Melt flow behavior in capillary extrusion of nanosized calcium carbonate‐filled poly(L‐lactic acid) biocomposites

Nanosized calcium carbonate (nano‐CaCO₃)‐filled poly‐L ‐lactide (PLLA) biocomposites were compounded by using a twin‐screw extruder. The melt flow behavior of the composites, including their entry pressure drop, melt shear flow curves, and melt shear viscosity were measured through a capillary rheometer operated at a temperature range of 170–200°C and shear rates of 50–10³ s^?1. The entry pressure drop showed a nonlinear increase with increasing shear stress and reached a minimum for the filler weight fraction of 2% owing to the “bearing effect” of the nanometer particles in the polymer matrix melt. The melt shear flow roughly followed the power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Hence, adding a small amount of nano‐CaCO₃ into the PLLA could improve the melt flow behavior of the composite. POLYM. ENG. SCI., 52:1839–1844, 2012. © 2012 Society of Plastics Engineers     

Glass bead-filled polypropylene part I: Rheological and mechanical properties

Five glass bead-filled polypropylene composites were rheologically characterized at 240°C using two rotational rheometers to obtain low shear-rate data and a capillary rheometer to obtain high shear-rate data. Both steady and dynamic properties were measured at low shear rates. Each composite was also injection molded into tensile and flexural test bars for a mechanical properties profile at 25°C. The tensile modulus was determined from a simple extensional deformation whereas the flexural modulus was determined from a three-point-bend test. The relative shear viscosity and relative loss modulus are different nonlinear functions of the volume fraction of beads at a constant shear rate, while the relative storage modulus appears to be a linear function of bead fraction. The relative viscosity decreases with increasing shear rate and the zero shear-rate data are in very good agreement with the Guth-Gold equation. The relative tensile modulus and relative flexural modulus are each linear functions of bead fraction over the entire range of filler concentration, 0-29 vol percent. From these data it is concluded that a simple correspondence between slow viscous flow and small strain elasticity does not exist for these composites.     

Nonlinear viscoelastic behavior of butadiene–acrylonitrile copolymers filled with carbon black

Various viscoelastic measurements including dynamic mechanical measurements in tension at 110 Hz from ?60° to 160°C, tensile stress relaxation measurements with 100% elongation at 25°, 54°, and 98°C, capillary flow measurements at 70°, 100°, and 125°C, and high-speed tensile stress–strain measurements carried to break at 25°, 56°, and 98°C were performed on four samples of carbon black-filled butadiene–acrylonitrile copolymers. All the data were treated with the same equation for time–temperature conversion. The capillary viscosity–shear rate curves were significantly lower than the complex viscosity–angular frequency curves, indicating “strain softening” with extrusion. The viscosity was estimated from the stress–strain relationship at the yield point. The viscosity as a function of the strain rate is significantly higher than the complex viscosity as a function of angular frequency, indicating “strain hardening” with extension. The strain softening and strain hardening are attributable to the structural changes upon deformation of the carbon black-filled elastomers. With the unfilled elastomers, neither strain softening nor strain hardening were observed in similar measurements.     

Effects of Extrusion Rate,Temperature, and Die Diameter on Melt Flow Properties During Capillary Flow of Low-Density-Polyethylene

The melt flow properties of a low-density polyethylene were measured at test temperatures varying from 140 to 170°C and in a wide range of extrusion rates by means of a capillary rheometer, to identify the influence of extrusion conditions (such as temperature, shear rate, and die diameter) on the melt flow behavior in the present paper. The results showed that the entry pressure drop increased nonlinearly with an increase of the piston speeds, and it decreased with an addition of the die diameter. The melt shear flow obeyed roughly the power law and the melt shear viscosity decreased approximately linearly with an increase of the true shear rates in a bi-logarithmic coordinate system. The dependence of the melt shear viscosity on temperature accorded approximately the Arrhenius expression. Under these experimental conditions, the entrance pressure drop increases as an exponential function with an addition of the channel contraction ratio.     

