CN109576529A - High-performance disperse copper alloy and preparation method thereof - Google Patents
High-performance disperse copper alloy and preparation method thereof Download PDFInfo
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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
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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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
Abstract
The present invention provides a kind of high-performance disperse copper alloys, wherein including the Al of mass percent meter2O30.04~0.9%, Cr0.1~1.0%, surplus are copper, and the present invention also provides the preparation methods of above-mentioned high-performance disperse copper alloy.High-performance disperse copper alloy provided by the invention, conductivity and intensity with higher simultaneously, it can get " double 80 copper alloys " that the optimal conductivity of current comprehensive performance is higher than 800MPa higher than 80%IACS, intensity using preparation method provided by the invention by the regulation of ingredient.
Description
Technical field
The invention belongs to powder metallurgical technologies, and in particular to high-performance disperse copper alloy and preparation method thereof.
Background technique
Al2O3Nano dispersion reinforced copper alloy is a kind of new structure with excellent combination physical property and mechanical property
Functional material, it has both high strength & high electric-conduction can be with good softening performance resistant to high temperatures.The common system of dispersion strengthening copper alloy
Preparation Method includes: mechanical mixing, coprecipitation, nitrate fusion method, internal oxidation etc..It is prepared at present using internal oxidition technology
Al2O3Nano dispersion reinforced copper alloy is maximally efficient preparation method.
The detailed process of internal oxidation is first by after the suitable Cu-Al alloy melting of ingredient, and the atomization of gas (water) body is dusted, then
It is mixed with suitable oxidant, heating carries out internal oxidition in closed container, and the oxygen that solute element Al is penetrated by diffusion into the surface is excellent
Initial oxidation generates Al2O3, composite powder is restored in hydrogen then, removes remaining Cu2O(CuAlO2), then by powder bag
It covers, vacuumize, squeezing or hot forging forming.CN104911383B, which is disclosed, a kind of prepares Al2O3The method of dispersion strengthening copper alloy,
The invention is with CuAl alloyed powder and Cu2O powder is raw material, is mixed in proportion, and internal oxidition is first carried out in nitrogen atmosphere, through broken
It is restored in hydrogen after broken, sieving, prepares Al2O3Disperse copper alloy powder, then high velocity compacted alloy powder is at green compact,
Finally green compact is placed directly in hot isostatic pressing furnace, hot isostatic pressing is carried out, obtains Al2O3Dispersion strengthening copper alloy, the invention use
High-speed pressing and forming obtains the green compact of high-compactness, directly carries out hot isostatic pressing, technical process without carrying out jacket to green compact
Simply, it is suitable for producing in batches.CN1291049C discloses a kind of dispersion strengthening copper alloy, aluminium in the dispersion strengthening copper alloy
Content is 0.05~0.6%, and surplus is copper, passes through mixing, cold etc. with nitrogen or the hydraulic atomized copper-Al alloy powder produced
Static pressure, heat treatment and etc. be prepared, which has both good conductive, heating conduction.
However, during internal oxidation preparation, if Al fails adequately from Copper substrate with Al2O3The shape of particle
Formula is sufficiently precipitated, then the intensity and conductivity of alloy can all be affected, and in the prior art, internal oxidation prepares the strong copper of disperse and closes
The Al content of gold is no more than 1.1wt%, and otherwise internal oxidition cannot be carried out sufficiently, corresponding A l2O3Nano dispersion reinforced copper alloy
Maximum intensity is usually no more than 620MPa, conductivity 75%IACS or so.
To sum up, although Al2O3Nano dispersion reinforced copper alloy have high strength & high electric-conduction can and it is good resistant to high temperatures soft
Change the potentiality of performance, however existing disperse copper alloy, be not possible to meet 3C, IT, AI, ehv power transmission, aerospace and
High-speed rail transportation field has high-intensitive and high conductivity requirement to Cu alloy material simultaneously.
Summary of the invention
To solve the problem of that existing disperse copper alloy is unable to reach double 80 copper alloy performances, the present invention in the prior art
The first purpose be to provide a kind of high-performance disperse copper alloy.
The second object of the present invention is to provide the preparation method of above-mentioned copper alloy.
To realize overwood purpose, the invention adopts the following technical scheme:
High-performance disperse copper alloy, the component including following mass percent meter:
Al2O30.04~0.9%,
Cr 0.1~1.0%,
Surplus is copper.
