热处理温度对热障涂层微观形貌及元素互扩散的影响

目的提高热障涂层抗氧化性能,并减小二次反应区的形成。方法采用真空电弧离子镀技术在二代单晶高温合金DD32表面制备NiCoCrAlYHf(HY5)金属粘结层,分别在870℃及1000℃下进行真空扩散处理,利用电子束物理气相沉积(EB-PVD)技术制备氧化钇部分稳定氧化锆(YSZ)陶瓷层。采用扫描电子显微镜(SEM)、电子探针(EPMA)以及能谱(EDS)等测试方法,研究高温循环氧化过程中热障涂层的微观形貌、成分及扩散机制,同时计算了1、125 h氧化时间下Al元素互扩散系数。结果经过1000℃热循环、1000℃热处理的涂层氧化质量增量的绝对值较小,氧化速率常数为7.21×10-4,抗循环氧化性能较好。1100℃热处理试样,从涂层表面到基体方向Ni、Al、Cr等元素分布都比较均匀,在涂层与基体界面处,元素含量变化较为平滑。870℃热处理试样,Ni等元素质量分数分布不均,在涂层与基体界面处元素含量陡然变化,元素均质化程度低。Al元素扩散系数随着浓度的增加而增大,随着氧化时间的延长,粘结层与高温合金之间的元素扩散程度加剧,Al元素扩散系数减小。经过125h循环氧化,粘结层/基体界面出现互扩散区,互扩散区局部区域富Cr,Al含量低。循环氧化250 h后,热障涂层试样扩散区下方有拓扑密堆相TCP析出,形成二次反应区SRZ。真空扩散温度为870℃的试样,二次反应区更加明显。结论金属粘结层在1000℃下进行真空热处理可以有效提高涂层的抗氧化性能。涂层内部元素均质化程度高,Al元素扩散速率慢。同时,扩散区宽度较小,二次反应区不明显。     

化学气相渗透法制备碳化硅界面涂层的沉积动力学研究

目的 研究沉积温度对SiC界面涂层微观形貌、结构和成分的影响,探讨SiC界面涂层的沉积动力学和沉积机理.方法 采用Factsage软件计算MTS-H2反应物体系热力学平衡后产物组成,采用化学气相渗透法(CVI)在碳化硅纤维上制备SiC界面涂层,采用SEM、TEM、XRD等分析测试技术对SiC涂层形貌、结构和成分进行分析.结果 在860～1060℃温度范围内,MTS-H2体系平衡后的主要产物有SiC、C等,并在该温度范围采用CVI工艺制备出了SiC界面涂层.结论 在860～1060℃温度范围内,提高沉积温度有利于增加SiC的产率.温度低于960℃时,制备的SiC界面涂层表面光滑;高于1060℃时,得到了表面具有团簇结构的涂层,并且随着沉积温度的升高,涂层的结晶度提高.沉积动力学计算结果表明,温度低于1060℃时,SiC的沉积过程受表面反应控制;温度高于1060℃时,沉积过程受扩散控制.采用CVI工艺制备出了单一立方相的SiC界面涂层,并且(111)晶面为SiC颗粒的优先生长晶面.     

化学气相渗透法制备碳化硅界面涂层的沉积动力学研究

目的研究沉积温度对SiC界面涂层微观形貌、结构和成分的影响,探讨SiC界面涂层的沉积动力学和沉积机理。方法采用Factsage软件计算MTS-H_2反应物体系热力学平衡后产物组成,采用化学气相渗透法(CVI)在碳化硅纤维上制备SiC界面涂层,采用SEM、TEM、XRD等分析测试技术对SiC涂层形貌、结构和成分进行分析。结果在860~1060℃温度范围内,MTS-H_2体系平衡后的主要产物有SiC、C等,并在该温度范围采用CVI工艺制备出了SiC界面涂层。结论在860~1060℃温度范围内,提高沉积温度有利于增加SiC的产率。温度低于960℃时,制备的SiC界面涂层表面光滑;高于1060℃时,得到了表面具有团簇结构的涂层,并且随着沉积温度的升高,涂层的结晶度提高。沉积动力学计算结果表明,温度低于1060℃时,SiC的沉积过程受表面反应控制;温度高于1060℃时,沉积过程受扩散控制。采用CVI工艺制备出了单一立方相的SiC界面涂层,并且(111)晶面为SiC颗粒的优先生长晶面。     

