CN109293366A - Can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics - Google Patents
Can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics Download PDFInfo
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- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
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Abstract
The invention discloses can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics, Polycarbosilane will be can be thermally cured and be dissolved into solution, and it is added in 3D printer, heated solution is to keeping the temperature a period of time after 70 DEG C~135 DEG C, it is ejected to again by spray head on 70 DEG C~135 DEG C of carrier, as solvent volatilizees, forming one layer of solid-state can be thermally cured Polycarbosilane, Polycarbosilane can be thermally cured as new carrier with solid-state again, it is sprayed next time, it repeats to spray, successively accumulation can be thermally cured the precast body that Polycarbosilane forms silicon carbide ceramics, precast body is put into Equipment for Heating Processing, it successively carries out removing solvent and can be thermally cured the processing of the crosslinking curing of Polycarbosilane, it places into pyrolysis oven, in argon atmosphere, after 1100~1200 DEG C are pyrolyzed, obtain 3D printing silicon carbide ceramics.The preparation method is simple, and raw material is single, and process flow is few, at low cost, and raw material is commercial product, high yield rate, high, the additive-free use of the product purity of preparation.
Description
Technical field
The invention belongs to 3D printing ceramic technology fields, and in particular to a kind of can be thermally cured Polycarbosilane 3D printing preparation
The preparation method of silicon carbide ceramics.
Background technique
Method currently used for preparing silicon carbide ceramics rapid shaping has: layer separated growth (abbreviation LOM);Melt deposition
Moulding (abbreviation FDM);Shaped deposition forms (abbreviation SDM);Stereolithography (abbreviation SLA);Precinct laser sintering (abbreviation SLS);
Ink-jet printing (abbreviation IJM).Huang little Ting is prepared for the ceramics of certain solid content with amphene, silicon carbide, binder, dispersing agent
Slurry is prepared for ceramic body (referring to " preparation of 3D printing silicon carbide ceramics and performance study ", Chinese silicate using 3D technology
Learn special cermacis branch, the 19th national high-performance ceramics Annual Conference abstract collection, 2016:1), patent CN
In 108409330A, the mixture for coating Polycarbosilane and silicon dioxide powder to silicon carbide powder obtains coated composite powder, with low concentration
Polycarbosilane solution is " ink ", forms printing powder using Direct Three-dimensional printing shaping machine and obtains ceramic green, then carries out high temperature
Sintering obtains silicon carbide ceramics.105601830 A of patent CN is disclosed using hyperbranched polycarbosilanes as main component, further includes
Reactive diluent, photoinitiator, additive photo-curing material technology of preparing and be used for 3D printing.Patent CN 104559196
A discloses a kind of colorless and transparent photocuring 3D printing material, the printed material include organopolysiloxane containing vinyl group,
Organopolysiloxane, photoinitiator, reinforcing filler, the auxiliary agent of silicon-hydrogen bond containing.102516866 A of patent CN discloses a kind of ultraviolet
Photo-curing material, including following weight percentage components: light-cured resin 40~60%;Photocuring diluent 25~45%;
Photoinitiator 2~10%;Ultraviolet light stable storage agent 0~0.8%;Nanofiller 0.5~30%;Levelling agent 0.2~1%.
So far, the preparation of 3D printing ceramics, according to the state of raw material can be divided into liquid and two kinds of solid-state.Solid-state 3D printing
Ceramic raw material is mixture composed by ceramic powder and certain binder, principle be binder coated in pyrolytic process or
Person is adhered ceramic powder, forms the ceramics with some strength, however ceramic powders and binder are originally two kinds of different plant species,
Its composition is different with property, it is difficult to form the uniform ceramics of composition.Liquid 3D printing ceramic raw material can be divided into ceramic slurry and molten
Two kinds of liquid blend, when 3D printing ceramic raw material is slurry, in order to guarantee that slurry stable uniformity needs to add stabilizer etc., surely
The addition for determining agent etc. will cause ceramic hole, unfavorable to ceramic performance.When 3D printing ceramic raw material is liquid blend, density
Not higher than 0.5g/cm3, silicon carbide ceramics density is 2.4~3.2g/cm3, it is desirable to fine and close carbonization is prepared by liquid material
Silicon ceramics, linear shrinkage ratio is high, it is difficult to ensure that yield rate.Trigger for optical solidification in liquid 3D printing ceramic raw material, stabilizer etc.,
Although it is most important in 3D printing molding, for example trigger for optical solidification provides light-cured performance etc., after shaping
During pyrolysis preparation ceramics, the additive of trigger for optical solidification, stabilizer etc. is decomposed, and hole and quality is equally caused to damage
It loses, the performance of ceramics is adversely affected, or even cause the cracking of ceramics broken.In summary, silicon carbide ceramics is direct
Quick shaping process is not yet mature.
