CN113061778B - In-situ amorphous particle reinforced copper alloy material - Google Patents
In-situ amorphous particle reinforced copper alloy material Download PDFInfo
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- CN113061778B CN113061778B CN202110182520.9A CN202110182520A CN113061778B CN 113061778 B CN113061778 B CN 113061778B CN 202110182520 A CN202110182520 A CN 202110182520A CN 113061778 B CN113061778 B CN 113061778B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/06—Permanent moulds for shaped castings
- B22C9/061—Materials which make up the mould
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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
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
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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
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/003—Moulding by spraying metal on a surface
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
Abstract
The invention belongs to the design and preparation technology of copper alloy and composite materials thereof, and particularly relates to an in-situ endogenetic amorphous particle reinforced copper alloy material. The material comprises alloying elements Cu and Ni (or Fe, Co), and added alloying elements Nb, Ta, Sn and B (or Si, B, C, Cr, Mo, Co, Ni, and Nb, Ta, B, Si, C, Nb, Fe and Mo) for promoting the separation of Cu and Ni (or Fe, Co). The alloy melt is subjected to liquid phase decomposition in the rapid cooling process to form two liquid phases of a Cu alloy and a Ni alloy (or Fe alloy and Co alloy), the matrix liquid phase Cu alloy and the second liquid phase Ni alloy (or Fe alloy and Co alloy) are respectively subjected to crystallization solidification and amorphous transformation, and the amorphous particle reinforced copper alloy material is formed in situ. In the in-situ endogenic amorphous particle reinforced copper alloy material, the interface of the reinforced phase and the metal matrix is well combined, the compactness of the material is high, and no brittle phase is generated at the interface.
Description
Technical Field
The invention belongs to the design and preparation technology of copper alloy and composite materials thereof, and particularly relates to an in-situ endogenetic amorphous particle reinforced copper alloy material.
Background
Pure copper has high thermal conductivity, electrical conductivity and excellent processing performance, and is a basic material of most electronic components. However, pure copper has low strength and hardness, and high thermal expansion coefficient, and is difficult to meet the requirements of practical application. Therefore, how to greatly improve the strength of the copper alloy on the premise of keeping a higher conductivity level becomes a key point of research and development in the field of copper materials. In order to meet the rapid development of technology and industry, ceramic particles (e.g., Al) 2 O 3 SiC) or fibers (e.g.: w) as a reinforcement added to metallic copper to form a copper-based composite material: see the Chinese patent (patent No. CN201610584289.5, publication No. CN 106)048275A), a method for preparing ceramic phase dispersion strengthened copper alloy; see the Chinese patent (patent No. CN201811571224.2, publication No. CN109440024A) and the preparation method of the tungsten fiber/copper-based composite board. The high-strength reinforcing bodies can improve the hardness of the alloy on the basis of keeping certain original plasticity of the copper alloy. However, the ceramic strengthening phase and the copper matrix phase have large differences in physical and chemical properties, which inevitably causes problems, such as: the ceramic and metal matrix have large difference in thermal expansion coefficients, resulting in poor bonding at the ceramic-metal interface.
Amorphous alloys have been widely used in recent years as reinforcements for composite materials because of their excellent properties such as high strength, high hardness, and excellent wear and corrosion resistance. Compared with a reinforcement body such as ceramic and the like, the amorphous alloy has better wettability with a matrix metal, so that the interface bonding between the reinforcement body and the matrix is improved. Referring to Chinese patent (patent No. CN201811298708.4, publication No. CN109439937A), "a method for preparing nickel-plated amorphous alloy particle reinforced aluminum matrix composite", an additional prefabricated nickel-based amorphous particle reinforced aluminum matrix composite is reported. From research reports at home and abroad, the method for preparing the amorphous phase reinforced metal matrix composite mainly comprises powder metallurgy, infiltration casting and the like. Among them, the powder metallurgy method, that is, after mixing amorphous powder and alloy powder prepared in advance uniformly according to a certain proportion, the powder is subjected to repeated deformation and crushing by high energy ball milling, etc., so that reinforcement is dispersed and distributed in an alloy matrix, see chinese patent (patent No. CN201610171752.3, publication No. CN105803236A), "an amorphous alloy reinforced aluminum-based composite material and its preparation method"; the infiltration casting method, i.e. casting the metal alloy melt into the space of the self-amorphous thin strip framework, and forming the amorphous and matrix metal composite structure after solidification, is described in journal papers: preparation of Ni-Nb-Ta metallic glass reinforced aluminum-based alloy-based composite Material by infiltration casting, Kuaiji (English) materials, Vol.50, 2004. These methods of adding an amorphous phase are directed to light alloys with low melting points such as aluminum alloys, magnesium alloys, etc.; the amorphous phase is easy to crystallize in the powder metallurgy and infiltration casting process, the amorphous phase and the metal matrix are easy to form a brittle reaction layer, the compactness of the material is not promoted, and the like; the powder metallurgy preparation process is complex, the production period is long, and the cost is high; the amorphous phase reinforced metal matrix composite material cannot be prepared by infiltration casting for the alloy with high melting point. Although the patent of invention (patent No. CN200710010038.7, publication No. CN101220445A) discloses an amorphous alloy spherical particle/crystalline alloy matrix composite material and a preparation method thereof, in-situ amorphous reinforced copper alloy and alloy components thereof are not explicitly disclosed.
