Effects of organoclay on the compatibility and interfacial phenomena of PE/EVA blends with UCST phase behavior

The compatibilization effects of organically modified nanoclay on the miscibility window, phase separation kinetics, biphasic morphology, interfacial tension, and final properties of polyethylene/ethylene vinyl acetate copolymer blends exhibiting UCST behavior have been investigated. Regardless of blend composition, intercalated nanoclay decreases the phase transition temperatures to lower values and changes the symmetry of phase diagram. The miscibility of PE and EVA phases in the amorphous regions of nanocomposites noticeably enhances and finer biphasic morphology is obtained by the incorporation of organoclay. The pinning influence of the nanofiller on polymer chain diffusion causes much slower phase separation kinetics for the nanocomposites. Similar to conventional compatibilizers such as block copolymers, the interfacial activity of nanoclay leads to a sharp decline in the interfacial tension of PE/EVA up to 2‐orders of magnitude. Moreover, the results show that imposing restrictions on the phase separation phenomenon increases the impact strength of the virgin blend and related nanocomposite. However, this improvement has been much more noticeable in the presence of nanoparticles, which is due to the simultaneous roles of organoclay as an effective compatibilizer and reinforcement. POLYM. COMPOS., 35:2329–2342, 2014. © 2014 Society of Plastics Engineers     

Reactive compatibilization of polystyrene/poly(ethylene–co–vinyl acetate) (EVA) blends

A reactive compatibilizer, mercapto‐functionalized EVA (EVASH), in combination with styrene‐butadiene block copolymer (SBS), was used to compatibilize the blends of polystyrene (PS) and ethylene–vinyl acetate copolymer (EVA). The reactive compatibilization was confirmed by the presence of insoluble material and from dynamic‐mechanical analysis. In addition to a more uniform morphology with small phase size, the compatibilization also provided excellent stabilization of the morphology, with an almost complete suppression of coarsening during annealing. As a consequence, a substantial increase on the elongation at break without significant influence on ultimate tensile strength was achieved for compatibilized blends with different compositions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 14–22, 2006     

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     

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     

Correlation between the morphology and dynamic mechanical properties of ethylene vinyl acetate/linear low‐density polyethylene blends: Effects of the blend ratio and compatibilization

The effects of the blend composition and compatibilization on the morphology of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were studied. The blends showed dispersed/matrix and cocontinuous phase morphologies that depended on the composition. The blends had a cocontinuous morphology at an EVA concentration of 40–60%. The addition of the compatibilizer first decreased the domain size of the dispersed phase, which then leveled off. Two types of compatibilizers were added to the polymer/polymer interface: linear low‐density polyethylene‐g‐maleic anhydride and LLDPE‐g phenolic resin. Noolandi's theory was in agreement with the experimental data. The conformation of the compatibilizer at the blend interface could be predicted by the calculation of the area occupied by the compatibilizer molecule at the interface. The effects of the blend ratio and compatibilization on the dynamic mechanical properties of the blends were analyzed from ?60°C to +35°C. The experiments were performed over a series of frequencies. The area under the curve of the loss modulus versus the temperature was higher than the values obtained by group contribution analysis. The loss tangent curve showed a peak corresponding to the glass transition of EVA, indicating the incompatibility of the blend system. The damping characteristics of the blends increased with increasing EVA content because of the decrease in the crystalline volume of the system. Attempts were made to correlate the observed viscoelastic properties of the blends with the morphology. Various composite models were used to model the dynamic mechanical data. Compatibilization increased the storage modulus of the system because of the fine dispersion of EVA domains in the LLDPE matrix, which provided increased interfacial interaction. Better compatibilization was effected at a 0.5–1% loading of the compatibilizer. This was in full agreement with the dynamic mechanical spectroscopy data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4526–4538, 2006     

