Oxygen‐ and light‐barrier properties of thermoformed packaging materials used for modified atmosphere packaging. evaluation of performance under realistic storage conditions

The oxygen transmission rate (OTR) of packaging materials used for modified atmosphere packaging (MAP) of chilled products varies extensively with temperature, relative humidity (RH) and material thickness after the thermoforming of packages. Two different polymer combinations were studied: APET/PE (tray) and PA/PE (lid). A temperature reduction of 8°C (in the interval 7–23°C) caused an OTR reduction of 26–48% depending on material type, degree of thermoforming and RH. A 2–3‐fold increase in OTR was observed for PA/PE film when measured at 100/100% RH compared to 0/100% RH, whereas the APET/PE trays were not affected by RH. Increased OTR was observed as a result of material thinning; however, the increase was not always directly proportional to the degree of material thinning. Even very small amounts of oxygen have, in combination with light exposure, significant effects on oxidative quality deterioration of many products. Consequently, the changes in OTR observed in this study emphasize the necessity of evaluating the performance of packaging materials under realistic storage conditions, in order to estimate the real oxygen content of a chosen package solution. The light transmission through the packaging material was found to be reduced to 0–30% (300–800 nm) by dyeing of the lid and/or addition of labels. Thus, it is easy to protect the products from light, at least partly. Copyright © 2005 John Wiley & Sons, Ltd.     

Influence of sorbed vegetable oil and relative humidity on the oxygen transmission rate through various polymer packaging films

In this study, the effect of a vegetable oil on the oxygen barrier properties of different polymer packaging materials [i.e. amorphous polyethylene terephtalate (APET), polypropylene (PP) and high density polyethylene (HDPE)] was investigated. The influence of both relative humidity and the combination of relative humidity and sorbed oil on the oxygen transmission rate (OTR) was studied. Regardless of the relative humidity, the APET film remained an excellent oxygen barrier even after storage in rapeseed oil for 40 days. An increased OTR was observed in both the PP and HDPE films stored for 40 days in rapeseed oil. The OTR of the HDPE films was altered to a much greater extent than the OTR of the PP film. The OTR of the HDPE film was also significantly increased for films stored for 20 days in rapeseed oil. The increase in OTR of an HDPE film stored for 40 days in rapeseed oil was between 36 and 44%, depending on the relative humidity, compared to the OTR through the virginal polymer. The amount of oil sorbed by the polymer films used decreased in the following order: HDPE ? APET > PP.     

Electrically Conductive Composite Powders and Compounds Produced with Solid State Synthesis

Electrically conductive composite powders and compounds were produced using a mechanical alloying method. As starting materials, copper powder and a mixture of butadiene-acrylonitrile-copolymer and polyvinylchloride were used. After alloying, the powderlike material consisted of a mixture of fine copper powder embedded in the polymer matrix. Milling resulted in a copper powder of particle size 300 nm to 2 μm. The alloyed powders were compacted at a pressure of 0.37 GPa at 90°C with a holding time of 1 minute. The resistivity of the compound was measured to be 8.6 × 10^-4 ohm-cm. The unusual reduction in particle size to the nanometer level and formation of spherically formed copper polymer composite particles is explained by the reactions of the copper atoms with cyano and other functional groups of the polar polymers. The structurally modified polymer forms a tight encapsulation coating on the surface of the copper, and the flat-formed metal particles are recovered in spherical form due to strong interfacial forces, resulting in increased electrical conductivity.     

Modelling Gas Transmission in Cylindrical Dynamic Accumulation Oxygen Transmission Rate Chambers to Explore Implications of Oxygen Sensor Location Relative to Samples

A model was developed to simulate oxygen accumulation in space and time within cylindrical dynamic accumulation chambers that are used to measure oxygen transmission rate (OTR) of materials. The model is based on Fick's law of diffusion and was validated against actual OTR measurements of polymer film samples. Measured OTR values and thicknesses were inputted into the model and oxygen concentrations outputted by the model. OTRs determined from the output of the model was in close agreement to within 0.3–3% of the measured OTR. Oxygen concentration versus time curves generated from model output oxygen concentrations and experimentally measured oxygen concentrations for three actual films were also in agreement. The model was then used to simulate results from three hypothetical test films at varying chamber lengths in order to evaluate effects of accumulation chamber dimensions relative to films on resulting OTR measurements. A typical design scenario was used, where the oxygen sensor is mounted on the chamber wall opposite the sample film. Results demonstrate that dynamic accumulation OTR instrument designers have considerable flexibility in choosing accumulation chamber dimensions because deviations in OTR are only expected to occur at impractically extreme chamber lengths (>10 m) for the entire envelope of OTRs expected for typical packaging films. Copyright © 2014 John Wiley & Sons, Ltd.     