Preferably, the component including following mass percent meter:
Al2O30.13~0.6%,
Cr 0.2~0.4%,
Surplus is copper.
The preparation method of above-mentioned high-performance disperse copper alloy, step include:
(1) aerosolization after Cu-Al, Cu-Cr melting is obtained into Cu-Al alloy powder and Cu-Cr alloy powder respectively；
(2) the Cu-Al alloy powder for obtaining step (1) and oxidant carry out internal oxidition processing after mixing, and obtain interior oxygen
Alloy powder；
(3) it is restored after being crushed the internally oxidized alloy powder that step (2) obtains, obtains Cu-Al2O3Dispersion strengthening copper alloy
Powder；
(4) by the Cu-Cr alloy powder that step (1) obtains and the Cu-Al that step (3) obtain2O3Dispersion strengthening copper alloy powder
Isostatic cool pressing obtains billet after end mixes；
(5) ageing treatment is carried out after forming the billet fine copper jacket of step (4).
Preferably, the partial size of the Cu-Al alloy powder and Cu-Cr alloy powder is less than 40 mesh.
Preferably, the oxidant includes Cu2O。
It is further preferred that the oxidant is Cu2O and Al2O3Mixture, Cu in the oxidant2The quality hundred of O
Dividing than content is 99.1~99.98%.
Oxidant the preparation method comprises the following steps:
It is 200 mesh powders that partial size is screened out from the Cu-Al alloy powder of step (1), in air heats powder
To 200~300 DEG C, so that powder surface uniform alumina is formed CuO, then powder is placed in closed container again, under nitrogen atmosphere
850 DEG C of heating 1.5h are up to the oxidant.The first purpose of 850 DEG C of high-temperature heatings is that Al is made to be completely oxidized to Al2O3, purpose it
Second is that CuO is decomposed into the biggish Cu of decomposition pressure2O.Ingredient in oxidant is mainly Cu2O, Cu2The mass percentage content of O
It is 99.1~99.98%, only remaining a small amount of Cu and Al2O3。
Preferably, the mass ratio of Cu-Al alloy powder described in step (2) and oxidant is 1:(0.002~0.06).
Preferably, the temperature of the internal oxidition processing is 800~900 DEG C, and the time of internal oxidition processing is 4~8h.
Preferably, the reduction carries out under an atmosphere of hydrogen, and the temperature of the reduction is 800~900 DEG C, the reduction
Time is 4~8h.
Preferably, the temperature of the timeliness is 400~500 DEG C, and the time of the timeliness is 1~3h.
In step (1), each element proportion in Cu-Al and Cu-Cr should meet wanting for high-performance disperse copper alloy of the present invention
It asks.
Preferably 1200~1230 DEG C of the temperature of Cu-Al alloy melting, preferably 1280~1320 DEG C of the temperature of Cu-Cr melting,
Aerosolization uses high pure nitrogen.
In step (3), the broken partial size of internally oxidized alloy powder is less than 50 mesh.
In step (5), fine copper is wrapped in the progress of argon gas room, first water seal hot extrusion after fine copper jacket, the temperature of water seal hot extrusion
Degree is 900~920 DEG C, and extrusion ratio is greater than 15:1, and then cold drawing or deformation 60~75% of swaging obtains bar, then by bar into
Row timeliness.
Cu-Cr alloy is a kind of typical precipitation strength type alloy, because of its high-intensitive and high conductivity, is drawn in integrated circuit
There is wide prospect of the application in the fields such as wire frame, high-speed rail contact line, high terminal adapter, accurate connector.It can be dissolved under high temperature
Chromium content in the base has 0.8wt%, and solid solubility only 0.03% at room temperature, therefore will be precipitated in ag(e)ing process
Phenomenon, alloy strength, conductivity rapid increase.However binary chromiumcopper Age-prrcipitation Phase thermal stability is poor, precipitated phase is easily
It grows up, to generate overaging, softening temperature is low, strongly limits the alloy in the large-scale use of high-end manufacture field.
