从生物能量学和生物电化学角度研究金属微生物腐蚀的机理

人类认知由微生物导致的金属腐蚀现象距今已有一个多世纪的历史。最近20年,微生物腐蚀(Microbiologically influenced corrosion,MIC)已成为金属腐蚀的一个研究热点。因为缺乏对MIC机理的深入了解和认识,人们甚至认为MIC是腐蚀领域中的一个"谜"。因此,迫切需要了解MIC的发生机理。最新的研究结果表明,金属的微生物腐蚀在本质上是一个生物电化学过程。在微生物与金属并存的环境中,当电子供体(如碳源)不存在或消耗掉之后,微生物用金属代替碳源获取电子,导致金属发生微生物腐蚀。另外一种腐蚀机理是,微生物的代谢产物(比如有机酸)导致金属腐蚀。腐蚀是一个能量释放的反应过程,微生物通过腐蚀金属得到维持其生命所必需的能量。目前,电化学方法已应用于微生物金属腐蚀研究,学者们提出了诸如"阴极去极化"等经典理论。但单纯从电化学角度研究微生物腐蚀金属可能得到一些片面的结论。随着对这一领域研究的不断深入人们认识到必须结合生物能量学以及生物电化学方面的知识,以更好地理解微生物影响金属腐蚀的进程。本文总结这方面的最新研究进展,并着重介绍"生物催化阴极还原"理论(Biocatalytic cathodic sulfate reduction,BCSR)和"电化学微生物腐蚀"理论(Electrical microbial influenced corrosion,EMIC)等最新的金属微生物腐蚀机理。本文主要从生物能量学和生物电化学方面介绍金属微生物腐蚀机理研究,这是目前国际上一种新的研究方法和思路。BCSR就是依据这一思路解释了微生物为什么和怎样腐蚀金属这一MIC研究领域中的这一难题。     

X100管线钢在库尔勒土壤模拟溶液中的微生物腐蚀特征

采用线性极化曲线和交流阻抗技术(EIS)结合扫描电子显微镜和能谱分析仪,研究了SRB对X100管线钢在库尔勒土壤模拟溶液中腐蚀行为的影响。实验结果表明:X100管线钢在无菌与含SRB模拟溶液中的腐蚀均属于中度腐蚀;SRB加剧了X100管线钢在库尔勒土壤中的腐蚀,但在浸泡17~35d过程中,微生物膜与腐蚀产物结合成的复合膜会在短时间内发生急剧抑制腐蚀作用;X100管线钢在无菌模拟溶液中的腐蚀倾向为随时间延长先减小后增大,含SRB时为先减小后增大再减小,腐蚀速率在无菌与含SRB模拟溶液中时均为随时间延长先减小后增大。     

X100管线钢在库尔勒土壤模拟溶液中的微生物腐蚀特征

采用线性极化曲线和交流阻抗技术(EIS)结合扫描电子显微镜和能谱分析仪,研究了SRB对X100管线钢在库尔勒土壤模拟溶液中腐蚀行为的影响。实验结果表明:X100管线钢在无菌与含SRB模拟溶液中的腐蚀均属于中度腐蚀;SRB加剧了X100管线钢在库尔勒土壤中的腐蚀,但在浸泡17~35d过程中,微生物膜与腐蚀产物结合成的复合膜会在短时间内发生急剧抑制腐蚀作用;X100管线钢在无菌模拟溶液中的腐蚀倾向为随时间延长先减小后增大,含SRB时为先减小后增大再减小,腐蚀速率在无菌与含SRB模拟溶液中时均为随时间延长先减小后增大。     

铁氧化菌作用下316L不锈钢点蚀电化学特性的研究

采用电化学测量、交流阻抗技术、扫描电镜观察和能谱分析等实验方法,研究了316L不锈钢在铁氧化菌(IOB)溶液中的腐蚀电化学行为,分析了炼油厂冷却水系统微生物腐蚀的特征及机制,结果表明,在含有IOB溶液中的自腐蚀电位(Ecorr)、点蚀电位(Epit)和极化电阻(Rp)均随浸泡时间的增加呈现出降-升-降的变化趋势;在含有IOB溶液中的腐蚀速率均大于在无菌溶液中;IOB的生长代谢活动及其生物膜的完整性和致密性影响了316L不锈钢表面的腐蚀过程,使不锈钢表面的钝化膜层腐蚀破坏程度增加,加速了316L不锈钢的点蚀.     

