A method for manufacturing a zirconium-yttrium alloy pipe target

Abstract

The application provides a preparation method of a zirconium-yttrium alloy pipe target material, which comprises the following steps: weighing metal zirconium and metal yttrium, dividing the metal zirconium into three parts, mixing the first part of the metal zirconium with the metal yttrium uniformly, loading the mixture into a crucible, and performing suspension smelting to obtain a first zirconium-yttrium alloy ingot; loading the second part of the metal zirconium into the crucible, and performing suspension smelting to obtain a first zirconium ingot; loading the third part of the metal zirconium into the crucible, and performing suspension smelting to obtain a second zirconium ingot; loading the first zirconium ingot into the bottom of the crucible, loading the first zirconium-yttrium alloy ingot into the middle of the crucible above the first zirconium ingot, loading the second zirconium ingot into the upper part of the crucible above the first zirconium-yttrium alloy ingot, and performing suspension smelting to obtain a second zirconium-yttrium alloy ingot; and performing suspension smelting on the second zirconium-yttrium alloy ingot again; and the method adopts a three-segment separate forming mode and suspension smelting again, so that the segregation problem caused by the floating of yttrium is solved.

Description

Technical Field

[0001] This invention relates to the field of alloy smelting technology, and in particular to a method for preparing a zirconium-yttrium alloy tube target. Background Technology

[0002] Zirconium-yttrium alloys are mainly used in hydrogen storage materials, high-purity hydrogen separation, aerospace, and other fields. Patent CN112030013 discloses a method for preparing zirconium-yttrium alloys. However, the conventional smelting technology used in this patent involves a complex melting process and unclear composition. Summary of the Invention

[0003] In view of the above-mentioned defects, the present invention proposes a method for preparing zirconium-yttrium alloy tube targets.

[0004] A method for preparing a zirconium-yttrium alloy tube target includes the following steps:

[0005] Material preparation: Weigh zirconium and yttrium in a weight ratio of 90%-92%:10%-8%, and divide the zirconium into three parts: part 1 (30±1%), part 2 (30±1%), and part 3 (40±1%).

[0006] Step 1: Preparation of a first zirconium-yttrium alloy ingot: Using a suspension melting furnace, the first part of metallic zirconium and metallic yttrium are mixed evenly and loaded into a crucible for suspension melting to obtain the first zirconium-yttrium alloy ingot;

[0007] Step 2: First Zirconium Ingot Smelting: Using a suspension melting furnace, the second batch of metallic zirconium is added to a crucible and subjected to suspension melting to obtain the first zirconium ingot;

[0008] Step 3: Smelting of the second zirconium ingot: Using a suspension melting furnace, the crucible containing the third portion of metallic zirconium is smelted in suspension to obtain the second zirconium ingot;

[0009] Step 4: Place the first zirconium ingot at the bottom of the crucible, place the first zirconium-yttrium alloy ingot in the middle of the crucible above the first zirconium ingot, and place the second zirconium ingot in the upper part of the crucible above the first zirconium-yttrium alloy ingot for suspension melting to obtain the second zirconium-yttrium alloy ingot.

[0010] Step 5: Turn the second zirconium-yttrium alloy ingot over so that the top is facing down, put it into a crucible, and perform suspension melting to obtain the zirconium-yttrium alloy ingot;

[0011] Step 6: Perform chemical analysis on the above zirconium-yttrium alloy ingot. The composition is: Zr: 90-92%, Y: 7.5-9.5%, and the remainder is unavoidable impurities.

[0012] In this invention, since zirconium metal has a higher specific gravity than yttrium metal, suspension melting is employed to avoid segregation caused by the difference in metal specific gravity during the smelting process. In this melting method, the flow of the molten metal within the furnace is a near-horizontal vortex. For the first zirconium-yttrium alloy ingot, yttrium and zirconium metal are first mixed and melted into a single alloy block. Then, the alloy ingot is placed in the center of the suspension melting furnace. During suspension melting, the probability of yttrium floating to the surface is relatively low. After tumbling and melting, a small portion of the yttrium floats to the surface, thus allowing the yttrium metal to diffuse within the height range of the alloy ingot, resulting in a uniform yttrium content throughout the ingot. Furthermore, the yttrium content is very low, approximately 10% of that of zirconium metal. If the three-stage molding method of this invention is not used, and instead the two metals are mixed uniformly before suspension melting, the problem of segregation caused by yttrium floating to the surface is more severe. Implementation

[0013] This invention provides a method for preparing a zirconium-yttrium alloy tube target, comprising the following steps:

[0014] Material preparation: Weigh zirconium and yttrium in a weight ratio of 90%-92%:10%-8%, and divide the zirconium into three parts: part 1 (30±1%), part 2 (30±1%), and part 3 (40±1%).

