铁质文物腐蚀产物β-FeOOH的产生及危害
Formation and Hazards of Corrosion Product β-FeOOH on Iron Cultural Relics
摘 要
综述了铁质文物腐蚀产物β-FeOOH的晶体结构、在铁质文物腐蚀中的生成过程以及对铁质文物的危害。β-FeOOH晶体具有隧道结构，隧道中通常含有Cl-，晶体表面也吸附Cl-。它是Cl-作用下铁质文物腐蚀的关键产物，通常在铁质文物出土后由FeCl2、Fe2（OH）3Cl等产物氧化水解生成，其生成过程是导致铁质文物迅速损坏的主要原因，生成后又会进一步参与腐蚀过程。其表面吸附的Cl-会直接引发新的腐蚀，而隧道结构中的Cl-则是铁质文物长期保存过程中的隐患。β-FeOOH是一种对铁质文物危害极大的腐蚀产物，在铁质文物保护过程中应对其进行针对性的处理。
腐蚀产物
腐蚀机理
四方纤铁矿
氯化物
iron cultural relic
corrosion product
corrosion mechanism
akaganeite
chloride
Abstract
The crystal structure of β-FeOOH, one of corrosion products of iron cultural relics, as well as its formation process and hazards to iron cultural relics are introduced. β-FeOOH crystal has a tunnel structure, the tunnel usually contains Cl- ions, and the crystal surface also adsorbs Cl- ions. β-FeOOH is a key corrosion product of iron cultural relics affected by Cl- ions, and commonly is formed through hydrolysis and oxidation of FeCl2 or Fe2(OH)3 Cl after excavation. The formation process of β-FeOOH mainly causes rapid deterioration of iron cultural relics, and it will participate in the further corrosion process after formation. The Cl- ions adsorbed on the surface of crystal will directly induce new corrosion, and the Cl- ions in the tunnel structure are potential risks in long-term preservation of iron cultural relics. β-FeOOH is a harmful corrosion product to iron cultural relics and should be treated in a targeted manner during the conservation of iron cultural relics.
中图分类号 K876.42 DOI 10.11973/fsyfh-202111001
所属栏目 专论
基金项目 国家重点研发计划项目（2020YFC1522100）；国家文物局重点科研基地自筹经费科研项目（2020ZCK111）
收稿日期 2019/12/12
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引用该论文: ZHANG Ran. Formation and Hazards of Corrosion Product β-FeOOH on Iron Cultural Relics[J]. Corrosion & Protection, 2021, 42(11): 1
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参考文献
【1】ZUCCHI F, MORIGI G, BERTOLASI V. Beta iron oxide hydroxide formation in localized active corrosion of iron artifacts[C]//BROWN B F, BURNETT H C, CHASE W T, et al. Corrosion and Metal Artifacts-A Dialogue Between Conservators and Archaeologists and Corrosion Scientists. Washington DC, USA:National Bureau of Standards, 1977:103-105.
【2】SELWYN L. Overview of archaeological iron:the corrosion problem, key factors affecting treatment, and gaps in current knowledge[C]//ASHTON J, HALLAM D. Metal 04:Proceedings of the International Conference on Metals Conservation. Canberra, Australia:National Museum of Australia, 2004:294-306.
【3】JEGDIĆ B, POLIC-RADOVANOVIĆ S, RISTIĆ S, et al. Corrosion processes, nature and composition of corrosion products of iron artefacts of weaponry[J]. Scientific Technical Review, 2011, 61(2):50-56.
【4】KNIGHT B. Why do some iron objects break up in store[C]//CLARKE R W, BLACKSHAW S M. Conservation of Iron. Greenwich, London:Trustees of the National Maritime Museum, 1982:50-51.
【5】KNIGHT B. A review of the corrosion of iron from terrestrial sites and the problem of post-excavation corrosion[J]. The Conservator, 1990, 14(1):37-43.
【6】THICKETT D. Post excavation changes and preventive conservation of archaeological iron[D]. London:University of London, 2012:291-294.
