Effect of ZrO2 on Crystallization Behavior and Microwave Dielectric Properties of Li2O-Al2O3-B2O3 Glass-Ceramics

doi:10.16552/j.cnki.issn1001-1625.2025.1087

Abstract

Abstract:

With the advancement of 5G， the demand for high-performance dielectric materials devices operating in microwave and millimeter-wave frequency bands is increasing. In this paper， Li₂O-Al₂O₃-B₂O₃（LAB） glass-ceramics were synthesized using the low-temperature co-fired method， capable of dense sintering and exhibiting excellent microwave dielectric properties at ultra-low temperature. The effect of ZrO₂ content on the crystallization behavior and microwave dielectric properties of LAB glass-ceramics was also studied. The results show that as ZrO₂ content increases from 0.2%（molar fraction， the same below） to 0.8%， the primary crystalline phase in LAB glass-ceramics is LiBO₂. The types and quantities of crystals remain essentially unchanged. The Avrami index n of glass-ceramics ranges from 3.05 to 3.89， indicating that the crystal growth mechanism in this system is primarily bulk crystallization. However， ZrO₂ content reduces the crystallization activation energy of glass-ceramics. The microstructure of LAB glass-ceramics exhibit increased porosity with increasing ZrO₂ content， consequently reducing its bulk density. Z1 glass-ceramics doped with 0.2% ZrO₂ is sintered at 650 ℃ for 7 h， yielding excellent microwave dielectric properties， microwave dielectric constant ε_r=7.5 and quality factor Q×f =16 958 GHz， the glass-ceramics is a promising candidate material for application in ultra-low temperature co-fired ceramics （ULTCC）.

Key words: Li₂O-Al₂O₃-B₂O₃ glass-ceramics, ultra-low temperature co-fired ceramics, ZrO₂, microwave dielectric property, crystallization activation energy, microstructure

CLC Number:

TQ171

NI Yubo, CHEN Zhibin, ZENG Guang, LUO Qiong, CHEN Qiao, LIU Jia, LI Wenjun, ZOU Aoqi, WANG Jing, TIAN Peijing, HAN Jianjun. Effect of ZrO₂ on Crystallization Behavior and Microwave Dielectric Properties of Li₂O-Al₂O₃-B₂O₃ Glass-Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 835-844.

Figures/Tables 11

Table 1 Composition of Z1~Z4 glass-ceramics

Sample	Molar fraction/%
Sample	Li₂O	Al₂O₃	B₂O₃	ZrO₂
Z1	50	4	46	0.2
Z2	50	4	46	0.4
Z3	50	4	46	0.6
Z4	50	4	46	0.8

Fig.1 Bulk densities of Z1~Z4 glass-ceramics sintered at 630~725 ℃ for 7 h

Fig.2 DSC curves of Z1~Z4 glass-ceramics at heating

Table 2 Characteristic temperature of samples in DSC curves

Sample No.	T_g/℃	T_p1/℃	T_p2/℃
Z1	227	328	491
Z2	228	331	499
Z3	225	333	506
Z4	224	336	505

Fig.3 XRD patterns of Z1~Z4 and LAB samples after sintering at 630， 650， and 670 ℃ for 7 h and XRD pattern of Z2 sample after sintering at temperatures ranging from 630 ℃ to 725 ℃ for 7 h

Fig.4 DSC curves of Z1~Z4 samples at heating rates of 5.0， 7.5， 10.0 and 15.0 ℃/min

Fig.5 Relationship fitting diagrams of ln?Tp2φ and 1Tp in Kissinger method and ln?φ and 1Tp in Ozawa method

Fig.6 Linear fitting result of ln?-ln?1-x and ln?φ for Z1~Z4 samples to obtain Avrami index n

Table 3 Crystallization activation energy and Avrami index n of Z1~Z4 samples

Sample	Crystallization activation energy/（kJ·mol^-1）		n
Sample	Kissinger	Ozawa	n
Z1	47	50	3.05
Z2	34	39	3.21
Z3	39	45	3.62
Z4	37	43	3.89

Fig.7 FE-SEM images of Z1~Z4 sintered at 650 ℃ for 7 h

Fig.8 Q×f and relative permittivity of Z1~Z4 glass-ceramics sintered at 630 ℃ to 725 ℃

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Effect of ZrO₂ on Crystallization Behavior and Microwave Dielectric Properties of Li₂O-Al₂O₃-B₂O₃ Glass-Ceramics

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