CN116768687A - High-sensitivity FEP-based energetic structural material and preparation method and application thereof - Google Patents

High-sensitivity FEP-based energetic structural material and preparation method and application thereof Download PDF

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Publication number
CN116768687A
CN116768687A CN202310773538.5A CN202310773538A CN116768687A CN 116768687 A CN116768687 A CN 116768687A CN 202310773538 A CN202310773538 A CN 202310773538A CN 116768687 A CN116768687 A CN 116768687A
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China
Prior art keywords
fep
structural material
metal
metal fluoride
active metal
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贺川
庄治华
刘金旭
蔡悦
李树奎
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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Abstract

The invention belongs to the technical field of energetic structural materials, and particularly relates to a high-sensitivity FEP-based energetic structural material, and a preparation method and application thereof. The invention provides a high-sensitivity FEP-based energetic structural material, which comprises FEP, active metal and metal fluoride; the active metal comprises aluminum and/or magnesium; the metal fluoride includes CoF 3 、FeF 3 、CuF 2 And BiF 3 One or more of them. The energetic structural material provided by the invention has higher reactivity and energy release efficiency.

Description

High-sensitivity FEP-based energetic structural material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energetic structural materials, and particularly relates to a high-sensitivity FEP-based energetic structural material, and a preparation method and application thereof.
Background
The Polytetrafluoroethylene (PTFE) -metal (Al, mg) material is a novel energetic structural material prepared by taking PTFE as a matrix and an oxidant, taking Al/Mg as a reducing agent and an enhancing phase and adopting a powder metallurgy method, and has certain structural strength, can also generate chemical reaction under the action of high-speed impact, releases a large amount of heat and has the purpose of double damage such as spark ignition, ignition and the like to a target. However, polytetrafluoroethylene (PTFE) -metal (Al, mg) energetic structural materials have low energy release efficiency and even cannot detonate when striking a target at a low speed, and severely limit the application of the materials in the field of battle.
Disclosure of Invention
The invention aims to provide a high-sensitivity FEP-based energetic structural material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-sensitivity FEP-based energetic structural material, which comprises FEP, active metal and metal fluoride;
the active metal comprises aluminum and/or magnesium;
the metal fluoride includes CoF 3 、FeF 3 、CuF 2 And BiF 3 One or more of them.
Preferably, the mass fraction of the FEP is 30-70%; the mass fraction of the active metal is 20-50%; the mass fraction of the metal fluoride is 10-40%.
The invention also provides a preparation method of the high-sensitivity FEP-based energetic structural material, which comprises the following steps:
pressing and forming a mixture containing FEP, active metal and metal fluoride to obtain a pressed blank;
and sintering the pressed compact to obtain the FEP-based energetic structural material with high sensitivity.
Preferably, the FEP has an average particle diameter of 0.2 to 20 μm; the average grain diameter of the active metal is 0.5-100 mu m; the average particle diameter of the metal fluoride is 1-20 mu m.
Preferably, the preparation method of the mixture containing FEP, active metal and metal fluoride comprises the following steps:
mixing FEP, active metal and metal fluoride, and ball milling;
or stirring and mixing FEP, active metal, metal fluoride and polar organic solvent, and drying.
Preferably, the ball milling medium used for ball milling comprises a first hard alloy grinding ball and a second hard alloy grinding ball;
the diameter of the first hard alloy grinding ball is 3mm, and the diameter of the second hard alloy grinding ball is 8mm;
the mass ratio of the first hard alloy grinding ball to the second hard alloy grinding ball is 5: 5-8: 2;
the mass ratio of the total mass of the FEP, the active metal and the metal fluoride to the ball milling medium is 1:2.5 to 5;
the rotation speed of the ball milling is 150-200 rpm, and the time is 2-4 h.
Preferably, the rotation speed of stirring and mixing is 500-1500 rpm, and the time is 2-4 h.
Preferably, the pressure of the compression molding is 100-200 MPa, and the pressure maintaining time is 0.5-5 min.
Preferably, the sintering is performed in an inert atmosphere;
the sintering temperature is 200-250 ℃, and the heat preservation time is 2-6 h.
The invention also provides the application of the high-sensitivity FEP-based energetic structural material prepared by the technical scheme or the preparation method of the technical scheme in the high-damage ammunition.
