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Journal of
Copyright © 2015 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 15, 6533–6540, 2015
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Functionalization of Titanium Alloy Surface by Graphene

Nanoplatelets and Metal Oxides: Corrosion Inhibition
Jayanta Mondal1 , Lauri Aarik1 , Jekaterina Kozlova1 , Ahti Niilisk1 , Hugo Mändar1 ,
Uno Mäeorg2 , Alda Simões3 , and Väino Sammelselg1
2
∗
1
Institute of Physics, University of Tartu, Tartu, 50411, Estonia
2
Institute of Chemistry, University of Tartu, Tartu, 50411, Estonia
3
ICEMS and Instituto Superior Técnico, University of Lisbon, 1049-001 Lisboa, Portugal

Corrosion inhibition of metallic substrates is an important and crucial step for great economical as
well as environmental savings. In this paper, we introduce an extra thin effective corrosion inhibitive
material having layered structure designed for protection and functionalization of Ti Grade 5 alloy
substrates. The coating consists of a first layer made of thin graphene nanoplatelets, on top of
which a multilayer Al2 O3 and TiO2 films is applied by low-temperature atomic layer deposition. The
amorphous structure of the metal oxide films was confirmed by micro-Raman and X-ray diffraction
analysis. Corrosion inhibition ability of the prepared coatings was analyzed by open circuit potential,
potentiodynamic plot and by voltammetric analysis, in aqueous potassium bromide solution. The
open circuit potential of theby
Delivered graphene-metal oxide coated
Publishing Technology to:substrate
Väino showed much passive nature
Sammelselg
IP: 193.40.2.92
than bare substrate or graphene On:
coated or Tue,
only 27 Oct
metal oxide2015 19:48:19
coated substrates. The localized cor-
Copyright: American
rosion potential of the graphene-metal Scientific
oxide coated, Publishers
only metal oxide coated, and bare substrates
were found 5.5, 3.0, and 1.1 V, respectively. In addition, corrosion current density values of the
graphene-metal oxide and only metal oxide coated substrates showed much more passive nature
than the bare and graphene coated substrates. Long immersion test in the salt solution further
clarified the effective corrosion inhibition of the graphene-metal oxide coated substrate. The ana-
lyzed results reflect that the graphene-metal oxide films can be used to prepare better and effective
corrosion inhibition coatings for the Ti Grade 5 alloy to increase their lifetime.
Keywords: Titanium Alloy, Graphene Nanoplatelets, Metal Oxides Laminate, Atomic Layer
Deposition (ALD), Corrosion Inhibition.

1. INTRODUCTION resistive graphene coatings applied on Fe, Cu, and Cu–Ni

Ti Grade 5 alloy, indicated also as Ti alloy or Ti-
6Al-4V, was the first Ti alloy developed for aerospace
applications.1 Under various environments, titanium spon-
taneously forms a passive layer of oxides on its surface,
which plays a decisive role to determine its corrosion
resistance.2 In the alloy, however, several oxides of iron,
aluminum and vanadium are reported to form in the pas-
sive layer, which affect the protective properties of the
passive film.3 Many efforts have been made to improve
the corrosion resistance of this alloy.4–9 Recently, barrier
properties of graphene have been reported in the literature,
which apparently increase the stability of several metals
and alloys. For example, reports are found on oxidation
∗
Author to whom correspondence should be addressed.
alloy surfaces,10
11 corrosion inhibitive graphene coatings
on Fe and Cu surfaces,12–14 and microbial corrosion resis-
tance of metallic substrates covered with graphene layer.15
In spite of these promising reports, it is a great challenge
to develop better, effective and stable corrosion inhibitive
coatings using graphene material. In order to protect the
metal surface, uniform and defect less coating of graphene
is needed. Thin films made of CVD graphene or graphene
nanoplatelets prepared from natural graphite usually pro-
vide incomplete coverage, leaving local defects at which
corrosion or unwanted oxidation processes may easily
develop, while serious doubts remain regarding the capa-
bility of industrial production of coated systems with good
adhesion. In our early studies, we investigated whether
graphene oxide (GO) or reduced graphene oxide (rGO)

J. Nanosci. Nanotechnol. 2015, Vol. 15, No. 9 1533-4880/2015/15/6533/008 doi:10.1166/jnn.2015.10775 6533

Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition Mondal et al.

