CN107460423B - A kind of preparation method of graphene/metal composite conductive coating - Google Patents
A kind of preparation method of graphene/metal composite conductive coating Download PDFInfo
- Publication number
- CN107460423B CN107460423B CN201710697354.XA CN201710697354A CN107460423B CN 107460423 B CN107460423 B CN 107460423B CN 201710697354 A CN201710697354 A CN 201710697354A CN 107460423 B CN107460423 B CN 107460423B
- Authority
- CN
- China
- Prior art keywords
- metal
- powder
- graphene
- graphene oxide
- modified graphene
- 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 104
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002905 metal composite material Substances 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000428 dust Substances 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 238000001238 wet grinding Methods 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 15
- 239000010959 steel Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000010285 flame spraying Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 claims description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000010891 electric arc Methods 0.000 claims description 4
- 238000007750 plasma spraying Methods 0.000 claims description 4
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- -1 sodium alkyl benzene Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000007751 thermal spraying Methods 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 238000007747 plating Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229910000570 Cupronickel Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Plasma & Fusion (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of preparation method of graphene/metal composite conductive coating, atomized metal pow der and grading steel ball are put into ball grinder in mass ratio, fill up after absolute ethyl alcohol with the rotating speed wet-milling of 200 ~ 400r/min for a period of time, then add graphene oxide powder and dispersant, wet-milling is for a period of time, then dried using vacuum drying chamber, then by obtained metal-modified graphene oxide powder；It is put into shower furnace and heat-treats, obtains metal-modified graphene composite powder；Finally metal-modified graphene composite powder is sprayed on metallic matrix using hot-spraying technique.The present invention first carries out raw material scattered and modification, then growth graphene is directly reduced in metal powder surface using suspended state thermal reduction, and the metal powder that surface growth has graphene is coated in metal base surface by the way of thermal spraying, metal dust softens through high-temperature fusion, metallurgical chemistry is carried out with metal base surface to be combined, and improves attachment degree of the coating on metallic matrix.
Description
Technical field
The present invention relates to a kind of preparation method of graphene/metal composite conductive coating, belong to conductive technical field.
Background technology
Fine silver be it is a kind of forge, plastic noble metal, there is good conduction and heat conductivility, in all metals,
It is best with the electric conductivity of silver.Based on the good electric conductivity of silver, metal base surface silver plating process occupies ten in battery production
Divide consequence.Traditional silver plating process is broadly divided into cyanide silver plating process and cyanide-free silver plating process.But due to cyanide
Silver plating liquid severe toxicity, has the shortcomings that pollution environment, the health for endangering the producer and treatment cost of waste liquor are higher, so people wish
Hope with other electroplating technologies to substitute cyanide to electroplate silver process.And the stability of cyanide-free silver plating process and the performance of coating and cyanogen
Compound silver plating process is compared, and also there are certain gap, can not be shown the excellent conductive capability of silver completely, therefore, be ground
It is of far-reaching significance and extremely urgent to make a kind of conductive coating nontoxic, stable, that electric conductivity is good and replace silver plating process.
Each carbon atom of graphene is SP2 hydridization, and a remaining P orbital electron forms big pi bond, and pi-electron can be with
Move freely, assign graphene excellent electric conductivity.Since interatomic force is very strong, at normal temperatures, even if surrounding carbon is former
Son collides, and the electronics in graphene is received to disturb also very little.Electronics is not susceptible to scatter when transmitting in graphene, electricity
Transport factor is 2 × 105cm2/（V·s）, 140 times of electron mobility about in silicon, its conductivity is up to 106S/m, is under room temperature
The optimal material of electric conductivity.
However, since graphene specific surface area is big, specific surface energy is higher, agglomeration is quite serious, it is difficult in Metal Substrate
It is dispersed on body；And graphene density is smaller, neither hydrophilic nor oleophylic, reactivity is relatively low so that it is changed
Property it is relatively difficult, various reasons result in graphene and metallic matrix coating difficulty is larger, and by graphene dispersion in colloid
In coated on metallic matrix, since resin is non-conductive, and agglomeration is serious, and the conduction for greatly destroying graphene is continuous
Property, its performance is also not satisfactory.Traditional metal based coating preparation method is difficult to prepare graphene-Metal Substrate of excellent performance
Coating.
