Particle size control method of perchlorate-based energetic double salt
By controlling the particle size of perchlorate-based energetic complex salts through inert gas flow disturbance, the problem of crystal morphology and particle size control of DAP-4 was solved, enabling safe, convenient, and environmentally friendly mass production and improving material performance.
Patent Information
- Application Number
- CN202510885972.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-11-07
AI Technical Summary
Existing technologies have difficulty effectively controlling the crystal morphology and particle size of DAP-4, a perchlorate-based energetic complex salt, which leads to adverse effects on subsequent material formulation and loading applications. Furthermore, traditional methods suffer from poor safety, high costs, and environmental risks.
An inert gas flow disturbance method is used to stir, disperse, and crystallize in a perchlorate-based energetic complex salt solution. By controlling the inert gas flow rate and feeding rate, the particle size can be precisely controlled to prepare a perchlorate-based energetic complex salt with uniform particle size.
The method for particle size control of perchloric acid-based energetic complex salts is simple, easy to implement, green and safe, suitable for mass production, improves the mechanical sensitivity and energy consistency of the material, and reduces safety risks and costs.
Smart Images
Figure CN120903998A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of energetic materials, and relates to a perchloric acid-based energetic double salt, in particular to a particle size control method of a perchloric acid-based energetic double salt. BACKGROUND
[0002] Energetic materials are the core energy carriers in the fields of national defense, aerospace and civil blasting, and their performance directly determines the damage effect of weapon systems, the propulsion effect of spacecraft and the precision of engineering blasting. According to different application scenarios, the specifications of the used energetic materials are also different. However, with the expansion of the reaction preparation system, it is difficult to effectively control the crystal morphology, surface defects and particle size distribution of the energetic materials. Research has found that these microstructures can significantly affect the mechanical sensitivity, charge density and energy consistency of the materials, and optimizing the crystal quality of the energetic materials can significantly improve their overall performance.
[0003] DAP-4 energetic material is a perchloric acid-based energetic double salt with perovskite structure formed by alternating organic cation salt of triethylene diamine and energetic oxidizer AP molecules. The material has good detonation performance and excellent heat resistance. In recent years, it has been found that DAP-4-based perforating charges have stronger penetration performance and better heat resistance than the currently used super-high-temperature heat-resistant explosive HNS, and are expected to be a candidate compound for the next generation of super-high-temperature heat-resistant explosives. However, during the synthesis of DAP-4, it is found that the crystallization process is abnormally rapid, and the crystal morphology, particle size and other parameters are difficult to control, often accompanied by problems such as crystal joint growth and a large number of crystal defects, which will adversely affect the subsequent material formulation preparation and charge application. At present, the methods for controlling the crystallization and particle size of energetic materials mainly include solvent-nonsolvent, microfluidic method and mechanical ball milling method. Compared with the mechanical ball milling method, the microfluidic method still has challenges in batch and large-scale preparation, in addition, the solvent-nonsolvent method has many variables and influencing factors, and often requires the use of a large amount of organic solvents, which has the problems of high cost and safety and environmental risk.
[0004] Therefore, it is necessary to further research and develop a particle size control technology that is easy to operate, convenient to control, green and environmentally friendly, and can be prepared in batches for perchloric acid-based energetic double salts, which will facilitate the practical application of DAP-4 energetic materials in formulations. SUMMARY
[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a particle size control method for perchloric acid-based energetic double salts, which solves the technical problem that the accuracy and convenience of the particle size control method in the prior art need to be further improved.
[0006] In order to solve the above technical problems, the technical scheme is adopted as follows:
[0007] A particle size control method of perchloric acid-based energetic double salt, which comprises the following steps: adding the perchloric acid-based energetic double salt solution into a sample collection bottle, and introducing inert gas into the sample collection bottle to disturb the perchloric acid-based energetic double salt solution, so that the perchloric acid-based energetic double salt is dispersed in the solvent in the sample collection bottle, and then crystallization and aging are carried out to obtain the particle size controlled perchloric acid-based energetic double salt.
