Photoinitiated crosslinking of ethylene‐vinyl acetate copolymers and characterization of related properties

Photoinitiated crosslinking of EVA in the presence of benzophenone (BP) as photoinitiator and triallyl isocyanurate (TAIC) as crosslinker and characterization of the related properties have been studied by gel determination, heat extension, DSC, DMTA, TGA, and mechanical measurements. The photoinitiated crosslinking efficiency of the EVA‐BP‐TAIC system and various factors affecting the crosslinking process, such as photoinitiator and crosslinker and their concentrations, irradiation temperature, and irradiation atmosphere were studied in detail and optimized by comparison of gel contents. The results show that the EVA samples with a thickness of 1 mm are readily crosslinked to a gel content of above 80% with 5 s UV‐irradiation under optimum conditions. The data from the heat extension and DSC show that the crosslinking density of photocrosslinked EVA increase and their crystallinities decrease with increasing the UV‐irradiation time. At the same time, photocrosslinking of EVA leads to a lowering of the melt temperature and a decrease of heat of fusion. The DMTA results show that photocrosslinking increases the amorphous phase and storage modulus of the crosslinked EVA, but does not change the glass transition temperature. The data from TGA and mechanical tests give evidence that the thermal stability and mechanical properties of photocrosslinked EVA samples are much better than those of the uncrosslinked EVA. POLYM. ENG. SCI., 47:1761–1767, 2007. © 2007 Society of Plastics Engineers     

Photocrosslinking of an ethylene–propylene–diene terpolymer and the characterization of its structure and mechanical properties

An ethylene–propylene–diene terpolymer (EPDM) was photocrosslinked under UV irradiation with benzil dimethyl ketal (BDK) as a photoinitiator and trimethylolpropane triacrylate (TMPTA) as a crosslinker. The efficiency of the photoinitiated crosslinking system EPDM–BDK–TMPTA, various factors affecting the crosslinking process (the photoinitiator and crosslinker and their concentrations, the irradiation time, the temperature, the atmosphere and UV‐light intensity, and the depth of the UV‐light penetration), and the mechanical properties of photocrosslinked EPDM were examined extensively through the determination of the gel contents, infrared spectra, and mechanical measurements. EPDM samples 3 mm thick were easily crosslinked with a gel content of about 90% after 30 s of UV irradiation under optimum conditions. The photoinitiating system of a suitable initiator combined with a multifunctional crosslinker such as BDK–TMPTA enhanced the efficiency of the photocrosslinking reaction, especially by increasing the initial rate of crosslinking. The gel content of photocrosslinked EPDM, which was determined by the content of diene in EPDM, the depth of the UV‐light penetration, and the light intensity, played a key role in increasing the mechanical properties of the photocrosslinked samples in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1837–1845, 2004     

Effect of trimethylolpropane triacrylate (TMPTA) on the properties of irradiated epoxidized natural rubber (ENR‐50), ethylene‐(vinyl acetate) copolymer (EVA), and an ENR‐50/EVA blend

The effect of trimethylolpropane triacrylate (TMPTA) monomer on the tensile properties, dynamic mechanical properties, and morphology of irradiated epoxidized natural rubber (ENR‐50), ethylene‐(vinyl acetate) copolymer (EVA), and an ENR‐50/EVA blend was investigated. The ENR‐50, EVA, and ENR‐50/EVA blend were irradiated by using a 3.0‐MeV electron‐beam apparatus at doses ranging from 20 to 100 kGy. The improvement of tensile properties and morphology with irradiation indicated the advantage of having irradiation‐induced crosslinks in these materials. Observation of the properties studied confirmed that TMPTA was efficient in enhancing the irradiation‐induced crosslinking of ENR‐50, EVA, and the ENR‐50/EVA blend. Addition of TMPTA improved the adhesion between the ENR‐50/EVA blend phases by forcing grafting and crosslinking at a higher irradiation dose (100 kGy). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers.     

