CN108264041A - Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material - Google Patents
Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material Download PDFInfo
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Abstract
Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material, belong to field of powder metallurgy.The invention solves the technical issues of due to graphene and the compound difficulty of metallic copper, the tensile strength of composite material is unsatisfactory.Graphene oxide and mantoquita are sufficiently mixed by the method for the present invention first, pass through the parameters such as controlling reaction temperature, pH value, Kocide SD is precipitated on graphene oxide sheet surface, these nanometer rods can not only lodge on graphene oxide sheet surface, form good combination, and help that self assembly occurs between piece and piece, so as to form the composite granule with lamellar structure.It is follow-up to obtain the graphene/Cu-base composites with microcosmic layer structure by reduction and sintering.The method of the present invention raw material is cheap, equipment and operation are simpler, is easy to carry out mass production, composite material has the advantages of intensity is high, conductive, thermal conductivity is good.
Description
Technical field
The invention belongs to field of powder metallurgy；More particularly to graphene oxide/copper oxide composite powder and its preparation side
Method, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material.
Background technology
The satisfactory mechanical property of copper and copper alloy, and processing performance is excellent, is easy to casting, plastic processing etc., it is prior
It is that copper and copper alloy have good anti-corrosion, heat conduction, electric conductivity, so they can be widely used in electric, mechanical system
It makes and waits industrial circles.But copper limits it more in all various deficiencies such as room temperature intensity, high-temperature behavior and polishing machine
It is widely applied.And with the fast development of modern aerospace, electronic technology, more higher want is proposed to the use of copper
It asks, i.e., on the basis of the physical properties such as good conduction, the heat conduction for ensureing copper, it is desirable that material has higher intensity, relatively low
Hot expansibility and good friction and wear behavior etc..Cu-base composites are exactly Development of Novel high-strength highly-conductive and high-wearing feature
One of direction of material.
Graphene is a kind of new material being made of single layer of carbon atom.It is superpower since it possesses the mechanical performance of superelevation
Conduction, the specific surface area of heat conductivility and super large the advantages that, therefore receive the extensive concern of researchers.Mono-layer graphite
The Young's modulus and tensile strength of alkene are up to 1TPa and 130GPa, electron mobility 200,000cm respectively2V-1s-1, while its
Specific surface area is up to 2600m2g-1, and density is only 2.2g cm3.These features cause graphene to increase as Cu-base composites
The excellent selection of strong body.
However, traditional method faces many problems in terms of graphene uniform dispersion and composite material preparation, it is difficult to make
The standby Cu-base composites haveing excellent performance.Therefore in recent years, researcher constantly proposes new method, it is desirable to be able to realize graphene
Enhancing to Cu-base composites.
Chu etc. (Phys Status Solidi A, 2014,211:184-190.) with reference to high-energy ball milling method and hot pressed sintering
Method successfully prepares graphene/Cu-base composites, and when graphene volume fraction is up to 8%, still can uniformly divide
It is dispersed in Copper substrate.The tensile yield strength of the material is 321MPa, elasticity modulus 105GPa.But studies have shown that high energy ball
Mill method can destroy graphene-structured, and the graphene of through a long time high-energy ball milling can be converted into agraphitic carbon, influence enhancing effect.
Hwang etc. (Advanced Materials, 2013,25:Graphene/copper 6724-6729) is prepared using molecular level mixing method
Based composites.Extension test the results show that volume fraction be 2.5% graphene/Cu-base composites elasticity modulus and bend
It is respectively 131GPa and 284MPa to take intensity, is equivalent to 1.3 times and 1.8 times of fine copper, but still there is a big difference with theoretical value.By
To the inspiration of nacre structure, Xiong etc. (Acs Nano, 2015,9:It is 6934-6943) that redox graphene (RGO) is molten
In perfusion to porous copper prefabricated component, RGO is adsorbed onto inside copper precast body hole in dry reduction process, then is compacted into multiple
Condensation material, this graphene/Cu-base composites have the brick mud structure of nacre, tensile strength 233MPa.Party's legal system
Although standby composite material strength increases compared to pure copper material, still much lower than expection.
Kim etc. (Nature Communication, 2013,4,2114:Mono-layer graphite 1-7) is prepared using nano-stack method
Alkene enhances copper-based and nickel-base composite material, obtains abnormal significant enhancing effect, and compressive strength respectively reaches 1.5 Hes
4GPa.The compression yield strength of graphene is improved 10 times, it is shown that graphene is used for metal-based compound material as reinforcement
The great potential of material.There is high compressive strength, but since technique is excessively complicated using the composite material that this method is prepared,
It is difficult to obtain larger composite material block, therefore be difficult to apply to extensive actual production.
