www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No.

5 18
Graphene nanocomposite coatings for protecting low-alloy steels from corrosion
By Robert V. Dennis, Lasantha T. Viyannalage, Anil V.
Gaikwad, Tapan K. Rout, and
Sarbajit Banerjee
A scalable roller-coating approach adapts new materials to
solving persistent corrosion problems using existing manu-
facturing methods.
Graphene
nanocomposite
coatings for
protecting low-
alloy steels from
corrosion
A
ceramic engineer or scientist
unfortunately must admit that
there is an unwelcome member of the fam-
ily among usiron oxide, or rust. This
unpleasant family member is disruptive at
best. More often it is destructive, nearly
impossible to control, and a consumer
of resources that are devoted to it in an
attempt to mitigate its impact or at least
slow it down. Metal bars, wires, and sheets
require protective coatings to prolong
their use on exposure to service environ-
ments wherein they inevitably encounter
corrodant species and conditions condu-
cive to the initiation of rust formation.
Society invests enormous amounts of time
and financial resources to rust preven-
tion, repair, and replacement. Indeed, the
Department of Defense has a long his-
tory of fighting rust (Figure 1), and the
Government Accountability Office esti-
mates that today the United States military
spends more than $20 billion per year in
corrosion-related expenses.
As the advanced manufacturing industry in the United
States rejuvenates, sustainable processes and materials will be
increasingly important.
1,2
New materials will offer opportuni-
ties for new solutions to old problems. Graphene and carbon
nanotubes represent a class of new materials with unique
Figure 1. Army truck cab assemblies enter-
ing massive rust-proofing ovens. The sheet
metal is treated with chemicals before
applying finishing coats to prevent rust.,
circa 1945.
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19 American Ceramic Society Bulletin, Vol. 92, No. 5 | www.ceramics.org
properties that are just beginning to find
applications in emerging and existing
industries. This article presents promis-
ing results of an activepassive approach
to protecting low-alloy steels from
corrosion using a nanocomposite coat-
ing comprising exfoliated graphene or
multiwalled carbon nanotubes dispersed
within a polyetherimide matrix.
Keeping rust at bay
The earliest reports of efforts to
prevent fouling of surfaces date back
to 412 BC when explorers coated the
wooden hulls of ships with tallow and
pitch poisoned with arsenic and sulfur
to keep barnacles at bay.
Today, zinc-based alloys are the gold
standard sacrificial electroactive cor-
rosion coatings for low-alloy steels. The
extent of protection is proportional to
the thickness of the coating, with inevi-
table cost penalties for sensitive compo-
nents requiring prolonged corrosion pro-
tection.
3
Zinc coatings are less ductile
than the steel substrates they protect.
Deformation of the steel can induce
flaking or cracking of the galvanic coat-
ing and compromise the coatings corro-
sion-resistance properties.
4
Furthermore,
zinc coatings are susceptible to fluctua-
tions in precursor prices, an issue that
has increased in importance in recent
years. Zinc and tin prices spiked dramat-
ically in 20052006, but have stabilized
since the discovery of new mines and
mitigation of supply chain restrictions.
Nevertheless, many steel companies
anticipate a severe shortage of zinc in
20 to 25 years resulting in substantial
research efforts dedicated to mitigating
reliance on this material.
Manufacturers used chromium and
various chromate coatings to plate
carbon steel, zinc, and aluminum
substrates for most of the last century
because of the ease of plating, excel-
lent corrosion resistance, remarkable
wear resistance, Vickers hardness
values ranging up to 1000 kg/mm
2
,
and lustrous surface finish.
5
However,
because of the potent carcinogenicity
of hexavalent chromium and environ-
mental concerns regarding disposal of
electroplating dips, and the harmful
effects of the mist created during the
plating process,
6
the European Unions
stringent regulations the Restriction
of Hazardous Substances (RoHS) direc-
tiveslimit chromate use to 0.1 wt%
in conversion coatings.
7
The growth of chrome electroplating
and metal-finishing shops paralleled the
boom in the US steel industry between
the late 19
th
century to the middle of
the 20
th
century as railroads linked
an integrated supply chain across the
Great Lakes region that would become
the bedrock of the manufacturing base.
