CN106744857B - 3D printing graphene-metallic composite, preparation method and application - Google Patents
3D printing graphene-metallic composite, preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of 3D printing graphene-metallic composites, preparation method and application.The preparation method is as follows: graphene quantum dot and/or graphene microchip and nano metal simple substance/nano metal chemical combination object are carried out mixed grinding shearing under ultrasonication by (1), composite slurry material or composite powder material is made, the frequency of ultrasound is 10-100KHz, and wherein the weight of graphene quantum dot and/or graphene microchip accounts for the 0.01%-35% of gross weight；(2) composite slurry material obtained or powder body material are dried.The invention provides laser sintered graphene metallics composite material and preparation method for 3D printing, obtained composite material has high rigidity, high intensity, corrosion-resistant, easily it is processed the superior function used, using laser sintered, quenching after 3D printing, promote composite material granular densification, and crystal grain is refined, so as to improve the mechanical performance of 3D printing product.
Description
Technical field
The present invention relates to graphene applied technical field, in particular to a kind of 3D printing graphene-metallic composite, system
Preparation Method and application.
Background technique
Single-layer graphene film is made of one layer of intensive carbon hexatomic ring, without any fault of construction, it with a thickness of
0.35nm or so is two-dimensional nano-carbon material most thin so far.Meanwhile it is also form other carbon group materials substantially single
Member can obtain the fullerene of zero dimension by warpage, curling obtains one-dimensional carbon nanotube and stacking and obtains three-dimensional graphite.Stone
Most basic repetition period unit is phenyl ring knot ditch the most stable in organic chemistry in black alkene, it be it is current until best two
Dimension nano material.There is only single layers for the graphene prepared in reality, also there is multilayer.Due to its unique structure, graphene
Various types of properties it is also very excellent.It is that most thin most light substance, the most thin reachable 0.34nm of thickness, specific surface area are in the world
2630m2/g, carrier mobility at room temperature are about 200,000 (cm2/ vs), it is known that one of highest material of intensity compares diamond
It is also hard, taller upper 100 times of the intensity steel more best than in the world.It possesses good toughness again simultaneously, and can be bent,
The theoretical Young's modulus of ideal graphite alkene reaches 1.0TPa, breaking strength 130GPa.Thermal coefficient is up to 5000W/mK, is current
Until it is highest.
Currently, researchers at home and abroad modify application aspect and have carried out more research, as in the compound of grapheme material
State's number of patent application: CN201610825355.3 discloses a kind of preparation method of nickel oxide/graphene oxide composite material, it
In order to solve that the existing metal oxide particle prepared in metal oxide/graphene composite material is big and partial size it is uneven and
The lower problem of specific capacitance.Chinese Patent Application No.: CN201610821003.0 discloses a kind of FeOOH/oxidation stone
The preparation method and applications of black alkene composite material.Iron oxyhydroxide/graphenoxide oxide composite material is by graphene oxide
The suspension of suspension and FeOOH is combined after according to volume ratio 1:1~2 mixing, dispersion by hydro-thermal method.In
State's number of patent application: CN201610804294.2 discloses a kind of preparation method of LiFePO4/graphene composite material.It should
Method mainly include by waste lithium iron phosphate battery positive plate by organic solvent immersion, ultrasonication, ball milling, roast, quench
Fire, with conductive black is baking mixed obtains LiFePO 4 material；Then it is molten natural flake graphite and sodium nitrate to be added to sulfuric acid
In liquid, graphene oxide is obtained by oxidations such as potassium permanganate；Finally obtained LiFePO 4 material and graphene oxide are mixed
It closes, using n-methyl-2-pyrrolidone as dispersing agent, ball milling is up to LiFePO4/graphene composite material.Chinese patent application
Number: CN201610768001.X discloses preparation method, the lithium-ion electric of a kind of stannic disulfide/graphene nanocomposite material
Pond cathode, lithium ion battery, preparation method step include hydro-thermal process, compound working procedure, and preparation method of the present invention makes curing
Tin directly carries out growth in situ on the surface of graphene, dry to obtain sheet stannic disulfide/graphene composite material by washing,
The material is applied to lithium ion battery negative material, effectively improves the stability and electric conductivity of material, promotes battery performance,