Properties and morphologies of elastomer blends modified with EPDM‐g‐poly[2‐dimethylamino ethylmethacrylate]

The graft copolymerization of 2‐dimethylamino ethylmethacrylate (DMAEMA) onto ethylene propylene diene mononer rubber (EPDM) was carried out in toluene via solution polymerization technique at 70°C, using dibenzoyl peroxide as initiator. The synthesized EPDM rubber grafted with poly[DMAEMA] (EPDM‐g‐PDMAEMA) was characterized with ¹H‐NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The EPDM‐g‐PDMAEMA was incorporated into EPDM/butadiene acrylonitrile rubber (EPDM/NBR) blend with different blend ratios, where the homogeneity of such blends was examined with scanning electron microscopy and DSC. The scanning electron micrographs illustrate improvement of the morphology of EPDM/NBR rubber blends as a result of incorporation of EPDM‐g‐PDMAEMA onto that blend. The DSC trace exhibits one glass transition temperature (T_g) for EPDM/NBR blend containing EPDM‐g‐PDMAEMA, indicating improvement of homogeneity. The physico‐mechanical properties after and before accelerated thermal aging of the homogeneous, and inhomogeneous EPDM/NBR vulcanizates with different blend ratios were investigated. The physico‐mechanical properties of all blend vulcanizates were improved after and before accelerated thermal aging, in presence of EPDM‐g‐PDMAEMA. Of all blend ratios under investigation EPDM/NBR (75/25) blend possesses the best physico‐mechanical properties together with the best (least) swelling (%) in brake fluid. Swelling behavior of the rubber blend vulcanizates in motor oil and toluene was also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Development of new thermoplastic elastomers from blends of polyethylene and ethylene–vinyl acetate copolymer by electron‐beam technology

Electron beam‐initiated crosslinking of films prepared from a blend of low‐density polyethylene (LDPE) and ethylene–vinyl acetate (EVA) containing 45% vinyl acetate, with ditrimethylol propane tetraacrylate (DTMPTA), was carried out over a range of radiation doses (20–500 kGy), concentration of DTMPTA (1–5 parts by weight), and blend compositions. The gel fraction of the films increases with increase in the irradiation dose, DTMPTA level, and EVA content of the blends. The mechanical and dynamic mechanical properties of the films are also changed with the above variables. Reprocessibility studies revealed that the blends irradiated at 50 kGy and below are thermoplastic elastomers with a low permanent set. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1877–1889, 2001     

Ethylene vinyl acetate/ethylene propylene diene terpolymer‐blend‐layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA‐45)/ethylene propylene diene terpolymer (EPDM) blend‐layered double hydroxide (LDH) nanocomposites have been prepared by solution blending of 1:1 weight ratio of EVA and EPDM with varying amounts of organo LDH (DS‐LDH). X‐ray diffraction and transmission electron microscopy analysis suggest the formation of partially exfoliated EVA/EPDM/DS‐LDH nanocomposites. Measurement of mechanical properties of the nanocomposites (3 wt% DS‐LDH content) show that the improvement in tensile strength and elongation at break are 35 and 12% higher than neat EVA/EPDM blends. Dynamic mechanical thermal analysis also shows that the storage modulus of the nanocomposites at glass transition temperature is higher compared to the pure blend. Such improvements in mechanical properties have been correlated in terms of fracture behavior of the nanocomposites using scanning electron microscopy analysis. Thermal stability of the prepared nanocomposites is substantially higher compared to neat EVA/EPDM blend, confirming the formation of high‐performance polymer nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

A novel intumescent flame‐retardant system for flame‐retarded LLDPE/EVA composites

A new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of high‐energy electron beam on low‐density polyethylene materials containing EVA

A series of low‐density polyethylene (LDPE) blends with different amounts of ethylene–vinyl–acetate (EVA) was prepared and irradiated with 10 MeV electron beam in the range of 0–250 kGy at room temperature in air. EVA was used as a compatibilizer and softener in four different amounts: 5, 10, 20, and 30 wt %, based on polyethylene (PE). The crosslinking of the samples was studied on the basis of gel‐content measurements as well as some thermal and mechanical properties of the specimens. The results indicated that the LDPE and LDPE–EVA blends could be crosslinked by a high‐energy electron beam, of which their thermal and mechanical properties changed effectively, however, because of EVA content of the polymer; the blends were more sensitive to lower doses of radiation. These studies were carried out to obtain a suitable compound for heat‐shrinkable tubes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1049–1052, 2004     

Free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid onto molten ethylene‐vinyl acetate copolymer

