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     

Recycling of multilayer packaging using a reversible cross-linking adhesive

Plastic-based multilayer packaging has an important function on the packaging market, but is currently not recyclable as the polymer layers used are usually thermodynamically immiscible. This work therefore follows the approach to prepare separable multilayer packaging using a packaging adhesive modified with thermally unstable adducts, and proposes a corresponding recycling process. For this purpose, typical multilayer structures (polyethylene (PE)// polyethylene terephtalate (PET), PET//aluminum, and PE//aluminum) were prepared by curing furan-/maleimide-functionalized polyurethane (PU)-prepolymers with a three-functional cross-linking agent. Adhesions of up to over 3N per 15 mm test specimen were measured or substrate failures of PET films were observed. However, heating in dimethylsulfoxide, the retro-Diels–Alder reaction takes place and the cross-linked adhesive turns thermoplastic and dissolves in the solvent. Thus, the laminate separates and the pure PE, PET, and aluminum foils can be recovered without any PU residue.     

Mass transfer study of chlorine dioxide gas through polymeric packaging materials

The mass transfer profile (permeability, diffusion, and solubility coefficients) of chlorine dioxide (ClO₂), a strong oxidizing agent that is used in food and pharmaceutical packaging, was determined through various common polymeric packaging materials. A continuous system for measuring permeation of ClO₂, using an electrochemical detector, was developed. It was observed that biaxially‐oriented poly(propylene), poly(ethylene terephthalate), poly(lactic acid), nylon, and a multilayer structure of ethylene vinyl acetate and ethylene vinyl alcohol were better barriers for gaseous ClO₂, as compared to polyethylene, poly(vinyl chloride), and polystyrene. The activation energies of permeation for ClO₂ through poly(ethylene terephthalate) and poly(lactic acid) were determined to be 51.05 ± 4.35 and 129.03 ± 2.82 kJ/mol, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, , 2009     

Modified atmosphere packaging bags of peanuts with effect of inhibition of aflatoxin growth

In this article, packaging bags composited with selective barrier film and moisture absorbent nonwoven fabrics were prepared to design a kind of functional bags, which can inhibit the growth of aflatoxin of peanuts. The influences of the super‐absorbent fiber (SAF) and jute fiber on the internal relative humidity (RH) were investigated. It is found that jute nonwoven/selective barrier film composite bag can prevent the growth of aflatoxin B₁ of peanuts under the environment studied in this article because peanuts with higher moisture content can reduce O₂ content inside the bag by the aerobic respiration, achieving the modified atmosphere packaging (MAP) effect. In addition, a low RH micro‐environment can be achieved by using SAF as moisture absorbent. It is promising to design a packaging bag with the effect of inhibition of the growth of aflatoxin of peanuts, by selecting proper moisture absorbent and selective barrier film of the composite bag. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40190.     

Oxygen transfer in co‐extruded multilayer active films for food packaging

Oxygen scavenger applications in flexible food packaging are still limited due to the difficulty to ensure scavenging activity during storage and throughout the product shelf life. To avoid fast inactivation of the scavenger, multilayer active structures can be realized by inserting the active layer between two or more inert layers. In this work, an unsteady‐state 1D reaction‐diffusion mass transfer model was developed for predicting and optimizing the barrier‐to‐oxygen performance and the physical configurations of the co‐extruded multilayer active films. The film configuration was a three‐layers structure composed of polyethylene terephthalate (PET) as external inert layers, and PET with a polymeric oxygen scavenger as the core reactive layer. Scavenging activity of the multilayer film increased with the reactive layer thickness. Oxygen absorption reaction at short times decreased proportionally with the thickness of the external layers. The most appropriate combinations of inert‐to‐active film thickness were studied and analyzed. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Effect of corn‐zein coating on the mechanical properties of polypropylene packaging films

In this study, a novel film structure of corn zein coated on polypropylene (PP) synthetic films for food packaging applications was developed, and the mechanical properties of the resulting coated film, as affected by the coating formulation, were investigated. Composite structures of PP films coated with corn zein were obtained through a simple solvent casting method. Different amounts of corn zein (5 and 15%) were dissolved in 70 and 95% aqueous ethanol solution at 50°C. Solutions of corn zein plasticized with poly(ethylene glycol) and glycerol (GLY) at various levels (20 and 50%) were applied on corona‐discharge‐treated PP. A statistical analysis based on full factorial design was performed to examine the influence of the coating formulation on the final properties of the corn‐zein‐coated PP films. A significant (p < 0.05) improvement in the coated film's mechanical properties was observed compared to those of the uncoated PP. The effect of the plasticization of the coating solutions was also quite significant. In general, GLY provided better improvements in the mechanical properties of the corn‐zein‐coated PP films. The statistical analysis of the results showed that the corn‐zein and plasticizer concentrations and plasticizer type used in the coating formulations were more effective parameters and had significant effects on the mechanical behavior of the coated PP films. In conclusion, corn‐zein coatings could have potential as alternatives to conventional synthetic polymers used in composite multilayer structures for food packaging applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Development of isotactic polypropylene and stearic acid-modified calcium carbonate composite: a promising material for microwavable packaging

