Journal of Molecular Structure 1044 (2013) 323–327

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Journal of Molecular Structure

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

Structural investigation of new vanadium–bismuth–phosphate glasses by IR

and ESR spectroscopy
N. Vedeanu a, O. Cozar b,d,⇑, R. Stanescu b, I.B. Cozar c, I. Ardelean b
a
Faculty of Pharmacy, Iuliu Hatßieganu University of Medicine and Pharmacy, RO-400023 Cluj-Napoca, Romania
b
Faculty of Physics, Babesß-Bolyai University, Kogalniceanu No. 1, 400084 Cluj-Napoca, Romania
c
National Institute for Research and Development of Isotopic and Molecular Technologies, Donath No. 71-103, P.O. 700, 400293 Cluj-Napoca, Romania
d
Academy of Romanian Scientists, Splaiul Independentei No. 54, RO-050094 Bucharest, Romania

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

Article history: IR spectra changes of the xV2O5(1  x)[0.8P2O50.2Bi2O3] glass system with 0 6 x 6 50 mol% show that
Available online 14 February 2013 vanadium oxide acts as a network modifier at low concentration (x 6 5 mol%), affecting especially the
Bi2O3 network. In the same time the phosphate groups (structures) impose their presence by themselves,
Keywords: fact which is illustrated by the increasing of the intensity of characteristic 910, 1040, 1230 cm1 bands.
V2O5 The IR bands belonging to the phosphate groups are strongly reduced for x P 10 mol% due to the phos-
P2O5 phate network depolymerization and to the appearance of new vibrations characteristic for PAOAV and
Bi2O3
VAOAV linkages, showing the network former role of V2O5. In the same time the changes observed in the
Glasses
IR
ESR spectra of these glasses are explained supposing the superposition of two signals, one with a well-
ESR resolved hyperfine structure typical for isolated V4+ ions and a broad line characteristic for clustered ions.
The line width dependence versus V2O5 content shows that dipole–dipole interactions exist between
vanadium ions until x = 5 mol% and the superexchange interactions prevail at high content
(x P 10 mol%).
Ó 2013 Published by Elsevier B.V.

1. Introduction from Q3 to Q2 to Q1 to Q0 as the ratio M2O/P2O5 = R passes from

Glasses containing transitional metal (TM) ions have been stud-
ied mainly because of their interesting optical, thermal and mag-
netic properties and for their potential applications. The
technological importance of these glasses requires a detailed
understanding of the molecular and structural chemistry in order
to help the determination of relationships between physical prop-
erties and their structural units [1–7].
Both P2O5 and Bi2O3 oxides are known as network formers but
Bi2O3 is an unconventional one [8].
Phosphate glasses are of large interest for a variety of techno-
logical applications due to several unique properties, such as high
thermal expansion coefficient, low viscosity, UV transmission or
electrical conduction [9,10].
The network of phosphate glasses contains a polymeric struc-
ture dominated by linkages between PO4 tetrahedra [1,11]. In the
case of vitreous P2O5, these groups are connected to adjacent units
by three of their four vertices; one place is occupied by a terminal,
double-bonded oxygen atom (DBO).
The structures of binary phosphate glasses are described by the
so-called Qs groups model. The phosphate structural groups pass
⇑ Corresponding author. Tel.: +40 748193339.
E-mail address: onuc.cozar@phys.ubbcluj.ro (O. Cozar).
0 to 1, 2 and finally to 3 [12,13].
Bismuth based glasses attracted a great deal of interest due to
their important applications in the field of glass ceramics, layers
for optical and optoelectronic devices, thermal and mechanical
sensors, reflecting windows, etc. [14–16]. These glasses are also
used to produce after appropriate annealing high temperature
ceramic superconductors [14,17]. In Bi2O3-based glasses the bis-
muth ions may appear in BiO3 pyramidal and BiO6 octahedral units
[18,19]. We mention also that Bi2O3 oxide is not a classical glass
former, due to its high polarizability and small field strength of
Bi3+ ions.
Generally the [BiOn] polyhedra are highly distorted due to the
lone pair electrons and thus the structural role played by Bi2O3
in glasses is complicated and poorly understood.
It is reported that Bi2O3 occupies both network-forming and
network-modifying positions in oxide glasses and therefore, the
physical properties of glasses containing Bi2O3 exhibit discontinu-
ous changes when the structural role of the cation switches over in
this way [20,21]. The role of Bi2O3 in phosphate glasses has been
investigated in several studies [22–27]. Daviero et al. found two
distinct oxygen shells in the Bi3+ environment and a mixed net-
work-former effect of Bi2O3 in Na2OBi2O3P2O5 glasses [22]. Shaim
et al. have reported that the incorporation of BiO6 octahedra into
the glass structure leads to the depolymerization of phosphate

