X射线光电子能谱在HTPB推进剂老化机理研究中的应用

采用X射线光电子能谱（XPS）法研究了HTPB推进剂在80℃热空气烘箱内分别老化0周、13周和24周的元素组成、化学价态及含量变化。通过拟合C,O,N,Cl等元素的XPS谱图,推测该推进剂在常温（25℃）贮存老化初期应是氧化交联,后期则出现降解断链,并认为NH4ClO4缓慢分解,攻击C C不饱和双键,使得C C双键含量降低是HTPB推进剂老化失效的主要原因。Al粉被包裹在推进剂粘合剂内部,XPS法未能检出Al粉。由于Al粉比较稳定,不参与推进剂老化过程,故XPS仍可用于HTPB推进剂老化机理研究。     

温度循环-应变作用下聚醚推进剂老化机理研究

目的 掌握聚醚推进剂在温度循环与应变耦合作用下的老化机理.方法 开展65～75℃温度循环和3％预应变耦合作用下的老化试验,针对不同老化时间的聚醚推进剂,分析抗拉强度、伸长率等力学性能的变化规律,以及表面微观损伤、分子官能团、反应热等微观损伤演变情况,综合推断聚醚推进剂宏观-微观关联老化机理.结果 随着老化时间延长,最大抗拉强度波动下降,最大伸长率先增大、后减小;高氯酸铵和聚醚粘合剂的分解峰温均向低温方向移动,位于1410 cm?1的高氯酸铵吸收峰增强,而位于1565、1725 cm?1的聚醚粘合剂中氨基甲酸酯、酰胺基团吸收峰下降;嵌在聚醚粘合剂内部的高氯酸铵逐渐暴露,且部分高氯酸铵颗粒与周围界面明显分离,并出现小孔洞.结论 在长期温度循环和预应变作用下,聚醚推进剂分子主链中酰胺基团的C—N键由于分子间结合力较弱而分解断链,破坏了分子主链网状交联结构,使得分散其中的AP粒子逐渐露出表面,并呈现部分断裂损伤特征,引起抗拉强度下降.     

固体推进剂老化过程影响因素及化学反应机理研究进展

基于固体推进剂的贮存老化,以NEPE推进剂和以HTPB推进剂为代表,综述了近年来固体推进剂老化进程中所受的各种影响因素、作用机制及化学反应机理研究进展。总结了温湿度、应力和环境气氛为代表的外部环境因素,配方性质、组分变化和添加剂等内部影响因素对推进剂老化及贮存失效期限的影响。分别从微观和宏观角度出发,分析了内外部各种影响因素加速或减缓固体推进剂老化进程的作用机制。此外,针对黏合剂、氧化剂、防老剂等化学组分,总结了固体推进剂贮存老化期间发生的氧化交联、分解、降解断链等主要化学反应,并分析了各个反应发生的机理及原因。最后,展望了未来固体推进剂老化影响因素研究的发展趋势,并为今后固体推进剂老化机理及失效模式研究提供了研究思路。     

拉伸加载下老化复合固体推进剂的损伤演化定量分析

目的 定量分析老化对拉伸加载下复合固体推进剂细观损伤演化的影响规律。方法 开展不同老化时间（0、32、74、98 d）下三组元端羟基聚丁二烯（HTPB）复合固体推进剂的热加速老化试验,以及老化后推进剂的微型哑铃形试验件在不同拉伸应变水平（0、5%、10%、20%、40%、50%）下的微CT扫描观测试验,并对扫描重构图像进行定量分析,获得老化对推进剂细观损伤演化的影响规律。结果 随拉伸应变增加,老化前后推进剂微CT图像的灰度均方差、平均孔隙率和图像的分形维数均呈非线性增加趋势,图像的灰度均值呈非线性减小趋势。在较低应变水平（<10%）下,上述参数受老化时间的影响不显著,但随拉伸应变增加（≥10%）和老化时间增长,灰度均方差、平均孔隙率、孔隙率增量和分形维数的数值整体增高,而灰度均值随老化时间的增长而降低,且不同老化时间下,分形维数与平均孔隙率之间存在正线性关系。结论 重构得到微CT图像的灰度均值、平均孔隙率和分形维数可作为表征参数,用于定量分析老化复合固体推进剂在拉伸载荷下的细观损伤和损伤的动态演化规律,推进剂的初始损伤和小应变下的损伤程度受老化的影响较弱,而老化时间对推进剂细观损...     

