MICROSCOPY RESEARCH AND TECHNIQUE 76:1186–1195 (2013)

A Polyaniline Based Intrinsically Conducting Coating

for Corrosion Protection of Structural Steels
TONGYAN PAN,1* AND ZHAOYANG WANG2
1
Department of Civil Engineering, The Catholic University of America, N.E., Washington, District of Columbia, 20064
2
Department of Mechanical Engineering, The Catholic University of America, N.E., Washington, District of Columbia, 20064

KEY WORDS corrosion; steels; coating; p-conjugated polymer; SKPFM

ABSTRACT Among the various corrosion protection strategies for structural steels, coating
techniques provide the most cost-effective protection and have been used as the primary mode of
corrosion protection. Existing coating techniques however have been used mainly for their bar-
rier capability and therefore all have a limited service life due to oxidation aging, electrolytic
degradation, or various inadvertent defects and flaws occurred in and after coating applications.
This work investigated the anti-corrosion potential of a p-conjugated polymer—polyaniline
(PANi), which was doped into an intrinsically conducting polymer and then included in a two-
layer coating system as a primer layer. To achieve a long service life, the primer layer was made
by mixing the conductive PANi in a waterborne poly-vinyl butyral solution to provide strong
adhesion to steel surface, and then topcoated with a layer of elastomer-modified polyethylene to
obtain extra mechanical and barrier protections. Two ASTM standard tests were conducted to
evaluate the corrosion durability and tensile adhesion of the two-layer system, in which the sys-
tem demonstrated superior performance. The Scanning Kelvin Probe Force Microscopy
(SKPFM) was used to provide the microscopic evidences for the outstanding performance.
Microsc. Res. Tech. 76:1186–1195, 2013. V 2013 Wiley Periodicals, Inc.
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INTRODUCTION stress (ASM International, 1995). In typical service con-

Steels are the primary metallic material used in man-
ufacturing and construction industries, owing to their
superior mechanical properties, high workability, toler-
ance of extreme temperatures, and relatively low pro-
duction cost. Industrially, steels with less than 0.2 wt %
carbon are known as mild steels that can barely pro-
duce any useful hardening effect upon quenching, while
the steels that do demonstrate applicable hardening
effects, usually but not necessarily containing over 0.2
wt % carbon, are commonly referred to as structural
steels (AISC, 2011). Structural steels each have a solid
heterogeneous microstructure including multiple met-
allurgical phases, i.e., crystalline grains of iron with
various impurities/inclusions within the grains or on
their boundaries (AISC, 2011; Bugayev et al., 2001;
Harvey, 1982). Such impurities/inclusions include a-
iron (bcc) andg-iron (fcc) embedded with inter-metallic
or non-metallic compounds including cementite, car-
bides, nitrides, and sulfides, and some extent of crystal-
line defects composed of point defects, line defects,
planar defects, and bulk defects. With different morphol-
ogies, sizes, and mechanical properties, the different
metallurgical phases forming a steel possess different
mechanical and electrochemical properties and each play
a different role in corrosion initiation under a given envi-
ronmental and stress condition (AISC, 2011; Bugayev
et al., 2001; Harvey, 1982; Wilson, 1975; Leffler, 1998).
Steel-based structural components in general are
designed to sustain a level of mechanical stress trans-
mitted from the loading on the structure, whether
static, dynamic, or combined (AASHTO, 2011). Many
structural steels are also under significant residual
ditions, steels are also subject to an environmental load,
i.e., corrosion, which fall in two general categories based
on the fundamental driving forces: (1) General Corro-
sion in which the occurrence of corrosion is independent
of the mechanical stress existent in the steel and (2)
Stress-Related Corrosion in which the occurrence of cor-
rosion interacts with mechanical stress sustained by
the steel, causing a level of damage greater than the
sum of the damages by corrosion and stress acting sepa-
rately. The four major types of Stress-Related Corrosion
are stress-corrosion cracking, corrosion fatigue, fretting
corrosion, and hydrogen-assisted cracking, each with a
unique occurrence mechanism (ASM International,
1986; Crooker and Leis, 1984; Hochmann et al., 1979;
Parkins, 2000). While General Corrosion often occurs in
quite corrosive conditions, Stress-Related Corrosion is
more ubiquitous and is even observed in very mild envi-
ronments where the damage by General Corrosion is
negligible (ASM International, 1986; Crooker and Leis,
1984; Hochmann et al., 1979; Parkins, 2000).