Thermal spraying utilizes certain heat source（Such as electric arc, plasma spraying or combustion flame）By powdered or Filamentous metal
Or nonmetallic materials are heated to melting or semi-molten state, then itself or compressed air is stayed to be ejected into certain speed by flame
Pretreated matrix surface, deposits and forms a kind of technology of the face coat with various functions.Have the following advantages that：1、
Basis material is unrestricted, can be metal and nonmetallic, can be sprayed on various basis materials；2. sprayable coating material
Expect extremely wide, plasma spray technology can be used to spray almost all of solid engineering material, such as hard alloy, ceramics, metal, stone
Ink etc.；3. basis material temperature rise is small in spraying process, stress and deformation are not produced；4. operating procedure is flexible, from workpiece
Shape limits, easy for construction；5. coating layer thickness can be from 0.01 to several millimeters；6. coating performance is varied, can be formed resistance to
Mill, anti-corrosion, heat-insulated, anti-oxidant, insulation, conduction, radiation protection etc. have the coating of various specific functions；It is 7. adaptable and economical
It is profitable.
The content of the invention
The defects of in order to overcome the prior art, the present invention provide a kind of preparation side of graphene/metal composite conductive coating
Method, first carries out raw material scattered and modification, is then directly reduced using suspended state thermal reduction in metal powder surface
Graphene is grown, and the metal powder that surface growth has graphene is coated in metal base surface by the way of thermal spraying, gold
Belong to powder through high-temperature fusion to soften, carry out metallurgy-chemical bond with metal base surface, improve coating on metallic matrix
Attachment degree.
A kind of preparation method of graphene/metal composite conductive coating, comprises the following steps that：
（1）Metal dust pre-processes
Atomized metal pow der and grading steel ball are put into ball grinder in mass ratio, fill up after absolute ethyl alcohol with 200 ~
The rotating speed wet-milling of 400r/min is t for a period of time1, form flaky metal powder；
（2）It is prepared by metal-modified graphene oxide powder
In step（1）In ball grinder in by weight percent than adding graphene oxide powder and dispersant, with 400 ~
The rotating speed wet-milling of 800r/min is t for a period of time2, then dried using vacuum drying chamber under the conditions of 80 DEG C, be made scattered equal
Even metal-modified graphene oxide powder；
（3）Suspended state heat-treats metal-modified graphene oxide powder
By step（2）Obtained copper-modified graphene oxide powder is put into progress suspended state thermal reduction in shower furnace,
Thermal reduction temperature is set as 400 DEG C ~ 1000 DEG C, and in shower furnace with certain flow velocity be passed through certain volume than protective gas
Argon gas and reducing gas hydrogen, reaction a period of time is t3, the graphene oxide on flaky metal powder is attached in metal powder
Last surface in situ reduction generation graphene, is cooled to room temperature, that is, obtains metal-modified graphene composite powder after reaction；
（4）It is prepared by metal-modified graphene composite powder coatings
Metal-modified graphene composite powder is sprayed on metallic matrix using hot-spraying technique.
Preferably, step（1）Described in metal dust be the conductive metal powder with high reproducibility, including copper powder, nickel
One or both of powder.
Preferably, step（1）Described in the mass ratio of metal dust and grading steel ball be 1:20~1:25, and grading steel ball
Grading be φ 25mm：φ55mm：φ75mm=2:3:5, the metal dust particle diameter is 5 ~ 10 microns.
Preferably, in step（2）In, based on quality percentage, the graphene oxide powder is step（1）Middle metal dust
1% ~ 10%, the dispersant be metal dust 0.01% ~ 0.1%.
Preferably, the dispersant is the surfactant containing conjugated bonds, including sodium alkyl benzene sulfonate, polyphenyl ethyl sulfonic acid
Sodium.
Preferably, the volume ratio of the hydrogen and argon gas is 5:95.
Preferably, the flow velocity of the argon gas and hydrogen is 2.3L/min ~ 15L/min.
Preferably, the t1For 2 ~ 3h, the t2For 1 ~ 2h, the t3For 5 ~ 30s.
