Journal of Advanced Ceramics

, Volume 8, Issue 1, pp 112–120 | Cite as

ZrC–ZrB2–SiC ceramic nanocomposites derived from a novel single-source precursor with high ceramic yield

  • Zhaoju YuEmail author
  • Xuan Lv
  • Shuyi Lai
  • Le Yang
  • Wenjing Lei
  • Xingang LuanEmail author
  • Ralf Riedel
Open Access
Research Article


For the first time, ZrC–ZrB2–SiC ceramic nanocomposites were successfully prepared by a single-source-precursor route, with allylhydridopolycarbosilane (AHPCS), triethylamine borane (TEAB), and bis(cyclopentadienyl) zirconium dichloride (Cp2ZrCl2) as starting materials. The polymer-to-ceramic transformation and thermal behavior of obtained single-source precursor were characterized by means of Fourier transform infrared spectroscopy (FT-IR) and thermal gravimetric analysis (TGA). The results show that the precursor possesses a high ceramic yield about 85% at 1000 °C. The phase composition and microstructure of formed ZrC–ZrB2–SiC ceramics were investigated by means of X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Meanwhile, the weight loss and chemical composition of the resultant ZrC–ZrB2–SiC nanocomposites were investigated after annealing at high temperature up to 1800 °C. High temperature behavior with respect to decomposition as well as crystallization shows a promising high temperature stability of the formed ZrC–ZrB2–SiC nanocomposites.


polymer derived ceramics single-source precursor ceramic nanocomposite 



Zhaoju Yu thanks National Natural Science Foundation of China (No. 51872246), Alexander von Humboldt Foundation, and Creative Research Foundation of Science and Technology on Thermo Structural Composite Materials Laboratory (No. 6142911040114) for financial support. Xingang Luan thanks the National Key R&D Program of China (No. 2017YFB0703200) for financial support.


