CN109970450B - Photosensitive ceramic liquid for 3D printing and ceramic part thereof - Google Patents
Photosensitive ceramic liquid for 3D printing and ceramic part thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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- B33Y10/00—Processes of additive manufacturing
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5603—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides with a well-defined oxygen content, e.g. oxycarbides
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- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention discloses a photosensitive ceramic liquid for photocuring 3D printing, which comprises: 74.3% -89.3% of photosensitive silicone oil, 8.7% -22.3% of silicone oil additive, 0.9% -2.6% of metal catalyst, 0-0.02% of coloring agent and 0.9% -2.0% of photoinitiator, wherein the photosensitive silicone oil is prepared from 74.6% -83.2% of epoxy-containing liquid polysiloxane and 13.8% -24.9% of acrylic acid. The ceramic part product with a good structure can be obtained by sintering.
Description
Technical Field
The invention belongs to the field of ceramics, and particularly relates to photosensitive ceramic liquid for photocuring 3D printing and a ceramic part prepared by using the photosensitive ceramic liquid as a raw material.
Background
The traditional ceramic preparation process such as a slurry forming method and a dry pressing forming method is difficult to form a near-net-shape complex structure, and mechanical processing causes damage to a blank microstructure and wastes time and labor. The manufacturing principle of 3D printing accumulation molding enables the ceramic to have the technical advantages of complex structure rapid molding and efficient production, and is very suitable for being used as a preparation mode of special-shaped ceramics.
The main application methods of 3D printing of ceramic materials are Stereolithography (SLA), Digital Light Processing (DLP), Selective Laser Sintering (SLS), Layered Object Manufacturing (LOM), inkjet printing (IJP), Fused Deposition Modeling (FDM). Wherein, 3D printing technology using photocuring technology as principle, such as stereolithography, digital optical processing and the like, the manufacturing precision can reach micron level, and the method is an excellent means for producing precise advanced ceramic structure materials.
The photocuring 3D printing can use two raw materials: one is a mixed slurry of photosensitive resin macromolecules and powder, and the other is a precursor polymer, wherein the former is a raw material mainly adopted in the existing photocuring 3D printing technology and is mainly used for manufacturing oxide ceramics such as zirconia, alumina, hydroxyapatite, calcium phosphate, silicon oxide and the like. In order to reduce the shrinkage rate of the blank in the sintering process, the photosensitive resin needs to uniformly bear as much ceramic powder as possible; in addition, powder and liquid resin optical parameters such as refractive index need to be well matched. As in the prior patent applications with publication numbers CN108191410A, CN109227877A, and CN108249930A, although the ceramic prepared from the ceramic slurry has the advantage of low shrinkage, in order to support more powder while maintaining low viscosity, good photocuring performance and resolution, solve the problems of low printing resolution caused by scattering of light, and preventing defects and cracks in the sintering densification process, multiple reagents are required to treat the powder in the preparation process, and multiple additives are added into the slurry, so that the preparation process is extremely complex and is not green and environment-friendly.
Compared with the defects, the precursor polymer does not have the problem of two-phase matching, the design scale of the material of the precursor ceramic preparation method can be reduced to a molecular level, and the method has the advantages of liquid-phase forming, low-temperature ceramic formation, good blank uniformity and the like, and is a raw material with the best application prospect in the 3D printing ceramic technology. However, the raw materials are currently studied less, and are basically not used as molding polymers after printing, and cannot be converted into ceramics through sintering. The preparation process is characterized by high solvent content, low silicon content, low viscosity, difficult cross-linking to form a compact network structure after temperature rise and sintering, no possibility of sintering a photocuring blank into a ceramic piece, easy severe shrinkage, cracking and breaking and extremely low strength.
Disclosure of Invention
In view of the above, the present invention is directed to a photosensitive ceramic liquid for 3D printing and a ceramic part thereof, so as to solve the above technical problems.
According to the invention, a precursor polymer is used as a raw material for photocuring 3D printing, silicon oil which is liquid at normal temperature is used as a ceramic Si source, the silicon oil is subjected to photosensitive modification at first, the effective formation of a photocuring crosslinking network is promoted, the use of a solvent can be avoided, meanwhile, micromolecule silicon oil is used as a liquid-phase flexible additive, the density of a ceramic part is improved, and a blank formed by 3D printing can be sintered to obtain a ceramic part product with a good structure.
The invention relates to a photosensitive ceramic liquid for photocuring 3D printing, which comprises: 74.3% -89.3% of photosensitive silicone oil, 8.7% -22.3% of silicone oil additive, 0.9% -2.6% of metal catalyst, 0-0.02% of coloring agent and 0.9% -2.0% of photoinitiator, wherein the photosensitive silicone oil is prepared from 74.6% -83.2% of epoxy-containing liquid polysiloxane and 13.8% -24.9% of acrylic acid.
