Tungsten-zirconium active material and method for producing the same

Abstract

The present application relates to the technical field of alloy material, and particularly relates to a tungsten-zirconium active material and a preparation method thereof. The tungsten-zirconium active material provided by the present application is prepared by using the following elements with mass percentage: W 55-85%, Zr 10-35%, and other elements 3-30%; the other elements are two or more of Ti, Nb, Hf and Mo. The content of W is controlled to be 55-85%, so that the density of the material is 11 g / cm 3 The above ensures high strength of the material, so that the material has kinetic energy penetration capacity; the content of Zr is more than 10%, so that the material has certain activity; the addition of other elements such as Ti, Nb, Hf and Mo inhibits the generation of W2Zr brittle phase, so that the plasticity of the tungsten-zirconium active material is improved. In combination with the specific preparation method, the prepared tungsten-zirconium active material has high strength, high density and high plasticity.

Description

Technical Field

[0001] This invention relates to the field of alloy materials technology, and in particular to a tungsten-zirconium active material and its preparation method. Background Technology

[0002] Tungsten-zirconium reactive material is an alloy material prepared through a specific process using high-density tungsten and highly reactive zirconium as the main elements. Under high-speed impact conditions, this material can release a large amount of chemical energy through its own reaction or by reacting with air. Replacing inert components such as fragments in traditional warheads with tungsten-zirconium reactive material can achieve a dual destructive effect combining kinetic energy penetration and chemical energy, significantly enhancing the destructive power of traditional warheads.

[0003] Tungsten-zirconium active alloys are typical high-strength brittle materials, with a quasi-static compressive strength exceeding 1000 MPa and a compressive strain of less than 1.5%. Under dynamic loading, their fracture strength can reach 2000 MPa, with a fracture strain below 3%. This low plasticity makes it difficult to guarantee the material's integrity during detonation-driven and target-penetrating processes. The brittleness of tungsten-zirconium alloys is mainly due to the formation of the W₂Zr brittle phase during the preparation process. Currently, the mainstream preparation process for tungsten-zirconium alloys is hot-pressing sintering, which involves high sintering temperatures (above 1500℃) and long sintering times (above 2 hours). During sintering, the formation of the W₂Zr brittle phase is difficult to avoid. Furthermore, excessively long sintering times can easily trigger the reaction between C in the high-strength graphite mold and the active material Zr, exacerbating the brittleness of the tungsten-zirconium alloy.

[0004] Therefore, how to improve the plasticity of tungsten-zirconium active materials while ensuring their high strength and density has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a tungsten-zirconium active material and its preparation method. The tungsten-zirconium active material provided by the present invention has high strength and high density while also having high plasticity.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a tungsten-zirconium active material, prepared by a specific method from the following elements in mass percentage: W 55-85%, Zr 10-35%, and other elements 3-30%; wherein the other elements are two or more of Ti, Nb, Hf, and Mo.

[0008] The specific preparation method includes the following steps:

[0009] Based on the above elemental composition, raw materials including tungsten powder, zirconium powder, and other element-corresponding metal powders are provided;

[0010] All raw material powders, except for tungsten powder, are ball-milled to obtain alloy powder;

[0011] The alloy powder is mixed with tungsten powder to obtain a mixed powder.

[0012] A metal foil is placed inside a graphite mold, and the mixed powder is placed in the graphite mold. The mixture is then rapidly hot-pressed and sintered at 1100–1300°C and 10–100 MPa for 10–60 min under vacuum or a protective atmosphere to obtain the tungsten-zirconium active material. The melting point of the metal foil is more than 200°C higher than the hot-pressing sintering temperature.

[0013] The density of the tungsten-zirconium active material is above 11 g / cm3, the quasi-static compressive strength is above 2050 MPa, the compressive strain is above 11.5%, the dynamic fracture strength is above 2200 MPa, and the dynamic fracture strain is above 13%.

[0014] Preferably, the other elements are Nb and Ti, or Mo and Ti, or Nb and Hf, or Nb, Hf and Ti.

[0015] This invention provides a method for preparing the tungsten-zirconium active material described above, comprising the following steps:

[0016] Based on the elemental composition of tungsten-zirconium active materials, raw materials including tungsten powder, zirconium powder, and other element-corresponding metal powders are provided;

[0017] All raw material powders, except for tungsten powder, are ball-milled to obtain alloy powder;

[0018] The alloy powder is mixed with tungsten powder to obtain a mixed powder.

