Super polyolefin blends achieved via dynamic packing injection molding: Tensile strength

The tensile strength of some polyolefin blends, HDPE/PP, HDPE/LDPE, HDPE/ LLDPE, and PP/LLDPE, achieved by dynamic packing injection molding have been investigated as a function of composition and melt temperature. Molecular architecture and phase behavior play an important role in chain orientation, hence the tensile strength. For HDPE, which has a linear structure, the highest enhancement of tensile strength is obtained. LDPE, which has a highly branched structure, the smallest enhancement is seen. PP and LLDPE lie in between. Super polyolefin blends with high tensile strength and high elongation have been obtained by this method. The shear‐induced morphologies with core in the center, oriented zone surrounding the core and skin layer were observed in the cross‐section areas of the samples. The tensile strength was found to be directly proportional to the area of the oriented zone. When the area of oriented zone is less than 35%, the tensile strength is not only the orientation dependency but the blending components dependency as well. When the area of oriented zone is more than 35%, however, our new finding is that the orientation will be the dominating parameter to determine the tensile strength of the blends, independent of the components, the composition, molecular architecture, phase behavior, and crystal morphology. The maximum tensile strength for all the polyolefin blends is extrapolated as to 230MPa, as the area of oriented zone reaches to 100%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 236–243, 2002     

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.     

The morphology and mechanical properties of dynamic packing injection molded PP/PS 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 immiscible blends of polypropylene (PP) and polystyrene (PS) achieved by dynamic packing injection molding (DPIM). The shear stress (achieved by DPIM) and interfacial interaction (obtained by using styrene-butadiene-styrene (SBS) as a compatibilizer) have a great effect on phase morphology thus mechanical properties. The shear-induced morphology with core in the center and oriented zone surrounding the core was observed in the cross-section areas of the samples. The phase inversion was also found to shift towards lower PS content under shear stress, at 70 wt% in the core and 30 wt% in the oriented zone, compared with 80 wt% for static samples (without shear). The tensile strength, tensile modules and impact strength were found largely increase by means of either shear stress or compatibilizer. The PS particle size is greatly reduced with adding of SBS, and the reduced particle size results in greater resistance to deformation, which causes the co-continuous structure at oriented zone change into droplet morphology. The morphology resulting from blending and processing was discussed based on effect of interfacial tension, shear rate, phase viscosity ratio and composition. The observed change of mechanical properties was explained based on the combined effect of phase morphology (droplet-matrix or co-continuous phase) and molecular orientation under shear stress.     

Ionomer compatibilised PA6/EVA blends: mechanical properties and morphological characterisation

The compatibilisation of PA6/EVA blends with the addition of an ionomer on the mechanical properties and morphology were studied as a function of ionomer concentration with the primary aim of enhancing the impact strength of PA6 by EVA. The level of EVA was kept at 20%, which formed the dispersed phase, and the ionomer content was varied from 0 to 1.6 wt%. It was found that notched Izod impact strength of PA6/EVA/ionomer blends increased with the incorporation of ionomer to about three times of the value for uncompatibilised PA6/EVA blends. Further, it was observed that on incorporation of the ionomer the tensile strength also increased significantly. Analysis of the tensile data using predictive theories indicated an enhanced interaction of the dispersed phase and the matrix. SEM studies of cryogenically fractured surfaces indicated a decrease in dispersed phase domain size with the addition of the ionomer, while the impact fractured surfaces of PA6/EVA blends indicated extensive deformation with the formation of rumples indicating increased interfacial adhesion as compared to PA6/EVA blends. An attempt has been made to evaluate the compatibilising efficiency of ionomer in PA6/EVA blends.     

Study on the morphology and properties of metallocene polyethylene and ethylene/vinyl acetate blends

Two commercial polymer materials, metallocene linear low density polyethylene (m‐LLDPE) and ethylene/vinyl acetate copolymer (EVA) have been used to form binary blends of various compositions. The mechanical properties, morphology, rheological behavior, dynamic mechanical properties, and crystallization of m‐LLDPE/EVA blends were investigated. It was found that with the addition of EVA, the fluidity and processability of m‐LLDPE were significantly improved, and the introduction of polar groups in this system showed no significant changes in mechanical properties at lower EVA content. As verified by morphology observation and differential scanning calorimetry analysis, miscible blends were formed within certain weight ratios. Dynamic mechanical property studies showed that flexibility of the blends was enhanced in comparion with pure m‐LLDPE, where the peak value of loss modulus shifted to lower temperature and its intensity was enhanced as EVA content increased, indicating the existence of more amorphous regions in the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 905–910, 2004     

