Mikrobielle Werkstoffzerstörung – Simulation,Schadensfälle und Gegenmaßnahmen für metallische Werkstoffe: Manganoxidierende Bakterien und Lochkorrosion an Turbinenteilen aus CrNi-Stahl in einem Laufkraftwerk

Microbial deterioration of materials – simulation, case histories and countermeasures for metallic materials: Manganese oxidizing bacteria and pitting of turbine components made of CrNi steel in a hydroelectric power plant In a hydroelectric power plant pitting corrosion of the turbine runner blades (material G-X 5 CrNi 13 4) and the discharge ring (X 3 CrNi 13 4) ocurred at chloride levels of 170 mg/l maximum. Both, potentiostatic stepwise experiments and immersion tests gave no indication for susceptibility to pitting or crevice corrosion of this material in such water. Analysis of calcareous deposits found on the metal surface revealed high amounts of manganese dioxide. It is shown experimentally, that the CrNi-steel can undergo chloride induced pitting corrosion if polarized by manganese dioxide. Manganese oxidizing bacteria and possibly fungi were found to form the deposits. This case may be considered as microbiologically influenced corrosion (MIC) under aerobic conditions.     

Corrosion behavior of carbon steel coated with a zinc-rich paint containing metallic compounds under wet and dry cyclic conditions

The corrosion behavior of carbon steel coated with a zinc-rich paint containing two metallic compounds, Al₂(SO₄)₃ and CaO, as anticorrosive additives was examined under wet and dry cyclic corrosion test conditions. The zinc-rich paint coating without the two metallic compounds formed a white corrosion product and red iron rust on the surface after the corrosion test, whereas the coating with the metallic compounds showed reduced surface corrosion products. The corrosion current density of the painted steel substrate decreased drastically due to the incorporation of metallic compounds in the paint. The zinc-rich paint coating modified with the metallic compounds contained dispersed simonkolleite (Zn₅(OH)₈Cl₂·H₂O) phase and possibly very fine CaSO₄ particles, which remarkably improved the protectiveness of the zinc-rich paint coating.     

金属衬板材料的发展及其磨损失效机制概述

综述了国内外金属衬板材料的发展历史与现状;指出了当前国内抗磨材料选用及研发等方面的不足之处;介绍了在不同服役条件下选用奥氏体锰钢,合金抗磨铸铁,低、中、高合金抗磨钢三大类型抗磨材料的利弊,以及纯磨粒磨损及腐蚀条件下磨损的失效机制及相关对策。     

Electrochemical codeposition of PMMA particles with zinc

Zinc matrix composite coatings containing polymethyl methacrylate (PMMA) particles were electrodeposited from an aqueous acidic (pH 2.0 and 4.0), lignosulfonate solution of zinc sulfate on low-carbon steel substrates, under galvanostatic, either constant or pulse current, plating conditions at current densities of 2 and 20 A dm⁻². The effect of particle inclusion on the deposit electrocrystallization was investigated by X-ray diffraction and scanning electron microscopy. The observed dependence of the PMMA content of the deposits on bath pH and applied current density was illustrated in terms of the particle surface charge variation and their interaction with the growing metal phase. The corrosion resistance of the composite coatings was evaluated by Tafel analysis.     

复合缓蚀剂对碳钢腐蚀率的影响研究

目的研究异抗坏血酸钠、六偏磷酸钠、D-葡萄糖酸钠和硫酸锌的复配物在软化水水质中对碳钢腐蚀率的影响。方法通过静态挂片和旋转挂片实验,研究不同浓度、pH值、温度等条件下,复合缓蚀剂对碳钢腐蚀率的影响,对腐蚀机理进行探讨。结果在软化水pH=10,缓蚀剂质量浓度为150 mg/L,温度为50℃的条件下,复合缓蚀剂对碳钢有较好的缓蚀效果,静态挂片实验中碳钢的腐蚀率为0.0303mm/a,缓蚀率为86.31%;旋转挂片实验中碳钢的腐蚀率为0.0350 mm/a,缓蚀率为96.12%。结论在软化水水质中,碳钢的腐蚀率随着复合缓蚀剂投药量、溶液pH值的增大而降低,随着温度的升高而增大。     

