阅读说明：本技术 一种空间网络结构复合含能材料及其制备方法 (Composite energetic material with space network structure and preparation method thereof ) 是由 陶俊 王晓峰 王浩 封雪松 薛乐星 于 2021-09-26 设计创作，主要内容包括：本发明公开了一种空间网络结构复合含能材料及其制备方法。所公开的材料制备原料包括六硝基六氮杂异戊兹烷、硝化细菌纤维素和铝粉,选用具有三维纳米网状结构的硝化细菌纤维素作为模板,来构筑三维网络结构六硝基六氮杂异戊兹烷/铝粉复合颗粒。制备方法包括中,硝化细菌纤维素溶于乙酸乙酯溶液中加入六硝基六氮杂异戊兹烷、铝粉,搅拌形成悬浊液；搅拌条件下滴入蒸馏水,滴加完之后超声震荡形成稳定均匀的乳液；将乳液缓慢滴加到常温蒸馏水中,过滤、用蒸馏水洗涤,得到所要制备的空间网络结构复合含能材料。本发明能有效提升六硝基六氮杂异戊兹烷/铝粉复合物的能量,降低复合物感度。(The invention discloses a composite energetic material with a space network structure and a preparation method thereof. The disclosed material preparation raw materials comprise hexanitrohexaazaisowurtzitane, nitrobacteria cellulose and aluminum powder, and nitrobacteria cellulose with a three-dimensional nano-net structure is selected as a template to construct hexanitrohexaazaisowurtzitane/aluminum powder composite particles with a three-dimensional network structure. The preparation method comprises the steps of dissolving nitrobacteria cellulose in ethyl acetate solution, adding hexanitrohexaazaisowurtzitane and aluminum powder, and stirring to form suspension; dripping distilled water under the stirring condition, and then ultrasonically oscillating to form stable and uniform emulsion; slowly dripping the emulsion into distilled water at normal temperature, filtering, and washing with distilled water to obtain the composite energetic material with the space network structure to be prepared. The method can effectively improve the energy of the hexanitrohexaazaisowurtzitane/aluminum powder compound and reduce the sensitivity of the compound.)

1. The composite energetic material with the space network structure is characterized in that the composite energetic material with the space network structure is prepared from the following raw materials in percentage by mass: 70-83% hexanitrohexaazaisowurtzitane; 3.2 to 6 percent of nitrobacteria cellulose; 11-24% of aluminum powder; and the sum of the mass percentages of the components is 100 percent.

2. The spatial network structure composite energetic material of claim 1, wherein the particle size of the hexanitrohexaazaisopentane is 80-120 μm.

3. The spatial network structure composite energetic material of claim 1, wherein the average molecular weight of the nitrobacterial cellulose is 2 ten thousand.

4. The spatial network structure composite energetic material as set forth in claim 1, wherein the spatial network structure composite energetic material is prepared from the following raw materials in percentage by mass: 79% of hexanitrohexaazaisowurtzitane, 6% of nitrobacterial cellulose and 15% of aluminum powder.

5. The method for preparing the composite energetic material with the space network structure as described in any one of claims 1 to 4, wherein the method comprises the following steps:

(1) preparing ethyl acetate solution of hexanitrohexaazaisowurtzitane and nitrobacterial cellulose at the temperature of 60-65 ℃;

(2) mixing aluminum powder with the solution prepared in the step (1) at the temperature of 60-65 ℃ to form suspension containing the aluminum powder;

(3) dripping distilled water with the temperature of 60-65 ℃ into the suspension with the temperature of 60-65 ℃, and uniformly mixing to prepare emulsion;

(4) and dropwise adding the emulsion into normal-temperature distilled water to prepare the composite energetic material with the space network structure.

6. The method for preparing the composite energetic material with the space network structure as claimed in claim 5 is characterized by further comprising the following steps:

(5) filtering, washing with distilled water, and drying to obtain the composite energetic material with the space network structure.

7. A mixed explosive is prepared from the spatial network structure composite energetic material and a desensitizer according to any one of claims 1 to 4, wherein the spatial network structure composite energetic material comprises the following components in percentage by mass: 98.6 percent; the desensitizer comprises the following components in percentage by mass: 1.4 percent.

