青铜文物腐蚀过程的模拟研究

中国腐蚀与防护学报

2006, Vol. 26

Issue (2): 94-99

研究报告

本期目录 | 过刊浏览

青铜文物腐蚀过程的模拟研究

张展适;陈少华;陈障茹;刘月妙

东华理工学院地球科学与资源信息管理系

SIMULATION STUDY ON THE CORROSION PROCESSES OF UNEARTHED BRONZE RELICS

Zhanshi Zhang;Shaohua Chen;Zhangru Chen;Yuemiao Liu

东华理工学院地球科学与资源信息管理系

全文: PDF(188 KB)

摘要: 采用地球化学模式程序EQ3/6，研究了青铜器蚀变过程.模拟结果表明，在土壤中常见的E h和pH及研究区的年平均温度条件下，溶液中铜离子的含量达到一定的浓度时，可以生成赤铜矿(当Cu≈00016 mol/L)、孔雀石及黑铜矿(当Cu≈0 0079mol/L)等次生矿物，溶液中Cu的存在形式也发生了变化，即CuCO3(aq)所占的比例不断减小，而Cu2+和CuO H+的含量则相继增高，且Cu2+的增幅大于CuOH+.青铜制品中的Cu在不同的E h和pH条件下腐蚀的产物是不同的.在研究的Eh(-02 V～07 V)和pH值(5～95) 范围内，赤铜矿的形成不受氧化—还原电位及酸碱度变化的影响；孔雀石和黑铜矿形成于较高pH值(>7)和较高的氧化—还原电位(>02 V)条件；而辉铜矿则形成于较低的pH值(<7) 和较低的Eh(<02 V)条件.水－青铜器相互作用的模拟研究结果表明，在作用过程中将依次生成赤铜矿、孔雀石、黑铜矿、白铅矿、锡石及在合金内层残留的自然Cu、Pb和Zn.在这一过程中溶液中Cu和Pb的含量逐渐降低，但Zn的行为则与Cu、Pb相反，即随着合金的溶解在溶液中的含量增加了.在上述模拟结果基础上，建立了青铜器腐蚀的化学作用过程，即青铜器的腐蚀大致可分为两个阶段：第一阶段生成黑铜矿和孔雀石，第二阶段生成白铅矿和锡石等矿物.上述模拟研究结果与现有的测定结果相吻合，同时还揭示了现有的常规研究所不能揭示的腐蚀过程，由此说明不仅可以应用地球化学模式程序来研究青铜器的腐蚀产物，还可以揭示青铜类文物的腐蚀过程及机理.

关键词 ：青铜器, 腐蚀产物, 腐蚀过程, 模拟研究, EQ3/6

Abstract：Modeling study of corrosion processes of unearthed bronze relics was preformed b y EQ3/6,a software package for geochemical modeling of aqueous system.It was rev ealed that:cuprite,malachite and tenorite are the three main kinds of copper-bea ring minerals which would be supersaturated when Cu concentration in the solutio n is high enough(higher than 0.0016 mol/L,0.0079 mol/L separately) under the stu dy conditions.Copper exists in the solution mainly as the species of CuCO3(aq) ,Cu2+ and CuOH+.The corresponding content of CuCO3(aq) would be decrea sed following the deposition of the copper-bearing minerals,nevertheless,Cu2 + and CuOH+ would be increased.The species of Cu and the saturation index of the copper-bearing minerals would be greatly affected by the Eh and pH va lues of the solution.Cuprite is supersaturated in the studied Eh and pH co nd ition(Eh=-0.2 V～0.7 V,pH=5～9.5).Malachite and tenorite are supersatura ted under the conditions Eh>0.2 V,pH>7,while chalcocite is supersaturated under the con d ition of pH<7 and Eh<0.2 V.Water-bronze interaction has been revealed that cuprite,malachite,tenorite,cerussite,cassiterite,copper,lead and tin would be f ormed in a sequence from the early stage to the later stage of the reaction.The simulation calculation also showed the different behavior between Cu and Zn.It h as demonstrated that Cu was leached off easily and the corresponding content in outer corrosion layer is lower than the interior layer,but Sn is just contrary. It is believed the corrosion processes of bronze could be divided into two stag es:at the first stage,cuprite,malachite and tenorite were formed;cassiterite ,cerussite and relic copper,lead and tin were formed in the second stage,which c an be found in the outer layer of bronze.The simulation result not only fixed th e natural corrosion products,but revealed the corrosion processes also which we could not understand by routine methods.So the geochemical modeling study can be used to simulate the bronze corrosion prod uct and its corrosion processes also.

Key words： bronze relics corrosion product corrosion process simulation study EQ3/6

收稿日期: 2005-01-10

ZTFLH:

P59

通讯作者: 张展适 E-mail: zhszhang@ecit.edu.cn

Corresponding author: Zhanshi Zhang E-mail: zhszhang@ecit.edu.cn

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引用本文:

张展适; 陈少华; 陈障茹; 刘月妙 . 青铜文物腐蚀过程的模拟研究[J]. 中国腐蚀与防护学报, 2006, 26(2): 94-99 .
Zhanshi Zhang, Shaohua Chen, Zhangru Chen, Yuemiao Liu. SIMULATION STUDY ON THE CORROSION PROCESSES OF UNEARTHED BRONZE RELICS. J Chin Soc Corr Pro, 2006, 26(2): 94-99 .

链接本文:

https://www.jcscp.org/CN/ 或 https://www.jcscp.org/CN/Y2006/V26/I2/94

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