Time‐temperature superposition principle applicability for blends formed of immiscible polymers

In this work, the linear viscoelastic behavior of PP/PS and PP/HDPE blends modified with SEBS and EPDM, respectively, was studied. Small amplitude oscillatory shear measurements were carried out at different temperatures, ranging from 190°C to 240°C. The storage (G') and loss (G") moduli curves obtained were horizontally shifted and curves of angle delta (δ) (δ = atan (G"/G')) as a function of complex shear modulus (G*), known as van Gurp plots, were obtained at several temperatures, to test the applicability of time‐temperature superposition principle (TTS) to these blends. The results showed that successful application of TTS depends on the flow energy of activation and horizontal shift factors of the individual components of the blend, on the interfacial properties of the blend and on the concentration of compatibilizer added to the blend. TTS application failed for PP/PS blend, but held for PP/HDPE blend. Addition of SEBS to PP/PS blends promoted successful TTS application at specific concentrations that corresponded to interfacial saturation of the dispersed phase. Addition of EPDM did not imply sensitive change on TTS application for the PP/HDPE blends.     

iPP/HDPE blends. II. Modification with EPDM and EVA

Past work has shown that addition of high-density polyethylene (HDPE) to polypropylene (PP) resulted in a significant reduction in the elongation at break and in the gate-region impact strength of injection molded articles. In this study, we report on the compatibilization of these blends with ethylene/propylene/diene monomer (EPDM) or ethylene/vinyl acetate (EVA) copolymers. EPDM is effective at improving the impact strength and gate puncture resistance of a 90/10 PP/HDPE blend. EVA, on the other hand, is effective at improving the impact strength and the elongation at break of this material. It was also found that EVA is a better impact modifier for PP than is EPDM. DSC analysis indicated that EPDM, when blended with PP, caused a significant reduction in the degree of crystallinity of the PP. This was not observed in the case of EVA/PP blends. Further, our results indicate that care must be taken in designating a particular material as a better compatibilizer than some other material. It is crucial that conditions be attached to the label compatibilizer, indicating in particular the desired mechanical properties of the blend. © 1996 John Wiley & Sons, Inc.     

Polymer Blends of PBT and PP Compatibilized by Epoxidized Ethylene Propylene Diene Rubber

Summary In this paper, ethylene-propylene-diene-rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM(eEPDM). The eEPDM were used to compatibilize poly(butylenes terephthalate)(PBT) and polypropylene(PP) blends in a haake mixer. FTIR results showed that the EPDM had been epoxidized. FTIR and torque test showed the epoxy functional groups in the eEPDM can react with the carboxylic acid or hydroxyl terminal groups in PBT at the interface to form PBT-g-EPDM copolymers. SEM observation showed that these in situ formed grafted copolymers tent to concentrate along the interface to reduce the interfacial tension at the melt and suppress coalescence by steric hindrance. higher quantity of eEPDM compatibilizer in the blend results in a better compatibilized blend in terms of finer phase domains. Notched Izod impact tests showed that both the adding of rubber and the formation of PBT-g-EPDM copolymer improved the toughness of PBT/PP blends.     

Interface modification of compatibilized polyethylene terephthalate/polypropylene blends: Effect of compatibilization on thermomechanical properties and thermal stability

Polyethylene terephthalate (PET) and polypropylene (PP) are incompatible thermoplastics because of differences in chemical structure and polarity, hence their blends possess inferior mechanical and thermal properties. Compatibilization with a suitable block/graft copolymer is one way to improve the mechanical and thermal properties of the PET/PP blend. In this study, the toughness, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA) of PET/PP blends were investigated as a function of different content of styrene‐ethylene‐butylene‐styrene‐g‐maleic anhydride (SEBS‐g‐MAH) compatibilizer. PET, PP, and SEBS‐g‐MAH were melt‐blended in a single step using the counter rotating twin screw extruder with compatibilizer concentrations of 0, 5, 10, and 15 phr, respectively. The impact strength of compatibilized blend with 10 phr SEBS‐g‐MAH increased by 300% compared to the uncompatibilized blend. Scanning electron microscope (SEM) micrographs show that the addition of 10 phr SEBS‐g‐MAH compatibilizer into the PET/PP blends decreased the particle size of the dispersed PP phase to the minimum level. The improvement of the storage modulus and the decrease in the glass transition temperature of the PET phase indicated an interaction among the blend components. Thermal stability of the PET/PP blends was significantly improved because of the addition of SEBS‐g‐MAH. J. VINYL ADDIT. TECHNOL., 23:45–54, 2017. © 2015 Society of Plastics Engineers     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

i-PP/HDPE blends. III. Characterization and compatibilization at lower i-PP contents

