HU Rong-zu , GAO Hong-xu , ZHAO Feng-qi , ZHANG Hai , MA Hai-xia , XU Kang-zhen
2009, 17(6):635-642. DOI: 10.3969/j.issn.1006-9941.2009.06.001
Abstract:Two general expressions and their six derived formulae for estimating the critical temperature (Tb) of thermal explosion for energetic materials (EMs) are derived from the Semenov′s thermal explosion theory and eight non-isothermal kinetic equations, using reasonable hypothesis. The initial temperature (T0i) at which DSC curve deviates from the baseline,the onset temperature (Tei), the kinetic parameters of exothermic decomposition reaction can be obtained from the non-isothermal DSC curve of EMs. The values of T00 and Te0 was obtained from the equation T0i or ei = T00 or e0 + a1 βi + a2 βi2 +…+aL-2βiL-2,i=1,2,…, L and then the values of Tb was calculated by the six derived formulae. The Tb results obtained with the six derived formulae for 1, 4, 5, 8-tertanitro-1,4,5,8-tetraazadifurazano[3,4-c:3′,4′-h] decalin and its parent compound, 1,3,4-trinitro-imidazolonone[4,5-b] furazano[3,4-e] piperazine and its parent compound, 1,3,4,8-tetranitro-imidazolinone[4,5-b] furazano[3,4-e] piperazine, 1,4,5,8- tetranitro -1,4,5,8-tetrazafurazano[3,4-b] decalin and 1,3,5-trinitro-1,3,5-triazafurazano[3,4-f] cycloheptane approximate well to each other.
HU Rong-zu , GAO Hong-xu , ZHAO Feng-qi , ZHANG Hai , ZHAO Hong-an , MA Hai-xia , XING Xiao-ling , XUE Liang
2009, 17(6):643-649. DOI: 10.3969/j.issn.1006-9941.2009.06.002
Abstract:Two mathematical expressions for calculating the kinetic parameters of exothermic decomposition reaction of energetic materials (EMs) are derived from peak temperature of DSC curves at constant heating rates based on Kooij′s formula and van′t Hoff′s formula, the corresponding numerical method for calculating the kinetic parameters are presented. The E results obtained with the two derived formulae and Kissinger′s method, Ozawa′s method, Tang′s method, Hu-Gao-Zhang method and integral isoconversional non-linear method (NL-INT) for 2,4,6-trinitro-2,4,6-triazacyclohexanone (Keto-RDX), approximate well to each other, showing that taking the value of a of 0.5 and the value of b of 0.003 are suitable for calculating the kinetic parameters by the two derived formulae.
JIAO Dong-ming , YANG Yue-cheng , QIANG Hong-fu , WU Wen-ming
2009, 17(6):650-654. DOI: 10.3969/j.issn.1006-9941.2009.06.003
Abstract:In order to explore the effect of bonding agents on the mechanical properties and chemical ageing resistance of hydroxyl-terminated polybutadiene (HTPB) solid propellant, molecular dynamics method and COMPASS force field were adopted to simulate the adsorption energy and mechanical properties of the interfaces constructed by HTPB, bonding agents and crystal faces of Al and Al/Al2O3. Then simulations were applied to estimate the diffusion coefficients of H2O and O2 in different bonding agents membranes. The results show that bonding agents increases the interaction of solid grain and HTPB, and improves elastic modul of Al/HTPB layer showing the enhancement of HTPB system rigidity. The trend of ability of restraining the diffusion of gas is consistent with experimental chemical ageing resistance of different bonding agents.
DUAN Xiao-hui , WEI Chun-xue , PEI Chong-hua , LI Jin-shan
2009, 17(6):655-659. DOI: 10.3969/j.issn.1006-9941.2009.06.004
Abstract:The crystal morphologies of α-and β-HMX were predicted by using attachment energy (AE) and Bravais-Friedel-Donnary-Harker (BFDH) models. The important crystal surfaces are (020), (011), 10-2), (11-1), 100) for β-HMX and (040),(220) and (111) for α -HMX. The analyses of the crystal surface structures show that (100) and (111) are greatly polar, and (020),(011),(11-1) and (220) are polar, while (10-2) and (040) are non-polar. It can be predicted that (100) and (111) are the important crystal surfaces in the proton solvents with strong polarity,and the appearance area of (020),(011),(11-1) and (220) is increased,and the (10-2) and (040) surfaces diminishes or disappeares,while the contrary cases occurs in the non-polar solvents.