【7】TURGOOSE S. The nature of surviving iron objects[C]//CLARKE R W, BLACKSHAW S M. Conservation of Iron. Greenwich, London:Trustees of the National Maritime Museum, 1982:1-7.
【8】TURGOOSE S. Structure, composition and deterioration of unearthed iron objects[C]//AOKI S. Current Problems in the Conservation of Metal Antiqutites. Tokyo:Tokyo National Research Institute of Cultural Properties, 1993:35-53.
【9】WANG Z S, XU C C, CAO X, et al. The morphology, phase composition and effect of corrosion product on simulated archaeological iron[J]. Chinese Journal of Chemical Engineering, 2007, 15(3):433-438.
【10】SELWYN L S, SIROIS P J, ARGYROPOULOS V. The corrosion of excavated archaeological iron with details on weeping and akaganéite[J]. Studies in Conservation, 1999, 44(4):217-232.
【11】STÅHL K, NIELSEN K, JIANG J Z, et al. On the akaganéite crystal structure, phase transformations and possible role in post-excavational corrosion of iron artifacts[J]. Corrosion Science, 2003, 45(11):2563-2575.
【12】AL-ZAHRANI A A. Chloride ion removal from archaeological iron and β-FeOOH[D]. Cardiff:University of Wales, 1999:14.
【13】GONZÁLEZ N, DE VIVIÉS P, DREWS M J, et al. Hunting free and bound chloride in the wrought iron rivets from the American Civil War submarine H. L. Hunley[J]. Journal of the American Institute for Conservation, 2004, 43(2):161-174.
【14】REGUER S, DILLMANN P, MIRAMBET F, et al. Investigation of Cl corrosion products of iron archaeological artefacts using micro-focused synchrotron X-ray absorption spectroscopy[J]. Applied Physics A:Materials Science & Processing, 2006, 83(2):189-193.
【15】REGUER S, MIRAMBET F, DOORYHEE E, et al. Structural evidence for the desalination of akaganeite in the preservation of iron archaeological objects, using synchrotron X-ray powder diffraction and absorption spectroscopy[J]. Corrosion Science, 2009, 51(12):2795-2802.
【16】马清林, 沈大娲, 永昕群. 铁质文物保护技术[M]. 北京:科学出版社, 2011:7-40.
【17】成小林, 梅建军, 陈淑英, 等. 不同保存环境下铁质文物中氯含量的分析[J]. 中国历史文物, 2010(5):25-31.
【18】成小林, 胥谞, 赵鹏. 山东蓬莱水城出土铁锚病害分析与保护处理[C]//中国文物保护技术协会第八次学术年会论文集.北京:科学出版社, 2014:17-25.
【19】刘薇, 张治国, 李秀辉, 等. 海洋出水古代铁器表面凝结物的分析研究[M]//中国文化遗产研究院. 文物科技研究:第七辑.北京:科学出版社, 2010:132-147.
【20】包春磊. 华光礁Ⅰ号出水铁器文物的腐蚀与保护措施[J]. 腐蚀与防护, 2012, 33(7):614-617, 625.
【21】包春磊, 贾世杰, 符燕, 等. 海南省博物馆馆藏出水古铁炮腐蚀产物分析[J]. 腐蚀与防护, 2014, 35(1):83-86, 90.
【22】包春磊, 贾世杰, 李剑, 等. 热带海洋出水铁炮的保护研究[J]. 腐蚀科学与防护技术, 2016, 28(2):189-192.
【23】林浩. 宁波象山港古铁锚化学成分及腐蚀机理分析[J]. 东方博物, 2006(3):68-71.
【24】王蕙贞, 朱虹, 宋迪生, 等. 秦汉铁器锈蚀机理探讨及保护方法研究[J]. 文物保护与考古科学, 2003, 15(1):7-11.
【25】陶宏. 盐业铁质文物锈蚀机理探讨[J]. 盐业史研究, 2000(3):31-37.
【26】戎岩. 申明铺遗址出土腐蚀铁器的微观分析[J]. 咸阳师范学院学报, 2012, 27(4):87-90.
【27】卢燕玲. 铁仔山古墓群出土铁器腐蚀病害与机理分析[J]. 中国文物科学研究, 2011(3):36-40.
