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Thermal Properties

1. Investigation on Thermal Pyrolysis of RDX by T-JUMP/FTIR

WANG Xiao-hong,ZHANG Gao,LIU Zi-ru,XIE Ming-zhao,PAN Qing,HENG Shu-yun
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China

Abstract: The pyrolysis process of RDX was investigated by using T-JUMP/FTIR test.The influence of temperature and pressure on the fast thermolysis process and the distributing law and relative quantity of gas products with respect to temperature and pressure were analyzed.The possible fast thermolysis mechanism of RDX was validated.The factors affecting the fast thermolysis mechanism were analyzed.The results show that the main gas products of RDX thermolysis are CO2,N2O,NO2,HNCO,NO,CO and HCN,which relative content have an evident change under different experiment conditions.Following pressure increase from 0.1MPa to 0.4MPa in 5s at 600℃,the ratios of NO2/NCN decrease and the HCN/N2O increase.The ratios of HCN/N2O increase following temperature increase at normal atmosphere.Two competition reaction are confirmed in the initial stage of RDX pyrolysis process.It is considered that the formation of HCN in two competing branches for RDX decomposition is favored at higher temperature and pressure in the range of 0.1-0.4MPa.

2. Study on Kinetics of the VNS Amination of 4-Amino-1,2,4-triazole and 2,4,6-Trinitromethylbenzene by HPLC

JIANG Si-yao,WU Yu-kai,LI Ji-nan,ZHOU Yan-xia,ZHOU Zhi-ming
School of Chemical Engineering and Environments,BeijingInstitute of Technology,Beijing 100081,China

Abstract: The kinetic model of the VNS amination reaction of 2,4,6-trinitromethylbenzene(TNT) and 4-amino-1,2,4-triazole(ATA) was investigated by monitoring the change of concentrations of reactant with time using HPLC method,the rate constants and activation energy of the reaction were obtained.The experimental results showed that study on kinetics of the VNS amination by HPLC was available.The rate constants at 25℃ and 35℃ are 0.36L•mol-1•min-1 and 0.63L•mol-1•min-1,respectively.The activation energy of the reaction was 42.74kJ•mol-1.The reaction is easy to process,and with the increase of temperature,the rate constant increases.

3. Relationships Between the Decomposition Heat (Q_(dec)) with the Adiabatic Temperature rise (T_(ad)),the Explosion Heat (Q_(CO_2)) and the Heat-temperature Quotient (Q_(dec)/T_p),and Q_(CO_2) with Q_(CO_2)/T_(ad) for C-H-N-O Polynitroaromatic Compounds

HU Rong-zu1,GAO Hong-xu1,ZHAO Feng-qi1,YANG De-suo2
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.Department of Chemistry,Baoji College of Arts and Science,Baoji Shaanxi 720017,China

Abstract: Four relationships are established,using the least-squares method,between the decomposition heat (Qdec) with the adiabatic temperature (Tad),the explosion heat (QCO2) and the decomposition heat divided by the peak absolute temperature (Tp) of DSC curve (Qdec/Tp),and QCO2 with QCO2/Tad.

4. Influence of 2,6-Diamino-3,5-dinitropyridine-1-oxide on Properties of RDX

HE Zhi-wei1,LIU Zu-liang1,WANG Ai-ling2
1.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
2.Shandong Machinery Group Co.,Ltd,Zibo Shandong 255201,China)

Abstract: In order to know the desensitizing efficiency of 2,6-diamino-3,5-dinitropyridine-1-oxide(ANPyO) on hexogen(RDX),ANPyO/RDX composites were prepared by crystal coating and mixing method respectively.The structures and properties of the two samples were characterized by SEM,laser particle size analysis,TG,DSC,mechanical sensitivity and detonation velocity tests.Results show that ANPyO has a better coating on RDX crystal coating than mixing method;the average particle sizes of the samples are situated between ANPyO and RDX,and the particle size distribution of sample in crystal coating is more uniform;the decomposition peak temperatures of the samples are lower than that of RDX,the thermal decomposition peak temperatures are higher 6～15℃ crystal coating than mixing method;in comparison with RDX and the sample obtained by mixing method the mechanical sensitivity of the samples are lower than that of RDX,and the mechanical sensitivity of the sample in crystal coating decreased more significant.

5. Kinetic Parameters of Explosive Decomposition Reaction of Trinitromethyl Explosives as a Function of Temperature

HU Rong-zu1,SONG Quan-cai2,DONG Hai-shan3,ZHAO Feng-qi1, GAO Hong-xu1,ZHAO Hong-an4,MA Hai-xia5
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.College of Material Science and Engineering,Beijing Institue of Techology,Beijing 100081,China
3.Institute of Chemical Materials,CAEP,Mianyang 621900,China
4.College of Communication Science and Engineering,Northwest Univerisity,Xi′an 710069,China
5.College of Chemical Engineering,Northwest Univerisity,Xi′an 710069,China)

Abstract: The time lag prior to explosion of six trinitromethyl explosives: 2,2,2-trinitroethyl-N-nitromethyl amine(TNMA),bis(2,2,2-trinitroethyl-N-nitro) ethylene diamine(BTNEDA),2,2,2-trinitroethyl-4,4,4-trinitrobutyrate(TNETB),bis(2,2,2-trinitroethyl) formal(BNTF),1,1,1,3tetranitropropane(TETNP) and bis(2,2,2-trinitroethyl-nitramine(BTNNA) at different temperature was measured by an explosion temperature test apparatus.The apparent activation energy(Eα) and pre-exponential constant(Aα) of the explosive decomposition reaction and the value of T corresponding to t=5s,Tt=5s,in Semenov′s equation for the relationship governing the time lag t,prior to explosion after heating to a temperature,T(K): lntlag,i=EαRTi-lnAα were calculated.The values of Eα obtained by integral isoconversional non-linear method were used to check the values of Eαobtained by plotting lntlag,i against 1/Ti.With the help of thermodynamic formulae,the thermodynamic parameters of activation [free energy of activation(ΔG≠),enthalpy of activation(ΔH≠) and entropy of activation(ΔS≠)] for the explosive decomposition reaction were calculated.The results show that:(1) the relative error between the values of Eα by plotting method and Eα is within ±5%;(2) the fact of Eα=Eα by the linear least-squares method indicates that:(a) the fraction of material reacted during the time lag prior to explosion at different temperature is equal;(b) the values of Eα and Aα obtained are acceptable and(c) assumption of adopting AαG(α) in derivation of Semenov′s formula are tenable;(3) using Tt=5s and ΔG≠ as criteria,the heat-resistance ability of six trinitromethyl explosives decreases in the order TNETBBTNFBTNEDATETNPTNMABTNNA.

6. Kinetic Study of the Explosive Decomposition Reaction of Small-scale Explosives Using the Time-to-explosion Experiment

HU Rong-zu1,ZHAO Feng-qi1,GAO Hong-xu1,ZHAO Hong-an2,FENG Guo-fu1,MA Hai-xia3,SONG Ji-rong3
1.Xi'an Modern Chemistry Research Institute,Xi'an 710065,China
2.College of Communication Science and Engineering,Northwest Univerisity,Xi'an 710069,China
3.College of Chemical Engineering,Northwest Univerisity,Xi'an 710069,China)

Abstract: The induction time(tind)prior to explosion of 10 explosives:3-nitro-1,2,4-triazol-5-one(NTO),lead 3-nitro-1,2,4-triazol-5-onate(PbNTO),potassium 3-nitro-1,2,4-triazol-5-onate(KNTO),ethyenediamine 3-nitro-1,2,4-triazol-5-onate(ENTO),composite explosives ammonium 3-nitro-1,2,4-triazol-5-onate(ANTO),JO-6,JOB-9003,JP-1,JD-1 and JH-16 at different temperature was measured by the time-to-explosion experiments of small-scale explosives.Their values of apparent activation energy(Eα)and pre-exponential constant(Aa)of the explosive decomposition reaction and critical temperature of thermal explosion(Tb),i.e.the values of T corresponding to tind=1000s in Semenov's equation were calculated from the relationship of lntint vs.1/Ti by the linear least-squares method.The values of Eα obtained by integral isoconversional non-linear method were used to check the values of Eα obtained by the linear-squares method.With the help of thermodynamic formulae,the thermodynamic parameters [free energy of activation(ΔG≠),enthalpy of activation(ΔH≠)and entropy of activation(ΔS≠)] of activation for the explosive decomposition reaction were calculated.The results show that(1)the heat-resistance ability of five single-compound explosives and five composite explosives using ΔG≠ and Tbas criteria decreases in the order NTOENTOANTOKNTOPbNTO and JP-1JD-1JO-6JOB-9003JH-6.(2)The fact of Eα=Eα indicates that the value of Aα obtained and assumption of adopting Aα G(α)in derivation of Semenov's formula are tenable.

7. Thermal Analysis of Viton A/Mg/NaNO_3 Fuel Rich System

ZOU Mei-shuai,GUO Xiao-yan,YANG Rong-jie,QIU Ri-yao
School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China)

Abstract: The thermal decomposition processes of magnesium,sodium nitrate,viton A and their mixing components were studied by differential thermal analysis(DTA) and thermogravimetry(TG) in order to obtain the condensed phase reaction mechanism of magnesium/sodium nitrate system.DTA and TG results showed that magnesium had a large mass loss after melting,the decomposition of sodium nitrate included different stages,and viton A decomposed completely in the narrow range of temperature.The thermal analysis for the mixtures indicated that the decomposition products of the viton A might react with magnesium,and with the decomposition products of sodium nitrate.The results suggest that fast decomposition of Mg/NaNO3 happened at 535℃,while it happened at about 380℃ after adding viton A to the system.

8. Influence of Several Metal-Oxide Catalyzers on Thermal Decomposition Performance of Double-base Propellant

DU Ping,LIAO Xin,WANG Ze-shan
School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: Thermal analysis(DTA) was adopted to study the thermal decomposition performance of double-base propellant by selecting several typical metal-oxides as catalyzers.The results show that the kinetic parameters of thermal decomposition reaction of the double-base propellants can be changed by some metal-oxide catalyzers.The activation energies and peak temperatures of thermal decomposition reaction of the doublebase propellants can be depressed by Fe2O3 and Pb3O4,and Fe2O3 has better effect.The activation energy and peak temperature of thermal decomposition reaction of double-base propellant can be raised by MoO3.Applying certain metal-oxide catalyzers to propellant,thermal decomposition performance and burning performance of propellant can be controlled.

9. Application of Pressure Data Obtained by Accelerating Rate Calorimeter

XU Zhi-xiang,HU Yi-ting,LIU Da-bin,YE Zhi-wen,WEI Yan-an
School of Chemical Engineering,Nanjing University of Science of Technology,Nanjing 210094,China)

Abstract: The pressure data of emulsion matrix and ammonium nitrate obtained by accelerating rate calorimeter experiments were treated,considering that the pressure data were available to analyze the thermal hazards of materials.Using the mechanism f(α)=1-α,the activation energy(E) of ammonium nitrate containing ferric nitrate based on pressure data is 197.35 kJ•mol-1,the value of E based on temperature data is 197.41 kJ•mol-1,indicating that it is available to use pressure data to analyze thermal hazards of materials and to calculate the activation energy of the reaction.

10. Thermal Decomposition Behavior of Emulsion Explosives Prepared by Multiple Emulsion

LUO Ning,LI Xiao-jie,WANG Xiao-hong,ZHANG Xiao-jun
The Department of Engineering Mechanics of State Key Laboratory of Structural Analysis for Industrial Equipment of Dalian University of Science,Dalian Liaoning 116024,China)

Abstract: Multiple emulsifier was prepared by T154,T155 and Span80.The thermal decomposition behaviors of four kinds of emulsion explosives prepared by multiple emulsifier agents were studied by DSC-TG technique.The thermal decomposition kinetic parameters of these emulsion explosives were calculated by Kissinger,Ozawa and atava-esták methods.Their thermal decomposition kinetic parameters and the most probable mechanism function were obtained by comparison of calculated results by three methods.

11. Cook-off Response Characteristics of Desensitizing RDX Explosive under Different Restriction Conditions

ZHI Xiao-qi,HU Shuang-qi,LI Juan-juan,XU Shuang-pei
North University of China,Taiyuan 030051,China)

Abstract: A slow cook-off test of desensitizing RDX cylinder with shells at a heating rate of 2 ℃/min is performed to investigate the response characteristics of desensitizing RDX explosive under different restriction conditions.The test results show that the response time increases with increasing the thickness of shell when material is same and drastic degree of explosive response weakens with the increase of the restriction.And the response time change with the change of physical characteristics of materials.The phenomenons are explained according to the theory of mechanics of materials and heat transfer,showing that the vulnerability of booster can be reduced by increasing thickness of shell and with the low thermal-conduct material.

12. Calculation Analysis of Thermal Stress of Propellant Grain in Ignition Process

WANG Ying-ze,ZHANG Xiao-bing
School of Power Engineering,NUST,Nanjing 210094,China)

Abstract: Based on the heat conduction mechanism of propellant grain in ignition process,the Fourier heat conduction law and non-Fourier heat conduction law are adopted to build the models describing the ignition process.The distribution of the thermal stress about propellant grain is achieved by the calculation formula of thermal stress.The mechanical property of the propellant grain and its fracture way is systematically analyzed by numerical calculation,and the microcosmic failure behaviors of the propellant grain under the conditions of thermal stress and combustion gas wave action in the ignition process are studied by the failure function.The reason of the breech blows is explored.

13. Thermal Decomposition Kinetics of Rock Emulsion Explosives

YIN Li1,GUO Zi-ru2,YANG Qing3
1.China Explosive Materials Trade Association,Beijing 100089,China
2.School of Chemical Engineering,Anhui University of Science and Technology,Huainan Anhui 232001,China
3.State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China)

Abstract: The thermal decompositions of emulsified bases of rock emulsion explosive and its two products sensitized by NaNO2 and NaNO2 and glass micro balloon respectively have been analyzed by DSC technique.The Flynn-Wall-Ozawa method,Friedman-Reich-Levi method,integral isoconversional non-linear method,Kissinger method,Achar method,Coats-Redfern method and Sˇatava-Sˇesták method were used to calculate the kinetic parameters such as activation energy,pre-exponential factor and to determine mechanism function.The results show that the three samples have almost the same activation energy and pre-exponential factor,which are about 110 kJ•mol-1 and 108-109 s-1,respectively.Their thermal decomposition mechanism are Avrami-Erofeev equation(n=2) at heating rates of 2.5,5.0 and 7.5 K•min-1and Jander equation(three-dimension diffusion,n=2) at the heating rates of 10 and 20 K•min-1.Therefore,the thermal decomposition behaviors of the three samples are almost the same,NaNO2 or glass micro balloon have little effect on the thermal decomposition of the emulsion base.

14. Thermal Decomposition Kinetics of 2,6-Diamino-3,5-dinitropyridine 1-oxide and Its Formulation Explosives

HE Zhi-wei1,GAO Da-yuan2,LIU Zu-liang1
1.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
2.Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang Sichuan 621900,China)

Abstract: The thermal decomposition processes of 2,6-diamino-3,5-dinitropyridine-1-oxide(ANPyO) explosive and its polymer bonded explosives were studied by TG at heating rates of 2.5,5,10,20 K•min-1,respectively.The thermal decomposition kinetic parameters and the mechanism functions of ANPyO explosive and its polymer bonded explosives were obtained by the integral iso-conversional non-linear(NL-INT) method and Ozawa′s method.The results show that ANPyO explosive and its polymer bonded explosives have good thermal stability below 210℃.The thermal decomposition mechanism of ANPyO explosive and its polymer bonded explosives are classified as random nucleation and growth of n=1.The activation energy(E),pre-exponential factor(A) and mechanism function of the thermal decomposition process of ANPyO explosive are 198.22 kJ•mol-1,2.743×1017 s-1 and f(α)=(1-α),respectively.The thermal decomposition kinetic equation for ANPyO is dαdt=kf(α)=A•eERT•f(α)=2.743×1017×(1-α)exp-2.384×104T.

15. Thermal Decomposition Characteristics of Double-base Propellant and Multi-nitrate Ester Propellant

GUO Song1,WANG Qing-song1,SUN Jin-hua1,LIAO Xin2,WANG Ze-shan2
1.State key Laboratory of Fire Science,University of Science and Technology of China,Hefei 230026,China
2.School of Chemical Engineering,Nanjing University of Technology,Nanjing 210094,China)

Abstract: The influence of initial mass with the unified volume on the thermal decomposition characteristics of the title propellants has been studied using a C80 calorimeter.The results show that as the initial mass increases,the exothermic peak on double-base propellant will shift to the lower temperature,the activation energy and the heat of reaction on double-base propellant decrease gradually,but the exothermic peak,the activation energy and the heat of reaction on multi-nitrate ester propellant do not shift.This difference is caused by extra HCHO produced by decomposition of TEGDN in NC/NG mixed system.

16. Thermal Decomposition Kinetics of RDX by TG-DSC-QMS-FTIR

LI Yan-chun,YAN Shi,CHENG Yi
School of Chemical Engineering, Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: The thermal decomposition process of RDX was investigated by TG-DSC-QMS-FTIR techniques.The result shows that RDX begins to decompose after melting.It is certain that the products have C,H2O,CH2O,N2O,CO,CO2 and NO2,maybe have CH4 and NH3,and have no NO.The kinetic parameters were calculated by non-linear regression.The results show that the decomposition process of RDX can be divided into three successive steps.The first step: activation energy 235kJ/mol,the pre-exponential factor log(A/s-1) 22,reaction order 0.64,the main products are CO2,NO2 and CH2O.The second step: activation energy 110kJ/mol, the pre-exponential factor log(A/s-1) 1.5,reaction order 1.7,the main products are N2O,H2O,CH4,NH3,C2O+/C3H+4,CN+/C2H+3 and CHO+/C2H+.The third step: activation energy 223kJ/mol,the pre-exponential factor log(A/s-1) 20.9,reaction order 4,the main products are C and CO.