Preferably, step（4）The hot-spraying technique includes flame-spraying, plasma spraying, laser spraying or electric arc
Spraying, the thickness of the metal-modified graphene composite powder coatings is 0.01 ~ 0.1mm.
Beneficial effect：The invention discloses a kind of preparation method of graphene/metal composite conductive coating, has following excellent
Point：（1）The present invention has first carried out ball milling pretreatment before graphene oxide is mixed with metal dust to metal dust, makes its shape
Slabbing structure, adds the contact area of graphene oxide and metal dust, also increases graphene reduction growing surface, has
Beneficial to the growth of graphene film Rotating fields；（2）The present invention makes graphene oxide and metallic catalyst powder using the method for suspended state
End and reducibility gas hydrogen come into full contact with reaction, with the prior art（The fastest response time >=15min）Compare, greatly reduce
Reaction time, while reduce reaction temperature, reduce energy consumption, and due to whole reaction process in flowing gas it is complete
Into reducing the contact between graphene sheet layer, alleviate the agglomeration of graphene；（3）The present invention to metal dust and
It is modified using the surfactant containing conjugated structure when graphene oxide is mixed, passes through surfactant
Conjugated structure and the big pi-conjugated system of graphene oxide produce powerful non-covalent interaction, so as to improve oxidation
The dispersiveness of graphene, with it is existing be modified by covalent bond effect compared with, the molecule knot of graphene oxide will not be destroyed
Structure so that the excellent properties of graphene can be played farthest；（4）The present invention is using hot-spraying technique in metallic matrix
Metal-modified powdered graphite is coated, is tied since metal dust can produce metallurgical-chemistry with metallic matrix in thermal spray process
Close, solve the problems, such as that adhesive force existing for existing hot-spraying technique is weak, while ensure that the electric conductivity of coating；（5）With it is existing
Directly compared in technology in the technique of metal base surface direct growth graphene, production can be achieved in each step of the invention
Serialization, can both form production integration, can also form industrial chain, flexible and changeable, and it is time-consuming it is short, easy to mass producing.
Brief description of the drawings
Fig. 1 is the scanned photograph of copper-modified graphene composite powder in embodiment 1；
Fig. 2 is the scanned photograph of nickel-modified graphene composite powder in embodiment 4；
Fig. 3 is the scanned photograph of ambrose alloy-modified graphene composite powder in embodiment 5.
Embodiment
It is in order to make those skilled in the art better understand the technical solutions in the application, real below in conjunction with the application
The attached drawing in example is applied, the technical solution in the embodiment of the present application is clearly and completely described, it is clear that described implementation
Example is merely a part but not all of the embodiments of the present application.It is common based on the embodiment in the application, this area
Technical staff's all other embodiments obtained without making creative work, should all belong to the application protection
Scope.
A kind of preparation method of graphene/metal composite conductive coating, comprises the following steps that：
（1）Metal dust pre-processes
Atomized metal pow der and grading steel ball are put into ball grinder in mass ratio, fill up after absolute ethyl alcohol with 200 ~
The rotating speed wet-milling of 400r/min is t for a period of time1, form flaky metal powder；
（2）It is prepared by metal-modified graphene oxide powder
In step（1）In ball grinder in by weight percent than adding graphene oxide powder and dispersant, with 400 ~
The rotating speed wet-milling of 800r/min is t for a period of time2, then dried using vacuum drying chamber under the conditions of 80 DEG C, be made scattered equal
Even metal-modified graphene oxide powder；
（3）Suspended state heat-treats metal-modified graphene oxide powder
By step（2）Obtained copper-modified graphene oxide powder is put into progress suspended state thermal reduction in shower furnace,
Thermal reduction temperature is set as 400 DEG C ~ 1000 DEG C, and in shower furnace with certain flow velocity be passed through certain volume than protective gas
Argon gas and reducing gas hydrogen, reaction a period of time is t3, the graphene oxide on flaky metal powder is attached in metal powder
Last surface in situ reduction generation graphene, is cooled to room temperature, that is, obtains metal-modified graphene composite powder after reaction；
（4）It is prepared by metal-modified graphene composite powder coatings
Metal-modified graphene composite powder is sprayed on metallic matrix using hot-spraying technique.
