Evaluation of a biocide effect upon microbiologically influenced corrosion of mild steel

The microbiologically influenced corrosion (MIC) is a very dangerous process, which affects the oil industry. The activity and microorganisms' growth at the pipelines steel cause surface modifications, which can induce a more complex corrosion process. The biocide evaluation for the MIC decrease has been normally based upon microbiological tests, and just a few references mention alternating methods which can be used as criteria for their evaluation. In this work, a commercial biocide was tested, using different electrochemical laboratory techniques, to determine its effect upon a biofilm generating bacteria consortium. Using microbiological techniques, the biocide lethal concentration was determined, and a concentration of 200 ppm was used to kill completely the consortium population in both, plancktonic and sessile parts. The electrochemical techniques: Polarisation Resistance (PR) and Electrochemical Impedance Spectroscopy (EIS), allowed describing the corrosion process associated to the microbial consortium and the biocide effect upon it.     

Development of microbially influenced corrosion on carbon steel in a simulated water injection system

Microbially influenced corrosion (MIC) on internal pipeline surfaces has become a severe problem during the water injection process in secondary oil recovery. The formation of a biofilm, normally dominated by sulfate‐reducing bacteria (SRB), is believed to be the critical step of the MIC process. A continuously fed biofilm simulating the water injection process was operated to investigate the influence of biofilm development on MIC behavior in the early phase of corrosion development. The development of the corrosion product film and biofilm was monitored for 5 months with electrochemical impedance spectroscopy, linear polarization resistance, scanning electron microscopy, 3D optical profiling, and direct weight measurement. MIC development was found to comprise three phases: initialization, transition, and stabilization. The initialization phase involved the formation of the corrosion product layer and the initial attachment of the sessile microbes on metal surface. In the transition phase, the MIC process gradually shifted from charge‐transfer‐controlled reaction to diffusion‐controlled reaction. The stabilization phase featured mature and compact biofilm on the metal surface, and the general corrosion rate (CR) decreased due to the diffusional effect, while the pitting CR was enhanced at a lower carbon source level, which supported the mechanism of direct electron uptake from the metal surface by SRB.     

弱极化曲线拟合技术在土壤腐蚀研究中的应用

在后插参比电极测量法的基础上,应用弱极化曲线拟合软件直接对极化曲线上弱极化区的数据进行拟合,求算动力学参数,从而估算出A3钢在黑潮土中不同水分含量下的腐蚀速度,与实际情况相比具有较好的对应性,并证实了钢铁材料在土壤中的腐蚀行为在大多数情况下受到阴极氧浓度极化的控制。     

Evaluation of sessile microorganisms in pipelines and cooling towers of some Iranian industries

Microbiologically influenced corrosion (MIC) is a kind of electrochemical corrosion that is enhanced by the effect of certain microorganisms including sessile bacteria. In this investigation, more than 200 samples collected from different systems of Iranian refineries have been examined (by culturing methods and observations) for corrosion-enhancing, biofilm-producing microorganisms such as sulfate-reducing bacteria (SRB), iron-oxidizing bacteria (IOB), heterotrophic biofilm-forming bacteria (HBB), and some eukaryotes such as fungi. This study showed the presence of microorganisms, such as SRB, HBB, thermophillic HBB, and yeasts, except for IOB. It was also revealed that biocides are used to reduce the number of planktonic (floating) bacteria, instead of the number of sessile bacteria, that form biofilms. Using surfactants, or washing with chemicals like chlorine or organic acids in overhauls, may destroy the biofilm and free the residential bacteria into the bulk solution, thus exposing them to the biocide. For thick biofilms, a chlorine or acid wash may also yield the same results.     

Microbial corrosion of galvanized steel by a freshwater strain of sulphate reducing bacteria (Desulfovibrio sp.)

