FOX-7在炸药中的应用述评

FOX-7是一种性能优异的不敏感单质炸药,也是今后在低易损弹药上推广应用的主要候选炸药之一。重点综述了国内外近年来报道的FOX-7在炸药中的应用及性能研究进展,包括FOX-7的合成制备、分子结构及晶型、表界面性能、热安定性能以及以FOX-7为基的炸药的机械感度、爆速、爆压、冲击波感度、小尺寸装药快速烤燃、慢速烤燃、子弹撞击试验等。其中,对FOX-7炸药不敏感性的评价方式主要是与相同状态的RDX基炸药和TNT炸药进行试验对比。指出FOX-7是一种具有应用价值的高能不敏感炸药,要实现FOX-7炸药在弹药中的应用,今后还要加强高品质、规模化、低成本FOX-7制备工艺技术研究以及FOX-7炸药在大尺寸战斗部中的装药技术研究。     

FOX-7与RDX混合比例对压装炸药慢速烤燃及冲击波感度的影响

利用慢速烤燃试验和冲击波感度试验研究了FOX-7与 RDX不同混合比例对炸药响应特性的影响。试验表明:当FOX-7的混入量（质量分数）低于72%时，炸药在慢速烤燃试验中的响应剧烈程度表现为爆轰反应，其临界起爆压力接近6.62 GPa；当FOX-7的混入量（质量分数）等于72%时，炸药在慢速烤燃试验中的响应剧烈程度由爆轰降至爆燃，其临界起爆压力升至7.27 GPa；当配方中完全采用FOX-7时，炸药在慢速烤燃试验中的响应剧烈程度由爆燃降至燃烧，临界起爆压力升至8.24 GPa。造成上述试验结果的原因可能是压装炸药在成型过程中因颗粒的破碎、重排作用使FOX-7对RDX形成包覆，进而改善了RDX材料点火增长速度快的本质特点。     

提高工艺安全性的FOX-7合成方法?

为了提高合成工艺的安全性,提出了一锅法制备1,1-二氨基-2,2-二硝基乙烯(FOX-7)的方法。控制反应体系温度在15℃左右,采用蠕动泵将浓硫酸连续地加入到2-甲基-4,6-二羟基嘧啶与二氯甲烷的悬浮液中,固体原料溶解后,再将发烟硝酸滴加到反应物料中,进行硝化反应;然后连续滴加水到反应器中,进行水解开环反应;再经过固液分离、洗涤和干燥,得到FOX-7。探讨了硝化剂的加料方式对收率和工艺安全性的影响。结果表明:惰性溶剂的引入,分散了反应物,硝化反应释放的热量可以及时扩散,物料温度控制更平稳,消除了物料团聚现象,而且与硝硫混酸加料相比,采用浓硫酸与发烟硝酸分步加料的方式,升温速率可降低51.0%,FOX-7的收率由63.0%提高到了82.6%,工艺的安全性显著提升。     

Thermal behavior, specific heat capacity and adiabatic time-to-explosion of G(FOX-7)

[H(2)NC(NH(2))(2)](+)(FOX-7)(-)-G(FOX-7) was prepared by mixing FOX-7 and guanidinium chloride solution in potassium hydroxide solution. Its thermal decomposition was studied under the non-isothermal conditions with DSC and TG/DTG methods. The apparent activation energy (E) and pre-exponential constant (A) of the two exothermic decomposition stages were obtained by Kissinger's method and Ozawa's method, respectively. The critical temperature of thermal explosion (T(b)) was obtained as 201.72 degrees C. The specific heat capacity of G(FOX-7) was determined with Micro-DSC method and theoretical calculation method and the standard molar specific heat capacity is 282.025Jmol(-1)K(-1) at 298.15K. Adiabatic time-to-explosion of G(FOX-7) was also calculated to be a certain value between 13.95 and 15.66s.     

