CN108425032B - Solidification preparation method of Cu-Cr electrical contact alloy with dispersion type composite solidification structure - Google Patents

Solidification preparation method of Cu-Cr electrical contact alloy with dispersion type composite solidification structure Download PDF

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CN108425032B
CN108425032B CN201810293417.XA CN201810293417A CN108425032B CN 108425032 B CN108425032 B CN 108425032B CN 201810293417 A CN201810293417 A CN 201810293417A CN 108425032 B CN108425032 B CN 108425032B
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alloy
electrical contact
solidification
particles
liquid
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CN108425032A (en
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赵九洲
陶杰
江鸿翔
张丽丽
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Institute of Metal Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • 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
    • C22C32/0047—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 carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—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 carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/025—Composite material having copper as the basic material

Abstract

The invention discloses a solidification preparation method of a Cu-Cr electrical contact alloy with a dispersion type composite solidification structure, and belongs to the technical field of Cu-Cr electrical contact alloy material preparation. By adding Cr to Cu-Cr alloy3C2And when liquid-liquid phase change occurs in the cooling process of the melt, the nucleating agent particles can be used as the nucleating substrate of the Cr-rich phase droplets, so that the nucleating rate of the Cr-rich phase droplets is greatly improved, and the formation of a dispersion type Cu-Cr alloy composite solidification structure is promoted. The method can be used for preparing high-quality Cu-Cr electrical contact alloy materials.

