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 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     

Radiation effects on HDPE/EVA blends

In this article, we discuss the radiation effects of high‐density polyethylene (HDPE)/ethylene–vinyl acetate (EVA) copolymer blends. In comparison with the low‐density polyethylene/EVA blends, the EVA content in the HDPE/EVA blends had a lower enhancement effect on radiation crosslinking by γ‐ray irradiation in air. The phenomenon is discussed with the compatibility, morphology, and thermal properties of HDPE/EVA blends. The HDPE/EVA blends were partly compatible in the amorphous region, and radiation crosslinking of the HDPE/EVA blend was less significant, although increasing the amorphous region's content of the HDPE/EVA blends and the vinyl acetate content of EVA were beneficial to radiation crosslinking. The good compatibility was a prerequisite for the enhancement effect of EVA on the radiation crosslinking of the polyethylene/EVA copolymer. The radiation crosslinking and the degradation mechanism of HDPE/EVA blends were examined quantitatively by a novel method, the step analysis process of irradiated HDPE/EVA blends with a thermal gravimetric analysis technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 553–558, 2002     

Dynamic mechanical behavior of high‐density polyethylene/ethylene vinyl acetate copolymer blends: The effects of the blend ratio,reactive compatibilization,and dynamic vulcanization

The effects of the blend ratio, reactive compatibilization, and dynamic vulcanization on the dynamic mechanical properties of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends have been analyzed at different temperatures. The storage modulus of the blend decreases with an increase in the EVA content. The loss factor curve shows two peaks, corresponding to the transitions of HDPE and EVA, indicating the incompatibility of the blend system. Attempts have been made to correlate the observed viscoelastic properties of the blends with the blend morphology. Various composite models have been used to predict the dynamic mechanical data. The experimental values are close to those of the Halpin–Tsai model above 50 wt % EVA and close to those of the Coran model up to 50 wt % EVA in the blend. For the Takayanagi model, the theoretical value is in good agreement with the experimental value for a 70/30 HDPE/EVA blend. The area under the loss modulus/temperature curve (LA) has been analyzed with the integration method from the experimental curve and has been compared with that obtained from group contribution analysis. The LA values calculated with group contribution analysis are lower than those calculated with the integration method. The addition of a maleic‐modified polyethylene compatibilizer increases the storage modulus, loss modulus, and loss factor values of the system, and this is due to the finer dispersion of the EVA domains in the HDPE matrix upon compatibilization. For 70/30 and 50/50 blends, the addition of a maleic‐modified polyethylene compatibilizer shifts the relaxation temperature of both HDPE and EVA to a lower temperature, and this indicates increased interdiffusion of the two phases at the interface upon compatibilization. However, for a 30/70 HDPE/EVA blend, the addition of a compatibilizer does not change the relaxation temperature, and this may be due to the cocontinuous morphology of the blends. The dynamic vulcanization of the EVA phase with dicumyl peroxide results in an increase in both the storage and loss moduli of the blends. A significant increase in the relaxation temperature of EVA and a broadening of the relaxation peaks occur during dynamic vulcanization, and this indicates the increased interaction between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2083–2099, 2003     

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.     

On the compatibilization and dynamic vulcanization of polyacetal/ethylene propylene diene terpolymer blends

This study describes an attempt to improve the impact resistance of polyacetal (POM)/ethylene propylene diene terpolymer (EPDM) blends by means of compatibilization and dynamic vulcanization. A commerical copolymer, poly(acrylic acid)-grafted polypropylene (PGP), has been used as a compatibilizer to control the phase morphology of the blend system. Dicumyl peroxide is used to dynamically vulcanize the EPDM elastomer in the blend. At temperatures higher than 185°C, the compatibilizer decreases the viscosity of compatibilized and dynamically vulcanized (cdv) POM/EPDM blends. Impact strength of the cdv blend system increases considerably with a marginal decrease in tensile yield stress and heat deflection temperature as the PGP content increases. The significant increase in impact strength seems to be due to the role of PGP as a linking agent for the binary blends rather than as a third component. Though dynamic mechanical studies do not indicate any compatibility in cdv-POM/EPDM blends, scanning electron microscopy reveals the strong interpenetrating interphase in the compatibilized blend system. Dynamic vulcanization raises elastic recovery and tensile modulus of the blends. Hysteresis energies of the blends increase consistently with the addition of PGP. The crystalline structure of POM is not affected by compatibilization and vulcanization. © 1994 John Wiley & Sons, Inc.     

