一种有机硅改性丙烯酸防污涂料的研究

目的通过在丙烯酸树脂分子中引入有机硅,制备一种具有低表面能的有机硅改性丙烯酸树脂CP-CC021。方法探讨合成工艺中有机硅单体和引发剂含量以及添加纳米级Si O2粒子填料对涂层性能的影响规律。结果获得了最大接触角的最佳工艺条件,添加纳米Si O2粒子增大了涂层的表面粗糙度,在涂层表面形成了大量微-纳结构状的突起,显著提高涂层的疏水性能。结论有机硅单体(VTMS)质量分数为23.0%,引发剂(AIBN)质量分数为0.50%,纳米Si O2粒子添加量(质量分数)为7.4%,得到的涂层接触角为126.1°。     

耐高温防腐涂料的研制

采用分子量适中的环氧树脂对反应性有机硅低聚物进行共聚改性,充分利用有机硅树脂的耐高温性和环氧树脂的防腐性及高附着力。以此共聚物为成膜物,再采用合适的固化剂,添加适当的颜填料配成涂料。结果表明,在与适当的底漆配合使用下,该涂料具有优异的耐高温性及防腐蚀性能。     

环境升温过程对常温固化环氧树脂热力学性能的影响

目的提高常温固化环氧树脂体系的高温使用性能。方法采用常温固化剂T31、中温固化剂IPDA以及高温固化剂DDM作为混合固化剂,对E-44型和AG-80型混合环氧树脂体系进行常温固化反应,并分析环境升温过程对固化物热力学性能的影响。通过DMA分析、热变形测量、固化度测试,分别评价室温固化环氧树脂在环境升温过程前后的玻璃化转变温度、热变形量及体系内部的固化反应程度变化,并通过吸水率测试和弯曲强度测试对玻璃纤维布增强常温固化环氧树脂基复合材料的耐湿热性能以及高温条件下的力学性能进行分析。结果环氧树脂常温固化物的tg为85.21℃,经1.5℃/min的平均升温速率加热至90℃之后,该环境升温过程使固化物的固化度增大至92%以上,tg增长为132.06℃的同时热变形温度增大。其复合材料耐湿热性能提高,且100℃时弯曲强度的保持率为65%,对于加热至120℃的环境升温过程,固化物的固化度接近96%,tg增长为144.45℃的同时热变形温度进一步提高,其复合材料耐湿热性能改善程度更加明显,且130℃时弯曲强度保持率仍接近60%。结论常温、中温、高温混合固化剂的合理复配有助于环氧树脂体系在环境升温变化的诱导条件下发生梯度式固化反应,使体系内部的交联固化程度迅速升至较高水平,可以有效提高其玻璃化转变温度,显著改善常温固化环氧树脂体系在高温条件下的热力学性能。     

阳离子表面活性剂改性树脂润湿和除油性能研究

以十六烷基三甲基溴化铵(CTAB)对苯乙烯离子交换树脂进行改性,制备CTAB改性树脂,并用改性树脂处理含乳化油废水.采用热失重法(TG)对改性前后的树脂进行热稳定性分析,并用Washburn压差法研究了水和正己烷在改性树脂表面上的润湿压差.结果表明,经过CTAB改性的树脂颗粒(R-CTAB)比未改性树脂(R-H)吸水量少且失水更加迅速,疏水性增强,在200℃时,R-CTAB比R-H的失重低9.40%.润湿性试验表明,经过CTAB改性后树脂的水的润湿性降低,正己烷的润湿性提高,改性树脂的表面润湿性能得以改变,疏水性更突出.处理含乳化油废水的试验表明,改性后树脂对油和浊度的去除率分别高于未改性树脂6.3%和9.5%.     

改性氧化镁脱硫废渣协效阻燃环氧树脂的研究

在分析氧化镁烟气脱硫废渣(MDWR)成分的基础上,用清洁的合成方法对氧化镁烟气脱硫废渣进行了改性,制备了含有类水滑石(HTLcs)的改性废渣(MMDWR),用电感耦合等离子体(ICP)、元素分析(SEM-EDAX)、X射线衍射(XRD)、红外(FTIR)、激光粒度测试仪(LLD)和BET测比表面等方法进行了表征.当m(MDWR)∶m(NaOH)∶m(Na2CO3)∶m(Al(OH)3)为40∶15:4:4时,制备的改性废渣的元素组成类似Mg-A1水滑石.合成滤液可完全回用.废渣经改性后粒径减小,粒径分布变窄,比表面积增大.将改性废渣用于协效阻燃环氧树脂,用热分析、氧指数测定等方法对改性废渣的阻燃、抑烟性能进行了评价.当膨胀型阻燃剂和改性废渣添加量分别为17％和3％时,环氧树脂的氧指数可达到30％.当废渣添加量为20％时,对环氧树脂具有良好的抑烟性能.改性废渣具有阻燃抑烟等综合性能,成本低,具有良好的应用前景.     

