Carbide dispersion strengthened molybdenum-rhenium alloy and preparation method thereof

Abstract

The invention relates to a carbide dispersion strengthened molybdenum-rhenium alloy and a preparation method thereof, and the carbide dispersion strengthened molybdenum-rhenium alloy comprises the following components in percentage by mass: 0.1-1.5% of carbide, 1-10% of rhenium and the balance of molybdenum, wherein the carbide is ZrC or TiC; the preparation method comprises the following steps that firstly, carbide, molybdenum powder and rhenium powder are prepared according to the proportion, ball milling is carried out under the inert protective atmosphere to form powder, cold pressing is carried out to form a blank, and the obtained blank is sintered at the high temperature to be compact; and secondly, deformation treatment is conducted on the sintered sample obtained in the first step under the high-temperature condition, and the carbide dispersion strengthened molybdenum-rhenium alloy is obtained after annealing. A small amount of rhenium is added into metal molybdenum, and a small amount of second-phase carbide particles are combined for dispersion strengthening, so that the strength of the molybdenum-rhenium alloy is synergistically improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of molybdenum-rhenium alloy materials, and in particular relates to a carbide dispersion-strengthened molybdenum-rhenium alloy and a preparation method thereof. Background Art

[0002] Molybdenum-rhenium alloy is a high-temperature alloy primarily composed of two elements: molybdenum (Mo) and rhenium (Re). Molybdenum is a metal with a high melting point, high strength, and good corrosion resistance, while rhenium is a rare metal with a high melting point and excellent high-temperature strength. The combination of these two elements gives MoR alloy excellent performance in high-temperature environments, including a high melting point (up to approximately 2600°C) and high-temperature strength, allowing it to withstand high-temperature loads. It also exhibits good corrosion resistance and excellent thermal conductivity. Therefore, it is used in aerospace applications such as rocket engines, gas turbines, and high-temperature structural parts; as well as in the energy sector, where it can be used in high-temperature components in nuclear reactors, such as heaters, heat exchangers, and coolers.

[0003] Patents CN108145157A and CN117802377A mention the excellent properties of molybdenum-rhenium alloys and propose methods for their preparation. However, adjusting the rhenium content in the molybdenum alloy only improves the overall toughness of the alloy, with limited improvement in alloy strength. During sample preparation, molybdenum-rhenium forms a solid solution structure, and significant grain growth occurs during high-temperature sintering, weakening the effects of improving the alloy's toughness and strength.

[0004] Patent CN117888015A proposes using yttrium oxide or metallic yttrium, metallic zirconium, and a nanocarbon source as a second-phase material to strengthen a molybdenum-rhenium alloy. However, the introduction of oxides and highly active nanocarbons can cause oxidation or carbonization of the molybdenum-rhenium during high-temperature sintering, weakening the alloy's strength.

[0005] Therefore, based on the above situation, the present application proposes a carbide dispersion strengthened molybdenum-rhenium alloy and a preparation method thereof. Summary of the Invention

[0006] The object of the present invention is to provide a carbide dispersion strengthened molybdenum-rhenium alloy and a preparation method thereof in order to solve the above problems.

[0007] The present invention achieves the above-mentioned purpose through the following technical solutions: The present invention provides a carbide dispersion-strengthened molybdenum-rhenium alloy. The carbide dispersion-strengthened molybdenum-rhenium alloy consists of the following components by mass percentage: 0.1-1.5% carbide, 1-10% rhenium, and the balance molybdenum, wherein the carbide is ZrC or TiC.

[0008] The present invention also provides a method for preparing a carbide dispersion strengthened molybdenum-rhenium alloy, comprising the following steps: Step 1: Carbide, molybdenum powder and rhenium powder are mixed in proportion, ball-milled into powder under an inert protective atmosphere, and cold-pressed into a blank, and the obtained blank is sintered at high temperature to achieve density; Step 2: The sintered sample obtained in step 1 is deformed under high temperature conditions, and a carbide dispersion-strengthened molybdenum-rhenium alloy is obtained after annealing.

[0009] As a further optimization solution of the present invention, in step 1, after ball milling, the carbide particle size is 0.01-1 micron, the molybdenum powder particle size is 0.1-5 micron, and the rhenium powder particle size is 0.1-5 micron.

