CN114551134A - Preparation method of grain-boundary-refined silver copper oxide electrical contact material - Google Patents
Preparation method of grain-boundary-refined silver copper oxide electrical contact material Download PDFInfo
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- CN114551134A CN114551134A CN202210005677.9A CN202210005677A CN114551134A CN 114551134 A CN114551134 A CN 114551134A CN 202210005677 A CN202210005677 A CN 202210005677A CN 114551134 A CN114551134 A CN 114551134A
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- copper oxide
- silver copper
- electrical contact
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
- C22C5/08—Alloys based on silver with copper as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/10—Technologies relating to charging of electric vehicles
- Y02T90/14—Plug-in electric vehicles
Abstract
The invention discloses a preparation method of a silver copper oxide electrical contact material for refining grain boundaries, which comprises the following steps: smelting Ag and Cu into a liquid phase, adding an additive, and stirring and crystallizing in a re-crystallizer to obtain AgCu alloy particles containing the additive; the content of Ag in the AgCu alloy particles is 83-95 wt%, the content of Cu is 4-14 wt%, and the balance is additive content; (2) oxidizing the AgCu alloy particles or material sections obtained in the step (1) into silver copper oxide particles; (3) pressing the silver copper oxide obtained in the step (2) into an AgCuO spindle; (4) and (4) sintering, extruding and molding the AgCuO spindle in the step (3) into the silver copper oxide electrical contact material with refined grain boundary. The invention has the advantages that the scheme improves the fusion welding resistance of the material by adding the high melting point item, refines the grain boundary, improves the oxidation energy barrier and refines the enhanced item particles.
Description
Technical Field
The invention belongs to the field of electrical contact materials, particularly belongs to the field of metal matrix composite materials, and particularly relates to a preparation method of a grain boundary refined silver copper oxide electrical contact material, which is mainly used for electrical elements in the fields of new energy automobiles, new capital construction and the like.
Background
With the requirement of the voltage and the current for the vigorous popularization and development of new energy automobiles, charging piles, 5G base stations, smart power grids and sealed relays, in order to improve the performances of fusion welding resistance, burning loss resistance, electric conductivity and the like of materials, material manufacturers are respectively remarkable, materials such as silver tin oxide, silver tin oxide indium oxide and the like are mainly improved, but silver-rich areas are easily formed in the process of arc corrosion of the silver tin oxide materials, and contact bonding is caused.
The silver-copper oxide is a silver-based oxide material which takes silver as a basic material, copper oxide and additives as an enhanced phase, is mainly applied to electrical elements such as electrical switches of relays, contactors, switches and the like, and the manufactured electrical contacts mainly have the functions of conducting and breaking current, resisting large current impact and the like. The main preparation methods of the silver copper oxide include a pre-oxidation method, internal oxidation, a traditional powder mixing method, a chemical method and the like. The methods have various advantages, the addition types of the material additives prepared by the traditional powder mixing method and the chemical method are not limited, but the prepared material has low compactness, coarse oxide particles and large consumption in the service life process; the traditional internal oxidation has large grain boundary, obvious oxide lean area and rich area, and because copper is easy to oxidize to form a copper oxide strengthening item with thicker particles, the preparation process is long, and the cost is high
Specifically, the following documents of the prior art are referred to above by search:
1) the preparation method disclosed in CN107523712B, chinese patent "a preparation process of silver-copper oxide composite material", is to infiltrate liquid phase Ag into the gaps between copper oxide and copper oxide to obtain a material; the above document 1) is that silver easily penetrates into the gap between the mixed powder of copper oxide and silver, and the material produced by this method has low strength, poor denseness, and is liable to deposit silver, and it is difficult to process other shapes.
2) The preparation method disclosed in CN111468718A, chinese patent "a silver copper oxide sheet electrical contact", is to prepare a silver copper oxide powder spindle, sinter and repress the spindle, and obtain a sheet contact with a surface coated with silver copper alloy by hydrogen reduction; document 2) a sheet contact of silver copper oxide coated silver copper structure is obtained by reduction using a spindle.
