NEAR-INFRARED PHOTOTHERMAL COUPLING CURING NON-OXIDE CERAMIC SLURRY AND ITS PREPARATION METHOD AND APPLICATION

Abstract

The invention presents a near-infrared photothermal coupling curing non-oxide ceramic slurry, along with its preparation method and application. The ceramic slurry consists of various raw materials, with weight fractions as follows: non-oxide ceramic powder (40?90 parts), photosensitive resin (0.5?20 parts), photosensitive monomer (1?40 parts), photoinitiator (0.25?4 parts), thermal initiator (0.25?4 parts), additive (0.75?5 parts), and up-conversion luminescent material (0.5?4 parts). The non-oxide ceramic powders can include Si.sub.3N.sub.4, TiN, BN, AlN, SiC, WC, TiC, ZrC, TiB.sub.2, and ZrB.sub.2. By combining the photochemical and photothermal dual curing system using near-infrared up-conversion, this invention addresses the issue of insufficient curing encountered in single photocuring or thermal curing processes. Moreover, by incorporating near-infrared light source-driven additive manufacturing, it enables rapid prototyping of high-solid-content non-oxide ceramic slurry, ultimately allowing for the fabrication of high-fidelity non-oxide ceramic structures.

Claims

1. The near-infrared photothermal coupling curing non-oxide ceramic slurry is composed of various raw materials with different weights, including: 40-90 parts of non-oxide ceramic powder 0.5-20 parts of photosensitive resin 1-40 parts of photosensitive monomer 0.25-4 parts of photoinitiator 0.25-4 parts of thermal initiator 0.75-5 parts of additives 0.5-4 parts of up-conversion luminescent material The non-oxide ceramic powders can include one or more of Si.sub.3N.sub.4, TiN, BN, AlN, SiC, WC, TiC, ZrC, TiB.sub.2, and ZrB.sub.2. The up-conversion luminescent materials can include one or more of Yb.sup.3+ or Tm.sup.3+ doped NaYF.sub.4, BaYF.sub.5, LiYF.sub.4, and NaYbF.sub.4. The doping amount of Yb.sup.3+ ranges from 0% to 30%, and the doping amount of Tm.sup.3+ ranges from 0.2% to 3.5%.

2. The near-infrared photothermal coupling curing non-oxide ceramic slurry described in claim 1 is characterized by the photosensitive resin, which can be one or more of resins containing acrylate double bonds, vinyl ether double bonds, or epoxy groups.

3. The near-infrared photothermal coupling curing non-oxide ceramic slurry described in claim 1 is characterized by the photosensitive monomer, which can be one or more of bifunctional acrylate monomers and multi-functional acrylate monomers.

4. According to claim 1, the near-infrared photothermal coupling curing non-oxide ceramic slurry is characterized by the photoinitiator, which can be one or more of bis(2,6-difluoro-3-pyrrolylphenyl) titanocene, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2-isopropylthioxanthone, camphorquinone, or [diethyl-(4-methoxybenzoyl) germanium]-(4-methoxyphenyl) methanone.

5. According to claim 1, the near-infrared photothermal coupling curing non-oxide ceramic slurry is characterized by the thermal initiator, which can be one or more of organic peroxide initiators, azo initiators, inorganic peroxide initiators, or redox initiators.

6. According to the near-infrared photothermal coupling curing non-oxide ceramic slurry described in claim 1, it is characterized by the additives, which can be one or more of defoamers, anti-settling agents, and rheological agents.

7. The preparation method of the near-infrared photothermal coupling curing non-oxide ceramic slurry described in claim 1 is characterized by the following steps: step 1) Disperse and mix 40-90 parts of non-oxide ceramic powder, 0.75-5 parts of additives, and 5-20 parts of anhydrous ethanol at high speed, and then remove the anhydrous ethanol through drying to obtain modified non-oxide ceramic powder. step 2) Obtain the photosensitive resin system by high-speed dispersion and mixing of 0.5-20 parts of photosensitive resin, 1-40 parts of photosensitive monomer, 0.5-4 parts of up-conversion luminescent material, and 0.25-4 parts of photoinitiator. step 3) Disperse and mix the modified non-oxide ceramic powder obtained in step 1), 0.25-4 parts of thermal initiator, and the photosensitive resin system obtained in step 2) at high speed to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

8. The application of the near-infrared photothermal coupling curing non-oxide ceramic slurry described in claim 1 is characterized by its use in the preparation of ceramic parts.

