CN115872752A - Ceramic slurry for photocuring 3D printing and preparation method thereof, and ceramic and preparation method thereof - Google Patents
Ceramic slurry for photocuring 3D printing and preparation method thereof, and ceramic and preparation method thereof Download PDFInfo
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- CN115872752A CN115872752A CN202211741698.3A CN202211741698A CN115872752A CN 115872752 A CN115872752 A CN 115872752A CN 202211741698 A CN202211741698 A CN 202211741698A CN 115872752 A CN115872752 A CN 115872752A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 117
- 238000010146 3D printing Methods 0.000 title claims abstract description 51
- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 polysiloxane Polymers 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims abstract description 3
- 230000002745 absorbent Effects 0.000 claims abstract description 3
- 239000012700 ceramic precursor Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000006096 absorbing agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000197 pyrolysis Methods 0.000 claims description 15
- BPTKLSBRRJFNHJ-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diol Chemical group OC1=CC(O)=CC=C1N=NC1=CC=CC=C1 BPTKLSBRRJFNHJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 11
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 claims description 2
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007639 printing Methods 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 7
- 239000011225 non-oxide ceramic Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007158 vacuum pyrolysis Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- MRQIXHXHHPWVIL-ISLYRVAYSA-N Sudan I Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C1=CC=CC=C1 MRQIXHXHHPWVIL-ISLYRVAYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- NYHMLROEJNBVEF-UHFFFAOYSA-N tris(trimethylsilyloxy)silylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C NYHMLROEJNBVEF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a ceramic slurry for photocuring 3D printing and a preparation method thereof, and a ceramic and a preparation method thereof, wherein the ceramic slurry comprises the following preparation raw materials in parts by weight: 30-70 parts of polysiloxane; 20-60 parts of a silane coupling agent; 5-20 parts of butyl acrylate; 0.1-5 parts of a photoinitiator; 0.01 to 0.5 portion of light absorbent. The ceramic slurry for photocuring 3D printing is used for printing, and the forming precision, the ceramic yield and the mechanical property are high.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to ceramic slurry for photocuring 3D printing and a preparation method thereof, and ceramic and a preparation method thereof.
Background
Compared with common oxide ceramics, non-oxide ceramics such as carbides, nitrides, carbonitrides, oxycarbides and the like have better heat resistance and chemical stability and more excellent mechanical properties, and components of the non-oxide ceramics can be used in extreme environments such as high temperature, strong corrosion and the like. However, the production of non-oxide ceramic components, in particular complex components, is relatively difficult. The 3D printing technology has subversive significance for the processing of complex ceramic components. Among a plurality of ceramic 3D printing technologies, the photocuring 3D printing technology has high forming precision and higher complexity of the structure. However, since many non-oxide ceramics generally have dark colors and strong light absorption, the slurry is difficult to cure, and a high-energy optical machine is required for curing, which has high requirements for 3D printing equipment. More importantly, the sintering temperature of the carbide or nitride ceramics is very high (generally more than 1500 ℃), which puts higher requirements on sintering equipment and also causes greater energy waste. In addition, the powder-based slurry is generally not high in molding accuracy due to the scattering effect of the ceramic particles on light. Therefore, the fabrication of non-oxide ceramic components of high strength, high precision and high complexity remains a non-trivial challenge.
The non-oxide ceramic is prepared by photocuring 3D printing of the polymer-derived ceramic precursor, and has the advantages of high molding precision and low pyrolysis temperature. And printing and forming can be carried out by adopting a common resin photocuring 3D printer, and the corresponding ceramic structure can be obtained after the cured ceramic precursor green body is pyrolyzed at high temperature in vacuum or inert atmosphere. At present, the polymer-derived ceramic precursor can be combined with a photocuring 3D printing technology to prepare non-oxide ceramic structures such as silicon carbide, silicon oxycarbide, silicon nitride, silicon carbonitride and the like. However, the forming accuracy of these techniques is still not high, and the ceramic yield is also low (typically 20% to 50%). The forming precision of common Stereolithography (SLA) and Digital Light Processing (DLP) 3D printing technologies can reach below 10 mu m, but the forming precision of polymer derived ceramic precursors manufactured by adopting the two photocuring 3D printing technologies reported in the literature is usually about 200 mu m and far less than the manufacturing precision requirement of high-precision parts.
