CN107414070A - A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof - Google Patents
A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof Download PDFInfo
- Publication number
- CN107414070A CN107414070A CN201710681073.5A CN201710681073A CN107414070A CN 107414070 A CN107414070 A CN 107414070A CN 201710681073 A CN201710681073 A CN 201710681073A CN 107414070 A CN107414070 A CN 107414070A
- Authority
- CN
- China
- Prior art keywords
- copper
- graphene
- composite powder
- preparation
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention discloses a kind of preparation method of uniform-spherical graphene/monocrystalline copper composite powder.First by commercial copper powder ball milling into copper sheet, and polyvinyl alcohol (PVA) coating decoration is carried out to surface, then adsorption and oxidation graphene obtains graphene oxide/copper composite powder of sheet in water slurry, then the composite powder reduced, remove PVA, assembling and densification, obtain the graphene/copper composite block with laminated construction.It is heat-treated by carrying out fusing point to composite block, finally gives the graphene with uniform-spherical pattern/monocrystalline copper composite powder.The present invention can control graphene content, sphericity and the particle size of final composite powder and Size Distribution by controlling graphene concentration, the size of original copper powder and the copper sheet lamellar spacing of absorption.Graphene prepared by the present invention/monocrystalline copper composite powder good sphericity, size tunable and particle diameter distribution is narrow have certain application prospect in fields such as increasing material manufacturings.
Description
Technical field
The present invention relates to a kind of preparation method of metal-based compound powder, specifically, a kind of uniform-spherical is referred to
Graphene/monocrystalline copper composite powder and preparation method thereof.
Background technology
The control of the preparation of metal dust and pattern is that metal 3D printing, thermal spraying and the metal dust such as metal injection molded add
The basis of work technology, and one of major reason that these technologies further develop is limited at present.Generally, these technologies are to powder
Major requirement be good sphericity and controllable particle size.Literature search to prior art is found, the most frequently used at present
The Method And Principle of manufacture metal dust be mainly based upon liquid-vapor interface, and the surface tension of liquid-liquid interface.Such as document
" Atomization process for metal powder " (atomization production of metal dust) (Materials
Science and Engineering:A383 (1) (2004) 1-6) use centrifugal spraying method and gas atomization be combined system
Standby metal dust and document " Characterisation of metal powders generated by a pressure-
Gas-atomiser " (sign of the metal dust of high pressure gas atomization production) (Materials Science and
Engineering:A 477 (1) (2008) 15-20) use high pressure gas atomization be based on liquid-vapor interface production metal dust
Method.Document " Effect of atomization variables on powder characteristics in the
(atomization variable is to powder property during hydraulic atomized by high-pressured water atomization process "
Influence) (Metal Powder Report 45 (1) (1990) 38-40.) use hydraulic atomized method and document " Hollow
Metallic microspheres produced by spark erosion " (spark erosion prepares hollow metal microballoon)
(Applied Physics Letters 85 (6) (2004) 940-942.) uses spark erosion method of the liquid nitrogen as dielectric fluid
It is the method based on liquid-liquid interface production metal/alloy powder.Up to date, document " Mono-disperse spherical
Cu-Zn powder fabricated via the low wettability of liquid/solid interface " (bases
The spherical ormolu powder being singly distributed is prepared in the low wetability of solid-liquid interface) (Applied Surface Science
357 (2015) 167-171.) just propose a kind of method of the production ormolu powder based on solid-liquid interface.The above
Method, it is usually applicable only to prepare the metal or alloy powder with single fusing point, the preparation of metal-based compound powder is also present
Certain difficulty.
