[Ag2BNOD] n energetic film, preparation method thereof and application of [Ag2BNOD] n energetic film in MEMS initiating explosive device

Abstract

The invention discloses a preparation method of a [Ag2BNOD] n energetic film, the [Ag2BNOD] n energetic film obtained through the preparation method and application of the [Ag2BNOD] n energetic film in an MEMS initiating explosive device, and relates to the technical field of energetic materials.The preparation method of the [Ag2BNOD] n energetic film specifically comprises the following steps that S1, a quartz glass substrate is ultrasonically cleaned with absolute ethyl alcohol, washed with water and air-dried, the quartz glass substrate is put into a sodium hydroxide solution to be soaked, washed with water and air-dried, and the [Ag2BNOD] n energetic film is obtained; soaking the quartz glass substrate in a mixed solution of ethanol, water and triaminopropyltriethoxysilane, washing the quartz glass substrate with water, and curing the quartz glass substrate at 90-110 DEG C for 0.5-2 hours to obtain a quartz glass substrate modified layer; s2, washing the quartz glass substrate modified layer obtained in the S1 with deionized water, soaking the quartz glass substrate modified layer in a silver nitrate solution, taking out the quartz glass substrate modified layer, washing the quartz glass substrate modified layer with deionized water, soaking the quartz glass substrate modified layer in a BNOD aqueous solution, and repeating the steps for 10-30 times to obtain a [Ag2BNOD] n energetic film; the preparation method is very suitable for automation, and the obtained energetic film can improve the energy output characteristic of the MEMS device and improve the ignition capability of the MEMS device.

Description

Technical Field

[0001] The present invention belongs to the technical field of energetic materials, and is specifically a [Ag2BNOD] n Energetic film, preparation method thereof and application thereof in MEMS pyrotechnics. Background Art

[0002] With the increasing demand for military and civilian equipment such as micro-spacecraft, smart airbags, and smart ammunition in modern technology, miniaturization, lightness, integration, and intelligent ignition devices are becoming the research direction of pyrotechnics technology. Among them, micro-electromechanical systems (MEMS) provide a technical approach for the development of MEMS pyrotechnic chips with excellent performance such as low-energy ignition, high-energy output, miniaturization, and high integration due to their high integration, ultra-miniaturization, and combination with digital logic circuits. However, the output energy of MEMS devices themselves is low and cannot reliably complete ignition and detonation. Therefore, it is necessary to integrate energetic materials into MEMS devices in the form of thin films to improve their energy output characteristics and increase the sparks sputtered during ignition, thereby improving their ignition ability. Since traditional charging methods such as press-fitting, pouring, and melting are not compatible with MEMS systems, domestic and foreign researchers have invested a lot of energy in exploring micro-charging methods.

[0003] At present, the research field of energetic films is mainly divided into thermite films, organic energetic films and energetic MOFs films. Among them, thermite films and organic energetic films are more studied. The stability of these two films is only maintained by the adhesion given by the film forming method during film formation. The film does not stabilize the morphology and composition of the film through chemical bonds, which in turn affects the ignition performance of the energetic film. Therefore, it is of great significance to improve the ignition performance of MEMS pyrotechnics by designing and preparing energetic MOFs films with good stability and good ignition performance. Summary of the invention

[0004] The object of the present invention is to provide a [Ag2BNOD] having good stability and good ignition performance n Preparation method of energetic thin film and obtained [Ag2BNOD] n Energetic films and their applications in MEMS pyrotechnics.

[0005] In order to solve the above technical problems, the present invention provides a [Ag2BNOD] n The method for preparing an energetic thin film is characterized by depositing [Ag2BNOD] layer by layer on the surface of a quartz glass substrate with hydrogen bonds removed from the surface n , and its specific preparation steps are as follows:

[0006] S1: modifying the quartz glass substrate: measuring 90% ethanol, water and triaminopropyltriethoxysilane in a volume ratio of 79-84:9-12:7-9, and ultrasonically dispersing for 2 minutes to obtain a mixed solution A; ultrasonically cleaning the quartz glass substrate in anhydrous ethanol solution for 10 minutes, rinsing with water, drying, and then soaking it in a 25% sodium hydroxide solution for 30 minutes, rinsing with water, drying, soaking the dried quartz glass substrate in the mixed solution A for 24 hours, rinsing with water, and curing it in an oven at 90-110°C for 0.5-2 hours to obtain a quartz glass substrate modified layer;

[0007] S2: Layer-by-layer deposition [Ag2BNOD] on the surface of the modified layer of the quartz glass substrate n : The modified quartz glass substrate obtained in S1 was rinsed with deionized water, immersed in a silver nitrate solution for 10 minutes, taken out and rinsed with deionized water, and then immersed in a BNOD aqueous solution for 10 minutes. The above steps were repeated 10-30 times to obtain [Ag2BNOD] n Energetic films.

