Effects of plasticizer on shear modification of polystyrene

The elastic and viscous properties of polymer melts may be affected by the shear history of the polymer. The extrudate swell of a polymer melt is primarily a manifestation of the elasticity of the polymer melt. In this study, a single screw extruder was used to impose different shear histories on a polystyrene polymer which was processed with and without added plasticizer. The extrudate swell and apparent viscosity of these melts were measured with a capillary rheometer. These characteristics of unplasticized polystyrene are almost not affected by the various preshearing processes. However, the extrudate swell and viscosity of polystyrene containing plasticizer are affected by plasticizer level, shear history and thermal history. After most of the plasticizer in the presheared plasticized polystyrene was extracted, the extrudate swell was still lower than that of the parent sheared polystyrene with the same shear history and the same plasticizer content. These results were obtained without significant changes in molecular weight. Shear modification by conventional process equipment may become impractical if the shear field intensity or dwell time of the material in the apparatus is limited. In such cases, shear refinability by standard process equipment may be observed if the coupling density in the polymer is reduced by some additional means, such as blending with a plasticizer.     

Effect of jet stretch on polyacrylonitrile as‐spun fiber formation

In this article, the effect of jet stretch ratio on the extrudate die‐swell effect of polyacrylonitrile spinning solution and the structure and properties of as‐spun fibers was systematically analyzed by means of X‐ray diffraction (XRD), electron microprobe analysis, and the measurement of die‐swell ratio, boiling‐water shrinkage, porosity, mechanical properties analysis, etc. It revealed the formation mechanism of the die‐swell effect and spin orientation and its influences on the structure and properties of as‐spun fibers. It showed that with the increase of the jet stretch ratio the die‐swell ratio became smaller, both the degree of spin orientation and the crystallinity increased, the microstructure of as‐spun fibers became compact and homogeneous, and the cross section tended to be circular. As a result, the breaking tenacity of as‐spun fibers and resultant precursors all increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3348–3352, 2007     

The numerical simulation of boger fluids: A viscometric approximation approach

A general-purpose finite element program has been used to simulate the flow of nonshear-thinning, highly elastic polymer solutions (Boger fluids). In particular, the creeping flow through an abrupt 4:1 circular and planar contraction is studied, as well as the flow at the exit of a capillary die for the determination of extrudate swell. Experimentally measured normal stress and viscosity data are included in a simple rheological model, based on the viscometric simplification of the CEF constitutive equation. Vortex size and intensity in the die entry and extrudate swell at the die exit increase rapidly, with elasticity level, in general agreement with experimental findings. It is shown that despite the limitations of the model, the viscometric approximation can be used to study the effect of normal stresses in cases where a main flow direction can unambiguously be defined. In die exit Flows, it can also provide an upper limit for the determination of extrudate swell, while Tanner's theory of elastic recovery provides the lower limit.     

Effect of die temperature on the flow of polymer melts. Part II: Extrudate swell

The effect of die wall temperature on the extrudate swell of polymer melts flowing through dies with single and dual circular channels was studied. Extrudate swell was measured at constant flow rates using an Instron capillary rheometer with a modified die section. It was found that under isothermal conditions, extrudate swell plotted against the average wall shear stress gave rise to a temperature independent correlation for polystyrene. Under non-isothermal conditions, such a correlation did not exist, which might be due to the change of wall shear stress in the axial direction. The extrudate swell in the non-isothermal cases can be better correlated with the wall shear stress at die exit. For the two-hole die, changes of die wall temperature varied both the flow rate ratio and the extru date swell ratio. The latter is, however, much less sensitive to the die wall temperature than the former.     