The invention provides a high-sensitivity FEP-based energetic structural material, which comprises FEP, active metal and metal fluoride; the active metal comprises aluminum and/or magnesium; the metal fluoride includes CoF 3 、FeF 3 、CuF 2 And BiF 3 One or more of them. In the present invention, FEP is a polymer modified by PTFE with a higher fluorine content, i.e. higher oxidizing; when the active metal and the metal fluoride in the energetic structural material are impacted, the reaction threshold of the active metal and the metal fluoride is lower, the active metal and the metal fluoride can be subjected to chemical reaction preferentially to release energy, and the polymer/metal is promoted to react so as to promote the materialThe energy release efficiency of the material further enables the energetic structural material provided by the invention to have higher reactivity and energy release efficiency.
Drawings
FIG. 1 is a diagram showing the results of the impact test of the energetic structures obtained in example 3 and comparative example 1.
Detailed Description
The invention provides a high-sensitivity FEP-based energetic structural material, which comprises FEP, active metal and metal fluoride;
the active metal comprises aluminum and/or magnesium;
the metal fluoride includes CoF 3 、FeF 3 、CuF 2 And BiF 3 One or more of them.
In the present invention, all components are commercially available products well known to those skilled in the art unless specified otherwise.
In the present invention, the mass fraction of the FEP is preferably 30 to 70%, more preferably 35 to 60%, still more preferably 40 to 50%; the mass fraction of the active metal is preferably 20 to 50%, more preferably 25 to 45%, and even more preferably 30 to 40%; the mass fraction of the metal fluoride is preferably 10 to 40%, more preferably 15 to 35%, and even more preferably 20 to 30%.
The invention also provides a preparation method of the high-sensitivity FEP-based energetic structural material, which comprises the following steps:
pressing and forming a mixture containing FEP, active metal and metal fluoride to obtain a pressed blank;
and sintering the pressed compact to obtain the FEP-based energetic structural material with high sensitivity.
The invention performs compression molding on a mixture containing FEP, active metal and metal fluoride to obtain a pressed blank.
In the present invention, the FEP, the reactive metal and the metal fluoride are all preferably added in the form of powder. In the present invention, the average particle diameter of the FEP is preferably 0.2 to 20. Mu.m, more preferably 5 to 10. Mu.m. In the present invention, the average particle diameter of the active metal is preferably 0.5 to 100 μm; the average particle diameter of the aluminum is preferably 0.5 to 10. Mu.m, more preferably 1 to 5. Mu.m; the average particle diameter of the magnesium is preferably 10 to 100. Mu.m, more preferably 20 to 80. Mu.m. In the present invention, the average particle diameter of the metal fluoride is preferably 1 to 20. Mu.m, more preferably 2 to 15. Mu.m, still more preferably 5 to 10. Mu.m.
In the present invention, the preparation method of the mixture containing FEP, active metal and metal fluoride preferably includes:
mixing FEP, active metal and metal fluoride, and ball milling;
or stirring and mixing FEP, active metal, metal fluoride and polar organic solvent, and drying.
In the invention, the ball milling medium used for ball milling preferably comprises a first hard alloy grinding ball and a second hard alloy grinding ball; the diameter of the first hard alloy grinding ball is preferably 3mm, and the diameter of the second hard alloy grinding ball is preferably 8mm; the mass ratio of the first hard alloy grinding ball to the second hard alloy grinding ball is preferably 5: 5-8: 2. in the present invention, the mass ratio of the total mass of the FEP, the active metal and the metal fluoride to the ball milling medium is preferably 1:2.5 to 5. In the present invention, the rotation speed of the ball mill is preferably 150 to 200rpm, and the time is preferably 2 to 4 hours. In the present invention, the ball milling is preferably performed in a ball milling pot.
The kind and amount of the organic solvent are not particularly limited, and those skilled in the art can be used. In the present invention, the rotation speed of the stirring and mixing is preferably 500 to 1500rpm, and the time is preferably 2 to 4 hours.
In the present invention, the pressure of the press molding is preferably 100 to 200MPa, and the dwell time is preferably 0.5 to 5min. In the present invention, the press molding is preferably compression molding, cold isostatic pressing or injection molding. The size of the compact is not particularly limited in the present invention, and those skilled in the art can be used.
After the pressed compact is obtained, the pressed compact is sintered to obtain the energetic structural material.
In the present invention, the sintering is performed in an inert atmosphere, preferably argon. In a specific embodiment of the present invention, the flow rate of argon is preferably 30mL/min.
In the present invention, the sintering temperature is preferably 200 to 250 ℃, more preferably 210 to 240 ℃, and even more preferably 220 to 230 ℃; the heating rate for heating to the sintering temperature is 30 ℃/h; the holding time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and still more preferably 3 to 4 hours. In the present invention, the sintering is preferably performed in an inert sintering furnace.
After the sintering, the present invention also preferably includes cooling the resulting material to room temperature.