Historically, small- and medium-sized
customized metal-finishing enterprises
dominated this sector, and, not surpris-
ingly, these businesses were buffeted
by the upheavals in the steel industry
starting from the 1970s.
Despite the nations increasing reli-
ance on imported steel, metal-finishing
shops continue to be important to the
manufacturing economy in traditional
steel towns across the Rust Belt.
In the BuffaloNiagara region that is
home to the primary authors of this
article, for example, the closing of the
Bethlehem Steel plant in Lackawanna,
N.Y., devastated the local economy.
Even so, the Brookings Institute esti-
mates the region provides more than
14,500 jobs directly related to metal
finishing, fabrication, and tool manu-
facturing and has enjoyed strong job
growth during the last two years.
Beyond the economics of the steel
industry, increasing alarm regarding the
environmental impact of heavy met-
als from the metal finishing industry
is reframing the national conversation
regarding the environmental conse-
quences of a manufacturing economy.
The Environmental Protection Agency
(EPA), the Occupational Safety and
Health Administration (OSHA), and
the National Institute for Occupational
Safety and Health (NIOSH) have
issued successively more restrictive reg-
ulations regarding disposal of chromi-
um-based effluents. The Clean Air Act,
the Clean Water Act, the Resources
Conservation and Recovery Act
(RCRA), and the Toxic Substances
Control Act
8
directly address chromium
concentrations in air, water, and soil.
As the BuffaloNiagara region, along
with other manufacturing towns, seeks
to once again seize the manufactur-
ing moment, there is opportunity for
a renewed focus on sustainability and
sustainable materials, process efficiency,
and additive approaches to manufac-
turing that could potentially bring
innovation to metal-finishing, joining,
and forming industries that will enable
them to once again be important driv-
ers of economic growth.
Hybrid nanocomposites: Putting
graphene to work in coatings
The vast array of materials that
have been tested as alternatives to
zinc and chromate coatings includes
engineered polymers, conductive poly-
mers, polysiloxanes, metal oxides, ther-
mally sprayed cermets, self-assembled
monolayers, active corrosion inhibitor
technologies, encapsulated monomers,
and bioactive or biomimetic materi-
als.
5,911
Polymeric coatings have shown
potential as corrosion inhibitors, but
adhere poorly to metal substrates.
12,13

Nanostructured coatings show promise,
but suffer from inherent porosity, which
creates channels for water and ions to
permeate the coating and corrode the
metal surface.
14
There is growing interest in design-
ing hybrid nanocomposites compris-
ing multiple components, where the
individual components act in concert
to deliver corrosion resistance, form-
ability, and adhesion to steel sub-
strates.
15,16
Herein, we present a hybrid
nanocomposite coating system that
combines the electroactivity of carbon
nanomaterials, such as multiwall carbon
nanotubes (MWCNT) and exfoliated
graphene, with the water impermeabil-
ity and excellent adhesion properties
of a specialty polymer, polyetherimide
(PEI). The nanocomposite protects
low-alloy steel substrates through an
activepassive approach, serving as
a physical barrier to water permeation,
preventing formation of ion channels at
the metal surface, and passivating the
metal/metal oxide surface through elec-
tron depletion at the interface, likely
through establishment of a Schottky
barrier.
3,9,17,18
Two coating systems were
studied: a graphene/PEI composite with
www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 5 20
Graphene nanocomposite coatings for protecting low-alloy steels from corrosion
high loading of the nanomaterial filler;
and a combined graphene/MWCNT/
PEI system with a much lower loading
of each filler to study synergistic effects
between the two types of carbon nano-
materials. (A MWCNT/PEI system also
was tested, but it showed no enhanced
corrosion-resistance properties.)
Graphene, a single-atom-thick layer
of sp
2
-hybridized carbon atoms, has
remarkable electronic, mechanical, and
thermal properties. Since their discov-
ery in 1991, carbon nanotubes have
been researched extensively. However,
their exceedingly high costs and
environmental concerns have slowed
large-scale commercial implementation.
Many methods for producing graphene
have been developed, but the facile
non-oxidative solution-phase exfolia-
tion of graphite is particularly interest-
ing, because it is scalable and avoids the
oxidative functionalization that tends
to disrupt the -conjugated structure
(pristine aromatic ring system), which
is critically important to many of gra-
phenes remarkable proper-
ties.