Disclosure of Invention
The invention aims to provide an in-situ endogenetic amorphous particle reinforced copper alloy material, which solves the bottleneck problem existing in the preparation method of the copper alloy and the composite material thereof on one hand, and solves the problem that the amorphous alloy is difficult to be used for reinforcing the copper alloy on the other hand.
The technical scheme of the invention is as follows:
an in-situ endogenetic amorphous particle reinforced copper alloy material, a matrix is crystalline copper alloy, and a reinforcing phase is amorphous particles of Ni base, Fe base or Co base; when the reinforcing phase is Ni-based amorphous particles, the alloy comprises the following components in percentage by atom: 6% -16%, Nb: 1% -7%, Ta: 0% -1.5%, Sn: 0% -1.4%, B: 0 to 0.2 percent of Cu, and the balance of Cu; when the reinforcing phase is Fe-based amorphous particles, the alloy comprises the following components in percentage by atom: 3.8% -18.4%, Si: 0% -3%, B: 0.05% -3%, C: 0% -3%, Cr: 0% -2.8%, Mo: 0% -3%, Co: 0% -7.8%, Ni: 0% -7.2%, Nb: 0 to 1.2 percent of Cu and the balance of Cu; when the reinforcing phase is Co-based amorphous particles, the alloy comprises the following components in percentage by atom: 2.7% -12.4%, Ta: 0% -2%, B: 1.5% -7.5%, Si: 0% -1.2%, C: 0% -3%, Nb: 0% -1.6%, Fe: 0% -4%, Mo: 0 to 0.4 percent of Cu, and the balance of Cu; the alloy melt is decomposed in a liquid phase in a rapid cooling process to form two liquid phases of a Cu alloy and a Ni alloy or a Fe alloy or a Co alloy, wherein the Cu alloy liquid phase is crystallized and solidified, the second liquid phase Ni alloy or the Fe alloy or the Co alloy is subjected to amorphous transformation, and the Ni-based or Fe-based or Co-based amorphous particle reinforced copper alloy material is formed in situ.
In the in-situ endogenetic amorphous particle reinforced copper alloy material and the Ni-based amorphous particle reinforced copper alloy material, elements Nb, Ta, Sn and B are distributed in Ni-based amorphous particles; in the Fe-based amorphous particle reinforced copper alloy material, elements Si, B, C, Cr, Mo, Co, Ni and Nb are distributed in Fe-based amorphous particles; in the Co-based amorphous particle reinforced copper alloy material, elements Ta, B, Si, C, Nb, Fe and Mo are distributed in the Co-based amorphous particles.
According to the in-situ endogenetic amorphous particle reinforced copper alloy material, the sizes of amorphous particles in a copper alloy matrix are distributed in a nanometer and micrometer double-scale mode, the size of the nanometer amorphous particles is 1-100 nanometers, and the size of the micrometer amorphous particles is 1-200 micrometers.