SRB对X70管线钢在喷气燃料中腐蚀行为的影响

目前,关于油水体系中微生物的腐蚀形成过程、腐蚀机理、检测和评价手段、影响因素以及腐蚀控制方法等研究尚不成熟。采用失重法、线性极化曲线和电化学阻抗谱技术,结合扫描电子显微镜(SEM)和能谱分析仪(EDS)研究了X70管线钢在含硫酸盐还原菌(SRB)的喷气燃料中的腐蚀行为。结果表明:X70管线钢在无菌介质中的腐蚀类型为局部腐蚀;在有菌介质中腐蚀比较严重,出现大面积溃疡状腐蚀区域并伴有大量鼓泡现象,浸泡初期腐蚀速率最大,随着浸泡时间的延长,腐蚀仍然在进行,但腐蚀速率有所下降,SRB参与并促进了X70管线钢的腐蚀,加速阴极反应,增大了X70管线钢的腐蚀倾向。     

碱液输储装置用12Cr13钢的热浓碱液腐蚀行为

目前对12Cr13钢在碱液中的腐蚀行为未见研究报道.采用浸泡试验通过调整流速、碱液浓度、浸泡时间等参数研究了12Cr13钢在热浓碱液中的腐蚀行为,以明确不同因素影响碱液腐蚀的规律及碱液腐蚀机理.结果表明:试验范围内12Cr13钢静态下的腐蚀速率大于动态下的,流速增大加速了试样的腐蚀及钝化膜的修复,促进了材料表面钝化膜的生成,降低了腐蚀速率.碱液浓度低(0～20％)时12Cr13钢以钝化为主,腐蚀速率较低,碱液浓度高(＞20％)时由于过钝化溶解,使腐蚀速率显著增大;在45％碱液中12Cr13钢经历着钝化膜的生成、过钝化溶解及钝化膜的修复过程,腐蚀速率随时间增大呈先增大后降低趋势,浸泡7d出现最大腐蚀速率;动态条件下这些过程被加速,腐蚀速率减小,约是静态下的1/2.     

P型单晶硅片在KOH溶液中腐蚀行为的电化学研究

采用电化学极化测量技术研究了p(100)和p(111)硅片在碱性KOH溶液中的腐蚀行为,考察了KOH溶液浓度、温度和硅片表面缝隙等因素对腐蚀行为的影响.结果表明:在室温下当KOH浓度为5～6 mol/L时硅片腐蚀速率最大;随着KOH腐蚀液温度增加,腐蚀速率增大,在50℃左右腐蚀速率增加显著;硅片表面缝隙会加剧硅的局部腐蚀,在同等实验条件下缝隙腐蚀速率比均匀腐蚀快一个数量级.     

B10铜镍合金海水加速腐蚀行为

B10铜镍合金具有优良的耐海水腐蚀性能,为研究其在海水中的腐蚀行为,取厦门天然海水,加入双氧水作为腐蚀加速剂,在室内模拟海水全浸腐蚀实验,采用失重法、电化学阻抗谱(EIS)技术分析B10合金在海水腐蚀中的腐蚀速率随腐蚀时间的变化规律,用不同腐蚀周期的电化学阻抗谱特征来表征工作面积为1cm~2的合金表面氧化膜的生长破坏情况。结合扫描电子显微镜(SEM)、能谱分析(EDX)、XPS和拉曼光谱技术分析B10合金表面腐蚀产物膜的成分以及B10合金在海水腐蚀中的腐蚀类型。结果表明,氧化膜的生成与破坏使得合金在海水中的瞬态腐蚀速率呈先减小后增大的趋势,腐蚀产物包含碱式氯化铜Cu_2(OH)_3Cl和氧化亚铜Cu_2O,腐蚀由点蚀开始,逐渐经历了晶间腐蚀-剥蚀。     

