Applied Surface Science 351 (2015) 1075–1080

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Applied Surface Science

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

Synthesis of lanthanum tungstate interconnecting nanoparticles by

high voltage electrospinning
Yanee Keereeta a,∗ , Titipun Thongtem b,c,∗∗ , Somchai Thongtem a,c
a
Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
c
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

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

Article history: Lanthanum tungstate (La2 (WO4 )3 ) interconnecting nanoparticles in the shape of fibers were successfully
Received 22 February 2015 synthesized by electrospinning in combination with high temperature calcination. In this research, cal-
Received in revised form 21 May 2015 cination temperature for the synthesis of the fibers evidently influenced the diameter, morphology and
Accepted 26 May 2015
crystalline degree. The crystalline monoclinic La2 (WO4 )3 fibers with 200–700 nm in diameter, two main
Available online 18 June 2015
Raman peaks at 945 and 927 cm−1 , FTIR stretching modes at 936 and 847 cm−1 , 2.02 eV energy gap and
415–430 nm blue emission were synthesized by calcination of inorganic/organic hybrid fibers at 750 ◦ C
Keywords:
for 5 h, characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron
Electrospinning
Lanthanum tungstate
microscopy (TEM), selected area electron diffraction (SAED), thermogravimetric analysis (TGA), Fourier
Photoluminescence transform infrared spectroscopy (FTIR), Raman spectroscopy, UV–visible spectroscopy and photolumi-
UV–visible absorption nescence (PL) spectroscopy. The surface of the composite fibers before calcination was very smooth. Upon
calcination the composite fibers at 750 ◦ C for 5 h, they were transformed into nanoparticles join together
in the shape of fibers with rough surface.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction Their novel characteristics show up as very large surface area

Nanostructure materials such as nanowires, nanorods, nano-
tubes and nanofibers have been very interesting for a number of
scientists and engineers [1,2]. Among them, 1 D nanofibers have
attractive properties and novel potential applications: reinforce-
ment, filtration, solar cells, electromagnetic shielding, non-wetting
textiles and liquid crystal devices [3–5]. Thus electrospinning tech-
nique has been become increasingly popular and is able to be used
for synthesizing nanofibers [6]. It is a process used for synthesizing
continuous polymeric fibers with nanometer diameter caused by
the action of an external electric field applied through liquid poly-
mers [3]. Upon applying an external electric field through sol–gel
solutions to synthesize polymeric fiber/inorganic composites, they
will be dried in ambient atmosphere. The polymer diameters are
reduced in size from micrometers to submicrometers/nanometers.
∗ Corresponding author. Tel.: +66 0 53 941924; fax: +66 0 53 943445.
∗∗ Corresponding author at: Department of Chemistry, Faculty of Science,
Chiang Mai University, Chiang Mai, 50200, Thailand. Tel.: +66 0 53 943344;
fax: +66 0 53 892277.
E-mail addresses: ynkeereeta@gmail.com (Y. Keereeta),
ttpthongtem@yahoo.com, ttpthongtem@gmail.com (T. Thongtem).
to volume ratio, flexibility in surface functionalities and supe-
rior mechanical properties [4]. Then the polymeric fiber-inorganic
composites are calcined at high temperature to form inorganic
nanofibers [7].
Crystalline tungstate such as CaWO4 , PbWO4 , ZnWO4 and
KGd(WO4 )2 has demonstrated excellent potential in stimulated
Raman scattering (SRS). The laser emission can be converted to
an applicable wavelength by doping with ionic rare-earth [8–10].
Stimulated Raman conversion with efficiency of 37% of a fiber-like
lanthanum tungstate crystal has been reported [11]. Lanthanum
tungstate (La2 (WO4 )3 ) biaxial crystal belongs to monoclinic struc-
ture with C2 /c space group [9]. Some properties about the crystal
are generally available. At present, connecting La2 (WO4 )3 nanopar-
ticles, an important material to enhance laser performance, have
not been reported.
To the best of our knowledge, no connecting La2 (WO4 )3
nanoparticles have ever been synthesized by a combination of elec-
trospinning and high temperature calcination. It is therefore for us
to use a mixture of inorganic reagents dissolved in poly(vinyl alco-
hol) (PVA) to synthesize inorganic–polymeric fibrous composites,
which would be transformed into interconnecting-nanoparticles’
fibers by subsequent high temperature calcination. This success
may lead to new industrial process by direct high voltage (H.V.)

