Please wait a minute...
中国腐蚀与防护学报  2016, Vol. 36 Issue (4): 328-334    DOI: 10.11902/1005.4537.2015.124
  研究报告 本期目录 | 过刊浏览 |
夹杂对自来水环境下304不锈钢腐蚀及金属离子溶出的影响
王永利,马利,熊良银,刘实()
中国科学院金属研究所特殊环境材料部 沈阳 110016
Effect of Inclusions on Corrosion and Dissolution of Metallic Ions of Stainless Steel 304 in Simulated Tap Water
Yongli WANG,Li MA,Liangyin XIONG,Shi LIU()
Materials for Special Environment Department, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
全文: PDF(3878 KB)   HTML
摘要: 

采用二苯碳酰二肼比色法分析测试了不同状态的304不锈钢样品在自来水环境下的Cr6+溶出规律,并对样品进行了微观组织分析。结果表明,不同状态的不锈钢材料中Cr6+溶出量差别很大,材料中的球状氧化物夹杂尺寸越大、数目越多,对应的Cr6+溶出量越高。采用粉末烧结的方法在金属中引入Cr2O3夹杂和Cr2O3+MnO2复合夹杂并测试Cr6+的溶出规律,结果显示MnO2的添加大幅度提高了Cr6+的溶出量,且氧化物添加量越多,Cr6+溶出量越大。证实了Cr/Mn复合氧化物夹杂分布 (尺寸和密度) 对不锈钢样品Cr6+溶出量有重要影响:在含Cl的水环境下,Cr/Mn复合氧化物夹杂既是Cr3+来源,又提供了氧化剂使Cr3+转化为Cr6+。这表明通过控制铸件或粉末冶金件中的Cr/Mn复合氧化物夹杂的尺寸和数目,可大幅度降低材料Cr6+的溶出量。

关键词 304不锈钢Cr6+夹杂Cr/Mn复合氧化物    
Abstract

Stainlesssteel 304 is being widely used in water supply system, and the dissolution of Cr6+ from materials of the system into tap water is one of the critical indexes of safety assessment. In the present work, different samples of stainless steel 304 components such as pipe, bar, plate, casting, and powder metallurgical product, were immersed in simulated tap water for 22 d, then the concentration of the dissolved Cr6+ in the water was determined by means of colorimetric of diphenylcarbazide with a spectrophotometer V-1800PC, while the microstructure of the samples before and after test was carefully examined by means of metallographic microscope MEF4A with image analysis system Q500 and SEM interms of morphology of grains, phase composition and distribution of inclusions etc. The results showed that the amount of dissolved Cr6+ versus time were quite different for sample to samples. The larger diameter and quantity of spherical inclusions in steels would be much favorable to the dissolution of Cr6+ for the same immersion period. In general, the spherical inclusions were complex oxides rich in Cr and Mn. In order to reveal the effect of MnO2 on the dissolution of Cr6+ from the steel, artificial inclusions of Cr2O3 and Cr2O3+MnO2 were introduced respectively into the steel by powder metallurgy, therewith the immersion test results showed that the dissolution of Cr6+ increased with the increasing amount of Cr2O3 and MnO2. These results confirm that the inclusions of Cr/Mn complex oxides play important role in the dissolution process of Cr6+, i.e. they are not only the source of Cr3+, but act also as oxidant to transform Cr3+ to Cr6+ in the Cl- contained solution. It can be inspired from these results that the Cr6+ dissolution could be significantly decreased by controlling the density and size of Cr/Mn oxides inclusions.

Key wordsstainless steel 304    hexavalent chromium    inclusion    Cr/Mn complex oxide
    

引用本文:

王永利,马利,熊良银,刘实. 夹杂对自来水环境下304不锈钢腐蚀及金属离子溶出的影响[J]. 中国腐蚀与防护学报, 2016, 36(4): 328-334.
Yongli WANG, Li MA, Liangyin XIONG, Shi LIU. Effect of Inclusions on Corrosion and Dissolution of Metallic Ions of Stainless Steel 304 in Simulated Tap Water. Journal of Chinese Society for Corrosion and protection, 2016, 36(4): 328-334.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2015.124      或      https://www.jcscp.org/CN/Y2016/V36/I4/328