In situ compatibilization of HDPE/PET blends

The reactive compatibilization of immiscible polymers such as high‐density polyethylene (HDPE) and poly(ethylene terephthalate) (PET) by interfacial grafting of maleic anhydride (MA) without initiator in the molten state was investigated in this study. Grafting reaction of MA onto HDPE was carried out in a Rheocord HAAKE mixer varying reaction parameters such as the temperature, the shear rate, and the time of reaction. Then, the purified copolymers were characterized by infrared spectrometry and the MA content of HDPE‐g‐MA copolymers was determined by volumetric titration. It has been shown that thermomechanical initiation is sufficient to reach grafting yield of 0.3 to 2.5 wt % of MA. We studied then the compatibilization of HDPE/PET blends by interfacial grafting of MA. The in situ interfacial reaction leads to the formation of HDPE‐g‐MA copolymer which acts as a compatibilizer in the blends. The foremost interest of this work is that it provides a simple way of compatibilization of immiscible blends of polyolefin and polyester in one transformation step without using free‐radical initiators. The mechanical properties of the blends are strongly improved by the addition of small quantities of MA. The SEM observations of the compatibilized blends show a deep modification of the structure (i.e., enhanced regularity in the nodule dispersion and better interfacial adhesion). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 874–880, 2001     

Dielectric properties of isotactic polypropylene/nitrile rubber blends: Effects of blend ratio,filler addition,and dynamic vulcanization

The dielectric properties of isotactic polypropylene/acrylonitrile–butadiene rubber blends have been investigated as a function of frequency with special reference to the effect of blend ratio. The dielectric properties measured were volume resistivity, dielectric constant (ϵ′), dissipation factor (tan δ), and loss factor (ϵ″). At high frequencies, a transition in relaxation behavior was observed whereby the dielectric constant of the blends decreased with frequency, whereas the loss tangent and loss factor increased on reaching a maximum. The variation of the dielectric properties with blend composition was correlated with blend morphology, and relationships were established with reference to blend composition. Experimental ϵ′ values were compared with theoretical predictions. The effect of the addition of fillers on the dielectric properties was also investigated for different fillers and filler loadings. It was found that silica filler increases the dissipation factor, whereas carbon black and cork gave a reverse trend. The variation in dielectric properties upon dynamic vulcanization of the rubber phase using different vulcanizing agents (such as sulfur, peroxide, and mixed systems) was also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 255–270, 1999     

Failure properties of thermoplastic elastomers from polyethylene/nitrile rubber blends: Effect of blend ratio,dynamic vulcanization,and filler incorporation

Thermoplastic elastomers from blends of high‐density polyethylene and acrylonitrile butadiene rubber were prepared by a melt‐blending technique. The blends were dynamically vulcanized using sulfur, peroxide, and mixed curing systems. The peroxide concentration was varied to obtain samples of varying degrees of crosslinking. The peroxide system showed better mechanical properties. The crosslink density determination by the equilibrium swelling method revealed that the enhancement in properties can be correlated to the extent of crosslinking. It is observed that the effect of dynamic vulcanization on the property improvement is much more pronounced in rubber‐rich blends. To study the effect of filler incorporation on mechanical properties, fillers such as carbon black, silica, silane‐treated silica, and cork‐filled samples were prepared. All filled systems, except cork filled, exhibited superior mechanical properties. Scanning electron micrographs of selected fractured surfaces were analyzed to study the failure mechanism of the different compositions. Various theoretical models were applied to correlate the observed mechanical behavior with that of theoretically predicted values. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2912–2929, 2006     

Effects of blend composition and dynamic vulcanization on the morphology and dynamic viscoelastic properties of PP/EPDM blends

