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     

Chemical modification of PP architecture: Strategies for introducing long-chain branching

Two strategies for introducing long chain branching (LCB) to a polypropylene homopolymer (PP) are evaluated in terms of the product's molecular weight and branching distributions, and in terms of melt-state shear and extensional rheological properties. Single step processes involving radical-mediated addition of PP to triallyl phosphate are shown to generate bimodal products with highly differentiated chain populations, while a two step sequence involving PP addition to vinyltriethoxysilane followed by moisture-curing is shown to generate more uniform architectures. As a result, the sequential approach can improve low-frequency shear viscosity and extensional strain hardening characteristics while staying below the polyolefin's gel point. The composition and molecular weight distribution transformations that underlie sequential LCB techniques are discussed.     

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.     

Influence of carrier fluid on the electrokinetic and rheological properties of shear thickening fluids

This paper presents a study on the influence of hydroxyl groups and oxygen atoms together with chain length and branching of carrier fluid on the rheological and electrokinetic properties of shear thickening fluid (STF). An STF is non-Newtonian fluid behaviour in which the increase of viscosity increases with the applied shear rate. Ethylene glycol, triethylene glycol, 1,3-propanediol, glycerin, poly(propylene glycol) of different molecular weight and poly(propylene glycol) triol were used as the carrier fluids (dispersants). Silica powder with an average particle size of 100 nm was used as the solid phase. Zeta potential, particle size distribution (by DLS technique), steady-state and dynamic rheological measurements were conducted. Experimental results indicate that a different amount of hydroxyl groups and oxygen atoms together with chain length and branching of carrier fluids have a significant influence on the intermolecular interactions thereby and on the rheological properties of suspensions. Depending on the composition, it is possible to control rheological properties. The use of a suitable carrier fluid allows the required pattern flow to be obtained, from Newtonian through shear thinning to shear thickening, given specific shear conditions.     

Effect of structure modification on rheological properties of biodegradable poly(ester‐urethane)

Biodegradable lactic acid based poly(ester‐urethanes) (PEU) were polymerized and their structure and rheological properties were characterized. The polymerization process comprised two steps: lactic acid monomer was oligomerized to low molecular weight prepolymer, and this was then linked to high molecular weight PEU with chain extender, 1,6‐hexamethylene diisocyanate. The properties of PEU were modified by varying the amount of chain extender from 1.05:1 to 1.35:1 (NCO/OH ratio). The modification was mostly seen in the molecular weight distribution of the polymers, which was broadened from 2.2 to 3.5 as the amount of chain extender was increased. The telechelicity of the prepolymer was found to play an essential role in successful linking of the prepolymer units. In addition, the rheological properties of poly(ester‐urethane) were determined with capillary and dynamic rheometers. All PEU samples were pseudoplastic and broadening of their molecular weight distribution was accompanied by increased viscosity and complex viscosity at low shear rates and increased shear thinning. The temperature dependency of the measurement was pronounced. Rheological measurements also showed that PEU starts to degrade at 100°C and further rise in temperature increases the rate of degradation significantly.     

Extrudate swell of high density polyethylene. Part I: Aspects of molecular structure and rheological characterization methods

Two high density polyethylene (HDPE) resins–samples 801 and 802–both nominally the same material, as they are taken from successive batches of the same commercial grade, are characterized for their molecular structure and rheological properties. Gel permeation chromatography (GPC) and low angle laser light scattering (LALLS) results must be interpreted in combination with rheological data to show the presence of somewhat more high molecular weight material in 802 that in 801. Small amplitude oscillatory shear, steady shear, and capillary shear measurements performed in different laboratories show consistently higher shear viscosity values at low shear rates for sample 802. Extensional viscosity measurements show similar results. The interpretation of rheological data in terms of molecular structure could be complicated by the possible presence of long chain branching (LCB). The zero shear viscosity and discrete relaxation spectrum is estimated for both samples. The small rheological difference between 801 and 802 forms the basic information for understanding their time dependent extrudate swell behavior, as will be described in Part II.     

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.     

多分散聚合物稀溶液体系的Rouse模型

本文将Rouse提出的均一分布球簧链式分子模型加以推广.得到了多分散体系的本构方程.对几种最常见的分子量分布,在稳态剪切流中,分别计算了它们的物质函数以及特性粘数与重均聚合度的关系.结果表明,这一线性模型的流变性质与聚合物的分子量分布有密切的关系;若通过物质函数的监测,则还能预示聚合反应的动态过程.     

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.     

Structure and Physical Properties of Polyethylenes obtained from Dual Catalysis Process

Polyethylenes with bimodal molecular weight distribution were synthesized by using dual catalyst systems. It is found that the molecular weight and its distribution is highly influenced by the molar ratio between the two catalytic centres, and that a synergistic effect exists, being the molecular weight of the products higher than that corresponding to the materials obtained from the isolated catalysts. What it is interesting is that the molecular weight distribution shape, the microstructure and the final polymer properties could be regulated by the selection of this ratio. Results from this study show that materials with a broad range of microstructures, crystallinities and mechanical properties are obtained. The correlations found show that although a double population of macromolecular species exists, both are able to co-crystallize to form a unique crystalline structure from dilute solution. Rheological testing point towards a pronounced shear thinning behaviour, very high relaxation times, and thermorheological complexity, suggesting the incorporation of long chain branching during the polymerisation process. In addition, simple additive models applied to the linear viscoelastic properties of the polymers, by using the rheological response of the pure components, are unable to explain the experimental results obtained, suggesting a tandem effect rather than a dual action between the two active centres.     

