CN107217171B - 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

Info

Publication number
CN107217171B
CN107217171B CN201710424067.1A CN201710424067A CN107217171B CN 107217171 B CN107217171 B CN 107217171B CN 201710424067 A CN201710424067 A CN 201710424067A CN 107217171 B CN107217171 B CN 107217171B
Authority
CN
China
Prior art keywords
rare earth
copper
oxide
preparation
liquid
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.)
Active
Application number
CN201710424067.1A
Other languages
Chinese (zh)
Other versions
CN107217171A (en
Inventor
肖翔鹏
田原晨
陈金水
李学帅
许海
朱清涛
郑朋艳
田英明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi University of Science and Technology
CNMC Albetter Albronze Co Ltd
Original Assignee
Jiangxi University of Science and Technology
CNMC Albetter Albronze Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangxi University of Science and Technology, CNMC Albetter Albronze Co Ltd filed Critical Jiangxi University of Science and Technology
Priority to CN201710424067.1A priority Critical patent/CN107217171B/en
Publication of CN107217171A publication Critical patent/CN107217171A/en
Application granted granted Critical
Publication of CN107217171B publication Critical patent/CN107217171B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses rare earth doped oxide Cu-base composites of a kind of liquid liquid and preparation method thereof, which includes 0.5%~4% rare earth oxide, and surplus is copper and inevitable impurity；During liquid liquid doping of the invention, first rare earth nitrades are mixed with part copper liquid liquid, with mixture solution is evaporated crystallization and drying and processing to obtain rare earth ketone acid ammonium crystal powder, it is roasted again, adulterates copper powder, reduction, compacting and sintering, obtains 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 performance are good, and simple process, 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
The present invention relates to Cu-base composites technical fields, copper-based multiple more particularly, to a kind of rare earth doped oxide of liquid liquid Condensation material and preparation method thereof.
Background technique
With the development of modernization, fine copper product is no longer satisfied the use demand of modern development, needs to prepare high property It can copper alloy.Rare earth element is added in copper not only can be improved the recrystallization temperature and room temperature creep-resistant property of copper alloy, and And the crisp transition temperature of modeling for being substantially reduced copper, increase elongation percentage.Since the thermodynamic property of rare earth oxide is quite stable, rare earth Doping copper alloy is not only commonly used for high-temperature structural material, but also 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. being used for microwave tube structure, conduction and spot-wedling electrode material； 4. the high-temperature component of aerospace.
Currently, rare earth oxide Cu-base composites generally use 1. prior powder metallurgy method: by rare earth oxide with it is pure Copper powder is uniformly mixed → compression moulding → sintering, and prior powder metallurgy method cannot realize the refinement of rare earth oxide particle simultaneously With distribution uniformity；2. mechanical alloying method: so that copper powder mixed, become with tiny rare earth oxide particle using high energy ball mill Shape makes powder reach the intimate-association state of atom level, until forming Alloy solid solution, and keeps rare earth oxide particle distribution equal It is even, it then suppresses, be sintered, shape.The crystallite dimension that the shortcomings that the method is is larger；3. composite electroplating: logical It crosses and the particles such as oxide, mineral and resin in plating solution and parent metal or alloy are co-deposited to cathode surface form Composite Coatings Layer.Even suspension is not easy to control in the plating solution for the rare earth oxide particles of the method；4. reactive spray-deposition method: utilizing oxygen-containing nitrogen Gas does atomization gas, and the RE in simultaneous oxidation Cu-RE alloy droplet produces tiny rare earth oxide particle, and then deposition obtains 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 liquid forms rare earth oxide particle with oxygen-containing atmosphere in-situ method under liquidus temperature, and aluminium alloy loses Isothermal solidification occurs after RE, to obtain the rare earth oxide particle of disperse on Copper substrate.
For the Cu alloy material containing particulates reinforcements, particle and basis material are on elasticity modulus and deformability There is a degree of mismatch, therefore inevitably generate local stress/strain at particle in deformation process and concentrate, It is easy the failure for inducing the formation of micro-crack and eventually leading to material.Additional particle size is bigger, deforms between particle and matrix Coordinate more difficult, is more easy to germinating, the extension of micro-crack, so that reduce material prolongs toughness.