Graphene is with its excellent mechanics, electrically and thermally performance causes extensive concern.At present, had and much ground
Study carefully and demonstrate graphene and can improve the mechanical property of metal material, such as document " Strengthening effect of
Single-atomic-layer graphene in metal-graphene nanolayered composites " are (monatomic
Enhancing effect of the layer graphene in metal-graphite alkene nano composite material) (Nature Communications 4 (2013)
2114) graphene/copper and graphene/nickel composite material strength prepared is up to 1.5GPa and 4.0GPa respectively, it is shown that graphite
The enhancing effect of alkene superelevation.In recent years, the research of lifting of the graphene for materials conductive heat conductivility also achieves certain
It is progressive.Such as document " Thermal properties of graphene-copper-graphene heterogeneous
In films " (hot property of graphene-copper-graphite alkene heterofilm) (Nano Letters 14 (3) (2014) 1497.), room
The heat conductivility of the copper foil of the lower graphene coated of temperature improves 24%;For another example document " Enhanced electrical and
Thermal conduction in graphene-encapsulated copper the nanowires " (copper of graphene coated
The enhancing of conductance and thermal conductivity in line) in (Nano Lett.15 (3) (2015) 2024), the copper cash electrical conductivity and heat of graphene coated
Conductance has sizable lifting.In addition, the nano particle of graphene coated prepared by chemical method is also deposited on lithium ion battery
Scape before application, such as document " Graphene encapsulated Fe3O4nanospindles as a superior anode
(graphene as excellent lithium ion battery anode material wraps up material for lithium-ion batteries "
Fe3O4Nanosphere) (Journal of Nanoscience&Nanotechnology 13 (6) (2013) 4364.).To sum up institute
State, graphene/composite metal powder may be in 3D printing, thermal spraying, metal injection molded, or even including electrocondution slurry, conduction
Have wide practical use in the technologies such as ink.However, at this stage, meet graphene/metal composite powder of use above requirement
Also there is very big challenge for the preparation at end.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, there is provided a kind of uniform-spherical graphene/monocrystalline copper composite powder
The preparation method at end, the present invention is by controlling the graphene oxide for adsorbing various concentrations, copper sheet lamellar spacing and crossing at fusing point heat
Science and engineering skill, the graphene/monocrystalline copper composite powder with different graphene concentration being obtained, it has a good sphericity, size tunable,
The characteristics of particle diameter distribution is narrow.
The present invention is achieved by the following technical solutions:First by commercial copper powder ball milling into copper sheet, and surface is carried out
Polyvinyl alcohol (PVA) coating decoration, then in water slurry adsorption and oxidation graphene obtain sheet graphene oxide/copper it is multiple
Powder is closed, then the composite powder is reduced, removes PVA, assembling and densification, obtains the stone with laminated construction
Black alkene/copper composite block.It is heat-treated by carrying out fusing point to composite block, finally gives the graphite with uniform-spherical pattern
Alkene/monocrystalline copper composite powder.
The preparation method of uniform-spherical graphene/monocrystalline copper composite powder provided by the invention, comprises the following steps:
(1) copper sheet is made in copper powder ball milling, after copper sheet Surface coating polyvinyl alcohol, is put into graphene oxide suspension and mixes
Stirring is closed to without black precipitate, filtering, obtains the sheet composite powder of copper sheet adsorption graphite oxide alkene;
(2) high-temperature process is carried out in hydrogen-argon-mixed atmosphere to the sheet composite powder in step (1) and removes PVA (poly- second
Enol) and redox graphene, then assembled and densification, obtain having graphene/copper of laminated construction compound
Block;The densification is the hot pressed sintering under vacuum or gas shield, discharge plasma sintering, microwave sintering
Middle one kind;
(3) fusing point processing was carried out to graphene/copper composite block of step (2), uniform-spherical is obtained after natural cooling
Graphene/monocrystalline copper composite powder, and there is preferable sphericity, controllable particle diameter and narrower particle diameter distribution.
Preferably, copper powder described in step (1) is any pattern powder, and size is 500 nanometers~300 microns.
Preferably, the thickness of copper sheet described in step (1) is 100 nanometers~10 microns.
Preferably, graphene oxide and the copper sheet volume ratio are 0.01 in the graphene oxide suspension:99.99 arrive
0.1:0.9.
