EFFECT OF COMPOSITION IN (Fe,Ni,Cr) (P,B) AND (Fe,Ni,Mo)B METALLIC GLASSES

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EFFECT OF COMPOSITION IN (Fe,Ni,Cr) (P,B) AND (Fe,Ni,Mo)B METALLIC GLASSES

C. Antonione, L. Battezzati, A. Lucci, G. Riontino, M. Tabasso, G. Venturello

To cite this version:

C. Antonione, L. Battezzati, A. Lucci, G. Riontino, M. Tabasso, et al.. EFFECT OF COMPOSITION

IN (Fe,Ni,Cr) (P,B) AND (Fe,Ni,Mo)B METALLIC GLASSES. Journal de Physique Colloques, 1980,

41 (C8), pp.C8-131-C8-134. �10.1051/jphyscol:1980834�. �jpa-00220340�

JOURNAL DE PHYSIQUE CoZZoque C 8 , suppZdment au n08, Tome 41, aoQt 198-0, page (28-131

EFFECT OF COMPOSITION IN ( F ~ ~ N ~ ~ c ~ ) ( P I B ) AND ( ~ e r ~ i r ~ o ) ~ METALLIC GLASSES

C. Antonione, L. Battezzati, A. Lucci, G. Riontino, M.C. Tabasso and G. Venture110

I s t i t u t o d i chimica Generale ed Inorganica, FacoZtd d i Farmacia, Universitd d i Torino, I t a Z i e

The e f f e c t o f chemical composition on the thermal s t a b i l i t y o f t h e amorphous s t a t e was s t u - d i e d on two s e r i e s o f Fe-Ni-based a l l o y s . A f i r s t s e r i e s i n c l u d e s No as t h i r d m e t a l l i c element, and B as m e t a l l o i d atom, a second one c o n t a i n s Cr as t h i r d metal component and B and P as m e t a l l o i d e l g ments.

Preparation and experimental methods

The amorphous a l l o y s were prepared by m e l t s p i n n i n g as -2 mm-wide and 0.02 mm-thick ribbons.

The Mo-containing s e r i e s i s c o n s t i t u t e d by (Fe,Mi ,Mo)B a l l o y s , w i t h FetNi content roughly constant (Fe ranging w i t h i n 84 and 43, and Ni w i t h i n 0 and 41 a t . % ). I n t h i s s e r i e s t h e concen- t r a t i o n o f Mo v a r i e s from 2 t o 8.5, and t h a t o f 6 from 10 t o 15 a t .

%.

The C r - c o n t a i n i n g s e r i e s can be described by t h e formula Fe44-xNi37CrxP15B4, x ranging from 0 t o 10.

The composition o f t h e amorphous a l l o y s was s y s t e m a t i c a l l y c o n t r o l l e d by chemical a n a l y s i s (atomic absorption, s p e c t r o g r a p h i t a l and spectro- photometric methods).

Specimens o f t h e d i f f e r e n t a l l o y s were exami ned by d i f f e r e n t i a l c a l o r i m e t r y (DSC). Two DSC c e l l s .(Du Pont and Rigaku-Denki) were used i n d i f - f e r e n t temperature ranges. Glass t r a n s i t i o n (T )

9 and c r y s t a l l i z a t i o n (Tx) temperatures Here d e t e r m i ned, as w e l l as the corresponding c r y s t a l l i z a t i o n

e n t h a l p i e s (aHx), a t t h e h e a t i n g r a t e o f 20 K/min.

For some a l l o y s , d i f f e r e n t i a l thermal a n a l y s i s (DTA) was c a r r i e d o u t up t o completion o f m e l t i n g . A c t i v a t i o n energies f o r c r y s t a l 1 i z a t i o n were eva- l u a t e d according t o Ozawa method ( 1 ) ( 2 ) .