Summary of the invention
Status in view of the above technology, the present invention is intended to provide one kind prepares silicon carbide can be thermally cured Polycarbosilane 3D printing
The preparation method of ceramics.
In order to achieve the above technical purposes, Polycarbosilane will be can be thermally cured sufficiently to dissolve in a solvent, is added after forming solution
Enter in 3D printer, after being heated to certain temperature, constant temperature sprays out hot solution to having certain temperature for a period of time, by spray head
On carrier, as solvent volatilizees, forming one layer of solid-state can be thermally cured Polycarbosilane, then can be thermally cured Polycarbosilane with solid-state to carry
Body is sprayed next time, repeats to spray, and successively forms 3D printing silicon carbide ceramics precast body after accumulation.Precast body is put into
In Equipment for Heating Processing, successively carries out removing solvent and can be thermally cured the crosslinking curing processing of Polycarbosilane.It places into pyrolysis oven,
Under the conditions of argon gas, after 1100~1200 DEG C are pyrolyzed, 3D printing silicon carbide ceramics is obtained.The solution manufacturing method is simple, former
Material list one, constituent is simple, and process flow is few, at low cost, and raw material is commercial product, and the Device-General of application, line is received
Shrinkage is not higher than 15%, 2.3~2.4g/cm of density3, high yield rate, the product purity height of preparation.
That is, the technical scheme is that can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method includes the following steps:
(1) Polycarbosilane and solvent will be can be thermally cured respectively according to 30~60wt% of mass percent and 70 DEG C~40wt%
Mix wiring solution-forming;
(2) by solution be added 3D printer in, after being heated to certain temperature, constant temperature for a period of time after, sprayed by spray head molten
On liquid to the carrier with certain temperature, with the volatilization of solvent in solution, solution, which becomes solid-state, can be thermally cured Polycarbosilane, then
It can be thermally cured Polycarbosilane using solid-state to be sprayed next time as carrier, successively form the pre- of 3D printing silicon carbide ceramics after accumulation
Body processed;
(3) precast body is carefully transferred in annealing device, in argon atmosphere, precast body is heat-treated, including
The removing of solvent and the crosslinking curing that can be thermally cured Polycarbosilane itself, obtain the precast body with some strength;
(4) precast body with some strength is put into pyrolysis oven, in argon atmosphere, high temperature pyrolysis is carried out to it, it is cold
But room temperature is arrived, 3D printing ceramic component is obtained.
In the step (1), as a kind of implementation, detailed process is as follows:
Polycarbosilane and solvent will be can be thermally cured to mix according to 30~60wt% of mass percent and 70 DEG C~40wt% respectively
Even wiring solution-forming;
Can be thermally cured the synthesis of Polycarbosilane: Polycarbosilane and vinyl silanes are made by hydrosilylation, molecule
Amount 1700~3200.
Preferably, what the Polycarbosilane was reset by polydimethylsiloxane Pintsch process, softening point 200~
300 DEG C, molecular weight 1500~2800.
Preferably, the Polycarbosilane (PVCS) that can be thermally cured only contains silicon, three kinds of carbon, hydrogen elements.
Preferably, the vinyl silanes are dimethyl divinyl silane, tetrapropylene base silane, tetravinyl silane
One of.
