Method for synthesizing nickel hydrazine nitrate based on ink-jet printing and application thereof

Abstract

The invention discloses a method for synthesizing nickel hydrazine nitrate based on ink-jet printing and application of the method, and belongs to the technical field of energetic materials. The method is based on an ink-jet printing technology and comprises the steps that nickel nitrate ink and hydrazine hydrate ink are prepared respectively, the viscosity of the nickel nitrate ink is adjusted through a binder, the surface tension and viscosity of the hydrazine hydrate ink are adjusted through the mass ratio of ethylene glycol to water, nickel nitrate and hydrazine hydrate are printed sequentially, and nickel hydrazine nitrate is obtained through in-situ preparation. According to the method, the nickel hydrazine nitrate initiating explosive can be printed on the medium in situ, complete hand-free operation in the charging process is achieved, and danger in the manual nickel hydrazine nitrate charging process is avoided. And meanwhile, fine control over the explosive loading amount can be achieved through ink-jet 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] Detonators are explosives that can explode under weak initial impulse energy, and the explosion speed can be increased to the maximum value in a very short time. They are easy to burn and turn into detonation. They are widely used in military and civil explosives industries. Nickel hydrazine nitrate is a coordination energetic material, which is characterized by smokeless, odorless and residue-free combustion. It has good development prospects in smokeless fireworks. As a detonator, nickel hydrazine nitrate has the advantages of low mechanical sensitivity and high flame sensitivity.

[0003] In recent years, in order to meet the requirements of miniaturization and intelligence of weapons and equipment, pyrotechnics are developing towards MEMS (Micro Electro-Mechanical Systems) with multiple functions, miniature structures and sequence integration. This requires the energy conversion element and the charge structure size to be in the micron level. Therefore, this puts forward higher requirements for the charge: it has a large detonation capacity and a small charge amount.

[0004] Inkjet printing has been shown to be beneficial for the small-scale deposition of functional inks, making up for the inability to perform sub-millimeter spatial control in current processes. Domestic and foreign scholars have preliminarily explored the research on micro-charging of energetic materials and micro-manufacturing of energetic devices at high precision, complex patterns, and micro-nano levels. However, due to the high sensitivity of detonators, there are no reports on the successful in-situ charging of detonators using inkjet printing methods. Summary of the invention

[0005] 1. Purpose of the Invention

[0006] The purpose of the present application is to provide a method for synthesizing nickel hydrazine nitrate based on inkjet printing and its application. Through the ink formula design, 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 detonating agent and realize the 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, the method comprising the following steps:

[0010] S1, configure ink

[0011] A nickel nitrate ink is prepared, wherein the nickel nitrate ink comprises nickel nitrate, water, ethanol and polyvinyl pyrrolidone; in the nickel nitrate ink, the ethanol is used to increase the solubility of the nickel nitrate and control the surface tension of the ink; and the polyvinyl pyrrolidone is used to control the viscosity of the ink;

[0012] Prepare hydrazine hydrate ink: the hydrazine hydrate ink comprises 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 with nickel nitrate ink, and then hydrazine hydrate is printed on the printed nickel nitrate ink layers with hydrazine hydrate ink;

[0015] S3, vacuum drying

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

[0017] Furthermore, in the nickel nitrate ink, the content of nickel nitrate is 0.3-0.6 g / mL. Furthermore, in the nickel nitrate ink, the content of nickel nitrate is 0.5-0.6 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, in the above hydrazine hydrate ink, the content of hydrazine hydrate is 0.2 to 0.6 g / mL. Furthermore, in the above nickel nitrate ink, the content of nickel nitrate is 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 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 equal to or slightly greater 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 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 special limitation on the printing medium, and it can be an pyrotechnic component of any structure, such as a semiconductor bridge.

[0027] Furthermore, in the above-mentioned S3 vacuum drying, 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 volatilized.

[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 above-mentioned Fujifilm Dimatix material printer DMP-2850 has 16 nozzles, which are driven by the piezoelectric elements of the Dimatix printer, which are much smaller than most laboratory-developed inkjet printers (eg, 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 to achieve safe in-situ charging of nickel hydrazine nitrate detonating explosives.

