Comparison of New Dynamic Accumulation Method for Measuring Oxygen Transmission Rate of Packaging against the Steady‐State Method Described by ASTM D3985

A new dynamic accumulation method for measuring the oxygen transmission rate (OTR) of packages and packaging films using robust and inexpensive fluorescence oxygen sensing technology has been developed. The method allows for oxygen to transfer through a given area of packaging or sample film and accumulate over time. The test volume incorporates a fluorescence‐based oxygen sensor that does not consume oxygen and therefore does not interfere with the real‐time measurement of oxygen concentration. The new method was tested against a widely used, commercially available instrument (Mocon Oxtran 2/20; Mocon, Inc., Minneapolis, MN, USA) designed around the steady‐state gas permeation measurement approach described by ASTM D3985. Sample films were chosen to provide comparison over several orders of magnitude of OTR. Specifically, sample films with OTR values in the range of 10¹, 10³ and 10⁴ ml O₂/m²/day were measured, and results using the two methods were compared. Results showed that the new dynamic accumulation method provides comparable results with the steady‐state method (ASTM D3985). Copyright © 2012 John Wiley & Sons, Ltd.     

Ambient oxygen ingress rate method—an alternative method to Ox‐Tran for measuring oxygen transmission rate of whole packages

The ambient oxygen ingress rate method (AOIR) is an alternative method to Ox‐Tran for measuring the oxygen transmission rates (OTR) of whole packages. The objective of the present work was (a) to compare OTR values obtained by the two methods, and (b) to evaluate the use of the AOIR method for measuring OTR at realistic food storage temperatures and humidity levels. The AOIR method gave equal OTR values compared to the Ox‐Tran method for the five different types of whole packages used in the experiment, with OTR values in the range 0.06–1.48 ml O₂/day. The repeatability of the AOIR method measured on an HDPE bottle was ±2.6% of the measured value in this experiment. This is slightly higher than the general specifications of the Ox‐Tran method (1% of reading for packages). However, the AOIR method can be considered to be a reliable, precise and cheap alternative method to the Ox‐Tran method for measuring OTR of whole packages. The capacity of the method is also high. The AOIR method showed satisfactory results when comparing OTR for packages tested under realistic food storage conditions covering 23°C/50% relative humidity (RH) and at 4°C/60% RH on the outside, combined with water (100% RH) or dry air inside the packages. Copyright © 2000 John Wiley & Sons, Ltd.     

Measurement of the Oxygen Transmission Rate of Co‐extruded Wine Bottle Closures Using a Luminescence‐Based Technique

The oxygen transmission rate (OTR) is a value commonly measured in different industries to evaluate oxygen flow through all types of packaging. The Mocon^® Ox‐tran^® method (Mocon Inc., Minneapolis, MN, USA) for measuring OTR is globally accepted and is recommended in different standards such as the ASTM (F1307‐02), but in practice, only a limited number of samples can be analysed, and the stabilisation of the measurement takes time. In this paper, a simple, non‐destructive technique allowing measurement of co‐extruded closure OTR is presented. The established protocol allows measurement of oxygen ingress through the closures or at the interface between closures and bottleneck and avoids possible leakages that can happen when bottlenecks are glued onto metallic plates. Oxygen permeating in the bottle is measured by a luminescence‐based technology using separate sensors supplied by PreSens^® (Precision Sensing GmbH, Regensburg, Germany). The simple set‐up and the use of a non‐destructive luminescence‐based technology make this an easy test to perform. Moreover, the development of a predictive model allows us to reduce the analysis time to one week. Comparison with the well‐established Mocon Ox‐tran method shows good accordance between the two techniques. This new method allows the measurement of more samples in less time without compromising analytical performance. This method could become a useful quality control procedure in the wine industry to assess OTR performances of closures. Copyright © 2011 John Wiley & Sons, Ltd.     