Preferably, the preparation method that can be thermally cured Polycarbosilane is with reference to (Gu Xishuan, Song Yong ability can be thermally cured
The synthesis of Polycarbosilane and performance [J] organosilicon material, 2015,29 (6): 462-468.): Polycarbosilane is dissolved in dimethylbenzene
In with dimethyl divinyl silane in mass ratio 1: 1, be placed in autoclave, be added platinum catalyst, vacuumize displacement High Purity Nitrogen
Gas, plus-pressure to 12.5MPa;110 DEG C of reaction 30h are heated under high pure nitrogen protection again;Cooling, vacuum distillation obtains
Product PVCS.PVCS is handled in nitrogen atmosphere to 400 DEG C, it can be achieved that fully crosslinked solidification, and gel content reaches 100%, hands over
After connection solidification, phenomena such as foaming does not occur in 1100~1200 DEG C of pyrolytic process, when turning to silicon carbide ceramics, flows, only occur
Volume contraction phenomenon, finally obtains fine and close silicon carbide ceramics, and ceramic yield is up to 78%.
In the step (2), as a kind of implementation, detailed process is as follows: solution being added in 3D printer, to molten
Liquid is heated, constant temperature for a period of time after, by spray head spraying hot solution to the carrier with certain temperature on, with molten in solution
The volatilization of agent, solution, which becomes solid-state, can be thermally cured Polycarbosilane, then using solid-state can be thermally cured Polycarbosilane carry out as carrier it is next
Secondary spraying successively forms the precast body of 3D printing silicon carbide ceramics after accumulation;
Preferably, the thermostat temperature of the hot solution is 70 DEG C~130 DEG C;
Preferably, the constant temperature time of the hot solution is 10~30min;
In the step (3), as a kind of implementation, detailed process is as follows: precast body is carefully transferred to heat treatment
In device, in argon atmosphere, precast body is heat-treated, removing including solvent and the friendship that can be thermally cured Polycarbosilane itself
Connection solidification, obtains the precast body with some strength;
In the step (4), as a kind of implementation, detailed process is as follows: detailed process is as follows: at step (3)
Precast body after reason under an argon atmosphere, with 1 DEG C/min~30 DEG C/min heating rate, is heated to 1100 DEG C~1200 DEG C,
Heat preservation 0.5h~5h hours, then cools to room temperature, obtains silicon carbide ceramics.
The present invention is can be thermally cured Polycarbosilane (PVCS) for raw material, in order to achieve the above technical purposes, first by thermosetting
Changing characteristic Polycarbosilane, sufficiently dissolution forms solution in a solvent, and is added in 3D printer, after being heated to certain temperature, constant temperature
For a period of time, it is sprayed out in hot solution to the carrier with certain temperature by spray head, as the solvent evaporates, forms one layer of solid-state
It can be thermally cured Polycarbosilane, then Polycarbosilane can be thermally cured as carrier using solid-state, sprayed next time, successively formed after accumulation
The precast body of 3D printing silicon carbide ceramics.Precast body is put into Equipment for Heating Processing, removing solvent is successively carried out and can be thermally cured
The crosslinking curing of Polycarbosilane is handled.It places into pyrolysis oven, under the conditions of argon gas, after 1100~1200 DEG C are pyrolyzed, obtains
3D printing silicon carbide ceramics.The solution manufacturing method is simple, and raw material is single, and constituent is simple, and process flow is few, at low cost,
Raw material is commercial product, the Device-General of application, linear shrinkage ratio 12~15%, and bulk density is 2.3~2.4g/c, finished product
Rate is high, and the product purity of preparation is high.
The present invention compared to the prior art the advantages of:
(1) preparation of printing solution of the present invention is simple, easily operated, under room temperature, can save for a long time.
(2) present invention to printer etc. without particular/special requirement, directly buy by required equipment Market;
(3) compared with the liquid material for being currently used for 3D printing ceramics, raw material of the invention is single, and ceramic product is forming
Homogeneity is more preferable in structure, and preparation process does not have any additive.
(4) present invention is compared with the solid feed for being currently used for 3D printing ceramics, the carbonized ceramic composed structure list of preparation
One.
(5) silicon carbide ceramics linear shrinkage ratio prepared by the present invention is low, high yield rate.