[0010] As a further optimization solution of the present invention, in step 1, the ball milling speed is 50-500 rpm / min.

[0011] As a further optimization solution of the present invention, in step 1, the sintering conditions are in an inert atmosphere, a reducing atmosphere or a vacuum condition, and the sintering temperature is 1500-2200°C.

[0012] As a further optimization solution of the present invention, in step 2, the deformation treatment method includes rolling, forging or rotary forging, and the temperature of the deformation treatment is 1000-1500°C.

[0013] As a further optimization solution of the present invention, in step 2, the annealing conditions are in an inert atmosphere, a reducing atmosphere or a vacuum condition, and the annealing temperature is 1000-1300°C.

[0014] The beneficial effects of the present invention are: The present invention adds a small amount of rhenium to metallic molybdenum and combines it with a small amount of second-phase carbide particles for dispersion strengthening, thereby synergistically improving the strength of the molybdenum-rhenium alloy. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 3. It is a morphology image and engineering stress-strain curve graph of the carbide dispersion strengthened molybdenum-rhenium alloy (ZrC 0.1%, rhenium 1%, balance molybdenum) of Example 1 of the present invention.

[0016] Figure 2 3. It is a morphology image and engineering stress-strain curve graph of the carbide dispersion strengthened molybdenum-rhenium alloy (ZrC 0.9%, rhenium 5%, balance molybdenum) of Example 2 of the present invention.

[0017] Figure 3 3. The morphology and engineering stress-strain curve of the carbide dispersion-strengthened molybdenum-rhenium alloy (ZrC 1.5%, rhenium 10%, balance molybdenum) of Example 3 of the present invention are shown.

[0018] Figure 4 3. The morphology and engineering stress-strain curve of the carbide dispersion-strengthened molybdenum-rhenium alloy (0.6% TiC, 3% rhenium, and the balance molybdenum) of Example 4 of the present invention are shown.

[0019] Figure 5 3. It is a morphology image and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (TiC 0.9%, rhenium 6%, balance molybdenum) of Example 5 of the present invention.

[0020] Figure 6 3. It is a morphology image and engineering stress-strain curve graph of the carbide dispersion strengthened molybdenum-rhenium alloy (TiC 1.2%, rhenium 9%, balance molybdenum) of Example 6 of the present invention.

[0021] Figure 7 1 is an engineering stress-strain curve of a molybdenum-rhenium alloy (5% rhenium, balance molybdenum) according to Comparative Example 1 of the present invention.

[0022] Figure 8 1 is an engineering stress-strain curve of the molybdenum alloy (ZrC 0.9%, balance molybdenum) of Comparative Example 2 of the present invention.

[0023] Figure 9 3 is an engineering stress-strain curve of the molybdenum alloy (TiC 0.9%, balance molybdenum) of Comparative Example 3 of the present invention.

[0024] Figure 10 10A is a comparison diagram of the engineering stress-strain curves of the carbide dispersion-strengthened molybdenum-rhenium alloy (ZrC 0.9%, rhenium 5%, balance molybdenum) of Example 2 of the present invention and the molybdenum-rhenium alloy (rhenium 5%, balance molybdenum) of Comparative Example 1, and 10B is a comparison diagram of the engineering stress-strain curves of the carbide dispersion-strengthened molybdenum-rhenium alloy (TiC 1.2%, rhenium 8%, balance molybdenum) of Example 7 and the molybdenum-rhenium alloy (rhenium 8%, balance molybdenum) of Comparative Example 4. DETAILED DESCRIPTION

[0025] The present application is described in further detail below in conjunction with the accompanying drawings. It is necessary to point out that the following specific implementation methods are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Technicians in this field can make some non-essential improvements and adjustments to the present application based on the above application content.

[0026] Material Unless otherwise specified, the methods used in this application are conventional methods known to those skilled in the art, and the reagents and other materials used are commercially available products unless otherwise specified.

