Limonene transport and mechanical properties of EVOH and nylon 6,6 films as influenced by RH

The transport properties of d‐limonene through ethylene vinyl alcohol copolymers (EVOH) and nylon 6,6 films as functions of relative humidity (RH) and temperature were studied. Permeation properties of these polymers were strongly influenced by temperature and RH. Compared to the EVOH films, the nylon 6,6 film had much greater limonene permeability. Mechanical property studies indicated that both the tensile modulus and yield strength of the EVOH films decreased with an increase in RH. The polymer changed from being stiff and brittle at low RH to being soft and ductile at high RH. In addition, ethylene content and orientation were found to affect the transport and mechanical properties of limonene through EVOH polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1949–1957, 2001     

Morphology and barrier properties of oriented blends of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalate) with poly(ethylene-co-vinyl alcohol)

Morphology and oxygen permeability studies were carried out for blends of poly(ethylene terephthalate), PET, and poly(ethylene 2,6-naphthalate), PEN, with poly(ethylene-co-vinyl alcohol), EVOH. PET/EVOH blends are seen as a possible substitute for poly(vinylidene chloride)-coated PET packaging films. The effects of several processing parameters such as draw temperature and draw ratio on blend morphology and barrier properties suggest that the morphology of the EVOH phase dictates to a large extent the oxygen permeabilities of these blends. The relationships between morphology and oxygen permeability and explained are explained by consideration of two-phase conduction models. The model of Fricke is found to be a good predictor of the barrier properties of the PET/EVOH system. The oxygen permeability of PET was reduced by a factor of 4.2 with the addition of 20 wt% EVOH and that of PEN by a factor of 2.7 with the addition of 15 wt% EVOH. Water vapor permeabilities and mechanical properties of PET and PEN were only slightly affected by the addition of 15 wt% EVOH.     

EVOH nanocomposite films with enhanced barrier properties under high humidity conditions

To improve the oxygen and water vapor barrier properties of ethylene vinyl alcohol, EVOH/EFG nanocomposite films under high humidity conditions, we successfully prepared highly exfoliated graphite (EFG) containing a monolayer or a few layers of graphene via rapid heating treatment and ultrasonication as confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), elemental analysis (EA), and nitrogen adsorption–desorption analysis. Six different EVOH/EFG nanocomposite films containing as‐prepared EFG were prepared via a solvent blend method and their physical and barrier properties at different relative humidities were investigated as a function of EFG content. Depending on the EFG content, oxygen transmission rate (OTR) decreased from 3.7 to 0.1 cc/m²/day at dry condition, and the difference in OTR between dry condition and humid condition decreased from 6.5 to 2.3 cc/m²/day. Barrier properties of the EVOH/EFG nanocomposite films were strongly dependent on their chemical structure and morphology. Crystallinity, tortuous path length, and hydrophobicity of EVOH/EFG nanocomposite films were enhanced by the addition of EFG. However, the thermal stability and glass transition temperature of the nanocomposite films were not improved by incorporation of EFG due to the weak interaction between EVOH and EFG. To maximize the performance of EVOH/EFG nanocomposite films, the compatibility of the polymer matrix and fillers needs to be improved. POLYM. COMPOS., 35:644–654, 2014. © 2013 Society of Plastics Engineers     

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.     

Thermal,mechanical, and gas barrier properties of ethylene–vinyl alcohol copolymer‐based nanocomposites for food packaging films: Effects of nanoclay loading

For the application of single‐layer food packaging films with improved barrier properties, an attempt was made to prepare ethylene‐vinyl alcohol (EVOH) copolymer‐based nanocomposite films by incorporation of organically modified montmorillonite nanoclays via a two‐step mixing process and solvent cast method. The highly intercalated tactoids coexisted with exfoliated clay nanosheets, and the extent of intercalation and exfoliation depended significantly on the level of clay loadings, which were confirmed from both XRD measurements and TEM observations. It was revealed that the inclusion of nanoclay up to an appropriate level of content resulted in a remarkable enhancement in the thermal, mechanical (tensile strength/modulus), optical, and barrier properties of the prepared EVOH/clay nanocomposite films. However, excess clay loadings gave rise to a reduction in the tensile properties (strength/modulus/elongation) and optical transparency due to the formation of clay tactoids with a larger domain size. With the addition of only 3 wt % clay, the oxygen and water vapor barrier performances of the nanocomposite films were substantially improved by 59 and 90%, respectively, compared to the performances of the neat EVOH film. In addition, the presence of clay nanosheets in the EVOH matrix was found to significantly suppress the moisture‐derived deterioration in the oxygen barrier performance, implying the feasibility of applying the nanocomposite films to single‐layer food packaging films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40289.     