Invention content
At present, the method for preparing graphene Cu-base composites has following several.Ball-milling method and molecular level mixing method are main
For the purpose of realizing homodisperse in Copper substrate of graphene, being designed to the composite construction of graphene and copper,
The performance for leading to composite material is not generally high.And although the composite material with layer structure can be obtained using adsorption method,
But since graphene and factors, the tensile strengths of composite material such as Copper substrate binding force is weak are unsatisfactory.Nano-stack method
It is most excellent that the composite material of preparation is undoubtedly performance, but such material is very thin, and to utilize CVD, graphene transfer and object
The multiple technologies such as physical vapor deposition, process is cumbersome, high to equipment requirement, is not suitable for mass production.
In view of the above problems, the present invention proposes a kind of to prepare graphene/copper composite material with microcosmic layer structure
Method, this method raw material is cheap, equipment and operation are simpler, is easy to carry out mass production, composite material has intensity high, leads
Electricity, the advantages of thermal conductivity is good.Graphene oxide and mantoquita are sufficiently mixed by the method for the present invention first, by controlling reaction temperature
Kocide SD is precipitated on graphene oxide sheet surface in the parameters such as degree, pH value, these nanometer rods can not only lodge in graphite oxide
Alkene piece surface, forms good combination, and helps that self assembly occurs between piece and piece, so as to be formed with lamellar structure
Composite granule.It is follow-up to obtain the graphene/Cu-base composites with microcosmic layer structure by reduction and sintering.
Graphene oxide/copper oxide composite powder of the present invention is after mixing copper salt solution and graphene oxide solution
It stirs evenly, then dropwise addition or disposable sodium hydroxide solution to the pH value that adds in are 7~15, and drying is obtained after being washed to neutrality
's；Specifically carry out in the steps below：5-120min is stirred after copper salt solution and graphene oxide solution are mixed；Then exist
It is added dropwise dropwise under the conditions of 1~45 DEG C or disposable sodium hydroxide solution to the pH value that adds in is 7~15, be washed with deionized water into
Property, it is dry to get to graphene oxide/copper oxide composite powder.
It further limits, the mantoquita in the copper salt solution is by copper acetate, copper formate, copper sulphate, copper nitrate or chlorination
One kind in copper or wherein several mixing (mixture, various mantoquitas between be mixed by any ratio).
The mass ratio of the graphene oxide and copper in copper salt solution is (0.001~10):100.
A concentration of 0.5~50mg/ml of the graphene oxide solution.
The concentration of sodium hydroxide solution is 0.5~25mol/L.
Sodium hydroxide solution is added dropwise at 10~30 DEG C.
The temperature of the drying is 70~200 DEG C.
Composite granule prepared by the method for the present invention has microcosmic layer structure.
The preparation method of microcosmic stratiform structure graphite alkene/carbon/carbon-copper composite material is completed by following step：
Step 1: be 200~400 DEG C, under reducing atmosphere condition in temperature, graphene oxide prepared by the above method/
Copper oxide composite powder carries out 0.5~10h of reduction treatment, and reducing atmosphere is hydrogen or the gaseous mixture of hydrogen and inert gas
Body；
Step 2: then handled with plasma electric spark sintering method, vacuum heating-press sintering method or jacket Hot rolling,
Obtain microstructure layer shape structure graphite alkene/carbon/carbon-copper composite material；
Wherein, the volume content of hydrogen is not less than 7% in mixed gas, and inert gas is argon gas, nitrogen, argon gas, nitrogen
In a kind of or wherein several mixing (mixture, various inert gases between be mixed by any ratio).
The electric spark sintering method response parameter is：Sintering temperature is 500~900 DEG C, and sintering pressure is 5~60MPa,
Sintering time is 3~60min.
The vacuum heating-press sintering response parameter is：Sintering temperature is 700~950 DEG C, sintering pressure for 20~
100MPa, sintering time are 3~240min.
The jacket hot rolling response parameter is：Rolling temperature is 500~800 DEG C, and lower bundle amount is 1%~70%.
