CN109182832B - Carbon nano tube reinforced copper-based alloy and powder injection molding process - Google Patents

Carbon nano tube reinforced copper-based alloy and powder injection molding process Download PDF

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CN109182832B
CN109182832B CN201811322029.6A CN201811322029A CN109182832B CN 109182832 B CN109182832 B CN 109182832B CN 201811322029 A CN201811322029 A CN 201811322029A CN 109182832 B CN109182832 B CN 109182832B
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CN109182832A (en
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邬均文
薛永超
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Jiangsu Gian Technology Co Ltd
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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
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0549—Hollow particles, including tubes and shells
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • 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
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling

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Abstract

The invention relates to a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and binder, carbon nanotube and CuCr1The invention also discloses a powder injection molding process, which comprises the steps of preparation, granulation, injection molding, degreasing and sintering to obtain a finished product; according to the invention, the finished product is prepared by the formula of the remnants marquee reinforced copper-based alloy and the injection molding method, and is efficient, convenient and fast.

Description

Carbon nano tube reinforced copper-based alloy and powder injection molding process
Technical Field
The invention relates to a carbon nano tube reinforced copper-based alloy and a powder injection molding process.
Background
The carbon nano tube reinforced copper alloy has the advantages of excellent heat conduction and electric conduction of the copper alloy, and also has the characteristics of low thermal expansion coefficient, good wear resistance, good heat-resistant strength and the like of the composite material. The high-voltage self-lubricating bearing is mainly applied to the fields of aviation, aerospace, energy sources, automobiles and the like, such as semiconductors, conductor rails, electrical contacts, self-lubricating bearings and the like. At present, the high-performance carbon nanotube reinforced copper alloy composite material is mainly obtained by plating copper or nickel and the like on the surface of carbon fiber, mixing the carbon fiber with copper or copper alloy powder, forming, sintering and forming, and combining post-treatment processes such as hot rolling and the like.
The carbon nano tube is not infiltrated with copper, and the interface bonding force of the composite material is relatively weak. At present, a carbon nano tube surface coating process is generally adopted to obtain a metal coating capable of increasing infiltration so as to improve the strength of the composite material. Therefore, the process has a relatively complex technical route and relatively high production cost.
SUMMARY OF THE PATENT FOR INVENTION
It is a first object of the present invention to provide a carbon nanotube reinforced copper-based alloy with high efficiency.
The technical scheme for realizing the purpose of the invention is as follows: the invention comprises carbon nano-tubes and CuCr1Alloy powder and a binder, wherein the specification of the nanotube is as follows: the length is 10-30 μm, the pipe diameter is 5-10nm, and the purity is more than or equal to 97%; the CuCr1The alloy powder comprises the following components: the content of Cr is 0.9-1.1%, the content of O is less than or equal to 0.15%, and the rest components are Cu elements; the CuCr1The specification of the alloy powder is as follows: d10 has a particle size distribution of 3-4 μm and D50 has a particle size distribution of9-10 μm, and D90 particle size distribution of 24.0-25 μm;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The binder is a plastic matrix binder.
The second purpose of the invention is to provide a powder injection molding process with advanced technology and high production efficiency.
The technical scheme for realizing the purpose of the invention is as follows: the invention comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injection molding: injecting the feeding raw material into a charging barrel of an injection machine, injecting the feeding raw material into a mould through a nozzle of the injection machine for forming, and demolding to obtain a carbon nano tube reinforced copper alloy composite material blank;
D. degreasing and sintering: at the temperature of 110 +/-10 ℃, the blank is catalytically degreased by oxalic acid with the purity of more than or equal to 99.6 percent, and then is sintered and molded for 2 to 4 hours at the temperature of 1040 +/-5 ℃ in hydrogen atmosphere.
The invention has the positive effects that: (1) the invention prepares the carbon nano tube reinforced copper alloy composite material part by designing and preparing the components of the copper alloy powder, preparing the feeding raw materials and combining the powder injection molding technology.
(2) Compared with pure copper, the CuCr1 alloy improves the wettability and the interface bonding force of the carbon nano tube and a copper matrix.
(3) The technology of the invention adopts a powder injection molding technology, and meets the requirements of the current advanced technology industry on high precision, high complex structure, high efficiency, large-scale production and the like of high-strength, high-heat-conductivity, high-wear-resistance copper and copper alloy parts with low thermal expansion coefficients.
Detailed Description
