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2222材料工程  2022, Vol. 50 Issue (7): 40-50    DOI: 10.11868/j.issn.1001-4381.2021.000833
  陶瓷增材制造专栏 本期目录 | 过刊浏览 | 高级检索 |
光固化3D打印陶瓷浆料及流变性研究进展
李文利1, 周宏志2, 刘卫卫1, 于海宁1, 王晶1, 巩磊1, 邢占文1,*()
1 苏州大学 机电工程学院, 江苏 苏州 215131
2 湖南理工学院 机械工程学院, 湖南 岳阳 414006
Research progress in ceramic slurries and rheology via photopolymerization-based 3D printing
Wenli LI1, Hongzhi ZHOU2, Weiwei LIU1, Haining YU1, Jing WANG1, Lei GONG1, Zhanwen XING1,*()
1 School of Mechanical and Electric Engineering, Soochow University, Suzhou 215131, Jiangsu, China
2 College of Mechanical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, Hunan, China
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摘要 

基于光固化技术原理的陶瓷3D打印因可制备尺寸精度高、表面光洁度好、显微结构均匀和力学性能优异的复杂结构陶瓷零件而备受关注，是实现高性能陶瓷零件增材制造的重要技术手段之一。该技术的核心是制备同时具有高固含量和良好打印适性要求的陶瓷浆料，其组成对固化效果和打印进程有着至关重要的影响。本文综述了立体光固化(stereolithography，SL)和数字光处理(digital light processing，DLP)两种主流光固化3D打印方法用于光固化陶瓷打印的技术方案和工作原理，比较了两者的优缺点。围绕近年来在陶瓷浆料领域的研究工作，讨论了单体/低聚物和稀释剂、分散剂、陶瓷颗粒物理性质以及固含量等对黏度、剪切稀化/增稠行为、黏弹性、屈服应力等流变行为的影响，并提出了光固化3D打印陶瓷浆料的主要发展趋势和面临的挑战，为构建高固含量光固化3D打印陶瓷浆料提供了一般性指导原则。
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李文利
周宏志
刘卫卫
于海宁
王晶
巩磊
邢占文
关键词 ： 陶瓷,  光固化,  3D打印,  固含量,  流变行为    
Abstract：

Ceramic 3D printing based on stereolithography has attracted wide attention because it can fabricate complex ceramic components with high dimensional accuracy, good surface finish, uniform microstructure, and excellent mechanical properties. It is one of the important technical means to achieve high-performance parts by additive manufacturing. The core of the technology is to prepare ceramic slurries with high solid loading and good printability, and its composition has a vital influence on the curing effect and printing process. In this review, two main additive manufacturing methods, stereolithography (SL) and digital light processing (DLP), commonly used in ceramic 3D printing were introduced, and advantages and disadvantages of the two methods were compared. Based on the research work in the field of ceramic slurries in recent years, the effects of monomer/oligomer and diluent, dispersant, physical properties of ceramic particles and solid loading on viscosity, shear thinning/thickening behavior, viscoelasticity, yield stress were discussed. Finally, the main development trends and challenges of ceramic slurries via stereolithography were put forward in, and a general guiding principle for the construction of ceramic slurries with high solid loading was provided.
Key words： ceramic    photopolymerization    3D printing    solid loading    rheological behavior
收稿日期: 2021-08-31      出版日期: 2022-07-18
中图分类号:  TB321  
基金资助:苏州市重点产业技术创新项目(SYG202040);苏州市重点产业技术创新项目(SGC2021063);江苏省三维打印装备与制造重点实验室开放基金项目(3DL202103);江苏省重点研发计划项目(BE2018010-4)
通讯作者: 邢占文     E-mail: xingzhanwen@suda.edu.cn
作者简介: 邢占文(1981—), 男, 副教授, 博士, 研究方向: 陶瓷增材制造技术与应用, 联系地址: 江苏省苏州市济学路8号苏州大学机电工程学院(215131), E-mail: xingzhanwen@suda.edu.cn
引用本文:   
李文利, 周宏志, 刘卫卫, 于海宁, 王晶, 巩磊, 邢占文. 光固化3D打印陶瓷浆料及流变性研究进展[J]. 材料工程, 2022, 50(7): 40-50.
