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Lithium Disilicate (Li2Si2O5): Mild Condition Hydrothermal Synthesis,

Characterization and Optical Properties

Article · December 2014

DOI: 10.7508/jns.2014.04.001

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Abdolali Alemi Shahin Khademinia

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 JNS 4 (2014) 407- 412

Lithium Disilicate (Li2Si2O5): Mild Condition Hydrothermal Synthesis,

Characterization and Optical Properties
Abdolali Alemi a, Shahin Khademinia a,* Murat Sertkolb
a
Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
b
Department of Physics Engineering, Istanbul Technical University, Maslak, 34469, TR

Article history: Abstract

Received 3/10/2014 Lithium disilicate nano-powders were synthesized via a mild
Accepted 9/11/2014
condition hydrothermal reaction at 180 ºC for 48 and 72 h with a non
Published online 21/12/2014
stoichiometric1:2 Li:Si molar ratio in NaOH aqueous solution using
Keywords: Li2CO3 and SiO2.H2O as raw materials. The synthesized materials
Chemical synthesis were characterized by powder X-ray diffraction (PXRD) technique
Nano-Structured material and Fourier transform infrared (FTIR) spectroscopy. The XRD data
Magnetic material showed that the obtained materials crystallized in a monoclinic
Cobalt
crystal structure with a space group of Ccc2. The morphologies of the
*Corresponding author: synthesized nanomaterials were studied by field emission scanning
E-mail address: electron microscope (FESEM). Ultraviolet–visible spectra showed
[email protected] that the nanostructured lithium disilicate powders had good light
Phone: 98 912 1936361 absorption properties in the ultraviolet light region. Photo
Fax: +98 21 88006076 luminescence spectra of the obtained materials were investigated in
an excitation wavelength of 281 nm. Cell parameter refinement data
of the obtained materials showed that with increasing the reaction
time, parameters a and b were increased. So there is an expansion in
the unit cell.
2014 JNS All rights reserved

1. Introduction in optical waveguide devices [8-13]. Different

Lithium ceramics have some technological experimental syntheses have been reported to
applications. Among these ceramics, lithium synthesize Li2Si2O5 nano materials such solid state
silicates have been investigated as breeder reaction, precipitation, sol–gel method, extrusion-
materials for nuclear fusion reactors, carbon spherodisation process, rotating/melting
dioxide absorbents, thermal expansion of glass procedures, combustion, electrochemical method,
ceramics and so many other applications [1-7]. and recently via hydrothermal method. However,
Lithium disilicate is used as pyroelectric materials most of the time, a mixture of Li2SiO3, Li2Si2O5,
408 S. Khademinia et al./ JNS 4 (2014) 407- 412