http://dx.doi.org/10.1016/j.apsusc.2015.05.194
0169-4332/© 2015 Elsevier B.V. All rights reserved.
1076 Y. Keereeta et al. / Applied Surface Science 351 (2015) 1075–1080
electrospinning. Phase, morphology, thermal properties, atomic
vibration and optical properties were intensively investigated and
discussed.
2. Experiment
Basing on the conventional sol–gel process, lanthanum
nitrate hexahydrate (99.0% La(NO3 )3 ·6H2 O) and ammonium
metatungstate hydrate (99.0% H26 N6 O40 W12 ·H2 O) with 2:3 molar
ratio of La:W were dissolved in 10 ml of deionized (DI) water.
The precursor solution was stirred for 10 min and mixed with
20 ml aqueous PVA (poly(vinyl alcohol), 72,000 MW) solution at
a temperature of 70 ◦ C with vigorous stirring. The mixture was
electrospun by a 15 kV applied electric voltage. A dense web of
PVA/La2 (WO4 )3 composite fibers was collected on a piece of cop-
per plate placed 15 cm away from the needle tip and divided into
several parts. To avoid the undesired oxidation process, each of the
parts was then heated in an argon atmosphere (inert gas) at 450,
550, 650 and 750 ◦ C for 3 h, and at 750 ◦ C for 4 and 5 h.
These products were further characterized by an X-ray diffrac-
tometer (XRD, SIEMENS D500) operating at 20 kV and 15 mA using
Cu-K␣ line in combination with the database of the Joint Com-
mittee on Powder Diffraction Standards (JCPDS) [12], a scanning
electron microscope (SEM, JEOL JSM-6335F) operating at 15 kV,
a transmission electron microscope (TEM, JEOL JEM-2010) oper-
ating at 200 kV, a Fourier transform infrared spectrometer (FTIR,
Bruker Tensor 27) with KBr as a diluting agent operating in the
range of 4000–400 cm−1 , a Raman spectrometer (T64000 HORIBA
Jobin Yvon) using a 50 mW and 514.5 nm wavelength Ar green
laser, a thermogravimetric analyzer (TGA, Shimadzu TGA-50) using
a heating rate of 5 ◦ C/min, a UV-visible spectrometer (Lambda
25 PerkinElmer) using a UV lamp with the resolution of 1 nm,
and a photoluminescence (PL) spectrometer (aVantes, AvaSpec-
2048TEC-USB2-2; Channel(s): 2; Software: Full, XLS; Grating: UB,
200–720 nm, and IB, 717–1000 nm) with a 345 nm fixed excitation
wavelength (Ocean Optics LLS-345) selection at room temperature.
3. Results and discussion
3.1. TGA
To determine the calcination temperature for removing the PVA
template in the fibrous precursor, the decomposition behavior of
the precursor was investigated by TGA. Fig. 1 shows the thermal
Fig. 1. TGA curves of PVA and La2 (WO4 )3 /PVA electrospun fibers.
behavior of PVA and La2 (WO4 )3 /PVA electrospun fibers character-
ized by TGA analyzer with a heating rate of 5 ◦ C/min. According to
the TGA curve of pure PVA, it was degraded and decomposed at a
temperature of about 500 ◦ C as follows. The first weight loss was
10.5% due to the evaporation of loosely bound water at 32–200 ◦ C.
The second was a large amount of 79.3% weight loss, predominantly
caused by the decomposition of PVA at 200–420 ◦ C. The third was
8.3% by the breaking of PVA backbone at 420–490 ◦ C. The weight
loss tended to terminate upon further heating to above 490 ◦ C.
When the La2 (WO4 )3 /PVA electrospun fibers were characterized,
the TGA curve indicates a significant weight loss of 63.5% in the
temperature range of 32–700 ◦ C. Over the range of the analysis,
