涂层老化评级方法标准中的问题探讨

对新实施的GB/T 1766-2008标准中存在的问题进行了分析与评述,指出起泡等级的数值设置在装饰性涂层综合评级体系中不合理,标准对起泡的要求太低;同时保护性涂层综合评级中对起泡的危害也不够重视。在综合评级的低等级和高等级评价中,对剥落与生锈的要求尺度不统一,低等级对小锈点比较宽容,高等级对大锈点的要求却较严格。标准在确定生锈、开裂、起泡等单项等级时要求不细,给单项等级评定造成困扰。另外,开裂、起泡单项等级的评定指标未量化,不利于提高数据准确性。     

熵值法在涂层老化指标权重确定中的应用

目的从防护涂层力学性能和外观评级两方面综合评价涂层老化程度。方法选取失光、变色、粉化、起泡、长霉、生锈、剥落、开裂、附着力等9项涂层老化指标,运用熵值法原理对涂层9项老化指标进行权重计算与分析。结果运用熵值法计算的TB06-9+TS70-60和TB06-9+TS96-71两种防护涂层海洋大气户外环境暴露5年的老化综合评价值均为3.88级,表明两种防护涂层的抗老化性能基本一致。结论采用熵值法可以有效确定失光、变色、粉化、起泡、长霉、生锈、剥落、开裂、附着力等涂层老化指标之间的权重关系,为多指标综合评价防护涂层老化结果提供了一种客观、真实、有效、科学的评价方法。     

三种除锈方式对Q235钢表面涂层耐蚀性能的影响

目的对比研究3种不同除锈方式(打磨除锈、先除锈后磷化、除锈-磷化一体化)处理Q235钢表面后,对涂层的耐腐蚀性能的影响。方法在3种除锈方式处理后的Q235钢表面喷涂石墨烯环氧富锌底漆,测试涂层的附着力,通过中性盐雾试验测试涂层的耐腐蚀性能。结果Q235钢经过除锈-磷化一体化处理后,表面性能变优,涂层附着力达到13.6MPa,1000h中性盐雾试验后,涂层不起泡、不脱落,腐蚀程度小。结论除锈-磷化处理Q235钢表面可有效提高防腐涂层的耐蚀性能,与先除锈后磷化相比,简化了工艺过程。     

三种可磨耗封严涂层的抗腐蚀性能

目的研究AHБ,CuAl/NiC和NiCrAl/NiC三种可磨耗涂层的抗腐蚀性能。方法对三种涂层试样进行盐雾试验、湿热试验和浸泡试验,并结合电化学测试分析不同涂层试样的抗腐蚀性能。结果 545 h的盐雾试验后,AHБ涂层的表面出现了一处微裂纹,CuAl/NiC涂层表明出现了涂层剥落现象,NiCrAl/NiC涂层的表面状况相对最好;三种涂层试样经过10个循环的湿热试验后均未见明显的腐蚀现象;经过15 d的浸泡试验后,NiCrAl/NiC涂层的表面状况相对较好,而AHБ涂层和CuAl/NiC涂层的表面状况相对较差;电化学测试结果也表明NiCrAl/NiC涂层的防护性能相对最好。结论 NiCrAl/NiC涂层的抗腐蚀性能相对较高,而AHБ涂层和CuAl/NiC涂层的抗腐蚀性能相对较低。     

飞机铝合金结构连接部位表面防护体系修理技术研究

目的研究飞机铝合金结构连接部位表面防护体系修理技术。方法根据飞机铝合金连接结构腐蚀损伤特点、原防护体系类型及服役环境特点等,选取修复材料和修复工艺,制定5种不同的表面防护体系修理方法,通过在飞机典型涂层加速试验环境谱下开展加速腐蚀试验,优选出适于飞机铝合金结构连接部位表面涂层损伤修理方法。结果加速试验2周期,采用RM4修理的试件,修复部位表面开始出现脱落现象。加速试验6周期,在紧固件区域,采用RM1,RM2,RM3,RM5修理的试件在变色、粉化、开裂、起泡和剥落指标上都属于优或者良,但在生锈指标上仅采用RM3修理的试件属于良;在非紧固件区域,采用RM1,RM2,RM3,RM5修理的试件在各指标上都属于优或者良。结论 RM3更适用于飞机铝合金结构连接部位表面防护体系修理。     

