Based on the internationally recognized perfect VIRIAL equation of state, the equation of state for detonation products of VLW explosives was established. The formation background of the equation of state for detonation products of VLW explosives was briefly described, and the derivation process of VLW equation was presented. The detonation performance parameters of military high explosives, civil industrial explosives, condensed phase explosives and gaseous fuel air explosives were calculated by using VLW equation. The thermodynamic functions of detonation products(internal energy, entropy, chemical potential, etc.)were derived. The results show that the parameters calculated by VLW equation are accurate and reasonable, and the calculation problem of advanced VIRIAL coefficient at high temperature(T^*>20)is successfully solved, and the properties of VIRIAL equation under detonation condition are accurately expressed.

In order to implement the application of Trimethylolethane trinitrate (TMETN) in the casting composite modified double base (CMDB) propellants for reducing the sensitivity, the plastication of TMETN other plasticizers on nitrocellulose (NC) was studied by molecular simulation and experimental methods. The interactions between different plasticizers and NC were calculated by Materials Studio 7.0, and then the test result of the curing effect, mechanical properties and mechanical sensitivity of the propellants containing different plasticizers were verified. The results showed that even though TMETN can make the impact sensitivity of propellant up to 58.6 cm, the friction sensitivity reduced to less than 40%, but when the content of TMETN exceeded a certain value, the propellant cannot plasticizing, only by adding nitrocellulose (NG) as assistant plasticizer or improve processing property. This was consistent with the theoretical calculation results of NG > NG/1,2,4-butanetriol trinitrate (BTTN)>TMETN for NC plasticizing effect.

The paper presents requirements for the N₂O decomposition catalyst and provides justification for the selection of components to develop its formulation. The methods to study the physical and chemical as well as catalytic properties of catalysts were developed, and the results of experimental studies on the properties of catalysts with different composition in the laboratory conditions were presented. The activity of samples of compact metal catalysts as well as samples of supported metal and oxide catalysts in the nitrous oxide decomposition reaction was studies. The methodology for determining the activity of catalysts in the decomposition reaction of N₂O is presented, as well as the design of an experimental reactor for determining the activity of the catalyst by the minimum temperature for the onset of the decomposition reaction of N₂O. In the course of the study, the following series of catalyst activity are determined in the N₂O decomposition reaction up to a temperature of 600℃: based on platinum group metals applied to the aluminum oxide carrier — Rh>Ru>Ir>Pt>Pd; based on simple oxides applied to the aluminum oxide carrier —CoO>Cr₂O₃, MnO₂>CuO>ZrO₂>NiO>Fe₂O₃. The following activity series for the most promising carriers are also determined: by the onset temperature of decomposition, ZrO₂>Al₂O₃-CaO>Al₂O₃-ZrO₂>Al₂O₃-AlN>θ-Al₂O₃>Al₂O₃-SiO₂>SiO₂>α-Al₂O₃; by the rate constants of N₂O decomposition, Al₂O₃-SiO₂>Al₂O₃-AlN>ZrO₂>Al₂O₃>Al₂O₃-ZrO₂>Al₂O₃-CaO>α - Al₂O₃>SiO₂. The paper presents the results of selecting the active component and carriers for the supported catalyst. The author proposes formulations of the nitrous oxide decomposition catalyst for bench testing in simulated engines.

The developments of amplification methods of nitrogen chains in energetic material synthesis were reviewed. The common reactions such as substitution reactions of N—X bonds by azido groups, electro-catalytic oxidation reactions of azide ions, diazo transfer reactions of primary amines, dimerization reactions of diimine, N-amination and nitration reactions, oxidative coupling reactions of amine groups, and diazo-coupling reactions of amine groups were summarized. The mechanisms of typical amplification reactions of nitrogen chains were also introduced. The structural evolution processes of ionic nitrogen chains such as N⁺₅, [N₇O]⁺, N^-₈, and organic compounds with all-nitrogen fragments such as N₃/N₄/N₅/N₆/N₇/N₈/N₁₀/N₁₁ chains were emphatically discussed. The possible synthetic routes of N^-₇, N₁₀ and N₁₂ chains and the development trends of this research field were pointed out. With 65 references.

