Method for synthesizing nickel hydrazine nitrate based on inkjet printing and application thereof

Abstract

The application discloses a method for synthesizing nickel hydrazine nitrate based on inkjet printing and application thereof, and belongs to the technical field of energetic materials. The method is based on inkjet printing technology, nickel nitrate ink and hydrazine hydrate ink are respectively configured, the viscosity of the nickel nitrate ink is adjusted by using a binder, the surface tension and the viscosity of the hydrazine hydrate ink are adjusted by using a mass ratio of ethylene glycol and water, the nickel nitrate and the hydrazine hydrate are printed in sequence, and nickel hydrazine nitrate is prepared in situ. The method can print the nickel hydrazine nitrate initiating explosive on a medium in situ, realizes complete hands-off operation in the charging process, and avoids the danger in the manual nickel hydrazine nitrate charging process. Meanwhile, the fine control of the charging amount can be realized by using the inkjet printing.

Description

Technical Field

[0001] The present application belongs to the technical field of energetic materials, and specifically relates to a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application. Background Art

[0002] Primary explosives are a type of explosive that explodes with relatively weak initial impulse energy, achieving maximum explosion velocity within a short period of time and easily transitioning from combustion to detonation. They are widely used in both military and civilian explosives industries. Nickel hydrazine nitrate is a coordinated energetic material characterized by smokeless, odorless, and residue-free combustion, offering promising development prospects in smokeless fireworks. As a primary explosive, nickel hydrazine nitrate offers advantages such as low mechanical sensitivity and high flame sensitivity.

[0003] In recent years, to meet the demands of miniaturization and intelligentization of weaponry, pyrotechnics are evolving toward microelectromechanical systems (MEMS), characterized by diverse functions, miniaturized structures, and sequential integration. This requires that the energy converter and charge structures be micron-sized. Consequently, this places higher demands on the charge: high explosive power combined with a low charge mass.

[0004] Inkjet printing has been shown to facilitate the small-scale deposition of functional inks, overcoming the limitations of current processes that limit submillimeter spatial control. Researchers both domestically and internationally have explored the high-precision, complex-patterned, micro- and nanoscale microfabrication of energetic materials and energetic devices. However, due to the high sensitivity of initiators, there are no reports of successful in-situ initiator charging using inkjet printing. Summary of the Invention

[0005] 1. Purpose of the Invention

[0006] The purpose of this application is to provide a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application. Through the formulation design of the ink, nickel hydrazine nitrate is successfully synthesized by inkjet printing and applied to the preparation of pyrotechnics, which can realize the safe in-situ charging of nickel hydrazine nitrate detonator and achieve fine control of the charging amount.

[0007] 2. Technical solution

[0008] In order to solve the above problems, the technical solutions adopted in this application are as follows:

[0009] The present application provides a method for synthesizing nickel hydrazine nitrate based on inkjet printing, which comprises the following steps:

[0010] S1, configure ink

[0011] A nickel nitrate ink is prepared, which contains nickel nitrate, water, ethanol, and polyvinyl pyrrolidone. In the nickel nitrate ink, ethanol is used to increase the solubility of nickel nitrate and control the surface tension of the ink; and polyvinyl pyrrolidone is used to control the viscosity of the ink.

[0012] Prepare hydrazine hydrate ink: the hydrazine hydrate ink includes hydrazine hydrate, water, and ethylene glycol; in the hydrazine hydrate ink, the ratio of ethylene glycol to water is adjusted to control the surface tension and viscosity of the solution;

[0013] S2, inkjet printing

[0014] On a printing medium, firstly, a plurality of nickel nitrate layers are printed using nickel nitrate ink, and then hydrazine hydrate is printed on the printed nickel nitrate ink layers using hydrazine hydrate ink;

[0015] S3, vacuum drying

[0016] The product obtained in step S2 is dried under vacuum.

[0017] Furthermore, the nickel nitrate ink has a nickel nitrate content of 0.3 to 0.6 g / mL. Still further, the nickel nitrate ink has a nickel nitrate content of 0.5 to 0.6 g / mL.

[0018] Furthermore, the mass percentage of the above-mentioned binder polyvinyl pyrrolidone is 4% to 6%.

[0019] Furthermore, in the nickel nitrate ink, the mass percentage of ethanol is 10% to 20%.

