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Palladium-based oxygen scavenger for food packaging: Choosing optimal hydrogen partial pressure
(2021)
Several packaging solutions for the food industry have to consider the harmful effects of oxygen within a pack for packaging of oxygen sensitive foods. This issue can be addressed by using oxygen scavengers. However, in adverse cases, conventional oxygen scavengers react too slowly to reduce the access of oxygen to sensible foods. Therefore, several alternative approaches for oxygen scavengers are in focus right now. In this work, an oxygen scavenger system based on vacuum-deposited palladium (Pd) on PET films was tested. Pd catalyzes the reaction of headspace oxygen, remaining in food packages, with hydrogen. The hydrogen can be provided by modified atmosphere packaging. To improve the substrate surface, an additional silicon oxide (SiOx) layer was applied to the films before Pd deposition. To determine the oxygen-scavenging activity, the Pd-metalized films were placed into airtight cells. These cells were flushed with a gas mixture containing 95 vol.-% nitrogen and 5 vol.-% hydrogen. Defined amounts of oxygen were injected into the cells. The kinetic parameters of Pd-metalized films were determined as a function of hydrogen and oxygen partial pressures and area of Pd-coated film. The effect of different cover films on Pd on the reaction rate was analyzed, too. By the results was shown that the oxygen-scavenging rate is strongly dependent on the proportion of hydrogen to oxygen. The oxygen-scavenging rate increases with a decreasing ratio of hydrogen to oxygen (with ratio 2.5:1 as the fastest tested condition). However, there has to be a sufficient hydrogen excess inside the headspace to reach overall highest oxygen-scavenging capacity (ratio up to 10.6:1 tested). For practical application in food packaging, it is important to adjust the hydrogen concentration in modified atmosphere packaging to residual oxygen present in packaging, to choose a sufficient area of Pd-metalized film as well as suitable cover film with high oxygen permeance. This publication provides recommendations for this purpose.
The water vapour transmission rate (WVTR) of packaging materials and edible coatings is one of their critical parameters for the shelf life of many food products. The water vapour transmission rates of flat bodies such as films are determined by permeation measurements which are a steady-state method. Another method is based on water vapour sorption measurements which is a non-steady-state method. It can be used only for mono-material flat bodies. It allows using smaller sample areas compared to permeation measurements. However, not much is known about how well both methods correlate with each other. Therefore, the aim of this study was to compare the WVTR results of different materials determined by both methods. The results of both methods differed by up to factor of three, measured at identical samples. In a few cases the difference was up to factor five. The exact reasons for these differences are unknown. Nonetheless, the water vapour sorption method is a suitable method to determine the magnitue of order of the water vapour transmission rate but not its exact value.
The oxygen permeability of films is relevant for packaging related and technical applications. An increasingly used test method for the measurement of oxygen permeability is the optical test method, because it allows a simple and cost-efficient measurement setup. This method is based on optical chemical sensors. However, not much is known about its validity. Therefore, method validation is necessary which is subject of this study. The optical method is compared with the carrier gas method for a variety of film samples. In the tested permeability range of 0.5–2500 cm3 (STP)·(m2 d bar)−1 both methods deviated less than 20% for zero and 50% relative humidity.
