High-resolution characterization of hexagonal boron nitride coatings exposed to aqueous and air oxidative environments
- 315 Downloads
Hexagonal boron nitride (h-BN) is believed to offer better passivation to metallic surfaces than graphene owing to its insulating nature, which facilitates blocking the flow of electrons, thereby preventing the occurrence of galvanic reactions. Nevertheless, this may not be the case when an h-BN-protected material is exposed to aqueous environments. In this work, we analyzed the stability of mono and multilayer h-BN stacks exposed to H2O2 and atmospheric conditions. Our experiments revealed that monolayer h-BN is as inefficient as graphene as a protective coating when exposed to H2O2. Multilayer h-BN offered a good degree of protection. Monolayer h-BN was found to be ineffective in an air atmosphere as well. Even a 10–15 layers-thick h-BN stack could not completely protect the surface of the metal under consideration. By combining Auger electron spectroscopy and secondary ion mass spectrometry techniques, we observed that oxygen could diffuse through the grain boundaries of the h-BN stack to reach the metallic substrate. Fortunately, because of the diffusive nature of the process, the oxidized area did not increase with time once a saturated state was reached. This makes multilayer (not monolayer) h-BN a suitable long-term oxidation barrier. Oxygen infiltration could not be observed by X-ray photoelectron spectroscopy. This technique cannot assess the chemical composition of the deeper layers of a material. Hence, the previous reports, which relied on XPS to analyze the passivating properties of h-BN and graphene, may have ignored some important subsurface phenomena. The results obtained in this study provide new insights into the passivating properties of mono and multilayer h-BN in aqueous media and the degradation kinetics of h-BN-coated metals exposed to an air environment.
Keywordshexagonal boron nitride protective coating local oxidation nanoscale two-dimensional (2D) materials
Unable to display preview. Download preview PDF.
This work has been supported by the Young 1000 Global Talent Recruitment Program of the Ministry of Education of China, the National Natural Science Foundation of China (Nos. 61502326, 41550110223, and 11661131002), the Jiangsu Government (No. BK20150343), the Ministry of Finance of China (No. SX21400213) and the National Basic Research Program of China (No. 2015CB932700). The Collaborative Innovation Center of Suzhou Nano Science & Technology, the Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices and the Priority Academic Program Development of Jiangsu Higher Education Institutions are also acknowledged. Part of this work was carried out with the excellent support of the Nanofabrication and Nanocharacterization Core Facility of CEITEC under CEITEC Nano project (No. LM2015041). P. B. and M. K. acknowledge support of Ministry of Education, Youth and Sports of the Czech Republic under the project CEITEC 2020 (No. LQ1601).
- Merkula, D. M.; Novikov, P. D.; Ivanenkov, V. N.; Sapozhnikov, V. V.; Lyakhin, Y. I. Utilization of EDN varnish for protection of metal sea-water sampling bottles against corrosion. Oceanology 1974, 14, 299–300.Google Scholar
- Cho, H. B.; Tokoi, Y.; Tanaka, S.; Suematsu, H.; Suzuki, T.; Jiang, W.; Niihara, K.; Nakayama, T. Modification of BN nanosheets and their thermal conducting properties in nanocomposite film with polysiloxane according to the orientation of BN. Compos. Sci. Technol. 2011, 71, 1046–1052.CrossRefGoogle Scholar
- Sattler, K. D. Handbook of Nanophysics: Functional Nanomaterials; CRC Press: Boca Raton, 2010.Google Scholar
- Hu, J. C.; Ji, Y. F.; Shi, Y. Y.; Hui, F.; Duan, H. L.; Lanza, M. A review on the use of graphene as a protective coating against corrosion. Ann. J. Materials Sci. Eng. 2014, 1, 16.Google Scholar
- Yu, Q.; Jauregui, L. A.; Wu, W.; Colby, R.; Tian, J.; Su, Z.; Cao, H.; Liu, Z.; Pandey, D.; Wei, D.; Chung, T. F.; Peng, P.; Guisinger, N. P.; Stach, E. A.; Bao, J.; Pei, S. S.; Chen, Y. P. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nat. Mater. 2011, 10, 443–449.CrossRefGoogle Scholar
- Liu, Z.; Gong, Y. J.; Zhou, W.; Ma, L. L.; Yu, J. J.; Idrobo, J. C.; Jung, J.; MacDonald, A. H.; Vajtai, R.; Lou, J. et al. Ultrathin high-temperature oxidation-resistant coatings of hexagonal boron nitride. Nat. Commun. 2013, 4, 2541.Google Scholar
- Haasch, R. T. X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES). In Practical Materials Characterization; Sardela, M., Ed.; Springer: New York, 2014; pp 93–132.Google Scholar
- Kaemmer, S. B. Introduction to Bruker’s ScanAsyst and PeakForce Tapping AFM Technology [Online]. AFM application notes. AN133, DS090, Rev. A0. http://www.bruker.com/products/surface-and-dimensional-analysis/atomic-force-microscopes/afm-application-notes/an133-introduction-to-brukers-scanasyst-and-peakforce-tapping.html (accessed Aug 23, 2016).Google Scholar
- Moelwyn-Hughes, E. A. The Kinetics of Reactions in Solution, 2nd ed.; Clarendon Press: Oxford, 1947.Google Scholar
- Senese, F. Will Hydrogen Peroxide Blacken Copper? [Online]. General Chemistry. http://antoine.frostburg.edu/chem/senese/ 101/redox/faq/h2o2-cu (accessed Aug 17, 2015).Google Scholar
- Jing, X.; Panholzer, E.; Song, X. X.; Grustan-Gutierrez, E.; Hui, F.; Shi, Y. Y.; Benstetter, G.; Illarionov, Y.; Grasser, T.; Lanza, M. Fabrication of scalable and ultra low power photodetectors with high light/dark current ratios using polycrystalline monolayer MoS2 sheets. Nano Energy 2016, 30, 494–502.CrossRefGoogle Scholar