A facile approach to fabricating graphene/waterborne epoxy coatings with dual functionalities of barrier and corrosion inhibitor

doi:10.1016/j.jmst.2021.07.061

Abstract

Abstract:

A facile and environmentally-friendly method is developed to prepare graphene/waterborne epoxy (WEP) composite coatings. The graphene nanosheets are produced with electrochemical-exfoliation in the solution containing surfactants, cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS). The nanosheets containing solution thus formed are subjected to a quick dialysis and then directly used as a diluent for WEP without any further treatment. This preparation method overcomes the commonly identified problems of aggregations and ‘corrosion promotion’ effect associated with graphene, and increases the impedance of the composite coatings by more than two orders of magnitude. The analysis of anticorrosion performance suggested that the presence of surfactants not only improves the dispersibility of graphene nanosheets but also endows the composite coatings with both barrier and corrosion inhibition capabilities. The strategy reported herein may pave the path to the large-scale production of graphene anticorrosion coatings.

Key words: Electrochemical-exfoliation graphene, Waterborne epoxy coatings, Anticorrosion, Inhibition

Suyun Liu, Xuewan Wang, Qi Yin, Xiongzhi Xiang, Xian-Zhu Fu, Xian-Zong Wang, Jing-Li Luo. A facile approach to fabricating graphene/waterborne epoxy coatings with dual functionalities of barrier and corrosion inhibitor[J]. J. Mater. Sci. Technol., 2022, 112: 263-276.

Figures/Tables 17

Fig. 1. Visual and schematic illustration of the electrochemical-exfoliation of graphene CTAB and SDS solution: (a) the color changes of SDS solution during electrochemical-exfoliation process and the obtained homogeneous G/SDS dispersion solution after ultrasound treatment, (b) electrochemical cell, (c) schematic diagram of the formation process of graphene nanosheets in surfactant-containing solution during electrochemical-exfoliation.

Fig. 2. (a) Tailored and (b) SEM images of GP, SEM images of the freeze-dried (c) C-G and (d) S-G nanosheets; AFM images and the corresponding heights of the (e, g) C-G and (f, h) S-G nanosheets.

Fig. 3. TEM morphologies of (a) C-G, (b) S-G and the corresponding HRTEM images of (c) C-G, (d) S-G nanosheets.

Fig. 4. (a) Raman spectra with the ID/IG ratios and (b) XPS survey spectra with C/O ratios for the C-G, S-G nanosheets and the raw GP.

Fig. 5. (a) Visual illustration of the dispersion stabilities of G/CTAB and G/SDS dispersion solution after 360 h standing time. The stereomicroscope morphologies of (b) WEP, (c) C-G/WEP and (d) S-G/WEP coatings.

Fig. 6. SEM images of the cross-sectional morphologies of (a, b) WEP, (c, d) C-G/WEP, and (e, f) S-G/WEP coatings.

Fig. 7. Water absorption curves for the free film of WEP, C-G/WEP and S-G/WEP samples in 3.5 wt.% NaCl solution.

Fig. 8. Nyquist plots of (a) WEP, (c) C-G/WEP, (d) S-G/WEP coatings in a 3.5 wt.% NaCl solution at 1 h to 72 h immersion time and (b) the corresponding equivalent circuit model.

Table 1. The average Rc values (Ω cm2) obtained from the EIS fitting results in 3.5 wt.% NaCl during different immersion time.

Coatings	Immersion time
Coatings	1 h	24 h	72 h
WEP coatings	6.89 × 10⁹	4.72 × 10⁸	3.52 × 10⁸
C-G/WEP coatings	1.97 × 10¹⁰	4.38 × 10⁹	1.63 × 10⁹
S-G/WEP coatings	1.56 × 10¹⁰	3.18 × 10⁹	1.36 × 10⁹

Fig. 9. Impedance plots of (a, b) C-G/ WEP, (c, d) S-G/WEP, and (e, f) WEP coatings on Q235 steel in 3.5 wt.% NaCl solution.

Fig. 10. (a) The obtained Rct values as a function of immersion time (with the corresponding equivalent circuit model inset), (a1) partial enlargement of (a), (b) the evolution of |Z|0.01 Hz, (c) OCP with immersion time in 3.5 wt.% NaCl solution for the coated Q235 steel steels.

