Research Progress on Sintering Densification Technology of h-BN Ceramics

doi:10.16552/j.cnki.issn1001-1625.2024.1042

Abstract

Abstract: Hexagonal boron nitride (h-BN) ceramics, as a type of high-performance structural-functional integrated composite ceramics material, have broad application prospects in aerospace, aviation, microelectronics, metallurgy, and other fields. However, due to the special layered structure and interlayer covalent bonds of h-BN, there are challenges in achieving density during the sintering process. In order to promote the densification of h-BN ceramics sintering and enhance their various properties, researchers have proposed new strategies based on traditional sintering techniques such as pressureless sintering (PLS), hot pressing sintering (HPS), spark plasma sintering (SPS), and reactive sintering (RS). Additionally, they have developed various new sintering technologies, including cold sintering (CSP), oscillating pressure sintering (OPS), and cross-linking pressureless bonding. This review comprehensively summarizes the recent advances in h-BN ceramics densification technology from the perspectives of both traditional and new sintering techniques. By comparing various traditional and new sintering technologies and combining them with typical applications of h-BN ceramics, it elucidates the development directions and application prospects of existing sintering technologies, aiming to provide references for the development and application of sintering densification technology for h-BN ceramics.

Key words: h-BN ceramics, sintering technology, densification, traditional sintering technology, new sintering technology

CLC Number:

TQ174.75

CHEN Yujie, LI Junsheng, LI Chenxiao, CHEN Yurong, WAN Fan. Research Progress on Sintering Densification Technology of h-BN Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2025, 44(2): 651-665.

