Article(id=1320098189642945536, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320098188355285873, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230957, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1701964800000, receivedDateStr=2023-12-08, revisedDate=1704643200000, revisedDateStr=2024-01-08, acceptedDate=null, acceptedDateStr=null, onlineDate=1792665534649, onlineDateStr=2026-10-22, pubDate=1726761600000, pubDateStr=2024-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792665534649, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792665534649, creator=13701087609, updateTime=1792665534649, updator=13701087609, issue=Issue{id=1320098188355285873, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='9', pageStart='2755', pageEnd='3090', issueExtLink='null', onlineDate='null', pubDate='1726761600000', pubDateStr='2024-09-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792665534341, creator='13701087609', updateTime=1792666312798, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320101453507711442, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320098188355285873, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320101453507711443, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320098188355285873, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=2934, endPage=2941, ext={EN=ArticleExt(id=1320098189844271104, articleId=1320098189642945536, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=High Strength and High Thermal Conductivity Si3N4 Ceramics Prepared by Spark Plasma Sintering Combined with High Temperature Heat Treatment, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

Silicon nitride (Si3N4) ceramics are considered to be one of the most promising ceramic substrate materials due to their good insulation, low coefficient of thermal expansion and high mechanical properties. However, the thermal conductivity of Si3N4 ceramics prepared by conventional methods is low (< 50 W·m-1·K-1), which greatly affects the reliability of chips and even causes the failure of electronic devices. New methods such as gas pressure sintering (GPS), and sintered reaction-bonded silicon nitride (SRBSN) have been employed to fabricate Si3N4 ceramics with high thermal conductivity and high bending strength. Nevertheless, the sintering temperature of both GPS and SRBSN is high and the holding time is too long, which lead to the high cost and limit its applications. Spark plasma sintering (SPS) can produce ceramics with high density in a relatively short time, while the short soaking time is not suitable to improve the thermal conductivity. High-temperature heat treatment can promote the growth of Si3N4 grains, and thus improves the thermal conductivity of Si3N4 ceramics. Therefore, it is expected that Si3N4 ceramics with high bending strength and high thermal conductivity can be prepared at a lower temperature and a shorter time by the combination of SPS and high-temperature heat treatment processes.

Methods

Si3N4 ceramics were prepared by SPS at 1 400, 1 500, 1 600 ℃ and 1 700 ℃ for 5 min using α-Si3N4, Y2O3 and MgSiN2 as raw materials. The obtained samples with the best overall properties were then selected and put into a gas pressure furnace to be heated at different temperatures (1 600, 1 700 ℃, and 1 800 ℃) for 3 h. Density and open porosity of the sintered samples were tested by Archimedes method. The phase composition of samples was analyzed by X-ray diffractometer (XRD). Samples were polished and then etched in molten NaOH at 500 ℃ for 20 s to observe the microstructures using a field emission scanning electron microscope (FESEM). The diameters of at least 200 grains in the SEM images were measured by Nano measure software and statistically analyzed to obtain the average grain size. The bending strength was examined via three-point bending test using an electronic universal testing machine. The thermal diffusion coefficient of Si3N4 ceramics was determined by a laser thermal conductivity analyzer.

Results and discussion

As the sintering temperature increased from 1400 ℃ to 1 700 ℃, the relative density of samples increased rapidly from 80.43% to 97.81% at first and then slowly to 99.09%. With the increase of sintering temperature, the viscosity of liquid phase produced by the reaction of sintering additives gradually reduced, and the rate of material transport improved during sintering process, which led to a higher densification. When sintering temperature reached to 1 600 ℃, the content of β-Si3N4 in sample reached 100%, indicating that the phase transition from α-Si3N4 to β-Si3N4 has been completed. The average grain size of samples gradually grew from 0.31 μm to 1.35 μm with the increase of sintering temperature from 1 400 ℃ to 1 700 ℃, and the thermal conductivity of the samples rapidly increased from 9.88 W·m-1·K-1 to 61.80 W·m-1·K-1, being attributed to the phase transition of α→β-Si3N4. Besides, the process of phase transition could purify the crystal lattice, while the increase of densification and grain growth reduced the scattering of phonons by defects such as pores, grain boundaries, and so on. Therefore, the thermal conductivity of the Si3N4 ceramics was improved.