[0008] Preferably, the silver nitrate aqueous solution in step S2 is obtained by dissolving 1.026 g of silver nitrate in 50 mL of water.

[0009] Preferably, the BNOD aqueous solution in step S2 is obtained by dissolving 1.019 g of BNOD in 50 mL of water.

[0010] Preferably, in step S1, the volume ratio of ethanol with a mass fraction of 90%, water, and triaminopropyltriethoxysilane is 82:10:8.

[0011] Preferably, in step S1, the temperature of the oven is set to 100° C. and the curing time is set to 1 hour.

[0012] Preferably, in step S2, the steps of soaking in silver nitrate solution, washing with water, and soaking in BNOD aqueous solution are repeated 20 times to obtain [Ag2BNOD] n Energetic films.

[0013] The present invention also provides a [Ag2BNOD] n The energetic film is deposited layer by layer on the surface of the quartz glass substrate with hydrogen bonds removed by the above preparation method [Ag2BNOD] n Prepared.

[0014] The present invention also provides a [Ag2BNOD] n The application of energetic film in MEMS explosive devices is characterized in that: the [Ag2BNOD] nThe energetic film is integrated on the MEMS device to improve the energy output characteristics of the MEMS device, increase the sparks sputtered during ignition, and improve its ignition capability.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] (1) 3,3'-Bis(1,2,4-oxadiazole)-5,5'-dimethylnitrate (BNOD) has excellent energy performance. Its theoretical density, heat of formation, detonation pressure and detonation velocity are as high as 1.82 g·cm -3 、592kJ·mol -1 , 32.2GPa and 8490m -1 The use of BNOD to construct the energetic film in the present invention can effectively improve the energy performance of the energetic film, thereby improving the energy output characteristics of the MEMS device, increasing the sparks sputtered during ignition, and improving its ignition capability.

[0017] (2) The quartz glass selected in the present invention has only a single component of SiO2, has high hardness, is resistant to high temperatures, has good electrical insulation and chemical stability. Using quartz glass as the substrate of the energetic film can greatly reduce the self-reaction of the energetic material caused by the substrate.

[0018] (3) The present invention adopts a layer-by-layer deposition method to control the density of energetic thin film deposition at the molecular scale, and the method is very suitable for automation, thereby promoting the reproducibility of synthesis. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 [Ag2BNOD] n Morphology of energetic films.

[0020] Figure 2 [Ag2BNOD] n DSC-TG curves of thermal properties of energetic films.

[0021] Figure 3 for [Ag2BNOD] n Graph of the ignition performance of energetic films.

[0022] Figure 4 is [Ag(ntz)] n High-speed photography of energetic thin film laser ignition.

[0023] Figure 5 This is a high-speed photograph of the energetic thin film laser ignition obtained in Comparative Example 2.

[0024] Figure 6 [Cd5(Mtta)9] was prepared by hydrothermal synthesis n Flow chart of energetic films.

[0025] Figure 7 [Cd5(Mtta)9] was prepared by hydrothermal synthesis n Morphology of energetic films. DETAILED DESCRIPTION

[0026] Example 1: [Ag2BNOD] n The method for preparing an energetic thin film is characterized by depositing [Ag2BNOD] layer by layer on the surface of a quartz glass substrate with hydrogen bonds removed from the surface n , and its specific preparation steps are as follows:

[0027] S1: Modifying the quartz glass substrate: taking anhydrous ethanol, water and triaminopropyltriethoxysilane in a volume ratio of 82:10:8, and ultrasonically dispersing for 2 minutes to obtain a mixed solution A; ultrasonically cleaning the quartz glass substrate in anhydrous ethanol solution for 10 minutes, rinsing with water, drying, and then soaking it in a sodium hydroxide solution with a mass fraction of 25% for 30 minutes, rinsing with water, drying, soaking the dried quartz glass substrate in the mixed solution A for 24 hours, rinsing with water, and curing it in an oven at 100°C for 1 hour to obtain a quartz glass substrate modified layer;

[0028] S2: Layer-by-layer deposition [Ag2BNOD] on the surface of the modified layer of the quartz glass substrate n : The modified quartz glass substrate obtained in S1 was rinsed with deionized water, immersed in a silver nitrate solution for 10 min, taken out and rinsed with deionized water, and then immersed in a BNOD aqueous solution for 10 min. The above steps were repeated 20 times to obtain [Ag2BNOD] n Energetic films.

[0029] The silver nitrate aqueous solution was prepared by dissolving 1.026 g of silver nitrate in 50 mL of water.

[0030] The BNOD aqueous solution was prepared by dissolving 1.019 g of BNOD in 50 mL of water.

