3D打印聚合物转化SiOC(Fe)陶瓷及其结构性能

3D printing of SiOC(Fe) polymer-derived ceramics and their structure-performance

摘要

将聚合物前驱体转化SiOC(Fe)陶瓷技术与光固化3D打印技术结合，成功开发出一种乙烯基二茂铁（VcFe）改性的聚合物前驱体光敏树脂。该树脂兼具较低黏度、高光敏性和良好固化强度，能够成形具有复杂几何结构和微纳特征的前驱体模型。在1000 ℃氩气气氛中裂解，获得形状完整、收缩均匀的SiOC(Fe)陶瓷部件（质量保留率为45.27%，密度为1.89 g/cm³，线收缩率为32.94%）。同时系统研究裂解过程中的物相演变规律与体积收缩规律特性，并表征陶瓷产物硬度（1000 ℃裂解后硬度达5.93 GPa）。本研究验证光固化3D打印技术结合聚合物前驱体转化陶瓷技术制备复杂结构SiOC(Fe)陶瓷的可行性，为该技术的应用提供指导。

Abstract

Integration of polymer-derived SiOC(Fe) ceramic technology with 3D printing successfully enables the development of a photosensitive polymer precursor resin modified with vinyl-ferrocene (VcFe). This resin combines low viscosity, high photosensitivity, and excellent curing strength, enabling fabrication of precursor models with complex geometric structures and micro-nano features. Following pyrolysis at 1000 ℃ in an argon atmosphere, structurally intact and uniformly shrunken SiOC(Fe) ceramic components are obtained, with a mass retention rate of 45.27%, a density of 1.89 g/cm³, and a linear shrinkage of 32.94%. The study systematically investigates phase evolution and volumetric shrinkage behavior during pyrolysis and characterized the ceramic hardness (achieving 5.93 GPa after pyrolysis at 1000 ℃). This work effectively validates the feasibility of fabricating complex-structured SiOC(Fe) ceramics via 3D printing combined with polymer-derived ceramic technology, providing guidance for its practical application.

关键词

3D打印 / 聚合物前驱体 / SiOC(Fe)陶瓷

Key words

3D printing / polymer precursor / SiOC(Fe) ceramics

参考文献

[1] PAWAR K . New trends in manufacturing in ceramic industry[J].International Journal of Ceramics and Ceramic Technology, 2016, 2(1): 18-20.

[2] FU Y L, XU G, CHEN Z W, et al. Multiple metals doped polymer-derived SiOC ceramics for 3D printing[J].Ceramics International, 2018, 44(10): 11030-11038.

[3] 梁栋, 何汝杰, 方岱宁. 陶瓷材料与结构增材制造技术研究现状[J].现代技术陶瓷, 2017, 38(4): 231-247.

[4] LIANG D, HE R J, FANG D N . Development of additive manufacturing of ceramics[J].Advanced Ceramics, 2017, 38(4): 231-247.

[5] PHAM D T, GAULT R S . A comparison of rapid prototyping technologies[J].International Journal of Machine Tools and Manufacture, 1998, 38(10/11): 1257-1287.

[6] 卢秉恒, 李涤尘. 增材制造(3D打印)技术发展[J].机械制造与自动化, 2013, 42(4): 1-4.

[7] LU B H, LI D C . Development of the additive manufacturing (3D printing) technology[J].Machine Building & Automation, 2013, 42(4): 1-4.

[8] WONG K V H A . A review of additive manufacturing[J].International Scholarly Research Notices, 2012, 2012(1): 208760.

[9] CAO J W, IDREES M, TIAN G Q, et al. Complex SiC-based structures with high specific strength fabricated by vat photopolymerization and one-step pyrolysis[J].Additive Manufacturing, 2021, 48: 102430.

[10] LI Z W, CHEN Z, LIU J Q, et al. Additive manufacturing of lightweight and high-strength polymer-derived SiOC ceramics[J].Virtual and Physical Prototyping, 2020, 15(2): 163-177.

[11] BADEV A, ABOULIATIM Y, CHARTIER T, et al. Photopolymerization kinetics of a polyether acrylate in the presence of ceramic fillers used in stereolithography[J].Journal of Photochemistry and Photobiology A, 2011, 222(1): 117-122.