【28】张红燕. 济南魏家庄遗址出土铁器腐蚀初步分析研究[M]//王浩天, 梁宏刚. 文物保护修复理论与实践——金石匠学之路.北京:科学出版社, 2014:1-24.
【29】王浩天, 张红燕, 梁宏刚, 等. 高度腐蚀矿化出土铁器的保护修复——以济南魏家庄出土铁釜的保护修复为例[J]. 江汉考古, 2017(5):108-116.
【30】申桂云. 铁质文物锈蚀机理及广西出土、出水铁质文物保护研究[J]. 辽宁省博物馆馆刊, 2009:508-542.
【31】SONG X W, BOIL J F. Variable hydrogen bond strength in akaganéite[J]. The Journal of Physical Chemistry C, 2012, 116(3):2303-2312.
【32】BERNAL J D, DASGUPTA D R, MACKAY A L. The oxides and hydroxides of iron and their structural inter-relationships[J]. Clay Minerals, 1959, 4(21):15-30.
【33】MACKAY A L. β-ferric oxyhydroxide[J]. Mineralogical Magazine and Journal of the Mineralogical Society, 1960, 32(250):545-557.
【34】SZYTUŁA A, BAŁANDA M, DIMITRIJEVIĆ Ž. Neutron diffraction studies of β-FeOOH[J]. Physica Status Solidi (a), 1970, 3(4):1033-1037.
【35】POST J E, BUCHWALD V F. Crystal structure refinement of akaganéite[J]. American Mineralogist, 1991, 76(1/2):272-277.
【36】CHAMBAERE D G, DE GRAVE E. A study of the non-stoichiometrical halogen and water content of β-FeOOH[J]. Physica Status Solidi (a), 1984, 83(1):93-102.
【37】ELLIS J, GIOVANOLI R, STUMM W. Anion exchange properties of β-FeOOH[J]. Chimia, 1976, 30(3):194-197.
【38】CHILDS C W, GOODMAN B A, PATERSON E, et al. The nature of iron in akaganéite (β-FeOOH)[J]. Australian Journal of Chemistry, 1980, 33(1):15-26.
【39】BLAND P A, KELLEY S P, BERRY F J, et al. Artificial weathering of the ordinary chondrite Allegan:implications for the presence of Cl- as a structural component in akaganeite[J]. American Mineralogist, 1997, 82(11/12):1187-1197.
【40】PATERSON R, RAHMAN H. The ion exchange properties of crystalline inorganic oxide-hydroxides:Part I.βFeOOH:a variable capacity anion exchanger[J]. Journal of Colloid and Interface Science, 1983, 94(1):60-69.
【41】CAI J, LIU J, GAO Z, et al.Synthesis and anion exchange of tunnel structure akaganeite[J]. Chemistry of Materials, 2001, 13(12):4595-4602.
【42】CORNELL R M, SCHWERTMANN U. The Iron Oxides-Structure, Properties, Reactions, Occurences and Uses[M]. 2nd ed. Weinheim:WILEY-VCH Verlag GmbH & Co. KGaA, 2003:104.
【43】THICKETT D, ODLYHA M. The formation and transformation of akaganeite[C]//HYSLOP E, GONZALEZ V, TROALEN L, et al. Metal 2013:Interim Meeting of the ICOM-CC Metal Working Group, Conference Proceedings. Edinburgh, Scotland:Historic Scotland, International Council of Museums, 2013:107-113.
【44】GALLAGHER K J, PHILLIPS D N. Hydrogen exchange studies and proton transfer in β iron(III) oxyhydroxide[J]. Chimia, 1969, 23(12):465-470.
【45】GILBERG M 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(2):50-56.
【46】TURGOOSE S. Post-excavation changes in iron antiquities[J]. Studies in Conservation, 1982, 27(3):97-101.
【47】KIYAMA M, TAKADA T. Iron compounds formed by the aerial oxidation of ferrous salt solutions[J]. Bulletin of the Chemical Society of Japan, 1972, 45(6):1923-1924.