[0008] Specifically, the method comprises the following steps:
[0009] Step one, solution preparation:
[0010] The perchloric acid-based energetic double salt is added into water, and the perchloric acid-based energetic double salt is completely dissolved under stirring to form a perchloric acid-based energetic double salt solution.
[0011] Step two, particle size control crystallization:
[0012] The perchloric acid-based energetic double salt solution is directly pumped into the sample collection bottle through a feeding pump at a set feeding rate, and inert gas is introduced into the sample collection bottle through a pipeline gas flow regulator at a set gas flow rate to disturb the perchloric acid-based energetic double salt solution, so that the perchloric acid-based energetic double salt is dispersed in the solvent in the sample collection bottle, and then crystallization and aging are carried out, and after the solution is crystallized and aged, filtration, washing and drying are carried out to obtain the particle size controlled perchloric acid-based energetic double salt.
[0013] The present application also has the following technical features:
[0014] In step one, the temperature of the water is 50-90 DEG C, and the concentration of the perchloric acid-based energetic double salt solution is 0.005-0.1 g / mL.
[0015] In step two, the feeding rate of the perchloric acid-based energetic double salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by the pipeline gas flow regulator, and the temperature control and the stirrer of the sample collection bottle are turned on to stabilize the temperature of the solvent in the sample collection bottle.
[0016] In step two, the inert gas is nitrogen or argon.
[0017] In step two, the feeding pump is a plunger pump.
[0018] In step two, the feeding rate of the perchloric acid-based energetic double salt solution is 10-150 mL / min, and the gas flow rate of the inert gas is 20-60 NL / min.
[0019] In step two, the solvent in the sample collection bottle is one or more than one combination of deionized water, ethanol, methanol, acetone and tetrahydrofuran.
[0020] In step two, the temperature of the solvent in the sample collection bottle is controlled in the range of 0-20℃.
[0021] In step two, the time for the crystallization aging is 15-120 min.
[0022] Preferably, in step one, the temperature of the water is 70℃; and the concentration of the perchloric acid-based energetic double salt solution is 0.083 g / mL.
[0023] Preferably, in step two, the inert gas is nitrogen; the feeding pump is a plunger pump; the feeding rate of the perchloric acid-based energetic double salt solution is 120 mL / min; in step two, the flow rate of the inert gas is 60 NL / min; the solvent in the sample collection bottle is tetrahydrofuran; the temperature of the solvent in the sample collection bottle is controlled at 0℃; and in step two, the time for the crystallization aging is 90 min.
[0024] Compared with the prior art, the present application has the following technical effects:
[0025] (I) Compared with the traditional particle size control method, the particle size control method of the present application uses inert gas as the material carrier of the perchloric acid-based energetic double salt DAP-4, controls the flow rate of the inert gas to make the aqueous solution of DAP-4 be disturbed by the gas flow, rapidly cut and dispersed into small droplets of different sizes, and rapidly crystallize and age in a low-temperature solvent, so that the target crystalline energetic material of a certain size can be obtained.
[0026] (II) The reaction parameters and conditions of the particle size control method of the present application are easy to control stably, and the method is especially suitable for the crystallization preparation of superfine DAP-4 energetic material.
[0027] (III) The particle size control method of the present application is simple and easy to operate, green, safe, environmentally friendly, easy to implement, and can be used for batch crystallization preparation. BRIEF DESCRIPTION OF DRAWINGS
[0028] Figure 1 It is a schematic diagram of the preparation principle of the particle size control of the perchloric acid-based energetic double salt.
[0029] Figure 2 It is an XRD pattern of the perchloric acid-based energetic double salt directly synthesized and prepared by the method of the present application.
