盐湖地区暴露25个月的碳钢表面锈层分析

通过扫描电镜(SEM)、电子探针(EPMA)、X射线衍射(XRD)、红外光谱(IRS)和电化学测试技术分析了碳钢在盐湖大气环境下暴露25个月后上下表面的锈层特征. 结果表明, 碳钢上下表面腐蚀量相似, 锈层中均富有Cl、Mg和Si等外来元素. 两个表面的腐蚀产物都主要由β-FeOOH、Fe8(O,OH)16Cl1.3和少量的γ-FeOOH组成, 最外部分的锈层中还检测到Fe3O4和δ-FeOOH. 电化学测试结果表明, 锈层对基体腐蚀具有抑制作用, 锈层保护性随暴露时间增加而增加.     

锈层下碳钢和耐候钢的微区和宏观腐蚀电化学行为

采用扫描电化学显微镜(SECM), 辅以极化曲线和电化学阻抗谱(EIS), 并结合SEM和XRD研究了耐候钢和碳钢在干湿交替环境下的腐蚀行为, 包括微区阳极溶解过程和阴极还原行为、 宏观腐蚀过程和微观结构及组成等. SECM测试结果表明, 锈层下碳钢和耐候钢的腐蚀过程都受阳极控制, 锈层的存在促进氧的还原. 宏观和微区电化学测试结果均表明, 在实验周期内, 初期形成的锈层降低了Fe阳极溶解速率, 从而提高碳钢和耐候钢的耐蚀性能, 后期形成的锈层由于其组成和结构特征的变化, 2种钢的腐蚀速率增加; 同时耐候钢的腐蚀速率较碳钢大, 且氧还原也较碳钢强, 有利于锈层的形成, 从而有利于长期的防护, 但是耐候钢的锈层在短期内并没有很好的保护性. 锈层不够致密, 呈疏松多孔状, 其组成主要有晶态的γ-FeOOH, Fe₃O₄和γ-Fe₂O₃等, 相同的干湿循环条件制备的耐候钢锈层较碳钢厚.     

锈层下碳钢的腐蚀电化学行为特征

采用极化曲线、线性极化电阻(LPR)和电化学阻抗(EIS)研究了海水中带锈碳钢的电化学行为,结果发现:长期浸泡的内锈层对电极过程有较大影响;短期浸泡,LPR和EIS测定的极化电阻(Rp)逐渐增大;而长期浸泡,Rp却逐渐减小;随着浸泡时间的延长,Rp出现了先增大后减小的变化趋势.将锈层逐层剥离后研究了碳钢的电化学行为,并结合傅里叶变换红外(FTIR)光谱和横截面结构分析表明,这主要是因为长期浸泡后,内锈层中出现了具有较高电化学活性的β-FeOOH,并且其含量随着浸泡时间的延长而逐渐增加.当进行电化学测试时,在对体系进行一定程度极化的过程中,β-FeOOH参与了阴极还原反应,使电极过程不再是简单的阳极金属溶解和阴极氧还原,加快了阴极反应速度,从而导致Rp逐渐减小.     

用丝束电极研究模拟碳化混凝土孔隙液中缓蚀剂对碳钢局部腐蚀的抑制行为

应用丝束电极(WBE)的电位/电流扫描技术, 研究了含Cl-的模拟碳化混凝土孔隙液中, Q345B碳钢局部腐蚀在空间和时间上的发生和发展特征, 同时比较了四乙烯五胺(TEPA)和亚硝酸钠缓蚀剂对局部腐蚀抑制能力的差异. 结果表明NO-2离子能快速渗透腐蚀产物层, 并抑制锈层下的碳钢活性溶解, 而乙烯胺由于在锈蚀层内的扩散速率低, 初期反而会促进锈层下的局部腐蚀, 随着烯胺分子扩散并吸附于锈蚀层/金属界面处, 碳钢活性溶解才受到抑制. 电化学阻抗谱(EIS)可反映局部腐蚀的萌发, 但难以表征缓蚀剂在碳钢表面的不均匀吸附特征. 基于丝束电极表面电位/电流分布所提出的局部腐蚀因子(LF), 可定量表征腐蚀的不均匀特征以及缓蚀剂对局部腐蚀的修复能力.     

