THÔNG TIN TÀI LIỆU
MINISTRY OF EDUCATION MINISTRY OF NATIONAL AND TRAINING DEFENCE ACADEMY OF MILITARY SCIENCE AND TECHNOLOGY NGUYEN MAU VUONG STUDY THE DEPENDENCE OF THERMAL DECOMPOSITION PROCESS AND VELOCITY OF DETONATION ON THE COMPOSITION OF EXPLOSIVE MIXTURE BASED ON HEXOGEN Major: Theoretical and Physical Chemistry Code: 44 01 19 SUMMARY OF DOCTORAL THESIS Ha Noi - 2020 CôBỘ GIÁO DỤC VÀ ĐÀO BỘ QUỐC PHỊNG TẠO VIỆN KHOA HỌC VÀ CƠNG NGHỆ QUÂN SỰ The work was completed in : Academy of Military Science and Technology, Ministry of Defence Science intructors: Assoc Prof Dr Ngo Van Giao Assoc Prof Dr Dang Van Duong Reviewer 1: Prof Dr Thai Hoang Vietnam Academmy of Science and Technology Reviewer 2: Assoc Prof Dr Dam Quang Sang Military Technical Academy Reviewer 3: Assoc Prof Dr Ninh Duc Ha Academy of Military Science and Technology The thesis is protected at the doctoral thesis evaluation council meeting at: Military Science and Technology Institute At: ……… , date: … /… /2020 Thesis can be searched at: - Academy of Military Science and Technology Library - National Library of Vietnam LIST OF SCIENTIFIC WORK PUBLISHED Nguyen Mau Vuong, Ngo Van Giao, Nguyen Ngoc Tu (2014), Thermal decomposition studies on cast mixture of TNT and RDX, Proceedings The 3th Academic Conference on Natural Science for Master and PhD Students from Asean Contries, Publishing House for Science and Technology, p.411-417 Nguyen Mau Vuong, Ngo Van Giao, Dang Van Duong (2015), Study the dependence of velocity of detonation on the composition of mixed explosive ТГ, Journal of Military Science and Technology Research, Issue number HH-VL, 10-2015, Academy of Military Science and Technology, p.220227 Nguyen Mau Vuong, Ngo Van Giao, Dang Van Duong (2015), Research into thermal decomposition of a mixture of RDX and insensitive, Proceedings The 4th Academic Conference on Natural Science for Young Scientists, Master and PhD Students from Asean Contries, Publishing House for Science and Technology, p.216-222 Nguyen Mau Vuong, Ngo Van Giao (2016), Study the dependence of velocity of detonation on the composition of mixed explosive A-IX-1, Journal of Chemistry and Application, number 1(33)/2016, Vietnam Chemical Association, p.42-44 Nguyen Mau Vuong, Ngo Van Giao, Dang Van Duong, Research results of dependence of explosive heat on the composition of explosive ТГ, Journal of Chemistry and Application, topical number (02) /2019, Vietnam Chemical Association, p.4-8 g OPENING The urgency of the thesis Hexogen or RDX is the common name of cyclonite; 1,3,5-trinitro1,3,5-triazocyclohecxan, hay cyclotrimetylen trinitramin, with the formula C3H6O6N6 RDX (symbol is , RDX) is one of the strong classic explosives RDX explosive has a high detonation velocity (8380 m/s at a density of 1.70 g/cm3), a high fertility force measured by the lead bomb method is (450 ÷ 520) ml However, RDX is highly sensitive (70 ÷ 80%), does not tolerate compression and decomposes before melting Therefore, people often use it in combination with a high-tech explosive (fusible, not decomposing when molten) like TNT to cast into the heart of bombs, mines, bullets, explosive primers or with domestication reduces sensitivity, increases compressive resistance to load into concave bullets, explosive ammunition destroys damage Currently, the military has invested in RDX'sproduction on an industrial scale Same with the TNT's production line, this line has been in production for the past time At the same time, the military has been and will continue to invest in production lines and repair of mortar bullets, antitank bullets and low-level anti-aircraft missiles However, studies on the process of thermal decomposition, the dependence of detonation velocity on the mixture components on the RDX platform, although already mentioned but still limited This research determines the ability of the technology to load mixed explosive into the bomb core, researching the effect of ingredients on explosive speed will determine the power of explosives This issue has also been studied but is not have much public documents Especially in our country, this subject has not been mentioned We received technology transfer, load making under contract, but there is no scientific basis to serve the design and manufacture of new types of ammunition suitable to the level of technology and combat capability for our army Therefore, the PhD student: "Studying the dependence of explosive speed and decomposition process on the composition of explosive mixture based on hexogen" is not only scientifically meaningful but also practical, urgent as a scientific basis for the research, design and manufacture of new types of ammunition suitable to the technological and operational conditions of the army In calculating the design of bullets and explosive blocks currently, the world has used the copyrighted software ANSYS (Autodyn, LS-Dyna), MSC (Nastran, Dytran) to simulate explosive effects with accuracy , very high reliability From these simulations, people shorten the time and money to come up with an optimal design for each type of product in accordance with the set goals Each ammunition design (or explosive device) will be optimized with a specific type of explosive g In the military, with the initial tactical specifications set for the design of ammunition, bombs and mines, especially with the use of concave explosive effect, the parameters put in the software for the most important explosive