THE STRUCTURE AND PROPERTIES OF PHOSPHATE GLASSES WITH TRANSITION METALS ELEMENTS

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THE STRUCTURE AND PROPERTIES OF PHOSPHATE GLASSES WITH TRANSITION

METALS ELEMENTS

J. Wasylak, J. Koprowaski, E. Czerwosz

To cite this version:

J. Wasylak, J. Koprowaski, E. Czerwosz. THE STRUCTURE AND PROPERTIES OF PHOSPHATE GLASSES WITH TRANSITION METALS ELEMENTS. Journal de Physique Colloques, 1982, 43 (C9), pp.C9-247-C9-251. �10.1051/jphyscol:1982945�. �jpa-00222474�

THE STRUCTURE AND PROPERTIES OF PHOSPHATE GLASSES WITH TRANSITION METALS ELEMENTS

J. Wasylak, J. Koprowaski and E. Czerwosz

University of Mining and Metallurgy, Department of Glass, 30 Miokiewiaza at. A-3,30-059 Krakow, Poland

Résumé.- Dans ce travail on a déterminé la formation du verre et quelques propriétés des verres du système : Ba(PO,)-Y 0 (MoO )-Ti02(Fe 0 ).Utili- sant l'analyse des spectres Raman on présente les données de la structure du système ci-dessus mentionné. On a constaté la présence des groupes struc- turels métaphosphates et orthophosphates ainsi que la présence des fragments cristallins, dans la matrice du verre, dans le cas du système Ba(PO.)„-Y 0 . Les propriétés électriques des verres : la résistance spécifique (pv), l'angle de perte (tg<Sx), la permittivitédiélectrique (er), indiquent le caractère di- électrique des verres, qui contiennent ï?0 et une semi-conduction pronon- cée pour les verres à contenu Fe 0 élevé.

Abstract. - Conditions of melting glasses of the Ba(PO„)„ - Y.O (MoO.) - Ti0_(Fe 0 ) system and some of the properties of the glasses are discussed.

Analysis of the Raman spectra was the source of information on the structure of the glasses. In the glass matrix of the Ba(PO,)_ - Y„0_ system were found structural metaphosphate and orthophosphate groups and crystal fragments.

Electric properties : specific resistance (pv), loss angle (tg6x) and permit- tivity (er) indicated, the dielectric character for the glasses with Y„0, and a highly semiconducting character for those with a greater content of Fe203.

1. Experimental. - Samples of 40-50 g of glasses were prepared in unglazed porcelain crucibles in a furnace with sillit rod resistors. Melting temperatures ranged from 1200 to 1400°C depending on the glass composition ; time of melting was 60 minutes.

Ba(P0 ) Y2°o> H MoO , L 0 , TiO , Fe 0 of purity grade "pure" were the batch com- ponents.

2. Results. - The vitreous state of the Ba(P0 ) - Y 0 (MoO ) - TiO (Fe 0 ) system (Fig. 1) was investigated. Maximum concentrations of introduced additions were : Ba(P03)2 - 40-MOO ; Y ^ - 0-H5 ; Mo03 - O T 3 0 ; Ti02 - 0^20 ; F e ^ - 0^40% mol.

Samples of glass of the Ba(P0 ) - Y 0 - TiO. system were transparent and those with TiO„ had a violet shade. Larger additions of Y„0 and TiO. to barium meta- phosphate increased chemical resistance of glass but they also made crystalliza- tion easier thus influencing diminution of the vitreous state region. MoO. and Fe20. were far more easily soluble in phosphate glass than in silicates.When there were more than 30-40% mol of the two oxides stratification of glass occurred. It

led to crystal formation which limited vitreous state region in the investigated system. Raman spectra of binary glass : Ba(P0,), - Y 0 TiO , Fe.O. are shown in Figure 2. i i Z 5 2 I Z

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1982945

JOURNAL DE PHYSIQUE

F i g u r e 1 - Domains of v i t r i f i c a t i o n of t h e s y s t e m s 1- Ba(P0 ⁾ -Y 0 -Ti02 ; 3 2 2 3 2- Ba(P0 ) -MOO -Fe203

3 2 3

F i g u r e 2 - The Raman s p e c t r a of t h e g l a s s e s of t h e Ba(P0 3 2 2 3 ) -Y 0 (MOO )-Ti02 3

(Fe 0 ) s y s t e m : 1-Ba(P03)2 ; 2 , 3 - Ba(P03)2 - Y2O3(10,15% m o l l ; 4 , 5 - Ba(PO ) -

2 3 3 2

T i 0 ( 1 0 , 2 0 % mol) ₂ ; 6-Ba(P03)2 - Fe 0 (10% mol) _{2 3}

.

