RAMAN SPECTRUM STUDIES OF THE COORDINATIONS OF ALUMINIUM AND BORON IN Na2O-Al2O3-B2O3-P2O5 GLASSES

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RAMAN SPECTRUM STUDIES OF THE

COORDINATIONS OF ALUMINIUM AND BORON

IN Na2O-Al2O3-B2O3-P2O5 GLASSES

Yin Yifen, Jiang Dehua, Chen Xiangsheng, Bian Beiya, Huang Xihuai

To cite this version:

J O U R N A L

DE PHYSIQUE

Colloque C8, supplCrnent au n012, Tome 46, d6cernbre 1985 page C8-311

RAMAN SPECTRUM STUDIES OF

THE

COORDINATIONS OF ALUMINIUM

AND BORON IN Na20-A1.203-B203-P205 GLASSES

Yin Yifen, Jiang Dehua, Chen Xiangsheng, Bian Beiya and Huanp, Xihuai

Shanghai I n s t i t u t e o f Ceramics, Academia S i n i c a , Shanghai, China

Rk.sun&Les Q t a t s de coordination d'aluminium et de bore dans l e v e r r e Na20- A1203-B203-P205 ont k t 6 Btudie par l a technique de s p e c t r o s w p i e

Raman.

L'etude montre que quand l e s ions de bore et d'aluminium e x i s t e n t simultane- ment dans l e v e r r e phosphate, il e s t possible que l e s ions de bore f o m e n t

les t g t r a i d r e s ED4 avant l e s ions d'aluminium. Et les n m b r e s de coordination de ces premiers sont t r o i s e t quatre e t ceux de A 1 quatre et s i x .

Abstract - The coordination s t a t e s of aluminium and boron i n Na20-A1203-B203- P205 g l a s s e s have been studied by means of lClaman spectroscopy. The study shows t h a t when boron and aluminium ions e x i s t simultaneously i n phosphate glasses, i t is p o s s i b l e t h a t boron ions form W4 tetrahedra p r i o r t o alumi- nium ions, and t h e former has t h r e e and four coordinations while t h e l a t t e r has four and s i x .

I - INTRLIDUCTION

W e have shown t h e Raman s p e c t r a of sodium aluminophosphate g l a s s e s i n reference / I / . The reason f o r such i n t e r e s t is t h e f a c t t h a t l e c t u r e s about Raman spectrum s t u d i e s of t h e s t r u c t u r e of g l a s s e s i n t h e Na 0-A1203-P205 system were r a r e l y

2

reported and t h a t c e r t a i n g l a s s e s i n t h i s system are good sodium ion conductors. I n order t o f u r t h e r improve t h e ion conductivity of t h e g l a s s e s , b o r i c oxide w a s added t o t h e t e r n a r y glasses.

A s is w e l l known, t h e r o l e of aluminium ions i n t h e g l a s s s t r u c t u r e is r a t h e r d i f - f e r e n t f r a n t h a t of boron ions. ~ 1 ' ~ ions which e x i s t i n 4 and 6 coordinations c m a c t as g l a s s forming and modifying cation respectively, while both 3 and 4 wordina- t i o n B ~ * ions are p a r t of t h e g l a s s network. There is no doubt t h a t t h i s makes t h e s t r u c t u r e of Na20-A1203-B203-P205 g l a s s e s m c h more complex than t h a t of Na20-A1203- P ₂ 0 glasses. A s a r e s u l t , t h e e f f e c t on t h e g l a s s conductivity is a l s o d i f f e r e n t . ₅ The a r t i c l e is aimed a t dealing with t h e g l a s s s t r u c t u r e through i n v e s t i g a t i n g t h e changes of boron and aluminium coordinations by means of Barnan spectroscopy.

JOURNAL DE PHYSIQUE

I1 - E X P E R I m A L

The designed canpositions of t h e g l a s s e s are shown i n t h e Figs. 1-3. P a r a l l e l polarized (XX) Raman s p e c t r a of g l a s s e s were measured on a Spex Ramalog spectro- meter a t a s c a t t e r i n g angle of go0. The e x c i t a t i o n source was t h e 51458 l i n e of A r ion laser. The laser power was 50tknw.

I11

-

DISCUSSION OF RESULTS

Table 1, where t h e Raman peaks of d i f f e r e n t kinds of groups which may appear i n t h e Na20-A1 _{2 3 2 5} 0 -P 0 g l a s s e s , is used as a reference f o r discussing t h e changes of Raman s p e c t r a due t o B203 added t o t h e glasses.

