CN115536483A

CN115536483A - Copper azide energetic film and preparation method thereof

Info

Publication number: CN115536483A
Application number: CN202211305457.4A
Authority: CN
Inventors: 李志敏; 雷国荣; 成闻川; 张建国; 张同来
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2022-10-24
Filing date: 2022-10-24
Publication date: 2022-12-30
Anticipated expiration: 2042-10-24
Also published as: CN115536483B

Abstract

The invention relates to a copper azide energetic film and a preparation method thereof, belonging to the technical field of energetic materials. The energy-containing membrane takes a hydrophobic porous reticular material as a carrier, and copper azide is uniformly and densely distributed on the single surface of the stainless steel net. Preparing a copper salt aqueous solution and an organic solution containing a ligand, wherein the organic solvent is immiscible with water and has a density smaller than that of water, placing a carrier on the surface of the aqueous solution, adding the organic solution, standing until the lower-layer aqueous solution is clear, uniformly covering the surface of the carrier with a precursor, taking out and drying to obtain a precursor film; then the precursor film is placed in an aqueous solution of azido acid for reaction for 5 to 20min at the temperature of minus 10 to 20 ℃, and the copper azide film is obtained after taking out and drying. The invention adopts a simple and feasible interface method to prepare a uniform and compact precursor film.

Description

Copper azide energetic film and preparation method thereof

Technical Field

The invention relates to a copper azide energetic film and a preparation method thereof, belonging to the technical field of energetic materials.

Background

The initiating explosive is an energetic material which is extremely sensitive to external stimulation and can rapidly complete Deflagration to Detonation Transition (DDT) after being initiated, the main energy output form of the initiating explosive is Detonation waves, and the next-stage explosive charge with lower sensitivity and higher power is detonated by the Detonation waves. The application of the initiating explosive is very wide, the image of the initiating explosive can be seen in various initiating explosive devices such as ignition, initiation and booster, and the initiating explosive devices play an indispensable role in various fields such as weaponry, aerospace, civil blasting equipment and the like. Therefore, the primary explosive plays an important role in the whole initiating explosive system and is an efficient ring energy element in the initiating explosive system. In recent years, in order to meet the requirements for information, miniaturization, and intelligence of weaponry, the development of firearms has been advanced to Micro-Electro-Mechanical systems (MEMS) firearms with diversified functions, information of transducer elements, miniaturized structures, and integrated sequences. The membrane energy conversion element is a novel membrane bridge type initiating explosive device, membrane materials in various shapes and structures are integrated on a substrate through an MEMS technology, the membrane energy conversion element has the advantages of low initiation energy, high safety, good reliability, miniaturization and the like, the preparation process of the membrane energy conversion element has good compatibility with the MEMS technology, and the membrane energy conversion element is widely applied to energy-containing devices such as a micro igniter, a micro initiation device, a micro thruster, a chip self-destruction device and the like. Compared with the common nano-metal composite initiation film, the initiation film based on copper azide has stronger initiation power, less charge and lower critical ignition energy. Because copper azide is sensitive, subsequent processing and forming cannot be carried out like other insensitive energetic materials, and the common method is to prepare a precursor into a film with a required structure and shape in advance through an in-situ preparation technology and then carry out azide operation. In 2017, shen et al (Shen Y, xu J, li N, et al. A micro-induced by in-situ synthesis of a three-dimensional porous copper sheet and an excitation performance [ J ]. Chemical Engineering Journal,2017, 326. In 2019, wang et al (Wang Q, J Han, zhang Y, et al, fibre of Copper Azide Film through Metal-Organic Framework for Micro-Initiator Applications [ J ]. ACS application Mater Interfaces,2019,11 (8): 8081-8.) produced a flexible Film from MOFT-CA by using an electrostatic spinning technology, after carbonization, the MOF precursor was put into a container of a photoinitiator, and finally a CA-C @ PF detonation Film with surface hydrophobicity was prepared through a gas-solid in-situ Azide reaction and a perfluorinated coating process, and CL-20 was successfully detonated. However, the gas-solid in-situ azide method has too long reaction time, and can completely react within more than 20 hours; and cuprous azide intermediate is generated in the reaction process, so that the product is usually a mixture of copper azide and cuprous azide, the stability of the product is not utilized, and the practical application of the gas-solid azide method is greatly limited due to the defects.

