Anti-Corrosive Graphene

Coatings: An Active—Passive
Alternative to Hexavalent
Chromium Coatings
Robert V. Dennis, Vincent Lee, Lasantha Viyannalage, Steven M. Henderson
and Sarbajit Banerjee

Department of Chemistry
University at Buffalo
sb244@buffalo.edu
 Outline

The “Rust Belt” and Hexavalent Chromium

Graphene: The New Carbon Age

Graphene Nanocomposites for Corrosion Protection: The

Story so Far

Commercialization and Outlook

 The “Rust” in the “Rust Belt”
Corrosion – deterioration of a material due to reactions with
its surrounding environment
 Requirements for rust
O2 formation
H 2O o Iron
O2 Na+ Fe2+/3+
Rust
-
Cl
Fe2O3 o Oxygen
Fe o Water
o Electrolytes
 Iron oxide does not form
O2 + 2 H2O + 4 e- → 4 OH- passivating layer
2 Fe → 2 Fe2+ + 4 e-
2 Fe + O2 + 2 H2O → 2 Fe(OH)2
 Degrades mechanical
strength
2 Fe(OH)2 + ½ O2 + H2O →  The cost of corrosion on the US
2 Fe(OH)3 economy is roughly $300 billion
annually
 Chromium-Based Coatings
 Chromium-based coatings
used heavily for the better
part of the last century
 Ease of plating technology
 Excellent corrosion and
wear resistance
 Lustrous surface finish
 Potent carcinogen
 Hard chrome electroplating
has lead to dangerously high
levels of Cr(VI) across the
USA  Regulating agencies include:
 Increased regulations Environmental Protection Agency
require development of a (EPA), Occupational Safety and Health
new “greener” alternative. (OSHA), NIOSH, and Environment
Canada
http://www.ewg.org/chromium6-in-tap-water/full-report
http://www.ec.gc.ca/
 Zinc Coatings

http://www.slamresources.com/investor-
center/market-outlook/

 Zinc galvanization is widely used to prevent corrosion on iron and steel

surfaces
 Excellent corrosion and wear resistance
 Steel companies don’t want to be held hostage by fluctuating costs of Zn
 An alternative to Zn would greatly reduce the use of Zn and lower
costs for steel companies
 The Active—Passive Approach
Passive: The coating serves as a “barrier layer” precluding
permeation of corrodants to the metal surface.

Active: An effective passivation layer is formed, which impedes

corrosion half-reactions. “Schottky barrier” at interface leads to
depletion of electrons.

Self-Healing (future): pH-sensitive leachable components that are

deposited as precipitates upon initiation of rust formation.
Active-Passive Approach: Graphene-PEI
Nanocomposite Coatings
 Graphene to the Rescue
 Graphene is a single layer of graphite in a honeycomb lattice
 Geim and co-workers synthesized graphene in 2004 through
mechanical exfoliation (Nobel Prize in Physics, 2010)
 High electrical conductivity
(mobilities >200,000 cm2/Vs)
 Excellent mechanical strength
 Tensile strength of ~1 TPa
 Light weight
 Hydrophobic
 Heat resistant

Geim, A. K.; Novoselov, K. S. Nat Mater 2007, 6, 183-191.

Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.;
Firsov, A. A. Science 2004, 306, 666-669.
Brian J. Schultz, Christopher J. Patridge, Vincent Lee, Cherno Jaye, Patrick D. Lysaght, Casey Smith, Joel
Barnett, Daniel A. Fischer, David Prendergast,* Sarbajit Banerjee,* Nature Commun., 2011, 2, 372/1-372/8.
Synthesis of Graphene
Unfunctionalized
Graphene (UFG)

UFG
UFG
microstructure

UFG solution

Graphite
 Why Polyetherimides?
 Properties: Polyamic
acid
 Hydrophobic
 Low moisture permeation/water
uptake
 Solvent resistant
 Temperature resistant
 Formable
 Flexible
 Great adhesion to the steel surface
Process for Preparing Coatings
UFG/PEI solutions
Polyamic 0.05% wt 0.10% 0. 5% 2.0% 5.0 %
acid UFG wt UFG wt UFG wt UFG wt UFG

UFG/polyamic acid solutions

1.7% wt. 1.3% wt. Blank 1.0% wt.
PEI
UFG UFG Steel UFG

Day 1

1.7% wt. 1.3% wt. 1.0% wt.

UFG UFG Blank UFG
PEI
Steel

Day 3
1.7% wt. 1.3% wt. 1.0% wt.
PEI Blank
UFG UFG UFG
Steel

Day 10

1.7% wt. 1.3% wt. Blank 1.0% wt.

UFG PEI UFG Steel UFG

Day 14
 Corrosion Rate
g Tested using Steel sample size:
𝑚2 ℎ ASTM G1 4 cm x 4 cm

An order of
magnitude
improvement with
a small loading of
UFG!
Coatings
Blank steel PEI 0.05% wt UFG 0.10% wt UFG

0. 5% wt UFG 2.0% wt UFG 5.0% wt UFG

 Testing Corrosion-Resistance
 Potentiodynamic polarization resistance measurements
 Standardized by ASTM G59

 Working electrode:
 Coated steel plate
 Reference electrode:
 Saturated calomel electrode
 Counter electrode:
 Pt strip
 Electrolyte:
 3.5% NaCl

𝑰𝒄𝒐𝒓𝒓 × 𝑲 × 𝑬𝑾
𝑪𝒐𝒓𝒓𝒐𝒔𝒊𝒐𝒏 𝑹𝒂𝒕𝒆 𝑪𝑹 =
𝝆

K = 3.27 x 10−3 mm g/μA cm yr

EW - Equivalent weight = 27.92 for steel
ρ = 7.87g/cm3 for steel
Tafel plot
Tafel plot
 Conclusions and Outlook
 Graphene-polyetherimide
coatings provide enhanced
corrosion resistance to low
alloy steel as verified by
qualitative, semi-quantitative,
and quantitative tests
 An active-passive mechanism
for corrosion inhibition is
proposed.
 PCT International filed
Outlook & Future
Directions
 Self-healing particles that are
released in response to
external stimuli (crack
formation, initiation of
rusting).
 Extension of methodology to
replace chromate conversion
coatings on aluminum.
 Nanostructured Mg-based
coatings.
Acknowledgements