CUI Cai-ping , HUANG Hui , DUAN Xiao-hui , ZENG Gui-yu , MA Yong-jun , PEI Chong-hua
2009, 17(6):660-663. DOI: 10.3969/j.issn.1006-9941.2009.06.005
Abstract:The RDX with fractal structures was prepared by the evaporation of solvent on glass substrate, and was characterized by scanning electronic microscope (SEM). The effects of solution concentration of RDX and surfactant on the fractal structure were studied. The formation mechanism for fractal structure of RDX was discussed. Results show that the different fractal structure of RDX can be obtained by means of non-equilibrium crystallization on glass substrate. The dendritic growth of RDX occurs with low concentration of RDX 16 mg·mL-1), while the random fractal growth occurs with high concentration of RDX (26 mg·mL-1). The influence of the surfactant of hexadecyl trimethyl ammonium chloride on the morphology of RDX is obviously.
JING Shi-ming , LI Ming , LONG Xin-ping
2009, 17(6):664-667. DOI: 10.3969/j.issn.1006-9941.2009.06.006
Abstract:Polymer bonded explosives are composites containing elastic energetic particles in a viscoelastic binder. The volume fraction of the elastic particles in PBX is normally greater than 80%, therefore using the classical analytical meso-mechanics model (Hashin-Shtrikman) to estimate the effective elastic modulus of TATB-based PBX is quite inaccurate. A new term named “interface bonding parameter” which contains the density of the bulk PBXs was promoted and a modified model of Hashin-Shtrikman was obtained. The samples with different densities were prepared, and their elastic modulus was measured, and the modified coefficients of the model were obtained to be 0.813(ρ/ρ0)8.64or 0.296(ρ/ρ0)8.68. The elastic modulus was calculated by the classical Hashin-Shtrikman model and by the modified model respectively. It shows that the modified model with “interface bonding parameter” can give more accurate results compared to that with the classical Hashin-Shtrikman model. The effective elastic modulus decays exponential with the decreasing of TATB-based PBX density, and the effective bulk modulus and the effective shear modulus are influenced by density to the same degree,and the exponents are about 8.6. The predicting and the experimental results are only 1% apart. It proves that the modified Hashin-Shtrikman can be used to predict the effective modulus of double-composition PBXs.
ZHANG La-ying , HENG Shu-yun , LIU Zi-ru , ZHANG Gao , SHAO Ying-hui , WANG Lin , ZHAO Feng-qi , TAN Hui-min
2009, 17(6):668-673. DOI: 10.3969/j.issn.1006-9941.2009.06.007
Abstract:The interactions for 3,3-bis(azidomethyl)oxetane/tetrahydrofuran copolymer (PBT) with hexanitrohexaazaisowurtzitane (CL-20), 3,4-dinitrofurazanfuroxan (DNTF), 1,3,3-trinitroazetidine (TNAZ) and ammonium nitrate (ADN) were studied by using pressure differential thermal analyzer (PDSC) and thermogravimetry-derivative thermogravimetry (TG-DTG). The results show that decomposition of CL-20 is accelerated by PBT, decomposition peak temperature of CL-20 in PBT/CL-20 is a drop in 33.7 ℃ compared with that of pure CL-20. A part of PBT is also accelerated to decompose for the effect of the CL-20 and (or) its decomposition products. Sublimation and volatilization of the DNTF and TNAZ may be restrained by macromolecule of PBT,and their decompositions are advanced about 100 ℃. Besides,PBT is also accelerated to decompose by the decomposed gas products of DNTF and TNAZ. The interaction for PBT with ADN and its condensed phase products is not evident,except for the restraint effect of PBT on the sublimation of AN as the products of ADN. However,the gas products of ADN exert an influence on the PBT and ADN.