[0019] A metal foil is placed inside a graphite mold, and the mixed powder is placed in the graphite mold. The mixture is then rapidly hot-pressed and sintered at 1100–1300°C and 10–100 MPa for 10–60 min under vacuum or a protective atmosphere to obtain the tungsten-zirconium active material. The melting point of the metal foil is more than 200°C higher than the temperature of the rapid hot-pressing sintering.

[0020] Preferably, the ball milling time is 2 to 10 hours, the rotation speed is 100 to 400 r / min, and the ball-to-material ratio is 2 to 3:1.

[0021] Preferably, the tungsten powder has a Fisher particle size of 3–10 μm; the zirconium powder has a Fisher particle size > 48 μm and the mass percentage of the powder is no more than 5%; the other elements have corresponding metal powders with a Fisher particle size of 10–20 μm.

[0022] Preferably, the tungsten powder is industrial tungsten powder; the zirconium powder is industrial-grade zirconium hydride powder; and the metal powders corresponding to the other elements are industrial-grade pure metal powders or hydride powders.

[0023] Preferably, the metal foil includes tantalum foil, zirconium foil, or titanium foil; the thickness of the metal foil is ≤0.05mm.

[0024] Preferably, the mixing is carried out in a three-dimensional mixer or a vibrating mixer, and the mixing time is 6 to 12 hours.

[0025] This invention provides a tungsten-zirconium active material, comprising, by mass percentage: 55-85% W, 10-35% Zr, and 3-30% other elements; wherein the other elements are two or more selected from Ti, Nb, Hf, and Mo. In this invention, the W content is 55-85%, resulting in a material density of 11 g / cm³. 3 The above ensures the material's high strength, giving it kinetic energy penetration capability; the Zr content is above 10%, ensuring the material has a certain degree of activity; the addition of other elements such as Ti, Nb, Hf, and Mo inhibits the formation of the brittle W2Zr phase, thereby improving the plasticity of the tungsten-zirconium active material.

[0026] The aforementioned tungsten-zirconium active material is prepared using a specific method. Specifically, this invention employs a two-step powder mixing method, which reduces the diffusion of tungsten powder with other powders and improves the interfacial bonding between tungsten particles and the binder phase. This invention uses metal foil protection, which reduces oxidation and carburization problems during the sintering process. This invention uses rapid hot-pressing sintering, which has a low sintering temperature and short sintering time, thus minimizing the formation of the W2Zr brittle phase, resulting in low energy consumption and a short overall preparation process.

[0027] The method of the present invention does not have high requirements for the raw material powder; industrial-grade powder can be used. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of a rapid hot pressing sintering equipment;

[0029] Figure 2 The image shows the microstructure of the tungsten-zirconium active material prepared in Example 1.

[0030] Figure 3 The image shows the microstructure of the tungsten-zirconium active material prepared in Example 3.

[0031] Figure 4 This is a microstructure diagram of the tungsten-zirconium active material prepared in Comparative Example 1;

[0032] Figure 5 This is a microstructure diagram of the tungsten-zirconium active material prepared in Comparative Example 3;

[0033] Figure 6 The image shows the microstructure of the tungsten-zirconium active material prepared in Comparative Example 4.

[0034] Figure 7 The image shows the microstructure of the tungsten-zirconium active material prepared in Comparative Example 5. Detailed Implementation

[0035] This invention provides a tungsten-zirconium active material, which is prepared by a specific method from the following elements in mass percentage: W 55-85%, Zr 10-35%, and other elements 3-30%; wherein the other elements are two or more of Ti, Nb, Hf and Mo.

[0036] The tungsten-zirconium active material provided by this invention comprises 55-85% W by weight, and in specific embodiments, it can be 55%, 60%, 65%, 70%, 75%, 80%, or 85%. This invention controls the W content to be 55-85%, resulting in a material density of 11 g / cm³. 3 The above ensures the high strength of the tungsten-zirconium active material, giving it kinetic energy penetration capability.

[0037] The tungsten-zirconium active material provided by this invention comprises 10-35% Zr by weight percentage, and in specific embodiments it can be 10%, 12%, 15%, 20%, 25%, 30%, or 35%. By controlling the Zr content within the above range, this invention ensures that the material has a certain level of activity.

