Journal of Non-Crystalline Solids 428 (2015) 151–155

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Journal of Non-Crystalline Solids

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Study on the effect of vanadium oxide in calcium phosphate glasses by
Raman, IR and UV–vis spectroscopy
D.A. Magdas a, N.S. Vedeanu b,⁎, D. Toloman a
National Institute for Research and Development for Isotopic and Molecular Technologies, RO-400293 Cluj-Napoca, Romania
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 UV–vis 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 modifications 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 modifier agent for
Available online xxxx
low vanadium content (less than 10 mol%) and that of glass network former for high vanadium content (higher
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 field of material science.
Vanadium; © 2015 Elsevier B.V. All rights reserved.

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 modifier
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 field 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 [1–3], low thermo-optical coeffi- “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 calcium–phosphate materials are biocompatible oxygen P_O, forming a three-dimensional cross-linked network [11].
and can be used as biomaterials [5–7]. 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 calcium–phosphate 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 modification of phosphate network [14].
the type of modifier 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 [15–17] 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 350–400 nm, and 580–680 nm and a third possible band in the UV
network modifiers a depolymerization of P2O5 vitreous skeleton ap- region originating from the electron transfer within the vanadium
pears conducting to the breaking of P–O–P bond and formation of termi- ion itself. The tetravalent vanadium ions are assumed to exist as vanadyl
nal oxygen atoms. xV2O5(100 − x)[P2O5·CaO] glass materials with ions [VO2+] and exhibit four characteristic weak bands at about 420 nm,
760–860 nm and ~1000 nm in addition to a possible UV band [18,19].
⁎ Corresponding author. The pentavalent vanadium ions correspond to the d° configuration
E-mail address: (N.S. Vedeanu). and thus will not give rise to d–d transitions but give a characteristic
0022-3093/© 2015 Elsevier B.V. All rights reserved.

The ratio of each valence of va. IR and UV–vis spectroscopic techniques that the progressive in.5 mW (low enough to avoid any sample alter- ation or decomposition).26]. temperature and vanadium con- of the IR spectra is of 2 cm−1.3 nm and the wavelength re- nadium ions in a glass generally depends on the type and composition peatability was ± 0. The mixtures were put into the furnace directly at this tem. Discussion Optical response of the samples was studied by using UV–vis ab- sorption spectra recorded from a JASCO V570 UV–vis-NIR Spectro. 1). Because the studied glasses leads to the formation of V–O–P and V–O–V new bands are large and asymmetric a deconvolution of each spectrum bonds and to an evolution regarding the role of V2O5 from simple mod. The wavelength accuracy was of ± 0. Fig. was necessary in order provide a more accurate band assignments and ifier to network glass former. Results glasses using EPR spectroscopy have shown that these ions are present as vanadyl ions in a C4v symmetry [20. XRD spectra of xV2O5(100 − x)[P2O5·CaO] glass system. The θ increment used for glass preparation [25. Experimental mental ones. 3. Three multiple measure. grooves per mm and Peltier — CCD cooler. 4. for the measurements was of 0.24] that vanadium ions in 400–2000 cm− 1 range. 500–1400 cm−1 region.23]. The spectra were obtained under using the 632. 1.2. tent. CaO and V2O5 of reagent grade purity. Magdas et al. 2.A.19]. Raman spectra The present work is an attempt to demonstrate with the help of Raman. 3 and the band assignments are given in Table 1. to follow and quantify the individual band evolution. The pattern obtained did not reveal any crystalline phase in all samples (Fig. 0 ≤ x ≤ 40 mol% are presented in Fig. powder mixing and mixture melting in sintered corundum crucibles at 1250 °C IR absorption spectra of xV2O5(1 − x)[P2O5·CaO] glass system with for 30 min. The spectral resolution was about 1.1.152 D. The samples were 3. 4. 1.3. UV–vis 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. IR spectra were recorded with a Bruker IFS66/DSP spectrometer in It was indicated in several papers [19.3 cm−1 Fig. The obtained glass samples were quenched by pouring the The specific IR bands of phosphate glasses are located in the molten glass on stainless steel plates. using the anhydrous KBr technique to avoid phosphate glasses occur mostly under the form of V3+ and V4+ ions.54 Å. Raman deconvoluted spectra photometer equipped with absolute reflectivity measurement JASCO ARN-475 accessory. / Journal of Non-Crystalline Solids 428 (2015) 151–155 charge transfer band at ~380 nm [18. The 3. IR spectra prepared by weighing suitable proportions of the components. The resolution pending by the nature of the host glass. . 0 ≤ x ≤ 40 mol%.1.5 cm−1. The experimental Raman spectra of xV2O5(100 − x)[P2O5·CaO] troduction of vanadium ions in the calcium phosphate network of the glass system with 0 ≤ x ≤ 40 mol% are presented in Fig. As a consequence we used for discussion the deconvoluted spectra instead of the experi- 2.8 nm emission line of a helium–neon laser. The starting materials used in the present investigation were (NH4)2HPO4. By increasing the V2O5 concentration.5.1 nm.21]. de- structural modifications caused by the ambient moisture. the addition of vanadium oxide. Our previous studies re- garding the local structure of vanadium ions in calcium–phosphate 3. 2. in the wavelength region of 200–1000 nm. A deconvoluted Raman spectrum is presented in Fig. 4. perature. samples of different concentration (0. 5 illustrates the UV–vis absorption spectra of four representative and the wave number accuracy was 0. 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 200–300 nm. the specific V2O5 vibrations Raman spectra were obtained with a Horiba Jobin Yvon system are located at: ~ 820 cm− 1 for V–O vibrations in V–O–V chains and equipped with Olympus BX41 optical microscope. a grating of 1800 ~1018 cm−1 for V_O vibrations [22. UV–vis absorption spectra laser power was about 1.1°. of the respective glass and melting conditions. The transformation of reflectance spectra The relative intensity of the band from 350 cm−1 is increasing with in absorbance spectra was obtained with an intern soft of apparatus. On the other hand. 10 and 40 mol%). 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 CuKα radiation with λ = 1. Experimental Raman spectra of xV2O5 (100 − x)[P2O5·CaO] glass system with Fig.

