CN110565169A - Method for cultivating Mo-Nb-W-Zr alloy single crystal seed crystal - Google Patents

Abstract

The invention discloses a method for cultivating a Mo‑Nb‑W‑Zr alloy single crystal seed crystal. The specific process of the method is: crystallizing a Mo‑Nb‑W‑Zr alloy polycrystalline blank and a Mo‑Nb alloy single crystal seed crystal The rod is placed in the melting chamber of the electron beam regional melting equipment and vacuumized, then heated and welded, and then cultivated to obtain a Mo‑Nb‑W‑Zr alloy single crystal seed. The present invention adopts the electron beam area melting method, uses the Mo-Nb alloy single crystal as the seed crystal to directly cultivate the Mo-Nb-W-Zr alloy single crystal seed crystal, and adjusts and controls the heating power of welding, Mo-Nb-W-Zr The rotation speed R of the alloy _{polycrystalline} blank and the ratio of the rotation speed R _{single crystal} of the Mo‑Nb alloy single crystal seed crystal bar and the incubation time can directly and efficiently grow the Mo‑Nb‑W‑Zr alloy single crystal seed , shorten the technological process and the cultivation cycle, and reduce the cultivation cost.

Description

A kind of cultivation method of Mo-Nb-W-Zr alloy single crystal seed crystal

technical field

The invention belongs to the technical field of seed crystal preparation, and in particular relates to a method for growing a Mo-Nb-W-Zr alloy single crystal seed crystal.

Background technique

There are various methods for cultivating single crystal seeds, such as Czochralski method (Czochralski method), strain annealing method, gas phase crystallization method, electrolysis method, distillation method and zone smelting method, etc. Among them, it is suitable for refractory metal single crystal The only methods for seed growth are Chowklarski method, strain annealing method and zone melting method.

The essence of cultivating metal single crystal seeds by the Chowklarski method is to immerse a metal wire with a very thin diameter into the melt. By controlling parameters such as temperature gradient, the melt gradually crystallizes on the lower surface of the wire with a specific structure. , after many times of repeated solidification, the metal single crystal seed crystal was cultivated. The disadvantage of the Chowklarski method is that it requires a small number of crystal grains in the structure of the lower end surface of the wire, a large number of cultivation times (not less than 5 times), a long cultivation time, and a suitable crucible material is required, and the crucible material may contaminate the molten metal. body, which is not conducive to the improvement of the purity of refractory metal materials and the cultivation of single crystal seed crystals.

The strain annealing method is a method of cultivating single crystal seed crystals based on the polymorphic solid phase transformation or recrystallization of metals. This method requires the metal polycrystalline material to be annealed at high temperature and for a long time, and the growth efficiency of the single crystal seed crystal is extremely low, and the diameter of the grown refractory metal single crystal seed crystal does not exceed 3mm.

The essence of cultivating refractory metal single crystal seeds by zone smelting is to heat the melting zone with the help of electron beams in a high-vacuum environment, maintain the stability of the melting zone through the balance of surface tension and gravity, and control the temperature gradient and chemical composition of the melting zone. Gradient, etc., after repeated trials within a certain period of time to grow a refractory metal single crystal seed. Since the 1950s, people have begun to explore the research work of cultivating refractory metal single crystal seeds by electron beam zone melting method and have made good progress. Since the 1960s, my country has begun to explore the research on the cultivation of refractory metal single crystal seeds by electron beam zone melting, and has successively cultivated pure W single crystal seeds, pure Mo single crystal seeds, pure Nb single crystal seeds and Mo-Nb alloy single crystal seed crystal. However, no matter what method is used to grow refractory metal single crystal seeds, the cultivation process is very complicated and lengthy, with low efficiency and high cost, and is limited to single crystal seeds of pure metal or binary infinite solid solution alloy system with relatively simple composition. Crystal cultivation.

