CN114293159B - Preparation method of nickel-based alloy target - Google Patents
Preparation method of nickel-based alloy target Download PDFInfo
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- CN114293159B CN114293159B CN202111548176.7A CN202111548176A CN114293159B CN 114293159 B CN114293159 B CN 114293159B CN 202111548176 A CN202111548176 A CN 202111548176A CN 114293159 B CN114293159 B CN 114293159B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 88
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 70
- 239000000956 alloy Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 nickel-chromium-aluminum-yttrium-silicon-boron Chemical compound 0.000 claims abstract description 60
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 53
- 229910001325 element alloy Inorganic materials 0.000 claims abstract description 49
- 238000003723 Smelting Methods 0.000 claims abstract description 43
- 239000007787 solid Substances 0.000 claims abstract description 40
- RFEISCHXNDRNLV-UHFFFAOYSA-N aluminum yttrium Chemical compound [Al].[Y] RFEISCHXNDRNLV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
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- 238000001192 hot extrusion Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
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Abstract
The invention discloses a preparation method of a nickel-based alloy target, and belongs to the field of metal target preparation. The method comprises the following steps: firstly, putting aluminum and yttrium together into a crucible in a vacuum smelting furnace, smelting to obtain aluminum yttrium intermediate alloy melt, and casting into a mould to obtain aluminum yttrium intermediate alloy; secondly, placing the aluminum-yttrium intermediate alloy, nickel, chromium, silicon and boron into a crucible in a vacuum smelting furnace together, smelting to obtain nickel-chromium-aluminum-yttrium-silicon-boron melt, and casting into a mould to obtain a nickel-based six-element alloy solid round ingot blank; and finally, sequentially carrying out hot isostatic pressing treatment, hot extrusion treatment, annealing, straightening and cooling and machining on the nickel-based six-element alloy solid round ingot blank to obtain the nickel-chromium-aluminum-yttrium-silicon-boron tube target. The method greatly improves the density of the nickel-based alloy, refines grains, overcomes the segregation problem of high and low melting point substances, and simultaneously effectively reduces the problems of oxygen content, shrinkage cavity, air holes and the like.
Description
Technical Field
The invention relates to a preparation method of a nickel-based alloy target, and belongs to the field of metal target preparation.
Background
The nickel-chromium-aluminum-yttrium-silicon coating has high-temperature oxidation resistance, high-temperature corrosion resistance and high-temperature abrasion resistance, and is widely applied to the bonding bottom layer of the aviation high-temperature heat-resistant coating or the thermal barrier coating. It can resist high temperature of 800-1000 deg.C, and can form compact oxide protecting film at high temperature to protect base metal from oxidation and prevent corrosion of environment medium. At present, the nickel-chromium-aluminum-yttrium-silicon alloy target is mainly obtained by a vacuum smelting technology. The melting point, density, thermal expansion coefficient and other properties of each element in the nickel-chromium-aluminum-yttrium-silicon alloy are greatly different. In the smelting process, the alloy cast ingot often has defects of uneven components, a large number of shrinkage cavities, air holes, cracks and the like, so that the production efficiency is low.
It is well known that the quality of the target has a critical determining effect on the performance of the sputtered film. This puts higher demands on the purity, grain size, uniformity, etc. of the target. In addition, the utilization rate of the rotary target material can reach more than 80%, and the utilization rate of the planar target material can only reach 30%. The utilization rate of the target material also directly influences the sputtering efficiency and cost of the target material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of a nickel-chromium-aluminum-yttrium-silicon rotary target. The method greatly improves the density of the nickel-based alloy, refines grains, overcomes the segregation problem of high and low melting point substances, and simultaneously effectively reduces the problems of oxygen content, shrinkage cavity, air holes and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the nickel-based alloy target comprises the following steps:
(1) Placing aluminum and yttrium together in a crucible in a vacuum smelting furnace, smelting to obtain aluminum-yttrium intermediate alloy melt, and casting the aluminum-yttrium intermediate alloy melt into a mould to obtain aluminum-yttrium intermediate alloy;
(2) Placing the aluminum-yttrium intermediate alloy, nickel, chromium, silicon and boron together in a crucible in a vacuum smelting furnace, smelting to obtain nickel-chromium-aluminum-yttrium-silicon-boron melt, and casting into a mould to obtain a nickel-base six-element alloy solid round ingot blank;
(3) Placing the solid round ingot blank of the nickel-based six-element alloy obtained in the step (2) into a hot isostatic pressing furnace for hot isostatic pressing treatment;
(4) Performing hot extrusion treatment on the nickel-based six-element alloy solid round ingot blank obtained in the step (3) to obtain a nickel-chromium-aluminum-yttrium-silicon-boron tube blank;
(5) And (3) sequentially annealing, straightening, cooling and machining the nickel-chromium-aluminum-yttrium-silicon-boron tube blank obtained in the step (4) to obtain the nickel-chromium-aluminum-yttrium-silicon-boron tube target.
