Crosslinking of polyvinyl chloride by electron beam irradiation in the presence of ethylene–vinyl acetate copolymer

Electron beam (EB) irradiation of polyvinyl chloride (PVC) was carried out in the presence of three different ethylene–vinyl acetate copolymers (EVA). The mechanical properties of the original and irradiated blends were tested. The gel content measurement, chlorine loss upon electron irradiation, and gel permeation chromatograph (GPC) were used to characterize the effect of EVA on the irradiation behavior of PVC/EVA blends. The content and the chemical structure of EVA in the blends had considerable effects on the mechanical properties and gel content of the blends. The incorporation of EVA into PVC blend can increase the gel content and reduce chlorine loss of the blends. The GPC analysis of the soluble part in the irradiated PVC samples showed that the addition of EVA into the PVC blend lowered the polydispersity of molecular weight of PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1571–1575, 2004     

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.     

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     

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     

Effect of dehydrochlorination of PVC on miscibility and phase separation of binary and ternary blends of poly(vinyl chloride), poly(ethylene-co-vinyl acetate) and poly(styrene-co-acrylonitrile)

The enhancement of miscibility at the lower critical solution temperature (LCST) of the blends poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN) and poly(vinyl chloride)/poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (PVC/EVA/SAN) was observed at the micron level. Such miscibility is attributed to the dehydrochlorination and formation of hydrogen bonds between blend components. However, macrolevel immiscibility of these blends heated to the LCST was observed. Such microdomain compatibility of these blends gives a synergistic character. Brittle-type failure observed for LCST samples testifies to the synergism in treated blends. ©1997 SCI     

Compatibilization mechanisms of nanoclays with different surface modifiers in UCST blends: Opposing effects on phase miscibility

The effects of organically modified and pristine nanoclays on the kinetics of thermodynamic equilibrium state attainment for semicrystalline binary blends of polyethylene (PE)/ethylene-vinyl acetate copolymer (EVA) have been investigated. Due to the non-equilibrium compatibilization mechanism, intercalated organoclay results in a slower rate of phase miscibility change at lower annealing temperatures, thereby worsening the PE/EVA compatibility state. In contrast to poorly dispersed pristine nanoclay, the homogeneous state is obtained at higher or equal rates by adding organoclay at higher annealing temperatures because of the dominant role of nanofiller equilibrium compatibilization mechanism. Phase diagrams of these UCST blends determined by a dynamic method shifts to higher temperatures by the incorporation of nanofillers and the unexpected reduction in miscibility window area is much more noticeable for nanocomposites having highly restricted molecular movements. This can verify that dynamic methods lose their efficiency for measuring the equilibrium phase diagram of polymer blends containing nanoparticles.     

Plastification of poly(vinyl chloride) by polymer blending

Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000     

Studies on miscibility of blends of poly (ethylene acrylic acid) and ethylene‐co‐vinyl acetate by melt rheology

Rheological behavior of blends of poly (ethylene‐acrylic acid) (EAA) and ethylene vinyl acetate (EVA) copolymer have been carried out at various temperatures, namely, 100, 110, and 120°C, and different shear rates from 61.33 to 613.30 s^?1 using a Monsanto Processability Tester. The melt viscosity of the blends shows synergism during processing. The activation energy of the blends is in the range 20.7–44.6 kJ/mol. Highest activation energy was observed for the blends containing 40–60% of EVA by weight. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1947–1954, 2005     

Viscoelastic and adhesion properties of hot-melts made with blends of ethylene-co-n-butyl acrylate (EBA) and ethylene-co-vinyl acetate (EVA) copolymers

