The impact of viscoelastic behavior and viscosity ratio on the phase behavior and morphology of polypropylene/polybutene‐1 blends

In this study, the influence of the viscosity ratio on the rheology, morphology, and interfacial interaction of polypropylene and polybutene‐1 (PB‐1) resins with various melt flow behaviors in the blend are investigated. A droplet‐matrix morphology is observed in the scanning electron microscope images for all formulations and the size of particles increased proportionally by increasing the viscosity ratio. Viscoelastic parameters of blends at various viscosity ratios and compositions are measured by small‐amplitude oscillation rheometry in the linear viscoelastic region. The Cole‐Cole plots showed a nearly semicircular arc for all compositions. This semicircular arc is observed while the viscosity ratio is lower than 1, and the Cole‐Cole plots deviated from the semicircular shape at PB‐1 content higher than 10 wt%. It is emphasized that, in addition to compatibility, the semi‐circularity of Cole‐Cole plots affects the size of the dispersed particles, which is under the influence of the viscosity ratio. It is found that the interfacial tensions of polypropylene and PB‐1 are not significantly different when changing the viscosity ratio and coarsening the morphology. The form relaxation times in the blends with lower viscosity ratios are shorter than the form relaxation times of the blends with higher viscosity ratios. J. VINYL ADDIT. TECHNOL. 21:94–101, 2015. © 2014 Society of Plastics Engineers     

Effect of Polyethylene Molecular Architecture on the Dynamic Viscoelastic Behavior of Polyethylene/Polyhexene-1 Blends and Its Correlation with Morphology

In the present work, the rheology, morphology, and interfacial interaction of polyethylene/polyhexane-1 (PE/PH-1) blends with various polyethylene types with different molecular architectures are investigated. The scanning electron microscopy (SEM) images showed a droplet-matrix morphology in all percentage of PH-1 for all blend systems and the size of droplets increased proportionally with PH-1 content. The minimum droplet size is observed for high-density polyethylene (HDPE)/PH-1 blends. The homogeneity of the blends at various compositions is assessed by using viscoelastic parameters determined by dynamic oscillation rheometry in the linear viscoelastic region. A distinct Newtonian plateau at low frequencies is perceived and the variations of complex viscosity (η*) versus angular frequency (ω) for all blend systems are in good agreement with Carreau-Yasuda model. The complex viscosity of samples at various percentages of PH-1 showed the negative deviation from mixing rule in low and high frequencies for all blend systems. The Cole-Cole plots deviated from semi-circular shape at higher percentages of PH-1 than 10wt% in the blends of low-density polyethylene (LDPE)/PH-1 and linear low-density polyethylene (LLDPE)/PH-1. By using emulsion theoretical model, the lowest interfacial tension is found for HDPE/PH-1 blends comparing with its counterparts based on LDPE and LLDPE and the best fitting with experimental data was observed for this blends system.     

Interfacial slip‐stick transition induced by reactive compatibilization in ethylene‐co‐butyl acrylate elastomer dispersed polyamide 6 blend subjected to high shear flow and extensional flow

The effect of phase interaction induced by reactive compatibilization during high shear and extensional flow in polyamide (PA6) and ethylene‐co‐butyl acrylate (EBA) blends was studied using advanced dual bore capillary rheometer. The viscosity‐composition behavior of the uncompatibilized PA6/EBA blends exhibited negative deviation behavior from log‐additivity rule. The interfacial slip mechanism, operative between the matrix PA6 and dispersed EBA during shear flow was studied by the use of Lin's and Bousmina‐Palierne‐Utracki (BPU) model for viscosity for the blends under the processing conditions. On the other hand, the compatibilized PA6/EBA‐g‐MAH^0.49/EBA blends with varying dispersed phase volume fraction show positive deviation behavior. The reactive compatibilizers EBA‐g‐MAH^0.49 and EBA‐g‐MAH^0.96 increased the phase interaction with adequate reduction in the dynamic interfacial tension, which favored the particle break‐up and stabilized the morphology in the compatibilized blends. The extensional viscosity of the blends has enhanced because of the inclusion of EBA in all the uncompatibilized and compatibilized blends. The melt elasticity and elasticity function were systematically studied from first normal stress coefficient functions (ψ₁). The variation in the recoverable shear strain (γ_R), shear rate dependent relaxation time (λ) and shear compliance (J_c) under various shear rates were thoroughly analyzed for all the blend compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effects of emulsion parameters on relaxation behaviors for immiscible polymer blends