their weight losses were divided into two different steps. The first
step weight loss of about 10.1% from 32 to 200 ◦ C was attributed
to the removal of absorbed water in the composites. The second
weight loss of 53.4% ranging from 200 ◦ C to 700 ◦ C was related to the
decomposition of PVA. Above 700 ◦ C, the TGA curve was still in the
same state or condition, indicating the complete thermal decom-
position. Pure crystalline La2 (WO4 )3 interconnecting nanoparticles
composing the fibers were obtained by heating at a temperature
above 700 ◦ C.
3.2. SEM, TEM and SAED
SEM images of the lanthanum tungstate/PVA composite fibers
both before and after calcination at different temperatures are
shown in Fig. 2a–f. Before calcination, the as-synthesized fibers
of the whole length were smooth surfaces and uniform diameter
due to the amorphous nature of polymeric PVA. La2 (WO4 )3 nuclei
blended in the fibers were unable to be detected. Possibly, the nuclei
were so tiny that they were unable to be detected by the present
analysis. The fibrous diameters were in the range of 300–845 nm.
Their lengths could be as long as several millimeters. Upon cal-
cination at 550 ◦ C for 3 h, the fiber surfaces became roughened.
Concurrently, the nearby lanthanum tungstate molecules nucle-
ated and grew out of the fibrous trunks as needle-like structure with
some appreciable change in diameter. At 650 ◦ C and 3 h calcination,
the fibers still retained their morphology with significant increase
in fibrous diameters and the needle-like structure became thicker.
Further increasing in the calcination temperature to 750 ◦ C for
3 h, 4 h and 5 h, the fibrous structure transformed into connecting
nanoparticles or crystallites instead of needle-like structure with
reduction in the fibrous diameter at this temperature by increasing
the calcination time due to the evaporation process. Distribution of
fibrous diameters at 750 ◦ C and 5 h calcination is shown in Fig. 2g.
These fibrous diameters were started to be counted from the small-
est to the largest. Their diameter distribution fitted very well with
a normal curve over the range of 200–700 nm with the average
diameter of 430 nm. The diameter reduction was observed due
to the removal of some polymeric species during heat treatment
processing.
Transmission electron microscopy was used to further iden-
tify the fibrous nature of lanthanum tungstate particles containing
in the fibers, as shown in Fig. 2h–j. The typical TEM images
of La2 (WO4 )3 fibers after calcination at 750 ◦ C for 5 h show the
average diameter of 200–300 nm, in consistent with the SEM anal-
ysis. Clearly, the fibers appear as interconnecting nanocrystals.
The darker region observed in the heat treated fibers repre-
sents areas of higher concentration of overlapping crystallites.
Selected area electron diffraction (SAED) pattern of the calcined
fibrous crystallite was composed of well-resolved concentric rings
of bright spots, indicating nanocrystalline nature of lanthanum
tungstate, belonging to monoclinic structure with C2 /c space group
(JCPDS No. 82-2068) [12] and identifying the presence of pure
nanocrystalline La2 (WO4 )3 fibers after calcination at 750 ◦ C for 5 h
in argon atmosphere.
 Y. Keereeta et al. / Applied Surface Science 351 (2015) 1075–1080 1077