were density, detonation velocity When changing these important parameters, the results obtained are completely different for a given design There will be parameters to ensure that the design achieves the optimal effect of the explosion, sometimes it is economically optimal while still ensuring the initial specifications Therefore, it is urgent to set up a manual of explosive systems (with all important parameters) At the same time, studying the thermal decomposition process will help determine the safe casting temperature range, the half-life of the drug depends on the storage temperature This is also the basis to determine the durability of the product and guide the storage conditions of ammunition storage The objectives of the thesis Research theoretical and experimental basis on the explosion process of two explosive explosives on the basis of RDX (T, A-IX-1) to build the orientation database for setting up a single explosive component suitable for use in researching and designing shaped bullets, concave bullets, bullets with strong destructive power; determine the safe casting temperature range, predict the life of the product based on the calculation of the half-life of explosives and indicate the importance of temperature factor to the life of the product in preservation process, fire safety of bullets and explosives The content of the thesis research - Calculate the dependence of oxygen balance, oxygen coefficient, assumed molecular formula, explosive heat on the composition of combined explosive T, A-IX-1 - Determination of kinematic parameters of the decomposition process when changing explosive components T nổ, A-IX-1 From there, calculate the half-life of explosives, predict product durability - Determining the experimental equation depending on the explosive speed, explosive heat on explosive components T, A-IX-1 Scientific, practical and new contributions of the thesis - Starting from the actual need to study these two types of explosives in order to build a database for the design of a single component in accordance with the requirements of the design and manufacture of bullets (especially concave bullet, bullet shaping), bombs and mines - Based on the method of thermal analysis, determining the safe casting temperature range, predicting the life of the product based on the calculation of the half-life of explosives and showing the importance of the factor temperature to the shelf life of the product during safe storage of fire and explosion g * Research Methods The project uses a combination of methods of theoretical calculation and empirical measurement with high precision on modern and advanced equipment and facilities (from the method of prototyping, uniform sample preparation) small errors to the use of modern, highprecision equipment) to establish reliable empirical laws * The layout of the thesis The thesis includes: Introduction, four chapters, conclusions, list of references Heading Describe the urgency of the thesis topic, general overview of the objectives, content, research methods, scientific and practical meanings of the thesis and briefly introduce the layout of the thesis Chapter I Overview Analyzing and evaluating the domestic and foreign research situation, related issues and issues to be addressed in the thesis Chapter II Research methods Presentation of prototyping methods, calculation methods and measurement methods for explosive explosives Chapter III Results and Discussion This chapter focuses on solving the researched content of the thesis CONTENTS OF THE THESIS CHAPTER I: OVERVIEW Regarding RDX explosives and RDX-based mixtures, analyzing and evaluating domestic and foreign research situation, related issues and issues to be addressed in the thesis CHAPTER II: SUBJECTS AND METHODS OF THE STUDY 2.1 Research subjects 2.1.1 Object: The research object of the thesis is ТГ and A-IX-1 explosive systems 2.1.2 Chemistry Korean chemicals (RDX), China: TNT, serezin, sudan, Malaysia: stearic acid; 2.2 Research Methods 2.2.1 Method of calculating oxygen balance and oxygen coefficient 2.2.2 Method of measurement and calculation of explosive heat 2.2.3 Methods and equipment for determining the explosion rate 2.2.4 Thermal analysis method 2.2.5 Conformity assessment method and thermal endurance by DSC 2.2.6 Method of calculating kinematic parameters 2.2.7 Scanning electron microscope SEM g 2.2.8 Measurement of particle size distribution by laser scattering 2.2.9 Method of manufacturing research samples 2.2.10 Methods for determining the composition of explosive products 2.2.11 Methods of processing empirical data CHAPTER III RESULTS AND DISCUSSION 3.1 Oxygen balance and oxygen factor and composition of explosive products 3.1.1 Calculation of factors and components of explosive products 3.1.1.1 Explosive system TГ Table 3.1 Oxygen balance and oxygen factor of some ТГ mixtures No Compound name ТГ-23 ТГ-25 ТГ-30 ТГ-35 ТГ-40 ТГ-45 ТГ-50 ТГ-55 ТГ-60 TNT, % RDX, % 23 25 30 35 40 45 50 55 60 77 75 70 65 60 55 50 45 40 Molecular formula assumption C3.90H5.77O6.00N5.32 C3.98H5.75O6.00N5.26 C4.18H5.70O6.00N5.11 C4.38H5.66O6.00N4.97 C4.58H5.61O6.00N4.82 C4.78H5.56O6.00N4.67 C4.98H5.51O6.00N4.52 C5.18H5.46O6.00N4.37 C5.38H5.41O6.00N4.22 Kb , % A, % -33.7 -34.7 -37.3 -40.0 -42.6 -45.2 -47.8 -50.4 -53.1 59.7 59.1 57.6 56.1 54.5 53.0 51.5 50.0 48.5 Based on the above results and applying the Avakian method to calculate the composition of explosive