A R T I C L E I N F O A B S T R A C T
Article history:
Received 17 May 2016 Oxygen scavengers which are based on oxidation of iron powder dispersed in a polymer matrix are
Received in revised form 2 January 2017 established in the packaging industry. They protect foods from oxygen. The iron particles have a diameter
Accepted 16 January 2017 of several micrometers, which is too high to allow thin layers in multilayer lm structures. A promising
Available online xxx alternative is a developed nanoscale oxygen scavenger which is subject of this study. The aim of this study
was to evaluate the oxygen absorption rate and the oxygen absorption capacity of nanoscale iron at 100%
Keywords: relative humidity and at dry conditions.
Nanoparticle Nanoscale oxygen scavengers (zero valent iron particles) were synthesized. Their reactivity was tested.
Oxidation
Furthermore, they were blended with a silicone matrix. The nanoscale oxygen scavenger absorbed
Coreshell nanoparticle
oxygen in wet (100% relative humidity) and dry conditions. At 100% relative humidity the reaction rate of
Active packaging
the powder was two to three times higher compared to non-nanoscale iron powder. The absorption rate
of the nanoscale iron dispersed in a silicon carrier was at least ten times higher at 100% relative humidity
compared to a commercially available iron based oxygen scavenger in a polyethylene or polypropylene
polymer matrix.
2017 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fpsl.2017.01.003
2214-2894/ 2017 Elsevier Ltd. All rights reserved.
Z. Foltynowicz et al. / Food Packaging and Shelf Life 11 (2017) 7483 75
bounds) and inorganic (e.g. metal powders) systems. Organic powder is already active in conditions of dehydrated and dry foods.
systems include Nylon MXD6 (a mainly aliphatic polyamide resin Crane assumed a passivating layer thickness of 3 nm (Crane, &
which contains meta-xylylene groups) blended with Poly(ethylene Scott, 2012). In this case a sphere is fully oxidised when the
terephthalate) (PET), ethylene methylacrylate cyclohexenylmethyl, diameter is 6 nm or less. At 20 nm diameter around 65 vol-% of the
cyclo-olen bonded chemically to a silicate backbone, low-density sphere is oxidised. The passivating layer consists of iron oxides or
polyethylene lled with oxygen scavengers made of powdered oxyhydroxides (Liu & Zhang, 2014). Also in humid conditions and
activated carbon impregnated with sodium erythorbate, polybu- in contact with electrolytes the reaction rate of nanoscale iron
tadiene, gallic acid and others (Amberg-Schwab, Weber, Burger, would be much faster than at iron powders with a diameter of
Nique, & Xalter, 2006; Dombre, Guillard, & Chalier, 2015; Goldhan several micrometres.
et al., 2007; Joven, Garcia, Arias, & Medina, 2014; Li, Tung, Paul, & Nanoscale iron powder is available as zero valent iron (ZV). In
Freeman, 2011; Mller, Sngerlaub, Kramer, Huber, & Fritsch, 2011; recent years it gained prominence in research because it catalyses
Mller, Welle, Rieblinger, & Sngerlaub, 2010 Piton & Rivaton, and/or oxidises the decomposition of contaminants such as
1996; Singh, Sngerlaub, Wani, & Langowski, 2012; Singh, Wani, & antibiotics, biocides, hexachlorobenzene, azo dyes and it can be
Sngerlaub, 2011; Schneider, Orzinski, Embs, Fritsch, & Weber, therefore applied for water treatments and decontamination (Crane
2006; Solis & Rodgers, 2001). Their oxidation is often catalysed, e.g. & Scott, 2012; Fang et al., 2011; Homem & Santos, 2011; Moon, Park, &
by cobalt compounds. Inorganic systems include polymers blended Park, 2011; Shih, Hsu, & Su, 2011; Zha et al., 2014; Xu & Wang, 2011).
with iron powder, different iron compounds and sodium sulphite Additionally it inactivates microbes (Diao & Yao, 2009). Several
(Cruz, Camilloto, & Pires, 2012; Foltynowicz, Kozak, & Fiedorow, groups measured the diameters of zero valent iron particles. The
2002; Gibis & Rieblinger, 2011; Galotto, Anfossi, & Guarda, 2009; smallest diameters were between 3 nm and 5 nm (Machado, Grosso,
Mller et al., 2010; Mller, 2013; Rooney, 1995; Singh et al., 2012, Nouws, Albergaria, & Delerue-Matos, 2014; Oropeza, Corea, Gmez-
2011). Oxygen scavengers differ in their absorption kinetics, Yez, Cruz-Rivera, & Navarro-Clemente, 2012).
