Analysis of corrosion scales formed on steel at high temperatures in hydrocarbons containing model naphthenic acids and sulfur compounds

Corrosive naphthenic acids and sulfur compounds in crude oils present a major challenge for refineries from a corrosion perspective. Although it is accepted that some sulfur compounds may form protective FeS scales on the metal surface and deter corrosion, attempting to correlate the characteristics of FeS scale with its protective properties has not been successful. Given the complex chemical compositions of real crudes, model sulfur compound and model naphthenic acids were used to mimic the corrosion by crude fractions in the present study. The iron sulfide scale formed by the model sulfur/acid compounds was challenged by naphthenic acids under high‐velocity conditions to examine its protectiveness against corrosion. Moreover, the scale was analyzed with transmission electron microscope/energy dispersive X‐ray spectroscopy technique, and a layer of iron oxide formed on the 5Cr steel was found when naphthenic acids were present in the solution. The iron oxide layer appeared to be important for maintaining protection against naphthenic acid corrosion, and further analysis revealed that it was composed of magnetite. Copyright © 2015 John Wiley & Sons, Ltd.     

十八烷基胺在铁上成膜结构和耐腐蚀性研究

十八烷基胺(ODA)应用于热力设备停用保护技术在国外开发较早[1－3],国内电厂这二年来应用该技术也日益增多,但由于基础研究做得较少,使用效果受到影响.1996年以来我们对ODA的成膜条件和机理进行了一些研究[4－6],本文利用交流阻抗、俄歇电子能谱、红外镜反射光谱、光电化学等方法对ODA的成膜结构和耐蚀性进行探讨,同时介绍ODA在电厂的应用情况.1实验实验材料为DT-4型纯铁.样品制备及交流阻抗测试见文献[4－6].　　俄歇能谱(AES)Perkin-ElmerPHI550ESCA/SAM.实验在机械工业部上海材料研究所进行.　　红外镜反射(SR)Bio-R…     

硫铁矿烧渣制备氧化铁黄和氧化铁红

对利用硫铁矿烧渣制备氧化铁黄和氧化铁红进行了研究。考察了影响硫铁矿烧渣还原、酸溶、中和、氧化等过程的各种因素。结果表明,在适宜的条件下,利用烧渣可以制备出用做颜料的氧化铁黄和氧化铁红。     

Corrosion-resistant coating of iron: A synergistic effect of electroactive poly(triphenylamine) coating with posttreatment for high-corrosion-protection efficiency

AbstractAn electroactive poly(triphenylamine) (PTPA-C6) is applied to the surface of iron as a corrosion-protection layer. The iron substrate coated with PTPA-C6 is thermally treated at different temperatures (up to 80°C) to study the effect of thermal treatment of PTPA-C6 on the corrosion behavior of iron. Experimental results indicate that the contact angle of the PTPA-C6 film increases from 81.6° at room temperature to 100° after thermal treatment at 80°C for 1 hr. The surface becomes more hydrophobic after thermal treatment, which will lower the penetration of water to the iron surface. Adhesion tests (ASTM 3359) indicate that adhesion between the PTPA-C6 and iron substrate is enhanced after thermal treatment. Additionally, a thin iron oxide layer formed between the PTPA-C6 and iron substrate as a passivation layer. The synergistic effect of these factors makes PTPA-C6 a very effective corrosion protection layer on iron substrate after appropriate thermal treatment. Corrosion protection efficiency increases from 90% of the pristine PTPA-C6 to 99.9% of the 80°C treated PTPA-C6.     

The Poisoning of Pyrite Surface upon Xanthate Adsorption by Cyanide in Mildly Acidic Media

Xanthate adsorbs on pyrite surface at mildly acidic pH, rendering mineral surface hydrophobic. By far, the electrochemical behavior of pyrite exposed to cyanide‐bearing solution has been reported in alkaline media. The impact of cyanide on the chemisorption of xanthate on pyrite in mildly acidic media is unclear. The present study clearly pictured the interfacial processes in pyrite‐xanthate‐cyanide system at pH 5 via methods of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is determined that cyanide blocks the formation of xanthate layer on pyrite surface over a broad range of potential, although the oxidation of xanthate in solution almost remains unaffected. The pyrite surface upon xanthate adsorption is poisoned by cyanide with the formation of iron cyanide complex.     