【48】RÉMAZEILLES C, REFAIT P. On the formation of β-FeOOH (akaganéite) in chloride-containing environments[J]. Corrosion Science, 2007, 49(2):844-857.
【49】WANG Q Y. Effects of relative humidity on the corrosion of iron:an experimental view[J]. The British Museum Technical Research Bulletin, 2007, 1:65-73.
【50】WATKINSON D, LEWIS M. SS Great Britain iron hull:modelling corrosion to define storage relative humidity[C]//ASHTON J, HALLAM D. Metal 04:Proceedings of the International Conference on Metals Conservation. Canberra, Australia:National Museum of Australia, 2004:88-102.
【51】WATKINSON D, LEWIS M T. Desiccated storage of chloride-contaminated archaeological iron objects[J]. Studies in Conservation, 2005, 50(4):241-252.
【52】LEWIS M R T. The influence of atmospheric moisture on the corrosion of chloride-contaminated wrought iron[D]. Cardiff:Cardiff University, 2009:196-206.
【53】THICKETT D. Analysis of iron corrosion products with Fourier transform infra-red and Raman spectroscopies[C]//PICOLLO M. Proceedings of the Sixth Infrared and Raman Users Group Conference (IRUG6). Italy:Instituto di Fisica Applicata "Nello Carrara" IFAC-CNR, 2004:86-93.
【54】RIMMER M B. Investigating the treatment of chloride-infested archaeological iron objects[D]. Cardiff:Cardiff University, 2010:39-40.
【2】SELWYN L. Overview of archaeological iron:the corrosion problem, key factors affecting treatment, and gaps in current knowledge[C]//ASHTON J, HALLAM D. Metal 04:Proceedings of the International Conference on Metals Conservation. Canberra, Australia:National Museum of Australia, 2004:294-306.
【3】JEGDIĆ B, POLIC-RADOVANOVIĆ S, RISTIĆ S, et al. Corrosion processes, nature and composition of corrosion products of iron artefacts of weaponry[J]. Scientific Technical Review, 2011, 61(2):50-56.
【4】KNIGHT B. Why do some iron objects break up in store[C]//CLARKE R W, BLACKSHAW S M. Conservation of Iron. Greenwich, London:Trustees of the National Maritime Museum, 1982:50-51.
【5】KNIGHT B. A review of the corrosion of iron from terrestrial sites and the problem of post-excavation corrosion[J]. The Conservator, 1990, 14(1):37-43.
【6】THICKETT D. Post excavation changes and preventive conservation of archaeological iron[D]. London:University of London, 2012:291-294.
【7】TURGOOSE S. The nature of surviving iron objects[C]//CLARKE R W, BLACKSHAW S M. Conservation of Iron. Greenwich, London:Trustees of the National Maritime Museum, 1982:1-7.
【8】TURGOOSE S. Structure, composition and deterioration of unearthed iron objects[C]//AOKI S. Current Problems in the Conservation of Metal Antiqutites. Tokyo:Tokyo National Research Institute of Cultural Properties, 1993:35-53.
【9】WANG Z S, XU C C, CAO X, et al. The morphology, phase composition and effect of corrosion product on simulated archaeological iron[J]. Chinese Journal of Chemical Engineering, 2007, 15(3):433-438.
【10】SELWYN L S, SIROIS P J, ARGYROPOULOS V. The corrosion of excavated archaeological iron with details on weeping and akaganéite[J]. Studies in Conservation, 1999, 44(4):217-232.
【11】STÅHL K, NIELSEN K, JIANG J Z, et al. On the akaganéite crystal structure, phase transformations and possible role in post-excavational corrosion of iron artifacts[J]. Corrosion Science, 2003, 45(11):2563-2575.
【12】AL-ZAHRANI A A. Chloride ion removal from archaeological iron and β-FeOOH[D]. Cardiff:University of Wales, 1999:14.
【13】GONZÁLEZ N, DE VIVIÉS P, DREWS M J, et al. Hunting free and bound chloride in the wrought iron rivets from the American Civil War submarine H. L. Hunley[J]. Journal of the American Institute for Conservation, 2004, 43(2):161-174.
