Brief Introduction to Metal Corrosion and Protection

本文简要阐明了为什么金属的腐蚀主要以电化学腐蚀的形式出现，剖析了腐蚀过程电化学动力学参数的物理意义，以及金属腐蚀的防护原理、常用的腐蚀防护方法乃至腐蚀过程的一些特殊应用。This paper explains why corrosion processes are usually electrochemical in nature, describes the significance of electrochemical kinetic parameters of corrosion process, and briefly introduces the principles of corrosion protection, the most common corrosion protection methods and some special application of corrosion processes.国家自然科学基金（21073111）作者联系地址：山东大学化学与化工学院，山东 济南 250100Author's Address: School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, Shandong, China通讯作者E-mail：[email protected]

A Comparative Study of Charge-Discharge Behaviors of α-PbO2 and β-PbO2 Cathodes

利用化学合成法分别制得α-PbO2和β-PbO2样品，采用XRD、SEM表征与观察两种不同晶型的PbO2样品. 由两种晶型PbO2粉末做成铅酸电池的活性正极，采用循环伏安、恒电流充放电以及电化学阻抗谱等电化学方法研究了其电化学性能. 结果表明，α-PbO2电极的放电容量较低，β-PbO2电极的放电容量较高，两种晶型PbO2粉末按不同配比制成复合电极有利于提高铅酸电池正极的充放电性能.The α-PbO2 and β-PbO2 powders were prepared using simple chemical synthetic methods, and their crystalline structures and surface morphologies were characterized with X-ray powder diffraction spectroscopy and scanning electron microscopy. Using the as-synthesized α-PbO2 and β-PbO2 powders as positive active materials, the electrochemical performance of the two PbO2 materials was investigated by means of cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy. The results indicate that the discharge capacity of α-PbO2 electrode is larger than that of β-PbO2; moreover, the composite electrodes made by α-PbO2 and β-PbO2 mixtures with different proportions are favorable for enhancing the charge-discharge cycle performance of PbO2 positive electrode.国家973项目计划（No. 2011CB935901）和山东大学自主创新基金（No. 2009JC019）资助作者联系地址：1. 山东大学化学与化工学院，山东 济南 250100； 2. 山东圣阳电源股份有限公司，山东 曲阜 273100Author's Address: 1. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China; 2. Shandong Sacred Sun Power Sources Co. LTD., Qufu 273100, Shandong, China通讯作者E-mail：[email protected]

Phase-Transfer Technique for Polymer-Protected Noble Metal Nanoparticles

依据聚乙烯吡咯烷酮(PVP)在水中的溶解度随温度升高而降低的特性,建立了将PVP保护的金、银、铂纳米粒子从水相转移到油相的简单而有效的相转移技术.方法是利用电化学还原法先于水溶液中制备粒度均匀的金属纳米粒子,然后向电化学合成后的金属纳米水溶胶中加入适量正丁醇,在搅拌条件下升温至80℃即可使金属纳米粒子从水相转移至有机相.纳米粒子的相转移效率很高,而且相转移后粒子在油相中分散很好,没有团聚现象发生.在此基础上进一步建立在油水混合体系电化学合成金属纳米粒子的实验方法,为收集纳米粒子和制备纳米粒子薄膜提供了新的有效途径.A novel phase-transfer method was developed based on the decrease of PVP's solubility in water with increasing temperature,by means of which PVP-protected gold,silver and platinum nanoparticles can be conveniently transferred from aqueous phase to 1-butanol phase.Monodispersed metal nanoparticles were electrochemically synthesized at first in the aqueous,and then 1-butanol of appropriate volume was added to the aqueous phase.Heating the oil-water mixture to 80 ℃ under vigorous stirring would make metal nanoparticles leave the aqueous phase and enter into the 1-butanol phase,with high phasetransfer efficiency and without aggregation between nanoparticles.An electrochemical method to synthesize metal nanoparticles in the oil-water mixtures was further established,which provides a new path for collection of nanoparticles and preparation of metal nanofilms.作者联系地址：山东大学化学与化工学院,哈尔滨工业大学(威海)海洋学院,山东师范大学理化分析测试中心,山东大学化学与化工学院,山东大学化学与化工学院,山东大学化学与化工学院 山东济南250100,山东威海264209,山东济南250014,山东济南250100,山东济南250100,山东济南250100Author's Address: 1,HUANG Ming-hu~2,ZHANG Xiao-kai~3, HUANG Shao-xin~1,PAN Wei~1,MA Hou-yi~*11.School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,Shandong,China,2.School of the Ocean,Harbin Institute of Technology at Weihai,Weihai 264209,Shandong,China;3.Analysis and Testing Center,Shandong Normal University,Jinan 250014,Shandong,Chin