Mechanical properties and morphology of PA6/EVA blends

The mechanical properties of blends of polyamide6 (PA6) and ethylene vinyl acetate (EVA) at a blending composition of 0–50 wt % EVA were studied. The notched Izod impact strength of PA6 increased with the incorporation of EVA, the increase being more than 100% compared to PA6 at 10% EVA. The tensile strength and the tensile modulus of the blends decreased steadily as the weight percent of EVA increased. Analysis of the tensile data using predictive theories indicated the extent of the interaction of the dispersed phase and the matrix up to 20 wt % EVA. SEM studies of the cryogenically fractured surfaces indicated increase in the dispersed phase domain size with EVA concentrations. On the other hand, impact fractured surfaces of PA6/EVA blends indicated debonding of EVA particles, leaving hemispherical bumps, indicating inadequate interfacial adhesion between PA6 and EVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1593–1606, 2002     

Ultrasonic measurement of orientation in HDPE/iPP blends obtained by dynamic packing injection molding

The orientation of polymer chain has a great effect on its mechanical properties, therefore, it is always an important issue on how to characterize, accurately and quickly, the orientation of polymer chain during processing. In this article, according to the property that ultrasound travels in different velocities in anisotropic media, normal incident shear wave was utilized to explore the orientation structure of HDPE/iPP blends obtained by dynamic packing injection molding. The ultrasonic technique is consistent with the 2D-WAXS in charactering the orientation degree of polymer chains, although ultrasonic technique focuses on the overall orientation of polymer blends while the 2D-WAXS reveals the crystalline orientation of each component. Our work demonstrates that ultrasonic technique might be a reliable, fast and easy way to characterize the orientation structure of crystalline polymer blends. The ultrasonic measurements were performed off-line, but the achievement provides the possibility for on-line detection of orientation structure in injection molding by using ultrasonic technique.     

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     

Phase morphology and toughening mechanism of polyamide 6/EPDM-g-MA blends obtained via dynamic packing injection molding

One of the most important findings in polymer-toughening is known as the critical matrix ligament thickness (τ_c) theory, which is directly related to both rubber concentration and average size of particles. All these studies assume that rubber particles are spherical and randomly distributed in the matrix. Rubber particles may be stretched and oriented along the shear flow direction in real processing. In this paper the effect of stretched and oriented rubber particles on the impact strength of PA6/EPDM-g-MA blends have been studied via dynamic packing injection molding (DPIM). The impact strength of specimens obtained by DPIM was found substantially increase at all the blends investigated, compared with the one obtained via conventional injection molding. Particularly, more than 30 kJ m⁻² increase of the impact strength was observed for specimens with a higher rubber content (more than 15 wt%). SEM results showed a remarkably decrease of rubber particle size and more uniform dispersion of the dynamic molded specimens. This can be attributed to the shear induced reaction at the interface between polyamide 6 and EPDM-g-MA during the packing stage. The rubber particles were found stretched along the melt shear flow direction when it is content above 15 wt%. A master curve can be also constructed by plotting the impact strength versus the inter-particle distance, indicating that Wu's criterion still works for blends with stretched and oriented rubber particles when the crack propagation direction is perpendicular to the orientation direction of rubber particles. The observed higher impact strength in dynamic specimens could be due to, in part, the enhanced flexural stiffness, which will absorb more energy during impact process when the fracture of IZOD bars is incomplete, but more importantly due to the existence of the stretched and oriented rubber particles, which are more efficient in slowing the velocity of crack propagation and thus cause higher impact resistance when the fracture propagation direction is perpendicular to the rubber oriented direction.     

Mechanical properties of recycled LDPE/EVA/ground tyre rubber blends: Effects of EVA content and postirradiation

Thermoplastic elastomers were prepared from recycled low density polyethylene [rLDPE] and virgin low density polyethylene (LDPE), respectively, ground tyre rubber (GTR), and ethylene vinyl acetate (EVA) copolymer. The amounts of the rLDPE and GTR were fixed at 40 and 30 wt %, respectively, in the formulations, whereas the LDPE and EVA contents varied each between 0 and 30 wt %. The fresh LDPE served for reduction of the melt viscosity and EVA was used for improving the elastomeric properties. Blends of different compositions (by varying the LDPE/EVA ratio) were produced by twin-screw extrusion and pelletized. Specimens were produced by injection molding and subjected to tensile and instrumented falling weight impact (IFWI) tests. To improve the mechanical performance of the blends, the injection molded specimens were electron beam irradiated at 150 kGy absorbed dose. Static tensile and hysteresis, IFWI and dynamic mechanical thermal analysis tests were performed on the specimens and the fracture surface was inspected with a scanning electron microscope. The results indicated that better rubber-like properties were achieved with increasing EVA content. Moreover, postirradiation proved to be very beneficial, especially for blends containing relative high amounts of EVA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Origin of various lamellar orientations in high-density polyethylene/isotactic polypropylene blends achieved via dynamic packing injection molding: bulk crystallization vs. epitaxy