[0038] The tungsten-zirconium active material provided by this invention comprises 3-30% other elements by mass percentage. In specific embodiments, this can be 3%, 8%, 10%, 15%, 20%, 23%, 26%, or 30%, preferably 8% or more (i.e., 8-30%). In this invention, the other elements are two or more of Ti, Nb, Hf, and Mo. As a preferred embodiment, the other elements are Nb and Ti, or Mo and Ti, or Nb and Hf, or Nb, Hf, and Ti. More preferably, when the other elements are Nb and Ti, the tungsten-zirconium active material comprises 5-20% Nb and 3-10% Ti. In embodiments, Nb can specifically be 6%, 7%, 10%, 13%, 15%, or 20%, and Ti can specifically be 3%, 5%, 8%, or 10%. When other element combinations are used, it is preferable that the total mass percentage of the other elements is 8-30%, and the ratio of each element is not particularly important. In embodiments of the present invention, when the other elements are Mo and Ti, the content of Mo can be 7% and the content of Ti can be 15%; when the other elements are Nb and Hf, the content of Nb can be 16% and the content of Hf can be 10%; when the other elements are Nb, Hf and Ti, the content of Nb can be 4%, the content of Hf can be 7%, and the content of Ti can be 3%.

[0039] In this invention, the addition of the other elements suppresses the formation of the brittle W2Zr phase, thereby improving the plasticity of the tungsten-zirconium active material. Furthermore, the addition of these other elements can accelerate the diffusion between the matrix tungsten and the binder phase, lowering the sintering temperature. This lower sintering temperature also contributes to improving the plasticity of the tungsten-zirconium active material.

[0040] In this invention, the density of the tungsten-zirconium active material is preferably 11 g / cm³. 3 The quasi-static compressive strength is preferably above 2050 MPa, the compressive strain is preferably above 11.5%, the dynamic fracture strength is preferably above 2200 MPa, and the dynamic fracture strain is preferably above 13%.

[0041] This invention provides a specific preparation method for the tungsten-zirconium active material described above, comprising the following steps:

[0042] Based on the elemental composition of tungsten-zirconium active materials, raw materials including tungsten powder, zirconium powder, and other element-corresponding metal powders are provided;

[0043] All raw material powders, except for tungsten powder, are ball-milled to obtain alloy powder;

[0044] The alloy powder is mixed with tungsten powder to obtain a mixed powder.

[0045] Metal foil is placed in a graphite mold, and then the mixed powder is placed in the graphite mold and rapidly hot-pressed and sintered under vacuum or protective atmosphere to obtain the tungsten-zirconium active material.

[0046] The melting point of the metal foil is more than 200°C higher than the temperature of rapid hot pressing sintering;

[0047] The rapid hot pressing sintering temperature is 1100-1300℃, the sintering pressure is 10-100MPa, and the sintering time is 10-60min.

[0048] Unless otherwise specified, all raw materials used in this invention are commercially available products well known in the art.

[0049] The present invention first provides raw material powder.

[0050] In this invention, the raw material powder includes tungsten powder, zirconium powder, and metal powders corresponding to other elements; the tungsten powder preferably has a Fisher particle size of 3-10 μm, and the tungsten powder is preferably industrial tungsten powder; the mass percentage of zirconium powder with a Fisher particle size >48 μm is preferably no more than 5%, and the zirconium powder is preferably industrial-grade zirconium hydride powder; the metal powders corresponding to other elements are preferably industrial-grade pure metal powders or hydride powders, and the Fisher particle size of the metal powders corresponding to other elements is preferably 10-20 μm.

[0051] In this invention, raw material powders other than tungsten powder are first ball-milled to obtain alloy powder.

[0052] In this invention, the ball milling time is preferably 2 to 10 hours, and in specific embodiments, it can be 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours; the ball milling speed is preferably 100 to 400 r / min, and in specific embodiments, it can be 100 r / min, 200 r / min, 300 r / min, or 400 r / min; the ball-to-material ratio is preferably 2 to 3:1, and in specific embodiments, it can be 2:1, 2.5:1, or 3:1. In this invention, the ball milling is preferably carried out under argon protection. This invention preferably uses a planetary ball mill for the ball milling.