[0020] Furthermore, in the nickel nitrate ink, the surface tension of the nickel nitrate ink is controlled to be 36.0-40.0 mN / m, and the viscosity is controlled to be 3.0-7.0 cps.

[0021] Furthermore, the hydrazine hydrate ink has a hydrazine hydrate content of 0.2 to 0.6 g / mL. Furthermore, the nickel nitrate ink has a nickel nitrate content of 0.5 to 0.6 g / mL.

[0022] Furthermore, in the above hydrazine hydrate ink, the mass ratio of ethylene glycol to water is 1:(3-4).

[0023] Furthermore, in the above-mentioned hydrazine hydrate ink, the surface tension of the hydrazine hydrate ink is controlled to be 40.0-46.0 mN / m, and the viscosity is controlled to be 9.0-12.0 cPs.

[0024] Furthermore, in the above-mentioned S2 inkjet printing, when the printing area is the same, the molar number of hydrazine hydrate is controlled to be equimolar or slightly larger than the molar number of nickel nitrate, and the shape can be controlled to have a characteristic size below 1 mm.

[0025] Furthermore, in the above-mentioned S2 inkjet printing, the volume of a single ink drop is 10 pL.

[0026] Furthermore, in the above-mentioned S2 inkjet printing, there is no particular limitation on the printing medium, which can be an pyrotechnic component of any structure, such as a semiconductor bridge.

[0027] Furthermore, in the vacuum drying step S3, the product obtained in S2 is placed in a vacuum oven and dried at 40°C for 6 to 12 hours to ensure that the solvent is fully evaporated.

[0028] Furthermore, the above-mentioned method for synthesizing nickel hydrazine nitrate based on inkjet printing uses a Fujifilm Dimatix material printer (DMP-2850), which is a DOD piezoelectric driven inkjet printer with the functions of adjusting the print head temperature, platen temperature, emission voltage, printing height, ink drop spacing and multiple repeated printing.

[0029] Furthermore, the printing nozzle diameter of the above-mentioned Fujifilm Dimatix material printer DMP-2850 is 21 μm.

[0030] Furthermore, the aforementioned Fujifilm Dimatix material printer DMP-2850 has 16 nozzles driven by the Dimatix printer's piezoelectric elements, which are much smaller than those of most laboratory-developed inkjet printers (e.g., typically 60 to 90 μm in diameter).

[0031] Furthermore, the jetting voltage of the above-mentioned Fujifilm Dimatix material printer DMP-2850 is 15 to 16.5 V, the jetting frequency is 5 kHz, and the inkjet spacing is 15 to 20 μm.

[0032] The present application also provides an application of the above-mentioned method for synthesizing nickel hydrazine nitrate based on inkjet printing in the preparation of pyrotechnic components, thereby realizing the safe in-situ charging of nickel hydrazine nitrate detonating explosives.

[0033] Furthermore, the above applications include printing synthetic nickel hydrazine nitrate on components such as semiconductor bridges.

[0034] This application also provides an energetic pyrotechnic component prepared by the above application.

[0035] The present application also provides an energetic pyrotechnic device, comprising the above-mentioned energetic pyrotechnic device component.

[0036] 3. Beneficial effects

[0037] Compared with the prior art, the present application has the following advantages:

[0038] (1) The present application provides a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application, wherein a binder is used to adjust the viscosity of nickel nitrate ink, ethanol is used to increase the solubility of nickel nitrate and control the surface tension of the ink, and the mass ratio of ethylene glycol and water is used to adjust the surface tension and viscosity of hydrazine hydrate ink. Nickel nitrate azide and hydrazine hydrate are printed in sequence, and nickel hydrazine nitrate is obtained by in-situ reaction. The shape and size of the nickel hydrazine nitrate (initiator) synthesized based on inkjet printing are controllable, especially as an initiator, the characteristic size can be controlled to be less than 1 mm. The thickness of the initiator can be adjusted according to the number of printed layers, which increases the flexibility of the initiator charge while ensuring safety.

[0039] (2) The present application provides a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application. The inkjet printing method is used to in-situ print the synthesized nickel hydrazine nitrate (initiator) on the pyrotechnic components (printing medium). The charging process is completely hands-free, avoiding the dangers of manual charging of nickel hydrazine nitrate.