Isotactic polypropylene (PP) composite films were developed, with incorporation of CaCO₃ particles as active filler. Stearic acid was used for the surface treatment of CaCO₃ to provide composite films having improved mechanical, thermal and barrier properties against oxygen as well as water vapor, in comparison to neat PP films. The filler was melt mixed with PP in a twin-screw extruder, and the films produced through melt blowing. A slight reduction in T _g values of the filled PP films was observed, along with an increase in the overall crystallization extent relative to neat PP films. X-ray diffraction data confirmed that the CaCO₃ particles served as a β-nucleating agent capable of promoting the formation of the β-crystalline phase of PP and reducing the spherulite size, with stearic acid-coated CaCO₃ being most effective in promoting these features. Exposing the films to microwave radiation altered their properties; at low irradiation power, the T _g values and the degree of β-crystallization were enhanced, and barrier properties against oxygen and water vapor showed improvements. In contrast, no significant changes in the appearance of the film surface were evident highlighting the potential of these PP-based composite films in microwave packaging applications.     

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 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.     

PET and aluminum recycling from multilayer food packaging using supercritical ethanol

Different properties, such as barriers to gas, light, flavor and water vapor, as well as flexibility, are necessary for the production of food packages. These properties may be obtained by combining different polymers. In spite of the advantages achieved with the use of multilayer films, the recycling process of such material is a challenging task. This study presents an alternative for recycling of a quite common food packaging kind, which contains polyethylene (PE), aluminum and poly(ethylene terephthalate) (PET) as a multilayer film. The multilayer packages were delaminated with acetone. PET was depolymerized by ethanol in supercritical conditions. The diethyl terephthalate (DET) was obtained as the main product, presenting high purity and yield of 80%. Also, metallic aluminum was obtained by the PET-depolymerizing process. The optimal reaction time was 120 min. The products were characterized by FTIR, ¹H NMR and ¹³C NMR spectroscopies, DSC and TGA.     

共混改性聚丙烯的研究

用双螺杆共混挤压机和熔融纺丝机,以PET、PE、EVA及另一牌号的PP对聚丙烯进行共混改性,讨论了这些共混物或共混纤维的相容性、流动性、可纺性和染色性。     

Hybrid multilayer thin-film fabrication by atmospheric deposition process for enhancing the barrier performance

In this paper, a multilayer barrier thin film, based on polyvinylidene difluoride (PVDF)–silicon dioxide (SiO₂), has been fabricated on a PET substrate through a novel method of joint fabrication techniques. The inorganic SiO₂ thin film was deposited using a roll-to-roll atmospheric atomic layer deposition system (R2R-AALD), while the organic PVDF layer was deposited on the surface of SiO₂ through the electrohydrodynamic atomization (EHDA) technique. The multilayer barrier thin films exhibited very good surface morphology, chemical composition, and optical properties. The obtained values for arithmetic surface roughness and water contact angle of the as-developed multilayer barrier thin film were 3.88 nm and 125°, respectively. The total thickness of the multilayer barrier thin film was 520 nm with a high optical transmittance value (85–90%). The water vapor transmission rate (WVTR) of the barrier thin film was ~?0.9?×?10^?2 g m^?2 day^?1. This combination of dual fabrication techniques (R2R-AALD and EHDA) for the development of multilayer barrier thin films is promising for gas barrier applications.     

Atmospheric pressure plasma treatment of amorphous polyethylene terephthalate for enhanced heatsealing properties

An atmospheric pressure plasma system has been used to treat amorphous polyethylene terephthalate (APET) to enhance its healseal properties to a polyethylene terephthalate (PET) film. The plasma treated APET sheet material was thermoformed into trays for use in the food packaging industry and heatsealed to a PET film. The heatsealing properties of the resulting package were assessed using the burst test technique. It was found that the plasma treatment significantly enhanced the adhesive properties and an increase in burst pressure from 18 to 35 kPa was observed for plasma treated food trays. The APET surface chemistry was assessed after plasma treatment where it was found that the plasma treatment had affected an increase in oxygen and an addition of nitrogen species to the polymer surface. The surface roughness (R_a) of the plasma treated samples was also observed to increase from 0.4 to 0.9 nm after plasma treatment.     

