绿色氧化锆(ZrO2)陶瓷饰品材料的光固化3D打印成形研究

Photocuring 3D Printing of Green Zirconia (ZrO2)Ceramic Jewelry Material

  • 摘要: 彩色氧化锆(ZrO2)陶瓷以其丰富的色彩,金属光泽以及优良生物亲和性等特点,在装饰材料以及艺术品领域得到了广泛关注。受限于氧化锆陶瓷的高强度和高硬度,复杂结构陶瓷饰品对模具要求高,成本高周期长,不利于个性化定制。激光立体光刻(SLA)作为一种无需模具的高精度3D打印技术,在复杂结构设计的个性化陶瓷饰品制造上极具潜力。然而该技术在打印高吸光度、高折射率彩色氧化锆材料方面还存在很多挑战,主要在于深色氧化锆的紫外光吸收性以及高折射率导致的光散射,进而造成固化层厚度小,容易分层甚至难以成形。本文基于SLA技术,以绿色氧化锆为研究对象,在绿色氧化锆光固化陶瓷浆料中引入低折射率SiO2作为紫外光传导介质,降低陶瓷浆料固液界面折射率差值以减少散射,增强紫外光透射,并通过流变力学、光固化动力学、物相结构、致色机理、力学性能等分析,优化打印成形工艺与脱脂烧结工艺,最终确定以15 vol.%SiO2掺入的绿色氧化锆色彩与力学综合性能表现较好。综上,通过在绿色氧化锆陶瓷浆料中加入15 vol.%SiO2,在1 450 ℃下烧结可以制备出色彩饱满,力学性能良好的复杂结构陶瓷饰品,满足绿色氧化锆陶瓷首饰在穿戴过程中的审美要求和实用性需求,并为彩色氧化锆陶瓷3D打印成形提供了新思路。

     

    Abstract: Coloured zirconia (ZrO2) ceramics have been widely used in the field of decorative materials and artwork because of their rich colour, metallic luster and excellent biocompatibility. Limited by the high strength and high hardness of zirconia ceramics, complex structure ceramic jewelry has high mold requirements, high cost and long cycle, which is not conducive to personalized customization. Laser stereo lithography apparatus (SLA), as a high-precision 3D printing technology without mold, has great potential in the manufacture of personalized ceramic jewelry with complex structural designs. However, this technology still has many challenges in printing high absorbance and high refractive index colour zirconia materials, mainly due to the ultraviolet light absorption of dark zirconia and light scattering caused by high refractive index, resulting in low curing layer thickness, easy layering and even difficult to form. In this study, based on SLA technology, green zirconia was taken as the research object, and low refractive index silica was introduced into green zirconia photocurable ceramic slurry as the ultraviolet light conduction medium, so as to reduce the difference of refractive index between solid and liquid interface of ceramic slurry, reduce the scattering and enhance the ultraviolet light transmission. Through the analysis of rheological mechanics, photocuring dynamics, phase structure, colour mechanism and mechanical properties, the printing forming process and degrease sintering process were optimized. Finally, it was determined that the green zirconia mixed with 15 vol.% silicon dioxide had better colour and mechanical properties. In summary, by adding 15 vol.% silica into the green zirconia ceramic slurry and sintering at 1 450 ℃, the complex structure ceramic jewelry with full colour and good mechanical properties can be prepared, which meets the aesthetic requirements and practical needs of green zirconia ceramic jewelry in the wearing process, and provides a new idea for the 3D printing of colored zirconia ceramics.

     

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