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     

Effect of electron radiation dose on oxidation of surface layers of polyethylene,polypropylene and poly(ethylene terephthalate) films

The results of oxidation of surface layers of irradiated films made of low-density polyethylene (LDPE), isotactic biaxially oriented polypropylene (BOPP) and poly(ethylene terephthalate) (PET) are discussed. The films were modified in the air atmosphere using a high-energy electron beam generated by a linear accelerator. Oxidation of surface layers of 3.7 nm thickness upon doses of up to 500 kGy was investigated by X-ray photoelectron spectroscopy. It was found that the extents of oxidation were ca. 22, 11 and 8% for BOPP, LDPE and PET, respectively.     

Selective surface modification of ethylene-vinyl acetate and ethylene polymer blend by UV–ozone treatment

Ethylene-vinyl acetate (EVA) copolymers intended for sport sole manufacturing may contain noticeable amounts of polyethylene (LDPE) for improving abrasion resistance and decrease cost; however, this blend (EVA–PE) had low polarity and showed poor adhesion. In this study an effective environmentally friendly and fast surface treatment based on UV–ozone has been used to increase the wettability, polarity and roughness of EVA–PE material. Both the length of the UV–ozone treatment and the distance between the material surface and the UV-radiation source were tested. The UV–ozone treated EVA–PE material was characterized by ATR-IR spectroscopy using Ge prism, water contact angle measurements, X-Ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Adhesion properties were obtained from T peel tests of as-received and UV–ozone treated EVA–PE/polyurethane adhesive/leather joints.The more extended length of treatment and the shorter UV source–substrate distance increased the wettability of the EVA–PE material. Oxidation of the EVA–PE surface was produced by UV–ozone treatment creating new carbonyl groups mainly, and the amounts of hydroxyl and carboxylic groups were increased. The UV–ozone treatment produced ablation and etching of the EVA–PE material surface, mainly in the vinyl acetate, creating a particular roughness consisting on ruffles with deep crevices; this topography was also produced by heating produced during UV–ozone treatment. For low length of UV treatment or high UV source–material distance, the modifications of the EVA–PE material were mainly produced in the ethylene causing the selective removal of vinyl acetate, whereas more aggressive conditions produced strong oxidation in the EVA–PE material. Finally, adhesive strength was noticeably increased in the UV–ozone treated EVA–PE/polyurethane adhesive joints, and a cohesive failure in the leather was obtained.     

Processing and characterization of multilayer films of poly(ethylene terephthalate) and surface-modified poly(tetrafluoroethylene)

Multilayer films were prepared from poly(tetrafluoroethylene) (PTFE) and poly(ethylene terephthalate) (PET) films together with using an adhesion promoting layer (tie-layer) consisting of ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and low density polyethylene (LDPE) blend. Na/naphthalene treatment and subsequent acrylic acid grafting were applied on the surfaces of PTFE for chemical modification. FT-IR spectroscopy, XPS analysis and surface energy measurements were performed to characterize the modified PTFE films. The analyses showed defluorination and oxidation of PTFE surface, and supported the acrylic acid grafting. The surface energy of modified surfaces enhanced with respect to unmodified one, which promoted adhesion. The multilayers were subjected to T-peel tests to measure the adhesion strength between PET and modified PTFE. Peel strength between the films increased with increasing E-MA-GMA amount in the tie-layer. A proportional dependence of peel strength on Na/naphthalene treatment time was observed for multilayers containing acrylic acid grafted or ungrafted PTFE. From SEM analysis, it was observed that the texture of the PTFE surface after modifications became rougher when compared to untreated PTFE. The peeled surfaces were also analyzed by SEM. The micrographs evidence that the energy absorbing mechanism is the plastic deformation of the tie-layer, which is responsible for obtaining high peel strengths.     