Corrosion management of today’s structural steels
relies heavily on large-scale and conservative protec-
tion strategies, such as all-inclusive coatings or surface
treatment, extensive cathodic protection, and the use
*Correspondence to: Tongyan Pan Assistant Professor of Engineering Materi-
als. The Catholic University of America, 620 Michigan Avenue, N.E., Washing-
ton, DC 20064, USA. E-mail: pan@cua.edu
Received 8 June 2013; accepted in revised form 11 August 2013
Contract grant sponsor: National Cooperative Highway Research Program
(NCHRP)’s IDEA; Contract grant number: NCHRP-157.
DOI 10.1002/jemt.22283
Published online 2 September 2013 in Wiley Online Library
(wileyonlinelibrary.com).

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V 2013 WILEY PERIODICALS, INC.
 PANi BASED ICP FOR CORROSION PROTECTION COATING SYSTEM
of stainless steels (FHWA, 2006; Revie and Uhlig,
2008; Wardhana and Hadipriono, 2003). The use of
cathodic protection and stainless steels are expensive.
Cathodic protection, either by galvanic protection or
impressed current, entails frequent inspection and
maintenance. Stainless steels, bearing high material
cost, are used mainly in critical parts of structures.
Most stainless steels, however, are susceptible to
stress-assisted corrosion, which has been criticized as
one major drawback of using stainless steels in struc-
tures (Revie and Uhlig, 2008). With the pros and cons
of the existing corrosion protection strategies, the coat-
ing technique provides the most cost-effective protec-
tion to steels, and thus far has been used as the
primary mode of corrosion protection for structural
steels. Today nearly all structural steels working in
open air (e.g., steel bridges), immersed in solutions or
alternate immersed conditions (e.g., reinforced con-
crete) are coated (FHWA, 2006; Revie and Uhlig, 2008;
Wardhana and Hadipriono, 2003).
Existing coating techniques, however, have been
used mainly for their barrier capability for prevention
of oxygen, water, and ions and therefore must cover
the entire surface of steel. These coatings however all
have a limited service life due to various mechanisms
such as oxidation aging, electrolytic degradation, vari-
ous inadvertent defects and flaws occurred in and after
the placement of coating materials, and most fre-
quently and destructively the delamination of coating
off substrate surface. When delaminated, aged,
degraded, or defected, a coating will lose most of its
barrier effect and therefore requires frequent and
costly inspection and maintenance (FHWA, 2006;
Revie and Uhlig, 2008; Wardhana and Hadipriono,
2003). The coating technique however has one very
attractive advantage, i.e., easy on-site application,
which in practices has proven to be highly cost- and
labor-effective and has greatly facilitated coating
repair and replacement (Revie and Uhlig, 2008).
To sum up, in the current knowledge of corrosion
management, the corrosion durability of structural
steels is controlled by (1) the durability of coatings in
resisting delamination and to a less extent oxidation
aging and electrolytic degradation, (2) the heterogene-
ous metallurgical inclusions in steel matrix, and (3)
the mode and magnitude of applied mechanical load-
ings. These controlling factors, in interaction with the
external environment, play a key role in the initiation
of a wide variety of corrosion such as the pitting, crev-
ice, filiform, or stress-related types of corrosion
(AASHTO, 2011; FHWA, 2006; Revie and Uhlig, 2008;
Wardhana and Hadipriono, 2003). The coating tech-
nique, being the primary mode of corrosion protection
for structural steels, however requires costly mainte-
nance. Within this context, to improve the cost-
effectiveness in managing stress-assisted corrosion of
structural steels, it is highly desirable to have a dura-
ble coating system that keeps the advantage of easy
application while possessing a significantly extended
service life to reduce maintenance cost.