The invention has the advantages and beneficial effects that:
1. the invention adds other alloy elements Nb, Ta, Sn and B (or Si, B, C, Cr, Mo, Co, Ni and Nb, Ta, B, Si, C, Nb, Fe and Mo) for promoting the liquid-liquid phase separation and amorphous transformation of Cu and Ni (or Fe, Co) on the basis of Cu-Ni (or Cu-Fe, Cu-Co) binary alloy, so that Ni- (Sn, B) - (Nb, Ta) -Cu (or Fe- (Si, B, C) - (Cr, Mo, Co, Ni, Nb) -Cu, Co- (Si, B, C) - (Ta, Nb, Fe, Mo) -Cu) alloy has the metallurgical characteristics of liquid component immiscible region, and through the optimized design of alloy components, the liquid-liquid phase separation of the alloy melt is preferentially generated before the amorphous transformation, and the Cu alloy and the Ni alloy (or Fe alloy, Cu-Co) are formed in situ, Co alloy) two liquid phases. Under the condition of rapid cooling, the second liquid phase Ni alloy (or Fe alloy and Co alloy) generates amorphous transformation, and amorphous particle reinforced copper alloy material is formed in situ. The method not only simplifies and shortens the preparation process and the cost of the composite material, but also points out the direction for developing novel high-performance metal materials.
2. The invention utilizes the phase separation metallurgy characteristic of immiscible alloy and the amorphous transformation characteristic of alloy, and adopts a rapid solidification technology to obtain an in-situ endogenic amorphous particle reinforced copper alloy material, wherein before the amorphous transformation of alloy melt, liquid-liquid phase separation is firstly carried out to form two liquid phases of Cu alloy and Ni alloy (or Fe alloy and Co alloy); in the subsequent rapid cooling process, the matrix liquid-phase Cu alloy is solidified and crystallized, the second liquid-phase Ni alloy (or Fe alloy and Co alloy) is subjected to amorphous transformation, and the amorphous particle reinforced copper alloy material is formed in situ. On the one hand, the amorphous phase after solidification can be ensured to be uniformly distributed in the metal matrix; on the other hand, compared with the traditional preparation process of copper alloy composite material powder metallurgy, the technology of the invention can avoid the problems of crystallization of second-phase amorphous particles, oxidation at a two-phase interface and the like caused in the processing process, and the interface between the amorphous particles and the metal matrix is better combined. In particular, the process for preparing the amorphous particle reinforced copper alloy material by the endogenetic mode is simple and has lower cost.
Drawings
FIG. 1 shows an alloy (Cu) of example 1 of the present invention 89.26 Ni 7.93 Nb 2.34 Ta 0.47 ) Scanning electron microscope photo of in-situ endogenetic amorphous particle reinforced copper alloy material prepared by rapid solidification technology.
FIG. 2 shows an alloy (Cu) of example 1 of the present invention 89.26 Ni 7.93 Nb 2.34 Ta 0.47 ) And (3) a high-resolution transmission electron micrograph of the in-situ endogenetic amorphous particle reinforced copper alloy material prepared by a rapid solidification technology.
FIG. 3 shows an alloy (Cu) of example 2 of the present invention 86.85 Ni 9.4 Nb 3.13 Ta 0.62 ) Scanning electron microscope photo of in-situ endogenetic amorphous particle reinforced copper alloy material prepared by rapid solidification technology.
FIG. 4 shows an alloy (Cu) of example 3 of the present invention 90 Co 5.95 Ta 0.8 B 3.25 ) Scanning electron microscope photo of in-situ endogenetic amorphous particle reinforced copper alloy material prepared by rapid solidification technology.
FIG. 5 shows an alloy (Cu) of example 4 of the present invention 92.5 Fe 5.85 Si 0.67 B 0.98 ) Scanning electron microscope photo of in-situ endogenetic amorphous particle reinforced copper alloy material prepared by rapid solidification technology.
Detailed Description
In the specific implementation process, the invention provides an alloy design and preparation technology of an in-situ endogenetic amorphous particle reinforced copper alloy material, which is characterized in that other alloy elements Nb, Ta, Sn and B (or Si, B, C, Cr, Mo, Co, Ni and Nb, Ta, B, Si, C, Nb, Fe and Mo) for promoting the liquid-liquid phase separation and the amorphous transformation of Cu and Ni (or Fe, Co) are added on the basis of a Cu-Ni (or Cu-Fe, Cu-Co) binary alloy, so that the Ni- (Sn, B) - (Nb, Ta) -Cu (or Fe- (Si, B, C) - (Cr, Mo, Co, Ni, Nb) -Cu, Co- (Si, B, C) - (Ta, Nb, Fe, Mo) -Cu) alloy has the metallurgical characteristics of a liquid component immiscible region, and the alloy melt is optimally designed before the amorphous transformation occurs, liquid-liquid phase separation is preferentially carried out to form a matrix liquid phase of the Cu alloy and a second liquid phase of the Ni alloy (or Fe alloy and Co alloy); in the subsequent rapid cooling process, the second liquid phase Ni alloy (or Fe alloy or Co alloy) is subjected to amorphous transformation, and the amorphous particle reinforced copper alloy material is formed in situ after solidification.