8. The blended explosive of claim 7, wherein the desensitizer is made from paraffin and graphite, and the paraffin comprises, by weight: 1.2 percent, and the graphite comprises the following components in percentage by mass: 0.2 percent.

Technical Field

The invention relates to a composite energetic material with a space network structure and a preparation method thereof, belonging to the field of explosive synthesis.

Technical Field

The requirement of local war for army to have very high maneuverability and the ability of destroying diversified targets in different environments puts forward very strict requirements on the carrying capacity of army and the destruction function of ammunition, the requirement that weapon ammunition has a multi-purpose function of one ammunition can realize the high-efficiency destruction of hard targets such as armored tanks, protection workers and the like and the soft destruction of surface targets such as fragment destruction and shock wave destruction and the like, and the multifunctional ammunition is very suitable for the charging of multifunctional ammunition, rocket ammunition, smart ammunition, individual weapon and special combat troops, can expand the variety of ammunition destruction targets and can improve the destruction efficiency of ammunition. This is also one of the important directions for the development of new high explosive technology and equipment applications to meet the demands of local warfare in foreign countries, especially in the united states. Therefore, there is an urgent need to develop an explosive formulation containing a small amount of aluminum powder that has both metal acceleration capability and shock wave damage.

Disclosure of Invention

In order to overcome the defects of the background art, the invention provides a preparation method of a composite energetic material with a space network structure.

Therefore, the composite energetic material with the space network structure provided by the invention comprises the following preparation raw materials in percentage by mass: 70-83% hexanitrohexaazaisowurtzitane; 4 to 6 percent of nitrobacteria cellulose; 11-24% of aluminum powder; and the sum of the mass percentages of the components is 100 percent.

Optionally, the particle size of the hexanitrohexaazaisowurtzitane is 80-120 μm.

Alternatively, the average molecular weight of the nitrocellulose is 2 ten thousand.

Optionally, the raw materials for preparing the spatial network structure composite energetic material comprise, by mass: 79% of hexanitrohexaazaisowurtzitane, 6% of nitrobacterial cellulose and 15% of aluminum powder.

Meanwhile, the invention also provides a preparation method of the composite energetic material with the space network structure. Therefore, the preparation method provided by the invention comprises the following steps:

(1) preparing ethyl acetate solution of hexanitrohexaazaisowurtzitane and nitrobacterial cellulose at the temperature of 60-65 ℃;

(2) mixing aluminum powder with the solution prepared in the step (1) at the temperature of 60-65 ℃ to form suspension containing the aluminum powder;

(3) dripping distilled water with the temperature of 60-65 ℃ into the suspension with the temperature of 60-65 ℃, and uniformly mixing to prepare emulsion;

(4) and dropwise adding the emulsion into normal-temperature distilled water to prepare the composite energetic material with the space network structure.

Further, the preparation method of the invention also comprises the following steps: (5) filtering, washing with distilled water, and drying to obtain the composite energetic material with the space network structure.

The invention also relates to a mixed explosive. The mixed explosive is prepared from the space network structure composite energetic material and a insensitive agent, wherein the weight percentage of the space network structure composite energetic material is as follows: 98.6 percent; the desensitizer comprises the following components in percentage by mass: 1.4 percent.

Optionally, the desensitizer is prepared from paraffin and graphite, and the mass percentage of the paraffin is as follows: 1.2 percent, and the graphite comprises the following components in percentage by mass: 0.2 percent.

The invention controls the process conditions to ensure that the periphery of the aluminum powder is surrounded by the nitrobacteria-containing cellulose rich in nitro groups, and the nitrobacteria cellulose can provide a good oxygen environment for the reaction of the aluminum powder in the composite energetic material, thereby ensuring the reaction completeness of the aluminum powder and improving the energy level of the composite energetic material.

According to the invention, nitrobacteria cellulose is used as a matrix, a nitrobacteria cellulose network structure is formed by preparation, and the CL-20 crystal and the aluminum powder crystal are embedded into the space network, so that nitrobacteria cellulose network intervals are arranged between the CL-20 crystal and between the CL-20 crystal and the aluminum powder crystal, the nitrobacteria cellulose with low sensitivity is firstly stimulated by external energy stimulation, and under the external stimulation, impact and friction between crystals are avoided, and the ignition probability is greatly reduced.

