CN106854718A - Structural material containing energy and its preparation method and application - Google Patents

Abstract

The invention discloses one kind containing can structural material, including following mass fraction component：10%~60% aluminum or aluminum alloy, 35% ~ 89.5% high desnity metal and 0.5%~5.0% metal oxide；Wherein, aluminum or aluminum alloy is successive substrates phase, and high desnity metal particle and metal oxide particle are evenly distributed in the successive substrates phase.The structural material containing energy has the advantages that high intensity, reaction latent heat and good impact-response characteristic high.

Description

Energetic structural materials and their preparation methods and applications

technical field

The invention belongs to the technical field of new materials, and in particular relates to an energetic structural material and its preparation method and application.

Background technique

High-efficiency damage is the fundamental purpose of long-range precision strikes. At present, the damage of weapons mainly depends on the warhead with traditional ammunition as the core. Therefore, the development of high-damage ammunition is one of the core tasks for upgrading long-range precision strike weapons. Traditional warheads are mainly composed of metal shells, explosives, and corresponding structural components. Explosives are the energy for warheads to damage targets. In order to improve the damage power of warheads, it is generally achieved by increasing the explosive loading and the explosive energy per unit mass. , due to the limitations of the conditions of use and the level of materials, there is a limit to the amount of explosives loaded, and it is very difficult to increase the energy density of explosives. In addition, the energy obtained by the damage element during the energy release and conversion process of the explosive is a small part of the total energy of the explosive, and a slight increase in the charge or energy density of the explosive does not necessarily bring about a large increase in the damage effect on the target. Therefore, the improvement of warhead damage efficiency needs to expand new technical approaches.

Energetic materials with high stability under common conditions, but high-speed impacts can trigger exothermic reactions between components are often called reactive materials (Reactive Materials, RMs), and reactive materials with high mechanical properties are called reactive structural materials or energetic structures. Material. The warhead fragments, drug-type cover, shell structure and other components are made of energetic structural materials, and the damage element is formed under the driving of the explosive explosion, and the critical energy required for the reaction is applied to the damage element through explosive loading, high-speed impact, etc. Prompting the reaction between its own components or between the components and the environment to release energy twice, can achieve ignition and detonation damage to the target. The application of energetic structural materials in ammunition is a new way to improve the performance of existing ammunition (Xu Songlin, Yang Shiqing, Zhang Wei, etc., Research on the mechanical properties of PTFE/Al reactive materials. Journal of High Pressure Physics, 2009, 23(5 ): 384~388. Yang Yi, Zheng Ying, Wang Kun, Research progress on high-density active materials and their damage effects, Weapon Materials Science and Engineering. 2013, 36(4): 81-85. Song Lei, Li Baofeng, Chen Hao , The U.S. Navy demonstrated the use of "high-density active materials" to increase the explosive power of warheads, Equipment Reference. 2011, 49: 32-33.).

The external forces that energetic structural materials bear during use mainly include compressive stress when explosives are driven, tensile stress when unloading in flight, compressive stress when impact decelerates, and tensile stress when penetrating the target and unloading. Therefore, energetic structural materials generally need to have The following characteristics: (1) have high enough strength, on the one hand, to ensure that the material can be used as a structural part such as a warhead shell, and on the other hand, ensure the integrity during the explosive drive and penetration of the target; (2) have a suitable Reaction latent heat and latent heat release ability ensure the energy release characteristics during high-speed impact; (3) Moderate density ensures the necessary penetration performance of the material.

In order to obtain energetic structural materials that meet the above requirements, the Chinese patent application number 201510733993.8 proposes a method for preparing energetic materials. This method uses molding and sintering methods to prepare energetic structural materials. The Al obtained by this method Compared with traditional Al/PTFE (Al: 26.4wt%; PTFE: 73.6wt%) energetic materials, /W/PTFE energetic materials have greatly improved compressive strength and density, and the reaction threshold of energetic materials also improved. However, the tensile strength of this type of material is low, generally not exceeding 30MPa.

