CN104846231B - Preparation method of copper-based graphene composite blocky material - Google Patents
Preparation method of copper-based graphene composite blocky material Download PDFInfo
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Abstract
The invention provides a preparation method of a copper-based graphene composite blocky material. The preparation method comprises carrying out in-situ mixing on a copper salt solution, reducing sugar, alkali and graphene as raw materials by a solution method so that graphene is uniformly dispersed in the copper solution, reducing copper into cuprous oxide by a hydrothermal reduction method, carrying out in-situ deposition on cuprous oxide particles on the graphene surface, reducing the cuprous oxide particles into copper particles by hydrogen, and carrying out discharge plasma sintering to obtain the copper-based graphene composite blocky material. The copper-based graphene composite blocky material has good graphene dispersibility, good adhesion of a copper base and a graphene reinforcing phase, high tensile strength and compressive strength, and good thermal conductivity.
Description
Technical field
The present invention relates to Cu-base composites technical field, more particularly to a kind of system of copper-base graphite alkene composite block material
Preparation Method.
Background technology
Copper is the good conductor of heat, and its thermal conductivity factor is 401W/mK, is only second to silver, is applied to field of electronics more.But
With the design of developing rapidly for modern industrial technology, instrument and equipment and parts it is compacter, especially electric and electronic field,
Appliance electronic component develops towards lighter, thinner, less direction, big energy density and little heat-dissipating space, for material
Heat conductivility put forward higher requirement, the single metal material of tradition can not meet design requirement, have both Metal Substrate
The metal-base composites of body and reinforcing component excellent properties receives extensive concern.
Graphene is a kind of new material with individual layer laminated structure being made up of carbon atom, be known world it is most thin,
Most hard nano material.The thermal conductivity factor of Graphene is up to 5300W/mK, and higher than CNT and diamond, intensity is reachable
130GPa, Young's modulus is up to 1TPa, and specific surface area is 2630m2g-1, it is preferable composite filling phase.
At present, the research of graphene composite material is concentrated mainly on polymer matrix graphene composite material field, and for
The research of Metal Substrate graphene composite material is less.This is faced with skill mainly due to the research of Metal Substrate graphene composite material
An art difficult problem：Graphene is weak with the adhesion of metallic matrix；In addition, the technical barrier for also existing is：Graphene is in metallic matrix
It is susceptible to reunite, it is expected excellent that this two big technical barrier causes the Metal Substrate Graphene block materials of current preparation to obtain
Different in nature energy.
Improving the method for metal and Graphene adhesion at present mainly has two kinds：A kind of method is in graphenic surface plating
The metallic particles such as nickel, copper, silver.But being related to plating or plating process the method, process is complicated, and uses to some extent more
Poisonous and harmful chemicals, is unfavorable for environmental protection and safety.Another kind of method is to carry out surface in graphenic surface addition functional group
It is modified.But the method is due to changing the surface texture of Graphene, so as to the performance of Graphene can be weakened.
The content of the invention
For the above-mentioned state of the art, the present invention is intended to provide a kind of preparation method of copper-base graphite alkene composite block material,
Good using graphene dispersion in copper-base graphite alkene block composite material obtained in the method, Copper substrate strengthens alternate with Graphene
With good adhesion, and with good thermal conductivity.
In order to realize above-mentioned technical purpose, the present inventor has found after many experiments, with copper salt solution, reducing sugar,
Alkali and Graphene are raw material, are mixed using solwution method is in situ, graphene uniform is dispersed in Copper substrate, then by hydro-thermal also
Copper reduction is cuprous oxide by former method, then by hydrogen reducing cuprous oxide particle to copper particle, finally by plasma discharging
Sintering, obtains copper-base graphite alkene composite block material, and the composite block material not only has a good thermal conductivity, and with compared with
High tensile strength and compressive strength, show that wherein copper-based enhancing with Graphene mutually have good adhesion.