In the aspect of alloy selection and design, the in-situ endogenic amorphous particle reinforced copper alloy material preferentially selects a Cu-Ni (or Cu-Fe, Cu-Co) binary alloy and other added alloy elements Nb, Ta, Sn and B (or Si, B, C, Cr, Mo, Co, Ni and Nb, Ta, B, Si, C, Nb, Fe and Mo) for promoting liquid-liquid phase separation and amorphous transformation of Cu and Ni (or Fe and Co). In the rapid cooling process of the alloy melt, liquid-liquid phase separation is firstly carried out to form two liquid phases of Cu alloy and Ni alloy (or Fe alloy and Co alloy), the liquid phase of a Cu alloy matrix is firstly solidified and crystallized under the rapid solidification condition, then the second liquid phase Ni alloy (or Fe alloy and Co alloy) is subjected to amorphous transformation, and the formed Ni-based (or Fe-based and Co-based) amorphous phase is distributed in a crystalline Cu alloy matrix as spherical particles. Therefore, when the reinforcing phase is Ni-based amorphous particles, the alloy comprises the following components in percentage by atom: 6% -16%, Nb: 1% -7%, Ta: 0% -1.5%, Sn: 0% -1.4%, B: 0 to 0.2 percent of Cu and the balance of Cu; when the reinforcing phase is Fe-based amorphous particles, the alloy comprises the following components in percentage by atom: 3.8% -18.4%, Si: 0% -3%, B: 0.05% -3%, C: 0% -3%, Cr: 0% -2.8%, Mo: 0% -3%, Co: 0% -7.8%, Ni: 0% -7.2%, Nb: 0 to 1.2 percent of Cu and the balance of Cu; when the reinforcing phase is Co-based amorphous particles, the alloy comprises the following components in percentage by atom: 2.7% -12.4%, Ta: 0% -2%, B: 1.5% -7.5%, Si: 0% -1.2%, C: 0% -3%, Nb: 0% -1.6%, Fe: 0% -4%, Mo: 0 to 0.4 percent of Cu and the balance of Cu. The size of amorphous particles in the copper alloy matrix is in nano (5-100 nm) + micron (1-100 micron) dual-scale distribution.
Firstly purchasing Ni, Nb, Ta, Cu, Fe, Si, Co, Ta, B, Mo, Cr and Sn metal raw materials with the purity of not less than 99.9 wt% from the market, carrying out surface cleaning treatment on the metal raw materials, placing the metal raw materials into a water-cooled copper crucible of an electric arc melting furnace according to designed alloy components, and keeping the air pressure of a chamber to be melted to be not more than 2.5 multiplied by 10 -3 And (2) after Pa, filling high-purity argon with the volume purity of 99.999% into the electric arc furnace until the air pressure of a smelting chamber reaches 0.03MPa, smelting a high-purity Ti ingot to absorb oxygen and other impurities remained in the electric arc furnace before smelting a metal raw material, further purifying protective gas, repeatedly smelting for 3-4 times while controlling the smelting current to be 200-300A when smelting the metal raw material, and thus obtaining the Ni- (Sn, B) - (Nb, Ta) -Cu (or Fe- (Si, B, C) - (Cr, Mo, Co, Ni, Nb) -Cu, Co- (Si, B, C) - (Ta, Nb, Fe, Mo) -Cu) master alloy ingot. After the mother alloy ingot is cooled, several grams of mother alloy are taken and placed in a quartz crucible, and the quartz crucible is vacuumized until the air pressure is not higher than 2.5 multiplied by 10 -3 The mother alloy is quickly melted by induction heating in a Pa vacuum environment, and the cooling speed is not lower than 10 3 ～10 6 And preparing the in-situ endogenetic amorphous particle reinforced copper alloy material by using the rapid solidification technologies of K/s single-roller melting and throwing, copper mold casting, copper mold spray casting and the like.
The present invention will be described in further detail below with reference to examples.
Example 1
In this embodiment, the chemical composition of the alloy is first designed, and based on the Cu — Ni binary alloy, other alloy elements Nb and Ta that cause liquid-liquid phase separation and amorphous transformation of Ni and Cu are added. The atomic ratio of the alloy element Cu is 89.26%, the atomic ratio of the alloy element Ni is 7.93%, the atomic ratio of the alloy element Nb is 2.34%, and the atomic ratio of the alloy element Ta is 0.47%.