The morphology and dynamic viscoelastic properties of isotactic polypropylene (PP) blended with oil-free/oil-extended ethylene–propylene–diene (EPDM) rubbers were studied. Unvulcanized and dynamically vulcanized blends with the compositions PP/EPDM = 50/50 and = 30/70 were investigated. The morphology was observed by phase contrasted atomic force microscopy. The dynamic viscoelastic properties were determined with a rheometer of plate–plate configuration. It was shown that the rheological behavior was strongly affected by both the composition and the morphology of the blends. Significant improvement in the flowability of the dynamically vulcanized blends was observed when oil-extended EPDM was used instead of the oil-free version. It was demonstrated that the rheological properties are mostly controlled by the elastomer phase at low frequencies, while in the high-frequency range the influence of PP becomes dominant. The peculiarities in the rheological behavior of the thermoplastic elastomers (uncured blends, TPE) and thermoplastic dynamic vulcanizates (TPV, dynamically cured blends) containing oil-extended EPDMs were traced to a limited compatibility between the PP and EPDM components in the melt. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of dynamic vulcanization on properties and morphology of nylon/SAN/NBR blends: A new compatibilization method of nylon/ABS blends

Dynamically vulcanized blends of nylon, styrene–acrylonitrile copolymer (SAN), and nitrile–butadiene rubber (NBR) were examined for mechanical properties, Shore D hardness, Vicat softening temperature, impact process, and phase morphology. The effect of a curing system such as phenolic formaldehyde resins (PF), dicumylperoxide (DCP), and a sulfur system on the mechanical properties of the nylon/SAN/NBR blends was studied, and dynamic vulcanization with a PF system was found to lead to outstanding toughness of the blends. The effect of PF content on the mechanical properties, Shore D hardness, and heat resistance of the nylon/SAN/NBR blends was also investigated. With increasing PF content the notched‐impact strength and Vicat softening temperature (VST) of the nylon/SAN/NBR (50/25/25) blends evidently improved, but tensile strength and Shore D hardness of the blends changed slightly. It can be concluded that the nylon/SAN/NBR (50/25/25) blends dynamically vulcanized by high‐content PF can attain excellent comprehensive mechanical properties, especially supertoughness, at room temperature. SEM was used to investigate the effect of dynamic vulcanization on disperse‐phase particle size, particle size distribution, and phase morphology. It was obvious that disperse‐phase particle size decreased with an increasing PF content. Thermal behavior and miscibility of dynamically vulcanized nylon/SAN/NBR with PF were investigated by DMTA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2057–2062, 2003     

Effect of the viscosity ratio on the morphology and properties of PET/HDPE blends with and without compatibilization

The influence of the molecular weight of polyethylene on the morphology and mechanical properties of blends of high‐density polyethylene (HDPE) dispersed as droplets in a poly(ethylene terephthalate) (PET) matrix at various compositions was investigated. The difference of morphologies can be easily explained by the influence of the molecular weight on the viscosity ratio and therefore, on the critical capillary number. The compatibilizing efficiency of copolymers containing glycidyl methacrylate groups was also addressed in relation to their nature, the protocol for their drying and the molecular weight of the HDPE phase. The increase of adhesion between PET and HDPE was found to have a larger influence on tensile properties than the reduction of interfacial tension. The amount of compatibilizer needed for adhesion improvement depends on the interfacial area that is defined by both the interfacial tension and viscosity ratio of the components. A qualitative relation between the optimum amount of compatibilizer and the critical capillary number can be written. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Three-dimensional phase morphologies in HDPE/EVA blends obtained via dynamic injection packing molding

The formation of phase morphology of injection molded HDPE/EVA blends, under the effect of shear stress, has been investigated in detail. The shear stress was induced by dynamic packing injection molding, by which a specimen is forced to move repeatedly in the model by two pistons that move reversibly with the same frequency during cooling. Two kinds of EVA with VA content 16 wt% (16EVA) and 33 wt% (33EVA) were used to investigate the effect of interfacial tension. The phase morphology was viewed both parallel and perpendicular to the shear flow direction, so one can get an overall three-dimensional phase morphology. Low shear stress provided by the pistons has a substantial effect on the phase morphology along the flow direction but is insignificant in the direction perpendicular to the flow direction. Generally, a much elongated and layer-like structure is formed along the flow direction, and spherical droplet-like morphology is formed perpendicular to the flow direction, and the degree of deformation of rubber particles also depends upon their size and elasticity as well as on the interfacial properties between matrix and dispersed phase. For static samples of HDPE/16EVA blends (without shearing), only droplet morphology is formed as 16EVA content increases from10 to 40 wt%. However, under the effect of shear stress (dynamic samples), both droplet and cylinder morphologies can be formed depending on the volume ratio. For static samples of HDPE/33EVA blends, not only droplet, but also cylinder and co-continuous morphology (perpendicular to flow direction) can be formed depending on the volume ratio. For dynamic samples of HDPE/33EVA blends, droplet, cylinder and co-continuous network (co-continuous in both parallel and perpendicular to flow direction) can be formed under the effect of shear stress. The formation of phase morphology is discussed based on interfacial interaction, viscosity ratio, shear stress, and phase inversion.     

