硅酸盐学报

光敏性聚硅氮烷无溶剂陶瓷浆料的光固化3D打印性能

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王子涵 ¹ , 李森 ¹ , 刘一阳 ¹ , 刘霆邦 ¹ , 何梅 ² , 张承双 ² , 王明存 ¹

硅酸盐学报 | 研究论文 2026,54(9): 3220-3231

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硅酸盐学报 |研究论文 2026 , 54 (9) : 3220 -3231

光敏性聚硅氮烷无溶剂陶瓷浆料的光固化3D打印性能

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王子涵¹, 李森¹, 刘一阳¹, 刘霆邦¹, 何梅², 张承双², 王明存¹

作者信息

^1．北京航空航天大学化学学院，北京 102206

^2．西安航天复合材料研究所，西安 710025

通讯作者:

王明存（1972—），男，副教授。

作者简介:

王子涵（2000—），女，硕士研究生。

3D Printing Properties of Photo-Sensitive Polysilazane Solvent-Free Ceramic Slurry in Digital Light Processing

Zihan WANG¹, Sen LI¹, Yiyang LIU¹, Tingbang LIU¹, Mei HE², Chengshuang ZHANG², Mingcun WANG¹

Affiliations

^1.School of Chemistry, Beihang University, Beijing 102206, China

^2.Xi'an Research Institute of Aerospace Composites, Xi'an 710025, China

Corresponding Author:

{WANG} Mingcun (1972-), male, Ph.D., Associate Professor. E-mail: mcwang@buaa.edu.cn

WANG Zihan (2000-), female, Master candidate. E-mail: wangzh1632025@163.com

出版时间: 2026-08-18 doi: 10.14062/j.issn.0454-5648.20250712

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摘要

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数字光处理（DLP）3D打印适合制备具有精细结构的陶瓷材料，其中，光敏性陶瓷前驱体是可打印浆料的关键原材料。聚硅氮烷PSZ-ViH在异氰酸酯丙烯酸乙酯ICA改性后的光敏性聚硅氮烷PSZ-ViH-ICA具有最大的光固化厚度（相比于PSZ-TViH和PSZ-H，PSZ-TViH是含端乙烯基和硅氢的聚硅氮烷，PSZ-H是含硅氢的聚硅氮烷）。液态光敏引发剂2，4，6-三甲基苯甲酰基磷酸乙酯TPO-L兼顾光固化活性与光敏性聚硅氮烷存放稳定性，通过优化光敏剂用量[5%（质量分数）]实现了透射深度（D_p=63.09 μm）与临界曝光强度（E_c=3.94 mJ/cm²）的平衡。加入陶瓷粉体的光敏性PSZ-ViH-ICA浆料，光固化厚度：SiO₂>Al₂O₃>ZrO₂>Si₃N₄>AlN。加入SiC粉体时光固化厚度极小（约为5 μm），而加入ZrB₂粉体则未固化。考虑到Si₃N₄粉体与聚硅氮烷化学组分一致、光固化厚度适中，本工作选其制备光敏性聚硅氮烷浆料。通过纳米级/微米级陶瓷粉体混合协同策略（5%微米级氮化硅+5%纳米级氮化硅），维持较好的光固化活性（透射深度52.80 μm），而且光固化样品密度提升至1.19 g/cm³。基于透射深度D_p与临界曝光强度E_c的朗伯-比尔定律模型，确定在DLP打印时以透射深度的2/3设定层厚，以临界曝光强度的3倍能量校准曝光时间，实现了光敏性聚硅氮烷浆料对于复杂结构（如蜂窝）的高精度打印。对于光敏性陶瓷浆料的DLP光固化样品，其断面形貌的SEM表征表明层间结合良好，实际打印层厚与预设单层固化厚度基本一致。光敏性聚硅氮烷无溶剂氮化硅陶瓷浆料的DLP光固化3D打印为复杂氮化硅陶瓷结构提供了可行的成型技术。

