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CORROSION BEHAVIOR OF AMORPHOUS IRON-BASE ALLOYS
M. Naka, K. Hashimoto, Koji Asami, T. Masumoto
To cite this version:
M. Naka, K. Hashimoto, Koji Asami, T. Masumoto. CORROSION BEHAVIOR OF AMOR- PHOUS IRON-BASE ALLOYS. Journal de Physique Colloques, 1980, 41 (C8), pp.C8-862-C8-866.
�10.1051/jphyscol:19808213�. �jpa-00220319�
JOURNAL D E PHYSIQUE Colloque C8, suppldment au n08, Tome 4 1 , aoGt 1980, pageC8-862
CORROSION BEHAVIOR OF AMORPHOUS IRON-BASE ALLOYS
M. Naka, K. Hashimoto, K. Asami and T. Masumoto
The Research I n s i t u t e for Iron, SteeZ and Other MetaZs, Tohoku University, 980 Sendai, Japan.
I. I n t r o d u c t i o n . . - R m o r p h o u s F e b a s e a l l o y s
p r o d u c e d b y r a p i d q u e n c h i n g f r o m t h e l i q u i d 0.1 N ySq
s t a t e p o s s e s s e x t r e m e l y h i g h c o r r o s i o n r e - E E s i s t a n c e when c e r t a i n a m o u n t s of c h r o m i u m
a r e a d d e d ( 1 - 3 ) . M e t a l l o i d e l e m e n t s r e - q u i r e d t o o b t a i n a m o r p h o u s s t r u c t u r e m a r k - e d l y a f f e c t t h e c o r r o s i o n r e s i s t a n c e o f t h e
a l l o y s . F u r t h e r t h e c h e m i c a l l y h o m o g e n e o u s 30 40
Alloying Content at%
n a t u r e o f a m o r p h o u s a l l o y s p r o v i d e s t h e
F i g . 1. C o r r o s i o n r a t e s o f a m o r p h o u s Fe- f o r m a t i o n o f a n u n i f o r m p a s s i v e f i l m . T h i s xp+13p-7C a l l o y s i n 0 . 1 ~ H SO where M is
t h e e l e m e n t s o f t h e f i r s t 3 o n a 9 p e r i o d . n a t u r e i m p a r t s t h e h i g h c o r r o s i o n r e s i s t -
a n c e o f t h e a l l o y s t
T h e p u r p o s e o f t h e p r e s e n t work i s t o i n - v e s t i g a t e t h e e f f e c t o f a d d i t i v e m e t a l l i c e l e m e n t s o n c o r r o s i o n p r o p e r t i e s o f a m o r - p h o u s Fe-P-C a l l o y s , a n d t h e e f f e c t o f c r y s t a l l i z a t i o n o n t h e c o r r o s i o n b e h a v i o r o f a m o r p h o u s Fe-1 CCr-13P-7C a n d Fe-36Ni- 1 4 C r - 1 2 P - 6 0 a l l o y s .
2. E x p e r i m e n t a l . - T h e m e l t s p i n n i n g m e t h o d h a s b e e n a p p l i e d t o t h e p r e p a r a t i o n o f a- m o r p h o u s a l l o y s w i t h a b o u t 2 mm i n w i d t h a n d 2 0 prn i n t h i c k n e s s , w h e r e M i s t r a n s i - t i o n e l e m e n t s b e l o n i n ~ t o t h e f i r s t , s e c o n d a n d t h i r d l o n g p e r i o d s i n t h e p e r i o d i c t a b l e . T h e n u m b e r a t t a c h e d t o r e s p e c t i v e e l e m e n t s d e n o t e s t h e n o m i n a l c o n t e n t i n a t o m i c p e r c e n t . C o r r o s i o n t e s t s a n d e l e c t r o c h e m i c a l m e a s u r e m e n t s w e r e c a r r i e d o u t i n 0.1N H2S04 a n d IN HC1, w h i c h a r e o p e n t o a i r . A c o r r o s i o n r a t e was e s t i m a t - e d f r o m t h e w e i g h t l o s s a f t e r i m m e r s i o n
plwi cmtent at%
F i g . 2. C o r r o s i o n r a t e s o f a m o r p h o u s Fe- xM-13P-7C a l l o y s i n 0.1N H SO w h e r e M i s t h e e l e m e n t s o f t h e s e c o n d 2 a n a ' t h i r d
p e r i o d s .