9. According to the application described in claim 8, the characteristic of the preparation method for ceramic parts is as follows: step 1) The near-infrared photothermal coupling curing non-oxide ceramic slurry is injected into a light-proof barrel of a printer, and bubbles are removed through centrifugation. step 2) The near-infrared photothermal coupling curing non-oxide ceramic slurry is printed using a near-infrared photo-assisted direct ink writing printer or a near-infrared photo-assisted stereolithography printer, forming the ceramic body according to the pre-designed pattern. step 3) The ceramic body is subjected to debinding and sintering processes to obtain ceramic parts.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0066] FIG. 1: Photograph of the grid structure body printed in Example 1

[0067] FIG. 2: Photograph of the block structure body printed in Example 2 of the implementation

[0068] FIG. 3: Diagram showing the test results of slurry curing thickness

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0069] The invention is described in detail in combination with the attached drawings and embodiments.

Embodiment 1

[0070] A preparation method for near-infrared photothermal coupling curing non-oxide ceramic slurry is provided. The method comprises the following steps:

[0071] (Step 1) Dispersing 62 parts per hundred parts of SiC powder (with an average particle size of 500 nm), 1.85 parts per hundred parts of BYK111, and 12.4 parts per hundred parts of anhydrous ethanol at a speed of 2400 r/min for 3 minutes. Subsequently, drying the mixture at 80? C. for 10 hours to remove the anhydrous ethanol, resulting in modified non-oxide ceramic powder.

[0072] (Step 2) Obtaining the photosensitive resin system by dispersing 10 parts of CN996NS photosensitive resin, 23 parts of DI-TMPTA photosensitive monomer, 1.5 parts of up-conversion particle ?-NaYF.sub.4 (with Yb.sup.3+ doping amount of 20% and Tm.sup.3+ doping amount of 0.5%), and 1 part of photoinitiator 819 at a speed of 1600 r/min for 4 minutes.

[0073] (Step 3) Dispersing the modified non-oxide ceramic powder obtained in step 1) (with a thermal initiator BPO content of 0.65 parts per hundred parts) and the photosensitive resin system obtained in step 2) at a speed of 2400 r/min for 4 minutes to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0074] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared in this embodiment was introduced into the light-proof barrel of the printer, and centrifugation was carried out at 5000 r/min for 5 minutes to remove any bubbles. Subsequently, the near-infrared photothermal coupling solidified non-oxide ceramic slurry was printed using a near-infrared photo-assisted direct ink writing printer, with extrusion driven by gas. The extrusion nozzle moved at a speed of 20 mm/s, and a laser with a wavelength of 980 nm was used. The laser power was set to 100 W/cm.sup.2, resulting in the formation of the grid ceramic body as shown in FIG. 1.

[0075] The obtained ceramic body underwent a debinding and sintering process. The debinding was performed at a temperature of 650? C., with a heating rate of 0.1? C./min, and a debinding time of 2 hours. The sintering process was conducted at a pressure of 0.4 MPa, a sintering temperature of 1450? C., a heating rate of 1? C./min, and a sintering time of 55 hours. As a result, the ceramic parts were successfully obtained.

Embodiment 2

[0076] A preparation method for near-infrared photothermal coupling curing non-oxide ceramic slurry is provided, comprising the following steps:

[0077] (Step 1) 70 parts by weight of SiC powder (average particle size of 500 nm), 2.1 parts by weight of BYK111, and 14 parts by weight of anhydrous ethanol were dispersed at 2500 r/min for 3 minutes. Subsequently, the mixture was dried at 80? C. for 8 hours to remove the anhydrous ethanol, resulting in the modified non-oxide ceramic powder.