The nickel-chromium-aluminum-yttrium-silicon-boron tube target prepared by the method comprises six elements, and the density and the melting point of different elements are different, so that aluminum and yttrium are smelted firstly to obtain an aluminum-yttrium intermediate alloy, and then the aluminum-yttrium intermediate alloy is smelted with other elements, and the problems that segregation and the like are easy to occur when high-melting-point metal and low-melting-point metal are smelted can be effectively prevented. By adopting vacuum induction melting, gas impurities can be prevented from being introduced, and electromagnetic stirring is used in the melting process, so that the nickel-based alloy melt is more uniform, and the components of the cast nickel-based six-element alloy solid round ingot blank are more uniform.
The compactness of the obtained nickel-based tube blank is greatly improved by adopting hot isostatic pressing and hot extrusion treatment, and coarse casting tissues are effectively crushed to obtain fine equiaxed grains. The nickel-based alloy round ingot blank obtained by vacuum smelting has cast defects such as slight microcracks, small-size air holes and the like, and the hot isostatic pressing can enable the microcracks and the small-size air holes to be closed, so that the compactness of the nickel-based alloy round ingot blank is improved. The nickel-based alloy tube target is obtained by carrying out hot extrusion operation on the nickel-based alloy round ingot blank, so that the problems of coarse internal structure, uneven grain distribution and the like of the as-cast alloy are solved. And the nickel-based alloy is shaped by adopting a hydraulic shaping machine, so that the subsequent machining of the rotary target is facilitated. The preparation method has good operability and high production efficiency, and can greatly save production cost.
As a preferred embodiment of the preparation method of the nickel-based alloy target material, in the step (1), the smelting temperature is 1300-1500 ℃ and the time is 5-15 min.
The melting point of yttrium is 1522 ℃, the melting point of aluminum is 660 ℃, and aluminum and yttrium can be melted in a vacuum melting furnace at 1300-1500 ℃.
As a preferred embodiment of the preparation method of the nickel-based alloy target material, in the step (2), the smelting temperature is 1500-1800 ℃ and the time is 5-15 min.
The melting points of nickel, chromium, silicon and boron are high, and the smelting temperature needs to be increased during smelting, so that all raw materials can be melted.
In the step (2), as a preferred embodiment of the preparation method of the nickel-based alloy target material, the mass fraction of each element in the nickel-based six-element alloy solid round ingot blank is as follows: cr:15% -20%, al:10% -15%, Y:0.2 to 1.0 percent, si:0.6 to 1.2 percent, B:0.05 to 0.1 percent, and the balance of Ni and other unavoidable impurities.
As a preferred embodiment of the preparation method of the nickel-based alloy target material, in the step (3), the hot isostatic pressing temperature is 1050-1200 ℃, the pressure is 80-150 Mpa, the time is 2-5 h, and the heating rate is 3-10 ℃/min.
