Hostname: page-component-669899f699-7xsfk Total loading time: 0 Render date: 2025-04-26T19:19:29.067Z Has data issue: false hasContentIssue false
  • English
  • Français

Facile preparation of macro-mesoporous zirconium titanate monoliths via a sol–gel reaction accompanied by phase separation

Published online by Cambridge University Press:  30 September 2019

Mingliang Sun ,
Tianbo Zhao ,
Zhaofei Ma  and
Zunfeng Li
Mingliang Sun
Affiliation:
Key Laboratory of Cluster Science of Ministry of Education, Beijing Institute of Technology, Beijing 102488, China
Tianbo Zhao*
Affiliation:
Key Laboratory of Cluster Science of Ministry of Education, Beijing Institute of Technology, Beijing 102488, China
Zhaofei Ma
Affiliation:
Key Laboratory of Cluster Science of Ministry of Education, Beijing Institute of Technology, Beijing 102488, China
Zunfeng Li
Affiliation:
Key Laboratory of Cluster Science of Ministry of Education, Beijing Institute of Technology, Beijing 102488, China
*
a)Address all correspondence to this author. e-mail: bit_bipt@126.com
Get access

Abstract

Macro-mesoporous zirconium titanate monoliths have been successfully prepared via a sol–gel process accompanied by phase separation, with poly(ethylene oxide) (PEO) as a phase separation inducer and N-methylformamide (NFA) as a gelation accelerator. The size and morphology of macropores are controlled by the PEO and NFA amount. By choosing appropriate starting composition, the co-continuous structure could be obtained. The as-dried gel is amorphous, the pore size is in the range of 0.05–0.5 μm, the porosity is 46%, and the surface area is 111 m2/g. After heat treatment at 500 °C, the gel transforms into the phase ZrTiO4, the macropore diameter decreases slightly, the porosity increases to 63%, and the surface area decreases to 40 m2/g. Moreover, the macroporous structure is well maintained, and the skeleton becomes dense and smooth. The samples have macropores, mesopores, and micropores before and after heat treatment.

Keywords

sol–gelporosityoxide
Type
Article
Information
Journal of Materials Research , Volume 34 , Issue 24 , 30 December 2019 , pp. 4066 - 4075
Copyright
Copyright © Materials Research Society 2019 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

