Materials Science and Engineering, 48 ( 1 9 8 1 ) 147 - 165
Review Paper
Designing the Composition and Heat Treatment of Magnetic Amorphous Alloys
T. M A S U M O T O
Research Institute for Iron, Steel and Other Metals, Tohoku University, Sendai (Japan)
T. E G A M I
Department of Materials Science and Engineering, and Laboratory for Research on the Structure of Matter,
University of Pennsylvania, Philadelphia, PA 19104 (U.S.A.) and Max-Planck-Institut fiir Metailforschung,
Institut fiir Physik, Stuttgart (F.R.G.)
(Received O c t o b e r 15, 1 9 8 0 )
SUMMARY
The amorphous alloys obtained by rapid
quenching are considered to have excellent
potential for industrial application. In selecting
an alloy for a specific application, however,
considerations in many areas are required. The
properties o f the amorphous alloys depend not
only on the chemical composition but also on
the quenching condition and the post-quench-
ing heat treatment. The response o f the alloy
to heat treatments again depends on the com-
position. Furthermore, often a combination
o f various properties is required for a particu-
lar application, and it is not necessarily easy
to find a single alloy which satisfies all the
requirements simultaneously. In this paper we
review some of the important factors which
have to be considered in designing the alloy
primarily for magnetic applications. It is not
intended to provide a comprehensive review
of all properties or effects, but an attempt is
made to illustrate the limitations and opportu-
nities in designing alloys for magnetic transition
metal-metalloid amorphous alloys. The sub-
jects covered include the composition depen-
dence o f the bulk physical and chemical prop-
erties o f the amorphous alloys, the effects o f
heat treatment on the structure-sensitive prop-
erties, the combined effects o f composition
and heat treatment which have seldom been dis~
cussed explicitly in the literature and the exam-
ples o f the alloy design for some applications.
1. I N T R O D U C T I O N
The amorphous alloys, or the metallic
glasses, produced b y continuous melt-quench-
ing processes are recognized as important
0025-5416/81/0000-0000/$02.50
147
materials for industrial applications as well
as for fundamental scientific research [1 - 6 ] .
Some of them show attractive engineering
characteristics, such as soft magnetic proper-
ties, high mechanical strength or good cor-
rosion resistance, which are equivalent or
superior to those of conventional crystalline
materials. It has frequently been suggested
that the amorphous alloys m a y have signifi-
cant applications in power transformers and
magnetic and electronic devices such as tape
recorder heads, amplifiers, inverters and
transducers. Their most serious disadvantages
as engineering materials are the thermal
instability against structural relaxation and
crystallization and the geometrical limitation
that the thickness must be less than a b o u t
80 pm. Fortunately, amorphous alloys can be
produced over a wide range of compositions,
and they are sensitive to mild heat treatments
which do not cause crystallization. Therefore
there are ample opportunities to design the
composition and heat treatment of alloys,
t h e r e b y tailoring them for specific applica-
tions, so as to avoid or minimize the short-
comings and to optimize the desired proper-
ties. Furthermore, in order for large-scale
applications to become a reality, superiority
in a single property over that of the conven-
tional material is often insufficient. The
replacement of crystalline materials b y the
amorphous alloys, or the development of
totally new uses of the materials, are more
likely to occur because of the unique com-
bination of properties that only an amorphous
alloy can have. For instance, the combination
o f soft magnetic properties, high hardness and
good corrosion resistance has never been
f o u n d for the crystalline metallic alloys, b u t
© Elsevier Sequoia/Printed in T h e N e t h e r l a n d s
148
it may be possible to find amorphous alloys
which show such a combination of properties,
provided that the composition and heat
treatments are carefully designed.
Our purpose in this paper is to review the
elements which need to be considered when
such an alloy design is attempted. It is not our
intention to provide a comprehensive review
of each property; this can be found elsewhere
[1 - 6]. Only the data from a few sources
have been used to illustrate the point that we
hope to make, thereby permitting us to
discuss the composition- and thermal-history-
dependent properties with minimum experi-
mental uncertainties.
2. ALLOY COMPOSITION
2.1. Composition ranges for amorphous
phase formation
The first step in designing the amorphous
alloys is to know the range of compositions
which allows the formation of an amorphous
phase by rapid quenching. This is by no means
an easy task because at present our knowledge
of glass-forming systems is very much limited,
and it is impractical to try to predict the glass-
forming ability theoretically; the existing
theory of glass formation [7 - 9], although
successful in explaining the glass-forming
mechanism, requires a knowledge of param-
eters which can be determined only after the
formation of the glassy phase. There are
established guidelines [10, 11] which help
the search for glass-forming compositions but
they also require the knowledge of phase
diagrams and heats of formation which are
often unavailable for complicated alloy
systems. Thus it is almost unavoidable that
some trial-and-error experimental processes
should be carried out, gradually expanding
the range of composition by replacing an
alloy component with another chemically
similar element.
The exact location of the boundary of
glass formation depends, at times critically,
on the details of the quenchirig technique.
Therefore improvements in the quenching
technique, together with improvements in
the alloy composition, are crucial in expand-
ing the range of glass formation. This subject,
however, will not be included in this review.
It is desirable to have a wide range of glass-
forming compositions, not only because it
permits a wider choice of properties but also
because it generally ensures good amorphous-
ness of the product. An alloy near the bound-
ary of the glass formation range with marginal
glass-forming ability cannot be produced
easily in the form of wide sheet, and the
temperature and duration of the heat treat-
ment which can be given to the alloy after
production become severely restricted. Fur-
thermore, as will be discussed in later sections,
structure-sensitive properties such as per-
meability become progressively worse as the
boundary of the glass-forming range is ap-
proached.
For application as soft magnetic materials
the alloys of transition metals (iron, cobalt
and nickel) and metalloid elements (boron,
carbon, phosphorus, silicon and germanium)
have been studied most extensively [5, 6].
At present, no other alloy systems appear to
have better characteristics than these alloys
do, in terms of performance, ease of produc-
tion and cost. Among these alloys, the binary
amorphous alloys are limited to the com-
binations of a transition metal with boron
or phosphorus, with the metalloid concentra-
tion from 15 to 25 at.%. Other metalloids are
not known to form binary amorphous alloys
with transition metals, at least by the melt-
quenching techniques. The glass-forming range
is significantly expanded when ternary alloy
systems are considered. Such ternary systems
include one transition metal plus two metalloid
elements, or two transition metal elements,
one of which is chromium or molybdenum
plus boron or carbon. For instance, the glass-
forming ranges in ternary iron-base alloys are
shown in Fig. 1 where it can be seen that the
addition of a second metalloid element to
Fe-P and Fe-B allows glass formation over
a wide range of compositions. It is also known
that binary transition metal-C systems which
3O 30 i i
P
20
51
10
10 20 30 10 20 30
B, at% P, at °1o
Fig. 1. Glass-forming ranges of ternary iron-base
alloys [12] : (a) F e - B - M ; (b) F e - P - M .

