CN110171973A - A kind of method of the graphene-based conductive structure of 3D printing high temperature resistant - Google Patents
A kind of method of the graphene-based conductive structure of 3D printing high temperature resistant Download PDFInfo
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Abstract
A kind of method of the graphene-based conductive structure of 3D printing high temperature resistant, the present invention relates to a kind of methods of 3D printing conductive structure.Solve the problems, such as existing graphene-based electrode slurry solid concentration it is low, molding after can contraction distortion cause structure to be difficult to maintain design shape and precision.Preparation method: one, graphene oxide is prepared；Two, graphene oxide/graphite 3D printing slurry is prepared；Three, graphene oxide/graphite 3D printing molding；Four, 3D printing graphene oxide/graphite high temperature reduction.The present invention is used for the graphene-based conductive structure of 3D printing high temperature resistant.
Description
Technical field
The present invention relates to a kind of methods of 3D printing conductive structure.
Background technique
Graphene is a kind of two-dimension nano materials with superior electrical conductivity energy and superhigh intensity, usually using before graphene
It drives body-graphene oxide and carries out also original preparation graphene macroform, but its molding difficulty is high, this is because graphene oxide is molten
When solid concentration improves, viscosity can steeply rise fluid viscosity, so as to cause printable graphene oxide solution solid concentration
Too low, a maximum of about of 10wt% will lead to up to 80% volume contraction in drying process after shaping, it is difficult to remain former
The shape and precision for the design that begins.
Summary of the invention
Meeting contraction distortion causes structure difficult after low, molding that the invention solves existing graphene-based electrode slurry solid concentrations
The problem of to maintain design shape and precision, and a kind of method of graphene-based conductive structure of 3D printing high temperature resistant is provided.
A kind of method of the graphene-based conductive structure of 3D printing high temperature resistant is to sequentially include the following steps:
One, graphene oxide is prepared:
1., by mass percent be 30%~70% the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide be mixed and stirred for
It is even, graphite is then added, under conditions of temperature is 50 DEG C~90 DEG C, keeps the temperature 2h~4.5h, deionized water is then added, stand
5h~for 24 hours, it obtains standing liquid；
The volume ratio for the concentrated sulfuric acid that the quality of the potassium peroxydisulfate and mass percent are 30%~70% be 1g:(3~
5)mL；The mass ratio of the potassium peroxydisulfate and phosphorus pentoxide is 1:(0.8~1.2)；The potassium peroxydisulfate and graphite
Mass ratio is 1:(1~1.2)；The quality of the potassium peroxydisulfate and the volume ratio of deionized water are 1g:(10~100) mL；
2., go to stand the supernatant of liquid, then taking precipitate filtering is that cleaning solution rinses using deionized water, up to washing
Cleaning solution after washing is neutrality, is finally dried, and pre-oxidation graphite is obtained；
3., under agitation, by pre-oxidize graphite be added to mass percent be 30%~70% the low temperature concentrated sulfuric acid,
After being uniformly dispersed, potassium permanganate is added, stirs 2h~5h, is eventually adding deionized water and mass percent is 10%~30%
Hydrogen peroxide, stirring obtain crude product until solution presentation glassy yellow；
The low temperature concentrated sulfuric acid temperature that the mass percent is 30%~70% is -10 DEG C~0 DEG C；The pre-oxidation
The volume ratio for the low temperature concentrated sulfuric acid that the quality and mass percent of graphite are 30%~70% is 1g:(40~50) mL；Described
The mass ratio for pre-oxidizing graphite and potassium permanganate is 1:(5~12)；The quality of the pre-oxidation graphite and the body of deionized water
Product is than being 1g:(50~100) mL；The hydrogen peroxide that the quality and mass percent of the pre-oxidation graphite are 10%~30%
Volume ratio be 1g:(10~20) mL；
4., crude product be add to deionized water stand 5h~12h, be then successively using deionized water and concentration
The hydrochloric acid of 0.5mol/L~1mol/L cleans, then rinses by cleaning solution of deionized water, until the cleaning solution after washing is neutrality,
The product after washing is finally packed into bag filter to dialyse 15 days~30 days, obtains graphene oxide solution；
The quality of the crude product and the volume ratio of deionized water are 1g:(50~100) mL；
Two, graphene oxide/graphite 3D printing slurry is prepared:
1., graphene oxide solution is subjected to concentration calibration；
2., when the mass percent of graphene oxide in graphene oxide solution be higher than 0.5%~4% when, to oxidation stone