References

[1] STEHLE Y, MEYER H M III, UNOCIC R R, et al. Synthesis of hexagonal boron nitride monolayer: control of nucleation and crystal morphology[J]. Chemistry of Materials, 2015, 27(23): 8041-8047.
[2] PEREVISLOV S N. Structure, properties, and applications of graphite-like hexagonal boron nitride[J]. Refractories and Industrial Ceramics, 2019, 60(3): 291-295.
[3] ZHANG Z W, HU S Q, CHEN J, et al. Hexagonal boron nitride: a promising substrate for graphene with high heat dissipation[J]. Nanotechnology, 2017, 28(22): 225704.
[4] JIANG P Q, QIAN X, YANG R G, et al. Anisotropic thermal transport in bulk hexagonal boron nitride[J]. Physical Review Materials, 2018, 2(6): 064005.
[5] CAO C C, YANG J W, YANG S B, et al. Pressureless welding of temperature-invariant multifunctionality body based on hydroxyl-functionalized boron nitride nanosheets and bifunctional monoethanolamine cross-linker[J]. Small, 2024, 20(38): e2401387.
[6] DUAN X M, WANG M R, JIA D C, et al. Anisotropic mechanical properties and fracture mechanisms of textured h-BN composite ceramics[J]. Materials Science and Engineering: A, 2014, 607: 38-43.
[7] GAO X J, YAN D M, CAO J W, et al. The study on the property and the microstructure of pressureless sintered h-BN ceramics[J]. Advanced Materials Research, 2015, 1104: 9-14.
[8] 雷玉成, 包旭东, 刘军, 等. 六方氮化硼无压烧结研究[J]. 兵器材料科学与工程, 2005, 28(4): 20-23.
LEI Y C, BAO X D, LIU J, et al. Research on pressureless sintering of hexagonal boron nitride[J]. Ordnance Material Science and Engineering, 2005, 28(4): 20-23 (in Chinese).
[9] HAGIO T, KOBAYASHI K, YOSHIDA H, et al. Sintering of the mechanochemically activated powders of hexagonal boron nitride[J]. Journal of the American Ceramic Society, 1989, 72(8): 1482-1484.
[10] WANG T B, JIN C C, YANG J, et al. Physical and mechanical properties of hexagonal boron nitride ceramic fabricated by pressureless sintering without additive[J]. Advances in Applied Ceramics, 2015, 114(5): 273-276.
[11] 王太保, 陆聪, 刘涛, 等. 浸渍-裂解工艺对无压烧结制备六方氮化硼陶瓷性能的影响[J]. 人工晶体学报, 2016, 45(3): 718-724+742.
WANG T B, LU C, LIU T, et al. Effect of impregnation-pyrolysis process on the properties of pressureless sintered hexagonal boron nitride ceramics[J]. Journal of Synthetic Crystals, 2016, 45(3): 718-724+742 (in Chinese).
[12] 王会媛. 3D打印制备h-BN-MAS复合陶瓷[D]. 哈尔滨: 哈尔滨工业大学, 2018: 10-19.
WANG H Y. Preparation of h-BN-MAS composite ceramics by 3D printing[D]. Harbin: Harbin Institute of Technology, 2018: 10-19 (in Chinese).
[13] ZHANG X, CHEN J X, LI X C, et al. Microstructure and mechanical properties of h-BN/Y₂SiO₅ composites[J]. Ceramics International, 2015, 41(1): 1279-1283.
[14] TIAN Z, LU J N, FENG X W, et al. Effects of cross-scale h-BN grains and orientation degree on the mechanical and thermal properties of BN-matrix textured ceramics[J]. Ceramics International, 2023, 49(8): 12481-12490.
[15] DENG Y C, WU S L, JIANG Y J, et al. Study on viscosity of the La₂O₃-SiO₂-Al₂O₃ slag system[J]. Metallurgical and Materials Transactions B, 2016, 47(4): 2433-2439.
[16] IFTEKHAR S, GRINS J, EDÉN M. Composition-property relationships of the La₂O₃-Al₂O₃-SiO₂ glass system[J]. Journal of Non-Crystalline Solids, 2010, 356(20/21/22): 1043-1048.
[17] NIU B, CAI D L, YANG Z H, et al. Anisotropies in structure and properties of hot-press sintered h-BN-MAS composite ceramics: effects of raw h-BN particle size[J]. Journal of the European Ceramic Society, 2019, 39(2/3): 539-546.
