CARBON 5 0 ( 2 0 1 2 ) 5 0 4 4 –5 0 5 1

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Novel anticorrosion coatings prepared from polyaniline/

graphene composites

Chi-Hao Chang a, Tsao-Cheng Huang a, Chih-Wei Peng a, Tzu-Chun Yeh a, Hsin-I Lu a,

Wei-I Hung a, Chang-Jian Weng a, Ta-I Yang b, Jui-Ming Yeh a,*
a
Department of Chemistry, Chung Yuan Christian University, Chung Li 32023, Taiwan, ROC
b
Department of Chemical Engineering, Chung Yuan Christian University, Chung Li 32023, Taiwan, ROC

A R T I C L E I N F O A B S T R A C T

Article history:
Received 28 February 2012
Accepted 24 June 2012
Available online 29 June 2012
We report on the exceptional application of polyaniline/graphene composites (PAGCs) for
corrosion protection of steel. The composites display outstanding barrier properties against
O2 and H2O compared with neat polyaniline and polyaniline/clay composites (PACCs). The
conductive filler, 4-aminobenzoyl group-functionalized graphene-like sheets (ABF-G) with
a relatively higher aspect ratio than organophilic clay nonconductive fillers, is a versatile
platform for polymer grafting that promotes better dispersion of the graphite within the
polymer matrix and lengthens the diffusion pathway that gases should effectively encoun-
ter. This concept can be used for other polymer/graphene composites.
 2012 Elsevier Ltd. All rights reserved.

1. Introduction protection of metallic substrate as compared with that of a

Corrosion protection plays a prominent role in the modern
metallic finishing industry. Previous surveys have shown that
corrosion is a very costly problem and has a major impact on
the economies of industrial nations. Therefore, many organic
and polymeric coatings have been employed to protect metals
against corrosion. Because electroactive polyaniline (PANI)
coatings were found to have better anticorrosion properties
than other polymers, PANI functionalized anticorrosion coat-
ings have received much attention in the past. The mecha-
nism for enhanced corrosion protection has been attributed
to an increase in the corrosion potential and the redox cata-
lytic capability of PANI in the formation of a passive metal
oxide layer [1–3].
To further enhance the corrosion protection performance
of PANI, Yeh et al. [4] have reported that well-dispersed non-
conductive clay in PANI with an aspect ratio of 200 [5–7]
could increase the length of the diffusion pathways for reac-
tive gases such as oxygen and water vapour in polymer coat-
ings and lead to a significant enhancement of the corrosion
neat polymer coating. Subsequently, the concept, in terms
of polymer/clay composites functioning as anticorrosive coat-
ings, has been applied to prepare a series of polymeric matri-
ces [8–10]. Recently, considerable amount of research work
has been reported on the fabrication of graphene/polymer
composites for various applications such as good mechanical
property [11], electrorheological property [12–14], and barrier
property [15,16]. The research activities associated with con-
ductive graphene with a relatively high aspect ratio of 500
[17] have evoked interest. The lower density and higher aspect
ratio of conductive graphene, as compared with that of non-
conductive clay platelets, initiated their potential application
as advanced gas barrier polymer composite films. For exam-
ple, Nguyen et al. [18] found that polystyrene (PS) film with
a low graphene loading was superior in reducing the relative
O2 permeability of PS compared with those of the best pub-
lished gas barrier results for polymer/clay composites. The
concept of preparing an advanced gas barrier in terms of
PS/graphene composites can also be applied to other polymer
systems.

* Corresponding author: Fax: +886 3 902653399.

