Die design for rigid PVC—the effect of die land length on extrudate swell

PVC profile extrusion compounds have a unique morphology. While other polymers gradually decrease in extrusion die swell with increasing length/thickness (L/D) ratio, PVC profile extrusion compounds have a low die swell, quite independent of the die's L/D ratio in the range of 5 to 20. The fact that the die land length can be changed without changing the extrudate swell is an important consideration, which makes die design and balancing dies simpler and easier for PVC profile extrusion compounds. While other polymers substantially increase extrudate swell with increased shear rate, the swell of the PVC profile compounds is not much affected by shear or extrusion rate. This unique behavior allows wider processing latitude in profile extrusion and faster extrusion rates than with other polymers. Another unique factor in the rheology of PVC profile extrusion compounds is that extrusion die swell increases with increasing melt temperature, while other polymers have decreasing die swell with increasing melt temperature. The unusual rheology of PVC profile extrusion compounds is attributed to its unique melt morphology, where the melt flow units are 1 um bundles and molecules that have low surface to surface interaction and entanglement at low processing temperatures but increased melting and increased entanglement at higher processing temperatures. Other polymers, unlike PVC, have melt flow at the molecular level.     

Particle size and molecular weight effects on the melt flow of emulsion PVC

The melt flow behavior of straight emulsion-polymerized PVC in a capillary extrusion rheometer has been found to depend upon both the molecular weight and the particle size of the sample. Observations of flow-rate, post-extrusion swell, and extrudate appearance, as functions of extrusion temperature and pressure, suggest that both molecular deformation and particle slippage are involved in the flow mechanism. The relative importance of these two modes of flow varies with extrusion conditions and with the PVC molecular weight and particle size. Particle slippage is favored by large particle size, high molecular weight, and low temperature and by a shear stress above a critical yield value. Apparent melt viscosity, swelling, and roughness are minimized under conditions corresponding to the maximum contribution of particle slippage. In the proper range of temperature and shear rate, straight emulsion PVC yields smooth, low-swell extrudates of excellent physical properties.     

Rheology,morphology, and mechanical and thermal properties of recycled PVC pipes

This article demonstrated the possibility of recycling PVC pipes by investigating the effect of adding PVC pipes (varying from 0 to 80 % wt) into two commercial PVC virgin grades on the rheological, morphological, mechanical, and thermal properties of the PVC blends. The results obtained showed an increase in the melt viscosity and no change in the die swell ratio as the concentration of the recycled PVC was increased. The die swell ratio was observed to increase with temperature, this being associated with the presence of gelation that occurred at high temperature. The optimum tensile and impact strengths were detected, the impact strength being explained by use of SEM micrographs of the fracture surface. The hardness result corresponded well to the density of the compounds. The glass transition, degradation, and heat-deflection temperatures were also found to shift with the recycled PVC loading. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2478–2486, 2001     

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.     

Capillary extrusion behavior of phenolphthalein poly(ether-ether-sulphone) (PES-C)

The capillary extrusion flow properties of novel engineering thermoplastic phenolphthalein poly(ether-ether-sulphone) (PES-C) have been investigated using capillary rheometer. The dependence of viscosity on the wall shear rate and temperatures were obtained. The flow activation energy was found to decrease with shear rate but to be constant with shear stress. The entrance effect was calculated and from which the extensional behavior was estimated using Cogswell's method. From the extrudate swell ratio the principal normal stress was evaluated and a temperature-independent correlation was observed when they were plotted against shear stress. The melt fracture phenomena were checked and discussed also. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:951–958, 1997     

The significance of capillary rheology testing temperature for predicting PVC extrudability

A rheological investigation of the saturated fatty acids as lubricants for PVC was made in a Sieglaff-McKelvey rheometer over a wide temperature range. Results reveal that with an increase in carbon chain, fatty acids became more effective in reducing the melt viscosity of PVC. It was also discovered that the maximum viscosity variation due to these materials was observed at 350°F. At test temperatures of 400°F and above, no major viscosity differences were observed. Furthermore, the changes in the melt viscosity were more pronounced at shear rates less than 200 sec^?1. The usefulness of the measured viscosity variations at the critical test temperature of 350°F was shown by extrusion. An excellent correlation between the apparent melt viscosity and extrusion melt temperature was found. The criticalness of the test temperature in assessing the effect of lubricants on PVC flow is discussed.     

