Influence of CuO and ZnO addition on the multicomponent phosphate glasses: Spectroscopic studies

Accepted Manuscript Influence of CuO and ZnO addition on the multicomponent phosphate glasses: spectroscopic studies Magdalena Szumera, Irena Wacławska, Justyna Sułowska PII:

S0022-2860(16)30120-X

DOI:

10.1016/j.molstruc.2016.02.026

Reference:

MOLSTR 22235

To appear in:

Journal of Molecular Structure

Received Date: 20 November 2015 Revised Date:

11 January 2016

Accepted Date: 7 February 2016

Please cite this article as: M. Szumera, I. Wacławska, J. Sułowska, Influence of CuO and ZnO addition on the multicomponent phosphate glasses: spectroscopic studies, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.02.026. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Influence of CuO and ZnO addition on the multicomponent phosphate glasses: spectroscopic studies Magdalena Szumeraa, Irena Wacławskaa, Justyna Sułowskaa

AGH University of Science and Technology in Krakow, Faculty of Materials Science and Ceramics,

RI PT

a

Department of Ceramics and Refractories, 30-059 Krakow, A. Mickiewicza 30, Poland

SC

Corresponding author: Magdalena Szumera, e-mail: [email protected]

M AN U

Abstract

The spectra of phosphate-silicate glasses from the P2O5-SiO2-K2O-MgO-CaO system modified with the addition of CuO or ZnO have been studied by means of FTIR, Raman and 31P MAS NMR spectroscopy. All glasses were synthesized by the conventional melt-quenching technique and their homogeneous chemical composition was controlled and confirmed. By using the aforementioned research techniques, the presence of structural units with various

TE D

degrees of polymerization was shown in the structure of analyzed phosphate-silicate glasses: Q3, Q2, Q1 and Q0. It was found that an increase in the content of CuO or ZnO in the composition of analyzed glasses, which are introduced at the expense of decreasing

EP

amounts of CaO and MgO, has a different influence on the phospho-oxygen network. It was shown that copper ions cause its gradual polymerization, while zinc ions cause its depolymerization. At the same time, polymerization of the silico-oxygen subnetwork was

AC C

found. Additionally, in the case of glasses containing increasing amounts of ZnO, a change of the role of zinc ions in the vitreous matrix was confirmed (from the modifier to a structureforming component).

Keywords: phosphate glasses, CuO and ZnO, FTIR, Raman and 31P MAS NMR spectroscopy

1. Introduction Phosphate glasses are an interesting material especially in connection with their diverse applications. They include: sealing materials, medical use and solid-state electrolytes [1], but 1

ACCEPTED MANUSCRIPT also containment of radioactive waste [2], as degradable tissue and bone scaffolds within the human body [3] and agro-fertilizers with controlled solubility [4,5]. Such a broad range of phosphate glass applications results from the possibility of broad modifications of their chemical composition. It is known that the structure of phosphate glasses consists of a 3dimensional network of corner-sharing PO4 tetrahedra, each of which is connected with a

RI PT

non-bridging P=O bond. This oxygen atom does not take part in the formation of polymerized phosphate anions as it does not build P-O-P oxygen bridges. It can, however, form bonds with a modifier cation, which results in the formation of Me-O-PO3 bonds, where Me is the modifier cation (Mg2+, Ca2+, Cu2+, Cu+, Zn2+, K+) [6]. The gradual introduction of

SC

growing amounts of modifying oxides into the structure of phosphate glasses usually results in their gradual depolymerization.

M AN U

In recent years, phosphate glasses modified by the addition of zinc and copper ions have enjoyed a great interest as they find unconventional applications as carriers of macro- and microelements, which are necessary for proper development of plants. It is known from literature data that copper plays the role of a modifier in the phosphate structure [7, 8, 9]. Depending on the ZnO content in the structure of glasses, the structural role of ZnO in many oxide glasses is unique since zinc oxide can act both as a glass former

TE D

and a glass modifier. As a glass former, ZnO enters the network with ZnO4 structural units. As a network modifier, zinc ion is octahedrally coordinated and behaves like conventional alkali oxide modifiers [10].

