Suppression of radiation‐induced oxidation of polymers by sputtered silicon oxide coating

Oxygen barrier coating on polymers was attempted to obtain polymeric composite materials with improved radiation resistance. Silicon oxide (SiO_1.6) films ranging from 120 to 240 nm thick were formed on polypropylene (PP) and polyethylene (PE) by radio frequency (RF) magnetron sputtering. Oxygen permeability after SiO_1.6 deposition was reduced significantly in all samples studied, indicating that silicon oxide is a useful gas barrier. The oxygen permeability coefficient of deposited films for PP was 1.7–2.2 × 10^?14 cm³‐cm/cm²/s/cmHg and that for PE was 2.8–4.8 × 10^?13 cm³‐cm/cm²/s/cmHg. We studied the effect of such films on the radiation resistance of polymers in the presence of oxygen by microscopic infrared (IR) absorption spectroscopy. Silicon oxide films 180 nm thick were deposited on the surfaces of PP and PE, and the formation of carbonyl groups after irradiation in air was measured as a function of depth from the surface. Results compared with those for uncoated PE and PP showed that the radiation‐induced polymer oxidation is dramatically suppressed by silicon oxide coating. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 186–190, 2002     

聚乙烯醇/淀粉/凤仙透骨草提取物复合膜制备及性能

以聚乙烯醇(Polyvinyl alcohol,PVA)、淀粉(Starch,ST)为原料,凤仙透骨草提取物(Impatiens balsamina extract,IBE)为抗菌剂,通过共混法制备抗菌复合膜,通过FTIR、XRD、SEM和热重分析对复合膜的形貌和结构进行表征及对力学、光学、阻隔、抑菌等性能测试分析。结果表明,IBE与PVA/ST基膜复合良好,制备的PVA/ST/IBE抗菌复合膜对大肠杆菌、白色葡萄球菌和枯草杆菌具有良好的抑菌作用,抑菌性能随着IBE含量的增加而逐渐提高；同时具有良好的力学强度,IBE添加量为12.5 mL的复合膜拉伸强度达到22.97±0.68 MPa,断裂伸长率相比PVA/ST基膜提升了79.22%；透明度有所下降,透光率下降了11.90%；氧气阻隔性能良好,氧气透过系数为1.771±0.196×10_-12 ^cm₃^.cm/(cm₂^.s.Pa),在环保包装、食品保鲜等领域具有广阔的应用前景。     

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.     

Fabrication and characteristics of graphene oxide/nanocellulose fiber/poly(vinyl alcohol) film

Poly(vinyl alcohol) (PVA), PVA/nanocellulose fiber (CNF), and PVA/CNF/graphene oxide (GO) films were prepared simply by casting stable aqueous mixed solutions. FTIR investigation indicated that hydrogen bonding existed between the interface of GO and PVA‐CNF. Scanning electron microscopy and X‐ray diffraction analysis showed that GO was uniformly dispersed in PVA‐CNF matrix. Introducing CNF into PVA caused a significant improvement in tensile strength, and further incorporating GO into PVA/CNF matrix led to a further increase. The tensile strength of the neat PVA film, PVA/CNF composite, and PVA/CNF/GO film (0.6 wt % GO) was 43, 69, and 80 MPa, respectively. Moreover, when incorporating 8 wt % CNF into PVA matrix, O₂ permeability and water absorption decreased from 13.36 to 11.66 cm³/m²/day and from 164.2% to 98.8%, respectively. Further adding 0.6 wt % GO into PVA/CNF matrix resulted in a further decrease of permeability and water absorption to 3.19 cm³/m²/day and 91.2%, respectively. Furthermore, for all composite samples, the transmittance of visible light was higher than 67% at 800 nm. CNF and GO‐reinforced PVA with high mechanical and barrier properties are potential candidates for packaging industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45345.     

Cellulose nanofibrils in biobased multilayer films for food packaging

The aim of this study was to evaluate a thin, TEMPO‐oxidized (2,2,6,6‐tetramethylpiperidine‐1‐oxyl–mediated oxidation) cellulose nanofibril (CNF) coating as a barrier layer in multilayer packaging films together with biobased polyethylenes. The purpose was also to explore the possible interactions between food products and the biobased films, and to evaluate the feasibility of these films for packaging of dry foods. CNF provided the biobased multilayer films with an oxygen barrier suitable for both demanding food products and modified atmosphere packaging (MAP). The MAP pouches made of these multilayer films retained their atmosphere and shape and protected ground hazelnuts from further oxidation for the storage time used in this study. However, irradiation used to sterilize packed foods and aroma compounds from clove in particular impaired the oxygen barrier property of the CNF layer, while the water vapor barrier property of the multilayer films remained unaffected. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44830.     

