Stable-initiation, low-sensitivity and high-explosion-heat fusion-cast explosive and preparation method thereof

Abstract

The invention provides a stable-initiation low-sensitivity high-explosion-heat fusion casting explosive and a preparation method of the stable-initiation low-sensitivity high-explosion-heat fusion casting explosive. The high-explosion-heat melt-cast explosive comprises the following components in percentage by mass: 57-77% of ETN, 15-20% of micron boron powder or micron aluminum powder, 2% of microcrystalline wax, 4% of nano graphite powder or nano boron nitride powder and the balance of DPA. The invention further relates to a preparation method of the stable-initiation low-sensitivity high-explosion-heat fusion-cast explosive. According to the invention, all the components are fully matched for use, and finally the casting explosive with the characteristics of high explosion heat, easy detonation, low mechanical sensitivity, low price and the like is prepared; the explosion heat is very high, and the actually measured explosion heat is greater than 9000 kJ / kg; the mechanical sensitivity is very low, and the actually measured friction sensitivity and impact sensitivity are similar to those of TNT; the detonation velocity is high, and the actually measured detonation velocity is greater than 6000 m / s; the price is very low and is about 371-487 yuan / kg.

Description

Technical Field

[0001] The present invention belongs to the field of propellants and explosives; in particular, it relates to a melt-cast explosive with stable initiation, low sensitivity, and high heat of explosion, and a preparation method thereof. Background Art

[0002] High heat of explosion explosives are very important military mixed explosives and can be used in important applications such as underwater explosives, thermobaric explosives, penetrator projectiles, and incendiary bombs. In the design process of the melt-cast explosive formula with high heat of explosion, in addition to the heat of explosion reaching 8000 kJ / kg, it is also required to consider factors such as the detonation performance, safety performance, price of the explosive, and whether it can be stably initiated in the existing initiation and detonation sequences.

[0003] At present, there are mainly four problems with existing high heat of explosion mixed explosives: (1) Since almost no heat of explosion of primary explosives exceeds 6000 kJ / kg, in order to increase the heat of explosion, an excessive amount of aluminum powder and oxidants (such as ammonium perchlorate, etc.) are added to the formula, while the fraction of primary explosives is too small, resulting in the high heat of explosion explosive prepared being unable to be initiated by traditional booster sequences. Even when using a large-diameter or extra-large-diameter booster column for initiation, its detonation performance is still very poor, and the detonation velocity is difficult to reach above 6000 m / s, and often the detonation is incomplete; (2) Due to the addition of a large amount of oxidants and aluminum powder, the impact and friction sensitivities of the agent are significantly increased, greatly reducing the safety performance of the mixed explosive; (3) The measured heat of explosion of traditional high heat of explosion agents is difficult to exceed 9000 kJ / kg; (4) The cost of traditional high heat of explosion agents is too high, and the manufacturing process is complex.

[0004] Therefore, there is an urgent need for a method to prepare a melt-cast explosive with characteristics such as high heat of explosion, easy initiation, low mechanical sensitivity, and low cost. Summary of the Invention

[0005] The purpose of the present invention is to provide a melt-cast explosive with stable initiation, low sensitivity, and high heat of explosion, and a preparation method thereof.

[0006] The present invention is achieved through the following technical solutions:

[0007] The present invention relates to a melt-cast explosive with stable initiation, low sensitivity, and high heat of explosion, comprising the following components in mass percentages:

[0008]

[0009]

[0010] Or comprising the following components in mass percentages:

[0011]

[0012] Preferably, the ETN is 1,2,3,4 - butanetetrol tetranitrate (Erythritol tetranitrate, C4H5N4O 12 ), and its price is about 25 yuan per kilogram;

[0013] The average particle size of the micron boron powder is 1 - 20 μm, and the price of this boron powder is about 500 yuan per kilogram;

[0014] The average particle size of the micron aluminum powder is 1 - 20 μm, and the price of the aluminum powder is about 80 yuan per kilogram;

[0015] The microcrystalline wax is a white amorphous solid wax, mainly composed of branched - chain saturated hydrocarbons with C 31 ~C 70 , containing a small amount of cyclic and straight - chain hydrocarbons, odorless and tasteless, with CAS No. 8001 - 75 - 0; the market price is about 150 yuan per kilogram. The addition of microcrystalline wax can significantly reduce the mechanical sensitivity of ETN and improve the mechanical properties of the ETN charge.

