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     

Monitoring of the discoloration on γ‐irradiated PE and EVA films to evaluate antioxidant stability

γ‐Irradiated films could provoke unexpected interaction with proteins for instance just after irradiation and not necessarily after 12 months indicating there is no more reactive species. The optical properties of two multilayer films [polyethylene (PE)/ethylene vinyl alcohol (EVOH)/PE and ethylene vinyl acetate (EVA)/EVOH/EVA] after different γ‐irradiation doses is then studied in this work. The investigation on these films, either non‐irradiated or γ‐irradiated (up to 270 kGy), is performed by colorimetry measurement over time (up to 12 months) to assess the generation of new species inside the materials. The color change is directly correlated with absorbed γ‐doses. Over time, the color decreases and goes back to its initial time level. This discoloration evolution could be therefore used as an indication of the completion of the generated species reactions induced by γ‐irradiation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46114.     

Oxygen barrier properties of polyketone/EVOH blend films and their resistance to moisture

Polyketone (PK) has excellent chemical and mechanical properties, but its use in food packaging is limited due to its oxygen barrier properties being insufficient for high-barrier film applications. To improve its oxygen barrier properties, PK has been blended with ethylene vinyl alcohol copolymer (EVOH), which is one of the highest oxygen barrier polymers in use today. The oxygen barrier properties under both dry and humid conditions, as well as the mechanical properties of PK/EVOH blend films were investigated in this study. These novel PK/EVOH blend films exhibited unusually low oxygen permeability values from 0.3 to 0.16 cc 20 μm m⁻² day⁻¹ atm⁻¹ with increasing EVOH content from 30 to 70 wt%, which are even lower than those of the ideal laminar model that expresses the theoretical minimum permeability values attainable for blended barrier films. These high oxygen barrier properties of PK/EVOH blend films can conceivably be attributed to the combination of two dominant effects: a tortuous diffusion path through the EVOH domains in the PK matrix and hydrogen bonding interactions between PK and EVOH. Furthermore, in high-humidity environments with retorting, the PK/EVOH blend films exhibited superior resistance to moisture over EVOH. Immediately after the retorting test, the oxygen permeability of the high-barrier PK/EVOH blend films with an EVOH content of 30–40 wt% increased by less than 3× the pre-retorting value, as opposed to 74× for EVOH. In addition, PK/EVOH blend films displayed superior stretching characteristics, with a breaking strain of over 300%, which are valuable for flexible packaging applications.     

EHA/PE复合薄膜的力学性能和阻透性能

分别使用氧气透过率分析仪、水蒸气透过率分析仪、拉伸试验机、紫外可见分光光度计以及差示扫描量热仪测试了乙烯乙烯醇共聚物(EVOH)、聚酰胺6(PA6)、EVOH/PA6(EHA)等薄膜以及EHA/聚乙烯(PE)复合薄膜的力学性能和阻透性能。结果表明,EVOH与PA6有较好的相容性,所制成的薄膜EHA与PE复合后的EHA/PE复合薄膜对氧气和水蒸气有良好的阻隔性,并且对可见光有很好的透过性,比较适合作食品包装材料。     

Effect of electron beam irradiation on the properties of ethylene‐(vinyl acetate) copolymer/natural rubber/organoclay nanocomposites

The effects of electron beam (EB) irradiation on the morphology, crosslink density, and tensile properties of EVA/SMR L (Standard Malaysian Rubber)/organoclay nanocomposites prepared by a melt‐blending technique were investigated. All the samples were irradiated by using a 3.0‐MeV EB apparatus with doses ranging from 50 to 200 kGy. Organoclay loading was varied from 0 to 10 phr (parts by weight per hundred parts of resin). X‐ray diffraction results and transmission electron microscopy images proved that the dispersion of organoclay in the nanocomposites was slightly improved by EB irradiation. The gel fraction yield for the nanocomposites increased with irradiation dose but decreased with organoclay loading. However, at 200 kGy, the gel fraction yield was almost the same at all organoclay loadings. Tensile strength and stress at 100% elongation increased proportionally with the irradiation dose. Elongation at break of the nanocomposites increased up to 100 kGy but then decreased at higher irradiation doses. The intercalation and exfoliation of the organoclay, the barrier effect, and the Hofmann degradation of the modification agent are the three major factors leading to the improvement of the properties of the irradiated nanocomposites. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

