苯并咪唑类缓蚀剂缓蚀性能的理论评价

采用量子化学计算和分子动力学模拟相结合的方法, 对2-巯基苯并咪唑(A)、2-氨基苯并咪唑(B)、2-甲基苯并咪唑(C)和苯并咪唑(D)等四种缓蚀剂抑制HCl对碳钢腐蚀的性能进行理论评价, 并对其缓蚀机理进行分析. 全局活性指数的计算表明, 四种分子中, 2-巯基苯并咪唑分子具有最强的反应活性; 对于其他三种分子, Fukui指数和全电子密度分布指出, 2-氨基苯并咪唑具有两个亲电攻击中心, 可在金属表面形成双中心吸附, 其缓蚀性能应优于2-甲基苯并咪唑和苯并咪唑; 缓蚀剂分子与三层铁原子表面相互作用的分子动力学模拟进一步确认2-甲基苯并咪唑比苯并咪唑在金属表面吸附更稳定. 综合量子化学计算和分子动力学模拟的计算结果, 四种缓蚀剂分子缓蚀效率的顺序应为A>B>C>D, 缓蚀性能的理论评价结论与实验结果相吻合.     

缓蚀剂膜抑制腐蚀介质扩散行为的分子动力学模拟

采用分子动力学模拟方法研究了4种腐蚀介质粒子(H₂O, H₃O⁺, HS^-和Cl^-)在6种不同烷基链长的1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂膜中的扩散行为. 计算了腐蚀介质粒子在不同缓蚀剂膜中的扩散系数、膜的自由体积分数、粒子与膜的相互作用能等, 并对缓蚀剂膜抑制腐蚀介质粒子扩散行为的微观机理进行了分析. 计算结果表明, 6种缓蚀剂膜均可有效阻碍腐蚀介质粒子向金属表面的扩散, 从而达到抑制或延缓腐蚀的目的; 随烷基链长的增加, 缓蚀剂膜对腐蚀介质粒子扩散行为的抑制能力逐渐增强; 同种缓蚀剂膜对正负离子H₃O⁺, HS^-和Cl^-比对中性的H₂O分子具有更强的扩散抑制能力.     

1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂缓蚀机理的理论研究

采用量子化学计算、分子动力学模拟和分子力学相结合的方法, 对6种不同烷基链长的1-(2-羟乙基)-2-烷基-咪唑啉缓蚀剂抑制H2S腐蚀的缓蚀机理进行研究, 并对其缓蚀性能进行评价. 前线轨道分布和Fukui指数表明, 6种缓蚀剂分子的反应活性区域均集中在分子的咪唑环上, 3个反应活性中心分别位于咪唑环上的N(4), N(7)和C(8)原子, 可使咪唑环在金属表面形成多中心吸附. 分子的反应活性及活性区域分布对烷基链长并不敏感. 单分子吸附能、膜的内聚能、吸附角和链间距的计算数据显示, 缓蚀剂膜的稳定性以及膜与金属基体的结合强度随链长的增加而增大; 当正构烷基碳链长度大于13时, 缓蚀剂可在金属表面形成一层高覆盖度、致密的疏水膜, 能有效阻碍溶液中的腐蚀介质向金属表面扩散, 从而达到阻碍或延缓腐蚀的目的.     

咪唑啉缓蚀剂在Fe(001)表面吸附行为的分子动力学模拟

采用分子动力学模拟方法研究了5种不同烷基链长的咪唑啉类缓蚀剂在Fe(001)表面的吸附行为和成膜机制,并对其缓蚀机理进行了深入分析.研究结果表明:咪唑啉分子的极性头基会吸附在金属表面上,而烷基碳链则背离金属表面,并通过自身的扭转形变实现稳定吸附;随着烷基链长的增加,缓蚀剂与金属基体的结合强度逐渐增加,所形成缓蚀剂膜的致密性也逐渐增大;致密的缓蚀剂膜能有效地阻碍腐蚀介质向金属表面扩散,从而达到延缓金属腐蚀的目的.5种缓蚀剂缓蚀性能的理论评价结果与实验结果吻合.     