[18] QIU B F, DUAN X M, ZHANG Z, et al. Microstructural evolution and mechanical properties of h-BN composite ceramics with Y₂O₃-AlN addition by liquid-phase sintering[J]. Rare Metals, 2020, 39(5): 555-561.
[19] TIAN Z, WANG Y, ZHANG Z, et al. Preparation of highly oriented h-BN based textured ceramics via grain rearrangement under DLP printing and low-pressure sintering[J]. Materials Letters, 2020, 268: 127584.
[20] 邹春荣, 沈同圣, 郭少军, 等. 一种氮化硅纳米纤维增强氮化硼陶瓷及其制备方法: CN110330349B[P]. 2020-10-30.
ZOU C R, SHENG T S, GUO S J, et al. A preparation method of silicon nitride nanofiber reinforced boron nitride ceramics: CN110330349B[P]. 2020-10-30 (in Chinese).
[21] FAZEN P J, REMSEN E E, BECK J S, et al. Synthesis, properties, and ceramic conversion reactions of polyborazylene. A high-yield polymeric precursor to boron nitride[J]. Chemistry of Materials, 1995, 7(10): 1942-1956.
[22] ESLAMI-SHAHED H, NEKOUEE K, EHSANI N. The effects of adding CNTs and GNPs on the microstructure and mechanical properties of hexagonal-boron nitride[J]. Ceramics International, 2020, 46(14): 22005-22014.
[23] XUE J X, LIU J X, XIE B H, et al. Pressure-induced preferential grain growth, texture development and anisotropic properties of hot pressed hexagonal boron nitride ceramics[J]. Scripta Materialia, 2011, 65(11): 966-969.
[24] QIU B F, DUAN X M, ZHANG Z, et al. Microstructure and room/elevated-temperature mechanical properties of hot-pressed h-BN composite ceramics with La₂O₃-Al₂O₃-SiO₂ addition[J]. Journal of the European Ceramic Society, 2020, 40(6): 2260-2267.
[25] QIU B F, DUAN X M, ZHANG Z, et al. Microstructural evolution of h-BN matrix composite ceramics with La-Al-Si-O glass phase during hot-pressed sintering[J]. Journal of Advanced Ceramics, 2021, 10(3): 493-501.
[26] ERTUG B, BOYRAZ T, ADDEMIR O. Microstructural aspects of the hot-pressed hexagonal boron nitride ceramics with limited content of boron oxide[J]. Materials Science Forum, 2007, 554: 197-200.
[27] 翟凤瑞, 单科, 李楠, 等. 氮化硼陶瓷的低温热压烧结及其性能研究[J]. 陶瓷学报, 2019, 40(4): 464-468.
ZHAI F R, SHAN K, LI N, et al. Study on properties of boron nitride ceramics prepared by low temperature hot-pressing sintering[J]. Journal of Ceramics, 2019, 40(4): 464-468 (in Chinese).
[28] NIU B, YANG Z H, CAI D L, et al. MAS-content dependence of the texture and fracture behavior of h-BN-MAS composite ceramics[J]. Ceramics International, 2019, 45(15): 18536-18542.
[29] WANG H Y, CAI D L, YANG Z H, et al. Influence of sintering temperature on the crystallization and mechanical properties of BN-MAS composites[J]. Journal of the American Ceramic Society, 2022, 105(5): 3590-3600.
[30] NIU B, CAI D L, YANG Z H, et al. Effects of sintering temperature on the microstructure and properties of h-BN ceramics with MAS as liquid sintering aid[J]. Ceramics International, 2020, 46(1): 1076-1082.
[31] LIAO N, NIU B, QIU B F, et al. Enhanced thermal shock resistance of BN-based composites sintered by hot-pressing with the introduction of nano oxides[J]. Materials Science and Engineering: A, 2019, 767: 138443.
[32] ZHANG Z, DUAN X M, QIU B F, et al. Anisotropic properties of textured h-BN matrix ceramics prepared using 3Y₂O₃-5Al₂O₃(-4MgO) as sintering additives[J]. Journal of the European Ceramic Society, 2019, 39(5): 1788-1795.
[33] GUILLON O, GONZALEZ-JULIAN J, DARGATZ B, et al. Field-assisted sintering technology/spark plasma sintering: mechanisms, materials, and technology developments[J]. Advanced Engineering Materials, 2014, 16(7): 830-849.
[34] HU J, SHEN Z. Grain growth by multiple ordered coalescence of nanocrystals during spark plasma sintering of SrTiO₃ nanopowders[J]. Acta Materialia, 2012, 60(18): 6405-6412.