[0030] Figure 3(a) is an SEM image and particle size distribution graph of DAP-4 perchloric acid-based energetic double salt with a particle size of 15.65 μm prepared by the method of the present application. 50
[0031] Figure 3(b) is an SEM image and particle size distribution graph of DAP-4 perchloric acid-based energetic double salt with a particle size of 15.65 μm prepared by the method of the present application. 50 SEM and particle size distribution of DAP-4 perchlorate based energetic double salt with particle size of 48.67 μm.
[0032] Figure 3(c) is a SEM of DAP-4 perchlorate based energetic double salt prepared using the method of the present application with a particle size of 48.67 μm. 50 SEM and particle size distribution of DAP-4 perchlorate based energetic double salt with particle size of 99.62 μm.
[0033] The specific content of the present application is further explained in detail in the following combined with examples. DETAILED DESCRIPTION
[0034] It should be noted that all materials and equipment in the present application, in the absence of special instructions, are known materials and equipment in the art. For example, DAP-4 is commonly used DAP-4 known in the art. The pipeline gas flow regulator is commonly used pipeline gas flow regulator known in the art.
[0035] In the present application, the DAP-4 is a known compound with a molecular formula of (C6H 14 N2) [NH4(ClO4)3].
[0036] The specific examples of the present application are given below, it should be noted that the present application is not limited to the following specific examples, any equivalent transformation made on the basis of the technical scheme of the present application falls within the protection scope of the present application.
[0037] Example 1:
[0038] The present example gives a particle size control method of DAP-4 perchlorate based energetic double salt, which comprises the following steps: weighing 8g of DAP-4 and adding it into 80mL of deionized water, stirring at 90℃ until completely dissolved to form a DAP-4 perchlorate based energetic double salt solution.
[0039] The feeding rate of the DAP-4 perchlorate based energetic double salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by the pipeline gas flow regulator, and the temperature control and stirrer of the sample collection bottle are turned on to stabilize the solvent temperature in the sample collection bottle.
[0040] Under the conditions of feeding rate of 10mL / min and inert gas nitrogen flow rate of 20NL / min, the DAP-4 perchlorate based energetic double salt solution is directly pumped into the sample collection bottle by the feeding pump at the set feeding rate, at the same time, the inert gas is introduced into the sample collection bottle by the pipeline gas flow regulator at the set gas flow rate to disturb the DAP-4 perchlorate based energetic double salt solution, and then the DAP-4 perchlorate based energetic double salt is dispersed in the 20℃ water in the sample collection bottle, and then crystallized and aged for 15min, filtered, washed and dried to collect the particle size controlled DAP-4 perchlorate based energetic double salt.
[0041] Example 2
[0042] The present embodiment provides a particle size control method for perchloric acid-based energetic double salt, which comprises the following steps: weighing 20 g of DAP-4 and adding it into 4 L of deionized water, stirring at 50°C until complete dissolution to form a perchloric acid-based energetic double salt solution.
[0043] The feeding rate of the perchloric acid-based energetic double salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by the pipeline gas flow regulator, and the temperature control and stirrer of the sample collection bottle are turned on to stabilize the solvent temperature in the sample collection bottle.
[0044] Under the conditions of a feeding rate of 50 mL / min and a nitrogen gas flow rate of 40 NL / min, the perchloric acid-based energetic double salt solution is directly pumped into the sample collection bottle by the feeding pump at the set feeding rate, and the inert gas is introduced into the sample collection bottle at the set gas flow rate by the pipeline gas flow regulator to disturb the perchloric acid-based energetic double salt solution, the perchloric acid-based energetic double salt is dispersed in the 0°C ethanol in the sample collection bottle, then crystallized and aged for 30 min, filtered, washed, and dried to collect the particle size controlled perchloric acid-based energetic double salt.
[0045] Example 3
[0046] The present embodiment provides a particle size control method for perchloric acid-based energetic double salt, which comprises the following steps: weighing 20 g of DAP-4 and adding it into 4 L of deionized water, stirring at 50°C until complete dissolution to form a perchloric acid-based energetic double salt solution.
[0047] The feeding rate of the perchloric acid-based energetic double salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by the pipeline gas flow regulator, and the temperature control and stirrer of the sample collection bottle are turned on to stabilize the solvent temperature in the sample collection bottle.
