Synthesis of clay–TiO2 nanocomposite thin films with barrier and photocatalytic properties for food packaging application

In this study, low‐density polyethylene (LDPE) nanocomposite films with two types of nanoparticles, TiO₂ (3 wt %) and Closite 20A (3 and 5 wt %), were prepared using a melt blow extrusion as an industrial method and their properties such as mechanical properties, water vapor, oxygen and carbon dioxide gas barrier, and antimicrobial activity were tested. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) were also performed to determine the degree of dispersion and exfoliation of nanoparticles. Mechanical test indicated that the reinforcement in the presence of the nanocomposites was more than that with their conventional counterparts, and the highest stiffness was achieved in a sample containing 5 wt % clay and 3 wt % TiO₂. Exfoliation of silicate layers and a good dispersion of TiO₂ nanoparticles in LDPE were achieved as confirmed by XRD and TEM. The gas barrier properties were improved after formation of the nanocomposites especially by insertion of 5 wt % of clay nanoparticles as a filler in the LDPE matrix. The photocatalytic effect of the nanocomposite film was carried out by antimicrobial evaluation against Pseudomonas spp. and Rhodotorula mucilaginosa and by ethylene removal test using 8 W ultraviolet (UV) lamps with a constant relative intensity of 1 mW cm^?2. The greatest effects were recorded by combining UVA illumination and active film. It was also proven that the photocatalyst thin film with improved barrier properties prepared by extrusion could be used in horticultural product packaging applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41764.     

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。     

Influence of carboxymethylation on the surface physical–chemical properties of glucuronoxylan and arabinoxylan films

Xylans were carboxymethylated in order to increase their anionic nature and thus tune their surface free energy (SFE) and hydrophilicity, which are of crucial importance in the majority of special applications. Fourier transform infrared spectroscopy and polyelectrolyte titration results confirmed the successful carboxymethylation of the xylan samples. The main aim of this study was to investigate the influences of carboxymethylation of glucuronoxylan and arabinoxylans on the surface physical and chemical properties of the films made from them. Films were prepared by the casting method, and their surface morphologies were analyzed by atomic force microscopy. The surface chemical compositions of the films were investigated using X‐ray photoelectron spectroscopy, and their influences on SFE, i.e., Lifshitz–van der Waals and electron donor and acceptor contributions, were determined using goniometry. The introduction of ～2 mmol/g of carboxyl groups into the glucuronoxylan or arabinoxylan molecular structures had a significant influence on the chemical and physical surface properties of the prepared films. Higher amounts of the carboxyl group present on the films' surfaces and higher surface roughness contributed to a significant increase (by 270%) in the electron donor component of SFE and to 40% improvements in the hydrophilicities of the films' surfaces. POLYM. ENG. SCI., 55:2706–2713, 2015. © 2015 Society of Plastics Engineers     

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.     

Keratin–polyhydroxyalkanoate melt‐compounded composites with improved barrier properties of interest in food packaging applications

Sustainable biocomposite materials based on the combination of polyhydroxyalkanoates with a keratin additive derived from poultry feathers were successfully developed via melt compounding. Suitable dispersions for low loadings of the additive in the biopolymeric matrix were achieved by the melt‐mixing technique. A good physical interaction between the polymeric matrix and the additive was observed by scanning electron microscopy (SEM). Reductions in water, limonene, and oxygen permeability of the pure polymer to less than a half of its initial value for the composite containing 1 wt % of keratin additive were achieved. This composition was also found to exhibit optimum mechanical performance. As a result, these materials offer significant potential in fully renewable packaging applications based on polyhydroxyalkanoates with enhanced barrier performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39947.     

Gas barrier changes and morphological alterations induced by retorting in ethylene vinyl alcohol–based food packaging structures

Ethylene vinyl alcohol (EVOH)–based packaging structures were analyzed in terms of both barrier properties and morphological alterations after a retorting process and as functions of ethylene content. From the results, it was found that the samples do have a substantial decrease in oxygen barrier properties and that the kinetics of recovery strongly depends on the copolymer ethylene fraction. A morphological deterioration was also observed as a result of retorting, particularly for packaging structures composed of EVOH copolymers of low ethylene contents. However, the polymer morphology and barrier properties were restored after a dry thermal treatment of the retorted samples. Interestingly, preannealing of copolymers of low ethylene content rendered them more resistant to the retorting process by means of promoting both a more robust crystallinity and a lower water sorption capacity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2192–2202, 2005     