Shear viscosity,extensional viscosity,and die swell of polypropylene in capillary flow with pressure dependency

The shear and extensional viscosities of a polypropylene resin were studied using a capillary rheometer and capillary dies of 1‐mm diameter and length of 10, 20, and 30 mm. Melt temperatures at 190, 205, and 220°C and shear rates between 100 and 5000 s^?1 were used. At the highest shear rate a visible melt fracture was observed. An equation relating the pressure drop and die length was derived with consideration of pressure effects on melt viscosities and the end effect. After the correction for pressure effects the true wall shear stress and end effect at zero pressure were calculated. The end effect showed a critical stress of melt fracture around 10⁵ Pa, and increased rapidly when shear stress increased above the critical stress. From shear stress the shear viscosity was calculated, and a power law behavior was observed. Extensional viscosity was calculated from the end effect and showed a decreasing trend when strain rate increased. After time–temperature superposition shift shear viscosity data correlated well, but an upward trend was observed in extensional viscosity when melt fracture occurred. Die swell ratio at different temperatures can be plotted as a function of wall shear stress and was higher for shorter dies. © 2002 Wiley Perioodicals, Inc. J Appl Polym Sci 84: 1269–1276, 2002; DOI 10.1002/app.10466     

Geometrical dependence of viscosity of polymethylmethacrylate melt in capillary flow

The shear viscosity of polymethylmethacrylate (PMMA) melt is particularly investigated by using a twin‐bore capillary rheometer at four temperatures of 210, 225, 240, and 255°C with different capillary dies. Experimental results show that the geometrical dependence of shear viscosity is significantly dependent on melt pressure as well as melt temperature. The measured shear viscosity increases with the decrease of die diameter at lower temperatures (210 and 225°C) but decreases with the decrease of die diameter at higher temperatures (240 and 255°C). Based on the deviation of shear viscosity curves and Mooney method, negative slip velocity is obtained at low temperatures and positive slip velocity is obtained at high temperatures, respectively. Geometrical dependence and pressure sensitivity of shear viscosity as well as temperature effect are emphasized for this viscosity deviation. Moreover, shear viscosity curve at 210°C deviates from the power law model above a critical pressure and then becomes less thinning. Mechanisms of the negative slip velocity at low temperatures are explored through Doolittle viscosity model and Barus equation, in which the pressure drop is used to obtain the pressure coefficient by curve fitting. Dependence of pressure coefficient on melt temperature suggests that the pressure sensitivity of shear viscosity is significantly affected by temperature. Geometrical dependence of shear viscosity can be somewhat weakened by increasing melt temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3384–3394, 2013     

Rheological behavior of uncured styrene‐butadiene rubber at low temperatures,pure and filled with carbon black

The flow behavior of an uncured styrene‐butadiene rubber (SBR) has been studied by using a specific preshearing capillary rheometer in the range of temperatures encountered in extrusion, i.e. between 40°C and 90°C. A pure SBR and various SBR compounds filled with different amounts of carbon black (from 17 to 33 wt%) have been characterized. It was observed, for all tested materials, that the flow curve could be divided in different parts: at low shear rate, the material exhibits a classical behavior, where stress increases regularly with the shear rate. Above a certain critical stress, flow features changed, characterized by the simultaneous onset of wall slip and upstream instabilities. This critical stress is independent of temperature but increases linearly with carbon black amount. Flow curves at different filler contents were superimposed, using a shift factor that varies with filler content. Two theories for time/filler content superposition were proposed. Finally, a general viscosity law for uncured SBR compounds was introduced. This law is based on a Carreau‐Yasuda equation, where zero‐shear viscosity and characteristic time depend on both temperature and filler content, through Arrhenius and Krieger‐Dougherty expressions, respectively. POLYM. ENG. SCI., 55:2156–2162, 2015. © 2015 Society of Plastics Engineers     

Capillary rheometry of raw elastomers,butadiene-acrylonitrile copolymers

Capillary rheometry of four butadiene-acrylonitrile copolymer raw elastomers was performed at 125°C over a wide shear rate range. The data were corrected for the effect of pressure on viscosity, for pressure loss in the barrel and at the capillary entrance, for the non-Newtonian velocity profile (Rabinowitsch correction) and for the temperature rise at high shear rates (shear heating). The corrected results were compared to the tensile stress strain data obtained at comparable strain rates. The agreement between the capillary flow data and the tensile stress strain data was quite good, however, some slight systematic differences were noted. The difference was interpreted as the consequence of slipping of materials at the capillary wall. Die swell values were measured and presented as functions of shear rate and capillary length. Extrudate distortions are described.     