Compared with a physically mixed CL-20/AL composite material, the space network structure composite energetic material has the advantages that the explosion heat is improved by 8.37 percent, and the sensitivity is obviously reduced; compared with PAX-29 explosive, the explosive prepared by adding a small amount of insensitive agent has 4.11% higher explosion heat and obviously lower sensitivity.

Drawings

FIG. 1 is a composite energetic material with a space network structure and 4% of nitrobacteria cellulose as a matrix (example 5);

FIG. 2 is a composite energetic material with a space network structure and 6% of nitrobacteria cellulose as a matrix (example 1);

FIG. 3 is a physical mixed CL-20/Al composite energetic material.

Detailed Description

Unless otherwise indicated, the terms and methods herein are understood or implemented using conventional practices of ordinary skill.

The preparation raw materials of the composite energetic material with the space network structure comprise (by mass percent): 70 to 75 percent of hexanitrohexaazaisowurtzitane, 3.2 to 4 percent of nitrobacteria cellulose and 11 to 12 percent of aluminum powder; 76 to 77 percent of hexanitrohexaazaisowurtzitane, 4 to 5 percent of nitrobacteria cellulose and 12 to 13 percent of aluminum powder; 77-80% of hexanitrohexaazaisowurtzitane, 5-6% of nitrobacteria cellulose and 13-18% of aluminum powder; or 80 to 83 percent of hexanitrohexaazaisowurtzitane, 5.5 to 6 percent of nitrobacteria cellulose and 18 to 24 percent of aluminum powder; and the sum of the mass percentages of the components is 100 percent.

The granularity of the hexanitrohexaazaisowurtzitane in the scheme of the invention is selected to be 80-120 mu m, and the granularity range is at least favorable for the free-flowing property and the compressibility of the mixed explosive and the molding of the pressed explosive molding powder. In the scheme of the invention, the average molecular weight of the nitrobacteria cellulose is selected to be 2 ten thousand, and the molecular weight is at least selected to be favorable for the balance between bonding and dissolution. Commercially available nitrocellulose is suitable for use in the present invention.

The scheme of the invention is further illustrated below with reference to examples.

The nitrocellulose used in the following examples was purchased from the university of southwest science and technology; the aluminum powder used in the following examples is available under the trade designation FLQT 4.

The proportion of CL-20 and Al powder in the formula of the physically mixed CL-20/Al composite energetic material used in the following examples is consistent with that of the composite energetic material with a space network structure in the corresponding examples, and the specific preparation method is that 100g of CL-20 and Al powder are weighed and added into a three-neck flask, 100mL of n-hexane is added to wet the CL-20 and Al powder, the stirring speed is controlled to be 100rpm, the stirring is carried out for 10min, and the filtering and drying are carried out to obtain the physically mixed CL-20/Al composite energetic material.

The following examples were also compared to a PAX-29 explosive studied in the United states, which consisted of 77% hexanitrohexaazaisowurtzitane, 15% aluminum powder, 4.8% bis (2, 2' -dinitropropyl) acetal/formal, and 3.2% cellulose acetate butyrate. The prior data report that the explosive heat of PAX-29 explosive is 7050J/g, the explosion velocity is 7800m/s, and the gurney coefficient is 3.0.

The explosion heat test experiment of the space network structure composite energetic material in the following embodiment is carried out according to the explosion heat measurement-adiabatic method of the small-dosage energetic compound of the enterprise standard Q/AY 734-2016, and the test method is as follows:

sieving a sample of the tested energetic compound, selecting a sample with the particle size of less than 60 mu m, weighing 3-5 g of the sample of the tested energetic compound, accurately weighing the sample to 0.0001g, and filling the accurately weighed sample particles into a ceramic tube, wherein the filling density reaches (40-50)% of the theoretical density;

taking a detonating fuse with the length of (100 +/-2) mm, accurately measuring the length of the detonating fuse to 1mm, enabling the detonating fuse to penetrate through the center of a ceramic tube filled with a sample, reserving detonating fuses with basically the same length at two ends of the ceramic tube, sealing two ports of the ceramic tube by using a copper foil adhesive tape, hanging the ceramic tube filled with the sample below a detonation heat bullet cover by using a suspension wire, keeping the distance between the detonating fuses and the bullet cover (6-8) cm, and respectively connecting two ends of the detonating fuse with two electrodes below the detonation heat bullet cover;