0022-2860/$ - see front matter Ó 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.molstruc.2013.01.078
324 N. Vedeanu et al. / Journal of Molecular Structure 1044 (2013) 323–327
chains and in such glasses pyrophosphate groups are prevailing for
low Bi2O3 content, whereas in Bi2O3-rich glasses, orthophosphate
groups become predominant structural units [23–25].
The increase of Bi2O3 content (0 6 x 6 15 mol%) in 50ZnOxBi2-
O3(50  x)P2O5 glasses results in the depolymerization of meta-
phosphate chains, whereas for higher Bi2O3 content
(20 6 x 6 35 mol%), the presence of isolated orthophosphate tetra-
hedra was detected [26,27].
The addition of transitional metal oxides, such as V2O5 in the
phosphate glasses, was investigated by several researchers [28–
34]. The vanadyl ion VO2+ incorporated in glasses, as spectroscopic
probe, is useful to characterize the glass local structure. The VO2+
ion, like other transitional metals, provide information about many
specific aspects as the geometry of the coordination polyhedra of
the transitional metal ions (local symmetry), the changes in the
coordination sphere, their distribution mode and type of interac-
tions between them, and indirectly on the organization of host ma-
trix [31–34].
In this paper, xV2O5(1  x) [0.8P2O50.2Bi2O3] glass system with
0 6 x 6 50 mol% was prepared and investigated by IR and ESR spec-
troscopy, in order to obtain further information about the local
symmetry, interactions and structural changes induced by the
increasing of V2O5 content in the phosphate–bismuthate matrix.
2. Experimental
In order to obtain the xV2O5(1  x) [0.8P2O50.2Bi2O3] glass sys-
tem (0 6 x 6 50 mol%) was first prepared the matrix [P2O5Bi2O3]
by mixing (NH4)2HPO4 with Bi2O3 and melting these admixtures
at 1250 °C for 5 min in a sintered corundum crucible using the
technique previously reported [11,29]. The matrix was crushed
and the resulting powder was mixed with appropriate amounts
of V2O5 before final melting at 1250 °C. The melted glasses were
cooled at room temperature by quickly pouring onto stainless steel
plates.
Because these glasses are hygroscopic the obtained samples
were kept into exicator surrounded by silicagel. All the oxides used
are from SIGMA–ALLDRICH and have the analytical high grade
purity.
The structure of samples was analyzed by means of X-ray dif-
fraction using a Bruker D8 Advanced X-ray diffractometer with a
graphite monochromator for Cu Ka radiation with k = 1.54 Å. The
pattern obtained did not reveal any crystalline phase in all samples
(Fig. 1).
Fig. 1. XRD diffractograms of xV2O5(1  x)[0.8P2O50.2Bi2O3] glasses.
The absence of sharp peaks in the diffraction pattern of all the
investigated glasses shows only the amorphous character without
any crystalline forms for these glasses.
IR spectra were recorded with a Bruker IFS66/DSP spectrometer
in 400–2000 cm1 range, using the anhydrous KBr technique to
avoid structural modifications caused by the ambient moisture.
The resolution of the IR spectra is of 2 cm1.
ESR measurements were performed at 9.4 GHz (X-band) at
room temperature using an ADANI Portable PS8400 (USA)
spectrometer.
3. Results and discussion
3.1. IR spectra
Fig. 2 shows the IR spectra of V2O5AP2O5ABi2O3 glasses in the
1500–400 cm1 range.
The specific bands for the phosphate–bismuth (0.8P2O5A0.2Bi2-
O3) network (x = 0 mol%) are situated in the following regions:
460–517 cm1, 690–775 cm1, 900–1040 cm1 and 1230 cm1.
The band from 460 cm1 is assigned to the bending vibrations of
OAPAO units, d(PO)2 modes of (PO 2 )n chain groups [10,32]. That
from 517 cm1 appears in 0.8P2O5A0.2BaO [34] and P2O5ACdO
[35] matrices around 530 cm1 and is assigned to harmonics of
bending vibrations of O@PAO linkages [32,36]. Its shifted to
517 cm1 in the present matrix may be attributed to overlapping
with stretching vibrations of BiAO bonds in strongly distorted
BiO6 octahedral units which appear at 465–510 cm1 in the
Bi2O3-based glasses and Bi2O3 oxide [15,23]. A small contribution
of these vibrations to 460 band may be also considered.
The weak bands from 690 and 775 cm1 are assigned to sym-
metric and asymmetric stretching vibrations of PAOAP linkages
[3,34]. The bands appeared at 900 cm1 and 1040 cm1 are attrib-
uted according to the literature data to the asymmetric stretching
modes of PAOAP linkages (PAOAP)as in linear metaphosphate
chain [32,36] and to PO23 end groups [3], respectively.
The band near 1230 cm1 is attributed to the asymmetric
stretching mode of the double bonded oxygen vibrations, mas(P@O)
[3,32].
The increasing in intensity of all discussed bands can be ob-
served (Fig. 2) with the increasing of V2O5 content till x = 5 mol%.
This fact may be attributed to the network modifier role of V2O5
by depolymerization of phosphate–bismuthate network, especially
on the Bi2O3 network. In the studied glasses both P2O5 and Bi2O3
Fig. 2. IR spectra of xV2O5(1  x)[0.8P2O50.2Bi2O3] glass system with
0 6 x 6 50 mol%.
 N. Vedeanu et al. / Journal of Molecular Structure 1044 (2013) 323–327 325

