CN112643022B - Copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in selective laser area - Google Patents
Copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in selective laser area Download PDFInfo
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- CN112643022B CN112643022B CN202011427359.9A CN202011427359A CN112643022B CN 112643022 B CN112643022 B CN 112643022B CN 202011427359 A CN202011427359 A CN 202011427359A CN 112643022 B CN112643022 B CN 112643022B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000010949 copper Substances 0.000 title claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 58
- 239000000843 powder Substances 0.000 title claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 26
- 239000000956 alloy Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002844 melting Methods 0.000 title claims abstract description 24
- 230000008018 melting Effects 0.000 title claims abstract description 24
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000713 high-energy ball milling Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000012216 screening Methods 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- -1 whiskers Substances 0.000 description 1
Classifications
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- B22F1/0003—
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
-
- 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
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in a selective laser region, which is characterized by comprising the following components in parts by weight: copper-based composite powder with the particle size of 40-50 mu m is used as a forming material, and the iron-based amorphous reinforced copper-based alloy is prepared by adopting a selective laser melting forming method, wherein the copper-based composite powder mainly comprises the iron-based amorphous powder and the copper alloy powder according to the mass ratio of 1: 9-1: 7. The invention has the advantages that: in the selective laser melting and forming process of the copper-based composite powder, liquid phase separation is carried out to form spherical amorphous iron particles by self-assembly, and the amorphous iron particles are dispersed in the copper-rich matrix; the iron-based amorphous reinforced copper-based alloy has excellent comprehensive properties of high strength, high corrosion resistance, high wear resistance, high heat conductivity and the like.
Description
Technical Field
The invention relates to copper-based composite powder for forming iron-based amorphous reinforced copper-based alloy by selective laser melting, belonging to the technical field of laser additive manufacturing.
Background
The copper alloy is formed by adding one or more other elements into pure copper serving as a matrix, has high strength and toughness, and has wide application prospect in the industrial field, such as being used for manufacturing electrical equipment such as generators, wires, cables, switching devices, transformers and the like, and heat-conducting devices such as heat exchangers, pipelines, flat plate collectors of solar heating devices and the like.
However, the use of copper alloys has been greatly limited due to insufficient strength, wear resistance and heat resistance of the copper alloys. The particle reinforced copper-based alloy introduces second phase particles such as fibers, whiskers, ceramics and other high-strength reinforced phase reinforced copper matrix into the copper matrix, increases the wear resistance of the copper matrix, and has good development prospect.
At present, the preparation method of the particle reinforced copper-based alloy mainly comprises an external reinforced phase method and an internal in-situ generation method, wherein the former generally adopts second-phase particles such as carbide, boride, nitride, oxide and the like which are directly mixed with copper-based alloy powder and prepared by a powder metallurgy method; the latter generally mixes the alloying elements forming the reinforcing particles with the copper-based alloy powder, causing it to undergo complex metallurgical chemical reactions at high temperatures, forming reinforcing phase particles in situ. However, the external reinforcing phase can be burnt at high temperature, so that the excellent performance of the reinforcing phase is lost, and the particle reinforced copper-based alloy is easy to induce cracking; the reinforcing phase formed by the in-situ synthesis method and the copper-based alloy have better wetting performance, but the volume, the form and the distribution of the formed reinforcing phase cannot be regulated and controlled.
The iron-based amorphous alloy serving as a novel structure and functional material not only has extremely high strength, wear resistance and corrosion resistance, but also shows excellent magnetic properties, and has wide application prospect. However, no literature report is found on the research on the improvement of the performance of the copper-based alloy by using the iron-based amorphous alloy as a reinforcing phase, and particularly, the copper-based composite powder has no characteristics of being completely suitable for selective laser melting and forming and can be successfully used for preparing the iron-based amorphous reinforced copper-based alloy with large size, complex structure, no crack, high strength, high conductivity, high wear resistance and high corrosion resistance.
Disclosure of Invention
Under the condition of high efficiency, the rapid manufacturing of the particle reinforced copper-based alloy with large size and complex structure is realized by adopting the selective laser melting forming technology. Therefore, the invention aims to provide copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in a selective laser area, the copper-based composite powder mainly comprises the following components in a mass ratio of 1: 9-1: 7: 8-10 wt.% of W, 4-6 wt.% of Cr, 1-3 wt.% of Mo, 1-3 wt.% of Ni, 3-5 wt.% of Si, 3-5 wt.% of B, 0.2-1 wt.% of C, 0.2-1.5 wt.% of Mn, HfO2 0.8～1.5wt.％，The balance being Fe; the chemical components of the copper alloy powder are as follows: 0.5-2 wt.% of Cr, 1-3 wt.% of Zr, 3-5 wt.% of P, and CeO20.2-1 wt.%, and the balance of Cu.
