CN114769585A - Cold spray forming method of Cu-Cr-Nb series alloy - Google Patents
Cold spray forming method of Cu-Cr-Nb series alloy Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 21
- 238000009718 spray deposition Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000005507 spraying Methods 0.000 claims abstract description 27
- 229910001257 Nb alloy Inorganic materials 0.000 claims abstract description 21
- 238000010288 cold spraying Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 230000007547 defect Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005488 sandblasting Methods 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000001856 aerosol method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000010290 vacuum plasma spraying Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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Abstract
The invention discloses a cold spray forming method of Cu-Cr-Nb alloy, which comprises the following steps: drying the screened Cu-Cr-Nb powder material; spraying Cu-Cr-Nb powder onto a substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb spraying layer; performing vacuum annealingFire treatment to eliminate the interface defect of the sprayed layer; precisely machining and removing the substrate material to obtain a Cu-Cr-Nb alloy formed piece. The method realizes the rapid forming of the Cu-Cr-Nb alloy, combines the subsequent low-temperature vacuum annealing treatment, performs the structure optimization, and eliminates the interface defect in the spraying layer. Due to the low-temperature treatment process, Cr2The Nb phase is not coarsened, the mechanical property of the alloy is ensured, the hardness of the Cu-Cr-Nb alloy formed by cold spraying can reach 200-300HV, and the size of the Cr2Nb phase is kept between 2 and 8 mu m.
Description
Technical Field
The invention relates to the technical field of copper alloy preparation, in particular to a cold spray forming method of a Cu-Cr-Nb alloy.
Background
Strengthening phase Cr in Cu-Cr-Nb alloy2The Nb phase is an intermetallic compound and has high melting point (about 1730 ℃) and high-temperature stability, so that the alloy has excellent performances of electric conduction, thermal expansion, creep resistance, high strength, high ductility, excellent low-frequency fatigue resistance and the like, and is an ideal material for a rocket engine combustion chamber lining. However, slow cooling of the alloy during normal melt casting production may result in Cr2The Nb phase is obviously coarsened, the size reaches 1 cm, and the strengthening effect is lost. Therefore, the alloy can only be prepared into powder by an aerosol method to prevent Cr2The Nb phase grows up. In order to apply the Cu-Cr-Nb material to a service scene, the Cu-Cr-Nb powder is solidified into a fully compact block material. The high temperature adopted by the hot isostatic pressing, vacuum plasma spraying and other technologies adopted at present still causes partial Cr2The Nb phase grains grow up. In addition, the current Cu-Cr-Nb powder curing process such as hot isostatic pressing, vacuum plasma spraying and the like has high cost and low efficiency, and limits the application and popularization of the materials.
In the patents CN111440963B, CN112553500A and CN110218897A, Cu-Cr-Nb alloy powder is prepared by adopting an aerosol method, then alloy preparation is realized by utilizing the processes of hot pressing, SPS and the like, the solidification temperature of the powder is higher than 800 ℃, and Cr cannot be avoided in the treatment process2The Nb phase coarsens to degrade the alloy properties. In addition, the method has higher cost and low production efficiency. Currently related to the production of Cu-Cr-Nb alloysThe preparation methods all have certain technical defects, and the effective inhibition of Cr is difficult2Coarsening the Nb phase and realizing high-efficiency production.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a cold spray forming method of a Cu-Cr-Nb alloy.
The invention is realized by the following technical scheme.
A cold spray forming method of a Cu-Cr-Nb alloy, characterized by comprising:
(1) drying the screened Cu-Cr-Nb powder material;
(2) spraying the Cu-Cr-Nb powder obtained in the step (1) onto a substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb spraying layer;
(3) carrying out vacuum annealing treatment on the Cu-Cr-Nb spray coating obtained in the step (2) to eliminate the interface defect of the spray coating;
(4) and (4) precisely processing the spray coating obtained in the step (3) to remove the base material, thereby obtaining a Cu-Cr-Nb alloy formed piece (plate or cylindrical piece).
Further, the atomic percentage composition of the Cu-Cr-Nb powder component in the step (1) comprises: cr 4-8 at.%, Nb2-4 at.%, and Cu and inevitable impurities as the rest.
Further, in the step (1), the grain diameter of Cu-Cr-Nb powder is 20-50 mu m, and Cr in the powder2The Nb phase size is less than 8 μm.