Morphology monitoring of PE/PBT blends by reactive processing

Polyethylene (PE)/poly(butylene terephthalate) (PBT) blends were in situ compatibilized during a processing operation by the addition of a partially hydroxylated ethylene vinyl acetate copolymer (EVAh). This copolymer, obtained from ethylene vinyl acetate (EVA), was as compatible with PE as EVA was before modification. In the presence of EVAh, the dispersion of PBT in the PE matrix was finer, and the interfacial adhesion was improved. These results are relevant for the compatibilization of PE/PBT blends. Moreover, such blends present good toluene barrier properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3568–3577, 2001     

Role of clay in compatibilization of immiscible high melt strength polypropylene and ethylene vinyl acetate copolymer blends

The compatibilization efficiency of organically modified layered silicates (clay) was studied for immiscible high melt strength polypropylene/ethyl vinyl acetate (EVA) blends for the first time. The size of the dispersed EVA phase in the polypropylene matrix decreased with addition of small amounts of clay (cloisite 20A) to the blend. Scanning electron micrographs (SEM) show an efficient mixing of polymers in the presence of clay. The X‐ray diffraction (XRD) and transmission electron microscopy patterns demonstrate that silicate layers are well dispersed within the phases and are also present at the interphase. This results in substantial size reduction of the dispersed phase. The blends show a drastic increase in mechanical properties with the addition of clay. Differential scanning calorimetry thermo grams further help in understanding blend miscibility in the presence of clay as denoted by the change in the melting range of the components and the crystallization behavior of the components. The dynamic rheology tests reveal a emulsion‐like behavior for the blend system as denoted by the presence of a curvature or kink at lower frequencies, which further increases for the system with clay particles due to decrease in size of the dispersed phase. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Processing‐induced degradation of nanoclay organic modifier in melt‐mixed PET/PE blends during twin screw extrusion at industrial scale: Effect on morphology and mechanical behavior

Immiscible PET/PE blends (80/20 wt %) were prepared on an industrial twin‐screw extruder with and without different types of commercially available montmorillonites (Cloisite® C15A, C10A, and 30B), containing organic surfactants differing by their polarities and their thermal stability). XRD and TEM observations evidence an intercalated structure, C15A leading to a better dispersion compared to C30B and C10A. The size of the PE dispersed phase decreases upon addition of organoclays (OMMT), suggesting an efficient compatibilization. The most efficient compatibilizing effect is observed in the case of C15A (smallest droplet size and narrowest size distribution). Nevertheless, elongation at break in tension and impact strength of PET/PE blends drastically decrease upon addition of OMMT, whatever the organoclay added, due to a possible degradation of the clay surfactant during melt compounding, which counteracts the nanofiller compatibilization effect. Furthermore, similar PET/PE/OMMT blends prepared at a lab scale using a microcompounder are ductile contrary to those compounded in the industrial extruder, which show a brittle behavior. This difference was ascribed to the extrusion residence time (much higher in an industrial extruder than in a lab micro‐compounder), which appeared to be a key parameter in controlling the clay surfactant degradation and thus the end‐use properties of such immiscible blends. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39712.     

Miscibility and adhesive properties of EVA‐based hot‐melt adhesives. II. Peel strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that were made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of the typical miscibility types and investigated their peel strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of peel strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the storage modulus of the blends whose curves tended to move toward higher temperature as tackifier content of blends increased when blend components were miscible as well as their maximum values of tan δ, or glass transition temperatures. It was characteristic for peel strength that there existed second peaks on peel strengths curves at ～ 100°C, which adhesive tensile strengths for the blends did not have. In terms of relationship between miscibility and HMA performances, we suggest that there are several factors other than miscibility that affect absolute values of peel strength more directly than miscibility; this idea has to be investigated further in the a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 726–735, 2002     

Morphology of polystyrene/poly(dimethyl siloxane) blends compatibilized with star polymers containing a γ-cyclodextrin core and polystyrene arms