That is, the technical solution adopted in the present invention is：A kind of preparation method of copper-base graphite alkene composite block material, including
Following steps：
(1) appropriate Graphene, the aqueous solution of reducing sugar and alkaline matter are added in mantoquita ethanol solution, mixing is equal
It is placed in after even in reactor, hydrothermal reduction reaction is carried out in isoperibol, makes copper reduction for cuprous oxide, then filtration reaction
Product, scrubbed, vacuum drying, obtains cuprous oxide Graphene composite powder；
(2) cuprous oxide Graphene composite powder obtained in hydrogen gas reduction step (1), cuprous oxide therein is reduced to
Copper, obtains copper-base graphite alkene composite granule；
(3) copper-base graphite alkene composite granule obtained in step (2) is put in graphite jig, electric discharge is put into after pre-molding
Plasma agglomeration stove, carries out discharge plasma sintering shaping in vacuum or protective atmosphere, obtains copper-base graphite alkene composite block
Body material.
The mantoquita is not limited, can be selected from copper nitrate, copper acetate, copper sulfate etc..
The reducing sugar is not limited, the one kind or two that can be selected from glucose, lactose, maltose, fructose, galactolipin etc.
Plant the mixing of the above.
The alkaline matter is not limited, can be selected from one or more in NaOH, potassium hydroxide, ammoniacal liquor etc.
Mixing.
In the copper-base graphite alkene composite block material, the mass percent of Graphene is preferably 0.01%~10%, remaining
Measure as copper.
In the step (1), the quality of Graphene is 1 with the mass ratio of copper：9999~10：90.In order to enter one
Step improves the thermal conductivity factor of Graphene composite block material, and the quality of Graphene is more preferably 5 with the mass ratio of copper：
9955~5：95.
In the step (1), Graphene is preferably dimensioned to be 5~15 μm, and thickness is preferably 0.4~6nm.
In the step (1), reaction temperature is preferably 60~120 DEG C.
In the step (1), the reaction time is preferably 2~4h.
In described step (1), in the washing process, according to pure deionized water washing reaction product, destructible
The dispersiveness of Graphene, according to absolute alcohol solution washing reaction product, is easily caused product pattern and property changes,
For this purpose, preferably, using alcohol and the mixing liquid washing reaction product of deionized water.It is further preferred that the mixing
In liquid, the volume ratio of alcohol and deionized water is 2:1~1:2.
In described step (2), reduction temperature is preferably 100~500 DEG C.
In described step (2), the recovery time is preferably 2~10 hours.
In the step (3), preload pressure is preferably 5~20MPa.
In the step (3), when using discharge plasma sintering shaping is carried out in a vacuum, vacuum is preferably 10- 4Pa~10-1Pa。
In the step (3), in SPS sintering process, heating rate is preferably 50 DEG C/min~500 DEG C/min, sintering temperature
Degree is preferably 400~1000 DEG C, and multiple pressure pressure is preferably 10MPa~100MPa, and temperature retention time is preferably 1~120min.
In the step (3), the time is pressed to be preferably 4~10min again.
In sum, compared with prior art, it is an advantage of the current invention that：
(1) on the one hand the inventive method efficiently avoid Graphene reunion, on the other hand not only have good heat conduction
Property, and the adhesion of Graphene and Copper substrate is improve, so as to have higher tensile strength and compressive strength, trace it to its cause
It is as follows：
The present invention makes graphene uniform be dispersed in Copper substrate using solwution method mixed powder in situ；Then hydrothermal reduction is utilized
Copper reduction is cuprous oxide by method, and in this process, part copper is reduced to the reaction of cuprous oxide to be occurred in graphenic surface,
That is the cuprous particle in-situ of partial oxidation is deposited on graphenic surface, obtains cuprous oxide particle and surface attachment cuprous oxide
The Graphene of grain, this not only efficiently avoid Graphene reunion, and graphenic surface in-situ preparation cuprous oxide, produces carbon
Oxygen key, so as to improve the adhesion of Graphene and surface copper particle；Finally by hydrogen reducing cuprous oxide particle, copper is obtained
The Graphene of particle-matrix and surface attachment copper particle, because graphenic surface adheres to copper particle, substantially increases Graphene
Strengthen the adhesion with Copper substrate.
