CN109438145B - High-detonation-heat aluminum-containing explosive and preparation method thereof - Google Patents
High-detonation-heat aluminum-containing explosive and preparation method thereof Download PDFInfo
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- CN109438145B CN109438145B CN201811597646.7A CN201811597646A CN109438145B CN 109438145 B CN109438145 B CN 109438145B CN 201811597646 A CN201811597646 A CN 201811597646A CN 109438145 B CN109438145 B CN 109438145B
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/08—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with a nitrated organic compound
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
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Abstract
The high-explosive-heat aluminum-containing explosive comprises the following components in percentage by mass: liquid fluororubber containing terminal functional groups: 5-20%; curing agent: 0.5-5%; main explosive: 35-80%; aluminum powder: 10-40% of liquid fluororubber containing terminal group functional groups, wherein the liquid fluororubber containing terminal group functional groups is carboxyl-terminated liquid fluororubber or hydroxyl-terminated liquid fluororubber with the number average molecular weight of 2000-18000; the curing agent is isocyanate curing agent or epoxy resin curing agent; the main explosive is one or more of RDX, HMX, CL-20, TATB, FOX-7 and LLM-105; the particle size of the aluminum powder is 50 nm-100 um. The formula of the invention can obviously improve the explosion heat of the explosive.
Description
Technical Field
The invention belongs to the technical field of military mixed explosives, and particularly relates to a high-explosive-heat aluminum-containing explosive and a preparation method thereof.
Background
With the higher demand of weapon ammunition such as rocket projectiles, shells, guided missiles and the like for high-efficiency damage power, the military mixed explosive also develops towards the direction of high explosive heat and high damage power. The aluminum-containing explosive has the excellent characteristics of high explosion heat, high explosion temperature, long chemical energy release time, high operational capability and the like, becomes an important series of military mixed explosives, and is widely applied to air weapon ammunition, underwater weapon ammunition, air ship weapon ammunition and air-to-ground weapon ammunition. The common adhesive for aluminum-containing explosives is an inert adhesive, including inert high polymer, insensitive agent and the like, and although the adhesive has a good insensitive coating effect, the combustion reaction rate of aluminum powder is difficult to effectively improve. Compared with the inert adhesive, the F element in the fluororubber can generate exothermic chemical reaction with Al, so that the use of the fluororubber as the adhesive can obviously improve the explosion heat of the aluminum-containing explosive. Commonly used solid fluororubber binders such as Viton rubber、F26、F246、F23The series of fluororubbers have good high temperature resistance, aging resistance and physical and mechanical properties, and the solid fluororubbers can be used as an adhesive for preparing press-fitting type aluminum-containing explosives. However, the solid fluororubber has high glass transition temperature, modulus and hardness, so that the compression molding preparation process of the aluminum-containing explosive is not good, and the aluminum-containing explosive is usually pressed at high temperature (not less than 80 ℃) and high pressure (not less than 200 MPa).
The liquid fluororubber containing the end group functional group inherits the excellent high temperature resistance, aging resistance and other properties of the traditional solid fluororubber, and compared with the solid fluororubber, the molecular weight is greatly reduced, so that the processing property is greatly improved, and the liquid fluororubber is more beneficial to utilization. The liquid fluororubber containing the terminal group functional group has fluidity at normal temperature, can be chemically cross-linked, cured and molded as polybutadiene rubber (HTPB) containing the terminal group, is used for preparing aluminum-containing explosives, and improves the moldability of the aluminum-containing explosives. The use of a liquid fluoroelastomer containing end-group functional groups as a binder helps to increase the detonation heat of an aluminum-containing explosive compared to an inert high polymer HTPB binder.
Disclosure of Invention
The invention aims to provide a high-detonation-heat aluminum-containing explosive and a preparation method thereof, wherein the high-detonation-heat aluminum-containing explosive disclosed by the invention has the advantages that the cross-linkable and solidified liquid fluororubber containing end group functional groups is used as an adhesive, so that the combustion reaction rate of aluminum powder is enhanced, and the detonation heat of the aluminum-containing explosive is obviously improved; meanwhile, the aluminum-containing explosive is prepared by a casting-curing molding process, and the method has a good molding process.
The technical scheme of the invention is that the high explosive heat aluminum-containing explosive comprises the following components in percentage by mass: liquid fluororubber containing terminal functional groups: 5-20%; curing agent: 0.5-5%; main explosive: 35-80%; aluminum powder: 10 to 40 percent.