After the heat treatment of sample sintered by SPS at 1 600 ℃, the relative density reduced in a certain degree compared with that of the untreated samples. The average grain size of β-Si3N4 in samples before heat treatment was 1.16 μm, and grows to 1.33 μm after heat treatment at 1 600 ℃. Rising the heat treatment temperature to 1 700 ℃ and 1 800 ℃, the average grain size of the samples grew to 1.35 μm and 1.51 μm, respectively. when heat treatment temperatures increased from 1 600 ℃ to 1 800 ℃, the thermal conductivity of the samples rosed from 50.87 W·m-1·K-1 to 57.36 W·m-1·K-1, 0.45% and 13.27% higher than that of the un-treated samples. Bending strength of samples decreased with the increase of heat treatment temperature. When heat treated at 1 800 ℃, the bending strength of sample reduced to 743 MPa. which still meet the requirement of bending strength >700 MPa for Si3N4 ceramic substrates.

Conclusions

The relative density, thermal conductivity, and β-Si3N4 content of the Si3N4 ceramics increases with the increase of SPS temperature. When SPS temperature was 1 600 ℃, the bulk sample was composed of β-Si3N4 with a high relative density of 98.78% and a thermal conductivity of 50.64 W·m-1·K-1. After heat treated at the same temperature, the thermal conductivity of the samples was improved, while the bending strength displayed the opposite trend. The thermal conductivity of samples heat-treated at 1 800 ℃ achieved 13.27% higher than that of the untreated sample, while the bending strength still exceed 700 MPa. Therefore, the combination of SPS and high-temperature heat treatment is a promising process to produce Si3N4 ceramics with high thermal conductivity and bending strength.

, authors=Tao LI, Bo ZHANG, Zhilei WEI, Kang DENG, Zhongqi SHI, authorsList=Tao LI, Bo ZHANG, Zhilei WEI, Kang DENG, Zhongqi SHI, authorCompany=null, correspAuthors=Zhongqi SHI, authorNote=

LI Tao (1998-), male, Master candidate. E-mail:

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SHI Zhongqi (1982-), male, Ph.D, Professor E-mail:
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采用放电等离子体烧结(SPS)结合高温热处理工艺,以α-Si3N4为主要原料、MgSiN2和Y2O3为复合烧结助剂制备出兼具高强度和高导热性能的Si3N4陶瓷,研究了SPS温度对Si3N4陶瓷致密化过程和热导率的影响,并分析了高温热处理温度对Si3N4陶瓷微观结构和性能的影响。结果表明,Si3N4陶瓷的致密度和热导率随着SPS温度的升高而提高,在1600 ℃保温5 min即可制备出致密度约为99%的Si3N4陶瓷样品。对其进行高温热处理发现,样品的热导率随着热处理温度的升高而提高,抗弯强度则与之相反。经1800 ℃热处理的样品,热导率为57.36 W·m-1·K-1,相较未经热处理的样品提升了13.27%,同时抗弯强度仍保持在743 MPa的较高水平。

, authors=李涛, 张博, 魏智磊, 邓康, 史忠旗, authorsList=李涛, 张博, 魏智磊, 邓康, 史忠旗, authorCompany=null, correspAuthors=史忠旗, authorNote=

李涛(1998—),男,硕士研究生。

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史忠旗(1982—),男,博士,教授。
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放电等离子体烧结结合高温热处理制备高强高导热氮化硅陶瓷
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李涛 , 张博 , 魏智磊 , 邓康 , 史忠旗
硅酸盐学报 | 研究论文 2024,52(9): 2934-2941
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硅酸盐学报 |研究论文 2024 , 52 (9) : 2934 -2941
放电等离子体烧结结合高温热处理制备高强高导热氮化硅陶瓷
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李涛 , 张博, 魏智磊, 邓康, 史忠旗
作者信息
  • 西安交通大学材料科学与工程学院,金属材料强度国家重点实验室,西安 710049
通讯作者:
史忠旗(1982—),男,博士,教授。
作者简介:

