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Article
Layer Control of Tubular Graphene for Corrosion Inhibition of Nickel Wires
An T. Nguyen, Wei-Cheng Lai, Bao Dong To, Duc Dung Nguyen, Ya-
Ping Hsieh, Mario Hofmann, Hung-Chih Kan, and Chia Chen Hsu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 09 Jun 2017
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Page 1 of 9 ACS Applied Materials & Interfaces

1
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3
Layer Control of Tubular Graphene for Corrosion Inhibition of Nickel
4 Wires
5
6 An T. Nguyenꜝ, Wei-Cheng Laiꜝ, Bao Dong Toꜝ, Duc Dung Nguyenꜝꜝ, Ya-Ping Hsiehꜜ, Mario
7
8
Hofmannꜛ, Hung-Chih Kanꜝ, Chia-Chen Hsuꜝ´ ⃰
9 ꜝDepartment of Physics, National Chung Cheng University, Ming-Hsiung, Chia-Yi, Taiwan 62102,
10
11 ꜝꜝDepartment of Materials Science and Engineering, National Tsing-Hua University, Hsinchu, Taiwan 30010,
12 ꜜGraduate Institute of Opto-Mechatronics, National Chung Cheng University, Ming-Hsiung, Chia-Yi, Taiwan 62102,
13 ꜛ Department of Physics, National Taiwan University, Taipei, Taiwan 10617
14
15 Keywords: nickel wire, graphene tube, graphene layer, anti-corrosion, thermal annealing
16
17 ABSTRACT: Corrosion protection of complex surface is an active area of research due to its importance to commercial
18 applications such as electrochemical fabrication. However, conventional coatings exhibit limited conductivity, thermal
19 stability, and durability and are thus not suitable. Recent work has shown the potential of graphene, a two-dimensional
20 carbon allotrope, for corrosion protection. The studies, however, limited themselves to simple planar geometries that
21 provide limited insight in the applicability to relevant morphologies, such as mesh electrodes and roughened surfaces. We
22 here study the corrosion protection ability of tubular graphene (TG) on Ni-wires as a model system for such complex ge-
23 ometries. TG-covered Ni wires of approximately 50 µm diameters were produced by the annealing of cellulose acetate
24 (CA) on Ni. The high quality of the TG coating was confirmed by Raman spectroscopy, scanning electron microscopy, and
25 electrical measurements. We show that the graphene layer number could be controlled by adjusting the CA membrane
26 quantity. We found a direct relation between the degree of corrosion inhibition with the variation of graphene layer
27 number. The increase of graphene layers on a Ni surface could enhance its corrosion inhibition in acidic, basic, and ma-
28 rine environments which shows the potential of our approach for future applications.
29
30
31
32 Introduction these studies limited themselves to planar structures that
33 Due to the limited resistance of metals under harsh envi- are not directly applicable to many important conditions.
34 ronments, metallic corrosion, which annually costs For example, wire-mesh structures are commonly em-
35 US$300 billion in the United States, 1 is a serious concern ployed to provide large surface-area electrodes and filter-
36 for many fields such as marine industry, pipelines, auto- ing membranes. However, it is unclear if the contact
37 motive transportation, construction industries, etc. Cor- points between neighboring wires will be reliably covered
38 rosion reaction is inevitable and more intense for any by graphene or act as weak spots in the corrosion barrier.
39 exposed metal parts. To protect various metals from cor- Ni wires exhibit superior properties such as high corro-
40 rosion, their surfaces are usually coated with paints or sion resistance, improved lubrication and hardness, which
41 galvanized layers, or decorated with oxide layers, 2 organ- can be suitably used in electronic components, transport
42 ic layers, 3 and polymers. 4 However, thermal and electri- and storage, temperature sensors, electrical resistance,
43 cal conductivities of metal are unfortunately decreased thermometers, etc. However, the enhancement of corro-
44 after the coating; the physical properties, such as appear- sion protection is necessary to extend the lifetime of Ni. 15-
45 ance, and optical property, are changed due to the thick- 17
Previous studies on the use of graphene, as a protecting
46 ness of the coating. To overcome these drawbacks, re- layer of Cu or Ni foils from the harsh environment, were
47 cently, graphene is applied as corrosive protecting layers mainly focused on material synthesized by chemical va-
48 on various metal substrates through the incorporation por deposition (CVD). 18,19 The CVD, a popular graphene
49 with paints 5-8 or wet-transferred graphene films on Cu fabrication process, usually takes several hours in a tube
50 and Ni foils. 9,10 Because of its remarkably chemical inert- furnace at around 1000 °C that may restrict the anticorro-
51 ness, ultrathin nanostructures, and stability up to 400 ºC sive application potential of graphene. We herein present
52 in an ambient atmosphere, graphene demonstrates excel- a simple process to fabricate tubular graphene (TG)-
53 lent performance for anticorrosion and antioxidation in covered interwoven Ni wires at the macroscopic scale
54 marine or saline environment. 11-14 Indeed, graphene coat- based on rapid thermal annealing of cellulose acetate (CA,
55 ed metal foils exhibit a corrosion rate that is several times C045A047A, Advantec) on Ni at a low vacuum condition.