17. Influence of Water Content in Emulsion Explosives Basic Substance on Their Thermal Decomposition and Calculation of Kinetic Parameters

MA Zhi-gang1,ZHOU yi-kun2,WANG Jin1
1.School of Chemical Engineering,Anhui University of Science and Technology,Huainan,Anhui Province,232001,China
2.Blasting Technology Research Institute,Academy of Sciences of Coal Mining)

Abstract: Two emulsion explosives basic substances with 3.46% and 12.27% water were prepared in order to study the influence of water content in emulsion explosives basic substances on the characteristics of thermal decomposition and chemical kinetic parameters.DSC and TG-DTG curves of the two samples under different heating rates were obtained by DSC-TG.Through comparing the extrapolated initial temperature,composition of emulsion basic substances and their curves,the influence of water content on the thermal stability and thermal dcomposition characteristics of basic substances was studied.Results show that at initial stage of heating up basic substances,the mass loss rate of basic substances is slow and steady and it is primarily caused by water loss no matter whether water content in basic substances is high or low.The water mainly comes from two sources: free water in basic substances and that released from some basic emulsion particles in broke emulsion basic substances when they are heated.The extrapolated initial temperature of low water-content basic substances is noticeably lower than that of high water-content basic substances.Compared with the common emulsion explosives basic substances,it is easier for powered emulsion explosives basic substances to decompose at a lower temperature. After the starting of decomposition,the heat release rate and mass loss of higher water-content basic substances is faster than that of lower water-content basic substances.The chemical kinetic parameters of the two emulsion explosives basic substances were calculated.

18. Thermal Decomposition Characteristics of Gram-level AP under the Constant Temperature Condition of 170℃

GUO Xin,NAN Hai,XI Peng,LI Xin
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal decomposition characteristics of gram-level AP at 170℃ is studied by using dry method at constant temperature and TG.The result shows that with increasing the heating time,the mass loss of gram-level AP increases,and the maximum mass loss reached in the second hour.The thermal decomposition processes of gram-level AP can be divided into three steps.The maximum mass loss is 32.19% and the maximum rate of reaction is 1.125 s-1.After heated at 170℃,the impact sensitivity of AP increases.

19. Thermal Safety of Plastic Bonded Explosives JH-94 and JO-96

HU Rong-zu,GAO Hong-xu,ZHAO Feng-qi
Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

Abstract: With the help of the onset temperature(Te) and peak temperature(Tp) from the non-isothermal DSC curves of PBX-JH-94 and PBX-JO-96 at different heating rates(β),the thermal decomposition activation energy(EK and EO) and pre-exponential constant(AK) obtained by Kissinger's method and Ozawa's method,the values of specific heat capacity(Cp),density(ρ) and thermal conductivity(λ) obtained by the specifications of standardization method GJB 772A-97-406.1,401.2 and 409.1,the decomposition heat(Qd,taking half-explosion heat),Zhang-Hu-Xie-Li's formula,Smith's equation and Wang-Du's formulas,the values(Te0 and Tp0) of Te and Tp corresponding to β→0,critical temperature of thermal explosion(Tb),adiabatic time-to-explosion(tTIad),thermal sensitivity probability density function [S(T)] vs.temperature(T) relation curves for infinite platelike,infinite cylindrical and spheroidic plastic bonded explosives JH-94 and JO-96 with half thickness and radius of 0.05m surrounded with surrounding of 373K,peak temperature corresponding to the maximum value of S(T) vs T relation curve(TS(T)max),safety degree(SD) and critical thermal explosion ambient temperature(Tacr) of PBX-JH-94 and PBX-JO-96 are obtained,showing that the thermal safety of PBX-JO-96 is greater than that of PBX-JH-94,and the accelerating tendency from adiabatic decomposition to explosion of the latter is less than that of the former.

20. Differential and Integral Isoconversional Non-linear Methods and Their Application in Physical Chemistry Study of Energetic Materials Ⅵ.Theory and Numerical Method Based on van′t Hoff-Ⅰ Formula

HU Rong-zu1,ZHAO Feng-qi1,GAO Hong-xu1,ZHANG Hai2,ZHAO Hong-an3,MA Haixia4
1.Xi′an Modern Chemistry Research Institute,Xi′an,710065,China
2.Department of Mathematics,Northwest University,Xi′an 710069,China
3.College of Communication Science and Engineering,Northwest University,Xi′an 710069,China
4.College of Chemical Engineering,Northwest University,Xi′an 710069, China)

Abstract: Eight typical differential and integral isoconversional non-linear equations based on van′t Hoff′s formula for computing the apparent activation energy(Eα) from isothermal and non-isothermal data are derived.The numerical methods of computing the value of Eα of decomposition reaction of energetic materials via the equations are presented.

21. Research on the Thermal Decomposition of NEPE Propellant Containing CL-20 by Situ/RSFT-IR

DING Li,ZHAO Feng-qi,PAN Qing,XU Si-yu,CHEN Zhi-qun
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal decomposition of NEPE propellant containing CL-20 was researched with the fast thermolysis reaction cell(gas reaction cell) in situ in conjunction with rapid scan Fourier transform infrared spectroscopy(fast thermolysis/RSFT-IR)and the solid reaction cell in situ in conjunction with rapid scan Fourier transform infrared spectroscopy(the solid reaction cell in situ /RSFT-IR).The gas product of thermal decomposition were obtained.The results show that:(1) the temperature of the volatilization and decomposition of NG increase by interaction of components and the temperature of decomposition of PEG decreases;(2) the thermal decomposition of CL-20, decompositing from solid phase directly,is different from that of RDX or HMX which melt before decomposition;(3) addition of AP shortens the process of decomposition and increase the heat release rate.

22. Effect of Potassium Picrate on Thermal Behavior and Ignition Properties of Nitramine Powder Containing RDX

WANG Zhi-xin1,2,LI Guo-xin1,JIANG Xin-guang1,LAO Yun-liang1,ZHANG Jian-fu2,LI Hao3
1.National Key Laboratory of Explosion Science and Technology,Beijing 100081,China
2.Military Representative Office of NO.474 PLA,Fushun Liaoning 113003,China
3.Military Representative Office in Dalian Area,Dalian Liaoning 110015,China)

Abstract: There are some disadvantages of nitramine powder containing RDX.First,it is difficult to ignite at low pressure;secondly,after being ignited the combustion pressure rises slowly.To improve its performance,the effect of potassium picrate on thermal behavior and ignition property of nitramine powder containing RDX was studied by DSC and a small closed bomb test.The results show that the decomposition exothermicity of KP compensates the melting endothermicity of RDX,potassium picrate can adjust the thermal behavior and improve the ignition property of nitramine powder,and the effect is more obvious when the mass proportion of KP to RDX is more than one.With the increase of the amount of KP in nitramine powder containing RDX,the ignition delay time can be reduced greatly and the ignition property can be improved.

23. Thermal Hazard in the Process of Mononitrotoluene Nitration

CHEN Li-ping1,CHEN Wang-hua1,LI Chun-guang2,PENG Jin-hua1,ZHANG You-ping2,LIU Rong-hai1,LU Li-ming3
1.Department of Safety Engineering,School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
2.Safety Technology Research Institute of Ordnance Industrial,Beijing 100053,China
3.MTEELER TOLEDO,Shanghai 200233,China)

Abstract: To get thermal hazard information in the process of forming dinitrotoluene from mononitrotoluene(MNT),DSC was used to test the thermal decomposition behaviors of these substance referred,and reaction calorimeter(RC1e) was used to study the heat generation in the reaction process.The results show that the decompositon of mixed acid easily took place and the onset temperature of decomposition reaction for mixed system after the reaction is 113.3℃.And the maximal temperature attainable by runaway of the desired synthetic reaction(MTSR) is lower than 100℃ if MNT dosing could stop as soon as cooling failure,or else,the adiabatic temperature arise can be higher than 140℃,and lead a secondary decomposition reaction.

24. Reaction Rule for Different Size PBX-2 Explosives in Fast Cook-off Test

DAI Xiao-gan,Lü Zi-jian,SHEN Chun-ying,XIANG Yong
Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: Fast cook-off tests for different size PBX-2 explosives were made by strengthening restriction.The temperature changing processes of different positions in the sample were measured by thermocouples,and the reaction degree of different size explosives was gained by blast pressure gauges.The reaction rule for different size PBX-2 explosives was analyzed by the results of fast cook-off test.The results show that the reaction of PBX-2 explosives is more violent with smaller size and weaker with larger size under the same thickness shell and definite restricted intension.

25. Numerical Modeling on the Accelerated Aging of GI-920 Explosive

GAO Da-yuan,HE Song-wei,HAN Yong,LU Bin
Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: The accelerated aging mechanism and effect of GI-920 explosive were analyzed to understand the effect of aging on detonation performances of GI-920 explosive.Based on the derived thermal decomposition kinetic equation,the density,composition and heat of formation on various decomposition extents of GI-920 explosive were calculated at accelerated aging temperatures of 70℃ and 75℃,respectively.The detonation parameters of GI-920 explosive under various aging conditions were computed by means of the VLWR code.The results show that the density,detonation velocity and detonation pressure were a little decreased after accelerated aging.

26. Thermal Decomposition Property of BNCP

ZHOU Jian-hua,CHENG Bi-bo,LI Jin-shan,LIU Jia-bin
Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: The thermal decomposition property of bis-(5-nitro-2H-tetrazolato-N2)tetraamine cobalt(Ⅲ) perchorate(BNCP) was investigated by DSC and compared with those of BTF and HNS-Ⅳ.The kinetic parameters of thermal decomposition of BNCP,BTF and HNS-Ⅳ were calculated by Kissinger′s method and Ozawa′s method.At 10℃/min BNCP has an exothermic peak on the DSC curve at 289.6℃,which is 25.4℃ larger than that of BTF,BNCP has the largest decomposition enthalpy compared with BNCP and BTF.BNCP is thermally stable under 100℃,which is confirmed by VST and TG. The apparent activation energy of thermal decomposition of BNCP by Kissinger′s method is 178.3kJ/mol,which is 46.4kJ/mol less than that of BTF and 43.1kJ/mol less than that of HNS-Ⅳ,and by Ozawa′s method is 187.5kJ/mol,being less about 33.8kJ/mol and 32.8kJ/mol than those of BTF and HNS-Ⅳ.

27. Experimental Study on Vulnerability Response of Propelling Charge to Thermal Stimuli

YANG Li-xia,ZHANG Zou-zou,LIU Lai-dong
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: In order to establish a method of assessing the vulnerability response of gun propellants and their charges,the vulnerability response characteristics and influence factors of typical propelling charge in fast cook-off test and slow cook-off test,and the mechanism of heat response were studied.The results indicate that the vulnerability response of the single-based propellant is the most intense under thermal stimuli,the response temperature of propellants to heating is consistent with the heat sensitivity(5s explosion temperature) of their formulation in slow cook-off test,the order from low to high is single-based propellant,TEGN propellant and double-based propellant,respectively,the higher the activation energy of propellants measured by DSC in high pressure,the more intense the vulnerability response is under thermal stimuli.

28. Thermal Behaviors of BAMO-AMMO and its Compatibility with Some Energetic Materials

SONG Xiu-duo,ZHAO Feng-qi,WANG Jiang-ning,GAN Xiao-xian,XIE Bo
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal behaviors of BAMO-AMMO,a copolymer of 3,3-diazidomethyl oxetane(BAMO) and 3-azidomethyl-3-methyl oxetane(AMMO),were investigated by DSC and TG-DTG.The compatibilities of BAMO-AMMO with some energetic materials including RDX,HMX,DNTF,Cl-20,AP,Al,NG,DIANP were discussed with vacuum stability test and DSC.The results indicate that thermal decomposition of BAMO-AMMO can be divided into two stages.The peak temperature of the first stage is 260.3℃,which is 51℃ higher than that of NC ;and the peak temperature of the second stage is 401.7℃.The compatibilities of BAMO-AMMO with RDX,HMX,Cl-20,AP,Al,NG and DIANP are better.The above-mentioned materials can be used as components in propellants.

29. The Interaction between the Components in NEPE Propellant Containing CL-20

DING Li,ZHAO Feng-qi,LIU Zi-ru, ZHANG La-ying,HENG Shu-yun
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal decomposition characteristics of NEPE propellant containing CL-20(CL-20-NEPE propellant) and interaction between the components,such as NG,CL-20 and AP in NEPE propellant containing CL-20,were studied by thermogravimetry(TG).The results show that the thermal decomposition of CL-20-NEPE propellant proceeds in three stages,firstly the volatilization and decomposition of nitrate ester,secondly the decomposition of PEG and CL-20,thirdly the decomposition of AP.The decomposition of NG and PEG in binder were improved with the existence of CL-20 and AP.The improving effect of CL-20 is greater than that of AP for the decomposition of NG and PEG in binder.The decomposition temperature of AP decrease because of the decomposition product of CL-20.The interaction between Al and other ingredients is not obvious.

30. Effect of DNTF Content on Thermal Decomposition Characteristics of CMDB Propellants

REN Xiao-ning,HENG SHU-yun,LIU Zi-ru,WANG Jiang-ning,ZHANG Gao,ZHENG Wei
Xi′an Mordern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal decomposition behaviors of four CMDB propellants with different DNTF content were investigated by PDSC and TG-DTG.The thermal decomposition characteristics and regulation of the propellants under different pressure conditions were analyzed.The effect of DNTF on the thermal decomposition characteristics of these propellants was studied.The results show that the content of DNTF had obvious influence on the thermal decomposition characteristics of CMDB propellants.The different additions of DNTF changed the decomposition regulation and made the decomposition process longer.The PDSC peaks of propellants were changed by pressure.

31. Combustion and Thermal Decomposition of Ammonium Dinitramide

ZHAI Jin-xian,YANG Rong-jie,LI Xiao-dong
School of Materials Science and Engineering,Beijing Institute of Technology, Beijing 100081, China)

Abstract: The effect of organ-metallic compound OME on the combustion and thermal decomposition of ammonium dinitramide (ADN) was investigated by burning rate measurement, DSC and TG. It is shown that OME can increase the burning rate of ADN within the pressure intervals of 1～12MPa. TG and DSC tests for ADN and ADN+1%OME indicate that the initial decomposition temperature of ADN can be decreased by the addition of OME noticeably. Furthermore the initial decomposition temperature of ADN is subject to the content of OME evidently. Kinetic analysis for DSC and TG data show that the activation energy of thermal decomposition of ADN has been decreased by about 30% by the addition of 1% OME to ADN.

32. Studies on the Combustion Characteristics and the Thermal Behavior of CMDB and NEPE Propellants with 1,3,3-Trinitroazetidine

LI Ji-zhen,ZHANG Wei,WANG Bo-zhou,FAN Xue-zhong,LIU Zi-ru
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The combustion characteristics of two types of propellants (TZ-CMDB and TZ-NEPE propellants) containing 1,3,3-trinitroazetidine (TNAZ) were studied by the determination of burning rate and analysis of flame structure, and the thermal behavior of TZ-CMDB and TZ-NEPE propellants were studied by TG-DTG and high pressure DSC. The effects of TNAZ on the combustion characteristics of the propellants and on the decomposition of other components in the propellants were described. The results show that the volatilization, sublimation or decomposition of TNAZ occur in the first mass-loss step on TG curve .With increasing the content of TNAZ in the propellants,the burning rate and pressure exponent of the propellants had little change and the flame of the propellants became less luminous. The decomposition of TNAZ was remitted to the second step on DSC curve where TNAZ decomposed together with RDX.

33. Study on the Deflagration Reaction Kinetics and Thermal Decomposition of Hexanitrohexaazaisowurtzitane

XIAO He-miao, YANG Rong-jie
School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081,China)

Abstract: An experimental equipment of measuring the deflagration delay time (τ) of energetic materials was built up. The values of τ of hexanitrohexaazaisowurtzitane (HNIW) were studied at the temperature of 507～547 K and pressure of 0.1～9.1 MPa. When temperature is increased, the deflagration delay time is decreased. The results show that at 507 K and 517 K, the high pressure (≥ 5 MPa ) makes τ increase, and at 527K and 537 K, the pressure does τ shorten. Deflagration reaction kinetic parameters at different pressures were calculated. The activation energy of deflagration reaction of HNIW increases with pressure. The thermal decomposition of HNIW at different temperatures (≤ 489 K) and pressures were investigated. The results show that pressure retards the thermal decomposition of HNIW.

34. The Influences of Solvents and Temperature on Polymorphs and Thermal Stability of ε-HNIW

LIU Jin-quan,OU Yu-xiang,JIN Shao-hua,CHEN Bo-ren
School of Science of Materials and Engineering,Beijing Institute of Technology, Beijing 100081,China)

Abstract: Polymorphs and thermal stability of hexanitrohexaazaisowurtzitane (HNIW) have attracted much attention of many researchers.ε-HNIW was heated at 70℃ for 4hours in four solvents (water, toluene, heptane and cyclohexane) respectively. The FTIR spectra and DTA curves of the four heated samples were recorded, and compared with the unheated sample. FTIR spectra indicate that the polymorphs of all heated ε-HNIW remain unchanged .DTA curves show that the differences of thermal decomposition peak temperature between the unheated sample and the four heated samples are 0～2.6℃, 0～2.6℃,1～1.9℃, and 0～2.5℃ at four heating rates of 2, 5,10 and 20℃/min respectively. In addition,the observed activation energy of the four heated samples has been obtained using both Kissinger method and Ozawa method . The error between the calculated results from these two methods rings ca 2%.It could be concluded that the thermal stability of the four heated samples exhibits no appreciable changes.

