硫酸盐还原菌对几种金属材料的腐蚀机理研究
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摘要
金属材料的微生物腐蚀给国民经济造成巨大的经济损失,硫酸盐还原菌(Sulfate reducing bacterial, SRB)是金属腐蚀中最重要的细菌之一。因此研究金属材料的SRB腐蚀的影响因素及防治方法对实际工业生产有着重要的意义。
本文用稀释试管法及平皿夹层厌氧法分离提取了SRB,采用电化学测试技术和微生物分析等方法系统研究了SRB对低合金钢、双相不锈钢和抗菌不锈钢的腐蚀行为及温度、pH值、流速等因素的影响规律。研究结果表明：
杆状SRB在低合金钢表面局部富集、附着,它通过阳极去极化作用加速低合金钢的腐蚀；三种低合金钢的耐蚀性降低顺序为：09Cr2AlMoRe、08Cr2AlMo、10CrMoAl。低合金钢在接菌海水中的腐蚀产物中S元素含量为9.23%,腐蚀产物主要为FeS。在SRB的菌液中,随着温度升高低合金钢的腐蚀速率增加,且腐蚀反应遵循Arrhenius关系。灭菌培养基+SRB介质中pH值为5～8范围内,pH=8时的腐蚀速率最大。
在灭菌海水+乳酸钠介质中加入SRB后,双相不锈钢的钝化膜遭受破坏,钝化膜电阻急剧降低,腐蚀电位发生负移,维钝电流密度增加,SRB加速了双相不锈钢的阳极溶解过程。含铜抗菌不锈钢NSSAM3对SRB的杀菌率为90.67%。SRB在对数生长期迅速繁殖,在NSSAM3表面吸附形成疏松、不均匀的生物膜加速了不锈钢的腐蚀。但随着时间延长,NSSAM3释放的铜离子浓度由2.735μg/mL增至8.590μg/mL,导致SRB菌体失去活性,丧失分裂增殖能力而最终死亡。因而NSSAM3在菌液中的阳极极化电流密度减少,交流阻抗值增加。XPS测试表明,SRB介质中浸泡未经打磨处理的NSSAM3的表面膜主要由FeS、FeS2、FeO、Fe2O3、CrO3和CrO42-组成,与无菌介质相比,由于铬的氧化物发生溶解,导致不锈钢的耐蚀性下降。
当培养基+SRB介质中硫酸根离子浓度较低时,其浓度的增加会加速10CrMoAl钢的腐蚀。在细菌生长初期加入10mmol/L的钼酸钠可以明显地减小10CrMoAl钢的腐蚀速率。新洁尔灭和戊二醛对7×104个/mL的SRB的最低杀菌浓度分别为300mg/L和60mg/L。相同浓度的新洁尔灭和戊二醛按体积比1：1.5复配,杀菌效率最高。
用溶胶凝胶法在304不锈钢表面制备的二氧化钛薄膜和在碳钢表面制备的Ni-P-纳米TiO2化学镀复合镀层对SRB腐蚀具有防护作用,在SRB菌液中长期浸泡后,仍可保持良好的耐蚀性能。
Microbiologically Influenced Corrosion caused huge economic losses to the national economy. Sulfate reducing bacterial (SRB) is one of the most important bacterial. It is very important to the actual industrial production to research on the impact factors of SRB corrosion and control methods.
In this paper, SRB is isolated and purified by culture dish sandwich anaerobic Method. The effect of SRB on corrosion behavior of low alloy steel, duplex stainless steel and antibacterial stainless steel and the effect law of temperature, pH and velocity on SRB corrosion were investigated by electrochemical testing technique and microorganism analysis. The results show that:
Bacilliform sulfate-reducing bacterial attaches and accumulates on local surface of low alloy steel. SRB accelerated corrosion of low alloy steel by anodic depolarization, the reducing order of corrosion resistance is 09Cr2AlMoRe、08Cr2AlMo、10CrMoAl. In SRB medium, the content of S element in corrosion product is 9.23%, which is mainly FeS. Depolarizing agent sulfides concentration increasing with temperature caused corrosion rate increase. Moreover, corrosion reaction follows Arrhenius relation. The corrosion rate is the highest when pH equals to 8.The corrosion rate increase with rotating speed and velocity.