MATERIAL AND METHODS
The current coating techniques of structural steels
entail a surface treatment with a primer layer followed
by a top-coating. An intermediate layer of organic
Microscopy Research and Technique
1187
TABLE 1. Formulation of the polyaniline-based intrinsically con-
ducting primer
(wt %)
Part I
Polyaniline 10.0
Poly-vinyl butyral 20.0
Titanium dioxide (TiO2) 5.0
Isopropyl alcohol ((CH3)2CHOH) 50.0
Talc (Mg3Si4O10(OH)2) 5.0
Water 10.0
Part II (wt %)
Phosphoric acid (H3PO4) 15.0
Isopropyl alcohol ((CH3)2CHOH) 65.0
Water 20.0
materials like epoxy is also commonly used between
the primer and topcoat to provide additional adhesion
and the protection of the primer and substrate. A com-
monly used primer layer today is the poly-vinyl buty-
ral resin pigmented with zinc tetroxy chromate and
phosphoric acid. On treatment of steel surface with
primer, a zinc-chromate coating along with the resin
coating form a 10–20 lm thick layer. The zinc-rich
primer, particularly the high toxicity of chromate, has
led to increasing interest in using non-toxic alterna-
tives. In recent years, the intrinsically conducting
polymers (ICPs) have received attentions to make such
environmentally friendly primers, including mainly
the polypyrrole (PPY) and polyaniline (PANi) doped
with different acceptors or donors. Based on the prom-
ising performance achieved thus far (DeBerry, 1985;
Kendig et al., 2003; Kinlen et al., 1997; Kowalski et al.,
2010; Sauvant-Moynot et al., 2008; Spinks et al.,
2002), this study explores the use of a PANi based
primer in a two-layer coating system and evaluates its
corrosion protective capability of structural steels.
The primer system consists of two parts as formu-
lated in Table 1. The resin part (Part I) was prepared
by adding isopropyl alcohol into poly-acrylic acid
doped PANi that was dispersed in water before dop-
ing. The mixture was then stirred to obtain a green-
color emeraldine salt solution. After being stirred for
60 min, the poly-vinyl butyral resin was added in the
solution and stirred for additional 24 h. Figure 1a
shows the molecular changes in the doping of PANi
and Figures 1b and 1c show the mixing of doped PANi
in the poly-vinyl butyral solution to make the primer
layer.
Immediately before coating, the Part I and Part II
were mixed in the ratio of 1:1 (wt/wt) and well
stirred. The mixture was spin-coated onto three
freshly cleaned carbon steel test coupons prepared
using the steel AISI/SAE 1045. The coating thick-
ness was measured to be about 15 lm after drying.
After the green-colored coating got dried in the air,
a layer of fluoroelastomer-modified polyethylene was
spin-coated as the topcoat at the thickness of about
40 lm. The topcoat also includes the titanium diox-
ide (Rutile) as the main pigment, mica and silica as
extender pigments, and dioctyl phosphate as a plas-
ticizer. The pigments were premixed for 60 min
before painting. Figure 2 shows the steel coupons
coated with the primer (left) and the two-layer coat-
ing system (right).
1188
Fig. 1. Molecular changes in doping of PANi (a) and mixing of doped PANi in polyvinyl-butyral solution (b).
Fig. 2. Steel coupons coated with: (a) primer only (20 lm); (b) primer and topcoat (40 lm). [Color figure
can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
ASTM Standard Tests
The developed coating system was first evaluated by
two ASTM standard tests, i.e., ASTM B 117—Standard
Practice for Operating Salt Spray (Fog) Apparatus
(ASTM International, 2011), and ASTM D 4541—
Standard Test Method for Pull-Off Strength of Coat-
ings Using Portable Adhesion Testers (ASTM Interna-
tional, 2002). The performance of the two-layer coated
steel panel in the Salt Spray test was compared to that
of a control steel panel coated only with the topcoat
material, i.e., the fluoroelastomer-modified polyethyl-
ene, at the thickness controlled to be 60 lm (same as
the total thickness of the two-layer coating) tested
under the same salt spray condition. Figure 3 shows
the two steel panels after 4,000 h salt fog exposure.
The fluoroelastomer-modified polyethylene coated
panel corrodes more severely than the two-layer sys-
tem coated panel, with apparent sign of delamination.
Figure 3a also shows the signs of the tensile adhesion
tested per ASTM D 4541.
SKPFM Characterization
Prior to top-coating, one primer-coated coupon (with
20 lm PANi-primer) was studied by Scanning Kelvin
Probe Force Microscopy (SKPFM). SKPFM is a power-
ful surface analysis technique for measuring the
atomic-level topography and surface corrosion electric
potential in terms of Volta potential difference (VPD),
T. PAN AND Z. WANG
as illustrated in Figure 4 on a Duplex steel surface.