Several hot-melts (HMAs) were prepared by using blends of ethylene-co-n-butyl acrylate (EBA) and ethylene-co-vinyl acetate (EVA) copolymers - EBA/EVA. HMAs were prepared with mixtures of EVA copolymers with 18 (EVA18) and 27 (EVA27) wt% vinyl acetate contents and EBA copolymer with 27 wt% n-butyl acrylate, polyterpene resin and mixture of microcrystalline and Fischer-Tropsch waxes. HMAs made with EBA/EVA blends showed lower viscosities and reduced shear thinning than the ones made with EBA or EVA due to differences in compatibility, but both the set time and the open time were not affected as they depended mainly on the wax nature and amount. The increase of the vinyl acetate (VA) content in EVA copolymer reduced the crystallinity of the EBA/EVA blends. Even EBA copolymer was more compatible with EVA27 than with EVA18 (the α- and β-transitions shown in DMTA plots were closer) and the compatibility did not vary with the EBA content in the blends. The addition of polyterpene resin and the mixture of waxes decreased the compatibility of the EBA/EVA blends, the higher compatibility was observed for the HMAs made with only one copolymer. The tack of the HMAs depended on their EBA/EVA contents, EBA/EVA27 HMAs showed broader temperature interval with higher tack, while the tack of EBA/EVA18 HMAs blend decreased and the temperature interval with tack was shortened and shifted to lower temperatures. Adhesion to polypropylene film was improved in HMAs made with 75 wt% EBA/25 wt% EVA18 and 50–75 wt% EBA/50-25 wt% EVA27. The adhesion to aluminum film of EBA or EVA hot melts was improved only in the joints made with EBA/EVA 27 HMAs, more noticeably when they contained higher EBA content.     

Tailoring viscoelastic and mechanical properties of the foamed blends of EVA and various ethylene‐styrene interpolymers

Foamed materials (EVA/ESI) have been prepared from blends of ethylene‐vinyl acetate copolymer (EVA) and ethylene‐styrene interpolymers (ESI) in the presence of various amounts of dicumyl peroxide (DCP). Four ESIs of different compositions were employed in this study; their styrene contents ranged from 30 to 73 wt% and their T_g ranged from −2 to 33°C. It has been found that microcellular morphology, degree of crosslinking and expansion ratio were strongly affected by the DCP concentration and the type of ESI employed. A minimum degree of crosslinking was required for making good foams and the same degree of crosslinking could be achieved by employing a smaller amount of DCP for an EVA/ESI blend having a higher styrene content. In contrast to other EVA blends, such as EVA/LDPE, these EVA/ESI blends exhibited no existence of any optimum DCP concentration, and the α glass transition temperatures of the foams varied with the ESI type, covering a wide span from 0°C to 37°C. Therefore, it was possible to tailor the T_g of an EVA/ESI blend by choosing an appropriate type of ESI. Furthermore, by correctly tailoring the T_g, the EVA/ESI foam could be made into a rubbery material with a custom‐designed damping factor. Tensile strength and modulus of the EVA/ESI foams increased generally with an increase in the styrene content, with the exception that ESIs with very low styrene content will confer on the blend a high modulus at small strain and a large elongation at break.     

Vinyl acetate content and electron beam irradiation directed alteration of structure,morphology, and associated properties of EVA/EPDM blends

A series of ethylene vinyl acetate/ethylene–propylene diene elastomer (EVA/EPDM) blends with four types of EVAs with various vinyl acetate (VA) content, are prepared without and with crosslinker, trimethylol propane triacrylate (TMPTA). These are irradiated by electron beam (EB). As the VA content increases, the gel content, i.e., degree of crosslinking of EVA/EPDM blends, is increased. With increase in VA content, the modulus and tensile strength are decreased but elongation at break is increased due to increase in amorphousness. On EB irradiation, modulus and tensile strengths are increased but at the cost of elongation at break. Crystallinities of all blends are decreased with increase in VA and EB crosslinking. The thermal stability of EVA/EPDM blend is decreased with increase in VA content but increased after EB irradiation. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) show that with increase in VA content the miscibility of two polymers keeps on increasing, which even become more after EB irradiation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43468.     

