CN115872752B - Ceramic slurry for photocuring 3D printing and preparation method thereof, ceramic and preparation method thereof - Google Patents
Ceramic slurry for photocuring 3D printing and preparation method thereof, ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 115
- 239000002002 slurry Substances 0.000 title claims abstract description 52
- 238000010146 3D printing Methods 0.000 title claims abstract description 50
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 polysiloxane Polymers 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006096 absorbing agent Substances 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 33
- 239000012700 ceramic precursor Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000000197 pyrolysis Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010438 heat treatment 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
- 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 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
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 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
- 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 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
- 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
- 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 11
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001000 micrograph Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 6
- 239000011225 non-oxide ceramic Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 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
- 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
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 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
Classifications
-
- 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a ceramic slurry for photo-curing 3D printing and a preparation method thereof, and 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 silane coupling agent; 5-20 parts of butyl acrylate; 0.1-5 parts of photoinitiator; 0.01 to 0.5 part of light absorber. The invention adopts the ceramic slurry for photo-curing 3D printing for printing, and has the advantages of very high molding precision, high ceramic yield and high mechanical property.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a ceramic slurry for photo-curing 3D printing and a preparation method thereof, and ceramic and a preparation method thereof.
Background
Non-oxide ceramics, such as ceramics of carbide, nitride, carbonitride, oxycarbide and the like, have better heat resistance and chemical stability and better mechanical properties than common oxide ceramics, and the component can be used in extreme environments of high temperature, strong corrosion and the like. However, the preparation of non-oxide ceramic components, particularly complex components, is difficult. The 3D printing technology has subversive significance for processing complex ceramic components. Among the many ceramic 3D printing techniques, the photo-curing 3D printing technique has high molding accuracy and can produce a structure with higher complexity. However, since many non-oxide ceramics are generally dark in color, have strong light absorption, and are difficult to cure, and require a high energy ray machine to cure, the requirements for 3D printing equipment are high. More importantly, the sintering temperature of carbide or nitride ceramics is very high (usually more than 1500 ℃), and higher requirements are put on sintering equipment, so that larger energy waste is caused. In addition, powder-based slurries generally have low molding accuracy due to scattering of light by the ceramic particles. Thus, the preparation of high strength, high precision and high complexity non-oxide ceramic components remains a not insignificant challenge.
The non-oxide ceramic is prepared by utilizing the photo-curing 3D printing polymer derivative ceramic precursor, and has the advantages of high molding precision and low pyrolysis temperature. And (3) printing and forming by adopting a common resin photo-curing 3D printer, and performing high-temperature pyrolysis on the cured ceramic precursor green body in vacuum or inert atmosphere to obtain the corresponding ceramic structure. Currently, polymer derived ceramic precursors can be used in combination with photo-curing 3D printing techniques to prepare non-oxide ceramic structures such as silicon carbide, silicon oxycarbide, silicon nitride, silicon carbonitride, and the like. However, the molding accuracy of these techniques is still not high, and the ceramic yield is also low (typically 20% to 50%). The molding accuracy of the common Stereolithography (SLA) and Digital Light Processing (DLP) 3D printing technologies can reach below 10 μm, but the molding accuracy of the polymer-derived ceramic precursor manufactured by the two photocuring 3D printing technologies reported in the literature is usually about 200 μm, which is far from reaching the manufacturing accuracy requirement of high-precision parts.
Therefore, it is necessary to develop a polymer ceramic paste which has high molding accuracy, high ceramic yield, good mechanical properties and can be used for photo-curing 3D printing.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the first aspect of the invention provides a 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 light-cured 3D printing.
The third aspect of the present invention also provides a ceramic.
The fourth aspect of the invention also provides a method for preparing the ceramic.
According to a first aspect of the present invention, there is provided a ceramic slurry for photo-curing 3D printing, comprising the following preparation raw materials in parts by weight:
the photocuring 3D printing ceramic slurry provided by the embodiment of the invention has at least the following beneficial effects:
(1) The invention adopts the ceramic slurry for photo-curing 3D printing for printing, and has very high molding precision. Butyl acrylate is added into the polysiloxane solution, so that the green strength of the cured ceramic precursor can be improved, and structural damage caused by separation of a high-precision three-dimensional structure from a release film in the printing process is avoided. By adding a proper amount of light absorber, a Digital Light Processing (DLP) 3D printer can be used for preparing a fine three-dimensional structure with a characteristic size as low as 8 mu m; in addition, the addition amount of butyl acrylate is small, so that the effects of reducing the viscosity of the system, improving the reactivity and improving the ceramic yield can be achieved.