熔盐法合成高导热磷化硼及其热管理性能研究

随着电力电子器件封装密度提高, 开发导热性能优异的热界面材料受到了广泛关注。绝大多数传统导热填料的热导率较低, 因此合成新型高导热填料是提高热界面材料导热性能的重要途径。本研究通过简单的熔盐法合成了高导热的磷化硼(BP)颗粒, 与氮化硼(h-BN)混合并通过搅拌和浇注的方法填充到环氧树脂(EP)基体中制备得到树脂基复合材料(BP-BN/EP)。实验结果表明：采用三盐法(NaCl : KCl : LiCl)合成的BP产率最高达到74%, 相对于单盐法(41%)和双盐法(39%)分别提高了33%和35%。对于BP-BN/EP复合材料, 复合材料的微结构显示BP和BN颗粒均匀分布在环氧树脂基体。当混合填料体积分数为30%时, 该复合材料的热导率达到1.81 W•m^-1•K^-1, 是纯树脂热导率(0.21 W•m^-1•K^-1)的8.6倍, 这与BP颗粒作为桥梁连接相邻BN颗粒形成导热网络有关。除此以外, 相较于不含BP的复合材料(SBN-BN/EP), BP-BN/EP复合材料展现出更加优异的热导率、热稳定性和较好的热力学性能。因此, 熔盐法合成的BP在热管理领域具有较大的应用前景。     

碱性染料与磷钨酸形成的新型电荷转移盐的制备与表征

报道了用Keggin结构的磷钨酸与碱性染料结晶紫、碱性藏红T和碱性湖兰BB反应形成的3种新型电荷转移盐。利用元素分析、差热-热重、变温红外、固体漫反射电子光谱对标题化合物的组成、热稳定性和光学性质进行了表征。     

Studies on energetic compounds part 8 : thermolysis of salts of HNO(3) and HClO(4)

The thermolysis of various substituted ammonium salts of nitric and perchloric acids has been reviewed in the present communication. The mechanistic aspects of thermal decomposition of these salts have been discussed critically. It has been observed that the proton transfer process do play a major role during thermolysis of these salts. The plausible decomposition pathways have also been described.     

YBa_2Cu_3O_(7-y)超导体合成机理

采用 TG-DTA 热分析和 X 射线衍射相结合的方法,研究了由不同原料制取单一相 YBa2-Cu_3O_(7-(?))超导体的合成反应机理。试验结果表明,YBa2Cu_3O_(7-(?))的形成经历两个反应阶段,首先形成 BaCuO_2和 Y_2Cu_2O_5,随后这两个二元复合氧化物化合形成 YBa2Cu_3O_(7-(?))。各步反应温度受钡盐种类控制,采用 Ba(NO_3)_2原料,在750℃即可表现出超导性,T_c 达86K。     

The thermal conductivity of the molten NaNO3-KNO3 eutectic between 525 and 590 K

Molten salts are one of the few remaining classes of fluids for which standardquality (±1% accuracy) data on thermal conductivity have not hitherto been available. We have therefore developed a new apparatus based on the transient hot-wire technique to obtain reference-quality measurements of the thermal conductivity of molten salts at high temperatures. Liquid metal-filled quartz capillaries served as insulated hot wires in our method, and in addition, a two-wire technique was used in order to obtain absolute values of the thermal conductivity. New data for the NaNO₃-KNO₃ eutectic between 525 and 590 K are reported in this paper and comparisons with other recent measurements are shown.     

Grain orientation studies in YBCO superconductors by molten salt synthesis

The molten salt or the flux method is utilized in this study to fabricate a grainoriented YBa₂Cu₃O_7−x superconductor. The formation of YBa₂Cu₃O_7−x in the presence of molten salts of Na, K, Li belonging to chloride and iodide systems does not appear feasible due to the instability of the superconducting phase in these salt systems. Studies using the “green phase,” Y₂BaCuO₅, as seed crystals suggest a two-stage approach in the formation of YBa₂Cu₃O_7−x . The process uses Y₂BaCuO₅ formed by molten salt synthesis which has been observed to be stable in water and against most of the salts. The 211 crystals can be mixed with oxides and converted to 123. Analysis of X-ray data and SEM micrographs indicates a certain degree of grain orientation, which can be further enhanced by tape-casting or not-forging.     