WANG Bo-zhou , LUO Yi-fen , ZHOU Yan-shui , LAI Wei-peng , LIU Qian
2009, 17(6):674-677. DOI: 10.3969/j.issn.1006-9941.2009.06.008
Abstract:The synthesis of 3-amino-4-amidoximinofurazan from malononitrile (MN) was proposed in the literature as four-step reaction: nitrosation, rearrangement, oximation and dehydration cyclization. In this paper the nitrosation was tracked via in situ IR, and 2-nitrosomalonitrile (NMN) and 2-oximinomalonitrile (OMN) (as a pair of isomer) were detected. In addition, the 3-demensional in situ IR spectra of —NO、 NOH and —OH, and the intensity history of characteristic peaks for —NO,CN and —OH during the nitrosation process were recorded and derived, which gives an insight into the nitrosation. But OMN was not successfully separated. As a product of reaction of MN with NaNO2 and that of reaction of sodium salt of OMN (NaOMN) with NH2OH, both of NaOMN and 1,3-diamino-1,2,3-trioximinopropane were obtained and characterized by IR, NMR, MS and elemental analysis. Based on what described above, we propose the following five-step mechanism for the title reaction: nitrosation, rearrangement, salification, oximation, and dehydration cyclization.
CAO Duan-lin , WANG Xiao-jun , YANG Cai-yun , SONG Lei , HAN Hao , ZHOU Jun-feng , CHANG Jun-fang
2009, 17(6):678-680. DOI: 10.3969/j.issn.1006-9941.2009.06.009
Abstract:1-Methyl-4,5-dinitroimidazole(4,5-MDNI) was synthesized from nitration of 1-methylimidazole. 4,5-Dinitroimidazole (4,5-DNI) displaying acidity was dissolved. The structure of 4,5-MDNI was characterized by IR,elemental analysis,1H NMR and MS. Effects of the temperature, reaction time and the ratios of fuming sulfuric acid to fuming nitric acid on its yield were studied by orthogonal test. The optimal reaction conditions for synthesizing 4,5-MDNI are obtained as follows: the yield of 4,5-MDNI is 60%, and reaction temperature is 105-115 ℃, and reaction time is 2 h, and the ratios of sulfuric acid and nitric acid is 1:1. The thermolysis property of 4,5-MDNI was studied by differential scanning calorimetry(DSC). Results show that the melting point of 4,5-MDNI is 78 ℃,and 4,5-MDNI has good thermal stability.
XU Ruo-qian , JI Yue-ping , DING Feng , WANG Wei , LAN Ying , LIU Ya-jing
2009, 17(6):681-684. DOI: 10.3969/j.issn.1006-9941.2009.06.010
Abstract:Taking 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione as initiator,boron-trifluoride etherate as catalyst, and 2-chlorooxirane as monomer,two polymers(polyepichlorohydrin(PECH)) with different molecular weights were synthesized by the opening-ring polymerization of epichlorohydrin. And then two bran-new tri-arms glycidyl azide polymer azide(GAPA) were obtained by the reaction of nitration and azidonation. The structure of GAPA was characterized by IR and GPC. Results show that the glass transition temperature of GAPA is -52.86 ℃,and its thermal decomposition temperature is 247.9 ℃. The superior properties of GAPA show that it can be used as an energetic plasticizer.