Fig. 11. SEM images and element total spectra of the underlying steel beneath (a) WEP coatings after 360 h immersion in 3.5 wt.% NaCl solution, (b) C-G/WEP and (c) S-G/WEP coatings after 720 h immersion, (d) the corresponding chemical composition of the underlying metal.

Fig. 12. Morphologies of the scratched regions for (a) WEP, (b) C-G/WEP, (c) S-G/WEP coatings after immersion in 3.5 wt.% NaCl solution for 6 h.

Fig. 13. Visual performances of (a, b) WEP, (c, d) C-G/WEP, (e, f) S-G/WEP coatings before (a, c, e) and after (b, d, f) 168 h exposed to salt spray test (sodium chloride concentration: 5 wt.%, temperature: 35 °C, the scratch with size of 4 cm in length is produced by a sharp blade.

Fig. 14. Schematic diagrams of corrosion behavior for WEP-coated Q235 steel (top) and our graphene-surfactant/WEP coated Q235 steel (bottom).

Table 2. Comparison of graphene synthesis, modification methods and anticorrosion performance by our method and the graphene WEP coatings reported in literature.

Coatings	Graphene preparation	Modification methods	Coatings’ preparation	Log\|Z\| growth	Refs.
C-G/WEPS-G/WEP	Electro-exfoliation	None	Dialyze and add into coatings	6.5-9.3 (720 h)	This work
Lignin-OH/G/WEP	Ultrasonic stripping	Synthesize lignin-OH, and lignin-OH/G	Filtration, wash, re-disperse in the coatings	2.9-4.1 (144 h)	[9]
Polydopamine-GO/WEP	Commercial	Synthesize polydopamine-GO	Wash, dry and disperse in the coatings	6.3-7.1 (960 h)	[20]
Ammonium-GO/WEP	Hummers’	Modify GO with silane, and synthesize ammonium-GO	Wash, dry and redisperse in the coatings	6.1-7.5 (960 h)	[45]
PA/GO/WEP	Commercial	Modify GO with phytic acid (PA/GO)	Centrifuge, wash and disperse PA/GO in the coatings	4.8-7.4 (840 h)	[46]
Lysine/GO/WEP	Commercial	Synthesize Lysine/GO	Centrifuge, wash Lysine/GO and disperse in the coatings	5.2-6.8 (1272 h)	[70]
G-GO/WEP	Hummers’	Blend G and GO	Disperse in the coatings	4.9-6.0 (720 h)	[71]
G-TA/WEP	Commercial	Synthesize G-TA with TA and KH560	Centrifugation and disperse in the coatings	5.4-8.8 (720 h)	[72]
PPy-GO/WEP	Hummers’	Wash and dry GO, synthesize PPy-GO	Wash, dry and disperse PPy-GO with Zn₃(PO₄)₂ to prepare coatings	4.3-4.5 (240 h)	[73]
HTMoO₄/GO/WEP	Hummers’	SynthesizeHT-MoO₄/GO	Wash, dry and re-disperse in the coatings	2.2-3.7 (240 h)	[74]
G/V₂O₅@PANI/WEP	Oxidation-reduction	Synthesize V₂O₅@PANI, and G/V₂O₅@PANI	Disperse G/V₂O₅@PANI in the coatings	6.4-8.2 (336 h)	[75]
PGO/WEP	Commercial	Modify GO with KH580, and synthesize PGO	Wash, dry and redisperse PGO in the coatings	6.1-7.2 (960 h)	[76]
SGO/WEP	Commercial	Modify GO by KH560, and treat with microwave	Centrifuge, wash and redisperse SGO in the coatings	6.3-9.5 (2160 h)	[77]
MGO/WEP	Hummers	Modify GO with silane coupling agent to obtain MGO	Wash, dry and disperse in the coatings	2.7-4.1 (720 h)	[78]

Table 2. Comparison of graphene synthesis, modification methods and anticorrosion performance by our method and the graphene WEP coatings reported in literature.

