Experimental investigations of the influence of molecular weight distribution on melt spinning and extrudate swell characteristics of polypropylene

An experimental study of the influence of molecular weight distribution on the melt spinning and extrudate swell of a series of polypropylenes of varying molecular weight and distribution is reported. Emphasis is given to effects of variations of molecular weight distribution. Narrowing the molecular distribution increases the slope of the elongational viscosity–elongation rate curve, stabilizes the spinline relative to both random disturbances and draw resonance, and decreases both instantaneous and delayed extrudate swell. These results are interpreted in terms of viscoelastic fluid mechanics and earlier experimental studies by the authors of the influence of molecular weight distribution on rheological properties. The influences of these rheological factors on spinline structure development is discussed.     

Elongational viscosity in the isothermal melt spinning of polypropylene

The elongational viscosity of polypropylene has been investigated by isothermal melt spinning, carried out over a range of experimental conditions. The filament diameter and the elongational force were measured for running filaments and the relationship between elongational viscosity and elongational strain rate reported. The elongational viscosity was observed to decrease in the vicinity of the spinneret and then remained constant before increasing along the thread line. An increase in elongational viscosity did not occur within the isothermal zone until the elongational flow was fully developed. The onset of an increase in elongational viscosity was determined from the constant total elongational strain. The degree of molecular orientation was also studied by birefringence measurements and was investigated as a function of elongational stress. At a high elongational stress, the relation between birefringence and elongational stress departed from linearity and exhibited a rapid increase which can be related to the increase in elongational viscosity.     

Apparent elongational viscosity of dilute polymer solutions

Apparent elongational viscosity studies were made on dilute solutions of high molecular weight polymers using a fiber spinning apparatus designed for low shear viscosity liquids with substantial elongational effects. The experimental method involved the flow of solutions of polyacrylamide and poly(ethylene oxide) from a tube into an evacuated vessel. Experimental results showed that the apparent elongational viscosity obtained from the jet shape increased linearly with the stretch rate.     

聚丙烯熔体拉伸流变行为的研究

采用双料筒毛细管流变仪,对两种不同摩尔质量的等规聚丙烯的剪切及拉伸流变行为进行了研究,并采用Cogswell方法计算了熔体的拉伸强度。结果表明：聚丙烯为假塑性流体,随着剪切速率的增加,熔体的表观剪切黏度下降,呈现出假塑性流体典型的“剪切变稀”行为。在相同的温度和剪切速率下,平均摩尔质量较小、分布较宽的聚丙烯的表观剪切黏度及拉伸黏度均较小,但熔体的拉伸强度较大,意味着其具有较好的流动性能,并具有较高的可拉伸性,可以达到较大的拉伸比。     

An experimental study of threadline dynamics with emphasis on the effect of molecular weight on the elongational viscosity of melt-spun poly(ethylene terephthalate)

A study of a melt-spun threadline has been carried out to determine the effect of molecular weight on the elongational viscosity of the polymer being spun. Polymer chosen for this study was poly(ethylene terephthalate) having different molecular weights. Conventional nonisothermal spinning of the polymers was carried out with cooling by free convection. Threadline surface temperatures were measured by a null-balance technique. Threadline tension at the take-up device was measured, and samples of the threadline were taken to obtain linear density profiles. Nonlinear least-squares fits were applied to the linear density data to obtain equations for velocity and elongation rate. These measurements were then used to determine the threadline elongational viscosity. Least-squares fits were made to a polynomial relating absolute temperature and elongation rate to the elengational viscosity. These results were then used to determine an activation energy of elongational flow which was found to decrease with elongation rate. Elongational viscosity was found to increase with molecular weight.     

