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2222材料工程  2019, Vol. 47 Issue (12): 143-150    DOI: 10.11868/j.issn.1001-4381.2018.000667
  研究论文 本期目录 | 过刊浏览 | 高级检索 |
混杂光固化3D打印树脂固化动力学性能
林广鸿, 尹敬峰, 黄鸿, 黄伟滨, 蔡慕华, 向洪平(), 刘晓暄
广东工业大学 材料与能源学院, 广州 510006
Photocuring kinetics properties of hybrid UV-curing resin for 3D printing
Guang-hong LIN, Jing-feng YIN, Hong HUANG, Wei-bin HUANG, Mu-hua CAI, Hong-ping XIANG(), Xiao-xuan LIU
School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
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摘要 

以环氧树脂(EPON828)和聚氨酯丙烯酸酯(RJ429)为基础树脂,采用自由基-阳离子混杂光固化体系来制备可用于3D打印的混杂光固化树脂,研究固化过程中自由基和阳离子光引发剂的种类、质量配比和加入量对光固化树脂固化动力学及其力学性能与成型精度的影响。结果表明:阳离子光引发剂Gencure 842和自由基光引发剂Doracur 1173为最佳复配引发剂,最佳质量比为0.75:1,最优加入量为6.0%(质量分数);环氧树脂828和聚氨酯丙烯酸酯429的最佳质量比为1:1,混杂光固化树脂的黏度为50.5Pa·s;光固化制品的拉伸强度和冲击强度分别为6.60MPa和8.28kJ·m-2,体积收缩率和翘曲度分别为-3.986%和3.62%,满足3D打印光敏树脂的成型要求。

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林广鸿
尹敬峰
黄鸿
黄伟滨
蔡慕华
向洪平
刘晓暄
关键词 光固化3D打印环氧树脂聚氨酯丙烯酸酯自由基-阳离子混杂光固化体积收缩    
Abstract

Free radical-cationic hybrid UV-curable resin applied to UV-cured 3D printing was developed with epoxy resin (EPON828) and polyurethane acrylate (RJ429) as photosensitive prepolymers. The influences of types, ratios and dosages of free radical and cationic photoinitiators on photocuring kinetics, mechanical properties and prototyping precision of hybrid UV-curing resin were investigated. The results show that cationic photoinitiator Gencure 842 and free radical photoinitiator Doracur 1173 are the most appropriate hybrid photoinitiators, with an optimum mass ratio of 0.75:1 and mass fraction of 6%. The optimum mass ratio of EPON828 and RJ429 is determined as 1:1, and the viscosity of the developed resin is 50.5Pa·s. The tensile strength, impact strength, volume shrinkage and warpage of UV-cured resin items are 6.60MPa, 8.28kJ·m-2, -3.986% and 3.62%, respectively. The hybrid UV-curing resin can basically satisfy the requirements of UV-cured 3D printing.

Key wordsUV-cured 3D printing    epoxy resin    polyurethane acrylate    free radical-cationic hybrid UV-curing    volume shrinkage
收稿日期: 2018-05-31      出版日期: 2019-12-17
中图分类号:  O631.3+4  
基金资助:国家自然科学基金项目(21604014);国家自然科学基金项目(51641302);广东省科技计划项目(2015B010122005)
通讯作者: 向洪平     E-mail: xianghongping@gdut.edu.cn
作者简介: 向洪平(1986-), 男, 副教授, 博士, 主要从事高分子光化学及光固化技术应用, 联系地址:广东省广州市广东工业大学材料与能源学院(510006), E-mail:xianghongping@gdut.edu.cn
引用本文:   
林广鸿, 尹敬峰, 黄鸿, 黄伟滨, 蔡慕华, 向洪平, 刘晓暄. 混杂光固化3D打印树脂固化动力学性能[J]. 材料工程, 2019, 47(12): 143-150.
Guang-hong LIN, Jing-feng YIN, Hong HUANG, Wei-bin HUANG, Mu-hua CAI, Hong-ping XIANG, Xiao-xuan LIU. Photocuring kinetics properties of hybrid UV-curing resin for 3D printing. Journal of Materials Engineering, 2019, 47(12): 143-150.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2018.000667      或      http://jme.biam.ac.cn/CN/Y2019/V47/I12/143
Fig.1  翘曲度测试示意图
Fig.2  混杂光固化树脂的聚合过程
Photoinitiator Absorption peak range/nm λmax/nm
Gencure 831 210-350 292
Gencure 842 208-300 239
Gencure 202 210-360 296
Table 1  阳离子引发剂的吸收峰范围和最大吸收波长
Fig.3  不同阳离子光引发剂引发环氧树脂828光固化反应的转化率
Photoinitiator Curing depth/mm Dry time/s Tensile strength/
MPa
Impact strength/(kJ·m-2)
Gencure 831 1.43 18 2.24 2.01
Gencure 842 3.21 10 3.89 2.65
Gencure 202 0.73 79 1.32 1.28
Table 2  不同阳离子光引发剂下环氧树脂828固化后的性能
Fig.4  不同Gencure 842加入量引发环氧树脂828光固化反应的转化率
Photoinitiator Absorption peak range/nm λmax/nm
Doracur 1173 225-413 331
Irgacure 651 240-360 317
Irgacure 184 240-335 280
TPO 350-400 380
Irgacure 369 325-335 440
Table 3  自由基光引发剂的吸收峰范围和最大吸收波长
Fig.5  不同自由基光引发剂引发聚氨酯丙烯酸树脂RJ429光固化反应的转化率
Fig.6  Gencure 842与不同自由基光引发剂复配引发环氧树脂828光固化反应的转化率
Fig.7  不同Doracur 1173加入量引发聚氨酯丙烯酸树脂RJ429光固化反应的转化率
Fig.8  不同复配光引发剂质量配比引发双键反应的转化率(a)和环氧基团反应的转化率(b)
Fig.9  不同复配光引发剂加入量引发双键反应的转化率(a)和环氧基团的反应转化率(b)
Fig.10  不同辐照强度下双键反应的转化率(a)和环氧基团反应的转化率(b)
Fig.11  环氧树脂828,丙烯酸树脂429与混杂光固化树脂的黏度
Fig.12  混杂光固化树脂的凝胶质量分数与硬度
Fig.13  混杂光固化树脂的拉伸强度与冲击强度
Fig.14  混杂光固化树脂固化样条
E/A Volume shrinkage/% Warpage/%
0 -7.278 11.27
0.50 -5.072 5.78
0.75 -4.559 5.06
1.00 -3.986 3.62
1.50 -3.927 4.12
2.00 -3.789 3.97
Table 4  混杂光固化树脂的体积收缩率和翘曲度
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