[0078] (Step 2) The photosensitive resin system was obtained by dispersing 10 parts of photosensitive resin 6215-100, 15.15 parts of photosensitive monomer DI-TMPTA, 1.5 parts of up-conversion particles ?-NaYF.sub.4 (with Yb.sup.3+ doping amount of 20% and Tm.sup.3+ doping amount of 0.5%), and 0.75 parts of photoinitiator 819 at 1600 r/min for 4 minutes.

[0079] (Step 3) The modified non-oxide ceramic powder obtained in Step 1), 0.50 parts by weight of thermal initiator BPO, and the photosensitive resin system obtained in Step 2) were dispersed at 2500 r/min for 4 minutes to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0080] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared in this embodiment was injected into the light-proof barrel of the printer, and the bubbles were removed by centrifugation at 6000 r/min for 7 minutes. Subsequently, the near-infrared light-thermal coupling curing non-oxide ceramic slurry was printed on the near-infrared photo-assisted direct ink writing printer, with extrusion driven by gas. The extrusion nozzle moved at a speed of 10 mm/s, while the laser had a wavelength of 980 nm and a power of 150 W/cm.sup.2. The result was the square ceramic body shown in FIG. 2.

[0081] The obtained ceramic body underwent debinding and sintering. The debinding temperature was set at 650? C., with a heating rate of 0.1? C./min, and the debinding process lasted for 2 hours. For sintering, a pressure of 0.4 MPa was applied, with a sintering temperature of 1450? C. The heating rate during sintering was 1? C./min, and the sintering time was 55 hours. As a result, ceramic parts were successfully obtained.

Embodiment 3

[0082] A preparation method for near-infrared photothermal coupling curing non-oxide ceramic slurry is provided. The method includes the following steps:

[0083] (Step 1) Disperse 81 parts per hundred parts of SiC powder (average particle size of 12500 nm), 2.43 parts per hundred parts of BYK111, and 16.2 parts per hundred parts of anhydrous ethanol at 2700 r/min for 3 minutes. Then, dry the mixture at 80? C. for 8 hours to remove the anhydrous ethanol, obtaining modified non-oxide ceramic powder.

[0084] (Step 2) Disperse 1 part per hundred parts of photosensitive resin CN996NS, 13.54 parts per hundred parts of photosensitive monomer DI-TMPTA, 1.3 parts per hundred parts of up-conversion particle NaYbF.sub.4 (with Tm.sup.3+ doping amount of 0.5%), and 0.44 parts per hundred parts of photoinitiator 819 at 1600 r/min for 4 minutes to obtain the photosensitive resin system.

[0085] (Step 3) Disperse the modified non-oxide ceramic powder obtained in Step 1), 0.29 parts per hundred parts of thermal initiator BPO, and the photosensitive resin system obtained in Step 2) at 2700 r/min for 4 minutes, resulting in the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0086] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared using this method was loaded into a light-proof barrel of the printer, and the bubbles were eliminated by centrifugation at a speed of 7500 r/min for 8 minutes. Subsequently, the slurry was printed using a near-infrared photo-assisted direct ink writing printer, with gas-driven extrusion. The extrusion nozzle moved at a speed of 5 mm/s, while the laser operated at a wavelength of 980 nm with a power of 200 W/cm.sup.2, resulting in the formation of a ceramic body.

[0087] The obtained ceramic body underwent sequential debinding and sintering processes. The debinding temperature was set at 650? C., and the temperature increased at a rate of 0.2? C./min. The debinding process lasted for 2 hours. For sintering, a pressure of 0.4 MPa was applied, and the sintering temperature reached 1450? C. at a heating rate of 1? C./min. The sintering duration was 55 hours, leading to the production of ceramic parts.

Embodiment 4

[0088] A method for preparing near-infrared photothermal coupling curing non-oxide ceramic slurry is provided. The method includes the following steps:

[0089] (Step 1) Disperse 75 parts by weight (phr) of Si.sub.3N.sub.4 powder with an average particle size of 500 nm, 2.25 phr of KH560, and 15 phr of anhydrous ethanol at a speed of 2600 r/min for 3 minutes. Then, dry the mixture at 80? C. for 8 hours to remove the anhydrous ethanol and obtain modified non-oxide ceramic powder.