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     

Mechanical and barrier properties of carbon nanotube reinforced PCL‐based composite films: Effect of gamma radiation

Carbon nanotube (CNT) reinforced (0.05–0.5% by wt) polycaprolactone (PCL)‐based composites were prepared by compression molding. Addition of 0.2% CNT caused a 131% improvement of tensile strength (TS) of PCL films. The tensile modulus (TM) and elongation at break (Eb) of PCL were also significantly improved with the addition of CNT. The water vapor permeability of PCL was 1.51 g·mm/m²·day but 0.2% CNT containing PCL films showed 1.08 g·mm/m²·day. Similarly, the oxygen transmission rate (OTR) of PCL films was found to decrease with the addition of CNT. But, carbon dioxide transmission rate (CO₂TR) of PCL film was improved due to incorporation of CNT. Effect of gamma radiation on PCL films and CNT reinforced PCL‐based composites were also studied. The TS of the irradiated (10 kGy) PCL films gained to 75% higher than control sample. The TS of the 0.2% CNT reinforced composite film was reached to 41 MPa at 15 kGy dose. The barrier properties of non‐irradiated and irradiated (10 kGy) PCL films and composites (0.2% CNT reinforced) were also measured. Both PCL films and composites showed lower values of WVP upon irradiation and indicated better water vapor barrier. The OTR and CO₂TR of the irradiated (10 kGy) PCL films and composites were decreased compared to their counterparts. Surface and interface morphologies of the composites were studied by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhancement of radiation‐resistant effect in ethylene–vinyl acetate copolymers by the formation of ethylene–vinyl acetate copolymers/clay nanocomposites

Ethylene–vinyl acetate (EVA) copolymers/clay nanocomposites, prepared by using nonreactive organophilic clay and reactive organophilic clay, were characterized by X‐ray diffraction and by high‐resolution transmission electron microscopy. The influence of gamma irradiation on the structure and properties of the pure EVA and EVA/clay nanocomposites was systematically investigated. In the presence of gamma radiation, the clay can effectively restrain the increase of the storage modulus of EVA/clay nanocomposites, which was supported by dynamical mechanical analysis. Gamma irradiation had almost no effect on the thermal properties of EVA/clay nanocomposites by using nonreactive organophilic clay, but it obviously improved the thermal stability of EVA/clay nanocomposites by using reactive organophilic clay. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2532–2538, 2005     

Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

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.     

Characterization,mechanical, and thermal properties of gamma irradiated starch films reinforced with mineral clay

Composite fabricated from starch and different concentrations of clay was prepared by solution casting method. The casted film was irradiated to different gamma irradiation doses 10, 20, 30, and 40 kGy. The dispersion of clay into starch was investigated by using X‐ray diffraction (XRD). The structural morphology of the composite was measured by scanning electron microscope and infrared spectroscopy. Film properties, such as water vapor transmission, mechanical, and thermal properties were also measured. The gel content and swelling behavior of the starch/clay composite were investigated. It was found that the gel content increases with increasing clay content and irradiation dose. The results obtained indicate that the starch/clay composite showed an increase in the tensile strength, thermal stability. Moreover, there is a decrease in water vapor transmission (WVRT) which improves its barrier properties. Both XRD and infrared spectroscopy showed that starch can be intercalated into the clay galleries. Also antibiotic drug Chlortetracycline HCl was loaded into the starch/clay composite by direct adsorption method. Chlortetracycline HCl adsorption capacity of composite was found to increase from 1.13 to 4.20 mg Chlortetracycline HCl per gram dry film with increasing amount of drug concentration. In vitro drug release studies in different buffer solutions showed that the basic parameters affecting the drug release behavior of the film are pH of the solution, drug concentration, and time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of surfactant and electron treatment on the electrical and thermal conductivity as well as thermal and mechanical properties of ethylene vinyl acetate/expanded graphite composites