(2) The ceramic yield can be greatly improved by introducing the silane coupling agent to replace the organic solvent, and can reach more than 60 percent by optimizing the material formula, which is greatly higher than 20-50 percent in the prior art. The ceramic yield is high, and meanwhile, the method 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 difficult, and the improvement of the strength of materials and structures is facilitated.
(3) The ceramic prepared by the ceramic slurry for 3D printing 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 substantially higher than the prior art.
According to some embodiments of the invention, the polysiloxane has the following chemical formula:
wherein R is 1 And R is 2 Independently selected from methyl or phenyl; x is more than 0 and less than 1. Thus, the selected polysiloxanes have a higher ceramic yield.
According to some embodiments of the invention, the polysiloxane grade is selected604、/>610 orAt least one of MK.
According to some embodiments of the invention, the silane coupling agent is a methacryloxy group or an acryloxy group; and methoxy or ethoxy silane coupling agents.
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 reactivity.
According to some embodiments of the invention, the silane coupling agent comprises at least one of 3- (methacryloxy) propyl trimethoxysilane, 3-methacryloxy propyl methyl dimethoxy silane, methacryloxy propyl triethoxy silane, methacryloxy propyl methyl diethoxy silane, gamma-methacryloxy propyl methyl dimethoxy silane, methacryloxy methyl triethoxy silane, methacryloxy methyl tris (trimethylsiloxy) silane, 3- (acryloxy) propyl trimethoxy silane, or acryloxy methyl trimethoxy silane.
According to some embodiments of the invention, the light absorber is sudan orange G. Thus, the light absorber of the present application is selected to be sudan orange G, which can improve molding accuracy.
According to some embodiments of the invention, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine 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 the ceramic slurry for photo-curing 3D printing, comprising the steps of:
s1, mixing polysiloxane and a silane coupling agent; adding acid to hydrolyze the mixture; obtaining a mixed solution;
and S2, mixing the mixed solution, butyl acrylate, a photoinitiator and a light absorber to obtain the photocuring ceramic slurry for 3D printing.
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, which is prepared by using the ceramic slurry described above or the ceramic slurry prepared according to the method described above as a raw material and adopting a photo-curing molding technology.
According to a fourth aspect of the present invention, there is provided a method of preparing 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 ℃; pyrolyzing under vacuum or inert atmosphere to obtain ceramic.
According to some embodiments of the invention, the step of pyrolyzing in step S120 is as follows:
(1) Heating to 350-400 ℃ at 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(2) Heating to 450-550 ℃ at 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(3) Heating to 600-700 ℃ at 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(4) Heating to 800-1400 ℃ at 1-5 ℃/min, and preserving heat for 2-4 hours;
(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 with 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 mu m.
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 foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph of viscosity versus shear rate for ceramic slurries of example 1 and comparative example 1;
FIG. 2 is a graph of the results of mechanical property testing of green ceramic precursor splines of experimental examples 1 and 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 microscope image of a three-dimensional OCtet-truss lattice structure of a green ceramic precursor of Experimental example 1 (minimum feature size as low as 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-trus lattice structure 3D printed using the ceramic slurry provided in comparative example 4;
fig. 6 is a scanning electron microscope image of a three-dimensional structure of silicon oxycarbide ceramic formed after vacuum pyrolysis in experimental example 1: a and b are Gyroid structures; c and d are I-WP structures;
FIG. 7 is a graph showing linear shrinkage and mass loss of green ceramic precursor of Experimental example 1 when pyrolyzed at different temperatures;
FIG. 8 is a compressive stress-strain curve of the silica carbide ceramic of the Gyroid and I-WP structures of experimental example 1;
FIG. 9 is a scanning electron microscope image of the array structure of the fumed silica ceramic Octet-trus of Experimental example 3;
FIG. 10 is a graph showing the compressive stress-strain curve of the oxide-lattice structure of the silicon oxycarbide ceramic of experimental example 3;
FIG. 11 is a scanning electron microscope image of the silica carbide ceramic Gyroid structure of Experimental example 4;
FIG. 12 is a scanning electron microscope image of the array structure of the silicon oxycarbide ceramic Octet-trus of experimental example 5.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
Example 1 provides a ceramic slurry for photo-curing 3D printing, the amount and preparation method of which are as follows:
s1, weighing604 polysiloxane 50 parts, 3- (methacryloyloxy) propyl trimethoxysilane 40 parts, and mixing the two, and stirring 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 10 parts of butyl acrylate, 1 part of photo-initiator 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 ceramic slurry.
