仿古铸铁在土壤中腐蚀行为的研究
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摘要
本论文以仿古铸铁为研究对象,采用动电位极化曲线技术、交流阻抗技术等电化学方法研究了土壤中的主要腐蚀性阴离子即C1~-、SO_4~(2-)、HCO_3~-等含量的变化对仿古铸铁腐蚀的影响。实验结果表明:模拟土壤介质中C1~-、SO_4~(2-)浓度的增大加速了仿古铸铁的腐蚀,而HCO_3~-则因参与产物膜的形成、破裂、修复而引起腐蚀速度的波动,导致腐蚀速度呈现为降低、上升、又降低的趋势。
采用动电位极化曲线技术、失重实验等研究了土壤中含水量的变化,以及土壤pH值的变化对仿古铸铁腐蚀的影响,结果表明:土壤含水量在15%-20%条件下仿古铸铁腐蚀程度最为严重;而在含水量较高或较低条件下腐蚀程度较轻;在相同含水量条件下土壤pH值的变化对仿古铸铁的腐蚀速度具有很大的影响,随着土壤pH值的降低,仿古铸铁的腐蚀速率增大。
通过浸泡实验,采用扫描电镜(SEM)、X射线衍射(XRD)、红外光谱(IR)、X射线光电子能谱(XPS)等技术研究仿古铸铁在模拟土壤介质中腐蚀产物的形貌和组成,并与出土宋代铁钱表面的腐蚀产物进行了对比。结果表明:腐蚀产物主要由FeOOH和绿锈组成。随着模拟土壤介质中含盐量的增大、含水量的增加,腐蚀产物变得更加致密。
磷化处理技术是化学稳定化处理技术之一,它可以使铁器表面活泼的铁锈转化形成一层不溶于水的结晶型磷酸盐转化膜。利用一种能够使仿古铸铁表面腐蚀产物转化为致密磷化膜的磷化液配方,通过CuSO_4点滴试验和扫描电镜(SEM)观察,探讨了磷化处理技术在铁器文物保护方面的应用。
The electrochemical methods of polarization curves, electrochemical impedance were used to study the corrosion of the archaeological iron caused by the variation of salt(Cl~-、SO_4~(2-)、HCO_3~-)that was in the soil. The results showed: the more the content of Cl~-, SO_4~(2-) in the soil, the severer the corrosion of archaeological iron. However, HCO_3~- induced the fluctuation of corrosion velocity because of its participation in the formation, cracking, and repairing of corrosion product.
The electrochemical methods of polarization curves and weight loss experiment were employed to study the corrosion of the archaeological iron in soil with different water content and pH. The results showed: corrosion of archaeological iron was in the highest severity when the water content came to the range of 15%-20% in the soil. In the same water content, the lower the pH of the soil, the higher corrosion rate of archaeological iron had.
The corrosion products at different phase on archaeological iron were investigated through immersion corrosion, scanning electron microscope (SEM), X-ray diffraction(XRD), infrared ray(IR) and X-ray photoelectron spectroscopy(XPS).The appearance and phase composition were presented, as was compared with the corrosion products that was on the surface of iron coin from Song Dynasty. The results showed: the corrosion products were mainly composed of FeOOH and Green rust. With the increasing of salt content and moisture content in simulating soil water, the corrosion products became more compact.
Phosphate treatment is one of the processing technics for chemical stabilization. A kind of phosphate dispensation was developed to convert the active rust on the surface of archaeological iron into a layer of crystal indissolvable phosphate film. The method of phosphorise in protecting archaeological iron was discussed though the experiment of dropping of CuSO_4 and scanning electron microscope (SEM).
采用动电位极化曲线技术、失重实验等研究了土壤中含水量的变化,以及土壤pH值的变化对仿古铸铁腐蚀的影响,结果表明:土壤含水量在15%-20%条件下仿古铸铁腐蚀程度最为严重;而在含水量较高或较低条件下腐蚀程度较轻;在相同含水量条件下土壤pH值的变化对仿古铸铁的腐蚀速度具有很大的影响,随着土壤pH值的降低,仿古铸铁的腐蚀速率增大。
通过浸泡实验,采用扫描电镜(SEM)、X射线衍射(XRD)、红外光谱(IR)、X射线光电子能谱(XPS)等技术研究仿古铸铁在模拟土壤介质中腐蚀产物的形貌和组成,并与出土宋代铁钱表面的腐蚀产物进行了对比。结果表明:腐蚀产物主要由FeOOH和绿锈组成。随着模拟土壤介质中含盐量的增大、含水量的增加,腐蚀产物变得更加致密。
磷化处理技术是化学稳定化处理技术之一,它可以使铁器表面活泼的铁锈转化形成一层不溶于水的结晶型磷酸盐转化膜。利用一种能够使仿古铸铁表面腐蚀产物转化为致密磷化膜的磷化液配方,通过CuSO_4点滴试验和扫描电镜(SEM)观察,探讨了磷化处理技术在铁器文物保护方面的应用。
The electrochemical methods of polarization curves, electrochemical impedance were used to study the corrosion of the archaeological iron caused by the variation of salt(Cl~-、SO_4~(2-)、HCO_3~-)that was in the soil. The results showed: the more the content of Cl~-, SO_4~(2-) in the soil, the severer the corrosion of archaeological iron. However, HCO_3~- induced the fluctuation of corrosion velocity because of its participation in the formation, cracking, and repairing of corrosion product.