(2) present invention sinters copper-base graphite alkene composite granule using discharge plasma sintering technique.
Discharge plasma sintering is by the way that the powder such as metal are loaded in the moulds made by material such as graphite, using upper and lower
Specific sintering power supply and pressing pressure are put on sintered powder by stamping and powered electrode, Jing discharge activations, thermoplastic deformation and cold
But a kind of new powder metallurgy sintered technology for producing high performance material is completed.Discharge plasma sintering has in pressure process
The characteristics of sintering, the pressurization in the plasma and sintering process of pulse current generation advantageously reduces the sintering temperature of powder.
Simultaneously low-voltage, the feature of high current, can make powder Fast Sintering fine and close.Unique sintering method can effectively reduce copper-based stone
The sintering temperature of black alkene composite, it is to avoid Graphene performance is destroyed, obtains high-performance copper graphene composite material.
(3) present invention adopts Graphene as raw material, compared with graphene oxide is as raw material, the material performance of the present invention
It is good；
(4) present invention using reducing sugar as reducing agent, compared with the reducing agents such as hydrazine hydrate, to human body and environment without
Evil, safety and environmental protection.
(5) in the present invention, Graphene content can adjust, and by adjusting Graphene content stone in the composite can be controlled
The distribution of black alkene, and then property anisotropy copper-base graphite alkene composite block material is obtained.Research discovery, low content stone
Black alkene is intended to random distribution, and high-load Graphene is intended to distribution of orientations.Also, when copper-base graphite alkene composite block material
In, when Graphene weight/mass percentage composition is 0.05%~5%, thermal conductivity factor and intensity are apparently higher than Copper substrate itself.
Description of the drawings
Fig. 1 is the XRD diffraction before and after cuprous oxide graphene composite powder Jing hydrogen reducings obtained in the embodiment of the present invention 1
Atlas analysis；
Fig. 2 is the outward appearance photo of copper-base graphite alkene composite block material obtained in the embodiment of the present invention 1；
Fig. 3 is the Raman pattern analysis results figure of copper-base graphite alkene composite block material obtained in the embodiment of the present invention 1.
Specific embodiment
Below with reference to drawings and Examples, the present invention will be further described, it should be pointed out that described below is implemented
Example is intended to be easy to the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
In the present embodiment, the preparation method of copper-base graphite alkene composite block material is as follows：
(1) copper nitrate is weighed for 99.8wt% according to copper content, prepares copper nitrate ethanol solution.
(2) Graphene is added in copper nitrate ethanol solution, the quality of Graphene is 2 with the mass ratio of copper：
998, ultrasonic agitation 1h；Add the glucose solution that concentration is 0.6M, ultrasonic agitation 0.5h；Then add in ultrasonic agitation
The sodium hydroxide solution of concentration 0.6M, obtains mixed solution.
Mixed solution is placed in into reactor, the hydrothermal reduction 2h in 80 DEG C of baking ovens；Gained product is filtered, recycling is gone
The mixing liquid of ionized water and ethanol is washed, and the volume ratio of alcohol and deionized water is 2 in the mixing liquid:1, Ran Houzhen
Empty 60 DEG C of dryings, obtain powdered product.
The powdered product is carried out into XRD tests, as a result as shown in figure 1, its main diffraction peak shows from cuprous oxide
In the hydrothermal reduction reaction, copper is reduced to cuprous oxide, and obtained powdered product main body is cuprous oxide Graphene composite powder
End.
(3) cuprous oxide Graphene composite powder obtained in step (2) is put in tube furnace, hydrogen is passed through, at 400 DEG C
Under the conditions of the cuprous oxide Graphene composite powder is reduced, the recovery time is 2h, obtains reduzate.