[0053] After obtaining the alloy powder, the present invention mixes the alloy powder with tungsten powder to obtain a mixed powder.

[0054] In this invention, the mixing is preferably carried out in a three-dimensional mixer or a vibrating mixer, and the mixing time is preferably 6 to 12 hours, which can be 6 hours, 8 hours, 10 hours or 12 hours in specific embodiments.

[0055] The purpose of the two-step powder mixing method in this invention is to reduce the diffusion of tungsten powder into other powders, and the mechanical alloying of other powders through ball milling can enhance the interfacial bonding between tungsten particles and the binder phase during subsequent sintering.

[0056] After obtaining the mixed powder, the present invention preferably sieves the mixed powder in a vacuum glove box with a mesh size of 100, and takes the sieved material for subsequent steps.

[0057] The present invention involves inserting metal foil into a graphite mold, and then placing the mixed powder in the graphite mold for rapid hot pressing and sintering under a protective atmosphere to obtain the tungsten-zirconium active material.

[0058] The present invention does not have any special requirements for the graphite mold; any graphite mold known in the art is acceptable.

[0059] In this invention, the melting point of the metal foil is at least 200°C higher than the rapid hot pressing sintering temperature. Preferably, the metal foil comprises tantalum foil, zirconium foil, or titanium foil, and the specific type can be selected based on the sintering temperature. Preferably, the thickness of the metal foil is ≤0.05 mm.

[0060] This invention inserts metal foil into the graphite mold to prevent direct contact between the powder and the graphite mold. Direct contact would trigger a reaction between the carbon (C) in the graphite mold and the active material Zr, exacerbating the brittleness of the tungsten-zirconium active material.

[0061] In this invention, the rapid hot-pressing sintering temperature is 1100–1300°C, and in specific embodiments, it can be 1100°C, 1200°C, or 1300°C; the rapid hot-pressing sintering pressure is 10–100 MPa, and in specific embodiments, it can be 10 MPa, 20 MPa, 40 MPa, 60 MPa, or 80 MPa; the sintering time is 10–60 min, and in specific embodiments, it can be 10 min, 20 min, 30 min, 40 min, 50 min, or 60 min. In this invention, the protective atmosphere is preferably a vacuum atmosphere or an argon atmosphere; when a vacuum atmosphere is used, the vacuum degree is preferably below 200 Pa, more preferably below 100 Pa.

[0062] Figure 1 This is a schematic diagram of a rapid hot pressing (RTP) sintering equipment. RTP is a powder metallurgy sintering technology that involves loading metal powders into a mold made of materials such as graphite, and applying DC power and pressing pressure to the powder using upper and lower die punches and energized electrodes. Compared to SPS sintering (spark plasma sintering), RTP does not use expensive pulsed power supplies, resulting in lower equipment costs. Furthermore, the Joule heating effect of the high current reduces sintering time.

[0063] The following detailed description of the tungsten-zirconium active material and its preparation method provided by the present invention, with reference to the embodiments, should not be construed as limiting the scope of protection of the present invention.

[0064] Example 1

[0065] (1) Preparation of 65W20Zr7Nb8Ti alloy powder (the number before the element is the mass percentage of the element in the alloy, the same below): Weigh tungsten powder, zirconium hydride powder, niobium hydride powder and titanium hydride powder in a vacuum glove box according to the alloy ratio.

[0066] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 6 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0067] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0068] (4) Place the titanium foil (thickness of 0.05 mm) into the graphite mold, and then put the sieved material obtained in step (3) into the mold and vibrate it.

[0069] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 40 MPa, hold for 10 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0070] The obtained tungsten-zirconium active material was sampled, the alloy microstructure was observed, and room temperature quasi-static compressive properties were tested (GB / T 7314-2005) and dynamic compression tests (GJB 8799-2015). The results are shown in Table 1 and... Figure 2 .

[0071] Table 1 Performance data of Example 1

[0072]

[0073] Figure 2 The image shows the microstructure of the tungsten-zirconium active material prepared in Example 1. Figure 2 As can be seen, the addition of Nb and Ti generates WNb. x Ti y The phase inhibited the formation of the W2Zr phase.

[0074] Example 2

[0075] (1) Preparation of 81W10Zr6Nb3Ti alloy powder (the number before the element is the mass percentage of the element in the alloy, the same below): Weigh tungsten powder, zirconium hydride powder, niobium hydride powder and titanium hydride powder in a vacuum glove box according to the alloy ratio.

