CN107217171A - A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof - Google Patents

A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof Download PDF

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CN107217171A
CN107217171A CN201710424067.1A CN201710424067A CN107217171A CN 107217171 A CN107217171 A CN 107217171A CN 201710424067 A CN201710424067 A CN 201710424067A CN 107217171 A CN107217171 A CN 107217171A
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rare earth
copper
oxide
liquid
preparation
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CN107217171B (en
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肖翔鹏
田原晨
陈金水
李学帅
许海
朱清涛
郑朋艳
田英明
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Jiangxi University of Science and Technology
CNMC Albetter Albronze Co Ltd
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Jiangxi University of Science and Technology
CNMC Albetter Albronze Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

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Abstract

The invention discloses rare earth doped oxide Cu-base composites of a kind of liquid liquid and preparation method thereof, the composite includes 0.5%~4% rare earth oxide, and surplus is copper and inevitable impurity；During the liquid liquid doping of the present invention, first rare earth nitrades are mixed with part copper liquid liquid, crystallized with mixture solution is evaporated with drying and processing to obtain rare earth ketone acid ammonium crystal powder, it is calcined again, the copper powder that adulterates, reduction, compacting and sinter, obtain the rare earth oxide copper-based material of transgranular distribution.The present invention can make most of rare earth oxide particles be located at copper powder intra-die, minority is distributed on crystal boundary, so that the wetability of prepared rare earth oxide Cu-base composites is good, consistency is high, intensity is high, excellent electric conductivity, processing characteristics good, and technique is simple, easy to operate, strong applicability.