[0027] method Example 1 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-1Re-0.1ZrC, which is composed of the following components by mass percentage: 0.1% ZrC, 1% rhenium, and the balance molybdenum; The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere; the ball milling speed is 50 rpm / min. After ball milling, the carbide particle size is 1 μm, the molybdenum powder particle size is 5 μm, and the rhenium powder particle size is 5 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to achieve densification under inert atmosphere at a temperature of 1500°C. Step 4: The sintered sample is deformed under high temperature conditions. The deformation treatment method is forging, and the deformation treatment temperature is 1500°C; Step 5: Annealing the deformed sample in an inert atmosphere at a temperature of 1300°C.

[0028] Example 2 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-5Re-0.9ZrC, which is composed of the following components by mass percentage: ZrC 0.9%, rhenium 5%, and the balance molybdenum; The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere. The ball milling speed is 120 rpm / min. After ball milling, the carbide particle size is 0.02 μm, the molybdenum powder particle size is 0.1 μm, and the rhenium powder particle size is 0.1 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to achieve compactness. The sintering conditions are reducing atmosphere and the sintering temperature is 1800°C. Step 4: The sintered sample is deformed under high temperature conditions. The deformation treatment method is rotary forging, and the deformation treatment temperature is 1400°C. Step 5: Anneal the deformed sample under vacuum conditions at a temperature of 1200°C.

[0029] Example 3 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-10Re-1.5ZrC, which is composed of the following components by mass percentage: ZrC 1.5%, rhenium 10%, and the balance molybdenum; The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere; the ball milling speed is 200 rpm / min. After ball milling, the carbide particle size is 1 μm, the molybdenum powder particle size is 2 μm, and the rhenium powder particle size is 2 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to achieve compactness. The sintering conditions are vacuum conditions and the sintering temperature is 2200°C. Step 4: The sintered sample is deformed under high temperature conditions by rolling at a temperature of 1200°C. Step 5: Annealing the deformed sample in a reducing atmosphere at a temperature of 1100°C.

[0030] Example 4 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-3Re-0.6TiC, which is composed of the following components by mass percentage: 0.6% TiC, 3% rhenium, and the balance molybdenum.

[0031] The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere; the ball milling speed is 300 rpm / min. After ball milling, the carbide particle size is 0.5 μm, the molybdenum powder particle size is 1 μm, and the rhenium powder particle size is 3 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to a high density under an inert atmosphere at a temperature of 1700°C. Step 4: The sintered sample is deformed under high temperature conditions by rolling at a temperature of 1000°C. Step 5: Annealing the deformed sample in an inert atmosphere at a temperature of 1000°C.

[0032] Example 5 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-6Re-0.9TiC, which is composed of the following components by mass percentage: 0.9% TiC, 6% rhenium, and the balance molybdenum.

[0033] The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere; the ball milling speed is 350 rpm / min. After ball milling, the carbide particle size is 0.5 μm, the molybdenum powder particle size is 2 μm, and the rhenium powder particle size is 3 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to achieve compactness. The sintering conditions are vacuum conditions and the sintering temperature is 2100°C. Step 4: The sintered sample is deformed under high temperature conditions. The deformation treatment method is rotary forging, and the deformation treatment temperature is 1300°C. Step 5: Anneal the deformed sample under vacuum conditions at a temperature of 1300°C.

[0034] Example 6 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-9Re-1.2TiC. The molybdenum-rhenium alloy consists of the following components by mass percentage: 1.2% TiC, 9% rhenium, and the balance molybdenum.

[0035] The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere; the ball milling speed is 400 rpm / min. After ball milling, the carbide particle size is 0.2 μm, the molybdenum powder particle size is 3 μm, and the rhenium powder particle size is 4 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to achieve densification. The sintering conditions are reducing atmosphere and the sintering temperature is 1900°C. Step 4: The sintered sample is deformed under high temperature conditions. The deformation treatment method is forging, and the deformation treatment temperature is 1100°C; Step 5: Annealing the deformed sample in an inert atmosphere at a temperature of 1200°C.

[0036] Example 7 This embodiment provides a carbide dispersion strengthened molybdenum-rhenium alloy Mo-8Re-1.2TiC. The molybdenum-rhenium alloy consists of the following components by mass percentage: 1.2% TiC, 8% rhenium, and the balance molybdenum.

