Electrochemical Studies on Corroding Metallic Electrodes in Frequency Domain

腐蚀金属电极的电化学频域测量研究进展──金属腐蚀与防护研究所电化学研究介绍之一曹楚南（金属腐蚀与防护国家重点实验室，金属腐蚀与防护研究所，沈阳１１００１５）腐蚀电化学是研究与腐蚀有关的电化学问题，具体的研究对象为腐蚀金属电极。虽然电化学中的基本原理和...The electrochemical studies on corroding metallic electrodes carried out in the State Key Laberatory for Corrosion and Protection are reviewed briefly: (1) General equations of faradaic admittance under potential-control condition were derived based on the stabillity conditions of steady processes. The faradaic admittance at mixed potential then was deduced based on these equations and the electrochemical impedance spectroscopy (EIS) at corrosion potentials in the solutions containing interface inhibitors was diseussed by application of the thecetical results obtained. (2) The spectral power density (SPD) curves for electrochemical noise (EN) during the initial stagu of pitting corrosion were observed for iron and stainless steels in various solutions. In all the svstems studied, the EN is "white" noise at very low frequencies and is f-n noise in higher frequency range. The value of n is within the range from 2 to 4. An equation for the SPD of the EN was derived and the observed phenomena were well elucidated.作者联系地址：沈阳金属腐蚀与防护国家重点实验室Author's Address: State Key laboratory for Corrosion and Protection of Metals, Institute of Corrosion and Protection of Metals, Academia Sinica, Wencui Road, Shenyang 11001

The Inhibition and Desorption Behavior of N,N-dipropynoxy Methyl Amine Trimethyl Phosphonate in Hydrochloride Acid

采用稳态极化曲线和交流阻抗测试技术研究了环己基二炔氧甲基胺氨基三甲撑膦酸盐在盐酸介质中的缓蚀作用机理和阳极吸脱附行为。对极化曲线实验数据按弱极化曲线模式进行拟合。研究结果表明，环己基二炔氧甲基胺膦酸盐在盐酸介质中的缓蚀机理为覆盖效应。吸附等温式符合Ｆｒｅｕｎｄｌｉｃｈ等温式。随缓蚀剂的脱附，阻抗谱在低频区出现感抗弧，且随脱附的进行而增大。The performance of inhibition mechanism and desorption behavior of the N,Ndipropynoxy methyl amine trimethyl phosphonate for iron in hydrochloride acid were investigated by means of static polarization and electrochern ical impedance spectroscopy technique.The data of the polarization curves were fitted by weak-polarization fitting technique.The results show that N,Ndipropynoxy methyl amine trimethyl phosphonate possesses high inhibiting efficiency and geometric blocking effect.It is also showed that this inhibitor obeys the Frendulich adsorption isotherm.With the increase of anodic potential,a low-frequency induce arc was observed.作者联系地址：中国科学院金属腐蚀与防护研究所Author's Address: State Key Laboratory for Corrosion and Protection,Institute of Corrosion and Protection of Metals,Chinese Academy of Sciences,Shenyang 11001

A Photoelectrochemical Investigation of A.C.Modulated Passive Films on 304 Stainless Steel in Weak-alkaline and Neutral Solution

采用光电化学方法—恒电位光电流测量技术研究了ＡＩＳＩ３０４不锈钢在０．ｌｍｏｌ／ＬＮａ＿２Ｂ＿４Ｏ＿７及０．５ｍｏｌ／ＬＮａ＿２ＳＯ＿４介质中载波钝化膜，光电流测量结果表明：光电流大小与电极电势、成膜条件及测量介质有关．载波钝化膜基本上是高度无序的非晶态膜．A photoelectrochemical investigation has been carried out on AISI 304 stainlesssteeI AV modulated passive film in 0.1mol/L Na_2B_4O_7 and 0.5 mol/L Na_2SO_4 solution.Photocurrentcurve depends on the potential、passive condition and testing solutions. The results of the measurementsindicate that the photoresponse is determined by the defects in the electronic structure of the films whenthe defects lead to localized states in the bandgap region. It is concluded that the passive film on AISI304 stainless steel is in a highly disordered amorphous state.作者联系地址：中国科学院金属腐蚀与防护研究所，金属腐蚀与防护国家重点实验室Author's Address: State Key Laboratory for Corrosion and Protection,Institute of Corrosion and Protection of Metals,Chinese Academy of Sciences,Shenyang 11001