C h a r a c t e r i z a t i o n o f t h e amorphous s t a t e and o f t h e c r y s t a l l i n e phases forming d u r i n g and a f - t e r c r y s t a l l i z a t i o n was made by X-ray d i f f r a c t i o n . Results and d i s c u s s i o n

Since t h e c o n c e n t r a t i o n o f t h e d i f f e r e n t e l e - ments i n the a1 l o y s covers a r e l a t i v e l y l a r g e ran- ge, t h e data a r e grouped i n such a way t o p o i n t o u t t h e e f f e c t o f t h e s i n g l e elements.

Mo-containing a l l o y s . (Fe,Ni,Mo)B a l l o y s e x h i b i t a two stage exothermic c r y s t a l l i z a t i o n process. The glass t r a n s i t i o n temperature wds de- t e c t e d o n l y i n a few cases and preceded t h e onset of t h e f i r s t c r y s t a l l i z a t i o n peak by about 25-30 K.

The effec.t o f Ni can be evidenced i n a group o f

Fig. 1

-

Feg4.5-xNixM~3.5Bi2 alloys.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1980834

JOURNAL DE PHYSfQUE

a l l o y s w i t h composition about Fe84.5-xNixHo3.5B12, where Po content i s i n f a c t 3.550.5 and B content i s 12.+1., w i t h t h e o n l y exception o f a l l o y s w i t h x =O (where B i s 13.5) and x = 32.5 (where B i s 10.).The

B: 13 a t . % ) .

S i m i l a r trends have been observed i n Fe-Ni-B a l l o y s i n the 20t40 a t . % P i and 1 5 ~ 1 8 a t . % B com- p o s i t i o n ranges (3, 4, 5) w h i l e a minimum i n t h e T curve has been observed i n correspondence o f the

g

Fe73Ni10B17 ( 4 ) and Fe70Ni10B20 ( 6 ) a l l o y s : i n t h e present work a Fe79NigMo2B10 a l l o y , which cannot be i n t r o d u c e d i n F i g . 1 due t o i t s low B and F?o con t e n t , shows, however, a low Tx temperature, 625 K.

F i g . 2 summarizes t h e e f f e c t o f Mo c o n t e n t on Tx o f the amorphous a l l o y s ; Fig. 2a r e f e r s t o a l - l o y s w i t h constant Ni (23 a t . % ) and B (13 a t . % ) concentration,Fig. 2b t o a l l o y s w i t h 20% Ni and 11.5% B, and F i g . 2c t o a l l o y s w i t h constant 12% B and 16-24% Ni c o n c e n t r a t i o n range. Mo i s shown t o increase Tx i n every group o f a l l o y s and i t seems t o be more e f f e c t i v e up t o a 5% content; a f u r t h e r increase o f s t a b i l i t y i s observed a t h i g h e r concen- t r a t i o n b u t a t r e n d towards s a t u r a t i o n o f t h e e f - f e c t seems probable. This appears t o be a q u i t e general behaviour: i n f a c t some systems, such as Fe78-xH0xSi OBI 2 3 Fe83,xM0xB1 7 ( 7, and Feg0-xM0xB20

f i r s t c r y s t a l l i z a t i o n onset temperature i s s l i g h t l y

decreased by i n c r e s i n g Ni c o n c e n t r a t i o n ( F i g . 1 ) , 725

though t h i s e f f e c t i s probably stressed i n t h e d i g

Mo,at0l0

Fig. 2

-

a) alloys with 2321 at.% Ni, 13 at.% B;

b) alloys with 2021 at.% Ni, 11.53.5 at.%

B; c) alloys with 203at.% Ni, 1221 at.% B.

(8), show an analogous tendency and even a maximum a t 10 a t . % Mo was found i n t h e Tx-at.% No curve r e - f e r r i n g t o Ni78-xMoxSi10B12 a l l o y s ( 7 ) . From c u r - ves i n F i g . 2 an i n i t i a l slope o f about 11 K/at.%

Mo can be estimated, which i s i n good agreement w i t h the f i g u r e s t h a t can be d e r i v e d from r e f e r e n - ces (7,8) and w i t h those found by Inoue e t a l . on Fe-, N i - and Co- based amorphous a l l o y s c o n t a i n i n g C i n s t e a d of B (9, 10).

