CN117701943A - Heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy and preparation method thereof - Google Patents
Heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy and preparation method thereof Download PDFInfo
- Publication number
- CN117701943A CN117701943A CN202311844265.5A CN202311844265A CN117701943A CN 117701943 A CN117701943 A CN 117701943A CN 202311844265 A CN202311844265 A CN 202311844265A CN 117701943 A CN117701943 A CN 117701943A
- Authority
- CN
- China
- Prior art keywords
- copper
- situ
- alloy
- rich
- nanoscale
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 154
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 146
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 134
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 132
- 239000000956 alloy Substances 0.000 title claims abstract description 132
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000005253 cladding Methods 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 43
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 38
- 230000006698 induction Effects 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 26
- 239000012071 phase Substances 0.000 claims description 21
- 230000010355 oscillation Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 230000001276 controlling effect Effects 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910001096 P alloy Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 238000002679 ablation Methods 0.000 abstract description 15
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 18
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 12
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910019580 Cr Zr Inorganic materials 0.000 description 3
- 229910019817 Cr—Zr Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002500 effect on skin Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010964 304L stainless steel Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses an isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy and a preparation method thereof, wherein the in-situ particle reinforced copper-based monotectic alloy comprises a plurality of cladding layers which are stacked in turn, each cladding layer is a heterostructure in which an iron-rich phase (hard phase) is dispersed and distributed in a copper-rich matrix (soft phase), and the heterostructure comprises three nanoscale particles: in-situ nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 . Wherein in-situ nanoscale iron-rich particles are dispersed and distributed in grains of a copper-rich matrix, and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 And in situ nanoscale amorphous oxide CrO 3 Distributed at the grain boundaries of the copper-rich matrix grains. The heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy provided by the invention has the advantages of excellent high-temperature stability, arc ablation resistance, high strength and toughness, fatigue resistance, radiation resistance and the like.
Description
Technical Field
The invention belongs to the technical field of laser additive manufacturing, and particularly relates to an isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy, and a preparation method and application thereof.
Background
Among Cu-based alloys, cu-Cr-Zr alloys are widely used in the fields of electric power, electronics, traffic, etc., due to their good electrical conductivity and toughness. However, at high temperatures of 400 ℃, cu due to rapid growth of Cr particlesThe toughness of the Cr-Zr alloy is greatly reduced, so that the thermal stability of the Cr-Zr alloy is poor, and the Cu-Cr-Zr alloy cannot form a compact oxide film, so that the high-temperature oxidation resistance of the Cu-Cr-Zr alloy is affected. Based on this, an Oxide Dispersion Strengthening (ODS) method is generally adopted to improve the high temperature performance of Cu-Cr-Zr alloy. For example, by introducing Al into Cu-Cr-Zr alloy 2 O 3 And Y 2 O 3 The particles can improve the high-temperature strength and the heat stability. However, mismatch of lattice parameters and elastic modulus between the ex-situ formed oxide particles and the matrix of the copper alloy tends to result in poor bond strength between the matrix of the copper alloy and the externally applied oxide particles and the creation of metallurgical defects, deteriorating the overall performance of the Cu-Cr-Zr alloy.
In order to improve the arc ablation resistance and the high-temperature service performance of the copper-based alloy, elements such as iron (Fe), chromium (Cr), molybdenum (Mo), nickel (Ni) and the like are added into copper to form the copper-based monotectic alloy, so that the arc ablation resistance, the high-temperature strength, the oxidation resistance and the radiation resistance of the copper-based monotectic alloy can be obviously improved. However, the mixing enthalpy of copper, iron and molybdenum is larger than zero, and the Cu-based monotectic alloy prepared by the conventional casting method is easy to form macrosegregation or layered structure, so that the application of the Cu-based monotectic alloy in the industrial field is greatly limited. In recent years, lamellar heterogeneous alloys have received extensive attention from researchers due to their unique structure and excellent properties. For example, the copper-based monotectic alloy with the structural characteristics has higher mechanical property through heterogeneous deformation reinforcement, and the immiscible heterogeneous interface makes alloy elements difficult to diffuse at high temperature, so that the high-temperature stability of the interface is increased, thereby improving the thermal stability, arc ablation resistance and irradiation resistance of the copper-based monotectic alloy.