Description

Solidification preparation method of Cu-Cr electrical contact alloy with dispersion type composite solidification structure
Technical Field
The invention relates to the technical field of Cu-Cr electrical contact alloy material preparation, in particular to a solidification preparation method of a Cu-Cr electrical contact alloy with a dispersion type composite solidification structure.
Background
Cu-Cr alloys are an important electrical contact material. The material requires that the Cr-rich phase is dispersed in a Cu matrix in a particle form. The phase diagram of the Cu-Cr alloy is shown in FIG. 1, with a metastable liquid component immiscible temperature regime (see dashed line in FIG. 1). When the homogeneous alloy melt is cooled to a temperature within the immiscible temperature range of the metastable liquid component, a liquid-liquid phase change occurs and Cr-rich phase droplets precipitate out of the melt. Because the specific gravity difference between two liquid phases is very large, the phenomenon of serious phase segregation and even two-phase layering is easily formed during the liquid-liquid phase change, so that the preparation of the Cu-Cr electrical contact alloy with a dispersion type solidification structure is very difficult, and the traditional casting method is difficult to obtain an alloy material with a uniform structure, which limits the preparation of the Cu-Cr electrical contact alloy by using the casting technology in industry. By adopting proper measures, the nucleation rate of the dispersed phase liquid drop is improved, so that the size and the migration speed of the dispersed phase liquid drop are reduced, the formation speed of phase segregation is slowed down, and the method is an effective way for preparing the Cu-Cr electrical contact alloy.
Disclosure of Invention
The invention aims to provide a solidification preparation method of a Cu-Cr electrical contact alloy with a dispersion type composite solidification structure. By adding micro-nano Cr into Cu-Cr alloy3C2The particles are used as a nucleating agent, and Cr is generated in the liquid-liquid phase change process of the Cu-Cr alloy3C2The particles can be used as nucleation substrates of Cr-rich phase droplets, thereby greatly improving the Cr-rich phase dropletsThe nucleation rate of the drops promotes the formation of the composite solidification structure of the dispersion Cu-Cr alloy.
The technical scheme of the invention is as follows:
a solidification preparation method of Cu-Cr electrical contact alloy with a dispersion type composite solidification structure adopts a casting technology, firstly, Cu-Cr alloy raw materials are smelted, and micro-nano-sized Cr is added into an obtained Cu-Cr alloy melt3C2The particles are used as nucleating agent, and then the melt is cast in a metal mould or a graphite mould for rapid cooling. When containing Cr3C2When liquid-liquid phase change occurs in the cooling process of the Cu-Cr alloy melt of the particles, Cr3C2The particles are used as nucleation substrates of the Cr-rich phase liquid drops, so that the nucleation rate of the Cr-rich phase liquid drops is improved, and the alloy solidification is promoted to form the Cu-Cr electrical contact alloy with a dispersion type composite solidification structure.
The Cr is3C2The size (particle diameter) of the particles is 0.01 to 20 μm.
The Cr is3C2The addition amount of the particles is 0.005-0.1 wt% of the weight of the Cu-Cr alloy.
In the Cu-Cr alloy raw material, the content of Cr element is 10-50 wt%.
The melting temperature of the Cu-Cr alloy raw material is TcSatisfy Tb+100℃<Tc<1650 deg.C, wherein TbIs the equilibrium liquid-liquid phase change temperature of the Cu-Cr electrical contact alloy.
The casting temperature of the Cu-Cr alloy is higher than TbSaid Cr being3C2The particles are added in the form of a charge.
In the prepared Cu-Cr electrical contact alloy, Cr is dispersed in a Cu matrix in a particle form.
The principle of the invention is as follows:
the invention adds micro-nano Cr to the Cu-Cr alloy3C2And (3) granules. The particles can be used as a nucleation substrate of Cr-rich phase liquid drops in the Cu-Cr alloy liquid-liquid phase transformation process, so that the nucleation rate of the Cr-rich phase liquid drops is greatly improved, and the acquisition of a diffusion type Cu-Cr alloy coagulation structure is promoted.
The invention has the beneficial effects that:
1. the invention utilizes heterogeneous nucleation technology to control the solidification kinetics of the Cu-Cr alloy, obtains the Cu-Cr alloy composite material with Cr dispersed in the Cu matrix in a particle form, and meets the industrial requirement.
2. The invention is particularly suitable for casting techniques with a relatively high cooling rate, such as: metal mold casting, graphite mold casting, and the like.
Drawings
FIG. 1 is a schematic phase diagram of a Cu-Cr alloy.
FIG. 2 shows Cr3C2Particle morphology.
FIG. 3 shows Cu-10 wt% Cr and Cu-10 wt% Cr-0.1 wt% Cr3C2A microstructure of an alloy specimen, wherein: (a) without addition of Cr3C2Particles; (b) 0.01 wt% of Cr is added3C2. In the figure, the matrix is a Cu-rich phase, and the dispersed particles are a Cr-rich phase.
FIG. 4 shows Cu-20 wt% Cr and Cu-20 wt% Cr-0.1 wt% Cr3C2A microstructure of an alloy specimen, wherein: (a) without addition of Cr3C2(ii) a (b) 0.1wt% of Cr is added3C2. In the figure, the matrix is a Cu-rich phase, and the dispersed particles are a Cr-rich phase.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings and examples.
When the Cu-Cr alloy is solidified, a solidification structure with serious segregation and even two-phase layering is easily formed, and the preparation is extremely difficult. The invention researches Cr3C2The influence of the particles on the solidification behavior and the structure of the Cu-Cr alloy is found, and micro-nano Cr is found3C2The particles can obviously improve the heterogeneous nucleation rate of Cr-rich phase liquid drops in the Cu-Cr alloy liquid-liquid phase change process, refine the solidification structure and promote the acquisition of a dispersion type solidification structure. Accordingly, the invention adds micro-nano Cr to the Cu-Cr alloy3C2And (4) granulating to prepare the dispersed Cu-Cr alloy composite material. FIG. 2 shows Cr3C2And (4) particle morphology graph. The Cu-Cr alloy structure prepared by the method is shown in fig. 3 and 4.
Example 1
As shown in FIG. 3, a Cu-10 wt% Cr alloy and Cu-10 wt% Cr-0.1 wt% Cr were cast using a copper mold3C2Alloy, the inner diameter of the copper mold is 5mm, and the temperature of the copper mold is room temperature before casting. Without addition of Cr3C2The Cr-rich phase in the granular sample exists in the form of coarse dendrites, and Cr is added3C2The Cr-rich phase in the alloy sample of the particles exists in a dispersed particle form and is uniformly distributed.
The preparation process comprises the following steps:
melting Cu-10 wt% Cr alloy and Cu-10 wt% Cr-0.1 wt% Cr in an electric arc furnace3C2And (3) alloying, heating to 1600 ℃, preserving the temperature for 2 minutes, and injecting the melt into a copper mold.
Example 2
As shown in FIG. 4, a Cu-20 wt% Cr alloy and Cu-20 wt% Cr-0.1 wt% Cr were cast using a copper mold3C2Alloy, the inner diameter of the copper mold is 5mm, and the temperature of the copper mold is room temperature before casting. Without addition of Cr3C2The Cr-rich phase in the granular sample exists in the form of coarse dendrites, and Cr is added3C2The Cr-rich phase in the alloy sample of the particles exists in a dispersed particle form and is uniformly distributed.
The preparation process comprises the following steps:
an electric arc furnace is used for smelting Cu-20 wt% Cr alloy and Cu-20 wt% Cr-0.1 wt% Cr3C2And (3) alloying, heating to 1600 ℃, preserving the temperature for 2 minutes, and injecting the melt into a copper mold.