Fig. 2. (a–f) SEM images of the La2 (WO4 )3 /PVA composite fibers before and after calcination at 550 ◦ C, 650 ◦ C and 750 ◦ C for 3 h, and at 750 ◦ C for 4 h and 5 h, respectively.
(g) Distribution of fibrous diameters and (h–j) TEM images and SAED pattern of the electrospun fibers after calcination at 750 ◦ C for 5 h.

3.3. XRD

Fig. 3 shows XRD patterns of La2 (WO4 )3 fibers with 750 ◦ C cal-
cination for 3 h, 4 h and 5 h. All XRD patterns of the as-synthesized
samples are in accordance with lanthanum tungstate, La2 (WO4 )3
(JCPDS No. 82-2068) [12]. Moreover, the samples synthesized at
750 ◦ C for 3 h and 4 h contain some impurity of La2 W2 O9 (JCPDS
No. 34-0704) [12]. Upon increasing in calcination time to 5 h, the
spectra became sharper and the XRD intensities were stronger. The
XRD pattern indicates high purity of the as-synthesized La2 (WO4 )3
without impurity detection. Crystalline degree of the product was
much improved. Thus, the calcination temperature of 750 ◦ C and 5 h
is appropriate for the synthesis of La2 (WO4 )3 fibers in this research.
Temperature was found to have influence on the crystalline degree
and purity of the La2 (WO4 )3 fibers as well. The intensity of diffrac-
tion peaks increases with increasing in the calcination temperature
and time, indicating the increase of crystalline degree and purity at
higher temperature and longer calcination time.