absorption capacity, time-temperature behavior, reactivity at For food packaging related applications Mu and Busolo did
different relative humidities and costs. experiments with nanoscale iron. Mu prepared nanoscale iron
One of the most important systems for packaging materials is from borohydride resulting in 110 nm particle size (Busolo &
the group of oxygen scavengers that contain iron powder (Chiang Lagaron, 2012; Mu et al., 2013). The nanoscale iron and iron with a
et al., 1997; Gibis & Rieblinger, 2011; Lehner, Schlemmer, & particle size of around 20 mm was mixed with activated carbon,
Sngerlaub, 2015; Mller et al., 2010; Singh et al., 2012; Singh et al., NaCl and calcium chloride in a weight ratio of 1:1:1:0.2. At 75%
2011; Sngerlaub et al., 2012). They are a mixture of a carrier relative humidity and 25 C nanoscale iron absorbed oxygen circa 9
polymer, iron powder with a particle diameter in the range of 10 to times faster than conventional iron. The compound absorbed circa
30 micrometres and a catalyst such as sodium chloride (NaCl) 220 cm3 oxygen per one gram of iron, which is circa 280 mg per one
(Chiang et al., 1997; Klein & Knorr, 1990; Lpez-Cervantes, gram of iron (density of oxygen at 25 C, 1013 mbar: 1.3093 mg
Snchez-Machado, Pastorelli, Rijk, & Paseiro-Losada., 2003; cm3). The oxygen absorption capacity was lower than the
Sngerlaub et al., 2012; Galotto et al., 2009). In dry conditions stoichiometric capacity of 430 mg oxygen per one gram iron.
metallic iron is inert even though it is a non-nobel metal. The Busolo used an iron containing kaolinite (Busolo & Lagaron, 2012).
reason for this property is that metallic iron forms on its surface a The average iron particle diameter was 115 nm. The iron containing
passivating layer in the thickness of several nanometres (Ohtsuka, kaolinite and a HDPE-powder compound with the iron containing
2012; McCafferty, 2010). At high relative humidity or in contact kaolinite were analysed. At 100% relative humidity the reaction
with liquid water the passivating layer reacts with water and rate was higher than at 50% relative humidity. Interestingly, zero
becomes porous, which makes this layer permeable for water valent iron modied bentonite and kaolinite are approved by the
vapour and oxygen. Therefore, metallic iron below this porous European Food Safety Authority (EFSA) as non-nanoform species
layer is accessible for water vapour and oxygen and can react then (EFSA 2013a, 2013b).
with both. The oxidation is catalysed be electrolytes, e.g. NaCl.
Galotto and Saengerlaub reported that oxygen scavengers with 1.1. Intention of the present study
iron powder start to react with oxygen at a relative humidity of 75%
or higher (Galotto et al., 2009; Sngerlaub et al., 2012). Results from For this study an oxygen scavenger based on nanoscale iron
Schindelholz indicate that reaction starts already at a lower (nano iron) was synthesised. The intention of this study was to
relative humidity (Schindelholz, Risteen, & Kelly, 2014). He showed measure and to evaluate its oxygen absorption rate and its oxygen
that steel in direct contact with NaCl had a low but detectable absorption capacity.
corrosion rate at 33% relative humidity. The corrosion rate
increased at higher relative humidity (>53%) by factor 300 to 2. Materials and methods
2500. In polymers with dispersed iron powder and NaCl the
property of non-nanoscale NaCl is used to absorb water vapour 2.1. Experimental plan
above 75% relative humidity (deliquescence point) and to solve in
the absorbed water (Ewing, 2005). The salt solution can then wet Table 1 shows the samples of this study. Samples were analysed
the surface of the metallic iron particles and catalyse the oxidation in measuring cells with dened headspace. The weight of iron
of iron by oxygen there. This behaviour explains the higher reaction powder was similar or in the same range at all samples as well as
rate of iron powder when the relative humidity is higher than 75% the headspace-sample ratio. Nanoscale iron was analysed in cells
(Galotto et al., 2009; Klein & Knorr, 1990; Sngerlaub et al., 2012). with and without a petri dish of water with the aim to evaluate the
An important property of oxygen scavengers is their reaction inuence of relative humidity on the reaction rate. Iron powder
rate. A strategy to increase the reaction rate is the reduction of was mixed with NaCl because this electrolyte catalyses the
particle diameters. The area of spheres increases by factor 10 when oxidation and because it is applied at oxygen scavengers with
the particle diameter decreases be factor 10. For example iron iron powder. The concentration of NaCl was varied to 1 and 10% w/
powder with a particle diameter of 10 nm instead of 10 mm will w to study the inuence of its concentration on the reaction rate.