Preferably, step（1）Described in metal dust be the conductive metal powder with high reproducibility, including copper powder, nickel
One or both of powder.
Preferably, step（1）Described in the mass ratio of metal dust and grading steel ball be 1:20~1:25, and grading steel ball
Grading be φ 25mm：φ55mm：φ75mm=2:3:5, the metal dust particle diameter is 5 ~ 10 microns.
Preferably, in step（2）In, based on quality percentage, the graphene oxide powder is step（1）Middle metal dust
1% ~ 10%, the dispersant be metal dust 0.01% ~ 0.1%.
Preferably, the dispersant is the surfactant containing conjugated bonds, including sodium alkyl benzene sulfonate, polyphenyl ethyl sulfonic acid
Sodium.
Preferably, the volume ratio of the hydrogen and argon gas is 5:95.
Preferably, the flow velocity of the argon gas and hydrogen is 2.3L/min ~ 15L/min.
Preferably, the t1For 2 ~ 3h, the t2For 1 ~ 2h, the t3For 5 ~ 30s.
Preferably, step（4）The hot-spraying technique includes flame-spraying, plasma spraying, laser spraying or electric arc
Spraying, the thickness of the metal-modified graphene composite powder coatings is 0.01 ~ 0.1mm.
Embodiment 1:
Sample 1：It is 5 microns of atomized copper powder end and grading steel ball by particle diameter（φ25：φ55：φ75=2:3:5）By matter
Amount ratio（1:20）It is put into ball grinder, fills up after absolute ethyl alcohol with the rotating speed wet-milling of 200r/min 2h for a period of time, form piece
Shape copper powder；Then by 1% graphene oxide powder and 0.01% polyphenyl ethyl sulfonic acid sodium, with the rotating speed wet-milling 2h of 400r/min
Afterwards, dried using vacuum drying chamber under the conditions of 80 DEG C, finely dispersed copper-modified graphene oxide composite powder is made；With
Suspended state thermal reduction calcining will be carried out in copper-modified graphene oxide powder composite powder input shower furnace afterwards, heat-treat temperature
It is set as 400 DEG C, and volume ratio is passed through as 95 using flow velocity 2.3L/min in shower furnace:5 argon gas and hydrogen, reaction time
For 30s, the graphene oxide being attached on flaky metal powder generates graphene, reaction knot in metal powder surface in-situ reducing
Beam, is cooled to room temperature, that is, obtains copper-modified graphene composite powder；Flame spraying process is finally used by copper-modified graphene
For composite powder coated on metallic matrix, it is 0.1mm to obtain copper-modified graphene composite powder coatings, measures its coating conductance
Rate is 86.5%IACS.
Embodiment 2:
Sample 2：It is 8 microns of atomized copper powder end and grading steel ball by particle diameter（φ25：φ55：φ75=2:3:5）By quality
Ratio（1:24）It is put into ball grinder, fills up after absolute ethyl alcohol with the rotating speed wet-milling of 350r/min 2.5h for a period of time, form piece
Shape copper powder；Then by 5% graphene oxide powder and 0.05% polyphenyl ethyl sulfonic acid sodium, with the rotating speed wet-milling 1.5h of 600r/min
Afterwards, dried using vacuum drying chamber under the conditions of 80 DEG C, finely dispersed copper-modified graphene oxide composite powder is made；With
Suspended state thermal reduction calcining will be carried out in copper-modified graphene oxide powder composite powder input shower furnace afterwards, heat-treat temperature
It is set as 600 DEG C, and volume ratio is passed through as 95 using flow velocity 4.6L/min in shower furnace:5 argon gas and hydrogen, reaction time
For 10s, the graphene oxide being attached on flaky metal powder generates graphene, reaction knot in metal powder surface in-situ reducing
Beam, is cooled to room temperature, that is, obtains copper-modified graphene composite powder；Flame spraying process is finally used by copper-modified graphene
For composite powder coated on metallic matrix, it is 0.05mm to obtain copper-modified graphene composite powder coatings, measures its coating conductance
Rate is 96.8%IACS.