nanoplatelets can act as corrosion inhibitors and found that was analyzed with Fourier Transform Infrared spectro-
both of them revealed great potential for control of corro- scope (FTIR; BXII, Perkin Elmer) using potassium bro-
sion of metal substrates.16 However, modifications of these mide (KBr) beam splitter and deuterated triglycine sulfate
materials are highly needed to prepare durable coatings. (DTGS) detector. All measurements were carried out by
So far, we have reported graphene oxide-polypyrrole (GO- micro-attenuated total reflectance (-ATR) cell using ZnSe
PPy) composite as a modification of this material.17
18 internal reflection element.
In the present work, we report further modification The surface morphology of Ti/rGO/laminated,
of this material as graphene-metal oxide composite. The Ti/laminated, Ti/rGO coated, and bare Ti alloy substrates
graphene-metal oxide coating was prepared using atomic were studied with high-resolution scanning electron
layer deposition (ALD) technique. The corrosion inhibi- microscope (HR-SEM; Helios NanoLab 600, FEI). The
tion ability of this coating was tested on Ti alloy substratesstructural properties of the coatings were analyzed using
using different electrochemical analysis techniques. The Raman scattering and X-ray diffraction (XRD; SmartLab,
results exhibit that the new coating has excellent corrosion Rigaku using CuK radiation) studies.
inhibition ability. Inspection of the coating was also made by producing
cross sections with Focused Ion Beam Scanning Electron
Microscope (FIB-SEM, Helios NanoLab 600, FEI). The
2. EXPERIMENTAL DETAILS corrosion inhibition ability of the substrates was assessed
Graphene oxide nanoplatelets were prepared from graphite by monitoring the open circuit potential (Eoc  and by
powder (lateral dimensions ≤2 m, thickness 2–6 nm, voltammetry and Tafel plots. All the electrochemical mea-
surface area 750 m2 /g, carbon content >98 wt%; Strem surements were done in 1 M aqueous KBr solution at
Chemicals) by modified Hummer’s method.19–21 The room temperature. The Eoc was measured under contin-
reduction of GO dispersion was carried out using iron uous immersion, for a period of 2 h. Potentiodynamic
powder and 37% hydrochloric acid (HCl) at room tem- polarization was carried out in two ways: one in the poten-
perature (22 ± 2  C). The detail preparation procedure is tial range −250 to +250 mV with scan rate 0.125 mV/s
reported in our early studies.16
22 The Ti Grade 5 alloy to determine passive current (presented as Tafel plots) and
(Sengewald) pieces of 20 mm × 20 mm (substrates) were the another with scan rate of 10 mV/s, for assessment
polished with abrasive paperDelivered
P240 and by
cleaned in an ultra- of the trans-passive potential. Reference 600 Potentio-
Publishing Technology to: Väino Sammelselg
sonic bath using ethanol and isopropanol (Alfa Aesar). In stat/Galvanostat
IP: 193.40.2.92 On: Tue, 27 (Gamry Instruments) was used for all the
Oct 2015 19:48:19
Copyright:
each solvent cleaning process was carried out for American electrochemical
30 min- Scientific measurements. Continuous immersion test
Publishers
utes. The thin rGO coating on the Ti alloy substrate was in 1 M KBr aqueous solution for a period of 40 days was
prepared by spin coating (Spin Coater CSS-05, PI-Kem) also carried through to investigate the coating durability.
at 1000 rpm. The 800 L of ∼0.2 mg/mL concentra-
tion water-ethanol rGO dispersion was used to coat the 3. RESULTS
substrates subsequently. The Al2 O3 and TiO2 films were The Raman spectra of the raw graphite powder, GO and
deposited on the rGO coated substrates by atomic layer rGO nanoplatelets on silicon (1 0 0) surface. The carbon
deposition (ALD) method. Throughout this text, the multi- material shows characteristic G and D bands-Figure 1. The
layer Al2 O3 and TiO2 films will be referred as “lami- G band at 1582 cm−1 arises from first order scattering of
nate.” The ALD deposition performed was as followed: phonon E2 g symmetry at the  point of the first Brillouin
The Al2 O3 and TiO2 films were deposited in a flow-type
low-pressure ALD reactor23 in a stream of pure nitrogen
gas (99,999%, AGA Estonia) at 125  C. The substrates
were coated with 200 cycles of Al2 O3 using precursors
Al(CH3 3 (TMA; 98%, Strem Chemicals) and Millipore
H2 O at the substrate temperature of 125  C with the ALD
sub-cycle periods of 3/2/2/5 s. Then, 200 cycles of TiO2
was deposited using TiCl4 (99.9%, Strem Chemicals) and
H2 O as precursors at the same substrate temperature with
the ALD sub-cycle periods of 2/2/2/5 s. The above growth
procedure was repeated for three times in order to accom-
plish six metal oxide nanofilms.
Both GO and rGO nanoplatelets were deposited onto
silicon substrate and studied with -Raman Spectroscope-
Microscope (in via Raman Microscope, Renishaw), with a
laser beam of 514 nm using 10% of the laser maximum Figure 1. Raman spectrum of graphite, graphene oxide, and reduced
intensity. The extent of reduction of the GO nanoplatelets graphene oxide on Si(1 0 0) surface.