The rare earth oxide dispersion strengthening copper alloy middle rare earth particle of ordinary powder metallurgy preparation 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, causes along crystal boundary Cracking.In addition, rare earth oxide particles size is larger, high stress/strain concentration is 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 needs 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, prolongs that toughness is high and processing Rare earth oxide Cu-base composites of good performance need to be current those skilled in the art with the industrial development for adapting at this stage The technical issues of member's urgent need to resolve.
Summary of the invention
The object of the present invention is 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 material is good, consistency is high, intensity is high, excellent electric conductivity, prolongs that toughness is high and processing performance is good.The present invention Another object be to provide the preparation methods of rare earth doped oxide Cu-base composites of above-mentioned liquid liquid a kind of.
To achieve the above object, the technical scheme adopted by the invention is that:
A kind of rare earth doped oxide Cu-base composites of liquid liquid, which is characterized in that the group including following weight percent Point: 0.5%~4% rare earth oxide, surplus are copper and inevitable impurity.
Preferably, the rare earth oxide is lanthana, cerium oxide, yttrium oxide, neodymia or terbium oxide.
A kind of preparation method of the rare earth doped oxide Cu-base composites of above-mentioned liquid liquid, comprising the following steps:
1) rare earth nitrades are soluble in water, it is mixed with part copper solution, adjusting pH value is 8~9, is obtained after mixing evenly The mixture of the colloidal sol of part copper containing rare earth；
2) citric acid is added in the mixture of the colloidal sol of part copper containing rare earth obtained into step 1) and carries out hydrothermal synthesis Reaction, then cools down, then filters, then dry, obtain rare earth part copper powder；
3) rare earth part copper powder obtained in step 2) is roasted, obtains rear-earth-doped oxidation copper；
4) by rear-earth-doped oxidation Copper-cladding Aluminum Bar obtained in step 3) into copper powder, then in flowing, dry hydrogen It is restored, obtains the mixed-powder of metallic copper and rare earth oxide；
5) blank is made through isostatic cool pressing in the mixed-powder of metallic copper obtained in step 4) and rare earth oxide；
6) blank obtained in step 5) is placed in hydrogen shield furnace and is pre-sintered, then frequency induction is burnt in a vacuum It is sintered in freezing of a furnace, obtains the rare earth oxide Cu-base composites of transgranular distribution.
Preferably, in the step 1), the rare earth nitrades are lanthanum nitrate, cerous nitrate, yttrium nitrate, neodymium nitrate or nitric acid Terbium.
Preferably, in the step 2), 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~for 24 hours；The filtering is carried out under alcohol and deionized water；The drying is at 80 DEG C Dry 10h~12h in~200 DEG C of vacuum oven.
Preferably, in the step 3), maturing temperature is 500 DEG C~600 DEG C, and calcining time is 4h~8h.
Preferably, in the step 4), the hydrogen reducing is at a temperature of 700 DEG C~900 DEG C with flowing, dry hydrogen Gas restores 4h~6h.
Preferably, in the step 5), pressure employed in the isostatic cool pressing is 250MPa~300MPa.
Preferably, in the step 6), 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 present invention provides a kind of rare earth doped oxide Cu-base composites of liquid liquid, are made of copper and rare earth oxide, Rare earth oxide is doped and added in copper alloy as particulates reinforcements, has both significantly improved the intensity of alloy, fatigue, wear-resisting and resistance to Corrosion energy, and refinement crystal grain can be played the role of during Composite Sintering, avoid crystal grain from further growing up；The present invention The rare earth doped oxide Cu-base composites of the liquid liquid of offer, other than plain particles reinforcing effect, also have it is good prolong it is tough Property, be in particular in: it is dense to reduce crystal boundary objectionable impurities while fine grain obdurability for the 1. further crystallite dimension of refinement Copper substrate Degree；2. rare earth oxide particles are distributed in transgranular rather than are located at crystal boundary, to reduce grain-boundary crack germinating and Edge crystal crack extension Trend；3. reducing rare earth oxide particles size to nanometer scale, make particle size to nanoscale, is not easily broken particle and boundary Emaciated face is viscous；The wetability 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 performance are good.
