CN105837214A - Preparation method of graphene product - Google Patents
Preparation method of graphene product Download PDFInfo
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- CN105837214A CN105837214A CN201610164587.9A CN201610164587A CN105837214A CN 105837214 A CN105837214 A CN 105837214A CN 201610164587 A CN201610164587 A CN 201610164587A CN 105837214 A CN105837214 A CN 105837214A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
Abstract
The invention discloses a preparation method of a graphene product. The method comprises the steps of: mixing graphene powder with SiC powder, adding the mixed powder into an organic solvent and dispersing the mixed powder uniformly to obtain a supersaturated graphene dispersion liquid slurry; mixing the supersaturated graphene dispersion liquid slurry with an organic adhesive uniformly under a dark condition to obtain a mixed slurry; loading the mixed slurry into 3D printing forming equipment, utilizing controllable ultraviolet beam, adopting a surface exposure or spot scanning mode to conduct layer-by-layer printing according to a three-dimensional model of a part so as to obtain a graphene product rough blank; and subjecting the graphene product rough blank to low temperature degreasing treatment and hot isostatic pressure treatment so as to obtain a compact graphene product. The method provided by the invention utilizes photocuring rapid forming principle, the shape of the graphene product is not restricted, the preparation method is convenient and rapid, and the product compactness is good, thus filling the blank of graphene product preparation on the market.
Description
Technical field
The invention belongs to technical field of material, be specifically related to the preparation method of a kind of graphene product.
Background technology
Graphene is the thinnest material, is also the most tough material, and fracture strength is than best steel also
Want high 200 times.It has again good elasticity simultaneously, and stretch range can reach the 20% of own dimensions.It
It it is the material that current nature is the thinnest, intensity is the highest.The current most potential application of Graphene is to become silicon
Succedaneum, manufacture superminiature transistor, be used for produce future supercomputer.Replace with Graphene
Silicon, the speed of service of computer processor will hundreds times soon.It addition, Graphene is the most fully transparent
, only absorb the light of 2.3%.These features make it be highly suitable as the raw material of transparent electron product,
Such as transparent touch display screen, luminous plaque and solar panel.
Manufacture method currently for graphene product is seldom seen in document, and major part is about Graphene
Application also rests on laboratory stage, lacks a kind of can preparing easily and fast and has high-compactness
The method of variously-shaped graphene product.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of graphene product, solve and there is no one at present
Preparation method can prepare the asking of variously-shaped graphene product with high-compactness easily and fast
Topic.
The technical solution adopted in the present invention is, the preparation method of a kind of graphene product, including following step
Rapid:
Step 1, preparation of raw material
Graphene powder is mixed with SiC powder, mixed-powder is added organic solvent, utilize ultrasound wave
Mixed-powder is made to be uniformly dispersed in organic solvent, it is thus achieved that supersaturation graphene dispersing solution slurry;Will satiety
Uniformly mix under the conditions of lucifuge with organic adhesive with graphene dispersing solution slurry, obtain mixed slurry.
Step 2, crude green body manufacture
Mixed slurry is loaded in 3D printing formation unit, utilize controllable UV Line beam, use face exposure
Or the mode of spot scan, successively print according to three-dimensional part model, make graphene product crude green body.
Step 3, post processing
Graphene product crude green body is carried out low-temperature defatted process, makes the organic adhesive evaporation in crude green body overflow;
Carry out hip treatment again, it is thus achieved that fine and close graphene product.
The feature of the present invention also resides in:
Preferably, the addition of SiC powder is the 0.1~1% of mixed-powder cumulative volume.
Preferably, organic solvent is NN-dimethylformamide, N-Methyl pyrrolidone or oxolane.
Preferably, organic adhesive is epoxy acrylic resin, urethane acrylate, polyester acrylic
One of ester, polyester acrylate resin or amino acrylic resin.
Preferably, every 10mL organic solvent adds 2mg~20mg mixed-powder, supersaturation Graphene
Dispersion liquid slurry is 3:2~3:7 with the volume ratio of organic adhesive.
Preferably, the layer thickness control successively printed is in 20~80 μm, and optical source wavelength is 200~400nm.
Preferably, when using face exposure, time of exposure is 0.1-3s;When using spot scan, spot diameter is
0.1~0.15mm, hot spot translational speed 1-300mm/min.
Preferably, the temperature of low-temperature defatted process 100 DEG C~800 DEG C, time 1-2h.
