High corrosion resistance film on rebar by cerium modification

doi:10.1016/j.jmst.2019.09.033

Abstract

Abstract:

A cerium film was prepared on the surface of rebar by chemical conversion method to enhance its corrosion resistance. The film in the simulated concrete pore solution was measured by electrochemical method, transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). The effect of temperature on film formation was studied, and the optimum temperature was determined at 35 °C. The film produced by too high formation temperature has more defects, resulting in the lower corrosion resistance. The Ce film resistance increased with time evolution until 800 h, then decreased and stabilized. The Ce film layer has a double-layer film structure, the upper layer is an oxide of cerium, and the underlayer is an oxide of iron. Results revealed that after being immersed in the simulated concrete pore solution, the corrosion resistance of the Ce film was enhanced by self-densification.

Key words: Ce film, Concrete simulation solution, Double-layer film, Self-densification

Hongze An, Zhengyi Xu, Guozhe Meng, Weihua Li, Yanqiu Wang, Bin Liu, Junyi Wang, Fuhui Wang. High corrosion resistance film on rebar by cerium modification[J]. J. Mater. Sci. Technol., 2021, 64: 73-84.

Figures/Tables 15

Fig. 1. Surface of Ce films treated at different temperatures (The inserts are macroscopic pictures).

Fig. 2. TEM results of Ce film-35 °C on a rebar: (a-d) Surface scan maps of Ce, Fe, O elements for the cross section of the HAADF image, and surface (e) the corresponding data in the deep blue region of the HAADF image, and (f) the longitudinal section of Ce film on a rebar with the corresponding fast Fourier transform (FFT) image.

Fig. 3. Polarization curves for rebar and Ce films treated at different temperatures in the simulated concrete pore solutions with 0.6 M NaCl.

Table 1 Electrochemical parameters obtained by fitting the curves.

Sample	E_corr (V)	i_p (μA/cm²)	E_pit (V)
Rebar	-0.26	24.31-32.30	-0.06
Ce film-25 ℃	-0.26	0.16-1.36	0.91
Ce film-35 ℃	-0.24	0.02-1.03	0.89
Ce film-45 ℃	-0.39	2.04-.11	0.41
Ce film-55 ℃	-0.26	0.37-1.95	0.87

Fig. 4. EIS of rebar and Ce films treated at different temperatures in simulated concrete pore solutions with 0.6 M NaCl: (a) Nyquist plots, and (b) the corresponding data of the charging transfer resistance Rt plots. The inset in the top right corner of (a) shows the corresponding equivalent electrical circuit.

Table 2 Key electrochemical parameters obtained by fitting the EIS data.

Sample	R_s (Ω cm²)	CPE_f (×10^-5S s-ⁿ cm^-2)	n₁	R_film (×10⁴ Ω cm²)	CPE_dl (×10^-5 S s-ⁿ cm^-2)	n₂	R_t (×10⁴ Ω cm²)
Rebar	5.83	8.46	0.91	0.20	27.45	0.77	0.42
Ce film-25 ℃	5.53	19.86	0.72	1.41	43.86	0.96	30.80
Ce film-35 ℃	3.63	9.99	0.81	0.48	6.35	0.54	44.85
Ce film-45 ℃	4.56	36.40	0.69	0.38	82.56	0.95	22.50
Ce film-55 ℃	4.16	37.82	0.68	0.38	110.10	0.99	9.01

Fig. 5. Charge transfer resistance (Rt) of Ce film-35 ℃ in simulated concrete pore solutions with 0.6 M NaCl changes with immersion time.

Fig. 6. Mott-Schottky curves of rebar (a), Ce film-25 ℃ (b), Ce film-35 ℃ (c), Ce film-45 ℃ (d), Ce film-55 ℃ (e) and the donor density in simulated concrete pore solutions with 0.1 M NaCl for rebar and Ce films treated at different temperatures (f).

Fig. 7. (a) Double-layer capacitance as a function of electrode potential curves for rebar (a), Ce film-25 ℃ (b), Ce film-35 ℃ (c), Ce film-45 ℃ (d), Ce film-55 ℃ (e), and the polarization curves in simulated concrete pore solutions with 0.1 M NaCl for the rebar and Ce films treated at different temperatures (f).

Table 3 Atomic percentage (at.%) of different temperature Ce film.

Sample	Ce 3d			Fe 2p
Sample	Ce₂O₃	CeO₂	Fe⁰	Fe²⁺	Fe³⁺
Ce film-25 ℃	29.12	70.88	0	0	0
Ce film-35 ℃	32.99	67.01	0	0	0
Ce film-45 ℃	25.00	75.00	0	0	0
Ce film-55 ℃	20.42	79.58	0	0	0

Table 4 Atomic percentage (at.%) of different temperature Ce films after immersion in simulated concrete pore solutions with 0.1 M NaCl for 4 h.

Sample	Ce 3d		Fe 2p
Sample	Ce₂O₃	CeO₂	Fe⁰	Fe²⁺	Fe³⁺
Ce film-25 ℃	55.49	44.51	0	0	0
Ce film-35 ℃	53.19	46.81	0	0	0
Ce film-45 ℃	54.84	45.16	0	0	0
Ce film-55 ℃	50.99	49.01	18.40	41.33	40.27

Fig. 8. XPS survey spectra of Ce films treated at different temperatures before (a) and after (b) 4 h of corrosion in simulated concrete pore solutions with 0.1 M NaCl.

Fig. 9. Core-level spectra of Ce 3d for Ce films treated at different temperatures before (a-d) and after (e-h) 4 h of immersion in simulated concrete pore solutions with 0.1 M NaCl.

Fig. 10. Core-level spectra of Fe 2p for Ce films treated at different temperatures after 4 h of immersion in simulated concrete pore solutions with 0.1 M NaCl: (a) Ce film-25 ℃; (b) Ce film-35 ℃; (c) Ce film-45 ℃; (d) Ce film-55 ℃.

Fig. 11. Proposed anti-corrosion process on surface of Ce film.

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