Li4SiO4, and SiO2 were obtained [14, 15, 18-23]. resultant solution was stirred further for 15 min.
Recently, we have reported the synthesis of highly The obtained solution was transferred into a 100-
crystalline and pure lithium disilicate nanomaterials mL Teflon lined stainless steel autoclave. The
through a mild condition via hydrothermal method autoclave was sealed and heated at 180°C for 48
at 180°C with lithium nitrate and silicic acid as raw (sample 1) or 72 h (sample 2). When the reaction
materials at 1:3 Li:Si molar ratio [24]. In the was completed, it cooled to room temperature by
present study, a hydrothermal route was explored water immediately. The prepared powder washed
successfully to synthesize nanostructure Li2Si2O5 with distilled water and dried at 110°C for 20 min
powders in a hydrothermal system of Li2CO3, under normal atmospheric conditions. And allowed
SiO2.H2O and NaOH. To the best of our to cool slowly to room temperature, a white powder
knowledge, there is no report on the synthesis of was collected.
nanostructure Li2Si2O5 crystallites by these raw
materials. 3. Result and discussion
3.1. Powder X-ray diffraction analysis
2. Materials and methods The crystal phases of the synthesized
nanomaterials with different reaction times for 48
All chemicals were of analytical grade, obtained
(S1) and 72(S2) h at 180°C were examined by
from commercial sources, Merck Company, and
powder X-ray diffraction technique. As shown in
used without further purification. Phase
figure 1, a pure highly crystalline phase of meta-
identifications were performed on a powder X-ray
stable Li2Si2O5 with Primitive orthorhombic
diffractometer D5000 (Siemens AG, Munich,
Bravais Lattice (space group of Pbcn) [14, 24-26]
Germany) using CuKα radiation. The morphology
was obtained after 48 h. By increasing the reaction
of the obtained materials was examined with a field
time to 72h, a mixture of meta-stable Li2Si2O5
emission scanning electron microscope (Hitachi
(space group of Pbcn) and Li2SiO3 with base-
FE-SEM model S-4160). Also, FT-IR spectra were
centered orthorhombic Bravais Lattice (space group
recorded on a Tensor 27 (Bruker Corporation,
of Cmc21) was obtained. The additional peaks in
Germany). Absorption and photoluminescence
figure 1a at 2 theta in about 18.9, 26.9 and 33.2
spectra were recorded on a Jena Analytik Specord
degrees are related to Li2SiO3 impurity phase, and
40 (AnalytikJena UK, Wembley, UK) and a
the peaks at about 11, 28 and 35 are corresponded
PerkinElmer LF-5 spectrometer (PerkinElmer,
to the residual SiO2 and Li2O (created from lithium
Waltham, MA, USA), respectively. Also, cell
carbonate in aqueous solution) [18-23]. However,
parameter refinement was reported by celref
as reported in some papers, a stable form of lithium
software version 3.
disilicate crystallizes with base-centered
monoclinic Bravais Lattice (the space group of
2.1. Experimental
In a typical synthetic experiment, 0.300 g (4.0 Ccc2) [27]. According to the XRD patterns, they
mmol) of Li2CO3 (Mw = 73.82 gmol−1) and 0.96 g show that with using lithium carbonate in
(16.0 mmol) of SiO2.H2O (Mw = 60.08 gmol−1) replacement of lithium nitrate as lithium ion source,
were added to 60 mL of hot aqueous solutions of the main phase is lithium disilicate in replacement
0.4M NaOH under magnetic stirring at 80°C. The of lithium metasilicate. However, there is a mixture
S. Khademinia et al./ JNS 4 (2014) 407- 412 409

of lithium metasilicate and lithium disilicate phases k where t is entire thickness of the
t
B 1 cos 
at 72h; while at 48h, there is a pure lithium
2

disilicate phase. But, in our another published

crystalline sample, λ is the x-ray diffraction
work, using 1:2 Li:Si molar ratio, the main phase
wavelength and is 0.154 nm, k is the Scherrer
was lithium metasilicate and with 1:3 Li:Si molar
constant and is 0.9, B1/2 of FWHM is the full width
ratio the main phase was lithium disilicate. So, we
at half its maximum intensity and ӨB is the half
can conclude that the metal salt is a main factor to
diffraction angle at which the peak location is.
synthesize a specific phase [7]. Interplanar spacing
(d) in the obtained crystalline material is calculated Table 1. Calculated Scherrer data for pure Li2Si2O5
via Bragg’s equation (nλ = 2dhkl sinθ). Thus nanomaterials S1 and S2 at 180°C in 0.4M NaOH
solution.
compared to those of the obtained materials at 48 h,
with increasing the reaction time, the diffraction Samp 2Ѳ Ѳ B1/2 B1/2 cosѲ t(n
lines in the powder XRD patterns of the le value (degree) (radian) m)
S1 24.6 12.33 0.657 0.011 0.976 12.3
nanoparticles of lithium disilicate shift to a lower 7 5 4 9 7
2Ө values (Δ2θ =24.67(48 h) − 24.60(72 h) = S2 24.6 12.30 0.427 0.007 0.977 19.0
0 0 4 0 4
0.07° and Δd = 3. 614 Å (72 h) – 3. 277 Å (48 h) =
0.337 Å. So, according to above calculations, there 3.2. Morphology analysis
is an expansion in the unit cell with increasing the the obtained material is layer-like, consisting of
reaction time from 48 to 72h. sheets with no regular edge shape. Figure 2
represents the SEM images of S2 at 180°C. Figure 2
shows that after 48h, the morphology of (a and b)
and d show the layer structure of the as-prepared
materials with no significant orientation. Figure 2c
shows a high magnification image of the obtained
material. It shows that the width size of the
materials is about 50-60 nm with the length size of
(figure 2b) about 2.5 µm.

Fig. 1. PXRD patterns of the synthesized Li2Si2O5

nanoparticles, where a is S1; b is S2 at 180°C.