products, the explosive decomposition reaction of explosives marks ТГ can be written as follows: ТГ-23: C17.27H25.54O26.54N23.54 = 3.02CO2 + 10.74H2O + 9.76CO + 2.03H2 + 4.49C +11.77N2 ТГ-25: C16.20H23.41O24.41N21.41= 2.73CO2 + 9.81H2O + 9.13CO + 1.89H2 + 4.34C + 10.70N2 ТГ-30: C14.16H19.32O20.32N17.32= 2.18CO2 + 8.03H2O + 7.92CO + 1.63H2 + 4.06C +8.66N2 ТГ-35: C12.70H16.39O17.39N14.39 = 1.79CO2 + 6.76H2O + 7.04CO + 1.43H2 + 3.86C +7.20N2 ТГ-40: C11.60H14.20O15.20N12.20 = 1.51CO2 + 5.82H2O + 6.37CO + 1.29H2 + 3.72C +6.10N2 ТГ-45: C10.75H12.50O13.50N10.50 = 1.29CO2 + 5.08H2O + 5.85CO + 1.17H2 + 3.62C +5.25N2 ТГ-50: C10.07H11.14O12.14N9.14 = 1.11CO2 + 4.49H2O + 5.42CO + 1.07H2 + 3.54C +4.57N2 ТГ-55: C9.51H10.02O11.02N8.02 = 0.97CO2 + 4.02H2O + 5.06CO + 0.99H2 + 3.48C +4.01N2 ТГ-60: C9.05H9.09O10.09N7.09 = 0.85CO2 + 3.62H2O + 4.76CO + 0.93H2 + 3.43C +3.55N2 3.1.1.2 Explosive system A-IX-1 Table 3.3 Oxygen balance and oxygen factor of dynamite A-IX-13 No Compound name A-IX-13 (6.5) A-IX-13 (6.0) A-IX-13 (5.5) A-IX-13 (5.0) RDX, % CTH, % 93.50 94.00 94.50 95.00 6.50 6.00 5.50 5.00 Molecular formula assumption C3.91H7.83O5.83N5.79 C3.84H7.69O5.85N5.81 C3.77H7.54O5.86N5.82 C3.69H7.40O5.87N5.84 Kb , % A, % -41.22 -39.71 -38.20 -36.70 62.43 62.76 63.08 63.41 g Table 3.4 Oxygen balance and oxygen factor of explosive A-IX-11 No Compound name A-IX-13 (6.5) A-IX-13 (6.0) A-IX-13 (5.5) A-IX-13 (5.0) RDX % 93.50 94.00 94.50 95.00 Serezin % 6.50 6.00 5.50 5.00 Molecular formula assumption C4.00H8.05O5.86N5.86 C3.92H7.89O5.87N5.87 C3.84H7.73O5.88N5.88 C3.76H7.56O5.89N5.89 Kb % A % -42.59 -40.98 -39.37 -37.75 62.34 62.67 63.00 63.34 Based on the above results and applying Avakian method to calculate the composition of explosive products, the decomposition reaction of explosive A-IX-13 can be approximated as follows: A-IX-1 (6.5): C4.05H8.12O6.04N6.00= 0.08CO2 + 3.32H2O + 2.56CO + 0.74H2 + 1.41C +3.00N2 A-IX-1 (6.0): C3.96H7.94O6.04N6.00 = 0.14CO2 + 3.26H2O + 2.50CO + 0.71H2 + 1.33C +3.00N2 A-IX-1 (5.5): C3.88H7.77O6.04N6.00 = 0.19CO2 + 3.21H2O + 2.44CO + 0.68H2 + 1.25C +3.00N2 A-IX-1 (5.0): C3.80H7.60O6.03N6.00 = 0.25CO2 + 3.15H2O + 2.38CO + 0.65H2 + 1.17C +3.00N2 Based on the above results and applying the Avakian method to calculate the composition of explosive products, the decomposition reaction of explosive A-IX-11 (5.0) can be approximated as follows: A-IX-1 (6.5): C4.10H8.25O6.00N6.00 = 0.03CO2 + 3.35H2O + 2.60CO + 0.77H2 + 1.47C +3.00N2 A-IX-1 (6.0): C4.01H8.06O6.00N6.00 = 0.08CO2 + 3.30H2O + 2.54CO + 0.74H2 + 1.39C +3.00N2 A-IX-1 (5.5): C3.83H7.70O6.00N6.00 = 0.14CO2 + 3.24H2O + 2.47CO + 0.70H2 + 1.30C +3.00N2 A-IX-1 (5.0): C3.83H7.70O6.00N6.00 = 0.20CO2 + 3.18H2O + 2.41CO + 0.67H2 + 1.22C +3.00N2 3.1.2 Experimental qualitative composition of explosive products The quantitative analysis is extremely complex and not enough equipment to implement so the subject has used the existing equipment to determine the calculation of the explosive product components of the combination explosive representative ТГ-50, A-IX-13 and A-IX-11 with CTH content of 5.5% Use NARL8514 Lightweight gas analyzer MODEL 4016, showing the results of explosive gas products on the gas chromatography clearly show the pic of CO2, CO, N2 O2 gas is made weak in explosive products of drugs A-IX-1, not existing in explosive products of explosives ТГ-50 The result is also consistent with the calculation of the oxygen balance and the oxygen coefficient of the explosives The more explosives there are negative (or A less positive) than the amount of oxygen in the explosive product The presence of oxygen in the composition of an explosion caused by itself in a bomb when a vacuum can not fully complete the atmosphere (oxygen-ready) reaches 0.03-0.04 bar, so the remaining stain for the A-IX-1 explosive product is reasonable For explosives ТГ-50 due to the more negative coefficient (-47.82%) It is recommended that the g oxygen itself involved in the reaction of the produced (C, CO) products is stronger and almost no stain is detected Using an infrared absorption measurement device Jasco 4600, the resulting absorption spectrometer of the liquid product is similared to the infrared absorption spectrum of the sample ionized distilled water samples As such, it is obvious that the condensation fluid on the main is H2O Use ofscanning electron micrograph JSM-6510 LV-X-ray dispersing probes for the composition of solid products of explosive A-IX13, A-IX-11, ТГ-50, theresults obtained from solid products show the apparent presence of carbon Besides, there are also elements: Cu, Zn, W, O, Cl, Si, Pb, K These elements are present as a result of decomposition of compounds that are in the fire medicine and explosive medicine in the copper differential The substances are: Si, KClO4, W, Pb (N3)2, Zn The casing is made from copper (Cu) The results are clearly visible to the existence of C, CO, CO2, N2, H2O in explosive decomposition products of all three types of explosives In addition, there are O2 in explosive products A-IX-1 Currently, there is no sufficiently sensitive measuring head to determine the presence of H2 in explosive products 3.2 Study the compatibility of the system RDX has the original distribution as shown in Figure 3.14, surface image as Figure 3.15 Photos of explosive surface TГ after mixing are shown in Figures 3.16 and 3.17 Pic 3.14 Particle size distribution of RDX Pic 3.15 SEM image of grain surface of RDX 10 g From the