Journal of Non-Crystalline Solids 428 (2015) 151155

Contents lists available at ScienceDirect

Journal of Non-Crystalline Solids

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

Study on the effect of vanadium oxide in calcium phosphate glasses by

Raman, IR and UVvis spectroscopy
D.A. Magdas a, N.S. Vedeanu b,, D. Toloman a
a
National Institute for Research and Development for Isotopic and Molecular Technologies, RO-400293 Cluj-Napoca, Romania
b
Iuliu Hatieganu University of Medicine and Pharmacy, Department of Pharmaceutical Physics, Biophysics, RO-400023 Cluj-Napoca, Romania

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

Article history: Vanadium doped calcium phosphate glass materials with progressive V2O5 content were prepared and analyzed
Received 10 June 2015 by Raman, IR and UVvis spectroscopy. The changes induced by the presence of different amounts of vanadium
Received in revised form 30 July 2015 ions and observed in the spectra were discussed in connection with the structural modications of the glass net-
Accepted 11 August 2015
work. Special attention was given to the dual role exerted by the vanadium ions, that of strong modier agent for
Available online xxxx
low vanadium content (less than 10 mol%) and that of glass network former for high vanadium content (higher
Keywords:
than 20 mol%). The preparation and the characterization of the materials using non-conventional former oxides
Calcium phosphate materials; like vanadium oxide can be considered as a new beginning in the eld of material science.
Vanadium; 2015 Elsevier B.V. All rights reserved.
IR;
Raman;
UVvis

1. Introduction 0 x 40 mol% consist of a polymer like structure of regular tetrahe-

Vanadium phosphate glasses continue to present high interest for
the researchers in the eld of material science mainly because of their
potential application. It was demonstrated in literature that such mate-
rials exhibit semiconducting behavior [13], low thermo-optical coef-
cient and large emission characteristics which make them suitable for
laser devices [4], but above all these properties, it is essential to under-
line that most of the calciumphosphate materials are biocompatible
and can be used as biomaterials [57]. Furthermore, vanadium added
in the calcium phosphate network can be an active agent in helping
body metabolism, helping in the growth of bones, although this metab-
olism it is not yet fully understood [8,9]. The theme is important and
represents one of our constant research interests. Even more, the addi-
tion of vanadium in the calciumphosphate network improves chemical
durability of the materials as it is known from literature [10].
The properties of phosphate materials are drastically determined by
the type of modier cation and by the degree of depolymerization of the
phosphate network and this is the aim of our present study. Vitreous
P2O5 has a three-dimensional network build up with PO4 tetrahedra in-
terconnected by three of their four corners. The fourth one is occupied
by terminal double-bonded oxygen atom. By introducing the glass
network modiers a depolymerization of P2O5 vitreous skeleton ap-
pears conducting to the breaking of POP bond and formation of termi-
nal oxygen atoms. xV2O5(100 x)[P2O5CaO] glass materials with
Corresponding author.
E-mail address: nicoletavedeanu@yahoo.com (N.S. Vedeanu).
drons based on PO4 linked groups, interrupted by the glass modier
ions, vanadium and calcium ions in our case. The basic structure of
phosphate glasses is represented by PO4 tetrahedra. The used terminol-
ogy to describe the tetrahedral units is the so-called Qn notation, where
n represents the number of bridging oxygen atoms (BOs) per PO4 tet-
rahedron. The pure vitreous P2O5 structure is characterized by Q3 tetra-
hedra having three bonding oxygen atoms and one double bonded
oxygen P_O, forming a three-dimensional cross-linked network [11].
Vanadium pentoxide V2O5, like P2O5 is considered to be a non-
conventional network former and in consequence phosphate glasses
doped with vanadium can be synthesized with high content of V2O5
(even more than 50 mol%) [12]. Oxides such as V2O5, Bi2O3, WO3, and
TeO2 do not form glass on their own, but mixed with conventional for-
mers they become glass formers for better structured glass networks
[13]. On the other hand, ions like Ca2 + may play a consistent role in
the modication of phosphate network [14].
Different valence states of vanadium in phosphate glasses are possi-
ble, as vanadium exists [1517] under the form of V3+, V4+ and V5+.
The trivalent vanadium ions normally exist in distorted octahedral coor-
dination with oxygen and exhibit two characteristic absorption bands at
350400 nm, and 580680 nm and a third possible band in the UV
region originating from the electron transfer within the vanadium
ion itself. The tetravalent vanadium ions are assumed to exist as vanadyl
ions [VO2+] and exhibit four characteristic weak bands at about 420 nm,
760860 nm and ~1000 nm in addition to a possible UV band [18,19].
The pentavalent vanadium ions correspond to the d conguration
and thus will not give rise to dd transitions but give a characteristic

