纳米涂层/铝合金在不同pH值的海水溶液中的腐蚀行为研究

目的评价纳米涂层/铝合金在不同pH值海水溶液中的腐蚀行为。方法通过测试纳米涂层/铝合金试样在不同pH值海水溶液中的EIS值,分析试样阻抗谱图及Bode谱图的演化规律,建立不同EIS图谱的不同电极阻抗模型,并采用ZView软件解析涂层体系不同时期的电化学阻抗谱,获得涂层电阻的变化趋势,及不同pH值海水浸泡的纳米涂层体系腐蚀失效速度。结果随着浸泡时间的增加及pH值的降低,纳米涂层/铝合金体系腐蚀损伤失效速率在浸泡前期整体趋势增大,但中后期由于腐蚀产物逐渐堵塞了涂层的微孔,腐蚀介质向铝合金表面渗透的速率逐渐减小。结论 pH为2.0海水浸泡下的3涂层失效最快,其次是pH为4.0海水浸泡下的2涂层,最后为p H为6.0海水浸泡下的1涂层,该涂层体系应采用等效电路模型C进行拟合。     

流动海水环境中人工破损有机涂层的劣化过程研究

目的研究流动海水环境中人工破损有机涂层的劣化过程。方法使用电化学阻抗谱(EIS)技术对比研究流动海水与静止海水环境中破损涂层的劣化行为,跟踪观察涂层宏观形貌演变。结果根据EIS响应特征,发现流动海水中的人工破损有机涂层劣化更快,且在浸泡后期流动海水中破损涂层没有形成扩散阻抗。根据涂层宏观形貌发展,发现静止海水中涂层仅围绕破损处出现了面积较小的锈点和鼓泡,而流动海水中涂层因劣化而产生的锈点和鼓泡面积更大且大量分布在整个涂层表面。结论当人工破损有机涂层在流动海水和静止海水环境的浸泡过程中,涂层劣化首先从人工破损处开始。破损处成为局部腐蚀反应主要的阳极区,破损处周围的区域和涂层内在缺陷处成为扩展腐蚀反应的阴极区。流动海水中涂层的腐蚀产物累积与脱落更加频繁,导致涂层劣化速度加快和基体金属腐蚀加剧。     

浸泡时间对两种涂层电化学腐蚀行为的影响

目的研究浸泡时间对两种涂层电化学腐蚀行为的影响。方法在质量分数为3.5%的Na Cl溶液中通入饱和CO_2气体,采用电化学方法、SEM形貌检测方法测量两种涂层在该溶液中不同浸泡时间下的动电位扫描极化曲线和表面形貌,对比分析两种涂层的电化学特征和防蚀性能。结果随着涂层浸泡时间的延长,自腐蚀电位E_(corr)逐渐降低,而电流密度逐渐增大;在浸泡时间相同的情况下,涂层A的自腐蚀电位E_(corr)比涂层B高,而电流密度比涂层B低,说明涂层A的耐蚀性能明显优于涂层B。结论涂层短时间浸泡(≤72 h)时,电化学阻抗谱为吸氧过程的单容抗弧,长时间浸泡(≥120 h)时则为析氢过程的2个容抗弧,其耐蚀性下降。     

7A04铝合金在周浸试验中的腐蚀行为研究

采用周期浸泡的腐蚀试验方法,并通过电化学阻抗谱(EIS)、扫描电子显微镜(SEM)等检测技术,研究了7A04铝合金的腐蚀行为和腐蚀机理.结果表明,7A04铝合金的腐蚀动力学符合幂函数规律,其腐蚀历程为由点蚀经短暂的晶间腐蚀后快速发展为剥蚀,EIS由高中频3个容抗弧和低频收缩的感抗弧组成.     

环氧富锌涂层对AZ91D镁合金的腐蚀防护能力研究

目的研究环氧富锌涂层对AZ91D镁合金的腐蚀防护能力。方法采用机械喷涂法在AZ91D镁合金表面制备一种保护性的环氧富锌涂层。采用电化学阻抗谱(EIS)研究环氧富锌涂层在0.5 mol/L的Na2SO4腐蚀溶液中的电化学腐蚀行为及其对镁合金的腐蚀防护能力。结果浸泡初期,环氧富锌涂层的阻抗谱中只出现一个时间常数,暗示着环氧富锌涂层优异的阻挡层作用;浸泡48 h后,环氧富锌涂层阻抗谱中出现两个时间常数,高频和低频时间常数分别对应环氧富锌涂层中高聚合的介电性质和锌粉的活性溶解;浸泡336 h后,环氧富锌涂层仍具有很高的阻抗模值,表明此时环氧富锌涂层对镁合金仍能提供良好的腐蚀防护。结论环氧富锌涂层在0.5 mol/L Na2SO4腐蚀溶液中能对AZ91D镁合金提供很好的腐蚀防护。     

