摘要
随着经济的高速发展,我国水体受到了不同程度的污染,特别是城市内湖,氮、磷污染尤为严重。目前,水体的富营养化已成为一种普遍现象。淡水体是金属材料服役的重要场所,淡水体富营养化将导致服役环境的改变,使金属材料腐蚀行为与规律发生变化。国内外关于金属在污染水体中的腐蚀研究,主要集中在污染水体对输水管道腐蚀的影响,合金在污染海水中的腐蚀规律与机理研究等方面,针对水体富营养化对金属腐蚀行为影响的研究较少。本论文工作在国家自然科学基金的资助下,以水工构筑物常用金属材料A3钢为研究对象,以富营养化东湖水为研究水体,开展了水体富营养化对碳钢腐蚀行为影响的研究。主要工作和研究结果如下：
(1)研究了水体富营养化对水质指标的影响。通过比较清洁水体(丹江口水库)和富营养化水体(东湖)一年的水质检测结果,发现水体富营养化后,水质指标发生的变化主要表现为溶解氧降低,总氮、总磷浓度增大,悬浮物和微生物含量增大,水体中有毒有害物质增多。
(2)采用现场试验和实验室模拟水体试验,研究了碳钢在富营养化淡水体(东湖)和清洁水体(丹江口水库)中的腐蚀类型、速率、产物和形貌特征,进一步证实了碳钢在污染淡水体(富营养化水体)中腐蚀比清洁水体中的慢这一规律；不同挂片深度对碳钢腐蚀影响的研究表明,A3钢的腐蚀速率随着挂片深度增加而加快。该现象是由不同水深处的光照差异引起了生物量的差异造成的。这一规律由我课题组首次报道,对于认识淡水环境中微生物覆盖对金属腐蚀的影响有较大意义；挂片季节对碳钢腐蚀影响的研究表明,受季节影响,A3钢夏季(2007,07-2008,07)挂片的腐蚀速率比冬季(2005,12-2006,12)的快。
(3)研究了富营养化水体主要水质污染物对碳钢腐蚀的作用机理。系统研究了富营养化淡水中水质污染指标：总氮(铵盐、硝酸盐、亚硝酸盐、有机氮物质)、总磷(磷酸盐、磷酸氢盐、磷酸二氢盐、有机磷物质)、化学需氧量(COD)、悬浮物(高岭土)、有机污染物质(有机磷农药、有机氮农药)对碳钢腐蚀的影响。结果表明：水流速度可忽略的条件下,A3钢的腐蚀速率随溶解氧浓度的增大而增大；随COD值的增大而减小,当COD值>120mg/L时,A3钢的腐蚀速度变化缓慢；随pH值的增大呈线性降低；随水体中总氮(TN)浓度的增大而减小。铵盐在淡水中对A3钢的腐蚀有诱发作用,主要影响A3钢阴极过程的吸氧反应。亚硝酸盐和硝酸盐主要抑制A3钢的阳极过程,对A3钢腐蚀具有减缓的作用；A3钢腐蚀速度随水体中总磷(TP)浓度的增加而减小。磷酸盐、磷酸氢盐、磷酸二氢盐和多聚磷酸盐对A3钢腐蚀都具有减缓作用,作用机理为在A3钢表面形成沉积膜,抑制了A3钢阳极反应过程；A3钢的腐蚀随水体中高岭土含量的增加而减小；水体中有机磷农药(亚磷酸二乙酯)能够促进A3钢的阳极反应,使其腐蚀速度加快；有机氮农药(氨基甲酸乙酯)对A3钢的阳极反应有抑制作用,减缓其腐蚀。
(4)研究了富营养化水体中微生物对碳钢腐蚀的影响。通过对东湖挂片表面的腐蚀产物膜内的细菌进行培养、分离、纯化筛选出7种优势菌。经鉴定,主要为Comamonas菌(丛毛单胞菌)和Pseudomonas菌(假单胞菌),少量Myroides菌；富营养化水体中氮、磷、小分子碳物质对细菌生长有促进的作用；腐蚀初期,淡水中微生物(细菌和藻类)在A3钢表面的覆盖能够减缓其腐蚀速率,它们参与腐蚀产物的形成过程,使产物膜更加致密,成分更加复杂。
(5)采用电化学方法研究了A3钢在富营养化水体中的腐蚀过程；提出富营养化水体中主要环境因子对碳钢腐蚀的作用机理模型；建立多变量灰色预测模型MGM(1,3),用于富营养化水体和清洁水体中A3钢腐蚀速率的预测研究。经残差检验、关联度检验和后验差检验,该模型的精度为一级。
With the rapid development of economy, water bodies especially the urban lakes are polluted by nitrogen and phosphorus in various degrees seriously in our country. At present, the eutrophication of water bodies has become a typical and widespread phenomenon. Fresh water is also an important place where the metal materials are being serviced. Water eutrophication will lead to the changes of the service environment, therefore corrosion behavior and laws of metal materials will be changed. From now on, studies on metal corrosion in water pollution mainly concentrated in pipeline corrosion impacted by the pollution of water bodies, and corrosion laws and mechanism of alloy in pollution seawater, etc. But the study on metal corrosion behavior impacted by eutrophic water is less reported. In this paper, supported by National Natural Science Fund, A3 steel which is common used at hydraulic structures is taken as the research object, and East Lake eutrophic water is chosen as the water body, The corrosion behavior of carbon steel impacted by eutrophic water are studied. The main works and study results are as follows:
(1) The study of influence on indicators of water quality by water eutrophication. Compared with the measurement results of water quality in one year between the clean water (Danjiangkou Reservoir) and the eutrophic water (Shuiguo Lake of East Lake), the changes of water quality indicators mainly has been found that the reducing of dissolved oxygen, the increasing of the concentration of total nitrogen and total phosphorus, the enhancing of the content of suspended solids and micro-organisms and the growing of the number of toxic and harmful substances in water after eutrophication.
