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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 56715674
www.elsevier.com/locate/ceramint

Preparation of UO2/TiO2 composite ceramic fuel by

sol gel-press forming method
Hui Wangn, Huawei Huang, Jinhong Liu
Nuclear Power Institute of China, Chengdu 610041, PR China

Received 10 October 2013; received in revised form 1 November 2013; accepted 2 November 2013
Available online 12 November 2013

Abstract

This paper studies the preparation of UO2/TiO2 composite ceramic fuel through sol gel-press forming. The research shows that at 1200
1300 1C, UO2/TiO2 composite ceramic grains are small, uniform and compact. Among them, UO20.5 wt%TiO2 has the highest density and
good mechanical strength at 1250 1C.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: UO2/TiO2; Composite ceramic; Densication; High burn-up

1. Introduction metal elements in UO2 to inhibit ssion gas release, improve

To develop nuclear power is an inevitable stage to solve the
contradiction between supply and demand of energy, maintain
sustainable economic development and protect the ecological
environment. Nuclear fuel element is considered as the core in
the nuclear reactor. Its performance directly affects the safety,
reliability, economy, performance and service life of the
reactor. In order to improve the efciency of nuclear power,
alleviate the handling and disposal pressure of spent fuel, it is a
long-term goal for nuclear power plants to develop fuel
elements with high burn-up and a long life. However, the
accident at Fukushima Nuclear Power Station caused by the
earthquake and tsunami in Japan in 2011 requires higher
standard for the development of nuclear fuel elements, which
lies in high inherent safety. Therefore, the developmental goal
of a new generation and the future of nuclear power is in the
pursuit of improving its inherent safety performance as well as
making greater economic benets.
Although UO2 ceramic nuclear fuel has many advantages,
for example, high burn-up, the deepening burn-up, however,
can result in sharp increase of the release rate of UO2 ssion
products and worse irradiation swelling [15]. So adding other
n
Corresponding author. Tel.: 86 13709081432; fax: 86 28 85903294.
E-mail address: qinghe5525@163.com (H. Wang).
irradiation resistance and corrosion resistance of fuel phase has
become an important research direction to improve fuel burn-
up [6,7]. The theoretical analysis and calculation by Japanese
scholars Takeo Fujino and others [8] show that under the high
burn-up of irradiation process, irradiation swelling of titanium-
doped UO2 pellets seldom changes. Before and after irradia-
tion, the thermal conductivity of titanium-doped UO2 pellets is
higher than that of UO2 pellets, which greatly improves fuel
irradiation performance and safety performance under high
burn-up. So in order to further deepen the fuel burn-up,
improve safety and economy of nuclear power, research and
development of UO2/TiO2 composite ceramic pellets with high
density and good microstructure will provide technical support
for nuclear power fuel with high inherent safety.
Preparation of UO2/TiO2 composite ceramic mainly lies in
the ball-milling method and powder metallurgic method [9].
But these two methods have the following drawbacks: (1) it is
easy to cause dust pollution and increase radioactive danger for
the staff. (2) Two kinds of ceramic powder are blended to be
pressed into pellets, which easily cause uneven distribution of
titanium and affect the microstructure and the performance
inside and outside the reactor. (3) Pellets made by powder
metallurgic method generally require higher sintering tempera-
ture (1700 1C), which increases the preparation cost of nuclear
fuel. And the sol gel-press forming method, characteristic of