Deionized water dilution is added in black alkene solution, and under conditions of revolving speed is 1000r/min~2500r/min, mechanical stirring
Then 30min~60min uses Probe Ultrasonic Searching, under conditions of ultrasonic power is the 50%~80% of full-load power, ultrasound
30min~240min obtains adjusting the graphene oxide solution after concentration；
When the mass percent of graphene oxide in graphene oxide solution is lower than 0.5%~4%, rotary evaporation is used
Device evaporates the moisture in graphene oxide solution under conditions of temperature is 40 DEG C~80 DEG C, obtains after adjusting concentration
Graphene oxide solution；
The mass percent of graphene oxide is 0.5%~4% in graphene oxide solution after the adjusting concentration；
3., by high purity graphite two-dimensional material with adjust concentration after graphene oxide solution mix, be in revolving speed
Under conditions of 1000r/min~2500r/min, 5min~30min is stirred using planetary vacuum defoamation blender, is aoxidized
Graphene/graphite 3D printing slurry；
The high purity graphite two-dimensional material and the mass ratio for adjusting the graphene oxide solution after concentration be 10:(6~
16)；
Three, graphene oxide/graphite 3D printing molding:
Graphene oxide/graphite 3D printing slurry is poured into dispensing plastic pin cylinder, dispensing syringe is then fixed on 3D and is beaten
On print machine shifting axle, finally dispensing syringe is connected to dispenser, and under conditions of extrusion pressure is 5pai~100pai, squeezed
Slurry out carries out 3D and beats under conditions of print speed is 5mm/s~40mm/s and bottom plate heating temperature is 20 DEG C~100 DEG C
Print obtains the sample of 3D printing preparation；
Four, 3D printing graphene oxide/graphite high temperature reduction:
The sample of 3D printing preparation is dried into 5h~12h in air, is subsequently placed in vacuum tube furnace, in inert atmosphere
Under, with heating rate be 1 DEG C/min~8 DEG C/min, temperature is warming up to 550 DEG C~1800 DEG C, then temperature be 550 DEG C~
Under conditions of 1800 DEG C, 1h~3h is kept the temperature, the method for completing the graphene-based conductive structure of 3D printing high temperature resistant.
Principle: after using high purity graphite two-dimensional material, under the premise of not increasing slurry viscosity, the whole solid phase of slurry
Content can be improved 60wt% or so, and have good rheological property, it is ensured that ceramic slurry while can be printed,
With lesser cubical contraction, only 20%, to ensure printing precision.
The beneficial effects of the present invention are:
The slurry that the method for the present invention is prepared has good rheological property, has good shearing-thin effect, with
Height under low shear rate stores up storage modulu, the high loss modulus under high-rate of shear, printing precision height (minimum feature
0.15mm), after the completion of drying and after heat treatment, planform, precision are remained intact, the graphene finally prepared/graphite 3D
Structure has shown good mechanical mechanics property (compression strength reaches as high as 38MPa) and structure precision, has good lead
Electrical property (conductivity 10000S/m~100000S/m), and it is considerable still having been shown after 1500 degree of high-temperature process
Mechanical strength (10MPa~30MPa), can be applicable on high temperature labyrinth conductive component.
A kind of method that the present invention is used for graphene-based conductive structure of 3D printing high temperature resistant.
Detailed description of the invention
Fig. 1 is the pictorial diagram of the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment one；
Fig. 2 is mechanical property figure, and a is the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment one, and b is to implement
The graphene-based conductive structure of 3D printing high temperature resistant prepared by example two, c are that 3D printing high temperature resistant prepared by embodiment three is graphene-based
Conductive structure, d are the graphene-based conductive structure of 3D printing high temperature resistant of example IV preparation, and 1 is after conductive structure air drying
Mechanical property, 2 be mechanical property of the conductive structure after temperature is 1000 DEG C of high-temperature process 3h, and 3 be conductive structure in temperature
For the mechanical property after 1500 DEG C of high-temperature process 3h；
Fig. 3 is the port scan electron microscope of the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment one；
Fig. 4 is graphene oxide/graphite 3D printing slurry viscosity-shear rate curve of one step 2 of embodiment preparation
Figure；
Graphene oxide/graphite 3D printing slurry modulus-stress diagrams that Fig. 5 is prepared for one step 2 of embodiment, 1
It is loss modulus for storage modulu, 2；
Fig. 6 is the pictorial diagram of the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment two.