fastening the explosion-heating bomb cover and the bomb body by using bolts, connecting a vacuum pump with a vent valve on the bomb cover, vacuumizing the explosion-heating bomb until the pressure reaches more than-0.095 MPa, closing the vent valve, connecting nitrogen with the vent valve on the bomb cover, opening the vent valve, slowly filling the nitrogen into the explosion-heating bomb until the pressure reaches 1.2-1.4 MPa, and closing the vent valve.

Checking the tightness of the explosive bomb, discharging nitrogen, vacuumizing the explosive bomb again until the pressure reaches more than-0.095 MPa, and closing a vent valve; putting the detonation bomb into an inner barrel of a calorimeter, connecting an ignition lead, adding distilled water with the mass of 24 +/-1 ℃ into the inner barrel, and accurately weighing 50mg, wherein the mass of the distilled water is 8.98 kg;

covering the upper cover of the calorimeter, and respectively inserting an inner barrel thermometer and an outer barrel thermometer into an inner barrel and an outer barrel of the calorimeter;

switching on a calorimeter power supply, starting an inner barrel stirring and outer barrel circulating pump, opening a cooling water valve, starting an automatic tracking temperature controller after about 1h, controlling the difference between the water temperature of the inner barrel and the water temperature of the outer barrel, enabling the water temperature of the inner barrel of the calorimeter to change within 15min to be not more than 0.003 ℃, the water temperature of the outer barrel to change not more than 0.02 ℃, and recording the water temperature t of the inner barrel₀Then igniting;

after ignition, the automatic tracking temperature controller controls the temperature of the outer barrel water to track the change of the inner barrel water temperature, when the change of the inner barrel water temperature is not more than 0.003 ℃ within 15min again, the water temperature t of the inner barrel of the calorimeter is recorded₁；

And (3) closing the calorimeter and the automatic tracking temperature controller, taking out the inner barrel thermometer and the outer barrel thermometer, opening an upper cover of the calorimeter, and detecting whether the bomb leaks air, wherein if so, the test is invalid.

And processing the test result according to a formula, testing the two times of explosion heat values of each sample in parallel, wherein the allowable error is less than 3%, and taking the average value of the two times of explosion heat values as the explosion heat value of the tested sample. Reference is made to the test method mentioned in the article "energy output characteristics of explosives on plasma initiation" (proceedings on explosives and powders, volume 40, No. 6, 2017).

Example 1:

the embodiment is implemented according to the following components in percentage by mass: 79% of hexanitrohexaazaisowurtzitane, 6% of nitrobacteria cellulose and 15% of aluminum powder.

The preparation method of this example is as follows:

(1) dissolution

Adding 200mL of ethyl acetate into 10g of hexanitrohexaazaisowurtzitane and 0.76g of nitrobacteria cellulose, and then placing the mixture in a water bath at the temperature of 60-65 ℃ for heating and stirring (400rpm) until all the solid is dissolved;

(2) preparation of turbid liquid

Adding 1.764g of aluminum powder into the mixed solution obtained in the step (1), keeping the temperature at 60-65 ℃, and uniformly mixing to form a suspension containing the aluminum powder;

(3) preparation of emulsions

Slowly dripping 50ml of distilled water which is heated to 60-65 ℃ in a water bath in advance into the suspension obtained in the step (2), keeping stirring and controlling the temperature to be 60-65 ℃ in the dripping process, and then carrying out ultrasonic oscillation for 5min after dripping is finished until stable and uniform emulsion is formed;

(4) preparation of composite energetic material with space network structure

Slowly dripping the emulsion into 4000ml of normal-temperature distilled water, and stirring in the dripping process; after the dropwise addition is finished, stirring is continued;

(5) filtering, washing with distilled water to obtain a compound sample to be prepared, and drying the compound sample in a constant-temperature water bath oven at 30 ℃ to obtain the composite energetic material with the space network structure.