56 slower compared with their corresponding bare counter- Compared with other typical methods, this approach is
57 parts. The graphene surface acts as an ultrathin imperme- safer because it can avoid the hazards of using explosive
58 able barrier, thus physically preventing direct interaction gaseous materials or toxic chemicals. Furthermore, it has
59 between the protected metal and reactants. However, advantages like less power consumption, and shorter pro-
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cessing time. Ni exhibits a melting point of 1455°C, which in this study as an appropriate solution for investigating
1 is much higher than the temperature of graphene growth the corrosion resistance of TG-covered nickel instead of
2 (950°C). Therefore, the macroscopic Ni wires used in our Na2SO4, or O2 as previously reported. 18,22,23 Nevertheless,
3 study can absolutely endure the high annealing tempera- we also determined the corrosion behavior of all the sam-
4 ture of graphene fabrication. ples in 3.5% NaCl, and 0.5M KOH solutions for further
5 understanding the role as a protective barrier of TG.
In this work, we first demonstrated the number of TG
6
layers could be controlled by adjusting the CA quantity. Electrochemical measurements of the TG-covered Ni
7 Then we investigated the degree of corrosion inhibition meshes were conducted in a three-electrode cell, contain-
8 with the variation of graphene layer number. We found ing a working electrode, a Pt-mesh counter electrode, and
9 that the increase of graphene layers on a Ni wire surface an Ag/AgCl/KCl reference electrode. The corrosion re-
10 could enhance its corrosion inhibition by serving as an sistances of the TGs were analyzed in acidic (0.05M, 0.1M,
11 ultrathin impermeable barrier, and making more tortuous and 0.5M HCl), basic (0.5M KOH) and salty (3.5% NaCl)
12 pathway of permeating solution. environments. The Tafel plots, the logarithm of the cur-
13 rent density (log i) vs. the electrode potential, were rec-
14 Experimental
orded by a Jiehan 5600 electrochemical workstation with
15 Fabrication of TG-covered Ni wires
a scan rate of 20 mV/s. The scan was repeated 3 times to
16 The TG-covered Ni wires (GNi) were fabricated by a check the reproducibility. All three polarization curves of
17 thermal annealing technique as reported in our previous each sample in 0.5M HCl solution were shown in Fig S1
18 works. 20,21 Ni was used as a transition metal catalyst for for reference. The second and third scans of each elec-
19 the surface precipitation of carbon atoms. First, a piece of trode were almost overlapped, indicating the repeatability
20 commercial interwoven Ni wires was cleaned by acetone of the measurement. Therefore, the third polarization
21 and rolling-pressed with different amounts of CA mem- curves of the four electrodes in different environments
22 brane (a solid carbon precursor). Note that the layers of were chosen for further study. Besides, the corrosion rela-
23 TGs were controlled by adjusting the CA membrane tive parameters, such as corrosion current density (icorr),
24 quantity (CA to Ni mesh area ratios (CA/Ni area ratio) of corrosion rate (CR), and corrosion potential (Ecorr) of dif-
25 1:16, 1:50, and 1:400); the GNi samples are subsequently ferent samples were obtained on the basis of the Tafel
26 denoted by GNi–1/16, GNi–1/50, and GNi–1/400, respec- plots and corrosion theory. 10,24,25 Icorr was determined in-
27 tively. Subsequently, the sample was annealed to 950ºC at directly from the intersection point of the asymptotic
28 a heating rate of 15.0°C/s in an infrared lamp annealing lines of both anodic and cathodic curves. The anodic oxi-
29 system; this temperature was maintained for 8 min at a dation and cathodic reduction reactions are as follows:
30 pressure of 0.6–0.8 × 10-3Torr. The sample was then
31 cooled to 500 °C at a cooling rate of 5.6°C/s, and from 500 Ni → Ni + 2e
(1)
32 °C to room temperature at a cooling rate of 0.48°C/s for