Thermodynamics of mixing of poly(vinyl chloride) and poly(ethylene-co-vinyl acetate)

The miscibility of poly(vinyl chloride) (PVC) and an ethylene-vinyl acetate copolymer with 85 wt[percnt] of vinyl acetate units (EVA85) has been studied by measuring the glass transition temperature and the enthalpy of mixing of several mixtures covering the whole composition range. An accurate thermal characterization as regards the specific heat of the two polymers and their blends has also been obtained. The enthalpy of mixing has been found negative for all the mixtures, indicating that specific interactions are involved between the polar groups of the two components. Particular attention has been paid also to the excess specific heat, which comes out positive for the PVC-rich blends and with a small negative value in a narrow region at high contents of EVA85. This finding is in agreement with negative and positive deviations that are observed for the glass transition temperature. Modelistic considerations about the type of interactions and the organization between PVC and EVA85 in the blends are proposed.     

Studies on preparation of immersion‐type polypropylene fragrant fiber. I. Formation of matrix fiber in the melt‐spinning process and its technique of immersion essential oil

Polypropylene/ethylene vinyl acetate (PP/EVA) blends were prepared in a plastic extruder with a static mixer. The thermodynamic compatibility, morphology, crystal form, and rheological behavior of PP/EVA blends were investigated by SEM, DSC, and rheology instruments. The results showed that PP and EVA were thermodynamically incompatible, the viscosity of the PP/EVA blends decreased with increase of shear rate in a range of temperature, the PP/EVA blends had a sea‐islands structure, and the crystalline zones remained in their original state and could not form mixed crystals in the PP/EVA blends. The PP/EVA blends were melt spun to prepare matrix fibers and the spinning conditions such as EVA content, the matching factor between pump delivery and winding velocity, and the melt‐spinning temperature were also determined. The sorption process of a matrix fiber for essential oils, adsorbed under various sorption conditions such as sorption time, sorption temperature, and EVA content, was also studied. The results revealed that the composite isotherm of the adsorption of matrix fiber for essential oil was characteristic of a U model. Through adsorbing essential oil, the immersion‐type PP fragrant fibers could be prepared with the matrix fiber. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1970–1979, 2003     

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

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

Miscibility of PVA/EVA systems by viscometry

Viscometric data were applied to characterize the miscibility of poly(vinyl chloride) (PVC)/poly(ethylene-co-vinyl acetate) (EVA) mixtures using six samples of EVAs with different vinyl acetate content in the copolymer. Relative viscosity vs composition plots showed the imiscibility of PVC/EVA 31 and PVC/EVA 41 blends. The variation of the reduced viscosity, _sp/C with the concentration, C, has been studied for 50:50 by weight blends of PVC/EVA 45, PVC/EVA 45A, PVC/EVA 50 and PVC/EVA 70 in tetrahydrofuran at 25°C. The presence of a sharp crossover and a consequent reduction of slope in _sp/C vs C plots showed that these systems are miscible for a concentration range which corresponds to the regime of dilute solution.     

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     

Viscoelastic and adhesion properties of EVA/tackifier/wax ternary blend systems as hot-melt adhesives

Two types of wax were added to a ethylene vinyl acetate (EVA) copolymer/aromatic hydrocarbon resin (tackifier) blend in the molten state and the miscibility, viscoelastic and adhesion properties of ternary blends as hot-melt adhesives (HMAs) were investigated. Miscibility and viscoelastic properties were studied using differential scanning calorimetry (DSC), Brookfield viscometry and dynamic mechanical thermal analysis (DMTA), and their adhesion strength was determined in terms of single lap shear strength. DSC thermograms of both types of waxes showed their melting peaks in a similar region to that of EVA/tackfier blend. It was difficult to evaluate the miscibility of ternary blends using DSC because the melting peaks of the waxes overlapped with those of the EVA/tackifier blend, although the glass transition temperature (T _g) of the ternary blend systems slightly increased with increasing wax concentration. However, their storage modulus (E′) increased slightly and loss tangent (tan δ) showed different peaks when two types of wax were added to the EVA/tackifier blend. Therefore, the miscibility of EVA/tackifier blend altered with addition of waxes. In addition, their melt viscosity decreased with increasing wax concentration. Furthermore, the adhesion strength of the ternary blends decreased with increasing wax concentration, despite the increment of storage modulus. These results suggested that the ternary blends of EVA/tackifier/wax were heterogeneous.     