can be made amorphous only b y sputtering
deposition can be melt quenched into very
stable amorphous alloys when chromium,
m o l y b d e n u m and/or tungsten are added [ 1 3 ] .
It is possible to estimate the critical cooling
rate semiquantitatively b y measuring the
m a x i m u m ribbon thickness at which it is
possible to form the a m o r p h o u s phase under
otherwise identical conditions; the critical
cooling rate should be inversely related to the
critical thickness. For the ternary system
Fes0MloNlo (where M and N are metalloids)
this m e t h o d indicates that the P - C and B-Si
combinations have the lowest critical cooling
rates among the various combinations of
metalloids and are therefore systems in which
it is easiest to form t h e amorphous phase. It is
not surprising therefore that the early studies
on ferromagnetic alloys were mostly on F e -
P - C alloys [ 1 ] .
The relative ease of glass formation of other
combinations can be shown by the following
list of combinations (in decreasing order of
ease of glass formation): P - C or B-Si, B-P,
B-C, P-Si, P - G e and B - G e [ 1 4 ] . However,
as shown below, the P - C combination is not
necessarily the best one for application when
other factors than the ease of formation are
considered.
2.2. Crystallization temperature
In order to ensure the thermal stability of
the alloy and to allow various heat treatments,
it is desirable that the crystallization tempera-
ture Tx remains high both in absolute value
and with respect to the glass transition
temperature. Although the quenching rate
has some minor effect on T~, the composition
is, of course, the most important parameter in
determining Tx. Figure 2 shows T~ for the
a m o r p h o u s FesoP2o-=Mx and FesoB20-xM~
alloys (M --=-B, C, P, Si or Ge). The effective-
ness in raising T~ decreases in the order
silicon, germanium, boron, carbon and
phosphorus. Among the ternary Feso(M,N)2o
systems the combination of b o r o n and silicon
results in the highest values of T~. As is
evident in Fig. 2, the mixing of t w o metal-
loids tends to increase Tx compared with
binary systems which contain only one
metalloid element. This is an e m b o d i m e n t of
the "confusion principle" which in essence
states that increased entropy of mixing sta-
bilizes the amorphous phase. Although it is
149
i
8OO
o
5i
E700
S
~, 600
,3
10 20 10 20
X X
Fig. 2. Crystallization temperature Tx of iron-base
alloys determined by diff.erential thermal analysis at a
heating rate of 5 °C rain -1 [12] : (a) Fe8oB20_xMx ;
(b) FesoP2o-xMx •
not a universal rule and there are many excep-
tions, the confusion principle at times serves
to select alloy compositions when pertinent
data are scarce. Replacing iron b y other
transition metals sometimes raises Tx. As
a general rule the addition of transition metal
elements with d and s electron concentrations
less than those of the base metal increases
Tx, when the base metal is iron, cobalt or
nickel [12, 15]. As will be mentioned in
Section 2.3, this behavior appears to be
related to the variation in cohesive energy
with electron concentration. A higher cohesive
energy implies a higher glass transition tem-
perature Tg as long as the structure remains
the same, and therefore generally a higher Tx.
It is interesting to note that the cohesive
energy of the B-Si alloys is lower than that
of B - C alloys, as estimated from the hard-
ness data. The higher values of Tx for the B -
Si alloys m a y be a reflection of the fact that
the Fe3 B and Fe3Si crystals have quite
different structures and are therefore mutually
insoluble, whereas Fe3B and Fe3C are struc-
turally more similar and an F e - B - C alloy
easily crystallizes into an Fe3(B,C) pseudo-
binary c o m p o u n d with an Fe3C(Ni3B) struc-
ture [16] ; an argument of this kind was first
p u t forward by Chen [ 1 7 ] .
2.3. Mechanical properties
As has been reviewed previously [4, 18 - 2 0 ] ,
the mech~inical properties of amorphous alloys
are characterized b y high values of elastic
limit, yield strength and hardness, together
with predominant ductility.
The detailed variations depend on the com-
position and appear to be directly related to
150