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.11.004
5672 H. Wang et al. / Ceramics International 40 (2014) 56715674
the following advantages, such as uniform chemical composi-
tion within the material, purity and crystal structure, and low
sintering temperature, has become the focus of research and
development of the preparation of composite ceramic materials
at home and abroad. But there is almost no research report on
the preparation of UO2/TiO2 composite ceramic fuel through
sol gel-press forming.
Nano-TiO2 and uranyl nitrate are the initial raw materials in the
experiments in this paper. By the method of sol gel-press forming,
UO2/TiO2 composite ceramic fuel with different contents of TiO2
(mass fraction: 0.5%, 1.0%, 1.5%, and 1.0%) is prepared and
sintered at different sintering temperatures (1150 1C, 1200 1C,
1250 1C, and 1300 1C). The paper studies the inuence of the
sintering temperatures and the content of TiO2 on the sintering
densication, grain sizes and crushing strength. In addition, it also
analyzes its microstructure and distribution of titanium elements
within the fuel. The results provide certain technological and
theoretical basis for the preparation and application of UO2/TiO2
composite ceramic fuel with high burn-up and high inherent safety
in advanced nuclear power.
2. Experimental method
Nano-TiO2 and uranyl nitrate are the initial raw materials. Raw
materials are calculated according to the mass fraction of TiO2,
0.5%, 1.0%, 1.5%, and 2.0%, in the nal product. Nano-TiO2
powder is dissolved in nitric acid and stirred at room temperature to
prepare titanium sol. Titanium sol is instilled slowly into ADUN
(uranyl nitrate) solution. A certain amount of urea and polypropy-
lene glycol are added when the solution is stirred to prepare a
hybrid sol. Then the hybrid sol is put into the crucible and heated
continuously. After a period of time, sol solidies into blocks and
loses liquidity. And then the block sample is dried and calcined at
the high temperature oven. The power after drying calcination is
pressed and molded rst and later sintered under the reducing
atmosphere to get dense UO2/TiO2 composite ceramic fuel pellets.
The sintering atmosphere is of H2. The sintering temperatures are:
1150, 1200, 1250 and 1300 1C. The water immersion method is
used to measure its density, the intensity meter to measure the
fracture strength of the materials and the image analyzer to measure
grain sizes. The scanning electron microscopy SEM is used to
observe material microstructures.
3. Results and discussion
3.1. The inuence of sintering temperatures and the content of
TiO2 on the density of composite ceramic fuel
Fig. 1 shows that when the sintering temperature is at 1150
1300 1C, titanium oxide can signicantly promote the sintering rate
of UO2. The sintered density of UO2/TiO2 composite ceramic fuel
is signicantly higher than that of UO2 fuel. With the increase of
sintering temperature, the densication of UO2/TiO2 composite
ceramic fuel enhances unceasingly. At the sintering temperature of
1250 1C, the theoretical sintered density of UO2/TiO2 composite
ceramic fuel is over 96%, reaching the highest degree of densi-
cation. But when the sintering temperature is further increased,
Fig. 1. The inuence of sintering temperatures and the content of TiO2 on the
density of composite ceramic fuel.
the sintered density of composite ceramic fuel has a downward
trend. It can also be seen from the picture that, in the whole
sintering temperature range, when TiO2 content is 0.5 wt%, the
densication of UO2/TiO2 composite ceramic fuel is most
signicant. With the increase of TiO2 content, the sintered density
of UO2/TiO2 composite ceramic fuel basic does not change. When
TiO2 content is more than 1.5 wt%, the sintered density of fuel
declines.
Therefore, the densication of UO2/TiO2 composite ceramic
fuel does not increase with the increase of TiO2 content and the
sintering temperature. When TiO2 content is 0.5 wt% and the
sintering temperature is 1250 1C, the theoretical sintered
density of UO2/TiO2 composite ceramic fuel is over 96%,
reaching the highest degree of densication. But when TiO2
content is over 0.5%, the sintered density of UO2/TiO2
composite ceramic fuel basic does not change basically. When
TiO2 content is more than 1.5 wt%, the sintered density of fuel
declines. This may be due to low solid solubility of TiO2 in
UO2. TiO2 which exceeds the solid solubility might affect
material migration as free phase dispersed particles, thus
hindering the sintering densication of UO2 and resulting in
a few changes or even slight reduction of the sintered density.
3.2. The inuence of sintering temperatures and the content of
TiO2 on the grain sizes of composite ceramic fuel
Fig. 2 shows that when the sintering temperature is at 1150
1300 1C, titanium oxide can effectively promote the grain
growth of UO2 microspheres. In the whole range of the
sintering temperatures, when TiO2 content is 0.5 wt%, the
grain growth of UO2/TiO2 composite ceramic fuel is most
signicant. With increase of TiO2 content, the grains of
UO2/TiO2 composite ceramic fuel grow slowly with a
slight downward trend. The grain sizes of UO2/TiO2 composite
ceramic fuel with the same content of TiO2 increase