Diamond-like carbon,a barrier coating for polymers used in packaging applications

Water and oxygen permeability measurements on two polymers, poly(ethylene terephthalate) and polypropylene, are presented as a function of diamond-like carbon coating thickness. Results show that reliable and reproducible coatings can be achieved on poly(ethylene terephthalate) such that levels of permeability are about 1 cc/m²/day for oxygen and 1.5 g/m²/day for water vapour, comparable to the levels for silicon oxides and aluminium coatings used in the packaging industry. The advantages conferred by diamond-like carbon over aluminium is primarily that of retaining optical transparency in the thickness of films used in this work (20 nm). The advantages of diamond-like carbon over silicon oxides is related to its intrinsic flexibility. Other advantages over other barrier films (e.g. polyvinylidine chloride) and coating technologies is the ability to recycle the used product. The permeability of diamond-like carbon-coated polypropylene to oxygen is in the range of 200 cc/m²/day, again comparable to results obtained with the other coatings. The optimum film thickness for poly(ethylene terephthalate) to minimize permeability was 20 nm. Atomic force microscopy revealed agglomerated structures (possibly graphitic) with the underlying substrate appearing smoother than the starting material. In comparison, polypropylene exhibited increased surface roughness under the same coating conditions.     

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.     

Synthesis,Characterization and O2 Permeability of Shape Memory Polyurethane Films for Fresh Produce Packaging

The aim of this work was to investigate the effect of film formulations in an effort to obtain a fresh produce packaging film with increased temperature sensitivity for gas permeability. Series of shape‐memory polyurethane (SMPU) were synthesized using poly(ethylene glycol) (PEG), 1,6‐hexamethylene diisocyanate, 1,4‐butanediol and castor oil (CO) and casted into films. The changes in thermal, viscoelastic, shape‐memory properties and oxygen permeability of the films were studied. The polyurethane films with 1500 g mol^?1 PEG showed a phase transition temperature (switching temperature) between 20 and 27°C. The SMPU consisting of 50/50 CO/PEG had a log E′ value of 8.32 Pa and showed good elasticity as low density polyethylene. SMPU prepared from 1500 g mol^?1 PEG with 50/50 CO/PEG and 40/60 butanediol/(PEG + CO) ratios showed excellent shape‐memory properties with shape recovery ratio >85% and shape fixity ratio >90%. This film had higher oxygen permeability and showed up to 67% increase in Q₁₀ value for oxygen permeability compared with commercial packaging films like low density polyethylene. This film can be used to develop smart packaging with increased thermally responsive gas permeability to similar levels observed in respiration rates of fresh produce. Copyright © 2016 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.     

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.     

Flexible and Tough Poly(lactic acid) Films for Packaging Applications: Property and Processability Improvement by Effective Reactive Blending

This study demonstrates a practical means to overcome inherent brittleness problem of poly(lactic acid) (PLA) and make PLA feasible as packaging material. PLA with suitable processability is utterly required for package manufacturers, where flexible, tough PLA film is essential for packers and end users. Highly flexible PLA films with 60‐fold increase in elongation at break (Eb) over that of the neat PLA were successfully produced by integrating effective reactive blending and economical film blowing process. The ‘two‐step’ blending was used to prepare PLA compound; poly(butylene adipate‐co‐terephthalate) (PBAT – another biodegradable polymer) was first blended with 0.5–1% chain extender (epoxy‐functionalized styrene acrylic copolymer) (ESA), followed by subsequent blending with PLA in twin‐screw extruder. Blown films of reactive blend of PLA/PBAT/ESA (80/20/1) showed impressively high Eb of 250% versus a very low Eb of 4% for the neat PLA. Resulting blown films still possessed high modulus of 2 GPa, yield stress of 50–60 MPa and good toughness of ~100 MPa. Significant enhancement in the film's ductility was attributed to homogeneous blend with developed fine strand‐like structure as a result of effective in situ compatibilization and good interfacial adhesion between the PLA and PBAT. PLA/PBAT/ESA blend also offered improved processability. Resulting films had acceptable haze of ~10% for common packaging, and clearer film close to PLA (≤2%) could be obtained by designing PLA skin layers in multilayer structure. Films of PLA/PBAT/1%ESA exhibit potential as packaging material; their mechanical and optical properties are comparable with or even exceed some existing films used in the market. Copyright © 2015 John Wiley & Sons, Ltd.     

Polyester/aluminium adhesion: improvement by heat treatments

Because of its industrial importance, poly(ethylene terephthalate) (PET) has been the subject of numerous studies concerning surface modifications in order to improve its bonding ability. Most of the previously reported surface treatments performed before the metallization provide good dry adhesion of vapour deposited metallic layers. However, food packaging applications also require good wet adhesion and strong oxygen barrier properties. Heat treatments have been found to improve these properties. Hence, the aim of this study was to isolate an efficient heat treatment for the metallized PET films suitable for industrial application. The adhesive performance of aluminized polyester films has been assessed by use of an ultrasonic vibration test. This revised version was published online in November 2006 with corrections to the Cover Date.     

