Rheological Properties of Thermoplastic Polyvinyl Alcohol and Polypropylene Blend Melts in Capillary Extrusions

A single screw extruder with a static mixer was used to prepare molten blends of thermoplastic polyvinyl alcohol (TPVA) and polypropylene (PP). The effects of shear rate, blending ratio and temperature on rheological properties for the blends in capillary extrusions were investigated, and ends correction was also carried out. Rheological parameters such as non-Newtonian index and activation energy were also calculated and evaluated. It was found that the viscosities of the blends were lower than those of TPVA and PP; moreover, the non-Newtonian indices and the activation energies of the blend melts were higher than those of the homopolymers. In particular, the blend with 60 wt% TPVA had the highest non-Newtonian indices and activation energies among blend melts. These results indicate that TPVA and PP blends are negative deviation blends. Furthermore, at a blending ratio of 60 wt% of TPVA, the shear-sensitivity of the viscosity was the lowest and the temperature dependence of the viscosity was the highest. In addition, an increase in temperature led to an increase in non-Newtonian index, therefore the shear-rate dependence of the blend viscosities decreased with a rise in temperature. As the shear rate was increased, the variation of the viscosity over blending ratios decreased while the activation energy of the blends decreased. Thus the effects of temperature and blending proportion on flow behavior were diminished by increasing shear rate.     

Melt Rheology and Morphology of Nitrile Rubber and Ethylene-Vinyl Acetate Copolymer Blends

The melt Theological behavior of nitrile rubber (NBR)/ethylene-vinyl acetate (EVA) copolymer blends was studied with special reference to the effect of the blend ratio, cross-linking systems, and shear rate using a capillary rheometer. At a given shear stress at 90°C, the viscosities of the blends vary slightly with composition. The effect of cross-linking systems [viz., sulfur (S), peroxide (DCP) and mixed (S+DCP) systems] on the viscosity of NBR/EVA blends is negligible. The melt viscosity of the blends decreases with increasing shear rate, showing pseudoplastic behavior. The flow behavior index values also support the pseudoplastic nature of these blends. Various theoretical models were used to predict the melt viscosity of the blends. Parameters such as die swell, principal normal stress difference, recoverable shear strain, and shear modulus were calculated to characterize the melt elasticity of these blends. The melt elasticity of the system was increased by the addition of NBR to EVA. The extrudate deformation at different shear rates was also studied. It was observed that as the shear rate increases, the extrudate surface exhibits a higher degree of deformation. The morphology of the extrudates of the blends at different shear rates has been examined by a scanning electron microscope. The morphology was found to be dependent on the blend ratio and shear rate.     

Blends of poly[ethylene(vinyl acetate)] and polychloroprene: Studies on capillary and dynamic flows

Rheological properties of the blends of poly[ethylene(vinylacetate)] (EVAc; vinylacetate content 28%) and polychloroprene (CR) have been measured through capillary and dynamic uniaxial elongational flows. Capillary flow indicates their shear thinning behavior. The decrease in the out of phase viscosities with increasing frequency is in accordance with the power law equation, whereas dynamic elongational viscosities follow nonlinear relationship in log-log plot with an initial increase at 11 Hz, followed by a very sharp drop. With an increase in temperature, the viscosity for capillary flow of all blends goes down due to their positive activation energy of flow but for dynamic elongational flow of EVAc blended with CR, viscosity increases, except for 30/70 blend and pure CR, in which case the dynamic elongational viscosity decreases with an increase in temperature. This abnormal behavior in dynamic elongational viscosity is due to the process of melting and recrystallization of EVAc at low heating rate (1°C/min) beyond the melting temperature. Capillary viscosities of all blends show positive deviation from the log additive values of pure polymers. But in the case of dynamic elongational flow, all blends show positive deviation at frequencies of 3.5 and 35 Hz and at higher temperatures (80–120°C). © 1997 John Wiley & Sons, Inc.     