The preparation method of the rare earth doped oxide Cu-base composites of liquid liquid provided by the invention, it is mixed by liquid liquor Rare earth nitrades, are mixed with part copper and are adjusted pH value, copper ion, rare earth ion is complexed mutually, formed by conjunction-reduction sintering The mixture of colloidal sol, and be sintered in a reducing atmosphere, composite material is made；During liquid liquid doping of the invention, first will Rare earth nitrades are mixed with part copper liquid liquid, are evaporated crystallization and drying and processing with by mixture solution to obtain Cu-RE Sour ammonium crystal powder, then it is roasted, adulterates copper powder, reduction, compacting and sintering, obtain the rare earth oxide of transgranular distribution Plasticity can be improved in Cu-base composites, 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 are wrapped to form nucleocapsid structure, and the rare earth part copper of subsequent core is also Original is reduced into copper at rare earth oxide, the part copper of outside, and rare earth oxide particles most of in this way are in copper powder intra-die, less Number is distributed on crystal boundary；The preparation method simple process of the rare earth doped oxide Cu-base composites of liquid liquid provided by the invention, Easy to operate, strong applicability.
Detailed description of the invention
Fig. 1 is the micro-organization chart of rare earth oxide Cu-base composites prepared by the present invention.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions only further illustrate feature and advantage of the 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, the component including following weight percent: 0.5% La2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (La2O3) mass percent be 0.5%.
1) rare earth lanthanum nitrate is soluble in water, it is mixed with part copper solution, adjusting pH value is 8, is contained after mixing evenly The mixture of Rare Earth Lanthanum part copper colloidal sol；
2) citric acid is added in the mixture of the colloidal sol of part copper containing Rare Earth Lanthanum obtained into step 1) and carries out hydro-thermal conjunction At reaction, temperature is 150 DEG C, filters in alcohol and deionized water after cooling, dries 10h in 180 DEG C of vacuum ovens, obtain To Rare Earth Lanthanum part copper powder；
3) Rare Earth Lanthanum part copper powder obtained in step 2) is roasted at 560 DEG C 6h, obtains rear earth lanthanum doping oxidation Copper；
4) gained rear earth lanthanum doping in step 3) 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) pole base is made through isostatic cool pressing in metallic copper and lanthana mixed-powder that step 4) obtains, pressure is 280MPa；
6) the pole base that step 5) obtains is placed in hydrogen shield furnace and carries out 800 DEG C, the pre-sintering of 4h, then in vacuum 1000 DEG C are carried out in Medium frequency induction sintering furnace, the sintering of 8h 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 40%, Brinell hardness 120HB, conductivity 90%IACS.
Embodiment 2
A kind of rare earth doped oxide Cu-base composites of liquid liquid, the component including following weight percent: 1.3% Ce2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Ce2O3) mass percent be 1.3%.
1) rare earth cerous nitrate is soluble in water, it is mixed with part copper solution, adjusting pH value is 8.5, is obtained after mixing evenly The mixture of the colloidal sol of part copper containing cerium；
2) citric acid is added in the mixture of the colloidal sol of part copper containing cerium obtained into step 1) and carries out hydro-thermal conjunction At reaction, temperature is 170 DEG C, filters in alcohol and deionized water after cooling, dries 10h in 200 DEG C of vacuum ovens, obtain To cerium part copper powder；
3) cerium part copper powder obtained in step 2) is roasted at 580 DEG C 6h, obtains rare-earth cerium doped oxidation Copper；
4) gained in step 3) 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) pole base is made through isostatic cool pressing in metallic copper and cerium oxide mixed-powder that step 4) obtains, pressure is 300MPa；
6) the pole base that step 5) obtains is placed in hydrogen shield furnace and carries out 820 DEG C, the pre-sintering of 6h, then in vacuum 980 DEG C are carried out in Medium frequency induction sintering furnace, the sintering of 10h 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 38%, Brinell hardness 135HB, conductivity 87%IACS.
Embodiment 3
