LDPE/PET laminated films modified with FeO(OH) × H2O,Fe2O3, and ascorbic acid to develop oxygen scavenging system for food packaging

The iron compounds (iron(III) oxide‐hydroxide monohydrate FeO(OH) × H₂O, iron(III) oxide Fe₂O₃, and ascorbic acid) were used as oxygen scavengers modifiers in laminating of polymer films. This oxygen‐scavenging system was coated on preselected films (low density polyethylene [LDPE] and polyethylene terephthalate [PET]) from which the laminates were formed. It presents the new form of composite material packaging that has the function of oxygen scavenging, which could be suitable for food packaging. The scope of the research included studies of morphology of oxygen scavengers by scanning electron microscope and their average particle size distribution measure by particle size analyzer, the effect of type, and concentration of these substances on viscosity of adhesive and seal strength of laminates. The Fourier‐transform infrared spectroscopy (FTIR) of laminates was also performed to observe the potential interaction of functional groups of polyurethane adhesives with oxygen scavenger components. The most important ability of the developed system for oxygen scavenging was confirmed by measuring oxygen concentration (% vol) in a headspace with the prepared laminates. The concentrations of selected oxygen scavengers (4‐6 wt%) and their combinations were studied. The most effective oxygen scavenger system integrated within the PE/PET composite film consists of 6 wt% ascorbic acid and 1 wt% FeO(OH) × H₂O, where the oxygen concentration of 1.0 vol% (±0.20 vol%) was obtained after 15 days of storage. It was found that in this system the oxygen scavenging reaction occurs through ascorbate oxidation to dehydroascorbic acid, which is catalyzed by reduction of Fe³⁺ to Fe2⁺ ions.     

Development of Palladium‐based Oxygen Scavenger: Optimization of Substrate and Palladium Layer Thickness

Oxygen scavenging films based on vacuum deposited palladium layers were developed to remove residual oxygen remaining in food packages after modified atmosphere packaging. Palladium (Pd) was coated on to a range of packaging films and in different thicknesses using magnetron sputtering technology. To improve the substrate surface, an additional silicon oxide (SiO_x) layer was also applied to the films before Pd deposition. To determine the oxygen scavenging activity, the scavenger films were placed into an airtight cell, which was flushed with a gas mixture containing 2 vol.% oxygen and 5 vol.% hydrogen. The results showed that the oxygen scavenging rate was strongly dependent on the coating substrate as well as on the Pd deposition thickness. Packaging films such as polyethylene terephthalate, aluminium oxide‐coated polyethylene terephthalate, oriented polypropylene and polylactic acid were found to be the most suitable substrates for Pd‐based oxygen scavengers. Moreover, it was demonstrated that the intermediate SiO_x layer between the substrate and the Pd layer led to a substantial increase in the oxygen scavenging activity rate (up to 33‐fold) for all applied packaging films. Additionally, it was shown that the optimal Pd layer thickness for the investigated oxygen scavenging films lies between 0.7 and 3.4 nm. The resulting scavenger films have the potential to scavenge residual headspace oxygen of sensitive foods within a matter of minutes leading to shelf life extension and overall quality improvements. Copyright © 2015 John Wiley & Sons, Ltd.     

Evaluation of absorption kinetics of oxygen scavenger sachets using response surface methodology

The performance of oxygen scavengers can be influenced by several conditions, such as temperature (T) and relative humidity (RH), which are considered to be the two major factors. Therefore, the development of new scavengers requires the study of their performance, with these conditions varied. In this paper, the response surface methodology (RSM) was used to study the performance of a newly developed oxygen scavenger sachet and to model the influences of T and RH and their interaction on the absorption capacity and rate constant of the developed sachet. Commercial oxygen scavenger sachets were used for comparison purposes. The oxygen absorption capacity and rate constant were evaluated with a 2² factorial design with a central point. The results showed that each absorber sachet presented a different behaviour and there were significant interactions between T and RH; so, the RSM was the most appropriate for these studies. The developed sachet presented a better performance compared with the commercial ones at 23°C and 53% RH, which represents the condition for commercialization at room temperature of foods of intermediary water activity, while in the extreme conditions (100% RH and 37°C) all sachets present a similar absorption capacity. Copyright © 2010 John Wiley & Sons, Ltd.     

