Rheological properties of blown film low-density polyethylene resins

Three blown-film-grade low-density-polyethylene (LDPE) resins were studied using different rheological techniques. Eccentric rotating disks (ERD), cone-plate viscometry, capillary rheometry, annular die extrusion, and non-isothermal stretching of a filament were used. The viscoelasticity of the melts was found to play a dominant role in the observed behavior. Extrudate appearance in annular flow, melt strength, and extensibility are affected by melt elasticity. A correlation was found between the maximum draw ratio of a filament stretched under non-isothermal conditions and minimum film thickness.     

Rheological properties of long chain branched polyethylene melts at high shear rate

Capillary extrusion experiments involving a number of polyethylenes with emphasis on assessing the effect of long chain branching (LCB) are performed. None of the metallocene catalyzed linear low density polyethylenes (mLLDPE) produced by Dow Chemicals, which are believed to have some level of LCB, show temperature dependence on the viscosity at the gross melt fracture regime. Furthermore, these materials do not show spurt or stick-slip flow, in contrast with most linear polyethylenes. LDPE and blends of LDPE with LLDPE having LCB also show the absence of stick-slip flow, but show temperature dependence on the viscosity. From these observations, we conclude that the stick-slip flow is very sensitive to the existence of LCB.     

Rheological and thermal properties of blends of low-density polyethylene and its ionomers

Melt rheology and DSC studies of blends of two ionomers′ ethylene-acrylic acid copolymers are reported, EAA (4.6 mole % AA) and EAA (6.5), as a function of their concentration and counter ion types with their precursor, a low-density polyethylene. Various isothermal dynamic measurements in the frequency range of 0.01 to 10 rad/sec, from 120 to 200°C, were made; and partial master curves of G′ and G″ were generated. Although the melts appeared to follow the conventional superposition principle, the Cole-Cole plots were found to be unsatisfactory in describing the miscibility of such blends. The analysis based on the calculations of activation energies and other supporting measurements such as Vicat softening and DSC thermal analysis indicate that such blends are immiscible and perhaps do not have LCST. The blends failed to follow the additivity rule. The Vicat softening measurements indicated variations in the morphology of blends. The DSC studies performed on various 50/50 blends clearly demonstrated phase immiscibility.     

Rheological properties of glass bead-filled low-density polyethylene composite melts in capillary extrusion

The melt flow of glass bead-filled low-density polyethylene composites in extrusion have been observed by using a capillary rheometer to investigate the effects of temperature, shear rate, and filler content on the rheological properties of the melts. The results show that the melt shear flow obeys a power law, and the dependence of the apparent shear viscosity, η_app, on temperature is in accord with an Arrhenius equation. At the same temperature and shear rate, η_app increases slightly with increasing the volume fraction of glass beads, but the flow behavior index decreases with increasing filler content. In addition, the first normal stress difference of the melts linearly increases with increasing wall shear stress. Good agreement is shown with the N₁ calculated with the equation presented in this article and the pressured data from the sample melts. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1451–1456, 1999     

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.     

支化PE的结构与性能

采用均相和负载α-二亚胺镍配合物催化乙烯聚合制备不同支化度的聚乙烯(PE),探讨支化度对PE密度、熔融行为、结晶度和晶型、热稳定性等的影响。随着支化度的增加,PE密度近于线性减小,熔点随之下降,结晶度呈线性下降,但热稳定性并不是单调下降。PE的差示扫描量热法升温曲线的熔融峰随着支化度增大而变低,熔融区域变宽;支化度达到48个/1 000 C时出现双峰,此时PE结晶度下降至13.0%,且衍射角为23°附近时,(200)晶面衍射峰消失,表明己转变为非结晶态的PE。     

Elongational flow properties of low-density polyethylene and linear low-density polyethylene from nonisothermal melt spinning experiments

Low-density polyethylene (LDPE) and also linear low-density polyethylene (LLDPE) resins can be characterized by the degree of strain hardening and down-gaging during elongation. A new method for the determination of the apparent elongational flow characteristics is presented. In a small scale apparatus, a molten monofilament is stretched under nonisothermal conditions similar to those found in tubular film extrusion. Measurement of resistance to elongational flow and apparent elongational strain rates permit the comparison of the process-ability of different resins under specified conditions. The effect of melt temperature and extension ratio are examined. The importance of the molecular structure of both LDPE and LLDPE resins on these properties is also outlined.     