Melt flow and fiber properties of copolyesters

The effect of modifying monomer [sodium 3,5-di(carbonethoxy)benzene sulfonate] contents range from 1.5 to 4.5 mol % on the melt flow and fiber properties of copolyesters (COPET) dyeable with basic dyes was investigated. An Instron capillary rheometer was used to obtain data over shear rates ranging from 10 to 10⁴ s^?1 at 265, 275, and 285°C. The COPET's flow properties as a function of temperature, inherent viscosity, melting point, and modifying monomer content were determined. The drawn fibers annealed in oil and air at 80, 110, 130, 150, 175, and 200°C were studied by means of measurements of shrinkage ratio, crystallinity, birefringence, long period, sonic rate, and static state flexibility of molecular chain. All these showed that the large side group, ? SO₃Na in COPET molecular chains causes an increase in chain rigidity and melt viscosity, and a decrease in crystallinity and orientation.     

Shear and extensional flow of a thermotropic liquid crystalline polymer

The flow of a thermotropic liquid crystalline polymer (unfilled and glass fiber filled) was studied using a capillary rheometer and an instrumented injection molding machine. Despite different thermal histories, the techniques gave similar results. From 330 to 350°C, viscosity was independent of temperature. At 340°C, where most measurements were carried out, pronounced shear-thinning occurred and the shear flow curves were nonlinear, the power law exponent decreasing from 0.51 at a shear rate of 10 s⁻¹ to 0.35 at 10⁴ s⁻¹. A previously reported model was used to derive elongational flow curves from die entry pressure data. Because of the nonlinearity of the flow curves, quadratic log-stress vs. log-strain rate plots were needed to model behavior over the strain rate region studied. The elongational flow curves were similar in shape to the shear flow curves, with an effective Trouton ratio of 30. Despite orientation and structure present in the melt, the extensional viscosities and Trouton ratios were within the range found with normal thermoplastic melts. The results suggest that extensional flow may be inhomogeneous, the flowing units possibly being partially ordered domains.     

Über die druckabhängigkeit der viskoelastischen und physikalisch-chemischen eigenschaften von polymeren, 8. Die viskosität von polyethylen bis 5000 bar

A new high pressure viscosimeter is described which permits rheological investigations up to 5000 bar and 200°C. The dependence on pressure and shear rate of the apparent viscosity of polyethylene is measured at 130, 155, and 190°C. Newtonian viscosity is calculated according to the method of Spencer and Dillon, its pressure coefficient decreases with pressure; crystallization induced by flow causes the pressure coefficient to increase abnormally. Free volume decreases in quite the same way as the pressure coefficient when pressure raised. From the slope of the log η_s-P_M-curve can be concluded that the pressure coefficient of non-Newtonian flow decreases with increasing pressure and shear rate.     

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.     

An evaluation of the pressure‐dependent melt viscosity of polyphenylsulfone

A method for the determination of pressure‐affected viscosity from capillary rheometry and pressure–volume–temperature (PVT) data was tested on polyphenylsulfone melt. Shear viscosity data evaluated at selected temperatures (345–375°C) were interlinked to the PVT data at pressures ranging from 1 to 200 MPa. According to the recently proposed correlation approach, a pressure‐dependent shear viscosity is derived from the relationship (verified on several commodity polymers) between temperature‐dependent viscosity and a free volume parameter computed using the Simha–Somcynsky equation of state. Finally, the predicted pressure‐viscosity coefficient was compared with the value obtained experimentally on a modified single piston rheometer. POLYM. ENG. SCI., 54:711–715, 2014. © 2013 Society of Plastics Engineers     

Viscosity of copolymers containing carbon black

The flow behavior of random copolymers of styrene and butyl methacrylate containing specific carbon blacks varying in surface area were studied at various temperatures and shear rates. Master curves of reduced viscosity as a function of shear rate were prepared for the pure copolymers at 150°C. The superposition required vertical and horizontal shifts, proportional to (a_T)^?1 and (a_T)^.53, respectively, where a_T is the shift factor. With the incorporation of carbon black, the viscous response is non-Newtonian exhibiting a yield stress at increasing filler concentration and surface area. Master curves of viscosity against shear rate were generated at fixed filler loadings and surface areas by using a single horizontal shift factor.     