Under the action of high temperature and high pressure in a hot isostatic press, the nickel-based six-element alloy solid round ingot blank has plastic deformation and creep behavior of hole defects such as internal looseness and the like, and further has diffusion behavior on the surface of a collapse area to finish hole healing, so that the alloy is more compact. The creep process is independent of the diffusion of solute atoms in a matrix, wherein the temperature and the pressure are two driving factors for the diffusion of solute atoms, the interaction of the two driving factors influences the healing rate of creep holes, the densification treatment process of the nickel-based six-element alloy solid round ingot blank by hot isostatic pressing is the result of the synergistic effect of multiple mechanical and multiple influencing factors, and the temperature, the time and the pressure are all factors influencing the hot isostatic pressing treatment. Under the hot isostatic pressing parameters, the cast defects such as microcracks, small-size air holes and the like in the nickel-based six-element alloy solid round ingot blank can be eliminated, and the density of the nickel-based alloy round ingot blank is improved.
As a preferred embodiment of the preparation method of the nickel-based alloy target material, in the step (4), the hot extrusion temperature is 1100-1300 ℃, and the hot extrusion speed is 10-30 cm/min.
The temperature of hot extrusion needs to be close to the heating temperature of a solid round ingot blank of the nickel-based six-element alloy, and the similar temperature can not cause the problems of micro-cracks, small-size air holes and the like of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank due to overlarge temperature difference.
In the step (4), the nickel-based six-element alloy solid round ingot blank needs to be heated before hot extrusion, the heating temperature is 1250-1450 ℃, and the heating time is 1-4 h.
When the heating temperature is 1250-1450 ℃ and the heating time is 1-4 h, the solid round ingot blank of the nickel-based six-element alloy is in a semi-molten state, and the molten crystalline phase structure can not be precipitated from the solid solution or be dispersed and precipitated as small particles.
As a preferred embodiment of the preparation method of the nickel-base alloy target material, in the step (5), the annealing temperature is 500-900 ℃ and the annealing time is 1-4 h.
The nickel-chromium-aluminum-yttrium-silicon-boron tube blank is annealed, so that the uniformity of the internal structure of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank can be improved.
As a preferred implementation mode of the nickel-based alloy target preparation method, in the step (5), the straightness of the straightened nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m.
The straightness of the straightened nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m, which is beneficial to the subsequent processing of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank and reduces the difficulty of the subsequent processing.
As a preferred embodiment of the preparation method of the nickel-based alloy target material, the vacuum degree of the vacuum melting furnace is less than 0.1Pa.
The vacuum degree of the vacuum smelting furnace is less than 0.1Pa, so that the formation of oxides of metal in the smelting process is effectively avoided.
Compared with the prior art, the invention has the beneficial effects that:
1) The nickel-base alloy is obtained through the vacuum smelting process, so that the oxygen content of the round ingot blank of the nickel-base alloy is greatly reduced, and the purity of the ingot blank is improved;
2) And (3) performing densification treatment by hot isostatic pressing to enable microcracks and small-size air holes to be closed, and improving the density of the solid round ingot blank of the nickel-base alloy.
3) Preparing a high-purity nickel alloy tube blank through hot extrusion, and effectively crushing coarse casting tissues in the high-purity nickel alloy tube blank;
4) The high-purity nickel alloy tube blank formed by hot extrusion is directly straightened by a straightener, the preparation flow is short, and the production time and the cost are saved.
5) The alloy target material obtained by the preparation method of the high-purity nickel alloy provided by the invention has high yield, fine grains and uniform internal structure;
6) The high-purity nickel alloy rotary target provided by the invention is more stable in sputtering, and uniform in film formation during use, so that a high-quality film with uniform thickness can be obtained, and the target utilization rate is improved.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a nickel-based alloy target of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples and the accompanying drawings.
FIG. 1 is a process flow diagram of a method for preparing a nickel-based alloy target of the present invention. The specific steps of the preparation method of the nickel-based alloy target material are shown in the following examples.