The Chinese patent No. 201410176443.6 proposes an energetic structural material, which is made by mixing and pressing Al powder, KClO ₃ powder and W powder. The material is sufficiently insensitive and does not react during the acceleration of the explosion, and has Greater penetrating power, and can produce chemical reactions to release energy, increasing the ability to damage targets. However, the material is formed by cold pressing after powder mixing, and the strength of the material mainly depends on the mechanical meshing force between the powders, and the strength is relatively low.

The Chinese patent application number 201610044485.3 proposes a fragment of energetic structural material, which is obtained by cold pressing after mixing nano-aluminum powder, transition metal oxide, oxidizer, ferrocene, high explosive and mixed binder. The energetic fragments prepared by this material have high energy density, good safety performance, easy initiation and strong arson ability, and will not react immediately when the explosive is driven, but a strong chemical reaction can occur during the penetration process and release extremely high heat, and It can generate hot, fluid reaction products at high temperature. The strength of the material is mainly determined by the binder, and the strength is still low.

The Chinese patent with the patent number 201110440556.9 and the Chinese patent with the application number 201510606975.3 proposed two methods for preparing tungsten-zirconium alloy energetic structural materials. The materials prepared by this method have relatively good mechanical properties, but the materials mainly rely on Zirconium reacts with oxygen in the environment to release energy, and its ability to release latent heat is poor. Therefore, the ignition of fuel oil and the detonation of explosives are generally effective, and it is possible only under specific conditions.

It can be seen that the current public reports on the comprehensive performance of energetic structural materials still have a certain distance from the actual demand.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, to provide an energetic structural material with high strength, high latent heat of reaction and good impact response characteristics, and to provide a material without adverse chemical reactions between components. The preparation method of the above-mentioned energetic structural material also provides the application of the energetic structural material in warheads.

In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:

An energetic structural material, comprising the following components in mass fraction:

Aluminum or aluminum alloy 10%～60%

High Density Metal 35%~89.5%, and

Metal oxide 0.5%～5.0%;

Wherein, aluminum or aluminum alloy is a continuous matrix phase, and high-density metals and metal oxides are evenly distributed in the continuous matrix phase.

In the aforementioned energetic structural material, preferably, the high-density metal is one or more of Ni, W, Ta, Hf, Ti and Zr.

For the aforementioned energetic structural material, preferably, the metal oxide is one or more of Fe ₂ O ₃ , Fe ₃ O ₄ , PbO, CuO, MnO ₂ , WO ₃ , Bi ₂ O ₃ and MoO ₃ .

In the aforementioned energetic structural material, preferably, the high-density metal is one or more of Ni, W or Ta.

For the aforementioned energetic structural material, preferably, the metal oxide is WO ₃ or MoO ₃ .

As a general inventive concept, the present invention also provides a method for preparing the aforementioned energetic structural material, comprising the following steps:

(1) Mixing: According to the formula of energetic structural materials, aluminum powder, high-density metal powder, and metal oxide powder are mixed to obtain mixed powder;

(2) Preforming: Cold pressing the mixed powder to obtain a preform;

(3) Sintering: The preform is sintered to obtain bulk energetic structural materials.

In the preparation method of the above energetic structural material, preferably, in the step (1), the particle size of the mixed powder is 0.1 μm to 50 μm; in the step (2), the cold pressing pressure is 100 MPa to 600 MPa , the time is 1min to 10min.

In the above method for preparing energetic structural materials, preferably, in the step (3), the sintering includes atmospheric pressure sintering and hot-press sintering.

In the preparation method of the above-mentioned energetic structural material, preferably, in the step (3), the sintering temperature is 300°C-600°C, and the holding time is 0.5h-3h; the pressure of the hot-press sintering is 100MPa ~600MPa.

As a general inventive concept, the present invention also provides an application of the above-mentioned energetic structural material or the energetic structural material prepared by the above-mentioned method for preparing the energetic structural material in warheads.