[35] SHEN Z J, JOHNSSON M, ZHAO Z, et al. Spark plasma sintering of alumina[J]. Journal of the American Ceramic Society, 2002, 85(8): 1921-1927.
[36] CHEN J J, CHENG J, ZHU S Y, et al. Tribological behavior under 1 200 ℃ elevated temperature of spark plasma sintered h-BN bulk[J]. Tribology International, 2024, 193: 109420.
[37] ZHAI F R, LI S, SUN J L, et al. Microstructure, mechanical properties and thermal shock behavior of h-BN-SiC ceramic composites prepared by spark plasma sintering[J]. Ceramics International, 2017, 43(2): 2413-2417.
[38] 翟凤瑞, 单科, 卢敏, 等. 六方氮化硼陶瓷的烧结及其结构与性能[J]. 硅酸盐学报, 2018, 46(6): 807-812.
ZHAI F R, SHAN K, LU M, et al. Structure and properties of hexagonal boron nitride ceramics by different sintering methods[J]. Journal of the Chinese Ceramic Society, 2018, 46(6): 807-812 (in Chinese).
[39] ZHAI F R, LU M, SHAN K, et al. Spark plasma sintering and characterization of mixed h-BN powders with different grain sizes[J]. Solid State Phenomena, 2018, 281: 414-419.
[40] YILMAZ Z, AY N. The investigation of synthesis and textured properties of in situ formed h-BN with spark plasma sintering[J]. Materials Chemistry and Physics, 2024, 316: 129043.
[41] YANG H T, FANG H L, YU H, et al. Low temperature self-densification of high strength bulk hexagonal boron nitride[J]. Nature Communications, 2019, 10(1): 854.
[42] 段小明, 杨治华, 王玉金, 等. 六方氮化硼(h-BN)基复合陶瓷研究与应用的最新进展[J]. 中国材料进展, 2015, 34(10): 770-782.
DUAN X M, YANG Z H, WANG Y J, et al. Research and application progress of hexagonal boron nitride (h-BN) based composite ceramics[J]. Materials China, 2015, 34(10): 770-782 (in Chinese).
[43] GAO X J, ZHANG C, MAN P, et al. Reaction mechanism and microstructure evolution of reaction sintered h-BN[J]. Journal of Wuhan University of Technology-Mater Sci Ed, 2017, 32(2): 345-348.
[44] GAO X J, ZHANG C, LI Z P, et al. Fabrications, microstructure and mechanical behaviors of h-BN matrix ceramic[J]. Optoelectronics and Advanced Materials-Rapid Communications, 2015, 9(7): 969-973.
[45] 高晓菊, 史超, 李蕾蕾, 等. h-BN陶瓷的制备与抗冲击性能研究[J]. 陶瓷学报, 2020, 41(4): 520-524.
GAO X J, SHI C, LI L L, et al. Study on the fabrication and impact resistance of reaction sintering h-BN ceramic[J]. Journal of Ceramics, 2020, 41(4): 520-524 (in Chinese).
[46] LIU K, WANG J, WU T, et al. Effects of carbon content on microstructure and mechanical properties of SiC ceramics fabricated by SLS/RMI composite process[J]. Ceramics International, 2020, 46(14): 22015-22023.
[47] 谢志鹏. 结构陶瓷[M]. 北京: 清华大学出版社, 2011.
XIE Z. Structural ceramics[M]. Beijing: Tsinghua University Press, 2011 (in Chinese).
[48] XIE Z P, LI S, AN L N. A novel oscillatory pressure-assisted hot pressing for preparation of high-performance ceramics[J]. Journal of the American Ceramic Society, 2014, 97(4): 1012-1015.
[49] HAN Y, LI S, ZHU T B, et al. An oscillatory pressure sintering of zirconia powder: rapid densification with limited grain growth[J]. Journal of the American Ceramic Society, 2017, 100(7): 2774-2780.
[50] 李双, 谢志鹏. 振荡压力烧结法制备高致密度细晶粒氧化锆陶瓷[J]. 无机材料学报, 2016, 31(2): 207-212.
LI S, XIE Z P. Preparation of zirconia ceramics with high density and fine grains by oscillatory pressure sintering[J]. Journal of Inorganic Materials, 2016, 31(2): 207-212 (in Chinese).
[51] 韩耀. 高性能结构陶瓷的振荡压力烧结与机理研究[D]. 北京: 清华大学, 2018: 95-103.
HAN Y. Oscillating pressure sintering and mechanism research of high performance structural ceramics[D]. Beijing: Tsinghua University, 2018: 95-103 (in Chinese).