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.     

Rheological characterization of linear low-density polyethylene–Fischer–Tropsch wax blends

The thermal and rheological behavior of blends of a Fischer–Tropsch (F-T) wax with linear low-density polyethylene (LLDPE) were investigated by differential scanning calorimetry and cone-and-plate rheometry. F-T wax is used as a possible low-cost processing aid alternative for LLDPE masterbatch applications. The melting- and crystallization thermograms indicated a two-phase solid-state morphology and full compatibility in the fully molten material. Both the high-melting and low-melting phase contained co-crystalized wax and polymer. Rheological data of F-T wax-LLDPE blends over the full composition range was also obtained. The zero-shear viscosity data was adequately predicted by the Friedman and Porter mixing rule: $\mathrm{\eta }={\left(w_p{\mathrm{\eta }}_p^{1/\mathrm{\alpha }}+{w_w\mathrm{\eta }}_w^{1/\mathrm{\alpha }}\right)}^{\mathrm{\alpha }}$ with α = 3.4. This implies that the melt viscosity is dominated by the effects of polymer chain entanglement and that the main consequence of adding the wax is to reduce the concentration of the polymer present. The complex viscosity also fitted this model albeit with α = 4.81. All Han plots, that is, plots of the logarithm of the storage modulus (G') against the logarithm of the loss modulus (G"), were linear. Within the experimental uncertainty, they were essentially unaffected by variations in blend composition, temperature and the applied angular frequency. Additionally, Cole–Cole plots were also in agreement that wax-LLDPE blends are miscible at melt state. This supports full miscibility of the F-T wax-LLDPE blend system down to temperatures as low as 120°C.     

Mechanical and flow properties of high-density polyethylene/low-density polyethylene blends

The recycling of plastic waste is of particular interest in large urban areas where municipal waste represents a large ecological problem. To achieve their objective (consumer products from plastic waste), formulators of a recycling program have to understand the implications of working with mixtures of different resins. Furthermore, in a multiphase system, the thermomechanical history experienced by the resins during processing represents an important link between operating conditions, resin properties, and final product performance. High-density polyethylene/low-density polyethylene (HDPE/LDPE) blends (10, 20, 35, 50, 65, 80, and 90 percent by weight HDPE) were melt blended in an internal mixer. A complete rheological characterization was performed on each blend. The resulting blends were extruded under different processing conditions. The extruded sheets were further characterized to determine their mechanical properties, The experimental results show important differences in the mechanical properties (transverse and longitudinal) of the sheets obtained from the blends. These differences are explained on the basis of the processing conditions (thermomechanical history) and the rheological properties of the molten blends.     

Temperature dependence of the properties of low-density polyethylene

The dynamic mechanical properties of low-density polyethylene melts were measured as a function of frequency and temperature using the Orthogonal Rheometer. These results were expressed in terms of the components G′ and G″ of the dynamic modulus and the components η′ and η″ of the dynamic viscosity. The functions J′, J″, η*, and G* were also calculated from the results. The method of reduced variables or time-temperature superpositions was attempted on the results. The classical method was found to require modification to be applied to these low-density polyethylenes. From this modified form of the reduced variables technique, the temperature dependence of the elastic and viscous parts of the response could be separated. The experimentally determined temperature dependence of the elastic part of the response was found not to be in accord with the accepted theory of rubber elasticity. The temperature dependence of the viscous part of the response is discussed in terms of the concept of flow activation energy, and clarification of this term is explored. It is concluded that the temperature dependent properties of polymer melts are best compared at equivalent time scales of response in the non-Newtonian region. In order to do this the temperature dependence of the elastic part of the response must be included explicitly in the reduction scheme.     