[12] CHEN Z W, LI J J, LIU C B, et al. Preparation of high solid loading and low viscosity ceramic slurries for photopolymerization-based 3D printing[J].Ceramics International, 2019, 45(9): 11549-11557.

[13] COLOMBO P, MERA G, RIEDEL R, et al. Polymer-derived ceramics: 40 years of research and innovation in advanced ceramics[J].Journal of the American Ceramic Society, 2010, 93(7): 1805-1837.

[14] HUNDLEY J M, ECKEL Z C, SCHUELLER E, et al. Geometric characterization of additively manufactured polymer derived ceramics[J].Additive Manufacturing, 2017, 18: 95-102.

[15] SUTTOR D, ERNY T, GREIL P, et al. Fiber-reinforced ceramic-matrix composites with a polysiloxane/boron-derived matrix[J].Journal of the American Ceramic Society, 1997, 80(7): 1831-1840.

[16] ROCHA R M, BRESSIANI J C, BRESSIANI A H A . Ceramic substrates of β-SiC/SiAlON composite from preceramic polymers and Al-Si fillers[J].Ceramics International, 2014, 40(9): 13929-13936.

[17] VIJAY V, BIJU V M, DEVASIA R . Active filler controlled polymer pyrolysis-a promising route for the fabrication of advanced ceramics[J].Ceramics International, 2016, 42(14): 15592-15596.

[18] 骆春佳, 宋燕, 周睿, 等 . 高性能陶瓷聚合物前驱体研究新进展[J].高分子通报, 2019(10): 53-63.

[19] LUO C J, SONG Y, ZHOU R, et al. The progress in polymer precursors for high performance ceramics[J].Polymer Bulletin, 2019(10): 53-63.

[20] HARSHE R, BALAN C, RIEDEL R . Amorphous Si(Al)OC ceramic from polysiloxanes: bulk ceramic processing, crystallization behavior and applications[J].Journal of the European Ceramic Society, 2004, 24(12): 3471-3482.

[21] IONESCU E, LINCK C, FASEL C, et al. Polymer-derived SiOC/ZrO₂ nanocomposites with excellent high-temperature stability[J].Journal of the American Ceramic Society, 2010, 93: 241-250.

[22] LIU C Q, PAN R, HONG C Q, et al. Effects of Zr on the precursor architecture and high-temperature nanostructure evolution of SiOC polymer-derived ceramics[J].Journal of the European Ceramic Society, 2016, 36(3): 395-402.

[23] XIA K D, LU C X, YANG Y . Improving the oxidation resistance of carbon fibers using silicon oxycarbide coatings[J].New Carbon Materials, 2015, 30(3): 236-243.

[24] GURLO A, IONESCU E, RIEDEL R, et al. The thermal conductivity of polymer-derived amorphous Si-O-C compounds and nano-composites[J].Journal of the American Ceramic Society, 2016, 99: 281-285.

[25] HOJAMBERDIEV M, PRASAD R M, FASEL C, et al. Single-source-precursor synthesis of soft magnetic Fe₃Si- and Fe₅Si₃-containing SiOC ceramic nanocomposites[J].Journal of the European Ceramic Society, 2013, 33(13/14): 2465-2472.

[26] CHEN L X, ZHAO J, WANG L, et al. In-situ pyrolyzed polymethylsilsesquioxane multi-walled carbon nanotubes derived ceramic nanocomposites for electromagnetic wave absorption[J].Ceramics International, 2019, 45(9): 11756-11764.

[27] 计晓琴, 孙德林, 余先纯, 等 . Fe³⁺掺杂活化木质素基木材陶瓷的制备及电化学性能[J].材料导报, 2019, 33(20): 3390-3395.

[28] JI X Q, SUN D L, YU X C, et al. Preparation and electrochemical performance of Fe³⁺-doped activated lignin basic woodceramics[J].Materials Reports, 2019, 33(20): 3390-3395.

基金资助

国家自然科学基金(51975384)

广东省普通高校重点领域专项(2022ZDZX3017)

广东省特支计划科技人才项目(2021TQ05Z151)

广东省自然科学基金面上项目(2024A1515010049)

深圳大学国防基础科研培育基金(GFPY-YB-2024-03)