Fusion Engineering and Design 113 (2016) 146–150

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Fusion Engineering and Design

journal homepage: www.elsevier.com/locate/fusengdes

Sol–gel followed by urea–acetone spherodization for preparation of

lithium titanate ceramics pebbles and preliminary characterization
S.K. Sinha a,∗ , S. Yadav a , P.M. Raole b
a
Department of Physics, Birla Institute of Technology, Patna 800014, India
b
Institute for Plasma Research, Bhat, Gandhinagar 382428, India

a r t i c l e i n f o a b s t r a c t

Article history: Lithium titanate ceramics pebbles were prepared by chemical method of sol. gel followed by urea-aceton
Received 25 September 2015 spherodization technique. Lithium titanate having monoclinic phase was obtained. Laser flash method
Received in revised form was used to study thermal conductivity and diffusivity of the ceramics. At near 472 K the average value
13 September 2016
of diffusivity was around 0.0052 cm2 s−1 while the specific heat capacity was 3101.3 J kg−1 K−1 while the
Accepted 28 October 2016
same two parameters had values of 0.0041 cm2 s−1 and 3894.4 J kg−1 K−1 at a temperature 1050 K. The
Available online 9 November 2016
crush strength of pebble was measured on Universal Testing Machine (UTM) and was found as 37.08 N.
The density was measured and found to be 2.8 g/cc (81.63% of TD of value 3.43 g/cc).
Keywords:
Lithium titanate © 2016 Elsevier B.V. All rights reserved.
Sol–gel followed by urea-acetone technique
Thermal conductivity
Crush strength

1. Introduction selectively dissolved in low HNO3 concentration [6]. Apart from

Lithium-based ceramics have been recognized as promising tri-
tium breeder material for fusion research reactor blankets [1–8].
These ceramics have excellent potential as tritium breeder because
of the ease of tritium recovery, excellent thermo-mechanical,
thermo physical properties and good irradiation behavior under
long-term irradiation at high temperature and large temperature
gradients. They are Li2 O, Li2 ZrO3 , LiAlO2 , Li4 SiO4 and Li2 TiO3 and
others. These materials are potentially regarded as the breeder
material for breeder blanket application in fusion reactor. Indeed
their inherent thermal stability and chemical inertness are signif-
icant safety advantages. The breeder blanket is a key component
of the fusion reactor because it directly involves tritium breeder
and energy extraction, both of which are critical to development of
fusion power.
Recently, attention shifted to lithium titanate (Li2 TiO3 ), when
it was proposed as the potential candidate material in a breeder
blanket because of several advantages over other similar materi-
als [4,5]. One of them is the ease with which tritium is recovered
at low temperature. Li2 TiO3 is especially a good material from the
viewpoint of reprocessing because lithium titanate Li2 TiO3 can be
∗ Corresponding author at: P.0. BV College, Patna 800014, India.
E-mail addresses: sk.sinha@bitmesra.ac.in, drsanjay1011@gmail.com
(S.K. Sinha).
that lithium density also play a significant role in tritium breeding
and its recovery, and also Li2 TiO3 pebbles have been supposed to
use in the blanket so it is required to produce/fabricate desirable
dense pebbles with desired thermal and mechanical properties.
It has been further recognized that lithium recovery is propor-
tional to some extent to its electrical conductivity so attention is
also shifted to fabricate desired geometry ceramics with required
electrical conductivity [7], microstructure and activation energy for
better production and recovery of tritium.
Fabrication of lithium titanate ceramics in pebble form is
reported to be much more suitable for breeder blanket applica-
tion as it produces optimum tritium in comparison of other shape
or state. K.Tsuchiya et al. were reported the fabrication of Li2 TiO3
pebbles by wet processes and achieved 80–85% TD, further they
reported successful control over particle size and density of the
pebbles by adopting dehydration and substitution reactions [1,2]. T.
Hoshino et al. had projected a sol. gel. method by help of which mass
decrease in Li2 TiO3 pebbles at elevated temperature can be pre-
vented by adding Li(Li2+x TiO3+y ), they further reported a method
of emulsion for fabrication and achieved pebble density in the rage
of 85% TD [3,4]. Different way of fabrication for Li2 TiO3 pebbles are
reported [1–10]. For breeder blanket application, one of the fore-
most requirements of pebble is related to proper mechanical crush
strength such that it can sustain in harsh environmental condition
of fusion reactor. Mandal et al. [11] had reported the fabrication of
lithium titanate pebbles by solid state method having dia 2 mm and