Development and compatibility assessment of new composite film based on sugar beet pulp and polyvinyl alcohol intended for packaging applications

In this study, interaction and compatibility between sugar‐beet pulp (SBP) and polyvinyl alcohol (PVA) in blend films was assessed. Film‐forming dispersions of different ratios of SBP to PVA (100/0, 75/25, 50/50, and 25/75) were cast at room temperature. The effects of adding PVA to SBP on the resulting film's physical, mechanical and barrier properties and thermal stability were investigated. X‐ray diffraction and environmental scanning electron microscopy (ESEM) were used to characterize the structure and morphology of the composites. When PVA was also added to the composite films, the films became softer, less rigid and more stretchable than pure SBP films. The addition of PVA gave significantly greater elongation at break (12.45%) and lower water vapor permeability (1.55 × 10^?10 g s^?1 m^?1 Pa^?1), but tensile strength did not markedly change, remaining around 59.68 MPa. Thermogravimetric analysis also showed that SBP/PVA film had better thermal stability than SBP film. The ESEM results showed that the compatibility of SBP50/PVA50 was better than those of other composite films. These results suggest that when taking all the studied variables into account, composite films formulated with 50% PVA are most suitable for various packaging applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41354.     

Roll-to-roll processable MXene-rGO-PVA composite films with enhanced mechanical properties and environmental stability for electromagnetic interference shielding

MXene films promise potential electromagnetic interference (EMI) shielding materials, but poor scalable processability, environmental instability, and weak mechanical properties severely restrict their applications. Herein, we engineer the large-area, high-performance, and compact nacre-like MXene-based composite films through cooperative co-assembly of Ti₃C₂T_X MXene and reduced graphene oxide (rGO) in the presence of polyvinyl alcohol (PVA). The resulting MXene-rGO-PVA composite films benefit from enhanced bonding strength and extra chain bridging effect of linear PVA molecules enriched with hydroxyl groups. Therefore, the composite film achieves high tensile strength (～238 MPa) and toughness (～1.72 MJ m^?3) while having high conductivity of ～32 S cm^?1. A significant EMI shielding effectiveness (41.35 dB) is also demonstrated, with an excellent absolute shielding effectiveness of ～20,200 dB cm² g^?1 at only 12-μm thickness. Moreover, due to the synergistic effect of multiple components, the composite films maintain a stable EMI shielding performance in harsh environments (sonication, hot/cold annealing, and acid solution) with mechanical properties that fluctuate only within 10% compared to the original film. More importantly, commercial polyethylene terephthalate release liner can be applied for the film coating, facilitating continuous roll-to-roll production of large-area films and future applications.     

Preparation and properties of poly(urethane acrylate) (PUA) and tetrapod ZnO whisker (TZnO‐W) composite films

Tetrapod zinc oxide whiskers (TZnO‐Ws) were successfully synthesized via a thermal oxidation method and confirmed using Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy. A series of poly(urethane acrylate) (PUA)/TZnO‐W composite films with various TZnO‐W contents were prepared via a UV curing method and their physical properties were investigated to understand their possible use as packaging materials. The morphological, thermal, mechanical, antibacterial and barrier properties of the PUA/TZnO‐W composite films were interpreted as a function of TZnO‐W content. The thermal stability, barrier properties and antibacterial properties of the composite films, which were strongly dependent upon their chemical and morphological structure, were enhanced as the TZnO‐W content increased. The oxygen transmission rate and water vapor transmission rate decreased from 614 to 161 cm³ m^?2 per day and 28.70 to 28.16 g m^?2 per day, respectively. However, the mechanical strength of the films decreased due to the low interfacial interaction and poor dispersion with high TZnO‐W loading. The enhanced barrier properties and good antibacterial properties of the PUA/TZnO‐W composite films indicate that these materials are potentially suitable for many packaging applications. However, further studies are needed to increase the compatibility of polymer matrix and filler. © 2012 Society of Chemical Industry     