(embodiment one)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 10 mu m, the pipe diameter is 10nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 0.9, the content of O is 0.15 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: d10 with a particle size distribution of 3 μm, D50 with a particle size distribution of 10 μm and D90 with a particle size distribution of 24.5 μm, wherein the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. granulating, namely preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing at the temperature of 110 ℃ by adopting oxalic acid purity, wherein the oxalic acid purity is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then in a hydrogen atmosphere,Keeping the mixture at 1040 ℃ for 2 to 4 hours for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(second embodiment)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 11 mu m, the pipe diameter is 9nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 0.92 percent, the content of O is 0.14 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: d10 with a particle size distribution of 4 μm, D50 with a particle size distribution of 9 μm and D90 with a particle size distribution of 25 μm, wherein the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing at 110 ℃ by using oxalic acid, wherein the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(third embodiment)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 12 mu m, the pipe diameter is 8nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 0.94 percent, the content of O is less than or equal to 0.13 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: the D10 particle size distribution is 3.5 mu m, the D50 particle size distribution is 9.5 mu m, the D90 particle size distribution is 24 mu m, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injection molding: injecting the feeding raw material into a charging barrel of an injection machine, injecting the feeding raw material into a mould through a nozzle of the injection machine for forming, and demolding to obtain a carbon nano tube reinforced copper alloy composite material blank;
D. degreasing and sintering: at the temperature of 110 ℃, oxalic acid is adopted for catalytic degreasing, the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(example four)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 13 mu m, the pipe diameter is 7nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 0.96 percent, the content of O is 0.12 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: the D10 particle size distribution is 3.4 mu m, the D50 particle size distribution is 9.2 mu m, the D90 particle size distribution is 24 mu m, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. granulating, namely preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing at 110 ℃ by using oxalic acid, wherein the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(fifth embodiment)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 15 mu m, the pipe diameter is 7nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 0.98 percent, the content of O is 0.11 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: the D10 particle size distribution is 3.6 mu m, the D50 particle size distribution is 9.5 mu m, the D90 particle size distribution is 24.6 mu m, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture with a binder for 2-3 hours to obtain a feed materialThe melt index is 1000-;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing at 110 ℃ by using oxalic acid, wherein the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(sixth embodiment)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 18 mu m, the pipe diameter is 9nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 1 percent, the content of O is 0.1 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: the D10 particle size distribution is 3.6 mu m, the D50 particle size distribution is 9.4 mu m, the D90 particle size distribution is 24.8 mu m, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then through the atmosphere protection mixing technology, under the temperature of 190 plus or minus 5℃,Under the protection of argon, the purity of the argon is more than or equal to 99.999 percent, and the carbon nano tube and CuCr are mixed1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injection molding: injecting the feeding raw material into a charging barrel of an injection machine, injecting the feeding raw material into a mould through a nozzle of the injection machine for forming, and demolding to obtain a carbon nano tube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing by oxalic acid at the temperature of 110 +/-10 ℃, wherein the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture for 2 to 4 hours at the temperature of 1040 +/-5 ℃ in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(seventh embodiment)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 22 mu m, the pipe diameter is 8nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 1.02 percent, the content of O is less than or equal to 0.09 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: d10 particle size distribution is 3-4 μm, D50 particle size distribution is 9-10 μm, D90 particle size distribution is 24.3 μm, the binder is plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: mixing the carbon nanotube reinforced copper-based alloy in a three-dimensional mixerMixing to obtain uniformly dispersed carbon nanotube and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. granulating, namely preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing at 110 ℃ by using oxalic acid, wherein the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(eighth embodiment)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 24 mu m, the pipe diameter is 8nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 1.06%, the content of O is 0.08%, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: the D10 particle size distribution is 3.8 mu m, the D50 particle size distribution is 9.2 mu m, the D90 particle size distribution is 24.6 mu m, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injection molding: injecting the feeding raw material into a charging barrel of an injection machine, injecting the feeding raw material into a mould through a nozzle of the injection machine for forming, and demolding to obtain a carbon nano tube reinforced copper alloy composite material blank;