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.     

Influence of shearing history on the rheological properties and processability of branched polymers. II. Optical properties of low-density polyethylene blown films

An investigation was performed to determine how optical properties of LDPE blown films changed when the material was subjected to extrusion shearing. In this study, shearing histories were given to the materials by designed extrusion shearing. Recognizable variations take place in haze and gloss of the blown film during the extrusion shearing. Such variations were expressed as a function of the processing index (PI), which was introduced in a preceding paper as a measure of the memory effect of shearing histories of LDPE. This means that the variations originate in a certain change in the cohesive state of the polymer molecules attributable to the shearing.     

Steady flow and dynamic viscoelastic properties of branched polyethylene

The presentation of viscoelastic properties of molten high polymers in a complex plane makes three characteristic rheologic parameters appear. These are examined for a series of commercial samples of low density polyethylene. For instance, it enables products to be recognized which are very similar as far as the melt index is concerned but have different molecular weight distribution, different long chain branching index and consequently different processing properties.     

Mechanical properties and morphology of high-density polyethylene/linear low-density polyethylene blend

The binary blend of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) in the range of composition from 100% HDPE to 100% LLDPE has been investigated for tensile and flexural properties and the morphology in the deformed state on tensile fracture. Tensile properties (initial modulus, yield stress, and elongation-at-yield, ultimate tensile strength and elongation-at-break, and work of yield and work of rupture) and flexural properties (flexural modulus and flexural yield stress) are studied as a function of blend composition. Behavior, in terms of these properties, is distinguishable in three zones of blend composition, viz. (i) HDPE-rich blend, (ii) LLDPE-rich blend, and (iii) the middle zone. In zones (i) and (ii), the variations of these properties are more or less linear, whereas in the middle region [i.e., zone (iii)], there is a reversal of trends in variation or sometimes a behavior opposite to the expected one. The results are explained on the basis of the effects of cocrystallization and the presence of octene-containing segments in the amorphous phase. Scanning electron micrographs of the tensile fracture surfaces are presented to illustrate the occurrence of transverse bands interconnecting the fibrils.     

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.     

Rheological and thermomechanical properties of long‐chain‐branched polyethylene prepared by slurry polymerization with metallocene catalysts

A series of polyethylene (PE) samples were prepared in a slurry polymerization with bis(cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂)/modified methylaluminoxane (MMAO) using a semibatch reactor. The samples had long‐chain branch densities (LCBDs) of a 0.03–1.0 branch per 10,000 carbons and long‐chain branch frequencies (LCBFs) up to a 0.22 branch per polymer molecule. The rheological and dynamic mechanical behaviors of these long‐chain branched PE samples were evaluated. Increasing the LCBF significantly increased the η₀'s and enhanced shear thinning. Long‐chain branching (LCB) also influenced the loss modulus and storage modulus. Increasing the LCBF led to enhanced G′ and G″ values at low shear rates and broader relaxation spectrums. The samples exhibited thermorheologically complex behavior. LCB also played a significant role in the dynamic mechanical behavior. Increasing the LCBF increased the stiffness of the polymer and enhanced the damping or energy dissipation. However, LCB had little influence on the crystalline structure of the PE. The α‐ and γ‐relaxations showed little dependence on the LCBF. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 307–316, 2004     

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 properties of corona modified cellulose/polyethylene composites

The rheological behavior of wood fiber/polyethylene composites made of corona treated constituents was investigated. Corona treatment of one or both of the constituents resulted in decreased melt viscosities relative to compounds containing untreated materials. The reduction of melt viscosity may originate from low molecular weight moieties formed on the surfaces of both polyethylene and cellulose during corona treatment. These may act as lubricants at interfaces. Also it was found that the corona treatment of fibers leads to higher packing volumes; this may result from a reduction in fiber length when treated fibers are processed under high shear conditions. As a result these fibers perturb the normal flow pattern in the melt to a lesser degree than the longer fibers of untreated cellulose.