Therefore, there is a need to develop a polymer ceramic slurry with high molding precision, high ceramic yield, good mechanical properties, and can be used for photocuring 3D printing.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the ceramic slurry for photocuring 3D printing, which can effectively improve the forming precision, the ceramic yield and the mechanical property.
The invention also provides a preparation method of the ceramic slurry for photocuring 3D printing.
The third aspect of the present invention also provides a ceramic.
The fourth aspect of the present invention also provides a method for producing the ceramic.
According to a first aspect of the present invention, there is provided a ceramic paste for photocuring 3D printing, including the following raw materials:
the ceramic slurry for photocuring 3D printing provided by the embodiment of the invention has at least the following beneficial effects:
(1) The ceramic slurry for photocuring 3D printing is used for printing, and the forming precision is very high. Butyl acrylate is added into the polysiloxane solution, so that the green strength of the cured ceramic precursor can be improved, and the structural damage caused by the separation of the high-precision three-dimensional structure from the release film in the printing process is avoided. By adding a proper amount of light absorbent, a fine three-dimensional structure with the characteristic size as low as 8 mu m can be prepared by adopting a Digital Light Processing (DLP) 3D printer; in addition, the effect of reducing the system viscosity, improving the reaction activity and improving the ceramic yield can be achieved by adding a small amount of butyl acrylate.
(2) The introduction of silane coupling agent to replace organic solvent can greatly improve the ceramic yield, and through the optimization of the material formula, the ceramic yield of the invention can reach more than 60 percent, which is greatly higher than the ceramic yield of 20 to 50 percent in the prior art. The ceramic has high yield, and simultaneously means that the gas products discharged in the high-temperature pyrolysis process are few, the structure is compact, the defects are few, the cracking is not easy, and the improvement of the strength of the material and the structure is facilitated.
(3) Pottery prepared from ceramic slurry for 3D printingThe porcelain has the advantage of strong mechanical property, and the specific strength is as high as 5.36 multiplied by 10 5 N m/kg, which is much higher than the prior art.
According to some embodiments of the invention, the polysiloxane has the following chemical structure:
wherein R is 1 And R 2 Independently selected from methyl or phenyl; x is more than 0 and less than 1. Thus, the polysiloxanes selected have a higher ceramic yield.
According to some embodiments of the invention, the silicone grade is selected
604、/>
610 or
At least one of MK.
According to some embodiments of the invention, the silane coupling agent is a compound containing a methacryloxy group or an acryloxy group; and a methoxy or ethoxy silane coupling agent.
The invention introduces a silane coupling agent containing methacryloxy (or acryloxy) and methoxy (or ethoxy) as a solvent for dissolving polysiloxane. The methacryloxy (or acryloxy) in the silane coupling agent can participate in the photocuring reaction, which is beneficial to improving the reaction activity.
According to some embodiments of the invention, the silane coupling agent comprises at least one of 3- (methacryloxy) propyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldiethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltri (trimethylsiloxy) silane, 3- (acryloxy) propyltrimethoxysilane, or acryloxymethyltrimethoxysilane.
According to some embodiments of the invention, the light absorber is sudan orange G. Thus, selecting the light absorber of the present application as sudan orange G can improve the molding accuracy.
According to some embodiments of the invention, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
According to a second aspect of the present invention, there is provided a method for preparing a photocurable ceramic paste for 3D printing, including the steps of:
s1, mixing polysiloxane and a silane coupling agent; adding acid to hydrolyze; obtaining a mixed solution;
and S2, mixing the mixed solution, butyl acrylate, a photoinitiator and a light absorber to obtain the photocuring 3D printing ceramic slurry.
According to some embodiments of the invention, the acid comprises at least one of hydrochloric acid, nitric acid, or sulfuric acid.
The third aspect of the present invention provides a ceramic prepared by using the ceramic slurry or the ceramic slurry prepared by the method as a raw material and using a photo-curing molding technique.
In a fourth aspect, the present invention provides a method for producing a ceramic, comprising the steps of:
s110, performing 3D printing on the ceramic slurry to obtain a ceramic precursor green body with a three-dimensional structure;
s120, placing the ceramic precursor green body at 400-1400 ℃; and pyrolyzing in vacuum or inert atmosphere to obtain the ceramic.