Multifunctional and pH-responsive dialdehyde cellulose/polyvinyl alcohol composite film reinforced with curcumin

The rational design of food packaging films with good antimicrobial activity, antioxidant activity, and monitorability is of great importance in intelligent packaging. In this study, an active composite film was prepared by adding curcumin to a dialdehyde cellulose (DAC)/polyvinyl alcohol (PVA) matrix. It was found that the Cur/DAC/PVA composite film exhibited optimal tensile strength at 30°C. The tensile strength of the composite film control PVA/DAC film was observed to increase by 176% due to the affection of hydrogen bonding. Under the influence of curcumin, the UV barrier property and antioxidant activity of the composite film were significantly increased, and the ABTS⁺• was removed by 0.5Cur/DAC/PVA up to 88% at low curcumin content. The water solubility and water vapor permeability were both reduced to some degree. It was also observed that composite film displayed an inhibitory effect on the growth of Staphylococcus aureus bacteria. Meanwhile, the Ritger and Peppas release model was used to study the release control capability of curcumin. Furthermore, the Cur/DAC/PVA composite film demonstrated excellent color response to pH, which it they could be used for intelligent packaging with real-time visual monitoring.     

Enhanced oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) blended with poly(acrylic acid) for packaging applications

To enhance the oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) (PVA) and expand its food packaging applicability, five crosslinked poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend films were prepared via esterification reactions between hydroxyl groups in PVA and carboxylic acid groups in PAA. The physical characteristics of the blends, including the thermal, barrier, mechanical and optical properties, were investigated as a function of PAA ratio. With increasing PAA content, the crosslinking density was significantly increased, resulting in changes in the chemical structure, morphology and crystallinity of the films. The oxygen transmission rate of pure PVA decreased from 5.91 to 1.59 cc m^?1 day^?1 with increasing PAA ratio. The water resistance, too, increased remarkably. All the blend films showed good optical transparency. The physical properties of the blend films were strongly correlated with the chemical structure and morphology changes, which varied with the PAA content. © 2016 Society of Chemical Industry     

食品软包装用透明高阻隔涂料：PVA涂料研究进展

聚乙烯醇（PVA）因其良好的透明性和成膜性以及优异的氧气和有机溶剂阻隔性，可用于透明、易回收、环境友好型的食品高阻隔软包装材料。但因其涂层对湿度敏感性差且不具备水蒸气阻隔性能而制约其发展。针对这一问题，目前主要有两种解决方法：一种是PVA化学交联，PVA能进行多元醇的酯化、醚化、缩醛化等化学反应；另一种是制备PVA-纳米复合涂料，PVA与纳米层状材料如蒙脱土（MMT）以及氧化石墨烯（GO）复合涂料的研究已取得较大进展。为此，分别从PVA的阻隔性及其影响因素、化学交联PVA涂料以及PVA-纳米复合涂料的最新研究进展进行了综述，分析了改性PVA涂料面临的问题，展望其未来研究方向。     

Biodegradable poly(vinyl alcohol)-based nanocomposite film reinforced with organophilic layered double hydroxides with potential packaging application

The continuously increasing plastic wastes and diminishing fossil resources have attracted global attention into research and development of biodegradable packaging materials. In the present study, organophilic layered double hydroxides (OLDH) intercalated with aliphatic long-chain molecules as reinforcing agents were incorporated into biodegradable poly(vinyl alcohol) (PVA) matrix by a solution casting method. FTIR, XRD and SEM were performed to analyze the structure of PVA/OLDH films. The OLDH nanosheets were well-dispersed in PVA matrix and formed strong interfacial interactions with the PVA chains, leading to remarkable improvements of optical property, mechanical performance, water vapor barrier property and thermal stability. At a loading of only 2% OLDH in PVA, we observed ~67% decrease in haze and ~66% increment in tensile strength in the composite film compared with pure PVA film. Furthermore, a 24.22% decrease in water vapor permeability (enhancement in water vapor barrier property) due to the addition of 0.5 wt% OLDH and enhanced thermal stability could be observed. These results revealed that the overall performance could be improved by introducing OLDH at very low loadings and that the PVA nanocomposite films have potential for future application in packaging films. Therefore, the use of high-performance PVA/OLDH nanocomposite films can evidently promote the application of biodegradable PVA materials in packaging industry.     