http://dx.doi.org/10.1016/j.fusengdes.2016.10.018
0920-3796/© 2016 Elsevier B.V. All rights reserved.
 S.K. Sinha et al. / Fusion Engineering and Design 113 (2016) 146–150 147

Fig. 1. (a): Photograph of spheridization of lithium titanate pebbles. (b): Lithium

titanate pebbles after sintering at 1100 ◦ C.

crush strength 25 N. In present work, chemical method of sol. gel.

technique followed by spherodization of lithium titanate with the
help of urea-acetone solution was adopted. Lithium titanate mon-
oclinic phase was obtained. No high temperature calcination was
needed in obtaining required phase. Laser flash method was used to
study thermal conductivity and diffusivity of the sample. At 472 K
the average value of diffusivity was observed as 0.0052 cm2 s−1
while the specific heat capacity was found as 3101.3 J kg−1 K−1 . The
crush strength of pebble was measured on UTM Machine and was
found as 37.08 N. The density was measured and found to be 2.8 g/cc
Fig. 2. (a) SEM micrograph of pebble sintered at 1100 ◦ C for three hours. (b) SEM
(81.63% of TD of value 3.43 g/cc) [12–14]. micrograph of pebble sintered at 1150 ◦ C for 3 h. (c) SEM micrograph of pebble
sintered at 1200 ◦ C for 3 h.

