MECHANICAL PROPERTIES OF (Fe, Co, Ni)-M-B
(M=Ti, Zr, Hf, V, Nb, Ta AND Mo) AMORPHOUS
ALLOYS WITH LOW BORON CONCENTRATION
A . Inoue, K. Kobayashi, M. Nose, T. Masumoto
To cite this version:
A . Inoue, K. Kobayashi, M. Nose, T. Masumoto. MECHANICAL PROPERTIES OF (Fe,
Co, Ni)-M-B (M=Ti, Zr, Hf, V, Nb, Ta AND Mo) AMORPHOUS ALLOYS WITH LOW
BORON CONCENTRATION. Journal de Physique Colloques, 1980, 41 (C8), pp.C8-831-C8834. <10.1051/jphyscol:19808204>. <jpa-00220309>
HAL Id: jpa-00220309
https://hal.archives-ouvertes.fr/jpa-00220309
Submitted on 1 Jan 1980
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CoZZoque C8, suppl6rnent au n08, Tome 41, aoct 1980, page C8-831
JOURNAL DE PHYSIQUE
MECHANICAL PROPERTIES OF ( ~ ,
e C o , ~ i ) - M -( M
G= T ~ ,Zr,
AMORPHOUS ALLOYS WITH LOW BORON CONCENTPATION
Inoue, K. ~ o b a ~ a s h i *M., Nose
A.
..,
*X
V, Nb,Ta AND
Hf,
MO)
and T. Masumoto
The research I n s k i t u t s for rron, S t e e l and Other Metals, Tohoku University, Sendai 980, Japan.
Japan Metals and Cherrticals Co. Ltd., Ohmama-cho 376-01, G u m , Japan.
Swnitomo Special Mztals Co. Ltd., Chsaka 564, Japan.
INTRODUCTION
I d e n t i f i c a t i o n of t h e as-quenched phases was made by
To d a t e a l a r g e number of amorphous a l l o y s have
c o n v e n t i o n a l X-ray d i f f r a c t i o n and t r a n s m i s s i o n e-
been produced by t h e m e l t quenching t e c h n i q u e .
l e c t r o n microscopy t e c h n i q u e s .
Broadly s p e a k i n g , t h e s e a l l o y s c a n be c l a s s i f i e d
ured by a V i c k e r s m i c r o h a r d n e s s t e s t e r w i t h a 100 g
i n t o two c a t e g o r i e s .
load.
One i s t h e m e t a l - m e t a l l o i d
t y p e c o n s i s t i n g of a t r a n s i t i o n m e t a l and a metall o i d element such a s P, S i , C o r B.
t h e e a r l y t r a n s i t i o n metal(e.g.,
The o t h e r is
T i , Zr e t c . ) a l l o y -
ed w i t h a l a t e t r a n s i t i o n m e t a l ( e . g . ,
etc.).
Co, N i , Cu
Most amorphous a l l o y s belong t o t h e former
Hardness was meas-
Each h a r d n e s s v a l u e was t h e a v e r a g e o f s e v e n
t o ten indentations.
C r y s t a l l i z a t i o n temperature
was examined by a d i f f e r e n t i a l thermal analyzer(DTA1
a t a h e a t i n g r a t e o f 8.33 x
K/s.
D u c t i l i t y was
e v a l u a t e d by measuring t h e r a d i u s of c u r v a t u r e a t
f r a c t u r e i n a s i m p l e bend t e s t / I / .
The deformed
t y p e and t h e y always c o n t a i n about 15-30 a t . % metal-
s t r u c t u r e and t h e f r a c t u r e s u r f a c e were observed by
l o i d elements.
a s c a n n i n g e l e c t r o n microscope.
On t h e o t h e r hand, t h e amorphous a l -
loys belonging t o t h e l a t t e r type usually contain
RESULTS
s o l u t e m e t a l s more t h a n a b o u t 30 a t . % a s e x e m p l i f i e d
f o r Cu-Ti,
Cu-Zr and Ni-Nb.
1.
Formation r a n g e of t h e amorphous phase
R e c e n t l y , we have found t h a t a n amorphous s i n -
The c o m p l e t e l y amorphous p h a s e i s o b t a i n e d i n
g l e phase i s formed i n a wide composition r a n g e of
wide c o m p o s i t i o n r a n g e s o f Co-Ti-B,
(Fe, Co, Hi)-IV o r V group t r a n s i t i o n metal-B
B, Ni-Zr-B,
r y a l l o y s containing l e s s than 10 at.%B.
terna-
Further,
t h e s e amorphous a l l o y s c o n t a i n l e s s t h a n a b o u t 20
Nb-B,
Fe-Hf-B,
Co-Ta-B,
Co-Hf-B,
Ni-Ta-B
Fe-Zr-B,
Ni-Hf-B,
and Co-Mo-B
Co-Zr-
Fe-Nb-B,
systems.
