Extensional flow of mica-filled polyethylene

Extensional flow of mica-filled high density polyethylene was studied at 150°C in a Rheometrics elongational rheometer. The constant strain-rate mode at a rate of 10⁻³ to 1.0 s⁻¹, and the constant stress mode were used. The mica content was 0, 25, 40, and 60 weight percent. In both testing modes, the steady state elongational viscosities were obtained; those for the filled samples were about ten to twenty times larger than the shear viscosity at corresponding (low) rates of deformation.     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. III. Elongational rheology

The elongational rheology of solutions of cellulose in the ionic liquid solvent 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) was measured at 80, 90, and 100°C; 8, 10, and 12 wt% cellulose; Hencky strains 5, 6, 7; and strain rates from 1 to 100 s^?1. Master curves were generated by shifting the elongational viscosity curves with respect to temperature and Hencky strain. Also, general master curves were generated by simultaneously shifting with respect to both temperatures and Hencky strain. From the Arrhenius plots of the temperature shift factors, the activation energy for elongational flow was determined. The elongational rheology of these solutions was elongational strain rate thinning similar to that of their shear behavior and polymer melts and they were also strain hardening. Both effects and the viscosity increased with cellulose concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Shear and extensional properties of short glass fiber reinforced polypropylene

Shear and extensional properties of a commercial short glass fiber reinforced polypropylene were carefully investigated using commercial rheometers and a novel on‐line rheometer. This on‐line slit rheometer, installed on an injection molding press, has been designed to measure the steady shear viscosity, the first normal stress difference, and the apparent extensional viscosity of polymer melts and composites for high strain rates up to 10⁵ s⁻¹ in shear and 200 s⁻¹ in extension. Our results show that the steady‐state viscosity measurements using the on‐line rheometer are in excellent agreement with those obtained using commercial rheometers. The steady‐state and the complex viscosities of the composites were found to be fairly close to that of the matrix, but the Cox‐Merz rule was not verified for the composites at high rates. The elasticity of the composites was found to be equal to that of the polypropylene matrix. The apparent extensional viscosity was obtained from the pressure drop in the planar converging die of the slit rheometer using the analyses proposed by Cogswell [1] and Binding [2]. The extensional viscosity of the polypropylene was found to be much larger than the shear viscosity at low strain rates with a Trouton ratio of about 40 that decreased rapidly with increasing strain rate down to the value of 4 at 200 s⁻¹. The extensional viscosity of the composites was also found to be close to that of the matrix, with values 35 and 5% larger for the 30 and 10 wt% reinforced polypropylenes, respectively. These results are compared with the predictions of the Goddard model [3], which are shown to overpredict our experimental results. POLYM. COMPOS. 26:247–264, 2005. © 2005 Society of Plastics Engineers.     

Measurement of the equibiaxial elongational viscosity of polystyrene using lubricated squeezing

The equibiaxial elongational viscosity of polystyrene was determined using a lubricated squeezing technique. Constant strain rates up to Hencky strains of 4.5 could be maintained by a newly constructed instrument. Test results from controlled stress and controlled strain rate measurement were consistent and yielded well-defined steady-state viscosities. Measurements appeared to be unaffected by sample geometry, although proper lubrication is important in achieving steady state. The measured biaxial viscosity appeared to be strain rate thinning above a biaxial strain rate of ≈ 0.01 s⁻¹ at 160°C. As anticipated in the Newtonian region, biaxial elongational viscosity was approximately six times the shear viscosity. Thinning indices of both shear and biaxial elongational viscosities were 0.75. Data obtained at various temperatures were shifted following the timetemperature superposition principle. The resulting master curve could be fitted by a Carreau model with n ≈ 0.3 and a time constant of 110 s.     