Has many advantages, such as good cycling stability, specific energy density is high.Chinese Patent Application No.: CN201610763257.1 discloses one
The preparation method of kind sesquioxide/graphene composite material, negative electrode of lithium ion battery, lithium ion battery, preparation method step
Including hydro-thermal process, compound working procedure, preparation method of the present invention makes di-iron trioxide nano particle uniform load in three-dimensional graphite
In the surface and cellular structure of alkene, dry to obtain sesquioxide/graphene composite material by washing, which is applied to
Lithium ion battery, have high capacity, have extended cycle life, low cost and easily large-scale production etc. excellent properties.Chinese patent Shen
Please number: CN201610764913.X discloses preparation method, the lithium-ion electric of a kind of manganese sulfide/graphene nanocomposite material
Pond cathode, lithium ion battery, preparation method step include hydro-thermal process, compound working procedure, and preparation method of the present invention makes manganese sulfide
Growth in situ is directly carried out on the surface of graphene, and dry to obtain manganese sulfide/graphene composite material by washing, the present invention is logical
Over cure manganese and three-dimensional redox graphene is compound the disadvantages of overcoming stability caused by its volume change poor, enhances it and lead
Electrically, to improve the performance of lithium ion battery, which is applied to lithium ion battery negative material, there is cyclical stability
Well, the advantages that specific energy density is high.Chinese Patent Application No.: CN201610748848.1 is related to a kind of porous with hierarchy
Molybdenum disulfide/the graphene composite material and its synthetic method of tiny balloon shape structure, belong to Micron-nano composites preparation with
The technical field of synthesis.It with big specific capacitance and excellent is followed when the composite material is used as electrode material for super capacitor
Ring stable charge/discharge illustrates wide application prospect.Chinese Patent Application No.: CN201610594377.3 is disclosed
A kind of to load the preparation method for having the fluorinated graphene composite material of nano silver, obtained composite material has excellent performance.In
State's number of patent application: a kind of manganese cobalt sulfide/graphene composite material preparation process of electrochemical performance, the preparation process
Middle electrochemical deposition uses three-electrode system, and working electrode is three-dimensional graphene foam, is platinized platinum to electrode, and reference electrode is
Ag/AgCl normal electrode.This technological operation is easy, and the structure of matter of preparation is stablized, and changing parameter can change the pattern of substance,
And then the chemical property of material is promoted, it can be used for large area and prepare electrode material.
In conclusion although by graphene and its composite material and technical application to more multi-field, and obtain performance improvement
And promotion, but the graphene with hard high-strength is due to interfacial energy height, intermolecular active force and chemical bond work
Reunion is necessarily easy to happen with strong.Therefore, since lamination and reunion occurs when being prepared into graphene composite material, no
The high rigidity of grapheme material, the performance advantage of high intensity and high thermal conductivity can be fully demonstrated, this problem limits it bigger
The application of range, broader field.
Summary of the invention
Present invention aims to solve the deficiencies of the prior art, and provides a kind of a kind of 3D printing graphene-metallic composites
Preparation method.3D printing graphene-metallic composite that the present invention is prepared has high rigidity, high intensity, resistivity low,
It is easily processed the superior function used, can be widely applied to the field of material processings such as dental implant, super electric drill；It is battery, super
Capacitor energy storage material field；Catalyst material field；Heat sink material field；Medical domain；Coating material field；Conductive oil
Ink；Photoelectricity, sensor material field；Biological related fields etc..
The present invention is achieved by the following technical solutions:
3D printing graphene-metallic composite preparation method, it is characterised in that include the following steps:
(1) by graphene quantum dot and/or graphene microchip and nano metal simple substance/Nanometallization under ultrasonication
It closes object and carries out mixed grinding shearing, composite slurry material or composite powder material is made, the ultrasonication is by ultrasonic head, ultrasound
Device or Vltrasonic device generate, and ultrasonic frequency is 10-100KHz, wherein the weight of graphene quantum dot and/or graphene microchip
Account for the 0.01%-35% of mixture total weight；
(2) composite slurry material obtained or powder body material are dried, obtain 3D printing graphene-Metals composite
Material.