Compared with the prior art, the present invention has the advantages of:

1. Compared with the existing energetic structural materials, the energetic structural material of the present invention is a metal-type energetic structural material, and the metal component content in the material is more than 95%; the aluminum or aluminum alloy in the material is The continuous matrix phase, other high-density metal particles and metal oxide particles are evenly distributed in the aluminum matrix phase, which has a certain strengthening effect and ensures the high strength of the material. In order to make aluminum form a continuous matrix phase during the forming process so that the energetic structural material has high strength, the mass content of low-density Al in the material is between 10% and 60%; in addition, 0.5-5.0wt% Al Metal oxides, the metal oxide content within this range has little effect on the strength of the material, and can change the impact response characteristics of the material without significantly changing the strength of the material, so that the energetic structural material has good impact response characteristics. Preferably, by adjusting the composition of the material, especially the content of heavy metal elements W, Ta and Hf, the density of the material can be changed within a certain range to meet the needs of different applications.

2. The energetic structural material of the present invention has high latent heat of reaction because the main components are all elements with high combustion calorific value. Under the action of impact load, in addition to the chemical reaction between material components, such as the reaction of Al and Ni to form AlNi, Al ₃ Ni ₂ and Al ₃ Ni, the reaction of Al and CuO to form Cu and Al ₂ O ₃ , etc., If there is oxygen in the environment, chemical reactions between material components and oxygen will also occur, such as the reaction of Al and O ₂ to generate Al ₂ O ₃ , the reaction of Zr and O ₂ to generate ZrO ₂ , etc., during which a large amount of heat.

3. The test shows that the content of aluminum or aluminum alloy, forming pressure, forming degree and holding time all have a great influence on the strength of energetic structural materials. The preparation method of the energy-containing structural material of the present invention ensures that the formed material has as high strength as possible through strict control of the forming process, and there is no adverse chemical reaction between components in the material, and no other phases are formed.

Description of drawings

Fig. 1 is the XRD spectrum of the Ni-Al energetic structural material of Example 1 of the present invention.

Fig. 2 is a fracture SEM image of the Ni-Al energetic structural material of Example 1 of the present invention.

Fig. 3 is a tensile curve of the Ni-Al energetic structural material of Example 1 of the present invention.

Fig. 4 is a photograph of the impact reaction of the Ni-Al energetic structural material of Example 1 of the present invention at an impact velocity of about 900 m/s.

Fig. 5 is a photograph of the impact reaction of the Ni-Al energetic structural material without adding metal oxides in Comparative Example 1 at an impact velocity of about 900 m/s.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

Example 1:

A Ni-Al energy-containing structural material of the present invention, comprising Al, Ni and metal oxide MoO ₃ , the mass ratio of Al, Ni and MoO ₃ is 48:50:2, wherein aluminum is the continuous matrix phase, Ni and _MoO3 is uniformly distributed in the Al matrix phase.

A preparation method of the Ni-Al energetic structural material of the above-mentioned present embodiment, comprising the following steps:

(1) Mixing: Weigh 240g of Al powder, 250g of Ni powder and 10g of MoO ₃ powder according to the mass ratio of Al powder, Ni powder and MO ₃ powder in the ratio of 48:50:2. Mix evenly in a ball mill, and the particle size of the obtained mixed powder is 0.5μm~20μm;

(2) Preforming: Weigh 200g of the mixed powder, spread it evenly on the bottom of the die, and then apply a pressure of 300MPa to the laid powder through the convex film and keep the pressure for 3min, then release the pressure;

(3) Sintering: raise the temperature of the above mold and the preform in the mold to 380°C at a rate of 5°C/min, keep the temperature constant for 90 minutes, then apply a pressure of 400MPa and keep the pressure constant for 5 minutes, and demould to obtain a Ni-Al energetic structure Material.

Figure 1 is the XRD spectrum of the Ni-Al energetic structural material of this example, as can be seen from the figure, the Ni-Al energetic structural material is mainly composed of metal Ni and Al, and there is no Ni-Al intermetallic compound phase . In addition, due to the low content of MoO ₃ in the material, no diffraction peak of MoO ₃ was observed.

Figure 2 is a fracture SEM image of the Ni-Al energetic structural material of this embodiment, it can be seen that the massive continuous matrix phase is Al, Ni particles and metal _oxide MoO3 particles are evenly distributed in the aluminum matrix phase.

