A cerium-reinforced rhenium alloy material and preparation method thereof

Abstract

The present invention discloses a cerium-reinforced rhenium alloy material and a preparation method thereof, relating to the technical field of rhenium alloy materials. The cerium-reinforced rhenium alloy material comprises the following components, measured by mass percentage: 10-25wt% molybdenum, 0.5-1.2wt% nickel, 1-3wt% manganese, 0.2-0.5wt% iridium, 0.003-0.008wt% indium, 0.01-0.04wt% tantalum, 1-3wt% aluminum, 0.05-0.15wt% scandium, 0.2-0.6wt% tungsten, 0.01-4wt% cerium oxide, 0.005-0.01wt% other rare earth elements, 0.001-0.004wt% nanofiller, and the balance being molybdenum and other inevitable impurities. The cerium-reinforced rhenium alloy material disclosed by the present invention has high high-temperature strength, good heat resistance and high hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of rhenium alloy materials, and in particular to a cerium-reinforced rhenium alloy material and a preparation method thereof. Background Art

[0002] MOCVD (a novel vapor phase epitaxial growth technology) is an important method for manufacturing semiconductor materials, devices, and thin films, with crucial applications in the chip manufacturing industry. The rhenium heating coils used in MOCVD require rapid heating and cooling. However, rhenium has a relatively high coefficient of thermal expansion, which can easily cause irreversible deformation during rapid heating and cooling, affecting heating performance and service life. While replacing pure rhenium with existing rhenium alloys improves these properties, they still suffer from insufficient high-temperature strength, an excessively high coefficient of thermal expansion, and the alloy's Vickers hardness needs to be further improved.

[0003] To address the above issues, patent document CN 106756157 B provides a method for preparing a molybdenum-rhenium-lanthanum alloy material, comprising the following steps: 1. Designing the composition of the molybdenum-rhenium-lanthanum alloy material, and then weighing nano-lanthanum oxide powder, rhenium powder, and molybdenum dioxide powder according to the designed composition; 2. Weighing the nano-lanthanum oxide powder again; 3. Mixing the nano-lanthanum oxide powders weighed in steps 1 and 2 uniformly, adding them to deionized water, dispersing them, and filtering to obtain a filtrate; 4. Adding the rhenium powder to the filtrate, dispersing them to obtain a mixed solution, which is then added to the molybdenum dioxide powder; 5. Reducing them using hydrogen to obtain a reduced material, sieving them, and mixing them to obtain a reduced alloy powder; 6. Isostatic pressing to obtain a compact, which is then sintered to obtain the molybdenum-rhenium-lanthanum alloy material. The alloy material of the invention has uniform and fine particles, fine grains in the slab fracture, clear and pure grain boundaries, and no visible agglomerated second-phase particles at the grain boundaries or within the grains, indicating that the nanoparticles in the alloy material of the invention are well dispersed and meet the technical requirements. However, its high temperature strength and thermal stability still need to be further improved. Summary of the Invention

[0004] The main purpose of the present invention is to provide a cerium-reinforced rhenium alloy material with high high-temperature strength, good heat-resistant stability and high hardness, and a preparation method thereof.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: a cerium-reinforced rhenium alloy material, which comprises the following components by mass percentage: 0.01-4wt% of cerium oxide, and the balance is rhenium and other inevitable impurities.

[0006] Preferably, the cerium-reinforced rhenium alloy material also includes the following components: 10-25wt% molybdenum, 0.5-1.2wt% nickel, 1-3wt% manganese, 0.2-0.5wt% iridium, 0.003-0.008wt% indium, 0.01-0.04wt% tantalum, 1-3wt% aluminum, 0.05-0.15wt% scandium, 0.2-0.6wt% tungsten, 0.005-0.01wt% other rare earth elements, and 0.001-0.004wt% nanofiller; the other rare earth elements are a mixture of cerium, dysprosium, and neodymium in a mass ratio of (2-4):(0.5-1.1):(0.1-0.3).

[0007] Preferably, the particle size of the nanofiller is 30-90 nm.