The liquid fluororubber containing the end group functional group contains fluorine atoms with strong electronegativity, the fluorine atoms are easy to accept electrons from reducing metal Al and release fluorine, and Al is oxidized to generate AlF3And emits heat. Oxidizing with Al to produce Al2O3In contrast, AlF is generated3Is easy to occur, andthe heat of reaction is higher. Therefore, the addition of the fluororubber to the aluminum-containing explosive is helpful for improving the explosion heat of the explosive.
Further, the liquid fluororubber containing terminal group functional groups has a number average molecular weight of 2000-18000 and is carboxyl-terminated liquid fluororubber or hydroxyl-terminated liquid fluororubber.
Further, the curing agent is an isocyanate curing agent or an epoxy resin curing agent.
Still further, the main explosive is one or more of RDX, HMX, CL-20, TATB, FOX-7 and LLM-105.
Further, the particle size of the aluminum powder is 50 nm-100 um.
The invention also provides a preparation method of the high-explosive-heat aluminum-containing explosive, which comprises the following steps:
(1) weighing the raw materials according to the mass percentage;
(2) dissolving the liquid fluorine rubber containing the end group functional group by using acetone;
(3) adding the main explosive and aluminum powder into the dissolved liquid fluororubber containing the end group functional group, and uniformly stirring;
(4) adding a curing agent into the mixture prepared in the step (3), and uniformly stirring;
(5) and putting the prepared material into a mould in a vacuum pouring mode, removing the solvent and a small amount of air carried in the slurry, and then heating, curing and forming.
Further, the mass ratio of the fluororubber to the acetone in the step (2) is 1: 1.
Further, the temperature of the heat curing molding in the step (5) is 65 ℃.
Compared with the prior art, the invention has the following beneficial effects:
when the fluorine-containing binder in the high detonation heat aluminum-containing explosive is used for an aluminum-containing explosive, compared with an aluminum-containing explosive adopting an inert binder HTPB, the detonation heat of the explosive can be increased by 4-7%; compared with the solid fluororubber adhesive, the aluminum-containing explosive can be prepared by a pouring-curing process, and the preparation process is good.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.
Example 1
A high explosive containing aluminium with high detonation heat has a formula shown in Table 1.
Table 1 high explosive heat aluminum containing explosive formulation of example 1
The preparation method of the high detonation heat aluminum-containing explosive comprises the following steps:
step (1): weighing the raw materials according to the formula in the table 1;
step (2): stirring and dissolving carboxyl-terminated liquid fluororubber by using an acetone solvent, wherein the mass ratio of the two is 1: 1;
and (3): respectively adding Al and RDX into the liquid fluororubber, and uniformly stirring and mixing.
And (4): and adding the curing agent epoxy resin E44 into the mixed material, and uniformly stirring.
And (5): and (3) putting the prepared material into a mould in a vacuum pouring mode, removing an acetone solvent and a small amount of air carried in the slurry, and then putting the mould into a high-temperature oven at 65 ℃ for heating and curing molding.
The prepared product was subjected to a performance test, the test results being as follows:
compared with the same explosive formula PBXN-109 adopting HTPB binder and the explosion heat of 6430kJ/kg, the explosion heat of the aluminum-containing explosive prepared by the embodiment of the invention is increased by 6.45%.
Example 2
A high explosive containing aluminium with high detonation heat has a formula shown in Table 2.
Table 2 high explosive heat aluminum containing explosive formulation of example 2
The preparation method of the high detonation heat aluminum-containing explosive comprises the following steps:
step (1): weighing the raw materials according to the formula in the table 2;
step (2): stirring and dissolving the hydroxyl-terminated liquid fluororubber by using an acetone solvent, wherein the mass ratio of the hydroxyl-terminated liquid fluororubber to the acetone solvent is 1: 1;
and (3): respectively adding Al and HMX into the liquid fluororubber, and uniformly stirring and mixing.
And (4): adding curing agent HDI tripolymer into the mixed material, and stirring and mixing uniformly.
And (5): and (3) putting the prepared material into a mould in a vacuum pouring mode, removing an acetone solvent and a small amount of air carried in the slurry, and then putting the mould into a high-temperature oven at 65 ℃ for heating and curing molding.
The prepared product was subjected to a performance test, the test results being as follows:
the actual measured explosion heat of the aluminum-containing explosive prepared in the embodiment of the invention is 7420kJ/kg, and compared with the explosion heat of 7130kJ/kg of the same explosive formula adopting HTPB (HTPB) binder, the explosion heat of the aluminum-containing explosive prepared in the invention is increased by 4.1%.