Galvanic Series of Metals and Effect of Alloy Compositions on Corrosion Resistance in Sanya SeawaterEI北大核心CSCD

With the development of ocean engineering, various metallic materials have been applied to the marine environment. It is an urgent requirement to study the galvanic series and alloy composition optimization of metallic materials in the tropical marine environment. In this work, open circuit potentials (OCP) and galvanic series of 36 kinds of metallic materials in Sanya seawater were studied. By considering the response of OCP to tidal changes, the anti-corrosion effects of alloying elements were also ana lyzed. The results show that the OCP of metallic materials in Sanya seawater has a large range. The galvanic series order of metallic materials from high to low in Sanya seawater is: nickel alloy, duplex stainless steel, austenitic stainless steel and pure copper, ferritic stainless steel, martensitic stainless steel, copper alloy, low alloy steel, carbon steel, cast iron, aluminum alloy and aluminum anode. Low-carbon high-alloy content carbon steel and high Cr, Ni contents stainless steel have higher OCP. The potential fluctuations of carbon steel with tidal changes involves two phases: (1) under the dynamics control, the OCP of carbon steel is more negative at high tide; (2) under the diffusion control, the OCP is more positive at high tide. The potential fluctuations of metallic materials reflect the effect of the corrosion product film on the change of ionization balance, and metals with less potential fluctuations have better inhibition on ion diffusion. In Sanya seawater, the carbon steel, which has more alloying content and less carbon content, has less potential fluctuations with the tidal changes and has good oxygen diffusion resistance. The potential fluctuations of austenitic stainless steel with tidal changes are less than that of ferritic stainless steel and martensitic stainless steel. After 2700 h immersion, austenitic stainless steel and martensitic stainless steel, which have a higher content of Mo, have more stable OCP. In other words, the corrosion film gets a better corrosion resistance. The OCP of aluminum anode in Sanya seawater environment increases when the oxygen content is brought up. The OCP of Zn-containing or Ga-containing aluminum anode remains relatively stable. Al bronze and T2 copper have less potential fluctuations with tidal changes, and perform good corrosion resistance in Sanya seawater.     

Influence of pH on corrosion behavior of carbon steel in simulated cooling water containing scale and corrosion inhibitors

In this paper, the influence of pH on the corrosion behavior of AISI 1020 carbon steel in simulated cooling water was investigated by using electrochemical and surface analysis methods. The results of polarization showed that the corrosion resistance of carbon steel increased with an increase in pH of the simulated water, and the corrosion control process changed from cathodic polarization to anode polarization control. The scale and corrosion inhibitor 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) had a certain anodic corrosion inhibition effect on carbon steel, whereas Zn²⁺ acted as a cathodic inhibitor for carbon steel in simulated water with pH 7–9. In simulated water containing both PBTCA and Zn²⁺, a good synergistic corrosion inhibition was found between PBTCA and Zn²⁺, and their corrosion inhibition effect on carbon steel was the best at pH 8. This was attributed to the formation of Zn(OH)₂ precipitate film in the cathode region and the formation of Zn–PBTCA complex film in the anode region at this pH.     

Accelerated Corrosion of Metallic and Reinforced Concrete Constructions when Connected to Lightning Conductors

Abstract

With the object of examining the influence on the corrosion of metallic and reinforced concrete constructions of their connection to lightning conductors (as is demanded by the regulations of some countries), the following measurements were made: (1) corrosion potentials of steel and copper specimens (in the form of sheets) in distilled water at 25°c vs time: (2) potentiostatic curves of steel and copper specimens (in the form of sheets) in distilled water at 25° c; (3) weight loss of steel and copper specimens in the form of sheets (in ASTM corrosion chamber) and in the form of tubes (by internal circulation of artificial sea water at 70° c) and of the reinforcements of reinforced concrete specimens (in circulating sea water at 25°c). All these experiments were done with the specimens both unconnected and connected to lightning conductors (or needles); in some cases artificial lightning was introduced. These experiments proved that connecting metallic specimens and reinforcements of reinforced concrete to lightning conductors (or metallic needles) increased their corrosion rate.