[0016] The nano - graphite powder is graphite powder with a nanostructure, and its one - dimensional size is less than 100 nm. The addition of nano - graphite powder can greatly reduce the mechanical sensitivity of ETN. The price of nano - graphite powder is about 8000 yuan per kilogram.

[0017] The nano - boron nitride powder is boron nitride powder with a nanostructure, and its one - dimensional size is less than 100 nm, accounting for 4 wt.% of the high - explosive heat - melting cast explosive. The addition of nano - boron nitride powder can also greatly reduce the mechanical sensitivity of ETN. The price of nano - boron nitride powder is about 9000 yuan per kilogram.

[0018] The DPA is diphenyl amine (C 12 H 11 N1), which is a stabilizer. A small amount of addition can very well inhibit the decomposition of ETN during storage. The CAS No. of DPA is 122 - 39 - 4. The market price of DPA is about 280 yuan per kilogram.

[0019] The present invention also relates to a preparation method of the above - mentioned stable - detonation and low - sensitivity high - explosive heat - melting cast explosive, including the following steps:

[0020] Step 1: Put a certain amount of ETN into a beaker and heat the beaker to 70 °C with a water bath;

[0021] Step 2: After the ETN is completely melted, add a certain amount of micron boron powder or micron aluminum powder, stir evenly, then add a small amount of microcrystalline wax, nano - graphite powder or nano - boron nitride, and a small amount of DPA, and gently stir evenly with a glass rod to obtain a uniform thin paste;

[0022] Step 3: Pour the thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After gradually cooling at room temperature, demold to obtain a melt-cast explosive charge of stable detonation and low sensitivity and high explosive power.

[0023] The mass percentages of the components involved in the above steps are as follows:

[0024]

[0025] Or include the following components with the following mass percentages:

[0026]

[0027] In the present invention, boron powder with low sensitivity and significantly higher combustion heat than aluminum powder is used as the combustion agent (Note: The combustion heat generated by the complete combustion of aluminum powder in oxygen is -31.0×10 3 kJ / kg, while the combustion heat generated by the complete combustion of boron powder in oxygen is -58.9×10 3 kJ / kg), thereby increasing the detonation heat of the mixed explosive.

[0028] The present invention uses a cheap, positive oxygen balance, extremely high detonation heat and high detonation sensitivity single-component high explosive, erythritol tetranitrate (ETN, C4H6N4O 12 ) as the carrier explosive. Since the oxygen balance of ETN is +5.3%, there is no need to add inorganic oxidants (such as ammonium perchlorate) that will cause a sharp increase in the mechanical sensitivity of the agent in the formula of the present invention; in addition, due to the very high detonation sensitivity of ETN, the mixed explosive is easily detonated sufficiently; and ETN is currently the single-component explosive with the highest detonation heat, and its measured detonation heat reaches -7631 kJ / kg, which is beyond the reach of most single-component explosives.

[0029] The present invention introduces microcrystalline wax, which can significantly reduce the mechanical sensitivity of ETN and improve the mechanical properties of the ETN charge.

[0030] The present invention introduces nano graphite powder or nano boron nitride powder. Due to the excellent lubricity and extremely high specific surface area of nano graphite powder or boron nitride powder (BN), a small amount of addition can significantly reduce the mechanical sensitivity of the agent without affecting the energy performance of the agent.

[0031] The present invention fully combines the above components to finally prepare a melt-cast explosive with the characteristics of high detonation heat, easy detonation, low mechanical sensitivity and low cost.