According to some embodiments of the invention, the step of pyrolyzing in step S120 is as follows:
(1) Heating to 350-400 ℃ at a speed of 0.1-1 ℃/min, and preserving the heat for 2-4 hours;
(2) Heating to 450-550 ℃ at a speed of 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(3) Heating to 600-700 ℃ at a speed of 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(4) Heating to 800-1400 deg.c at 1-5 deg.c/min and maintaining for 2-4 hr;
(5) Cooling to room temperature at 1-5 deg.c/min.
Thus, the ceramic yield can be further improved by the pyrolysis step described above.
According to some embodiments of the invention, in step S110, the parameters of the 3D printing are: ultraviolet light wavelength of 405nm and light intensity of 5-150 mW/cm 2 The exposure time is 0.5-15 s, and the thickness of each layer is 5-20 μm.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph of the viscosity as a function of shear rate for the ceramic slurries of example 1 and comparative example 1;
FIG. 2 is a graph showing the results of mechanical property tests on ceramic precursor green specimens of Experimental example 1 and Experimental example 2;
FIG. 3 is a photo-cured 3D printed in-plane precision test chart (in-plane precision up to 5 μm) of the ceramic slurry of example 1;
FIG. 4 is a scanning electron micrograph of the three-dimensional octet-tress lattice structure of the ceramic precursor green body of Experimental example 1 (minimum feature size down to 8 μm);
FIG. 5 is a scanning electron microscope image (very poor molding accuracy) of a ceramic precursor green body having a three-dimensional octet-tress lattice structure 3D printed with the ceramic slurry provided in comparative example 4;
FIG. 6 is a scanning electron micrograph of a three-dimensional structure of a silicon oxycarbide ceramic formed after vacuum pyrolysis according to Experimental example 1: a and b are Gyroid structures; c and d are I-WP structures;
FIG. 7 is a graph of linear shrinkage and mass loss of green ceramic precursors of Experimental example 1 when pyrolyzed at various temperatures;
FIG. 8 is a graph of compressive stress-strain curves for Gyroid and I-WP structural silicon oxycarbide ceramics of Experimental example 1;
FIG. 9 is a scanning electron microscope image of the Ocet-tress lattice structure of the silicon oxycarbide ceramic of Experimental example 3 after pyrolysis;
FIG. 10 is a graph of compressive stress-strain curves for the Octet-tress lattice structure of the silicon oxycarbide ceramic of Experimental example 3;
FIG. 11 is a scanning electron micrograph of a Gyroid structure of a silicon oxycarbide ceramic of Experimental example 4;
FIG. 12 is a scanning electron microscope image of the Ocet-tress lattice structure of the silicon oxycarbide ceramic of Experimental example 5.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
Example 1
Example 1 provides a photocurable ceramic paste for 3D printing, the amount and preparation method of which are as follows:
s1, weighing
604, 50 parts of polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 10 parts of butyl acrylate, 1 part of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorber Sudan orange G into the mixed solution, and stirring until the mixture is completely dissolved to obtain the ceramic slurry.
Example 2
s1, weighing
50 parts of 610 polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing and stirring the two until the two are completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 5 parts of butyl acrylate, 1 part of photoinitiator phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorber Sudan orange G into the mixed solution, and stirring until the light absorber Sudan orange G is completely dissolved to obtain the ceramic slurry.
Example 3
Example 3 provides a photocurable ceramic paste for 3D printing, the amount and preparation method of which are as follows:
s1, weighing
50 parts of MK polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two components, stirring until the components are completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 10 parts of butyl acrylate, 1 part of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorber Sudan orange G into the mixed solution, and stirring until the mixture is completely dissolved to obtain the ceramic slurry.
Example 4
s1, weighing
604 45 parts of polysiloxane and 35 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 5 parts of butyl acrylate, 2 parts of photoinitiator phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.05 part of light absorber Sudan orange G into the mixed solution, and stirring until the light absorber Sudan orange G is completely dissolved to obtain the ceramic slurry.
Example 5
Example 5 provides a photocurable ceramic paste for 3D printing, in the following amounts and preparation method:
s1, weighing
604 60 parts of polysiloxane and 30 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 20 parts of butyl acrylate, 2 parts of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.2 part of light absorber Sudan orange G into the mixed solution, and stirring until the mixture is completely dissolved to obtain the ceramic slurry.