CUI Qing-zhong , JIAO Qing-jie , LIU Shuai
2009, 17(6):685-688. DOI: 10.3969/j.issn.1006-9941.2009.06.011
Abstract:The carbon nano-tubes/potassium nitrate (CNTs/KNO3) composites were prepared by recrystalization and neutralization method respectively. Micro-morphologies and thermal decomposition properties were characterized by scanning electron mitroscope (SEM), X-ray diffraction (XRD), specific surface area (SSA and differential scanning calorimeter (DSC). The results show that KNO3 is coated on the surface of CNTs by two methods. SSA of the nano-CNTs/KNO3 composites by recrystalization decreases about 113.9 m2·g-1<./sup> compared with that of CNTs, while the thermal decomposition temperature is the same as that of KNO3. SSA of the nano-CNTs/KNO3 composites prepared by neutralization decreases about 138.7 m2·g-1<./sup> compared with that of CNTs, and the thermal decomposition temperature decreases about 28 ℃ compared with that of KNO3. Results show that in neutralization, CNTs has catalytic effect on the thermal decomposition of KNO3.
JIANG Xia-bing , LIANG Yi-qun , ZHANG Jing-lin , CHEN Jian-shen
2009, 17(6):689-693. DOI: 10.3969/j.issn.1006-9941.2009.06.012
Abstract:In the process of silica(SiO2) sol transiting into gel, the definite mixture of acetone, N,N-dimethylformamide(DMF) and hexogen(RDX) and the mixture of acetic ester and fluorine rubber(FPM2602) were added sequentially, and the sub-transparent white 80% RDX/SiO2 booster membranes were obtained by pulley and manual spin coating methods. Results show that when the molar ratio of silicic acid tetracthyl ester (TEOS) to ethanol is 1:4, with the proper decreasing of the molar ratio between ethanol and water, the ductility of membrane and the particle size of RDX decrease. When the sol ages at 60 ℃, the viscosity of sol solution increases from 3 Pa·s to 13 Pa·s at gel point with the increasing of aging time, and the membranes acquired by spin coating is thin and smooth. The SEM photographs show that the spheroidal SiO2 with particle size of 300-500 nm adheres on the surface of RDX and forms a blocklike composite membrane element of RDX/SiO2 with size of 3-5 μm,which is a new-type booster membrane.
SHENG Di-lun , MA Feng-e , ZHANG Yu-feng , ZHU Ya-hong , CHEN Li-kui , YANG Bin
2009, 17(6):694-698. DOI: 10.3969/j.issn.1006-9941.2009.06.013
Abstract:The single crystal of tetraamminediazido cobalt(Ⅲ) perchlorate(DACP) was prepared,and its crystal structure was determined by a X-ray single crystal diffractometer. The results show that the crystal is triclinic belonging to space group of P-1 with crystal parameters of the unit cell dimensions: a =0.74229(9)nm,α =93.244(2)°; b=1.2127314) nm,β =100.074(2)°; c=1.8124(2)nm,γ =98.033(2)°, volume V=1.5851(3) nm3, Z =6,calculated density Dc=1.952 mg·mm-3,absorption coefficient μ=1.901 mm-1, F(000)=948. The compound is very sensitive to laser with a wavelength of 635 nm.
FENG Hong-yan , ZHU Shun-guan , ZHANG Lin , LI Yan , SHEN Rui-qi
2009, 17(6):699-703. DOI: 10.3969/j.issn.1006-9941.2009.06.014
Abstract:The energy transfer mechanism between semiconductor bridge (SCB) plasma and the explosives was studied. The possible energy effect forms were mentioned and discussed by the mode of capacitor discharge. Some special ignition tests were designed and carried out to validate some energy transfer mechanisms including the thermal conduction between SCB and the explosive material, SCB plasma shock effect and permeability heat effect. A continuum model was developed to analyze the heat transfer from SCB plasma to explosive particles. The spherical heat transfer models of three primary explosive particles lead styphnate (LTNR), nickel hydrazine azide (NHA and nickel hydrazine nitrate (NHN) were calculated by Fourier analysis and numerical simulation. The minimum ignition voltages of three explosive particles were 11 V, 15 V and 39 V respectively. The ignition tests show that heat transfer coefficients of medicaments affect ignition attributions of SCB. The smaller heat transfer coefficient is, the smaller minimum ignition voltage is. The simulated results show that the permeability heat effect is the main energy effect form in the SCB ignition tests.
