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1 硫酸盐还原菌对热镀锌钢材氢渗透行为的影响 1, 2, 1,2, 1 (1., ; 2., ) 摘要 : 采用 Devanathan-Stachurski 双面电解池检测氢渗透电流技术和扫描电镜分析, 研究了热镀锌钢材在灭菌海水灭菌培养基和接种了硫酸盐还原菌 (SRB) 的培养基等 3 种介质中的氢渗透行为氢渗透电流检测结果表明, 培养基的部分组分对热镀锌钢材的氢渗透行为有促进作用, 试样在灭菌培养基中的氢渗透电流密度的平均值比在灭菌海水中提高了约 6 倍尽管活性 SRB 代谢产生的 S 2 和 HS 能够促进热镀锌钢材的氢渗透行为, 但是, 由 SRB 及其代谢产物和它们所黏附的腐蚀产物所形成的致密微生物膜减少了氢的析出和试样对氢的吸收量, 导致热镀锌钢材氢渗透行为最终被抑制, 因此, 试样在接菌培养基中的氢渗透电流密度的平均值比其在灭菌培养基中降低 77% 扫描电镜分析表明, 热镀锌钢材在灭菌海水中能够形成腐蚀产物膜, 而暴露于灭菌培养基中的试样表面未形成明显的腐蚀产物膜, 但在接菌培养基中试样表面能形成黏附了腐蚀产物的致密微生物膜的附着, 表明热镀锌钢材表面的微生物膜与其氢渗透行为之间存在明显的相关性关键词 : 硫酸盐还原菌 ; 氢渗透 ; 镀锌层 ; 阴极保护中图分类号 : TG172.2; TG172.5 文献标识码 : A 文章编号 : (2011) ,, [1], ;,,,, [2] : : Zn 2e Zn 2+ (1) : O 2 + 2H 2 O + 4e 4OH (2) H 2 O + e H + OH (3) [3],, (SRB),, SRB [4-11],, SRB,, D-S SRB 3 1 材料与实验方法 1.1 材料及试样制备 48 / 2011 / 35 / mm ( 10~15 μm), 2.0 cm 600#, 1.2 SRB 菌种及培养和计数 SRB, SRB, SRB SRB : 0.50 g K 2 HPO 4 3H 2 O, 1.00 g NH 4 Cl, 0.50 g Na 2 SO 4, 0.10 g CaCl 2, 2.00 g MgSO 4, 3.50 g, 1.00 g 1L, min, 0.50 g Fe(NH 4 ) 2 (SO 4 ) 2 7H 2 O 0.10 g,, 30min, : ; : : ( ), (Y2008E09) : (1983-),,,, ;,, : , yanlee@ms.qdio.ac.cn

2 MPN SRB, SRB 1.3 腐蚀形貌观察 2.0 cm 2.0 cm SRB 3, 7d,, ; SRB,, 2.5% SEM KYKY-2800, 20 kv 1.4 氢渗透电流检测 2 实验结果 2.1 SRB 的生长曲线 2 SRB, SRB 1 (0~4 d),, SRB ; 2 (4~6 d),, SRB ; 3 ( 7 ),, SRB, Kuang [12] SRB Devanathan- Stachurski ( 1),, (, 300 g/l;, 60 g/l;, 37.5 g/l; ph 3.0), 0.90 ma/cm 2 5 min; 0.20 mol/l NaOH, +200 mv( - ) 0.20 μa/cm 2,, 500 ml 1h, 30 min 20 ml,, SRB, 495 ml, 5 ml SRB, 1 Fig. 1 Schematic diagram of equipment for hydrogen permeation current measurement Fig. 2 2 SRB SRB growing process in the culture medium 2.2 热镀锌钢材在腐蚀介质中的氢渗透曲线 3 3,, 8, 50 μa/cm 2,, 2, 150 μa/cm 2, 2 :, 3 6,, 热镀锌钢材在腐蚀介质中的表面微观形貌 4 3 Marine Sciences / Vol. 35, No. 1 /

3 7d, ( 4(a)); ( 4(b));,, SRB, ( 4(c)) Fe 2+,,, [3] 3 讨论 3.1 培养基组分对热镀锌钢材氢渗透的影响 3,, 39.7 μa/cm μa/cm 2, 627% 4,,, Fe 2+ -,, ; Cl -, [13] ; ph, 3 Fig. 3 Hydrogen permeation current density curves for hot-dip galvanized steel in sterilized seawater, sterilized midium and medium inoculated with SRB 4 7 Fig. 4 (a) ; (b) ; (c) SEM images of hot-dip galvanized steel immersed in sterilized seawate(a), sterilized medium(b) and medium inoculated with SRB(c) for 7d [3],,,,, -, 3.2 SRB 对热镀锌钢材氢渗透行为的影响 ( 3) 2, 50 / 2011 / 35 / 1

4 2~8 ;, μa/cm 2, 65.9 μa/cm 2, 77%, SRB ( 4), SRB [5-6] 16Mn API X56,, SRB Javaherdashtia [14], SRB 3.5%NaCl ( ) Vigdorovich [7], St3 6 mmol/lh 2 S SRB 1,, SRB,, SRB (10 d),, KüHr [15], : 4Fe 2+ +SO H 2 O FeS+ 3Fe(OH) 2 + 2OH - (4), ;, -, SRB, (1) (3) : SO H S 2- +4H 2 O ( ) (5) Zn 2+ + S 2- ZnS (6) Zn OH - Zn(OH) 2 (7) Fe 2+ + S 2- FeS (8) Fe OH - Fe(OH) 2 (9), (4) FeS Fe(OH) 2, ZnS Zn(OH) 2, : H + + S 2- HS - (10) H + + HS - H 2 S (11) H 2 S HS - S 2- [6], SRB, 3 2 SRB SRB 4~6 d,, 7, SRB, SRB, H 2 S HS - S 2-, H 2 S HS - S 2- Zn 2+ Fe 2+,,, ;, 4,,,, SRB,,,,,,,, SRB SRB, SRB,,,,,,, SRB, SRB 3 结论 SRB, SRB, Marine Sciences / Vol. 35, No. 1 /

