Heterogeneous tungsten-rhenium alloy and preparation method and application thereof
By adding a gradient transition layer and second-phase doping between the tungsten-rhenium alloy layer and the pure tungsten layer, and combining it with hot pressing sintering process, the interfacial bonding problem of tungsten-rhenium alloy under extreme working conditions was solved, realizing the preparation of heterogeneous tungsten-rhenium alloy with high wear resistance and low cost, and promoting its application in ultra-high temperature structural parts and wear-resistant components.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-26
- Publication Date
- 2026-04-14
AI Technical Summary
Existing technologies are insufficient to effectively address the stable application of tungsten-rhenium alloys under extreme conditions, especially the interface detachment caused by interfacial bonding issues and material property differences, and traditional preparation methods are costly.
A heterogeneous tungsten-rhenium alloy system combining a tungsten-rhenium alloy layer and a pure tungsten layer was developed. By adding a gradient transition layer and a second phase doping at the interface, and using metallic elements such as yttrium and lanthanum to refine the grains and improve the interfacial bonding strength, the heterogeneous tungsten-rhenium alloy was prepared by combining hot pressing sintering and other processes.
This study achieved the preparation of tungsten-rhenium alloys with high interfacial strength and low cost, significantly improving the wear resistance and density of the material, reducing the amount of tungsten-rhenium alloy used, and avoiding interfacial detachment caused by differences in properties.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of powder metallurgy and high-performance metal composite materials, and in particular to a heterogeneous tungsten-rhenium alloy, its preparation method and application. Background Technology
[0002] Tungsten (W), a refractory metal, plays an irreplaceable and crucial role in cutting-edge fields such as defense, aerospace, and nuclear industry due to its excellent properties, including high melting point, high density, high hardness, low sputtering rate, and low coefficient of thermal expansion. However, pure tungsten materials suffer from fatal shortcomings such as poor room temperature plasticity and toughness, and high-temperature recrystallization embrittlement, which greatly limits its stable application under extreme conditions. To overcome these technical challenges, the materials science field typically employs alloying methods, introducing rhenium (Re) to prepare W-Re alloys. Studies show that the solid solution strengthening effect of rhenium can significantly improve the room temperature plasticity and high-temperature strength of materials; however, due to the scarcity of rhenium resources and its volatile price, its industrial application is limited by cost.
[0003] In recent years, researchers have attempted to incorporate carbide and oxide second phases into W-Re alloys, successfully achieving grain refinement and improved high-temperature stability through the dispersion strengthening effect of these ultrafine particles. However, the high price of rhenium still limits the application of tungsten-rhenium alloys. It is worth noting that tungsten-rhenium alloys, as structural materials, are primarily used in friction scenarios, where the properties of the end contact areas are crucial. By preparing dissimilar materials, using high-performance tungsten-rhenium alloys at the ends and pure tungsten at the non-contact ends, the amount of tungsten-rhenium alloy used can be reduced while meeting application requirements. Traditional dissimilar alloy preparation methods often involve welding and spraying, which result in poor bonding strength. Furthermore, traditional cold isostatic pressing-forging processes are also difficult to use for dissimilar tungsten-rhenium alloys, as the significant differences in properties at the joint make them prone to fracture.
[0004] Therefore, it is necessary to develop a method for preparing high-performance heterogeneous tungsten-rhenium alloys to promote the further application of tungsten-rhenium alloys. Summary of the Invention
[0005] Based on this, the purpose of this invention is to overcome the shortcomings of the prior art and provide a heterostructured tungsten-rhenium alloy with high interfacial strength and low cost, as well as its preparation method and application.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a heterogeneous tungsten-rhenium alloy, comprising a tungsten-rhenium alloy layer and a pure tungsten layer, wherein the tungsten-rhenium alloy layer and the pure tungsten layer are adjacent; the tungsten-rhenium alloy layer comprises a mixture A, wherein the mixture A comprises the following components in mass percentage: rhenium 15-25%, tungsten carbide 3-10%, metallic elements 0.2-2%, and the balance being tungsten; And / or, the pure tungsten layer includes a mixture B, which comprises the following components in mass percentage: 0.2-2% metal elements, with the balance being tungsten.