EP

Numerous literature reports show that both in two-component CuO-P2O5 [8] and threecomponent systems P2O5-Na2O-CuO [9, 10] copper gradually introduced at the expense of

AC C

P2O5 or Na2O influences progressing depolymerization of the vitreous structure, which is manifested by gradual transformation of the three-dimensional network formed from phosphorus-oxygen tetrahedra (type Q3) to the metaphosphate chain structure, which is formed from phosphorus-oxygen units of the Q2.type. Such results of research were obtained using FTIR, Raman, XPS [7] spectroscopy methods as well as

31

P MAS NMR [8]. It

results from them that an increase in the CuO addition in the structure of phosphate glasses influences the formation of P-O-Cu bonds, which gradually replace P-O-Na bonds, which is accompanied by an increase in the density of the glasses under analysis. Similar research results are presented in [12].

2

ACCEPTED MANUSCRIPT Equally comprehensive literature data can be found for phosphate glasses modified by an increasing amount of ZnO. The authors of studies [13, 14, 15] agree on the influence of zinc ions on the structure of two-component glasses from the P2O5-ZnO system, which are introduced in small amounts (up to 0.8% mol) to the chemical composition of tested glasses. Using Raman and

31

P MAS NMR spectroscopies, they showed that an increase in the ZnO

RI PT

content in their chemical composition initially influences a decrease in the phosphorusoxygen units of the Q3 type with a simultaneous increase in the phosphorus-oxygen units of the Q2 type. A further increase in the ZnO content in the structure of the aforementioned glasses influenced further depolymerization of their structure and larger amounts of

SC

structural units of the Q1 type and isolated units of the Q0 type. The influence of larger amounts of ZnO on the structure of phosphate glasses was analyzed in [16], in which 46%

M AN U

mol ZnO was introduced into the glass composition. Also, with such a considerable ZnO content, information about its depolymerizing influence on the structure of considered glasses was obtained, which was registered in the form of the decreasing part of phosphorus-oxygen units of the Q2 type at the expense of the increasing share of units of the Q1 and Q0 type. The simultaneous increase in the number of non-bridging oxygen atoms was also emphasized. The research obtained by the Authors was previously confirmed by NMR

TE D

and XPS examinations [17].

It should be emphasized that there is scarce information on the influence of selected transition elements on the structure of phosphate glasses containing a small amount of

EP

another structure-forming component in the form of SiO2. The literature provides the influence of molybdenum ions on the structure of glasses from such a system [18, 19];

AC C

however, the influence of manganese ions [20] and zinc ions [21] was analyzed only in terms of their thermal characteristics. Therefore, for the purposes of this study, research was undertaken with a view to explaining both the influence and the role of the growing amount of CuO and ZnO on the structure of multicomponent glasses from the P2O5-SiO2-K2O-MgOCaO system. The following spectroscopic methods were used for this purpose: FTIR, Raman and 31P MAS-NMR. The possibility of using such multicomponent glasses as a new generation of fertilizers with a controlled, slow release rate of the nutrients for plants, should also be emphasized.

2. Experimental 3

ACCEPTED MANUSCRIPT A homogenous phosphate-silicate glasses from the P2O5-SiO2-K2O-MgO-CaO system with increasing contents of ZnO and CuO were prepared. The glasses were produced by traditional melting of raw materials mixture, i.e. (NH4)2HPO4, SiO2, K2CO3, MgO, CaCO3, CuO and ZnO at 1100oC. Amorphous state of glasses was confirmed using the X-ray diffraction method (X’Pert PRO Diffractometer, Philips) and the chemical composition of chosen glasses

RI PT

was controlled by X-ray fluorescence spectroscopy using ARL Advant ‘XP spectrometer, the results are shown in the Table 1.

FTIR spectroscopic measurements of the glasses were conducted with a Bruker Vertex 70v spectrometer using the transmission mode and spectra were registered with absorbance

SC

scale. The samples had the form of pellets made of the glasses mixed with KBr. Spectra were collected after 124 scans with 4 cm-1 resolution. Positions of bands on the MIR spectra were

M AN U

determined automatically by Win-IR software.

Raman studies were carried out using Horriba Yvon Jobin Lab-RAM HR micro-Raman spectrometer equipped with a CCD detector. Excitation wavelength of 532 nm was used and beam intensity was about 10 mW. Acquisition time was set to 30 s. The position of bands on the Raman spectra was defined automatically in Win-IR.