Nano boron nitride laminated poly(ethyl methacrylate)/poly(vinyl alcohol) composite films imprinted with silver nanoparticles as gas barrier and bacteria resistant packaging materials

Herein, nano boron nitride (BN) laminated poly(ethyl methacrylate) (PEMA)/poly(vinyl alcohol) (PVA) nanocomposite films are fabricated by using a simple in situ polymerization technique with incorporation of silver nanoparticles (Ag NPs). Structural investigations of PEMA/PVA/Ag@BN nanocomposite thin films are carried out by Fourier-transform infrared spectroscopy, dynamic light scattering, X-ray diffraction analysis, ¹H nuclear magnetic resonance, ¹³C nuclear magnetic resonance, and mass spectrometry. The change in morphology of PEMA/PVA matrix due to the reinforcement of BN platelets are identified by electron microscopic studies. The unique tortuous paths are achieved by the dispersion of BN platelets by which gas penetration is restricted with enhancing the barrier properties of the material by 6.5 folds at 5 wt% BN content as compared with neat PEMA/PVA. Acid and alkali resistant along with biodegradability behavior of as-synthesized nanocomposites are studied. From limiting oxygen index (LOI) results, it is found that the prepared materials are fire retardant in nature owing to effective reinforcement of BN layers. Antibacterial activities of PEMA/PVA/Ag@BN nanocomposite are studied by Xanthomonas citri or axonopodis pv. Citri, Escherichia coli, and Xanthomonas oryzae pv. Oryzae because of Ag NPs reinforcement. The substantial improvements in gas barrier, fire retardant, and antibacterial properties enable the materials for packaging application.     

Surface modification of atmospheric plasma activated BOPP by immobilizing chitosan

Summary Chitosan was immobilized onto plasma activated biaxially oriented polypropylene (BOPP) films aimed at producing antimicrobially active barrier film for food packaging applications. 1% chitosan dissolved into 0.1 M acetic acid was mixed with 0.1% glutaraldehyde (cross-linking agent) and applied onto N₂-plasma + NH₃ activated BOPP film. Amount of immobilized chitosan was 1.8 g/m². Films had strong antimicrobial activity against both Bacillus subtilis and Escherichia coli and they reduced the oxygen transmission rate (OTR) measured in dry conditions from 1500 down to 27 cm³/(m²·24 h). Migration tests for determining the total amounts of substances migrating into food simulants (3% acetic acid, 95% ethanol and iso-octane) indicated, that chitosan coating was permanently immobilized onto BOPP without any leaching (total migration < 2 mg/dm²), thus it met the requirements stipulated in Directive 2002/72/EC relating to plastic materials and articles intended to come into contact with foodstuffs. The results suggest that chitosan treated BOPP films may be exploited in various food packaging applications requiring high oxygen barrier and/or antimicrobially active packaging materials.     

Preparation of Starch/PVA/CaCO3 Nanobiocomposite Films: Study of Fire Retardant,Thermal Resistant,Gas Barrier and Biodegradable Properties

Starch/PVA/CaCO₃ nanobiocomposite films were prepared by the solution casting method. The prepared nanobiocomposite films were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) methods. The fire retardant, tensile strength and thermal properties of nanobiocomposite films were enhanced with increasing percentage of CaCO₃. When the concentration of nano-CaCO3 was increased, the oxygen permeability of starch/PVA/CaCO₃ was reduced. The increase in fire retardant and oxygen barrier properties along with improvement in thermal and tensile properties of nanobiocomposite may enable the material suitable for packaging application.     

Packaging‐related properties of alkyd‐coated,wax‐coated,and buffered chitosan and whey protein films

Packaging‐related properties of coated films of chitosan–acetic acid salt and whey protein concentrate (WPC) were studied. Chitosan (84.7% degree of deacetylation) and WPC (65–67% protein) were solution cast to films. These films are potential oxygen barriers for use in packaging. Coatings of wax or alkyds were used to enhance the water‐barrier properties. The packaging‐related properties of chitosan films treated in a buffering solution, with a pH of 7.8, were also investigated. The coated films were characterized with respect to Cobb absorbency, overall migration to water, water vapor transmission rate, and oxygen permeability. The creasability and bending toughness were determined. The wax was a more efficient barrier to liquid water and 90–95% relative humidity than the alkyd. However, the alkyd‐coated material had superior packaging‐converting properties. The alkyd‐coated WPC and chitosan–salt films were readily folded through 180° without any visible cracks or delamination. The overall migration from the alkyd‐coated materials was below the safety limit, provided the coat weight was higher than 7.5 mg/cm² on WPC and 2.1 mg/cm² on chitosan–salt. The barrier properties of chitosan film under moist conditions were improved by the buffer treatment. However, the buffering also resulted in shrinkage of the film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 60–67, 2004     