19
We denote exfoli-
ated graphene derived from
ultrasonication of graphite
in N-methylpyrrolidone
(NMP) as unfunctionalized
graphene (UFG).
Several approaches exist
for dispersing graphene
and MWCNTs in polymer
matrices, although com-
posites with PEI have not
been reported to the best
of our knowledge.
20,21
PEI
is an optimal candidate for
the polymer host matrix
because of its flexibility,
high glass transition tem-
perature (155C), excel-
lent thermal stability,
and radiation resistance,
while also serving as a
perfect host for carbon
nanofillers through
stacking.
3,17,20,22,23
The lat-
ter noncovalent stacking
mode describes the attrac-
tive interactions between
aromatic ring systems
derived primarily from the
alignment of positive and negative
electrostatic potentials on adjacent aro-
matic rings. Using in-situ polymeriza-
tion, the carbon nanomaterials disperse
in the PEI precursor (poly(amic acid),
PAA) prior to polymerization, results
in improved dispersion of the nano-
structured carbon fillers in the eventual
polymer matrix. The uniform disper-
sion of nanomaterial in the matrix,
along with the remarkable adhesion of
the tailored PEI to the steel substrate,
facilitates improved corrosion resistance
under accelerated corrosion testing
conditions (Figure 2).
3,17
A manufacturing perspective
Applying coatings in a continuous
process to low-alloy steel must be fully
scalable, allow for high-throughput
integration with rolling or casting pro-
cesses, enable precise control of coating
thickness, and not require expensive
capital equipment. We have devel-
oped coating formulations that can be
applied through standard wire-bar and
spray-coating processes. The former
translates readily to roller-coating (gra-
vure, reverse roll, and knife-over-roll)
methods, which tend to be preferred by
many metal-finishing shops and steel
mills, thereby requiring little retooling.
In past work, we also demonstrated
electroplating of graphene onto metal
substrates from an aqueous solution
using a process similar to chrome
electroplating.
24
Although the results
reported here correspond to NMP dis-
persions, research proceeds on aqueous
analogs of these formulations.
Graphene is a potential sustainable
replacement for metals, such as zinc
and chromium, especially if graphite
byproducts from the steel industry can
be transformed to high-quality gra-
phene. The cost of sustainable coatings
can represent a major impediment to
their widespread adoption. As with
any new material and the absence of
economies of scale, reliable financial
projections are yet to be conclusively
established for the graphene production.
Nevertheless, some industry leaders sug-
gest that a price goal of $20 per pound
for graphene is attainable in the short
term and that costs of production could
soon be as low as $5 per pound. Given
the low graphene loadings in our formu-
lations and the high efficacy of much
thinner coatings (an order of magnitude
thinner than sacrificial metallic coat-
ings), the price proposition of the mate-
rials presented here is quite attractive.
Related to sustainable manufac-
turing, previous work demonstrated
the use of blast furnace gases to grow
directly well-adhered layers of carbon
nanotubes, multilayered graphene, and
carbon nanofibers onto low-alloy steel
substrates.
25
After deposition of PEI,
the carbon-nanomaterial/PEI composite
coatings provide excellent corrosion
resistance.
17
This method represents an
attractive route for designing a closed-
loop process that reduces the carbon
footprint of steel plants while adding
value to steel substrates.
Corrosion rate drops two orders
of magnitude
We synthesized UFG from natu-
ral flake graphite through ultrasonic
Figure 2. Synthesis and coating of nanomaterialPEI
composite coatings. SEM image of graphene platelets,
chemical structure of polyamic acid, photograph of the
graphene/PAA dispersions, photographs of two coating
methods (wire-bar coating and spray coating) and an
oven used for curing, and, lastly, photographs of the
coatings on steel.
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21 American Ceramic Society Bulletin, Vol. 92, No. 5 | www.ceramics.org
exfoliation of graphite
powder in NMP. The
MWCNTs used in this
study are more than 99
percent pure by weight
and have outer diameters
1318 nm with lengths
330 m.