Then purchasing Ni, Nb, Ta and Cu metal raw materials with the purity of not less than 99.9 wt% from the market, cleaning the surfaces of the metal raw materials, and weighing the metal raw materials according to the designed alloy componentsThe metal raw material is placed in a water-cooled copper crucible of an electric arc melting furnace. Vacuumizing the arc melting furnace to the air pressure of 2.0 x 10 -3 After Pa, filling high-purity argon with the volume purity of 99.999% into the electric arc furnace until the air pressure of the smelting chamber reaches 0.03MPa so as to protect the alloy from being oxidized in the smelting process; before smelting Ni, Nb, Ta and Cu metal raw materials, firstly smelting a high-purity Ti ingot to absorb residual oxygen and other impurities in an electric arc furnace and further purifying protective gas; when metal raw materials of Ni, Nb, Ta and Cu are smelted, smelting current is controlled to be 200-300A (250A in the embodiment), and smelting is repeated for 3 times, so that a Ni-Nb-Ta-Cu master alloy ingot is obtained. After the mother alloy ingot is cooled, 6 g of the mother alloy is taken and placed in a quartz crucible, and the quartz crucible is vacuumized until the air pressure is not higher than 2.5 multiplied by 10 -3 Pa (2.0X 10 in this example) -3 Pa) under vacuum environment, rapidly melting the master alloy by induction heating, and preparing the in-situ endogenetic amorphous particle reinforced copper alloy material by a rapid solidification technology.
Scanning Electron Microscope (SEM) is adopted to observe the prepared in-situ endogenetic amorphous particle reinforced copper alloy material sample, as shown in figure 1. The Ni-Nb-Ta phase exists in the form of spherical particles. The high-resolution transmission electron microscope (HRTEM) confirmed that the Ni-Nb-Ta phase was an amorphous phase, as shown in FIG. 2. SEM and HRTEM results show that the Ni-Nb-Ta amorphous particle size presents nano + micron dual-scale distribution, and the average size of Ni-Nb-Ta particles measured by quantitative metallographic analysis software is about 53 nm. In this embodiment, the size range of the nano amorphous particles is 3 to 20 nanometers, and the size range of the micro amorphous particles is 1 to 3 micrometers.
Example 2
In this embodiment, the chemical composition of the alloy is first designed, and based on a Cu — Ni binary alloy, other alloying elements Nb and Ta that cause liquid-liquid phase separation and amorphous transformation of Ni and Cu are added. The atomic ratio of the alloy element Cu is 86.85%, the atomic ratio of the alloy element Ni is 9.4%, the atomic ratio of the alloy element Nb is 3.13%, and the atomic ratio of the alloy element Ta is 0.62%.
Then purchasing Ni, Nb, Ta and Cu metal raw materials with the purity of not less than 99.9 wt% from the market, cleaning the surfaces of the metal raw materials, and then cleaning the surfaces of the metal raw materials according to the following proportionAccording to the designed alloy components, the weighed metal raw materials are placed in a water-cooled copper crucible of an electric arc melting furnace. Vacuum-pumping the arc melting furnace to the pressure of 1.5 × 10 -3 After Pa, filling high-purity argon with the volume purity of 99.999% into the electric arc furnace until the air pressure of the smelting chamber reaches 0.03MPa so as to protect the alloy from being oxidized in the smelting process; before smelting Ni, Nb, Ta and Cu metal raw materials, firstly smelting a high-purity Ti ingot to absorb residual oxygen and other impurities in an electric arc furnace and further purifying protective gas; when metal raw materials of Ni, Nb, Ta and Cu are smelted, smelting current is controlled to be 200-300A (250A in the embodiment), and smelting is repeated for 4 times, so that a Ni-Nb-Ta-Cu master alloy ingot is obtained. After the master alloy ingot is cooled, 8 g of master alloy is taken and placed in a quartz crucible, and the quartz crucible is vacuumized until the air pressure is not higher than 2.5 multiplied by 10 -3 Pa (1.5X 10 in this example) -3 Pa) under vacuum environment, rapidly melting the master alloy by induction heating, and preparing the in-situ endogenetic amorphous particle reinforced copper alloy material by a rapid solidification technology.