[0090] (Step 2) Disperse 5 portions of photosensitive resin 6215-100, 15.35 portions of photosensitive monomer TMPTA, 1.4 portions of up-conversion particles NaYbF.sub.4 (with Tm.sup.3+ doping amount of 0.5%), and 0.60 portions of photoinitiator 819 from Changxing Materials Industry Co., Ltd. at a speed of 1600 r/min for 4 minutes to obtain the photosensitive resin system.

[0091] (Step 3) Disperse the modified non-oxide ceramic powder obtained in Step 1), 0.40 phr of thermal initiator TBPB, and the photosensitive resin system obtained in Step 2) at a speed of 2600 r/min for 4 minutes to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0092] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared in this embodiment was injected into the light-proof barrel of the printer, and the bubbles were removed by centrifugation at 7000 r/min for 7 minutes. Subsequently, the near-infrared photothermal coupling curing non-oxide ceramic slurry was printed using a near-infrared photo-assisted direct ink writing printer, with extrusion driven by gas. The extrusion nozzle moved at a speed of 8 mm/s, and the laser had a wavelength of 980 nm. The laser power was set at 150 W/cm.sup.2, resulting in the fabrication of a ceramic body.

[0093] The obtained ceramic body was subjected to a debinding and sintering process. The debinding temperature was set at 650? C., and the heating rate to reach this temperature was 0.3? C./min. The debinding process lasted for 3 hours. Subsequently, the ceramic body was subjected to a sintering process under a pressure of 0.15 MPa. The sintering temperature was set at 1750? C., and the heating rate to reach this temperature was 0.60? C./min. The sintering process lasted for 30 hours, resulting in the production of ceramic parts.

Embodiment 5

[0094] The near-infrared photothermal coupling curing non-oxide ceramic slurry is prepared using the following method:

[0095] (Step 1) Disperse 65 parts of SiC powder (average particle size of 500 nm), 1.9 parts of BYK111, and 13.0 parts of anhydrous ethanol at 2500 r/min for 3 minutes. Then, dry the mixture at 80? C. for 10 hours to remove the anhydrous ethanol and obtain modified non-oxide ceramic powder.

[0096] (Step 2) Disperse 3 parts of photosensitive resin CN996NS, 27 parts of photosensitive monomer TMPTA, 1.6 parts of up-conversion particle ?-NaYF.sub.4 (with Yb.sup.3+ doping amount of 20% and Tm.sup.3+ doping amount of 0.5%), and 0.9 parts of photoinitiator 819 at 1800 r/min for 4 minutes to obtain the photosensitive resin system.

[0097] (Step 3) Disperse the modified non-oxide ceramic powder obtained in step 1), 0.6 parts of thermal initiator BPO, and the photosensitive resin system obtained in step 2) at 2500 r/min for 4 minutes to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0098] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared using this method was utilized as follows. First, the slurry was injected into the light-proof barrel of a printer, and any bubbles present were removed through centrifugation at a speed of 5000 r/min for 5 minutes. Subsequently, the near-infrared light-thermal coupling curing non-oxide ceramic slurry was printed on a near-infrared photo-assisted stereolithography printer. The laser scanning speed during printing was set to 2000 mm/s, the laser wavelength was 980 nm, and the laser power was 80 W/cm.sup.2. This process resulted in the fabrication of a ceramic body with desired characteristics.

[0099] The obtained ceramic body then underwent debinding and sintering in sequential steps. Debinding was conducted at a temperature of 650? C., with a heating rate of 0.1? C./min and a duration of 2 hours. Subsequently, the ceramic body was subjected to sintering under a pressure of 0.4 MPa, at a temperature of 1450? C., with a heating rate of 1? C./min, and a sintering time of 55 hours. Through these processes, the desired ceramic parts were obtained.

