Orientation effects on the deformation and fracture properties of high‐density polyethylene/ethylene vinyl acetate (HDPE/EVA) blends

In this paper, the tensile deformation and fracture toughness of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends, obtained by dynamic packing injection moulding, have been comprehensively investigated in different directions of rectangle samples, including longitudinal, latitudinal and oblique directions relative to the flow direction. Two kinds of EVA were used with VA content 16 wt% (16EVA) and 33 wt% (33EVA) to control the interfacial interactions. The results indicate that molecular orientation and interfacial interaction play very important roles to determine the tensile behaviour and fracture toughness. Biaxial‐reinforcement of tensile strength was seen for HDPE/16EVA blends but only uniaxial‐reinforcement was observed for HDPE/33EVA blends. The difference is caused by the different interfacial interactions as highlighted by the peel test, scanning electron microscopy (SEM) observation as well as theoretical evaluation. Very high impact strength, decreasing with increasing EVA content, was observed when the fracture propagation is perpendicular to the shear flow direction, while a low impact strength, increasing slightly increasing with EVA content, was seen when the fracture propagation is parallel to the shear flow. The fracture of oblique samples is always along the flow direction instead of along the impact direction or tensile direction. The tensile behaviour and fracture toughness are discussed on the basis of the formation of transcrystalline zones, orientation of EVA particles and matrix toughness of HDPE in different directions. Copyright © 2004 Society of Chemical Industry     

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.     

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.     

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.     

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.     

Influence of coalescence and interfacial tension on the morphology of PP/HDPE compatibilized blends

In this paper, the compatibilization of polypropylene (PP)/high-density polyethylene (HDPE) blend was studied through morphological and interfacial tension analysis. Three types of compatibilizers were tested: ethylene-propylene-diene copolymer (EPDM), ethylene-vinylacetate copolymer (EVA) and styrene-ethylene/butylene-styrene triblock copolymer (SEBS). The morphology of the blends was studied by scanning electron microscopy. The interfacial tension between the components of the blends was evaluated using small amplitude oscillatory shear analysis. Emulsion curves relating the average radius of the dispersed phase and the interfacial tension to the compatibilizer concentration added to the blend were obtained. It was shown that EPDM was more efficient as an emulsifier for PP/HDPE blend than EVA or SEBS. The relative role of interfacial tension reduction and coalescence reduction to particle size reduction was also addressed. It was observed that the role of coalescence reduction is small, mainly for PP/HDPE (90/10) blends compatibilized by EPDM, EVA or SEBS. The results indicated that the role of coalescence reduction to particle size reduction is lower for blends for which interfacial tension between its components is low at compatibilizer saturation.     

Effect of rubber content on morphology and thermal and rheological behaviors of acrylonitrile-butadiene rubber/poly(ethylene-co-vinyl acetate)/organoclay nanocomposites

Thermoplastic elastomer nanocomposites based on acrylonitrile butadiene rubber (NBR) and poly(ethylene-co-vinyl acetate) (EVA) with different weight ratios (20, 40 and 60 wt% of NBR) and 5 wt% of organocaly (OC) were prepared in an internal mixer. The results obtained from X-ray diffraction and transmission electron microscopy (TEM) micrographs showed that due to the OC–EVA interaction, nearly all of the clay platelets were exfoliated. Scanning electron microscope (SEM) was used to investigate the particle size and phase morphology. SEM images for the unfilled blends revealed a two-phase structure in which the NBR domains were dispersed into the EVA phase. However, for the blend containing 60 wt.% of NBR, a co-continuous morphology was exhibited. The addition of OC decreased the NBR domain size significantly in which NBR remained as a dispersed phase even for the blend having the highest amount of NBR studied. Young's modulus and yield stress increased, but elongation at break and stress at break decreased for the nanocomposites in comparison with that of the unfilled materials. Thermal studies indicated that although OC decreased the degree of crystallinity and crystallization temperature of EVA slightly, it showed no effect on EVA melting temperature in comparison with that of the unfilled samples. It was also found that the nanocomposites behaved as shear thinning fluids over the entire range of angular frequency and the values of storage modulus and stress relaxation modulus of the nanocomposite containing 20 wt% of NBR was even higher than that of the NBR alone.     