Scanning Electron Microscope (SEM) was used to observe the prepared in-situ grown amorphous particle reinforced copper alloy material sample, as shown in fig. 3. The Ni-Nb-Ta amorphous phase exists mainly in the form of spherical particles, and a small amount of fibrous Ni-Nb-Ta amorphous phase exists. The average size of the Ni-Nb-Ta amorphous phase particles was determined to be about 129nm by quantitative metallographic analysis software. In this embodiment, the size range of the nano amorphous particles is 5 to 50 nanometers, and the size range of the micro amorphous particles is 2 to 7 micrometers.
Example 3
In this embodiment, the chemical composition of the alloy is first designed, and based on a Cu-Co binary alloy, other alloying elements Ta and B that cause liquid-liquid phase separation and amorphous transformation of Cu and Co are added. The atomic ratio of the alloy element Cu is 90%, the atomic ratio of the alloy element Co is 5.95%, the atomic ratio of the alloy element B is 3.25%, and the atomic ratio of the alloy element Ta is 0.08%.
Then purchasing Co, Ta, B and Cu metal raw materials with the purity of not less than 99.9 wt% from the market, cleaning the surfaces of the metal raw materials, and putting the weighed metal raw materials into an electric arc for melting according to designed alloy componentsIn a water-cooled copper crucible of the smelting furnace. Vacuum-pumping the vacuum melting furnace to the air pressure of 1.0 x 10 -3 After Pa, filling high-purity argon with the volume purity of 99.999% into the electric arc furnace until the air pressure of the smelting chamber reaches 0.03MPa so as to protect the alloy from being oxidized in the smelting process; before smelting Co, Ta, B and Cu metal raw materials, firstly smelting a high-purity Ti ingot to absorb residual oxygen and other impurities in an electric arc furnace and further purifying protective gas; when Co, Ta, B and Cu metal raw materials are smelted, smelting current is controlled to be 200-300A (250A in the embodiment), and smelting is repeated for 3 times, so that a Co-Ta-B-Cu master alloy ingot is obtained. After the mother alloy ingot is cooled, 4 g of mother alloy is taken and placed in a quartz crucible, and the quartz crucible is vacuumized until the air pressure is not higher than 2.5 multiplied by 10 -3 Pa (in this example, 1.0X 10 -3 Pa) under vacuum environment, rapidly melting the master alloy by induction heating, and preparing the in-situ endogenetic amorphous particle reinforced copper alloy material by a rapid solidification technology.
Scanning Electron Microscope (SEM) was used to observe the prepared in-situ grown amorphous particle reinforced copper alloy material sample, as shown in fig. 4. The Co-Ta-B amorphous phase exists in the form of spherical particle morphology particles, the particle size presents nanometer + micrometer dual-scale distribution, and the average size of the Co-Ta-B particles is about 150nm and the volume fraction is about 23 percent as measured by quantitative metallographic analysis software. In this embodiment, the size range of the nano amorphous particles is 5 to 20 nm, and the size range of the micro amorphous particles is 1 to 10 μm.
Example 4
In this embodiment, the alloy chemical composition is first designed, and based on a Cu — Fe binary alloy, other alloy elements Si and B are added to cause liquid-liquid phase separation and amorphous transformation of Cu and Fe. The atomic ratio of the alloy element Cu is 92.5%, the atomic ratio of the alloy element Fe is 5.85%, the atomic ratio of the alloy element B is 0.98%, and the atomic ratio of the alloy element Si is 0.67%.
Then purchasing Fe, Si, B and Cu metal raw materials with the purity of not less than 99.9 wt% from the market, cleaning the surfaces of the metal raw materials, and putting the weighed metal raw materials into a water-cooled copper crucible of an arc melting furnace according to designed alloy components. Melting furnaceVacuum-pumping to pressure of 1.0 × 10 -3 After Pa, filling high-purity argon with the volume purity of 99.999% into the electric arc furnace until the air pressure of the smelting chamber reaches 0.03MPa so as to protect the alloy from being oxidized in the smelting process; before smelting Fe, Si, B and Cu metal raw materials, firstly smelting a high-purity Ti ingot to absorb residual oxygen and other impurities in an electric arc furnace and further purifying protective gas; when the metal raw materials of Fe, Si, B and Cu are smelted, the smelting current is controlled to be 200-300A (250A in the embodiment), and the smelting is repeated for 3 times, so that the Fe-Si-B-Cu master alloy ingot is obtained. After the master alloy ingot is cooled, 10 g of master alloy is taken and placed in a quartz crucible, and the quartz crucible is vacuumized until the air pressure is not higher than 2.5 multiplied by 10 -3 Pa (2.5X 10 in this example) -3 Pa) under vacuum environment, rapidly melting the master alloy by induction heating, and preparing the in-situ endogenetic amorphous particle reinforced copper alloy material by a rapid solidification technology.