阴离子和硫酸盐还原菌作用下管线钢腐蚀行为的研究进展

近年来,在油气输送过程中,管线泄漏事故屡次发生,这不仅会威胁管线的安全运行,而且会造成环境的污染和巨大的经济损失。腐蚀是造成管线泄漏事故的主要原因。管线钢被广泛地铺设于土壤或海底等环境中,而这些环境通常具有十分复杂的腐蚀特性,如腐蚀性阴离子、微生物、温度、溶解氧、pH值等多种因素都会对管线钢的腐蚀造成影响。因此,在这些因素的共同作用下,管线钢的腐蚀问题不可避免。其中阴离子和硫酸盐还原菌(Sulfate-reducing bacteria,SRB)是造成管线钢腐蚀最主要的因素。在管线钢服役环境中,可能存在Cl~-、SO_4~(2-)、CO_3~(2-)、NO_3~-、S~(2-)等腐蚀性阴离子,其中Cl~-与SO_4~(2-)最为普遍,相关研究较为充分。有关Cl~-对管线钢腐蚀影响规律的研究结果较统一,即随着Cl~-浓度的升高,管线钢的腐蚀速率加快。而有关SO_2-4对管线钢腐蚀的影响规律,目前的观点尚不统一。此外,研究者们在SRB对管线钢腐蚀行为影响方面也做了大量的研究工作。部分研究结果表明,SRB的新陈代谢会加速管线钢腐蚀,还有研究认为SRB会在管线钢表面生成生物膜保护金属,减缓管线钢腐蚀的发生。如今,研究者们意识到管线钢腐蚀的影响因素是多种环境因素共同作用的结果,不能取决于单一环境因素。因此,阴离子与SRB的协同作用对管线钢腐蚀行为的影响成为了目前学术界的研究焦点。研究发现,当阴离子与SRB共同存在时,阴离子会改变SRB的活性,进而影响管线钢的腐蚀行为。目前研究主要集中于Cl~-与SRB共存时,Cl~-浓度反映介质中的盐度,盐类可以通过改变微生物水中的渗透压,影响细菌物质运输,从而改变微生物活性。当腐蚀介质中Cl~-含量较高时,SRB的生长繁殖会被抑制,大部分SRB细胞脱水死亡,不会发生明显的微生物腐蚀,但在Cl~-含量不高且适宜SRB生长的环境中,SRB会与Cl~-共同作用,导致金属发生明显的微生物腐蚀。本文分别综述了阴离子与SRB对管线钢腐蚀行为的影响,总结了SRB与阴离子的协同作用对管线钢腐蚀行为影响的研究现状,提出了当前研究的缺陷与不足并对未来的研究进行了展望。     

硫酸盐还原菌对船体低合金裸钢腐蚀行为的影响

船体舱室底部存积的油污水为腐蚀微生物的生长繁殖提供了有利条件。为了研究腐蚀微生物硫酸盐还原菌(SRB)对某新型船体低合金钢腐蚀的影响,采用荧光显微技术、失重分析、电化学分析、腐蚀产物成分分析及微区成分分析等手段,研究了取自舱底环境中分离提纯的SRB对船体低合金钢腐蚀行为的影响。结果表明,在SRB腐蚀初期,胞外聚合物(EPS)对全面腐蚀有一定的抑制作用,但随着时间的延长,铁硫化合物层可作为阴极与裸露部位的小阳极发生反应,加上SRB的共同作用,加速局部破裂处的阳极溶解,促进点蚀。在整个浸泡周期内,船体低合金钢在SRB介质中的腐蚀电流密度均大于灭菌介质中的,且年平均腐蚀速率是灭菌介质中的1.36倍。     

Probability density fittings of corrosion test-data: Implications on C6H15NO3 effectiveness on concrete steel-rebar corrosion

In this study, corrosion test-data of steel-rebar in concrete were subjected to the fittings of the Normal, Gumbel and the Weibull probability distribution functions. This was done to investigate the suitability of the results of the fitted test-data, by these distributions, for modelling the effectiveness of C₆H₁₅NO₃, triethanolamine (TEA), admixtures on the corrosion of steel-rebar in concrete in NaCl and in H₂SO₄ test-media. For this, six different concentrations of TEA were admixed in replicates of steel-reinforced concrete samples which were immersed in the saline/marine and the microbial/industrial simulating test-environments for seventy-five days. From these, distribution fittings of the non-destructive electrochemical measurements were subjected to the Kolmogorov–Smirnov goodness-of-fit statistics and to the analyses of variance modelling for studying test-data compatibility to the fittings and testing significance. Although all fittings of test-data followed similar trends of significant testing, the fittings of the corrosion rate test data followed the Weibull more than the Normal and the Gumbel distribution fittings, thus supporting use of the Weibull fittings for modelling effectiveness. The effectiveness models on rebar corrosion, based on these, identified 0.083% TEA with optimal inhibition efficiency, η = 72.17± 10.68%, in NaCl medium while 0.667% TEA was the only admixture with positive effectiveness, η = 56.45±15.85%, in H₂SO₄ medium. These results bear implications on the concentrations of TEA for effective corrosion protection of concrete steel-rebar in saline/marine and in industrial/microbial environments.     

