Effect of chlorine dioxide gas on physical,thermal, mechanical,and barrier properties of polymeric packaging materials

The effects of gaseous chlorine dioxide (ClO₂) on properties and performance of 10 selected polymeric packaging materials, including polyethylene (PE), biaxially oriented poly(propylene), polystyrene, poly(vinyl chloride), poly(ethylene terephthalate) (PET), poly(lactic acid), nylon, and a multilayer structure of ethylene vinyl acetate (EVA)/ethylene vinyl alcohol (EVOH), were evaluated. Physical, mechanical, barrier, and color properties as well as infrared (IR) spectra were assessed before and after polymer samples were exposed to 3600 ppmV ClO₂ gas at 23°C for 24, 168, and 336 h. The IR spectra of the ClO₂‐treated samples revealed many changes in their chemical characteristics, such as the formation of polar groups in the polyolefin, changes in functional groups, main chain scission degradation, and possible chlorination of several materials. The ClO₂‐treated PE samples showed a decrease in tensile properties compared with the untreated (control) films. Decreases in moisture, oxygen, and/or carbon dioxide barrier properties were observed in the treated PE, PET, and multilayer EVA/EVOH/EVA samples. A significant increase (P < 0.05) in the barrier to O₂ was observed in the ClO₂‐treated nylon, possibly the result of molecular reordering, which was found through an increase in the crystallinity of the material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Morphology,resistivity, and thermal behavior of EVOH/carbon black and EVOH/graphite composites prepared by simple saponification method

Poly(ethylene‐co‐vinyl alcohol) (EVOH)/carbon black (CB) and EVOH/graphite (GP) electro‐conductive composites were prepared by saponification of poly(ethylene‐co‐vinyl acetate) (EVA)/CB and EVA/GP composites in ethanol/KOH solution. The electrical resistivity change and positive temperature coefficient (PTC) behavior of these composites were investigated. The volume resistivity of EVA/CB and EVA/GP composites was decreased with saponification time. It can be observed that EVA/CB10 and EVA/GP05 composites showed a significant reduction in resistivity after saponification for 1 h. With the increase in saponification time, PTC peak temperature of both composites was shifted at a higher temperature. Tensile properties, morphology, and thermal behavior of the prepared composites have been also evaluated using universal test machine, scanning electron microscopy, and differential scanning calorimetry, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Radiation effects on poly(propylene) (PP)/ethylene–vinyl acetate copolymer (EVA) blends

Radiation effects on poly(propylene)/ethylene–vinyl acetate copolymer (PP/EVA) blends are discussed. Increasing the EVA content enhanced the crosslinking effect of radiation in PP/EVA blends. This effect was significant when the EVA content was ≥50% in PP/EVA blends that were exposed to γ‐ray irradiation in air. This phenomenon is discussed in relation to the compatibility, morphology, and thermal properties of PP/EVA blends. The results indicate that the effect is dependent on the compatibility, the increase in the amorphous region content, and the EVA content in PP/EVA blends. The possible mechanism of radiation crosslinking or degradation in irradiated PP/EVA blends was studied quantitatively by a novel method, a “step analysis” process, and thermal gravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3420–3424, 2002     

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     

Radiation‐induced oxygen scavenging activity in EVOH copolymers

Oxygen scavenging capacity has been observed for the first time in an ethylene‐vinyl alcohol (EVOH29, i.e., 29 mol % of ethylene) copolymer as a consequence of electron beam irradiation at doses of 30 and 90 kGy. This oxygen blocking activity is thought to arise from the reaction of oxygen with the free radicals formed during the irradiation process and it has been observed to be dependent of the irradiation dose, i.e., the higher the dose, the longer the time the polymer is able to react with oxygen. The characterization of the irradiated polymeric samples has been carried out through DSC and FT‐IR and the oxygen transmission rate has been measured as a function of time and compared with the properties of the nonirradiated material. A drop in the melting point and in the enthalpy of fusion and broader peaks were observed after irradiation, which indicated changes in the morphology of the copolymer. Through FT‐IR, a slight decrease in the crystallinity of the irradiated EVOH29 was observed at the highest irradiation dose and several bands arise which correspond to the formation of degradation products such as aldehydes and ketones after irradiation. Those radiolysis compounds were identified through gas chromatography coupled to mass spectroscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effects of ionizing radiation in ethylene-vinyl alcohol copolymers and in composites containing microfibrillated cellulose