[0037] The preparation method of the molybdenum-rhenium alloy comprises the following steps: Step 1: Weigh carbide, molybdenum powder, and rhenium powder in proportion and ball mill them under an inert atmosphere; the ball milling speed is 450 rpm / min. After ball milling, the carbide particle size is 0.05 μm, the molybdenum powder particle size is 2 μm, and the rhenium powder particle size is 5 μm. Step 2: Fill the ball mill powder into the mold and cold press it into a blank. The operation must be carried out under an inert protective atmosphere. Step 3: Sinter the green body in a high-temperature furnace to achieve densification. The sintering conditions are inert atmosphere and the sintering temperature is 2000℃. Step 4: The sintered sample is deformed under high temperature conditions. The deformation treatment method is rotary forging, and the deformation treatment temperature is 1300°C. Step 5: Anneal the deformed sample under vacuum conditions at a temperature of 1000°C.

[0038] Comparative Example 1 This comparative example provides a molybdenum-rhenium alloy Mo-5Re, which is composed of the following components in mass percentage: 5% rhenium and the balance molybdenum; the preparation method is the same as that in Example 2, and after ball milling, the particle size of the molybdenum powder and the particle size of the rhenium powder are both consistent with those in Example 2.

[0039] Comparative Example 2 This comparative example provides a molybdenum alloy Mo-0.9ZrC, which is composed of the following components by mass percentage: 0.9% ZrC and the balance molybdenum; the preparation method is the same as that of Example 2, and after ball milling, the particle size of the carbide ZrC and the particle size of the molybdenum powder are both consistent with those of Example 2.

[0040] Comparative Example 3 This comparative example provides a molybdenum alloy Mo-0.9TiC, which is composed of the following components by mass percentage: 0.9% TiC and the balance molybdenum; the preparation method is the same as that of Example 5, and after ball milling, the particle size of the TiC carbide and the particle size of the molybdenum powder are both consistent with those of Example 5.

[0041] Comparative Example 4 This comparative example provides a molybdenum-rhenium alloy Mo-8Re, which is composed of the following components by mass percentage: 8% rhenium and the balance molybdenum. The preparation method is the same as that of Example 7. After ball milling, the particle size of the carbide TiC and the particle size of the molybdenum powder are both the same as those of Example 7.

[0042] Experimental test: The molybdenum-rhenium alloys of Examples 1-6 were characterized and analyzed, and the alloys of Examples 1-7 and Comparative Examples 1-4 were subjected to room temperature tensile tests. The test results Figure 1-10 As shown, the details are as follows: like Figure 1 As shown, the morphology and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (ZrC 0.1%, rhenium 1%, balance molybdenum) prepared in Example 1; the tensile strength is 580 MPa and the elongation is 38%.

[0043] like Figure 2 As shown, the morphology and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (ZrC 0.9%, rhenium 5%, balance molybdenum) prepared in Example 2; the tensile strength is 720 MPa and the elongation is 33%.

[0044] like Figure 3 As shown, the morphology and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (ZrC 1.5%, rhenium 10%, balance molybdenum) prepared in Example 3; the tensile strength is 930 MPa and the elongation is 25%.

[0045] like Figure 4 As shown, the morphology and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (TiC 0.6%, rhenium 3%, balance molybdenum) prepared in Example 4; the tensile strength is 590 MPa and the elongation is 35%.

[0046] like Figure 5 As shown, the morphology and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (TiC 0.9%, rhenium 6%, balance molybdenum) prepared in Example 5; the tensile strength is 850 MPa and the elongation is 31%.

[0047] like Figure 6 As shown, the morphology and engineering stress-strain curve of the carbide dispersion strengthened molybdenum-rhenium alloy (TiC 1.2%, rhenium 9%, balance molybdenum) prepared in Example 6; the tensile strength is 920 MPa and the elongation is 24%.

[0048] like Figure 7 As shown in FIG, the engineering stress-strain curve of the molybdenum-rhenium alloy (5% rhenium, balance molybdenum) prepared in Comparative Example 1; the tensile strength is 420 MPa and the elongation is 29%.

[0049] like Figure 8 As shown in FIG, the engineering stress-strain curve of the molybdenum alloy (ZrC 0.9%, balance molybdenum) prepared in Comparative Example 2; the tensile strength is 640 MPa and the elongation is 33%.

