Localized Corrosion and Phase Transformation of Simulated Archaeological Iron

Abstract

Abstract: The corrosion behaviors of simulated archaeological iron in solution(0.06 mol·L^-1 NaCl+0.03 mol·L^-1 Na₂SO₄+0.01 mol·L^-1 NaHCO₃)simulating soil water composition was investigated by potentialdynamic polariza-tion,constant potential polarization,and simulated occluded cell(O.C.)galvanostatic tests.X-ray diffraction(XRD), energy dispersive spectrometry(EDS),and scanning electron microscope(SEM)were used to study the corrosion morphology and the evolution of corrosion product.The objective was to discover the transformation process of archaeological iron,and determine the distribution of chlorinated corrosion products.The results showed that the presence of crevice,cavities,and channels facilitates the localized corrosion under rusts;the autocatalytic effect in-creases the concentration of Fe²⁺,Cl^-,and SO₄^2-,and promotes local acidification within the crevices and cavities. Meanwhile,the phase transformation of corrosion products is concluded to proceed by means of two ways.One is that the ferrous ions are transformed into different kinds of FeOOH via the intermediate Fe(II)-Fe(III)hydroxyl-salt (i.e.Green Rusts);the other is that the Fe²⁺ ions are transformed into FeCl₂,FeCl₃,and orange powders akaganeite at the crevices and cavities.

Key words: corrosion, corrosion product, iron, chlorine

摘要： The corrosion behaviors of simulated archaeological iron in solution(0.06 mol·L^-1 NaCl+0.03 mol·L^-1 Na₂SO₄+0.01 mol·L^-1 NaHCO₃)simulating soil water composition was investigated by potentialdynamic polariza-tion,constant potential polarization,and simulated occluded cell(O.C.)galvanostatic tests.X-ray diffraction(XRD), energy dispersive spectrometry(EDS),and scanning electron microscope(SEM)were used to study the corrosion morphology and the evolution of corrosion product.The objective was to discover the transformation process of archaeological iron,and determine the distribution of chlorinated corrosion products.The results showed that the presence of crevice,cavities,and channels facilitates the localized corrosion under rusts;the autocatalytic effect in-creases the concentration of Fe²⁺,Cl^-,and SO₄^2-,and promotes local acidification within the crevices and cavities. Meanwhile,the phase transformation of corrosion products is concluded to proceed by means of two ways.One is that the ferrous ions are transformed into different kinds of FeOOH via the intermediate Fe(II)-Fe(III)hydroxyl-salt (i.e.Green Rusts);the other is that the Fe²⁺ ions are transformed into FeCl₂,FeCl₃,and orange powders akaganeite at the crevices and cavities.

关键词: corrosion, corrosion product, iron, chlorine

WANG Zise, XU Chunchun, DONG Xiqing. Localized Corrosion and Phase Transformation of Simulated Archaeological Iron[J]. , 2008, 16(2): 299-305.

王紫色, 许淳淳, 董希青. Localized Corrosion and Phase Transformation of Simulated Archaeological Iron[J]. , 2008, 16(2): 299-305.