Microbially influenced corrosion of galvanized steel was investigated exposing coupons (2.0 × 2.0 cm) to culture of sulphate reducing bacteria strain Desulfovibrio sp. The coupons were exposed to the SRB culture for 4, 8, 24, 72, 96, 168, 360 and 744 h along with a control set in uninoculated medium. The results from the present study suggest that SRB were responsible for the corrosion of the galvanized steel. The corrosion rate of galvanized steel was not be correlated with the number of sessile SRB cells. Also Desulfovibrio sp. had an ability to produce EPS (Extracellular Polimeric Substances) and biodegrade the carbohydrate, that is the predominant component of the EPS produced by them. When Desulfovibrio sp. cells were in logarithmic phase, the concentration of dissolved zinc in the bulk solution was very toxic for Desulfovibrio desulfuricans.     

陕北某天然气处理厂回注水处理系统腐蚀影响因素研究

目的考察陕北某天然气处理厂回注系统的腐蚀情况,保证系统安全生产。方法在水质分析的基础上,用现场材质20#钢和计划替换钢材L316研究回注水处理系统的腐蚀现状,随后选择腐蚀最严重环节的水样为介质,采用静态失重法考察温度、pH值、溶解氧、细菌对20#钢材腐蚀速率的影响。结果陕北某气田气井产出水的总矿化度较高(30 000 mg/L左右),其中Ca²⁺、Mg²⁺等金属阳离子的含量较高,腐蚀速率随水介质中溶解氧含量的增加均呈上升趋势,在80℃、溶解氧为5.07 mg/L时,腐蚀速率最大,达到0.4001mm/a。随着细菌含量的增大,腐蚀速率上升,腐蚀速率由0.1065 mm/a(TGB 60个/m L,SRB 6个/m L)增加到0.2155 mm/a(TGB 6×10~4个/m L,SRB 6×10~3个/m L)。pH值为5.9时,腐蚀速率为0.3039 mm/a;当pH值为8.5时,腐蚀速率降至0.0710 mm/a。结论通过做好回注水处理系统pH调节、杀菌和隔氧等工作,可以减轻系统的腐蚀。     

硫酸盐还原菌对铜镍合金腐蚀的影响

利用电化学测试技术，在实验室条件下研究了硫酸盐还原菌(SRB)对铜镍合金腐蚀行为的影响。实验结果表明，SRB的存在使电极开路电位明显负移，极化电阻在细菌生长后期迅速降低。在含SRB的溶液中，铜镍合金表面会形成由腐蚀产物和SRB等组成的混合膜，腐蚀速度受到Cu通过混合膜向电极表面扩散速度的控制。     

胞外聚合物对飞机油箱2024铝合金腐蚀行为影响

目的 探究飞机油箱内有积水存在的环境中硫酸盐还原菌分泌的胞外聚合物（EPS）对飞机油箱2024铝合金腐蚀行为的影响,为飞机油箱中微生物腐蚀与防护提供理论依据。方法 针对航煤中微生物滋生导致飞机油箱材料2024铝合金腐蚀失效的问题,通过傅里叶红外光谱（FT-IR）分析EPS的组成,并利用电感耦合等离子体发射光谱仪（ICP-MS）分析金属离子含量,采用表面分析法和电化学法研究了硫酸盐还原菌EPS在模拟飞机油箱积水环境中诱导飞机油箱2024铝合金的腐蚀行为。结果 与无EPS添加的介质条件相比,在相同的试验条件下,EPS导致航煤积水模拟溶液中的2024铝合金腐蚀电流密度减小,腐蚀产物膜呈疏松多孔的形貌,腐蚀形貌以点蚀为主。试验结束时,2024铝合金在EPS质量浓度为200 mg/L的模拟溶液中腐蚀速率大致为无EPS添加的模拟溶液中的1/10。当溶液中EPS质量浓度为100 mg/L和200 mg/L时,尽管EPS与Al3+络合产生的EPS-金属络合物会促进2024铝合金试样阳极溶解速度,但起主要影响的是抑制溶解氧扩散减缓阴极吸氧反应,抑制腐蚀的效果与EPS浓度仍成正比。结论 航煤积水模拟溶液中...     