35. The Effect of Nano-LaCoO_3 on the Thermal Decomposition and Sensitivity of RDX Explosive Mixture

XUE Ai-lian, HUANG Yin-sheng, KANG Cong-cheng, WANG Ying-hua, LI Ji
School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: The effect of nano-LaCoO_3 on the thermal decomposition characteristics of RDX explosive mixture containing ammonium perchlorate was investigated by DSC and DTA. The results show that nano-LaCoO_3 has catalytic activities to the thermal decomposition characteristics of RDX explosive mixture. The results of sensitivity tests show that the nano-LaCoO_3 makes the impact sensitivity and thermal sensitivity of these explosive mixture decrease and the friction sensitivity of the mixture increase.

36. Evaluation of the Reactivity of HMX with Materials by Use of the Time to Complete Melting and Decomposing (TCMD) of Isothermal DSC Curve

HU Rong-zu~(1,2),ZHAO Feng-qi~1,GAO Sheng-li~2,SONG Ji-rong~3, SHI Qi-zhen~2
1. Xi′an Modern Chemistry Research Institute, Xi′an 710065, China
2. Department of Chemistry, Northwest University, Xi′an 710069, China
3. College of Chemical Engineering, Northwest University, Xi′an 710069, China)

Abstract: The isothermal DSC measurement is used to test the reactivity of various materials with HMX by measuring the time to complete melting and decomposing (TCMD). The results show that TCMD is an accurate screening criterion for materials which will be added to and in contact with HMX.

37. Ignition Performance of Fuel-rich Solid Propellants Containing Magnesium-Aluminum

XIAO Xiu-you~1, LI Bao-xuan~1, WANG Yu-ling~2, WANG Ying-hong~1, HU Song-qi~1
1. College of Astronautics, Northwestern Polytechnic University, Xi′an710072, China
2. Second Artillery engineering college, Xi′an710025, China)

Abstract: The ignition performance of fuel-rich propellants which contain metal fuel such as Magnesium-Aluminum powders or combines of Magnesium-Aluminum powders and Boron powders is measured with Crawford bomb and the pressure conditions of ignition experiment are atmosphere and pressurized separately. The contents of AP oxidizer and Magnesium-Aluminum alloy fuel in propellant samples are from 30% to 53% and from 20% to 40% respectively. Experimental results reveal that the ignition performances of propellant samples under the fixed heat input condition are closely related to oxidizer content and its particle size distribution. The kinds of metal fuel as well as its contents also have influences on ignition delay time in some degree. The catalyst and pressure almost have no effects on ignition delay time. The method of testing ignition delay is simple, easy and reliable, and can satisfy the need of tailoring fuel-rich propellant formulations

38. Nonisothermal Kinetics of Free-radical Polymerization of 2,2-Dinitropropyl Acrylate

ZHANG Gong-zheng,WANG Fang
School of Chemical Engineering and Environment,Beijing Institute of Technology,Beijing 100081,China)

Abstract: The free-radical bulk polymerization of 2,2-dinitropropyl acrylate(DNPA) in the presence of 2,2′-azobisisobutyronitrile(AIBN) was investigated by nonisothermal DSC method.Kissinger and Ozawa methods were applied to determine the activation energy(Ea) and reaction order of the free-radical polymerization.The results show that the peak temperature of exothermic polymerization increases with the increasing heating rate at DSC curves in different heating rates.The reaction order of nonisothermal polymerization of DNPA in the presence of AIBN is approximately 1.The average activation energy of the free-radical polymerization is(89.3±1) kJ • mol-1.

39. Adiabatic Decomposition of No.3 Permissible Expanded Ammonium Nitrate Explosive

ZHOU Xin-li,LIU Zu-liang,Lü Chun-xu
School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: In order to investigate the thermal stability and thermal decomposition properties of a new kind of permissible expanded ammonium nitrate explosive,adiabatic thermal decomposition of No.3 permissible expanded ammonium nitrate explosive is studied by accelerating rate calorimeter. Temperature,pressure and temperature rise versus time curves,pressure and temperature rise versus temperature curves are obtained respectively.Thermal decomposition results indicate that its adiabatic thermal decomposition is divided into three stages,and kinetic parameters such as apparent activation energy Ea=239.718 kJ/mol,pre-exponential factor A=4.697×1024 min-1and reaction heat ΔH=621.66 J/g have been calculated respectively,according to measurement data.The test results show that initial decomposition temperature of No.3 permissible expanded ammonium nitrate explosive is higher than 214.75 ℃,and possesses better thermal stability,so it can be safely used in coal mine.

40. Thermal Decomposition Behavior and Non-isothermal Decomposition Reaction Kinetics of CL-20 with Leads Salts as Catalyst

XU Jin-xiang
Beijing University of Science and Technology,Beijing 100081,China)

Abstract: The thermal behavior and kinetic parameters of the exothermic decomposition reaction of hexanitrohexaazaisowurtzitane(CL-20) and systems CL-20/PbCO3,CL-20/φ-Pb and CL-20/β-Pb in a temperature-programmed mode have been investigated by means of DSC and TG-DTG.In order to obtain their kinetic parameters of the decomposition reaction,the six differential and integral methods were employed.The results show that the kinetic model function in differential form is f(α)=4(1-α)[-ln(1-α)]3/4 and the mechanism of the exothermic decomposition reaction of CL-20,CL-20/φ-Pb and CL-20/β-Pb is nucleation and growth mechanism(Avrami-Erofeev equation n=1/4).

41. Investigation on Thermal Decomposition of Mixed Systems of AP with RDX and HMX by DSC-TG-FTIR

LIU Zi-ru,SHI Zhen-hao,YIN Cui-mei,ZHAO Feng-qi
Xi′an Modern Chemistry Research Institute,Xi′an 710065 ,China)

Abstract: The thermal decomposition of RDX/AP,HMX/AP and RDX/HMX/AP mixed systems were investigated by DSC,TG-DTG and simultaneous DSC-TG-FTIR.The characteristic values of DSC and TG-DTG curves and the gas products of decomposition for the systems mixed with AP were measured and compared with those for RDX and HMX components and RDX/HMX system.The results show that there is a strong interreaction of AP with RDX and HMX,especially with HMX.The carbon oxides such as CO,CO2 and CH2O also appear in decomposition temperature range of AP that not contain carbon for the mixed systems,showing that the part products or residual of RDX and HMX decompositions are simultaneously decomposed with AP for these mixed systems.

40. Decomposition Mechanism and Non-isothermal Reaction Kinetics of Cerium Citrate

YI Jian-hua,ZHAO Feng-qi,GAO Hong-xu,XU Si-yu,HU Rong-zu,WANG Yuan
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal behavior,mechanism and kinetic parameters of the exothermic decomposition reaction of cerium citrate(CITCe) in a temperature-programmed mode have been investigated by means of DSC,TG/DTG and condensed phase thermolysis/FTIR.The kinetic equations of the decomposition reaction have been obtained.The results show that there are one dehydration stage and two exothermic reaction stages in the decomposition of cerium citrate.The apparent activation energy and pre-exponential factor of the main exothermic decomposition reaction at 0.1MPa are 148.59kJ•mol-1and 1011.64s-1,respectively.The kinetic equation can be expressed as:dα/dt=1011.81(1-α)[-ln(1α)]1/3e-1.79×104/T,and the mechanism obeys Avrami-Erofeev equation with n=2/3.The critical temperatures of thermal explosion of cerium citrate obtained from the onset temperature(Te) and the peak temperature(Tp) are: Tbe=527.09K,Tbp=542.71K.ΔS≠,ΔH≠ and ΔG≠ of the reaction are calculated as: 16.82J•mol-1•K-1,163.11kJ•mol-1 and 158.74kJ•mol-1.

41. Research on the Interaction between CL-20 and NC-NG System via DSC/TG-MS

WANG Xiao-hong,HENG Shu-yun,ZHANG Gao,LIU Zi-ru,SHI Zhen-hao,TAN Hui-min2
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.School of Material Science and Engineer,Beijing Institute of Technelogy,Beijing 100081,China)

Abstract: The interaction between CL-20 and NC-NG system was investigated by using DSC/TG-MS technique.The result shows that on the grinded condition,the decomposition process of CL-20 and NC-NG systems has no obvious chemistry interaction,but have some physics interaction.CL-20 makes that the sublimation process of NG move up evidently,the total proton peak temperature move forward,and the decomposition process of CL-20 and NC-NG systems delay,the total proton peak temperature move backwards.

42. Thermal Decomposition Performance of JMZ Propellants and Related Compositions

HE Wei-dong,XU Wan-yu
Department of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: The thermal decomposition performance of JMZ gun propellants containing PET(copolyether of tctrahydrofuran and epoxy ethane) binder and their related compositions was studied by TG and DTA.The activation energy of thermal decomposition reaction of some different formulations was calculated by Kissinger′s method.The thermal decomposition process and related factors affecting the process were analyzed.The results show that DTA curves of PET propellants indicate two exothermic peaks.With increasing the contents of NC,the activation energy of PET propellant system elevates when NC is added to the propellant system.Results show that thermal decomposition process of PET propellants can be divided into two stages: the first stage is the volatilization and decomposition of mixed nitrate and NC,and the second step is the decomposition of nitramine and PET.The addition of NC in the propellant system makes the thermal stability of the propellant system increase.

43. Determination of Probable Mechanism Function and Kinetic Parameters of Thermal Decompostion Reaction of Double-base Propellant by a Single Non-isothermal DSC Curve

HU Rong-zu,ZHAO Feng-qi,GAO Hong-xu,XU Si-yu,YI Jian-hua,GAO Yin
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Under linear temperature increase condition,thermal behaviors,mechanism function and kinetic parameters of thermal decomposition reaction of double-base gun propellant CB0617 obtained with a model CDR-1 DSC instrument are reported.The data are fitted to the integral,differential and exothermic rate equations by linear least-squares,iterative,combined dichotomous and least-squares methods,respectively.The apparent activation energy(Ea),pre-exponential constant(A) and probable mechanism function in differential form of thermal decomposition reaction of double-base propellant CB0617 obtained by the logical choice method are 145.23kJ/mol,1013.27s-1 and f(α)=(1-α)0.90,respectively.The values of Ea and A are in good agreement with the calculated values: Ea=146.31kJ/mol and A=1013.35s-1 obtained by the integral equation and Ea=148.77kJ/mol and A=1013.69s-1 obtained by the differential equation.

44. Study on Interaction of Double-base Component with Some High Energy Oxidizers by Thermal Analysis

ZHANG La-ying1,HENG Shu-yun1,LIU Zi-ru1,ZHANG Gao1,ZHAO Feng-qi1,TIAN Hui-min2
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.School of Material Science and Engineering,Beijing Insititute of Technology,Beijing 100081,China)

Abstract: The PDSC and TG-DTG techniques were used to investigate the interactions of double-base component with CL-20,DNTF, TNAZ and ADN.The results show that the interaction of CL-20,DNTF,TNAZ,ADN with double-base component is not obvious at normal pressure,but became stronger at high pressure.The decomposition products of the double-base component in the mixture system can accelerate the decomposition of these high energy oxidizers at high pressure.

45. Thermal Decomposition Behavior of Mixed Nitric Ester Gun Propellant under Dynamic Atmosphere

XU Si-yu,YI Jian-hua,JIA Yong-jie,ZHANG La-ying,PEI Qing,LI Shang-wen
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Thermal decomposition behavior of gun propellant containing triethyleneglycol dinitrate(TEGDN) was studied by TG and DSC techniques under dynamic atmosphere.The results show that the thermal decomposition process of mixed nitric ester gun propellant is divided into two stages: nitric ester evaporates and decomposes in the first stage,nitrocellulose(NC) and C2 decompose in the second stage.The lost weight and DTG peak point of the two stage processes changed with the different proportions of TEGDN and NG.There is only one obvious exothermic peak in the DSC curves under different pressures,and the peak temperature decreases with pressure increase.

46. Non-isothermal Thermal Decomposition Reaction Kinetics of TEGDN Gun Propellant

YI Jian-hua1,XU Si-yu1,MA Xiao-dong2,ZHENG Lin1,GAO Hong-xu1,ZHAO Feng-qi1,HU Rong-zu1
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.Miliary Office,Xi′an North Huian Chemical Industrial Lt.Co.,Xi′an 710302,China)

Abstract: The decomposition reaction kinetics of gun propellant TG0604 was investigated by non-isothermal method with TG-DTG under atmospheric pressure and ambulatory atmosphere conditions.The results show that there are two reaction stages in the decomposition process of gun propellant TG0604.The decomposition reaction mechanism of stage I obeys Mample single-file law with n=1,the kinetic parameters are obtained as: Ea=79.09kJ•mol-1,A=107.40s-1,and the kinetic equations can be expressed as:dα/dt=107.40(1-α)e-0.95×104/T;The decomposition reaction mechanism of stage II obeys three-step chemical reaction rule,the kinetic parameters are obtained as: Ea=214.79kJ•mol-1,A=1021.49s-1 and the kinetic equations can be expressed as:dα/dt=1021.19(1-α)3e-2.58×104/T.The critical temperatures of thermal explosion of gun propellant TG0604 obtained from the onset temperature(Te) and the peak temperature(Tp) are: Tbe=461.51K,Tbp=478.17K.ΔS≠,ΔH≠ and ΔG≠ of the two stages are calculated as: for stage I,-86.70J•mol-1•K-1,80.54kJ•mol-1 and 417.98kJ•mol-1;for stage II,214.78J•mol-1•K-1,236.95kJ•mol-1 and 136.07kJ•mol-1.

47. The Thermal Decomposition Kinetics of Water Gel Explosives

WANG Jin1,MA Zhi-gang1,LIU Zhi-bing2
1.Anhui University of Science and Technology,Huainan Anhui 232001,China
2.Blasting Technology Research Unit of Coal General Institute,Huaibei Anhui 235039,China)

Abstract: In order to study the thermal decomposition characteristics and the kinetic parameters of water gel explosives,the initial temperature and the maximum peak temperature of the thermal decomposition reaction of rock water gel explosive and coal mine permissible water gel explosive have been determined by means of non-isothermal thermogravimetry(TG) and differential scanning calorimetry(DSC) at heating rates of 2.5,5.0,10.0,20.0,40.0K/min-1.The kinetic parameters of the reaction for water gel explosives are calculated by Kissinger method and Ozawa method.With the help of these parameters,the rate constants of the reaction at 120℃,150℃,250℃ are obtained and the iso kinetic temperature point is calculated.The result shows that the thermal stability of coal mine permissible water gel explosive is better than that of rock water gel explosive.

48. Analysis and Test on Combustible Gas Output Dynamic Parameter Features of Initiating Explosive Devices

FU Yong-jie1,2,YAN Nan1
1.State Key Laboratory of Prevention and Control of Explosion Disasters,Beijing Institute of Technology,Beijing 100081,China
2.92493 Army 89 Unit,Huludao Liaoning 125000,China)

Abstract: Based on the research of overseas and domestic initiating explosive device handbooks and the investigation of user units,the signal features representing the combustible gas output power parameters,such as pressure,thrust,acceleration,temperature,displacement and speed,are synthetically analyzed for the present initiating explosive devices.The characteristic quantity ranges about parameter type,amplitude and response frequency are presented.Based on output characteristics of various kinds of initiating explosive devices,sensor,signal amplifier and data acquisition instruments are selected and a multiplexed measuring system of initiating explosive device test dynamic parameter is established.Many physical quantity can be tested at the same time in one test via this system.More information and analyses of the relation between the parameters can be received.These features have an important value for the design of initiating explosive device output performances and the establishment of their measurement system.

49. The Light Detection of Free Radical on HMX,CL-20 and DNTF

MA Hai-xia1,2,SONG Ji-rong2,HU Rong-zu3,ZHAO Feng-qi3
1.Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094,China;
2.College of Chemical Engineering/Shannxi Key Laboratory of Physico-Inorganic Chemistry,Northwest University,Xi′an 710069,China
3.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: In order to investigate the safety and instantanity of thermal decomposition process of energetic material,the free radicals of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX),hexanitrohexaaz-aisowurzitane(HNIW,CL-20) and 3,4-dinitrofurazanfuroxan(DNTF) were measured by Electron Spin Resonance(ESR).In the same light intensity and time-interval,the ESR spectrometris of the three compounds were obtained.The results show that the free radical signal of DNTF appeared without light,however,the free radical signal of CL-20 and HMX appeared after receiveing some energy from the light.The quantites of their free radical was increased with the time expanded under the light and the signal of DNTF is the strongest among the three energetic materials.

50. Thermal Decomposition Characteristics of PYX

CHANG Hai
School of Natural and Applied Science,Northwest Polytechnical University,Xi′an 710072,China)

Abstract: The thermal decomposition process of 2,6-hexanitrodiphenyl-amine-3,5-dinitropyridine(PYX) was investigated by TG/DTG,TG/FTIR,TG/MS and therolysis rapid scan FTIR coupling techniques.The results show that the thermal decomposition process can be divided into two steps: the C-NO2 is omerizating to C-ONO,cyclization of-NH-and-NO2,releasing NO and forming polyacryl compounds in the first step,and polyacryl compounds decomposing and releasing HCN,CO,CO2 and H2O gases in the second step.

