A transient method of measuring the water vapour permeability of packaging films. II. Iterative determination of permeability

Principles of the conversion of a measured electrical signal to the relative humidity units have been worked out according to a theory of the method and the measuring system for water vapour permeability through packaging films measurement. The method and the system were based on sorptive sensor reaction inertia analysis. The constants of the measuring vessel were determined by means of the dish method for fixed measurement conditions. Using the developed theory, water vapour permeability was determined for the chosen films. The results obtained were in close agreement with values determined by the dish method and additionally for PET-50 film also in close agreement with the literature data. The uncertainty of the results obtained by this method was estimated. The relative mean uncertainty (α = 0.05) was B_p ≃ 1.1% and the relative maximum uncertainty of a single result B_pmax = 3.1%.     

Measurement of permeability for packaging films to d-limonene vapour at low levels

A method that utilizes permeation cells in conjunction with gas chromatography was developed to measure permeation of d-limonene vapour through packaging materials at very low gradient concentrations. The same method, when properly adjusted, can be used to determine the effect of temperature and relative humidity on permeation. The suitability of the method for its intended use was demonstrated by generating permeation data for polyester (Mylar) and oriented polypropylene (OPP) films at d-limonene vapour concentration gradients as low as 0.54 ppm. The ability to measure permeability at such low concentration levels, where the permeability coefficient approaches a virtually constant value, is of considerable importance. The permeation behaviour of packaging materials at even lower concentrations, most typical of foods, can be obtained by extrapolation. Thus, flavour loss through the package and shelf-life can be estimated in a more reliable manner.     

Porous Ultrahigh Gas‐Permeable Polypropylene Film and Application in Controlling In‐pack Atmosphere for Asparagus

Porous polypropylene (PP) films with greater gas permeability and lower permeability ratios (β) than existing commercial films were developed for fresh produce packaging. PP containing high content of beta‐form crystal was biaxially stretched under controlled conditions. Resulting porous films with uniquely high oxygen transmission rate (OTR) of 2 659 000 cm³?m^?2?d^?1, water vapor transmission rate of 67 g?m^?2?d^?1, and β value of 0.76 was used as a “breathable window” attached to the less permeable commercial BOPP (biaxially oriented PP) lidding film. Various sizes/areas of the breathable windows were designed and tested on packaging asparagus of 400 g, at 5°C. Results demonstrated that in‐pack O₂ and CO₂ concentrations could be practically controlled and modified by changing areas of the breathable windows. Altered porous high OTR area directly affected total gas permeation of the package. Optimum gas composition of Ο₂ and CΟ₂ within the recommended controlled atmosphere for asparagus, stored at 5°C, was effectively created and maintained in the package containing 25 cm² breathable window (15% of total film lid's area). The shelf life of asparagus under optimum modified atmosphere was extended to 29 days, as compared with <3 days in the normal, low OTR tray sealed with BOPP lidding film. Clearly, these developed porous ultrahigh permeable PP films can be useful materials in designing high OTR package with desirable in‐pack O₂ and CO₂ concentrations. Copyright © 2013 John Wiley & Sons, Ltd.     

A Multi‐functional Biofilm Used as an Active Insert in Modified Atmosphere Packaging for Fresh Produce

We developed a multi‐functional agar‐based biofilm for fresh produce packaging by modulating its CO₂ absorption and water vapour absorption functions. The film was prepared from solutions containing agar as a matrix and a water vapour absorbent, glycerol as a plasticizer, and sodium carbonate (SC) and/or sodium glycinate (SG) as a CO₂ absorbent. The optical, mechanical, and CO₂ and water vapour absorption properties of SC, SG, and SC/SG films were investigated. Multi‐functional films tended to show poor mechanical properties, with a hard texture and an opaque and yellowish colour. The three films had different CO₂ absorption capacities and coefficients, with SC film showing the highest absorption, followed by SC/SG and SG films. The water absorption coefficients were much higher than those of CO₂, with the opposite dependence on the absorbent compound. The multi‐functional benefits of the developed film were shown by using the film for modified atmosphere packaging (MAP) of shiitake mushrooms as an insert label. A tailored MAP design for shiitake mushrooms was produced based on mass transfer mathematical models. The package attached with SC film label was capable of generating the desired internal atmosphere and thus showed the best quality preservation in terms of colour, firmness, flavour score, and bacterial growth after 5‐day storage. A tailored MAP system with our multi‐functional film can provide an optimal modified atmosphere for CO₂‐sensitive fresh commodities, preserve their quality, and extend their shelf life. Copyright © 2015 John Wiley & Sons, Ltd.     