A rheological study of the low molecular weight butyl polymer

A rheological study has been performed to characterize the low molecular weight butyl polymers using a couette coni-cylindrical viscometer. The bulk viscosity was determined as a function of temperature, weight-average molecular weight, viscosity-average molecular weight, and shear rate. The temperature dependence of the viscosity, while adequately represented by the Williams, Landel, and Ferry equation, is best described by an Arrhenius equation for the temperature range investigated. The viscosity is shown to vary with the 3.5th power of the weight-average molecular weight above a critical molecular weight and to the 1st power below this molecular weight. Although the ratio of the weight-average molecular weight to the number-average molecular weight usually affects the flow properties of polymers, this was not true for the polymers investigated. The bulk viscosity was found to be independent of the molecular weight distribution for the temperature and shear rate range studied. It has been shown that a definite relationship exists between the bulk viscosity and the viscosity-average molecular weight as determined by dilute solution viscosity. A mathematical model has been developed to relate these two parameters as a function of temperature and shear rate.     

干法纺丝用聚间苯二甲酰间苯二胺溶液的流变性能

研究了聚间苯二甲酰间苯二胺溶液的固体质量分数、相对分子质量、温度对溶液流变性能的影响。结果表明:聚间苯二甲酰间苯二胺溶液的流变性能受溶液固体质量分数、相对分子质量、温度的影响明显,聚合物相对分子质量增大、溶液固体质量分数增加均使溶液表观黏度增大,温度升高使溶液表观黏度减小,溶液表观黏度随剪切速率的变化幅度较小。试验结果表明:适合干法纺丝的聚间苯二甲酰间苯二胺溶液的固体质量分数为31%³5%,特性黏度为1.6 dL/g左右,纺丝时原液温度范围为5035%,特性黏度为1.6 dL/g左右,纺丝时原液温度范围为50¹20℃。     

Thermal and rheological studies on the molecular composition and structure of metallocene‐ and Ziegler–Natta‐catalyzed ethylene–α‐olefin copolymers

The relationship between the molecular structure and the thermal and rheological behaviors of metallocene‐ and Ziegler–Natta (ZN)‐catalyzed ethylene copolymers and high‐density polyethylenes was studied. Of special interest in this work were the differences and similarities of the metallocene‐catalyzed (homogeneous) polymers with conventional coordination‐catalyzed (heterogeneous) polyethylenes and low‐density polyethylenes. The short‐chain branching distribution was analyzed with stepwise crystallization by differential scanning calorimetry and by dynamic mechanical analysis. The metallocene copolymers exhibited much more effective comonomer incorporation in the chain than the ZN copolymers; they also exhibited narrower lamellar thickness distributions. Homogeneous, vanadium‐catalyzed ZN copolymers displayed a very similar comonomer incorporation to metallocene copolymers at the same density level. The small amplitude rheological measurements revealed the expected trend of increasing viscosity with weight‐average molecular weight and shear‐thinning tendency with polydispersity for the heterogeneous linear low‐density polyethylene and very‐low‐density polyethylene resins. The high activation energy values (34–53 kJ/mol) and elevated elasticity found for some of our experimental metallocene polymers suggest the presence of long‐chain branching in these polymers. This was also supported by the comparison of the relationship between low shear rate viscosity and molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1140–1156, 2002     

Effect of molecular weight and molecular weight distribution on the rheological properties of aqueous poly(ethylene oxide) solution

The effect of the molecular weight and the molecular weight distribution on the rheological properties of aqueous poly(ethylene oxide) (PEO) solutions has been investigated with four PEO samples differing in their M_w, M_w/M_n and purity. The main result of this study is that the steady shear viscosity as well as the complex dynamic viscosity of the samples with broad molecular weight distribution greatly differed from the viscosities of the samples having a narrow molecular weight distribution. Furthermore, the samples with broad molecular weight distribution showed a distinct molecular weight dependent non-Newtonian behavior at increasing shear rates and frequencies. This behavior was not observed for the sample with a narrow molecular weight distribution. Both effects are mainly attributed to the influence of the high molecular weight fraction in the PEO samples of broad molecular weight distribution. The often reported degradation of PEO solutions was not observed within the time scale of our experiment.     