3.4. FTIR and Raman analysis

To explain the structure of La2 (WO4 )3 fibers, they were char-

acterized by FTIR. Fig. 4 provides further insight into the vibration
of the PVA (72,000 MW) and the La2 (WO4 )3 /PVA composite fibers
with and without calcination at 450 ◦ C, 550 ◦ C, 650 ◦ C for 3 h, and
at 750 ◦ C for 3 h, 4 h and 5 h within the range between 4000
and 400 cm−1 . Consider the PVA spectrum, it obviously reveals Fig. 3. XRD patterns of La2 (WO4 )3 /PVA electrospun fibers after calcination at 750 ◦ C
the major band associated with poly(vinyl alcohol) with the for 3 h, 4 h and 5 h, comparing to those of the JCPDS database.
1078 Y. Keereeta et al. / Applied Surface Science 351 (2015) 1075–1080
Fig. 4. FTIR spectra of PVA and La2 (WO4 )3 /PVA electrospun fibers before and after
calcination at 450 ◦ C, 550 ◦ C, 650 ◦ C for 3 h, and at 750 ◦ C for 3 h, 4 h and 5 h.
O–H stretching of alcohol at 3387 cm−1 . The vibrational band at
2943 cm−1 refers to the C–H stretching of alkyl groups, including
the C O stretching band appearing at 1721 cm−1 , the bending band
of CH2 at 1448 cm−1 and the C–O of carboxyl stretching band at
1098 cm−1 [13–15]. For the as-electrospun La2 (WO4 )3 /PVA fibers,
additional three main modes were detected. The band at 1647 cm−1
is related to the O–H deformation vibration of water. The next band
at 1384 cm−1 is due to the oscillation in NO3 − groups of the residual
La(III) salts [16]. The infrared vibration modes at 1091, 933, 887 and
780 cm−1 are the characteristic bands of tungstate groups [16–18].
After calcination at high temperature, the fibers with 450 ◦ C calci-
nation show IR absorption at 1551 cm−1 and 830 cm−1 , which are
specified as the residual PVA and characteristic band of tungstate
groups, respectively. At the temperature of 550 ◦ C and above, the
vibration bands of PVA were no longer detected, indicating that
the PVA was totally removed by the high temperature calcination
process. The evidence for the structure of La2 (WO4 )3 is confirmed
from the vibrational modes at 936, 847, 807, 759, 680, 471 and
446 cm−1 , which are the characteristic bands of La2 (WO4 )3 [17] and
were more evidence by increasing in the calcination temperature
to 750 ◦ C.
In this research, Raman spectroscopy was also studied to con-
firm the fibrous products. The Raman spectra of La2 (WO4 )3 /PVA
electrospun fibers with 450 ◦ C, 550 ◦ C, 650 ◦ C and 750 ◦ C calcination
for 3 h are shown in Fig. 5. The presence of the broad peaks of Raman
spectrum of the La2 (WO4 )3 /PVA as-electrospun fibers with 450 ◦ C
and 3 h calcination proves that the fibers are not perfect crystal. The
fibers were a mixture of amorphous and crystalline phases. When
the calcination temperatures were increased to 550 ◦ C, 650 ◦ C and
750 ◦ C, the La2 (WO4 )3 crystal was improved and the crystalline
degree was increased, especially at 750 ◦ C calcination. The good
crystalline degree promotes the atoms to simultaneously vibrate at
Fig. 5. Raman spectra of La2 (WO4 )3 /PVA electrospun fibers after calcination at
450 ◦ C, 550 ◦ C, 650 ◦ C and 750 ◦ C for 3 h.
the same mode and the peaks correspond to the internal vibrational
modes of La2 (WO4 )3 according to the Td point group symmetry
[17]. The La2 (WO4 )3 Raman spectrum of the fibers after calcination
at 750 ◦ C shows the high frequency peaks at 945 and 927 cm−1 due
to the symmetric A1 (1 ) vibrations of the two types of WO4 units,
WI O4 and WII O4 , respectively. The Raman peaks at 840, 801 and
783 cm−1 were specified as the F2 (␯3 ) vibrations in WI O4 and those
at 819, 728 and 704 cm−1 were assigned as the F2 (3 ) vibrations in
WII O4 . The peak at 388 cm−1 was specified as E(2 ) vibration in
WI O4 , and the Raman peaks at 354 and 340 cm−1 were interpreted
as E(2 ) vibrations in WII O4 reported by Burcham and Wachs [17].
3.5. UV–visible absorption and PL emission
UV–visible absorption and the (˛h)2 versus h␯ plot of
La2 (WO4 )3 /PVA electrospun fibers after calcination at 750 ◦ C for
5 h are shown in Fig. 6. The plot indicates a monotonic decreasing
of the photonic absorbance attenuated through the fibrous solid.