Embodiment 3:
Sample 3：It is 10 microns of atomized copper powder end and grading steel ball by particle diameter（φ25：φ55：φ75=2:3:5）By matter
Amount ratio（1:25）It is put into ball grinder, fills up after absolute ethyl alcohol with the rotating speed wet-milling of 400r/min 3h for a period of time, form piece
Shape copper powder；Then by 10% graphene oxide powder and 0.1% polyphenyl ethyl sulfonic acid sodium, with the rotating speed wet-milling 2h of 800r/min
Afterwards, dried using vacuum drying chamber under the conditions of 80 DEG C, finely dispersed copper-modified graphene oxide composite powder is made；With
Suspended state thermal reduction calcining will be carried out in copper-modified graphene oxide powder composite powder input shower furnace afterwards, heat-treat temperature
It is set as 1000 DEG C, and volume ratio is passed through as 95 using flow velocity 9.4L/min in shower furnace:5 argon gas and hydrogen, during reaction
Between be 5s, be attached to graphene oxide on flaky metal powder and generate graphene, reaction in metal powder surface in-situ reducing
Terminate, be cooled to room temperature, that is, obtain copper-modified graphene composite powder；Flame spraying process is finally used by copper-modified graphite
For alkene composite powder coated on metallic matrix, it is 0.08mm to obtain copper-modified graphene composite powder coatings, measures its coating electricity
Conductance is 90.1%IACS.
Embodiment 4:
Sample 4：By the atomization nickel by powder and grading steel ball that particle diameter is 5 microns（φ25：φ55：φ75=2:3:5）By quality
Ratio（1:22）It is put into ball grinder, fills up after absolute ethyl alcohol with the rotating speed wet-milling of 400r/min 3h for a period of time, form sheet
Nickel powder；Then by 8% graphene oxide powder and 0.08% polyphenyl ethyl sulfonic acid sodium, after the rotating speed wet-milling 2h of 800r/min,
Dried using vacuum drying chamber under the conditions of 80 DEG C, finely dispersed nickel-modified graphene oxide composite powder is made；Then will
Suspended state thermal reduction calcining, thermal reduction temperature setting are carried out in nickel-modified graphene oxide powder composite powder input shower furnace
For 600 DEG C, and volume ratio is passed through as 95 using flow velocity 3.5L/min in shower furnace:5 argon gas and hydrogen, reaction time is
5s, the graphene oxide being attached on Nickel Powder reduce generation graphene in Nickel Powder surface in situ, and reaction terminates, and cools down
To room temperature, that is, obtain nickel-modified graphene composite powder；Flame spraying process is finally used by nickel-modified graphene composite powder
Coated on metallic matrix, it is 0.05mm to obtain nickel-modified graphene composite powder coatings, measures its coating electrical conductivity and is at end
83.1%IACS。
Embodiment 5:
Sample 3：By the atomization cupro-nickel powder that particle diameter is 5 microns（Mass ratio is 1:1）With grading steel ball（φ25：φ55：φ
75=2:3:5）Example in mass ratio（1:20）It is put into ball grinder, fills up after absolute ethyl alcohol with one section of the rotating speed wet-milling of 400r/min
Time 3h, forms sheet ambrose alloy powder；Then by 10% graphene oxide powder and 0.05% neopelex, with
After the rotating speed wet-milling 2h of 800r/min, dried using vacuum drying chamber under the conditions of 80 DEG C, finely dispersed cupro-nickel-modification is made
Graphene oxide composite powder；It will then suspend in cupro-nickel-modified graphene oxide powder composite powder input shower furnace
State thermal reduction calcining, thermal reduction temperature are set as 1000 DEG C, and in shower furnace using flow velocity 2.5L/min be passed through volume ratio as
95:5 argon gas and hydrogen, reaction time 5s, the graphene oxide being attached on Nickel Powder are former on sheet of copper nickel powder surface
Position reduction generation graphene, reaction terminate, are cooled to room temperature, that is, obtain cupro-nickel-modified graphene composite powder；Finally using fire
Nickel-modified graphene composite powder is coated on metallic matrix by flame spraying coating process, is obtained nickel-modified graphene composite powder and is applied
Layer is 0.01mm, and it is 102%IACS to measure its coating electrical conductivity.（The proportioning of cupro-nickel powder can be by people in the art in the present invention
Member is allocated according to the actual requirements, is described in detail so not adding.）
The flow velocity of the present invention for being passed through gas is determined according to sinking speed of the powder in shower furnace, the present invention
In, composite powder is blown into by inert gas above shower furnace, and the sinking speed of powder is to be based on particle sinking speed meter
Calculate what model obtained, belong to the conventional technical means of those skilled in the art's grasp, be described in detail so not adding, and to make powder in stove
In be in suspended state, then the gas flow rate being passed through should be greater than being equal to particle sinking speed, at the same to ensure particle be not easy by
Gas takes shower furnace out of, and those skilled in the art can select appropriate gas flow rate according to the actual requirements.