33 yielding the TG-covered Ni wires. O + 2H O + 4e
→ 4OH
(2)
34 The chamber size of our annealing system is 2×2 cm . 2

35 The CR was calculated through the corrosion current

Consequently, that is the largest size of TG mesh that we density using the following formula [10]:
36 can fabricate. However, it is possible to fabricate larger
37  ×  × 
graphene films if bigger furnace is employed. CR = (3)
38  × 
Characterizations
39
40 A scanning electron microscope (SEM, Hitachi, S-3000H) where K is a corrosion rate constant (3272 mm per A per
41 was used to examine the morphologies and dimensions of cm per year), EW is the equivalent weight (29 g for Ni), ρ
42 the TG meshes; while a Raman spectroscope (Horiba, is the density (8.9 g/cm3 for Ni), and A is the sample area
43 XploRA ONE), and an atomic force microscope (AFM, (1×2 cm2).
44 XE70) were used to investigate the crystallographic and Results and Discussion
45 layered structures of the TGs. An ultrahigh resolution
The thickness and quality of graphene synthesized on
46 analytical electron microscope operated at 200 kV
interwoven meshes were characterized after removal of
47 (HRAEM, JEOL-2100F) was used to determine the number
the Ni (the details on the removal process can refer to
48 of graphene layers. The sheet resistance of the samples
[20,21]). The morphology of the TG grown on the Ni mesh
49 was measured using a four-point probe instrument at
at 950 °C, with a 1:50 area ratio of CA membrane to Ni
50 room temperature. The energy-dispersive X-ray (EDX) of
mesh, was examined using the FESEM at different magni-
51 the FESEM (JSM-6500F) was used to analyze elemental
fications, as displayed in Fig. 1a–c. The TGs maintained
52 composition of the woven TGs. The X-ray photoelectron
the woven structure of the Ni template, and fully covered
53 spectroscopy (XPS) was used to analyze the surface chem-
the Ni wires without containing any void. The graphene
54 ical properties of the TG.
tubes had diameters of approximately 50µm, and were
55 Electrochemical measurement constructed of continuous micron-sized graphene do-
56 Ni is inert in neutral and alkaline environments because mains, which can be clearly observed on the surface of
57 of the passivation of the Ni surface through an outgrow- both TG and GNi (see Fig. 1a, S2a). Small wires remained
58 ing NiO layer 15. This passive film is dissolved when im- in the core of every graphene tube were caused by carbon
59 mersed in acidic environment. Therefore, HCl was chosen impurities formed during the annealing process. 21 The
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EDX analysis revealed the complete removal of the Ni

1 core after the etching process; the compositions of the TG
2 mesh were carbon (89.3wt.%) and oxygen (10.7wt.%).
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16 Fig. 1. (a−c) SEM images at different magnifications of the Fig. 2. (a) Typical Raman spectra obtained from the surface
o
17 TG sample annealed at 950 C with CA/Ni area ratio of 1:50, of the three TG samples; Raman maps of I2D/IG ratio of the
18 (d) the sheet resistance dependence of TGs on the initial CA three samples annealed with different CA/Ni area ratios of (b)
19 quantity; the insets show the optical images of the TG–1/50 1:16, (c) 1:50, and (d) 1:400.
20 and TG–1/16 meshes, (e) C 1s scan and the deconvolution of
2 3
the TG-1/50 show sp , sp bonding and oxygen-attached car- Fig. 2a shows the typical Raman spectra of the TG meshes
21 annealed at 950 oC with different CA/Ni area ratios. In
bon functional groups.
22 addition, Fig. S4 displays Raman spectra of these meshes
23 We also carried out EDX analysis on the GNi and found randomly obtained from 15 points on the surface of each
24 its oxygen concentration is quite low (0.16 wt.%) (see Fig. sample. All three samples exhibited extremely weak D
25 S2c). The abundant oxygen (10.7 wt.%) found in the TG peaks at〜1335 cm-1 indicating negligible defects on the
26 sample is due to the wet etching process of Ni wires. Since TGs surfaces.
