Journal Home > Volume 9 , issue 1

Ultra-high temperature ceramics (UHTCs) are considered as a family of nonmetallic and inorganic materials that have melting point over 3000 ℃. Chemically, nearly all UHTCs are borides, carbides, and nitrides of early transition metals (e.g., Zr, Hf, Nb, Ta). Within the last two decades, except for the great achievements in the densification, microstructure tailoring, and mechanical property improvements of UHTCs, many methods have been established for the preparation of porous UHTCs, aiming to develop high-temperature resistant, sintering resistant, and lightweight materials that will withstand temperatures as high as 2000 ℃ for long periods of time. Amongst the synthesis methods for porous UHTCs, sol–gel methods enable the preparation of porous UHTCs with pore sizes from 1 to 500 μm and porosity within the range of 60%–95% at relatively low temperature. In this article, we review the currently available sol–gel methods for the preparation of porous UHTCs. Templating, foaming, and solvent evaporation methods are described and compared in terms of processing–microstructure relations. The properties and high temperature resistance of sol–gel derived porous UHTCs are discussed. Finally, directions to future investigations on the processing and applications of porous UHTCs are proposed.


menu
Abstract
Full text
Outline
About this article

Sol–gel derived porous ultra-high temperature ceramics

Show Author's information Fei LIa( )Xiao HUANGbJi-Xuan LIUaGuo-Jun ZHANGa( )
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Institute of Functional Materials, Donghua University, Shanghai 201620, China
Institute for the Conservation of Cultural Heritage, Shanghai University, Shanghai 200444, China

Abstract

Ultra-high temperature ceramics (UHTCs) are considered as a family of nonmetallic and inorganic materials that have melting point over 3000 ℃. Chemically, nearly all UHTCs are borides, carbides, and nitrides of early transition metals (e.g., Zr, Hf, Nb, Ta). Within the last two decades, except for the great achievements in the densification, microstructure tailoring, and mechanical property improvements of UHTCs, many methods have been established for the preparation of porous UHTCs, aiming to develop high-temperature resistant, sintering resistant, and lightweight materials that will withstand temperatures as high as 2000 ℃ for long periods of time. Amongst the synthesis methods for porous UHTCs, sol–gel methods enable the preparation of porous UHTCs with pore sizes from 1 to 500 μm and porosity within the range of 60%–95% at relatively low temperature. In this article, we review the currently available sol–gel methods for the preparation of porous UHTCs. Templating, foaming, and solvent evaporation methods are described and compared in terms of processing–microstructure relations. The properties and high temperature resistance of sol–gel derived porous UHTCs are discussed. Finally, directions to future investigations on the processing and applications of porous UHTCs are proposed.

Keywords:

