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     

Blends of nylon/acrylonitrile butadiene rubber: Effects of blend ratio,dynamic vulcanization and reactive compatibilization on rheology and extrudate morphology

The melt flow behavior of thermoplastic elastomers from nylon and nitrile rubber (NBR) was studied as a function of blend ratio, dynamic crosslinking, compatibilization and temperature. The morphology of the extrudates, i.e., the size, shape and distribution of the domains, was analyzed. Uncompatibilized and compatibilized blends showed pseudoplastic behavior. The viscosity of the blends showed positive deviation from a linear rule of mixtures. Compatibilization using chlorinated polyethylene (CPE) increased the melt viscosity of the blends. The addition of the compatibilizer decreased the domain size of the dispersed phase, followed by an increase after a critical concentration of the compatibilizer, where the interface was saturated. The influence of dynamic vulcanization on the rheological behavior was also studied. The extrudate morphology depended on blend ratio, compatibilization and shear rate.     

Melt rheology of HDPE/EVA blends: The effects of blend ratio,compatibilization, and dynamic vulcanization

The melt rheological behavior of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends has been examined with reference to the effect of blend ratio, shear stress, and temperature. The HDPE/EVA blends exhibit pseudoplastic behavior, and the observed rheological behavior of the blends was correlated with the extrudate morphology. The experimental values of the viscosity were compared with the theoretical models. The effect of maleic‐ and phenolic‐modified PE compatibilizers on the viscosity of H₇₀ blend was analyzed and found that compatibilization did not significantly increase the viscosity. The effect of dynamic vulcanization and temperature on the viscosity was also analyzed. The activation energy of the system decreased with increase in EVA content in the system. The phase continuity and phase inversion points of the blends were theoretically predicted and compared with the experimental values. The melt flow index (MFI) values of the blends were also determined and found that the MFI values decreased with increase in EVA content in the system. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

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 dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

The effect of mercapto‐modified EVA on rheological and dynamic mechanical properties of NBR/EVA blends

The effect of mercapto‐modified ethylene vinyl acetate copolymer (EVALSH) on the rheological and dynamic mechanical properties of acrylonitrile butadiene rubber (NBR) and ethylene vinyl acetate copolymer (EVA) blends was evaluated at different blend compositions. The addition of 5 phr of EVALSH in the blends resulted in an increase of the melt viscosity and a substantial decrease of the extrudate swell ratio. These results can be attributed to the interactions occurring between the double bond of the NBR phase and the mercapto groups along the EVALSH backbone. The power–law index also presents a slight increase in the presence of EVALSH, indicating a decrease in the pseudoplastic nature of the compatibilized blends. The reactive compatibilization of NBR/EVA blends with EVALSH was also confirmed by the decrease of damping values and an increase of glass transition temperature, in dynamic mechanical analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2335–2344, 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     

Melt rheological properties of polypropylene/SEBS (styrene–ethylene butylene–styrene block copolymer) blends

Study of melt rheological properties of the blends of polypropylene (PP) with styrene–ethylene butylene–styrene block copolymer (SEBS), at blending ratios 5–20% SEBS, is reported. Results illustrate the effects of (i) blend composition and (ii) shear rate or shear stress on melt viscosity and melt elasticity and the extrudate distortion. In general, blending of PP with SEBS results in a decrease of its melt viscosity, processing temperatures, and the tendency of extrudate distortion. However, the properties depend on blending ratio. A blending ratio around 5–10% SEBS seems optimum from the point of view of desirable improvement in processability behavior.     

Studies on the melt flow behavior of thermoplastic elastomers from polypropylene—Natural rubber blends

The melt flow behavior of thermoplastic polypropylenenatural rubber blends has been evaluated with specific reference to the effects of blend ratio, extent of dynamic crosslinking of the rubber phase and temperature, on viscosity, flow behavior index, and deformation of the extrudate. The proportion of rubber in the blend and the extent of dynamic crosslinking of the rubber phase were found to have profound influence on the viscosity of the blends at lower shear stresses. But at higher shear stresses, the effect of blend ratio on viscosity was comparatively less for the uncrosslinked blends than that for the crosslinked blends. At lower shear stress, the viscosity of the blend increased with increase in degree of crosslinking but at higher shear stress, the effect of crosslinking on viscosity was found to vary depending on the ratio of the plastic and rubber components in the blend. The deformation of the extrudates was also very much dependent on both blend ratio and degree of crosslinking.     