27 we only used GNi samples for electrochemical measure-
28 ments, the low concentration of oxygen should have mi- Moreover, two characteristics peaks of graphene (G peak
at〜1584 cm-1 and 2D peak at〜2671 cm-1) were clearly ob-
29 nor effect on the anti-corrosion property of the TG. Note
30 that the CA membrane quantity was adjusted to vary the served. The intensity ratio of 2D peak to G peak (I2D/IG)
31 layer numbers of TGs. Specifically, the CA/Ni area ratio decreased with increase of CA/Ni area ratio. The same
32 was chosen to be 1:16, 1:50, and 1:400, and the three sam- trend was also observed in the Raman spectral mapping
33 ples were denoted by TG–1/16, TG–1/50, and TG–1/400, of I2D/IG intensity ratio taken from three samples in a
34 respectively. The electron transparency of the TG struc- 50x50 µm2 region as displayed in Fig. 2b-d. It implies
35 tures shown in Fig. 1c and S3 indicates that the walls of more graphene layers were formed in the TGs if larger
36 the graphene tubes are thin. The optical images of the quantity of CA was used. 28,29
37 TG–1/50, and TG–1/16 meshes (see the insets of Fig. 1d) To determine the wall thicknesses of TGs, AFM technique
38 demonstrated free-standing, and great flexibility of the was employed. An unzipped TG was firstly obtained by O2
39 TGs. The TG–1/16, which more CA membrane was used, is plasma technique (illustrated in Fig. S5a) because of the
40 darker than the TG–1/50, representing that more gra- nature of hollow tubular structure. The upper half TG was
41 phene layers are formed under these conditions. oxidized and removed away while the bottom half gra-
42 Another evidence to support this inference is the sheet phene was kept unchanged. The unzipped TG was formed
43 resistance measurement results of three TG meshes and laid on a silica substrate after the Ni etching process.
44 shown in Fig. 1d. The sheet resistance of the TG mesh Fig. 3a-c show the AFM results measured at one position
45 slightly decreased with the increase of CA/Ni area ratio. of three unzipped TGs; the wall thicknesses were deter-
46 Since the sheet resistance is inversely proportional to the mined to be 1.8 nm, 1.3nm and 1.0 nm for TG-1/16, TG-1/50
47 thickness of graphene layers, the result indicates thicker and TG-1/400, respectively. To systematically investigate
48 graphene layers was formed under higher CA/Ni area ra- the effect of the CA/Ni area ratio on the layer thickness of
49 tio. 26 The C 1s XPS spectrum of graphene tubes (TG-1/50) the TG, wall thicknesses at 10 random positions of each
50 displayed in Fig. 1e can be deconvoluted into four compo- TG sample were measured by AFM and their results are
51 nents corresponding to the following chemical states: the plotted in Fig. S5b-d. Fig. 3d plots the average and stand-
52 components at 284.5 eV, and 285.4 eV are respectively ard deviation of wall thickness of each TG sample versus
53 assigned to the carbon sp2, and sp3; the components at the CA/Ni area ratio determined from Fig. S5b-d. As ex-
54 286.0 eV, and 288.7 eV correspond to the O–C–O, and O– pected, the average thickness of the TG increased when
55 C=O functional groups, respectively. The TG exhibited a more CA was used for the growth of the TG.
56 high sp2/sp3 ratio of 6, further presenting good structural
57 quality of graphene lattices. 27
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23 Fig. 3. AFM measurements of the unzipped TG samples fabricated with CA/Ni area ratio of (a) 1:16, (b) 1:50, (c) 1:400. The corre-
24 sponding insets at the bottom of each image show the thickness difference of two selected points (graphene edge thickness); (d)
25 the TG wall thickness of the TG samples fabricated with different CA amounts; HRAEM images with magnified parts in the in-
26 sets taken on the wall-edges of the TGs fabricated with CA/Ni area ratio of (e) 1:16, (f), 1:50 and (g) 1:400 .