Distinctive features of free‐radical grafting of trans‐ethylene‐1,2‐dicarboxylic acid (TEDA) onto macromolecules of molten ethylene‐vinyl acetate copolymer (EVA) in the course of reactive extrusion have been investigated along with structure, mechanical characteristics, and high‐elastic properties of molten functionalized products (EVA‐g‐TEDA). It is shown that EVA‐g‐TEDA yield depends on both the peroxide initiator concentration and content of vinyl acetate units in the copolymer molecular structure. At functionalization, acid grafting is accompanied by secondary reactions of macromolecular degradation and crosslinking. With a low‐peroxide initiator concentration (0.1 wt %), degradation prevails; with a higher (0.3 wt %) concentration, crosslinking of macromolecules prevails. It is reported that monomers being grafted attach mostly over secondary carbon atoms in the polymer chain. EVA‐g‐TEDA appears to have a less perfect crystal structure with a lower‐melting temperature and crystallinity as against the starting polymer. The functionalized products display enhanced rigidity and lower deformability in comparison with the initial copolymer. Variations in the swelling ratio and melt strength of EVA‐g‐TEDA depend on the course of competing secondary processes of macromolecular degradation and crosslinking. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the particle size of expandable graphite on the thermal stability,flammability, and mechanical properties of high‐density polyethylene/ethylene vinyl‐acetate/expandable graphite composites

In this article, high‐density polyethylene/ethylene vinyl‐acetate copolymer (HDPE/EVA) composites filled with two different particle sizes (45 and 150 µm) of expandable graphite (EG) were prepared by using a twin‐screw extruder. The thermal stability, flammability, and mechanical properties of HDPE/EVA/EG composites were investigated by thermogravimetric analysis (TGA), cone calorimeter test (CCT), tensile test, and scanning electron microscopy (SEM). The results from TGA and CCT indicated that EG significantly enhanced the thermal stability and fire resistance of HDPE/EVA blend. The thermal stability and flame retardancy of HDPE/EVA/EG composites were improved with decreasing particle size of EG. Although the onset of weight loss of the flame‐retardant composites occurred at a lower temperature than that of HDPE/EVA blend, the flame‐retardant composites produced a large amount of char residue at a high temperature. The consolidated char layer formed a barrier, which could reduce heat, low‐molecular transfer, and air incursion, and thus enhanced the flame retardancy. The data from the tensile test showed that the addition of EG deteriorated the mechanical properties; however, the tensile stress and strain of HDPE/EVA/EG composites increased with decreasing the particle size of EG owing to the strong interface adhesion between polymer matrix and inorganic particles. POLYM. ENG. SCI., 54:1162–1169, 2014. © 2013 Society of Plastics Engineers     

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     

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.     

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     

Improving the properties of reclaimed waste tire rubber by blending with poly(ethylene‐co‐vinyl acetate) and electron beam irradiation

Scrap rubber reclamation is one of the most desirable approaches to solve the disposal problem of used tires. However, reclaimed tire rubber (RTR) has not gained enough attention due to its poor properties. In this work, the effects of poly(ethylene‐co‐vinyl acetate) (EVA) addition and electron beam (EB) irradiation on the properties of RTR were studied. The RTR/EVA blends containing 100–0 wt % of RTR were prepared in the internal mixer followed by EB irradiation with doses ranging from 50 to 200 kGy. The RTR/EVA blends were subjected to mechanical, gel content, thermal, and morphological analysis. It was found that the addition of EVA to RTR improved the mechanical properties of RTR. However, results revealed that RTR undergoes irradiation‐induced crosslinking in a relatively lesser extent as compared to EVA. This observation is associated with the stabilization and radical scavenging effects of additives, which are present in the RTR matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41649.     

