CN112795801B - Preparation method of graphene-based reinforced carbon-copper composite material - Google Patents
Preparation method of graphene-based reinforced carbon-copper composite material Download PDFInfo
- Publication number
- CN112795801B CN112795801B CN202011581386.1A CN202011581386A CN112795801B CN 112795801 B CN112795801 B CN 112795801B CN 202011581386 A CN202011581386 A CN 202011581386A CN 112795801 B CN112795801 B CN 112795801B
- Authority
- CN
- China
- Prior art keywords
- graphene
- powder
- copper
- preparation
- composite material
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 37
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 33
- 239000010453 quartz Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 13
- LTPQFVPQTZSJGS-UHFFFAOYSA-N 1$l^{4},3,5$l^{4},7-tetrathia-2,4,6,8-tetrazacycloocta-1,4,5,8-tetraene Chemical compound [N]1S[N]S[N]S[N]S1 LTPQFVPQTZSJGS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 24
- 229910052802 copper Inorganic materials 0.000 abstract description 23
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract 1
- 239000010955 niobium Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- C22C1/0425—Copper-based alloys
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- 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
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—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
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/40—Carbon, graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
Abstract
The invention discloses a preparation method of a graphene-based reinforced carbon-copper composite material, which comprises the following steps: (1) preparing graphene; (2) surface activation treatment; (3) mixing; (4) spark plasma sintering. Rapidly discharging a carbon source with high carbon content, and generating easily stripped laminated graphene at a high temperature within one second; activating the surface of the prepared graphene to enable the generated sulfur-nitrogen-containing heterocyclic group-containing graphene to be in a three-dimensional structure; uniformly mixing copper, niobium and graphene under the action of ultrasound and ball milling in a molten state, and preparing the graphene reinforced copper matrix by using a spark plasma sintering technology. The preparation method can effectively improve the mechanical property of the graphene-copper base, and is low in cost and easy to operate.
Description
Technical Field
The invention relates to the technical field of preparation of composite materials, in particular to a preparation method of a graphene-based reinforced carbon-copper composite material.
Background
Graphene is the thinnest, highest strength, toughest, best heat transfer property and electrical conductivity nano material discovered so far, has excellent electrical property, high thermal conductivity, high Young modulus and excellent tensile strength, and becomes an ideal reinforcing phase in a high-performance metal matrix composite material due to excellent comprehensive performance; the advantages of graphene are fully exerted, the composite material with high performance and excellent structural function integration performance is prepared, and breakthroughs of metal materials are brought.
Copper and copper alloy have excellent electric conductivity and heat conductivity, good plasticity, toughness and ductility, are widely applied in the electronic, electrical and mechanical manufacturing industry and occupy an important position in modern industrial systems. As known from domestic and foreign documents, the graphene serving as a reinforcing phase is added into a copper matrix, so that the comprehensive performance of the composite material can be effectively improved, crystal grains can be refined by adding a small amount of graphene, a good reinforcing effect is achieved, and meanwhile, the good lubricating property of the graphene has obvious effects on reducing the friction coefficient of the composite material and effectively improving the friction and wear performance of the composite material.
However, current technology can produce small amounts of perfect graphene, or tons of oligomeric graphene blocks; since the discovery of high quality graphene in 2004, whether monolithic or stacked in several layers, the cost of manufacturing and purification on an industrial scale has remained high. The compatibility between single-layer graphene sheets and other materials is poor due to strong van der Waals force between the single-layer graphene sheets, and the sheets are easy to stack to form thicker graphite particles which lose the singular performance of graphene; the surface chemical structure of the graphene is changed through the functional modification of the graphene, so that the graphene is endowed with new performance. Therefore, it is important to solve the problems of producing graphene with low cost and high quality and modifying the surface of graphene.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene-based reinforced carbon-copper composite material, which aims to solve the problem of performance reduction caused by difficulty in synthesis and uneven dispersion of graphene.