Epitaxial growth of high-density polyethylene (HDPE) onto lamellae of isotactic polypropylene (iPP), with HDPE chains inclined about 50° to that of iPP, has been achieved for the first time in their blends via dynamic packing injection molding. Even more, the epitaxial growth was found to be dependent on composition of the blends. The sequence of crystallization is not the dominant factor, but the fact that iPP crystallizes before HDPE is prerequisite for epitaxial growth of PE. Various lamellar orientations with composition can be explained by the competition between bulk crystallization and epitaxy at interfaces (i.e. iPP lamellae). In 20PP (20 wt% iPP by weight in blends), HDPE can readily crystallize in the bulk as a result of shear, and no epitaxial growth of PE is observed. For 80PP, however, bulk crystallization of HDPE can be depressed due to lack of nuclei in its bulk, resulting from a much finer droplets dispersed in the iPP matrix, and then epitaxial growth prevails.     

木质素填充LDPE、EVA对复合物性能的影响

以木质素为填充剂分别与低密度聚乙烯(LDPE)、乙烯-乙酸乙烯酯共聚物(EVA)共混,经双螺杆造粒机共混挤出造粒,再经吹塑成膜。研究了木质素/LDPE、木质素/EVA共混物薄膜的表面形貌、力学性能、热性能和红外光谱。热分析表明木质素与EVA共混物的热稳定性比木质素与LDPE的共混物热稳定性好;红外光谱分析表明木质素与EVA分子间产生了强烈的相互作用,扫描电镜分析表明木质素与EVA共混的相容性较好,力学性能分析表明低于30%的木质素与LDPE、EVA共混力学性能较好。     

Morphology and elastic properties of PP/EVA polymer blends

Several polypropylene–ethylene vinyl acetate (PP/EVA) copolymers with compositions ranging from 90/10 to 10/90 PP/EVA were prepared and characterized in terms of their morphology by transmission and scanning electron microscopy, and their mechanical properties were also studied. The results show a wide range of spatial structures which correlate well to the corresponding measurements of elastic modulus of the blends.     

Cure characteristics,morphology, mechanical properties,and aging characteristics of silicone rubber/ethylene vinyl acetate blends

Silicone rubber/ethylene vinyl acetate (SR/EVA) rubber mixes with different ratios were prepared by using dicumyl peroxide (DCP) and benzoyl peroxide (BP) as curing agents. The vulcanization characteristics such as cure kinetics, activation energy, and cure rate of the blends were analyzed. The effects of blend ratio and curing agents on the mechanical properties such as stress–strain behavior, tensile strength, elongation at break, tear strength, relative volume loss, hardness, flex crack resistance, and density of the cured blends have been investigated. Almost all the mechanical properties have been found to be increased with increase in EVA content in the blends particularly in DCP‐cured systems. The increment in mechanical properties of the blends with higher EVA content has been explained in terms of the morphology of the blends, attested by scanning electron micrographs. Attempts have been made to compare the experimental results, from the evaluation of mechanical properties, with relevant theoretical models. The aging characteristics of the cured blends were also investigated and found that both the DCP‐ and BP‐cured blends have excellent water and thermal resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1069–1082, 2006     

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     

Tensile properties in the oriented blends of high-density polyethylene and isotactic polypropylene obtained by dynamic packing injection molding

In this article, tensile properties have been discussed in terms of phase morphology, crystallinity and molecular orientation in the HDPE/iPP blends, prepared via dynamic packing injection molding, with aid of scanning electron microscopy (SEM), differential scanning calorimetry (DSC) as well as two dimensional X-ray scattering (2D WAXS). For the un-oriented blends, the tensile properties (tensile strength and modulus) are mainly dominated by the phase morphology and interfacial adhesion related to the influenced crystallization between HDPE and iPP component. A maximum in tensile strength and modulus is found at iPP content in the range of 70-80 v/v%. As for the oriented blends, however, the presence of dispersed phase in the blends, independent of phase morphology and crystallinity, always makes tensile properties to be deteriorated through reducing molecular orientation of matrix. It is molecular orientation of matrix that determines the tensile properties of oriented blends. In the blends with HDPE as matrix, steep decreasing of tensile properties is related to the rapid reducing of molecular orientation of HDPE, whereas in the blends with iPP as a major component, slight decreasing of molecular orientation of iPP results in slight reducing of tensile properties. Other factors, such as interfacial properties and phase morphology, seem to be little contribution to the modulus and tensile strength.     