Influence of ethylene vinyl acetate on the spinnability and mechanical properties of poly(propylene)/zeolite‐Ag blend fibers

The spinnability and mechanical properties of poly(propylene) (PP)/zeolite‐supported Ag⁺ (zeolite‐Ag)/ethylene vinyl acetate (EVA) ternary blend fibers were studied. It was found that the spinning temperature of the ternary blend fibers was decreased in the presence of EVA. The addition of 2 wt % EVA substantially improved the spinnability of the blend system by enhancing its flowability. It was also found that the ternary fiber with EVA₂₈ (28 wt % vinyl acetate content) showed balanced improvement of mechanical properties by a concomitant increase in modulus and tensile strength. The improvements of spinnability and mechanical properties suggested that a core–shell structure of zeolite‐Ag/EVA₂₈ particles, with zeolite‐Ag as the core and EVA₂₈ as the shell, was formed and remained during the melt‐mixing process of the blended chips and during the course of fiber processing. EVA probably enhanced the binding between the zeolite‐Ag and the PP matrix, as made evident in SEM microphotographs. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1460–1466, 2005     

Toughening and compatibilization of polypropylene/polyamide‐6 blends with a maleated–grafted ethylene‐co‐vinyl acetate

In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006     

Polymer electrolyte membranes prepared by EB‐crosslinking of sulfonated poly(ether ether ketone) with 1,4‐butanediol

Crosslinked sulfonated poly(ether ether ketone) (SPEEK) membranes were prepared through the electron beam (EB)‐irradiation crosslinking of SPEEK/1,4‐butanediol under various irradiation conditions and used as a proton exchange membrane (PEM) for fuel cell applications. The crosslinked membranes were characterized by gel fraction, a universal testing machine (UTM), dynamic mechanical analysis (DMA), and small‐angle X‐ray scattering (SAXS). The gel fraction of the crosslinked membranes was used to estimate the degree of crosslinking, and the gel fraction was found to be increased with an increase of the crosslinker content and EB‐absorbed dose. The UTM results indicate that a brittle EB‐crosslinked membrane becomes more flexible with an increase in the crosslinker content. The DMA results show that the EB‐crosslinked membranes have well‐developed ionic aggregation regions and the cluster T_g of membranes decrease with an increase in the 1,4‐butanediol crosslinker content. The SAXS results show that the Bragg and persistence distance of crosslinked membranes increase with an increase in the crosslinker content. The proton conductivities of the EB‐crosslinked membranes were more than 9 × 10^?2 S/cm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41760.     

Characterization of epoxidized natural rubber/ethylene vinyl acetate (ENR‐50/EVA) blend: Effect of blend ratio

Epoxidized natural rubber/Ethylene vinyl acetate copolymer (ENR‐50/EVA) blends with different ratios were prepared by using a Haake internal mixer. The effect of the blend ratio on the processing, tensile properties (such as tensile strength, elongation at break, Young's modulus and stress–strain behavior), morphology, dynamic mechanical properties, and thermal properties has been investigated. The tensile properties increase with the increase of EVA content, whereas the stabilization torque increases with the increase of ENR‐50 content in the blend. In 40:60 and 50:50 blend of ENR‐50/EVA, both the phases exist as continuous phases, producing a co‐continuous morphology. At these blend ratio, the drastic change in properties were noted, indicating that the phase inversion occurs. The results on dynamic mechanical properties revealed that the blends are compatible. Blending of ENR‐50 and EVA lead to the improvement in thermal stability and 50:50 blend ratios is the most stable blend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1504–1515, 2006     

Preparation and properties of reactive polyurethane polyacrylate blends based on carbonyl‐hydrazide reaction

A new reactive polyurethane/polyacrylate (PU/PA) blend was developed by mixing a core–shell polyacrylate latex containing keto groups in shell layer and a polyurethane dispersion incorporating multiple hydrazide groups which was synthesized by introducing the poly‐hydrazide groups into the end of the vinyl‐terminated polyurethane chains. Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC) results indicated that poly‐hydrazide groups had been incorporated in the polyurethane chains. Transmission electron microscopy (TEM) micrograph revealed that polyacrylate particles had a clear core–shell structure. The results of FTIR, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) indicated that the crosslinking reaction between two polymer systems had happened and crosslinking structure could effectively improve the compatibility between PA and PU. Thermogravimetric analysis (TGA) and mechanical tests results suggested that crosslinking structure could enhance the thermal stability and mechanical properties of blends. The influence of the PA content and the n(? CO? )/n(? NHNH₂) ratio on the hardness, water resistance, solvent resistance, and gel fraction of the blend films were comprehensively studied. The optimal PA content and n(? CO? )/n(? NHNH₂) ratio was 30% and 1.5:1 in this experiment, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44443.     

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