Electronic Supplementary Material (ESI) for Nanoscale.

This journal is © The Royal Society of Chemistry 2015

Supporting Information
Efficient Anti-corrosive Coating of Cold-rolled Steel in Seawater Environment using
Oil-based Graphene oxide Ink
Y. N. Singhbabua,b, B. Sivakumara,b, J. K. Singhb, H. Baparib, A. K. Pramanickb and Ranjan K

Sahu*,a,b

G (a)
Intensity (a.u.)

2D

1000 1500 2000 2500 3000

Raman Shift (cm-1)

Shoulder 2D (b)
Intensity (a.u.)

2500 2550 2600 2650 2700 2750 2800 2850 2900

Raman Shift (cm-1)

Fig. S1 (a) The Raman data of commercial graphite powder (Alfa Aesar). (b) The 2D peak is
separately plotted to show the shoulder of the peak.
 2D
(b)
D G
Intensity (a.u)

(a) D 2D
G

500 1000 1500 2000 2500 3000 3500

Raman shift (cm-1)

Fig. S2 Raman spectra of the prepared under the optimized heating temperature and time; (a)
graphene oxide and (b) Ni added graphene oxide from the AA plant.
 C1s
Intensity (a.u.)

O1s
K1s
Ca1s

550 500 450 400 350 300

B.E. (eV)
Fig. S3 The XPS spectrum of the obtained graphene oxide by heating the AA plant at 1000 C.
The spectrum shows the Ca1s, K1s and strong O1s peak.
 Intensity(a.u.) C1s C=C

-OH
C=O


294 292 290 288 286 284 282 280 278 276

B.E.(eV)

Fig. S4 Shows the deconvoluted C1s XPS spectrum of the obtained graphene oxide by heating
the AA plant at 1600 C for 1 h.
 1500
Potential (mV) vs SCE

1000

500
f
e d c b a
0

-500

-1000
10-6 10-5 10-410-3 10-2 10-1 100 101 102 103 104 105 106
Current (A/cm2)

Fig. S5 Shows the potentiodynamic polarization curves of ink coated CR steel as a function of
loading.(a) bare,(b) oil, (c) 0.5 g, (d) 1 g, (e) 1.5 g and (f) 2 g graphene oxide.
 (a) (b)

(c) (d)

(e) (f)

Fig. S6 Depicts the optical image of the CR steel substrates before and after polarization test; (a,
b) bare, (c, d) oil coated and (e, f) ink coated. The images show that there is almost no
dissolution of CR steel in the case of ink coating, whereas the mild dissolution is observed in the
case of oil coated CR steel and severe dissolution in the case of the bare CR steel (black spots of
the polarized substrate are damaged area).

.
 (a) (b)

(c) (d)

Fig. S7 Represents the optical image of ink coated CR steel; (a) before and (b) after the adhesion
test. We have also measured the adhesion test of the oil coated CR steel for comparison; (c)
before and (d) after the test. The images clearly show that there is no peeling of the coating
indicating the coating has good adherence to the surface of CR steel. The digital photographs of
the respective substrate after adhesion test are shown in the inset to (b) & (d). The experiment
was carried out as per the ASTM D-3359.
 B A
O1s
Intensity (a. u.)

540 538 536 534 532 530 528 526

B.E.(eV)

Fig. S8 Shows the O1s XPS spectrum of the polarized (line) and unpolarized (symbol) bare CR
steel substrate. The broad peak contains the peaks pertaining to the lattice oxygen (A) and
hydroxyl groups (B). The data of polarized substrate show that the intensity of B peak is more
intense than the A peak, indicating the generated OH- ions during the electrochemical test are
attached on its surface.
 C1s

O1s
Intensity (a.u.)

No Fe 2p peak

(a)
N1s
(b)

800 700 600 500 400 300 200

B.E.(eV)

Fig. S9 XPS spectrum of the oil (a) and ink coated (b) CR steel. The spectrum does not show the
signature of Fe2p peak, indicating the underneath steel surface is covered fully by the coating
material.
 C-C / C=C
C1s (a) O1s (b)

Intensity (a.u)
Intensity (a.u)

OH
-COO

Kβ Kβ

300 295 290 285 280 275 270 265 545 540 535 530 525 520
B.E. (eV) B.E. (eV)
C-C / C=C (c) (d)
C1s O1s
Intensity (a.u)
Intensity (a.u)

OH
-COO

Kβ Kβ

300 295 290 285 280 275 270 265 545 540 535 530 525 520
B.E. (eV) B.E.(eV)

Fig. S10 Shows the XPS spectrum of the oil coated (a & b) and ink coated (c & d) CR steel
before (symbol) and after (line) polarization test. The C1s spectrum shows the presence of COO
and phenolic OH functional groups. It is noted that the position of the C1s peak is unaltered in
both the oil and ink coated CR steel. Whereas, the shifting in the position of the O1s peak
towards lower binding energy is observed in the case of oil coated CR steel and a very marginal
change in the position is seen in ink coated CR steel after polarization. This shifting is due to the
formed Fe2O3 and the oxygen functional groups of the oil coating. As in ink coated CR steel,
there is almost no Fe2O3 and therefore, no shifting occurs in the O1s spectrum.
 (a) (b) (c)

31.94o 50.61o 55.11o

Fig. S11 Depicts the digital image of the water drop on the CR steel substrates in the contact
angle measurement test; (a) bare, (b) oil coated and (c) ink coated.