3) CN109420511A, a preparation method of a silver copper oxide material, discloses a preparation method of a silver copper oxide nano material by adding ammonia water into silver nitrate and copper nitrate solution and carrying out chemical reduction; document 3) is a method of obtaining silver by chemical reduction and obtaining silver-copper oxide powder by thermal decomposition, and this method is poor in material awareness, and fine silver-copper oxide particles can be obtained by adjusting parameters, but it is difficult to clean, and the chemical milling is high in cost, and has a great influence on the environment and a great difficulty in environmental protection treatment.
4) Chinese patent CN107130134B, a silver-copper oxide composite electrical contact material and a preparation method thereof, discloses a preparation method of a silver-copper oxide material by melting silver and copper into liquid, preparing alloy powder by atomization, reducing at high temperature with hydrogen, ball-milling, oxidizing at high pressure, isostatic pressing, sintering, and extruding. In the document (4), after the silver and the copper are alloyed in a melting furnace, silver-copper alloy powder is formed by an atomizing device, and the powder is reduced by hydrogen, ball-milled and finally oxidized to obtain silver-copper oxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a silver copper oxide electrical contact material with refined grain boundaries. According to the scheme, the high-melting-point item is added, so that the fusion welding resistance of the material is improved, the grain boundary is refined, the oxidation energy barrier is improved, and the enhanced item particles are refined.
In order to realize the purpose, the technical scheme of the invention comprises the following steps:
(1) smelting Ag and Cu into a liquid phase, adding an additive, and stirring and crystallizing in a crystallizer to obtain AgCu alloy particles containing the additive; the content of Ag in the AgCu alloy particles is 83-95 wt%, the content of Cu is 4-14 wt%, and the balance is additive content;
(2) oxidizing the AgCu alloy particles obtained in the step (1) into silver copper oxide particles;
(3) pressing the silver copper oxide particles obtained in the step (2) into an AgCuO spindle;
the further setting is that the aperture of the crystallizer is 1mm-3mm.
The method is further provided that the additive composition in the step (1) is as follows:
Sn:0.5-2wt％；Zn:0-0.5％；Ni:0.25％；Pt:0.5-1％。
further setting that in the step (1), Ag, Cu and additives are firstly smelted in a smelting furnace, after refining, the alloy liquid is recrystallized in a crystallizer, and cooling is carried out to obtain AgCu alloy particles or wire segments containing the additives, wherein the diameters of the spherical particles are as follows: 1mm-3mm, the diameter of the material section-shaped particles is as follows: 1mm-3mm, material length: 10mm-30mm, wherein the stirring speed in the crystallizer is 5r/min-15r/min, and the cooling water temperature is 0-60 ℃.
The further setting is that the oxidation temperature in the step (2) is firstly pre-oxidized for 0.5 hour in the air atmosphere at 450-500 ℃, and then the oxidation time is continued for 3-6 hours under the oxygen pressure of 0.1-1 MPa and the temperature of 650-780 ℃.
Further setting the step (3) of pressing the ingot into a cylindrical ingot in a hydraulic press, wherein the pressure is 20MPa-80MPa, the pressure maintaining time is 5s-30s, and the diameter of the ingot is 80cm-120 cm.
It is further provided that said step (4) comprises the sub-steps of:
(a) sintering an AgCuO spindle at 800-860 ℃ for 2.5-4 hours;
(b) the sintered spindle is extruded into the diameter of 750-830 DEG C
Drawing the wire with the corresponding specification, and processing and forming the contact with the required shape and specification.