Preferably, the method described in step (1) in copper sheet Surface coating polyvinyl alcohol is molten for the copper sheet is put into PVA
Centrifugation is stirred in liquid, takes precipitation.Wherein, PVA solution concentration is 0.1wt%~3wt%.
Preferably, in step (1), after copper sheet Surface coating polyvinyl alcohol, the copper sheet that polyvinyl alcohol coats first is added
Water slurry is made in water;Place into graphene oxide suspension.
Preferably, in step (1), described graphene oxide suspension concentration is 0.1mg/mL~10mg/mL, the oxygen
The piece footpath size of graphite alkene is 0.1~100 micron, and piece thickness is 0.5~5 nanometer.
Preferably, in step (2), the temperature of the high-temperature process is 300 DEG C~700 DEG C, and soaking time is 30~240 points
Clock.
Preferably, in step (3), the fusing point heat treatment temperature crossed stated is 1080 DEG C~1300 DEG C, soaking time is 10~
60 minutes.
Uniform-spherical graphene/monocrystalline copper composite powder prepared by the above method.
In the present invention, in final composite powder, graphene uniform is coated on single crystal Cu ball surface, and graphene content
Realize controllable adjustment, while final composite powder good sphericity, size tunable and particle diameter distribution is narrow.
The principle of the present invention:
In the methods of the invention, first have to multiple in copper sheet adsorption graphite oxide alkene preparation sheet graphene oxide/copper
Powder is closed, the step principle mainly has at 3 points:(1) the original copper sphere of powder is worn into copper sheet with graphene two-dimensional structure to match;(2)
Copper sheet Surface coating PVA can realize the good combination of Copper substrate and graphene oxide, and PVA can when temperature is more than 200 DEG C
Removed with decomposing;(3) mixed in suspension, uniform suction of the graphene on copper sheet surface can be realized by Electrostatic Absorption
It is attached.Then, composite powder is removed PVA and redox graphene is handled.Compound copper sheet has very big draw ratio, has
Beneficial to layer structure is self-assembly of, the graphene/copper composite block with laminated construction is obtained by densification afterwards.
The dispersed of graphene is the basis for preparing uniform-spherical graphene/monocrystalline copper composite powder in block composite material.
Afterwards, fusing point heat treatment was carried out to composite block, refers to that the temperature in slightly above fine copper fusing point is heat-treated,
Now the copper in composite is melted into liquid, and graphene fusing point is very high, and graphene and copper are not dissolved, at high temperature also not
Chemically react, so being still solid-state.Therefore, liquid copper surrounding is coated by solid graphite alkene, and surface both energy difference
Cause its wetability poor greatly.Wetability is mainly by equilibrium contact angular impulse, and equilibrium contact angle can be represented with young's formula:
Wherein γsIt is the surface energy of solid phase, γlIt is the surface energy of liquid phase, γslIt is the interface energy between solid phase and liquid phase.
The surface energy of liquid copper is up to 1400mJ/m in fusing point2;The surface energy γ of redox graphenesShould be between graphene
Surface energy (46.7mJ/m2) and graphene oxide surface energy (62.1mJ/m2) between, the surface energy (54.8mJ/m with graphite2)
Closely.Therefore, one can consider that the equilibrium contact angle of liquid copper and redox graphene and liquid copper and graphite
Contact angle is suitable, is 140 °.Therefore, liquid copper and graphene wetability are very poor, and contact angle is very high, it is intended to are formed spherical.Separately
On the one hand, in the absence of external forces, liquid has under surface tension effects shrinks its surface area to reduce surface automatically
The trend of energy, and in the solid of given volume, the surface area of spheroid is minimum, and surface energy is minimum, and state is most stable.Therefore work as
When liquid copper touches graphenic surface, have and be punctured into spherical trend so as to form spherical particle.Graphite after powder cooling
Alkene is evenly coated at spherical particle surface, and high-temperature process causes the copper ball of inside to have the structure of monocrystalline;Simultaneously as graphene
Being uniformly distributed in Copper substrate, obtained spherical particle good sphericity, particle diameter distribution are narrow.The particle size of spherical particle is by original
Beginning copper powder size and copper sheet lamellar spacing determine that the particle diameter distribution uniformity is related to the content of graphene.Therefore, we can lead to
Cross this method and obtain graphene/monocrystalline copper composite powder, and make it have preferable sphericity, controllable particle diameter and narrower
Particle diameter distribution.