results of the calculation of the decomposition rate constant, found that at the same temperature, the rate constant decreases with increasing TNT content in the mixture This is due to the offset effect, between the activation energy E falling and the pre-factor (frequency) Z decreasing [4], [5] According to the Arrhenius equation, kT is inversely proportional to E and proportional to Z It can be seen that Z decreases when the concentration of TNT increases due to the thickening of the RDX particles due to TNT, making the opportunity for contact between RDX particles plummeted This effect is greater than the activation energy reduction effect E when the TNT content increases Therefore, in general, the reaction rate kT decreases with increasing TNT content From this constant, we can calculate the half-life at different temperatures as shown in Table 3.20 On this basis, we can see that the durability of the product depends largely on the storage temperature Table 3.20 The half-life of ТГ mixture Compound name ТГ-60.0 ТГ-57.5 10 oC 2.88x1008 3.21x1008 The half - life at different temperatures, years 20 oC 30 oC 40 oC 50 oC 07 06 05 1.74x10 1.27x10 1.09x10 1.09x1004 07 06 05 1.91x10 1.37x10 1.16x10 1.14x1004 75 oC 6.18x1001 6.28x1001 ТГ-55.0 ТГ-52.5 ТГ-50.0 7.59x1008 1.10x1009 2.07x1009 4.15x1007 5.78x1007 1.03x1008 2.74x1006 3.68x1006 6.22x1006 2.16x1005 2.80x1005 4.50x1005 1.99x1004 2.50x1004 3.83x1004 9.34x1001 1.09x1002 1.51x1002 ТГ-47.5 5.38x1009 2.43x1008 1.35x1007 9.03x1005 7.13x1004 2.37x1002 ТГ-45.0 1.10x10 10 4.65x10 08 2.41x10 07 1.52x10 06 1.13x10 05 3.29x1002 10 5.28x10 08 2.70x10 07 1.66x10 06 1.22x10 05 3.43x1002 No ТГ-42.5 1.28x10 ТГ-40.0 2.72x1010 1.05x1009 5.04x1007 2.94x1006 2.04x1005 5.08x1002 ТГ-37.5 1.12x10 11 3.88x10 09 1.67x10 08 8.77x10 06 5.54x10 05 1.11x1003 11 5.11x10 09 2.11x10 08 1.07x10 07 6.53x10 05 1.21x1003 10 11 ТГ-35.0 1.55x10 12 ТГ-32.5 2.70x1011 8.45x1009 3.32x1008 1.61x1007 9.38x1005 1.58x1003 13 ТГ-30.0 4.44x10 11 10 08 07 06 2.06x1003 14 ТГ-27.5 5.66x1011 1.66x1010 6.12x1008 2.79x1007 1.54x1006 2.29x1003 15 ТГ-25.0 2.02x10 11 09 08 06 05 7.30x1002 16 ТГ-23.0 1.17x1012 2.53x1006 3.33x1003 1.33x10 5.80x10 3.22x1010 5.04x10 2.10x10 1.12x1009 2.35x10 9.41x10 4.83x1007 1.33x10 5.11x10 From table 3.20, it is shown that storage temperature greatly affects product durability In the normal temperature range in our country (about 10-50 oC), this type of explosive has a half-life of about 10 times when reducing 10 oC of storage temperature Durability decreases sharply when the storage temperature is near the melting point of TNT The higher the RDX content, the higher the durability of the mixture and vice versa the greater the concentration of TNT, the lower the product durability In fact, TNT is easier to melt and more degraded than RDX Therefore, during 11 g Activation energy, kJ/mol storage, to increase the shelf life of the product, it is necessary to cool the storage, especially the warehouses in areas with high weather temperatures during the year Based on the calculation results of the activation energy E and the pre-exponential factor the Z of the explosive mixtures ТГ, we can establish the dependence of these two quantities on the mixture components as shown in Figure 3.44 and 3.45 260,0 250,0 240,0 230,0 220,0 210,0 200,0 190,0 180,0 y = -1.5776x + 287.51 r² = 0.9872 20,0 30,0 40,0 TNT, % 50,0 60,0 Pre-exponential factor ,s-1 Pic 3.44 Graph of dependence of activation energy on TNT content in explosive mixture ТГ 1,20E+26 1,00E+26 8,00E+25 6,00E+25 y = 5.E+30.e-0.428x r² = 0.9874 4,00E+25 2,00E+25 1,00E+18 20,0 30,0 40,0 50,0 TNT, % 60,0 70,0 Pic 3.45 Dependent graph of the pre-exponential factor the Z to the TNT content in the explosive mixture ТГ Thus, on the basis of these two types of graphs, we can approximate the activation energy, the pre-exponential factor the Z of a mixture of dynamite ТГ with specific components whose RDX content is in the range ( 40 ÷ 77)% or TNT content is in the range (23 ÷ 60)% with high reliability (r2 is greater than 0.98) 12 g Activation energy of the mixture depends on the TNT content following the first order equation: y = -1.5776x + 287.51 with correlation coefficient r2 = 0.9872 The pre-exponential factor the Z of the mixture depends on the TNT content following the equation: y = 5.1030.e-0.428x with the correlation coefficient r2 = 0.9874 From this, we can determine the decomposition rate constant and predict the durability through the half-life of a mixture of ТГ with specific components within the studied 3.3.2 Explosive system A-IX-1 3.3.2.1 CTH components Based on the results of DTA measurement and Kissinger's equation graph, the value of activating energy E, pre-exponential factor Z and the reaction rate constant at temperature (T) are determined as table 3.27 Table 3.27 Kinetic parameters and decomposition reaction constants of A-IX-13 No Compound name RDX A-IX-13 (M1) A-IX-13 (M2) A-IX-13 (M3) A-IX-13 (M4) E, kJ.mol-1 252.579 164.384 158.631 142.868 134.437 Z, s-1 1.17 x1026 8.17x1016 2.47x1016 4.74x1014 5.40x1013 kT, s-1 1.17 x1026x e-30380/T 8.17x1016x e-19772/T 2.47x1016x e-19080/T 4.74x1014x e-17184/T 5.40x1013x e-16170/T It is important to calculate the equation for the decomposition reaction rate based on the temperature of T The result of calculating the decomposition rate constant at different temperatures is given in Table 3.28 Table 3.28 The decomposition reaction rate of a