The invention has the advantages that:
according to the method, the AgCu alloy is firstly smelted into a liquid phase, additives such as Sn, Zn, Pt and Ni are added to increase the dislocation of the AgCu alloy material, and the crystal boundary is refined by recrystallization in a crystallizer under the action of external force, so that the uniformity of the alloy is improved, the crystal boundary is refined, the oxidation energy barrier is reduced, the oxidation speed is increased, the crystal boundary and the crystal grain are refined, the wear resistance of the silver copper oxide is improved, the material consumption is reduced, and the action times of the silver copper oxide in the arc erosion process of a contact are ensured. In addition, the required round-like alloy particles or linear material sections are obtained through the mesh structure with the aperture of the crystallizer being 1mm-3mm and through the adjustment of the solution temperature and the cooling temperature, copper is easy to oxidize in the air, the crystallization is refined, the specific surface area is increased, a better silver copper oxide structure is obtained, and then the compact fine-particle silver copper oxide material is obtained through ingot pressing and extrusion.
Compared with the prior art, the material has high hardness, high tensile strength and low resistivity. Wear resistance and consumption reduction, and the service life of the contact under the service condition is prolonged. The copper oxide has good thermal stability, is not easy to decompose into copper and oxygen, and has good fusion welding resistance. The material of the invention is widely used in the fields of new energy and new infrastructure.
The method of the invention refines the silver-copper crystal boundary and improves the performance, and has the advantages of simple preparation process, short flow, no use of chemical reagents such as acid, alkali and the like in the whole process, product conformity with the legislation such as European Union quantity instruction and the like, and environment-friendly preparation process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive labor.
FIG. 1 is a process flow diagram of the preparation method of the present invention;
FIG. 2 is a diagram of the gold phase prepared by the process of the present invention in example II;
FIG. 3 is a diagram of an extrusion phase of gold by conventional atomized sintering.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Examples
99.99 percent of silver, 99.5 percent of Cu, 99.5 percent of Sn, 99.5 percent of Zn,99.5 percent of Pt and 99.9 percent of Ni powder are melted into liquid phase in a melting furnace according to the mass ratio shown in the table 1, the liquid phase is refined and transferred into a crystallizer, the aperture of the crystallizer is 1mm-3mm, the stirring speed in the crystallizer is 5r/min-15r/min, the cooling water temperature is 0 ℃ -60 ℃, 1mm-3mm ball-like particles or thin wire sections with the diameter of 1mm-3mm and the length of 10mm-30mm are obtained, the oxidation temperature is pre-oxidized in the air atmosphere at 450 ℃ -500 ℃ for 0.5 hour, the oxygen pressure is 0.1MPa-1MPa, the temperature is 650 ℃ -780 ℃, the oxidation time is 3h-6h, the pressure maintaining time of the oxidized materials in a hydraulic press with the pressure of 20-80 Mpa is 5s-30s, the diameter size of a spindle is 80cm-120cm, the spindle is sintered and extruded into a diameter of
Drawing the required specification.
