Metal-Organic Framework (MOF)/Epoxy Coatings: A Review
<p>Metal-organic framework (MOF); (<b>a</b>) combination of building blocks of MOF, with different types of metal atoms as the nodes and various kinds of carboxylic ligands as the organic linkers, used in the fabrication of exquisite structures [<a href="#B39-materials-13-02881" class="html-bibr">39</a>], (<b>b</b>) The number of different kinds of fabricated MOF structures (Source: The Cambridge Structural Database (CSD)) [<a href="#B64-materials-13-02881" class="html-bibr">64</a>] revealing that more than 70,000 different structures of MOFs have been introduced prior to 2016. The exponential trend in the number of publications released in the last decade extracted from the Scopus database (based on the keywords of “metal-organic framework” and “MOF”) can be observed.</p> "> Figure 2
<p>Schematic illustration of the major synthesis routes from solvothermal and microwave to electrochemical techniques with different ranges of temperature and fabrication time applied in MOF synthesis; unique features of MOFs such as chemical/thermal stability, designable morphology, tailorable crystal size, large surface area, and excellent porous structure; typical applications of MOFs such as energy storage, supercapacitors, sensing, and catalysis; and the synthesis mechanism [<a href="#B7-materials-13-02881" class="html-bibr">7</a>,<a href="#B13-materials-13-02881" class="html-bibr">13</a>].</p> "> Figure 3
<p>Chemical structure of diglycidyl ether bisphenol-A (DGEBA) epoxy resin.</p> "> Figure 4
<p>The possible reaction between the MIL-101 MOF and the epoxy resin and the schematic view of the diffusion of epoxy into the pores of MOF [<a href="#B70-materials-13-02881" class="html-bibr">70</a>]. Similar to the outcome of studies performed on halloysite nanotubes (HNTs), using the potential of inner functional groups (in the case of HNTs, inside the nanotubes and in the case of MOF, inside the nanocages) has a significant effect on the crosslinking of epoxy resin. In fact, functional groups contributed to curing reactions from the internal surface of minerals (denoted as secondary curing agents or extra cure sites) keeping the stoichiometry balanced when gelation takes place. Above conversion of gelation (α<sub>g</sub>), curing agent molecules can hardly access the epoxide groups; therefore, curing will remain incomplete as a consequence of contacts between cure moieties being substantially limited or even stopped. In such a situation, the excess sites contributed from reactive groups of internal structure compensate for incomplete cure arising from gelation. MOF has a high potential for being considered as such a highly reactive mineral.</p> "> Figure 5
<p>Schematic of the self-healing mechanism of the corrosion inhibitor encapsulated MOF/epoxy coatings [<a href="#B83-materials-13-02881" class="html-bibr">83</a>].</p> "> Figure 6
<p>Fire retardancy mechanism of epoxy-containing phosphorus flame retardant loaded MOF [<a href="#B101-materials-13-02881" class="html-bibr">101</a>].</p> ">
Abstract
:1. Introduction
2. MOFs in Epoxy Coatings
2.1. Anti-Corrosion Properties
2.2. Flame-Retardant Properties
2.3. Other Properties
3. Future Ahead of MOFs for Coating Applications
Author Contributions
Funding
Conflicts of Interest
References
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Epoxy/MOF Composite-Based Materials for Corrosion Inhibition | |||||
---|---|---|---|---|---|
No | MOFs | Corrosion Inhibitor | Corrosive Media | Main Findings | Reference |
1 | ZIF-8 | Hollow mesoporous silica nanoparticles (HMSN)-BTA | 3.5 wt.% NaCl solution | After 30 days of immersion in the corrosive solution, the values of film resistance (Rf) of the epoxy coatings with HMSN-BTA@ZIF-8 were much higher than 108 Ω cm2, while values decreased to only about 106 Ω cm2 for the neat epoxy. | [81] |