[0007] This invention provides a tungsten-rhenium alloy / pure tungsten heteromaterial bonding system, overcoming three key technological challenges: interfacial bonding, performance differences between heteromaterials, and short-process manufacturing. This is of significant value in promoting the application of tungsten-rhenium materials in ultra-high temperature structural components, wear-resistant parts, and other fields. This invention can reduce the amount of tungsten-rhenium alloy used. By forming a heteromaterial from high-performance tungsten-rhenium alloy and tungsten powder, the heteromaterial can possess both high wear resistance and a lower cost.
[0008] The tungsten-rhenium alloy layer and the pure tungsten layer described in this invention are both doped with a second phase. The addition of the second phase can hinder grain boundary diffusion, resulting in fine grains in both the tungsten-rhenium alloy layer and the pure tungsten layer. The excellent mechanical properties of the tungsten-rhenium alloy can more effectively improve its wear resistance, while the excellent mechanical properties of pure tungsten can reduce the property differences between it and the tungsten-rhenium alloy layer, avoiding interface detachment caused by inconsistent interface deformation due to excessive property differences between the two materials.
[0009] Preferably, the metallic element is at least one selected from yttrium, lanthanum, cerium, and zirconium.
[0010] Preferably, the metal element can be in powder form.
[0011] Preferably, the heterogeneous tungsten-rhenium alloy further includes a gradient transition layer located between the tungsten-rhenium alloy layer and the pure tungsten layer.
[0012] During actual experiments, the inventors discovered that when the heterogeneous tungsten-rhenium alloy further includes a gradient transition layer located between the tungsten-rhenium alloy layer and the pure tungsten layer, the interfacial bonding strength is higher, the amount of tungsten-rhenium alloy used is less, and the prepared heterogeneous tungsten-rhenium alloy has greater density and finer grain size, with more obvious grain refinement and densification effects.
[0013] Preferably, the rhenium content of the gradient layer decreases from the tungsten-rhenium alloy layer to the pure tungsten layer.
[0014] Preferably, the gradient transition layer comprises mixture A and mixture B; the weight ratio of mixture A to mixture B is (20-80):(80-20); more preferably, the weight ratio of mixture A to mixture B is 1:1.
[0015] Optionally, the weight ratio of mixture A and mixture B is one or a range of two of the following: 20:80, 30:70, 40:60, 50:50, 70:30, and 80:20.
[0016] Preferably, in the heterojunction tungsten-rhenium alloy, the gradient transition layer has a weight percentage of 1%-10%, the tungsten-rhenium alloy layer has a weight percentage of 10%-90%, and the pure tungsten layer has a weight percentage of 10%-90%.
[0017] More preferably, in the heterogeneous tungsten-rhenium alloy, the gradient transition layer has a weight percentage of 5%, the tungsten-rhenium alloy layer has a weight percentage of 45%, and the pure tungsten layer has a weight percentage of 50%.
[0018] Furthermore, the present invention provides a method for preparing the aforementioned heterotungsten-rhenium alloy, comprising the following steps: (1) Tungsten and rhenium are mixed to obtain tungsten-rhenium pre-alloy powder. Tungsten carbide and metal elements are mixed into the tungsten-rhenium pre-alloy powder and ball-milled to obtain mixture A. Tungsten powder and metal elements are mixed and ball-milled to obtain mixture B. (2) The hydrogen-reduced mixture A and mixture B are layered and laid out, and hot pressing sintering, spark plasma sintering or hot isostatic pressing is performed under a protective atmosphere. After cooling, the heterogeneous tungsten-rhenium alloy is obtained.
