CN114769585B - Cold spray forming method of Cu-Cr-Nb alloy - Google Patents
Cold spray forming method of Cu-Cr-Nb alloy Download PDFInfo
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- 229910001257 Nb alloy Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000009718 spray deposition Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000005507 spraying Methods 0.000 claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 238000010288 cold spraying Methods 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 230000007547 defect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 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
- 239000002245 particle Substances 0.000 claims description 4
- 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
- 238000003754 machining Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005488 sandblasting Methods 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007514 turning 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
- 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
- 239000013590 bulk material Substances 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
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface
-
- 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
Abstract
The invention discloses a cold spray forming method of a 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; carrying out vacuum annealing treatment to eliminate interface defects of the spray coating; and (5) precisely machining to remove the base material to obtain the Cu-Cr-Nb alloy forming piece. The method of the invention realizes the rapid forming of Cu-Cr-Nb alloy, and combines the subsequent low-temperature vacuum annealing treatment to carry out tissue optimization, thereby eliminating the interface defect inside the spray coating. Because of adopting the low-temperature treatment process, cr 2 The 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 Cr2Nb phase size is kept 2‑8μm。
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 alloy 2 The Nb phase is an intermetallic compound and has high melting point (about 1730 ℃) and high-temperature stability, so that the alloy has excellent electric conduction, thermal expansion, creep resistance, high strength, high ductility, excellent low-frequency fatigue resistance and other performances, and is an ideal material for the inner liner of the rocket engine combustion chamber. However, cr is caused by slow cooling of the alloy during ordinary casting preparation 2 The 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 Cr 2 The Nb phase grows. In order to apply the Cu-Cr-Nb material to service scenarios, it is also necessary to solidify the Cu-Cr-Nb powder into a fully dense bulk material. The technologies of hot isostatic pressing, vacuum plasma spraying and the like adopted at present still can cause partial Cr due to higher temperature 2 The Nb phase particles grow. In addition, the existing curing process of Cu-Cr-Nb powder such as hot isostatic pressing, vacuum plasma spraying and the like has higher cost and lower efficiency, and limits the application and popularization of the materials.
In the patent CN111440963B, CN112553500A, CN110218897A, the Cu-Cr-Nb alloy powder is prepared by adopting an aerosol method, then the alloy preparation is realized by adopting hot pressing, SPS and other processes, and the powder curing temperature is equalAbove 800 ℃, cr cannot be avoided in the treatment process 2 The Nb phase coarsens and reduces the alloy properties. In addition, the cost of the method is high, and the production efficiency is low. The current preparation method of the Cu-Cr-Nb alloy has certain technical defects, and is difficult to effectively inhibit Cr 2 The Nb phase coarsens and achieves efficient production.
Disclosure of Invention
The invention provides a cold spray forming method of Cu-Cr-Nb alloy aiming at the defects existing in the prior art.
The invention is realized by the following technical scheme.
A method for cold spray forming of a Cu-Cr-Nb-based alloy, the method 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 sprayed layer;
(3) Carrying out vacuum annealing treatment on the Cu-Cr-Nb spraying layer obtained in the step (2) so as to eliminate interface defects of the spraying layer;
(4) And (3) carrying out precision machining on the spray coating obtained in the step (3) to remove the base material, thereby obtaining the Cu-Cr-Nb alloy forming piece (plate or cylindrical piece).
Further, the atomic percentage composition of the Cu-Cr-Nb powder component in the step (1) comprises: cr 4-8at%, nb 2-4at%, and Cu and unavoidable impurities in balance.
Further, the Cu-Cr-Nb powder in the step (1) has a particle size of 20-50 mu m, and Cr in the powder 2 The 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 a rotating speed of 80-150 rpm for spraying.
Further, the process parameters sprayed by the cold spraying equipment 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.
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 molded article had a microstructure of Cr 2 The Nb phase has a size of 2-8 mu m, no interface defect exists in the tissue, and the Vickers hardness reaches 200-300 HV.
The invention relates to a method for preparing Cu-Cr-Nb alloy, which is a process of accelerating solid metal powder to supersonic speed by utilizing high-pressure gas at a temperature lower than the melting point of a material by utilizing a cold spraying technology and continuously spraying the metal powder onto a substrate material, so that powder particles are subjected to strong plastic deformation and are accumulated into blocks. Is a manufacturing process based on high deformation rate and large deformation. The cold spraying has the advantages of high deposition rate, unrestricted thickness of the coating, lower residual thermal stress, uneasy oxidation of the material, etc.
The invention has the beneficial technical effects that the cold spraying technology is applied to solidification forming of Cu-Cr-Nb powder, so that the rapid forming of Cu-Cr-Nb alloy is realized, and the subsequent low-temperature vacuum annealing treatment is combined to perform tissue optimization, so that the interface defect in the sprayed layer is eliminated. Because of adopting the low-temperature treatment process, cr 2 The 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 Cr 2 The Nb phase size is kept between 2 and 8 μm.