CO-
A s ex-
a t . % of t h e IV o r V group t r a n s i t i o n m e t a l s and t h u s
amples, F i g . 1 shows t h e f o r m a t i o n r a n g e s o f qhe
I
amorphous phase i n Fe-Nb-B, Co-Nb-B, Co-Ta-B and
a r e i n t e r e s t i n g m a t e r i a l s from i n d u s t r i a l p o i n t of
Ni-Ta-B
view because of h i g h c o n c e n t r a t i o n of f e r r o m a g n e t i c
t i a l f o r t h e f o r m a t i o n of amorphous phase.
e l e m e n t s s u c h a s Fe, Co and N i .
The aim of t h i s
systems i n which t h r e e e l e m e n t s a r e essenOn t h e
o t h e r hand, t h e f o r m a t i o n r a n g e s of t h e o t h e r amor-
paper i s t o p r e s e n t t h e composition r a n g e o f Fe, Co
phous a l l o y s a r e o m i t t e d because amorphous s i n g l e
o r Ni-IV o r V group t r a n s i t i o n metal-B
p h a s e h a s been formed i n Co-Ti / 2 / ,
t e r n a r y amor-
(Fe, Co, Ni)-Zr
phous p h a s e and t h e composition dependence of me-
/3,4/
c h a n i c a l p r o p e r t i e s of t h e s e amorphous a l l o y s .
t h e a d d i t i o n of B i s n o t always n e c e s s a r y f o r t h e
and (Fe, Co, Ni)-Hf
/5,6/
f o r m a t i o n of amorphous phase.
EXPERIMENTAL
o r V group t r a n s i t i o n metal-B
systems such a s (Fe, Co, Ni)-(Ti,
Mo)-B.
ternary
Z r , Hf, V. Nb, Ta,
M i x t u r e s of p u r e m e t a l s and boron were m e l t -
ed i n a r g o n atmosphere i n a n a r c - o r a n i n d u c t i o n
furnace.
As s e e n i n t h e f i g -
u r e , t h e s e amorphous a l l o y s a r e l i m i t e d t o t h e
A l l o y s used i n t h e p r e s e n t wprk q r e of , t h e Fe,
Co o r N i - I V
b i n a r y s y s t e m s and
Continuous r i b b o n specimens o f 1 mm w i d t h
r a n g e more t h a n a b o u t 2 at.%B and t h e a l l o y i n g
ele-
ments a r e l i m i t e d t o t h e r a n g e s of 10-14 at.%Nb f o r
Fe-Nb-B,
Co-Ta-B
7-22 at.%Nb f o r Co-Nb-B,
8-20 a t . % T a f o r
and 10-23 at.%Ta f o r Ni-Ta-B.
The forma-
t i o n r a n g e becomes narrower i n t h e o r d e r of t h e CoZr-B > Co-Hf-B
> Co-Ti-B
> Co-Nb-B
> Co-Ta-B
> Fe-
and 0.02 mm t h i c k n e s s were p r e p a r e d by m e l t s p i n -
Zr-B > Fe-Hf-B
> Ni-Zr-B
> Ni-Hf-B
> Ni-Ta-B
> Fe-
ning.
Nb-B systems and no amorphous p h a s e was found i n
T y p i c a l l y , t h e amount of a l l o y s melted i n
one r u n was a b o u t 2 g and t h e r o t a t i o n speed of t h e
t h e a l l o y systems o f (Fe, Ni)-Ti-B,
s t e e l r o l l e r ( 2 0 cm i n d i a m e t e r ) was a b o u t 6000 rpm.
B. Ni-Nb-B
and Fe-Ta-B.
Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19808204
(Fe, Co, Nil-V-
JOURNAL DE PHYSIQUE
Crystalline
C
Amorphous
6
0
2
4
6
8
10
Boron ( at0l0)
F i g . 1 Composition r a n g e s f o r t h e f o r m a t i o n of
amorphous s i n g l e phase i n t h e Fe-Nb-B, CoNb-B, Co-Ta-B and Ni-Ta-B systems.