A star polymer with a γ-CD core and PS arms is used to compatibilize blends of the immiscible polymers PS and PDMS. The mechanism of compatibilization is threading of the CD core by PDMS and subsequent solubilization in the PS matrix facilitated by the star arms. Spun-cast films of this blend are examined with optical microscopy, scanning electron microscopy and atomic force microscopy. Blends without CD-star exhibit large-scale phase separation, whereas those containing CD-star exhibit very homogeneous morphologies in the optical microscope and nanometer-sized phase domains in the AFM. The effect of PDMS molecular weight on the blend morphology is insignificant. The morphology of the compatibilized films does not change significantly after annealing at 125 °C for 3 days, indicating that the CD-star polymer effectively stabilizes these blends at temperatures where both polymers are mobile and could otherwise undergo large-scale phase separation. The degree of compatibilization in these blends is correlated with the molar ratio of PDMS repeat units to CD-star molecules.     

Influence of crosslinking on crystallization,rheological, and mechanical behaviors of high density polyethylene/ethylene‐vinyl acetate copolymer blends

High density polyethylene (HDPE)/ethylene‐vinyl acetate copolymer (EVA) blends with selective crosslinking the EVA phase were prepared and the crystallization, rheological, and mechanical behaviors were studied. Selective crosslinking of EVA component could greatly improve both tensile and impact strengths of the HDPE‐rich blends and influence melting enthalpy at different annealing temperature in successive self‐nucleation and annealing procedure. Dynamic mechanical analysis reveals that glass transition temperatures of both the HDPE and EVA components are lowered upon blending and are raised upon crosslinking. The uncrosslinked HDPE/EVA blends are unstable in the melt and show increment in storage modulus (G′) and decay in loss tangent (tanδ) with annealing time associated with phase coarsening. However, morphology of selectively crosslinked blends in the melt state is highly unstable, characterized by a fast migration of uncrosslinked HDPE component out of the crosslinked EVA phase to the surface resulting in a rapid decay in G′ and an increment in tanδ at the early stage of annealing. POLYM. ENG. SCI., 54:2848–2858, 2014. © 2014 Society of Plastics Engineers     

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     

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.     

Miscibility and adhesive properties of ethylene vinyl acetate copolymer (EVA)‐based hot‐melt adhesives. I. Adhesive tensile strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that are made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of typical miscibility types and measured their adhesive tensile strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of adhesive tensile strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the glass transition temperature (T_g) of the blends that became higher as tackifier content of blends increased when blend components were miscible. In terms of HMA performances, we suggest that factors other than miscibility affect absolute values of adhesive tensile strength more directly than miscibility; this idea has to be investigated further in a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 719–725, 2002     

A correlation between morphology and mechanical performance of injected-molded PE/EVA/clay nanocomposites: Insight into phase miscibility and interfacial phenomena

In this study, the correlations between the mechanical performance and structural properties of injected-molded polyethylene (PE)/ethylene-vinyl acetate copolymer (EVA)/nanoclay (NC) nanocomposites are investigated by revisiting the interfacial phenomena and miscibility state of the component pairs. The effects of different parameters including the injection molding temperature, mixing sequence in melt-compounding process, blend composition, and nanoclay loading are studied. A great complexity arises in the filling and cooling process of the injected-molded parts owing to the phase behavior of the polyolefin blend, crystallization, and morphological changes. The injection molding temperature positively influences the elastic modulus, tensile strength and impact strength of PE/EVA/NC systems through the improvements in the PE/EVA partial miscibility, mutual solubility, and interfacial interactions of PE/clay and PE/EVA pairs. By applying a two-step mixing process before the injection molding, more nanoclay stacks with smaller thicknesses and larger clay interlayer spacing are formed. The stronger pinning effect of nanoparticles in the second mixing sequence retards the phase separation phenomenon of PE/EVA blend during the cooling stage. As a result of improved mutual PE/EVA solubility, the elastic modulus and tensile strength decrease and the impact resistance increases in the PE-rich systems. On the other hand, an opposite trend for these properties is found for the EVA-rich systems.     