http://dx.doi.org/10.1016/j.jnoncrysol.2015.08.012
0022-3093/ 2015 Elsevier B.V. All rights reserved.
152 D.A. Magdas et al. / Journal of Non-Crystalline Solids 428 (2015) 151155
charge transfer band at ~380 nm [18,19]. The ratio of each valence of va-
nadium ions in a glass generally depends on the type and composition
of the respective glass and melting conditions. Our previous studies re-
garding the local structure of vanadium ions in calciumphosphate
glasses using EPR spectroscopy have shown that these ions are present
as vanadyl ions in a C4v symmetry [20,21].
The present work is an attempt to demonstrate with the help of
Raman, IR and UVvis spectroscopic techniques that the progressive in-
troduction of vanadium ions in the calcium phosphate network of the
studied glasses leads to the formation of VOP and VOV new
bonds and to an evolution regarding the role of V2O5 from simple mod-
ier to network glass former.
2. Experimental
The starting materials used in the present investigation were
(NH4)2HPO4, CaO and V2O5 of reagent grade purity. The samples were
prepared by weighing suitable proportions of the components, powder
mixing and mixture melting in sintered corundum crucibles at 1250 C
for 30 min. The mixtures were put into the furnace directly at this tem-
perature. The obtained glass samples were quenched by pouring the
molten glass on stainless steel plates.
Raman spectra were obtained with a Horiba Jobin Yvon system
equipped with Olympus BX41 optical microscope, a grating of 1800
grooves per mm and Peltier CCD cooler. The spectra were obtained
under using the 632.8 nm emission line of a heliumneon laser. The
laser power was about 1.5 mW (low enough to avoid any sample alter-
ation or decomposition). The spectral resolution was about 1.3 cm1
and the wave number accuracy was 0.5 cm1. Three multiple measure-
ments per sample were done to check for the potential micron-range
heterogeneity and for the effects of sample orientation.
IR spectra were recorded with a Bruker IFS66/DSP spectrometer in
4002000 cm 1 range, using the anhydrous KBr technique to avoid
structural modications caused by the ambient moisture. The resolution
of the IR spectra is of 2 cm1.
The structure of samples was analyzed by means of X-ray diffraction
using a Bruker D8 Advanced X-ray diffractometer with a graphite
monochromator for CuK radiation with = 1.54 . The increment
for the measurements was of 0.1. The pattern obtained did not reveal
any crystalline phase in all samples (Fig. 1).
Optical response of the samples was studied by using UVvis ab-
sorption spectra recorded from a JASCO V570 UVvis-NIR Spectro-
photometer equipped with absolute reectivity measurement
JASCO ARN-475 accessory. The transformation of reectance spectra
in absorbance spectra was obtained with an intern soft of apparatus.
Fig. 1. XRD spectra of xV2O5(100 x)[P2O5CaO] glass system.
The wavelength accuracy was of 0.3 nm and the wavelength re-
peatability was 0.1 nm.
3. Results
3.1. Raman spectra
The experimental Raman spectra of xV2O5(100 x)[P2O5CaO]
glass system with 0 x 40 mol% are presented in Fig. 2. Because the
bands are large and asymmetric a deconvolution of each spectrum
was necessary in order provide a more accurate band assignments and
to follow and quantify the individual band evolution. As a consequence
we used for discussion the deconvoluted spectra instead of the experi-
mental ones. A deconvoluted Raman spectrum is presented in Fig. 3
and the band assignments are given in Table 1.
3.2. IR spectra
IR absorption spectra of xV2O5(1 x)[P2O5CaO] glass system with
0 x 40 mol% are presented in Fig. 4.
The specic IR bands of phosphate glasses are located in the
5001400 cm1 region. On the other hand, the specic V2O5 vibrations
are located at: ~ 820 cm 1 for VO vibrations in VOV chains and
~1018 cm1 for V_O vibrations [22,23].
3.3. UVvis absorption spectra
Fig. 5 illustrates the UVvis absorption spectra of four representative
samples of different concentration (0.5; 1; 10 and 40 mol%). UVvis ab-
sorption spectra of these samples were recorded at room temperature
in the wavelength region of 2001000 nm.
It was indicated in several papers [19,24] that vanadium ions in
phosphate glasses occur mostly under the form of V3+ and V4+ ions, de-
pending by the nature of the host glass, temperature and vanadium con-
tent. All the spectra revealed the appearance of two peaks in the UV
region centered around 200300 nm, peaks that are assigned to trace
to trace iron impurities due to a possible contamination of raw materials
used for glass preparation [25,26].
4. Discussion
4.1. Raman deconvoluted spectra
The relative intensity of the band from 350 cm1 is increasing with
the addition of vanadium oxide. By increasing the V2O5 concentration,
Fig. 2. Experimental Raman spectra of xV2O5 (100 x)[P2O5CaO] glass system with
0 x 40 mol%.
 D.A. Magdas et al. / Journal of Non-Crystalline Solids 428 (2015) 151155 153