The relaxation behaviors of the binary immiscible blends reflected on the plots of the storage modulus and the imaginary part of complex viscosity were investigated using the Maxwell and the Palierne models. It was revealed that the peaks in the high‐ and low‐frequency regions on the complex viscosity imaginary part plot are owing to the relaxations of the blend and deformed dispersed droplets, respectively. Based on these two models, six emulsion parameters (interfacial tension, relaxation times and viscosities of two components, and dispersed phase volume fraction) were investigated in terms of their effects on the shape features of the plots of the imaginary part of complex viscosity and the Cole–Cole. The results showed that the viscosities of two components and dispersed phase volume fraction play key roles in the radii of the two circular arcs on the Cole–Cole plot. Furthermore, the two circular arcs are well separated in the case of lower interfacial tensions and dispersed phase viscosities, shorter matrix relaxation times, and higher matrix viscosities and dispersed phase volume fractions. The total relaxation time of the deformed dispersed droplets increases with increasing the viscosities of two components, especially with decreasing the interfacial tension. Three types of polymer blends were prepared and their dynamic frequency sweep testing results demonstrated the effectiveness of the corresponding predicted results. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39690.     

Rheological and viscoelastic properties of multiphase acrylic rubber/fluoroelastomer/polyacrylate blends

Dynamic viscoelastic properties and dynamic mechanical properties of blends of acrylate rubber (ACM), fluoroelastomer and polyacrylate plastics have been investigated with a rheometer (ARES RDA III) at a frequency (ω) range of 0.1 to 100 rad.s^?1. The analysis of thermorheological properties revealed that the dynamic moduli and dynamic viscosity of blends varied with the composition of the ACM/FKM blend and the level and type of polyfunctional acrylates. The blends showed negative deviation of the dynamic viscosity additive rule. Higher polyfunctional acrylates induced phase separations and showed temperature dependency. It was found that the data of the blends did not follow the Cole‐Cole plot of miscibility and the plot of log G′‐log G″ of the blend showed composition dependency. The dynamic mechanical analysis exhibited lower tan δ values for blends containing higher functional acrylates. Stress relaxation measurements showed longer periods of relaxation for all blends.     

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     

Thermal behavior and morphological and rheological properties of polypropylene and novel elastomeric ethylene copolymer blends

The thermal behavior including melting and crystallization behavior and morphological and rheological properties of the blends based on an isotactic polypropylene and a novel maleated elastomeric ethylene copolymer were investigated in this work. The addition of an elastomer to polypropylene (PP) was found not to change the PP crystalline structure significantly when cooled quickly from the melt. On recrystallization at a lower cooling rate, the elastomer promotes the formation of β?pseudohexagonal PP in PP‐rich blends. In elastomer‐rich compositions, heterogeneous nucleation is hindered and homogeneous nucleation takes place. These phenomena are revealed by morphology observation: that, with increasing of the elastomer content, the system undergoes PP continuous, dual‐phase continuity and PP‐dispersed morphologies. The blend viscosity at a low shear rate range increases continuously with increasing elastomer content and shows positive deviations from the additivity rule. In the terminal zone, the dynamic storage modulus of the blends shows positive deviation from the simple mixing rule and the maximum deviation lies in the composition range of dual‐phase continuity which could be caused by a large increase in the interfacial tension. The Cox–Merz rule does not hold for the blends because of the two‐phase heterogeneous structure and its variation in steady and oscillatory shear flow. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3430–3439, 2002     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005     

Correlation of rheology and morphology and estimation of interfacial tension of immiscible COC/EVA blends