For the present invention using graphene oxide and mantoquita as raw material, cheap, equipment and operation are simpler, are easy to carry out
Mass production；
Compared with the preparation methods such as traditional molecular level mixing method and ball-milling method, the present invention can obtain having microcosmic stratiform knot
The composite material of structure can realize the design to material structure.
Composite material prepared by the present invention has many advantages, such as intensity height, and conduction, thermal conductivity are good.
Description of the drawings
Fig. 1 is by the composite granule of freeze-drying in specific embodiment one；
Fig. 2 is the metallographic photograph that composite material surface shows microcosmic layer structure after excessive erosion in specific embodiment one
Piece；
Fig. 3 is the stress strain curve of one composite material of specific embodiment；
Fig. 4 is the XRD spectra that composite granule is prepared under different temperatures；
Fig. 5 is 20 DEG C of SEM photographs for preparing composite granule；
Fig. 6 is 40 DEG C of SEM photographs for preparing composite granule；
Fig. 7 is 50 DEG C of SEM photographs for preparing composite granule；
Fig. 8 is the stress strain curve of the composite material prepared under different temperatures；
Fig. 9 is the XRD spectra of the composite granule prepared under different pH value；
Figure 10 is the stress strain curve of the composite material prepared under different pH value.
Specific embodiment
Specific embodiment one：Graphene oxide/copper oxide composite powder of present embodiment be in the steps below into
Capable：Copper acetate is dissolved in deionized water and obtains the copper salt solution of a concentration of 0.29mol/L, by copper salt solution and concentration 1mg/ml
Graphene oxide solution according to copper in graphene oxide and mantoquita mass ratio 0.0066:It is stirred after 100 proportioning mixing
30min；Then sodium hydroxide solution to the pH value that concentration 4mol/L is added dropwise dropwise under the conditions of 20 DEG C is 13.6, uses deionized water
Neutrality is washed till, is dried under the conditions of 110 DEG C to get to graphene oxide/copper oxide composite powder (microcosmic layer structure).
Graphene oxide/the copper oxide composite powder obtained using present embodiment prepares microcosmic stratiform structure graphite
The method of alkene/carbon/carbon-copper composite material is completed by following step：
Step 1: being 400 DEG C, under reducing atmosphere condition in temperature, graphene oxide/copper oxide composite powder is carried out
Reduction treatment 5h, reducing atmosphere are the hydrogen of hydrogen content 17% (volume) and the mixed gas of argon gas；
Step 2: then being handled with plasma electric spark sintering method, sintering temperature is 600 DEG C, sintering pressure
40MPa, sintering time 5min are to get to graphene/composite copper material of the graphene volume fraction 2.5% of microcosmic layer structure
Material.The conductivity of the composite material is 65.67%IACS.
The composite granule and composite material prepared to present embodiment is tested, as a result as shown in Figs. 1-3.
As shown in Figure 1, the copper compound in the composite granule that prepared by present embodiment will be aoxidized in the form of nano-sheet
Graphene film coats completely.
As shown in Figure 2, the composite material through oversintering shows the structure of microcosmic stratiform.
From the figure 3, it may be seen that the tensile strength of composite material prepared by present embodiment method reaches 748MPa, about fine copper
5 times.
Specific embodiment two：Graphene oxide/copper oxide composite powder of present embodiment be in the steps below into
Capable：Copper acetate is dissolved in deionized water and obtains the copper salt solution of a concentration of 0.28mol/L, by copper salt solution and concentration 1mg/ml
Graphene oxide solution according to copper in graphene oxide and mantoquita mass ratio 0.0136:It is stirred after 100 proportioning mixing
30min；Then sodium hydroxide solution to the pH value that concentration 4mol/L is added dropwise dropwise under the conditions of 20 DEG C is 13.6, uses deionized water
Neutrality is washed till, is dried under the conditions of 110 DEG C to get to graphene oxide/copper oxide composite powder (microcosmic layer structure).
Graphene oxide/the copper oxide composite powder obtained using present embodiment prepares microcosmic stratiform structure graphite
The method of alkene/carbon/carbon-copper composite material is completed by following step：
Step 1: being 400 DEG C, under reducing atmosphere condition in temperature, graphene oxide/copper oxide composite powder is carried out
Reduction treatment 5h, reducing atmosphere are the hydrogen of hydrogen content 17% (volume) and the mixed gas of argon gas；
Step 2: then being handled with plasma electric spark sintering method, sintering temperature is 600 DEG C, sintering pressure
40MPa, sintering time 5min are to get to the graphene/copper composite material of the graphene volume fraction 5% of microcosmic layer structure.