LIU Ling , LI Guo-xin , JIANG Xin-guang , LAO Yun-liang
2009, 17(6):704-707. DOI: 10.3969/j.issn.1006-9941.2009.06.015
Abstract:In order to study the regulation of burning rate and combustion characteristics in high burning rate work device, and ensure the thrust output stability of the device, a burning rate test by optical fiber was introduced and the ignition-combustion rate of pyrotechnic short-pulse propelling work device was tested. Results show that the combustion process has a non-parallel layer burning characteristic, and the distributions of burning rate exist in three different diagnostic burning zones (the parallel layer combustion zone, the transition combustion zone and the stable convection zone) along the burning direction, the stable burning rate of the propelling device reaches the maximum when the charge density is 1.45 g·cm-3.
DAI Meng-yan , HU Bi-ru , WU Wen-jian
2009, 17(6):708-712. DOI: 10.3969/j.issn.1006-9941.2009.06.016
Abstract:By using of high-speed photograph techniques, thermogravimetric analysis (TG), differential thermal analysis(DTA) and scanning electron microscope (SEM), the combustion process of fog aerosol and formation of condensation nucleus were investigated. Results show that the high temperature and pressure air mass with a large amount of high temperature condensation nucleus is produced after the combustion of fog aerosol,and the temperature and pressure decrease rapidly with the air mass ascending. The particle size distribution of condensation nucleus is 0.2-1 μm and its main component is NaCl. The growing process of condensation nucleus and the forming of fog droplet are related with the supersaturation produced by the cooling and expanding of the air mass.
LIANG Hua-qiong , YONG Lian , TANG Chang-liang , CHEN Xue-ping , HUANG Jiao-hu
2009, 17(6):713-716. DOI: 10.3969/j.issn.1006-9941.2009.06.017
Abstract:The interfaces between RDX and binder are easily debonded because of improper bonding choice and pressing process conditions. The RDX-based polymer bonded explosives(PBXs) with F2311 and acrylonitrile-acrylate respectively were pressed by steel to study the pressing damage mechanisms. Results show that proper pressing conditions decrease the pressing damage in the shaping samples. The proper bonding improves the properties of the shaping samples. When acrylonitrile-acrylate is used in shaping RDX-based explosives, the properties of the samples are better than that of samples with F2311.
LIU Li-rong , ZHI Hui-zhen , LUO Jun , Lü Chun-xu
2009, 17(6):717-721. DOI: 10.3969/j.issn.1006-9941.2009.06.018
Abstract:Two new acidic ionic liquids catalysts-HNIL·NO3- and HNIL·HSO4- were employed as Lewis acid catalysts for nitration of toluene. The effects of kind of catalyst, dosage of catalyst, nitrated reaction time and temperature, acetic anhydride and recovered catalyst, etc. on the selectivity of nitration of toluene were investigated. With 95% nitric acid as nitrating reagent and CCl4 as solvent at the presence of acetic anhydride. The results show high selectivity when the temperature is controlled at 55 ℃, and the nitrated reaction time is 60 min. The o/p (ratio of ortho to paro isomer of toluene nitration ) ratio is 1.12 in product distribution of toluene nitration. It is lower than1.67 using sulfonitric acid as catalyst. The yield of products is 99.4%. The catalyst can be reutilized up to five times with little decrease in activity.
SHUAI Jun-feng , JIANG Jian-wei , WANG Shu-you , MENG Jian-bing , XIE Chang-you
2009, 17(6):722-725. DOI: 10.3969/j.issn.1006-9941.2009.06.019
Abstract:The damage effects of compound reactive fragment on steel target were studied. Using Ф12.7 mm ballistic gun, the tests of compound reactive fragment penetrating A3 steel target were carried out and recorded by a high speed camera. Results show that phenomenon of burning and explosion are obvious while reactive fragments penetrate target. The effect of deflagration produced by compound fragments with titanium powder and PTFE materials are better than that of fragments with aluminum powder and PTFE materials. The compound reactive fragment with thicker shell have a better penetrating effect on target. Comparing with the same dimension of inert steel fragment, the hole diameter of penetrating target is increased by about 40% for compound reactive fragment.
