CN109161718A - A kind of heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive and preparation method thereof - Google Patents
A kind of heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive and preparation method thereof Download PDFInfo
- Publication number
- CN109161718A CN109161718A CN201811126085.2A CN201811126085A CN109161718A CN 109161718 A CN109161718 A CN 109161718A CN 201811126085 A CN201811126085 A CN 201811126085A CN 109161718 A CN109161718 A CN 109161718A
- Authority
- CN
- China
- Prior art keywords
- alloy
- temperature
- dispersion strengthening
- copper alloy
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 85
- 238000005728 strengthening Methods 0.000 title claims abstract description 64
- 239000006185 dispersion Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 103
- 239000000956 alloy Substances 0.000 claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 59
- 239000010949 copper Substances 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 91
- 239000007789 gas Substances 0.000 claims description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 44
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 12
- 229910001278 Sr alloy Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000001192 hot extrusion Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910017818 Cu—Mg Inorganic materials 0.000 claims description 5
- 238000013021 overheating Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910000846 In alloy Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229910018138 Al-Y Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- 229910018134 Al-Mg Inorganic materials 0.000 description 6
- 229910018467 Al—Mg Inorganic materials 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- -1 meanwhile Substances 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017824 Cu—Fe—P Inorganic materials 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
-
- 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
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- 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
-
- 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
-
- 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
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F2003/208—Warm or hot extruding
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses heat-resisting dispersion strengthening copper alloys of a kind of high-strength highly-conductive and preparation method thereof, including following component: metal oxide 0.01-10.00wt.%, Mg 0.025-0.075wt.%, Sr 0.01-0.05wt.%, surplus Cu；Wherein, metal oxide Y2O3、Al2O3、V2O3、Cr2O3、Mn2O5, one of ZrO, NbO, SnO, MgO or a variety of.The present invention introduces Mg element in Cu- metal oxide alloy, it was found that equally distributed Mg element can enter the channel inside powder effectively as oxygen element in Copper substrate, thus in the preparation process of copper alloy, by introducing a certain proportion of Mg element in Cu-X alloy, alloy powder internal oxidation can be made more sufficiently more evenly；In internal oxidition treatment process of the invention, revolution atmosphere furnace is sealed using voluntarily automatic push multi-temperature zone and directly prepares dispersion strengthening copper alloy powder, operation is simpler, and the process flow for preparing dispersion strengthening copper alloy powder is greatly shortened；Crystal boundary migration also can promote using high/low temperature circulation technology in technique of the invention, further increase the diffusivity of oxygen.
Description
Technical field
The invention belongs to Nanoalloy field of material technology, and in particular to a kind of heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive
And preparation method thereof.
Background technique
Copper is excellent conductor material, its conductivity is only second to silver in a metal.Traditional fine copper (such as T1, TU1, TP2
Deng) intensity is not high, and heat-resisting ability is poor, it cannot use under high temperature environment.Alloy element is added in fine copper to be mentioned
Its high intensity and anti-annealing softening performance, as solution strengthening Cu-Ce, Cu-Mg, Cu-Sn, Cu-Ag and precipitation strength Cu-Ni-Si,
The alloys such as Cu-Fe-P, Cu-Cr-Zr.But either solid solution strengthened alloy or precipitation strengthening alloy, one side alloying element
Addition makes its conductivity be affected, and on the other hand when temperature is more than 500 DEG C, mechanical properties decrease is quickly.With science and technology
Rapid development, the heat-resistant stability of copper alloy with high strength and high conductivity is proposed in fields such as nuclear energy, space flight and aviation, high energy electron devices
Higher requirement, some materials require it to be up to 800 DEG C using temperature, it is therefore desirable to develop heat-resistance high-strength high-conductivity copper alloy.
Dispersion strengthening copper alloy is a kind of new function copper alloy mutually strengthened by nano-diffusion, and hardening constituent is generally
Ceramic particle, it is immiscible with Copper substrate therefore smaller on the influence of the conductivity of alloy, meanwhile, ceramic particle compares at high temperature
Stablize, the ceramic particle of Nano grade also can effectively pin dislocation, make alloy have stronger annealing softening resistant to high temperatures and anti-height
Warm creep properties.Therefore, dispersion strengthening copper alloy be nuclear power system radiator, it is large-scale integrated circuit lead frame, high-power
The ideal material of asynchronous motor rotor, resistance welding electrode, point vacuum microwave tube, high-thrust rocket etc..
The preparation method of dispersion strengthening copper alloy main still mechanical alloying method and internal oxidation.Mechanical alloying method is
Copper and ceramic particle are subjected to high-energy ball milling and obtain mixed-powder, hot pressing or hot extrusion molding then are carried out to mixed-powder；Such as
In a kind of preparation method for Zirconium oxide dispersion strengthening copper alloy that patent CN 108149044A is announced, by copper powder and zirconium oxide
Powder under nitrogen protection, is prepared for oversaturated Cu-ZrO in ball milling 30-48 hours2Powder；But the alloy of this method preparation produces
Raw ceramic enhancement phase size and distribution are unable to control, and the impurity of ball-grinding machine, pole are readily incorporated in ma process
The performance of material is affected greatly, so it is difficult to use in industrialization.Internal oxidation generally uses Cu2O is oxidant to alloy powder
Middle element is aoxidized, and is then formed by following process.As to disclose a kind of dispersion copper compound by 105132736 A of patent CN
Material and preparation method thereof uses Cu-Al-Y alloy powder and oxidant Cu2O is raw material, the oxygen in mixing, compacting, sintering
The processes such as change, extruding, forging are prepared for Cu-Al2O3-Y2O3Disperse carbon/carbon-copper composite material, conductivity up to 80%IACS, but due to
It is difficult to restore after sintering internal oxidition base molding, therefore residual oxygen is unable to control.For another example 105838911 A of CN is equally used
Oxidant Cu2O carries out internal oxidition, is then prepared for Cu-Al using isostatic cool pressing and cold deformation2O3Disperse carbon/carbon-copper composite material, but by
In no densification and hot extrusion process, conductivity is only 68%IACS.In addition, the process described above, internal oxidation layer
Depth great reduction with the raising of the content of the second phase constituent, keeps dispersion strengthening copper alloy internal oxidition incomplete, preparation
The great decline of dispersion strengthening copper alloy conductivity.