The local glass structure was investigated using 31P MAS NMR spectroscopy. The solid state P MAS NMR spectra were measured by the APOLLO console (Tecmag) using the 7 T/89 mm

TE D

31

superconducting magnet (Magnex). A Bruker HP-WB high-speed MAS probe equipped with the 4 mm zirconia rotor and the KEL-F cap was used to spin the sample at 4 and 8 kHz, for 31

P measurements, respectively. A single 3 ls rf pulse, corresponding to p/2 flipping

EP

the

angle, was applied. The acquisition delay in accumulation was 30 s, and 128 scans were 31

P measurements. A 50 Hz Lorentzian line broadening was applied to the

AC C

acquired in the

spectra, which was equal to about 0.4 ppm for the phosphorus. The frequency scale in ppm was referenced to TMS and 85 mol% H3PO4 for the 31P spectra.

3. Results and discussion 3.1.

FTIR spectroscopy

FTIR spectra of the tested phosphate glasses are presented in Fig. 1. FTIR spectra of all discussed glasses modified with the addition of CuO or ZnO (Cu41P or Zn41P) show considerable similarity. They are characterized by the presence of three main absorption bands with maxima located within the following waveform ranges: 1400-1200, 1200-850, 4

ACCEPTED MANUSCRIPT 800-650 and 650-400 cm-1. It should be noted that the conventional Q-site notion was used in the interpretation of the results [22]. 1400-1200 cm-1 range Within this wavenumber range, one band is present in FTIR spectra of analyzed glasses from the maximum at approx. 1280 cm-1. Literature data [23, 24] report that their presence is

RI PT

related to doubly bonded oxygen vibration vas(P=O) modes and/or anti-symmetrical vibrations of PO2- groups (in Q2 units). A small addition of CuO or ZnO (2% mol) introduced at the expense of the CaO and MgO content does not change the location of these bands. The introduction of larger amounts of CuO into the composition of these glasses does not result

SC

in a shift in their location towards lower wavenumber values (from 1285 to 1276 cm-1). An increase in the ZnO content in an amount of up to 15 % mol did not cause a change in the

M AN U

position of the band under analysis, while the addition of 30 mol% of this ingredient contributed to a significant shift of its position towards lower wavenumber values (approx. 1282 cm-1).

Such behavior implies that both CuO and ZnO, introduced at the expense of MgO and CaO result in the breaking of P=O bonds and the formation of bonds of the P-O-Cu or P-O-Zn type. At the same time, it should be emphasized that for glasses from the Zn41P group, the

subnetwork. 1200-850 cm-1 range

TE D

discussed effect implies a stronger impact of copper ions on the phosphorus-oxygen

EP

Three further bands situated at approx. 1100, 1000 and 900 cm-1 (1200-850 cm-1) for both groups of glasses (Cu41P and Zn41P) were assigned to the next range of wavenumbers.

AC C

The first of these is assigned to the combination of P-O and Si-O stretching vibration of combination of P-O-P and P-O-Si bridging (in Q2 units) [25]. With higher CuO (15-30 mol%) or ZnO (30 mol%) content in the glass composition, their location moves towards lower wavenumbers; it is particularly visible for 30Cu41P glass. On this basis, conclusions are drawn about a depolymerizing influence of copper and zinc ions on the phosphate-silicate structure. The two other bands (at approx. 1000 and 900 cm-1) originate from the asymmetric stretching vibrations of P-O-P in in Q2 units [25, 26]; however, no significant influence of the addition of CuO or ZnO on the change of their position was found. 850-650 cm-1 range 5

ACCEPTED MANUSCRIPT Bands from this range of wavenumbers can be assigned to coupled vibrations of P-O and SiO stretching coordinates of Si-O-Si, Si-O-P and P-O-P linkages [25, 27]. No change in the band position was found for either group of glasses (Cu41P or Zn41P). 650-400 cm-1 range Bands from this range of wavenumbers are related to bending vibrations. Literature data [9,

RI PT

27] imply that bands from this range may be assigned to the combination of bending vibrations of O-Si-O and O-P-O bonds [25, 29, 30]. An increase in the CuO content, which was introduced at the expense of the MgO and CaO content did not influence a change in the band position from this range of wavenumbers. Only in the case of the group of Zn41P

SC

glasses, can a slight shift of the position of these bands be observed towards lower wavenumbers (from 491 to 485 cm-1). This shows a slight increase in the degree of disorder

M AN U

of the structure composed of phosphorus-silicon-oxygen tetrahedra.

The obtained FTIR results show that both an increase in the CuO and ZnO content introduced at the expense of reducing the MgO and CaO content into the structure of analyzed glasses influences the breaking of P=O bonds and has a depolymerizing effect on the phosphate-

3.2.

