聚合反应时间对聚酰亚胺基碳膜结构和性能的影响研究

目的 系统研究前驱体聚合反应时间对PI膜及其碳化、石墨化后薄膜结构和性能的影响规律。方法 通过调整聚合合成聚酰胺酸（PAA）溶液过程中的反应时间,制备石墨膜前驱体聚酰亚胺（PI）原膜,将不同工艺条件下制得的PI膜进行碳化、石墨化处理,得到高导热率石墨膜。利用扫描电镜、红外光谱、拉曼光谱仪和LFA激光闪射仪对制备的PI膜、碳化膜及石墨膜的微观结构和热导率进行检测。结果 随聚合反应时间的延长,PI膜酰亚胺化程度和石墨膜的石墨化程度及导热性能先增高、后降低。反应时间为3 h时,制得的石墨膜结构致密,石墨片层取向性好,导热性能最好,热导率可达765.2W/(m·K)。结论 PI膜前驱体聚合反应时间显著影响PI膜酰亚胺化的程度和有序度,进而影响石墨膜的定向性和导热性能。     

聚酰亚胺基石墨膜材料研究进展

综述了聚酰亚胺基石墨膜材料的研究进展,简述了聚酰亚胺薄膜的分类、合成方法及其应用,详细介绍了聚酰亚胺制备石墨膜的方法,碳化和石墨化过程中涉及的分子结构和其形貌以及性能的变化过程。阐述了制备石墨膜过程中的机理,进而分析了影响聚酰亚胺基石墨膜性能的因素,主要包括了化学结构、烧结工艺以及复合薄膜中掺杂组分对结构和性能的影响。其后,通过近年来国内外的专利情况,分析了石墨膜材料的应用方向,总结并展望了未来聚酰亚胺基石墨膜材料的发展方向。     

TiO2薄膜光催化剂的制备及其活性

用活化反应蒸发技术制备了不同附载条件的TiO2薄膜光催化剂，膜厚度在0．5μm－1.2μm之间，经400℃退火后用XRD测定其晶型结构，发现无定型TiO2已部分转变为锐钛矿型。薄膜光催化剂连续使用两次活性会下降，用HCl冲洗活性即可恢复。考察了不同波长的电光源和不同辐射强度的太阳光下两种催化剂薄膜的活性比较，结果发现短波长电光源下（254nm）膜厚度以0．5μm最佳，而强烈辐射的太阳光下膜厚度以1.2μm最佳。     

空间粒子辐射环境下石墨膜力学性能的演变规律

目的将石墨膜置于9×10^5~9×10^7 rad(Si)总剂量下获得辐射改性石墨膜材料,探讨空间粒子辐射作用下石墨膜拉伸强度的演变规律。方法采用SEM、XRD、煅烧分析及XPS等手段分析石墨膜的结构及成分。结果石墨膜为有序堆积的层状结构,层间距为0.3355 nm,碳的质量分数高达99.75%,挥发分的质量分数为0.04%,灰分的质量分数为0.21%,XPS只检测到C1s及O1s峰。石墨膜的平均热膨胀系数为负值,且其峰值仅为-1.33×10^-6/℃,具备出色的结构稳定性。空间粒子辐射环境模拟试验表明,随着辐射剂量的升高,石墨膜的拉伸强度逐渐衰减,在更高剂量辐射下,石墨膜的拉伸强度趋向稳定。通过Raman光谱仪对辐射石墨膜结构的分析,揭示了力学性能的演变机理。结论辐射石墨膜的拉伸强度与其缺陷含量有很大的相关性,未经过辐射的原始石墨膜的缺陷含量最低,其拉伸强度最大,随着石墨膜的缺陷含量逐渐增多,其拉伸强度逐渐降低。     

C/C复合材料不同碳基体的纳米压痕行为研究

目的研究碳基体微观结构对材料整体性能的影响。方法用酚醛浸渍-碳化、中温煤沥青浸渍-碳化、甲烷为碳源前驱体,经化学气相沉积制备得到不同碳基体C/C复合材料。采用偏光显微镜对C/C复合材料不同碳基体的显微结构进行观察分析,采用XRD和Raman光谱对C/C复合材料的树脂碳基体、沥青碳基体和热解碳基体的微晶尺寸进行表征,以玻璃碳作为参比样品,通过纳米压痕测试不同碳基体试样的弹性模量和硬度。结果碳基体为热解碳和沥青碳的石墨微晶缺陷少,完整度较好,石墨化程度高。玻璃碳和树脂碳基体中石墨微晶排列紊乱,有序度低,石墨化程度低。酚醛浸渍-碳化得到的树脂碳的微晶尺寸Lc最小,为1.69 nm,弹性模量和硬度最大,分别为(23.17±0.54) GPa和(3.26±0.10) GPa;光滑层热解碳和粗糙层热解碳的弹性模量和硬度次之;沥青碳的微晶尺寸最大,Lc为9.36nm,而弹性模量和硬度最小,分别为(12.53±2.29) GPa和(0.72±0.14) GPa。结论不同碳基体的C/C复合材料中,碳基体的石墨化度越高,微晶尺寸越大,各向异性越显著,材料的弹性模量和硬度越低。     