i n t h e s o l u t i o n s a t 3 0 3 K I P o l a r i z a t i o n c u r v e s w e r e m e a s u r e d b y p o t e n t i o d y n a m i c m e t h o d w i t h a p o t e n t i a l s w e e p r a t e o f 2 . 3 7 ~ 1 o - ~ v S - I a t r o o m t e m p e r a t u r e . T h e a n n e a l e d s p e c i m e n s w e r e p o l i s h e d w i t h e m e r y p a p e r d i p p e d i n c y c r o h e x a n e p r i o r t o p o l a r - i z a t i o n m e a s u r e m e n t . T h e q u a n t i t a t i v e a n a l y s i s o f c o m p o s i t i o n s o f s u r f a c e f i l m a n d u n d e r l y i n g m a t r i x w a s p e r f o r m e d b y t h e X-ray p h o t o - e l e c t r o n s p e c t r o s c o p y m e t h o d r e p o r t e d b y s o m e o f t h e p r e s e n t a u t h o r s ( 4 ) .
Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19808213
I n t e g r a t e d i n t e n s i t i e s o f p h o t o - e l e c t r o n s w e r e o b t a i n e d f o r F e 2 p , V
3 / 2 2P 3 / 2 ' z r 3 d 3 / z , s / z , Nb 3d3/2, 5 / 2 P d 3 d 3 / 2 , 5 / ~ 9
P t s p e c t r a .
4f 5 / 2 , 7 / 2
3. R e s u l t s a n d D i s c u s s i o n . - F i g s . 1 a n d 2 s h o w t h e c o r r o s i o n r a t e s o f a m o r p h o u s Fe- xM-13P-7C a l l o y s i n 0.1N H2S04 a s a f u n c - t i o n o f t h e c o n t e n t o f a l l o y i n g e l e m e n t M.
T h e a d d i t i o n of c e r t a i n a m o u n t s o f Cr o r N O
i s e f f e c t i v e . T i , Zr o r CU a d d e d b y small a m o u n t s e f f e c t i v e l y i n c r e a s e s t h e c o r r o s i o n r e s i s t a n c e . T h e a d d i t i o n o f e l e m e n t s l e s s n o b l e t h a n F e d e c r e a s e s t h e c o r r o s i o n r a t e o f a l l o y i n t h e o r d e r o f V , C r a n d T i i n t h e f i r s t l o n g p e r i o d a n d i n t h e o r d e r o f Nb, No a n d Z r i n t h e s e c o n d l o n g p e r i o d . T h e a d d i t i o n o f W i s a l s o e f f e c t i v e i n d e c r e a s i n g t h e c o r r o s i o n r a t e .
On t h e o t h e r h a n d , t h e a d d i t i o n o f e l e - m e n t s n o b l e r t h a n i r o n t e n d s t o d e c r e a s e t h e c o r r o s i o n r a t e o f t h e a l l o y i n t h e o r d e r o f Rh, Ru a n d P d i n t h e s e c o n d l o n g p e r i o d . T h e a d d i t i o n o f P t a l s o i n c r e a s e s t h e c o r r o s i o n r e s i s t a n c e .
F i g s . 3 a n d 4 s h o w a n o d i c p o l a r i z a t i o n c u r v e s o f a m o r p h o u s Fe-xM-13P-7C a l l o y s . T h e a m o r p h o u s Fe-13P-7C a l l o y p o s s e s s h i g h c h e m i c a l r e a c t i v i t y a n d d o e s n o t p a s s i v a t e a n o d i c a l l y i n v a r i o u s s o l u t i o n s . N e v e r - t h e l e s s , a l l t h e Fe-N-13P-7C a l l o y s t e n d t o p a s s i u a t e a n o d i c a l l y i n 0.1N H2S04.