Specific embodiment
Specific embodiment 1: a kind of method of the graphene-based conductive structure of 3D printing high temperature resistant of present embodiment be by with
Lower step carries out:
One, graphene oxide is prepared:
1., by mass percent be 30%~70% the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide be mixed and stirred for
It is even, graphite is then added, under conditions of temperature is 50 DEG C~90 DEG C, keeps the temperature 2h~4.5h, deionized water is then added, stand
5h~for 24 hours, it obtains standing liquid；
The volume ratio for the concentrated sulfuric acid that the quality of the potassium peroxydisulfate and mass percent are 30%~70% be 1g:(3~
5)mL；The mass ratio of the potassium peroxydisulfate and phosphorus pentoxide is 1:(0.8~1.2)；The potassium peroxydisulfate and graphite
Mass ratio is 1:(1~1.2)；The quality of the potassium peroxydisulfate and the volume ratio of deionized water are 1g:(10~100) mL；
2., go to stand the supernatant of liquid, then taking precipitate filtering is that cleaning solution rinses using deionized water, up to washing
Cleaning solution after washing is neutrality, is finally dried, and pre-oxidation graphite is obtained；
3., under agitation, by pre-oxidize graphite be added to mass percent be 30%~70% the low temperature concentrated sulfuric acid,
After being uniformly dispersed, potassium permanganate is added, stirs 2h~5h, is eventually adding deionized water and mass percent is 10%~30%
Hydrogen peroxide, stirring obtain crude product until solution presentation glassy yellow；
The low temperature concentrated sulfuric acid temperature that the mass percent is 30%~70% is -10 DEG C~0 DEG C；The pre-oxidation
The volume ratio for the low temperature concentrated sulfuric acid that the quality and mass percent of graphite are 30%~70% is 1g:(40~50) mL；Described
The mass ratio for pre-oxidizing graphite and potassium permanganate is 1:(5~12)；The quality of the pre-oxidation graphite and the body of deionized water
Product is than being 1g:(50~100) mL；The hydrogen peroxide that the quality and mass percent of the pre-oxidation graphite are 10%~30%
Volume ratio be 1g:(10~20) mL；
4., crude product be add to deionized water stand 5h~12h, be then successively using deionized water and concentration
The hydrochloric acid of 0.5mol/L~1mol/L cleans, then rinses by cleaning solution of deionized water, until the cleaning solution after washing is neutrality,
The product after washing is finally packed into bag filter to dialyse 15 days~30 days, obtains graphene oxide solution；
The quality of the crude product and the volume ratio of deionized water are 1g:(50~100) mL；
Two, graphene oxide/graphite 3D printing slurry is prepared:
1., graphene oxide solution is subjected to concentration calibration；
2., when the mass percent of graphene oxide in graphene oxide solution be higher than 0.5%~4% when, to oxidation stone
Deionized water dilution is added in black alkene solution, and under conditions of revolving speed is 1000r/min~2500r/min, mechanical stirring
Then 30min~60min uses Probe Ultrasonic Searching, under conditions of ultrasonic power is the 50%~80% of full-load power, ultrasound
30min~240min obtains adjusting the graphene oxide solution after concentration；
When the mass percent of graphene oxide in graphene oxide solution is lower than 0.5%~4%, rotary evaporation is used
Device evaporates the moisture in graphene oxide solution under conditions of temperature is 40 DEG C~80 DEG C, obtains after adjusting concentration
Graphene oxide solution；
The mass percent of graphene oxide is 0.5%~4% in graphene oxide solution after the adjusting concentration；
3., by high purity graphite two-dimensional material with adjust concentration after graphene oxide solution mix, be in revolving speed
Under conditions of 1000r/min~2500r/min, 5min~30min is stirred using planetary vacuum defoamation blender, is aoxidized
Graphene/graphite 3D printing slurry；
The high purity graphite two-dimensional material and the mass ratio for adjusting the graphene oxide solution after concentration be 10:(6~
16)；
Three, graphene oxide/graphite 3D printing molding:
Graphene oxide/graphite 3D printing slurry is poured into dispensing plastic pin cylinder, dispensing syringe is then fixed on 3D and is beaten
On print machine shifting axle, finally dispensing syringe is connected to dispenser, and under conditions of extrusion pressure is 5pai~100pai, squeezed