环氧富锌-石墨烯涂层在中性盐雾和高低温循环浸泡中的失效研究

目的 研究20#钢表面环氧富锌-石墨烯涂层在中性盐雾和高低温循环浸泡(3.5％NaCl溶液,45℃12 h+RT 12 h)试验中的失效过程与行为.方法 采用电化学交流阻抗(EIS)测试、开路电位(OCP)监测、扫描电镜观察与分析(SEM/EDS)以及红外光谱(FTIR)等方法研究涂层在两种试验环境中的失效特征和对20#钢的保护作用,并探讨涂层失效的低频阻抗评价标准.结果 涂层试样分别在中性盐雾79 d和高低温循环浸泡160 d后,表面开始出现锈点,失去对基体的保护作用,此时低频阻抗(|Z|0.01 Hz)值降至7×104?·cm2左右.除了屏蔽作用以外,环氧富锌-石墨烯涂层还可为钢基体提供一定的阴极保护作用,其中高低温浸泡环境中的阴极保护作用时间略长.在两种加速试验环境中,涂层后期的失光率均处于"明显失光",色差值达到或接近"较大变色".红外光谱显示,涂层中的特征官能团未发生明显的变化.结论 通常利用低频阻抗(|Z|0.01 Hz)低于1×106?·cm2来衡量有机涂层(不含导电颗粒)失效的判据,不适用于评价碳钢表面的环氧富锌-石墨烯涂层体系,对于该体系的失效评价可能需要再降低近2个数量级,约为7×104?·cm2左右.     

车辆装备涂层局部微小破损对防护性能的影响研究

目的探究车辆装备有机涂层在微小破损之后性能的变化情况,并通过完好涂层防护能力的对比分析,间接预测微小破损涂层的服役寿命。方法利用某型现役装备涂层作为试验样本,进行综合环境下的循环加速腐蚀试验,最后利用EIS分析实验数据,分析两者防护性能的差别。结果完好涂层与破损涂层的防护性能均出现了大幅度的下降,两者在经过10个周期的腐蚀试验之后,都失去了防护能力,出现了大面积锈迹。完好涂层的低频阻抗模值|Z|0.1 Hz在试验初期处于1010Ω·cm2数量级,最后下降到106Ω·cm2以下;初始状态破损涂层的低频阻抗模值|Z|0.1 Hz为1.2×105Ω·cm2,9个腐蚀周期之后下降至5.7×103Ω·cm2,下降了2个数量级。结论破损涂层在腐蚀初期更多地表现出电容性质,其试验初期的防护能力大约相当于完好涂层经历6~7次循环试验之后的防护能力,破损部分随着腐蚀周期的变化呈现“钝化—溶解—再钝化—再溶解”的周期性变化规律。     

军绿有机涂层和金属漆涂层全浸泡下的腐蚀行为对比研究

目的针对车辆装备长期在高盐雾、高湿热、高日照等恶劣的气候环境下使用,会受到腐蚀影响的现状,探究现役军用有机涂层防护性能。方法采用电化学阻抗谱技术研究军绿有机涂层和金属漆涂层在3.5%NaCl溶液中的腐蚀电化学行为,分析这两种涂层在浸泡期间的电化学阻抗谱特征,通过拟合等效电路得到涂层电阻R_c和涂层电容C_c,并用这两个电化学参数评价军绿有机涂层和金属漆涂层的耐蚀性能。结果军绿有机涂层抗腐蚀介质渗透能力很强,而金属漆涂层抗腐蚀介质渗透能力稍弱。结论两种涂层都表现出很好的防护性能,且金属漆涂层在腐蚀后期的防护性能要优于军绿有机涂层。     

基于SOM-SVM组合分类器的涂层防护性能研究

目的为避免EIS,EN技术可能出现的问题,建立一个准确、高效的评价模型,以探究现役军用有机涂层防护性能。方法利用电化学阻抗谱(EIS)、电化学噪声(EN)技术分析了两种军车有机涂层在循环暴露试验中的腐蚀行为,提取低频阻抗模值|Z|_(0.1 Hz)与涂层噪声电阻R_n两种电化学评价参数作为自组织神经网络(SOM)的输入训练样本,同时结合支持向量机(SVM)方法建立涂层防护性能组合分类器。结果将涂层失效过程自适应地分为涂层防护性能良好、防护性能下降、基本失效三个阶段。结论所建立的SOM-SVM组合分类器对于辅助分析涂层防护性能具有可行性。     

阴极极化对人为破损907A涂层钢腐蚀行为的影响

采用改性厚浆环氧防锈漆作为涂层材料,研究了不同破损率的涂层对907A钢腐蚀特性及阴极保护效果的影响,测定了不同涂层破损率的907A钢在天然海水中的电化学阻抗谱和极化电流。结果表明,随着浸泡时间的延长,在自腐蚀电位下,2种试样基体的腐蚀程度都不断地加剧。在-0.85 V（vs.SCE）极化电位下,破损率为1%的试样,阴极极化对破损处涂层的破坏作用大于对钢基体的保护作用,未达到预期保护效果;对于破损率为5%的试样,由于涂层缺陷处基体上形成较厚的钙镁沉积层从而减缓了金属腐蚀。     

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.     

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.     

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.     

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.     

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.     

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.     

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.