Fig. 3. Deconvoluted Raman spectra of xV2O5 (100 x)[P2O5CaO] for 0.5 mol%. Fig. 4. IR spectra of xV2O5(100 x)[P2O5CaO] glass system with 0 x 40 mol%.

(PO3)2 groups increases when the long chains of the metaphosphates

the 350 cm1 band becomes more intense and gets wider. The growth
of these bands, attributed to the bending mode of the phosphate (PO4)
polyhedra, is related to the strong depolymerization of the long phos-
phate chains [27]. Around ~500 cm1 bending and torsion vibrations
occur and they have been assigned to the vanadium cation motion vi-
brations and chain conformation [28]. With the progressive addition
of V2O5 oxide, the number of PO4 units strongly increases, a fact that is
also related to the drastic depolymerization of phosphate network. A
symmetric stretching vibration of the PO bonds of the orthophosphate
(PO34) unit, (Q0) respectively is centered at about 606 cm1. The in-
tensity of this band increases with the addition of vanadium oxide due
to the same depolymerization effect.
The band at 705 cm1 derives from the POP symmetric stretch of
the bridging oxygen atoms in Q2 species whereas the band at 780 cm1
arises from the asymmetric vibrations of the same species [29]. With the
increase of vanadium oxide content these bands decrease strongly in in-
tensities as a direct effect of the phosphate network depolymerization.
New features appear around 900 cm1 with the increases of V2O5
content, attributed to symmetric stretching vibrations of VOV and
OVO linkages. By addition of vanadium oxide these bands increase
in intensity and for concentrations x 20% these become the most in-
tense features of the spectrum. The same tendency was observed for
970 cm1 band, which can be assigned to a superposition of symmetric
stretching vibration of Q0 tetrahedra with the stretching vibrations of
V_O bond [30]. The increase of these bands indicates both the depoly-
merization of phosphate network and an increased number of V_O
bonds. The (PO3)2 end-of-chain asymmetric stretching vibrations are
present in our spectra at about 1038 cm 1. The concentration of
are replaced by the small phosphate units [31].
Around 1145 cm1 the symmetric stretching motion appears specif-
ic for the two non-bridging oxygen NBO atoms bonded to phosphorous
atoms (PO2) in the Q2 phosphate chains [29,3234]. As it can be ob-
served in the case of the other two bands from 705 cm 1 and
780 cm1, characteristic to long phosphate chains, this band decreases
also in intensity with the increase of vanadium oxide content. At the
same time, the same tendency was observed in the case of the band cen-
tered at 1172 cm1 which is assigned to strained (PO2) symmetric
(strained structural units, possibly three- or four-membered rings)
[35]. This band is present in Raman spectra only for low vanadium con-
centrations; for x 5% it disappears from the spectra.
The band centered around 1260 cm1 due to symmetric stretching
vibration of double bond P_O strongly decreases in intensity by addi-
tion of V2O5 because the formation of VO_P bond type that weaken
the P_O bond. The reduced force between P and O atoms will lead to
the formation of free oxygen atoms which will be involved in the new
formed VO bonds [1].
From these considerations we can conclude that by increasing vana-
dium oxide content a strong depolymerization appears in the glass
structure. Beside this, the specic bands of vanadium oxide become
more intense and for high V2O5 these bands become the dominant fea-
tures of the spectra. It can be noted that thus, the vanadium atom pre-
fers to bridge with resulting oxygen atoms from the depolymerization
process instead of bridging with P atoms, producing therefore their
own networks. In this case vanadium oxide acts as a network former,
similar to the previously reported results for xV2O5(100 x)NaPO3
glass system [12].