2 | ZIF-8 | Zinc Gluconate (ZnG) | 3.5 wt.% NaCl solution | Incorporation of ZnG@ZIF-8 as a corrosion inhibitor revealed no signs of corrosion in the epoxy, even after 40 days of immersion. | [82] |
3 | Ce-MOF | BTA | 3.5 wt.% NaCl solution | Incorporation of 3 wt.% BI loaded Ce-MOF@ tetraethyl orthosilicate (TEOS) into the epoxy coating improved the charge transfer resistance by 1.5% after 2 h of immersion. | [83] |
4 | ZIF-7 | BTA | 0.1 M HCl solution | The epoxy coating doped with ZIF-7@BTA exhibited a superior barrier performance, which provided 99.4% inhibition efficiency. | [84] |
5 | Cu-MOF | BTA | 3.5 wt.% NaCl solution | Incorporation of 2 wt.% BTA-Cu-MOF into epoxy exhibited a corrosion potential of 0.492 V, which was ca. 26.5 times the value of the polarization resistance of the blank epoxy. | [85] |
6 | ZIF-7 | - | 0.1 M HCl solution | The coating resistance of 1.7% ZIF incorporated epoxy was ca. 2 times of that of the blank epoxy after 72 h of immersion. | [86] |
7 | MOF-5 | - | 3.5 wt.% NaCl solution | Dopamine@MOF-5 effectively delayed penetration of corrosive solution into the coating for 480 h. | [87] |
8 | ZIF-8 | - | 5 wt.% NaCl solution | RHS *@ZIF-8 structure improved early-stage corrosion inhibition of epoxy with no essential damage in the coating. | [88] |
9 | ZIF-8 | - | 3.5 wt.% NaCl solution | By addition of graphene oxide (GO)@ZIF-8, the cathodic delamination resistance, and wet adhesion strength were improved by about 73% and 60%, respectively. | [89] |
Epoxy-MOF Composite-Based Materials for Flame Retardancy | |||||
---|---|---|---|---|---|
No | MOFs | Flame Retardant | Flame Tests | Main Findings | Reference |
1 | Co-MOF | Di (para-aminobenzoic acid) phenyl phosphate amide | CC 1 SSTF 2 | Decrease in pHRR and THR by 28% and 18.6%, respectively, by incorporating 2 wt.% of phosphorus-Co-MOF. | [97] |
2 | ZIF-8 ZIF-67 MIL-101 (Fe) | - | CC | 2 wt.% of Co-MOF/epoxy, Zn-MOF/epoxy, and Fe-MOF/epoxy composites burnt relatively slowly, and the reduction in pHRR in the composites was 31.3%, 27.8%, and 18.6%, respectively. | [98] |
3 | NH2-MIL-101 (Al) | Phosphorus-nitrogen-containing ionic liquid (IL@NH2) | LOI 3 CC | Addition of 3 wt.% IL modified-MOF (IL@NH2-MIL-101 (Al)) increased the LOI value of the epoxy to 29.8%, decreased pHRR by 51.2%, smoke production rate by 37.8%, and CO release rate by 44.8% with respect to those of blank epoxy. | [99] |
MOFs as the Modifiers of Other Properties | |||
---|---|---|---|
No | MOFs | Main Findings | Reference |
1 | MOF-5 | Incorporation of 0.3% wt. MOF-5 led to 68% rise in the impact strength and 230% increase in the fracture energy of epoxy. | [104] |
2 | UiO-66 * UiO-66-NH2 | The values of tensile strength and elongation at break for UiO-66-NH2/EP were 40.4 MPa and 2.60%, respectively, which were higher than those of neat epoxy (35.2 MPa and 1.94%, respectively) and UiO-66/epoxy (37.0 MPa and 2.56%, respectively). | [103] |
3 | ZIF-8 | Addition of 25 vol.% ZIF-8 increased the Young’s modulus by 20% and decreased the dielectric constant of epoxy from 3.9 to 3.2 at 100 kHz. | [107] |
4 | ZIF-8 | The dielectric constant of the epoxy/ZIF-8 composite (0.3 wt.%) was decreased from 4.12 to 3.45. | [108] |
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Seidi, F.; Jouyandeh, M.; Taghizadeh, M.; Taghizadeh, A.; Vahabi, H.; Habibzadeh, S.; Formela, K.; Saeb, M.R. Metal-Organic Framework (MOF)/Epoxy Coatings: A Review. Materials 2020, 13, 2881. https://doi.org/10.3390/ma13122881
Seidi F, Jouyandeh M, Taghizadeh M, Taghizadeh A, Vahabi H, Habibzadeh S, Formela K, Saeb MR. Metal-Organic Framework (MOF)/Epoxy Coatings: A Review. Materials. 2020; 13(12):2881. https://doi.org/10.3390/ma13122881
Chicago/Turabian StyleSeidi, Farzad, Maryam Jouyandeh, Mohsen Taghizadeh, Ali Taghizadeh, Henri Vahabi, Sajjad Habibzadeh, Krzysztof Formela, and Mohammad Reza Saeb. 2020. "Metal-Organic Framework (MOF)/Epoxy Coatings: A Review" Materials 13, no. 12: 2881. https://doi.org/10.3390/ma13122881