Production of active PET films: evaluation of scavenging activity

The current trends in packaging technology are focusing on the development of functional materials that interact with the environment and with the food, playing an effective role in the preservation of quality. In particular, the so‐called active packaging technologies were developed as a response to the market needs for minimally treated foodstuffs, in order to preserve their freshness and flavours by regulating the gas composition of the packaging headspace through active scavengers. One of the most promising approaches for this technology is the incorporation of active scavengers into a polymeric matrix. Nevertheless, the design and the production of a functional and efficient active flexible package can be difficult to realize because of the complexity of the system. This work was thus focused on the production and the analysis of monolayer polyester films containing an oxygen scavenger. The active film was obtained by adding the active phase into a polyethylene terephthalate matrix during the extrusion process. The barrier properties of the films were investigated by means of conventional permeability measurement, to assess their activity with respect to oxygen. Additionally, the oxygen absorption of the active samples was analysed by an innovative oxygen meter system, in order to determine their scavenging capacity and reaction kinetics. The analysis of colour was carried out on packaged fresh apple slices, to verify if the active films produced were able to limit the oxidation processes on a sensitive food. Finally, the optical properties of the samples were investigated through haze measurements. Copyright © 2007 John Wiley & Sons, Ltd.     

Designing Efficient Oxygen Scavenging Coating Formulations for Food Packaging Applications

Modified atmosphere packaging is widely used to prolong the shelf life of many oxygen‐sensitive items including food, pharmaceuticals, work of art and so on. For food packaging applications, we investigated the effectiveness of oxygen scavenging coatings and flexographic printing ink formulations made using water soluble and water insoluble ascorbate enzyme systems. The present study summarizes the effects of various parameters on the oxygen scavenging rates and other performance aspects of the formulations. It is shown that; the initial oxygen scavenging rate can be increased by increasing the surface area of Calcium Ascorbate crystals and addition of catalyst or edible oil; addition of a catalyst like TiO₂ or Alumina and an edible oil in Ascorbate and laccase‐based formulations induces a synergistic effect upon the rate of scavenging oxygen from the packages; an efficient oxygen scavenging coating formulation can be made using water soluble Calcium Ascorbate and insoluble Ascorbate Palmitate containing enzyme and substrate; designing an efficient oxygen scavenging formulation using water insoluble Ascorbate Palmitate can reduce or eliminate formation of effluent which has potential to change the aperral of food items inside the package; an adverse effect of some binders which cause a reduction in the oxygen scavenging rate can be eliminated by making blends of different binders. Copyright © 2013 John Wiley & Sons, Ltd.     

Oxygen Scavengers Based on Titanium Oxide Nanotubes for Packaging Applications

Oxygen scavengers are commonly used in packaged foods and other oxygen sensitive goods because of the advantages they offer in maintaining quality and extending shelf life. The performance of oxygen scavengers can be influenced by several conditions, such as ambient temperature and relative humidity. We recently studied oxygen scavenging at room temperature using titanium oxide nanotubes (TONT). Prior work showed that TONTs can have oxygen uptake rates of up to three orders of magnitude higher compared with commercially available iron‐based scavengers at room temperature. However, the effect of humidity was not established. This research investigates the potential of TONTs as oxygen scavengers in packaging applications such as modified atmosphere packaging as well as a colour indicator. As opposed to commercial scavengers that need water to be active, TONT performs at their best in dry conditions, making them a strong potential candidate for pharmaceutical and medical devices industries. Copyright © 2017 John Wiley & Sons, Ltd.     