To understand the rheological behavior of 3,4-dinitropyrazole(DNP)/HMX suspension under different influencing factors, the rheological properties of DNP/HMX suspension were tested by using a Brookfield R/S rheometer,and the effects of HMX content, particle size, particle gradation, system temperature and chemical additives on rheological behaviors of suspensions were measured. Results show that DNP is an Newtonian fluid and its apparent viscosity is about 16.4mPa·s, which is 82% higher than TNT and 140% higher than DNAN. At the same shear rate, the apparent viscosity of DNP/HMX melt-cast explosive suspensions increases with the increase of solid content. When the solid content is 30%, the suspension is similar to an Newtonian fluid. However, when the solid content is higher than 30%, the apparent viscosity decreases exponentially with the increase of shear rate. In addition, the apparent viscosity of suspensions decrease with the increase of particle size or system temperature. The flow activation energies increase from 29211J/mol to 38458J/mol when the temperature rises from 95℃ to 105℃. Furthermore, when the solid content is 60%, the optimal mass ratio of HMX particles with average particle size(d₅₀)of 16.6μm and 575.6μm is 1:5, and the apparent viscosity of suspension is the smallest. N-methyl-4-nitroaniline(MNA)makes the apparent viscosity of suspensions decrease, while cellulose acetate butyrate(CAB)and microcrystalline wax-80(MV80)make the apparent viscosity of suspensions increase.

In order to study the influence of negative pressure environment on explosion shock wave, the experiment of negative pressure explosion was carried out in a designed adjustable vacuum explosion vessel. PCB pressure sensor was used to measure the overpressure of shock wave at fixed position of tank axis. The overpressure time history curves of the explosion shock wave at different negative pressure environments of 0,-20,-40,-60,-80,-90kPa were analyzed. The results show that the peak overpressure of the first and the second shock wave at the measuring point is reduced when the negative pressure of the explosion environment is reduced. The overpressure is decreased significantly under negative pressure environment of -40kPa and -99kPa. The velocity of explosion shock wave is related to the density of propagation medium, that is, the lower the negative pressure is, the thinner the gas is, and the faster the propagation velocity of shock wave is. The velocity of explosion shock wave increases with the decrease of negative pressure, and there is no correlation with the decrease of overpressure. Negative pressure environment does not change the amount of gas products produced by the explosion of detonator in the vessel. In the near absolute vacuum environment, the explosion shock wave mainly propagates by detonation products, and the increase of shock wave velocity is limited by the movement speed of detonation products. So the explosion shock wave is weak in intensity and decays rapidly.

Starting from 2-bromo-2-nitropropane-1,3-diol, tert-butylamine and 37% formaldehyde, an energetic compound of 1,3,5-trinitrohexahydropyrimidine(TNHP)was achieved with a total yield of 33%(or 21.11%)through a synthetic procedure including condensation-cyclization, nitration and NaBH₄(or KI)carbon-bromine cleavage reduction. The structure of TNHP as well as its synthetic intermediates were characterized by IR, NMR, elemental analysis and MS techniques. The single crystal of TNHP was prepared and determined via X-ray single crystal diffraction analysis, its physicochemical and detonation properties were further studied by experimental and theoretical methods. The results show that TNHP crystallizes in monoclinic with the space group of P2₍₁₎/c with a crystal density of 1.787g/cm³. Its decomposition temperature is 150.6℃,and the calculated heat of formation, detonation velocity and impact activity are -50.49kJ/mol, 8388m/s and 22.5J, respectively, indicating a potential application prospect in the field of explosives.

To study the effect of by-products on the properties of chlorine-free TATB synthesized by phloroglucinol method, column chromatography was used to effectively separate the trace by-products contained in TATB. The by-products were qualitatively analyzed by FTIR, NMR and MS. Thermal decomposition properties of TATB and by-products were studied by differential scanning calorimetry and thermogravimetry; Based on the density functional theory, some detonation performance parameters of TATB and by-products were calculated. The results show that the by-products in TATB are 1-amino-3,5-diethoxy-2,4,6-trinitrobenzene(AETB)and 1,3-diamino-5-ethoxy- 2,4,6-trinitrobenzene(EDATB). There are some differences between the thermal decomposition properties of by-products and TATB. Both TATB and by-products have only one thermogravimetric process, but the initial temperature and rate of the by-product mass loss process are much lower than that of TATB. At the same heating rate, the exothermic decomposition peak temperatures of AETB and EDATB are 109.2℃ and 121.4℃ lower than those of TATB, respectively. TATB only has one exothermic decomposition process at higher temperatures. EDATB and AETB have obvious endothermic melting phenomena at lower temperatures, and the exothermic decomposition gradually occurs when the temperature continues to rise to a certain value, and the thermal stability of the by-products is much lower than that of TATB. The detonation heat values of the by-products calculated by density functional theory(DFT)are very close to that of TATB, but the values of density, detonation velocity and detonation pressure are all lower than those of TATB.