The relative humidity level in the immediate vicinity of objects such as foods and technical items has an influence on transpiration and undesired relative humidity dependent reactions on their surfaces such as water vapour condensation, chemical reactions and microbial growth. Desirable are therefore materials that regulate the relative humidity to predefined levels in closed spaces such as in packagings and also in housing spaces. Such materials should be able to adjust the surface humidity of objects via water vapour diffusion in the gas phase without being in direct contact. A strategy to create such humidity regulating materials is the use of substances that absorb and desorb high amounts of water vapour, such as sodium chloride. Sodium chloride (NaCl) particles absorb water vapour at a relative humidity above 75% at 23 degrees C and then they form NaCl solution. NaCl solution desorbs water vapour when the relative humidity in the immediate vicinity decreases below the equilibrium relative humidity of that salt solution. Therefore, this system is able to regulate the relative humidity in its immediate vicinity. A strategy to provide free space in polymeric structures for the NaCl solution is the creation of cavities by foaming and stretching. However, only little knowledge exists about the influence of the combination of both processes on the functional properties of humidity regulating films with salt as active substance. Hence, the aim of this study was to investigate how and to which extend foaming and/or stretching affects the functional properties, i.e. water vapour sorption and mechanical properties, of polypropylene (PP) films containing NaCl particles. For this study, foamed and non-foamed PP with 3 and 6 weight-% NaCl were extruded into films. In the next step, some of these samples were biaxially stretched and their structures, water vapour absorption, porosities and mechanical strengths were analysed. The only-foamed films had a porosity of 0.3, the porosity of only-biaxially stretched films was between 0.1 and 0.2. The porosity increased to 0.7 when the films were first foamed and stretched afterward. Foamed and then stretched films with 6 wt.-% NaCl absorbed a high amount of water vapour from air with a value of 0.8 g H2O/g film at 97% relative humidity. Stretching of filled and non-filled foamed films also resulted in higher mechanical strength of the pure matrix polymer in comparison to the pure matrix polymer of non-stretched films. By the results of this study is shown that humidity regulating films with high water vapour sorption capacity can be produced via extrusion, foaming and stretching processes which are established processes in the polymer industry.
The aim of this study was to evaluate the influence of relative humidity (RH) on the oxygen permeability and water vapour transmission rate (WVTR) of whey protein coated Polyethylene terephthalate (PET) or whey protein monolayer films. Furthermore, the activation energies for the permeability of oxygen, carbon dioxide and nitrogen as well as the permselectivities under different set of temperatures were measured. The results showed that the permeability values through the whey protein coating and whey protein film increased with increasing RH. The water vapour permeability measured at 50% RH of (9.3 ± 0.6)−10 cm3 (STP) cm cm−2 s−1 Pa−1 increased to (16.2 ± 0.9)−10 cm3 (STP) cm cm−2 s−1 Pa−1 at 85% RH. An increase in temperature showed an expected increase of the permeability in both uncoated PET and the whey protein monolayer. The permselectivity of whey protein film was determined and the calculated ratios of the permselectivity (P(N2)/P(O2)/P(CO2):1/(4–6/(34–35)) differed from the simplified ratios given in the literature (P(N2)/P(O2)/P(CO2):1/4/16). Furthermore the calculated activation energy values for whey (51 kJ mol−1) were in agreement with other studies.
Oxygen scavengers are used to reduce the oxygen permeation of packaging (active barrier) and to absorb oxygen from its direct environment, e.g., a headspace of packaged food. Few oxygen scavenger coatings have been developed. Therefore, in this study, a novel oxygen scavenger coating has been developed. It is based on inorganic–organic polymers (ORMOCER®). The oxygen absorption reaction is activated by UV light. The scavenger was synthesized, coated on aluminum foil, subsequently dried and afterwards laminated with a polyethylene sealing layer. UV light activates the oxygen scavenging reaction. The oxygen absorption capacity, measured at 23 °C and 0% r.h., was 242 ± 8 mg oxygen/g scavenger coating. When the oxygen scavenger coating layer was laminated by using a two-component polyurethane laminating adhesive, the absorption capacity was hardly reduced, with a measured absorption capacity of 223 ± 18 mg oxygen/g scavenger coating. In an experimental packaging sample with the oxygen scavenger coating with a thickness (dry) of 3 µm and 18 µm, near-zero mbar oxygen partial pressure was reached by the non-laminated oxygen scavenger coatings within two days, and within about 20 days when laminated with a polyurethane laminating adhesive and a PE-layer on the oxygen scavenger layer. The oxygen partial pressure was kept near zero mbar for 500 days, whereas in the experimental packaging without oxygen scavenger, the oxygen partial pressure increased to 110 mbar during this time. The developed oxygen scavenger based on inorganic–organic polymers can be applied as wet chemical coating on various surfaces with standard application procedures. Application scenarios are oxygen-sensitive goods such as food, pharmaceutical products and cosmetics.