[0076] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 6 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0077] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0078] (4) Place the titanium foil (thickness of 0.05 mm) into the graphite mold, and then put the sieved material obtained in step (3) into the mold and vibrate it.

[0079] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 40 MPa, hold for 10 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0080] The obtained tungsten-zirconium active material was sampled, the alloy microstructure was observed, and room temperature quasi-static compression performance was tested (GB / T 7314-2005) and dynamic compression test (GJB 8799-2015). The results are shown in Table 2.

[0081] Table 2 Performance data of Example 2

[0082]

[0083] Example 3

[0084] (1) Preparation of 76W10Zr7Hf4Nb3Ti alloy powder: Tungsten powder, zirconium hydride powder, hafnium hydride powder, titanium hydride powder, and niobium hydride powder were weighed in a vacuum glove box according to the alloy ratio.

[0085] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 10 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0086] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0087] (4) Place the titanium foil (thickness of 0.05 mm) into the graphite mold, and then put the sieved material obtained in step (3) into the mold and vibrate it.

[0088] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 80 MPa, hold for 30 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0089] Samples of the obtained tungsten-zirconium active material were taken, the alloy microstructure was observed, and room temperature quasi-static compressive properties and dynamic compression tests were conducted. The results are shown in Table 3 and 4. Figure 3 .

[0090] Table 3 Performance data of Example 3

[0091]

[0092]

[0093] Figure 3 The image shows the microstructure of the tungsten-zirconium active material prepared in Example 3. Figure 3 As can be seen, the addition of Nb, Ti, and Hf generates WNb. x Ti y Hf zThe phase inhibited the formation of the W2Zr phase.

[0094] Example 4

[0095] (1) Preparation of 68W10Zr7Mo15Ti alloy powder: tungsten powder, zirconium hydride powder, titanium hydride and molybdenum powder were weighed in a vacuum glove box according to the alloy ratio.

[0096] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 10 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0097] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0098] (4) Place the titanium foil (thickness of 0.05 mm) into the graphite mold, and then put the sieved material obtained in step (3) into the mold and vibrate it.

[0099] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1100 °C, sinter at 20 MPa, hold for 40 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0100] The obtained tungsten-zirconium active material was sampled, the alloy microstructure was observed, and room temperature quasi-static compression performance and dynamic compression test were conducted. The results are shown in Table 4.

[0101] Table 4 Performance data of Example 4

[0102]

[0103] Example 5

[0104] (1) Preparation of 62W12Zr16Nb10Hf alloy powder: tungsten powder, zirconium hydride powder, hafnium hydride powder and niobium hydride powder were weighed in a vacuum glove box according to the alloy ratio.

[0105] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 10 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0106] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0107] (4) Place the titanium foil (thickness of 0.05 mm) into the graphite mold, and then put the sieved material obtained in step (3) into the mold and vibrate it.

[0108] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1200 °C, sinter at 60 MPa, hold for 20 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0109] The obtained tungsten-zirconium active material was sampled, the alloy microstructure was observed, and room temperature quasi-static compression performance and dynamic compression test were conducted. The results are shown in Table 5.

[0110] Table 5 Performance data of Example 5

[0111]

[0112] Comparative Example 1

[0113] The difference from Example 1 is that Nb and Ti elements were not added. The specific steps are as follows:

[0114] (1) Preparation of 65W35Zr alloy powder (the number before the element is the mass percentage of the element in the alloy): Weigh tungsten powder and zirconium hydride powder in a vacuum glove box according to the alloy ratio.

[0115] (2) Weigh the tungsten powder and zirconium hydride powder into a ball mill jar, fill it with argon gas for protection, mix the powder in a vibrating mixer for 10 hours, and then sieve it in a vacuum glove box with a mesh size of 100. Take the sieve material.

[0116] (3) Place the titanium foil into the graphite mold, then put the sieved material obtained in step (2) into the mold and vibrate it.

[0117] (4) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 40 MPa, hold for 10 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0118] Samples of the obtained tungsten-zirconium active material were taken, the alloy microstructure was observed, and room temperature quasi-static compressive properties and dynamic compression tests were conducted. The results are shown in Table 6 and 7. Figure 4 .