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.     

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。     

Properties of bacterial cellulose produced in grape medium by native isolate Gluconacetobacter sp

During the production of grape wine, the occurrence of thick leathery pellicle at the air‐liquid interface was found as a contaminant. The pellicle produced was investigated with a view to use as biodegradable polymer. The bacterium that is responsible for the pellicle production was isolated, characterized and identified as Gluconacetobacter sp. Pellicle was produced in pasteurized grape extract as well as in HS medium by the isolated organism in static conditions. The purified film was subjected for Fourier transform infrared spectroscopy and C¹³ solid NMR spectroscopy analysis, which confirmed the pellicle to be a cellulosic material. Scanning Electron Micrograph showed ultra fine network structure along with cells. The films were tested for its physicomechanical characters, barrier and thermal properties. The films of 25‐μ thickness showed very high tensile strength (41.158 MPa) and elongation of 0.987 mm. The thermal properties of the films were characterized by Differential scanning calorimetry and Thermo gravimetric analysis. The melt peak temperature was found to be 111.65°C. The percentage of weight loss was found to be 20% at 327.86°C. Barrier properties (oxygen transmission rate and water vapor transmission rate), indicated a high oxygen barrier but low water barrier. This is the first report on the barrier properties of bacterial cellulose from Gluconacetobacter sp. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Physical properties of silk fibroin/chitosan blend films

Silk fibroin/chitosan blend films were examined through IR spectroscopy to determine the conformational changes of silk fibroin. The effects of the fibroin/chitosan blend ratios (chitosan content) on the physical and mechanical properties were investigated to discover the feasibility of using these films as biomedical materials such as artificial skin and wound dressing. The mechanical properties of the blend films containing 10–40% chitosan were found to be excellent. The tensile strength, breaking elongation, and Young's modulus were affected by the chitosan contents of the blend films, which were also related to the density and degree of swelling. The coefficient of water vapor permeability of the blend films increased linearly with the chitosan content, and the values of 1000–2000 g m^?2 day^?1 were comparable to those of commercial wound dressings. Silk fibroin/chitosan blend films had good oxygen and water vapor permeabilities, making them useful as biomaterials. In particular, the blend film containing 40–50% chitosan showed very high oxygen permeability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 928–934, 2001     

Oxygen barrier and enthalpy of melting of multilayer EVOH films after pressure‐assisted thermal processing and during storage

Pressure‐assisted thermal processing (PATP) is an advanced thermal process involving application of elevated pressures above 600 MPa on a preheated food for a holding time of 3 to 5 min, causing the volumetric temperature of food to increase above 100°C, to inactivate bacterial spores and enzymes. This study evaluated the influence of PATP on two state‐of‐the‐art multilayer EVOH films. Flexible pouches containing water as the food simulant were made from the two films and processed at 680 MPa for 3 min at 105°C and 680 MPa for 5 min at 100°C. Each film was investigated for its oxygen transmission rates (OTRs), melting temperature (T_m), enthalpy of melting (ΔH), and overall crystallinity before (control) and after processing. The changes in OTRs and total ΔH of the two films were also analyzed during a storage period of 240 days in ambient conditions after processing. Results showed a significant (P < 0.05) increase in the OTRs of the two films after PATP. However, PATP did not cause a significant (P > 0.05) change in the T_m and ΔH of the two films. The overall crystallinity of film A decreased, but improved slightly for film B after PATP. A recovery in the OTRs of the two films occurred during storage. The films also showed changes in the total ΔH measured during the storage period, which was used to explain the changes in the oxygen barrier properties. The OTR of both films remained below 2 cc/m² day, which is required in packaging applications for shelf‐stable foods with a 1‐year shelf life. This work demonstrates the advantages of using multilayer films containing EVOH as the barrier layer in PATP applications to produce shelf‐stable foods. This work also highlights the advantage of, DSC analysis for studying the physical ageing of polymers during storage. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of polypropylene/octadecane composite films and their use in the packaging of cherry tomatoes