In order to understand the reaction kinetics and end point of curing of azide binder/non-isocyanate bonding system, the curing behaviors of glycidyl azide polymer/bis-propargyl-succinate(GAP/BPS)bonding system were investigated by using non-isothermal and isothermal microcalorimetry according to Kissinger and Crane equations. The results show that the curing reaction has the maximum heat release when the molar ratio of —C≡C— and —N₃ is 1. The apparent activation energy, pre-exponential factor, reaction order and curing reaction heat for the curing reaction of GAP/BPS bonding system are 80.33kJ/mol, 10^8.42s^-1, 0.94 and -1357.69J/g, respectively. The characteristic temperatures of curing reaction system are calculated by curve fitting, and the values of gelation temperature, curing temperature and post-curing temperature are 313.87, 316.18 and 338.55K, respectively. Autocatalytic phenomenon exists in the curing reaction process of the GAP/BPS bonding system. The function relation between the curing time and the curing temperature is also fitted with y=4.13×10¹⁰e^{-0.064 41x}+5.029.

To study the effect of particle size gradation on the rheological properties of CL-20 based explosive ink, the CL-20 samples with diameters of 400nm and 4μm and seven kinds of CL-20 based explosive inks with different particle size gradations were prepared. The viscosity of the CL-20 based explosive inks were tested by Brookfield(CPS)rheometer and the corresponding rheological data was obtained. The non-Newtonian index, yield value and thixotropic index were calculated. The results show that the particle size gradation of explosives has a significant effect on the rheological properties of explosive inks. With the increase of CL-20(d₅₀=4μm)content, the viscosity of explosive inks first decreases and then increases. At the same time, the non-Newtonian index first increases and then decreases, and the yield value and the thixotropic index also generally decrease first and then increase. When the mass ratio of CL-20 with particle sizes of 400μm and 4μm in the explosive ink is 1:2, the maximum non-Newtonian index is 0.41; the yield value and the thixotropic index are both at the minimum(26.73 and 8.74, respectively),showing that under this particle size grading condition, the explosives inks have better rheological properties.

To meet the needs of internal tensile stress test of polymer bonded explosives(PBX), a test method for internal tensile stress of PBX based on hydraulic fracturing method was established by using the hydraulic fracturing method and the modified test of hole edge stress state. To verify the validity of the method, the universal material testing machine was applied to simulate the internal tensile stress of the component. And the hydraulic fracturing stress test experiments under different tensile stresses were carried out on a self-built PBX hydraulic fracturing testing platform. The results show that the internal tensile stress of PBX explosive can be qualitatively described by hydraulic fracturing method directly, and the test results have a good correlation with the pre-stress(correlation coefficient is 98.90%). However, it can not be described quantitatively. Through uniaxial tensile test of the sample with hole, the effective stress concentration coefficient of the hole edge is obtained. Then, the corresponding correction coefficient of the hole edge stress state is introduced to modify the hydraulic fracturing method. The corrected stress value is in good agreement with the pre-stress, and the average relative error is 10.67%. The established testing method is not limited by the testing depth, and the magnitude and direction of tensile stress can be measured theoretically. Therefore, it is a quantitative test method for the internal tensile stress of PBX explosives based on the hydraulic fracturing method.

To better understand the evolution law and phase transition behavior of CL-20 crystal structure,high pressure phase transition of ε-CL-20 was investigated in the range of 0-50GPa by in-situ Raman and infrared spectrum method in diamond anvil cell, respectively. The results show that there are two phase transitions in the CL-20 crystal during the whole pressurization process. The first transition starts at 4.2GPa and completes at about 7.5GPa, which is considered to be the γ phase transition from the ε phase to the lower symmetry. The reason of the phase transition is that the direction of nitro group outside the cage ring changes under the action of pressure, and the molecular configuration transition caused by the reset of electron cloud density. The second phase transition occurs at 14.2-18.9GPa, which belongs to the crystal structure transition from γ phase to the ζ phase.After pressure release,Raman and infrared spectra return to atmospheric pressure state, indicating that the phase transition process of the CL-20 crystal is reversible.