Investigations of environmental stress cracking resistance of HDPE/EVA and LDPE/EVA blends

HDPE/poly(ethylene‐co‐vinylacetate) (EVA) and low‐density polyethylene (LDPE)/EVA blends were tested and compared with respect to their environmental stress cracking resistance (ESCR) using the Bell‐telephone test. The time to failure in the ESCR test improves with increasing EVA content, and considerable improvements were produced for LDPE/EVA blends while small improvements were observed for HDPE/EVA blends. Thermal, rheological, mechanical, and morphological studies were conducted which established a quantitative relationship between morphological features and composition. Furthermore, the failed specimens were further characterized by scanning electron microscopy and fractographic methodology to investigate the failure mechanism for ESCR samples. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39880.     

反应挤出就地增容HDPE/PS合金

在单螺杆挤出机上,利用路易斯酸实现了大分子间的Friedel—Crafts烷基化反应。考察了不同催化剂体系、催化剂用量及工艺条件对合金性能的影响。结果显示：对于质量比为70．0：30．0的高密度聚乙烯／聚苯乙烯合金体系,通过反应挤出,可以就地生成接枝共聚物;苯乙烯单体的加入有利于接枝物的形成;加入0．8份AlCl3、0．5份苯乙烯单体,控制合适的螺杆温度以及螺杆转速为60r／min时,合金的综合性能较好。     

Super polyolefin blends achieved via dynamic packing injection molding: the morphology and mechanical properties of HDPE/EVA blends

As a part of long-term project aimed at super polyolefin blends, in this work, we report the mechanical reinforcement and phase morphology of the blends of high-density polyethylene (HDPE) and ethylene vinyl acetate (EVA) achieved by dynamic packing injection molding. The shear stress (achieved by dynamic packing injection molding) and interfacial interaction (obtained by using EVA with different VA content) have a great effect on phase morphology and thus mechanical properties. The super HDPE/EVA blends having high modulus (1.9–2.2 GPa), high tensile strength (100–120 MPa) and high impact strength (six times as that of pure HDPE) have been prepared by controlling the phase separation, molecular orientation and crystal morphology of the blends. The phase inversion was also found to shift towards lower EVA content under shear stress. The enhancement of tensile strength and modulus originates from the formation of oriented layer, while the high impact strength is related to shear induced phase morphology. DSC studies indicated that the shish kebab crystal structure that also contributes to the enhancement of tensile strength is formed in the oriented layer. The dramatic improvement of impact strength may result from the formation of microfibers and elongated EVA particles along the flow direction. Wu's toughening theory was found non-applicable for the elongated and oriented rubber particles, and a brittle–ductile–brittle transition was observed with increasing EVA content.     

动态硫化法制备SBR/PP共混物的研究

采用动态硫化技术,在双辊开炼机上制备ＳＢＲ／ＰＰ共混物,并研究不同硫化体系、共混比、混炼时间、炭黑用量、环烷油用量和流动助剂用量对共混物力学性能的影响。结果表明：选用低结晶度且熔融指数小的ＰＰ与ＳＢＲ共混,采用半有效硫化体系,橡塑比为７０／３０￣６０／４０,共混时间为９ｍｉｎ时,共混物综合力学性能较好。通过正交试验得出：炭黑用量增大,共混物的拉伸强度、硬度增大而扯断伸长率降低;环烷油、流动助剂用量     

动态硫化NR／PP共混材料的配方研究

研究了PP的牌号、橡塑共混比、硫化体系对动态硫化NB／PP共混物性能的影响。实验表明：采用牌号为EPS－30R的PP,硫磺有效硫化体系、酚醛树脂硫化体系或HVA－2硫化体系制得的胶料性能较好,与Vitacom9001的性能接近。