The conductivity of the composite material is 69.12%IACS.
Specific embodiment three：Graphene oxide/copper oxide composite powder of present embodiment be in the steps below into
Capable：Copper acetate is dissolved in deionized water and obtains the copper salt solution of a concentration of 0.29mol/L, by copper salt solution and concentration 1mg/ml
Graphene oxide solution according to copper in graphene oxide and mantoquita mass ratio 0.0066:It is stirred after 100 proportioning mixing
30min；Then sodium hydroxide solution to the pH value that concentration 4mol/L is added dropwise dropwise under the conditions of 40 DEG C is 13.6, uses deionized water
Neutrality is washed till, is dried under the conditions of 110 DEG C to get to graphene oxide/copper oxide composite powder (microcosmic layer structure).
Graphene oxide/the copper oxide composite powder obtained using present embodiment prepares microcosmic stratiform structure graphite
The method of alkene/carbon/carbon-copper composite material is completed by following step：
Step 1: being 400 DEG C, under reducing atmosphere condition in temperature, graphene oxide/copper oxide composite powder is carried out
Reduction treatment 5h, reducing atmosphere are the hydrogen of hydrogen content 17% (volume) and the mixed gas of argon gas；
Step 2: then being handled with plasma electric spark sintering method, sintering temperature is 600 DEG C, sintering pressure
40MPa, sintering time 5min are to get to graphene/composite copper material of the graphene volume fraction 2.5% of microcosmic layer structure
Material.The conductivity of the composite material is 69.04%IACS.
Specific embodiment four：Graphene oxide/copper oxide composite powder of present embodiment be in the steps below into
Capable：Copper acetate is dissolved in deionized water and obtains the copper salt solution of a concentration of 0.29mol/L, by copper salt solution and concentration 1mg/ml
Graphene oxide solution according to copper in graphene oxide and mantoquita mass ratio 0.0066:It is stirred after 100 proportioning mixing
30min；Then sodium hydroxide solution to the pH value that concentration 4mol/L is added dropwise dropwise under the conditions of 20 DEG C is 8, is washed with deionized water
To neutrality, dried under the conditions of 110 DEG C to get to graphene oxide/copper oxide composite powder (microcosmic layer structure).
Graphene oxide/the copper oxide composite powder obtained using present embodiment prepares microcosmic stratiform structure graphite
The method of alkene/carbon/carbon-copper composite material is completed by following step：
Step 1: being 400 DEG C, under reducing atmosphere condition in temperature, graphene oxide/copper oxide composite powder is carried out
Reduction treatment 5h, reducing atmosphere are the hydrogen of hydrogen content 17% (volume) and the mixed gas of argon gas；
Step 2: then being handled with plasma electric spark sintering method, sintering temperature is 600 DEG C, sintering pressure
40MPa, sintering time 5min are to get to graphene/composite copper material of the graphene volume fraction 2.5% of microcosmic layer structure
Material.The conductivity of the composite material is 64.09%IACS.
Specific embodiment five：Present embodiment it is different from specific embodiment four be to replace using vacuum heating-press sintering
For the plasma electric spark sintering method of step 2, sintering temperature is 800 DEG C, sintering pressure 50MPa, sintering time 10min.
Other steps and parameter are identical with specific embodiment four.
Specific embodiment six：Present embodiment is different from specific embodiment four to be using jacket hot rolling replacement step
Rapid two plasma electric spark sintering method, rolling temperature are 600 DEG C, and lower bundle amount is 40%.Other steps and parameter and specific reality
It is identical to apply mode four.
Using following verification experimental verification invention effects：
Graphene oxide/copper oxide composite powder is prepared under experiment one, different temperatures.
Graphene oxide/copper oxide composite powder carries out in the steps below：Copper acetate is dissolved in deionized water to obtain
To the copper salt solution of a concentration of 0.29mol/L, by the graphene oxide solution of copper salt solution and concentration 1mg/ml according to oxidation stone
The mass ratio 0.0066 of black alkene and copper in mantoquita:30min is stirred after 100 proportioning mixing；Then in 20 DEG C, 40 DEG C or 50 DEG C conditions
Under the sodium hydroxide solution of concentration 4mol/L to pH value is added dropwise dropwise is 13.6, be washed with deionized water to neutrality, in 110 DEG C of conditions
Lower drying is to get to graphene oxide/copper oxide composite powder.