the cohesive energy of the alloy. Several i i i

/
examples of such behavior are shown in Figs. 3 1100 r~o~-~M;I -I F%~0
and 4. The microhardness, Young's modulus LF x'xJ
and yield strength change linearly with the
concentrations of outer d and s electrons (the lOOO / 4
electron-to-atom ratio) of the constituent
metallic elements. Together with the behavior
of Tx, these results indicate that the cohesive
energy of the alloy changes linearly with the
electron-to,atom ratio, the result expected
from a simple rigid band argument. This
simple behavior results presumably from the
very similar atomic structures of these alloys.
The hardness of the iron-base amorphous
alloys depends on the metalloid concentration, 0 5 10 15 20
as shown in Fig. 5. The Fe-B alloys have the M .at'/.
Fig. 5. Microhardness of iron-base alloys with various
metalloid compositions [ 12 ].
900
\o
g00 highest values of hardness, as expected from
Cr z ~.~ the generally high cohesive energy of the
Z
j ~7oo ~\o o boron alloys.
13
Ti//V 600 \ The hardness values decrease in the order
B-C, B-Si, B-P, B-Ge, P-C, P-Si and P-Ge.
"o __~Mn 500
Evidently the radius of the metalloid element
\ ~ 7 8 elo 9
is also an important factor. The smaller the
Cu ~ Co
700
Ni
radius, the higher is the hardness (and hence
the cohesive energy) provided that the elec-
tron-to-atom ratio is constant.
600 ~ t t
0 10 20 30 40 2.4. Corrosion resistance
Y
Some of the amorphous alloys have an
Fig. 3. M i c r o h a r d n e s s o f F e - P - C - b a s e p s e u d o b i n a r y
extremely high resistance against pitting and
a l l o y s F e 8 o _ y M y P 1 3 C 7 . The inset s h o w s a p l o t against
the average outer electron concentration of the tran- crevice corrosion as well as against general
sition metals (the electron-to-atom ratio e/a) [15]: corrosion in acidic and neutral solutions. This
×, Ti; A, V; e, Cr; m, Fe; o, Co; o, Ni. superior corrosion resistance is attributed to
the microscopic chemical and physical homo-
geneity of the surfaces of the amorphous
95 3.4 o

o o
alloys and to the rapid formation of highly
800 oo Oo 90 3.0 o~o °o
protective passive f i l l s on the surfaces be-
85 °2.6 cause of the high concentration of metalloid
z 750
° ~:2 ' ;.6 ',o'.c
850 • 95 elements [22]. The corrosion resistance is one
of the most conspicuous characteristics of
-o
some of the amorphous alloys, and the com-
'90
.~ coo bination of this and the soft magnetic proper-
ties make the amorphous alloy quite attractive
in various applications.
85

750 The corrosion resistance, however, is not

0 10 20
i L ubiquitous in amorphous alloys but is rather
10 20 0 10 20
(a)
(b)
M, at'/.
M. ot'I. (,~
"c" .. ='l. drastically dependent on composition. Fig-
Fig. 4. (a) Microhardness, (b) Young's modulus and
ures 6 and 7 show the composition depen-
(c) yield strength of Feso_yMyP13C7 alloys, together dence of the corrosion rate in sodium chloride
with plots against the electron concentration (the and hydrochloric acid solutions for iron-base
electron-to-atom ratio e/a) [21]. and cobalt-base amorphous alloys.
 151