Figure 3 depicts the
overall process for depos-
iting of PEI nanocom-
posite coatings. Briefly,
PAA is synthesized
by copolymerization
of an anhydride and
diamines in the pres-
ence of UFG and UFG/
MWCNTs. The desired
concentration of UFG
or MWCNTs is added to
the NMP and ultrasoni-
cated to create a visually
nonscattering solution
prior to polymerization.
The nanomaterial filler
disperses well in the
viscous UFG/PAA (or
UFG/MWCNT/PAA)
(Figure 2) allowing it
to be roller coated onto
freshly cleaned and
degreased low-alloy steel
substrates (Figure 3). PEI
is synthesized in-situ on
the steel surface through
an imidization reaction.
Although the mecha-
nism details have not yet
been fully investigated,
results show that the
in-situ imidization proto-
col yields coatings with
substantially improved
adhesion of the polymer
to steel, fashioning a
robust composite with
a dry coating thickness
of 1520 m.
3,17,26
The
m-phenylendiamine
component prevents
crystallization of the
polymer and improves
flexibility and formabil-
ity as the coating adopts
the contours of the low-
alloy steel surface.
3
The nanocomposite coatings were
deposited by wire-bar coating (chemical
coating) onto a clean cold-rolled steel
surface using either an automatic film
applicator or a spray coating method
(Figure 2). The PAA was cured at
150C for 5 min, followed by a 250C
curing step for 5 min to complete the
imidization of the PEI (Figure 3) and to
remove residual NMP.
We characterized the UFG synthe-
sized for use in the PEI nanocompos-
ites by scanning electron microscopy
and transmission electron microscopy
as shown in Figure 4. UFG tends to
agglomerate into large fragments on dry-
ing as shown in Figures 4(a) and 4(b).
However, Figures 4(c) and 4(d) show
that the UFG morphology is sheet like,
adding to the flexibility of the coating
and the formability of coated pieces.
Notably, the agglomeration and
phase segregation of UFG in nano-
composites is substantially mitigated
by the in-situ polymerization approach.
MWCNTs and graphene interact
strongly with polyimides via strong
stacking interactions. Because of the
structural similarity of these materials,
good wettability and chemical compat-
ibility between the matrix and the filler
are expected.
20,27
The PAA envelopes
the UFG platelets, and PAA chains
interacting with UFG likely impart
steric stabilization to the UFG colloids
in NMP. Figure 2 shows the highly
concentrated, stable UFG/PAA disper-
sions without phase segregation or floc-
culation of the UFG filler after several
months. Figures 4(e) and 4(f) show
high purity of the MWCNTs with outer
diameters of 1318 nm and lengths of
330 m. Analogous to UFG, bundling
of MWCNTs is mitigated by ultrasonic
treatment in NMP.
Photographs of the coatings are
depicted in Figure 2. A top-view
inspection of coatings in the SEM
reveals a fairly smooth surface finish
with no cracks or visible pinholes.
Furthermore, we observed no phase seg-
regation of UFG or MWCNT fillers at
the surface.
MWCNT and UFG sheets are
dispersed in the PEI matrix, as the
SEM images of cross-sections of cryo-
Figure 3. Schematic depictions of (a) UFG/PEI and (b)
UFG/MWCNT/PEI nanocomposite coatings on steel. The
wavy lines represent PEI polymer, the web-like sheets
represent graphene, and the tubes are MWCNTs.
(
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Figure 4. (a) and (b) SEM images of UFG, (c) and (d)
TEM images of UFG, (e) SEM image of MWCNTs, and
(f) TEM image of MWCNTs.
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(a)
(b)
(c) (d)
(e) (f)
(a)
(b)
www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 5 22
Graphene nanocomposite coatings for protecting low-alloy steels from corrosion
fractured surfaces of the free-standing
composite samples show (Figure 5).
Figures 5(a) and 5(b) show the PEI is
relatively featureless. In contrast, clear-
ly visible UFG and MWCNTs protru-
sions appear in the fractured composite
surfaces (Figures 5(c)5(f)). Figures
5(c) and 5(e) show that the MWCNTs
and UFG sheets are well dispersed,
and, again, there is no visible phase
segregation of the fillers from the PEI
matrix. The images further
suggest the presence of an
amorphous polymer coat-
ing around the UFG sheets
and individual MWCNTs.