In subsequent papers the results of pilot plant and full scale experiments under natural conditons will be presented.     

Acidic/caustic alternating corrosion on carbon steel pipes in heat exchanger of ethylene plant

Caustic embrittlement, a kind of stress corrosion cracking (SCC), is always encountered on materials under stresses amid caustic environment. Acidic corrosion is another familiar degradation on materials contacting acidic media. However, it has been seldom studied what effect would be resulted in on materials that are exposed to an acidic/caustic alternating environment. In this paper, failure events were discovered on the carbon steel pipes under such an alternating service condition due to frequent sharp fluctuations of the heat medium's (process water) pH values in a heat exchanger. What is more, even chloride ions and sulfur element were detected, i.e., pitting corrosion was involved as well. In order to identify the causes of the failure, matrix materials of the pipes were examined, failure defects on pipe surfaces were investigated, particularly the process water was thoroughly inspected via a series of characterization methods. Based on the analysis results, a novel four‐level mechanism from microscopic scale to macroscopic scale was tentatively proposed to explain such an acidic/caustic alternating corrosion.     

The corrosion of carbon steel by wet elemental sulphur

The corrosion behaviour of carbon steel in wet elemental sulphur under both aerobic and anaerobic conditions is reported. The corrosion reaction was studied as a function of the initial pH of the system and the particle size of sulphur. Catastrophic corrosion is observed after an induction period which is found to be a function of the initial pH of the system, the particle size of the sulphur and the presence or absence of oxygen. Corrosion potential measurements suggest that the observed catastrophic corrosion process is subject to catalysis of the cathodic reaction. A possible mechanism for the corrosion reaction is discussed.     

海水环境中金属材料腐蚀磨损及耐磨防腐一体化技术的研究进展

随着"建设海洋强国"战略的实施,发展海洋装备、建设海洋工程成为推进和实施国家海洋战略的重要内容。鉴于海洋装备长期服役于海洋环境,因此海洋工程材料的腐蚀损伤是不可回避的关键问题,尤其是海洋装备中的运转部件,如海水泵、阀、海水液压传动系统、水下作业机器手、深海勘探和开采装备等面临腐蚀与磨损的耦合损伤。基于此,针对典型金属材料在海水环境中的腐蚀磨损失效行为及机理,综述了服役工况、腐蚀介质、电化学及材料因素对典型金属材料(如不锈钢、钛合金、铝合金、镍合金)在海水环境中腐蚀磨损性能的影响,综合分析了服役工况、腐蚀介质浓度、p H值、外加电位与材料性能之间的关系,阐明了金属材料腐蚀磨损过程中腐蚀、磨损及其交互作用。在此基础上,对比了一系列耐磨与防腐一体化涂层技术,如PVD涂层、热喷涂涂层、电镀涂层及聚合物粘结涂层的腐蚀磨损性能及典型应用,分析了耐磨与防腐一体化防护材料对腐蚀磨损性能的优化机理,以期为解决金属材料的腐蚀磨损问题提供有益借鉴。     

Investigations on the protection effect of filling materials for post‐tensioning systems under construction conditions

About the long‐term protection behaviour of corrosion protection materials (filling materials) for prestressed systems under critical environmental conditions is only little known. The corrosion protection effect is usually based on theoretical considerations and is proven by short‐term tests. The selection of the different products is mainly made according to economical or workability criteria. In a research project the barrier effect of different commercial corrosion protection materials (waxes as well as oil‐based greases) against water, their tendency for undercutting as well as their additional corrosion protection effect were investigated. The exposure tests were carried out with non‐stressed as well as stressed prestressing steel specimens which were subjected to critical conditions (condensed water, artificial soil solution, direct soil contact). Parallel to these long‐term exposure tests the applicability of different electrochemical techniques and their significance with respect to testing the corrosion protection ability and water absorption was evaluated. Within the project a suitable method for simple testing the performance of corrosion protection materials under real conditions was developed. By means of a small compact cell submicroscopical reactions of the used sensors could be measured. The high sensitivity of this measuring technique enables the detection of degradation processes at thin protection layers.     

