高强不锈钢在海水环境中的阴极保护行为研究

目的 研究不同阴极极化电位下高强不锈钢的极化行为,确定某高强不锈钢合理的阴极保护电位区间。方法 通过动电位极化测试以及电化学阻抗测试等电化学测试手段,研究此种高强不锈钢在海水中的阴极反应过程,通过不同极化电位下的恒电位极化测试,结合扫描电子显微镜和能谱仪,观察分析试样表面的腐蚀产物,研究阴极极化电位对高强不锈钢表面阴极产物膜的影响规律,以及对高强不锈钢在海水中的阴极保护效果。结果 动电位极化测试表明,在‒0.50~‒0.90 V,只需要施加很小的阴极电流,就可使极化电位发生显著变化。电化学阻抗谱测试及拟合结果表明,极化电位在‒0.70 V时,电极反应的电荷转移电阻最大,此时腐蚀被完全抑制。恒电位极化测试发现,随着电位负移,极化电流密度整体上呈现先减小、后增大的趋势。用能谱仪分析其表面产物发现,钙镁沉积层的致密度呈现先增加、后降低的趋势。结论 此种高强不锈钢在海水环境中施加阴极电位为‒0.50~‒1.00 V时,可以得到有效保护。     

锌合金高温阳极在FPSO工艺水舱的性能研究

目的 研究船东指定型号的锌合金牺牲阳极在模拟工艺水舱环境中的电化学性能。方法 参照NACE TM 0190—2012中的电化学测试方法,测试该锌合金阳极在不同模拟环境下的工作电位、电化学容量等,结合舱壁材料的动电位极化测试,评估该阳极在工艺水舱环境中的电化学性能,以及是否满足舱壁阴极保护的要求。结果 在55 ℃模拟溶液中,阳极的工作电位、电化学容量等测试结果均比较满意,所有指标均达到了NACE标准中对锌合金阳极在常温环境中的要求。测试温度为80 ℃时,试样的电化学容量略有下降,工作电位明显正移。环境温度对舱壁材料也产生了明显影响,高温下舱壁试样的自腐蚀电位负移,同时自腐蚀电流增加。结论 在55 ℃的工艺水舱环境下,该锌合金高温阳极满足舱壁的阴极保护需求,但在80 ℃的舱室极限高温下,该阳极不宜长期服役,有欠保护的风险。此外,在实际中,建议定期监测涂层状态和阴极保护电位。     

几种牺牲阳极在干湿交替条件下的自放电行为比较

模拟海水与空气的干湿交替条件,对四种海船常用牺牲阳极的自放电行为进行了研究。通过测定工作电位、发生电流、溶解性能、溶解产物成分,分析了四种牺牲阳极在经历不同间浸工作周期后的电化学性能,特别是再活化性能。结果表明:在干湿交替条件下,Zn-Al-Cd阳极的电化学性能降低幅度最大,Al-Zn-In-Cd阳极次之,它们均不适合在此环境中使用;Al-Zn-In-Mg-Ti的电化学性能比前两者好,Al-Zn-In-Mg-Ga-Mn则最适合作为干湿交替环境中的牺牲阳极。     

铝合金牺牲阳极深海应用性能研究

目的评价铝合金牺牲阳极在深海环境的电化学性能。方法通过利用中国船舶重工集团公司第七二五研究所深海试验技术和装置,原位测量三种铝合金牺牲阳极在南海1200 m深海环境的电化学性能。结果三种阳极在1200 m深海环境下的开路电位均在?1.17 V左右,工作电位在?1.11～?0.91 V范围内。1#和2#阳极的实际电容量小于2400A?h/kg,电流效率约为80%,表面存在明显的优先溶解和晶粒脱落现象,表面腐蚀产物有结壳现象发生。3#阳极的实际电容量约为2500A?h/kg,电流效率大于85%,表面微观溶解形貌相对均匀,但表面存在大面积未溶解区域,且腐蚀产物不易脱落。结论该研究结果为深海工程装备阴极保护设计提供了支撑。     

Al-Zn-In系牺牲阳极在间浸环境中的性能研究

目的探究4种常用Al-Zn-In系牺牲阳极(Al-Zn-In、Al-Zn-In-Cd、Al-Zn-In-Mg-Ti、Al-Zn-In-Mg-Ga-Mn)在海水间浸环境中的电化学性能。方法采用恒电流法对4种阳极的开路电位、工作电位、实际电容量、电流效率及溶解形貌等进行研究,并结合电化学阻抗谱、动电位极化曲线等方法进行分析。结果在间浸环境中,Al-Zn-In、Al-Zn-In-Mg-Ti、Al-Zn-In-Mg-Ga-Mn的电流效率均在88.92%以上,3种阳极的工作电位在-0.96~-1.10 V波动,能满足碳钢在间浸环境中的保护需要。Al-Zn-In-Mg-Ga-Mn阳极溶解形貌均匀,Al-Zn-In和Al-Zn-In-Mg-Ti阳极溶解形貌略差。Al-Zn-In-Cd阳极电流效率仅为80.95%,工作电位在-0.93~-1.10 V波动,溶解形貌不均匀,电化学性能最差。研究发现,Al-Zn-In-Cd阳极表面附着的腐蚀产物多次在空气环境中脱水,并形成壳层,导致电位正移,阻碍阳极的进一步活化。结论在间浸环境中,4种阳极的电化学性能由好到差依次为Al-Zn-In-Mg-Ga-Mn阳极、Al-Zn-In阳极、Al-Zn-In-Mg-Ti阳极、Al-Zn-In-Cd阳极,前3种阳极适用于间浸环境中海洋结构物的阴极保护。     