The mechanical properties of high-density polyethylene (HDPE)-rich i-PP/HDPE blends were studied. Two grades of HDPE were investigated, one with a melt viscosity close to that of the polypropylene (PP) and the other having a much lower melt viscosity. Compatibilization of the 10/90 i-PP/HDPE blend with three copolymers (an ethylene/propylene/diene [EPDM] copolymer and two ethylene/vinylacetate [EVA] copolymers, differing in their VA content) was also investigated. Blends of PP with the low melt viscosity HDPE displayed poor mechanical properties. It was not possible to improve these properties sufficiently with EPDM or EVA. In the case where viscosity matching was achieved between PP and HDPE, addition of i-PP (up to 30%) to HDPE resulted in a large drop in the impact strength of the blends, compared to that of the neat HDPE. A large drop (>50%) was also observed in the ultimate tensile elongation. However, the flexural modulus, yield stress, and ultimate tensile strength all increased with the introduction of i-PP into HDPE. Modification of these blends with an EPDM resulted in the return of all properties to values very close to those of the neat HDPE. The ultimate tensile elongation of the EPDM-modified i-PP/HDPE blend even exceeded that of the virgin HDPE. It was also found that although EVAs can be used to compatibilize these blends these additives were not as effective as was the EPDM. © 1996 John Wiley & Sons, Inc.     

Double‐yielding behavior in injection‐molded polycarbonate/high‐density polyethylene/ethylene–vinyl acetate copolymer blends

A uniaxial tensile test was performed for polycarbonate (PC)/high‐density polyethylene (HDPE)/ethylene–vinyl acetate copolymer (EVA) blends with a fixed EVA content but various PC contents. The double‐yielding phenomenon and its composition dependence, as observed in the PC/HDPE blend, were again detected. EVA did not serve as a successful compatibilizer of PC and HDPE in the PC/HDPE/EVA blend. The incorporation of EVA resulted in a larger size and a more irregular shape of the PC fibers, as indicated in the scanning electron microscope observations; this, consequently, produced a higher serious stress concentration in the blend. This more complicated and instable morphology produced different double‐yielding behaviors in the PC/HDPE/EVA blends compared with the binary one. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheology, Morphology and Estimation of Interfacial Tension of LDPE/EVA and HDPE/EVA Blends

Summary Rheological characteristics and morphology of low-density polyethylene (LDPE) /ethylene vinyl acetate copolymer (EVA) and high-density polyethylene (HDPE)/EVA blends were compared. Morphological examinations clearly reveal a two-phase morphology in which the LDPE/EVA blends have smaller dispersed domain size than HDPE/EVA Furthermore, LDPE/EVA shows a finely interconnected morphology at 50wt% of EVA while HDPE/EVA exhibits a coarse co-continuous morphology at the same composition. The morphological observations can be attributed to the lower viscosity ratio and lower interfacial tension in the LDPE/EVA system. The Palierne model also successfully fits to the experimental data giving higher values for interfacial tension of HDPE/EVA system as compared to LDPE/EVA.     

VC／BA共混物增容PVC／HDPE共混体系的研究

采用氯乙烯—丙烯酸丁酯(VC/BA)共混物作为聚氯乙烯(PVC)/高密度聚乙烯(HDPE)共混物的增容剂,通过冲击实验、拉仲实验、动态力学分析,系统地研究了共混体系性能与其结构之间的关系。通过Brabender流变仪测定了VC/BA共混物增容PVC/HDPE共混体系的流变性能。结果表明,VC/BA共混物是PVC/HDPE共混体系的良好增容剂。在一定范围内,VC/BA共混物与HDPE对PVC有协同增韧效应。vC/BA和HDPE的加入改善了PVC的塑化和流变性能     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Influence of compatibilizers on mechanical properties,crystallization, and morphology of polypropylene/scrap rubber dust blends