This study reports on the effect of gamma radiation on morphological, thermal, and water barrier properties of pure ethylene vinyl alcohol copolymers (EVOH29 and EVOH44) and its biocomposites with the nanofiller microfibrillated cellulose (2 wt %). Added microfibrillated cellulose (MFC) preserved the transparency of EVOH films but led to a decrease in water barrier properties. Gamma irradiation at low (30 kGy) and high doses (60 kGy) caused some irreversible changes in the phase morphology of EVOH29 and EVOH44 copolymers that could be associated to crosslinking and other chemical alterations. Additionally, the EVOH copolymers and the EVOH composites reduced the number of hygroscopic hydroxyl functionalities during the irradiation processing and novel carbonyl based chemistry was, in turn, detected. As a result of the above alterations, the water barrier properties of both neat materials and composites irradiated at low doses were notably enhanced, counteracting the detrimental effect on water barrier of adding MFC to the EVOH matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Oxygen permeation resistance of polyethylene,polyethylene/ethylene vinyl alcohol copolymer,polyethylene/modified ethylene vinyl alcohol copolymer,and polyethylene/modified polyamide–ethylene vinyl alcohol copolymer bottles

The oxygen permeation resistance of polyethylene (PE), polyethylene/ethylene vinyl alcohol copolymer (PE/EVOH), polyethylene/modified ethylene vinyl alcohol copolymer (PE/MEVOH), and polyethylene/modified polyamide–ethylene vinyl alcohol copolymer (PE/MPAEVOH) bottles was investigated. The oxygen permeation resistance improved significantly after the blending of ethylene vinyl alcohol copolymer (EVOH) barrier resins in PE matrices during blow molding; less demarcated EVOH laminas were found on the fracture surfaces of the PE/EVOH bottles. Surprisingly, the oxygen permeation resistance of the PE/MEVOH bottles decreased significantly, although more clearly defined modified ethylene vinyl alcohol copolymer (MEVOH) laminas were found for the PE/MEVOH bottles as the compatibilizer precursor contents present in the MEVOH resins increased. In contrast, after the blending of modified polyamide (MPA) in EVOH resins, more demarcated modified polyamide–ethylene vinyl alcohol copolymer (MPAEVOH) laminar structures were observed in the PE/MPAEVOH bottles as the MPA contents present in the MPAEVOH resins increased. In fact, with proper MPAEVOH compositions, the oxygen permeation resistance of the PE/MPAEVOH bottles was even better than that of the PE/EVOH bottles. These interesting oxygen barrier and morphological properties of the PE, PE/EVOH, PE/MEVOH, and PE/MPAEVOH bottles were investigated in terms of the free volumes, barrier properties, and molecular interactions in the amorphous‐phase structures of the barrier resins present in their corresponding bottles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2528–2537, 2004     

Thermal,structural, and optical properties of γ‐irradiated poly(vinyl alcohol)/poly(ethylene glycol) thin film

Poly(vinyl alcohol)/poly(ethylene glycol) (PVA/PEG) copolymer was prepared using casting technique. The obtained PVA/PEG thin films have been irradiated with gamma rays with doses ranging from 1.5 to 20 Gy. The resultant effect of gamma irradiation on the thermal properties of PVA/PEG has been investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The onset temperature of decomposition T_o and activation energy of thermal decomposition E_a were calculated, results indicating that the PVA/PEG thin film decomposes in one main weight loss stage. Also, the gamma irradiation in dose range 4–12 Gy led to a more compact structure of PVA/PEG copolymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition. The variation of transition temperatures with gamma dose has been determined using DTA. The PVA/PEG thermograms were characterized by the appearance of an endothermic peak due to melting of crystalline phase. In addition, structural property studies using X‐ray diffraction and infrared spectroscopy were performed on both nonirradiated and irradiated samples. Furthermore, the transmission of the PVA/PEG samples and any color changes were studied. The color intensity (E was greatly increased with increasing the gamma dose and was accompanied by a significant increase in the blue and green color components. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface analysis and printability studies on electron beam-irradiated thermoplastic elastomeric films from LDPE and EVA blends

The electron beam-initiated surface modification of films prepared from various blends of low-density polyethylene (LDPE), ethylene vinyl acetate (EVA), and ditrimethylol propane tetraacrylate (DTMPTA) was carried out over a range of radiation doses (20-500 kGy) and concentrations of DTMPTA. The films were characterized by Fourier transform infrared-attenuated total reflectance (FT-ATR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), contact angle measurements, and peel adhesion. The printability of the films was also measured. FT-ATR and XPS revealed that the surface polarity of the films made from a 50 : 50 blend of LDPE and EVA increased up to a radiation dose of 100 kGy, compared with the unirradiated sample. The polarity decreased after 100 kGy radiation. Surface pitting and roughness were observed in the SEM photomicrographs of the same films, irradiated at higher radiation doses. Higher values of the surface energy were obtained at 100 kGy for the samples without DTMPTA and for the samples containing 3 wt% DTMPTA. Excellent printability was observed for all the films irradiated above an irradiation dose of 20 kGy. The data on the printability and peel adhesion of the irradiated films could be explained by surface energy, XPS, and SEM results.     