基于癸二酸二异辛酯的环保型复合缓蚀剂对钢筋的缓蚀效应

应用缓蚀剂控制混凝土中钢筋的腐蚀具有高效、廉价和易操作等优点,越来越受腐蚀研究者的关注。近年来,对环保型缓蚀剂的需求日益增加。因此,本工作发展了由癸二酸二异辛酯、D-葡萄糖酸钠和硫酸锌组成的环保型复合缓蚀剂并应用电化学测试技术和表面分析方法研究其对钢筋的缓蚀作用。结果表明,Q235钢筋在pH为11.00,含0.5 mol∙L^-1 NaCl的模拟污染的混凝土孔隙液中处于活化状态并发生局部腐蚀。含有59 mmol∙L^-1癸二酸二异辛酯,0.5 mmol∙L^-1 D-葡萄糖酸钠和1.5 mmol∙L^-1硫酸锌组成的复合缓蚀剂对钢筋具有良好的协同缓蚀效应,在模拟污染混凝土孔隙液中和水泥砂浆试样中对钢筋的缓蚀效率分别达到96.8%和90.0%。该复合缓蚀剂是一种混合型缓蚀剂,对钢筋腐蚀的阴极反应和阳极反应均有抑制作用。     

丙烯腈在Cu(100)表面化学吸附的密度泛函理论研究

利用密度泛函方法, 模拟金属铜原子簇Cu₁₄(9,4,1)的(100)表面, 对丙烯腈(CH₂＝CHCN)在Cu(100)面上不同吸附位的吸附状况进行了理论研究. 结果表明: 丙烯腈分子通过端位N原子垂直吸附在金属表面上为弱化学吸附, 部分电荷从丙烯腈分子转移至铜金属簇; 由N原子的孤对电子与金属铜形成弱σ共价键; 顶位是最佳吸附位, 吸附能为40.7391 kJ•mol^－1, N原子与金属表面间的平衡距离为0.2279 nm; 其次为桥位和穴位, 吸附能分别为36.2513和30.2158 kJ•mol^－1, 平衡距离为0.2194和0.2886 nm; 吸附后C≡N键的强度降低, 活化了丙烯腈分子. 化学吸附使体系的熵减小, 是由于丙烯腈分子的平动和转动因吸附而被限制.     

酸性湖蓝7在LDO上吸附性能及机理的研究

探讨了Mg/Al＝3的水滑石焙烧产物(MgAl-LDO)对染料酸性湖蓝7(AB7)的吸附性能及其机理. 考察了不同因素对MgAl-LDO吸附AB7性能的影响, 并研究了吸附过程的热力学机理. 实验结果表明: MgAl-LDO对AB7具有优异的吸附性能, 在288 K, pH＝6.74条件下, 0.33 g·L^-1 MgAl-LDO对150 mg·L^-1AB7溶液的吸附容量和去除率分别达到446.9 mg·g^-1和99.31%. 热力学研究表明: MgAl-LDO对AB7的吸附过程同时符合Langmuir 和 Freundlich等温吸附方程, 并且是个放热、自发的过程. 计算所得的吉布斯自由能绝对值在8～10 kJ·mol^-1, 这主要是由染料分子与水滑石层板的氢键作用产生, 结合Materials Studio 5.5软件模拟AB7染料分子在MgAl-LDHs上的排列分布, 推测MgAl-LDO对AB7的吸附机理是表面吸附作用. 同时, 经4次回收, LDO对AB7的去除率仍达到85%以上.     

模拟水中白铜B30耐蚀性影响因素的光电化学研究

用动电位伏安法和光电化学方法对模拟水中白铜B30耐蚀性影响因素进行了研究. 白铜B30表面膜显示p-型光响应, 光响应来自电极表面的Cu₂O层, 在模拟水溶液中表面膜的半导体性质会发生转变, 由p-型转为n-型; 在不同 Cl^－, SO₄^2－浓度的模拟水溶液中, 电位正向扫描时呈现阳极光电流, 电位负向扫描时随着Cl^－, SO₄^2－离子浓度的增加, 光响应由p-型向n-型转变, 阳极光电流峰面积与阴极光电流峰面积之比增大, 耐蚀性能降低; 随着温度的升高, 白铜B30的耐蚀性能降低; 在pH＝7～9之间, 其耐蚀性能随着pH的升高而提高, 当pH＞9时, 其耐蚀性能随着pH的升高呈降低趋势.     

高温沉淀铁基催化剂上费托合成含氧化合物生成机理的研究

采用漫反射原位红外光谱法及化学捕获方法,考察了费托合成过程中高温沉淀铁基催化剂表面吸附物种的变化,并探讨了含氧化合物的生成机理。结果表明,CO在高温沉淀铁基催化剂上有线式和桥式两种吸附态存在,同时,CO的吸附在催化剂表面生成大量含氧化合物前驱体。费托原位实验捕获到了一些较关键的中间产物:表面乙酸盐、表面酰基、甲氧基等。同时发现高温沉淀铁基催化剂表面具有以下反应共性:醇类可与表面羟基结合生成烷氧基团;催化剂表面的吸附分子具有氧化性;一些基础化学物质如OH^-、晶格氧等可以与甲醇或乙醛分子发生反应。对CH₃OH + CO及CH₃I + CO + H₂两个反应的化学捕获实验表明,酰基是C₂⁺含氧化合物的重要中间产物,酰基加氢是形成C₂⁺含氧化合物的关键步骤。根据表面中间产物及反应特性,得到了高温沉淀铁基催化剂上费托合成含氧化合物的生成机理。     

