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.     

安徽省内电网设备常用钢材大气腐蚀试验研究

目的针对在安徽省内H1、R1及T28三个站点自然环境下暴露1年后的Q235、40Cr及镀锌钢,开展腐蚀速率、腐蚀产物及腐蚀层形貌的研究,探讨其大气腐蚀机理。方法采用称量法计算腐蚀质量损失,通过光学及电子显微镜法观察腐蚀层表面及截面形貌,用电子能谱仪测试微区成分,用X-射线衍射法测试腐蚀层的物相构成。结果 Q235、40Cr的大气腐蚀产物为Fe OOH、Fe3O4、Fe(OH)3及FeSO4,镀锌钢则为Zn O及Zn SO4。Q235、40Cr腐蚀层表面分布着绒球状的α-FeOOH及片状的γ-FeOOH,镀锌钢大气腐蚀层致密,但T28站点镀锌钢表面形成点状的腐蚀坑,腐蚀防护能力降低。结论同一站点三种钢腐蚀速率大小次序为40CrQ235镀锌钢,站点R1钢的腐蚀速率最大,站点T28的腐蚀速率最小。     

典型耐候钢在江津大气环境中暴晒1 a的腐蚀行为

目的 研究3种典型耐候钢在江津大气环境中暴晒1 a的初期腐蚀行为。方法 采用户外大气挂片、腐蚀质量损失、SEM、XRD、电化学等方法,研究Q355NH、Q460FRW、Q690的腐蚀速率、锈层形貌、锈层物相和锈层电阻,并与Q345碳钢进行对比。结果 耐候钢和碳钢在大气暴晒初期的腐蚀规律是一致的,Q355NH、Q460FRW、Q690和Q345碳钢的腐蚀速率分别为0.050 9、0.053 6、0.047 8、0.055 mm/a,Q690的腐蚀速率最小,约为碳钢的87%。耐候钢和碳钢的锈层都主要由α-FeOOH、γ-FeOOH和Fe₂O₃组成,耐候钢的锈层更致密,裂纹更少。Q355NH、Q460FRW、Q690的锈层电阻值分别为821.3、1 005、1 080?·cm²,碳钢为101.68?·cm²,耐候钢的锈层电阻值约为碳钢的10倍。Cr和Cu元素在耐候钢的锈层中富集明显。结论 耐候钢的腐蚀速率低于碳钢,3种耐候钢的耐蚀性顺序为Q690>Q355NH>Q460FRW。Cr和Cu元素在...     

热带海洋大气环境中钢腐蚀异常原因分析

采用Q235钢和Cor-TenA钢在中国海南万宁市离海边不同距离进行不同暴露时间、朝向和不同样品表面状态的大气暴露试验，用SEM和X射线衍射对锈层和腐蚀产物进行分析，结果表明：万宁站长期暴露钢的大气腐蚀出现的所谓“异常”现象正是高湿热海洋性大气腐蚀性特征的反映。其产生原因是：在高湿热、高日照、强辐射强度和高C1^-浓度的综合作用下，使建立起来的锈层。随时间的推移起加速腐蚀作用造成的。决定钢大气腐蚀的主要环境因素是湿热气候和C1^-浓度。     

30CrMnSiA高强钢在北京地区的大气腐蚀研究

利用失重分析、形貌观察、断面分析和电化学交流阻抗谱等研究了30CrMnSiA高强钢在北京地区大气腐蚀的动力学规律和腐蚀特征。结果表明,30CrMnSiA高强钢在北京的大气腐蚀速率经历了腐蚀初期由快到慢和腐蚀3 a后由慢到快的过程。在大气暴露1,2,3,5 a的30CrMnSiA样品中,暴露3 a的样品锈层最致密,对侵蚀性离子的阻挡作用最强,相应腐蚀速率最低;30CrMnSiA高强钢在大气腐蚀的锈层既可以生长得非常致密,也可因为过厚产生内应力,从而导致锈层破裂;3 a后,30CrMnSiA样品锈层的开裂加速了腐蚀。     