2. Material and methods

2.1. Fabrication of lithium titanate
Required weight of Titanium (IV) butoxide was taken and
dissolved in a small amount of ethanol to make the solution concen-
trated. Limited amount of citric acid was weighed and diluted with
minimum amount of distilled water to prepare the citrate solution.
Ammonia solution was added to the citrate solution to adjust the pH
of the solution around 9.0. Solutions as obtained were mixed under
vigorous and continuous stirring for more than half an hour while
keeping the temperature of the hot plate around 30 ◦ C. pH of the
titanium sol so obtained was monitored and kept at 9.0 through-
out the process. pH value was monitored by taking out sample from
hot plate and checking the pH value manually. Ammonia solution
was added to maintain the pH value. Lithium nitrate solution was
obtained by dissolving the required amount of lithium nitrate pow-
der to the distilled water. The lithium nitrate solution was added
drop wise to the titanium sol by simultaneously monitoring the pH
148 S.K. Sinha et al. / Fusion Engineering and Design 113 (2016) 146–150
Fig. 3. XRD pattern of calcined Li2 TiO3.
of the solution. Materials were taken considering stiochemetry of
final product. The whole solution was left under constant stirring
for next 2 h, while the temperature of the hot plate was increased
up to 80 ◦ C. After 2 h, stirring rate was kept under 250 rpm while
temperature of the hot plate was kept at 80 ◦ C for the next 4–6 h
and then stirring was switched off and obtained sol was left till
the formation of highly viscous yellowish transparent gel. A small
amount was calcined at 800 ◦ C for 3 h for phase analysis or XRD (X-
ray diffraction). The XRD confirms the preparation of pure phase
of lithium titanate (Li2 TiO3 ). The intensity peaks are found at var-
ious 2theta angles which matched with the JCPDS data file and
confirmed the lithium titanate of monoclinic phase [15–20].
2.2. Process of ceramic pebbles preparation
Urea solution was prepared in hydrochloric acid. Urea solution
and aceton were mixed in a molecular proportion 3:1 and heated
and stirred at 40 ◦ C for 15 min. Now this solution was acting as an
organic binder known as triacetonediurea [17]. Triacetonediurea
is having empirical formula C11 H20 N4 O2 . There is increase in sur-
face tension against air due to mixing of urea in acetone results
into better pebble formation capacity. Precursor sol was dropped
in the urea-acetone solution through a nozzle and gel spheres were
formed due to the dehydrating and binding nature of the urea-
acetone and the effect of surface tension. The gel spheres were
aged in solution for sufficient time to acquire sufficient stability.
The aging process was carried out at 35 ◦ C in air. The gel spheres
were dried in different stages. Photographs of lithium titanate peb-
bles are displayed in Fig. 1(a) and(b). SEM micrograph of pebble
sintered at 1100 ◦ C, 1150 ◦ C, 1200 ◦ C at socking time 3 h are shown
in Fig. 2(a–c) respectively.
2.3. Characterizations
Crystallographic phase analysis of the lithium titanate powder
calcined at 800 ◦ C for three hours were carried out by X ray diffrac-
tion (Rigaku RAD-C, 12 KW) using Cu K ␣. XRD pattern is shown in
Fig. 3. Density of the sintered lithium titanate pebbles were mea-
sured by using Wensar model HPB220 and is displayed in Fig. 4. Bulk
density of sinter specimens were determined by Archimedes prin-
ciple. Sintered samples were weighted in dry state. Samples were
immersed in mercury and kept under a vacuum desiccators for 2 h
to ensure that murcury filled up the open pores completely. Then,
soaked and suspended weights were measured. The bulk density
were calculated as follows:
Wd = Dry weight of the sample,
Ws = Soaked weight of the sample,
Wa = Suspended weight of the sample.
Bulk density = Wd * Density of mercury/Ws − Wa
Thermal conductivity, diffusivity and specific heat capacity of
the sample sintered at 1100 ◦ C for three hours in air atmosphere
were carried out at two different temperatures (at 199 K and
784 K) results are shown in Table 1. Samples were made by apply-
ing varying low-pressure i.e. 5 to 20 psi followed by sintering at
1100 ◦ C, 1150 ◦ C and 1200 ◦ C for three hours. SEM test of prepared
pellets were done. Clear grains can be observed in SEM micro-
graphs.Thermal conductivity and diffusivity test was carried out
of the sample having thickness 0.2095 cm and diameter 12.7 mm.
Crush strength test of pebble was done by universal testing machine
(UTM) and is shown in Fig. 5.
3. Results and discussions
3.1. Phases of the product
The XRD confirms the preparation of pure phase lithium titanate
(Li2 TiO3 ). The intensity peaks were found at various 2␪ angles
which match with the JCPDS data file and confirms the lithium
titanate monoclinic phase. Debye Scherer formula was used to
obtain the average crystallite size of the sample powder which was
found to be around 35 nm. The observed peaks were matched with
JCPDS file (PDF 33-0831) which confirmed the C2/c space group
monoclinic structure.
3.2. Densification
The bulk density of lithium titanate pebbles was calculated
while the average diameter of pebbles were measured and found
in the range of 1.8–2.0 mm. Grain size of pebble was found as
0.5–2 ␮m as per the SEM micrograph. The calculated bulk density
 S.K. Sinha et al. / Fusion Engineering and Design 113 (2016) 146–150 149

3.0

2.8
Variation of density with temperature
2.6

2.4

Density (g/cc) 2.2

2.0

1.8

1.6

1.4

1.2

1.0

700 800 900 1000 1100 1200

o
Temperature ( C)

Fig. 4. Variation of Density with temperature in Li2 TiO3.

Table 1
Thermal conductivity, diffusivity and specific heat capacity of the sintered Li2 TiO3 pellets sintered at 1100 ◦ C.