51. Interrupted-burning Test Study of Interaction between Plasma and Propellants

XIAO Zheng-gang,YING San-jiu,XU Fu-ming,HOU Bao-guo
Department of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: Interrupted-burning phenomena of different propellants such as triethyeneglycol dinitrate(TEGDN),double-base propellants,nitramine propellants and single-base propellants ignited by plasma are studied by interrupted-burning setup.With the help of the obtained microscopy images of recovered specimens and interrupted-burning pressure vs.time curves,the interaction rule between plasma and propellants with different formulas is discussed.The results show that burning surface of propellants is not regular because of plasma ablation and radiation.Ignition delay time of different propellants is not same and ignition delay time of TEGDN propellants is the shortest and the ignition by plasma easily takes place.The physicochemical properties of propellants,such as ingredient of propellant and additive,surface statue,optical adsorption coefficient and thermal conduction coefficient,et al,have significant effect on their plasma ignition performance.

52. Thermal Decomposition Characteristics of Trimethylolpropane Trinitrate

CUI Jian-lan1,2,ZHANG Yi1,CAO Duan-lin1
1.Department of Chemical Engineering,North University of China,Taiyuan 030051,China
2.The College of Pharmaceuticals & Biotechnology,Tianjin University,Tianjin 300072,China)

Abstract: The thermal decomposition characteristics of trimethylolpropane trinitrate(TMPTN) were investigated by means of high pressure DSC.It is showed that even though the structure of TMPTN is similar to that of nitroglycerin(NG) and trimethylolethane trinitrate(TMETN),the thermal decomposition characteristics of TMPTN is different from that of NG and TMETN.At normal pressure,the DSC curve of TMPTN has two peaks: one is melting endothermic peak and the other is exothermic decomposition peak,while NG has only an endothermic peak and TMETN has an exothermic decomposition peak,without melting endothermic peak.At the condition of high pressure,TMPTN has two similar peaks, but the melting endothermic peak is not evident comparing with that at normal pressure.The shape,temperature and quantity of heat of decomposition peak greatly change with different pressures.The kinetic parameters of thermal decomposition of TMPTN are obtained,and the decomposition mechanism of TMPTN is preliminarity analyzed.

53. Thermal Decomposition Property of Superfine Hexanitrostilbene(HNS-Ⅳ)

ZHOU Jian-hua,CHI Yu,WANG Xin-feng,LI Jin-shan,SHEN Yong-xing
Institute of Chemical Materials,CAEP,Mianyang Sichuan province 621900,China)

Abstract: In order to obtain the thermal decomposition property of superfine hexanitrostilbene(HNS-Ⅳ),the thermal decomposition of superfine hexanitrostilbene(HNS-Ⅳ) was investigated by DSC-TG technique.The kinetic parameters of thermal decomposition of HNS-Ⅳ were calculated by Kissinger method and Ozawa′s method.Experimental results show that the thermal stability of HNS-Ⅳ is comparative to that of HNS-Ⅱ.The apparent activation energy of thermal decomposition of HNS-Ⅳ obtained by Kissinger and Ozawa′s methods are 221.4kJ/mol and 220.3kJ/mol,respectively,being 27kJ/mol less than that of thermal decomposition of HNS-Ⅱ under static air condition.

54. Thermal Decomposition Kinetics of F_(2314) Bonder

GAO Da-yuan,HE Bi,HE Song-wei,ZHOU Jian-hua,SHEN Yong-xing
Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: The thermal decomposition process of F_(2314)bonder is studied by the DSC-TG curves at the heating rates 5,10 and 20K/min and in the tempeature range of 20～500℃.The thermal decomposition kinetic parameters and the mechanism function of F_(2314) bonder are obtained by Coats-Redfern method.The results show that the initial temperature of F_(2314) bonder on TG curves are approximately same,the final temperature increases with increasing the heating rate.At the same time,DSC curve at a heating rate of 10K/min consists of one endothermic melting peak and one exothermic decomposition peak.The F_(2314) bonder have better thermal stability at temperatures lower than 360℃.The activation energy,pre-exponential factor and mechanism function of thermal decomposition of the F_(2314) bonder are 294.76kJ/mol,10~(21.62)s~(-1) and f(α)=(1-α)~(4),respectively.

55. Thermal Decomposition of AP Catalyzed by Carbon-Coated Iron,Cobalt and Nickel Nano-Composite Materials

ZHAO Jun~1,XU Fu-ming~1,ZHOU Weiliang~1,LIU Jian-min~2
1.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
2.Xi′an Northern Huian Chemical Industry Co.Ltd.,Xi′an 710302,China)

Abstract: Carbon-coated Ni,Co and Fe nano-composite materials were prepared by pyrolysis of M-exchanged cation exchange resin(M-PAA) at 400℃,500℃,600℃,and their catalytic effects on the thermal decomposition of ammonium perchlorate(AP) were also studied.X-ray diffraction(XRD) and transmission electron microscope(TEM) results showed that the average particle sizes of Ni,Co and Fe in M/C obtained at 500℃(M/C-500) were 13nm,18nm and 20nm,respectively.DTA was employed to test the thermal decomposition of AP in the M/C and AP mixture.Results indicated that the catalysis of M/C-500 incrcases with increasing the content of M/C-500 and the decomposition temperature at high temperature decomposition zone of AP was lowered with the addition of M/C,and the high temperature decomposition peaks of AP lowered as much as about 54.5℃,79.3℃ and(156.2℃),respectively with addition of Ni/C-500,Fe/C-500 and Co/C-500.The high and low temperature decomposition peaks of AP overlapped with addition of Co/C-500.

56. Thermal Decomposition of RDX and HMX Explosives Part III: Mechanism of Thermal Decomposition

LIU Zi-ru~1,LIU Yan~2,FAN Xi-ping ~3,ZHAO Feng-qi~1
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.Beijing Chemical Defense ResearchInstitute,Beijing 102205,China
3.Beijing Institute of Technology,Beijing 100081,China)

Abstract: The thermal decomposition mechanism of RDX and HMX were in brief reviewed.The competing reactions of N-N and C-N bonds splitting occurred in initial stage of RDX and HMX decomposition are affected by the experimental conditions and sample phase state.The main gas products of decomposition were identified by DSC-FTIR coupling technique.The changes of the main function groups in condensed phase were measured by a in situ thermolysis cell/FTIR technique.The main gas products of RDX and HMX decomposition consist of N_2O,CH_2O,CO,CO_2,H_2O and HCN.The double peaks appear on the curves of temperature dependence of IR absorbance of CH_2O and H_2O for RDX.The two different rates of IR absorption intensities occur on temperature dependence of 1589cm~(-1)and 1278cm~(-1)bands attributed to-NNO_2 for RDX.On the basis of view point for the competing reactions,the results of thermal analyses and product analyses for RDX and HMX decompositions are explained.

57. Thermal Decomposition Characteristics of a Novel High Energy Density Material DNTF

REN Xiao-ning,WANG Jiang-ning,YIN Cui-mei,YU Hong-jian,HENG Shu-yun,YUE Pu
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The thermal decomposition of 3,4dinitrofurazanofuroxan(DNTF) and its interreaction with catalyst were investigated by using DSC and TG.The decomposition characteristics and regulation of DNTF under different pressure conditions were analyzed.The results showed that when the pressure increase,the endothermic fusion peak temperature of DNTF is almost constant,but the major exothermic decomposition peak temperature at 2MPa shifts to higher temperature and the decomposition become more violent.Compared to the atmospheric,the decomposition heat gain obviously and with increasing of the pressure the secondary decomposition peak after the main decomposition peak is gradually obvious.Under the pressure function,the decomposition gasouss products enhance the catalytic effect to product in coacervate phase,appearing the secondary decomposition.The kinetic parameters of DNTF decomposition were obained,and the values of E_a and lnA are 58.8kJ/mol and 1.08s~(-1) for ambient pressure,and 205.1kJ/mol and 33.64s~(-1) for 2MPa respectively.These results show that the significant changes in decomposition process occur under high pressure.The effects of pressure and catalyst on the thermal decomposition process of DNTF is obtained.

58. Thermal Decomposition Performance of High-Energy TEGDN Propellant

XU Wan-yu,HE Wei-dong,ZHANG Ying
Chemistry School,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: Thermal decomposition effect of TEGDN propellant caused by RDX content has been studied by TG and DSC.The results show that thermal decomposition process of high-energy TEGDN accomplished stage by stage,nitric ester thermal decomposition in the first stage and RDX thermal decomposition in the second.With RDX content increasing,quantity of heat decrease in the first stage and increase in the second stage.Heat in each stage has exponential relation with RDX content,and thermal weightlessness has linear relation with RDX content.The results provide academic and experimental basis for the application of the propellant.

59. Investigation on Thermal Behavior of PYX by Infrared Spectral Analysis

JIN Peng-gang,CHANG Hai,CHEN Zhiqun,PAN Qing,LIU Zi-ru,WANG Yuan
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: In order to study the thermal behavior of PYX,the whole process of the thermal decomposition of PYX was investigated by thermolysis in-situ cell rapid scan IR,Temperature-Jump rapid scan IR and TG-IR coupling techniques.The condensed and gas products in thermal decomposition process were measured.The possible thermal decomposition mechanism was proposed.The thermal decomposition process of PYX can be divided into two stages at least.The frist step is the isomerization of C-NO_2 and the cyclazocine of C-NO_2and(-NH),forming NO and some polyacryl compounds.The second step is the decomposition of polyacryl compounds,releasing HCN,CO,CO_2 and H_2O gases.

60. The Effects of Combustion Catalyst on the Thermal Decomposition of ADN

WAN Dai-hong~1,FU Qin~2,HUANG Hong-yong~2,LU Guo-qiang~2
1.Institute of Aerospace and Material Engineering,Nation University of Defence Technology Changsha 410073,China
2.Shanghai Xinfeng Chemical Institute,Huzhou zhejiang 313002,China)

Abstract: The effects of about ten kinds of combustion catalyst on the thermal decomposition of ADN were thoroughly studied by DTA and TG experiments under linear temperature increase condition and isothermal TG experiment.The kinetic parameters of the thermal degradation of ADN and mixture of ADN/catalyst was calculated by the DTA results at heating rate of 2,5,10,20℃•min~(-1).The results show that the catalysts(except Fe_2O_3) containing Fe or Cu obviously affect the thermal decomposition of ADN and make the thermolysis peak temperature decrease and the rate of mass loss of ADN expedite.The effects of the catalysts containing Cu were more salient,and their catalytic mechanism attribute to coacervation phase catalysis,and the catalytic mechanism of the catalysts which contains Fe belong to gas phase catalysis.While the catalysts containing ammonium salt or Ca as a result of NH_3 produced which bates proton diverting or better thermal stability matter coming into being during the thermal decomposition of mixture of ADN/catalyst,make the thermolysis peak temperature(T_p) and activation energy(E_a) of ADN increase,restraining the thermal decomposition of ADN.

61. Advance of Thermal Decomposition Chemistry of Energetic Materials under Combustion Condition

LIU Zi-ru,ZHANG La-ying
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: New advance of recent years in the investigation of thermal decomposition chemistry of energetic materials under combustion condition was reviewed.The contents consist of the thermal decomposition at simulated combustion condition,interaction of the components of energetic maerials,an influence of physical state on thermolysis and measurement techniques etc.The objects of study were remarked which are the great importance of elementray reaction of thermal decomposition to build combustion new model of propellants,the interactions of oxidants with adhesives and catalysts,and the influence of grain size and phase transition of the oxidants on the processes of combustion and decomposition.

62. Calculation of Thermal Decomposition Kinetic Parameters of B/KNO_3

JIANG Ming~(1,2),LONG Xin-ping~1, YAN Nan
1.School of Mechanics and Electronic Beijing Institute of Technology,Beijing 100081,China
2.Institute of Chemical Materials,CAEP,Mianyang 621900,China)

Abstract: On the basis of DSC curves of B/KNO_3 igniter powder,the apparent activation energy E of thermal decomposition is calculated with Kissinger′s methods and the probable mechanism function is available from master plot method.Kinetic parameters E and pre-exponential factor A are calculated with integration method at different heating rates.The results show that with the heating rate increasing,E and A decrease little,but in good accord with the E and A calculated with non-mechanism function.

63. Correlation between Structure Thermal Decomposition Characteristics and Burning Rate of the Monopropellants

WANG Yi~1,ZHAO Wei-bing~1,SONG Hong-chang~2,BAI Hua-ping~2,LIU Guan-li~3
1.The 705 Research Institute, China Shipbuilding Industrial Corporation, Xi′an710075, China
2. College of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
3.Office of Airman Military Representative Stationed in Northwest, Xi′an 710025, China)

Abstract: The correlation between structure, thermal decomposition characteristics and burning rate of the monopropellants, including AP, HMX, RDX, CL-20 and NQ, was studied by the steady state combustion model based on the single-dimensional gas flow of solid propellants. The combustion characteristics of the monopropellants were estimated by the improved model of burning rate, whose algorithm was based on the structures and thermal decomposition characteristics of the high energy materials. With the help of the comparison of the measured and predicted burning rates of the monopropellants, the rationality of hypothesis of the improved model was substantiated.

64. Thermal Decomposition of CL-20/DNTF/FOX-12-CMDB Propellant

WANG Jiang-ning~(1,2),FENG Chang-gen~1, TIAN Zhang-hua~2
1.Beijing Institute of Technology, Beijing 100081, China
2. Xi′an Modern Chemistry Research Institute, Xi′an 710065,China)

Abstract: The pressure differential scanning calorimetry (PDSC) was used to investigate the thermal decomposition behavior of CL-20(or DNTF or FOX-12)CMDB propellant. The result indicated that there are two exothermic peaks of CL-20-CMDB or DNTF-CMDB propellant. The first exothermic peak is due to decomposition of the double base binder, and the second exothermic peak is caused by the decomposition of CL-20 or DNTF. There is only one exothermic peak of FOX-12-CMDB propellant, showing that FOX-12 and double base binder(NC and NG,i.e.)are decomposed at the same time.

65. Effect of Several Additives on Thermal Characteristics of Ammonium Nitrate

LI Yi~(1,2), HUI Jun-ming~1
1.Chemical Engineering School,Nanjing University of Science & Technology, Nanjing210094, China
2.Institute of Chemical Material, CAEP, Mianyang621900, China)

Abstract: The crystal transformation and thermal decomposition rule of ammonium nitrate (AN) with additives were studied by using differential scanning calorimetry (DSC). The way and the mechanism of enhancing the stability of AN under normal temperature and stimulating its thermal activity under high temperature were searched. The experimental results proved that some organic additives have a stabilizing effect on AN crystal phase which is indicated by the fact of decreasing the thermal effect of crystal transformation. These additives, including sawdust, cotton fibre, phosphonic acid, potassium chloride and potassium bichromate accelerated the thermal decomposition of AN under high temperature and made the exothermic temperature advance and energy releasing enhance more abruptly.

66. Thermal Decomposition of RDX and HMX Part II: Kinetic Parameters and Kinetic Compensation Effects

LIU Zi-ru, YIN Cui-mei, LIU Yan, Fan Xi-ping, ZHAO Feng-qi
Xi′an Modern Chemistry Research Institute, Xi′an710065, China)

Abstract: The kinetic parameters of thermal decompositions of RDX and HMX explosives were obtained by using DSC,DTA and TG-DTG. It is shown that the differential kinetic parameters and mechanism functions appear in various stages of thermal decomposition for RDX and HMX. The decomposition processes and kinetic parameters of RDX and HMX are markedly affected by test conditions, specimen state and test method, and the "kinetic compensation effect"and "isokinetic points(temperatures)" exist in these parameters.

67. Flash Pyrolysis Studies of [Co (CHZ)_3](ClO_4)_2

SUN Yuan-hua, ZHANG Tong-lai, ZHANG Jian-guo, MA Gui-xia, WANG Shao-zong
nology, Beijing 100081, China)

Abstract: ZThe main solid products from the conventional thermal decomposition can be determined by TG、DSC technology. To investigate the thermal decomposition behavior of [Co (CHZ)_3](ClO_4)_2 (CoCP) further, the T-jump/FT-IR spectroscopy was used to determine the main gaseous products evolved from the thermolysis of CoCP in real time. CoCP was flash-pyrolyzed to the set temperature under 1 atm. The control voltage trace can detect the thermal events occurring within the sample as it decomposes. With the help of rapid scanning Fourier transform infrared (FT-IR) spectroscopy, 12 specific IR-active gas products (NO,HCN,NH_3,HNCO,CO_2,CO,HCl and so on) were resolved during the flash pyrolysis process, of which CO is the most novel product, NO and HCN are the dominant gases containing nitrogen, the dominant gases containing carbon are CO, CO_2 and H_2C=O. The concentration change curves of the main gaseous products vs. time are also put forward.