Radiation effects on LDPE/EVA blends

Radiation effects of low‐density polyethylene/ethylene‐vinyl acetate copolymer (LDPE/EVA) blends were discussed. EVA content in the LDPE/EVA blends was an enhancement effect on radiation crosslinking of LDPE/EVA blends, and the highest radiation crosslinking was obtained when the EVA content was reached at 30% when irradiated by γ‐ray in air. The phenomenon was discussed with the compatibility, morphology, and thermal properties of LDPE/EVA blends and found that the enhanced radiation crosslinking of the LDPE/EVA blends was proportional to the good compatibility, the increasing degree of the amorphous region's content of the LDPE/EVA blends, and the vinyl acetate content of EVA. We also found that the vinyl acetate of EVA in the blends is easily oxidized by γ‐ray irradiation in air. The possible radiation crosslinking and degradation mechanism of LDPE/EVA blends was discussed quantitatively with a novel method “step‐analysis” process of irradiated LDPE/EVA blends in the thermal gravimetric analysis (TGA) technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1296–1302, 2002     

Toughening effects of ethylene–vinyl acetate copolymers with different vinyl acetate content and viscosity on nylon 1010 blends

Nylon 1010 blends with ethylene–vinyl acetate copolymer (EVA) and maleated ethylene–vinyl acetate (EVA‐g‐MAH) were prepared through melt blending. The vinyl acetate (VA) content and viscosity of EVA significantly affected the notched impact strength of nylon/EVA/EVA‐g‐MAH (80/15/5) blends. The nylon/EVA/EVA‐g‐MAH blends with high notched impact strength (over 60 kJ/m²) were obtained when the VA content in EVA ranged from 28 to 60 wt%. The effect of VA content on the notched impact strength of blends was related to the glass transition temperature for EVA with high VA content and crystallinity for EVA with low VA content. For nylon blends with EVA with the same VA content, low viscosity of EVA led to high notched impact strength. Fracture morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends showed that blends with ductile fracture behavior usually had large matrix plastic deformation, which was the main energy dissipation mechanism. A relationship between the notched impact strength and the morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends was well correlated by the interparticle distance model. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Effect of electron beam irradiation and vinyl acetate content on the physicochemical properties of LDPE/EVA blends

The radiation‐induced crosslinking, compatibility, and surface modification of low density polyethylene/ethylene vinyl acetate blends (LDPE/EVA) were investigated. The structural and physical properties were characterized in terms of gel content, hot set, mechanical properties, contact angle, and surface free energy. The highest crosslink density was obtained at 20 wt % of EVA. Gel content of LDPE/EVA blends was increased with increasing irradiation dose, vinyl acetate (VA), and EVA contents. The hot set results are consistent with the gel content data. Mechanical testing showed that the tensile strength of samples increased with increasing irradiation dose up to 180 kGy, whereas the elongation at break was decreased with increasing irradiation dose. Contact angle measurements showed that the surface hydrophillicity of LDPE blend was increased with increasing irradiation dose and contents of both VA and EVA. The surface free energy was greatly dependent on irradiation dose and content of both VA and EVA. The total surface free energies of different LDPE formulations were in the range 17.25–32.51 mN/m, in which the polar (^pσ) and disperse (^dσ_s) values were within the range 16.52–26.6 and 0.9–5.91 mN/m, respectively. In conclusion, electron beam irradiation and blending LDPE with EVA improved the wettability or adhesion properties of LDPE/EVA blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007