Abstract: The elemental composition and chemical states of the surface film of silver-electroplated deposits with different treatment and aging time have been investigated by means of XPS and AES. The results showed: ( 1 ) Fresh deposit U0, stored indoors in a transparent desiccator for 5 days, was composed of the elements silver, oxygen, sulphur, chlorine and the matrix metal copper in addition to contaminating elements carbon, potassium and nitrogen; the content of elemental silver of a series of untarished deposits U0 and U1 decreased steadily with time, while elemental oxygen increased almost linearly. ( 2 ) The distributions of the elements silver and oxygen of deposit U1, treated with NaCl solution, were the same in Auger line scan, but for deposit U2, treated with Na2S solution, the coexistence regions of the elements silver and sulphur partly replaced those of silver and oxygen.The atomic ratio of S/Ag differed with the treatment of the silver deposit. The ratios for deposit U3, stored indoors in a transparent desiccator for 500 days, and for deposit Ts,stored indoors in a transparent desiccator containing air with 1% H2S for 24 hours, were much greater than that for deposit T1 which is exposed to sunlight outdoors for 24 hours. ( 3 ) The two dimensional Auger parameter plot showed that Ag2O amounted to 19% of the total silver in deposit T1, and was practically nil in deposit U0. (4) The anti-tarishing ability of fresh deposit increased markedly after treatment with certain reducing or complexing agents. Based on these results, the tarnishing mechanism and anti-tarishing principle were discussed.

摘要： 用电子能谱(XPS和AES)研究了不同处理与历程的镀银层表面膜的元素组成和化学态,结果表明:(1)于干燥器内存放5天后的新鲜镀层(U_O)由元素银、氧、硫、氯和基底金属铜和沾污元素碳、钾和氮组成,随着存放时间增加,一系列未变色镀层(U_O与U_1)的元素银含量有规律地减少而氧几乎线性增加;(2)用NaCl溶液处理的镀层(U_1)的元素银、氧的分布在AES线扫描中一致,而用 Na_2S处理的镀层(U_2)的元素银、硫共存区部分取代了银、氧共存区,硫银原子比按下列顺序递减,即:室内干燥器内500天后的镀层(U_3)及室内干燥器内含1%H_2S的大气中24小时后的镀层(T_s)大于暴露室外大气中日光下24小时后的镀层(T_1);(3)由两维俄歇参数图发现在T_1已上面有19%的银为Ag_2O,而U_o上面仅有少量;(4)新鲜镀层用某些还原剂或络合剂处理后的防变色能力明显增加. 依据上述结果讨论了变色机理和防银变色原则.