The copper-based composite powder is prepared by the following steps:
(1) for the preparation of the iron-based amorphous alloy powder: vacuum arc melting, atomizing and screening to form iron-based amorphous alloy powder with the granularity of 60-80 mu m;
(2) for the preparation of copper alloy powder: carrying out vacuum high-frequency induction melting, atomizing and screening to form copper alloy powder with the granularity of 60-80 mu m;
(3) the method comprises the steps of putting iron-based amorphous alloy powder and copper alloy powder in a high-energy ball mill according to the mass ratio of 1: 9-1: 7, uniformly mixing, and then screening, activating, drying, chemically plating nickel, filtering, washing, drying and screening to obtain copper-based composite powder with the granularity of 40-50 microns and used for melting and forming the iron-based amorphous reinforced copper-based alloy in a laser selective area.
Compared with the copper-based composite powder produced by the prior art, the copper-based composite powder for the iron-based amorphous reinforced copper-based alloy formed by selective laser melting has the following advantages:
(1) the iron-based amorphous alloy powder and the copper alloy powder are mixed by a high-energy ball mill, mutual diffusion reaction can occur, and then chemical nickel plating treatment is carried out, so that not only can copper alloy elements be effectively protected from being oxidized in the selective laser melting forming process, but also the sphericity of the copper-based composite powder can be ensured, and the copper-based composite powder is favorable for spreading in the selective laser melting forming process.
(2) In the selective laser melting and forming process, the iron-based amorphous alloy powder and the copper alloy powder are completely melted and have metallurgical chemical reaction, and because Cu and Fe as well as Cu and Cr are immiscible alloy systems, liquid phase separation can occur between the Cu and Fe as well as the Cu and Cr to form spherical iron-based amorphous particles which are dispersed and distributed in the copper-rich matrix, so that the iron-based amorphous reinforced copper-based alloy is formed, and the alloy has excellent comprehensive properties of high strength, high conductivity, high wear resistance, high corrosion resistance and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
The invention relates to copper-based composite powder for forming iron-based amorphous reinforced copper-based alloy by selective laser melting, which mainly comprises iron-based amorphous powder and copper alloy powder in a mass ratio of 1: 9-1: 7, wherein the iron-based amorphous powder comprises the following chemical components: w8.5 wt.%, Cr 5.2 wt.%, Mo 2.5 wt.%, Ni 2.4 wt.%, Si 3.5 wt.%, B4.5 wt.%, C0.5 wt.%, Mn 1.2 wt.%, HfO20.85 wt.%, balance Fe; the chemical components of the copper alloy powder are as follows: cr 1.5 wt.%, Zr 1.2 wt.%, P4.2 wt.%, CeO20.8 wt.%, with the balance being Cu.
The preparation process comprises the following steps: firstly, preparing iron-based amorphous alloy powder: vacuum arc melting, atomizing and screening to form iron-based amorphous alloy powder with the granularity of 60-80 mu m; next, copper alloy powder was prepared: carrying out vacuum high-frequency induction melting, atomizing and screening to form copper alloy powder with the granularity of 60-80 mu m; and finally, placing the iron-based amorphous alloy powder and the copper alloy powder in a high-energy ball mill according to the mass ratio of 1: 9-1: 7, uniformly mixing, and then screening, activating, drying, chemically plating nickel, filtering, washing, drying and screening to obtain copper-based composite powder with the granularity of 40-50 microns.