Preferably, hip treatment temperature 1000 DEG C~1350 DEG C, pressure 100MPa~200MPa,
Time 0.2-3h.
The invention has the beneficial effects as follows, the present invention uses 3D printing technique to manufacture graphene product, it is possible to side
Just the problem, quickly preparing the variously-shaped graphene product with high-compactness, and Graphene system
The shape of product is unfettered, and operation is simple, manufactures efficiency high, the graphene product interior solid prepared,
The defect such as pore-free, slag inclusion.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail, but the present invention does not limit
In these embodiments.
The invention provides the preparation method of a kind of graphene product, comprise the following steps:
Step 1, preparation of raw material
Adding SiC powder mix homogeneously in graphene powder, SiC powder addition is that mixed-powder is overall
Long-pending 0.1~1%, the addition of SiC powder can strengthen the adhesion within graphene product.Then will be mixed
Closing powder to add organic solvent and disperse, adding proportion is: every 10mL organic solvent adds 2mg~
20mg mixed-powder.High-power ultrasonics is utilized to make mixed-powder be uniformly dispersed in organic solvent, it is thus achieved that
Supersaturation graphene dispersing solution slurry;Organic solvent preferably following three kinds: DMF, it may be assumed that NN-dimethyl
Methanamide (boiling point: 153 DEG C, self-ignition point: 445 DEG C);NMP, it may be assumed that N-Methyl pyrrolidone (boiling point:
203 DEG C, burn point: 346 DEG C);THF, it may be assumed that oxolane, (boiling point: 203 DEG C, burn point: 346 DEG C).
Then supersaturation graphene dispersing solution slurry is uniformly mixed with organic adhesive, obtain mixed slurry.
Organic adhesive is for bonding during 3D printing-forming/solidified forming graphene product 3 D stereo knot
Structure, it is ensured that the structural strength before graphene product crude green body sintering, simultaneously energy in low-temperature defatted sintering process
Enough spillings rapidly.In order to ensure solidified forming quality and precision, it is necessary to select laser curing velocity very fast and viscous
Spend relatively low organic adhesive, preferably epoxy acrylic resin, urethane acrylate, polyester acrylic
Ester, polyester acrylate resin or amino acrylic resin.Supersaturation graphene dispersing solution slurry is viscous with organic
The volume ratio connecing agent is preferably 3:2~3:7.It addition, for ensureing the good mobility of slurry, mixed process and
Storing process should be avoided seeing light, particularly avoids ultraviolet light and irradiates.
Step 2, crude green body manufacture
Mixed slurry is loaded in 3D printing formation unit, utilize controllable UV Line beam, use face exposure
Or the mode of spot scan, successively print according to three-dimensional part model, make graphene product crude green body.Successively
The layer thickness control printed is in 20~80 μm, and optical source wavelength is 200~400nm.Expose according to face, expose
The light time is 0.1-3s;According to spot scan, spot diameter is 0.1~0.15mm, hot spot translational speed
1-300mm/min。
Step 3, post processing
Made graphene product crude green body is inserted in low-temperature sintering stove, at a temperature of 100 DEG C~800 DEG C
Low-temperature defatted process 1-2h, makes the organic adhesive evaporation in crude green body overflow;It is placed in again in high temperature insostatic pressing (HIP) stove,
Hip treatment is carried out under the conditions of temperature 1000 DEG C~1350 DEG C, pressure 100MPa~200MPa,
Obtain fine and close graphene product.
The graphene product consistency that the present invention prepares is higher, steady quality, to raw-material utilization rate
Height, and manufacturing speed is fast, the part that energy forming shape is especially complex, the finest, is suitable for small lot
Produce.
Embodiment 1
The preparation method of a kind of graphene product, specifically includes following steps:
(1) prepared by raw material
The synthesis of epoxy acrylic resin: acrylic acid and epoxy resin molar ratio are 1:1~1.05, ring
Epoxy resins is the most excessive, is possible to prevent the acrylic acid of remaining that base material and cured film are had harmful effect, but residual
The epoxy radicals stayed also can affect the bin stability of resin.Bisphenol-a epoxy acrylate select E-51 or
E-44, phenol aldehyde type epoxy resin selects F-51 or F-44.Catalyst selects catalysis activity high, product viscosity
Low triphenylphosphine, antimony triphenyl, chromium acetylacetonate, consumption (mass fraction) is 0.1%~3%.