Rheological properties of poly(vinyl chloride) / epoxidized natural rubber blends. Part II: The effect of processing variables

The effect of processing variables on the rheological properties of PVC/ENR blends was investigated. The role of crosslinking in determining the flow behavior of blends was also examined by means of dynamically cured blends. It was found that PVC/ENR blends yield melts that are power law fluids. The flow of the melts improves with an increase in temperature and shear rate. However, the introduction of crosslinks reverses this trend, although under more rigorous conditions, the influence of crosslinks is superseded, and subsequently, flow becomes shear rate and temperature dependent. PVC/ENR systems also manifested elastic phenomena. The dependence of the elastic phenomena such as die swell and melt fracture on L/D ratio of the die was demonstrated.     

Rheological properties of metallocene isotactic polypropylenes

Rheological properties of metallocene‐catalyzed isotactic polypropylenes (MET‐PP) were evaluated in comparison with those of Ziegler–Natta‐catalyzed isotactic polypropylenes (ZN‐PP) and MET‐PP was generally characterized in a rheological aspect. Based on the characterization, various flow processibilities and their effect on the higher order structure and product properties of the processed article were estimated. The capillary flow properties at various temperatures, elongational flow properties, and dynamic viscoelasticities of MET‐PPs and ZN‐PPs with various melt flow indexes (MFIs) were measured. Furthermore, as an example of application of rheological analysis, the selection of proper raw resin and processing conditions in the sheet‐extrusion of MET‐PP was studied. MET‐PP shows the following rheological features due mainly to the narrow molecular weight distribution in comparison with ZN‐PP with equivalent MFI to that of MET‐PP: while the viscosities at low shear rates are lower, those at high shear rates are higher. Although there is little difference in the loss modulus G″ (viscosity), the storage modulus G′ (elasticity) is very (about one decade) lower. The die swell is much smaller. The entrance pressure loss and end correction coefficient are lower. The critical shear rate at which a melt fracture begins to occur is lower. The melt tension, elongational viscosity, and melt flow index ratio are lower. The flow activation energy is slightly lower. The zero‐shear viscosity obeys the 3.4th‐power law independent of catalyst. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2157–2170, 2002     

Structural characteristics,rheological properties,extrusion, and melt spinning of 60/40 poly(hydroxybenzoic acid-coethylene terephthalate) (PHB/PET)

The rheological properties, extrusion, and melt spinning characteristics, and concomitant morphological features of 60/40 PHB/PET aromatic copolyester have been investigated. The material flows at temperatures above 190°C, but all crystallites may not melt completely until about 250°C. The material exhibits a yield stress value in shear flow. In fact, yield stress values were measured over a range of temperature from 190 to 260°C and estimated at higher temperatures. Extrudate swell measurements were also made in the same range. Significant extrudate swell does not occur until the fluid is at a temperature where the yield stress is approximately 1/50th of its maximum value. Extrudates are fibrillar in character and exhibit significant levels of crystalline orientation. The level of crystalline orientation in melt spun fibers does not vary significantly with drawdown ratio, since it is apparently developed to near its limiting extent during its flow through the die. All of these responses are similar to those observed in melt flow/processing studies of thermotropic liquid crystalline hydroxypropylcellulose.     

高填充性聚丙烯基纳米复合材料挤出胀大行为研究

使用毛细管流变仪考察了3种高填充聚丙烯（PP）纳米复合材料的挤出胀大行为,研究了口模温度、剪切速率、熔体压力、纳米粒子填充比例和纳米粒子形貌对PP纳米复合材料熔体挤出胀大比的影响。结果表明,3种PP纳米复合体系熔体的挤出胀大比均随口模温度的增加而减小,且大致呈线性关系;随着剪切速率的增大而增加,且随着填料填充比例的增加有减小的趋势;随着熔体压力的增大而增加,并且随着熔体压力的增加,其挤出胀大比随填料填充比例的增加而减小的幅度下降;3种颗粒形貌纳米粒子填充体系中,在相同的体积分数和温度下,片状结晶纳米氢氧化镁［Mg（OH）2］填充体系熔体挤出胀大比最小,球状纳米碳酸钙（CaCO3）填充体系熔体挤出胀大比最大,棒状粒子埃洛石纳米管（HNTs）填充体系熔体挤出胀大比介于两者之间。     

