琉璃工艺品的3D打印成型研究

3D PRINTING OF COLORED GLAZE

戚慧琳

11849156

硕士

材料工程领域工程

严明

2020-05-29

2020-07-20

哈尔滨工业大学

深圳

铕镝掺杂铝酸锶（SrAl2O4: Eu2+, Dy3+）是一种长余辉发光材料，能持续较长时间发光状态，近年来被用作制备琉璃工艺品。当前制作结构复杂的琉璃工艺品的方法主要是脱蜡铸造法，需要制作数种不同材质的模具。整个流程包含十余道工序，制作难度大、生产成本高而且成功率相对较低。基于这种情况，本课题致力于自行研制一种低粘度的新型光敏树脂为分散介质，进而开发一种高固含量、适用于3D打印（光固化立体成型或数字光处理）的琉璃/光敏树脂浆料，通过优化3D打印参数和脱脂烧结工艺得到高质量、外形复杂的琉璃样品。优化后的光敏树脂各成分配比为2 wt.%光引发剂、18 wt.%预聚物、80 wt.%活性稀释剂。这种光敏树脂在所有制备的光敏树脂中流动性最佳，并被应用于后续的实验环节。本文探讨了琉璃粉末含量、分散剂含量、粉末粒径以及制备方法对琉璃/光敏树脂浆料粘度的影响。结果表明，使用三辊研磨机可以成功制备固含量78 wt.%，粘度小于3000 mPa·s的琉璃/光敏树脂浆料。先后使用了两款3D打印机：Form 2和 DLP 800d对制得的琉璃浆料进行3D打印测试。由于DLP 800d打印机激光功率更高、工艺参数可调，进而可以调节浆料的固化深度，最终打印出质量更高的琉璃生坯。优化的打印参数如下：层厚50 μm，曝光时间7000 ms，亮度65。对琉璃生坯的脱脂烧结工艺进行了探索。边长8 mm、固含量78 wt.%的实心正方体在去除琉璃生坯内的全部有机物后依旧可以维持原样品外观。可行的脱脂工艺如下：室温至50 ℃之间以约2 ℃/min的速率进行升温，50-500 ℃之间以0.1 ℃/min的速度升温，500 ℃至600 ℃以约2 ℃/min进行升温，在整个加热过程中辅以一定的保温时间。在1400 ℃、180 MPa（氩气气氛）的状态下进行热等静压烧结6 h，可以获得致密度96.26%，硬度为845.1 HV的琉璃样品，样品在X轴、Y轴和Z轴方向的线性收缩率分别是8.50%、7.50%和10.50%。本课题围绕着3D打印琉璃材料开创性地进行了一系列研究和分析，获得了致密度相对较高的琉璃样品，证明了使用DLP技术制备琉璃工艺品的可行性。

SrAl2O4: Eu2+, Dy3+ is a persistent afterglow material that can intensively glow for a long time. In recent years, it has been utilized to prepare colored glaze crafts. The current method to fabricate colored glaze works with complex shape is lost wax casting which requires the production of several models with different materials. The entire process includes more than ten procedures with high produce difficulty, high cost and a relatively low success rate. Based on this, the aim of this project is to develop a high solid loading slurry of raw colored glaze powder dispersed in a novel photosensitive resin with low viscosity synthesized by ourselves, suitable for 3D printing (stereolithography or digital lighting processing) and obtain high quality colored glaze samples with complex shapes after improving 3D printing parameters, debinding curve and sintering process.The optimal formulation of photosensitive resin is 2 wt.% photoinitiator, 18 wt.% prepolymer, and 80 wt.% reactive diluent. It exhibited the best fluidity among all prepared photosensitive resins and was used in follow-up research. The influence of colored glaze powder content, dispersant content, powder particle size, and preparation method on the viscosity of colored glaze/photosensitive resin slurry was described in this dissertation. The results showed that 78 wt.% colored glaze/photosensitive resin slurries with a viscosity < 3000 mPa·s were successfully prepared by a three-roll grinder. 3D printing of prepared colored glaze slurries were tested successively using two 3D printers: Form 2 and DLP 800d. Due to higher laser power and adjustable printing parameters, cure depth of slurry could be modified and better colored glaze green parts were printed with the DLP 800d printer. The printing parameters were optimized as follows: 50 μm layer thickness, 7000 ms exposure time and 65 brightness. Further study included the investigation on debinding and sintering process of colored glaze green parts. 8 mm solid cube (78 wt.% solid content) kept its original appearance with the removal of all polymers from the colored glaze green part. The feasible debinding process is as follows: 2 ℃/min heating rate between room temperature and 50 ℃, 0.1 ℃/min between 50 ℃ and 500 ℃ and 2 ℃/min between 500 ℃ and 600 ℃ with holding time for several times throughout the heating process. Colored glaze component with 96.26% density and 845.1 HV hardness was fabricated after a subsequent hot isostatic pressing (HIP) under 1400 ℃ and 180 MPa (Ar atmosphere) for 6 h, whose linear shrinkages of X-axis, Y-axis and Z-axis were 8.50%, 7.50% and 10.50%, respectively.The project pioneered a series of researches and analyses centering around 3D printing of colored glaze and achieved colored glaze samples with relative high density, indicating the feasibility of the preparation of colored glaze handicrafts via a DLP process.

3D 打印 铝酸锶（SrAl2O4: Eu2+ Dy3+） 琉璃 光固化立体成型 数字光处理 脱脂烧结

3D printing SrAl2O4: (Eu2+ Dy3+) colored glaze stereolithography digital lighting processing debinding & sintering

中文

联合培养

南方科技大学

戚慧琳. 琉璃工艺品的3D打印成型研究[D]. 深圳. 哈尔滨工业大学,2020.