3-nitro-1,2,4-triazole-5-ketone / zirconium dioxide composite nano energetic material and preparation method thereof

Abstract

The present application relates to a kind of 3-nitro-1,2,4-triazole-5-ketone / zirconium dioxide composite nano energetic material and its preparation method, the material is composed of "core" and "shell" two parts."Core" is NTO particle, and 3-nitro-1,2,4-triazole-5-ketone particle with particle size of 500-5000nm is obtained by spray drying."Shell" is nano zirconium dioxide particle with particle size of 5-300nm.3-nitro-1,2,4-triazole-5-ketone / zirconium dioxide composite nano energetic material is prepared using ultrasonic mixing effect.The composite nano energetic material prepared by the present application has high energy density of 3-nitro-1,2,4-triazole-5-ketone, conductivity of zirconium dioxide, and excellent insensitivity and strong anti-metal corrosion of composite nano material.The preparation process of this method is simple, the cost is low, nano zirconium dioxide can be uniformly coated on the energetic material 3-nitro-1,2,4-triazole-5-ketone particle, and the particle size and thickness of the composite material can be controlled, with good application prospect.

Description

Technical Field

[0001] This invention relates to the field of energetic materials technology, specifically to a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite nanomaterial and its preparation method. Background Technology

[0002] 3-Nitro-1,2,4-triazol-5-one (NTO) is a promising insensitive energetic material with high energy density, good thermal stability, and appropriate mechanical sensitivity, and is frequently used as an important component of high-power missile munitions and solid propellants. However, the hydrogen (H) in the NTO molecule is readily released into the environment, causing severe corrosion to the metal casing of the warhead. Therefore, researchers in related fields urgently need to find suitable methods to solve this current problem.

[0003] Zirconia is a material with excellent properties such as high melting point, high hardness, high corrosion resistance, and high density, and it has wide applications in the industrial field. Due to its relatively good electrical conductivity, maintaining a certain level of conductivity under different temperature and humidity conditions, it also has wide applications in the electronics industry. By attaching zirconium dioxide nanoparticles to the surface of NTO particles, the acidity of the NTO particles can be effectively suppressed through coating, reducing corrosion of the warhead metal materials and improving safety and compatibility. Furthermore, the conductivity of zirconium dioxide can be used to quickly transfer static electricity generated by accidental stimuli such as friction and shear during the use of energetic materials, avoiding the formation of hot spots and enhancing the safety performance of explosives. However, no research has been reported in this area yet.

[0004] Therefore, a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial and its preparation method are urgently needed in the industry. Summary of the Invention

[0005] Based on the above analysis, the present invention aims to provide a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial and its preparation method. The 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial obtained by this method simultaneously possesses the high energy density of 3-nitro-1,2,4-triazol-5-one, the conductivity of zirconium dioxide, and the advantages of excellent insensitivity and strong resistance to metal corrosion of composite nanomaterials. The preparation process is simple and low-cost. The nano-zirconium dioxide can be uniformly coated on the particles of the energetic material 3-nitro-1,2,4-triazol-5-one. The particle size and thickness of the composite material can be controlled, showing good application prospects.

[0006] This invention is achieved through the following technical means:

[0007] This invention discloses a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial, comprising:

[0008] It consists of two parts: the core and the shell; among which:

[0009] The "core" consists of NTO particles with a particle size of 500–5000 nm.

[0010] The "shell" consists of nano-zirconia particles with a particle size of 5–300 nm.

[0011] This invention also discloses a method for preparing 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterials, comprising:

[0012] (1) Preparation of the nucleus: At room temperature, a certain mass of NTO raw material is dissolved in a solvent to prepare a precursor solution. Different process parameters such as nitrogen inlet flow rate, inlet temperature, and feed rate are set in the spray dryer. After the instrument is filled with nitrogen, the precursor solution is introduced into the instrument under the action of a peristaltic pump. Under the action of hot nitrogen, the solvent evaporates rapidly, and the NTO particles fall into the collection bottle under the action of centrifugal force, finally obtaining refined NTO particles.