A kind of rare earth doped oxide Cu-base composites of liquid liquid, the component including following weight percent: 2.5% Y2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Y2O3) mass percent be 2.5%.
1) rare earth yttrium nitrate is soluble in water, it is mixed with part copper solution, adjusting pH value is 8.3, is obtained after mixing evenly The mixture of the colloidal sol of part copper containing rare-earth yttrium；
2) citric acid is added in the mixture of the colloidal sol of part copper containing rare-earth yttrium obtained into step 1) and carries out hydro-thermal conjunction At reaction, temperature is 180 DEG C, filters in alcohol and deionized water after cooling, dries 8h in 200 DEG C of vacuum ovens, obtain To rare-earth yttrium part copper powder；
3) rare-earth yttrium part copper powder obtained in step 2) is roasted at 600 DEG C 6h, obtains rare earth Yt doped oxidation Copper；
4) gained in step 3) 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 yttrium oxide；
5) pole base is made through isostatic cool pressing in metallic copper and yttrium oxide mixed-powder that step 4) obtains, pressure is 260MPa；
6) the pole base that step 5) obtains is placed in hydrogen shield furnace and carries out 840 DEG C, the pre-sintering of 6h, then in vacuum 1000 DEG C are carried out in Medium frequency induction sintering furnace, the sintering of 10h obtains yttrium oxide Cu-base composites.
Sintered product is Cu, Y through XRD material phase analysis2O3, the consistency of the yttrium oxide Cu-base composites of preparation is 99.1%, elongation percentage 36%, Brinell hardness 147HB, conductivity 85%IACS.
Embodiment 4
A kind of rare earth doped oxide Cu-base composites of liquid liquid, the component including following weight percent: 3.1% Nd2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Nd2O3) mass percent be 3.1%.
1) rare earth neodymium nitrate is soluble in water, it is mixed with part copper solution, adjusting pH value is 8.6, is obtained after mixing evenly The mixture of the colloidal sol of part copper containing rare earth neodymium；
2) citric acid is added in the mixture of the colloidal sol of part copper containing rare earth neodymium obtained into step 1) and carries out hydro-thermal conjunction At reaction, temperature is 150 DEG C, filters in alcohol and deionized water after cooling, dries 8h in 190 DEG C of vacuum ovens, obtain To rare earth neodymium part copper powder；
3) rare earth neodymium part copper powder obtained in step 2) is roasted at 570 DEG C 6h, obtains rare earth neodymium doping oxidation Copper；
4) gained rare earth neodymium doping in step 3) 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) pole base is made through isostatic cool pressing in metallic copper and neodymia mixed-powder that step 4) obtains, pressure is 280MPa；
6) the pole base that step 5) obtains is placed in hydrogen shield furnace and carries out 840 DEG C, the pre-sintering of 6h, then in vacuum 990 DEG C are carried out in Medium frequency induction sintering furnace, the sintering of 10h 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 35%, Brinell hardness 153HB, conductivity 84%IACS.
Embodiment 5
A kind of rare earth doped oxide Cu-base composites of liquid liquid, the component including following weight percent: 3.9% Tb2O3, surplus is copper and inevitable impurity.
The present embodiment middle rare earth (Tb2O3) mass percent be 3.9%.
1) rare earth terbium nitrate is soluble in water, it is mixed with part copper solution, adjusting pH value is 8.4, is obtained after mixing evenly The mixture of the part copper colloidal sol of terbium containing rare earth；
2) citric acid is added in the mixture of the part copper colloidal sol of terbium containing rare earth obtained into step 1) and carries out hydro-thermal conjunction At reaction, temperature is 180 DEG C, filters in alcohol and deionized water after cooling, dries 8h in 180 DEG C of vacuum ovens, obtain To rare earth terbium part copper powder；
3) rare earth terbium part copper powder obtained in step 2) is roasted at 580 DEG C 6h, obtains the terbium doped oxidation of rare earth Copper；
4) gained rare earth in step 3) 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) pole base is made through isostatic cool pressing in metallic copper and terbium oxide mixed-powder that step 4) obtains, pressure is 270MPa；
6) the pole base that step 5) obtains is placed in hydrogen shield furnace and carries out 860 DEG C, the pre-sintering of 6h, then true 1000 DEG C are carried out in aerial frequency induction sintering furnace, the sintering of 10h 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 33%, Brinell hardness 164HB, conductivity 82%IACS.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. A variety of modifications for these embodiments are it will be apparent that as 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 the principles and novel features disclosed herein Widest range.