李涛(1998—),男,硕士研究生。

High Strength and High Thermal Conductivity Si3N4 Ceramics Prepared by Spark Plasma Sintering Combined with High Temperature Heat Treatment
Tao LI , Bo ZHANG, Zhilei WEI, Kang DENG, Zhongqi SHI
Affiliations
  • State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, China
  • Corresponding Author:
    SHI Zhongqi (1982-), male, Ph.D, Professor E-mail:

    LI Tao (1998-), male, Master candidate. E-mail:

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20230957
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采用放电等离子体烧结(SPS)结合高温热处理工艺,以α-Si3N4为主要原料、MgSiN2和Y2O3为复合烧结助剂制备出兼具高强度和高导热性能的Si3N4陶瓷,研究了SPS温度对Si3N4陶瓷致密化过程和热导率的影响,并分析了高温热处理温度对Si3N4陶瓷微观结构和性能的影响。结果表明,Si3N4陶瓷的致密度和热导率随着SPS温度的升高而提高,在1600 ℃保温5 min即可制备出致密度约为99%的Si3N4陶瓷样品。对其进行高温热处理发现,样品的热导率随着热处理温度的升高而提高,抗弯强度则与之相反。经1800 ℃热处理的样品,热导率为57.36 W·m-1·K-1,相较未经热处理的样品提升了13.27%,同时抗弯强度仍保持在743 MPa的较高水平。

氮化硅  /  放电等离子体烧结  /  高温热处理  /  热导率  /  抗弯强度
Introduction

Silicon nitride (Si3N4) ceramics are considered to be one of the most promising ceramic substrate materials due to their good insulation, low coefficient of thermal expansion and high mechanical properties. However, the thermal conductivity of Si3N4 ceramics prepared by conventional methods is low (< 50 W·m-1·K-1), which greatly affects the reliability of chips and even causes the failure of electronic devices. New methods such as gas pressure sintering (GPS), and sintered reaction-bonded silicon nitride (SRBSN) have been employed to fabricate Si3N4 ceramics with high thermal conductivity and high bending strength. Nevertheless, the sintering temperature of both GPS and SRBSN is high and the holding time is too long, which lead to the high cost and limit its applications. Spark plasma sintering (SPS) can produce ceramics with high density in a relatively short time, while the short soaking time is not suitable to improve the thermal conductivity. High-temperature heat treatment can promote the growth of Si3N4 grains, and thus improves the thermal conductivity of Si3N4 ceramics. Therefore, it is expected that Si3N4 ceramics with high bending strength and high thermal conductivity can be prepared at a lower temperature and a shorter time by the combination of SPS and high-temperature heat treatment processes.

Methods

Si3N4 ceramics were prepared by SPS at 1 400, 1 500, 1 600 ℃ and 1 700 ℃ for 5 min using α-Si3N4, Y2O3 and MgSiN2 as raw materials. The obtained samples with the best overall properties were then selected and put into a gas pressure furnace to be heated at different temperatures (1 600, 1 700 ℃, and 1 800 ℃) for 3 h. Density and open porosity of the sintered samples were tested by Archimedes method. The phase composition of samples was analyzed by X-ray diffractometer (XRD). Samples were polished and then etched in molten NaOH at 500 ℃ for 20 s to observe the microstructures using a field emission scanning electron microscope (FESEM). The diameters of at least 200 grains in the SEM images were measured by Nano measure software and statistically analyzed to obtain the average grain size. The bending strength was examined via three-point bending test using an electronic universal testing machine. The thermal diffusion coefficient of Si3N4 ceramics was determined by a laser thermal conductivity analyzer.