Wherein each molecule of the epoxy-containing liquid polysiloxane at least contains two epoxy groups connected with silane, the epoxy group content is 2-10%, and the viscosity is 50-200 mPa.
The acrylate with photosensitive property is introduced into the liquid polysiloxane in an epoxy ring-opening mode, so that the obtained photosensitive silicone oil has a considerable amount of secondary hydroxyl groups, the photosensitive silicone oil can be effectively activated, the reaction property is enhanced, meanwhile, the ring-opening reaction enables the branched chains of the photosensitive silicone oil to be increased, the hardness of chain segments is improved, the rapid crosslinking of subsequent photocuring and the rapid release of stress in the crosslinking process are facilitated, and the shrinkage cracking risk of sintering is reduced.
Wherein the silicone oil additive is dimethyl silicone oil or hydroxyl silicone oil; the metal catalyst is dibutyltin dilaurate or tetrabutyl titanate; the coloring agent is lipid coloring agent, preferably Sudan III and Sudan IV; the photoinitiator is a free radical photoinitiator, preferably 2,4, 6-trimethyl benzoyl phenyl phosphonic acid ethyl ester (TPO-L) and 2,4, 6-trimethyl benzoyl phosphonic acid ethyl ester (TPO). The silicon oil additive can improve the brittleness of a ceramic blank, and can form a gas release channel in a compact structure in the pyrolysis process, so that gas molecules can be smoothly discharged, the internal stress of the blank is further relieved, the blank is prevented from cracking, and the density of a ceramic piece is improved.
A preparation method of a photocuring 3D printed ceramic part comprises the following steps:
(1) uniformly mixing 74.3-89.3% of photosensitive silicone oil, 8.7-22.3% of silicone oil additive, 0.9-2.6% of metal catalyst, 0-0.02% of coloring agent and 0.9-2.0% of photoinitiator to obtain photosensitive ceramic liquid;
(2) printing and molding the photosensitive ceramic liquid by using a photocuring 3D printer to obtain a blank body;
(3) and sintering the green body to obtain the ceramic piece.
Wherein the photosensitive silicone oil is prepared by the following steps: mixing 74.6-83.2% of epoxy-containing liquid polysiloxane, 13.8-24.9% of acrylic acid and 0.04-0.07% of modified catalyst, and heating at 90-120 ℃ for 3-8 hours; wherein, the modified catalyst is an amine catalyst, preferably any one of N, N-dimethylcyclohexylamine, N-dimethylbenzylamine and triethylamine.
Wherein the 3D printing parameters of the step (2) are as follows: 50 μm of single layer, 5-10s of single layer exposure time and 1.5-6mJ/cm of unit area exposure energy2。
Wherein the sintering system in the step (3) is as follows: the temperature is raised from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, and the temperature is kept at 1000 ℃ for 1 h.
Compared with the prior art, the invention has the beneficial effects that:
the photosensitive ceramic liquid for 3D printing provided by the invention is a single-phase pure liquid, does not contain a solvent, does not contain solid substances such as ceramic powder, fillers and the like, can be used as a printing raw material to greatly improve the printing resolution, has high Si content, is good in photocuring performance obtained by photosensitive modification in advance, can be cured after being exposed for 5-10s when the single-layer printing thickness is set to be 50 mu m, has high printing resolution, has high mechanical strength for a printing blank, is clear in blank details and complete in structure, is moderate in silicone oil hardness, is beneficial to crosslinking forming and stress release, avoids the problem of poor sinterability such as cracking and the like caused by the escape of a large amount of decomposed substances in the sintering process, has high sintering densification degree, and can obtain a complete, compact and ceramic piece with considerable mechanical strength.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a photograph of a model preset in a digital light processing apparatus used in the present invention.
FIG. 2 is a three-dimensional microscopic photograph with super depth of field of a ceramic blank obtained by photocuring 3D printing of the photosensitive ceramic liquid obtained by the present invention.
FIG. 3 is a three-dimensional microscopic photograph of a ceramic part made according to the present invention.
FIG. 4 is a three-dimensional microscope photograph with super depth of field of a ceramic part prepared from photosensitive ceramic liquid without adding hydroxyl silicone oil or dimethyl silicone oil.