References

Wang, C.L., Lee, H.Y., Azough, F., and Freer, R.: The microstructure and microwave dielectric properties of zirconium titanate ceramics in the solid solution system ZrTiO4–Zr5Ti7O24. J. Mater. Sci. 32, 1693 (1997).CrossRefGoogle Scholar
Zhang, S.X., Li, J.B., Cao, J., Zhai, H.Z., and Zhang, B.: Preparation, microstructure and microwave dielectric properties of ZrxTi1−xO4 (x = 0.40–0.60) ceramics. J. Eur. Ceram. Soc. 21, 2931 (2001).CrossRefGoogle Scholar
Wakino, K., Minai, H., and Tamura, H.: Microwave characteristics of (Zr, Sn)TiO4 and BaO–PbO–Nd2O3–TiO2 dielectric resonators. J. Am. Ceram. Soc. 67, 278 (1984).CrossRefGoogle Scholar
Leoni, M., Viviani, M., Battilana, G., Fiorello, A.M., and Viticoli, M.: Aqueous synthesis and sintering of zirconium titanate powders for microwave components. J. Eur. Ceram. Soc. 21, 1739 (2001).CrossRefGoogle Scholar
Chang, D.A., Lin, P., and Tseng, T.Y.: Optical properties of ZrTiO4 films grown by radio-frequency magnetron sputtering. J. Appl. Phys. 77, 4445 (1995).CrossRefGoogle Scholar
Troitzsch, U. and Ellis, D.J.: High-PT study of solid solutions in the system ZrO2–TiO2: The stability of srilankite. Eur. J. Mineral. 16, 577 (2004).CrossRefGoogle Scholar
Dondi, M., Matteucci, F., and Cruciani, G.: Zirconium titanate ceramic pigments: Crystal structure, optical spectroscopy and technological properties. J. Solid State Chem. 179, 233 (2006).CrossRefGoogle Scholar
Cosentino, I.C., Muccillo, E.N.S., and Muccillo, R.: Development of zirconia–titania porous ceramics for humidity sensors. Sens. Actuators, B 96, 677 (2003).CrossRefGoogle Scholar
Ličina, V., Gajović, A., Moguš-Milanković, A., Djerdj, I., Tomašić, N., and Su, D.S.: Correlation between the microstructure and the electrical properties of ZrTiO4 ceramics. J. Am. Ceram. Soc. 91, 178 (2008).CrossRefGoogle Scholar
Rouhani, P., Salahinejad, E., Kaul, R., Vashaee, D., and Tayebi, L.: Nanostructured zirconium titanate fibers prepared by particulate sol–gel and cellulose templating techniques. J. Alloys Compd. 568, 102 (2013).CrossRefGoogle Scholar
Cheng, Y.L., Zhang, W.H., Liao, X.P., and Shi, B.: Preparation of porous and fibrous SO42−/TiO2–ZrO2 solid acid using collagen fiber as template and its catalytic behaviour in esterification reaction. Chem. Res. Appl. 26, 1066 (2014).Google Scholar
Devi, K.B., Singh, K., and Rajendran, N.: Sol–gel synthesis and characterisation of nanoporous zirconium titanate coated on 316L SS for biomedical applications. J. Sol-Gel Sci. Technol. 59, 513 (2011).CrossRefGoogle Scholar
Hu, M.Z.C., Payzant, E.A., Booth, K.R., Rawn, C.J., Hunt, R.D., and Allard, L.F.: Ultrafine microsphere particles of zirconium titanate produced by homogeneous dielectric-tuning coprecipitation. J. Mater. Sci. 38, 3831 (2003).CrossRefGoogle Scholar
Gajović, A., Djerdj, I., Furić, K., Schlögl, R., and Su, D.S.: Preparation of nanostructured ZrTiO4 by solid state reaction in equimolar mixture of TiO2 and ZrO2. Cryst. Res. Technol. 41, 1076 (2006).CrossRefGoogle Scholar
Luca, V., Drabarek, E., Griffith, C.S., and Hanley, T.L.: Understanding the supramolecular self-assembly of zirconium titanate mesophases formed from the poly(ethylene oxide) surfactant Brij-58. Chem. Mater. 22, 3832 (2010).CrossRefGoogle Scholar
Luca, V., Soler-Illia, G.J.A.A., Angelomé, P.C., Steinberg, P.Y., Drabarek, E., and Hanley, T.L.: Striving for order and compositional homogeneity in bulk mesoporous zirconium titanium mixed metal oxides from triblock copolymers and metal chlorides. Microporous Mesoporous Mater. 118, 443 (2009).CrossRefGoogle Scholar
Sham, E.L., Aranda, M.A.G., Farfan, M., Gottifredi, J., Martínez-Lara, M., and Bruque, S.: Zirconium titanate from sol–gel synthesis: Thermal decomposition and quantitative phase analysis. J. Solid State Chem. 139, 225 (1998).CrossRefGoogle Scholar
Lu, Q.F., Chen, D.R., and Jiao, X.L.: Synthesis of long ZrTiO4 fibers by a sol–gel process free of organic components. J. Mater. Chem. 13, 1127 (2003).CrossRefGoogle Scholar