【14】REGUER S, DILLMANN P, MIRAMBET F, et al. Investigation of Cl corrosion products of iron archaeological artefacts using micro-focused synchrotron X-ray absorption spectroscopy[J]. Applied Physics A:Materials Science & Processing, 2006, 83(2):189-193.
【15】REGUER S, MIRAMBET F, DOORYHEE E, et al. Structural evidence for the desalination of akaganeite in the preservation of iron archaeological objects, using synchrotron X-ray powder diffraction and absorption spectroscopy[J]. Corrosion Science, 2009, 51(12):2795-2802.
【16】马清林, 沈大娲, 永昕群. 铁质文物保护技术[M]. 北京:科学出版社, 2011:7-40.
【17】成小林, 梅建军, 陈淑英, 等. 不同保存环境下铁质文物中氯含量的分析[J]. 中国历史文物, 2010(5):25-31.
【18】成小林, 胥谞, 赵鹏. 山东蓬莱水城出土铁锚病害分析与保护处理[C]//中国文物保护技术协会第八次学术年会论文集.北京:科学出版社, 2014:17-25.
【19】刘薇, 张治国, 李秀辉, 等. 海洋出水古代铁器表面凝结物的分析研究[M]//中国文化遗产研究院. 文物科技研究:第七辑.北京:科学出版社, 2010:132-147.
【20】包春磊. 华光礁Ⅰ号出水铁器文物的腐蚀与保护措施[J]. 腐蚀与防护, 2012, 33(7):614-617, 625.
【21】包春磊, 贾世杰, 符燕, 等. 海南省博物馆馆藏出水古铁炮腐蚀产物分析[J]. 腐蚀与防护, 2014, 35(1):83-86, 90.
【22】包春磊, 贾世杰, 李剑, 等. 热带海洋出水铁炮的保护研究[J]. 腐蚀科学与防护技术, 2016, 28(2):189-192.
【23】林浩. 宁波象山港古铁锚化学成分及腐蚀机理分析[J]. 东方博物, 2006(3):68-71.
【24】王蕙贞, 朱虹, 宋迪生, 等. 秦汉铁器锈蚀机理探讨及保护方法研究[J]. 文物保护与考古科学, 2003, 15(1):7-11.
【25】陶宏. 盐业铁质文物锈蚀机理探讨[J]. 盐业史研究, 2000(3):31-37.
【26】戎岩. 申明铺遗址出土腐蚀铁器的微观分析[J]. 咸阳师范学院学报, 2012, 27(4):87-90.
【27】卢燕玲. 铁仔山古墓群出土铁器腐蚀病害与机理分析[J]. 中国文物科学研究, 2011(3):36-40.
【28】张红燕. 济南魏家庄遗址出土铁器腐蚀初步分析研究[M]//王浩天, 梁宏刚. 文物保护修复理论与实践——金石匠学之路.北京:科学出版社, 2014:1-24.
【29】王浩天, 张红燕, 梁宏刚, 等. 高度腐蚀矿化出土铁器的保护修复——以济南魏家庄出土铁釜的保护修复为例[J]. 江汉考古, 2017(5):108-116.
【30】申桂云. 铁质文物锈蚀机理及广西出土、出水铁质文物保护研究[J]. 辽宁省博物馆馆刊, 2009:508-542.
【31】SONG X W, BOIL J F. Variable hydrogen bond strength in akaganéite[J]. The Journal of Physical Chemistry C, 2012, 116(3):2303-2312.
【32】BERNAL J D, DASGUPTA D R, MACKAY A L. The oxides and hydroxides of iron and their structural inter-relationships[J]. Clay Minerals, 1959, 4(21):15-30.
【33】MACKAY A L. β-ferric oxyhydroxide[J]. Mineralogical Magazine and Journal of the Mineralogical Society, 1960, 32(250):545-557.
【34】SZYTUŁA A, BAŁANDA M, DIMITRIJEVIĆ Ž. Neutron diffraction studies of β-FeOOH[J]. Physica Status Solidi (a), 1970, 3(4):1033-1037.