Novel Electrochemical Method for Synthesis of Nanostructured Materials of Noble Metals Based on Poly(N-Vinylpyrrolidone) (PVP)

以不同聚合度的聚乙烯吡咯烷酮(PVP)作为金纳米团簇的稳定剂和形状控制剂,应用电化学还原方法制备尺寸可控的金纳米晶体.借助PVP聚合物的动态伸缩和卷曲特性将电化学还原得到的金纳米粒子前驱体组装成线状和环状的纳米粒子聚集体,再由不稳定前驱体粒子的定向聚集制备厚度为几十纳米的金纳米棱柱.并用分步电化学还原法合成核壳结构的金银纳米复合粒子.本文为制备不同形状和结构的贵金属纳米结构材料提供了一种可行的电化学合成新方法.Gold nanocrystals with controllable size were synthesized through a simple electroreduction method using poly(N-vinylpyrrolidone)(PVP) of different polymerization degree as both stabilizer and shape-controller for gold nanoclusters.Individual gold nanoparticles spontaneously assembled into the wire-and ring-shaped nanoparticle aggregates depending on the PVP's dynamic stretching and curling,and precursor nanoparticles grew into flat,single-crystalline nanoprisms with thickness of dozens of nanometers based on the oriented aggregation between particles.Besides,core-shell Au/Ag nanoparticles were conveniently synthesized through two-step electroreduction of noble metal ions in the presence of PVPK30.The electrochemical synthetic method based on PVP provides a new path for preparation of noble metal nanostructured materials with different shape and structure.作者联系地址：山东大学化学与化工学院,山东师范大学理化分析测试中心,哈尔滨工业大学(威海)海洋学院,山东大学化学与化工学院,山东大学化学与化工学院,山东大学化学与化工学院 山东济南250100,山东济南250014,山东威海264209,山东济南250100,山东济南250100,山东济南250100Author's Address: 1,ZHANG Xiao-kai~2,HUANG Ming-hu~3,HUANG Shao-xin~1,FENG Xing-li~1,MA Hou-yi~*11.School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,Shandong,China,2.Analysis and Testing Center,Shandong Normal University,Jinan 250014,Shandong,China,3.School of the Ocean,Harbin Institute of Technology at Weihai,Weihai 264209, Shandong,Chin

Preparation and Catalytic Activity of Nanostructured Pd and Au-Pd Thin Films

应用电位扫描法将Pd(II)离子沉积到玻碳电极表面,形成纳米结构的金属钯薄膜电极.然后在酸性溶液中控制适当的阴极电位,使该薄膜电极的钯吸收足量的活性氢,进而以吸收的氢作还原剂将Au(III)离子还原,制得Au-Pd双金属薄膜电极.扫描电镜、循环伏安法等测试表明,该电极Au-Pd沉积层对乙醇的氧化具有很高的电催化活性.The nanostructured Pd thin films were directly formed on the glassy carbon electrode(GCE) substrates by using potential cycling method.The as-prepared Pd thin films deposited onto the GCE were able to absorb enough amount of hydrogen in acidic solutions at the cathodic potentials more negative than the hydrogen evolution potential.Moreover,the absorbed hydrogen could be used as the reducing agent to reduce gold(III) ions to Au nanoclusters,thereby forming bimetallic Au-Pd thin films on the GCE substrate.SEM and cyclic voltammetry characterization demonstrated that the Au-Pd thin films display much higher catalytic activity towards the electro-oxidation of ethanol than the pure Pd thin films.作者联系地址：山东大学化学与化工学院,山东大学化学与化工学院,山东大学化学与化工学院,山东大学化学与化工学院 山东济南250100,山东济南250100,山东济南250100,山东济南250100Author's Address: School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,Shandong,Chin