Phase morphology development of polypropylene/ethylene-octene copolymer blends: effects of blend composition and processing conditions

Summary Blends of polypropylene (PP)/ethylene-octene copolymer (EOC) was studied. The influences of blend composition and processing conditions on phase morphology development of the blends were investigated by scanning electron microscopy (SEM) in detail. The minor composition formed the dispersed phase and the major composition formed the continuous phase, and the blends formed interpenetrating co-continuous morphology just at the intermediate concentration. The effect of concentration on phase coarsening was explained by the increase of dispersed phase coalescence with dispersed phase concentration’s increase. Phase coarsening and phase fine dispersing were studied. The effect of mixing time on phase morphology development of the blends was investigated, the PP/EOC (80/20) blends has already formed a well-established droplet/matrix morphology after 1.5 min of mixing, and the similar blends phase morphology persisted until 11 min of mixing. The most prominent phenomenon is that the dispersed phase domain deformed from spherical droplet to elliptical droplet, even fibrillar or sheet morphology as the rotor speed increased. The increase of shear rate and elasticity ratio was applied to interpret this phenomenon.     

Phase morphology and stability of co-continuous (PPE/PS)/PA6 and PS/PA6 blends: effect of rheology and reactive compatibilization

(PPE/PS)/PA6 and PS/PA6 blends were prepared by means of melt-extrusion. They were compatibilized using the reactive styrene-maleic anhydride copolymer with 2 wt% maleic anhydride (SMA2). The effect of compatibilization on the phase inversion and the stability of the resulting co-continuous blend structures were investigated using scanning electron microscopy, dissolution and extraction experiments. The onset of co-continuity shifted towards lower PA6 concentrations according to the change in blend viscosity ratio. The melting order of the components inside the extruder could result in a change in the observed co-continuity interval in slowly developing phase morphologies. The unmodified co-continuous blends were not stable and did break-up into a droplet/matrix type of morphology upon annealing in the melt depending on the blend composition. Although the stability of the threads during annealing improved upon compatibilization because of the lower resulting interfacial tension, the decreased possibility for recombination and coalescence during flow reduced the co-continuous region for the compatibilized blends. It is proposed that a dynamic equilibrium between break-up and recombination phenomena after the initial network formation is necessary to maintain the network structure.     

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     

Factors influencing encapsulation behavior in composite droplet-type polymer blends

In this study the influence of the molecular weight of the dispersed phase components on encapsulation effects in the composite droplet phase was examined for high density polyethylene (HDPE)/PS/PMMA ternary blends. Three different blends composed of various PS and PMMA materials dispersed in an HDPE matrix were prepared using an internal mixer. The morphology was studied by light and electron microscopy. Current models used for predicting encapsulation effects and composite droplet formation in ternary systems (based on static interfacial tension) predict in all cases that PS will encapsulate the PMMA. However, in one case, an unexpected encapsulation of PS by PMMA was observed. It was found that arguments based on the effect of viscosity ratio or the absolute viscosity of the different dispersed phases do not explain that discrepancy. In addition, the reversal of that latter composite droplet morphology from PMMA encapsulating PS to PS encapsulating PMMA was observed upon annealing treatment. Considering all the above, a conceptual model was developed to predict encapsulation effects in composite droplet type systems based on the use of a dynamic interfacial tension (i.e. taking into account the elasticity of the polymer components). Calculations based on the dynamic interfacial tension model, using elasticities based on constant shear stress, were able to account for all of the observed encapsulation effects in this study.     