Compared with prior art, the present invention has advantages below:(1) can prepare at this stage without graphene/monocrystalline
Copper composite powder, graphene can control the graphene content in composite powder while Copper Powder Surface is evenly distributed;(2) make
Standby powder good sphericity, size tunable and particle diameter distribution is narrow;(3) it is any pattern not have requirement to the pattern of original copper powder
Original copper powder may pass through the technology and spherical graphene/copper composite powder be prepared;(4) by the compound of high-temperature process
Powder, compared to both direct mixing, graphene and copper bond strength are high;(5) it is other graphene/composite metal powders
Preparation provides a kind of new approaches.
Brief description of the drawings
The preparation technology flow chart of Fig. 1 uniform-sphericals graphene/monocrystalline copper composite powder.
Fig. 2 0.5vol% graphenes/monocrystalline copper composite powder electronic scanner microscope (SEM) figure.
Fig. 3 1.5vol% graphenes/monocrystalline copper composite powder SEM figures.
Embodiment
Embodiment of the present invention is further described below in conjunction with accompanying drawing:Following examples are using technical solution of the present invention before
Carry and being implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to it is following
Embodiment.
Commercial copper powder described in following examples is the atomization pure copper powder of 325 mesh 99%;Graphene oxide solution used
It is to be obtained by 0.5~5 μm of particle diameter, 1~3nm of thickness graphite oxide ultrasonic disperse, monolithic, piece footpath size is 0.1~100 micro-
Rice, piece thickness are 0.5~5 nanometer;Ball milling copper thickness is 100 nanometers~10 microns;The PVA concentration of cladding be 0.1wt%~
3wt%;Graphene oxide suspension concentration is 0.1mg/mL~10mg/mL;The graphene oxide of absorption is with copper volume ratio
0.01:99.99 to 0.1:0.9.;Under atmosphere of hydrogen high-temperature process remove the temperature of PVA and redox graphene for 300 DEG C~
700℃;Densification is included in hot pressed sintering, discharge plasma sintering, microwave sintering under vacuum or gas shield
Middle one kind;Fusing point heat treatment temperature is crossed as 1080 DEG C~1300 DEG C, soaking time is 10~120 minutes.Finally sample is observed with SEM
Product pattern, and characterize monocrystalline steel structure with EBSD.
Embodiment 1
About 500 nanometers of the piece footpath of graphene oxide in graphene oxide suspension, about 1 nanometer of thickness.
Commercial pure copper powder is worn into copper sheet, about 300 nanometers of thickness by 35 hertz of wet ball grinding 5h first, and put in copper sheet
Enter the PVA solution that concentration is 1wt% and stirring, after copper sheet Surface coating PVA, centrifuging and taking precipitation, aqueous suspension is made in precipitation
Liquid is mixed with the graphene oxide suspension that concentration is 1mg/mL so that graphite oxide in graphene oxide suspension
Alkene is 0.5 with copper volume ratio:99.5, the composite powder of copper sheet adsorption graphite oxide alkene is made, then above-mentioned composite powder
Under 5% hydrogen/argon atmospher, 450 DEG C of insulation 2h processing remove PVA and redox graphene, and to the composite powder after reduction
Hot pressed sintering processing is carried out after the accumulation of end, 930 DEG C, pressure 50MPa of sintering temperature, heat-insulation pressure keeping 20 minutes, is obtained with lamination
The composite block of structure;1100 DEG C of heat treatments are carried out to above-mentioned composite block, obtain spherical graphene/monocrystalline copper composite powder
Pattern result such as Fig. 2, and can be seen that copper particle is monocrystalline by section EBSD.