T h e a d d i t i o n o f C r t o Fe-13P-7C a l l o y r e - d u c e s t h e a n o d i c c u r r e n t d e n s i t y m o s t e f - f e c t i v e l y a n d l e a d s t o s p o n t a n e o u s p a s s i v a - t i o n w i t h a n i n c r e a s e i n c h r o m i u m c o n t e n t . T h e a d d i t i o n o f No o r W i s a l s o e f f e c t i v e f o r a n o d i c p a s s i v a t i o n i n 0.1N H2sO4 .
F i g . 5 i l l u s t r a t e s t h e f r a c t i o n o f c a t i -
Potential V(SCE)
F i g , 3 . A n o d i c p o l a r i z a t i o n c u r v e s o f amor- p h o u s Fe-xM-13P-7C a l l o y s i n 0.1N H2S04, w h e r e M i s T i , V , C r , Zr, W o r No.
F i g . 4. A n o d i c p o l a r i z a t i o n c u r v e s o f a m o r - p h o u s Fe-xN-13P-7C a l l o y s i n O.1N H2S04, w h e r e N i s Nn, Co, N i , Cu, P d o r P t . o n s i n t h e s u r f a c e f i l m s f o r m e d o n Fe-WLN a l l o y s c o n t a i n i n g t h e m e t a l l i c e l e m e n s M L N 4
l e s s n o b l e t h a n i r o n . T h e p a s s i v e f i l m f o r m e d o n Fe-1OV d o e s n o t c o n t a i n V i ' o n a n d c o n s i s t s e x c l u s i v e l y o f f e r r o u s a n d f e r r i c i o n s a s c a t i o n s . . F u r t h e r , a r e m a r k a b l e e n r i c h m e n t o f c a t i o n s o f a l l o y i n g e l e m e n t s t a k e s p l a c e i n t h e s u r - f a c e f o r m e d o n Fe-IOU, Fe-5V, Fe-2Nb a n d F e - 1 Z r a l l o y s i n t h e a c t i v e r e g i o n i n c l u d - i n g t h e o p e n c i r c u i t p o t e n t i a l . On t h e o t h e r h a n d , a m o r p h o u s Fe-NN a l l o y s c o n t a i n - i n g m e t a l l i c e l e m e n t s N N n o b l e r t h a n F e s u c h a s N i , P d a n d P t d o n o t s h o w a n en- r i c h m e n t o f t h e a l l o y i n g e l e m e n t s i n t h e s u r f a c e f i l m f o r m e d i n t h e a c t i v e r e g i o n s a s c a n b e s e e n i n F i g . 5.
JOURNAL DE PHYSIQUE
0 mm Fe-2w3pn Zrm R-lZr.13PX H on FcDN.13P X
. WmFrS3W13PX A Fl m W5R-UPX , , , ,
7 - f .
B U L K P ( E W - ( I ~ 42 o o u a6 a8 10 12 1 4 16
ALLOY RXIWED Potential V(%)
F i g . 5. C a t i o n s f r a c t i o n s i n s u r f a c e f i l m s o n a m o r p h o u s Fe-13P-7C a l l o y s c o n t a i n i n g V, Nb, Z r , N i , Pd o r P t i n 0.1N H2S04.
F i g . 6. ~ t o m i c r a t i o s o f n o b l e m e t a l s t o t h e sum o f i r o n a n d n o b l e m e t a l s i n a l l o y i m m e d i a t e l y u n d e r t h e s u r f a c e f i l m .
The c o n c e n t r a t i o n o f N i i o n i n t h e s u r f a c e f i l m f o r m e d on t h e Fe-1ONi a l l o y i n t h e a c t i v e r e g i o n i s n e a r l y t h e same a s t h e a t o m i c r a t i o o f N i t o t h e sum o f ~i a n d F e i n t h e b u l k a l l o y . The N i i o n i s n o t f o u n d i n t h e p a s s i v e f i l m . The s u r f a c e f i l m f o r m e d o n t h e Fe-NN-13P-7C a l l o y s i n b o t h a c t i v e a n d p a s s i v e r e g i o n s c o n s i s t s e x c l u - s i v e l y o f f e r r o u s a n d f e r r i c i o n s a s c a t i - on, The p a s s i v a t i o n o f amorphous ~ e - X N - 1 3 ~ - 7C a l l o y s t o o k p l a c e b y t h e f o r m a t i o n o f h y - d r a t e d i r o n o x y - h y d r o x i a e f i l m .
