Mixing in reactive extrusion of low-density polyethylene melts: Linear vs. branched

The melt flows of linear low-density polyethylene (LLDPE) and branched low-density polyethylene (LDPE) have been compared in a fully intermeshing co-rotating twin-screw extruder. The polyethylene melts were selected in order to investigate the effects of the melt rheology on the mixing. Their shear vicosity curves are quite similar, but the LDPE has a markedly higher apparent extensional viscosity over a wide range of stretch rates. The stagger of the paddles in the mixing zone of the extruder creates axial pressure-driven axial flow can have significant extensional strain components. Residence time distributions obtained in the melt zones of the extruder with tracer dye reveal that the LDPE has a narrower residence time distribution than the LLDPE over a wide range of operating conditions. The axial dispersion for the LDPE is significantly lower than the axial dispersion for the LLDPE. This is attributed to the greater extensional viscosity of the LDPE. During the reactive extrusion process, solid maleic anhydride and polyethylene were added at the feed port but the peroxide provides better control of the crosslinking reaction. Residence time distributions measured for the chemically more reactive LLDPE melt indicate reduced levels of axial mixing with reaction. The reduction in mixing is due to a crosslinking reaction that occurs in parallel to the grafting reaction. This change in mixing is smaller than the difference in mixing between LDPE and LLDPE.     

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.     

Comparison between a linear and a branched low-density polyethylene

Two low-density polyethylenes, a linear low-pressure (LLDPE) and a branched high-pressure (LDPE), have been compared. Their shear and extensional behavior and melt fracture phenomena have been investigated, and some mechanical and optical properties of their blown films have been measured. The rheological analysis showed major differences between the samples, both in shear viscosity and in elongational viscosity. The LLDPE exhibited two types of melt fracture, the first of which—a fine scale extrudate roughness—was not shown by the LDPE and appeared at a very low shear rate. The concomitance in LLDPE of a high shear viscosity and a low elongational viscosity and the presence of melt fracture at low shear rate resulted in its more difficult processing into film. The mechanical properties of the LLDPE film approached those of high-density polyethylene while the optical characteristics were in the range of LDPE. Such a coexistence of properties makes LLDPE an interesting material for film production.     

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

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

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

Elongation viscosity estimates of linear low-density polyethylene/ low-density polyethylene blends

The elongational viscosity (EV) of two series of linear low-density polyethylene/low-density polyethylene blends was estimated using an entry flow analysis. The difference, t ? n, between the power law index t of the elongational viscosity and the power law index n of the viscosity, is proportional to the LDPE content for both series of blends investigated. Comparison of the EV of the LLDPE/LDPE blend estimated from the analysis of the flow into an orifice die to the EV value estimated from the analysis of the flow into a capillary die with a flat entry, showed that the difference in geometry had little effect on the EV estimates.     

Rheological aspects and film processability of poly (lactic acid)/linear low-density polyethylene blends

Poly (lactic acid) (PLA) and Linear low-density polyethylene (LLDPE) were compounded in a corotating twin screw extruder. PE-g-glycidyl methacrylate was also added as a reactive compatibilizer in PLA/LLDPE blend system, which lowered interfacial tension between PLA and LLDPE. Blown films were prepared by using a single-screw extruder for all compounded blends. The investigation of the rheological properties of a polymeric system is very important to study the processability and understand structure-property relationship in blown films. In the present research work, the rheological properties have been investigated to assess the processability of blown films of PLA/LLDPE blends. Oscillatory shear rheology viscoelastic spectra showed an increase in the storage and loss moduli with the increase in LLDPE and compatibilizer content, which indicated pronounced viscoelastic behavior of PLA with the addition of LLDPE and compatibilizer. A steady increase in the value of extensional viscosity as a function of time was observed with the addition of LLDPE and compatibilizer in PLA. The blends with higher LLDPE content exhibited much more prominent strain hardening characteristics than those with lower LLDPE content.     

Effects of the processing conditions and blending with linear low-density polyethylene on the properties of low-density polyethylene films

Effects of blending low-density polyethylene (LDPE) with linear low-density polyethylene (LLDPE) were studied on extrusion blown films. The tensile strength, the tear strength, the elongation at break, as well as haze showed more or less additivity between the properties of LDPE and LLDPE except in the range of 20–40% where synergistic effects were observed. The LLDPE had higher tensile strength and elongation at break than did the LDPE in both test directions, as well as higher tear strength in the transverse direction. The impact energies of the LLDPE and the LDPE were approximately the same, but the tear strength of the LLDPE was lower than that of LDPE in the machine direction. The comparative mechanical properties strongly depend on the processing conditions and structural parameters such as the molecular weight and the molecular weight distribution of both classes of materials. The LLDPE in this study had a higher molecular weight in comparison to the LDPE of the study, as implied from its lower melt flow index (MFI) in comparison to that of the LDPE. The effects of processing conditions such as the blow-up ratio (BUR) and the draw-down ratio (DDR) were also studied at 20/80 (LLDPE/LDPE) ratio. Tensile strength, elongation at break, and tear strength in both directions became equalized, and the impact energy decreased as the BUR and the DDR approached each other.     

