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Journal of Non-Crystalline Solids 428 (2015) 151155

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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-


drons based on PO4 linked groups, interrupted by the glass modier
Vanadium phosphate glasses continue to present high interest for ions, vanadium and calcium ions in our case. The basic structure of
the researchers in the eld of material science mainly because of their phosphate glasses is represented by PO4 tetrahedra. The used terminol-
potential application. It was demonstrated in literature that such mate- ogy to describe the tetrahedral units is the so-called Qn notation, where
rials exhibit semiconducting behavior [13], low thermo-optical coef- n represents the number of bridging oxygen atoms (BOs) per PO4 tet-
cient and large emission characteristics which make them suitable for rahedron. The pure vitreous P2O5 structure is characterized by Q3 tetra-
laser devices [4], but above all these properties, it is essential to under- hedra having three bonding oxygen atoms and one double bonded
line that most of the calciumphosphate materials are biocompatible oxygen P_O, forming a three-dimensional cross-linked network [11].
and can be used as biomaterials [57]. Furthermore, vanadium added Vanadium pentoxide V2O5, like P2O5 is considered to be a non-
in the calcium phosphate network can be an active agent in helping conventional network former and in consequence phosphate glasses
body metabolism, helping in the growth of bones, although this metab- doped with vanadium can be synthesized with high content of V2O5
olism it is not yet fully understood [8,9]. The theme is important and (even more than 50 mol%) [12]. Oxides such as V2O5, Bi2O3, WO3, and
represents one of our constant research interests. Even more, the addi- TeO2 do not form glass on their own, but mixed with conventional for-
tion of vanadium in the calciumphosphate network improves chemical mers they become glass formers for better structured glass networks
durability of the materials as it is known from literature [10]. [13]. On the other hand, ions like Ca2 + may play a consistent role in
The properties of phosphate materials are drastically determined by the modication of phosphate network [14].
the type of modier cation and by the degree of depolymerization of the Different valence states of vanadium in phosphate glasses are possi-
phosphate network and this is the aim of our present study. Vitreous ble, as vanadium exists [1517] under the form of V3+, V4+ and V5+.
P2O5 has a three-dimensional network build up with PO4 tetrahedra in- The trivalent vanadium ions normally exist in distorted octahedral coor-
terconnected by three of their four corners. The fourth one is occupied dination with oxygen and exhibit two characteristic absorption bands at
by terminal double-bonded oxygen atom. By introducing the glass 350400 nm, and 580680 nm and a third possible band in the UV
network modiers a depolymerization of P2O5 vitreous skeleton ap- region originating from the electron transfer within the vanadium
pears conducting to the breaking of POP bond and formation of termi- ion itself. The tetravalent vanadium ions are assumed to exist as vanadyl
nal oxygen atoms. xV2O5(100 x)[P2O5CaO] glass materials with 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].
Corresponding author. The pentavalent vanadium ions correspond to the d conguration
E-mail address: nicoletavedeanu@yahoo.com (N.S. Vedeanu). 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- The wavelength accuracy was of 0.3 nm and the wavelength re-
nadium ions in a glass generally depends on the type and composition peatability was 0.1 nm.
of the respective glass and melting conditions. Our previous studies re-
garding the local structure of vanadium ions in calciumphosphate 3. Results
glasses using EPR spectroscopy have shown that these ions are present
as vanadyl ions in a C4v symmetry [20,21]. 3.1. Raman spectra
The present work is an attempt to demonstrate with the help of
Raman, IR and UVvis spectroscopic techniques that the progressive in- The experimental Raman spectra of xV2O5(100 x)[P2O5CaO]
troduction of vanadium ions in the calcium phosphate network of the glass system with 0 x 40 mol% are presented in Fig. 2. Because the
studied glasses leads to the formation of VOP and VOV new bands are large and asymmetric a deconvolution of each spectrum
bonds and to an evolution regarding the role of V2O5 from simple mod- was necessary in order provide a more accurate band assignments and
ier to network glass former. to follow and quantify the individual band evolution. As a consequence
we used for discussion the deconvoluted spectra instead of the experi-
2. Experimental mental ones. A deconvoluted Raman spectrum is presented in Fig. 3
and the band assignments are given in Table 1.