sol–gel, ultra-high temperature ceramics, porous ceramics, processing, microstructure
Received: 20 December 2018 Revised: 10 April 2019 Accepted: 15 April 2019 Published: 05 February 2020 Issue date: February 2020
References(63)
[1]
GJ Zhang, DW Ni, J Zou, et al. Inherent anisotropy in transition metal diborides and microstructure/property tailoring in ultra-high temperature ceramics—A review. J Eur Ceram Soc 2018, 38: 371-389.
[2]
WC Bao, S Robertson, JX Liu, et al. Structural integrity and characteristics at lattice and nanometre levels of ZrN polycrystalline irradiated by 4 MeV Au ions. J Eur Ceram Soc 2018, 38: 4373-4383.
[3]
Y Lu, J Zou, FF Xu, et al. Volatility diagram of ZrB2-SiC-ZrC system and experimental validation. J Am Ceram Soc 2018, 101: 3627-3635.
[4]
Z Ji, V Rubio, J Binner. Thermoablative resistance of ZrB2-SiC-WC ceramics at 2400 ℃. Acta Mater 2017, 133: 293-302.
[5]
GJ Zhang, ZY Deng, N Kondo, et al. Reactive hot pressing of ZrB2-SiC composites. J Am Ceram Soc 2004, 83: 2330-2332.
[6]
WG Fahrenholtz, GE Hilmas. Ultra-high temperature ceramics: Materials for extreme environments. Scr Mater 2017, 129: 94-99.
[7]
E Wuchina, M Opeka, S Causey, et al. Designing for ultrahigh-temperature applications: The mechanical and thermal properties of HfB2, HfCx, HfNx and αHf(N). J Mater Sci 2004, 39: 5939-5949.
[8]
MM Opeka, IG Talmy, EJ Wuchina, et al. Mechanical, thermal, and oxidation properties of refractory hafnium and zirconium compounds. J Eur Ceram Soc 1999, 19: 2405-2414.
[9]
A Paul, DD Jayaseelan, S Venugopal, et al. UHTC composites for hypersonic applications. American Ceramic Society Bulletin 2012, 91: 22-29.
[10]
JF Justin, A Jankowiak. Ultra high temperature ceramics: densification, properties and thermal stability. Aerosp J 2011: 1-11.
[11]
RV Krishnarao, VV Bhanuprasad, G Madhusudhan Reddy. ZrB2–SiC based composites for thermal protection by reaction sintering of ZrO2+B4C+Si. J Adv Ceram 2017, 6: 320-329.
[12]
KX Gui, FY Liu, G Wang, et al. Microstructural evolution and performance of carbon fiber-toughened ZrB2 ceramics with SiC or ZrSi2 additive. J Adv Ceram 2018, 7: 343-351.
[13]
RJ He, ZL Qu, D Liang. Rapid heating thermal shock study of ultra high temperature ceramics using an in situ testing method. J Adv Ceram 2017, 6: 279-287.
[14]
WG Fahrenholtz, EJ Wuchina, WE Lee, et al. Ultra-high Temperature Ceramics: Materials for Extreme Environment Applications. Hoboken (USA): John Wiley & Sons, Inc., 2014.
[15]
M Scheffler, P Colombo. Cellular Ceramics: Structure, Manufacturing, Properties and Applications. New York: Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
[16]
C Tallon, GV Franks. Multi-scale porous ultra-high temperature ceramics. Final project report. Sponsored by Asian Office of Aerospace Research and Development. Grant Number: AOARD-134068. 2015: 43.
[17]
JC Du, XH Zhang, CQ Hong, et al. Microstructure and mechanical properties of ZrB2–SiC porous ceramic by camphene-based freeze casting. Ceram Int 2013, 39: 953-957.
[18]
E Landi, D Sciti, C Melandri, et al. Ice templating of ZrB2 porous architectures. J Eur Ceram Soc 2013, 33: 1599-1607.
[19]
E Sani, L Mercatelli, JL Sans, et al. Porous and dense hafnium and zirconium ultra-high temperature ceramics for solar receivers. Opt Mater 2013, 36: 163-168.
[20]
XX Jin, LM Dong, Q Li, et al. Thermal shock cracking of porous ZrB2-SiC ceramics. Ceram Int 2016, 42: 13309-13313.
[21]
F Li, XG Wang, X Huang, et al. Preparation of ZrC/SiC porous self-supporting monoliths via sol–gel process using polyethylene glycol as phase separation inducer. J Eur Ceram Soc 2018, 38: 4806-4813.