68. Kinetics of the First Order Autocatalytic Decomposition Reaction of Nitrocellulose(11.92% N)

HU Rong-zu~(1,2), NING Bin-ke~(1,2), YANG Zheng-quan~2,Song Ji-rong~1, GAO Sheng-Li~
1 mistry, Northwest University, Xi′an710069, China
2. Xi′an Modern Chemistry Research Institute, Xi′an710065, China
3. Ordnance Engineering Institute, Shijiazhuang050000, China)

Abstract: The kinetics of the first order autocatalytic decomposition reaction of nitrocellulose (NC, 11.92%N) was studied by using DSC. The results show that the DSC curve for the initial 50% of conversion degree of NC can be described by the first order autocatalytic equationdydt=-10~(16.4)exp-210380RTy-10~(16.7)exp-171500RTy(1-y)and that for the latter 50% conversion degree of NC described by the reaction equationsdydt=-10~(16.3)exp-174280RTy(n=1)anddydt=-10~(16.8)exp-171300RTy~(2.71)(n≠1)

69. Thermal Decomposition of RDX and HMX Part I: Characteristic Values of Thermal Analysis

LIU Zi-ru, LIU Yan, FAN Xi-ping, ZHAO Feng-qi, YIN Cui-mei
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: In this paper the thermal decompositions of RDX and HMX explosives were investigated by using DSC and TG-DTG. The influence of experimental condition, including sample size, heating rate and ambient pressure under static and dynamic pressure, on the thermal behaviors was considered. The exothermic decomposition of HMX is sharper than that of RDX, the reason mainly being the solid-liquid phase change occurring for decomposition of the former. Thus the self-heating and auto-catalysis of sample for HMX are stronger than those for RDX

70. Kinetics of the Exothermic Decomposition Reaction for 1, 1′-dimethyl-5,5′- azotetrazole Monohydrate

ZHAO Feng-qi~(1,2), HU Rong-zu~(1,2), CHEN Pei~(1), LUO Yang~(1), SONG Ji-rong~(2), GAO Sheng-li~(2), CHEN San-ping~(2), SHI Qi-zhen~(2)
2. Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The kinetic parameters of the exothermic decomposition reaction of 1,1′-dimethyl-5,5′-azotetrazole monohydrate (1,1′-DMATZM) in a temperature-programmed mode have been studied by means of DSC, indicating that the empirical kinetic model function in differential form, apparent activation energy (Ea) and pre-exponential factor (A) of this reaction are (1-α)~(-1.53),114.1 kJ/mol and 10~(8.72) s~(-1), respectively. The critical temperature of thermal explosion of the compound is 215.45 ℃.

71. Thermal Stability and Thermal Decomposition Mechanism for Novel Polyazidophosphates

OU Yu-xiang~1, YE Ling~2, WANG Jian-long~1, CHEN Bo-ren~1
1. School of Materials Sciences and Engineering, Beijing Institute of Technology, Beijing100081,China
2. Department of Chemistry, Capital University of Medicine Sciences,Beijing100054,China)

Abstract: The thermal stability of two novel chain polyazidophosphates——tri(β-azidoethyl) phosphate(TAEP)and 2,2-di(chloromethyl)-1,3-Propylenetetra(β-azidoethyldiphosphate (MPAEDP) and two novel bicyclic azidophosphates——l-oxo-4-(β-azidoethoxycarbonyl) (or(β,β′- diazidoisoPropoxycarbonyl))-2,6,7-trioxy-phosphabicyclo[2.2.2]octane (AEPEP and AIPEPA) were measured by DSC.The kinetic parameters (Ea, Aa and ka) were calculated by kissinger and Ozawa methods. In addition, the possible decomposition mechanism is suggested.

72. Kinetics of the Exothermic Decomposition Reaction for 2,5,7,9-Tetranitro-2,5,7,9-tetrazabicyclo nonanone

ZHAO Feng-qi~(1,2), HU Rong-zu~(1,2), CHEN Pei~2, LUO yang~2, WANG Bo-zhou~2, YANG De-suo~3, GAO Sheng-li~1, ZHAO Hong-an~1, SHI Qi-zhen~1
2. Xi'an Modern Chemistry Research Institute, Xi'an710065, China
3. Baoji College of Arts and Science, Baoji721007, China)

Abstract: The kinetic parameters of the exothermic decomposition reaction of the title compound in a temperature-programmed mode have been investigated by means of DSC. The kinetic model function in differential form, apparent activation energy (Ea) and pre-exponential factor (A) of this reaction are 3(1-α)~(23), 204.7 kJ/mol and 10~(20.89) s~(-1), respectively. The critical temperature of thermal explosion of the compound is 188.81 ℃. The values of ΔS~≠, ΔH~≠ and ΔG~≠of this reaction are 141.6 J/(mol•K), 200.9 kJ/mol and 136.8 kJ/mol, respectively.

73. The Thermal Decomposition of NEPE Propellant (Ⅲ) Thermal Decomposition of HMX/RDX/AP-NEPE Propellant

PAN Qing,WANG Yuang,CHEN Zhiqun
Xi′an Modern Chemistry Research Institute,Xi′an710065,China )

Abstract: Two simultaneous device of the fast thermlysis reaction cell (gas reaction cell)in situ in conjunction with rapidscan fourier transform infrared spectascopy(RSFTIR),and the solid reaction cell in situ/RSFTIR were used to measure the gas products and condensed phase products of the thermal decomposition of HMX/RDX/APNEPE propellant in real time.Under linear temperature increase condition,the thermal decomposition characteristics of HMX/RDX/APNEPE propellant were obtained.The results indicate that the catalytic action of AP to the thermal decomposition process was obvious.

74. Estimation of the Critical Increase Temperature Rate of Thermal Explosion of Nitrocellulose Using Non-isothermal DSC

HU Rongzu1,2,Guo Pengjiang3, SONG Jirong1, ZHANG Hai3,XIA Zhiming3, NING Binke2, FANG Yan1, SHI Qizhen1, LIU Rong4, LU Guie5,JIANG Jinyou5
Northwest University, Xi'an710069, China

Abstract: A method of estimating the critical increase temperature rate of thermal explosion for the first order autocatalytic decomposition reaction system using nonisothermal DSC is presented. Information is obtained on the increasing rate of temperature in nitrocellulose containing 11.92% of nitrogen when the first order autocatalytic decomposition converts into thermal explosion.

75. Molecular Structure and Thermal Decomposition Mechanism of Semicarbazide Hydrochloride

MA Guixia1, ZHANG Tonglai1, ZHANG Jianguo1, MIAO Yanling1, YU KaiBei2
Beijing Institute of Technology, Beijing100081, China)

Abstract: The single crystal of semicarbazide hydrochloride was cultivated. It was characterized by using the xray singlecrystal diffraction analysis, element analysis and FTIR technique. The crystal is orthorhombic system, belongs to space group P212121, and the unit cell parameters are as followings: a=0.4672(1) nm,b=0.7547(1) nm,c=1.3209(2) nm;V=0.4657(9) nm3, Z=4;Dc=1.591　g/cm3;F(000)=232. Its thermal decomposition mechanisms were also studied by using DSC and TGDTG techniques. The thermal decomposition processes of semicarbazide hydrochloride consist of an endothermic melting procedure and three exothermic decomposition procedures continuously, and it decomposed totally up to 400 ℃.

76. Analysis on Adiabatic Decomposition Safety of Rock Emulsion Explosive Using Accelerating Rate Calorimeter

ZHOU Xinli,LIU Zuliang,LU Chunxu
Nanjing University of Science & Technology,Nanjing210094, China)

Abstract: The adiabatic decomposition of rock emulsion explosive has been studied by an accelerating rate calorimeter. The curves of thermal decomposition temperature and pressure versus time, selfheating rate and pressure versus temperature and pressure conversion rate versus time were obtained. The kinetic parameters such as apparent activation energy and preexponential factor were calculated. The decomposition history and safety of emulsion explosive were analysed. It was indicated that the rock emulsion explosive possesses better stability and safety.

77. The Thermal Safety of a New Kind of Initiating Explosives BNCP

ZHANG Rui, FENG Changgen, YAO Pu
Beijing Institute of Technology, Beijing100081,China)

Abstract: The thermal safety of BNCP is studied with the experimental methods. The DSC and TG tests of BNCP were carried out. Compared with Pb(N3)2 and CP, the temperature of decompose of BNCP is lower and the Ea of BNCP is larger. A cookoff test system was designed and the cookoff tests were carried out to study the thermal safety of BNCP. The results show that the thermal safety of BNCP is good when the environmental temperature is below 240℃. It has a long storage time when the environmental temperature is below 90℃. BNCP was detonated when the environmental temperature is about 266℃. The cookoff temperature of BNCP is 248～260℃.

78. Pseudo-Inverse Matrix Method —— A New Method to Deal with the Adiabatic Test Data

ZHU Huaqiao, QIAN Xinming,FU Zhimin
Beijing Institute of Technology, Beijing100081, China)

Abstract: A pseudoinverse matrix method to deal with the test data for accelerating rate calorimeter (ARC) is presented. The kinetic parameters of thermal decomposition for 4nitrotoluene2sulfonic acid are calculated the pseudoinverse matrix method. The reliability of the new method is tested by data simulation. It is showed that the pseudoinverse matrix has advantage over other similar methods on adiabatic test data.

79. Study on Thermal Function of Hexanitrohexaazaisowurtzitane

XU Rong, CHEN Song lin, ZHOU Jian hua
Institute of Chemical Materials ,CAEP, Mianyang 621900, China)

Abstract: This paper described theresult of thermolysis reaction kinetics and thermoanalyisi of CL 20, According to the data of vacuum constant temperature thermolysis experiment and corresponding curve at the 90℃~140℃, the experience formula of decomposing 0.1% under different temperature was and dat of CL 20: was than Ea =187.6 kj/mol, A =6.9×1023, heat of decomposition 2957 J/g, the blast point in 5s is 282.2℃, critical temperature is 224℃.

80. Kinetics of the Exothermic Decomposition Reaction and Critical Temperature of the Thermal Explosion for 7-Amino-4,6-Dinitrobenzofuroxan (ADNBF)

LEI Ying jie 1, ZHU Chun hua 2, HU Rong zu 2, WANG Bo zhou 2
1. Beijing Institute of Technology, Beijing 100081, China
2. Xi'an Modern Chemistry Research Institute, Xi'an 710065, China)

Abstract: The rapid thermal decomposition of 7 amino 4,6 dinitrobenzofuroxan (ADNBF) was examined by DSC and FT IR spectroscopy. The critical temperature of thermal explosion was obtained from the non isothermal DSC curves.

81. The Effect of Optical Properties of Propellants and Their Composition on Ignition Characteristics

NIU He lin, LI Shu fen
University of Science and Technology of China, Hefei 230026, China)

Abstract: Ignition delay time of NEPE propellant without considering in depth absorption of radiation is obtained using concept of conversion coefficient and ignition delay time of NEPE propellant determined at various igniting heat fluxes. Their relative errors at various igniting heat fluxes are calculated. Relative errors will be significant with the increase of igniting heat fluxes so that in depth absorption of radiation must be considered at relatively high igniting heat fluxes. Minimum absorption coefficient is valuable in whether in depth absorption of radiation should be considered or nor, while constructing ignition model of propellant.

82. Study on Internal Compatibility of SEFAE Composite Fuel by Method of Single non-isothermal DSC Curve

SONG Shu zhong, CHEN Wang hua, PENG Jin hua
Chemical School of Nanjing University of Science and Technology, Nanjing 210094,China)

Abstract: At present, the Ozawa method is widely used to evaluate the internal compatibility of explosives, which always results in large amount of experimental workload.In our lab ,a single non isothermal DSC curve method was employed to calculate kinetic parameters of thermal decomposition,by which the internal compatibility of SEFAE composite fuel can be evaluated.By comparison,we have found that the deviation between the two methods is very small. The experimental results also show that SEFAE composite fuel is of good internal compatibility.

83. New Method of Adopting the Temperature Sensitivity of Gun Propellant

WANG Qiong lin
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: Decreasing the temperature sensitivity of gun propellant is very important to a cartridge, but how to get it is practically very difficult. This paper investigates many reported test results and concludes a new method to adopting the temperature sensitivity of gun propellant. The method mainly relates to the internal hole of the propellant grain, the softness of grain surface, free volume of cartridge and strength of ignition.

84. The Catalyzed Decomposition of Ammonium Perchlorate

YIN Cui mei, LIU Zi ru, KONG Yang hui
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The influences of multiple catalysts and an energetic catalyst on thermal decomposition of ammonirm perchlorate (AP) at various pressures were investigated by pressure differential thermal analysis (PDTA). The influence of three catalysts used to this study on the high temperature decomposition is independent of the grain size of AP. On the basis of the kinetic parameters of decomposition, it was interpreted that there is the different catalytic mechanism in the decomposition of AP at various pressures. The pressure exponents of burn of the propellants can be related to the rates of the catalyzed decomposition of AP at various pressures.

85. Combustion Properties of Nitroamine Monopropellants

LIU Yun-fei, AN Hong-mei, YANG Rong-jie
Beijing Institute of Technology, Beijing 100081, China)

Abstract: The behaviors of the thermal decomposition of HMX, RDX and CL-20 were determine d. The energies of the nitroamine monopropellants were calculated by theory and the combustion properties of nitroamine monopropellants were determined with the measurement system for the combustion process of propellant.The results indicat e that the temperature of thermal decomposition of CL-20 is lower and its energ y is higher. The burning rate of CL-20 is two times of the burning rate of HMX and the pressure exponent of burning rate of CL-20 is corresponded with that of HMX.

86. Thermal Decomposition Mechanism of RDX in Inertial Solvents

SHU Yuan-jie, DUBIKHIN V V, NAZIN G M, MANELIS G B
Institute of Chemical Materials, CAEP, Mianyang 621900, China)

Abstract: Solvents can be divided into inertial and active groups according to their effec ts on RDX decomposition rate. Active solvents accelerate RDX decomposition rate, inertial solvents do not affect RDX decomposition rate or inhibit RDX decomposi tion because of their large viscosity. In this paper thermal decomposition mecha nism of RDX in inertial solvents was studied by means of special Brudon apparatu s. On basis of N-NO 2 bond dissociation many secondary reactions were outlined , and with these reactions our own and related literature experimental facts can be explained: in ertial solvent effect on RDX decomposition rate, effect of RDX concentration in benzene on RDX thermal gas producing and the formation of nitr oso-RDX. The outlined mechanism makes the knowledge of thermal decomposition of nitramine in solutions one step forward.

87. The Influence of High Pressure of Static and Dynamic Atmosphere on the Thermal Decomposition of Energetic Materials

LIU Yan, LIU Zi ru, QIU Gang
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The thermal decomposition of energetic materials such as CL 20、HMX、RDX、NC、NG、NG+NC were investigated by using the methods of differential scanning calorimetry (DSC)、pressure differential scanning calorimetry (PDSC) in static and dynamic atmosphere and the influence of high pressure of static and dynamic atmosphere on the thermal decomposition of these energetic materials are discussed in this paper. As a result, it is showed that the thermolysis of energetic materials influenced by different pressure of static and dynamic atmosphere can be divided into three species: 1. The thermal decomposition are influenced by pressure and dynamic atmosphere simultaneously; 2. The thermal decomposition are influenced neither by the pressure nor by the dynamic atmosphere; 3. The thermal decomposition are influenced only by the pressure.

88. Analysis on the Relationship Between Thermal Decomposition Properties and Combustion Stability of Propellants

LI Li, ZHAO Bao chang, YANG Dong
College of Chemistry & Environmental Seience, Nanjing Normal Univ ersity, Nanjing 210097, China)

Abstract: There exists a relationship of increasing function between the combustion stability and the thermal decomposition complexity of propellants. The relationship is more likely to be statistical than to be analytical. Through the changing of apparent decomposition activation energy ( E a ) of sub face during the combustion of propellant, the influence of thermal decomposition properties on combustion stability is exerted. When the circumstance pressure and the temperature are low, the thermal decomposition properties of sub face are similar to those determined under common thermal analysis conditions. To the propellants with relatively complex decomposition process, as the circumstance pressure and the temperature increase, the decomposition mechanism and apparent activation energy of the sub face will change. The rule by which the decomposition rate varies with pressure will be different. And unstability occurs in the combustion process. However, to propellants with relatively simple thermal decomposition process this will not happen. In addition, this paper also suggests that the reason for high burning rate pressure exponent is deflagration of some components in propellant.

89. The Effect of Reacting Fraction on the Thermal Decomposition Kinetic Parameters of Comp B

HE De chang, XU Jun pei, LIU De run
Beijing Institute of Technology, Beijing 100081, China)

Abstract: In this paper, the thermal decomposition of the thermal treated COMP B is studied by DSC 7. The survey shows that the activation energy influenced by the reacting fraction is decreasing with reacting fraction increasing.

90. Preparation and the Flash Pyrolysis of 4-Amino-1,2,4-triazol-5-one(ATO)

ZHANG Jian guo, ZHANG Tong lai
Beijing Institute of Technology, Beijing 100081, China)

Abstract: Amino 1,2,4 triazol 5 one(ATO) was prepared in this paper. Its conventional thermal decomposition was described by DSC technology. The flash pyrolysis of ATO was investigated by T jump/FT IR spectroscopy. The concentration change curve of the main gaseous remains was put forward.

91. Experimental Study on Thermal Decomposition Performance of Deterred Gun Propellant

XIAO Zheng gang, YING San jiu, XU Fu ming
Nanjing University of Science and Technology, Nanjing 210094, China)

Abstract: In this article, a study on the thermal decomposition and the ignition behavior of deterred powder penetrated by variety of deterrents wity the different concentration is conducted through the Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). The threshold thermal decomposition temperature of TG and DSC curves could qualitatively characterize the ignition properties of the deterred gun propellant. The traditional viewpoint is that the ignition temperature should increase, but the experimental results show that for the kind of deterrents and their concentration using in this experiments, the threshold thermal decomposition temperature of TG curves and DSC curves doesn't increase, but decreases little, and the endotherm amount of DSC curves decrease obviously. The brief analysis on the experimental results is presented.

