耐压视窗玻璃材料体系及性能研究

doi:10.16552/j.cnki.issn1001-1625.2025.0943

摘要/Abstract

摘要：

耐压视窗玻璃的性能及其物理钢化效果因材料体系不同而存在显著差异。本文以钠钙硅玻璃、无碱铝硅玻璃、3.3硼硅玻璃及4.0硼硅玻璃四种典型耐压视窗玻璃为研究对象，测试了四种玻璃热学和力学的基本性能，根据拉曼光谱和核磁共振谱分析阐释了四种玻璃性能差异的结构原因，依据黏温特性及热学和力学性能研究了四种玻璃提升强度的物理钢化机制。研究发现：在成分上，钠钙硅玻璃因高碱金属和碱土金属氧化物含量形成断键网络；在结构上，无碱铝硅玻璃出现［AlO₄］、［AlO₅］结构，硼硅玻璃出现［BO₃］、［BO₄］结构。成分与结构的共同因素导致四种玻璃三维网络结构存在差异性，进而影响了它们的性能。在性能上，钠钙硅玻璃和无碱铝硅玻璃在钢化温度至转变温度区间内黏度的变化更剧烈，且具有更高的弹性模量与热膨胀系数，故能形成更高的表面压应力，强度提升显著。研究结果对于耐压视窗玻璃的研制开发具有指导意义。

关键词: 耐压视窗玻璃, 结构, 性能, 强度, 物理钢化, 表面压应力

Abstract:

The performance and physical tempering effect of pressure resistant window glass are significantly different due to different material systems. This study investigated four types of glass for pressure resistant window glass： sodium calcium silicate glass， alkali-free aluminosilicate glass， 3.3 borosilicate glass， and 4.0 borosilicate glass. Their fundamental thermal and mechanical properties were tested. The structural reasons for the differences in the properties of four types of glass were explained by Raman spectroscopy and nuclear magnetic resonance spectroscopy. The physical tempering mechanism for increasing strength of four types of glass was studied based on the viscosity temperature characteristics， thermal and mechanical properties. The study finds that： in terms of composition， sodium calcium silicate glass forms bond breaking network due to its high content of alkali metal and alkaline earth metal oxides. In terms of structure， alkali-free aluminosilicate glass appears ［AlO₄］ and ［AlO₅］ structures， and borosilicate glass appeares ［BO₃］ and ［BO₄］ structures. The common factors of composition and structure lead to the differences in the three-dimensional network structure of the four types of glass， which affect their performance. In terms of performance， the viscosity of sodium calcium silicate glass and alkali-free aluminosilicate glass changes more violently from tempering temperature to transition temperature， and have higher elastic modulus and thermal expansion coefficient， so they can form higher surface compressive stress and significantly improve strength. The research results have guiding significance for the research and development of pressure resistant window glass.

Key words: pressure resistant window glass, structure, performance, strength, physical tempering, surface compressive stress

中图分类号:

TQ171

王浩枫, 廖其龙, 竹含真, 王衍行, 李现梓, 杨鹏慧, 田昊东, 祖成奎. 耐压视窗玻璃材料体系及性能研究[J]. 硅酸盐通报, 2026, 45(3): 884-893.

WANG Haofeng, LIAO Qilong, ZHU Hanzhen, WANG Yanhang, LI Xianzi, YANG Penghui, TIAN Haodong, ZU Chengkui. Material System and Performance of Pressure Resistant Window Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 884-893.

图/表 16

表1 不同体系玻璃的组分

Table 1 Composition of glass in different systems

Glass system	Composition （mole fraction）/%
Glass system	SiO₂	Al₂O₃	CaO	B₂O₃	MgO	BaO	Na₂O
Sodium calcium silicate glass	67~68	0~1	11~12	—	5~6	—	15~16
Alkali-free aluminosilicate glass	65~66	10~11	11~12	1~2	9~10	2~3	—
3.3 borosilicate glass	78~79	3~4	0~1	12~13	0~1	—	5~6
4.0 borosilicate glass	77~78	2~3	1~2	11~12	1~1.5	0~1	6~7

表2 不同体系玻璃的性能参数

Table 2 Performance parameters of glass in different systems

Glass system	Bending strength σ_b/MPa	Hardness/GPa	Modulus of elasticity/GPa	Coefficient of thermal expansion/（10^-6 ℃）	Density/ （g·cm^-3）
Sodium calcium silicate glass	94	5.48	70.3	9.0	2.50
Alkali-free aluminosilicate glass	98	6.39	88.6	4.7	2.66
3.3 borosilicate glass	146	6.13	58.4	3.6	2.23
4.0 borosilicate glass	131	6.18	59.2	4.2	2.27