As shown in Fig. 1 ~ 3 be respectively embodiment 1,4,5 in copper-modified graphene composite powder scanned photograph, from Fig. 1
As can be seen that dispersed copper powder particles in graphene film, graphene is thicker for layer structure, there is a small amount of fold, but
Continuity is still kept, shows that graphene and copper metal particle combining case are good；From figure 2 it can be seen that in graphene film
Dispersed nickel by powder particle, but since graphene layer is grown in nickel particle surface in situ, based on nickel metallic particles
Intercalation, causes that graphene layer structure is thicker, and fold increases, and has a small amount of discontinuity；From figure 3, it can be seen that graphene layer
Between and surface be covered with cupro-nickel metallic particles, be evenly distributed, without agglomeration, and graphene surface is smooth, maintains good
Continuity.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or use the present invention.
Two kinds of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and the principles and novel features disclosed herein phase one
The most wide scope caused.
Claims (6)
- A kind of 1. preparation method of graphene/metal composite conductive coating, it is characterised in that：Comprise the following steps that：（1）Metal dust pre-processesAtomized metal pow der and grading steel ball are put into ball grinder in mass ratio, filled up after absolute ethyl alcohol with 200 ~ 400r/min Rotating speed wet-milling be t for a period of time1, form flaky metal powder；（2）It is prepared by metal-modified graphene oxide powderIn step（1）In ball grinder in by weight percent than adding graphene oxide powder and dispersant, with 400 ~ 800r/ The rotating speed wet-milling of min is t for a period of time2, then dried using vacuum drying chamber under the conditions of 80 DEG C, finely dispersed gold be made Category-modified graphene oxide powder；The dispersant is the surfactant containing conjugated bonds, is sodium alkyl benzene sulfonate or polyphenyl ethyl sulfonic acid sodium；（3）Suspended state heat-treats metal-modified graphene oxide powderBy step（2）Obtained metal-modified graphene oxide powder is put into progress suspended state thermal reduction in shower furnace, thermal reduction Temperature is set as 400 DEG C ~ 1000 DEG C, and in shower furnace with certain flow velocity be passed through certain volume than protective gas argon gas and Reducing gas hydrogen, reaction a period of time is t3, the graphene oxide on flaky metal powder is attached in metal powder surface In-situ reducing generates graphene, is cooled to room temperature after reaction, that is, obtains metal-modified graphene composite powder；The argon The flow velocity of gas and hydrogen is 2.3L/min ~ 15L/min；（4）It is prepared by metal-modified graphene composite powder coatingsMetal-modified graphene composite powder is sprayed on metallic matrix using hot-spraying technique；The t1For 2 ~ 3h, the t2For 1 ~ 2h, the t3For 5 ~ 30s.
- A kind of 2. preparation method of graphene/metal composite conductive coating according to claim 1, it is characterised in that step Suddenly（1）Described in metal dust be the conductive metal powder with high reproducibility, including one or both of copper powder, nickel powder.
- A kind of 3. preparation method of graphene/metal composite conductive coating according to claim 2, it is characterised in that step Suddenly（1）Described in the mass ratio of metal dust and grading steel ball be 1:20~1:25, and the grading of grading steel ball is φ 25mm：φ 55mm：φ75mm=2:3:5, the metal dust particle diameter is 5 ~ 10 microns.
- A kind of 4. preparation method of graphene/metal composite conductive coating according to claim 3, it is characterised in that Step（2）In, based on quality percentage, the graphene oxide powder is step（1）The 1% ~ 10% of middle metal dust, it is described scattered Agent is the 0.01% ~ 0.1% of metal dust.