The reduzate is carried out into XRD tests, its result is copper diffraction maximum as shown in figure 1, obtaining diffraction maximum, shows this
During cuprous oxide be reduced to copper, the reduzate be copper-base graphite alkene composite powder.
(4) weigh copper-base graphite alkene composite powder obtained in a certain amount of step (3) and be put into pre-molding in the moulds of Φ 20, in advance
Pressure pressure 5MPa；Composite after precompressed is put in discharge plasma sintering stove together with mould carries out vacuum discharge plasma
Sintering, vacuum is 10-2Pa.The discharge plasma sintering process is：Heating rate is 100 DEG C/min, and sintering pressure is
40MPa, sintering temperature is 800 DEG C, and in sintering temperature 10min is incubated, and multiple pressure pressure is 50MPa, presses the time to be 7min again.Sintering
After obtain a diameter of Φ 20, thickness for 5mm copper-base graphite alkene composite block material.
Fig. 2 is the exterior appearance figure of copper-base graphite alkene composite block material obtained above, shows the block materials tissue
Even compact, there is bright metallic luster.The density for measuring the block materials using Archimedes principle is 8.605g/cm3,
That is, the block materials have very high consistency.
Raman atlas analysis are carried out to copper Graphene composite block material obtained above, as a result as shown in figure 3, showing inspection
Obvious Graphene Characteristic Raman peak is measured, and there is no significant change with the Raman trace analysis of Graphene raw material, illustrated stone
Black alkene is not reunited in preparation process, and structure is not destroyed.
The tensile strength test results of copper-base graphite alkene composite block material obtained above show that its tensile strength is
350MPa, than the tensile strength of the in kind obtained pure copper material without Graphene 20% is improved.
The compressive strength test result of copper-base graphite alkene composite block material obtained above shows, its compressive strength
480MPa, is 1.5 times of the in kind compressive strength of the obtained pure copper material without Graphene.
The heat conduction result of copper-base graphite alkene composite block material obtained above shows that it is perpendicular to in-plane thermal conductivity
For 432K/ (mK), than the in kind obtained pure copper material without Graphene 15% is higher by.In-plane and perpendicular to
Thermal conductivity ratio is 0.9 on in-plane.
Embodiment 2：
A kind of preparation method of copper-base graphite alkene composite block material is provided in the present embodiment as follows：
(1) copper sulphate is weighed for 99wt% according to copper content, prepares copper sulphate ethanol solution.
(2) Graphene is added in copper sulphate ethanol solution, the quality of Graphene is 1 with the mass ratio of copper：99,
Ultrasonic agitation 2h；Add the glucose solution that concentration is 0.5M, ultrasonic agitation 1h；Then concentration is added in ultrasonic agitation
The potassium hydroxide solution stirring of 0.5M, obtains mixed solution.
Mixed solution is placed in into reactor, the hydrothermal reduction 4h in 80 DEG C of baking ovens；Gained product is filtered, recycling is gone
The mixing liquid of ionized water and ethanol is washed, and the volume ratio of deionized water and alcohol is 1 in the mixing liquid:1, Ran Houzhen
Empty 80 DEG C of dryings, obtain powdered product.
Described in similar embodiment 1, the powdered product is carried out into XRD tests, shows main diffraction peak from cuprous oxide,
Show that in the hydrothermal reduction reaction, copper is reduced to cuprous oxide, obtained powdered product main body is cuprous oxide Graphene
Composite powder.
(3) cuprous oxide Graphene composite powder obtained in step (2) is put in tube furnace, hydrogen is passed through, at 300 DEG C
Under the conditions of the cuprous oxide Graphene composite powder is reduced, the recovery time is 2h, obtains reduzate.