[0031] The [Ag2BNOD] obtained in this example n Morphological characterization of energetic films, such as Figure 1 , found [Ag2BNOD] n The energetic film consists of irregular blocks [Ag2BNOD] n Crystal stacking, film thickness is about 1.8μm; for [Ag2BNOD] n Thermal performance tests of energetic films, such as Figure 2 It was found that there was an obvious exothermic peak near 217℃, and there was an obvious thermal weight loss in the TG curve at the corresponding temperature; by nIgnition performance test of energetic films, such as Figure 3 , found [Ag2BNOD] n The flame height of the energetic film can reach 11.2 mm, and the ignition duration can reach 450 μs. The results show that [Ag2BNOD] n Energetic films have excellent ignition properties.

[0032] Comparative Example 1: The preparation steps of the energetic film in this comparative example are the same as those in Example 1, except that 3-nitro-1-H-1,2,4-triazole (Hntz) is used as the energetic ligand to replace the BNOD energetic ligand in Example 1.

[0033] like Figure 4 The flame height and continuous ignition time of the energetic film prepared in this comparative example after laser ignition are 5 mm and 200 μs respectively, and its performance is inferior to that of the energetic film obtained by using BNOD energetic ligand in Example 1.

[0034] Comparative Example 2: The steps for preparing the energetic film in this comparative example are the same as those in Example 1, except that copper foil is used as the substrate in this comparative example instead of the quartz glass substrate in Example 1.

[0035] like Figure 5 The ignition performance of the energetic film prepared in this comparative example was characterized by laser ignition. The flame height and continuous ignition time were 7 mm and 250 μm, respectively. The ignition performance was inferior to that of the energetic film prepared using a quartz glass substrate.

[0036] Comparative Example 3: Figure 6 Preparation flow chart of the medium-energy film. This comparative example adopts the hydrothermal synthesis method to prepare [Cd5(Mtta)9] n Energetic films, characterize their morphology, such as Figure 7 As shown, its thickness is difficult to effectively control.

[0037] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A [Ag2BNOD] n A method for preparing an energetic film, characterized in that: By layer-by-layer deposition of [Ag2BNOD] on the surface of a quartz glass substrate with dehydrogenated surface bonds n , and its specific preparation steps are as follows: S1: modifying the quartz glass substrate: measuring 90% ethanol, water and triaminopropyltriethoxysilane in a volume ratio of 79-84:9-12:7-9, and ultrasonically dispersing for 2 minutes to obtain a mixed solution A; ultrasonically cleaning the quartz glass substrate in anhydrous ethanol solution for 10 minutes, rinsing with water, drying, and then soaking it in a 25% sodium hydroxide solution for 30 minutes, rinsing with water, drying, soaking the dried quartz glass substrate in the mixed solution A for 24 hours, rinsing with water, and curing it in an oven at 90-110°C for 0.5-2 hours to obtain a quartz glass substrate modified layer; S2: Layer-by-layer deposition [Ag2BNOD] on the surface of the modified layer of the quartz glass substrate n : The modified quartz glass substrate obtained in S1 was rinsed with deionized water, immersed in a silver nitrate solution for 10 minutes, taken out and rinsed with deionized water, and then immersed in a BNOD aqueous solution for 10 minutes. The above steps were repeated 10-30 times to obtain [Ag2BNOD] n Energetic films.

2. A [Ag2BNOD] according to claim 1 n The method for preparing an energetic film is characterized by: The silver nitrate aqueous solution in step S2 is obtained by dissolving 1.026 g of silver nitrate in 50 mL of water.

3. A [Ag2BNOD] according to claim 2 n The method for preparing an energetic film is characterized by: The BNOD aqueous solution in step S2 is obtained by dissolving 1.019 g of BNOD in 50 mL of water.

4. A [Ag2BNOD] according to claim 3 n The method for preparing an energetic film is characterized by: In the step S1, the volume ratio of ethanol with a mass fraction of 90%, water, and triaminopropyltriethoxysilane is 82:10:

8.

5. A [Ag2BNOD] according to claim 3 n The method for preparing an energetic film is characterized by: In step S1, the temperature of the oven is set to 100° C., and the curing time is set to 1 hour.

6. A [Ag2BNOD] according to claim 3 n The method for preparing an energetic film is characterized by: In step S2, the steps of soaking in silver nitrate solution, washing with water, and soaking in BNOD aqueous solution are repeated 20 times to obtain [Ag2BNOD] n Energetic films.

7. A [Ag2BNOD] as claimed in any one of claims 1 to 6 n [Ag2BNOD] prepared by the preparation method of energetic thin film n An energetic film, characterized in that It is a process of layer-by-layer deposition of [Ag2BNOD] on the surface of a quartz glass substrate with dehydrogenated surface bonds. n Prepared.

8. [Ag2BNOD] as claimed in claim 7 n The application of energetic film in MEMS explosive devices is characterized by: The [Ag2BNOD] n The energetic film is integrated on the MEMS device to improve the energy output characteristics of the MEMS device, increase the sparks sputtered during ignition, and improve its ignition capability.

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