Table 1 material composition scheme units: wt.%
| Examples of the invention | Ag％ | Cu％ | Sn％ | Zn％ | Ni％ | Pt％ |
| Example one | 93.25 | 4 | 2 | - | 0.25 | 0.5 |
| Example two | 84 | 14 | 0.75 | 0.5 | 0.25 | 0.5 |
| Example three | 90 | 9.25 | 0.5 | - | 0.25 | 1 |
TABLE 2 comparison of physical Properties of the materials
From the physical properties of the materials in Table 2, there is a decrease in the bulk resistance of the materials. Because the oxide particles are fine, the hardness and tensile strength of the material are higher than those of the prior internal oxidation process, but the elongation is good, so that the processing plasticity of the material is improved. Meanwhile, after the oxide reinforcing phase particles are refined, the surface area of the oxide is increased, and the oxide is uniformly and finely distributed in the silver matrix, so that the heat resistance of the material is improved, the fusion welding resistance of the material is improved, the hardness is improved, the material abrasion is improved, a large-current switching phenomenon is caused when a new power switch for construction is used, the hardness is below HV0.3, the deformation is easily caused in the impact process of a moving contact and a static contact, the non-conduction is caused, and the service life is influenced. FIG. 2 is a metallographic picture of AgCuO having a silver content of about 83% in the present example; FIG. 3 is a metallographic picture of a material of AgCuO with a silver content of about 83% by adopting atomization, sintering and extrusion technologies. From 200 times the metallographic phase of the example of the invention, fine copper oxide particles were distributed on a silver matrix. Therefore, the grain boundary is refined through external stirring force of the re-crystallizer, and the grains are obviously refined through gradient oxidation adjustment, so that the design effect is achieved.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (7)
1. A preparation method of a silver copper oxide electrical contact material with refined grain boundary is characterized by comprising the following steps:
(1) smelting Ag and Cu into a liquid phase, adding an additive, and stirring and crystallizing in a crystallizer to obtain AgCu alloy particles or wire segments containing the additive; the content of Ag in the AgCu alloy is 83-95 wt%, the content of Cu is 4-14 wt%, and the balance is additive content;
(2) oxidizing the AgCu alloy particles or the wire segments obtained in the step (1) into silver copper oxide particles;
(3) pressing the silver copper oxide particles or the wire segments obtained in the step (2) into an AgCuO spindle;
(4) and (4) sintering, extruding and molding the AgCuO spindle in the step (3) into the silver copper oxide electrical contact material with refined grain boundaries.
2. The method for preparing the grain boundary refined silver copper oxide electrical contact material according to claim 1, wherein the method comprises the following steps: the aperture of the crystallizer is 1mm-3mm.
3. The method for preparing the grain boundary refined silver copper oxide electrical contact material according to claim 1, wherein the method comprises the following steps: the additive composition in the step (1) is as follows:
Sn:0.5-2wt％；Zn:0-0.5％；Ni:0.25％；Pt:0.5-1％。
4. the method for preparing the silver copper oxide electrical contact material with the refined grain boundary according to claim 1, characterized in that: in the step (1), Ag, Cu and additives are firstly smelted in a smelting furnace, alloy liquid is recrystallized in a crystallizer after refining, AgCu alloy particles or wire sections containing the additives are obtained after cooling, and the diameters of spherical particles are as follows: 1mm-3mm, or the diameter of the material section-shaped particles is as follows: 1mm-3mm, material length: 10mm-30mm, wherein the stirring speed in the crystallizer is 5r/min-15r/min, and the cooling water temperature is 0-60 ℃.
5. The method for preparing the grain boundary refined silver copper oxide electrical contact material according to claim 1, wherein the method comprises the following steps: the oxidation temperature in the step (2) is pre-oxidized for 0.5 hour in the air atmosphere at 450-500 ℃, and then the oxidation time is continued for 3-6 hours under the oxygen pressure of 0.1-1 MPa and the temperature of 650-780 ℃.
6. The method for preparing the grain boundary refined silver copper oxide electrical contact material according to claim 1, wherein the method comprises the following steps: and (3) pressing the ingot in a hydraulic machine to form a cylindrical ingot, wherein the pressure is 20-80 Mpa, the pressure maintaining time is 5-30 s, and the diameter of the ingot is 80-120 cm.
7. The method for preparing the grain boundary refined silver copper oxide electrical contact material according to claim 1, wherein the method comprises the following steps: the step (4) comprises the following substeps:
(a) sintering an AgCuO spindle at 800-860 ℃ for 2.5-4 hours;
(b) the sintered spindle is extruded into the diameter of 750-830 DEG C
Drawing the wire with the corresponding specification, and processing and forming the contact with the required shape and specification.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115927899A (en) * | 2022-12-13 | 2023-04-07 | 温州中希电工合金有限公司 | Silver copper oxide contact material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115927899A (en) * | 2022-12-13 | 2023-04-07 | 温州中希电工合金有限公司 | Silver copper oxide contact material and preparation method thereof |
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