Development and characterization of PET/Fish Gelatin–nanoclay composite/LDPE laminate

A three‐layer laminate film was developed with the following structure: polyethylene terephthalate (PET)/fish gelatin (FG)–nanoclay composite/low‐density polyethylene (LDPE). The FG–nanoclay composite material functioned as the oxygen barrier layer and demonstrated comparable oxygen barrier properties when compared with a similar laminate utilizing ethylene vinyl alcohol as the barrier layer at a relative humidity (RH) of up to 50%. The introduction of nanometer‐sized filler clay into the FG matrix lowered the oxygen permeability (OP) because of the tortuosity effect of the clay particles. In addition, the FG–nanoclay composite film exhibited bond strengths similar to both LDPE and PET. The hydrophilic nature of FG significantly increases OP under high (>50%) RH conditions. However, this new FG laminate film could be a possible alternative for packaging designers desiring a more sustainable packaging material for low‐RH (<50%) applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Oxygen transmission rates of packages at ambient,chill and freezing temperatures measured by the AOIR method

The ambient oxygen ingress rate (AOIR) method is an alternative or supplementary method to Ox‐Tran for measuring the oxygen transmission rate (OTR) of packages. The method has high capacity, requires relatively inexpensive equipment and measures OTR at different temperatures and humidity conditions. The aim of this study was, on the one hand, to study the effect of temperature on the OTR for packages produced from different polymer materials and laminates, and on the other hand to evaluate the suitability of the AOIR method at freezing temperature conditions. The OTR for 10 packages with different polymer compositions was measured at 23°C, 6°C and ?25°C. The AOIR method was shown to be a reliable test method for measuring OTR of packages at all the applied test conditions, also at frozen storage temperature. The OTR for the packages decreased with lower temperatures, especially for the packages with the highest OTR values at 23°C. In order to avoid higher packaging expenses than necessary to obtain the required shelf‐life for different food products, the OTR for alternative packages should be measured at the temperature and humidity conditions of intended use. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of packaging oxygen transmission rate on the shelf life of ready-to-heat foods susceptible to postcontamination during refrigerated and illuminated storage

Since more and more pressure is exerted to reduce the use of plastic packaging materials, optimizing the use of food packaging is opportune. The aim of this study was to evaluate the combined effect of packaging materials, spanning a range of oxygen transmission rates (OTR), and retail illumination, on the microbial shelf life and safety of refrigerated ready-to-heat foods. Cooked potato slices were packaged in OPA/PP bags with a high OTR (28.85 ccO₂/m²/d) and OPA-EVOH/PP bags with a low OTR (6.57 ccO₂/m²/d). Cooked composite meals were packaged in tray and foil combinations, also spanning a range of OTR: PP trays (2.09 ccO₂/tray/d) with OPA/PP foils (28.85 ccO₂/m²/d), PP trays with OPA-EVOH/PP (6.57 ccO₂/m²/d) foils, and PET trays (0.07 ccO₂/tray/d) with PET top foil (32.86 ccO₂/m²/d) . The packages were stored in a dark environment, or under fluorescent or LED light. Due to the rapid growth of lactic acid bacteria, the microbial shelf life of both food products was largely unaffected by the type of barrier. Illumination at 1000 lux for 12 hours per day led to temperature differences significantly affecting microbial growth. Based on the results, it could be concluded that re-evaluating packaging material choices for these foods may prove valuable, since the use of high-barrier multilayer packaging materials may be considered as a case of overpackaging.     

Preparation, Electrical, and Dielectric Characterization of Crosslinked Polyvinyl Alcohol-Phosphotungstic Acid Nanocomposites

The work presents the electrical and dielectric characterization of proton-conducting, chemically-crosslinked nanocomposites of polyvinyl alcohol (PVA) and phosphotungstic acid (PTA). The composite membranes were prepared by in situ crosslinking of the polymer matrix in solution form, containing PTA. The electrical and dielectric properties of the membranes were investigated as a function of blending composition, crosslinking density, and temperature. The conductivity of these membranes shows a temperature dependence of Arrhenius type and highest conductivity of 3.31 × 10^-3 S cm^-1 was obtained. The activation energies for proton conduction were found to be in the range of 15.28-40.62 kJ mol^-1.     