The excellent dispersion
of the carbon nanomateri-
als in the PEI matrix is
likely a result of the
interactions between the
-conjugated graphene
basal planes and the aro-
matic moieties on the
polymer backbone.
17,20,23,27,28

Such excellent dispersion
of the conductive fillers
helps prevent delamination
of the composite coating
from the metal and appears
to aid formation of a pas-
sivation layer at the metal
surface.
Potentiodynamic electrochemi-
cal tests (following the ASTM-G59
standard) measured corrosion behavior
of coated samples, bare steel, and gal-
vanized steel in saline environments.
Figure 6 plots current density versus
potential for samples tested in 3.5%
NaCl solution. The current density for
nanocomposite-coated samples was sev-
eral orders of magnitude less (down to
about 10
9
A/cm
2
) than bare low-alloy
steel and galvanized steel (which have
current densities on the order of about
10
5
A/cm
2
). This correlates directly to
diminished corrosion of the steel surface
and demonstrates the efficacy of the
coatings as barrier materials. The poten-
tiodynamic measurements provide fur-
ther evidence of the formation of a pas-
sivation band from 0.243 V to 0.576 V
for the 20 wt% UFG/PEI nanocomposite
coating and from 0.010 V to 0.576 V for
the 2 wt% UFG/MWCNT/PEI coating.
The formation of a passivation band for
the nanocomposite coatingsbut not
for PEI alonesuggests that the conduc-
tive carbon nanomaterials are important
in forming the passivation layer at the
metal surface.
9,17,26

Furthermore, incorporating UFG and
MWCNTs in the coatings shifts the
potentiodynamic plots to more posi-
tive potentials, suggesting more noble
behavior for these systems. Although
the precise nature of the passivation
layer remains unclear, a Schottky bar-
rier often is seen at metal/nanotube
and metal/graphene junctions and
requires more bias to facilitate electron
transfer.
29,30
This type of potential bar-
rier at the interface likely impedes the
corrosion reaction by restricting the
flow of electrons to the steel surface,
which is required for oxidation. Also,
By Joshua Caris
MesoCoat Inc. (Euclid, Ohio) has developed a
high-density infrared (HDIR) process for applying
a uniform, metallurgically bonded metal layer
or cladto carbon-steel surfaces for corrosion-
and wear-resistance applications. Clad materials
include the nickel-based superalloy, Alloy 625,
and stainless steels as well as composites
containing tungsten and chrome carbides. This
new technology has the potential to be a game
changer, especially in the emerging oil sands
and shale gas industries.
The advantages of this technology are
Fast application rate (coverage of 75280 ft
2
/h
with a single system);
Low potential heat input to the substrate (small
heat-affected zone);
True metallurgical bond (bond strength greater
than 75,000 psi);
Lower initial cost, lowest life cycle cost (50
percent reduction); and
Better cladding (smooth, pinhole free, low dilu-
tion, and no decarburization).
HDIR processing is a heating and coating appli-
cation technology that developed concurrently
with lamp design improvements using broad
frequency thermal emitters, such as plasma arc
lamps and tungsten filament bulbs. Coupling
these irradiation sources with reflectors of vari-
ous geometries achieves the required irradiance
(W/cm
2
) for surface processing.
Tungsten filament lamps typically operate at
temperatures between 2000 K and 4000 K. The
Planck blackbody distribution peaks in the IR
range. However, there is a broad distribution
through the visible range, and the light appears
white.
Plasma arc lamps electrically induce a noble gas
plasma within a water-cooled, fused quartz tube.
These ceramic components are critical, because
they are transparent within the IR, permitting
containment of the plasma and transmission of
the light required to melt and fuse the cladding.
(A slurry loaded with cladding powders is depos-
ited on the surface to be clad.)
Oak Ridge National Laboratory developed the
plasma arc lamp technology for cladding sur-
faces in the early 2000s. Recently, MesoCoat
purchased exclusive rights to the technology and
has since commercialized it.