[0119] Table 6 Performance data for Comparative Example 1

[0120]

[0121] Figure 4 The image shows the microstructure of the tungsten-zirconium active material prepared in Comparative Example 1. Figure 4As can be seen from the data, compared with Examples 1 and 2, W and Zr formed the W2Zr phase, resulting in lower plasticity.

[0122] Comparative Example 2

[0123] The difference from Example 1 is that no titanium foil protection was added. The specific steps are as follows:

[0124] (1) Preparation of 65W20Zr7Nb8Ti alloy powder: tungsten powder, zirconium hydride powder, niobium hydride powder and titanium hydride powder were weighed in a vacuum glove box according to the alloy ratio.

[0125] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 6 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0126] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0127] (4) Load the sieved material obtained in step (3) into the mold without adding metal foil, and compact the powder.

[0128] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 40 MPa, hold for 10 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0129] The obtained tungsten-zirconium active material was sampled, the alloy microstructure was observed, and room temperature quasi-static compression performance was tested (GB / T 7314-2005) and dynamic compression test (GJB 8799-2015). The results are shown in Table 7.

[0130] Table 7 Performance data for Comparative Example 2

[0131]

[0132] As can be seen from Table 7, compared with Example 1, Comparative Example 2 showed an increase in the content of C and O impurities due to the lack of titanium foil protection, and a decrease in the fracture strain under both quasi-static and dynamic compression.

[0133] Comparative Example 3

[0134] The difference from Example 1 is that a one-step powder mixing method is used, and the specific steps are as follows:

[0135] (1) Preparation of 65W20Zr7Nb8Ti alloy powder: Weigh tungsten powder, zirconium hydride powder, niobium hydride powder and titanium hydride powder in a vacuum glove box according to the alloy ratio.

[0136] (2) Weigh all the metal powders and put them into a ball milling jar. Pour argon gas for protection and then perform planetary ball milling for 6 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0137] (3) The powder from step (2) is sieved in a vacuum glove box to a mesh size of 100, and the sieved material is collected.

[0138] (4) Place the titanium foil into the graphite mold, put the sieved material obtained in step (3) into the mold, and vibrate to compact it.

[0139] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 40 MPa, hold for 10 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0140] Samples of the obtained tungsten-zirconium active material were taken, the alloy microstructure was observed, and room temperature quasi-static compressive properties and dynamic compression tests were conducted. The results are shown in Table 8 and 9. Figure 5 .

[0141] Table 8 Performance data for Comparative Example 3

[0142]

[0143] Figure 5 The image shows the microstructure of the tungsten-zirconium active material prepared in Comparative Example 3. Figure 5 As can be seen from the example, compared with Example 1, Comparative Example 3, due to the use of one-step powder mixing, has more intense diffusion of Nb and Ti, a reduced amount of pure W phase, and the matrix phase (tungsten-rich phase) interconnected into sheets, which reduces the plasticity of the alloy.

[0144] Comparative Example 4

[0145] The difference from Example 1 is that the sintering temperature is reduced to 1000℃. The specific steps are as follows:

[0146] (1) Preparation of 65W20Zr7Nb8Ti alloy powder: tungsten powder, zirconium hydride powder, niobium hydride powder and titanium hydride powder were weighed in a vacuum glove box according to the alloy ratio.

[0147] (2) Weigh all the metal powders and put them into a ball milling jar. Pour argon gas for protection and then perform planetary ball milling for 6 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0148] (3) The powder from step (2) is sieved in a vacuum glove box to a mesh size of 100, and the sieved material is collected.

[0149] (4) Place the titanium foil into the graphite mold, put the sieved material obtained in step (3) into the mold, and vibrate to compact it.

[0150] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1000 °C, sinter at 40 MPa, hold for 10 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0151] Samples of the obtained tungsten-zirconium active material were taken, the alloy microstructure was observed, and room temperature quasi-static compressive properties and dynamic compression tests were conducted. The results are shown in Table 9 and 1. Figure 6 .

[0152] Table 9 Performance data for Comparative Example 4

[0153]

[0154]

[0155] Figure 6 The image shows the microstructure of the tungsten-zirconium active material prepared in Comparative Example 4. Figure 6 As can be seen from the data, compared with Example 1, Comparative Example 4 shows more obvious pore defects due to the lower sintering temperature, and the plasticity of the tungsten zirconium active material is also relatively reduced.