92. Study on Decomposition and Impact Sensitivity of ε-Hexanitrohexaazaisowurtzitane in Three Particle Sizes

XU Yong jiang, JIN Shao hua, OU Yu xiang, SONG Quan cai
Beijing Institute of Technology, Beijing 100081, China)

Abstract: The thermal decomposition of ε hexanitrohexaazaisowurtzitane (ε HNIW) in various particle sizes has been studied and formal kinetic parameters E and A were obtained. The impact sensitivity of ε HNIW corresponding particle sizes was determined, and the influence of particle sizes on formal kinetic parameters and impact sensitivity has been analyzed .

93. Thermal Decomposition Characteristics of GAP Fuel-rich Propellant Ingredients

ZHU Hui, ZHANG Wei, WANG Chun hua, TONG Yu she
National University of Defense Technology, Changsha 410073, China)

Abstract: The thermal characteristics of GAP fuel rich propellant ingredients, such as AP, KP, AP/KP and GAP, were studied by DSC method. The action of some TMOs on the thermal decomposition characteristics of the ingredients was investigated in this paper. The results showed that the action of the TMOs on the thermal decomposition reactions of GAP, AP and KP was different.

94. Effect of B_(12)H_(12)[N(C_2H_5)_4]_2 on Combustion Property of NEPE Propellant

CHEN Fu tai, TAN Hui min, LUO Yun jun
School of Chemical Engineering & Materials Science, Beijing Institute of Technology, Beijing 100081, China)

Abstract: The effect of B 12 H 12 [N(C 2H 5) 4] 2 (YL 6) on combustion property of NEPE solid propellant was studied. The compatibility of YL 6 and nitrate ester, the effect of YL 6 on the curing reaction and on the thermal decomposition behavior of ammonium perchlorate and nitroamino compounds were studied by Differential Scanning Calorimetry (DSC). It was observed that YL 6 exhibited not so good compatibility with nitrate ester which accelerated the thermal decomposition of nitroamino compounds but had little effect on ammonium perchlorate and on the curing reaction. When YL 6 was applied to NEPE solid propellant, the burning rate of propellant increased comparing to plumbean citrate as burning rate catalyst and the pressure exponent was effectively brought down to 0.13 in high pressure which was called platform phenomenon.

95. Effect of B_(12)H_(12)[N(C_2H_5)_4]_2 on Combustion Property of NEPE Propellant

CHEN Fu tai, TAN Hui min, LUO Yun jun
School of Chemical Engineering & Materials Science, Beijing Institute of Technology, Beijing 100081, China)

Abstract: The effect of B 12 H 12 [N(C 2H 5) 4] 2 (YL 6) on combustion property of NEPE solid propellant was studied. The compatibility of YL 6 and nitrate ester, the effect of YL 6 on the curing reaction and on the thermal decomposition behavior of ammonium perchlorate and nitroamino compounds were studied by Differential Scanning Calorimetry (DSC). It was observed that YL 6 exhibited not so good compatibility with nitrate ester which accelerated the thermal decomposition of nitroamino compounds but had little effect on ammonium perchlorate and on the curing reaction. When YL 6 was applied to NEPE solid propellant, the burning rate of propellant increased comparing to plumbean citrate as burning rate catalyst and the pressure exponent was effectively brought down to 0.13 in high pressure which was called platform phenomenon.

96. Influence of Humidity on the Thermal Self-ignition on Propellant

CHEN Ming hua, JIANG Jin yong, LU Gui er, LIU Li bin
Ordnance Engineering Institute, Shijiazhuang 050000, China)

Abstract: A experimental method of measuring thermal self ignition of propellant in different humidity is introduced. Thermal self ignition times of single base propellant and double base propellant in different humidity are measured by this method. The experimental result is discussed and analyzed.

97. Determination of Chemical Kinetic Parameters of Single-base Propellant with Microcalorimetry

LU Gui e, JIANG Jin yong, CHEN Ming hua
The PLA 59163th unit,Shijiazhuang 050000,China)

Abstract: The chemical kinetic parameters of single base propellant are determinated using microcalorimetry and the experimental conditions are studied.The results obtained are very imporant for the study of the decomposition mechanism and safety of gun propellant.

98. Study on the Thermal Decomposition Kinetics of Expanded Ammonium Nitrate

LU Ming, LIU Hui ying
Chemical Engineering School, NUST, Nanjing 210094, China)

Abstract: The thermogravimetry (TG) curves of common industrial ammonium nitrate and expanded ammonium nitrate are given in this paper. The thermal decomposition activation energys of common industrial ammonium nitrate and expanded ammonium nitrate are calculated. The reaction mechanism and kinetics equation of the thermal decomposition of common industrial ammoniun nitrate and expanded ammonium nitrate are studied.

99. A Study on the Denitration Kinetics of Highly Nitrated Nitrocellulose

NING Bin ke, YANG Zheng quan, LIU Rong, WANG Yuan, PAN Qing , HU Rong Zu
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The denitration kinetics of the highly nitrated nitrocellulose (HNNC) containing 14.14% of nitrogen was studied by means of the thermal technique of solid reaction cell in situ in conjunction with rapid scan Fourier transform infrared spectroscopy (RSFT IR) for measuring the condensed phase decomposition products in real time. The kinetic parameters such as activiation energy and pre exponential factor of the denitration reaction were computerized by using the modified Coats Redfern method. On the basis of the results obtained, a differential knietic equation of describing the denitration reaction of HNNC in the temperature range 403～465K was proposed.

100. Thermal Behavior of 2,2,8,8 Tetranitro 4,6 Dioxa 1,9 Pelargonic Dinitrate in Liquid State

HU Rong zu, WU Shan xiang, CAI Bing yuan
Xian Modern Chemistry Research Institute, Xian 710065, China)

Abstract: Under isothermal and non isothermal conditions, the kinetic parameters of the thermal decomposition process of the title compound in liquid state are studied by means of highly sensitive Bourdon manometer and DSC. The results show that the apparent activation energy and pre exponential constant of above mentioned reaction are 156 kJmol -1 and 10 15.2 s -1 , respectively.

101. Thermal Decomposition of EAK Intermolecular Explosive

ZHAO Sheng xiang, ZHANG Yi an, HU Huan xing, LU Chun xu
Xian Modern Chemistry Research Institute, Xian 710065, China)

Abstract: The decomposition of EAK( Ethylenediamine Dinitrate Ammonium Nitrate Potassium Nitrate) eutectic intermolecular explosive was investigated by means of DSC. The interaction between oxidizer AK and reductant EDD made the eutectic mixture presenting a sharply automatical decomposition reaction.From the non isometic DSC curves, the kinetic parameters of decomposition of EAK were obtained.

102. Studies on Effect of NGu Ignition Property of Nitramine Propellant

DU Cheng zhang,YANG Yang
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: In this paper, Differential Scanning Calorimetry (DSC) and propellant ignition and combustion simulator studied the effect of NGu on the ignition property of NG NG RDX propellant system. The experiments prove that NGu can improve the ignition property of NC NG RDX nitramine propellants and the effect is more obvious when the proportion of NGu∶RDX is more than 1.

103. Investigation on Thermal Decomposition Characteristics of Trimethylolethane Trinitrate( TMETN)

ZHAO Feng qi, CHEN Pei, LI Shang wen
Xian Modern Chemistry Research Institute,Xian 710065,China)

Abstract: The thermal decomposition characteristics of trimethylolethane trinitrate(TMETN) have been investigated by means of pressure DSC. Rusults show that, even though TMETN has the similar structure to nitroglycerin (NG), TMETN has totally different thermal decomposition characteristics. At normal pressure, TMETN has an exothermic decomposition peak, while NG has an endothermic peak ; at the condition of pressure, TMETN has two exothermic peaks. The shape, temperature and quantity of heat of the two peaks change with the increase of pressure. The kinetic parameters of TMETN have been obtained, and TMETNs decomposition mechanism has been also analysed.

104. The Effect of Complex Salt of Lead/Copper on the Thermal Decomposition Reaction of NC

PAN Qing, WANG Yuan
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The effect of complex salt of lead/copper on the thermal decomposition of NC is measured by the device of solid reaction cell in situ/RSFT IR. The functional relationship between the percent content of catalyst and temperature of denitration of 50% in NC is presented.

105. Thermal Stability of LTNR after Coating

CAI Zheng qian
Nanjing University of Science and Technology, Nanjing 210094,China)

Abstract: Thermal stability of LTNR and LTNR Coated with 2% shellac and 1.8% graphite or 2.7%～4.5% bitumen is investigated by using DTA, VST, isothermal loss weight, and ignation determination. The results indicate that the stability of the LTNR Coated with 2% shellac and 1.8% graphite is between the stability of LTNR without coating and that of LTNR Coated with 2.7%～4.5% bitumen.

106. Thermal Decomposition of Polyurethane Bonded Propellants

Luo Shanguo Chen Futai Tan Huimin
Beijing Institute of Technology,Beijing 100081)

Abstract: The effect of various NEPE propellant ingredients on the thermal decomposition characteristics of polyurethane binder was investigated with Thermogravimetry (TG) and Differential Scaning Calorimetry(DSC).The thermal stability of polyurethane binder varies with different ingredients contained and the thermogravity generally proceeds in two stages,first the volatilization and decomposition of NG/BTTN, AP or HMX, then the pyrolysis of polyurethane.Free radicals produced by the decomposition of energetic ingredients(NG/BTTN, AP,HMX) may initialize the degradation of polyurethane while the degradation of polyurethane promotes the decomposition of energetic ingredients .Black crabon, nitrocellulose and coupling agent increase the stability of polyurethane binder whereas aluminum powder accelerates its degradation.As a result of these inter effects, the decomposition of NEPE starts with nitrate ester,followed by the subsequent degradation of AP and HMX.

107. Thermal Decomposition of the Mixtures of RDX 、HMX and Organic Flame Retardants

Jin Shaohua Song Quancai
Beijing Institute of Technology, Beijing 100081)

Abstract: It has been studied that the formal thermo decomposition kinetics of the binary mixtures of RDX、HMX and some flame retardants by using DTA technique in this work. Formal kinetic parameters: E、A 、k were obtanined, and the linear correlation between the decompositon reaction rate constant k and the inhibiting coefficient of combustion rate K at 400℃ and different pressures were analysed.

108. The Study on Combustion Property of Nitramine Propellant Containing HNS

Li Xinrui Yang Dong Zhao Baochang
Nanjing University of Science and Technology, Nanjing 210094)

Abstract: Compared to RGD7 (containing NGu),the p t curves of RHD6(containing HNS)at different temperature draw close to each other,thus lowering the burning rate temperature coefficient of nitramine propellant.The extinguishment test shows that the burning area of RHD6 can compensate for the loss gas producing rate which decreases with temperature dropping.Kinetic parameters of thermal decomposition estimated form DSC curves also reveal that HNS may decrease the activation energy of the system.

109. Importance of Thermal Decomposition Data on Studying Critical Process Temperature

He Jiyu Tian Linxiang Chen Shaozhen Dai Jianwu
Beijing Institute of Technology, Beijing 100081)

Abstract: The effects of initial temperature, increasing rate of temperature on the propellant thermal decomposition have been studied by DSC. These are the basis of studying critical processing temperature for propellants.

110. Thermal Decomposition and Combustion Properties of Keto RDX Propellant

Li Li Zhao Baochang Zhang Yuejun Qu Wenchao Yang Dong
Nanjing University of Science & Technology, College of Chemical Engineering, Nanjing 210094)

Abstract: The thermal decomposition properties of 7 propellants which contain Keto RDX (2,4,6 trinitro 2,4,6 triazacyclohexanone) are investigated by DSC technique. Closed bomb tests are also done on 3 of them. The DSC data are fitted to kinetic equations to get kinetic parameters(E a, A,n). Burning rate pressure(u P) curves of the 3 propellants are calculated from the closed bomb test data. Turning analysis is carried out on the u P curves. The result shows that adding Keto RDX to propellants can raise the burning rates of the propellants and lower their apparent activation energies(E a) of thermal decomposition. The burning rate pressure exponent (v) of propellants containint Keto RDX is higher in low pressure region than that in high pressure region. Presence of Keto RDX and RDX simultaneously in a propellant is disadvantageous to the stability of thermal decomposition and combustion of the propellant. Propellant composed of Keto RDX and double based binder has lower burning rate pressure exponent than propellant composed of RDX and double based binder. The pressure exponent may less than 1.0.

111. Effect of Superfine Cu 2O Powder on the Thermal Decomposition Characteristics of Components of RDX/AP/HTPB Propellants

Liu Jingfeng Tian Deyu Deng Pengfen
China Defense Science and Technology Information Center, Beijing 100036)

Abstract: The superfine Cu 2O(0.2μm) powder was obtained through the redox reaction in microemulsion. The effect of superfine Cu 2O, ordinary Cu 2O(3μm), YB, QC and their different combinations on the thermal decomposition characteristics of AP, RDX and RDX/AP(mass ratio 1∶2) was studied by DTA, The experimental results indicate that the addition of superfine Cu 2O or its combination with YB is effective in decreasing the activation energy of AP and RDX/AP.

112. Thermal Decomposition Characteristics of Several Main Ingredients Used in CMDB Propellants

Liu Suoen Zhao Fengqi Liu Ziru
Xian Modern Chemistry Research Institute, Xian 710065)

Abstract: By using high pressure DSC, the decomposition behavior of several main ingredients (NC,NG,RDX, HMX etc.) used in CMDB propellant has been investigated under different pressure. The relationship between the thermal decomposition behavior and pressure is revealed and the effect of various ingredients on the combustion property is also discussed.

113. The phase Diagrams of TX and HX for Binary System of TEAN H 2O

Kong Yanghui Liu Ziru Yin Cuimei Hou Jianping
Xian Modern Chemistry Research Institute,Xian 710065)

Abstract: Abstract Thermal behaviour of the binary system of TEAN H 2O at low temperature has been investigated by DSC and the phase diagrams of TX( the correlation of the liquidus temperature with the composition) and HX( the correlation of the apparent heat of fusion with the composition) for the system were constructed. It is found that system is a simple binary system, whose eutectic temperature is -16.2℃ and eutectic compositions are TEAN/H 2O=

114. Thermal Decomposition of Explosives — A Comparation of Data, Obtained by Isothermal and Nonisothermal (DTA) Technique

Jin Shaohuo Song Quancai
Beijing Institute of Technology,Beijing 100081)

Abstract: A comparation has been made for kinetic data of thermal decomposition of explosives, obtained by isothermal and nonisothermal technique. For samples, which decompose relatively slow and evaporate quickly, the difference between data, obtained by iso and nonisothermal technique is great,for samples, which decompose in solid state and more quickly, the difference of data is not regular. The reason of these phenomena has been analysed.

115. The Effects of Boron Particle Surface Coating on the Thermal Decomposition of Fuel rich Propellant

Li Shufen Jin Rongchao
University of Science and Technology of China,Hefei 230026)

Abstract: By means of DTA、TG and DSC,the effects of boron particle surface coating on the thermal decomposition of B/Mg/AP/HTPB fuel rich propellant were studied.AP(NH 4ClO 4) 、KP(KClO 4) or LiF are used as coating materials.The experimental results show that it is useful for increasing the reactive activities of boron and promoting thermal analysis of fuel to coat the surface of boron particles.

116. A Study on the Catalysis Thermal Decomposition of Composite Solid Propellant

Peng Wangda Zhu Hui Zhang Ren
National University of Defense Technology,Changsha 410073)

Abstract: The Catalytic thermal decomposition of composite propellant has been investigated in the paper.A large number of thermal decomposition parameters and action laws for various catalysts have been obtained.

117. Thermal Behavior and Thermolysis Kinetics of the Explosive Trans-1,4,5,8-Tetranitro-1,4,5,8-Tetraazadecalin (TNAD)

Qi-Long Yan [Xi'an Modern Chemistry Research Institute, Xi'an, 710065 (China)], Xiao-Jiang Li [Xi'an Modern Chemistry Research Institute, Xi'an, 710065 (China)],Zhi-Qun Chen [Xi'an Modern Chemistry Research Institute, Xi'an, 710065 (China)],Xiao-Ning Ren [Xi'an Modern Chemistry Research Institute, Xi'an, 710065 (China)],Li-Hua Nie [Department of Material Science and Engineering, Xi'an University of Science and Technology, Xi'an, 710054 (China)], Propellants, Explosives, Pyrotechnics, 34: 357–362

Abstract: Trans-1,4,5,8-Tetranitro-1,4,5,8-Tetraazadecalin (TNAD), a cyclic nitroamine, has been studied with regard to the kinetics and mechanism of thermal decomposition, using thermogravimetry (TG), IR spectroscopy, and pressure differential scanning calorimetry (PDSC). The IR spectra of TNAD have also been recorded, and the kinetics of thermolysis has been followed by non-isothermal TG. The activation energy of the solid-state process was determined by using the Flynn-Wall-Ozawa method. Compared with the activation energy obtained from the Ozawa method, the reaction mechanism of the exothermic process of TNAD was classified by the Coats-Redfern method as a nucleation and nuclear growth (Avrami equation 1) chemical reaction (α=0.30–0.60) and a 2D diffusion (Valensi equation) chemical reaction (α=0.60–0.90). Ea and ln A were established to be 330.14 kJ mol−1 and 29.93 (α=0.30–0.60) or 250.30 kJ mol−1 and 21.62 (α=0.60–0.90).