Table 1 shows the crystal sizes of the as-

synthesized nanomaterials in different NaOH molar
ratios calculated via Scherrer equation, using the
peak at h k l (040) corresponds to Li2Si2O5 phase,
Fig. 2. SEM images of S1.
410 S. Khademinia et al./ JNS 4 (2014) 407- 412

Figure 3 shows typical FESEM images of the S2 smaller than those of the standard sample.
at 180°C. From the typical FESEM images of S2, at However, parameters a and b for S2 are larger than
low magnification in figure 3 (a and b) we can see those of S1 but parameter c for S2 is smaller than
that with increasing the reaction time from 48h to that of S1. Because, in SEM images we found that
72h, the morphology of the obtained materials are the particle sizes of the S2 are larger than those of
in a nearly rod and wire forms and the rods have S1, so we can conclude that parameter a and b are
nearly homogenous morphology with the size of the main factor on the size of the materials [24].
about 3-4 µm in length, and 360-480 nm in width
and the wires with the size of about 60 nm in Table 2. Cell parameter refinement plot of Li2Si2O5
showing an expansion along the a and b directions in the
thickness and 2-3µm in length, as shown in figure
unit cell.
3b and c. However, as shown in figure 3c, the
whole sizes of the obtained materials (layers Sample a b c
compared to rod structure) synthesized at 72h are JCPDS:14- 5.8 14. 4.8
322) 0 66 1
larger than that of 48h. Also, with comparing to our Sample 1 5.8 14. 4.8
another work [7], with using lithium carbonate as 4 49 0
Sample 2 5.8 14. 4.8
lithium ion source at 1:2 Li:Si molar ratio, in 5 51 0
replacement of lithium nitrate, at 1:2 molar ratio,
the morphology of the obtained materials in the 3.3. Optical properties
Figure 4 shows the FTIR spectra of the
case of lithium disilicate changed to nano rods and
synthesized materials S1 and S2 at 180°C. It is clear
layers. So, it shows that the reactant type is a main
that the peaks at 467.27 and 557.21 cm-1 are
factor affect on the morphology of the obtained
assigned to O-Si-O bending vibration and the peaks
materials [7].
at 650.61, 759.41 and 766.27 cm-1 are assigned to
symmetric stretching vibration of Si-O-Si. Also, the
peaks at 932.94, 111.26 and 1253.86 cm-1 are
assigned to asymmetric stretching vibration of Si-
O-Si and the peak at 3422.80 cm-1 is assigned to the
vibration for H2O [28, 29].

Fig. 3. SEM images of (S2).

Table 2 shows the cell parameter refinement

data of the synthesized nanomaterials. It is clear
that parameters a and b values of the as- Fig. 4. FTIR spectra of the synthesized Li2Si2O5
nanomaterials, where a is S1 and b is S2.
synthesized materials are larger and parameter c is
S. Khademinia et al./ JNS 4 (2014) 407- 412 411

Figure 5 shows UV–visible spectra of the pure and S2, respectively. So, there is a red shift in the
phase Li2Si2O5 powders produced by the emission spectra with increasing the reaction time
hydrothermal reaction at 180ºC for 48 and 72h, from 48 to 72h.
respectively. No obvious difference could be
detected from two UV–visible spectra, except for a
slight little blue shift of nano materials synthesized
at 72h relative to that of 48h. A sharp absorption
band at 283 and 278 nm is observed respectively
for S1 and S2. The band gap energy estimated from
UV–visible is 4.38 eV, and 4.46 eV. According to
our another works on the synthesis of lithium
silicates, we found that with increasing the reaction
time from 48 to 72h, and increasing the particle
size, there is a blue shift in the absorption
wavelength and so the calculated band gap is Fig. 6. Photoluminescence spectra of the synthesized
increased [30]. So we can conclude that the particle Li2Si2O5 nanomaterials (λex = 281 nm), where a is S1 and
size is a factor on the calculated band gap. It means b is S2.

that for increasing the band gap we should increase

the particle size.
4. Conclusion
In summary, uniform rod and layer like lithium
disilicate were successfully synthesized by a simple
hydrothermal method. We found that the reaction
time has a main effect on the morphology of the
products. UV–vis electronic absorption and
emission spectra of the synthesized materials were
investigated. Also, cell parameter refinement was
calculated by celref software version 3 and showed
that the parameters have influences on the size of
the obtained materials.

Acknowledgements
The authors express their sincere thanks to the
Fig. 5. UV-vis spectra of the synthesized Li2Si2O5 authorities of Tabriz University for financing the
nanomaterials, where a is S1 and b is S2. project.

Figure 6 represents the room-temperature References

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