[0008] Preferably, the nanofiller is a mixture of zirconium oxide, boron carbide, and silicon boride in a mass ratio of (1-3):1:(0.8-1.2).

[0009] The present invention also provides a method for preparing the cerium-reinforced rhenium alloy material, comprising the following steps:

[0010] Step 1, ball milling: Mix the ingredients according to weight to obtain a mixture, place the mixture in a ball mill, add anhydrous ethanol as a process control agent, and ball mill for 25 to 30 hours. After drying, place the mixture in an agate mortar and grind for 30 to 40 minutes;

[0011] Step 2: Deoxidation treatment: Deoxidation treatment is performed on the powder after ball milling;

[0012] Step 3, isostatic pressing and sintering: the deoxidized powder is subjected to isostatic pressing to obtain a compact, which is then placed in a sintering furnace for sintering to obtain a cerium-reinforced rhenium alloy material.

[0013] Preferably, the mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:(6-10).

[0014] Preferably, the drying temperature in step 1 is 60-80° C. and the drying time is 6-8 h.

[0015] Preferably, the deoxidation treatment in step 2 is specifically as follows: placing the ball-milled powder in a vacuum glove box, setting the temperature to 78-92° C., introducing nitrogen, maintaining the nitrogen pressure at 0.095 MPa-0.11 MPa, maintaining the pressure for 3-5 hours, and completing the treatment, sealing and setting aside.

[0016] Preferably, the pressing force of the isostatic pressing in step 3 is 120 MPa to 250 MPa, and the holding time of the isostatic pressing is 0.5 min to 10 min.

[0017] Preferably, the sintering in step 3 is carried out at a hydrogen flow rate of 3 to 6 m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 850~1350℃, and the time is 1-3h; the high-temperature sintering temperature is 1950~2450℃, and the time is 10-18h.

[0018] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0019] (1) The preparation method of the cerium-enhanced rhenium alloy material provided by the present invention has a simple process, convenient operation, high preparation efficiency and finished product qualification rate, does not require special equipment, and does not require modification of existing production. It has low energy consumption and is suitable for industrial production.

[0020] (2) The cerium-enhanced rhenium alloy material provided by the present invention comprises the following components, in percentage by mass: 10-25 wt% of molybdenum, 0.5-1.2 wt% of nickel, 1-3 wt% of manganese, 0.2-0.5 wt% of iridium, 0.003-0.008 wt% of indium, 0.01-0.04 wt% of tantalum, 1-3 wt% of aluminum, 0.05-0.15 wt% of scandium, 0.2-0.6 wt% of tungsten, 0.01-4 wt% of cerium oxide, 0.005-0.01 wt% of other rare earth elements, 0.001-0.004 wt% of nanofillers, and the balance being rhenium and other inevitable impurities; by rationally selecting the types and formulas of the components, the components can better exert synergy, and they cooperate with each other and work together, so that the cerium-enhanced rhenium alloy material has high high-temperature strength, good heat resistance and stability, and high hardness.

[0021] (3) The cerium-reinforced rhenium alloy material provided by the present invention has cerium oxide particles pinned around the powder particles. During the sintering process, these cerium oxide particles greatly increase the driving energy required for grain boundary movement, hinder grain boundary movement at high temperatures, thereby achieving the effect of improving high-temperature strength and reducing its thermal expansion coefficient.

[0022] (4) The cerium element reinforced rhenium alloy material provided by the present invention comprises a nanofiller which is a mixture of zirconium oxide, boron carbide and silicon boride in a mass ratio of (1-3):1:(0.8-1.2); through the interaction between its components, adding the nanofiller to the alloy material can make the material structure denser and form solid solution strengthening; through the selection of size and component type, the surface and interface effects, small size effect, quantum size effect and macroscopic quantum tunneling effect of the nanomaterial can be fully utilized, so that they can be uniformly dispersed in the alloy matrix, thereby improving performance stability and thereby improving high temperature strength and high temperature resistant dimensional stability.