  1. [1]
    Li J, Fu ZY, Wang WM, et al. Preparation of ZrC by self-propagating high-temperature synthesis. Ceram Int 2010, 36: 1681–1686.CrossRefGoogle Scholar
  2. [2]
    Pi H, Fan S, Wang Y. C/SiC–ZrB2–ZrC composites fabricated by reactive melt infiltration with ZrSi2 alloy. Ceram Int 2012, 38: 6541–6548.CrossRefGoogle Scholar
  3. [3]
    Li Q, Dong S, Wang Z, et al. Fabrication and properties of 3-D Cf/SiC–ZrC composites, using ZrC precursor and polycarbosilane. J Am Ceram Soc 2012, 95: 1216–1219.CrossRefGoogle Scholar
  4. [4]
    Fahrenholtz W G, Hilmas GE, Talmy IG, et al. Refractory diborides of zirconium and hafnium. J Am Ceram Soc 2007, 90: 1347–1364.CrossRefGoogle Scholar
  5. [5]
    Miller-Oana M, Neff P, Valdez M, et al. Oxidation behavior of aerospace materials in high enthalpy flows using an oxyacetylene torch facility. J Am Ceram Soc 2015, 98: 1300–1307.CrossRefGoogle Scholar
  6. [6]
    Jiang DL. Fine Ceramics Materials. Beijing: Substance Press, 2000. (in Chinese)Google Scholar
  7. [7]
    Lucas R, Davis CE, Clegg WJ, et al. Elaboration of ZrC–SiC composites by spark plasma sintering using polymer-derived ceramics. Ceram Int 2014, 40: 15703–15709.CrossRefGoogle Scholar
  8. [8]
    Wang H, Chen X, Gao B, et al. Synthesis and characterization of a novel precursor-derived ZrC/ZrB2 ultra-high-temperature ceramic composite. Appl Organomet Chem 2013, 27: 79–84.CrossRefGoogle Scholar
  9. [9]
    Zhou H, Gao L, Wang Z, et al. ZrB2–SiC oxidation protective coating on C/C composites prepared by vapor silicon infiltration process. J Am Ceram Soc 2010, 93: 915–919.CrossRefGoogle Scholar
  10. [10]
    Shi X-H, Huo J-H, Zhu J-L, et al. Ablation resistance of SiC–ZrC coating prepared by a simple two-step method on carbon fiber reinforced composites. Corros Sci 2014, 88: 49–55.CrossRefGoogle Scholar
  11. [11]
    Dong ZJ, Liu SX, Li XK, et al. Influence of infiltration temperature on the microstructure and oxidation behavior of SiC–ZrC ceramic coating on C/C composites prepared by reactive melt infiltration. Ceram Int 2015, 41: 797–811.CrossRefGoogle Scholar
  12. [12]
    Hu C, Niu Y, Huang S, et al. In-situ fabrication of ZrB2–SiC/SiC gradient coating on C/C composites. J Alloys Compd 2015, 646: 916–923.CrossRefGoogle Scholar
  13. [13]
    Li L, Li H, Li Y, et al. A SiC–ZrB2–ZrC coating toughened by electrophoretically-deposited SiC nanowires to protect C/C composites against thermal shock and oxidation. Appl Surf Sci 2015, 349: 465–471.CrossRefGoogle Scholar
  14. [14]
    Gleiter H. Nanostructured materials: State of the art and perspectives. Nanostruct Mater 1995, 6: 3–14.CrossRefGoogle Scholar
  15. [15]
    Sawaguchi A, Toda K, Niihara K. Mechanical and electrical properties of silicon nitride-silicon carbide nanocomposite material. J Am Ceram Soc 1991, 74: 1142–1144.CrossRefGoogle Scholar
  16. [16]
    Ionescu E, Kleebe H-J, Riedel R. Silicon-containing polymer-derived ceramic nanocomposites (PDC-NCs): Preparative approaches and properties. Chem Soc Rev 2012, 41: 5032–5052.CrossRefGoogle Scholar
  17. [17]
    Wang X-G, Zhang G-J, Xue J-X, et al. Reactive hot pressing of ZrC–SiC ceramics at low temperature. J Am Ceram Soc 2013, 96: 32–36.CrossRefGoogle Scholar
  18. [18]
    Wu W-W, Zhang G-J, Kan Y-M, et al. Reactive hot pressing of ZrB2–SiC–ZrC ultra high-temperature ceramics at 1800. J Am Ceram Soc 2006, 89: 2967–2969.Google Scholar
  19. [19]
    Wang L, Jiang W, Chen L. Rapidly sintering nanosized SiC particle reinforced TiC composites by the spark plasma sintering (SPS) technique. J Mater Sci 2004, 39: 4515–4519.CrossRefGoogle Scholar
  20. [20]
    Sarin P, Driemeyer PE, Haggerty RP, et al. In situ studies of oxidation of ZrB2 and ZrB2–SiC composites at high temperatures. J Eur Ceram Soc 2010, 30: 2375–2386.CrossRefGoogle Scholar
  21. [21]
    Yuan J, Hapis S, Breitzke H, et al. Single-source-precursor synthesis of hafnium-containing ultrahigh-temperature ceramic nanocomposites (UHTC-NCs). Inorg Chem 2014, 53: 10443–10455.CrossRefGoogle Scholar
  22. [22]
    Wen Q, Xu Y, Xu B, et al. Single-source-precursor synthesis of dense SiC/HfCxN1−x-based ultrahigh-temperature ceramic nanocomposites. Nanoscale 2014, 6: 13678–13689.CrossRefGoogle Scholar
  23. [23]
    Cai T, Liu D, Qiu WF, et al. Polymer precursor-derived HfC–SiC ultrahigh-temperature ceramic nanocomposites. J Am Ceram Soc 2018, 101: 20–24.CrossRefGoogle Scholar
  24. [24]
    Cheng J, Wang X, Wang H, et al. Preparation and high-temperature behaviour of HfC–SiC nanocomposites derived from a non-oxygen single-source-precursor. J Am Ceram Soc 2017, 100: 5044–5055.CrossRefGoogle Scholar
  25. [25]