27
the TGs in this study. Fig. 4a−c show the Tafel polariza-
28
tion curves of the graphene-coated Ni wire samples
29
measured in different HCl concentrations (0.05M, 0.1M,
30
and 0.5M). Bare Ni mesh was used for comparison. Note
31
that the number of graphene layers was controlled by
32
adjusting the amount of CA as aforementioned. The Tafel
33
plots of the GNi samples exhibited a clear decrease in
34
both anodic and cathodic reaction rates, especially for the
35
strongest acid solution (0.5M), suggesting that the gra-
36
phene layer has the capability to inhibit corrosion caused
37
by chloride ions by slowing down the ionic diffusion and
38
reaction with the Ni surface. The CR values of all the
39
samples (see Fig. 4d) in different concentrations of acid
40
solutions were calculated by using formula (3). All the
41
samples exhibited low CR in the lowest concentration of
42 0.05 M. Nevertheless, the GNi samples still had lower CR
43 compared with that of the bare Ni; e.g. it is 4.55 × 10-12 m/s
44 Fig. 4. (a), (b), (c) The potentiodynamic polarization curves
for the GNi-1/400 sample, about 0.38 times of the bare Ni
45 of the bare Ni and GNi samples in 0.05M HCl, 0.1M HCl, and
(11.97 × 10-12 m/s). While the CR values of the GNi–1/50,
46 0.5M HCl, respectively; (d) the corresponding corrosion rates
of the Ni and GNi extracted from the Tafel plots.
and GNi–1/16 samples were slightly lower than that of the
47 GNi-1/400. The increase of graphene layers can indeed
48 Furthermore, HRAEM taken on the wall-edge areas allows promote the corrosion protection property of TGs as evi-
49 directly determination of the graphene layer number as denced by the lower values of CR. The corrosion behav-
50 displayed in Fig. 3e-g. The TG wall of the TG-1/16 consist- iors in the 0.1 M and 0.5 M HCl solutions followed a simi-
51 ed of 8 graphene layers, while they were 5 layers, and 3-4 lar trend like in the 0.05M HCl, except CR values of sam-
52 layers for the TG-1/50, and TG-1/400 samples, respectively. ples increased with the increase of the acidic concentra-
53 The results provided strong evidence of graphene layered tion. In the highest concentration (0.5M), the GNi-1/16
54 structure, and the finding is consistent with those of Ra- sample indeed exhibited the strongest anticorrosion per-
55 man spectra, AFM and sheet resistance results. formance compared with the other three samples. Note
56 that the bare Ni sample was corroded very quickly, about
Anti-corrosion capability
57 4.9 times faster than that of the GNi–1/16.
58 Chloride ions, which exhibit a very strong corrosion capa-
59 bility, were used to study the anti-corrosion properties of
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Table 1. Polarization parameters of the bare Ni, GNi-1/400, GNi-1/50, GNi-1/16 in the different environments at
1 300K
2
3 Sample Ni GNi-1/400 GNi-1/50 GNi-1/16
4
5 CR (m/s) CR (m/s) PE (%) CR (m/s) PE (%) CR (m/s) PE (%)
6 -11 -12 -12 -12
HCl 0.05M 1.2×10 4.55×10 62.0 3.15×10 73.7 2.87×10 76
7
8 HCl 0.1M 1.22×10-11 8.1×10-12 33.9 3.7×10-12 69.8 2.74×10-12 77.6
9 HCl 0.5M -11 -12
62.0 -12
73.7 -12
79.6
3.01×10 11.4×10 7.9×10 6.14×10
10
-12 -13 -13 -13
11 NaCl 3.5% 1.0×10 4.15×10 58.3 3.0×10 69.8 2.68×10 73.1
12 KOH 0.5M 2.08×10 -13
1.25×10 -13
39.7 8.1×10 -14
61.1 6.4×10 -14
69.1
13
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32
33
34
35
Fig. 5. (a), (b) Potentiodynamic polarization curves of the graphene/Ni and bare Ni samples in 3.5% NaCl and 0.5M KOH , re-
36
spectively; (c) the corresponding corrosion rates of the samples extracted from the Tafel plots, (d) the corrosion current densi-
37 ties vs. the number of graphene layers in the different environments; (e), (f) the Nyquist, and Bode plots, together with their
38 corresponding fitting curves (solid lines), obtained in 0.1M HCl electrolyte for the Ni (black), and GNi-1/16 (red) samples, respec-
39 tively.
