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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.
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.
Polymer materials that regulate the relative humidity in their environment are relevant for applications in the packaging and building sectors. By integration of salts in polymer structures, such materials are able to absorb and desorb high amounts of water vapor. In this study, films of polylactic acid and polypropylene with dispersed calcium chloride (2 and 4 wt %) were produced and biaxially stretched to induce the formation of cavities. The resulting cavities in these films account up to 10 vol % and are able to contain emerging calcium chloride solution formed by water vapor absorption. These films absorb reversibly up to 15 wt % water vapor at 75% relative humidity at 23 °C. This absorption behavior is described by effective diffusion and effective sorption coefficients. Using a simple model, the effective water vapor diffusion coefficient of these films can be estimated from the permeation coefficient of the polymer and the sorption coefficient of the absorber.
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.