These lamps operate at a much higher tem-
perature, approximately 10,000 K. At this
temperature, the constrained plasma acts as a
blackbody emitter with a peak primarily in the
ultraviolet range. However, there are distinct IR
peaks characteristic of the noble gas, argon in
this case, superimposed on the blackbody back-
ground radiation. This high-intensity spectrum
is collected and carefully reflected and directed
to melt the slurry of corrosion- or wear-resistant
alloy or composite to the surface of a component
in what MesoCoat calls the CermaClad process.
The focused plasma arc lamp emission has
measured heat irradiances of 5002000 W/
cm
2
, which encompass the irradiance regime
New uses for carbon steel pipe thanks to corrosion- and wear-resistant claddings
Figure 5. Cryo-fractured SEM images of (a) and (b) PEI
(without filler), (c) and (d) 2 wt% UFG/MWCNT/PEI,
and (e) and (f) 20 wt% UFG/PEI.
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(a) (b)
(c)
(d)
(e) (f)
23 American Ceramic Society Bulletin, Vol. 92, No. 5 | www.ceramics.org
the hybridization of graphene with
metal surfaces can open a bandgap in
the semimetallic graphene, resulting in
semiconducting behavior for the metal/
UFG interfaces.
31,32
Charge depletion
from the passivating semiconducting
layer also could suppress corrosion.
The photographs in Figure 7 provide
a qualitative measure of the relative
corrosion rates of the various test sub-
strates of samples immersed in 3.5%
NaCl solution for various durations:
0 h; 234.5 h; 1,752 h; and 3,144 h
(the end of the immersion test). After
234.5 h exposure, extensive red rust
formed on the low-alloy steel surface.
Similarly, white powdery deposits on
the galvanized sample suggest sacrificial
corrosion of the zinc layer. The nano-
composite coatings and the filler-free
PEI coating show no visible signs of
corrosion. After 1,752 h of exposure to
3.5% NaCl solution, red rust formation
on the galvanized steel sample indicates
complete oxidation of the galvanic
coating. The coating of the PEI-coated
steel has partially delaminated, allow-
ing for corrosion to begin. In contrast,
the UFG/PEI and UFG/MWCNT/PEI
nanocomposite systems appear to have
avoided such a fate. Finally, after com-
pletion of this test at 3,144 h, extensive
corrosion across the test substrates is
apparent for all
samples, except
for the two coated
with 20 wt% UFG/
PEI and 2 wt%
UFG/MWCNT/
PEI. Some specks
of corrosion are
apparent for the
latter two samples,
especially under
microscopic exam-
ination, but they
are clearly superior
to PEI alone or
galvanized steel
for protecting the
low-alloy steel
substrates from
corrosion. (Despite
the differences in
appearance in the photographs, the two
samples corroded approximately the
same amount.)
Weight-loss measurements pro-
vide a more quantitative perspective
of the inhibitory properties of the
nanocomposite coatings. The weight-
loss measurements of the samples
shown in Figure 7 were conducted per
ASTM-G1. According to this protocol,
the corrosion rate (CR) in millimeters
per year is
CR = 87.6(W/DAt) (1),
where 87.6 is a constant, W the weight
loss in milligrams, D the density of
the metal in g/cm
3
, A the surface area
exposed to the NaCl solution in cm
2
,
and t the duration of exposure to the
NaCl solution in hours. The calculated
CR values for the samples are listed
in Table 1. The 20 wt% UFG/PEI
nanocomposite coating corrodes almost
three orders of magnitude slower than
of continuous-wave lasers, but with several
unique differences. Laser-processing light has
a relatively small beam diameter from a mono-
chromatic light source. HDIR processing takes
advantage of a broad spectrum of irradiation
with a focus area that corresponds to the diam-
eter and length of the quartz tube containing the
plasma. Because the irradiances are similar, a
qualitative comparison is that laser processing
is like a brush used to paint a portrait, while
HDIR focused plasma processing is like a roller
for painting a wall.
Figure 1(a) shows the interior pipe surface arc
lamp just after ignition. To clad the pipe interior,
the 10-inch-diameter pipe translates over a
lance onto which the lamp is mounted. Once
the pipe is extended fully over the lance, the
lamp is brought to operating power, and the
rotating pipe translates over the lamp (Figure
1(b)).