40
41 We also measured the Tafel polarization curves of the all the samples were two-order magnitude lower than
42 GNi samples in 3.5% NaCl solution to investigate the cor- those of obtained in HCl solutions because of the inert-
43 rosion inhibition property of the TG coating in a marine ness of Ni in the basic environment. A passive film
44 environment. As expected, the icorr values of all the sam- formed on Ni surface in alkaline environments prevented
45 ples followed a similar trend (the GNi samples exhibited Ni from further corrosion. However, this passive film will
46 lower icorr compared with that of the bare Ni), but were be dissolved when it is immersed in acidic environment,
47 much lower than those in the HCl solution (see Fig. 5a, d). resulting in the high CR values of Ni in the HCl solutions.
48 This is reasonable because of the strong oxidation of Ni in In the KOH solution, the increase of graphene layers still
49 acidic environment. slightly increased the anti-corrosion capability as evi-
50 Furthermore, as indicated in Fig. 5c, the CR values of the denced by the lower values of corrosion rate and corro-
51 GNi meshes decreased with the increase of thickness of sion current.
52 the TGs and they were lower than that of the bare Ni The corrosion potentials (Ecorr), typically referred to the
53 mesh, suggesting the TG coating indeed improved anti- pitting point, of the GNi–1/400, GNi–1/50, and GNi–1/16
54 corrosion capability of the Ni mesh. We also investigated samples shifted toward more negative values, whereas the
55 the anticorrosion property of the TG coating in 0.5M corresponding icorr values were few times decrease, com-
56 KOH solution (see Fig. 5b-d). Note that the CR values of pared with those of the bare Ni. This indicates the gra-
57
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phene is primarily playing a role as an inhibitor of the TGs makes them serve as excellent barriers against the
1 cathodic reactions, i.e. O + 2H O + 4e
→ 4OH
. 30,31 diffusion of ions such as H+, OH—, and Cl—. Besides, more
2 graphene layers can lead to more tortuous pathway of
The corrosion protection efficiency (PE) of each GNi
3 permeating water.
sample was determined by using the formula (4) and the
4
result was used to evaluate the effectiveness of the corro- The electrochemical impedance spectroscopy (EIS)
5
sion inhibition of each sample, EIS, measured by a CHI660E electrochemical workstation,
6
7 
 was used to evaluate the anticorrosion mechanism of TG.
PE % = 
× 100% (4) Under EIS examination, a small sinusoidal perturbation
8
9 was applied to the sample, and the impedance modulus
10 where i0corr is the corrosion current density of bare Ni, and |Z| was recorded as a function of frequency ω, which al-
11 iccorr is the corrosion current density of the GNi mesh. lows further analysis of the anticorrosion behavior of the
12 Table 1 summarizes CR and PE values of all the samples TG layers; the Bode (or Nyquist) plot generally offers the
13 studied in this work obtained under HCl (with different information on the corroding surface, since the electro-
14 solution concentrations), KOH and NaCl solutions. As chemical impedance includes a complex number with a
15 revealed in Table 1, the PE values increased with increase real component (Zreal) and an imaginary component
16 of thickness of the TGs in aforementioned solutions. The (Zimaginary).
17 highest PE values obtained were approximately 76–80% The Nyquist and Bode plots obtained in 0.1M HCl electro-
18 from the GNi–1/16 sample in HCl, which are comparable lyte for the Ni, and GNi-1/16 samples are shown in Fig. 5e,
to that of the graphene-covered steel as reported. 11 and 5f, respectively. The larger impedance modulus of
19
20 To investigate the stability of graphene coating, SEM im- the GNi-1/16 in the Bode plot indicates the increase of Ni
21 ages of the Ni, and GNi-1/50 before and after the corro- corrosion resistance by graphene coating, and are con-
22 sion test in HCl solution were obtained and are displayed sistent with the behavior of a graphene-protected metal
23 in Fig. S6a, and b, respectively. The morphology of the with minor defects in the protective coating. 10,11 The
24 bare Ni was clearly corroded and became rough after the Nyquist plot of the two samples consisted of two different
25 corrosion test, while the morphology of the GNi-1/50 re- regions: a semicircle which is attributed to the total
26 mained unchanged. Furthermore, Raman spectra ran- charge transfer capacity between Ni and its oxide films,
27 domly obtained at 5 points on the sample surface are and a linear region which is related to the resistance
28 shown in Fig. S6c,which were comparable to those of the against the diffusion of corrosive species. By fitting the
29 freshly prepared counterpart (see Fig. S4b), indicating the data to an equivalent circuit model (illustrated in the in-
30 absence of damage to the graphene after corrosion meas- set of Fig. 5f), 18,31 the corrosion behavior of bare Ni and