图1 不同体系玻璃的拉曼光谱

Fig.1 Raman spectra of of glass in different systems

表3 钠钙硅玻璃拉曼光谱的主要波数及振动类型

Table 3 Main wave numbers and vibration types in Raman spectra of sodium calcium silicate glass

Wave number/cm^-1	Type of vibration
455	Si—O—Si bond bending vibration
570	Si—O—Si bond bending vibration
791	Si—O—Si bond bending vibration of ［SiO₄］ structural unit
943	Si—O—Si bond bending vibration of bridging oxygen between ［SiO₄］
1 100	Si—O—Si bond antisymmetric stretching vibration

表4 无碱铝硅玻璃拉曼光谱的主要波数及振动类型

Table 4 Main wave numbers and vibration types in Raman spectra of alkali-free aluminosilicate glass

Wave number/cm^-1	Type of vibration
484	Si—O—Si bond bending vibration
797	Si—O—Al bond stretching vibration between ［AlO₄］ and ［SiO₄］
1 022	Si—O—Si bond antisymmetric stretching vibration
1 441	B—O bond stretching vibration

表5 硼硅玻璃拉曼光谱的主要波数及振动类型

Table 5 Main wave numbers and vibration types in Raman spectra of borosilicate glass

Wave number/cm^-1	Type of vibration
453	Si—O—Si bond bending vibration
800	［BO₃］ symmetric stretching vibration
927	Symmetrical stretching vibration of plane borate unit BO $3 3 -$
1 065	Stress vibration of B—O bond
1 138 （4.0 borosilicate glass）	Si—O bond stretching vibration of ［SiO₄］ structural unit
1 204 （3.3 borosilicate glass）	Symmetric stretching vibration of B—O bond in borate unit B₂O $5 4 -$
1 402~1 421	B—O bond bending vibration， corresponding to ［BO₃］ connection ［BO₄］
1 485	B—O bond stretching vibration， corresponding to ［BO₃］ connection ［BO₃］

表5 硼硅玻璃拉曼光谱的主要波数及振动类型

Table 5 Main wave numbers and vibration types in Raman spectra of borosilicate glass

Wave number/cm^-1	Type of vibration
453	Si—O—Si bond bending vibration
800	［BO₃］ symmetric stretching vibration
927	Symmetrical stretching vibration of plane borate unit BO $3 3 -$
1 065	Stress vibration of B—O bond
1 138 （4.0 borosilicate glass）	Si—O bond stretching vibration of ［SiO₄］ structural unit
1 204 （3.3 borosilicate glass）	Symmetric stretching vibration of B—O bond in borate unit B₂O $5 4 -$
1 402~1 421	B—O bond bending vibration， corresponding to ［BO₃］ connection ［BO₄］
1 485	B—O bond stretching vibration， corresponding to ［BO₃］ connection ［BO₃］

图2 硼硅玻璃和无碱铝硅玻璃的11B和27Al MAS NMR谱及高斯去卷积拟合曲线

Fig.2 11B and 27Al MAS NMR spectra and Gaussian deconvolution fitting curves of borosilicate glass and alkali-free aluminosilicate glass

表6 四种玻璃网络连接强度计算结果

Table 6 Calculation results of connection strength for four types of glass networks

Glass system	Sodium calcium silicate glass	Alkali-free aluminosilicate glass	3.3 borosilicate glass	4.0 borosilicate glass
Connection strength/kJ	1 193.83	1 275.34~1 308.77	1 479.49~1 492.04	1 464.36~1 472.23

图3 玻璃的应力分布示意图（P为外加载荷）

Fig.3 Schematic diagrams of stress distribution of glass （P is external load）

表7 四种玻璃物理钢化前后的抗弯强度

Table 7 Bending strength of four types of glass before and after physical tempering

Glass system	Bending strength/MPa
Glass system	Annealed glass	Physical tempered glass （T_d+50 ℃）	Physical tempered glass （T_d +110 ℃）
Sodium calcium silicate glass	98	340	392
Alkali-free aluminosilicate glass	102	364	403
3.3 borosilicate glass	150	213	263
4.0 borosilicate glass	134	244	280

图4 四种玻璃的热膨胀曲线

Fig.4 Thermal expansion curves of four types of glass

图5 四种玻璃在一定温度范围内的黏温曲线

Fig.5 Viscosity temperature curves of four types of glass

表8 四种玻璃的钢化温度、膨胀软化温度和转变温度

Table 8 Tempering temperature， expansion softening temperature， and transition temperature of four types of glass

