Elaboration and Characterization of Active Films Containing Iron–Montmorillonite Nanocomposites for O2 Scavenging
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.1.1. Synthesis of MMT-Fe
2.1.2. Processing of MMT-Fe/LLDPE Films
2.2. Methods
2.2.1. Structural and Morphological Analysis
2.2.2. Thermal Properties
2.2.3. O2 and Vapor Barrier Properties
2.2.4. Oxygen-Scavenging Capacity
2.2.5. Iron Content by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)
2.2.6. Mössbauer Spectroscopy
2.3. Modeling of Oxygen Adsorption in the Active Nanocomposite
2.3.1. Modeling of O2 Adsorption for Iron Nanoparticles
2.3.2. Modeling of O2 Adsorption for an Active Nanocomposite
2.3.3. Numerical Simulations
2.4. Statistics
3. Results
3.1. Structural and Morphological Characterization of the MMT-Fe and MMT-Fe/LLDPE Films
3.2. Effect of MMT-Fe Content on the Thermal Stability of LLDPE Nanocomposite Films
3.3. Mössbauer Spectroscopy Study of the Active Nanocomposite
3.4. Oxygen-Scavenging Capabilities for MMT-Fe and Active Nanocomposites
3.5. Oxygen and Water Vapor Barrier Properties of LLDPE/MMT-Fe Active Film Composite
3.6. Modeling the Oxygen-Scavenging Activity
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Appendix A
Appendix B
References
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Sample * | Composition | |||
---|---|---|---|---|
LLDPE wt % | PE-g-MA wt % | MMT wt % | MMT-Fe wt % | |
LLDPE | 100 | |||
LLDPE.Fu15 | 85 | 15 | ||
LLDPE.Fu15.MMT3 | 82 | 15 | 3 | |
LLDPE.Fu5.MMT5 | 80 | 15 | 5 | |
LLDPE.Fu15.MMT-Fe3.75 | 81.25 | 15 | 3.75 | |
LLDPE.Fu15.MMT-Fe6.25 | 78.75 | 15 | 6.25 |
Sample | Heat of Fusion (J/g) | Tm (°C) | Crystallinity | Temp. Onset Degradation (°C) | Temp. Endset Degradation (°C) |
---|---|---|---|---|---|
LLDPE | 104 ± 10 | 122.1 ± 0.5 | 35.8 ± 3.6 | 416 ± 9 | 475 ± 4 |
LLDPE.Fu15 | 104 ± 8 | 121.3 ± 1.2 | 35.7 ± 3.1 | 416 ± 2 | 457 ± 2 |
LLDPE.Fu15.MMT3 | 104 ± 5 | 121.9 ± 0.7 | 34.8 ± 0.9 | 416 ± 22 | 478 ± 19 |
LLDPE.Fu15.MMT5 | 99 ± 10 | 122.2 ± 1.0 | 31.3 ± 0.6 | 429 ± 9 | 480 ± 4 |
LLDPE.Fu15.MMT-Fe3.75 | 107 ± 2 | 121.6 ± 0.4 | 36.3 ± 0.7 | 419 ± 5 | 468 ± 3 |
LLDPE.Fu15.MMT-Fe6.25 | 102 ± 4 | 122.3 ± 1.2 | 34.5 ± 1.2 | 418 ± 7 | 466 ± 2 |
Sample | Component | δ (mm/s) | Δ (mm/s) | Γ (mm/s) | BHF (T) | Area (%) |
---|---|---|---|---|---|---|
MMT-Fe | Fe1−xBx | 0.08 | −0.03 | 0.47 | 30.8 | 53 |
Fe2+ para | 1.25 | 3.03 | 0.66 | - | 6 | |
Fe2+ magn | 1.21 | −2.78 | 1.72 | 15.0 | 6 | |
Fe3+ oxide | 0.37 | −0.12 | 0.60 | 49.0 | 35 | |
Fresh LLDPE.Fu15.MMT-Fe6.25 | Fe1−xBx type1 | 0.00 | 0.00 | 0.60 | 25.00 | 3 |
Fe1−xBx type2 | 0.24 | 0.00 | 0.86 | - | 8 | |
Fe2+ para | 1.28 | 3.09 | 0.64 | - | 4 | |
Fe2+ magn | 1.21 | −2.07 | 1.14 | 19.45 | 10 | |
Fe3+ oxide type1 | 0.34 | 0.00 | 0.85 | 51.62 | 75 | |
Fe3+ oxide type 2 | 0.41 | 0.00 | 2.5 | 47.17 | ||
LLDPE.Fu15.MMT-6.25 after four months of oxidation | Fe1−xBx type1 | 0.00 | 0.00 | 0.60 | 24.55 | 3 |