SKPFM has been evaluated extensively in the author’s
existing research (Pan, 2012a,b; Pan and Sun, 2012).
The fundamental principle of SKPFM in measuring
VPD is based on the concept of work function U of a
metallic material, which is defined as the minimum
work required for extracting an electron from inside
the sample to a position just outside the sample that is
far enough to eliminate contributions from image
forces (see Fig. 4a) (Pan, 2012a,b; Pan and Sun, 2012;
Trasatti, 1991). Work function is equivalent to the dif-
ference in energy between the vacuum level and Fermi
level indicated in Figure 5a as Evac and EF, respec-
tively. Work function U therefore consists of two parts
per Eq. (1) for samples carrying no electrical charges,
i.e., the chemical work le—the chemical energy needed
to transfer the electron from the infinity into the sam-
ple, and the dipole or surface potential related work
evthat takes into account the electrostatic work to
transport the electron through the dipole layer of sam-
ple surface, wherev is the potential drop between just
inside the bulk material and just outside of it (Pan,
2012b; Pan and Sun, 2012; Trasatti, 1991).
U52le 1ev52ðle 2evÞ (1)
For more general objects that carry electrical
charges such as a SKPFM probe (the Kelvin probe—
Microscopy Research and Technique
 PANi BASED ICP FOR CORROSION PROTECTION COATING SYSTEM
KP in Fig. 5d) and a metallic sample in corrosion stud-
ies, an additional work term is needed to transfer the
electron from just outside the sample surface to a posi-
tion absolute vacuum or infinitely far away (see Fig.
5b). The additional component can be calculated as ew,
with which a generalized work function U* can be
defined per Eq. (2) as the work required for extracting
an electron from within the sample (Point A in Fig. 5b)
to infinitely far away, for example, Point B in Figure
5b in the absolute vacuum. The symbol w is the Volta
potential which is equivalent to the potential drop
Fig. 3. 4000-h salt spray test of AISI 1045 panels: (a) primer and
topcoated; (b) top-coated only. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]
Fig. 4. SKPFM measurement of topography and VPD of steel surfaces. [Color figure can be viewed in
the online issue, which is available at wileyonlinelibrary.com.]
Microscopy Research and Technique
1189
from infinitely far away to a location just outside the
surface.
U 52le 1ev1ew52ðle 2ev2ewÞ (2)
The sum of the dipole/surface potential v and Volta
potential w gives the Galvani potential u, which is the
potential drop between the bulk sample and the vac-
uum level infinitely far away from the surface.
/5v1w (3)
The absolute electrode potential Eabs of a sample
covered by a liquid layer (or an oxide film, an organic
or polymer coating) (see Fig. 5c) can be defined, based
on the concept of work function, as the minimum
potential needed to transfer an electron from the
Fermi level, through the metal/liquid (oxide or coating)
interface (with the potential drop of D/ElM ), the liquid
(oxide or coating) and its surface layer to a position
just outside the liquid (oxide or coating) (Pan, 2012b;
Pan and Sun, 2012; Trasatti, 1991). Eabs per Eq. (4)
can be derived from Eq. (1) by adding an additional
term D/ElM 5/M 2/El , the potential drop at the metal/
liquid (oxide or coating) interface (with “El” means
“electrolyte”), and replacing the v with the dipole/sur-
face potential of the liquid (oxide or coating) surface
vS. UM2S is the generalized work function of an elec-
tron that is transferred following the path A!C, i.e.,
from within the sample (e.g., an electrode) to a position
outside the liquid (oxide or coating) layer covering the
sample (see Fig. 5c) (Pan, 2012b; Pan and Sun, 2012;
Trasatti, 1991).
1  l 
Eabs 5 UM2S 5 2 e 1D/El M 1vS (4)
e e
1190 T. PAN AND Z. WANG
Fig. 5. Schematic illustration of the working principles of SKPFM. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]
According to Figure 5d, if an electron is transferred
following the path A!B!C instead of A!C, Eq. (5) is
obtained, with wM and wS being the Volta potentials
outside the metal and outside the liquid (oxide or
coating).