Slurry out carries out 3D and beats under conditions of print speed is 5mm/s~40mm/s and bottom plate heating temperature is 20 DEG C~100 DEG C
Print obtains the sample of 3D printing preparation；
Four, 3D printing graphene oxide/graphite high temperature reduction:
The sample of 3D printing preparation is dried into 5h~12h in air, is subsequently placed in vacuum tube furnace, in inert atmosphere
Under, with heating rate be 1 DEG C/min~8 DEG C/min, temperature is warming up to 550 DEG C~1800 DEG C, then temperature be 550 DEG C~
Under conditions of 1800 DEG C, 1h~3h is kept the temperature, the method for completing the graphene-based conductive structure of 3D printing high temperature resistant.
The beneficial effect of present embodiment is: the slurry that present embodiment method is prepared has good
Rheological property has good shearing-thin effect, stores up storage modulu with the height under low shear rate, the height under high-rate of shear
Loss modulus, printing precision height (minimum feature 0.15mm), after the completion of drying and after heat treatment, planform, precision are kept
It is intact, the graphene finally prepared/graphite 3D structure shown good mechanical mechanics property (compression strength 30MPa~
50MPa) and structure precision, have good electric conductivity (10000S/m~100000S/m), and passing through 1500 degree of high temperature
Considerable mechanical strength (10MPa~30MPa) still has been shown after processing, can be applicable to high temperature labyrinth conductive component
On.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: step 1 1. described in stone
Ink is high-purity crystalline flake graphite, and partial size is 50 mesh~1000 mesh.It is other same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one or two: step 1 4. in
The dialysis bag retention molecular weight is 14000.It is other the same as one or two specific embodiments.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: step 2 3. in
The high purity graphite two-dimensional material is high-purity graphite powder or the other graphene of micro/nano level, the high-purity graphite powder
Partial size be 100 mesh~10000 mesh；The purity of the high-purity graphite powder is 99.9% or more.Other and specific embodiment party
Formula one to three is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: described is high-purity
Spend the mixture that graphite powder is one or both of crystalline flake graphite and natural graphite.It is other with one to four phase of specific embodiment
Together.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: institute in step 4
The inert atmosphere stated is argon atmosphere or nitrogen atmosphere.It is other identical as specific embodiment one or five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: step 1 1. in
The concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide that mass percent is 30%~70% are mixed and stirred for uniformly, being then added
Graphite keeps the temperature 3h~4.5h, is then added deionized water under conditions of temperature is 80 DEG C~90 DEG C, stands 12h~for 24 hours, obtains
To standing liquid.It is other identical as specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: step 1 4. in
Crude product is add to deionized water and stands 8h~12h, then successively using deionized water and concentration be 0.8mol/L~
The hydrochloric acid of 1mol/L cleans, then rinses by cleaning solution of deionized water, until the cleaning solution after washing is neutrality, it finally will washing
Product afterwards is packed into bag filter and dialyses 15 days~20 days, obtains graphene oxide solution.Other and specific embodiment one to seven
It is identical.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: step 2 2. in
When the mass percent of graphene oxide in graphene oxide solution is higher than 0.5%~4%, add into graphene oxide solution
Enter deionized water dilution, and under conditions of revolving speed is 1500r/min~2500r/min, mechanical stirring 40min~60min, so
Probe Ultrasonic Searching is used afterwards, and under conditions of ultrasonic power is the 50%~70% of full-load power, ultrasonic 60min~240min is obtained
Graphene oxide solution to after adjusting concentration；
When the mass percent of graphene oxide in graphene oxide solution is lower than 0.5%~4%, rotary evaporation is used
Device evaporates the moisture in graphene oxide solution under conditions of temperature is 60 DEG C~80 DEG C, obtains after adjusting concentration