[0013] (2) Preparation of the shell: Take nano-zirconia in a non-solvent, stir and then disperse ultrasonically;

[0014] (3) Preparation of composite nano energetic materials: Take a certain mass of refined NTO particles into a beaker, add a small amount of non-solvent, stir to prepare a suspension, add nano zirconium dioxide dispersion dropwise to the suspension under stirring, then perform ultrasonic mixing, and finally centrifuge, wash and vacuum dry to obtain 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite nano energetic materials.

[0015] Furthermore, the size of the NTO raw material in step (1) is in the range of 10 to 1000 μm.

[0016] Furthermore, the purity of the NTO raw material in step (1) is ≥98%.

[0017] Further, the NTO solvent in step (1) is either deionized water or acetone, and the mass-to-volume ratio of NTO particles to solvent is (2-50) g: (100-500) mL.

[0018] Further, in step (1), the nitrogen inlet flow rate is 2-10 L / min, the inlet temperature is 55-120℃, and the feed rate is 1-10 mL / min.

[0019] Furthermore, the particle size of the nano-zirconia in step (2) is 5-300 nm.

[0020] Further, the non-solvent mentioned in step (2) is any one of anhydrous ethanol, ethyl acetate, diethyl ether, and isopropanol.

[0021] Further, the mass-to-volume ratio of nano-zirconia to non-solvent in step (2) is (0.1-1) g: (20-100) mL.

[0022] Furthermore, the stirring speed in step (2) is 150-500 r / min, and the stirring time is 30-60 min.

[0023] Furthermore, the ultrasonic dispersion frequency and power in step (2) are 40kHz and 300W, the ultrasonic time is 20-120min, and the ultrasonic temperature is 30-60℃.

[0024] Further, the non-solvent mentioned in step (3) is any one of anhydrous ethanol, ethyl acetate, diethyl ether, and isopropanol, and the mass-volume ratio of refined NTO particles to non-solvent is (5-20) g: (10-50) mL.

[0025] Furthermore, the stirring speed in step (3) is 200-650 r / min, and the stirring time is 10-50 min.

[0026] Furthermore, the dropping rate in step (3) is 5 to 30 mL / min.

[0027] Furthermore, the ultrasonic frequency and power in step (3) are 20kHz and 800W respectively, the ultrasonic time is 3-40min, and the ultrasonic temperature is 25-50℃.

[0028] Furthermore, the centrifugation speed in step (3) is 500-5000 r / min, and the centrifugation time is 5-30 min.

[0029] Furthermore, the washing process described in step (3) involves washing 2 to 4 times with a mixture of anhydrous ethanol and / or ethyl acetate.

[0030] Furthermore, the drying conditions described in step (3) are carried out under vacuum drying at 55–105°C for 4–12 hours.

[0031] The present invention also discloses a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial prepared according to any of the above preparation methods.

[0032] The beneficial effects of this invention are as follows:

[0033] 1. This invention enables the loading of nano-zirconia onto the surface of refined NTO particles using a simple method, thereby preparing NTO particle / zirconia composite nano energetic materials with a core-shell structure. The core-shell structure is distinct, has a wide adjustable range, a simple process, low cost, and a wide range of applications.

[0034] 2. The 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial prepared by this invention has the high-energy insensitivity characteristics of refined NTO particles. On the other hand, the coating of nano-zirconium dioxide solves the problem of acid release from NTO particles, effectively inhibits acid escape, enhances the material's resistance to metal corrosion, and also improves the conductivity of the energetic composite material, further optimizing the safety performance.

[0035] 3. The 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial prepared by this invention can adjust the particle size of NTO particles and the coating thickness of nano-zirconium dioxide, thereby meeting the requirements of different fields or environments and broadening the application range of NTO particles. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0037] Figure 1 The microstructure of the refined NTO particles prepared according to Example 1 of the method provided by the present invention is shown.

