硅酸盐学报

3D打印制备金属盐掺杂熔石英玻璃

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彭可 ¹^,² , 付华龙 ¹^,² , 于天宇 ¹^,² , 吴攀 ¹^,² , 姚佳慧 ¹^,² , 陈明君 ¹^,²

硅酸盐学报 | 研究论文 2024,52(5): 1562-1569

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硅酸盐学报 |研究论文 2024 , 52 (5) : 1562 -1569

3D打印制备金属盐掺杂熔石英玻璃

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彭可¹^,², 付华龙¹^,², 于天宇¹^,², 吴攀¹^,², 姚佳慧¹^,², 陈明君¹^,²

作者信息

^1．哈尔滨工业大学机器人技术与系统国家重点实验室，哈尔滨 150001

^2．哈尔滨工业大学机电工程学院，哈尔滨 150001

通讯作者:

于天宇（1987—），男，博士，教授。

作者简介:

彭可（1999—），女，硕士研究生。

3D Printing Fabrication of Metal Salt-Doped Fused Silica Glass

Ke PENG¹^,², Hualong FU¹^,², Tianyu YU¹^,², Pan WU¹^,², Jiahui YAO¹^,², Mingjun CHEN¹^,²

Affiliations

^1.State Key Laboratory of Robotics and System, Harbin Institute of Technology, Harbin 150001, China

^2.School of Mechatronics Engineering, Harbin Institute of Technology, Harbin 150001, China

Corresponding Author:

YU Tianyu (1987-), male, Ph.D., Professor. E-mail: tianyuyu@hit.edu.cn

PENG Ke (1999-), female, Master candidate. E-mail: pengke190929@163.com

出版时间: 2024-05-20 doi: 10.14062/j.issn.0454-5648.20230573

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摘要

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增材制造技术在制造复杂形状零件方面具有显着的优势，然而熔石英玻璃的3D打印技术仍有待开发。基于液晶显示3D打印成型技术，研究了脱脂、金属掺杂、烧结等工艺，并制备了致密透明的熔石英玻璃样件，研究掺杂Cr³⁺、Co²⁺2种金属离子的熔石英玻璃致密化和光学吸收特性。研究发现掺杂含Cr³⁺、Co²⁺ 2种金属离子的熔石英玻璃具有独特的光学吸收性能，掺杂熔石英玻璃能保持无定型结构，可对特定波段光谱进行过滤，掺杂Cr³⁺的绿色熔石英玻璃对波长471 nm的蓝光和波长660 nm的红光过滤明显；掺杂Co²⁺的蓝色熔石英玻璃对波长597 nm的黄光和波长662 nm的红光过滤明显，在集成复杂光学元件结构应用方面拥有一定的潜力。

关键词

熔石英玻璃 / 液晶显示成型 / 3D打印 / 金属盐掺杂

Abstract

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Introduction

Additive manufacturing has attracted recent attention for glass fabrication due to its advantages to manufacture parts with complex geometries. In 3D printing, various techniques such as fused deposition modeling, selective laser melting, direct ink writing, and stereolithography are developed for glass fabrication. For its high printing accuracy, fast speed, and excellent surface quality, stereolithography shows a great potential in fabricating fused quartz glass with intricate structures and optical lenses. This paper was to enhance the optical performance of fused quartz glass including optical absorption, photoluminescence and light scattering properties via infusing metal ions into the glass. We investigated the metal salt solution immersion, debinding and sintering processes based on liquid crystal display 3D printing technology. We fabricated a fused silica glass doped with Cr³⁺ and Co²⁺ metal ions.

Methods

A homogeneous solution of photopolymer was prepared via mixing 60% 2-hydroxyethyl methacrylate, 10% triethylene glycol diacrylate, and 30% phenoxyethanol. 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, Sudan orange G, and diethyl phthalate were added to the solution and dispersed for 5 min. Silica nanoparticles of 53% (in mass fraction) were then added and dispersed by a dissolver for 10 min. The photosensitive paste was cured using an LCD 3D printer. Subsequently, the printed parts were heated at 600 ℃ for 2 h, and then soaked in a metal ions solution for 1 h. After being air-dried at 50 ℃ for 1 h, the doped debinding part was sintered at 1 280 ℃ for 2 h. Metal ion-doped glass in the furnace can be obtained after cooling to room temperature.

