Al-Zn-Sn-Ce牺牲阳极干湿交替环境电化学性能研究

目的 为满足高强钢装备的阴极保护要求,开展新型干湿交替环境牺牲阳极电化学性能测试,评价材料的阴极保护效果。方法 采用高温熔炼方法,制备Al-Zn-Sn-Ce低电位牺牲阳极试样,进行不同浸水率下(干湿态环境时间比为1:1、3:1和7:1)的干湿交替环境牺牲阳极电化学性能试验、电化学表征测试及腐蚀微观形貌表征,通过对比试验数据和材料形貌表征结果,综合分析铝合金牺牲阳极在干湿交替环境下的电化学性能,探究干湿交替环境因素对阳极溶解行为的影响。结果 Al-Zn-Sn-Ce牺牲阳极在多种试验环境下的工作电位为‒0.70~‒0.81 V(vs. SCE),符合高强钢阴极保护电位需求,阳极表面溶解形貌相对均匀,表面阴阳极电化学微区分布均匀。随着干湿态试验环境时间比的增加,阳极工作电位出现正移,干态环境下表面腐蚀产物的沉积和结壳导致阳极活化溶解能力下降,而干湿态环境时间比最大时,阳极自腐蚀反应得到一定的抑制,阳极电流效率均保持在75%以上。结论 随着干湿态试验环境时间比的增加,牺牲阳极在干湿交替试验环境中的工作电位出现正移。由于干态环境下表面腐蚀产物的沉积和结壳,导致阳极活化溶解能力下降,但自腐蚀反应得到抑制。Al-0.7Zn-0.1Sn-0.1Ce低电位牺牲阳极在复杂干湿交替环境中表现出良好的阴极保护性能。     

干湿交替频率对有机涂层失效过程的影响

目的研究干湿交替频率对有机涂层失效过程的影响。方法应用电化学阻抗谱技术,结合浸泡过程中涂层表面以及基底金属的形貌变化,对比研究高频率干湿交替环境和低频率干湿交替环境下,浸泡初期、浸泡中期、浸泡末期有机涂层的失效过程及特征。结果高频率干湿交替环境下,涂层在浸泡初期、中期、末期所经历的时长分别为13、2、5d,而低频干湿交替环境下,涂层在浸泡初期、中期、末期所经历的时长分别为18、4、46 d。对比来看,高频率干湿交替显著缩短了浸泡后期的时长,加速涂层失效过程。此外,高频干湿交替使涂层起泡位置分布均匀,基底金属均匀腐蚀,这与低频干湿交替环境恰好相反。结论高频率干湿交替环境下,涂层失效较快,涂层剥离及基底金属腐蚀较均匀。     

低频率干湿交替环境中有机涂层失效过程

目的 研究低频率干湿循环条件下的有机涂层失效过程。方法 应用电化学阻抗谱技术,结合浸泡过程中涂层表面以及基底金属的形貌变化,对比研究全浸环境和低频率干湿交替环境下,浸泡初期、浸泡中期、浸泡末期有机涂层的失效过程及特征。结果 低频率干湿交替环境下,涂层在浸泡初期、中期、末期所经历的时长分别为18、4、46天,较全浸环境来讲,显著缩短了浸泡中期的时长,同时也显著延长了浸泡末期的时长。两种环境下的涂层均发生明显的局部剥离,且基底金属也均有明显的局部腐蚀。结论 低频率干湿交替环境明显延长了涂层的失效过程,且此环境下基底金属出现了明显的局部腐蚀。     

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。     

铝合金表面阳极化层环境损伤失效行为研究

目的研究7B04铝合金硫酸阳极化层环境作用下的失效行为,分析单独盐雾试验和环境谱作用下阳极化层的损伤行为和影响因素。方法通过中性盐雾试验和环境谱周期性试验(盐雾试验+温度试验)研究了硫酸阳极化层在不同腐蚀时间或不同腐蚀周期下的腐蚀损伤变化过程,并采用体视显微镜和扫描电子显微镜(SEM)观察了不同腐蚀时间下或不同腐蚀周期下的表面形貌,结合有限元方法研究了阳极化层与铝合金基体热膨胀系数不匹配引起的热应力,定量分析了热应力对阳极化层失效行为的影响。结果经历中性盐雾试验和环境谱试验的硫酸阳极化层损伤失效现象是不一样的,中性盐雾试验中硫酸阳极化层主要呈鼓起开裂失效,而环境谱试验中硫酸阳极化层以开裂剥落失效为主。结论中性盐雾试验中硫酸阳极化层主要是腐蚀介质通过表面微孔进入基体,导致基体腐蚀阳极化层鼓起,而环境谱试验因温度作用产生的热应力引起了硫酸阳极化层的开裂,形成了腐蚀介质进入基体的通道,引起阳极化层的剥落。     

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。     

FPSO工艺水舱阳极快速消耗原因分析

目的 研究FPSO工艺水舱中铝牺牲阳极消耗过快的原因。方法 参照GB 17848—1999牺牲阳极电化学性能试验方法,对比水舱环境与普通环境下,在役阳极的电化学性能数据,并模拟水舱环境,监测阳极工作时实际的发生电流与工作电位等情况,据此分析牺牲阳极在工艺水舱中消耗过快的原因。结果 在常温（25 ℃）、常温充空气、高温（65 ℃）充空气等条件下,阳极的电化学容量分别是2522.07、2464.29、1943.74 Ah/kg,且高温（65 ℃）充空气环境下阳极的晶间腐蚀较其他两组试验严重许多,说明温度是影响阳极电化学容量的关键因素。在模拟工艺水舱环境下,实测的阳极发生电流最高可达100 mA。将工艺水与海水1:5稀释后,实测的保护电流密度最高达45 mA,说明工艺水中存在大量的去极化剂,是造成阳极快速消耗的又一重要因素。结论 工艺水舱环境下,阳极发生严重的晶间腐蚀,严重影响了阳极的电化学容量,使阳极寿命缩短。工艺水成分中含大量去极化剂,使船舱所需的保护电流密度大大增加,促使阳极发生电流加大,亦缩短了阳极的实际服役寿命。     

铝合金阳极氧化膜防护性能及失效规律研究

目的研究不同腐蚀环境条件下铝合金阳极氧化膜层的防护作用及失效规律。方法采用中性盐雾、酸性盐雾试验方法进行加速试验,对无划线试样腐蚀外观和附着力以及有划线试样的腐蚀形貌等进行检测和考核分析。结果获得了4种铝合金材料阳极氧化膜层在不同试验环境条件下的防护性能、腐蚀失效、附着力变化以及抗腐蚀扩展性能等试验数据。结论铝合金材料类型对未封闭处理的阳极氧化膜的耐腐蚀扩展性能影响明显。封闭处理能够提高铝合金阳极氧化膜的综合防护性能。     

汗液作用下铝合金眼镜架腐蚀失效分析

通过金相分析、扫描电子显微镜(SEM)观察和能谱分析等检测方法,对某铝合金/硫酸阳极氧化膜眼镜架在汗液环境中的腐蚀失效行为进行了失效分析,结果表明:铝合金/酸阳极氧化膜在汗液环境中发生了严重的腐蚀,腐蚀形式以点蚀为主,局部出现裂纹,腐蚀均发生在阳极氧化膜完整性发生缺陷的部位,铝合金基体在晶界上优先发生腐蚀,点蚀坑生长和裂纹扩展均沿晶界进行;阳极氧化膜完整的区域,阳极氧化膜腐蚀不明显.     

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。     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.     

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.