31 urements. graphene-covered Ni samples can be quantitatively calcu-
32 Moreover, the GNi-1/50 was immersed in 3.5% NaCl solu- lated.
33 tion for 8 months to investigate long-term stability of the Table 2: Equivalent circuit parameters of the Ni, and GNi-
34 graphene coating. As shown in the Fig S7a, b, the mor- 1/16 in 0.1M HCl solution
35 phology of the sample preserved that of the fresh sample
-7 -5
36 (see Fig. S6b). Fig. S7c displays Raman spectra randomly CPE×10 Cdl×10 R2 R1 Rcorr
37 obtained at five points on the sample surface; low D peaks
-1 -2 n -2
38 indicated negligible defects for this sample. The Tafel Sample (Ω cm s ) n (Fcm ) (Ωcm2) (Ωcm2) (Ωcm2)
39 plots of the sample in acidic and marine electrolytes were
Ni 9.85 0.87 4.06 56.64 29.02 85.7
40 measured in comparison with the freshly prepared coun-
41 terpart (see Fig. S8). The corrosion current densities of GNi-1/16 3.11 0.96 3.59 145.5 36.83 182.3
42 two curves in both environments were only slightly dif-
The graphene-covered Ni electrode exhibited lower elec-
43 ferent. These results displayed long-term stability of the
trolyte/metal interface capacitance (Cdl, 35.9 µFcm-2)
44 graphene coatings in corrosion environment.
compared to that of the bare Ni (see table 2). This implies
45 Overall, the icorr of a GNi sample was smaller than that of the effectiveness of the graphene coating in providing
46 the counterpart Ni, indicating that the TG coating indeed separation between the Ni and the corrosive environ-
47 enhances its corrosion resistance. The GNi–1/16 exhibited ment. Since the capacitance is inversely proportional to
48 the lowest icorr in different environments (see Fig. 5d), the distance of charge separation, lower Cdl of the gra-
49 representing its best corrosion resistance. Note that the phene-covered Ni refers to a lower exposure of Ni surface
50 GNi–1/16 has the thickest graphene layers among all the to active species.
51 samples. By contrast, the GNi–1/400 with the thinnest
52 The corrosion resistance (Rcorr) can be estimated as the
graphene layers exhibited the highest icorr compared with
53 sum of resistance (R1) against electrolyte exposure to gra-
the other two GNi samples. This trend can be additionally
54 phene (or oxide) through defects, and interface resistance
evidenced by the I–V curves in the different environments
55 (R2) between the electrolyte and graphene/Ni (or ox-
as shown in Fig. S9, with a suppression of ionic conduc-
56 ide/Ni). 31 A corrosion resistance of 182.3 Ωcm2 was found
tion through the TG coating. The impermeability of the
57 for the GNi-1/16, 2.1 times larger than that of the bare Ni.
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The exponent of constant phase element (CPE), n, of the AUTHOR INFORMATION

1 GNi is 0.96, closer to 1 compared to that of the bare Ni,
2 indicating capacitor behavior (resistor behavior if n is Corresponding Author
3 close to 0). ⃰ Corresponding author. Tel: +886-5-2720411 ext.66305
4 E-mail address: phycch@ccu.edu.tw
Overall, the EIS results, together with the potentiody-
5
namic polarization results, indicate the graphene coatings ACKNOWLEDGMENT
6
as an excellent barrier layer that prevents direct contact
7 between Ni and corrosive environment, resulting in the This study was financially supported by the Ministry of Sci-
8 decrease of the anodic reaction rate.
ence and Technology (MOST) of the Republic of China (Tai-
9 wan) (MOST 104-2112-M-194-002-MY3). Dr. An T. Nguyen
10 Conclusions acknowledges the support of postdoctoral fellowships from
11 The layers of the TGs were controlled by adjusting the CA MOST, Taiwan.
12 membrane quantity during the thermal annealing process.
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