Effect of chain structure on the melt rheology of modified polypropylene

The effect of molecular structure of polypropylene (PP) on the melt rheological properties were investigated for electron irradiated polymer and di-2-ethylhexyl peroxy dicarbonate (EHPC)-treated polymer. The modifications were examined in terms of the rheological behaviors, molecular weight distribution, and the degree of branching. The high melt strength PP was obtained by irradiating with 50 and 80 kGy and adding EHPC. The modified PPs showed the strain hardening in the uniaxial elongational viscosity, though the linear elongational viscosity was lower than that of the unmodified PP. Low angle laser light-scattering measurements of the modified PPs showed the interesting results; high irradiation doses such as 50 and 80 kGy caused higher molecular weight chains branching. Nevertheless, the long branching chains were not detected for the EHPC modified PP, which also showed the strain hardening in uniaxial elongational flow. In this article, the relation between chain structure and rheological properties is discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1493–1500, 1999     

Assessment of length and bundle distribution of dilute single‐walled carbon nanotubes by viscosity measurements

Rheological measurements have long been an invaluable technique in studying mechanical and structural properties of polymers. Measurements on dilute, noninteracting polymer solutions allow the determination of macromolecular structural information, such as molecular weight. This analysis has been complicated by molecular polydispersity; thus, average effects are more commonly reported. Here, we demonstrate polydispersity characterization for rod‐like polymers like single‐walled carbon nanotubes (SWCNTs). By extending the theory of the rheological behavior of rigid rods, we determine the distribution of length and bundle size in suspensions of SWCNTs by a simple rheological method. The method is based on measuring the viscosity of dilute suspended SWCNTs over a shear rate range spanning the Newtonian and shear‐thinning regimes. We show that a log‐normal distribution in length with minimal bundling accurately describes the viscosity measurements. This rapid new method yields the SWCNT length distribution while relying on bulk samples, which are less prone to artifacts. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1499–1508, 2014     

The effect of molecular weight and weight distribution upon polymer melt rheology

A major objective in polymer rheology is to predict a fluid's response to a general deformation from molecular information. A method has been developed which allows one to predict the viscoelastic properties of polymer melts from a limited amount of rheological and molecular data for the polymer. The input parameters are: (a) zero-shear viscosity; (b) molecular weight distribution; (c) temperature and density; and (d) constants relating Graessley's relaxation time to the Rouse relaxation time. The technique then “simulates” a discrete relaxation spectrum using G′ and G″ data from the Rouse theory and finally requires that a continuum model of polymer viscoelasticity be fit to shear viscosity data predicted by Graessley's theory. Examples of the utility of the procedure are given to illustrate the role of molecular weight and weight distribution in determining rheological behavior.     

Shear,tack, and peel of polyisobutylene: Effect of molecular weight and molecular weight distribution

The effect of polymeric molecular weight and molecular weight distribution on pressure-sensitive adhesive performance was studied in a model system of commercial polyisobutylenes. Molecular weight was characterized by size exclusion chromatography and membrane osmometry. Pressure sensitive adhesive performance was assessed by shear, peel, and probe tack testing based on standardized test methods. Lower molecular weight polyisobutylenes (Mw < 600,000) are successful in peel and probe tack testing due to their ability to flow quickly and wet the substrate test surface. They do not function as well in shear, however, where the polymer must resist flow under a load. High molecular weight species, by contrast, perform well in shear resistance tests and less successfully in peel and probe tack testing. Where high and low molecular weight polyisobutylenes are blended to broaden the molecular weight distribution while maintaining constant weight average molecular weight, adhesive performance in shear, peel, and probe tack are improved. All of the adhesive properties tested were found to have their foundation in some fundamental rheological properties of the polymers (e.g., shear viscosity and tensile creep compliance). This suggests the use of fundamental rheological characterization for screening of adhesive formulations over more empirical adhesive testing methods.     

橡胶型氯化聚乙烯结构研究

研究橡胶型氯化聚乙烯(CPE)的氯分布、相对分子质量及其分布、残余结晶度及流变性能。结果表明，橡胶型CPE的氯原子主要以单取代的形式存在于分子链上；4种橡胶型CPE的-↑Mw由大到小顺序为CPE6335，CPE6135，CPE6235，CPEl40B，-↑Mw越大，CPE的门尼粘度越小；橡胶型CPE的氯含量越大、氯原子分布越均匀，其残余结晶度越小；橡胶型CPE熔体为剪切变稀流体。     

A study of rheological properties of cellulose diacetate in acetone solution at low and high shear rates

The rheological properties of cellulose diacetate (CDA) with different intrinsic viscosity (IV) and different concentration in acetone solutions were studied at low and high shear rates. The zero-shear viscosity increased and the structural index increased, when the IV of CDA was increased or the acetone solution concentration was increased. Evidence suggested that a sulfate structure may be forming. It is shown that the increase of hemicellulose and sulfur content is associated with an increase of chain entanglements between CDA molecules and the abnormal increase of solution zero-shear viscosity. At a high shear rate, the correlation curve between inlet pressure drop and solution concentration obtained by Bagley method analysis shows an inflection point, which appears to be the critical concentration at which the cellulose diacetate molecular chains in the solution form a long range entangled elastic network. After the concentration exceeds a certain range of above critical points, the entanglement of the molecular chains in the solution is significantly enhanced. The zero shear viscosity inflection point concentration calculated by the rheological curve with low shear velocity and the inlet pressure drop inflection point concentration calculated by the capillary rheological calculation have good consistency.