Effects of Bi/Zn and B/Zn on Structure and Properties of Low-Melting-Point Glass of BiBZn System for Laser Sealing of Vacuum Glazing

doi:10.16552/j.cnki.issn1001-1625.2025.0961

Abstract

Abstract:

Laser sealing technology is a high-precision， high-efficiency modern welding technique that offers the advantages of high energy density and the ability to locally heat the material. Applying laser sealing technology to vacuum glazing sealing can effectively reduce the substrate de-tempering of vaccum glazing caused by traditional overall heating sealing methods. This paper focused on the laser sealing technology and the glass of Bi₂O₃-B₂O₃-ZnO （BiBZn） system as the research subject. The paper explored the effects of Bi/Zn and B/Zn on the structure and properties of BiBZn system low-melting-point glass and developed a lead-free low-melting-point glass powder suitable for laser sealing of vacuum glazing. The lead-free low-melting-point glass components is 40.0Bi₂O₃-32.5B₂O₃-27.5ZnO， and the coefficient of thermal expansion is 100×10^-7 K^-1（50~250 ℃）， which is well-matched with the coefficient of thermal expansion of sodium-calcium-silicon substrate glass （92×10^-7 K^-1， 50~250 ℃）. The softening temperature of glass is 388 ℃， and it has good fluidity， making it suitable for laser sealing of vacuum glazing. Under the processing conditions of laser power of 36 W， pulse width of 20 ns， the obtained sealing layer has no crystal precipitation， and the sealing strength is 3.67 MPa， higher than the general level （2 MPa）.

Key words: Bi₂O₃-B₂O₃-ZnO （BiBZn）, low-melting-point glass, lead-free, laser sealing, vacuum glazing

CLC Number:

TQ171

HE Zhe, LI Jingwei, MA Xuan, SHI Lifen, JIAO Jinxu, ZHOU Junjie, WANG Weiwei, LI Changqing, WANG Peng, PENG Shou, LI Hong. Effects of Bi/Zn and B/Zn on Structure and Properties of Low-Melting-Point Glass of BiBZn System for Laser Sealing of Vacuum Glazing[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 871-883.

Figures/Tables 17

Fig.1 Schematic diagram of laser sealing vacuum glazing

Table 1 Glass composition with variations in Bi/Zn components

Sample No.	Mole fraction/%
Sample No.	Bi₂O₃	B₂O₃	ZnO
BiZn-1	60	30	10
BiZn-2	55	30	15
BiZn-3	50	30	20
BiZn-4	45	30	25
BiZn-5	40	30	30
BiZn-6	35	30	35
BiZn-7	30	30	40

Fig.2 XRD patterns， CTE curves， DSC curves， and line graph of characteristic temperatures and CTE of different Bi/Zn glasses

Fig.3 Infrared spectra and Raman spectra of different Bi/Zn glasses

Table 2 Infrared absorption bands and vibration types of BiBZn system glass

Wave number/cm^-1	Corresponding vibration
720	Symmetric stretching vibration of Bi—O bond in ［BiO₃］^［19］， bending vibration of O₃B—O—BO₃ in ［BO₃］^［20］
1 150	B—O bond vibration in ［BO₃］^［21-22］
1 300	Asymmetric stretching vibration of O—B—O bond in ［BO₄］ ^［23］

Table 3 Raman spectra bands and vibration types of BiBZn system glass

Wave number/cm^-1	Corresponding vibration
350	Bi—O—Bi bond vibration in ［BiO₆］^［24］
620	B—O—B bond bending vibration in ［BO₃］^［21-22］， Bi—O bond stretching vibration in ［BiO₆］^［25］
1 200~1 320	Bi—O bond vibration in ［BiO₃］^［26］

Fig.4 Variation of flow column morphology with temperature of BiZn-1 to BiZn-7 glass

Fig.5 Variation curves of diameter of BiZn-1 to BiZn-7 glass flow column with temperature and XRD patterns of BiZn-1 to BiZn-7 glass flow column at 450 ℃

Table 4 Glass composition with variations in Bi/Zn components

Sample No.	Mole fraction/%
Sample No.	Bi₂O₃	B₂O₃	ZnO
BZn-1	40.0	30.0	30.0
BZn-2	40.0	32.5	27.5
BZn-3	40.0	35.0	25.0
BZn-4	40.0	37.5	22.5
BZn-5	40.0	40.0	20.0

Fig.6 XRD patterns， CTE curves， DSC curves， line graph of characteristic temperatures and CTE of different B/Zn glasses

Fig.7 Infrared spectra and Raman spectra of different B/Zn glasses

Fig.8 Variation of flow column morphology with temperature of BZn-1 to BZn-5 glass

Fig.9 Variation curves of diameter of BZn-1 to BZn-5 glass flow column with temperature and XRD patterns of BZn-1 to BZn-5 glass flow column at 450 ℃

Table 5 Laser parameters

Laser parameter	Value
Laser power/W	200
Maximum pulse energy/MJ	1.5
Adjustable frequency range/kHz	1~4 000
Central wavelength/nm	1 064
Power regulation range/%	10~100
Beam diameter/mm	7
Focal diameter/mm	0.05

Table 6 Sealing strength at different laster pulse widths

Sample No.	Pulse width/ns	Power/W	Sealing strength/MPa
A3-1	20	28	0.92
A3-2	20	32	1.58
A3-3	20	36	3.67
A3-4	20	40	2.31
A3-5	60	36	2.03
A3-6	60	40	1.88
A3-7	60	44	2.36
A3-8	60	48	1.31
A3-9	100	40	1.32
A3-10	100	44	1.20
A3-11	100	48	1.54
A3-12	100	52	2.52
A3-13	100	56	1.30

Fig.10 Sealing strength at different laster pulse

Fig.11 XRD patterns of sealing layers at different laster widths under 40 W power pulse widths under 40 W power

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