Summary of the invention
It is oxidable completely that the object of the present invention is to provide one kind, and the heat-resisting dispersion-strengthened Cu of high-strength highly-conductive that residual oxygen is controllable
Alloy and preparation method thereof.
This heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive of the present invention, according to mass percent, including following component: metal
Oxide 0.01-10.00wt.%, Mg 0.025-0.075wt.%, Sr 0.01-0.05wt.%, surplus Cu；Wherein, golden
Category oxide is Y2O3、Al2O3、V2O3、Cr2O3、Mn2O5, one of ZrO, NbO, SnO, MgO or a variety of.
Preferably, the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive, according to mass percent, including following component: metal
Oxide 0.04-5.0wt.%, Mg 0.01-0.05wt.%, Sr 0.01-0.02wt.%, surplus Cu.
The preparation method of this heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive of the present invention, comprising the following steps:
(1) prepared by Cu-X-Mg alloy powder: by elemental copper, Cu-X intermediate alloy, Cu-Mg intermediate alloy by the ratio set
Example melts in vacuum melting furnace, and melt is carried out Overheating Treatment after fusing, and after Overheating Treatment, melt is poured into atomising device,
Under conditions of high-purity Ar gas, Cu-X-Mg alloy melt is atomized by Cu-X-Mg alloy powder by atomizer；
(2) it the internal oxidition processing of Cu-X-Mg alloy powder: after the Cu-X-Mg alloy powder sieving in step 1), is placed in
In ceramic vessel, is then sealed in revolution atmosphere furnace in multi-temperature zone and carry out internal oxidition processing, obtain dispersion strengthening copper alloy powder；
(3) removal of residual oxygen: the dispersion strengthening copper alloy powder in step (2) is mixed with Cu-Sr alloy powder in V-type
It is mixed in material machine, obtains mixed-powder；
(4) form: the resulting mixed-powder cold moudling of step (3) and vacuum copper sheet jacket, then hot extrusion molding, obtains
To the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive.
In the step (1), one of X Y, Al, Cr, Zr, V, Mn, Nb, Sn metal or a variety of, X in Cu-X alloy
Mass percent is 5-20%；Mg mass percent is 5-10% in Cu-Mg alloy；The X oxide ultimately generated in alloy is total
Quality and the mass ratio of Mg are (60-120): 1, preferably (80-100): 1；Fusion temperature is 1180 DEG C -1380 DEG C, overheat
Treatment temperature is 1250 DEG C -1450 DEG C；Ar air pressure is 4.0 × 105Pa~6.0 × 105Pa。
In the step (2), after sieving, the partial size of Cu-X-Mg alloy powder should be less than 200 mesh.
In the step (2), internal oxidition processing the following steps are included:
A) under protection of argon gas, revolution Heating Zone Temperature is risen to 300-400 DEG C, Cu-X-Mg alloy powder is pushed to
Heating zone is turned round, argon gas is closed, opens burner hearth revolute function, is 5-20 revs/min in revolving speed, oxygen flow 0.5-1.0L/
Under conditions of min, 0.5-1h is kept the temperature；
B) oxygen is closed, leads to Ar gas shielded, the temperature of internal oxidition heating zone is risen to 800-900 DEG C, by Cu-X-Mg alloy
Powder is pushed into internal oxidition heating zone, keeps the temperature 0.5-1h, and Cu-X-Mg alloy powder is then pushed to revolution heating zone, heat preservation
Then 0.5-1h carries out circulation isothermal holding in internal oxidition heating zone and revolution heating zone, cycle-index is 2-4 times；
C) heating zone 1 is closed, internal oxidition Heating Zone Temperature is down to 700-800 DEG C of reduction temperature, powder is pushed into interior oxygen
Change heating zone, close argon gas, changes atmosphere into hydrogen, gas flow 0.5-1.0L/min, soaking time 1-3h, hydrogen is used in reduction
For High Purity Hydrogen, dew point is -40 DEG C or less；
D) by treated, Cu-X-Mg alloy powder pushes to cooling zone, takes out obtain dispersion-strengthened Cu conjunction after cooling
Bronze end.
In the step (3), the percentage composition of Sr is that the partial size of 5~10%, Cu-Sr alloy should be less than in Cu-Sr alloy
300 mesh；The mass ratio of the X oxide gross mass and Sr that ultimately generate in alloy is (100-200): 1；Mixing speed is 60-
110rpm；Incorporation time is 30-60min.
In the step (4), cold pressing pressure 350-500MPa, pressure maintaining 30-60s, vacuum degree in the copper sheet jacket
It is 10-2Pa hereinafter, it is 900 DEG C -950 DEG C that the hot extrusion, which squeezes temperature, the extrusion ratio of the hot extrusion 10:1-20:1 it
Between.