(2) By field tests and water body simulation tests in laboratory, corrosion type, rate, products and morphology of carbon steel in eutrophic freshwater (East Lake water) and cleaning water (Danjiangkou Reservoir)are researched, and further results confirm the law that carbon steel corrosion rate in pollution water (eutrophic water) is slower than that in clean water; the study on carbon steel corrosion impacted by different hanging depth of sample shows that A3 steel corrosion rate increases with the depth of hanging. This phenomenon is due to the difference of biomass caused by different illumination at different hanging depth. This law is first reported by my group, it is significant to understand the impact of microorganism to metal corrosion in freshwater environment; the study of metal corrosion impacted by the season of hanging sample shows that seasonal impact, the corrosion rate of A3 steel hanged at summer (2007,07-2008,07) is faster than the that hanged at winter (2005,12-2006,12).
(3) The study on corrosion mechanism of carbon steel caused by main water pollutants in eutrophic water. The influence of water pollution indicators for the carbon metal corrosion has been researched in the eutrophic freshwater which has total nitrogen (ammonium, nitrate, nitrite, organic nitrogen substance), total phosphorus (phosphate, hydrogen phosphate, dihydric phosphate, organophosphorus material), chemical oxygen demand (COD), suspended solids (kaolin), organic pollutants (organophosphorus pesticide, organonitrogen pesticide). The results show that:in case of that the rate of water flow can be neglected, A3 steel corrosion rate increases with the concentration of dissolved oxygen, decreases with the COD value, when COD> 120mg/L, the change of A3 steel corrosion rate is slow, lower linear with pH value increasing, decreases with the concentration of total nitrogen (TN) in water. Ammonium in fresh water is an inducement of corrosion of A3 steel, mainly impacting oxygenation reaction of A3 steel cathode process. Nitrite and nitrate mainly inhibits A3 steel anodic process, which reduces the corrosion of A3 steel; A3 steel corrosion rate decreases with total phosphorus (TP) concentration in water. phosphate, hydrogen phosphate, dihydric phosphate and polyphosphate reduce the corrosion of A3 steel, because deposition film is formed on the surface of A3 steel, which restrains A3 steel anodic process; A3 steel corrosion rate decreases with kaolinite content; organophosphorus pesticide (diethyl phosphite) in water can promote A3 steel anodic process to accelerate the corrosion of carbon steel; organonitrogen pesticide (urethane) inhibits A3 steel anodic reaction, reducing the corrosion of A3 steel.
(4) The study on corrosion of carbon steel impacted by bacteria in eutrophication water. By cultivating, separating and purifying bacteria in corrosion product film on the surface of sample hanged in East Lake, and 7 kinds of dominant bacteria are screened out and identified. The bacteria are mainly belonging to the species of Comamonas and Pseudomonas, and small amounts are belonging to the species of Myroides. Nitrogen, phosphorus and small molecule can promote the growth of bacteria, and the initial stages of corrosion, the surface of A3 steel covered by microbe (bacteria and algae) in freshwater can slow down the corrosion rate, they participate in forming the corrosion product, and make the product film compact and component complex.
(5) Discussing the corrosion mechanism of A3 steel in eutrophic water using electrochemical methods; putting forward an function mechanism model of main environmental factors in eutrophic water to carbon steel corrosion; Multiple Grey Predicting Model MGM(1,3) is established to predict A3 steel corrosion behavior in the clean freshwaters and eutrophic freshwaters respectively, and the accuracy of MGM(1, 3) is one grade.
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