[0015] Step 1: Preparation of a first zirconium-yttrium alloy ingot: Using a suspension melting furnace, the first part of metallic zirconium and metallic yttrium are mixed evenly, loaded into a crucible, and subjected to suspension melting to obtain the first zirconium-yttrium alloy ingot;

[0016] Step 2: First Zirconium Ingot Smelting: Using a suspension melting furnace, the second batch of metallic zirconium is added to a crucible and subjected to suspension melting to obtain the first zirconium ingot;

[0017] Step 3: Smelting of the second zirconium ingot: Using a suspension melting furnace, the crucible containing the third portion of metallic zirconium is smelted in suspension to obtain the second zirconium ingot;

[0018] Step 4: Place the first zirconium ingot at the bottom of the crucible, place the first zirconium-yttrium alloy ingot in the middle of the crucible above the first zirconium ingot, and place the second zirconium ingot in the upper part of the crucible above the first zirconium-yttrium alloy ingot for suspension melting to obtain the second zirconium-yttrium alloy ingot.

[0019] Step 5: Turn the second zirconium-yttrium alloy ingot over so that the top is facing down, put it into a crucible, and perform suspension melting to obtain the zirconium-yttrium alloy ingot;

[0020] Step 6: Perform chemical analysis on the above zirconium-yttrium alloy ingot. The composition is: Zr: 90-92%, Y: 7.5-9.5%, and the remainder is unavoidable impurities.

[0021] Furthermore, in step one, the suspension melting process involves: evacuating to 10...-3 Under vacuum conditions, argon gas was introduced to -0.045 Pa for suspension melting. The melting power was gradually adjusted from 4 kW to 170 kW, and the melting time was 12 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain the first zirconium-yttrium alloy ingot.

[0022] Furthermore, in step two, the suspension melting process involves: evacuating to 10... -3 Under vacuum conditions, argon gas was introduced to -0.045 Pa for suspension melting. The melting power was gradually adjusted from 4 kW to 170 kW, and the melting time was 12 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain the first zirconium ingot.

[0023] Furthermore, in step three, the suspension melting process is as follows: evacuate to a vacuum environment of 10⁻³, fill with argon gas to -0.045 Pa, and carry out suspension melting. The melting power is gradually adjusted from 4 kW to 170 kW, the melting time is 12 minutes, and after cooling and removing from the furnace, the surface is cleaned to obtain the second zirconium ingot.

[0024] Furthermore, in step four, the suspension melting process involves vacuuming to 10... -3 Under vacuum conditions, argon gas was introduced to -0.040 Pa for suspension melting. The melting power was gradually adjusted from 35 kW to 285 kW, and the melting time was 20 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain the second zirconium-yttrium alloy ingot.

[0025] Furthermore, in step five, the suspension melting process involves vacuuming to 10... -3 Under vacuum conditions, argon gas is introduced to -0.040 Pa for suspension melting. The melting power is gradually adjusted from 35 kW to 300 kW, and the melting time is 18 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain zirconium-yttrium alloy ingots.

[0026] Furthermore, it also includes the following steps: Step 7: Forging; Step 8: Annealing; Step 9: Drilling. Example 1

[0027] Step 1: Preparation of a primary zirconium-yttrium alloy ingot: Using a suspension melting furnace, weigh 1503g of metallic zirconium and 497g of metallic yttrium, mix them in a φ90mm crucible, and evacuate to 10°C. -3 Under vacuum conditions, argon gas is introduced to -0.045 Pa for suspension melting. The melting power is gradually adjusted from 4 kW to 170 kW, and the melting time is 12 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain a primary zirconium-yttrium alloy ingot.

[0028] Step 2: Weigh 1500g of zirconium metal raw material into a suspension melting furnace and melt it in a 90mm crucible, evacuating the vacuum to 100°C. -3Under vacuum conditions, argon gas was introduced to -0.045 Pa for suspension melting. The melting power was gradually adjusted from 4 kW to 170 kW, and the melting time was 12 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain the first metallic zirconium ingot.