Temperature in (◦ C) Thermal diffusivity (cm2 s−1 ) Specific heat capacity (J kg−1 K−1 ) Thermal conductivity (Wm−1 K−1 )

Shots Average Shorts Average Shorts Average

0.0051 3258.1 2.5544

199 0.0052 0.0052 2944.5 3101.3 2.2125 2.3834
0.0053

0.0041 3991.0 2.3001

784 0.0041 0.0041 4219.9 3894.4 2.5532 2.3421
0.0042 3472.3 2.1728

50 in density of pebbles were observed. The maximum density of the

F verses t graph F=37.08N t=41.46 sec. pebbles was found near 1100 ◦ C.
Breaking Point
40
3.3. Thermal behaviors
Load(F in N)

30 Thermal conductivity and diffusivity of the Li2 TiO3 pellet sin-

20
10
0
0 10 20 30
Time(in sec.)
Fig. 5. Load vs Time curve for Li2 TiO3 pebble sintered at 1100 ◦ C.
was 2.8 g/cm3 (81.63% of TD value 3.43), similar work was reported
by Tsuchiya et al. [6]. Change in density with sintering temperature
is shown in Fig. 5. The graph suggests the variation of the observed
density at the elevated temperature. Measurement was performed
from 700 ◦ C to 1250 ◦ C. The sphericity of the pebbles (defined as
the ratio of minimum diameter to the maximum diameter) was
0.91. The graph also suggests that with this method one can pre-
pare dense pebbles. With further raise in temperature the decrease
tered at 1100 ◦ C for three hours in air atmosphere was carried out.
Pellet was tested for thermal conductivity, thermal diffusivity and
specific heat capacity at two temperatures 199 ◦ C and 784 ◦ C using
Laser flash apparatus and compared with the available data. Details
are given in Table 1.
Thermal conductivity, thermal diffusivity and specific heat
capacity are related by equations
Kth = ␳Cp␣
40 50 60 70 80
Where k is thermal conductivity in W/mK, ␳ is the density in g/m3 .
Thermal conductivity of a porous material varies not only with
porosity, but also with the grain size and pore shape, the pore distri-
bution, the cracks and so on [22]. These variables may be affected by
starting materials, preparation procedure and temperature history
of the specimen reported by Shigeru Saito et al. [23].
There is an equation in common use, describing the influence
of porosity on thermal conductivity, the modified Maxwell-Eucken
equation, which is as follows [24,25]
K = Ko ∗ (1 − P)/(1 + ␤p)
Where KO (W/mk) is the thermal conductivity when the density is
100% T.D., porosity in non-dimensional units and ␤ is an empirical
parameters.
150 S.K. Sinha et al. / Fusion Engineering and Design 113 (2016) 146–150
The thermal conductivity of the sample at room temperature is
about 3 W/mK, falling to 2.2 W/mK from 425 K to 625 K after which
it rises gradually to 2.6 W/mK at 1000 K reported by Davis et al.
[17]. As the table suggests, at near 472 K the average value of dif-
fusivity is around 0.0052 cm2 s−1 while the specific heat capacity
is 3101.3 J kg−1 K−1 while the same two parameters have numeri-
cal values of 0.0041 cm2 s−1 and 3894.4 J kg−1 K−1 around 1057 K.
This shows that both the thermal conductivity as well as the spe-
cific heat capacity increase with rise in temperature. While thermal
conductivity depends both on density as well as porosity, hence it
first decrease, attains a minimum and further increase up to 1100 K.
Trends of present reported value of thermal diffusivity, thermal
conductivity and specific heat capacty are similar as reported by
workers [22–24] for sample L100 having relative density 80%.
3.4. Crush strength
The crush strength was measured using UTM (universal testing