[0019] Preferably, in step (1), the mixture A is subjected to hydrogen reduction to obtain a composite powder with low oxygen content; the mixture B is subjected to hydrogen reduction to obtain a composite powder with low oxygen content.
[0020] Preferably, the hydrogen reduction process is as follows: hydrogen reduction is performed at a reduction temperature of 900℃-1000℃ for 0.5-2 hours.
[0021] Preferably, in step (2), the hot pressing sintering temperature is 1500-2200℃, the hot pressing sintering pressure is 20-100 MPa, and the holding time is 0.5-3 h; the pressure direction is perpendicular to the interlayer interface.
[0022] More preferably, in step (2), the hot pressing sintering temperature is 1800-2000℃.
[0023] More preferably, in step (2), the pressure of hot pressing sintering is 50-100 MPa.
[0024] Furthermore, the present invention provides the application of the aforementioned heterojunction tungsten-rhenium alloy in the fields of ultra-high temperature structural components and wear-resistant parts.
[0025] Compared to existing technologies, the advantages of this invention are as follows: This invention provides a tungsten-rhenium alloy / pure tungsten heteromaterial bonding system, overcoming three key technological challenges: interface bonding, performance differences between heteromaterials, and short-process manufacturing. This is of significant value in promoting the application of tungsten-rhenium materials in ultra-high temperature structural components, wear-resistant parts, and other fields. This invention can reduce the amount of tungsten-rhenium alloy used. By forming a heteromaterial from high-performance tungsten-rhenium alloy and tungsten powder, the heteromaterial can possess both high wear resistance and a lower price.
[0026] The tungsten-rhenium alloy layer and the pure tungsten layer described in this invention are both doped with a second phase. The addition of the second phase can hinder grain boundary diffusion, resulting in fine grains in both the tungsten-rhenium alloy layer and the pure tungsten layer. The excellent mechanical properties of the tungsten-rhenium alloy can more effectively improve its wear resistance, while the excellent mechanical properties of pure tungsten can reduce the property differences between it and the tungsten-rhenium alloy layer, avoiding interface detachment caused by inconsistent interface deformation due to excessive property differences between the two materials. Attached Figure Description
[0027] Figure 1 This is a schematic diagram of the heterogeneous tungsten-rhenium alloy prepared in Example 2 of the present invention; wherein, 1 is a pure tungsten layer, 2 is a gradient transition layer, and 3 is a tungsten-rhenium alloy layer; Figure 2 Here is a photograph of the heterogeneous tungsten-rhenium alloy prepared in Example 1; Figure 3 Metallographic images of the interface of the heterotungsten-rhenium alloy prepared in Example 1; Figure 4 EDS image of the interface of the heterotungsten-rhenium alloy prepared in Example 1; Figure 5 Metallographic image of the interface of the heterotungsten-rhenium alloy prepared for Comparative Example 1; Figure 6 Metallographic images of the interface of the heterogeneous tungsten-rhenium alloy prepared for Comparative Example 2. Detailed Implementation
[0028] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below in conjunction with the accompanying drawings and specific embodiments. The purpose is to provide a detailed understanding of the invention, not to limit it. All other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention. Unless otherwise specified, the experimental reagents and instruments designed in the embodiments and comparative examples of this invention are commonly used reagents and instruments, all of which are commercially available. Unless otherwise specified, the experimental methods used in the embodiments and comparative examples are conventional methods; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.
[0029] The raw materials of this invention will now be further described, but are not limited to the following raw materials: The rhenium powder was purchased from Jiangxi Copper Technology Research Institute Co., Ltd. Tungsten carbide was purchased from Ganzhou Huamao Tungsten Materials Co., Ltd. The metallic element (yttrium powder) was purchased from Zhongnuo New Materials Co., Ltd. The metallic element (lanthanum powder) was purchased from Zhongnuo New Materials Co., Ltd. The tungsten powder was purchased from Ganzhou Huamao Tungsten Materials Co., Ltd.
