CAJ | 학술논문

青铜器锈蚀研究能够揭示出青铜器腐蚀机理，为制定科学的保护措施提供重要的参考资料。目前，青铜器锈蚀研究主要从其外部锈蚀产物入手，通过锈蚀组成结构分析，探讨其腐蚀机理。本文选择了保存较好青铜器本体样品进行了内部锈蚀情况研究。首先采用金相制备技术，通过打磨、抛光和超声清洗处理后，制备了断面相组织形态清晰的24件秦早期青铜器青铜本体样品。然后利用共聚焦显微拉曼光谱仪对样品夹杂物进行了光谱学研究，发现其物相为PbCO3和PbO及Cu2 O ，都属于常见的青铜合金腐蚀产物。样品金相组织中圆形或者大面积无规则亮灰色区域为C u2 O ，反映出青铜器表面不仅易于形成一定厚度C u2 O锈蚀层，在相界之间也容易发生氧化反应生成C u2 O ，存在合金内部和外部同时发生腐蚀生成赤铜矿锈蚀的情况。此外，拉曼光谱分析显示黑灰色物质主要为铅腐蚀产物———PbCO3和PbO ，反映出铅元素的腐蚀过程：Pb→PbO→PbCO3。在铸造态青铜合金组织中，铅一般呈近圆形颗粒状态分布在相界之间。青铜器内部分布的铅颗粒在土壤埋藏环境中会发生氧化反应生成PbO ，再与地下水中溶解的CO2－3发生化学反应生成比较稳定的PbCO3。结果表明：外界腐蚀因素（水、溶解氧和碳酸根等）能够通过合金中相界间通道进入青铜器内部，在相界表面逐步发生反应形成以金属氧化物为主的腐蚀产物。
청동기수식연구능구게시출청동기부식궤리，위제정과학적보호조시제공중요적삼고자료。목전，청동기수식연구주요종기외부수식산물입수，통과수식조성결구분석，탐토기부식궤리。본문선택료보존교호청동기본체양품진행료내부수식정황연구。수선채용금상제비기술，통과타마、포광화초성청세처리후，제비료단면상조직형태청석적24건진조기청동기청동본체양품。연후이용공취초현미랍만광보의대양품협잡물진행료광보학연구，발현기물상위PbCO3화PbO급Cu2 O ，도속우상견적청동합금부식산물。양품금상조직중원형혹자대면적무규칙량회색구역위C u2 O ，반영출청동기표면불부역우형성일정후도C u2 O수식층，재상계지간야용역발생양화반응생성C u2 O ，존재합금내부화외부동시발생부식생성적동광수식적정황。차외，랍만광보분석현시흑회색물질주요위연부식산물———PbCO3화PbO ，반영출연원소적부식과정：Pb→PbO→PbCO3。재주조태청동합금조직중，연일반정근원형과립상태분포재상계지간。청동기내부분포적연과립재토양매장배경중회발생양화반응생성PbO ，재여지하수중용해적CO2－3발생화학반응생성비교은정적PbCO3。결과표명：외계부식인소（수、용해양화탄산근등）능구통과합금중상계간통도진입청동기내부，재상계표면축보발생반응형성이금속양화물위주적부식산물。
The present paper analyzes the interior rust that occurred in bronze alloy sample from 24 pieces of Early Qin bronze wares .Firstly ,samples were processed by grinding ,polishing and ultrasonic cleaning to make a mirror surface .Then ,a confo-cal micro-Raman spectrometer was employed to carry out spectroscopic study on the inclusions in samples .The conclusion indi-cated that corrosive phases are PbCO3 ,PbO and Cu2 O ,which are common rusting production on bronze alloy .The light-colored circular or massive irregular areas in metallographic structure of samples are proved as Cu2O ,showing that bronze wares are not only easy to be covered with red Cu2 O rusting layer ,but also their alloy is easy to be eroded by atomic oxygen .In other words , the rust Cu2 O takes place in both the interior and exterior parts of the bronze alloy .In addition ,Raman spectrum analysis shows that the dark grey materials are lead corrosive products ———PbCO3 and PbO ,showing the corroding process of lead element as Pb→PbO→PbCO3 .In the texture of cast state of bronze alloy ,lead is usually distributed as independent particles between the dif-ferent alloy phases .The lead particles in bronze alloy would have oxidation reaction and generate PbO when buried in the soil , and then have chemical reaction with CO2 -3 dissolved in the underground water to generate PbCO3 ,which is a rather stable lead corrosive production .A conclusion can be drawn that the external corrosive factors (water ,dissolved oxygen and carbonate ,etc) can enter the bronze ware interior through the passageway between different phases and make the alloy to corrode gradually .