In order to achieve the purpose, the invention provides a preparation method of a graphene-based reinforced carbon-copper composite material, which comprises the following steps:
(1) preparation of graphene
Carrying out high-voltage discharge on carbon source powder, completely cooling, taking out reactants, repeatedly washing, filtering and drying to obtain graphene powder;
(2) surface activation treatment
Heating graphene powder in an inert gas atmosphere; dissolving tetranitrogen tetrasulfide solid in carbon disulfide liquid, heating, gasifying, introducing into graphene powder, and keeping the temperature; after the reaction is finished, introducing inert gas again to exhaust the gas in the graphene powder until the graphene powder is cooled to room temperature; wherein, the volume fraction of tetranitrogen tetrasulfide in the carbon disulfide liquid is 3-5%;
(3) mixing
Adding the object obtained in the step (2) into an ethanol solution, and oscillating under the ultrasonic condition to obtain a dispersion liquid; then sequentially adding copper powder and niobium powder into the dispersion liquid, and carrying out ball milling on the dispersion liquid to obtain mixed liquid; heating the mixed liquid to 80-85 ℃ and continuously stirring until the mixed liquid is semi-dry, and drying to obtain copper-niobium-graphene mixed powder;
(4) spark plasma sintering
Sintering the copper-niobium-graphene mixed powder obtained in the step (3) by spark plasma in vacuum, and cooling to obtain the copper-niobium-graphene mixed powder; wherein the sintering temperature is 700-750 ℃, and the sintering time is 5-7 min.
The beneficial effect who adopts above-mentioned scheme is: firstly, carbon source powder can be rapidly heated by Joule to provide gram-level graphene in a short time, then the graphene powder can be subjected to surface activation treatment under an inert condition to synthesize a sulfur and nitrogen group on the graphene, and the group types in the graphene subjected to surface treatment mainly comprise pyrrole type nitrogen, graphite type nitrogen, thiophene type sulfur, graphite type sulfur and a novel sulfur and nitrogen heterocyclic group; on one hand, nitrogen atoms and sulfur atoms are respectively combined with graphene to generate four groups of pyrrole type nitrogen, graphite type nitrogen, thiophene type sulfur and graphite type sulfur; on the other hand, the nitrogen in the five-membered heterocycle is bonded to one carbon atom and donates two P electrons to the pi system. The sulfur element is introduced by substituting one of carbon atoms in the other six rings and combining with one nitrogen atom in the five-membered heterocycle, so that a three-dimensional graphene structure containing a nitrogen-sulfur group is formed. Doping graphite type nitrogen inIn the plane of graphitic carbon and with three SPs2The carbon atoms are bonded. The graphene containing the sulfur-nitrogen group, copper powder and niobium powder are subjected to ball milling and heating to obtain the graphene composite copper-based material, and finally, the graphene in the obtained copper-based composite material can be uniformly distributed through spark plasma sintering, so that the agglomeration phenomenon is avoided.
Further, the carbon source in the step (1) is one of coal, petroleum coke, biochar and carbon black, and the carbon content is more than 90%.
The beneficial effect who adopts above-mentioned scheme is: the cheap carbon source with high carbon content can greatly improve the economic benefit for production, and graphene prepared by discharging the carbon source with carbon content more than 90% is in layered overlapping distribution, is easy to strip and does not need purification operation.
Further, the specific steps of the high-voltage discharge in the step (1) include: placing carbon source powder in a sample tube to enable the powder to be located at the middle position of the sample tube; putting a sample tube filled with carbon source powder into a discharger group, connecting positive and negative electrodes at two ends of the sample tube, and performing high-voltage discharge on the powder by using the discharger group; wherein the discharge voltage is 400-450V, the discharge time is 200-300 ms, and the pressure of the gas in the device is normal pressure.
Furthermore, the sample tube is a quartz or ceramic sample tube, is in a circular tube shape, and has a diameter of 5 cm-10 cm.
The beneficial effect who adopts above-mentioned scheme is: the sample tube with the larger diameter can produce more graphene at one time, but the sample tube with the diameter of more than 10cm produces impure graphene, so that the sample tube with the diameter of 5-10 cm is most suitable; the flat sample tube is beneficial to improving the cooling rate.
Further, in the high-voltage discharge process in the step (1), the temperature of the wall of the sample tube is less than 60 ℃, and the gas temperature is not more than 3100K.
The beneficial effect who adopts above-mentioned scheme is: graphene with good performance and high content cannot be synthesized at a temperature lower than or higher than the temperature; particularly, when the gas temperature reaches 3100K, the effect of synthesizing the graphene is best.
Further, in the step (2), the inert gas is argon or helium.
Further, the heating temperature of the graphene powder in the step (2) is 800-.
Further, the raw materials used in the mixing process of step (3) are prepared from graphene powder: copper powder: the niobium powder consists of 3-5:80-90:3-5 by mass.