TE D

silicate structure.

Raman spectroscopy

The influence of the addition of CuO and ZnO on the structure of analyzed phosphate-silicate glasses is presented in the form of Raman spectra in Fig. 2. The fact should be emphasized

EP

that the similarity of the Raman spectra of glasses is modified by both the addition of CuO and ZnO, i.e. in a manner similar for FTIR spectra. In both groups of glasses, the Raman

AC C

spectra reveal three main bands at about 1180, 705 and 340 cm-1. For both groups of glasses, the band at approx. 1180 cm-1 is characterized by asymmetry both on the side of lower and higher wavenumbers and the highest intensity as compared to the other bands. According to the literature data [31, 32, 33], these bands may be ascribed to (PO2)sym stretching mode of non-bridging oxygens in Q2 structural units. It should be noticed that the introduction of increasing amounts of CuO into the analyzed glasses at the expense of reducing amounts of MgO and CaO results in a shift of the location of this band towards lower wavenumber values (from 1181 to 1174 cm-1), thus indicating depolymerization of the phospho-oxygen subnetwork.

6

ACCEPTED MANUSCRIPT The introduction of increasing amounts of ZnO at the cost of the CaO and MgO content into the analyzed glasses, on the other hand, does not influence the position of this band, which may mean that the environment of non-bridging oxygen atoms does not change. In both groups of glasses, the band discussed above (1180 cm-1) has an inflection at approx. 1250 cm-1, which is assigned to the asymmetric vibrations vas(PO2) of the non-bridging

RI PT

oxygen atoms bonded to phosphorus atoms (O-P-O) in Q2 units [34].

Within the main band (at approx. 1180 cm-1), also the presence of another broad shoulder was found on the side of lower wavenumber values at approx. 1035 cm-1. This band disappears in the group of Cu41P glasses, while in the case of glasses from the Zn41P group,

SC

its intensity decreases. Its position does not change in either of the analyzed groups of glasses.

M AN U

The identification of this glass may refer to both the phospho-oxygen and silico-oxygen subnetworks. Literature data indicate that the presence of such an inflection may be derived from asymmetrical stretching vibrations (PO3)2- [35] and / or from non-bridging (PO2)sym oxygen atoms [36] in the Q1 units of phosphate tetrahedra. Considering the fact that the analyzed structure is a mixed phosphate-silicate structure, these bands can be assigned to

TE D

the Si-O– stretching vibrations in Q3, Q2 and Q1 units in the silico-oxygen subnetwork [25, 29, 37, 38], resulting from the presence of network-modifying cations. The behavior presented above implies that, together with an increase in the CuO or ZnO content in the structure of analyzed glasses, the number of structural units in the phospho-oxygen subnetwork of the

EP

Q1 type decreases, which may indicate progressing depolymerization of the phospho-oxygen subnetwork and a gradual reduction in the content of broken Si-O– bonds, which, in turn,

AC C

would prove gradual polymerization of the silico-oxygen subnetwork (an increase in the Si-OSi bridging bonds). This conclusion is formed in accordance with the results of research on glasses with reversed silicate-phosphate matrix modified by copper ions, introduced at the expense of the number of calcium and magnesium ions [39]. The next band at approx. 705 cm-1 was assigned to the symmetrical stretching vibration of bridging oxygen atoms (P-O-P) in Q2 units [32, 40]. Both its position and intensity change. It should be emphasized that a small band appears at approx. 640 cm-1 in both analyzed groups. This band is derived from the P-O-P symmetric stretching vibration of the long-chain phosphate glasses (Q3 structural units) [35]. In both groups of glasses, its position shifts 7

ACCEPTED MANUSCRIPT slightly towards lower values of wavenumbers, which is especially visible for glasses modified by the addition of CuO (from 643 cm-1 to 637 cm-1). It may be an effect of the increase in phosphate chain lengths [41, 42]. This confirms earlier suppositions about the occurring polymerization of the phospho-oxygen subnetwork of the analyzed glasses. As regards the range of low wavenumbers, a band was registered at approx. 340 cm-1, its

RI PT

presence was not found for the 0Cu/0Zn41P glass, which does not contain copper or zinc ions in its composition. This band is assigned to bending modes of the phosphate polyhedral with copper or zinc cations [43, 44]. In the case of classes from the Cu41P group, the position of this band is shifted towards higher wavenumbers (from 337 to 348 cm-1), without

SC

changing its intensity. In the case of glasses modified by the addition of ZnO introduced into glasses at the expense of the MgO and CaO content, neither the position or intensity

M AN U

changes. The presence of these bands may indicate the formation of P-O-Cu or P-O-Zn linkages.