Alkoxide route to La0.5Sr0.5CoO3 epitaxial thin films on SrTiO3

An all alkoxide based sol–gel route was investigated for preparation of epitaxial La_0.5Sr_0.5CoO₃ (LSCO) films on 100 SrTiO₃ (STO) substrates. Films with 20–30 to 80–100 nm thickness were prepared by spin-coating 0.2–0.6 M (metal) solutions on the STO substrates and heat treatment to 800 °C at 2 °C min^− 1, 30 min, in air. The films were epitaxial with a cube-on-cube alignment and the LSCO cell was strained to match the STO substrate of 3.905 Å closely; a and b = 3.894 Å and 3.897 Å for the 20–30 and 80–100 nm films, respectively. The c-axis was compressed to 3.789 Å and 3.782 Å for the 20–30 and 80–100 nm films, respectively, which resulted in an almost unchanged cell volume as compared to polycrystalline film and nano-phase powders prepared in the same way. The SEM study showed mainly very smooth, featureless surfaces, but also some defects. A film prepared in the same way on an -Al₂O₃ substrate was dense and polycrystalline with crystallite sizes in the range 10–50 nm and gave cubic cell dimensions of a_c = 3.825 Å. The conductivity of the ca 30–40 nm thick polycrystalline film was 1.7 mΩcm, while the epitaxial 80–100 nm film had a conductivity of around 1.9 mΩcm.     

Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composites

Composites of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were synthesized by a modified Hummers method and a solution-mixing method. GO was fully exfoliated in the PVA/GO composites. GO did not affect the crystallization of PVA during solvent evaporation. GO is itself an excellent gas barrier without any chemical reduction. The oxygen permeability of the PVA/GO (0.3 wt.%) composite coated film was 17 times lower than that of the pure poly(ethylene terephthalate) (PET) film, with 92% light transmittance at 550 nm. Composites of PVA and reduced graphene oxide (RGO) were synthesized by performing chemical reduction using hydrazine monohydrate. The oxygen permeability of the PVA/RGO (0.3 wt.%) composite coated film was 86 times lower than that of the pure PET film, with 73% light transmittance at 550 nm. The reduction of oxygen permeability was mainly attributed to the reduced oxygen solubility in the PVA/GO composite film, while it was attributed to both the reduced oxygen diffusivity and solubility in the PVA/RGO composite film.     

Dielectric Properties of (C60 + C70)—Ferroelectric Liquid Crystal Composite

A stable composite of fullerene and ferroelectric liquid crystal (FLC) has been obtained. Analysis of the frequency dependence of imaginary part of complex dielectric permittivity showed that orientation of the liquid crystal (LC) in the composite is close to homeotropic. At temperatures above 329 K, the composite conductance is determined by the conductance of fullerene. At 344 K, the composite conductance is 3.2 × 10^-8 Ω^-1 m^-1, and the activation energy for the temperature dependence of conductance is 0.99 eV. At temperatures below 329 K, the composite properties are determined by the LC, and the frequency dependences of the components of complex dielectric permittivity showed dispersion due to rotation of molecular dipoles around the helicoid (Goldstone mode) axis. The relaxation time is close to 1 msec and almost equal to the value obtained for homeotropically oriented LC.     

Matrices of water-soluble drug using natural polymer and direct compression method

The objective of this research was to find an optimum Carrageenan matrix formulation with the desired drug release and physical properties prepared by direct compression. In order to achieve this, matrices containing 10% theophylline, different Carrageenan level, and different excipient were prepared and evaluated. A selected matrix containing 40% Carrageenan and lactose fast flo was tested for dissolution in three different dissolution media (distilled water, 0.1 N HCl, and phosphate buffer pH 7.4). The same formulation was also tested for dissolution at 50 rpm, 100 rpm, and 150 rpm, and using different dissolution apparatus (Apparatus 1 and 2).

All matrices showed a decrease in drug release as the polymer level was increased. Only Avicel PH-101 did not show any significant difference between matrices prepared with 30% and 40% polymer. At 10% polymer level, it appears that the type of diluent used controls the drug release. However, at high polymer level, 30% and 40%, it appears that the polymer level controls the drug release. Phosphate buffer pH 7.4 and 0.1 N HCl increase drug release and appear to increase Carrageenan solubility and decrease gel formation. Also, as the rotational speed of the apparatus was increased, the integrity of the gel layer was decreased, and the release of drug was increased. The drug release from Carrageenan matrices appears to follow the diffusion model for inert matrix up to 90 min. After 90 min, the drug release follows a zero-order model.

This study demonstrated that matrices using Carrageenan can be successfully prepared by direct compression.     