BOPP专用树脂的流变行为研究

利用高压毛细管流变仪,对三种不同BOPP专用树脂的流变性能进行测定,BOPP专用料均表现为剪切应力随剪切速率增加而增加,但增加速率明显减弱,表观粘度随剪切速率增加而减小的特点,具有明显的假塑性的流动行为。通过分析温度、剪切速度和分子量及其分布对树脂的表观粘度的影响,确定不同树脂改善熔体粘度最有效的方法。     

Rheological and solid wall boundary condition characterization of unvulcanized elastomers and their compounds

An extensive fundamental investigation of the rheological properties and solid wall boundary condition shear stress of elastomers and elastomer–carbon black compounds has been carried out. The elastomers were an emulsion butadiene–styrene copolymer (SBR 1500) and a polybutadiene. Shear flow rheological properties were measured using a newly designed sandwich rheometer, in both constant shear rate and creep modes as well as in a capillary rheometer. A constant elongation rate rheometer for elastomers was developed. Stress relaxation measurements were also carried out in the sandwich rheometer. The shear viscosity of the gum elastomers exhibits a constant very high shear zero viscosity (8 × 10⁸ Pa.s for SBR 1500 at 100°C) and decreases with increasing shear rate. The compounds exhibit yield values of similar magnitude to carbon black compounds of molten plastics. Only the SBR 1500 and its compounds were studied in the elongational flow mode. It was not possible to achieve a steady state in these experiments. An apparatus for measurement of shear stress as a function of velocity (shear rate) at a specified pressure was developed. The instrument, which we call a friction tester, was used not only to determine wall shear stress but to investigate the regime of flow and potentially determine conditions for the onset of slip. Evidence of changing flow regimes were found, and the implications discussed.     

The effect of random branching on the balance between flow and mechanical properties of polyamide-6

The rheological and mechanical properties of a series of linear and randomly branched polyamide 6 samples, with varying molar mass and varying degree of moderate branching, have been investigated.As expected, it was found that random long-chain branching has a pronounced effect on the rheological behaviour of the materials in both shear and extensional flow. The zero shear viscosity increases with branching while the flow curve becomes more shear thinning. Randomly branched materials have an enhanced melt strength in elongational flow. Although branched, the materials show perfect melt stability in their rheology.The mechanical properties show minor differences between the linear and the moderately branched samples and are mainly dependent on the weight average molar mass. A small increase in modulus, yield stress and failure stress and a decrease in the strain at break are found, which is probably due to increased molecular orientation in the plane of injection moulding. The IZOD impact strength is similar to what is normally found for linear polyamide-6, and independent of branching. Also the fracture toughness K_IC is not affected by the incorporation of random branching. However, it is clearly dependent on the weight average molar mass.By using random branched polyamide-6, molecular weights and related mechanical properties can be obtained that are out of reach for linear polyamide-6.     

Transient uniaxial orientation of flexible polymer chains in a wide range of elongation rates

Affine evolution of chain end-to-end vectors distribution function is derived analytically for non-linear polymer liquids subjected to uniaxial elongational flow, controlled by time-evolution of chain deformation coefficients. Peterlin approximation for non-Gaussian chain elasticity is applied, with Padè approximation for the inverse Langevin function. The approach enables calculations of transient molecular deformation coefficients in entire range of elongation rates and times.Equations controlling time evolution of the molecular deformation coefficients in elongational flow are solved analytically with an assumption of dominating elongational component. The approach allows to decouple evolution equations and obtain an approximate closed form analytical formula describing time evolution of the molecular deformation with high accuracy, in particular at higher elongation rates, above the Gaussian limit.Predictions of the analytical formula are compared with numerical computations to evaluate the approximation and ranges of its validity.The analytical formula enables predicting evolution of average functions in non-linear systems, such as free energy, tensile stress, molecular orientation, etc. The formula is used to discuss molecular vs. macroscopic deformation in wide range of elongation rates and times, as well as evolution of stress, axial orientation factor, apparent elongational viscosity.     