Fe-50Cu纳米涂层的制备及氧化行为

为探讨晶粒尺寸变化对多相合金氧化行为的影响,采用磁控溅射技术制备了Ｆｅ－５０Ｃｕ过饱和固溶体纳米涂层,并利用热重实验对比研究了该涂层与同成分的铸态合金在８００℃空气中的氧化行为。结果表明,铸态合金中形成了包括铁和铜的氧化物及其复合氧化物在内的复杂外氧化膜,同时发生了铁的内氧化。涂层中发生了铁的单一外氧化,但涂层退化后,合金基体中仍出现铁的内氧化。这种氧化模式的转变机制在于涂层尺寸的纳米化显著扩展了     

A Study on Corrosion Processes of Archaeological Glass from the Valencian Region (Spain) and its Consolidation Treatment

The combined use of scanning electron microscopy/energy dispersive X-ray microanalysis (SEM/EDX) and square wave voltammetry (SQWV), is used for studying the corrosion processes that have taken place in buried glass from different archaeological sites in the Valencian Region (Spain). The procedures permit a parallel investigation of morphology and chemical composition. Determination of the chemical composition of the glasses and their alteration crust and identification of the elements responsible for the colour has been also carried out using energy dispersive X-ray microanalysis. The electrochemical response of samples attached to paraffin-impregnated graphite electrodes reveals the presence of different iron and manganese oxide species in the browning areas of the corroded glass. Image analysis applied to microphotographs obtained by means of SEM led to the determination of morphological parameters concerning the corrosion phenomena occurring on the surface of the fragments such as thickness of the corrosion layer and its laminated structure. Additionally, measurement of the thickness of the film of polymer used as coating in the consolidation treatments has been carried out using cryo-scanning electron microscopy (cryo-SEM) combined with image analysis.     

Progresses of coal liquefaction catalysts in Japan

Research and development of catalysts and their performances for coal liquefaction are reviewed, enphasizing the contribution of recent 20 years from Japan. A variety of iron based catalysts were extensively examined to define the pyrrhotite as the active species produced in the liquefaction process. Synthetic pyrite, synthesized hydroxy ferric oxide, finely ground pyrite and limonite have been applied in the process development of coal liquefaction. Iron impregnation onto coal particles using waste water was examined also in a continuous-flow reactor. Finer particles were found to reduce significantly the amount of the catalyst to obtain the same oil yield. Usefulness of such catalysts is proved in the continuous operation of a large scale pilot plant. Iron, iron–nickel, and iron–molybdenum sulfides were found to be active catalysts when they are supported on nano-particles of carbon. Catalysts for recovery and repeated use and for selective aromatic ring opening are under current research.     

熔盐热腐蚀的电化学交流阻抗谱研究

采用电化学阻抗谱技术研究了Ｎｉ３Ａｌ、ＩＮ１００和ＩＮ７３８合金在７００℃熔融（Ｎａ,Ｋ,Ｌｉ）２ＳＯ４中的腐蚀行为．结果表明,Ｎｉ３Ａｌ和ＩＮ１００合金的腐蚀呈典型的扩散控制特征,在合金表面形成疏松的腐蚀层;而ＩＮ７３８合金因在表面形成保护性的Ｃｒ２Ｏ３膜,腐蚀不受扩散控制．提出了等效电路并计算了相应的电化学参数．     

Adsorptive passivation of iron by organic acid anions

Studies on the iron passivation by organic acid anions in aqueous solutions are briefly reviewed. It is shown that the passivation can be caused only by their adsorption, retarding both the iron dissolution and the formation of oxide films. Earlier, it had been believed that oxide films play a dominant role in the iron passivation in neutral solutions. The recent viewpoint is that such nonoxide iron passivation can occur in solutions of salts of not only aromatic amino acids (sodium phenylantranilate and its substitutes), but other carboxylic acids as well. An important role of chemisorption and hydrophobic properties of anions for the formation of adsorption passive films is emphasized. New possibilities for inhibitor protection of iron against corrosion, which is based on adsorptive passivation, are pointed out.Translated from Elektrokhimiya, Vol. 40, No. 12, 2004, pp. 1503–1507.Original Russian Text Copyright © 2004 by Kuznetsov.     

Chemical modification of iron oxide surface with organosilicon and organophosphorous compounds

The feasibility of modifying iron oxides (α-Fe₂O₃, γ-Fe₂O₃, and an oxide covering the surface of carbonyl iron) with various organosilicon and organophosphorous compounds has been studied. It has been shown that the surfaces of these oxides can be successfully modified with ethoxysilanes and diethyl ester of butylphosphonic acid. Resultant grafted layers have being found to be rather hydrolytically and thermally stable. The effect of the modification on the corrosion and erosion stability of carbonyl iron has been investigated. It has been demonstrated that the modifying layers can efficiently protect carbonyl iron particles from corrosion.     