Comparative example 1
Comparative example 1 provides a photocurable ceramic paste for 3D printing, the amount and preparation method of which are as follows:
s1, weighing
604, 50 parts of polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 1 part of photoinitiator phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorber Sudan orange G into the mixed solution, and stirring until the mixture is completely dissolved to obtain the ceramic slurry.
Comparative example 2
Comparative example 2 provides a photocurable ceramic paste for 3D printing, the amount and preparation method of which are as follows:
s1, weighing
604, 50 parts of polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 10 parts of trimethylolpropane triacrylate, 1 part of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorber Sudan orange G into the mixed solution, and stirring until the materials are completely dissolved to obtain the ceramic slurry.
Comparative example 3
Comparative example 3 provides a photocurable ceramic paste for 3D printing, the amount and preparation method of which are as follows:
s1, weighing
604, 50 parts of polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 10 parts of 1, 6-hexanediol diacrylate, 1 part of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorber Sudan orange G into the mixed solution, and stirring until the materials are completely dissolved to obtain the ceramic slurry.
Comparative example 4
Comparative example 4 provides a photocurable ceramic paste for 3D printing, which was used in the following amounts and prepared by the following methods:
s1, weighing
604, 50 parts of polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxy silane, and mixing the two, stirring the mixture until the mixture is completely dissolved; adding 0.2 part of hydrochloric acid with the concentration of 0.5mol/L into the mixed solution, and continuously stirring for 12 hours to perform hydrolysis reaction;
s2, adding 10 parts of butyl acrylate, 1 part of photoinitiator phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide and 0.1 part of light absorber Sudan I into the mixed solution, and stirring until the mixture is completely dissolved to obtain the ceramic slurry.
Experimental examples 1 and 2
Experimental examples 1 to 2 provide a ceramic, and a preparation method thereof is as follows:
s110, 3D printing is carried out on the ceramic slurry of the embodiment 1 and the ceramic slurry of the comparative example 1 by adopting a molar formula (BMF) S130 photocuring 3D printer, and a ceramic precursor green body with a three-dimensional Octet-tress lattice structure is obtained; a triple-period extremely-small curved surface structure comprising a Gyroid structure and an I-WP structure is printed on the ceramic slurry composition of the embodiment 1; the 3D printing parameters are as follows: ultraviolet light wavelength of 405nm and light intensity of 52.5mW/cm 2 Exposure time 1s, 5 μm per layer thickness.
S120, pyrolyzing the ceramic precursor green body under a vacuum condition to obtain ceramic, wherein the pyrolyzing step is as follows:
(1) Heating to 400 ℃ at a speed of 0.25 ℃/min, and keeping the temperature for 4 hours;
(2) Heating to 500 deg.C at a rate of 0.25 deg.C/min, and maintaining for 4 hr;
(3) Heating to 650 ℃ at a speed of 0.25 ℃/min, and preserving heat for 4 hours;
(4) Heating to 800-1400 deg.c at 1 deg.c/min and maintaining for 2 hr;
(5) Then cooled to room temperature at 2 ℃/min.
Experimental example 3
Experimental example 3 provides a ceramic, which is prepared as follows:
s110, 3D printing is carried out on the ceramic slurry in the embodiment 2 by adopting a molar mass (BMF) S130 photocuring 3D printer, so as to obtain a ceramic precursor green body with a three-dimensional structure; the 3D printing parameters are as follows: ultraviolet light wavelength of 405nm and light intensity of 52.5mW/cm 2 And the exposure time is 2s, the printed three-dimensional model is an octet-tress lattice structure, and the thickness of each layer is 5 mu m.
S120, putting the ceramic precursor green body in an argon atmosphere for pyrolysis to obtain ceramic, wherein the pyrolysis step is as follows:
and (3) placing the printed three-dimensional lattice structure in a tubular furnace, heating to 400 ℃ at the speed of 0.25 ℃/min under the condition of introducing argon, preserving heat for 4 hours at 500 ℃ and 650 ℃ respectively, then heating to 1000 ℃ at the speed of 1 ℃/min, preserving heat for 2 hours, and cooling to room temperature at the speed of 2 ℃/min. And pyrolyzing the ceramic precursor green body in an argon atmosphere heating process to obtain silicon oxycarbide ceramic.