- A kind of 5. preparation method of graphene/metal composite conductive coating according to claim 4, it is characterised in that institute The volume ratio for stating hydrogen and argon gas is 5:95.
- 6. according to a kind of preparation method of graphene of claim 1 ~ 5 any one of them/metal composite conductive coating, its feature It is, step（4）The hot-spraying technique includes flame-spraying, plasma spraying, laser spraying or electric arc spraying, the gold The thickness of category-modified graphene composite powder coatings is 0.01 ~ 0.1mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710697354.XA CN107460423B (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of graphene/metal composite conductive coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710697354.XA CN107460423B (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of graphene/metal composite conductive coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107460423A CN107460423A (en) | 2017-12-12 |
| CN107460423B true CN107460423B (en) | 2018-05-04 |
Family
ID=60549759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710697354.XA Active CN107460423B (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of graphene/metal composite conductive coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107460423B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108504976B (en) * | 2018-04-10 | 2020-08-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of metal-graphene composite coating |
| CN110386831B (en) * | 2018-04-18 | 2021-09-10 | 中南大学 | Graphite mold with hardened wear-resistant layer and preparation method and application thereof |
| CN108515185A (en) * | 2018-04-25 | 2018-09-11 | 北方工业大学 | Graphene coated flake metal powder material and preparation method thereof |
| CN108866469A (en) * | 2018-07-27 | 2018-11-23 | 合肥岑遥新材料科技有限公司 | A kind of metal matrix ceramic composites for furnace roller thermal spraying on surface |
| CN109207984B (en) * | 2018-08-20 | 2020-10-16 | 中国科学院金属研究所 | Preparation method of corrosion-resistant antibacterial anti-biological fouling multifunctional metal-based protective coating |
| CN109778105A (en) * | 2019-03-07 | 2019-05-21 | 上海海洋大学 | A kind of amorphous composite coating and preparation method thereof |
| CN111139424B (en) * | 2019-12-31 | 2021-08-27 | 陕西斯瑞新材料股份有限公司 | Stainless steel wet hydrogen preparation method for improving thermal emissivity and application |
| EP3854502A1 (en) * | 2020-01-23 | 2021-07-28 | ABB Schweiz AG | A composite and method of preparation thereof |
| CN112139512B (en) * | 2020-08-25 | 2021-12-21 | 湖南大学 | Preparation method of copper-based composite material precursor powder |
| CN112570242A (en) * | 2020-12-17 | 2021-03-30 | 中国科学院宁波材料技术与工程研究所 | Design method of electric field assisted cold spraying equipment |
| CN112646470A (en) * | 2020-12-17 | 2021-04-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method of electric field assisted cold spraying graphene-based coating |
| CN112993084A (en) * | 2021-02-04 | 2021-06-18 | 合肥工业大学 | Preparation method of Ag-rGO film with excellent photoelectric property |
| CN113150599A (en) * | 2021-03-26 | 2021-07-23 | 杭州安誉科技有限公司 | High-thermal-conductivity PCR reaction tube and preparation process thereof |
| CN112938944B (en) * | 2021-04-09 | 2023-09-12 | 常州富烯科技股份有限公司 | Preparation method of graphene film |
| CN115558379B (en) * | 2022-10-31 | 2023-09-15 | 广东宝伯力新材料科技有限公司 | Preparation method of carbon steel polyurethane terrace |
| CN115652244B (en) * | 2022-12-26 | 2023-04-18 | 广州市尤特新材料有限公司 | Rotary silicon-phosphorus alloy target material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
| CN102719693A (en) * | 2012-06-11 | 2012-10-10 | 上海交通大学 | Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof |
| CN102917981A (en) * | 2010-05-14 | 2013-02-06 | 巴斯夫欧洲公司 | Method for encapsulating metals and metal oxides with graphene and use of said materials |
| CN104711443A (en) * | 2015-03-18 | 2015-06-17 | 上海和伍新材料科技有限公司 | Graphene/copper composite and preparation method thereof |
| CN105838913A (en) * | 2016-04-08 | 2016-08-10 | 上海和伍复合材料有限公司 | Graphene/nickel composite material and preparation method thereof |