FIG. 5 is a photograph of another ceramic body obtained by photocuring 3D printing of the photosensitive ceramic liquid obtained by the present invention.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
Example 1:
the preparation of the photosensitive ceramic liquid and the ceramic piece for photocuring 3D printing comprises the following steps:
(1) uniformly mixing 79.2% of epoxy silicone oil, 19.8% of acrylic acid and 1% of triethylamine, heating at 105 ℃ for 6 hours, and cooling to obtain photosensitive silicone oil;
(2) adding dimethyl silicone oil accounting for 10% of the mass of the photosensitive silicone oil, dibutyltin dilaurate accounting for 1%, TPO-L accounting for 1% and Sudan III accounting for 0.02% of the mass of the photosensitive silicone oil obtained in the step (1) into the photosensitive silicone oil, and uniformly mixing to obtain photosensitive ceramic liquid;
(3) putting the photosensitive ceramic liquid obtained in the step (2) into digital light processing 3D printing equipment, and setting printing parameters to be single layer 50 mu m, single layer exposure time to be 5s and unit area exposure energy to be 6mJ/cm2Printing according to a preset model to obtain a ceramic blank;
(4) and (4) sintering the ceramic blank obtained in the step (3) in a high-temperature argon tube type furnace to obtain the silicon-oxygen-carbon ceramic piece, wherein the shrinkage rate of the ceramic piece relative to the blank is 35%, and the compression strength is 18 MPa.
Example 2:
the preparation of the photosensitive ceramic liquid and the ceramic piece for photocuring 3D printing comprises the following steps:
(1) uniformly mixing 81.7% of epoxy silicone oil, 16.3% of acrylic acid and 2% of N, N-dimethylcyclohexylamine, heating at 95 ℃ for 5 hours, and cooling to obtain photosensitive silicone oil;
(2) adding hydroxyl silicone oil accounting for 20% of the mass of the photosensitive silicone oil, tetrabutyl titanate accounting for 2.5%, TPO accounting for 1% and Sudan IV accounting for 0.02% of the mass of the photosensitive silicone oil obtained in the step (1) into the photosensitive silicone oil, and uniformly mixing to obtain photosensitive ceramic liquid;
(3) putting the photosensitive ceramic liquid obtained in the step (2) into digital light processing 3D printing equipment, and setting printing parameters to be 50 micrometers for a single layer, setting exposure time of the single layer to be 7s, and setting exposure energy per unit area to be 3mJ/cm2Printing according to a preset model to obtain a ceramic blank;
(4) and (4) sintering the ceramic blank obtained in the step (3) in a high-temperature argon tube type furnace to obtain the silicon-oxygen-carbon ceramic piece, wherein the shrinkage rate of the ceramic piece relative to the blank is 38%, and the compression strength is 20 MPa.
Example 3:
the preparation of the photosensitive ceramic liquid and the ceramic piece for photocuring 3D printing comprises the following steps:
(1) uniformly mixing 8.32% of epoxy silicone oil, 13.8% of acrylic acid and 3% of triethylamine, heating at 90 ℃ for 3 hours, and cooling to obtain photosensitive silicone oil;
(2) adding hydroxyl silicone oil accounting for 30% of the mass of the photosensitive silicone oil, tetrabutyl titanate accounting for 3%, TPO-L accounting for 2% and Sudan III accounting for 0.01% of the mass of the photosensitive silicone oil obtained in the step (1) into the photosensitive silicone oil, and uniformly mixing to obtain photosensitive ceramic liquid;
(3) putting the photosensitive ceramic liquid obtained in the step (2) into digital light processing 3D printing equipment, and setting printing parameters to be single layer 50 mu m, single layer exposure time of 10s and unit area exposure energy of 2.8mJ/cm2Printing according to a preset model to obtain a ceramic blank;
(4) and (4) sintering the ceramic blank obtained in the step (3) in a high-temperature argon tube type furnace to obtain the silicon-oxygen-carbon ceramic piece, wherein the shrinkage rate of the ceramic piece relative to the blank is 40%, and the compression strength is 20 MPa.
Example 4:
the preparation of the photosensitive ceramic liquid and the ceramic piece for photocuring 3D printing comprises the following steps:
(1) uniformly mixing 74.6% of epoxy silicone oil, 24.9% of acrylic acid and 0.5% of N, N-dimethylbenzylamine, heating at 120 ℃ for 8 hours, and cooling to obtain photosensitive silicone oil;
(2) adding dimethyl silicone oil accounting for 15% of the mass of the photosensitive silicone oil, dibutyltin dilaurate accounting for 1.5% of the mass of the photosensitive silicone oil and TPO accounting for 2.5% of the mass of the photosensitive silicone oil obtained in the step (1) into the photosensitive silicone oil, and uniformly mixing the mixture without adding a coloring agent to obtain photosensitive ceramic liquid;
(3) putting the photosensitive ceramic liquid obtained in the step (2) into digital light processing 3D printing equipment, and setting printing parameters to be single layer 50 mu m, single layer exposure time of 6s and unit area exposure energy of 5mJ/cm2Printing according to a preset model to obtain a ceramic blank;
(4) and (4) sintering the ceramic blank obtained in the step (3) in a high-temperature argon tube type furnace to obtain the silicon-oxygen-carbon ceramic piece, wherein the shrinkage rate of the ceramic piece relative to the blank is 38%, and the compression strength is 18 MPa.