Amorphous a1 l o y s w i t h B concentrations ranging f r o m 10 t o 15 at.% were s t u d i e d i n t h e present work t o evidence t h e effect of B. As shown i n F i g . 3, t h e increase of c o n c e n t r a t i o n o f B seems t o produ- ce a t f i r s t a s t a b i l i z a t i o n o f t h e amorphous a l l o y s f o l l o w e d by a decrease i n Tx. A l l o y s w i t h 13.5%

a n d l O % B h a v e a g r e a t d i f f e r e n c e i n Ni concentration, as a l r e a d y noticed, (0% and 3 2 . 9 r e s p e c t i v e l y ) and an o v e r l a p p i n g of t h e concurrent e f f e c t o f both

700 gram by t h e concurrent e f f e c t o f B, due t o i t s ab-

normal c o n c e n t r a t i o n f o r t h e two a l l o y s w i t h x = 0 750

and x = 32.5 as mentioned above. I t i s t o be noted

7 2 5 t h a t a l s o the a l l o y w i t h x = 23 has a r e l a t i v e l y

h i g h e r Tx value, b o t h B and Mo having t h e h i g h e s t 733.

contents allowed i n t h e s e l e c t e d band (Mo: 4 at.%;

@

~7

0

1 3 5 7 9

-

B

,at

Fig. 3

-

B (Ni: 0 at.%).

elements i s t o be considered. The o t h e r a l l o y s o f t h i s group have Ni contents ranging from 15 t o 23 at.%; Mo c o n c e n t r a t i o n i s n e a r l y constant a t 4 a t % These r e s u l t s cover a c o n c e n t r a t i o n range t h a t does n o t p e r m i t a s i g n i f i c a n t comparison w i t h l i t 2 r a t u r e data, where i t should be noted t h a t d i s c o r - dant data are,however,present f o r t h e (Fe,Ni)lOO-x Bx systems; some authors found a s t a b i l i z a t i o n of a l l o y s w i t h i n c r e a s i n g B content (5), w h i l e ano- t h e r one r e p o r t s an o p p o s i t e e f f e c t (3); on t h e o t h e r hand, t h e r e i s agreement on t h e s t a b i l i z i n g e f f e c t o f B i n the FelOO-xBx system (3,5,11,12).

X r a y a n a l y s i s was performed on specimens quenched i n t h e DSC c e l l w i t h l i q u i d N2 a t a r a t e o f about 150 K/min a f t e r completion o f the f i r s t c r y s t a l l i z a t i o n peak. It showed t h e presence o f a bcc s o l i d s o l u t i o n a t 0-15% Ni and of a f c c , s o l i d s o l u t i o n a t h i g h e r Ni concentration. Between 15 and 20%.Ni t h e bcc s o l i d s o l u t i o n f i r s t l y formed transforms d u r i n g t h e second peak t o a fcc phase.

A t the same time, t h e remaining B - r i c h amorphous phase transforms t o a t e t r a g o n a l Fe3B type phase, i n the low Ni content a l l o y s , and t o a cubic Fep3 B6 t y p e phase, i n t h e o t h e r cases.

The e f f e c t o f c o n c e n t r a t i o n on t h e onset tem- p e r a t u r e o f t h e second c r y s t a l l i z a t i o n peak i s n o t

as c l e a r as f o r t h e f i r s t one; Ni c o n t e n t seems n o t t o i n f l u e n c e i t appreciably, w h i l e h i g h B and Yo c o n c e n t r a t i o n s appear t o s t a b i l i z e t h e amorphous phase. The onset temperature range f o r t h e second c r y s t a l l i z a t i o n peak extends from about 800 t o 871

-

Fe56Ni22.5M08.5B13'