E-mail address: juiming@cycu.edu.tw (J.-M. Yeh).
0008-6223/$ - see front matter  2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2012.06.043
 CARBON 5 0 ( 20 1 2 ) 5 0 4 4–50 5 1
Based on previous studies [18–23], polymer/graphene com-
posites could potentially replace polymer/clay composites in
advanced gas (e.g. O2 and H2O) barrier applications. In this
work, novel PANI/graphene composite anticorrosion coatings
are first presented and investigated by series of a electro-
chemical corrosion measurements. PANI/clay composite
coatings (the procedures are given in the Supplementary
Material) were also prepared as a control. To the best of our
knowledge, there has been no report on the application of
polymer/graphene composites as anticorrosive coating mate-
rials to date.
We obtained graphene-like sheets grafted with 4-amin-
obenzoyl groups by Friedel–Crafts acylation (‘direct’ electro-
philic substitution reaction) with 4-aminobenzonic acid
(ABA) in polyphosphoric acid (PPA)/phosphorous pentoxide
(P2O5) as a mild and noncorrosive medium. This procedure
was first developed by Baek et al., [24–27] and has been widely
applied to functionalize carbon-based nanomaterials (e.g. car-
bon nanotubes [28–30], fullerenes [31], and nanodiamond
[32]). The subsequent chemical oxidation polymerization of
the aniline monomers with different amounts of 4-amin-
obenzoyl group-functionalized graphene-like (ABF-G) sheets
was conducted in ammonium persulfate (APS)/1.0 M aqueous
hydrochloric acid to yield PAGCs. The PAGCs were then com-
pletely worked-up and analyzed (Fig. 1, Fig. S1 in the Supple-
mentary Material). We found that the corrosion protection
performance of PAGCs is superior not just to PANI but also
to PACCs with the same filler loading (0.5 wt.%) due to better
barriers for both O2 and H2O(g).
2. Experimental
2.1. Materials
ABA, PPA, P2O5, APS, (4-carboxybutyl)triphenylphosphonium
bromide (intercalating agent), and N-methyl-2-pyrrolidinone
Fig. 1 – Preparation of PANI/graphene composites (PAGCs).
5045
(NMP) were purchased from Aldrich Chemical Inc., and used
as-received without further purification, unless otherwise
specified. Both 1.0 M HCl and 1.0 M NH4OH were prepared by
diluting concentrated ammonia and hydrochloric acid
(Riedel-de Haen) with distilled water for preparing the acidic
and basic aqueous media, respectively. Graphite powders
(CAS No. 7782-42-5, particle size <45 lm, 99.99 + % purity)
were also obtained from Aldrich Chemicals Inc., and aniline
(Sigma–Aldrich) was doubly distilled under a reduced pres-
sure. Montmorillonite clay (PK805), purchased from Pai-Kong
ceramic company, was used and had a cation exchange
capacity (CEC) value of 98 meq/100 g. All reagents were re-
agent level unless otherwise stated.
2.2. Instrumentation
Fourier-transform infrared spectroscopy (FT-IR) was obtained
at a resolution of 4.0 cm1 with an FT/IR spectrometer (FT/IR-
4100) at room temperature over a range of 4000–650 cm1.
Thermogravimetric analysis (TGA) was conducted in air and
nitrogen flows at a heating rate of 10 C/min over a tempera-
ture range of 35–700 C using a DuPont TA Q50. The scanning
electron microscope (SEM) employed in this work is a Hitachi
S-2300, and transmission electron microscopy (TEM) was per-
formed using a JEOL-200FX at an accelerating voltage of
120 kV. The samples were dispersed in NMP, and copper grids
were then prepared by dipping them into the NMP solution
and removing to dry. X-ray photoelectron spectroscopy (XPS)
was performed on a Kratos Axis Ultra DLD. A wide-angle
X-ray diffraction (WXRD) study was performed on a Rigaku
D/MAX-3C OD-2988N X-ray diffractometer with a copper tar-
get (k = 0.15418 nm) at a scanning rate of 4/min. Electrochem-
ical measurements of the corrosion potential (Ecorr),
polarization resistance (Rp), corrosion current density (Icorr),
and corrosion rate (CR) of coated steel electrodes were ob-
tained using a VoltaLab 40 potentiostat/galvanostat with an
5046 CARBON 5 0 ( 2 0 1 2 ) 5 0 4 4 –5 0 5 1
electrochemical corrosion cell consisting of a graphite rod
counter electrode, a saturated calomel electrode reference
electrode, and a working electrode. Gas permeability (O2 per-
