Synergistic Effect of NaCl and SO2 on the Initial Atmospheric Corrosion of Zinc Under Wet-Dry Cyclic Conditions

doi:10.1007/s40195-018-0863-9

Abstract

Abstract:

The synergistic effect of NaCl and SO₂ on the atmospheric corrosion of zinc has been studied at equivalent total but different ratios of molar deposition rate under wet-dry cyclic conditions. The results show that the corrosion rates, corrosion morphologies and the composition of the corrosion products are strongly influenced by the molar deposition rate ratio of NaCl and SO₂ (NaCl/SO₂). The corrosivity of NaCl and SO₂ toward zinc increases in order of SO₂＜1:3＜3:1＜NaCl＜1:1. The corrosion morphology is patchy corrosion for Group 1:1, while it is pocking corrosion for the other four experimental groups. The corrosion product containing sulfur and chlorine detected on zinc is Gordaite (NaZn₄SO₄(OH)₆Cl·6H₂O), which has quite porous structure and was supposed to cause the patchy corrosion tendency of zinc in Group 1:1. In addition, soluble zinc corrosion products, which can inhibit the atmospheric corrosion process of zinc, were found on zinc samples in Groups 1:3 and SO₂ and connected to the lower corrosion rates of zinc in these two groups.

Key words: Atmospheric, corrosion, Zinc, Synergistic, effect, Corrosivity, Corrosion, morphology, Gordaite

Yin Qi, Wang Zhen-Yao, Liu Miao-Ran, Pan Chen. Synergistic Effect of NaCl and SO₂ on the Initial Atmospheric Corrosion of Zinc Under Wet-Dry Cyclic Conditions[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(6): 780-796.

Figures/Tables 17

Table 1 Deposition rates of the salts in each experimental group

Salts	NaCl	3:1	1:1	1:3	SO₂
NaCl Deposition rate (mg m^-2 d^-1)	1170	877.5	585	292.5	0
NaHSO₃ Deposition rate (mg m^-2 d^-1)	0	520.5	1141	1561.5	2082
Molar deposition rate ratio	-	3:1	1:1	1:3	-

Fig. 1 Thickness loss of the zinc samples in various groups

Fig. 2 XRD patterns of the corroded zinc samples: a Group NaCl; b Group 3:1; c Group 1:1; d Group 1:3; e Group SO2

Fig. 3 FTIR spectroscopies of the corrosion products on zinc samples: a Group NaCl; b Group 3:1; c Group 1:1; d Group 1:3; e Group SO2

Table 2 Corrosion products detected by XRD and FTIR on the corroded zinc samples

Groups	Corrosion products
NaCl	Zn₅(OH)₈Cl₂·H₂O Zn(OH)₂ Zn₅(CO₃)₂(OH)₆
3:1	NaZn₄SO₄(OH)₆Cl·6H₂O Zn₅(OH)₈Cl₂·H₂O Zn(OH)₂ Zn₅(CO₃)₂(OH)₆
1:1	NaZn₄SO₄(OH)₆Cl·6H₂O Zn(OH)₂ Zn₅(CO₃)₂(OH)₆
1:3	NaZn₄SO₄Cl(OH)₆·6H₂O Na₂Zn(SO₄)₂·4H₂O^a Zn₅(CO₃)₂(OH)₆
SO₂	Na₂Zn(SO₄)₂·4H₂O^a ZnSO₄·H₂O^a Zn₄SO₄(OH)₆·H₂O

Fig. 4 Surface photographs of the corroded zinc samples: a Group NaCl; b Group 3:1; c Group 1:1; d Group 1:3; e Group SO2

Fig. 5 Surface morphologies of the zinc samples after removal of the corrosion products: a, b Group NaCl; c, d Group 3:1; e, f Group 1:1; g, h Group 1:3; i, j Group SO2

Fig. 6 Corrosion products morphologies on corroded zinc samples in Group NaCl: a-c the surface morphologies, d the cross section morphology

Fig. 7 Corrosion products morphologies on corroded zinc samples in Group SO2: a-c the surface morphologies, d the cross section morphology

Table 3 Element composition of the points marked in Figs. 6 and 7 examined by EDS

Points	Zn (at%)	O (at%)	Cl (at%)	S (at%)
A	15.4	81.8	2.80	-
B	29.9	56.3	13.8	-
C	27.2	72.2	0.540	-
D	30.3	64.6	5.08	-
E	7.31	79.7	-	13.0
F	28.2	66.6	-	5.21
G	28.7	63.7	-	7.60

Fig. 8 SEM images of the surface morphologies on corroded zinc samples: a, b Group 3:1; c-e Group 1:1; f-h Group 1:3

Table 4 Element composition of the points marked in Fig. 8 examined by EDS

Points	Zn (at%)	O (at%)	Cl (at%)	S (at%)
A	15.7	74.6	4.87	4.79
B	24.2	64.5	9.75	1.62
C	16.4	73.4	4.88	5.34
D	17.4	81.3	0.310	1.03
E	7.20	78.8	-	14.0
F	19.2	69.7	5.09	5.95

Table 5 Element composition of zinc corrosion products

Compounds	Zn (at%)	O (at%)	Cl (at%)	S (at%)
Zn₅(OH)₈Cl₂·H₂O	31.2	56.2	12.5	-
NaZn₄SO₄(OH)₆Cl·6H₂O	18.2	72.7	4.54	4.54
Zn₄SO₄(OH)₆·5H₂O	20.0	75.0	-	5.00
Na₂Zn(SO₄)₂·4H₂O	6.67	80.0	-	13.3
ZnSO₄·H₂O	14.3	71.4	-	14.3

Fig. 9 SEM-EDS mapping in the frame area of the cross section of the corroded zinc sample in Group 3:1

Fig. 10 SEM-EDS mapping in the frame area of the cross section of the corroded zinc sample in Group 1:1

Fig. 11 SEM-EDS mapping in the frame area of the cross section of the corroded zinc sample in Group 1:3

Fig. 12 Higher magnification SEM images of cross section in Group 1:1 marked in Fig. 10

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Synergistic Effect of NaCl and SO₂ on the Initial Atmospheric Corrosion of Zinc Under Wet-Dry Cyclic Conditions

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