Example 2
Example 2 provides a ceramic paste for photo-curing 3D printing, the amount and preparation method of which are as follows:
s1, weighing610 polysiloxane 50 parts, 3- (methacryloyloxy) propyltrimethoxysilane 40 parts, mixing the two, stirring until 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 5 parts of butyl acrylate, 1 part of photo-initiator 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 ceramic slurry.
Example 3
Example 3 provides a ceramic paste for photo-curing 3D printing, the amount and preparation method of which are as follows:
s1, weighing50 parts of MK polysiloxane and 40 parts of 3- (methacryloyloxy) propyl trimethoxysilane, and mixing the two, and 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 10 parts of butyl acrylate, 1 part of photo-initiator 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 ceramic slurry.
Example 4
Example 4 provides a ceramic paste for photo-curing 3D printing, the amount and preparation method of which are as follows:
s1, weighing604 45 parts of polysiloxane, 35 parts of 3- (methacryloyloxy) propyl trimethoxysilane, and mixing the two, and stirring 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 5 parts of butyl acrylate, 2 parts of photo-initiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.05 part of light absorber Sudan orange G into the mixed solution, and stirring until the mixture is completely dissolved to obtain ceramic slurry.
Example 5
Example 5 provides a ceramic paste for photo-curing 3D printing, the amount and preparation method of which are as follows:
s1, weighing60 parts of polysiloxane, 30 parts of 3- (methacryloyloxy) propyl trimethoxysilane, and mixing the two, and stirring 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 enable the mixed solution to undergo 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 ceramic slurry.
Comparative example 1
Comparative example 1 provides a ceramic paste for photo-curing 3D printing, which is used in the following amount and preparation method:
s1, weighing604 polysiloxane 50 parts, 3- (methacryloyloxy) propyl trimethoxysilane 40 parts, and mixing the two, and stirring 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 1 part of photo-initiator 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 ceramic slurry.
Comparative example 2
Comparative example 2 provides a ceramic paste for photo-curing 3D printing, which is used in the following amount and preparation method:
s1, weighing604 polysiloxane 50 parts, 3- (methacryloyloxy) propyl trimethoxysilane 40 parts, and mixing the two, and stirring 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 10 parts of trimethylolpropane triacrylate, 1 part of photo-initiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.1 part of light absorbent Sudan orange G into the mixed solution, and stirring until the mixture is completely dissolved to obtain ceramic slurry.
Comparative example 3
Comparative example 3 provides a ceramic paste for photo-curing 3D printing, which is used in the following amount and preparation method:
S1、weighing and weighing604 polysiloxane 50 parts, 3- (methacryloyloxy) propyl trimethoxysilane 40 parts, and mixing the two, and stirring 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 10 parts of 1, 6-hexanediol diacrylate, 1 part of photo-initiator 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 ceramic slurry.
Comparative example 4
Comparative example 4 provides a ceramic paste for photo-curing 3D printing, which is used in the following amount and preparation method:
s1, weighing604 polysiloxane 50 parts, 3- (methacryloyloxy) propyl trimethoxysilane 40 parts, and mixing the two, and stirring 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 enable the mixed solution to undergo hydrolysis reaction;
s2, adding 10 parts of butyl acrylate, 1 part of photo-initiator phenyl bis (2, 4, 6-trimethylbenzoyl) 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 ceramic slurry.
Experimental examples 1 to 2
Experimental examples 1-2 provide a ceramic, the preparation method of which is as follows:
s110, performing 3D printing on the ceramic slurry of the example 1 and the comparative example 1 by adopting a Moire equation (BMF) S130 photocuring 3D printer to obtain a ceramic precursor green body with a three-dimensional Octet-trus lattice structure; triple period extremely small curved structures, including Gyroid structures and I-WP structures, were also printed on the ceramic slurry combinations of example 1; the 3D printing parameters are: ultraviolet light with wavelength of 405nm and light intensity of 52.5mW/cm 2 The exposure time was 1s, and the thickness of each layer was 5. Mu.m.
S120, placing the ceramic precursor green body under a vacuum condition for pyrolysis to obtain ceramic, wherein the pyrolysis steps are as follows:
(1) Heating to 400 ℃ at a speed of 0.25 ℃/min, and preserving heat for 4 hours;
(2) Raising the temperature to 500 ℃ at 0.25 ℃/min, and preserving the heat for 4 hours;
(3) Raising the temperature to 650 ℃ at 0.25 ℃/min, and preserving the heat for 4 hours;
(4) Heating to 800-1400 ℃ at 1 ℃/min, and preserving heat for 2 hours;
(5) And then cooled to room temperature at 2 ℃/min.