Further, the ultrasonic oscillation time in the step (3) is 1-2 hours, and the ball milling time is 0.5-1 hour.
Further, the cooling process of step (4) further comprises increasing the pressure from the beginning of cooling until the end of cooling, wherein the increasing pressure condition is: gradually increasing the pressure from 40MPa to 50-55 MPa at the rate of 0.1MPa per minute.
In summary, the invention has the following advantages:
1. the high-temperature high-pressure electrification is utilized to rapidly discharge the cheap carbon source with high carbon content, so that the graphene can be efficiently and rapidly prepared, and the problems of high preparation cost and difficult stripping of the graphene are solved;
2. activating the surface of the graphene to enable the surface of the graphene to have a nitrogen-containing and sulfur-containing group; the method comprises the following steps of simultaneously processing graphene by using tetranitrogen tetrasulfide and carbon disulfide to generate a novel sulfur-nitrogen heterocyclic group, so that the graphene is in a three-dimensional structure, and the conductivity of the graphene is enhanced;
3. in the preparation process of the graphene reinforced copper base, the graphene in the obtained copper base composite material is uniformly distributed by utilizing ultrasonic waves, a ball mill and a spark plasma sintering means, so that the problem that the graphene is agglomerated in the copper base in the past is solved.
Drawings
Fig. 1 is a schematic view of an apparatus for preparing laminated graphene;
FIG. 2 is a morphogram of graphene nitrogen sulfur heterocycle;
fig. 3 is a flow chart of graphene-reinforced copper-based preparation.
Detailed Description
Example 1
The invention provides a preparation method of a graphene-based reinforced carbon-copper composite material, which comprises the following steps:
(1) preparation of graphene
Placing carbon black powder in a quartz tube to enable the powder to be in the middle of the quartz tube; putting a quartz tube filled with carbon black powder into a discharger group, connecting positive and negative copper electrodes at two ends of the quartz tube, and performing high-voltage discharge on the powder by using the discharger group, wherein the discharge voltage is 400V, the discharge time is 200ms, and the gas pressure in the device is normal pressure, so that the electrified rapid heating process is completed; after the quartz tube is completely cooled, taking out the reactant, repeatedly washing, filtering and drying to obtain graphene powder;
(2) surface activation treatment
Putting the graphene powder into the quartz tube again, and introducing argon gas to exhaust air in the quartz tube; keeping an argon gas environment, and heating the graphene powder to 800 ℃; dissolving tetranitrogen tetrasulfide solid in carbon disulfide liquid to ensure that the volume fraction of tetranitrogen tetrasulfide in the carbon disulfide liquid is 3 percent, then slowly heating to 280 ℃, gasifying and introducing into a sample tube, and keeping the temperature of 800 ℃ for 1 h; after the reaction is finished, introducing argon gas again to exhaust the gas in the quartz tube until the quartz tube is cooled to room temperature, and obtaining the graphene containing the sulfur-nitrogen group;
(3) mixing
Adding the substance obtained in the step (2), namely the graphene containing the sulfur and nitrogen groups into an absolute ethyl alcohol solution, and oscillating for 1h by utilizing the action of ultrasonic waves to obtain a dispersion liquid of the graphene containing the sulfur and nitrogen groups; then, sequentially adding copper powder and niobium powder into the dispersion liquid containing the sulfur-nitrogen group-containing graphene, and performing ball milling for 0.5h by using a ball milling technology to obtain ball-milled mixed liquid; heating the mixed liquid in a water-proof way, keeping the water temperature at 80 ℃ and continuously stirring until the mixed liquid is in a semi-dry state; placing the powder in a drying box for drying to obtain copper-niobium-graphene mixed powder, wherein the mass ratio of the object obtained in the step (2), copper powder and niobium powder is 3:80: 3;
(4) spark plasma sintering
Sintering the copper-niobium-graphene mixed powder by spark plasma under vacuum for 5 minutes at 700 ℃ to obtain a required size; the pressure was gradually increased from the start of cooling, and the applied pressure was gradually increased from 40MPa to 50MPa at a rate of 0.1MPa per minute until the end of cooling.