[22]
F Li, X Huang. Preparation of highly porous ZrB2/ZrC/SiC composite monoliths using liquid precursors via direct drying process. J Eur Ceram Soc 2018, 38: 1103-1111.
[23]
F Li, Z Kang, X Huang, et al. Preparation of zirconium carbide foam by direct foaming method. J Eur Ceram Soc 2014, 34: 3513-3520.
[24]
WG Fahrenholtz, GE Hilmas. Ultra-high temperature ceramics: Materials for extreme environments. Scr Mater 2017, 129: 94-99.
[25]
F Li, MS Liang, XF Ma, et al. Preparation and characterization of stoichiometric zirconium carbide foams by direct foaming of zirconia sols. J Porous Mater 2015, 22: 493-500.
[26]
XX Jin, LM Dong, HY Xu, et al. Effects of porosity and pore size on mechanical and thermal properties as well as thermal shock fracture resistance of porous ZrB2-SiC ceramics. Ceram Int 2016, 42: 9051-9057.
[27]
V Medri, M Mazzocchi, A Bellosi. ZrB2-based sponges and lightweight devices. Int J Appl Ceram Technol 2011, 8: 815-823.
[28]
GV Franks, C Tallon, AR Studart, et al. Colloidal processing: Enabling complex shaped ceramics with unique multiscale structures. J Am Ceram Soc 2017, 100: 458-490.
[29]
A Feinle, MS Elsaesser, N Hüsing. Sol–gel synthesis of monolithic materials with hierarchical porosity. Chem Soc Rev 2016, 45: 3377-3399.
[30]
K Okada, T Isobe, KI Katsumata, et al. Porous ceramics mimicking nature—Preparation and properties of microstructures with unidirectionally oriented pores. Sci Technol Adv Mater 2011, 12: 064701.
[31]
AR Studart, UT Gonzenbach, E Tervoort, et al. Processing routes to macroporous ceramics: A review. J Am Ceram Soc 2006, 89: 1771-1789.
[32]
P Colombo. In praise of pores. Science 2008, 322: 381-383.
[33]
YB Qian, WG Zhang, M Ge, et al. Frictional response of a novel C/C-ZrB2-ZrC-SiC composite under simulated braking. J Adv Ceram 2013, 2: 157-161.
[34]
XZ Guo, XB Cai, L Zhu, et al. Preparation and properties of SiC honeycomb ceramics by pressureless sintering technology. J Adv Ceram 2014, 3: 83-88.
[35]
JM Wu, XY Zhang, J Xu, et al. Preparation of porous Si3N4 ceramics via tailoring solid loading of Si3N4 slurry and Si3N4 poly-hollow microsphere content. J Adv Ceram 2015, 4: 260-266.
[36]
HB Wu, J Yin, XJ Liu, et al. Aqueous gelcasting and pressureless sintering of zirconium diboride foams. Ceram Int 2014, 40: 6325-6330.
[37]
F Li, X Huang, GJ Zhang. Preparation of ultra-high temperature ceramics-based materials by sol–gel routes. In Recent Applications in Sol-gel Synthesis. C Usha, Ed. InTech, 2017.
[38]
AE Danks, SR Hall, Z Schnepp. The evolution of ‘sol–gel’ chemistry as a technique for materials synthesis. Mater Horiz 2016, 3: 91-112.
[39]
K Nakanishi, K Kanamori, Y Tokudome, et al. Sol–gel processing of porous materials. In Handbook of Solid State Chemistry. R Dronskowshi, S Kikkawa, A Stein, Eds. New York: Wiley-VCH Verlag GmbH & Co. KGaA, 2017.
[40]
MD Sacks, CA Wang, ZH Yang, et al. Carbothermal reduction synthesis of nanocrystalline zirconium carbide and hafnium carbide powders using solution-derived precursors. J Mater Sci 2004, 39: 6057-6066.
[41]
M Dollé, D Gosset, C Bogicevic, et al. Synthesis of nanosized zirconium carbide by a sol–gel route. J Eur Ceram Soc 2007, 27: 2061-2067.
[42]
CL Yan, RJ Liu, YB Cao, et al. Carbothermal synthesis of submicrometer zirconium carbide from polyzirconoxane and phenolic resin by the facile one-pot reaction. J Am Ceram Soc 2012, 95: 3366-3369.
[43]
CE Ang, T Williams, A Seeber, et al. Synthesis and evolution of zirconium carbide via sol–gel route: Features of nanoparticle oxide-carbon reactions. J Am Ceram Soc 2013, 96: 1099-1106.