Experimental example 3
Experimental example 3 provides a ceramic, which is prepared by the following method:
s110, performing 3D printing on the ceramic slurry of the embodiment 2 by adopting a Moir' S (BMF) S130 photocuring 3D printer to obtain a ceramic precursor green body with a three-dimensional structure; the 3D printing parameters are: ultraviolet light with wavelength of 405nm and light intensity of 52.5mW/cm 2 The exposure time is 2s, the three-dimensional model is printed as an OCtet-truss lattice structure, and the thickness of each layer is 5 mu m.
S120, placing the ceramic precursor green body in an argon atmosphere for pyrolysis to obtain ceramic, wherein the pyrolysis steps are as follows:
placing the printed three-dimensional lattice structure in a tube furnace, heating to 400 ℃ at a speed of 0.25 ℃/min under the condition of introducing argon, preserving heat for 4 hours at 500 ℃ and 650 ℃ respectively, heating to 1000 ℃ at a speed of 1 ℃/min, preserving heat for 2 hours, and cooling to room temperature at a speed of 2 ℃/min. And pyrolyzing the ceramic precursor green body into silicon oxycarbide ceramic in the heating process of argon atmosphere.
Experimental example 4
Experimental example 4 provides a ceramic, which is prepared in the same manner as in Experimental example 1, except that the raw material is comparative example 2.
Experimental example 5
Experimental example 5 provides a ceramic, which is prepared in the same manner as in Experimental example 1, except that the raw material is comparative example 3.
Performance detection
The ceramic slurries provided in example 1 and comparative example 1 were tested for viscosity using a rheometer and the results are shown in FIG. 1 at a shear rate of10s -1 In this case, the viscosity of the ceramic slurry to which butyl acrylate was added in example 1 was only 0.17 Pa.s, whereas the viscosity of the ceramic slurry to which butyl acrylate was not added in comparative example 1 was 0.61 Pa.s. The addition of butyl acrylate greatly reduces the viscosity of the ceramic slurry, and is beneficial to high-precision 3D printing and forming.
FIG. 2 is a graph of the results of mechanical property testing of green ceramic precursor splines of experimental examples 1 and 2; butyl acrylate is added in the experimental example 1, butyl acrylate is not contained in the experimental example 2, the mechanical strength of the material is improved by more than one time after butyl acrylate is added, and the elongation is improved by more than 4 times. The enhancement of the mechanical property of the precursor green compact is beneficial to 3D printing forming of a high-precision three-dimensional structure, and damage to the structure in the separation process of the structure and the release film is avoided.
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. Printing of the ceramic slurry provided in this model test example 1 using a Moire Fair (BMF) S130 photo-curing 3D printer with an in-plane exposure accuracy, the light intensity was set at 32mW/cm 2 The exposure time was 2s, the thickness of the printed layer was 5 μm, and 4 layers were printed altogether. The test results are shown in FIG. 3, with the printable line width being as thin as 5 μm, indicating that the highest in-plane molding accuracy of the material can be up to 5 μm.
FIG. 4 is a scanning electron microscope image of a green ceramic precursor having a three-dimensional octet-trus lattice structure, as 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 ottet-trus lattice structure, which was 3D printed using the ceramic slurry provided in comparative example 4, and the printing apparatus and printing parameters were the same as example 1, but the ceramic slurry prepared by adding the same amount of the light absorber sudan I as in example 1 was very poor in structural molding accuracy, and the rod diameter size was as high as 45 μm.
FIG. 6 is a scanning electron microscope image of the printed Gyroid and I-WP of Experimental example 1 after vacuum pyrolysis at 1100 ℃. The green sizes of the two structures are about 960 mu m multiplied by 960 mu m, the total size of the ceramic structure after pyrolysis is only 700 mu m multiplied by 700 mu m, wherein the minimum feature size of the Gyroid structure is 11 mu m, and the minimum feature size of the I-WP structure is only 5 mu m, 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 feature sizes reaching micron level of various types.