咪唑啉酰胺在电偶电极表面的吸附行为

采用原子力显微镜技术研究了有机阳离子缓蚀剂(咪唑啉酰胺)在电偶电极表面的吸附行为, 并探讨了其腐蚀抑制机理. 结果表明, 金属表面的过剩电荷较大地影响缓蚀剂分子的吸附行为. 在1%的NaCl溶液中, 碳钢电极表面带有过剩的负电荷；不锈钢电极表面带有过剩的正电荷；碳钢电极和不锈钢电极耦合后, 其表面分别带有过剩的正电荷和负电荷. 在耦合前阳离子缓蚀剂分子仅吸附在碳钢表面, 耦合后缓蚀剂分子在偶对的阴极(不锈钢)和阳极(碳钢)表面均有吸附, 但缓蚀剂分子在碳钢表面的吸附强度和覆盖度较之耦合前降低, 缓蚀剂的腐蚀抑制能力减弱.     

Croton lechleri Extracts as Green Corrosion Inhibitors of Admiralty Brass in Hydrochloric Acid

Croton lechleri, commonly known as Dragon’s blood, is a tree cultivated in the northwest Amazon rainforest of Ecuador and Peru. This tree produces a deep red latex which is composed of different natural products such as phenolic compounds, alkaloids, and others. The chemical structures of these natural products found in C. lechleri latex are promising corrosion inhibitors of admiralty brass (AB), due to the number of heteroatoms and π structures. In this work, three different extracts of C. lechleri latex were obtained, characterized phytochemically, and employed as novel green corrosion inhibitors of AB. The corrosion inhibition efficiency (IE%) was determined in an aqueous 0.5 M HCl solution by potentiodynamic polarization (Tafel plots) and electrochemical impedance spectroscopy, measuring current density and charge transfer resistance, respectively. In addition, surface characterization of AB was performed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques. Chloroform alkaloid-rich extracts resulted in IE% of 57% at 50 ppm, attributed to the formation of a layer of organic compounds on the AB surface that hindered the dezincification process. The formulation of corrosion inhibitors from C. lechleri latex allows for the valorization of non-edible natural sources and the diversification of the offer of green corrosion inhibitors for the chemical treatment of heat exchangers.     

实用电极材料体系的共焦显微拉曼光谱研究(英文)

本文简要介绍了实验室内有关利用共焦显微拉曼光谱于某些实用电极材料 (表面 )性能研究的结果 .具体的研究实例包括 :尖晶石锂锰氧化物中Li+ 的嵌入 脱出过程 ,AB5 型金属氢化物电极表面氧化物的性能和钢筋电极表面钝化膜及其孔蚀过程 .     

Analysis of pitting corrosion rate

A method for estimating pitting corrosion rate is proposed. The method is based on the analysis of anodic and cathodic voltammograms that were measured on the specimens of two types: on the test specimen coated with an oxide film, which formed under the open-circuit conditions, and on the specimen, whose surface was totally activated with aggressive ions. The use of Tafel portions of these voltammograms in various combinations enables us to estimate the corrosion potential and corrosion current for general corrosion proceeding in the induction period, for pitting corrosion at the initial stage of its development, for a highly developed pitting corrosion, when the major area of specimen surface is occupied with pits, and also in the intermediate case.     

Natural Product-Derived Phosphonic Acids as Corrosion Inhibitors for Iron and Steel

Organic acids, typically derived from an oil-based value chain, are frequently used as corrosion inhibitors in industrial metal working fluids. The criteria for selection of these corrosion inhibitors have changed in the last decades, and are today not only performance-driven, but influenced by ecological considerations, toxicity and regulatory standards. We present scalable semisynthetic approaches to organic corrosion inhibitors based on phosphonic acids from renewable resources. They have been evaluated by chip filter assay, potentiodynamic polarization measurements, electrochemical impedance measurements and gravimetry for corrosion protection of iron and steel in an aqueous environment at slightly alkaline pH. The efficacy of several phosphonic acids tested was found to be strongly dependent on structural features influencing molecular self-assembly of protective layers, and the solubility of salts formed with di- and trivalent cations from the media or formed during corrosion. A carboxyphosphonic acid (derived from castor oil) was found to have remarkable anticorrosive effects in all media tested. We attribute the anticorrosion properties of this carboxyphosphonic acid to the formation of particularly stable protective layers on the metal surface. It might thus serve as a commercially attractive substitute for current acidic corrosion inhibitors, derived from renewable resources.     