Transport Coefficients of Eucalyptol through Various Polymeric Films

This study presents the determination of the transport properties of eucalyptol, which is a key aroma compound in fresh tropical herbs through different polymeric packaging materials. Packaging films used in this study were polyethylene, polypropylene, Nylon, polyethylene terephthalate and polylactide (PLA1 and PLA2). Test films were immersed in the 1000 ppm of aroma compound and stored in amber vials. The concentrations of aroma compounds extracted from films were determined using gas chromatography. Diffusion, solubility, permeability and partition coefficients were calculated from sorption kinetics. Results show that the diffusion and solubility coefficients of eucalyptol were lowest in PLA1 and highest in polyethylene. Solubility coefficients were associated with partition coefficients as well as solubility parameters and contact angle values. Primary factor determining solubility was affinity between the aroma compounds and the polymeric films. Transport coefficients of eucalyptol in the vapor phase followed the same trends as in the liquid phase with about 3‐fold greater. Understanding interaction phenomenon between the key aroma compound and major packaging films may contribute to improvements in film selection and the design of food packaging applications. Finding from this research contributes toward future development of the high‐aroma barrier materials. Copyright © 2011 John Wiley & Sons, Ltd.     

The effect of high‐pressure food processing on the sorption behaviour of selected packaging materials

The sorption behaviour and flavour‐scalping potential of selected packaging films in contact with food simulant liquids (FSLs) (ethanol and acetic acid solutions) were evaluated after high‐pressure processing (HPP). The films used were monolayer polypropylene (PP), a multilayer (polyethylene/nylon/ethylene vinyl alcohol/polyethylene: PE/nylon/EVOH/PE), film and a metallized (polyethylene terephthalate/ethylene–vinyl acetate/linear low‐density polyethylene: metallized PET/EVA/LLDPE) material. D‐limonene was used as the sorbate and was added to each of the FSLs. After HPP treatment at 800 MPa, 10 min, 60°C, the amount of D‐limonene sorbed by the packaging materials and the amount remaining in the FSL was measured. Untreated controls (1 atm, 60°C and 40°C) were also prepared. Extraction of the D‐limonene from the films was performed using a purge/trap method. D‐limonene was quantified in both the films and the FSL, using gas chromatography (GC). The results showed that D‐limonene concentration, in both the films and the food simulants, was not significantly affected by HPP, except for the metallized PET/EVA/LLDPE. Significant differences in D‐limonene sorption were found in comparison with the control pouches. The results also showed that changes in temperature significantly affected the sorption behaviour of all films. Copyright © 2004 John Wiley & Sons, Ltd.     

Properties of antimicrobial plastics containing traditional food preservatives

Traditional food preservatives, sodium benzoate, sodium nitrite, potassium sorbate and sodium lactate, were incorporated into synthetic plastics, low‐density polyethylene (LDPE), poly(maleic acid‐co‐olefine), polystyrene (PS) and polyethylene terephthalate (PET), aimed at producing antimicrobial packaging material for foodstuffs. The study was undertaken on plaques (thickness 2 mm) and films (thickness 70–120 µm), whose antimicrobial test results clearly differed. Plaques containing 15% sodium nitrite inhibited both Aspergillus niger and Bacillus subtilis, whereas the same concentration of sodium benzoate and potassium sorbate had activity only against B. subtilis. Sodium lactate‐containing samples did not have any antimicrobial activity and none of the samples inhibited Escherichia coli. Antimicrobial substances added into PS and PET produced the strongest activities; however, due to the brittle structure of these materials, they were not tested further. Thus, more thorough tests for antimicrobial activity, migration and oxygen and water vapour permeability were carried out using LDPE films with 2.5–15% sodium benzoate and sodium nitrite. The effects of both substances on permeability properties were negligible. Although the total migration into food simulants measured from the films in many cases exceeded the limit value of 10 mg/dm², no antimicrobial activity was observed. Copyright © 2003 John Wiley & Sons, Ltd.     