锌铝镁镀层和纯锌镀层在典型大气环境中初期腐蚀行为研究

目的 增加对不同大气环境中锌铝镁镀层钢腐蚀行为的了解,研究中国地区不同气候条件下1 a内锌铝镁镀层钢腐蚀产物的组成和腐蚀速率。方法 采用SEM、GDS、XRD研究了纯锌(GI)镀层材料和锌铝镁合金(ZM)镀层材料的结构,对比研究了GI镀层和ZM镀层在吐鲁番、江津、青岛以及万宁4个大气试验站的腐蚀试验。结果 万宁GI的腐蚀速率为ZM的4.56倍,江津GI的腐蚀速率为ZM的3.76倍,青岛GI的腐蚀速率为ZM的2.84倍,吐鲁番GI的腐蚀速率为ZM的2.42倍,对于GI镀层和ZM镀层,按腐蚀速率从大到小的顺序依次为万宁、青岛、江津、吐鲁番。江津和万宁GI镀层的自腐蚀电流密度较小,万宁ZM镀层的自腐蚀电流密度最小。锌的大气腐蚀速率主要受相对湿度、氯离子含量、SO2含量等影响,主要通过影响腐蚀产物组成来影响锌的腐蚀速率。腐蚀产物的保护性受其化学组成、导电性、黏附性、致密性、溶解性、厚度、形态和亲水性等因素影响,不同的锈层结构对阴极氧还原的抑制作用不一样,高氯环境对GI的保护性腐蚀产物Zn5(CO3)2(OH)6有较大的破坏性,在高碱性环境下,容易使腐蚀产物转变成疏松导电的ZnO。在高氯环境中,由于镀层中MgZn2的阳极溶解,释放出可与OH反应的Mg²⁺以形成氢氧化镁(Mg(OH)2)。在ZM表面用Mg(OH)2代替氧化锌被认为可以降低阴极氧还原反应(ORR),具有缓冲阴极位置的pH值升高的作用,能使碱式碳酸锌变得稳定,显著提升耐腐蚀性。结论 ZM镀层材料在高盐高湿环境下能形成稳定的腐蚀产物,降低阴极氧还原速率,在典型大气环境下具有广阔的应用前景。     

Cu-Al-Mn-Zn-Zr形状记忆合金在NaCl溶液中的腐蚀行为

通过动态电位极化测量、电化学阻抗谱(EIS)和X射线光电子能谱(XPS)研究铜基形状记忆合金(Cu-Al-Mn-Zn-Zr)在3.5%NaCl(质量分数)溶液中的腐蚀行为。腐蚀开始时,形状记忆合金表面形成的氧化产物不断覆盖合金表面,导致腐蚀速率降低。合金在NaCl溶液中浸泡4 d后,腐蚀产物层变厚及更加疏松多孔,导致腐蚀速率增大,合金表面的腐蚀反应机理由极化控制向扩散控制转变。在NaCl溶液中浸泡6~15 d后,试样的扩散阻抗随氧化层厚度的增加而增大。在整个腐蚀过程中,合金的腐蚀机理发生改变,耐蚀性能持续提高。腐蚀产物主要为CuO、ZnO、Al2O3、MnO/Mn2O3、MnO2和Al(OH)3。腐蚀过程中腐蚀产物由Cu2O转变为CuO,由Al2O3转变为Al(OH)3。     

“A study on the effect of Co,Cr and Ti on the corrosion of FE40AL intermetallic in molten NaCl–KCl mixture”

The effect of the addition of 3 at% Cr, Co or Ti on the corrosion behavior of Fe40Al intermetallic alloy in 1 M NaCl:1 M KCl mixture at 750 °C has been carried out by using electrochemical techniques. Techniques included potentiodynamic polarization curves, linear polarization resistance and electrochemical impedance spectroscopy measurements. It has been found that the addition of either Cr, Co or Ti decreased the corrosion rate of Fe40Al intermetallic by almost five times due to the formation of a passive layer, absent in the base alloy. This was because the diffusion of Al towards the top of the alloy for the establishment of a protective Al₂O₃ layer was enhanced by the presence of these alloying elements. The corrosion rate for the base alloy was under diffusion control of the reactants, whereas that for alloyed intermetallic was under charge transfer control.     