At present, only Russia, China and the United States can grow large-scale refractory metal single crystal seeds in the world, and they are limited to pure refractory metal single crystals and binary alloy system single crystal seeds. Russia and the United States are still in the research stage for the cultivation of ternary and more than ternary refractory metal alloy single crystal seeds. However, due to the important and special application fields of such materials, both Russia and the United States have imposed a technical blockade on my country. Therefore, my country can only carry out the development of multi-component refractory metal single crystal materials through independent innovation, including the cultivation of multi-component refractory metal single crystal seed crystals.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for growing a Mo-Nb-W-Zr alloy single crystal seed crystal in view of the above-mentioned deficiencies in the prior art. The method adopts the electron beam regional melting method, using the Mo-Nb alloy single crystal as the seed crystal to directly grow the Mo-Nb-W-Zr alloy single crystal seed crystal, by adjusting and controlling the heating power of welding, Mo-Nb-W-Zr The rotation speed R of the alloy _{polycrystalline} blank and the ratio of the rotation speed R _{single crystal} of the Mo-Nb alloy single crystal seed crystal ingot and the incubation time can directly and efficiently grow the Mo-Nb-W-Zr alloy single crystal seed , shorten the technological process and the cultivation cycle, and reduce the cultivation cost.

In order to solve the above-mentioned technical problems, the technical solution adopted in the present invention is: a method for growing a Mo-Nb-W-Zr alloy single crystal seed crystal, which is characterized in that the method comprises the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline blank and the Mo-Nb alloy single crystal seed crystal ingot coaxially on the displacement mechanism fixture in the melting chamber of the electron beam area melting equipment, and both are located in the circle of the cathode filament center position, and then vacuumize the smelting chamber until the degree of vacuum is not greater than 1.0×10 ^-3 Pa; the diameter of the Mo-Nb alloy single crystal seed crystal ingot is 20 mm to 40 mm;

Step 2, by controlling the input high-voltage operating voltage and electron beam current, the Mo-Nb-W-Zr alloy polycrystalline blank and the Mo-Nb alloy single crystal seed crystal ingot in the smelting chamber after the vacuum treatment in step 1 are processed Heating, when the heating power is 5.5kW～6.5kW, the Mo-Nb-W-Zr alloy polycrystalline blank and the Mo-Nb alloy single crystal seed crystal ingot are welded, and then by adjusting the Mo-Nb-W-Zr alloy polycrystalline The ratio of the rotation speed R of the crystal billet R _polycrystal and the rotation speed R _{single crystal} of the Mo-Nb alloy single crystal seed crystal rod is cultivated for 15min to 30min to obtain the Mo-Nb-W-Zr alloy single crystal seed crystal; the Mo - The crystal orientation of the Nb-W-Zr alloy single crystal seed crystal is consistent with the crystal orientation of the Mo-Nb alloy single crystal seed crystal rod, and the R _polycrystal /R _{single crystal} is 0.8-1.2.

The present invention adopts the electron beam area melting method, uses the Mo-Nb alloy single crystal as the seed crystal to directly cultivate the Mo-Nb-W-Zr alloy single crystal seed crystal, and adjusts and controls the heating power of welding, Mo-Nb-W-Zr The ratio of the rotation speed R of the alloy _{polycrystalline} blank to the rotation speed R _{of the polycrystalline} and Mo-Nb alloy single crystal seed crystal ingots, and the incubation time, directly and efficiently grow the Mo-Nb-W-Zr alloy single crystal seed crystal. The present invention firstly adjusts and controls the heating power of welding to avoid the excessive viscosity of the fusion zone in the welding process, which is not conducive to the diffusion of alloy elements W and Zr in the Mo-Nb-W-Zr alloy polycrystalline blank, and the resulting alloy elements W and Zr Zr segregation also prevents the temperature gradient of the melting zone from being too small due to the low viscosity of the melting zone, ensuring the cultivation and growth of the Mo-Nb-W-Zr alloy single crystal seed crystal; then by adjusting and controlling the Mo-Nb-W- The ratio of the rotational speed R polycrystalline of the Zr alloy polycrystalline blank to the rotational speed R _{single crystal} of the Mo-Nb alloy single crystal seed rod avoids the rotational speed R _{polycrystalline} of the Mo-Nb-W-Zr alloy _{polycrystalline} blank If it is too slow, the uneven distribution of alloy elements Nb, W, and Zr in the melting zone of the Mo-Nb-W-Zr alloy polycrystalline billet will easily lead to the formation of a polycrystalline structure in the Mo-Nb-W-Zr alloy single crystal seed crystal, while avoiding the The rotation speed R of the Mo-Nb-W-Zr alloy _{polycrystalline} blank is too fast, which destroys the equilibrium state of the melting zone force, which causes the temperature gradient of the melting zone to fluctuate sharply, resulting in the growth of the Mo-Nb-W-Zr alloy single crystal seed crystal. failure; and then by adjusting the cultivation time to ensure the uniform distribution of alloying elements inside the melting zone, avoiding the formation of single crystal structure due to segregation of alloying elements caused by too short cultivation time, so as to ensure the smooth cultivation of single crystal seed crystal and avoid the cultivation time Excessive length and excessive heat accumulation inside the melting zone lead to a decrease in the viscosity of the melting zone, which destroys the balance of the melting zone force and causes the melting zone to collapse, thereby making it impossible to grow Mo-Nb-W-Zr alloy single crystal seeds; in addition, using The genetic characteristics of the crystal, through the selection and control of the crystal orientation of the Mo-Nb alloy single crystal seed crystal, combined with the cultivation process, ensure the crystal orientation and quality of the Mo-Nb-W-Zr alloy single crystal seed crystal.

