A high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment and a preparation method thereof

Abstract

The present invention discloses a high entropy alloy reaction structure material capable of releasing energy in an oxygen-free environment and a preparation method thereof, wherein the general formula of the high entropy alloy is TiZrVAlTaO. The high entropy alloy reaction structure material provided by the present invention introduces oxygen elements, realizes a single-phase solid solution structure of Ti, Zr, V, O, Ta, and Al elements, and exhibits the characteristics of high activity and high strength plasticity. At the same time, the strength of the alloy is significantly higher than that of the existing reaction structure material, which makes the high entropy alloy reaction structure material have the characteristics of high strength, high activity, and self-reaction. Due to the design of active elements, the alloy material still has significant energy release characteristics in an oxygen-free environment.

Description

Technical Field

[0001] The present invention relates to the technical field of alloy materials, and in particular to a high-entropy alloy reaction structure material capable of releasing energy in an oxygen-free environment and a preparation method thereof. Background Art

[0002] Reactive structural materials have the characteristics of structural and energy integration. During service under strong dynamic loads, reactive structural materials rapidly undergo explosion and combustion reactions, releasing violent chemical energy.

[0003] At present, traditional reactive structural materials are usually composite materials, such as metal-fluoropolymer, metal-oxide, metal-metal composite, etc., which have low structural strength and are difficult to meet the requirements for material strength during high dynamic load service. Alloy reactive structural materials need to undergo redox reactions with oxygen in the environment to release additional chemical energy and increase the destructive power.

[0004] However, in practical applications, reactive structural materials often face oxygen-deficient or oxygen-free environments such as high altitude and underwater, and current reactive structural materials cannot react in oxygen-free environments.

[0005] Multi-principal element high entropy alloy is a new type of metal material with designable composition and controllable performance developed in recent years. It subverts the traditional alloy design concept of single metal element and is a solid solution alloy formed by fusing multiple elements in equiatomic or near-atomic ratios.

[0006] The design concept of high entropy alloys realizes the "free design" and combination of alloy components at the atomic level. Combined with the adjustment of preparation and heat treatment processes, solid solution materials with excellent comprehensive performance can be obtained. Through the optimization of the main elements, high entropy alloy-type reaction structure materials that can undergo chemical reactions under strong dynamic conditions can be designed, so that they can still have energy release characteristics in an oxygen-free environment.

[0007] Although theoretically, the design concept of high entropy alloys can be used to design materials that can still release energy in an oxygen-free environment, there are still no reports of high entropy alloy reaction structure materials that can release energy in an oxygen-free environment. This is mainly because no one has conducted research in the relevant field on the existing high entropy alloys, and no materials with relevant properties have appeared. Therefore, there is still a blank in the reaction structure materials that react in an oxygen-free environment. Summary of the invention

[0008] The purpose of the present invention is to provide a high entropy alloy reaction structure material that can release energy in an oxygen-free environment and a preparation method, so as to solve the technical problem that the high entropy alloy materials produced in the prior art cannot release energy in an oxygen-free environment.

[0009] In order to solve the above technical problems, the present invention specifically provides the following technical solutions:

[0010] In the first aspect of the present invention, a high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment is provided. The general formula of the high entropy alloy is TiZrVAlTaO, and the content of each element is as follows in terms of atomic percentage:

[0011] Ti: 40%-65%;

[0012] Ta: 10%-35%;

[0013] Zr: 1%-25%;

[0014] Al: 1%-10%;

[0015] V: 1%-10%;

[0016] O: 1%-5%.

[0017] Furthermore, the general formula of the high entropy alloy is TiZrVAlTaO, and the content of each element in atomic percentage is as follows:

[0018] Ti: 45%-60%;

[0019] Ta: 20%-30%;

[0020] Zr: 15%-20%;

[0021] Al: 5%-10%;

[0022] V: 1%-5%;

[0023] O: 1%-3%.

[0024] In a second aspect of the present invention, a method for preparing a high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment is provided, comprising the following steps:

[0025] Batching: batching clean Ti element particles, Zr element particles, V element particles, TiO2 particles, Al element particles and Ta element particles according to the atomic content ratio;

[0026] Melting: sending the above ingredients to a magnetic levitation induction melting furnace and melting them in a vacuum environment to obtain a cast alloy;

[0027] Hot isostatic pressing: The cast alloy prepared after smelting is subjected to hot isostatic pressing to obtain a high entropy alloy reaction structural material.