Embodiment 6

[0100] The near-infrared photothermal coupling curing non-oxide ceramic slurry can be prepared using the following steps:

[0101] (Step 1) Disperse 70 parts by weight of Si.sub.3N.sub.4 powder (average particle size of 500 nm), 2.40 parts of KH560, and 16 parts of anhydrous ethanol at a speed of 2800 r/min for 4 minutes. Then, dry the mixture at 80? C. for 7 hours to remove the anhydrous ethanol and obtain modified non-oxide ceramic powder.

[0102] (Step 2) Disperse 5 parts of photosensitive resin 6215-100, 20.35 parts of photosensitive monomer TMPTA, 1.3 parts of up-conversion particles NaYbF.sub.4 (Tm.sup.3+ doping amount of 0.5%), and 0.55 parts of photoinitiator 819 from Changxing Materials Industry Co., Ltd. at a speed of 1900 r/min for 4 minutes to obtain the photosensitive resin system.

[0103] (Step 3) Disperse the modified non-oxide ceramic powder obtained in step 1), 0.40 parts of thermal initiator TBPB, and the photosensitive resin system obtained in step 2) at a speed of 2800 r/min for 4 minutes to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0104] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared according to this embodiment was injected into the light-proof barrel of the printer, and the bubbles were removed by centrifugation at a speed of 7000 r/min for 7 minutes. Subsequently, the near-infrared light-thermal coupling curing non-oxide ceramic slurry was printed using a near-infrared photo-assisted stereolithography printer. The laser scanning speed was set to 2200 mm/s, the laser wavelength was 980 nm, and the laser power was 90 W/cm.sup.2, resulting in the fabrication of the ceramic body.

[0105] The obtained ceramic body was subjected to debinding and sintering processes. The debinding temperature was maintained at 650? C. with a heating rate of 0.3? C./min, and the debinding process lasted for 3 hours. The sintering process was conducted under a pressure of 0.15 MPa, at a sintering temperature of 1750? C. with a heating rate of 0.60? C./min, and the sintering time was set to 30 hours. Through these steps, the final ceramic parts were successfully obtained.

Comparative Embodiment 1

[0106] A method for preparing near-infrared photothermal coupling curing non-oxide ceramic slurry is described. The method comprises the following steps:

[0107] (Step 1) Disperse 62 parts per hundred parts of SiC powder (with an average particle size of 500 nm), 1.85 parts per hundred parts of BYK111, and 12.4 parts per hundred parts of anhydrous ethanol at a speed of 2400 r/min for 3 minutes. Then, dry the mixture at 80? C. for 10 hours to remove the anhydrous ethanol, resulting in modified non-oxide ceramic powder.

[0108] (Step 2) Disperse 10 parts of photosensitive resin CN996NS, 23.65 parts of photosensitive monomer DI-TMPTA, 1.5 parts of up-conversion particles ?-NaYF.sub.4 (with Yb.sup.3+ doping amount of 20% and Tm.sup.3+ doping amount of 0.5%), and 1 part of photoinitiator 819 at a speed of 1600 r/min for 4 minutes to obtain the photosensitive resin system.

[0109] (Step 3) Disperse the modified non-oxide ceramic powder obtained in Step 1) and the photosensitive resin system obtained in Step 2) at a speed of 2400 r/min for 4 minutes to obtain the near-infrared light-cured non-oxide ceramic slurry.

[0110] The near-infrared light-cured non-oxide ceramic slurry prepared according to this embodiment was used for printing purposes. After removing the bubbles through centrifugation at 5000 r/min for 5 minutes, the near-infrared photothermal coupling solidified non-oxide ceramic slurry was printed using a near-infrared photo-assisted direct ink writing printer. The extrusion was driven by gas, with the extrusion nozzle moving at a speed of 20 mm/s. The laser used had a wavelength of 980 nm, and the laser power was set at 100 W/cm.sup.2. The resulting product was a ceramic body.

[0111] To further process the ceramic body, it underwent a debinding and sintering process. The debinding temperature was set at 650? C., with a heating rate of 0.1? C./min. The debinding time was 2 hours. However, due to incomplete curing prior to heat treatment, cracking occurred during the debinding process.