References

1 Dillmann, N.P., Bellot-Gurlet, L., Beranger, G., “Corrosion of iron archaeological artefacts in soil: Characterization of the corrosion system”, Corros. Sci., 47 (2), 515-535 (2005).
2 Wei, B.M., “The theory and application of metal corrosion”, Chemical Industry Press, Beijing (1984). (in Chinese)
3 Scott, D.A., Seeley, N.J., “The washing of fragile iron artifacts”, Stud. Conserv., 32, 73-76 (1987).
4 Turgoose, S., “The corrosion of archaeological iron during burial and treatment”, Stud. Conserv., 30, 13-18 (1985).
5 Selwyn, S., Mccinnon, W.R., Argyropulos, V., “Models for chloride ion diffusion in archaeological iron”, Stud. Conserv., 46, 109 (2001).
6 Reguer, S., Dillmann, P.H., Irambet, F., Bellot-Gurlet, L., “Local and structural characterisation of chlorinated phases formed on ferrous archaeological artefacts by μXRD and μXANES”, Nuclear Instrum. and Methods in Phys. Res. B, 240, 500-504 (2005).
7 Turgoose, S.,“Postexcavation changes in iron antiquities”, Studi. Conserv., 27, 97-101 (1982).
8 WANG, J.L., XU, C.C., “Chemical behavior of bronze localized corrosion in soil”, J. Chem. Ind. Eng. (China), 55 (7), 1135-1139 (2004). (in Chinese)
9 Refait, P.H., “Mechanisms of formation and structure of green rust one in aqueous corrosion of iron in the presence of chloride ions”, Corros. Sci., 40 (9), 1547-1560 (1998).
10 Refait, P.H., “The anionic species competition in iron aqueous cor-rosion: Role of various green rust compounds”, Corros. Sci., 39 (9), 1699-1710 (1997).
11 Abdelmoula, M., “Conservation electron m ssbauer spectroscopy and X-ray diffraction studies of the formation of carbonate-containing green rust one by corrosion of metallic iron in NaHCO₃ and Na-HCO₃+NaCl solutions”, Corros. Sci., 38 (4), 623-633 (1996).
12 Refait, P.H., “The transformation of chloride-containing green rust one into sulphated green rust two by oxidation in mixed Cl-and 2 4 SO ”, Corros. Sci., 36 (1), 55-65 (1994).
13 North, N.A., “Corrosion products on marine iron”, Stud. Conserv., 27, 75-83 (1982).
14 Selwyn, S., Sierois, P.J., Argyropulos, V., “The corrosion of exca-vated archaeological iron with details on weeping and akaganeite”, Stud. Conserv., 44, 217-232 (1998).
15 Kenny, S.A., Kurt, N., Jiang, J.Z., Bente, L., Jonathan, C.H., Poul, N., Jettie, V.L., “On the akaganéite crystal structure, phase transfor-mations and possible role in postexcavational corrosion of iron artifacts”, Corros. Sci., 45, 2563-2575 (2003).
16 Gil, M.L.A., Santos, A., Bethencourt, M., García, S.T., Fernández., B., Velod, A., Gago-Duport, L., “Use of X-ray and other techniques to analyse the phase transformation induced in archaeological cast iron after its stabilisation by the electrolytic method”, Anal. Chim. Acta, 494, 245-254 (2003).
17 Rémazeilles, C., Refait, P.H., “On the formation of β-FeOOH (aka-ganéite) in chloride-containing environments”, Corros. Sci., 49 (2), 844 (2007).
18 Xia, L.T., Wei, H., “Chemical-electrochemical dissolution mecha-nism for pitting corrosion of low alloyed cast irons in nature sea-water”, Chin. J. Mechan. Eng., 38 (9), 140-144 (2002). (in Chinese)
19 Stahl, K., Nielsen, K., Jiang, J.Z., Lebech, B., Jonathan, C.H., Norby, P., Lanschot, J.V., “On the akaganeite crystal structure, phase trans-formations and possible role in post-excavational corrosion of iron artifacts”, Corros. Sci., 45, 2563-2575 (2003).
20 Wang, Z.S., Xu, C.C., Wang, J.L., “Appearance and formation process of corrosion products on archaeological iron in simulated soil media”, J. Chem. Ind. Eng. (China), 56 (12), 2373-2379 (2005). (in Chinese)
21 Wang, Z.S., Xu, C.C., Cao, X., Xu, B., “The morphology, phase composition and effect of corrosion product on simulated archaeo-logical iron”, Chin. J. Chem. Eng., 15 (3), 433-438 (2007).