5 , SRB : [1],,. [J]. ( ), 2007, 28(8): [2] TANG Xiao, ZHANG Yuzhi, LIU Meng, et al. BEM analysis for galvanic corrosion of hot dip galvanized steel immersed in seawater[j]. Journal of Materials Science and Techonology, 2009, 25(2): [3]. [D]. :, [4] Vigdorovich V I, Vigdorovich M V, Ryazanov A V, et al. Suppressing sulfate-reducing bacteria, as well as hydrogen diffusion through steel, by inhibitors of AMDOR IC Type[J]. Protection of Metals, 2007, 43(1): [5],, 偲,. 16Mn [J]., 2008, 20(2): [6] ZHU Yongyan, HUANG Yanliang, ZHENG Chuanbo, et al. The hydrogen permeation investigation of API X56 steel in sea mud[j]. Materials and Corrosion, 2007, 58(6): [7] Vigdorovich V I., Zavershinskii A N.The effect of SRB on the hydrogen diffusion through a steel membrane, and the bactericide action of dihydroxyazo compounds[j]. Protection of Mentals, 2003, 39(1): [8],,. 1Cr13 [J]., 2003, 17(2): [9],,,. Q235 [J]., 2007, 21(3): [10],. [J]., 2004, 28(9): [11],,,. [J]., 2006, 30(11): [12] KUANG Fei, WANG Jia, LI Yan,et al. Effects of sulfate-reducing bacteria on the corrosion behavior of carbon steel[j]. Electrochimica Acta, 2007, 52(20): [13]. NaCl [J]., 1995, 9(2): [14] Javaherdashtia R, Singh Ramanb R K, Panterc C, et al. Microbiologically assisted stress corrosion cracking of carbon steel in mixed and pure cultures of sulfate reducing bacteria[j]. International Biodeterioration & Biodegradation, 2006, 58 (1): [15] Kühr V W, Vander V. The graphitization of cast iron as an electrochemical process in anaerobic soils[j]. Water, 1934: / 2011 / 35 / 1

6 Effect of SRB on hydrogen permeation of hot-dip galvanized steel ZHANG Yu-zhi 1, 2, ZHANG Da-lei 1, 2, LI Yan 1 (1. Institute of Oceanology, Chinese Academy of Sciences, Qingdao , China; 2. Graduate School of the Chinese Academy of Sciences, Beijing , China) Received: Oct., 12, 2009 Key words: sulphate reducing bacteria, hydrogen permeation, zinc coating, cathodic protection Abstract: Hydrogen permeation testing with Devanathan-Stachurski cell and SEM analytical method were used to study the hydrogen permeation behavior of hot-dip galvanized steel in sterilized seawater, sterilized medium and medium inoculated with SRB. The results showed hydrogen permeation behavior of galvanized steel was promoted by some components of the medium. The average hydrogen permeation current density of the sample in sterilized medium was 6 times higher than which in sterilized seawater. The compact film formed by SRB, metabolites of SRB and corrosion products decreased the hydrogen adsorption of the sample although S 2- and HS - produced by active SRB could promote the hydrogen peameation behavior, which resulted in the average hydrogen permeation current density of galvanized steel in medium inoculated with SRB 77% lower than which in sterilized medium. SEM results showed few products adhered on the sample immersed in sterilized medium, but a film of corrosion products was formed on the sample immersed in sterilized seawater, and a biofilm of SRB and its metabolites together with the film of corrosion products was formed on the the sample immersed in medium inoculated with SRB, indicating a obvious relation between the biofilm and hydrogen permeation of galvanized steel. ( 本文编辑 : 张培新 ) ( 上接第 47 页 ) Analysis of diarrhetic shellfish poisoning toxins in shellfishes collected from the coastal waters of south Zhejiang ZHANG Shu-gang, ZOU Qing, CHEN Lei, GAO Jun-zhang (Wenzhou Marine Environmental Monitoring Center Station, SOA, Wenzhou , China) Received: Jan., 15, 2010 Key words: coastal waters of south Zhejiang; high performance liquid chromatography; diarrhetic shellfish poisoning Abstract: Forty samples belonging to 10 species of shellfishes were collected in coastal waters of south Zhejiang. Diarrhetic shellfish poisoning (DSP) toxins were detected in 9 samples with high performance liquid chromatography (HPLC). The contents of DSP were between 0.07 to 5.87 μg/g; 7 samples (17.5%) exceeded the safety threshold. The positive rate and over-standard rate of DSP were mainly presented in Summer and the south. Mytilus edulis, Sinnovacula constricta, Tegillarca granosa and Cyclina sinensis showed high contents of DSP toxins. Moreover cultured shellfishes had stronger ability to accumulate DSP than wild shellfishes. ( 本文编辑 : 梁德海 ) Marine Sciences / Vol. 35, No. 1 /

12-1b T Q235B ML15 Ca OH Table 1 Chemical composition of specimens % C Si Mn S P Cr Ni Fe

12-1b T Q235B ML15 Ca OH Table 1 Chemical composition of specimens % C Si Mn S P Cr Ni Fe * - - 100084 Q235B ML15 Ca OH 2 DOI 10. 13204 /j. gyjz201508023 STUDY OF GALVANIC CORROSION SENSITIVITY BETWEEN ANY COUPLE OF STUD WELDMENT OR BEAM Lu Xinying Li Yang Li Yuanjin Department of Civil Engineering