Graphene oxide solution.It is other identical as specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: will in step 4
The sample of 3D printing preparation dries 5h~10h in air, is subsequently placed in vacuum tube furnace, under an inert atmosphere, with heating
Speed is 5 DEG C/min~8 DEG C/min, and temperature is warming up to 550 DEG C~1000 DEG C, is then 550 DEG C~1000 DEG C in temperature
Under the conditions of, keep the temperature 1h~2h.It is other identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
A kind of method of the graphene-based conductive structure of 3D printing high temperature resistant is to sequentially include the following steps:
One, graphene oxide is prepared:
1., the concentrated sulfuric acid, 84g potassium peroxydisulfate and 84g phosphorus pentoxide that 280mL mass percent is 70% mixed and stir
It mixes uniformly, 100g graphite is then added, under conditions of temperature is 80 DEG C, keep the temperature 4.5h, 8000mL deionized water is then added,
12h is stood, obtains standing liquid；
2., go to stand the supernatant of liquid, then taking precipitate filtering is that cleaning solution rinses using deionized water, up to washing
Cleaning solution after washing is neutrality, is finally dried, and pre-oxidation graphite is obtained；
3., under agitation, by 100g pre-oxidation graphite be added to 4600mL mass percent be 70% low temperature it is dense
Sulfuric acid after being uniformly dispersed, is added 600g potassium permanganate, stirs 2h, be eventually adding 5000mL deionized water and 1000mL mass hundred
The hydrogen peroxide that score is 30%, stirring obtain crude product until mixture presentation glassy yellow；
The low temperature concentrated sulfuric acid temperature that the mass percent is 30%~70% is -8 DEG C；
4., crude product be add to deionized water stand 12h, the use of deionized water and concentration is successively then 1mol/L
Hydrochloric acid cleaning, then using deionized water be that cleaning solution rinses, until the cleaning solution after washing be it is neutral, finally by the production after washing
Object is packed into bag filter and dialyses 15 days, obtains graphene oxide solution；
The quality of the crude product and the volume ratio of deionized water are 1g:50mL；
Two, graphene oxide/graphite 3D printing slurry is prepared:
1., graphene oxide solution is subjected to concentration calibration；
2., the mass percent of graphene oxide is higher than 2% in graphene oxide solution, into graphene oxide solution plus
Enter deionized water dilution, and under conditions of revolving speed is 2500r/min, then mechanical stirring 60min uses Probe Ultrasonic Searching,
Under conditions of ultrasonic power is the 50% of full-load power, ultrasonic 60min obtains adjusting the graphene oxide solution after concentration；
The mass percent of graphene oxide is 2% in graphene oxide solution after the adjusting concentration；
3., 10g high purity graphite two-dimensional material and 15g adjusted to the graphene oxide solution after concentration mix, in revolving speed
Under conditions of 2500r/min, 15min is stirred using planetary vacuum defoamation blender, graphene oxide/graphite 3D is obtained and beats
Printing paste material；
Three, graphene oxide/graphite 3D printing molding:
Graphene oxide/graphite 3D printing slurry is poured into dispensing syringe, dispensing syringe is then fixed on 3D printing
On machine shifting axle, finally dispensing syringe is connected to dispenser, and under conditions of extrusion pressure is 20pai, squeezes out slurry,
Under conditions of print speed is 15mm/s and bottom plate heating temperature is 30 DEG C, the sample of 3D printing preparation is obtained；
The syringe needle of the dispensing syringe is the flexible syringe needle that internal diameter is 0.41mm；
Four, 3D printing graphene oxide/graphite high temperature reduction:
The sample of 3D printing preparation is dried into 5h in air, is subsequently placed in vacuum tube furnace, under an inert atmosphere, with
Heating rate is 5 DEG C/min, temperature is warming up to 1000 DEG C, and under conditions of temperature is 1000 DEG C, keeps the temperature 1h, obtain 3D and beat
Print the graphene-based conductive structure of high temperature resistant.
Step 1 1. described in graphite be high-purity crystalline flake graphite, partial size be 325 mesh.