The s p e c t r a were o b t a i n e d u s i n g a Ar 2+ l a s e r ( w a v e l e n g t h 5 1 4 . 5 nm, power 200 mW).

The s p e c t r u m of t h e g l a s s w i t h 10% mol Y 2 0 3 ( F i g . 2 , c u r v e 2) was t y p i c a l f o r v i - t r e o u s b a r i u m m e t a p h o s p h a t e (340, 480, 698, 1030, 1155, 1245 ctn-I). The b a n d s w e r e a t t r i b u t e d a f t e r ( 1 ) t o o s c i l l a t i o n s o f t h e f o l l o w i n g g r o u p s o f m e t a p h o s p h a t e c h a i n : 690 - v (POP), 1030 - V a s (POP), 1155 - V ( 0 PO ) , 1245 - v as

svm svm

(0'-PO-). As Y203 c o n t e n t i n c r e a s e d ( t o 15% mol) s h a r p p e a k s a p p e a r e d i n t h e s p e c -

t h e v i t r e o u s l a t t i c e ( 2 , 3 ) . New s h a r p peaks a p p e a r e d a t t h e h i g h f r e q u e n c y r e g i o n of t h e spectrum. They c o u l d n o t b e a t t r i b u t e d n e i t h e r t o t h e metasphophate s t r u c - t u r e n o r t o t h e c r y s t a l s t r u c t u r e of Y 0 It c o u l d b e assumed t h a t t h e y o r i g i n a t e d

2 3 '

from o s c i l l a t i o n s of mixed Y203 - PO system a l t h o u g h i t was d i f f i c u l t t o s a y how 3

t h e y were l i n k e d ; o r t h a t t h e y were of e l e c t r o n i c o r i g i n . The s p e c t r a of g l a s s e s w i t h 10% mol T i 0 2 b e l o n d i n g t o t h e Ba(P03)2-Ti02 system ( F i g . 2 , c u r v e 4 ) showed t h e p r e s e n c e of s t r o n g bands c h a r a c t e r i s t i c of metaphosphate g l a s s (680, 1155, 1250 cm-1) and of t h r e e medium i n t e n s i v e bands (613, 895, 1003, 1078 cm-1) c h a r a c - t e r i s t i c of o r t h o p h o s p h a t e s t r u c t u r e . I n t e n s i t i e s of t h e bands c o r r e s p o n d i n g t o meta-and o r t h o p h o s p h a t e were e q u a l f o r t h e g l a s s w i t h 20% mol T i 0 which i n d i c a t e d t h a t t h e y c o n t a i n e d a g r e a t e r amount of o r t h o p h o s p h a t e g r o u p s . o n l y t h e g l a s s w i t h 10% mol Fe 0 of t h e Ba(P03)2 - Fe 0 system showed t h e Raman s p e c t r u m . I t s bands

2 3 2 3

had a complex meta - and o r t h o p h o s p h a t e s t r u c t u r e . Very h i g h f l u o r e s c e n c e of t h e remaining g l a s s e s of t h e system made r e c o r d s of t h e Raman s p e c t r a i m p o s s i b l e . G l a s s e s of t h e Ba(P03)2 - MOO system d i d n o t show t h e Raman s p e c t r a . G l a s s s t r u c -