[0038] Figure 2 The microstructure of the 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial prepared according to Example 3 of the method provided by the present invention is shown. Detailed Implementation

[0039] The present invention will now be described in detail with reference to embodiments and accompanying drawings. However, it should be understood that the embodiments and drawings are for illustrative purposes only and do not constitute any limitation on the scope of protection of the present invention. All reasonable modifications and combinations included within the inventive spirit of the present invention fall within the scope of protection of the present invention.

[0040] Example 1

[0041] A method for preparing a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial includes the following steps:

[0042] (1) Preparation of the nucleus: At room temperature, 5g of NTO raw material with a particle size of 300μm was dissolved in 100mL of deionized water to prepare a precursor solution. In a spray dryer, the nitrogen inlet flow rate was set to 4L / min, the inlet temperature was 55℃, and the feed rate was 3mL / min. After the instrument was filled with nitrogen, the precursor solution was introduced into the instrument under the action of a peristaltic pump. Under the action of hot nitrogen, the solvent evaporated rapidly, and the NTO particles fell into the collection bottle under the action of centrifugal force, finally obtaining refined NTO particles.

[0043] (2) Preparation of shell: Take 0.2g of nano-zirconia with a particle size of 50nm and put it in 40mL of anhydrous ethanol. Stir at 200r / min for 30min. Then, ultrasonically disperse it at a frequency of 40kHz and a power of 300W for 20min and an ultrasonic temperature of 30℃.

[0044] (3) Preparation of composite energetic nanomaterials: 5g of refined NTO particles were placed in a beaker, 10mL of anhydrous ethanol was added, and a suspension was prepared by stirring at 200r / min for 10min. Under stirring, the nano-zirconia dispersion was added dropwise to the suspension at a rate of 5mL / min. Then, ultrasonic mixing was performed at a frequency of 20kHz and a power of 800W for 5min and a temperature of 25℃. Finally, the mixture was centrifuged at 1000r / min for 10min, washed twice with anhydrous ethanol, and dried at 60℃ for 4h to obtain 3-nitro-1,2,4-triazol-5-one / zirconia composite energetic nanomaterials.

[0045] Example 2

[0046] A method for preparing a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial includes the following steps:

[0047] (1) Preparation of the nucleus: At room temperature, 10g of NTO raw material with a particle size of 400μm was dissolved in 200mL of deionized water to prepare a precursor solution. In a spray dryer, the nitrogen inlet flow rate was set to 5L / min, the inlet temperature was 60℃, and the feed rate was 4mL / min. After the instrument was filled with nitrogen, the precursor solution was introduced into the instrument under the action of a peristaltic pump. Under the action of hot nitrogen, the solvent evaporated rapidly, and the NTO particles fell into the collection bottle under the action of centrifugal force, finally obtaining refined NTO particles.

[0048] (2) Preparation of shell: Take 0.1g of nano-zirconia with a particle size of 20nm in 20mL of anhydrous ethanol, stir at 300r / min for 40min, and then ultrasonically disperse at a frequency of 40kHz and a power of 300W for 30min and an ultrasonic temperature of 40℃.

[0049] (3) Preparation of composite energetic nanomaterials: 8g of refined NTO particles were placed in a beaker, 20mL of ethyl acetate was added, and the mixture was stirred at 250r / min for 20min to prepare a suspension. Under stirring, the nano-zirconia dispersion was added dropwise to the suspension at a rate of 6mL / min. Then, the mixture was ultrasonically mixed at a frequency of 20kHz and a power of 800W for 10min at a temperature of 30℃. Finally, the mixture was centrifuged at 1500r / min for 15min, washed three times with ethyl acetate, and dried at 80℃ for 6h to obtain 3-nitro-1,2,4-triazol-5-one / zirconia composite energetic nanomaterials.

[0050] Example 3

[0051] A method for preparing a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial includes the following steps:

[0052] (1) Preparation of the nucleus: At room temperature, 20g of NTO raw material with a particle size of 100μm was dissolved in 300mL of acetone to prepare a precursor solution. In a spray dryer, the nitrogen inlet flow rate was set to 6L / min, the inlet temperature was 65℃, and the feed rate was 6mL / min. After the instrument was filled with nitrogen, the precursor solution was introduced into the instrument under the action of a peristaltic pump. Under the action of hot nitrogen, the solvent evaporated rapidly, and the NTO particles fell into the collection bottle under the action of centrifugal force, finally obtaining refined NTO particles.