Exploring the effects of montmorillonite and halloysite nanotubes on mechanical,optical and barrier properties of poly (butylene adipate-co-terephthalate) blown films: Implications for sustainable packaging and food storage

Biodegradable packaging plastics combining good mechanical properties and low gas permeability is required to avoid environmental and food safety concerns. This study explores the impact of montmorillonite (MMT) and halloysite nanotubes (HNT), on the mechanical, optical, and oxygen permeability of blown film poly (butylene adipate-co-terephthalate) (PBAT) composites. The morphology of the films was evaluated by x-ray diffraction (XRD), differential scanning calorimetry and scanning electron microscopy. Good distribution/dispersion of clays is found in the PBAT-MMT films. Besides, there is an increase in the crystallinity of PBAT due to the nucleating effect of HNT. Improvement in the tensile strength and elongation at break in the machine direction is obtained up to a clay content of 1.5 vol%. The incorporation of 1.5 vol% of MMT and 1 vol% of HNT leads to a reduction in the oxygen permeability of the PBAT film by 29% and 38% respectively. Furthermore, the films remain transparent regardless of clay content. Finally, the feasibility of the films for food storage is tested in grapes, obtaining extended shelf life. The favorable mechanical, barrier and optical properties of the biodegradable films, along with the scalable production process, make them attractive for application in the storage and preservation of food products.     

Influence of incorporation of ZnO nanoparticles and biaxial orientation on mechanical and oxygen barrier properties of polypropylene films for food packaging applications

In this work, the effect of zinc oxide (ZnO) concentration and shape on processing and properties of new biaxially oriented polypropylene (BOPP)‐ZnO nanocomposites was studied. The use of spherical nanoparticles and nanorods was expected to differently influence the properties of the final material. Films of isotactic polypropylene prepared with different ZnO incorporation were biaxially oriented under conditions of temperature and strain rate that were similar to those encountered in a commercial film process. Scanning electron microscopy analysis was performed to visualize the dispersion degree of the ZnO nanoparticles in the polymer matrix and to observe the surface and the orientation of the elongated nanoparticles. Furthermore, the prepared ZnO‐BOPP nanocomposites were evaluated for both mechanical and oxygen barrier property enhancement. A good combination of mechanical and oxygen barrier properties was obtained for the ZnO‐BOPP films. This result makes the ZnO‐BOPP nanocomposite a proper material for applications such as food packaging. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of ultrasound on the morphology and properties of polypropylene/inorganic filler composites

The effects of ultrasonic irradiation on the rheology, structure, and properties of PP/inorganic filler composites were studied. Scanning electron microscopy showed that ultrasound increased the orientation degrees of acicular fillers to the flow direction. WAXD indicated that ultrasound vibration induced sheet fillers orient with its surface perpendicular to the direction of the ultrasound vibration. The orderly rearrangements of fillers in the polymer melt induced by ultrasound vibration can reduce the steric hindrances in the flow field and increase the flowability of the PP/inorganic filler composites. The effect of ultrasound on reducing the apparent viscosities is very prominent, especially at lower shear rate. Ultrasound has an even more marked effect on reducing the apparent viscosities of composites containing fillers of larger size. With ultrasound vibration, the mechanical properties of the composites are also improved because of the orientation and uniform dispersion of fillers in the matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1553–1560, 2005     

Effect of ultrasound on extrusion of polypropylene/ethylene–propylene–diene terpolymer blend: Processing and mechanical properties

The effects of ultrasonic irradiation on extrusion processing and mechanical properties of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends are examined. Results show that appropriate irradiation intensity can prominently decrease die pressure and apparent viscosity of the melt, increase output, as well as increase toughness of PP/EPDM blends without harming rigidity. In case the blends are extruded with ultrasonic irradiation twice, the impact strength of the blend rises sharply at 50–100 W ultrasonic intensity, and amounts to more than 900 J/m, 1.5 times as high as that of blend without ultrasonic irradiation. Scanning electron microscopy observation shows that with ultrasonic irradiation, morphology of uniform dispersed EPDM phase and good adhesion between EPDM and PP matrix was formed in PP/EPDM blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3519–3525, 2003     

Nanolayer enhancement of biaxially oriented polypropylene film for increased gas barrier