Raman spectroscopy indicated that an increase in the amount of CuO or ZnO introduced into the composition of glasses, at the expense of decreasing amounts of CaO and MgO, influences the phospho-oxygen subnetwork present in the analyzed structure in a different way. It was shown that copper ions cause its gradual polymerization, while zinc ions cause its

found.

31

31

P MAS-NMR

EP

3.3.

TE D

depolymerization. At the same time, polymerization of the silico-oxygen subnetwork was

P MAS NMR spectra of the tested glasses modified with the addition of CuO or ZnO,

AC C

together with component bands obtained after the process of their decomposition, are presented in Fig. 3. Detailed information about the content of the values of these spectral parameters are included in Table 2. In the analysis of the obtained 31P MAS-NMR spectra of tested glasses, the spectrum of the 0Cu41P / 0Zn41P sample, which does not contain CuO or ZnO was adopted as the reference point. The spectrum decomposition process for this glass made it possible to find one band with a significant half-width, which was situated within the range of negative values of chemical shifts (-28.9 ppm). This band is assigned to the presence of phosphorus-oxygen units of the Q2 type in the structure of this glass [22, 32, 45]. Spectra of glasses containing CuO/ZnO in an amount of up to 15 mol.% constitute a superposition of two Gaussian peaks, which show two various environments of the 8

ACCEPTED MANUSCRIPT phosphorus atom. However, a further increase in the composition of glasses with both CuO or ZnO (30 mol.%) influences another change in the environment of phosphorus atoms. For glasses containing copper ions, the spectrum for 30Cu41P is a superposition of three component lines and for the 30ZnO41P glass, it is a superposition of four component lines. It is concluded from the obtained 31P MAS NMR results that the addition of CuO/ZnO in the

RI PT

amount of 4 mol.% causes depolymerization of the phosphate-silicate glasses, which is confirmed by the appearance of component bands related to phosphorus-oxygen units of the Q1 type [22, 32, 45] (-10 and -11 ppm for glasses 4Cu41P and 4Zn41P, respectively). A further increase in the CuO content up to 15% mol does not influence the change of the

SC

position of these components; however, an increase in the relative content of phosphorusoxygen units of the Q2 type occurs (from 84 to 94%) with a simultaneous decrease in the

M AN U

relative content of more weakly polymerized phosphorus-oxygen units of the Q1 type (from 16 to 6%). This indicates the occurrence of gradual polymerization of the phospho-oxygen subnetwork. An increase in the CuO content up to 30 mol%, which is introduced at the expense of the reduced amounts of MgO and CaO, influences further transformation of the phospho-oxygen subnetwork, which is manifested by the occurrence of phosphorus-oxygen units of the Q3 type in the 31P MAS NMR spectrum of the 30Cu41P glass of at -44 ppm [22,

TE D

32, 45], which indicates progressing polymerization of the phospho-oxygen subnetwork. The registered change confirms the results obtained from Raman spectroscopy regarding the phospho-oxygen subnetwork.

EP

Also for glasses from the P2O5-SiO2-K2O-MgO-CaO system modified with the addition of ZnO in an amount of 4-15% mol, the presence of two main bands was found with a chemical shift

AC C

corresponding to the frequency of -26 and -11 ppm. Just as in the case of glasses from the Cu41P group, they were assigned to the presence of structural units of the Q2 (-26 ppm) and Q1 (-11 ppm) types. If growing amounts of ZnO were introduced into the composition of analyzed glasses, no significant changes in their position were found or in the share of peak components in the spectrum related to the presence of the aforementioned units (Table 2). The form of the 31P MAS NMR spectrum was changed significantly when the amount of the ZnO modifying oxide was 30% mol. In this situation, additional two component bands appeared in the MAS-NMR spectrum with chemical shifts of -6 and 0 ppm. Such frequencies correspond to the presence of Q1 and Q0 units [9, 46] and their presence would suggest progressing depolymerization of the phospho-oxygen structure. It should be emphasized 9

