SYNTHESIS OF NANO-SIZED ZIRCONIA CERAMICS
VIA A PRECERAMIC POLYMER METHOD
Translated from Novye Ogneupory, No. 2, pp. 40 – 44, February 2014.
Original article submitted October 14, 2013.
Polyzirconoxane (PZO) was prepared by a one-pot reaction of zirconium oxychloride octahydrate (ZOC) with
acetylacetone. Triethylamine was added dropwise into a mixture of zirconium oxychloride octahydrate,
acetylacetone, and methanol to get stable PZO. The PZO polymer was characterized by the techniques of Fou
rier transform infrared spectra (FTIR), nuclear magnetic resonance (
H-NMR), and gel permeation chroma
tography (GPC). The precursor was air-stable and soluble in common organic solvents. The thermal behavior
of PZO consisted of three stages, namely, loss of water and solvent, decomposition of organic residues, and
dehydroxylation of ZrOH into ZrO
. Pyrolysis of this polymer at 1000°C in nitrogen provides nanosized ZrO
with spherical morphology and size of 50 – 100 nm.
Keywords: polyzirconoxane; zirconium oxychloride octahydrate; zirconia; nanosized
Among various transition metal oxides, zirconium oxide
) has been considered as an important mate-
rial due to several unique properties that make it versatile for
a number of applications. It can be effectively applied as cat-
alysts [1, 2], catalyst supports [3, 4], dielectric materials
[5, 6], high-performance ceramic materials [7, 8], chemical
sensors [9, 10], solid oxide fuel cells [11, 12], as well as soli
tary photocatalytic materials [13, 14]. Thus far, it has been
one of the most promising oxides for functional and struc
A lot of methods have been explored for synthesizing
zirconia, including precipitation, sol-gel technology, thermal
decomposition, hydro-thermal treatment, and the precursor
method. Among this, the preceramic polymer method is a
relatively new and effective approach for preparing advanced
ceramics by thermal decomposition of the polymers .
The main advantages of such method of synthesizing poly
mer derived ceramics are the applicability of polymer-pro
cessing techniques, the homogeneity of the precursors on a
molecular level, the low processing temperatures when com-
pared to conventional powder sintering methods, and the
possibility of synthesizing new compounds. Using this
chemical approach, one can tailor the chemistry and poly-
merization of the starting molecular precursor to adjust the
composition and viscoelastic properties of the derived
preceramic polymer and therefore prepare complex shapes
(films, fibers, coatings) and ceramic matrix composites in a
wide variety of systems. Despite the numerous studies based
on the precursor synthesis routes for the different classes of
preceramic polymers, such as polysilanes, polysiloxanes,
polysilazanes, etc., only a few papers have focused on the
synthesis of preceramic polymer for ZrO
by chemical reac
Polyzirconoxane (PZO) [16, 17], as precursors for pre
paring zirconia (ZrO
) ceramics, is an alkane- and arene-sol
uble, water-free polymer. Ethyl acetoacetate (Hetac) has
been used to react with zirconium oxychloride in the pres
ence of triethylamine to synthesize polyzirconoxanes (PZOs)
as precursors for preparing zirconia (ZrO
) fibers [18 – 21].
Ethylene glycol (EG) was reported to react with zirconium
oxychloride to synthesize EG-PZO . In present paper, we
use inorganic zirconium oxychloride as zirconium source
and acetylacetone as ligand to synthesize a new precursor for
; its characterization, properties and pyrolytic
behavior were also investigated.
Refractories and Industrial Ceramics Vol. 55, No. 1, May, 2014
1083-4877/14/05501-0063 © 2014 Springer Science+Business Media New York
School of Materials Science and Engineering, China University
of Mining and Technology, Xuzhou 221116, China.
Laboratory of Advanced Polymer Materials, Institute of Chemis
try, Chinese Academy of Sciences, Beijing 100190, China.
School of Chemical Engineering and Technology, China Univer
sity of Mining and Technology, Xuzhou 221116, China.