Zirconium boride reinforced beryllium-based composite material and preparation method thereof
By preparing zirconium boride-reinforced beryllium-based composite materials, the problems of insufficient plasticity and strength of beryllium-based alloys in extreme environments have been solved, achieving high density and excellent room temperature and high temperature performance, which is suitable for high-temperature components in aerospace.
Patent Information
- Application Number
- CN202511306120.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-12
- Publication Date
- 2026-01-20
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The application of beryllium-based alloys in extreme environments is limited, mainly due to their poor room temperature plastic deformation ability and significant strength reduction at high temperatures.
A zirconium boride-reinforced beryllium-based composite material with a uniform fine-grained structure is prepared by mixing zirconium boride powder and beryllium powder, followed by ball milling, cold isostatic pressing, primary sintering, and secondary sintering. The sintering process is controlled to ensure the high density and high strength of the material.
This improves the room temperature plastic deformation capacity and high temperature strength retention of beryllium-based composite materials, meeting the requirements of high-temperature aerospace components, and at a low cost.
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of beryllium-based alloy processing, and particularly relates to a zirconium boride reinforced beryllium-based composite material and a preparation method thereof. BACKGROUND
[0002] The beryllium-based alloy has irreplaceability in the fields of aerospace (such as satellite structural parts), nuclear reactors (neutron reflectors) and high-precision optical devices due to its extremely low density (1.85 g / cm 3 ), excellent specific stiffness (elastic modulus / density ratio), excellent thermal stability (linear expansion coefficient as low as 11.4 x 10 -6 / K) and neutron moderation capacity. However, the hexagonal close-packed (HCP) crystal structure of beryllium leads to poor room temperature plastic deformation capability (elongation < 3%) and significant strength reduction at high temperatures (> 500 DEG C), which seriously restricts its application in extreme environments. SUMMARY
[0003] One of the purposes of the present application is to provide a preparation method of a zirconium boride reinforced beryllium-based composite material, which has a large relative density, good room temperature plastic deformation capability, large room temperature tensile strength and high strength retention rate at high temperatures (> 500 DEG C), and low cost.
[0004] The second purpose of the present application is to provide a zirconium boride reinforced beryllium-based composite material.
[0005] In order to achieve one of the above purposes, the present application adopts the following technical solutions:
[0006] A preparation method of a zirconium boride reinforced beryllium-based composite material, the preparation method comprising the following steps:
[0007] Step S1, mixing zirconium boride powder and beryllium powder, and then ball milling to obtain a uniform composite powder;
[0008] Step S2, sequentially performing cold isostatic pressing, first sintering, second sintering and natural cooling on the uniform composite powder to obtain the zirconium boride reinforced beryllium-based composite material.
[0009] Further, in the step S1, the mass ratio of the zirconium boride powder and the beryllium powder is 1-10: 90-99.
[0010] Further, in the step S1, the mass ratio of the zirconium boride powder and the beryllium powder is 4-6: 94-96.
[0011] Further, in the step S1, the ball milling time is 4-24 h.
[0012] Further, in the step S2, the pressure of the cold isostatic pressing is 195-205 MPa.
[0013] Further, in the step S2, the specific process of the first sintering is as follows:
[0014] The composite material blank obtained after the cold isostatic pressing is heated to 550-650 DEG C under an argon atmosphere and sintered for 30-60 min.
[0015] Further, in the step S2, the specific process of the second sintering is as follows:
[0016] The composite material blank after the first sintering is heated to 1050-1200 DEG C under a vacuum condition with a vacuum degree less than 10 -3 Pa and sintered for 90-160 min.
[0017] In order to achieve the above-mentioned second purpose, the present application adopts the following technical scheme:
[0018] A zirconium diboride reinforced beryllium matrix composite material is prepared by the preparation method.
[0019] Further, the relative density of the zirconium diboride reinforced beryllium matrix composite material is 96-98.2%, the tensile strength at room temperature is greater than 400 MPa, the elongation is greater than or equal to 4%, and the strength retention rate at 500 DEG C is >80%.