Radiation effects on HDPE/EVA blends

In this article, we discuss the radiation effects of high‐density polyethylene (HDPE)/ethylene–vinyl acetate (EVA) copolymer blends. In comparison with the low‐density polyethylene/EVA blends, the EVA content in the HDPE/EVA blends had a lower enhancement effect on radiation crosslinking by γ‐ray irradiation in air. The phenomenon is discussed with the compatibility, morphology, and thermal properties of HDPE/EVA blends. The HDPE/EVA blends were partly compatible in the amorphous region, and radiation crosslinking of the HDPE/EVA blend was less significant, although increasing the amorphous region's content of the HDPE/EVA blends and the vinyl acetate content of EVA were beneficial to radiation crosslinking. The good compatibility was a prerequisite for the enhancement effect of EVA on the radiation crosslinking of the polyethylene/EVA copolymer. The radiation crosslinking and the degradation mechanism of HDPE/EVA blends were examined quantitatively by a novel method, the step analysis process of irradiated HDPE/EVA blends with a thermal gravimetric analysis technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 553–558, 2002     

Improvement of compatibility of poly(ethylene terephthalate) and poly(ethylene octene) blends by γ‐irradiation

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene octene) (POE) were prepared by melt blending with various amounts of trimethylolpropane triacylate (TMPTA). The mechanical properties, phase morphologies, and gel fractions at various absorbed doses of γ‐irradiation have been investigated. It was found that the toughness of blends was enhanced effectively after irradiation as well as the tensile properties. The elongation at break for all studied PET/POE blends (POE being up to 15 wt %) with 2 wt % TMPTA reached 250–400% at most absorbed doses of γ‐irradiation, approximately 50–80 times of those of untreated PET/POE blends. The impact strength of PET/POE (85/15 wt/wt) blends with 2 wt % TMPTA irradiated with as little as 30 kGy absorbed dose exceeded 17 kJ/m², being approximately 3.4 times of those of untreated blends. The improvement of the mechanical properties was supported by the morphology changes. Scanning electron microscope images of fracture surfaces showed a smaller dispersed phase and more indistinct inter‐phase boundaries in the irradiated blends. This indicates increased compatibility of PET and POE in the PET/POE blends. The changes of the morphologies and the enhancement of the mechanical properties were ascribed to the enhanced inter‐phase boundaries by the formation of complex graft structures confirmed by the results of the gelation extraction and Fourier Transform Infrared analyses. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of thermal and morphological characteristics on mechanical responses of polypropylene/γ‐irradiated elastomer blends

The approach of this paper is to examine the mechanical responses of polypropylene (PP)/γ‐irradiated ethylene acrylic elastomer blends and subsequently compare them with the PP/unirradiated ethylene acrylic elastomer blends. Thorough correlations were drawn between the mechanical characteristics of blends and their morphological, thermal, thermomechanical, and fractured surface morphological aspects. The idea of carrying out γ‐irradiation was to introduce crosslinking points in the elastomer phase. For better understanding, correlations between the impact test results and the fractured surface morphologies were analyzed. The limited tensile properties of PP/γ‐irradiated elastomer blends were attributed not only to the poor interfacial adhesion, obtained by fitting with several theoretical mechanical models, but also to the substantially higher elastomer particle size in the blends than in the PP/unirradiated elastomer blends. The higher loss modulus and tan δ values for PP/unirradiated elastomer blends along with the attainment of much smaller particles of elastomers were responsible for the phenomenal increase in impact properties, which was actually attributed to the formation of crazes inside the dispersed phase during applied impact stress. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46597.     

Effect of electron beam radiation on structural changes of trimethylol propane trimethacrylate,ethylene vinyl acetate,and their blends

The effect of electron beam irradiation at different radiation doses (2, 5, 10, 15, and 20 Mrad) on trimethylol propane trimethacrylol propane trimethacrylate (TMPTMA), ethylene vinyl acetate (EVA, 12% vinyl acetate content), and their blends (0.5, 1, 1.5, 2, 2.5, 3, and 5 parts/100 parts EVA) was investigated. An IR study showed some residual unsaturations retained in irradiated pure TMPTMA, while in blends all unsaturations were used up at a very early stage of irradiation. The concentration of the carbonyl group due to air oxidation increased in pure EVA and blends, but it reached a maximum at the 1.5-part TMPTMA level and 5-Mrad dose. some ether linkages were formed during irradiation in pure EVA and the blends, although in pure EVA the concentration of ether linkages reached a maximum at the 2-Mrad dose and then decreased and in the blends it increased with an increase in radiation dose. Gel content showed an increasing trend with an increase in radiation dose, but it increased marginally with TMPTMA level. A blend of EVA with 1 part TMPTMA produced more gel than pure EVA at the same irradiation dose. © 1996 John Wiley & Sons, Inc.     