mixture of A-IX-13 No Compound name A-IX-13 (M1) Constant reaction decomposition rate at different temperature, s-1 10 oC 20 oC 30 oC 40 oC 50 oC 60 oC 16 16 16 16 16 7.62x10 7.64x10 7.65x10 7.67x10 7.69x10 7.70x1016 A-IX-13 (M2) A-IX-13 (M3) A-IX-13 (M4) 2.31x1016 4.46x1014 5.10x1013 2.32x1016 4.47x1014 5.11x1013 2.32x1016 4.48x1014 5.12x1013 2.33x1016 4.48x1014 5.13x1013 2.33x1016 4.49x1014 5.14x1013 2.33x1016 4.50x1014 5.15x1013 From the results of the calculation of the decomposition rate constant, found that at the same temperature, the rate constant decreases with increasing the content of CTH in the mixture This is due to the offset effect between activating energy E and decreasing pre-exponential factor (frequency) Z According to the Arrhenius equation, kT is inversely proportional to E and proportional to Z It can be seen that Z decreases when the concentration of bio-energy increases due to the thickening of the RDX particles because the self-created domesticated explosives makes the opportunity for contact between RDX particles are falling sharply This 13 g effect is greater than the activation energy reduction E effect when the bioenergy content increases Therefore, in general, the reaction rate kT decreases with increasing bio-energy content From this constant, the half-life can be calculated at different temperatures as shown in Table 3.29 On this basis, it can be seen that the durability of the product greatly depends on the storage temperature Table 3.29 The half-life of a mixture of domesticated A-IX-13 A-IX-13 (M1) 10 oC 5.87x1005 The half - life at different temperatures, years 20 oC 30 oC 40 oC 50 oC 04 03 02 5.41x10 5.84x10 7.26x10 1.03x1002 60 oC 1.64x1001 A-IX-13 (M2) A-IX-13 (M3) A-IX-13 (M4) 1.70x1005 1.07x1004 2.65x1003 1.70x1004 1.35x1003 3.78x1002 6.81x1000 1.18x1000 4.99x10-1 No Compound name 1.98x1003 1.95x1002 6.11x1001 2.65x1002 3.19x1001 1.11x1001 4.01x1001 5.84x1000 2.24x1000 Activation energy, kJ/mol From table 3.29, we see that storage temperature greatly affects product durability In the normal temperature range in our country (about 10-50 oC), this type of explosive has a half-life of about 10 times when reducing 10 oC of storage temperature Durability decreases sharply when the storage temperature is near the melting point of stearic acid (67-70) oC The greater the RDX content, the higher the durability of the mixture and vice versa the higher the content of the CTH, the more the product durability decreases In fact, stearic acid and serezin have a much lower melting point than RDX Therefore, during storage, to increase the shelf life of the product, it is necessary to cool the storage, especially the warehouses in areas with high weather temperatures during the year Based on the results of calculating the activation energy E and the pre-exponential factor the Z of the explosive mixtures A-IX-1, we can establish the dependence of these two quantities on the composition as shown in the figure 3.56 and 3.57 170,0 160,0 150,0 140,0 y = -21.118x + 271.49 r² = 0.9704 130,0 4,5 5,0 5,5 6,0 CTH, % 6,5 7,0 Pic 3.56 Graph of the dependence of activation energy A-IX-13 on the content of CTH 14 Pre-exponential factor , 1/s g 1,40E+17 1,20E+17 1,00E+17 8,00E+16 6,00E+16 y = 2E+28e-5.184x r² = 0.9636 4,00E+16 2,00E+16 0,00E+00 4,5 5,0 5,5 6,0 CTH, % 6,5 7,0 Pic 3.57 Graph of dependence of the pre-exponential coefficient of A-IX-13 on the content of CTH Thus, on the basis of these two types of graphs, we can approximate the activation energy, the pre-exponential factor the Z of an AIX-1 explosive mixture (self-contained substances) Specifically, the content of RDX is in the range (93.5 ÷ 95.0)% or the content of CTH is in the range (5.0 ÷ 6.5)% with high reliability (r2 is greater than 0.96) ) Activation energy of the mixture depends on the content of CTH (including substances) according to the first-order equation: y = -21.118x + 271.49 with a correlation coefficient r2 = 0.9704 The pre-exponential factor the Z of the mixture depends on the content of CTH (including substances) according to the equation: y = 2.10-197.e-5.1836x with the correlation coefficient r2 = 0.9636 From this, it is possible to determine the decomposition rate constant and predict the durability through the half-life of A-IX-1 mixture when the RDX content (or the mixture of domesticated substances) is determined in explosive 3.3.2.2 With CTH component Based on DTA measurement results and Kissinger's equation graph, we can determine the value of activating energy E, pre-exponential factor the Z and constant reaction rate kT at temperature (T) as shown in Table 3.35 According to the results in Table 3.35, it was found that: Activation energy decreases with increasing concentration of bio-energy (serezin) This also has similarities with the use of substances in CTH However, the activation energy of these A-IX-1 models is much lower than that of using substances in CTH This means that to stimulate the thermal decomposition of this A-IX-1 mixture we will need more energy 15 g Table 3.35 Kinetic parameters and reaction rate constants of A-IX-11 No Compound A-IX-11 (M5) A-IX-11 (M6) A-IX-11 (M7) A-IX-11 (M8) E, kJ.mol-1 233.8 231.5 228.3 219.8 Z, s-1 3.03x1024 1.64x1024 7.17x1023 7.43x1022 kT, s-1 3.03x1024x e-28126/T 1.64x1024x e-27850/T 7.17x1023x e-27459/T 7.43x1022x e-26440/T It is important to calculate the equation for the decomposition reaction rate based on the temperature