Melt-quenched
e u t e c t i c (Fe, Co)-Nb and (Co, Ni)
-Ta b i n a r y a l l o y s show a c r y s t a l l i n e s t r u c t u r e witho u t any t r a c e of amorphous phase.
On t h e o t h e r
I
hand, t h e a l l o y s w i t h a s 1 o w ' a s . a b o u t 2 at.%B show
a n amorphous s t r u c t u r e .
4
io b i;
M
From t h e s e f a c t s , i t i s
1;
1;
io
i2
(at '10 )
concluded t h a t t h e s i m u l t a n e o u s d i s s o l u t i o n of Nb o r
Ta and B enhances t h e amorphous-forming tendency of
their alloys.
That i s , i t i s assumed t h a t t h e bond-
i n g f o r c e between m e t a l and m e t a l a s w e l l a s m e t a l
and m e t a l l o i d p l a y s a n i m p o r t a n t r o l e i n t h e format i o n o f a n amorphous phase i n t h e a l l o y s i n v e s t i g a t e d i n t h e p r e s e n t work.
T h i s assumption a l s o
r e c e i v e s s u p p o r t from t h e f a c t t h a t metal-metal
type
amorphous phase i s formed i n t h e b i n a r y a l l o y systems c o n s i s t i n g of Fe, Co o r N i and T i , Zr or'Hf
which a r e c o n s i d e r e d t o p o s s e s s s t r o n g e r bonding
f o r c e compared w i t h t h a t between Fe, Co o r N i and Nb
o r Ta.
2.
Fig. 2
Mechanical p r o p e r t i e s
The V i c k e r s h a r d n e s s values(Hv) of (Fe, Co, Ni)
94-xMxB6(M=Ti,
Zr, Hf, Nb and Ta) t e r n a r y amorphous
a l l o y s a r e p l o t t e d a s a f u n c t i o n o f t h e concentrat i o n of a l l o y i n g e l e m e n t s M i n F i g . 2 .
A s seen i n
Change i n V i c k e r s hardness(Hv) f o r Fe9,i-xMx
B6, C O ~ ~ - ~ M ,and
B ~ N~CJ~-~M,B~(M=T~,
Z r , Hf,
Nb and Ta) amorphous a l l o y s w i t h t h e amount
of a l l o y i n g elements M.
t h e a l l o y s c o n t a i n i n g Hf and d e c r e a s e s i n t h e o r d e r
of Zr > Ta > T i > Nb.
T h i s tendency i s t h e same i n
t h e t h r e e a l l o y systems o f Fe, Co and N i , i n d i c a t -
t h e f i g u r e ( a ) , ( b ) and ( c ) , t h e h a r d n e s s v a l u e s
i n g t h a t t h e bonding f o r c e between M and Fe, Co o r
i n c r e a s e s i g n i f i c a n t l y w i t h i n c r e a s i n g amount of
N i o r M and B d e c r e a s e s i n t h e o r d e r o f Hf > Zr >
a l l o y i n g e l e m e n t s , i n d i c a t i n g t h a t t h e bonding f o r c e
Ta > T i > Nb.
between a l l o y i n g element M and B i s much s t r o n g e r
i s a b o u t 1000 DPN f o r CogoHfl4B6 a l l o y .
t h a n t h a t between Fe, Co o r N i and B.
F u r t h e r , one
can n o t i c e t h a t t h e hardness value is highest f o r
The h i g h e s t h a r d n e s s v a l u e o b t a i n e d
F i g u r e 3 shows t h e change i n t h e V i c k e r s hardn e s s o f (Fe, Co, Ni)88-xM12Bx
amorphous a l l o y s w i t h
the B concentration.
amorphous a l l o y s was examined a s a f u n c t i o n of a g i n g
The h a r d n e s s v a l u e i n c r e a s e s
w i t h i n c r e a s i n g B c o n t e n t and t h e i n c r e a s i n g r a t e i s
t e m p e r a t u r e f o r 3600 s and t h e d a t a a r e shown i n
l a r g e s t f o r t h e Co-base a l l o y s .
T a b l e I t o g e t h e r w i t h t h e c r y s t a l l i z a t i o n tempera-
Further, similar t o
t h a t f o r (Fe, Co, Ni)g4-xMxB6 a l l o y s , t h e h a r d n e s s
t u r e ( T x ) , Tf/Tx and h a r d n e s s .
v a l u e d e c r e a s e s i n t h e o r d e r of Hf > Zr > Ta > Nb
determined a s b e i n g t h e b e g i n n i n g p o i n t of t h e f i r s t
exothermic peak on t h e DTA c u r v e s .