Step 1 4. described in dialysis bag retention molecular weight be 14000.
Step 2 3. in described in high-purity graphite powder be crystalline flake graphite.
High-purity graphite powder partial size described in step 2 is 10000 mesh；The purity of the high-purity graphite powder is
99.9% or more.
Inert atmosphere described in step 4 is argon atmosphere.
Embodiment two: the present embodiment is unlike embodiment one: step 2 2. in aoxidize stone in graphene oxide solution
The mass percent of black alkene is higher than 0.5%, and deionized water dilution is added into graphene oxide solution, and is 2500r/ in revolving speed
Under conditions of min, then mechanical stirring 60min uses Probe Ultrasonic Searching, in 50% condition that ultrasonic power is full-load power
Under, ultrasonic 60min obtains adjusting the graphene oxide solution after concentration；Graphene oxide solution after the adjusting concentration
The mass percent of middle graphene oxide is 0.5%.It is other to be the same as example 1.
Embodiment three: the present embodiment is unlike embodiment one: step 2 2. in aoxidize stone in graphene oxide solution
The mass percent of black alkene is higher than 1%, and deionized water dilution is added into graphene oxide solution, and is 2500r/ in revolving speed
Under conditions of min, then mechanical stirring 60min uses Probe Ultrasonic Searching, in 50% condition that ultrasonic power is full-load power
Under, ultrasonic 60min obtains adjusting the graphene oxide solution after concentration；Graphene oxide solution after the adjusting concentration
The mass percent of middle graphene oxide is 1%.It is other to be the same as example 1.
Example IV: the present embodiment is unlike embodiment one: step 2 2. in aoxidize stone in graphene oxide solution
When the mass percent of black alkene is lower than 4%, oxidation stone is evaporated under conditions of temperature is 60 DEG C using rotary evaporating device
Moisture in black alkene solution obtains adjusting the graphene oxide solution after concentration；Graphene oxide after the adjusting concentration
The mass percent of graphene oxide is 4% in solution.It is other to be the same as example 1.
Fig. 1 is the pictorial diagram of the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment one.As seen from the figure, the knot
Structure print quality is high, structural integrity, no significant defect, and printing precision is good (minimum feature 0.3mm).
Fig. 2 is mechanical property figure, and a is the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment one, and b is to implement
The graphene-based conductive structure of 3D printing high temperature resistant prepared by example two, c are that 3D printing high temperature resistant prepared by embodiment three is graphene-based
Conductive structure, d are the graphene-based conductive structure of 3D printing high temperature resistant of example IV preparation, and 1 is after conductive structure air drying
Mechanical property, 2 be mechanical property of the conductive structure after temperature is 1000 DEG C of high-temperature process 3h, and 3 be conductive structure in temperature
For the mechanical property after 1500 DEG C of high-temperature process 3h.As seen from the figure, the conductive structure of the method preparation is in 1500 DEG C of high-temperature process
Still good mechanical strength is kept, has good high temperature resistance with the compression strength of 12.9MPa afterwards.
Fig. 3 is the port scan electron microscope of the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment one；By scheming
It is found that graphite powder is mutually well dispersed with graphene oxide, it is tightly combined, structural homogeneity is good, without obvious pore structure.
Fig. 4 is graphene oxide/graphite 3D printing slurry viscosity-shear rate curve of one step 2 of embodiment preparation
Figure, Fig. 5 are graphene oxide/graphite 3D printing slurry modulus-stress diagrams of one step 2 of embodiment preparation, and 1 is storage
Modulus is deposited, 2 be loss modulus.As seen from the figure, the increase of shear rate, slurry viscosity decline is obvious, has typical shearing
Dilute change effect, under conditions of mild method, slurry has higher storage modulu and solid property is presented, in shearing force
Under conditions of, slurry has higher loss modulus, fluid behaviour is showed, to ensure that slurry is suitable under pressure
Benefit is extruded.
Fig. 6 is the pictorial diagram of the graphene-based conductive structure of 3D printing high temperature resistant prepared by embodiment two, as seen from the figure the knot
Structure precision is high, and minimum feature is up to 0.15mm.