Physicochemical properties of irradiated and loaded LDPE films with polyfunctional monomers

Polyfunctional monomers (PFMs), namely, trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate were blended with low‐density polyethylene (LDPE) and exposed to different doses of EB irradiation. Fourier transform infrared and ultraviolet and UV–vis spectroscopy of the unirradiated, irradiated, unloaded, and PFMs‐loaded LDPE films were studied under various irradiation doses up to 300 kGy. The degree of crosslinking and oxidative degradation, as measured by the spectroscopic parameters, were dependent on both the irradiation dose and the type of loaded PFMs. For all of the loaded monomers, the extent of crosslinking increased at different rates as a function of irradiation dose. TMPTMA monomer was the most efficient in enhancing the crosslinking of LDPE films compared to the other loaded monomers. However, the unloaded LDPE film showed the least extent of crosslinking. In addition, the EB‐radiation‐induced changes, such as trans‐vinylene formation, a decrease in vinyl and vinylidene unsaturation; and carbonyl double‐bond formation and change in crystallinity were correlated. The importance of these results on the prediction of the role of polyfunctional monomers in the production of crosslinked polymers is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2025–2035, 2003     

Investigation of radiation-crosslinked foam of LDPE/EVA blends

Low-density polyethylene/ethylene–vinyl acetate copolymer (LDPE/EVA) blend was irradiated by γ-ray and then expanded by heat as a foamed material. The EVA content in the LDPE/EVA blend was benefited to form a gel. The gel fraction values of LDPE/EVA blend with 30% EVA content were higher than those of other blends in a same given dose; its gel fraction value was 1.7 times as those values of the LDPE without EVA. The gel fractions of the LDPE/EVA blend were increased with radiation dose in oxygen, in air, and in nitrogen, and the formation of gel was limited by oxygen. The oxidation products of the foam of the LDPE/EVA blend were observed in nitrogen, in oxygen by Fourier transform IR spectra. The LDPE/EVA blend system has no protection effect from oxidation in comparison with the LDPE system without EVA, which has less oxidation product than those without EVA in a same given gel fraction. The gel fraction of the LDPE/EVA blend around 25–35%, radiation dose 25±5 kGy, irradiated by γ-ray in air or in nitrogen, with higher expansion ratio (19), smaller cell diameter (0.175 mm), lower apparent density (0.042 g/cm³), higher tensile strength (0.40 MPa), and longer elongation at break (290–360%) foam of the LDPE/EVA blend were selected. These were optimum condition for application in this system. The relations among gel fraction of the LDPE/EVA blend, expansion ratio, apparent density, average cell diameter, and mechanical properties of the foam were discussed. © 1996 John Wiley & Sons, Inc.     

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.     

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     

Effect of electron beam radiation on the performance of biodegradable Bionolle-jute composite

To study the radiation effect on the physical, thermal, mechanical and degradable properties of biodegradable polymer Bionolle (chemosynthetic polyester poly(1,4-butylene succinate)), Bionolle films prepared by compression molding process and were irradiated with electron beam (EB) radiation of different doses. Gel content was found to increase with increase of radiation dose. Tensile strength of Bionolle was enhanced when Bionolle film was exposed under 20 kGy radiation. The loss of tensile strength of both unirradiated and irradiated Bionolle is 70% and 8% due to thermal aging at 70°C for 30 days. Both irradiated and unirradiated films of Bionolle were subjected to different degradation test in compost (soil burial), enzyme and storage degradation both in outdoor and indoors conditions. The loss of weight due to soil (compost) degradation test decreased with increase of radiation dose. The loss of weights of irradiated samples were found to be very less within the first three months of compost degradation. After 120 days, tensile strength of the Bionolle films irradiated at 20 kGy and 100 kGy were 68 MPa and 40 MPa, respectively, compared to the value (30 MPa) of the unirradiated Bionolle samples. Loss of tensile strength of irradiated Bionolle due to storage degradation like in roof, ground and indoors was minimum compared to unirradiated Bionolle. The weight loss due to enzymatic degradation was found to be decreased with increase of radiation dose. The tensile strength of jute reinforced Bionolle composites (23 wt.-% jute content) irradiated at 20 kGy was found to be higher (22%) than that of an unirradiated composite.     