Table 1. Raman peaks of d i f f e r e n t kinds of groups which may appear i n t h e Na20-A1 0 -P (

2 3 2 peaks

6'

1280, 1170, 700, 645 / 2 , 3 / 1120, 540 131 1112, 540 /3/ 1060-1080, 720 1'41 760 /5/ 1040, 600, 470, 300 111

.

g l a s s e s

1. Fig. 1 shows t h e Raman s p e c t r a of 45Na2O.xB2O3.(5-x)Al2O3-50P2O5 and 40Na20.

xB203~(10-x)A1203~50P205 a c i d i c glasses. Compared with t a b l e 1,

i t

becames c l e a r t h a t t h e peaks which appear i n both f i g s . l a and d can be a t t r i b u t e d t o t h e vibra- t i o n of g l a s s network which c o n s i s t s of major numbers of (F03);- chains and r i n g s , a small number of ( ~ ~ 0and (~ ~ ~) ~~ 0-groups. When A1203 ~ ~ ) ~ -

is

replaced by B203 up t o 10 mou, t h e Raman s p e c t r a (cf

.

f i g s . lb-c, e-h) show no g r e a t changes, except t h e

gradual disappearance of t h e peak a t 540

&'

caused by ( ~ ~ 0and (~ ~ ~) ~~ -0 ~ ~ ) ~ -groups. Disappearance of t h e polyphosphate groups r e s u l t i n g from t h e replacement of

A1203 by B 0 may be i n t e r p r e t e d t h a t t h e r e is a difference between coordination 2 3

s t a t e s of aluminium i n phosphate and borate glasses. When adding A1203 t o borate g l a s s e s with low alkali-to-boron r a t i o s , boroxol groups form again because of t h e replacement of ED4 t e t r a h e d r a i n borate r i n g s by A104 t e t r a h e d r a / 6 , 7 / . I n o t h e r words, the ~ 1i o n s form A 1 0 u n i t s p r i o r t o B + ~ ~ + ions i n borate glasses. However, it

4

has been proved t h a t i n a c i d i c Na20-A1203-P205 g l a s s e s with A1203/P20510.63, nearly a l l of ~ 1 + ~ ions

are

six

coordinated. The r o l e of ~ 1 ' ~ ions i n t h e g l a s s s t r u c t u r e is t h e same as t h a t of ~ a + ions / I / . A s soon as B203 is added t o t h e s e glasses, we think it is possible t h a t some of them may scavenge t h e necessary oxygen ions from

peaks due t o borate rings with

E

D

u n i t s (720, 750 and 780 & l / 7 / )

are

observed. 4

This might mean t h a t a t low concentration of boron ions, it

is

present as "loose" E 0 4 tetrahedra i n the phosphate network.

Fig. 1. Raman spectra of 45Na20.xB2O3. Fig. 2. Raman spectra of 45Na20-xB2O3- (5-x)A1203-50P205 (a-c) and 40Na20. ( 10-x) -A1203. 45P205 glasses.

xB 0

-

(10-x)A1203-50P205 glasses (d-h)

.

2 3

2. Fig.2 shows t h e Raman spectra of 45Na 0.xB203-(10-x)A1203.45P 0 neutral glasses.

265

C8-3 14 JOURNAL

DE

PHYSIQUE

B203, t h e peak a t 1080

6'

due t o (P 0 )& groups vanishes, and peaks a t 1120 and 540

6'

due t o ( ~ ~ ( 3 ~ ) ~ - and (P4013)b7groups tend t o vanish tm. A t t h e same tlme, t h e peak a t 760

6 .

caused by A104 tetrahedra f i r s t degenerates i n t o shouldei, then t h e shoulder is replaced by t h e a t 770-780

6

'

a t t r i b u t e d t o tetraborate groups with ED4 u n i t s /7/, and it seems t o display a s t r u c t u r a l c h a r a c t e r i s t i c similar t o t h e 45Na20-l0B2O3-45P205 glass (cf. fig.2e). The regular change i n spectra again show t h a t , with substituting B203 f o r A1203, 81t3 ions change frcm 4 i n t o 6 coordination and phosphate network polymerizes. The ultimate r e s u l t of these changes must have offered 0= ions, boron ions needed f o r changing from 3 i n t o 4 coordination.