Inhibition of N,N'-o-phenylen-bis(3-methoxysalicylidenimine) on Copper in Halide Solutions

应用恒电位稳态极化和交流阻抗技术研究了希夫碱—邻香兰素邻苯二胺 (V_oPh_V)在中性NaCl或NaBr溶液中对金属铜阳极溶解和腐蚀的缓蚀作用 .通过比较铜在空白溶液与含有V_o_Ph_V溶液中的电化学行为解释了V_o_Ph_V的缓蚀机制 .此外还研究了V_o_Ph_V自组装膜在Na Cl溶液中对铜腐蚀的缓蚀效应 .Inhibition of N,N'_o_phenylen_bis(3_methoxysalicylidenimine)(V_o_Ph_V)on corrosion and anodic disslution of copper in neutral NaCl and NaBr solutions was investigated in terms of potentiostatic steady_state polarization and A.C. impedance techniques.The inhibition mechanism of V_o_Ph_V to copper corrosion was interpreted in detail by comparing the electrochemical behaviors of copper in halide solutions with or without V_o_Ph_V. Besides,the inhibition effect of self_assembled V_o_Ph_V film on copper corrosion in NaCl was also studied.作者联系地址：山东大学化学学院!山东济南25100,山东大学化学学院!山东济南25100,山东大学化学学院!山东济南25100,山东大学化学学院!山东济南25100,山东大学化学学院!山东济南25100Author's Address: College of Chemistry,Shandong University,Jinan 250100 Chin

Preparations and Corrosion Protection Investigations of Diethylene Triamine Penta(Methylene Phosphonic Acid)-Zn2+ Conversion Coatings on Cold Rolled Steel Substrates

本文通过调节二乙烯三胺五甲叉膦酸酯（DTPMPA）与Zn2+浓度以及溶液的pH值，将冷轧钢板浸泡于含有DTPMPA和Zn2+的混合溶液中即可在基体表面形成颜色均匀且具优异腐蚀防护性能的DTPMPA-Zn2+化学转化膜. 使用 SEM 和 EDS 研究了DTPMPA-Zn2+转化膜的表面形貌和元素组成，利用FTIR和XPS光谱方法探究了化学转化膜的表面官能团、化学组分及官能团与基底的结合方式，进而通过电化学阻抗谱（EIS）和极化曲线方法探究了DTPMPA浓度及成膜溶液pH值对化学转化膜的耐蚀性能的影响. 研究发现，DTPMPA与Zn2+共存时，二者发生螯合反应，并以Zn2+为交联剂通过多层组装在冷轧钢基体表面形成外观为蓝色的、厚度较为均匀的DTPMPA-Zn2+螯合物薄膜. 当成膜溶液的 pH=3.0、DTPMPA浓度为0.2%（除特别指出外，全文浓度均为质量百分数）、Zn2+浓度为0.044%时，化学转化膜展现出最优异的防腐性能，对基体的腐蚀保护效率可达91.6%.Novel diethylene triamine penta(methylene phosphonic acid) (DTPMPA)-zinc ion (Zn2+) conversion coatings with uniform blue color and excellent corrosion protection were directly formed on the cold rolled steel (CRS) substrates by immersing a CRS plate into the film-forming solutions containing the appropriate concentrations of DTPMPA and Zn2+ ion at the proper pH. In this paper, surface morphologies and elemental compositions of DTPMPA-Zn2+ conversion coatings were characterized by SEM and EDS, respectivey. The surface functional groups, chemical constituents and binding modes to the substrates were investigated by means of FTIR and XPS methods. The influences of DTPMPA concentrations and pH values on the corrosion protection properties of the DTPMPA-Zn2+ conversion coatings were studied using electrochemical impedance spectroscopy (EIS) and polarization measurements. The results revealed that DTPMPA reacted with Zn2+ ions, forming the DTPMPA-Zn2+ chelate under the coexistence condition of both substances. Moreover, the chelate would be deposited onto the CRS substrate through the cross-linking of Zn2+ ions and form three-dimensional DTPMPA-Zn2+ thin films with uniform blue color and thickness. This kind of conversion coating exhibited the best corrosion resistance performance with the protection efficiency of 91.6% when the concentrations of DTPMPA and Zn2+ ion were 0.2wt% and 0.044wt%, respectively, in the film-forming solutions at pH = 3.0.国家自然科学基金项目（No. 21673130）资助作者联系地址：1. 山东大学化学与化工学院，山东 济南 250100; 2. 中国科学院海洋研究所，山东 青岛 266071Author's Address: 1. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China; 2. Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China通讯作者E-mail：[email protected]