Rheology and morphology of cyclic olefin copolymer (COC) / ethylene vinyl acetate copolymer (EVA) immiscible blends with droplet and co-continuous morphologies were experimentally examined and theoretically analyzed using emulsion and micromechanical models. The blends showed an asymmetric phase diagram in which the EVA-rich blends had smaller dispersed size domains as compared to the COC-rich blends. This could be explained based on the higher melt elasticity and viscosity of COC as compared to EVA determined by the rheological investigations. The rheological tools were used to investigate the miscibility of the blends. From the melt viscosity data it is found that the COC/EVA blends show a positive deviation behavior at all compositions which is a hint for strong interaction between the COC and EVA. Analysis of Cole-Cole and Han diagrams revealed that COC/EVA blends, at high EVA contents, were more compatible than COC-rich blends. For the droplet morphology, Palierne model was more successful but, by increasing the dispersed phase content some deviation was observed. In the co-continuous region, the Coran model was in good correspondence with the experimental data as compared to the Veenstra’s model. The storage and loss modulus of EVA-rich blends had a better correspondence with the Palierne model than the COC-rich blends which further confirmed the morphological findings. Interfacial tension calculated for the COC/EVA blends using the Palierne model, were about 1.2 and 15 mN/m² for EVA-rich (10/90) and COC-rich blends (90/10), respectively. In both EVA-rich and COC-rich systems the interfacial tension increased with increasing the dispersed phase content.     

Phase morphology and melt viscoelastic properties in blends of ethylene/vinyl acetate copolymer and metallocene-catalysed linear polyethylene

The aim of this study was to determine the linear viscoelastic properties of a series of ethylene/vinyl acetate copolymer/metallocene-catalysed polyethylene (mPEs) blends. Newtonian viscosity showed a pronounced positive deviation from the double reptation model, which assumes miscibility or, at least, cooperative relaxation between the mixed species. Enhanced values of steady-state compliance and elastic indices with respect to those of the pure components were also noted. These features are typical of emulsion-like polymer blends and are thought to arise from additional relaxation processes associated with dispersed phase deformability. Application of the Palierne model for emulsions of two viscoelastic liquids showed good agreement with our experimental dynamic results at both ends of the phase diagram. However, the model failed at intermediate compositions. Through the application of several rheological criteria we were able to locate the phase inversion concentration at a weight fraction of w=0.60 in the mPEs. It is suspected that, in this composition range, a fully co-continuous phase develops due to the phase inversion mechanism, which has considerable effects on the viscoelastic properties of the blends.     

Morphology and rheological properties of polypropylene/reactive elastomer blends

The relation of morphology to the linear viscoelastic properties for polymer blends consisting of an inert polypropylene and an elastomeric dispersed phase, made of two miscible copolymers, EVA and EMA, was investigated. The rheological properties of the elastomeric phase were modified by crosslinking in presence of an organometallic catalyst. The activation energy for the transesterification reaction taking place between EVA and EMA has been determined by following the increases of the complex viscosity with time and temperature. The Palierne model has been used to describe the linear viscoelastic behavior of the blends, and to estimate the interfacial tension between the immiscible components. The model was shown to describe relatively well the linear viscoelastic properties of reactive and nonreactive blends containing 30% or less elastomer. In parallel, the morphology of reactive and nonreactive blends (i.e. without catalyst in the elastomeric phase), before and after rheological experiments, has been determined using scanning electron microscopy. The size of the dispersed elastomeric particles for reactive blends prepared using an internal mixer was found to be, in most cases, much smaller than that for nonreactive blends.     

Morphological properties,rheological behaviors,and phase interaction of nylon 11/polypropylene blends by in situ reactive compatibilization and dispersion through polyhydroxybutyrate

The current research discusses the reactive compatibilization of nylon 11 (PA11) and polypropylene (PP) using maleic anhydride grafted PP (PP-g-MA) through an extruder. PP phase is dispersed in PA11 by coalescence and droplet break-up mechanism by using polyhydroxybutyrate (PHB) as a dispersion agent that induces uniform interaction between the blend components. The reactive compatibilization ensures the mixing of polymers, and the consistent interaction of phases is controlled by dispersion. All of the blends were processed through melt processing at different compositions using a twin-screw extruder. Scanning electron microscopy was used to determine the morphologies of the binary and ternary blends. Surface tension and interfacial tension of the homopolymer characterizes the interaction of the polymers at interphase. The interaction of PHB/PA11 appeared preferable than that of PHB/PP, elaborating on the efficient dispersion and droplet formation of the PP phase. The compatibilizer maleic anhydride grafted PP (PP-g-MA) imparts a drastic effect on the compatibility of PA11-PP and PA11-PHB-PP blends and reduces PP phase particle size, which indicates the affinity of PHB and PP. The encapsulation of PP by PHB was seen in the expectation of minimum free energy models. The rheological measurements were used to understand the phase separation within blends. These measurements were also applied to understand the interaction between PA11-PP-PHB phases. The modulus values and viscosity ratio of the blends were measured to follow the chain relaxation in the melt. In the Cole–Cole plot, it was found that the reduction in PP phase size influences the relaxation of chains of blends.     