An order of magnitude improvement in the oxygen barrier of biaxially oriented polypropylene (BOPP) films was achieved using a layer-multiplying, forced assembly process. The improvement was achieved without sacrificing clarity and toughness of the films. Sheets with 33 alternating layers of polypropylene (PP) (17 layers) and poly(?-caprolactone) (PCL) (16 layers) were coextruded using layer-multiplication and two thick PP skins were added to the multilayered core as the last step in the continuous coextrusion process. The sheets were subsequently biaxially oriented to draw ratios from 4 × 4 to 6 × 6. Biaxial orientation at elevated temperature reduced the thickness of the melted PCL layers from the microscale to the nanoscale, which created 2-dimensional confinement for subsequent crystallization of the PCL layers. It was anticipated that the PCL layers would recrystallize as highly oriented, in-plane lamellae that would resemble single crystals. However, the PCL lamellae were oriented perpendicular to the film surface, which actually facilitated oxygen permeation through the PCL layers and increased the oxygen permeability of the oriented films. Crystallization as on-edge lamellae was attributed to nucleation by the polypropylene surface. However, the surface nucleation was prevented by inserting buffer polystyrene (PS) layers in between the PCL and PP layers. In this case, the PCL lamellae were oriented in-plane. With the very high aspect ratio lamellar crystals oriented perpendicular to the flux direction, the permeation pathway of oxygen became very tortuous and the oxygen barrier was significantly improved.     

Gas permeability and mechanical properties of polystyrene–polypropylene blends

Permeability to water vapor and oxygen, elastic modulus, tensile strength, and impact strength of polystyrene–polypropylene and high-impact polystyrene–polypropylene blends were determined as functions of blend composition and morphology. Three types of styrene–butadiene block copolymers were tested as compatibilizers and found to improve mechanical properties of blends. The experimental data on permeability and modulus were compared with the predictions for the studied binary and ternary blends. The predictive scheme employs a two-parameter equivalent box model and the data on phase continuity of constituents calculated using general equations derived from percolation theory. Blends with decreased permeability and plausible mechanical properties were proposed with regard to intended applications in food packaging. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2615–2623, 1998     

Kinetics of diffusion of a pollutant from a recycled polymer through a functional barrier: Recycling plastics for food packaging

Recycled polymers containing a pollutant can be used for food packaging if the food is protected by a functional barrier made of virgin polymer. The mathematical treatment of the diffusion of pollutant through the packaging is established when the diffusivity is constant and when there is no transfer through the packaging-food interface. A functional barrier not only reduces but also delays migration during a lag phase. An increase in the relative thickness of the functional barrier dramatically increases its efficiency. Practical examples are presented. The difficulties of control of migration through functional barriers are pointed out. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 597–607, 1997     

Influence of melt processing on biodegradable nisin‐PBAT films intended for active food packaging applications

Biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) films incorporated with different levels of the antimicrobial peptide nisin were developed by melt processing. Structural, morphological, thermal, mechanical, and antimicrobial properties of the films were determined. The X‐ray diffraction patterns exhibited decreasing levels of intensity at 2θ values as the concentration of nisin increased. Scanning electron microscopy showed a heterogeneous morphology when higher amounts of nisin were incorporated. The antimicrobial films tested presented no significant differences in the melting temperature (123–125°C), and the crystallization temperature ranged from 69 to 75°C. The addition of nisin caused no significant modification in tensile strength values. However, results of Young's modulus and deformation at break differed significantly among samples. Active films demonstrated inhibition against the Gram‐positive bacterium Listeria monocytogenes. These results demonstrated that PBAT/nisin films produced by melt processing present a great potential for use as active food packaging materials aiming enhanced food safety. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43212.     

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.     

LDPE‐based blends and films stabilized with nonreleasing polymeric antioxidants for safer food packaging

Several novel random copolymers of ethylene and 1‐olefin counits bearing a highly efficient phenolic antioxidant moiety placed at different distances from the polymerizable double bond were prepared in the presence of a metallocene catalyst. These copolymers were melt‐blended with an antioxidant‐free LDPE in an internal batch mixer to obtain innovative materials containing nonreleasing polymeric antioxidants suitable for safer food packaging applications. Blends and films, obtained by compression molding, were tested for their thermal and thermo‐oxidative stability by thermogravimetric analysis both in dynamic and isothermal conditions. Films containing the macromolecular antioxidants showed a longer induction time before O₂ uptake starts and, consequently, a higher degradation temperature than neat LDPE or LDPE containing a low molecular weight commercial additive. Aging tests demonstrated that the new polymeric antioxidants also exert a valid protection against photo‐oxidation. Eventually, migration tests demonstrated the absence of any trace of products containing the antioxidant moiety when the films were kept in contact with a food simulant. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PLA抗菌/抗氧化活性包装薄膜在食品中的应用及其安全性评价