Coatings	Graphene preparation	Modification methods	Coatings’ preparation	Log\|Z\| growth	Refs.
C-G/WEPS-G/WEP	Electro-exfoliation	None	Dialyze and add into coatings	6.5-9.3 (720 h)	This work
Lignin-OH/G/WEP	Ultrasonic stripping	Synthesize lignin-OH, and lignin-OH/G	Filtration, wash, re-disperse in the coatings	2.9-4.1 (144 h)	[9]
Polydopamine-GO/WEP	Commercial	Synthesize polydopamine-GO	Wash, dry and disperse in the coatings	6.3-7.1 (960 h)	[20]
Ammonium-GO/WEP	Hummers’	Modify GO with silane, and synthesize ammonium-GO	Wash, dry and redisperse in the coatings	6.1-7.5 (960 h)	[45]
PA/GO/WEP	Commercial	Modify GO with phytic acid (PA/GO)	Centrifuge, wash and disperse PA/GO in the coatings	4.8-7.4 (840 h)	[46]
Lysine/GO/WEP	Commercial	Synthesize Lysine/GO	Centrifuge, wash Lysine/GO and disperse in the coatings	5.2-6.8 (1272 h)	[70]
G-GO/WEP	Hummers’	Blend G and GO	Disperse in the coatings	4.9-6.0 (720 h)	[71]
G-TA/WEP	Commercial	Synthesize G-TA with TA and KH560	Centrifugation and disperse in the coatings	5.4-8.8 (720 h)	[72]
PPy-GO/WEP	Hummers’	Wash and dry GO, synthesize PPy-GO	Wash, dry and disperse PPy-GO with Zn₃(PO₄)₂ to prepare coatings	4.3-4.5 (240 h)	[73]
HTMoO₄/GO/WEP	Hummers’	SynthesizeHT-MoO₄/GO	Wash, dry and re-disperse in the coatings	2.2-3.7 (240 h)	[74]
G/V₂O₅@PANI/WEP	Oxidation-reduction	Synthesize V₂O₅@PANI, and G/V₂O₅@PANI	Disperse G/V₂O₅@PANI in the coatings	6.4-8.2 (336 h)	[75]
PGO/WEP	Commercial	Modify GO with KH580, and synthesize PGO	Wash, dry and redisperse PGO in the coatings	6.1-7.2 (960 h)	[76]
SGO/WEP	Commercial	Modify GO by KH560, and treat with microwave	Centrifuge, wash and redisperse SGO in the coatings	6.3-9.5 (2160 h)	[77]
MGO/WEP	Hummers	Modify GO with silane coupling agent to obtain MGO	Wash, dry and disperse in the coatings	2.7-4.1 (720 h)	[78]

Fig. 15. Comparison of the log|Z| improvement by our method and the reported graphene/WEP coatings reported in the literature. The number in the circle is the Ref. No.

