Journal of Sol-Gel Science and Technology

, Volume 86, Issue 2, pp 365–373 | Cite as

Microstructure and thermal shock behavior of sol–gel introduced ZrB2 reinforced SiBCN matrix

  • Yang Miao
  • Zhihua Yang
  • Wenxian Wang
  • Dechang Jia
  • Yibing Cheng
  • Yu Zhou
Original Paper: Industrial and technological applications of sol-gel and hybrid materials


Here we assess the effects of selected methods of introducing ZrB2 in SiBCN matrix on microstructure and thermal shock properties prepared by spark plasma sintering (SPS). In one approach Zirconium n-propoxide (ZNP), the precursor of zirconia was introduced then reacted with amorphous BN(C) from the matrix, forming ZrB2 phase, labeled as SZ1; A second approach is to introduce ZNP, boric acid, and furfuryl alcohol (C5H6O2) (FA), the precursor of zirconia, boron oxide, and carbon in SiBCN matrix by sol–gel method to form ZrB2 through carbon/borothermal reduction, labeled as SZ2. Results show that ZrB2 particles are distributed homogeneously in SiBCN matrix. For SZ2 system, the grain sizes of ZrB2 (100–500 nm) are much smaller than SZ1 composites(1–1.5 µm). SZ2 shows a higher diffusion rate (16.5 mm2/s) than SZ1 (12.8 mm2/s) at room temperature, and the high-temperature diffusion rate are very close to each other. After rapid quenching, residual stresses are caused by coefficient of thermal expansion mismatch and temperature gradient within the sample. On the other hand, the oxidized products formed on the surface during high temperature exposure could also contribute to thermal stresses causing spallation and enhancing damage.


