Ion Exchanged Stress Evolution and High-Speed Strain Strength Characterization of Lithium Aluminosilicate Ultra-Thin Glass

doi:10.16552/j.cnki.issn1001-1625.2025.1073

Abstract

Abstract:

This study investigates the stress formation and relaxation mechanisms of lithium aluminosilicate （LAS） ultra-thin glass during ion exchange （IOX） process. By constructing a coupled theoretical framework of “Fickian interdiffusion-chemical free volume expansion-elastic constraint”， a stress calculation formula suitable for thin-plate conditions was derived. Effects of temperature （380~500 ℃） and time on surface compressive stress （CS）， depth of layer （DOL）， and central tension linear density （CTLD） were systematically analyzed. The results show that during short-cycle IOX in pure NaNO₃ molten salt， CTLD value follows a typical single-peak evolution trend of “rapid rise-peak-decline.” As temperature increases， the peak CTLD value decreases from 34 000 MPa to 27 000 MPa， reflecting the competing mechanisms between diffusion-driven stress accumulation and free-volume dissipation-induced relaxation. Based on the inversion of mass gain measurements， the mutual diffusion coefficient is extracted （D₀≈1.078 79×10^-12 cm²/s， E_a≈83.29 kJ/mol）. Combined with experimental CTLD data， a first-order kinetic model for the free-volume index B（t） is constructed， revealing a quantitative relationship among “temperature-viscosity-relaxation rate”. This study suggests that CTLD provides a more accurate characterization of the impact resistance of ultra-thin glass under high-speed strain conditions compared to conventional CS and DOL parameters， providing a theoretical basis for optimizing the strengthening process of ultra-thin glass.

Key words: ultra-thin glass, ion exchange, CTLD, free volume index, stress relaxation, high-speed strain

CLC Number:

TQ171

HU Wei, TIAN Yingliang, HUANG Wenze. Ion Exchanged Stress Evolution and High-Speed Strain Strength Characterization of Lithium Aluminosilicate Ultra-Thin Glass[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 794-805.

Figures/Tables 11

Fig.1 CTLD-IOX time curves of mixed molten salt IOX glass at 380， 440 and 500 ℃

Fig.2 CTLD-IOX time curve of IOX glass in pure NaNO3 molten salt at different temperatures

Fig.3 Relationship between mass change of IOX glass and IOX time at 380， 440 and 500 ℃ in pure NaNO3 molten salt

Fig.4 Relationship between free-volume index B of IOX glass and IOX time at 380， 440 and 500 ℃ in pure NaNO3 molten salt

Fig.5 B-t data and fits to a first-order kinetic model at 380， 440 and 500 ℃

Table 1 Fitted parameters of first-order kinetic model for B-t at 380, 440 and 500 ℃

T/℃	T/K	a=B_∞	b=B₀-B_∞	c=exp（-k）	B₀=a+b
380	653.15	0.966 58	1.761 61	0.999 78	2.728 19
440	713.15	0.862 27	3.432 38	0.999 64	4.294 65
500	773.15	0.418 35	4.521 29	0.999 45	4.939 64

Fig.6 First-order single-exponential decay model fit of B-t

Fig.7 First-order single-exponential decay model fit of B-t fitting parameters a（B∞） and IOX temperature T fitting parameters a+b（B0） and IOX temperature T

Fig.8 Linear fit of B-t fitting parameters b（B0-B∞） and IOX temperature T

Fig.9 Linear fit of B-t fitting parameters c， k and IOX temperature T

Fig.10 Comparison between actual value and calculated value of CTLD at 380， 440 and 500 ℃