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

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

Cocrystallization and miscibility studies of blends of ultrahigh molecular weight polyethylene with conventional polyethylenes

Ultrahigh molecular weight polyethylene (UHMWPE) was mechanically mixed with conventional polyethylenes (LLDPE, HDPE, and LLDPE) using an internal mixer. Rheological studies of these blends suggest that UHMWPE seems to be miscible with LLDPE, HDPE, and LDPE in the melt state. Yield characteristics are observed in all blend systems, particularly in high UHMWPE blend compositions. Differential scanning calorimetry and small-angle light scattering studies show that cocrystallization takes place in the blends of UHMWPE/LLDPE and UHMWPE/HDPE blends. However, separate crystals are formed in UHMWPE/LDPE. The formation of separate crystals may be attributed to long chain branching of conventional low-density polyethylene. Tensile properties of the former two blends vary almost linearly with blend compositions, while deviations are seen in the latter UHMWPE/LDPE blends.     

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     

Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties

Novel degradable materials based on ternary blends of natural rubber (NR)/linear low-density polyethylene (LLDPE)/thermoplastic starch (TPS) were prepared via simple blending technique using three different types of natural rubber (i.e., unmodified natural rubber (RSS#3) and ENR with 25 and 50 mol% epoxide). The evolution of co-continuous phase morphology was first clarified for 50/50: NR/LLDPE blend. Then, 10 wt% of TPS was added to form 50/40/10: NR/LLDPE/TPS ternary blend, where TPS was the particulate dispersed phase in the NR/LLDPE matrix. The smallest TPS particles were observed in the ENR-50/LLDPE blend. This might be attributed to the chemical interactions of polar functional groups in ENR and TPS that enhanced their interfacial adhesion. We found that ternary blend of ENR-50/LLDPE/TPS exhibited higher 100 % modulus, tensile strength, hardness, storage modulus, complex viscosity and thermal properties compared with those of ENR-25/LLDPE/TPS and RSS#3/LLDPE/TPS ternary blends. Furthermore, lower melting temperature (T _m) and heat of crystallization of LLDPE (?H) were observed in ternary blend of ENR-50/LLDPE/TPS compared to the other ternary blends. Also, neat TPS exhibited the fastest biodegradation by weight loss during burial in soil for 2 or 6 months, while the ternary blends of NR/LLDPE/TPS exhibited higher weight loss compared to the neat NR and LLDPE. The lower weight loss of the ternary blends with ENR was likely due to the stronger chemical interfacial interactions. This proved that the blend with ENR had lower biodegradability than the blend with unmodified NR.     

Linear-low-density polyethylene melt rheology: Extensibility and extrusion defects

This paper investigates three aspects of linear-low-density polyethylene (LLDPE) rheological properties: shear viscosity variations with shear rate and temperature, tensile behavior determined with an extensiometer, and extrusion defects. The differences in shear viscosity variation with shear rate and temperature between LLDPE and LDPE (low-density polyethylene) are shown. These differences, attributed to wider molecular weight distribution and to long chain branching (LCB) in LDPE, involve different extrusion behaviors. The lack of LCB in LLDPE can be demonstrated by comparison of the measured Newtonian viscosity with the value of the same parameter calculated from molecular weight distribution and composition law of Newtonian viscosities. The lack of LCB leads to good melt extensibility, which is shown by tensile properties of polyethylene melts determined with a non-isothermal extensiometer. The melt fracture phenomenon is studied because it promotes surface defects on bubbles in film application. Extrudate distortions are examined at the laboratory extruder outlet. This test shows differences between LLDPE and LDPE, but also between some LLDPE samples.     