[0023] (5) The cerium-reinforced rhenium alloy material provided by the present invention comprises a mixture of cerium, dysprosium, and neodymium in a mass ratio of (2-4):(0.5-1.1):(0.1-0.3). By rationally selecting the components and proportions, the addition of the cerium-reinforced rhenium alloy material to the alloy material further enhances the high-temperature strength and reduces its thermal expansion coefficient. By rationally selecting the preparation process, the resulting alloy material exhibits excellent overall performance and stability, a high cost-effectiveness, and high economic and social value. DETAILED DESCRIPTION

[0024] The following description is intended to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are merely examples, and those skilled in the art may conceive of other obvious variations.

[0025] Example 1

[0026] A cerium-reinforced rhenium alloy material comprises the following components, calculated by mass percentage: 1wt% of cerium oxide, and the balance of rhenium and other inevitable impurities.

[0027] A method for preparing the cerium-strengthened rhenium alloy material comprises the following steps:

[0028] Step 1, ball milling: Mix the ingredients according to weight to obtain a mixture, place the mixture in a ball mill, add anhydrous ethanol as a process control agent, and ball mill for 25 hours. After drying, place the mixture in an agate mortar and grind for 30 minutes;

[0029] Step 2: Deoxidation treatment: Deoxidation treatment is performed on the powder after ball milling;

[0030] Step 3, isostatic pressing and sintering: the deoxidized powder is subjected to isostatic pressing to obtain a compact, which is then placed in a sintering furnace for sintering to obtain a cerium-reinforced rhenium alloy material.

[0031] The mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:6; the drying temperature in step 1 is 60°C and the time is 6h; the deoxidation treatment in step 2 is specifically as follows: the powder after ball milling is placed in a vacuum glove box, the temperature is set to 78°C, nitrogen is introduced, and the nitrogen pressure is maintained at 0.095Mpa for 3 hours. After the treatment is completed, it is sealed and set aside; the pressing force of the isostatic pressing in step 3 is 180MPa, and the holding time of the isostatic pressing is 1min.

[0032] The sintering in step 3 is carried out at a hydrogen flow rate of 3m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 1150°C and the time is 1h; the high-temperature sintering temperature is 1950°C and the time is 10h.

[0033] Example 2

[0034] A cerium-reinforced rhenium alloy material comprises the following components, calculated by mass percentage: 15 wt% molybdenum, 0.7 wt% nickel, 1.5 wt% manganese, 0.3 wt% iridium, 0.005 wt% indium, 0.02 wt% tantalum, 1.5 wt% aluminum, 0.07 wt% scandium, 0.3 wt% tungsten, 2 wt% cerium oxide, 0.007 wt% other rare earth elements, 0.002 wt% nanofiller, and the balance being rhenium and other unavoidable impurities.

[0035] The other rare earth elements are a mixture of cerium, dysprosium and neodymium in a mass ratio of 2.5:0.7:0.15; the particle size of the nanofiller is 50 nm; and the nanofiller is a mixture of zirconium oxide, boron carbide and silicon boride in a mass ratio of 1.5:1:0.9.

[0036] A method for preparing the cerium-strengthened rhenium alloy material comprises the following steps:

[0037] Step 1, ball milling: The components were mixed according to weight to obtain a mixture, which was placed in a ball mill. Anhydrous ethanol was added as a process control agent, and the mixture was ball milled for 26 hours. After drying, the mixture was placed in an agate mortar and ground for 33 minutes.

[0038] Step 2: Deoxidation treatment: Deoxidation treatment is performed on the powder after ball milling;

[0039] Step 3, isostatic pressing and sintering: the deoxidized powder is subjected to isostatic pressing to obtain a compact, which is then placed in a sintering furnace for sintering to obtain a cerium-reinforced rhenium alloy material.

[0040] The mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:7; the drying temperature in step 1 is 65° C. and the drying time is 6.5 h.

[0041] The deoxidation treatment in step 2 is specifically as follows: the ball-milled powder is placed in a vacuum glove box, the temperature is set to 83° C., nitrogen is introduced, and the nitrogen pressure is maintained at 0.099 MPa for 3.5 hours. After the treatment is completed, the box is sealed and set aside.