Specific embodiment
Below with reference to embodiment, present invention is further described in detail, it should be pointed out that embodiment described below purport
It is being convenient for the understanding of the present invention, and is not playing any restriction effect to it.
Embodiment 1:
It is as follows with the preparation process that can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics:
Step 1: can be thermally cured the preparation of Polycarbosilane, with reference to (Gu Xishuan, Song Yong ability can be thermally cured the conjunction of Polycarbosilane
At and performance [J] organosilicon material, 2015,29 (6): 462-468.): by Polycarbosilane (commercially available, molecular weight 2800, softening point
300 DEG C) be dissolved in dimethylbenzene with tetravinyl silane (commercially available) l:l in mass ratio, be placed in autoclave, be added platinum catalyst,
Vacuumize displacement high pure nitrogen, plus-pressure to 12.5MPa;110 DEG C of reaction 30h are heated under high pure nitrogen protection again;
Cooling, vacuum distillation obtains solid product PVCS.
It is characterized, the molecular weight that can be thermally cured Polycarbosilane is that 3150, PVCS is handled in nitrogen atmosphere to 400 DEG C, can
Realize fully crosslinked solidification, gel content reaches 100%, and the Polycarbosilane after crosslinking curing was pyrolyzed at 1100~1200 DEG C
In, phenomena such as foaming does not occur when turning to silicon carbide ceramics, flows, volume shrinkage phenomenon only occurs, finally obtains fine and close carbon
SiClx ceramics, ceramic yield is up to 80%.
Step 2: preparing solution according to mass ratio 3: 7 for can be thermally cured Polycarbosilane and the dimethylbenzene that prepare in step 1,
Prepared solution is added in 3D printer, solution is carried out to be heated to 100 DEG C, after keeping the temperature 10min, thermosol is sprayed by spray head
On the carrier of liquid to 100 DEG C, spray head is apart from carrier 1mm, and as the solvent evaporates, one layer of solid-state of formation can be thermally cured poly- on carrier
Carbon silane, the same manner carry out spraying hot solvent on newly formed solid-state Polycarbosilane again, and forming one layer of new solid-state can heat
Solidify Polycarbosilane, repeats to spray hot solvent, after successively accumulation solid-state can be thermally cured Polycarbosilane, it is prefabricated to form silicon carbide ceramics
Body;
Step 3: precast body is carefully transferred in annealing device, in argon atmosphere, is warming up to 130 with 3 DEG C/min
DEG C, 6h is handled, after removing solvent completely, continues to be warming up to 195 DEG C with 3 DEG C/min, keeps the temperature 1h, be further continued for 3 DEG C/min heating
To 400 DEG C, 1h is kept the temperature, the crosslinking curing that can be thermally cured Polycarbosilane is realized, obtains the precast body with some strength, gel contains
Amount 100%;
Step 4: the precast body that step 3 is obtained is put into pyrolysis oven, in argon atmosphere, is warming up to 2 DEG C/min
It 1100 DEG C, after keeping the temperature 1h, is cooled to room temperature to obtain 3D printing silicon carbide ceramics, bulk density 2.4g/cm3
Embodiment 2:
It is as follows with the preparation process that can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics:
Step 1: can be thermally cured the preparation of Polycarbosilane, with reference to (Gu Xishuan, Song Yong ability can be thermally cured the conjunction of Polycarbosilane
At and performance [J] organosilicon material, 2015,29 (6): 462-468.): by Polycarbosilane (commercially available, molecular weight 1500, softening point
200 DEG C) be dissolved in dimethylbenzene with dimethyl divinyl silane (commercially available) in mass ratio 1: 1, be placed in autoclave, be added platinum urge
Agent vacuumizes displacement high pure nitrogen, plus-pressure to 12.5MPa;110 DEG C of reactions are heated under high pure nitrogen protection again
30h;Cooling, vacuum distillation obtains solid product PVCS.It is characterized, the molecular weight that can be thermally cured Polycarbosilane is 1726, in nitrogen
Processing is to 400 DEG C, it can be achieved that fully crosslinked solidification in atmosphere, and the Polycarbosilane after 100%. crosslinking curing of gel content is 1100
Phenomena such as~1200 DEG C were pyrolyzed, and foaming, flowing does not occur when turning to silicon carbide ceramics, only occurs volume shrinkage phenomenon, most
Fine and close silicon carbide ceramics is obtained eventually, and ceramic yield is up to 78%.