Figure 2(a) shows a wear-resistant cermet clad-
ding on a white-cast-iron substrate (20 mm
35 mm 150 mm). The cladding is composed
of angular tungsten carbide particles in a
Ni-Cr-B-Si alloy matrix and was applied in two
stages with an overlap region (designated by the
yellow box in Figure 2(a)). Optical micrographs
reveal uniform distribution of WC particles at
the surface (Figure 2(a)) and at the interface
(Figure 2(b)). Figure 2(b) also shows an absence
of microcracking in the white cast iron despite
multiple thermal cycles. Current plans for wear-
resistant claddings such as these are to combine
a flat-plate cladding technology with the pro-
cessing understanding of interior pipe clad with
Alloy 625 and apply wear-resistant claddings on
large-area pipe interior surfaces for use in oil
sand fields in Alberta, Canada.
Joshua Caris is a metallurgist at MesoCoat Inc.
Contact: Joshua Caris at jcaris@mesocoat.com.
n
Figure 1. Plasma arc lamp during (a)
ignition sequence and (b) processing of
a 10-inch-diameter carbon steel pipe.
Figure 2. A white-cast-iron sample (a)
clad with WC composite and microstruc-
tures of the (b) surface and (c) interface
between cladding and substrate.
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Potential vs. SCE (V)
Figure 6. Potentiodynamic plots showing the relatively enhanced
corrosion resistance provided by the composite coatings as
compared with the behavior of the PEI coating (without fillers),
uncoated steel, and galvanized steel. A scan rate of 1.67 mV/s
was used with a platinum strip and standard calomel electrode
as the counter and reference electrodes, respectively.
(a)
(b)
(b)
(a)
(c)
www.ceramics.org | American Ceramic Society Bulletin, Vol. 92, No. 5 24
Graphene nanocomposite coatings for protecting low-alloy steels from corrosion
bare low-alloy steel. The inclusion of
UFG or MWCNTs also reduces corro-
sion by an order of magnitude over the
pure polymeric coating.
Conclusions
In summary, tests show that two novel
nonmetallic nanocomposite systems protect
low alloy steels from corrosion. The in-situ
copolymerization of an anhydride and a
diamine is used to prepare PAA in the pres-
ence of UFG and MWCNTs. PAA disperses
and stabilizes the carbon nanomaterials in
NMP through interactions. Roller coat-
ing and subsequent imidization of the nano-
composite blends yields well-adhered UFG/
PEI and UFG/MWCNT/PEI coat-
ings on steel. The nanocomposite
coatings combine the water imper-
meability and excellent formability
of the polymer with the electroac-
tivity of the carbon nanomaterial
fillers. Potentiodynamic testing and
saltwater immersion tests indicate
more than three orders of enhance-
ment in efficacy of corrosion pro-
tection as compared with bare steel.
The developed nanocomposites
represent a scalable solution for
replacement of hexavalent chro-
mium in anticorrosive coatings.
Acknowledgments
This work was supported by
Tata Steel and the New York State
Pollution Prevention Institute.
About the authors
Robert V. Dennis is a gradu-
ate student and Lasantha T.
Viyannalage is a postdocotal
researcher at the University at
Buffalo, The State University of
New York, Buffalo, N.Y. Sarbajit
Banerjee is an associate professor
in the Department of Chemistry,
also at University at Buffalo.
Anil V. Gaikwad and Tapan K.
Rout are research associates with
the Research & Development
Department, Tata Steel Ltd.,
Jamshedpur, India. Contact:
Sarbajit Banerjee at sb244@buffalo.edu.
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Table 1. Corrosion rate of samples
Sample Corrosion rate (mm/year)
Galvanized steel 3.87 10
2
Uncoated low-alloy steel 1.22 10
1
PEI coating 9.24 10
3
2 wt% UFG/MWCNT/PEI coating 5.52 10
4
20 wt% UFG/PEI coating 8.46 10
4
Figure 7. Saltwater (3.5% NaCl) immersion mea-
surements on (a) galvanized steel, (b) uncoated
low-alloy steel, (c) low-alloy steel with PEI coating,
(d) low-alloy steel with 2 wt% UFG/MWCNT/PEI
coating, and (e) low-alloy steel with 20 wt% UFG/
PEI coating. Sample exposure diameter 3.5 cm.
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