In addition, if the copper-based monotectic alloy with lamellar isomerism is subjected to dispersion strengthening by separating out the multi-element in-situ nano-scale particles, the toughness, high-temperature stability, arc ablation resistance and irradiation resistance of the copper-based monotectic alloy can be further improved, and the metallurgical defects of the ex-situ oxide dispersion strengthening copper alloy can be eliminated. However, research reports on heterogeneous multi-element in-situ nano-particle reinforced copper-based meta-crystal alloy and preparation method thereof are not found at home and abroad.
Disclosure of Invention
In view of the above, the invention provides an isomerism multi-element in-situ nano particle reinforced copper-based monotectic alloy, a preparation method and application thereof, wherein the isomerism multi-element in-situ nano particle reinforced copper-based monotectic alloy has a layered heterostructure which is in a copper-rich matrix (soft phase) with iron-rich phase (hard phase) dispersed. The heterostructure comprises in-situ nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 Three kinds of nanometer level grains, in-situ nanometer level iron-rich grains dispersed inside the grains of copper-rich matrix, and in-situ nanometer level intermetallic compound Cr 12 Fe 36 Mo 10 And in situ nanoscale amorphous oxide CrO 3 Distributed at grain boundaries between copper-rich phase matrix grains. The heterostructure has the advantages of excellent high-temperature heat stability, arc ablation resistance, high strength and toughness, fatigue resistance, irradiation resistance and the like, and has very wide application prospects in the fields of high-speed rail transit, electronics, aerospace and the like.
The first object of the invention is to provide an isomerically multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy.
The second aim of the invention is to provide a preparation method of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy.
The third object of the invention is to provide an application method of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy.
The first object of the present invention can be achieved by adopting the following technical scheme:
the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy comprises a plurality of cladding layers which are stacked in sequence, wherein each cladding layer is a heterostructure in which an iron-rich phase is dispersed and distributed in a copper-rich matrix, and the heterostructure comprises in-situ nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 The in-situ nanoscale iron-rich particles are dispersed and distributed on crystal grains of the copper-rich matrixIn-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 And in situ nanoscale amorphous oxide CrO 3 Distributed at the grain boundaries of the copper-rich matrix grains.
Further, the size of the in-situ nanoscale iron-rich particles is 60-80 nm, and the in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 The size of the nano-scale amorphous oxide CrO is 20-50 nm 3 The size of (C) is 30-60 nm.
Further, the iron-rich phase is composed of iron-rich grains, and the size of the iron-rich grains is 8-15 mu m; the copper-rich matrix is composed of copper-rich grains, and the size of the copper-rich grains is 1-5 mu m.
The second object of the invention can be achieved by adopting the following technical scheme:
the preparation method of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy comprises the following steps:
s1: the copper-based monotectic alloy powder is placed in an automatic powder feeder, and the chemical components are as follows: 15 to 25.5wt.% of Fe, 5 to 7.3wt.% of Cr, 2.5 to 3.5wt.% of Ni, 0.1 to 0.5wt.% of Si, 4 to 10wt.% of Mo and the balance of Cu;
s2: the distance between the induction heating coil and the surface of the substrate is regulated to be 2-7 mm, the induction heating power is 35-80 kW, the induction heating temperature is 400-700 ℃, and the oxygen content in the laser-induction composite cladding additive manufacturing cabin is 2-5 vol%;
s3: positioning a laser beam and a powder nozzle of an automatic powder feeder in an induction heating area to realize the coupling of a laser heat source and an induction heating source; blowing copper-based monotectic alloy powder into a molten pool formed by a composite heat source by using a powder nozzle, and simultaneously introducing oxygen in a cabin into the molten pool; controlling the stirring intensity of the laser beam in the molten pool and the flowing direction of the molten pool so as to induce the liquid phase separation of copper and iron or copper and molybdenum to form copper-based monotectic alloy with a layered heterostructure;
s4: after removing the laser-induction composite cladding heat source, rapidly solidifying the molten copper-based monotectic alloy powder on the surface of the substrate to form a single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy, thereby completing a cladding layer;
s5: after the composite cladding is finished for one layer, returning the laser head, the induction heating coil and the powder nozzle to the initial position during the processing of the current layer, and rising the thickness distance of the current layer along the Z axis;
s6: repeating the steps S2 to S5 until the manufacturing of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is completed;
s7: and carrying out heat treatment on the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy to eliminate internal stress generated in the manufacturing process, and obtaining the final heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy.
Further, the heat treatment process parameters in step S7 are as follows: the temperature is 400-600 ℃ and the time is 2-3 hours.