Microbiologically influenced corrosion of steels by thermophilic and mesophilic bacteria

Bacterial influenced corrosion of AISI 316 stainless steels (SS) and ASTM A36 carbon steel by two strains of sulfate reducing bacteria (SRB) were analyzed. Thermophilic and mesophilic bacteria were isolated from the condensate fluid of “Los Azufres”, a geothermal electric field located in the State of Michoacan at Central Mexico. Anaerobic corrosion tests were carried out for 15, 30 and 60 days in lactate‐containing media at 50 °C and 40 °C. Scanning electron microscopy (SEM) was used to determine corrosion morphology. Pitting density was determined with an optical microscope. Corrosion potential, anodic potentiodynamic polarization curves and pH values were measured under anaerobic conditions. Results show that the microbial activity influenced the overall corrosion process, whereas, pitting corrosion and localized attack corrosion (LAC) were found. The anodic polarization curves show that passivation and activation processes should take place on the steel surface of the sample and pH decreases as the exposure time increases.     

The anoxic corrosion behaviour of carbon steel in anoxic alkaline environments simulating a Swiss L/ILW repository environment

The Swiss waste management programme foresees that low- and intermediate-level radioactive waste will be disposed of in a deep geological repository constructed in Opalinus Clay. Gas generation is expected in the repository due to the decomposition of organic materials and the corrosion of metals, with carbon steel being the primary source. The corrosion behaviour of mild steel under anoxic conditions has been studied over the course of several years to better understand the long-term hydrogen evolution profile under anticipated repository conditions. Steel, either bare or encased within mortar, was tested in water vapour or immersed in electrolytes representative of aged cement waters at 50°C. The corrosion rate was measured indirectly through the hydrogen analysis using a solid-state probe. The hydrogen evolution behaviour of grout was also monitored to more accurately determine the hydrogen generating from the corrosion of the embedded steel. For steel in water vapour or in alkaline environments, embedded in cementitious material or immersed in simulated aged cement pore water, corrosion rates were invariably <1 nm/year after several years of analysis.     

铁细菌对L245钢腐蚀行为的影响研究

采用挂片、电化学实验和SEM等手段研究了L245钢在含有铁细菌(FB)的页岩气压裂产出水中的腐蚀行为。结果表明:有、无FB压裂产出水都会对L245钢造成腐蚀,但失重分析和极化曲线分析都证明FB的存在促进了L245钢的腐蚀;电化学阻抗拟合结果表明,在不含FB的页岩气压裂产出水中,L245钢的腐蚀速率在前5 d逐渐增大,后快速减小。在含有FB的页岩气压裂产出水中,L245钢的腐蚀速率先减小,至8 d后逐渐增大。SEM分析结果表明,两种体系生成了不同的腐蚀产物膜。     

铁基非晶基涂层的HVOF制备及耐腐蚀性能(英文)

以工业原材料制备的铁基非晶合金、镍铬合金、碳化钨颗粒的混合粉末为原材料,采用高速火焰喷涂技术制备铁基非晶基涂层。通过分析铁基非晶基涂层分别在1 mol/L盐酸、氯化钠、硫酸和氢氧化钠溶液中的动态极化特性,研究其腐蚀阻抗。采用扫描电子显微镜(SEM)分析涂层的腐蚀形貌。结果表明:铁基非晶基涂层具有优良的耐蚀性能,而且在含氯离子溶液中,表现出比304L奥氏体不锈钢更高的腐蚀阻抗。在1 mol/L盐酸溶液中,铁基非晶基涂层的腐蚀电流密度和钝化电流密度分别为132.0μA/cm2和9.0 mA/cm2,在1 mol/L氯化钠溶液中分别为2.5μA/cm2和2.3 mA/cm2,且表现出一个宽的自钝化区间。其优异的耐蚀性能表明铁基非晶基粉末可以作为一种耐腐蚀、耐磨损的工程材料。     