It, can be with the shape of copper chromium intermetallic compound simultaneously because the limitation of Cr solid solubility in copper, therefore after Cr content is more than 0.8wt%
Formula occurs, and brittleness is caused to increase, and intensity generally in 600MPa or so, can be such that its intensity further increases by severe deformation, but strong
The increase of degree will lead to elongation significant decrease.If improving its intensity by alloying on the basis of copper chromium alloy,
Conductivity can significantly reduce, and when intensity reaches 800MPa or so, conductivity is below 65%IACS.Therefore, because Al2O3Nanometer is more
It dissipates strengthened copper alloy and Cu-Cr alloy the problems of respectively, therefore can not prepare and meet the defeated change of 3C, IT, AI, super-pressure
Urgently needed for electricity, aerospace and high-speed rail transportation field, conductivity is higher than the copper of 80%IACS, intensity higher than 800MPa and closes
Gold.
Beneficial effects of the present invention
During internal oxidation preparation, if Al fails adequately from Copper substrate with Al2O3The form of particle is abundant
It is precipitated, then the intensity and conductivity of alloy can all be affected, and in the prior art, internal oxidation prepares the Al of the strong copper alloy of disperse
Content is no more than 1.1wt%, and otherwise internal oxidition cannot be carried out sufficiently, corresponding A l2O3Nano dispersion reinforced copper alloy it is most high-strength
Degree is usually no more than 620MPa, conductivity 75%IACS or so.
Cu-Cr alloy is a kind of typical precipitation strength type alloy, has the chromium of 0.8wt% that can be solid-solubilized under high temperature
In matrix, but solid solubility only 0.03% at room temperature, therefore will occur precipitation phenomenon in ag(e)ing process, alloy strength, conductivity are fast
Speed rises.It, can be with copper chromium intermetallic compound after Cr content is more than 0.8wt% due to the limitation of Cr solid solubility in copper
Form occur, brittleness increase, intensity is generally in 600MPa or so, although its intensity can be made to further increase by severe deformation,
But elongation significantly reduces.It can also be by improving its intensity, but conductivity meeting by alloying on the basis of copper chromium alloy
It significantly reduces, therefore the prior art can not be made and meet 3C, IT, AI, ehv power transmission, aerospace and high-speed rail transportation
Conductivity and intensity urgently needed for field are higher than the copper alloy of 800MPa.
In the present invention, nanometer Al is obtained by internal oxidition2O3Particle, by Precipitation nanoscale Cr phase after cold deformation, one
Nanoscale Al not only may be implemented in aspect2O3Particle and the Ao Luowan of Cr phase strengthen；Secondly, already existing nanometer when cold deformation
Grade Al2O3Particle, can hinder the recrystallization of Precipitation nanoscale Cr phase, so that alloy be made also to retain processing hardening and sub- knot
Structure is strengthened；Third, although recrystallization process is suppressed when timeliness, the residual stress formed during cold working is disappeared
It removes, to realize the high-ductility of alloy, conductivity is also significantly improved.High-performance disperse copper alloy provided by the invention,
Conductivity and intensity with higher simultaneously.
Using preparation method provided by the present invention, the optimal conduction of current comprehensive performance can get by the regulation of ingredient
Rate be higher than 80%IACS, intensity higher than 800MPa " double 80 copper alloys " (i.e. simultaneously meet condition conductivity higher than 80%IACS,
Intensity is higher than the copper alloy of 800MPa).
Specific embodiment
The following is specific embodiments of the present invention, and further retouches to technical solution of the present invention work in conjunction with the embodiments
It states, however, the present invention is not limited to these examples.
Embodiment 1
This example provides a kind of proportion of high-performance disperse copper alloy, the component including following mass percent meter:
Al2O30.13%, Cr 0.2%, copper 99.67%.
Embodiment 2
This example provides the proportion of another high-performance disperse copper alloy, the component including following mass percent meter:
Al2O30.6%, Cr0.4%, copper 99%.
Embodiment 3
This example provides the preparation method of high-performance disperse copper alloy, step includes:
(1) aerosolization after Cu-Al, Cu-Cr melting is obtained into Cu-Al alloy powder and Cu-Cr alloy powder respectively；
(2) the Cu-Al alloy powder for obtaining step (1) and oxidant carry out internal oxidition processing after mixing, and obtain interior oxygen
Alloy powder；
(3) it is restored after being crushed the internally oxidized alloy powder that step (2) obtains, obtains Cu-Al2O3Dispersion strengthening copper alloy
Powder；
(4) by the Cu-Cr alloy powder that step (1) obtains and the Cu-Al that step (3) obtain2O3Dispersion strengthening copper alloy powder
Isostatic cool pressing obtains billet after end mixes；
(5) ageing treatment is carried out after forming the billet fine copper jacket of step (4).