Description

A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof
Technical field
It is copper-based multiple more particularly, to a kind of rare earth doped oxide of liquid liquid the present invention relates to Cu-base composites technical field Condensation material and preparation method thereof.
Background technology
With the development of modernization, fine copper product can not meet the use demand of modern development, it is necessary to prepare high property Can copper alloy.Rare earth element is added in copper can not only improve the recrystallization temperature and room temperature creep-resistant property of copper alloy, and And the crisp transition temperature of modeling of copper is substantially reduced, increase elongation percentage.Due to the thermodynamic property quite stable of rare earth oxide, rare earth Doping copper alloy is not only commonly used for high-temperature structural material, and is also widely used in functional material, can be applicable to：1. vacuum contact material Material；2. conductive elastomer and circuit lead frame material；3. it is used for microwave tubular construction, conductive and spot-wedling electrode material； 4. the high-temperature component of Aero-Space.
At present, rare earth oxide Cu-base composites are generally using 1. prior powder metallurgy method：By rare earth oxide with it is pure Copper powder is well mixed → compressing → sintering, and prior powder metallurgy method can not realize the refinement of rare earth oxide particle simultaneously With distribution uniformity；2. mechanical alloying method：Copper powder and tiny rare earth oxide mix particles, change are made using high energy ball mill Shape, powder is reached the intimate-association state of atom level, until forming Alloy solid solution, and make the distribution of rare earth oxide particle equal It is even, then suppress, sinter, shape.The shortcoming of the method is that obtained crystallite dimension is larger；3. composite electroplating：It is logical Cross and the particles such as the oxide in plating solution, mineral and resin and parent metal or alloy are co-deposited to cathode surface formation Composite Coatings Layer.Even suspension is difficult to control the rare earth oxide particles of the method in the plating solution；4. reactive spray-deposition method：Utilize oxygen-containing nitrogen Gas is the RE in atomization gas, simultaneous oxidation Cu-RE alloy droplets, produces tiny rare earth oxide particle, and then deposition is obtained The rare earth oxide Cu-base composites of certain volume.Oxygen content control in the method is more difficult；5. liquid phase in-situ reaction：Will Cu-RE alloy liquids form rare earth oxide particle under liquidus temperature with oxygen-containing atmosphere in-situ method, and aluminium alloy loses Isothermal solidification occurs after RE, so as to obtain the rare earth oxide particle of disperse on Copper substrate.
For the Cu alloy material containing particulates reinforcements, particle is with matrix material on modulus of elasticity and deformability There is a certain degree of mismatch, therefore inevitably local stress/strain produced at particle in deformation process and concentrate, Easily induce the formation of micro-crack and ultimately result in the failure of material.Additional particle size is bigger, is deformed between particle and matrix Coordinate more difficult, be more easy to germinating, the extension of micro-crack, so that reduce material prolongs toughness.
Rare earth oxide dispersion strengthening copper alloy middle rare earth particle prepared by ordinary powder metallurgy is predominantly located at crystalline substance In boundary, stress/strain concentrates on grain boundaries in deformation process so that micro-crack often germinates in grain boundaries, triggers along crystal boundary Cracking.In addition, rare earth oxide particles size is larger, high stress/strain, which is concentrated, to be also easy to cause particle/basal body interface unsticking And breakage of particles, further speed up failure process.The rare earth oxide disperse that factors above causes ordinary powder metallurgy to prepare is strong The plasticity for changing copper alloy does not meet the demand of deformation deep processing yet.
Therefore, how to provide that a kind of wetability is good, consistency is high, intensity is high, excellent electric conductivity, toughness of prolonging is high and processing Rare earth oxide Cu-base composites of good performance, are current people in the art with the industrial development needs adapted at this stage The technical problem of member's urgent need to resolve.
The content of the invention
It is an object of the invention to provide a kind of rare earth doped oxide Cu-base composites of liquid liquid, the rare earth oxide is copper-based The wetability of composite is good, consistency is high, intensity is high, excellent electric conductivity, toughness of prolonging is high and processing characteristics is good.The present invention Another object be to provide a kind of preparation method of the rare earth doped oxide Cu-base composites of above-mentioned liquid liquid.