钙处理对桥梁钢耐大气腐蚀性能的影响

以NaCl+NaHSO₃溶液为腐蚀介质,采用干/湿周浸加速腐蚀实验、失重分析、XRD、SEM和电化学方法,研究了钙(Ca)处理对桥梁钢在湿热工业-海洋大气中腐蚀行为的影响. 结果表明：Ca处理前后,实验钢的腐蚀深度随时间变化曲线总体符合幂函数W=Atn分布规律,锈层主要由非晶物质和少量晶体α-FeOOH、β-FeOOH、γ-FeOOH、Fe₃O₄组成. 微量Ca能促进铁素体生成、强化钢表面保护膜,以阻止裸钢的快速腐蚀;还能细化钢组织晶粒、抑制腐蚀产物的晶体转变,以细化锈层颗粒、减少锈层缺陷产生,进而改善锈层的致密性.     

渗铝钢在海水中的电化学行为研究

应用化学浸泡实验,电化学测试技术研究渗铝钢在海水中的电化学行为.试验表明,在海水中渗铝钢的腐蚀电位比20#钢的负,其阳极活性大于后者,在低电位下发生阳极溶解.20#钢和渗铝钢的腐蚀速率分别为5.80mg/dm2·d和3.36mg/dm2·d.渗铝钢在海水中具有优良的耐蚀性能是由于环境遮断和电偶保护的综合效果.其腐蚀产物含有氯离子,说明氯离子参与海水中的腐蚀过程,是导致腐蚀的主要原因.渗铝钢除了表层形成的Al、Fe化合物和致密、连续、具有高效防护作用Al的氧化物保护膜外,Al Fe合金层起到牺牲阳极的电化学保护作用.     

饱和NaCl溶液浸泡下混凝土试块中有机阻锈剂对钢筋腐蚀行为的影响

利用电化学阻抗谱(EIS)、半电池腐蚀电位(Ecorr)和宏观电池腐蚀电流密度(Icorr)测量技术,在饱和NaCl溶液浸泡的硬化混凝土试块中,研究了4种醇胺基阻锈剂对钢筋电极腐蚀电化学行为的影响和长期阻锈性能.在浸泡初始的100d内,与空白样相比,添加阻锈剂后钢筋电极腐蚀电位升高,阻抗膜值增大,腐蚀电流密度值降低,表明电极表面处于钝态,阻锈剂表现出良好的阻锈性能.随浸泡时间延长,电极腐蚀电位和阻抗膜值下降,腐蚀电流密度增大.浸泡后期,除添加醇胺基CI-4样外,电极电位和腐蚀电流密度与空白样相比无明显差别,表明电极由钝态转变为活性腐蚀状态.但添加CI-4样品,钢筋电极始终保持在钝化状态,阻锈性能最好.基于阻锈剂与Cl-间的竞争吸附,分析探讨了可能的阻锈机理.     

3.5% NaCl饱和Ca(OH)2溶液中醇胺缩聚物对碳钢腐蚀的抑制

利用动电位极化, 电化学阻抗谱(EIS)和表面形貌观察方法, 并结合量子化学计算, 在3.5% NaCl饱和Ca(OH)₂ 溶液中研究探讨了山梨醇与二乙烯三胺缩聚物(SDC)对碳钢腐蚀的抑制行为. 结果表明: SDC的加入可有效降低碳钢的腐蚀电流密度, 提高碳钢的点蚀电位, 表明阻绣剂对Cl^-诱导的局部腐蚀具有良好的抑制作用, 为混合型阻锈剂; 且在所研究浓度范围内, 随添加浓度增加, 缓蚀效率提高. 化合物对碳钢腐蚀的抑制主要源自阻锈剂分子在碳钢表面的静电吸附, 且吸附遵循Langmuir等温吸附规律.     

