3-硝基-1,2,4-三唑-5-酮银盐的合成和热分解性能

将3-硝基-1,2,4-三唑-5-酮(NTO)的钠盐水溶液与硝酸银水溶液反应,制备了3-硝基-1,2,4-三唑-5-酮银盐(AgNTO·2H2O).用DSC、TG分析了其热行为,AgNTO·2H2O盐的热分解过程分为4个阶段:脱水、硝基的断裂和分解、三唑环的断裂分解和无机物的初步生成、最终分解为无机物.最大分解温度在2...     

3-硝基-1,2,4-三唑-5-酮金属盐的制备和热分解机理

制备了NTO的Li、Na、K、Mg、Ca、Sr、Ba、Mn、Co、Ni、Pr、Nd和Sm盐,提出了这十一种NTO金属盐的热分解机理。     

3-硝基-1,2,4-三唑-5-酮金属盐的制备和热分解机理

制备了NTO的Li、Na、K、Mg、Ca、Sr、Ba、Mn、Co、Ni、Pr、Nd和Sm盐,提出了这十一种NTO金属盐的热分解机理。     

2-羟基-4-甲氧基二苯甲酮合铜(Ⅱ)配合物的合成与表征

合成了一种新的2-羟基-4-甲氧基二苯甲酮合铜(Ⅱ)配合物,并用热重、红外光谱、紫外光谱等手段进行了表征。TG分析结果表明,配合物中金属离子与配体的化学计量比为1∶2,且该配合物在220℃以下结构保持稳定,在220~550℃存在两个失重阶段,均为其热分解过程,最终分解产物为CuO。IR分析得出,配体中羰基氧、邻位羟基氧与金属离子配位。紫外光谱分析则进一步证实了上述IR结果,同时表明,配合并未改变2-羟基-4-甲氧基二苯甲酮的性质,配合物仍然具有吸收紫外线的能力。     

NTO及其盐的制备、表征与应用

3-硝基-1，2，4-三唑-5-酮（NTO）及其盐类是具有广泛应用前景的钝感含能材料，20世纪80年代以来受到国内外学者的普遍重视。综述NTO及其盐类的制备、表征和应用方面的研究成果，介绍了国外研究的3大类NTO基炸药配方，总结了NTO盐的研究现状，并指出了今后的研究重点。     

1,2-双(苯并咪唑-2-甲氧基)苯合锌配合物的合成、热稳定性及电化学性质研究

合成了1,2-双(苯并咪唑-2-甲氧基)苯合锌配合物[ZnL]SO4,用元素分析、红外光谱对其结构进行了表征。热分析数据表明,该配合物具有较好的热稳定性,热分解起始温度为282.3℃,配合物有4次失重过程,最终的分解产物是ZnO。用电化学方法研究了配合物的电化学性质及其与DNA的键合性质。循环伏安实验结果表明,配合物与DNA作用后峰电流明显降低,且与dsDNA的作用明显强于ssDNA,因此,该配合物有望用于dsDNA和ssDNA的识别探针。     

1-氨基-1-肼基-2,2-二硝基乙烯碱金属盐的制备及对改性双基推进剂主组分热分解的催化作用

1-氨基-1-肼基-2,2-二硝基乙烯（AHDNE）与氢氧化钾或碳酸铯反应得到相应的碱金属盐AHDNE-K 和AHDNE-Cs。 通过元素分析和红外光谱对其进行结构表征;采用单晶X射线衍射分析法测定了AHDNE-K的单晶结构,DSC技术研究了两种金属盐对3种改性双基推进剂主组分HMX、RDX和NC/NG热分解的影响。结果表明,AHDNE-K对NC/NG有明显的催化效果,使分解温度降低了约24 ℃,能量增加了1 316 J·g^-1。     

NTO炸药研究进展

综述了3-硝基-1,2,4-三唑-5-酮(NTO)炸药的合成、结晶、含能盐和压装、浇铸、熔铸三大系列混合炸药及相关性能、应用研究进展。NTO爆速为8 200 m/s,感度大于88 cm,性能良好,利用它的高能与低感可研制出应用于IM的混合炸药,是RDX最有前景的替代物。     