meation) experiments were performed using a GTR-31 ana-
lyzer (Yangimoto Co.). Conductivity measurements were
made with a four-point probe connected to a Keithley 2400
voltmeter constant-current source system. All samples were
in the form of compacted disk pellets 1.26 cm in diameter
and approximately 0.6 cm in thickness. The conductivity val-
ues were averaged over 10 measurements.
2.3. Procedure for exfoliation and functionalization of
graphite with ABA in PPA/P2O5
Graphene and graphene-like sheets were obtained by a direct
electrophilic substitution reaction in a PPA/P2O5 medium, and
the graphite powders were exfoliated and functionalized with
ABA in a 500 ml glass flask with a high torque mechanical stir-
rer and nitrogen inlet and outlet. The ABA (0.5 g, 3.6 mmol),
graphite powders (0.5 g), PPA (83% P2O5 assay: 20.0 g), and
P2O5 (5.0 g), were stirred in the flask under dry nitrogen purge
at 130 C for 3 days. At the end of the reaction, water was
added to the flask, and the precipitate was collected by suc-
tion filtration (Soxhlet-extracted with water for three days
and then with methanol for another three days). Finally, the
resultant was freeze-dried for three days, yielding the ABF-G
sheets [24].
2.4. PANI/graphene composite (PAGC) thin film
preparation
Aniline monomers (0.1 mol) were added to 400 ml of 1.0 M HCl
and various amounts of ABF-G (0.1, 0.25, and 0.5 wt.%) were
completely dispersed in the solution under magnetic stirring
with brief ultrasonication to accelerate the dispersion. Upon
addition of APS (0.025 mol) in 20 mL of 1.0 M HCl, the solution
was stirred for six hours in an ice bath. The as-synthesized
HCl-doped PAGC precipitates were then obtained by filtering
and drying under dynamic vacuum at 40 C for two days.
The final PAGCs in base form were obtained by immersing
Fig. 2 – (a) FT-IR spectra of pristine graphite and ABF-G. (b) TGA thermograms of pristine graphite and ABF-G in air at a heating
rate of 10 C/min.
the HCl-doped PAGCs into 400 mL of 1.0 M NH4OH under mag-
netic stirring for 4 h at room temperature, followed by filtra-
tion and drying under vacuum at 40 C for two days. A 0.3 g
sample of the PAGCs in base form was dissolved in 10 mL of
NMP under magnetic stirring at room temperature for one
day. The solution was cast onto a substrate (e.g. a microscope
glass slide), and the solvent was evaporated at 90–100 C in a
flame hood for one day. The sample-coated glass substrate
was then immersed in distilled water to yield free-standing
PAGC films (Fig. S1).
3. Results and discussion
From the FT-IR spectra (Fig. 2a), the pristine graphite powders
are distinguished by their relatively featureless spectrum and
ABF-G exhibits a strong carbonyl (C@O) stretching peak at
1654 cm1, with the primary amines (–NH2) appearing at
1593 cm1 which corresponds to the N–H bend vibration.
These results confirmed that the graphene-like sheets were
covalently linked to the 4-aminobenzoyl groups to success-
fully yield ABF-G [24–27]. To quantitatively estimate the
amount of ABA in ABF-G, the powder samples were subjected
to TGA. While the pristine graphite powders showed no
weight loss up to 600 C in air, ABF-G started to lose weight
at around 600 C, which could be attributed to thermal
decomposition of the ABA moiety. The degree of functionali-
zation from the gradual mass loss of ABF-G suggested that
around 38 wt.% had been edge-functionalized (Fig. 2b). In
nitrogen, pristine graphite was stable to 900 C, while the
ABF-G showed a weight loss of approximately 26 wt.% at
750 C (Fig. S2). The large difference in weight loss between
the air and nitrogen experiments was because a portion of
the aromatic 4-aminobenzoyl moieties were carbonized
under inert conditions and became thermally stable char
[24–27]. Further evidence for functionalization of ABF-G came
from XPS, which revealed a N 1s peak in the spectrum with
little increase of the oxygen content compared with pristine
graphite (Fig. S3 and Table S1). Moreover, the level of exfolia-
tion was investigated through WAXD patterns; the pristine
graphite powders showed a strong peak at 26.54 (d-spacing
 CARBON 5 0 ( 20 1 2 ) 5 0 4 4–50 5 1 5047