The h i g h e s t h a r d n e s s v a l u e i n t h e s e a l l o y
systems.
Tx i s t h e t e m p e r a t u r e
As summarized
b e n e a t h t h e t a b l e , Tf/Tx d e c r e a s e s i n t h e o r d e r of
systems i s a b o u t 1000 DPN f o r CogoHfl2Bg a l l o y s .
(Co, Ni)-(Nb,
Ta) > Ni-(Zr,
Fe-Nb > Fe-(Zr,
hardness.
H f ) > Co-(Ti,
Zr, H f ) ,
H f ) , i n c o n t r a s t t o t h e o r d e r of
That i s , t h e e m b r i t t l e m e n t tendency i n -
c r e a s e s w i t h i n c r e a s i n g bonding f o r c e among t h e cons t i t u e n t elements i n t h e a l l o y s .
DISCUSSION
'
The e f f e c t o f a l l o y a d d i t i o n on t h e Tx and H,
of amorphous a l l o y s h a s been examined by some invest i g a t o r s 17-11/
5
0
0
Fig. 3
~
2
L
Boron (at%)
6
B
0
2
L
Boron (at%)
6
B
0
2
L
6
8
period o r t h e V I group i n t h e periodic t a b l e .
Baon ( a t % )
Change i n V i c k e r s hardness(Hv) f o r Fegg-,
M12Bx,
and Ni88-xM12~x(M=Ti, Zr,
Hf, Nb and Ta) amorphous a l l o y s w i t h B content.
A l l t h e amorphous a l l o y s of t h e p r e s e n t s y s t e m s
p o s s e s s good bend d u c t i l i t y , a s i n t h e c a s e o f t y p i c a l metal-metalloid
Ductile-brittle
o r metal-metal amorphous a l l o y s .
How-
e v e r , t h e r e i s h a r d l y any s y s t e m a t i c i n f o r m a t i o n on
such a n e f f e c t f o r amorphous a l l o y s c o n t a i n i n g t h e
I V and V group m e t a l s ( T i , Z r , Hf, Nb, Ta) w i t h high
r e a c t i v i t y and h i g h m e l t i n g p o i n t .
The p r e s e n t i n -
v e s t i g a t i o n s p r o v i d e some i n s i g h t i n t o t h e r o l e of
t h e s e r e f r a c t o r y m e t a l s on t h e s t r e n g t h of amorphous
alloys.
t r a n s i t i o n b e h a v i o r of Feg2M12B6,
The h a r d n e s s v a l u e s of (Fe, Co, Ni)82M12B6(M=
Cog2M12Bg and Nis2M12B6(M=Ti, Zr, Hf, Nb and Ta)
Table I
f o r t h e t r a n s i t i o n m e t a l s ( T i , V , Cr,
Mo, W , Mn, Fe, Co, N i , Cu) b e l o n g i n g t o t h e f o u r t h
C r y s t a l l i z a t i o n temperature(Tx), c r i t i c a l
f r a c t u r e t e m p e r a t u r e ( T f ) , Tf/T, and V i c k e r s
hardness(Hv) f o r Fe82(Zr, Hf, Nb)12B6, Cog2
( T i , Z r , Hf, Nb, Ta)12B6 and Ni82(Zr, Hf,
Ta)12Bg t e r n a r y amorphous a l l o y s .
T i , Zr, Hf, Nb and Ta) t e r n a r y amorphous a l l o y s a r e
p l o t t e d a g a i n s t t h e g r o u p number of a l l o y i n g e l e ments M i n F i g . 4.