Further, in step S3, the stirring intensity of the laser beam in the molten pool is controlled by adjusting the laser beam power, the oscillation frequency, the cladding speed and the amplitude, wherein the laser beam power is 3-12 kW, the composite cladding speed is 0.6-10 m/min, the laser beam oscillation frequency is 250-800 Hz, and the laser beam amplitude is: x-axis direction-3 mm and Y-axis direction-3 mm.
Further, in step S3, the flow direction of the molten pool is controlled by adjusting a laser beam scanning path, which is circular or spiral.
Further, the substrate is pretreated before the step S2, and nickel-phosphorus alloy with the thickness of 5-40 mu m is electroplated on the pretreated substrate, so that the bonding strength between the substrate and the copper-based monotectic alloy is improved.
Further, the base material is an iron alloy, a copper alloy or an aluminum alloy.
The third object of the present invention can be achieved by adopting the following technical scheme:
an application method of an isomerism multi-element in-situ nano particle reinforced copper-based monotectic alloy is based on the isomerism multi-element in-situ nano particle reinforced copper-based monotectic alloy or the application of the isomerism multi-element in-situ nano particle reinforced copper-based monotectic alloy prepared by the preparation method in the fields of high-speed rail transit, electronics and aerospace.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy and a preparation method thereof, wherein the isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy comprises a plurality of cladding layers which are stacked in sequence, each cladding layer is a heterostructure with iron-rich phases dispersed and distributed in a copper-rich matrix, and the heterostructure comprises in-situ nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 The in-situ nanoscale iron-rich particles are dispersed and distributed in the grains of the copper-rich matrix, and the in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 And in situ nanoscale amorphous oxide CrO 3 Distributed at the grain boundaries of the copper-rich matrix grains. Compared with the conventional Cu-Cr-Zr alloy, the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy has the unique structural characteristics, so that the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy has excellent high-temperature stability, arc ablation resistance, high strength and toughness, fatigue resistance, irradiation resistance and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the macrostructure of a layered heterostructure of an heterogeneous multi-in-situ nanoparticle reinforced copper-based meta-crystal alloy of example 1 of the present invention;
FIG. 2 is a microscopic schematic view of three nanoscale particles precipitated in situ in the heterogeneous multi-element in situ nanoparticle-reinforced copper-based meta-crystal alloy of example 1 of the present invention;
wherein, the 1-iron-rich phase, the 2-copper-rich matrix and the 3-in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 4-in situ nanoscale amorphous oxide CrO 3 5-iron-rich grains, 6-copper-rich matrix grain boundaries, 7-in-situ nanoscale iron-rich grains, and 8-copper-rich grains.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons of ordinary skill in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention. It should be understood that the description of the specific embodiments is intended for purposes of illustration only and is not intended to limit the scope of the present application.
Example 1:
the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy provided by the embodiment comprises a plurality of cladding layers which are stacked in sequence, wherein each cladding layer is a heterostructure in which an iron-rich phase is dispersed and distributed in a copper-rich matrix, and the heterostructure comprises three nanoscale particles: in-situ nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 Wherein in-situ nanoscale iron-rich particles are dispersed and distributed in grains of a copper-rich matrix, and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 And in situ nanoscale amorphous oxide CrO 3 Distributed at the grain boundaries of the copper-rich matrix grains.
Wherein, the size of the in-situ nanoscale iron-rich particles is 60-80 nm, and the in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo10 has a size of 20-50 nm and is in-situ nano-scale amorphous oxide CrO 3 The size of (C) is 30-60 nm.
Wherein the iron-rich phase is composed of iron-rich grains, and the size of the iron-rich grains is 8-15 mu m; the copper-rich matrix is composed of copper-rich grains, and the size of the copper-rich grains is 1-5 mu m.
The heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has excellent high-temperature stability, arc ablation resistance, high strength and toughness, fatigue resistance, irradiation resistance and other performances due to the heterostructure with the structural characteristics.
Example 2:
the embodiment provides a preparation method of an isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy, which comprises the following specific steps:
(1) Taking a 316L stainless steel plate as a base material, and carrying out oil removal, rust removal or electroplating treatment on the surface of the base material; placing copper-based monotectic alloy powder into a charging hopper of an automatic powder feeder;
the copper-based monotectic alloy powder comprises the following chemical components: 20wt.% of Fe, 5wt.% of Cr, 3wt.% of Ni, 0.5wt.% of si, 10wt.% of Mo, and the balance Cu.