Inoculating of SRB into the sterile seawater plus sodium lactate medium, the passive film of duplex stainless steels is damaged; the corrosion potentials turn negative, passive current densities increase. Sterilization rate of antibacterial stainless steel contained copper to SRB is 90.67%. SRB rapidly propagate in logarithmic grow period and form loose biofilm on the surface of NSSAM3, which induces the sensitivity to local corrosion. However, the concentration of Cu2+ in SRB medium increases to 8.590μg/mL from 2.735μg/mL with increasing time, anodic polarization current density of NSSAM3 decreases and polarization resistance increases .XPS indicadesthat the surface film of NSSAM3 with no polshing in SRB is made of FeS、FeS2、FeO、Fe2O3、CrO3 and CrO42-. Compare to sterile medium, the corrosion resistance of NSSAM3 decreases because of chrome oxide being dissolved.
When sulfate ion concentration in the medium is lower than 1.0%, its concentration increases will accelerate the SRB induced corrosion. By adding 10 mmol/L of sodium molybdate in bacterial growth beginning, the corrosion rate of 10CrMoAl steel can be significantly reduced. We must add appropriate amount of sodium molybdate before forming a biofilm on the metal surface if we want to prevent SRB corrosion. The minimum bactericidal concentration of Glutaraldehyde and Bromogeramine to 7×104 cfu/mL of SRB are 300mg/L and 60mg/L, respectively. The same concentration Bromogeramine and glutaraldehyde mixed at volume ratio of 1:1.5 have the most efficient sterilization.
Titanium dioxide thin film on the surface of 304 stainless steel prepared by sol-gel method and Ni-P-nano-TiO2 composite coatings of electroless plating on carbon steel have a protective role on SRB corrosion, they may still maintain a good corrosion resistance after they were long-term immersed in the SRB bacteria.
本文用稀释试管法及平皿夹层厌氧法分离提取了SRB,采用电化学测试技术和微生物分析等方法系统研究了SRB对低合金钢、双相不锈钢和抗菌不锈钢的腐蚀行为及温度、pH值、流速等因素的影响规律。研究结果表明：
杆状SRB在低合金钢表面局部富集、附着,它通过阳极去极化作用加速低合金钢的腐蚀；三种低合金钢的耐蚀性降低顺序为：09Cr2AlMoRe、08Cr2AlMo、10CrMoAl。低合金钢在接菌海水中的腐蚀产物中S元素含量为9.23%,腐蚀产物主要为FeS。在SRB的菌液中,随着温度升高低合金钢的腐蚀速率增加,且腐蚀反应遵循Arrhenius关系。灭菌培养基+SRB介质中pH值为5～8范围内,pH=8时的腐蚀速率最大。
在灭菌海水+乳酸钠介质中加入SRB后,双相不锈钢的钝化膜遭受破坏,钝化膜电阻急剧降低,腐蚀电位发生负移,维钝电流密度增加,SRB加速了双相不锈钢的阳极溶解过程。含铜抗菌不锈钢NSSAM3对SRB的杀菌率为90.67%。SRB在对数生长期迅速繁殖,在NSSAM3表面吸附形成疏松、不均匀的生物膜加速了不锈钢的腐蚀。但随着时间延长,NSSAM3释放的铜离子浓度由2.735μg/mL增至8.590μg/mL,导致SRB菌体失去活性,丧失分裂增殖能力而最终死亡。因而NSSAM3在菌液中的阳极极化电流密度减少,交流阻抗值增加。XPS测试表明,SRB介质中浸泡未经打磨处理的NSSAM3的表面膜主要由FeS、FeS2、FeO、Fe2O3、CrO3和CrO42-组成,与无菌介质相比,由于铬的氧化物发生溶解,导致不锈钢的耐蚀性下降。
当培养基+SRB介质中硫酸根离子浓度较低时,其浓度的增加会加速10CrMoAl钢的腐蚀。在细菌生长初期加入10mmol/L的钼酸钠可以明显地减小10CrMoAl钢的腐蚀速率。新洁尔灭和戊二醛对7×104个/mL的SRB的最低杀菌浓度分别为300mg/L和60mg/L。相同浓度的新洁尔灭和戊二醛按体积比1：1.5复配,杀菌效率最高。
用溶胶凝胶法在304不锈钢表面制备的二氧化钛薄膜和在碳钢表面制备的Ni-P-纳米TiO2化学镀复合镀层对SRB腐蚀具有防护作用,在SRB菌液中长期浸泡后,仍可保持良好的耐蚀性能。
Microbiologically Influenced Corrosion caused huge economic losses to the national economy. Sulfate reducing bacterial (SRB) is one of the most important bacterial. It is very important to the actual industrial production to research on the impact factors of SRB corrosion and control methods.