Acrylic acid is exothermic reaction with epoxy ring-opening esterification, and therefore initial reaction stage control temperature is extremely important, logical
Often epoxy resin is heated to 80~90 DEG C, dropping acrylic acid, catalyst and inhibitor mixture, control
Reaction temperature 100 DEG C, sampling and measuring acid number simultaneously, it is warming up to 110~120 DEG C to the reaction later stage, makes acid
Value is decreased to less than 5mgKOH/g stopped reaction, is cooled to 80 DEG C of dischargings standby.Due to epoxy acid esters viscosity
Relatively big, 20% reactive diluent and appropriate polymerization inhibitor can be added when being cooled to 80 DEG C.Conventional activity is dilute
Releasing agent is three glycerol diacrylates, trimethylolpropane trimethacrylate, and conventional polymerization inhibitor is right
Methoxyphenol, hydroquinone, 2,5-dimethyl hydroquinone, 2,6-toluene di-tert-butyl phenol etc., resistance
Poly-agent addition is about the 0.01%~1% of resin quality.
Weigh 198g graphene powder and the mixing of 2gSiC powder, be added into 1000L DMF, utilize big
Power ultrasonic by dispersed for mixed-powder uniformly, it is thus achieved that supersaturation graphene dispersing solution slurry.Again will
Supersaturation graphene dispersing solution slurry adds the epoxy acrylic resin prepared the most fully under the conditions of lucifuge
Mixing, obtains mixed slurry.Supersaturation graphene dispersing solution slurry with epoxy acrylic resin volume ratio is
3:7。
(2) crude green body manufacture
Mixed slurry loads 3D print in Stereolithography equipment, utilize controllable UV Line beam, use
The mode of face exposure, successively prints according to three-dimensional part model, and thickness is 80 μm, and optical source wavelength is 400nm,
Time of exposure is 3s, successively makes graphene product crude green body.
(3) post processing
Made graphene product crude green body is inserted in low-temperature sintering stove, carries out low-temperature defatted place at 800 DEG C
Reason 2h, makes organic adhesive overflow, volatilizees.Again the graphene product crude green body after defat is inserted heat etc. quiet
In pressure stove, 1350 DEG C, under 200MPa, carry out hip treatment 3h, it is thus achieved that fine and close Graphene
Goods.
Embodiment 2
The preparation method of a kind of graphene product, specifically includes following steps:
(1) prepared by raw material
The synthesis of urethane acrylate be utilize polyisocyanates, long chain diol, crylic acid hydroxy ester and
Catalyst reaction synthesis of polyurethane acrylate.Catalyst can be selected for tertiary amines, metallic compound and organic
Phosphorus.Can be selected for different polyisocyanates and the urethane acrylate of long chain diol acquisition different structure.
The synthesis of urethane acrylate is to utilize isocyano and long chain diol and dihydroxypropyl in isocyanates
Hydroxyl reaction in ester, formed ammonia ester bond and prepared.
In the present embodiment, synthesis of polyurethane acrylate method is: by 2mol diisocyanate and a certain amount of
Dibutyl tin laurate adds in reactor, is warmed up to 40~50 DEG C, slowly dropping 1mol glycol, reaction
After 1h, it is warmed up to 60 DEG C, measures nco value to value of calculation, addition 2mol crylic acid hydroxy ester and
Quantitative hydroquinone of polymerization retarder, is warming up to 70~80 DEG C, until nco value is zero.In view of NCO
There is bigger toxicity, can suitably make crylic acid hydroxy ester the most excessive during reaction, make NCO group react
Completely.
Weigh 20g graphene powder and the mixing of 0.02g SiC powder, be added into 100L NMP, utilize
High-power ultrasonics by dispersed for mixed-powder uniformly, it is thus achieved that supersaturation graphene dispersing solution slurry.Again
Supersaturation graphene dispersing solution slurry is added under the conditions of lucifuge the urethane acrylate resin prepared and fills
Divide mixing, obtain mixed slurry.Supersaturation graphene dispersing solution slurry and urethane acrylate resin volume ratio
For 3:5.
(2) crude green body manufacture
Mixed slurry is loaded in 3D printing formation unit, utilize controllable UV Line beam, use face exposure
Mode, successively print according to three-dimensional part model, thickness is 60 μm, and optical source wavelength is 350nm, expose
The light time is 2s, successively makes graphene product crude green body.