The invention also provides the application of the high-sensitivity FEP-based energetic structural material prepared by the technical scheme or the preparation method of the technical scheme in the high-damage ammunition. The present invention is not particularly limited to the specific embodiments of the application, and may be employed as is well known to those skilled in the art.
For further explanation of the present invention, a high sensitivity FEP-based energetic structural material, a method for preparing the same and applications thereof, provided by the present invention, will be described in detail below with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
40g of FEP powder having an average particle diameter of 10 μm, 40g of aluminum powder having an average particle diameter of 5 μm and 20g of FeF having an average particle diameter of 2 μm were mixed 3 Placing the powder into a ball milling tank, and respectively adding hard alloy grinding balls with diameters of 3mm and 8mm (wherein the mass ratio of the 3mm grinding balls to the 8mm grinding balls is 8:2), wherein the total mass ratio of the powder to the grinding balls is 1:2.5, ball milling for 2 hours under the condition of 200 rpm;
the obtained mixed powder is pressed and molded by adopting a compression molding process to obtain a pressed compact with the size of*51mm, wherein the pressing pressure is 100MPa and the dwell time is 30s;
placing the obtained pressed compact into an inert sintering furnace, and introducing argon into the inert sintering furnace at a flow rate of 30mL/min for 10min; and then heating to 220 ℃ at a heating rate of 30 ℃/h, preserving heat for 2h, and cooling to room temperature to obtain the high-sensitivity FEP-based energetic structural material.
Example 2
40g of FEP powder having an average particle diameter of 10 μm, 40g of aluminum powder having an average particle diameter of 5 μm and 20g of BiF having an average particle diameter of 2 μm were mixed 3 Placing the powder into a ball milling tank, and respectively adding hard alloy grinding balls with diameters of 3mm and 8mm (wherein the mass ratio of the 3mm grinding balls to the 8mm grinding balls is 8:2), wherein the total mass ratio of the powder to the grinding balls is 1:2.5, ball milling for 4 hours under the condition of 200 rpm;
the obtained mixed powder is pressed and molded by adopting a compression molding process to obtain a pressed compact with the size of*51mm, wherein the pressing pressure is 100MPa and the dwell time is 30s;
placing the obtained pressed compact into an inert sintering furnace, and introducing argon into the inert sintering furnace at a flow rate of 30mL/min for 10min; and then heating to 220 ℃ at a heating rate of 30 ℃/h, preserving heat for 2h, and cooling to room temperature to obtain the high-sensitivity FEP-based energetic structural material.
Example 3
45g of FEP powder having an average particle diameter of 10 μm, 25g of aluminum powder having an average particle diameter of 5 μm and 30g of CuF having an average particle diameter of 5 μm were mixed 2 Placing the powder into a ball milling tank, and respectively adding hard alloy grinding balls with diameters of 3mm and 8mm (wherein the mass ratio of the 3mm grinding balls to the 8mm grinding balls is 8:2), wherein the total mass ratio of the powder to the grinding balls is 1:2.5, ball milling for 4 hours under the condition of 150 rpm;
filling the obtained mixed powder into a container with a size ofIn a rubber mold, the wall thickness of the mold is 1.5mm, and then the mixed powder is pressed and molded by adopting a cold isostatic press to obtain a pressed compact, wherein the pressing pressure is 200MPa, and the pressure maintaining time is5min;
Placing the obtained pressed compact into an inert sintering furnace, and introducing argon into the inert sintering furnace at a flow rate of 30mL/min for 10min; and then heating to 220 ℃ at a heating rate of 30 ℃/h, preserving heat for 4h, and cooling to room temperature to obtain the high-sensitivity FEP-based energetic structural material.
Comparative example 1
An energetic structural material was prepared as in example 3, except that CuF was not added 2
Performance testing
The energetic structural materials prepared in examples 1-3 and comparative example 1 were subjected to Hopkinson pressure bar test under the same conditions, and specific test conditions are: atmospheric pressure condition was 3atm, sample size wasThe results of the fire area test are shown in Table 1, and the physical diagrams of the fire generated in the test of example 3 and comparative example 1 are shown in FIG. 1;
TABLE 1 test results of energetic structural materials obtained in examples 1-3 and comparative example 1
Area of fire/cm 2
Example 1 29
Example 2 33
Example 3 34
Comparative example 1 21
As can be seen from Table 1 and FIG. 1, under the same experimental conditions, the energetic structural material provided by the invention has a higher fire area, which indicates that the ratio of the energetic structural material participating in the reaction is increased, i.e. the sensitivity of the material under the impact condition is also improved.
Although the foregoing embodiments of the present invention have been described in detail, it is to be understood that this invention is not limited to the particular embodiments disclosed, as other embodiments may be devised in light of the foregoing description.

