氯化铵盐粒导致的铜初期大气腐蚀行为研究

目的研究在氯化铵存在条件下,铜的大气腐蚀行为。方法采用扫描电子显微镜(SEM)、能谱(EDS)、傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、滴定法和电化学等方法来确定铜的大气腐蚀过程和腐蚀产物。结果随着暴露时间的延长,铜的腐蚀质量损失变大,平均腐蚀速率变小。在氯化铵存在条件下,铜表面生成了Cu_2O、Cu_2(OH)_3Cl和Cu_2(OH)_2CO_3,其中Cu_2O为主要腐蚀产物,其质量占腐蚀产物总质量的97%以上。结论氯化铵的存在会对铜造成很强的腐蚀,随着暴露时间的延长,铜的腐蚀变得严重,但是暴露后期腐蚀速率将会减缓。     

2A12铝合金在模拟溶液中的周浸腐蚀行为

采用干湿周浸实验、失重法和电化学阻抗谱研究了2A12铝合金在0.6mol/L NaCl和0.6mol/L NaCl 0.02mol/L NaHSO3两种溶液中的腐蚀行为与规律, 利用扫描电镜(SEM)、能谱(EDX)和红外光谱(FTIR) 观察分析腐蚀产物表面形貌、结构和组成,测试了材料的力学性能.研究表明,随腐蚀时间的延长,腐蚀产物不断增多,失重增加,力学性能下降,阻抗模值逐渐减小;腐蚀产物形貌以团状和块状为主,在0.6mol/L NaCl溶液中腐蚀产物主要为铝的氯化物和氧化铝,在0.6mol/L NaCl 0.02mol/L NaHSO3溶液中腐蚀产物主要为氧化铝、铝的硫酸盐水合物和铝的氯化物;由于NaCl和NaHSO3共同作用,2A12合金在0.6mol/L NaCl 0.02mol/L NaHSO3溶液中腐蚀电流密度高,阻抗模值相对较小,腐蚀速率较高,腐蚀后失重大,力学性能下降幅度较大,腐蚀更严重.     

氧化聚合型包覆技术（OTC）在热带海洋大气环境螺栓中的应用

目的 研究氧化聚合型技术(OTC)在热带海洋大气环境中对高强螺栓的防护效果。方法 在三亚大气腐蚀试验站开展OTC包覆和未保护的高强螺栓6 a的大气曝晒试验,通过扫描电镜(SEM)、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)和激光共聚焦显微镜(LSCM)开展腐蚀形貌和成分分析,通过质量损失试验考察OTC包覆和未保护的高强螺栓的腐蚀行为。结果 未经保护的螺栓表面生成大量棕红色的腐蚀产物,XRD分析表明,其主要成分为α-Fe OOH、β-Fe OOH、γ-Fe OOH、Fe3O4和Fe₂O₃等,其中β-Fe OOH晶体结构中含有Cl–,会加速基体腐蚀。经LSCM分析,螺栓垫片整体呈全面腐蚀状态,但同时发生局部腐蚀,最深的点蚀坑达120μm以上。经OTC技术保护的高强螺栓,仅在底部出现少量棕色物质,大部分仍呈现原有的黑色基体表面,OTC包覆螺栓6 a的腐蚀速率约为未保护螺栓的腐蚀速率1/15,OTC包覆垫片表面未出现明显腐蚀。结论 氧化聚合型包覆技术显著降低了高强螺栓的腐蚀速率,具有优良的耐腐蚀性能,在热带海洋大气环境对高强螺栓起到良好的长...     

锌在模拟工业大气环境下的腐蚀行为研究

目的研究不同时间下锌在SO2环境中的腐蚀特性。方法采用室内加速试验法,向大气加速腐蚀箱中通入25 mg/L SO2气体,进行模拟工业大气环境下的加速腐蚀试验。对腐蚀后金属材料进行质量增量测量和电化学测试,通过XRD,SEM等表征锌腐蚀产物及腐蚀形貌,研究腐蚀特性。结果初期阶段锌在SO2环境中的腐蚀速率逐渐增加,到腐蚀后期逐渐降低,1/Rct值先增大后减小,锌的腐蚀产物中的元素包括Zn,O和少量的S,主要产物为Zn4SO4(OH)6。结论初期在锌表面生成的腐蚀产物疏松,SO2能够通过产物层到达基体,促进腐蚀,不具有保护性。到后期,产物增多并且致密使SO2与基体接触的概率降低,从而使腐蚀速率减缓。     

T2铜在不同海水飞溅条件下的腐蚀性能差异

目的研究T2铜在不同飞溅条件下的腐蚀行为。方法通过对T2铜在三亚热带海水飞溅区进行0.5、1、2 a三个周期的环境试验,采用扫描电子显微镜、X射线衍射仪对其腐蚀产物形貌、物相进行分析,使用电化学工作站对带锈样品进行分析。结果 T2铜在堤岸飞溅区和堤岸内飞溅区腐蚀速率随时间的延长逐渐下降。在飞溅区,不同周期T2铜的腐蚀产物为表面较薄的氧化层,且存在分层现象,主要由外层疏松的绿色Cu2(OH)3Cl和内层致密的棕色Cu_2O组成。不同试验周期,两处飞溅区试样表面的腐蚀产物都较为平整,堤岸飞溅区腐蚀产物层的平均厚度大于堤岸内飞溅区,腐蚀形貌均为均匀腐蚀。两处飞溅区锈层均由Cu_2O和Cu2(OH)3Cl相构成,堤岸飞溅区锈层主要为Cu_2O和Cu2(OH)3Cl相,堤岸内飞溅区锈层主要为Cu_2O相,存在少量Cu2(OH)3Cl相。结论在同一试验地点进行飞溅试验,由于飞溅条件不同,2a内铜的腐蚀速率、腐蚀产物等会存在差异。     