are network former oxides, but P2O5 forms more organized long
range structures (polymeric chains) than Bi2O3. In the same time
it is in competition with Bi2O3 tendency of being a network former
which prevents the appearance of characteristic phosphate struc-
tural units. The addition of V2O5 which is a network modifier, acts
mainly on the weak component of phosphate–bismuthate lattice
(Bi2O3) allowing a better formation of phosphate groups (struc-
tures) and thus an increase in intensity of the characteristic bands.
On the other hand no supplementary bands appear in this case.
Relevant changes, the shift of certain bands and the appearance
of other new bands, can be observed in the IR spectra for
x P 10 mol%.
Thus in the low wavenumber region new bands appear at:
465 cm1, 505 cm1, 550 cm1 and 630 cm1. Three bands at
675 cm1, 710 cm1 and 770 cm1 can be seen around 700 cm1
region. In the high wavenumber region the bands at 910 cm1,
972 cm1, 1035 cm1 and 1080 cm1 prevail in the IR spectrum.
The bands in 465–630 cm1 range are due to the lattice vibra-
tions in vanadium oxide network [37,38]. The PAOAP bonds in Fig. 3. Representative ESR spectra of xV2O5(1  x)[0.8P2O50.2Bi2O3] glass system.
Q1 phosphate structures are broken with the addition of V2O5
oxide and replaced by PO4 isolated tetrahedral units (Q0 units).
Thus the bands from 700 cm1 region may be attributed accord- Hs ¼ b0 g jj Bz Sz þ b0 g ? ðBx Sx þ By Sy Þ þ Ajj Sz Iz þ A? ðSx Ix þ Sy Iy Þ; ð1Þ
ing to the literature data to bending vibration of P@O units [39], where b0 – Bohr magneton, g|| and g\ – components of g tensor, Bx,
that from 675 cm1, and to symmetric stretching vibrations of By, Bz – components of the magnetic field, Sx, Sy, Sz – components of
PAOAP rings [40] those from 710 cm1 and 770 cm1. the electron spin operator, Ix, Iy, Iz – components of the nucleus spin
The new bands from 972 cm1 and 1035 cm1 may be attrib- operator, A|| and A\ – principal components of the hyperfine cou-
uted to VAO bonds and also to the polyvanadate (clustered) ions pling tensor.
formations [41]. Also the absorption from 1080 cm1 is due to The values of the magnetic field for the hfs peaks from the par-
the vibrations of the isolated V@O vanadyl groups in VO5 trigonal allel and perpendicular absorption bands are given by the follow-
bipyramids [42]. ing equations [27]:
At x = 50 mol%, the bands characteristic for the phosphate net-   
work are strongly attenuated in intensity, except those specific 63 A2?
Bjj ðmÞ ¼ Bjj ð0Þ  mAjj   m2  ð2Þ
for methaphosphate chains (900 cm1) and methaphosphate 4 2Bjj ð0Þ
rings (1000 cm1) [12] and are covered by VAO vibrations. Thus
the broad bands around 910 cm1 and 1090 cm1 may be assigned   
63 ðA2jj þ A2? Þ
to the symmetric vibrations of VAO bonds of the VO4 tetrahedra in B? ðmÞ ¼ B? ð0Þ  mA?   m2  ð3Þ