The electrochemical methods of polarization curves and weight loss experiment were employed to study the corrosion of the archaeological iron in soil with different water content and pH. The results showed: corrosion of archaeological iron was in the highest severity when the water content came to the range of 15%-20% in the soil. In the same water content, the lower the pH of the soil, the higher corrosion rate of archaeological iron had.
The corrosion products at different phase on archaeological iron were investigated through immersion corrosion, scanning electron microscope (SEM), X-ray diffraction(XRD), infrared ray(IR) and X-ray photoelectron spectroscopy(XPS).The appearance and phase composition were presented, as was compared with the corrosion products that was on the surface of iron coin from Song Dynasty. The results showed: the corrosion products were mainly composed of FeOOH and Green rust. With the increasing of salt content and moisture content in simulating soil water, the corrosion products became more compact.
Phosphate treatment is one of the processing technics for chemical stabilization. A kind of phosphate dispensation was developed to convert the active rust on the surface of archaeological iron into a layer of crystal indissolvable phosphate film. The method of phosphorise in protecting archaeological iron was discussed though the experiment of dropping of CuSO_4 and scanning electron microscope (SEM).
引文
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[5]张艳成,何积铃,吴荫顺,韩汝芬.模拟文物铸铁的阴极保护行为[J].腐蚀科学与防护技术,1997,9(3):228-230
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[7]杜嘉鸿,陈兰云.纳米材料在文物保护中的应用探索[J].探矿工程(岩土钻掘工程),2002(2):5-6
[8]黄允兰,林碧霞,等.古代铁器腐蚀产物的结构特征[J].文物保护与考古科学,1996,8(1):26-27
[9]王君龙,程德润.环境对文物的影响与控制[J].延安大学学报(自然科学版),1998(2),54
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[12]中泽骥,苏贵桥.铸铁的电化学腐蚀机理[J].现代铸铁,2002(1):13-14
[13]张安富.响钢铁大气腐蚀的因素[J].材料保护,1989,22(2):16-19
[14]张文青,石声泰,等.金属腐蚀手册[M].上海:上海科学出版社,1987.102-106
[15]冯西桥,金名惠,黄辉桃.金属材料在土壤中的腐蚀速度与土壤电阻率[J].华中科技大学学报,2001,5(5)103-106
[16]曹楚南.中国材料的自然环境腐蚀[M].北京:化学工业出版社,2005.35
[17]尹桂勤,等.土壤腐蚀研究方法概述[J].腐蚀科学与防护技术,2004(11):16
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[19]钱逸泰.结晶化学[M].北京:中国科技大学出版社,2005,321-322
[20]李金柱,赵闰彦,等.腐蚀和腐蚀控制手册[M].北京:国防工业出版社,1988.35-38
[21]Foley RT.Role of the Chloride Iron Corrosion[J].Corrosion-NACE,1970,26(2):58-68
[22]S.Turgoose.Post-excavation Changes in Iron Antiquities[J].Studies in Conversation,1982,27:97-101
[23]Mark R,Seeley N J.The identity of compounds containing chloride ions in marine iron corrosion products:a critical review[J].Studies in Conservation.1981,26,50-56
[24]Turgoose.S.The corrosion of archaeological iron during burial and treatment[J].Studies in conservation,1985,30:13-18
[25]N.A.North,I.D.Macleod.Corrosion of Metals:68-81
[26]Aoke Shige,Hirao Yoahimitse.Stabilization of archaeological iron[A].Reports on the 13th international symposium on the conversation and restoration of cultural property[C].1989:80-85
[27]David A.Scott,Nigel J.Seeley.The Washing of Fragile Iron Artifacts[J].Studies in Conservation.1987,32:73-76
[28]Evnas U R,金属材料的耐腐蚀性[M].北京:科学出版社,1968.68-70
[29]谭伟,徐滨士,韩文政,等.水陆装甲车车体锈层分析[J].腐蚀科学与防护技术,2003,15(2):113-116
[30]Matsui T R,et al,Application of ion chromatography of conservation of archaeological iron objects[A].international ion chromatography symposium[C].1998
[31]Ludovic Legrand.The oxidation of carbonate green rust into ferric phase:solid-state reaction or transformation via solution[J].Geochimica et Cosmochimica Acta,2004,68(17):3497-3507
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