直写3D打印聚酰亚胺-氧化硅气凝胶复合材料

王鲁凯; 门静; 冯军宗; 姜勇刚; 冯坚

doi:10.13801/j.cnki.fhclxb.20230726.001

直写3D打印聚酰亚胺-氧化硅气凝胶复合材料

doi: 10.13801/j.cnki.fhclxb.20230726.001

国防科技大学　空天科学学院，新型陶瓷纤维及其复合材料重点实验室，长沙 410073

基金项目: 湖南省自然科学基金(2023JJ30632)

详细信息

通讯作者:
冯坚，博士，研究员，博士生导师，研究方向为纳米多孔气凝胶隔热材料　E-mail: fengj@nudt.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2023-06-09
- 修回日期: 2023-07-04
- 录用日期: 2023-07-13
- 网络出版日期: 2023-07-26
- 刊出日期: 2024-04-15

Direct-write 3D printing of polyimide-silica aerogel composites

Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Funds: Hunan Provincial Natural Science Foundation of China (2023JJ30632)

摘要

摘要: 特定几何体结构对实际应用场景中高效发挥气凝胶材料功能效应有着至关重要的影响。然而，受限于气凝胶的脆性、耗时制造周期和较差模具设计性，传统制造技术在气凝胶定制成型方面仍存在着挑战。直写3D打印技术可实现气凝胶按需塑型，并赋予气凝胶兼容材料组成和功能特性。本文提出了一种基于双通道互混挤出方式的直写3D打印策略，用于制备聚酰亚胺-氧化硅(OBS)气凝胶复合材料。受益于挤出过程中墨水与催化剂之间的流体扩散混合效应，化学酰亚胺化固化得以顺利实现，3D打印OBS气凝胶复合材料呈现出高结构完整性和高形状保真度。借助直写3D打印技术的空间组装优势，OBS气凝胶复合材料形成毫米、微米、纳米多尺度形貌，其中，微米尺度复合结构使3D打印OBS气凝胶复合材料表现出良好力学性能(杨氏模量高达14.4 MPa)；纳米尺度多孔结构特征，如低密度(0.208 g·cm⁻³)、高表面积(373 m²·g⁻¹)和集中孔径分布(20~30 nm)，赋予3D打印OBS气凝胶复合材料优异隔热性能(热导率低至21.25 mW·m⁻¹·K⁻¹)。尽管本文仅关注于3D打印OBS气凝胶复合材料，但该3D打印策略的成功实施将为增材制造其他种类气凝胶复合材料提供了经验借鉴。
- 3D打印 /
- 氧化硅 /
- 聚酰亚胺 /
- 气凝胶 /
- 复合材料
Abstract: The specific geometry has a crucial impact on the function of aerogel materials in application scenarios. However, conventional manufacturing technology remains challenging in the customized shaping of aerogels due to the fragility of aerogels, time-consuming manufacturing cycles, and poor designability of molds. Direct-write 3D printing technology has been applied to achieve the on-demand shaping of aerogels, imparting aerogels with compatible material composition and functional characteristics. In this work, a direct-write 3D printing strategy based on dual-channel intermixing extrusion was proposed to prepare polyimide-silica (OBS) aerogel composites. Benefiting from the efficient fluid diffusion intermixing between inks and catalysts during extrusion processes, chemical imidization solidification can be successfully achieved, and 3D-printed OBS aerogel composites show high structural integrity and high shape fidelity. Depending on the advantages of the spatial assembly of direct-write 3D printing technology, OBS aerogel composites have formed multi-scale morphologies of millimeters, micrometers, and nanometers. In micron scale, the composite structure enables 3D-printed OBS aerogel composites to display excellent mechanical properties (Young's modulus up to 14.4 MPa). Meanwhile, nanoscale pore structure features, such as low density (0.208 g·cm⁻³), high surface area (373 m²·g⁻¹), and concentrated poren diameter distribution (20-30 nm), impart 3D-printed OBS aerogel composites with excellent thermal insulation performance (thermal conductivity as low as 21.25 mW·m⁻¹·K⁻¹). Although our work only focuses on OBS aerogel composites, the successful implementation of this 3D printing strategy would provide guidelines for additive manufacturing of other aerogel composites.
- 3D printing /
- silica /
- polyimide /
- aerogel /
- composite

HTML全文

图 1 墨水的流变性能：(a) 黏度与剪切速率之间对数坐标关系图；(b) 储能模量(G')、损耗模量(G'')与剪切应力之间对数坐标关系图；(c) 墨水的流变性能参数对比图；(d) 可逆氢键交联结构示意图

Figure 1. Rheological properties of inks: (a) Log-log plots of apparent viscosity versus the shear rate; (b) Log-log plots of storage modulus (G') and loss modulus (G'') versus the shear stress; (c) Comparison of rheological performance index of different inks; (d) Schematic illustration of reversible hydrogen-bond crosslinking structure