FIG. 7 is a graph showing linear shrinkage and mass loss of green ceramic precursor of Experimental example 1 when pyrolyzed at different temperatures; at 800 ℃ pyrolysis, the linear shrinkage is 21.6%, the mass loss is 33.1%, and the corresponding ceramic yield is 66.9%; at 1100 ℃ pyrolysis, the linear shrinkage was 26.9%, the mass loss was 39.8%, and the corresponding ceramic yield was 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 |
From the above table, the photo-curing 3D printing ceramic slurry of the invention has better ceramic yield during pyrolysis.
FIG. 8 is a compressive stress-strain curve of silica carbide ceramics of the Gyroid and I-WP structures after pyrolysis of Experimental example 1. Although the density is only 0.28g/cm 3 But the compression strength is up to 112MPa and 150MPa, and the corresponding specific strength is up to 4 multiplied by 10 5 N.m/kg and 5.36×10 5 N·m/kg。
FIG. 9 shows the structure of an OCtet-truss silicon oxycarbide ceramic having a density of only 0.143g/cm after pyrolysis of 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 4.16X10 5 N·m/kg。
FIG. 11 is a scanning electron microscope image of a silica carbide ceramic of a Gyroid structure after pyrolysis in Experimental example 4. The 3D printing parameters and the pyrolysis process are the same as in experimental example 1. However, as can be seen from a scanning electron microscope, the ceramic slurry prepared from trimethylolpropane triacrylate has poor printing effect and low molding accuracy, and many holes in the structure are blocked.
FIG. 12 is a scanning electron microscope image of a silicon oxycarbide ceramic with a octet-trus lattice structure after pyrolysis in Experimental example 5. The 3D printing parameters and the pyrolysis process are the same as in experimental example 1. However, as can be seen from a scanning electron microscope, the ceramic slurry prepared from 1, 6-hexanediol diacrylate has poor printing effect, and a plurality of places in the structure are damaged, and the main reason is that the green strength is low, so that the structure is damaged when the green body is separated from the release film in the printing process.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (6)
1. The ceramic slurry for photo-curing 3D printing is characterized by comprising the following preparation raw materials in parts by weight:
the light absorber is Sudan orange G;
the silane coupling agent comprises at least one of 3- (methacryloxy) propyl trimethoxy silane, 3-methacryloxy propyl methyl dimethoxy silane, methacryloxy propyl triethoxy silane, methacryloxy propyl methyl diethoxy silane, gamma-methacryloxy propyl methyl dimethoxy silane, methacryloxy methyl triethoxy silane, 3- (acryloxy) propyl trimethoxy silane or acryloxy methyl trimethoxy silane;
the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
the preparation method of the ceramic slurry for photo-curing 3D printing comprises the following steps: mixing polysiloxane and silane coupling agent; adding acid to hydrolyze the mixture; obtaining a mixed solution; and mixing the mixed solution, butyl acrylate, a photoinitiator and a light absorber to obtain the ceramic slurry for photocuring 3D printing.
2. The photo-curable 3D printing ceramic paste according to claim 1, wherein the polysiloxane has a chemical structural formula as follows:
wherein R is 1 And R is 2 Independently and separatelySelected from methyl or phenyl, 0 < x < 1.
3. The method for preparing a ceramic paste for photo-curing 3D printing according to any one of claims 1 to 2, comprising the steps of:
s1, mixing polysiloxane and a silane coupling agent; adding acid to hydrolyze the mixture; obtaining a mixed solution;
and S2, mixing the mixed solution, butyl acrylate, a photoinitiator and a light absorber to obtain the photocuring ceramic slurry for 3D printing.
4. A ceramic, characterized in that the ceramic is prepared by using the ceramic slurry according to any one of claims 1 to 2 or the ceramic slurry prepared by the method according to claim 3 as a raw material and adopting a photocuring molding technology.
5. The method for preparing ceramic according to claim 4, comprising the steps of:
s110, performing 3D printing on the ceramic slurry according to any one of claims 1-2 to obtain a ceramic precursor green body with a three-dimensional structure;
s120, placing the ceramic precursor green body at 400-1400 ℃; pyrolyzing under vacuum or inert atmosphere to obtain ceramic.
6. The method of producing ceramic according to claim 5, wherein the pyrolysis in step S120 is as follows:
(1) Heating to 350-400 ℃ at 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(2) Heating to 450-550 ℃ at 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(3) Heating to 600-700 ℃ at 0.1-1 ℃/min, and preserving heat for 2-4 hours;
(4) Heating to 800-1400 ℃ at 1-5 ℃/min, and preserving heat for 2-4 hours;
(5) Cooling to room temperature at 1-5 deg.c/min.
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