[52] HAN Y, LI S, ZHU T B, et al. An oscillatory pressure sintering of zirconia powder: densification trajectories and mechanical properties[J]. Journal of the American Ceramic Society, 2018, 101(5): 1824-1829.
[53] 韩耀, 谢志鹏, 李海燕, 等. 新型振荡压力烧结工艺对高性能氮化硼陶瓷微观结构和性能的影响[J]. 硅酸盐学报, 2021, 49(12): 2549-2555.
HAN Y, XIE Z P, LI H Y, et al. Effect of oscillatory pressure sintering process on microstructure and properties of boron nitride ceramics with high performance[J]. Journal of the Chinese Ceramic Society, 2021, 49(12): 2549-2555 (in Chinese).
[54] CANNON R M, CARTER W C. Interplay of sintering microstructures, driving forces, and mass transport mechanisms[J]. Journal of the American Ceramic Society, 1989, 72(8): 1550-1555.
[55] ROLLETT A D, SROLOVITZ D J, ANDERSON M P. Simulation and theory of abnormal grain growth: anisotropic grain boundary energies and mobilities[J]. Acta Metallurgica, 1989, 37(4): 1227-1240.
[56] JIANG R, SHI Z Y, ZHAO W, et al. Vacancy-assisted growth mechanism of multilayer hexagonal boron nitride on a Fe₂B substrate[J]. The Journal of Physical Chemistry Letters, 2020, 11(20): 8511-8517.
[57] CAO C C, YANG J W, YANG S B, et al. Pressureless consolidation of boron nitride fiber ceramics via a chemical bonding approach[J]. Journal of the European Ceramic Society, 2023, 43(12): 5223-5230.
[58] GUO J, GUO H Z, BAKER A L, et al. Cold sintering: a paradigm shift for processing and integration of ceramics[J]. Angewandte Chemie (International Edition), 2016, 55(38): 11457-11461.
[59] SENGUL M Y, GUO J, RANDALL C A, et al. Water-mediated surface diffusion mechanism enables the cold sintering process: a combined computational and experimental study[J]. Angewandte Chemie (International Edition), 2019, 58(36): 12420-12424.
[60] MARIA J P, KANG X Y, FLOYD R D, et al. Cold sintering: current status and prospects[J]. Journal of Materials Research, 2017, 32(17): 3205-3218.
[61] GUO H Z, BAKER A, GUO J, et al. Cold sintering process: a novel technique for low-temperature ceramic processing of ferroelectrics[J]. Journal of the American Ceramic Society, 2016, 99(11): 3489-3507.
[62] GUO H Z, BAYER T J M, GUO J, et al. Cold sintering process for 8%Y₂O₃-stabilized ZrO₂ ceramics[J]. Journal of the European Ceramic Society, 2017, 37(5): 2303-2308.
[63] KÄHÄRI H, TEIRIKANGAS M, JUUTI J, et al. Improvements and modifications to room-temperature fabrication method for dielectric Li₂MoO₄ ceramics[J]. Journal of the American Ceramic Society, 2015, 98(3): 687-689.
[64] GUO J, GUO H Z, HEIDARY D S B, et al. Semiconducting properties of cold sintered V₂O₅ ceramics and co-sintered V₂O₅-PEDOT: pss composites[J]. Journal of the European Ceramic Society, 2017, 37(4): 1529-1534.
[65] BAKER A, GUO H Z, GUO J, et al. Utilizing the cold sintering process for flexible-printable electroceramic device fabrication[J]. Journal of the American Ceramic Society, 2016, 99(10): 3202-3204.
[66] GUO H Z, GUO J, BAKER A, et al. Cold sintering process for ZrO₂-based ceramics: significantly enhanced densification evolution in yttria-doped ZrO₂[J]. Journal of the American Ceramic Society, 2017, 100(2): 491-495.
[67] FUNAHASHI S, GUO J, GUO H Z, et al. Demonstration of the cold sintering process study for the densification and grain growth of ZnO ceramics[J]. Journal of the American Ceramic Society, 2017, 100(2): 546-553.
[68] ZHU J Y, LI F, HOU Y Z, et al. Near-room-temperature water-mediated densification of bulk van der Waals materials from their nanosheets[J]. Nature Materials, 2024, 23(5): 604-611.