微量元素锰和镍缩二脲配合物的合成、表征与热分解

以硫酸镍或硫酸锰及缩二脲为原料,在甲醇溶液中合成了镍和锰的缩二脲配合物[Ni(bi)2]SO4和[Mn(bi)2]SO4,用滴定分析、元素分析、红外光谱和X射线粉末衍射对产物进行了表征,并研究了配合物的热分解过程。结果表明,镍和锰离子都与缩二脲中的羰基氧原子配位。镍配合物的热分解过程包含缩二脲和金属盐的氧化分解,残余物为氧化镍;而锰配合物的热分解过程仅为缩二脲的分解,残余物为硫酸锰。     

5,5′-偶氮四唑过渡金属含能配合物对RDX和HMX热分解行为的影响

用DSC研究了5种5,5′-偶氮四唑过渡金属配合物MATZ(H2O)n(M=Mn,Ni,Zn,n=6;M=Co,Pb,n=3;ATZ=5,5′-偶氮四唑离子)对RDX和HMX热分解行为的影响。用分解峰温、热爆炸临界温度等特征参数评价了含配合物的二元混合物与纯组分的热分解行为。结果表明,配合物对RDX的影响大于对HMX的。含配合物的二元混合物的热分解行为与纯组分的热分解行为类似,配合物的分解影响了RDX和HMX的热分解特征参数。     

NTO及其盐的制备、表征与应用(续)

2．2．2晶体结构 杨利等人、冯长根等人、马海霞等人对制备的NTO胺盐的晶体结构进行了研究，确定了它们的分子结构和晶体学参数，李加荣对一些早期的研究成果进行了概述，结果见表12。研究表明：目前制备出的NTO胺盐全部为离子型化合物，除ANTO和GNTO各含1分子结晶水外，其他NTO胺盐均不含结晶水。     

NTO与黏结剂的界面作用

采用DCAT 21型动态接触角/表面张力仪测量了NTO、GAP、HTPB、聚氨酯的接触角,通过接触角计算出NTO、GAP、HTPB、聚氨酯的表面自由能,并计算了NTO与GAP、HTPB、聚氨酯之间的黏合功W和铺展系数S。NTO-GAP、NTO-HTPB和NTO-聚氨酯界面之间的黏合功分别为114.59、76.13和101.81N/m,铺展系数为63.57、33.14和53.27 N/m。结果表明,NTO与GAP、HTPB、聚氨酯界面之间的相互作用大小顺序为NTO-GAPNTO-聚氨酯NTO-HTPB。红外光谱研究结果也显示,NTO-聚氨酯的界面相互作用比NTO-HTPB的界面相互作用强。     

Chemical Kinetics of the Thermal Decomposition of NTO

The kinetics of thermal decomposition of 3‐nitro‐2,4‐dihydro‐3H‐1,2,4‐triazol‐5‐one (NTO) in the temperature interval from 200 °C to 260 °C was investigated using a glass Bourdon gauge. The overall decomposition reaction includes two distinct stages: the fast first‐order decomposition and the subsequent autocatalytic reaction. The importance of the first stage increases with increasing decomposition temperature and decreasing loading density of the Bourdon gauge (m/V). A period of preliminary heating, at a lower temperature, strongly influences the autocatalytic stage when the decomposition is carried out at a higher temperature. In the temperature domain 200–220 °C, the Arrhenius constants of the decomposition reaction are found to be close to the values usually observed for nitrocompounds: E=173 kJ/mol and log₁₀ k≈12.5 (s⁻¹). It is shown that a simple model of NTO decomposition based on an autocatalytic reaction of the m‐th order can describe the course of the decomposition at high temperature but the m number appears to be excessively high, up to 4. A new model of the decomposition is developed, including an initial monomolecular reaction, decomposition of the crystalline substance, and an autocatalytic reaction of NTO dissolved in liquid decomposition products. This model gives the common order of autocatalysis, m=1.     