machine). A sintered pebble was placed between flat surfaces of
a specially designed load cell. The compressive load was applied
on the pebble under the test. Pressure on pebble was gradually
increased till the pebble cracked. The observed graph is shown in
Fig. 5. Experimental data curve peak point represent that pebble
cracked at load 37.08 N.
In the present report, the crush strength of the sintered Li2 TiO3
pebbles was observed as 37.08 N for pebble having dia 2 mm,
1.5 ␮m grains and density 2.8 g/cm3 . D. Mandal et al. had reported
the crushed strength in the range of 16–20 N [11]. Y.Futamura
reported that crush strength was found to be 30 N of the peb-
bles having 4–10 ␮m grains, 85% dense 1.2 mm pebbles size, 40 N,
40–140 ␮m grains, 78% dense, 1.2 mm 40N, 1–20 ␮m grains 67%
dense, 1.6 mm pebbles size respectfully [21]. K.Tsuchiya et al. has
reported the crush strength as 73.4 N for pebble having dia 1.5 mm,
2.86 ␮m grains and density 2.86 gm/cm3 [2]. It has also been
reported [25], about the decrease in the crush strength due to
sweeping of hydrogen gas. It has also been studied and inferred
that the mechanical strength of solid breeding materials is largely-
concerned with Ti valence ratio and Li/Ti ratio [20–21].
4. Conclusions
A method of sol. gel. followed by urea-aceton spheridization was
used for preparation of lithium titanate ceramics pebbles. The pure
phase nano-crystalline lithium titanate was successfully obtained
with an average crystallite size of 23 nm. Thermal conductivity
measurement on the sintered pellets supports the earlier study on
this material, which is compatible for the blanket application in
fusion reactor. The Crush strength of the sintered Li2 TiO3 pebbles
was found as 37.08 N/pebbles and density achieved was 2.8 gm/cc
(81.63% of TD). Thermal conductivity at 300 K was found as 3 W/mK.
Acknowledgements
We thankfully acknowledge the help rendered by Dr. Manoran-
gan kar (IIT Patna) for providing facility for crush strength
measurement. Help in taking thermal conductivity measurement
by Dr. Ansu J. kailath of NML Jamshedpur is thankfully acknowl-
edge. Permission by Vice Chancellor, BIT Mesra and Director, BIT
Patna to conduct experiments and to use measurement facility was
highly helpful in completion of the project. We would like to thank
the Board of Research in Fusion Science & Technology (BRFST), Insti-
tute for Plasma Research, Gandhinagar, Government of India, for
financial support (Project code: NFP/MAT/A10-02).
References
[1] K. Tsuchiya, H. Kawamura, Development of wet process with substitution
reaction for the mass production of Li2 TiO3 pebbles, J. Nucl. Mater. 283–287
(2000) 1380–1384.
[2] K. Tsuchiya, H. Kawamura, T. Takayama, Control of particle size and density of
Li2 TiO3 pebbles fabricated by indirect wet process, J. Nucl. Mater. 345 (2005)
239–244.
[3] T. Hoshino, Fumiaki Oikawa, Trial fabrication test of advanced tritium breeder
using sol-gel method, Fusion Eng. Des. 86 (9–11) (2011) 2172–2175.
[4] T. Hoshino, M. Nakamichi, Development of fabrication technologies for
advanced breeding functional materials for DEMO Reactors, Fusion Eng. Des.
87 (5–7) (2012) 486–492.
[5] Xiangwei Wu, Zyaoyin Wen, Xiaoxiong Xu, Zhonghua Gu, Xiaohe Xu,
Optimization of a wet chemistry method for fabrication of Li2 TiO3 pebbles, J.
Nucl. Mater. 373 (2008) 206–211.
[6] K. Tsuchiya, H. Kawamura, Fabrication development and preliminary
characterization of Li2 TiO3 pebbles by wet chemistry, J. Nucl. Mater. 258–263