Example 1
The embodiment provides a preparation method of a nickel-based alloy target, which comprises the following steps:
(1) Placing aluminum and yttrium together in a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 10min when the smelting temperature is up to 1400 ℃ to obtain aluminum yttrium intermediate alloy melt; then casting into a mould to obtain an aluminum yttrium intermediate alloy;
(2) Placing aluminum yttrium intermediate alloy, nickel, chromium, silicon, boron and other element metals into a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 10min when the smelting temperature is up to 1400 ℃, so as to obtain nickel-chromium aluminum yttrium silicon boron melt; casting the nickel-chromium-aluminum-yttrium-silicon-boron melt into a graphite mold, and cooling to room temperature to obtain a nickel-based six-element alloy solid round ingot blank; wherein the mass fraction of each element in the cast ingot is as follows: cr:15% -20%, al:10% -15%, Y:0.2 to 1.0 percent, si:0.6 to 1.2 percent, B:0.05 to 0.1 percent, and the balance of Ni and other unavoidable impurities;
(3) And vacuumizing the hot isostatic pressing furnace until the vacuum degree of the hot isostatic pressing furnace is less than or equal to 100Pa, and filling inert gas or nitrogen into the hot isostatic pressing furnace. Filling inert gas or nitrogen, and then directly placing the cooled nickel-base alloy solid round ingot blank into a hot isostatic pressing furnace for heating and pressurizing; the hot isostatic pressing temperature of the hot isostatic pressing furnace is 1150 ℃, the hot isostatic pressing heating speed of the hot isostatic pressing furnace is 6 ℃/min, the hot isostatic pressing pressure of the hot isostatic pressing furnace is 110Mpa, and the heat preservation time is 4h under the hot isostatic pressing temperature and the hot isostatic pressing pressure; cooling along with the furnace to enable the microcracks and the small-size air holes to be closed, so that the density of the nickel-based six-element alloy solid round ingot blank is improved;
(4) Placing the nickel-based six-element alloy solid round ingot blank obtained in the step (3) into a heating furnace, setting the heating temperature to 1350 ℃ and the heating time to 3h, so that the nickel-based six-element alloy solid round ingot blank is in a semi-molten state, and ensuring that a soluble crystalline phase structure is not precipitated from solid solution or is dispersed and precipitated as small particles;
designing an extrusion die for preparing the nickel-based six-element alloy according to the size of a product, and installing the die in a double-acting reverse extruder; preheating the extrusion cylinder and the extrusion rod at 1200 ℃, and uniformly coating lubricant on the surface of the extrusion cylinder; and taking out the heated nickel-based six-element alloy billet, uniformly coating lubricant on the outer surface of the nickel-based six-element alloy billet, and transferring the nickel-based six-element alloy billet to an extrusion cylinder for 20s. The extrusion speed is controlled to be 20cm/min, and under the combined action of the double-acting reverse extruder and the die, the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is extruded slowly from the outlet of the double-acting reverse extruder;
(5) Recrystallizing and annealing the cooled nickel alloy tube blank at 700 ℃, and preserving heat for 2 hours to improve the uniformity of internal tissues;
(6) Adopting a hydraulic shaping machine to shape the recrystallized annealed nickel-chromium-aluminum-yttrium-silicon-boron tube blank, so that the straightness of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m; transferring the nickel-chromium-aluminum-yttrium-silicon-boron tube blank into water for cooling;
(7) Cutting the straightened and cooled nickel-chromium-aluminum-yttrium-silicon-boron tube blank on a numerical control machine tool, and carrying out rough and fine machining on the outer circle, the inner circle and the length to obtain the nickel-chromium-aluminum-yttrium-silicon-boron tube target. Wherein, the unilateral feed amount is 0.05-0.10 mm, and the dimensional accuracy and the surface roughness of the finished nickel-chromium-aluminum-yttrium-silicon-boron tube target meet the specified requirements; in the turning process, cooling liquid needs to be sprayed to achieve the cooling effect.
Example 2
The present embodiment provides a method for preparing a nickel-based alloy target, and the difference between the present embodiment and embodiment 1 is that: in step (5), the annealing temperature is 900 ℃.
Example 3
The present embodiment provides a method for preparing a nickel-based alloy target, and the difference between the present embodiment and embodiment 1 is that: in step (5), the annealing time was 4 hours.
