Influence of Particle Size of Glass Powder on Densification Behavior and Properties of CaO-B2O3-La2O3/Al2O3 LTCC Composite Material

doi:10.16552/j.cnki.issn1001-1625.2025.1205

Abstract

Abstract:

Driven by the demands of microwave and high-speed communication applications， low temperature co-fired ceramic（LTCC） technology has attracted significant attention owing to their advantages in device miniaturization and high-frequency integration， where the particle size of glass powder serves as a key factor determining sintering behavior and performance of ceramic substrates. In this study， the CaO-B₂O₃-La₂O₃/Al₂O₃ LTCC composite materials were employed to systematically investigate the influence of particle size of glass powder on sintering densification and comprehensive material performance of sintered substrates. The crystalline phases and microstructures of the sintered substrates were characterized using X-ray diffraction （XRD）， thermomechanical analysis（TMA）， and scanning electron microscope（SEM）， while the dielectric properties across different frequencies were evaluated with a network analyzer. The results indicate that the particle size of glass powder directly affects the densification process and crystallization behavior of the material. When the particle size of glass powder is 1.64 μm and the distribution is concentrated， the green tapes exhibit the lowest surface roughness of 121 nm. The porosity of the sintered substrates is only 5.142%， showing the highest density of 3.129 g/cm³. At the same time， it has a maximum dielectric constant of 6.681（20 GHz） and a lower dielectric loss of 1.058×10^-3（20 GHz）， and the bending strength reaches a maximum of 217.946 MPa.. In contrast， excessively fine particle size of glass powder leads to slurry agglomeration and premature crystallization， causing mismatched densification and grain growth and ultimately deteriorating the final density. This study highlights the key role of particle size of glass powder on sintering behavior and provides a reference for the subsequent design of high-frequency LTCC composite materials.

Key words: particle size of glass powder, composite ceramics, LTCC, sintering densification, dielectric property, sintered substrate

CLC Number:

TQ174

LYU Zibin, CAO Yu, HE Kun, NA Hua, LYU Jinyu, HAI Yun, XU Bo, HAN Bin, WANG Yanhang, ZU Chengkui. Influence of Particle Size of Glass Powder on Densification Behavior and Properties of CaO-B₂O₃-La₂O₃/Al₂O₃ LTCC Composite Material[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(4): 1354-1367.

Figures/Tables 18

Fig.1 Particle size distribution of powder for casting

Table 1 Particle size information of glass powders

Sample	Particle size/μm
Sample	D₀	D₁₀	D₅₀	D₉₀	D₁₀₀
S-1	0.18	0.37	1.31	3.08	16.18
S-2	0.51	0.95	1.64	4.84	12.83
S-3	0.32	0.58	2.01	3.87	10.97
S-4	0.61	1.23	2.37	7.55	15.67
Al₂O₃	0.56	1.02	2.55	4.77	10.14

Fig.2 Viscosity-shear rate curves of casting slurry with different particle sizes of glass powder

Fig.3 Density， weight loss during sintering， and surface roughness of green tapes

Fig.4 Surface microstructure of different green tapes

Fig.5 3D surface microstructure and surface roughness curves of green tapes

Fig.6 Sintering shrinkage curves of green tapes at different heating rates

Fig.7 Relationship between ln［T×d（ΔL/L0）/dT］ and 1/T of green tapes at different heating rates

Fig.8 Sintering activation energy of green tapes

Fig.9 Sintering process of CBL/Al2O3 LTCC composite materials

Fig.10 DSC curves of glass powder

Table 2 Tp at different heating rates

Heating rate/ （℃·min^-1）	S-1		S-2		S-3		S-4
Heating rate/ （℃·min^-1）	T_p1/℃	T_p2/℃	T_p1/℃	T_p2/℃	T_p1/℃	T_p2/℃	T_p1/℃	T_p2/℃
5	737.4	771.2	740.5	773.2	742.7	778.1	745.5	781.6
10	747.9	787.6	750.8	788.4	754.3	795.3	756.6	798.5
15	754.8	801.2	759.2	799.7	761.2	805.7	763.4	807.9
20	761.3	811.5	763.3	809.8	765.7	814.8	768.3	818.1

Fig.11 Crystallization activation energy， viscosity-temperature curve， and characteristic softening temperature of glass samples

Fig.12 BSE image of S-1 sample after sintering at 700 ℃

Fig.13 Sintering system， crystal phase composition， and DSC curves of sintered samples

Fig.14 Cross-section microstructure and porosity of sintered substrates with different glass particle sizes of glass powder