XRD spectra such as Fig. 4 of graphene oxide/copper oxide composite powder is prepared under different temperatures, as shown in Figure 4, when
When reaction temperature is 20 DEG C and 40 DEG C, the diffraction maximum in the XRD spectra of composite granule corresponds to Kocide SD and copper oxide respectively
Crystal face；And when reaction temperature reaches 50 DEG C, in XRD spectra, the characteristic peak of Kocide SD disappears, and the feature of copper oxide only occurs
Peak.This illustrates higher reaction temperature (less than 50 DEG C), and the Kocide SD in composite granule can be made to be completely converted into copper oxide.
The SEM photograph of composite granule is prepared under different temperatures as shown in Figs. 5 to 7.When reaction temperature is 20 DEG C, composite powder
Copper oxide and Kocide SD mainly exist in the form of nanometer sheet in body, and size is in 500nm or so.When reaction temperature rises to 40 DEG C
When, nanometer sheet is reduced in size to 200~300nm.When reaction temperature reaches 50 DEG C, the nanometer sheet in composite granule is converted to
Nanorod structure.
The tensile stress strain curve of composite material (referring to the method for specific embodiment one) prepared under different temperatures
As shown in Figure 8.The ultimate tensile strength of composite material prepared under the conditions of room temperature, 40 DEG C and 50 DEG C be respectively 748MPa,
625MPa and 288MPa.As can be seen that as the raising of reaction temperature, the tensile strength of composite material are gradually reduced, work as reaction
When temperature reaches 50 DEG C, without apparent yield point elongation in load-deformation curve, that is to say, that be broken from ductile rupture and become crisp
Property fracture.This is primarily due to, and when reaction temperature is relatively low, NaOH, which is added drop-wise in copper salt solution, generates Cu (OH)2, Cu (OH)2Band is just
Electricity generates strong interaction so that GO sheet surfaces Adsorption of Cu (OH) with electronegative GO2So as to avoid between lamella
Overlap joint, so through reduction, after sintering processes, graphene can be also uniformly dispersed in Copper substrate, and plays the effect of enhancing
Fruit；And (it is higher than 50 DEG C) when reaction temperature is higher, more CuO (as shown in Figure 9) is generated in reaction system, with the liter of temperature
Height, the warm-up movements of CuO in the solution aggravate, and easily combine and grow up, and the binding force of CuO and GO is weak between particle, it is impossible to GO
It forms effectively cladding, graphene also easily to reunite, eventually leading to the tensile strength of composite material reduces.
The XRD spectra of the composite granule prepared under different pH value is as shown in Figure 9.When pH value is 5.9 and 6.6, in spectrogram
Diffraction maximum mostly come from basic copper acetate；With the raising of pH value, the diffraction maximum of basic copper acetate fades away, and occurs
The characteristic peak of Kocide SD and copper oxide.It is very big that this illustrates that pH value influences the object phase composition of composite granule.
The tensile stress strain curve of composite material (referring to the method for specific embodiment one) prepared under different pH value
As shown in Figure 10.The ultimate tensile strength of composite material prepared under the conditions of being 5.9,6.6 and 13.6 in pH value is 514MPa,
459MPa and 748MPa.As can be seen that the composite material strength prepared under conditions of pH shows acidity is relatively low.This be mainly because
For that although basic copper acetate crystallizes in the form of sheets, due to generating a large amount of water and carbon dioxide during its pyrolytic, can generate a large amount of
Hole defect, therefore be unfavorable to the intensity for improving composite material.
Claims (10)
1. graphene oxide/copper oxide composite powder, it is characterised in that the composite granule is by copper salt solution and graphite oxide
It is stirred evenly after the mixing of alkene solution, it is 7~15 that sodium hydroxide solution to pH value, which is then added dropwise, and drying is obtained after being washed to neutrality
's.
2. the preparation method of graphene oxide/copper oxide composite powder as described in claim 1, it is characterised in that the preparation
Method carries out in the steps below：
5-120min is stirred after copper salt solution and graphene oxide solution are mixed；Then hydrogen-oxygen is added under the conditions of 1~45 DEG C
It is 7~15 to change sodium solution to pH value, is washed with deionized water to neutrality, dry to get to graphene oxide/Cu oxide composite powder
Body.
