交流干扰下碱性环境中富锌环氧涂层失效机制研究

目的 揭示碱性环境下交流干扰对富锌环氧涂层失效机制的影响.方法 以富锌环氧涂层为研究对象,以X80钢为基体,手工涂敷形成带涂层的X80钢样品,通过五点测试法确定涂层厚度为(25±5)μm,施加交流干扰电压.通过电化学测试,研究涂层样品在3％(质量分数)NaOH溶液中随浸泡时间的电化学阻抗变化特征,揭示交流电对富锌环氧涂层的作用机制.结果 在碱性环境下,锌粉更有利于活化,但是反应速率也更快,导致活化的锌粉表面能够迅速形成腐蚀产物Zn(OH)2和Zn(OH)42-,阻止锌粉之间的电连接,同时基体Fe在碱性环境中容易发生钝化,极大地减弱了涂层与金属基体的湿结合力.当交流干扰存在时,活化锌粉的反应过程非常迅速,以至于不能形成有效的电连接和阴极保护.结论 交流干扰能够抑制锌颗粒的活化过程(ZnO→Zn(OH)2/Zn(OH)42-),促进活化锌颗粒的反应过程,削弱锌的阴极保护作用.     

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。     

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。     

海水淡化装置内舱碳钢防护涂层寿命预测研究

目的获得海水淡化装置内舱碳钢防护涂层的耐热老化寿命。方法通过调整设备的温度及压力,模拟低温多效蒸发器半浸区工作环境,进行为期20个月的浸泡加速试验。以涂层的附着力随老化时间的变化情况、涂层颜色变化情况、涂层浸泡前后微观形貌和阻抗值为评判依据,在老化经验公式的基础上进行外推计算,进行涂层热老化寿命预测。结果该涂料在该区域经过20个月的挂片试验,涂层表面均未出现起泡、锈蚀、开裂、脱落等失效现象;表面色差变化趋势相对稳定;干态附着力为10.9 MPa,经过20个月的测试,附着力为8.95 MPa;0.01 Hz低频阻抗(|Z|0.01 Hz)条件下,其电化学交流阻抗值由浸泡前的1.8×10^8Ω·cm^2下降为浸泡后的7.9×10^6Ω·cm^2。涂层阻抗的数量级虽有所下降,但仍然具有较高的阻抗值,具有较好的保护性能。经过老化经验公式进行外推计算,预测海水淡化装置内舱碳钢防护涂层的热老化寿命为13.33年。结论海水淡化装置内舱防护涂料具有长寿命热老化重防腐作用。     

沿海地区输电铁塔防护涂层耐腐蚀性能研究

目的研究沿海地区输电铁塔防护涂层体系的腐蚀失效行为,评估涂层的防护性能,为铁塔防护涂层寿命体系评定和修复提供试验依据。方法分别采用热镀锌、热镀锌/冷涂锌复合涂层、热镀锌/带锈环氧涂层三种技术方案,对铁塔角钢材料进行防腐保护,采用中性盐雾方法模拟沿海环境对试样进行耐蚀性测试,通过试样表面形貌观察、极化曲线、以及阻抗谱等电化学手段对保护效果进行评价。结果热镀锌、热镀锌/冷涂锌复合涂层在盐雾150 h出现大面积腐蚀,热镀锌/带锈环氧涂层在盐雾2000 h未发生明显腐蚀。结论热镀锌/带锈环氧涂层的耐蚀性能优于热镀锌/冷涂锌漆和热镀锌涂层。     

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。     

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.     

基于电化学阻抗的直升机涂层日历寿命评估方法

目的研究直升机涂层在使用过程中的日历寿命评估方法。方法分析影响直升机涂层日历寿命的主要因素,给出涂层日历寿命分散性和差异性的原因,确定关键评估技术。以某型高原直升机涂层日历寿命评估为例,开展8个周期的加速试验,选取电化学阻抗模值(|Z|f=0.1 Hz)描述涂层性能退化失效过程。结果涂层电化学阻抗模值与加速周期满足函数关系。结论应力疲劳影响涂层性能退化,在环境因素和较高局部应力共同作用下,涂层性能退化更明显。该涂层性能不满足6年高原日历寿命。     

环氧涂层在不同温度海水中的失效行为研究

目的研究环氧涂层在不同温度海水环境中的腐蚀失效行为。方法采用电化学阻抗谱(EIS)技术研究两种海水环境中涂层的EIS特征,同时分析涂层电阻和涂层电容的变化,以研究环氧涂层防护性能随浸泡时间的变化。结果涂层在15℃海水中浸泡1440 h时,阻抗值下降至106?·cm2以下,而在30℃海水中仅浸泡72h时,阻抗值就已下降至106?·cm2。随着浸泡时间的增加,涂层在15℃海水中的EIS响应由高阻抗的单容抗弧变为双容抗弧,而在30℃的海水中,EIS响应首先由单容抗弧演变为双容抗弧,随后又出现了明显的Warburg扩散阻抗特征。涂层电容在两种温度的海水中均呈上升趋势,电阻呈下降趋势。结论涂层在30℃海水中的劣化速度加快,是因为升高温度能够降低涂层与金属间的结合力,加快了海水向涂层内部渗透的速率。由于温度的升高加快了溶解氧的扩散速率,使得氧扩散过程成为腐蚀反应的控制步骤,从而导致了涂层在30℃海水中的EIS响应出现了明显的Warburg扩散阻抗特征。当环氧涂层在15℃与30℃的海水中浸泡1800 h时,其防护性能的变化可以分为快速下降、缓慢下降、趋于稳定三个阶段。     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.