[0020] In summary, the scheme of the present application has the following technical effects:
[0021] The present application forms a low-temperature stable beryllium matrix composite material blank with an open hole structure through the first sintering, which facilitates the gas escape during the final sintering and avoids the local overheating during the final sintering, which leads to the rapid grain growth; the present application realizes the near full densification (>98% TD) of the beryllium matrix composite material at a higher temperature through the second sintering, reduces the residual porosity, and improves the mechanical properties (such as the tensile strength and the fatigue life) of the beryllium matrix composite material; the present application utilizes the pinning effect of ZrB2 to maintain the dispersion distribution during the first sintering and the second sintering, further hinders the grain boundary migration, obtains a uniform fine-grained structure, improves the strength and toughness of the beryllium matrix composite material, and improves the sintering density of the zirconium diboride reinforced beryllium matrix composite material; the relative density of the zirconium diboride reinforced beryllium matrix composite material of the present application is 96-98.2%, the tensile strength at room temperature is greater than 400 MPa, the plastic deformation capacity at room temperature is good (i.e., the elongation is greater than or equal to 4%), the brittleness of the beryllium matrix alloy is improved, the strength retention rate at 500 DEG C is >80%, the high-temperature performance is stable, the cost is low, and the demand of aerospace high-temperature components is met. DETAILED DESCRIPTION
[0022] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.
[0023] The present embodiment provides a preparation method of a zirconium diboride reinforced beryllium matrix composite material, which comprises the following steps:
[0024] In step S1, the zirconium diboride powder and the beryllium powder are mixed and then ball milled to obtain a uniform composite powder.
[0025] In the present embodiment, a small amount of zirconium diboride powder is added to uniformly disperse ZrB2 particles (nano / micron) in the beryllium matrix, hinder dislocation movement, inhibit beryllium grain growth, refine grains, thereby improving the room temperature and high temperature strength (yield strength, creep resistance) of the beryllium matrix composite material, enhancing the toughness of the beryllium matrix composite material, improving the strength retention rate of the beryllium matrix composite material at 500°C, and being suitable for ultra-high temperature environments (such as rocket nozzles and nuclear reactor components). Meanwhile, ZrO2+B2O3 generated by the oxidation of ZrB2 at high temperatures forms a dense oxide layer to prevent oxygen from further diffusing to the beryllium matrix, delay the oxidation rate of the beryllium matrix, improve the service life of the beryllium matrix composite material in high-temperature oxidation environments (such as atmospheric reentry vehicle thermal protection), reduce the generation of toxic oxides (BeO) of beryllium, and improve safety.
[0026] In the present embodiment, the mass ratio of the zirconium diboride powder to the beryllium powder is 1-10:90-99, and preferably 4-6:94-96.
[0027] In the present embodiment, the ball milling time is 4-24h, and preferably 10-16h.
[0028] In step S2, the uniform composite powder is sequentially subjected to cold isostatic pressing, primary sintering, secondary sintering and natural cooling to obtain a zirconium diboride reinforced beryllium matrix composite material.
[0029] Since the beryllium powder has high hardness and poor plasticity, a higher pressure is required to realize close packing between particles, reduce porosity and improve the density of the beryllium blank. As a hard ceramic phase, ZrB2 needs sufficient pressure to uniformly embed with the beryllium powder to avoid deformation or cracking due to uneven density during subsequent sintering. However, too high pressure will harden the surface of beryllium particles, thereby inhibiting sintering densification, and too high pressure increases equipment load and cost. Therefore, the present embodiment adopts a pressure of 195-205MPa for cold isostatic pressing.
[0030] The specific process of the primary sintering in the present embodiment is as follows:
[0031] The composite blank obtained after cold isostatic pressing is heated to 550-650℃ under argon atmosphere and sintered for 30-60min.