Polypropylene blends containing a dispersed phase of scrap rubber dusts obtained from sport shoes manufacture; midsole (M, vulcanized EVA foam) and outsole (O, vulcanized rubber blend of NR, SBR, and BR) were studied. The influence of various compatibilizers on the mechanical properties of these blends were investigated. Significant development of impact strength was attained by using 6 and 10 phr of styrene–ethylene–butylene–styrene (SEBS) and maleic anhydride‐grafted styrene–ethylene–butylene–styrene (SEBS‐g‐MA) as compatibilizers for both compounds filled with midsole and outsole dusts. The tensile strength of each compound was slightly decreased when the compatibilizer loading increased, whereas the elongation at break was significantly increased. The enhancements of the impact strength and the elongation at break are believed to arise from reduction of interfacial tension between two phases of the rubber and the PP, which results in some reduction of the particle size of the fillers. Scanning electron microscopy (SEM) confirmed the evidence of the reduction of scrap rubber dust into small rubber particle sizes in the compound, and also showed the occurrence of some fibrils. Optical microscopy (crossed polars) observations suggested that the addition of the rubber dust resulted in a less regular spherulite texture and less sharp spherulite boundaries. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 148–159, 2002     

Morphological stability of postconsumer PET/HDPE blends

Summary The morphological stability and the mechanical properties of postconsumer polyethylene terephthalate (PET) and high density polyethylene (HDPE), at different composition with and without compatibilizer were investigated. The blends were prepared in an internal mixer and in a twin screw-extruder at different stretching ratio. For uncompatibilized blends, (previously prepared by extrusion), the particle size of the dispersed phase increases after being reprocessed in an internal mixer. However, in the case of compatibilized blend the particle size remains constant. Consequently, the compatibilizer reduces interfacial mobility, coalescence effects and stabilizes the morphology. The mechanical properties are also modified by the presence of the compatibilizer, mainly the elongation at break. Received: 14 January 2000/Accepted: 16 August 2000     

Influence of composition on the linear viscoelastic behavior and morphology of PP/HDPE blends

In this paper the influence of temperature and composition on the dynamic behavior and morphology of polypropylene (PP)/high-density polyethylene (HDPE) blends were studied. The blend composition ranged from 5 to 30 wt% of dispersed phase (HDPE) and the temperatures ranged from 180 to 220 °C. The interfacial tension between PP and HDPE at temperatures of 180, 200 and 220 °C was obtained from fitting Palierne's emulsion model [1] to the experimental data of PP/HDPE blends with different compositions and from the weighted relaxation spectra of PP/HDPE blends with different compositions, following Gramespacher and Meissner [2] analysis. The interfacial tension between PP and HDPE as inferred from the rheological measurements was shown to depend on PP/HDPE blend composition. However, the results indicated that there is a range of PP/HDPE blend composition for which interfacial tension between PP and HDPE is constant. Considering these values, it was shown that interfacial tension between PP and HDPE decreases linearly with increasing temperature.     

Linear viscoelastic behavior of compatibilized PMMA/PP blends

In this work, the morphology and linear viscoelastic behavior of PMMA/PP blends to which a graft copolymer PP‐g‐PMMA has been added was studied. The copolymer concentration varied from 1 to 10 wt % relative to the dispersed phase concentration. The rheological data were used to infer the interfacial tension between the blended components. It was observed that PP‐g‐PMMA was effective as a compatibilizer for PMMA/PP blends. For PP‐g‐PMMA concentration added below the critical concentration of interface saturation, two rheological behaviors were observed depending on the blend concentration: for 70/30 blend, the storage modulus, at low frequencies, increased as compared to the one of the unmodified blend; for 90/10 blend, it decreased. For 90/10 blend, the relaxation spectrum presented an interfacial relaxation time related to the presence of the compatibilizer (τ_β). For PP‐g‐PMMA concentrations added above the critical concentration of interface saturation, the storage modulus of all blends increased as compared with the one of the unmodified blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The Effect of Epoxidized Natural Rubber (ENR-50) or Polyethylene Acrylic Acid (PEA) as Compatibilizer on Properties of Ethylene Vinyl Acetate (EVA)/Natural Rubber (SMR L) Blends

The effect of epoxidized natural rubber (ENR) or polyethylene acrylic acid (PEA) as a compatibilizer on properties of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends was studied. 5 wt.% of compatibilizer was employed in EVA/SMR L blend and the effect of compatibilizer on tensile properties, thermal properties, swelling resistance, and morphological properties were investigated. Blends were prepared by using a laboratory scale of internal mixer at 120°C with 50 rpm of rotor speed. Tensile properties, thermal properties, thermo-oxidative aging resistance, and oil swell resistance were determined according to related ASTM standards. The compatibility of EVA/SMR L blends with 5 wt.% of compatibilizer addition or without compatibilizing agent was compared. The EVA/SMR L blend with compatibilizer shows substantially improvement in tensile properties compared to the EVA/SMR L blend without compatibilizer. Compatibilization had reduced interfacial tension and domain size of ethylene vinyl acetate (EVA)/natural rubber (SMR L) blends.     