蒙皮涂层在地中海气候和热带沙漠气候过渡地区的腐蚀行为模拟

目的再现地中海和热带沙漠过渡气候环境下飞机蒙皮涂层的腐蚀特征。方法采用单项试验、组合循环试验等方式对涂层试样开展模拟加速试验,观察涂层的腐蚀形态。采用扫描电镜和X射线光电子能谱分析技术研究样品表面的显微形貌及元素含量变化情况。结果盐雾试验、周期浸泡试验和湿热-盐雾-光老化组合循环试验中,样品均出现了起泡现象,这几种试验方法均强化了腐蚀介质Cl?的作用。盐雾试验和湿热-盐雾-光老化组合循环试验中的腐蚀形态与实际使用中出现的腐蚀现象基本一致。周期浸泡试验中,除起泡外,涂层还出现了实际使用过程中未出现的玷污现象。结论盐雾试验的模拟效率最高,蒙皮涂层出现起泡主要是当地大气和地下水中Cl?的作用。     

梯度化环氧涂层的制备与结构研究

目的提高环氧涂层的耐候性能,简化多层涂层体系的施工工艺。方法以氨基官能团硅树脂和聚酰胺为固化剂,共同固化环氧树脂,利用硅树脂中聚硅氧烷链段的表面迁移特性,制备得到一种聚硅氧烷/环氧梯度化层,探讨制备过程中硅树脂的用量和所用溶剂对涂层组成和结构的影响规律,采用扫描电镜-X射线能谱(SEM-EDS)、红外光谱(FTIR)、水接触角等方法对涂层结构进行表征。结果选用氨基官能团硅树脂与聚酰胺质量配比为2:8、二甲苯和正丁醇质量配比为1:1作为溶剂,得到的复合涂层表面富集聚硅氧烷链,同时底面含大量聚酰胺链段,具有链段分布的梯度化的结构。该梯度化清漆涂层经960 h盐雾老化后,无起泡、开裂、锈蚀等现象发生,具有优良防腐性能;经960 h人工加速紫外老化,失光率与色差仅为1%和8.9%,耐候性能优于常规环氧涂层。结论通过氨基官能团硅树脂和聚酰胺共固化,使环氧涂层表面富集聚硅氧烷链段,形成梯度化结构,具有耐候、防腐一体化的功能。     

有机涂层户外曝晒与加速试验对比研究

利用加速试验环境谱开展了有机涂层加速腐蚀试验。采用腐蚀程度对比方法,将试验结果与经自然曝晒的有机涂层进行对比研究,从失光、变色、粉化、起泡、开裂、剥落和基体腐蚀等特性,以及腐蚀的宏、微观形貌,对涂层分子链在降解程度等方面进行分析,证实了文中采用的加速试验环境谱模拟性好,并具有约2个周期当量自然曝晒1a的相关性。     

某型飞机腐蚀关键结构含涂层模拟件腐蚀行为研究

目的研究某型飞机腐蚀关键结构防护涂层体系的腐蚀失效行为,评估涂层的防护性能,为整机日历寿命体系评定和飞机大修提供试验依据。方法在编制加速环境谱的基础上,对模拟件进行环境谱作用下的加速腐蚀试验。结果在经过修理前后两个阶段的加速腐蚀后,模拟件在铆钉连接区域表面涂层均出现不同程度的鼓包、开裂、剥落等老化现象。结论腐蚀关键结构表面防护涂层体系总体上能够满足首翻期和翻修间隔期内结构的表面防腐要求,但在外场使用维护中应针对铆钉、螺钉连接件周围等腐蚀敏感部位加强防护,一旦出现涂层老化、破损等损伤需要及时进行局部修复。在科学、合理的外场使用维护条件下,可以适当延长飞机的进厂大修时间。     

飞机用缓蚀剂性能分析

目的延缓或抑制飞机结构腐蚀的发生。方法选择飞机维护中具有工程应用基础的5种不同类别(TFHS-15,LPS03316,Cor-Ban 35,Corrosion X Aviation,WD 40)的缓蚀剂,采用GM9540P加速腐蚀环境谱(包括盐雾、湿热和干燥等3个模块)对5种缓蚀剂的性能进行评价。结果喷涂TFHS-15试验件表面无气泡、剥落和变色,喷涂Cor-Ban 35的试验件表面无气泡和剥落,有轻微变色,这两种缓蚀剂的防护等级为10级;喷涂Corrosion X Aviation试验件表面少量剥落,防护等级为9级;喷涂LPS03316的试验件表面微量脱落和轻微变色,防护等级为8级;喷涂WD 40的试验件表面大量脱落和变色,防护等级为1级。结论经过加速腐蚀循环试验对试验件进行对比,TFHS-15和Cor-Ban 35两种缓蚀剂在飞机中使用时施工性能和防护性能最好。这两种缓蚀剂可以作为飞机腐蚀预防的有效手段,在军机中推广应用。     

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.     

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.     

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.     

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.     

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

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

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.     

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.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.