Rheological properties of poly(trimethylene terephthalate) in capillary flow

The shear viscosity, extensional viscosity, and die swell of the PTT melt were investigated using a capillary rheometer. The results showed that the PTT melt was a typical pseudoplastic fluid exhibiting shear thinning and extensional thinning phenomena in capillary flow. There existed no melt fracture phenomenon in the PTT melt through a capillary die even though the shear rate was 20,000 s^?1. Increasing the shear rate would decrease the flow activation energy and decline the sensitivity of the shear viscosity to the melt temperature. The molecular weight had a significant influence on the flow curve. The flow behavior of the PTT melt approached that of Newtonian fluid even though the weight‐molecular weight was below 43,000 s^?1 at 260°C. The extensional viscosity decreased with the increase of the extensional stress, which became more obvious with increasing the molecular weight. The sensitiveness of the extensional viscosity to the melt temperature decreased promptly along with increasing the extensional strain rate. The die swell ratio and end effect would increase along with increasing the shear rate and with decreasing the temperature, which represented that the increase of the shear rate and the decrease of temperature would increase the extruding elasticity of the PTT melt in the capillary die. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 705–709, 2005     

Effect of extrusion temperature on elongational flow behavior of PVC melt

The effect of the sample extrusion temperature between 160° and 180°C on the elongational flow properties of a low molecular weight suspension PVC (unplasticized) has been studied with the Rheometrics Extensional Rheometer. The results of both the tensile creep measurements at a constant stress of 24 KPa and the stretching experiment at a constant strain rate of 0.01 sec^?1 indicated the existence of a rheological transition at 185°C marked by the dual valued flow activation energy and also by the temperature dependence of the tensile stress-strain curves. Increasing extrusion temperature increased both the flow activation energy and the extensional viscosity below the transition temperature.     

Characterization of the rheological behavior of UHMWPE gels using parallel plate rheometry

The effects of shear flow, temperature, and gel concentration on the rheological behavior of the ultrahigh-molecular-weight polyethylene (UHMWPE) gel in gel spinning process were investigated. The gel point was determined using parallel plate rheometry in rotation mode with controlled stress. Likewise, the flow curves at various temperatures were determined with controlled shear rate from 10⁻² to 10 s⁻¹. Whereas the shear storage modulus (G′) was obtained in oscillation mode with controlled strain from 1 to 100%. The result shows that the gel point of the UHMWPE gel increases with increasing gel concentration. The result from the strain sweep indicates that G′ of the gel is 1.5 × 10³ Pa, and it exhibits a plateau at low strain, but it is reduced with increasing strain. At low shear rates, for temperatures above gel point, all flow curves exhibit a plateau, then go down with increasing shear rate. Studying contributions from UHMWPE gel concentration, temperature, and shear rate for rheological view, we found that spinning at 6% UHMWPE (MW : 1.4 × 10⁶ g/mol) gel and 140°C gives the best effect on formation of fiber structure. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1009–1016, 1998     

Determination of steady-state elongational viscosity for rubber compounds using bell-mouthed dies

A bell-mouthed die geometry was designed to cause convergent flow at a constant, uniform, elongational strain rate. An equation was derived, which showed that steady-state elongational viscosity could be calculated from a plot of pressure drop due to elongation against a simple function of die length. To obtain values of pressure drop due to elongation, it was necessary to correct the total pressure drop measured across the bell-mouthed dies for the contribution from shear occurring near the die wall. For this purpose, a simplified shape for the bell-mouthed dies was assumed, comprising several parallel sided segments. Applying a formula to pressure drop data measured across straight dies corresponding to these segments gave an estimate of the pressure drop due to shear across the bell-mouthed dies. Pressure drops due to elongation were determined by subtracting the pressure drop due to shear from the total pressure drop measured across the bell-mouthed dies. Measurements were also carried out with lubrication to validate the shear correction method. The results indicate that for the compound used in this study, a combination of bell-mouthed and straightsided dies can be used in a conventional capillary rheometer to determine steady-state elongational viscosity. An elongational viscosity of 190 kPa s at 90°C and at a strain rate of 10 s⁻¹ was determined for a simple styrene-butadiene rubber compound. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1139–1150, 1997     