The above-mentioned cultivation method of a Mo-Nb-W-Zr alloy single crystal seed crystal is characterized in that, in step 2, Mo-Nb-W- Zr alloy single crystal seed crystal. The lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet is heated by electron beam and its lower end face is changed from solid to liquid state, and the lower end face of the Mo-Nb-W-Zr alloy polycrystalline billet is kept in the state by controlling the power. liquid state, and then melt the upper end surface of the Mo-Nb alloy single crystal seed crystal rod by controlling the electron beam and make the upper end surface change from solid to liquid state, and then use gravity to make the Mo-Nb-W-Zr alloy polycrystalline blank The end face is fused with the upper end face of the Mo-Nb alloy single crystal seed crystal rod, and then cultivated, so that the Mo-Nb-W-Zr alloy single crystal seed crystal is cultivated on the end face of the Mo-Nb alloy single crystal seed crystal rod.

The above-mentioned cultivation method of a Mo-Nb-W-Zr alloy single crystal seed crystal is characterized in that the mass content of Nb in the Mo-Nb-W-Zr alloy single crystal seed crystal described in step 2 is 0.1%～ 20%, the mass content of W is 0.1%-1.0%, and the mass content of Zr is 0.01%-1.0%. The Mo-Nb-W-Zr alloy single crystal seed crystal with the above composition is beneficial to the smooth generation of the Mo-Nb-W-Zr alloy single crystal seed crystal rod.

Compared with the prior art, the present invention has the following advantages:

1. The present invention adopts the electron beam regional melting method, and directly cultivates the Mo-Nb-W-Zr alloy single crystal seed crystal with the Mo-Nb alloy single crystal as the seed crystal, by adjusting and controlling the heating power of welding, Mo-Nb-W -The ratio of the rotational speed R of the Zr alloy polycrystalline blank to the rotational speed R _{single crystal} of the Mo-Nb alloy single crystal seed crystal bar, and the incubation time, to directly and efficiently cultivate the Mo-Nb-W-Zr alloy single The crystal seed crystal shortens the process flow and the cultivation cycle, and reduces the cultivation cost.

2. The diameter of the Mo-Nb-W-Zr alloy single crystal seed crystal bar prepared by the present invention is 20mm-40mm, and the crystal orientation deviation angle is stably controlled at 0-2°.

3. The invention has simple process and high efficiency, and is suitable for popularization.

The technical solutions of the present invention will be described in further detail below through examples.

Detailed ways

Example 1

This embodiment includes the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 18mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 20mm and a crystal orientation of <110> in the electron beam melting equipment The displacement mechanism fixture in the smelting chamber is located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 1.0×10 ^{- 3} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 2.0%, the mass content of W is 0.5%, and the mass content of Zr is 0.01%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal bar is 3.0%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 5.5kW-5.7kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline blank rod and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} , to 0.8～ 0.9 for 18 minutes of incubation to obtain a Mo-Nb-W-Zr alloy single crystal seed crystal rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed crystal bar grown in this example is 20 mm, the crystal orientation is <110>, and the crystal orientation deviation angle is 1.35°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed crystal is 2.0%, the mass content of W is 0.5%, and the mass content of Zr is 0.01%.

Comparative example 1

The difference between this comparative example and Example 1 is that the heating power during the cultivation process is 5.1kW-5.4kW.