(2) The oxygen content in the cabin body is changed by controlling the pressure in the forming cabin, wherein the oxygen content is as follows: o5wt.%;
(3) Adjusting the distance between the induction heating coil and the surface of the substrate, so that the substrate can be heated by effectively realizing the surface skin effect; wherein, the distance between the heating coil and the surface of the substrate is 2mm, the induction heating power is 80kW, and the temperature of the substrate heated by induction is 700 ℃;
(4) Positioning a laser beam and a powder nozzle of an automatic powder feeder in an induction heating area to realize the combination of a laser heat source and an induction heating source, blowing copper-based monotectic alloy powder into a molten pool formed by the combination heat source by using the powder nozzle, starting to implement high-frequency oscillation laser-induction combined cladding, regulating and controlling the stirring intensity of the laser beam in the molten pool by regulating the power, oscillation frequency, cladding speed and amplitude of the laser beam, and regulating and controlling the flow direction of the molten pool by regulating a laser beam scanning path;
wherein the laser power is 12kW, the composite cladding speed is 0.6m/min, and the laser beam oscillation frequency is 800Hz; the composite cladding direction is taken as the X-axis direction, the transverse direction of the copper-based monotectic alloy is taken as the Y-axis, the direction vertical to the surface of the substrate is taken as the Z-axis direction, and the amplitude of the laser beam is as follows: x-axis direction-3 mm, Y-axis direction-3 mm, and laser beam oscillation scanning pattern is circular.
(5) After removing the laser-induction composite cladding heat source, the molten copper-based monotectic alloy powder is rapidly solidified and formed into a single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy;
the single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has a heterostructure in which an iron-rich phase (hard phase) is dispersed and distributed in a copper-rich matrix (soft phase), and three nanoscale particles are precipitated in situ: in-situ nanoscale iron-rich particles with an average size of 65nm; in-situ nanoscale intermetallic compounds having an average size of 30nm; the average size of the in-situ nanoscale amorphous oxide is 45nm.
(6) After the composite cladding is finished for one layer, returning the laser head, the induction heating coil and the powder nozzle to the initial position in the processing of the previous layer, rising the thickness distance of the current layer along the Z axis, and repeating the steps (3) - (5) until the manufacturing of the heterogeneous multi-element in-situ nano particle reinforced copper-based monotectic alloy is completed;
(7) Removing the base material by adopting a linear cutting method to obtain the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy;
(8) By carrying out heat treatment on the alloy for 3 hours at 600 ℃, the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy with excellent high temperature stability, arc ablation resistance, toughness, fatigue performance, irradiation resistance and other performances is obtained.
After the composite cladding of the technological parameters is completed, when the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is heated at 700-950 ℃, the growth of crystal grains is not obvious, and the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has excellent high-temperature stability; the arc ablation resistance of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is improved by 8 times compared with that of Cu-Cr-Zr alloy; the tensile strength of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy reaches 1100MPa, the elongation is 16%, and the fatigue limit reaches 560MPa; the irradiation resistance of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is improved by 6 times compared with that of Cu-Cr-Zr alloy.
Example 3:
the embodiment provides a preparation method of an isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy, which comprises the following specific steps:
(1) Taking a 304L stainless steel plate as a base material, and carrying out oil removal, rust removal or electroplating treatment on the surface of the base material; placing copper-based monotectic alloy powder into a charging hopper of an automatic powder feeder;
the copper-based monotectic alloy powder comprises the following chemical components: 25.5wt.% fe, 7.3wt.% cr, 3.5wt.% ni, 0.3wt.% si, 6wt.% Mo, the balance Cu.
(2) The oxygen content in the cabin body is changed by controlling the pressure in the forming cabin, wherein the oxygen content is as follows: o3wt.%;
(3) Adjusting the distance between the induction heating coil and the surface of the substrate, so that the substrate can be heated by effectively realizing the surface skin effect; the distance between the heating coil and the surface of the substrate is 4mm, the induction heating power adjusting range is 60kW, and the temperature of the substrate heated by induction is 670 ℃;
(4) Positioning a laser beam and a powder nozzle of an automatic powder feeder in an induction heating area to realize the combination of a laser heat source and an induction heating source, blowing copper-based monotectic alloy powder into a molten pool formed by the combination heat source by using the powder nozzle, starting to implement high-frequency oscillation laser-induction combined cladding, regulating and controlling the stirring intensity of the laser beam in the molten pool by regulating the power, oscillation frequency, cladding speed and amplitude of the laser beam, and regulating and controlling the flow direction of the molten pool by regulating a laser beam scanning path;
wherein the laser power is 9kW, the composite cladding speed is 8m/min, and the laser beam oscillation frequency is 600Hz; the composite cladding direction is taken as the X-axis direction, the transverse direction of the copper-based monotectic alloy is taken as the Y-axis, the direction vertical to the surface of the substrate is taken as the Z-axis direction, and the amplitude of the laser beam is as follows: x-axis direction-2 mm, Y-axis direction-2 mm, and laser beam oscillation scanning pattern is circular.
