Professional Documents
Culture Documents
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
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%.
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
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-
brations of V_O bonds. References
Thus, by adding vanadium oxide a strong depolymerization appears
in these glasses. Moreover, the specic bands of vanadium oxide be- [1] J.E. Garbarczyk, P. Machowski, M. Wasiucionek, L. Tykarski, R. Bacewicz, A.
Aleksiejuk, Studies of silvervanadatephosphate glasses by Raman, EPR and im-
come more intense with the addition of V2O5 fact that is also supported pedance spectroscopy methods, Solid State Ionics 136 (2000) 10771083.
by Raman bands at this concentration. [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.
4.3. UVvis absorption spectra Mater. Electron. 14 (2003) 215221.
[4] J. Livage, J.P. Jollivet, E. Tronc, Electronic properties of mixed valence oxide gels, J.
For the spectra of low vanadium content (0.5 and 1 mol%), beside Non-Cryst. Solids 121 (1990) (1990) 3539.
[5] T. Kitsugi, T. Yamamuro, T. Nakamura, S. Katani, T. Kokubo, H. Takeuchi, Four calci-
the UV peaks, a weak absorption peak appears at ~ 340 nm belonging um phosphate ceramics as bone substitutes for non-weight-bearing, Biomaterials
to V3 + ions [19] and other two absorption bands centered at about 14 (1993) 216224.
D.A. Magdas et al. / Journal of Non-Crystalline Solids 428 (2015) 151155 155
[6] T. Kitsugi, T. Yamamuro, T. Nakamura, M. Oka, H. Tacheuchi, Transmission electron [24] N. Kerkouri, M. Haddad, M. Et-tabirou, A. Chahine, I. Laanab, FTIR, Raman, EPR and
microscopy observations at the interface of bone and four types of calcium phos- optical absorption spectral studies on V2O5-doped cadmium phosphate glasses,
phate ceramics with different calcium/phosphorus molar ratios, Biomaterials 16 Physica B 406 (2011) 31423148.
(1995) 11011107. [25] D. Moncke, D. Ehrt, Irradiation induced defects in glasses resulting in the photoion-
[7] R. Li, A.E. Clark, L.L. Hench, An investigation of bioactive glass powders by solgel ization of polyvalent dopants, Opt. Mater. 25 (2004) 425437.
processing, J. Appl. Biomater. 2 (1991) 231239. [26] S.Y. Marzouk, F.H. Elbatal, Ultravioletvisible absorption of gamma-irradiated tran-
[8] S.B. Etcheverry, D.A. Barrio, Vanadium and bone: relevance of vanadium compounds sition metal ions doped in sodium metaphosphate glasses, Nucl. Inst. Methods
in bone cell, chapter 15/ACS symposium series 974, Am. Chem. Soc. (2007) 204216 Phys. Res. B 248 (2006) 90102.
(PubMed). [27] A. Mogus-Milankovic, A. Santic, A. Gajovic, D.A. Day, Spectroscopic investigation of
[9] S.B. Etcheverry, D.A. Barrio, Vanadium and bone development: putative signaling MoO3Fe2O3P2O5 and SrOFe2O3P2O5 glasses. Part I, J. Non-Cryst. Solids 325
pathways, Can. J. Physiol. Pharmacol. 84 (7) (2006) 677686. (2003) 7684.
[10] F.H. El-Batal, Y.M. Hamdy, S.Y. Marzouk, UVvisible and infrared absorption spectra [28] A. Mogus-Milankovic, L. Pavic, S.T. Reis, D.E. Day, M. Ivanda, Structural and electrical
of transition metals-doped lead phosphate glasses and the effect of gamma irradia- properties of Li2OZnOP2O5 glasses, J. Non-Cryst. Solids 356 (2010) 715719.
tion, J. Non-Cryst. Solids 355 (2009) 24392447. [29] M.A. Karakassides, A. Saranti, I. Koutselas, Preparation and structural study of binary
[11] E. Metwalli, M. Karabulut, D.L. Sidebottom, M.M. Morsi, R.K. Brow, Properties and phosphate glasses with high calcium and/or magnesium content, J. Non-Cryst.
structures of copper ultraphosphate glasses, J. Non-Cryst. Solids 344 (2004) Solids 347 (2004) 6979.