[0050] like Figure 9 As shown in FIG, the engineering stress-strain curve of the molybdenum alloy (TiC 0.9%, balance molybdenum) prepared in Comparative Example 3; the tensile strength is 700 MPa and the elongation is 40%.

[0051] like Figure 10 As shown in Figure A, a comparison of the engineering stress-strain curves of the carbide dispersion-strengthened molybdenum-rhenium alloy (0.9% ZrC, 5% rhenium, and the balance molybdenum) of Example 2 and the molybdenum-rhenium alloy (5% rhenium, the balance molybdenum) of Comparative Example 1 shows that the engineering stress that the carbide dispersion-strengthened molybdenum-rhenium alloy of Example 2 can withstand is significantly higher than that of the molybdenum-rhenium alloy of Comparative Example 1, indicating that the use of ZrC can improve the strength and toughness of the carbide dispersion-strengthened molybdenum-rhenium alloy; like Figure 10 As shown in Figure B, by comparing the engineering stress-strain curves of the carbide dispersion strengthened molybdenum-rhenium alloy (TiC 1.2%, rhenium 8%, balance molybdenum) of Example 7 and the molybdenum-rhenium alloy (rhenium 8%, balance molybdenum) of Comparative Example 4, it can be seen that the engineering stress that the carbide dispersion strengthened molybdenum-rhenium alloy of Example 7 can withstand is significantly higher than that of the molybdenum-rhenium alloy of Comparative Example 4, which shows that the use of TiC can greatly improve the strength of the carbide dispersion strengthened molybdenum-rhenium alloy.

[0052] For molybdenum-rhenium alloys, carbide dispersion enhancement can improve the performance of molybdenum-rhenium alloys, which is of great significance. First, carbides can refine the molybdenum-rhenium alloy grains and prevent dislocation movement, thereby significantly improving the strength of the alloy at high temperatures. This is particularly important for the application of molybdenum-rhenium alloys in aerospace and other fields; at the same time, carbide dispersion distribution can inhibit the phase change of molybdenum-rhenium alloys at high temperatures and improve their thermal stability, which is crucial for extending the service life of components and improving system reliability.

[0053] The above-described embodiments merely illustrate several implementations of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, and all such variations and improvements fall within the scope of protection of the present invention.

Claims

1. A carbide dispersion strengthened molybdenum-rhenium alloy, characterized in that: The carbide dispersion strengthened molybdenum-rhenium alloy consists of the following components by mass percentage: 0.1-1.5% carbide, 1-10% rhenium, and the balance molybdenum, wherein the carbide is ZrC or TiC.

2. A method for preparing the carbide dispersion strengthened molybdenum-rhenium alloy according to claim 1, characterized in that: The following steps are involved: Step 1: Carbide, molybdenum powder and rhenium powder are mixed in proportion, ball-milled into powder under an inert protective atmosphere, and cold-pressed into a blank, and the obtained blank is sintered at high temperature to achieve density; Step 2: The sintered sample obtained in step 1 is deformed under high temperature conditions, and a carbide dispersion-strengthened molybdenum-rhenium alloy is obtained after annealing.

3. The method for preparing a carbide dispersion strengthened molybdenum-rhenium alloy according to claim 2, wherein: In step 1, after ball milling, the carbide particle size is 0.01-1 micron, the molybdenum powder particle size is 0.1-5 micron, and the rhenium powder particle size is 0.1-5 micron.

4. The method for preparing a carbide dispersion strengthened molybdenum-rhenium alloy according to claim 2, wherein: In step 1, the ball milling speed is 50-500 rpm / min.

5. The method for preparing a carbide dispersion strengthened molybdenum-rhenium alloy according to claim 2, wherein: In step 1, the sintering conditions are in an inert atmosphere, a reducing atmosphere or a vacuum condition, and the sintering temperature is 1500-2200°C.

6. The method for preparing a carbide dispersion strengthened molybdenum-rhenium alloy according to claim 2, wherein: In step 2, the deformation treatment method includes rolling, forging or rotary forging, and the temperature of the deformation treatment is 1000-1500°C.

7. The method for preparing a carbide dispersion strengthened molybdenum-rhenium alloy according to claim 2, wherein: In step 2, the annealing condition is in an inert atmosphere, a reducing atmosphere or a vacuum condition, and the annealing temperature is 1000-1300°C.

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