[0042] The pressing force of the isostatic pressing in step 3 is 120 MPa, and the holding time of the isostatic pressing is 2 min; the sintering in step 3 is carried out at a hydrogen flow rate of 4 m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 950°C and the time is 1.5h; the high-temperature sintering temperature is 1970°C and the time is 12h.

[0043] Example 3

[0044] A cerium-reinforced rhenium alloy material comprises the following components, calculated by mass percentage: 19 wt% molybdenum, 0.9 wt% nickel, 2 wt% manganese, 0.35 wt% iridium, 0.006 wt% indium, 0.025 wt% tantalum, 2 wt% aluminum, 0.1 wt% scandium, 0.4 wt% tungsten, 3 wt% cerium oxide, 0.008 wt% other rare earth elements, 0.0025 wt% nanofiller, and the balance being rhenium and other unavoidable impurities.

[0045] The other rare earth elements are a mixture of cerium, dysprosium and neodymium in a mass ratio of 3:0.9:0.2; the particle size of the nanofiller is 70 nm; and the nanofiller is a mixture of zirconium oxide, boron carbide and silicon boride in a mass ratio of 2:1:1.

[0046] A method for preparing the cerium-strengthened rhenium alloy material comprises the following steps:

[0047] Step 1, ball milling: Mix the ingredients according to weight to obtain a mixture, place the mixture in a ball mill, add anhydrous ethanol as a process control agent, and ball mill for 28 hours. After drying, grind in an agate mortar for 35 minutes;

[0048] Step 2: Deoxidation treatment: Deoxidation treatment is performed on the powder after ball milling;

[0049] Step 3, isostatic pressing and sintering: the deoxidized powder is subjected to isostatic pressing to obtain a compact, which is then placed in a sintering furnace for sintering to obtain a cerium-reinforced rhenium alloy material.

[0050] The mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:8; the drying temperature in step 1 is 70° C. and the drying time is 7 hours.

[0051] The deoxidation treatment in step 2 is specifically as follows: the ball-milled powder is placed in a vacuum glove box, the temperature is set to 88° C., nitrogen is introduced, and the nitrogen pressure is maintained at 0.1 MPa for 4 hours. After the treatment is completed, the box is sealed and set aside.

[0052] The pressing force of the isostatic pressing in step 3 is 150 MPa, and the holding time of the isostatic pressing is 6 min; the sintering in step 3 is carried out at a hydrogen flow rate of 4.5 m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 1000°C and the time is 2h; the high-temperature sintering temperature is 2050°C and the time is 15h.

[0053] Example 4

[0054] A cerium-reinforced rhenium alloy material comprises the following components, calculated by mass percentage: 23 wt% molybdenum, 1.1 wt% nickel, 2.5 wt% manganese, 0.45 wt% iridium, 0.007 wt% indium, 0.035 wt% tantalum, 2.5 wt% aluminum, 0.13 wt% scandium, 0.5 wt% tungsten, 3.5 wt% cerium oxide, 0.009 wt% other rare earth elements, 0.0035 wt% nanofiller, and the balance being rhenium and other unavoidable impurities.

[0055] The other rare earth elements are a mixture of cerium, dysprosium and neodymium in a mass ratio of 3.5:1:0.25; the particle size of the nanofiller is 80 nm; and the nanofiller is a mixture of zirconium oxide, boron carbide and silicon boride in a mass ratio of 2.5:1:1.1.

[0056] A method for preparing the cerium-strengthened rhenium alloy material comprises the following steps:

[0057] Step 1, ball milling: The components were mixed according to weight to obtain a mixture, which was placed in a ball mill, and anhydrous ethanol was added as a process control agent. The mixture was ball milled for 29 hours. After drying, the mixture was placed in an agate mortar and ground for 39 minutes.