Example 2
The invention provides a preparation method of a graphene-based reinforced carbon-copper composite material, which comprises the following steps:
(1) preparation of graphene
Placing carbon black powder in a quartz tube to enable the powder to be in the middle of the quartz tube; putting a quartz tube filled with carbon black powder into a discharger group, connecting positive and negative copper electrodes at two ends of the quartz tube, and performing high-voltage discharge on the powder by using the discharger group, wherein the discharge voltage is 425V, the discharge time is 250ms, and the gas pressure in the device is normal pressure, so that the electrified rapid heating process is completed; after the quartz tube is completely cooled, taking out the reactant, repeatedly washing, filtering and drying to obtain graphene powder;
(2) surface activation treatment
Putting the graphene powder into the quartz tube again, and introducing argon gas to exhaust air in the sample tube; keeping an argon gas environment, and heating the graphene powder to 900 ℃; dissolving tetranitrogen tetrasulfide solid in carbon disulfide liquid to ensure that the volume fraction of tetranitrogen tetrasulfide in the carbon disulfide liquid is 4 percent, slowly heating to 300 ℃, gasifying and introducing into a quartz tube, and keeping the temperature of 900 ℃ for 75 min; after the reaction is finished, introducing argon gas again to exhaust the gas in the quartz tube until the quartz tube is cooled to room temperature, and obtaining the graphene containing the sulfur-nitrogen group;
(3) mixing
Adding the substance obtained in the step (2), namely the graphene containing the sulfur and nitrogen groups into an absolute ethyl alcohol solution, and oscillating for 1.5 hours by utilizing the ultrasonic action to obtain a dispersion liquid of the graphene containing the sulfur and nitrogen groups; then adding copper powder and niobium powder into the dispersion liquid containing the sulfur-nitrogen group-containing graphene in sequence, and performing ball milling for 45 minutes by using a ball milling technology to obtain ball-milled mixed liquid; heating the mixed liquid in a water-proof way, keeping the water temperature at 83 ℃ and continuously stirring until the mixed liquid is semi-dry; placing the powder in a drying box for drying to obtain copper-niobium-graphene mixed powder; wherein the mass ratio of the object obtained in the step (2), the copper powder and the niobium powder is 4:85: 4;
(4) plasma sintering by fire
Sintering the copper-niobium-graphene mixed powder by spark plasma under vacuum at 725 ℃ for 6 minutes to obtain a required size; the pressure was gradually increased from the start of cooling, and the applied pressure was gradually increased from 40MPa to 53MPa at a rate of 0.1MPa per minute until the end of cooling.
Example 3
The invention provides a preparation method of a graphene-based reinforced carbon-copper composite material, which comprises the following steps:
(1) preparation of graphene
Placing carbon black powder in a quartz tube to enable the powder to be in the middle of the quartz tube; putting a quartz tube filled with carbon black powder into a discharger group, connecting positive and negative copper electrodes at two ends of the quartz tube, and performing high-voltage discharge on the powder by using the discharger group, wherein the discharge voltage is 450V, the discharge time is 300ms, and the gas pressure in the device is normal pressure, so that the electrified rapid heating process is completed; after the quartz tube is completely cooled, taking out the reactant, repeatedly washing, filtering and drying to obtain graphene powder;
(2) surface activation treatment
Putting the graphene powder into the quartz tube again, and introducing argon gas to exhaust air in the quartz tube; keeping an argon gas environment, and heating the graphene powder to 1000 ℃; dissolving tetranitrogen tetrasulfide solid in carbon disulfide liquid to ensure that the volume fraction of tetranitrogen tetrasulfide in the carbon disulfide liquid is 5 percent, slowly heating to 350 ℃, gasifying and introducing into a sample tube, and keeping the temperature of 1000 ℃ for 1.5 hours; after the reaction is finished, introducing argon gas again to exhaust the gas in the sample tube until the quartz tube is cooled to room temperature, and obtaining the graphene containing sulfur-nitrogen groups;
(3) mixing
Adding the substance obtained in the step (2), namely the graphene containing the sulfur and nitrogen groups into an absolute ethyl alcohol solution, and oscillating for 2 hours by utilizing the action of ultrasonic waves to obtain a dispersion liquid of the graphene containing the sulfur and nitrogen groups; then adding copper powder and niobium powder into the dispersion liquid containing the sulfur-nitrogen group-containing graphene in sequence, and performing ball milling for 1h by using a ball milling technology to obtain ball-milled mixed liquid; heating the mixed liquid in a water-proof way, keeping the water temperature at 85 ℃ and continuously stirring until the mixed liquid is semi-dry; placing the powder in a drying box for drying to obtain copper-niobium-graphene mixed powder; wherein the mass ratio of the object obtained in the step (2), the copper powder and the niobium powder is 5:90: 5;
(4) spark plasma sintering
Sintering the copper-niobium-graphene mixed powder by spark plasma under vacuum for 7 minutes at 750 ℃ to obtain a required size; the pressure was gradually increased from the start of cooling, and the applied pressure was gradually increased from 40MPa to 55MPa at a rate of 0.1MPa per minute until the end of cooling.