Table 1
The assignments and relative areas of different vibration bands from Raman spectra of xV2O5 (100 x)[P2O5CaO] glass system.

(cm1) Assignments Relative areas dependence of vibrational bands versus V2O5 concentrations (x mol%)a

0.5a 5a 20a

530 Bending vibrations of PO4 polyhedra 5.2 1.9 0.01

606 (PO)symstretch. Q0 0.7 0.8 1
705 (POP)symstretch. Q2 11.7 11.7
780 (POP)asymstretch. Q2 12.7 6.5 6.5
900 Symmetric stretching vibrations of VOV and OVO linkages 3 47.7
970 (PO4)symstretch Q0 and (V_O)symstretch 5.57 11.2 24.7
1038 (PO3)2asymstretch 7.9 18.6 11.9
1145 (PO2)symstretch Q2 23.5 28.3 7.5
1172 Strained (PO2)symstretch 8.36
1260 (P_O)symstretch 10.7 7.8 0.6
a
Relative areas were calculated with an error of 3%5%.
154 D.A. Magdas et al. / Journal of Non-Crystalline Solids 428 (2015) 151155
Fig. 5. Optical absorption spectra of xV2O5(100 x)[P2O5CaO] glass system with
0 x 40 mol%.
4.2. IR spectra
It is well known from literature that in the case of phosphate glasses
the shape of Raman bands are better visualized compared with the IR
ones, probably because Raman spectroscopy generates a signal from
the depth of the sample and not only from the surface [36,37], but IR
spectra, complementary to Raman spectra, underlined and supported
our conclusions.
Thus, the band around 550 cm1 is attributed to OPO bending vi-
brations in Q1 groups [36]. By addition of vanadium oxide this band
shifts to higher wavenumber due to the depolymerization of the phos-
phate network. Other IR bands at 760 cm1 and 900 cm1 are assigned
to the symmetric and asymmetric modes of POP bonds in Q1 units, re-
spectively [33]. A band shift from 760 cm1 to higher wave number is
observed in the spectra with the increase of vanadium oxide content.
The observed tendency is directly related with the modication of P
OP bond length with the depolymerization of phosphate network
[11]. The 1125 cm1 band is associated with the asymmetric stretching
vibrations in Q2 groups (PO3)2 [36]. By adding vanadium oxide this
band decreases in intensity and for a concentration x 20 mol% it
disappears from the spectrum. The progressive vanishing of this band,
which is characteristics for the long phosphate chains is related to the
gradual depolymerization of phosphate network. The broad band from
12001400 cm 1 is attributed to both asymmetric stretching of the
double bonded oxygen vibrations [38] and to the (P_O) symmetric
stretching vibrations [39]. A decrease in intensity of this band is ob-
served for high concentrations of V2O5 due to the symmetric stretching
vibrations of VO_P linkages which allow the weakness of P_O bond
[11,20,2731].
For high concentrations of vanadium oxide (x 20% mol) in IR spec-
tra a shoulder at about ~820 cm1 attributed to symmetric stretching
vibrations in VOV chains appears [22,23]. Also, the band around
1100 cm1 becomes broader by addition of V2O5 due to the superposi-
tion of the two bands corresponding to vibration of PO3 4 groups and vi-
brations of V_O bonds.
Thus, by adding vanadium oxide a strong depolymerization appears
in these glasses. Moreover, the specic bands of vanadium oxide be-
come more intense with the addition of V2O5 fact that is also supported
by Raman bands at this concentration.
4.3. UVvis absorption spectra
For the spectra of low vanadium content (0.5 and 1 mol%), beside
the UV peaks, a weak absorption peak appears at ~ 340 nm belonging