Disclosure of Invention

In view of the above, the present invention provides a copper azide energetic film and a preparation method thereof.

In order to realize the purpose, the technical scheme of the invention is as follows:

the energetic copper azide membrane takes a hydrophobic porous reticular material as a carrier, and is uniformly and densely distributed on a single surface of a stainless steel net.

Preferably, the carrier is a stainless steel mesh.

A preparation method of a copper azide energetic film comprises the following steps:

(1) Preparing a precursor film by adopting an interface method: preparing a copper salt aqueous solution and an organic solution containing a ligand, wherein the organic solvent is immiscible with water and has a density lower than that of water, placing a carrier on the surface of the aqueous solution, adding the organic solution, standing until the lower-layer aqueous solution is clear, uniformly covering the surface of the carrier with a precursor, taking out and drying to obtain a precursor film;

(2) Converting the precursor into copper azide by using a liquid-phase in-situ azide method: and (3) placing the precursor film into an aqueous solution of azido acid, reacting for 5-20 min at-10-20 ℃, taking out and drying to obtain the copper azide film.

Preferably, in the step (1), the copper salt is one or more of copper nitrate, copper sulfate, copper chloride and copper acetate.

Preferably, in the step (1), the ligand is more than one of 2-methylimidazole and benzimidazole.

Preferably, in the step (1), the organic solvent is one or more of hexanol, octanol, ethyl acetate and cyclohexane. More preferably, the organic solvent is n-octanol, which has a high viscosity and a reaction interface that is not easily fluctuated.

Preferably, in the step (1), the concentration of the copper salt aqueous solution is 0.1-0.8M, the concentration of the organic solution containing the ligand is 0.1-0.8M, and the interfacial reaction time is 1-24 h. More preferably, in step (1), the concentration of the aqueous solution of copper salt is 0.2 to 0.4M, and the concentration of the organic solution containing a ligand is 0.2 to 0.4M.

Preferably, in the step (2), the concentration of the aqueous solution of the azido acid is 0.05-1M.

Advantageous effects

1. The invention adopts a simple and feasible interface method to prepare a uniform and compact precursor film.

2. Compared with a gas-solid azide method, the method has the advantages of short reaction time, simple process and mild conditions, and is a novel micro-charge forming method.

Drawings

FIG. 1 is a sample of the copper 2-methylimidazole film described in example 1.

FIG. 2 is a diagram of a sample of the copper azide energetic film described in example 3.

FIG. 3 is a Scanning Electron Microscope (SEM) image of the copper 2-methylimidazole film described in example 1.

FIG. 4 is an SEM image of the copper azide energetic film described in example 3.

FIG. 5 is a diagram of the process of ignition of the copper azide energetic film described in example 3.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Example 1

Preparing a 0.2M n-octanol solution of 2-methylimidazole and a 0.2M aqueous solution of copper nitrate, and dissolving the n-octanol solution and the copper nitrate solutions by ultrasonic waves and continuous stirring by using a glass rod; adding 10mL of copper nitrate aqueous solution into a 25mL small glass bottle, shearing a stainless steel net into a size with the length multiplied by the width of 1.5cm multiplied by 1.5cm, sequentially carrying out ultrasonic treatment in ethanol and deionized water for 10min to remove impurities on the surface, gently placing the stainless steel net on the surface of the copper nitrate aqueous solution by using forceps, slowly dropwise adding 10mL of n-octanol solution of 2-methylimidazole onto the stainless steel net, reacting for 12h, taking out the porous stainless steel net, respectively washing with the deionized water and the ethanol, and drying to obtain the 2-methylimidazolium thin film taking the stainless steel net as a substrate, wherein the size is 1.