海洋环境Al-Zn-In-Mg-Ti牺牲阳极腐蚀防护研究

以Al-Zn-In-Mg-Ti牺牲阳极为研究对象,在海洋环境下做车辆的牺牲阳极腐蚀防护试验。采用电位自动记录仪采集浸入海水期间车体的动态电位,绘制时间-电位（t-E）曲线图,并分析数据;采用扫描电镜（SEM）和X射线衍射（XRD）等方法对牺牲阳极试样表面腐蚀形貌及成分进行了分析。结果发现,Al-Zn-In-Mg-Ti牺牲阳极增加了车体电位的稳定性,使车体电位部分极化到-800 mV;车体电位达到平衡的时间为7 min,加速了车体电位达到平衡的时间;Al-Zn-In-Mg-Ti牺牲阳极腐蚀产物在表面形成致密氧化层,并在干湿交替的作用下形成龟裂的裂纹,阻止了牺牲阳极的进一步反应。     

Al-Zn-In系铝合金牺牲阳极电化学性能研究

目的研究三种不同成分Al-Zn-In系铝合金牺牲阳极在常规海水环境中的电化学性能。方法使用牺牲阳极电流效率测试和表面形貌观察等方法。结果三种不同成分铝合金牺牲阳极的电流效率均超过了90%,其中成分3的阳极表面溶解最均匀,呈现均匀溶解形貌,并且未见明显的腐蚀坑和晶间腐蚀现象。结论Al-Zn-In系铝合金牺牲阳极中,加入一定量的In、Zn和适量的Si,可以提高牺牲阳极的电化学性能,三种不同成分Al-Zn-In系铝合金牺牲阳极中,成分3牺牲阳极具有最优异的电化学性能。     

压载舱锌阳极失效原因分析及实验室研究

目的 找到压载舱锌阳极失效原因,并提出整改方案。方法 对服役环境进行调研、阳极化学成分检测、电化学性能检测以及阳极表面形貌检测。结果 干湿交替以及高温的环境是造成锌阳极发生钝化的主要原因。在干湿交替环境下,阳极腐蚀表面晶粒松散,晶界宽度大,发生晶间腐蚀和晶粒脱落,造成了阳极失效。结论 通过该项目的实验研究,得出了锌阳极的适用条件,在干湿交替的环境以及高温环境(50 ℃)下,不推荐使用锌阳极,建议使用铝阳极。     

阳极化对SP700钛合金/2A12铝合金偶对电偶腐蚀影响研究

目的 研究阳极化处理对SP700钛合金与2A12铝合金电偶对的腐蚀行为和机理的影响。方法 采用电化学极化曲线测试法对阳极氧化处理前后的SP700钛合金的耐蚀性能进行初步研究,并以此作为边界条件,采用有限元数值模拟的方法,对不同状态的SP700钛合金与2A12铝合金组成的偶对电偶腐蚀情况进行模拟计算。同时,开展电偶对的电偶腐蚀试验,对模拟结果进行验证。此外,通过对电偶腐蚀后的试件表面微观形貌进行表征,进一步分析不同电偶对的腐蚀规律差异。结果 SP700钛合金阳极氧化前的自腐蚀电位为‒283 mV,腐蚀电流密度为6.164×10^‒9 A/cm²;氧化后的自腐蚀电位为‒270 mV,腐蚀电流密度为8.589×10^‒10 A/cm²。SP700钛合金阳极氧化前与2A12铝合金的试验和仿真平均电偶电流密度分别为6.81、6.76 μA/cm²;SP700钛合金阳极氧化后与2A12铝合金的试验和仿真平均电偶电流密度分别为2.58、2.54 μA/cm²。结论 SP700钛合金表面阳极化处理可有效降低与铝合金之间电偶腐蚀的敏感性。     

浸水率对低合金钢海水腐蚀行为的影响

目的计算不同浸水率试样的平均腐蚀速率,并与全浸条件下的腐蚀行为进行对比研究。方法采用电化学测量技术,测量不同干湿循环后试样在海水中的开路电位、极化电阻和电化学交流阻抗,分析不同浸水率对低合金钢电化学性能的影响。利用三维视频显微镜观察不同浸水率试样的腐蚀形貌,采用X射线分析仪分析锈层组成。结果干湿交替条件下低合金钢的腐蚀速率比全浸条件下增大1个数量级,自腐蚀电位正移150 mV左右,极化电阻增大2个数量级;且随着浸水率增大,腐蚀速率减小,自腐蚀电位无明显变化,试验初期电阻增大,但是试验后期无明显变化。结论观察腐蚀形貌和锈层组成,全浸条件下以FeOOH为主,干湿交替条件下出现较多的Fe3O4。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.