Studies on binary and ternary blends of polypropylene with SEBS,PS, and HDPE. I. Melt rheological behavior

Studies are reported on melt rheological behavior of some binary and ternary blends of polypropylene (PP) with one or two of the following polymers: styrene–b-ethylene butylene–b-styrene triblock copolymer (SEBS), polystyrene (PS), and high-density polyethylene (HDPE). Blend composition of the binary blends PP/X or ternary blends PP/X/Y were so chosen that the former represent addition of 10 wt % X to PP while the latter represent 10 wt % addition of X or Y to the PP/Y or PP/X blend of constant composition 90:10 by weight, X/Y being SEBS, PS, or HDPE. Measurements were made on a capillary rheometer using both temperature elevation and constant temperature methods to study the behaviors prior to flow and in the flow region. Flow behavior, measured at a constant temperature (200°C) and varying shear stress (from 1.0 to 5.0 × 10⁶ dyn/cm²) to evaluate melt viscosity and melt elasticity parameters, is discussed for its dependence on the nature of the blend. Extrudate distortion, studied as a function of shear stress to evaluate the critical shear stress for the onset of extrudate distortion, showed differences in the tendency for extrudate distortion or melt fracture of these different blends. Also discussed is the effect of melt viscosity and melt elasticity on extrudate distortion behavior at the critical condition, which showed a unique critical value of the ratio (melt elasticity parameter)^1/2 (melt viscosity) for all these blends. Blend morphologies before and after the flow through the capillary are investigated through scanning electron microscopy, and their correlations with rheological parameters of the melt are discussed.     

共聚聚丙烯(cPP)/线型低密度聚乙烯(LLDPE) 共混体系的流变与结晶形为

用毛细管流变仪研究了共聚聚丙烯(cPP)与线型低密度聚乙烯(LLDPE)共混物熔体的流变行为.讨论了共混物的组成、切应力和剪切速率对熔体流变行为和熔体粘度的影响.测定了不同配比共混物熔体的非牛顿指数.结果表明共混物熔体属假塑性流体,但共混体系粘度随LLDPE加入量的增加变化不大.DSC结晶曲线及扫描电镜(SEM)照片表明,LDPE的加入使cPP的结晶温度变化不大,但对晶体形态有一定影响.LLDPE对cPP有一定的增韧改性作用,当LLDPE质量分数为15%时,共混物的冲击强度增幅在40%左右,而拉伸强度保持率为80%.     

Rheological behavior of highly filled ethylene propylene diene rubber compounds

The rheological behavior of highly filled ethylene propylene diene rubber (EPDM) compounds was studied with respect to the effect of curative system, grafted rubber, shear rate, temperature and die swell using a Monsanto Processability Tester (MPT) to gain an understanding of the molecular parameters that control the surface finish. All systems show pseudoplastic behavior. At a particular shear rate, shear viscosity increases with blend ratio. The dependence of flow behavior on extrusion velocity indicates a surface effect. The extrudate die swell and maximum recoverable deformation are related by a linear relationship, which is independent of sulfur/accelerator ratio, extrusion temperature and shear rates and blend ratio. The principal normal stress difference increases nonlinearly with shear stress. Activation energy decreases with shear rate in most cases. The faster relaxing system produces extrudate of better surface quality.     

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.     

PP/EVA/COPET共混物流变性能的研究

采用CFT-500型毛细管流变仪研究了聚丙烯/乙烯-醋酸乙烯酯/碱溶性聚酯(PP/EVA/COPET)共混物的流变性能。结果表明:PP/EVA/COPET共混物出现剪切变稀现象,非牛顿指数小于1,熔体为假塑性流体;熔体表观粘度随EVA含量的增加呈现先减小后增大趋势,并随温度的上升而下降;EVA质量分数为15%的共混物的表观粘度最低,粘流活化能最小。     

Effects of blend ratio and vulcanizate powders on the processability of silicone rubber/fluororubber blends