Silica gel is a well-known desiccant. Through dispersion of silica gel in a polymer, films can be made that absorb and desorb water vapor. The water vapor absorption becomes reversible by exposing such films to a water vapor pressure below that of the water vapor pressure during absorption, or by heating the film. The intention of this study was to achieve a better understanding about the water vapor absorption, permeability (H2O, N2, O2, CO2), and mechanical properties of films with dispersed silica gel. Low-density polyethylene (PE-LD) monolayer films with a nominal silica gel concentration of 0.2, 0.4, and 0.6 g dispersed silica gel per 1 g film (PE-LD) were prepared and they absorbed up to 0.08 g water vapor per 1 g of film. The water vapor absorption as a function of time was described by using effective diffusion coefficients. The steady state (effective) water vapor permeation coefficients of the films with dispersed silica gel were a factor of 2 to 14 (8.4 to 60.2·10−12 mg·cm·(cm2·s·Pa)−1, 23 °C) higher than for pure PE-LD films (4.3·10−12 mg·cm·(cm²·s·Pa)−1, 23 °C). On the other hand, the steady state gas permeabilities for N2, O2, and CO2 were reduced to around one-third of the pure PE-LD films. An important result is that (effective) water vapor permeation coefficients calculated from results of sorption and measured by permeation experiments yielded similar values. It has been found that it is possible to describe the sorption and diffusion behavior of water by knowing the permeability coefficient and the sorption capacity of the film (Peff.≈Seff.⋅Deff.). The tensile stress changed only slightly (values between 10 and 14 N mm−2), while the tensile strain at break was reduced with higher nominal silica gel concentration from 318 length-% (pure PE-LD film) to 5 length-% (PE-LD with 0.6 g dispersed silica gel per 1 g film).
Polymers with dispersed desiccants are relevant for various packaging applications to protect packaged goods from water vapor. The intention of this study was to analyze and to describe a relevant system. Therefore, films with calcium oxide (CaO) were investigated, because such materials are hardly described in scientific literature. Monolayer films with 0.14 to 0.51 g dispersed CaO per 1 g film (PE‐LD) were prepared and they absorbed up to 0.2 g water vapor per 1 g of film. The water vapor absorption was described by effective diffusion coefficients. By the use of effective diffusion coefficients and the absorption capacity, the absorption behavior of layers with various thicknesses can be estimated. The steady state (effective) water vapor permeation coefficients of the films with dispersed CaO were a factor of 2 to 24 (8.4 to 101.5 mg cm [cm2 s Pa]–1 × 1012, at 23 °C) higher than for pure PE‐LD films (4.26 mg cm [cm2 s Pa]−1 × 1012, 23 °C). The tensile stress changed only slightly (pure PE‐LD: 9.5 N mm−2; PE‐LD with 0.14 g dispersed CaO per 1 g film: 8.1 N mm−2; PE‐LD with 0.51 g dispersed CaO per 1 g film: 10.5 N mm−2), while the tensile strain at break was reduced with higher CaO concentration from 318% (pure PE‐LD) to 10% (PE‐LD with 0.51 g dispersed CaO per 1 g film). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47460.
Polymers with dispersed desiccants are relevant for various packaging applications to protect packaged goods from water vapor. The intention of this study was to analyze and to describe a relevant system. Therefore, films with calcium oxide (CaO) were investigated, because such materials are hardly described in scientific literature. Monolayer films with 0.14 to 0.51 g dispersed CaO per 1 g film (PE-LD) were prepared and they absorbed up to 0.2 g water vapor per 1 g of film. The water vapor absorption was described by effective diffusion coefficients. By the use of effective diffusion coefficients and the absorption capacity, the absorption behavior of layers with various thicknesses can be estimated. The steady state (effective) water vapor permeation coefficients of the films with dispersed CaO were a factor of 2 to 24 (8.4 to 101.5 mg cm [cm(2) s Pa](-1) x 10(12), at 23 degrees C) higher than for pure PE-LD films (4.26 mg cm [cm(2) s Pa](-1) x 10(12), 23 degrees C). The tensile stress changed only slightly (pure PE-LD: 9.5 N mm(-2); PE-LD with 0.14 g dispersed CaO per 1 g film: 8.1 N mm(-2); PE-LD with 0.51 g dispersed CaO per 1 g film: 10.5 N mm(-2)), while the tensile strain at break was reduced with higher CaO concentration from 318% (pure PE-LD) to 10% (PE-LD with 0.51 g dispersed CaO per 1 g film). (c) 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47460.