贮存老化条件下固体火箭发动机内弹道性能变化

研究了某型固体火箭发动机在贮存期间内弹道性能受推进剂药柱老化影响的变化规律。通过热加速老化试验．研究了HTPB推进荆的燃烧速度受老化影响情况：基于药柱材料的粘弹性本构关系,并考虑贮存环境温度波动、内压载荷和自重效应。对复合固体推进剂药柱完全固化后贮存老化条件下的变形进行了三维有限元分析。基于加速老化试验数据和数值仿真分析结果．对老化后固体火箭发动机的内弹道性能进行了分析。     

白炭黑补强氟硅橡胶热空气老化机理研究

目的研究热空气老化过程中白炭黑补强氟硅橡胶的老化机理。方法开展不同加速老化温度点下白炭黑补强氟硅橡胶热空气老化试验,对老化过程中材料的力学性能进行研究,同时采用热重分析、衰减全反射红外光谱、交联密度分析以及固体核磁等技术,对200℃热空气老化过程中材料的微观结构变化进行分析。结果低温环境中白炭黑氟硅橡胶拉伸强度和扯断伸长率变化较小,高温环境中变化趋势增大,邵尔A硬度在整个老化过程中没有明显变化。结论白炭黑补强氟硅橡胶的老化机理主要是交联键的断裂和侧链三氟丙基的分解,同时还可能伴随有部分主链的破坏。     

复合固体推进剂定应变‒温度循环加速试验方法研究

目的 建立复合固体定应变–温度循环加速试验方法。方法 采用MSC.PATRAN有限元分析软件,仿真计算某型贴壁浇铸固体火箭发动机从零应力温度(68 ℃)固化降温至常温(20 ℃)的极值点von Mises应变最大值,利用自制应变加载装置对复合固体推进剂施加定应变。分析固体火箭发动机长期库房贮存的温度变化规律,在兼顾模拟性和加速性的基础上,设计并开展复合固体推进剂在4组不同应力水平下的温度循环加速试验。选用合适的性能退化模型和加速寿命模型,评估复合固体推进剂的可靠库房贮存寿命。结果 某型固体火箭发动机从零应力温度固化降温至常温的极值点von Mises应变最大值为9.4%,复合固体推进剂4组温度循环加速试验的最高试验温度分别为75、75、60、60 ℃,温差分别为5、10、15 ℃,单个循环时长均为24 h。复合固体推进剂在4组温度循环加速试验条件下的老化性能参数均为最大抗拉强度保留率,且在置信度为0.9时,其退化规律均符合指数型性能老化数学模型。结合失效临界值,计算出置信度0.9时的最低加速寿命分别为59、100、203、342 d。基于修正Coffin-Manson模型,利用多元回归分析方法,计算得到复合固体推进剂在长期库房贮存环境(最高温度298 K,年平均温差15 K)下,置信度0.9时的最低贮存寿命为20 a。结论 在兼顾模拟性和加速性的基础上,建立了复合固体推进剂定应变?温度循环加速试验方法,并利用指数型性能退化模型和修正Coffin-Manson加速寿命模型,快速获得复合固体推进剂的最低库房贮存寿命,为下一步开展固体火箭发动机装药贮存寿命预估奠定基础。     

钝感推进剂用粘合剂的共聚改性研究进展

主要从线性共聚和星形共聚2方面综述了对现有聚醚类粘合剂共聚改性以及合成新型粘合剂的研究进展。探讨了共聚作用特别是嵌段共聚通过调节分子链的序列结构来改善聚合物性能的有效方法,以及星形共聚物特殊的超支化分子结构对聚合物性能的影响。希望能为兼具高能量与低感度固体推进剂用粘合剂的设计开发提供新思路和技术支撑。     

ABS湿热海洋大气环境室内外老化行为及相关性研究

目的 研究丙烯腈(Acrylonitrile)、丁二烯(Butadiene)、苯乙烯(Styrene)3种单体的三元共聚物(Acrylonitrile-Butadiene-Styrene,ABS)在湿热海洋大气环境室内外的老化行为及其相关性。方法 开展湿热海洋大气暴露(室外)试验及多因子循环加速老化(室内)试验,通过观测外观形貌、力学、化学结构等性能变化,定性探究ABS室内外老化规律。通过灰色关联度与主成分分析,定量探索ABS室内外老化行为的相关性。结果 ABS黄色指数等与表面性能相关的指标在户外暴露6个月及室内加速老化300 h左右就基本达到饱和值50和45,而与整体性能相关的拉伸强度在老化过程中先下降、后上升,断裂伸长率、冲击强度、缺口冲击强度等指标在户外暴露2个月或室内老化200 h快速下降近60%后,再缓慢降低。分子链中丁二烯单体的双键或苯环侧链中的季碳受到环境中光、氧、水等的作用,分解生成酮与羟基。通过主成分分析,将ABS多种性能指标组合成综合老化指标,客观定量评价ABS室内外老化灰色关联度高达0.93。结论ABS老化是分子链断链及交联的动态竞争过程,湿热海洋大气环境室内外老化行为的相关性较高。     

氧化絮凝复合床水处理技术的应用

由主电极和粒子电极构成的氧化絮凝复合床内 ,在一定的操作条件下便会产生一定数量的、具有极强氧化性能的羟基自由基和新生态的混凝剂 ,与废水中的污染物发生诸如催化氧化分解、混凝和吸附等作用 ,使之迅速被去除。     

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.     

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.