[0028] Furthermore, the purity of the Ti element particles is 99.9%, the purity of the Zr element particles is 99.95%, the purity of the V element particles is 99.9%, the purity of the TiO2 particles is 99.9%, the purity of the Ta element particles is 99.95%, and the purity of the Al element particles is 99.95%;

[0029] Among them, the above-mentioned metal particles are all clean raw materials for removing oxide scale.

[0030] Furthermore, the elements contained in the above metal particles are calculated by atomic percentage:

[0031] Ti: 45%-60%;

[0032] Ta: 20%-30%;

[0033] Zr: 15%-20%;

[0034] Al: 5%-10%;

[0035] V: 1%-5%;

[0036] O: 1%-3%.

[0037] Furthermore, during alloy smelting, the raw materials are fed in the following feeding order:

[0038] Firstly, Ti element particles, Zr element particles and Al element particles are added to form a master alloy;

[0039] Then TiO2 particles are added and smelted 2-3 times to form a single-phase solid solution structure master alloy;

[0040] Then, Ta element particles and V element particles are added in sequence for smelting to form a single-phase solid solution structure, that is, a cast solid solution alloy.

[0041] Furthermore, the above smelting step is specifically as follows: -3 Pa vacuum environment is used for smelting 6 to 10 times, each smelting temperature is between 2000℃ and 2200℃, each smelting time is 15 to 20 minutes, after the alloy composition is uniform, it is poured into the mold and cooled naturally in a vacuum protection environment.

[0042] Furthermore, the hot isostatic pressing step is carried out in a vacuum or inert gas protected atmosphere, the hot isostatic pressing temperature is 1000-1050° C., the pressure is 150-180 MPa, and the holding time is 10 hours.

[0043] Furthermore, the holding time of the hot isostatic pressing is 10 hours, and the cooling rate is 50°C / min.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. The high entropy alloy reaction structure material provided by the present invention introduces oxygen element, realizes the structure of single-phase solid solution of Ti, Zr, V, O, Ta and Al elements, and realizes Ti-O type, Al-O type and Zr-O type redox reaction by itself during impact loading through uniform mixing of O element at atomic level, showing the characteristics of high activity and high strength plasticity. At the same time, the strength of the alloy is significantly higher than that of the existing reaction structure material, which makes the high entropy alloy reaction structure material have the characteristics of high strength, high activity and self-reaction. Due to the design of active elements, the alloy material still has significant energy release characteristics in an oxygen-free environment.

[0046] 2. The high entropy alloy preparation method provided by the present invention comprises the following steps: firstly adding Ti, Zr and Al to form an intermediate alloy, then adding TiO2 particles, and then sequentially adding Ta and V for smelting, and performing hot isostatic pressing. Under specific smelting conditions and isostatic pressing conditions, the alloy is a single-phase BCC structure with high strength and self-reaction energy release characteristics, and its internal organizational structure is uniform, and it has excellent static and dynamic compression strength and plasticity at room temperature, so as to obtain a high entropy alloy reaction structure material with high energy release characteristics in an oxygen-free environment. The process is simple, safe and reliable, and the magnetic suspension smelting process adopted has good density and phase structure stability, and is easy for industrial mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the implementation methods of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the implementation methods or the description of the prior art. Obviously, the drawings in the following description are only exemplary, and for ordinary technicians in this field, other implementation drawings can be derived from the provided drawings without creative work.

[0048] Figure 1 This is a physical picture of the high entropy alloy ingot of the present invention;

[0049] Figure 2 The static and dynamic mechanical performance diagrams of the first embodiment of the present invention;

[0050] Figure 3 This is a diagram showing the damage effect of a ballistic target in an oxygen-free environment according to the first embodiment of the present invention. DETAILED DESCRIPTION

[0051] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0052] Current reactive structural materials cannot react in an oxygen-free environment, and therefore do not meet the application requirements of reactive structural materials in oxygen-deficient or oxygen-free environments such as high altitude and underwater. Although theoretically, materials that can still have energy release properties in an oxygen-free environment can be designed through the design concept of high entropy alloys.