07
corrosion resistance as well as in terms ui the

06
~
, ~. ~:.---"
t 3"1. NoC( °7I
06 jx~ko'~ 3% No El
ease of glass formation.
The effect of metal addition is dependent
~, OS 0~k ~:~,¢~-- . . . . . . also on the metalloid composition. As shown
~. ,
in Fig. 6, the corrosion rates of the phosphorus-
BI3C? containing alloys are t w o to three orders of
B13SiT
~ 0.3
03 Nn magnitude lower than those w i t h o u t phos-
~'7 B13P7
O~ Ni,Co phorus, in 3% NaC1 solution. The difference is
~ 02 }B7
more pronounced in aggressive solutions such
0.1 01- ZIr Cr, Mo.W as 1 N HCI. The corrosion resistance decreases
0
in the order phosphorus, silicon or carbon,
0 4 6 8 1o 2 4 6 8 10
(a) Cr, o t % (b) M,o,',. and boron. The corrosion resistance of the
alloys containing boron is hardly improved b y
Fig. 6. Corrosion rate of iron-base alloys in 3% the addition of chromium.
NaCl solution [23 - 26] : (a) (Fe,Cr)80M20 ; (b)
(Fe,M)so P13 C7. Thus the most effective combination of
metal and metalloid elements is the group Via
elements chromium, m o l y b d e n u m and tung-
sten plus phosphorus. Unfortunately these
10 1C __ 3 0 C r - 2 M o stainless ,,p~
elements have adverse effects on the magnetic
- - 304 stainless ( , e ~ ~"
properties; b o t h the magnetic m o m e n t and
~ rxBZO the Curie temperature are drastically reduced
1 -" 7
on replacing iron b y chromium, m o l y b d e n u m
C~O , FeWxP13C 7
or tungsten. Therefore, again a careful exam-
ination of various properties is necessary in
01 FeMoxPi3 C 7 selecting an o p t i m u m composition.
CrxP?3 B7
The iron-base amorphous alloys which have
a low corrosion resistance, especially those
0~-- Hostel'oy X
10 20 0 10 20
containing phosphorus, often exhibit a delayed
ALloying Element, X at % fracture p h e n o m e n o n under tension in air
Fig. 7. Corrosion rate of iron- and cobalt-base alloys [ 27 ]. This t y p e of fracture is induced, prob-
in 1 N HCI solution [23 - 26]. The horizontal bars ably because of the embrittlement b y hydrogen
indicate the corrosion rate of typical corrosion-
resistant crystalline alloys. absorbed from the environment under stress.
Therefore the delayed fracture can be avoided
The iron- or cobalt-base alloys w i t h o u t any b y adding chromium, m o l y b d e n u m or tung-
other metals are chemically unstable even sten, thereby preventing decomposition of
compared with their crystalline counterparts. water on the surface.
However, the corrosion resistance is drama-
tically improved b y the addition of other 2.5. Magnetic properties
metallic elements. For the iron-base alloys The magnetic properties of interest for
containing phosphorus, the improvement is applications are dependent on the alloy com-
most pronounced when copper replaces part position either directly or indirectly through
of the iron and is followed b y titanium, the microstructure of the alloy. In this section
chromium, zirconium, m o l y b d e n u m , tungsten, we review the bulk properties which are
vanadium, niobium, nickel, cobalt and man- directly dependent on the composition,
ganese, in decreasing order of effectiveness. namely the r o o m temperature magnetization
This tendency is even more distinct in 1 N and the Curie temperature. The magneto-
HC1 solution which is more aggressive. Al- striction will be treated separately in Sec-
though the addition of a small a m o u n t of tion 2.6. The structure-sensitive properties
copper, titanium or zirconium very effectively such as coercivity and permeability will be
increases t h e corrosion resistance, it makes discussed in Section 3.
the formation o f the a m o r p h o u s phase signif- Many data have been compiled and reviewed
icantly more difficult. However, the addition in several papers [5, 6, 2 8 ] . However, there is
of chromium, m o l y b d e n u m or tungsten considerable scatter and disagreement among
produces satisfactory results in terms of the them, so that it m a y be useful to reassess the
152

r
1so I
as U
o
180
160 C (Fe8oC2o)

~ 140 "-x...Os

cq 120 16o "<"" "- (F~oG~o)

~ 10o B
g, 150 ( Feso P2o)
80 Fe8oP2O: ....... , (Feso Ge2o)
750 (Tc>Tx) ~Ge'-
~...,, 800
60 "~ s

Tc ~ &'°'°"~ 700 ~ f ~ ~ ' ~ S i - - ~ ; ~-> ! ( Fe8oSi Zo)

Fe-B~ " m~ Tc 700
."" . -"
-~Tc ~ 600~
%
FeeoB20

6 5 0 ~ . ~ A ~ . . -
(FeBoB2o)

,ool
I-- C...._. ~ ' (Fee0 C 2o)
500
L L
10 15 20
B or P, 215
at.'/,
3J0 35

Fig. 8. T h e saturation magnetization o s at room tem-

FeB°P20 ~
o
I
5
I '
10
I
15
" ~(Fee°P20)
20
perature and the Curie temperature T c of binary M , at°/o
iron- and cobalt-base alloys: [], ref. 29; x , ref. 30; Fig. 9. The saturation magnetization o s and the
$, ref. 31; o, e, refs. 32 and 33. Curie temperature T c of ternary iron base alloys
Fe80 B20 - x Mx, Fe80 P20-x Mx : - - - , extrapolations
effect of metalloid composition on the in- [32,33].
trinsic properties qualitatively, using limited
b u t consistent sources of data.
Figure 8 shows the composition dependence
of saturation magnetization as at r o o m tem-
perature and the Curie temperature Tc for
-.~ 85
the binary amorphous alloys F e - B , F e - P and p
C o - B . Both os and T c of cobalt-base alloys ~ 8o
decrease as the concentration o f b o r o n is 75
increased, because of the magnetic dilution b y (Tc>Tx}
and the charge transfer from b o r o n atoms. On
the contrary, Tc o f iron-base alloys increases
as the metalloid concentration is increased.
Furthermore an unusually low spin wave
stiffness and the Invar effect were observed
i i i
for iron-rich alloys [ 3 4 ] , indicating the pos- 0 5 io 15
X
sible presence of antiferromagnetic interaction
Fig. 10. The saturation magnetization os and the
for some F e - F e pairs with close separation
Curie temperature T c of Co75B25_xM x (M -= C, P,
[35]. Si, Ge, As) [36].
The values of os and Tc for various com-
binations o f metalloids axe shown in Figs. 9 B-Si or B - C - S i are likely to be used. For the
and 10. In terms o f enhancing the value of cobalt-based alloys the effects of metalloids
Tc o f iron-base alloys, the metalloids rank in are similar for Tc and as. Both of them are
the order germanium, silicon, boron, carbon reduced in the order carbon, boron, phos-
and phosphorus. Similar results were obtained phorus, silicon, germanium and arsenic.
b y Chen et al. [ 3 7 ] . However, the value o f os
is highest for boron, silicon and carbon and is 2.6. Magnetoelastic properties
less with germanium and phosphorus, in that The saturation magnetostriction value ks
order. Unfortunately there is no combination for the iron-base alloys is from 30 X 10 -8 to
which maximizes both os and Tc simul- 50 × 10 -6 at r o o m temperature [38, 3 9 ] .
taneously. There is a strong correlation between the
For applications which require high mag- values of ks and Ms 2, possibly because of the
netic induction, the iron-base alloys with B-C, structural similarity of these alloys. The
 153