Fig.15 Mechanical and dielectric properties of sintered substrate samples

Table 3 Performance comparison of commercial products， previously reported LTCC materials and S-2 sample prepared in this study

Property	Commercial products^［22］			Reported LTCC materials			This study
Property	Dupont 951	Ferro A6M	Heraeus CT700	李子杰等^［23］	刘明等^［24］	韦鹏飞等^［25］	This study
Sintering temperature/℃	<900	<900	<900	850	875	850	850
Fired density/（g·cm^-3）	3.100	2.500	—	2.940	3.170	3.120	3.129
Permittivity	7.80（3 GHz）	5.90（10 MHz）	7.00（1 kHz）	9.69 （1 MHz）	25.18（7 GHz）	7.98（10 MHz）	6.68（20 GHz）
Dielectric loss	0.006 0（3 GHz）	0.002 0（10 MHz）	0.002 0（1 kHz）	—	0.000 9（7 GHz）	0.001 5（10 GHz）	0.001 1（20 GHz）
Flexural strength/MPa	320	130	240	153	165	—	218

References 25

[1]	李　斌，杨　军，张　波，等. 微波系统级封装的特点研究与应用进展［J］. 空间电子技术， 2025， 22（增刊1）： 100-113.
	LI B， YANG J， ZHANG B， et al. Research and application progresses of microwave system in package［J］. Space Electronic Technology， 2025， 22（supplement 1）： 100-113 （in Chinese）.
[2]	黄　进，蒲芸娜，梁超余. 低温共烧陶瓷的增材制造技术综述［J］. 电子机械工程， 2025， 41（5）： 27-33+53.
	HUANG J， PU Y N， LIANG C Y. A review on additive manufacturing of low temperature co-fired ceramics［J］. Electro-Mechanical Engineering， 2025， 41（5）： 27-33+53 （in Chinese）.
[3]	KEMETHMÜLLER S， HAGYMASI M， STIEGELSCHMITT A， et al. Viscous flow as the driving force for the densification of low-temperature co-fired ceramics［J］. Journal of the American Ceramic Society， 2007， 90（1）： 64-70.
[4]	肖汉宁，李　格. 粉体粒度对K₂O-Al₂O₃-SiO₂系微晶玻璃析晶动力学的影响［J］. 湖南大学学报（自然科学版）， 2018， 45（6）： 85-89.
	XIAO H N， LI G. Effect of particle size on crystallization kinetics of K₂O-Al₂O₃-SiO₂ glass-ceramics［J］. Journal of Hunan University （Natural Sciences）， 2018， 45（6）： 85-89 （in Chinese）.
[5]	WANG F L， ZHANG W J， CHEN X Y， et al. Synthesis and characterization of low CTE value La₂O₃-B₂O₃-CaO-P₂O₅ glass/cordierite composites for LTCC application［J］. Ceramics International， 2019， 45（6）： 7203-7209.
[6]	SEO Y J， SHIN D J， CHO Y S. Phase evolution and microwave dielectric properties of lanthanum borate-based low-temperature co-fired ceramics materials［J］. Journal of the American Ceramic Society， 2006， 89（7）： 2352-2355.
[7]	王　胜，郭凯彬，袁超鹏，等. 超细粉体对水泥净浆流变行为影响研究［J］. 硅酸盐通报， 2017， 36（11）： 3625-3629+3635.
	WANG S， GUO K B， YUAN C P， et al. Effect of ultrafine powder on rheological behavior of cement paste［J］. Bulletin of the Chinese Ceramic Society， 2017， 36（11）： 3625-3629+3635 （in Chinese）.
[8]	张　平，穆宁波，李　波. Yb₂O₃掺杂对镁铝硅系微晶玻璃烧结和性能的影响［J］. 电子元件与材料， 2022， 41（10）： 1007-1013.
	ZHANG P， MU N B， LI B. Effects of Yb₂O₃ doping on sintering and properties of MgO-Al₂O₃-SiO₂ glass-ceramics［J］. Electronic Components and Materials， 2022， 41（10）： 1007-1013 （in Chinese）.
[9]	GAN L， HUANG Y J， JIANG J， et al. A novel high-performance Bi-based glass-Al₂O₃ composite system for LTCC applications［J］. Journal of the American Ceramic Society， 2025， 108（12）： e70157.
[10]	KINGERY W D. Densification during sintering in the presence of a liquid phase. I. theory［M］//Sintering Key Papers. Dordrecht： Springer Netherlands， 1990 ： 383-394.
[11]	BIAN J J， YU Q， HE J J. Tape casting and characterization of Li_2.08TiO₃-LiF glass free LTCC for microwave applications［J］. Journal of the European Ceramic Society， 2017， 37（2）： 647-653.