Melt rheological properties of reactive compatibilized HDPE/PET blends

Melt rheological properties of high density polyethylene and poly(ethylene terephthalate) (HDPE/PET) blends compatibilized by an ethylene–butyl acrylate–glycidyl methacrylate terpolymer (EBAGMA) were studied by means of a HAAKE torque rheometer and a capillary rheometer. The phase morphology of the blends was evaluated by a scanning electron microscope (SEM). The results showed that the melts of blends behave pseudoplasticity. The addition of EBAGMA strengthens the interfacial adhesion between HDPE and PET and improves the phase dispersion due to reactive compatibilization. It was observed that the balance torque, melt viscosity, and sensitivity of melt viscosity to shear rate of the melts increase with increasing content of EBAGMA, but the melt flow index and activation energy decrease. At the same time, the plasticizing time is shortened indicating that the processability of the compatibilized blends has been improved. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of different curing systems on heat shrinkability and mechanical properties of ethylene vinyl acetate/epoxidized natural rubber blends

Ethylene vinyl acetate (EVA)/epoxidized natural rubber (ENR) blends containing 10 and 30 wt % ENR were prepared by using an internal mixer. Five different types of curing systems were employed: dicumyl peroxide (DCP), sulfur (S), phenolic resin (Ph), DCP + S, and DCP + Ph. DCP could crosslink with both EVA and ENR while S and Ph were curing agents for ENR. The DCP system provided the lowest tensile properties and tear strength because of low crosslinking in ENR phase. Addition of sulfur or phenolic resin increased the mechanical properties due to a better vulcanization of the rubber phase. The mechanical properties of the blends decreased with increasing ENR content. The rubber particle size in the blends containing 30% ENR played a more important role in the mechanical properties than the blends containing 10% ENR. ENR particle size did not affect heat shrinkability of EVA and a well vulcanized rubber phase was not required for high heat shrinkage. Furthermore, heat shrinkage of the blends slightly changed as the ENR content increased for all curing systems. With regard to the mechanical properties and heat shrinkability, the most appropriate curing system was DCP + Ph and in the case the 10 wt % ENR content produced a more favorable blend. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and mechanical properties of uncrosslinked and chemically crosslinked polyethylene/ethylene vinyl acetate copolymer blends

Uncrosslinked and chemically crosslinked binary blends of low‐ and high‐density polyethylene (PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt‐mixing process using 0–3 wt % tert‐butyl cumyl peroxide (BCUP). The uncrosslinked blends revealed two distinct unchanged melting peaks corresponding to the individual components of the blends, but with a reduced overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced compatibility between EVA and polyethylene, with LDPE being more compatible than HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the addition of BCUP, and only the corresponding PE melting point was observed at a lowered temperature. But blended with 40% EVA, two peaks still existed with a slight shift toward lower temperatures. Changes of mechanical properties with blending ratio, crosslinking, and temperature had been dominated by the extent of crystallinity, crosslinking degree, and morphology of the blend. A good correlation was observed between elongation‐at‐break and morphological properties. The blends with higher level of compatibility showed less deviation from the additive rule of mixtures. The deviation became more pronounced for HDPE/EVA blends in the phase inversion region, while an opposite trend was observed for LDPE/EVA blends with co‐continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3261–3270, 2007     

Effect of flexibility of ethylene vinyl acetate and crystallization of polypropylene on the mechanical properties of i‐PP/EVA blends

Polymer blend technology has been widely used for the past several years for the modification or enhancement of mechanical properties of polymers to obtain an overall balance of properties over those of the constituents. Despite its interesting mechanical and thermal properties, the impact strength of polypropylene leaves wide scope for improvement. A series of blends of ethylene vinyl acetate (EVA) copolymer with an impact grade of isotactic polypropylene (i‐PP) were prepared by single screw extrusion at 0–0.32 volume fraction of the dispersed phase. The mechanical properties such as tensile behavior, elongation‐at‐break, and impact strength of these blends systems as well as crystallinity were evaluated. Crystallinity data have been used in greater depth to support the mechanical properties. Differential scanning calorimetry studies conducted to study the modification in crystallinity of the crystalline component, i‐PP, of the blend revealed that the rubber component of the blend enhanced the crystallinity of i‐PP phase by providing sites for nucleation. Tensile modulus and strength decreased while the impact strength and breaking elongation enhanced with blending elastomer concentration. The improved properties of these PP/EVA blends are encouraging for carrying out further work on this system (composites) and suggest potential high impact strength applications for PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012