Experimental example 4
Experimental example 4 provided a ceramic, which was prepared in the same manner as in experimental example 1, except that the raw material was comparative example 2.
Experimental example 5
Experimental example 5 provided a ceramic, which was prepared in the same manner as in experimental example 1, except that the raw material was comparative example 3.
Performance detection
The viscosities of the ceramic slurries provided in example 1 and comparative example 1 were measured using a rheometer, and the results are shown in FIG. 1 at a shear rate of 10s -1 In this case, the viscosity of the ceramic slurry to which butyl acrylate was added in example 1 was only 0.17 pas, whereas the viscosity of the ceramic slurry to which butyl acrylate was not added in comparative example 1 reached 0.61 pas. The addition of the butyl acrylate greatly reduces the viscosity of the ceramic slurry, and is favorable for high-precision 3D printing and forming.
FIG. 2 is a graph showing the results of mechanical property tests of ceramic precursor green specimens of Experimental example 1 and Experimental example 2; in the experimental example 1, butyl acrylate is added, the experimental example 2 does not contain butyl acrylate, the mechanical strength of the material is improved by more than one time after the butyl acrylate is added, and the elongation is improved by more than 4 times. The enhancement of the mechanical property of the precursor green body is beneficial to 3D printing forming of a high-precision three-dimensional structure, and the structure is prevented from being damaged in the separation process of the release film.
Models were designed containing a series of lines of different widths (4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm) with a line pitch of 50 μm. The model was printed using a Mohs Square (BMF) S130 photocuring 3D Printer to test the in-plane exposure accuracy of the ceramic paste provided in example 1 with a light intensity set at 32mW/cm 2 Exposure time 2s, print layer thickness 5 μm, 4 layers total. The test result is shown in fig. 3, the width of the printable line is 5 μm at the thinnest, which shows that the highest in-plane molding precision of the material can reach 5 μm.
FIG. 4 is a scanning electron micrograph of a green ceramic precursor having a three-dimensional octet-tress lattice structure shown in Experimental example 1, with a minimum feature size of up to 8 μm.
Fig. 5 is a scanning electron microscope image of a ceramic precursor green body having a three-dimensional octet-tress lattice structure 3D printed with the ceramic slurry provided in comparative example 4, the printing equipment and printing parameters being the same as those of example 1, but with the ceramic slurry prepared by adding the same amount of the light absorber sudan I as in example 1, the structural molding precision is very poor, and the rod diameter dimension is as high as 45 μm.
FIG. 6 is a scanning electron microscope image of Gyroid and I-WP three-cycle extremely-small curved surface structures printed in Experimental example 1 after vacuum pyrolysis at 1100 ℃. The green sizes of the two structures are about 960 microns multiplied by 960 microns, the total sizes of the pyrolyzed ceramic structures are only 700 microns multiplied by 700 microns, the minimum feature size of the Gyroid structures is 11 microns, and the minimum feature size of the I-WP structures is only 5 microns, which shows that the ceramic slurry has very good forming precision and printing effect, and can print high-precision three-dimensional lattice structures and curved surface structures with the feature sizes of the various types reaching the micron level.
FIG. 7 is a graph of linear shrinkage and mass loss of green ceramic precursors of Experimental example 1 when pyrolyzed at various temperatures; when pyrolyzed at 800 ℃, the linear shrinkage was 21.6%, the mass loss was 33.1%, corresponding to a ceramic yield of 66.9%; when pyrolyzed at 1100 ℃, the linear shrinkage was 26.9%, the mass loss was 39.8%, corresponding to a ceramic yield of 60.2%.
Accordingly, the ceramic yields of examples 1 to 5 and comparative examples 2 to 3 were tested at a pyrolysis temperature of 1100 ℃. The results are shown in table 1:
TABLE 1
| Ceramic yield% | |
| Example 1 | 60.2 |
| Example 2 | 60.8 |
| Example 3 | 61.3 |
| Example 4 | 60.6 |
| Example 5 | 62.7 |
| Comparative example 2 | 45.2 |
| Comparative example 3 | 48.0 |
As can be seen from the above table, the ceramic slurry for photocuring 3D printing according to the present invention has a good ceramic yield upon pyrolysis.