with temperature rise. Especially when the sintering tempera-
ture exceeds 1250 1C, the grain sizes increase more signi-
cantly. When the TiO2 content is 0.5 wt% and the sintering
 H. Wang et al. / Ceramics International 40 (2014) 56715674
Fig. 2. The inuence of sintering temperatures and the content of TiO2 on the
grain sizes of composite ceramic fuel.
temperature is 1300 1C, the grain size of UO2/TiO2 composite
ceramic fuel reaches the maximum.
From the above-mentioned experiment results, large grains
of UO2 can be obtained by adding a small amount of TiO2.
A large amount may hinder the grain growth. Temperature has
a great inuence on grain growth. The higher the temperature
is, the faster the material migration rate and the grain growth
are. The experimental results from Fig. 2 are consistent with
other material grain growth laws, namely, the higher the
sintering temperature is, the larger the grain size is.
3.3. The inuence of sintering temperatures and the content of
TiO2 on the strength of composite ceramic fuel
Crushing strength tests are done on UO2/TiO2 composite
ceramic fuel samples which have been sintered at 1150 1C,
1200 1C, 1250 1C, and 1300 1C with different contents of
TiO2. The inuence of sintering temperatures and the content
of TiO2 on the crushing strength of composite ceramic fuel is
shown in Fig. 3. According to Fig. 3, at 1150 1C, 1200 1C,
1250 1C and 1300 1C, the variation tendency of the strength of
UO2/TiO2 composite ceramic fuel is basically consistent with
that of different contents of TiO2 which means that when TiO2
in the composite ceramic materials increases from 0 to 0.5 wt
%, the strength of the sample greatly increases. When TiO2
content increases from 0.5 wt% to 2.0 wt%, the strength of the
sample varies a little with a slight downward trend.
From the analysis of Figs. 1 and 2, when TiO2 is 0.5 wt% in
the composite ceramic fuel, the densication degree of the
sample is high, so the sample has higher exural strength.
When the TiO2 is 0.5 wt% at 1300 1C, composite ceramic fuel
has the highest exural strength of 24.5 MPa. The increase of
TiO2 has little impact on the sintering and strength of
composite ceramic fuel. This kind of phenomenon is identical
to the situation of the inuence of TiO2 content on the sintered
density.
5673
Fig. 3. The inuence of sintering temperatures and the content of TiO2 on the
strength of UO2/TiO2 composite ceramic fuel.
3.4. The analysis of the microstructure and titanium
distribution of UO2/TiO2 composite ceramic fuel
Fig. 4 shows microscopic structure (SEM) and the titanium
element distribution of UO20.5 wt%TiO2 composite ceramic
fuel at different sintering temperatures. It can be seen that there
is no obvious free phase in the sintered body of UO20.5 wt%
TiO2 composite ceramic fuel. Composite ceramic grains are
small, uniform and closely arranged with good compactness.
In addition, after UO20.5 wt%TiO2 composite ceramic fuel is
sintered at 1200 1C, 1250 1C and 1300 1C, titanium is uni-
formly distributed within the fuel grains. Therefore, it also
illustrates that the sintered body of UO20.5 wt%TiO2 com-
posite ceramic fuel forms a stable solid solution with good
sintering property and mechanical strength.
If the inuence of TiO2 content and sintering temperatures
on the sintered density, grain sizes and crushing strength of
composite ceramic fuel samples is taken into account as a
whole, UO20.5 wt%TiO2 composite ceramic fuel samples
with 0.5 wt% TiO2 at 1200 1C has a good sintering effect with
high sintered density and exural strength as well as uniform
growth of grain sizes and good microstructure. Therefore,
0.5 wt% of TiO2 and the sintering temperature of 1250 1C are
suitable for the preparation of UO20.5 wt%TiO2 composite
ceramic fuel with high density and strength as well as good
microstructure.
4. Conclusion
(1) When TiO2 in the composite ceramic fuel increases from 0
to 0.5 wt%, the sintering performance of the sample greatly
increases. But when TiO2 content increases from 0.5 wt%
to 2.0 wt%, the sintered density of the sample varies a
little.
(2) When TiO2 in the composite ceramic fuel increases from 0
to 0.5 wt%, the crushing strength of the sample greatly
increases. But when TiO2 content increases from 0.5 wt%
to 2.0 wt%, the strengths of the sample change a little.
5674 H. Wang et al. / Ceramics International 40 (2014) 56715674
Fig. 4. SEM diagram and titanium distribution of UO20.5 wt%TiO2 composite ceramic fuel at different sintering temperatures. (a) 1200 1C, (b) 1250 1C and (c) 1300 1C.
(3) Within the whole range of sintering temperatures, when
TiO2 is 0.5 wt%, the grain growth of UO2/TiO2 composite
ceramic fuel is most signicant. With the increase of TiO2
content, the grain sizes of UO2/TiO2 composite ceramic
fuel vary a little.
(4) If the inuence of composite materials composition and
sintering temperatures on the sintering performance of the
materials is taken into account as a whole, 0.5 wt% of TiO2
and the sintering temperature of 1250 1C are suitable for
the preparation of UO2/TiO2 composite ceramic fuel with
high density and strength, uniform grain sizes as well as
good microstructure.
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