or four-membered rings) tensity of this band increases with the addition of vanadium oxide due [35].2 24. the specific bands of vanadium oxide become tense features of the spectrum. The reduced force between P and O atoms will lead to tensities as a direct effect of the phosphate network depolymerization. for x ≥ 5% it disappears from the spectra.5 6. IR spectra of xV2O5(100 − x)[P2O5·CaO] glass system with 0 ≤ x ≤ 40 mol%. The band at 705 cm−1 derives from the P–O–P symmetric stretch of The band centered around 1260 cm−1 due to symmetric stretching the bridging oxygen atoms in Q2 species whereas the band at 780 cm−1 vibration of double bond P_O strongly decreases in intensity by addi- arises from the asymmetric vibrations of the same species [29]. At the also related to the drastic depolymerization of phosphate network.5 28. ic for the two non-bridging oxygen NBO atoms bonded to phosphorous phate chains [27]. The concentration of glass system [12].7 6. the same tendency was observed in the case of the band cen- symmetric stretching vibration of the P–O bonds of the orthophosphate tered at 1172 cm−1 which is assigned to “strained” (PO2) symmetric (PO3−4) unit. which can be assigned to a superposition of symmetric tures of the spectra. Q2 12. Beside this. this band decreases of V2O5 oxide.36 – – 1260 (P_O)symstretch 10. a fact that is also in intensity with the increase of vanadium oxide content. (strained structural units. (Q0) respectively is centered at about 606 cm−1. characteristic to long phosphate chains. With the progressive addition 780 cm−1. The increase of these bands indicates both the depoly. content.A.5a 5a 20a 530 Bending vibrations of PO4 polyhedra 5.5 900 Symmetric stretching vibrations of V–O–V and O–V–O linkages – 3 47. The same tendency was observed for more intense and for high V2O5 these bands become the dominant fea- 970 cm−1 band.9 1145 (PO2)symstretch Q2 23.2 1. bonds.57 11. This band is present in Raman spectra only for low vanadium con- to the same depolymerization effect. D. . In this case vanadium oxide acts as a network former. 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. attributed to the bending mode of the phosphate (PO4) Around 1145 cm−1 the symmetric stretching motion appears specif- polyhedra. A same time. 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]. centrations.6 a Relative areas were calculated with an error of 3%–5%. of these bands. As it can be ob- occur and they have been assigned to the vanadium cation motion vi. With the tion of V2O5 because the formation of V–O_P bond type that weaken increase of vanadium oxide content these bands decrease strongly in in. producing therefore their merization of phosphate network and an increased number of V_O own networks.8 0. Magdas et al. structure. attributed to symmetric stretching vibrations of V–O–V and From these considerations we can conclude that by increasing vana- O–V–O linkages.5 1172 Strained (PO2)symstretch 8.8 1 705 (POP)symstretch. the P_O bond. 4.9 0.3 7. Around ~500 cm−1 bending and torsion vibrations atoms (PO2) in the Q2 phosphate chains [29. The in. Table 1 The assignments and relative areas of different vibration bands from Raman spectra of xV2O5 (100 − x)[P2O5·CaO] glass system. (PO3)2− groups increases when the long chains of the metaphosphates the 350 cm−1 band becomes more intense and gets wider. Deconvoluted Raman spectra of xV2O5 (100 − x)[P2O5·CaO] for 0.5 mol%. the number of PO4 units strongly increases. ν (cm−1) Assignments Relative areas dependence of vibrational bands versus V2O5 concentrations (x mol%)a 0. process instead of bridging with P atoms.7 1038 (PO3)2−asymstretch 7. It can be noted that thus. Q2 11.32–34]. served in the case of the other two bands from 705 cm− 1 and brations and chain conformation [28]. is related to the strong depolymerization of the long phos.7 7.6 11. possibly three.9 18. / Journal of Non-Crystalline Solids 428 (2015) 151–155 153 Fig.7 0.7 970 (PO4)symstretch Q0 and (V_O)symstretch 5.01 606 (P–O)symstretch. The growth are replaced by the small phosphate units [31]. the formation of free oxygen atoms which will be involved in the new New features appear around 900 cm−1 with the increases of V2O5 formed V–O bonds [1]. 3. 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.7 – 780 (POP)asymstretch. Fig.7 11. Q0 0.