η₀—Initial apparent viscosity; τ₀—Yield stress

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图 2 基于双通道混合挤出方式的直写3D打印技术：(a) Z字形结构中墨水与催化剂发生流体扩散混合的示意图；(b) 直写3D打印OB₇S₁₂气凝胶复合材料(b1)和OB₇S₁₀C₂气凝胶复合材料(b2)的过程照片

Figure 2. Direct-write 3D printing technology based on the specific methodology of two-channel intermixing extrusion: (a) Schematic illustration of the fluid diffusion intermixing of inks and catalysts in a zig-zag structure; (b) Optical photographs of direct-write 3D printing processes of OB₇S₁₂ aerogel composites (b1) and OB₇S₁₀C₂ aerogel composites (b2)

Sc—Supercritical; TEA—Triethylamine

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图 3 3D打印OB₇S₁₀C₂气凝胶格栅的多尺度形貌：(a) 采用1.35 mm喷嘴打印的气凝胶格栅结构的光学照片；((b)~(f)) 格栅精细结构的超景深显微镜照片；(g) 格栅横截面的表面粗糙度；((h)~(k)) OB₇S₁₀C₂气凝胶复合材料的SEM图像

Figure 3. Multi-scale morphologies of 3D-printed OB₇S₁₀C₂ aerogel grids: (a) Optical photographs of aerogel grids printed with nozzles with a diameter of 1.35 mm; ((b)-(f)) Ultra-depth three-dimensional microscopic images of fine structures in grids; (g) Surface profile of cross-sectional structure in grids; ((h)-(k)) SEM images of OB₇S₁₀C₂ aerogel composites

CNT—Carbon nanotube

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图 4 3D打印OBS气凝胶复合材料的孔结构特征：(a) 氮气吸附-脱附等温线；(b) 孔径分布曲线

Figure 4. Pore structure characteristics of 3D-printed OBS aerogel composites: (a) Nitrogen adsorption-desorption isotherms; (b) Pore diameter distributions

V—Volume of pore

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图 5 3D打印OBS气凝胶复合材料的化学组成：(a) FTIR图谱；(b) TG-DSC曲线

Figure 5. Chemical composition of 3D-printed OBS aerogel composites: (a) FTIR spectra; (b) TG-DSC curves

T_5%—Temperature for sample with 5wt% decomposition; T_d—Decomposition temperature of samples

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图 6 3D打印OBS气凝胶复合材料的力学与隔热性能：(a) 轴向和径向压缩示意图；((b), (e)) 压缩应力-应变曲线；((c), (f)) 杨氏模量和5%应变处压缩强度；(d) 3D打印OBS气凝胶的热导率

Figure 6. Mechanical and thermal performances of 3D-printed OBS aerogel composites: (a) Schematic illustration of mechanical compression in axis and radius directions; ((b), (e)) Compression stress-strain curves; ((c), (f)) Young's moduli and compressive strength at 5% strain; (d) Thermal conductivity of 3D-printed OBS aerogels

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表 1 3D打印聚酰亚胺-氧化硅(OBS)气凝胶及其复合材料的墨水配方

Table 1. Ink formula of 3D printing polyimide-silica (OBS) aerogels and their composites

Sample name abbreviation	ODA-BPDA/ wt%	Silica/ wt%	Carbon nanotube/wt%	Solvent/ wt%
OB₇S₁₂	7.0	12.0	0.0	81.0
OB₉S₁₂	9.0	12.0	0.0	79.0
OB₇S₁₀C₂	7.0	10.0	2.0	81.0
OB₇S₈C₄	7.0	8.0	4.0	81.0
Note: ODA—4, 4-diaminodiphenyl ether; BPDA—3, 3', 4, 4'-bi-phenyltetracarboxylic dianhydride.

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表 2 3D打印OBS气凝胶复合材料的孔结构数据

Table 2. Pore structure data of OBS aerogels and their composites

Sample	Density/(g·cm⁻³)	Shrinkage/%	Specific surface area^a/(m²·g⁻¹)	Mean pore diameter^b/nm	Pore volume^c/ (cm³·g⁻¹)
OB₇S₁₂	0.208	0.74	370	30.8	3.69
OB₉S₁₂	0.234	1.36	373	30.8	2.99
OB₇S₁₀C₂	0.223	3.29	285	21.7	2.19
OB₇S₈C₄	0.224	1.37	279	20.9	2.00
Notes: a—Specific surface area obtained by the BET theory; b and c—Mean pore diameter and pore volume obtained by the BJH method; BET—Brunauer-Emmett-Teller; BJH—Barrett-Joyner-Halenda.

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