硅酸盐学报

Li₂O-ZnO-MgO-Al₂O₃-SiO₂微晶玻璃析晶行为和性能

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王浩铭 ¹ , 李路瑶 ² , 王静 ¹ , 韩建军 ¹ , 储静远 ³

硅酸盐学报 | 先进玻璃材料技术与产业发展专题—研究论文 2025,53(10): 2777-2790

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硅酸盐学报 |先进玻璃材料技术与产业发展专题—研究论文 2025 , 53 (10) : 2777 -2790

Li₂O-ZnO-MgO-Al₂O₃-SiO₂微晶玻璃析晶行为和性能

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王浩铭¹, 李路瑶², 王静¹, 韩建军¹, 储静远³

作者信息

^1．武汉理工大学先进玻璃材料全国重点实验室，武汉 430070

^2．武汉理工大学汽车工程学院，武汉 430070

^3．中国建材国际工程集团有限公司，上海 200063

通讯作者:

王静（1988—），女，博士，研究员。

作者简介:

王浩铭（2000—），男，硕士研究生。

Crystallization Behavior and Properties of Li₂O-ZnO-MgO-Al₂O₃-SiO₂ Glass-Ceramics

Haoming WANG¹, Luyao LI², Jing WANG¹, Jianjun HAN¹, Jingyuan CHU³

Affiliations

^1.National Key Laboratory of Advanced Glass Materials, Wuhan University of Technology, Wuhan 430070, China

^2.School of Automotive Engineering, Wuhan University of Technology, Wuhan 430070, China

^3.China Triumph International Engineering Co., Ltd., Shanghai 200063, China

Corresponding Author:

WANG Jing (1988-), female, Ph.D., Professor. E-mail: wangj@whut.edu.cn

WANG Haoming (2000-), male, Master candidate. E-mail: 1589337868@qq.com

出版时间: 2025-10-20 doi: 10.14062/j.issn.0454-5648.20250282

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摘要

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采用熔融-热处理法制备了Li₂O-ZnO-MgO-Al₂O₃-SiO₂（LZMAS）微晶玻璃，研究了Li₂O含量从0~6%（摩尔分数）对玻璃的结构、析晶行为及性能的影响。结果表明：Li₂O含量增加，玻璃网络聚合度和析晶活化能呈现降低的趋势。不含Li₂O的微晶玻璃析出晶相只有尖晶石晶相及SnO₂；当Li₂O含量为2%时，则有β-石英固溶体和尖晶石晶相形成。随着Li₂O含量继续增加到4%，β-锂辉石晶相出现，β-石英固溶体晶相消失。Li₂O含量为2%的基础玻璃在850 ℃晶化2 h后，晶粒分布均匀且尺寸较小，平均晶粒尺寸为28 nm，具有较高的可见光透过率~84%，且维氏硬度及弯曲强度分别可以达到8.62 GPa、199 MPa。这种材料具备优异的光学及力学性能，在光电元件、透明装甲等领域具有重要的应用价值。

关键词

尖晶石 / 微晶玻璃 / β-石英固溶体 / 弯曲强度 / 维氏硬度 / 热膨胀系数

Abstract

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Introduction

As phase-engineered composites integrating amorphous and crystalline domains, glass-ceramics synergistically retain a high transparency of vitreous materials, while achieving ceramic-like mechanical robustness. Transparent glass-ceramics include systems such as ZnO-MgO-Al₂O₃-SiO₂, Li₂O-Al₂O₃-SiO₂, etc., in which the precipitation of spinel crystalline phase can be controlled in ZnO-MgO-Al₂O₃-SiO₂ (ZMAS) system. The spinel crystal phase has a high Mohs hardness as well as a high modulus of elasticity, so the ZMAS system glass-ceramics with a spinel crystal phase has superior mechanical properties. The introduction of Li₂O into ZMAS glass-ceramics can refine the grain size and also promote the precipitation of crystal phases such as β-quartz solid solution with a low coefficient of thermal expansion, which can adjust the overall coefficient of thermal expansion of the glass-ceramics and improve the thermal shock resistance of the glass-ceramics. β-quartz solid solution crystals are close to the refractive index of the glass, which can significantly reduce the scattering of light and improve the transparency of the glass-ceramics. In this work, Li₂O-ZnO-MgO-Al₂O₃-SiO₂ glass system was selected as a research subject to investigate the effect of Li₂O content on the crystallization behavior and properties of the glass. The study revealed that the introduction of Li₂O exerted a modulating effect on the crystallization behavior, optical properties, and mechanical performance of the glass-ceramics.