[0053] (2) Preparation of shell: Take 0.2g of nano-zirconia with a particle size of 50nm and put it into 30mL of anhydrous ethanol. Stir at 400r / min for 50min. Then, ultrasonically disperse it at a frequency of 40kHz and a power of 300W for 40min and an ultrasonic temperature of 45℃.

[0054] (3) Preparation of composite energetic nanomaterials: 10g of refined NTO particles were placed in a beaker, 30mL of diethyl ether was added, and the mixture was stirred at 300r / min for 30min to prepare a suspension. Under stirring, the nano-zirconia dispersion was added dropwise to the suspension at a rate of 8mL / min. Then, the mixture was ultrasonically mixed at a frequency of 20kHz and a power of 800W for 20min at a temperature of 40℃. Finally, the mixture was centrifuged at 2000r / min for 10min, washed four times with ethyl acetate, and dried at 90℃ for 8h to obtain 3-nitro-1,2,4-triazol-5-one / zirconia composite energetic nanomaterials.

[0055] Example 4

[0056] A method for preparing a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial includes the following steps:

[0057] (1) Preparation of the nucleus: At room temperature, 30g of NTO raw material with a particle size of 600μm was dissolved in 500mL of acetone to prepare a precursor solution. In a spray dryer, the nitrogen inlet flow rate was set to 8L / min, the inlet temperature was 80℃, and the feed rate was 6mL / min. After the instrument was filled with nitrogen, the precursor solution was introduced into the instrument by a peristaltic pump. Under the action of hot nitrogen, the solvent evaporated rapidly, and the NTO particles fell into the collection bottle under the action of centrifugal force, finally obtaining refined NTO particles.

[0058] (2) Preparation of shell: Take 0.5g of nano-zirconia with a particle size of 100nm and put it into 50mL of anhydrous ethanol. Stir at 300r / min for 40min. Then, ultrasonically disperse it at a frequency of 40kHz and a power of 300W for 45min and an ultrasonic temperature of 55℃.

[0059] (3) Preparation of composite energetic nanomaterials: 15g of refined NTO particles were placed in a beaker, 40mL of isopropyl ketone was added, and a suspension was prepared by stirring at 400r / min for 35min. Under stirring, the nano-zirconia dispersion was added dropwise to the suspension at a rate of 15mL / min. Then, ultrasonic mixing was performed at a frequency of 20kHz and a power of 800W for 25min and at a temperature of 45℃. Finally, the mixture was centrifuged at 3000r / min for 20min, washed three times with anhydrous ethanol and ethyl acetate and a mixed solution (volume ratio of 1:1), and dried at 100℃ for 6h to obtain 3-nitro-1,2,4-triazol-5-one / zirconia composite energetic nanomaterials.

[0060] Example 5

[0061] A method for preparing a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial includes the following steps:

[0062] (1) Preparation of the nucleus: At room temperature, 40g of NTO raw material with a particle size of 800μm was dissolved in 500mL of acetone to prepare a precursor solution. In a spray dryer, the nitrogen inlet flow rate was set to 10L / min, the inlet temperature was 90℃, and the feed rate was 9mL / min. After the instrument was filled with nitrogen, the precursor solution was introduced into the instrument by a peristaltic pump. Under the action of hot nitrogen, the solvent evaporated rapidly, and the NTO particles fell into the collection bottle under the action of centrifugal force, finally obtaining refined NTO particles.

[0063] (2) Preparation of shell: Take 0.8g of nano-zirconia with a particle size of 300nm in 100mL of anhydrous ethanol, stir at 500r / min for 60min, and then ultrasonically disperse at a frequency of 40kHz and a power of 300W for 50min and an ultrasonic temperature of 60℃.