Fig. 3 is the tensile curve of the Ni-Al energetic structural material of this embodiment, as can be seen from the figure, the tensile strength of the Ni-Al energetic structural material is about 230MPa, which is much greater than that of the PTFE/Al energetic structural material ( not exceeding 30MPa).

In addition, it is calculated that the density of the Ni-Al energetic structural material is about 4.10g/cm ³ , and the mass content of high combustion calorific value elements Al and Ni is about 96%.

Comparative example 1:

The preparation method of the Ni—Al energetic structural material in this comparative example is the same as that in Example 1, the only difference being that the material does not include metal oxide MoO ₃ .

Fig. 4 is the photo of the impact reaction of the Ni-Al energetic structural material of Example 1 of the present invention at an impact velocity of about 900m/s; Fig. 5 is the Ni-Al energetic structural material of Comparative Example 1 at about 900m/s Shock reaction photos at 900m/s impact velocity. Comparing Figures 4 and 5, it can be seen that the Ni-Al energetic structural material with metal oxide MoO3 added in Example ₁ has a large reaction flare area at an impact velocity of 900m/s, while no metal oxide is added in Comparative Example 1. The Ni-Al energetic structural material of MoO ₃ has a very small reaction flare area at the same impact velocity, which shows that the Ni-Al energetic structural material of Example 1 of the present invention has good impact response characteristics.

Example 2:

A Ni-Al-W energetic structural material of the present invention, including Al, high-density metal Ni and W, and metal oxides MoO ₃ , WO ₃ , the mass ratio of Al, Ni, W, MoO ₃ and WO ₃ is 17:19:60:2:2, wherein aluminum is a continuous matrix phase, and Ni, W, MoO ₃ and WO ₃ are evenly distributed in the aluminum matrix phase.

(1) Mixing: Weigh 85g of Al powder, 95g of Ni powder and 300g of W powder according to the mass ratio of Al powder, Ni powder, W powder, MoO ₃ and WO ₃ powder in the ratio of 17:19:60:2:2 10g of MO ₃ powder and 10g of WO ₃ powder, mix the weighed powders uniformly in a ball mill, and the particle size of the obtained mixed powder is 0.5 μm ~ 20 μm;

(2) Preforming: Weigh 200g of the mixed powder and spread it evenly on the bottom of the die, then apply a pressure of 300MPa to the laid powder through the convex film and keep the pressure for 3min, then release the pressure;

(3) Sintering: raise the above-mentioned mold and the preform in the mold to 400°C at a rate of 5°C/min, keep the temperature constant for 90min, then apply a pressure of 400MPa and keep the pressure constant for 5min, and demould to obtain Ni-Al-W containing capable structural materials.

The mass content of high combustion heat value elements Al and Ni in the energetic structural material is about 37%, the density is about 8.0g/cm ³ , and the tensile strength is about 210MPa.

Example 3:

An Al-W-Ta energetic structural material of the present invention, comprising Al, high-density metal W and Ta, and metal oxide WO ₃ , the mass ratio of Al, W, Ta and WO ₃ is 20:34:43: 3. Among them, aluminum is the continuous matrix phase, and W, Ta and WO ₃ are evenly distributed in the aluminum matrix phase.

(1) Mixing: Weigh 100g of Al powder, 170g of W powder, 215g of Ta powder and 15g of WO ₃ powder according to the mass ratio of Al powder, W powder, Ta powder and WO ₃ powder in the ratio of 20:34:43:3 , mix the weighed various powders uniformly in a ball mill, and the particle size of the obtained mixed powder is 0.5 μm ~ 50 μm;

(2) Preforming: Weigh 200g of the mixed powder and spread it evenly on the bottom of the die, then apply a pressure of 400MPa to the laid powder through the convex film and keep the pressure for 3min, then release the pressure;

(3) Sintering: raise the temperature of the above mold and the preform in the mold to 480°C at a rate of 5°C/min, keep the temperature constant for 90 minutes, then apply a pressure of 500 MPa and keep the pressure constant for 5 minutes, and demold to obtain Al-W-Ta containing capable structural materials.

