KR20120017328A - High density and high performance plastic bonded explosive and the fabrication method thereof - Google Patents

Abstract

PURPOSE: High density and high performance composite explosive powder using hexanitro hexaaza isowurtzitane(HNIW) and a method for manufacturing the same are provided to improve the performance of the explosive powder and alleviate the sensitivity to external impacts of the explosive powder by using HNIW, acrylate elastomeric copolymer, dioctyl adipate(DOA), and graphite. CONSTITUTION: High density and high performance composite explosive powder includes HNIW as molecular explosive powder, acrylate elastomeric copolymer as a binder, DOA as a plasticizer, and graphite as an additive. The contents of the HNIW, the acrylate elastomeric copolymer, the DOA, and the graphite are in a range between 92.0 and 94.0 weight%, between 1.5 and 2.0 weight%, between 4.5 and 5.5 weight%, and between 0.2 and 0.8 weight%, respectively. The molecular explosive powder includes Cl-1 and Cl-5 at the weight ratio of 2:1 to 4:1. A method for manufacturing the explosive powder includes the following: the acrylate elastomeric copolymer and the DOA are dissolved in a volatile organic solvent to form a polymer solution; the HNIW and the graphite is dispersed in water to form a dispersion solution; the polymer solution is mixed with the dispersion solution to form explosive powder particles; and the explosive powder particles are collected and dried.

Description

High-density, high-performance composite powder using HNIV and its manufacturing method {HIGH DENSITY AND HIGH PERFORMANCE PLASTIC BONDED EXPLOSIVE AND THE FABRICATION METHOD THEREOF}

The present invention relates to a high-density, high-performance composite powder, and more particularly to hexanitrohexaazaisourchitan (H.N.I.doubles, hereinafter HNIW), acrylate elastomer, dioctylphthalic acid (D.O. A, high-density, high-performance compressed composite powder using DOA) and graphite, and a method of manufacturing the same.

Compression type explosives are granulated powder type powders in which a high explosive is added to a powder and agglomerates the high explosive in a powder form. Compression-type gunpowder is generally used as the main charge or booster for highly precise weapon systems.

In the preparation of the compression type composite powder, the selection of the solvent used, the amount of use and the coating method are determined according to the characteristics of the molecular powder and the binder. The binder should be dissolved in a solvent with good solubility to form a liquid polymer solution.When the polymer solution is injected into a slurry solution (dispersion) dispersed in water, the polymer binder may be dissolved due to the difference in solubility of the solvent in water. Uniform coating and coagulation in powdery high explosives is a key principle in the manufacture of compression type explosives. At this time, the larger the difference in solubility between water and solvent, the easier the particle size of the product can be controlled.

According to the surface properties of the molecular powder and the binder, the compression type compound powder is sensitive to external stimuli when the binder is not properly coated on the molecular powder.

In the case of gunpowder, sensitivity means that the gunpowder can ignite and explode under the action of undesired disordered physical phenomena such as external heat or shock.

High precision weapon systems require safe, high explosive properties that are less sensitive. In general, the closer to the theoretical maximum density (TMD) of the charge gunpowder, the less pores or defects in the gunpowder are insensitive to external shocks. This packing density varies considerably depending on which binder is used.

SUMMARY OF THE INVENTION An object of the present invention is to provide a composite powder insensitive to external impact and a method of manufacturing the same while maintaining the characteristics of the high-performance composite powder.

The object of the present invention is a high-density, high-performance composite powder comprising HNIW as a molecular powder, an acrylate elastomer as a binder, a DOA as a plasticizer and graphite as an additive, and (a) an acrylate elastomer and a DOA in a volatile organic solvent. Dissolving a to form a polymer solution, (b) dispersing HNIW and graphite in water to form a dispersion including graphite coated particles on the HNIW surface, and (c) dispersing the dispersion solution and the polymer solution. It can be achieved by a high-density, high-performance composite powder manufacturing method comprising the step of mixing to form the composite powder particles and (d) recovering the composite powder particles by the filtration process and drying.

According to the present invention, it is possible to provide a high-performance, high-density composite powder that is insensitive to external impact and a manufacturing method thereof easily at a speed of 9.0 km / sec, and is highly applicable to a precision weapon system to be developed in the future. do.

1 is a flow chart of a manufacturing process of a high-density high-performance composite powder according to an embodiment of the present invention.