To achieve the above object, the technical solution adopted in the present invention is：
A kind of rare earth doped oxide Cu-base composites of liquid liquid, it is characterised in that include the group of following percetage by weight Point：0.5%~4% rare earth oxide, surplus is copper and inevitable impurity.
It is preferred that, the rare earth oxide is lanthana, cerium oxide, yittrium oxide, neodymia or terbium oxide.
A kind of preparation method of the rare earth doped oxide Cu-base composites of above-mentioned liquid liquid, comprises the following steps：
1) it is rare earth nitrades are soluble in water, mixed with part copper solution, regulation pH value is 8~9, is obtained after stirring The mixture of the colloidal sol of part copper containing rare earth；
2) to step 1) in the obtained colloidal sol of part copper containing rare earth mixture in add citric acid and carry out Hydrothermal Synthesiss Reaction, then cools down, then filters, then dry, obtain rare earth part copper powder；
3) by step 2) in obtained rare earth part copper powder be calcined, obtain rear-earth-doped oxidation copper；
4) by step 3) in obtained rear-earth-doped oxidation Copper-cladding Aluminum Bar into copper powder, then in flowing, the hydrogen dried Reduced, obtain the mixed-powder of metallic copper and rare earth oxide；
5) by step 4) in the mixed-powder of obtained metallic copper and rare earth oxide blank is made through isostatic cool pressing；
6) by step 5) in obtained blank be placed in hydrogen shield stove and carry out pre-sintered, then frequency sensing is burnt in a vacuum It is sintered in freezing of a furnace, obtains the rare earth oxide Cu-base composites of transgranular distribution.
It is preferred that, the step 1) in, the rare earth nitrades are lanthanum nitrate, cerous nitrate, yttrium nitrate, neodymium nitrate or nitric acid Terbium.
It is preferred that, the step 2) in, the hydrothermal synthesis reaction is to carry out in a water bath, bath temperature be 150 DEG C~ 200 DEG C, water bath time is 12h~24h；The filtering is carried out under alcohol and deionized water；The drying is at 80 DEG C 10h~12h is dried in~200 DEG C of vacuum drying chamber.
It is preferred that, the step 3) in, sintering temperature is 500 DEG C~600 DEG C, and roasting time is 4h~8h.
It is preferred that, the step 4) in, the hydrogen reducing is with flowing, the hydrogen dried at a temperature of 700 DEG C~900 DEG C Gas reduces 4h~6h.
It is preferred that, the step 5) in, the pressure employed in the isostatic cool pressing is 250MPa~300MPa.
It is preferred that, the step 6) in, the pre-sintering temperature is 700 DEG C~900 DEG C, and soaking time is 2h~6h；Very Aerial frequency induction sintering temperature is 900 DEG C~1100 DEG C, and soaking time is 8h~10h.
The invention provides a kind of rare earth doped oxide Cu-base composites of liquid liquid, it is made up of copper and rare earth oxide, Rare earth oxide is doped and added in copper alloy as particulates reinforcements, both the significant intensity for improving alloy, fatigue, wear-resisting and resistance to Corrosion energy, and crystal grain thinning can be played during Composite Sintering, it is to avoid the effect that crystal grain is further grown up；The present invention The rare earth doped oxide Cu-base composites of liquid liquid of offer, in addition to plain particles enhancing effect, also prolong tough with good Property, it is in particular in：1. the crystallite dimension of Copper substrate is further refined, crystal boundary objectionable impurities is reduced while fine grain obdurability dense Degree；2. rare earth oxide particles are distributed in transgranular rather than positioned at crystal boundary, are extended with reducing grain-boundary crack germinating and Edge crystal crack Trend；3. reduce rare earth oxide particles size to nanometer scale, make particle size to nanoscale, particle is not easily broken and boundary Emaciated face is glued；The wetabilitys of the rare earth doped oxide Cu-base composites of liquid liquid provided herein is good, consistency is high, intensity Height, excellent electric conductivity, processing characteristics are good.
The preparation method for the rare earth doped oxide Cu-base composites of liquid liquid that the present invention is provided, it is mixed by liquid liquor Conjunction-reduction sintering, rare earth nitrades are mixed with part copper and pH value is adjusted, copper ion, rare earth ion is mutually complexed, are formed The mixture of colloidal sol, and be sintered in reducing atmosphere, composite is made；During the liquid liquid doping of the present invention, first will Rare earth nitrades are mixed with part copper liquid liquid, are crystallized with mixture solution is evaporated with drying and processing to obtain Cu-RE Sour ammonium crystal powder, then it is calcined, the copper powder that adulterates, reduction, compacting and sinter, obtain the rare earth oxide of transgranular distribution Cu-base composites, can improve plasticity, in plastic history, can reduce grain-boundary crack germinating and Edge crystal crack extension becomes Gesture；The preparation method is that being initially formed the rare earth part copper containing rare earth element, and induced by nucleus of rare earth part copper The forming core crystallization of part copper, Cu-RE acid amide by part copper is wrapped to form nucleocapsid structure, and the rare earth part copper of subsequent core is also Original is into rare earth oxide, and the part copper of outside is reduced into copper, and so most of rare earth oxide particles are few in copper powder intra-die Number is distributed on crystal boundary；The preparation method technique of the rare earth doped oxide Cu-base composites of liquid liquid that the present invention is provided is simple, Easy to operate, strong applicability.