[12]	JEAN J H， CHANG C R. Cofiring kinetics and mechanisms of an Ag-metallized ceramic-filled glass electronic package［J］. Journal of the American Ceramic Society， 1997， 80（12）： 3084-3092.
[13]	路　标，张树人，周晓华，等. 粒度对CaO-B₂O₃-SiO₂系LTCC材料性能的影响［J］. 电子元件与材料， 2010， 29（2）： 34-36.
	LU B， ZHANG S R， ZHOU X H， et al. Effect of particle size distribution on the properties of CaO-B₂O₃-SiO₂ system LTCC material［J］. Electronic Components and Materials， 2010， 29（2）： 34-36 （in Chinese）.
[14]	曹　禹，徐　博，韩　滨，等. La₂O₃-B₂O₃-CaO-P₂O₅玻璃/Al₂O₃复合低温共烧陶瓷材料介电性能优化［J］. 硅酸盐学报， 2025， 53（10）： 2841-2853.
	CAO Y， XU B， HAN B， et al. Optimization of dielectric properties for La₂O₃-B₂O₃-CaO-P₂O₅ glass/Al₂O₃ low-temperature co-fired ceramic composite［J］. Journal of the Chinese Ceramic Society， 2025， 53（10）： 2841-2853 （in Chinese）.
[15]	CHEN Z R， CHEN X Y， ZHANG W J， et al. Sintering behavior and dielectric properties of La₂O₃-B₂O₃-CaO-P₂O₅ glass/Al₂O₃ composites for LTCC applications［J］. Journal of Materials Science： Materials in Electronics， 2020， 31（21）： 18581-18589.
[16]	SEBASTIAN M T， JANTUNEN H. Low loss dielectric materials for LTCC applications： a review［J］. International Materials Reviews， 2008， 53（2）： 57-90.
[17]	CHIANG C C， WANG S F， WANG Y R， et al. Densification and microwave dielectric properties of CaO-B₂O₃-SiO₂ system glass-ceramics［J］. Ceramics International， 2008， 34（3）： 599-604.
[18]	RAYSSI C， KOSSI SEL， DHAHRI J， et al. Frequency and temperature-dependence of dielectric permittivity and electric modulus studies of the solid solution Ca_0.85Er_0.1Ti_1- _x Co₄ _x_/3O₃ （0≤x≤0.1）［J］. RSC Advances， 2018， 8（31）： 17139-17150.
[19]	CHEN X Y， BAI S X， LI M， et al. Synthesis， characterization， and dielectric properties of low loss LaBO₃ ceramics［J］. Journal of the European Ceramic Society， 2013， 33（16）： 3001-3006.
[20]	XIE H D， LI F， CHEN C， et al. Microwave dielectric properties of LaPO₄ ceramics synthesized by a hydrothermal method［J］. Journal of Inorganic Materials， 2015， 30（8）： 882-886.
[21]	YANG H C， ZHANG S R， WEN Q Y， et al. Synthesis of CaAl₂ _x B₂O₄₊₃ _x ： novel microwave dielectric ceramics with low permittivity and low loss［J］. Journal of the European Ceramic Society， 2021， 41（4）： 2596-2601.
[22]	LUO X F， REN L C， HU Y K， et al. Fabrication and performance of dielectric tape based on CaO-B₂O₃-SiO₂ glass/Al₂O₃ for LTCC applications［J］. Ceramics International， 2018， 44（6）： 6354-6361.
[23]	李子杰，何　峰，范云飞，等. CaO含量对CBAS玻璃/Al₂O₃低温共烧陶瓷的影响［J］. 硅酸盐通报， 2022， 41（11）： 3969-3978.
	LI Z J， HE F， FAN Y F， et al. Effect of CaO content on CBAS glass/Al₂O₃ low temperature co-fired ceramic［J］. Bulletin of the Chinese Ceramic Society， 2022， 41（11）： 3969-3978 （in Chinese）.
[24]	刘　明，许晓颖，赵　拓，等. 中介电常数Ca-B-Si-O玻璃/Ca _x Mg_1- _x TiO₃系LTCC材料的低温烧结与介电性能研究［J］. 陶瓷学报， 2025， 46（3）： 539-545.
	LIU M， XU X Y， ZHAO T， et al. Low temperature sintering and dielectric properties of Ca-B-Si-O glass/Ca _x Mg_1- _x TiO₃ LTCC materials with medium dielectric constant［J］. Journal of Ceramics， 2025， 46（3）： 539-545 （in Chinese）.
[25]	韦鹏飞，周洪庆，李国铭. CaO-Al₂O₃-B₂O₃-SiO₂玻璃/Al₂O₃系低温共烧陶瓷流延工艺优化及性能研究［J］. 南京工业大学学报（自然科学版）， 2022， 44（6）： 633-639.
	WEI P F， ZHOU H Q， LI G M. Optimization and properties of CaO-Al₂O₃-B₂O₃-SiO₂ glass/Al₂O₃ low temperature co-fired ceramic tape casting［J］. Journal of Nanjing University of Technology （Natural Science Edition）， 2022， 44（6）： 633-639 （in Chinese）.

