Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering

doi:10.15541/jim20230588

Abstract

Abstract:

Boron carbide possesses excellent properties and has a wide range of applications, but its production cost is relatively high. To address this issue, boron carbide-C composite powder was directly used, synthesized by carbothermal reduction method, as the raw material without any crushing and purification. Boron carbide composites were prepared through silicon infiltration reaction sintering, yielding material properties comparable to those prepared from commercially available boron carbide powder, which effectively reduced its preparation cost. This study mainly investigated the influence of the molar ratio of carbon to boron in the synthesis of powder on the phase composition, microstructure and properties of boron carbide ceramic composite materials, and explored the toughening mechanism of boron carbide ceramic composites. With the increase of the molar ratio of carbon to boron, the atomic ratio of carbon to boron in the synthesized boron carbide powder increases, as well as the content of free C, which coats the surface of the boron carbide particles at the molar ratio of 2.01. The phase composition of the boron carbide composite materials is B₁₂(C,Si,B)₃, SiC and Si. With the increase of carbon-boron molar ratio, the content of boron carbide and free Si in the composite decrease, while the content of SiC, the size of large SiC region, and the number of large SiC regions and SiC nanoparticles increase. Formation of large SiC regions decreases the strength and toughness of the material, while creation of SiC nanoparticles contributes to improvement of strength and toughness. When the carbon to boron molar ratio is 1.35, the composite exhibits the highest flexural strength and fracture toughness, reaching 338 MPa and 4.06 MPa∙m^1/2, respectively.

Key words: boron carbide, carbothermal reduction method, silicon infiltration reaction sintering, molar ratio of carbon to boron, microstructure

CLC Number:

TQ174

ZHENG Yawen, ZHANG Cuiping, ZHANG Ruijie, XIA Qian, RU Hongqiang. Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering[J]. Journal of Inorganic Materials, 2024, 39(6): 707-714.

Figures/Tables 9

Fig. 1 XRD patterns of synthesized powders under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

Fig. 2 SEM secondary electron images of synthesized powders under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

Fig. 3 XRD patterns of B4C composite materials prepared under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

Fig. 4 SEM backscatter images of B4C composite materials prepared under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

Table 1 Volume fraction of B4C composite materials and phase size of SiC under different nC/nB conditions

n_C/n_B	Volume fraction/%			D_mean/μm
n_C/n_B	B₁₂(B,C,Si)₃	SiC	Si	SiC
1.35	57.21	19.47	23.32	5.32
1.75	56.71	24.68	18.61	5.59
1.93	52.57	36.24	11.18	6.18
2.01	51.98	38.07	9.95	5.99

Fig. 5 SEM secondary electron images of B4C composite materials prepared under different nC/nB conditions (a) nC/nB=1.35; (b) nC/nB=1.75; (c) nC/nB=1.93; (d) nC/nB=2.01

Fig. 6 Volume density and open porosity of B4C composite materials under different nC/nB conditions

Fig. 7 Mechanical properties of boron carbide composite materials under different nC/nB conditions (a) Vickers hardness; (b) Bending strength; (c) Fracture toughness

Fig. 8 Indentation crack propagation images of boron carbide composite material obtained at nC/nB=2.01 (a, b) Crack deflection; (c) Particle pullout