[0032] The present invention has the following advantages:

[0033] (1) The present invention fully combines the above components to finally prepare a cast explosive with the characteristics of high heat of explosion, easy initiation, low mechanical sensitivity, and low cost; its heat of explosion is very high, and the measured heat of explosion is greater than 9000 kJ / kg.

[0034] (2) The stable initiation and low-sensitivity high-explosive cast explosive prepared by the present invention has very low mechanical sensitivity, and the measured friction sensitivity and impact sensitivity are similar to those of TNT;

[0035] (3) The stable initiation and low-sensitivity high-explosive cast explosive prepared by the present invention has a relatively high detonation velocity, and the measured detonation velocity is greater than 6000 m / s;

[0036] (4) The stable initiation and low-sensitivity high-explosive cast explosive prepared by the present invention has a very low price, about 371 - 487 yuan per kilogram.

[0037] (5) In the formula of the stable initiation and low-sensitivity high-explosive cast explosive prepared by the present invention, the mass fraction of the high-detonation-sensitivity explosive ETN is greater than 57 - 77 wt.%, and the detonation sensitivity of ETN itself is very high, which enables the product explosive column to be easily completely initiated by an electric detonator plus a traditional booster explosive column. Description of the Drawings

[0038] Figure 1 is the SEM photograph of nano-graphite powder;

[0039] Figure 2 is the SEM photograph of nano-boron nitride powder. Detailed Embodiments

[0040] The present invention will be described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments are only further descriptions of the present invention, but the protection scope of the present invention is not limited to the following embodiments.

[0041] Example 1

[0042] This example relates to a preparation method of an ETN-based high-explosive cast explosive column, including the following steps:

[0043] Step 1: Put 77 grams of ETN into a beaker and heat the beaker to 70 °C in a water bath;

[0044] Step 2: After the ETN is completely melted, add 15 grams of micron boron powder thereto, stir evenly, then add 2 grams of microcrystalline wax, 4 grams of nano-graphite powder, and 2 grams of diphenylamine, and gently stir evenly with a glass rod to obtain a uniform thin paste;

[0045] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0046] Example 2

[0047] This example relates to a preparation method of an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0048] Step 1: Put 74 g of ETN into a beaker, and then heat the beaker to 70 °C using a water bath;

[0049] Step 2: After the ETN is completely melted, add 18 g of micron-sized boron powder to it. After stirring evenly, add 2 g of microcrystalline wax, 4 g of nano-sized graphite powder, and 2 g of diphenylamine, and gently stir evenly with a glass rod to obtain a uniform thin paste;

[0050] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0051] Example 3

[0052] This example relates to a preparation method of an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0053] Step 1: Put 72 g of ETN into a beaker, and then heat the beaker to 70 °C using a water bath,;

[0054] Step 2: After the ETN is completely melted, add 20 g of micron-sized boron powder to it. After stirring evenly, add 2 g of microcrystalline wax, 4 g of nano-sized graphite powder, and 2 g of diphenylamine, and gently stir evenly with a glass rod to obtain a uniform thin paste,;

[0055] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0056] Example 4

[0057] This example relates to a preparation method of an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0058] Step 1: Put 77 g of ETN into a beaker, and then heat the beaker to 70 °C using a water bath,;

[0059] Step 2: After the ETN is completely melted, add 15 grams of micron boron powder to it. After stirring evenly, add 2 grams of microcrystalline wax, 4 grams of nano boron nitride powder, and 2 grams of diphenylamine. Gently stir with a glass rod to obtain a uniform thin paste.

[0060] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0061] Example 5

[0062] This example relates to a preparation method of an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0063] Step 1: Put 74 grams of ETN into a beaker, and then heat the beaker to 70 °C using a water bath.

[0064] Step 2: After the ETN is completely melted, add 18 grams of micron boron powder to it. After stirring evenly, add 2 grams of microcrystalline wax, 4 grams of nano boron nitride powder, and 2 grams of diphenylamine. Gently stir with a glass rod to obtain a uniform thin paste.