Effect of the addition of acrylonitrile/ethylene–propylene–diene monomer (EPDM)/styrene graft copolymer on the morphology–properties relationships in poly(styrene‐co‐acrylonitrile)/EPDM rubber blends

Blends of poly(styrene‐co‐acylonitrile) (SAN) with ethylene–propylene–diene monomer (EPDM) rubber were investigated. An improved toughness–stiffness balance of the SAN/EPDM blend was obtained when an appropriate amount of acrylonitrile–EPDM–styrene (AES) graft copolymer was added, prepared by grafting EPDM with styrene–acrylonitrile copolymer, and mixed thoroughly with both of the two components of the blend. Morphological observations indicated a finer dispersion of the EPDM particles in the SAN/EPDM/AES blends, and particle size distribution became narrower with increasing amounts of AES. Meanwhile, it was found that the SAN/EPDM blend having a ratio of 82.5/17.5 by weight was more effective in increasing the impact strength than that of the 90/10 blend. From dynamic mechanic analysis of the blends, the glass‐transition temperature of the EPDM‐rich phase increased from ?53.9 to ?46.2°C, even ?32.0°C, for the ratio of 82.5/17.5 blend of SAN/EPDM, whereas that of the SAN‐rich phase decreased from 109.2 to 108.6 and 107.5°C with the additions of 6 and 10% AES copolymer contents, respectively. It was confirmed that AES graft copolymer is an efficient compatibilizer for SAN/EPDM blend. The compatibilizer plays an important role in connecting two phases and improving the stress transfer in the blends. Certain morphological features such as thin filament connecting and even networking of the dispersed rubber phase may contribute to the overall ductility of the high impact strength of the studied blends. Moreover, its potential to induce a brittle–ductile transition of the glassy SAN matrix is considered to explain the toughening mechanism. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1685–1697, 2004     

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.     

Modified interfacial tensions measured in situ in ternary polymer blends demonstrating partial wetting

An in situ Neumann triangle-focused ion beam-atomic force microscopy (NT-FIB-AFM) method has been used to measure modified PS/HDPE interfacial tensions in ternary PS/PP/HDPE blends prepared by melt mixing and demonstrating partial wetting. The ternary blend was modified with SEB, SB and SEBS copolymers. Results related to the position of the PS droplet at the interface show that a symmetrical diblock copolymer is somewhat more efficient in decreasing the interfacial tension compared to an asymmetrical one of similar molecular weight, while the SEBS triblock copolymer appears to have no effect at all. Using the NT-FIB-AFM method, the lowest modified PS/HDPE interfacial tension is 3.0 ± 0.4 mN/m for the symmetric diblock, compared to 4.2 ± 0.6 mN/m (N = 34) for the unmodified interface. This corresponds to an apparent areal density in SEB copolymer equal to 0.16 ± 0.03 molecules/nm², which is near reported saturation values. By varying the concentration of the copolymer, an emulsification curve reporting the value of the PS/HDPE modified interfacial tension as a function of the apparent areal density of the copolymer at the PS/HDPE interface has been obtained. The interfacial tension values obtained by the NT-FIB-AFM approach are significantly higher than the 0.5 ± 0.2 mN/m (N = 3) result obtained by using the classical breaking thread method with the same materials. This discrepancy does not appear to be due to a poor migration of the copolymer to the PS/HDPE interface, but could instead be attributed to the interfacial elasticity of the compatibilized interface, a phenomena that has not been accounted for so far in experimental studies on the morphology of compatibilized multicomponent polymer blends.     

Compatibilization of PP/PE blends and scraps with Royalene: Mechanical properties,SAXS, and WAXS

PP/PE 93/7 model virgin blends and recycled scraps were compatibilized with Royalene (EPDM/PE 65/35 blend) and mechanically tested. No differences in impact and tensile properties between them were found. However, the tensile-impact strength increased almost twice with 10%-compatibilized sample in comparison with uncompatibilized ones. The yield stress of blends containing 10% Royalene decreased to 75–80% of the original value. This effect is in agreement with microhardness measurements; the increase in the compatibilizer content causes softening of the blend. The elongation at break and elongation at yield do not depend on the compatibilizer concentration. The compatibilizer does not influence the degree of crystallinity (WAXS data) of the blends either. Vickers microhardness is in good agreement with Tabor's relationship. The differences between long periods of HDPE in Royalene and LDPE in PP/PE blends (SAXS) proved PE/EPDM interaction. The interaction plays a key role in the toughening of PP/PE blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008