[0053] However, there are still no reports on high entropy alloy reactive structural materials that can release energy in an oxygen-free environment. This is mainly because no research has been conducted on the existing high entropy alloys in the relevant field, and no materials with relevant properties have appeared. Therefore, there is still a blank in reactive structural materials that react in an oxygen-free environment.

[0054] The difficulty in using the design concept of high entropy alloys to design materials that can still have energy release characteristics in an oxygen-free environment lies in how to design the composition of the elements inside the high entropy alloy, and how to design the atomic ratio between the elements based on the elemental composition, so that the high entropy alloy can have energy release characteristics in an oxygen-free environment.

[0055] like Figure 1 As shown, the present invention provides a high entropy alloy reaction structural material that can release energy in an oxygen-free environment. The general formula of the high entropy alloy is TiZrVAlTaO. In terms of atomic percentage, the content of each element is as follows:

[0056] Ti: 40%-65%;

[0057] Ta: 10%-35%;

[0058] Zr: 1%-25%;

[0059] Al: 1%-10%;

[0060] V: 1%-10%;

[0061] O: 1%-5%.

[0062] As a preferred embodiment, the general formula of the high entropy alloy is TiZrVAlTaO, and the content of each element in atomic percentage is as follows:

[0063] Ti: 45%-60%;

[0064] Ta: 20%-30%;

[0065] Zr: 15%-20%;

[0066] Al: 5%-10%;

[0067] V: 1%-5%;

[0068] O: 1%-3%.

[0069] The special feature of the present application is that, through the design of alloy elements, a single-phase solid solution material containing O is cleverly formed, so that the high-entropy alloy reaction structure material still has significant energy release characteristics in an oxygen-free environment.

[0070] The three elements Ti, Zr and Al give the material a high energy content. Through the uniform mixing of the O element at the atomic level, the material can realize Ti-O, Al-O and Zr-O redox reactions during impact loading, so that it still has significant energy release characteristics in an oxygen-free environment.

[0071] When the O content is high, an obvious brittle intermetallic compound structure will be produced, making the material as a whole brittle and difficult to be used in actual engineering. Therefore, the O content ratio is more important. In this application, the O content has a specific ratio and cannot be higher than 3%. In addition, the addition of Ta elements can effectively improve the plasticity of the material, and the addition of a small amount of V can improve the solid solution strength of the material.

[0072] After designing the composition and ratio of the internal elements of the high-entropy alloy, how to produce high-entropy alloy reactive structural materials that can release energy in an oxygen-free environment becomes the next technical difficulty.

[0073] In order to solve this problem, a method for preparing a high entropy alloy reaction structural material that can release energy in an oxygen-free environment is provided below, comprising the following steps:

[0074] Batching: batching clean Ti element particles, Zr element particles, V element particles, TiO2 particles, Al element particles and Ta element particles according to the atomic content ratio;

[0075] Melting: sending the above ingredients to a magnetic levitation induction melting furnace and melting them in a vacuum environment to obtain a cast alloy;

[0076] Hot isostatic pressing: The cast alloy prepared after smelting is subjected to hot isostatic pressing to obtain a high entropy alloy reaction structural material.

[0077] In this preparation method, magnetic levitation smelting can ensure the clean characteristics of smelting and avoid contamination by impurity elements. In order to avoid contamination by impurity elements, further, the purity of the Ti element particles is 99.9%, the purity of the Zr element particles is 99.95%, the purity of the V element particles is 99.9%, the purity of the TiO2 particles is 99.9%, the purity of the Ta element particles is 99.95%, and the purity of the Al element particles is 99.95%;

[0078] Among them, the above-mentioned metal particles are all clean raw materials for removing oxide scale.

[0079] When designing alloy elements, oxygen was creatively introduced, but how to add oxygen is the key and difficulty of this application.

[0080] In the present application, TiO2 particles are cleverly used as a carrier for adding the O element. During the smelting process, TiO2 must be added strictly according to the smelting order, that is, TiO2 particles are added after the TiZrAl intermediate alloy is formed. Otherwise, brittle alloy phases such as oxides will appear, resulting in material brittleness.

[0081] The elements contained in the above metal particles are calculated by atomic percentage:

[0082] Ti: 45%-60%;

[0083] Ta: 20%-30%;

[0084] Zr: 15%-20%;

[0085] Al: 5%-10%;

[0086] V: 1%-5%;

[0087] O: 1%-3%.