to V3 + ions [19] and other two absorption bands centered at about
450 nm and 690 nm. The band at about 450 nm is attributed according
to the literature to tetravalent vanadyl (VO2+) ions [19] and the band at
about 690 nm belongs to the trivalent vanadium ions [17]. Our previous
EPR data [21] demonstrated also that up to 10 mol% isolated V4+ ions
are present mostly in a distorted C4V symmetry.
For the sample with 10 mol% vanadium oxide, a broad band in
300500 nm spectral range and other two weak peaks centered at
~680 nm and ~ 910 nm appeared. The rst band is attributed to the con-
tribution of both tetravalent vanadyl (VO2+) ions and pentavalent V5+
ions. The second peak is attributed to V3+ ions and the third one to tet-
ravalent vanadyl (VO2+) ions [40].
The appearances of these bands are correlated with our previous EPR
results [21,41,42]. Up to 10 mol% V2O5 the number of V4+V4+ clusters
increase due to strong dipoledipole interactions, but for x 10 mol%
vanadium content the superexchange interactions are prevalent be-
tween the resonance centers.
On the other hand, Raman spectra have shown that at ~ 10 mol%
V2O5 an important depolymerization of the vitreous network occurs
and in consequence free electrons are produced in the vitreous network
[19]. From the combination of V4 + with such free electrons new V3+
ions appear.
In the case of the sample with 40 mol% vanadium oxide, the preva-
lent band in the spectrum is centered at about 380 nm, which indicates
the existence of vanadium ions mainly as V3+ ions as a consequence of
network depolymerization and re-organization imposed by the higher
vanadium ions concentration.
The visual appearances of all prepared samples support also our as-
sumption that the studied glasses favor the presence of the two low va-
lance state forms of vanadium. The color of our samples varies from
bluishlight green color (specic for vanadyl ions [19]) for low vanadi-
um content to greendark green color (specic for V3+ ions [19]) with
the increase of V2O5 content.
5. Conclusion
Raman spectra provided a better image on the structural changes of
the studied phosphate system, mostly because Raman bands are
narrower than IR bands for phosphate glasses, but both IR and Raman
spectra revealed the phosphate network depolymerization with in-
creasing V2O5 content because there is a reduction of strength in the
connection between P and O atoms that cause non-bridging oxygen
atoms involved in new VOV linkages. In the case of vanadium
doped glasses, at high concentration (x N 20 mol%) the bands belonging
to the vibration in V2O5 groups dominate the spectra while the bands
belonging to the phosphate chains are strongly reduced except the spe-
cic bands of the small phosphate units. From this structural investiga-
tion it can be said that vanadium prefers to bridge with the oxygen that
do not take part in the PO4 units making new structures and in conse-
quence it acts as a network former.
UVvis spectra of the investigated glasses have shown the presence
of vanadium ions under the form of V4+ and V3+ ions as the literature
reports.
References
[1] J.E. Garbarczyk, P. Machowski, M. Wasiucionek, L. Tykarski, R. Bacewicz, A.
Aleksiejuk, Studies of silvervanadatephosphate glasses by Raman, EPR and im-
pedance spectroscopy methods, Solid State Ionics 136 (2000) 10771083.
[2] E.E. Assem, K.R. Mahmoud, T. Sharshar, C. Siligardi, Structure, magnetic and positron