Described in similar embodiment 1, the reduzate is carried out into XRD tests, show that diffraction maximum is copper diffraction maximum, shown
Cuprous oxide is reduced to copper during being somebody's turn to do, and the reduzate is copper-base graphite alkene composite powder.
(4) weigh copper-base graphite alkene composite powder obtained in a certain amount of step (3) and be put into pre-molding in the moulds of Φ 20, in advance
Pressure pressure 10MPa；Composite after precompressed is put in discharge plasma sintering stove together with mould carry out vacuum discharge etc. from
Son sintering, vacuum is 10-2Pa.The discharge plasma sintering process is：Heating rate is 80 DEG C/min, and sintering pressure is
40MPa, sintering temperature is 600 DEG C, and in sintering temperature 5min is incubated, and multiple pressure pressure is 60MPa, presses the time to be 5min again.Sintering
After obtain a diameter of Φ 20, thickness for 5mm copper-base graphite alkene composite block material.
The even tissue of copper-base graphite alkene composite block material obtained above is fine and close, there is bright metallic luster, has
High consistency.
Similar embodiment 1, to copper Graphene composite block material obtained above Raman atlas analysis are carried out, and are as a result shown
Obvious Graphene Characteristic Raman peak is detected, and there is no significant change with the Raman trace analysis of Graphene raw material, illustrate stone
Black alkene is not reunited in preparation process, and structure is not destroyed.
The compressive strength test result of copper-base graphite alkene composite block material obtained above shows that its compressive strength is more than
600MPa, is the twice of the in kind compressive strength of the obtained pure copper material without Graphene.
Similar embodiment 1, the heat conduction result of copper-base graphite alkene composite block material obtained above shows, its in-plane
Thermal conductivity is 427K/ (mK), and than the in kind obtained pure copper material without Graphene 13% is higher by.In-plane and
Thermal conductivity ratio is 1.5 on in-plane.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
For the specific embodiment of the present invention, the present invention is not limited to, all any modifications made in the spirit of the present invention,
Supplementary or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of copper-base graphite alkene composite block material, is characterized in that：Comprise the steps：
(1) appropriate Graphene, the aqueous solution of reducing sugar and alkaline matter are sequentially added in mantoquita ethanol solution, mixing is equal
It is placed in after even in reactor, hydrothermal reduction reaction occurs in isoperibol, make copper reduction be cuprous oxide, partial oxidation is cuprous
Particle in-situ is deposited on graphenic surface, obtains the Graphene of cuprous oxide particle and surface attachment cuprous oxide particle, so
Product is filtered afterwards, wash, be vacuum dried, obtain cuprous oxide Graphene composite powder；
(2) cuprous oxide Graphene composite powder obtained in hydrogen gas reduction step (1), cuprous oxide therein is reduced to copper, obtains
To copper-base graphite alkene composite granule, i.e. copper particle-matrix and the Graphene of surface attachment copper particle；
(3) copper-base graphite alkene composite granule obtained in step (2) is put in graphite jig, be put into after pre-molding electric discharge etc. from
Sub- sintering furnace, carries out discharge plasma sintering shaping in vacuum or protective atmosphere, obtains copper-base graphite alkene composite block material
Material；
The quality of Graphene is 1 with the mass ratio of copper：9999~10：90；
In the step (1), hydrothermal temperature is 60~120 DEG C, and the reaction time is 2~4h；
In the washing process, using alcohol and the mixing liquid washing reaction product of deionized water, in the mixing liquid,
The volume ratio of alcohol and deionized water is 2:1~1:2.
2. the preparation method of copper-base graphite alkene composite block material as claimed in claim 1, is characterized in that：The mantoquita is selected from
One or more mixture in copper nitrate, copper acetate, copper sulfate.
3. the preparation method of copper-base graphite alkene composite block material as claimed in claim 1, is characterized in that：The reducing sugar
One or more mixture in glucose, lactose, maltose, fructose, galactolipin.