Resistivity and PTC behaviour of electro-conductive PVOH/MWNT and EVOH/MWNT nanocomposites

Electro-conductive poly(vinyl alcohol)/multi-walled carbon nanotube (PVOH/MWNT) and poly(ethylene-co-vinyl alcohol) (EVOH)/MWNT nanocomposites were prepared by precipitation saponification method. The MWNT was functionalised by electron beam irradiation in air at 1200?kGy doses. The electrical resistivity, thermal and mechanical properties, and positive temperature coefficient (PTC) behaviour of these nanocomposites were investigated. The melting and crystallisation peak temperatures of both nanocomposite systems were shifted at a higher temperature with the increase in saponification time. Their crystallinity and mechanical strength also increased with saponification time, indicating an increase in intermolecular hydrogen bond between vinyl alcohol groups. With the saponification time, PTC peak temperature of EVA28/MWNT and EVA40/MWNT nanocomposites was shifted at a higher temperature and followed by a negative temperature coefficient (NTC) of resistivity. However, the saponified PVAc/MWNT nanocomposites showed only NTC behaviour over a temperature range of 30–140°C.     

Stress relaxation in low‐shrink‐force polyolefin films

The morphology and stress relaxation of coextruded five‐layer LLDPE (linear low‐density polyethylene)/EVA (ethylene‐vinyl‐acetate) copolymer films were studied. Increasing VA (vinyl acetate) content in EVA causes a decrease of shrink tension in the films, which can be explained by a decrease in amount of crystallinity. The relaxation time spectrum of the coextruded crosslinked LLDPE/EVA films is similar to the relaxation time spectrum of crosslinked LLDPE film at room temperature. However, at elevated temperatures, an additional peak appears on the spectrum of coextruded film. The cause of this peak is temperature‐ and stress‐induced recrystallization of EVA during the relaxation test. This recrystallization was confirmed with DSC and wide angle X‐ray analysis. Polym. Eng. Sci. 44:1716–1720, 2004. © 2004 Society of Plastics Engineers.     

Investigation on the formation mechanisms of hydrogels made by combination of γ‐ray irradiation and freeze‐thawing

Hydrogels based on poly(vinyl alcohol) (PVA)/water‐soluble chitosan (ws‐chitosan)/glycerol were prepared by γ‐ray irradiation, freeze‐thawing, and combination of γ‐ray irradiation and freeze‐thawing, respectively. The influence of freeze‐thawing cycles, the irradiation doses, and the sequence of freeze‐thawing and irradiation processes on the rheological, swelling, and thermal properties of these hydrogels was investigated to evaluate the formation mechanisms of hydrogels made by combination of irradiation and freeze‐thawing. For hydrogels made by freeze‐thawing followed by irradiation, the physical crosslinking is destroyed partially while chemical crosslinking is formed by irradiation. However, the chemical crosslinking density reduces with the increase of freeze‐thawing cycles. Hydrogels made by irradiation followed by freeze‐thawing bear less degree of physical crosslinking with the increase of irradiation dose for the increased chemical crosslinking density. It is found that these hydrogels own larger swelling capacity and better transparent appearance than those made by freeze‐thawing followed by irradiation. Moreover, the former hydrogels have larger mechanical strength than the latter at low freeze‐thawing cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

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.     

Morphology,Resistivity, and PTC behavior of EVOH/CB composites prepared by solvent‐casting saponification and precipitation saponification

Poly(ethylene‐co‐vinyl alcohol)/carbon black (EVOH/CB) composites were prepared by a solvent‐casting saponification (‐D) and precipitation saponification (‐P) methods with a poly(ethylene‐co‐vinyl acetate)/CB (EVA/CB) toluene suspension. The effects of the CB content and saponification time on the morphology, electrical resistivity, thermal, and mechanical properties of EVA/CB composites were examined. The volume resistivity (ρ _v) of the EVA/CB‐D and EVA/CB‐P samples decreased significantly with increasing CB content and the percolation threshold of such composites was determined about 10 wt%. At 10 wt% of CB content, the ρ _v of EVA/CB‐D composite decreased significantly with the saponification time, whereas ρ _v of EVA/CB‐P composites did not change. As the saponification time increased, EVA/CB25wt% composites form cavity structure which CB is usually located in oval cavities larger than the particles themselves. This oval cavity structure almost resembles extruded high‐density polyethylene (HDPE)/CB composites. The morphology and PTC behavior of prepared composites were compared with those of HDPE/CB and the mechanism of PTC and NTC effects was discussed. POLYM. COMPOS., 38:1462–1473, 2017. © 2015 Society of Plastics Engineers