[0030] Examples and Comparative Examples Example 1 The present invention provides a heterogeneous tungsten-rhenium alloy, comprising a tungsten-rhenium alloy layer and a pure tungsten layer, wherein the tungsten-rhenium alloy layer and the pure tungsten layer are adjacent to each other; The tungsten-rhenium alloy layer includes a mixture A, which comprises the following components by mass percentage: 23.75% rhenium, 4% tungsten carbide, 1% metallic element (yttrium powder), and the balance being tungsten; The pure tungsten layer includes a mixture B, which comprises the following components by mass percentage: 1% metal element (yttrium powder) and the balance being tungsten.
[0031] The preparation method is as follows: (1) Tungsten and rhenium are mixed to obtain tungsten-rhenium pre-alloy powder, tungsten carbide and metal elements are mixed into the tungsten-rhenium pre-alloy powder, and the mixture is ball-milled to obtain the mixture A; tungsten powder and metal elements are mixed and ball-milled to obtain the mixture B; the mixture A is hydrogen-reduced to obtain a composite powder with low oxygen content; the mixture B is hydrogen-reduced to obtain a composite powder with low oxygen content; the specific process of the hydrogen reduction treatment is: hydrogen reduction at a reduction temperature of 1000℃ for 1 h; (2) The hydrogen-reduced mixture A and mixture B are layered and laid out, wherein the mass ratio of mixture A to mixture B is 1:1. Under a protective atmosphere, hot pressing sintering is carried out at a temperature of 1800℃ and a pressure of 100 MPa. The holding time is 0.5 h. After cooling, the heterogeneous tungsten-rhenium alloy is obtained.
[0032] Example 2 The present invention provides a heterogeneous tungsten-rhenium alloy, comprising a tungsten-rhenium alloy layer, a gradient transition layer, and a pure tungsten layer, wherein the tungsten-rhenium alloy layer, the gradient transition layer, and the pure tungsten layer are sequentially adjacent, and the gradient transition layer is located between the tungsten-rhenium alloy layer and the pure tungsten layer; The tungsten-rhenium alloy layer includes a mixture A, which comprises the following components by mass percentage: 23.75% rhenium, 4% tungsten carbide, 1% metallic element (yttrium powder), and the balance being tungsten; The pure tungsten layer includes a mixture B, which comprises the following components by mass percentage: 1% metal element (yttrium powder) and the balance being tungsten.
[0033] The gradient transition layer comprises mixture A and mixture B; the weight ratio of mixture A to mixture B is 1:1.
[0034] The preparation method is as follows: (1) Tungsten and rhenium are mixed to obtain tungsten-rhenium pre-alloy powder, tungsten carbide and metal elements are mixed into the tungsten-rhenium pre-alloy powder, and the mixture is ball-milled to obtain the mixture A; tungsten powder and metal elements are mixed and ball-milled to obtain the mixture B; the mixture A is hydrogen-reduced to obtain a composite powder with low oxygen content; the mixture B is hydrogen-reduced to obtain a composite powder with low oxygen content; the specific process of the hydrogen reduction treatment is: hydrogen reduction at a reduction temperature of 1000℃ for 1 h; (2) The hydrogen-reduced mixture A, the mixture of mixture A and mixture B, and mixture B are layered and laid out, wherein the mass ratio of layer A, the mixed layer of A and B, and layer B are 45:5:50. Under a protective atmosphere, hot pressing sintering is carried out at a temperature of 1800℃ and a pressure of 100 MPa. The holding time is 0.5 h. After cooling, the heterogeneous tungsten-rhenium alloy is obtained.
[0035] Example 3 Compared with Example 2, the only difference is that the metal elements used in the tungsten-rhenium alloy layer, the gradient transition layer, and the pure tungsten layer are different, and lanthanum powder is used instead.
[0036] Example 4 Compared with Example 2, the only difference is the selection of parameters for hot pressing sintering in step (2) of the preparation process. The hot pressing sintering temperature is 2000℃, the hot pressing sintering pressure is 60MPa, and the holding time is 3h.