Pass through Conductivity Calculation formula k=after testing structural resistance using multimeter using volume conductance test method
3D printing high temperature resistant prepared by L/RS (R resistance, S sectional area, L length, k conductivity) calculating acquisition embodiment one is graphene-based to be led
Electric structure conductivity is 53100S/m.
Dimensional measurement is carried out to the sample of the 3D printing preparation of example IV step 3 preparation, then by 3D printing preparation
Sample dries 5h in air, carries out dimensional measurement again, and the product for being computed example IV preparation is received with lesser volume
Shrinkage, only 20%.
Claims (10)
1. a kind of method of the graphene-based conductive structure of 3D printing high temperature resistant, it is characterised in that a kind of 3D printing high temperature resistant graphene
The method of base conductive structure is to sequentially include the following steps:
One, graphene oxide is prepared:
1., by mass percent be 30%~70% the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide be mixed and stirred for uniformly, so
After graphite is added, under conditions of temperature is 50 DEG C~90 DEG C, keeps the temperature 2h~4.5h, be then added deionized water, stand 5h~
For 24 hours, it obtains standing liquid；
The volume ratio for the concentrated sulfuric acid that the quality and mass percent of the potassium peroxydisulfate are 30%~70% is 1g:(3~5)
mL；The mass ratio of the potassium peroxydisulfate and phosphorus pentoxide is 1:(0.8~1.2)；The matter of the potassium peroxydisulfate and graphite
Amount is than being 1:(1~1.2)；The quality of the potassium peroxydisulfate and the volume ratio of deionized water are 1g:(10~100) mL；
2., go stand liquid supernatant, taking precipitate filtering, then using deionized water be cleaning solution rinse, until wash after
Cleaning solution be neutrality, finally dry, obtain pre-oxidation graphite；
3., under agitation, by pre-oxidize graphite be added to mass percent be 30%~70% the low temperature concentrated sulfuric acid, dispersion
After uniformly, potassium permanganate is added, stirs 2h~5h, is eventually adding the peroxide that deionized water and mass percent are 10%~30%
Change hydrogen, stirring obtains crude product until solution presentation glassy yellow；
The low temperature concentrated sulfuric acid temperature that the mass percent is 30%~70% is -10 DEG C~0 DEG C；The pre-oxidation graphite
Quality and mass percent be 30%~70% the volume ratio of the low temperature concentrated sulfuric acid be 1g:(40~50) mL；The pre- oxygen
The mass ratio of graphite and potassium permanganate is 1:(5~12)；The quality of the pre-oxidation graphite and the volume ratio of deionized water
For 1g:(50~100) mL；The body for the hydrogen peroxide that the quality and mass percent of the pre-oxidation graphite are 10%~30%
Product is than being 1g:(10~20) mL；
4., crude product be add to deionized water stand 5h~12h, be then successively using deionized water and concentration
The hydrochloric acid of 0.5mol/L~1mol/L cleans, then rinses by cleaning solution of deionized water, until the cleaning solution after washing is neutrality,
The product after washing is finally packed into bag filter to dialyse 15 days~30 days, obtains graphene oxide solution；
The quality of the crude product and the volume ratio of deionized water are 1g:(50~100) mL；
Two, graphene oxide/graphite 3D printing slurry is prepared:
1., graphene oxide solution is subjected to concentration calibration；
2., when the mass percent of graphene oxide in graphene oxide solution be higher than 0.5%~4% when, to graphene oxide
Deionized water dilution is added in solution, and under conditions of revolving speed is 1000r/min~2500r/min, mechanical stirring 30min~
Then 60min uses Probe Ultrasonic Searching, under conditions of ultrasonic power is the 50%~80% of full-load power, ultrasonic 30min~
240min obtains adjusting the graphene oxide solution after concentration；
When the mass percent of graphene oxide in graphene oxide solution is lower than 0.5%~4%, filled using rotary evaporation
It sets, under conditions of temperature is 40 DEG C~80 DEG C, evaporates the moisture in graphene oxide solution, obtain adjusting the oxygen after concentration
Graphite alkene solution；
The mass percent of graphene oxide is 0.5%~4% in graphene oxide solution after the adjusting concentration；
3., by high purity graphite two-dimensional material with adjust concentration after graphene oxide solution mix, revolving speed be 1000r/min
Under conditions of~2500r/min, 5min~30min is stirred using planetary vacuum defoamation blender, obtains graphene oxide/stone