References 37

[1]	KIM D W， KIM S W， LEE G， et al. Fabrication of practical deformable displays： advances and challenges［J］. Light： Science & Applications， 2023， 12： 61.
[2]	RIGHINI G C， FERRARI M， LUKOWIAK A， et al. Flexible glass： myth and photonic technology［J］. Materials， 2025， 18（9）： 2010.
[3]	CONSOLARO A， MAFFEIS M， GALUPPI L， et al. High performance windows for applications in space. Open problems and challenges［J］. Glass Structures & Engineering， 2025， 10（4）： 24.
[4]	田英良，李俊杰，杨宝瑛，等. 化学增强型超薄碱铝硅酸盐玻璃发展概况与展望［J］. 燕山大学学报， 2017， 41（4）： 283-292.
	TIAN Y L， LI J J， YANG B Y， et al. Development and prospect of chemically strengthened ultra-thin alkali alumina silicate glass［J］. Journal of Yanshan University， 2017， 41（4）： 283-292 （in Chinese）.
[5]	胡　伟，谈宝权，覃文城，等. 化学强化玻璃的发展现状及研究展望［J］. 玻璃与搪瓷， 2018， 46（3）： 44-50.
	HU W， TAN B Q， QIN W C， et al. Development and prospects of chemically strengthened glasses［J］. Glass & Enamel， 2018， 46（3）： 44-50 （in Chinese）.
[6]	姜　宏. 铝硅酸盐超薄电子玻璃［J］. 玻璃， 2022， 49（9）： 1-8.
	JIANG H. Aluminosilicate ultra-thin electronic glass［J］. Glass， 2022， 49（9）： 1-8 （in Chinese）.
[7]	胡　伟，尹勇明，孟　鸿. 热处理对锂铝硅玻璃微观结构及机械性能的影响［J］. 硅酸盐通报， 2023， 42（7）： 2613-2620.
	HU W， YIN Y M， MENG H. Effect of heat treatment on microstructure and mechanical properties of lithium aluminum silicon glass［J］. Bulletin of the Chinese Ceramic Society， 2023， 42（7）： 2613-2620 （in Chinese）.
[8]	MACRELLI G， MAURO J C， VARSHNEYA A K. Coupling of diffusion and chemical stress： the case of ion exchange in glass［J］. Journal of the American Ceramic Society， 2021， 104（11）： 5599-5613.
[9]	MAO J Y， YUAN J， GUO Z Q， et al. Enhancing bending performance of ultrathin flexible glass through chemical strengthening［J］. International Journal of Applied Glass Science， 2024， 15（3）： 267-275.
[10]	XU Y N， LIU S， DING L F， et al. Ion exchange of glass under high pressure［J］. Scripta Materialia， 2024， 251： 116221.
[11]	LEE E H， ROGERS T G， WOO T C. Residual stresses in a glass plate cooled symmetrically from both surfaces［J］. Journal of the American Ceramic Society， 1965， 48（9）： 480-487.
[12]	GARFINKEL H M， KING C B. Ion concentration and stress in a chemically tempered glass［J］. Journal of the American Ceramic Society， 1970， 53（12）： 686-691.
[13]	VARSHNEYA A K. Influence of strain energy on kinetics of ion exchange in glass［J］. Journal of the American Ceramic Society， 1975， 58（3/4）： 106-109.
[14]	SANE A Y， COOPER A R. Stress buildup and relaxation during ion exchange strengthening of glass［J］. Journal of the American Ceramic Society， 1987， 70（2）： 86-89.
[15]	GREEN D J， TANDON R， SGLAVO V M. Crack arrest and multiple cracking in glass through the use of designed residual stress profiles［J］. Science， 1999， 283（5406）： 1295-1297.
[16]	SHEN J W， GREEN D J. Prediction of stress profiles in ion exchanged glasses［J］. Journal of Non-Crystalline Solids， 2004， 344（1/2）： 79-87.
[17]	GÜZEL A S， USTA M， ÖZTÜRK Y. Ion-exchange diffusion kinetics and compressive stress analysis of float soda lime silicate glasses［J］. Journal of the Australian Ceramic Society， 2021， 57（4）： 1331-1342.
[18]	TRUSHKOVA L A， KELINA R L， VIKTOROVA Y N， et al. Stress relaxation in glasses strengthened by ion exchange［J］. Glass and Ceramics， 1981， 38（10）： 511-513.