Extrudate swell and texture of PS,LDPE, ABS,PVC melts and their blends in extrusion capillary flow using a magnetic die

The extrudate swell behavior and extrudate texture of various thermoplastic melts, namely, polystyrene (PS), low‐density polyethylene (LDPE), acrylonitrile‐butadiene styrene (ABS) copolymer, poly(vinyl chloride) (PVC), and their blends, were examined weith a magnetic die system in a constant‐shear‐rate capillary rheometer at a shear rate range 5–28 s^?1 and a temperature range 170–230 °C. The extrudate swell results obtained from the magnetic die were then compared with those produced by a nonmagnetic die. The results showed that the extrudate swell increased with shear rate, but decreased with temperature. In a pure polymer system, up to 25% increase in the extrudate swell was observed with the application of the magnetic field to the PS melt, and the effect decreased in the order ABS > LDPE > PVC. The extrudate swell changes were associated with the changes in rheological properties of the melts. The extrudate textures of the ABS and PVC melts were improved by the magnetic field. In PS/LDPE or PS/ABS blend, it was found that the magnetic die resulted in higher values of the extrudate swell than the nonmagnetic die for all blends, the magnetic effect being less as the LDPE or ABS content was increased. For PS/LDPE system, the extrudate swell of the PS melt did not change much with addition of 20% LDPE, but slightly decreased at the LDPE loading of 40%. At higher LDPE loadings, the extrudate swell increased towards the value of the pure LDPE melt. For PS/ABS system, the extrudate swell ratio progressively decreased with increasing ABS content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 509–517, 2002     

An experimental investigation of capillary extrudate swell in relation to parison swell behavior in blow molding

An experimental study was carried out to study and characterize the capillary extrudate swell and parison swell behavior in extrusion blow molding of two commercial blow molding grade high density polyethylene resins. The capillary extrudate swell behavior of these resins were determined employing a capillary rheometer and a special thermostatting chamber. Parison swell behavior was determined using an Impco A13-R12 reciprocating screw blow molding machine in conjunction with cinematography and pinch-off. The experimental conditions under which capillary extrudate and parison swell data can be related are elucidated. Excellent agreement is found between the area swell values determined on the basis of capillary and parison swell experiments.     

Experimental studies on radial extrudate swell and velocity profiles of flowing PS melt in an electro‐magnetized die of an extrusion rheometer

This article investigates the radial extrudate swell and velocity profiles of polystyrene melt in a capillary die of a constant shear‐rate extrusion rheometer, using a parallel coextrusion technique. An electro‐magnetized capillary die was used to monitor the changes in the radial extrudate swell profiles of the melt, which is relatively novel in polymer processing. The magnetic flux density applied to the capillary die was varied in a parallel direction to the melt flow, and all tests were performed under the critical condition at which sharkskin and melt fracture did not occur in the normal die. The experimental results suggest that the overall extrudate swell for all shear rates increased with increasing magnetic flux density to a maximum value and then decreased at higher densities. The maximum swelling peak of the melt appeared to shift to higher magnetic flux density, and the value of the maximum swell decreased with increasing wall shear rate and die temperature. The effect of magnetic torque on the extrudate swell ratio of PS melt was more pronounced when extruding the melt at low shear rates and low die temperatures. For radial extrudate swell and velocity profiles, the radial swell ratio for a given shear rate decreased with increasing r/R position. There were two regions where the changes in the extrudate swell ratio across the die diameter were obvious with changing magnetic torque and shear rate, one around the duct center and the other around r/R of 0.65–0.85. The changes in the extrudate swell profiles across the die diameter were associated with, and can be explained using, the melt velocity profiles generated during the flow. In summary, the changes in the overall extrudate swell ratio of PS melt in a capillary die were influenced more by the swelling of the melt around the center of the die. Polym. Eng. Sci. 44:2298–2307, 2004. © 2004 Society of Plastics Engineers.     

Experimental study on extrudate swell and die geometry of profile extrusion

The objective of this study was to determine the die swell behavior of a polymer melt and to design a die for forming a polymeric extrudate with a desired shape using profile extrusion. Polystyrene pellets were chosen to perform the profile extrusion experiments. First, the polystyrene pellets were melted and pushed through a quarter ring profile. The profile of the swelled extrudate agreed with the numerical predictions. A modified die was designed to produce a quarter ring profile extrudate based on the direct extrusion problem (DEP) prediction. Polystyrene pellets were also melted and pushed through the modified die. The experimental results were close to the computational results. The melting temperature, die length, and melting residence time affect die swell behavior. The die swell ratio becomes smaller as the melting temperature and melting residence time are increased. As the die length is increased, the die swell ratio is lowered. According to the die geometry predictions, an extrudate with the desired profile can be made precisely.     