References 78

[1]	B. Zhang, J. Duan, Y. Huang, B. Hou, J. Mater. Sci. Technol. 71 (2021) 1-11. DOI URL
[2]	F. Zhang, P. Ju, M. Pan, D. Zhang, Y. Huang, G. Li, X. Li, Corros. Sci. 144 (2018) 74-88. DOI URL
[3]	A. Nautiyal, M. Qiao, T. Ren, T. Huang, X. Zhang, J. Cook, M.J. Bozack, R. Farag, Eng. Sci. 4 (2018) 70-78.
[4]	H. Du, X. Ren, D. Pan, Y. An, Y. Wei, X. Liu, L. Hou, B. Liu, M. Liu, Z. Guo, Adv. Compos. Hybrid Mater. 4 (2021) 401-414. DOI URL
[5]	J. Liu, J. Zhang, J. Tang, L. Pu, Y. Xue, M. Lu, L. Xu, Z. Guo, ES Mater. Manuf. 10 (2020) 29-38.
[6]	A.M. Madhusudhana, K.N.S. Mohana, M.B. Hegde, S.R. Nayak, K. Rajitha, N.K. Swamy, Adv. Compos. Hybrid Mater. 3 (2020) 141-155. DOI URL
[7]	M. Zhang, M. Dong, S. Chen, Z. Guo, Eng. Sci. 3 (2018) 67-76. DOI URL
[8]	Q. Zhu, J. Liu, X. Wang, Y. Huang, Y. Ren, W. Song, C. Mu, X. Liu, F. Wei, C. Liu, ES Mater. Manuf. 9 (2020) 48-54.
[9]	S. Wang, Z. Hu, J. Shi, G. Chen, Q. Zhang, Z. Weng, K. Wu, M. Lu, Appl. Surf. Sci. 484 (2019) 759-770. DOI URL
[10]	Y. He, Q. Chen, S. Yang, C. Lu, M. Feng, Y. Jiang, G. Cao, J. Zhang, C. Liu, Compos. Part A Appl. Sci. Maunf 108 (2018) 12-22.
[11]	D. Pan, Q. Li, W. Zhang, J. Dong, F. Su, V. Murugadoss, Y. Liu, C. Liu, N. Naik, Z. Guo, Compos. Part B Eng. 209 (2021) 108609. DOI URL
[12]	L. Shi, G. Song, P. Li, X. Li, D. Pan, Y. Huang, L. Ma, Z. Guo, Compos. Sci. Technol. 201 (2021) 108522. DOI URL
[13]	H. Kang, Q. Shao, X. Guo, A. Galaska, Y. Liu, Z. Guo, Eng. Sci. 1 (2018) 78-85.
[14]	Y. Ye, H. Chen, Y. Zou, H. Zhao, J. Mater. Sci. Technol. 67 (2021) 226-236. DOI URL
[15]	R.B. Ashok, C.V. Srinivasa, B. Basavaraju, Adv. Compos. Hybrid Mater. 3 (2020) 365-374. DOI URL
[16]	J. Li, P. Zhang, H. He, S. Zhai, Y. Xian, W. Ma, L. Wang, ES Energy Environ. 4 (2019) 41-47.
[17]	K. Shi, Y. Shen, Y. Zhang, T. Wang, Eng. Sci. 5 (2019) 66-72.
[18]	X. Jing, J. Wei, Y. Liu, B. Song, Y. Liu, Eng. Sci. 11 (2020) 44-53.
[19]	U.S. Gupta, M. Dhamarikar, A. Dharkar, S. Tiwari, R. Namdeo, Adv. Compos. Hybrid Mater. 3 (2020) 530-540. DOI URL
[20]	M. Cui, S. Ren, H. Zhao, Q. Xue, L. Wang, Chem. Eng. J. 335 (2018) 255-266. DOI URL
[21]	S. Liu, L. Gu, H. Zhao, J. Chen, H. Yu, J. Mater. Sci. Technol. 32 (2016) 425-431. DOI URL
[22]	H. Gu, C. Ma, J. Gu, J. Guo, X. Yan, J. Huang, Q. Zhang, Z. Guo, J. Mater. Chem. C 4 (2016) 5890-5906. DOI URL
[23]	H. Yan, M. Cai, W. Li, X. Fan, M. Zhu, J. Mater. Sci. Technol. 54 (2020) 144-159. DOI URL
[24]	J. Wang, Y. Liu, Z. Fan, W. Wang, B. Wang, Z. Guo, Adv. Compos. Hybrid Mater. 2 (2019) 1-33. DOI URL
[25]	Y. Chen, Z. Guo, R. Das, Q. Jiang, ES Food Agrofor. 2 (2020) 12-21.
[26]	L. Wang, X. Shi, J. Zhang, Y. Zhang, J. Gu, J. Mater. Sci. Technol. 52 (2020) 119-126. DOI