[0156] Comparative Example 5

[0157] The difference from Example 1 is that the sintering time is 120 minutes, and the specific steps are as follows:

[0158] (1) Preparation of 65W20Zr7Nb8Ti alloy powder (the number before the element is the mass percentage of the element in the alloy, the same below): Weigh tungsten powder, zirconium hydride powder, niobium hydride powder and titanium hydride powder in a vacuum glove box according to the alloy ratio.

[0159] (2) Weigh out the metal powders other than tungsten powder and put them into a ball mill jar. Pour argon gas for protection and then perform planetary ball milling for 6 hours at a speed of 300 r / min. The ball-to-material ratio is 3:1.

[0160] (3) The weighed tungsten powder is put into the ball-milled powder and mixed in a vibrating mixer for 10 hours. Then, it is sieved in a vacuum glove box with a mesh size of 100 and the sieve material is taken.

[0161] (4) Place the titanium foil (thickness of 0.05 mm) into the graphite mold, and then put the sieved material obtained in step (3) into the mold and vibrate it.

[0162] (5) Place the mold containing alloy powder in a rapid hot pressing sintering furnace, evacuate to below 100 Pa, sinter at 1300 °C, sinter at 40 MPa, hold for 120 min, and cool with the furnace after holding to obtain tungsten zirconium active material.

[0163] The obtained tungsten-zirconium active material was sampled, the alloy microstructure was observed, and room temperature quasi-static compressive properties (GB / T 7314-2005) and dynamic compression tests (GJB 8799-2015) were performed. The results are shown in Table 10 and... Figure 7 .

[0164] Table 10 Performance data for Comparative Example 5

[0165]

[0166] Figure 7 The image shows the microstructure of the tungsten-zirconium active material prepared in Comparative Example 5. Figure 7 As can be seen from the above, compared with Example 1, Comparative Example 5 has a longer sintering temperature and time, resulting in sufficient diffusion between tungsten and other elements, no pure W phase, and the matrix phase (tungsten-rich phase) is connected to each other in sheets, which greatly reduces the plasticity of the alloy.

[0167] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a tungsten-zirconium active material, characterized in that, It is prepared by a specific method from the following elements in mass percentage: W 55~85%, Zr 10~35%, and other elements 3~30%; wherein the other elements are Mo and Ti, or Nb and Hf; The specific preparation method includes the following steps: Based on the above elemental composition, raw materials including tungsten powder, zirconium powder, and other element-corresponding metal powders are provided; All raw material powders, except for tungsten powder, are ball-milled to obtain alloy powder; The alloy powder is mixed with tungsten powder to obtain a mixed powder. A metal foil is placed inside a graphite mold, and the mixed powder is placed in the graphite mold. The mixture is then rapidly hot-pressed and sintered at 1100~1300℃ and 10~100MPa for 10~60min under vacuum or a protective atmosphere to obtain the tungsten-zirconium active material. The melting point of the metal foil is more than 200℃ higher than the hot-pressing sintering temperature. The density of the tungsten-zirconium active material is 11 g / cm³. 3 The above-mentioned quasi-static compressive strength is above 2050MPa, compressive strain is above 11.5%, dynamic fracture strength is above 2200MPa, and dynamic fracture strain is above 13%.

2. The preparation method according to claim 1, characterized in that, The ball milling time is 2-10 hours, the rotation speed is 100-400 r / min, and the ball-to-material ratio is 2-3:

1.

3. The preparation method according to claim 1, characterized in that, The tungsten powder has a Fisher particle size of 3~10μm; the zirconium powder has a Fisher particle size >48μm and the mass percentage of the powder is no more than 5%; the other elements have corresponding metal powders with a Fisher particle size of 10~20μm.

4. The preparation method according to claim 1 or 3, characterized in that, The tungsten powder is industrial tungsten powder; the zirconium powder is industrial-grade zirconium hydride powder; and the metal powders corresponding to the other elements are industrial-grade pure metal powders or hydride powders.

5. The preparation method according to claim 1, characterized in that, The metal foil includes tantalum foil, zirconium foil, or titanium foil; the thickness of the metal foil is ≤0.05mm.

6. The preparation method according to claim 1, characterized in that, The mixing is carried out in a three-dimensional mixer or a vibrating mixer, and the mixing time is 6~12 hours.

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