Effect of temperature on transgranular and intergranular stress corrosion crack velocity of Ag–Au alloys

The effect of temperature on both the transgranular and the intergranular stress corrosion crack velocity of silver–gold alloys in a 1 M KCl solution was studied for temperatures ranging from 25 to 80 °C by means of slow strain rate experiments. At a constant potential and a constant elongation rate, the crack propagation rate was higher the higher the temperature. Transgranular stress corrosion cracking (TGSCC) velocity was found to change with the temperature, as well as with the potential, in the same way as intergranular stress corrosion cracking (IGSCC) velocity. In the region of potentials where the crack velocity was not controlled by ion diffusion in the crack, it was concluded that TGSCC and IGSCC for Ag–Au alloys in KCl solutions were controlled by the same stress corrosion cracking mechanism.     

外部电位对蚀孔或裂缝扩展阶段闭塞区腐蚀行为的影响

采用恒电位模拟闭塞电池装置研究外部电位对局部腐蚀闭塞区的影响，在蚀孔或裂缝的扩展阶段，即当闭塞区溶液的ｐＨ值已经降到临界值以下时，外表面阴极极化使闭塞区电位负移，腐蚀率变小，闭塞区电位与外部电位呈线性关系，闭塞区腐蚀率与外部电位呈指数关系，对外表面施加阳极极化时，闭塞区的电位和腐蚀率不随极化电位而变化，闭塞区内外的电位差主要来自内外溶液的扩散电位差和离子的电迁移欧姆降。     

Corrosion behavior of low‐alloy steel in the presence of Desulfovibrio caledoniensis

Sulfate‐reducing bacteria (SRB) are shown to be common inhabitants of oil reservoirs. Desulfovibrio caledoniensis isolated from a production well was used in this study. After an incubation period of 1 month with the SRB culture, two layers of corrosion products with different compositions were detected on the test coupons. The Tafel plots showed that the corrosion potential exhibited a cathodic shift and the corrosion rates increased with the incubation time. The analysis of the Nyquist diagrams revealed that the diffusion process begins to dominate with time in bacteria containing medium. These results are in good accordance with the Tafel data.     

A study of the corrosion of aluminum alloy 2024-T3 under thin electrolyte layers

The corrosion of aluminum alloy 2024-T3 (AA2024-T3) under thin electrolyte layers was studied in 3.0 wt% sodium chloride solutions by cathodic polarization and electrochemical impedance spectroscopy (EIS) method. The cathodic polarization measurements show that, when the electrolyte layer is thicker than 200 μm, the oxygen reduction current is close to that of the bulk solution. But in the range of 200-100 μm, the oxygen reduction current is inversely proportional to the layer thickness, which shows that the oxygen diffusion through the electrolyte layer is the rate-determining step for the oxygen reduction process. In the range of 100 μm to about 58 μm, the oxygen reduction current is slightly decreased probably due to the formation of aluminum hydroxide or the change of the diffusion pattern from 2-dimensional diffusion to one-dimensional diffusion. The further decrease in electrolyte layer thickness increase the oxygen reduction current to some extent again, because the diffusion of oxygen plays more important role in thin electrolyte layers.The EIS measurements show that the corrosion is controlled by the cathodic oxygen reduction at the initial stage, showing the largest corrosion rate at the electrolyte layer thickness of 105 μm. But at the later stage of corrosion, the anodic process begin to affect the corrosion rates and the corrosion rates show a maximum at 170 μm, which may be the thickness where the corrosion changes from cathodic control to anodic control. The corrosion rate under the very thin electrolyte layer (62 μm in this study) is even smaller than that in bulk solution, this is due to that the anodic process is strongly inhibited.     