Studies on corrosion inhibition of steel reinforcement by phosphate and nitrite

This work deals with the effectiveness of sodium phosphates and nitrites used as inhibitors against steel corrosion in concrete reinforcement. First, concrete pore water was simulated with several alkaline solutions. Then, reinforced concrete specimens with inhibitors added in fresh concrete mix are immersed in chloride solution. The effectiveness of inhibitors was assessed by applying electrochemical techniques, namely Electrochemical Impedance Spectroscopy (EIS), Polarisation Curves (PC), and Open Circuit Potential (OCP) measurements. The final concrete condition was analysed with Scanning Electronic Microscopy (SEM), X-Ray Diffraction (XRD) and Infrared Spectroscopy (FT-IR).In solutions simulating concrete contaminated with chloride, the influence of the inhibitors on the steel corrosion was assessed by (PC) and (EIS). The results obtained show that phosphate prevents pitting corrosion when its content is equal to chloride concentration, and that nitrite only contributes to increase the value of pitting potential. Corrosion rate is reduced with both inhibitors at the different contents tested.For reinforced concrete specimens immersed in chloride solution, their conditions were assessed by applying EIS. The results indicate that after 1 year of immersion with the two inhibitors the corrosion rate decreased. Then, after 3 years of immersion no influence of inhibitors on the corrosion rate was observed. However a significant increase in concrete electrical resistance was observed when inhibitors were present. Visual examinations showed that all steel bars were corroded in the presence of chlorides.Results from analytical tests done on the concrete after 3 years of immersion show that as far as the final concrete condition is concerned, the tested inhibitors did not change the type of compounds in concrete. But the final free chloride content remained higher than the critical chloride threshold. The results of FT-IR technique showed that nitrites are likely washed out of concrete during immersion in chloride solution and phosphates interfere with the equilibrium between CO₃ ^2? and HCO₃ ^? in concrete.The main conclusion of this study is: the efficiency of the tested inhibitors decreases with time, after two years of immersion in chloride solution.     

Effectiveness of corrosion inhibitors in contaminated concrete

Four types of corrosion inhibitors (calcium nitrite at two dosages, calcium nitrate at three dosages and two organic inhibitors at their recommended dosages) were evaluated at five different levels of contamination, i.e., 0.8% chloride; 0.8% chloride plus 1.5% SO₃; seawater; brackish water; and unwashed aggregates. Concrete specimens were used to assess the effect of corrosion inhibitors on the compressive strength of concrete and reinforcement corrosion. The results indicated that the corrosion inhibitors investigated in this study did not adversely affect the compressive strength of concrete. Furthermore, calcium nitrite was efficient in delaying the initiation of reinforcement corrosion in the concrete specimens contaminated with chloride, while both calcium nitrite and calcium nitrate mitigated the corrosive effects of chloride plus sulfate salts or sea water. In the concrete specimens prepared with brackish water or unwashed aggregates, all the inhibitors were effective in reducing the rate of reinforcement corrosion. The type and dosage of corrosion inhibitor were observed to be dependent on the nature and level of contamination.     

混凝土微生物腐蚀防治研究现状和展望

介绍了混凝土微生物腐蚀的危害,结合混凝土微生物腐蚀的作用机理,分析了国内外混凝土微生物腐蚀防治措施的研究现状和存在的问题,并展望了未来的发展趋势.     

Effects of surface washing on the mitigation of concrete corrosion under sewer conditions

This study systematically investigated the potential of mitigating sulfide induced sewer concrete corrosion by surface washing. Washing interrupted the corrosion activity of concrete coupons by increasing the surface pH and decreasing the H₂S uptake rates (SUR). The SUR recovered to the level prior to washing within 60–140 days. The slowest recovery rate was from the most severely corroded coupon. However, no significant difference was observed for concrete mass loss of the washed and unwashed coupons after 54 months. The results suggest that frequent washing at short intervals of a few months might be needed to control corrosion over a long term.     

Effect of corrosion layer of steel bar in concrete on time-variant corrosion rate

Corrosion current density of steel bar in concrete was measured in active corrosion process under a designed artificially controlled climate environment. The active corrosion process shows the characteristics of the time-variant corrosion rate, and the three phases of the corrosion process are presented. The corrosion rate decreases at first; this is followed by a steady state phase; finally after concrete cover cracking caused by corrosion, an ascending phase of the corrosion rate is observed. The mechanism of the time-variation characteristics is discussed based on the microstructure of the interfacial transition zone (ITZ) between steel bars and concrete at different corrosion levels. The microstructure shows that the porous interfacial transition zone gradually transforms into a dense corrosion layer composed of concrete and corrosion products due to expansion of the corrosion products. The layer is called as corrosion layer for short in this paper. The main reason for the descent of the corrosion rate is that transportation of oxygen and moisture is retarded due to the dense corrosion layer. When the equilibrium between rates of consumption and transportation of oxygen is reached, the corrosion rate tends to be steady. The concrete cover cracking offers new access for transporting oxygen and the corrosion rate speeds up.     