Further, the nano metal simple substance be nanoscale zirconium, titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminium,
One or more of iron, cobalt, chromium, manganese, tin, iridium, ruthenium, indium, lanthanide series metal.
Further, the nano metal chemical combination object be zirconium oxide, molybdenum disulfide, tungsten disulfide, lead oxide, vulcanized lead,
Nickel hydroxide, nickel oxide, nickel phosphide, copper oxide, silver oxide, palladium chloride, zinc oxide, aluminium oxide, iron oxide, iron phosphide, vulcanization
Cobalt, lead sulfate, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferric metasilicate lithium, titanium
Sour lithium, cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, cadmium hydroxide,
Cadmium sulfide, chromium oxide, manganese oxide, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yttrium oxide, zirconium oxide, zirconium silicate, yttrium oxide,
One of iridium chloride, iridium complex, silver oxide, ruthenium-oxide, bismuth ruthenate, ruthenic acid lead, scandium oxide, indium oxide, magnesia are several
Kind.
Further, the mixed grinding shearing of step (1) refer specifically to mixture under solid phase or liquid-phase condition into
The shearing of row physical grinding.
As an implementation, the mixed grinding shearing of step (1) is specifically to carry out mixture under solid phase conditions
Physical grinding shearing, it is preferable that grinding pressure 1-200MPa, milling time 1-24h.Solid phase mixing under condition of high voltage is ground
It grinds scissors and cuts, not only make mixture dispersion, mixing more evenly, improve the uniformity of its dispersion mixing, more effectively reach prevention
The stacking and reunion of graphene quantum dot and/or graphene microchip, conducive to the compound action and enhancing of graphene and metallics
Binding force.
As another embodiment, step (1) mixed grinding shearing be specifically by mixture under liquid-phase condition into
Row physical grinding shearing, it is preferable that grinding pressure 1-250MPa, milling time 1-12h, temperature are 2-18 DEG C, the liquid
Phase condition be water, ethyl alcohol, acetone, polyethylene glycol, polyvinyl alcohol, formamide, N-Methyl pyrrolidone, acetonitrile, methanol, propyl alcohol,
Acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, ethyl acetate, ether, isopropyl ether, methylene chloride, chloroform, bromine second
The combination of one of alkane, benzene, carbon tetrachloride, carbon disulfide, hexamethylene, hexane, kerosene or a variety of solvents to dissolve each other.High pressure
Under the conditions of the shearing of liquid phase physical grinding, similarly can reach the effect of above-mentioned solid phase mixed grinding shearing, can also prevent under low temperature
Violent Brownian movement generation is reunited again when only there is high temperature.Preferably, temperature is 4-6 DEG C.
Further, the drying means of step (2) is atmosphere pressure desiccation, low pressure seasoning, boulton process, supercritical drying
One of dry method or spray drying process, drying temperature are 30-1000 DEG C, drying time 10-600min.
The present invention also provides a kind of 3D printing graphene-metallic composites, which is characterized in that by above-mentioned preparation method
It obtains.
The present invention also provides a kind of applications of 3D printing graphene-metallic composite, which is characterized in that beats the 3D
Graphene-metallic composite is printed after 3D printing, is sintered using laser system, quenching, laser frequency 30-
800kHz, laser power 30-180W, spot diameter 0.1-2mm, scanning speed 0.2-5mm/s, sweep span 0.1-
1.0mm obtains laser sintered 3D printing product.
The beneficial effects of the present invention are:
3D printing graphene-metallic composite preparation method through the invention, so that graphene avoids when applying
Lamination and reunion, and 3D printing graphene prepared by the present invention answers metallics composite material have high rigidity, high intensity, resistance to
Burn into shock resistance, resistivity are low, are easily processed the superior function used, using laser sintered, quenching after 3D printing, promote
It is densified into composite material granular, and refines crystal grain, mechanical performance, electric property, calorifics so as to improve 3D printing product
Energy.It can be widely applied to the field of material processings such as dental implant, super electric drill；Battery, ultracapacitor energy storage Material Field；It urges
Agent Material Field；Heat sink material field；Medical domain；Coating material field；Electrically conductive ink；Photoelectricity, sensor material field；
Biological related fields etc..