Al2O3/Ni-P-SiC复合涂层组织与性能的研究

目的 采用化学复合镀技术对微弧氧化进行封孔,进而得到抗烧蚀性能优良的Al2O3/Ni-P-SiC复合涂层。方法 通过采用扫描电镜(SEM)、光学金相显微镜(OM)、显微硬度仪(Microhardness Tester)、X射线衍射仪(XRD)、氧–乙炔烧蚀试验(Oxy-Acetylene Ablation Test)等方法,对复合涂层的表面形貌、截面形貌、厚度、显微硬度、物相和抗烧蚀性能等进行分析。结果 陶瓷层原始表面完全被化学镀层覆盖,所制得的复合涂层厚度均匀,化学镀层与陶瓷层紧密嵌合。镀液中的SiC浓度对镀覆的速度、镀层中SiC粒子的共沉积量有着较大的影响。当粒子质量浓度为16~20 g/L时,颗粒的共沉积量较大。化学复合镀60 min可以得到厚度20 μm左右的Ni-P-SiC镀层,SiC颗粒分布均匀。当镀液中SiC质量浓度为16 g/L时,镀层具有最高的硬度。对比未处理、仅微弧氧化和Al2O3/Ni-P-SiC复合涂层试样,Al2O3/Ni-P-SiC复合涂层试样具有最佳的抗烧蚀性能。结论 Al2O3/Ni-P-SiC复合涂层均匀、致密,具有良好的抗烧蚀。     

Cf/SiC 复合材料表面 HfO2涂层的制备及其抗热冲击性能研究

目的研究等离子喷涂条件下Cf/SiC复合材料表面HfO_2涂层的物相、显微组织及其抗热冲击性能。方法通过水热合成和喷雾造粒制备出HfO_2粉体,并利用等离子喷涂在Cf/SiC复合材料表面制备HfO_2涂层,研究涂层的物相、显微组织和抗热冲击性能。结果水热合成的纳米HfO_2为单斜相结构,颗粒的平均粒径为10~15nm;等离子喷涂制备的HfO_2涂层组织中存在微裂纹和孔隙,涂层为单斜相结构,且经1350℃热处理后涂层的相结构未发生改变。等离子喷涂的HfO_2涂层与Cf/SiC复合材料基体结合良好,未观察到涂层、基体间界面分离的现象。经1350℃、50周次的空冷热冲击试验后,涂层未发生破坏失效;在1350℃水冷热冲击条件下,热循环20次时涂层表面出现剥落,27次时脱落面积50%。结论通过等离子喷涂制备的HfO_2涂层与Cf/SiC复合材料基体结合良好,涂层能够抵御1350℃空冷、50周次热冲击,且未发生破坏失效,涂层的1350℃水冷热循环寿命达27次。     

30CrMnSiA钢有机涂层电化学研究

目的研究30Cr Mn Si A钢零部件表面在只涂有1层H06-076底漆状态下的抗腐蚀能力。方法在试验过程中采用加速环境谱,利用电化学阻抗谱(EIS)方法研究30Cr Mn Si A钢试样表面在只涂有1层H06-076底漆状态下的腐蚀情况。结果涂有1层H06-076底漆的30Cr Mn Si A试样只经历了1个周期的加速环境谱就发生了腐蚀。电化学阻抗谱(EIS)方法测得的涂层失效与宏观观察到的基体金属腐蚀吻合较好。电化学阻抗谱(EIS)方法测得的10 Hz处相位角的变化规律与0.1Hz处阻抗模值的变化规律一致。结论 30Cr Mn Si A在只涂1层H06-076底漆的情况下其抗腐蚀性能很差,在外场大气环境中使用极易发生腐蚀。利用电化学阻抗谱(EIS)方法可有效表征有机涂层涂覆下的金属腐蚀行为并评估涂层的保护性能。     