The diameter of the Mo-Nb-W-Zr alloy seed crystal bar prepared in this comparative example is 20mm, and the phenomenon of incomplete penetration occurs many times in the melting zone. The Mo-Nb-W-Zr alloy polycrystalline billet bar and the Mo-Nb The rotation of the alloy single crystal seed crystal rod is blocked and the motor is automatically shut down. According to the XRD test, the Mo-Nb-W-Zr alloy seed crystal bar prepared in this comparative example is a polycrystalline structure; through the electronic probe analysis test of the chemical composition, the alloy in the Mo-Nb-W-Zr alloy seed crystal bar The segregation of elements W and Zr is greater than ±5%.

Comparative example 2

The difference between this comparative example and Example 1 is that the heating power is 6.6kW-6.8kW during the cultivation process.

The diameter of the Mo-Nb-W-Zr alloy seed crystal rod prepared in this embodiment is 23mm, and the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod forms independent small droplets many times, and makes the melting zone Multiple fractures occurred, resulting in the impossibility of growth of Mo-Nb-W-Zr alloy single crystal seed crystals. According to the XRD test, the Mo-Nb-W-Zr alloy seed rod prepared in this comparative example has a polycrystalline structure.

Comparative example 3

The difference between this comparative example and Example 1 is: the rotation speed of the Mo-Nb-W-Zr alloy polycrystalline blank bar and the rotation speed R of the Mo-Nb alloy single crystal seed _crystal rod in the cultivation process The ratio, that is, R _{polycrystalline} /R _{single crystal} , is 0.6-0.7.

The diameter of the Mo-Nb-W-Zr alloy seed crystal bar prepared in this comparative example is 22mm, and during the welding process, the flow discontinuity occurs in the melting zone. According to the XRD test, the Mo-Nb-W-Zr alloy seed crystal bar prepared in this comparative example is a polycrystalline structure; through the electronic probe analysis test of the chemical composition, the alloy in the Mo-Nb-W-Zr alloy seed crystal bar Elements W and Zr are unevenly distributed, and their segregation degrees are greater than ±8%.

Comparative example 4

The difference between this comparative example and Example 1 is: the rotation speed of the Mo-Nb-W-Zr alloy polycrystalline blank bar and the rotation speed R of the Mo-Nb alloy single crystal seed _crystal rod in the cultivation process The ratio of R _{polycrystalline} /R _{single crystal} is 1.3-1.4.

The diameter of the Mo-Nb-W-Zr alloy seed crystal bar prepared in this comparative example is 24mm, and the melting zone overflows many times, and the shape of the Mo-Nb-W-Zr alloy seed crystal is irregular. According to the XRD test, the Mo-Nb-W-Zr alloy seed rod prepared in this comparative example has a polycrystalline structure.

Comparative example 5

The difference between this comparative example and Example 1 is that the incubation time is 14 minutes.

The diameter of the Mo—Nb—W—Zr alloy seed rod prepared in this comparative example is 20 mm, and the shape is regular. Tested by XRD, the Mo-Nb-W-Zr alloy seed crystal bar prepared by this comparative example is a polycrystalline structure; through the microstructure of the Mo-Nb-W-Zr alloy seed crystal bar observed by metallographic method (optical microscope), It can be seen that there are still a small amount of crystal grains that have not been swallowed; after the electronic probe analysis and test of the chemical composition, the distribution of alloying elements W and Zr in the Mo-Nb-W-Zr alloy seed crystal bar is uneven, and the segregation degree is greater than ±5%.

Comparative example 6

The difference between this comparative example and Example 1 is that the incubation time is 31 minutes.

The diameter of the Mo-Nb-W-Zr alloy seed crystal bar prepared in this comparative example is 21 mm. During the cultivation process, the melting zone overflowed, and the shape of the Mo-Nb-W-Zr alloy seed crystal was uneven. According to the XRD test, the Mo-Nb-W-Zr alloy seed crystal rod prepared before the melting zone overflowed was single crystal structure; the Mo-Nb-W-Zr alloy seed crystal rod prepared after the melting zone overflowed was Polycrystalline organization.

To sum up, the Mo-Nb-W-Zr alloy single crystal seeds cannot be grown in Comparative Examples 1 to 6.