Impact of mechanical loading on the corrosion of steel reinforcement in concrete structures

This paper presents results of an experimental investigation on the effect of mechanical loading on the corrosion of steel reinforcement in concrete. Reinforced concrete beams were cast, subjected to mechanical loadings and then exposed to corrosive environment. Successive drying and wetting cycles using 3% sodium chloride salt solution were used to accelerate the corrosion attack. Electrochemical techniques such as macrocell corrosion current, linear polarization resistance (LPR), corrosion potential (E _corr ) and electrochemical impedance spectroscopic (EIS), were used to evaluate the corrosion behavior of the reinforcement. Also, chloride penetration profile and visual inspection of the beam rebars were obtained. The results shows that the pre-exposure mechanical load has no influence on the corrosion initiation or corrosion rate thereafter, unless it reaches to some limit where it develops connected cracks through which the chloride ions flow and depassivate the rebars. The load of 25% of the ultimate capacity seems to be the critical load limit where some microcracks onset to be connected, facilitate the chloride ions flow, and initiate the rebar corrosion.     

Electromagnetic Metrology on Concrete and Corrosion

To augment current methods for the evaluation of reinforcing bar (rebar) corrosion within concrete, we are exploring unique features in the dielectric and magnetic spectra of pure iron oxides and corrosion samples. Any signature needs to be both prominent and consistent in order to identify corrosion within concrete bridge deck or other structures. In order to measure the permittivity and propagation loss through concrete as a function of temperature and humidity, we cut and carefully fitted samples from residential concrete into three different waveguides. We also poured and cured a mortar sample within a waveguide that was later measured after curing 30 days. These measurements were performed from 45 MHz to 12 GHz. Our concrete measurements showed that the coarse granite aggregate that occupied about half the sample volume reduced the electromagnetic propagation loss in comparison to mortar. We also packed ground corrosion samples and commercially available iron-oxide powders into a transmission-line waveguide and found that magnetite and corrosion sample spectra are similar, with a feature between 0.5 GHz and 2 GHz that may prove useful for quantifying corrosion. We also performed reflection (S₁₁) measurements at various corrosion surfaces and in loose powders from 45 MHz to 50 GHz. These results are a first step towards quantifying rebar corrosion in concrete.     

Nondestructive Evaluation of Fiberglass Wrapped Concrete Bridge Columns

Many in-service concrete bridge decks and columns built before the advent of epoxy coated bars show cracking and spalling of the concrete due to corrosion of the steel reinforcement. In cold regions, the corrosion rate of concrete bridge decks and columns is accelerated by the use of deicing solutions in winter. The corrosion of the steel rebars causes cracking, delamination, and spalling of reinforced concrete structures and increases the cost of rehabilitation and maintenance operations. In Wisconsin (USA), fiberglass wrapping has been used for corrosion protection of reinforced concrete columns. In this methodology, a fiberglass wrap is placed as a barrier between the concrete surface and the surrounding environment and is expected to reduce the detrimental effect of traffic splashing of deicing solutions. This paper describes a study aimed at evaluating the effectiveness of fiberglass wrapping in controlling and reducing the rate of corrosion in bridge concrete columns. Field tests included nondestructive wave propagation and half-cell potential methods. Nondestructive evaluation results were examined and compared to chloride ion (Cl⁻) intrusion measurements. The data show that fiberglass wrapping helps in arresting the chloride ion ingress to the columns, however, it does not help reduce corrosion rates in chloride contaminated concrete columns.     

Effect of polyvinylpyrrolidone on the corrosion resistance of steel

The effect of polyvinylpyrrolidone (PVP) on the corrosion resistance of steel reinforced concrete was assessed by measuring the corrosion potential, linear polarization resistance and AC impedance during 60 days immersion in NaCl and NaCl + PVP solutions. Polarization resistance (R_p) values of PVP added reinforced concrete were much higher than those without PVP. The relationship between corrosion potential and linear polarization resistance was analysed. Results from corrosion potential measurements were well comparable with the linear polarization resistance data. AC impedance spectra revealed that the resistance of PVP mixed electrodes was also quite higher than the other electrodes. The mechanical properties of concrete were measured. It was observed that the compressive strength of concrete had increased approximately 44% in the specimens containing PVP.