Measurement of oxygen transmission rate through foamed materials for bottle closures

The determination of the oxygen transmission rate (OTR) through closures in glass bottles is becoming increasingly important for quality control of different batches and for development purposes. The Mocon method for measuring OTR is globally accepted and used in different applications. However, one of the major drawbacks this method presents when applied to bottle/closures systems is the long time required to obtain stable measurements when 40 mm long closures are tested. This paper describes a method to obtain OTR values with samples of reduced thickness with much shorter measurements time, since the condition of steady state during measurements is achieved faster and compares the estimated full‐length commercial closure OTR with experimental values. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

A Review and Evaluation of Prediction Models of Gas Permeation for a Blended Flexible Packaging Film

Barrier properties of blended film, such as oxygen permeability, are a collective behaviour contributed by different resins. This study reviews 10 most widely used prediction models of gas permeation for two‐phase blended film along with their assumptions and the interconnection and similarities between these models. Two blended blown films, LDPE/EVOH and PET/PEN, were produced representing two different permeability ratios of matrix‐to‐disperse phase. Effective oxygen permeability of the blended films was predicted by the models and compared with measured values. Scanning electron microscopy (SEM) micrographs of both films were obtained to understand the morphology in relation to gas permeation. The Fricke model and the effective medium theory model are recommended in this study to predict effective permeability of a blended flexible packaging film. Copyright © 2016 John Wiley & Sons, Ltd.     

Layer-by-layer assembly of thin film oxygen barrier

Thin films of sodium montmorillonite clay and cationic polyacrylamide were grown on a polyethylene terephthalate film using layer-by-layer assembly. After 30 clay–polymer layers are deposited, with a thickness of 571 nm, the resulting transparent film has an oxygen transmission rate (OTR) below the detection limit of commercial instrumentation (< 0.005 cc/m²/day/atm). This low OTR, which is unprecedented for a clay-filled polymer composite, is believed to be due to a brick wall nanostructure comprised of completely exfoliated clay in polymeric mortar. With an optical transparency greater than 90% and potential for microwaveability, this thin composite is a good candidate for foil replacement in food packaging and may also be useful for flexible electronics packaging.     

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.     

Quality of orange juice in barrier packaging material

The vitamin C content and the colour of orange juice made from concentrate were measured during 9 months of storage at 20°C either under artificial light or in darkness. The packaging materials used were glass, standard monolayer polyethylene terephthalate (PET) and multilayer PET (PET/nylon and oxygen scavenger/PET) containers. In this experiment, all bottles were sealed with aluminium foil in order to avoid any cap effect. The results showed that in plastic packaging materials, the loss of vitamin C was related to the oxygen permeability, and that glass provided the best preservation of ascorbic acid. No statistical difference (p < 0.05) was revealed between the vitamin C content in the juice stored under artificial light or in darkness, whatever the packaging used. The modification of colour was studied with the L, a* and b* values during storage at 20°C under artificial light. L and b* decreased, revealing a reduction of lightness and yellow colour of the juice, whereas a* increased, due to the formation of brown pigments. This change in colour was partly related to the oxygen permeability of the packaging used. The losses of aroma compounds by permeation through the bottle (PET) and the cap (high‐density polyethylene, HDPE) have also been investigated. The results showed that permeation mainly took place through the cap. The use of a multilayer cap [HDPE with internal barrier layer of low‐density polyethylene (LDPE)/EvOH/LDPE] considerably limited the permeation of the aroma compounds studied, whatever the PET bottle used. Copyright © 2007 John Wiley & Sons, Ltd.     

Influence of composition on structure and barrier properties of active PET films for food packaging applications

A very attractive solution in food packaging technology is the functionalization of packaging materials by incorporating an active phase into polymeric matrices. Nowadays, the applications of active substances into flexible packaging are very limited due to difficulties in realizing performing films by common manufactory processes. This work is focused on the production and characterization of monolayer poly(ethylene terephtalate) (PET) active films at different concentrations of an oxygen scavenger by cast extrusion process. Rheological, thermal, morphological analyses and oxygen absorption measurements were carried out on the produced samples to investigate the structure of active PET films and to determine their scavenging properties. Overall migration analyses were performed on active films to asses their safety in use with foodstuff, and finally the produced films were used to package fresh banana slices for evaluating their capability in quality foods preservation. Copyright © 2010 John Wiley & Sons, Ltd.