Mass transfer from and through packaging materials

The use of polymer films for food packaging requires a knowledge of their transport properties under varying conditions. The permeability to gases and water vapour of the packaging films at the specific conditions of use, i.e. temperature, relative humidity and pressure gradient, are needed for selecting the optimum packaging system to ensure the required shelf-life of the packed product. Migration from, and absorption by, plastic films also play an important role in their selection. The 0₂ and CO₂ permeabilities of three plastic films at four different temperatures were evaluated and shown to follow the Arrhenius relationship in the range tested. The effects of four thicknesses of one film on its permeability are also reported. Three methods to evaluate migration from polymeric films were compared using different weight/volume ratios. The extraction method recommended by the FDA, using n-hexane in a stirred flask, was found to be best. The shelf-life of Matzoth (Jewish Passover bread) packed in polyethylene (stored at 25°C) was found to be longer than the shelf-life of those packed in the higher barrier PVDC/PE. This was apparently due to the absorption of undesirable oxidation compounds, given off from the Matzoth by the PE, which were not absorbed at detectable levels by the PVDC/PE.     

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.     

Properties of Transglutaminase Crosslinked Whey Protein Isolate Coatings and Cast Films

Whey protein is an excellent barrier material, potentially providing the low oxygen permeability and water vapour transmission rate required for packaging materials for sensitive foods. A topical issue is how to reduce the permeability of the whey protein‐based layers. One possible strategy is to apply crosslinking agents. In the present study, the enzyme transglutaminase (TG) was used for this purpose, and the following properties have been measured: oxygen permeability, water vapour transmission rate, effective water vapour diffusion, sorption and permeation coefficients, swellability, light transmission and surface energy. The use of TG was found to reduce the oxygen permeability, reduce the water vapour transmission rate and reduce the effective water vapour diffusion coefficient of the whey protein layers. This study also showed that it was possible to use sorption experiments to approximate the water vapour transmission rates. This work is novel because it deals with the packaging‐related properties of whey films crosslinked with TG. Previous studies have focused on the influence of TG on protein formulations or on the measurement of film properties, which is of little relevance for packaging applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and characterisation of starch/agar nanocomposite films for food packaging application

In the present work cassava starch/agar Ag and ZnO nanocomposite films were prepared by the solution casting method. The structural, physical and antimicrobial properties of the nanocomposite films were studied as a function of the concentration of Ag and ZnO nanoparticles. The results of the thermogravimetric analysis showed 8–15% degradation of both the nanocomposite films at 150°C endorsing the thermal stability of the films. Scanning electron microscopic analysis reveals the uniform blending of Ag and ZnO nanoparticles with a starch/agar matrix with tiny waves like appearance on the surface. The incorporation of Ag and ZnO nanoparticles in the film was found to reduce the moisture content, water solubility and water vapour permeability with increase in the concentration of Ag and ZnO nanoparticles. The growth kinetics study of Pseudomonas aeruginosa and Staphylococcus aureus in the presence of Ag and ZnO blended nanocomposite films showed promising results especially against Gram‐negative P. aeruginosa. Thus, the film synthesised in the present study bears the potential to be used as active packaging material to prevent food from bacterial contamination and spoilage.Inspec keywords: casting, microorganisms, scanning electron microscopy, nanoparticles, food preservation, solubility, thermal analysis, zinc compounds, food processing industry, food products, thermal stability, permeability, antibacterial activity, food packaging, contaminationOther keywords: water vapour permeability, food packaging, solution casting method, structural properties, physical properties, antimicrobial properties, water solubility, agar nanocomposite film, starch nanocomposite film, Pseudomonas aeruginosa, Staphylococcus aureus, bacterial contamination prevention, spoilage prevention, scanning electron microscopic analysis, thermogravimetric analysis, temperature 150.0 degC, Ag, ZnO     

Effect of Sn Doping on the Crystallization Kinetics of Amorphous TlInS<Subscript>2</Subscript> Films

The crystallization of amorphous Sn-doped TlInS₂ films into three polymorphs has been studied by kinematic electron diffraction. The results demonstrate that the crystallization of 30-nm-thick amorphous films produced by thermal evaporation in high vacuum can be described by the Avrami–Kolmogorov equation: V_τ = V₀[1–exp(–kτ^m)]. Kinematic electron diffraction patterns of the TlIn_1–хSn_xS₂ films have been used to assess the effect of doping with Sn on the growth dimensionality and the activation energy for the crystallization of the amorphous films and the unit-cell parameters of the resultant crystalline materials. Doping extends the temperature range and effective activation energy for the crystallization of the amorphous films.     