[0037] Example 5 Compared with Example 2, the only difference is the selection of parameters for hot pressing sintering in step (2) of the preparation process. The hot pressing sintering temperature is 1500℃, the hot pressing sintering pressure is 100MPa, and the holding time is 3h.
[0038] Example 6 Compared with Example 2, the only difference is the selection of parameters for hot pressing sintering in step (2) of the preparation process. The hot pressing sintering temperature is 2200℃, the hot pressing sintering pressure is 30MPa, and the holding time is 2h.
[0039] Example 7 Compared with Example 2, the only difference is the selection of mixture A and mixture B, while the preparation method is exactly the same, and the mass ratio of layer A, the mixed layer of A and B, and layer B are 45:5:50 respectively; Specifically, the tungsten-rhenium alloy layer includes a mixture A, which comprises the following components by mass percentage: 18% rhenium, 8% tungsten carbide, 0.5% metallic element (yttrium powder), and the balance being tungsten; The pure tungsten layer includes a mixture B, which comprises the following components by mass percentage: 0.3% metal element (yttrium powder) and the balance being tungsten.
[0040] The gradient transition layer comprises mixture A and mixture B; the weight ratio of mixture A to mixture B is 1:1.
[0041] Example 8 Compared with Example 2, the only difference is the weight ratio of mixture A and mixture B in the gradient transition layer. The weight ratio of mixture A and mixture B is 30:70. The preparation method is exactly the same, and the mass ratio of layer A, layer A and layer B is 45:5:50.
[0042] Example 9 Compared with Example 2, the only difference is the weight ratio of mixture A and mixture B in the gradient transition layer. The weight ratio of mixture A and mixture B is 40:60. The preparation method is exactly the same, and the mass ratio of layer A, layer A and layer B is 45:5:50.
[0043] Example 10 Compared with Example 2, the only difference is the weight ratio of mixture A and mixture B in the gradient transition layer. The weight ratio of mixture A and mixture B is 70:30. The preparation method is exactly the same, and the mass ratio of layer A, layer A and layer B is 45:5:50.
[0044] Comparative Example 1 Compared to Example 1, the only difference is that no metal element is added; The tungsten-rhenium alloy layer includes a mixture A, which comprises the following components in mass percentage: rhenium 23.75%, tungsten carbide 4%, and the balance being tungsten; The pure tungsten layer includes a mixture B, which comprises the following components by mass percentage: 100% tungsten powder.
[0045] Comparative Example 2 Compared with Example 1, the only difference is that the parameters for hot pressing sintering in step (2) of the preparation process are different, and no pressure treatment is performed; the sintering temperature is 1800℃, the sintering pressure is 0 MPa, and the holding time is 0.5h.
[0046] Performance testing Density test: The density was measured using the Archimedes method, and the test method met the national standard GB / T 10421-2025 Determination of density of sintered metal friction materials. The density was obtained by dividing the density measured by an analytical balance by the theoretical density.
[0047] Grain size test: The grain size was measured using the intercept method, and the test method met the national standard GB / T 6394-2017 Method for Determination of Average Grain Size of Metals. The calculation software was Image J.
[0048] Interface bond strength test: The bond strength was obtained by room temperature tensile test. The test conditions of the sample met the requirements of the national standard GB / T 7964-2020 for room temperature tensile testing of sintered metallic materials. The tensile strain rate was 0.0024 s⁻¹. -1 .
[0049] The test results are shown in Table 1.
[0050] Table 1 As shown in the table above, the tungsten-rhenium alloy layer and pure tungsten layer prepared by this invention have high density and fine grain size. The bonding strength between the two layers is between 580-823 MPa. Without the addition of an intermediate transition layer, the bonding strength between the two layers can reach 750 MPa, and with the addition of the intermediate transition layer, the bonding strength can be increased to a maximum of 823 MPa, significantly improving the bonding strength. In addition, all embodiments can save on the use of tungsten-rhenium alloy material, reducing the amount of tungsten-rhenium alloy used by ≥50%.