FIG. 8 is a graph of compressive stress-strain curves for silicon oxycarbide ceramics of Gyroid and I-WP structures after pyrolysis in Experimental example 1. Although its density is only 0.28g/cm 3 But compressive strengths as high as 112MPa and 150MPa, corresponding specific strengths as high as 4X 10 5 N.m/kg and 5.36X 10 5 N·m/kg。
FIG. 9 shows an octet-tress silicon oxycarbide ceramic structure having a density of only 0.143g/cm after pyrolysis in Experimental example 3 3 . The compressive stress-strain curve of the structure is shown in FIG. 10, the compressive strength is 59.5MPa, and the corresponding specific strength is as high as 4.16 multiplied by 10 5 N·m/kg。
Fig. 11 is a scanning electron microscope image of Gyroid-structured silicon oxycarbide ceramic after pyrolysis in experimental example 4. The 3D printing parameters and the pyrolysis process were the same as in experimental example 1. However, as can be seen from the scanning electron microscope image, the ceramic slurry prepared by trimethylolpropane triacrylate has poor printing effect, low molding precision and many holes in the structure are blocked.
FIG. 12 is a scanning electron microscope image of an octet-tress lattice structure silicon oxycarbide ceramic after pyrolysis in Experimental example 5. The 3D printing parameters and the pyrolysis process were the same as in experimental example 1. However, as can be seen from the scanning electron microscope image, the ceramic slurry prepared by using 1, 6-hexanediol diacrylate has poor printing effect, and many places in the structure are damaged, mainly because the green strength is low, and the structure is damaged when the green and release films are separated in the printing process.
While the present invention has been described in detail with reference to the embodiments thereof, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The ceramic slurry for photocuring 3D printing is characterized by comprising the following preparation raw materials in parts by weight:
2. the photocurable ceramic paste for 3D printing according to claim 1, wherein the polysiloxane has the following chemical structural formula:
wherein R is 1 And R 2 Independently selected from methyl or phenyl, 0 < x < 1.
3. The photocurable ceramic paste for 3D printing according to claim 1, wherein the silane coupling agent is a compound containing a methacryloxy group or an acryloxy group; and a methoxy or ethoxy silane coupling agent.
4. The photocurable 3D printing ceramic paste according to claim 3, wherein the silane coupling agent comprises at least one of 3- (methacryloyloxy) propyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldiethoxysilane, γ -methacryloxypropylmethyldimethoxysilane, methacryloxymethyltriethoxysilane, 3- (acryloxy) propyltrimethoxysilane, or acryloxymethyltrimethoxysilane.
5. The photocurable ceramic paste for 3D printing according to claim 1, wherein the light absorber is sudan orange G.
6. The photocurable ceramic paste for 3D printing according to claim 1, wherein the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
7. The method for preparing the ceramic paste for photocuring 3D printing according to any one of claims 1 to 6, characterized by comprising the steps of:
s1, mixing polysiloxane and a silane coupling agent; adding acid to hydrolyze; obtaining a mixed solution;
and S2, mixing the mixed solution, butyl acrylate, a photoinitiator and a light absorbent to obtain the ceramic slurry for photocuring 3D printing.
8. A ceramic prepared by using the ceramic slurry according to any one of claims 1 to 6 or the ceramic slurry prepared by the method according to claim 7 as a raw material and using a photo-curing molding technique.
9. The method for preparing a ceramic according to claim 8, comprising the steps of:
s110, 3D printing is carried out on the ceramic slurry according to any one of claims 1 to 6, and a ceramic precursor green body with a three-dimensional structure is obtained;
s120, placing the ceramic precursor green body at 400-1400 ℃; and pyrolyzing in vacuum or inert atmosphere to obtain the ceramic.
10. The method for preparing ceramic according to claim 9, wherein the step of pyrolysis in step S120 is as follows:
(1) Heating to 350-400 ℃ at a speed of 0.1-1 ℃/min, and preserving the heat for 2-4 hours;
(2) Heating to 450-550 ℃ at a speed of 0.1-1 ℃/min, and preserving the heat for 2-4 hours;
(3) Heating to 600-700 ℃ at a speed of 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(4) Heating to 800-1400 deg.c at 1-5 deg.c/min and maintaining for 2-4 hr;
(5) Cooling to room temperature at 1-5 deg.c/min.
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