海生物附著对钢板管椿腐蚀之影响

为了解海生物对钢板管椿腐蚀之影响 ,将SS4 1金属试片浸渍于高雄港 #1 4码头水深 3m处及实验室人造海水中 .试验期间 ,以DC直流动电位极化曲线扫描与AC交流电阻抗分析现场量测各试片的瞬间腐蚀速率 .结果发现 :宏观地看 ,海生物在金属 (或锈层 )表面的附著可以减缓金属腐蚀 ,但从微观 (micro)的观点推论 ,海生物在金属表面的附著亦可以造成氧差或浓度差异电池 ,促成局部腐蚀 .此外 ,等效电路的模拟 ,有助于了解海生物附著对金属腐蚀的影响 ,即随浸渍时间的延长 ,金属表面因锈层增厚且趋于致密 ,以致锈层电阻增加 ;又因海生物种类不同 ,含水量不同 ,海生物电阻可能会有极大的差异     

含O2高温高压CO2环境中3Cr钢腐蚀产物膜特征

采用高温高压反应釜分别开展3Cr钢在CO2和O2共存、单独CO2和单独O2三种气体条件下的腐蚀实验,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散X射线能谱(EDS)和电化学方法研究了3Cr钢在高温高压含有O2的CO2环境中的腐蚀产物膜特征.结果表明,在含有O2的CO2的条件下,3Cr钢表面腐蚀产物膜疏松多孔,主要成分为FeCO3、Fe3O4和Fe2O3,腐蚀产物中未见明显Cr元素富集,3Cr钢表现出点蚀的腐蚀形态.3Cr钢在高温高压含O2的CO2腐蚀条件下内外膜层电阻(Rf1、Rf2)和电荷传递电阻Rt均比仅含有CO2腐蚀环境的低,双电层电容(Cdl)和内外膜层电容(Cf1、Cf2)均比仅含有CO2腐蚀环境的高.含有O2的CO2条件下,其保护性显著低于单一CO2条件下形成的腐蚀产物膜.提出了在含O2的CO2气体条件下,3Cr钢表面存在由多种物质组成的腐蚀产物,这导致腐蚀产物疏松多孔,不会形成单一CO2条件下存在的显著提高腐蚀产物膜保护性的Cr(OH)3层,从而促进了3Cr钢的析氢腐蚀和酸性介质中的吸氧腐蚀的机理.     

镀锌扁钢电力接地材料在NaCl介质中的腐蚀特性

应用极化曲线、电化学阻抗谱和中性盐雾腐蚀试验法,研究电力接地材料镀锌扁钢在5%NaCl溶液中的腐蚀行为,扫描电子显微镜（SEM）、X射线衍射仪（XRD）观察与表征镀锌扁钢样品腐蚀的表面形貌及其产物性质.结果表明,在20～60℃温度范围内,镀锌扁钢腐蚀电流随温度升高而增大,60℃时腐蚀速率达到0.8408mA.cm-2（...     

Electrochemical study of the corrosion behaviour of carbon steel in fracturing fluid

Corrosion behaviour of carbon steel (K-55) in fracturing fluid was studied with a rotation cylinder electrode, under static and rotation conditions by means of several electrochemical techniques which are as follows: open circuit potential (OCP) decay, potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS). The corrosion rate was determined by weight loss measurements. The electrode surface after a prefixed immersion time was characterised by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results indicated that carbon steel showed anodic dissolution behaviour that increased under rotating condition. The cathodic polarisation current density also increased with the electrode rotation due to the increased oxygen diffusion on the electrode surface. Two different oxide layers were formed: a dark, thin layer of magnetite tightly adhering to the electrode surface, characterised by localised corrosion spots, and a porous reddish layer of poorly adhering hematite (Fe₂O₃) and maghemite (γ-Fe₂O₃). Under higher rotation rate, the developed oxide layer was not so stable, owing to the shear stress induced between the solution and the specimen surface, enhancing the corrosion rate.     