Polypropylene (PP)/octadecane (OD) composite films were prepared via twin‐screw extrusion, and their chemical, morphological, thermal, and surface properties and oxygen and water vapor permeabilities were analyzed as functions of the OD content and temperature. OD was dispersed well in the PP matrix, and two phases (i.e., the PP and OD portions) were present in the PP/OD composite films. When the temperature was increased from 10 to 30 °C, both the oxygen transmittance rate and the water vapor transmittance rate of the PP/OD composite films increased sharply because of the influence of the OD content. These results were related to the temperature‐dependent changes in the morphological structure, such as changes in the the tortuous paths and crystallinity in the composite films because of the addition of OD. In the storage test, the PP/OD (83:17) composite films continuously controlled the gas concentration of the headspace and protected against environmental factors; this reduced the enzymatic activity and led to higher quality cherry tomatoes compared to the case when the pure PP and MP33000 films were used. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44087.     

Thermal and barrier properties of EVOH/EFG nanocomposite films for packaging applications: Effect of the mixing method

Ethylene‐vinyl alcohol copolymer (EVOH)/exfoliated graphite (EFG) nanocomposite films were prepared by precoating EFG on the EVOH surface and conducting a successive melt‐extrusion process. Their physical properties were strongly dependent on the EFG content and the mixing method, which strongly affected the morphology and surface properties of the nanocomposite films. The hydrophobicity and water resistance property of EVOH increased by incorporating hydrophobic EFG and their effects were more pronounced in the precoating method, which is related to good dispersion of EFG in EVOH and an enhanced crystalline structure. The incorporation of EFG into EVOH by the precoating method more effectively diminished the dependence of the relative humidity on the oxygen transmission rate of pure EVOH and increased the oxygen barrier properties of EVOH at a high relative humidity. The incorporation of EFG into EVOH by the precoating method also induced relatively more enhanced thermal stability. These results suggest the feasibility of the application of moisture‐sensitive EVOH resin for food packaging films. POLYM. COMPOS., 37:1744–1753, 2016. © 2014 Society of Plastics Engineers     

Effect of gamma irradiation on the oxygen barrier properties in ethyl-vinyl acetate/ethylene-vinyl alcohol/ethyl-vinyl acetate multilayer film

The potential changes of single-use plastic materials (EVA/EVOH/EVA multilayer film in this study) used in biopharmaceutical and food-packaging industries are investigated after several gamma irradiation doses: 30, 50, 115, and 270 kGy, and for nonsterilized samples (0 kGy) from a point of view of mechanical properties, thermal properties and permeability properties. Tensile tests, differential scanning calorimetry (DSC), oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) are performed on the multilayer film. For irradiation doses below 50 kGy, thermal and water vapor barrier properties are not altered. For higher doses (50 to 270 kGy), mechanical, thermal and water vapor barrier properties are slightly altered whereas oxygen barrier property decreases from 13 to 27 cm³.m⁻².day⁻¹. This slight change is shown not to happen due to chain entanglement or chain mobility loss in the amorphous phase of the different polymers. It rather comes from a change of the chemical environment of the EVOH layer.     

Micromorphology,mechanical, crystallization and permeability properties analysis of HA/PBAT/PLA (HA,hydroxyapatite; PBAT,poly(butylene adipate‐co‐butylene terephthalate); PLA,polylactide) degradability packaging films

In this study, the self‐made nano‐hydroxyapatite (HA) and poly(butylene adipate‐co‐butylene terephthalate) copolyesters (PBAT) were used as fillers, and composite films of HA/PLA (PLA, polylactide) and HA/PBAT/PLA systems were prepared. The micromorphology, mechanical properties, thermal properties, crystallinity, water vapor permeability and oxygen permeability of the composite films were studied. The results show that the self‐made HA has a porous rod‐like structure with a size of 30–50 nm. PBAT was dispersed uniformly in the HA/PLA matrix in the form of spherical particles and formed many pores and holes. The tensile strength, elongation at break and modulus of elasticity of HA/PLA composite films were increased by adding 10 wt% PBAT. The addition of HA and PBAT played a synergistic function in improving the crystallinity of the composite films. The water vapor and oxygen permeabilities of HA/PLA and HA/10%PBAT/PLA composite films can be regulated by adjusting the amount of HA. The results of this study indicate that composite films with higher water vapor and oxygen permeabilities exhibit great potential for applications in green packaging and fresh‐keeping packaging. © 2019 Society of Chemical Industry     