Comparative Embodiment 2

[0112] A method for preparing a near-infrared photothermal coupling curing non-oxide ceramic slurry is described, involving the following steps:

[0113] (Step 1) Disperse 70 parts per hundred parts of SiC powder (with an average particle size of 500 nm), 2.1 parts per hundred parts of BYK111, and 14 parts per hundred parts of anhydrous ethanol at a speed of 2500 r/min for 3 minutes. Then, dry the mixture at 80? C. for 8 hours to remove the anhydrous ethanol and obtain modified non-oxide ceramic powder.

[0114] (Step 2) Disperse 10 portions of photosensitive resin 6215-100 from Changxing Materials Industry Co., Ltd., 15.9 portions of photosensitive monomer DI-TMPTA, and 1.5 portions of up-conversion particles ?-NaYF.sub.4 (with Yb.sup.3+ doping amount of 20% and Tm.sup.3+ doping amount of 0.5%) at a speed of 1600 r/min for 4 minutes to obtain the resin system.

[0115] (Step 3) Disperse the modified non-oxide ceramic powder obtained in step 1), 0.50 parts per hundred parts of thermal initiator BPO, and the photosensitive resin system obtained in step 2) at a speed of 2500 r/min for 4 minutes to obtain the near-infrared thermal curing non-oxide ceramic slurry.

[0116] The near-infrared thermosetting non-oxide ceramic slurry prepared in this embodiment was injected into the light-proof barrel of the printer, and the bubbles were removed by centrifugation at 6000 r/min for 7 minutes. Subsequently, the near-infrared photothermal coupling solidified non-oxide ceramic slurry was printed using a near-infrared photo-assisted direct ink writing printer with gas-driven extrusion. The extrusion nozzle moved at a speed of 10 mm/s, and the laser wavelength used was 980 nm. A laser power of 150 W/cm.sup.2 was applied to obtain a ceramic body.

[0117] The obtained ceramic body underwent debinding and sintering sequentially. The debinding process involved heating the ceramic body to a temperature of 650? C., with a heating rate of 0.1? C./min, and maintaining this temperature for 2 hours. However, due to incomplete curing before heat treatment, cracking occurred during the debinding process.

Comparative Embodiment 3

[0118] A preparation method of near-infrared photothermal coupling curing non-oxide ceramic slurry is described. The method comprises the following steps:

[0119] (Step 1) 90.5 phr SiC powder with an average particle size of 12500 nm, 2.43 phr BYK111, and 18.1 phr anhydrous ethanol were dispersed at 3000 r/min for 4 minutes. The dispersion was then dried at 80? C. for 8 hours to remove the anhydrous ethanol and obtain modified non-oxide ceramic powder.

[0120] (Step 2) The photosensitive resin system was obtained by dispersing 0.5 phr of photosensitive resin CN996NS, 3.3 phr of photosensitive monomer HDDA, 2 phr of photosensitive monomer DI-TMPTA, 1 phr of up-conversion particle NaYbF.sub.4 (with a Tm.sup.3+ doping amount of 0.5%), and 0.17 phr of photoinitiator 784. The dispersion was carried out at 1600 r/min for 4 minutes.

[0121] (Step 3) The modified non-oxide ceramic powder obtained from step 1), 0.10 phr thermal initiator BPO, and the photosensitive resin system obtained from step 2) were dispersed for 5 minutes at a speed of 3000 r/min to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0122] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared using this method was injected into the light-proof barrel of the printer, and the bubbles were removed by centrifugation at 9000 r/min for 8 minutes. Subsequently, the slurry was printed on a near-infrared photo-assisted direct ink writing printer with extrusion driven by gas. The laser used had a wavelength of 980 nm, and the laser power was set to 200 W/cm.sup.2. However, due to the high viscosity of the slurry, extrusion became challenging.