Stearate intercalated layered double hydroxides: effect on the physical properties of dextrin-alginate films

Glycerol-plasticized dextrin-alginate films were prepared by solution casting. They contained a fixed amount (16.6% mass/dry film mass) of functional filler based on the reaction products of the LDH, Mg₄Al₂(OH)₁₂CO₃·3H₂O, and stearic acid (SA). The films were characterized using infrared (IR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effect of filler composition on water vapour permeability and film stiffness was determined. The ratio of stearic acid (SA) to the LDH (Mg₄Al₂(OH)₁₂CO₃·3H₂O) was varied over the full composition range. Infrared spectroscopy and X-ray diffraction studies confirmed that the SA intercalated into the LDH. The Young’s modulus of films attained a maximum value (more than double the value for the neat film) at a filler composition of 60% SA. The water vapour permeability showed a broad minimum at filler compositions of 50–80% SA. Scanning electron microscopy revealed that in this composition range the filler assumes a high-aspect-ratio platelet morphology. This contrasts with the sand rose morphology of the LDH starting material and the globular dispersion of 100% SA in the film.     

Cat-CVD SiN passivation films for OLEDs and packaging

A Roll-to-roll type catalytic chemical vapor deposition (Cat-CVD) apparatus was developed for the application to flexible organic light-emitting diode (OLED) displays and packaging. Silicon nitride (SiN_x) films were prepared by this roll-to-roll type apparatus at temperatures below 60 °C. It was found that these SiN_x films are highly moisture resistant, and the water vapor transmission rate (WVTR) on plastic substrates could be lowered to 0.01 g/m² day. Roll-to-roll type Cat-CVD is one of the most promising methods for the preparation of barrier films for OLED displays and packaging.     

Effects of active chitosan-flaxseed mucilage-based films on the preservation of minced trout fillets: A comparison among aerobic,vacuum, and modified atmosphere packaging

The objectives of the current study were to examine physical–mechanical, structural, and morphological characteristics of chitosan-flaxseed mucilage films enriched with Ziziphora clinopodioides essential oil (ZEO; 0%, 0.25%, and 0.5%) and sesame oil (SO; 0% and 0.75%) and to provide useful information for the preservation of minced trout fillet's using antimicrobial films under aerobic, vacuum, and modified atmosphere conditions for 16 days. The films showed thickness, tensile strength, puncture force, puncture deformation, water vapor transmission rate, water vapor permeability, swelling index, and oxygen permeability values ranging 0.082–0.86 mm, 33.34–46.83 MPa, 25.69–53.08 N, 11.45–28.45 mm, 17.48–26.73 g/m² h, 8.57–12.49 × 10⁻⁴ g mm/m² h Pa, 12.45–38.43%, and 3.02–13.32 × 10⁻¹² cm³/m² s Pa, respectively. The following order of effect on the microbial spoilage population of treated samples was found in the applied packaging methods: modified atmosphere packaging > vacuum packaging > aerobic packaging. The final microbial population of treated samples was 0.35–4.91 log CFU/g lower than the controls after 16 days of refrigerated storage. At the end of the storage, the total volatile base nitrogen, peroxide value, and thiobarbituric acid reactive substances of untreated samples were 34.02–48.6 mg of N/100 g, 1.43–2.32 meq of peroxide/1000 g, and 3.33–4.24 mg of malondialdehyde/kg, respectively. The lowest corresponding values were recorded for the treated samples with ZEO 0.5% + SO 0.75% films by 14.26–17.73 mg of N/100 g, 0.48–0.86 meq of peroxide/1000 g, and 1.08–1.48 mg of malondialdehyde/kg, respectively.     

Photocatalysis and characterization of the gel-derived TiO2 and P-TiO2 transparent thin films

The gel-derived TiO₂ and P-TiO₂ transparent films coated on fused-SiO₂ substrates were prepared using a spin-coating technique. Effects of phosphorus dopants and calcination temperature on crystal structure, crystallite size, microstructure, light transmittance and photocatalytic activity of the films were investigated. By introducing P atoms to Ti-O framework, the growth of anatase crystallites was hindered and the crystal structure of anatase-TiO₂ could withstand temperature up to 900 °C. The photocatalytic activities of the prepared films were characterized using the characteristic time constant (τ) for the photocatalytic reaction. The titania film with a smaller τ value possesses a higher photocatalytic ability. After exposing to 365-nm UV light for 12 h, the P-TiO₂ films calcined between 600 °C and 900 °C can photocatalytically decomposed ≥ 84 mol% of the methylene blue in water with corresponding τ ≤ 7.1 h, which were better than the pure TiO₂ films prepared at the same calcination temperature.     