Co 0

~9 ~ ~ oo

/ / \\\\-T~oM~o

Fe I k k
.2 .4 .6 .8 Ni
I" Ni

Fig. 11. Saturation magnetostriction k s of the

(Fe,Co,Ni)7sSisB14 pseudoternary system at room
temperature [40].
0 20 4o
Ni Ni(ot °/o) --
Fig. 14. Dependence of the zero-magnetostriction line
on the metalloid concentration. The compositions
are Ta70SiloB20 , Ta74SiloB16 and Ta78SisB14 [43].

¢O .~- ~L 16,~o-' T, &~T.

Fess B17
Fe .2 .4 .6 .8 Co
Co T~ Til 'i2~'j
Fig. 12. Zero-magnetostriction line for the
(Fe,Co,Ni)7sSisB14 pseudoternary system. The
saturation induction at room temperature is also
shown [ 41 ].
Co

I I I I I
300 &O0 500 600 700
T(K)
Fig. 15. Linear thermal expansion ,;kL/L of iron-base
binary amorphous alloys [44].

• .~j/:
0 .05 .10 Cr~b Mo To .20 22
PM
Fig. 13. Zero-magnetostriction lines for the ~20 ~ 0 e
(Fe,Coj~I)78SisB14 pseudoternary system [42].

Co-Ni-base alloys have a negative X,, and as U3

a result some cobalt- or nickel-rich alloys with 1.4

small concentrations of iron show zero mag-
netostriction, as shown in Figs. 11 and 12. 1.2
- I00 0 100 200 300 400
Figure 13 shows the zero-magnetostriction T(°C)
lines for pseudoternary systems (Fe,Co,M)7 s- Fig. 16. Temperature dependence of Young's modulus
SisB:4 where M stands for various transition for Fe83B17 Mloy for various applied magnetic fields
elements [42]. The zero-magnetostriction line [461.
becomes displaced when the total metalloid
concentration is changed, as shown in Fig. 14. Invar behavior or zero thermal expansion was
The volume magnetostriction of iron-base observed for F e ~ B : 7 as shown in Fig. 15
alloys is generally positive and contributes [ 4 4 ] . Because of the high permeability the
negatively to thermal expansion. As a result, magnetic effect on Young's modulus, or the
154
AE effect, is quite large [45]. For appropriate
compositions the A E effect makes the Young's
modulus temperature independent over a
wide range of temperatures (Fig. 16). This
Elinvar effect has been observed in FessBzs,
FemCr4B15 and FessPz5 [46].
3. H E A T T R E A T M E N T
3.1. Thermal behavior of amorphous alloys
Various properties of the amorphous
alloys undergo significant changes when the
alloys are subjected to a heat treatment at a
temperature and duration insufficient to
cause crystallization. Some of the changes
are beneficial for applications, but others are
harmful. It is therefore important to know
the mechanism of these changes and to design
the optimum heat treatment accordingly.
It may be worthwhile to note that the ques-
tion of the thermal behavior is also pertinent
in considering the melt-quenching process
itself. Since the quenching rate is finite, even
the as-quenched samples are, strictly, partially
annealed. Relatively slowly quenched samples
show characteristics of the well-annealed
samples, such as brittleness. Therefore the
properties of the as-quenched samples are not
unique to the alloy composition but depend
on the quenching rate. When the amorphous
alloy is subjected to a heat treatment, three
distinct types of atomic rearrangement take
place, other than the crystallization. They are
diffusion and changes in the topological short-
range order (TSRO) and in the compositional
short-range order (CSRO) [47]. The most
fundamental parameter is the TSRO which
describes the way that the atoms are den-
sely packed, and hence the density of struc-
tural defects or the free volume. The TSRO
governs the kinetics of the atomic diffusion
and relaxation.
3.1.1. Topological short-range order
Since the amorphous alloys are obtained
by rapid quenching from the melt, the as-
quenched atomic structure is not quite stabi-
lized, and it contains a high density of struc-
tural defects [48]. A heat treatment near the
glass transition temperature Tg relaxes the
structure and annihilates the structural defects.
The change in the structure due to this relaxa-
tion has recently been observed directly by X-
ray diffraction [49, 50], and it was found that
the structural defects were fairly well delocal-
ized, extending over several atomic distances.
Therefore a collective atomic motion rather
than a single atomic diffusion jump is required
to annihilate such a defect, and the structural
relaxation occurs in a higher temperature
range than the diffusion. The kinetics of the
change in TSRO is described by
RTSRO kT lnt t + It
- (1 )
{to(T)
as shown in Fig. 17.
Since the TSRO governs the kinetics of
most of the phenomena related to the atomic
transport in the amorphous alloys, this In t
behavior is observed quite frequently for
many properties.
I I I I
r0 rc ~ -
0.05 0 ....~- 3 5 0
~_o
-~ 0/ 0 """ 0~"" O" ' ' " . ~ 0. - 300
~_o
c,," ~0"" ..._.-..- 2 5 0
0 I I I t t
5 15 30 60 120
TIME (rnin)
Fig. 17. Kinetics of the change in the T S R O parameter
RTSRO d e t e r m i n e d f r o m a diffraction study (for a
definition o f the parameter, see ref. 49).
3.1.2. Compositional short-range order
The CSRO of the chemically very different
species must be well established even in the
liquid state, but the CSRO between elements
chemically similar to each other, e.g. iron and
nickel, may be significantly temperature
dependent and may respond to annealing
[47]. At present, there is no direct structural
observation of the effect of annealing
on CSRO, but the change in the Curie tem-
perature (Fig. 18) and the magnetically in-
duced anisotropy are believed to be due to
the thermal change in the CSRO. The phys-
ically relevant CSRO is that of nearest neigh-
bors, so that the atomic rearrangements which
change the CSRO are more short range than
those for the TSRO. Therefore the tempera-
ture range in which the changes in the CSRO
take place is lower than that for the TSRO