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

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

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     

Etching of a low-density polyethylene film by fuming nitric acid

Low-density polyethylene (LDPE) films were treated with fuming nitric acid (FNA). The surface characteristics and also the insertion of polar groups like on the etched LDPE film surface were measured by SEM, IR and XPS analyses, respectively. The mechanical performance of a laminate of the etched film with epoxy resin and also the printability of the etched film surface were tested and compared with the unetched sample. The surface roughening and the presence of polar groups enhance the mechanical strength of the laminate of FNA-treated film due to mechanical interlocking and chemical interaction. The printability of the treated film surface is also superior to that of the untreated LDPE film surface.     

Improvement of Physicochemical Properties of Rubber Blends Between Nonirradiated and Irradiated Rubber Latexes by Radiation Vulcanization

Abstract

Nonirradiated natural rubber latex (NRL) and irradiated (12 kGy) rubber latex were blended in ratios of 100:0, 85:15, 65:35, 50:50, 35:65, 15:85, and 0:100 (v/v) to improve properties of the rubber latex. The blends were irradiated using different irradiation doses (0–20 kGy) in the presence of a radiation vulcanization accelerator (RVA), normal butyl acrylate (n-BA). The physicochemical properties of the nonirradiated latex, irradiated latex, and blend films were determined after leaching with distilled water. It was observed that the tensile strengths of the blend films increases with an increase in the content of the irradiated proportion and radiation doses. The composition of the blends and the doses of radiation were optimized. The maximum tensile strength (31.41 MPa) was found for the 50:50 composition of the blend with a 5 kGy radiation dose. The 100:0 blends, when irradiated, give the highest tensile strength (27.69 MPa) with 12 kGy but a 15:85 nonirradiated blend gives the tensile strength of 26.18 MPa.     

Characterization of EPDM Vulcanizates Modified with Gamma Irradiation and Trichloroisocyanuric Acid and Their Adhesion Behavior with Natural Rubber

The adhesion strength between surface-modified vulcanized ethylene propylene diene methylene (EPDM) rubber and unmodified natural rubber (NR) was investigated by a 180° peel test. Surface modification of EPDM vulcanizate was carried out by two different techniques: (a) irradiation of the surface by gamma radiation in the presence and absence of trimethylol propane triacrylate (TMPTA) as a sensitizer and (b) chemical treatment of the surface with trichloroisocyanuric acid (TCICA). The modified EPDM surface was thoroughly characterized by attenuated total reflection infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray sulfur mapping (EDX), surface energy measurements, and free sulfur and gel content analysis. The joint between the modified vulcanized EPDM and the unmodified unvulcanized NR was prepared by a co-curing method. The adhesion strength between these two surfaces was found to depend on the nature of oxidation, roughness of the joining surfaces, and extent of blooming of sulfur on the modified surface. Surface modification of EPDM sample with 1 kGy of gamma irradiation in the presence of 10 wt% TMPTA resulted in a good increase in the adhesion strength between EPDM and NR (～76% improvement over the untreated sample). On the other hand, for the trichloroisocyanuric acid modified sample, maximum improvement of adhesion strength was observed at 0.5 wt% of TCICA (～29% improvement in comparison with the untreated sample).     

Surface analysis of poor printability PVC films

Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to analyze the surfaces of PVC films with poor printability. FTIR indicated that, independent of formulation, the migrating species were metal carboxylates. Different techniques penetrate the surface to different depths allowing examination of a range of surface layers. XPS indicated that, in the worst case, the upper surface layer was comprised almost exclusively of a mixed metal carboxylate. Atom percentages obtained by XPS indicated hydrolysis of the mixed metal carboxylate at the vinyl surface.     