Effects of die temperature on extrudate swell in screw extrusion

Extrusion of a hot polymer melt through a cooler die zone substantially increases the extrudate swell of some thermoplastics. This effect was examined for commercial samples of low-density polyethylene, polypropylene, and polystyrene. Two conflicting effects come into play during extrusion of a thermoplastic. Colder melt temperatures promote increased extrudate swell, but the same conditions also facilitate molecular disentanglement and reduced melt elasticity and die swell. Since the extrusion process itself may affect the relation between die swell and melt temperature, laboratory-scale measurements for the design of processes like blow molding are better carried out with small-scale screw extruders than with capillary rheometers. For some applications it may be advantageous to use a polymer whose die swell is particularly responsive or unresponsive to die temperature variations. The procedure described in this article can be used effectively to monitor this characteristic.     

Numerical simulations of annular extrudate swell of polymer melts

Numerical viscoelastic simulations were carried out using a K-BKZ type of separable integral constitutive equation. Both reversible and irreversible models were tried for several types of damping functions to calculate the annular extrudate behavior of high-density polyethylene (HDPE). There are two aims in this study; first, to clarify the properties of these dumping functions, and second, to investigate the influence of rheological characteristics on annular extrudate swell. In these numerical simulations, relaxation spectrum and shear viscosity were fixed, and the other characteristics were varied. The reversional response of the damping function mainly has an effect on the magnitude of the area swell even if the die is straight. The irreversible model expresses the experimental results of annular extrudate swell better than the reversible model. The accurate fitting of N1 by the damping model is important for predicting it. The magnitude of N1 predicted from the Wagner exponential model is lower than that of the PSM model, and the area swell shows the same tendency as N1. A modified PSM model that allows the N1 curve to shift can fit the magnitude of area swell. The relationship between the diameter and thickness of the extrudate depends on N2/N1, and it was estimated by simple linear elasticity of solids. The time dependent viscosity varies with the type of damping function, and it influences the time-dependent swell.     

Swell and distortions of high-density polyethylene extruded through capillary dies

The effect of varying the die entrance angle and the die length on extrudate swell and on the onset of extrudate distortion in capillary extrusion has been studied. Using theory from the literature, we have analyzed the contribution to the total pressure drop from the elongational and shear deformation in the entrance region, and from the capillary pressure drop in the land region of the die. From the contribution of the elongational deformation, we obtained an estimate for the elongational viscosity of the polymer. The same analysis was used to study the influence of the die geometry on the stick-slip instability. It is found that the elongational component at the inlet region mainly influences the extrudate distortions. The onset of the stick-slip instability occurs within 10% at a wall stress τ_w of 0.3MPa, where τ_w is calculated from expressions assuming fully developed flow. The variation around this average value is systematic with changes in die geometry, and the observed variations are probably due to the non-homogeneous pressure field in the die. We also propose a model for predicting extrudate swell. Input to the model are material parameters obtainable from oscillatoric measurements of the loss and storage modulus and residence times calculated from the geometry of the die. The swell model includes a fitting parameter that sets the overall scale of the swell.     

High weissenberg number simulation of an annular extrudate swell using the differential type constitutive equation

Annular extrudate swell simulations at high Weissenberg numbers were made using a differential type constitutive equation. The streamline-upwinding method with a sub-element for extra stress components, which is called SU4 × 4, is one of the best mixed finite element methods for computation of viscoelastic flows. Planar and capillary extrudate swell calculations at high Weissenberg numbers (We > 1000) were accomplished by SU4 × 4. However, annular extrudate swell simulations at high We by SU4 × 4 were not successful. The calculated We was less than about 4. A new calculation technique using a Newton-Raphson discretization of the equation of motion was developed. This technique is called a “new under-relaxation method.” The calculated We of annular extrudate swell simulation by the new under-relaxation method with SU4 × 4 was about 6～250 times larger than those by SU4 × 4. Reasonable calculation results were obtained in an annular flow and a capillary extrudate swell by this method, and the reliability and the utility of the new under-relaxation method are shown. It is now possible to consider the swell shapes of annular extrudate under industrially useful conditions. The calculated swelling ratios were also compared with experimental ones.     

