光学传感器辅助氧气消耗法评估灰口铁的腐蚀状态
Evaluation of the Corrosion State of Gray Iron by Optical Sensor Assisted Oxygen Consumption Method
摘 要
采用光学传感器辅助氧气消耗法研究了不同湿度下灰口铸铁样片的腐蚀速率。用体视显微镜、扫描电子显微镜（SEM）、显微傅里叶变换红外光谱（FT-IR）、X射线衍射（XRD）、X射线光电子能谱（XPS）对样片表面锈蚀产物的形貌和结构进行表征。结果表明：随着环境湿度的升高，灰口铸铁样片的氧气消耗速率明显增加，相对湿度80%下的耗氧速率是30%条件下的20倍；所有湿度条件下样片表面均产生两种不同宏观表现的锈蚀区域，一种是以有机酸腐蚀产物为主的红棕色区域，一种是发生明显刻蚀的花纹状区域；两种区域内都存在有机酸锈蚀产物、不同晶相的羟基氧化铁（FeOOH）、不同晶相的三氧化二铁（Fe2O3）和氧化亚铁（FeO）；其中有机酸产物来源于调湿材料的自由释放。
灰口铸铁
腐蚀
文物保护
oxygen consumption
gray cast iron
corrosion
heritage conservation
Abstract
The corrosion rate of gray cast iron samples under different humidity was studied by optical sensor assisted oxygen consumption method. The morphology and structure of the corrosion products on the sample surface were characterized by stereomicroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results showed that with the increase of ambient humidity, the oxygen consumption rate of gray cast iron samples increased significantly. The oxygen consumption rate at 80% relative humidity was 20 times that at 30%. At all humidity, there were two different kinds of corrosion areas on the samples' surface. One of them was the reddish-brown area dominated by organic acid corrosion products, and the other was the obviously etched pattern area. There were organic acid corrosion products, ferrous oxide (FeO), hydroxyl iron oxide (FeOOH) and iron oxide (Fe2O3) in different crystal phases in the both regions. The organic acid product was caused by the free release of fiber humidity control material.
中图分类号 TG174 DOI 10.11973/fsyfh-202210012
所属栏目 试验研究
基金项目 国家重点研发计划（2020YFC1522100）
收稿日期 2022/3/14
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引用该论文: XU Mengying,WANG Keqing,ZHANG Ran. Evaluation of the Corrosion State of Gray Iron by Optical Sensor Assisted Oxygen Consumption Method[J]. Corrosion & Protection, 2022, 43(10): 76
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【3】许淳淳, 于凯, 于淼. 铁质文物复合封护剂防蚀性能研究[J]. 腐蚀与防护, 2004, 25(6):231-233, 241.
【4】MATTHIESEN H, WONSYLD K. In situ measurement of oxygen consumption to estimate corrosion rates[J]. Corrosion Engineering, Science and Technology, 2010, 45(5):350-356.
【5】MATTHIESEN H. A novel method to determine oxidation rates of heritage materials in vitro and in situ[J]. Study in conservation, 2007, 52:271-280.
【6】THICKETT D. Oxygen depletion testing of metals[J]. Heritage, 2021, 4:2377-2389.
【7】WATKINSON D E, RIMMER M B, EMMERSON N J. The influence of relative humidity and intrinsic chloride on post-excavation corrosion rates of archaeological wrought iron[J]. Stud Conserv, 2019, 64(8):456-471.
【8】SCOTT D A. 古代和历史时期金属制品金相学与显微结构[M]. 北京:科学出版社, 2012.
【9】陈建立, 杨琮, 张焕新, 等. 福建武夷山城村汉城出土铁器的金相实验研究[J]. 文物, 2008(3):88-96.
【10】孟哲, 贾振斌, 魏雨. δ-FeOOH的制备及热处理产物的FTIR光谱[J]. 过程工程学报, 2004, 4(2):146-149.
【11】SRIVASTAVA V, KUMAR S. Formation of hierarchical structures of Fe2O3 by the liquid-liquid interface technique[J]. Cryst Eng Comm, 2014, 16:11122-11126.
【12】BRIGGS D, SEAH M P. Practical Surface Analysis Second Edition Volume1, Auger and X-ray Photoelectron Spectroscopy[M]. New York:John Wiley & Sons, 1996.
【13】YOGEV D, EFRIMA S. Novel silver metal liquid-like films[J]. J Phys.Chem., 1988, 92(20):5754-5760.
【14】YAMASHITA T, HAYES P. Effect of curve fitting parameters on quantitative analysis of Fe0.94O and Fe2O3 using XPS[J]. J Electron Spectrosc Relat Phenom, 2006, 152(1/2):6-11.
【15】YAMASHITA T, HAYES P. Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials[J]. Appl Surf Sci, 2008, 254:2441-2449.
【16】JIA C J, SUN L D, LUO F, et al. Large-scale synthesis of single-crystalline iron oxide magnetic nanorings[J]. J Am Chem.Soc., 2008, 130(50):16968-16977.
【17】FUJII T D E, GROOT F M F, SAWATZKY G A, et al. In situ XPS analysis of various iron oxide films grown by NO2-assisted molecular-beam epitaxy[J]. Phys Rev B:Condens Matter Mater Phys, 1999, 59, 3195.
【18】ZHANG D, ZHANG X, NI X, et al. Fabrication and characterization of Fe3O4 Octahedrons via an EDTA-Assisted Route[J]. Cryst Growth Des, 2007, 7(10):2117-2119.
【19】BRUNDLE C R, CHUANG T J, WANDELt K. Core and valence level photoemission studies of iron oxide surfaces and the oxidation of iron[J]. Surf Sci, 1977, 68:459-468.
【20】GRAAT P C J, SOMERS M A J. Simultaneous determination of composition and thickness of thin iron-oxide films from XPS Fe 2p spectra[J]. Appl Surf Sci, 1996, 100:36-40.
【21】MILLS P, SULLLIVAN J L. A study of the core level electrons in iron and its three oxides by means of X-ray photoelectron spectroscopy[J]. J Phys D:Appl Phys, 1983, 16(5):723-732.
【22】THEVUTHASAN S, KIM Y J, YI S I, et al. Surface structure of MBE-grown α-Fe2O3(0001) by intermediate-energy X-ray photoelectron diffraction[J]. Surf Sci, 1999, 425:276-286.
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