Melt rheology and morphology of LLDPE/EVA blends: Effect of blend ratio,compatibilization, and dynamic crosslinking

The melt rheological properties of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were investigated with special reference to the effect of blend ratio, temperature, shear rate, compatibilization, and dynamic vulcanization. The melt viscosity of the blends determined with a capillary rheometer is found to decrease with an increase of shear rate, which is an indication of pseudoplastic behavior. The viscosity of the blend was found to be a nonadditive function of the viscosities of the component polymers. A negative deviation was observed because of the interlayer slip between the polar EVA and the nonpolar LLDPE phases. The melt viscosity of these blends decreases with the increased concentration of EVA. The morphology of the extrudate of the blends at different shear rates and blend ratios was studied and the size and distribution of the domains were examined by scanning electron microscopy. The morphology was found to depend on shear rate and blend ratio. Compatibilization of the blends with phenolic‐ and maleic‐modified LLDPE increased the melt viscosity at lower wt % of compatibilizer and then leveled off. Dynamic vulcanization is found to increase the melt viscosity at a lower concentration of DCP. The effect of temperature on melt viscosity of the blends was also studied. Finally, attempts were made to correlate the experimental data on melt viscosity and cocontinuity region with different theoretical models. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3210–3225, 2002     

Melt rheology and morphology of physically compatibilized natural rubber–polystyrene blends by the addition of natural rubber-g-polystyrene

Blends of natural rubber (NR) and polystyrene (PS) were prepared by melt mixing in a Brabender plasticorder and by solution casting using chloroform as the casting solvent. Earlier studies have indicated that these blends are incompatible and immiscible, and their compatibility can be improved by the addition of a graft copolymer of NR and PS (NR-g-PS). The rheological behavior of these blends has been carried out in the presence and absence of the compatibilizer using a capillary rheometer and a melt flow indexer. The effects of blend ratio, processing techniques (melt mixing versus solution casting), shear stress, and temperature on the rheological behavior have been studied in detail. Both in the presence and absence of the copolymer, the blends showed a decrease in viscosity with an increase of shear stress, indicating pseudoplastic nature. Solution-cast blends showed a higher viscosity as compared to melt-mixed blends. The viscosity versus composition curve of both melt-mixed and solution-cast blends showed negative deviation from the additivity at a higher shear rate region. This is associated with the interlayer slip between the highly incompatible NR and PS phases. The effects of graft copolymer loading and temperature on solution-cast blends were studied, and it was found that as the copolymer loading increases, the shear viscosity increases. This is due to the high interfacial interaction between the two components in the presence of the copolymer. The copolymer, in fact, locates at the interface and makes the interface more broad. However, at higher loading of the copolymer, the viscosity of the blends decreases. This may be associated with the formation of micelles, which have a plasticizing action on the viscosity of the blends. Melt elasticity parameters like principal normal stress difference, recoverable elastic shear strain, and die swell were evaluated. Master curves have been generated using modified viscosity and shear rate functions that contain the melt flow index as a parameter. The extrudate morphology of the blends was studied using a scanning electron microscope. Addition of the copolymer reduces the domain size of the dispersed phase, followed by a leveling off at a higher concentration. The leveling off is an indication of interfacial saturation. The interparticle distance also decreased followed by a leveling off at a higher loading of the copolymer. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2673–2690, 1998     

Rheological behavior in the molten state and solution of hyperbranched polyester of fourth and fifth generation