Brief description of the drawings
Fig. 1 is the micro-organization chart of the rare earth oxide Cu-base composites prepared by the present invention.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that these descriptions simply further illustrate the feature and advantage of the present invention, rather than to the limit of the claims in the present invention System.
Embodiment 1
A kind of rare earth doped oxide Cu-base composites of liquid liquid, include the component of following percetage by weight：0.5% La2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (La2O3) mass percent be 0.5%.
1) it is rare earth lanthanum nitrate is soluble in water, mixed with part copper solution, regulation pH value is 8, is contained after stirring The mixture of Rare Earth Lanthanum part copper colloidal sol；
2) to step 1) in the obtained colloidal sol of part copper containing Rare Earth Lanthanum mixture in add citric acid and carry out hydro-thermal conjunction Into reaction, temperature is 150 DEG C, is filtered after cooling in alcohol and deionized water, dries 10h in 180 DEG C of vacuum drying chambers, obtain To Rare Earth Lanthanum part copper powder；
3) by step 2) in obtained Rare Earth Lanthanum part copper powder 6h is calcined at 560 DEG C, obtain rear earth lanthanum doping oxidation Copper；
4) by step 3) in gained rear earth lanthanum doping it is cupric oxide doped into copper powder, then in 800 DEG C of stove hydrogen atmospheres Middle reduction, obtains the mixed-powder of metallic copper and lanthana；
5) by step 4) pole base is made through isostatic cool pressing in obtained metallic copper and lanthana mixed-powder, and pressure is 280MPa；
6) by step 5) obtained pole base is placed in hydrogen shield stove and carries out 800 DEG C, 4h pre-sintering, then in vacuum 1000 DEG C are carried out in Medium frequency induction sintering furnace, 8h sintering obtains lanthana Cu-base composites.
Sintered product is Cu, La through XRD material phase analysis2O3, the consistency of the lanthana Cu-base composites of preparation is 99%, elongation percentage is 40%, and Brinell hardness is 120HB, and electrical conductivity is 90%IACS.
Embodiment 2
A kind of rare earth doped oxide Cu-base composites of liquid liquid, include the component of following percetage by weight：1.3% Ce2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Ce2O3) mass percent be 1.3%.
1) it is rare earth cerous nitrate is soluble in water, mixed with part copper solution, regulation pH value is 8.5, is obtained after stirring The mixture of the colloidal sol of part copper containing cerium；
2) to step 1) in the obtained colloidal sol of part copper containing cerium mixture in add citric acid and carry out hydro-thermal conjunction Into reaction, temperature is 170 DEG C, is filtered after cooling in alcohol and deionized water, dries 10h in 200 DEG C of vacuum drying chambers, obtain To cerium part copper powder；
3) by step 2) in obtained cerium part copper powder 6h is calcined at 580 DEG C, obtain rare-earth cerium doped oxidation Copper；
4) by step 3) in gained it is rare-earth cerium doped cupric oxide doped into copper powder, then in 850 DEG C of stove hydrogen atmospheres Middle reduction, obtains the mixed-powder of metallic copper and cerium oxide；
5) by step 4) pole base is made through isostatic cool pressing in obtained metallic copper and cerium oxide mixed-powder, and pressure is 300MPa；
6) by step 5) obtained pole base is placed in hydrogen shield stove and carries out 820 DEG C, 6h pre-sintering, then in vacuum 980 DEG C are carried out in Medium frequency induction sintering furnace, 10h sintering obtains cerium oxide Cu-base composites.
Sintered product is Cu, Ce through XRD material phase analysis2O3, the consistency of the cerium oxide Cu-base composites of preparation is 99.1%, elongation percentage is 38%, and Brinell hardness is 135HB, and electrical conductivity is 87%IACS.
Embodiment 3
A kind of rare earth doped oxide Cu-base composites of liquid liquid, include the component of following percetage by weight：2.5% Y2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Y2O3) mass percent be 2.5%.
1) it is rare earth yttrium nitrate is soluble in water, mixed with part copper solution, regulation pH value is 8.3, is obtained after stirring The mixture of the colloidal sol of part copper containing rare-earth yttrium；