Cyclic Voltammetric Investigation of the Axial Coordination Effects of Pyridine on the Redox Behaviours of (TPP)Co

本文考察了吡啶（Ｐｙ）对（ＴＰＰ）Ｃｏ在１，２－二氧乙烷中的电化学氧化还原行为的影响，观察到当存在一定量Ｐｙ时，Ｃｏ（Ⅲ）／Ｃｏ（Ⅱ）还原过程出现两个还原峰，分别在０．２５和－０．４０Ｖ（ｖｓ．ＳＣＥ）两处．由于吡啶在电极表面的吸附，在远小于形成二轴向Ｐｙ配合物的加入量时，Ｃｏ（Ⅲ）／Ｃｏ（Ⅱ）还原过程表现出了二个吡啶轴向配合物的伏安行为．证明在０．２５Ｖ与－０．４０Ｖ两个还原峰分别对应于一个和两个Ｐｙ分子配位的Ｃｏ（Ⅲ）／Ｃｏ（Ⅱ）还原峰．本工作还观察到了Ｃｏ（Ⅱ）／Ｃｏ（Ⅰ）还原受吡啶影响的伏安图变化过程，证实在－１．２Ｖ（ＳＣＥ）的还原峰是（ＴＰＰ）Ｃｏ（Ｐｙ）的直接电极还原．给出了Ｐｙ存在下（ＴＰＰ）Ｃｏ金属中心电化学氧化还原电位发生负移的机理．The electrochemistry of (TPP)Co in presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. Upon the addition of pyridine to the solution, two reduction peaks of Co(Ⅲ)/Co(Ⅱ) at 0.25 and -0.40 V (SCE) were observed. It was infered that the peaks were belong to the reductions of the complex compounds with one and two axial pyridine, (TPP)Co(Ⅲ)(Py) and (TPP)Co(Ⅲ)(Py)2. Even though the mole ratio of added pyridine was less than 1 the reduction of Co(Ⅲ)/Co(Ⅱ) still mainly occured at -0.40 V, which evidently resulted from pyridine adsorption on the electrodes. Besides, it was observed that the reduction peak of Co(Ⅱ)/Co(Ⅰ) was shifted to -1.20 V (SCE) with large amount of added pyridine. The new reduction peak could be attributed to the direct reduction of the axially coordination complex (TPP)Co(Ⅱ)(Py). The mechanisms of the effect of pyridine on the electrochemical redox behaviours of (TPP)Co were given.作者联系地址：中国科学院金属腐蚀与防护研究所金属腐蚀与防护国家重点实验室,中国科学技术大学化学系Author's Address: a State Kay Lab. for Corrosion and Protection, Inst. of Corrosion and Protection of Metals, Chinese Academy of Sciences, shenyang 110015b Dept. of chem., Univ. of

The Memory Effect of MH-Ni Battery

放电深度 (DOD)、放电速率、循环次数对MH Ni电池的记忆效应影响很大 .经过几次全充放循环可以消除记忆效应 .记忆效应的存在与Zn无关 .电池在低DOD循环过程中 ,其放电电位、放电容量一开始下降很快 ,然后逐渐趋于某一值 ,并且放电电流越小 ,相应的最高充电电压越低 .若放电电流增加 ,在随后的第一周充放电过程中最高充电电压迅速增加、放电容量显著小于稳定值 .最后探讨了导致记忆效应的原因 ,并给出了若干消除或减弱记忆效应的设想The memory effect of MH Ni battery was investigated. The depth of discharge, discharge rate and cycle number influence the memory effect greatly. A few completely full charge/discharge cycles could eliminate it. The existence of the memory effect had nothing to do with zinc element. During the course of life cycling at low DOD (degree of discharge),the smaller the discharge current was, the lower was the maximum charge voltage. In addition, discharge voltage and discharge capacity drop fast at the beginning, gradually leveled off at about a value. If the discharge current was increased, the discharge capacity was obviously less than the stabilized value and maximum charge voltage was also changed suddenly. At last, the cause of the memory effect is discussed, and tentative recommendations to eliminate or mitigate the appearance of the memory effect phenomena are given.作者联系地址：浙江大学化学系!浙江杭州310027,浙江大学化学系!浙江杭州310027,浙江大学化学系!浙江杭州310027,浙江大学化学系!浙江杭州310027Author's Address: Dept. of Chem., Zhejiang Univ., Hangzhou City, 310027, Chin