Example 4
The embodiment provides a preparation method of a nickel-based alloy target, which comprises the following steps:
(1) Placing aluminum and yttrium together in a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 15min when the smelting temperature is up to 1300 ℃ to obtain aluminum yttrium intermediate alloy melt; then casting into a mould to obtain an aluminum yttrium intermediate alloy;
(2) Placing aluminum yttrium intermediate alloy, nickel, chromium, silicon, boron and other element metals into a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 15min when the smelting temperature is up to 1500 ℃, so as to obtain nickel-chromium aluminum yttrium silicon boron melt; casting the nickel-chromium-aluminum-yttrium-silicon-boron melt into a graphite mold, and cooling to room temperature to obtain a nickel-based six-element alloy solid round ingot blank; wherein the mass fraction of each element in the cast ingot is as follows: cr:15% -20%, al:10% -15%, Y:0.2 to 1.0 percent, si:0.6 to 1.2 percent, B:0.05 to 0.1 percent, and the balance of Ni and other unavoidable impurities;
(3) And vacuumizing the hot isostatic pressing furnace until the vacuum degree of the hot isostatic pressing furnace is less than or equal to 100Pa, and filling inert gas or nitrogen into the hot isostatic pressing furnace. Filling inert gas or nitrogen, and then directly placing the cooled nickel-base alloy solid round ingot blank into a hot isostatic pressing furnace for heating and pressurizing; the hot isostatic pressing temperature of the hot isostatic pressing furnace is 1050 ℃, the hot isostatic pressing heating speed of the hot isostatic pressing furnace is 3 ℃/min, the hot isostatic pressing pressure of the hot isostatic pressing furnace is 80Mpa, and the heat preservation time is 5h under the hot isostatic pressing temperature and the hot isostatic pressing pressure; cooling along with the furnace to enable the microcracks and the small-size air holes to be closed, so that the density of the nickel-based six-element alloy solid round ingot blank is improved;
(4) Placing the nickel-based six-element alloy solid round ingot blank obtained in the step (3) into a heating furnace, setting the heating temperature to 1250 ℃ and the heating time to 4 hours, so that the nickel-based six-element alloy solid round ingot blank is in a semi-molten state, and ensuring that a soluble crystalline phase structure is not precipitated from solid solution or is dispersed and precipitated as small particles;
designing an extrusion die for preparing the nickel-based six-element alloy according to the size of a product, and installing the die in a double-acting reverse extruder; preheating the extrusion cylinder and the extrusion rod at 1100 ℃, and uniformly coating lubricant on the surface of the extrusion cylinder; and taking out the heated nickel-based six-element alloy billet, uniformly coating lubricant on the outer surface of the nickel-based six-element alloy billet, and transferring the nickel-based six-element alloy billet to an extrusion cylinder for 20s. The extrusion speed is controlled to be 10cm/min, and under the combined action of the double-acting reverse extruder and the die, the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is extruded slowly from the outlet of the double-acting reverse extruder;
(5) Recrystallizing and annealing the cooled nickel alloy tube blank at 700 ℃, and preserving heat for 1 hour to improve the uniformity of internal tissues;
(6) Adopting a hydraulic shaping machine to shape the recrystallized annealed nickel-chromium-aluminum-yttrium-silicon-boron tube blank, so that the straightness of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m; transferring the nickel-chromium-aluminum-yttrium-silicon-boron tube blank into water for cooling;
(7) Cutting the straightened and cooled nickel-chromium-aluminum-yttrium-silicon-boron tube blank on a numerical control machine tool, and carrying out rough and fine machining on the outer circle, the inner circle and the length to obtain the nickel-chromium-aluminum-yttrium-silicon-boron tube target. Wherein, the unilateral feed amount is 0.05-0.10 mm, and the dimensional accuracy and the surface roughness of the finished nickel-chromium-aluminum-yttrium-silicon-boron tube target meet the specified requirements; in the turning process, cooling liquid needs to be sprayed to achieve the cooling effect.