[0040] (3) The present application provides a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application, which adopts Fujifilm Dimatix material printer DMP-2850 inkjet printing. The amount of each droplet is controlled at the pL level. The amount of droplets can be controlled according to the size of the pattern, thereby controlling the loading amount of the synthesized nickel hydrazine nitrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is the SEM image of the synthesized nickel hydrazine nitrate sample;

[0042] Figure 2 This is a sample image of nickel hydrazine nitrate printed on a substrate;

[0043] Figure 3 This is the infrared spectrum of the synthesized nickel hydrazine nitrate sample. DETAILED DESCRIPTION

[0044] The present application is further described below with reference to specific embodiments.

[0045] It should be noted that the terms such as "upper", "lower", "left", "right", and "middle" cited in this specification are only for the convenience of description and are not used to limit the scope of implementation. Changes or adjustments to their relative relationships should be regarded as the scope of implementation of this application without substantially changing the technical content.

[0046] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0047] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0048] As used herein, the term "about" is used to provide flexibility and imprecision associated with a given term, measurement, or value. One skilled in the art can readily determine the degree of flexibility for a particular variable.

[0049] As used herein, the term "at least one of" is intended to be synonymous with "one or more of." For example, "at least one of A, B, and C" explicitly includes only A, only B, only C, and combinations of each thereof.

[0050] Concentration, amount and other numerical data can be presented in range format in this article.Should be understood that such range format is only used for convenience and brevity, and should be flexibly interpreted as not only including the numerical value clearly described as range limit, but also including all independent numerical values ​​or subranges encompassed within the scope, just as each numerical value and subrange are clearly described.For example, the numerical range of about 1 to about 4.5 should be interpreted as not only including the limit value of 1 to about 4.5 clearly described, but also including independent numerals (such as 2,3,4) and subranges (such as 1 to 3,2 to 4 etc.).The same principle is applicable to the scope of only narrating a numerical value, such as "less than about 4.5", which should be interpreted as including all above-mentioned values ​​and scopes.In addition, no matter how the breadth of described scope or feature is, this explanation should be applicable.

[0051] Example 1

[0052] This embodiment provides a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application. Specifically, it includes:

[0053] S1, configure ink

[0054] Prepare nickel nitrate ink: Take 18 mL of deionized water and 2 mL of anhydrous ethanol, mix well, and then add 2 g of PVP (polyvinyl pyrrolidone). After it is fully dissolved, take 1 mL of the solution and add 0.5 g of nickel nitrate to it to prepare 0.5 g / mL nickel nitrate ink; the surface tension is 36 mN / m and the viscosity is 6.8 cPs.

[0055] To prepare hydrazine hydrate ink, take 0.5 g of 85% hydrazine hydrate solution (volume approximately 0.59 mL), add 0.3 mL of water and 0.1 mL of ethylene glycol to it to make a 0.5 g / mL hydrazine hydrate solution; the surface tension is 41 mN / m and the viscosity is 11 cPs;

[0056] S2, inkjet printing

[0057] Nickel nitrate ink was loaded into the DMP-2850 and the printing parameters were set as follows: voltage 15 V, frequency 5 kHz, nozzle temperature 30°C, drop spacing 20 μm, voltage rise / fall within 1 μs, pulse duration ~6.4 μs, and 100% printing potential.

[0058] In this embodiment, the printing medium is a silicon dioxide substrate (1.5 mm × 1.8 mm); the printing area is 0.6 mm × 0.6 mm, the number of layers is 10, and then the hydrazine hydrate ink is replaced to print 11 layers. At this time, the molar number of hydrazine hydrate is slightly greater than the molar number of nickel nitrate, which is conducive to the full reaction.

[0059] S3, vacuum drying

[0060] The in-situ printed semiconductor bridge containing nickel hydrazine nitrate was placed in a vacuum oven and dried at 40° C. for 6 h to obtain a finished product.

[0061] Figure 1 is the SEM image of the synthesized nickel hydrazine nitrate sample; Figure 2 This is a sample image of nickel hydrazine nitrate printed on a substrate; Figure 2 This is the infrared spectrum of the synthesized nickel hydrazine nitrate sample.

[0062] Example 2

[0063] Take 19mL of deionized water and add 1mL of anhydrous ethanol, while keeping other conditions unchanged, to prepare nickel nitrate ink. It was found that the change of ethanol content had almost no effect on the viscosity, and the surface tension was 40mN / m, so the finished nickel hydrazine nitrate product could be successfully printed.