[0065] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0066] Example 6

[0067] This example relates to a preparation method of an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0068] Step 1: Put 72 grams of ETN into a beaker, and then heat the beaker to 70 °C using a water bath.

[0069] Step 2: After the ETN is completely melted, add 20 grams of micron boron powder to it. After stirring evenly, add 2 grams of microcrystalline wax, 4 grams of nano boron nitride powder, and 2 grams of diphenylamine. Gently stir with a glass rod to obtain a uniform thin paste.

[0070] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0071] Example 7

[0072] This example relates to a preparation method of an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0073] Step 1: Place 57 g of ETN into a beaker, and then heat the beaker to 70 °C using a water bath.

[0074] Step 2: After the ETN is completely melted, add 35 g of micron-sized aluminum powder thereto. After stirring evenly, add 2 g of microcrystalline wax, 4 g of nano-sized graphite powder, and 2 g of diphenylamine, and gently stir evenly with a glass rod to obtain a homogeneous thin paste.

[0075] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and pre-heated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0076] Example 8

[0077] This example relates to a method for preparing an ETN-based high-explosive melt-cast explosive charge, including the following steps:

[0078] Step 1: Place 57 g of ETN into a beaker, and then heat the beaker to 70 °C using a water bath.

[0079] Step 2: After the ETN is completely melted, add 35 g of micron-sized aluminum powder thereto. After stirring evenly, add 2 g of microcrystalline wax, 4 g of nano-sized boron nitride powder, and 2 g of diphenylamine, and gently stir evenly with a glass rod to obtain a homogeneous thin paste.

[0080] Step 3: Carefully pour the hot thin paste into an aluminum alloy mold pre-coated with vaseline and pre-heated to 50 °C. After cooling at room temperature, demold to obtain an ETN-based high-explosive melt-cast explosive charge.

[0081] Perform performance tests on the ETN-based high-explosive melt-cast explosive charges prepared in the above Examples 1-8, and the test results are shown in Table 1:

[0082] Table 1

[0083]

[0084]

[0085] In the above Table 1, the detailed information of each component is as follows:

[0086] TNT is trinitrotoluene, C7H6N5O6; RDX is cyclonite, C3H6N6O6; HMX is octogen, C4H8N6O8; DNTF is 3,4-dinitrofurazanyl oxidofurazan, C6N8O8; ETN is 1,2,3,4-butanetetraol tetranitrate, C4H6N4O 12。The theoretical detonation velocity and theoretical detonation heat were calculated by the EXPLO5 software, which is a genuine software purchased and authorized for use by the Performance Testing Center of Detonating Explosives in North University of China. The measured detonation velocity was determined by the electrical measurement method for detonation velocity in Method 702.1 of GJB 772-97, and the testing unit was the Performance Testing Center of Detonating Explosives in North University of China. The measured detonation heat was determined by the adiabatic method for detonation heat in Method 702.1 of GJB 772-97, and the testing unit was the Performance Testing Center of Detonating Explosives in North University of China. The impact sensitivity was tested by the test method for impact sensitivity of explosives in GB / T 21567-2008. The larger the impact sensitivity value, the lower the sensitivity of the explosive. The testing unit was the Performance Testing Center of Detonating Explosives in North University of China. The friction sensitivity was tested by the test method for friction sensitivity of explosives in GB / T 21566-2008. The larger the friction sensitivity value, the lower the sensitivity of the explosive. The testing unit was the Performance Testing Center of Detonating Explosives in North University of China.

[0087] The data in Table 1 show that the detonation velocity of the high-explosive melt-cast explosive prepared by the present invention is comparable to that of TNT and belongs to the range of high explosives.

[0088] The data in Table 1 show that the detonation heat of the high-explosive melt-cast explosive prepared by the present invention is very high, and the measured detonation heat reaches up to -9532 kJ / kg at most, which is much higher than the measured detonation heat of the reported high-detonation-heat explosives at present.