Example 5
The embodiment provides a preparation method of a nickel-based alloy target, which comprises the following steps:
(1) Placing aluminum and yttrium together in a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 5min when the smelting temperature is up to 1500 ℃ to obtain aluminum yttrium intermediate alloy melt; then casting into a mould to obtain an aluminum yttrium intermediate alloy;
(2) Placing aluminum yttrium intermediate alloy, nickel, chromium, silicon, boron and other element metals into a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 5min when the smelting temperature is up to 1800 ℃ to obtain nickel-chromium aluminum yttrium silicon boron melt; casting the nickel-chromium-aluminum-yttrium-silicon-boron melt into a graphite mold, and cooling to room temperature to obtain a nickel-based six-element alloy solid round ingot blank; wherein the mass fraction of each element in the cast ingot is as follows: cr:15% -20%, al:10% -15%, Y:0.2 to 1.0 percent, si:0.6 to 1.2 percent, B:0.05 to 0.1 percent, and the balance of Ni and other unavoidable impurities;
(3) And vacuumizing the hot isostatic pressing furnace until the vacuum degree of the hot isostatic pressing furnace is less than or equal to 100Pa, and filling inert gas or nitrogen into the hot isostatic pressing furnace. Filling inert gas or nitrogen, and then directly placing the cooled nickel-base alloy solid round ingot blank into a hot isostatic pressing furnace for heating and pressurizing; the hot isostatic pressing temperature of the hot isostatic pressing furnace is 1200 ℃, the hot isostatic pressing heating speed of the hot isostatic pressing furnace is 10 ℃/min, the hot isostatic pressing pressure of the hot isostatic pressing furnace is 150Mpa, and the heat preservation time is 2h under the hot isostatic pressing temperature and the hot isostatic pressing pressure; cooling along with the furnace to enable the microcracks and the small-size air holes to be closed, so that the density of the nickel-based six-element alloy solid round ingot blank is improved;
(4) Placing the nickel-based six-element alloy solid round ingot blank obtained in the step (3) into a heating furnace, setting the heating temperature to 1450 ℃, and heating for 1h to enable the nickel-based six-element alloy solid round ingot blank to be in a semi-molten state, so as to ensure that a soluble crystalline phase structure is not precipitated from solid solution or is dispersed and precipitated as small particles;
designing an extrusion die for preparing the nickel-based six-element alloy according to the size of a product, and installing the die in a double-acting reverse extruder; preheating the extrusion cylinder and the extrusion rod at 1300 ℃, and uniformly coating lubricant on the surface of the extrusion cylinder; and taking out the heated nickel-based six-element alloy billet, uniformly coating lubricant on the outer surface of the nickel-based six-element alloy billet, and transferring the nickel-based six-element alloy billet to an extrusion cylinder for 20s. The extrusion speed is controlled to be 30cm/min, and under the combined action of the double-acting reverse extruder and the die, the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is extruded slowly from the outlet of the double-acting reverse extruder;
(5) Recrystallizing and annealing the cooled nickel alloy tube blank at 500 ℃, and preserving heat for 2 hours to improve the uniformity of internal tissues;
(6) Adopting a hydraulic shaping machine to shape the recrystallized annealed nickel-chromium-aluminum-yttrium-silicon-boron tube blank, so that the straightness of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m; transferring the nickel-chromium-aluminum-yttrium-silicon-boron tube blank into water for cooling;
(7) Cutting the straightened and cooled nickel-chromium-aluminum-yttrium-silicon-boron tube blank on a numerical control machine tool, and carrying out rough and fine machining on the outer circle, the inner circle and the length to obtain the nickel-chromium-aluminum-yttrium-silicon-boron tube target. Wherein, the unilateral feed amount is 0.05-0.10 mm, and the dimensional accuracy and the surface roughness of the finished nickel-chromium-aluminum-yttrium-silicon-boron tube target meet the specified requirements; in the turning process, cooling liquid needs to be sprayed to achieve the cooling effect.