Fig. 3 – TEM images of PAGCs05 at (a) low magnification and (b) high magnification.

Fig. 4 – Tafel plots for (a) bare steel, (b) PANI-coated, (c) PAGCs01-coated, (d) PACCs05-coated, (e) PAGCs025-coated, and
(f) PAGCs05-coated electrodes measured in 3.5 wt.% NaCl aqueous solution.

of 3.37 Å), while the peak intensity of ABF-G decreased by listed in Table 1; generally, a higher Ecorr and a lower Icorr,
approximately 70% due to the delamination of the graphite Rp, and CR indicate better corrosion protection.
into a-few-layer graphene sheets and individual graphene The Rp values were calculated from the Tafel plots, accord-
[24–27] (Fig. S4). ing to the Stearn-Geary equation [33,34]:
SEM images obtained from the pristine graphite showed ba bc
that the surface was smooth and clean but was rough and un- Rp ¼ ð1Þ
2:303ðba þ bc ÞIcorr
even after functionalization due to the attachment of the 4-
aminobenzoyl moieties [24–27] (Fig. S5). Besides which, from where, Icorr is determined by the intersection of the linear por-
the TEM images of ABF-G, we could clearly observe exfoliated tions of the anodic and cathode curves, and ba and bc are the
individual graphene and graphene-like sheets that had a high anodic and cathodic slopes (DE/Dlog I), respectively.The CR
degree of crystallinity (Fig. S6). TEM images of the PAGCs with was calculated as [35]:
0.5 wt.% ABF-G loadings (PAGCs05) distinctly revealed that Icorr ðA=cm2 Þ  MðgÞ
CRðmm=yearÞ ¼ ð2Þ
ABF-G is well dispersed in the PANI matrix, which suggested Dðg=cm3 Þ  V
good compatibility between PANI and ABF-G. The shape of
where M is the molecular weight, V is the valence, 3270 is con-
the ABF-G in the PANI is crumpled and wrinkled due to the
stant, and D is the density. The protection efficiency (PEF%)
flexibility (Fig. 3).
was evaluated using [36]
The corrosion protection behavior of bare steel and PAG-
Cs01, PAGCs025, PAGCs05, and PACCs05-coated steel in a cor- R1 1
p ðuncoatedÞ  Rp ðcoatedÞ
PEF % ¼  100% ð3Þ
rosive medium (3.5 wt.% aqueous NaCl electrolyte) under R1
P ðcoatedÞ
potentiodynamic polarization conditions is presented in
The PAGCs exhibited the best anti-corrosion capability as
Fig. 4. The corrosion protection of the sample-coated steel
evidenced by the highest and lowest values of Ecorr and Icorr
can be observed from the values of Ecorr, Rp, Icorr, and CR, as
(which corresponds to a lower corrosion rate), respectively,
5048 CARBON
Table 1 – Electrochemical corrosion measurements and barrier properties of prepared coating materials.
Compound Electrochemical corrosion measurements
code
Ecorr (mV) Rp (kX cm2) Icorr (lA/cm2)
Barea 789 2.48 14.71
PANI 647 14.43 3.70
PAGCs01 601 32.85 1.61
PAGCs025 568 65.40 0.82
PAGCs05 537 135.22 0.38
PACCs05 584 33.11 1.38
a
Polished steel used for test.
compared to the bare steels and PANI coatings. Undoubtedly,
as the ABF-G loading was increased further, the protection
ability was enhanced. The mechanism of the enhanced corro-
sion protection effect of the PAGC coating might be a result of
the well-dispersed ABF-G in the PANI matrix that increases
the tortuosity of the diffusion pathways for oxygen and water
vapour. The corrosion and rust formation on steel involves
several steps and oxidation and reduction equations [37].
Fe ! Fe2þ þ 2e
Fe2þ ! Fe3þ þ 1e
O2 ðgÞ þ 2H2 O þ 4e ! 4OH
2Fe2þ ðaqÞ þ O2 ðgÞ þ 2H2 O ! 2FeOOH þ 2Hþ
It could be seen that there is need for sufficient H2O and O2 for
the formation of rust and dissolution of the steel for causing
corrosion. If any of these processes are prevented, the corro-
sion is inhibited and the coating becomes effective for corro-
sion prevention. Therefore, it is reasonable to believe that
increasing the tortuosity of the diffusion pathways is able to
effectively prevent the H2O and O2 from accessing the sub-
strate surface, leading a good anticorrosion property. More-
over, we also compared the corrosion protection abilities of
PAGCs and PACCs, and the results revealed that PAGCs05
was superior to PACCs05 at the same loading. We assume that