Wherein, the partial size of Cu-Al alloy powder and Cu-Cr alloy powder is less than 40 mesh.
In step (2), the ratio of Cu-Al alloy powder and oxidant is 1:(0.002~0.06), oxidant Cu2O。
Oxidant the preparation method comprises the following steps:
It is 200 mesh powders that partial size is screened out from the Cu-Al alloy powder of step (1), in air heats powder
To 200~300 DEG C, so that powder surface uniform alumina is formed CuO, then powder is placed in closed container again, under nitrogen atmosphere
850 DEG C of heating 1.5h are up to the oxidant.The first purpose of 850 DEG C of high-temperature heatings is that Al is made to be completely oxidized to Al2O3, purpose it
Second is that CuO is decomposed into the biggish Cu of decomposition pressure2O.Ingredient in oxidant is mainly Cu2O, Cu2The mass percentage content of O
It is 99.1~99.98%, only remaining a small amount of Cu and Al2O3。
The temperature of internal oxidition processing is 800~900 DEG C, and the time of internal oxidition processing is 4~8h.
Reduction carries out under an atmosphere of hydrogen, and the temperature of reduction is 800~900 DEG C, and the time of reduction is 4~8h.
The temperature of timeliness is 400~500 DEG C, and the time of timeliness is 1~3h.
In step (1), each element proportion in Cu-Al and Cu-Cr should meet wanting for high-performance disperse copper alloy of the present invention
It asks.
Preferably 1200~1230 DEG C of the temperature of Cu-Al alloy melting, preferably 1280~1320 DEG C of the temperature of Cu-Cr melting,
Aerosolization uses high pure nitrogen.
In step (3), the broken partial size of internally oxidized alloy powder is less than 50 mesh.
In step (5), fine copper is wrapped in the progress of argon gas room, first water seal hot extrusion after fine copper jacket, the temperature of water seal hot extrusion
Degree is 900~920 DEG C, and extrusion ratio is greater than 15:1, and then cold drawing or deformation 60~75% of swaging obtains bar, then by bar into
Row timeliness.
Embodiment 4
This example is prepared for high-performance disperse copper alloy A, and concrete condition is as follows:
The Cu-Al alloy that Al content is 0.5wt% is subjected to melting at 1210 DEG C, prepared using high pure nitrogen atomization,
Alloy powder of the partial size less than 40 mesh is screened out, after it is mixed with oxidant, is obtained after 900 DEG C of progress internal oxiditions handle 6h
The broken rear 900 DEG C of hydrogen reducing 6h of powder are obtained Cu-Al by internally oxidized alloy powder2O3Dispersion strengthening copper alloy powder.
Cu-0.7wt%Cr alloy carries out melting at 1300 DEG C, carries out high pure nitrogen atomization preparation Cu-Cr alloy powder.
By above-mentioned 50% Cu-Al2O3Dispersion strengthening copper alloy powder is mixed with 50% Cu-Cr alloy powder, Leng Dengjing
Pressure, argon gas room fine copper jacket, 910 DEG C of water seal hot extrusions, extrusion ratio 20:1, cold deformation 65% of swaging, 450 DEG C timeliness 2 hours,
Obtain high-performance disperse copper alloy A.
Embodiment 5
This example is prepared for high-performance disperse copper alloy B, and concrete condition is as follows:
The Cu-Al alloy that Al content is 0.3wt% is subjected to melting at 1210 DEG C, prepared using high pure nitrogen atomization,
Alloy powder of the partial size less than 40 mesh is screened out, after it is mixed with oxidant, is obtained after 900 DEG C of progress internal oxiditions handle 6h
The broken rear 900 DEG C of hydrogen reducing 6h of powder are obtained Cu-Al by internally oxidized alloy powder2O3Dispersion strengthening copper alloy powder.
Cu-0.6wt%Cr alloy carries out melting at 1300 DEG C, carries out high pure nitrogen atomization preparation Cu-Cr alloy powder.
By above-mentioned 50% Cu-Al2O3Dispersion strengthening copper alloy powder is mixed with 50% Cu-Cr alloy powder, Leng Dengjing
Pressure, argon gas room fine copper jacket, 910 DEG C of water seal hot extrusions, extrusion ratio 20:1, cold deformation 70% of swaging；In 450 DEG C of timeliness 2h, obtain
To high-performance disperse copper alloy B.