2) to step 1) in the obtained colloidal sol of part copper containing rare-earth yttrium mixture in add citric acid and carry out hydro-thermal conjunction Into reaction, temperature is 180 DEG C, is filtered after cooling in alcohol and deionized water, dries 8h in 200 DEG C of vacuum drying chambers, obtain To rare-earth yttrium part copper powder；
3) by step 2) in obtained rare-earth yttrium part copper powder 6h is calcined at 600 DEG C, obtain rare earth Yt doped oxidation Copper；
4) by step 3) in gained it is rare earth Yt doped cupric oxide doped into copper powder, then in 860 DEG C of stove hydrogen atmospheres Middle reduction, obtains the mixed-powder of metallic copper and yittrium oxide；
5) by step 4) pole base is made through isostatic cool pressing in obtained metallic copper and yittrium oxide mixed-powder, and pressure is 260MPa；
6) by step 5) obtained pole base is placed in hydrogen shield stove and carries out 840 DEG C, 6h pre-sintering, then in vacuum 1000 DEG C are carried out in Medium frequency induction sintering furnace, 10h sintering obtains yittrium oxide Cu-base composites.
Sintered product is Cu, Y through XRD material phase analysis2O3, the consistency of the yittrium oxide Cu-base composites of preparation is 99.1%, elongation percentage is 36%, and Brinell hardness is 147HB, and electrical conductivity is 85%IACS.
Embodiment 4
A kind of rare earth doped oxide Cu-base composites of liquid liquid, include the component of following percetage by weight：3.1% Nd2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Nd2O3) mass percent be 3.1%.
1) it is rare earth neodymium nitrate is soluble in water, mixed with part copper solution, regulation pH value is 8.6, is obtained after stirring The mixture of the colloidal sol of part copper containing rare earth neodymium；
2) to step 1) in the obtained colloidal sol of part copper containing rare earth neodymium mixture in add citric acid and carry out hydro-thermal conjunction Into reaction, temperature is 150 DEG C, is filtered after cooling in alcohol and deionized water, dries 8h in 190 DEG C of vacuum drying chambers, obtain To rare earth neodymium part copper powder；
3) by step 2) in obtained rare earth neodymium part copper powder 6h is calcined at 570 DEG C, obtain rare earth neodymium doping oxidation Copper；
4) by step 3) in gained rare earth neodymium doping it is cupric oxide doped into copper powder, then in 870 DEG C of stove hydrogen atmospheres Middle reduction, obtains the mixed-powder of metallic copper and neodymia；
5) by step 4) pole base is made through isostatic cool pressing in obtained metallic copper and neodymia mixed-powder, and pressure is 280MPa；
6) by step 5) obtained pole base is placed in hydrogen shield stove and carries out 840 DEG C, 6h pre-sintering, then in vacuum 990 DEG C are carried out in Medium frequency induction sintering furnace, 10h sintering obtains neodymia Cu-base composites.
Sintered product is Cu, Nd through XRD material phase analysis2O3, the consistency of the neodymia Cu-base composites of preparation is 98.6%, elongation percentage is 35%, and Brinell hardness is 153HB, and electrical conductivity is 84%IACS.
Embodiment 5
A kind of rare earth doped oxide Cu-base composites of liquid liquid, include the component of following percetage by weight：3.9% Tb2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Tb2O3) mass percent be 3.9%.
1) it is rare earth terbium nitrate is soluble in water, mixed with part copper solution, regulation pH value is 8.4, is obtained after stirring The mixture of the part copper colloidal sol of terbium containing rare earth；
2) to step 1) in the obtained part copper colloidal sol of terbium containing rare earth mixture in add citric acid and carry out hydro-thermal conjunction Into reaction, temperature is 180 DEG C, is filtered after cooling in alcohol and deionized water, dries 8h in 180 DEG C of vacuum drying chambers, obtain To rare earth terbium part copper powder；
3) by step 2) in obtained rare earth terbium part copper powder 6h is calcined at 580 DEG C, obtain the terbium doped oxidation of rare earth Copper；
4) by step 3) in gained rare earth it is terbium doped cupric oxide doped into copper powder, then in 850 DEG C of stove hydrogen atmospheres Middle reduction, obtains the mixed-powder of metallic copper and terbium oxide；
5) by step 4) pole base is made through isostatic cool pressing in obtained metallic copper and terbium oxide mixed-powder, and pressure is 270MPa；
6) by step 5) obtained pole base is placed in hydrogen shield stove and carries out 860 DEG C, 6h pre-sintering, then true 1000 DEG C are carried out in aerial frequency induction sintering furnace, 10h sintering obtains terbium oxide Cu-base composites.
Sintered product is Cu, Tb through XRD material phase analysis2O3, the consistency of the terbium oxide Cu-base composites of preparation is 98.8%, elongation percentage is 33%, and Brinell hardness is 164HB, and electrical conductivity is 82%IACS.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair , under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention. A variety of modifications for these embodiments are it will be apparent that defined herein one for those skilled in the art As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty Widest range.