Epoxy polymer coating to prevent the corrosion of aluminum nanoparticles

Aluminum nanoparticles were coated by epoxy polymer in order to prevent the corrosion reaction. The coverage of the epoxy polymer film was controlled from 0% to 100%, which changed the corrosion rate of nanoparticles quantitatively. The surface of the polymer coating was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the corrosion resistance of these nanoparticles was estimated by the wet/dry corrosion test on platinum (Pt) plate with a NaCl solution. From a TEM analysis, 10 mass% polymer‐coated Al particles in the synthesis were almost 100% covered on the surface by a polymer film of 10 nm thick. On the other hand, 3 mass% polymer‐coated Al was partially covered by a film. In the AFM–Kelvin force microscopy, the potential around the Al particles had a relatively low value by the polymer coating, which indicated that the conductivity of the Al was isolated from Pt plate by the polymer. Both the corrosion and H₂ evolution reaction rates were quantitatively reduced by the mass% of polymer coating. In the case of 10 mass% coated sample, there was very little corrosion of Al nanoparticles. This fact suggested that the electrochemical reaction was suppressed by the polymer coating. Thus, it was found that the corrosion reaction rate of Al nanoparticles could be quantitatively suppressed by the mass% of epoxy coating. Copyright © 2015 John Wiley & Sons, Ltd.     

Superhydrophobic ceria on aluminum and its corrosion resistance

Superhydrophobic ceria on the aluminum substrate was fabricated, and its corrosion resistance was investigated by different techniques. For example, the so‐obtained superhydrophobic sample was immersed into the NaCl aqueous solution, and the variations in the surface wettability as well as the surface morphology were monitored; potentiodynamic polarization in the NaCl aqueous solution was adopted to evaluate its electrochemical corrosion resistance; a droplet of the aqueous solution HCl was dripped onto the superhydrophobic surface, and the corrosion process as well as the surface morphology after corrosion was monitored. The experimental results showed that the superhydrophobic ceria possessed a good corrosion resistance because of the entrapped air in the solid/liquid interface. Copyright © 2016 John Wiley & Sons, Ltd.     

SNAP溶胶组成对镁合金涂层耐蚀性的影响

本文利用纳米自组装颗粒工艺(SNAP)在AZ31B镁合金表面制备了防腐涂层。通过透射电镜(TEM)和扫描电镜(SEM)观察及电化学阻抗谱(EIS)、电导率测试等,对SNAP溶胶的纳米粒子形态和电导率,以及SNAP涂层的表面形貌和耐蚀性进行了测试,研究了不同含量的有机硅烷前躯体3-缩水甘油醚丙基三甲氧基硅烷(GPTMS)和正硅酸乙酯基硅烷(TEOS)、溶剂水、助溶剂无水乙醇、交联剂三乙烯四胺(TETA)等对镁合金SNAP涂层耐蚀性的影响。研究结果表明,随着溶胶中TEOS和TETA含量的增大,镁合金涂层耐蚀性呈先增大后减小的趋势;随着溶胶中水含量的增大,镁合金涂层耐蚀性提高;溶胶中无水乙醇的含量较低时,对镁合金涂层耐蚀性的影响较小。     

Sol–gel synthesis of silica containers using a corrosion inhibitor,catamine AB,as a templating agent

It has been shown that silica container particles containing a large amount (~1 g/g of SiO₂) of a corrosion inhibitor, catamine AB, can be obtained, with the inhibitor being loaded at the stage of the sol–gel synthesis of the particles by using catamine micelles as a template. Being introduced into an H₂S-containing aggressive aqueous medium, such containers protect rather efficiently carbon steel from hydrogen-sulfide corrosion and hydrogenation. The protection effect seems to be realized via not only the release (desorption) of catamine AB molecules from the containers, but also the adsorption of the products of gradual dissolution of silica matrix on the surface of metal being protected.     

Laser treatment of A286 superalloy: corrosion resistance of the treated surface

Laser controlled melting of metal surface provides a local treatment with improved surface properties such as corrosion resistance. In the present study, laser surface treatment of iron base superalloy (A286) is carried out. The corrosion resistance of the laser‐treated surface is examined through potentiodynamic tests using 0.5 N NaCl solution. The microstructural and morphological changes in the laser‐treated layer are investigated incorporating scanning electron microscopy (SEM), X‐ray diffraction (XRD) and energy dispersive spectroscopy. The residual stress formed at the laser‐treated surface is measured using the XRD technique. It is found that laser treatment enhances corrosion resistance of A286 superalloy surface, which is attributed to the formation of fine grains and dense layer at the treated surface. Although locally scattered few corrosion induced microcracks are observed at the treated surface, they are not extended to form large cracks or crack network at the surface. Copyright © 2012 John Wiley & Sons, Ltd.     

SERS技术对聚天冬氨酸缓蚀性能的研究

SERS技术对聚天冬氨酸缓蚀性能的研究;缓蚀作用;表面增强拉曼散射