[0029] Step 3: Weigh 2000g of metallic zirconium raw material using a suspension melting furnace and melt it in a φ90mm crucible. Evacuate the furnace to a vacuum level of 10⁻³ and then fill it with argon gas to -0.045Pa for suspension melting. The melting power is gradually adjusted from 4kw to 170kw, and the melting time is 12 minutes. After cooling and removing the material from the furnace, clean the surface to obtain the second metallic zirconium.

[0030] Step 4: Place the first zirconium ingot obtained from step 2 into the bottom of a φ140mm crucible, place the first zirconium-yttrium alloy ingot obtained from step 1 into the middle of the crucible, and place the second zirconium ingot obtained from step 3 into the top of the crucible. Evacuate the crucible to 10°C. -3 Under vacuum conditions, argon gas is introduced to -0.040 Pa for suspension melting. The melting power is gradually adjusted from 35 kW to 285 kW, and the melting time is 20 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain a secondary zirconium-yttrium alloy ingot.

[0031] Step 5: Place the zirconium-yttrium alloy ingot obtained in Step 4, top down and reversed, into a φ140mm crucible, and evacuate to 10°C. -3 Under vacuum, argon gas was introduced to -0.040 Pa for suspension melting. The melting power was gradually adjusted from 35kw to 300kw, and the melting time was 18 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain 5400g of zirconium-yttrium alloy ingot.

[0032] Step Six: Data Analysis. Chemical analysis was performed on the smelted zirconium-yttrium alloy ingot: Zr: 92.03%, Y: 7.88%, Al: 0.005%, Fe: 0.01%, Si: 0.010%, Cr: 0.001%, C: 0.005%, S: 0.003%, O: 0.015%, N: 0.010%.

[0033] The above analysis shows that the effective elements zirconium and yttrium content reaches 99.91%, the raw material input is 1503+1500+2000+497=5500g, and the alloy yield is 5400 / 5500=98.18%. Example 2

[0034] Step 1: Preparation of a primary zirconium-yttrium alloy ingot: Using a suspension melting furnace, weigh 1494g of metallic zirconium and 489g of metallic yttrium, mix them in a φ90mm crucible, and evacuate to 10°C. -3Under vacuum conditions, argon gas is introduced to -0.045 Pa for suspension melting. The melting power is gradually adjusted from 4 kW to 170 kW, and the melting time is 12 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain a primary zirconium-yttrium alloy ingot.

[0035] Step 2: Weigh 1505g of zirconium metal raw material into a suspension melting furnace and melt it in a 90mm crucible, evacuating the vacuum to 100°C. -3 Under vacuum conditions, argon gas was introduced to -0.045 Pa for suspension melting. The melting power was gradually adjusted from 4 kW to 170 kW, and the melting time was 12 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain the first metallic zirconium ingot.

[0036] Step 3: Weigh 2002g of metallic zirconium raw material using a suspension melting furnace and melt it in a φ90mm crucible. Under a vacuum environment of 10-3, argon gas is introduced to -0.045Pa for suspension melting. The melting power is gradually adjusted from 4kw to 170kw, and the melting time is 12 minutes. After cooling and removing it from the furnace, the surface is cleaned to obtain the second metallic zirconium.

[0037] Step 4: Place the first zirconium ingot obtained from step 2 into the bottom of a φ140mm crucible, place the first zirconium-yttrium alloy ingot obtained from step 1 into the middle of the crucible, and place the second zirconium ingot obtained from step 3 into the top of the crucible. Evacuate the crucible to 10°C. -3 Under vacuum conditions, argon gas is introduced to -0.040 Pa for suspension melting. The melting power is gradually adjusted from 35 kW to 285 kW, and the melting time is 20 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain a secondary zirconium-yttrium alloy ingot.

[0038] Step 5: Place the zirconium-yttrium alloy ingot obtained in Step 4, top down and reversed, into a φ140mm crucible, and evacuate to 10°C. -3 Under vacuum, argon gas was introduced to -0.040 Pa for suspension melting. The melting power was gradually adjusted from 35kw to 300kw, and the melting time was 18 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain 5380g of zirconium-yttrium alloy ingot.

[0039] Step Six: Data Analysis. Chemical analysis was performed on the smelted zirconium-yttrium alloy ingot: Zr: 91.89%, Y: 7.95%, Al: 0.006%, Fe: 0.01%, Si: 0.020%, Cr: 0.002%, C: 0.016%, S: 0.002%, O: 0.02%, N: 0.02%.

