圆明园琉璃瓦片状云母氧化铁的形成机理
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摘要
使用光学显微镜、EDXRF、SEM、XPS和XRD对圆明园出土的部分黄色琉璃瓦釉黄中泛红现象进行分析,以研究琉璃瓦的变色机理。分析表明:琉璃瓦的釉层属于一种铅硅系玻璃,釉层呈现黄中泛红现象是由于红色区域和黄色区域中Fe存在形式不同所致,釉层红色区域中Fe主要是以α-Fe_2O_3晶体形式存在,黄色区域中Fe是以Fe~(3+)与Fe~(2+)的形式存在。这种现象产生的本质是由于黄色区域中的Fe~(2+)在高温条件下被O_2氧化为Fe~(3+),然而高温导致釉层流失,进而导致釉层中的Fe~(3+)析出富聚为六角片状的α-Fe_2O_3晶体颗粒所致。α-Fe_2O_3显红色又被称为云母氧化铁红,是非常重要的防锈防腐涂料以及珠光颜料。
This experiment analyzes the diffused red in yellowing phenomenon of partial yellow glazed tiles unearthed from Yuanmingyuan by means of optical microscope,EDXRF,SEM,XPS,and XRD in order to study the color change mechanism. The analyses suggest that the glaze layer of the sample tiles belongs to a kind of lead silicate glass and that the diffused red in yellowing phenomenon of glaze is due to the different forms of Fe within the glaze layer,with α-Fe_2O_3 crystal dominating the red area and Fe~(3+)and Fe~(2+)existing simultaneously in the yellow area. The study shows the phenomenon can be explained by the process of oxidation of Fe~(2+)into Fe~(3+)in the yellow area at high temperature during which glaze layers are lost. It further results in abundant precipitation of Fe~(3+)in the form of hexagonal plate α-Fe_2O_3 crystal particle,which is also called micaceous iron oxide red being very important rust preventive and pearlescent pigment.
This experiment analyzes the diffused red in yellowing phenomenon of partial yellow glazed tiles unearthed from Yuanmingyuan by means of optical microscope,EDXRF,SEM,XPS,and XRD in order to study the color change mechanism. The analyses suggest that the glaze layer of the sample tiles belongs to a kind of lead silicate glass and that the diffused red in yellowing phenomenon of glaze is due to the different forms of Fe within the glaze layer,with α-Fe_2O_3 crystal dominating the red area and Fe~(3+)and Fe~(2+)existing simultaneously in the yellow area. The study shows the phenomenon can be explained by the process of oxidation of Fe~(2+)into Fe~(3+)in the yellow area at high temperature during which glaze layers are lost. It further results in abundant precipitation of Fe~(3+)in the form of hexagonal plate α-Fe_2O_3 crystal particle,which is also called micaceous iron oxide red being very important rust preventive and pearlescent pigment.
引文
[1]李家治.中国科学技术史[M].北京:科学出版社,1998.
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[3]赵静,李伟东,鲁晓珂.故宫琉璃瓦的保护研究[M].上海:上海科学技术出版社,2010.
[4]Lee H.The ruins of Yuanmingyuan:Or,how to enjoy a national wound[J].Modern China,2008,35(2):155-190.
[5]赵兴华.万园之园圆明园[J].江苏绿化,1995(6):16-17.
[6]岳升阳.颐和园、圆明园周边地区的历史文化与区域改造[J].北京联合大学学报(人文社会科学版),2004,2(1):39-45.
[7]王开玺.英军焚毁圆明园事件与“国际法”[J].北京师范大学学报(社会科学版),2012(2):55-65.
[8]杨根,高苏,王若昭,等.中国古代建筑琉璃釉色考略[J].自然科学史研究,1985(1):54-58.
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[10]Bo W,Gao F,Ma H.Preparation and XPS studies of macromolecule mixed-valent Cu(I,II)and Fe(II,III)complexes[J].Journal of Hazardous Materials,2007,144(1/2):363-368.
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[13]Muhler M,Schloegl R,Ertl G.Chem Inform abstract:the nature of the iron oxide-based catalyst for dehydrogenation of ethylbenzene to styrene.Part 2.Surface chemistry of the active phase[J].Cheminform,1993,138(14):413-444.
[14]Yamashita T,Hayes P.Analysis of XPS spectra of Fe2+,and Fe3+,ions in oxide materials[J].Applied Surface Science,2008,254(8):2 441-2 449.
[15]Mayer T.Black spots on carbon steel after contact to lubricating oil with extreme pressure additives:an XPS study[J].Applied Surface Science,2001,179(1):257-262.
[16]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].Applied Surface Science,1996,100/101(2):36-40.
[17]Mekki A,Holland D,Mcconville C F,et al.An XPS study of iron sodium silicate glass surfaces[J].Journal of NonCrystalline Solids,1996,208(208):267-276.
[18]马红钦,谭欣,朱慧铭,等.La1-xCexFe O3钙钛石高变催化剂的XPS研究[J].中国稀土学报,2003,21(4):445-448.
[19]曹智,叶红齐,周永华.片状氧化铁的特性、制备及应用[J].涂料工业,2003,33(7):53-55.