Comparative example 1
The comparative example provides a preparation method of a nickel-based alloy target, which comprises the following steps:
(1) Placing aluminum and yttrium together in a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 10min when the smelting temperature is up to 1400 ℃ to obtain aluminum yttrium intermediate alloy melt; then casting into a mould to obtain an aluminum yttrium intermediate alloy;
(2) Placing aluminum yttrium intermediate alloy, nickel, chromium, silicon, boron and other element metals into a crucible in a vacuum smelting furnace, vacuumizing and heating by induction, wherein the vacuum degree is less than 0.1Pa, and keeping the temperature for 10min when the smelting temperature is up to 1400 ℃, so as to obtain nickel-chromium aluminum yttrium silicon boron melt; casting the nickel-chromium-aluminum-yttrium-silicon-boron melt into a graphite mold, and cooling to room temperature to obtain a nickel-based six-element alloy solid round ingot blank; wherein the mass fraction of each element in the cast ingot is as follows: cr:15% -20%, al:10% -15%, Y:0.2 to 1.0 percent, si:0.6 to 1.2 percent, B:0.05 to 0.1 percent, and the balance of Ni and other unavoidable impurities;
(3) Placing the nickel-based six-element alloy solid round ingot blank obtained in the step (2) into a heating furnace, setting the heating temperature to 1350 ℃ and the heating time to 3 hours, so that the nickel-based six-element alloy solid round ingot blank is in a semi-molten state, and ensuring that a soluble crystalline phase structure is not precipitated from solid solution or is dispersed and precipitated as small particles;
designing an extrusion die for preparing the nickel-based six-element alloy according to the size of a product, and installing the die in a double-acting reverse extruder; preheating the extrusion cylinder and the extrusion rod at 1200 ℃, and uniformly coating lubricant on the surface of the extrusion cylinder; and taking out the heated nickel-based six-element alloy billet, uniformly coating lubricant on the outer surface of the nickel-based six-element alloy billet, and transferring the nickel-based six-element alloy billet to an extrusion cylinder for 20s. The extrusion speed is controlled to be 20cm/min, and under the combined action of the double-acting reverse extruder and the die, the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is extruded slowly from the outlet of the double-acting reverse extruder;
(4) Recrystallizing and annealing the cooled nickel alloy tube blank at 700 ℃, and preserving heat for 2 hours to improve the uniformity of internal tissues;
(5) Adopting a hydraulic shaping machine to shape the recrystallized annealed nickel-chromium-aluminum-yttrium-silicon-boron tube blank, so that the straightness of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m; transferring the nickel-chromium-aluminum-yttrium-silicon-boron tube blank into water for cooling;
(6) Cutting the straightened and cooled nickel-chromium-aluminum-yttrium-silicon-boron tube blank on a numerical control machine tool, and carrying out rough and fine machining on the outer circle, the inner circle and the length to obtain the nickel-chromium-aluminum-yttrium-silicon-boron tube target. Wherein, the unilateral feed amount is 0.05-0.10 mm, and the dimensional accuracy and the surface roughness of the finished nickel-chromium-aluminum-yttrium-silicon-boron tube target meet the specified requirements; in the turning process, cooling liquid needs to be sprayed to achieve the cooling effect.
Effect example 1
The nickel chromium aluminum yttrium silicon boron tube targets obtained in examples 1-5 and comparative example 1 were tested and the test results are shown in table 1.
The testing method of each performance comprises the following steps:
oxygen content: the sample is placed in a high purity graphite crucible and oxygen in the sample reacts with carbon in the graphite crucible to form carbon monoxide (CO) at temperatures up to 3000 ℃ in an atmosphere of an inert gas such as helium, the oxygen being detectable by an infrared detector as carbon dioxide (CO 2), carbon monoxide (CO) or both.
Density: the solid density tester is a novel specific gravity tester developed by combining the modern micro-solid technology with the Archimedes principle. The working principle is that an equation is formed by deduction and transformation of a buoyancy and density calculation formula, firstly, a high-precision solid analytical balance is utilized to respectively calculate the weight w1 of an object to be measured in the air and the weight w2 of the object to be measured in water, the value of w1-w2 is calculated, the density of water defaults ρ=1, and the density value of a sample can be calculated by establishing the equation through Vsample=Vdrainage: ρ=w1/(w 1-w 2).
Grain size: firstly, sequentially carrying out rough grinding and fine grinding by using 250, 600, 1000 and 2000-mesh sand paper, mechanically polishing by using diamond grinding paste with the granularity of 0.5 micron, then corroding by using a proper corrosive agent, observing a microstructure by using a DM 40000M optical microscope, randomly taking ten photos from each place of a sample, and carrying out statistical averaging by using Nano Measurer software to obtain the average grain size of the sample.
Yield rate: and determining the number of good products of the nickel-chromium-aluminum-yttrium-silicon-boron tube blank according to the principle that factors such as crack-free, hole-free shrinkage, density, impurity content, oxygen content, grain size and the like accord with customer specifications. The yield is the number of good products/smelting number.