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.     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and properties of ultrahigh molecular weight polyethylene processed under a consecutive elongational flow

Herein, a novel eccentric rotor extruder (ERE) capable of generating a continuous elongational flow was used to process ultrahigh molecular weight polyethylene (UHMWPE) without any processing aids and then compare with a conventional rotational batch mixer based on a shear flow. The morphological and rheological characterization verify that the technique based on the elongational flow could effectively reduce melting defects and yield more homogeneous morphology within the extruding samples relative to the conventional bath mixing based on a shear flow. The extrusion processing under an elongational flow can largely maintain the viscosity average molecular weight (M_η) of the UHMWPE nascent powder with only a 5.0% decrease at 200 °C, implying considerably low thermal oxidative degradation in sharp contrast to the conventional processing with significantly reduced M_η by 40.3%. Furthermore, the crystallinity for the sample prepared under an elongational flow is lower than that processed under a shear flow. These differences lies in the higher normal stress, rapider heat transfer and shorter duration generated by the ERE.     

Modeling of nonlinear extensional and shear rheology of low-viscosity polymer melts

The hierarchical multi-mode molecular stress function (HMMSF) model developed by Narimissa and Wagner [Rheol. Acta 54, 779–791 (2015), and J. Rheol. 60, 625–636 (2016)] for linear and long-chain branched (LCB) polymer melts were used to analyze the set of transient elongational and shear viscosity data of two LCB low-density polyethylenes (1840H and 2426 k), and a linear poly-(ethylene-co-α-butene), PEB A-780090 as reported by [Li et al. J. Rheol. 64, 177 (2020)], who had developed a new horizontal extensional rheometer to extend the lower limits of elongational viscosity measurements of polymer melts. Comparison between model predictions and elongational stress growth data reveals excellent agreement within the experimental window, and good consistency with shear stress growth data, based exclusively on the linear-viscoelastic relaxation spectrum and only two nonlinear model parameters, the dilution modulus G_D for extensional flows, and in addition a constraint release parameter for shear flow.     

On the mechanisms for drag reduction: A viscoelastic evaluation based on a bead-spring model

Two possible drag reduction mechanisms were examined by studying the viscoelastic effects of polymer solutions for the separate cases of oscillatory shear flow and elongational flow. The constitutive equation used was based on a modified dumbbell molecular model which predicts non-Newtonian viscosity and both the primary and the secondary normal stress differences. It can be shown that when this constitutive equation is arranged in the form of the Oldroyd model, the latter becomes a special case of this more general equation. The present results show that viscoelastic effects on the mean local rate of energy dissipation of a fluid element in an oscillatory motion are negligibly small. However, such effects introduce very large increases in the elongational viscosity as the stretching rate exceeds a certain limiting value and the flow time exceeds the terminal relaxation time of the fluid. The relative merits of these findings as possible explanations of turbulent drag reduction are briefly discussed.     

Orientation development in thermotropic liquid crystal polymers

Thermotropic liquid crystal polymers are a new class of polymeric materials that consist of rigid backbone molecules and thus, even in the quiescent condition, take extended chain conformation to form optically anisotropic melts. A systematic investigation was carried out on how this type of material responds to two basic flow fields: shear and elongation. Rheological properties of the polymer in these flow fields have also been measured. It was found that a high level of molecular orientation was readily obtained by elongational flow but not with shear flow. Specifically, extraordinarily high orientation was obtained when the melt was subjected to small elongational strains, whiel shear strain or shear rate had little effect. A possible mechanism to explain these behaviors is illustrated based on the existing observations or theories of rodlike molecules. This finding was used to interpret the orientation distribution in the extruded and injection-molded articles.     