(3) post processing
Made graphene product crude green body is inserted in low-temperature sintering stove, carries out low-temperature defatted place at 500 DEG C
Reason 1.5h, makes organic adhesive overflow, volatilizees.The graphene product crude green body after defat is inserted heat etc. again
In static pressure stove, 1200 DEG C, under 150MPa, carry out hip treatment 1h, it is thus achieved that fine and close graphite
Alkene goods.
Embodiment 3
The preparation method of a kind of graphene product, specifically includes following steps:
(1) prepared by raw material
Weigh 20g graphene powder and the mixing of 0.2g SiC powder, be added into 100L THF, utilize big
Power ultrasonic by dispersed for mixed-powder uniformly, it is thus achieved that supersaturation graphene dispersing solution slurry.Again will
Supersaturation graphene dispersing solution slurry adds urethane acrylate under the conditions of lucifuge and is sufficiently mixed,
To mixed slurry.Supersaturation graphene dispersing solution slurry and urethane acrylate volume ratio are 3:2.
(2) crude green body manufacture
Mixed slurry is loaded in 3D printing formation unit, utilize controllable UV Line beam, use spot scan
Mode, successively print according to three-dimensional part model, thickness is 40 μm, and optical source wavelength is 350nm, light
Spot diameter is 0.15mm, and hot spot translational speed 1mm/min successively makes graphene product crude green body.
(3) post processing
Made graphene product crude green body is inserted in low-temperature sintering stove, carries out low-temperature defatted place at 200 DEG C
Reason 1h, makes organic adhesive overflow, volatilizees.Again the graphene product crude green body after defat is inserted heat etc. quiet
In pressure stove, 1000 DEG C, under 120MPa, carry out hip treatment 1h, it is thus achieved that fine and close Graphene
Goods.
Embodiment 4
The preparation method of a kind of graphene product, specifically includes following steps:
(1) prepared by raw material
Weigh 2g graphene powder and the mixing of 0.006g SiC powder, be added into 10L THF, utilize big
Power ultrasonic by dispersed for mixed-powder uniformly, it is thus achieved that supersaturation graphene dispersing solution slurry.Again will
Supersaturation graphene dispersing solution slurry adds polyester acrylate resin under the conditions of lucifuge and is sufficiently mixed,
To mixed slurry.Supersaturation graphene dispersing solution slurry and polyester acrylate resin volume ratio are 3:3.
(2) crude green body manufacture
Mixed slurry is loaded in 3D printing formation unit, utilize controllable UV Line beam, use spot scan
Mode, successively print according to three-dimensional part model, thickness is 20 μm, and optical source wavelength is 300nm, light
Spot diameter is 0.1mm, and hot spot translational speed 300mm/min successively makes graphene product crude green body.
(3) post processing
Made graphene product crude green body is inserted in low-temperature sintering stove, carries out low-temperature defatted place at 100 DEG C
Reason 1h, makes organic adhesive overflow, volatilizees.Again the graphene product crude green body after defat is inserted heat etc. quiet
In pressure stove, 1000 DEG C, under 100MPa, carry out hip treatment 20min, it is thus achieved that fine and close graphite
Alkene goods.
Embodiment 5
The preparation method of a kind of graphene product, specifically includes following steps:
(1) prepared by raw material
Weigh 2g graphene powder and the mixing of 0.014g SiC powder, be added into 10L NMP, utilize big
Power ultrasonic by dispersed for mixed-powder uniformly, it is thus achieved that supersaturation graphene dispersing solution slurry.Again will
Supersaturation graphene dispersing solution slurry adds polyester acrylate resin under the conditions of lucifuge and is sufficiently mixed,
To mixed slurry.Supersaturation graphene dispersing solution slurry and polyester acrylate resin volume ratio are 3:4.
(2) crude green body manufacture
Mixed slurry is loaded in 3D printing formation unit, utilize controllable UV Line beam, use spot scan
Mode, successively print according to three-dimensional part model, thickness is 25 μm, and optical source wavelength is 200nm, light
Spot diameter is 0.15mm, and hot spot translational speed 150mm/min successively makes graphene product crude green body.
(3) post processing
Made graphene product crude green body is inserted in low-temperature sintering stove, carries out low-temperature defatted place at 120 DEG C
Reason 1h, makes organic adhesive overflow, volatilizees.Again the graphene product crude green body after defat is inserted heat etc. quiet
In pressure stove, 1000 DEG C, under 100MPa, carry out hip treatment 20min, it is thus achieved that fine and close graphite
Alkene goods.