As shown i n t h e p r e v i o u s sec-
t i o n , t h e h a r d n e s s v a l u e d e c r e a s e s i n t h e o r d e r of
7
CrystdlizaAlloy System
tion Temp
( at "1. )
Tx ( K )
Critical Frac- T
ture Temp
Tf (K,x3.6ks)
Kx
Vickers
Hardness
HV (DPN)
FeazZrtzBs
868
563
0.64
845
Fe~zttflzBs
8 85
598
0.68
920
Fes~NbrSo
8 2 0
623
0.76
790
CorzTtnBs
833
61 3
0.74
890
CoezZrqaBe
782
648
0.83
850
COazHflzb
820
698
0.85
935
C0azN4aBs
705
743
1.05
690
ComTalaBe
723
753
1.04
765
NimZrtzBe
7 03
683
0.97
675
NiaMlaBs
7 25
693
0.96
630
Nis2TaqzBs
6 53
6 93
1.06
585
3 ITx
: (Co,Ni)-(Nb.Ta)
Fe-( 2r.M )
-
> Ni-(Zr .Hf)> Co-(Ti,Zr,M),%Nb >
Tx.Hv: Fe-(2r.M) > Co-(Ti.Zr,Hf ).Fe-Nb
(Co.Ni)-(M.Ta)
> Ni-(Zr.Ht >
Fig. 4
Change i n V i c k e r s hardness(H,) f o r Fe82M12
Bg, Cog2Ml2Bg and Ni82M12Bg(M=Ti, Z r , H f ,
Nb and Ta) amorphous a l l o y s w i t h g r o u p nwnb e r i n t h e p e r i o d i c t a b l e . The v a l u e
marked w i t h a s t e r i s k i s a n e x t r a p o l a t e d one
from t h e d a t a of Co71-77Ti17-23Bg amorphous
alloys.
JOURNAL DE PHYSIQUE
Hf > Zr > Ta > T i > Nb f o r t h e Fe-,
Co- and Ni-base
a l l o y s , i n d i c a t i n g t h e tendency t h a t t h e h a r d n e s s o f
v a l u e s and t h e d i f f e r e n c e o f e l e c t r o n e g a t i v i t y b e t ween t h e b a s e m e t a l ( F e , C o , Ni) and M o r t h e m e t a l -
t h e amorphous a l l o y s i n c r e a s e s w i t h i n c r e a s i n g d i f -
l o i d ( B ) and M.
f e r e n c e o f t h e group number a n d / o r t h e p e r i o d i c num-
and one c a n n o t i c e t h a t t h e l a r g e r t h e d i f f e r e n c e i n
The r e s u l t i s shown i n F i g s . 5 and 6
b e r between t h e b a s e m e t a l ( F e , Co o r Ni) and t h e a l -
e l e c t r o n e g a t i v i t y , the higher i s t h e hardness.
loying element.
a n a p p a r e n t l i n e a r r e l a t i o n s h i p was n o t e s t a b l i s h e d
We t r i e d t o e x p l a i n t h e r e a s o n f o r
Such
s u c h a tendency by v a r i o u s f a c t o r s such a s a v e r a g e
between t h e h a r d n e s s v a l u e s and t h e o t h e r f a c t o r s .
o u t e r e l e c t r o n concentration, atomic s i z e , electro-
J u d g i n g from t h e f a c t t h a t t h e h a r d n e s s v a l u e s a r e
n e g a t i v i t y and t h e h a r d n e s s and m e l t i n g p o i n t of
s i g n i f i c a n t l y i n f l u e n c e d by t h e d i f f e r e n c e of t h e
i n t e r m e t a l l i c compounds i n (Fe, Co, Ni)-M b i n a r y a l -
e l e c t r o n e g a t i v i t y among t h e c o n s t i t u e n t e l e m e n t s , i t
l o y s which have been c o n s i d e r e d t o b e i m p o r t a n t f o r
is concluded t h a t a s t r o n g c h e m i c a l bonding between
u n d e r s t a n d i n g t h e e f f e c t of a l l o y i n g e l e m e n t s 17-
t h e b a s e m e t a l ( F e , Co, Ni) and M(Ti, Z r , Hf, Nb, Ta)
111.
or B
A s a r e s u l t , we have found f o r (Fe, Co, Ni)g2
M12B6 t e r n a r y amorphous a l l o y s t h a t t h e r e e x i s t s a n
and M p l a y s a n i m p o r t a n t r o l e i n t h e h a r d n e s s
of t h e amorphous a l l o y s found i n t h e p r e s e n t work.
a p p a r e n t l i n e a r r e l z t i o n s h i p between t h e h a r d n e s s
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I
I
/I/
A . Inoue, T. Masumoto and H. M. Kimura, J.
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Res. I n s t . Tohoku Univ.
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A. Inoue, K. Kobayashi, C. Suryanarayana and T.
/2/
Masumoto, S c r i p t a Met.
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119.
K. H. J . Buschow and N. M. Beekmans, Phys. Rev.
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B
19
(1979) 3843.
141 M. Nose and T. Masumoto, S c i . Rep. Res. I n s t .
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Fig. 5
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Difference of Electronegativity between
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Fig. 6
R e l a t i o n between V i c k e r s hardness(Hv) and
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