The copper-based composite powder of the invention adopts the technological parameters of selective laser melting and forming as follows: the laser power is 100-300W, the spot diameter is 80 mu m, the laser scanning speed is 500-5000 mm/s, the thickness of the layered slice is 80-100 mu m, the lap ratio between two continuous layers is 50%, the selective laser melting forming is carried out in a mode that the laser scanning directions between two continuous layers are mutually vertical, and the main performance indexes of the obtained iron-based amorphous reinforced copper-based alloy are as follows: the wear resistance is 8-10 times of that of brass, the corrosion resistance is equivalent to that of brass, the conductivity is 50-65% IACS, the fracture strength is 0.8-1.2 GPa, and the elongation is 15-30%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A copper-based composite powder for melting and forming an iron-based amorphous reinforced copper-based alloy in a selective laser area is characterized in that: the copper-based composite powder mainly comprises iron-based amorphous powder and copper alloy powder in a mass ratio of 1: 9-1: 7, wherein the iron-based amorphous powder comprises the following chemical components: 8-10 wt.% of W, 4-6 wt.% of Cr, 1-3 wt.% of Mo, 1-3 wt.% of Ni, 3-5 wt.% of Si, 3-5 wt.% of B, 0.2-1 wt.% of C, 0.2-1.5 wt.% of Mn, HfO20.8-1.5 wt.%, the balance being Fe; the chemical components of the copper alloy powder are as follows: 0.5-2 wt.% of Cr, 1-3 wt.% of Zr, 3-5 wt.% of P, and CeO20.2-1 wt.%, and the balance of Cu; and carrying out high-energy ball milling and mixing on the iron-based amorphous powder and the copper alloy powder to generate mutual diffusion reaction, and then carrying out chemical nickel plating treatment.
2. The copper-based composite powder for the selective laser melting forming of the iron-based amorphous reinforced copper-based alloy according to claim 1, wherein: the chemical components of the iron-based amorphous powder are as follows: w8.5 wt.%, Cr 5.2 wt.%, Mo 2.5 wt.%, Ni 2.4 wt.%, Si 3.5 wt.%, B4.5 wt.%, C0.5 wt.%, Mn 1.2 wt.%, HfO20.85 wt.%, balance Fe; the chemical components of the copper alloy powder are as follows: cr 1.5 wt.%, Zr 1.2 wt.%, P4.2 wt.%, CeO20.8 wt.%, with the balance being Cu.
3. The copper-based composite powder for the selective laser melting forming of the iron-based amorphous reinforced copper-based alloy according to claim 1, wherein: the particle size of the copper-based composite powder is 40-50 mu m.
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| CN202011427359.9A CN112643022B (en) | 2020-12-09 | 2020-12-09 | Copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in selective laser area |
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| CN202011427359.9A CN112643022B (en) | 2020-12-09 | 2020-12-09 | Copper-based composite powder for melting and forming iron-based amorphous reinforced copper-based alloy in selective laser area |
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| CN114472923B (en) * | 2022-01-21 | 2023-04-07 | 航发优材(镇江)增材制造有限公司 | Selective laser melting forming manufacturing process for copper alloy lattice structure |
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| CN100442402C (en) * | 2005-11-16 | 2008-12-10 | 安泰科技股份有限公司 | Iron-base non-crystal alloy powder, magnetic powder core with excellent high frequency performance and preparation process thereof |
| CN106995906A (en) * | 2010-03-19 | 2017-08-01 | 科卢斯博知识产权有限公司 | Iron-chromium-molybdenum base hot spray powder and its manufacture method |
| JP2015503028A (en) * | 2011-11-21 | 2015-01-29 | クルーシブル インテレクチュアル プロパティ エルエルシーＣｒｕｃｉｂｌｅ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ Ｌｌｃ | Alloying of Fe-based bulk amorphous alloys |
| CN104178656A (en) * | 2014-08-21 | 2014-12-03 | 青岛骏泽盛泰智能科技有限公司 | Cu-Fe composite material |
| CN105154709B (en) * | 2015-07-17 | 2017-11-14 | 河南科技大学 | High chrome copper material and preparation method thereof |
| CN108080636B (en) * | 2017-12-18 | 2019-09-27 | 暨南大学 | A kind of method that selective laser fusing shaped hollow richness iron particle enhances copper-based monotectic alloy |
| CN107900341B (en) * | 2017-12-18 | 2019-08-30 | 暨南大学 | A kind of method of selective laser fusing forming large scale high-performance monotectic alloy |
| CN109434118B (en) * | 2018-10-30 | 2020-07-10 | 华中科技大学 | Preparation and forming method of amorphous reinforced metal matrix composite |
| CN111441046B (en) * | 2020-03-27 | 2022-05-31 | 安徽科技学院 | Iron-based amorphous nanocrystalline dual-phase structure composite coating and preparation method thereof |
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