lifetime studies on CaOZrO2SiO2 glass system doped with vanadium oxide, J. Phys.
D. Appl. Phys. 39 (2006) 734736.
[3] M.M. El-Desoky, Small polaron transport in V2O5NiOTeO2 glasses, J. Mater. Sci.
Mater. Electron. 14 (2003) 215221.
[4] J. Livage, J.P. Jollivet, E. Tronc, Electronic properties of mixed valence oxide gels, J.
Non-Cryst. Solids 121 (1990) (1990) 3539.
[5] T. Kitsugi, T. Yamamuro, T. Nakamura, S. Katani, T. Kokubo, H. Takeuchi, Four calci-
um phosphate ceramics as bone substitutes for non-weight-bearing, Biomaterials
14 (1993) 216224.
 D.A. Magdas et al. / Journal of Non-Crystalline Solids 428 (2015) 151155
[6] T. Kitsugi, T. Yamamuro, T. Nakamura, M. Oka, H. Tacheuchi, Transmission electron
microscopy observations at the interface of bone and four types of calcium phos-
phate ceramics with different calcium/phosphorus molar ratios, Biomaterials 16
(1995) 11011107.
[7] R. Li, A.E. Clark, L.L. Hench, An investigation of bioactive glass powders by solgel
processing, J. Appl. Biomater. 2 (1991) 231239.
[8] S.B. Etcheverry, D.A. Barrio, Vanadium and bone: relevance of vanadium compounds
in bone cell, chapter 15/ACS symposium series 974, Am. Chem. Soc. (2007) 204216
(PubMed).
[9] S.B. Etcheverry, D.A. Barrio, Vanadium and bone development: putative signaling
pathways, Can. J. Physiol. Pharmacol. 84 (7) (2006) 677686.
[10] F.H. El-Batal, Y.M. Hamdy, S.Y. Marzouk, UVvisible and infrared absorption spectra
of transition metals-doped lead phosphate glasses and the effect of gamma irradia-
tion, J. Non-Cryst. Solids 355 (2009) 24392447.
[11] E. Metwalli, M. Karabulut, D.L. Sidebottom, M.M. Morsi, R.K. Brow, Properties and
structures of copper ultraphosphate glasses, J. Non-Cryst. Solids 344 (2004)
128134 (n).
[12] G. Tricot, L. Montagne, L. Delevoye, G. Palavit, V. Kostoj, Redox and structure of sodi-
umvanadophosphate glasses, J. Non-Cryst. Solids 345 (2004) 5660.
[13] C.N. Reddy, V.C.V. Gowda, R.P.S. Chakradhar, Elastic properties and structural studies
on leadborovanadate glasses, J. Non-Cryst. Solids 354 (2008) 3240.
[14] V.C.V. Gowda, R.V. Anavekar, Elastic properties and spectroscopic studies of lithium
lead borate glasses, Ionics 10 (2004) 103108.
[15] G.D. Khatak, N. Tabet, Local structure and redox state of vanadium in strontium
vanadate glasses, J. Electron Spectrosc. Relat. Phenom. 136 (2004) 257264.
[16] E.E. Assem, Effect of replacing calcium oxide with calcium halide on crystallization
and some physical properties of calcium vanadium phosphate glass ceramics,
Physica B 406 (2011) 421425.
[17] G.D. Khattak, A. Mekki, L.E. Wenger, X-ray photoelectron spectroscopy (XPS) and
magnetic susceptibility studies of vanadium phosphate glasses, J. Non-Cryst. Solids
355 (2009) 21482155.
[18] A.M. Nassar, N.A. Ghoneim, Vanadium contribution in different glasses in view of
the ligand eld theory, J. Non-Cryst. Solids 46 (1981) 181195.
[19] F.H. ElBatal, M.A. Marzouk, A.M. Abdelghany, UVvisible and infrared absorption
spectra of gamma irradiated V2O 5 doped in sodium phosphate, lead phosphate,
zinc phosphate glasses: a comparative study, J. Non-Cryst. Solids 357 (2011)
10271036.
[20] N. Vedeanu, O. Cozar, I. Ardelean, B. Lendl, D.A. Magdas, Raman spectroscopic study
of CuOV2O5P2O5CaO glass system, Vib. Spectrosc. 48 (2008) 259262.
[21] N. Vedeanu, O. Cozar, I. Ardelean, S. Filip, Spectroscopic investigation on some calci-
umphosphate glasses, J. Optoelectron. Adv. Mater. 8 (3) (2006) 11351139.