(1998) 1985–1990.
[7] T. Hoshino, Development of fabrication technologies for advanced tritium
pebbles by the sol-gel method, Fusion Eng. Des. 88 (9–10) (2013) 2264–2267.
[8] Xiangwei Wu, Zhaoyin Wen, Bin Lin, Xiaogang Xu, Sol–gel synthesis and
sintering of nano-size Li2 TiO3 powder, Mater. Lett. 62 (6–7) (2008) 837–839.
[9] Xiangwei Wu, Zhaoyin Wen, Jinduo Han, Xiaoxiong Xu, Bin Lin, Fabrication of
Li2 TiO3 pebbles by water-based sol–gel method, Fusion Eng. Des. 83 (1)
(2008) 112–116.
[10] Min Guo, et al., Synthesis of novel nitrogen-doped lithium titanate with
ultra-high rate capability using melamine as a solid nitrogen source, J. Mater.
Chem. A 3 (2015) 10753–10759.
[11] D. Mandal, et al., Synthesis & fabrication of lithium-titanate pebbles for ITER
breeding blanket by solid state reaction & spherodization, Fusion Eng. Des. 85
(5) (2010) 819–823, http://dx.doi.org/10.1016/j.fusengdes.2010.06.018.
[12] P. Gierszewski, et al., Review of properties of lithium metatitanate, Fusion
Eng. Des. 39–40 (1 September) (1998) 739–743.
[13] M. Vijayakumar, S. Kerisit, Z. Yang, G.L. Graff, J. Liu, J.A. Sears, S.D. Burton, K.M.
Rosso, Combined 6,7Li NMR and molecular dynamics study of Li diffusion in
Li2TiO3, J. Phys. Chem. 113 (2009) 20108–20116, http://dx.doi.org/10.1021/
jp9072125.
[14] H. Kleykamp, Phase equilibria in the Li–Ti–O system and physical properties
of Li2TiO3, Fusion Eng. Des. 61 (2002) 361–366.
[15] Laumann Andreas, Jensen Ørnsbjerg, Kirsten Marie, Tyrsted Christoffer,
In-situ synchrotron X-ray diffraction study of the formation of cubic Li2 TiO3
under hydrothermal conditions, Eur. J. Inorg. Chem. 14 (2011) 2221–2226,
http://dx.doi.org/10.1002/ejic.201001133.
[16] B.S. Sahu, S. Bhatacharyya, P. Chaudhuri, R. Mazumder, Synthesis and
sintering of nanosize Li2TiO3 ceramic breeder powder prepared by
autocombustion technique, J. Mater. Sci. 23 (2013) 234.
[17] D.A.H. Hanaor, M.H.H. Kolb, Y. Gan, M. Kamlah, R. Knitter, Solution based
synthesis of mixed-phase materials in the Li2 TiO3 -Li4 SiO4 system, J. Nucl.
Mater. 456 (2014) 151–161, http://dx.doi.org/10.1016/j.jnucmat.2014.09.028.
[18] R.P. Maloney, H.J. Kim, J.S. Sakamoto, Lithium Titanate Aerogel for Advanced
Lithium-ion Batteries, Department of Chemical Engineering and Materials
Science, Michigan State University, 2016 http://pubs.acs.org/doi/pdf/10.1021/
am3002742.
[19] J.P. Kopasz, et al., Tritium release from lithium titanate, a low-activation
tritium breeding material, J. Nucl. Mater. 212–215 (1994) 927–931.
[20] C.E. Johnson, G.W. Hollenberg, N. Roux, H. Watanabe, Current experimental
activities for solid breeder development, Fusion Eng. Des. 8 (1989) 145–153.
[21] D. Cruz, H. Pfeiffer, S. Bulbulian, Synthesis of the lithium metatitanate by the
modified combustion method, Solid State Sci. 8 (2006) 470–476.
[22] Shigeru Saito, Kunihiko Tsuchiy, Hiroshi Kawamura, Takayuki Terai, Satoru
Tanaka, Density dependence on thermal properties of Li Ti O pellets, J. Nucl.
Mater. 253 (1998) 213–218.
[23] G. Ondracek, B. Schulz, The porosity dependence of the thermal conductivity
for nuclear fuels, J. Nucl. Mater. 46 (1973) 253–258.
[24] Y. Takahashi, T. Terai Ohsato, H. Kawamura, Thermal Conductivity of Li Al O2 ,
Li Si O3 , Li Zr O3 , Adv. Ceram. 27 (1989) 199–218.
[25] J.W. Davis, A.A. Haasz, Fusion Research Group, University of Toronto Institute
for Aerospace Studies, 4925 Dufferine St. North York, ON, Canada M3H 5T6,
2016.