Concentration-dependent growth and morphology of doped polyaniline nanowires

Polyaniline nanowires with entangled network structures were synthesised through an electropolymerisation route using a step galvanostatic method on titanium substrate. The morphology of the synthesised polyaniline was investigated by scanning electron microscopy and transmission electron microscopy. The dependence of morphology on the concentration and duration of synthesis has also been studied. Structural characterisation has been done by UV–VIS spectroscopy and Fourier transform infrared spectroscopy. The concentration of the monomer and the duration of synthesis affect the morphology as well as the amount of nanowires deposited.     

高速撞击下温压炸药的响应敏感性

采用自行设计的动态加载装置对HMX基、HMX/NTO基和HMX/FOX-7基3种温压炸药撞击响应规律进行了研究,获得炸药的临界点火速度,并通过密闭燃烧罐分析撞击后回收试样的燃烧特性。结果表明:3种温压炸药药柱在高速撞击下均经历了冲击、塑性变形、破碎飞散和点火反应阶段;HMX基、HMX/NTO基和HMX/FOX-7基温压炸药的临界点火速度分别为302.9、312.3 m/s和315.3 m/s,NTO和FOX-7能够提高温压炸药的临界点火速度;分析撞击后回收试样的燃烧特性发现,与HMX基温压炸药相比,HMX/NTO基和HMX/FOX-7基温压炸药升压时间分别增加了103.6%和103.3%,升压速率分别降低了17.3%和21.1%,且撞击后的燃烧速率显著降低。     

A simple synthesis of amine-derivatised superparamagnetic iron oxide nanoparticles for bioapplications

Adsorption of 3-aminopropyltriethoxysilane (APTS) on magnetite nanoparticles during its formation has been investigated to optimise the preparation of stable aqueous dispersion of amine derivatised magnetite nanoparticles. APTS adsorbs chemically on the surface of magnetite particle modifying its surface which is evident from thermal and C, H, N analysis. The variation of particle size has been observed with change of APTS concentration. X-ray diffractogram shows the formation of pure inverse spinel phase magnetite with average crystallite size 7 nm when equimolar (Fe₃O₄: APTS = 1:1) quantity of APTS was used during its synthesis. The presence of free surface –NH₂ groups and Fe–O–Si bonds was observed by FTIR. Raman spectrum further confirms the presence of surface –NH₂ groups. Transmission electron microscopy shows formation of particles of average size between 7 nm and 12 nm. The effective hydrodynamic diameter of the APTS coated particle agglomerates is 45.8 nm in stable aqueous colloidal dispersion, which is evident from photon correlation spectroscopy. VSM measurements at room temperature of both silanised and unsilanised magnetite shows their superparamagnetic nature with saturation magnetisation 41 e.m.u/g and 56 e.m.u/g, respectively. Avidin has been immobilised on the surface through glutaraldehyde, which demonstrates the possibility of the synthesised material to be used in protein immobilisation to form bioactive magnetic particles.     

Al含量对热爆反应合成Al／TiC复合材料的影响

本文利用热爆反应合成法制备了Ａｌ／ＴｉＣ复合材料，研究了反应合成过程中，温度特性以及Ａｌ含量对其的影响，结果表现：在反应合成过程中的Ａｌ的熔化，然后是陶瓷相的合成反应，并且随着Ａｌ含量的增加，反应最高温度降低，而反应起始温度和反应持续时间基本不变。此外，研究了Ａｌ含量对反应生成 影响。     

三元混合氯化盐NaCl-KCl-MgCl2对合金的腐蚀特性实验研究

熔盐是目前太阳能热电站中应用最广泛的储热蓄热材料。为满足太阳能热发电系统对于熔盐的储热需求,该文将304、316L、321、310S不锈钢置于550℃的三元混合氯化盐NaCl-KCl-MgCl₂（7：1：2）体系中,开展混合熔盐的腐蚀特性实验研究,并探讨其中的腐蚀机理。研究结果表明,在三元混合氯化盐NaCl-KCl-MgCl₂（7：1：2）体系中,310S表现出较好的耐腐蚀性能,304的耐腐蚀性较差。MoO₃、NiO、TiO₂氧化物的生成可提高316L、310S、321不锈钢的耐腐蚀性能;混合氯化盐在高温下生成的Cl₂是不锈钢腐蚀的重要原因,外部空气中的O₂和H₂O会进入熔盐侧与合金发生反应,加剧腐蚀。     