Transient shear and extensional properties of biodegradable polycaprolactone

Transient shear and extensional properties of two grades of partially crystalline biodegradable aliphatic polyesters, poly ε caprolactone (PCL), were investigated at three different temperatures. Uniaxial extensional viscosity at a constant strain rate was obtained using the Meissner apparatus. The magnitudes of the stress-over-shoot during stress growth experiments were smaller than those typically observed for other polymers. Higher melt temperature and higher strain led to faster relaxation, while the lower molecular weight PCL 767 relaxed faster than the higher molecular weight PCL 787. The relaxation moduli are independent of strain for strain values below 0.1. Transient extensional measurements were conducted at strain rates of 0.01 to 1.0 s⁻¹. At small stresses the extensional viscosity has the threefold value of shear viscosity as predicted by Trouton. There appeared to be no steady state regime for either grade of PCL studied and as a result η_e(ε) could not be determined. The departure from the linear limit is fastest for the highest extensional rate. Extension thickening behavior is observed at Hencky strains ranging from 1.0 to 2.0. PCL 767 displayed greater extension thickening than PCL 787 at the same temperatures. The Wagner integral constitutive equation was found to give an acceptable fit to the stress growth data in shear and extension, with the fit being better for PCL 767 than for PCL 787.     

Flow and crystallization of saturated fatty acid methyl esters and their binary mixtures

Demand for biodiesel has increased due to being a more environmentally-friendly fuel. Cold weather operation of biodiesel is challenging due to fatty acid methyl ester (FAME) content in biodiesel. Saturated FAMEs crystallize at relatively high temperatures, increase the viscosity of biodiesel, and can clog fuel lines. Here, several factors altered crystallization temperature (CT) of FAMEs, including composition, shear rate, and cooling rate. The crystallization of pure and binary mixtures of methyl palmitate, methyl myristate, and methyl stearate were studied under shear flow and static conditions. Static phase CTs of pure methyl palmitate, methyl myristate, and methyl stearate were 26, 14, and 35°C, respectively. In binary mixtures, CTs were depressed up to 7°C, which agreed with freezing point depression theory. Increasing shear rate up to 100 s⁻¹ decreased CT by 2°C compared to static conditions. Decreasing cooling rate from 1 to 0.1°C/min increased CT less than 2°C. Overall, FAME composition altered CT more than shear flow or cooling rate for pure and binary mixtures of three FAMEs.     

Melt rheology of blends of semicrystalline polymers. I. Degradation and viscosity of poly(ethylene terephthalate)–polyamide-6,6 mixtures

Melt rheology of poly(ethylene terephthalate)–polyamide-6,6, and their blends was studied between 240°C and 300°C, in capillary and rotational rheometers. The flow curves were determined in the range of rate shear from about 10^?2to 10⁵ (s^?1). The results indicate a considerable degree of compatibility, presence of associations between the two types of macromolecules, and cocrystallization. A new mechanism of flow for the blends has been proposed. The study also considers the kinetics of thermal degradation.     

Elongational viscosity of polymer melts: A lubricated skin-core flow approach

Previous work by this research group has shown that the use of a lubricated skin/core flow of polymer melts and a hyperbolic converging die results in an essentially pure elongational flow at a constant elongational strain rate in the core. The previous work was carried out on a laboratory-scale coextrusion system in a planar slit die; tracer particles and an image analysis system were used to confirm the predicted behavior. In this work, the technique was implemented first on the coextruder assembly, as a planar elongational rheometer, and then on a commercial capillary rheometer, as a uniaxial elongational rheometer for polymer melts. The later is achieved by replacing the standard capillary die with a hyperbolic axisymmetric die. A two-laycred billet is prepared for placement in the rheometer barrel by completely encapsulating the core polymer (the polymer to be analyzed) with a low-viscosity polyethylene skin. Commercial grades of polypropylenes, syndiotactic polystyrene, and nylon-66 were analyzed using this technique. Elongational viscosity at high extensional rates can be determined with this method; values in excess of 500 s⁻¹ have already been achieved. © 1996 John Wiley & Sons, Inc.     

