Robert R. Harl

We report the use of atomically thin layers of graphene as a protective coating that inhibits corrosion of underlying metals. Here, we employ electrochemical methods to study the corrosion inhibition of copper and nickel by either growing graphene on these metals, or by mechanically transferring multilayer graphene onto them. Cyclic voltammetry measurements reveal that the graphene coating effectively suppresses metal oxidation and oxygen reduction. Electrochemical impedance spectroscopy measurements suggest that while graphene itself is not damaged, the metal under it is corroded at cracks in the graphene film. Finally, we use Tafel analysis to quantify the corrosion rates of samples with and without graphene coatings. These results indicate that copper films coated with graphene grown via chemical vapor deposition are corroded 7 times slower in an aerated Na(2)SO(4) solution as compared to the corrosion rate of bare copper. Tafel analysis reveals that nickel with a multilayer graphene film grown on it corrodes 20 times slower while nickel surfaces coated with four layers of mechanically transferred graphene corrode 4 times slower than bare nickel. These findings establish graphene as the thinnest known corrosion-protecting coating.

This report describes methods to produce large-area films of graphene oxide from aqueous suspensions using electrophoretic deposition. By selecting the appropriate suspension pH and deposition voltage, films of the negatively charged graphene oxide sheets can be produced with either a smooth "rug" microstructure on the anode or a porous "brick" microstructure on the cathode. Cathodic deposition occurs in the low pH suspension with the application of a relatively high voltage, which facilitates a gradual change in the colloids' charge from negative to positive as they adsorb protons released by the electrolysis of water. The shift in the colloids' charge also gives rise to the brick microstructure, as the concurrent decrease in electrostatic repulsion between graphene oxide sheets results in the formation of multilayered aggregates (the "bricks"). Measurements of water contact angle revealed the brick films (79°) to be more hydrophobic than the rug films (41°), a difference we attribute primarily to the distinct microstructures. Finally, we describe a sacrificial layer technique to make these graphene oxide films free-standing, which would enable them to be placed on arbitrary substrates.

We report a new surface-initiated polymerization strategy that yields superhydrophobic polymethylene (PM) films from initially smooth substrates of gold and silicon. The films are prepared by assembling a vinyl-terminated self-assembled monolayer, followed by exposure of the surface to a 0.1 M solution of borane, and polymerizing from the borane sites upon exposure to a solution of diazomethane at -17 degrees C. Surface-initiated polymethylenation (SIPM) presents rapid growth in relation to other surface-initiated reactions, producing PM films thicker than 500 nm after 2 min of reaction and 3 microm after 24 h of reaction. AFM and SEM images show the presence of micro- and nanoscale features that enable the entrapment of air when exposed to water. Consistent with this result, these films exhibit advancing water contact angles greater than 160 degrees, dramatically different than 103 degrees measured for smooth PM films, and hysteresis values ranging from 2 degrees to 40 degrees, depending on the substrate and polymerization time. The superhydrophobic character of the films results in the entrapment of air at the polymer/solution interface to provide remarkable resistances greater than 10(10) Omega x cm(2) against the transport of aqueous redox probes and cause the film to behave as a "perfect" capacitor.

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to Graphene: Corrosion-Inhibiting CoatingDhiraj Prasai, Juan Carlos Tuberquia, Robert R. Harl, G. Kane Jennings, Bridget R. Rogers, and Kirill I. Bolotin*Cite this: ACS Nano 2012, 6, 5, 4540Publication Date (Web):April 18, 2012Publication History Received23 March 2012Published online18 April 2012Published inissue 22 May 2012https://doi.org/10.1021/nn301293jCopyright © 2012 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views2525Altmetric-Citations14LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (40 KB) Get e-AlertsSUBJECTS:Coating materials,Two dimensional materials,X-ray photoelectron spectroscopy Get e-Alerts