[0089] The data in Table 1 show that due to the addition of microcrystalline wax, nano-graphite or nano-boron nitride, the mechanical sensitivity of the high-explosive melt-cast explosive prepared by the present invention is very low and is close to that of TNT.

[0090] The data in Table 1 show that under the initiation and detonation action of No. 8 electric detonator and PBXN-5 detonating explosive column (Φ10 mm×10 mm), the explosive columns prepared in all examples can detonate normally and completely.

[0091] The data in Table 1 show that the price of the high-explosive melt-cast explosive prepared by the present invention is very cheap and is close to that of TNT.

[0092] As Figure 1 and Figure 2 shown, it can be seen that the one-dimensional sizes of the nano-graphite and nano-boron nitride used in the present invention are both less than 100 nm, and they have excellent sensitivity reduction effects. In addition, it should be emphasized that the detonation heat values involved in the present invention are the heat generated during the detonation of the explosive, rather than the combustion heat of the explosive; because for the same explosive, the value of the combustion heat is usually much larger than the detonation heat value.

[0093] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which does not affect the essence of the present invention.

Claims

1. A stable detonating and low-sensitivity high-explosive melt-cast explosive, characterized in that, Comprising the following components in mass percentages: Or comprising the following components in mass percentages:

2. The stable detonation and low-sensitivity high-explosive melt-cast explosive according to claim 1, characterized in that, The ETN is 1,2,3,4-butanetetrol tetranitrate; The average particle size of the micron boron powder is 1 - 20 μm; The average particle size of the micron aluminum powder is 1 - 20 μm; The microcrystalline wax is a white amorphous solid wax, mainly composed of branched-chain saturated hydrocarbons with carbon numbers from C 51 to C 70 , containing a small amount of cyclic and straight-chain hydrocarbons, odorless and tasteless, with a CAS No. of 8001-75-0; The nano graphite powder is graphite powder with a nanostructure, and its one-dimensional size is less than 100 nm; The nano boron nitride powder is boron nitride powder with a nanostructure, and its one-dimensional size is less than 100 nm; The DPA is diphenylamine, and the CAS No. is 122 - 39 - 4.

3. A preparation method of a stable detonation and low-sensitivity high-explosive melt-cast explosive as described in claim 1, characterized in that, Comprising the following steps: Step 1, put a certain amount of ETN into a beaker and heat the beaker to 70 °C using a water bath; Step 2, after the ETN is completely melted, add a certain amount of micron boron powder or micron aluminum powder, stir evenly, then add a small amount of microcrystalline wax, nano graphite powder or nano boron nitride, and a small amount of DPA, and gently stir evenly with a glass rod to obtain a uniform thin paste; Step 3, pour the thin paste into an aluminum alloy mold pre-coated with vaseline and preheated to 50 °C, gradually cool it at room temperature, then demold to obtain a stable detonation and low-sensitivity high-explosive melt-cast explosive charge; The mass percentages of the components involved in the above steps are as follows: Or comprising the following components in mass percentages:

4. The preparation method of the stable detonation and low-sensitivity high-explosive melt-cast explosive according to claim 3, characterized in that, The average particle size of the micron boron powder is 1 - 20 μm; The average particle size of the micron aluminum powder is 1 - 20 μm; The microcrystalline wax is a white amorphous solid wax, mainly composed of branched-chain saturated hydrocarbons with C 51 ~C 70 , containing a small amount of cyclic and straight-chain hydrocarbons, odorless and tasteless, with a CAS No. of 8001-75-0; The nano graphite powder is graphite powder with a nanostructure, and its one-dimensional size is less than 100 nm; The nano boron nitride powder is boron nitride powder with a nanostructure, and its one-dimensional size is less than 100 nm; The DPA is diphenylamine, and the CAS No. is 122 - 39 - 4.

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