[0058] Step 2: Deoxidation treatment: Deoxidation treatment is performed on the powder after ball milling;

[0059] Step 3, isostatic pressing and sintering: the deoxidized powder is subjected to isostatic pressing to obtain a compact, which is then placed in a sintering furnace for sintering to obtain a cerium-reinforced rhenium alloy material.

[0060] The mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:9.5; the drying temperature in step 1 is 75° C. and the drying time is 7.5 h.

[0061] The deoxidation treatment in step 2 is specifically as follows: the ball-milled powder is placed in a vacuum glove box, the temperature is set to 90° C., nitrogen is introduced, and the nitrogen pressure is maintained at 0.105 MPa for 4.5 hours. After the treatment is completed, the box is sealed and set aside.

[0062] The pressing force of the isostatic pressing in step 3 is 210 MPa, and the holding time of the isostatic pressing is 5 min; the sintering in step 3 is carried out at a hydrogen flow rate of 5.5 m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 1220°C and the time is 2.5h; the high-temperature sintering temperature is 2230°C and the time is 17h.

[0063] Example 5

[0064] A cerium-reinforced rhenium alloy material comprises the following components, calculated by mass percentage: 25 wt% molybdenum, 1.2 wt% nickel, 3 wt% manganese, 0.5 wt% iridium, 0.008 wt% indium, 0.04 wt% tantalum, 3 wt% aluminum, 0.15 wt% scandium, 0.6 wt% tungsten, 4 wt% cerium oxide, 0.01 wt% other rare earth elements, 0.004 wt% nanofiller, and the balance being rhenium and other unavoidable impurities.

[0065] The other rare earth elements are a mixture of cerium, dysprosium and neodymium in a mass ratio of 4:1.1:0.3; the particle size of the nanofiller is 90 nm; and the nanofiller is a mixture of zirconium oxide, boron carbide and silicon boride in a mass ratio of 3:1:1.2.

[0066] A method for preparing the cerium-strengthened rhenium alloy material comprises the following steps:

[0067] Step 1, ball milling: Mix the ingredients according to weight to obtain a mixture, place the mixture in a ball mill, add anhydrous ethanol as a process control agent, and ball mill for 30 hours. After drying, place the mixture in an agate mortar and grind for 40 minutes;

[0068] Step 2: Deoxidation treatment: Deoxidation treatment is performed on the powder after ball milling;

[0069] Step 3, isostatic pressing and sintering: the deoxidized powder is subjected to isostatic pressing to obtain a compact, which is then placed in a sintering furnace for sintering to obtain a cerium-reinforced rhenium alloy material.

[0070] The mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:10; the drying temperature in step 1 is 80° C. and the drying time is 8 hours.

[0071] The deoxidation treatment in step 2 is specifically as follows: the ball-milled powder is placed in a vacuum glove box, the temperature is set to 92°C, nitrogen is introduced, and the nitrogen pressure is maintained at 0.11 MPa for 5 hours. After the treatment is completed, the product is sealed and set aside. The pressing force of the isostatic pressing in step 3 is 240 MPa, and the holding time of the isostatic pressing is 10 min.

[0072] The sintering in step 3 is carried out at a hydrogen flow rate of 6m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 1350°C and the time is 3h; the high-temperature sintering temperature is 2400°C and the time is 18h.

[0073] Comparative Example 1

[0074] This example provides a cerium-reinforced rhenium alloy material, the formulation and preparation method of which are substantially the same as those of Example 1, except that iridium, indium, and cerium oxide are not added.

[0075] Comparative Example 2

[0076] This example provides a cerium-reinforced rhenium alloy material, the formulation and preparation method of which are substantially the same as those of Example 1, except that scandium, other rare earth elements, and nanofillers are not added.

[0077] Comparative Example 3

[0078] This example provides a molybdenum-rhenium-cerium alloy, which is prepared according to the method of Example 1 in CN 106756157 B.

[0079] In order to illustrate the technical effects of the embodiments of the present invention, the relevant performance of each product was tested with reference to the current national standards of my country. The test results are shown in Table 1.