[19]	SHEN J W， GREEN D J， TRESSLER R E， et al. Stress relaxation of a soda lime silicate glass below the glass transition temperature［J］. Journal of Non-Crystalline Solids， 2003， 324（3）： 277-288.
[20]	KIRCHNER K A， MAURO J C. Entropy production during ion exchange of glass［J］. Journal of the American Ceramic Society， 2024， 107（2）： 880-896.
[21]	ARAUJO R J， LIKITVANICHKUL S， THIBAULT Y， et al. Ion exchange equilibria between glass and molten salts［J］. Journal of Non-Crystalline Solids， 2003， 318（3）： 262-267.
[22]	MAURO J C. Materials kinetics： transport and rate phenomena［M］. Amsterdam： Elsevier， 2021.
[23]	GY R. Ion exchange for glass strengthening［J］. Materials Science and Engineering： B， 2008， 149（2）： 159-165.
[24]	胡　伟. 高强度锂铝硅玻璃及透明微晶玻璃工艺工程研究［D］. 北京：北京大学， 2025.
	HU W. Study on process engineering of high strength Li-Al-Si glass and transparent microcrystalline glass［D］. Beijing： Peking University， 2025 （in Chinese）.
[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]	胡伟，覃文城，谈宝权，等. 锂铝硅玻璃、锂铝硅化学强化玻璃及其制备方法与应用： CN110240419B［P］. 2021-11-05.
	HU W， QIN W C， TAN B Q， et al. Preparation method and application of lithium-aluminum-silicate glass and chemically strengthened lithium-aluminum-silicate glass： CN110240419B［P］. 2021-11-05 （in Chinese）.
[27]	LACHARME J P. Measurement of sodium and potassium diffusion coefficients in mixed （Na₂O‐K₂O） glasses［J］. CR Acad Sci， Ser C， 1970， 270（16）： 1350-1353.
[28]	LI X Y， JIANG L B， WANG Y， et al. Correlation between K⁺-Na⁺ diffusion coefficient and flexural strength of chemically tempered aluminosilicate glass［J］. Journal of Non-Crystalline Solids， 2017， 471： 72-81.
[29]	SEAMAN J H， LEZZI P J， BLANCHET T A， et al. Degradation of ion-exchange strengthened glasses due to surface stress relaxation［J］. Journal of Non-Crystalline Solids， 2014， 403： 113-123.
[30]	VARSHNEYA A K. Fundamentals of the glassy state［M］//Fundamentals of Inorganic Glasses. Amsterdam： Elsevier， 1994： 13-25.
[31]	COHEN M H， TURNBULL D. Molecular transport in liquids and glasses［J］. The Journal of Chemical Physics， 1959， 31（5）： 1164-1169.
[32]	COHEN M H， GREST G S. Liquid-glass transition， a free-volume approach［J］. Physical Review B， 1979， 20（3）： 1077-1098.
[33]	MCGRAW D A. A method for determining Young’s modulus of glass at elevated temperatures［J］. Journal of the American Ceramic Society， 1952， 35（1）： 22-27.
[34]	SPINNER S. Elastic moduli of glasses at elevated temperatures by a dynamic method［J］. Journal of the American Ceramic Society， 1956， 39（3）： 113-118.
[35]	LANCELOTTI R F， RODRIGUES A C M， ZANOTTO E D. Structural relaxation dynamics of a silicate glass probed by refractive index and ionic conductivity［J］. Journal of the American Ceramic Society， 2023， 106（10）： 5814-5821.
[36]	XU J J， ZHANG Y Z， ZHANG Y J， et al. Modeling of ternary ion exchange and stress evolution in lithium-containing glass［J］. Journal of the American Ceramic Society， 2025， 108（3）： e20217.
[37]	ZHANG Y J， XU J J， CHEN T D， et al. Phase field modeling of fracture mechanics for ion-exchanged glass considering large viscoelastic deformation， mechanic-electrochemical coupling［J］. Engineering Fracture Mechanics， 2024， 309： 110396.