Prediction of dynamic and transient rheological properties of polystyrene and high-density polyethylene melts from the molecular weight distribution

A model relating the steady-shear melt viscosity and elasticity to the molecular weight distribution in HDPE and polystyrene melts has been extended to predict the dynamic viscosity, modulus, and loss modulus. Limitations in the model as applied to the dynamic properties are discussed. The model is also applied to the transient response of stress growth during steady shearing. This application is considered useful because it may help describe nonsteady-state flow of polymer melts in short dies and cyclic operations as employed in commercial molding equipment.     

An empirical model relating the molecular weight distribution of high-density polyethylene to the shear dependence of the steady shear melt viscosity

An empirical model has been developed to relate molecular weight distribution to the shear dependence of the steady shear viscosity in high-density polyethylene melts. It uses a molecular weight, M_c, which partitions molecular weights into two classes; those below M_c contribute to the viscosity as they do at zero shear, and those above M_c contribute to the viscosity as though they were of molecular weight M_c at zero shear. Each individual molecular weight species contributes on the basis of its weight fraction. M_c is proposed to be a unique function of the shear rate. Using this method of treating the molecular weight distribution, and the zero shear relation for relating η0 to molecular weight, the calculated steady shear viscosities at various shear rates for polyethylene samples of widely varying polydispersities agree well with experimental results. The model makes no judgment on the existence or importance of entanglements in non-Newtonian behavior since it has no specific parameters involving an entanglement concept. Use of the model suggests that for the samples studied, only the upper portion of the molecular weight distribution contributes toward the experimentally observed decrease of steady shear viscosity with shear rate for shear rates of up to 10,000 sec^?1. The lower molecular weight species are assumed to behave in a Newtonian manner.     

Effects of molecular weight distribution and long-chain branching on the viscoelastic properties of high- and low-density polyethylene melts

Using the Han slit/capillary rheometer, rheological measurements were taken of several commercially available low- and high-density polyethylene melts, namely, three low-density polyethylene samples of Chemplex Corp. (CX 1005, CX 1016, and CX 3020), three low-density polyethylene samples of U.S. Industrial Chemicals Co. (NA 205, NA 244, and NA 279), two high-density polyethylene samples of Union Carbide Corp. (DMDJ 5140 and DMDJ 4306), and two high-density polyethylene samples of Mitsui Petrochemical Industries, LTD. Molecular characterization of these samples was carried out by the resin suppliers. The rheological measurements included (1) entrance pressure drop, (2) exit pressure, (3) pressure gradient, (4) die swell ratio. These then permitted us to determine the shear viscosity and normal stress differences. The rheological measurements were interpreted to identify the effects of long-chain branching and molecular weight distribution on the rheological properties of polyethylenes in the light of the existing molecular viscoelasticity theories. It was found that fluid elasticity is greater for polymers having a broader molecular weight distribution and that, for polymers having more long-chain branching, viscosities are lower while elasticities are higher.     

Correlation between steady state flow curve and molecular weight distribution for polyethylene melts

This article uses Graessley's theory of viscosity to predict the flow curve for several high-density and low-density polyethylene melts using the molecular weight distribution data obtained from the gel permeation chromatograph. The agreement with the experimental flow curve obtained from the Weissenberg rheogoniometer and the Instron rheometer was not quantitative for many high-density polyethylenes studied here. For the low-density polyethylenes, it was shown that the agreement between the theory and the experiment was good even though the molecular weight distribution data were not corrected for long-chain branching. For these samples, the experimental relaxation time τ₀ obtained by superposition of the data with the theoretical master curve was of the order of the Rouse relaxation time τ_R. The systematic increase in the ratio τ_R/τ₀ was ascribed to the increase in the molecular weight or to the increased number of long-chain branches.     

The effect of molecular weight distribution on polyethylene film properties

Polymer molecular weight heterogeneity affects the rheological properties of polymer melts such as melt viscosity, fracture and die swell. These rheological properties affect the conversion of the polymer from the bulk resin state to its final usable form. In this particular study, the effect of molecular weight distribution on polyethylene blown film characteristics was studied. The effect of the molecular weight heterogeneity on the rheological characteristics of the polymer in the molten state and its effect on the film properties is presented. The properties studied included film gloss, haze, tear resistance and film impact strength. This study shows that broadening the molecular weight distribution increases haze and reduces film gloss. Further, it was shown that a linear relationship exists between film gloss and external haze. Both values are measures of surface irregularities in the film which are affected by the drawing characteristics of the polymer. A broader molecular weight distribution results in increased impact strength as measured by the Dart Drop Impact Test. This is, it is believed, a result of the increase in long chain branching of the higher molecular weight fractions of the polymer which cause a higher degree of molecular weight entanglement at the branch sites. In contrast the tear strength is reduced as the molecular weight distribution broadens because of the low molecular weight fraction in the broad spectrum material which tend to decrease resistance to tear.     