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
3D printing graphene-the metallic composite of the present embodiment, preparation method include the following steps:
(1) under ultrasonic probe effect (ultrasonic frequency be 10KHz) by graphene quantum dot and nano zirconium oxide powder
It being mixed with the mass ratio of 1:19, mixture is ground as solvent high-pressure physics using polyethylene glycol and is sheared, pressure 250MPa, when
Between be 1h, temperature be 2 DEG C, be made composite slurry material；
(2) composite slurry material obtained is dried in vacuo, pressure 150Pa, drying time 60min, it is dry
Temperature is 30 DEG C, obtains 3D printing graphene-metallic composite.
In other embodiments, graphene quantum dot can also use graphene microchip or graphene quantum dot and graphene
The mixture of microplate replaces；Vacuum drying pressure can be within the scope of 150-1000Pa, drying time 5-60min.
Embodiment 2
3D printing graphene-metallic composite application method of embodiment 1 is: 3D printing graphene-metal is multiple
Condensation material is sintered, quenching after 3D printing using fiber laser system, laser frequency 70kHz, and laser power is
100W, spot diameter 0.2mm, scanning speed 0.5mm/s, sweep span 0.7mm obtain laser sintered 3D printing product.
Embodiment 3
3D printing graphene-the metallic composite of the present embodiment, preparation method include the following steps:
(1) under ultrasound reactor effect (ultrasonic frequency be 100KHz) by graphene microchip and nano-titanium dioxide
Powder is mixed with the mass ratio of 1:25, is used ball mill pure water to grind for solvent high-pressure physics and is sheared, pressure 180MPa,
Time is 12h, and temperature is 18 DEG C, and composite slurry material is made；
(2) composite slurry material obtained being subjected to constant pressure and dry, drying time 200min, drying temperature is 80 DEG C,
Obtain 3D printing graphene-metallic composite.
In other embodiments, the drying time of constant pressure and dry can be in 100-500min, and drying temperature is at 50-120 DEG C
In range.
Embodiment 4
3D printing graphene-metallic composite application method of embodiment 3 is: 3D printing graphene-metal is multiple
Condensation material is sintered, quenching after 3D printing using argon laser system, laser frequency 200kHz, and laser power is
180W, spot diameter 0.1mm, scanning speed 0.5mm/s, sweep span 0.9mm obtain laser sintered 3D printing product.
Embodiment 5
3D printing graphene-the metallic composite of the present embodiment, preparation method include the following steps:
(1) (ultrasonic frequency is 50KHz) mixes graphene microchip and nano zirconium oxide powder under ultrasonic probe effect
It closes, wherein graphene microchip weight accounts for the 0.01% of gross weight, and it is ground and is sheared as solvent high-pressure physics using pure water, pressure 1MPa,
Time is 6h, and temperature is 4~6 DEG C, and composite powder material is made；
(2) composite slurry material obtained being spray-dried, drying time 45min, drying temperature is 1000 DEG C,
Obtain anhydrous composite powder material.
In other embodiments, nano zircite can use nanoscale molybdenum disulfide, tungsten disulfide, lead oxide, vulcanization
Lead, nickel hydroxide, nickel oxide, nickel phosphide, copper oxide, silver oxide, palladium chloride, zinc oxide, aluminium oxide, iron oxide, iron phosphide, sulphur
Change cobalt, lead sulfate, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferric metasilicate lithium,
Lithium titanate, cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, hydroxide
Cadmium, cadmium sulfide, chromium oxide, manganese oxide, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yttrium oxide, zirconium oxide, zirconium silicate, oxidation
One of iridium, iridium chloride, iridium complex, silver oxide, ruthenium-oxide, bismuth ruthenate, ruthenic acid lead, scandium oxide, indium oxide, magnesia or
It is several to replace；The drying time of spray drying can be within the scope of 30-100min.