Comparing Example 1 with Comparative Example 1 to Comparative Example 6, it can be seen that the present invention controls the welding heating power, the ratio of the rotational speed of the polycrystalline blank rod to the rotational speed of the single crystal seed crystal, and the incubation time during the melting process in the electron beam suspension region. , so that the melting zone is fully melted during the cultivation of single crystal seeds, and the alloy elements in the melting zone are evenly distributed, avoiding the segregation of alloy elements in the melting zone and the destruction of the balance of surface tension and gravity in the melting zone during single crystal seed cultivation, ensuring The stable cultivation of single crystal seed crystals, and the effective control of the crystal orientation deviation angle of single crystal seed crystals, obtain high-quality Mo-Nb-W-Zr alloy single crystal seed crystal rods.

Example 2

This embodiment includes the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 20mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 24mm and a crystal orientation of <100> in the electron beam area melting equipment The fixtures of the displacement mechanism in the smelting chamber are located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 8.6×10 ^{- 4} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 0.1%, the mass content of W is 0.8%, and the mass content of Zr is 0.55%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal rod is 3.1%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 5.6kW～5.9kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline blank rod and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} , to 0.8～ 1.0 for 15 minutes to obtain a Mo-Nb-W-Zr alloy single crystal seed crystal rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed crystal rod grown in this example is 24 mm, the crystal orientation is <100>, and the crystal orientation deviation angle is 0.60°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed rod is 0.1%, the mass content of W is 0.8%, and the mass content of Zr is 0.55%.

Example 3

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 25mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 28mm and a crystal orientation of <100> in the electron beam area melting equipment The displacement mechanism fixture in the smelting chamber is located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 1.0×10 ^{- 3} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 4.8%, the mass content of W is 0.4%, and the mass content of Zr is 0.38%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal bar is 6.2%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 5.8kW～6.1kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline blank rod and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} , to 0.8～ 1.1 Cultivate for 20 minutes to obtain a Mo-Nb-W-Zr alloy single crystal seed crystal rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed rod grown in this example is 20 mm, the crystal orientation is <100>, and the crystal orientation deviation angle is 1.17°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed rod is 4.8%, the mass content of W is 0.4%, and the mass content of Zr is 0.38%.

Example 4

This embodiment includes the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 24 mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 30 mm and a crystal orientation of <100> in the electron beam melting equipment The fixtures of the displacement mechanism in the smelting chamber are located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 9.2×10 ^{- 4} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 7.3%, the mass content of W is 0.1%, and the mass content of Zr is 0.09%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal bar is 3.1%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 5.9kW～6.3kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline billet bar and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} , to 0.9～ 1.2 Incubate for 15 minutes to obtain a Mo-Nb-W-Zr alloy single crystal seed crystal rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed crystal bar grown in this example is 30mm, the crystal orientation is <100>, and the crystal orientation deviation angle is 0°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed rod is 7.3%, the mass content of W is 0.1%, and the mass content of Zr is 0.09%.

Example 5

This embodiment includes the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 29 mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 36 mm and a crystal orientation of <211> in the electron beam area melting equipment The displacement mechanism fixture in the smelting chamber is located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 6.0×10 ^{- 4} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 9.8%, the mass content of W is 1.0%, and the mass content of Zr is 1.0%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal rod is 6.2%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 6.0kW～6.4kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline blank rod and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} , to 0.8～ 1.0 for 25 minutes to obtain a Mo-Nb-W-Zr alloy single crystal seed rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed crystal bar grown in this example is 36mm, the crystal orientation is <211>, and the crystal orientation deviation angle is 0.18°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed rod is 9.8%, the mass content of W is 1.0%, and the mass content of Zr is 1.0%.

Example 6

This embodiment includes the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 35mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 40mm and a crystal orientation of <111> in the electron beam area melting equipment The displacement mechanism fixture in the smelting chamber is located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 1.0×10 ^{- 3} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 15.6%, the mass content of W is 0.3%, and the mass content of Zr is 0.96%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal rod is 6.2%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 6.2kW～6.5kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline blank rod and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} , to 0.8～ 1.2 Incubate for 28 minutes to obtain a Mo-Nb-W-Zr alloy single crystal seed crystal rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed rod grown in this example is 40 mm, the crystal orientation is <111>, and the crystal orientation deviation angle is 1.59°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed rod is 15.6%, the mass content of W is 0.3%, and the mass content of Zr is 0.96%.