[27]	I. Bustero, I. Gaztelumendi, I. Obieta, M.A. Mendizabal, A. Zurutuza, A. Ortega, B. Alonso, Adv. Compos. Hybrid Mater. 3 (2020) 31-40. DOI URL
[28]	H. Yang, Q. Li, Z. Wang, H. Wu, Y. Wu, P. Hou, X. Cheng, E.S. Mater. Manuf. 12 (2021) 29-34.
[29]	H. Liu, Y. Mao, E.S. Mater. Manuf. 13 (2021) 3-22.
[30]	J. Gu, J. She, Y. Yue, ES Energy Environ. 9 (2020) 15-27.
[31]	N. Nidamanuri, Y. Li, Q. Li, M. Dong, Eng. Sci. 9 (2020) 3-16.
[32]	Y. Zhou, P. Wang, G. Ruan, P. Xu, Y. Ding, ES Mater. Manuf. 11 (2021) 20-29.
[33]	G. Cui, Z. Bi, R. Zhang, J. Liu, X. Yu, Z. Li, Chem. Eng. J. 373 (2019) 104-121. DOI URL
[34]	R. Ding, S. Chen, J. Lv, W. Zhang, X. Zhao, J. Liu, X. Wang, T. Gui, B. Li, Y. Tang, W. Li, J. Alloy. Compd. 806 (2019) 611-635. DOI
[35]	Y. Wu, W. Zhao, Y. Qiang, Z. Chen, L. Wang, X. Gao, Z. Fang, Carbon 159 (2020) 292-302.
[36]	Y. Ye, D. Yang, D. Zhang, H. Chen, H. Zhao, X. Li, L. Wang, Chem. Eng. J. 383 (2020) 13.
[37]	F. Jiang, W. Zhao, Y. Wu, Y. Wu, G. Liu, J. Dong, K. Zhou, Appl. Surf. Sci. 479 (2019) 963-973. DOI URL
[38]	M. Schriver, W. Regan, W.J. Gannett, A.M. Zaniewski, M.F. Crommie, A. Zettl, ACS Nano 7 (2013) 5763-5768. DOI PMID
[39]	J. Ding, H. Zhao, D. Ji, B. Xu, X. Zhao, Z. Wang, D. Wang, Q. Zhou, H. Yu, J. Mater. Chem. A 7 (2019) 2864-2874. DOI URL
[40]	W. Sun, T. Wu, L. Wang, Z. Yang, T. Zhu, C. Dong, G. Liu, Compos. Part B Eng. 173 (2019) 8.
[41]	B. Xue, M. Yu, J. Liu, S. Li, L. Xiong, X. Kong, J. Electrochem. Soc. 163 (2016) C798-C806.
[42]	M. Behzadnasab, S.M. Mirabedini, K. Kabiri, S. Jamali, Corros. Sci. 53 (2011) 89-98. DOI URL
[43]	W. Li, T. Shang, W. Yang, H. Yang, S. Lin, X. Jia, Q. Cai, X. Yang, ACS Appl. Mater. Interfaces 8 (2016) 13037-13050. DOI URL
[44]	Z. Zhao, L. Guo, L. Feng, H. Lu, Y. Xua, J. Wang, B. Xiang, X. Zou, Eur. Polym. J. 120 (2019) 13.
[45]	Y. Tian, Y. Xie, F. Dai, H. Huang, L. Zhong, X. Zhang, Surf. Coat. Technol. 383 (2020) 125227. DOI URL
[46]	X. Zhou, H. Huang, R. Zhu, R. Chen, X. Sheng, D. Xie, Y. Mei, Prog. Org. Coat. 143 (2020) 105601.
[47]	R. Mohammadkhani, M. Ramezanzadeh, S. Saadatmandi, B. Ramezanzadeh, Chem. Eng. J. 382 (2020) 122819. DOI URL
[48]	S. Amrollahi, B. Ramezanzadeh, H. Yari, M. Ramezanzadeh, M. Mandavian, Compos. Part B Eng. 173 (2019) 14.
[49]	W. Zheng, W. Chen, T. Feng, W. Li, X. Liu, L. Dong, Y. Fu, Prog. Org. Coat. 138 (2020) 9.
[50]	X. Xing, X. Xu, J. Wang, W. Hu, Appl. Surf. Sci. 479 (2019) 835-846. DOI URL
[51]	S. Pei, Q. Wei, K. Huang, H. Cheng, W. Ren, Nat. Commun. 9 (2018) 145. DOI URL
[52]	W.S. Hummers, R.E. Offeman, J. Am. Chem. Soc. 80 (1958) 1339. DOI URL