[0032] The present embodiment preliminarily removes residual stress and partially densifies through one-time sintering, avoiding deformation or cracking caused by direct high-temperature sintering. At the same time, the composite blank after cold isostatic pressing forms an open-pore structure, facilitating gas escape during final sintering. The low-temperature stable blank obtained after one-time sintering avoids local overheating during final sintering, which leads to rapid grain growth, reduces interface reaction (e.g., formation of brittle Be2Zr phase) during final sintering, and eliminates adsorbed gas (e.g., H2O, O2) in the blank at a lower temperature, reducing pores and oxidation during final sintering.
[0033] The specific process of the secondary sintering in the present embodiment is as follows:
[0034] The composite blank after one-time sintering is heated to 1050-1200℃ under vacuum condition with a vacuum degree less than 10 -3 Pa and sintered for 90-160min.
[0035] In order to avoid that neither too high nor too low temperature can promote the sintering process or cause over-sintering, the temperature of the secondary sintering (i.e., high-vacuum sintering) in the present embodiment is controlled at 1050-1200℃, achieving complete densification and optimizing the interface bonding of ZrB / Be.
[0036] The present embodiment forms a low-temperature stable beryllium-based composite blank with an open-pore structure through one-time sintering, facilitating gas escape during final sintering and avoiding local overheating during final sintering, which leads to rapid grain growth. The present embodiment enables the beryllium-based composite to achieve near-full densification (>98% TD) at a higher temperature through secondary sintering, reducing residual porosity and improving the mechanical properties (e.g., tensile strength and fatigue life) of the beryllium-based composite. The present embodiment utilizes the pinning effect of ZrB2 to maintain a dispersed distribution during one-time sintering and secondary sintering, further hindering grain boundary migration, obtaining a uniform fine-grained structure, improving the strength and toughness of the beryllium-based composite, and increasing the sintering density of the zirconium boride reinforced beryllium-based composite. The relative density of the zirconium boride reinforced beryllium-based composite of the present embodiment is 96-98.2%, the room-temperature tensile strength is greater than 400MPa, the room-temperature plastic deformation capability is good (i.e., elongation is greater than or equal to 4%), the brittleness of the beryllium-based alloy is improved, the strength retention rate at 500℃ is >80%, the high-temperature performance is stable, the cost is low, and the demand of aerospace high-temperature components is met.
[0037] Another embodiment provides a zirconium boride reinforced beryllium-based composite prepared by the preparation method given in the above embodiments.
[0038] The relative density of the zirconium boride reinforced beryllium matrix composite material of the embodiment is 96-98.2%, the tensile strength at room temperature is greater than 400 MPa, the elongation is greater than or equal to 4%, and the strength retention rate at 500 DEG C is greater than 80%.
[0039] The technical scheme of the present application is described below with specific embodiments:
[0040] Embodiment 1:
[0041] Step S1, the zirconium boride powder and the beryllium powder are mixed uniformly by a ball mill at a mass ratio of 4:96, and then ball-milled for 8 hours to obtain a uniform composite powder.
[0042] Step S2, the uniform composite powder is cold isostatic pressed by a pressure of 200 MPa, and the composite material blank obtained after cold isostatic pressing is heated to 550 DEG C under an argon atmosphere, and then sintered for 30 minutes, and then the composite material blank after primary sintering is heated to 1100 DEG C under a vacuum condition with a vacuum degree less than 10 -3 Pa, and then sintered for 90 minutes, and then naturally cooled after sintering to obtain a zirconium boride reinforced beryllium alloy.
[0043] The relative density of the zirconium boride reinforced beryllium matrix composite material of the embodiment is 97.5%, the tensile strength at room temperature is 405 MPa, the elongation is 4.2%, and the strength retention rate at 500 DEG C is 84%.
[0044] Embodiment 2:
[0045] Step S1, the zirconium boride powder and the beryllium powder are mixed uniformly by a ball mill at a mass ratio of 10:90, and then ball-milled for 24 hours to obtain a uniform composite powder.