The compactness of the graphene product that embodiment of the present invention 1-5 is prepared is good, internal pore-free, slag inclusion
Etc. defect, market product requirement all can be met, and different, the demand of difformity part can be met.
The present invention uses 3D printing technique to manufacture graphene product, and shape is unfettered, it is possible to convenient, fast
Speed prepares the variously-shaped graphene product with high-compactness, has filled up the blank on market, tool
There is the biggest market value.
Above description of the present invention is section Example, but the invention is not limited in above-mentioned concrete reality
Execute mode.Above-mentioned detailed description of the invention is schematic, is not restrictive.Every employing this
Bright material and method, in the case of without departing from present inventive concept and scope of the claimed protection, institute
Within having concrete expansion all to belong to protection scope of the present invention.
Claims (9)
1. the preparation method of a graphene product, it is characterised in that comprise the following steps:
Step 1, preparation of raw material
Graphene powder is mixed with SiC powder, mixed-powder is added organic solvent, utilize ultrasound wave
Mixed-powder is made to be uniformly dispersed in organic solvent, it is thus achieved that supersaturation graphene dispersing solution slurry;Will satiety
Uniformly mix under the conditions of lucifuge with organic adhesive with graphene dispersing solution slurry, obtain mixed slurry;
Step 2, crude green body manufacture
Mixed slurry loads 3D print in Stereolithography equipment, utilize controllable UV Line beam, use
Face exposure or the mode of spot scan, successively print according to three-dimensional part model, make graphene product crude green body;
Step 3, post processing
Graphene product crude green body is carried out low-temperature defatted process, makes the organic adhesive evaporation in crude green body overflow;
Carry out hip treatment again, it is thus achieved that fine and close graphene product.
The preparation method of graphene product the most according to claim 1, it is characterised in that described SiC
The addition of powder is the 0.1~1% of mixed-powder cumulative volume.
The preparation method of graphene product the most according to claim 1, it is characterised in that described in have
Machine solvent is NN-dimethylformamide, N-Methyl pyrrolidone or oxolane.
The preparation method of graphene product the most according to claim 1, it is characterised in that described in have
Machine bonding agent is epoxy acrylic resin, urethane acrylate, polyester acrylate, polyester acrylic
One of resin or amino acrylic resin.
The preparation method of graphene product the most according to claim 1, it is characterised in that described stone
Ink alkene powder with the proportionate relationship of described organic solvent is: add 2mg~20mg in every 10mL organic solvent
Graphene powder;Described supersaturation graphene dispersing solution slurry with the volume ratio of described organic adhesive is
3:2~3:7.
The preparation method of graphene product the most according to claim 1, it is characterised in that described by
The layer thickness control that layer prints is in 20~80 μm, and optical source wavelength is 200~400nm.
The preparation method of graphene product the most according to claim 1, it is characterised in that described beat
When India side formula uses face exposure, time of exposure is 0.1-3s;When described printing type uses spot scan, hot spot
A diameter of 0.1~0.15mm, hot spot translational speed 1-300mm/min.
The preparation method of graphene product the most according to claim 1, it is characterised in that described low
The temperature 100 DEG C~800 DEG C of temperature ungrease treatment, time 1-2h.
The preparation method of graphene product the most according to claim 1, it is characterised in that described heat
Isostatic pressed treatment temperature 1000 DEG C~1350 DEG C, pressure 100MPa~200MPa, time 0.2-3h.
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CN107353004B (en) * | 2017-07-18 | 2020-07-14 | 中国科学院上海硅酸盐研究所 | Method for preparing three-dimensional graphene through direct extrusion type 3D printing |
CN110028329A (en) * | 2018-01-11 | 2019-07-19 | 航天特种材料及工艺技术研究所 | A kind of high heat-conducting ceramic based composites and preparation method thereof |
CN109825087A (en) * | 2019-01-31 | 2019-05-31 | 江南大学 | A kind of protective materials of the high negative poisson's ratio pilotaxitic texture of novel 3D printing |
CN115403390A (en) * | 2022-09-20 | 2022-11-29 | 吉林大学 | Method for preparing porous carbon skeleton by photocuring 3D printing through high-solid-content/low-transmittance carbon-based slurry |
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