Effect of dynamic cross-linking on phase morphology and dynamic mechanical properties of polyamide 12/ethylene vinyl acetate copolymer blends

Dynamic cross-linking of polyamide 12 (PA12) and ethylene vinyl acetate copolymer (EVA) blends in the mixing chamber of a torque rheometer was investigated. EVA was selectively cross-linked within the PA12 phase through free radical reactions using dicumyl peroxide. The torque level and temperature in the torque rheometer chamber were monitored to follow the evolution of the EVA cross-linking during the dynamic cross-linking process. The degree of cross-linking of EVA in the PA12/EVA materials was estimated based on the gel content (insoluble EVA fraction). The PA12/EVA phase morphology was investigated by scanning electron microscopy. The solid viscoelastic properties were investigated by dynamic mechanical thermal analysis (DMTA). The morphology, interfacial tension and viscoelastic results showed the immiscible nature of this system. The morphology of the blends was observed and the results revealed a two-phase system. The PA12/EVA 70/30 showed disperse-phase morphology, however a co-continuous phase was observed in blend ratios of 50/50 and 60/40. The dynamic cross-linking process resulted in a more stable EVA phase morphology with disperse and interconnected structures in the thermoplastic PA12 domains.     

Linear low-density polyethylene/high-density polyethylene blends: Effect of high-density polyethylene content on die swell and flow instability

This work aimed to evaluate the effect of high-density polyethylene (HDPE) content and of shear rate on the die swell and flow instability of linear low-density polyethylene (LLDPE)/HDPE blends. The results showed that the die swell of the LLDPE/HDPE blends increased with the increase in the shear rate. At high shear rates, the increase in the HDPE content led to an increase in the die swell of LLDPE/HDPE blends. The surface morphology analysis of the extrudates by optical and scanning electron microscopy revealed the presence of sharkskin and stick–slip flow instabilities in LLDPE and LLDPE/HDPE blends at the shear rates investigated. These instabilities were attenuated with the addition of HDPE and almost disappeared in the LLDPE/HDPE blend containing 50 wt% of HDPE.     

Anisotropy and instability of the co-continuous phase morphology in uncompatibilized and reactively compatibilized polypropylene/polystyrene blends

The present work describes the anisotropy and instability observed upon the formation of co-continuous phase morphologies in model polystyrene/polypropylene melt-extruded blends. Uncompatibilized and reactively compatibilized blends using amino-terminated polystyrene, PS-NH₂, and maleic anhydride grafted polypropylene, PP-MAh, reactive precursors were investigated. Differences in phase morphology are discussed based on the viscoelastic properties of the components used, the blend composition and, the type and content of the compatibilizer precursor employed. As expected, for the same polystyrene grade at a concentration in the blend below 20 wt%, a polypropylene matrix having a higher viscosity enables the formation of a more co-continuous phase morphology than a less viscous one, as quantified by solvent extraction. The co-continuous phase morphology developed was found to exhibit a highly elongated structure upon melt flow through the die of the extruder. Isotropic co-continuity, observed inside the barrel of extruder, was transformed into anisotropic phase co-continuity in the form of interconnected infinite strands of the minor phase highly oriented in the extrusion direction.When the blends were thermally annealed, a 50/50 PS/PP co-continuous blend exhibits a substantial phase coarsening from micro- to millimeter scale without alteration of the phase co-continuity. The reactive compatibilization of the polypropylene and the polystyrene phases using 5 wt% PP-graft-PS, reactively in situ generated was able to significantly retard the phase evolution process.     

Shear induced shish-kebab structure in PP and its blends with LLDPE

In order to better understand the effect of shear stress on the crystal morphology and orientation of polyolefins, dynamic packing injection molding was used to prepare oriented pure polypropylene (PP) and its blends with linear low density polyethylene (LLDPE). The obtained samples were characterized via 2d-SAXS, 2d-WAXD and AFM. Macroscopically, shear induced morphology with surface skin, central core and oriented layer between the skin and the core was observed in the cross-section areas of the samples. For pure PP, a highly oriented structure was seen in the sheared layer but much less oriented structure exists in the core. The orientation in the skin lies in between. The shish-kebab structure, composed of stretched chains (shish) and layered crystalline lamellae (kebabs), was found in the sheared layer. Shish structure exists mainly in the skin layer and oriented spherulits dominates in the core. For PP/LLDPE (50/50) blends, a change of phase morphology from less-phase-separated structure (homogeneous) in the skin, to co-continuous structure in the sheared layer and sea-island structure in the core was observed. PP formed a shish-kebab structure in all the three layers. And on the other hand, a very unique crystal morphology and lamellar orientation of LLDPE were obtained, with the lamellar stack oriented either perpendicularly or 45-50° away from the shear flow direction.     