Claims (10)

1. A high sensitivity FEP-based energetic structural material comprising FEP, reactive metal and metal fluoride;
the active metal comprises aluminum and/or magnesium;
the metal fluoride includes CoF 3 、FeF 3 、CuF 2 And BiF 3 One or more of them.
2. The high sensitivity FEP-based energetic structural material of claim 1, wherein the FEP is 30-70% by mass; the mass fraction of the active metal is 20-50%; the mass fraction of the metal fluoride is 10-40%.
3. The method for producing a high sensitivity FEP-based energetic structural material according to claim 1 or 2, characterized by comprising the steps of:
pressing and forming a mixture containing FEP, active metal and metal fluoride to obtain a pressed blank;
and sintering the pressed compact to obtain the FEP-based energetic structural material with high sensitivity.
4. The method according to claim 3, wherein the FEP has an average particle diameter of 0.2 to 20 μm; the average grain diameter of the active metal is 0.5-100 mu m; the average particle diameter of the metal fluoride is 1-20 mu m.
5. The method of claim 3, wherein the method of preparing the mixture comprising FEP, reactive metal and metal fluoride comprises:
mixing FEP, active metal and metal fluoride, and ball milling;
or stirring and mixing FEP, active metal, metal fluoride and polar organic solvent, and drying.
6. The method according to claim 5, wherein the ball milling media used for the ball milling comprises a first cemented carbide ball and a second cemented carbide ball;
the diameter of the first hard alloy grinding ball is 3mm, and the diameter of the second hard alloy grinding ball is 8mm;
the mass ratio of the first hard alloy grinding ball to the second hard alloy grinding ball is 5: 5-8: 2;
the mass ratio of the total mass of the FEP, the active metal and the metal fluoride to the ball milling medium is 1:2.5 to 5;
the rotation speed of the ball milling is 150-200 rpm, and the time is 2-4 h.
7. The method according to claim 5, wherein the stirring and mixing speed is 500-1500 rpm for 2-4 hours.
8. The method according to claim 3, wherein the pressure of the press molding is 100 to 200MPa and the dwell time is 0.5 to 5min.
9. A method of preparation according to claim 3, wherein the sintering is carried out in an inert atmosphere;
the sintering temperature is 200-250 ℃, and the heat preservation time is 2-6 h.
10. The use of the high sensitivity FEP-based energetic structural material according to claim 1 or 2 or the high sensitivity FEP-based energetic structural material prepared by the preparation method according to any one of claims 3 to 9 in high destructive ammunition.
CN202310773538.5A 2023-06-27 2023-06-27 High-sensitivity FEP-based energetic structural material and preparation method and application thereof Pending CN116768687A (en)

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Citations (5)

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US20190030789A1 (en) * 2017-03-21 2019-01-31 Purdue Research Foundation 3d printed fluoropolymer-based energetic compositions
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Patent Citations (5)

* Cited by examiner, † Cited by third party
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US20040020397A1 (en) * 2002-03-28 2004-02-05 Nielson Daniel B. Low temperature, extrudable, high density reactive materials
US20190030789A1 (en) * 2017-03-21 2019-01-31 Purdue Research Foundation 3d printed fluoropolymer-based energetic compositions
CN107963951A (en) * 2017-12-25 2018-04-27 湖北航天化学技术研究所 A kind of micro- sodium structure Al-FeF3Hybrid fuel and preparation method thereof
CN115043689A (en) * 2022-06-06 2022-09-13 南京理工大学 Thermite containing carbon skeleton and preparation method thereof
CN115819161A (en) * 2022-11-21 2023-03-21 北京理工大学 Preparation method of boron-based active material energetic micro-pill

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