Examples 1-4 the default model used in step (3) is shown in FIG. 1. The model is a cylinder with the diameter of 2cm, and the inside of the model is of a hollow structure. The formed blank is shown in figure 2, the diameter of the formed blank is 2cm +/-0.1 cm, and the formed blank is consistent with the structure of the model. Sintering the ceramic blank in a high-temperature argon tube furnace to obtain the silicon-oxygen-carbon ceramic piece, wherein the sintering system is to heat the ceramic blank from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, keep the temperature at 1000 ℃ for 1h, cool the ceramic blank along with the furnace and take the ceramic blank out. The ceramic part has the structure consistent with the model as shown in figure 3, has the advantages of shrinkage compared with the size of a blank, good surface appearance and quality, no local deformation, no defects such as cracks, air holes and the like. Comparing fig. 3 and fig. 4, it can be seen that, compared with the photosensitive ceramic liquid without adding dimethyl silicone oil or hydroxyl silicone oil, the photosensitive ceramic liquid of the present invention has a more regular structure and a more compact structure. The photosensitive ceramic liquid prepared in the examples 1 to 4 can also be printed on other green bodies with complex structures, as shown in the attached figure 5.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A photosensitive ceramic fluid for photocuring 3D printing, comprising, in mass fraction: 74.3 to 89.3 percent of photosensitive silicone oil, 8.7 to 22.3 percent of silicone oil additive, 0.9 to 2.6 percent of metal catalyst, 0 to 0.02 percent of coloring agent and 0.9 to 2.0 percent of photoinitiator; wherein, the photosensitive silicone oil is prepared by 74.6 to 83.2 percent of liquid polysiloxane containing epoxy groups, 13.8 to 24.9 percent of acrylic acid and the balance of modified catalyst; each molecule of the epoxy-containing liquid polysiloxane at least contains two epoxy groups connected with silane, the epoxy group content is 2-10%, and the viscosity is 50-200mPa & s; the silicone oil additive is dimethyl silicone oil or hydroxyl silicone oil.
2. The photosensitive ceramic fluid for photocurable 3D printing according to claim 1, wherein the metal catalyst is dibutyltin dilaurate or tetrabutyl titanate; the coloring agent is lipid coloring agent; the photoinitiator is a free radical photoinitiator.
3. The photosensitive ceramic fluid for photocurable 3D printing according to claim 1, wherein the colorant is sudan iii or sudan iv; the photoinitiator is 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate or 2,4, 6-trimethyl benzoyl ethyl phosphonate.
4. A preparation method of a photocuring 3D printed ceramic part comprises the following steps:
(1) uniformly mixing 74.3-89.3% of photosensitive silicone oil, 8.7-22.3% of silicone oil additive, 0.9-2.6% of metal catalyst, 0-0.02% of coloring agent and 0.9-2.0% of photoinitiator to obtain photosensitive ceramic liquid;
(2) printing and molding the photosensitive ceramic liquid by using a photocuring 3D printer to obtain a blank body;
(3) sintering the green body to obtain a ceramic piece;
the photosensitive silicone oil is prepared by the following steps: mixing 74.6-83.2% of epoxy-containing liquid polysiloxane, 13.8-24.9% of acrylic acid and the balance of modified catalyst, and heating at 90-120 ℃ for 3-8 hours;
each molecule of the epoxy-containing liquid polysiloxane at least contains two epoxy groups connected with silane, the epoxy group content is 2-10%, and the viscosity is 50-200mPa & s;
the silicone oil additive is dimethyl silicone oil or hydroxyl silicone oil.
5. The method of preparing a photocurable 3D printed ceramic article according to claim 4, wherein the modifying catalyst is an amine catalyst.
6. The method for preparing a photocured 3D printed ceramic part according to claim 4, wherein the modification catalyst is any one of N, N-dimethylcyclohexylamine, N-dimethylbenzylamine and triethylamine.
7. The method for preparing a photocured 3D printed ceramic part according to claim 4, wherein the 3D printing parameters of step (2) are: 50 μm of single layer, 5-10s of single layer exposure time and 1.5-6mJ/cm of unit area exposure energy2。
8. The method for preparing a photocured 3D printed ceramic part according to claim 4, wherein the sintering schedule of step (3) is as follows: the temperature is raised from room temperature to 1000 ℃ at the heating rate of 2 ℃/min, and the temperature is kept at 1000 ℃ for 1 h.
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| CN110903089A (en) * | 2019-11-27 | 2020-03-24 | 辽宁大学 | SiOC ceramic prepared by 3D printing and preparation method thereof |
| CN115010877B (en) * | 2022-05-27 | 2023-11-24 | 深圳大学 | Carbon-oxygen-silicon ceramic precursor, thick compact ceramic piece and 3D printing preparation method thereof |
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