have a 1000 times bigger surface area. Due to the fact that the For comparison oxygen scavenger lms containing the commer-
passivating layer of metallic iron is several micrometres thick and cially available oxygen scavenger SHELFPLUS1 O2 were provided by
forms in dry conditions or at very low relative humidity such iron Fraunhofer IVV. The system SHELFPLUS1 O2 is an oxygen scavenger
76 Z. Foltynowicz et al. / Food Packaging and Shelf Life 11 (2017) 7483
Table 1
Experimental plan of samples for testing oxygen absorption kinetics and oxygen absorption capacity, all experiments were done at 23 C; initial oxygen concentration: 20.95
vol.-%.
with iron particles that is blended with polymer and extruded to and nanoscale iron were chosen after pre-trials. The aim was to
separate layers in multilayer lm structures. The technology and the cover maximum amount of nanoscale iron powder with a
intellectual property rights for the oxygen scavenger SHELFPLUS1 O2 minimum amount of silicone.
were formerly owned by BPAmoco and Ciba Specialty Chemicals and Then, the components were thoroughly mixed using a
are now owned by Albis Plastic GmbH (Hamburg, Germany) mechanical stirrer until a homogeneous mixture and afterwards
(Anonymous, 2001; Anonymous, 2009). 0.45 g of the Gumosil AD-1S B component (crosslinking catalyst)
(Sip Silikony, Poland) was added. The whole set-up was intensively
2.2. Iron powder and salt mixed another time to achieve a uniform catalyst distribution.
Stirring was carried out at room temperature.
The analysed iron powder was acquired from Riedel-de-Haen, The synthesized dense mass of rubber-like consistence was
Seelze, Germany. It has a particle size up to 212 mm. NaCl was from formed into the form of discs of various dimensions and
the European salt company GmbH & Co. KG, Hannover, Germany. It thicknesses, which were left for 2030 min for complete polymer-
was milled with a mortar prior of the experiments. ization. The crosslinking of rubbers was accelerated by heating up
to 50 C. All activities were performed in argon atmosphere in
2.3. Synthesis of nanoscale iron order to prevent reaction with oxygen during preparation.
The nanoscale iron was embedded in a silicone matrix, which 2.8. Elemental analysis
had the task to reduce the access of oxygen during handling.
Directly before testing, the samples were cut in the middle in two Elemental analysis was performed using the EDS type detector
parts of equal size to increase access of oxygen during the Ultra Dry Silicon Drift X-ray Detector (SDD, Thermo Fisher
experiments. The sample is shown in Fig. 1. Scientic, USA).
Scanning electron microscopy (SEM) studies were carried out Peaks visible in Fig. 2 at angle 2 theta 52.5;77.3;99.7;124 come
using an apparatus SU3500 (Hitachi, Japan) equipped with from alpha iron phase, which conrms that synthesized nanoscale
detectors SE and BSE under given magnication. iron is in form of alpha iron. There are several allotropic forms of
pure iron: alfa, beta, gamma, epsilon. Each has a different crystal
Fig. 4. Oxygen partial pressure in measuring cells; 1: dry nanoscale iron powder; 2:
structure. a-iron, also known as ferrite, is the most stable form of nanoscale iron powder at 100% relative humidity.
iron at normal temperatures which has a body-centred cubic (bcc)
crystal structure. The number of atoms exposed on the crystal
surface determines the metal reactivity, for example with oxygen.
g-iron is able to bind six atoms of oxygen more than a-iron,
however it exists >1000 C. The X-ray difractogram furthermore
showed that there were no impurities in the sample, such as iron
oxides or iron hydroxides.
Fig. 3a presents SEM of pure nanoscale iron at a magnication of
2000. Regular grains of cluster-like structure of the size of less than
200 nm can be observed without any agglomerates. Under the
higher magnication, i.e. 300 k (Fig. 3b) it can be seen that this
agglomerates consist of nanoscale sized particles of less than
10 nm size with a very regular distribution, conrmed by
secondary electron image (SEI) analysis (SEI were taken on the
same region) of iron atom distribution presented on Fig. 3c.