Blends of photovoltaic-grade ethylene–vinylacetate copolymers and low-density ethylene–octene copolymers,their morphology and their thermal,mechanical, and rheological properties

Blends of photovoltaic-grade ethylene–vinyl acetate copolymer (EVA), defined by high VA-content and low crystallinity, and low-density ethylene–octene copolymer (EO) have been investigated with regard to their processing, thermal and mechanical properties as well as their morphology. It was found that the amount of EO in the blend has a strong influence on the shear thinning behavior, melt viscosity and therefore the required extrusion temperature and resulting ability to incorporate temperature-sensitive additives like a peroxidic crosslinking agent. A phase separated morphology was found for all blend compositions, though partial miscibility leading to co-crystallization was observed for EVA rich blends. EO rich blends show lower glass transition and higher melting point compared to neat EVA and exhibit higher elastic modulus at elevated temperatures as well as greater elongation at break during tensile testing while the light transmission is diminished. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47714.     

Blends of chlorinated isotactic polypropylene with poly(ethylene-co-vinyl acetate) I. Effect of component polymers composition on the blend miscibility

Chlorinated isotactic polypropylenes (CPP) having various chlorine contents were blended with poly(ethylene-co-vinyl acetate)s (EVA) having various vinyl acetate (VA) contents. The blends were made by casting films from dilute THF solutions and miscibility of the blends was identified by single glass transition temperature, which was confirmed by DSC and dynamic mechanical measurements. Based on the miscibility data from a large number of CPP/EVA combinations, a miscibility map was depicted where CO equivalent weight (CO-EQW) of EVA was plotted against chlorine equivalent weight (Cl-EQW) of CPP. Though an attractive interaction between CPP and EVA could be detected in all the miscible and immiscible blend pairs, miscibility of the CPP/EVA blends could solely be observed in a relatively narrow range of Cl-EQW ca. 65–100 and CO-EQW ca. 170–230.     

The effects of blend ratio,compatibilization and dynamic vulcanization on permeation of gases through HDPE/EVA blends

The effects of blend ratio, compatibilization and vulcanization on the permeability of O₂ and N₂ gas through HDPE/EVA blends were analyzed. As the volume fraction of EVA in the blend increases the permeability increases. The variation in permeability is correlated with the phase morphology. Oxygen exhibits a higher permeability than nitrogen because the “kinetic diameter” of N₂ is greater than that of O₂. The O₂/N₂ selectivity of HDPE is higher than that of EVA and as a result the selectivity decreases with increase in EVA content in the system. The O₂ and N₂ permeabilities decrease and O₂/N₂ selectivity increase upon compatibilization and dynamic vulcanization. The experimental gas permeabilities in HDPE/EVA blends are compared with several theoretical models of permeation.     

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 ionomeric compatibilizers on the morphology and properties of amorphous polyester/polyamide blends

The utilization of sulfonated polyester ionomers as minor‐component compatibilizers in blends of an amorphous polyester and polyamide was investigated. The blends were prepared using twin‐screw extrusion and compared to solution blends to investigate the effect of elevated temperatures and shear mixing on blend miscibility and/or phase behavior. The phase domain sizes of the solution blends with respect to ionomer content were studied using small angle light scattering (SALS) and phase contrast optical microscopy. The thermal and mechanical properties of the extruded blends were investigated using dynamic mechanical analysis (DMA) and tensile testing while the morphology was investigated using environmental scanning electron microscopy (ESEM). The interactions between the sulfonate group of the ionomer and the polyamide were characterized using FT‐IR spectroscopy. Binary blends of the amorphous polyester and polyamide were immiscible with poor mechanical properties, while blends containing the polyester ionomer as a minor‐component compatibilizer showed a significant reduction in the dispersed domain sizes and enhanced ultimate mechanical properties. The compatibilization mechanism is attributed to specific interactions between the sulfonate groups on the polyester ionomer and the amide groups of the polyamide. Polym. Eng. Sci. 44:1721–1731, 2004. © 2004 Society of Plastics Engineers.