(5) After removing the laser-induction composite cladding heat source, the molten copper-based monotectic alloy powder is rapidly solidified and formed into a single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy;
the single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has a heterostructure in which an iron-rich phase (hard phase) is dispersed and distributed in a copper-rich matrix (soft phase), and three nanoscale particles are precipitated in situ: in-situ nanoscale iron-rich particles with an average size of 75nm; in-situ nanoscale intermetallic compounds with an average size of 40nm; the in-situ nanoscale amorphous oxide has an average size of 50nm.
(6) After the composite cladding is finished for one layer, returning the laser head, the induction heating coil and the powder nozzle to the initial position in the processing of the previous layer, rising the thickness distance of the current layer along the Z axis, and repeating the steps (3) - (5) until the manufacturing of the heterogeneous multi-element in-situ nano particle reinforced copper-based monotectic alloy is completed;
(7) Removing the base material by adopting a linear cutting method to obtain the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy;
(8) By carrying out heat treatment on the alloy for 2 hours at the temperature of 550 ℃, the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy with excellent high temperature stability, arc ablation resistance, toughness, fatigue performance, irradiation resistance and other performances is obtained.
After the composite cladding of the technological parameters is completed, when the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is heated at 700-900 ℃, the growth of crystal grains is not obvious, and the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has excellent high-temperature stability; the arc ablation resistance of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is improved by 6 times compared with that of Cu-Cr-Zr alloy; the tensile strength of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy reaches 1010MPa, the elongation is 12%, and the fatigue limit reaches 510MPa; the irradiation resistance of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy is improved by 5 times compared with that of Cu-Cr-Zr alloy.
Example 4:
the embodiment provides a preparation method of an isomerism multielement in-situ nanoparticle reinforced copper-based monotectic alloy, which comprises the following specific steps:
(1) Taking a brass plate as a base material, and carrying out oil removal, rust removal or electroplating treatment on the surface of the base material; placing copper-based monotectic alloy powder into a charging hopper of an automatic powder feeder;
the copper-based monotectic alloy powder comprises the following chemical components: 15wt.% Fe, 5.3wt.% Cr, 2.5wt.% Ni, 0.1wt.% Si, 4wt.% Mo, the balance being Cu.
(2) The oxygen content in the cabin body is changed by controlling the pressure in the forming cabin, wherein the oxygen content is as follows: o2wt.%;
(3) Adjusting the distance between the induction heating coil and the surface of the substrate, so that the substrate can be heated by effectively realizing the surface skin effect; wherein, the adjusting range of the distance between the heating coil and the surface of the substrate is 7mm, the adjusting range of the induction heating power is 35kW, and the temperature of the substrate which is heated by induction is 400 ℃;
(4) Positioning a laser beam and a powder nozzle of an automatic powder feeder in an induction heating area to realize the combination of a laser heat source and an induction heating source, blowing copper-based monotectic alloy powder into a molten pool formed by the combination heat source by using the powder nozzle, starting to implement high-frequency oscillation laser-induction combined cladding, regulating and controlling the stirring intensity of the laser beam in the molten pool by regulating the power, oscillation frequency, cladding speed and amplitude of the laser beam, and regulating and controlling the flow direction of the molten pool by regulating a laser beam scanning path;
wherein the laser power is 3kW, the composite cladding speed is 10m/min, and the laser beam oscillation frequency is 250Hz; the composite cladding direction is taken as the X-axis direction, the transverse direction of the copper-based monotectic alloy is taken as the Y-axis, the direction vertical to the surface of the substrate is taken as the Z-axis direction, and the amplitude of the laser beam is as follows: the X-axis direction is-3-0 mm, the Y-axis direction is-3-0 mm, and the laser beam oscillation scanning pattern is spiral.