ACCEPTED MANUSCRIPT that the simultaneous appearance of bands from the Q1 and Q0 units indicates the presence of the phosphate-isolated tetrahedra, which would constitute an unambiguous confirmation of the occurring depolymerization of the phospho-oxygen structure. This conclusion was also confirmed by Raman spectroscopy as regards the phospho-oxygen subnetwork. It is, however, worth noticing that the appearance of two bands from structural units of the 31

P MAS NMR spectrum may be attributed to the

RI PT

Q1 type (at -6 and -11 ppm) in the

formation of Q1 sites covalently linked to one zinc cation, and forming P–O–Zn linkages in the glass network, just like the P–O–Pb and P–O–Al linkages formed in the lead-phosphate and aluminophosphate glasses, respectively [9, 47]. This can mean that with even higher

forming component apart from the role of a modifier. 31

P MAS NMR tests indicated the presence of structural units with

M AN U

The obtained results of

SC

contents of ZnO in the structure of analyzed glasses, it can also play the role of structure-

various degrees of polymerization in the structure of analyzed phosphate-silicate glasses: Q3, Q2, Q1 and Q0. On the basis of the behavior of the obtained bands, it was found that the introduction of growing amounts of copper and zinc ions into the structure of analyzed glasses has various effects on the analyzed phospho-oxygen subnetwork. It was shown that growing numbers of copper ions cause its gradual polymerization, which is confirmed on the

TE D

basis of the appearance of a band assigned to Q3 units with a higher degree of polymerization and due to changes occurring in relative contents of individual bands. For glasses modified by the addition of increasing amounts of ZnO, progressing

EP

depolymerization of the phospho-oxygen subnetwork and a change of the role of zinc ions in the vitreous matrix were confirmed - from the modifier function to a structure-forming

AC C

component.

4. Conclusions

Based on spectroscopic studies (FTIR, Raman and 31P MAS NMR), the influence of CuO and ZnO addition on the structure of phospho-silicate glasses from the P2O5-SiO2-K2O-MgO-CaO system was evaluated. FTIR spectroscopy made it possible to confirm the modifying role of copper and zinc ions in the tested vitreous structure. On the basis of these results, the loosening of the structure was confirmed as well as the formation of P-O-Cu or P-O-Zn linages at the expense of breaking some of the P=O bonds.

10

ACCEPTED MANUSCRIPT The use of Raman spectroscopy and

31

P MAS NMR made it possible to identify structural

changes occurring under the influence of introduced ions both in phospho-oxygen and silicooxygen subnetworks. On the basis of Raman spectra, the effect of polymerization of the silico-oxygen subnetwork under the influence of growing amounts of CuO was found. Both Raman and 31P MAS NMR spectra confirmed a different influence of copper and zinc ions on

RI PT

the phospho-oxygen subnetwork. It was shown that copper ions cause its gradual polymerization, while zinc ions influence its depolymerization. Simultaneous use of a few spectroscopic methods confirmed that zinc ions change its role in the tested vitreous matrix.

of a structure-forming component in higher contents.

SC

At lower zinc contents, zinc fulfils the function of a structure modifier, while it plays the role

M AN U

Acknowledgements The work was supported by Faculty of Materials Science and Ceramics AGH – University of Science and Technology No. 11.11.160.617. 5. References

[9] [10] [11] [12] [13] [14] [15]

EP

TE D

M. Karabulut, E. Melnik, R. Stefan, J. Non-Cryst. Solids. 288 (2001) 8-17. P. Stoch, M. Ciecińska, J. Therm. Anal. Calorim. 108 (2012) 705–9. M. Bitar, C. Knowles J, M.P. Lewis, V. Salih, J. Mater. Sci.-Mater. M. 16 (2005) 1131–6. Y.S. Lee, W.H. Kang. Mater. Sci. Forum. 449-452 (2004) 737-740. D. Cacaina, S. Simon, Optoelectron. Adv. Mater. 5(1) (2003) 191-4. R.K. Brow, C.A. Click, T.M. Alam, J. Non-Cryst. Solids. 274 (2000) 9-16. P. Shih, S. Yung i T. Chin, J. Non-Cryst. Solids. 224 (1998) 143-52. E. Metwalli, M. Karabulut, D. Sidebottom, M. Morsi, R. Brow, J. Non-Cryst. Solids. 344 (2004) 128-34. P. Shih, J. Ding i S. Lee, Mater. Chem. Phys. 80 (2003) 391-96. P. Pascuta, G. Borodi, N. Jumate, I. Vida-Simiti, D. Viorel, E. Culea, J. Alloys Compd. 504 (2010) 479-83. P. Shih, T. Chin, Mater. Chem. Phys. 60 (1999) 50-57. A. Chahine, M. Et-tabirou, M. Elbenaissi, M. Haddad, J. Pascal, Mater. Chem. Phys. 84 (2004) 341-47. J. Wiench, M. Pruski, B. Tischendorf, J. Otaigbe, B. Sales, J. Non-Cryst. Solids. 263-264 (2000) 101-110. B. Tischendorf, J. Otaigbe, J. Wiench, M. Pruski, B. Sales, J. Non-Cryst. Solids. 282 (2001) 147-58. K. Meyer, J. Non-Cryst. Solids. 209 (1997) 227-39.