PAGCs have a better corrosion protection ability than PACCs
because PAGCs exhibit a higher gas barrier as we discuss be-
low.A more tortuous path is forced upon the gas molecules
passing through the polymeric matrix by the inclusion of
the ABF-G, retarding the progress of the phenomenon. This
results in a macroscopically observable reduced permeability
that is thought to effectively enhance the corrosion protec-
tion. As we know, the higher the filler matrix interfacial area
and aspect ratio, the more tortuous the path, hence the great-
er reduction in permeability. According to previous reports [5–
7,17–23], the aspect ratio of graphene (500) is higher than
that of clay (220). Moreover, ABF-G disperses well in PANI
and maximizes the interfacial area. Thus, we could assume
that the PAGCs are better gas barriers than PACCs.The oxygen
permeability of the free-standing film was investigated by
using a Yanaco GTR-31 gas permeability analyzer (GPA). The
gas permeability is calculated by the following equation
q=t
P ¼ l=ðp1  p2 Þ 
A and exhibits a high aspect ratio which is advantageous for
5 0 ( 2 0 1 2 ) 5 0 4 4 –5 0 5 1
CR PEF (%) Coating Thickness Barrier properties
(mm/year) (lm)
O2 (Barrier) H2O
(g/m2h)
17.22 · 102 – – – –
4.33 · 102 4.82 30 0.7513 168.44
1.88 · 102 12.63 31 0.3380 67.32
0.96 · 102 25.35 28 0.2254 45.57
0.44 · 102 53.49 29 0.1056 19.98
1.61 · 102 12.43 31 0.3091 61.96
where P is the gas permeability [cm3 (STP) cm/(cm2 s cm Hg)],
q/t is the volumetric flow rate of the gas permeate [cm3 (STP)/
s], l is the membrane thickness [cm], A is the effective mem-
brane area [cm2], and p1 and p2 are the pressures (cm Hg) on
the high- and low-pressure sides of the membrane, respec-
tively. The O2 transmission rate is obtained by gas chromatog-
raphy, from which the O2 permeability is calculated [2,8–
10,33]. In addition, using similar apparatus to our previously
published papers [8], we performed experiments to measure
ð4Þ
the water vapour permeability wherein the feed solution is
ð5Þ not in contact with the membrane. The feed solution was
ð6Þ vaporized first and subsequently permeated through the
membrane with an effective area of 10.2 cm2. The perme-
ð7Þ ation rate was determined by measuring the weight of perme-
ate. The tested free-standing film used for the molecular
barrier measurements was prepared with a film thicknesses
of 45 lm. Compared with the molecular barriers of PANI,
the free-standing PAGC films with low ABF-G loadings (e.g.
0.1 wt.%) showed a reduction of approximately 55 and 60%
of the O2 and H2O permeabilities, respectively, as depicted in
Fig. 5 and listed in Table 1. Furthermore, it is noteworthy that
a further increase of the ABF-G loading resulted in further
enhancement of the barrier property of the PAGCs. Moreover,
in Fig. 5, it is clear that PAGCs05 exhibited a better gas barrier
property than PACCs05 (a reduction of approximately 66 and
68% of the O2 and H2O permeabilities, respectively) that could
be attributed to the higher aspect ratio of the ABF-G [5–7,17–
23]. This results confirmed that PAGCs are more advanced
gas barrier materials and are more suitable anticorrosion coat-
ing materials than PACCs. This also suggests that polymer/
graphene composites are a potential advanced anticorrosion
coating candidate to replace traditional polymer/clay compos-
ites, where the diffusing gas molecule would encounter a
more tortuous path in traversing the polymer/graphene com-
posite coatings. (Fig. 6)
Electrical properties of the doped-specimens, including
PANI, PAGCs, and PACCs, were also measured by the four-
probe method on powder-pressed pellets at room tempera-
ture (Table S2). The average conductivity of PAGCs increased
with increasing ABF-G loading and was better than that of
PANI. For example, the conductivity of PAGCs with a
0.5 wt.% ABF-G loading was 1.40 · 102 S/cm, one order of
magnitude higher than the value for PANI (1.09 · 103 S/cm).
The results suggest that the graphene is a conductive filler
ð8Þ
 CARBON 5 0 ( 20 1 2 ) 5 0 4 4–50 5 1 5049