Further, the base material in the step (2) is a copper plate or a cylindrical copper material with a surface subjected to sand blasting.
Further, in the step (2), the base material is fixed on a rotating shaft with the rotating speed of 80-150 rpm for spraying.
Further, the process parameters of spraying by using the cold spraying equipment in the step (2) comprise: the carrier gas is one of compressed air, nitrogen or argon, the pressure of the carrier gas is 2-6 MPa, the preheating temperature is 400-500 ℃, the distance between the surface of the substrate material and the nozzle outlet of the spray gun is 30-60 mm, and the moving speed of the spray gun is 3-10 mm/s.
Further, the annealing temperature of the vacuum annealing treatment in the step (3) is 600-800 ℃, and the treatment time is 1.5-3 h.
Further, the obtained Cu-Cr-Nb alloy formed article has a microstructure of Cr2The size of the Nb phase is 2-8 mu m, no interface defect exists in the structure, and the Vickers hardness reaches 200-300 HV.
The invention relates to a method for preparing Cu-Cr-Nb alloy, which is a process for accelerating metal powder to supersonic speed by using high-pressure gas at the temperature lower than the melting point of the material and continuously spraying the metal powder onto a substrate material by using a cold spraying technology so as to enable powder particles to generate strong plastic deformation and be accumulated into blocks. The method is a manufacturing process based on high deformation rate and large deformation. The cold spraying has the advantages of high deposition rate, unlimited coating thickness, low residual thermal stress, difficult material oxidation and the like.
The invention has the beneficial technical effects that the cold spraying technology is applied to the solidification forming of the Cu-Cr-Nb powder, the rapid forming of the Cu-Cr-Nb alloy is realized, the subsequent low-temperature vacuum annealing treatment is combined, the structure optimization is carried out, and the interface defect in the spraying layer is eliminated. Due to the low-temperature treatment process, Cr2The Nb phase is not coarsened, the mechanical property of the alloy is ensured, the hardness of the Cu-Cr-Nb alloy formed by cold spraying can reach 200-300HV, Cr2The Nb phase size is kept between 2 and 8 mu m.
Drawings
FIG. 1 is a microstructure pattern of Cu-Cr-Nb alloy obtained by the invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the Cu-Cr-Nb series alloy cold spraying preparation method comprises the following steps:
(1) selecting Cu-4 at.% Cr-2 at.% Nb with grain size of 25 μm and Cr content2Drying the powder with the Nb phase size of less than 5 mu m for 30min in a vacuum drying oven at the temperature of 80 ℃ to obtain a cold spraying powder raw material; an electrolytic copper plate subjected to sand blasting after cold rolling is selected as a base material, and the base material is fixed on a rotating shaft with the rotating speed of 120 rpm.
And 2, spraying the Cu-Cr-Nb powder onto the substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb spraying layer. The technological parameters of cold spraying are as follows: the carrier gas is compressed air, the pressure of the carrier gas is 3MPa, the preheating temperature is 420 ℃, the distance between the surface of the substrate material and the nozzle outlet of the spray gun is 50mm, and the spray gun moves up and down at the moving speed of 5 mm/s.
And 3, putting the Cu-Cr-Nb spray coating obtained in the step 2 into a vacuum annealing furnace for annealing treatment at 650 ℃ for 2 hours.
And 4, turning the sprayed layer annealed in the step 3 to remove the substrate material to obtain a finished Cu-Cr-Nb alloy forming piece. Cr in alloy2The Nb phase size is still kept less than 5 μm, and the alloy hardness is 215 HV.
Example 2:
the Cu-Cr-Nb series alloy cold spraying preparation method comprises the following steps:
(1) selecting Cu-8 at.% Cr-4 at.% Nb with grain size of 50 μm and Cr content2Drying the powder with the Nb phase size of 2-5 mu m for 20min in a vacuum drying oven at the temperature of 90 ℃ to obtain a cold spraying powder raw material; an electrolytic copper cylinder subjected to sand blasting after cold rolling is selected as a base material, and the base material is fixed on a rotating shaft with the rotating speed of 150 rpm.
And 2, spraying Cu-Cr-Nb powder onto the substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb spraying layer. The technological parameters of cold spraying are as follows: the carrier gas is nitrogen, the pressure of the carrier gas is 5MPa, the preheating temperature is 450 ℃, the distance between the surface of the substrate material and the outlet of the nozzle of the spray gun is 40mm, and the spray gun moves up and down at the moving speed of 6 mm/s.