Beneficial effects of the present invention: 1) present invention introduces Mg element in Cu- metal oxide alloy, we send out for the first time
Equally distributed Mg element can enter the channel inside powder effectively as oxygen element in present Copper substrate, thus in copper alloy
In preparation process, by introducing a certain proportion of Mg element in Cu-X alloy, alloy powder internal oxidation can be made more sufficiently more
Uniformly；2) in internal oxidition treatment process of the invention, revolution atmosphere furnace is sealed using voluntarily automatic push multi-temperature zone and is directly prepared
Dispersion strengthening copper alloy powder avoids traditional internal oxidation and needs to carry out the complicated work such as oxidant preparation, internal oxidition, broken
Skill, operation is simpler, and the process flow for preparing dispersion strengthening copper alloy powder is greatly shortened；And in technique of the invention
Crystal boundary migration also can promote using high/low temperature circulation technology, further increase the diffusivity of oxygen；3) present invention is closed using Cu-Sr
Gold is used as secondary reduction agent, can effectively remove alloy internal residual oxygen；4) present invention process method is simple, can prepare disperse phase and contain
Amount is the dispersion strengthening copper alloy of 0.05wt%~10.0wt%, disperse phase fine uniform inside alloy, the dispersion-strengtherning of acquisition
Copper alloy excellent combination property has high-intensitive, high conductivity and softening resistant to high temperatures compared with oxygen-free copper (such as C10100, TU1)
Ability, σ0.26~17 times higher than oxygen-free copper, conductivity may be applied not only to the electricity of heavy current impact up to 60~98%IACS
Welding resistance electrode is also particularly well suited for the big load high-precision piece such as nuclear power system heat conducting pipe, electrovacuum helix, particle accelerator
Manufacture.
Detailed description of the invention
Fig. 1 is the automatic push multi-temperature zone sealing revolution atmosphere furnace schematic diagram of designed, designed.
The transmission electron microscope photo of the copper alloy prepared in Fig. 2 embodiment 4.
Specific embodiment
Embodiment 1
The heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive in the present embodiment, according to mass percent, including following component: Al2O3
2.0wt%, Y2O32.0wt%, Mg 0.05wt%, Sr 0.02wt%, surplus Cu.
According to dispersion strengthening phase content, by oxygen-free copper, Cu-10wt%Al intermediate alloy, Cu-10wt%Y intermediate alloy,
Cu-5wt%Mg intermediate alloy is 578:85:126:8 in mass ratio, is melted in 1200 DEG C of vacuum melting furnaces, after fusing
By melt overheat to 1300 DEG C, atomising device is then poured into, (wherein Ar air pressure is 5.0 × 10 with high-purity Ar gas5Pa) pass through mist
Change device and Cu-Al-Y-Mg alloy melt is atomized into Cu-Al-Y-Mg alloy powder, gained atomized powder directly carries out mechanical picker
Point, obtain Cu-Al-Y-Mg alloy powder of the partial size less than 200 mesh.
Cu-Al-Y-Mg alloy powder is put into ceramic vessel, automatic push multi-temperature zone sealing revolution gas is placed directly within
(structure in multi-temperature zone sealing revolution atmosphere furnace is as shown in Figure 1) carries out internal oxidition processing in atmosphere furnace, and concrete operations are as follows:
A) under protection of argon gas, 1 temperature of heating zone is risen to 350 DEG C, Cu-Al-Y-Mg alloy powder is pushed into heating
Area 1 closes argon gas, opens burner hearth revolute function, 10 revs/min of revolving speed, leads to oxygen, oxygen flow 1.0L/min keeps the temperature 1h.
B) oxygen is closed, leads to Ar gas shielded, 2 temperature of heating zone is risen to 850 DEG C of internal oxidition temperature, Cu-Al-Y-Mg is closed
Bronze end pushes to heating zone 2, keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating zone again
2,0.5h is kept the temperature, then automatic push go back to heating zone 1, keep the temperature 0.5h, push to heating zone 2 again, keep the temperature 0.5h, push again
Heating zone 1 is gone back to, 0.5h is kept the temperature.
C) it is then switched off heating zone 1,2 temperature of heating zone is down to 800 DEG C of reduction temperature, powder is pushed into heating zone 2,
Argon gas is closed, atmosphere is changed into hydrogen (hydrogen is High Purity Hydrogen, and dew point is -40 DEG C or less), gas flow 1.0L/min, when heat preservation
Between 3h.
D) the Cu-Al-Y-Mg alloy powder after reduction treatment is pushed into cooling zone, taken out after cooling, obtain disperse
Strengthened copper alloy powder.
According to mass ratio it is 249 by Cu-5wt%Sr alloy powder that dispersion strengthening copper alloy powder and granularity are 300 mesh:
1,30min is uniformly mixed in V-type batch mixer, mixing revolving speed is 100rpm, obtains mixed-powder.
By mixed-powder pressure be 400MPa under cold moudling 60s, then in vacuum degree 10-2Under the conditions of Pa is below,
Copper sheet jacket is carried out, 900 DEG C of temperature is then squeezed, under conditions of extrusion ratio is between 10:1, is hot extruded into bar to get high-strength
High conductivity and heat heat resistance dispersion strengthening copper alloy stick.
Copper alloy bar obtained in the present embodiment is tested for the property, main performance is as follows: yield strength σ0.2=
614MPa, tensile strength sigmab=651MPa, conductivity g=61%IACS.By Copper alloy bar manufactured in the present embodiment through 900 DEG C of hydrogen
Performance is as follows after gas shielded annealing 1h: yield strength σ0.2=595MPa, tensile strength sigmab=637MPa, conductivity g=61.8%
IACS.It can be seen that alloy has excellent high-strength highly-conductive and softening performance resistant to high temperatures.
Comparative example 1
The heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive in this comparative example, according to mass percent, including following component: Al2O3
2.0wt%, Y2O32.0wt%, Sr 0.02wt%, surplus Cu.