6534 J. Nanosci. Nanotechnol. 15, 6533–6540, 2015

Mondal et al. Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition
zone of graphite and involves in-plane bond stretching of
sp2 carbon pairs,24
25 whereas the D band at 1350 cm−1
arises from breathing mode of K (kappa) point phonons of
A1 g symmetry. The D band appears only in disordered car-
bon materials and its intensity is connected to the presence
of six-fold aromatic rings.24–26 High values for the ratio of
the integrated intensities of the D and G bands (ID /IG  are
usually taken as an indication of disorder in the graphitic
structures. In the present case, the ID /IG ratio values for
graphite and GO were found 0.97 and 0.90, respectively.
The lower ratio value for GO indicates well ordered struc-
ture in the material. After chemical reduction, the ID /IG
ratio was increased to 1.18, suggesting an increase of the
disorder level of the material. A similar increase of the
ratio ID /IG has been reported in the literature.27–32 Alter-
natively, this increase could result from the smaller lateral
scale of graphene flakes, which would increase the con-
centration of defects.27
33 However, it has been suggested
also that GO is an amorphous state and that the graphitic
state can only recover after reduction, which means that
the ID /IG ratio cannot be directly compared between these
two states.25
34 The presence of a large number of hydroxyl
and epoxy groups in the GO structure decrease the rela-
tive number of aromatic rings, diminishing the intensity
of 2D band.28 Such decrease in aromaticity agrees well
with the low electrical conductivity of GO. After chemical
reduction, most of the oxygenated functional groups were
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removed, increasing both the aromaticity and the electrical
IP: 193.40.2.92 On: Tue, a27well-defined
conductivity in the rGO structure. This reduction American
Copyright: process Scientific Publishers
could be limited if the aromatic areas in rGO are small
and thus the relative intensity of D band is in sum increas-
ing, leading to the increase of ID /IG ratio. The S3 band
−1
observed at 2882 cm is the combined reflection of D and
G bands.
The extent of reduction of GO material was analyzed by
FTIR spectroscopy as well. The spectrum of GO-Figure 2-
−1
shows two strong peaks at 3422 and 1117 cm . The first
one was due to stretching vibration of both structural O–H
groups and adsorbed water molecules, whereas the sec-
ond one was due to typical C–O structural vibration. The
Figure 2. FTIR spectrum of graphene oxide (dotted line), and reduced
graphene oxide (solid line).
J. Nanosci. Nanotechnol. 15, 6533–6540, 2015
C–H, O C–H, C O, and C C stretching vibrations
were also found, at 2924, 1706, 1567, and 1382 cm−1 ,
respectively.35–38 After chemical reduction, the high inten-
sity peaks assigned strongly diminished, although some
bands were maintained in the rGO spectrum. The band
corresponding to O–H groups appeared at 3427 cm−1 ,
which was also observed for the KBr matrix, whereas
the band at 1633 cm−1 can be assigned to stretching of
the adsorbed water molecules.39–41 During the reduction
step, the carboxyl groups present in the GO are not eas-
ily reduced.42 These groups could remain untouched dur-
ing reduction process and are most probably localized
at the edges of graphene nanoplatelets. Their presence
should not deleteriously influence the electronic properties
of graphene nanoplatelets. The spectra also contain a com-
ponent from the skeletal vibration of un-oxidized graphitic
domains.39–42
The rGO coated sample was reasonably homogeneous
and had good surface coverage by the rGO nanoplatelets-
Figure 3(a). A few pores seen at the surface are not
expected to extend throughout the coating, as it consists of
several layers of graphene nanoplatelets. When the lami-
nate is applied directly on the substrate, the oxides take
round-shaped features that seem to follow roughly the
morphology of the substrate-Figure 3(b). When applied
onto the GO layer, however, the morphology of the lam-
inate to:
is Väino