And 3, putting the Cu-Cr-Nb spray coating obtained in the step 2 into a vacuum annealing furnace for annealing treatment at 700 ℃ for 3 hours.
And 4, turning the sprayed layer annealed in the step 3 to remove the substrate material to obtain a finished Cu-Cr-Nb alloy cylindrical piece. Cr in alloy2The Nb phase size is still kept between 2 and 5 mu m, and the alloy hardness is 289 HV.
Example 3:
the Cu-Cr-Nb series alloy cold spraying preparation method of the present embodiment includes the following steps:
(1) selecting Cu-6 at.% Cr-3 at.% Nb with grain size of 40 μm and Cr content2Drying the powder with the Nb phase size of 4-8 mu m for 30min in a vacuum drying oven at the temperature of 85 ℃ to obtain a cold spraying powder raw material; an electrolytic copper plate subjected to sand blasting after cold rolling is selected as a base material, and the base material is fixed on a rotating shaft with the rotating speed of 100 rpm.
And 2, spraying the Cu-Cr-Nb powder onto the substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb spraying layer. The technological parameters of cold spraying are as follows: the carrier gas is argon, the pressure of the carrier gas is 4MPa, the preheating temperature is 480 ℃, the distance between the surface of the substrate material and the nozzle outlet of the spray gun is 45mm, and the spray gun moves up and down at the moving speed of 4 mm/s.
And 3, putting the Cu-Cr-Nb spray coating obtained in the step 2 into a vacuum annealing furnace for annealing treatment at 675 ℃ for heat preservation for 3 hours.
And 4, turning the spray coating annealed in the step 3 to remove the substrate material to obtain the finished Cu-Cr-Nb alloy plate. Cr in alloy2The Nb phase size is still kept less than 8 μm, and the alloy hardness is 256 HV.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (8)
1. A cold spray forming method for a Cu-Cr-Nb alloy, characterized by comprising:
(1) drying the screened Cu-Cr-Nb powder material;
(2) spraying the Cu-Cr-Nb powder obtained in the step (1) onto a substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb spraying layer;
(3) carrying out vacuum annealing treatment on the Cu-Cr-Nb spraying layer obtained in the step (2);
(4) and (4) removing the substrate material from the spray coating obtained in the step (3) to obtain a Cu-Cr-Nb alloy forming piece.
2. The cold spray forming method of a Cu-Cr-Nb-based alloy according to claim 1, wherein the atomic percentage composition of the Cu-Cr-Nb powder component in the step (1) includes: cr 4-8 at.%, Nb2-4 at.%, and Cu and inevitable impurities as balance.
3. The cold spray forming method of a Cu-Cr-Nb series alloy according to claim 1, wherein the grain size of the Cu-Cr-Nb powder in the step (1) is 20 to 50 μm, and Cr in the powder is2The Nb phase size is less than 8 μm.
4. The cold spray forming method of a Cu-Cr-Nb based alloy according to claim 1, wherein the base material in the step (2) is a copper plate or a cylindrical copper material whose surface is subjected to sand blasting.
5. The cold spray forming method of a Cu-Cr-Nb system alloy according to claim 1, wherein the step (2) comprises spraying the base material while fixing the base material on a rotating shaft rotating at 80 to 150 rpm.
6. The cold spray forming method of a Cu-Cr-Nb series alloy according to claim 1, wherein the process parameters sprayed by the cold spray device in the step (2) include: the carrier gas is one of compressed air, nitrogen or argon, the pressure of the carrier gas is 2-6 MPa, the preheating temperature is 400-500 ℃, the distance between the surface of the substrate material and the nozzle outlet of the spray gun is 30-60 mm, and the moving speed of the spray gun is 3-10 mm/s.
7. The cold spray forming method of a Cu-Cr-Nb series alloy according to claim 1, wherein the annealing temperature of the vacuum annealing in the step (3) is 600 to 800 ℃, and the processing time is 1.5 to 3 hours.
8. The cold spray forming method of a Cu-Cr-Nb alloy according to claim 1, wherein the Cu-Cr-Nb alloy formed article obtained has a microstructure containing Cr2The size of the Nb phase is 2-8 mu m, no interface defect exists in the structure, and the Vickers hardness reaches 200-300 HV.
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