磁场作用下的微生物腐蚀研究进展

磁体周围存在磁场,磁体间的相互作用就是以磁场作为媒介的,磁场力包括洛伦兹力和安培力.概述了磁场对微生物和金属腐蚀过程的影响,包括对单一细菌和混菌体系、电化学控制和浓差极化控制的电化学过程的影响.归纳了磁场作用于微生物金属腐蚀的防控方法,包括微生物竞争手段、缓蚀杀菌剂的应用以及存在的不足等问题.在此基础上,重点综述了近年来磁场条件下金属微生物腐蚀的研究进展,分析了磁场对于微生物生长特性和生物膜形成的影响,分别以不同微生物存在的体系、电化学过程控制的类型等方面展开详细讨论.针对磁场存在的环境,总结了微生物对金属的腐蚀机理,包括生物膜理论、离子干涉理论、自由基理论等.最后结合磁场对金属腐蚀过程的相关机理,展望了后续磁场对微生物腐蚀防控的研究方向.     

滨海盐土中典型供水管材腐蚀机理的土壤加速腐蚀研究

基于土壤加速腐蚀实验,采用失重法和电化学测试手段研究了滨海盐土中球墨铸铁、灰口铸铁和碳钢3种典型供水管材的腐蚀规律、腐蚀层结构变化以及腐蚀的阴阳极反应动力学过程。结果表明：3种材质在滨海盐土中的腐蚀行为规律一致。腐蚀主要分为点蚀诱导期、点蚀发展期和稳定腐蚀期3各阶段;腐蚀初期和中期主要受电荷传递控制,且随着腐蚀的进行,电荷传递电阻快速上升;腐蚀稳定期,氧的扩散成为了腐蚀的控制步骤。3种材质腐蚀的极化曲线均出现明显的阴极扩散和阳极活化双重控制的现象,其中阴极扩散控制作用更为明显。     

铝基钎料真空钎焊接头的腐蚀性

采用NaCl的质量分数为3．5％的溶液对四种Al-Si-Cu钎料的真空钎焊接头进行全浸试验，对腐蚀后的钎焊接头进行观察，分析接头的腐蚀类型，研究接头的腐蚀机理，对Cu的晶界偏析及扩散进行了讨论。结果表明，铝基钎料真空钎焊后的接头仍然存在腐蚀问题，腐蚀产物为A1Cl3、Al(OH)3、Al(OH)2Cl，腐蚀类型有点蚀和晶间腐蚀；并且随着Cu含量的增加腐蚀加重，Cu的偏析与扩散对接头腐蚀行为产生重要的影响，在晶界形成他Cu，使晶界周围形成贫Cu区，与晶粒内部处于钝态的αAl存在较大电位差，构成局部腐蚀电池，形成晶间腐蚀。     

Diffusion mechanism of dezincification in double-phase brass exposed to seawater

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钛表面钛钯合金层耐蚀性能及耐蚀机理研究

采用磁控溅射沉积钯膜层+热扩散技术在工业纯钛表面制备Ti-Pd合金层,研究了Ti-Pd合金层的耐蚀性能,用重量法评价了合金层的腐蚀速率,分析了不同样品经腐蚀后的表面形貌和成分。结果表明:Ti-Pd合金层在37%(质量分数,下同) HCl溶液和80%H_2SO_4溶液中的腐蚀速率比纯钛降低了2个数量级。Ti-Pd合金层经37%HCl腐蚀后,表面含有Ti、Pd、O元素,表面有微小的点蚀坑。Ti-Pd合金层经80%H_2SO_4腐蚀后,表面含有Ti、Pd、S、O元素,表面有亚微米级的点蚀坑。提出了Ti-Pd合金层的耐蚀机理:微量的Pd和Ti O2组成的钝化膜使表面腐蚀电位提高,产生耐蚀效果。