Melt elasticity behavior and extrudate characteristics of rigid poly(vinyl chloride)/epoxidized natural rubber miscible blends

A study on the melt elasticity behavior and extrudate characteristics of melts of rigid poly(vinyl chloride), PVC, and rigid poly(vinyl chloride)/epoxidized natural rubber (ENR) miscible blends were conducted. Extrusion studies were carried out in a capillary rheometer and examinations of the surface characteristics of the extrudate were made by taking photomicrographs in a scanning electron microscope. The anomalous behavior in the die swell ratio of rigid PVC arising from the particle agglomerates continued in its blends up to 50 wt% composition of ENR. Temperature independence for high ENR blends was noted for the principal normal stress difference and elastic shear modulus, when shear stress was held constant. Recoverable shear strain and die swell ratio behaved identically in terms of blend composition and processing temperature. Factors which control the extrudate distortion and melt fracture of the melts of rigid PVC/ENR systems were fusion of particle agglomerates and strength of melts. Diamond cavitations were typical of the extrudate surface of PVC melts as those of the fracture surface of the tensile failure of PVC. Conditions to obtain a smooth extrudate surface of rigid PVC melts in blends with ENR have been found to be the low ENR content, low shear rate, or stress and high processing temperature.     

The rheological properties of vinyl chloride–vinyl acetate copolymers

Copolymers of vinyl chloride–vinyl acetate have been prepared with different vinyl acetate contents and molecular weights and under different polymerization conditions. A rheological study of these copolymers indicates that they behave in some ways like externally plasticized PVC. For instance, as the vinyl acetate content increases, the melt viscosity decreases, the flow activation energy decreases, and the copolymer becomes more Newtonian. However, the critical shear rate for melt fracture increases, resembling the addition of elastic polymers to PVC. An increase in copolymer molecular weight has a similar effect on the rheological behavior as in PVC, except that the flow activation energy is observed to increase rather than decrease. Decreasing the polymerization temperature affects the flow properties of the copolymer, probably due to changes in degree of branching and crystallinity. A copolymer made by the delayed addition of vinyl chloride, having a more random structure than one made by the conventional batch method, exhibited quite different flow behavior. It had a lower melt viscosity, higher critical shear rate, and lower flow activation energy.     

Thermal and structural effects of poly(vinyl chloride)/(wood flour) compound gelation in the Brabender mixer

The processing of two unplasticized compounds of poly(vinyl chloride) (PVC) with and without wood flour (WF) was performed in a Brabender mixing chamber, at various chamber temperatures between 130 and 200°C and at a shear rate of 12.61 s^?1. The test was carried out up to the time corresponding to the equilibrium state of the torque, and the variations of torque and real melt temperature as functions of time were analyzed. It was found that the addition of WF led to fusion at lower chamber temperature and that during gelation, stronger self‐heating effects occurred in the WF‐filled PVC compound. Various characteristics of the real temperature gelation curves of PVC with and without the WF filler were observed and are discussed. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

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     

A study of extrudate distortion in controlled-rheology polypropylenes

The melt fracture characteristics of controlled-rheology polypropylenes (CRPP) were studied by means of capillary rheometry experiments. CRPPs were produced through reactive extrusion of a commodity polypropylene resin using various peroxide concentrations. These materials exhibited lower molecular weights and narrower molecular weight distributions than those of the starting commodity resin. The CRPP materials studied were found to exhibit only gross melt fracture. At extremely high shear rates and relatively low temperatures, a sigmoidal flexure was observed in the flow curve of certain CRPPs. Generally, it was found that the severity of melt fracture decreased with increasing shear rate for a given material and temperature and in some cases, the extrudates exhibited completely smooth surfaces. Also, the severity of surface distortions was reduced when high L/D dies were employed at a given shear rate. The critical shear stress for the melt fracture onset was found to increase with decreasing molecular weight and polydispersity, and correlations have been developed between the critical stress values and the polymer polydispersity and shear compliance.     