Electrochemical characterisation of protective organic coatings for food packaging

A very common material for food packaging is steel, in the form of metallic containers (cans), in particular for beverage packaging. The corrosion degradation of the packaging must be carefully controlled, not only because the packaging integrity must be preserved, but also in order to avoid any significant contamination of the food or drink, compromising the flavour. In order to increase the coating performance and the food compatibility, new organic coatings are under development with very high protective properties, with the final aim to increase the shelf life of the product. An electrochemical characterisation is often used to study the protective performance of organic coatings on metal substrate for various applications. Some different coatings for food packaging were considered in the present study, including materials with different chemical composition and different pigments content. The protective properties were quantified using electrochemical impedance spectroscopy (EIS) measurements, comparing the electrochemical substrate activity with electrochemical noise (EN) and scanning Kelvin probe (SKP) measurements. The influence of mechanical deformations on the protective properties was also investigated. The results obtained on the studied coatings confirmed the validity of the electrochemical approach and showed that, in general, the coatings containing pigments (TiO₂) have better performance than clearcoats, while comparing the different polymers, epoxy–phenolic coatings have a better corrosion protection than epoxy–melamine coatings.     

High oxygen barrier property of polyethylene composite films with bilayer polyvinyl alcohol coating for emergency foods in high-humidity environments

The limited oxygen barrier of polyethylene (PE) films has restricted their further application in food packaging, like emergency foods. Although its oxygen barrier property can be improved by applying a polyvinyl alcohol (PVA) coating, the application of PVA/PE composite films in high-humidity environments is still challenging. Hence, this study aimed to enhance the oxygen barrier properties of PVA/PE composite films in high-humidity environments. Specifically, PVA coatings were modified by the itaconic acid (IA) and magnesium-aluminum layered double hydroxides (LDH), and then applied to PE films as bilayer coating. Because of the unique bilayer coating on the PE surface, the oxygen barrier property of PVA/PE composite film (IA/LDH-p) in high-humidity environments has been further improved. The results confirmed that IA/LDH-p had an oxygen permeability coefficient of 1.92 ± 0.16 × 10⁻¹⁶ cm³ cm/(cm² s Pa) under a high-humidity environment test, 82.42% better than that of single-layer coating coated on PE surface. After being stored at RH 90% for 36 h, the tensile strength and elongation at break values of IA/LDH-p were 27.20 MPa and 919.63%, respectively. Overall, this obtained PVA/PE composite films showed great potential for application in emergency foods packaging, particularly in high-humidity environments.     

塑料输液容器用聚丙烯组合盖外盖材料增韧研究

采用聚乙烯（PE）、弹性体及其他助剂增韧改性聚丙烯（PP）,熔融共混挤出造粒制备塑料输液容器用PP组合盖（拉环式）外盖材料。通过正交试验优化了各组分之间的配比,考察了弹性体、PE对PP组合盖（拉环式）外盖材料力学性能及外盖拉环开启力的影响。结果表明,弹性体用量对复合材料的性能影响最显著,当弹性体用量从15份（质量份,下同）增加到30份时,材料的冲击强度先增大后减小,最高达35 kJ/m2,拉伸强度减小,外盖拉环开启力减小,最小达64 N;扫描电子显微镜观察显示,当弹性体的用量小于25份时,弹性体在体系中分散均匀;综合考虑,满足外盖拉环开启力小、拉伸强度大和冲击强度大的最佳配方为PP 65份, PE 20份,弹性体25份,抗氧剂及其他助剂共5份。     

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。     

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.     

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

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

Al2O3/h-BN/epoxy based electronic packaging material with high thermal conductivity and flame retardancy

The long-term and stable operation of integrated circuits and microelectronics requires packaging epoxy resin (EP) exhibit high thermal conductivity for efficient heat dissipation, and excellent flame retardancy in case of thermal runaway. We achieved such EP composite via filling poly-dopamine (PDA) modified nanoscale Al₂O₃ spheres and microscale h-BN sheets. The PDA modification increases the compatibility between fillers and EP and largely reduces the viscosity, improving the dispersion of fillers in EP thus the thermal conductivity of EP composites. In addition, NH₃, H₂O, and N₂ generated during the combustion of phenolic hydroxyls and aminos in PDA combined with the physical barrier effect of Al₂O₃ and h-BN can improve the flame retardancy of EP composites. As a consequence, the EP composite filled with PDA modified Al₂O₃ (26.67 wt%) and h-BN (13.33 wt%) (i.e., PDA-BNAO/EP) shows a thermal conductivity of 1.192 W/mK (654.9% of EP), a peak heat release rate of 194.9 W/g (33.8% of EP), and total heat release of 15.2 kJ/g (54.5% of EP), respectively. What's more, the viscosity of PDA-BNAO/EP is 20,443 mPa s, which is only 20% of BNAO/EP (whose viscosity is 102,281 mPa s). More importantly, the PDA-BNAO/EP has good dynamic mechanical properties with the storage modulus of 14.69 Gpa, glass transition temperature of 91.9°C and good electrical insulation, which is desired for packaging of microelectronics. PDA-BNAO/EP composite should be a promising candidate for widespread packaging materials of microelectronics.