Step 2: preparing solution according to mass ratio 6: 4 for can be thermally cured Polycarbosilane and the dimethylbenzene that prepare in step 1,
Prepared solution is added in 3D printer, heated solution is to 130 DEG C, after keeping the temperature 10min, sprays hot solution extremely by spray head
On 130 DEG C of carrier, spray head is apart from carrier 0.8mm, and forming one layer of solid-state as the solvent evaporates, on carrier can be thermally cured poly- carbon
Silane then carries out spraying hot solvent on newly formed solid-state Polycarbosilane again, formed one layer of new solid-state can be thermally cured it is poly-
Carbon silane repeats to spray hot solvent, after successively accumulation solid-state can be thermally cured Polycarbosilane, forms silicon carbide ceramics precast body;
Step 3: precast body is carefully transferred in annealing device, in argon atmosphere, is warming up to 135 with 6 DEG C/min
DEG C, 5h is handled, after removing solvent completely, continues to be warming up to 255 DEG C with 6 DEG C/min, keeps the temperature 1h, be further continued for 6 DEG C/min heating
To 400 DEG C, 1h is kept the temperature, the precast body with some strength, gel content 100% are obtained;
Step 4: the precast body that step 3 is obtained is put into pyrolysis oven, in argon atmosphere, is warming up to 6 DEG C/min
It 1100 DEG C, after keeping the temperature 1h, is cooled to room temperature to obtain 3D printing silicon carbide ceramics, linear shrinkage ratio 15%, bulk density 2.3g/cm3
Embodiment 3:
It is as follows with the preparation process that can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics:
Step 1: can be thermally cured the preparation of Polycarbosilane, same as Example 2.
Step 2: preparing solution according to mass ratio 6: 4 for can be thermally cured Polycarbosilane and the hexamethylene that prepare in step 1,
Prepared solution is added in 3D printer, heated solution is to 70 DEG C, after keeping the temperature 10min, sprays hot solution to 70 by spray head
DEG C carrier on, spray head is apart from carrier 0.8mm, as the solvent evaporates, on carrier formed one layer of solid-state can be thermally cured poly- carbon silicon
Alkane then carries out spraying hot solvent on newly formed solid-state Polycarbosilane again, and forming one layer of new solid-state can be thermally cured poly- carbon
Silane repeats to spray hot solvent, after successively accumulation solid-state can be thermally cured Polycarbosilane, forms silicon carbide ceramics precast body;
Step 3: precast body is carefully transferred in annealing device, in argon atmosphere, is warming up to 135 with 6 DEG C/min
DEG C, 5h is handled, after removing solvent completely, continues to be warming up to 255 DEG C with 6 DEG C/min, keeps the temperature 1h, be further continued for 6 DEG C/min heating
To 400 DEG C, 1h is kept the temperature, the precast body with some strength, gel content 100% are obtained;
Step 4: the precast body that step 3 is obtained is put into pyrolysis oven, in argon atmosphere, is warming up to 6 DEG C/min
It 1100 DEG C, after keeping the temperature 1h, is cooled to room temperature to obtain 3D printing silicon carbide ceramics, linear shrinkage ratio 15%, bulk density 2.4g/cm3
Comparative example 1:
A kind of preparation process can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics is as follows:
Step 1: Polycarbosilane (molecular weight 1900,260 DEG C of softening point) and dimethylbenzene are molten according to the preparation of mass ratio 6: 4
Prepared solution is added in 3D printer liquid, and heated solution after keeping the temperature 10min, sprays hot solution by spray head to 130 DEG C
To 130 DEG C of carriers, spray head is apart from carrier 0.8mm, and as the solvent evaporates, one layer of solid-state of formation can be thermally cured poly- on carrier
Carbon silane, keeping spray head to can be thermally cured with new support solid-state is still 0.8mm at a distance from Polycarbosilane, in the newly formed poly- carbon of solid-state
Spraying hot solvent is carried out on silane again, forming one layer of new solid-state can be thermally cured Polycarbosilane, repeats spraying operation, successively accumulates
After solid-state can be thermally cured Polycarbosilane, silicon carbide ceramics precast body is formed;
Step 3: precast body is carefully transferred in annealing device, in argon atmosphere, is warming up to 135 with 6 DEG C/min
DEG C, 5h is handled, after removing solvent completely, continues to be warming up to 255 DEG C with 6 DEG C/min, keeps the temperature 1h, be further continued for 6 DEG C/min heating
To 400 DEG C, 1h is kept the temperature, is cooled to room temperature, precast body has melted the pattern to collapse without 3D printing, gel content 0%.