[20]王莉玮,袁占辉,林棋.新型片状氧化铁的合成以及在珠光颜料中的应用[J].闽江学院学报,2013,34(2):113-118.
[21]袁晰,叶红齐,刘辉.片状Fe2O3的制备及其生长机理[J].中南大学学报(自然科学版),2010,41(5):1 718-1 723.
[22]任冬寅,尚志新,盖国胜,等.冲击磨制备云母氧化铁及其重防腐涂料应用[J].中国粉体技术,2012,18(5):40-44.
[23]刘跃进,李振民,李功军,等.水热法合成云母氧化铁结晶条件[J].化工学报,2004,55(5):846-849.
[24]刘昭成.硫铁矿烧渣水热法制备云母氧化铁及其基础理论研究[D].长沙:中南大学,2011.
[25]王晓霞.熔盐法合成片状氧化铁粉体的研究[D].长沙:中南大学,2005.
[26]范凤松,张骞.云母氧化铁的合成及表征[J].有色金属科学与工程,2015,6(5):57-62.
[27]刘波,张深根,潘德安,等.一种冷轧铁泥制备云母氧化铁的方法:CN102923789A[P].2013-02-13.
[2]李庆全,刘建业.中国古代琉璃建筑技术[M].北京:中国建筑工业出版社,1987.
[3]赵静,李伟东,鲁晓珂.故宫琉璃瓦的保护研究[M].上海:上海科学技术出版社,2010.
[4]Lee H.The ruins of Yuanmingyuan:Or,how to enjoy a national wound[J].Modern China,2008,35(2):155-190.
[5]赵兴华.万园之园圆明园[J].江苏绿化,1995(6):16-17.
[6]岳升阳.颐和园、圆明园周边地区的历史文化与区域改造[J].北京联合大学学报(人文社会科学版),2004,2(1):39-45.
[7]王开玺.英军焚毁圆明园事件与“国际法”[J].北京师范大学学报(社会科学版),2012(2):55-65.
[8]杨根,高苏,王若昭,等.中国古代建筑琉璃釉色考略[J].自然科学史研究,1985(1):54-58.
[9]张福康.中国古陶瓷的科学[M].上海:上海人民美术出版社,2000.
[10]Bo W,Gao F,Ma H.Preparation and XPS studies of macromolecule mixed-valent Cu(I,II)and Fe(II,III)complexes[J].Journal of Hazardous Materials,2007,144(1/2):363-368.
[11]Hawn D D,Dekoven B M.Deconvolution as a correction for photoelectron inelastic energy losses in the core level XPS spectra of iron oxides[J].Surface&Interface Analysis,1987,10(2/3):63-74.
[12]Roosendaal S J,Asselen B V,Elsenaar J W,et al.The oxidation state of Fe(100)after initial oxidation in O2[J].Surface Science,1999,442(3):329-337.
[13]Muhler M,Schloegl R,Ertl G.Chem Inform abstract:the nature of the iron oxide-based catalyst for dehydrogenation of ethylbenzene to styrene.Part 2.Surface chemistry of the active phase[J].Cheminform,1993,138(14):413-444.
[14]Yamashita T,Hayes P.Analysis of XPS spectra of Fe2+,and Fe3+,ions in oxide materials[J].Applied Surface Science,2008,254(8):2 441-2 449.
[15]Mayer T.Black spots on carbon steel after contact to lubricating oil with extreme pressure additives:an XPS study[J].Applied Surface Science,2001,179(1):257-262.
[16]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].Applied Surface Science,1996,100/101(2):36-40.
[17]Mekki A,Holland D,Mcconville C F,et al.An XPS study of iron sodium silicate glass surfaces[J].Journal of NonCrystalline Solids,1996,208(208):267-276.
[18]马红钦,谭欣,朱慧铭,等.La1-xCexFe O3钙钛石高变催化剂的XPS研究[J].中国稀土学报,2003,21(4):445-448.
[19]曹智,叶红齐,周永华.片状氧化铁的特性、制备及应用[J].涂料工业,2003,33(7):53-55.
[20]王莉玮,袁占辉,林棋.新型片状氧化铁的合成以及在珠光颜料中的应用[J].闽江学院学报,2013,34(2):113-118.
[21]袁晰,叶红齐,刘辉.片状Fe2O3的制备及其生长机理[J].中南大学学报(自然科学版),2010,41(5):1 718-1 723.
[22]任冬寅,尚志新,盖国胜,等.冲击磨制备云母氧化铁及其重防腐涂料应用[J].中国粉体技术,2012,18(5):40-44.
[23]刘跃进,李振民,李功军,等.水热法合成云母氧化铁结晶条件[J].化工学报,2004,55(5):846-849.
[24]刘昭成.硫铁矿烧渣水热法制备云母氧化铁及其基础理论研究[D].长沙:中南大学,2011.
[25]王晓霞.熔盐法合成片状氧化铁粉体的研究[D].长沙:中南大学,2005.
[26]范凤松,张骞.云母氧化铁的合成及表征[J].有色金属科学与工程,2015,6(5):57-62.
[27]刘波,张深根,潘德安,等.一种冷轧铁泥制备云母氧化铁的方法:CN102923789A[P].2013-02-13.