Fig. 5 – Permeability and vapour permeability rates of PANI, PAGCs (PAGCs01, PAGCs025, PAGCs05), and PACCs05.

Fig. 6 – Schematic representation of O2 and H2O following a tortuous path through a PACCs and PAGCs.

forming conducting networks in a polymer matrix [38–40].
However, we found that the electrical conductivity of the PAC-
Cs (0.7 · 102 S/cm) was slightly lower than PANI because the
clay platelets are nonconductive and its incorporation causes
a decrease in the PANI Mw value, reflecting a decreased elec-
trical conductivity; this phenomenon has also been observed
by Yeh’s group [9,41,42]. Thus, it could be concluded that the
incorporation of ABF-G into PANI more effectively promotes
the corrosion protection performance as well as increasing
the electrical conductivity. The high conductivity enable PAG-
Cs to have a great potential for various electronic and opto-
electronic applications.
4. Conclusion
coatings were shown to effectively protect steel because of
the good O2 and H2O gas barrier. Well-dispersed graphene,
with a relatively high aspect ratio compared with clay, in a
polymer matrix enhances the gas barrier and is responsible
for the highly desirable anticorrosion properties that make
PAGCs much more effective than PACCs. As such, PAGCs have
an excellent potential to be used as corrosion protection coat-
ing materials. Because it is easy to obtain the graphene precur-
sor, graphite, as it is naturally abundant, and the
functionalized graphene can serve as a conductive nanofiller
for other polymers (such as epoxy, polyimide, polyurethane,
etc.), we believe that polymer/graphene composites will
launch a new era of corrosion protection materials in the fu-
ture and completely replace traditional polymer/clay
composites.

In conclusion, we have presented the first demonstration of

polymer/graphene composites that incorporate ABF-G in PANI Acknowledgments
for corrosion protection coatings. The composites were ob-
tained by exfoliating and functionalizing by direct electro- This research was supported by the National Science Council
philic substitution reaction in a PPA/P2O5 medium. The of the Republic of China under Grant Numbers NSC 98-2113-
5050 CARBON 5 0 ( 2 0 1 2 ) 5 0 4 4 –5 0 5 1
M-033-001-MY3 and NSC 100-2811-M-033-012. We thank Prof.
Li Yuan-Yao (Instruments Center at National Chung Cheng
University) for his help with XPS measurements.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.carbon.2012.06.043.
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