Linear low-density polyethylene/high-density polyethylene blends: Effect of high-density polyethylene content on die swell and flow instability

This work aimed to evaluate the effect of high-density polyethylene (HDPE) content and of shear rate on the die swell and flow instability of linear low-density polyethylene (LLDPE)/HDPE blends. The results showed that the die swell of the LLDPE/HDPE blends increased with the increase in the shear rate. At high shear rates, the increase in the HDPE content led to an increase in the die swell of LLDPE/HDPE blends. The surface morphology analysis of the extrudates by optical and scanning electron microscopy revealed the presence of sharkskin and stick–slip flow instabilities in LLDPE and LLDPE/HDPE blends at the shear rates investigated. These instabilities were attenuated with the addition of HDPE and almost disappeared in the LLDPE/HDPE blend containing 50 wt% of HDPE.     

Physical properties of poly(ethylene adipate)/low-density polyethylene blends

Mechanical and rheological properties of poly(ethylene adipate) (PEA)/low-density polyethylene (LDPE) blends were investigated. DSC results showed that there is no miscibility between PEA and LDPE. Tensile strength decreases with increasing PEA content, while the modulus increases. Elongation at break decreases with increasing PEA content. A rheological constitutive equation was used for describing and predicting the steady-state shear viscosity of PEA/LDPE blend. The suggested equation was successfully able to describe and predict viscosity of the blend as functions of shear rate and temperature. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1745–1750, 1997     

BMDPE／LDPE／LLDPE共混熔体的流变行为与力学性能

研究了双峰中密度聚乙烯（BMDPE），低密度聚乙烯（LDPE）与线型低密度聚乙烯（LLDPE）共混熔体的流变行为和力学性能，讨论了共混物的组成，剪切应力和剪切速率以及温度对熔体流变行为，熔体粘度和膨胀比的影响，测定了不同配比熔体的非牛顿指数，熔体流动速率，粘流活性能及屈服应力，断裂应力和断裂伸长率，为BMDPE的加工和使用以及开发高性能价格比的PE材料提供了依据。     

Tensile stress measurements on linear and branches low-density polyethylene melts. Interpretation of results with a generalized Maxwell model

Dynamic shear experiments in the linear range of deformation and extensional tests at constant strain rate have been carried out on a linear low-density polyethylene (LLDPE) melt and on two branched low-density polyethylene (LDPE) melts with different amounts of long-chain branching. Both the dynamic shear moduli and the tensile stress obey the time–temperature superposition principle. A simple model based on a nonaffine generalized Maxwell model with two relaxation times is proposed to describe the rheological behavior in elongation of these melts. Close agreement between the model and the experimental data can be obtained by adjusting the two relaxation times and the “slip parameter” of entanglements. The variations of these parameters with strain rate and their relationship with molecular structure are discussed.     

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     

Melt spinning flow behaviour of high-density polyethylene blended with low-density polyethylene

ABSTRACT

The melt spinning flow behaviour of a high-density polyethylene (HDPE) blended with a low-density polyethylene (LDPE) was studied using a melt spinning technique in temperature ranging from 160 to 200°C and die extrusion velocity varying from 9 to 36?mm?s^?1. The results showed that the melt apparent extension viscosity of the blends was higher than those of the LDPE and HDPE; the melt apparent extension viscosity decreased with increasing temperature; while the melt apparent extension viscosity increased with increasing extension strain rate when the extension strain rate was lower than 0.2?s^?1, and then decreased; the melt apparent extension viscosity reached up to a maximum value when extension strain rate was about 0.2?s^?1; the relationship between the melt apparent extension viscosity and the LDPE weight fraction did not follow the mixing rule.     

Rheology modifier additive for enhanced processability of polyethylene for blown-Film applications

Polyethylene is a versatile polymer suitable for a large variety of flexible and rigid packaging applications. Its mechanical and rheological properties can be tuned across a wide range by controlling its molecular architecture, such as the amount and distribution of olefinic comonomers (short chain branching), long chain branching, and molecular weight distribution. Linear low-density polyethylene (LLDPE) is known for its high toughness which enables downgauged film structures and low-density polyethylene (LDPE) is known for its excellent shear thinning and melt strength which enables enhanced processability and high throughput, such as on blown film lines. In order to obtain a balance of toughness and processability on films produced on blown film lines, blends of LLDPE and LDPE are commonly used. In this paper, we describe additive-based approaches, including a new product, DOWLEX™ (TM = trademark of the Dow Chemical Company (“Dow”) or an affiliated company of Dow) GM AX01, which enhances melt strength and other rheological properties of polyethylene, enabling fabrication of films with lower LDPE content while still maintaining excellent rheological properties and higher toughness versus conventional LLDPE/LDPE blends. The higher toughness enables downgauging without loss of mechanical properties, which in turn reduces consumption of polymer resulting in a more sustainable solution.