Thermal degradation of polypropylene in a capillary rheometer

Melt viscosity of a polypropylene (PP) resin was measured in a capillary rheometer between 220 and 260°C. The melt viscosity showed a power law behavior with strong shear rate dependence. The effects of temperature and shear rate on the degradation were studied in the rheometer by heating at 260 and 280°C, and extruding at shear rates up to 10000 sec ?1 . Melt flow index (MFI) of samples after shearing and heating treatment was measured to characterize the molecular weight change. An increase in MFI was found for PP sheared at high temperature. Heating for longer time also increased MFI. Increase of shear rate had a small effect on increasing MFI at 260°C but produced a larger effect at 280°C. A constant increment in MFI was observed in PP subjected to high temperature processing and was attributed to degradation due to oxygenated products.     

Correlation between entry pressure losses and elongation viscosity of polyethylene melts

The correlation between the entry pressure drop and elongation viscosity during entry converging flow of polymer melts was discussed in this article. The entry pressure drop during extrusion of a low density polyethylene (LDPE) melt and a linear low density polyethylene (LLDPE) melt was measured by means of a capillary rheometer under test conditions with temperature of 170 °C and shear rate varying from 10 to 300 s⁻¹. The results showed that the entry pressure drop increased nonlinearly with an increase of the shear stain rate, and the variation of entry pressure drop of the two melts was close to each other. The melt elongation viscosity of the two resins was estimated using Cogswell equation from the measured entry pressure drop data, and the predictions were compared with the melt extension viscosity measured by using a melt spinning technique published in literature. It was found that the melt extension viscosity from entry converging flow was slightly lower than that from melt spinning technique under the same temperature and extension strain rate.     

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.     

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     

An experimental study of the relationship between rheological properties and spinnability in the dry spinning of cellulose acetate–acetone solutions

The elastic and viscous properties of five cellulose acetate–acetone solutions, varying from 19.9% to 28.6% solids concentration, are independently determined at 60°C by capillary rheometry techniques. The viscous flow behavior of the solutions is determined over four decades of shear rate. The Bagley analysis is used to determine the entrance pressure drop and the true shear stress at various shear rates. A plot of the entrance pressure drop at the maximum experimental shear rate versus solution concentration undergoes a rapid increase in slope at 24.0% solids concentration, the significance of which is discussed with respect to the development of an elastically deformable chain entanglement network. The die swell behavior of the solutions at 60°C is determined on a commercial-type dry-spinning apparatus. When the die swell ratio is plotted versus volumetric flow rate, all five solutions are found to possess a characteristic curve with a distinct maximum. Photographs illustrating the variation of die swell with volumetric flow rate are shown. Die swell measurements are also shown to correlate well with entrance pressure drop measurements. The degree of spinnability of each cellulose acetate–acetone solution at 60°C is found by determining first godet speed at which one or more threads break abruptly. Spinnability is found to go through a maximum at 24.0% solids concentration. The rheological measurements and spinnability results are discussed through the aid of a single rheological parameter incorporating both elastic and viscous solution responses.     

Effects of extrusion conditions on rheological behavior of acrylonitrile–butadiene–styrene terpolymer melt

The influence of temperatures and flow rates on the rheological behavior during extrusion of acrylonitrile–butadiene–styrene (ABS) terpolymer melt was investigated by using a Rosand capillary rheometer. It was found that the wall shear stress (τ_w) increased nonlinearly with increasing apparent shear rates and the slope of the curves changed suddenly at a shear rate of about 10³ s^?1, whereas the melt‐shear viscosity decreased quickly at a τ_w of about 200 kPa. When the temperature was fixed, the entry‐pressure drop and extensional stress increased nonlinearly with increasing τ_w, whereas it decreased with a rise of temperature at a constant level of τ_w. The relationship between the melt‐shear viscosity and temperature was consistent with an Arrhenius expression. The results showed that the effects of extrusion operation conditions on the rheological behavior of the ABS resin melt were significant and were attributable to the change of morphology of the rubber phase over a wide range of shear rates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 606–611, 2002