The control of dissolved oxygen content in probiotic yoghurts by alternative packaging materials

Probiotic bacteria, added to yoghurt to impart health benefits, require a low‐oxygen environment for maximum viability. The aim of this experiment was to produce yoghurt with minimal oxygen content using packaging systems. Three packaging systems were evaluated for the effect they exert on the dissolved oxygen content of two types of yoghurt. High‐impact polystyrene (the Australian yoghurt industry's material of choice) was compared with new oxygen‐barrier material and an oxygen‐scavenging active packaging system. Stirred‐type and set‐type yoghurts were observed in each packaging material for dissolved oxygen content, over a normal shelf‐life for yoghurt. Oxygen‐barrier packaging combined with an oxygen‐scavenging material was found to be the most effective system, particularly when used with set‐type yoghurt. Set‐type yoghurt was found to be more conducive to oxygen reduction using packaging methods. Copyright © 2003 John Wiley & Sons, Ltd.     

Long‐time Performance of Bottles Made of PET Blended with Various Concentrations of Oxygen Scavenger Additive Stored at Different Temperatures

Blending of poly(ethylene terephthalate) (PET) with oxygen scavenger additives is a way to reduce ingress of oxygen into PET bottles made of these blends. The objective is to reduce oxidation of packaged beverages and oils. However, few studies were performed about the long‐time influence of temperature on PET bottles with oxygen scavenger additives. Such knowledge is relevant for the development of accelerated tests. In this study, the influence of temperature on oxygen permeation of PET bottles with the oxygen scavenger additives MXD6 or Oxyclear® was examined. PET bottles made of blends of PET with 2, 5 and 8 wt.?% MXD6, respectively, or with 2 wt.?% Oxyclear® were filled with deoxygenated water. The bottles were stored at 5, 23, 38 and 55 °C up to 5 years. Oxygen partial pressure of the water in the bottles was measured regularly. As expected, oxygen partial pressure increased earlier at higher temperature because of faster exhaustion of the oxygen scavenger. Oxygen partial pressure of water in PET bottles with 8 wt.?% MXD6 was below 10 mbar even after 5 years storage time at 5 and 23 °C. Oxygen absorption capacity of activated MXD6 was at least 76 mg/g. This study shows that PET bottles with oxygen scavengers are able to reduce the oxygen ingress for several years, even at elevated temperatures. Copyright © 2017 John Wiley & Sons, Ltd.     

Adjustable Intermolecular Interactions Allowing 2D Transition Metal Dichalcogenides with Prolonged Scavenging Activity for Reactive Oxygen Species

There is an increasing demand for control over the dimensions and functions of transition metal dichalcogenides (TMDs) in aqueous solution toward biological and medical applications. Herein, an approach for the exfoliation and functionalization of TMDs in water via modulation of the hydrophobic interaction between poly(ε‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) and the basal planes of TMDs is reported. Decreasing the hydrophobic PCL length of PCL‐b‐PEG from 5000 g mol^?1 (PCL₅₀₀₀) to 460 g mol^?1 (PCL₄₆₀) significantly increases the exfoliation efficiency of TMD nanosheets because the polymer–TMD hydrophobic interaction becomes dominant over the polymer–polymer interaction. The TMD nanosheets exfoliated by PCL₄₆₀‐b‐PEG₅₀₀₀ (460‐WS₂, 460‐WSe₂, 460‐MoS₂, and 460‐MoSe₂) show excellent and prolonged scavenging activity for reactive oxygen species (ROS), but each type of TMD displays a different scavenging tendency against hydroxyl, superoxide, and 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) radicals. A mechanistic study based on electron paramagnetic resonance spectroscopy and density functional theory simulations suggests that radical‐mediated oxidation of TMDs and hydrogen transfer from the oxidized TMDs to radicals are crucial steps for ROS scavenging by TMD nanosheets. As‐prepared 460‐TMDs are able to effectively scavenge ROS in HaCaT human keratinocytes, and also exhibit excellent biocompatibility.     