[0064] (3) Preparation of composite energetic nanomaterials: 20g of refined NTO particles were placed in a beaker, 50mL of anhydrous ethanol was added, and a suspension was prepared by stirring at 500r / min for 40min. Under stirring, the nano-zirconia dispersion was added dropwise to the suspension at a rate of 20mL / min. Then, ultrasonic mixing was performed at a frequency of 20kHz and a power of 800W for 35min and a temperature of 50℃. Finally, the mixture was centrifuged at 5000r / min for 25min, washed 4 times with anhydrous ethanol, ethyl acetate and a mixed solution (volume ratio 2:1), and dried at 105℃ for 9h to obtain 3-nitro-1,2,4-triazol-5-one / zirconia composite energetic nanomaterials.

[0065] Experimental Example 1

[0066] Effect verification

[0067] according to Figure 1 As can be seen from the refined NTO particles obtained in Example 1, after the spray drying process, the NTO particles are refined to the nanoscale.

[0068] Figure 2 The microstructure of the 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial prepared according to Example 3 of the method provided by the present invention can be seen. It can be seen that the nano-zirconium dioxide is well coated on the surface of NTO particles, forming a relatively uniform core-shell structure.

[0069] The above detailed description further illustrates the purpose, technical solution, and beneficial effects of the invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial, comprising: (1) Preparation of the nucleus: At room temperature, NTO raw material with a particle size of 10-1000 μm and a purity of ≥98% is dissolved in a solvent. The mass-volume ratio of NTO raw material to solvent is (2-50) g: (100-500) mL. A precursor solution is prepared, and the solvent is selected from either deionized water or acetone. Nitrogen gas is introduced into a spray dryer. After the instrument is filled with nitrogen gas, the precursor solution is pumped into the spray dryer to obtain NTO particles with a particle size of 500-5000 nm as the nucleus. (2) Preparation of the shell: Nano-zirconia and non-solvent are mixed and stirred at a mass-volume ratio of (0.1-1) g: (20-100) mL and then ultrasonically dispersed to obtain zirconia particles with a particle size of 5-300 nm as the shell; the non-solvent is selected from any one of anhydrous ethanol, ethyl acetate, diethyl ether, and isopropanol; (3) Preparation of composite energetic nanomaterials: Take a certain mass of the core, add a small amount of non-solvent, stir to prepare a suspension, and add the shell dropwise into the suspension while stirring. Then, perform ultrasonic mixing, and finally centrifuge, wash and vacuum dry to obtain 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterials.

2. The preparation method according to claim 1, wherein: The nitrogen inlet flow rate in step (1) is 2-10 L / min, the inlet temperature is 55-120℃, and the feed rate is 1-10 mL / min.

3. The preparation method according to claim 1, wherein: The stirring speed in step (2) is 150-500 r / min, and the stirring time is 30-60 min; The ultrasonic dispersion frequency is 40kHz, the dispersion power is 300W, the dispersion time is 20-120min, and the ultrasonic temperature is 30-60℃.

4. The preparation method according to claim 1, wherein: The non-solvent mentioned in step (3) is selected from any one of anhydrous ethanol, ethyl acetate, diethyl ether, and isopropanol; The mass-to-volume ratio of the core to the non-solvent is (5-20) g: (10-50) mL; The stirring speed is 200–650 r / min, and the stirring time is 10–50 min; The dropping rate is 5–30 mL / min.

5. The preparation method according to claim 1, wherein: The ultrasonic frequency and ultrasonic power in step (3) are 20kHz and 800W respectively, the ultrasonic time is 3-40min, and the ultrasonic temperature is 25-50℃. The centrifugation speed is 500–5000 r / min, and the centrifugation time is 5–30 min; The washing solution is selected from any one or a mixture of two of anhydrous ethanol and ethyl acetate, and the washing is performed 2 to 4 times. The drying temperature is 55–105℃, and the drying time is 4–12 hours.

6. A 3-nitro-1,2,4-triazol-5-one / zirconium dioxide composite energetic nanomaterial prepared by any of the preparation methods according to claims 1 to 5.

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