Claims (9)
1. can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics, it is characterised in that lower method and step:
(1) Polycarbosilane and solvent will be can be thermally cured to mix according to 30~60wt% of mass percent and 70 DEG C~40wt% respectively
Wiring solution-forming;
(2) solution is added in 3D printer, heated solution after keeping the temperature a period of time, is ejected to 70 DEG C~135 DEG C by spray head
On 70 DEG C~135 DEG C of carrier, as solvent volatilizees, formed one layer it is solid can be thermally cured Polycarbosilane, then with it is solid can
Heat cure Polycarbosilane is new support, is sprayed next time, repeats to spray, successively accumulation can be thermally cured Polycarbosilane and form carbon
The precast body of SiClx ceramics;
(3) precast body is carefully transferred in annealing device, in argon atmosphere, precast body is heat-treated, including solvent
Removing and can be thermally cured the crosslinking curing of Polycarbosilane itself, obtain precast body;
(4) precast body is put into pyrolysis oven, in argon atmosphere, high temperature pyrolysis is carried out to it, room temperature is cooled to, obtains 3D printing
Silicon carbide ceramics.
2. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: can be thermally cured Polycarbosilane: being made by Polycarbosilane and vinyl silanes by hydrosilylation, molecule
Amount 1700~3200.
3. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: preferably, what the Polycarbosilane was reset by polydimethylsiloxane Pintsch process, softening point 200
~300 DEG C, molecular weight 1500~2800;
Preferably, the Polycarbosilane (PVCS) that can be thermally cured only contains silicon, three kinds of carbon, hydrogen elements;
Preferably, the vinyl silanes are dimethyl divinyl silane, in tetrapropylene base silane, tetravinyl silane
It is at least one.
4. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: solvent is at least one of dimethylbenzene, toluene, hexamethylene.
5. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: the carrier is easy to the plate removed with precast body, such as glass plate in the step (2).
6. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: in the step (3),
The solvent removal temperature are as follows: be warming up to 70 DEG C~135 DEG C with 1 DEG C/min~5 DEG C/min heating rate, keep the temperature 3h
~30h.Preferably, the solvent removal temperature are as follows: with 2 DEG C/min~3 DEG C/min heating rate be warming up to 70 DEG C~
135 DEG C, keep the temperature 5h~10h.
7. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: in the step (3), the crosslinking curing temperature that can be thermally cured Polycarbosilane itself are as follows: de- with solvent
Except temperature is starting point, 200 DEG C~300 DEG C are warming up to 0.5 DEG C/min~3 DEG C/min heating rate, after keeping the temperature 2h~8h,
400 DEG C are warming up to 3 DEG C/min~10 DEG C/min heating rate, keeps the temperature 1h~8h.
8. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: detailed process is as follows in the step (4):
Under argon atmosphere, by step (3) treated precast body, with 400 DEG C for starting point, with 2 DEG C/min~20 DEG C/min
Heating rate is warming up to 1100 DEG C~1200 DEG C, keeps the temperature 1h~2h hours, then cools to room temperature, obtain 3D printing silicon carbide
Ceramics.
9. according to claim 1 a kind of can be thermally cured the preparation side that Polycarbosilane 3D printing prepares silicon carbide ceramics
Method, it is characterized in that: in the step (4), the silicon carbide ceramics linear shrinkage ratio 12~15% prepared, bulk density is 2.3~
2.4g/cm3。
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