Effect of grafting of acrylic acid onto PET film surfaces by UV irradiation on the adhesion of PSAs

To improve the peel strength between a pressure-sensitive adhesive (PSA) and its substrate, grafting of acrylic acid (AA) onto the surface of poly(ethylene terephthalate) (PET) film was carried out. After AA was coated onto the surface of PET films using a spin coater, the coated PET films were irradiated by UV. To investigate the surface chemistry and topography of the PET-g-AA films, the grafted surface of the PET films was characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning probe microscopy (SPM). From these investigations, the effects of grafting of AA at the surface of PET by UV irradiation were discussed. In addition, to determine the effect of grafting on the adhesion between PSA polymer and PET-g-AA films, peel strength was measured after the PSA/PET-g-AA system was cured at various temperatures. As the esterification between PSA polymer and PET-g-AA films occurred in the interfacial region, the peel strength of the PSA/PET-g-AA system generally increased with increasing curing temperature.     

Chemical modification of LDPE film

Low‐density polyethylene (LDPE) film was chemically modified by chromic acid treatment to generate polar groups on the surface. The film samples were etched by chromic acid with variation of temperature at a constant time (30 min) and variation of time at a constant temperature (room temperature = 26°C). The variation of weight and thickness of the film samples before and after etching was measured. The surface morphology of the etched films was studied by Scanning Electron Microscopy (SEM). IR and XPS analysis revealed the introduction of polar groups like  COOH, 〉CO,  SO₃H on the etched LDPE film surface, which exhibited improved printability. Etching also enhanced adhesion with epoxy resin. The mechanical properties of the laminates of the two specimens of the same film sample with epoxy resin were also measured. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1041–1048, 1999     

Gamma radiation aging of EVA/EPDM blends: Effect of vinyl acetate (VA) content and radiation dose on the alteration in mechanical,thermal, and morphological behavior

A series of ethylene vinyl acetate (EVA)/ethylene‐propylene diene elastomer (EPDM) blends (50/50 ratio) with four types of EVAs were prepared using brabender type batch mixer followed by compression molding. All compression‐molded samples were exposed to gamma radiation at 500, 1000, and 1500 kGy doses and were subjected to mechanical, compression set, thermal and morphological test. The % retention in tensile strength, elongation, and hardness were found higher for higher vinyl acetate (VA) containing radiation aged EVA/EPDM blends. The compression set value was decreased with increase of VA content. The thermal degradation kinetics of high VA containing irradiated blend (EVA40/EPDM) (EVA40 is 40%VA containing EVA) was found slower than those of lower VA containing blend (EVA18/EPDM). The surface morphology for EVA18/EPDM sample was transformed into more irregular one with more cracks and fragmented segments by aging at 1500 kGy dose while surface for EVA40/EPDM sample was found comparatively smooth, fine, and continuous with very few cracks and fragmented parts at similar dose. Thus, from the measured properties and morphology, it was revealed that the degree of degradation of blends kept on decreasing with increase in VA content. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46216.     

Electron beam-initiated surface modification of elastomers

Ethylene-propylene diene monomer (EPDM) containing dicyclopentadiene (DCPD) and ethylidene norbornene (ENB) as the termonomers, styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR) have been surface-modified by 10% methyl ethyl ketone (MEK) solutions of trimethylol propane triacrylate (TMPTA) at an irradiation dose of 100 kGy. The irradiation dose and TMPTA concentration were optimized using samples treated with 2, 5, 10, 20, and 50% TMPTA and 50, 100, 200, and 500 kGy doses. Two per cent solutions of acrylate rubber having diene, chloro, and epoxy groups at the reactive sites and tripropyleneglycol diacrylate (TPGDA) and tetramethylol methane tetracrylate (TMMT) were also employed as the surface modifiers. The level and nature of the vulcanization system were varied. The modified rubbers were characterized by attenuated total reflection infrared (ATR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and contact angle measurements. IR and XPS studies confirmed the generation of polar groups such as C=O and -C-O-C on the surfaces. The contact angles and the surface energy change with the nature of the modifiers, rubbers, diene monomers, the crosslinking system and the level of the curing agent. The total surface energy and the thermodynamic work of adhesion of the different systems have been correlated with the amount and the nature of the polar groups generated.     

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