【35】POST J E, BUCHWALD V F. Crystal structure refinement of akaganéite[J]. American Mineralogist, 1991, 76(1/2):272-277.
【36】CHAMBAERE D G, DE GRAVE E. A study of the non-stoichiometrical halogen and water content of β-FeOOH[J]. Physica Status Solidi (a), 1984, 83(1):93-102.
【37】ELLIS J, GIOVANOLI R, STUMM W. Anion exchange properties of β-FeOOH[J]. Chimia, 1976, 30(3):194-197.
【38】CHILDS C W, GOODMAN B A, PATERSON E, et al. The nature of iron in akaganéite (β-FeOOH)[J]. Australian Journal of Chemistry, 1980, 33(1):15-26.
【39】BLAND P A, KELLEY S P, BERRY F J, et al. Artificial weathering of the ordinary chondrite Allegan:implications for the presence of Cl- as a structural component in akaganeite[J]. American Mineralogist, 1997, 82(11/12):1187-1197.
【40】PATERSON R, RAHMAN H. The ion exchange properties of crystalline inorganic oxide-hydroxides:Part I.βFeOOH:a variable capacity anion exchanger[J]. Journal of Colloid and Interface Science, 1983, 94(1):60-69.
【41】CAI J, LIU J, GAO Z, et al.Synthesis and anion exchange of tunnel structure akaganeite[J]. Chemistry of Materials, 2001, 13(12):4595-4602.
【42】CORNELL R M, SCHWERTMANN U. The Iron Oxides-Structure, Properties, Reactions, Occurences and Uses[M]. 2nd ed. Weinheim:WILEY-VCH Verlag GmbH & Co. KGaA, 2003:104.
【43】THICKETT D, ODLYHA M. The formation and transformation of akaganeite[C]//HYSLOP E, GONZALEZ V, TROALEN L, et al. Metal 2013:Interim Meeting of the ICOM-CC Metal Working Group, Conference Proceedings. Edinburgh, Scotland:Historic Scotland, International Council of Museums, 2013:107-113.
【44】GALLAGHER K J, PHILLIPS D N. Hydrogen exchange studies and proton transfer in β iron(III) oxyhydroxide[J]. Chimia, 1969, 23(12):465-470.
【45】GILBERG M 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(2):50-56.
【46】TURGOOSE S. Post-excavation changes in iron antiquities[J]. Studies in Conservation, 1982, 27(3):97-101.
【47】KIYAMA M, TAKADA T. Iron compounds formed by the aerial oxidation of ferrous salt solutions[J]. Bulletin of the Chemical Society of Japan, 1972, 45(6):1923-1924.
【48】RÉMAZEILLES C, REFAIT P. On the formation of β-FeOOH (akaganéite) in chloride-containing environments[J]. Corrosion Science, 2007, 49(2):844-857.
【49】WANG Q Y. Effects of relative humidity on the corrosion of iron:an experimental view[J]. The British Museum Technical Research Bulletin, 2007, 1:65-73.
【50】WATKINSON D, LEWIS M. SS Great Britain iron hull:modelling corrosion to define storage relative humidity[C]//ASHTON J, HALLAM D. Metal 04:Proceedings of the International Conference on Metals Conservation. Canberra, Australia:National Museum of Australia, 2004:88-102.
【51】WATKINSON D, LEWIS M T. Desiccated storage of chloride-contaminated archaeological iron objects[J]. Studies in Conservation, 2005, 50(4):241-252.
【52】LEWIS M R T. The influence of atmospheric moisture on the corrosion of chloride-contaminated wrought iron[D]. Cardiff:Cardiff University, 2009:196-206.
【53】THICKETT D. Analysis of iron corrosion products with Fourier transform infra-red and Raman spectroscopies[C]//PICOLLO M. Proceedings of the Sixth Infrared and Raman Users Group Conference (IRUG6). Italy:Instituto di Fisica Applicata "Nello Carrara" IFAC-CNR, 2004:86-93.
【54】RIMMER M B. Investigating the treatment of chloride-infested archaeological iron objects[D]. Cardiff:Cardiff University, 2010:39-40.
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