Rheology of low nematic transition temperature thermotropic liquid crystalline copolyester HBA/HQ/SA

The rheology of a liquid crystalline copolyester of hydroxybenzoic acid, hydroquinone, and sebacic acid (HBA/HQ/SA copolyester) was studied on both a rotational and a capillary rheometer. DSC studies show that the copolyester has a crystalmesophasic and a broad mesophasic-isotropic transition at 170°C and 220°C. Optical texture observations show the mesophase is characterized by line defect textures, which are characteristic of a nematic structure. At 220°C, both isotropic and nematic phases coexist with the latter being the major. As temperature reaches 250°C, a clear dominance of isotropic phase is observed. At this temperature, the nematic phase of irregular shapes randomly disperses within the isotropic matrix. Subsequent rheological studies were thus conducted in crystal/nematic biphase, single nematic phase, nematic/isotropic biphase, and the near single isotropic phase. Dynamic strain sweep measurements show that a linear viscoelastic region exists at all temperatures tested. The maximum strain amplitude for the linear viscoelastic region is found to be highly structure dependent; it is > 100% in the nematic phase, ∼20% in the biphases, and only about 5% in the isotropic phase. The concurrence of curves obtained at different temperatures in a Cole-Cole plot of G′ vs. G″ indicates similar structures in the nematic phase and biphases. Measurements of steady shear viscosity using a rotational rheometer and a roundhole capillary rheometer show that in the nematic phase the copolyester behaves as a shear thinning fluid for a wide shear rate range of 1 ∼ 10,000 s⁻¹, in which the power law index is about 0.6 ∼ 0.8, and the viscosity is < 10 Pa.s at shear rates >1 s⁻¹.     

Molecular orientation of polydimethylsiloxane induced by elongational and shearing strains

A study examining the molecular orientation of poly(dimethylsiloxane) for different combinations of elongational and shear strains is presented. Three different cases were studied: (1) pure elongational strain; (2) increasing shear and decreasing elongational strains; (3) increasing shear and increasing elongational strains. The experiments were performed in a converging flow cell (at room temperature), where elongational and shearing strain rates achieved values of 370 s^?1 and 640 s^?1 respectively. Values of the Hermans orientation function were obtained from measurements of birefringence and polarization angles while strain rates were estimated from laser Doppler anemometry velocity measurements. Prospects for predicting molecular orientation from the stress-optical laws and rheological flow models are outlined and commented on.     

Relationships between processing conditions and rheological behavior of polyethylenes

The rheological properties of high‐density polyethylene melts were found to change drastically after treatment with oxygen or peroxide. Unusual features of the treated melts in shear flow (190°C) included (a) increase in length of time to reach steady state values of shear stress in start‐up experiments; (b) a non‐reproducibility of the low‐shear rate sections of the flow curves measured at increasing and decreasing shear rate; (c) an increase of viscosity at low shear rates compared to the neat sample. Under non‐stationary extensional flow (a regime of constant force) the treatment leads to a change in shape of the strain development with time, an increase of the apparent elongational viscosity, and an increase in time to break. At 150–170°C, the rheological behavior of the treated polyethylenes is completely identical to the corresponding behavior of the untreated. These results, together with data from IR‐spectroscopy and GPC suggest the following mechanism: The oxidation or peroxidation leads to reactive sites in the polymer chain that incorporate a few long branches during the initial contact with oxygen or peroxide. These reactive sites remain in the polymer after cooling/solidification and can become activated again upon heating to 190°C causing additional changes in molecular structure. Formation of the long‐chain branches results in an increased resistance of the melt to extensional deformation, and an improvement in processing behavior, as well as the quality of bottles produced by the blow‐molding process. Polym. Eng. Sci. 44:615–624, 2004. © 2004 Society of Plastics Engineers.     