This study presents an investigation of the electrical and thermal conductivities of composites based on an ethylene vinyl acetate (EVA) copolymer matrix and nanostructured expanded graphite (EG). To improve the EG dispersion in EVA, EG sheets were modified by treating them with the anionic surfactant sodium dodecyl sulphate (SDS) in water. The modified SDS‐EG platelets, after being filtered and dried, were melt‐mixed with EVA to prepare the composites. Finally, both EVA/EG and EVA/SDS‐EG composites were subjected to 50 kGy electron beam (EB) irradiation. SEM images confirm that the irradiated EVA/EG samples had improved interfacial adhesion, while the irradiated EVA/SDS‐EG samples showed even better interfacial adhesion. The gel contents of the irradiated samples without and with SDS treatment increased with increase in EG loading. The EVA/EG composites exhibited a sharp transition from an insulator to a conductor at an electrical percolation threshold of 8 wt %, but with SDS‐EG the electrical conductivity was extremely low, showing no percolation up to 10 wt % of filler. The EB irradiation had no influence on electrical conductivity. The thermal conductivity linearly increased with EG content, and this increase was more pronounced in the case of SDS‐EG, but decreased after EB irradiation. The thermal properties were little influenced by EB irradiation, while better polymer–filler interaction and better filler dispersion as a result of SDS treatment, and the EB irradiation initiated formation of a cross‐linked network, had a positive effect on the tensile properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42396.     

Performance of polyethylene/ethylene-vinyl alcohol copolymer/polyethylene multilayer films using maleated polyethylene blends

Blends of linear low density polyethylene (LLDPE) and linear low density polyethylene grafted with maleic anhydride (LLDPE-gMA) were used to promote adhesion between LLDPE and ethylene-vinyl alcohol copolymer (EVOH) in a coextruded three layer flat film, trying to avoid the use of a tie layer. These particular films could be an option when the equipment for a five layer system is not available. The effect of the modified polymer on the surface of cast films was characterized through contact angle measurements. T-peel strength, and oxygen and water vapor transmission rate of the multilayer films were measured as a function of LLDPE-gMA content. Compressed films with 0%, 0.03%, and 0.08% of maleic anhydride (MA) were also analyzed by infrared spectroscopy (FTIR). The increased T-peel strength observed when using MA contents higher than 0.08% suggests a good interfacial adhesion between layers. This increase could be associated with specific interactions between the LLDPE-gMA and the EVOH, as the development of covalent bonds through the reaction of the anhydride with the EVOH hydroxyl groups across the interface. This was proved by the FTIR analysis that showed an increase in the ester band absorbance with an increase on the maleated polymer content and bonding time indicating that a chemical reaction occurred, at the interface. The observed changes on the oxygen and water vapor barrier properties of the films were not significant.     

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.     

Permeation of oxygen and water vapor through EVOH films as influenced by relative humidity

The transport properties of oxygen and water vapor through EVOH films as functions of relative humidity (RH) and temperature were studied. The results of oxygen and water vapor permeation demonstrated that temperature and RH markedly affected barrier properties of these films. In general, the EVOH films had minimal oxygen and water vapor permeabilities at a low RH, attributed to the reduced mobility of the polymer resulting from strong interactions between small water molecules and the polymeric matrix at low RH. Beyond 75% RH, the permeabilities increased considerably. In addition, the barrier performance of the EVOH films was found to be dependent on their ethylene content and orientation. From the experimental data, semiempirical equations describing oxygen transmission rates (O₂TR) as functions of RH and temperature were developed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1866–1872, 2001     

Mechanical and barrier properties of thermoplastic whey protein isolate/ethylene vinyl acetate blends

Crude oil is becoming scarcer and more expensive, resulting in alternative biobased or partially biobased materials gaining importance in the field of plastic packaging and encouraging the development of naturally derived, protein‐based plastics (Endres, 2009; Jones and McClements, Compreh. Rev. Food Sci. Food Safety 2010, 9, 374; Khwaldia et al., Compreh. Rev. Food Sci. Food Safety 2010, 9, 374). A strategy to improve extrusion processing behavior of proteins is the blending with other polymers. In this study ethylene vinyl acetate (EVA) was used for such purpose. The aim of this study was to determine the properties of blends of thermoplastic whey protein (TPP) and ethylene vinyl acetate (EVA). Mechanical and barrier properties were tested. Blends of differing TPP/EVA ratio were produced and extruded into flat films. Morphological analysis of the blends shows immiscibility of the TPP and EVA, greatly influencing the mechanical properties. Young's modulus measurements shows the values approached that of pure EVA with increasing EVA ratios. At values of about 21 MPa, corresponding to EVA ratios of 30% (w/w) and above, continuous extrusion including material take‐off was possible. At higher whey protein ratios in the blends the water vapor transmission rate increased, i.e., the higher water vapor transmission rate of whey protein compared with EVA dominated this property. This study showed that whey proteins can be utilized for extrusion by blending with EVA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41172.     