TABLE 1
With respect to example 1, comparative example 1 was not densified by hot isostatic pressing, and the density of the resulting nickel-base alloy was lower than in the other examples; second, there is a significant increase in oxygen content. The invention is proved to carry out densification treatment by hot isostatic pressing, eliminates microcracks generated in the target material and closed small-size air holes, and increases the yield of the nickel-based alloy. The temperature and time of heat treatment after hot extrusion are respectively increased in the embodiment 2 and the embodiment 3, and the hot extrusion procedure can effectively crush the coarse casting tissues in the high-purity copper pipe blank; the nickel-based target material is subjected to a recovery recrystallization process, and broken grains are again nucleated and grown. When the temperature of recrystallization is too high, or the recrystallization time is too long, the crystal grains will sufficiently grow and exhibit a non-uniform phenomenon. In example 4, the casting temperature, the hot isostatic pressing temperature and the extrusion temperature were both high; in a proper casting temperature range, the higher the casting temperature is, the gas impurities can be effectively removed; in the densification process, the alloy density is increased due to the higher temperature of the extrusion temperature such as heat. In example 5, the casting temperature, the hot isostatic pressing temperature and the extrusion temperature were both low, and the oxygen content was slightly higher and the density was slightly lower than in example 4.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that the technical scheme of the invention may be modified or equally substituted without departing from the spirit and scope of the technical scheme of the invention.
Claims (4)
1. The preparation method of the nickel-based alloy target is characterized by comprising the following steps of:
(1) Placing aluminum and yttrium together in a crucible in a vacuum smelting furnace, smelting to obtain aluminum-yttrium intermediate alloy melt, and casting the aluminum-yttrium intermediate alloy melt into a mould to obtain aluminum-yttrium intermediate alloy;
(2) Placing an aluminum-yttrium intermediate alloy, nickel, chromium, silicon and boron into a crucible in a vacuum smelting furnace together, smelting to obtain nickel-chromium-aluminum-yttrium-silicon-boron melt, and casting into a mould to obtain a nickel-base six-element alloy solid round ingot blank, wherein the mass fractions of elements in the nickel-base six-element alloy solid round ingot blank are as follows: cr:15% -20%, al:10% -15%, Y:0.2 to 1.0 percent, si:0.6 to 1.2 percent, B:0.05 to 0.1 percent, and the balance of Ni and other unavoidable impurities;
(3) Placing the solid round ingot blank of the nickel-based six-element alloy obtained in the step (2) into a hot isostatic pressing furnace for hot isostatic pressing treatment;
(4) Carrying out hot extrusion treatment on the nickel-based six-element alloy solid round ingot blank obtained in the step (3) to obtain a nickel-chromium-aluminum-yttrium-silicon-boron tube blank, wherein the hot extrusion temperature is 1100-1300 ℃, and the extrusion speed is 10-30 cm/min;
(5) Sequentially annealing, straightening and cooling the nickel-chromium-aluminum-yttrium-silicon-boron tube blank obtained in the step (4), and machining to obtain a nickel-chromium-aluminum-yttrium-silicon-boron tube target, wherein the annealing temperature is 500-900 ℃ and the annealing time is 1-4 hours;
in the step (1), the smelting temperature is 1300-1500 ℃ and the smelting time is 5-15 min;
in the step (2), the smelting temperature is 1500-1800 ℃ and the smelting time is 5-15 min;
in the step (3), the temperature of the hot isostatic pressing is 1050-1200 ℃, the pressure is 80-150 MPa, the time is 2-5 h, and the heating rate is 3-10 ℃/min.
2. The method according to claim 1, wherein in the step (4), the solid round ingot of the nickel-based six-element alloy is heated at 1250-1450 ℃ for 1-4 hours before hot extrusion.
3. The method according to claim 1, wherein in the step (5), the straightness of the straightened nickel-chromium-aluminum-yttrium-silicon-boron tube blank is less than 1mm/m.
4. The method of claim 1, wherein the vacuum degree of the vacuum melting furnace is less than 0.1Pa.
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