quite different—Figure 3(c). The surface has
Sammelselg
Oct 2015 19:48:19
globular structure, with small grains, of
approximately 0.1 m; this structure is typical for amor-
phous metal oxides and the nucleation and growth of metal
oxides on the rGO surface is clearly good as the laminate
covers the surface homogeneously. The cross section of the
Ti/rGO/laminated substrate-Figure 3(d)-shows a thin dark
layer of rGO nanoplatelets covered by a striped structure
that corresponds to the six sublayers of metal oxides lam-
inate, finally covered with Pt protective coating deposited
locally with the FIB (grey granulated sheet). The coat-
ing has a total thickness of ∼200 nm and it is compact
and continuous, thus covering homogeneously the rGO
film. The first Al2 O3 sublayer, deposited directly onto the
rGO surface, covers the graphene layer well, which is
not common for CVD or micromechanically extracted nat-
ural graphene.43 This means that some water molecules
or OH-groups were physisorbed on the surface of rGO
nanoplatelets before the growth and act as active sites
for the adsorption of the aluminum precursor and helping
nucleation as well as growth of the Al2 O3 .44 The adsorp-
tion of small molecules such as H2 O, NH3 , O3 and NO2
on graphene has been reported because of a partial charge
transferring from graphene to N/O atoms.45–48 Moreover,
due to defective structure of the rGO nanoplatelets it can
be also easier to cover with metal oxide films using ALD
technique.
It is known that nucleation of TiO2 directly onto
graphene is difficult, as the basal plane of graphene is
6535
Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition
(a)
(c)
Figure 3. HR-SEM images of surfacesDelivered by Publishing
of (a) rGO, (b) Al2 O3 /TiO2Technology
cross-section of rGO/Al2 O3 /TiO2 laminatedIP:
Ti-5193.40.2.92
substrate.
Copyright: American Scientific Publishers
unreactive.49
50 With this procedure, the growth of TiO2
film becomes easier, as it is applied on the Al2 O3 layer.
The alumina film thus acts as an “adhesion layer,” mak-
ing the growth of TiO2 film easier than on the graphene
surface directly.
The Raman spectra of the rGO with and without lami-
nate (Fig. 4) shows a change in ID /IG ratio as well as a shift
of G band after ALD lamination, which provide informa-
tion about the nature and structure of the metal oxide films
Figure 4. Raman spectrum of rGO/Al2 O3 /TiO2 laminated, and rGO
coated Ti-5 substrates.
6536
Mondal et al.
(b)
(d)
to:rGO/Al
laminated, and (c) Väino Sammelselg
2 O3 /TiO2 laminated Ti-5 substrates; and of (d) FIB-made
On: Tue, 27 Oct 2015 19:48:19
on the graphene surface. The ID /IG peak ratio before and
after lamination was found of 0.95 and 0.97, respectively.
The G peak positions for the above were measured at 1595
and 1592 cm−1 , respectively. These changes indicate that
the oxygen of the Al2 O3 film is not chemically bonded
with rGO nanoplatelets. For chemically bonded oxide, the
ID /IG ratio should have increased and the G band posi-
tion should have downshifted significantly.44
51 Some low
intensity bands at 170, 438, and 613 cm−1 can also be
observed in Figure 4 and reveal an amorphous structure of
the oxide film, as expected for films grown at relatively
low temperature.50
52–54
The X-ray diffraction (XRD) patterns for the both lam-
inated substrates, with and without rGO film-Figure 5-
confirms that the deposited oxides are amorphous. In fact,
the introduction of the rGO layer affected the relative
intensity of the main peaks, but the diffraction peaks mea-
sured are the same and correspond to the spectrum of tita-
nium alloy.
The corrosion inhibition of titanium and its alloys in
chloride medium is recognized as remarkably good. The
naturally formed passive oxide layer on it is quite stable
against moist chloride, ClO−2 , hypochlorous acid, and salts
like NaCl, KCl, NH4 Cl, MgCl2 , BaCl2 , CuCl2 , and FeCl3
neutral solutions.55 However, passive metals and alloys can
be prone to pitting corrosion under aggressive conditions,
J. Nanosci. Nanotechnol. 15, 6533–6540, 2015
Mondal et al. Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition

Figure 7. Tafel plots of the bare, rGO coated, Al2 O3 /TiO2 laminated,
and rGO/Al2 O3 /TiO2 laminated substrates measured in 1 M KBr aqueous
solution.
Figure 5. XRD pattern of the rGO/Al2 O3 /TiO2 laminated (curve 1) and
Al2 O3 /TiO2 laminated (curve 2) Ti-5 substrates, and a model pattern for
pure Ti.
around −200 mV, whereas the sample with the laminate
only had a shift of −400 mV, which indicates that it was
more susceptible to the cathodic polarization, i.e., more
particularly in the presence of some halide salts. Among
reactive.
halide salts, bromides seem to be the most aggressive to
From the potentiadynamic plots, the passive current den-
titanium alloys.56 For that reason, the corrosion inhibition
ability of the prepared coatings was studied in aqueous sity (Ipass  was determined and is presented in Table I. The
potassium bromide solution. rGO film increases the passive current, possibly due to
As a primary investigation the polarization analysis of increased surface conductivity or active area, whereas the
the substrates were carried out for 2 hours in continuous samples with the laminate (both with and without the rGO
immersion. The open circuit potential of the various sys- underneath) had the lowest passive current dissolution. The
tems is plotted in Figure 6. slope of the cathodic branch of the polarization plots is
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same in all Sammelselg
cases, indicating that the reduction reac-
The potential was quite stable IP: in all the samples
193.40.2.92 On:forTue, tion
27 Oct 2015 19:48:19
the duration of the experiment, whichCopyright:
is normal American is probably
for pas- Scientific Publishers the same, which at this pH should be the
sive systems and reveals stable systems, with no signs of reduction of dissolved oxygen. The pitting potential was
pitting corrosion. The OCP of all the systems was in the determined from fast anodic polarization curves shown
region of passivity according to the Pourbaix diagrams. 57 in Figure 8. The pitting potential (Epitt  of the bare and
Still, the laminate caused a shift to more active potentials, rGO-coated substrates were found 1.1 and 0.4 V, respec-
probably due to the presence of the aluminum oxide. The tively. The E pit for the only laminated and rGO/laminated
systems with the rGO layer (both with and without the substrates were found as high as 3.0 and 5.5 V, respec-
laminate) had a shift of ∼100 mV in the anodic direction. tively. Above analysis, suggests that the rGO/laminated
The polarization plots given in Figure 7 were obtained coating exhibits much better inhibition ability than others
starting from a cathodic potential. The corrosion poten- by increasing Eoc and lowering Ipass density. The inhibi-
tials obtained from the curves are all shifted in cathodic tion ability is thus significantly increased upon introduc-
direction compared to the OCP values, due to the changes ing rGO nanoplatelets film between metallic substrate and
induced by the cathodic part of the experiment on the sur- metal oxide layers. The detailed analysis result is given in
face and also in the local pH. The potential shifts were all Table I.
Finally, the surface microstructures of the substrates
were investigated upon long-term immersion test in the
salt solution. The bare substrate was remarkably destroyed
after the test (Fig. 9), whereas the rGO and just lami-
nated substrates were affected by corrosive bromide anions

Table I. Open circuit potential (Eoc , passive current density (Ipass , and
pitting potential (Epit  values.

Sample Eoc (mV, SCE) Ipass (nA/cm2 ) Epit (V, SCE)

Ti bare −40 22 1.1

Ti/rGO 70 140 0.4
Ti/laminate −120 003 3.0
Figure 6. Open circuit potential (Eocp) of the bare and coated sub-
Ti/rGO/laminate 80 01 5.5
strates measured in 1 M KBr aqueous solution.

J. Nanosci. Nanotechnol. 15, 6533–6540, 2015 6537

Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition Mondal et al.

(a)

Figure 8. Voltammetry plots of the bare, rGO coated, Al2 O3 /TiO2 lam-
inated, and rGO/Al2 O3 /TiO2 laminated Ti-5 substrates measured in 1 M
KBr aqueous solution.

(b)
(Figs. 10 (a), (b)). At the same time rGO/laminated sub-
strate remained unaffected—no visible coating delamina-
tion or coating breakdown was noticed (Fig. 10(c)).

