“黑漆古”耐腐蚀机理探讨

“黑漆古”铜镜的表面由非金属层和过渡层组成,价电子结构分析指出,非金属层主要成分Sn_1-xCu_xO₂具有与SnO₂相近的稳定性,而实验数据分析发现,过渡层中,δ相铜锡合金与Sn_1-xCu_xO₂的相界上存在着重合位置点阵(CSL)结构,这种结构降低了相界面上铜原子的能量,使这部分δ相晶粒也十分稳定,从而使整个“黑漆古”表面具有耐腐蚀性能。 关键词：     

蔡侯编钟的粉状锈研究

“粉状锈”被称为青铜文物的“癌症”,多少年来,国内外有关专家对于粉状锈的控制和根治始终未能取得明显的进展。本文详细介绍了用XRD,SEM,TEM以及XRFA等方法分析一块被粉状锈严重腐蚀的蔡侯编钟残片的结果,指出粉状锈的主要成分是氯铜矿(Cu_2(OH)_3C1)、赤铜矿(Cu_2O)以及结晶状况甚差的锡石(SnO_2)。而编钟基体内存在的和粉状锈成分相同的腐蚀沟漕,则表明粉状锈腐蚀是一种晶间腐蚀过程。显然,这一发现对粉状锈的形成机理研究有着十分重要的意义。     

A Study on Kinetics of the Bronze Powder-Corrosion Development

HCl acid was applied to the surface of the self-prepared Cu-Sn-Pb alloy, and the methods of IR-REF, IR-PAS, XRD, SPM, SEM, TEM and pH were employed to study the forming process and the developing speed of the bronze powder-corrosion Cu_2(OH)_3Cl (PC). It is found that the corrosion develops fast in acid environment at room temperature; the corrosion Cu_2(OH)_3Cl with valence Cu~(2+) forms from alloy through the intermediate corrosion CuCl with valence Cu~+; PC is contagious, which can pollute the fresh bronze alloy from the corroded sample by air; when CuCl is oxidized to produce Cu_2(OH)_3Cl, Cu~(2+) cation forms at the same time, and both the oxidizing reactions have zero-order reaction with respect to O_2 in the air; the P1 formation reaction has first-order reaction with respect to Cull; in enormous distilled water Cu_2(OH)_3Cl forms from CuCl through the intermediate product Cu_2O.All the results above are discussed in the present article, and the mechanism of PC formation is studied further. The r     

等离子TLC-DSERS应用于多环芳烃的检测研究

多环芳烃(PAHs)作为一种持久性有机污染物,不仅污染生态环境还危害人体健康。因此,PAHs的鉴别至关重要。本研究建立一种高灵敏度的等离子体薄层色谱(pTLC)与动态表面增强拉曼光谱(DSERS)联用的方法,现场检测食用油中嵌二萘。混合样品中的PAHs在pTLC芯片上被有效分离,并在紫外光下可视化,然后在便携式拉曼光谱仪上进行DSERS检测。此外,固定相的等离子体特性可以增强PAHs的荧光并且较小的金纳米粒子可以提供更高的分离效率和更低的理论塔板高度。pTLC-DSERS方法的灵敏度低至0.1 ppb,比TLC-SERS方法高近4个数量级。结果表明,pTLC-DSERS方法具有对混合物中的PAHs快速分离和灵敏检测的潜力。     

RESEARCH ON POWDERY CORROSION OF THE SERIALS BELLS FROM CAI HOU TOMB

"Powdery corrosion" is called "cancer" of cultural relics of bronze. For many years theexperts concerned at home and abroad cannot make distinct progress in the control or cure ofpowdery corrosion. This paper introduces in detail analyses of XRD, SEM. TEM and XRFA on afragment of serials bells with serious powdery corrosion from the Cai Hou Tomb, pointingout that the components of powdery corrosion are mainly atacamite (Cu_2(OH)_3Cl), cuprite(Cu_2O) and cassiterite (SnO_2) in the worse crystalline state. In the bell's matrix, there arecorrosion gullies which has the same phase components as the powdery corrosion. Obviously,this discovery has very important significance for studying the formation mechanism ofpowdery corrosion.     

青铜器粉状锈生长过程的动力学研究

在Cu-Sn-Pb合金表面用盐酸腐蚀加工,并采用红外反射光谱(IR-REF)、红外光声光谱(IR-PAS)、X射线衍射(XRD)及分光光度(SPM)等分析方法研究粉状锈(Cu_2(OH)_3Cl)的生长过程和发展速度。结果表明,在酸性环境中锈体生长迅速;二价铜锈的生成需通过一价铜锈(CuCl)这一中间产物;粉状锈有传染性;CuCl在水中继续氧化生成Cu_2(OH)_3Cl的同时,有Cu~(2+)离子伴随产生。本文计算了锈体生长的反应级数、速度常数及表现活化能,对反应机理及伴随现象进行了探讨。     

青铜器粉状锈生成机理研究

摸拟自然界条件,在仿古青铜合金表面进行人工腐蚀,得到与古青铜器粉状锈类似的化学物质.对粉状锈的生成条件进行分析,认为氯化物、水份及氧化气氛是基本要素,而氯离子的存在是关键. 本工作始终保持对试样的结构及成分进行监测,有利于揭示事物的真象. 本文以实验及热力学计算结果为依据,对粉状锈形成的化学机理进行了探讨,认为粉状锈的延展迅速是由于两个恶性化学循环的结果.     

A STUDY ON THE CHEMICAL MECHANISM FOR POWDER CORROSION OF BRONZE ALLOY

A Cu-Sn-Pb alloy modelled after an antique was cast and the powder-corrosion (P-C) was prepared on it under simulated natural conditions. The main components of the corrosion are much like those of the ancient bronze powder corrosion. It is found that chloride, water and oxygen are the essential factors for P-C formation of which chlorine plays the most important role. According to the results of expriments and thermodynamic calculations, the chemical mechanism of the copper desease was studied. It is pointed out that the fast spread of P-C is caused by two vicious circles.     

氯化亚铜氧化反应的化学动力学初探

多数被发掘的古代青铜文物表面都附着有某些钢锈,其中以粉状锈(Cu_2(OH)_3Cl)对铜器的腐蚀最为严重.迄今已有一些文献介绍粉状锈的生成机理,但对其反应过程的动力学研究尚未见报导。作为青铜合金中含量最丰的元素铜,被氧化腐蚀是分步进行的.本工作主要用X-光衍射及分光光度法对一价铜锈CuCl在潮湿环境中进行氧化反应的速度常数及表观活化能进行测定核算;对反应的中间产物及伴随现象进行分析探讨。