 
1 nenmacher et al., 1991a,b; Pan, 2011; Pan and Lu, 2011;
Eabs 5 U1 wM 2wS (5)
e
Based on the concept of absolute electrode potential,
if a metallic SKPFM probe is connected to the sample
by a metallic wire and positioned near the surface of
the electrolyte as shown in Figure 5d, Eq. (6) can be
obtained corresponding to the three paths, considering
that the work function difference between two points
is a constant for a given situation. It is noted that the
work required for an electron to transfer from the
metal sample into the SKPFM probe (via the metallic
wire) is negligible.
 l  1  
1
Eabs 5 UM2S 5 2 e 1D/El M 1vS 5 U M
1 w M
2w S
e e e point-by-point basis during the lift mode rescan
1 KP  KP S

5 U 1 w 2w
e
(6)
The measurement of the VPD (wKP2wS) is what the
SKPFM probe technique measures. In engineering
practices, frequently it is not the value of the absolute
electrode potential (or work function) of the probe tip
but a relative electrode potential (or work function) of
the tip measured w.r.t. a reference electrode, for exam-
ple the standard hydrogen electrode, SCE or Ag/AgCl
electrode. The absolute electrode potential is related to
the relative electrode potential or corrosion potential
w.r.t. the standard hydrogen electrode by Eq. (7),
where E0(H2)abs is the potential of the standard hydro-
gen electrode in the absolute electrode potential scale,
which is a value between 4.44 and 4.85 V.
EcorSHE 5Eabs 2E0 ðH2 Þabs
The electrode potential hence refers to the potential
drop across the metal/liquid (oxide or coating) interface
including the electrical double layer. As discussed
before, the absolute electrode potential is not directly
measurable and usually a reference electrode potential
is measured w.r.t. a standard electrode. The electrode
potential is frequently referred to as the Open Circuit
Potential (OCP) or corrosion potential in practices.
The working mechanism of SKPFM is based on the
existence of atomic-level corrosion potential and the
implementation of the theoretical principles discussed
above via the standard Atomic Force Microscopy (Non-
Pan and van Duin, 2011a,b; Pan and Xi, 2011). SKPFM
operation involves first scanning the sample surface in
the AFM tapping mode to determine the topography on
a line-by-line basis, and then rescanning across the sur-
face at a fixed height, i.e., in the “lift mode” with the
metal-coated or doped silicon cantilever lifted to a fixed
distance from the surface, typically 100 nm. The tapping
piezo is turned off in the rescan, and an AC voltage
Vacsin(xt) is applied to the tip to stimulate oscillations of
the cantilever (Nonnenmacher et al., 1991a,b).
The AC voltage Vacsin xt is connected to the VPD Dw
over the capacitor formed by the SKPFM cantilever/tip
and the metallic sample. The magnitude of tip oscilla-
tions at the stimulating frequency x is nulled on a
through adding to the tip a DC voltage Vdc that balan-
ces the VPD Dw. Accordingly, SKPFM nulls the first
harmonic of the force exerted by an electric AC field on
the charged cantilever/tip (Nonnenmacher et al.,
1991a,b). The electric energy stored in the capacitor
formed by tip/cantilever and sample is given in Eq. (8)
in terms of its capacitance C and the potential V of the
electrical field in the capacitor per Eq. (9) (Nonnen-
macher et al., 1991a,b).
1
Wcapacitor 5 V 2 C (8)
2
V5Dw2Vdc 1Vac sin ðxtÞ (9)
The electrical force in the capacitor can be obtained
as the gradient of the potential V per Eq. (10).
(7) dWcapacitor 1 2 dC
Fe 52 5 V (10)
dz 2 dz
Plugging Eq. (9) in Eq. (10) and considering the trig-
onometric relation: sin 2 ðxtÞ5 ð12cos2ð2xtÞÞ, Eq. (10) even-
tually turns into Eq. (11) that forms the basis for the
nulling mechanism in SKPFM, which is achieved by
Microscopy Research and Technique
 PANi BASED ICP FOR CORROSION PROTECTION COATING SYSTEM 1191

Fig. 6. SKPFM scanned topography (a) and VPD (b) of PANi-primer coated steel. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.com.]

Fig. 7. SKPFM scanned topography (a) and VPD (b) of fluoroelastomer-modified polyethylene coated
steel. [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

applying a DC voltage Vdc equal to the VPD, i.e.,
Vdc 5Dwreference
Sample . Therefore, nulling of the force directly
yields the measurement of VPD in SKPFM.