[44]
T Cai, WF Qiu, D Liu, et al. Synthesis of ZrC–SiC powders by a preceramic solution route. J Am Ceram Soc 2013, 96: 3023-3026.
[45]
C Ziegler, A Wolf, W Liu, et al. Modern inorganic aerogels. Angew Chem Int Ed 2017, 56: 13200-13221.
[46]
CJ Brinker, GW Scherer. Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing. San Diego (USA): Academic Press Inc., 1990.
[47]
ZH Ji, L Ye, XY Tao, et al. Synthesis of ordered mesoporous ZrC/C nanocomposite via magnesiothermic reduction at low temperature. Mater Lett 2012, 71: 88-90.
[48]
CJ Brinker, GW Scherer. Drying. In Sol-Gel Science. CJ Brinker, GW Scherer, Eds. San Diego (USA): Academic Press, 1990: 452-513.
[49]
F Li, WC Bao, DW Ni, et al. A thermoset hybrid sol for the syntheses of zirconium carbide–silicon carbide foam via replica method. J Porous Mater 2019, 26: 409-417.
[50]
K Nakanishi, N Tanaka. Sol–gel with phase separation. Hierarchically porous materials optimized for high- performance liquid chromatography separations. Acc Chem Res 2007, 40: 863-873.
[51]
B Basnet, N Sarkar, JG Park, et al. Al2O3–TiO2/ZrO2–SiO2 based porous ceramics from particle-stabilized wet foam. J Adv Ceram 2017, 6: 129-138.
[52]
EF Krivoshapkina, PV Krivoshapkin, AA Vedyagin. Synthesis of Al2O3–SiO2–MgO ceramics with hierarchical porous structure. J Adv Ceram 2017, 6: 11-19.
[53]
CR Rambo, J Cao, O Rusina, et al. Manufacturing of biomorphic (Si, Ti, Zr)-carbide ceramics by sol–gel processing. Carbon 2005, 43: 1174-1183.
[54]
S Venugopal, EE Boakye, A Paul, et al. Sol-gel synthesis and formation mechanism of ultrahigh temperature ceramic: HfB2. J Am Ceram Soc 2014, 97: 92-99.
[55]
XY Tao, WF Qiu, H Li, et al. Synthesis of nanosized zirconium carbide from preceramic polymers by the facile one-pot reaction. Polym Adv Technol 2010, 21: 300-304.
[56]
F Li, X Huang, GJ Zhang. Scalable foaming assisted synthesis of ZrC nanopowder by carbothermal reduction. Ceram Int 2015, 41: 3335-3338.
[57]
N Leventis, N Chandrasekaran, AG Sadekar, et al. The effect of compactness on the carbothermal conversion of interpenetrating metal oxide/resorcinol-formaldehyde nanoparticle networks to porous metals and carbides. J Mater Chem 2010, 20: 7456-7471.
[58]
XX Jin, XH Zhang, JC Han, et al. Thermal shock behavior of porous ZrB2–SiC ceramics. Mater Sci Eng 2013, 588: 175-180.
[59]
K Schwartzwalder, H Somers, AV Somers. Method of making porous ceramic articles. U.S. patent 3 090 094, May 1963.
[60]
UT Gonzenbach, AR Studart, E Tervoort, et al. Ultrastable particle-stabilized foams. Angew Chem Int Ed 2006, 45: 3526-3530.
[61]
UT Gonzenbach, AR Studart, E Tervoort, et al. Tailoring the microstructure of particle-stabilized wet foams. Langmuir 2007, 23: 1025-1032.
[62]
UT Gonzenbach, AR Studart, E Tervoort, et al. Stabilization of foams with inorganic colloidal particles. Langmuir 2006, 22: 10983-10988.
[63]
S Zhang, DL Zhao. Aerospace Materials Handbook. Boca Raton (USA): CRC Press, 2012.
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 20 December 2018
Revised: 10 April 2019
Accepted: 15 April 2019
Published: 05 February 2020
Issue date: February 2020

Copyright

© The author(s) 2019

Acknowledgements

Financial support from the National Natural Science Foundation of China (Nos. 51602324 and 51532009) and the Fundamental Research Funds for the Central Universities (No. 2232018D3-32) are gratefully acknowledged.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. 

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permission requests may be sought directly from editorial office.

Return