Comparative example 1
A method of preparing a graphene-reinforced copper-based composite (wherein different graphene modification methods are employed), comprising:
(1) under the ice bath condition, under the mechanical stirring, adding crystalline flake graphite powder into 98% concentrated sulfuric acid, then adding sodium nitrate accounting for 80 wt% of the graphite powder and potassium permanganate accounting for 4 times of the graphite powder, and reacting for 120min under ice bath;
(2) heating the solution treated in the step (1) to 40 ℃, keeping the temperature constant for 5 hours, adding deionized water and hydrogen peroxide which both account for 5% of the volume of the solution, stirring for 3 hours, continuing adding deionized water and hydrogen peroxide which account for 3% of the volume of the solution, stirring for 3 hours, adding hydrochloric acid with the volume concentration of 5%, and centrifuging and washing until no sulfate ions exist, thereby obtaining graphene oxide;
(3) putting graphene oxide into a hydrazine hydrate solution with the concentration of 10 wt% for reduction, wherein the reduction temperature is 90 ℃, and the reduction time is 2 hours, so as to obtain graphene;
(4) ultrasonically dispersing graphene powder into an ethanol solution, and mixing the graphene powder with the ethanol solution according to the ratio of nano copper powder: adding nano copper powder into graphene according to the weight ratio of 100:1, and uniformly stirring by ultrasonic to obtain mixed slurry;
(5) ball-milling the mixed slurry by using a high-energy ball mill, then carrying out centrifugal separation on the mixed slurry, and drying in vacuum to obtain graphene/nano copper powder composite particles;
(6) pre-compressing the composite particles under the protection of nitrogen to obtain a prefabricated member;
(7) and sintering the prefabricated member by electric spark under the following sintering conditions: the vacuum degree is 0.2Pa, the applied pressure is 60MPa, the sintering temperature is 650 ℃, and the sintering time is 10 min.
Comparative example 2
A method of graphene reinforced copper-based composites (in which graphene is not modified or any pre-treatment applied) comprising:
(1) mixing graphene, nano copper powder and nano cobalt powder to obtain a mixed material, putting the mixture into absolute ethyl alcohol according to the volume ratio of 2:1 of the ethyl alcohol to the mixed powder, and vibrating on an electromagnetic oscillator for 1 hour to carry out physical dispersion to obtain mixed slurry; wherein the mass ratio of the graphene to the nano copper powder to the nano cobalt powder is 0.1:5: 94.9;
(2) placing the mixed slurry into a ball mill to perform ball milling for 2 hours to obtain composite powder, wherein the rotating speed in the ball milling process is 100r/min, the ball-to-material ratio is 5:1, the composite powder is dried in a forced air drying oven for 5 hours and then is subjected to annealing treatment, the annealing temperature is 100 ℃, and the annealing time is 30 minutes;
(3) pressing and molding the annealed powder in a graphite mold, wherein the size of the graphite mold is 40mm x 30mm (r x h), the pressing force is 20MPa, and the loading time is 10 min;
(4) putting the whole pressed block powder graphite mould into SPS sintering equipment, carrying out hot-pressing sintering, wherein the sintering temperature is 750 ℃, the sintering vacuum degree is 2020MPa, the sintering pressing force is 3020MPa, the heating rate is 50 ℃/min, the cooling rate is 5 ℃/min, keeping the temperature for 2min, and taking out the block composite material when cooling to room temperature by water cooling;
(5) carrying out hot extrusion on the block composite material to obtain the block composite material; wherein the extrusion temperature is 600 ℃ and the extrusion ratio is 9: 1.