To improve the quality of explosive powder press molding, taking the JO-9159 explosive column with size of Φ26mm×22mm as an example, a modeling method that regards explosive powder as a continuum was adopted,and the Shima-Oyane material model and advanced nonlinear Msc.Marc were applied to build a simulation model of the powder pressing process. The variation of powder displacement and relative density at different locations was analyzed, and the effects of pressing rate and initial density on the relative density and springback amount of explosive powder after molding were also researched. The results show that the Shima-Oyane material model can simulate the powder pressing process well.The flow between the explosive powder and the mold contact area is relatively slow, the pressing rate and the initial density affect the quality of the explosive powder after molding,and the increase in initial relative density helps to improve the quality of explosive powder after molding. When the pressing rate is in the range of 230—250mm/s, the relative density of the powder after molding is relatively uniform and the springback amount is small. Therefore, the quality of powder molding is better.

To study the combustion characteristics of ammonium perchlorate/hydroxyl-terminated polybutadiene(AP/HTPB)at subatmospheric pressure, a two-dimensional sandwich model was established by using a three-step reaction kinetics mechanism, coupled with gas-solid phases. The AP/HTPB micro-combustion was simulated at 20-80kPa, and compared with the combustion characteristics of AP/HTPB at high pressure of 4MPa. The results show that the first step reaction in the BDP model is close to the burning surface under subatmospheric pressure, and it has a high heat release, which plays a dominant role in the combustion process of AP/HTPB propellant. Different pressure in the combustion process leads to distinct flame characteristics. Diffusion and mixing processes coexist in the flame under subatmospheric pressure, but only diffusion flame under high pressure. Compared to the high pressure condition, flame under the subatmospheric pressure is far from the burning surface and has a large area. The temperature distribution of gas-solid phases is distinct due to the difference of heat transfer area and heat release rate at high and low pressures, thus affecting the shape of the burning surface. The junction of AP and HTPB under subatmospheric pressure is prominent relative to the whole burning surface, while the junction under high pressure is depressed relative to the whole burning surface.

In order to study the effect of particle size of reduced PbSnO₃ on the combustion properties and stability of Al/HMX/CMDB propellants, six kinds of Al/HMX/CMDB propellants containing reduced PbSnO₃ with different particle sizes were prepared by dry sieve test. Their burning rate, time needed for color change of methyl-violet, pressure exponent and safe storage life were studied by burning rate target line test, methyl violet test and thermal accelerated aging test. Results show that the catalytic activity of Pb²⁺ and SnO₂ increases gradually with particle size of reduced PbSnO₃ decreases from 7.0μm to 2.5μm.The burning rates of the propellant increase gradually in the range of 15 to 20MPa, and the pressure exponent decreases from 0.30 to 0.17. As the particle size of reduced PbSnO₃ decreases, the self-catalysis of the propellant accelerates and the stability of the propellant decreases. When the particle size of reduced PbSnO₃ ranges from 2.5μm to 3.5μm, the stability of the propellant decreases significantly.

In order to improve the performance of ammonium perchlorate(AP)so as to improve the combustion performance of composite solid propellant, nano ZnO cubic catalyst(n-ZnO/cube)was synthesized by AP assisted metal organic framework(MOF)thermal decomposition method. Its morphology was characterized by XRD,FESEM,TEM, and its specific surface area and pore size distribution were analyzed. Its effect on the thermal decomposition of AP was analyzed by TG-DTA. The effects of n-ZnO/cube on the process performance, safety performance, mechanical properties and combustion performance of HTPE propellant were tested. The results show that the large specific surface area of 70.5m²/g and a large number of pore structures of n-ZnO/cube catalyst decrease the high temperature decomposition peak of AP from 413 ℃ to 279℃, increase the heat release from 584J/g to 1520J/g, and decrease the decomposition activation energy from 151.1kJ/mol to 65.3kJ/mol. The burning rate(20℃, 6.86MPa)of HTPE propellant increases from 12.01mm/s to 16.16mm/s when 2%(mass fraction)n-ZnO/cube is added into the propellant. The process performance, safety performance, mechanical properties, burning rate pressure index(0.42, 20℃, 3-16MPa)and burning rate temperature sensitivity coefficient(2.02×10^-3 /℃, -55-70℃, 6.86MPa)are not affected significantly, showing that nano ZnO cubic structure has good catalytic performance on thermal decomposition of AP, and it is a potential burning modifier for HTPE propellant.