AC C

[1] [2] [3] [4] [5] [6] [7] [8]

11

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

[16] B. Sales, J. Otaigbe, G. Beall, L. Boatner, J. Ramey, J. Non-Cryst. Solids. 226 (1998) 28793. [17] R. Brow, D. Tallant, S. Myers, C. Phifer, J. Non-Cryst. Solids. 191 (1995) 45-55. [18] M. Szumera, Spectrochim. Acta A. 137 (2015) 111–115. [19] M. Szumera, Mater. Lett. 135 (2014) 147–150. [20] M. Szumera, I. Wacławska, J. Sułowska, J. Therm. Anal. Calorim. DOI: 10.1007/s10973015-5010-5. [21] J. Sułowska, I. Wacławska, M. Szumera, J. Therm. Anal. Calorim. DOI 10.1007/s10973015-5044-8 [22] R.K. Brow, J. Non-Cryst. Solids 263&264 (2000) 1-28. [23] S.Y. Marzouk, Mater. Chem. Phys. 114 (2009) 188–193. [24] L. Abbas, L. Bih, A. Nadii, Y. Elamraui, J. Therm. Anal. Calorim. 90 (2007) 453–8. [25] I. R. Chakraborty, R. A. Condrate, Phys. Chem. Glasses. 26 (1985) 68-73. [26] N.K. Mohan et. al., J Alloys Compd. 458 (2008) 66-76. [27] F.H. El Batal, Y.M. Hamdy, S.Y. Marzouk, J. Non-Cryst. Solids, 355 2439-2447 (2009) [28] C. Dayanand, G. Bhikshamaiah, V. Jaya Tyagaraju, M. Salagram, A.S.R. Krishna Murthy, J. Mater. Sci. Lett. 31 (1996) 1945 [29] J. Sułowska, I. Wacławska, Z. Olejniczak, Vib. Spectrosc. 65 (2013) 44; [30] M. Sitarz, J. Mol. Struct. 887 (2008) 237; M. Sitarz, J. Non-Cryst. 357 (2011) 1603; [31] J. Šubcík, L. Koudelka, P. Mošner, L. Montagne, G. Tricot, L. Delevoye, I. Gregora, J. Non-Cryst. Solids 356 (2010) 2509–2516; [32] R.K. Brow, et al., J. Non-Cryst. Solids 191 (1995) 45-55. [33] J. Schwarz, et. al. J. Opotoelectron. Adv. Mater. 6 (3) (2004) 737-746. [34] M. El Hezzat, M. Et-tabirou, L. Montagne, E. Bekaert, G. Plavit, A. Mazzah, P. Dhamelincourt, Matter. Lett. 58 (2003) 60–66 [35] D.A. Magdas et al., J. Mol. Struct. 1056–1057 (2014) 314–318. [36] S. Sreehari Sastry, B. Rupa Venkateswara Rao, Bull. Mater. Sci., 38 (2015) 475-482. [37] M. Szumera, Spectrochim. Acta A. 129 (2014) 601–608. [38] S. Agathopoulos, D.U. Tulyaganov, J. M. G. Ventura, S. Kannan, A. Saranti, M. A. Karakassides, J. M. F. Ferreira, J. Non-Cryts. Solids, 352 (2006) 322-328 [39] J. Sułowska, I. Wacławska, Z. Olejniczak, Vib. Spectrosc. 65 (2013) 44-49. [40] L. Koudelka, I. Rösslerová, J. Holubová, P. Mošner, L. Montagne, B. Revel, J. Non-Cryst. Solids. 357 (2011) 2816–2821. [41] J.E. Pemberton, L. Latifzadeh, J.P. Fletcher, S.H. Risbud, Chem. Mater. 3 (1991) 195– 200. [42] A. Bertoluzza, M.A. Battaglia, R. Simoni, D.A. Long, J. Raman Spectrosc. 14 (1983) 178– 183. [43] S.S. Sastry, B.R.V. Rao, Physica B4. 34 (2014) 159–164; [44] M.A. Karakassides, A. Saranti, I. Koutselas, J. Non-Cryst. Solids 347 (2004) 69–79. [45] R.J. Kirkpatrick, R.K Brow, Solid State Nucl. Mag. 5 (1995) 9-21.