[22] I. Ardelean, C. Andronache, C. Campean, P. Pascuta, Structural investigation of
xFe2O3 (100 x)[P2O5CaO] and x(Fe2O3V2O5)(100 x)[P2O5CaO] glass sys- [41] N.S. Vedeanu, D.A. Magdas, The inuence of some transition metal ions in lead- and
tems by IR spectroscopy, Mod. Phys. Lett. B 45 (2004) 18111816.
[23] L. Stanescu, E. Indrea, I. Ardelean, M. Coldea, I. Bratu, D. Stanescu, Some contribu-
tions to the investigation of V2O5MoO2 system, Rev. Roum. Phys. 21 (9) (1976)
939951.
155
[24] N. Kerkouri, M. Haddad, M. Et-tabirou, A. Chahine, I. Laanab, FTIR, Raman, EPR and
optical absorption spectral studies on V2O5-doped cadmium phosphate glasses,
Physica B 406 (2011) 31423148.
[25] D. Moncke, D. Ehrt, Irradiation induced defects in glasses resulting in the photoion-
ization of polyvalent dopants, Opt. Mater. 25 (2004) 425437.
[26] S.Y. Marzouk, F.H. Elbatal, Ultravioletvisible absorption of gamma-irradiated tran-
sition metal ions doped in sodium metaphosphate glasses, Nucl. Inst. Methods
Phys. Res. B 248 (2006) 90102.
[27] A. Mogus-Milankovic, A. Santic, A. Gajovic, D.A. Day, Spectroscopic investigation of
MoO3Fe2O3P2O5 and SrOFe2O3P2O5 glasses. Part I, J. Non-Cryst. Solids 325
(2003) 7684.
[28] A. Mogus-Milankovic, L. Pavic, S.T. Reis, D.E. Day, M. Ivanda, Structural and electrical
properties of Li2OZnOP2O5 glasses, J. Non-Cryst. Solids 356 (2010) 715719.
[29] M.A. Karakassides, A. Saranti, I. Koutselas, Preparation and structural study of binary
phosphate glasses with high calcium and/or magnesium content, J. Non-Cryst.
Solids 347 (2004) 6979.
[30] Y.M. Moustafa, K. El-Egili, Infrared studies on the structure of sodium phosphate
glasses, J. Non-Cryst. Solids 240 (1998) 144153.
[31] G.L. Saout, P. Simon, F. Fayon, A. Blin, Y. Vaills, Raman and infrared study of
(PbO)x(P2O5)(1 x) glasses, J. Raman Spectrosc. 33 (2002) 740746.
[32] J. Koo, B. Bae, H.K. Na, Raman spectroscopy of copper phosphate glasses, J. Non-
Cryst. Solids 212 (1997) 173179.
[33] M. Scagliotti, M. Villa, G. Chiodelli, Short range order in the network of the
borophosphate glasses: Raman results, J. Non-Cryst. Solids 93 (1987) 350360.
[34] J.E. Pemberton, L. Latifzadeh, J.P. Fletcher, S.H. Risbud, Raman spectroscopy of calci-
um phosphate glasses with varying CaO modier concentrations, Chem. Mater. 3
(1991) 195200.
[35] J.J. Hudgens, R.K. Brow, D.R. Tallant, S.W. Martin, Raman spectroscopy study of the
structure of lithium and sodium ultraphosphate glasses, J. Non-Cryst. Solids 223
(1998) 2131.
[36] A.M. Emov, IR fundamental spectra and structure of pyrophosphate glasses along
the 2ZnOP2O5 2Me2OP2O5 join (Me being Na or Li), J. Non-Cryst. Solids 209
(1997) 209226.
[37] R.K. Brow, Review: the structure of simple phosphate glasses, J. Non-Cryst. Solids
263264 (2000) 128.
[38] B.V.R. Chowdari, K.I. Tan, W.T. Chia, R. Gopalakrishnam, X-ray photoelectron spec-
troscopic studies of molybdenum phosphate glassy system, J. Non-Cryst. Solids
119 (1990) 95102.
[39] J.J. Hudgens, S.W. Martin, Glass transition and infrared spectra of alkali, anhydrous
lithium phosphate gasses, J. Am. Ceram. Soc. 76 (1994) 16911696.
[40] C.R. Bamford, Color Generation and Control in Glass: Glass Science and Technology,
vol. 2, Elsevier, Amsterdam, 1977.
calciumphosphate glasses, J. Alloys Compd. 534 (2012) 9396.
[42] IR and Raman investigations on V2O5P2O5BaO glass system with opto-electronic
potential, J. Non-Cryst. Solids 358 (2012) 18811885.