Wenli LI, Hongzhi ZHOU, Weiwei LIU, Haining YU, Jing WANG, Lei GONG, Zhanwen XING. Research progress in ceramic slurries and rheology via photopolymerization-based 3D printing. Journal of Materials Engineering, 2022, 50(7): 40-50.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2021.000833      或      http://jme.biam.ac.cn/CN/Y2022/V50/I7/40
Fig.1  光固化3D打印技术原理
(a)立体光固化；(b)数字光处理
Fig.2  光固化陶瓷浆料的主要组成
Monomer Functionality Viscosity/(mPa·s) Refractive index Reference
2-HEA 1 10 1.445 [42-43]
HEMA 1 11 1.453 [17]
ACMO 1 12-15 1.512 [12, 44]
IBOA 1 2-9 1.476 [45-46]
HDDA 2 5-10 1.455 [10, 31-33]
DEGDA 2 12 1.463 [47]
PEG400DA 2 26 1.465 [32, 44, 48]
TPGDA 2 10-15 1.450 [9, 49]
NPGPO2DA 2 17 1.446 [45]
TMPTA 3 80-140 1.474 [10, 35, 50]
DPHA 5/6 4000-7000 1.488 [37]
Table 1  陶瓷浆料中常用的光固化单体
Diluent Viscosity/(mPa·s) Refractive index Reference
Phenoxyethanol (POE) 1.539 [17]
Glycerol (glycerin) 950 1.474 [51-52]
Polyethylene glycol (PEG) 60-100 1.465 [18]
Decahydronaphthalene (decalin) 2-3 1.474 [46]
Butoxyethyl acetate (BEA) 2 1.413 [37]
Butyl phthalate (DBP) 6-7 1.490 [6]
Camphor Solid [53]
Table 2  陶瓷浆料中常用的稀释剂
Name Chemical description Reference
Oleic acid Unsaturated carboxylic acid (18 carbons) [31, 54-55]
KH560 Silane coupling 3-glycidoxypropylthrimethoxysilane [12, 44]
Anti-Terra-U100 Salt of unsaturated polyamine amides and low-molecular acidic polyesters [5]
BYK-W 969 A solution of a hydroxy-functional alkylammonium salt of an acidic copolymer [56]
Disper BYK-111 Copolymer with an acid group [35, 57-58]
Solsperse 41000 100% active polymeric dispersant compatible with UV-curable systems [13, 15]
Variquac CC 42 NS Polypropoxy quaternary ammonium chloride [44, 59-60]
Table 3  陶瓷浆料中常用的分散剂
Ceramic Particle size/μm Solid loading/% Viscosity/(mPa·s) Reference
Alumina 0.4 45 1620 [34]
Alumina 0.4 40 2020 [42]
Alumina 0.6 44.2 25000(30 s-1) [12]
Zirconia 0.09 45 2300 [13]
Zirconia 0.385 40 2900 [59]
Alumina+zirconia 0.4+0.2 40 380 [48]
Alumina+zirconia 0.430+0.143 50 32000(30 s-1) [5]
Silica 2.29 50 110 [8]
Calcium phosphate 1.57 48 160 [53]
Hydroxyapatite 3.97 40 3700(10 s-1) [24]
Zirconia 13+0.02(70∶30) 50 6200(30 s-1) [35]
Alumina 1.66 58 [40]
Table 4  典型陶瓷浆料组成中颗粒粒径、固含量和黏度
Fig.3  不同固含量陶瓷浆料黏度曲线[38]
Fig.4  随形非接触支撑策略示意图[5]
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