[0048] Under the conditions of a feeding rate of 50 mL / min and a nitrogen gas flow rate of 40 NL / min, the perchloric acid-based energetic double salt solution is directly pumped into the sample collection bottle by the feeding pump at the set feeding rate, and the inert gas is introduced into the sample collection bottle at the set gas flow rate by the pipeline gas flow regulator to disturb the perchloric acid-based energetic double salt solution, the perchloric acid-based energetic double salt is dispersed in the 0°C ethanol in the sample collection bottle, then crystallized and aged for 30 min, filtered, washed, and dried to collect the particle size controlled perchloric acid-based energetic double salt.
[0049] Example 4
[0050] The embodiment provides a particle size control method of a perchloric acid-based energetic complex salt, and the method comprises the following steps: weighing 300 g of DAP-4 and adding the DAP-4 into 3 L of deionized water, stirring at 80 DEG C until the DAP-4 is completely dissolved, and forming a perchloric acid-based energetic complex salt solution.
[0051] The feeding rate of the perchloric acid-based energetic complex salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by a pipeline gas flow regulator, and the temperature control and the stirrer of the sample collection bottle are turned on, so that the solvent temperature in the sample collection bottle is stabilized.
[0052] The feeding pump is used as the feeding pump, the feeding rate is 150 mL / min, the inert gas nitrogen flow rate is 60 NL / min, the perchloric acid-based energetic complex salt solution is directly pumped into the sample collection bottle at the set feeding rate by the feeding pump, the inert gas is introduced into the sample collection bottle at the set gas flow rate by the pipeline gas flow regulator, the perchloric acid-based energetic complex salt solution is subjected to gas flow disturbance, the perchloric acid-based energetic complex salt is stirred and dispersed in the 0 DEG C acetone in the sample collection bottle, then crystallization aging is performed for 120 min, and filtration, washing and drying are performed, so that the particle size controlled perchloric acid-based energetic complex salt is collected.
[0053] Embodiment 5:
[0054] The embodiment provides a particle size control method of a perchloric acid-based energetic complex salt, and the method comprises the following steps: weighing 300 g of DAP-4 and adding the DAP-4 into 3 L of deionized water, stirring at 80 DEG C until the DAP-4 is completely dissolved, and forming a perchloric acid-based energetic complex salt solution.
[0055] The feeding rate of the perchloric acid-based energetic complex salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by a pipeline gas flow regulator, and the temperature control and the stirrer of the sample collection bottle are turned on, so that the solvent temperature in the sample collection bottle is stabilized.
[0056] The feeding pump is used as the feeding pump, the feeding rate is 150 mL / min, the inert gas nitrogen flow rate is 60 NL / min, the perchloric acid-based energetic complex salt solution is directly pumped into the sample collection bottle at the set feeding rate by the feeding pump, the inert gas is introduced into the sample collection bottle at the set gas flow rate by the pipeline gas flow regulator, the perchloric acid-based energetic complex salt solution is subjected to gas flow disturbance, the perchloric acid-based energetic complex salt is stirred and dispersed in the 0 DEG C acetone in the sample collection bottle, then crystallization aging is performed for 120 min, and filtration, washing and drying are performed, so that the particle size controlled perchloric acid-based energetic complex salt is collected.
[0057] The feeding pump is used as the feeding pump, the feeding rate is 150 mL / min, the inert gas nitrogen flow rate is 60 NL / min, the perchloric acid-based energetic complex salt solution is directly pumped into the sample collection bottle at the set feeding rate by the feeding pump, the inert gas is introduced into the sample collection bottle at the set gas flow rate by the pipeline gas flow regulator, the perchloric acid-based energetic complex salt solution is subjected to gas flow disturbance, the perchloric acid-based energetic complex salt is stirred and dispersed in the 0 DEG C acetone in the sample collection bottle, then crystallization aging is performed for 120 min, and filtration, washing and drying are performed, so that the particle size controlled perchloric acid-based energetic complex salt is collected.