During attenuation, the absorption was controlled by two photon
energy (h) ranges. When the photon energy was greater than the
energy gap, the absorption was linearly increased with the increas-
ing of photon energy. The steep inclination of the linear portion of
the curve was caused by the UV absorption for charged diffusion
from the highest occupied molecular orbital (HOMO) to the low-
est unoccupied molecular orbital (LUMO). The energy difference
between the HOMO and LUMO (frontier orbitals) is specified as the
HOMO–LUMO gap characterized by a certain crystal momentum
vector (k vector) in the Brillouin zone, and is able to be used to pre-
dict the spectrum color. For the photon energy with less than the
energy gap, the absorption curve became different from linearity,
 Y. Keereeta et al. / Applied Surface Science 351 (2015) 1075–1080
Fig. 6. UV–visible absorption of La2 (WO4 )3 /PVA electrospun fibers after calcination
at 750 ◦ C for 5 h.
due to the UV absorption for charged diffusion relating to different
defects. In general, the excited state is not stable. The photogen-
erated electrons would recombine with the photogenerated holes
by releasing energy as a photonic spectrum with different colors
relating to the HOMO–LUMO energy gap. When the momentum of
electrons and holes is the same in both the CB and the VB, the elec-
trons could directly emit a photonic spectrum, relating to the direct
energy gap. In some cases, electrons must pass through an interme-
diate state and transfer momentum to the crystal lattice, and the
electronic diffusion is related to an indirect energy gap. By extrap-
olating the linear portion curve of the (˛h)2 versus h plot to zero
absorption (inset of Fig. 6), its direct energy gap was determined
to be 2.02 eV. In fact, energy gap is controlled by several factors
such as the electronegativity of transition metal ions, connectivity
of the polyhedrons, deviation in the O–W–O bonds, distortion of
the (WO4 )2− tetrahedrons, growth mechanism, and degree of struc-
tural order-disorder in the lattice [19], including different defects
residing in the crystal.
Fig. 7 shows a photoluminescence (PL) emission spectrum of
La2 (WO4 )3 /PVA electrospun fibers after calcining at a temperature
Fig. 7. PL emission of La2 (WO4 )3 /PVA electrospun fibers after calcination at 750 ◦ C
for 5 h.
1079
of 750 ◦ C for 5 h. PL emission of lanthanum tungstate with
monoclinic structure is not clearly understood. In particular, the
literature has reported several hypotheses to explain mechanisms
responsible to the PL emission. Grobelna [20] had a profound study
on the photoluminescence properties of luminescent materials
consisting of Ln2−x Tbx (WO4 )3 (where Ln = Gd(III) or La(III)) incor-
porated into silica xerogel, a low intensity broad peak at 420 nm
ascribed to the (WO4 )2− groups’ emission. Kodaira et al. [21] stud-
ied the photoluminescence behavior of Eu3+ ions doped into the
RE2 (WO4 )3 matrix (RE = La and Gd). The compound was found to
present low intensity broad bands from 420 to 570 nm assigned
to the O–W ligand-to-metal charge-transfer states. In the present
research, an excitation wavelength of 345 nm related to the UV
range was used. The PL spectrum mainly consisted of intrinsic peak
with its surrounding shoulders, caused by some defects and impu-
rities and interpreted as extrinsic transition. The intrinsic peak is
due to the 1 T2 →1 A1 diffusion of electrons within (WO4 )2− anions
[22,23]. The emission peak is in the spectral range of 415–430 nm
(blue color) — having the potential application for photonic sensors
and devices.
4. Conclusions
Crystalline monoclinic La2 (WO4 )3 fibers were successfully syn-
thesized by the electrospinning technique in combination with the
high temperature calcination. At 750 ◦ C and 5 h calcination, the
product was composed of nanoparticles joined together shaped
like fibers with two main Raman peaks at 945 and 927 cm−1 , FTIR
stretching vibration modes at 936 and 847 cm−1 , 2.02 eV energy
gap, and 415–430 nm blue emission—one of the promising materi-
als for different applications.
Acknowledgement
