Near-infrared photothermal coupling curing non-oxide ceramic slurry and its preparation method and application

Patent metadata

Field	Value
Publication number	US-12435007-B2
Application number	US-202318362361-A
Country	US
Kind code	B2
Filing date	Jul 31, 2023
Priority date	Oct 21, 2022
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

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 3 N 4 , TiN, BN, AlN, SiC, WC, TiC, ZrC, TiB 2 , and ZrB 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.

First claim

What is claimed is:

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 powders;
0.5-20 parts of a photosensitive resin;
1-40 parts of a photosensitive monomer;
0.25-4 parts of a photoinitiator;
0.25-4 parts of a thermal initiator;
0.75-5 parts of additives; and
0.5-4 parts of up-conversion luminescent materials;
wherein the non-oxide ceramic powders include one or more of Si 3 N 4 , TiN, BN, AlN, SiC, WC, TiC, ZrC, TiB 2 , and ZrB 2 ,
wherein the up-conversion luminescent materials include one or more of Yb 3+ or Tm 3+ doped NaYF 4 , BaYF 5 , LiYF 4 , and NaYbF 4 , and
wherein a doping amount of Yb 3+ ranges from 0% to 30%, and a doping amount of Tm 3+ ranges from 0.2% to 3.5%.

2. The near-infrared photothermal coupling curing non-oxide ceramic slurry of claim 1 , wherein the photosensitive resin is 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 of claim 1 , wherein the photosensitive monomer is one or more of bifunctional acrylate monomers and multi-functional acrylate monomers.

4. The near-infrared photothermal coupling curing non-oxide ceramic slurry of claim 1 , wherein the photoinitiator is 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. The near-infrared photothermal coupling curing non-oxide ceramic slurry of claim 1 , wherein the thermal initiator is one or more of organic peroxide initiators, azo initiators, inorganic peroxide initiators, or redox initiators.

6. The near-infrared photothermal coupling curing non-oxide ceramic slurry of claim 1 , wherein the additives are one or more of defoamers, anti-settling agents, and rheological agents.

7. A preparation method of the near-infrared photothermal coupling curing non-oxide ceramic slurry of claim 1 comprising the following steps:
step 1) dispersing and mixing 40-90 parts of the non-oxide ceramic powder, 0.75-5 parts of the additives, and 5-20 parts of anhydrous ethanol at high speed, and then removing the anhydrous ethanol through drying to obtain a modified non-oxide ceramic powder;
step 2) obtaining a photosensitive resin system by high-speed dispersion and mixing of 0.5-20 parts of the photosensitive resin, 1-40 parts of the photosensitive monomer, 0.5-4 parts of the up-conversion luminescent materials, and 0.25-4 parts of the photoinitiator; and
step 3) dispersing and mixing the modified non-oxide ceramic powder obtained in step 1), 0.25-4 parts of the 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. An application of the near-infrared photothermal coupling curing non-oxide ceramic slurry of claim 1 in a preparation method of ceramic parts, the preparation method of the ceramic parts comprising:
step 1) injecting the near-infrared photothermal coupling curing non-oxide ceramic slurry into a light-proof barrel of a printer, and removing bubbles through centrifugation;
step 2) printing the near-infrared photothermal coupling curing non-oxide ceramic slurry by using a near-infrared photo-assisted direct ink writing printer or a near-infrared photo-assisted stereolithography printer, and forming a ceramic body according to a pre-designed pattern; and
step 3) debinding and sintering the ceramic body to obtain the ceramic parts.

Assignees

• Univ Jiangnan

Inventors

• Liu Ren
• Sang Xinxin
• Zhao Yongqin
• Miao Jiatao

Classifications

• C09K11/7773

  with alkali or alkaline earth metal · CPC title

• C09K11/025

  non-luminescent particle coatings or suspension media · CPC title

• C04B2235/9646

  Optical properties · CPC title

• C04B2235/606

  Drying · CPC title

• C04B2235/6026

  Computer aided shaping, e.g. rapid prototyping · CPC title