While silicone rubber has a much lower shear viscosity than that of fluororubber, the viscosity of silicone rubber/fluororubber blends is closer to that of silicone rubber. All rubber compositions show pseudoplastic behavior. While the viscosity of a 50/50 silicone rubber/fluororubber blend increases on replacement of the silicone rubber by silicone rubber vulcanizate powder (SVP), the effect of fluororubber replacement by the corresponding fluororubber vulcanizate powder (FVP) on the shear viscosity is less pronounced. The difference in viscosity between SVP‐replaced silicone rubber and FVP‐replaced fluororubber becomes less prominent at higher shear rates. Fluororubber exhibits a higher extrudate die swell than that of silicone rubber. The die swell of the silicone rubber/fluororubber blends is higher than are the figures obtained by the additivity rule. Replacement of constituent rubbers in the blend by the corresponding vulcanizate powders causes an increase in the die swell. While the silicone rubber extrudate surface is smooth, the fluororubber extrudate shows melt fracture. The extrudate surfaces of the silicone rubber/fluororubber blends are similar to that of the silicone rubber extrudate. Replacement of constituent rubbers by the corresponding vulcanizate powders increases the roughness of the extrudate surface, which is more prominent in the case of silicone rubber replacement by SVP. SVP can replace 50% of silicone rubber and FVP can replace 75% of fluororubber in the 50/50 silicone rubber/fluororubber blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2377–2387, 2003     

Structure and properties of dynamically cured EPDM/PP blends

The structure and properties of polyolefin blends of ethylene–propylene–diene terpolymer (EPDM) and polypropylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured with PP under shear with dicumyl peroxide (DCP) at different shear conditions (blend–cure). Blends were also prepared for comparison from EPDM which were dynamically cured in the absence of PP and blended later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastic composition were studied. In blend–cure, the melt viscosity increased with increasing DCP concentration in blends of 75% EPDM and 25% PP, but it decreased with increasing DCP concentration in blends of 75% PP and 25% EPDM. In cure–blend, however, the melt viscosity increased with increasing DCP concentration for all compositions. The melt viscosity decreased with increasing intensity of the shear mixing presumably due to the formation of the smaller segregated microdomain of the crosslinked EPDM gels in both blend–cure and cure–blend materials. The crystallization rate was higher in EPDM/PP blends than in PP homopolymer. The crystallization rates for various blending conditions were also compared.     

共聚聚丙烯／茂金属线形低密度聚乙烯共混体系的流变行为与结晶行为

用毛细管流变仪研究了冲击性能相对优良的共聚聚丙烯(cPP)与茂金属低密度聚乙烯(m-PE—LLD)共混物熔体的流变行为。讨论了共混物的组成、剪切应力和剪切速率对熔体流变行为、熔体粘度的影响。测定了不同cPP及m—PE—LLD配比的共混物熔体的非牛顿指数。结果表明：共混物熔体属假塑性流体，但其粘度随m—PE—LLD加入量的增加变化不大。DSC分析及微观形态分析表明，m-PE—LLD的加入使cPP的结晶温度提高，具有异相成核作用。m-PE—LLD对cPP有明显的增韧作用，当m—PE—LLD含量为15％时，共混物的冲击强度明显提高，增幅在75％左右，而拉伸强度保持率为85％以上。     

Effect of E/P ratio and VA content on flow behavior of EPDM and EVA blends

The effect of E/P ratio of EPDM rubber and VA content of EVA copolymer on the flow behavior along with the extrudate morphology of EVA and EPDM blends have been studied as a function of shear rate and processing temperature. High E/P ratio EPDM rubber and low VA content EVA render high viscosities to the blend within the temperature range studied. The same trends hold true for extrudate swell. Stored elastic energy and relaxation time are higher for high E/P ratio EPDM and low VA content EVA. However, compositions with low E/P ratio EPDM exhibit higher shear modulus. At a particular blend composition these rheological parameters show a change in their pattern. Melt fracture occurs to a larger extent for the high E/P ratio EPDM in its blend with low VA content EVA. © 1994 John Wiley & Sons, Inc.     

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     

动态硫化氯化丁基橡胶/聚丙烯酸乙酯共混物的熔体流变行为

研究了由不同动态硫化时间制备的氯化丁基橡胶(CIIR)和聚丙烯酸乙酯(PEA)共混物熔体的流变行为。结果表明,在不同的动态硫化时间里,CIIR／PEA共混物熔体的黏度均随着剪切速率的增加而先增后减,共混物熔体显示出膨胀性流动和假塑性流动相复合的复杂流变行为;动态硫化时间越长,熔体的最大黏度越小,动态硫化时间越短,熔体的最大黏度越大。在高剪切速率下,共混物熔体均具有适宜于模塑的良好流动性。