多层沉积SiC涂层与石墨基体的界面表征

目的制备并表征在柔性石墨纸基体上化学气相沉积(CVD)的多层SiC涂层,及其界面结构、界面处的元素分布等。方法以柔性石墨纸为基体、甲基三氯硅烷(MTS)为硅源、H2为载气和还原剂、Ar为稀释气,在1030～1070℃温度区间通过真空感应高温炉在石墨基体上分5次制备了多层SiC涂层。通过SEM和EDS表征并分析该涂层的表面结构和切面结构,以及涂层与基体界面处的元素分布。结果在石墨基体上有效制得了多层SiC涂层,获得的SiC涂层具有明显的两级颗粒结构。经EDS分析确认,在不同沉积层,C与Si的比例的不同。结论实验证实SiC与基体石墨具有良好化学相容性。SiC涂层表面表观致密,纳米尺度堆积颗粒表观致密,但在微米尺度的堆积颗粒间存在空隙。多层涂层间具有1～3μm的不致密SiC间隙。涂层一侧距界面10μm处的元素分布显示,Si和C元素化学计量比趋近于1︰1,可以认为是涂层的过渡层。     

基于高通量测序解析碳化温度对麻秆电极微生物群落影响

采用Solixa高通量测序技术比较了1 000℃和1 800℃碳化麻秆制备电极OCP-1000和OCP-1800在生物电化学系统运行过程中形成的生物膜微生物群落结构差异.测序分别获得OCP-1000和OCP-1800附着生物膜16S rRNA基因V3区优化序列4 231和5 263条,经过97%相似度归并后获得OTUs数量分别为1 187和1 338个.α多样性指数(Chao、Shannon指数)分析表明碳化温度越低,电极生物膜微生物多样性越丰富.电极OCP-1000和OCP-1800生物膜中优势菌群均为Proteobacteria、Firmicutes和Bacteroidetes,这3个门的细菌在OCP-1000生物膜含量分别为66%、10%和9%,但在电极OCP-1800生物膜中含量分别为71%、7%和9%.不同碳化温度制备的麻秆电极在生物电化学系统运行过程形成的生物膜不仅存在共有细菌种类,也含有独特菌种,说明电极制备过程碳化温度影响电极生物膜微生物群落结构.     

硝基清漆膜厚度对硝基清漆VOCs释放的影响

利用自制的小型环境测试舱,研究了硝基清漆膜厚度对挥发性有机物(VOCs)释放的影响.漆膜厚度分别为296,508,715,799,960μm,测试条件为:温度为25.0℃,相对湿度为23.9%,空气流量为0.75m3/h,空气流速为3.4cm/s,支持板为不锈钢盘.采用真空采样罐采集舱出口空气,用气相色谱(GC-FID)分析测试.确定了5种主要VOCs(甲基环乙烷、甲苯、乙苯、间/对二甲苯和邻二甲苯)的浓度,并以一阶衰减模型对浓度进行模拟计算得到释放速率.结果表明,漆膜厚度并不影响VOCs的峰值浓度和初始释放速率,但漆膜越厚,VOCs的浓度衰减越慢,衰减速率越小.     

载Pt石墨催化臭氧化降解水中草酸的研究

以石墨为催化剂载体,以H₂PtCl₆·6H₂O为贵金属活性组分前驱物,采用等体积浸渍法制备了Pt/石墨催化剂.对Pt/石墨催化臭氧化、石墨催化臭氧化以及单独臭氧氧化降解草酸的效果进行了研究.结果表明,在本实验条件下,单独臭氧氧化、石墨催化臭氧化和Pt/石墨催化臭氧化草酸的去除率分别为3.0%、47.6%和99.3%.Pt的负载可以显著地提高石墨催化臭氧化的效果.以草酸的去除效率为催化活性指标对Pt/石墨催化剂的制备条件进行了优化.结果表明,石墨载体的预处理没有提高Pt/石墨催化剂的活性.Pt/石墨催化剂最佳制备条件为：以水为溶剂,浸渍时间24　h,活性组分Pt的负载量为1.0%,氢还原温度为350℃.所制备催化剂经重复使用5次,草酸去除率仍超过90％.     

基于数字图像相关方法的石墨高温杨氏模量测试

目的为了得到石墨在高温环境下的杨氏模量,为飞行器热防护系统和高温热结构的设计提供可靠的技术保障。方法基于数字图像相关(DIC)方法和通电电阻加热技术,建立一套测量材料在高温环境下力学性能的测试系统。利用该系统,测量高温下石墨试样的表面应变场和应力-应变曲线,计算相应温度下的杨氏模量。在1400℃实验环境下,采用基于DIC与高温引伸计的方法同时测量超高温陶瓷试件的拉伸应变数据,并进行比较验证。结果在1400℃实验环境下,采用基于DIC与高温引伸计方法测得超高温陶瓷的应变-时间曲线吻合良好,方差为1.3×10-7。1200~1900℃高温环境下,石墨的杨氏模量随温度的升高呈线性增长趋势。结论采用基于DIC方法准确有效,该方法可方便快速地实现对石墨材料在高温环境下杨氏模量的测量。另外,该方法也可应用于其他导电材料杨氏模量的测试。     

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.