ZHAO Jun , LIAO Xin , WANG Ze-shan
2009, 17(6):726-730. DOI: 10.3969/j.issn.1006-9941.2009.06.020
Abstract:Based on the fast change of pressure in closed bomb tests, a heat flux equation focused on pressure factor was deducted. A one-dimensional semi-infinite model of calculating inwall heat transfer in closed bomb tests was established and the expression of heat transfer was obtained. The model was validated by double base aromatic-3 (SF-3), TEGDN (TG) propellant and triple-base propellant. The results show that the error between corrected whole heat loss and theoretical whole heat loss is less than 10%,and the burning rate pressure index of SF-3 propellant obtained is close to the expected value.
ZHANG Xian-feng , ZHAO Xiao-ning
2009, 17(6):731-739. DOI: 10.3969/j.issn.1006-9941.2009.06.021
Abstract:Multifunctional Energetic Structural Material (MESM) is a new type of functional material with comprehensive utilization of chemical and kinetic energy. The development of MESM and its application were introduced. The experimental techniques of MESM under shock load, reaction mechanism, and theoretical model were reviewed. The application of shock-induced chemical reactions (SICR) model and empirical molecular dynamic methods which were use to describe the reaction process of MESM were introduced. The current application and the prospects of MESM were reviewed.
LI Ya-nan , SHU Yuan-jie , ZHANG Zhi-zhong
2009, 17(6):740-744. DOI: 10.3969/j.issn.1006-9941.2009.06.022
Abstract:Common methods of furoxan ring formation were analyzed. Main preparation reactions of cyanide oxide and their advantages and disadvantages were summarized, such as the reaction of hydroxamic chloride and weak base,the reaction of aldehyde oxime and nitric oxide, the reaction of hydrazide potassium salt and oxidants, et al. Dimerization reaction of cyanide oxide leads to formation the furoxan derivatives with symmetrical substituent groups. The properties of some symmetrical furoxan derivatives were listed.
GE Zhen , LUO Yun-jun , GUO Kai , Lü Yong , JIU Yong-bin
2009, 17(6):745-750. DOI: 10.3969/j.issn.1006-9941.2009.06.023
Abstract:The polymers of 3, 3-diazidomethyloxetane (BAMO) are typical high-energy and high-density energetic polymers. The development of synthesizing BAMO monomer, BAMO homopoymer and copolymers was reviewed, and future study about them was also prospected in this paper. BAMO-AMMO and BAMO-GAP energetic thermoplastic elastomers are widely used. Cation livng polymerization is major synthesizing method of BAMO polymers.
LIU Yong , XIONG Ying , SHU Yuan-jie , LIU Xue-yong , ZHONG Fa-chun , ZHANG Yong , SUN Yi
2009, 17(6):751-752. DOI: 10.3969/j.issn.1006-9941.2009.06.024
Abstract:9-Hydroxy-9-acetenylanthrone was synthesized and characterized, and its fluorescence quenching with TNT in chloroform was investigated.
MENG Zi-hui , YANG Feng-min , LI Qing-xia , ZHOU Zhi-ming
2009, 17(6):753-754. DOI: 10.3969/j.issn.1006-9941.2009.06.025
Abstract:Recrystallization of 1, 3, 5-triamino-2, 4, 6-trinitrobenzene(TATB) in five kinds of ionic liquids, including 3-ethyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium tetrafluoroborate, 3-butyl-1-methylimidazolium hexafluorophosphorus, 3-hexyl-1-methylimidazolium bromine and 3-butyl-1-methylimidazolium chloride([Bmim]Cl) was investigated. TATB can be dissolved in [Bmim]Cl, and the thermal stability of TATB improved after recrystalization in the ionic liquid was also investigated. The exothermic temperature of the recrystalized TATB (375 ℃) which is higher than that of raw TATB (363 ℃) indicats that the stability of recrystalized TATB is improved.
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Editorial Board of Chinese Journal of Energetic Materials
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