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.     

Numerical simulation of permeation through vacuum‐coated laminate films

The material usage in the packaging market of Germany has decreased over the last few years. This trend results from the substitution of heavy packages with light‐weight, flexible materials. In this context, aluminium foil‐based multilayer films have been partly replaced by metallized laminates in food packaging technology. Other coating materials, such as Al₂O₃ or SiO_x, are used where transparent films are desired. The disadvantage of these vacuum‐coated layers is the existence of pinholes which allow diffusion processes, in contrast to aluminium foil‐based multilayer films. In this study the barrier behaviour of vacuum coated laminate films was predicted by numerical simulation. The results are presented in terms of dimensionless parameters so that they may be transferred to analogous problems. This model provides a method to calculate the oxygen permeation through coated laminates. However, it is invalid for condensable gases such as water vapour. The simulation is suited for characterizing the influence of the compound structure on the barrier properties of vacuum coated laminate films. The results are verified by comparing the calculated with measured values. Copyright © 2002 John Wiley & Sons, Ltd.     

Degradation kinetics of thiamine hydrochloride in directly compressed tablets iii water vapour transmission through free and applied eudragit films

Abstract

Water vapour transmission through free and applied film of four Eudragit resins namely, E₁₀₀, L₁₀₀ and RS₁₀₀ to directly compressed thiamine hydrochloride tablets was investigated. The type of Eudragit film influenced both water vapour transmission and moisture absorption characteristics of the tablets compressed with either single or binary blend of vehicles. The moisture absorption rate constant K_a, for a given batch was found to be a function of vapour pressure, P, and film thickness, L. The relationship between K_a and either of these parameters is exponental and may be expressed as K_a = A exp (x/P) and K_a = K*_a exp (-x*L). In general, film coating with Eudragit resins affected the physical characteristics of the tablets. The rate of drug release, K has an exponentially relationship as K_e K_o exp (-c/L).     

Development of a mathematical model for the effect of temperature and relative humidity on the water vapour permeability of plastic films

The water vapour permeability constants of three flexible films (LDPE, PET and a laminate of both films) were determined at 20, 30 and 40 °C and from 55 to 90% relative humidities. The relationship between permeability and temperature followed the Arrhenius model for the three films. The relative humidity also influenced the permeability of the films. A mathematical model describing permeance (P/X - the permeability of laminates or films) as a function of external relative humidity and temperature was developed. The model can be used to predict the permeance of the three films at different temperatures and relative humidities.     

A critical assessment of methods for the determination of the shear stress amplitude in multiaxial fatigue criteria belonging to critical plane class

Multiaxial high cycle fatigue criteria based on the critical plane approach necessitate unambiguous definitions of the amplitude and mean value of the shear stress (τ_a and τ_m) acting on the material planes. Four of the existing definitions relate the values of τ_a and τ_m to a geometrical element of the curve described by the tip of the shear stress vector (curve Ψ), respectively, the radius of the Minimum Circumscribed Circle, the Longest Chord, the Longest Projection, the diagonal of the Maximum Rectangular Hull (MRH).In this paper a critical assessment of the above definitions is proposed, focusing on that based on the concept of MRH, which is the most recently developed. The main issues of the comparison are the uniqueness of the solution in the determination of τ_a and τ_m, the ability to differentiate proportional and non-proportional stresses, the differences of the values of τ_a obtained by each of the 4 methods for differently shaped curves Ψ.     

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.     

Noise and optimum filtering in spectrometers with semiconductor detectors operating at elevated temperatures

This paper deals with the contribution of excess noise of a simple surface-barrier semiconductor detector to the total noise of a detector-preamplifier system when operating at elevated temperatures. Assuming a conventional CR-RC-type filter, the variance of noise output is determined. A new term “second noise-corner time constant” τ_f is proposed. The expression for relative signal-to-noise ratio as a function of the noise- (τ_c and τ_f), as well as circuit- (τ_F and τ) time constants is derived. This is also presented in a graphical form.