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第 10 期 刘 琳，等: 二唑缓蚀膜的制备及抗腐蚀性能 ·1789·

进行了 Mulliken 电荷分布和 Fukui 指数的计算，结 到金属表面，阻断腐蚀介质向金属基底的移动，阻
果列于表 3。从表 3 可以看出，PPD 的 N13、N14 碍了金属腐蚀的发生。本文结果可指导筛选出具有
（13、14 为原子的编号）具有较大的亲电指数 Fukui 缓蚀性能的 S、N 杂环化合物，同时可对同类缓蚀
（+）数值，说明上述原子可能是亲电反应的活性位 剂分子结构加以恰当的修饰和改造以进一步增强缓
点；而 N13、N14 同时具有较大的亲核指数 Fukui 蚀性能。
（–）数值，说明原子也可能是亲核反应位点。N13
参考文献：
和 N14 同时具有较大的 Fukui（–）和 Fukui（+）数
[1] Chang Chunfang (常春芳), Zeng Weimin (曾为民), Ma Yulu (马玉
值，说明它们既可以提供电子形成配位键，也可以 录), et al. The corrosion inhibition effects of ATA and its complex
接受电子形成反馈键 [15] 。 with PASP on carbon steel in 3.5% NaCl solution[J]. Surface
Technology (表面技术), 2010, 39(6): 46-50.
[2] Li Xianghong (李向红), Deng Shuduan (邓书端), Fu Hui (付惠),
et al. Corrosion inhibition of cationic cassava starch graft copolymer
for steel in HCl solution[J]. Fine Chemicals (精细化工), 2017, 34(3):
319-325.
[3] Zhang Honghong (张红红), Xie Yan (谢彦), Liu Yuanwei (刘元伟),
et al. Inhibition of mild steel corrosion in hydrochloric acid solution
by salicylaldehyde thiosemicarbazone[J]. Chinese Journal of Applied
Chemistry (应用化学), 2015, 32(6): 720-725.
[4] Liu Linfa (刘林法), Liu Jinxiang (刘金祥), Zhang Jun (张军), et al.
Molecular dynamics simulation of the corrosive medium diffusion
behavior inhibited by the corrosion inhibitor membranes[J]. Chemical
Journal of Chinese Universities (高等学校化学学报), 2010, 31(3):
537-541.
[5] Kong Desheng (孔德生), Wan Lijun (万立骏), Chen Shehao (陈慎
图 8 PPD 分子的最优构型、HOMO 和 LUMO 豪 ), et al. Progress in STM study of corrosion inhibitor
Fig. 8 Optimized molecular structures, HOMO and LUMO self-assembled monolayers (SAMs) on metals[J]. Corrosion &
Protechion (腐蚀与防护), 2003, 24(10): 415-420.
表 3 PPD 量化计算参数 [6] Schreiber F. Structure and growth of self-assembling monolayers[J].
Table 3 Quanturn chemistry parameters of corrosion inhibitor Progress in Surface Science, 2000, 65(5): 151-257.
PPD [7] Liu Lin (刘琳), Yu Zhuohan (俞卓汗), Zhang Siqian (张思倩).
Research on the inhibition performance of rare-earth cerium
原子 电荷 Fukui（–） Fukui（+）
conversion film for X70 pipeline steel in carbon dioxide-saturated
C12 0.412 0.059 solution[J]. Materials Review: Research (材料导报 B: 研究篇),
N13 –0.254 0.076 0.058 2013, 27(12): 107-109.
N14 –0.252 0.075 0.058 [8] Liu Liu (刘柳), Cao He (曹贺), Zhang Chen (张晨), et al. Inhibition
performance of aspartic acid and schiff base[J]. Journal of Shenyang
C15 0.412 0.059
University of Chemical Technology (沈阳化工大学学报), 2013,
O16 –0.437 27(4): 297-301.
注：表中只列出 Fukui 数值较大的数据。 [9] Shubha H N, Venkatesha T V, Pavithra M K, et al. Surface
modification of mild steel by a self-assembled cetyl-trimethyl
3 结论 ammonium bromide (CTAB) monolayer: Evaluation of its corrosion
protection property[J]. Progress in Organic Coatings, 2016, 90(5):
267-276.
（1）合成产物 2,5-二苯基-1,3,4-二唑(PPD)在碳 [10] Qian Jianhua (钱建华), Zhang Siqian (张思倩), Liu Lin (刘琳), et al.
钢表面自组装形成 PPD 分子膜，通过对缓蚀膜的表 Corrosion inhibition of copper by L-lysine acid self assembled
征和电化学测试得到以下结论：随着 PPD 溶液浓度 monolayers[J]. Materials Review: Research (材料导报 B: 研究篇),
2015, 29(3): 98-106.
和组装时间的增加，缓蚀效率增大，最佳组装条件 [11] Ibrahim A A, El-Mossalomy E H. Synthesis and characterization of
为：室温下，在 4 mmol/L 组装液中组装 12 h，缓蚀 Cu (Ⅱ) complexes with some thiazole dye derivatives and its
application in corrosion inhibition[J]. Pigment & Resin Technology,
效率高达 91.95%。
2002, 31(6): 375-380.
（2）吸附热力学分析表明，PPD 在钢表面的吸 [12] Balaskas A C, Curioni M, Thompson G E. Effectiveness of
附遵循 Langmuir 吸附等温方程。金相显微镜及 XPS 2-mercaptobenzothiazole, 8-hydroxyquinoline and benzotriazole as
corrosion inhibitors on AA 2024-T3 assessed by electrochemical
测试结果显示，PPD 在碳表面形成了保护膜，能有 methods[J]. Surface & Interface Analysis, 2015, 47(11): 1029-1039.

效抑制 Cl 对碳钢的腐蚀，在海水和油田水环境中具 [13] He Y, Yang R, Zhou Y, et al. Water-soluble thiosemicarbazide-
有较好的应用前景。 imidazole derivative as an efficient inhibitor protecting P110 carbon
steel from CO 2 corrosion[J]. Anti-Corrosion Methods and Materials,
（3）量化计算结果表明，PPD 分子中的 N 原子 2016, 63(6): 437-444.
具有较强的电荷和亲电/亲核活性，从而稳定地吸附 [14] Guo Rui (郭睿), Cheng Min (程敏), Li Xiaofang (李晓芳), et al.