碳纳米管内分立的纳米铁粒子的热氧化性能研究

研究了纳米铁填充的碳纳米管基复合纤维在空气中的热氧化性能。结果表明：一般在室温即被氧化的铁(Fe)纳米粒子在170 ℃仍然具有良好的稳定性。这一方面是由于碳纳米管的保护作用所致,另一方面碳纳米管末端的Fe纳米粒子在室温下即迅速被氧化成反尖晶石型Fe₃O₄/γ-Fe₂O₃,170 ℃以下能有效阻止氧分子向碳纳米管内扩散。因此,170 ℃可以被看作氧分子扩散进入碳纳米管腔的极限温度。在170 ℃以下时,氧分子无法渗透Fe₃O₄ /γ-Fe₂O₃晶格在管腔中形成氧分子。当温度高于170 ℃时,氧分子渗透发生,管腔内的Fe纳米粒子由靠近管末端位置到内部逐渐被氧化。由于相对良好的热氧化稳定性,Fe填充碳纳米管基复合纤维的铁磁性将可以在更高温度范围内得以保持。     

Mössbauer study of corrosion of mild steel induced by acid rain

Room temperature corrosion studies have been made on the rust of commercially available mild steel in a simulated acid rain environment using the method of transmission Mössbauer spectroscopy. The main corrosion products identified are α-FeOOH, γ-FeOOH, and a product with unfamiliar parameters which seems to be amorphous in nature (being very large linewidth ?2.5 mm/s) and may be considered as an intermediate phase. A small amount of γ-Fe₂O₃ (6–8%) is also observed.     

Degradation of passive layers of iron studied by conversion electron Mössbauer spectroscopy

Integral electron Mössbauer spectroscopy (ICEMS) and additionally some electrochemical methods were used to characterize the passivation process of iron (low carbon steel) in sulfate, sulfate+sulfite (a possible model solution of acid rain) solutions and in phospate buffer. The phase compositions and thicknesses of the passive layers formed due to the electrochemical polarizations were analyzed in dependence on the duration of the anodic passivations and on the pH of the used electrolytes. The passive layer, as determined from the Mössbauer spectra, consists mainly of -FeOOH, however in sulfite containing sulfate aqueous solution at pH 3.5 Fe₃C and despite ex-situ circumstances FeSO₄·H₂O was detected after the shortest polarization time. The film thickness, which was found to grow nearly linearly with polarization time in pure sulfate solution and in phospate buffer, reached a maximum of 60–160 nm (depending on pH) in sulfate+sulfite solution after a passivation time of about 4 hours. It has been proved, that HSO₃ ^–-ion, which is contained by acid rain, initiate pit formation under acid conditions and so enforces the corrosion of iron. The experimental results furthermore suggest, that not the whole oxidic layer is responsible for the passivity but only a very thin intermediate layer formed between an inner oxide layer of a cubic structure and the rhombic oxide (-FeOOH) cover.     

Iron oxyhydroxide nanoparticles formed by forced hydrolysis: dependence of phase composition on solution concentration

Nanoparticles of single-phase lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) have been synthesized by forced hydrolysis of ferric nitrate with no other additives, and the particles have been characterized by XRD, FT-IR and TEM. At low Fe(NO(3))(3) concentrations the hydrolysis product is predominantly γ-FeOOH, while at high concentrations it is α-FeOOH. These particles are nanometers in size and fall within narrow particle size distributions. The dependence of the oxyhydoxide phase on ferric nitrate concentration is attributed to two thermodynamic factors, the enthalpy of formation and the surface enthalpy of hydration at the oxide-water interface (which is a function of surface area). Two potential mechanisms for the phase-specific growth are proposed that explain the solution concentration dependence of the phase formed. Three other common nanoscale particles (α-Fe(2)O(3), Fe(3)O(4) and γ-Fe(2)O(3)) have also been prepared by relatively simple thermal/chemical treatment of the γ-FeOOH nanoparticles.