118. Effect of Zn Powders on the Thermal Decomposition of Ammonium Perchlorate

Meirong Song1 [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou 730000 (P. R. China), Laboratory for Special Functionary Materials, Henan University Kaifeng, 475001 (P. R. China), Graduate School of the Chinese Academy of Science, Beijing 100049 (P. R. China)],Miao Chen2, [State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Lanzhou, 730000 (P. R. China)],Zhijun Zhang3 [Laboratory for Special Functionary Materials, Henan University, Kaifeng 475001 (P. R. China)], Propellants, Explosives, Pyrotechnics, 33: 261–265.

Abstract: In this paper, the catalytic effect of Zn nanopowders on thermal decomposition of ammonium perchlorate (AP) as well as those of Zn micropowders has been investigated using differential thermal analysis (DTA). The results show that both nanometer and micrometer Zn powders show similar excellent catalytic effect on the decomposition of AP, while the total heat releases of AP added by Zn nanopowders are generally higher than those of AP added by Zn micropowders. In addition, an attempt has been made to explain the observed results with the help of theoretical considerations and data generated during this work.

119. An Investigation on Thermal Decomposition of DNTF-CMDB Propellants

Wei Zheng, Jiangning Wang, Xiaoning Ren, Laying Zhang, Yanshui Zhou [Xi'an Modern Chemistry Research Institute, Xi'an 710065 (P. R. China)], Propellants, Explosives, Pyrotechnics, 32: 520–524.

Abstract: The thermal decomposition of DNTF-CMDB propellants was investigated by pressure differential scanning calorimetry (PDSC) and thermogravimetry (TG). The results show that there is only one decomposition peak on DSC curves, because the decomposition peak of DNTF cannot be separated from that of the NC/NG binder. The decomposition of DNTF can be obviously accelerated by the decomposition products of the NC/NG binder. The kinetic parameters of thermal decompositions for four DNTF-CMDB propellants at 6 MPa were obtained by the Kissinger method. It is found that the reaction rate decreases with increasing content of DNTF.

120. Effect of Fe2O3 in Fe2O3/AP Composite Particles on Thermal Decomposition of AP and on Burning Rate of the Composite Propellant

Zhenye Ma1[Nanjing University of Technology, Nanjing, 210009 (P. R. China) and National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing, 210094 (P. R. China)], Fengsheng Li2, Huaping Bai2 [National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing, 210094 (P. R. China)], Propellants, Explosives, Pyrotechnics, 31: 447–451.

Abstract: A technique of composite processing of Fe2O3 and ammonium perchlorate (AP) was employed in making the propellant. The effects of composite processing of Fe2O3 on catalytic activity, on the thermal decomposition of AP, and on the burning rate of the composite propellant were investigated in this paper. Fe2O3/AP composite particles were prepared by a novel solvent-nonsolvent method. The results show that AP is successfully coated on the surface of Fe2O3. Composite processing of Fe2O3 and AP can improve the catalytic activity of Fe2O3. Fe2O3 exhibits better catalytic effect with increasing Fe2O3 content. The larger interface between Fe2O3 and AP and lower density of composite propellant (with the added Fe2O3/AP composite particles) are responsible for the enhancement of the catalytic activity of Fe2O3.

121. Preparation of Cu/CNT Composite Particles and Catalytic Performance on Thermal Decomposition of Ammonium Perchlorate

Cui Ping1 [National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing, Jiangsu 210094 (P. R. China) and School of Chemistry and Chemical Engineering, AnHui University of Technology, Maanshan, Anhui 243002 (P. R. China)], Fengsheng Li2, Zhou Jian2, Jiang Wei2 [National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing, Jiangsu, 210094 (P. R. China)], Propellants, Explosives, Pyrotechnics, 31: 452–455.

Abstract: Composite particles of carbon nanotubes (CNTs) and Cu were prepared by a chemical reduction method. Characterization of Cu/CNT composite particles was performed by TEM, SEM, FT-IR, XRD, XPS, AAS, DTA and EDS. The results show that the surface of CNTs is covered by Cu particles, and that the diameter of Cu/CNT composite particles gets larger than that of CNTs. Furthermore, in the presence of Cu/CNT composite particles, the peak temperature of the high-temperature decomposition of ammonium perchlorate (AP) decreased by 126.3 °C, and the peak of the low-temperature decomposition disappeared. Compared with a sample of simply mixed Cu and CNTs, the peak temperature of the high-temperature decomposition of AP-Cu/CNTs composite particles decreased by 11.4 °C. Compared with Cu, the peak temperature of the high-temperature decomposition of AP-Cu/CNT composite particles decreased by 20.9 °C. This work shows that the catalytic performance of Cu on the thermal decomposition of AP can be improved by compounding with CNTs.

122. An Azido Ester Plasticizer, 1,3-Di(Azidoacetoxy)-2,2-Di(Azidomethyl)Propane (PEAA): Synthesis, Characterization and Thermal Properties

Qiu Shaojun1, Fan Huiqing1 [State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, P.R. China], Gao Chao2, Zheng Xiaodong2, Gan Xiaoxian2 [Xi'an Modern Chemistry Research Institute, Xi'an 710065, P.R. China], Propellants, Explosives, Pyrotechnics, 31: 205–208.

Abstract: A polyazido compound, 1,3-di(azidoacetoxy)-2,2-di(azidomethyl)propane (PEAA) was synthesized and identified. Thermal properties of PEAA, such as the glass transition temperature (Tg), differential scanning calorimetry (DSC) and thermogravimetric analysis (DTG) were investigated in detail. Two steps in the course of thermal decomposition of PEAA were observed clearly, and some gases, carbon monoxide, carbon dioxide, nitrogen, hydrocyanic acid, methane and 2-methyl-1,3-butadiene were identified as decomposition products by in situ cell FTIR. The pyrolysis mechanism was also proposed.

123. The Interrelation Between the Thermal Decomposition of Lead Salt and the Platonization Mechanism of Double-Base Propellants

Yang Dong1, Song Hongchang1 [Nanjing University of Science and Technology, Nanjing 210094(P.R. China)], Li Shangwen2 [Xi'an Modern Chemistry Research Institute, Xi'an 710061(P.R. China)], Propellants, Explosives, Pyrotechnics, 23: 77–81.

Abstract: The effects of carbon black, cupric adipate and RDX on the thermal decomposition behaviour of lead flake in double-base system are investigated by DSC measurement. The results show that the thermal decomposition peak of lead flake decomposition shifts to lower temperature with the addition of carbon black, cupric adipate and RDX, and the exotherm heat of lead flake increases with the addition of carbon black and RDX.
DSC results are compared with the burning characteristics of practical plateau propellants, the chemical reactions involving lead salts near the burning surface are assumed. The mechanism of the effects of ballistic modifiers and RDX on the phenomenon of platonization are discussed.

124. Studies on the critical temperature of thermal explosion for 3-Nitro-1,2,4-triazol-5-one (NTO) and its salts

Xie Yi, Hu Rongzu, Yang Chaoqing, Feng Guofu, Zhou Jihua [Xian Modern Chemistry Research Institute, Xian 710061, Shaanxi (People's Republic of China)], Propellants, Explosives, Pyrotechnics, 17: 298–302.

Abstract: The critical temperature of thermal explosion for 3-nitro-1,2,4-triazol-5-one (NTO) and its ethylenediammonium salt (ENTO), potassium salt (KNTO), copper salt (CuNTO) and lead salt (PbNTO) were obtained using the stationary theory of thermal explosion, the calculation formula of estimating the critical temperature of thermal explosion under non-isothermal DSC condition, and the determination method for the critical temperature of thermal explosion of small-scale solid explosive and its data treatment method. The results of the four methods are agreeable to each other, whose differences are within 5%. The results indicate that the heat-resistance ability of NTO and its salts and of the common explosives, cyclotetramethylenetetranitramine (HMX), cyclotrimethylenetrinitramine (RDX), pentaerythritoltetranitrate (PETN) and tetryl decreases in the order HMX > NTO > ENTO > KNTO > RDX > PETN > tetryl > PbNTO > CuNTO.

125. Studies on Thermal Decomposition of Energetic Nitrourea Salts

Xiao Heming1,* [East China Institute of Technology, Nanjing, China (PRC); *Correspondence: Xiao Heming, East China Institute of Technology, Nanjing, China (PRC)], Yuan Jinhua2, Xin Xinquan2, Dai Anbang2 [Coordination Chemistry Institute, Nanjing University, Nanjing, China (PRC)], Propellants, Explosives, Pyrotechnics, 14: 28–30.

Abstract: Thermal decomposition of nitrourea salts (K, Na, Ag, Ba) was studied in hydrogen atmosphere, helium atmosphere and vacuum by gas chromatography and mass spectrometry. The evolution of dinitrogen oxide, water, hydrazine, nitrogen dioxide and the formation of cyanate salts during thermodecomposition of nitrourea salts in helium and hydrogen were confirmed. In vacuum the evolved gaseous products changed to dinitrogen oxide, water, nitrogen monoxide, nitrogen gas indicating that interreaction between evolved gaseous products occurred. The same solid products – cyanate salts – are formed showing vacuum having no effects upon the decomposition mechanism.

126. The Characteristic Temperature Method to Estimate Kinetic Parameters from DTA curves and to evaluate the compatibility of explosives

Z. R. Liu, C. M. Yin, C. H. Y. Wu, M. N. Chang [Xian Modern Chemistry Research Institute, Xian (China)], Propellants, Explosives, Pyrotechnics, 11: 10–15.

Abstract: The thermal analysis technique was used to rapidly evaluate the compatibility of explosives with contacted materials. The three kinetic parameters viz. activation energy E, reaction order n and pre-exponential factor A were calculated from three characteristic temperatures of a single DTA curve. The compatibility was evaluated from the four parameters E, n and the characteristic temperatures Tm (peak maximum) and To (decomposition starting point on the DTA curve). The results are compared to those obtained from the gasometric method.

127. Effect of Drying Methods on Structure of RDX/RF Composite Energetic Materials

ZHANG Juan ,NIE Fu-de ,YU Wei-fei ,GUO Qiu-xia ,ZENG Gui-yu , chinese journal of energetic materials,2009,17(1):23~26.

Abstract: Hexahydro-1,3,5-trinitro-1,3,5-triazine/resorcinol-formaldehyde (RDX/RF) aerogel and xerogel were prepared by supercritical fluid drying method and freezing drying method. The structure of RDX/RF composites were characterized by scanning electron microscopy (SEM),BET method,X-ray power diffraction (XRD) and differential scanning calorimetry (DSC). The results show that supercritical fluid drying method can get RDX/RF aerogel of typical nano-pore structures and high surface areas. Freezing drying destroys the framework of gels and leads to the rapid decreasing of surface areas of gels. The mean crystal size of RDX in RDX/RF aerogels is between 34-38 nm,and in RDX/RF xerogels is between 50-100 nm. The thermal decomposition temperature of RDX/RF aerogels decreases by about 14-25 ℃,and of RDX/RF xerogels decreases by about 2-7 ℃.

128. Thermal Behaviors of CL-20 Systems Mixed with Three Binders by Gasometric Method

He Shao-rong, Heng Shu-yun, Zhang Lin-jun, chinese journal of energetic materials,2010,18(1):37~41

Abstract: The thermal behaviors of CL-20 mixed with three binders ((NC+NG),PET and PBT) at 160-200 ℃ were investigated by NBK LAWA gasometric measuring system. The thermal behaviors were described from the changes of evolved gases and decomposition kinetics. Results show that the apparent activation energies of CL-20 and its mixed systems with (NC+NG),PET and PBT are 176.68，176.31，136.12 and 127.0 kJ•mol-1, respectively. There is less influence of (NC+NG) binder on the decomposition rate and the apparent activation energy of CL-20. The heterogeneous gas/condensed phase reactions between gas products from CL-20 initial decomposition and PET or PBT decrease appear activation energies and increase obviously decomposition rates for CL-20/PET and CL-20/PBT systems. While the mechanism functions of CL-20 decomposition in the three systems are not changed by (NC+NG), PET and PBT

129. Compatibility of Double-base Propellant with Priming Composition

Wang Lin, Liu Zi-ru, Zhang La-ying, He Shao-rong, Yue Pu, Han Fang, Zhang Lin-jun, chinese journal of energetic materials,2010,18(1):47~50

Abstract: The compatibility of two double-base propellants (SB-1 and SB-2) and priming composition (WX-percussion composition) was studied by differential scanning calorimeter (DSC) and vacuum stability test (VST). The DSC results show that in the mixed systems WX-percussion composition/SB-1 and WX-percussion composition/SB-2,thermal decomposition peak temperatures of WX-percussion composition is increased by 8.8 ℃ and 7.4 ℃, respectively. Then,it can be considered that the two mixture systems are compatible. It is found in VST method that the net increment values of released gases for the two mixture systems are less than 0.6 mL•g-1 and the two systems are judged to be compatible. The peak temperature rise on DSC for WX-percussion composition in the two mixture systems was analyzed and discussed by the “topochemistry” principle,and it is proposed that the processes of thermal decomposition are inhibited by azido nitramine(DA) and nitroglycerine(NG) gases from their evaporation and (or) gasification.

130. Review on Homopolymer of Energetic Binders

ZHOU Yang ,LONG Xin-ping ,SHU Yuan-jie , chinese journal of energetic materials,2010,18(1):115~120

Abstract: In recent years, much attention was paid to new energetic binders used in high-energy solid propellants,which were synthesized from ring opening of oxirane and oxetane with different energetic groups. The relationships between the different energetic groups and physical and chemical properties，such as densities,heats of formation,melting point and mechanical properties,were reviewed. Finally, the possibility of this type of energetic binders used in PBX explosives was discussed by comparing their strongpoint and disadvantages.

131. Preparation and Properties of TOATF

LI Wei-wen ,LI Zhan-xiong ,WANG Wan-jun , chinese journal of energetic materials,2009,17(1):11~13   
       
Abstract: Using 3,4-diaminofurazan (DAF) as starting materials,and lead tetracetate as oxidation reagent,macrocyclic compound of 3,4: 7,8: 11,12: 15,16-tetrafurazano-1,2,5,6,9,10,13,14-octaazacyclohexadeca-1,3,5,7,9,11,13,15-octaene (TATF) was obtained as intermediate. The 3,4: 7,8: 11,12: 15,16-tetrafurazano-1,2,5,6,9,10,13,14-octaazacyclohexadeca-1,3,5,7,9,11,13,15-octaene-1,5,9,11-tetraoxide (TOATF) was synthesized followed by oxidation reaction using Caro′s acid as oxidation reagent. The total yield is 35.3%. The structure of macrocyclic compounds was identified by NMR,FT-IR,MS and elemental analysis. TOATF was identified to be thermal stable by TG technique. The compatibility of TOATF with RDX and HMX was studied using DSC method,and the result show that TOATF is compatible with RDX.
   
132. Thermal Behaviors of NTO-Based PBXs and their Compatibilities with Metals

ZUO Yu-fen,NIE Fu-de,YU Wei-fei,TIAN Xin,ZOU Jian-hua and LIU Shi-jun,Chinese journal of energetic materials,2009,17(1):55~53,86

Abstract: The thermal behaviors of three NTO-based PBXs and their compatibilities with aluminum,copper and stainless steel were investigated using TG-DSC and vacuum stability test(VST). Results show that: (1) A small amount of gases are produced from the three PBXs,suggesting their good thermal stability. When the PBXs contact with aluminum,copper and stainless steel,the additional amount of gas is less than 3.0 mL•(5 g) -1,and the decreasing values of peak temperatures are less than 2.0 ℃,showing their good compatibilities. (2) The peak temperatures of the decomposition of NTO and HMX in PBXs are lower than that of the pure explosives,indicating that the coexisting of these explosive can mutually accelerate their decomposition at high temperature

133. Interaction of NG/NC with AND

ZHANG La-ying,HENG Shu-yun,LIU Zi-ru,ZHANG Gao,ZHAO Feng-qi and TAN Hui-min, chinese journal of energetic materials,2009,17(1):95~98

Abstract: The interactions of double-base component mixture of nitroglycerin and nitrocellulose (NC/NG) with ammonium dinitramide (ADN) were investigated by pressure differential scanning calorimetry (PDSC),thermogravimetry-derivative thermogravimetry (TG-DTG) and vacuum stability test (VST). The results show that the decomposition exothermic peak temperature of NG in the NC/NG is 207.0 ℃,but drops down to 159.8 ℃ in the (NC/NG)/ADN system. The peak temperature drops down further to 153.6 ℃ at high pressure. The decomposition peak temperature of NC/ADN is a drop in 4.8 ℃ by comparison with NG/ADN. The greater part of ADN is not accelerated to promote decomposition by NG. It is shown that the effect of NC to ADN is strongly than NG to ADN. Besides,the compatibility between NC/NG and ADN was evaluated by VST. The increaser volume of gas products for mixed system is more than 11 mL,and is of “excessive” rating. It is proved that a strong interaction of NC/NG with ADN occurs also at 90 ℃

134. Specific Heat Capacities of Carbohydrazide Perchloric Acid Coordination Compounds

QIAO Xiao-jing,HAO Zhi-jian,FAN Fan and SUN Cui-na, chinese journal of energetic materials,2009,17(1):103~106

Abstract: The specific heat capacity of carbohydrazide perchloric acid energetic coordination compounds was studied by differential scanning calorimetry (DSC). The specific heat capacity of ［Co(CHZ) 3］(ClO4)2 was mensurated at 50-140 ℃ and the specific heat capacity of ［Mn(CHZ) 3］(ClO4)2,［Zn(CHZ) 3］(ClO4)2 and ［Ni(CHZ) 3］(ClO4)2 was mensurated at 50-200 ℃. The equations of the specific heat capacity changing with the temperature are fitted by the least square method,i.e.R≥0.985,SD≤0.060. The equations of the specific heat capacity of ［Mn(CHZ) 3］(ClO4)2 and ［Zn(CHZ) 3］(ClO4)2 are functions of second degree at 50.1-131.2 ℃ and that of ［Ni(CHZ) 3］(ClO4)2 is the function of four degree at 50.1-142.9 ℃,however that of ［Mn(CHZ) 3］(ClO4)2,［Zn(CHZ) 3］(ClO4)2 and ［Ni(CHZ) 3］(ClO4)2 are functions of three degree at the other temperature,and that of ［Co(CHZ) 3］(ClO4)2 is the function of three degree. ［Co(CHZ) 3］(ClO4)2 and ［Ni(CHZ) 3］(ClO4)2 were analyzed by method of TG and FTIR. TG curves show that only ［Co(CHZ) 3］(ClO4)2 loses weight after 140 ℃. FTIR spetra of two samples heated are different from that of the originals.