Drawings
FIG. 1 is a microstructure chart of a Cu-Cr-Nb alloy obtained by the invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Unless defined otherwise, all technical and scientific terms 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 be limiting of the scope of the present invention. Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
the cold spraying preparation method of the Cu-Cr-Nb alloy comprises the following steps:
(1) The atomic percentage composition is selected to be Cu-4at percent Cr-2at percent Nb, the grain diameter is 25 mu m, cr 2 Drying the powder with Nb phase size smaller than 5 μm in a vacuum drying oven at 80 ℃ for 30min to obtain cold spray 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 a 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 carrier gas pressure 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 a moving speed of 5 mm/s.
And step 3, placing 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 spray coating annealed in the step 3 to remove the base material, and obtaining a finished Cu-Cr-Nb alloy forming part. Cr in alloy 2 The Nb phase size remains less than 5 μm and the alloy hardness is 215HV.
Example 2:
the cold spraying preparation method of the Cu-Cr-Nb alloy comprises the following steps:
(1) The atomic percentage composition is selected to be Cu-8at percent Cr-4at percent Nb, the grain diameter is 50 mu m, cr 2 Drying Nb phase powder with the size of 2-5 mu m in a vacuum drying oven at 90 ℃ for 20min to obtain 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 the Cu-Cr-Nb powder onto a 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 was nitrogen, the carrier gas pressure was 5MPa, the preheating temperature was 450 ℃, the distance between the surface of the base material and the nozzle outlet of the spray gun was 40mm, and the spray gun was moved up and down at a moving speed of 6 mm/s.
And step 3, placing the Cu-Cr-Nb spray coating obtained in the step 2 into a vacuum annealing furnace for 700 ℃, and carrying out annealing treatment for 3 hours.
And 4, turning the spray coating annealed in the step 3 to remove the base material, and obtaining a finished Cu-Cr-Nb alloy cylindrical part. Cr in alloy 2 The Nb phase size remained 2-5 μm, and the alloy hardness was 289HV.
Example 3:
the cold spraying preparation method of the Cu-Cr-Nb alloy comprises the following steps:
(1) The atomic percentage composition is selected to be Cu-6at percent Cr-3at percent Nb, the grain diameter is 40 mu m, cr 2 Drying the powder with Nb phase size of 4-8 μm in a vacuum drying oven at 85deg.C for 30min to obtain cold spray 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 a 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 carrier gas pressure 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 a moving speed of 4 mm/s.
And step 3, placing the Cu-Cr-Nb spray coating obtained in the step 2 into a vacuum annealing furnace for annealing treatment at 675 ℃ and preserving heat for 3 hours.
And 4, turning the spray coating annealed in the step 3 to remove the base material, and obtaining the finished Cu-Cr-Nb alloy plate. Cr in alloy 2 The Nb phase size remains less than 8 μm and the alloy hardness is 256HV.
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention and is not intended to be limiting. It should be noted that, for those skilled in the art, other equivalent modifications can be made in light of the technical teaching provided by the present invention, and the present invention can be implemented as the scope of protection.
Claims (5)
1. A method for cold spray forming of a Cu-Cr-Nb-based alloy, the method comprising:
(1) Drying the screened Cu-Cr-Nb powder material, wherein the Cu-Cr-Nb powder comprises the following components in atomic percent: cr 4-8at percent, nb2-4at percent, the balance of Cu and unavoidable impurities, wherein the particle size of Cu-Cr-Nb powder is 20-50 mu m, and Cr in the powder is as follows 2 Nb phase size is smaller than 8 mu m;
(2) Spraying the Cu-Cr-Nb powder obtained in the step (1) onto a rotating substrate material by using cold spraying equipment to obtain a Cu-Cr-Nb sprayed layer;
(3) Carrying out vacuum annealing treatment on the Cu-Cr-Nb spraying layer obtained in the step (2); the annealing temperature of the vacuum annealing treatment in the step (3) is 600-800 ℃, and the treatment time is 1.5-3 hours;
(4) And (3) removing the base material from the spray coating obtained in the step (3) to obtain the Cu-Cr-Nb alloy forming piece.
2. The method of cold spray forming a Cu-Cr-Nb based alloy according to claim 1, wherein the base material in the step (2) is a surface-blasted copper plate or a cylindrical copper material.
3. The method of cold spray forming a cu—cr—nb alloy according to claim 1, wherein the step (2) is performed by fixing a base material to a rotating shaft having a rotation speed of 80 to 150 rpm.
4. The method of cold spray forming of Cu-Cr-Nb based alloy according to claim 1, wherein the process parameters sprayed by the cold spray apparatus in 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.
5. The method of cold spray forming a Cu-Cr-Nb-based alloy according to claim 1, wherein the obtained Cu-Cr-Nb-based alloy forming member has a microstructure of Cr 2 The size of the Nb phase is 2-8 mu m, no interface defect exists in the tissue, and the Vickers hardness reaches 200-300 HV.
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