Sliding Wear Characteristics and Corrosion Behaviour of Selective Laser Melted 316L Stainless Steel

Stainless steel is one of the most popular materials used for selective laser melting (SLM) processing to produce nearly fully dense components from 3D CAD models. The tribological and corrosion properties of stainless steel components are important in many engineering applications. In this work, the wear behaviour of SLM 316L stainless steel was investigated under dry sliding conditions, and the corrosion properties were measured electrochemically in a chloride containing solution. The results show that as compared to the standard bulk 316L steel, the SLM 316L steel exhibits deteriorated dry sliding wear resistance. The wear rate of SLM steel is dependent on the vol.% porosity in the steel and by obtaining full density it is possible achieve wear resistance similar to that of the standard bulk 316L steel. In the tested chloride containing solution, the general corrosion behaviour of the SLM steel is similar to that of the standard bulk 316L steel, but the SLM steel suffers from a reduced breakdown potential and is more susceptible to pitting corrosion. Efforts have been made to correlate the obtained results with porosity in the SLM steel.     

海洋环境下金属材料微生物腐蚀研究进展

海洋环境下的微生物易附着在金属材料表面形成生物膜,进而导致金属材料表面的微生物腐蚀(MIC)。分析了海洋环境下常见的易导致腐蚀的微生物种类及其特征,如硫酸盐还原菌(SRB)、铁氧化细菌(IOB)、产酸菌(APB)与产粘液菌(SPB)等,归纳了船舶与海洋平台涉及的微生物腐蚀及其与材料摩擦磨损的协同作用。在此基础上,重点综述了近年来碳钢、不锈钢与铜合金在海洋环境下的微生物腐蚀研究进展,包括溶解氧(DO)浓度、胞外聚合物(EPS)、生物膜微观形态等因素对碳钢MIC的影响,不锈钢在MIC过程中钝化膜与Cr元素化合物形态与含量变化,微生物抵抗Cu离子毒性机制以及铜合金在MIC过程中出现的脱合金成分腐蚀。对比了碳钢、不锈钢与铜合金表面在MIC中由生物膜、腐蚀产物与钝化膜形成的复合表面层结构差异。并从阴极去极化理论与微生物电化学腐蚀理论的角度解释了MIC,总结了两种理论间的关联性与局限性,指出了一些亟待解决的问题。     

FV（520）B不锈钢在CO2/H2S共存条件下的腐蚀行为

目的研究长输管线压缩机叶片材料FV(520)B不锈钢在高含H_2S、H_2O、CO_2条件下的腐蚀行为。方法利用高温高压反应釜模拟特定工况,在H_2S分压为0.9 MPa、CO_2分压为0.6 MPa、温度为150℃的条件下于5 g/L的氯化钠溶液中制备硫化腐蚀层,利用XPS、SEM、XRD等手段对腐蚀层的成分及结构进行分析。结果 FV(520)B不锈钢的腐蚀速率逐渐降低,试样表面粗糙度先增大后下降,腐蚀产物主要为FeCO_3、Fe_3O_4、FeS、FeS_2、S、Cr_2S_3、Cr_2O_3和Cr(OH)_3。结论在腐蚀前期,FeS的形成速率大于FeS_2、S,腐蚀产物颗粒不断长大。形成完整的Cr_2O_3、Cr(OH)_3保护膜后,腐蚀得到抑制,此时腐蚀反应主要为FeS_2、S的生成,试样表面腐蚀产物颗粒尺寸变小,试样表面粗糙度降低。     

硼酸缓冲溶液中pH值和腐蚀产物对低碳钢活化/钝化敏感性的影响

研究了在pH值分别为8,9和10的除氧硼酸缓冲溶液中,低碳钢腐蚀产物对其活化/钝化敏感性的影响.实验结果表明,在pH值为8时,低碳钢一直处于活性溶解状态,不受腐蚀产物影响;在pH值为9和10时,表面腐蚀产物使低碳钢钝化,其腐蚀电位最后稳定于钝化区间.XPS和XRD等分析结果表明,腐蚀产物由FeB(OH)12B4O7和γ...