128134 (n). [30] Y.M. Moustafa, K. El-Egili, Infrared studies on the structure of sodium phosphate
[12] G. Tricot, L. Montagne, L. Delevoye, G. Palavit, V. Kostoj, Redox and structure of sodi- glasses, J. Non-Cryst. Solids 240 (1998) 144153.
umvanadophosphate glasses, J. Non-Cryst. Solids 345 (2004) 5660. [31] G.L. Saout, P. Simon, F. Fayon, A. Blin, Y. Vaills, Raman and infrared study of
[13] C.N. Reddy, V.C.V. Gowda, R.P.S. Chakradhar, Elastic properties and structural studies (PbO)x(P2O5)(1 x) glasses, J. Raman Spectrosc. 33 (2002) 740746.
on leadborovanadate glasses, J. Non-Cryst. Solids 354 (2008) 3240. [32] J. Koo, B. Bae, H.K. Na, Raman spectroscopy of copper phosphate glasses, J. Non-
[14] V.C.V. Gowda, R.V. Anavekar, Elastic properties and spectroscopic studies of lithium Cryst. Solids 212 (1997) 173179.
lead borate glasses, Ionics 10 (2004) 103108. [33] M. Scagliotti, M. Villa, G. Chiodelli, Short range order in the network of the
[15] G.D. Khatak, N. Tabet, Local structure and redox state of vanadium in strontium borophosphate glasses: Raman results, J. Non-Cryst. Solids 93 (1987) 350360.
vanadate glasses, J. Electron Spectrosc. Relat. Phenom. 136 (2004) 257264. [34] J.E. Pemberton, L. Latifzadeh, J.P. Fletcher, S.H. Risbud, Raman spectroscopy of calci-
[16] E.E. Assem, Effect of replacing calcium oxide with calcium halide on crystallization um phosphate glasses with varying CaO modier concentrations, Chem. Mater. 3
and some physical properties of calcium vanadium phosphate glass ceramics, (1991) 195200.
Physica B 406 (2011) 421425. [35] J.J. Hudgens, R.K. Brow, D.R. Tallant, S.W. Martin, Raman spectroscopy study of the
[17] G.D. Khattak, A. Mekki, L.E. Wenger, X-ray photoelectron spectroscopy (XPS) and structure of lithium and sodium ultraphosphate glasses, J. Non-Cryst. Solids 223
magnetic susceptibility studies of vanadium phosphate glasses, J. Non-Cryst. Solids (1998) 2131.
355 (2009) 21482155. [36] A.M. Emov, IR fundamental spectra and structure of pyrophosphate glasses along
[18] A.M. Nassar, N.A. Ghoneim, Vanadium contribution in different glasses in view of the 2ZnOP2O5 2Me2OP2O5 join (Me being Na or Li), J. Non-Cryst. Solids 209
the ligand eld theory, J. Non-Cryst. Solids 46 (1981) 181195. (1997) 209226.
[19] F.H. ElBatal, M.A. Marzouk, A.M. Abdelghany, UVvisible and infrared absorption [37] R.K. Brow, Review: the structure of simple phosphate glasses, J. Non-Cryst. Solids
spectra of gamma irradiated V2O 5 doped in sodium phosphate, lead phosphate, 263264 (2000) 128.
zinc phosphate glasses: a comparative study, J. Non-Cryst. Solids 357 (2011) [38] B.V.R. Chowdari, K.I. Tan, W.T. Chia, R. Gopalakrishnam, X-ray photoelectron spec-
10271036. troscopic studies of molybdenum phosphate glassy system, J. Non-Cryst. Solids
[20] N. Vedeanu, O. Cozar, I. Ardelean, B. Lendl, D.A. Magdas, Raman spectroscopic study 119 (1990) 95102.
of CuOV2O5P2O5CaO glass system, Vib. Spectrosc. 48 (2008) 259262. [39] J.J. Hudgens, S.W. Martin, Glass transition and infrared spectra of alkali, anhydrous
[21] N. Vedeanu, O. Cozar, I. Ardelean, S. Filip, Spectroscopic investigation on some calci- lithium phosphate gasses, J. Am. Ceram. Soc. 76 (1994) 16911696.
umphosphate glasses, J. Optoelectron. Adv. Mater. 8 (3) (2006) 11351139. [40] C.R. Bamford, Color Generation and Control in Glass: Glass Science and Technology,
[22] I. Ardelean, C. Andronache, C. Campean, P. Pascuta, Structural investigation of vol. 2, Elsevier, Amsterdam, 1977.
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. calciumphosphate glasses, J. Alloys Compd. 534 (2012) 9396.
[23] L. Stanescu, E. Indrea, I. Ardelean, M. Coldea, I. Bratu, D. Stanescu, Some contribu- [42] IR and Raman investigations on V2O5P2O5BaO glass system with opto-electronic
tions to the investigation of V2O5MoO2 system, Rev. Roum. Phys. 21 (9) (1976) potential, J. Non-Cryst. Solids 358 (2012) 18811885.
939951.