典型铝合金在江津自然大气环境中的腐蚀行为研究

通过在我国江津典型工业污染大气环境进行大气暴晒实验,测定了1060纯铝、2A12铝合金和7A04铝合金在该地区的腐蚀速率,利用扫描电子显微镜（SEM）、能量色散X射线谱（EDX）、红外光谱（FT—IR）和X射线衍射仪（XRD）观察分析3种铝合金腐蚀表面形貌、元素分布和腐蚀产物结构。结果表明：随腐蚀时间的延长,铝及其合金腐蚀产物不断增多,失重数值增加,腐蚀失重与时间的关系呈幂函数规律（C—A t^n）;腐蚀产物形貌呈块状或粒状,呈现不均匀的凹凸形貌;腐蚀产物主要为Al（OH）3和Al2（SO4）3·14H2O;耐蚀性能由强至弱依次为1060〉2A12〉7A04。     

纯铝在SO2气氛溶液中的腐蚀行为研究

采用扫描电镜（SEM/EDX）、失重法、交流阻抗谱和局部交流阻抗研究了纯铝1060在0.004mol/L Na2SO4 （pH=3.1）溶液中的腐蚀行为和规律。研究结果表明,纯铝1060在模拟溶液中连续浸泡720h后,材料质量损失与浸泡时间的关系符合指数规律即C=A·tⁿ;腐蚀产物形貌为不规则的团状或块状,分析表明腐蚀产物为氢氧化铝和硫酸铝水合物;交流阻抗结果显示纯铝1060腐蚀速率随浸泡时间的延长逐渐降低;局部交流阻抗图谱显示材料表面局部阻抗随时间而变化,并形成点蚀。     

铜在干湿交替条件下的大气腐蚀

以(NH4)2SO4(0.01 mol/L) NaHSO3(0.01 mol/L) NaCl(0.01 mol/L)为腐蚀介质,采用干湿交替复合循环试验,利用XPS、SEM表面分析技术,研究了HSO3-、Cl-和NH4 对铜的腐蚀影响,探讨了铜在该试验条件下的腐蚀机制.结果表明,铜在该条件下的质量损失随试验时间呈线性增加,其腐蚀率基本恒定,腐蚀产物不具有保护性;腐蚀产物主要为Cu2O、CuO及碱式硫酸铜.XPS分析技术用于腐蚀表面的化学成分测定是很有效的.     

X80钢在库尔勒和高pH值土壤模拟溶液中的腐蚀行为

通过浸泡质量损失法、动电位极化和交流阻抗等方法研究了X80管线钢在库尔勒和高pH值（0.5mol/L Na2CO3＋1 mol/L NaHCO3）土壤模拟溶液中的腐蚀行为,并对宏观腐蚀形貌进行了观察,采用X-射线衍射仪测试了腐蚀产物膜的组成。结果表明,X80管线钢在高pH值土壤模拟溶液中腐蚀很轻微,而在库尔勒土壤模拟溶液中则发生了严重的腐蚀,其腐蚀速率约是高pH值土壤模拟溶液中的3倍。这主要是因为X80管线钢在库尔勒土壤模拟溶液中表现出活性溶解状态,形成的腐蚀产物膜疏松、易脱落,保护性很差;在高pH值土壤模拟溶液中则很容易钝化,形成的碳酸亚铁腐蚀产物膜具有一定的阻隔效应,产生了明显的保护作用,腐蚀速率因此很低。     

模拟海水环境中8-羟基喹啉对B10铜合金的缓蚀行为研究

目的 研究模拟海水环境中8-羟基喹啉(8-HQ)对B10铜合金的缓蚀行为.方法 采用动电位极化曲线、电化学阻抗谱(EIS)和失重法等手段,研究不同浓度8-HQ在1 mol/L NaCl溶液中对铜合金的缓蚀效果,并采用傅里叶变换红外光谱仪对铜合金表面的锈层成分进行分析.结果 中时,其自腐蚀电流密度减小,阻抗模值增大.随着8-HQ浓度的升高,8-HQ对铜合金的缓蚀效率表现出先升高、后下降的阶段性特征.当铜合金浸泡在10 mg/L 8-HQ的NaCl溶液中时,阻抗模值和缓蚀效率随着浸泡时间的延长总体表现出增大的趋势.同时,对锈层的红外光谱分析进一步证明了Cu(8-HQ)2的存在.结论 8-HQ的存在减小了铜合金在NaCl溶液中的腐蚀速率,这与8-HQ在铜合金表面形成了保护膜,阻止氧从溶液中向阴极区域迁移有关.当8-HQ的质量浓度为10 mg/L时,其对铜合金的缓蚀效果最佳,并且该浓度下铜合金的耐腐蚀性能随着浸泡时间的延长持续上升.主要原因是8-HQ和Cu2+形成的[Cu(Ⅱ)HQ]络合膜与不断增厚的CuCl2保护膜在铜合金表面产生协同作用,从而抑制了电极的腐蚀反应.     

