Self-assembling anchored film basing on two tetrazole derivatives for application to protect copper in sulfuric acid environment

doi:10.1016/j.jmst.2020.04.005

Abstract

Abstract:

Two tetrazole compounds (BTA, BTTA) self-assembled on copper substrate and their inhibition effect toward copper corrosion in 0.5 M H₂SO₄ was evaluated through atomic force microscopy (AFM), scanning electron microscopy (SEM), weight loss measurement along with electrochemical techniques including electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. Results indicate that BTTA can provide superior inhibition performance to BTA, and the highest inhibition efficiency values of 96.3% (BTA) and 99.8% (BTTA) were achieved respectively at 2 mM. Both tetrazole inhibitor films follow Langmuir model concerning both physical and chemical adsorption, which can be verified by X-ray photoelectronic spectroscopy (XPS) analysis. Besides, the negative value of adsorption free energy infers a spontaneous adsorption process of these tetrazole compounds on Cu surface. Molecular dynamics (MD) simulation reveals stronger multiple anchor adsorption of BTTA molecules than BTA because of the existence of S atom.

Key words: Copper, Corrosion inhibitor, Adsorption, Anticorrosion, MD simulation

Yujie Qiang, Hao Li, Xijian Lan. Self-assembling anchored film basing on two tetrazole derivatives for application to protect copper in sulfuric acid environment[J]. J. Mater. Sci. Technol., 2020, 52: 63-71.

Figures/Tables 13

Fig. 1. Schematic diagram of proposed anchored tetrazole films on Cu surface.

Fig. 2. SEM images of copper after immersion in various test solutions: (a) blank-24 h; (b) BTA-24 h; (c) BTTA-24 h.

Fig. 3. 2D and 3D AFM images of copper after immersion in various test solutions: (a, d) blank-4 h; (b, e) BTA-4 h; (c, f) BTTA-4 h.

Fig. 4. Height profile of copper surfaces made along the marked line in Fig. 3.

Fig. 5. Nyquist diagrams of copper with BTA (a) and BTTA (b) in various test solutions after 20 min immersion.

Fig. 6. Bode diagrams of copper with BTA (a) and BTTA (b) in various test solutions after 20 min immersion.

Fig. 7. The used equivalent circuits in fitting EIS data process for copper in blank solution (a) and in presence of tetrazole inhibitor (b).

Table 1 Impedance parameters of copper in different test environments.

C (mM)	R_s (Ω cm²)	R_f (Ω cm²)	R_ct (Ω cm²)	C_f (μF cm^-2)	n₁	C_dl (μF cm^-2)	n₂	W (?10^-2 Ω cm² s^1/2)	η (%)	χ² ×10^-3
Blank	1.4	-	365 ± 32	-	-	14.2	0.75	1.7	-	2.31
BTA
0.5	1.1	53.7 ± 4.8	1143 ± 52	4.9	0.97	2.8	0.77	0.01	68.1	4.45
1	0.6	117.6 ± 10.5	2068 ± 97	2.4	1	1.2	0.73	0.2	82.4	3.62
1.5	5.8	154.4 ± 10.2	3173 ± 105	2.3	0.97	1.3	0.72	0.2	88.5	1.47
2	1.6	183.1 ± 15.4	9346 ± 284	2.1	1	0.8	0.68	0.1	96.1	1.98
BTTA
0.5	4.8	112.5 ± 9.6	1622 ± 86	4.7	0.97	2.1	0.67	0.8	77.5	2.80
1	1.1	1458 ± 88	3719 ± 152	1.6	1	1.1	0.73	0.6	90.2	6.23
1.5	0.9	1410 ± 69	12,137 ± 556	1.2	1	0.6	0.70	0.1	97.0	1.02
2	0.7	2116 ± 125	67,621 ± 1945	1.2	0.99	0.5	0.69	0.01	99.5	2.46

Fig. 8. Tafel graphs of copper with BTA (a) and BTTA (b) in various test solutions.

Table 2 Polarization parameters of copper in various test environments.

C (mM)	E_corr (mV/SCE)	i_corr (μA cm^-2)	β_c (mV dec^-1)	β_a (mV dec^-1)	η (%)
Blank	-38 ± 3	28.87 ± 2.12	-483.0	42.1	-
BTA
0.5	-30 ± 4	12.08 ± 1.04	-158.8	250.6	58.2
1	7 ± 3	8.02 ± 0.76	-188.9	154.0	72.2
1.5	-50 ± 2	5.32 ± 0.45	-145.4	240.3	81.6
2	20 ± 2	1.08 ± 0.09	-159.6	103.4	96.3
BTTA
0.5	-2 ± 3	10.43 ± 0.74	-138.4	89.9	63.9
1	-4 ± 2	5.89 ± 0.47	-127.4	112.1	79.6
1.5	-20 ± 3	1.72 ± 0.11	-154.5	104.1	94.0
2	-1 ± 2	0.056 ± 0.005	-172.8	81.4	99.8

Fig. 9. Weight loss data of copper and corresponding Langmuir isotherms: (a, b) BTA; (c, d) BTTA.

Fig. 10. XPS spectra of copper adsorbed with tetrazole inhibitors: (a) XPS survey spectra; (b) XPS-N1s-BTA; (c) XPS-N1s-BTTA; (d) XPS-S2p-BTTA.

Fig. 11. Adsorption equilibrium configurations of studied compounds on Cu(111) surface: (a) BTA; (b) BTTA; (c) BTAH+; (d) BTTAH+.

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