Claims (8)

1. a kind of preparation method of the rare earth doped oxide Cu-base composites of liquid liquid, which comprises the following steps:
1) rare earth nitrades are soluble in water, it is mixed with part copper solution, adjusting pH value is 8~9, is obtained after mixing evenly containing dilute The mixture of native part copper colloidal sol；
2) citric acid is added in the mixture of the colloidal sol of part copper containing rare earth obtained into step 1) and carries out hydrothermal synthesis reaction, Then it cools down, then filters, then dry, obtain rare earth part copper powder；
3) rare earth part copper powder obtained in step 2) is roasted, obtains rear-earth-doped oxidation copper；
4) it by rear-earth-doped oxidation Copper-cladding Aluminum Bar obtained in step 3) into copper powder, is then carried out in flowing, dry hydrogen Reduction, obtains the mixed-powder of metallic copper and rare earth oxide；
5) blank is made through isostatic cool pressing in the mixed-powder of metallic copper obtained in step 4) and rare earth oxide；
6) blank obtained in step 5) is placed in hydrogen shield furnace and is pre-sintered, then frequency induction sintering furnace in a vacuum In be sintered, obtain the rare earth oxide Cu-base composites of transgranular distribution；
The rare earth oxide Cu-base composites include the component of following weight percent: 0.5%~4% rare-earth oxidation Object, surplus are copper and inevitable impurity.
2. preparation method according to claim 1, which is characterized in that in the step 1), the rare earth nitrades are nitre Sour lanthanum, cerous nitrate, yttrium nitrate, neodymium nitrate or terbium nitrate.
3. preparation method according to claim 1, which is characterized in that in the step 2), the hydrothermal synthesis reaction is It carries out in a water bath, bath temperature is 150 DEG C~200 DEG C, and water bath time is 12h~for 24 hours；It is described filtering be alcohol and go from What son carried out under water；The drying is drying 10h~12h in 80 DEG C~200 DEG C of vacuum oven.
4. preparation method according to claim 1, which is characterized in that in the step 3), maturing temperature be 500 DEG C~ 600 DEG C, calcining time is 4h~8h.
5. preparation method according to claim 1, which is characterized in that in the step 4), restored in the hydrogen It is at a temperature of 700 DEG C~900 DEG C with flowing, dry hydrogen reducing 4h~6h.
6. preparation method according to claim 1, which is characterized in that in the step 5), adopted in the isostatic cool pressing Pressure is 250MPa~300MPa.
7. preparation method according to claim 1, which is characterized in that in the step 6), 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。
8. preparation method according to claim 1, which is characterized in that the rare earth oxide is lanthana, cerium oxide, oxygen Change yttrium, neodymia or terbium oxide.
CN201710424067.1A 2017-06-07 2017-06-07 A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof Active CN107217171B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710424067.1A CN107217171B (en) 2017-06-07 2017-06-07 A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710424067.1A CN107217171B (en) 2017-06-07 2017-06-07 A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107217171A CN107217171A (en) 2017-09-29
CN107217171B true CN107217171B (en) 2019-05-24