(5) After removing the laser-induction composite cladding heat source, the molten copper-based monotectic alloy powder is rapidly solidified and formed into a single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy;
the single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has a heterostructure in which an iron-rich phase (hard phase) is dispersed and distributed in a copper-rich matrix (soft phase), and three nanoscale particles are precipitated in situ: in-situ nanoscale iron-rich particles with an average size of 77nm; in-situ nanoscale intermetallic compounds having an average size of 44nm; the in-situ nanoscale amorphous oxide has an average size of 53nm.
(6) After the composite cladding is finished for one layer, returning the laser head, the induction heating coil and the powder nozzle to the initial position in the processing of the previous layer, rising the thickness distance of the current layer along the Z axis, and repeating the steps (3) - (5) until the manufacturing of the heterogeneous multi-element in-situ nano particle reinforced copper-based monotectic alloy is completed;
(7) Removing the base material by adopting a linear cutting method to obtain the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy;
(8) By carrying out heat treatment on the alloy at 400 ℃ for 2 hours, the heterogeneous multi-element in-situ nanoparticle reinforced copper-based meta-crystal alloy with excellent high-temperature stability, arc ablation resistance, toughness, fatigue performance, irradiation resistance and other performances is obtained.
After the composite cladding of the technological parameters is completed, when the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is heated at 700-800 ℃, the growth of crystal grains is not obvious, and the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has excellent high-temperature stability; the arc ablation resistance of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is improved by 5 times compared with that of Cu-Cr-Zr alloy; the tensile strength of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy reaches 950MPa, the elongation is 14%, and the fatigue limit reaches 480MPa; the irradiation resistance of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is improved by 3 times compared with that of Cu-Cr-Zr alloy.
In the step (1) of the above examples 2 to 4, after the substrate is pretreated, a nickel-phosphorus alloy having a thickness of 5 to 40 μm is further plated on the pretreated substrate to improve the bonding strength between the substrate and the copper-based monotectic alloy.
The preparation methods provided in the above embodiments 2 to 4 add Mo, cr, ni and other elements into the processing material, and control the oxygen content during the cladding process by using the oscillation laser-induction composite cladding technology, so that the prepared copper-based meta-crystal alloy obtains a heterostructure with uniform structure, and simultaneously precipitates nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr at the reduction site in the heterostructure 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 Finally, heat treatment is carried out on the alloy to eliminate the alloy in the preparation processThe generated internal stress ensures that the obtained heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy has excellent high-temperature heat stability, arc ablation resistance, high strength and toughness, fatigue resistance, irradiation resistance and other performances.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can make equivalent substitutions or modifications according to the technical solution and the inventive concept of the present invention within the scope of the present invention disclosed in the present invention patent, and all those skilled in the art belong to the protection scope of the present invention.
Claims (10)
1. The heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is characterized by comprising a plurality of cladding layers which are stacked in sequence, wherein each cladding layer is a heterostructure in which an iron-rich phase is dispersed and distributed in a copper-rich matrix, and the heterostructure comprises in-situ nanoscale iron-rich particles and in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 In-situ nanoscale amorphous oxide CrO 3 The in-situ nanoscale iron-rich particles are dispersed and distributed in the grains of the copper-rich matrix, and the in-situ nanoscale intermetallic compound Cr 12 Fe 36 Mo 10 And in situ nanoscale amorphous oxide CrO 3 Distributed at the grain boundaries of the copper-rich matrix grains.
2. The heterogeneous multi-in-situ nanoparticle reinforced copper-based meta-crystal alloy of claim 1 wherein the in-situ nanoscale iron-rich particles are 60-80 nm in size and the in-situ nanoscale intermetallic Cr 12 Fe 36 Mo 10 The size of the nano-scale amorphous oxide CrO is 20-50 nm 3 The size of (C) is 30-60 nm.
3. The heterogeneous multi-in-situ nanoparticle reinforced copper-based meta-crystal alloy of claim 1 wherein the iron-rich phase is comprised of iron-rich grains having a size of 8-15 μιη; the copper-rich matrix is composed of copper-rich grains, and the size of the copper-rich grains is 1-5 mu m.
