Additive Manufacturing of Transparent Multi-component Nanoporous Glasses

Fabrication of glass with complex geometric structures by digital additive manufacturing (3D printing) presents a paradigm shift in glass design and molding processes. Till now, 3D printing glasses have suffered from limited printed glass materials and the low resolution of particle-based or fused glass technologies. Herein, a high-resolution 3D printing of transparent nanoporous glass is presented, by the combination of transparent photo-curable sol-gel printing compositions and digital light processing (DLP) technology. Multi-component glass, including binary (Al2O3-SiO2), ternary (ZnO-Al2O3-SiO2, TiO2-Al2O3-SiO2), and quaternary oxide (CaO-P2O5-Al2O3-SiO2) nanoporous glass objects with complex shapes, high spatial resolutions, and multi-oxide chemical compositions are fabricated, by DLP printing and subsequent sintering process. The uniform nanopores of Al2O3-SiO2-based nanoporous glasses with the diameter (~6.04 nm) which is much smaller than the visible light wavelength, result in high transmittance (> 95%) at the visible range. The high surface area of printed glass objectives allows post-functionalization via the adsorption of functional guest molecules. We successfully demonstrated the photoluminescence and hydrophobic modification of 3D printed glass objectives. This work extends the scope of 3D printing to transparent nanoporous glasses with complex geometry and facile functionalization, making them available for a wide range of applications.

采用数字化增材制造（3D打印）制备具有复杂几何结构的玻璃，为玻璃设计与成型工艺带来了范式革新。迄今为止，3D打印玻璃仍面临打印用玻璃材料种类有限、基于颗粒或熔融玻璃技术的分辨率偏低等问题。本研究通过结合透明光固化溶胶-凝胶打印配方与数字光处理（DLP）技术，实现了透明纳米多孔玻璃的高分辨率3D打印。通过DLP打印结合后续烧结工艺，本研究成功制备出具备复杂形貌、高空间分辨率及多氧化物化学组成的多组分纳米多孔玻璃构件，涵盖二元（Al₂O₃-SiO₂）、三元（ZnO-Al₂O₃-SiO₂、TiO₂-Al₂O₃-SiO₂）以及四元氧化物（CaO-P₂O₅-Al₂O₃-SiO₂）体系。Al₂O₃-SiO₂基纳米多孔玻璃的均匀纳米孔径约为6.04 nm，远小于可见光波长，使其在可见光波段具备高于95%的高透光率。所打印玻璃构件的高比表面积，使其可通过吸附功能性客体分子实现后功能化改性。本研究成功实现了3D打印玻璃构件的光致发光与疏水改性。本研究将3D打印的应用范畴拓展至具备复杂几何结构与简易功能化改性能力的透明纳米多孔玻璃，为其在多领域的广泛应用提供了可能。