[0051] Figure 1 This is a schematic diagram of the heterogeneous tungsten-rhenium alloy prepared in Example 2 of the present invention; wherein, 1 is a pure tungsten layer, 2 is a gradient transition layer, and 3 is a tungsten-rhenium alloy layer; Figure 2 This is a photograph of the heterogeneous tungsten-rhenium alloy prepared in Example 1.
[0052] Figure 3 Metallographic images of the interface of the heterotungsten-rhenium alloy prepared in Example 1; Figure 4 The image shows an EDS image of the interface of the heterogeneous tungsten-rhenium alloy prepared in Example 1. As can be seen from the image, the tungsten-rhenium alloy and pure tungsten powder prepared in this invention are densely bonded and have very fine grains. There is a Re gradient layer between the tungsten-rhenium layer and the pure tungsten layer. This is an added transition layer added without manual powder spreading. It is thin and prone to stress concentration, thereby reducing the bonding force. Figure 5 The image shows the metallographic image of the interface of the heterogeneous tungsten-rhenium alloy prepared for Comparative Example 1. The prepared sample has a relatively large grain size. Figure 6 The image shows the metallographic structure of the heterogeneous tungsten-rhenium alloy interface prepared for Comparative Example 2. The prepared sample has a porous structure.
[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A heterogeneous tungsten-rhenium alloy, characterized in that, It includes a tungsten-rhenium alloy layer and a pure tungsten layer, which are adjacent to each other; the tungsten-rhenium alloy layer includes a mixture A, which includes the following components in mass percentage: rhenium 15-25%, tungsten carbide 3-10%, metallic elements 0.2-2%, and the balance being tungsten; And / or, the pure tungsten layer includes a mixture B, which comprises the following components in mass percentage: 0.2-2% metal elements, with the balance being tungsten.
2. The heterogeneous tungsten-rhenium alloy as described in claim 1, characterized in that, The metallic element is at least one of yttrium, lanthanum, cerium, and zirconium.
3. The heterogeneous tungsten-rhenium alloy as described in claim 1, characterized in that, It also includes a gradient transition layer located between the tungsten-rhenium alloy layer and the pure tungsten layer.
4. The heterogeneous tungsten-rhenium alloy as described in claim 3, characterized in that, The gradient transition layer comprises mixture A and mixture B; the weight ratio of mixture A to mixture B is (20-80):(80-20).
5. The heterojunction tungsten-rhenium alloy as described in claim 1 or 3, characterized in that, In the heterojunction tungsten-rhenium alloy, the gradient transition layer has a weight percentage of 1%-10%, the tungsten-rhenium alloy layer has a weight percentage of 10%-90%, and the pure tungsten layer has a weight percentage of 10%-90%.
6. A method for preparing a heterogeneous tungsten-rhenium alloy as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) Tungsten and rhenium are mixed to obtain tungsten-rhenium pre-alloy powder. Tungsten carbide and metal elements are mixed into the tungsten-rhenium pre-alloy powder and ball-milled to obtain mixture A. Tungsten powder and metal elements are mixed and ball-milled to obtain mixture B. (2) The hydrogen-reduced mixture A and mixture B are layered and laid out, and hot pressing sintering, spark plasma sintering or hot isostatic pressing is performed under a protective atmosphere. After cooling, the heterogeneous tungsten-rhenium alloy is obtained.
7. The method for preparing heterogeneous tungsten-rhenium alloy as described in claim 5, characterized in that, In step (2), the hot pressing sintering temperature is 1500-2200℃, the hot pressing sintering pressure is 20-100Mpa, and the holding time is 0.5-3h.
8. The application of a heterogeneous tungsten-rhenium alloy as described in any one of claims 1-5 in the field of ultra-high temperature structural components and wear-resistant parts.