典型航空装备用金属材料在不同酸性盐雾环境下的腐蚀效应及机理

目的对比分析硫酸盐雾试验和盐雾/SO2复合试验的环境效应及机理差异。方法针对硫酸盐雾试验和ASTM G85附录A4-X4中的盐雾/SO2复合试验两种酸性盐雾试验方法,选取3种金属试片(4130高强度合金钢镀铬、40CrNiSi合金钢镀镍、2A12铝合金导电氧化)和2种合金钢自锁螺母(30CrMnSiA镀镉钝化螺母、30CrMnSiA镀锌钝化螺母)作为试验对象,对其开展两种酸性盐雾试验条件下的腐蚀试验,采用扫描电子显微镜、能谱分析研究各试验件表面生成的腐蚀产物形貌及组分特征,对比分析两种试验条件下的环境效应及机理差异,并结合耦合多电极矩阵(CMAS)测试技术,对比分析两种酸性盐雾试验条件下的环境腐蚀性特点及严酷性差异,初步探讨了两种试验条件与外场舰载平台环境的相关性关系。结果盐雾/SO2复合试验条件下CMAS电极的腐蚀深度达到同周期硫酸盐雾试验下的10倍左右。盐雾/SO2复合试验下,试样表面腐蚀产物中均检测出S元素的存在。相比于硫酸盐雾试验,盐雾/SO2复合试验与外场舰载平台环境具有更好的一致性。结论美军现行的盐雾/SO2复合试验方法与外场舰载平台环境具有更好的相符性。     

用ACM技术评估低合金钢大气腐蚀及环境腐蚀严酷性

将低合金钢与铜偶合．制成Cu／Fe电偶腐蚀电池(ACM),通过薄液膜下的ACM技术．研究了4种低合金钢的大气腐蚀行为差异,研究结果与其在典型大气环境下的曝露腐蚀结果一致。通过在江津、宜昌(三峡坝区)、武汉三地的ACM长期监测和环境因素监测获得了3个典型环境下ACM腐蚀电量与环境因素之间的多元线性回归分析方程．并与Q235钢在上述3个地区的大气曝露腐蚀试验所获得的结果进行了比较．探讨了采用ACM技术评估大气腐蚀严酷性的可能性。     

SO2在碳钢初期大气腐蚀中的作用

通过自建的模拟大气腐蚀系统,借助金相显微镜、扫描电镜(SEM/EDX)、X-射线衍射(XRD)和x-射线光电子能谱(XPS),研究了SO2对碳钢初期大气腐蚀行为的影响,并进一步用原子力显微镜从更微观的角度观察了在SO2环境中初期阶段腐蚀形貌变化.研究结果表明:在SO2污染大气环境中,随SO2浓度的升高碳钢腐蚀加快.在体积分数为5×10(-6)SO2的大气环境中,碳钢和耐候钢表面腐蚀主要以条状物生长,随着SO2浓度的升高,腐蚀产物的形貌发生改变,在体积分数为5×10(-5)SO2的大气环境中,条状锈和胞状锈同时生长.在锈层中S元素以FeSO4·4H2O的形式存在,腐蚀产物中还有γ-FeOOH.SO2在初期阶段加速了碳钢的腐蚀,降低了碳钢的耐蚀性.     

铜的大气腐蚀研究

综述了各种因素对铜大气腐蚀的影响,其中介绍了单一气体SO2、NOx、O3及混合气体协同作用对铜大气腐蚀的影响。在铜腐蚀中,SO2 NO2的协同效应只有在一个相对高的湿度(90%)下才发生。SO2 O3的协同效应要强于SO2 NO2的协同效应,这可以解释为什么铜在富含O3的乡村环境中有高的腐蚀率。重点阐述了硫酸铵微粒的影响,在硫酸铵的临界相对湿度(CRH)时,铜的腐蚀率和机制变化很显著;同时介绍了铜的几种腐蚀产物及其形成机制。简述了研究铜大气腐蚀的常用实验方法和几种表征手段,并展望了铜大气腐蚀的研究趋势。     

曝晒位置对纯铜热带海洋大气环境腐蚀性能的影响研究

目的研究不同离岸曝晒位置对纯铜热带海洋大气环境腐蚀性能的影响。方法通过对T2铜在三亚热带海滨离岸不同距离进行24个月的大气曝晒试验,结合大气Cl~-在相应位置的沉积量及湿度变化情况,并采用扫描电子显微镜、X射线能谱仪和XRD等对其腐蚀产物形貌、成分和物相进行分析。结果 T2铜热带海洋大气腐蚀以均匀腐蚀为主,其平均腐蚀速率随离岸距离的增加、曝晒时间的延长而下降。腐蚀产物为双层结构,外层为具有疏松结构的绿色Cu_2(OH)_3Cl,内层为致密的Cu_2O。随着离岸距离的增加、暴露时间的延长,试样表面电解液介质中Cl~-浓度越大,T2铜腐蚀产物中Cu_2(OH)_3Cl含量增加,但腐蚀产物生成主要以Cu_2O相为主。结论腐蚀速率与盐雾沉积量与离岸距离变化关系存在差异,盐雾沉积量先升后降,在离岸80 m处有最大值,由于大气相对湿度的影响,导致T2铜腐蚀速率在离岸0 m处有最大值,在离岸80 m处有极大值。     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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