4 4B? ð0Þ
glass structure and to the vibrations of the isolated V@O double
bonds in VO5 trigonal bipyramids [42], respectively. where m is the magnetic nuclear quantum number for vanadium
The 1230 cm1 band also decrease in amplitude due to the de- nucleus having the values: ±1/2, ±3/2, ±5/2 and ±7/2.
crease of the P2O5 content and shortening of the phosphate chain
hm
length. This fact suggests that V2O5 acts in this concentration range Bjj ð0Þ ¼ ð4Þ
g jj bo
as a network former which converts P@O bonds to bridging oxygen
upon formation of PAOAV bonds analogue with PAOACu and
PAOAFe bonds reported in the papers [3,32]. hm
B? ð0Þ ¼ ð5Þ
So, we may finally conclude that vanadium atoms bridge with g ? bo
non-bridging oxygen of PO4 units and V2O5 oxide acts as a network where m is the microwave frequency.
former. The reduction of the bonding force between P and O atoms ESR parameters of vanadium ions in the studied glasses are gi-
leads to the appearance of more non-bridging oxygen ions which ven in Table 1, they being in good agreement with other results re-
are involved in the new VAO bonds. Finally, the phosphate groups ported in literature [33].
are isolated in the vanadate network and in consequence V2O5 acts These data show that g|| < g\ < ge and A|| > A\, and correspond to
for x P 10 mol% as a network former instead of a network modifier. vanadyl ions in square pyramidal site as C4v symmetry. The vana-
dyl oxygen is attached axially above the V4+ site along the z-axis
3.2. ESR spectra (V@O bond), while the sixth oxygen forming the OAVO4AO unit
lies axially bellow the V4+ site in opposition with ‘‘yl’’ oxygen.
ESR spectra of some glasses from xV2O5(1  x)[0.8P2O5(0.2Bi2- The predominant axial distortion of the VO2+ octahedral oxygen
O3] system with 0 6 x 6 50 mol% are given in Fig. 3. For low con- complex along V@O direction may be the reason for nearly equal
tent of V2O5 (x 6 5 mol%) these spectra show a well resolved g and A values for all glass samples [31,43].
hyperfine structure (hfs) typical for vanadyl ions in a C4v symme- Fermi contact interaction term K, dipolar hyperfine coupling
try. The 16-line feature with eight parallel and eight perpendicular parameter P and MO coefficients are evaluated by using the
lines is typical of the unpaired (3d1) electron of VO2+ ion associated expressions [44]:
with 51V isotope (I = 7/2) in an axially symmetric crystal field
[29,30]. This distribution mode of vanadium ions in phosphate ma- Ajj þ 2A?
K¼ ð6Þ
trix is a result of its polymeric structure which can fix the metallic Ajj  A?
ions in some specific positions.
These spectra can be described by the following spin Hamilto- Ajj þ 2A?
P¼ ð7Þ
nian [31,34]: 3K
326 N. Vedeanu et al. / Journal of Molecular Structure 1044 (2013) 323–327