To improve the mechanical properties of combustible cartridge cases composed of hexogen(RDX)and cellulose acetate(CA), carbon fiber(CF)was added in the basic formulation,and the microcellular combustible cartridge cases with CF were fabricated by the supercritical carbon dioxide(SC-CO₂)foaming technique. The inner structure of combustible cartridge cases with CF was investigated by the scanning electron microscopy, and the mechanical property was studied by impact test. The results show that the impact strength of combustible cartridge cases is improved by adding prober CF, and the impact strength increases with increasing the content of CF. The impact strength of unfoamed combustible cartridge cases increases from 5.11kJ/m² to 8.20kJ/m² when the content of CF is 1.0%, and the increment is 60.47%. The cell diameter increases with increasing the saturation pressures, foaming temperatures and foaming times, and the cell ruptures and collapses when temperature is higher than 130℃. The impact strength of combustible cartridge cases reduces after foaming. Compared with the sample prepared by the free foaming, the impact strength of sample prepared by the constrained foaming technology is improved from 5.93kJ/m² to 6.34kJ/m² when the foaming time is 180s.

To predict the function failure reflected in the change of interior ballistic performance caused by deterrent migration during act: storage of deterred gun propellant for firearms, the Fick's second law and the relationship between diffusion coefficient and diffusion activation energy were used to establish a prediction methodology of function failure threshold value of deterred gun propellant for firearms, with the premises of the same deterred layer structure and the same interior ballistic performance. Three kinds of deterred gun propellants were stored at 75℃ and 85℃ respectively, and the diffusion activation energy of each gun propellant was calculated by this method. The chamber pressure function failure threshold value of three kinds of deterred gun propellants at 65℃ was predicted based on the value at 75℃, and it was compared to the tested value at 65℃ by interior ballistic experiment. The results show that the deviations between the predicted and measured values are 10.3%, 2.9% and 7.9% respectively. Based on the average diffusion activation energy at 65, 75 and 85℃, the functional failure thresholds of the gun propellants at different temperatures are calculated. And the requirements for the maximum storage temperature of the three deterred gun propellants with different formulations are put forward to meet the 17 years'storage life requirements of conventional ammunition.

To investigate the damage processes of the adhesive interfaces of solid rocket motors at meso-scale, in-situ tensile tests were conducted. The damage process of the adhesive interface in an in-situ tensile test was observed by scanning electron microscopy(SEM), and the SEM images at different tensile strains were obtained. Digital image correlation method was adopted to analyze these images, and the strain field of the adhesive interface during the in-situ tensile test was achieved. The results show that, during the in-situ tensile process of the adhesive interface, when the external tensile strain was small, the damage is mainly located at the interface of the propellant/liner, while the damage to the propellant is small. As the external tensile strain increases, the particle-binder interfaces are damaged. Then the damaged area expands continuously, eventually resulting in a damage through the entire adhesive interface. The combination of SEM and digital image correlation can be effectively used for measurement of the deformation field of the meso-scale damage of the adhesive interface, and provid a new method for analyzing the damage process. During the in-situ tensile process, the whole strain fields increases with increasing the tensile strain, and ε_x is much greater than ε_y and ε_xy. When the external tensile strain increases from 5% to 25%, the peak value of mean strain ε^-_x in x direction, which located in liner, increases from 0.07 at 5% to 1.25 at 25%. When the external tensile strain increases from 25% to 28%, the ε^-_x of propellant increases sharply. When the adhesive interface fails, the ε^-_x of propellant is about 1.85.

To investigate the damage processes of the adhesive interfaces of solid rocket motors at meso-scale, in-situ tensile tests were conducted. The damage process of the adhesive interface in an in-situ tensile test was observed by scanning electron microscopy(SEM), and the SEM images at different tensile strains were obtained. Digital image correlation method was adopted to analyze these images, and the strain field of the adhesive interface during the in-situ tensile test was achieved. The results show that, during the in-situ tensile process of the adhesive interface, when the external tensile strain was small, the damage is mainly located at the interface of the propellant/liner, while the damage to the propellant is small. As the external tensile strain increases, the particle-binder interfaces are damaged. Then the damaged area expands continuously, eventually resulting in a damage through the entire adhesive interface. The combination of SEM and digital image correlation can be effectively used for measurement of the deformation field of the meso-scale damage of the adhesive interface, and provid a new method for analyzing the damage process. During the in-situ tensile process, the whole strain fields increases with increasing the tensile strain, and ε_x is much greater than ε_y and ε_xy. When the external tensile strain increases from 5% to 25%, the peak value of mean strain ε^-_x in x direction, which located in liner, increases from 0.07 at 5% to 1.25 at 25%. When the external tensile strain increases from 25% to 28%, the ε^-_x of propellant increases sharply. When the adhesive interface fails, the ε^-_x of propellant is about 1.85.