Methods

The parent glasses were prepared by a melting method, and the components were designed as (54-x) SiO₂-17 Al₂O₃-x Li₂O-3 Na₂O-14 ZnO-7 MgO-3 ZrO₂-2 SnO₂ (%, x=0, 2, 4, 6). The glass was melted at 1600 ℃ for 3 h. The glass solution was poured into a copper abrasive tool that was preheated at 590 ℃ for moulding. The formed glass blocks were annealed in an annealing furnace at 590 ℃ for 5 h to remove the internal stresses in the glass, and the glass was cut into blocks with the thickness of 1.5 mm for subsequent testing. The chemical state of the elements in the base glass was characterized by a model ESCALAB250Xi X-ray photoelectron spectrometer (XPS, Thermo Fisher Co., USA). A glass powder was used for testing, corrected using the electron binding energy of C1s. The DSC curve of glass was determined by differential scanning calorimetry (DSC).. The crystalline phase of the prepared samples was examined by an X-ray diffractometer. The base glass and microcrystalline glass microstructures were analyzed by a model Ultra Plus field emission scanning electron microscope (FESEM, Zeiss Co., Germany) with an additional Ultim Max 65 energy spectrometer (JSM-IT800). The optical properties of the glass and microcrystalline glass samples after double-sided optical grade polishing were characterized by a model UV3600 UV-visible spectrophotometer (UV-vis, Shimadzu Co., Japan). The Vickers hardness of the polished glass samples was measured by a model HV-1000A microhardness tester (Huayin Co., China) with a load of 1.96 N and a dwell time of 10 s. Each glass specimen underwent five replicate measurements to minimize experimental errors. The coefficient of thermal expansion (CTE) was determined by a model DIL 402C thermal dilatometer (Netzsch Co., Germany). The glass was cut into some rectangular bars with the sizes of 4 mm × 4 mm × 25 mm for dilatometric analysis.

Results and discussion

The free oxygen content in the glass network increases with the increase of Li₂O content from 0 to 6% (in mole), leading to a reduction in the degree of network polymerization. This structural change can reduce the glass transition temperature from 745 ℃ (i.e., at 0 mol% Li₂O) to 664 ℃ (i.e., at 6% Li₂O). The β-quartz solid solutions form as the Li₂O content increases to 2%. The temperature required for the formation of β-spodumene crystals decreases as the Li₂O content further increases, leading to an increase in the β-spodumene crystalline phase content and suppression of spinel crystal precipitation. The transmittance also undergoes a sharp decline due to the influence of large-sized β-spodumene crystals. The glass-ceramics with 2% Li₂O content, after crystallization at 850 ℃, exhibit a superior performance (i.e., a Vickers hardness of 8.62 GPa, a transmittance of 84%, and a flexural strength of 199 MPa).

Conclusions

Increasing Li₂O content from 0 to 6% could promote the depolymerization of the glass network, leading to a reduction in the glass transition temperature. At 2% Li₂O, this composition effectively suppressed grain agglomeration and promoted the formation of β-quartz solid solution crystalline phases, thereby enhancing the transparency of the glass-ceramics. The coexistence of spinel phases and β-quartz solid solution improved the comprehensive properties of the glass-ceramics (i.e., a Vickers hardness of~8.62 GPa and a flexural strength of~199 MPa).

Key words

spinel / glass-ceramics / β-quartz solid solution / flexural strength / Vickers hardness / thermal expansion coefficient

引用本文

王浩铭, 李路瑶, 王静, 韩建军, 储静远. Li₂O-ZnO-MgO-Al₂O₃-SiO₂微晶玻璃析晶行为和性能. 硅酸盐学报, 2025 , 53 (10) : 2777 -2790 . DOI: 10.14062/j.issn.0454-5648.20250282

Haoming WANG, Luyao LI, Jing WANG, Jianjun HAN, Jingyuan CHU. Crystallization Behavior and Properties of Li₂O-ZnO-MgO-Al₂O₃-SiO₂ Glass-Ceramics[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (10) : 2777 -2790 . DOI: 10.14062/j.issn.0454-5648.20250282

基金

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国家自然科学基金(52272008)
上海市2022年度科技创新行动计划国际科技合作项目(22520730500)

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2025年第53卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250282

接收时间：2024-04-15
首发时间：2026-10-21
出版时间：2025-10-20

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出版历史

收稿日期：2024-04-15
修回日期：2025-05-06

基金

国家自然科学基金(52272008)

上海市2022年度科技创新行动计划国际科技合作项目(22520730500)

作者信息

^1．武汉理工大学先进玻璃材料全国重点实验室，武汉 430070

^2．武汉理工大学汽车工程学院，武汉 430070

^3．中国建材国际工程集团有限公司，上海 200063

通讯作者:

王静（1988—），女，博士，研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250282

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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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