Scanning Electron Microscope (SEM) was used to observe the prepared in-situ grown amorphous particle reinforced copper alloy material sample, as shown in fig. 5. The Fe-Si-B amorphous phase exists in the form of spherical particle morphology particles, and the particle size presents nano + micron dual-scale distribution. In this embodiment, the size range of the nano amorphous particles is 50 to 100 nm, and the size range of the micro amorphous particles is 1 to 3 μm.
The embodiment result shows that compared with the traditional powder metallurgy preparation process of the ceramic reinforced copper alloy composite material, in the in-situ endogenetic amorphous particle reinforced copper alloy material, the interface of the reinforced phase and the metal matrix is well combined, the material compactness is high, no brittle phase is generated at the interface, the problems of amorphous phase crystallization, two-phase interface oxidation and the like caused in the processing process can be avoided, and the preparation method has the characteristics of simple process, short production period, lower cost and the like.
Claims (1)
1. An in-situ endogenetic amorphous particle reinforced copper alloy material is characterized in that a matrix is crystalline copper alloy, and a reinforcing phase is Ni-based amorphous particles; when the reinforcing phase is Ni-based amorphous particles, the alloy comprises the following components in percentage by atom: 6% -16%, Nb: 1% -7%, Ta: 0.47% -1.5%, Sn: 0% -1.4%, B: 0 to 0.2 percent of Cu and the balance of Cu; the alloy melt is decomposed into two liquid phases of Cu alloy and Ni alloy in the process of rapid cooling, wherein the liquid phase of the Cu alloy is crystallized and solidified, the second liquid phase Ni alloy is subjected to amorphous transformation, and a Ni-based amorphous particle reinforced copper alloy material is formed in situ;
in the Ni-based amorphous particle reinforced copper alloy material, elements Nb, Ta, Sn and B are distributed in Ni-based amorphous particles;
the sizes of amorphous particles in the copper alloy matrix are distributed in a nanometer and micrometer scale, the size of the nanometer amorphous particles is 1-100 nanometers, and the size of the micrometer amorphous particles is 1-200 micrometers.
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| KR20070106887A (en) * | 2006-05-01 | 2007-11-06 | 학교법인연세대학교 | Cu-based two phase metallic glass alloys with multi-pass deformation property |
| CN101220446A (en) * | 2007-01-12 | 2008-07-16 | 中国科学院金属研究所 | Amorphous alloy spherical particle/amorphous alloy base composite material and manufacturing method thereof |
| CN101220445A (en) * | 2007-01-12 | 2008-07-16 | 中国科学院金属研究所 | Amorphous state alloy spherical particle/crystalline state alloy base composite material and manufacturing method thereof |
| CN102682945A (en) * | 2012-05-11 | 2012-09-19 | 西北工业大学 | Fe-Co-Si-B-Cu in-situ composite material with amorphous-crystalline double-layer structure and preparation method thereof |
| CN102861920A (en) * | 2012-10-17 | 2013-01-09 | 厦门大学 | Crystalline/amorphous composite powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070106887A (en) * | 2006-05-01 | 2007-11-06 | 학교법인연세대학교 | Cu-based two phase metallic glass alloys with multi-pass deformation property |
| CN101220446A (en) * | 2007-01-12 | 2008-07-16 | 中国科学院金属研究所 | Amorphous alloy spherical particle/amorphous alloy base composite material and manufacturing method thereof |
| CN101220445A (en) * | 2007-01-12 | 2008-07-16 | 中国科学院金属研究所 | Amorphous state alloy spherical particle/crystalline state alloy base composite material and manufacturing method thereof |
| CN102682945A (en) * | 2012-05-11 | 2012-09-19 | 西北工业大学 | Fe-Co-Si-B-Cu in-situ composite material with amorphous-crystalline double-layer structure and preparation method thereof |
| CN102861920A (en) * | 2012-10-17 | 2013-01-09 | 厦门大学 | Crystalline/amorphous composite powder and preparation method thereof |
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