Sample C Mn P S Si Cr Ni Fe
GB/T 1220-1992 ≤0.07 ≤2.00 ≤0.035 ≤0.03 ≤1.00 17.0~20.0 8.00~11.00 Bal.
1#Casting 0.046 0.89 0.032 0.006 0.54 17.9 8.63 Bal.
2# Casting 0.042 1.05 0.037 0.007 0.63 18.2 8.34 Bal.
Plate 0.034 0.47 0.035 0.006 1.08 18.12 8.08 Bal.
Bar 0.050 1.43 0.030 0.006 0.47 18.20 8.45 Bal.
Pipe --- 0.68 --- --- 0.50 19.51 8.03 Bal.
Powder metallurgy --- 0.68 --- --- 1.39 19.97 9.70 Bal.
表1  样品成分分析结果
图1  不同状态304不锈钢样品的Cr6+溶出规律
图2  5种304不锈钢样品的晶粒形貌
图3  不同样品的δ铁素体形貌
图4  棒材和2#铸件中的σ脆性相形貌
图5  5种不同样品的夹杂分布
图6  2#铸件中大尺寸球状夹杂物的BSE像
图7  MnO2对Cr6+溶出规律的影响
图8  Ni-Cr2O3-MnO2烧结体中Cr2O3+MnO2含量对Cr6+溶出量的影响
[1] Li Q P, Zhang X H, Jia Y L.Effects of cast iron and chromeplate tap on over-night tap water quality[J]. Prev. Med. Tribune, 2006, 12: 41
[1] (李庆平, 张秀绘, 贾永莲. 铸铁和镀铬水龙头对过夜自来水水质的影响[J]. 预防医学论坛, 2006, 12: 41)
[2] Chen B H, Zhu H G, Qu W D.Introduction of the world health organization guidelines for drinking-water quality[J]. J. Environ. Health,2000, 17: 247
[2] (陈秉衡, 朱惠刚, 屈卫东. 世界卫生组织饮用水质量基准简介[J]. 环境与健康杂志, 2000, 17: 247)
[3] Wu Y Y, Qu J H, Liu H J, et al.Mutual influences of different pipes and static drinking water[J]. Tech. Equip. Environ. Pollut. Control, 2005, 6(7): 44
[3] (吴元英, 曲久辉, 刘会娟等. 不同管材水管与静态自来水水质间的相互影响[J]. 环境污染治理技术与设备, 2005, 6(7): 44
[4] Percival S L, Knapp J S, Edyvean R G J,et al.Biofilms, mains water and stainless steel[J]. Water. Res., 1998, 32: 2187
[5] Gu J L.Control measures for tap water quality in developed countries[J]. Overview Disaster Prevent., 2013, (6): 72
[5] (顾锦龙. 世界发达国家保障自来水水质的做法[J]. 防灾博览, 2013, (6): 72
[6] Andersen H, Olsson C-OA, Wegrelius L. Critical pitting temperatures in sodium chloride and ferric chloride solutions-determined using the 'Avesta cell' [J]. Mater. Sci. Forum, 1998, 289-292: 925
[7] Fang X Y, Wang W G, Guo H, et al.Corrosion behaviors of random and special grain boundaries in a sensitized 304 stainless steel [A]. Proceedings of Sino-Swedish Structural Materials Symposium[C]. Beijing, 2007: 339
[8] Wang R.Corrosivity study of light gauge stainless steel pipe in living water [D]. Beijing: Beijing University of Technology, 2012
[8] (王睿. 薄壁不锈钢管在生活供水中腐蚀性试验研究 [D]. 北京: 北京工业大学, 2012)
[9] Yu X F.Study of the intergranular corrosion of stainless steel (304,316) by experimental and theroretical methods [D]. Ji'nan: Shandong University, 2010
[9] (于晓飞. 304、316不锈钢晶界腐蚀的实验与理论研究 [D]. 济南:山东大学, 2010)
[10] Du N, Tian W M, Zhao Q, et al.Pitting corrosion dynamics and mechanisms of 304 stainless steel in 3.5%NaCl solution[J]. Acta Metall. Sin., 2012, 48: 807