12

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

[46] F. Döhler, A. Mandlule, L. van Wüllen, M. Friedrich, D.S. Brauer, Mater. Chem. B, 3 (2015), 1125-1134. [47] S. Parabhakar, K.J. Rao, C.N.R. Rao, Chem. Phys. Lett. 139 (1987) 96-102.

13

ACCEPTED MANUSCRIPT List of Figures: Fig. 1. FTIR absorption spectra of CuO (a) or ZnO (b) addition phosphate glasses. Fig. 2. Raman spectra of CuO (a) or ZnO (b) addition phosphate glasses.

RI PT

Fig. 3. 31P MAS NMR spectra of CuO (a) or ZnO (b) addition phosphate glasses.

List of Tables: Table 1 The nominal chemical composition of glasses and determined by the X-ray Fluorescence Spectrometry (XRF) (in brackets) in mol.%

AC C

EP

TE D

M AN U

SC

Table 2. 31P MAS NMR parameters of selected glasses from P2O5-SiO2-K2O-CaO-MgO-CuO / ZnO system.

14

ACCEPTED MANUSCRIPT Table 1 The nominal chemical composition of glasses and determined by the X-ray Fluorescence Spectrometry (XRF) (in brackets) in mol.% SiO2

P2O5

K2O

CaO

MgO

0Cu/Zn41Si

6 (6.3)

41 (41.2)

6 (6.2)

19 (19.6)

28 (26.7)

2Cu41P

6

41

6

18

27

2

4Cu41P

6 (6.2)

41 (41.4)

6 (6.2)

17 (16.9)

26 (25.3)

4 (4.0)

8Cu41P

6

41

6

16

23

8

15Cu41P

6 (5.9)

41 (40.9)

6 (6.0)

13 (12.9)

19 (18.7)

15 (15.6)

30Zn41P

6

41

6

7

10

30

2Zn41P

6

41

6

18

4Zn41P

6 (5.8)

41 (41.5)

6 (6.1)

17 (17.4)

26 (25.1)

4 (4.1)

8Zn41P

6

41

6

16

23

8

15Zn41P

6 (5.3)

41 (40.6)

6 (5.8)

13 (13.8)

19 (18.2)

15 (16.3)

30Zn41P

6

41

6

7

10

30

SC 27

M AN U

TE D EP AC C

CuO

ZnO

RI PT

Glass name

2

ACCEPTED MANUSCRIPT Table 2. 31P MAS NMR parameters of selected glasses from P2O5-SiO2-K2O-CaO-MgO-CuO / ZnO system. Relative amounts n of Q sites [%]

13.9

-26 -10

15 Cu41P

30 Cu41P

FWHM [ppm]

-28.9

100

0 Zn41P

-28.9

13.9

100

4 Cu41P

15 10

84 16

4 Zn41P

-26 -11

13 10

81 19

-26 -9

14 10

94 6

15 Zn41P

-26 -11

13 10

79 21

-27 -44 -11

16 13 8

86 11 3

30 Zn41P

14 7 3 4

63 24 7 6

[ppm]

EP

TE D

Full width at half maximum

AC C

*

No

-27 -11 -6 0

*

RI PT

0 Cu41P

No

Relative amounts of n Q sites [%]

Chemical shift [ppm]

*

SC

FWHM

M AN U

Chemical shift [ppm]

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT Highlight

EP

TE D

M AN U

SC

RI PT

Glasses from the P2O5-SiO2-K2O-CaO-MgO-CuO(ZnO) systems were analysed A copper ions cause gradual polymerization of the phosphor-oxygen subnetwork A zinc ions cause depolymerization of the phosphor-oxygen subnetwork Spectroscopic methods showed polymerization effect on the silico-oxygen subnetwork A change of the role of zinc ions in the vitreous matrix was confirmed

AC C

1. 2. 3. 4. 5.