4. The preparation method of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is characterized by comprising the following steps of:
s1: the copper-based monotectic alloy powder is placed in an automatic powder feeder, and the chemical components are as follows: 15 to 25.5wt.% of Fe, 5 to 7.3wt.% of Cr, 2.5 to 3.5wt.% of Ni, 0.1 to 0.5wt.% of Si, 4 to 10wt.% of Mo and the balance of Cu;
s2: the distance between the induction heating coil and the surface of the substrate is regulated to be 2-7 mm, the induction heating power is 35-80 kW, the induction heating temperature is 400-700 ℃, and the oxygen content in the laser-induction composite cladding additive manufacturing cabin is 2-5 vol%;
s3: positioning a laser beam and a powder nozzle of an automatic powder feeder in an induction heating area to realize the coupling of a laser heat source and an induction heating source; blowing copper-based monotectic alloy powder into a molten pool formed by a composite heat source by using a powder nozzle, and simultaneously introducing oxygen in a cabin into the molten pool; controlling the stirring intensity of the laser beam in the molten pool and the flowing direction of the molten pool so as to induce the liquid phase separation of copper and iron or copper and molybdenum to form copper-based monotectic alloy with a layered heterostructure;
s4: after removing the laser-induction composite cladding heat source, rapidly solidifying the molten copper-based monotectic alloy powder on the surface of the substrate to form a single-channel heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy, thereby completing a cladding layer;
s5: after the composite cladding is finished for one layer, returning the laser head, the induction heating coil and the powder nozzle to the initial position during the processing of the current layer, and rising the thickness distance of the current layer along the Z axis;
s6: repeating the steps S2 to S5 until the manufacturing of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is completed;
s7: and carrying out heat treatment on the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy to eliminate internal stress generated in the manufacturing process, and obtaining the final heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy.
5. The method according to claim 4, wherein the heat treatment process parameters in step S7 are: the temperature is 400-600 ℃ and the time is 2-3 hours.
6. The method according to claim 4, wherein in step S3, the stirring intensity of the laser beam in the molten pool is controlled by adjusting the power, the oscillation frequency, the cladding speed and the amplitude of the laser beam, wherein the power of the laser beam is 3-12 kW, the composite cladding speed is 0.6-10 m/min, the oscillation frequency of the laser beam is 250-800 Hz, and the amplitude of the laser beam is: x-axis direction-3 mm and Y-axis direction-3 mm.
7. The method according to claim 4, wherein in step S3, the flow direction of the molten pool is controlled by adjusting a laser beam scanning path, which is circular or spiral.
8. The method according to claim 4, wherein the substrate is pretreated before step S2, and the pretreated substrate is electroplated with a nickel-phosphorus alloy having a thickness of 5 to 40 μm to improve the bonding strength between the substrate and the copper-based monotectic alloy.
9. The method according to any one of claims 4 to 8, wherein the base material is an iron alloy, a copper alloy or an aluminum alloy.
10. An application method of the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy is characterized in that the heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy prepared based on any one of claims 1-3 or the preparation method of any one of claims 4-9 is applied to the fields of high-speed rail transit, electronics and aerospace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311844265.5A CN117701943B (en) | 2023-12-29 | 2023-12-29 | Heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311844265.5A CN117701943B (en) | 2023-12-29 | 2023-12-29 | Heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117701943A true CN117701943A (en) | 2024-03-15 |
| CN117701943B CN117701943B (en) | 2024-05-03 |
Family
ID=90160772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311844265.5A Active CN117701943B (en) | 2023-12-29 | 2023-12-29 | Heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117701943B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001107802A (en) * | 1999-10-06 | 2001-04-17 | Mitsubishi Materials Corp | Piston ring composite wear resisting ring with cooling cavity excellent in high temperature wear resistance and thermal conductivity |
| CN110724841A (en) * | 2019-11-07 | 2020-01-24 | 中南大学 | Preparation method of immiscible alloy and continuous casting equipment |
| CN112605396A (en) * | 2020-12-09 | 2021-04-06 | 暨南大学 | Method for melting and forming iron-based amorphous reinforced copper-based monotectic composite material in selective laser area |