新型EVOH/PE⁃RT合金包覆PE⁃RT双层阻氧管的制备及性能研究

针对市场上常见的阻氧管存在难以热熔回收再用的问题,制备了新型乙烯?乙烯醇共聚物（EVOH）/耐热聚乙烯（PE?RT）合金包覆PE?RT双层阻氧管,其内层工作管为PE?RT材质,外层为EVOH/PE?RT合金阻隔材料;研究了EVOH和相容剂含量对EVOH/PE?RT合金阻隔膜阻氧性能的影响,并对新型双层阻氧管的氧气透过量和热熔回收情况以及新型双层阻氧管回收料的力学性能进行了测试。结果表明,EVOH/PE?RT合金阻隔膜的氧气透过量随EVOH含量的增加而降低,随相容剂含量的增加而上升;含30 %（质量分数,下同）EVOH、64 % PE?RT和6 %相容剂的新型双层阻氧管的氧气透过量接近市售3层、5层阻氧管,并且能够实现热熔回收,回收料具有较好的力学性能。     

Linking morphology changes to barrier properties of polymeric packaging for microwave‐assisted thermal sterilized food

It is a priority to develop polymeric packaging that can withstand microwave‐assisted thermal sterilization (MATS) and maintain the quality of low‐acid foods during long‐term storage. In this study, we explored changes in the morphology of pouch films with two multi‐layer structures. The films are based on barrier layers of metal oxide‐coated poly(ethylene terephthalate) (PET) (film A) and ethylene vinyl alcohol (EVOH) (film B). A 8‐oz model food in pouches was processed with MATS (F₀ = 9.0 min) and stored at 23, 35 and 45 °C for up to 12 months. Findings reveal that the oxygen barrier of film A was influenced by the coating and crystallinity of PET. The oxygen barrier of film B was primarily affected by the moisture content of the EVOH polymer. Results also show that changes in barrier properties depended on storage temperature. Recrystallization in polymer might be an important morphological change that occurs during storages. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45481.     

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 and water vapor gas barrier poly(ethylene naphthalate) films by deposition of SiOx plasma polymers from mixture of tetramethoxysilane and oxygen

SiO_x films were deposited from a mixture of tetramethoxysilane (TMOS) and oxygen on poly(ethylene 2,6‐naphthalate) film using ion‐assisted plasma polymerization technique (Method II) and conventional plasma polymerization technique (Method I), and were compared in chemical composition and gas barrier properties. Methods I and II were different in electrical circuit between electrodes (anode and cathode) and electric power supply. In Method I, the anode electrode was grounded, and the cathode electrode was coupled to the discharge power supply. In Method II, the anode electrode was connected with the discharge power supply, and the cathode electrode was grounded. There was not large difference in SiO_x deposition rate between the plasma polymerizations by Methods I and II. Plasma polymers deposited from TMOS/O₂ mixtures by Method II possessed smaller C/Si and O/Si atomic ratios than those deposited by Method I and showed advantage in gas barrier properties. The oxygen and water vapor permeation rates were 0.08–0.13 cm³ m^?2 day^?1 atm^?1 at 30°C at 90% RH and 0.244–0.276 g m^?2 day^?1 at 40°C at 90% RH, respectively. From these results, it can be concluded that the ion‐assisted plasma polymerization is a useful technique for deposition of gas barrier SiO_x thin films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 915–925, 2007     

The effect of relative humidity gradient on water vapor permeance of lipid and lipid-hydrocolloid bilayer films

The water vapor (WV) permeance of lipid and lipid-hydrocolloid films exposed to relative humidity (RH) gradients of 100–0%, 100–50%, 100–65% and 100–80% RH were determined. The lipids used were beeswax (BW) or a blend of BW and acetylated monoglycerides (AG). Hydrocolloids used were methylcellulose, carboxymethylcellulose or ethylcellulose (EC). All films, except those containing EC, exhibited increased water vapor permeance as the RH gradient was reduced by raising the low-end RH. This increase in permeance was apparently caused by hydration and swelling across the entire film thickness, thus facilitating water movement through the film. Because of its hydrophobicity, EC likely lessened this swelling. Knowledge of the WV properties of edible films at relatively small gradients in the upper half of the RH spectrum, such as those used in this study, is useful because these conditions are far more common to foods than are the 100–0% gradients that are often used when evaluating films. Even though the WV permeance of BW and BW/AG films increased greatly at the 100–80% RH gradient, as compared to gradients ranging from 100–65% to 100–0%, they still possess WV barrier properties sufficient to be useful for foods.