Embodiment 6
This example is prepared for high-performance disperse copper alloy C, and concrete condition is as follows:
The Cu-Al alloy that Al content is 0.6wt% is subjected to melting at 1210 DEG C, prepared using high pure nitrogen atomization,
Alloy powder of the partial size less than 40 mesh is screened out, after it is mixed with oxidant, is obtained after 900 DEG C of progress internal oxiditions handle 8h
The broken rear 900 DEG C of hydrogen reducing 8h of powder are obtained Cu-Al by internally oxidized alloy powder2O3Dispersion strengthening copper alloy powder.
Cu-0.8wt%Cr alloy carries out melting at 1320 DEG C, carries out high pure nitrogen atomization preparation Cu-Cr alloy powder.
By above-mentioned 50% Cu-Al2O3Alloy powder is mixed with 50% Cu-Cr alloy powder, isostatic cool pressing, argon gas room
Fine copper jacket, 910 DEG C of water seal hot extrusions, extrusion ratio 20:1, cold deformation 60% of swaging；In 450 DEG C of timeliness 2h, high-performance is obtained more
Dissipate copper alloy C.
Detect example
The high-performance disperse Cu alloy material prepared to embodiment 4~6 has carried out performance test, and the results are shown in Table 1.
1 the performance test results of table
Claims (9)
1. high-performance disperse copper alloy, which is characterized in that the component including following mass percent meter:
Al2O30.04~0.9%,
Cr 0.1~1.0%,
Surplus is copper.
2. high-performance disperse copper alloy according to claim 1, which is characterized in that the group including following mass percent meter
Point:
Al2O30.13~0.6%,
Cr 0.2~0.4%,
Surplus is copper.
3. according to claim 1 or the preparation method of any one of 2 high-performance disperse copper alloys, which is characterized in that step packet
It includes:
(1) aerosolization after Cu-Al, Cu-Cr melting is obtained into Cu-Al alloy powder and Cu-Cr alloy powder respectively；
(2) the Cu-Al alloy powder for obtaining step (1) and oxidant carry out internal oxidition processing after mixing, and obtain internal oxidition conjunction
Bronze end；
(3) it is restored after being crushed the internally oxidized alloy powder that step (2) obtains, obtains Cu-Al2O3Dispersion strengthening copper alloy powder；
(4) by the Cu-Cr alloy powder that step (1) obtains and the Cu-Al that step (3) obtain2O3Dispersion strengthening copper alloy powder is mixed
Isostatic cool pressing obtains billet after even；
(5) ageing treatment is carried out after forming the billet fine copper jacket of step (4).
4. the preparation method of high-performance disperse copper alloy according to claim 3, which is characterized in that the Cu-Al alloyed powder
The partial size of end and Cu-Cr alloy powder is less than 40 mesh.
5. the preparation method of high-performance disperse copper alloy according to claim 3, which is characterized in that the oxidant includes
Cu2O。
6. the preparation method of high-performance disperse copper alloy according to claim 3, which is characterized in that Cu- described in step (2)
The mass ratio of Al alloy powder and oxidant is 1:(0.002~0.06).
7. the preparation method of high-performance disperse copper alloy according to claim 3, which is characterized in that the internal oxidition processing
Temperature is 800~900 DEG C, and the time of internal oxidition processing is 4~8h.
8. the preparation method of high-performance disperse copper alloy according to claim 3, which is characterized in that the reduction is in nitrogen atmosphere
Lower progress is enclosed, the temperature of the reduction is 800~900 DEG C, and the time of the reduction is 4~8h.
9. the preparation method of high-performance disperse copper alloy according to claim 3, which is characterized in that the temperature of the timeliness is
400~500 DEG C, the time of the timeliness is 1~3h.
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| CN112921256A (en) * | 2019-12-05 | 2021-06-08 | 南京理工大学 | Preparation method of copper alloy bar with bamboo joint and hard core gradient structure |
| CN114959342A (en) * | 2022-05-30 | 2022-08-30 | 河南科技大学 | Method for improving processing performance of aluminum oxide dispersion strengthening copper-based composite material |
| CN116043052A (en) * | 2023-01-16 | 2023-05-02 | 中南大学 | Nano dispersion strengthening copper alloy and preparation method and application thereof |
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