According to the dispersion strengthening phase content of design, by oxygen-free copper, Cu-10wt%Al intermediate alloy, among Cu-10wt%Y
Alloy presses 586:85:126, is melted in 1200 DEG C of vacuum melting furnaces, then pours melt overheat to 1300 DEG C after fusing
Enter atomising device, (wherein Ar air pressure is 5.0 × 10 with high-purity Ar gas5Pa) Cu-Al-Y alloy melt is atomized by atomizer
At Cu-Al-Y alloy powder, gained atomized powder directly carries out mechanical grading, obtains Cu-Al-Y alloy of the partial size less than 200 mesh
Powder.
Cu-Al-Y alloy powder is put into ceramic vessel, automatic push multi-temperature zone sealing revolution atmosphere is placed directly within
(structure in multi-temperature zone sealing revolution atmosphere furnace is as shown in Figure 1) carries out internal oxidition processing in furnace, and concrete operations are as follows:
A) under protection of argon gas, 1 temperature of heating zone is risen to 350 DEG C, Cu-Al-Y alloy powder is pushed into heating zone 1,
Argon gas is closed, burner hearth revolute function is opened, 10 revs/min of revolving speed, leads to oxygen, oxygen flow 1.0L/min keeps the temperature 1h.
B) oxygen is closed, leads to Ar gas shielded, 2 temperature of heating zone is risen to 850 DEG C of internal oxidition temperature, by Cu-Al-Y alloy
Powder pushes to heating zone 2, keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating zone 2 again,
0.5h is kept the temperature, then automatic push go back to heating zone 1, keep the temperature 0.5h, push to heating zone 2 again, keep the temperature 0.5h, push back again
Heating zone 1 keeps the temperature 0.5h.
C) it is then switched off heating zone 1,2 temperature of heating zone is down to 800 DEG C of reduction temperature, powder is pushed into heating zone 2,
Argon gas is closed, atmosphere is changed into hydrogen (hydrogen is High Purity Hydrogen, and dew point is -40 DEG C or less), gas flow 1.0L/min, when heat preservation
Between 3 hours.
D) the Cu-Al-Y alloy powder after reduction treatment is pushed into cooling zone, taken out after cooling, obtain dispersion-strengtherning
Copper alloy powder.
According to mass ratio it is 249 by Cu-5wt%Sr alloy powder that dispersion strengthening copper alloy powder and granularity are 300 mesh:
1,30min is uniformly mixed in V-type batch mixer, mixing revolving speed is 100rpm, obtains mixed-powder.It is in pressure by mixed-powder
Cold moudling 60s under 400MPa, then in vacuum degree 10-2Under the conditions of Pa is below, copper sheet jacket is carried out, temperature is then squeezed
900 DEG C, under conditions of extrusion ratio is between 10:1, bar is hot extruded into get the heat-resisting dispersion strengthening copper alloy stick of high-strength highly-conductive.
Copper alloy bar obtained in this comparative example is tested for the property, main performance is as follows: yield strength σ0.2=
574MPa, tensile strength sigmab=599MPa, conductivity g=42.4%IACS；This comparative example Copper alloy bar is protected through 900 DEG C of hydrogen
Performance is as follows after shield annealing 1h: yield strength σ0.2=525MPa, tensile strength sigmab=553MPa, conductivity g=43.8%
IACS。
By being compared with embodiment 1, it is found that other conditions are constant, in the case where lacking Mg, in comparative example 1
Intensity and the equal decrease to some degree of conductivity, this presence for being primarily due to Mg can greatly improve alloy powder internal oxidition journey
Degree greatly improves the electric conductivity and mechanical property of dispersion strengthening copper alloy.
Embodiment 2
The heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive in the present embodiment, according to mass percent, including following component: Al2O3
3.0wt%, Cr2O33.0wt%, Mg 0.075wt%, Sr 0.04wt%, surplus Cu.Contained according to the dispersion strengthening phase of design
Amount, by oxygen-free copper, Cu-10wt%Al intermediate alloy, Cu-10wt%Cr intermediate alloy, Cu-5wt%Mg intermediate alloy press quality
Than being melted in 1180 DEG C of vacuum melting furnaces, by melt overheat to 1250 DEG C after fusing, then for 490:127:164:12
Atomising device is poured into, (wherein Ar air pressure is 6.0 × 10 with high-purity Ar gas5Pa) Cu-Al-Cr-Mg alloy is melted by atomizer
Body is atomized into Cu-Al-Cr-Mg alloy powder, and gained atomized powder directly carries out mechanical grading, obtains partial size less than 200 purposes
Cu-Al-Cr-Mg alloy powder.
Cu-Al-Cr-Mg alloy powder is put into ceramic vessel, the sealing revolution of automatic push multi-temperature zone is placed directly within
(structure in multi-temperature zone sealing revolution atmosphere furnace is as shown in Figure 1) carries out internal oxidition processing in atmosphere furnace, and concrete operations are as follows:
A) under protection of argon gas, 1 temperature of heating zone is risen to 350 DEG C, Cu-Al-Cr-Mg alloy powder is pushed into heating
Area 1 closes argon gas, opens burner hearth revolute function, 10 revs/min of revolving speed, leads to oxygen, oxygen flow 1.0L/min keeps the temperature 1h.
B) oxygen is closed, leads to Ar gas shielded, 2 temperature of heating zone is risen to 850 DEG C of internal oxidition temperature, by Cu-Al-Cr-Mg
Alloy powder pushes to heating zone 2, keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating again
Area 2 keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating zone 2 again, keeps the temperature 0.5h, pushes away again
It sends heating zone 1 back to, keeps the temperature 0.5h.