For the copper base prepared in examples 1 to 3 and comparative examples 1 to 2, a universal material testing machine was used for the flexural strength data detection, a thermal conductivity tester was used for the thermal conductivity data detection, and a vickers hardness test was used, and the obtained data are shown in table 1:
TABLE 1 comparison of basic copper-based Properties
As can be seen from table 1, the preparation method of the graphene adopted by the graphene in the comparative example 1 is to prepare the graphite powder into simple graphene through oxidation-reduction reaction, and then apply the graphene to enhance the conductivity of the copper base, so that the copper base prepared in the comparative example 1 has slight advantages in conductivity, relatively weak in thermal conductivity, and low in vickers hardness; comparative example 2 uses commercially available graphene directly, and does not perform any modification work on it, so that each property is lower than the data of the examples when it is subsequently used in a composite material.
The copper base prepared by the preparation method of the invention has higher flexural strength and Vickers hardness than the performance of untreated copper and the performance of the copper base treated by the comparative example 1-2, the heat conductivity coefficient can reach 397W/mk, the density is lighter, and the copper base is more suitable for the electronic and electrical industry and the mechanical manufacturing industry.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (10)
1. A preparation method of a graphene-based reinforced carbon-copper composite material is characterized by comprising the following steps:
(1) preparation of graphene
Carrying out high-voltage discharge on carbon source powder, completely cooling, taking out reactants, repeatedly washing, filtering and drying to obtain graphene powder;
(2) surface activation treatment
Heating graphene powder in an inert gas atmosphere; dissolving tetranitrogen tetrasulfide solid in carbon disulfide liquid, heating, gasifying, introducing into graphene powder, and keeping the temperature; after the reaction is finished, introducing inert gas again to exhaust the gas in the graphene powder, and then cooling to room temperature; wherein, the volume fraction of tetranitrogen tetrasulfide in the carbon disulfide liquid is 3-5%;
(3) mixing
Adding the object obtained in the step (2) into an ethanol solution, and oscillating under the ultrasonic condition to obtain a dispersion liquid; then sequentially adding copper powder and niobium powder into the dispersion liquid, and carrying out ball milling on the dispersion liquid to obtain mixed liquid; heating the mixed liquid to 80-85 ℃ and continuously stirring until the mixed liquid is semi-dry, and drying to obtain copper-niobium-graphene mixed powder;
(4) spark plasma sintering
Sintering the copper-niobium-graphene mixed powder obtained in the step (3) by spark plasma in vacuum, and cooling to obtain the copper-niobium-graphene mixed powder; wherein the sintering temperature is 700-750 ℃, and the sintering time is 5-7 min.
2. The preparation method of the graphene-based reinforced carbon-copper composite material according to claim 1, wherein the carbon source in the step (1) is one of coal, petroleum coke, biochar and carbon black, and the carbon content is more than 90%.
3. The preparation method of the graphene-reinforced carbon-copper-based composite material according to claim 1, wherein the specific steps of the high-voltage discharge in the step (1) comprise: placing carbon source powder in a sample tube to enable the powder to be located at the middle position of the sample tube; putting a sample tube filled with carbon source powder into a discharger group, connecting positive and negative electrodes at two ends of the sample tube, and performing high-voltage discharge on the powder by using the discharger group; wherein the discharge voltage is 400-450V, the discharge time is 200-300 ms, and the pressure of the gas in the device is normal pressure.
4. The preparation method of the graphene-reinforced carbon-copper-based composite material according to claim 3, wherein the sample tube is a quartz or ceramic sample tube, is in a shape of a circular tube, and has a diameter of 5cm to 10 cm.
5. The preparation method of the graphene-based reinforced carbon-copper composite material according to claim 3, wherein in the high-voltage discharge process in the step (1), the temperature of the wall of the sample tube is less than 60 ℃, and the gas temperature is not more than 3100K.
6. The preparation method of the graphene-based reinforced carbon-copper composite material according to claim 1, wherein the inert gas in the step (2) is argon or helium.
7. The method for preparing the graphene-based reinforced carbon-copper composite material as claimed in claim 1, wherein the graphene powder in the step (2) is heated at a temperature of 800-.
8. The preparation method of the graphene-based reinforced carbon-copper composite material according to claim 1, wherein the mass ratio of the object obtained in the step (2) in the step (3), the copper powder and the niobium powder is 3-5:80-90: 3-5.
9. The preparation method of the graphene-based reinforced carbon-copper composite material according to claim 1, wherein the ultrasonic oscillation time in the step (3) is 1-2 hours, and the ball milling time is 0.5-1 hour.