| CN106591822A (en) * | 2016-11-28 | 2017-04-26 | 广东工业大学 | Preparation method and application of graphene strengthened copper base composite coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102528068B (en) * | 2012-01-16 | 2014-07-30 | 中国科学院过程工程研究所 | Device and method for preparing superfine nickel powder |
| CN102965664A (en) * | 2012-11-27 | 2013-03-13 | 大连理工大学 | Graphene-reinforced nickel-based composite coating material and laser cladding technology thereof |
-
2017
- 2017-08-15 CN CN201710697354.XA patent/CN107460423B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102917981A (en) * | 2010-05-14 | 2013-02-06 | 巴斯夫欧洲公司 | Method for encapsulating metals and metal oxides with graphene and use of said materials |
| CN102329976A (en) * | 2011-09-06 | 2012-01-25 | 上海交通大学 | Preparation method of graphene reinforced metal-matrix composite |
| CN102719693A (en) * | 2012-06-11 | 2012-10-10 | 上海交通大学 | Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof |
| CN104711443A (en) * | 2015-03-18 | 2015-06-17 | 上海和伍新材料科技有限公司 | Graphene/copper composite and preparation method thereof |
| CN105838913A (en) * | 2016-04-08 | 2016-08-10 | 上海和伍复合材料有限公司 | Graphene/nickel composite material and preparation method thereof |
| CN106591822A (en) * | 2016-11-28 | 2017-04-26 | 广东工业大学 | Preparation method and application of graphene strengthened copper base composite coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107460423A (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107460423B (en) | A kind of preparation method of graphene/metal composite conductive coating | |
| CN105209178B (en) | Ternary ceramics hot spray powder and painting method | |
| CN105951094B (en) | A kind of method that laser melting coating prepares carbon nanotubes enhancing coating | |
| Wang et al. | Laser surface remelting of plasma sprayed nanostructured Al2O3–13wt% TiO2 coatings on titanium alloy | |
| CN107354421B (en) | A kind of preparation method of graphene-copper-amorphous composite coating | |
| CN101838807B (en) | Laser cladding coating material for inlet valve and exhaust valve of engine and coating thereof | |
| CN109014179A (en) | A kind of preparation method and product of 3 D-printing spherical metal base nano ceramic composite material | |
| CN102828137A (en) | High-temperature alloy surface nanometer composite coating and preparation method thereof | |
| CN104162662A (en) | Surface modified amorphous alloy powder, manufacturing method and coating manufactured through surface modified amorphous alloy powder | |
| CN110202133A (en) | A kind of nano aluminum oxide dispersion strengthens the preparation method and application of copper-based composite powder | |
| Li et al. | Achieving in-situ alloy-hardening core-shell structured carbonyl iron powders for magnetic abrasive finishing | |
| CN107881500A (en) | A kind of high-strength wearable shock resistance and high adhesion force coating material and preparation method thereof | |
| CN102162079A (en) | Low-oxygen-content high-yield spherical aluminum bronze alloy powder for thermal spraying and preparation method thereof | |
| CN104630688B (en) | A kind of method for preparing Thermal Barrier Coatings | |
| CN102127729B (en) | Soldering strengthening method for thermal sprayed coating on surface of metal material | |
| CN106835120B (en) | A kind of austenitic stainless steel self-lubricating abrasion-resistant anti-corrosion coating | |
| CN113278960B (en) | Novel plasma surfacing Fe-Mo 2 FeB 2 Method for producing a transition layer | |
| CN103817341B (en) | A kind of preparation method of high heat release nickel-based composite pow-der | |
| CN111378964A (en) | Method for preparing carbon nanotube reinforced coating by supersonic laser deposition | |
| CN105734480B (en) | Method for improving corrosion resistance of lead-cooled neutron reactor structural component | |
| CN113953533B (en) | Method for printing copper-based composite coating by selective laser melting of metal nano powder ink | |
| KR100797827B1 (en) | Method of coating on carbon fiber-epoxy composite | |
| JPS6191323A (en) | Formation of particle-dispersed surface coating layer | |
| CN106521482B (en) | A kind of ceramic coating and preparation method thereof using laminar flow plasma | |
| CN110280773A (en) | A kind of preparation method of low-temperature self-propagating composite material |
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 |