of T The results of calculating the decomposition rate constant at different temperatures are given in Table 3.36 Table 3.36 The decomposition reaction rate constants of A-IX-11 No Compound A-IX-11 (M5) A-IX-11 (M6) A-IX-11 (M7) A-IX-11 (M8) Constant reaction decomposition rate at different temperature, s-1 10 oC 20 oC 30 oC 40 oC 50 oC 75 oC 24 24 24 24 24 2.74x10 2.75x10 2.76x10 2.77x10 2.78x10 2.79x1024 24 24 24 24 24 1.48x10 1.49x10 1.49x10 1.50x10 1.50x10 1.51x1024 23 23 23 23 23 6.51x10 6.53x10 6.55x10 6.57x10 6.59x10 6.63x1023 6.77x1022 6.79x1022 6.81x1022 6.83x1022 6.85x1022 6.89x1022 From the results of the calculation of the decomposition rate constant, it is found that at the same temperature, the rate constant decreases with increasing the content of bio-energy (serezin) in the mixture This is due to the offset effect between activating energy E and decreasing pre-factor (frequency) Z [4], [5] According to the Arrhenius equation, kT is inversely proportional to E and proportional to Z Similarly, it can be seen that Z decreases when the content of TNT (serezin) increases due to the thickening of RDX particles by CTH (serezin) has made the opportunity for contact between RDX particles sharply decrease This effect is greater than the activation energy reduction effect E when the content of bioenergy (serezin) increases In general, the reaction rate kT decreases with increasing concentration of bio-energy (serezin) From the result of this constant, the half-life can be calculated at different temperatures as shown in Table 3.37 On this basis, we can see that the durability of the product depends largely on the storage temperature Table 3.37 The half-life of A-IX-11 A-IX-11 (M5) A-IX-11 (M6) 10 oC 1.05x1011 7.36x1010 The half - life at different temperatures, years 20 oC 30 oC 40 oC 50 oC 09 08 06 3.55x10 1.49x10 7.69x10 4.76x1005 09 08 06 2.56x10 1.11x10 5.90x10 3.75x1005 75 oC 9.14x1002 7.66x1002 A-IX-11 (M7) A-IX-11 (M8) 4.22x1010 1.11x1010 1.54x1009 4.58x1008 5.68x1002 2.93x1002 No Compound 6.98x1007 2.33x1007 3.86x1006 1.44x1006 2.55x1005 1.05x1005 From table 3.37, it is shown that storage temperature greatly influences product durability In the normal temperature range in our country (about 10-50 oC), this type of explosive has a half-life of about 10 times when reducing 10 oC of storage temperature Durability decreases 16 g sharply when the storage temperature is near the melting point of serezin The content of CTH increases, the durability of products decreases and vice versa In fact, serezin has a much lower melting point than RDX Therefore, during storage, to increase the shelf life of the product, it is necessary to cool the storage, especially those in areas with high weather temperatures during the year Based on the results of calculating the activation energy E and the pre-exponential factor the Z of the explosive mixtures A-IX-1, we can establish the dependence of these two quantities on the composition as shown in the figure 3.66 and 3.67 Activation energy, kJ/mol 240,0 235,0 230,0 225,0 y = -9.0606x + 280.47 r² = 0.9076 220,0 215,0 4,5 5,0 5,5 6,0 CTH, % 6,5 7,0 Pic 3.66 Graph of dependence of activating energy A-IX-11 on the content of CTH Pre-exponential factor , 1/s 3,50E+24 3,00E+24 2,50E+24 y = 7.E+29.e-2.39x r² = 0.9041 2,00E+24 1,50E+24 1,00E+24 5,00E+23 0,00E+00 4,5 5,0 5,5 6,0 CTH, % 6,5 7,0 Pic 3.67 Graph of dependence of exponential factor of A-IX-11 on content of CTH Thus, on the basis of these two graphs, we can calculate the approximate activation energy, the pre-exponential factor the Z of an explosive mixture of A-IX-1 ( is serezin) with specific composition If the 17 g content of RDX is within (93.5 ÷ 95.0)% or the content of CTH is in the range (5.0 ÷ 6.5)% with high reliability (r2 is greater than 0.90) Activation energy of the mixture depends on the content of bioenergy (serezin) following the first order equation: y = -9.0606x + 280.47 with the correlation coefficient r2 = 0.9076 The pre-exponential factor Z of the mixture depends on the content of bio-energy (serezin) according to the equation: y = 7.1029.e-2.39x with the correlation coefficient r2 = 0.9041 From this, we can determine the decomposition rate constant and predict the durability through the half-life of A-IX-1 mixture (type domestication is serezin) Comment: Thus, it can be seen that when increasing the content of domestication, the temperature of the mixture begins to melt significantly The above result confirms that the safe temperature range for the use of AIX-1 explosive with hypersensitivity mixture (serezin, stearic acid, sudan) or a domestication (serezin) is (293 ÷ 473) K or (20 ÷ 200) oC However, temperature is extremely important in preserving to avoid degradation of product quality Therefore, always keep cool, low temperature is the decisive condition to the time of storage and use of the product 3.4 Dependence of explosive heat on explosive components 3.4.1 Explosive system TГ Experimental equation of explosive energy on the content of TNT and RDX as shown in Figure 3.68 Q, kcal/kg 1400,0 1380,0 1360,0 1340,0 1320,0 1300,0 1280,0 1260,0 y = -3.101x + 1461.332 r² = 0.999 20,0 30,0 40,0 50,0 60,0 TNT, % Fig 3.68 Graph the dependence of the explosive heat of ТГ into the TNT content It can be concluded: The explosive heat of the explosive explosive mixture ТГ depends on the TNT content according to the first order equation: y = -3.101x + 1461.332 with