Further, the compound energetic material with the space network structure prepared by the embodiment is used for preparing corresponding explosives: specifically, 493g of the spatial network structure composite energetic material is added into a water chestnut type coating machine, the temperature of the coating machine is controlled to be 75 ℃, 6g of 68# paraffin and 1g of graphite are added, the sense of the spatial network structure composite energetic material is reduced, the spatial network structure composite energetic material is endowed with a compression molding function, the stirring speed is controlled to be 40 revolutions per minute, and the stirring is carried out for 20 minutes; and (5) reducing the temperature to normal temperature, and continuing mechanically stirring for 10min to obtain the explosive based on the space network structure composite energetic material.

Performance test data show that: compared with a physically mixed CL-20/Al composite material, the composite energetic material with the hollow network structure prepared by the embodiment has the advantages that the explosion heat is improved by 8.37 percent, and the sensitivity is obviously reduced; compared with PAX-29 explosive, the mixed explosive prepared by adding a small amount of insensitive agent has the advantages of 4.11% improvement of explosion heat, equivalent explosion speed and obviously reduced sensitivity.

Example 2:

the present example was carried out with reference to the following mass percentages: 70% of hexanitrohexaazaisowurtzitane, 6% of nitrobacteria cellulose and 24% of aluminum powder. The preparation procedure is as in example 1.

Performance test data show that: in the embodiment, the explosion heat of the space network structure composite energetic material is improved by 8.02 percent compared with that of a physically mixed CL-20/Al composite material, and the sensitivity is obviously reduced; compared with PAX-29 explosive, the explosive prepared by adding a small amount of insensitive agent has 8.51% higher explosion heat and obviously lower sensitivity.

Example 3:

the present example was carried out with reference to the following mass percentages: 83% of hexanitrohexaazaisowurtzitane, 6% of nitrobacteria cellulose and 11% of aluminum powder. The preparation procedure is as in example 1.

Performance test data show that: in the embodiment, the explosion heat of the space network structure composite energetic material is improved by 7.73 percent compared with that of a physically mixed CL-20/Al composite material, and the sensitivity is obviously reduced; the mixed explosive prepared by adding a small amount of insensitive agent has the same explosion heat as the PAX-29 explosive, the explosion speed is improved to a certain extent, and the sensitivity is slightly reduced.

Example 4:

the present example was carried out with reference to the following mass percentages: 77% of hexanitrohexaazaisowurtzitane, 3.2% of nitrobacteria cellulose and 15% of aluminum powder. The preparation procedure is as in example 1.

Performance test data show that: in the embodiment, the explosion heat of the space network structure composite energetic material is improved by 4.83 percent compared with that of a physically mixed CL-20/Al composite material, and the sensitivity is obviously reduced; compared with PAX-29 explosive, the mixed explosive prepared by adding a small amount of insensitive agent has the advantages that the detonation heat is improved by 3.78 percent, the detonation velocity is equivalent, and the sensitivity is obviously reduced.

Example 5:

the present example was carried out with reference to the following mass percentages: 83% of hexanitrohexaazaisowurtzitane, 4% of nitrobacteria cellulose and 13% of aluminum powder. The preparation procedure is as in example 1.

Performance test data show that: in the embodiment, the explosion heat of the space network structure composite energetic material is improved by 5.04 percent compared with that of a physically mixed CL-20/Al composite material, and the sensitivity is obviously reduced; compared with PAX-29 explosive, the mixed explosive prepared by adding a small amount of insensitive agent has the advantages that the explosion heat is improved by 3.25%, the explosion speed is improved to a certain extent, and the sensitivity is slightly reduced.

The performance of the above examples and the related comparative products were tested, wherein the explosion heat of the mixed explosive based on the spatial network structure composite energetic material was tested according to the GJB772A 701.1.1 constant temperature method and the adiabatic method, the friction sensitivity was tested according to the GJB772A-97 method 602.1 explosion probability method, and the impact sensitivity was tested according to the GJB772A-97 method 601.1 explosion probability method. The test results are given in table 1 below:

TABLE 1 physical Properties, detonation Properties and sensitivity of spatial network structured composite energetic materials

It should be noted that the above-mentioned embodiments are only preferred examples of the present invention, and do not limit the present invention, and those skilled in the art should make equivalents based on the spirit and principle of the present invention within the protection scope of the present invention.