The starting materials used in the present investigation were
(NH4)2HPO4, CaO and V2O5 of reagent grade purity. The samples were 3.2. IR spectra
prepared by weighing suitable proportions of the components, powder
mixing and mixture melting in sintered corundum crucibles at 1250 C IR absorption spectra of xV2O5(1 x)[P2O5CaO] glass system with
for 30 min. The mixtures were put into the furnace directly at this tem- 0 x 40 mol% are presented in Fig. 4.
perature. The obtained glass samples were quenched by pouring the The specic IR bands of phosphate glasses are located in the
molten glass on stainless steel plates. 5001400 cm1 region. On the other hand, the specic V2O5 vibrations
Raman spectra were obtained with a Horiba Jobin Yvon system are located at: ~ 820 cm 1 for VO vibrations in VOV chains and
equipped with Olympus BX41 optical microscope, a grating of 1800 ~1018 cm1 for V_O vibrations [22,23].
grooves per mm and Peltier CCD cooler. The spectra were obtained
under using the 632.8 nm emission line of a heliumneon laser. The 3.3. UVvis absorption spectra
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 Fig. 5 illustrates the UVvis absorption spectra of four representative
and the wave number accuracy was 0.5 cm1. Three multiple measure- samples of different concentration (0.5; 1; 10 and 40 mol%). UVvis ab-
ments per sample were done to check for the potential micron-range sorption spectra of these samples were recorded at room temperature
heterogeneity and for the effects of sample orientation. in the wavelength region of 2001000 nm.
IR spectra were recorded with a Bruker IFS66/DSP spectrometer in It was indicated in several papers [19,24] that vanadium ions in
4002000 cm 1 range, using the anhydrous KBr technique to avoid phosphate glasses occur mostly under the form of V3+ and V4+ ions, de-
structural modications caused by the ambient moisture. The resolution pending by the nature of the host glass, temperature and vanadium con-
of the IR spectra is of 2 cm1. tent. All the spectra revealed the appearance of two peaks in the UV
The structure of samples was analyzed by means of X-ray diffraction region centered around 200300 nm, peaks that are assigned to trace
using a Bruker D8 Advanced X-ray diffractometer with a graphite to trace iron impurities due to a possible contamination of raw materials
monochromator for CuK radiation with = 1.54 . The increment used for glass preparation [25,26].
for the measurements was of 0.1. The pattern obtained did not reveal
any crystalline phase in all samples (Fig. 1). 4. Discussion
Optical response of the samples was studied by using UVvis ab-
sorption spectra recorded from a JASCO V570 UVvis-NIR Spectro- 4.1. Raman deconvoluted spectra
photometer equipped with absolute reectivity measurement
JASCO ARN-475 accessory. The transformation of reectance spectra The relative intensity of the band from 350 cm1 is increasing with
in absorbance spectra was obtained with an intern soft of apparatus. the addition of vanadium oxide. By increasing the V2O5 concentration,

Fig. 2. Experimental Raman spectra of xV2O5 (100 x)[P2O5CaO] glass system with
Fig. 1. XRD spectra of xV2O5(100 x)[P2O5CaO] glass system. 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 are replaced by the small phosphate units [31].
of these bands, attributed to the bending mode of the phosphate (PO4) Around 1145 cm1 the symmetric stretching motion appears specif-
polyhedra, is related to the strong depolymerization of the long phos- ic for the two non-bridging oxygen NBO atoms bonded to phosphorous
phate chains [27]. Around ~500 cm1 bending and torsion vibrations atoms (PO2) in the Q2 phosphate chains [29,3234]. As it can be ob-
occur and they have been assigned to the vanadium cation motion vi- served in the case of the other two bands from 705 cm 1 and
brations and chain conformation [28]. With the progressive addition 780 cm1, characteristic to long phosphate chains, this band decreases
of V2O5 oxide, the number of PO4 units strongly increases, a fact that is also in intensity with the increase of vanadium oxide content. At the
also related to the drastic depolymerization of phosphate network. A same time, the same tendency was observed in the case of the band cen-
symmetric stretching vibration of the PO bonds of the orthophosphate tered at 1172 cm1 which is assigned to strained (PO2) symmetric
(PO34) unit, (Q0) respectively is centered at about 606 cm1. The in- (strained structural units, possibly three- or four-membered rings)
tensity of this band increases with the addition of vanadium oxide due [35]. This band is present in Raman spectra only for low vanadium con-
to the same depolymerization effect. centrations; for x 5% it disappears from the spectra.