Lubrication mechanism of poly(vinyl chloride) compounds: Changes upon PVC fusion (gelation)

Poly(vinyl chloride) (PVC) compounds perform best with adequate metal lubrication and polymer‐to‐polymer lubrication of PVC primary particle flow units. Much of the mechanism for the lubrication of PVC has been elucidated over the years. One point has not been completely understood, which is the “lubricant failure” at higher processing temperatures where the compound is known to become less ductile. This result is contrary to what might be expected with better PVC fusion (gelation). This article discusses the mechanism involved, which is lubricant inversion, where the lubricant goes from the continuous phase, as a surfactant coating all the PVC primary particle flow units at lower melt temperatures, to become the discontinuous phase at higher melt temperatures. J. VINYL. ADDIT. TECHNOL., 11:57–62, 2005. © 2005 Society of Plastics Engineers     

Impact strength and morphology in poly(vinyl chloride) window profiles –relationship with gelation level

Abstract

The impact strength resistance of extruded PVC window profiles is a result of the combined effects of the interaction of their intrinsic material properties and processing/fabrication variables. Intrinsic variables include all the components of the formulation, such as the type and level of impact modifier and filler. As such, an appropriate level of toughness can be achieved by selecting the type and amount of rubber particles present in the matrix. However, the impact properties of poly(vinyl chloride) (PVC) profiles are also drastically affected by the thermal and shear history of the PVC matrix. The effect of processing on mechanical properties is explored by altering the temperature profile set on the extruder, and by varying the shear heating phenomena using different lubrication balances. The gelation level of any PVC formulation tends to increase with the level of work on the material, i.e. with increased melt temperature and shear history. The study reported in the present paper is intended to quantify the degree of fusion of the primary crystallites as a function of the melt temperature, and show the dependence of the toughness of the extruded profiles on the resulting free volume. Free volume in PVC extruded profiles depends on the degree of the gelation of the matrix and also on the cooling rate of the melt. As extrusion output increases, cooling of the melt is so fast that polymer chains have much less time to recover and reach a state of minimum entropy. Upon physical aging, the free volume tends to decrease. The reduction in free volume changes the non-equilibrium state of the glass phase, thus reducing the toughness of the material, and causing embrittlement under certain test conditions.

Finally, the effect of filler level and type of impact modifier (two intrin sic variables) on the impact strength of extruded profiles with various levels of free volume are presented.     

Influence of crystallinity in the curing mechanism of PVC plastisols

The influence of the crystalline areas observed in poly(vinyl chloride) (PVC) the mechanical and thermal properties of PVC plastisols was studied. Several industrial‐degree PVC resins were used to obtain a broad range of molecular weights and processing conditions for PVC plastisols. The gelation process was fully studied at different temperatures and was related to the existence of crystalline areas at high temperatures, even near the glass transition. A simple explanation of the phenomena observed during the gelation of plasticized PVC is proposed, according to the variation in the mechanical and thermal properties at different temperatures. The final gelation was obtained at 140–150°C, which was a lower temperature than those at the beginning of the thermal degradation process. The thermodynamic aspects of the gelation of plasticized PVC were mainly controlled by the PVC resin properties, whereas the plasticizer only influenced the diffusion and stability of the material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 538–544, 2004     

PVC/EVA共混物的研究

本文研究了混炼温度和时间对PVC/EVA共混物抗冲性能的影响,发现加入聚乙烯,共混体系的抗冲击强度能进一步提高.用TEM观察了PVC/EVA的形态结构,采用Brabender塑化仪和毛细管流变仪研究了共混物的塑化和熔体流变行为.通过计算机对实验结果进行二元线性回归,建立了共混物的熔体粘度与剪切应力和温度相关联的数学模型.     

PVC melt rheology III: The effect of order and molecular weight on the shear rate dependence

The effect of polymerization temperature on the melt flow behavior of PVC of varying molecular weights has been studied over a wide shear rate range. For the same molecular weight, higher melt viscosities are observed for polymers prepared at lower temperatures. The shear rate dependence of the viscosity vs molecular weight plot is shown to be nonlinear over the shear rates examined. The inability to achieve a limiting zero-shear viscosity is discussed.