Fig. 3. (a) SaEM picture of pure nanoscale iron under 2000 fold magnication. (b) SbEM picture of pure nanoscale iron under 300 000-fold magnication. (c) ScEI image of
nanoscale iron distribution in the same region of the sample as at Fig. 3b.
Z. Foltynowicz et al. / Food Packaging and Shelf Life 11 (2017) 7483 79
Fig. 6. Iron powder samples after 50 days, stored at 100% relative humidity, 23 C; left: non-nanoscale iron powder with 1% w/w NaCl; right: nanoscale iron powder of this
study.
Table 2
Water content and water activity/equilibrium humidity of the samples.
Table 3
Parameters for the calculation of normalized reaction constants.
Table 4
Oxygen absorption capacities of different oxygen scavengers.
iron powder of this study qualies as oxygen scavenger. The Theoretically, the above described two-step consecutive rate
absorption capacity was in the range of oxygen absorption capacity process should on the assumption of steady-state oxidation of
of other oxygen scavengers reported by other research groups nanoscale iron (i.e. when the amount of oxygen permeated in the
(Table 4). matrix is approximately equal to the amount of oxygen used up for
oxidation) be accounted as a double-exponential decay function
3.6. Elaboration of oxygen absorption kinetics for embedded nanoscale (Atkins & de Paula, 2006).
iron In order to prove, illustrate and quantify these statements, let us
analyse the relative oxygen concertation data shown in Fig. 9. The
As it has been discussed above, the present work aims in data were obtained from an experimental layout where nanoscale
generation of background for industrial application of oxygen iron powder was embedded in a casted silicon and the oxygen
scavenger systems based on nanoscale iron embedded in oxygen- concertation measurements were carried out in a hermetically
permeable matrices (e.g. packaging polymer plastic lms). This closed glass bottle where a piece of silicon with nanoscale iron was
application calls for a more detailed study of oxygen absorption placed. The initial oxygen concentration in the bottle was
kinetics in such systems. Indeed, Eq. (2) enables a very simplied approximately [O2]0 4.6%.
description of the oxygen absorption kinetics as a rst-order
unimolecular decay of oxygen during the time (Atkins & de Paula,
2006). This description is convenient for implementation of DIN
6139-2 standard measurements of oxygen absorption since it
enables straightforward comparison of scavenging performance of
different systems. However, the performance of systems where a
scavenging material (e.g. powder of nanoscale iron) is embedded in
a permeable matrix can only be optimized on the basis of a detailed
study. This must account the complexity of a two-step consecutive
rate process that comprises, rstly, oxygen permeation into a
matrix, and, secondly, its subsequent xation by nanoscale iron in
accordance with a generalized direct iron oxidation reaction:
5Fe + (7/2)O2 ! Fe2O3 + Fe3O4. (3)
The relative oxygen concentration [O2]/[O2]0 was then derived In following studies the nanoscale iron should be integrated in
and plotted versus time as shown in Fig. 9. Two data-tting polyethylene and polypropylene matrices which are commonly
procedures were then applied. used plastics in the packaging industry. The barrier improvement
Firstly, the rst-order exponential decay curve tting (dashed- by the active absorption of oxygen should be tested. Additionally,
dotted curve in the plot in Fig. 9) was used. This resulted in the the reaction rate at low relative humidity depending in the particle
Eq. (4) and the squared Pearsons correlation coefcient size should be determined.
R2 = 0.99804.
Acknowledgements
O2 1
ekt ; where the reaction rate k 0:1676 0:0025h : 4
O2 0
Authors would like to acknowledge the Danish Ministry of
It can be concluded that the results of the rst-order decay Higher Education and Science, the Agency for Science, Technology
approximation are reasonably good and it can be used for standard and Innovation for providing nancial support for this research in
calculations of the oxygen absorption rate. At the same time, it can the frame of the Performance Contract X4 Production in
be clearly seen that this approximation falls short of correct Denmark in 2014 and 2015. We also appreciate the support of
description of the scavenging kinetics at the beginning of the the Fraunhofer IVV for providing resources from which parts of the
process and after approximately 12 h from its initiation. This analysis were nanced. Furthermore we thank Veronika Florian for
obviously happens because at these stages the reaction rate is doing absorption experiments and the anonymous reviewers for
especially sensitive to the permeation of oxygen into silicon their valuable suggestions
matrix, and the process is far from quasi- stationarity.
Then, the second-order exponential decay curve tting (solid References
curve in the plot in Fig. 9) was applied. This resulted in the Eq. (5)
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O2
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