The rheological behavior in the molten state and solution of hyperbranched polyol polyesters (HBPs) obtained by one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both (HBP1‐4, HBP1‐5) was studied. Under conditions of dynamic oscillatory shear, all HBPs presented a shear‐thinning behavior and under steady shear they showed a Newtonian behavior. Also, the steady shear viscosities decreased with increasing temperature. The behavior of HBPs was mainly viscous, except for the HBP4P that showed higher storage modulus and reduction of complex viscosity when increasing the angular frequency. The HBPs presented higher complex viscosity than steady shear and they did not follow the Cox‐Merz rule. The HBPs in solution presented a plateau region at shear rate lower than 40 s⁻¹ but a shear‐thickening behavior at shear rate higher than 40 s⁻¹. The viscosities of HBPs in solution (in the plateau region) and molten state increase in the following order: HBP5P > HBP1‐5 > HBP4P > HBP1‐4 > HBP4 > HBP5. These results are not in agreement with the values of the number average molar mass obtained by vapor pressure osmometry due to different interaction between HBPs molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological behavior of blends of natural rubber and styrene–butadiene rubber latices

The rheological behavior of blends of natural rubber (NR) and styrene–butadiene rubber (SBR) latices has been studied with reference to the effects of blend ratio, shear rate, surface-active agents (casein and sodium carboxymethyl cellulose), and temperature. When the SBR content was less than 50%, the viscosities of the blends appeared to be a nonadditive function of the viscosities of the constituent homopolymers; i.e., a positive deviation was observed. This was due to the structural buildup of the SBR domains. The SBR domains underwent agglomeration and consequently so-called microflocculation took place. The viscosities of all the blends were found to decrease with increase of temperature and shear rate. The increase in temperature and shear rate marginally weakened the structural buildup as evidenced by the lowering of viscosity. As the SBR content in the system increased, the pseudoplasticity of the blend increased. Even in the presence of surface-active agents the blends showed composition-dependent positive deviation. However, surface-active agents marginally reduced the extent of structural buildup by reducing the microflocculation behavior of SBR domains. © 1995 John Wiley & Sons, Inc.     

Rheological and thermal properties of thermoplastic natural rubbers based on poly(methyl methacrylate)/epoxidized‐natural‐rubber blends

Epoxidized natural rubbers (ENRs) with epoxide levels of 10, 20, 30, 40, and 50 mol % were prepared. The ENRs were later blended with poly(methyl methacrylate) (PMMA) with various blend formulations. The mixing torque of the blends was observed. The torque increased as the PMMA contents and epoxide molar percentage increased in the ENR molecules. Furthermore, the shear stress and shear viscosity of the polymer blends in the molten state increased as the ENR content and epoxide molar percentage increased in the ENR molecules. Chemical interactions between polar groups in the ENR and PMMA molecules might be the reason for the increases in the torque, shear stress, and viscosity. All the ENR/PMMA blends exhibited shear‐thinning behavior. This was observed as a decrease in the shear viscosity with an increase in the shear rate. The power‐law index of the blends decreased as the ENR contents and epoxide molar percentage increased in the ENR molecules. However, the consistency index (or zero shear viscosity) increased as the ENR contents and epoxide molar percentage increased. A two‐phase morphology was observed with scanning electron microscopy. The small domains of the minor components were dispersed in the major phase. For the determination of blend compatibility, two distinct glass‐transition‐temperature (T_g) peaks from the tan δ/temperature curves were found. Shifts in T_g to a higher temperature for the elastomeric phase and to a lower temperature for the PMMA phase were observed. Therefore, the ENR/PMMA blends could be described as partly miscible blends. According to the thermogravimetry results, the decomposition temperatures of the blends increased as the levels of ENR and the epoxide molar percentage increased. The chemical interactions between the different phases of the blends could be the reason for the increase. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3561–3572, 2004     

Rheological and mechanical properties of poly(lactic acid)/polystyrene polymer blend

Properties modification by blending polymers has been an area of immense interest. In this work, rheological and mechanical properties of poly(lactic acid)/polystyrene (PLA/PS) blends were investigated. PLA/PS blends in different ratios were prepared using a laboratory scale single screw extruder to obtain (3 mm) granules. Rheological properties were studied using a capillary rheometer and the Bagley’s correction was performed. True shear rate (γ _r ), true shear stress (τ _r ), and true viscosity (η _r ) were determined, the relationship between true viscosity and (1/T) was studied for PLA70 blend and the flow activation energy at a constant shear stress (E _τ ) and a constant shear rate (E _γ ) was determined. The mechanical property measurements were performed at room temperature. Stress at break and strain at break were determined. The results showed that PLA/PS blend exhibited a typical shear-thinning behavior over the range of the studied shear rates, and the viscosity of the blend decreased with increasing PLA content. Also it was found that no equal-viscosity temperature exists between PLA and PS. The mechanical results showed immiscibility between PLA and PS in the blend.     