correlation coefficient r2 = 0.999 Where x is the TNT content (% mass) 18 g 3.4.2 Explosive system A-IX-1 3.4.2.1 CTH components The equation obtains the result as a graph as shown in Figure 3.69 Q, kcal/kg 1365,0 1360,0 1355,0 1350,0 1345,0 1340,0 1335,0 1330,0 1325,0 y = -21.005x + 1463.185 r² = 0.996 4,5 5,0 5,5 6,0 6,5 7,0 CTH, % Fig 3.69 Graph of dependence of explosive heat of A-IX-13 on content of CTH Thus, it can be concluded: The explosive heat of A-IX-1 mixed explosive (kcal/kg) at the density of 1.62 g/cm3 depends on the content of CTH (including substances) according to the first-order equation : y = 21.005x + 1463.185 with correlation coefficient r2 = 0.996 In which, x is the content of CTH (% mass) 3.4.2.2 CTH component We obtain the result of the equation as the graph in Figure 3.70 Q, kcal/kg 1360,0 1355,0 1350,0 1345,0 1340,0 1335,0 1330,0 1325,0 1320,0 1315,0 y = -21.620x + 1461.740 r² = 0.998 4,5 5,0 5,5 6,0 6,5 7,0 CTH, % Pic 3.70 Graph of dependence of explosive heat of A-IX-11 on the content of CTH Thus, it is possible to conclude: The explosive heat of A-IX-1 mixed explosive (1 domesticated substance) at the density of 1.62 g/cm3 depends on the content of CTH according to the first order equation: y = - 19 g 21.620x + 1461.740 with the correlation coefficient r2 = 0.998 In which, x is the content of CTH (% mass) 3.5 Dependence on explosion rate on explosive components 3.5.1 Explosive system TГ 3.5.1.1 Dependent equation of explosive density The result is obtained as the graph in Figure 3.71 𝜌, mg/cm3 1760 1740 1720 1700 1680 1660 y = -1.884x + 1783.563 r² = 0.986 10,0 20,0 30,0 40,0 50,0 60,0 70,0 TNT, % Pic 3.71 Graph of dependence of the highest molding density of explosives TГ (mg/cm3) on TNT content (%) Thus, we can conclude: The highest casting density of explosive TГ (mg/cm3) depends on the content of TNT (x,%) in the first order: y = 1.884x + 1783.563 with r2 = 0.986 3.5.1.2 Dependent equation for velocity of detonation on TNT content a At the same density We built the graph as Figure 3.72 D, m/s 8000,0 7900,0 7800,0 7700,0 7600,0 7500,0 7400,0 7300,0 y = -15.350x + 8288.087 r² = 0.996 20,0 25,0 30,0 35,0 40,0 45,0 50,0 55,0 60,0 65,0 TNT, % Fig 3.72 Graph of dependence of velocity of detonation of TГ (m/s) on TNT content (%) at density of 1.60 g/cm3 20 g Thus, we can conclude: Explosive speed of explosives TГ depends on the composition of TNT in the first order function: y = -15.350x + 8288.087 with correlation coefficient r2 = 0.996 b At the highest casting density We built the graph as shown in Figure 3.73 D, m/s 8300,0 8200,0 8100,0 8000,0 7900,0 7800,0 7700,0 7600,0 7500,0 7400,0 7300,0 y = -21.733x + 8729.624 r² = 0.980 15,0 20,0 25,0 30,0 35,0 40,0 45,0 50,0 55,0 60,0 65,0 TNT, % Fig 3.73 The dependent graph of velocity of detonation of TГ (m/s) in the TNT content (%) at highest casting density Thus, we can conclude: The velocity of detonation of explosive TГ (mg/cm3) depends on the content of TNT (%) at the highest casting density according to the first order function: y = -21.733x + 8729.624 with correlation coefficient r2 = 0.980 Based on the above equations, we can approximate the highest casting density parameter, corresponding explosion rate at that density or explosion rate at commonly used density of 1.60 g/cm3 of any TГ mixture has TNT content of about (23 ÷ 60)% or RDX of about (40 ÷ 77)% 3.5.2 Explosive system A-IX-1 3.5.2.1 With CTH components The most common domestication mixture for making A-IX-1 is: 60% serezin + 38.8% stearic acid + 0.2% sudan Using the above domestication mixture results in a graph as shown in Figure 3.74 Thus, we can conclude: The velocity of explosive of A-IX-13 depends on the composition of CTH with the first function: y = 146.494x + 7024.091 with correlation coefficient r2 = 0.995 21 g D, m/s 8000,0 7950,0 7900,0 7850,0 7800,0 7750,0 7700,0 y = -146.49x + 8708.8 r² = 0.995 4,5 5,0 5,5 6,0 7,0 CTH, % 6,5 Fig 3.74 Graph of dependence of velocity of detonation of A-IX-13 on content of CTH (%) 3.5.2.2 With CTH component We can use a single-component domestication for A-IX-1 To make a comparison with the domesticated mixture of substances, we use the domesticated substance, serezin We obtain the result as the graph in Figure 3.75 D, m/s y = -146.14x + 8686.2 r² = 0.991 8000,0 7950,0 7900,0 7850,0 7800,0 7750,0 7700,0 4,5 5,0 5,5 6,0 6,5 7,0 CTH, % Fig 3.75 Graph of dependence of velocity of detonation of A-IX-11 on content of CTH (%) Thus, we can conclude: + Explosive speed of explosive A-IX-11 depends on the composition of CTH with the first function: y = 146.138x + 7005.658 with correlation coefficient r2 = 0.991 + Based on the newly developed empirical equations, we can calculate the approximate explosion rate of A-IX-1 (using domesticated substance serezin) at any RDX content in the range (93.5 ÷ 95)% with high accuracy 22 g 3.6 Some domesticated chemicals are expected to be used for RDX Mixed explosives are made from RDX and domestication in proportion as table 3.48 The test samples were heated at 10 ° C/min in an inert atmosphere at 50 mg/min The device used is DSC 131 SETARAM The domesticated chemicals used to domesticate RDX not exceed 20% Therefore, to study the compatibility of domesticated substances, we arrange the ratio of RDX/CTH to 80/20 (by weight) Table 3.48 Component ratio (% m/m) of the test samples No Compound name RDX CTH M1 80 % 20% Parafin M2 80 % 20% silicon M3 80 % 20% wax8 