    Cai T, Qiu W-F, Liu D, et al. Synthesis of soluble poly-yne polymers containing zirconium and silicon and corresponding conversion to nanosized ZrC/SiC composite ceramics. Dalton Trans 2013, 42: 4285–4290.CrossRefGoogle Scholar
  26. [26]
    Lu Y, Chen F, An P, et al. Polymer precursor synthesis of TaC–SiC ultrahigh temperature ceramic nanocomposites. RSC Adv 2016, 6: 88770–88776.CrossRefGoogle Scholar
  27. [27]
    Li Y, Han W, Li H, et al. Synthesis of nano-crystalline ZrB2/ZrC/SiC ceramics by liquid precursors. Mater Lett 2012, 68: 101–103.CrossRefGoogle Scholar
  28. [28]
    Colombo P, Mera G, Riedel R, et al. Polymer-derived ceramics: 40 years of research and innovation in advanced ceramics. J Am Ceram Soc 2010, 93: 1805–1837.Google Scholar
  29. [29]
    Yu Z, Huang M, Fang Y, et al. Modification of a liquid polycarbosilane with 9-BBN as a high-ceramic-yield precursor for SiC. React Funct Polym 2010, 70: 334–339.CrossRefGoogle Scholar
  30. [30]
    Yu Z, Yang L, Min H, et al. Single-source-precursor synthesis of high temperature stable SiC/C/Fe nanocomposites from a processable hyperbranched polyferrocenylcarbosilane with high ceramic yield. J Mater Chem C 2014, 2: 1057–1067.CrossRefGoogle Scholar
  31. [31]
    Yu Z, Yang L, Zhan J, et al. Preparation, cross-linking and ceramization of AHPCS/Cp2ZrCl2 hybrid precursors for SiC/ZrC/C composites. J Eur Ceram Soc 2012, 32: 1291–1298.CrossRefGoogle Scholar
  32. [32]
    Wen Q, Feng Y, Yu Z, et al. Microwave absorption of SiC/HfCxN1−x/C ceramic nanocomposites with HfCxN1−x–carbon core–shell particles. J Am Ceram Soc 2016, 99: 2655–2663.CrossRefGoogle Scholar
  33. [33]
    Li S, Zhang L, Huang M, et al. In situ synthesis and microstructure characterization of TiC–TiB2–SiC ultrafine composites from hybrid precursor. Mater Chem Phys 2012, 133: 946–953.CrossRefGoogle Scholar
  34. [34]
    Yu Z, Pei Y, Lai S, et al. Single-source-precursor synthesis, microstructure and high temperature behavior of TiC–TiB2–SiC ceramic nanocomposites. Ceram Int 2017, 43: 5949–5956.CrossRefGoogle Scholar
  35. [35]
    Amorós P, Beltrán D, Guillem C, et al. Synthesis and characterization of SiC/MC/C ceramics (M = Ti, Zr, Hf) starting from totally non-oxidic precursors. Chem Mater 2002, 14: 1585–1590.CrossRefGoogle Scholar
  36. [36]
    Drezdzon MA. The Manipulation of Air Sensitive Compounds. Chichester: John Wiley & Sons, 1986.Google Scholar
  37. [37]
    Huang TH, Yu ZJ, He XM, et al. One-pot synthesis and characterization of a new, branched polycarbosilane bearing allyl groups. Chin Chem Lett 2007, 18: 754–757.CrossRefGoogle Scholar
  38. [38]
    Bianchini D, Barsan MM, Butler IS, et al. Vibrational spectra of silsesquioxanes impregnated with the metallocene catalyst bis(η5-cyclopentadienyl)zirconium(IV) dichloride. Spectrochim Acta A 2007, 68: 956–969.CrossRefGoogle Scholar
  39. [39]
    Cho M-S, Kim B-H, Kong J-I, et al. Synthesis, catalytic Si–Si dehydrocoupling, and thermolysis of polyvinylsilanes [CH2CH(SiH2X)]n (X = H, Ph). J Organomet Chem 2003, 685: 99–106.CrossRefGoogle Scholar
  40. [40]
    Corey JY, Rooney SM. Reactions of symmetrical and unsymmetrical disilanes in the presence of Cp2MCl2/nBuLi (M = Ti, Zr, Hf). J Organomet Chem 1996, 521: 75–91.CrossRefGoogle Scholar
  41. [41]
    Horáček M, Pinkas J, Gyepes R, et al. Reactivity of SiMe2H substituents in permethylated titanocene complexes: Dehydrocoupling and ethene hydrosilylation. Organometallics 2008, 27: 2635–2642.CrossRefGoogle Scholar
  42. [42]
    Takahashi T, Hasegawa M, Suzuki N, et al. Zirconium-catalyzed highly regioselective hydrosilation reaction of alkenes and X-ray structures of silyl(hydrido)zirconocene derivatives. J Am Chem Soc 1991, 113: 8564–8566.CrossRefGoogle Scholar
  43. [43]
    Mocaer D, Pailler R, Naslain R, et al. Si–C–N ceramics with a high microstructural stability elaborated from the pyrolysis of new polycarbosilazane precursors. Part I: The organic/inorganic transition. J Mater Sci 1993, 28: 2615–2631.Google Scholar
  44. [44]
    Zaheer M, Schmalz T, Motz G, et al. Polymer derived non-oxide ceramics modified with late transition metals. Chem Soc Rev 2012, 41: 5102–5116.CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.College of MaterialsKey Laboratory of High Performance Ceramic Fibers (Xiamen University), Ministry of EducationXiamenChina
  2. 2.College of MaterialsFujian Key Laboratory of Advanced Materials (Xiamen University)XiamenChina
  3. 3.College of Materials Science and EngineeringHuaqiao UniversityXiamenChina
  4. 4.Science and Technology on Thermostructural Composite Materials LaboratoryNorthwestern Polytechnical UniversityXi’anChina
  5. 5.Technische Universität DarmstadtInstitut für MaterialwißsenschaftDarmstadtGermany

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