3. the preparation method of graphene oxide/copper oxide composite powder according to claim 1, it is characterised in that mantoquita
Mantoquita in solution is by one kind in copper acetate, copper formate, copper sulphate, copper nitrate or copper chloride or wherein several mixing.
4. the preparation method of graphene oxide/copper oxide composite powder according to claim 1, it is characterised in that described
The mass ratio of graphene oxide and copper in copper salt solution is (0.001~10):100.
5. the preparation method of graphene oxide/copper oxide composite powder according to claim 1, it is characterised in that described
A concentration of 0.5~50mg/ml of graphene oxide solution.
6. the preparation method of graphene oxide/copper oxide composite powder according to claim 1, it is characterised in that described
Concentration of sodium hydroxide solution is 0.5~25mol/L.
7. the preparation method of graphene oxide/copper oxide composite powder according to claim 1, it is characterised in that 10
Sodium hydroxide solution is added dropwise at~30 DEG C.
8. the preparation method of graphene oxide/copper oxide composite powder according to claim 1, it is characterised in that described
Dry temperature is 70~200 DEG C.
9. the preparation method of microcosmic stratiform structure graphite alkene/carbon/carbon-copper composite material, it is characterised in that microcosmic stratiform structure graphite alkene/copper
The preparation method of composite material is completed by following step：
Step 1: it is 200~400 DEG C, under reducing atmosphere condition in temperature, by graphene oxide described in claim 1/copper oxygen
Graphene oxide/copper oxide composite powder prepared by compound composite granule or claim 2~9 any one the method
0.5~10h of reduction treatment is carried out, reducing atmosphere is hydrogen or the mixed gas of hydrogen and inert gas；
Step 2: then with plasma electric spark sintering method, vacuum heating-press sintering method or jacket Hot rolling handled to get
To microcosmic stratiform structure graphite alkene/carbon/carbon-copper composite material；
Wherein, the volume content of hydrogen is not less than 3% in mixed gas, and inert gas is argon gas, in nitrogen, argon gas, nitrogen
A kind of or wherein several mixing.
10. the preparation method of microcosmic stratiform structure graphite alkene/carbon/carbon-copper composite material according to claim 9, it is characterised in that
The electric spark sintering method response parameter is：Sintering temperature be 500~900 DEG C, sintering pressure be 5~80MPa, sintering time
For 3~60min；The vacuum heating-press sintering response parameter is：Sintering temperature is 700~950 DEG C, sintering pressure for 20~
100MPa, sintering time are 3~240min；The jacket hot rolling response parameter is：Rolling temperature is 500~800 DEG C, lower bundle
Measure is 1%~70%.
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| CN111020260A (en) * | 2019-12-13 | 2020-04-17 | 昆明理工大学 | Preparation method of layered copper-based composite material |
| CN111375774A (en) * | 2020-04-29 | 2020-07-07 | 西安稀有金属材料研究院有限公司 | Preparation method of graphite-copper-molybdenum-based composite material for electronic packaging |
| CN112011706A (en) * | 2019-05-30 | 2020-12-01 | 哈尔滨工业大学 | Batch preparation method of carbon nanosheet reinforced copper-based composite material |
| CN112011705A (en) * | 2019-05-30 | 2020-12-01 | 哈尔滨工业大学 | Batch preparation method of nano-carbon reinforced copper-based composite material |
| CN113061768A (en) * | 2021-03-22 | 2021-07-02 | 中南大学 | Preparation method of dispersion-strengthened copper-based composite material |
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| CN112011705A (en) * | 2019-05-30 | 2020-12-01 | 哈尔滨工业大学 | Batch preparation method of nano-carbon reinforced copper-based composite material |
| CN111020260A (en) * | 2019-12-13 | 2020-04-17 | 昆明理工大学 | Preparation method of layered copper-based composite material |
| CN111020260B (en) * | 2019-12-13 | 2021-07-23 | 昆明理工大学 | Preparation method of layered copper-based composite material |
| CN111375774A (en) * | 2020-04-29 | 2020-07-07 | 西安稀有金属材料研究院有限公司 | Preparation method of graphite-copper-molybdenum-based composite material for electronic packaging |
| CN113061768A (en) * | 2021-03-22 | 2021-07-02 | 中南大学 | Preparation method of dispersion-strengthened copper-based composite material |
| CN113061768B (en) * | 2021-03-22 | 2023-08-25 | 中南大学 | Preparation method of dispersion strengthening copper-based composite material |
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