Melt rheology of segmented polyamides: Effect of block molecular weight

Segmented polyamides, also known as polyether‐ester‐amides, are composed of polyether and polyamide structural units. The rheological behavior of segmented polyamides with respect to the variations in the molecular weight of hard and soft blocks has been studied using a Monsanto Processability Tester. These systems exhibit pseudoplastic flow behavior. The shear viscosity of the segmented polyamides decreases with a decrease in hard block molecular weight up to 1500. However, at low shear rates, the shear viscosity shows marginal change with an increase in soft segment molecular weight. The equilibrium die swell increases with an increase in shear rate, but decreases with increasing temperature. The stress relaxation study of the segmented polyamides reveals that the stress developed during extrusion relaxes exponentially for all the systems. The equilibrium die swell at a fixed temperature and shear rate, the time required to relax a fixed amount of stress and the stress developed after a certain time interval decrease with a decrease in hard block molecular weight up to 1500, but increase with an increase in soft segment molecular weight. The activation energy of the melt flow process increases with the rate of shear in most of the cases. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1739–1747, 1999     

Shear and elongational rheology of polyethylenes with different molecular characteristics. II. Elongational rheology

The elongational viscosities of polyethylenes with different molecular characteristics were measured at different Hencky strains and temperatures with a capillary rheometer by the replacement of the capillary cylindrical die with a hyperbolic converging die. The hyperbolic shape of the die established a purely elongational flow field at a constant elongational strain rate throughout the die. The effects of molecular characteristics such as the molecular weight, molecular weight distribution, and long‐chain branching and processing conditions such as the temperature and Hencky strain on the elongational rheology of the polyethylene samples were studied. Good master curves were generated for temperature and Hencky strain shifting and simultaneous shifting with respect to both the temperature and Hencky strain. Both the molecular weight distribution and long‐chain branching seemed to promote strain rate thinning and reduce the elongational viscosity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1184–1194, 2007     

Steady-state behavior of ring polymers in dilute flowing solutions via Brownian dynamics

A bead and spring model is considered for the Brownian dynamics simulation of the behavior of cyclic polymer chains (rings) in a dilute solution under shear or elongational flow. Finite extensibility, excluded volume, and hydrodynamic interaction are taken into account to make the polymer model as realistic as possible. In shear flow, the deformation of the chain and the shear rate viscosity dependence (the flow curve), are studied and characterized. In elongational flow, the coil-stretch phenomenon is described and the relationship between the critical elongational rate and the molecular weight is given. The qualitative behavior obtained for ring polymers is analogous to that of linear polymers.     

Nonlinear rheological behavior of a novel oil displacing agent

In this work, the shear and elongational rheologies have been investigated for a newly developed oil displacing agent, polymeric surfactant‐PSf. It was found that the PSf solutions exhibited Newtonian, shear‐thinning, and shear‐thickening behavior, respectively, depending on the polymer concentration and shear rate, and Cox–Merz rule was not applicable to these systems. The first normal stress difference (N₁) versus shear rate plots for PSf were complicated, which varied with the composition of the solutions. The uniaxial elongation in capillary breakup experimental results indicated that Exponential model could be used to fit the experimental data of the PSf solutions at lower polymer concentrations. In addition, it was found that PSf was more effective in improving shear viscosity than partially hydrolyzed polyacrylamide, but not in the case of elongational viscosity. The experimental results indicated that the microstructural mechanisms are responsible for the rheological behavior of the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40813.     

Steady-state behavior of star polymers in dilute flowing solutions via Brownian dynamics

A bead and spring model is considered for the Brownian dynamics simulation of the behavior of regular star polymer chains in a dilute solution under both shear flow and extensional (or elongational) flow. Finite extensibility, excluded volume, and hydrodynamic interaction are taken into account to make the polymer model as realistic as possible. The behavior of star-like chains in flow is similar to that of linear and ring polymers. Thus, dependence of a given property with the arm molecular weight is analogous to that found for linear polymers when using the total molecular weight. In shear flow, the deformation of the chain and the shear rate viscosity dependence (the flow curve), are studied. We find a slope for the shear-thinning region of the flow curve close to −2/3. In elongational flow the coil-stretch transition is characterized by giving the relationship between the critical elongational rate and the arm molecular weight, which turns out to be similar to the power law found in linear chains.