Table 1
ESR parameters of V4+ ions in xV2O5(1  x)[0.8P2O50.2Bi2O3] glass system.a

x g|| g\ A|| A\ K P b22 e2p

mol% 104 cm1 104 cm1 104 cm1
0.3 1.91 1.98 197 77 0.84 139 1.04 0.91
3 1.92 1.99 199 78 0.83 142 1.16 0.90
5 1.93 2.00 198 79 0.84 140 1.08 0.94
10 1.92 1.99 195 77 0.85 137 1.10 0.92
20 1.92 2.00 198 78 0.83 141 1.14 0.90
a
The error on g value is 0.01 and 1  104 cm1 on the A values.

 
7 Ajj  A? 7 5
b22 ¼  ðg e  g jj Þ þ ðg  g ? Þ
6 P 6 12 e
D? ðg e  g ? Þ
e2p ¼
2kb22
where D\ = 15,100 cm1, k = 170 cm1 and ge = 2.0023.
The estimated value for K (0.84) indicates a poor contribution
of the vanadium 4s orbital to the vanadyl bond in these glasses (Ta-
ble 1). The dipolar hyperfine coupling parameter value
P(109  104cm1) is similar with that reported for other phos-
phate glasses containing vanadium ions [45,46].
The MO coefficients (Table 1) show a ionic character for both p
bonds in xOy base – pyramidal plane (b22 ffi 1) and with vanadyl
oxygen (e2p ffi 0:92).
The dipole–dipole interactions prevail between V4+ ions in the
composition range of x < 5 mol%. This fact is suggested by the com-
position dependence of the line-width of first (DB1) and second
(DB2) hfs-peaks from the parallel absorption (Fig. 4.) which in-
crease with V2O5 content proving the diminution of V4+AV4+ dis-
tance. For x < 5 mol% V2O5 the network is dominated by P2O5
oxide which has a polymeric structure (organized at long range)
and fixes metallic ions in some specific positions, finally determin-
ing an isolated distribution species without interaction between
paramagnetic ions (V4+). By increasing the V2O5 content, this leads
to the depolymerization of phosphate network which affects (de-
stroys) isolated distribution mode of metallic ions allowing the
appearance of dipole–dipole interactions between them. For this
reason, ESR data suggest the network modifier role of V2O5 with
the depolymerization of the phosphate network.
At high content of vanadium oxide (x P 10 mol%), the ESR spec-
ð8Þ
tra may be regarded as a superposition of two ESR signals, one with
a well-resolved hfs typical for isolated VO2+ ions and another one
consisting in a broad line typical for associated (clustered)
V4+AV4+ ions. The number of associated ions increases with the
ð9Þ
increasing of V2O5 content and the presence of superexchange
interaction in V4+AO2AV4+ chains appears. These vanadate struc-
tures which isolate the phosphate groups at high V2O5 content is in
accord with the network former role of this metallic oxide.
Analyzing the shape of ESR spectra from Fig. 3, it can be noticed
that up to 5 mol% V2O5 the number of V4+ ions which are forming
in the P2O5Bi2O3 vitreous matrix is relatively small. The proportion
of these ions is considerable higher for high content of V2O5, which
determines the appearance of the superexchange magnetic inter-
actions between V4+ ions.
4. Conclusions
IR spectra of the studied glasses (for x 6 5 mol%) pointed out the
network modifier role of V2O5 especially on Bi2O3 lattice which al-
lows the phosphate groups to impose better their presence by
increasing their characteristic bands intensity. For x P 10 mol%
these spectra show the significant reduction of the bonding force
between P and O atoms, and the appearance of new PAOAV and
VAOAV bonds (structures) suggests the network former role of
V2O5.
ESR spectra of glasses with x 6 5 mol% are characteristic for iso-
lated vanadyl ions in axially symmetric crystal field and dipole–di-
pole interactions exist between paramagnetic ions. At high V2O5
content (x P 10 mol%) the spectra consist of a broad line character-
istic for associated (clustered) ions and the superexchange interac-
tions prevail between vanadium ions.
Both IR and ESR data show that up to x = 5 mol%, V2O5 acts as a
network modifier and for x P 10 mol% it acts as a network former,
the new PAOAV and VAOAV groups appearing in the vanadate–
bismuthate network.