Modell zur Beschreibung der rheologischen Eigenschaften von Blends aus HDPE und langkettenverzweigtem linearem Polyethylen niederer Dichte

The rheological properties of blends of high-density polyethylene (HDPE) and linear polyethylene of low density with an amount of long-chain branching (HBPE) synthesized with metallocene catalysts were investigated regarding the dependence of the shear viscosity from the shear rate over the whole composition range. While the pure HDPE shows a strong decrease in viscosity with increasing shear rate, the decrease for HBPE is much less distinctive. For a shear rate of about 300 s^–1 both products show similar viscosities. The viscosities of the blends, in dependence from the shear rate, show a nonlinear change between the characteristics of the pure components HDPE and HBPE. This behaviour could be described with a mathematical model, for which especially rational functions together with often used rheological model terms gave good results. Finally, besides the decrease of the viscosity with increasing shear rate, the exponent in the Ostwald-de Waele law was discussed as measure for the intrinsic viscosity. The threshold value, i. e. the Merrington effect during extrusion, was calculated as measure for the elastic amounts in the polymer melt, and their dependence from the shear rate and from the composition was expressed mathematically and discussed. It was observed that the treshold value shows a less significant change in dependence from the shear rate than the pure components do.     

Particle dimensions in polystyrene/polyethylene blends as a function of their melt viscosity and of the concentration of added graft copolymer

Apparent particle dimensions in blends of low density polyethylene (PE) and polystyrene (PS) made by mixing in the molten state have been measured and have been shown to depend on the viscosity of the mixed system. At a certain shearing rate small particles of the dispersed polymer are obtained if the polymer in excess has a high viscosity. At a higher concentration however this effect is counteracted completely if the dispersed phase has a low viscosity and thus lowers the overall viscosity. Coalescence is affected in the same way and the size of the particles increases greatly with increasing concentrations. If a highly viscous polymer is dispersed in a low viscosity polymer matrix relatively large particle sizes will be found at the preset shearing rate mentioned above. With increasing concentration of the highly viscous dispersed phase the particle size decreases due to the increasing viscosity. This effect is counteracted by coalescence leading to a relatively slow increase of particle size with concentration. Addition of surfactants such as graft copolymers based on PS and PE leads to smaller particle sizes as expected.     

Melt rheology and elasticity of natural rubber—ethylene–vinyl acetate copolymer blends

The melt rheology of blends of natural rubber (NR) and ethylene–vinyl acetate copolymer (EVA) has been studied with reference to the effects of blend ratio, cross-linking systems, shear stress, and temperature. When EVA formed the dispersed phase, the viscosity of the blends was found to be a nonadditive function of the viscosities of the component polymers at lower shear region, i.e., a positive deviation was observed. This behavior has been explained based on structural buildup of dispersed EVA domains in the continuous NR matrix. The effect of the addition of silica filler on the flow characteristics of the blends has been investigated. The melt elasticity parameters such as die swell, principal normal stress difference, recoverable shear strain, and elastic shear modulus of NR–EVA blends were also evaluated. © 1993 John Wiley & Sons, Inc.     