The high-density, high-performance composite powder of the present invention comprises HNIW as a molecular powder, acrylate elastomer (hereinafter as HyTemp) as a binder, DOA as a plasticizer and graphite as an additive. In the high-density, high-performance complex powder, the performance and sensitivity vary greatly depending on the molecular powder and the binder. The present invention uses the molecular weight HNIW and the HyTemp to which chlorine reactive cure site monomer is added. Graphite is used as an additive to reduce the sensitive properties of the gunpowder. HyTemp used as a binder in the present invention has excellent solubility in volatile organic solvents such as ethyl acetate, which facilitates coating coagulation of powdery high explosives, and has compression advantages at room temperature.

The HNIW may be 92.0 to 94.0% by weight, the HyTemp may be 1.5 to 2.0% by weight, the DOA may be 4.5 to 5.5% by weight, and the graphite may be 0.2 to 0.8% by weight. The molecular powder may be a mixture of CL-1 having an average particle diameter of 200 μm and CL-5 having an average particle diameter of 5 μm, and mixing CL-1 and Cl-5 in a weight ratio of 2: 1 to 4: 1. It may be.

Method for producing a high-density high-performance composite powder of the present invention comprises the steps of (a) dissolving HyTemp and dioxylphthalic acid in a volatile organic solvent to form a polymer solution, (b) dispersing HNIW and graphite in water to the graphite on the surface of the HNIW Forming a dispersion comprising the coated particles, (c) mixing the dispersion with the polymer solution to form a composite powder particle; And (d) recovering and drying the composite powder particles by a filtration process. 1 is a flowchart of a manufacturing process of a high-density high-performance composite powder according to an embodiment of the present invention possible.

The volatile organic solvent of step (a) may be at least one selected from the group consisting of ethyl acetate, methyl ethyl ketone and toluene, may be 10 to 25 times the weight of the binder, step (a) is 50 ℃ to 70 ℃ It may be made in. The mixture is sufficiently stirred for about 5 hours to form a liquid polymer solution.

HNIW of step (b) may be a mixture of CL-1 and CL-5 in 2: 1 to 4: 1. By mixing particles of different sizes, the voids between the large particles are made very small, thereby reducing the overall void and providing the insensitive properties insensitive to external impact. In the mixing of particles of different sizes, the size and mixing ratio of the particles are variously applicable. Water may be 10 to 30 times the weight of the HNIW, step (b) may be made at 50 ℃ to 70 ℃, preferably 60 ℃ to 65 ℃. In order to assist the dispersion of HNIW in step (b), gelbatol may be further added in an amount of 0.001 to 0.004% by weight relative to water. Step (b) may be sufficient stirring for at least 30 minutes.

Step (c) is a process of forming the composite powder particles, when the binder is coated on the HNIW may be made to grow larger particles through the aging process for 10 to 20 minutes. As the particles grow to the particle size to the desired particle size, the remaining solvent may be completely removed by additionally injecting the process water so that the ratio of the total amount is 20 to 25 times based on the amount of the solvent. In addition, depending on the properties of the binder may have a somewhat ductile properties, to remove this property is about 10 minutes of hardening (hardening) process.

The method may further include a distillation step of heating to about 100 ° C. after step (c) to recover residual solvent dissolved in water, and then cooling. Care must be taken not to change the size or shape of the particles during this process.

The method may further include washing with water to remove the trace residual solvent, followed by a drying step to remove the water to obtain the composite powder particles, and the drying of the step (d) has a water content of 0.5% by weight of the composite powder particles. Preferably, it may be carried out until it is 0.1% by weight or less.

Example

Hereinafter, the present invention will be described in more detail by way of examples. However, this is only one embodiment of the present invention, the present invention is not limited thereto.

In the following examples, HNIW was used by Dongin Chemical Co., Ltd., binder HyTemp was manufactured by Zeon Chemical, USA, DOA was used by Aekyung Holding Products, and graphite was used by Asbury, USA.

Example 1

A composite powder having the following composition was prepared.

Explosives-HNIW 92.0% by weight (Use the ratio of CL-1 and CL-5 at 3: 1.)