Claims (9)

1. a kind of rare earth doped oxide Cu-base composites of liquid liquid, it is characterised in that include the component of following percetage by weight： 0.5%~4% rare earth oxide, surplus is copper and inevitable impurity.
2. the rare earth doped oxide Cu-base composites of liquid liquid according to claim 1, it is characterised in that the rare earth oxygen Compound is lanthana, cerium oxide, yittrium oxide, neodymia or terbium oxide.
3. a kind of preparation method of the rare earth doped oxide Cu-base composites of liquid liquid described in claim 1, it is characterised in that Comprise the following steps：
1) it is rare earth nitrades are soluble in water, mixed with part copper solution, regulation pH value is 8~9, is obtained after stirring containing dilute The mixture of native part copper colloidal sol；
2) to step 1) in the obtained colloidal sol of part copper containing rare earth mixture in add citric acid and carry out hydrothermal synthesis reaction, Then cool down, then filter, then dry, obtain rare earth part copper powder；
3) by step 2) in obtained rare earth part copper powder be calcined, obtain rear-earth-doped oxidation copper；
4) by step 3) in obtained rear-earth-doped oxidation Copper-cladding Aluminum Bar into copper powder, then carried out in flowing, the hydrogen dried Reduction, obtains the mixed-powder of metallic copper and rare earth oxide；
5) by step 4) in the mixed-powder of obtained metallic copper and rare earth oxide blank is made through isostatic cool pressing；
6) by step 5) in obtained blank be placed in hydrogen shield stove and carry out pre-sintered, then frequency induction sintering furnace in a vacuum In be sintered, obtain the rare earth oxide Cu-base composites of transgranular distribution.
4. preparation method according to claim 3, it is characterised in that the step 1) in, the rare earth nitrades are nitre Sour lanthanum, cerous nitrate, yttrium nitrate, neodymium nitrate or terbium nitrate.
5. preparation method according to claim 3, it is characterised in that the step 2) in, the hydrothermal synthesis reaction is Carry out in a water bath, bath temperature is 150 DEG C~200 DEG C, water bath time is 12h~24h；It is described filtering be alcohol and go from What son was carried out under water；The drying is that 10h~12h is dried in 80 DEG C~200 DEG C of vacuum drying chamber.
6. preparation method according to claim 3, it is characterised in that the step 3) in, sintering temperature is 500 DEG C~ 600 DEG C, roasting time is 4h~8h.
7. preparation method according to claim 3, it is characterised in that the step 4) in, the hydrogen reducing is 700 DEG C~900 DEG C at a temperature of with flowing, dry hydrogen reducing 4h~6h.
8. preparation method according to claim 3, it is characterised in that the step 5) in, adopted in the isostatic cool pressing Pressure is 250MPa~300MPa.
9. preparation method according to claim 3, it is characterised in that the step 6) in, the pre-sintering temperature is 700 DEG C~900 DEG C, soaking time is 2h~6h；Vacuum intermediate-frequency induction sintering temperature be 900 DEG C~1100 DEG C, soaking time be 8h~ 10h。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113337747A (en) * 2021-05-31 2021-09-03 合肥工业大学 Preparation method of high-strength and high-conductivity copper alloy
CN113528878A (en) * 2021-07-15 2021-10-22 合肥工业大学 Method for regulating and controlling electrical contact material Cu-Y2O3 alloy by using alloy element Ti
CN115852195A (en) * 2022-07-21 2023-03-28 合肥工业大学 Method for preparing Y-La-O phase modified copper alloy material by film pressing

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CN102994798A (en) * 2012-09-25 2013-03-27 南昌大学 Method for preparing rare earth oxide dispersion strengthened copper
CN105220050A (en) * 2015-09-29 2016-01-06 河南科技大学 A kind of doped with rare-earth oxide molybdenum-copper matrix material and preparation method thereof

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CN102703746A (en) * 2012-06-12 2012-10-03 徐梁冰 Method for preparing Y2O3-strengthened copper by acid-base copper etching waste solution
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Publication number Priority date Publication date Assignee Title
CN113337747A (en) * 2021-05-31 2021-09-03 合肥工业大学 Preparation method of high-strength and high-conductivity copper alloy
CN113528878A (en) * 2021-07-15 2021-10-22 合肥工业大学 Method for regulating and controlling electrical contact material Cu-Y2O3 alloy by using alloy element Ti
CN115852195A (en) * 2022-07-21 2023-03-28 合肥工业大学 Method for preparing Y-La-O phase modified copper alloy material by film pressing
CN115852195B (en) * 2022-07-21 2024-01-26 合肥工业大学 Method for preparing Y-La-O phase modified copper alloy material by film pressing

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