References 26

[1]	SONG Q, ZHANG Z H, HU Z Y, et al. Microstructure and mechanical properties of super-hard B₄C ceramic fabricated by spark plasma sintering with (Ti₃SiC₂+Si) as sintering aid. Ceramics International, 2019, 45(7):8790.
[2]	SONG S, BAO C, WANG B. Effect of the addition of carbon fibres on the microstructure and mechanical properties of reaction bonded B₄C/SiC composites. Journal of the European Ceramic Society, 2016, 36(8): 1905.
[3]	MOSHTAGHIOUN B M, CUMBRERA-HERNÁNDEZ F L, GÓMEZ-GARCÍA D, et al. Effect of spark plasma sintering parameters on microstructure and room-temperature hardness and toughness of fine-grained boron carbide (B₄C). Journal of the European Ceramic Society, 2013, 33(2):361.
[4]	ZHAO X, ZOU J, JI W, et al. Processing and mechanical properties of B₄C-SiC_w ceramics densified by spark plasma sintering. Journal of the European Ceramic Society, 2022, 42(5): 2004.
[5]	WANG S, GAO S, XING P, et al. Pressureless liquid-phase sintering of B₄C with MoSi₂ as a sintering aid. Ceramics International, 2019, 45(10):13502.
[6]	BARICK P, JANA D C, THIYAGARAJAN N. Effect of particle size on the mechanical properties of reaction bonded boron carbide ceramics. Ceramics International, 2013, 39(1):763.
[7]	SURI A K, SUBRAMANIAN C, SONBER J K, et al. Synthesis and consolidation of boron carbide: a review. International Materials Reviews, 2013, 55(1):4.
[8]	FOROUGHI P, CHENG Z. Understanding the morphological variation in the formation of B₄C via carbothermal reduction reaction. Ceramics International, 2016, 42(14):15189.
[9]	AHMED Y M Z, EL-SHEIKH S M, EWAIS E M M, et al. Controlling the morphology and oxidation resistance of boron carbide synthesized via carbothermic reduction reaction. Journal of Materials Engineering and Performance, 2017, 26(3):1444.
[10]	董开朝.Na₂CO₃添加剂对碳化硼制备的影响及其作用机理的研究. 沈阳: 东北大学硕士学位论文, 2019.
[11]	于国强, 刘维良, 欧阳瑞丰, 等. 碳热还原法制备碳化硼粉末的工艺研究. 中国陶瓷, 2012, 48(6):58.
[12]	ALIZADEH A, TAHERI-NASSAJ E, EHSANI N. Synthesis of boron carbide powder by a carbothermic reduction method. Journal of the European Ceramic Society, 2004, 24(10/11):3227.
[13]	KANANATHAN J, SOFIAH A G N, SAMYKANO M, et al. Influence of boric acid (H₃BO₃) concentration on the physical properties of electrochemical deposited nickel (Ni) nanowires. IOP Conference Series: Materials Science and Engineering, 2017, 257: 012033.
[14]	HAYUN S, WEIZMANN A, DARIEL M P, et al. Microstructural evolution during the infiltration of boron carbide with molten silicon. Journal of the European Ceramic Society, 2010, 30(4):1007.
[15]	HAYUN S, FRAGE N, DARIEL M P. The morphology of ceramic phases in B_xC-SiC-Si infiltrated composites. Journal of Solid State Chemistry, 2006, 179(9):2875.
[16]	HAYUN S, WEIZMANN A, DARIEL M P, et al. The effect of particle size distribution on the microstructure and the mechanical properties of boron carbide-based reaction-bonded composites. International Journal of Applied Ceramic Technology, 2009, 6(4):492.
[17]	ZHANG C, XIA Q, HAN L, et al. Fabrication of carbon-coated boron carbide particle and its role in the reaction bonding of boron carbide by silicon infiltration. Journal of the European Ceramic Society, 2022, 42(3):860.
[18]	CHEN Z F, SU Y C, CHENG Y B. Formation and sintering mechanisms of reaction bonded silicon carbide-boron carbide composites. Key Engineering Materials, 2007, 352: 207.
[19]	赵祖德. 复合材料固-液成形理论与工艺. 北京: 冶金工业出版社, 2008.
[20]	PATEL M, SUBRAHMANYAM J, PRASAD V V B, et al. Processing and characterization of B₄C-SiC-Si-TiB₂ composites. Materials Science and Engineering: A, 2010, 527(16/17):4109.
[21]	CHAIM R, HEFETZ M. Effect of grain size on elastic modulus and hardness of nanocrystalline ZrO₂-3 wt%Y₂O₃ ceramic. Journal of Materials Sciences, 2004, 39(9):3057.
[22]	THÉVENOT F. Boron carbide-a comprehensive review. Journal of the European Ceramic Society, 1990, 6(4):205.
[23]	DOWLING N. Mechanical behavior of materials:engineering methods for deformation, fracture, and fatigue. Upper Saddle River: Pearson Education Inc., 2012.
[24]	BARSOUM M, BARSOUM M W. Fundamentals of Ceramics. New York: The McGraw-Hill Companies Inc., 2002.
[25]	GUO S, TODD R I. Quantitative optical fluorescence microprobe measurements of stresses around indentations in Al₂O₃ and Al₂O₃/SiC nanocomposites: the influence of depth resolution and specimen translucency. Acta Materialia, 2011, 59(7):2637.
[26]	ZHANG C, RU H, WANG W, et al. The role of infiltration temperature in the reaction bonding of boron carbide by silicon infiltration. Journal of the American Ceramic Society, 2014, 97(10):3286.