Binder-HyTemp 2.0 wt%

Plasticizer-DOA 5.5 wt%

Additive-Graphite 0.5 wt%

First, HyTemp and DOA were sufficiently dissolved in ethyl acetate at 60 ° C. for 5 hours. At this time, the amount of ethyl acetate was used 20 times the weight of the binder. HNIW and graphite were sufficiently dispersed in water to which dispersant gelbatol was applied and then heated to 60 ° C. At this time, the amount of water was used in 16.0 ~ 18.0 times the amount of solvent used. After injecting the dissolved solution into the dispersion in which the raw powder is dispersed, and after observing the particle size of the particles to reach the appropriate size of particles, the total amount of water is 20 to 25 times based on the amount of solvent. Water was injected to harden the ductile particles. After the curing process the contents were distilled to 100 ° C.

Example 2

The same process as in Example 1, but the composition was prepared by varying the composition of each component.

Explosives-HNIW 94.0 wt%

Binder-HyTemp 1.5 wt%

Plasticizer-DOA 4.0 wt%

Additive-Graphite 0.5 wt%

Comparative Example 1

Unlike Example 1, a composite powder was prepared without adding graphite. A composite powder was prepared in the same manner except for the addition of the additive graphite.

Explosives-HNIW 92.0 wt%

Binder-HyTemp 2.0 wt%

Plasticizer-DOA 6.0 wt%

Hereinafter, various experimental results performed on the composite powder prepared through the Examples and Comparative Examples are shown. A uses DOS as a plasticizer and B uses H. M. X (cyclotetramethylene- tetranitramine, hereinafter HMX) as an explosive material. Composition A is from US PBXW-16 presentation (NDIA IM & EMTS 2001).

Table 1 shows the density measurement results of the gunpowder.

Furtherance Theoretical density
(TMD, g / cm ³ ) Compression Density (g / cm ³ ) Example 1 HNIW: HyTemp: DOA: Graphite
= 92: 2: 5.5: 0.5 1.884 1.881 (99.84% TMD) Comparative Example 1 HNIW: HyTemp: DOA
= 92: 2: 6 1.873 1.873 (100.0% TMD) A HNIW: HyTemp: DOS
= 92: 2: 6 1.883 1.859 (98.73% TMD) B HMX: HyTemp: DOA
= 96: 1: 3 1.829 1.794 (98.09% TMD)

As shown in Table 1, the compression density of the composition used in this example is higher than the composition B using the maximum HMX. In Example 1 and Comparative Example 1 of the present invention, the theoretical density (TMD) is similar to A, but the compression density is improved to confirm that the 99.5% or more of the theoretical density.

The Large Scale Gap Test was conducted on the composite powder prepared in Example 1. The L.S.G.T test is a comparative test performed to measure the sensitivity to the external impact of a solid gunpowder. When a gun of a certain thickness is inserted between the gunpowder and the auxiliary gun and the auxiliary gun is blown, the auxiliary gun To determine the 50% response of the gunpowder in response to the explosion impact, the sensitivity of the gunpowder to the external impact depending on the number of cards between the gunpowder and the auxiliary charge. In other words, the smaller the number of cards, the safer gunpowder is insensitive to external impact.

Table 2 shows the results of sensitivity measurement against external impact.

Furtherance Number of cards Pressure (kbar) Compression Density (g / cm ³ ) Example 1 HNIW: HyTemp: DOA: Graphite
= 92: 2: 5.5: 0.5 169 29.85 1.868 Comparative Example 1 HNIW: HyTemp: DOA
= 92: 2: 6 183 24.82 1.873 A HNIW: HyTemp: DOS
= 92: 2: 6 185 24.50 1.883 B HMX: HyTemp: DOA
= 96: 1: 3 177 26.82 1.796 C HNIW: HyTemp: BDNPFF
= 92: 2: 6 217 17.05 1.921

Table 2 shows the results of L.S.G.T of gunpowder using HyTemp as a binder, and compared the results of similar compositions. C replaces the plasticizer DOA with BDNPFF [bis (2,2-dinitropropyl) -formal / formal], an energy-containing plasticizer, and the thickness of one card was 0.25 mm. It was confirmed that the composite powder according to the present invention using graphite as an additive is much insensitive to external impact and is a safe powder.

The speed of explosion of the composite powder of Example etc. was measured.