Effect of reactive compatibilization on the interfacial slip in nylon‐6/EPR blends

The viscosity of uncompatibilized polymer blends often shows a negative deviation from a log‐additivity rule at shear rates relevant to processing. This deviation has been attributed to interfacial slip, which is related to the loss of entanglements at the interface. In this work interfacial slip and the effect of reactive compatibilization on this phenomenon are studied in blends consisting of ethylene‐propylene rubber and nylon‐6. The viscosity and morphology of blends with various compositions and compatibilizer content are investigated systematically. The results indicate that interfacial slip can indeed be important in uncompatibilized systems whereas it is suppressed in compatibilized blends. This is further supported by a study of the viscosity of multilayer structures. Both the effect of reactive compatibilization and of the number of layers on the rheology are studied. Again it is demonstrated that reactive compatibilization suppresses interfacial slip.     

Continuity development in polymer blends of very low interfacial tension

Phase continuity development and co-continuous morphologies are highly influenced by the nature of the interface in immiscible polymer blends. Blends of ethylene-propylene-diene terpolymer (EPDM) and polypropylene (PP) possess an interfacial tension of about 0.3 mN/m and provide an interesting model system to study the detailed morphology development in a very low interfacial tension binary system. A variety of blends with viscosity ratios of 0.2-5.0 and shear stresses of 11.7-231.4 kPa were considered. Using a variety of sophisticated morphology protocols it is shown that at low blend compositions, the dispersed phase actually exists as stable fibers of extremely small diameter of 50-200 nm and the continuity develops by fiber-fiber coalescence. An analysis using break-up times from Tomotika theory also supports the notion of highly stable dispersed fiber formation. These results challenge the current view of the dispersed phase as small spherical droplets. It is shown, under these conditions, that a seven-fold variation in the viscosity ratio has virtually no influence on % continuity or morphology, while a large change in the matrix shear stress from 11.7 to 90.9 kPa has an important effect on pore diameter. Both sides of the continuity diagram are studied and highly symmetrical continuity behavior is observed with composition. In fact a single master continuity curve is observed for these blends varying in viscosity ratio from 0.7-5.0 and with shear stresses from 11.7-90.9 kPa. Although the glass transition temperatures indicate that these materials are completely immiscible after melt mixing and cooling, it is shown that the blends demonstrate the morphological features of a partially miscible system. These results support a concept that the blend was partially miscible during melt blending, at which time the gross morphological features of the blend were developed, but becomes fully phase separated upon cooling. It appears that the quenching of the EPDM/PP blend from the melt is rapid enough to preserve the imprint of that partial miscibility on the gross blend morphology.     

Rheological behavior and mechanical properties of high‐density polyethylene blends with different molecular weights

The dynamic rheological and mechanical properties of the binary blends of two conventional high‐density polyethylenes [HDPEs; low molecular weight (LMW) and high molecular weight (HMW)] with distinct different weight‐average molecular weights were studied. The rheological results show that the rheological behavior of the blends departed from classical linear viscoelastic theory because of the polydispersity of the HDPEs that we used. Plots of the logarithm of the zero shear viscosity fitted by the Cross model versus the blend composition, Cole–Cole plots, Han curves, and master curves of the storage and loss moduli indicated the LMW/HMW blends of different compositions were miscible in the melt state. The tensile yield strength of the blends generally followed the linear additivity rule, whereas the elongation at break and impact strength were lower than those predicted by linear additivity; this suggested the incompatibility of the blends in solid state. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of different molecular weights of polyhexene-1 on the morphology and rheology of cyclic olefin copolymer blends