3. Fig. 3 shows t h e Raman spectra of 45Na20~x13203~(20-x)A1203~35P205 alkaline glasses. A s compared with t a b l e 1, it is obvious t h a t fig.3a can be a t t r i b u t e d t o

t h e vibration of Am4 groups. Substituting B203 f o r A1203 up t o 20 ml%, t h e develop- ment of aluminophosphate network can be observed as follows: Am4

-

Alpo4+A104

-

A ~ o ~ + ( P , ~ ) P- 1040 an-' 1040 760 760 1065 ( ~ ~ 0 ~ ) ~ - + ( ~\ ~ 0+ ~( ~~ )~ ~0

-

-~ ~ ) ~ -e 1060

1120

(P 0 )5-

+

(P 013) 6 3

\L.-L~

11 0 cm

Frcm what is mentioned above, it can be deduced t h a t s u b s t i t u t i n g B203 f o r A1203

d f i r s t leads t o t h e depolymerization of Am4

network, and then urges t h e polymerization

c of phosphate network. The l a t t e r process is very s i n i l a r t o those i n acidic and netural glasses. However, t h e r o l e of boron i n phosphate glasses with higher B203 seeins t o be unique. For 45Na20.20B2O3-35P 0 glass,

-12 5

b besides-strong peak a t 1120 cm due t o tri- and tetraphosphate groups, its Raman spec-

x=o

_trum

a l s o shows t h e peaks

at

1035. 730.685 and 640 6 ' ( c f . fig.3e). The peaks a t 730 a 685 and 640

6'

can be associated with t h e I I I I I I I I I I I I vibrations of diborate groups with two ED4 200 600 1000 ,400 (cm-'

)

u n i t s and ring-type metaborate groups with

one NED on each ED3 u n i t /7/. But t h e peak Fig. 3.

Raman

spectra of 45Na20e a t 1035

6

'

cannot be so readily assigned

-

u n i t . Although t h i s peak a l s o appears i n t h e Raman spectrum of A1203=5 mol% g l a s s ( c f . fig.3d), it can not be linked with t h e v i b r a t i o n of A m 4 groups, because A1203 is absent i n t h e 20 mol% B203 g l a s s . On t h e o t h e r hand, T, Tsuchiya e t 61 / 8 / point- ed out t h a t t h e Raman peaks of t h e c r y s t a l l i n e RW4 were found a t 485 and 1130

&',

and t h e r a t i o between t h e i r s c a t t e r i n g i n t e n s i t y was about 4. The peak a t 485 an-'

-1

w a s not found i n figs.3d-e, s o we have no reason t o associate 1035

cm

peak with t h e v i b r a t i o n of

BFO

₄ groups i n which t h e excess of negative charge on t h e El4 u n i t s is compensated by t h e excess of p o s i t i v e charge on t h e FQ4 u n i t s . I n other words, t h e P=O double bond is open i n t h i s case. In order t o d i s t i n g u i s h it frcm ( B P O ~ ) - groups i n which t h e excess of negative charge on t h e E04 u n i t s is a t p e n s a t e d by t h e

0

~ a + ions, t h e above-mentioned BF04 groups are w r i t t e n a s ( m 4 )

-

Our t e n t a t i v e conclusion is t h a t t h e 1035 peak is due t o ( B P O ~ ) - groups.

I V

- CONCLUSIONS

In Na20-A1 0 -B 0 -P 0 glasses, both aluminium and boron ions have two types of _{2 3 2 3 2 5} coordination, t h e former has 4 and 6 while t h e l a t t e r has 3 and 4. Viith t h e increase i n t h e r a t i o of B20/A1203, aluminium and boron ions change from 4 i n t o 6 and from 3 i n t o 4 respectively. I t means t h a t when B + ~ and ~ 1 ' ~ ions e x i s t simul-

+

taneously i n phosphate glasses, 3 ions form E04 t e t r a h e d r a p r i o r t o ~ 1 ' ~ ions. I n ,

g l a s s e s containing higher B203, S- of B + ~ ions e x i s t i n t h e f o m of borate gmups with non-bridging oxygens.

/ 1 / J i n Yifen, Jiang Dehua, Chen Xiangsheng and Huang Xihuai, Acta Optical S i n i c a 4 (1984) 842.

-

/ 2 /

9

.

C.

60604~2,

Oniiiuka u Cnek@xckonuSI

13

(1982) 492.

/3/ W. Bues and H. W. Gehreke, Z. Anorg. Allg. Chemie 288 (1956) 291. /4/ T. J. Hanwick and P. 0. Hoffman, J. Chem. Phys.

19

(1951) 708.

/ 5 / N. I w w t o , Y. Tsunawaki, T. H a t t o r i and A. Mitsuishi, Phys. Chern. Glasses 19 (1978) 141.

-

/6/ Huang Pengnian, J i n Yifen and b a n g Xihuai, Acta Physica S i n i c a

3

(1984) 523. / 7 / W. Konijnendijk, P h i l i p s Research Reports Supp. Xo.1 (1975) 30.