The effect of trimethylol propane tetraacrylate (TMPTA) and organoclay loading on the properties of electron beam irradiated ethylene vinyl acetate (EVA)/natural rubber (SMR L)/organoclay nanocomposites

Ethylene vinyl acetate (EVA)/natural rubber (SMR L)/organoclay nanocomposites were prepared by melt blending technique with 0–10 phr organoclay loading and 3 phr TMPTA. Electron beam initiated crosslinking on these samples was carried out using a 3.0 MeV electron beam machine with doses ranging from 50 to 200 kGy. XRD results proved that dispersion of organoclay in the nanocomposites was slightly improved by irradiation with TMPTA. This was further supported by transmission electron microscopy images, where the nanoscale dispersion of organoclay was more homogenous throughout the irradiated polymer matrix compared to nonirradiated samples. TMPTA also increased the gel fraction yield, tensile properties and thermal stability of the irradiated neat EVA/SMR L and its nanocomposites. TMPTA was found to act as a crosslink initiator, which promotes crosslink bridges via free radical mechanism in EVA/SMR L matrix. SEM observation shows that the fracture behavior of the irradiated neat EVA/SMR L and its nanocomposites with TMPTA is significantly different compared to the fracture behavior of the nonirradiated neat EVA/SMR L. The distinct failure surface structure formed in the irradiated samples with TMPTA explains the overall higher value of tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High oxygen barrier multilayer EVOH/LDPE film/foam

High oxygen barrier film/foam system had been developed using multilayer coextrusion technology. The film/foams contained alternating ethylene–vinyl alcohol (EVOH) copolymer film layers and low‐density polyethylene (LDPE) foam layers. To ensure good adhesion and layer integrity, the LDPE was preblended with LDPE grafted maleic anhydride. The layered structure of film/foam was characterized by scanning electron microscopy. The film/foams showed adjustable density, oxygen permeability, and mechanical properties by changing the film and foam composition. Film/foam with 10% EVOH film layer was successfully thermoformed at room temperature. The cells in the foam layer were observed to deform during the mechanical forming process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46425.     

聚乳酸水蒸气阻隔性的改性

聚乳酸(PLA)用于产品包装时不仅要满足所必需的力学性能、化学稳定性、透明性、印刷性以及热封性等,还要满足产品对阻隔性的要求.采用共混、添加助剂的方法以提高PLA对水蒸气的阻隔作用.结果显示:乙烯-乙烯醇共聚物(EVOH)、有机蒙脱土(OMMT)的加入可以降低PLA的水蒸气透过率(WVTR),且随着其含量的增加,WVTR值逐渐减小,当EVOH质量含量达到50％时,WVTR值减小了61％,OMMT含量达到9％时,WVTR值减小了58％;在OMMT/PLA共混物中加入聚癸二酸丙三醇酯(PGS)后,WVTR值增加.     

Mechanical and thermal properties of EVA blended with biodegradable ethyl cellulose

In this study, biodegradable blend of Poly (Ethylene‐co‐Vinyl Acetate) (EVA) and Ethyl Cellulose (EC) were prepared. Ethylene vinyl alcohol (EVOH) copolymer was used as an interfacial compatibilizer to enhance adhesion between EVA and EC. The melt blended compatibilized biocomposites were examined for mechanical and thermal properties as per the ASTM standards. It has been found that the EC has a reinforcing effect on EVA leading to enhanced tensile strength and also impart biodegradability. Thus, a high loading of 50% EC could be added without compromising much on the mechanical properties. Analysis of the tensile data using predictive theories showed an enhanced interaction of the dispersed phase (EC) and the matrix (EVA). The compatibilizing effects of EVOH on these blends were confirmed by the significant improvement in the mechanical properties comparable with neat EVA as also observed by SEM microscopy. The TGA thermograms exhibits two‐stage degradation and as EC content increases, the onset temperature for thermal degradation reduces. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010