Compression condition Speed (km / sec) Density (g / cm 3) Example 1 Pressure: 25,000 psi
Temperature: 50 ℃
Diameter: 36 mm 9.036 1.881 Comparative Example 1 Pressure: 25,000 psi
Temperature: 50 ℃
Diameter: 36 mm 9.054 1.873 B Pressure: 25,000 psi
Temperature: 50 ℃
Diameter: 36 mm 8.720 1.794

As shown in Table 3, the composition B using the maximum HMX showed a speed reduction of about 8.72 km / sec, whereas the speed reduction of Example 1 and Comparative Example 1 of the present invention using only 92% of the HNIW was 9.0 km / sec or more. It can be seen that the characteristics of the gunpowder.

Rapid and slow heating tests were performed on the composite powder prepared in Example 1, and the results are shown in Table 4. The rapid heating test is to rapidly heat a carcass filled with explosives using gasoline to measure the temperature change and cook-off temperature in the carcass in an environment similar to the fire test, and to collect the test carcass collected after the cook-off. The response of gunpowder to the debris is determined by UN Test Series-7 (see Table 5). The slow heating test is to put the explosive-filled carcass into a thermally insulated wooden oven, and then heat the surface temperature of the carcass to 107 ° C for the first 1 hour using an electric heater, and then heat the temperature inside the oven for 7 hours. The temperature is maintained so that the body is thermally equilibrated and then heated until the body reacts at a heating rate of 3.3 ° C. per hour. After the reaction, the time taken for the reaction, the reaction temperature and the reaction phenomenon are measured to evaluate the properties.

Fast cook-off Slow cook-off Example 1 Burning (2 tests) Burning (2 tests) A Explosion (2 tests) Detonation (2 tests)

Reaction Type EM Behavior Criteria  I Detonation
(Detonation) -Strong shock waves that damage adjacent structures
-Formation of large pits Ⅱ Partial explosion
(Partial Detonation) Pit size is proportional to the amount of detonated energy substance
-Large fragments occur Ⅲ explosion
(Explosion) -Large fragmentation in the form of violent destruction
-Combustion material is scattered around Ⅳ deflagration
(Deflagration) -If the test body exceeds 3 pieces
-Combustion material is scattered around Ⅴ Combustion
(Burning) -The test bodies are scattered not violently
-No fragments exceeding 15m

According to Table 4 it can be seen that the composite powder according to the present invention is a powder that is much safer in thermal properties than the US composition PBXW-16 composition (A).

Claims (10)

A high density high performance composite powder comprising HNIW as a molecular powder, an acrylate elastomer as a binder, DOA as a plasticizer and graphite as an additive. According to claim 1, wherein the HNIW 92.0 to 94.0% by weight, the acrylate elastomer 1.5 to 2.0% by weight, the DOA 4.5 to 5.5% by weight and graphite 0.2 to 0.8% by weight of a high density high performance composite. The high-density, high-performance composite powder of claim 1, wherein the molecular powder is a mixture of CL-1 and Cl-5 in a weight ratio of 2: 1 to 4: 1. (a) dissolving an acrylate elastomer and DOA in a volatile organic solvent to form a polymer solution;
(b) dispersing HNIW and graphite in water to form a dispersion comprising the graphite coated particles on the HNIW surface;
(c) mixing the dispersion solution with the polymer solution to form composite powder particles; And
(d) recovering and drying the composite powder particles by a filtration process
High density high performance composite powder manufacturing method comprising a. The method of claim 4, wherein the volatile organic solvent of step (a) is at least one selected from the group consisting of ethyl acetate, methyl ethyl ketone and toluene, and is 10 to 25 times the weight of the binder, step (a) is 50 to Method of producing a high-density high-performance composite powder that is made at 70 ℃. The method of claim 4, wherein the HNIW of step (b) is a mixture of CL-1 and CL-5 in a 2: 1 to 4: 1, the water is 10 to 30 times the weight of the HNIW, step (b) High density high performance composite powder production method that is made at 50 to 70 ℃. The method of claim 4, wherein step (b) further comprises adding gelbatol to the dispersant at 0.001 to 0.004% by weight relative to water. The process of claim 4, wherein after step (c):
(c ') adding water to remove residual solvent and curing the composite powder particles; The process of claim 4, wherein after step (c):
(C '') further comprising the step of recovering the residual solvent and then cooling. The method of claim 4, wherein the drying of step (d) is such that the water content of the composite powder is 0.5% or less.