Glass system	Tempering temperature （T_d+50 ℃）/℃	Tempering temperature （T_d+110 ℃）/℃	Expansion softening temperature/℃	Transition temperature/℃
Sodium calcium silicate glass	667	727	617	556
Alkali-free aluminosilicate glass	829	889	779	711
3.3 borosilicate glass	701	761	651	527
4.0 borosilicate glass	721	781	671	573

表9 四种玻璃不同钢化温度对应的黏度值

Table 9 Viscosity values of four types of glass at different tempering temperatures

Tempering temperature	Viscosity/（Pa·s）
Tempering temperature	Sodium calcium silicate glass	Alkali-free aluminosilicate glass	3.3 borosilicate glass	4.0 borosilicate glass
T_d+50 ℃	10^7.9	10^8.8	10^9.2	10^9.1
T_d+110 ℃	10^6.5	10^7.0	10^7.7	10^7.6

表10 不同钢化温度下四种玻璃的黏度变化速率

Table 10 Viscosity change rate of four types of glass at different tempering temperatures

Tempering temperature	Viscosity change rate/10¹¹
Tempering temperature	Sodium calcium silicate glass	Alkali-free aluminosilicate glass	3.3 borosilicate glass	4.0 borosilicate glass
T_d+50 ℃	2.26	2.13	1.44	1.70
T_d+100 ℃	1.47	1.41	1.07	1.21

表11 不同钢化温度下四种玻璃的表面压应力

Table 11 Surface compressive stress of four types of glass at different tempering temperatures

Empering temperature	Surface compressive stress/MPa
Empering temperature	Sodium calcium silicate glass	Alkali-free aluminosilicate glass	3.3 borosilicate glass	4.0 borosilicate glass
T_d+50 ℃	162	198	82	106
T_d +110 ℃	280	326	164	191