Example 2

Preparing a 0.4M n-octanol solution of 2-methylimidazole concentration and a 0.4M aqueous solution of copper nitrate, and dissolving the solutions by ultrasonic waves and continuous stirring by using a glass rod; adding 10mL of copper nitrate aqueous solution into a 25mL small glass bottle, shearing a stainless steel net into a size with the length multiplied by the width of 1.5cm multiplied by 1.5cm, carrying out ultrasonic treatment in ethanol and deionized water for 10min to remove impurities on the surface, gently placing the stainless steel net on the surface of the copper nitrate aqueous solution by using forceps, slowly dropwise adding 10mL of n-octanol solution of 2-methylimidazole onto the stainless steel net, reacting for 24h, taking out the porous stainless steel net, washing with the deionized water and the ethanol respectively, and drying to obtain the 2-methylimidazole copper film taking the stainless steel net as a substrate.

Example 3

Preparing a sodium azide solution with the concentration of 0.2M, adding a hydrochloric acid solution with the equimolar weight and mass fraction of 37%, adding the 2-methylimidazolium copper film into the azido acid solution under the ice bath condition, reacting for 20min, washing with ethanol, and drying to obtain a final product, namely the copper azide film, as shown in figure 2.

Example 4

Preparing a 0.4M sodium azide solution, adding a hydrochloric acid solution with an equimolar amount and mass fraction of 37%, adding the 2-methylimidazolium copper film into the hydrazoic acid solution under an ice bath condition, reacting for 10min, washing with ethanol, and drying to obtain the final product copper azide film.

Performing morphology characterization on the precursor film and the converted copper azide film by using an SEM (scanning electron microscope), wherein the surface of the 2-methylimidazole copper film is a planar structure formed by stacking flaky crystals together, as shown in FIG. 3; the surface of the copper azide film is a compact planar structure formed by interweaving copper azide nanowires, as shown in fig. 4.

And (3) performing an initiation test on the copper azide film, wherein the copper azide film is successfully initiated and shows good explosion performance, as shown in figure 5.

In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.

Claims

1. A copper azide energetic film is characterized in that: the energy-containing membrane takes a hydrophobic porous reticular material as a carrier, and copper azide is uniformly and densely distributed on the single surface of the stainless steel net.

2. The energetic copper azide film as set forth in claim 1 wherein: the carrier is a stainless steel mesh.

3. A method for producing the energetic copper azide film according to claim 1 or 2, wherein: the method comprises the following steps:

(1) Preparing a copper salt aqueous solution and an organic solution containing a ligand, wherein the organic solvent is immiscible with water and has a density lower than that of water, placing a carrier on the surface of the aqueous solution, adding the organic solution, standing until the lower-layer aqueous solution is clear, uniformly covering the surface of the carrier with a precursor, taking out and drying to obtain a precursor film;

(2) And (3) placing the precursor film into an aqueous solution of azido acid, reacting for 5-20 min at-10-20 ℃, taking out and drying to obtain the copper azide film.

4. The method of claim 3, wherein the copper azide energetic film is prepared by: in the step (1), the copper salt is more than one of copper nitrate, copper sulfate, copper chloride and copper acetate.

5. The method of claim 3, wherein the copper azide energetic film is prepared by: in the step (1), the ligand is more than one of 2-methylimidazole and benzimidazole.

6. The method of claim 3, wherein the copper azide energetic film is prepared by: in the step (1), the organic solvent is more than one of hexanol, octanol, ethyl acetate and cyclohexane.

7. The method of claim 6, wherein the copper azide energetic film is prepared by: the organic solvent is n-octanol.

8. The method of claim 6, wherein the copper azide energetic film is prepared by: in the step (1), the concentration of the copper salt aqueous solution is 0.1-0.8M, the concentration of the organic solution containing the ligand is 0.1-0.8M, and the interface reaction time is 1-24 h.

9. The method of claim 8, wherein the copper azide energetic film is prepared by: the concentration of the copper salt aqueous solution is 0.2-0.4M, and the concentration of the organic solution containing the ligand is 0.2-0.4M.

10. The method of claim 3, wherein the copper azide energetic film is prepared by: in the step (2), the concentration of the aqueous solution of the azido acid is 0.05-1M.