[53]	D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L. B. Alemany, W. Lu, J.M. Tour, ACS Nano 4 (2010) 4806-4814. DOI URL
[54]	K. Kakaei, K. Hasanpour, J. Mater. Chem. A 2 (2014) 15428-15436. DOI URL
[55]	M. Yusuf, M.A. Khan, M. Otero, E.C. Abdullah, M. Hosomi, A. Terada, S. Riya, J. Colloid Interface Sci. 493 (2017) 51-61. DOI URL
[56]	F. Arjmand, J. Wang, L. Zhang, J. Mater. Eng. Perform. 25 (2016) 809-819. DOI URL
[57]	S. Javadian, A. Youseﬁ, J. Neshati, Appl. Surf. Sci. 285 (2013) 674-681. DOI URL
[58]	ISO 2808-2007, Paints and varnishes Determination of ﬁlm thickness, International Standard, 2007.
[59]	S. Liu, L. Liu, Y. Li, F. Wang, J. Mater. Sci. Technol. 39 (2020) 48-55. DOI URL
[60]	S. Daradmare, S. Raj, A.R. Bhattacharyya, S. Parida, Compos. Part B Eng. 155 (2018) 1-10. DOI URL
[61]	K. Parvez, Z. Wu, R. Li, X. Liu, R. Graf, X. Feng, K. Muellen, J. Am. Chem. Soc. 136 (2014) 6083-6091. DOI URL
[62]	S. Pei, H. Cheng, Carbon N Y 50 (2012) 3210-3228. DOI URL
[63]	A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Phys. Rev. Lett. 97 (2006) 187401. DOI URL
[64]	J. Pellessier, Y. Gang, Y. Li, ES Mater. Manuf. 13 (2021) 66-75.
[65]	S. Qiu, W. Li, W. Zheng, H. Zhao, L. Wang, ACS Appl. Mater. Interfaces 9 (2017) 34294-34304. DOI URL
[66]	Y. Wang, Z. Gu, J. Liu, J. Jiang, N. Yuan, J. Pu, J. Ding, Surf. Coat. Technol. 360 (2019) 276-284. DOI URL
[67]	F. Meng, L. Liu, Y. Cui, F. Wang, J. Mater. Sci. Technol. 64 (2021) 165-175. DOI URL
[68]	S. Liu, L. Liu, H. Guo, E.E. Oguzie, Y. Li, F. Wang, Electrochem. Commun. 98 (2019) 110-114. DOI URL
[69]	G. Gupta, N. Birbilis, A.B. Cook, A.S. Khanna, Corros. Sci. 67 (2013) 256-267. DOI URL
[70]	X. Zhou, H. Huang, R. Zhu, X. Sheng, D. Xie, Y. Mei, Prog. Org. Coat. 136 (2019) 105200.
[71]	F. Zhong, Y. He, P. Wang, C. Chen, Y. Lin, Y. Wu, J. Chen, Appl. Surf. Sci. 488 (2019) 801-812. DOI
[72]	Y. He, C. Chen, G. Xiao, F. Zhong, Y. Wu, Z. He, React. Funct. Polym. 137 (2019) 104-115. DOI URL
[73]	Q. Zhu, E. Li, X. Liu, W. Song, M. Zhao, L. Zi, X. Wang, C. Liu, Compos. Part A Appl. Sci. Manuf. 130 (2020) 105752. DOI URL
[74]	N. Thuy Duong, N. Anh Son, T. Boi An, V. Ke Oanh, T. Dai Lam, P. Thanh Thao, N. Scharnagl, M.L. Zheludkevich, T. Thi Xuan Hang, Surf. Coat. Technol. 399 (2020) 126165. DOI URL
[75]	F. Zhong, Y. He, P. Wang, C. Chen, H. Yu, H. Li, J. Chen, React. Funct. Polym. 151 (2020) 13.
[76]	H. Huang, Y. Tian, Y. Xie, R. Mo, J. Hu, M. Li, X. Sheng, X. Jiang, X. Zhang, Prog. Org. Coat. 146 (2020) 105724.
[77]	J. Cui, W. Shan, J. Xu, H. Qiu, J. Li, J. Yang, Compos. Sci. Technol. 200 (2020) 108438. DOI URL
[78]	H. Li, C. Xue, L. Gao, X. Wang, H. Wei, H. Nan, G. Wang, H. Lin, Prog. Org. Coat. 150 (2021) 105974.