehensively investigated. Measurement of the melt rheological properties of PLA is complicated by degradation effects but the addition of 0.35 wt% tris(nonylphenyl) phosphite (TNPP) provides excellent stabilization over a range of temperatures. Master curves of dynamic viscosity constructed using time‐temperature superposition show significant dispersion for unstabilized samples; this behavior is accompanied by a loss of molecular weight. TNPP stabilized samples show excellent superposition throughout the entire frequency range and minimal loss in molecular weight. For the linear architecture, the Cox‐Merz rule is valid for a large range of shear rates and frequencies. The branched architecture deviates from the Cox‐Merz equality and blends show intermediate behavior. Both the zero shear viscosity and the elasticity (as measured by the recoverable shear compliance) Increase with increasing branched content. The viscosities of both the unstabilized samples and the TNPP stabilized samples roughly obey a log additivity mixing rule. The recoverable shear compliance is monotonic in blend composition and a mixing rule for this property is also presented. For the linear chain, the compliance is independent of temperature but this behavior is apparently lost for the branched and blended materials. Tensile and thermal properties of the blends are also measured and found to be roughly equal within the statistical error of the experiments. The results suggest that excellent control over rheological behavior of PLA is possible through blending chain architectures without compromising mechanical properties.     

Rheological study of the miscibility of LLDPE/LDPE blends and the influence of Tmix

The miscibility of LLDPE and LDPE blends and the influence of mixing temperature (T_mix) are discussed. Adequate amounts of antioxidants were added during melt blending. Dynamic and steady shear measurments were carried out at 190°C in a Rheometrics Mechanical Spectrometer 800.The dependence of rheological properties on blend composition indicated that blends of LLDEPE (butene) and LDPE mixed at 190°C and 220°C are only partially miscible; immiscibilty is likely to occur around the 50/50 composition and in the LDPE‐rich blends. Blends at 190°C are likely miscible in the LLDPE‐rich range. Tncreaasing T_mix did improve the miscibility of LLDPE/LDPE blends at 190°C or influence the dynamic sher properties (η′ or G′) of the “pure” resins of blends. Suggested that the molecular order [see Hussein and Williams, J. Non‐Newt. Fluid Mech., 86 105 (1999); Hussein and Williams, Macromol. Rapid Commun., 19 , 323 (1998)] and mismatch of the molecular conformations of different polyethylene structures provide an explanation for the immiscibility of polyethylenes. Agreement was observed between themeasured dynamic properities and theortical predictions of Palierne and Bousmina‐Karner emulsion models.     

Miscibility analysis in LLDPE/LDPE blends via thermorheological analysis: Correlation with branching structure

This article describes correlation between thermorheological properties and the miscibility of LLDPE/LDPE blends. Samples of LLDPE/LDPE with the blending ratio of 5/95, 10/90, 25/75, 50/50, 75/25, and 90/10 were prepared via melt mixing in a twin screw extruder. Both applied polyethylenes are varying in their long‐chain branches. Five methods including the time–temperature superposition (TTS) principle, van Gurp–Palmen plot, Cole–Cole curve, zero‐shear viscosity as a function of concentration, and relaxation spectrum were employed to examine the miscibility behavior of the samples. The results obtained by these methods indicated the immiscibility of the LLDPE/LDPE blends except the one with 10 wt% LLDPE content. Moreover, Scholz and Einstein models used for further checking of miscibility of the blends showed consistent results. Also, by using the Scholz model, the value of α/R, ratio of interfacial tension to droplet radius, for the blend with 95 wt% LLDPE content was estimated as 876 N m^?2 that was comparable with prior values found for LLDPE/LDPE blends. The potential of thermorheological approach as an alternative powerful tool for analyzing LCB and miscibility issues in PE blends could be highlighted. POLYM. ENG. SCI., 54:1081–1088, 2014. © 2013 Society of Plastics Engineers     

Phase diagrams of polyethylene blends by Raman spectroscopy

Summary The Raman internal mode region analysis of polyethylene (PE) is extended to studies of blends of different PEs so as to obtain a phase diagram showing the magnitude of crystalline (P_c), amorphous (P_a) and interfacial (P_b) phases at different compositions. The non-cocrystallizable HDPE/LDPE blends shows additivity in phase structure with blend composition. Enlarged share of P_b is seen for compatible blends of HDPE/LLDPE and especially for HDPE with VLDPE of low crystallinity. This method offers an easy access to direct observing compatibility of different PEs on a molecular level. Supported by Chinese Petrochemical Corporation (SINOPEC)     

Thermorheology as a method to analyze long-chain branched polyethylenes

This paper presents correlations between polyethylenes of different compositions and branching architectures and their viscoelastic behavior in dependence on the temperature and demonstrates how effectively rheological experiments can be used for analytical purposes. Long-chain branched polyethylenes are known to be thermorheologically complex. But the thermorheological complexity of long-chain branched linear low-density metallocene polyethylenes (LCB-mLLDPE) differs from that of low-density polyethylenes (LDPE) in the way that the activation energy of LDPE becomes constant by a temperature-dependent modification of the moduli whereas a constant activation energy cannot be obtained for LCB-mLLDPE. These findings are explained by the assumption that the LCB-mLLDPE investigated consist of at least two species with distinctly different activation energies. This interpretation is supported by the thermorheological analysis of a blend of known parts of an LDPE and a linear low-density polyethylene (LLDPE). A thermorheological complexity was found similar to that of the LCB-mLLDPE which reflects the different activation energies of the two components. Results of that kind make it possible to get information on the composition of LCB-mLLDPE not available from common analytical methods.