APP@MOFs核-壳结构型阻燃剂制备及其在环氧树脂中的应用研究北大核心CSCD

采用微胶囊改性技术,以高效阻燃剂聚磷酸铵(APP)为内核、多功能金属有机框架材料(ZIF-8)为外壳,合成了新型核-壳结构型阻燃剂(APP@ZIF-8),并将其用于环氧树脂(EP)中制备阻燃复合材料,通过一系列测试分析来表征APP@ZIF-8的结构特征、评估其耐水性能,并采用锥形量热仪法研究了EP复合材料的阻燃、抑烟减毒性能。结果表明：经ZIF-8的包裹实现了APP溶解度降低、耐水性能显著提升;掺入10 wt%的APP@ZIF-8后,EP复合材料的热释放速率峰值(pHRR)、烟气释放速率峰值(pSPR)和CO释放速率峰值(pCOP)较纯EP分别降低了61.3%、43.6%和60.5%,使EP复合材料的阻燃性能和抑烟减毒性能均得到提升,这主要得益于APP@ZIF-8在燃烧过程中促进了致密炭层的形成(残余炭量较纯EP提高了367.1%),抑制了可燃产物和毒性烟气的扩散,此项工作为环氧树脂的阻燃改性提供了一种新思路。     

底盘发动机排烟管高温涂料耐腐蚀性能对比分析与应用

目的 针对底盘发动机排烟管在某海洋大气环境中腐蚀防护难度大的问题,对4种高温涂料进行耐腐蚀性能对比分析与应用。方法 分别采用试片高温试验、户外暴露试验和排烟管实装实地验证等方法对3种改性有机硅、1种无机硅酸盐共4种高温涂层的耐高温、耐腐蚀性能及应用效果进行测试与分析。结果 高温涂层试片的高温试验、户外暴露试验结果表明,3种改性有机硅涂层600 ℃的耐高温性能、耐腐蚀性能优于无机硅酸盐涂层,但试片经600 ℃高温烧蚀后进行户外暴露试验的结果表明,石墨掺杂有机硅涂层耐蚀性优于其余3种涂层,无机硅酸盐涂层优于氟树脂改性有机硅、环氧改性有机硅涂层。排烟管实装实地验证试验则表明,石墨掺杂有机硅涂料受到高温氧化、降水冷却、常温腐蚀等频繁交替作用下,腐蚀较快,氟树脂改性有机硅涂层的防护性较好,环氧改性有机硅涂层在高温区域腐蚀明显,无机硅酸盐涂层中锌粉和铸铁基体存在明显腐蚀。结论 相对于传统的银粉漆,4种高温涂层显著改善了排烟管的腐蚀防护性能。在上述4种试验条件下,4种高温涂层的耐高温、耐腐蚀等性能各有优劣,需要根据4种涂层各自的性能不足进行改进。在实际工况条件下,氟树脂改性有机硅耐涂层满足发动机排烟管在某海洋大气环境中不低于1 a免维护的使用要求,其他2种有机硅涂层、1种无机硅酸盐涂层则需要一定程度维护。     

改性壳聚糖吸附剂的合成及对镉离子的吸附性能

通过丁二酸酐、可分散的纳米二氧化硅(简称DNS)和壳聚糖经过系列反应得到改性壳聚糖。通过FTIR光谱、热重分析和SEM研究了改性壳聚糖的性能。FTIR表明壳聚糖与DNS通过丁二酸酐桥连为一个高分子聚合物;扫描电镜分析结果显示,改性壳聚糖呈现近似球状,形成了一些孔和缝隙分布于微粒的表面及内部;热重分析结果表明,改性壳聚糖的热性能有较大提高。研究了改性壳聚糖微粒吸附Cd2+时pH值、时间、用量对吸附的影响,结果表明其吸附最佳条件为:pH=5,吸附时间为2 h,吸附剂的投加量为0.1 g。改性壳聚糖具有较强的吸附Cd2+的能力,其吸附量最高可达3.789 8 mmol/g,吸附率最高可达79.12%。     

高性能聚醚醚酮紫外光加速老化行为研究

目的 研究特种工程塑料聚醚醚酮(PEEK)在紫外光照射实验室加速条件下的老化行为。方法 对PEEK塑料采取紫外线光老化方式进行试验,对老化前后的样品进行外观变化、力学性能、热性能、微观结构表征与分析,明确紫外环境因素对材料的性能影响,进而确定PEEK塑料在紫外光条件下的老化行为。结果 随着紫外光老化时间的增加,PEEK样品表面变黄,颜色加深,出现鼓包与裂纹等宏观与微观损伤。样品内部力学性能、热性能、红外特征吸收峰、元素含量与价态没有明显变化,样品表面热性能下降,傅里叶变换衰减全反射红外光谱(ATR-FTIR)特征吸收峰变化明显。结论 PEEK塑料表面对紫外光比较敏感,在紫外光的照射下容易发生表层的分解,短时间内不会引起材料整体热性能及力学性能的明显变化。     

基于纳米TiO2添加的新型航空涂料性能研究

目的解决纳米TiO_2在涂料中的团聚问题,同时实现增强涂层防腐蚀、疏水性能和耐紫外老化性能。方法以氯醚树脂为航空涂料的主要成膜物质,以经氟硅烷改性后的金红石型纳米TiO_2颗粒为主要吸光剂和疏水剂,配合其他合适填料和颜料制备一种新型航空涂料,通过拉拔法、硬度测试法、电化学极化曲线法、接触角测试法和人工紫外加速老化等测试手段分别对涂层的力学性能、电化学性能、疏水性能和耐紫外老化性能进行研究。结果改性后的金红石型纳米TiO_2颗粒的分散性及与氯醚树脂的相容性得到改善。当添加量为2%~3%时,涂层腐蚀防护性能、表面疏水性、耐紫外老化性能达到最佳,附着力、硬度等力学性能达到航空涂料的基本使用要求。结论该涂料有效地解决了纳米TiO_2在涂料中的团聚问题,提高了涂层的防腐蚀、疏水性能和耐紫外老化性能。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

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.     

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.