QO I I
A N N E A L I N G T I M E S , rain
~o- ,~o/~:,-~
\\\\
• 40 ,.~k~,
/ / /'/Io •~,~'~'~...
z_ Io
° /7///2/ -""-~-~
o
I00 200 300
ANNEALING TEMPERATURE, "C
Fig. 18. Isochronal annealing curves of T c for
Fe27Ni53P14B 6 alloy [ 5 1 ] .
and coincides with the range for diffusion.
However, the kinetics of the CSRO changes
determined from the behavior of Tc appear
to be governed b y the TSRO; as t h e TSRO is
increased, the rate of the change in the CSRO
becomes slower [ 5 2 ] .
3.1.3. Diffusion
For the as-quenched amorphous alloys,
stress relaxation and mechanical creep due to
atomic diffusion become appreciable at
temperatures as low as 150 °C, so that a
knowledge of diffusivity is required in design-
ing a device which m a y be exposed to elevated
temperatures.
In discussing the diffusivity it is most im-
portant to recognize that the diffusion in the
melt-quenched amorphous alloys occurs be-
cause of the structural defects [ 4 8 ] , so that
it is d e p e n d e n t on the thermal history of the
sample [ 53 ]. The conventional expression
D ( T ) = Do exp - - ~ - ~
should not be used indiscriminately to cal-
culate the temperature dependence of the
diffusivity, since b o t h D o and AE are depen-
dent on temperature and time. At sufficiently
high temperatures approaching Tg, the acti-
vation energy for the structural relaxation
(TSRO) which is time and temperature de-
p e n d e n t through [49]
AE = 0IRTsRO
appears to coincide with that for diffusion
[ 5 4 ] , so that the diffusivity depends on the
time as
155
d
D(t) - (4)
t+ to
The diffusivity is high if the sample is very
rapidly quenched and it is low if it is either
slowly quenched or annealed.
• •
~.~ 3.2. Magnetic anisotropy
The magnetic anisotropy in the melt-
quenched alloy results from t w o origins:
(1) the magnetostrictive anisotropy due to
internal stresses [55 - 57] and (2) the field-
400
induced anisotropy due to the directional
CSRO [58, 5 9 ] . In the as-quenched state the
alloy tends to have a highly inhomogeneous
distribution of internal stresses which are
produced during the rapid solidification
process. The local easy direction can be either
in or o u t of the plane of the ribbon. As a
result the remanent magnetization is less
than half of the saturation magnetization,
and a magnetic field of up to 100 Oe is re-
quired to saturate the magnetization along
the length of the ribbon. The magnetostric-
tive anisotropy can be annealed o u t b y a
heat treatment at temperatures high enough
to induce sufficient diffusion. The kinetics
again follow approximately a In t behavior.
The field-induced anisotropy is obtained b y
annealing the alloy in an external magnetic
field. Annealing under stress also results in a
similar effect. This anisotropy is believed to
be caused b y directional ordering of like
pairs of atoms, or directional CSRO, judged
from the composition dependence [58, 5 9 ] .
Directional CSRO results in magnetic aniso-
t r o p y , either via an anisotropic exchange
interaction or via the crystal field effect
[ 6 0 ] . This annealing is effective only below
(2) Tc, since the real driving force to change the
CSRO is the exchange field; an external •
field simply aligns the spins and thus sets the
direction of the induced anisotropy within
each domain.
As might be expected if the anisotropy is
due to directional nearest-neighbour CSRO,
it can be changed reversibly or reorientated
b y annealing with the field in a new direc-
tion [ 6 1 ] . The kinetics of the reorientation
is again In t [ 6 2 ] , indicating that the change
(3) in TSRO controls the kinetics of reorienta-
tion. If the sample is well annealed in advance,
the reorientation could show the exponential
kinetics expected from the first-order rate
156
equation, since the TSRO is already stabilized
and does not change much, so that the dif-
fusivity is roughly constant during the re-
orientation. However, the activation energy
observed should depend on the TSRO deter-
mined by the preannealing, and it would not
be surprising if the values determined by
different researchers disagree; these values are
not intrinsic constants which depend only on
composition.
3.3. The Curie temperature
The Curie temperature is primarily de-
termined by composition as has been dis-
cussed. However, it can also be changed by
heat treatment, sometimes by more than 10%.
This phenomenon is considered to be also due
to the change in the nearest-neighbor CSRO
[47]. In some Fe-Ni alloys it is possible to
achieve local thermodynamic equilibrium of
the CSRO, since the kinetics of the CSRO
are faster than those of the TSRO or of
crystallization. In this case T c can be changed
reversibly by heat treatment (Fig. 19). Such
local equilibrium can also be attained for
TSRO, above Tg. In most of the transition
metal-base alloys, however, crystallization
intervenes before equilibrium is reached
[54]; in other words, Tg is often higher
than Tx. In alloy systems other than Fe-Ni,
equilibrium CSRO has not been observed.
The heat treatment of Co-Ni alloys results
in a more complex and heterogenous mag-
netic behavior [63].
! r I I I I
I10
250°C
,o , - '
I00
~-° 9~i 3oo.c
90 3 0 min
85 __ AS QUENCHED
i I ] I I I
500
TOTAL ANNEALING TIME (rnin)
Fig. 19. Change in T C of Fe27Ni53P14B6 due to
cyclic annealing at 250 °C and 300 °C for 60 rain
and 30 min respectively [47 ].
3.4. Permeability
There are many possible mechanisms to
determine the coercivity of magnetic amor-
phous alloys, such as pinning by inclusions,
internal stresses, surface roughness etc., and it
is quite difficult to isolate the principal
mechanism for each sample. The initial sus-
ceptibility or the permeability Po which is
determined by the ease with which domain
walls make small displacements is slightly
less complex and is primarily dependent on
the internal stresses and the induced magnetic
anisotropy. In an alloy with non-zero mag-
netostriction, the permeability in the as-
quenched state is mainly determined by the
internal stresses created during the rapid
quench, which can be removed by a heat
treatment. Therefore a heat treatment gener-
ally increases the permeability. The situation
is different for a zero-magnetostriction alloy
in which the internal stress has no effect. A
heat treatment at a temperature below Tc
has an effect of imprinting the domain pat-
tern present, by inducing the anisotropy
along the direction of the magnetization in
each domain and within the domain walls.
Thus the permeability is decreased when
the alloy is annealed at temperatures below
Tc. However, the decrement can be recovered
to a large extent by heat treating the sample
at above Tc and rapidly quenching, say into
water, as shown in Fig. 20 [43, 65]. Recent
studies have shown that this "annealing"
effect can occur even at room temperature
(Fig. 21) and is observed as the magnetic
after-effect or the decrease in the permea-
105 Tx
6
I I :
-~ 25
20
15
io 4
~J0 <
5
~'~ O
i /
103 i i I i i • i
100 200 300 400 500
A n n e a l i n g temperature, *C
Fig. 20. Dependence of permeability of a zero-
magnetostriction alloy (Fe0.06Co0.ss)74Si10B16 on
annealing temperature. Each annealing treatment was
carried o u t for 30 min followed by quenching into
water: curve 1, as-quenched sample; curve 2, sam-
ple annealed at 420 °C and water q u e n c h e d ; curve 3,
sample annealed at 420 °C and slowly cooled (150 °C
h - 1 ) to room temperature [64].
 157