3

t u r e a n a l y s i s of t h e system was c o n f i r m e d by changes of g l a s s p r o p e r t i e s a s func- t i o n of molar c o n c e n t r a t i o n of t h e i n t r o d u c e d a d d i t i o n s . G l a s s d e n s i t y i n c r e a s e d p r o p o r t i o n a l l y t o m o l a r c o n c e n t r a t i o n of o x i d e s : Y203, T i 0 2 , Moo3, Fe203. I t ran- ged from 3.6080 t o 4.130 gcm-J. o x i d e a d d i t i o n s t o t h e b a s e g l a s s e s caused a de- c r e a s e of e x p a n s i o n c o e f f i c i e n t a . It was r e l a t e d t o a g r e a t e r bond s t r e n g t h b e t - ween p h o s p h a t e p o l y h e d r a a n d a h i g h e r r i g i d i t y of s t r u c t u r a l s k e l e t o n . Expansion c o e f f i c i e n t ranged from 138.0 t o 1 1 5 . 7 x 10-7 deg-1. R e s i s t i v i t y measurements of t h e g l a s s e s of i n v e s t i g a t e d system showed a l i n e a r c h a r a c t e r of t h e dependence l o g ~ ~ - ~ / ~ a t t e m p e r a t u r e range 350-20°C ( F i g . 3 ) . Diagrams f o r some g l a s s e s mf t h e b i n a r y s y s t e m s a l l o w e d t h e c a l c u l a t i o n of t h e f o l l o w i n g c o n s t a n t s : a c t i v a - t i o n e n e r g y of c o n d u c t i o n mechanisms EA ; a, and T K - l O O i . e . t e m p e r a t u r e a t which

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E l e c t r i c p r o p e r t i e s of g l a s s e s of t h e Ba(P03)2 - ^{Y203(Mo0 )} - Ti02(Fe203) s y s t e m . 3

JOURNAL DE PHYSIQUE

Ohm

F i g u r e 3- R e s i s t i v i t y o f t h e g l a s s e s of t h e B ~ ( P O ~ ) ~ - Y ~ O ~ ( M O O ~ ) - T ~ O ~ ( F ~ ~ O ~ ) a g a i n s t t e m p e r a t u r e : 1-Ba(P03) 2; 2-Ba(P03) 2-Y203 ( 10%) ; 3-Ba(P03) 2-Ti02 ( 1 0%) ; 4-Ba(P03) 2-

Moo3 (1 0%) ; 5,6,7-Ba (P03) -Fe203 ( 10-30%)

.

F i g u r e s 4 and 5 show t h e d i a g r a m s of t h e dependences E r = f ( T ) and t g 6 x = f ( T ) , r e s p e c t i v e l y , a t 1 kHz f r e q u e n c y . The d i a g r a m s showed t h a t 10% mol Y 2 0 3 and 10% mol T i 0 improved d i e l e c t r i c p r o p e r t i e s of g l a s s . G l a s s e s w i t h t h e s e o x i d e s d e m o n s t r a t e 3 a g r e a t t e m p e r a t u r e s t a b i l i t y of d i e l e c t r i c c o n s t a n t cr = 10-11 a t t e m p e r a t u r e n o t g r e a t e r t h a n 200°C. Values of t h e i r d i e l e c t r i c l o s s were a l s o

F i g u r e 4 - P e r m i t t i v i t y o f t h e g l a s s e s of t h e Da(P03)2 - Y203 - ^(Moo3) - Ti02(Fe203) system i n t h e t e m p e r a t u r e r a n g e 20-350°C.

OH groups i n t h e b a s e g l a s s . G l a s s e s w i t h Fe203 showed a d i f f e r e n t c h a r a c t e r of c o n d u c t i o n . Semiconducting c h a r a c t e r of c o n d u c t i o n i n c r e a s e d w i t h i n c r e a s i n g Fe 0 c o n t e n t : a c t i v a t i o n e n e r g y of c o n d u c t i o n mechanisms was lowered and d i e -

2 3

l e c t r i c p o l a r i z a b i l i t y i n c r e a s e d . T h i s i s r e l a t e d t o t h e p r e s e n c e of a i l a r g e amount of u n s a t u r a t e d bonds of ~ e ~ + a n d ~ e i n t h e g l a s s m a t r i x and an e a s y mechanism of ~ + e l e c t r o n jump between t h e c a t i o n s .

F i g u r e 5 - Tangent of t h e l o s s a n g l e ( t g d x ) of t h e g l a s s e s of t h e Ba(P0 ) -

3 2 y203 ( M o o 3 ) - ~ i o 2 ( ~ e 0 ) system i n t h e t e m p e r a t u r e r a n g e 20-350°C.

2 3

R e f e r e n c e s

1. L a z a r i e v (A.N.)- K o l e b a t i e l n y j e s p e k t r y i s t r o j e n i e s i l i k a t o v , Nauka, L e n i n g r a d , 1968.

2. White (W.B.)and Keramidas (V.G.),Spectrochim. Acta, 1972, 28A, 501.

3. Schaack ( G . ) and K i j n i n g s t e i n ( J . P .), J. Opt. Soc. Am., I 9 7 0 , 6 0 , - 1 1 10.