The mass content of high combustion heat value elements Al and Ta in the energetic structural material is about 63%, the density of the material is about 8.05g/cm ³ , and the tensile strength is about 280MPa.

Example 4:

A kind of Al-Ni-Ta-Zr energetic structural material of the present invention, comprises Al, high-density metal Ni, Ta and Zr, and metal oxide WO ₃ , the mass ratio of Al, Ni, Ta, Zr and WO ₃ is 32:14:43:10:1, wherein aluminum is a continuous matrix phase, and Ni, Ta, Zr and WO ₃ are uniformly distributed in the aluminum matrix phase.

(1) Mixing: Weigh 160g of Al powder, 70g of Ni powder and 215g of Ta powder according to the mass ratio of Al powder, Ni powder, Ta powder, Zr powder and WO ₃ powder in the ratio of 32:14:43:10:1 , Zr powder 50g and WO ₃ powder 5g, mix the various powders that have been weighed evenly in a ball mill, and the particle size of the resulting mixed powder is 0.5 μm ~ 50 μm;

(2) Preforming: Weigh 200g of the mixed powder and spread it evenly on the bottom of the die, then apply a pressure of 400MPa to the laid powder through the convex film and keep the pressure for 3min, then release the pressure;

(3) Sintering: raise the temperature of the above mold and the preform in the mold to 400°C at a rate of 5°C/min, keep the temperature constant for 90min, then apply a pressure of 500MPa and keep the pressure constant for 5min, demould, and obtain Al-Ni-Ta- Zr energetic structural material.

The mass content of high combustion heat value elements Al, Ni, Ta and Zr in the energetic structural material is about 99%, the density of the material is about 5.35g/cm ³ , and the tensile strength is about 200MPa.

The above descriptions are only preferred implementations of the present invention, and the scope of protection of the present invention is not limited to the above examples. All technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims (10)

1. An energetic structural material, characterized in that it comprises the following components in mass fraction: Aluminum or aluminum alloy 10%～60% High Density Metal 35%~89.5%, and Metal oxide 0.5%～5.0%; Wherein, aluminum or aluminum alloy is a continuous matrix phase, and high-density metals and metal oxides are evenly distributed in the continuous matrix phase. 2. The energetic structural material according to claim 1, wherein the high-density metal is one or more of Ni, W, Ta, Hf, Ti and Zr. 3. The energetic structural material according to claim 2, wherein the metal oxides are Fe ₂ O ₃ , Fe ₃ O ₄ , PbO, CuO, MnO ₂ , WO ₃ , Bi ₂ O ₃ and MoO One or more of ₃ . 4. The energetic structural material according to claim 3, wherein the high-density metal is one or more of Ni, W or Ta. 5 . The energetic structural material according to claim 4 , wherein the metal oxide is WO ₃ or MoO ₃ . 6. A method for preparing the energetic structural material according to any one of claims 1 to 5, comprising the following steps: (1) Mixing: According to the formula of energetic structural materials, aluminum powder, high-density metal powder, and metal oxide powder are mixed to obtain mixed powder; (2) Preforming: Cold pressing the mixed powder to obtain a preform; (3) Sintering: The preform is sintered to obtain bulk energetic structural materials. 7. The method for preparing energetic structural materials according to claim 6, characterized in that, in the step (1), the particle size of the mixed powder is 0.1 μm to 50 μm; in the step (2), the The cold pressing pressure is 100MPa-600MPa, and the time is 1min-10min. 8 . The method for preparing energetic structural materials according to claim 7 , wherein in the step (3), the sintering includes atmospheric pressure sintering and hot-press sintering. 9. The preparation method of energetic structural materials according to claim 8, characterized in that, in the step (3), the sintering temperature is 300°C-600°C, and the holding time is 0.5h-3h; The pressure of the hot pressing sintering is 100MPa-600MPa. 10. An energetic structural material as described in any one of claims 1 to 5 or an energetic structural material prepared by the method for preparing an energetic structural material as described in any one of claims 6 to 9 in the warhead in the application.