[0040] The above analysis shows that the effective elements zirconium and yttrium content reaches 99.84%, the raw material input is 1494+489+1505+2002=5490g, and the zirconium and yttrium alloy yield is 5380 / 5490=97.99%. Example 3

[0041] Step 1: Preparation of a primary zirconium-yttrium alloy ingot: Using a suspension melting furnace, weigh 1504g of metallic zirconium and 500g of metallic yttrium, mix them in a φ90mm crucible, and evacuate to 10°C. -3 Under vacuum conditions, argon gas is introduced to -0.045 Pa for suspension melting. The melting power is gradually adjusted from 4 kW to 170 kW, and the melting time is 12 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain a primary zirconium-yttrium alloy ingot.

[0042] Step 2: Weigh 1498g of zirconium metal raw material into a suspension melting furnace and melt it in a 90mm crucible, evacuating the vacuum to 100°C. -3 Under vacuum conditions, argon gas was introduced to -0.045 Pa for suspension melting. The melting power was gradually adjusted from 4 kW to 170 kW, and the melting time was 12 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain the first metallic zirconium ingot.

[0043] Step 3: Weigh 1998g of metallic zirconium raw material using a suspension melting furnace and melt it in a φ90mm crucible. Under a vacuum environment of 10-3, argon gas is introduced to -0.045Pa for suspension melting. The melting power is gradually adjusted from 4kw to 170kw, and the melting time is 12 minutes. After cooling and removing it from the furnace, the surface is cleaned to obtain the second metallic zirconium.

[0044] Step 4: Place the first zirconium ingot obtained from step 2 into the bottom of a φ140mm crucible, place the first zirconium-yttrium alloy ingot obtained from step 1 into the middle of the crucible, and place the second zirconium ingot obtained from step 3 into the top of the crucible. Evacuate the crucible to 10°C. -3 Under vacuum conditions, argon gas is introduced to -0.040 Pa for suspension melting. The melting power is gradually adjusted from 35 kW to 285 kW, and the melting time is 20 minutes. After cooling and removing from the furnace, the surface is cleaned to obtain a secondary zirconium-yttrium alloy ingot.

[0045] Step 5: Place the zirconium-yttrium alloy ingot obtained in Step 4, top down and reversed, into a φ140mm crucible, and evacuate to 10°C. -3 Under vacuum conditions, argon gas was introduced to -0.040 Pa for suspension melting. The melting power was gradually adjusted from 35 kW to 300 kW, and the melting time was 18 minutes. After cooling and removing from the furnace, the surface was cleaned to obtain 5420 g of zirconium-yttrium alloy ingot.

[0046] Step Six: Data Analysis. Chemical analysis was performed on the smelted zirconium-yttrium alloy ingot: Zr: 92.11%, Y: 7.84%, Al: 0.004%, Fe: 0.015%, Si: 0.018%, Cr: 0.002%, C: 0.003%, S: 0.002%, O: 0.02%, N: 0.02%.

[0047] The above analysis shows that the effective elements zirconium and yttrium content reaches 99.95%, the raw material input is 1504+500+1498+1998=5500g, and the alloy yield is 5420 / 5500=98.55%.

[0048] After step six, the embodiments 1, 2, and 3 described above require machining, which mainly includes the following steps seven, eight, and nine.

[0049] Step Seven: Forging. The large-particle-size body-centered cubic internal structure of the zirconium-yttrium alloy ingot is radially forged and crushed at high temperature to form a billet with a uniform fine-grained microstructure. Preheating to 80-100℃ for 20 seconds using medium-frequency induction heating, followed by a uniform, leak-free coating of glass powder. To prevent the zirconium-yttrium alloy ingot from absorbing oxygen and nitrogen during heat treatment, which could lead to brittleness, reduced plasticity, and poor processing performance, a high-temperature resistant material (T1350 glass powder) needs to be coated on the surface for protection. To ensure uniform heating within the material, a programmed, uniform addition method should be used to avoid localized instantaneous heating that could alter the material's microstructure. A medium-frequency induction heating of 20-30KW for 20 seconds, preheating to 80-100℃, and then coating with T1350 high-temperature glass powder are planned. Heated to 1100℃ by 800 kW medium frequency heating, held for 30 minutes, the color upon exiting the furnace is dark red, the final forging temperature is ≥650℃, and the material is roughened to φ280-290mm by 1600T free forging, then drawn to about φ110mm, and pickled to form zirconium yttrium tube material billet.