The morphology and rheological behavior of cyclic olefin copolymer (COC) blends with two molecular weights of polyhexene-1 (PH-1, PH-1-UH [ultra-high]) were investigated at a wide range of compositions. Morphology of the blends at low concentrations of polyhexene-1 s showed a droplet-matrix structure and changed to a co-continuous morphology at intermediate concentrations. The rheological Cole-Cole plots and viscosity versus composition confirmed immiscibility of the blends. The interfacial interaction of blends phases was investigated and Complex viscosity and storage modulus versus frequency were measured and the results were consistent with high interfacial strength between the COC and high concentrations of PH-1-UH which increases the melt strength of the blends. Relaxation time spectra and Tan δ versus frequency curves were analyzed and these results were consistent with a high degree of entanglements between the COC and PH-1-UH chains in the PH-1-UH-rich compounds which in turn increased the elasticity. Damping factor measurements and calculation of interfacial tension using emulsion models showed that in the COC-rich blends, the interfacial interaction COC/PH-1 blends is higher than that of the COC/PH-1-UH blends and thus the elasticity and particles form relaxation time of the PH-1 blends are higher compared to PH-1-UH blends.     

Effect of blend ratio on bulk properties and matrix-fibril morphology of polypropylene/nylon 6 polyblend fibers

Ternary blends of polypropylene (PP), nylon 6 (N6) and polypropylene grafted with maleic anhydride (PP/N6/PP-g-MAH) as compatibilizer with up to 50 wt% of N6 were investigated. PP-g-MAH content was varied from 2.5 to 10%. Blends of the two polymers PP/N6 (80/20) without the compatibilizer were also prepared using an internal batch mixer and studied. The ternary blends showed different rheological properties at low and high shear rates. The difference depended on the amount of N6 dispersed phase. Co-continuous morphology was observed for the blend containing 50% N6. This blend also exhibited higher viscosity at low shear rate and lower viscosity at high shear rates than the value calculated by the simple rule of mixture. At higher shear rates, viscosity was lower than that given by the rule of mixture for all blend ratios. An increase in viscosity was observed in the 80/20 PP/N6 blend after the concentration of the interfacial agent (PP-g-MAH) was increased. Polyblends containing up to 30% N6 could be successfully melt spun into fibers. DSC results showed that dispersed and matrix phases in the fiber maintained crystallinity comparable to or better than the corresponding values found in the neat fibers. The dispersed phase was found to contain fibrils. By using SEM and LSCM analyses we were able to show that the N6 droplets coalesced during melt spinning which led to the development of fibrillar morphology.     

Dynamic shear rheological behavior of PP/EPR in‐reactor alloys synthesized by multi‐stage sequential polymerization process

The rheological behavior, morphology, and mechanical properties of in‐reactor alloy of polypropylene (PP)/ethylene propylene rubber (EPR) synthesized by multi‐stage sequential polymerization process are studied in this article. The relationship between polymerization parameters, morphology, and rheological properties are evaluated by scanning electron microscopy (SEM) and small amplitude oscillation rheometry in the linear viscoelastic region. The electron microscopy of samples is showed that by increasing switching frequency in polymerization time, the size of EPR particles decrease. By increasing switching frequency, the curves of complex viscosity against angular frequency of samples are shifted to higher values at low range of shear rates with no significant change at higher frequencies in Power‐law region. The modified Cole‐Cole plots revealed the enhanced melt elasticity by increasing switching frequency up to 230°C. The plot of phase angle versus absolute value of complex modulus G* is used for the evaluation of matrix‐droplets interaction at various temperatures. It is observed two different behaviors before and after 230°C which is the evidence of the change in relaxation mechanism of the blend components because of coarsening the rubber particles in the phase separation process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheology of polycarbonate/linear low density polyethylene blends

The flow behavior of linear low density polyethylene blended with polycarbonate (LLDPE/PC) was studied at 245°C using an Instron Capillary Rheometer and a Rheometrics Mechanical Spectrometer. The capillary measurements were repeated several times for each crosshead speed and capillary. The averaged values were corrected for shear heating as well as the pressure, entrance-exit, and power-law fluid effects. In spite of the utmost care, blend results were erratic with a standard deviation of 25 to 35 percent. Analysis of the capillary data suggested a telescopic flow with the lower viscosity component of the blend migrating toward the capillary wall. The experimental difficulties resulted from the flow and time induced variations of blend morphology. By contrast, the dynamic shear test results were found to be rapid and reproducible with a standard deviation for the complex viscosity of blends not exceeding four percent. The shear moduli of blends indicated the presence of an apparent (time dependent) yield stress, originating from interaction between domains of the dispersed phase. At frequencies exceeding a critical value, shear coalescence of the dispersed phase was observed near the rim of the rheometer plates.