135. Estimation of Critical Temperatures of Hot-spot Initiation in Energetic Materials

HU Rong-zu,GAO Hong-xu,ZHAO Feng-qi,ZHANG Hai,GOU Ming,ZHAO Hong-an,WANG Xi-jun and MA Hai-xia, chinese journal of energetic materials,2009,17(2):127~130

Abstract: Bruckman-Guillet′s formula for calculating the critical temperature of hot-spot initiation(Tcr) in energetic materials(EMs) was derived. A numerical method of estimating the value of Tcr was presented. The corresponding computer program was programmed. The literature values ofTcr of nine EMs: PETN,RDX,HMX,EDNA,tetryl,EDADN,AN,NG and TNT,were certificated with the programmed program,considering that the programmed program is suitable for fast computation of Tcr and reported values of Tcr for eleven EMs: TATB,HNS,HNDACO,HHTDD,BTNDNG,keto-RDX,BTNEDA,PBX-JH-94,PBX-JO-96,TB propellant M32 and TB propellant SD are believable to a certain extent.

136. Electrical Conductivity and Reaction Zone Width Measurement of Detonation Process for Cast TNT/RDX Compositions

JIAO Qing-jie,JIN Zhao-xin and XU Xin-chun, chinese journal of energetic materials,2009,17(2):178~182.

Abstract: The coaxial measurement of electrical conductivity was improved by using shock initiation method,and the conductivity formula was derived. The suitable shock wave pressure was input to limit the shock wave reverberation in reaction zone and instability in detonation growth. And the conductivity curves of cast TNT and TNT/RDX compositions were studied. The chemical reaction times and the reaction zone widths were acquired by analyzing the inflexions in curves. Results show that the maximal conductivity decreases with the increasing of RDX in cast TNT/RDX compositions. The reaction time of cast TNT is about 0.08 μs, and the reaction zone widths of cast TNT and several TNT/RDX compositions are about 0.4 mm and 0.5 mm respectively.

137. Cook-off Test of DNAN Explosive

WANG Hong-xing,WANG Xiao-feng,LUO Yi-ming and JIANG Fang-fang, chinese journal of energetic materials,2009,17(2):183~186

Abstract: The thermal safety of 2,4-dinitroanisole(DNAN) explosive was studied by cook-off test. The self-ignition temperature,the delay time of thermal explosion and the critical temperature for the thermal explosion of DNAN were obtained,and the test results were compared with that of TNT. The results show that the self-ignition temperature of DNAN is 346.7 ℃,the temperature of 5 s explosion point is 374.1 ℃, and activation energy is 48.37 kJ•mol-1. Under the ambient temperature of 220 ℃,when DNAN is placed for 48 h, DNAN is nonflammable. DNAN is semi-burned under the ambient temperature of 230 ℃. When the temperature reaches above 240 ℃, thermal decomposition reaction of DNAN occurs. The delay time of thermal explosion was obtained from theoretical calculation at 100 ℃. Results show that DNAN is stable and safe in the melting process of temperature below 100 ℃.

138. Effects of Ammonium Nitrate on Energy Performance of Gun Propellant

HE Zeng-di,LIU You-ping,HE Li-ming and XIAO Zhong-liang, chinese journal of energetic materials,2009,17(2):202~205

Abstract: The effects of ammonium nitrate on energy of gun propellant were studied. The explosion heat at constant volume, isochoric adiabatic flame temperature, specific energy, covolume and specific volume of propellant gas were calculated by the minimum free energy method. The specific energy and covolume were tested by closed-bomb method. The explosion heat was tested by heat insulation method. The calculated results show that when the contents of ammonium nitrate are 58.49%,50.07% and 43.13%,the explosion heat,the flame temperature and the specific energy of gun propellant are 4743.2 kJ•kg-1,3075.9 K and 1049.6 kJ•kg-1, respectively. The testing results show that when the contents of ammonium nitrate are 50.0% and 40.0%, the explosion heat and the specific energy of gun propellant are increased by 23.6% and 5.0% respectively comparing with that of single-base propellant. With the increasing of content of ammonium nitrate, changes of explosion heat and specific energy are consistent with the calculated results.

139. Effect of Coating on Some Properties of a New Explosive 2，6-Diamino-3，5-dinitropyridine-1-oxide

HE Zhi-wei,GAO Da-yuan,FANG Dong and LIU Zu-liang, chinese journal of energetic materials,2009,17(3):299~303

Abstract: 2，6-Diamino-3，5-dinitropyridine-1-oxide (ANPyO) was coated with fluorine rubber F2311 and nitrile-butadiene rubber (NBR) by means of solution-water suspending-distillation method. The structures and properties of ANPyO and coated samples were characterized by Fourier transform infrared spectroscopy (FTIR)，scanning electron microscope (SEM)，differential scanning calorimetry (DSC)，thermograimetry (TG)，and impact and friction sensitivity tests. Results show that the decomposition peak temperatures of coated ANPyO are decreased by 8.3 ℃ and 7.8 ℃，and decomposition heats of coated ANPyO are increased by 282.4 J•g-1 and 41.5 J•g-1，and the particles of coated ANPyO become bigger. In FTIR spectra，N—H spectral characteristic absorption bands have 2 cm-1 and 3.9 cm-1 red shifts to 3280.6 cm-1 and 3367.4 cm-1respectively，and nitrogen atom in pyridine spectral characteristic absorption band has a 5.8 cm-1 red shift to 1232.4 cm-1. The impact sensitivity of coated ANPyO decreases from 16% to 14% and 10%，and the friction sensitivity decreases from 30% to 26% and 28%，respectively.

140. Refining and Properties of 2,6-Diamino-3,5-dinitropyridine-1-oxide

HE Zhi-wei,CHENG Jian and LIU Zu-liang, chinese journal of energetic materials,2009,17(4):392~395

Abstract: In order to study the properties of 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO), the three refined samples of ANPyO were prepared by recrystallization from the solvents of trifluoroacetic acid(CF3COOH), dimethyl sulfoxide(DMSO) and N,N-dimethyl formamide(DMF) respectively, and the properties of the three samples were compared. Results show that the particle size of ANPyO prepared by recrystallization from CF3COOH distributes from 2 μm to 70 μm and its BET specific surface area is 0.454 m2•g-1. The differential scanning calorimetry (DSC) analysis and thermal decomposition kinetics calculation show that, compared with ANPyO prepared by recrystallization from DMSO and DMF, enthalpy of decomposition of ANPyO（CF3COOH） is 1021.46 J•g-1, and the temperature of the exothermic peak is 370.69 ℃, and its activation energy is 279.63 kJ•mol-1 at a heating rate of 10 K•min-1. Impact and friction sensitivity of ANPyO prepared by recrystallization from CF3COOH are 20% and 18%, respectively.

141. Effects of DNP on Thermolysis and Combustion Characteristics of CMDB Propellant

QI Xiao-fei,YAN Qi-long,WANG Han and ZHANG La-ying, chinese journal of energetic materials,2009,17(4):451~454

Abstract: The effects of 1, 4-dinitropiperazine (DNP) on the combustion characteristics and thermolysis of CMDB propellants were studied by differential scanning calorimetry (DSC) and burning rate test. Results show that the thermolysis of RDX in propellants are affected obviously by DNP, and the burning rate and pressure index of CMDB propellants decrease with the increasing of DNP content. These phenomena become more evident when the pressure is 12-18 MPa. In addition, when the DNP content increases to 20% (DN3), there is an extra thermal decomposition peak of DNP which is separated from the main exothermic peak, and there is a lower exothermic peak beside it with the pressure increasing to 9 MPa.

142. Thermal Decomposition Kinetic Behavior of Emulsion Explosives

LUO Ning,LI Xiao-jie,WANG Xiao-hong and CUI Xin, chinese journal of energetic materials,2009,17(4):463~466

Abstract: Thermal decomposition characteristics of five emulsion explosives were studied by DSC-TG at the heating rates of 2.0, 2.5, 7.5, 10 K•min-1, and the thermal decomposition mechanisms were deduced by means of model-free function of Ozawa method and Costs-Redfern method and ?atava-?esták method. Results show that the activation energies calculated by the three methods are approximate, and the rationalities of thermal decomposition kinetic parameters of five emulsion explosives are verified so as to deduce the most possible mechanism functions of thermal decomposition characteristic of emulsion explosives. For sample 1, it is random nucleation and lateral overgrowth mechanism, for samples 2 or 5, it is Mample Power pricnciple n=2/3 mechanism, for samples 3 or 4, it is three dimension diffuse, 3D mechanism

143. Effect of Magnesium Based Hydrogen Storage Materials on the Properties of Composite Solid Propellant

LIU Lei-li,LI Feng-sheng,ZHI Chun-lei,SONG Hong-chang and LI Peng, chinese journal of energetic materials,2009,17(5):501~504

Abstract: The thermal decomposition behaviors of ammonium perchlorate (AP) and AP/Al/HTPB composite solid propellant in the presence of magnesium based hydrogen storage materials(Mg 2NiH 4,Mg 2Cu-H and MgH 2)were studied by DSC. The results show that 5% magnesium based hydrogen storage materials has obvious catalytic effect on the thermal decomposition of AP,and 1.3% magnesium based hydrogen storage materials obviously decreases the thermal decomposition temperature and increases heat release of AP/Al/HTPB composite propellant. The burning rates of AP/Al/HTPB composite solid propellant (8 MPa) are increased by 3.5%, 14.4% and 13.9% respectively with addition of 1.3% Mg 2NiH 4, Mg 2Cu-H and MgH 2. There is a clear relationship between hydrogen content of magnesium based hydrogen storage materials and its effect, and MgH 2 shows obvious effect among magnesium based hydrogen storage materials due to its large hydrogen content. By catalyzing the thermal decomposition of AP, magnesium based hydrogen storage materials shows good catalytic effect on thermal decomposition of AP/Al/HTPB composite solid propellant.

144. Estimation of Critical Temperature of Thermal Explosion for Some Furazano-fused Cyclic Compounds Using Non-isothermal DSC

HU Rong-zu,GAO Hong-xu,ZHAO Feng-qi,ZHANG Hai,MA Hai-xia and XU Kang-zhen, chinese journal of energetic materials,2009,17(6):635~642

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.

145. Theory and Numerical Method of Calculating the Kinetic Parameters of Exothermic Decomposition Reaction of Energetic Materials from Peak Temperature of DSC Curves at Constant Heating Rates

HU Rong-zu,GAO Hong-xu,ZHAO Feng-qi,ZHANG Hai,ZHAO Hong-an,MA Hai-xia,XING Xiao-ling and XUE Liang, chinese journal of energetic materials,2009,17(6):643~649

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

146. Interactions of PBT with Some High Energy Oxidizers by Thermal Analysis

ZHANG La-ying,HENG Shu-yun,LIU Zi-ru,ZHANG Gao,SHAO Ying-hui,WANG Lin,ZHAO Feng-qi and TAN Hui-min, chinese journal of energetic materials,2009,17(6):668~673

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.

147. Effects of Thermal Ageing on Mechanical Properties of PBX Based on TATB

WEI Xing-wen,LI Jing-ming,TU Xiao-zhen,Wang Pei and ZHOU Xiao-yu, chinese journal of energetic materials,2010,18(2):157~161

Abstract: The accelerated thermal aging tests of PBX based on TATB were carried out by using a hot air oven from 55 ℃ to 75 ℃. The mechanical properties such as tensile strength, elongation at failure and modulus were measured before and after aging. Morphology of rapture section from tensile test at 55 ℃ was observed by using scanning electric microscopy (SEM). Results show that the mechanical properties and the interfacial mechanism between binder and TATB crystal do not undergo changes significant during the aging period.

148. Ignition Temperature of 2Al/Fe2O3 Thermite

ZHANG Song-lin,WU Bin,QIN Zhi-gui and ZHANG Qing-ming, chinese journal of energetic materials,2010,18(2):162~166

Abstract: Ignition temperature of 2Al/Fe2O3 thermite was studied by analysis and experiments. Failure temperature of aluminum particle oxide film was analyzed according to the weight,resistance and appearance of aluminum powder undergoing different temperatures. Critical ignition temperatures of thermite spheres with different radii were calculated by Frank-Kamenetskii theory and measured by a high-temperature muffle furnace. Results show that the protective film fails almost completely at the melting point of aluminum,and ignition occurs at temperature of about 1600 K, and the independent of the volume of thermite sphere and ignition temperature is not correctly calculated by the Frank-Kamenetskii theory of homogeneous combustible system.

149. Reaction Behavior for PBX-2 Explosive at Different Heating Rate

DAI Xiao-gan,HUANG Yi-min,Lü Zi-jian and SHEN Chun-ying, chinese journal of energetic materials,2010,18(3):282~285

Abstract: Cook-off tests for PBX-2 explosive with different heating rates of 3,5,10,25,105 ℃•min-1 were carried out. Temperature changing processes in sample radius and sample center were recorded by thermocouples,and the reaction degree of PBX-2 explosive was gained by blast pressure gauges. Reaction behavior for PBX-2 explosive was analyzed macroscopically under heat effect. The results of the tests initially show that the reaction degree for PBX-2 explosive is reduced with high heating rate in cook-off test. Numerical simulation was made for PBX-2 explosive by Arrhenius method. Calculated temperature is accord with experimental result.

150. Safety Property of FOX-7 and HTPB Propellants with FOX-7

CHEN Zhong-e,LI Zhong-you,YAO Nan,LEI Qing and WANG DU, chinese journal of energetic materials,2010,18(3):316~319

Abstract: Sensitivities of FOX-7(RDX)and HTPB propellants with FOX-7(RDX ) were studied by means of DSC-TG,sensitivity test apparatus. Results show that the apparent activation energy of FOX-7 is 245.2 kJ•mol-1 and the major exothermic DSC peak temperature is 222.13 ℃,and friction sensitivity is less than 68% while impact sensitivity is over 25.0 J. Compared with RDX formulations,mechanical sensitivities and electrostatic discharges of HTPB propellants with FOX-7 reduce remarkably. When the content of FOX-7 is 15% in HTPB/AP propellants,the violent decomposition of AP is weakened evidently and the major exothermic DSC peak is about 260 ℃ which is 40 ℃ lower than that of RDX/HTPB formulations.

151. Submicron TATB Preparation, characterization and performance testing

Sovereign, Jing-lin, Chen Yafang, "Explosive", 2007, (2): 29-31

Abstract: Solvent - non solvent re-refining of the crystalline average size was prepared for the 520.9nm of submicron TATB, and scanning electron microscope photographs were compared. Ultrafine TATB on the performance of tests to zero-gap and small gap test flash point test as the basis to study fine TATB's energy output and thermal sensitivity. The results show that compared with the raw material TATB, submicron TATB the outbreak points up to 3.22%, steel engraving is increased by 8.51%, and their causes analyzed theoretically.

152. Nano CoFe2O4 Preparation and Thermal Decomposition of AP

Wu Bingheng, Shuang-Qi Hu "Energetic Materials", 2009, 17 (3): 278-282

Abstract: With oil/water interface reaction between the chemical precipitation of nano CoFe2O4 precursor thermal decompositioncharacteristics, using XRD, TEM calcined at different temperatures generated Nano CoFe2O4 were characterized by DSC of different levels of ammonium perchlorate CoFe2O4 nano (AP) the catalytic decomposition. The results showed that: 300ºC or so have begun the formation of spinel CoFe2O4, with increasing temperature, crystallization become completely, while graduallyincreasing the grain size particles, 500ºC is available under the smaller particle size, nano-crystalline spinel good CoFe2O4; in the AP after adding nano CoFe2O4 enable the AP at a lower temperature thermal decomposition occurs, and on AP thermal decomposition with the increase of its content.

153. Thermal and Numerical Method of Calculating the kinetic parameters of Exothermic Decomposition Reaction of Energetic from Peak Temperature of DSC Curves at Constant Heating Rates

Hu Rong-zu, Gao Hong-xu, Zhao Feng-qi, Zhang Hai, Hong-an, Ma Hai-Xia, Xing Xiao-ling

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 (NL-INT) for 2,4,6-trinitro-2,4,6-triazacyclohexanone (Keto-RDX), approximate well to each other the value, 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.