ZnO/SiO2复合薄膜的制备及其阻隔性能研究

目的为了进一步提高氧化锌(ZnO)沉积复合薄膜对氧气的阻隔能力,探索其应用于食品和药品包装材料的可行性。方法采用射频磁控溅射技术(RF),以ZnO和二氧化硅(SiO2)为靶材,在PET塑料表面同时沉积,制备ZnO/SiO2复合薄膜包装材料,并详细分析SiO2的引入对ZnO沉积膜微观结构和阻隔能力的影响,优化ZnO/SiO2的制备工艺。结果SiO2的引入,使ZnO纳米颗粒的形状由片状燕麦变成了球形,当功率密度比PSiO2/PZnO为0.67,氩气流量为20 mL/min,沉积时间为20 min,工作气压为0.5 Pa时,ZnO/SiO2复合薄膜的氧气透过率降低为0.462 mL/(m^2·d),水蒸气透过率有所增加,为0.367 g/(m^2·d)。结论引入合适比例的SiO2,可有效提升ZnO沉积层对氧气渗入的阻隔能力,但SiO2引入量过高时,会加剧纳米裂纹,对复合薄膜的阻隔能力不利。     

Prediction of oxygen transmission rate for thermoformed trays

There is a desire in the food industry to be able to estimate the oxygen transmission rate (OTR) of packages by knowing the permeability data of unconverted sheet/film, instead of measuring the OTR of packages. Due to thermoforming, the permeability of a material changes and therefore it is difficult to estimate the permeability (OTR) of converted trays from the OTR values of unconverted material. This paper evaluates the possibilities and limitations of predicting the OTR of thermoformed trays. Different methods for the calculation of OTR due to thickness measurements were compared. The use of theoretical thickness was satisfactory in the calculation of OTR of trays based on the OTR of unconverted sheet, area and thickness. Both linear and quadratic regression models were evaluated. Validation of the regression models was made by comparing the measured and calculated OTR of trays made of PS/EVOH/PE, A‐PET/PE, PS/PE and PP/PE. These trays were manufactured on different thermoforming machines, different processing parameters and different sizes of mould. None of the models (linear and quadratic) were suitable for the calculation of OTR of trays made of PS/PE and PP/PE. Both linear and quadratic models gave satisfactory agreement with measured values for trays made of both PS/EVOH/PE and A‐PET/PE. This case study indicates that a general equation for the calculation of OTR for different polymer combinations was not possible to generate. The equations presented in this paper are strictly applicable only for the polymer combinations used in this experiment, and can not be considered as general equations. Copyright © 2004 John Wiley & Sons, Ltd.     

Microperforation of Three Common Plastic Films by Laser and Their Enhanced Oxygen Transmission for Fresh Produce Packaging

Three different plastic films of biaxially oriented polypropylene (BOPP), biaxially oriented polyethylene terephthalate (BOPET) and low‐density polyethylene (LDPE) were perforated using Nd‐YAG laser. Effects of laser pulse energy were examined by varying energies from 50 to 250 mJ where the pulse duration and pulse repetition were kept constant at 10 ns and 1 Hz, respectively. It was found that perforation diameters of all films increased with increasing pulse energies. Observed perforations were different among the three film types. Explanation was contributed to material inherent property and its interaction with laser. Incorporation of an inorganic filler (i.e. silica based anti‐blocking agent used in packaging film) of 0.5 wt% into the LDPE films (0.5Si‐LDPE) could improve perforation performance for LDPE. This was attributed to an increased thermal diffusivity of the 0.5Si‐LDPE film. Commercial BOPET and BOPP films containing 97 microholes/m² (hole diameter of ~100 µm) showed an improvement in oxygen transmission rates (OTR) of 18 and 5 times that of the neat films without perforation. In the case of perforated 0.5Si‐LDPE films having similar perforations of 97 microholes/m² and perforation diameter of 100 µm, a two‐fold increase of OTR was obtained. Gas transmission rates of the microperforated films were measured based on the static method. Measured OTR and CO₂TR values of the three films with varying perforation diameters in a range of ~40–300 µm were compared and discussed. Overall results clearly indicate that perforation by laser is an effective process in developing breathable films with tailored oxygen transmission property for fresh produce packaging. Copyright © 2014 John Wiley & Sons, Ltd.     