[0050] Step 8: Annealing. After heat treatment and forging, the zirconium-yttrium alloy ingot forms a fine-grained internal structure with surface oxidation and nitridation, increasing hardness and making hard machining more difficult. Therefore, the billet needs to be vacuum annealed to ensure complete recrystallization of the internal grains. Under high temperature and vacuum conditions, the billet releases some oxygen and nitrogen, softening it and making it easier to machine. After annealing, samples are taken for transverse and longitudinal phase analysis. Complete recrystallization in both directions is required, with a recrystallization degree greater than 90%. The annealing process uses 500℃ / 30min + 800℃ / 30min + 1100℃ / 90min, followed by natural cooling. After annealing, the recrystallization degree of the billet reaches over 90%, making it suitable for machining.

[0051] Step Nine: Drilling, Encasing, and Extrusion. An electrical discharge machining (EDM) is used to drill a hole in the center of the vanadium billet, and a copper cladding is used for extrusion to form a zirconium-yttrium tube billet. The billet is then machined and calibrated to produce the zirconium-yttrium tube.

Claims

1. A method of producing a zirconium-yttrium alloy pipe target material, characterized by It comprises the following steps: Preparation: according to the weight ratio of 90%-92%:10%-8%, the metal zirconium and the metal yttrium are weighed, and the metal zirconium is divided into three parts, which are 30±1% first part, 30±1% second part and 40±1% third part respectively; Step one: preparation of primary zirconium-yttrium alloy ingot: using a suspension melting furnace, the first part of the metal zirconium and the metal yttrium are mixed uniformly, loaded into a crucible, and subjected to suspension melting to obtain a first zirconium-yttrium alloy ingot; Step two: first zirconium ingot melting: using a suspension melting furnace, the second part of the metal zirconium is added to the crucible and subjected to suspension melting to obtain a first zirconium ingot; Step three: second zirconium ingot melting: using a suspension melting furnace, the third part of the metal zirconium is added to the crucible and subjected to suspension melting to obtain a second zirconium ingot; Step four: the first zirconium ingot is loaded into the bottom of the crucible, the first zirconium-yttrium alloy ingot is loaded into the middle of the crucible above the first zirconium ingot, and the second zirconium ingot is loaded into the upper part of the crucible above the first zirconium-yttrium alloy ingot, and subjected to suspension melting to obtain a second zirconium-yttrium alloy ingot; Step five: the second zirconium-yttrium alloy ingot is turned upside down and loaded into the crucible, and subjected to suspension melting to obtain a zirconium-yttrium alloy ingot; Step six: chemical analysis is performed on the above zirconium-yttrium alloy ingot, and the component content is: Zr: 90-92%, Y: 7.5-9.5%, and the rest is inevitable impurities.

2. The method of producing a zirconium-yttrium alloy pipe target according to claim 1, wherein The step one is a process of suspension smelting: vacuumizing to 10 -3 In the vacuum environment, the argon is filled to -0.045 Pa, the suspension smelting is carried out, the smelting power is gradually adjusted from 4 kw to 170 kw, the smelting time is 12 minutes, the surface is cleaned after cooling and discharging, and the first zirconium yttrium alloy ingot is prepared.

3. The method of producing a zirconium-yttrium alloy pipe target according to claim 1, wherein In the second step, the process of suspension smelting is as follows: vacuumizing to 10 -3 In the second step, the process of suspension smelting is as follows: vacuumizing to 10 In the second step, the process of suspension smelting is as follows: vacuumizing to 10 4. The method of claim 1, wherein the zirconium-yttrium alloy pipe target is prepared by the steps of: In the third step, the process of suspension smelting is as follows: vacuumizing to 10 -3 In the third step, the process of suspension smelting is as follows: vacuumizing to 10 In the third step, the process of suspension smelting is as follows: vacuumizing to 10 ​ 5. The method of claim 1, wherein the zirconium-yttrium alloy pipe target is prepared by the steps of: In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 -3 In the fourth step, the process of suspension smelting is vacuum extraction to 10 ​ 6. The method for preparing the zirconium-yttrium alloy tube target as described in claim 1, characterized in that... In the step five, the process of suspension smelting is vacuum extraction to 10 -3 In the vacuum environment, the argon is filled to -0.040 Pa, the suspension smelting is carried out, the smelting power is gradually adjusted from 35 kw to 300 kw, the smelting time is 18 minutes, the surface is cleaned after cooling and discharging, and the zirconium-yttrium alloy ingot is prepared.

7. The method for preparing the zirconium-yttrium alloy tube target as described in claim 1, characterized in that... It further comprises the following steps: Step seven: forging; Step eight: annealing; Step nine: punching.