光电催化降解磺基水杨酸的研究

建立了以利浆工艺制得的ＴｉＯ２／Ｎｉ为工作电极、泡沫镍为对电极、饱和甘汞电极为参比电极的光电催化反应体系，研究了在磺基水杨酸（ＳＳａｌ）的光电催化降解过程中，外加才溶液ｐＨ值对降解的影响。实验发现，外加阳极偏压为７００ｍＶ时，ＳＳａｌ能发生有效降解，降解速率受溶液ｐＨ值的影响；随着ＳＳａｌ降解的进行，阳极表面电阻出现较大的变化。另外还研究了ＳＳａｌ光电催化降解过程中的电流变化特征

The Effects of Metallic Cobalt Abbition on the Performance of Pasted Nickel Electrodes

活 性物质 为化学共 沉积锌的 Ｎｉ（ Ｏ Ｈ） ２ ，并 物理 掺杂 钴粉 的泡 沫镍 涂 膏式 镍电 极 表现出高的 放电比 容量和循 环稳定性 ，其中 钴 可以 显著 提 高镍 电 极活 性物 质 利用 率， 这是 由于 第 一次活化充 电时由 Ｃｏ 形 成导电 性能良好 的 Ｃｏ Ｏ Ｏ Ｈ 提高了放 电深度， 循环过程 中的容量 稳定 性是 锌和钴协同 作用的 结果，特别 是共沉 积锌，它可 以抑制 γ＿ Ｎｉ Ｏ Ｏ Ｈ 的形成 从而缓 解镍电极 的膨胀 ．The Ni_foam pasted nickel electrodes prepared by coprecipitated Ni 1_X Zn X(OH) 2 with and without cobalt power addition have been studied. The electrode with addition of metallic cobalt showed a higher performance both in discharge capacity and cycle life.It is known from the experiment results that the addition of Co can remarkably increase the active material utilization which is suggested to be improvement of discharge depth due to the conducting CoOOH formed in the first activation charging.The superior capacity during cycling could be attributed to the synergistic action of zinc and cobalt addition,especially to the coprecipitatation of zinc hydroxide which is suggested to be the inhibition of γ_NiOOH formation.作者联系地址：浙江大学化学系!杭州310027,浙江大学化学系!杭州310027,浙江大学化学系!杭州310027,浙江大学化学系!杭州310027,浙江大学化学系!杭州310027Author's Address: Dept.of Chem.,Zhejiang Univ.,Hangzhou 31002

Corrosion Performance of Epoxy Coatings by Chemical Modification with Silanes

利用"活性"与"非活性"硅烷化学改性环氧涂层以提高其耐蚀性."活性"硅烷指含有可以与环氧树脂的环氧端基发生开环反应官能团的硅烷,通常为氨基硅烷;"非活性"硅烷指不与环氧端基发生反应,但在有机锡催化剂存在下可与环氧树脂骨架上的羟基发生缩合反应的硅烷.红外光谱显示,两类硅烷均可成功接枝在环氧树脂上.电化学阻抗谱(EIS)和加速腐蚀试验(Machu试验)测试表明,经硅烷化学改性后的环氧涂层均能提高其耐蚀性能.The improvement of corrosion performance of epoxy coatings by modification with "active" and "non-active" silanes is presented."Active" silanes are defined as ones having functional groups that can react with the epoxy groups in the epoxy resin,usually amino-silanes."Non-active" silanes are defined as ones not reacting with the epoxy groups,but can react with the hydroxyl groups in the epoxy backbone by the condensation reactions under the catalysis of organic tin compounds.The FTIR results showed that both the "active" and "non-active" silanes had been successfully grafted onto the epoxy resin.Electrochemical impedance spectroscopy(EIS) and accelerated corrosion test(Machu test) showed that the corrosion performance of epoxy coatings could be improved by chemical modification with both the "active" and "non-active" silanes.作者联系地址：浙江大学化学系;中国人民解放军第三军医大学化学教研室;中国科学院金属研究所金属腐蚀与防护国家重点实验室;Author's Address: 1.Department of Chemistry,Zhejiang University,Hangzhou 310027,China;2.Department of Chemistry,Third Military Medicine University,Chongqing 400038,China;3.State Key Laboratory for Corrosion and Protection,Institute of Metal Research,Chinese Academy of Sciences,Shenyang 110016,Chin