中温NaCl-水蒸气协同作用下铁的腐蚀机理

应用电偶电流测试法研究在中温固态NaCl盐膜-水蒸气协同作用下,纯铁的腐蚀电化学反应机理.交流阻抗(EIS)法和SEM测试表明,阻抗谱能有效地表征材料表面氧化膜的存在以及反应过程氧化物的变化趋势,其中金属的氧化层电阻与腐蚀速率之间有较好的对应关系.     

Characteristics of CO2 corrosion scale formed on P110 steel in simulant solution with saturated CO2

The SEM, X‐ray diffraction (XRD), and XPS were employed to systematically characterize the component and microstructure of the corrosion scale formed on P110 steel exposed to carbon dioxide (CO₂) environment. A loose and porous microstructure in corrosion scale was observed under turbulent flow condition for 120 h at 100 °C with a carbon dioxide partial pressure of 4 MPa in which the principal component was iron carbonate (FeCO₃), whereas at 160 °C the corrosion scale was composed mainly of FeCO₃ and a little amount of FeO(OH). In addition, complex carbonate (Mg,Fe)CO₃ was produced because some Fe positions in FeCO₃ lattice were substituted by Mg. It showed that a double‐layer structure of corrosion scale was observed at 160 °C compared with the result at 100 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of thermal treatment on hydrophilicity and corrosion resistance of Ti surface

Surface treatment of titanium (Ti) surface has been extensively studied to improve its properties for biomedical applications, including hydrophilicity, corrosion resistance, and tissue integration. In this present work, we present the effects of thermal oxidation as surface modification method on metallic titanium (Ti). The Ti foils were oxidized at 300°C, 400°C, 500°C, and 600°C under air atmosphere for 3 hours, which formed oxide layer on Ti surface. The physicochemical properties including surface chemistry, roughness, and thickness of the oxide layer were evaluated in order to investigate how these factors affected surface hydrophilicity, microhardness, and corrosion resistance properties of the Ti surface. The results revealed that surfaces of all oxidized samples were modified by formation of titanium dioxide layer, of which morphology, phase, and thickness were changed according to the oxidized temperatures. Increasing oxidation temperature led to the formation of thicker oxide layer and phase transformation of anatase to rutile. The presence of the oxide layer helped the improvement of corrosion resistance and microhardness. The most improvement in surface roughness was found in the specimens treated at 400°C, which significantly improved surface hydrophilicity. But both surface roughness and hydrophilicity reduced when oxidized at 500°C and 600°C, suggesting that hydrophilicity was dominated by the surface roughness. In addition, this surface treatment did not reduce the biocompatibility of the metallic Ti substrates against murine osteoblasts (MC3T3).     

A study on vertical distribution of elements and their chemical states in Yatsu tideland sediments

We have clarified vertical distribution of thirty and more elements in the Yatsu tideland sediment by instrumental neutron activation analysis (INAA) and prompt g-ray analysis (PGA). The distributions of elements were categorized into three groups according the tendency of each vertical distribution. Chemical states of iron in the sediments were investigated by Mössbauer spectroscopy. In the distribution of iron species, maximum pyrite distribution was found in the middle layer. Paramagnetic high-spin Fe²⁺ distributed complementarily to pyrite, suggesting that the Fe²⁺ was used for pyrite formation.     

Elucidating the mode of action of a corrosion inhibitor for iron

Two polymetallic iron(III) complexes 1 and 2 have been synthesised from the known corrosion inhibitor 3-(4-methylbenzoyl)-propionic acid HL1 and their crystal structures determined. Coordination geometries extracted from these structures have been used as the basis for molecular modelling onto idealised iron(III) oxide surfaces as an aid to understanding the efficacy of inhibitors of the 4-keto acid type. The proposed mode of action involves 1,3-bridging didentate coordination of the carboxylate function of L1 to two FeIII ions, hydrogen-bond formation between the 4-keto group of L1 and a bridging surface hydroxy group, as well as close packing of the aromatic end groups, which should generate a hydrophobic barrier on the surface. Adsorption isotherm experiments have been used to compare the strengths of binding of related carboxylic acids onto iron(III) oxide surfaces and indicate that the presence of the 4-keto function leads to the formation of significantly more stable surface complexes.     