C) it is then switched off heating zone 1,2 temperature of heating zone is down to 800 DEG C of reduction temperature, powder is pushed into heating zone 2,
Argon gas is closed, atmosphere is changed into hydrogen (hydrogen is High Purity Hydrogen, and dew point is -40 DEG C or less), gas flow 1.0L/min, when heat preservation
Between 2h.
D) the Cu-Al-Cr-Mg alloy powder after reduction treatment is pushed into cooling zone, taken out after cooling, obtain disperse
Strengthened copper alloy powder.
According to mass ratio it is 124 by Cu-5wt%Sr alloy powder that dispersion strengthening copper alloy powder and granularity are 300 mesh:
1,30min is uniformly mixed in V-type batch mixer, mixing revolving speed is 100rpm, obtains mixed-powder.It is in pressure by mixed-powder
Cold moudling 60s under 400MPa, then in vacuum degree 10-2Under the conditions of Pa is below, copper sheet jacket is carried out, temperature is then squeezed
900 DEG C, under conditions of extrusion ratio is between 10:1, bar is hot extruded into get the heat-resisting dispersion strengthening copper alloy stick of high-strength highly-conductive.
To Copper alloy bar obtained in the present embodiment respectively at 900 DEG C, 950 DEG C and 1000 DEG C, under hydrogen atmosphere, burn
1h calculates the expansion rate of copper alloy bar, shown in result table 1.
Comparative example 2
The heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive in this comparative example, according to mass percent, including following component: Al2O3
3.0wt%, Cr2O33.0wt%, Mg 0.075wt%, surplus Cu.
According to the dispersion strengthening phase content of design, by oxygen-free copper, Cu-10wt%Al intermediate alloy, among Cu-10wt%Cr
Alloy, Cu-5wt%Mg intermediate alloy are 497:127:164:12 in mass ratio, are melted in 1180 DEG C of vacuum melting furnaces,
Melt overheat is then poured into atomising device to 1250 DEG C after fusing, (wherein Ar air pressure is 6.0 × 10 with high-purity Ar gas5Pa)
Cu-Al-Cr-Mg alloy melt is atomized into Cu-Al-Cr-Mg alloy powder by atomizer, gained atomized powder directly carries out
Mechanical grading obtains Cu-Al-Cr-Mg alloy powder of the partial size less than 200 mesh.
Cu-Al-Cr-Mg alloy powder is put into ceramic vessel, the sealing revolution of automatic push multi-temperature zone is placed directly within
(structure in multi-temperature zone sealing revolution atmosphere furnace is as shown in Figure 1) carries out internal oxidition processing in atmosphere furnace, and concrete operations are as follows:
A) under protection of argon gas, 1 temperature of heating zone is risen to 350 DEG C, Cu-Al-Cr-Mg alloy powder is pushed into heating
Area 1 closes argon gas, opens burner hearth revolute function, 10 revs/min of revolving speed, leads to oxygen, oxygen flow 1.0L/min keeps the temperature 1h.
B) oxygen is closed, leads to Ar gas shielded, 2 temperature of heating zone is risen to 850 DEG C of internal oxidition temperature, by Cu-Al-Cr-Mg
Alloy powder pushes to heating zone 2, keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating again
Area 2 keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating zone 2 again, keeps the temperature 0.5h, pushes away again
It sends heating zone 1 back to, keeps the temperature 0.5h.
C) it is then switched off heating zone 1,2 temperature of heating zone is down to 800 DEG C of reduction temperature, powder is pushed into heating zone 2,
Argon gas is closed, atmosphere is changed into hydrogen (hydrogen is High Purity Hydrogen, and dew point is -40 DEG C or less), gas flow 1.0L/min, when heat preservation
Between 2h.
D) the Cu-Al-Cr-Mg alloy powder after reduction treatment is pushed into cooling zone, taken out after cooling, obtain disperse
Strengthened copper alloy powder.
By dispersion strengthening copper alloy powder pressure be 400MPa under cold moudling 60s, then in vacuum degree 10-2Pa or less
Under conditions of, copper sheet jacket is carried out, 900 DEG C of temperature is then squeezed, under conditions of extrusion ratio is between 10:1, is hot extruded into stick
Material is to get the heat-resisting dispersion strengthening copper alloy stick of high-strength highly-conductive.
To Copper alloy bar obtained in this comparative example respectively at 900 DEG C, 950 DEG C and 1000 DEG C, under hydrogen atmosphere, burn
1h calculates the expansion rate of copper alloy bar, shown in result table 1.
Dispersion strengthening copper alloy hydrogen annealed expansion performance (unit: mm) prepared by 1 embodiment 2 of table and comparative example 2
As can be known from the results of Table 1, the non-gassing phenomenon of two groups of alloy surfaces of embodiment 2 and comparative example 2, but implement
The hydrogen annealed expansion rate of the resulting dispersion strengthening copper alloy of example 2 is 0.000, and the resulting dispersion strengthening copper alloy of comparative example 2 is then sent out
Apparent size expansion is given birth to, this illustrates that the addition of Sr in this patent further eliminates residual oxygen in alloy, improves alloy
Hydrogen annealed expansion performance.
Embodiment 3
The heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive in the present embodiment, according to mass percent, including following component: Al2O3
1.0wt%, ZrO 1.0wt%, Mg 0.02wt%, Sr 0.02wt%, surplus Cu.
According to the dispersion strengthening phase content of design, by oxygen-free copper, Cu-10wt%Al intermediate alloy, among Cu-10wt%Zr
Alloy, Cu-5wt%Mg intermediate alloy are 854:53:85:4 in mass ratio, are melted in 1300 DEG C of vacuum melting furnaces, are melted
Melt overheat is then poured into atomising device to 1400 DEG C after change, (wherein Ar air pressure is 4.0 × 10 with high-purity Ar gas5Pa) lead to
It crosses atomizer and Cu-Al-Zr-Mg alloy melt is atomized into Cu-Al-Zr-Mg alloy powder, gained atomized powder directly carries out machine
Tool screening, obtains Cu-Al-Zr-Mg alloy powder of the partial size less than 200 mesh.
Cu-Al-Zr-Mg alloy powder is put into ceramic vessel, the sealing revolution of automatic push multi-temperature zone is placed directly within
(structure in multi-temperature zone sealing revolution atmosphere furnace is as shown in Figure 1) carries out internal oxidition processing in atmosphere furnace, and concrete operations are as follows:
A) under protection of argon gas, 1 temperature of heating zone is risen to 350 DEG C, Cu-Al-Zr-Mg alloy powder is pushed into heating
Area 1 closes argon gas, opens burner hearth revolute function, 10 revs/min of revolving speed, leads to oxygen, oxygen flow 1.0L/min keeps the temperature 1h.
B) oxygen is closed, leads to Ar gas shielded, 2 temperature of heating zone is risen to 850 DEG C of internal oxidition temperature, by Cu-Al-Zr-Mg
Alloy powder pushes to heating zone 2, keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating again
Area 2 keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating zone 2 again, keeps the temperature 0.5h, pushes away again
It sends heating zone 1 back to, keeps the temperature 0.5h.
C) it is then switched off heating zone 1,2 temperature of heating zone is down to 800 DEG C of reduction temperature, powder is pushed into heating zone 2,
Argon gas is closed, atmosphere is changed into hydrogen (hydrogen is High Purity Hydrogen, and dew point is -40 DEG C or less), gas flow 1.0L/min, when heat preservation
Between 2h.
D) the Cu-Al-Zr-Mg alloy powder after reduction treatment is pushed into cooling zone, taken out after cooling, obtain disperse
Strengthened copper alloy powder.
According to mass ratio it is 249 by Cu-5wt%Sr alloy powder that dispersion strengthening copper alloy powder and granularity are 300 mesh:
1,30min is uniformly mixed in V-type batch mixer, mixing revolving speed is 100rpm, obtains mixed-powder.It is in pressure by mixed-powder
Cold moudling 60s under 400MPa, then in vacuum degree 10-2Under the conditions of Pa is below, copper sheet jacket is carried out, temperature is then squeezed
900 DEG C, under conditions of extrusion ratio is between 10:1, bar is hot extruded into get the heat-resisting dispersion strengthening copper alloy stick of high-strength highly-conductive.
To the mechanical behavior under high temperature of Copper alloy bar obtained in the present embodiment, its yield strength σ at 700 DEG C is measured0.2=
405MPa, tensile strength sigmab=423MPa.It can be seen that copper alloy made from the present embodiment has excellent high temperature resistance, it can be in height
Temperature is lower to be used.
Embodiment 4
The heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive in the present embodiment, according to mass percent, including following component: Al2O3
2.5wt%, Mg 0.025wt%, Sr 0.02wt%, surplus Cu.
According to the dispersion strengthening phase content of design, among oxygen-free copper, Cu-10wt%Al intermediate alloy, Cu-5wt%Mg
Alloy is 687:106:4 in mass ratio, is melted in 1200 DEG C of vacuum melting furnaces, by melt overheat to 1300 after fusing
DEG C, atomising device is then poured into, (wherein Ar air pressure is 5.0 × 10 with high-purity Ar gas5Pa) Cu-Al-Mg is closed by atomizer
Golden melt atomization directly carries out mechanical grading at Cu-Al-Mg alloy powder, gained atomized powder, obtains partial size less than 200 purposes
Cu-Al-Mg alloy powder.
Cu-Al-Mg alloy powder is put into ceramic vessel, automatic push multi-temperature zone sealing revolution atmosphere is placed directly within
(structure in multi-temperature zone sealing revolution atmosphere furnace is as shown in Figure 1) carries out internal oxidition processing in furnace, and concrete operations are as follows:
A) under protection of argon gas, 1 temperature of heating zone is risen to 350 DEG C, Cu-Al-Mg alloy powder is pushed into heating zone
1, argon gas is closed, burner hearth revolute function is opened, 10 revs/min of revolving speed, leads to oxygen, oxygen flow 1.0L/min keeps the temperature 1h.
B) oxygen is closed, leads to Ar gas shielded, 2 temperature of heating zone is risen to 850 DEG C of internal oxidition temperature, Cu-Al-Y-Mg is closed
Bronze end pushes to heating zone 2, keeps the temperature 0.5h, and then automatic push go back to heating zone 1, keeps the temperature 0.5h, pushes to heating zone again
2,0.5h is kept the temperature, then automatic push go back to heating zone 1, keep the temperature 0.5h, push to heating zone 2 again, keep the temperature 0.5h, push again
Heating zone 1 is gone back to, 0.5h is kept the temperature.
C) it is then switched off heating zone 1,2 temperature of heating zone is down to 800 DEG C of reduction temperature, powder is pushed into heating zone 2,
Argon gas is closed, atmosphere is changed into hydrogen (hydrogen is High Purity Hydrogen, and dew point is -40 DEG C or less), gas flow 1.0L/min, when heat preservation
Between 3h.
D) the Cu-Al-Mg alloy powder after reduction treatment is pushed into cooling zone, taken out after cooling, it is strong to obtain disperse
Change copper alloy powder.
According to mass ratio it is 249 by Cu-5wt%Sr alloy powder that dispersion strengthening copper alloy powder and granularity are 300 mesh:
1,30min is uniformly mixed in V-type batch mixer, mixing revolving speed is 100rpm, obtains mixed-powder.It is in pressure by mixed-powder
Cold moudling 60s under 400MPa, then in vacuum degree 10-2Under the conditions of Pa is below, copper sheet jacket is carried out, temperature is then squeezed
900 DEG C, under conditions of extrusion ratio is between 10:1, bar is hot extruded into get the heat-resisting dispersion strengthening copper alloy stick of high-strength highly-conductive.
TEM test is carried out to Copper alloy bar obtained in the present embodiment, observes the microstructure of Cu alloy material, result
As shown in Fig. 2, we can push away from ingredient figure it is seen that being uniformly distributed the nanoparticle of 5-50nm in copper alloy
It surveys, which should be Al2O3, illustrate that method of the invention during the preparation process can be by nanoscale Al2O3It is evenly dispersed
In copper alloy, have the function that disperse enhances copper alloy.
Claims (9)
1. a kind of heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive, according to mass percent, including following component: metal oxide
0.01-10.00wt.%, Mg 0.025-0.075wt.%, Sr 0.01-0.05wt.%, surplus Cu；Wherein, metal aoxidizes
Object is Y2O3、Al2O3、V2O3、Cr2O3、Mn2O5, one of ZrO, NbO, SnO, MgO or a variety of.
2. the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 1, which is characterized in that high-strength highly-conductive is heat-resisting more
Strengthened copper alloy is dissipated, according to mass percent, including following component: metal oxide 0.04-5.0wt.%, Mg 0.01-
0.05wt.%, Sr 0.01-0.02wt.%, surplus Cu.
3. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 1, comprising the following steps:
(1) prepared by Cu-X-Mg alloy powder: elemental copper, Cu-X intermediate alloy, Cu-Mg intermediate alloy are existed in the ratio of setting
It is melted in vacuum melting furnace, melt is subjected to Overheating Treatment after fusing, after Overheating Treatment, melt is poured into atomising device, in height
Under conditions of pure Ar gas, Cu-X-Mg alloy melt is atomized by Cu-X-Mg alloy powder by atomizer；
(2) after the Cu-X-Mg alloy powder sieving in step 1), ceramics the internal oxidition processing of Cu-X-Mg alloy powder: are placed in
In container, is then sealed in revolution atmosphere furnace in multi-temperature zone and carry out internal oxidition processing, obtain dispersion strengthening copper alloy powder；
(3) removal of residual oxygen: by the dispersion strengthening copper alloy powder in step (2) with Cu-Sr alloy powder in V-type batch mixer
In mixed, obtain mixed-powder；
(4) form: the resulting mixed-powder cold moudling of step (3) and vacuum copper sheet jacket, then hot extrusion molding, obtains height
Strong high conductivity and heat heat resistance dispersion strengthening copper alloy.
4. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 3, which is characterized in that described
In step (1), one of X Y, Al, Cr, Zr, V, Mn, Nb, Sn metal or a variety of, X mass percent is in Cu-X alloy
5-20%；Mg mass percent is 5-10% in Cu-Mg alloy；The matter of the X oxide gross mass and Mg that are ultimately generated in alloy
The ratio between amount is (60-120): 1, fusion temperature is 1180 DEG C -1380 DEG C, and Overheating Treatment temperature is 1250 DEG C -1450 DEG C；Ar air pressure
It is 4.0 × 105Pa~6.0 × 105Pa。
5. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 4, which is characterized in that alloy
In the mass ratio of X oxide gross mass and Mg that ultimately generates be (80-100): 1.
6. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 3, which is characterized in that described
In step (2), after sieving, the partial size of Cu-X-Mg alloy powder should be less than 200 mesh.
7. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 3, which is characterized in that described
In step (2), internal oxidition processing the following steps are included:
A) under protection of argon gas, revolution Heating Zone Temperature is risen to 300-400 DEG C, Cu-X-Mg alloy powder is pushed into revolution
Argon gas is closed in heating zone, opens burner hearth revolute function, is 5-20 revs/min in revolving speed, oxygen flow is 0.5-1.0L/min's
Under the conditions of, keep the temperature 0.5-1h；
B) oxygen is closed, leads to Ar gas shielded, the temperature of internal oxidition heating zone is risen to 800-900 DEG C, by Cu-X-Mg alloy powder
It is pushed into internal oxidition heating zone, keeps the temperature 0.5-1h, Cu-X-Mg alloy powder is then pushed into revolution heating zone, keeps the temperature 0.5-1h,
Then circulation isothermal holding is carried out in internal oxidition heating zone and revolution heating zone, cycle-index is 2-4 times；
C) heating zone 1 is closed, internal oxidition Heating Zone Temperature is down to 700-800 DEG C of reduction temperature, powder is pushed into internal oxidition and is added
Argon gas is closed in hot-zone, changes atmosphere into hydrogen, gas flow 0.5-1.0L/min, soaking time 1-3h, reduction is high with hydrogen
Pure hydrogen, dew point are -40 DEG C or less；
D) by treated, Cu-X-Mg alloy powder pushes to cooling zone, takes out obtain dispersion strengthening copper alloy powder after cooling
End.
8. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 3, which is characterized in that described
In step (3), the percentage composition of Sr is 5-10% in Cu-Sr alloy, and the partial size of Cu-Sr alloy should be less than 300 mesh；In alloy most
Throughout one's life at X oxide gross mass and Sr mass ratio be (100-200): 1；Mixing speed is 60-110rpm；Incorporation time
For 30-60min.
9. the preparation method of the heat-resisting dispersion strengthening copper alloy of high-strength highly-conductive according to claim 3, which is characterized in that described
In step (4), cold pressing pressure 350-500MPa, pressure maintaining 30-60s, vacuum degree is 10 in the copper sheet jacket-2Pa hereinafter,
It is 900 DEG C -950 DEG C that the hot extrusion, which squeezes temperature, and the extrusion ratio of the hot extrusion is between 10:1-20:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811126085.2A CN109161718B (en) | 2018-09-26 | 2018-09-26 | High-strength high-conductivity heat-resistant dispersion-strengthened copper alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811126085.2A CN109161718B (en) | 2018-09-26 | 2018-09-26 | High-strength high-conductivity heat-resistant dispersion-strengthened copper alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109161718A true CN109161718A (en) | 2019-01-08 |
| CN109161718B CN109161718B (en) | 2020-05-19 |
Family
ID=64880323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811126085.2A Active CN109161718B (en) | 2018-09-26 | 2018-09-26 | High-strength high-conductivity heat-resistant dispersion-strengthened copper alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109161718B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH055141A (en) * | 1991-06-26 | 1993-01-14 | Sumitomo Metal Mining Co Ltd | Copper or copper-silver alloy metal oxide composite material and production thereof |
| CN101240387A (en) * | 2007-11-23 | 2008-08-13 | 中南大学 | Cu-Al2O3 nano strengthened dispersion alloy and preparation method thereof |
| CN101956094A (en) * | 2010-10-15 | 2011-01-26 | 哈尔滨工业大学深圳研究生院 | High-strength and high-conductivity dispersion-strengthened alloy and preparation method thereof |
| CN104164587A (en) * | 2014-08-01 | 2014-11-26 | 烟台万隆真空冶金股份有限公司 | Compact dispersion-strengthened copper-base composite material |
-
2018
- 2018-09-26 CN CN201811126085.2A patent/CN109161718B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH055141A (en) * | 1991-06-26 | 1993-01-14 | Sumitomo Metal Mining Co Ltd | Copper or copper-silver alloy metal oxide composite material and production thereof |
| CN101240387A (en) * | 2007-11-23 | 2008-08-13 | 中南大学 | Cu-Al2O3 nano strengthened dispersion alloy and preparation method thereof |
| CN101956094A (en) * | 2010-10-15 | 2011-01-26 | 哈尔滨工业大学深圳研究生院 | High-strength and high-conductivity dispersion-strengthened alloy and preparation method thereof |
| CN104164587A (en) * | 2014-08-01 | 2014-11-26 | 烟台万隆真空冶金股份有限公司 | Compact dispersion-strengthened copper-base composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109161718B (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108103381B (en) | High-strength FeCoNiCrMn high-entropy alloy and preparation method thereof | |
| CN107363262B (en) | Preparation method and application of high-purity compact spherical titanium-zirconium alloy powder | |
| CN109182882B (en) | Preparation method of high-strength oxide dispersion-strengthened Fe-based alloy | |
| CN100436634C (en) | Zero-sintering and hydrogen-expansion nano-diffusion reinforced Cu-Al2O3 alloy and its production | |
| CN110029246B (en) | Preparation method of yttrium oxide dispersion strengthened copper alloy | |
| CN105063403A (en) | Preparation method of copper matrix graphene alloy | |
| CN109207766A (en) | A kind of controllable high aluminium content Cu-Al of tissue2O3Nano-diffusion copper alloy preparation process | |
| CN105087981B (en) | Preparation method for welding-resistant ablation-resistant Cu-nano Al2O3 Cr contact material | |
| CN110129609B (en) | Preparation method of zirconium dioxide dispersion strengthened copper alloy | |
| CN105506329B (en) | Preparation method for Cu-Al2O3 nano dispersion strengthened alloy with high Al2O3 concentration | |
| CN105132772A (en) | Low-cost non-rare-earth type high-strength magnesium alloy and preparing method thereof | |
| CN109778005A (en) | A kind of TiAl alloy and preparation method thereof with excellent deformability | |
| CN101942591A (en) | Method for fast preparing molybdenum-copper alloy | |
| CN108977693B (en) | A kind of recrystallization high-strength titanium alloy and preparation method thereof | |
| CN115044794B (en) | Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof | |
| CN109332717B (en) | Preparation method of spherical molybdenum titanium zirconium alloy powder | |
| CN101942592A (en) | Method for preparing molybdenum copper alloy by activated sintering | |
| CN109207762A (en) | A method of tungsten molybdenum copper composite material is prepared with microwave sintering | |
| CN107502771A (en) | A kind of preparation method of nano-TiC particle reinforced aluminum matrix composites | |
| CN114799155A (en) | Preparation method of ceramic particle reinforced refractory high-entropy alloy | |
| CN113122745B (en) | Preparation method of silver tin oxide composite electric contact material | |
| CN105803283A (en) | Nb-Si-Ti-W-Cr alloy bar and production method thereof | |
| CN113337786A (en) | Nano zirconium oxide/amorphous alloy composite material and preparation method thereof | |
| CN116944518A (en) | Method for forming CuAlFe shape memory alloy structure by ultra-fine SLM (selective laser melting) | |
| Li et al. | Effect of short-time hot repressing on a Ag-SnO2 contact material containing CuO additive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230516 Address after: Room 502, Building 3, Zone A, Jindaoyuan Phase I Industrial Plant, No. 169 Huizhi Middle Road, Yuelu District, Changsha City, Hunan Province, 410006 Patentee after: Hunan Gaochuang Kewei New Materials Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University |
|
| TR01 | Transfer of patent right |