Embodiment 2
About 500 nanometers of the piece footpath of graphene oxide in graphene oxide suspension, about 1 nanometer of thickness.
Commercial copper powder is worn into copper sheet, about 300 nanometers of thickness by 35 hertz of wet ball grinding 5h first, and is put into copper sheet
PVA solution and stirring of the concentration for 1wt%,
After copper sheet Surface coating PVA, centrifuging and taking precipitation, by the oxidation that water slurry is made in precipitation with concentration is 3mg/mL
Graphene suspension is mixed so that graphene oxide and copper volume ratio are 1.5 in graphene oxide suspension:
98.5, the composite powder of copper sheet adsorption graphite oxide alkene is made, then above-mentioned composite powder under 5% hydrogen/argon atmospher,
450 DEG C of insulation 2h processing remove PVA and redox graphene, and the composite powder accumulation after reduction is carried out at hot pressed sintering
Reason, 930 DEG C, pressure 50MPa of sintering temperature, heat-insulation pressure keeping 20 minutes, obtains the composite block with laminated construction;To above-mentioned multiple
Close block and carry out 1100 DEG C of heat treatments, obtain spherical graphene/monocrystalline copper composite powder pattern result such as Fig. 3, and by cutting
Face EBSD can be seen that copper particle is monocrystalline.
It is above the part preferred embodiment of the present invention, it should be appreciated that the present invention also has other embodiments, than
Such as change the material mixture ratio and parameter value in above-described embodiment, this is it will be apparent to those skilled in the art that be to be easy to reality
Existing.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of preparation method of uniform-spherical graphene/monocrystalline copper composite powder, it is characterised in that comprise the following steps:
(1) copper sheet is made in copper powder ball milling, after copper sheet Surface coating polyvinyl alcohol, is put into graphene oxide suspension mixing and stirs
Mix to without black precipitate, filtering, obtain the sheet composite powder of copper sheet adsorption graphite oxide alkene;
(2) after carrying out high-temperature process in hydrogen-argon-mixed atmosphere to the sheet composite powder in step (1), then accumulated and caused
Densification process, obtain the graphene/copper composite block with laminated construction;The densification is to be protected in vacuum or gas
It is a kind of in hot pressed sintering, discharge plasma sintering, microwave sintering under shield;
(3) fusing point processing was carried out to graphene/copper composite block of step (2), uniform-spherical graphite is obtained after natural cooling
Alkene/monocrystalline copper composite powder.
2. according to the preparation method described in claim l, it is characterised in that:The size of copper powder described in step (1) is 500 nanometers
~300 microns.
3. according to the preparation method described in claim l, it is characterised in that:The thickness of copper sheet described in step (1) is 100 nanometers
~10 microns.
4. according to the preparation method described in claim l, it is characterised in that:In step (1), in the graphene oxide suspension
Graphene oxide is 0.01 with the copper sheet volume ratio:99.99 to 0.1:0.9.
5. according to the preparation method described in claim l, it is characterised in that:In the poly- second of copper sheet Surface coating described in step (1)
The method of enol is to be put into the copper sheet to stir in PVA solution to centrifuge, and takes precipitation;The PVA solution concentration be 0.1wt%~
3wt%.
6. according to the preparation method described in claim l, it is characterised in that:In step (1), in copper sheet Surface coating polyvinyl alcohol
Afterwards, the copper sheet that polyvinyl alcohol coats first is added into water and water slurry is made;Place into graphene oxide suspension.
7. according to the preparation method described in claim l, it is characterised in that:In step (1), described graphene oxide suspension
Concentration is 0.1mg/mL~10mg/mL, and the piece footpath size of the graphene oxide is 0.1~100 micron, and piece thickness is received for 0.5~5
Rice.