关键词

光敏性聚硅氮烷 / 陶瓷浆料 / 数字光处理3D打印 / 光固化

Abstract

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Introduction

Additive Manufacturing (AM), also known as 3D printing, is widely used due to its advantages such as high design freedom, no need for molds, mass customization, and the ability to construct complex shaped components. The existing 3D printing methods are developed, among which DLP technology has the advantages of fast printing speed, high dimensional accuracy, no need for molds, close to net shape, and high mechanical performance. Ceramic materials are widely used as high-temperature structural functional materials due to their high temperature resistance, oxidation resistance, corrosion resistance, and mechanical properties. However, compared with metal and polymer materials, ceramic materials are still immature in 3D print processing, facing some problems such as limited availability of suitable raw materials, difficulty in optimizing ratios, high costs, poor process stability, and limited mechanical properties. To overcome the problems above, combining photopolymerization 3D printing with ceramic sintering technology becomes an effective method. In this study, ceramic powder and photosensitive preceramic were ground to obtain a uniform slurry with a good flowability, and then high-precision green bodies were formed through DLP.

Methods

Polysilazane PSZ-ViH containing both vinyl and Si-H was prepared via ammonified of trimethylchlorosilane, methyltrichlorosilane, methylvinyldichlorosilane, and methylhydrogendichlorosilane. Referring to the reaction conditions above, a Vi-terminated/Si-H containing polysilazane PSZ-TViH was obtained with dimethylvinylchlorosilane, methyltrichlorosilane, and methyldichlorosilane as raw materials. Si-H containing polysilazane LSZ-H was obtained with trimethylchlorosilane, methyltrichlorosilane, and methyldichlorosilane as raw materials. When 2-isocyanatoethyl acrylate (ICA) was used as a modifier, the reaction occurred under stirring in dark conditions at room temperature for 24 h. 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester (TPO-L) was added as a photosensitizer and stirred in dark conditions for 10 min. PSZ-ViH and Si₃N₄ powders with different mass fractions were ground, ICA and TMPTA were added, and then followed by TPO-L. Finally, a photosensitive polysilazane-based ceramic slurry was obtained after stirring in the dark for 10 min.

The photosensitive slurry was photo-cured and formed on the DLP printer Photon Mono 4k. The infrared spectra were determined by Fourier transform infrared spectroscopy (FT-IR). The curing thickness of photosensitive resin or slurry at different exposure durations was measured on a coating thickness gauge (HC622) by an iron-based F probe and an iron reference block. The rheological properties of photosensitive slurries were characterized by a rotary rheometer (DESKTOP BKLJ9S3), with steady-state shear rate scanning at room temperature and dynamic temperature, respectively. The thermo-behavior was characterized by differential scanning calorimetry (DSC) on a model Mettler Toledo DSC1 Q2000 thermal analyzer, and thermogravimetric analysis (TGA) on a model Discovery TGA 55 thermal analyzer with an argon gas flow rate of 40 mL/min and a heating rate of 10 ℃/min, respectively. The density of photo-cured printed parts was measured by the Archimede displacement method. The cross-sectional morphology of the material was characterized by field emission scanning electron microscopy (FESEM, Hitachi S4800), and the sample (ion sputter coated Pd layer) was fixed on the sample stage with conductive adhesive at an acceleration voltage of 5 kV and a vacuum degree of ≤ 10^-4 Pa.