Comparative Embodiment 4

[0123] A method for preparing near-infrared photothermal coupling curing non-oxide ceramic slurry is provided. The method includes the following steps:

[0124] (Step 1) Disperse 75 parts per hundred parts of Si.sub.3N.sub.4 powder (average particle size of 500 nm), 2.25 parts per hundred parts of KH560, and 15 parts per hundred parts of anhydrous ethanol at a speed of 2600 r/min for 3 minutes. Then, dry the mixture at 80? C. for 8 hours to remove the anhydrous ethanol and obtain modified non-oxide ceramic powder.

[0125] (Step 2) Disperse 5 portions of photosensitive resin 6215-100, 16.75 portions of photosensitive monomer TMPTA, and 0.60 portions of photoinitiator 819 from Changxing Material Industry Co., Ltd. at a speed of 1600 r/min for 4 minutes to obtain the photosensitive resin system.

[0126] (Step 3) Disperse the modified non-oxide ceramic powder obtained from step 1), 0.40 parts per hundred parts of thermal initiator TBPB, and the photosensitive resin system obtained from step 2) at a speed of 2600 r/min for 4 minutes to obtain the near-infrared photothermal coupling curing non-oxide ceramic slurry.

[0127] The near-infrared photothermal coupling curing non-oxide ceramic slurry prepared by this embodiment was injected into the light-proof barrel of the printer, and the bubbles were removed by centrifugation at 7000 r/min for 7 minutes. Subsequently, the slurry was printed on a near-infrared photo-assisted direct ink writing printer using gas extrusion. The extrusion nozzle moved at a speed of 8 mm/s, and a laser with a wavelength of 980 nm and a power of 150 W/cm.sup.2 was used. However, it was not possible to achieve the desired ceramic body with in-situ shape preservation.

Testing Embodiment

[0128] The implementation examples were tested using rheological tests, slurry curing performance tests, and mechanical property tests, and the properties of the ceramic slurry and ceramic prepared in proportion are presented in Table 1. The testing standards and methods are described as follows: [0129] (1). Viscosity test: The viscosity of the slurry was measured using a viscometer at a shear rate of 30 rad/s. This measurement provides an indication of the flow behavior of the slurry. [0130] (2). Slurry curing performance test: The ceramic slurry was placed in a test tank and irradiated with near-infrared light of a specific intensity. After a certain period of time, the solidified sample was obtained. The uncured slurry was then washed with anhydrous ethanol. The thickness of the solidified sample was measured using a vernier caliper. Each group of samples was repeated five times to obtain an average thickness. In this test, a near-infrared light intensity of 150 W/cm.sup.2 was used, and the curing time was set to 3 seconds. The schematic diagram of the slurry curing thickness test is shown in FIG. 3. [0131] (3). Three-point bending strength test: The three-point bending strength of the ceramic sample was tested using a universal testing machine according to the standard GB/T 6569-2006 fine ceramic bending strength test method. This test evaluates the mechanical strength of the ceramic material.

TABLE-US-00001 TABLE 1 Viscosity Curing performance of of ceramic slurry Ceramic ceramic Curing thickness, properties slurry ?m (Near infrared three-point Viscosity, light intensity 150 bending Pa .Math. s W/cm.sup.2, curing strength (30 rad/s) time 3 seconds) (Mpa) Embodi- 16.4 1376 414.5 ment 1 Embodi- 28.6 1264 420.4 ment 2 Embodi- 45.8 1481 423.6 ment 3 Embodi- 40.3 965 491.1 ment 4 Embodi- 14.6 1168 441.2 ment 5 Embodi- 19.4 1046 504.3 ment 6 Com- 15.8 223 It was not completely parative cured before heat embodi- treatment, and ment 1 cracking occurred during debinding. Com- 27.5 627 It was not completely parative cured before heat embodi- treatment, and ment 2 cracking occurred during debinding. Com- 163.2 parative embodi- ment 3 Com- 39.6 125 Failed to in situ parative curing molding embodi- ment 4

[0132] The above is only the preferred implementation method of the invention. It should be pointed out that for ordinary technicians in the technical field, some improvements and embellishments can be made without breaking away from the principle of the invention. These improvements and embellishments should also be regarded as the scope of protection of the invention.