V e l e m e n t was d e f i c i e n t o n t h e s u r f a c e of Fe-IOV a l l o y i m m e d i a t e l y u n d e r s u r f a c e f i l m . The a l l o y i n g e l e m e n t s i n a n d e r l y i n g a l l o y w e r e n o t f o u n d f o r o t h e r Fe-NLN a l l o y s s u c h
asFe-Nb a n d Fe-Zr. I n c o n t r a s t t o t h i s . f a c t s , a l l o y i n g e l e m e n t s N,,, n o b l e r t h a n
F e a r e c o n c e n t r a t e d i n t h e a l l o y s u r f a c e
F i g . 7. DTA c u r v e s o f amorphous Fe-1OCr- 13P-7C a n d Fe-36Ni-14Cr-12P-6B a l l o y s .
on Fe-NLN-1 3P-7C a l l o y s a s c a n b e s e e n i n F i g . 6.
The a d d i t i o n o f a l l o y i n g e l e m e n t s s u c h a s C r a n d T i l e s s n o b l e t h a n F e i n c r e a s e s t h e c o r r o s i o n r e s i s t a n c e i n t h e a c t i v e r e g i o n b y i m p r o v i n g t h e p r o t e c t i v e q u a l i t y o f c o r - r o s i o n p r o d u c t f i l m i n w h i c h t h e c a t i o n s o f a l l o y i n g e l e m e n t s a r e s i g n i f i c a n t l y e n r i c h - ed.
Even i f t h e p a s s i v i t y o f a l l o y i n g e l e - m e n t s s u c h a s V , Nb a n d Mo i s n o t s t a b l e i n t h e p a s s i v e r e g i o n , t h e a l l o y i n g a s s i s t s t h e f o r m a t i o n o f p a s s i v e h y d r a t e d i r o n o x y - h y d r o x i d e f i l m b y d e c r e a s i n g t h e d i s s o l u - t i o n r a t e o f a l l o y p r i o r t o p a s s i v e f i l m f o r m a t i o n . The i m p r o v e m e n t o f c o r r o s i o n r e s i s t a n c e b y a l l o y i n g w i t h e l e m e n t s s u c h a s N i , Pd a n d P t n o b l e r t h a n F e i s i n t e r - p r e t e d i n t e r m s of t h e d e c r e a s e i n t h e a n o d i c a c t i v i t y o f a l l o y s .
The e f f e c t o f c r y s t a l l i z a t i o n o n c o r r o - s i o n b e h a v i o r o f Fe-1OCr-13P-7C a n d Fe- 36Ni-14Cr-12P-6B a l l o y s h a s b e e n examined.
F i g . 7 shows t h e DTA c u r v e s o f t w o a l l o y s . B o t h a l l o y s p o s s e s s t w o m a i n p e a k s a n d one
s m a l l a n d b r o a d peak. By X-ray d i f f r a c -
ar Time min
F i g . 8. C h a n g e s i n t h e c o r r o s i o n p o t e n t i a l s ( ~ n IN H C ~ ) o f F e - 1 0 C ~ 1 3 P - 7 C a l l o y s
a n n e a l e d a t 7 0 3 a n d 7 2 3 K a n d Fe-36Ni-14Cr- 1 2 P - 6 0 a l l o y s a n n e a l e d a t 6 3 5 a n d 7 0 3 K.
t i o n a n a l y s i s t h e f i r s t p h a s e ( t e r m e d MSI) was p r o v i d e d t o b e b c c f o r Fe-1OCr a l l o y a n d f c c f o r F e - 3 6 N i - 1 4 C r a l l o y . T h e s e c o n d p h a s e ( t e r m e d t C s I 1 ) o c c u r s a t t h e s e c o n d p e a k . C h a n g e t a 1 . ( 5 ) h a v e r e p o r t e d t h a t t h e R S I l f o r F e - 3 6 N i - 1 4 C r a l l o y i s t e t r a g - o n a l - b o d y c e n t e r e d Ni3P t y p p h a s e . F i g . 8 d e m o n s t r a t e s t h e c h a n g e i n c o r r o s i o n p o t e n - t i a l o f t h e a n n e a l e d a l l o y i n IN HC1.