The band at 705 cm1 derives from the POP symmetric stretch of The band centered around 1260 cm1 due to symmetric stretching
the bridging oxygen atoms in Q2 species whereas the band at 780 cm1 vibration of double bond P_O strongly decreases in intensity by addi-
arises from the asymmetric vibrations of the same species [29]. With the tion of V2O5 because the formation of VO_P bond type that weaken
increase of vanadium oxide content these bands decrease strongly in in- the P_O bond. The reduced force between P and O atoms will lead to
tensities as a direct effect of the phosphate network depolymerization. the formation of free oxygen atoms which will be involved in the new
New features appear around 900 cm1 with the increases of V2O5 formed VO bonds [1].
content, attributed to symmetric stretching vibrations of VOV and From these considerations we can conclude that by increasing vana-
OVO linkages. By addition of vanadium oxide these bands increase dium oxide content a strong depolymerization appears in the glass
in intensity and for concentrations x 20% these become the most in- structure. Beside this, the specic bands of vanadium oxide become
tense features of the spectrum. The same tendency was observed for more intense and for high V2O5 these bands become the dominant fea-
970 cm1 band, which can be assigned to a superposition of symmetric tures of the spectra. It can be noted that thus, the vanadium atom pre-
stretching vibration of Q0 tetrahedra with the stretching vibrations of fers to bridge with resulting oxygen atoms from the depolymerization
V_O bond [30]. The increase of these bands indicates both the depoly- process instead of bridging with P atoms, producing therefore their
merization of phosphate network and an increased number of V_O own networks. In this case vanadium oxide acts as a network former,
bonds. The (PO3)2 end-of-chain asymmetric stretching vibrations are similar to the previously reported results for xV2O5(100 x)NaPO3
present in our spectra at about 1038 cm 1. The concentration of 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

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.
Fig. 5. Optical absorption spectra of xV2O5(100 x)[P2O5CaO] glass system with On the other hand, Raman spectra have shown that at ~ 10 mol%
0 x 40 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+
4.2. IR spectra ions appear.
In the case of the sample with 40 mol% vanadium oxide, the preva-
It is well known from literature that in the case of phosphate glasses lent band in the spectrum is centered at about 380 nm, which indicates
the shape of Raman bands are better visualized compared with the IR the existence of vanadium ions mainly as V3+ ions as a consequence of
ones, probably because Raman spectroscopy generates a signal from network depolymerization and re-organization imposed by the higher
the depth of the sample and not only from the surface [36,37], but IR vanadium ions concentration.
spectra, complementary to Raman spectra, underlined and supported The visual appearances of all prepared samples support also our as-
our conclusions. sumption that the studied glasses favor the presence of the two low va-
Thus, the band around 550 cm1 is attributed to OPO bending vi- lance state forms of vanadium. The color of our samples varies from
brations in Q1 groups [36]. By addition of vanadium oxide this band bluishlight green color (specic for vanadyl ions [19]) for low vanadi-
shifts to higher wavenumber due to the depolymerization of the phos- um content to greendark green color (specic for V3+ ions [19]) with
phate network. Other IR bands at 760 cm1 and 900 cm1 are assigned the increase of V2O5 content.
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. 5. Conclusion
The observed tendency is directly related with the modication of P
OP bond length with the depolymerization of phosphate network Raman spectra provided a better image on the structural changes of
[11]. The 1125 cm1 band is associated with the asymmetric stretching the studied phosphate system, mostly because Raman bands are
vibrations in Q2 groups (PO3)2 [36]. By adding vanadium oxide this narrower than IR bands for phosphate glasses, but both IR and Raman
band decreases in intensity and for a concentration x 20 mol% it spectra revealed the phosphate network depolymerization with in-
disappears from the spectrum. The progressive vanishing of this band, creasing V2O5 content because there is a reduction of strength in the
which is characteristics for the long phosphate chains is related to the connection between P and O atoms that cause non-bridging oxygen
gradual depolymerization of phosphate network. The broad band from atoms involved in new VOV linkages. In the case of vanadium
12001400 cm 1 is attributed to both asymmetric stretching of the doped glasses, at high concentration (x N 20 mol%) the bands belonging
double bonded oxygen vibrations [38] and to the (P_O) symmetric to the vibration in V2O5 groups dominate the spectra while the bands
stretching vibrations [39]. A decrease in intensity of this band is ob- belonging to the phosphate chains are strongly reduced except the spe-
served for high concentrations of V2O5 due to the symmetric stretching cic bands of the small phosphate units. From this structural investiga-
vibrations of VO_P linkages which allow the weakness of P_O bond tion it can be said that vanadium prefers to bridge with the oxygen that
[11,20,2731]. do not take part in the PO4 units making new structures and in conse-
For high concentrations of vanadium oxide (x 20% mol) in IR spec- quence it acts as a network former.
tra a shoulder at about ~820 cm1 attributed to symmetric stretching UVvis spectra of the investigated glasses have shown the presence
vibrations in VOV chains appears [22,23]. Also, the band around of vanadium ions under the form of V4+ and V3+ ions as the literature
1100 cm1 becomes broader by addition of V2O5 due to the superposi- reports.
tion of the two bands corresponding to vibration of PO3 4 groups and vi-
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