Results and discussion

After debinding and sintering, the printed fused quartz glass parts are densified. The removal of organic binder from the debinding parts causes a contraction of the parts. The micropores disappear after the sintering process, resulting in dense parts that are colorless and transparent. Furthermore, a high concentration of the doped mental ions leads to an extensive crystallization and reduces the transparency of the samples.

Based on the Raman spectra of parts doped with Cr³⁺ and Co²⁺ and commercial glass KN7980, four characteristic peaks of fused silica glass appear, confirming that the finished parts are fused silica glass. In the Raman spectra of the fused silica, the characteristic peaks at 896 cm^-1 and 985 cm^-1 doped with Cr³⁺ correspond to the polymerized chromate species and the Cr—O stretching vibration of discrete chromate species (CrO₄^2-), respectively. This indicates that chromium oxide crystallization occurs in fused silica glass doped with a certain concentration of Cr³⁺. The XRD patterns show that Cr³⁺ induces a crystal precipitation in the fused silica glass, for characteristic peaks of quartz at 2θ of 26.43° and cristobalite at 2θ of 63.56° and 67.91° in the glass doped with Cr³⁺. The characteristic diffraction peaks in the glass doped with Co²⁺ appearing at 2θ of 32.2°, 47.7° and 57.4° are consistent with those of CoO.

The absorption spectra of the glass doped with 2.042 μmol/cm³ concentration of Cr³⁺ reveal that the bands at 471 nm and 660 nm are due to the spin-allowed transition A_2g(F)→⁴T_1g(F) and ⁴A_2g(F)→⁴T_2g(F), respectively. Consequently, Cr³⁺-doped fused silica glass can absorb blue light at 471 nm and red light at 660 nm. The absorption spectra of the parts doped with 12.249 μmol/cm³ concentration of Co²⁺ indicate that the bands at 597 nm and 662 nm result from the spin-allowed transition ⁴T_1g(F)→⁴T_1g(P) and ⁴T_1g(F)→⁴A_2g(F), respectively. Co²⁺-doped fused silica glass shows absorption of blue light at 597 nm and red light at 662 nm. Doping the glass with metal ions imparts unique optical and structural properties to the glass, so that chromium- and cobalt-containing glasses have applications in industries, such as Integrated optics, filters, fiber lasers and near-infrared laser materials.

Conclusions

LCD 3D printing technology was used to produce optical components of fused silica glass doped with Cr³⁺ and Co²⁺ metal ions, having the superior properties, compared with commercial glass KN7980. The Cr³⁺-doped green fused silica glass had a great filtering ability for blue light (471 nm) and red light (660 nm). The Co²⁺-doped blue fused silica glass had a great filtering ability for yellow light (597 nm) and red light (662 nm). The filtering performance of multilayered silica glass could be deliberately tailored to enhance its performance since the filtering ability of silica glass was correlated to the metal ion doping concentration.

Key words

fused silica glass / liquid crystal display / 3D printing / metal salt doping

引用本文

彭可, 付华龙, 于天宇, 吴攀, 姚佳慧, 陈明君. 3D打印制备金属盐掺杂熔石英玻璃. 硅酸盐学报, 2024 , 52 (5) : 1562 -1569 . DOI: 10.14062/j.issn.0454-5648.20230573

Ke PENG, Hualong FU, Tianyu YU, Pan WU, Jiahui YAO, Mingjun CHEN. 3D Printing Fabrication of Metal Salt-Doped Fused Silica Glass[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (5) : 1562 -1569 . DOI: 10.14062/j.issn.0454-5648.20230573

基金

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国家自然科学基金委青年项目(52005133)

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2024年第52卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230573

接收时间：2023-08-02
首发时间：2026-10-22
出版时间：2024-05-20

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收稿日期：2023-08-02
修回日期：2023-08-22

基金

国家自然科学基金委青年项目(52005133)

作者信息

^1．哈尔滨工业大学机器人技术与系统国家重点实验室，哈尔滨 150001

^2．哈尔滨工业大学机电工程学院，哈尔滨 150001

通讯作者:

于天宇（1987—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230573

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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