Design and Fabrication of the High Efficient Platinum-Nanoporous Gold Catalysts

使用去合金法制备了孔径和孔壁均匀的纳米多孔金(NPG)电极.研究发现NPG对甲酸、甲醛的氧化具有很高的电催化活性.如在NPG基体再沉积微量的铂,不仅明显改善了NPG的结构稳定性,而且由于Pt、Au两组分之间的协同效应而使该催化剂对有机小分子的电催化氧化具有比纯铂更高的催化活性和更强的抗催化毒物能力.The nanoporous gold(NPG) electrodes with uniform pore sizes and ligaments were prepared by using a simple dealloying method.The as-prepared NPG showed high catalytic activity towards the oxidation of formic acid and formaldehyde.After tiny amount of platinum was deposited onto the NPG substrate,not only the structure stability of NPG was greatly improved,but also the Pt-Au bimetallic catalysts displayed the better catalytic activity and the stronger poison resistance towards the electrooxidation of small organic molecules than the bulk platinum due to synergistic effect between Au and Pt compositions.作者联系地址：山东大学化学与化工学院;Author's Address: School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,Chin

渠灌类型区农业高效用水模式与产业化示范

本项目针对我国北方渠灌类型区用水效率低下、灌溉管理粗放等主要技术问题，提出了采用有利于机械化施工的U型渠道衬砌结构形式与复合土工膜相结合的板膜复合离渗抗冻胀结构形式；在对传统农田地面灌水技术进行改进与提高的基础上，提出了节水型田间地面灌水新技术；研制开发出了U型渠道抛物线型量水堰CAD设计软件和移动式渠道量水堰板、渠道防渗接缝新材料聚硫密封胶及冷施工新技术、ON——100波涌灌溉间歇控制设备，以及指导灌区科学用水管理与确定作物高效灌溉制度的专家决策系统；并将上述创新性技术与可在渠类型区应用的多项节水技术进行组装、集成，凝练出渠灌类型区农业高效用水技术体系，实现了工程节水、农艺节水与管理节水的有机结合；创建了农业高效用水试验示范样板，形成了易于推广，可移植性强的集工程建设、技术服务、灌溉管理与运行机制于一体的渠灌区农业高效用水模式。特点：本项目具有以下4个特点：1、技术成果实现了工程节水、农艺节水与管理节水的有机统一。2、研制开发出的节水技术设备不仅具有创新性，而且便于应用推广。3、为实现灌区用水按方收费与科学管理等提供了技术支撑。4、提出了易于推广，可移植性强、集工程建设、技术服务、灌溉管理与运行机制于一体的渠灌区农业高效用水模式