[0058] In the embodiment, Figure 1A schematic diagram of the method for preparing the perchloric acid-based energetic double salt with controllable particle size is shown, Figure 2 By comparing the XRD patterns of the directly synthesized and the perchloric acid-based energetic double salt prepared by the method of the application, it can be found that the crystal form of the DAP-4 prepared by the method of particle size control does not change obviously, the peak type is sharp and the intensity is good, which indicates that the prepared aluminum hydride material has good crystallization quality. Figures 3(a) to 3(c) The SEM images and particle size distribution diagrams of the perchloric acid-based energetic double salt prepared by the method of the application with different particle sizes are shown, and it can be seen that with the increase of the particle size, the morphology of the prepared DAP-4 also gradually changes, and the particle size increases obviously.
Claims
1. A method for controlling the particle size of a perchloric acid-based energetic double salt, characterized in that, The method is characterized in that inert gas is introduced while the perchloric acid-based energetic double salt solution is added, the inert gas is used to disturb the perchloric acid-based energetic double salt solution in the sample collection bottle, the perchloric acid-based energetic double salt is stirred and dispersed in the solvent in the sample collection bottle, and then crystallization and aging are performed to obtain the perchloric acid-based energetic double salt with controlled particle size.
2. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, The method comprises the following steps: Step one, solution preparation: The perchloric acid-based energetic double salt is added into water, and the perchloric acid-based energetic double salt is completely dissolved under stirring to form a perchloric acid-based energetic double salt solution; Step two, particle size control crystallization: The perchloric acid-based energetic double salt solution is directly pumped into the sample collection bottle through a feeding pump at a set feeding rate, and inert gas is introduced into the sample collection bottle through a pipeline gas flow regulator at a set gas flow rate to disturb the perchloric acid-based energetic double salt solution, the perchloric acid-based energetic double salt is stirred and dispersed in the solvent in the sample collection bottle, and then crystallization and aging are performed, and the perchloric acid-based energetic double salt with controlled particle size is collected after filtration, washing and drying.
3. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step one, the temperature of the water is 50-90 DEG C, and the concentration of the perchloric acid-based energetic double salt solution is 0.005-0.1 g / mL.
4. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step two, the feeding rate of the perchloric acid-based energetic double salt solution is controlled by pre-setting the feeding rate of the feeding pump, the gas flow rate of the inert gas is controlled by the pipeline gas flow regulator, and the temperature control and the stirrer of the sample collection bottle are turned on to stabilize the temperature of the solvent in the sample collection bottle.
5. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step two, the inert gas is nitrogen or argon, and the feeding pump is a plunger pump.
6. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step two, the feeding rate of the perchloric acid-based energetic double salt solution is 10-150 mL / min, and the gas flow rate of the inert gas is 20-60 NL / min.
7. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step two, the solvent in the sample collection bottle is one or more than one combination of deionized water, ethanol, methanol, acetone and tetrahydrofuran.
8. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step two, the temperature of the solvent in the sample collection bottle is controlled within the range of 0-20 DEG C.
9. The method of claim 1, wherein the high nitrate-based energetic double salt particle size control method is characterized by, In step two, the crystallization and aging time is 15-120 min.
10. The method of claim 1, wherein the high nitrate-based energetic double salt has a particle size of about 1 to about 100 microns. In step one, the temperature of the water is 70 DEG C, and the concentration of the perchloric acid-based energetic double salt solution is 0.083 g / mL; In step two, the inert gas is nitrogen, the feeding pump is a plunger pump, the feeding rate of the perchloric acid-based energetic double salt solution is 120 mL / min, in step two, the gas flow rate of the inert gas is 60 NL / min, the solvent in the sample collection bottle is tetrahydrofuran, the temperature of the solvent in the sample collection bottle is controlled at 0 DEG C, and the crystallization and aging time in step two is 90 min.