Results and discussion

PSZ-ViH with vinyl as side groups can be chemically modified with 2-Isocyanatoethylacrylate, and PSZ-ViH-ICA shows the maximum light-curing depth compared with PSZ-TViH-ICA and PSZ-H-ICA. Liquid photoinitiator TPO-L can equilibrate light reactivity and shelf-life via optimizing the TPO-L amount, leading to a good balance of transition depth (D_p=63.09 μm) and threshold exposure intensity (E_c=3.94 mJ/cm²). As a result, TPO-L can be chosen as a suitable photoinitiator in DLP processing for polysilazane slurry. Among the ceramic powders introduced in the slurry, the light-curing depth follows an order of SiO₂>Al₂O₃ > ZrO₂ > Si₃N₄ > AlN. SiC slurry shows a low light-curing depth, while ZrB₂ slurry cannot be light cured totally. Silicon nitride powder is applied as a slurry additive due to the proper light-curing depth and similar chemical components compared with polysilazane adhesive. Ideal light reactivity and higher material density can be realized by synergistic effect of combination addition of micro-sized and nano-sized Si₃N₄. Based on the model of the relationship between transition depth (D_p) and threshold exposure intensity (E_c), the processing parameters are determined (i.e., the layer width is 2/3 of transition depth, the exposure time is adjusted according to three times of threshold exposure intensity). DLP pringting with a high precision of polysilazane slurry can be realized for the production of complex structures (e.g., cellular structure). An interlayered adhesion occurs and the width of single layer is almostly equal to the setting value via analyzing the fracture morphology of light-curing samples with different powder contents and particle sizes.

Conclusions

The distribution of vinyl groups in polysilazane molecules significantly affected the crosslinking density and curing depth. Polysilazane PSZ-ViH containing vinyl side groups had a larger photopolymerization thickness than PSZ-TViH with terminated vinyl groups due to the uniform distribution of active sites in the former.

The photosensitizer screening experiment showed that liquid 2,4,6-trimethylbenzoyl phosphate ethyl ester TPO-L balanced the photo-curing activity and storage stability. The balance between transmission depth and critical exposure intensity could be achieved via optimizing the TPO-L dosage, making it a suitable photosensitizer for polysilazane slurry.

Oxide/nitride powders (such as SiO₂ and Si₃N₄) could ensure a light penetration due to their low refractive index and light color, while carbide/boride powders (such as SiC and ZrB₂) could suffer from severe light attenuation due to their high refractive index and dark color. The density of the photocured sample increased to 1.19 g/cm³ via mixing nano-/micro-sized ceramic powders (i.e., 5% 2 μm Si₃N₄ and 5% 20 nm Si₃N₄), and reducing the light scattering loss (i.e., transmission depth 52.80 μm), which verified the feasibility of micro-/nano-sized synergy in photosensitive polysilazane slurry.

Based on the theoretical model of transmission depth D_p and critical exposure intensity E_c, the processing parameters in DLP were proposed, i.e., the layer thickness was set at 2/3 of the transmission depth (h=2D_p/3), and the exposure time was calibrated to equal to three times of the energy of the critical exposure intensity (t=3E_c/I), thus achieving a high-precision DLP printing of complex structures such as honeycomb.

Key words

light sensitive polysilazane / ceramic slurry / digital light processing / light-curing

引用本文

王子涵, 李森, 刘一阳, 刘霆邦, 何梅, 张承双, 王明存. 光敏性聚硅氮烷无溶剂陶瓷浆料的光固化3D打印性能. 硅酸盐学报, 2026 , 54 (9) : 3220 -3231 . DOI: 10.14062/j.issn.0454-5648.20250712

Zihan WANG, Sen LI, Yiyang LIU, Tingbang LIU, Mei HE, Chengshuang ZHANG, Mingcun WANG. 3D Printing Properties of Photo-Sensitive Polysilazane Solvent-Free Ceramic Slurry in Digital Light Processing[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (9) : 3220 -3231 . DOI: 10.14062/j.issn.0454-5648.20250712

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国防科工局稳定支持项目(02007000192025601)

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2026年第54卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250712

接收时间：2025-09-26
首发时间：2026-10-22
出版时间：2026-08-18

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收稿日期：2025-09-26
修回日期：2025-10-29

基金

国防科工局稳定支持项目(02007000192025601)

作者信息

^1．北京航空航天大学化学学院，北京 102206

^2．西安航天复合材料研究所，西安 710025

通讯作者:

王明存（1972—），男，副教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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