Example 3
A high explosive containing aluminium with high detonation heat has a formula shown in Table 3.
Table 3 high explosive heat aluminum containing explosive formulation of example 3
The preparation method of the high detonation heat aluminum-containing explosive comprises the following steps:
step (1): weighing the raw materials according to the formula in table 3;
step (2): stirring and dissolving the hydroxyl-terminated liquid fluororubber by using an acetone solvent, wherein the mass ratio of the hydroxyl-terminated liquid fluororubber to the acetone solvent is 1: 1;
and (3): respectively adding Al, FOX-7 and RDX into the liquid fluororubber, and uniformly stirring and mixing.
And (4): adding the curing agent N-100 into the mixed material, and uniformly stirring.
And (5): and (3) putting the prepared material into a mould in a vacuum pouring mode, removing an acetone solvent and a small amount of air carried in the slurry, and then putting the mould into a high-temperature oven at 65 ℃ for heating and curing molding.
The prepared product was subjected to a performance test, the test results being as follows:
the explosive containing aluminum prepared by the embodiment of the invention has the explosion heat of 6310 kJ/kg.
Example 4
A high explosive containing aluminium with high detonation heat has a formula shown in Table 4.
Table 3 high explosive heat aluminum containing explosive formulation of example 4
The preparation method of the high detonation heat aluminum-containing explosive comprises the following steps:
step (1): weighing the raw materials according to the formula in table 4;
step (2): stirring and dissolving the hydroxyl-terminated liquid fluororubber by using an acetone solvent, wherein the mass ratio of the hydroxyl-terminated liquid fluororubber to the acetone solvent is 1: 1;
and (3): respectively adding Al and CL-20 into the liquid fluororubber, and uniformly stirring and mixing.
And (4): adding the curing agent N-100 into the mixed material, and uniformly stirring.
And (5): and (3) putting the prepared material into a mould in a vacuum pouring mode, removing an acetone solvent and a small amount of air carried in the slurry, and then putting the mould into a high-temperature oven at 65 ℃ for heating and curing molding.
The prepared product was subjected to a performance test, the test results being as follows:
the explosive containing aluminum prepared by the embodiment of the invention has the explosion heat of 7905 kJ/kg.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A high-detonation-heat aluminum-containing explosive is characterized by comprising the following components in percentage by mass:
liquid fluororubber containing terminal functional groups: 5-20%;
curing agent: 0.5-5%;
main explosive: 35-80%;
aluminum powder: 10-40%;
the liquid fluororubber containing the terminal group functional group is carboxyl-terminated liquid fluororubber or hydroxyl-terminated liquid fluororubber with the number average molecular weight of 2000-18000.
2. The high explosive heating aluminum containing explosive according to claim 1, wherein the curing agent is an isocyanate curing agent or an epoxy resin curing agent.
3. The high explosive heat of aluminum containing explosive of claim 2, wherein the primary explosive is one or more combination of RDX, HMX, CL-20, TATB, FOX-7, LLM-105.
4. The high explosive heat aluminum containing explosive of claim 1, wherein the aluminum powder has a particle size of 50nm to 100 um.
5. A method for preparing a high explosive containing aluminium according to any of claims 1 to 4, which comprises the following steps:
(1) weighing the raw materials according to the mass percentage;
(2) dissolving the liquid fluorine rubber containing the end group functional group by using acetone;
(3) adding the main explosive and aluminum powder into the dissolved liquid fluororubber containing the end group functional group, and uniformly stirring;
(4) adding a curing agent into the mixture prepared in the step (3), and uniformly stirring;
(5) and putting the prepared material into a mould in a vacuum pouring mode, removing the solvent and a small amount of air carried in the slurry, and then heating, curing and forming.
6. The method for preparing the high explosive heating aluminum containing explosive according to claim 5, wherein the mass ratio of the fluororubber to the acetone in the step (2) is 1: 1.
7. The method for preparing a high explosive containing aluminum according to claim 5, wherein the temperature for thermosetting molding in the step (5) is 65 ℃.
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| CN115784818A (en) * | 2021-08-20 | 2023-03-14 | 北京理工大学 | Preparation method of high-molecular fluorine-rich oxidant-based aluminothermic high-explosive-heat industrial explosive |
| CN115322063B (en) * | 2022-08-11 | 2024-01-02 | 湖北航天化学技术研究所 | Polymer bonded explosive and preparation method thereof |
| CN116023199B (en) * | 2022-12-29 | 2024-04-05 | 湖北航天化学技术研究所 | High-heat-explosion fluorine-rich explosive and preparation method thereof |
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