T h e E c o r r . o f ' Fe-1 O C r a l l o y d e c r e a s e s m a r k e d l y f r o m +0.6 t o -0.4 V b y t h e p r e - c i p i t a t i o n o f MSII. On t h e o t h e r h a n d , t h e E c o r r . o f F e - 3 6 N i - 1 4 C r a l l o y d e c r e a s e s s l i g h t l y b y t h e p r e c i p i t a i o n o f MSII.
P o t e n t i o d y n a r n i c p o l a r i z a t i o n c u r v e s o f t h e a l l o y s a r e s h o w n i n F i g . 9 a n d 1 0 . T h e p r e c i p i t a i o n o f NSI i n F e - C r a n d Fe-36Ni- 1 4 C r i n c r e a s e s t h e a n o d i c c u r r e n t d e n s i t y b y t w o o r t h r e e o r d e r s o f m a g n i t u d e c o m p a r - e d w i t h t h a t o f a m o r p h o u s a l l o y s , a n d f u r - t h e r t h e p r e c i p i t a t i o n o f M S I I i n c r e a s e s t h e a n o d i c c u r r e n t d e n s i t y b y t w o o r d e r o f m a g n i t u d e , c o m p a r e d w i t h t h a t o f a l l o y s c o n t a i n i n g MSI.
T h e h i g h r e a c t i v i t y o f t h e c r y s t a l l i z e d a l l o y s a r i s e s f r o m c r y s t a l d e f e c t s s u c h a s
g r a i n b o u n d a r i e s a n d d i s l o c a t i o n s .
F i g . 9. C h a n g e s i n t h e a n o d i c c u r r e n t d e n - s i t i e s o f Fe-1OCr-13P-7C a l l o y a n n e a l e d a t 7 0 3 K , i n I N HC1.
Potential V(SCE)
F i g . 1 0 . C h a n g e s i n t h e a n o d i c c u r r e n t d e n s i t i e s o f Fe-36Ni-14Cr-12P-60 a n n e a l e d a t 7 0 3 K , i n IN HC1.
4. Conclusion.- All alloying elements M except manganese more or less increase the corrosion resis- tance of amorphous Fe-M-13P-7C alloys in various acidic solutions. The effectiveness of the addition of elements more active than iron in increasing the corrosion resistance of the amorphous alloys is de- pendent upon the passivation capability of alloying element itself. The addition of alloying elements more active than iron increases the corrosion resis- tance in the active region by improving the protec- tive quality of corrosion product film in which the cations of alloying elements are significantly con- centrated. Even if the passivity of alloying ele- ments is not stable in the passive region of alloys,
C8-866 JOURNAL DE PHYSIQUE
the alloying assists the formation of passive
hydrated iron oxy-hydroxide film by decreasing the R e f e r e n c e s
dissolution rate prion to the passive film formation. ( 1 ) N a K a r e , ~ ~ ~K. a n d masurnoto h i ~ ~T., t ~
On the other hand, the improvement of corrosion J , J a p a n I n s t . M e t a l s 3 8 ( 1 9 7 4 ) 8 3 5 .
resistance by a1 loying with elements nobler than ( 2 ) Kasurnoto T. a n d H a s h i r n o t o K., Ann. R e v .
iron has been interpreted in terms of the increase M a t e r . S c i . , 8 ( 1 9 7 8 ) 2 1 5 .
in the anodic activity of alloys. ( 3 ) Naka PI., H a s h i r n o t o K. a n d Nasurnoto T., J. N o n - c r y s t . S o l i d s 2 8 ( 1 9 7 8 ) 4 0 3 . ( 4 ) Asarni K., H a s h i r n o t o K. a n d s h i r n o d a i r a
S., C o r r o s . S c i . , 1 8 ( 1 9 7 8 ) 1 5 1 . ( 5 ) Chang H. a n d S a s t r i S., rCet. T r a n s . ,
8 ~ ( 1 9 7 7 ) 1 0 6 3 .