Effect of the partially hydrolyzed EVA‐h content on the morphology,rheology, and mechanical properties of PA12/EVA blends

In this article, a hydrolyzed EVA copolymer (EVA‐h) was chosen as an interfacial agent of PA12/EVA blends. The effect of EVA‐h addition (5 and 10 wt% in relation to EVA phase) on morphological, interfacial and mechanical properties of the systems was investigated. The polymer blends were melt processed in an interpenetrating co‐rotating twin‐screen extruder. The EVA‐h practically did not change the continuity index of the blends. However, it resulted in the reduction of the size of the dispersed EVA phase in polyamide. EVA‐h contributed to the reduction of the interfacial tension (4.6 – 0.32 mN/m) and the formation of a stable morphology. The EVA‐h improved the interaction between PA12 and EVA phases, being its effect more pronounced on the elastic modulus and hardness properties. The behavior of the mechanical properties confirmed the compatibilizer effect EVA‐h in the blends. POLYM. ENG. SCI., 58:335–344, 2018. © 2017 Society of Plastics Engineers     

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.     

微注射成型PP/ABS共混物相形态

采用传统注射成型和微注射成型制备了聚丙烯/丙烯腈丁二烯苯乙烯共聚物（PP/ABS）共混物的2种尺寸的矩形样条,并对其相形态和力学性能进行了研究。结果表明,2种样条的相形态差异很大,传统注射成型样条皮层分散相变形较大,且在ABS含量达到50 %(质量分数,下同)时,仍为分散相形态;而芯层分散相呈球形,在ABS含量为40 %时呈共连续结构;微注射成型由于剪切速率较高,冷却速率较快,样条皮层和芯层相形态没有太大的差异,分散相变形均较大,在ABS含量为50 %时呈现共连续结构,即相反转区域向ABS含量较高的方向移动;随着ABS含量的增加,2种样条的拉伸强度逐渐降低。     

Morphology development during blending of immiscible polymers in screw extruders

The present work reports evolution of morphology from initial (presence of striation) to final (droplet formation) stages in a single‐screw extruder. Morphology development during the blending process controls the final size of the dispersed phase, which in turn significantly affects the properties of the blends. The experiments were carried out using a 70/30 wt% polypropylene/ethylene vinyl acetate (PP/EVA) blend; samples were collected along the length of the screw, by screw pullout experiment, to analyze the size and size distribution of the dispersed phase present both as striated layers and subsequently as droplets. Average size of the dispersed phase and standard deviation were taken into account to monitor the morphology evolution along the length of the screw. Pre‐breakup morphology development was studied by analyzing the sample collected from the feed zone of the extruder in terms of upper and lower layers along the cross section of screw channel. Examination of micrographs revealed the existence of pattern of ordered striations along the length of the melting zone containing striations from average size of 1000 μm down to 50 μm decreasing rapidly along the length of the screw. The breakup process was captured at the start of compression zone where step‐up in the shear as well as elongational flow was applied due to decrease in the channel depth along the compression zone. The observed droplet size formed by the breakup of filaments is found to be in accordance with theory. The final droplet size is found to be governed by the emulsification process occurring as a result of stretching, breakup and coalescence in the metering section of the screw and is in the order of 2 μm.     

Melt rheology and elasticity of natural rubber—ethylene–vinyl acetate copolymer blends

The melt rheology of blends of natural rubber (NR) and ethylene–vinyl acetate copolymer (EVA) has been studied with reference to the effects of blend ratio, cross-linking systems, shear stress, and temperature. When EVA formed the dispersed phase, the viscosity of the blends was found to be a nonadditive function of the viscosities of the component polymers at lower shear region, i.e., a positive deviation was observed. This behavior has been explained based on structural buildup of dispersed EVA domains in the continuous NR matrix. The effect of the addition of silica filler on the flow characteristics of the blends has been investigated. The melt elasticity parameters such as die swell, principal normal stress difference, recoverable shear strain, and elastic shear modulus of NR–EVA blends were also evaluated. © 1993 John Wiley & Sons, Inc.