The thermal stability of tungsten glasses is higher than that of molybdenum ones. ... The phosphate glasses compared to borate and silicate ones have very ...
MATEC Web of Conferences 5, 04012 (2013) DOI: 10.1051/matecconf/20130504012 c Owned by the authors, published by EDP Sciences, 2013
Preparation and characterization of phosphate glass system A2 MnMP2 O10 (A = Li, Na, K) and (M = W, Mo) M. Moutataouia1 , M. Lamire1 and M. Taibi2 1
´ Laboratoire de Physico-Chimie des Materiaux Inorganiques, Faculte´ des Sciences A¨ın Chock, Casablanca, Morocco 2 ´ e´ Mohammed V Agdal, Laboratoire de Physico-Chimie des Materiaux, ´ Universit ENS Avenue Mohamed Bel Hassan El Ouazzani, BP. 5118, Takaddoum - Rabat, Maroc
Abstract. New materials based glassy phosphates and transition elements A2 MnMP2 O10 (A = Li, Na, K) and (M = Mo, W) were prepared by direct fusion of the mixture of the reactants followed by quenching in the air. Analysis by X-ray diffraction showed that the obtained materials are amorphous. Differential scanning calorimetry DSC was used to determine the glass transition (Tg) and crystallization (Tc) temperatures. The thermal stability of tungsten glasses is higher than that of molybdenum ones. Tungsten plays, certainly, a role of cross-linking polyphosphate groups by creating more covalent new bonds P-O-W and W-O-W. Moreover, it has been shown that lithium glasses are more stable than sodium and potassium, probably due to the potassium hygroscopy. Raman analysis confirms that the studied glasses have similar structures and the predominant structural units are PO4 , P2 O7 and MO6 polyhedra (M = W, Mo, Mn).
INTRODUCTION The phosphate glasses compared to borate and silicate ones have very interesting physical properties. The low melting temperature of phosphate and their ability to vitrify make easy their development. They are characterized by low glass transition temperatures and high thermal expansion coefficients. These characteristics, allow them to be used for original applications: sealing glasses , oxidation resistant coatings, their interesting optical properties permit them to be operate as template for laser , waste containment matrixes. However, the use of these materials is limited by their low chemical durability. To overcome this drawback, the corrosion resistance of phosphate glasses has been improved by the introduction of cations that enhance the glassy network against the hydrolysis (P-O-M more covalent). Include Al3+ , Fe3+ , Pb2+ [3, 4] or anions such as N3− that increase the linking entities phosphate . Thus some phosphate-based glasses have comparable or higher durability to silicate glasses and are used as containment of waste . In order to obtain new performance phosphate glassy materials, we have prepared and characterized the glasses system A2 MnMP2 O10 with (A = Li, Na, K) and (M = W, Mo). 1. PREPARATION OF GLASSES The preparation of A2 MnMP2 O10 glass with (A = Li, Na, K) and (M = W, Mo) is formed by direct heating, in air, the mixture of ANO3 , MnCO3 , MO3 (M = W, Mo) and (NH4 )2 HPO4 . Reagents, taken in stoichiometric proportion, are finely ground to obtain a homogeneous mixture. The reaction takes place in a platinum crucible. A first heat treatment is performed at 200◦ C to decompose the ammonium dihydrogen phosphate (NH4 )2 HPO4 and a second at 400◦ C to decompose the manganese carbonate MnCO3 . The temperature is then gradually raised to
600◦ C to decompose completely nitrates of alkali metals ANO3 . The fusion is reached by heating the mixture at 900◦ C for 20 to 30 minutes. The resulting liquid is then quenched on a nacelle preheated to 200◦ C to avoid thermal shock. The obtained glasses are brown. These materials were characterized by: X-ray diffraction, density measurement, differential scanning calorimetry DSC and Raman vibrational spectroscopy. 2. RESULTS 2.1. XRD, density measurement, DSC The diffractograms X of prepared materials are typical of non crystallized compounds (no diffraction lines); therefore they confirm they are amorphous. Measurements of density and molar volume of A2 MnWP2 O10 and A2 MnMoP2 O10 (A = Na, K, Li) glasses show that for all the glasses (tungsten and molybdenum) the density increases gradually as the molecular weight of alkali metal increases. The glass transition Tg and crystallization Tc temperature are determined from the DSC thermograms (Figure 1). We note the evolution of Tg and Tc as a function of alkali ions, glasses tungsten and molybdenum ones. We fond that the glass transition temperature Tg increases from lithium to potassium. 2.2. Study by Raman Spectroscopy Raman spectra are reported in figures (2 and 3). The analysis of these spectra shows that their appearance is identical and indicates that their structures are almost similar. The most intense Raman band observed at 920 cm−1 , decreases in intensity and width in the order Li> Na>K.
