环境温度对复合固体推进剂贮存老化微观损伤作用机制研究

目的研究复合固体推进剂在环境温度作用下的微观损伤机制。方法开展复合固体推进剂实验室高温加速老化试验,分析不同损伤程度下的化学官能团和损耗因子的变化规律,综合推断环境温度作用下的微观损伤机制。结果复合固体推进剂在环境温度作用下,氧化剂AP一直不断地分解释放出活性成分,攻击HTPB粘合剂主链,使粘合剂主链初期主要发生交联反应,生成多种氧化产物如过氧化物、醛基、酯基。在老化后期,粘合剂主链开始断链,断链位置应该为R—CO—NH或C=C处,使得R—CO—NH、C=C含量随着老化时间的增加而逐渐降低。结论在环境温度的作用下,复合固体推进剂同时发生氧化交联和分解断链两种反应,但老化初期氧化交联占主导,老化后期主要发生分解断链。     

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。     

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。     

某推进剂低温加速老化试验研究

目的考查某推进剂在-10℃和-28℃这两个温度下性能随老化时间的变化趋势。方法采用低温加速老化试验。结果在低温下老化推进剂最大抗拉强度先下降然后逐渐升高,伸长率变化趋势较为复杂。常温正常拉伸速度条件下伸长率基本在初始值附近波动,低温快速拉伸条件下伸长率直线下降。结论低温下推进剂老化力学性能的变化趋势与高温老化不尽相同,造成这种差异的原因可能是老化机理不同所致。     

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。     

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。     

基于状态监测和老化试验的火箭发动机寿命评估方法研究

通过分析某型固体火箭发动机的结构,对发动机状态监测系统的微型传感器进行了合理布局,从而得到危险区域的最大应变值。采用加速老化试验,得到推进剂在不同老化温度下延伸率随老化时间的变化曲线。通过化学反应速率,建立不同老化温度下力学性能参数和老化时间的关系,从而确定某贮存温度下推进剂延伸率与贮存时间的关系。将发动机危险点处最大应变与贮存时间的变化关系进行比较,得到推进剂的贮存寿命。     

PBT基推进剂热分解特性与慢烤行为关系研究

目的 研究PBT(3,3–二叠氮甲基氧丁环–四氢呋喃共聚醚)基推进剂慢速烤燃响应情况与热分解特性之间的关系。方法 采用差示量热扫描仪和慢速烤燃试验,研究推进剂在不同固含量(通过改变高氯酸铵含量来调整)和不同铝粉含量下的热分解温度变化情况,计算不同组分含量下推进剂的热分解动力学参数,对比分析PBT基推进剂固、铝粉含量变化对热分解特性及慢速烤燃行为影响。结果 固含量从78%下降至75%时,配方中AP(高氯酸铵)的高、低温热分解温度和热分解活化能均会下降。铝粉质量分数从18%下降至5%时,配方中AP的高、低温热分解温度和热分解活化能均会下降。当采用78%的固含量时,配方无法通过慢烤试验,而采用75%的固含量,铝粉质量分数为18%、5%时,均能通过慢烤试验。结论 根据热分析及慢烤试验结果可认为,固含量变化对慢烤响应程度变化有较大影响,Al粉含量变化对配方慢烤响应程度的影响较小。影响配方慢烤响应程度主要由AP高温分解控制,AP高温分解活化能越低,越有利于推进剂通过慢速烤燃测试。     

HTPB推进剂老化性能湿热影响分析

目的 掌握HTPB推进剂老化过程中,温度和湿度对其力学性能的影响及贡献程度.方法 对HTPB推进剂进行不同湿热条件下的加速老化试验,并测量不同老化时间推进剂的质量损失分数和力学性能,结合推进剂在温度和湿度下的作用机理,对质量损失分数随老化时间的变化规律进行分析,以最大拉伸强度作为性能指标,对HTPB推进剂湿热老化过程进行湿热双因素方差分析.结果 湿度对HTPB推进剂质量损失分数的影响起主导作用,在75％～85％有一个湿度拐点值,大于或小于这个拐点值,推进剂遵循不同的质量损失分数变化规律.温度和湿度对推进剂最大抗拉强度方差分析的F值均大于其临界值,影响显著.相比而言,湿度的影响更加显著,整个老化过程中,温度和湿度的影响作用表现出先增加、后下降的趋势.温湿交互作用在试验前期和后期对推进剂的影响不显著,而在试验中期较为显著,同样呈现出先增大、后减小的规律.结论 湿度对推进剂最大拉伸强度影响的贡献率最大,温度次之,交互作用最小.从时间轴上看,湿度的贡献率表现为单调递增趋势,温度为单调递减趋势,交互作用呈现抛物线趋势.     

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.     

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

ＲｅｍｏｖａｌｏｆｈｅａｖｙｍｅｔａｌｓｆｒｏｍｓｅｗａｇｅｓｌｕｄｇｅｂｙｌｏｗｃｏｓｔｉｎｇｃｈｅｍｉｃａｌｍｅｔｈｏｄａｎｄｒｅｃｙｃｌｉｎｇｉｎａｇｒｉｃｕｌｔｕｒｅＷｕＱｉｔａｎｇ，ＮｙｉｒａｎｄｅｇｅＰａｓｃａｓｉｅ，ＭｏＣｅｈｕｉＦ...     

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.     

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.     

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.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.