Extrudate swell of high density polyethylene. Part II: Time dependency and effects of cooling and sagging

For two high density polyethylene resins, the isothermal time dependency of extrudate swell has been measured. Very minor differences in the large molecular weight part of the molecular weight distribution, hardly detectable with gel permeation chromatography and low angle laser light scattering techniques, dramatically influence the time dependency of extrudate swell as well as the maximum swell attainable. The presence of larger molecules in sample 802 than in 801 is reflected in a lower short time (after seconds) and a larger long time (after minutes) or maximum extrudate swell value. Extruding the polymers through a capillary die L:D = 30:2 mm into air at ambient temperature allows only the short time swelling behavior to be observed, because cooling and sagging of the strand.     

Melt extrudate swell behavior of multi‐walled carbon nanotubes filled‐polypropylene composites

The extrudate swell behavior of polypropylene (PP) composite melts filled with multi‐walled carbon nanotubes (MWCNTs) was studied using a capillary rheometer in a temperature range from 190 to 230°C and at various apparent shear rates varying from 50 to 800 s⁻¹. It was found that the values of the extrudate swell ratio of the composites increased nonlinearly with increasing apparent shear rates, while the values of the extrudate swell ratio decreased almost linearly with increasing temperature. The values of the melt extrudate swell ratio increased approximately linearly with increasing shear stress, while decreased approximately nonlinearly with an increase of the MWCNT weight fraction. In addition, the extrudate swell mechanisms were discussed with observation of the fracture surface of the extrudate using a scanning electronic microscopy. This study provides a basis for further development of MWCNTs reinforced polymer composites with desirable mechanical and thermal properties. POLYM. COMPOS., 38:2433–2439, 2017. © 2015 Society of Plastics Engineers     

Swell of extrudate from an annular die

Diameter and thickness swells have been measured as functions of time and wall shear rate for three high density polyethylenes at 170°C and one polypropylene at 190°C. By extruding into an oil having the same temperature and density as the extrudate, it was possible to measure isothermal swell in the absence of drawdown. Seventy to 80 percent of the swell occurs in the first one or two seconds, while several minutes are required to reach an equilibrium state. Relationships between various swell parameters, including parison weight swell and capillary extrudate swell, are examined. Important differences between the behavior of the polyethylenes and that of the polypropylene are noted.     

The effect of extrudate swell on modeling the film blowing process

The extrudate swell effect has not received sufficient attention in modeling the film blowing process. This effect is addressed in this paper, and as an ab initio study, only viscous fluids were considered. The problem region was separated into two zones; the extrudate swell zone and the film blowing zone. The annular extrudate swell problem was solved using a finite element method. The film blowing process was modeled following Pearson and Petrie's (4) work. Although only viscous fluids were considered, the simulation results show a remarkable difference when swelling was included in the modeling. Viscoelastic fluids, which are more realistic for polymer melts, were not investigated here because of the so called high Weisenberg number problem. This is an open area still under investigation.     

Extrudate swell during the melt spinning of fibers—influence of rheological properties and take-up force