Example 7

This embodiment includes the following steps:

Step 1. Place the Mo-Nb-W-Zr alloy polycrystalline billet bar with a diameter of 26 mm and the Mo-Nb alloy single crystal seed crystal bar with a diameter of 32 mm and a crystal orientation of <110> in the electron beam area melting equipment The fixtures of the displacement mechanism in the smelting chamber are all located at the center of the cathode filament circle, and then the smelting chamber is vacuumed to a vacuum degree of 8.1×10 ^{- 4} Pa; the Mo-Nb-W-Zr alloy polycrystalline The mass content of Nb in the billet bar is 20%, the mass content of W is 0.7%, and the mass content of Zr is 0.29%; the mass content of Nb in the Mo-Nb alloy single crystal seed crystal bar is 3.1%;

Step 2, by controlling the input high-voltage working voltage and electron beam current to the Mo-Nb-W-Zr alloy polycrystalline blank bar and Mo-Nb alloy single crystal seed crystal in the smelting chamber after the vacuum treatment in step 1 The rod is heated, and when the heating power is 5.8kW～6.1kW, the lower end surface of the Mo-Nb-W-Zr alloy polycrystalline billet rod and the upper end surface of the Mo-Nb alloy single crystal seed crystal rod are welded, and then passed Adjust the rotation speed R _polycrystal of Mo-Nb-W-Zr alloy polycrystalline billet bar and the ratio of rotation speed R _{single crystal} of Mo-Nb alloy single crystal seed crystal rod, that is, R _polycrystal /R _{single crystal} is 1.0～ 1.2 Incubate for 30 minutes to obtain a Mo-Nb-W-Zr alloy single crystal seed crystal rod.

After testing, the diameter of the Mo-Nb-W-Zr alloy single crystal seed rod grown in this example is 32 mm, the crystal orientation is <110>, and the crystal orientation deviation angle is 0.39°. Mo-Nb-W-Zr alloy The mass content of Nb in the single crystal seed rod is 20%, the mass content of W is 0.7%, and the mass content of Zr is 0.29%.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.

Claims (3)

1. A method for cultivating Mo-Nb-W-Zr alloy single crystal seeds is characterized by comprising the following steps:

Step one, coaxially placing Mo-Nb-W-Zr alloy polycrystalline blank and Mo-Nb alloy single crystal seed crystal rod on a displacement mechanism clamp in a melting chamber of electron beam zone melting equipment, wherein the displacement mechanism clamp and the cathode filament ring are both positioned at the central position of a cathode filament circle, and then carrying out vacuum-pumping treatment on the melting chamber until the vacuum degree is not more than 1.0 multiplied by 10^-3Pa; the diameter of the Mo-Nb alloy single crystal seed crystal rod is 20-40 mm;

Step two, heating the Mo-Nb-W-Zr alloy polycrystalline blank and the Mo-Nb alloy single crystal seed crystal rod in the smelting chamber subjected to the vacuumizing treatment in the step one by controlling input high-voltage working voltage and electron beam current, welding the Mo-Nb-W-Zr alloy polycrystalline blank and the Mo-Nb alloy single crystal seed crystal rod when the heating power is 5.5 kW-6.5 kW, and then adjusting the rotation speed R of the Mo-Nb-W-Zr alloy polycrystalline blank_{Polycrystalline}And the rotation speed R of the Mo-Nb alloy single crystal seed crystal rod_{Single crystal}Culturing for 15min to 30min according to the ratio to obtain Mo-Nb-W-Zr alloy single crystal seed crystals; the crystal orientation of the Mo-Nb-W-Zr alloy single crystal seed crystal is consistent with that of the Mo-Nb alloy single crystal seed crystal rod, and the R is_{Polycrystalline}/R_{Single crystal}0.8 to 1.2.

2. The method for growing the Mo-Nb-W-Zr alloy single crystal seeds of claim 1, wherein in the second step, the Mo-Nb-W-Zr alloy single crystal seeds are grown on the end surface of the Mo-Nb alloy single crystal seed crystal rod.

3. The method for cultivating a Mo-Nb-W-Zr alloy single crystal seed crystal according to claim 1, wherein in the second step, the Mo-Nb-W-Zr alloy single crystal seed crystal contains Nb 0.1-20 wt%, W0.1-1.0 wt%, and Zr 0.01-1.0 wt%.