[0080] As can be seen from Table 1, the cerium-reinforced rhenium alloy material disclosed in the embodiment of the present invention has greater high-temperature strength and lower linear expansion coefficient, and greater hardness than the comparative example product. The addition of scandium, other rare earth elements, nanofillers, iridium, indium, and cerium oxide are all beneficial to improving the above-mentioned properties. The performance of the final product is the result of the synergistic effect of the various raw material components.

[0081] Table 1

[0082] project 1000℃ yield strength Vickers hardness Average linear expansion coefficient (20-1000℃) unit MPa Hv <![CDATA[×10 -6 / ℃]]> Example 1 1310 380 6.316 Example 2 1328 383 6.245 Example 3 1340 390 6.079 Example 4 1353 395 5.901 Example 5 1368 397 5.815 Comparative Example 1 1189 312 8.834 Comparative Example 2 1203 305 7.168 Comparative Example 3 1068 297 9.237

[0083] The above embodiments are only descriptions of the preferred embodiments of the present invention and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary engineering technicians in this field should fall within the scope of protection determined by the claims of the present invention.

Claims

1. A cerium-reinforced rhenium alloy material, characterized in that: The invention is made of the following components, calculated by mass percentage: 0.01-4wt% of cerium oxide, the balance of which is rhenium and other inevitable impurities; and the following components: 10-25wt% of molybdenum, 0.5-1.2wt% of nickel, 1-3wt% of manganese, 0.2-0.5wt% of iridium, 0.003-0.008wt% of indium, 0.01-0.04wt% of tantalum, 1-3wt% of aluminum, 0.05-0.15wt% of scandium, 0.2-0.6wt% of tungsten, 0.005-0.01wt% of other rare earth elements, and 0.001-0.004wt% of nanofiller. The other rare earth elements are a mixture of cerium, dysprosium, and neodymium in a mass ratio of (2-4):(0.5-1.1):(0.1-0.3); the particle size of the nanofiller is 30-90 nm; The nanofiller is a mixture of zirconium oxide, boron carbide and silicon boride in a mass ratio of (1-3):1:(0.8-1.2); The preparation method of the cerium element reinforced rhenium alloy material comprises the following steps: step 1, ball milling mixing: mixing the components by weight to obtain a mixed material, placing the mixed material in a ball mill, adding anhydrous ethanol as a process control agent, and ball milling for 25 to 30 hours. After drying, the mixed material is placed in an agate mortar and ground for 30 to 40 minutes; step 2, deoxidation treatment: deoxidizing the powder after the ball milling treatment; step 3, isostatic pressing and sintering: isostatic pressing the deoxidized powder to obtain a compact, and then placing the compact in a sintering furnace for sintering to obtain a cerium element reinforced rhenium alloy material; the sintering in step 3 is carried out at a hydrogen flow rate of 3 to 6 m 3 / h atmosphere; the sintering process includes pre-sintering and high-temperature sintering after the pre-sintering; the pre-sintering temperature is 850~1350℃, and the time is 1-3h; the high-temperature sintering temperature is 1950~2450℃, and the time is 10-18h.

2. The cerium-reinforced rhenium alloy material according to claim 1, characterized in that: The mass ratio of anhydrous ethanol to the mixed material in step 1 is 1:(6-10).

3. The cerium-reinforced rhenium alloy material according to claim 1, characterized in that: The drying temperature in step 1 is 60-80° C. and the drying time is 6-8 hours.

4. The cerium-reinforced rhenium alloy material according to claim 1, characterized in that: The deoxidation treatment in step 2 is specifically as follows: the ball-milled powder is placed in a vacuum glove box, the temperature is set to 78-92°C, nitrogen is introduced, and the nitrogen pressure is maintained at 0.095MPa-0.11MPa for 3-5 hours. After the treatment is completed, the powder is sealed and set aside.

5. The cerium-reinforced rhenium alloy material according to claim 4, characterized in that: The pressing force of the isostatic pressing in step 3 is 120 MPa to 250 MPa, and the holding time of the isostatic pressing is 0.5 min to 10 min.