[0046] Step S2, the uniform composite powder is cold isostatic pressed by a pressure of 205 MPa, and the composite material blank obtained after cold isostatic pressing is heated to 600 DEG C under an argon atmosphere, and then sintered for 50 minutes, and then the composite material blank after primary sintering is heated to 1200 DEG C under a vacuum condition with a vacuum degree less than 10 -3 Pa, and then sintered for 120 minutes, and then naturally cooled after sintering to obtain a zirconium boride reinforced beryllium alloy.
[0047] The relative density of the zirconium boride reinforced beryllium matrix composite material of the embodiment is 98.2%, the tensile strength at room temperature is 402 MPa, the elongation is 4.1%, and the strength retention rate at 500 DEG C is 87%.
[0048] Embodiment 3:
[0049] Step S1, the zirconium boride powder and the beryllium powder are mixed uniformly by a ball mill at a mass ratio of 1:99, and then ball-milled for 4 hours to obtain a uniform composite powder.
[0050] Step S2, the uniform composite powder is cold isostatic pressed by using the pressure of 195MPa, and the composite material blank obtained after cold isostatic pressing is heated to 650℃ under argon atmosphere, and after one-time sintering for 60min, the composite material blank after one-time sintering is heated to 1050℃ under the vacuum condition of the vacuum degree less than 10 -3 Pa, and after two-time sintering for 160min, the sintered composite material is naturally cooled to obtain the beryllium alloy reinforced by zirconium boride.
[0051] The relative density of the zirconium boride reinforced beryllium matrix composite material of the embodiment is 96%, the tensile strength at room temperature is 400MPa, the elongation is 4.0%, and the strength retention rate at 500℃ is 80%.
[0052] The above embodiments only express several implementation manners of the application, and the description is relatively specific and detailed, but it should not be understood as the limitation to the patent scope of the application. It should be pointed out that, for the ordinary skilled in the art, several modifications and improvements can be made without departing from the concept of the application, and these all belong to the protection scope of the application. Therefore, the patent protection scope of the application should be subject to the appended claims.
Claims
1. A method of producing a zirconium diboride reinforced beryllium matrix composite material, characterized in that, The preparation method comprises the following steps: Step S1, mixing zirconium boride powder and beryllium powder, and then ball milling to obtain a uniform composite powder; Step S2, sequentially performing cold isostatic pressing, primary sintering, secondary sintering and natural cooling on the uniform composite powder to obtain a zirconium boride reinforced beryllium matrix composite material.
2. The production method according to claim 1, characterized by, In the step S1, the mass ratio of the zirconium boride powder to the beryllium powder is 1-10:90-99.
3. The production method according to claim 2, characterized by, In the step S1, the mass ratio of the zirconium boride powder to the beryllium powder is 4-6:94-96.
4. The production method according to claim 3, characterized by, In the step S1, the ball milling time is 4-24h.
5. The production method according to any one of claims 1 to 4, characterized by, In the step S2, the cold isostatic pressing pressure is 195-205MPa.
6. The production method according to claim 5, wherein In the step S2, the specific process of the primary sintering is as follows: Under an argon atmosphere, the composite material blank obtained after cold isostatic pressing is heated to 550-650℃, and sintered for 30-60min.
7. The preparation method according to claim 6, characterized in that, In the step S2, the specific process of the secondary sintering is as follows: The vacuum degree is less than 10 -3 The composite material blank after the first sintering is heated to 1050-1200℃ under a vacuum condition with a vacuum degree less than 10 Pa, and sintered for 90-160 min.
8. A zirconium diboride reinforced beryllium matrix composite, characterized in that, The zirconium boride reinforced beryllium matrix composite material is prepared by the preparation method in any one of claims 1-7.
9. The zirconium boride reinforced beryllium matrix composite of claim 8, wherein, The relative density of the zirconium boride reinforced beryllium matrix composite material is 96-98.2%, the tensile strength at room temperature is greater than 400MPa, the elongation is greater than or equal to 4%, and the strength retention rate at 500℃ is >80%.