ZrB2 SiBCN Sol–gel SPS Microstructure Thermal shock behavior 



Yang Miao would like to acknowledge the scholarship from the CSC (China scholarship Council). The authors give thanks to the National Natural Science Foundation of China for support (NSFC, Grant no. 51621091, 51072041, 50902031 and 51021002). The authors also thank Richard M. Laine (Dept. Of Materials Science and Engineering, University of Michigan, USA) for help with the language use.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Yang Z-H, Jia D-C, Duan X-m, Zhou Y (2010) Microstructure and thermal stabilities in various atmospheres of SiB0.5C1.5N0.5 nano-sized powders fabricated by mechanical alloying technique. J Non-Cryst Sol 356:326–333CrossRefGoogle Scholar
  2. 2.
    Bechelany MC, Salameh C, Viard A, Guichaoua L, Rossignol F, Chartier T, Bernard S, Miele P (2015) Preparation of polymer-derived Si–B–C–N monoliths by spark plasma sintering technique. J Eur Ceram Soc 35:1361–1374CrossRefGoogle Scholar
  3. 3.
    Gottardo L, Bernard S, Gervais C, Weinmann M, Miele P (2012) Study of the intermediate pyrolysis steps and mechanism identification of polymer-derived SiBCN ceramics. J Mater Chem 22:17923–17933CrossRefGoogle Scholar
  4. 4.
    Tang B, Zhang Y, Hu S, Feng B (2016) A dense amorphous SiBCN(O) ceramic prepared by simultaneous pyrolysis of organics and inorganics. Ceram Int 42:5238–5244CrossRefGoogle Scholar
  5. 5.
    Longbiao L (2016) Effects of temperature, oxidation and fiber preforms on interface shear stress degradation in fiber-reinforced ceramic-matrix composites. Mater Sci Eng: A 674:588–603CrossRefGoogle Scholar
  6. 6.
    Long X, Shao C, Wang H, Wang J (2015) Synthesis and characterization of a polyborosilazane/Cp2ZrCl2 hybrid precursor for the Si–B–C–N–Zr multinary ceramic. Dalton Trans 44:15463–15469CrossRefGoogle Scholar
  7. 7.
    Guo Q, Li J, Shen Q, Zhang L (2012) Preparation and characterization of ZrB2–SiC–Zr2Al4C5 composites by spark plasma sintering-reactive synthesis (SPS-RS) method. Mater Sci Eng: A 558:186–192CrossRefGoogle Scholar
  8. 8.
    Zou J, Liu J, Zhao J, Zhang G-J, Huang S, Qian B, Vleugels J, Van der Biest O, Shen JZ (2014) A top-down approach to densify ZrB2–SiC–BN composites with deeper homogeneity and improved reliability. Chem Eng J 249:93–101CrossRefGoogle Scholar
  9. 9.
    Licheri R, Musa C, Orrù R, Cao G (2015) Influence of the heating rate on the in situ synthesis and consolidation of ZrB2 by reactive Spark Plasma Sintering. J Eur Ceram Soc 35:1129–1137CrossRefGoogle Scholar
  10. 10.
    Guo W-M, Vleugels J, Zhang G-J, Wang P-L, Van der Biest O (2010) Effect of heating rate on densification, microstructure and strength of spark plasma sintered ZrB2-based ceramics Scr Mater 62:802–805CrossRefGoogle Scholar
  11. 11.
    Ushakov SV, Navrotsky A, Green DJ (2012) Experimental approaches to the thermodynamics of ceramics above 1500°C. J Am Ceram Soc 95:1463–1482CrossRefGoogle Scholar
  12. 12.
    Wu W-W, Xiao W-L, Estili M, Zhang G-J, Sakka Y (2013) Microstructure and mechanical properties of ZrB2–SiC–BN composites fabricated by reactive hot pressing and reactive spark plasma sintering. Scr Mater 68:889–892CrossRefGoogle Scholar
  13. 13.
    Monteverde F (2007) Ultra-high temperature HfB2–SiC ceramics consolidated by hot-pressing and spark plasma sintering. J Alloy Compd 428:197–205CrossRefGoogle Scholar
  14. 14.
    Anselmi-Tamburini U, Garay JE, Munir ZA (2005) Fundamental investigations on the spark plasma sintering/synthesis process. Mater Sci Eng: A 407:24–30CrossRefGoogle Scholar
  15. 15.
    Bernard-Granger G, Guizard C (2007) Spark plasma sintering of a commercially available granulated zirconia powder: I. Sintering path and hypotheses about the mechanism(s) controlling densification. Acta Mater 55:3493–3504CrossRefGoogle Scholar
  16. 16.
    Zhang L, Hao S, Liu B, Shum HC, Li J, Chen H (2013) Fabrication of ceramic microspheres by diffusion-induced sol-gel reaction in double emulsions. ACS Appl Mater Interfaces 5:11489–11493CrossRefGoogle Scholar
  17. 17.
    Ang C, Seeber A, Williams T, Cheng Y-B (2014) SPS densification and microstructure of ZrB2 composites derived from sol–gel ZrC coating. J Eur Ceram Soc 34:2875–2883CrossRefGoogle Scholar
  18. 18.
    Yadhukulakrishnan GB, Karumuri S, Rahman A, Singh RP, Kaan Kalkan A, Harimkar SP (2013) Spark plasma sintering of graphene reinforced zirconium diboride ultra-high temperature ceramic composites. Ceram Int 39:6637–6646CrossRefGoogle Scholar
  19. 19.
    Zhang P, Jia D, Yang Z, Duan X, Zhou Y (2013) Influence of ball milling parameters on the structure of the mechanically alloyed SiBCN powder. Ceram Int 39:1963–1969CrossRefGoogle Scholar
  20. 20.
    Li D, Yang Z, Jia D, Hu C, Liang B, Zhou Y (2015) Preparation, microstructures, mechanical properties and oxidation resistance of SiBCN/ZrB2–ZrN ceramics by reactive hot pressing. J Eur Ceram Soc 35:4399–4410CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.College of Materials Science and EngineeringTaiyuan University of TechnologyTaiyuanChina
  2. 2.Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of TechnologyHarbinChina
  3. 3.State Key Laboratory of Advanced Welding and Joining, Harbin Institute of TechnologyHarbinChina
  4. 4.Department of Materials Engineering, Monash UniversityClaytonAustralia

Personalised recommendations