Family

ID=59948569

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710424067.1A Active CN107217171B (en) 2017-06-07 2017-06-07 A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107217171B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113337747B (en) * 2021-05-31 2023-04-18 合肥工业大学 Preparation method of high-strength and high-conductivity copper alloy
CN113528878B (en) * 2021-07-15 2022-02-11 合肥工业大学 Method for regulating and controlling electrical contact material Cu-Y2O3 alloy by using alloy element Ti
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102703746A (en) * 2012-06-12 2012-10-03 徐梁冰 Method for preparing Y2O3-strengthened copper by acid-base copper etching waste solution
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS597526A (en) * 1982-07-05 1984-01-14 Inoue Japax Res Inc Electrode material used for wire-cut electric discharge machining

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102703746A (en) * 2012-06-12 2012-10-03 徐梁冰 Method for preparing Y2O3-strengthened copper by acid-base copper etching waste solution
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

Also Published As

Publication number Publication date
CN107217171A (en) 2017-09-29

Similar Documents

Publication Publication Date Title
CN104630532B (en) A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material
CN112391556B (en) High-strength high-conductivity Cu-Cr-Nb alloy reinforced by double-peak grain size and double-scale nanophase
CN110331325B (en) Nano-alumina reinforced copper-based composite material and preparation method thereof
CN107217171B (en) A kind of rare earth doped oxide Cu-base composites of liquid liquid and preparation method thereof
EP3726549A1 (en) Rare earth permanent magnet material and preparation method therefor
CN105931784B (en) A kind of corrosion-resistant permanent-magnet material containing cerium mischmetal and preparation method thereof
CN109585113A (en) A kind of preparation method of Sintered NdFeB magnet
CN113789464A (en) Ceramic phase reinforced refractory high-entropy alloy composite material and preparation method thereof
CN110229986B (en) Rare earth tungsten-molybdenum alloy for electrode and preparation method thereof
CN105603247A (en) Graphene reinforced copper-rare earth based electrical contact material and preparing method thereof
CN111206164A (en) Preparation method of high-performance ultra-fine grain molybdenum-lanthanum alloy
CN115044794B (en) Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof
CN107282938B (en) A kind of rear-earth-doped tungsten powder and preparation method thereof
CN102161097A (en) Preparation method of novel fine grained tungsten copper electrode material
CN113337747B (en) Preparation method of high-strength and high-conductivity copper alloy
CN112410597B (en) Preparation method of nano WC dispersion strengthened copper
CN116497293B (en) High-temperature-resistant oxidation-resistant tungsten-lanthanum alloy wire and preparation method thereof
CN112226702A (en) Tungsten oxide alloy material and preparation method thereof
CN115780798A (en) Nano boron carbide/copper composite material and preparation method thereof
CN106810260B (en) Preparation method of tungsten carbide-based non-binding phase hard alloy
CN109047788A (en) A kind of ultrafine yttria Doped Tungsten composite nanometre powder preparation method of cyclic oxidation reduction
CN110983087B (en) Method for improving oxide distribution in yttrium oxide dispersion strengthening tungsten alloy
CN107513636B (en) Liquid liquid adulterates Al2O3- TiC Cu-base composites and preparation method thereof
CN110699566B (en) CaMn7O12Reinforced low-expansion high-thermal-conductivity copper-based composite material and preparation method thereof
CN109355523B (en) Ag/Zn2SnO4Conductive alloy and preparation method thereof

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