7B04铝合金海洋性大气腐蚀研究

通过在青岛和海南开展的7B04铝合金户外大气暴露试验,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7B04铝合金在海洋性大气环境中的腐蚀动力学规律和腐蚀特征。结果表明,在青岛和海南等海洋性大气环境中,7B04铝合金腐蚀初期以点蚀形式萌生,随后向均匀腐蚀发展;腐蚀过程均经历了腐蚀速率由高到低的过程,且腐蚀失重与时间的关系均可用幂函数显著回归;电化学阻抗谱分析表明当腐蚀产物足够厚时,7B04铝合金海洋性大气腐蚀的电化学过程由侵蚀性离子的扩散步骤来控制。     

6A01-T5铝合金/304不锈钢的缝隙腐蚀行为研究

目的 研究6A01-T5铝合金和304不锈钢异种金属间的缝隙腐蚀行为规律。方法 采用常温常压浸泡腐蚀方法,结合SEM、EDS、XRD和白光干涉检测,对6A01-T5铝合金/304不锈钢缝隙结构在碱性Na Cl溶液中的腐蚀行为进行研究。结果 6A01-T5铝合金/304不锈钢缝隙腐蚀表现为在缝口处产生沿缝口方向的凹陷渠,在缝内,以局部减薄和腐蚀坑为主,并随着腐蚀时间的延长,腐蚀程度逐渐加重。不同区域腐蚀产物的形貌和成分组成不尽相同,缝外暴露区的腐蚀产物表现为晶体颗粒状,主要成分为Ca CO3和Al(OH)3等铝的腐蚀产物。缝口附近沿缝口方向形成一层有明显界线的腐蚀产物覆盖层,缝隙内部的腐蚀产物相对较少,表现为尺寸相对较小的结块,主要成分为Al(OH)3等铝的腐蚀产物。结论 在6A01-T5铝合金与304不锈钢非电连接情况下,6A01-T5铝合金/304不锈钢缝隙内2种金属分别独立发生缝隙腐蚀,因2种金属在腐蚀过程中争夺O2,使得304不锈钢对6A01-T5铝合金的缝隙腐蚀起到抑制作用。     

2A12铝合金在EXCO溶液中腐蚀损伤形貌演化分析

目的探索2A12铝合金在EXCO溶液中腐蚀损伤形貌的演化规律。方法开展实验室内2A12铝合金的加速腐蚀实验。为实现表面粗糙度与腐蚀损伤相关性的定量研究,首先采用3D扫描成像仪对实验样品进行扫描,取得样品微观几何特征,实现表面粗糙度值的数字化定量表征。观察样品在EXCO溶液中腐蚀损伤的发生发展过程、腐蚀形貌的演化过程,测量腐蚀样品蚀坑深度,并分析表面粗糙度对样品腐蚀损伤的影响。结果当腐蚀时间不超过6 h时,2A12铝合金样品在EXCO溶液中的腐蚀类型主要为点蚀,随着时间的延长,将向全面腐蚀发展。粗糙度值高的试件表面有打磨时形成的较深表面纹理,这些纹理制约了点蚀坑的扩展,使蚀坑沿纹理的方向发展,有演化为微裂纹的可能性,蚀坑边界的不规则处也会萌生微裂纹。粗糙度值较小的样品,腐蚀损伤也较小,但粗糙度对腐蚀损伤的影响随时间的延长而减弱。结论常温下,2A12铝合金在EXCO溶液中首先发生点蚀,由于蚀坑向四周扩展的速度快于深度方向,使腐蚀类型从点蚀向全面腐蚀演变。表面粗糙度对2A12铝合金样品腐蚀损伤形貌的演化有重要影响,表面微观几何特征通过制约蚀坑扩展方向的方式来改变样品的腐蚀行为,并造成腐蚀损伤的明显差异。随着腐蚀时间的延长,材料逐渐失去其原有表面微观几何特征,表面粗糙度对腐蚀行为的影响下降。     

模拟酸雨大气环境中Cl-浓度对镀锌钢腐蚀行为的影响

目的研究模拟酸雨环境中Cl-浓度对镀锌钢腐蚀行为的影响与作用机理。方法以p H为3.05的模拟酸雨溶液作为空白溶液,在每升空白溶液中分别加入0.01,0.1和0.5 mol的Na Cl,浸泡3天和7天后取出试样,进行形貌、成分分析以及电化学分析。结果浸泡后镀锌钢表面形成的腐蚀产物主要为Na Zn4SO4Cl(OH)6·6H2O。随着溶液中Cl-浓度的增加,镀锌钢的腐蚀电位逐渐减小,腐蚀电流密度逐渐增大,阻抗值逐渐减小。结论通过不同时间的浸泡,随着溶液中Cl-浓度的增加,镀锌钢表面腐蚀产物对基体都有一定的保护作用,但保护作用逐渐减小,尤其在浸泡3天时的变化最明显。     

新型防腐涂层对直升机典型结构材料防护性能研究

目的研究新型防腐涂层对直升机典型结构用铝合金及复合材料在热带海洋性气候环境下的防护性能,并与原防护涂层进行对比。方法通过测试涂层腐蚀后的形貌、光泽度、色差、电化学阻抗等,对比新/原涂层对直升机典型结构用铝合金和复合材料的防护性能。结果经过2年腐蚀后,新涂层表面无明显变化,而原涂层表面有轻微腐蚀,光泽度和色差下降较大。电化学阻抗测试表明,暴露前后涂层结构无明显变化,涂层阻抗值呈现持续下降的趋势,但是原涂层阻抗下降更快。结论新涂层对直升机典型铝合金和复合材料有更好的防护性,更加适于海洋性环境的使用。     

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.     

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

ＲｅｍｏｖａｌｏｆｈｅａｖｙｍｅｔａｌｓｆｒｏｍｓｅｗａｇｅｓｌｕｄｇｅｂｙｌｏｗｃｏｓｔｉｎｇｃｈｅｍｉｃａｌｍｅｔｈｏｄａｎｄｒｅｃｙｃｌｉｎｇｉｎａｇｒｉｃｕｌｔｕｒｅＷｕＱｉｔａｎｇ，ＮｙｉｒａｎｄｅｇｅＰａｓｃａｓｉｅ，ＭｏＣｅｈｕｉＦ...     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.