Synthesis and characterization of NiFe2O4 nanosheet via polymer assisted co-precipitation method

Nickel ferrite (NiFe₂O₄) nanosheet has been synthesised by the polymer assisted co-precipitation method. The synthesised nanosheet was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), high-resolution scanning electron microscopy (HRSEM), thermal analysis and vibrating sample magnetometry (VSM). The results showed that the as synthesised NiFe₂O₄ has sheet like morphology with good crystalline nature. The nanosheet was formed through random aggregation of magnetic nanoparticles. Ferromagnetic property was exhibited by the nanosheet with saturation magnetization M_s = 35 emu/g, remanent M_r = 8.6 Oe and coercive force H_c = 192 emu/g.     

几种硫鎓盐类光产酸剂的合成与性质

硫鎓盐类光产酸剂因其较高的产酸效率和好的热稳定性而广泛应用于化学增幅光致抗蚀剂中。本论文选择不同的酚化合物为原料,使之与二甲基亚砜和氯化氢反应,合成了一系列硫鎓盐化合物,研究了其在有机溶剂中的溶解性、热稳定性、紫外吸收性质及其光解特性。以低压汞灯为曝光光源,测定了该类光产酸剂的光解量子效率在0.2—0.7范围。     

Synthesis and features of binary cobaltite spinels

The main developments in the synthesis of cobaltites are surveyed. Solid state reactions between oxides, thermal decomposition of mechanical mixtures of transition metal salts, the use of complex compounds as precursors, mechanochemical synthesis, deposition of cobaltites on supports and cobaltite synthesis by thermal treatment of coprecipitated compounds are discussed and the specific advantages and disadvantages of each method pointed out. The binary spinel cobaltites find applications as materials in many fields, their main importance being as catalysts. In order to achieve high specific surface area, cobaltite synthesis by thermal treatment of coprecipitated precursors proves to be the most promising method. Different kinds of precursors are regarded. Transition metal basic salts are promising for the synthesis of binary mixed oxides and, in particular, of cobaltites. The conditions suited by the coprecipitated precursors for the synthesis of cobaltites with preset properties, such as high-dispersity, homogeneity, a definite stoichiometry and a low impurity content, are indicated. Special attention is paid to hydroxidecarbonates. Their use as precursors ensures these demands for the final product and also evolution of toxic gases during the thermal decomposition is avoided.     

Field emission and I–V characteristics of template synthesised nickel nanowires on semiconducting substrate

Ion track technology makes it possible to produce a low cost template for the synthesis of nanowires. In this article, spin-coated polycarbonate films have been irradiated by energetic 150?MeV Ni ion at a fluence of 8E7, followed by UV irradiation and chemical etching in aqueous NaOH (6N,?29°C). Ni nanowires were electrochemically synthesised in the pores created in the polycarbonate film. The nanostructures thus synthesised were morphologically analysed using scanning electron microscopy and further studied for their electrical and field emission properties.     

微热量热计法研究几种盐对硝酸铵晶变的影响

硝酸铵(AN)中添加质量分数5%的无机盐并碾磨混合,通过微热量热计研究4种常用无机盐对AN晶型Ⅳ~Ⅰ型转变的影响。结果表明:两种氯盐使AN晶型Ⅱ~Ⅰ型开始转变的温度明显提前;4种无机盐使AN晶型Ⅳ~Ⅲ型转化温度降低;硝酸钾使AN晶型Ⅲ~Ⅱ型转变温度提高约7℃,氯化钾提高约3℃;氯化钾可以使AN晶型的Ⅳ~Ⅲ型、Ⅲ~Ⅱ型相转变焓降低,使晶型转变难度增大;氯化钠使AN晶型转变焓明显增大,促进AN晶型转变。