[0064] Example 3

[0065] In two experiments, 0.5g and 1.5g of PVP were added, respectively, to prepare nickel nitrate ink. The experiments found that the change in PVP concentration had little effect on surface tension, primarily affecting viscosity. The viscosities of the nickel nitrate inks in the two experiments were 4.12 cPs and 5.80 cPs, respectively. All other conditions were the same as in Example 1, and the finished nickel hydrazine nitrate was successfully printed.

[0066] Example 4

[0067] The solvent component ethylene glycol:deionized water mass ratio was increased from 1:3 to 1:4, and the hydrazine hydrate ink was prepared. The viscosity decreased from 12 cPs to 9 cPs. When the other conditions were the same as in Example 1, printing was also possible, and the finished nickel hydrazine nitrate product was successfully printed.

[0068] Comparative Example 1

[0069] I added 4 mL of ethanol to 16 mL of deionized water, leaving all other conditions unchanged, to create nickel nitrate ink. However, the measured surface tension was too low, causing the ink to overflow and fail to form single droplets. Consequently, the nickel nitrate ink failed to print.

[0070] Comparative Example 2

[0071] Hydrazine hydrate inks were prepared with solvent components of ethylene glycol and deionized water in a mass ratio of 1:2 and 1:1, respectively, while other conditions remained unchanged. The viscosity of both inks was too high, and the ink could not be squeezed out of the nozzle, resulting in failure to print.

Claims

1. A method for synthesizing nickel hydrazine nitrate based on inkjet printing, characterized in that, The method comprises the following steps: S1, configure ink Prepare nickel nitrate ink, which contains nickel nitrate, water, ethanol, and polyvinyl pyrrolidone; the nickel nitrate ink has a surface tension of 36.0 to 40.0 mN / m and a viscosity of 3.0 to 7.0 cps; Prepare hydrazine hydrate ink: the hydrazine hydrate ink includes hydrazine hydrate, water, and ethylene glycol; the surface tension of the hydrazine hydrate ink is 40.0 to 46.0 mN / m, and the viscosity is 9.0 to 12.0 cPs; S2, inkjet printing On a printing medium, firstly, a plurality of nickel nitrate layers are printed using nickel nitrate ink, and then hydrazine hydrate is printed on the printed nickel nitrate ink layers using hydrazine hydrate ink; S3, vacuum drying The product obtained in step S2 is dried under vacuum.

2. A method for synthesizing nickel hydrazine nitrate based on inkjet printing according to claim 1, characterized in that, In the nickel nitrate ink, the content of nickel nitrate is 0.3-0.6 g / mL; the mass percentage of polyvinyl pyrrolidone is 4%-6%; and the mass percentage of ethanol is 10%-20%.

3. A method for synthesizing nickel hydrazine nitrate based on inkjet printing according to claim 2, characterized in that, In the hydrazine hydrate ink, the hydrazine hydrate content is 0.2-0.6 g / mL; and the mass ratio of ethylene glycol to water is 1:(3-4).

4. A method for synthesizing nickel hydrazine nitrate based on inkjet printing according to claim 3, characterized in that, In the S2 inkjet printing, when the printing area is the same, the molar number of hydrazine hydrate is controlled to be equimolar or slightly greater than the molar number of nickel nitrate.

5. A method for synthesizing nickel hydrazine nitrate based on inkjet printing according to claim 4, characterized in that, In the S2 inkjet printing, the volume of a single ink drop is 10 pL.

6. The method for synthesizing nickel hydrazine nitrate based on inkjet printing according to claim 5, wherein: In the S2 inkjet printing, a Fujifilm Dimatix material printer was used.

7. The method for synthesizing nickel hydrazine nitrate based on inkjet printing according to claim 5, wherein: When printing, the Fujifilm Dimatix material printer DMP-2850 has an ejection voltage of 15 to 16.5 V, an ejection frequency of 5 kHz, and an inkjet spacing of 15 to 20 μm.

8. Use of the method for synthesizing nickel hydrazine nitrate based on inkjet printing according to any one of claims 1 to 7 in the preparation of pyrotechnic device components.

9. The pyrotechnic component prepared in the application of claim 8.

10. An energetic explosive device, characterized in that: The energetic pyrotechnic device comprises the pyrotechnic device component according to claim 9.

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