[10] (杜楠, 田文明, 赵晴等. 304不锈钢在3.5%NaCl溶液中的点蚀动力学及机理[J]. 金属学报, 2012, 48: 807)
[11] Apte A D, Tare V, Bose P.Extent of oxidation of Cr(III) to Cr(VI) under various conditions pertaining to natural environment[J]. J. Hazard. Mater., 2006, 128B: 164
[12] Eary L E, Rai D.Kinetics of Cr(III) oxidation by manganese dioxide[J]. Environ. Sci. Technol., 1987, 21: 1187
[13] Fendorf S E, Zasoski R.Chromium (III) oxidation by β-MnO2. Part I: characterization[J]. J. Environ. Sci. Technol., 1992, 26: 79
[14] Myers C R.The effects of chromium (VI) on the thioredoxin system: Implications for redox regulation[J]. Free Radical Biol. Med., 2012, 52: 2091
[15] Linos A, Petralias A, Christophi C A, et al.Oral ingestion of hexa-valent chromium through drinking water and cancer mortality in an industrialarea of Greece-An ecological study[J]. Environ. Health-Glob., 2011, 10: 50
[16] Kaprara E, Kazakis N, Simeonidis K, et al.Occurrence of Cr (VI) in drinking water of Greece and relation to the geological background[J]. J. Hazard. Mater., 2015, 281: 2
[17] Barceloux D G.Chromium[J]. J. Clin. Toxicol., 1999, 37: 173
[18] Lindsay D R, Farley K J, Carbonaro R F.Oxidation of CrIII to CrVI during chlorination of drinking water[J]. J. Environ. Monit., 2012, 14: 1789
[1] 张浩, 杜楠, 周文杰, 王帅星, 赵晴. 模拟海水溶液中Fe3+对不锈钢点蚀的影响[J]. 中国腐蚀与防护学报, 2020, 40(6): 517-522.
[2] 骆鸿,高书君,肖葵,董超芳,李晓刚. 磁控溅射工艺对CrN薄膜及其腐蚀行为的影响[J]. 中国腐蚀与防护学报, 2019, 39(5): 423-430.
[3] 史伟宁,杨树峰,李京社. 不锈钢中诱发局部腐蚀的贫Cr区研究进展[J]. 中国腐蚀与防护学报, 2019, 39(4): 281-290.
[4] 彭文山,侯健,丁康康,郭为民,邱日,许立坤. 深海环境中304不锈钢腐蚀行为研究[J]. 中国腐蚀与防护学报, 2019, 39(2): 145-151.
[5] 廖彤,马峥,李蕾蕾,马秀敏,王秀通,侯保荣. Fe2O3/TiO2纳米复合材料对304不锈钢的光生阴极保护性能[J]. 中国腐蚀与防护学报, 2019, 39(1): 36-42.
[6] 刘辉,邱玮,冷滨,俞国军. 304和316H不锈钢在LiF-NaF-KF熔盐中的腐蚀行为研究[J]. 中国腐蚀与防护学报, 2019, 39(1): 51-58.
[7] 张思齐,杜楠,王梅丰,王帅星,赵晴. 阴极面积对3.5%NaCl溶液中304不锈钢稳态点蚀生长速率的影响[J]. 中国腐蚀与防护学报, 2018, 38(6): 551-557.
[8] 黄勇, 王善林, 王帅星, 龚玉兵, 柯黎明. 含硫化物夹杂铁基块体非晶合金在HCl溶液中的腐蚀行为[J]. 中国腐蚀与防护学报, 2018, 38(2): 203-209.
[9] 艾莹珺,杜楠,赵晴,黄世新,王力强,文庆杰. 温度对304不锈钢亚稳蚀孔萌生和稳态蚀孔几何特征的影响[J]. 中国腐蚀与防护学报, 2017, 37(2): 135-141.
[10] 沈杰,刘卫,王铁钢,潘太军. 304不锈钢双极板表面TiN涂层的腐蚀和导电行为研究[J]. 中国腐蚀与防护学报, 2017, 37(1): 63-68.
[11] 方玉荣,付朝阳. 酸性FeCl3溶液中304不锈钢的超声腐蚀和缓蚀行为[J]. 中国腐蚀与防护学报, 2015, 35(4): 305-310.
[12] 叶超, 杜楠, 田文明, 赵晴, 朱丽. pH值对304不锈钢在3.5%NaCl溶液中点蚀过程的影响[J]. 中国腐蚀与防护学报, 2015, 35(1): 38-42.
[13] 许洪梅, 柳伟, 曹立新, 苏革, 高荣杰. 304不锈钢表面ZnO/TiO2复合薄膜的制备与光生阴极防腐蚀性能研究[J]. 中国腐蚀与防护学报, 2014, 34(6): 507-514.
[14] 程从前, 曹铁山, 王冬颖, 姚景文, 王健, 关锰, 赵杰. Cr13不锈钢在盐酸溶液喷射冲刷作用下的表面腐蚀形貌表征[J]. 中国腐蚀与防护学报, 2014, 34(5): 439-444.
[15] 王斌, 周翠, 李良君, 胡红梅, 朱加祥. X100管线钢焊接接头抗HIC性能研究[J]. 中国腐蚀与防护学报, 2014, 34(3): 237-242.