D. degreasing and sintering: at the temperature of 110 ℃, oxalic acid is adopted for catalytic degreasing, the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(example nine)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 25 mu m, the pipe diameter is 7nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 1.08 percent, the content of O is less than or equal to 0.06 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: the D10 particle size distribution is 3.6 mu m, the D50 particle size distribution is 9.3 mu m, the D90 particle size distribution is 24.9 mu m, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. granulating, namely preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing at 110 ℃ by using oxalic acid, wherein the purity of the oxalic acid is more than or equal to 99.6 percent, and the degreasing rate is more than or equal to 7.3 percent. Then keeping the mixture at 1040 ℃ for 2-4 hours in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
(example ten)
The invention provides a carbon nano tube reinforced copper-based alloy, which comprises a carbon nano tube and CuCr1Alloy powder and a binder, and the specification of the nanotube is as follows: the length is 26 mu m, the pipe diameter is 9nm, and the purity is more than or equal to 97 percent; CuCr1The alloy powder comprises the following components: the content of Cr is 1.1 percent, the content of O is 0.14 percent, and the rest components are Cu elements; CuCr1The specification of the alloy powder is as follows: d10 particle size distribution of 3.8The particle size distribution of D50 is 9.1 μm, the particle size distribution of D90 is 25 μm, and the binder is a plastic matrix binder;
CuCr1the weight of the carbon nanotubes accounts for 99.4 percent of the total weight, and the weight of the carbon nanotubes accounts for 0.6 percent of the total weight.
The invention also relates to a powder injection molding process, which comprises the following steps:
A. preparing and feeding: fully mixing the carbon nano tube reinforced copper-based alloy in a three-dimensional mixer to obtain uniformly dispersed carbon nano tubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. granulating, namely preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injecting the feeding material into the material barrel of the injection machine, injecting the feeding material into the mold through the nozzle of the injection machine for molding, and demolding to obtain a carbon nanotube reinforced copper alloy composite material blank;
D. degreasing and sintering, namely performing catalytic degreasing by using oxalic acid (the purity is more than or equal to 99.6%) at the temperature of 110 +/-10 ℃, wherein the degreasing rate is more than or equal to 7.3%. Then keeping the mixture for 2 to 4 hours at the temperature of 1040 +/-5 ℃ in hydrogen atmosphere for sintering and forming, wherein the sintering density is more than or equal to 8.4g/cm3；
The main technical indicators of the obtained finished product are as follows: the density rho is more than or equal to 8.4g/cm3Hardness Hv80-100 HV0.3The yield strength sigma s is more than or equal to 280Mpa, the tensile strength is more than or equal to 400Mpa, the electric conductivity IACS is more than or equal to 70 percent, the heat conductivity coefficient is more than or equal to 220W/mk, the thermal expansion coefficient is less than or equal to 10 multiplied by 10-6 DEG C-1。
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. A carbon nanotube reinforced copper-based alloy comprises carbon nanotubes and is characterized in that: also comprises CuCr1Alloy powder and a binder, wherein the specification of the nanotube is as follows: the length is 10-30 μm, the pipe diameter is 5-10nm, and the purity is more than or equal to 97%; the CuCr1The alloy powder comprises the following components: the content of Cr is 0.9-1.1%, the content of O is less than or equal to 0.15%, and the rest components are Cu elements; the CuCr1The specification of the alloy powder is as follows: d10 particle size distribution is 3-4 μm, D50 particle size distribution is 9-10 μm, and D90 particle size distribution is 24.0-25 μm;
CuCr1the weight of the carbon nano tube accounts for 99.4 percent of the total weight, and the weight of the carbon nano tube accounts for 0.6 percent of the total weight;
the binder is a plastic matrix binder.
2. A powder injection molding process, comprising the steps of:
A. preparing and feeding: fully mixing the carbon nanotube reinforced copper-based alloy in claim 1 in a three-dimensional mixer to obtain uniformly dispersed carbon nanotubes and CuCr1An alloy powder mixture; then, the carbon nano tube and CuCr are mixed by an atmosphere protection mixing technology, the purity of argon is more than or equal to 99.999 percent at the temperature of 190 +/-5 ℃ under the protection of argon1Mixing the alloy powder mixture and the binder for 2-3 hours, wherein the melt index of the obtained feed is 1000-1200g/10 min;
B. and (3) granulation: preparing the feed mixed in the preparation method of the carbon nano tube copper-based alloy into a feed raw material for injection in a fixed particle form by a granulator;
C. injection molding: injecting the feeding raw material into a charging barrel of an injection machine, injecting the feeding raw material into a mould through a nozzle of the injection machine for forming, and demolding to obtain a carbon nano tube reinforced copper alloy composite material blank;
D. degreasing and sintering: at the temperature of 110 +/-10 ℃, the blank is catalytically degreased by oxalic acid with the purity of more than or equal to 99.6 percent, and then is sintered and molded for 2 to 4 hours at the temperature of 1040 +/-5 ℃ in hydrogen atmosphere.
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