[0033] Furthermore, the above application includes printing the synthesized nickel hydrazine nitrate on components such as semiconductor bridges.

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

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

[0036] 3. Beneficial effects

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

[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 nickel hydrazine nitrate (explosive) synthesized based on inkjet printing has controllable shape and size, especially as an explosive, the characteristic size can be controlled to be less than 1 mm. The thickness of the explosive can be adjusted according to the number of printed layers, which increases the flexibility of the explosive 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, and the amount of each drop 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 a 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 in conjunction with specific embodiments.

[0045] It should be noted that the terms such as "upper", "lower", "left", "right", "middle", etc. 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 otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled 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 conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0048] As used herein, the term "about" is used to provide flexibility and imprecision associated with a given term, measurement or value. The degree of flexibility for a particular variable can be easily determined by one skilled in the art.

[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" expressly 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 herein.It should be understood that such range format is only used for convenience and simplicity, and should be flexibly interpreted as not only including the numerical value clearly described as range limit, but also including all single numerical values ​​or sub-ranges contained in the range, just as each numerical value and sub-range 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 single numerals (such as 2,3,4) and sub-ranges (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 the above-mentioned values ​​and ranges.In addition, no matter how the breadth of the described range 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 add 2 g of PVP (polyvinyl pyrrolidone); after 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] Prepare hydrazine hydrate ink: take 0.5 g (volume about 0.59 mL) of hydrazine hydrate solution with a mass fraction of 85%, add 0.3 mL of water and 0.1 mL of ethylene glycol to prepare 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 DMP-2850, and the printing parameters were set as follows: voltage 15 V, frequency 5 kHz, nozzle temperature 30 °C, ink drop spacing 20 μm, voltage rise / fall within 1 μs, pulse duration ~6.4 μs, 100% printing potential;

[0058] In this embodiment, the printing medium is a silicon dioxide substrate (1.5mm×1.8mm); the printing area is 0.6mm×0.6mm, 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 a 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, keep other conditions unchanged, and prepare nickel nitrate ink. It is found that the change of ethanol content has almost no effect on viscosity. The surface tension is 40mN / m, and the nickel hydrazine nitrate product can be successfully printed.

[0064] Example 3

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

[0066] Example 4

[0067] The mass ratio of the solvent component ethylene glycol: deionized water is changed from 1:3 to 1:4, and the hydrazine hydrate ink is prepared. The viscosity is changed from 12 cPs to 9 cPs, and the viscosity becomes smaller. When the other conditions are the same as those in Example 1, the printing can also be carried out, and the hydrazine nitrate nickel product is successfully printed.

[0068] Comparative Example 1

[0069] Take 16mL of deionized water and add 4mL of ethanol, and keep other conditions unchanged to prepare nickel nitrate ink. At this time, the surface tension is too small, the ink keeps overflowing, and a single droplet cannot be formed. Nickel nitrate ink cannot be printed.

[0070] Comparative Example 2

[0071] The solvent components ethylene glycol: deionized water mass ratios were respectively configured to be 1:2 and 1:1, and other conditions remained unchanged to prepare hydrazine hydrate ink. The viscosity was too high, and the ink could not be squeezed out of the nozzle and could not be printed.

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 A nickel nitrate ink is prepared, wherein the nickel nitrate ink comprises nickel nitrate, water, ethanol, and polyvinyl pyrrolidone; the surface tension of the nickel nitrate ink is 36.0 to 40.0 mN / m, and the viscosity is 3.0 to 7.0 cps; Prepare hydrazine hydrate ink: the hydrazine hydrate ink comprises hydrazine hydrate, water and ethylene glycol; the surface tension of the hydrazine hydrate ink is 40.0-46.0 mN / m, and the viscosity is 9.0-12.0 cPs; S2, inkjet printing On a printing medium, firstly a plurality of nickel nitrate layers are printed with nickel nitrate ink, and then hydrazine hydrate is printed on the printed nickel nitrate ink layers with 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, characterized in that: 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, characterized in that: The above-mentioned Fujifilm Dimatix material printer DMP-2850 has a jetting voltage of 15 to 16.5 V, a jetting 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 as described in any one of claims 1 to 7 in the preparation of pyrotechnic components.

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

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

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