1 2 dC
Fe 5 ðVdc 2Dwreference
Sample Þ  1ðDwreference
Sample 2Vdc Þ
2 dz
dC 1 2 2 dC
 Vac sin ðxtÞ  1 ½Vac 2Vac cos ð2xtÞ 
dz 4 dz
Figure 6 shows the surface VPD measured by
SKPFM on a steel coupon coated with a 20 lm thick
layer of PANi primer, in comparison to the VPD in Fig-
ure 7 of a control coupon coated with a 20 lm thick
layer of fluoroelastomer-modified polyethylene, i.e.,
the topcoat material. To initiate the corrosion of sub-
strate steel, a microscopic breach was made at the cen-
ter location of the left edge of the coated steel sample,
with the substrate steel exposed to air. Both coated
coupons were first soaked in a 0.5 M NaCl solution for
30 min, and then shifted to a humid atmospheric
condition (RH 5 90%) and kept therein 2 h for corro-
sion development. The SKPFM topography mea-
sured on the PANi-primer coated sample vs. the
fluoroelastomer-modified polyethylene coated sample
are also shown in Figures 6 and 7. The darker colored
regions shown in the VPD figures (Figs. 6b and 7b)
indicate more negative Volta potential that is more
likely to initiate anodic reaction. When such negative
Volta potential becomes negative enough with respect
to the surrounding areas, active corrosion will start.
(11) To further reveal the anti-corrosion effect and possi-
ble mechanisms of PANi, one region of an AISI 1045
steel sample was coated with 20 lm PANi-based
primer side by side with a second region coated with
20 lm fluoroelastomer-modified polyethylene. The
sample was then subjected to 60-h Salt Fog exposure
per ASTM B 117. Figure 8 shows the coating-removed
substrate surface of the two regions, with the
fluoroelastomer-modified polyethylene coated surface
on the left portion vs. the PANi-primer coated surface
on the right portion of the sample. The PANi-based
primer well preserves the shining steel surface as just
polished, whereas the fluoroelastomer-modified poly-
ethylene coated part shows obvious oxidation.
RESULTS AND DISCUSSIONS
The ASTM B 117 evaluates corrosion resistance of
coated steel specimens exposed to salt fog in an

Microscopy Research and Technique

1192 T. PAN AND Z. WANG
Fig. 8. Fluoroelastomer-modified polyethylene vs. PANi coated steel surface (coating materials
removed). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
environmental chamber, and the ASTM D 4541 meas-
ures the pull-off strength of a coating to the coated sur-
face. After 5,000 h, the maximum testing hours
according to ASTM B 117, the blistering and rusting of
the two-layer coated steel panels, as shown in Figure
3a, were rated to be 10—the highest score on a scale of
0–10, which indicates no blistering or rusting or less
than 0.01% of rust occurred. The undercutting was
rated as 0, which further implies excellent protection
of the substrate steel by the two-coat system. The pull-
off strength (psi), per ASTM D 4541, on the 5,000-h
Salt Spray tested samples was averaged to be 505 psi,
which is significantly higher than 200 psi, the thresh-
old value of good paintings by the Society for Protec-
tive Coatings (SSPC, 1995). The benefit of using the
primer-topcoat system came from different sources, of
which the strong binding strength of the poly-vinyl
butyral to steel surface plays an important role in pre-
venting the ingress of oxygen, water, and ions to the
coating–substrate interface. This strong barrier func-
tionality is important for the overall performance of
the coating system.
In comparison, the control steel panel coated with
fluoroelastomer-modified polyethylene (40 lm in thick-
ness) in Figure 3b shows much severe corrosion under
the same corrosion condition (specified by ASTM B
117). Moreover, not only obvious rust materials can be
seen in the scratch, significant coating delamination
also shows up on both sides of the scratch. However,
only slight sign of rust can be seen in the scratch made
on the two-layer coated panel, with no sign of delami-
nation. This phenomenon shows that the primer plays
an important role in corrosion protection, considering
the same overall thickness of coating(s) used on these
two panels. One major mechanism of coating delami-
nation is the high pH due to oxygen reduction at the
coating–substrate interface, generated at cathodic
locations in an active corrosion (Leblanc and Frankel,
2002). The lower level of delamination on the primer-
topcoat coated substrate steel suggests that a lower
level of oxygen reduction occurred than that on the
steel panel coated only by the fluoroelastomer-
modified polyethylene. This may benefit from the
shifted oxygen reduction location from the coating–
substrate interface to other locations such as the coat-
ing–solution interface, a phenomenon known as oxy-
gen smearing-out (Spinks et al., 2002).