4. DISCUSSION
The graphene nanoplatelets was prepared by chemical
reduction of graphene oxide dispersion. Homogeneous and
good surface coverage property of the nanoplatelets was
confirmed by SEM images and FIB-made cross sections.
The adhesion, stability and passivity of the graphene
nanoplatelets were increased by covering with amorphous
Al2 O3 and TiO2 layers usingDelivered by Publishing
atomic layer Technology to: Väino Sammelselg
deposition tech-
IP: 193.40.2.92
nique. The formed amorphous metal oxide films effec- On: Tue, 27 Oct 2015 19:48:19
Copyright: American Scientific Publishers
tively minimized the defects in the graphene coating. The (c)
polarization, Potentiodynamic polarization and Voltamme-
try analyses reflect that the better and effective corro-
sion protective coating can be prepared by graphene-metal
oxide composite coating. The pitting potential for the
graphene-metal oxide coating determined is well above
the oxidation potential for oxygen evolution, which is a
consequence of the dielectric properties of the films. An
excellent correlation was observed between the passive

Figure 10. HR-SEM images of the (a) rGO coated, (b) Al2 O3 /TiO2
laminated, and (c) rGO/Al2 O3 /TiO2 laminated substrates after 40 days
exposure in 1 M KBr aqueous solution.

Figure 9. HR-SEM image of uncoated Ti alloy substrate after 40 days
exposure in 1 M KBr aqueous solution.
current and the pitting potential, i.e., the lower the passive
current, the higher the pitting potential. The reduced GO
does not impart any protection to the Ti substrate, whereas
the best performance is given by the rGO/Al2 O3 /TiO2 coat-
ing. The cathodic branch of the curves has nearly the same
slope in all the systems, but in different current values. In
fact, the cathodic reaction is favored on the rGO compared
to the bare substrate.

6538 J. Nanosci. Nanotechnol. 15, 6533–6540, 2015

Mondal et al. Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition
The long time exposure tests provided only moderate
agreement with the electrochemical measurements. Thus,
the laminated sample (no rGO), which had the lowest
OCP, did not withstand the immersion, as most of the
coating was lost. The rGO resisted surprisingly well, i.e.,
it remained on the surface, although the actual state of
the alloy underneath cannot be observed. The rGO thus
has good adhesion to the substrate but little resistance to
anodic polarization. When metal oxide films applied on
the rGO, the total system clearly exhibited the best per-
formance, both to spontaneous delamination and to anodic
polarization. The effect is probably not connected only
with the barrier property of the graphene, but is also work-
ing as a suppressor of local electrical fields on the surface
of oxidized metal substrate.
From the viewpoint of our experimental data analysis,
we demonstrated that the rGO-metal oxide composite coat-
ing can be used as an effective corrosion inhibitor. There-
fore, this material can be applied to prepare a better and
effective inhibition coating for the titanium alloy substrate.
5. CONCLUSIONS
We have investigated corrosion inhibition ability of the
graphene-metal oxide composite coatings on the Ti Grade
5 alloy substrates. A modified graphene based coating
was produced by atomic layer deposition of multilayer of
Al2 O3 and TiO2 on grapheneDelivered coating. The by Publishing TechnologyI. to:
coating of rGO
IP: 193.40.2.92 On: Tue, 27 Oct
platelets did not improve the corrosionCopyright: the sys- Scientific Publishers S. Krishnamurthy, R. Goodhue, J. Hutchison,
stability of American
tem by itself, but it worked as a primer for the application
and adhesion of the atomic layer deposited oxide layers.
The system with the rGO/Al2 O3 /TiO2 coating revealed not
only lower passive current under applied potential but also
a significantly higher pitting potential and good stability
during long exposure in KBr aqueous salt solution making
it a promising system for the corrosion protection of the
metal alloy substrates.
Acknowledgments: The first three authors are thank-
ful for European Social Funds of Doctoral Studies and
Internationalization Program DoRa for financial support-
ing. This work is also supported by Estonian Ministry of
Education and Science by projects TK117, IUT2-24 and
12164T.
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Received: 16 October 2014. Accepted: 17 December 2014.

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IP: 193.40.2.92 On: Tue, 27 Oct 2015 19:48:19
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6540 J. Nanosci. Nanotechnol. 15, 6533–6540, 2015