发动机黏接界面损伤破坏过程细观数值仿真

目的 揭示拉伸加载下发动机黏接界面的损伤破坏规律,以及典型参数对该损伤破坏过程的影响规律。方法 以建立的含预制宏观裂纹的硝酸酯增塑聚醚（NEPE）推进剂装药的黏接界面结构的细观有限元模型为基础,开展发生推进剂内聚损伤破坏、推进剂/衬层黏接界面损伤破坏和混合型损伤破坏的数值仿真计算,讨论不同损伤破坏形式下的裂纹扩展规律,以及推进剂基体强度、颗粒/基体黏接界面模量和强度、推进剂/衬层黏接界面模量和强度对损伤位置和损伤程度等的影响规律。结果 颗粒/基体黏接界面的“脱湿”是发生推进剂内聚损伤破坏时的主要损伤形式,损伤临界应变阈值约为30%。推进剂/衬层黏接界面损伤破坏时,裂纹扩展路径与预制裂纹方向一致。混合型损伤破坏包括颗粒/基体黏接界面“脱湿”、推进剂/衬层黏接界面脱黏和推进剂基体撕裂,裂纹在推进剂/衬层黏接界面发生扩展的临界应变阈值约为20%,颗粒/基体黏接界面发生“脱湿”损伤及裂纹扩展的临界应变阈值约为60%。推进剂基体强度、颗粒/基体黏接界面强度和推进剂/衬层黏接界面强度对装药黏接界面结构损伤破坏的影响更为显著,前2个参数的增大均能导致发生“脱湿”损伤的位置向推进剂/衬层黏接界面移动,...     

界面层对纤维增韧陶瓷基复合材料力学性能影响的研究进展

以短切碳纤维增韧陶瓷基复合材料、连续碳纤维增韧陶瓷基复合材料、碳化硅纤维增韧陶瓷基复合材料为对象,综述了近年来关于界面层对FTCMCs破坏模式影响的实验研究工作。从微观力学模型建立、多尺度损伤分析两方面总结归纳了考虑界面层的FTCMCs力学性能模拟分析方法,提出建立切合实际的物理模型以及开发更先进的多尺度分析方法,是解决复杂服役环境下FTCMCs性能表征难题的有效途径。通过多场耦合多尺度建模分析方法来表征和优化FTCMCs的复杂服役环境下性能,系统揭示界面层等微观结构与宏观复合材料性能的对应关系,进而指导工艺设计,均是未来纤维增韧陶瓷基复合材料界面层的重点研究方向。     

低压等离子喷涂制备ZrB2-TiC复合涂层 及其烧蚀性能研究

目的探索低压等离子喷涂制备ZrB_2-TiC复合涂层工艺及其烧蚀性能。方法采用喷雾造粒技术制备适用于低压等离子喷涂的ZrB_2-TiC球形粉体,再采用低压等离子喷涂技术在高强石墨基体表面制备ZrB_2-TiC复合涂层。利用氧-乙炔火焰考核涂层的抗烧蚀性能,采用红外测温仪测试烧蚀过程中涂层的表面温度,分别采用扫描电镜、EDS及XRD分析涂层的表截面形貌、元素及物相。结果 ZrB_2-TiC复合涂层呈等离子喷涂层状结构特征,内部孔隙率达到10.8%,涂层与高强石墨之间的结合强度约5.4 MPa。喷涂后涂层产生了ZrTiB4、ZrTiC2新相。涂层经过2000℃氧乙炔烧蚀5min后,保持完整,未出现裂纹及剥落,烧蚀深度仅为2～5μm。结论采用低压等离子喷涂可在石墨表面制备性能优良的ZrB_2-TiC复合涂层,涂层可有效抵御氧乙炔火焰的烧蚀。     

C/C-SiC-ZrB2复合材料表面SiC/ZrB2-SiC/SiC涂层的制备及抗氧化烧蚀性能研究

目的研究C/C-SiC-ZrB_2复合材料表面SiC/ZrB_2-SiC/SiC涂层的制备、抗氧化烧蚀性能与机理。方法选择ZrB_2和SiC改性的C/C复合材料为基体,通过包埋-刷涂法在C/C-SiC-ZrB_2复合材料表面制备了SiC/ZrB_2-SiC/SiC多重抗氧化涂层,并对复合材料的微结构、抗氧化烧蚀性能与机理进行分析和研究。结果制备了一种三层结构的SiC/ZrB_2-SiC/SiC超高温陶瓷复合涂层,获得了风洞考核试验下的复合材料微结构变化、线烧蚀率等试验数据,并得到了C/C-SiC-ZrB_2复合材料的氧化烧蚀机理。结论 SiC/ZrB_2-SiC/SiC涂层对C/C-SiC-ZrB_2复合材料的抗氧化和耐烧蚀性能具有明显提升,有效提高了C/C-SiC-ZrB_2复合材料的综合热防护性能。     

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.     

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.     

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.     

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.     

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.     

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.     

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.