Fe1−xBx type2 | 0.30 | 0.00 | 1.11 | - | 3 | |
Fe2+ para | 1.30 | 3.04 | 0.56 | - | 3 | |
Fe2+ magn | 1.21 | −2 | 1.81 | 19.52 | 5 | |
Fe3+ oxide type1 | 0.37 | 0.00 | 1.27 | 50.76 | 86 | |
Fe3+ oxide type 2 | 0.41 | 0.00 | 2.5 | 46.16 |
Film | O2 Adsorption Capacity mg O2/g of Absorber | Ref. |
---|---|---|
PE.Fu15.MMT-Fe6.25 film | 55 ± 2 | This work |
PE.Fu15.MMT-Fe3.75 film | 31 ± 2 | This work |
Polymer with iron powder and additives (“SHELFPLUS”); masterbatch | 26–48 | [36] |
O2Block1 (NanoBioMatters S.L., Paterna, Spain); masterbatch | >10–25 | [37] |
Cyclo-olefin bonded to a silicate backbone “ORMOCER1”; lacquer | 90 | [38] |
Nanoscale iron in silicon matrix | >32 ± 80 | [7] |
Polyolefin films containing 10 wt % of iron modified kaolinite | 5.7 | [9] |
Nanoscale iron powder | >68 ± 2 | [7] |
Nanoscale iron-MMT powder | 122 | [15] |
Stoichiometric capacity of iron | 394 | [15] |
Symbol | Definition | Unit | Value | Source |
---|---|---|---|---|
Thickness of the nanocomposite sample | 296 × 10−6 | This work | ||
Surface area of a single side of the nanocomposite film sample | 0.1376 | This work | ||
Volume of the headspace | 458 × 10−6 | This work | ||
Mass fraction of iron in the sample | 0.22 | This work | ||
Mass fraction of zerovalent iron | 0.11 | This work | ||
Mass fraction of bivalent iron | 0.14 | This work | ||
Molar mass of iron | 55.8 × 10−3 | |||
Apparent density of the nanocomposite, taken as the corresponding value for the pure polymer (LLDPE) | 918 | [15] | ||
oxidation | 2.4 × 10−6 | [15] | ||
oxidation | 3.2 × 10−5 | [15] | ||
oxidation | 0.19 | [15] | ||
oxidation | 0.40 | [15] | ||
Apparent O2 diffusivity in the nanocomposite, taken as the corresponding value for the pure polymer (LLDPE) | 1.68 × 10−11 | [39] | ||
O2 solubility in the nanocomposite material | m−3 | 3.54 × 10−6 | [40] | |
Biot number | dimensionless | 1 × 105 | This work | |
Ideal gas constant | 8.314 | |||
Temperature of the experiment | 293.15 | This work |
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Kombaya-Touckia-Linin, E.-M.; Gaucel, S.; Sougrati, M.T.; Stievano, L.; Gontard, N.; Guillard, V. Elaboration and Characterization of Active Films Containing Iron–Montmorillonite Nanocomposites for O2 Scavenging. Nanomaterials 2019, 9, 1193. https://doi.org/10.3390/nano9091193
Kombaya-Touckia-Linin E-M, Gaucel S, Sougrati MT, Stievano L, Gontard N, Guillard V. Elaboration and Characterization of Active Films Containing Iron–Montmorillonite Nanocomposites for O2 Scavenging. Nanomaterials. 2019; 9(9):1193. https://doi.org/10.3390/nano9091193
Chicago/Turabian StyleKombaya-Touckia-Linin, Erland-Modeste, Sébastien Gaucel, Moulay T. Sougrati, Lorenzo Stievano, Nathalie Gontard, and Valérie Guillard. 2019. "Elaboration and Characterization of Active Films Containing Iron–Montmorillonite Nanocomposites for O2 Scavenging" Nanomaterials 9, no. 9: 1193. https://doi.org/10.3390/nano9091193