Effect of hydrodynamics on dynamics of phase separation in polystyrene/poly(vinyl methyl ether) blend

Polystyrene/poly(vinyl methyl ether) (PS/PVME) phase diagram was assessed by rheological tools and by on-line microscopy observations both under quiescent and shear flow conditions. Shear flow was found to induce both mixing and demixing of the mixture depending on the amplitude of the imposed shear rate. Viscoelastic properties of PS/PVME blends were also measured under steady shear flow near the phase separation temperature. At lower shear rate, flow enhances concentration fluctuation and induces phase segregation. At high shear rate, flow suppresses fluctuations and the polymer mixture keeps its miscible state. Several rheological signatures of phase transition were found. In steady shear flow, a secondary plateau in viscosity was observed when the temperature was close to T_s whereas, at the start-up shear flow, transient shear stress showed a second overshoot after a few minutes of shearing.     

Phase morphology development and melt rheological behavior in nylon 6/polystyrene blends

Phase morphology development in immiscible blends of polystyrene (PS)/nylon 6 was investigated. The blends were prepared by melt blending in a twin‐screw extruder. The influence of the blend ratio, rotation speed of the rotors, and time of mixing on the phase morphology of the blends was carefully analyzed. The morphology of the samples was examined under a scanning electron microscope (SEM) and the SEM micrographs were quantitatively analyzed for domain‐size measurements. From the morphology studies, it is evident that the minor component, whether PS or nylon, forms the dispersed phase, whereas the major component forms the continuous phase. The 50/50 PS/nylon blend exhibits cocontinuous morphology. The continuity of the dispersed phase was estimated quantitatively based on the preferential solvent‐extraction technique, which suggested that both phases are almost continuous at a 50/50 blend composition. The effect of the rotor speed on the blend morphology was investigated. It was observed that the most significant breakdown occurred at an increasing rotor speed from 9 to 20 rpm and, thereafter, the domain size remained almost the same even when the rotor speed was increased. The studies on the influence of the mixing time on the blend morphology indicated that the major breakdown of the dispersed phase occurred at the early stages of mixing. The melt rheological behavior of the blend system was studied using a capillary rheometer. The effect of the blend ratio and the shear stress on the melt viscosity of the system was investigated. Melt viscosity decreased with increase in the shear stress, indicating pseudoplastic behavior. With increase of the weight fraction of PS, the melt viscosity of the system decreased. The negative deviation of the measured viscosity from the additivity rule indicated the immiscibility of the blends. The domain size versus the viscosity ratio showed a minimum value when the viscosities of the two phases were matched, in agreement with Wu's prediction. The morphology of the extrudates was analyzed by SEM. From these observations, it was noted that as the shear rate increased the particle size decreased considerably. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3537–3555, 2002     

Extrusion of PE/PS blends with supercritical carbon dioxide

The effects of dissolved supercritical carbon dioxide on the viscosity and morphological properties were investigated for polyethylene/polystyrene blends in a twin-screw extruder. The viscosities of the blend/CO₂ solutions were measured using a wedge die mounted on the extruder. A considerable reduction of viscosity was found when CO₂ was dissolved in the blend. It was observed that the dissolution of CO₂ into PE/PS blends, regardless of the CO₂ content used, led to decreased shear thinning behavior resulting in an increase of the power law index from 0.29 to 0.34. The cell structures of foamed PE/PS blends showed a typical dependence of pressure and CO₂ concentration, with higher operating pressures and CO₂ content leading to a smaller cell size. Also, it was noted that the size of the dispersed PS phase in the PE/PS phase blends decreased by increasing the CO₂ concentration, and that the dispersed PS phase domains were highly elongated in the direction normal to the cell radius.     