综述了聚乳酸（PLA）抗菌/抗氧化活性薄膜在食品包装中的应用及其安全性评价的研究进展,主要从PLA抗菌/抗氧化活性薄膜及其在食品包装中的应用和PLA材料的安全性评价3个方面进行了归纳总结,旨在为PLA抗菌/抗氧化活性包装薄膜研究提供参考。     

Preparation and properties of poly(propylene carbonate) and nanosized ZnO composite films for packaging applications

A series of polypropylene carbonate (PPC)/ZnO nanocomposite films with different ZnO contents were prepared via a solution blending method. The morphological structures, thermal properties, oxygen permeability, water sorption, and antibacterial properties of the films were investigated as a function of ZnO concentration. While all of the composite films with less than 5 wt % ZnO exhibited good dispersion of ZnO in the PPC matrix, FTIR and SEM results revealed that solution blending did not lead to a strong interaction between PPC and unmodified ZnO. As such, poor dispersion was induced in the composite films with a high ZnO content. By incorporating inorganic ZnO filler nanoparticles, the diffusion coefficient, water uptake in equilibrium, and oxygen permeability decreased as the content of ZnO increased. The PPC/ZnO nanocomposite films also displayed a good inhibitory effect on the growth of bacteria in the antimicrobial analysis. The enhancement in the physical properties achieved by incorporating ZnO is advantageous in packaging applications, where antimicrobial and environmental‐friendly properties, as well as good water and oxygen barrier characteristics are required. Furthermore, UV light below ～ 350 nm can be efficiently absorbed by incorporating ZnO nanoparticles into a PPC matrix. ZnO nanoparticles can also improve the weatherability of a PPC film. In future research, the compatibility and dispersion of the PPC matrix polymer and the inorganic ZnO filler nanoparticles should be increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Development and oxygen scavenging performance of three‐layer active PET films for food packaging

Polymeric active materials represent an innovative food packaging concept that has been introduced to improve the quality of foods and to enhance their shelf life. In this article, the effect of the inclusion of an oxygen scavenger in a polymeric matrix, realizing multilayer active polyester films by coextrusion process, is analyzed. In particular, three layer active films, at different mass ratios of the layers, were produced to form symmetrical "ABA" structures comprising polyethylene terephthalate (PET) with a polymeric oxygen scavenger (OS) as core layer and pure PET as external layers. Oxygen scavenging tests conducted on the multilayer active structures have pointed out the role of the relative layer thickness in controlling the scavenging capacity, the activity time and the oxygen absorption rate. A modeling of the scavenging phenomena, which combines a quasi steady‐state distribution in the skin layers with a flat profile of O₂ content in the active core layer, can explain the experimentally observed oxygen absorption rate at short times. Moreover, steady state oxygen transport measurements, performed when the scavenger reactive capacity is exhausted, have shown that the presence of the active phase slightly reduces the O₂ permeability, compared with the neat PET. The effect, which progressively increases with the amount of active phase in the film formulation, was related to the different morphological state developed on processing. Finally, preliminary shelf life tests on fresh‐cut untreated apples suggest that the developed three layer active films have a significant potential in the shelf‐life extension of oxygen sensitive food products. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41465.     

Influence of stretching ratio and salt concentration on the porosity of polypropylene films containing sodium chloride particles

The incorporation of salt in a polymer matrix could potentially achieve a humidity‐regulating film system of high porosity for packaging applications. In this study, sodium chloride (NaCl) powder was used as a model substance for humidity‐regulating fillers in polypropylene films. A polypropylene homopolymer was extrusion‐blended with NaCl at concentrations of 0.03, 0.06, 0.12, and 0.24 g NaCl·g film^–1. Films were produced and were subsequently oriented mono and biaxially. At stretching ratios (SRs) of between 2 and 25 a porosity of 20% v/v to 50% v/v was achieved. The porosity positively correlated with the SR. An empirical model based on ellipsoids that approximated the correlation between the SR and the porosity was developed. This correlation offers a basis for further studies on other salt‐polymer systems that have undergone differing orientation processes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013