8. according to the preparation method described in claim l, it is characterised in that:In step (2), the temperature of the high-temperature process is
300 DEG C~700 DEG C, soaking time is 30~240 minutes.
9. according to the preparation method described in claim l, it is characterised in that:In step (3), described crosses fusing point heat treatment temperature
For 1080 DEG C~1300 DEG C, soaking time is 10~60 minutes.
10. according to uniform-spherical graphene/monocrystalline copper composite powder that in claim 1-9 prepared by any method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710681073.5A CN107414070A (en) | 2017-08-10 | 2017-08-10 | A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710681073.5A CN107414070A (en) | 2017-08-10 | 2017-08-10 | A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107414070A true CN107414070A (en) | 2017-12-01 |
Family
ID=60437795
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710681073.5A Pending CN107414070A (en) | 2017-08-10 | 2017-08-10 | A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107414070A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108515189A (en) * | 2018-04-02 | 2018-09-11 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene carbon/carbon-copper composite material |
CN114054762A (en) * | 2021-11-23 | 2022-02-18 | 上海交通大学 | Graphene/metal matrix composite material preparation method based on graphene defect regulation |
CN114974647A (en) * | 2021-02-18 | 2022-08-30 | 上海新池能源科技有限公司 | Ultrahigh-conductivity wire and cable and preparation method thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048017A1 (en) * | 2002-11-22 | 2004-06-10 | Mitsui Mining & Smelting Co.,Ltd. | Copper flake powder, method for producing copper flake powder, and conductive paste using copper flake powder |
CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
CN103938011A (en) * | 2013-01-17 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Graphene/metal-based composite material with heat conduction anisotropy and electric conduction anisotropy and preparation method thereof |
CN104259469A (en) * | 2014-09-11 | 2015-01-07 | 南京大学 | Manufacturing method of micron and nanometer metal spherical powder |
CN104475745A (en) * | 2014-12-04 | 2015-04-01 | 南京大学 | Spherical brass alloy powder manufacture method |
CN104475742A (en) * | 2014-12-04 | 2015-04-01 | 南京大学 | Manufacturing method of iron-based amorphous soft magnetic alloy spherical powder |
CN104493184A (en) * | 2014-11-27 | 2015-04-08 | 南京大学 | Manufacturing method of spherical bronze alloy powder |
CN104625046A (en) * | 2015-02-06 | 2015-05-20 | 南京大学 | Manufacturing method of micrometer and nanometer composite spherical metal powder of core-shell structure |
CN104711443A (en) * | 2015-03-18 | 2015-06-17 | 上海和伍新材料科技有限公司 | Graphene/copper composite and preparation method thereof |
CN104831100A (en) * | 2015-05-04 | 2015-08-12 | 北京航空航天大学 | Method for preparing graphene reinforced metal-based composite material through discharge plasma (SPS) sintering |
CN105081310A (en) * | 2015-08-31 | 2015-11-25 | 哈尔滨理工大学 | Method for preparing grapheme reinforced aluminum matrix composite material |
-
2017
- 2017-08-10 CN CN201710681073.5A patent/CN107414070A/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004048017A1 (en) * | 2002-11-22 | 2004-06-10 | Mitsui Mining & Smelting Co.,Ltd. | Copper flake powder, method for producing copper flake powder, and conductive paste using copper flake powder |
CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
CN103938011A (en) * | 2013-01-17 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Graphene/metal-based composite material with heat conduction anisotropy and electric conduction anisotropy and preparation method thereof |
CN104259469A (en) * | 2014-09-11 | 2015-01-07 | 南京大学 | Manufacturing method of micron and nanometer metal spherical powder |
CN104493184A (en) * | 2014-11-27 | 2015-04-08 | 南京大学 | Manufacturing method of spherical bronze alloy powder |
CN104475745A (en) * | 2014-12-04 | 2015-04-01 | 南京大学 | Spherical brass alloy powder manufacture method |
CN104475742A (en) * | 2014-12-04 | 2015-04-01 | 南京大学 | Manufacturing method of iron-based amorphous soft magnetic alloy spherical powder |