纳米复合薄膜及其在果蔬保鲜中的应用

纳米复合包装薄膜一般为聚合物基纳米复合材料,可分为纳米材料/合成聚合物复合材料与纳米材料/天然聚合物复合材料。阐述了这2种复合材料的制备方法和性能特点,综述了纳米TiO2复合薄膜、纳米SiO2复合薄膜、纳米CaCO3复合薄膜、纳米银复合薄膜在果蔬保鲜中的应用研究,并展望了纳米复合薄膜在果蔬保鲜应用方面的研究方向。     

A comparative study of oxygen transmission rates through polymer films based on fluorescence quenching

Information on oxygen permeability through polymer films is essential for some applications, especially in food packaging where the control of oxygen levels can be critical in avoiding food spoilage. A permeability testing device using fluorescence‐based optical oxygen sensing was developed as a potential new instrument for measuring the oxygen permeability of packaging films. The fluorescence‐based permeability tester was validated against two existing commercial oxygen permeability measuring devices, the Mocon Ox‐Tran 2/20 and PBI‐Dansensor OPT‐5000. Oxygen transmission rates (OTR) of polylactide (PLA) and nanoclay‐reinforced PLA films, as well as polyethylene/poly(ethylene terephthalate) (PE/PET) and polypropylene/poly(ethylene terephthalate) (PP/PET) laminated films were determined at 23°C and 50% relative humidity using each of these instruments. No significant differences were observed between mean OTR values obtained by the fluorescence method and the corresponding values obtained using the OPT‐5000 but significantly lower values were measured when using the Mocon Ox‐Tran 2/20. In general, oxygen permeability data for the tested films were within the range of values found in the literature; however, in terms of further development, the fluorescence‐based technique gave OTR with relatively high standard deviation compared to the commercial methods and equipment modifications to address this issue are considered desirable. Copyright © 2010 John Wiley & Sons, Ltd.     

Improved polymer nanocomposite dielectric breakdown performance through barium titanate to epoxy interface control

A composite approach to dielectric design has the potential to provide improved permittivity as well as high breakdown strength and thus afford greater electrical energy storage density. Interfacial coupling is an effective approach to improve the polymer-particle composite dielectric film resistance to charge flow and dielectric breakdown. A bi-functional interfacial coupling agent added to the inorganic oxide particles’ surface assists dispersion into the thermosetting epoxy polymer matrix and upon composite cure reacts covalently with the polymer matrix. The composite then retains the glass transition temperature of pure polymer, provides a reduced Maxwell-Wagner relaxation of the polymer-particle composite, and attains a reduced sensitivity to dielectric breakdown compared to particle epoxy composites that lack interfacial coupling between the composite filler and polymer matrix. Besides an improved permittivity, the breakdown strength and thus energy density of a covalent interface nanoparticle barium titanate in epoxy composite dielectric film, at a 5 vol.% particle concentration, was significantly improved compared to a pure polymer dielectric film. The interfacially bonded, dielectric composite film had a permittivity ∼6.3 and at a 30 μm thickness achieved a calculated energy density of 4.6 J/cm³.     

Preceramic polymer derived cellular ceramics

Ceramic foams were prepared by a self-blowing process of a poly(silsesquioxane) melt at 270 °C. The cell size, the interconnectivity density and the shape of the foam cells were adjusted by a thermal pre-curing procedure of the polymer at 200 °C. Inorganic fillers were used to modify processing behaviour and properties of the pyrolysed ceramic foam. After pyrolysis in inert atmosphere at 1200 °C ceramic composite foams with a total porosity up to 87% were obtained. The open cell ceramic foams had a mean cell diameter of 1.2 mm and a mean strut thickness of 0.2 mm. Interpenetrating phase composites (IPCs) were fabricated by infiltrating the open cellular ceramic preform with Mg alloy melt at 680 °C and a pressure of 86 MPa. The mechanical properties were found to depend on the reactions between the metal and the ceramic forming MgO, Mg₂Si and Al₁₂Mg₁₇ as the major reaction products. The IPCs showed a significantly higher creep resistance at 135 °C, compression strength and elastic modulus compared to the unreinforced magnesium alloys.     

A rapid method to determine the barrier requirements for dehydrated oatmeal product using flexible packaging films

Product was packaged in two types of flexible packaging films, poor moisture-high oxygen barrier and high moisture-poor oxygen barrier, and stored under standard tropical conditions. Physical, chemical and biological changes were investigated regularly to find the shelf-life determining factors. Control samples were packaged in glass bottles and stored at 0°C. OTR and WVTR of packaging films were measured. Packaging film permeability and analytical data, obtained from storage tests, were used to determine the barrier requirements for dehydrated oatmeal product, intended for distribution and storage in a tropical climate for 9 months shelf-life. © 1997 John Wiley & Sons, Ltd.