钢在自然环境中的大气腐蚀研究进展

回顾了近年来钢在自然环境中的大气暴露腐蚀试验和腐蚀行为预测的研究。重点介绍了钢的腐蚀失重规律、环境因素和钢的化学成分对钢的大气腐蚀影响以及锈层分析的研究;此外,还介绍了幂函数预测模型、灰色模型和神经网络预测模型的研究进展。     

Cl-作用下AerMet100钢在盐雾环境中的 微区电化学行为

目的对Cl~-作用下AerMet100钢在盐雾环境中的腐蚀和微区电化学行为进行研究。方法通过开展盐雾腐蚀试验,对AerMet100钢的腐蚀形貌和腐蚀产物进行研究分析。盐雾试验不同时间后,通过SKP测试,得到试样的表面电位分布,通过Gauss拟合,对试样表面扫描开尔文电位的分布和变化情况进行分析。结果 AerMet100钢在盐雾腐蚀试验过程中的腐蚀行为从点蚀开始,逐渐发展为均匀腐蚀。腐蚀产物分为内外两层,外层疏松,内层致密。由于腐蚀反应过程中生成大量铁的氧化物及羟基氧化物,因此,内外层腐蚀产物中含有大量的Fe、O元素;内外锈层中均含有少量的Cl元素,表明Cl~-参与了腐蚀反应过程;内外锈层中Cr、Co、Ni等合金元素的存在,使得锈层具有离子选择性、致密性,加速了锈层的产生。未腐蚀的试样表面电位分布比较均匀,集中程度较高,即电位差较小,总体电位差为152 mV,有少量表面活性点随机分布,此时试样表面阴极和阳极分布不规则。盐雾试验3天后,试样表面电位正移,分布趋于分散,电位差增大,总体电位差为270m V,产生较为明显的阴极区和阳极区,由于吸附在试样表面活性点附近的Cl~-破坏了表面的氧化膜,腐蚀情况逐渐发生。盐雾试验6天后,试样表面电位进一步升高,分布更为分散,电位差略有减小,总体电位差为180 mV,由于腐蚀产物层的不断扩展,试样表面已经分为明显的较大面积的阴极区和阳极区。结论 Cl~-的侵蚀作用破坏了基体表面的氧化膜,使得AerMet100钢的腐蚀在夹杂物处发生。腐蚀产物能够阻碍Cl~-的渗透,对基体具有保护作用。     

碳钢和耐候钢加速腐蚀实验研究

通过对Q235碳钢和09CuPCrNi耐候钢的周期浸润加速腐蚀实验所得到的锈层结构的XRD和拉曼光谱分析表明:γ-Fe2O3、γ-FeOOH和α-FeOOH是构成锈层的主要腐蚀产物.锈层中最终形成的稳定的α-FeOOH腐蚀产物所占比例和分布都将影响耐候钢的耐蚀性能.耐候钢中的Cr可在表面形成致密的氧化膜,同时Cr在缺陷处沉淀析出,可以加速锈层中缺陷的愈合,从而可抵御大气中水气及其有害离子的侵入,防止基体金属进一步腐蚀.因此,增加耐候钢中的Cr的含量将有助于提高耐候钢的耐蚀性能.     

涂膜耐候钢大气暴露及锈层结构的研究

涂膜JT345耐候钢在青岛、沈阳、北京等地大气环境下曝晒2年,表现出良好的耐腐蚀性能,采用电子探针、X射线衍射等对大气挂片锈层形貌、结构、组成进行了分析,发现JT345耐候钢表面锈层主要由γ-FeOOH、α-FeOOH和Fe3O4组成.改性涂层处理可加速耐候钢表面生成致密保护性锈层,该锈层中富集大量的Cr、Cu、P等.     

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。     

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.