Ultra-high molecular weight high-density polyethylene as a gear material

Tests have been made for use of a high-density polyethylene of ultra-high molecular weight as a gear material. The gears had a diametral pitch of 10 and 30 teeth. They were tested in mesh with a steel gear of the same size in two operating conditions: (1) in still air without lubrication, and (2) in oil with generous lubrication. The effects of speed, temperature, and initial lubrication on the load capacity of the gears were tested and an equation was developed to express the limits of these gears operating without lubrication. In the lubricated conditions, the influence of oil flow and its temperature on the gear teeth temperature were evaluated. The wear of the plastic gear was measured in both operating conditions and wear rate was calculated as a function of the load and gear life. Curves are presented suggesting design limits of the gears in the two operating conditions. There are also recommendations on the center distance setting and the backlash to use.     

Oscillating flow behavior of high-density polyethylene melts

The oscillating flow behavior of a variety of high-density polyethylene and copolymer samples was studied in a constant displacement rate rheometer. At any plunger velocity, the period of the oscillations decreases linearly with melt depth, suggesting a resonance phenomenon. As plunger velocity is increased, the load waveform changes in a regular manner that indicates a progressive increases in the proportion of each cycle spent on the right-hand branch of the flow curve. Little difference was found in the shear stress at which oscillating flow began for samples differing in molecular weight, molecular weight distribution, and manufacturing process. However, the shear rate at which oscillating flow begins depends, strongly on both molecular weight and distribution. Oscillating flow is shifted to higher shear rates by broadening distribution, reducing molecular weight, increasing temperature, or decreasing the L/D ratio of the capillary.     

Influence of molecular weight distribution on the elasticity and processing properties of polypropylene melts

In a study of the flow behavior of polymer melts a semi-empirical viscometric equation has been used which contains an elasticity parameter relating the shear dependence of the viscosity to the normal-stress effect. The way in which both these effects are influenced by the molecular weight distribution of the polymers investigated is shown, and the influence of melt elasticity on polymer processing behavior is discussed. From previously published viscosity data the elasticity parameter has been determined for a number of polypropylene grades, and the possibility of classifying these grades according to a characteristic time constant is indicated.     

Effects of molecular weight distribution and branching on rheological properties of polyolefin melts

The objective of this work was to determine the relationships among molecular and melt parameters of polyolefins. The polyolefins studied are polypropylene, poly-1-butene, poly-1-hexene, poly-1-dodecene, these have regularly spaced short-chain branches. Conclusions from previous work, as well as some new data, on polyethylene are given. As the molecular weight increases, the critical shear rate decreases but the melt viscosity and non-Newtonian ratio increase. As the molecular weight distribution broadens, the critical shear rate decreases, whereas the normal forces and the non-Newtonian ratio increase. Increasing the number of short-chain branches increases the energy of activation and the melt viscosity but decreases the non-Newtonian ratio. As the length of the short-chain branches increases, the non-Newtonian ratio increases, but the melt viscosity, critical shear rate, and energy of activation decrease. Increasing the number of long-chain branches decreases the non-Newtonian ratio, but the normal forces and the melt viscosity increase. Such information allows the polymer chemist to design a polyolefin molecule having the critical melt properties required for a given production technique.     

Thermal and rheological properties of polyethylene blends with bimodal molecular weight distribution

Polyethylene blends with bimodal molecular weight distribution were prepared by blending a high molecular weight polyethylene and a low molecular weight polyethylene in different ratios in xylene solution. The blends and their components were characterized by the high temperature gel permeation chromatograph (GPC), different scanning calorimetry (DSC), and small amplitude oscillatory shear experiments. The results showed that the dependence of zero‐shear viscosity (η₀) on molecular weight followed a power law equation with an exponent of 3.3. The correlations between characteristic frequency (ω₀) and polydispersity index, and between dynamic cross‐point (G_x) and polydispersity index were established. The complex viscosity (η^*) at different frequencies followed the log‐additivity rule, and the Han‐plots were independent of component and temperature, which indicated that the HMW/LMW blends were miscible in the melt state. Moreover, the thermal properties were very similar to a single component system, suggesting that the blends were miscible in the crystalline state. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A three-parameter equation for molecular weight distribution of low-density polyethylene

A new three-parameter distribution function is proposed which fits best the experimental molecular weight distribution curves of branched lowdensity polyethylenes. The data were interpreted from GPC measurements, and a special computer program was utilized in order to derive the best values of the empirical constants a, b, and c.     