Composite Energetic Materials Containing Nitrotriazalone Formed by Molecular Inclusion

The explosive properties of inclusion compounds containing the monoanion of the energetic compound 3‐nitro‐1,2,4‐triazol‐5‐one (NTO⁻) non‐covalently bound to either of two larger, energetic, receptor complexes, namely 1‐(2,4‐dinitrophenyl)‐1,4,7,10‐tetraazacyclododecanezinc(II) or 1‐(2,4‐dinitrophenyl)‐1,4,7,10‐tetraazacyclododecanecopper(II), both as their monoperchlorate salts, are reported. The sensitivity of the receptor host–guest complexes to electrostatic discharge or friction was not found to differ from that displayed by the separate components. However, for thermal sensitivity it was found that whereas NTO⁻ desensitized the Zn(II) receptor complex it sensitized the Cu(II) receptor complex. For sensitivity to impact, measured using the Rotter impact test, it was found that NTO⁻ sensitized the Zn(II) receptor complex, but desensitized the Cu(II) receptor complex.     

含能燃烧催化剂NTO铅正盐的合成与性能

以3–硝基–1,2,4–三唑–5–酮(NTO)为原料,经中和反应和复分解反应"一锅法"合成了含能燃烧催化剂NTO铅正盐NP,收率达99%以上,并采用红外光谱、元素分析等对其结构进行了鉴定,NP分子式为C2H2N4O4Pb。产物NP的密度为4.24 g/cm3,DSC分解峰温为246.7℃和369.0℃,生成热为–889.9 J/g,撞击感度为68%,摩擦感度为100%,特性落高H50>91 cm,饱和水溶液pH值为6.8。     

NTO盐热爆炸临界温度的数值计算

提出了由一组热爆炸温度和实测爆炸延滞期数据计算含能材料热爆炸临界温度（Ｔｂ）的一种数值方法。编制了该法的计算机程序。ＥＮＴＯ、ＰｂＮＴＯ、ＡＮＴＯ和ＫＮＴＯ的Ｔｂ计算和文献值相差在６％以内。     

From Synthesis to Formulation and Final Application

Meeting the requirements for insensitive munitions remains a complex route, where all the steps of the production process have to be addressed. NTO is a choice component, especially for large munitions. Various compositions have been optimized, which are now available, in pressed or cast PBX as well as melt cast formulations. Standard products such as RDX have been improved by the synthesis or crystallization methods, giving reduced sensitivity formulations. Some cast PBX can sustain severe shaped charge jet impacts, thanks to their large critical diameter, and are candidates as main filling of large munitions such as IM Mk82. The formulation step is addressing not only new binder principles, allowing an increase in the filler and thus energy contents, but also a bi‐component innovative method to get a semi continuous filling process where the pot life is no longer an issue. Finally a partial toolset for designing IM features is proposed with a recent example of successful application.     

Synthesis and Energetic Properties of Imidazolium and 2‐Methylimidazolium Salts of 3‐Nitro‐1,2,4‐Triazol‐5‐One

Two new energetic salts of 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) were described. Imidazole and 2‐methylimidazole salt of NTO decomposes exothermically at 217 and 258 °C respectively. Detonation parameters calculated for 2‐methylimidazole salt are significantly smaller than that of 2,4,6‐trinitrotoluene (TNT) but these parameters estimated for imidazole salt are comparable with that of TNT. Structure of new compounds were investigated with NMR and IR spectroscopy. Impact and friction sensitivity determined for new compounds are smaller than for pure NTO, so they are more safe during handling.     

Energetic Residues from the Detonation of IMX‐104 Insensitive Munitions

The development of insensitive munitions by NATO countries is an ongoing effort. Less‐sensitive ingredients in both explosives and propellants will ensure the protection of deployed troops against an unwanted reaction to an external stimulus on the munitions stockpile. In the US Army, current efforts are directed towards the development of melt cast insensitive explosive formulations. Various formulations, mainly based on DNAN and NTO, have been developed and are now being fielded. Our research goal is to measure the deposition rate of energetics compounds from various insensitive munitions detonation scenarios. Our hypothesis is that the relative insensitiveness of these formulations leads to slightly higher deposition rates than conventional explosive formulations. This paper describes detonation residues research on mortar rounds containing IMX‐104 explosive. Analyses indicate that high‐order detonation residues are slightly greater for this formulation than for conventional munitions. However, blow‐in‐place detonations (BIPs) resulted in much higher residues deposition, indicating that a larger donor charge is required for efficient detonation. The highly soluble compound NTO was particularly problematic, with BIP deposition approaching 95 % of the original load. Toxicological studies of NTO are not finalized, leaving considerable uncertainty regarding the feasibility of approving these rounds for distribution.