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。     

High oxygen barrier materials from paper to regenerated cellulose films

A transparent, bendable, high oxygen barrier cellulose-based film was prepared, which has far better oxygen barrier properties than conventional polyethylene, polypropylene and cellophane materials. A series of regenerated cellulose films (RCs) were prepared from filter paper lacking oxygen barrier properties under different cellulose concentrations and gelation times. It was shown that the cellulose concentration and gel time had a greater effect on the oxygen barrier properties of RCs. When the cellulose concentration was 4 wt% and the gel time was 3 h, the RCs obtained the lowest oxygen permeability coefficient (OPC) down to 2.21 × 10⁻¹⁷ cm³ cm cm⁻² s⁻¹ Pa⁻¹. The films have a tensile strength of 109.5 MPa, an elongation at break of 27.3% and a light transmission rate of 89%. In further, molecular dynamics simulations showed that when the filter paper was converted to RCs, the increase in hydrogen bonding and the decrease in free volume between cellulose chains caused a decrease in the diffusion coefficient of oxygen. As a novel biobased high oxygen barrier material, the film has broad application prospect in packaging and chemical industry.     

The impact of microwave‐assisted thermal sterilization on the morphology,free volume,and gas barrier properties of multilayer polymeric films

Microwave‐assisted thermal sterilization (MATS) is an advanced thermal process that utilizes microwave (MW) energy for in‐package food sterilization. Benefits include much shorter processing times than conventional retort sterilization. This research explores how MATS affects the performance of high‐barrier multilayer polymeric films compared with conventional retort sterilization. The gas barrier, morphological, and free volume packaging properties of these films may influence the shelf‐life of shelf‐stable foods. In this study, we applied X‐ray diffraction (XRD) and positron annihilation lifetime spectroscopy in order to investigate film morphology and free volume characteristics, respectively. Results show that the conventional retort process affected gas barrier properties more than MATS processing did which could be explained by the morphological and free volume changes in the polymeric films. XRD revealed improved crystalline morphology of MW‐treated films in terms of overall crystallinity as compared with retort sterilization. On the other hand, higher free volume increase in MW‐treated films could be explained by the different heating mechanisms involved in MATS and retort sterilization. Overall, the oxygen transmission rate for both films remained below 2 cc/m²‐day after MATS and retort sterilization required for packaging applications for shelf‐stable foods. This work provides the basis for understanding the gas‐barrier changes of multilayer polymeric films after MATS application using Materials Science techniques. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40376.     

Improved ferroelectric properties in KBiFe2O5-polymer composite film

Composite films of KBiFe₂O₅ and PVA were prepared with a varied weight percentage of PVA by spin coating method on platinised silicon wafer. The composite films were characterised for dielectric and ferroelectric properties in comparison to pure KBiFe₂O₅thick film. The frequency dependent permittivity measurement indicated a higher contribution of space charge/interfacial polarization in KBiFe₂O₅ thick film than that in the KBiFe₂O₅ -PVA composite films. The ferroelectric properties in composite films were enhanced due to the reduction in leakage current and they showed well saturated polarization hysteresis loops. The remanent polarization value in KBiFe₂O₅ -PVA composite film (Pr?=?3.7?μC/cm²) was found to be 2.5 times higher than that of the pure KBiFe₂O₅ film (Pr?=?1.45?μC/cm²) and with the increase in PVA percentage, the remanent polarization values also increased. The space charge dominated conduction in pure KBiFe₂O₅ became transformed to field assisted ionic conduction in the KBiFe₂O₅ composite films. The polymeric matrix in KBiFe₂O₅ composites helped in reducing the leakage current of pure KBiFe₂O₅ by four orders of magnitude and further reduced with the increase in the PVA content in the composite. The composite films showed fatigue free polarization even after 10⁸ switching cycles whereas the polarization degradation in KBiFe₂O₅ film was 30% around 10⁸switching cycles.