硫酸根离子对铁在弱碱性溶液中阳极溶解和钝化行为的影响

采用浸泡实验, 电化学测试和表面分析技术研究了硫酸根离子浓度对铁在稀碳酸氢钠溶液中开路状态和阳极极化行为的影响. 在无硫酸根离子及含有少量硫酸根离子的碳酸氢钠溶液中, 铁的开路电位约为(-0.225±0.005) V, 并呈现钝化状态, 其电化学阻抗很大, 腐蚀速率较低. 在含有较高浓度硫酸根离子的碳酸氢钠溶液中, 铁的开路电位为(-0.790±0.010) V并呈现活性溶解状态, 其电化学阻抗较小, 腐蚀速率较高, 同时阳极极化曲线上能观察到活化-钝化转变现象. 由于铁在含有较高浓度硫酸根离子的碳酸氢钠溶液中处于活化状态, 阳极极化曲线上存在数个电流峰. 足够高的硫酸根离子浓度会导致铁表面预先形成或转变而成的氧化膜失效. 相比于自然曝氧状态, 在除氧条件下较低的硫酸根离子浓度即可引起铁在碳酸氢钠溶液中由钝态向活性溶解态的转变.     

Production of a biomimetic Fe(I)-S phase on pyrite by atomic hydrogen beam surface reactive scattering

Molecular beam surface scattering and X-ray absorption spectroscopic experiments were employed to study the reaction of deuterium atoms with a pyrite, FeS(2) (100), surface and to investigate the electronic and geometric structures of the resulting Fe-S phases. Incident D atoms, produced by a radiofrequency plasma and expanded in an effusive beam, were directed at a pyrite surface held at various temperatures from ambient up to 200 °C. During exposure to the D-atom beam, D(2)S products were released with a thermal distribution of molecular speeds, indicating that the D atoms likely reacted in thermal equilibrium with the surface. The yield of D(2)S from the surface decreased approximately exponentially with exposure duration, suggesting that the surface accessible sulfur atoms were depleted, thus leaving an iron-rich surface. This conclusion is consistent with X-ray absorption measurements of the exposed surfaces, which indicated the formation of a layered structure, with elemental iron as the outermost layer on top of a formally Fe((I))-S phase as an intermediate layer and a formally Fe((II))-S(2) bulk pyrite layer at lower depths. The reduced Fe((I))-S phase is particularly remarkable because of its similarity to the catalytically active sites of small molecule metalloenzymes, such as FeFe-hydrogenases and MoFe-nitrogenases.     

Development of nanostructured polyaniline dispersed smart anticorrosive composite coatings

Modern engineering science and nanotechnology have hastened the development of high performance corrosion‐resistant coatings having a broad spectrum of effectivity under a wider range of hostile environments. The formulation of such coating systems is expected to cause a major revolution in the corrosion world. Conducting polymers have recently proved to be an effective alternative to phosphate–chromate pretreatment that is hazardous due to toxic hexavalent chromium. Moreover, improvements in environmental impact can be achieved by utilizing nanostructured particulates in coating and eliminating the requirement of toxic solvents. The paper reports some preliminary investigations on the corrosion resistance performance of nanostructured methyl orange (MO)‐doped polyaniline (PANI)/castor oil polyurethane (COPU) composite coatings on mild steel (MS). The nanostructure of the MO‐PANI was confirmed by transmission electron microscopy (TEM). The corrosion protective performance was evaluated by physico‐mechanical properties, corrosion rate, and open circuit potential measurements. These coatings were found to act as “corrosion sensors” by exhibiting different colors when placed in acid as well as alkaline media. The protective behavior of coatings was attributed to the formation of a passive iron oxide/dopant layer at the metal‐coating interface that impedes the penetration of the corrosive ions. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of anodic oxidation on corrosion properties of Al coating by arc spraying in seawater

A layer of Al coatings was prepared on the S355 steel by arc spraying, which was conducted by anodic oxidation treatment; the morphologies, chemical element compositions and phases of Al coating, and anodic oxide layer were analyzed with field emission scanning electron microscope (FESEM), energy dispersive spectrometer (EDS) and X‐ray diffraction (XRD), respectively. The corrosion protections of Al coating before and after anodic oxidation were discussed with a seawater immersion test; the corrosion resistance mechanisms of Al coating and anodic oxide layer in the seawater were also investigated. The results show that the thickness of Al coating is about 300 µm by arc spraying, the sample surfaces become loose after seawater immersion corrosion and Cl^? and O^2? penetrate into the substrate from the cracks, destroying the binding properties of coating–substrate, and the coating fails. After anodic oxidation, the oxide layer is formed in the surface of Al coating with the thickness of about 30 µm; the corrosion products are mainly composed of Al(OH)₃, which barraged the holes caused by seawater corrosion. The corrosion cracks are formed during the corrosion, while the number and depth of cracks decrease obviously after anodic oxidation treatment. The corrosion of Al coating becomes the local corrosion after anodic oxidation treatment, and the grains are smaller, which are easily nucleated to form a new corrosion resistance layer. Copyright © 2015 John Wiley & Sons, Ltd.