Claims (3)

1. A solidification preparation method of Cu-Cr electrical contact alloy with a dispersion type composite solidification structure is characterized by comprising the following steps: the method adopts a casting technology, firstly, a Cu-Cr alloy raw material is smelted, and micro-nano Cr is added into the obtained Cu-Cr alloy melt3C2The particles as nucleating agent when containing Cr3C2When liquid-liquid phase change occurs in the cooling process of the Cu-Cr alloy melt of the particles, Cr3C2The particles are used as nucleation substrates of the Cr-rich phase liquid drops, so that the nucleation rate of the Cr-rich phase liquid drops is improved; solidifying the melt to form Cu-Cr alloy with a dispersion type composite solidification structure;
the Cr is3C2The diameter of the particles was 0.01 ~ 20 microns;
the Cr is3C2The addition amount of the particles is 0.005 ~ 0.1.1 wt% of the weight of the Cu-Cr alloy melt;
in the Cu-Cr alloy raw material, the content of Cr element is 10 ~ 50 wt%.
2. The solidification preparation method of the Cu-Cr electrical contact alloy with the dispersion-type composite solidification structure according to claim 1, characterized by comprising the following steps: the melting temperature of the Cu-Cr alloy raw material isT cSatisfy the following requirementsT b+100℃<T c<1650 deg.C, whereinT bIs the equilibrium liquid-liquid phase change temperature of the Cu-Cr alloy.
3. The solidification preparation method of the Cu-Cr electrical contact alloy with the dispersion-type composite solidification structure according to claim 1 or 2, characterized by comprising the following steps: in the Cu-Cr electrical contact alloy, Cr is dispersed in a Cu matrix in a particle form.
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US4954170A (en) * 1989-06-30 1990-09-04 Westinghouse Electric Corp. Methods of making high performance compacts and products
JP2846941B2 (en) * 1990-10-30 1999-01-13 本田技研工業株式会社 Electrode material and method for manufacturing electrode material
JP3456224B2 (en) * 1993-06-11 2003-10-14 マツダ株式会社 Manufacturing method of aluminum alloy member
JP3317179B2 (en) * 1997-03-06 2002-08-26 三菱マテリアル株式会社 Method for producing Fe, C-containing copper alloy
JP2007018835A (en) * 2005-07-07 2007-01-25 Hitachi Ltd Electric contact for vacuum circuit breaker and its manufacturing method
CN100513009C (en) * 2007-08-03 2009-07-15 钢铁研究总院 Method for dispersion implanting fine heterogeneous particles during metal freezing course and added raw material
CN101255510B (en) * 2008-03-26 2013-01-23 晶能光电（江西）有限公司 High-strength high-conductive chromium-copper and preparation thereof
CN101565803A (en) * 2009-06-03 2009-10-28 北京科技大学 Heat treatment method for improving strength and conductivity of copper alloy of Cu-Cr series
CN103540788B (en) * 2013-10-14 2016-08-10 北京科技大学 A kind of preparation method of Cr nanostructured crystal grain copper
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