[1]	Lingli Chen, Yueting Shi, Sijun Xu, Junle Xiong, Fang Gao, Shengtao Zhang, Hongru Li. Enhanced adsorption of target branched compounds including antibiotic norfloxacin frameworks on mild steel surface for efficient protection: An experimental and molecular modelling study [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 212-227.
[2]	Hammad Saulat, Jianhua Yang, Tao Yan, Waseem Raza, Wensen Song, Gaohong He. Tungsten incorporated mobil-type eleven zeolite membranes: Facile synthesis and tuneable wettability for highly efficient separation of oil/water mixtures [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 242-252.
[3]	Minjie Shi, Nianting Chen, Yue Zhao, Cheng Yang, Chao Yan. Facile wet-chemical fabrication of bi-functional coordination polymer nanosheets for high-performance energy storage and anti-corrosion engineering [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 118-127.
[4]	Yanli Zhang, Zhengkun Hou, Dong Yao, Xiaomin Qiu, Hongru Zhang, Peizhe Cui, Yinglong Wang, Jun Gao, Zhaoyou Zhu, Limei Zhong. Energy, exergy, economic and environmental comprehensive analysis and multi-objective optimization of a sustainable zero liquid discharge integrated process for fixed-bed coal gasification wastewater [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 341-354.
[5]	Linlin Su, Meijun Chen, Li Gong, Hua Yang, Chao Chen, Jun Wu, Ling Luo, Gang Yang, Lulu Long. Boost activation of peroxymonosulfate by iron doped K_2-xMn₈O₁₆: Mechanism and properties [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 88-97.
[6]	Yueting Shi, Junhai Zhao, Lingli Chen, Hongru Li, Shengtao Zhang, Fang Gao. Double open mouse-like terpyridine parts based amphiphilic ionic molecules displaying strengthened chemical adsorption for anticorrosion of copper in sulfuric acid solution [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 233-246.
[7]	Jixiang Liu, Xin Zhou, Gengfei Yang, Hui Zhao, Zhibo Zhang, Xiang Feng, Hao Yan, Yibin Liu, Xiaobo Chen, Chaohe Yang. Conceptual carbon-reduction process design and quantitative sustainable assessment for concentrating high purity ethylene from wasted refinery gas [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 290-308.
[8]	Yuhan Zhu, Jia Wei, Jun Li. Decontamination of Cr(VI) from water using sewage sludge-derived biochar: Role of environmentally persistent free radicals [J]. Chinese Journal of Chemical Engineering, 2023, 56(4): 97-103.
[9]	Iltaf Khan, Chunjuan Wang, Shoaib Khan, Jinyin Chen, Aftab Khan, Sayyar Ali Shah, Aihua Yuan, Sohail Khan, Mehwish K. Butt, Humaira Asghar. Bio-capped and green synthesis of ZnO/g-C₃N₄ nanocomposites and its improved antibiotic and photocatalytic activities: An exceptional approach towards environmental remediation [J]. Chinese Journal of Chemical Engineering, 2023, 56(4): 215-224.
[10]	Hany M. Abd El-Lateef, Mai M. Khalaf, K. Shalabi, Antar A. Abdelhamid. Multicomponent synthesis and designing of tetrasubstituted imidazole compounds catalyzed via ionic-liquid for acid steel corrosion protection: Experimental exploration and theoretical calculations [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 304-319.
[11]	Xueguang Li, Mengyan Yu, Changfa Zhang, Xiangtong Li, Guangqing Liu, Jianjun Dai, Chunbao Zhou, Yang Liu, Jie Fu, Yingwen Zhang, Bang Yao. Co-pyrolysis of soybean soapstock with iron slag/aluminum scrap, and characterization and analysis of their products [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 25-36.
[12]	Qingming Ma, Jianhong Xu. Green microfluidics in microchemical engineering for carbon neutrality [J]. Chinese Journal of Chemical Engineering, 2023, 53(1): 332-345.
[13]	Kuo Lin, Zhongjie Shen, Qinfeng Liang, Jianliang Xu, Haifeng Liu. The study of the effect of gas-phase fluctuation on slag flow and refractory brick corrosion in the slag tapping hole of an entrained-flow gasifier [J]. Chinese Journal of Chemical Engineering, 2022, 47(7): 271-281.
[14]	N. M'hanni, T. Anik, R. Touir, M. Galai, M. Ebn Touhami, E.H. Rifi, Z. Asfari, S. Bakkali. Effect of additives on nickel-phosphorus deposition obtained by electroless plating: Characterization and corrosion resistance in 3%(mass) sodium chloride medium [J]. Chinese Journal of Chemical Engineering, 2022, 44(4): 341-350.
[15]	Qi Liu, Gao Cheng, Ming Sun, Weixiong Yu, Xiaohong, Zeng, Shichang Tang, Yongfeng li, Lin Yu. A facile preparation of hausmannite as a high-performance catalyst for toluene combustion [J]. Chinese Journal of Chemical Engineering, 2022, 44(4): 392-401.