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Figure 1. DSC curves of glasses Li2 MnWP2 O10 (1), Na2 MnWP2 O10 (2), K2 MnWP2 O10 (3), Li2 MnMoP2 O10 (4), Na2 MnMoP2 O10 (5) and K2 MnMoP2 O10 (6). 0,5
923 278 373
377 269 272 373
643 563 634 559
the impact of the latter within the glass network. If the molar volume remains constant, we can conclude that the cation introduced is placed in the cavities of the network. A decrease in the molar volume shows that the introduced cation strengthens the network: it decreases the chaining of oxygen ions. An increase in molar volume is indicative of a network expansion . We can thus explain the decrease of the molar volume by network cross-linking . The analysis of the DSC curves (Fig. 1) of two sets of glasses (Tungsten (W), molybdenum (Mo)) allowed us to identify several types of thermal stability. The first on tungsten glasses which have higher Tg than molybdenum ones, the second type relates to molybdenum glasses which have a difference (Tc-Tg) relatively low (94 to 144◦ C) compared to tungsten glasses, the third observation corresponds to the absence of exothermic crystallization peaks for both Na2 MnWP2 O10 and K2 MnWP2 O10 glasses. Therefore their thermal stability could not be evaluated numerically, but it is probably very high. In addition, the difference (Tc-Tg) (>170◦ C): Case of (lithium - tungsten) glass is higher than that on the molybdenum glass, confirming the high thermal stability of these glasses. The fourth type relates to K2 MnMoP2 O10 glass having two exothermic peaks (510 and 545◦ C) rather broad. They, probably, can be attributed to two crystalline phases. The behavior of studied glasses is close to that of A2 MgWP2 O10 (A = K, Cs, Rb) . The stability of the glasses devote them a great importance for future applications. For example, it is known that a temperature difference DT less than 100◦ C is suitable in industrial processes.
ν (cm )
Figure 2. Raman spectra of the glasses Li2 MnWP2 O10 (1), Na2 MnWP2 O10 (2) and K2 MnWP2 O10 (3). 0,7
761 643 563
634 559 634 559 -1
ν (cm )
Figure 3. Raman spectra of the glasses Li2 MnMoP2 O10 (4), Na2 MnMoP2 O10 (5) and K2 MnMoP2 O10 (6).
3. DISCUSSION 3.1. Density, thermal stability In the case of glasses with tungsten and molybdenum, the density increases gradually as the molecular weight of the alkali metal increases. It is known that changes in the molar volume (Vm) depend on the molecular weight of alkali metal ions introduced into the glass. This reflects
In last few years , numerous studies on the structure of the glasses were conducted. Nevertheless, the study of the structure of glasses is not easy to implement because they are characterized by a substantial disorder and a lack of large-scale three-dimensional periodicity. Vibrational spectroscopy (Raman and infrared) was the most suitable techniques for study of the glassy materials. Previous studies  have reported that the addition of various oxides to P2 O5 leads the depolymerization of the network and the formation of different structures. It is also known that the structure of the glass depends on the O/P (oxygen/phosphorus) ratio and on the properties of the introduced oxides. The studied glasses contain MO3 (M = W, Mo), MnO and oxides of alkali A2 O (A = Li, Na, K). Oxides of alkali ions are considered as network modifiers. However, oxides and MO3 do not readily form the glass network. The O/P ratio for A2 O - MnO - P2 O5 composition is 3.5 and corresponds to a pyrophosphate structure. The addition of MO3 increases the O/P ratio in A2 MnMP2 O10 glasses to 5. The real O/P is probably close to 3.5 than 5 because the W(Mo)O3 oxides does not act as modifiers. The structure of the glass may be composed mainly of the pyrophosphate Q1 and orthophosphate Q0 groups (Qn : n is the number of bridging oxygen atoms by PO4 tetrahedron). A great similarity was found between the Raman spectra of A2 MnMP2 O10 glasses studied in this work and those of [Rb2 MgWO2 (PO4 )2 ] crystalline
phases (13) which consist of PO4 groups, octahedra WO6 and MgO6 . That suggests that the A2 MnMP2 O10 glassy network contains also the same structural units. However, the presence of Raman bands near 750 cm−1 not observed in the crystal structure of Rb2 MgWO2 (PO4 )2 and which can be assigned to symmetric stretching modes of P2 O7 groups indicates that the A2 MnMP2 O10 glass structure is formed of a large amount of pyrophosphate. We note that the Raman bands near 920 cm−1 decrease in intensity and width in the order Li > Na > K, they can be assigned to symmetric vibrations of MO6 octahedra (M = Mn, W, Mo). A Raman band very similar and with the same intensity was observed for the [(80-0.8x)NaPO3 (20-0.2x)BaF2 -xWO3 ] glasses . The high intensity of this band, probably, indicates that the MO6 octahedra are more distorted. The Raman band 1040 cm−1 can be attributed to symmetric and asymmetric stretching of PO3 terminal group . The Raman band near 750 cm−1 can be attributed to symmetric vibration modes of pyrophosphates POP units (Q1 ). Early studies on phosphates showed a band near 640 cm−1 which is characteristic of deformation vibrations of metaphosphate groups (P3 O9 )3− . The band observed at 550 cm−1 can be assigned to deformation vibrations of pyrophosphates and orthophosphates groups. Raman bands observed between 270 and 370 cm−1 can be assigned to deformation vibrations of MO6 octahedra resulting from short (M-O) and long (O-M-O) links. 4. CONCLUSION The X-ray diffraction analysis showed that the synthesized materials are amorphous. The differential scanning calorimetry (DSC) confirmed that the thermal stability of tungsten glasses is higher than that of molybdenum ones. Tungsten plays, probably, a role of crosslinking polyphosphate groups by creating P-O-W and W-O-W bonds more covalent, which justified their thermal stability. The analysis by Raman of A2 MnMoP2 O10 (A = Li, Na, K) and (M = W, Mo) glass compositions showed that their structure is mainly formed by pyrophosphates groups and P-O-T , T-O-T (T = Mn, W, Mo) chains similar to those existing in other phosphate glassy materials.
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