Macan, J., Gajovic, A., and Ivankovic, H.: Porous zirconium titanate ceramics synthesized by sol–gel process. J. Eur. Ceram. Soc. 29, 691 (2009).CrossRefGoogle Scholar
Koc, S.N.: Zirconium titanate synthesis by diethanol amine based sol–gel route. J. Sol-Gel Sci. Technol. 38, 277 (2006).Google Scholar
Feinle, A., Elsaesser, M.S., and Hüsing, N.: Sol–gel synthesis of monolithic materials with hierarchical porosity. Chem. Soc. Rev. 45, 3377 (2016).CrossRefGoogle ScholarPubMed
Nakanishi, K.: Pore structure control of silica gels based on phase separation. J. Porous Mater. 4, 67 (1997).10.1023/A:1009627216939CrossRefGoogle Scholar
Tokudome, Y., Fujita, K., Nakanishi, K., Miura, K., and Hirao, K.: Synthesis of monolithic Al2O3 with well-defined macropores and mesostructured skeletons via the sol–gel process accompanied by phase separation. Chem. Mater. 19, 3393 (2007).CrossRefGoogle Scholar
Backlund, S., Smatt, J.H., Rosenholm, J.B., and Lindén, M.: Template-free sol–gel synthesis of hierarchically macro- and mesoporous monolithic TiO2. J. Dispersion Sci. Technol. 28, 115 (2007).10.1080/01932690600992662CrossRefGoogle Scholar
Konishi, J., Fujita, K., Oiwa, S., Nakanishi, K., and Hirao, K.: Crystalline ZrO2 monoliths with well-defined macropores and mesostructured skeletons prepared by combining the alkoxy-derived sol–gel process accompanied by phase separation and the solvothermal process. Chem. Mater. 20, 2165 (2008).CrossRefGoogle Scholar
Guo, X.Z., Li, W.Y., Nakanishi, K., Kanamori, K., Zhu, Y., and Yang, H.: Preparation of mullite monoliths with well-defined macropores and mesostructured skeletons via the sol–gel process accompanied by phase separation. J. Eur. Ceram. Soc. 33, 1967 (2013).CrossRefGoogle Scholar
Guo, X.Z., Zhu, W.J., Cai, X.B., Liu, S.X., and Yang, H.: Preparation of monolithic aluminium titanate with well-defined macropores via a sol–gel process accompanied by phase separation. Mater. Des. 83, 314 (2015).CrossRefGoogle Scholar
Guo, X.Z., Nakanishi, K., Kanamori, K., Zhu, Y., and Yang, H.: Preparation of macroporous cordierite monoliths via the sol–gel process accompanied by phase separation. J. Eur. Ceram. Soc. 34, 817 (2014).CrossRefGoogle Scholar
Sun, M.L., Zhao, T.B., Li, Z.F., Ma, Z.F., Wang, J., and Li, F.Y.: Sol–gel synthesis of macro-mesoporous Al2O3–SiO2–TiO2 monoliths via phase separation route. Ceram. Int. 42, 15926 (2016).CrossRefGoogle Scholar
Kim, T., Oh, J., Park, B., and Hong, K.S.: Correlation between strain and dielectric properties in ZrTiO4 thin films. Appl. Phys. Lett. 76, 3043 (2000).CrossRefGoogle Scholar
Konishi, J., Fujita, K., Nakanishi, K., Hirao, K., Morisato, K., Miyazaki, S., and Ohira, M.: Sol–gel synthesis of macro-mesoporous titania monoliths and their applications to chromatographic separation media for organophosphate compounds. J. Chromatogr. A 1216, 7375 (2009).CrossRefGoogle ScholarPubMed
Zhu, L.Y., Xu, D., Yu, G., and Wang, X.Q.: Preparation and characterization of zirconium titanate fibers with good high temperature performance. J. Sol-Gel Sci. Technol. 49, 341 (2009).CrossRefGoogle Scholar
Naumkin, A.V., Kraut-Vass, A., Gaarenstroom, S.W., and Powell, C.J.: NIST X-ray Photoelectron Spectroscopy Database: NIST Standard Reference Database 20, Version 4.1 (2012). http://srdata.nist.gov/xps.Google Scholar
Moulder, J.M.F., Stickle, W.F.W., Sobol, W.F., and Bomben, K.D.: Handbook of X-ray Photoelectron Spectroscopy (Perkin-Elmer, Eden Prairie, 1992).Google Scholar
Zhu, K.R., Zhang, M.S., Chen, Q., and Yin, Z.: Size and phonon-confinement effects on low-frequency Raman mode of anatase TiO2 nanocrystal. Phys. Lett. A 340, 220 (2005).CrossRefGoogle Scholar
Ikawa, H., Yamada, T., Kojima, K., and Matsumoto, S.: X-ray photoelectron spectroscopy study of high-temperature and low-temperature forms of zirconium titanate. J. Am. Ceram. Soc. 74, 1459 (1991).CrossRefGoogle Scholar