In this paper, SRB is isolated and purified by culture dish sandwich anaerobic Method. The effect of SRB on corrosion behavior of low alloy steel, duplex stainless steel and antibacterial stainless steel and the effect law of temperature, pH and velocity on SRB corrosion were investigated by electrochemical testing technique and microorganism analysis. The results show that:
Bacilliform sulfate-reducing bacterial attaches and accumulates on local surface of low alloy steel. SRB accelerated corrosion of low alloy steel by anodic depolarization, the reducing order of corrosion resistance is 09Cr2AlMoRe、08Cr2AlMo、10CrMoAl. In SRB medium, the content of S element in corrosion product is 9.23%, which is mainly FeS. Depolarizing agent sulfides concentration increasing with temperature caused corrosion rate increase. Moreover, corrosion reaction follows Arrhenius relation. The corrosion rate is the highest when pH equals to 8.The corrosion rate increase with rotating speed and velocity.
Inoculating of SRB into the sterile seawater plus sodium lactate medium, the passive film of duplex stainless steels is damaged; the corrosion potentials turn negative, passive current densities increase. Sterilization rate of antibacterial stainless steel contained copper to SRB is 90.67%. SRB rapidly propagate in logarithmic grow period and form loose biofilm on the surface of NSSAM3, which induces the sensitivity to local corrosion. However, the concentration of Cu2+ in SRB medium increases to 8.590μg/mL from 2.735μg/mL with increasing time, anodic polarization current density of NSSAM3 decreases and polarization resistance increases .XPS indicadesthat the surface film of NSSAM3 with no polshing in SRB is made of FeS、FeS2、FeO、Fe2O3、CrO3 and CrO42-. Compare to sterile medium, the corrosion resistance of NSSAM3 decreases because of chrome oxide being dissolved.
When sulfate ion concentration in the medium is lower than 1.0%, its concentration increases will accelerate the SRB induced corrosion. By adding 10 mmol/L of sodium molybdate in bacterial growth beginning, the corrosion rate of 10CrMoAl steel can be significantly reduced. We must add appropriate amount of sodium molybdate before forming a biofilm on the metal surface if we want to prevent SRB corrosion. The minimum bactericidal concentration of Glutaraldehyde and Bromogeramine to 7×104 cfu/mL of SRB are 300mg/L and 60mg/L, respectively. The same concentration Bromogeramine and glutaraldehyde mixed at volume ratio of 1:1.5 have the most efficient sterilization.
Titanium dioxide thin film on the surface of 304 stainless steel prepared by sol-gel method and Ni-P-nano-TiO2 composite coatings of electroless plating on carbon steel have a protective role on SRB corrosion, they may still maintain a good corrosion resistance after they were long-term immersed in the SRB bacteria.
引文
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