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银币表面自组装膜抗变色性能及成膜机理

Anti-tarnish Characteristics and Formation Mechanism of Self-Assembled Monolayers on Surface of Silver Coins

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【作者】 梁成浩杨长江黄乃宝金光明

【Author】 Liang Chenghao 1 , Yang Changjiang 2 , Huang Naibao 1 , Jin Guangming 1 (1.Dalian Maritime University, Dalian 116026, China) (2.Kunming University of Science and Technology, Kunming 650093, China)

【机构】 大连海事大学昆明理工大学

【摘要】 利用化学方法在银币表面制备了十八烷基硫醇组装膜(C18SHSAMs),并通过电化学技术研究了其在0.5mol/LNaCl+0.01mol/LNa2S溶液中的抗变色性能。结果表明:银表面形成SAMs后腐蚀电位正移30mV;阴极氧去极化和阳极银的硫化过程均受到抑制,对阴极极化过程的阻滞作用较阳极极化过程明显;银表面成膜后,容抗弧、电荷传递系数Rt增大,双电层电容Cd降低。有效提高银币的抗变色性能。银表面C18SHSAMs的形成过程符合两阶段模型。膜初始吸附阶段(I)为2级Langmuir吸附,重整结晶阶段(Ⅱ)为1级Langmuir吸附,动力学公式分别为,Ⅰ阶段:ctctt11.7061.706,Ⅱ阶段:0.5471ectt。速率常数与温度的关系为ln(k)=–5826/T+26.5,自组装过程表观活化能E=48.4kJ/mol,化学吸附为控制步骤。

【Abstract】 Octadecanethiol (C18SH) self-assembled monolayers (SAM) were prepared on the silver coin surface.The anti-tarnish characteristics of C18SH SAMs were investigated in 0.5 mol/L NaCl+0.01 mol/L Na 2 S solution by an electrochemical technique.The results indicate that silver’s corrosion potential moves by 30 mV to positive direction after forming SAMs.C18SH SAMs could inhibit oxygen depolarization and silver sulfuration.The inhibition effect for cathode process is better than that for anode.After SAMs is formed on the surface of silver, the silver coin’s charge-transfer resistance increases and double layer capacitance decreases.The formation of SAMs on silver is in accordance with a two-phase model.In the initial stage, the adsorption obeys two grade Langmuir equation, which is 1.7061 1.706 ct t ct.In the latter stage, the adsorption is the process of reforming and recrystallization, and is in accordance with one grade Langmuir equation, which is 0.5471 ct te.The relationship between rate constant and temperature is ln(k)=–5826/T+26.5 during absorption.The apparent activation energy of self-assembled process is 48.4 kJ/mol and the self-assembled process is controlled by chemical adsorption.

【基金】 国家高技术研究发展计划项目(2009AA05Z120)
  • 【文献出处】 稀有金属材料与工程 ,Rare Metal Materials and Engineering , 编辑部邮箱 ,2013年07期
  • 【分类号】TG174.4
  • 【被引频次】4
  • 【下载频次】185
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