SKPFM is capable of measuring the VPD and topog-
raphy of coated metallic surface over the coating
layers. The surface VPD measured by the SKPFM
shown in Figures 6b and 7b reveals the microscopic
mechanisms of corrosion protection enabled by the
PANi-based primer. Under the same corrosion environ-
ment, the sample coated with the PANi-based primer
shows significantly less negative VPD than the sample
coated with fluoroelastomer-modified polyethylene
only, which suggests that the substrate steel coated
with the primer is in a rather passive state, i.e., with
no or a low level of active corrosion. In contrast, the
fluoroelastomer-modified polyethylene coated sample
experienced an active filiform corrosion starting from
the left-hand side microscopic breach originally made
to initiate corrosion. More importantly, the two surface
VPD maps shown in Figures 6b and 7b demonstrate
very different potential distribution patterns in
regions away from the microscopic breach. Figure 6b
shows a more uniform potential distribution than that
in Figure 7b. The more uniform potential distribution
on the PANi-coated sample indicates a lower electric
potential gradient, and thereby a more passive surface
than that coated by the fluoroelastomer-modified poly-
ethylene. The PANi (Emeraldine Salt) based primer as
such demonstrates the functionality of passivating or
ennobling substrate surface, which has been reported
by other researchers for different metallic materials.
The topography measured by the SKPFM is shown in
Figures 6a and 7a. A portion of delamination can be
easily seen in Figure 7a due to the filiform corrosion
underneath as indicated in Figure 7b. The sample
coated with the PANi-based primer shows no sign of
delamination. The very different levels of surface oxi-
dation shown in Figure 8 further suggest the enno-
bling mechanism of the PANi primer.
The major coating system used today for structural
steels is the three-layer system including a zinc-rich
primer, an epoxy based intermediate layer, and a resin
Microscopy Research and Technique
 PANi BASED ICP FOR CORROSION PROTECTION COATING SYSTEM
Fig. 9. Doping of nondegenerate p-conjugated polymers: Transition from semiconductor to ICP. [Color
figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
topcoat. The epoxy and resin materials in general are
susceptible to delamination, aging, electrolytic degra-
dation, or inadvertent defects (Epstein, 1997; Stenger-
Smith et al., 1998a). The zinc-rich primer, as the sacri-
fice anode in the system when the galvanic corrosion is
initiated, will be irreversibly depleted (Epstein, 1997;
Stenger-Smith et al., 1998a). The existing coatings
hence require costly maintenance or replacement. The
existing coatings thus have been used primarily for
their barrier functionality and barely offer any correc-
tive benefits, which means that once steel corrosion
gets initiated at a location on steel surface, such as by
coating degradation or inadvertent flaws/defects, the
pitting, crevice, or filiform forms of corrosion will
develop at the location. Accordingly, it is desirable that
for the best protection effect both preventive and cor-
rective functionalities be enabled in one single system.
The PANi-primer based two coat system as developed
in this study constitutes such a multifunctional
system.
ICPs are a special group of organic polymer that pos-
sesses the property of electrical conductivity in parallel
to the advantageous properties of generic polymeric
materials in strength, flexibility, elasticity, stability,
and ease of handling (Pron and Rannou, 2002). The
conductivity stems from the doping of p-conjugated
polymers by acceptors (p-type) or donors (n-type), and
thus depends on the level of doping. In the undoped
state, the p-conjugated polymers are typical semicon-
ductors with clearly separated conductive and valence
bands. For degenerate p-conjugated polymers like pol-
yacetylene, upon doping the polymer chains, one of the
solitons (main chain defects) is ionized to yield a
charged soliton and a neutral anti-soliton in an associ-
ated pair. As the degree of doping increases (around 30
Microscopy Research and Technique
1193
wt % for polyacetylene), a large soliton band will form
that can close the band gap, making the polymer con-
ductive (Bredas et al., 1982). For non-degenerate p-
conjugated polymers like PANi, ionization of the poly-
mer chains by doping gives rise to polaron levels (main
chain defects) localized inside the band gap. From the
left-end to the right-end of Figure 9, the energy levels
continuously grow as the density of introduced charges
(doping density) increases (Bredas et al., 1982). The
Fermi level, which sits midway between the lowest
unoccupied and the highest occupied levels, during the
doping process, gradually moves to one edge of the
band gap. Ultimately, the rise of polaronic bands can
fully occupy the highest occupied molecular orbital
and lowest unoccupied molecular orbital bands, and
the electrical conductivity of the polymer is governed
by the hopping mechanisms between polaronic states.