CN104625046A (en) * | 2015-02-06 | 2015-05-20 | 南京大学 | Manufacturing method of micrometer and nanometer composite spherical metal powder of core-shell structure |
CN104711443A (en) * | 2015-03-18 | 2015-06-17 | 上海和伍新材料科技有限公司 | Graphene/copper composite and preparation method thereof |
CN104831100A (en) * | 2015-05-04 | 2015-08-12 | 北京航空航天大学 | Method for preparing graphene reinforced metal-based composite material through discharge plasma (SPS) sintering |
CN105081310A (en) * | 2015-08-31 | 2015-11-25 | 哈尔滨理工大学 | Method for preparing grapheme reinforced aluminum matrix composite material |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108515189A (en) * | 2018-04-02 | 2018-09-11 | 大同新成新材料股份有限公司 | A kind of preparation method of graphene carbon/carbon-copper composite material |
CN108515189B (en) * | 2018-04-02 | 2021-05-04 | 大同新成新材料股份有限公司 | Preparation method of graphene-copper composite material |
CN114974647A (en) * | 2021-02-18 | 2022-08-30 | 上海新池能源科技有限公司 | Ultrahigh-conductivity wire and cable and preparation method thereof |
CN114054762A (en) * | 2021-11-23 | 2022-02-18 | 上海交通大学 | Graphene/metal matrix composite material preparation method based on graphene defect regulation |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Luo et al. | Surface and interface engineering of silicon‐based anode materials for lithium‐ion batteries | |
CN105624445B (en) | A kind of graphene strengthens the preparation method of Cu-base composites | |
CN104700961B (en) | A kind of graphene/silver composite material and preparation method thereof | |
CN106216705B (en) | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder | |
Mou et al. | Cu-Cu bonding enhancement at low temperature by using carboxylic acid surface-modified Cu nanoparticles | |
CN103752822B (en) | A kind of composite granule and preparation method thereof | |
CN106205935B (en) | A kind of amorphous state soft magnetism composite magnetic powder core and preparation method thereof | |
CN111719087B (en) | Preparation method of medical CuFe alloy powder | |
CN104846231A (en) | Preparation method of copper-based graphene composite blocky material | |
CN107414070A (en) | A kind of uniform-spherical graphene/monocrystalline copper composite powder and preparation method thereof | |
CN104475742A (en) | Manufacturing method of iron-based amorphous soft magnetic alloy spherical powder | |
CN105112694A (en) | Preparation method of magnesium base graphene alloy | |
CN105355881B (en) | A kind of graphene composite material and preparation method thereof | |
CN106711415A (en) | Porous silicon composite negative electrode material and preparation method thereof | |
CN112222419A (en) | Method for preparing nano molybdenum powder by regulating nucleation and growth processes and application | |
CN112222418B (en) | Method for preparing nano tungsten powder by regulating nucleation and growth processes and application | |
Wang et al. | Brief review of nanosilver sintering: manufacturing and reliability | |
Liu et al. | Pressureless sintering bonding using hybrid microscale Cu particle paste on ENIG, pure Cu and pre-oxidized Cu substrate by an oxidation–reduction process | |
CN111687425B (en) | Core-shell structure nano material and preparation method thereof | |
CN107570698A (en) | A kind of graphene coated titanium composite powder material and preparation method thereof | |
Zhang et al. | Advances of synthesis methods for porous silicon-based anode materials | |
CN103252506B (en) | Preparation method of nanometer molybdenum powder containing homodisperse carbon nano tubes | |
Okuno et al. | High cycle stability of nanoporous Si composites in all-solid-state lithium-ion batteries | |
CN105316501A (en) | Rare earth-magnesium-based hydrogen storage alloy and preparation method thereof | |
CN105798319A (en) | Preparation method and device for silver-tungsten electrical contact material as well as electrical contact material and electrical contact |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171201 |
|
RJ01 | Rejection of invention patent application after publication |