Iron Carbides: Control Synthesis and Catalytic Applications in COx Hydrogenation and Electrochemical HER

Catalytic transformation of CO_x (x = 1, 2) with renewable H₂ into valuable fuels and chemicals provides practical processes to mitigate the worldwide energy crisis. Fe‐based catalytic materials are widely used for those reactions due to their abundance and low cost. Novel iron carbides are particularly promising catalytic materials among the reported ferrous catalysts. Recently, a series of strategies has been developed for the preparation of iron carbide nanoparticles and their nanocomposites. Control synthesis of FeC_x‐based nanomaterials and their catalytic applications in CO_x hydrogenation and electrochemical hydrogen evolution reaction (HER) are reviewed. The discussion is focused on the unique catalytic activities of iron carbides in CO_x hydrogenation and HER and the correlation between structure and catalytic performance. Future synthesis and potential catalytic applications of iron carbides are also summarized.     

High Rate Magnesium–Sulfur Battery with Improved Cyclability Based on Metal–Organic Framework Derivative Carbon Host

Mg batteries have the advantages of resource abundance, high volumetric energy density, and dendrite‐free plating/stripping of Mg anodes. However the injection of highly polar Mg²⁺ cannot maintain the structural integrity of intercalation‐type cathodes even for open framework prototypes. The lack of high‐voltage electrolytes and sluggish Mg²⁺ diffusion in lattices or through interfaces also limit the energy density of Mg batteries. Mg–S system based on moderate‐voltage conversion electrochemistry appears to be a promising solution to high‐energy Mg batteries. However, it still suffers from poor capacity and cycling performances so far. Here, a ZIF‐67 derivative carbon framework codoped by N and Co atoms is proposed as effective S host for highly reversible Mg–S batteries even under high rates. The discharge capacity is as high as ≈600 mA h g^?1 at 1 C during the first cycle, and it is still preserved at ≈400 mA h g^?1 after at least 200 cycles. Under a much higher rate of 5 C, a capacity of 300–400 mA h g^?1 is still achievable. Such a superior performance is unprecedented among Mg–S systems and benefits from multiple factors, including heterogeneous doping, Li‐salt and Cl^? addition, charge mode, and cut‐off capacity, as well as separator decoration, which enable the mitigation of electrode passivation and polysulfide loss.     

Characterization of polyethylene terephthalate/polyaniline blends as potential antioxidant materials

Polyethylene terephthalate (PET) blends with a nanorod form of polyaniline (NR-PANI), formed by a falling pH synthesis, were prepared by dispersion in a melt of PET at 265 °C. Blends with 1, 2 and 3 wt% NR-PANI loading were prepared. Optical microscopy revealed an even distribution of NR-PANI particles within the PET matrix. The blends were characterized using FTIR, XPS, DSC and DMTA. Melt flow index values suggested hydrolysis of PET chains to lower molecular weight units when NR-PANI was blended. Some PET hydrolysis was also evident from the increasing oxygen to carbon ratios with an increased NR-PANI content in the blends. While the PET glass transition temperature remained relatively unaffected, the degree of PET crystallinity was increased with the addition of NR-PANI. The electrical conductivity as well as the free radical scavenging capacity of PET increased with greater NR-PANI loading in the matrix. The mechanical properties of PET, however, declined with NR-PANI loading suggesting a lack of adequate interfacial adhesion between the NR-PANI particles and the PET matrix.     

Photothermal‐Responsive Microporous Nanosheets Confined Ionic Liquid for Efficient CO2 Separation

2D materials hold promising potential for novel gas separation. However, a lack of in‐plane pores and the randomly stacked interplane channels of these membranes still hinder their separation performance. In this work, ferrocene based‐MOFs (Zr‐Fc MOF) nanosheets, which contain abundant of in‐plane micropores, are synthesized as porous supports to fabricate Zr‐Fc MOF supported ionic liquid membrane (Zr‐Fc‐SILM) for highly efficient CO₂ separation. The micropores of Zr‐Fc MOF nanosheets not only provide extra paths for CO₂ transportation, and thus increase its permeance up to 145.15 GPU, but also endow the Zr‐Fc‐SILM with high selectivity (216.9) of CO₂/N₂ through the nanoconfinement effect, which is almost ten times higher than common porous polymer SILM. Furthermore, based on the photothermal‐responsive properties of Zr‐Fc MOF, the performance is further enhanced (35%) by light irradiation through a photothermal heating process. This provides a brand new way to design light facilitating gas separation membranes.     