Results and discussion

As the sintering temperature increased from 1400 ℃ to 1 700 ℃, the relative density of samples increased rapidly from 80.43% to 97.81% at first and then slowly to 99.09%. With the increase of sintering temperature, the viscosity of liquid phase produced by the reaction of sintering additives gradually reduced, and the rate of material transport improved during sintering process, which led to a higher densification. When sintering temperature reached to 1 600 ℃, the content of β-Si3N4 in sample reached 100%, indicating that the phase transition from α-Si3N4 to β-Si3N4 has been completed. The average grain size of samples gradually grew from 0.31 μm to 1.35 μm with the increase of sintering temperature from 1 400 ℃ to 1 700 ℃, and the thermal conductivity of the samples rapidly increased from 9.88 W·m-1·K-1 to 61.80 W·m-1·K-1, being attributed to the phase transition of α→β-Si3N4. Besides, the process of phase transition could purify the crystal lattice, while the increase of densification and grain growth reduced the scattering of phonons by defects such as pores, grain boundaries, and so on. Therefore, the thermal conductivity of the Si3N4 ceramics was improved.

After the heat treatment of sample sintered by SPS at 1 600 ℃, the relative density reduced in a certain degree compared with that of the untreated samples. The average grain size of β-Si3N4 in samples before heat treatment was 1.16 μm, and grows to 1.33 μm after heat treatment at 1 600 ℃. Rising the heat treatment temperature to 1 700 ℃ and 1 800 ℃, the average grain size of the samples grew to 1.35 μm and 1.51 μm, respectively. when heat treatment temperatures increased from 1 600 ℃ to 1 800 ℃, the thermal conductivity of the samples rosed from 50.87 W·m-1·K-1 to 57.36 W·m-1·K-1, 0.45% and 13.27% higher than that of the un-treated samples. Bending strength of samples decreased with the increase of heat treatment temperature. When heat treated at 1 800 ℃, the bending strength of sample reduced to 743 MPa. which still meet the requirement of bending strength >700 MPa for Si3N4 ceramic substrates.

Conclusions

The relative density, thermal conductivity, and β-Si3N4 content of the Si3N4 ceramics increases with the increase of SPS temperature. When SPS temperature was 1 600 ℃, the bulk sample was composed of β-Si3N4 with a high relative density of 98.78% and a thermal conductivity of 50.64 W·m-1·K-1. After heat treated at the same temperature, the thermal conductivity of the samples was improved, while the bending strength displayed the opposite trend. The thermal conductivity of samples heat-treated at 1 800 ℃ achieved 13.27% higher than that of the untreated sample, while the bending strength still exceed 700 MPa. Therefore, the combination of SPS and high-temperature heat treatment is a promising process to produce Si3N4 ceramics with high thermal conductivity and bending strength.

silicon nitride  /  spark plasma sintering  /  high temperature heat treatment  /  thermal conductivity  /  bending strength
李涛, 张博, 魏智磊, 邓康, 史忠旗. 放电等离子体烧结结合高温热处理制备高强高导热氮化硅陶瓷. 硅酸盐学报, 2024 , 52 (9) : 2934 -2941 . DOI: 10.14062/j.issn.0454-5648.20230957
Tao LI, Bo ZHANG, Zhilei WEI, Kang DENG, Zhongqi SHI. High Strength and High Thermal Conductivity Si3N4 Ceramics Prepared by Spark Plasma Sintering Combined with High Temperature Heat Treatment[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 2934 -2941 . DOI: 10.14062/j.issn.0454-5648.20230957
  • 国家自然科学基金青年科学基金项目(52302069)
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doi: 10.14062/j.issn.0454-5648.20230957
  • 接收时间:2023-12-08
  • 首发时间:2026-10-22
  • 出版时间:2024-09-20
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  • 收稿日期:2023-12-08
  • 修回日期:2024-01-08
基金
国家自然科学基金青年科学基金项目(52302069)
作者信息
    西安交通大学材料科学与工程学院,金属材料强度国家重点实验室,西安 710049

通讯作者:

史忠旗(1982—),男,博士,教授。
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小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
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