Acknowledgements

This work was supported by Project Number PN II – IDEI code

129/2008 and ‘‘Iuliu Hatieganu’’ University of Medicine and Phar-
macy, Grant No. 27020/42/15.11.2011.

References

[1] R.K. Brow, J. Non-Cryst. Solids 1 (2000) 263.

Fig. 4. Composition dependence of the first (DB1) and second (DB2) hfs-peaks line-
widths from the parallel absorption bands versus V2O5 content (the error bars are
provided under 5% error limits).
[2] Z.M. Da Costa, W.M. Pontuscka, J.M. Giehl, C.R. Da Costa, J. Non-Cryst. Solids
352 (2006) 3663.
[3] P.Y. Shih, J.Y. Ding, S.Y. Lee, Mater. Chem. Phys. 80 (2003) 391.
[4] H. Hosono, H. Kawazoe, T. Kanazawa, J. Non-Cryst. Solids 37 (1980) 427.
[5] S. Gupta, N. Khanijo, A. Mansingh, J. Non-Cryst. Solids 181 (1995) 58.
[6] L.D. Bogomolova, V.N. Jackin, V.N. Lazukin, T.K. Pavlushkina, V.A. Shmuckler, J.
Non-Cryst. Solids 28 (1978) 375.
[7] G. Tricot, L. Montagne, L. Delevoye, G. Palavit, V. Kostoj, J. Non-Cryst. Solids
345–346 (2004) 56.
[8] I. Ardelean, S. Cora, D. Rusu, Physica B 403 (2008) 3682.
 N. Vedeanu et al. / Journal of Molecular Structure 1044 (2013) 323–327 327