| CN113005446A (en) * | 2021-02-24 | 2021-06-22 | 暨南大学 | Method and device for oscillating laser-induction hybrid cladding wear-resistant ablation-resistant copper-based coating |
| CN113061778A (en) * | 2021-02-07 | 2021-07-02 | 中国科学院金属研究所 | In-situ amorphous particle reinforced copper alloy material |
| CN114000009A (en) * | 2021-09-29 | 2022-02-01 | 宁波兴业盛泰集团有限公司 | Copper-iron intermediate alloy with uniform components and preparation method thereof |
| CN114472922A (en) * | 2022-01-20 | 2022-05-13 | 暨南大学 | Method for manufacturing copper-based monotectic high-entropy alloy through ultrahigh-speed laser-induction composite cladding and material increase |
-
2023
- 2023-12-29 CN CN202311844265.5A patent/CN117701943B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001107802A (en) * | 1999-10-06 | 2001-04-17 | Mitsubishi Materials Corp | Piston ring composite wear resisting ring with cooling cavity excellent in high temperature wear resistance and thermal conductivity |
| CN110724841A (en) * | 2019-11-07 | 2020-01-24 | 中南大学 | Preparation method of immiscible alloy and continuous casting equipment |
| CN112605396A (en) * | 2020-12-09 | 2021-04-06 | 暨南大学 | Method for melting and forming iron-based amorphous reinforced copper-based monotectic composite material in selective laser area |
| CN113061778A (en) * | 2021-02-07 | 2021-07-02 | 中国科学院金属研究所 | In-situ amorphous particle reinforced copper alloy material |
| CN113005446A (en) * | 2021-02-24 | 2021-06-22 | 暨南大学 | Method and device for oscillating laser-induction hybrid cladding wear-resistant ablation-resistant copper-based coating |
| CN114000009A (en) * | 2021-09-29 | 2022-02-01 | 宁波兴业盛泰集团有限公司 | Copper-iron intermediate alloy with uniform components and preparation method thereof |
| CN114472922A (en) * | 2022-01-20 | 2022-05-13 | 暨南大学 | Method for manufacturing copper-based monotectic high-entropy alloy through ultrahigh-speed laser-induction composite cladding and material increase |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117701943B (en) | 2024-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112391556B (en) | High-strength high-conductivity Cu-Cr-Nb alloy reinforced by double-peak grain size and double-scale nanophase | |
| CN106148756B (en) | The preparation method of one Albatra metal | |
| EP3440229A2 (en) | Aluminum alloys having iron, silicon, vanadium and copper, and with a high volume of ceramic phase therein | |
| CN107012356B (en) | A kind of high-intensity high-conductivity copper based alloy blank of graphene-containing and preparation method thereof | |
| CA2888692C (en) | Ti-included oxide dispersion strengthened copper alloy and method for manufacturing dispersed copper | |
| CN114472922B (en) | Method for manufacturing copper-based monotectic high-entropy alloy through ultrahigh-speed laser-induction composite cladding and material increase | |
| CN104746068B (en) | It is a kind of for copper-based coating of ferrous alloy surface laser cladding and preparation method thereof | |
| JP2018135585A (en) | Metal member and method for manufacturing clad layer | |
| KR102251066B1 (en) | BCC materials of titanium, aluminum, niobium, vanadium and molybdenum, and products made therefrom | |
| KR20180123221A (en) | Alpha-beta titanium alloys with aluminum and molybdenum, and products made therefrom | |
| CN112030030B (en) | High-strength high-conductivity copper alloy wire and preparation method thereof | |
| CN114654128B (en) | TC4 titanium alloy metal powder core flux-cored welding strip and preparation method thereof | |
| Ma et al. | Formation mechanism and microstructural and mechanical properties of in-situ Ti–Ni-based composite coatings by laser metal deposition | |
| CN113061779B (en) | Additive manufacturing method of nanoparticle reinforced titanium-based composite material based on selective electron beam melting | |
| CN109454233B (en) | Method for producing metal product | |
| CN117701943B (en) | Heterogeneous multi-element in-situ nanoparticle reinforced copper-based monotectic alloy and preparation method thereof | |
| CN108441666B (en) | Ti2Preparation method of AlC particle reinforced copper-based composite material | |
| CN114535859B (en) | Nickel-steel composite material arc 3D printing welding wire and preparation and additive manufacturing method | |
| CN113061778B (en) | In-situ amorphous particle reinforced copper alloy material | |
| CN112643022B (en) | Copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in selective laser area | |
| Zhong et al. | Fabrication of nanoparticulate reinforced metal matrix composites by laser cladding | |
| Deshmukh et al. | A Review on Twin Wire Arc Additive Manufacturing of Metals and Alloys: Microstructure and Mechanical Properties | |
| CN1555065A (en) | High strength high conductivity copper base composite material and its preparing method | |
| CN114273815B (en) | Solid welding wire for preparing iron-based isometric crystal alloy material through electric arc additive manufacturing and preparation method thereof | |
| CN117696918B (en) | Method for manufacturing copper steel dissimilar metal by laser composite additive and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |