CN107557609A - A kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof - Google Patents

A kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof Download PDF

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CN107557609A
CN107557609A CN201710831279.1A CN201710831279A CN107557609A CN 107557609 A CN107557609 A CN 107557609A CN 201710831279 A CN201710831279 A CN 201710831279A CN 107557609 A CN107557609 A CN 107557609A
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copper alloy
strengtherning
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alumina particle
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CN107557609B (en
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李增德
李卿
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GRIMN Engineering Technology Research Institute Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
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Abstract

The invention belongs to powder metallurgy pink collar domain, and in particular to a kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof.Al in the oxidant of the present invention2O3Content is 0.2~2.4wt% (mass percent), γ Al2O3Content:>=95%, γ Al2O3Average grain diameter D is less than 30nm.Alloy is prepared using the Cu Al alloyed powders of water atomization or nitrogen atomization as raw material, synthesized by liquid phase reactor, hydrogen desiccation, compacting, densification, the process such as finishing, obtain the single-phase nano alumina particles dispersion strengthening copper alloy of excellent combination property.The present invention is to combine liquid phase medium oxygen supply and in-situ reactive synthesis phase, a kind of new " adaptivity " the liquid phase original reactive synthesis technique developed.Compared with the existing technology there is the advantages such as production procedure is short, technique is simple, material property is stable, for widening application and development of the material in high-end technology field, preparation technology and its theory significance for improving dispersion strengthening copper alloy are great.

Description

A kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof
Technical field
The invention belongs to copper alloy powder metallurgy pink collar domain, it is related to a kind of single phase nano alumina particle dispersion-strengtherning Copper alloy and preparation method thereof.
Technical background
Dispersion strengthening copper alloy is by fusing point is high, hardness is big, the ceramic particle of good thermal stability and chemical stability is equal Even disperse it is distributed in a kind of Cu alloy material formed in Copper substrate.It is compared to other schedule of reinforcements, dispersion-strengtherning Reinforcing particle do not dissolve and grow up at high temperature, On Dislocation Motion and crystal boundary migration have strong inhibition, show Improve the intensity and high temperature resistance softening properties of material with writing, while the influence that particle scatters to free electron is smaller, Therefore the electrical conductivity of Copper substrate will not substantially be reduced.The application of dispersion strengthening copper alloy is very extensive, is related to electronics, machinery, system Make, nearly all field such as engineer applied, Aero-Space, be particularly applicable to all kinds of resistance welding electrodes, high current welding cable, Large-scale integrated circuit lead frame, platinotron structural material, various heat exchange materials, mold materials, conticaster knot Brilliant device liner and structural wood materials and parts, divertor vertical target timber-used fin, nuclear fusion in the TOKAMAK device of thermonuclear reactor Power electric generator and its cooling tube, the antenna mirror design of ITER applications, rocket chamber and rocket nozzle, all kinds of particles The numerous areas such as accelerator, electromagnetic launch system, pulse magnetic field conductive material, electric automobile, bullet train.
The performance of strengthened dispersion alloy depends on the intrinsic property of selected disperse phase.It is used as in Copper substrate more The species of dephasing has a lot, mainly includes:(1) various oxides:Al2O3、ThO2、BeO、ZrO2、CrO2Deng;(2) various boronations Thing, carbide, nitride, silicide:BN、TiB2, TiC, TaC, WC, TiN, AlN, SiC etc.;(3) intermetallic compound: Fe3Al、Ni3Al etc..The species of reasonable selection disperse phase can play the strengthening effect of disperse phase to greatest extent, therefore selection needs Follow certain principle:Diffusing particle fusing point itself is high, hardness is big, Stability Analysis of Structures under high temperature, does not dissolve;In Copper substrate Solid solubility is small, and diffusion rate is relatively low;Interface binding power between diffusing particle and matrix is stronger;Diffusing particle is in Copper substrate Granule size, distribution, volume content, shape, spacing are suitable.Al2O3And Y2O3The property under tiny and high temperature Deng oxide particle particle diameter Can be stable, Copper substrate can be added into and be allowed to the Dispersed precipitate in matrix, so as to prepare oxide dispersion intensifying copper.Wherein Cu-Al2O3Dispersion strengthening copper alloy is a kind of excellent high-strength, high to lead alloy material.Due to the nanoscale Al of Dispersed precipitate2O3 Particle serves the effect of dispersion-strengtherning to Copper substrate, and therefore, the alloy has high intensity, high rigidity, high conductivity and height soft Change the characteristics such as temperature.There is tissue stabilization, high without phase transformation, yield strength and tensile strength.Normal temperature hardness is high, hardness with The rise fall of temperature is small, and high-temperature creep resistance is good.Heat, conductivity are high.Processing characteristics is excellent, and softening temperature is up to It is 930 DEG C, higher in copper alloy, tungsten copper (1000 DEG C) conductance but is below, heat dispersion is between tungsten copper (220W/m.k) And between fine copper (390W/m-k).Hardness is more than HRB 84, and intensity is high, and fatigue behaviour and anti-wear performance are good.
Al is prepared at present2O3The main method of dispersion strengthening copper alloy has:Internal oxidation, coprecipitation, sol-gel process, Reaction ball milling method, Mixed volatile oil, reactive spray-deposition method etc..Wherein internal oxidation is current heavy industrialization batch production High-performance Al2O3The most important means of dispersion strengthening copper alloy, its specific preparation process are as follows:Cu-Al (0.1~ 1.2wt%) melting → water atomization or nitrogen atomization powder → with oxidant mix → closed container internal oxidition → hydrogen in dry And reduce → jacket processing → compacting (high temperature insostatic pressing (HIP) or hot pressing etc.) → hot extrusion molding → follow-up finishing → product inspection → Product packaging.But patent is not to hardening constituent Al both at home and abroad2O3Phase structure be controlled.Correlative study shows, γ-Al2O3 Compared with α-Al2O3With more excellent performance, its crystal structure is easy to the interface that Copper substrate forms coherence or half coherence, is advantageous to more Distribution is dissipated, and reduces the influence to electron scattering.Not yet find to Al at present2O3The relevant report of particle phase composition.
The content of the invention
The present invention provides a kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof, particular technique Scheme is as follows:
A kind of copper alloy of single phase nano alumina particle dispersion-strengtherning, there is following technical characteristic:
(1) composition:Al2O3:0.2~2.4% (mass percent);
(2) aluminum oxide phase:γ-Al2O3Content:>=95%;
(3) alumina particle:Aluminum oxide average grain diameter D is less than 30nm.
For the copper alloy of single phase nano alumina particle dispersion-strengtherning described above, its specific preparation method, including with Lower step:
(1) raw material prepares:Water atomization or nitrogen atomization produce the Cu-Al alloyed powders of -80 mesh;
(2) liquid phase reactor synthesizes:Cu-Al alloyed powders, oxidant and abrading-ball are closed in ball grinder, pressed on ball mill Take out, be dehydrated after certain technique ball milling;
(3) hydrogen desiccation:Liquid phase reactor synthesis composite powder is dried under hydrogen protective atmosphere;
(4) suppress:The dried composite powder is suppressed on cold isostatic press;
(5) it is densified:The pressed compact is used into vacuum-sintering+hot extrusion technique, hot pressing+hot extrusion technique or high temperature insostatic pressing (HIP) + hot extrusion technique carries out densification;
(6) finish:Pressed compact after the densification is finished, obtains various section bars.
In step (1), the Cu-Al alloys powder raw material is at least one in water atomization or nitrogen atomization Cu-Al alloyed powders Kind, wherein aluminium content is 0.1~1.2wt%, and granularity requirements are -80 mesh.
In step (2), described oxidant is hydrogen peroxide solution or supersaturated ozone solution, by liquid oxidizer and original Material Cu-Al alloyed powders are prepared by a certain percentage.
In step (2), described abrading-ball is fine copper ball, ratio of grinding media to material 4:1~10:1.
In step (2), described ball mill is agitating ball mill or tumbling ball mill.
In step (2), described ball-milling technology is batch (-type) ball-milling technology, and ball milling is shut down 30 minutes after 2~6 hours, with Ensure that caused heat make it that powder temperature is too high in mechanical milling process, causes the alumina particle of produced in situ excessive;Shutting down During add described oxidant, allow reaction in-situ consistent to carry out, the alumina particle high purity of production, size are thin Small and disperse.Ball-grinding machine band water cooling function best results.It is 36~72 hours to accumulate Ball-milling Time.
In step (2), the total oxygen-supplying amount of oxidant in ball grinder is added as Al content in Cu-Al alloyed powders in ball grinder 1.1~1.3 times.
In step (2), the dehydrating process is centrifuge dewatering or compressed air filter-press dehydration.
In step (3), described hydrogen desiccation technique is 600~800 DEG C, soaking time 3~6 hours, and hydrogen flowing quantity is 20L/ minutes, come out of the stove after drying, sieved after broken, obtain the Cu-Al of -80 mesh2O3Composite granule.
In step (4), described isostatic cool pressing technique is 180~240MPa of pressing pressure, 5~30 minutes dwell times, Three-level release.
In step (5), described vacuum-sintering densification is:Vacuum-sintering, 900~950 DEG C of temperature, insulation 2~3 Hour, vacuum≤3 × 10-2Pa;
In step (5), described vacuum hotpressing densification is:Vacuum heating-press sintering, temperature are 850~950 DEG C, are protected Warm 2~3 hours, moulding pressure 40MPa time, pressing time are 30 minutes, vacuum≤3 × 10-2Pa;
In step (5), described high temperature insostatic pressing (HIP) densification is:Alloy green compact are subjected to vacuum canning, it is true in jacket Reciprocal of duty cycle≤3 × 10-2Pa, then inserts in hot isostatic press and is densified, and concrete technology is:Pressure 100MPa, temperature 850~950 DEG C, heat-insulation pressure keeping time 2 h.
In step (5), the ingot blank after described densification is squeezed into the single-phase of 16~20mm of diameter at 920 DEG C and received Rice alumina particle dispersion strengthening copper alloy.
In step (6), by 16~20mm of diameter of hot extrusion bar cold drawing to 11~16mm of diameter.
Beneficial effects of the present invention are as follows:
The preparation method of the present invention, using water atomization or the Cu-Al alloy powder raw materials of nitrogen atomization, passes through the oxidation of liquid phase Single-phase γ-Al are produced in mechanical milling process2O3, with reference to the modern times powder metallurgy densification process obtain it is single-phase nano oxidized Alumina particles dispersion strengthening copper alloy bar, this method can be realized in existing powder metallurgy production line, easily accomplish scale production, And production efficiency is high.
The copper alloy bar of single phase nano alumina particle dispersion-strengtherning in the present invention, height is provided for welding welding industry By force, height is led, high temperature resistance softens, the raw material guarantee of wear-resisting copper alloy so that dispersion strengthening copper alloy combination property has matter Improve, promote the development of Domestic Automotive Industry, electronics industry middle and high end parts.
Brief description of the drawings
Fig. 1:The copper alloy preparation technology flow chart of single phase nano alumina particle dispersion-strengtherning.
Embodiment
The present invention relates to a kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof, specifically include Following steps:1 raw material prepares;2 liquid phase reactors synthesize;3 hydrogen desiccations;4 compactings;5 densifications;6 finishing.
1 it is further illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of copper alloy bar of single phase nano alumina particle dispersion-strengtherning, its preparation technology comprise the following steps:
(1) raw material prepares:The Cu-Al alloyed powders produced using water atomization or nitrogen atomization, screen the powder below 80 mesh End is used as raw material, Al content 0.6wt%, and granular size is -80 mesh;
(2) liquid phase reactor synthesizes:20 kilograms of material powder in step (1) is taken, is placed in agitating ball mill, 40 liters is added and goes The fine copper ball of ionized water and 80 kilograms of diameter 6mm, ball-milling technology are batch (-type) ball-milling technology, and ball milling is shut down 30 minutes after 3 hours, It is 36 hours to accumulate Ball-milling Time.Aluminium content according to adding in Cu-Al alloyed powders calculates H2O2Usage amount, 10 parts of decile And divide 10 times and be intermittently added agitating ball mill in shutdown.Treat to separate abrading-ball with powder using screen cloth after the completion of ball-milling technology, and Powder is dehydrated using centrifuge.
(3) hydrogen desiccation:Composite powder after dehydration is fitted into material boat, inserted in hydrogen furnace, hydrogen desiccation technique is 800 DEG C, 4 hours during insulation, hydrogen flowing quantity is 20L/ minutes, is come out of the stove after material is down to room temperature, is sieved after broken, obtains -80 Purpose Cu-Al2O3Composite granule.
(4) suppress:By the dried Cu-Al2O3Composite granule loads gum cover, binds, and completely cuts off the dirt of pressure medium Dye, then inserts in cold isostatic press and is suppressed, and isostatic cool pressing technique is pressing pressure 200MPa, 8 minutes dwell times, and three After level release, pressed compact is obtained.
(5) it is densified:By the Cu-Al2O3Pressed compact is inserted in vacuum sintering funace, be evacuated to vacuum≤3 × 10-2Pa, electrified regulation, 950 DEG C are warming up to, are incubated 3 hours, then start to pressurize, pressure 40MPa, pressurize 30 minutes, then let out Pressure, cools to room temperature with the furnace, obtains Cu-Al2O3Alloy.Then by Cu-Al at 920 DEG C2O3Alloy extrusion is into diameter 20mm's Extruded barses.
(6) finish:By the finished product bar of the diameter 20mm of hot extrusion bar cold drawing to diameter 16mm.
Single phase nano alumina particle dispersion strengthening copper alloy bar manufactured in the present embodiment, its leading indicator are:Al2O3: 1.3wt%, γ-Al2O3Content:>=96%, γ-Al2O3Average grain diameter D is less than 28nm;Single phase nano alumina particle disperse is strong Change copper alloy main performance:Hardness is more than 80HRB, and conductance is more than 80%IACS, and tensile strength is more than 580MPa.
Embodiment 2
A kind of copper alloy bar of single phase nano alumina particle dispersion-strengtherning, its preparation technology comprise the following steps:
(1) raw material prepares:The Cu-Al alloyed powders produced using water atomization or nitrogen atomization, screen the powder below 80 mesh End is used as raw material, Al content 0.1wt%, and granular size is -80 mesh;
(2) liquid phase reactor synthesizes:20 kilograms of material powder in step (1) is taken, is placed in tumbling ball mill, 50 liters is added and goes The fine copper ball of ionized water and 200 kilograms of diameter 5mm, ball-milling technology are batch (-type) ball-milling technology, and ball milling shuts down 30 points after 6 hours Clock, accumulation Ball-milling Time are 72 hours.Aluminium content according to adding in Cu-Al alloyed powders calculates the use of ozone water solution Amount, 10 parts of decile are simultaneously intermittently added agitating ball mill points for 10 times in shutdown.Treat after the completion of ball-milling technology using screen cloth by abrading-ball with Powder is separated, and powder is dehydrated using centrifuge.
(3) hydrogen desiccation:Composite powder after dehydration is fitted into material boat, inserted in hydrogen furnace, hydrogen desiccation technique is 600 DEG C, 2 hours during insulation, hydrogen flowing quantity is 20L/ minutes, is come out of the stove after material is down to room temperature, is sieved after broken, obtains -80 Purpose Cu-Al2O3Composite granule.
(4) suppress:By the dried Cu-Al2O3Composite granule loads gum cover, binds, and completely cuts off the dirt of pressure medium Dye, then inserts in cold isostatic press and is suppressed, and isostatic cool pressing technique is pressing pressure 180MPa, 20 minutes dwell times, After three-level release, pressed compact is obtained.
(5) it is densified:By the Cu-Al2O3Pressed compact is inserted in vacuum canning, and Vacuum Package, soldering, in vacuum canning Vacuum≤3 × 10-2Pa, the interior vacuum canning for having alloy is then inserted into high temperature insostatic pressing (HIP) stove, vacuumizes, reaches at room temperature Argon gas is filled with after 13.332Pa, pressure is reached 10MPa, is started to warm up, is boosted, to 850 DEG C, pressure 100MPa, heat-insulation pressure keeping 2 Hour, subsequent pressure release, cool to room temperature with the furnace, obtain Cu-Al2O3Alloy.Then by Cu-Al at 920 DEG C2O3Alloy extrusion Into diameter 16mm extruded barses.
(6) finish:By the diameter 16mm of hot extrusion bar cold drawing to diameter 13mm or diameter 11mm finished product rod Material.
The copper alloy bar of single phase nano alumina particle dispersion-strengtherning manufactured in the present embodiment, its leading indicator are: Al2O3:0.24wt%, γ-Al2O3Content:>=97%, γ-Al2O3Average grain diameter D is less than 20nm;Single phase nano alumina particle Dispersion strengthening copper alloy main performance:Hardness is more than 65HRB, and conductance is more than 90%IACS, and tensile strength is more than 476MPa.

Claims (10)

1. a kind of copper alloy of single phase nano alumina particle dispersion-strengtherning, it is characterised in that mainly including following technical characteristic:
(1) composition:Al2O3:0.2~2.4% (percentage by weight);
(2) aluminum oxide phase:γ-Al2O3Content:>=95%;
(3) alumina particle:Aluminum oxide average grain diameter D is less than 30nm.
2. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 1, its It is characterised by, comprises the following steps:
(1) raw material prepares:- 80 mesh Cu-Al alloyed powders that water atomization or nitrogen atomization are produced;
(2) liquid phase reactor synthesizes:Cu-Al alloyed powders, oxidant and abrading-ball are closed in ball grinder, by certain on ball mill Take out, be dehydrated after technique ball milling;
(3) hydrogen desiccation:Liquid phase reactor synthesis composite powder is dried under protective atmosphere;
(4) suppress:The dried composite powder is suppressed on cold isostatic press;
(5) it is densified:The pressed compact is used into vacuum-sintering+hot extrusion technique, hot pressing+hot extrusion technique or high temperature insostatic pressing (HIP)+heat Extrusion process carries out densification;
(6) finish:Pressed compact after the densification is finished, obtains various section bars.
3. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, Cu-Al alloys powder raw material described in step (1) is at least one in water atomization or nitrogen atomization Cu-Al alloyed powders Kind, wherein aluminium content is 0.1~1.2wt%, and granularity requirements are -80 mesh.
4. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, the oxidant described in step (2) is hydrogen peroxide solution or supersaturated ozone solution, by liquid oxidizer and original Material Cu-Al alloyed powders are prepared by a certain percentage.
5. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, the abrading-ball described in step (2) is fine copper ball, ratio of grinding media to material 4:1~10:1.
6. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, the ball-milling technology described in step (2) is batch (-type) ball-milling technology, and ball milling is shut down 30 minutes after 2~6 hours, is tired out Product Ball-milling Time is 36~72 hours.
7. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, the total oxygen-supplying amount of oxidant in ball grinder is added in step (2) as Al content in Cu-Al alloyed powders in ball grinder 1.1~1.3 times.
8. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, dehydrating process described in step (2) is centrifuge dewatering or compressed air filter-press dehydration.
9. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, the hydrogen desiccation technique described in step (3) is 600~800 DEG C, soaking time 3~6 hours, and hydrogen flowing quantity is 20L/ minutes, come out of the stove after drying, sieved after broken, obtain the Cu-Al of -80 mesh2O3Composite granule.
10. a kind of preparation method of the copper alloy of single phase nano alumina particle dispersion-strengtherning according to claim 2, its It is characterised by, the high temperature insostatic pressing (HIP) densification described in step (5) is:Alloy green compact are subjected to vacuum canning, it is true in jacket Reciprocal of duty cycle≤3 × 10-2Pa, then inserts in hot isostatic press and is densified, and concrete technology is:Pressure 100MPa, temperature 850~950 DEG C, heat-insulation pressure keeping time 2 h.
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CN110184489A (en) * 2019-06-11 2019-08-30 中山麓科睿材科技有限公司 A kind of preparation process of alumina dispersion-strenghtened copper alloy
CN111850377A (en) * 2020-06-18 2020-10-30 江苏大学 In-situ Al2O3Preparation method of particle reinforced aluminum matrix composite
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CN114703391A (en) * 2022-03-25 2022-07-05 华中科技大学 Nano-oxide dispersion strengthened copper alloy and preparation method thereof
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CN109161824A (en) * 2018-09-28 2019-01-08 河南科技大学 A kind of Al2O3With the preparation method of TiB mixing enhancement copper-base composite material and preparation method thereof, copper alloy raw material powder
CN110184489A (en) * 2019-06-11 2019-08-30 中山麓科睿材科技有限公司 A kind of preparation process of alumina dispersion-strenghtened copper alloy
CN111850377B (en) * 2020-06-18 2022-03-22 江苏大学 In-situ Al2O3Preparation method of particle reinforced aluminum matrix composite
CN111850377A (en) * 2020-06-18 2020-10-30 江苏大学 In-situ Al2O3Preparation method of particle reinforced aluminum matrix composite
CN112322922A (en) * 2020-11-14 2021-02-05 中国兵器科学研究院宁波分院 Powder metallurgy preparation method of dispersion copper-copper laminated composite material
CN112322922B (en) * 2020-11-14 2022-04-22 中国兵器科学研究院宁波分院 Powder metallurgy preparation method of dispersion copper-copper laminated composite material
CN113122747B (en) * 2021-04-22 2021-11-16 合肥工业大学 Cu- (WC-Y) with excellent mechanical property2O3) Method for preparing composite material
CN113122747A (en) * 2021-04-22 2021-07-16 合肥工业大学 Cu- (WC-Y) with excellent mechanical property2O3) Method for preparing composite material
CN114703391A (en) * 2022-03-25 2022-07-05 华中科技大学 Nano-oxide dispersion strengthened copper alloy and preparation method thereof
CN114752808A (en) * 2022-04-19 2022-07-15 有研工程技术研究院有限公司 High-strength high-conductivity copper alloy composite material and preparation method thereof
CN115747553A (en) * 2022-11-10 2023-03-07 合肥工业大学 Method for preparing Cu-based composite material by using deionized water as process control agent and oxidant
CN115747553B (en) * 2022-11-10 2023-12-01 合肥工业大学 Method for preparing Cu-based composite material by using deionized water as process control agent and oxidant
CN115652174A (en) * 2022-11-11 2023-01-31 宁波博威合金材料股份有限公司 Aluminum oxide dispersion strengthened copper alloy and preparation method and application thereof
CN115652174B (en) * 2022-11-11 2024-02-02 宁波博威合金材料股份有限公司 Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof

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