Effect of entrance geometry on the capillary flow of cellulose acetate–acetone solution

Capillary flow data were obtained for a 27.5% solution of cellulose acetate in acetone. The solution temperature was 50°C, and the range of apparent shear rates investigated was 1.7 × 10⁵ to 1.7 × 10⁶ sec^?1. Capillaries having tapered entrance angles of 37.88° to 120.63° were used. A power-law model was adequate to describe the shear stress at the wall (τ_w) and the corrected shear rate \documentclass{article}\pagestyle{empty}\begin{document}$(\dot \gamma )$\end{document} relationship. Entrance angle affected the entrance pressure drop corrected for kinetic energy, (ΔP_0,c); ΔP_0,c increased as the angle widened. Treating the entrance flow as an elongational flow situation facilitated superposition of the Delta;P_0,c data on a single curve. Estimated elongational viscosities decreased with increasing applied stress.     

A new rheometer measuring infrared dichroism in molten polymers subjected to transient and steady shear flow

A rotational parallel plate rheometer that enables simultaneous measurement of the transient or steady-state rheological properties and infrared dichroism was designed and constructed to study orientation in molten polymers. Measurements can be carried out at shear rates between 0.05 and 300 s⁻¹ and at temperatures between 20 and 300°C. Both shear stress and axial normal force together with dichroism are continuously measured during shear flow. Infrared dichroism data for polypropylene showed excellent agreement with data obtained with a FTIR-instrument. The Hermans orientation function for molten poly(dimethyl siloxane) at steady state showed a strong shear-rate dependence in the region 0.1−20 s⁻¹. Rheological data for molten poly(dimethyl siloxane) agrees with data obtained from a conventional rheometer.     

Viscosity of polydimethylsiloxane gum: Shear and temperature dependence from dynamic and capillary rheometry

The rheology of Dow Corning polydimethylsiloxane gum (PDMS/silicone gum) was studied over a time range of 10^?2 to 10⁵ s^?1 and a temperature range of 23–150°C using both capillary and dynamic rheometry. A low shear Newtonian region is observed at room temperature below 0.01 rad/s (increasing to 0.1 rad/s at 150°C) for which an Arrhenius activation energy for a viscous flow of 13.3 kJ/mol was determined. The Cox–Merz rule for merging of shear and complex viscosities is found to be valid up to 10 s^?1. Viscosity is found to be independent of temperature above 100 s^?1, where terminal power‐law flow is encountered. This is exhibited in the dynamic data as equal plateau moduli for the various temperature curves. Gross wall slippage is seen in capillary flows above approximately 100 s^?1, corresponding to a stress value of 70–100 kPa. Slip‐stick (spurt) flow is not observed. The viscosity data are best fitted by the Carreau–Yasuda model with a fitting parameter a of 0.7, a power‐law index n of 0.05 (low because of slip effect), and a zero shear viscosity of 32 kPa s at 23°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2533–2540, 2002     

Validation of cogswell's convergent flow analysis

The behavior of two polymers, namely, low-density and linear low-density polyethylenes, was studied in transient and steady-state shear and elongational flows. The predictions of Wagner's model with a damping function using a generalized invariant were calculated. The model appears to be suitable for predictions of the shear and elongational transient flows on the range of strains experimentally tested. The shear flow curves can also be recovered by the model on a very broad range of shear rates. The model is then used to assess extensional data obtained with the convergent flow analysis proposed by Cogswell. © 1996 John Wiley & Sons, Inc.     

Melt Flow Properties During Capillary Extrusion of Linear Low-Density Polyethylene

Abstract

The melt flow properties of a linear low-density polyethylene (LLDPE) were measured by means of a capillary rheometer under the experimental conditions of temperatures from 220° to 260°C and apparent shear rates varying from 12 to 120 s^?1. The end pressure drop (ΔP _end) was determined by employing the Bagley's plotting method. The results showed that ΔP _end increased nonlinearly with increasing shear stress. The end pressure fluctuation phenomenon was observed at lower shear stress level, and several plateau regions were generated in the end pressure drop-shear stress curves, suggesting onset of the wall-slip phenomenon during die extrusion of the resin melt. The critical shear stress with onset end pressure fluctuation phenomenon increased with a rise of temperature. Furthermore, the melt shear flow did not strictly obey the power law. The melt shear viscosity decreased nonlinearly with increasing shear stress and with a rise of temperature, whereas the dependence of the melt shear viscosity on the test temperature accorded with a formula similar to the Arrhenius expression.