Influence of Particle Size of Glass Powder on Densification Behavior and Properties of CaO-B₂O₃-La₂O₃/Al₂O₃ LTCC Composite Material

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 18

References 25

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LIU Hongrui, MA Denghao, CHEN Ke, CHENG Yehong, WANG Honglei, YU Jinshan, ZHOU Xingui. Dielectric Property and Microwave Absorption Performance of Hot-Pressing Sintering SiCN Ceramics [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(4): 1324-1334.
[2]	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.
[3]	HUANG Xuehui, CHEN Wenzhen, DENG Penghui, HU Xiang’ao. Preparation and Properties of Aluminum Titanate-Cordierite Composite Ceramics [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(6): 2241-2249.
[4]	BI Lunan, LI Ling, SONG Tao, WANG Yingying, LYU Jiaqi, LU Xiang, HAN Zhuoqun, WANG Yang. Preparation of High-Performance BaTiO₃ Piezoelectric Ceramics by Stereolithography 3D Printing [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(5): 1764-1771.
[5]	LYU Xuming, ZHANG Yunhan, SHI Guohua, WANG Jiawei, SUN Xiaohong. Thermal Shock Resistance of AlN/YAlO₃ Composite Ceramics [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(2): 659-665.
[6]	CUI Tangyin, WANG Peng, LIU Ruixiang, WANG Hongsheng, CAO Junchang, CHEN Dongjie. Analysis of Influencing Factors on Dielectric Properties of Fused Quartz Ceramics [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(2): 666-672.
[7]	WANG Xin, HAN Bingqiang, MIAO Zheng, CHEN Junfeng, YAN Wen. Effect of MgCl₂·6H₂O Solution on Properties of Periclase-Magnesia Alumina Spinel Refractories [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(2): 719-726.
[8]	HU Kaiwen, WANG Ying, LI Chengzhuo, DENG Tengfei. Preparation of CaO·6Al₂O₃-Al₂O₃ Composite Ceramics by Ferrotitanium Slag Phase Reconstruction [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(11): 4119-4129.
[9]	DING Donghai, WU Xingxing, XIAO Guoqing, GUAN Bowen, JIN Endong. Microwave-Induced Self-Healing Performance of Asphalt Mixtures with Coal Gasification Slag [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(11): 4185-4194.
[10]	ZHANG Jie, CHEN Qiao, LIU Jia, LI Luyao, WANG Jing, HAN Jianjun. Effect of CuO on Crystallization Behavior and Microwave Dielectric Properties of Cordierite Glass-Ceramics [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(10): 3843-3851.
[11]	LI Wei, GAI Xuezhou, WANG Yuequn. Large Strain Piezoelectric Ceramics for Engineering Applications Prepared by Solid-State Synthesis Method [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(7): 2597-2602.
[12]	WANG Xing, ZOU Helin. Influences of In-Situ Annealing and Deposition Temperature of Bottom Electrodes on Properties of PZT Films [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(2): 743-750.
[13]	ZHAN Lingli, JIA Han, ZHANG Xiaofeng, LI Hong, XIE Jun, XIONG Dehua. Preparation and Properties of MgO-Al₂O₃-SiO₂ Glass-Ceramics with Different Al₂O₃/SiO₂ Ratios [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(12): 4490-4500.
[14]	LIN Congyi, TAO Honglei, LI Wei. Low Temperature Sintering and Microwave Dielectric Properties of MnO₂-CuO-TiO₂ Co-Doped Al₂O₃ Ceramics [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(10): 3764-3768.
[15]	YING Xiaoyun, LIU Jun, QIAO Wenhao, ZHOU Ming, LUO Ying. Cold Sintering Preparation and Dielectric Properties of 0-3 Type Barium Strontium Titanate/Polytetrafluoroethylene Composites [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(7): 2574-2583.