Hollow PtPdRh Nanocubes with Enhanced Catalytic Activities for In Vivo Clearance of Radiation‐Induced ROS via Surface‐Mediated Bond Breaking

Catalytic nanomaterials can be used extrinsically to combat diseases associated with a surplus of reactive oxygen species (ROS). Rational design of surface morphologies and appropriate doping can substantially improve the catalytic performances. In this work, a class of hollow polyvinyl pyrrolidone‐protected PtPdRh nanocubes with enhanced catalytic activities for in vivo free radical scavenging is proposed. Compared with Pt and PtPd counterparts, ternary PtPdRh nanocubes show remarkable catalytic properties of decomposing H₂O₂ via enhanced oxygen reduction reactions. Density functional theory calculation indicates that the bond of superoxide anions breaks for the energetically favorable status of oxygen atoms on the surface of PtPdRh. Viability of cells and survival rate of animal models under exposure of high‐energy γ radiation are considerably enhanced by 94% and 50% respectively after treatment of PtPdRh nanocubes. The mechanistic investigations on superoxide dismutase (SOD) activity, malondialdehyde amount, and DNA damage repair demonstrate that hollow PtPdRh nanocubes act as catalase, peroxidase, and SOD analogs to efficiently scavenge ROS.     

Covalent‐Organic‐Framework‐Based Li–CO2 Batteries

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials constructed from designer molecular building blocks that are linked and extended periodically via covalent bonds. Their high stability, open channels, and ease of functionalization suggest that they can function as a useful cathode material in reversible lithium batteries. Here, a COF constructed from hydrazone/hydrazide‐containing molecular units, which shows good CO₂ sequestration properties, is reported. The COF is hybridized to Ru‐nanoparticle‐coated carbon nanotubes, and the composite is found to function as highly efficient cathode in a Li–CO₂ battery. The robust 1D channels in the COF serve as CO₂^– and lithium‐ion‐diffusion channels and improve the kinetics of electrochemical reactions. The COF‐based Li–CO₂ battery exhibits an ultrahigh capacity of 27 348 mAh g^?1 at a current density of 200 mA g^?1, and a low cut‐off overpotential of 1.24 V within a limiting capacity of 1000 mAh g^?1. The rate performance of the battery is improved considerably with the use of the COF at the cathode, where the battery shows a slow decay of discharge voltage from a current density of 0.1 to 4 A g^?1. The COF‐based battery runs for 200 cycles when discharged/charged at a high current density of 1 A g^?1.     

A High‐Capacity O2‐Type Li‐Rich Cathode Material with a Single‐Layer Li2MnO3 Superstructure

A high capacity cathode is the key to the realization of high‐energy‐density lithium‐ion batteries. The anionic oxygen redox induced by activation of the Li₂MnO₃ domain has previously afforded an O3‐type layered Li‐rich material used as the cathode for lithium‐ion batteries with a notably high capacity of 250–300 mAh g^?1. However, its practical application in lithium‐ion batteries has been limited due to electrodes made from this material suffering severe voltage fading and capacity decay during cycling. Here, it is shown that an O2‐type Li‐rich material with a single‐layer Li₂MnO₃ superstructure can deliver an extraordinary reversible capacity of 400 mAh g^?1 (energy density: ≈1360 Wh kg^?1). The activation of a single‐layer Li₂MnO₃ enables stable anionic oxygen redox reactions and leads to a highly reversible charge–discharge cycle. Understanding the high performance will further the development of high‐capacity cathode materials that utilize anionic oxygen redox processes.     

Active packaging of UHT milk to prevent the development of stale flavour during storage

Indirectly processed UHT milk was packaged in Intasept^TM aseptic pouches with (treatment) or without (control) oxygen‐scavenging film and stored for 14 weeks at 26 ± 0.3°C. Samples were analysed at 0, 4, 8 and 14 weeks for dissolved oxygen, stale flavour volatiles (methyl ketones and aldehydes) and free fatty acids. Discriminative subjective analysis of odour by a consumer panel was also conducted. The oxygen‐scavenging film was shown to significantly (p < 0.05) reduce dissolved oxygen content by 23–28% during storage. Significant reductions of 23–41% were also observed for some stale flavour volatiles, including three methyl ketones and two aldehydes. Free fatty acid levels remained far below threshold values, indicating that lipolytic rancidity would not interfere with the subjective analysis. However, the consumer panel failed to detect a significant difference in odour between the treatment and control samples. Copyright © 2006 John Wiley & Sons, Ltd.     

Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO2RR)

In the face of the global energy challenge and progressing global climate change, renewable energy systems and components, such as fuel cells and electrolyzers, which close the energetic oxygen and carbon cycles, have become a technology development priority. The electrochemical oxygen reduction reaction (ORR) and the direct electrochemical carbon dioxide reduction reaction (CO₂RR) are important electrocatalytic processes that proceed at gas diffusion electrodes of hydrogen fuel cells and CO₂ electrolyzers, respectively. However, their low catalytic activity (voltage efficiency), limited long‐term stability, and moderate product selectivity (related to their Faradaic efficiency) have remained challenges. To address these, suitable catalysts are required. This review addresses the current state of research on Pt‐based and Cu‐based nanoalloy electrocatalysts for ORR and CO₂RR, respectively, and critically compares and contrasts key performance parameters such as activity, selectivity, and durability. In particular, Pt nanoparticles alloyed with transition metals, post‐transition metals and lanthanides, are discussed, as well as the material characterization and their performance for the ORR. Then, bimetallic Cu nanoalloy catalysts are reviewed and organized according to their main reaction product generated by the second metal. This review concludes with a perspective on nanoalloy catalysts for the ORR and the CO₂RR, and proposes future research directions.     

Bamboo‐Like Nitrogen‐Doped Carbon Nanotube Forests as Durable Metal‐Free Catalysts for Self‐Powered Flexible Li–CO2 Batteries

The Li–CO₂ battery is a promising energy storage device for wearable electronics due to its long discharge plateau, high energy density, and environmental friendliness. However, its utilization is largely hindered by poor cyclability and mechanical rigidity due to the lack of a flexible and durable catalyst electrode. Herein, flexible fiber‐shaped Li–CO₂ batteries with ultralong cycle‐life, high rate capability, and large specific capacity are fabricated, employing bamboo‐like N‐doped carbon nanotube fiber (B‐NCNT) as flexible, durable metal‐free catalysts for both CO₂ reduction and evolution reactions. Benefiting from high N‐doping with abundant pyridinic groups, rich defects, and active sites of the periodic bamboo‐like nodes, the fabricated Li–CO₂ battery shows outstanding electrochemical performance with high full‐discharge capacity of 23 328 mAh g^?1, high rate capability with a low potential gap up to 1.96 V at a current density of 1000 mA g^?1, stability over 360 cycles, and good flexibility. Meanwhile, the bifunctional B‐NCNT is used as the counter electrode for a fiber‐shaped dye‐sensitized solar cell to fabricate a self‐powered fiber‐shaped Li–CO₂ battery with overall photochemical–electric energy conversion efficiency of up to 4.6%. Along with a stable voltage output, this design demonstrates great adaptability and application potentiality in wearable electronics with a breath monitor as an example.     

Cooling performance of several CO2/propane mixtures and glide matching with secondary heat transfer fluid

This paper presents the cooling performance of several CO₂/propane mixtures measured in air-conditioning test rig at several conditions. The discharge pressure of CO₂/propane mixtures is reduced with increasing mole fraction of propane and their reduced values coincide approximately with the circulation concentrations of propane. Since propane is the refrigerant having a higher refrigerating effect and a much lower vapor density than CO₂, adding propane to CO₂ improves the system efficiency and reduces the cooling capacity. The temperature glide effect of CO₂/propane mixtures on the cooling performance was analyzed based on the experimental data. To utilize the temperature glide effect successfully, a sufficient heat exchange area is required, and the temperature gradient of refrigerant must be similar to that of secondary heat transfer fluid. It is better the temperature change of refrigerant can prevent pinching with that of the secondary heat transfer fluid.