Embodiment 6
3D printing graphene-metallic composite application method of embodiment 5 is: 3D printing graphene-metal is multiple
Condensation material is sintered, quenching after 3D printing using carbon dioxide laser system, laser frequency 87kHz, and laser power is
150W, spot diameter 0.2mm, scanning speed 0.2mm/s, sweep span 0.2mm obtain laser sintered 3D printing product.
Embodiment 7
3D printing graphene-the metallic composite of the present embodiment, preparation method include the following steps:
(1) graphene microchip is mixed with nanometer zirconium metal powder under ultrasonic probe effect, wherein graphene is micro-
Piece accounts for the 20% of mixture total weight, is sheared using solid phase physics polishing high pressure abrasive, pressure 1MPa, time 1h, is made
Composite powder material；
(2) composite slurry material obtained is subjected to supercritical drying, pressure 5000Pa, temperature is 35 DEG C, when dry
Between be 600min, obtain 3D printing graphene-metallic composite.
In other embodiments, nanometer zirconium metal powder can also by nanoscale titanium, lead, nickel, copper, silver, molybdenum, gold, palladium,
One or more of zinc, aluminium, iron, cobalt, chromium, manganese, tin, iridium, ruthenium, indium, lanthanide series metal replace；The pressure of supercritical drying can be with
Within the scope of 5000-10000Pa, temperature is 30-80 DEG C, drying time 100-500min.
Embodiment 8
3D printing graphene-metallic composite application method of embodiment 7 is: 3D printing graphene-metal is multiple
Condensation material is sintered, quenching after 3D printing using carbon dioxide laser system, laser frequency 30kHz, and laser power is
30W, spot diameter 2mm, scanning speed 5mm/s, sweep span 1mm obtain laser sintered 3D printing product.
Embodiment 9
3D printing graphene-the metallic composite of the present embodiment, preparation method include the following steps:
(1) (ultrasonic frequency is 100KHz) by graphene quantum dot, graphene microchip and is received under ultrasonic probe effect
Rice molybdenum disulfide powder is mixed, and wherein the gross weight of graphene quantum dot and graphene microchip accounts for the 35% of mixture total weight,
Mixture is subjected to high pressure abrasive shearing, pressure 200MPa under solid phase conditions, the time is for 24 hours, composite powder material to be made；
(2) composite slurry material obtained is subjected to supercritical drying, pressure 10000Pa, temperature is 80 DEG C, when dry
Between be 10min, obtain 3D printing graphene-metallic composite.
In other embodiments, nano molybdenum disulfide powder can also be by nanoscale zirconium oxide, tungsten disulfide, oxidation
Lead, vulcanized lead, nickel hydroxide, nickel oxide, nickel phosphide, copper oxide, silver oxide, palladium chloride, zinc oxide, aluminium oxide, iron oxide, phosphorus
Change iron, cobalt sulfide, lead sulfate, LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, silicon
Sour iron lithium, lithium titanate, cobalt acid lithium, LiMn2O4, nickel ion doped, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide,
Cadmium hydroxide, cadmium sulfide, chromium oxide, manganese oxide, tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yttrium oxide, zirconium oxide, silicic acid
Zirconium, yttrium oxide, iridium chloride, iridium complex, silver oxide, ruthenium-oxide, bismuth ruthenate, ruthenic acid lead, scandium oxide, indium oxide, in magnesia
One or more replace.
Embodiment 10
3D printing graphene-metallic composite application method of embodiment 9 is: 3D printing graphene-metal is multiple
Condensation material is sintered, quenching after 3D printing using argon laser system, laser frequency 800kHz, and laser power is
100W, spot diameter 1mm, scanning speed 3mm/s, sweep span 0.1mm obtain laser sintered 3D printing product.
The invention is not limited to above embodiment, if not departing from the present invention to various changes or deformation of the invention
Spirit and scope, if these changes and deformation belong within the scope of claim and equivalent technologies of the invention, then this hair
It is bright to be also intended to encompass these changes and deformation.