[0088] After determining the ratio between the elements, the order of adding materials must be controlled during the smelting process. If the raw materials are added in a random order, intermetallic compounds will be formed, and the resulting alloy will not meet the requirements. Therefore, in this preparation method, the order of adding raw materials is particularly important.

[0089] Here, when alloy melting is carried out, the raw materials are fed in the following feeding order:

[0090] Firstly, Ti element particles, Zr element particles and Al element particles are added to form a master alloy;

[0091] Then TiO2 particles are added and smelted 2-3 times to form a single-phase solid solution structure master alloy;

[0092] Then, Ta element particles and V element particles are added in sequence for smelting to form a single-phase solid solution structure, that is, a cast solid solution alloy.

[0093] First, Ti, Zr, and Al elements are synthesized into a master alloy, and then TiO2 is added and smelted 2-3 times to form a single-phase solid solution structure master alloy, and then Ta particles and V particles are added in turn for smelting to form a single-phase solid solution structure. Otherwise, an O-rich brittle intermetallic compound phase will appear, making it difficult to form a solid solution structure.

[0094] The key point of this preparation method is that TiO2 must be added strictly according to the smelting order during the smelting process, that is, TiO2 particles are added after the TiZr master alloy is formed, otherwise brittle alloy phases such as oxides will appear, resulting in material brittleness.

[0095] The above smelting steps are specifically as follows:-3 Pa vacuum environment is used for smelting 6 to 10 times, each smelting temperature is between 2000℃ and 2200℃, each smelting time is 15 to 20 minutes, after the alloy composition is uniform, it is poured into the mold and cooled naturally in a vacuum protection environment.

[0096] The hot isostatic pressing step is carried out in a vacuum or inert gas protected atmosphere, the hot isostatic pressing temperature is 1000-1050° C., the pressure is 150-180 MPa, and the holding time is 10 hours.

[0097] The holding time of the hot isostatic pressing is 10 hours, and the cooling rate is 50° C. / min.

[0098] The melting point of this material is about 2000°C. In this method, the hot isostatic pressing temperature is controlled at around 0.5Tm. If the temperature is too low, it will be difficult to eliminate the casting defects. If the temperature is too high, overburning may occur, damaging the initial structure of the material.

[0099] In the preparation method, the main function of hot isostatic pressing is to homogenize the cast alloy, eliminate the segregation of cast elements, and further improve the product quality.

[0100] The following is further described in conjunction with specific embodiments:

[0101] Embodiment 1:

[0102] 1) Alloy composition (in terms of atomic percentage): Ti: 50%, Zr: 16%, Ta: 25%, Al: 5%, V: 2%, O: 2%.

[0103] 2) Preparation method:

[0104] Batching: the clean Ti element particles, Zr element particles, TiO2 particles, V element particles, Al element particles and Ta element particles with the oxide scale removed are batched according to the mass percentage of 27.13%, 16.89%, 0.92%, 1.18%, 1.56% and 52.33%;

[0105] Melting: the above ingredients are sent to a magnetic suspension induction melting furnace, and the order of adding the ingredients is: first add Ti element particles, Zr element particles, and Al element particles to form an intermediate alloy;

[0106] Then TiO2 particles are added and smelted twice to form a single-phase solid solution structure master alloy;

[0107] Then add Ta element particles and V element particles in turn for smelting.

[0108] The specific smelting conditions are: at 10 -3Smelting was performed 6 times in a vacuum environment of Pa, each melting temperature was 2000℃, each melting time was 15 minutes, and after the alloy composition was uniform, it was poured into a mold with a diameter of 100mm and cooled naturally in a vacuum protection environment;

[0109] Hot isostatic pressing: The cast alloy prepared after smelting is placed in a hot isostatic pressing device protected by inert gas, the pressure is set to 180MPa, the temperature is set to 1050℃, the temperature is kept at room temperature for 10 hours, the pressure holding time is 10 hours, the cooling rate is 50℃ / min, and a high entropy alloy reaction structure material is obtained. The alloy ingot morphology is obtained as follows Figure 1 shown.

[0110] Test method:

[0111] The density is tested by the Archimedes drainage method.

[0112] According to GB / T23370-2009 and GB / T8167-2008, the alloy prepared above was subjected to quasi-static compression and dynamic compression at room temperature, and static and dynamic deformation critical failure stress tests were performed.