固相缩聚半芳香透明聚酰胺的流变性能

采用毛细管流变仪对固相缩聚半芳香透明聚酰胺(Semi-AromaticTransparent Polyamide,简称SATPA)的流变性能进行了研究。研究结果表明:固相缩聚SATPA熔体属假塑性流体,非牛顿指数随剪切速率的增大而减小;表观黏度随温度、剪切速率和剪切应力的升高而降低。随着剪切速率的增大,黏流活化能减小,表观黏度对于温度的敏感性减弱。     

Morphological,thermal, and rheological properties of nylon/acrylonitrile-butadiene-styrene alloys

Melt blends of nylon-6/modified ABS (acrylonitrile-butadiene-styrene terpolymer) have been prepared using a single screw extruder. Electron microscopic observations revealed that the rubber particles are as finely dispersed as in ABS. Both the heat of fusion and the dynamic storage modulus of the blends were linear functions of the blend composition. The melting point of nylon crystallites and glass transition temperatures of poly(acrylonitrile-co-styrene) (AS) and the rubber phase in ABS and the amorphous phase in nylon were almost independent of the composition. Very high Izod impact strength was achieved over a broad compositional range. These facts suggest that the nylon and the modified ABS are not mixed on a molecular level although there must be sufficient interaction between them. The melt viscosities were increased with an increase in the ABS component. In the region of less than 65% ABS, the viscosities bend off to the zero-shear viscosity at low shear rates. Above 65% ABS, the viscosity curves were expressed by a power law fluid. The power law index decreased with an increase in the ABS content. The activation energy of flow vs. composition curve indicated a discontinuous point between 60% and 70% ABS. The phase inversion takes place at about 65% ABS, judging from the rheological point of view.     

PPESK／PS共混物流变性能的研究

以溶液共沉淀的方法制备了含二氮杂萘联本结构的聚芳醚砜酮（PPESK）。聚苯乙烯（PS）共混物，用毛细管流变仪测定了共混物的流为性能。结果表明，在本实验条件下，PPESK／PS共混物熔体属假塑性非牛顿汉体，其熔体粘度随PS含量的增加、温度的升高、剪切速率的增大而下降。PS的加入有利于改善PPESK的熔融加工流动性。     

Rheological and curing properties of reactive blending products of epoxidised natural rubber and cassava starch

Abstract

Epoxidised natural rubber (ENR) has been prepared and used as a blending ingredient together with a compatibiliser for blending of natural rubber (air dry sheet, ADS) and cassava starch. Mooney viscosities of the blends were quantified at 100°C and rheological properties in terms of shear stress and shear viscosity were plotted against shear rates. The results showed that pure ENR gave a lower Mooney viscosity, shear stress, and shear viscosity than blends with cassava starch. Mooney viscosity, shear stress, and shear viscosity for the blends increased with increasing levels of starch. At the same level of cassava starch blended, the highest values of these quantities were observed for the blends with ENR. The blend of ADS with ENR as a compatibiliser showed lower values than those of ENR itself, but higher than those of ADS with the starch. The results are described in terms of the level of chemical interaction between polar groups in ENR and in cassava starch. Curing behaviour for compounds of ENR, ADS, and ADS with ENR as a compatibiliser were studied. The results found that ENR exhibited a long delay (～ 10 min) before the vulcanisation took place compared with 1 min for ADS compounds. In the curing curve for ENR, an equilibrium value at maximum torque was not found indicating that the stiffness of the ENR compounds still increased with increasing testing time until 60 min. Stiffness of the ENR compounds also increased with increasing levels of cassava starch.     

Rheological properties of ethylene ionomer neutralized with binary metal cation

The roles of ionic bonding in molten ethylene ionomers without ionic aggregates were rheologically characterized in linear regions under shear. We have measured melt viscosities of ethylene-methacrylic acid (EMAA) ionomers by means of dynamic shear experiment. The samples used in this study were binary mixtures selected from Na, Mg and Zn salts of EMAA (MAA=5.4 mol%). The dynamic shear properties revealed that the time-material superposition is applicable to these ionomer blends in a temperature range from 140 to 200 °C. It was also found that these binary mixtures unexpectedly give decreases of zero shear viscosities obtained from a time-material superposition, if the cations were selected from different metal groups such as alkali, alkaline earth and transition metals. This behavior can be explained by the acid-cation exchange mechanism.