mostly because Raman bands are vibrations in Q2 groups (PO3)2− [36]. underlined and supported The visual appearances of all prepared samples support also our as- our conclusions. Wasiucionek. J. Mater.A. Raman spectra have shown that at ~ 10 mol% 0 ≤ x ≤ 40 mol%. the band around 550 cm−1 is attributed to O–P–O bending vi. [3] M. For the spectra of low vanadium content (0. 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. Katani. .5 and 1 mol%). In the case of the sample with 40 mol% vanadium oxide. Our previous EPR data [21] demonstrated also that up to 10 mol% isolated V4+ ions are present mostly in a distorted C4V symmetry. The broad band from atoms involved in new V–O–V linkages. T. 5. 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]. Moreover. [5] T. belonging to the phosphate chains are strongly reduced except the spe- served for high concentrations of V2O5 due to the symmetric stretching cific bands of the small phosphate units. um content to green–dark green color (specific for V3+ ions [19]) with phate network. sumption that the studied glasses favor the presence of the two low va- Thus. Magdas et al. to the symmetric and asymmetric modes of P–O–P bonds in Q1 units. Bacewicz.20.37]. From this structural investiga- vibrations of V–O_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. the specific bands of vanadium oxide be. Assem.E. H. Phys.E. Also.P. K. T. Biomaterials to V3 + ions [19] and other two absorption bands centered at about 14 (1993) 216–224. A. The appearances of these bands are correlated with our previous EPR results [21. T. R. P. re- spectively [33]. / Journal of Non-Crystalline Solids 428 (2015) 151–155 450 nm and 690 nm. 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. A decrease in intensity of this band is ob. Mahmoud. Livage. From the combination of V4 + with such free electrons new V3+ 4. 4. Machowski. IR spectra ions appear. Sci. D. C. Kokubo. Tykarski.2. Studies of silver–vanadate–phosphate glasses by Raman. A band shift from 760 cm−1 to higher wave number is observed in the spectra with the increase of vanadium oxide content. By adding vanadium oxide this narrower than IR bands for phosphate glasses. Up to 10 mol% V2O5 the number of V4+–V4+ clusters increase due to strong dipole–dipole interactions. 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. EPR and im- come more intense with the addition of V2O5 fact that is also supported pedance spectroscopy methods. Garbarczyk. tion of the two bands corresponding to vibration of PO3− 4 groups and vi- brations of V_O bonds. but for x ≥ 10 mol% vanadium content the superexchange interactions are prevalent be- tween the resonance centers. UV–vis absorption spectra Mater. Takeuchi. lance state forms of vanadium. magnetic and positron lifetime studies on CaO–ZrO2–SiO2 glass system doped with vanadium oxide. 14 (2003) 215–221.R.154 D. Optical absorption spectra of xV2O5(100 − x)[P2O5·CaO] glass system with On the other hand. 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. tra a shoulder at about ~820 cm−1 attributed to symmetric stretching UV–vis spectra of the investigated glasses have shown the presence vibrations in V–O–V chains appears [22. S. spectra. J.3. E. but IR vanadium ions concentration. Jollivet. 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 color of our samples varies from brations in Q1 groups [36]. Appl. Electronic properties of mixed valence oxide gels.41.42]. a broad band in 300–500 nm spectral range and other two weak peaks centered at ~680 nm and ~ 910 nm appeared. Aleksiejuk. L. The second peak is attributed to V3+ ions and the third one to tet- ravalent vanadyl (VO2+) ions [40]. by adding vanadium oxide a strong depolymerization appears in these glasses. 5. References Thus. Fig. The progressive vanishing of this band. by Raman bands at this concentration. Siligardi. quence it acts as a network former. Nakamura. J. Conclusion The observed tendency is directly related with the modification of P– O–P bond length with the depolymerization of phosphate network Raman spectra provided a better image on the structural changes of [11]. Sharshar. Four calci- the UV peaks. 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]. [1] J. a weak absorption peak appears at ~ 340 nm belonging um phosphate ceramics as bone substitutes for non-weight-bearing. Solids 121 (1990) (1990) 35–39.27–31].23]. El-Desoky. 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