Black 3D printing slurry；
The mass ratio of graphene oxide solution after the high purity graphite two-dimensional material and adjusting concentration is 10:(6~16)；
Three, graphene oxide/graphite 3D printing molding:
Graphene oxide/graphite 3D printing slurry is poured into dispensing plastic pin cylinder, dispensing syringe is then fixed on 3D printer
On shifting axle, finally dispensing syringe is connected to dispenser, and under conditions of extrusion pressure is 5pai~100pai, squeezes out slurry
Material carries out 3D printing, obtains under conditions of print speed is 5mm/s~40mm/s and bottom plate heating temperature is 20 DEG C~100 DEG C
The sample prepared to 3D printing；
Four, 3D printing graphene oxide/graphite high temperature reduction:
The sample of 3D printing preparation is dried into 5h~12h in air, is subsequently placed in vacuum tube furnace, under an inert atmosphere,
With heating rate be 1 DEG C/min~8 DEG C/min, temperature is warming up to 550 DEG C~1800 DEG C, then temperature be 550 DEG C~
Under conditions of 1800 DEG C, 1h~3h is kept the temperature, the method for completing the graphene-based conductive structure of 3D printing high temperature resistant.
2. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, it is characterised in that step
Rapid one 1. described in graphite be high-purity crystalline flake graphite, partial size be 50 mesh~1000 mesh.
3. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, it is characterised in that step
Rapid one 4. described in dialysis bag retention molecular weight be 14000.
4. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, it is characterised in that step
Rapid two 3. described in high purity graphite two-dimensional material be high-purity graphite powder or the other graphene of micro/nano level, described is high-purity
The partial size for spending graphite powder is 100 mesh~10000 mesh；The purity of the high-purity graphite powder is 99.9% or more.
5. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 4, it is characterised in that institute
The high-purity graphite powder stated is the mixture of one or both of crystalline flake graphite and natural graphite.
6. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, it is characterised in that step
Inert atmosphere described in rapid four is argon atmosphere or nitrogen atmosphere.
7. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, feature is in step
One 1. in by mass percent be 30%~70% the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide be mixed and stirred for uniformly, so
After graphite is added, under conditions of temperature is 80 DEG C~90 DEG C, keeps the temperature 3h~4.5h, be then added deionized water, stand 12h~
For 24 hours, it obtains standing liquid.
8. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, feature is in step
One 4. in crude product be add to deionized water stand 8h~12h, the use of deionized water and concentration is successively then 0.8mol/
The hydrochloric acid of L~1mol/L cleans, then rinses by cleaning solution of deionized water, until the cleaning solution after washing is neutrality, finally will
Product after washing is packed into bag filter and dialyses 15 days~20 days, obtains graphene oxide solution.
9. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, feature is in step
Two 2. in when the mass percent of graphene oxide in graphene oxide solution be higher than 0.5%~4% when, it is molten to graphene oxide
Deionized water dilution is added in liquid, and under conditions of revolving speed is 1500r/min~2500r/min, mechanical stirring 40min~
Then 60min uses Probe Ultrasonic Searching, under conditions of ultrasonic power is the 50%~70% of full-load power, ultrasonic 60min~
240min obtains adjusting the graphene oxide solution after concentration；
When the mass percent of graphene oxide in graphene oxide solution is lower than 0.5%~4%, filled using rotary evaporation
It sets, under conditions of temperature is 60 DEG C~80 DEG C, evaporates the moisture in graphene oxide solution, obtain adjusting the oxygen after concentration
Graphite alkene solution.
10. a kind of method of graphene-based conductive structure of 3D printing high temperature resistant according to claim 1, feature is in step
Sample in four by 3D printing preparation dries 5h~10h in air, is subsequently placed in vacuum tube furnace, under an inert atmosphere,
With heating rate be 5 DEG C/min~8 DEG C/min, temperature is warming up to 550 DEG C~1000 DEG C, then temperature be 550 DEG C~
Under conditions of 1000 DEG C, 1h~2h is kept the temperature.
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