4. the preparation method of copper-base graphite alkene composite block material as claimed in claim 1, is characterized in that：The alkaline matter
One or more mixture in NaOH, potassium hydroxide, ammoniacal liquor.
5. the preparation method of the copper-base graphite alkene composite block material as described in any claim in Claims 1-4, it is special
Levying is：In the step (1), the quality of Graphene is 5 with the mass ratio of copper：9995~5：95.
6. the preparation method of the copper-base graphite alkene composite block material as described in any claim in Claims 1-4, it is special
Levying is：In the step (2), reduction temperature is 100~500 DEG C.
7. the preparation method of copper-base graphite alkene composite block material as claimed in claim 6, is characterized in that：The step (2)
In, the recovery time is 2~10 hours.
8. the preparation method of the copper-base graphite alkene composite block material as described in any claim in Claims 1-4, it is special
Levying is：In the step (3), preload pressure is 5~20MPa.
9. the preparation method of the copper-base graphite alkene composite block material as described in any claim in Claims 1-4, it is special
Levying is：In the step (3), in SPS sintering process, heating rate is 50 DEG C/min~500 DEG C/min, and sintering temperature is 400
~1000 DEG C, multiple pressure pressure is 10MPa~100MPa, and temperature retention time is 1~120min.
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| CN105525124B (en) * | 2016-02-02 | 2017-07-07 | 天津大学 | Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method |
| CN105973956B (en) * | 2016-04-28 | 2018-12-21 | 衡阳师范学院 | Detect the complex film modified acetylene black electrode of graphene-cuprous oxide and detection method of vanillic aldehyde in food |
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| CN106623976A (en) * | 2016-12-29 | 2017-05-10 | 陕西理工学院 | Preparation method of graphene-metal-based bulk composite material |
| CN108264041B (en) * | 2016-12-31 | 2019-12-24 | 哈尔滨工业大学 | Graphene oxide/copper oxide composite powder, preparation method thereof and preparation method of graphene/copper composite material with micro-layered structure |
| CN107557602B (en) * | 2017-10-18 | 2019-03-26 | 北京科技大学 | A kind of preparation method of graphene enhancing ODS copper |
| CN108580885B (en) * | 2018-04-09 | 2021-03-16 | 西安交通大学 | Preparation method of graphene coated powder with core-shell structure |
| CN111172420A (en) * | 2018-12-02 | 2020-05-19 | 苏州大德碳纳米科技有限公司 | Preparation method of copper-based nano material added with fullerene or fullerene carbon powder |
| CN109513926B (en) * | 2018-12-20 | 2020-12-15 | 昆明理工大学 | Preparation method of CNT-GO/Cu composite material with hierarchical structure |
| CN110408969B (en) * | 2019-08-09 | 2021-05-25 | 常州大学 | Preparation method of high-thermal-conductivity copper-based graphene composite material |
| CN111375774B (en) * | 2020-04-29 | 2023-02-21 | 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 |
| CN113061768B (en) * | 2021-03-22 | 2023-08-25 | 中南大学 | Preparation method of dispersion strengthening copper-based composite material |
| CN113927041B (en) * | 2021-09-17 | 2022-10-11 | 中国科学院深圳先进技术研究院 | Graphene copper-based composite material and preparation method and application thereof |
| CN114000003A (en) * | 2021-10-22 | 2022-02-01 | 昆明理工大学 | Preparation method of graphene/carbon dot synergistically-reinforced copper-based composite material |
| CN114855020A (en) * | 2022-05-18 | 2022-08-05 | 深圳市明鑫工业材料有限公司 | Preparation process of oxygen-free copper-based high-strength composite material |
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| CN103030170A (en) * | 2013-01-16 | 2013-04-10 | 哈尔滨工业大学 | Preparation method for cuprous oxide/reduced graphene oxide composite functional material |
| CN103952588B (en) * | 2014-05-08 | 2016-04-13 | 江西理工大学 | High-strength highly-conductive Graphene Cu-base composites and preparation method thereof |
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