Research on ICPs today has resulted in a number of
p-conjugated polymers as promising coating materials
for corrosion protection, including mainly PPY, PANi,
polythiophene, and poly(2,5-bis(N-methyl-N-hexyla-
mino)-p-phenylene vinylene) (Bredas et al., 1982; Pron
and Rannou, 2002; Stenger-Smith, 1998b). To make
practical applications, ICPs must also provide satisfac-
tory binding to substrate surface and good durability
in service conditions. To meet these two goals, ICPs
have been used as the primer—either directly depos-
ited on metallic surface or as microscopic or nanoscale
powder mixed in an organic matrix that has good bind-
ing with the metallic surface—coated with an interme-
diate and/or a top layer. The topcoated ICP structures
have been enabled to give comparable binding and
durability performances to the existing non-conductive
coatings as demonstrated in this study. With combined
ennobling, oxygen smearing-out, and barrier
1194 T. PAN AND Z. WANG
capacities, the ICP-based coating system can offer sig-
nificantly improved corrosion protection over the exist-
ing non-ICP based coatings. Furthermore, ICP-based
coating systems, like the one developed in this study,
offers significant environmental benefits over the
existing non-ICP based coatings. The ICP-based coat-
ing system does not include conventional toxic/carcino-
genic heavy-metal anti-corrosion pigments such as
chromates and lead compounds, while providing
heavy-duty corrosion protections. The ICP-based coat-
ing hence provides a viable alternative to meet the
urgent needs of chromium-free coatings for steels and
general metallic materials at large. For structural
steels specifically, this technology offers high effective-
ness, friendliness to the environment, scratch toler-
ance, lower cost, and longer service life.
SUMMARY AND CONCLUSIONS
This work investigated the potential use of an ICP,
i.e., a poly-acrylic acid doped PANi, to make a primer
layer in a corrosion protection coating system. When
mixed in poly-vinyl butyral that provides strong bind-
ing to steel surface and topcoated with a layer of
elastomer-modified polyethylene, the two-layer system
can be expected to have a longer service life and
replace the existing zinc-rich coating systems. Two
ASTM standard tests were performed to evaluate the
overall corrosion durability and tensile adhesion (pull-
off strength) of the system, in which the system dem-
onstrated superior performance. The SKPFM was
used to reveal the microscopic anti-corrosion mecha-
nisms of the ICP-based primer. The PANi-based pri-
mer, when topcoated with a layer of fluoroelastomer-
modified polyethylene, provides strong binding to the
substrate surface, superior corrosion protection by
potential mechanisms of surface ennobling and oxygen
smearing-out, and significant environmental benefits
over the existing non-ICP based coatings.
Looking to the future, the intrinsically conductive
polymers are a new type of anti-corrosion materials
that have shown both preventive and corrective
corrosion-protection effects on steels. Recently, ICP
materials have been tried to make smart coating sys-
tems that in general take a layered-structure form
including an ICP primer covered by one or two epoxy
or urethane layers, like the configuration studied in
this work. A smart system in general refers to one that
possesses the capability to autonomously provide the
as-needed service. Thus in a truly ICP-based smart
coating system, the ICP primer is also expected to
release corrosion inhibitor (usually the counter ions of
ICP dopant) to stop the inadvertently initiated corro-
sion for the purpose of self-healing. The release of cor-
rosion inhibitor can be triggered by the corrosion
potential or current at the onset of corrosion initiated
at the exposed substrate sites. When sufficient corro-
sion inhibitor material is accumulated at these sites,
initiated corrosion can be depressed (by the inhibitor).
Plus the surface ennobling and oxygen smearing-out
capabilities as demonstrated in this study, the ICP-
based primer under the protection of a topcoat and
intermediate layer (if any) will provide both preventive
and corrective protections launched in a smart mode.
At this standing point, the PANi-based primer as pro-
posed in this study builds a steady foundation for the
future development of truly smart ICP-based coating
systems for general metallic materials.
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