We wish to thank Chiang Mai University (CMU) for financial
support through the CMU Research Fund.
References
[1] Q. Cui, X. Dong, J. Wang, M. Li, Direct fabrication of cerium oxide hollow
nanofibers by electrospinning, J. Rare Earth 26 (2008) 664–669.
[2] Z.W. Fu, J. Ma, Q.Z. Qin, Nanostructured LiCoO2 and LiMn2 O4 fibers fab-
ricated by a high frequency electrospinning, Solid State Ion. 176 (2005)
1635–1640.
[3] J.M. Deitzel, J. Kleinmeyer, D. Harris, N.C. Beck Tan, The effect of processing
variables on the morphology of electrospun nanofibers and textiles, Polymer
42 (2001) 261–272.
[4] Z.M. Huang, Y.Z. Zhang, M. Kotaki, S. Ramakrishna, A review on polymer
nanofibers by electrospinning and their applications in nanocomposites, Comp.
Sci. Technnol. 63 (2003) 2223–2253.
[5] Y. Li, Z. Huang, Y. Lü ˇ , Electrospinning of nylon-6,66,1010 terpolymer, Eur.
Polym. J. 42 (2006) 1696–1704.
[6] P.K. Panda, S. Ramakrishna, Electrospinning of alumina nanofibers using differ-
ent precursors, J. Mater. Sci. 42 (2007) 2189–2193.
[7] J.Y. Li, H. Dai, Q. Li, X.H. Zhong, X.F. Ma, J. Meng, X.Q. Cao, Lanthanum zir-
conate nanofibers with high sintering-resistance, Mater. Sci. Eng. B 133 (2006)
209–212.
[8] F.B. Xiong, X.H. Gong, Y.F. Lin, Y.J. Chen, Q.G. Tan, Z.D. Luo, Y.D. Huang, Spec-
troscopic characteristics of Pr3+ in biaxial La2 (WO4 )3 crystal, Appl. Phys. B 86
(2007) 279–286.
[9] Y. Chen, X. Lin, Z. Luo, Y. Huang, Spectroscopic properties of Nd3+ ions in
La2 (WO4 )3 crystal, Chem. Phys. Lett. 381 (2003) 598–604.
[10] Y. Chen, X. Lin, Z. Luo, Y. Huang, Spectroscopic properties of Er3+ ions in
La2 (WO4 )3 crystal, Opt. Mater. 27 (2004) 625–633.
[11] Y. Urata, S. Wada, H. Tashiro, T. Fukuda, Fiber-like lanthanum tungstate crys-
tal for efficient stimulated Raman scattering, Appl. Phys. Lett. 75 (1999)
636–638.
[12] Powder Diffract. File, JCPDS-ICDD, 12 Campus Boulevard, Newtown Square, PA
19073-3273, U.S.A., 2001.
[13] S. Rajendran, M. Sivakumar, R. Subadevi, M. Nirmala, Characterization of
PVA-PVdF based solid polymer blend electrolytes, Phys. B 348 (2004)
73–78.
1080 Y. Keereeta et al. / Applied Surface Science 351 (2015) 1075–1080
[14] H.S. Mansur, R.L. Oréfice, A.A.P. Mansur, Characterization of poly(vinyl alco-
hol)/poly(ethylene glycol) hydrogels and PVA-derived hybrids by small-angle
X-ray scattering and FTIR spectroscopy, Polymer 45 (2004) 7193–7202.
[15] H.S. Mansur, C.M. Sadahira, A.N. Souza, A.A.P. Mansur, FTIR spectroscopy char-
acterization of poly (vinyl alcohol) hydrogel with different hydrolysis degree
and chemically crosslinked with glutaraldehyde, Mater. Sci. Eng. C 28 (2008)
539–548.
[16] B. Grobelna, M. Szabelski, K. Kledzik, A.M. Kłonkowski, Luminescent properties
of Sm(III) ions in Ln2 (WO4 )3 entrapped in silica xerogel, J. Non-Cryst. Solid 353
(2007) 2861–2866.
[17] L.J. Burcham, I.E. Wachs, Vibrational analysis of the two non-equivalent, tetra-
hedral tungstate (WO4 ) units in Ce2 (WO4 )3 and La2 (WO4 )3 , Spectrochim. Acta
Part A 54 (1998) 1355–1368.
[18] M. Galceran, M.C. Pujol, M. Aguiló, F. Díaz, Sol–gel modified Pechini method for
obtaining nanocrystalline KRE(WO4 )2 (RE = Gd and Yb), J. Sol-Gel Sci. Technol.
42 (2007) 79–88.
[19] J.C. Sczancoski, L.S. Cavalcante, M.R. Joya, J.W.M. Espinosa, P.S. Pizani, J.A.
Varela, E. Longo, Synthesis, growth process and photoluminescence properties
of SrWO4 powders, J. Colloid Interface Sci. 330 (2009) 227–236.
[20] B. Grobelna, Luminescence based on energy transfer in xerogels doped with
Ln2−x Tbx (WO4 )3 , J. Alloys Compd. 440 (2007) 265–269.
[21] C.A. Kodaira, H.F. Brito, M.C.F.C. Felinto, Luminescence investigation of Eu3+ ion
in the RE2 (WO4 )3 matrix (RE = La and Gd) produced using the Pechini method,
J. Solid State Chem. 171 (2003) 401–407.
[22] A. Phuruangrat, T. Thongtem, S. Thongtem, Synthesis of lead molybdate and
lead tungstate via microwave irradiation method, J. Cryst. Growth 311 (2009)
4076–4081.
[23] J.W. Yoon, J.H. Ryu, K.B. Shim, Photoluminescence in nanocrystalline MMoO4
(M = Ca, Ba) synthesized by a polymerized complex method, Mater. Sci. Eng. B
127 (2006) 154–158.