Claims (7)
1.3D prints graphene-metallic composite preparation method, it is characterised in that includes the following steps:
(1) by graphene quantum dot and/or graphene microchip and nano metal simple substance/nano metal chemical combination object under ultrasonication
Carry out mixed grinding shearing, be made composite slurry material or composite powder material, the mixed grinding shearing refer specifically to by
Mixture carries out physical grinding shearing under solid phase or liquid-phase condition, cuts when mixture carries out physical grinding under solid phase conditions
It cuts, grinding pressure 1-200MPa, milling time 1-24h, when mixture carries out physical grinding shearing under liquid-phase condition, grinds
Mill pressure is 1-250MPa, and milling time 1-12h, temperature is 2-18 DEG C, and the ultrasonication is by ultrasonic head, ultrasonic device or surpasses
Acoustic device generates, and ultrasonic frequency is 10-100KHz, and wherein the weight of graphene quantum dot and/or graphene microchip accounts for mixing
The 0.01%-35% of object gross weight；
(2) composite slurry material obtained or powder body material are dried, obtain 3D printing graphene-metallic composite.
2. the preparation method of 3D printing graphene-metallic composite according to claim 1, it is characterised in that: described
Nano metal simple substance be nanoscale zirconium, titanium, lead, nickel, copper, silver, molybdenum, gold, palladium, zinc, aluminium, iron, cobalt, chromium, manganese, tin, iridium, ruthenium,
One or more of indium, lanthanide series metal.
3. the preparation method of 3D printing graphene-metallic composite according to claim 1, it is characterised in that: described
Nano metal chemical combination object is zirconium oxide, molybdenum disulfide, tungsten disulfide, lead oxide, vulcanized lead, nickel hydroxide, nickel oxide, phosphatization
Nickel, copper oxide, silver oxide, palladium chloride, zinc oxide, aluminium oxide, iron oxide, iron phosphide, cobalt sulfide, lead sulfate, LiFePO4, phosphorus
Sour manganese lithium, phosphoric acid vanadium lithium, vanadium phosphate sodium, lithium ferric manganese phosphate, manganese silicate of lithium, ferric metasilicate lithium, lithium titanate, cobalt acid lithium, LiMn2O4, nickel
LiMn2O4, nickle cobalt lithium manganate, cobalt oxide, titanium oxide, titanium boride, vanadium oxide, cadmium hydroxide, cadmium sulfide, chromium oxide, manganese oxide,
Tin oxide, antimony oxide, tungsten oxide, bismuth oxide, yttrium oxide, zirconium oxide, zirconium silicate, yttrium oxide, iridium chloride, iridium complex, oxidation
One or more of silver, ruthenium-oxide, bismuth ruthenate, ruthenic acid lead, scandium oxide, indium oxide, magnesia.
4. the preparation method of 3D printing graphene-metallic composite according to claim 1, it is characterised in that: step
(1) liquid-phase condition is water, ethyl alcohol, acetone, polyethylene glycol, polyvinyl alcohol, formamide, N-Methyl pyrrolidone, acetonitrile, first
Alcohol, propyl alcohol, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, ethyl acetate, ether, isopropyl ether, methylene chloride, chlorine
The group of one of imitative, bromoethane, benzene, carbon tetrachloride, carbon disulfide, hexamethylene, hexane, kerosene or a variety of solvents to dissolve each other
It closes.
5. the preparation method of 3D printing graphene-metallic composite according to claim 1, it is characterised in that: step
(2) drying means is in atmosphere pressure desiccation, low pressure seasoning, boulton process, supercritical drying or spray drying process
One kind, drying temperature are 30-1000 DEG C, drying time 10-600min.
6.3D prints graphene-metallic composite, which is characterized in that is obtained by any preparation method of Claims 1 to 5
It arrives.
7.3D prints the application of graphene-metallic composite, which is characterized in that by 3D printing graphene-described in claim 6
Metallic composite is sintered, quenching after 3D printing using laser system, laser frequency 30-800kHz, laser power
For 30-180W, spot diameter 0.1-2mm, scanning speed 0.2-5mm/s, sweep span 0.1-1.0mm, laser burning is obtained
Tie 3D printing product.
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| KR102456578B1 (en) * | 2017-07-14 | 2022-10-20 | 삼성전자주식회사 | Hardmask composition, method of manufacturing the same and method of forming patterned layer using hardmask composition |
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