10. The preparation method of the graphene-reinforced carbon-copper composite material according to claim 1, wherein the cooling process in the step (4) further comprises increasing the pressure from the beginning of cooling to the end of cooling, wherein the increasing pressure condition is as follows: gradually increasing the pressure from 40MPa to 50-55 MPa at the rate of 0.1MPa per minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011581386.1A CN112795801B (en) | 2020-12-28 | 2020-12-28 | Preparation method of graphene-based reinforced carbon-copper composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011581386.1A CN112795801B (en) | 2020-12-28 | 2020-12-28 | Preparation method of graphene-based reinforced carbon-copper composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112795801A CN112795801A (en) | 2021-05-14 |
| CN112795801B true CN112795801B (en) | 2021-09-07 |
Family
ID=75805155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011581386.1A Active CN112795801B (en) | 2020-12-28 | 2020-12-28 | Preparation method of graphene-based reinforced carbon-copper composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112795801B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113604697B (en) * | 2021-08-13 | 2023-03-24 | 哈尔滨工业大学 | Preparation method of graphene-loaded copper-reinforced copper-based high-thermal-conductivity composite material capable of self-assembly adsorption under ultrasonic oscillation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5116082B2 (en) * | 2007-04-17 | 2013-01-09 | 住友精密工業株式会社 | High thermal conductivity composite material |
| CN104671237B (en) * | 2015-02-04 | 2016-08-17 | 浙江大学 | A kind of devices and methods therefor preparing graphene film based on plasma |
| US20190292671A1 (en) * | 2018-03-26 | 2019-09-26 | Nanotek Instruments, Inc. | Metal matrix nanocomposite containing oriented graphene sheets and production process |
| CN109003826B (en) * | 2018-07-27 | 2019-12-17 | 福州大学 | preparation method of N and S double-doped graphene-graphene nanoribbon aerogel |
| CN109251051B (en) * | 2018-09-14 | 2020-01-14 | 西南交通大学 | Carbon nanofiber reinforced pantograph composite carbon sliding plate and preparation method thereof |
-
2020
- 2020-12-28 CN CN202011581386.1A patent/CN112795801B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112795801A (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101980583B (en) | Method for preparing graphite electrode of quartz crucible | |
| CN108145169B (en) | High-strength high-conductivity graphene reinforced copper-based composite material, and preparation method and application thereof | |
| CN104556022A (en) | Method for preparing expanded microcrystal graphite material from microcrystal graphite | |
| CN102583346B (en) | Method for preparing special graphite | |
| CN112795801B (en) | Preparation method of graphene-based reinforced carbon-copper composite material | |
| CN106881466A (en) | Rare earth modified grapheme strengthens the preparation method of metal-based compound bar | |
| CN102268686A (en) | Electrochemical method for reducing solid metal oxide in molten salt to synthesize high-melting-point metal carbide under low temperature | |
| JP2013535400A (en) | Apparatus, method and composition for the manufacture of silicon nitride nanostructures | |
| CN116462509B (en) | Isostatic pressure graphite for photovoltaic and preparation method and application thereof | |
| GB2465912A (en) | Process for preparing powder of niobium suboxides or niobium | |
| CN110436928A (en) | High-performance nano twin boron carbide ceramics block materials and preparation method thereof | |
| CN101798638A (en) | Method for producing chromium metal by using carbon reduction two-step method | |
| CN101704678A (en) | Self-propagation high-temperature synthesizing preparation method of TiB2-TiC complex ceramic micropowder | |
| CN104402450B (en) | One is prepared Ti fast based on thermal explosion low temperature reaction2The method of AlN ceramic powder | |
| CN101704674A (en) | Method for preparing titanium diboride ceramic micro powder by self-propagation high temperature synthesis | |
| CN109437132B (en) | Production method of titanium nitride powder | |
| CN113151705A (en) | ZK60 magnesium alloy preparation method based on SPS technology | |
| CN117263706A (en) | Wear-resistant low-resistance carbon material and preparation method thereof | |
| KR20080076598A (en) | Nano tantallum powder | |
| CN110627518A (en) | Preparation method of high-strength composite graphite electrode | |
| KR100368054B1 (en) | Synthesis of fine cobalt powders | |
| CN112427648B (en) | Preparation method and preparation device of metal molybdenum powder | |
| CN110127660B (en) | Method for preparing porous carbon nanomaterial by microwaves | |
| CN115433009A (en) | Sagger for graphitizing and purifying battery negative electrode and preparation method thereof | |
| KR20080076597A (en) | Nano tantallum powder |
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 |