[9] B.C. Sales, Mater. Res. Soc. Bull. 12 (1987) 32. [29] L.D. Bogomolova, V.N. Jackin, V.N. Lazukin, T.K. Pavlushkina, V.A. Shmuckler, J.
[10] Y.M. Moustafa, A. El-Adawy, Phys. Status Solidi A179 (2000) 83. Non-Cryst. Solids 375 (1978) 28.
[11] K. Meyer, Phys. Chem. Glasses 39 (1998) 108. [30] A. Shames, O. Lev, B. Josefzon-Kuyavskaya, J. Non-Cryst. Solids 163 (1993)
[12] Y.M. Moustafa, K. El-Egili, J. Non-Cryst. Solids 240 (1998) 144. 105.
[13] E. Lippma, M. Magi, A. Samoson, G. Englehardt, A.R. Grimmer, J. Am. Chem. Soc. [31] V.P. Seth, S. Gupta, A. Jindal, S.K. Gupta, J. Non-Cryst. Solids 263 (1993)
102 (1980) 4889. 162.
[14] S. Bale, M. Purinima, Ch. Srinivasu, S. Rahman, J. Alloys Compd. 457 (2008) 545. [32] H. Doweidar, Y.M. Moustafa, K. El-Egli, I. Abbas, Vib. Spectrosc. 91 (2005) 37.
[15] I. Ardelean, D. Rusu, J. Opt. Adv. Mater. 10 (2008) 66. [33] I. Ardelean, O. Cozar, N. Vedeanu, D. Rusu, C. Andronache, J. Mater. Sci.: Mater.
[16] C. Stehle, C. Vira, D. Vira, D. Hogan, S. Feller, M. Affatigato, Phys. Chem. Glasses Electron. 18 (2007) 963.
39 (1998) 83. [34] N. Vedeanu, R. Stanescu, S. Filip, I. Ardelean, O. Cozar, J. Non-Cryst. Solids 358
[17] T. Komatsu, R. Sato, K. Imai, K. Matusita, T. Yamashita, Jpn. J. Appl. Phys. 27 (2012) 1881.
(1998) L550. [35] C. Ivasßcu, I.B. Cozar, L. Dărăban, G. Damian, J. Non-Cryst. Solids 359 (2013) 60.
[18] Y. Dimitriev, V.T. Mihailova, J. Sci. Lett. 9 (1990) 1251. [36] P. Bergo, S.T. Reis, W.M. Pontuschka, J.M. Prison, C.C. Motta, J. Non-Cryst. Solids
[19] S. Hazra, A. Ghosh, Phys. Rev. B56 (1997) 13. 336 (2004) 159.
[20] S. Simon, M. Todea, J. Non-Cryst. Solids 352 (2006) 2947. [37] S. Blanchard, J. Chim. Phys. 61 (1964) 747.
[21] V.C. Gowda, C.N. Reddy, K.C. Radha, R.V. Anavekar, J. Etourneau, K.J. Rao, J. [38] L. Stanescu, E. Indrea, I. Ardelean, M. Coldea, I. Bratu, D. Stanescu, Rev. Roum.
Non-Cryst. Solids 353 (2007) 1150. Phys. 21 (1976) 939.
[22] S. Daviero, L. Montagne, G. Palavit, G. Mairesse, S. Beliu, V. Briois, J. Phys. Chem. [39] U. Selvaraj, K.J. Rao, J. Non-Cryst. Solids 72 (1985) 315.
Solids 64 (2003) 253. [40] M.C.R. Shastry, K.J. Rao, J. Spectrochim. Acta A 46 (1990) 1581.
[23] S. Rani, S. Sanghi, A. Agarwal, N. Ahlawat, J. Alloys Compd. 477 (2009) 504. [41] H. Miyata, K. Fujii, T. Ono, Y. Kubokawa, T. Ohno, F. Hatayama, J. Chem. Soc.
[24] A. Shaim, M. Et-Tabirom, Phys. Chem. Glasses 42 (2001) 381. Faraday Trans. I (83) (1987) 675.
[25] A. Shaim, M. Et-Tabirou, L. Montagne, G. Palavit, Phys. Chem. Glasses 37 (2002) [42] Y. Dimitriev, V. Dimitriev, J. Non-Cryst. Solids 122 (1990) 133.
3459. [43] P.G. Prakash, J.L. Rao, Spectrachim. Acta A61 (2005) 2595.
[26] B. Elouadi, M. Ouchetto, E.I.H. Arbib, N. Amraoui, Phase Trans. 13 (1988) 219. [44] D. Kivelson, S.K. Lee, J. Chem. Phys. 41 (1964) 1896.
[27] J. Jiraik, L. Koudelka, J. Pospisil, P. Mosner, L. Montagne, L. Delevoye, J. Mater. [45] O. Cozar, I. Ardelean, V. Simon, L. David, V. Mih, N. Vedeanu, Appl. Magn.
Sci. 42 (2007) 8592. Reson. 16 (1999) 529.
[28] R. Ravikumar, V. Rajagopal Reddy, A.V. Chandrasekhar, B.J. Reddy, P.S. Rao, J. [46] N.V. Ramana, K. Sivakumar, S. Rahman, D.S. Babu, S.G. Satyanarayan, G.S.
Alloys Compd. 272 (2002) 337. Sastry, J. Mater. Sci. Lett. 8 (1989) 1221.