Properties of bamboo flour/high-density polyethylene composites reinforced with ultrahigh molecular weight polyethylene

In order to improve the properties of bamboo-plastic composites (BPCs), bamboo flour/high-density polyethylene (HDPE) composites were reinforced with ultrahigh molecular weight polyethylene (UHMWPE). The effects of UHMWPE on properties of composites were studied. The crystallinity of composites decreased slightly. Compared with non-UHMWPE added bamboo powder/HDPE composite, the composite with 6 wt % UHMWPE, showed decrease in water absorption to 0.41%, whereas its tensile strength and flexural strength increased to 34.51 and 25.88 MPa, respectively, a corresponding increase of 34.59 and 12.87%. The temperatures corresponding to initial degradation temperature (T_initial) and maximum degradation temperature (T_max) of the composite increased from 282.7 and 467.4 °C to 288.5 and 474.7 °C respectively. Scanning electron microscopic images showed that UHMWPE was well dispersed and fully extended as long fibers in the composite, forming a “three-dimensional physically cross-linked network structure,” which contributed to the improved properties of the composites. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48971.     

Dynamic mechanical properties of polymer melts: The dependence of viscoelastic properties on molecular weight distribution

An investigation of the dynamic mechanical properties of several molten polymers was performed using the Maxwell Orthogonal Rheometer. Relaxation spectra derived from experimental data for the terminal region of viscoelastic response indicate that as molecular weight distribution broadens, terminal relaxation phenomena associated with molecular disentanglement and translation extend over a corresponding wider frequency range. The same data indicate that a true maximum relaxation time beyond which no elastic response is observed exists for the materials studied. Moreover, the maximum relaxation time corresponds to the reciprocal of the frequency where the dynamic viscosity deviates from its zero-shear value. Thus an estimate of the time necessary for complete elastic recovery in polymer melts is readily obtained experimentally.     

Experimental investigation of the influence of molecular weight distribution on the rheological properties of polypropylene melts

An experimental study of steady shear and elongational flow Theological properties of a series of polypropylene melts of varying molecular weight and distribution is reported. Broadening the molecular weight distribution increases the non-Newtonian character of the shear viscosity function and increases the principal normal stress differences at fixed shear stress. The behavior is compared to earlier rheological property-molecular weight studies. Correlations are developed for these properties in terms of molecular structure. Elongational flow studies indicate that for commercial and broader molecular weight distribution samples, ready failure by neck development occurs and the elongational viscosity appears to decrease with increasing elongation rate. For narrower molecular weight distribution samples, the elongational viscosity is an increasing function of elongation rate, The implication of these experimental results to viscoelastic fluid constitutive equations and polymer melt processing is developed.     

Rheological properties of polypropylene/high-density polyethylene blend melts. I. Capillary flow properties

Three kinds of isotactic polypropylenes (PP) with different melt flow indexes (MFIs) were melt-blended with three kinds of high-density polyethylenes (HDPE) with different MFI using a screw extruder, and the morphologies and capillary flow properties such as flow curve, entrance effect, Barus effect, and melt fracture were studied. When HDPE contents were 70 wt % or above and PP particles formed the disperse phase, the size of the particles decreased with decreasing viscosity of PP. When HDPE contents were 30 wt % or below and HDPE particles formed the disperse phase, the size of the particles was minimum when the viscosities of PP and HDPE were similar. The die swell ratios of the blends were higher than those of the components. On the other hand, the entrance correction coefficients of the blends were intermediate between those of the components. There was no correlation between the die swell ratio and the entrance corretion coefficient. Therefore, it is not always appropriate to regard the entrance correction coefficient as a measure of melt elasticity in the case of inhomogeneous polymer systems such as PP/HDPE blend.     

Experimental study on the effect of molecular weight and chemical composition distribution on the mechanical response of high-density polyethylene

This article aims to appraise the effect of microstructure comprising molecular weight distribution and chemical composition distribution on the mechanical properties of high-density polyethylene (HDPE). HDPE resins were synthesized using several titanium–magnesium-supported Ziegler–Natta catalysts in the industrial gas phase reactor under the same polymerization condition. Gel permeation chromatography and crystallization elution fractionation (CEF) were conducted on the resins to characterize the molecular weight and comonomer distribution. Crystallization, thermal and rheological behavior were evaluated following differential scanning calorimetry, polarization light microscopy, and rheometric mechanical spectrometry. The resins with higher soluble fraction in trichlorobenzene below 80°C (highly branched low molecular weight chains) exhibited longer crystallization time based on the crystallization kinetic obtained from the Avrami model. Rheological determination of the molecular weight between entanglements (M_e) and the average lamella thickness based on the Gibbs–Thomson equation revealed that the entanglement density and impact strength decreased, and the average lamella thickness increased with an increase in the ratio of CEF eluted fraction below 80°C to the crystallizable fraction in the range of 80–90°C.