C r - c o n t a i n i n g a l l o y s . Amorphous a l l o y s Fe44-xNi37CrxP15B4 were s t u d i e d t o p o i n t o u t t h e e f f e c t o f C r . P and B concentrations are f i x e d -

w i t h i n -

+

_+

Fig. 4

-

44-x 37 x 15 4

Both T and Tx a r e increased by i n c r e a s i n g C r 9

c o n c e n t r a t i o n (Fig. 4). Slopes o f about 5 and, res- p e c t i v e l y , 4 K/at.% Cr can be evaluated - f o r t h e fwo curves. The e f f e c t i v e n e s s o f C r i n i n c r e a s i n g thermal s t a b i l i t y o f t h e amorphous s t a t e i s there- f o r e lower w i t h r e s p e c t t o t h a t found i n t h e present work f o r 110; t h i s agrees w i t h t h e r e s u l t s obtained f o r C-based amorphous a l l o y s by Inoue e t a l . ( 9 ) (10).

JOURNAL DE PHYSIQUE

w

Fig. 5

-

Fig. 5 shows a decrease of c r y s t a l l i z a t i o n enthalpy versus i n c r e a s i n g C r content. U n c e r t a i n t y beincj evaluated a t about

+

For t h i s group of a l l o y s , non-isothermal k i n e t i c s o f c r y s t a l l i z a t i o n has been studied; con- s t a n t h e a t i n g r a t e s ranging from 2.5 t o 80 K/min were used, and, f o l l o w i n g t h e method proposed by Ozawa ( 1 ) ( 2 ) , a c t i v a t i o n energy f o r c r y s t a l l i z a t i o n was determined. The values obtained range w i t h i n about 390 and 410 KJ/mol f o r t h e a l l o y s w i t h d i f - f e r e n t C r concentration, w i t h an u n c e r t a i n t y evaluable a t about

+

X-ray d i f f r a c t i o n r e s u l t s show t h e forma- t i o n o f two phases d u r i n g t h e c r y s t a l l i z a t i o n p r o - cess: a m e t a l l i c f c c s o l i d s o l u t i o n and a mixed boride-phosphide phase. For t h e f i r s t one, a value o f 0.357 t o 0.359 nm i s obtained f o r t h e c u b i c l a t t i c e parameter, according t o t h e d i f f e r e n t C r c o n c e n t r a t i o n i n t h e a l l o y . The s e m i m e t a l l i c phase i s c o n s t i t u t e d by a t e t r a g o n a l mixed boride-phosphi de o f t h e type Fe3P, w i t h parameters a. r a n g i n g from 0.903 t o 0.889 nm,and co, from 0.443 t o 0.438 nm.

REFERENCES

1. T. OZAWA: J. Therm. Anal.,

2,

2. C . ANTONIONE, L. BATTEZZATI, A. LUCCI, G. RION _- TINO, G. VENTURELLO: S c r i p t a !.let., 12, 1011 (1978).

-

3. J.L. WALTER: Mater.Sci

.

2,

4. B.G. LEWIS, H.A. DAVIES, K.D. WARD: Proc. 3 r d I n t . Conf. Rapidly Quenched Metals, Brighton, J u l y 1978; B. Cantor ed., The Metal Society, London

1,

(1978).

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Proc. Spring Review Course, York, A p r i l 1979, publ. by I n s t . o f M e t a l 1 u r g i s t s , London (1 979).

6. F.E. LUBORSKY, Mater. S c i . Eng.,

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8. H.J.V. NIELSEN: S o l i d S t a t e Comm. ,g,239 (1979).

9. A. INOUE, T. NAOHARA, T. MASUHOTO: Trans. JIM, 20, 329 (1 979).

-

10. A. INOUE, T. NAOHARA, T. MASUMOTO, K. KUMADA:

Trans. JIM,

0,

11. El. MATSUURA: S o l i d S t a t e Comm.,

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12. T. KEFENY, I. VINCZE, B. FOGARASSY, S. ARAJS:

see r e f . 4, p. 291.