参考文献 26

[1]	LAI Y L， GU F L， YU J X， et al. Environment dependence of hardness and fracture toughness of soda lime silica glass in humid and liquid conditions［J］. Journal of Non-Crystalline Solids， 2021， 569： 120985.
[2]	TO T， JENSEN L R， SMEDSKJAER M M. On the relation between fracture toughness and crack resistance in oxide glasses［J］. Journal of Non-Crystalline Solids， 2020， 534： 119946.
[3]	孔　勇，肖卓豪，程　灵，等. 高硬度透明微晶玻璃的研究进展与应用［J］. 陶瓷学报， 2022， 43（6）： 994-1006.
	KONG Y， XIAO Z H， CHENG L， et al. Research progress and application status of high hardness transparent glass-ceramics［J］. Journal of Ceramics， 2022， 43（6）： 994-1006 （in Chinese）.
[4]	KOIKE A， AKIBA S， SAKAGAMI T， et al. Difference of cracking behavior due to Vickers indentation between physically and chemically tempered glasses［J］. Journal of Non-Crystalline Solids， 2012， 358（24）： 3438-3444.
[5]	DIX S， SCHULER C， KOLLING S. Digital full-field photoelasticity of tempered architectural glass： a review［J］. Optics and Lasers in Engineering， 2022， 153： 106998.
[6]	WANG J X， ZHAO M H， GUO J Q. The classification method of different glasses is clear and composition analysis［J］. Highlights in Science， Engineering and Technology， 2022， 21： 362-367.
[7]	PHILLIPS J C. Structure and selectively enhanced Raman spectra of high-silica alkali-silicate glasses［J］. Physical Review B， 1985， 32（8）： 5350-5355.
[8]	MUNIZ R F， SOARES V O， MONTAGNINI G H， et al. Thermal， optical and structural properties of relatively depolymerized sodium calcium silicate glass and glass-ceramic containing CaF₂ ［J］. Ceramics International， 2021， 47（17）： 24966-24972.
[9]	BECHGAARD T K， SCANNELL G， HUANG L P， et al. Structure of MgO/CaO sodium aluminosilicate glasses： Raman spectroscopy study［J］. Journal of Non-Crystalline Solids， 2017， 470： 145-151.
[10]	LIAN M， WANG T， WEI C. Effect of B₂O₃ and basic oxides on network structure and chemical stability of borosilicate glass［J］. Ceramics， 2024， 7（2）： 516-529.
[11]	ZHANG M H， LIN J， YE S， et al. The effects of boron trioxide on the structure and degradation behaviour of borosilicate bioactive glass［J］. Materials Technology， 2023， 38（1）： 2199581.
[12]	青礼平，韦　奔，肖子凡，等. Al₂O₃和B₂O₃对铝硼硅酸盐玻璃结构和热学性能的影响［J］. 玻璃， 2024， 51（2）： 29-33+42.
	QING L P， WEI B， XIAO Z F， et al. Effect of Al₂O₃ and B₂O₃ on the structure and thermal properties of aluminum borosilicate glasses［J］. Glass， 2024， 51（2）： 29-33+42 （in Chinese）.
[13]	蒋新朝. 硅酸盐玻璃的力学性能研究［D］. 济南：齐鲁工业大学， 2021.
	JIANG X Z. The study on the mechanical properties of silicate glass［D］. Jinan： Qilu University of Technology， 2021 （in Chinese）.
[14]	蒋新朝，刘树江，沈建兴. 钠钙硅玻璃的网络联接程度对力学性能的影响［J］. 陶瓷学报， 2020， 41（5）： 722-728.
	JIANG X Z， LIU S J， SHEN J X. Effect of network connectivity on mechanical properties of soda lime silica glass［J］. Journal of Ceramics， 2020， 41（5）： 722-728 （in Chinese）.
[15]	SUN K H. Fundamental condition of glass formation［J］. Journal of the American Ceramic Society， 1947， 30（9）： 277-281.
[16]	LEE S K， YI Y S， CODY G D， et al. Effect of network polymerization on the pressure-induced structural changes in sodium aluminosilicate glasses and melts： ²⁷Al and ¹⁷O solid-state NMR study［J］. The Journal of Physical Chemistry C， 2012， 116（3）： 2183-2191.
[17]	LEE A C， LEE S K. Network polymerization and cation coordination environments in boron-bearing rhyolitic melts： insights from ¹⁷O， ¹¹B， and ²⁷Al solid-state NMR of sodium aluminoborosilicate glasses with varying boron content［J］. Geochimica et Cosmochimica Acta， 2020， 268： 325-347.
[18]	MANARA D， GRANDJEAN A， NEUVILLE D R. Advances in understanding the structure of borosilicate glasses： a Raman spectroscopy study［J］. American Mineralogist， 2009， 94（5/6）： 777-784.
[19]	KATO Y， YAMAZAKI H， KUBO Y， et al. Effect of B₂O₃ content on crack initiation under Vickers indentation test［J］. Journal of the Ceramic Society of Japan， 2010， 118（1381）： 792-798.
[20]	NEUVILLE D R， CORMIER L， MASSIOT D. Al coordination and speciation in calcium aluminosilicate glasses： effects of composition determined by ²⁷Al MQ-MAS NMR and Raman spectroscopy［J］. Chemical Geology， 2006， 229（1/2/3）： 173-185.
[21]	王照猛，朱雪梅，陈淑勇，等. 分子动力学模拟研究混合碱土金属对无碱硼铝硅酸盐玻璃结构和性能的影响［J］. 硅酸盐通报， 2020， 39（10）： 3340-3346.
	WANG Z M， ZHU X M， CHEN S Y， et al. Effect of mixed alkaline earth on structure and properties of alkali-free boron aluminum silicate glasses via molecular dynamics simulations［J］. Bulletin of the Chinese Ceramic Society， 2020， 39（10）： 3340-3346 （in Chinese）.
[22]	杨雨婷，李浩田，宋　斌，等. 氧化铝含量对玻璃原子间作用力影响的第一性原理计算［J］. 材料科学与工程学报， 2024， 42（6）： 883-887.
	YANG Y T， LI H T， SONG B， et al. First-principles calculation of the effect of alumina content on interatomic forces in glass［J］. Journal of Materials Science and Engineering， 2024， 42（6）： 883-887 （in Chinese）.
[23]	丁志松. 高硬高抗碎裂钙铝硅准三元玻璃的组分设计探索［D］. 武汉：武汉理工大学， 2022.
	DING Z S. Research on composition design of calcium aluminosilicate quasi ternary glasses with high hardness and crack resistance［D］. Wuhan： Wuhan University of Technology， 2022 （in Chinese）.
[24]	BÓ M D， HOTZA D. Numerical modeling and statistical analysis of the effect of thermomechanical properties on residual stresses in feldspar-based ceramic materials after thermal tempering［J］. International Journal of Ceramic Engineering & Science， 2024， 6（2）： e10208.
[25]	田英良，孙诗兵. 新编玻璃工艺学［M］. 北京：中国轻工业出版社， 2009.
	TIAN Y L， SUN S B. New glass technology［M］. Beijing： China Light Industry Press， 2009 （in Chinese）.
[26]	王衍行，杨鹏慧，李现梓，等. 物理钢化玻璃的研究进展［J］. 材料导报， 2024， 38（11）： 62-69.
	WANG Y H， YANG P H， LI X Z， et al. Research progress on physical tempered glass［J］. Materials Reports， 2024， 38（11）： 62-69 （in Chinese）.