石膏的直写成型：可打印石膏浆料的研制

doi:10.15541/jim20210606

无机材料学报 ›› 2022, Vol. 37 ›› Issue (3): 338-346.DOI: 10.15541/jim20210606 CSTR: 32189.14.10.15541/jim20210606

所属专题：【制备方法】3D打印(202409)

石膏的直写成型：可打印石膏浆料的研制

周红莉¹(), 蔡志勇¹, 王小锋¹(), 曾婧², 冯艳¹, 彭超群¹, 王日初¹

1.中南大学材料科学与工程学院, 长沙 410083
2.中南大学冶金与环境学院, 长沙 410083

收稿日期:2021-10-02 修回日期:2021-12-02 出版日期:2022-03-20 网络出版日期:2021-12-24
通讯作者: 王小锋, 副教授. E-mail: wangxiaofeng@csu.edu.cn
作者简介:周红莉(1996-), 女, 硕士研究生. E-mail: summertimezhl@163.com

Direct Ink Writing of Gypsum: Developing a Printable Gypsum Paste

ZHOU Hongli¹(), CAI Zhiyong¹, WANG Xiaofeng¹(), ZENG Jin², FENG Yan¹, PENG Chaoqun¹, WANG Richu¹

1. School of Materials Science and Engineering, Central South University, Changsha 410083, China
2. School of Metallurgy and Environment, Central South University, Changsha 410083, China

Received:2021-10-02 Revised:2021-12-02 Published:2022-03-20 Online:2021-12-24
Contact: WANG Xiaofeng, associate professor. E-mail: wangxiaofeng@csu.edu.cn
About author:ZHOU Hongli (1996-), female, Master candidate. E-mail: summertimezhl@163.com
Supported by:
Natural Science Foundation of Hunan Province(2020JJ4729)

摘要/Abstract

摘要：

石膏是雕像、建筑和铸造模具(合金和陶瓷)的常用材料。采用直写成型(Direct Ink Writing, DIW)打印石膏可避免其他3D打印技术(如Binder Jetting, PBBJ等)中存在水化反应不充分等问题, 获得高强度3D打印石膏。为了延缓水化反应获得充足的打印操作时间, 本研究通过添加缓凝剂和增稠剂, 研制了一种适用于直写成型的石膏浆料, 并打印了多种石膏三维结构(如蜘蛛网和木材堆积结构等)。结果表明, 质量分数为0.6%柠檬酸(Citric Acid, CA)的缓凝效果最好, 极大地减少了石膏流动性的经时损失。质量分数为0.3%羟丙基甲基纤维素(Hydroxypropyl Methylcellulose, HPMC)的增稠效果最好, 使石膏浆料具有良好的打印性能。CA的选择性吸附使得石膏晶体定向生长, 延长水化反应时间, 但一定程度降低石膏强度。HPMC加速石膏浆料中絮凝结构形成, 导致其粘度和剪切弹性模量升高。直写成型3D石膏件的抗压强度约为20 MPa, 远高于PBBJ等方法制备的石膏件的抗压强度。

关键词: 直写成型, 石膏, 缓凝剂, 增稠剂, 流变性能, 铸造

Abstract:

Gypsum is a common material for statues, building, and casting molds (alloys and ceramics). Due to the incomplete hydration reaction between water and gypsum, it is difficult to print high-strength gypsum products using 3D printing techniques such as Binder Jetting. To enhance its strength, the hydration reaction should be completely performed, which could be fulfilled by direct ink writing (DIW). However, the reaction in the gypsum paste for DIW is so fast that less time is left for operating a 3D printer. In this work, a printable gypsum paste with a reasonable setting time was developed to print 3D gypsum structures via direct ink writing. A retarder and a thickener were introduced into the paste to prolong its setting time for operating and tailor its rheological property for printing, respectively. The setting time, expansion and rheological properties of the pastes were tested by the Vicat apparatus, consistometer and rheometer, respectively. The results show that citric acid (CA) is a suitable retarder, although decreases its compressive strength due to the directional grown gypsum crystals resulting from the selective adsorption of CA on gypsum powder, while hydroxypropyl methylcellulose (HPMC) is an acceptable thickener, which affects forming flocculation structure in the paste, resulting in higher viscosity and shear modulus. Optimal amounts of CA and HPMC for the printable gypsum paste are 0.6% and 0.3% (in mass), respectively. Three-dimensional gypsum structures such as spider web and scaffold are successfully printed via direct ink writing, which compressive strength is around 20 MPa, much higher than that printed via Binder Jetting.

Key words: direct ink writing, gypsum, retarder, thickener, rheological property, casting

中图分类号:

TQ174

周红莉, 蔡志勇, 王小锋, 曾婧, 冯艳, 彭超群, 王日初. 石膏的直写成型：可打印石膏浆料的研制[J]. 无机材料学报, 2022, 37(3): 338-346.

ZHOU Hongli, CAI Zhiyong, WANG Xiaofeng, ZENG Jin, FENG Yan, PENG Chaoqun, WANG Richu. Direct Ink Writing of Gypsum: Developing a Printable Gypsum Paste[J]. Journal of Inorganic Materials, 2022, 37(3): 338-346.

图/表 6

Fig. 1 Effect of retarders on gypsum paste (a) Setting time vs content of retarder; (b) Fluidity vs content of citric acid (CA) in the gypsum paste; (c) Shear elastic modulus vs shear stress; (d) Yield stress vs content of CA

Fig. 2 Effect of thickener on gypsum paste (a) Setting time vs content of thickeners; (b) Fluidity vs content of thickener; (c) Shear modulus of elasticity of HPMC with different dosage; (d) Yield stress vs content of HPMC

Fig. 3 Structures and microstructures of printed 3D gypsum (a, d) Scaffold structure with three horizontal lines and three vertical lines appearing alternately and periodically in the Z-axis, the cross angle is 60°; (b, e) Spider structure consisting of alternate layers of radial and circular rods; (c, f) Scaffold structure with three horizontal lines and three vertical lines appearing alternately and periodically in the Z-axis, the cross angle is 45°; (g-i) Microstructure of printed gypsum parts

Fig. 4 Compressive strength of different gypsum samples3 Discussion

Fig. 5 XRD patterns at different hydration time for gypsum pastes with different agents (a) 0.6% (in mass) citric acid gypsum at different hydration time; (b) 0.6% (in mass) citric acid and 0.3% (in mass) HPMC at different hydration time

Fig. 6 SEM images of gypsum at different hydration time (a-d) Gypsum with 0.6% (in mass) CA at different hydration time ((a) 5 min, (b) 12 min, (c) 20 min, (d) 300 min (final setting time)); (e-f) Gypsum with 0.6% (in mass) CA and 0.3% (in mass) HPMC at different hydration time ((e) 5 min, (f) 12 min, (g) 20 min, (h) 320 min (final setting time))

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石膏的直写成型：可打印石膏浆料的研制

Direct Ink Writing of Gypsum: Developing a Printable Gypsum Paste

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