A theoretical and experimental study has been carried out on extrudate swell B, especially the influence of rheological properties and applied take-up force on the emerging melt. The problem is analyzed in terms of (1) dimensional analysis, (2) force–momentum balances, (3) partially constrained elastic recovery. Analyses in terms of force–momentum balances are only able to give extrudate swell B in the asymptote of high Reynolds numbers. For low Reynolds numbers, they simply relate the take-up force to the pressure field in the spinneret. Increasing the take-up force predicts a decrease in the exit pressure. The partially constrained elastic recovery theory yields an expression for B as a decreasing function of applied take-up force. Specifically, this is where B(0) is the extrudate swell in the absence of applied forces, λ_eff is the effective relaxation time, μ is viscosity (both evaluated at the capillary wall), and D is the spinneret capillary diameter. An experimental study of extrudate swell of several rheologically characterized melts (high density polyethylene, low-density polyethylene, polypropylene, polystyrene) has been carried out at 180°C by four different methods (frozen, annealed in hot silicone oil, photographed emerging into air, photographed emerging through 180°C silicone oil) in the absence of applied take-up forces. Extrudate swell for a melt emerging from dies with differing diameters correlates with capillary-wall shear rate. A comparison of extrudate swell with normal stress–shear stress ratio shows the best agreement for frozen extrudates and photographs of melts emerging into air. The data is compared to the Tanner theory of extrudate swell. B has been determined during melt spinning and shown to be a function of take-up force for both a high-density polyethylene and polypropylene melt. B decreases rapidly with applied take-up stresses. The results are compared to the predictions of the partially constrained elastic recovery theory.     

Experimental studies on extrudate swell behavior of PS and LLDPE melts in single and dual capillary dies

Extrudate swell behavior of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts was investigated using a constant shear rate capillary rheometer. Two capillary dies with different design configurations were used, one being a single flow channel and the other being a dual flow channel. A number of extrudate swell related parameters were examined, and used to explain the discrepancies in the extrudate swell results obtained from the single and dual flow channel dies, the parameters including output rate and output rate ratio, power law index, wall shear rate, wall shear stress, melt residence time, pressure drop induced temperature rise, flow channel position relative to the barrel centerline, and the flow patterns. It was found in this work that the power law index (n value) was the main parameter to determine the output rate ratio and the extrudate swell between the large and small holes for the dual flow channel die: the greater the n value the lower the output rate ratio and thus decreased extrudate swell ratio. The differences in the extrudate swell ratio and flow properties for PS and LLDPE melts resulted from the output rate ratio and the molecular chain structure, respectively. The extrudate swell was observed to increase with wall shear rate. The discrepancies in the extrudate swell results from single and dual dies for a given shear rate were caused by differences in the flow patterns in the barrel and die, and the change in the melt velocities flowing from the barrel and in the die to the die exit. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1713–1722, 2003     

多腔精密医用导管挤出胀大的数值模拟分析

采用Polyflow软件对多腔精密医用导管在内腔无注气/注气两种条件下的挤出胀大行为进行了数值模拟分析,直观地反映了挤出胀大后制品截面形状的变化规律,以及注气条件下不同内腔压力差时挤出胀大行为,获得了导管截面变形与压力差之间的关系。这为机头口模的设计及改进提供了理论依据。模拟结果表明:在无注气情况下,胀大后的截面形状与口模的截面形状存在较大的区别,引入注气条件后,制品截面形状受挤出胀大和气压的双重影响,变形更为复杂,必须合理地控制气体的压力及流量。适当的气体压力和压力差可以起到改善制品截面形状的作用,但过大或过小的压力将对制品截面形状的改善起到反作用。     

Compensating for die swell in the design of profile dies

Because of the effects of die swell, the final shape of an extrudate is often substantially different from that of the exit opening of the die. As a result, the design of profile dies producing complex shapes often involves more than just “balancing” the die but also compensating for the effects of die swell. Typically, a successful design of such dies is achieved only through much “cut and try,” However, with the use of a fully three‐dimensional finite element flow algorithm along with quick mesh generating capabilities, the usual cut and try involved in the design of many profile dies can be greatly reduced, if not eliminated. This paper demonstrates how the effects of die swell can be compensated for in the design of profile dies. For profiles with one plane of symmetry, this includes compensating for the sideways translation of the extrudate as well as the change in shape that the extrudate experiences. Completely asymmetric profiles undergo a “twisting” downstream of the die. This twisting, which appears not to have been reported in the literature (at least for isothermal extrusion), is also accounted for here, along with the change in shape that the extrudate undergoes. The translation or twisting of profiles downstream of a die is often attributed to non‐Newtonian or non‐isothermal effects. Only isothermal Newtonian examples are considered here. These results clearly show that asymmetry of the profile will result in a translation and twisting of the extrudate even in the isothermal Newtonian case.