~.r(%) phous state [71] and structural relaxation

t2=
5 perature (Fig. 23) [72] and the decrease in
0 - - i * ~ I
0 100 200
T(K)
Fig. 21. Magnetic after~effect of Fe40Ni40P14B6
at various temperatures, determined by the rate of
decay of the permeability [66].
bility with time, the so-called disaccommoda-
tion [67]. This is an important phenomenon
from both practical and scientific points of
view and deserves further attention.
3.5. Embrittlement
Another harmful effect of heat treatment
is that it causes embrittlement of iron-
containing amorphous alloys. In some cases the
alloy becomes so brittle after annealing that
it cannot be handled without breaking. Since
the combination of excellent magnetic and
mechanical properties is the most attractive
feature of the amorphous alloys, this loss of
ductility by annealing is a serious problem.
It has been proposed that the segregation of
phosphorus might be the cause of embrittle-
ment [68] ; however, the evidence is against
this idea [69, 70]. Other mechanisms
proposed to explain t h e embrittlement in-
clude incipient phase separation in the amor-
150'
(Fig. 22) [72]. These are, in fact, somewhat
related, as will be discussed in Section 4.
The observed kinetics of the effect of anneal-
ing on the ductile-to-brittle transition tem-
the activation volume during the mechanical
creep [73] strongly suggest that it is struc-
tural relaxation which drastically reduces the
300 ability of the alloy to flow like a liquid under
stress, thereby causing embrittlement. In re-
lating the structural relaxation to the mechan-
ical properties, however, the bonding charac-
teristics of the constituent elements have to
be considered. Transition metals with un-
filled d bands, such as iron, show directional
bonding and hence show a higher resistance
to flow. From such a point of view, it is
readily understood that iron-base alloys
always become brittle after structural relaxa-
tion, while nickel-base alloys are not embrittled
even after partial crystallization, as shown in
Figs. 24 and 25 [74].
i q i
Ta
300 ~ 523K
4OO
200 J°~I~ ~ _ . . 47~,,
423K
100 O ~
i L h i
15 30 60 120
Annealing Time (rain)
o o Fig. 23. Effect of annealing on the shift of the
ductile-to-brittle transition temperature Tdbt of Fe40-
Ni40P14B 6. T a denotes the annealing temperature
o 0