[0113] The test results are shown in the following table:

[0114]

[0115]

[0116] The following conclusions can be drawn from the analysis of the above table:

[0117] The embodiment shows that the density of the high entropy alloy provided by the present invention is 7.5-8.9 g / cm 3 The quasi-static compressive strength of the material is greater than 2000MPa, and the dynamic compressive strength is greater than 2500MPa, and it has high energy release characteristics in an oxygen-free environment.

[0118] The high entropy alloy reaction structural material provided by the present invention was used to impact an aluminum plate at 2200 m / s in a ballistic gun experiment, and it was found that the hole expansion damage area was significantly higher than that of a steel projectile under the same conditions, indicating that the material can be used in an oxygen-free or oxygen-deficient service environment.

[0119] There are significant energy release damage characteristics under impact loading conditions in an anaerobic environment.

[0120] The above embodiments are only exemplary embodiments of the present application and are not intended to limit the present application. The protection scope of the present application is defined by the claims. Those skilled in the art may make various modifications or equivalent substitutions to the present application within the essence and protection scope of the present application, and such modifications or equivalent substitutions shall also be deemed to fall within the protection scope of the present application.

Claims

1. A high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment, characterized in that: The general formula of the high entropy alloy is TiZrVAlTaO, and the content of each element in atomic percentage is as follows: Ti: 40%-65%; Ta: 10%-35%; Zr：1%-25%； Al：1%-10%； V：1%-10%； O：1%-3%； Preparation method of the high entropy alloy The following steps are involved: Batching: batching clean Ti element particles, Zr element particles, V element particles, TiO2 particles, Al element particles and Ta element particles according to the atomic content ratio; Melting: sending the above ingredients to a magnetic levitation induction melting furnace and melting them in a vacuum environment to obtain a cast alloy; Hot isostatic pressing: The cast alloy prepared after smelting is subjected to hot isostatic pressing to obtain a high entropy alloy reaction structure material; Among them, when alloy smelting is carried out, the raw materials are fed in the following feeding order: Firstly, Ti element particles, Zr element particles and Al element particles are added to form a master alloy; Then TiO2 particles are added and smelted 2-3 times to form a single-phase solid solution structure master alloy; Then, Ta element particles and V element particles are added in sequence for smelting to form a single-phase solid solution structure, that is, a cast solid solution alloy. The hot isostatic pressing step is carried out in a vacuum or inert gas protected atmosphere, the hot isostatic pressing temperature is 1000-1050° C., the pressure is 150-180 MPa, and the holding time is 10 hours.

2. The high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment according to claim 1, characterized in that: The general formula of the high entropy alloy is TiZrVAlTaO, and the content of each element in atomic percentage is as follows: Ti: 45%-60%; Ta: 20%-30%; Zr：15%-20%； Al：5%-10%； V：1%-5%； O：1%-3%。 3. A method for preparing a high entropy alloy reaction structural material that can release energy in an oxygen-free environment, characterized in that: The preparation method includes the preparation method of the high entropy alloy according to claim 1, and the preparation method is used to prepare the high entropy alloy according to claim 1.

4. The method for preparing a high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment according to claim 3, characterized in that: The purity of the Ti element particles is 99.9%, the purity of the Zr element particles is 99.95%, the purity of the V element particles is 99.9%, the purity of the TiO2 particles is 99.9%, the purity of the Ta element particles is 99.95%, and the purity of the Al element particles is 99.95%; Among them, the above-mentioned metal particles are all clean raw materials for removing oxide scale.

5. The method for preparing a high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment according to claim 4, characterized in that: The elements contained in the above metal particles are calculated by atomic percentage: Ti: 45%-60%; Ta: 20%-30%; Zr：15%-20%； Al：5%-10%； V：1%-5%； O：1%-3%。 6. The method for preparing a high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment according to claim 5, characterized in that: The above smelting steps are specifically as follows: -3 The alloy is melted 6 to 10 times under a vacuum environment of Pa, each melting temperature is between 2000°C and 2200°C, and each melting time is 15 to 20 minutes. After the alloy composition is uniform, it is poured into a mold and cooled naturally under a vacuum protection environment.

7. The method for preparing a high entropy alloy reaction structural material capable of releasing energy in an oxygen-free environment according to claim 6, characterized in that: The holding time of the hot isostatic pressing is 10 hours, and the cooling rate is 50° C. / min.

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