M4 80 % 20% polyisobutylen M5 80 % 20% PE wax M6 80 % 20% nilon Table 3.49 Results of measuring DSC thermal parameters of samples No Compound name Peak temperature, Tp Δ Tp Conclude M1 242.1806 -0.8929 Compatible M2 247.6181 4.5446 Compatible M3 242.0036 -1.0699 Compatible M4 240.0661 -3.0074 Compatible M5 248.5072 5.4337 Compatible M6 240.9862 -2.0873 Compatible RDX 243.0735 Thus, based on the above result table and according to STANAG 4147, we can conclude: In addition to the substances (serezin, stearic acid, sudan), some of the following substances can be used to domesticate RDX explosives: parafin , silicon, wax 8, polyisobutylene, PE wax, nylon Thus, substances (paraffin, silicon, wax 8, serezin) can be used to domesticate not only for HMX but also for RDX In addition, some other substances (PE wax, polyisobutylene, nylon) can also be used to domesticate RDX However, this is only an initial guide to the use of this domesticated substance for RDX on a compatible basis In order to confirm whether the above substances are truly domesticated for RDX, it is necessary to study in detail the effect of the composition of these substances on the other physical and chemical properties of the mixture 23 g CONCLUDE With the implemented contents, the thesis has achieved the following main results and contributions: I Main results - Analyzing surface morphology by SEM images of ТГ and A-IX-1 samples, it is clear that the surface of the RDX particles is covered by TNT or CTH, this is the cause of reducing branching and increasing disconnecting the circuit during the explosion of dynamite RDX according to the free radical mechanism - A DTA curve was established, the measurement results of ТГ and A-IX-1 mixed explosive decomposition were measured in the atmospheric environment, Kissinger's equations were established based on the results obtained from the DTA schema Calculation of kinematic parameters: activation energy, exponential coefficient (frequency), reaction rate constant corresponding to each ratio of substances in explosive mixture AIX-1, ТГ The result is that the kT rate constant decreases with increasing TNT content in ТГ samples or when the CTH content increases gradually in A-IX-1 samples This clarifies the domestication of RDX of TNT and CTH - Formulated the equation for the reaction rate constant decomposition at temperature T for each substance From there, help determine the half-life of each substance and determine the durability of these explosives depending on the storage temperature - Measure the physical parameters of the sample to give the melting temperature of the ТГ samples close to the melting point of TNT, suitable technological characteristics for processing in service of manufacturing and filling explosive types of bullets - Explosive speed, explosive heat of ТГ explosives decreased as TNT content increased and explosive speed, explosive heat of dynamite AIX-1 also decreased with increasing CTH content The results obtained are empirically consistent with the theoretical calculations and conform to the kinematic parameters E, Z, kT by DTA thermal analysis method - It is expected to add some substances that can be used to domesticate RDX explosives: paraffin, silicon, wax 8, polyisobutylene, PE wax, nylon based on compatibility calculation 24 g II New contributions of the thesis - Determined the compatibility of TNT, tame substance and RDX from thermal analysis of explosive materials, determined the kinematic parameters of thermal decomposition process of explosive systems ТГ (range of RDX content from 40% to 77%) and A-IX-1 (range of RDX content from 93.5% to 95%) - corresponding to the explosive systems currently used to produce and repair bullets, bombs, mines - Experimental graph has been established on the dependence of activation energy E, the pre-exponential factor Z of the above two explosive systems on the mixture From there, formulate the equation for the reaction rate constant decomposition at temperature T for each explosive with a certain component ratio This allows determining the halflife and predicting the durability of explosives depending on storage temperature - On the basis of determining the regularity of the density, velocity of explosive as well as explosive heat into the composition of the explosive system, it is possible to calculate and select the appropriate component to serve the fabrication and loading of explosive into bullets III The next research direction of the thesis Continuing to study the dependence of explosive speed and thermal decomposition process of explosive mixtures on the basis of RDX and other domestication substances to set up a manual for explosives engineers to get That is the basis to apply the calculation and design of a single component suitable for new design bullets ...CơBỘ GIÁO DỤC VÀ ĐÀO BỘ QUỐC PHỊNG TẠO VIỆN KHOA HỌC VÀ CÔNG NGHỆ QUÂN SỰ The work was completed in : Academy of Military Science and Technology, Ministry of Defence Science... topical number (02) /2019, Vietnam Chemical Association, p.4-8 1 g OPENING The urgency of the thesis Hexogen or RDX is the common name of cyclonite; 1,3,5-trinitro1,3,5-triazocyclohecxan, hay cyclotrimetylen... dependence of explosive speed and decomposition process on the composition of explosive mixture based on hexogen" is not only scientifically meaningful but also practical, urgent as a scientific basis
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