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ARTICLE
Graphene: Corrosion-Inhibiting
Coating
Dhiraj Prasai, Juan Carlos Tuberquia, Robert R. Harl, G. Kane Jennings, and Kirill I. Bolotin,*
Institute for Nanoscale Science and Engineering, Department of Physics and Astronomy, Department of Chemical and Biomolecular Engineering,
Vanderbilt University, Nashville, Tennessee 37235, United States
n intense eort is underway to nd
coatings that inhibit the process of
metal corrosion, a problem costing
US industries more than $200 billion
annually.1 Corrosion can be inhibited or
controlled by introducing a stable protective layer made of inert metals,2 conductive
polymers,3 or even thiol-based monolayers 4
between a metal and a corrosive environment. However, these protective coatings
have their limitations. Thiolated SAMs can
only be assembled onto some metals (e.g.,
gold and copper) and do not withstand
temperatures higher than 100 C.5 Polymeric coatings are relatively thick and may
signicantly change the physical properties
of the underlying material. Recent advances
in the growth techniques of graphene8 are
expected to enable commercial viability of
large-area graphene lms.
Graphene, a single atomic monolayer of
graphite, possesses a unique combination
of properties that are ideal for corrosioninhibiting coating in applications such as
microelectronic components (e.g., interconnects, aircraft components, and implantable
devices). Graphene is chemically inert,
stable in ambient atmosphere up to 400 C,6
ABSTRACT
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 eectively 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 lm. Finally, we use
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Tafel analysis to quantify the corrosion rates of samples with and without graphene coatings.
These results indicate that copper lms coated with graphene grown via chemical vapor
deposition are corroded 7 times slower in an aerated Na2SO4 solution as compared to the
corrosion rate of bare copper. Tafel analysis reveals that nickel with a multilayer graphene lm
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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 ndings
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* Address correspondence to
kirill.bolotin@vanderbilt.edu.
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Published online
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Figure 1. (a) Gr/Cu sample prepared via chemical vapor deposition, and its Raman spectrum exhibiting characteristic G and
2D peaks. Inset represents schematic of foils mounted onto PTFE 3-electrode cell where copper tape (1) is attached to the
sample and 0.4 cm2 of active area (2) is exposed to the NaSO4 electrolyte. (b) Gr/Ni sample (patches of multilayer graphene
grown via chemical vapor deposition on Ni) and tr2Gr/Ni and tr4Gr/Ni samples, where graphene was mechanically transferred
onto nickel surface, along with their respective Raman spectra.
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CVD-04) via CVD. We grow Gr/Cu using the wellestablished recipes that yield high-quality, predominantly single layer graphene in the case of Gr/Cu,7 as
confirmed by Raman spectroscopy (Figure 1a). Cu foils,
25 m thick, are cut into small strips and placed inside a
fused silica tube and heated using a hot wall furnace.
The Cu foil is first heated at 1000 C under a 2 sccm flow
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Figure 2. (a) Cyclic voltammetry measurements (electrolyte is 0.1 M Na2SO4) in the potential window 700 to 200 mV for bare
Cu and Gr/Cu samples. Blue line corresponds to the measurement with nitrogen bubbled through the solution. (b) XPS core
level spectrum of Cu (ambient), Cu (100 mV), and Cu (sputter cleaned) samples. The region (i) contains a shoulder due to CuO,
the region (ii) contains a peak due to Cu2O/Metallic Cu. (c) SEM images of Cu and Gr/Cu sample before and after CV scan.
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Anodic reaction:
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Cu f Cu2 2e
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f 4OH
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These two reactions complement each other so that impeding one of them slows the overall corrosion process.
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Figure 3. (a) Tafel plots of Cu and Gr/Cu samples. Best ts are represented by dotted lines. Inset: Raman spectrum of the Gr/Cu
sample after completing Tafel analysis displays small defect-related D peaks. (b) Corrosion rates of Cu and Gr/Cu samples
extracted from Tafel plots. (c) Corrosion rates of bare Ni samples and the samples where graphene was transferred onto Ni
substrate.
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and are comparable to the literature values.23 Graphene grown via CVD was found to signicantly slow
down corrosion. For Gr/Cu samples the corrosion rate
was 7.85 10 14 ( 3.5 10 14 m/s, a reduction of 7
times compared to the bare sample, and for Gr/Ni
1.71
10 15 m/s, a reduction of 20 times was
observed (Figure 3b). Remarkably, graphene, which is
only atomically thick, provides the corrosion reduction
that is comparable to conventional organic coatings
that are more than ve times thicker.24
We have similarly extracted the corrosion rates for
samples where the graphene lms grown on copper
were mechanically transferred onto a target nickel
substrate. We have found that a single layer of
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Figure 4. (a) Bode magnitude plots of Gr/SiO2, Cu, and Gr/Cu samples (solid symbols). Best ts to the equivalent circuit models
are solid lines. (b) Equivalent circuit model used in modeling Gr/SiO2 devices. (c) Equivalent circuit model for Cu and Gr/Cu
devices.
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CONCLUSION
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We have demonstrated that single-layer and multilayer graphene lms can serve as corrosion-inhibiting
coatings and developed quantitative models that describe the passivation mechanism. We expect that the
proposed method of corrosion passivation is quite
versatile and is applicable not just to nickel and copper
but to arbitrary metallic surfaces that are either smooth
or rough.31 Furthermore, our data indicate that corrosion occurs in the cracks of graphene. The eciency of
the corrosion inhibition may be greatly enhanced by
developing protocols to grow highly uniform and
large-grain graphene and by performing high delity
mechanical transfer of graphene onto various metallic
surfaces. Finally, we demonstrate that a combination of
simple electrochemical techniques can be eectively
used to characterize the graphene protective coatings.
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Supporting Information Available: Elemental surface analysis using XPS to conrm the absence of electrochemical
oxide formation on Cu and Gr/Cu samples. This material
is available free of charge via the Internet at http://pubs.
acs.org.
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