o oO ; oo [721.
i , , t

100 °-7~
o /r o
0 500I ~ ~
0/ o
o //o • ©
o
e ? MS-11

4.00 J \ \ 'x e~=0.02

i---

\ \ ~=.%' \~. bcc

e~=10 \ \\ xx
300 J Arnorpblous \\ \\
0 i i 0 -£ I l I i
100 200 --3 0 400 10 10 2 10 3 10 4 10 5
Test Temperature ( K ) Aging Time (rain)
Fig. 22. Temperature dependence of the twist angle Fig. 24. Kinetics of crystallization and embrittlement
81 (e) where a crack starts and the twist angle (92 (o) of Fe78SiloB12 alloys. Ef denotes the fracture
where the crack ends with fracture of a notched strain in bending. MS-I is the crystalline ~-Fe phase
Fe40Ni40P14B 6 alloy in the as-quenched state. '['he plus amorphous matrix; MS-II is a metastable state
sample is brittle below about 155 K (for details see which is a mixture of crystalline a-Fe and Fe3(Si,B )
ref. 72). [74].
158
500
i i i 1
~-~'-~.~ ... E, =0.02
Amorphous ~ -"
f.c.c.
300
I I I I
10 10 2 10 3 10 ~
Aging Time(rain)
Fig. 25. Kinetics of crystallization and embrittlement
of Ni75SisB17 alloy [74].
4. COMBINED EFFECTS OF COMPOSITION AND
HEAT TREATMENT
4.1. Composition dependence of annealing
effect
The effects of heat treatment discussed in
Section 3 depend in various ways on the com-
position of the alloy. The bulk properties
which are relevant in determining the anneal-
ing effect, such as the Curie temperature in
magnetic annealing, are composition depen-
dent; thus the composition directly affects
the thermal behavior. In some cases it is pos-
sible to predict the effect of annealing, given
a knowledge of these properties. However,
the composition also affects the thermal
behavior of the alloy in a more subtle way,
through the short-range order. Unfortunately,
this is one of the areas where we lack direct
experimental data, so that at present much of
the discussion has to be based on conjecture.
It appears that there is a correlation between
some of the structure-sensitive properties,
such as magnetic permeability and embrit-
tling tendency, and the ease of formation of
the amorphous phase or the crystallization
temperature. On a microscopic level the
glass-forming tendency corresponds to the
ease of producing atomic disorder [7]. A
system with a high glass-forming tendency
maintains structural homogeneity, in the
sense of uniform disorder, during quenching
and subsequent annealing, without forming
nuclei of crystallization or phase segregation.
It also follows that structural defects are more
easily produced in a good glass-forming
system, so that such a system should respond
more effectively to annealing than a poor
glass-forming system, even when they are
both produced at the same quenching rate.
In the following we shall discuss several
examples of the composition dependence of
the annealing effect, to illustrate both the
direct effects and the indirect effects of the
alloy composition on the thermal behavior
(other than crystallization) of the amorphous
alloys.
4.2. Induced magnetic anisotropy
105 The field-induced magnetic anisotropy is
considered to be caused primarily by the
directional CSRO, or the atomic pairing, as
has been mentioned. The evidence is that the
magnitude of the induced anisotropy K, is
approximately proportional to c2(1 -- c) ~
where c is the concentration of one of the
alloy components, when appropriately nor-
malized with respect to magnetization [58,
59]. A typical composition dependence of
K, in the Fe-Ni-Co system is shown in
Fig. 26, together with Tc.
The maximum in K~ occurs when the con-
centrations of iron and cobalt are about
equal and when a small amount of nickel is
added, indicating that the directional CSRO
between iron and cobalt is the principal
mechanism of the induced anisotropy. Nickel,
which is non-magnetic by itself in this amor-
phous alloy system, also contributes to K,
by allowing the directional pair ordering of
magnetic atoms. However, a high concentra-
tion of nickel results in a low value of K~
partly because of magnetic dilution and per-
haps more significantly partly reducing Tc,
thereby making the short-range diffusivity at
Tc too low to produce equilibrium CSRO
during the annealing.
Ni
(O " ~"
Fe ~ Co
0 .2 ./, .6 .8
Co
Fig. 26. Induced anisotropy K u (erg cm - 3 ) ( ~ ) of
(Fe,Ni,Co)78SisB14 pseudoternary system obtained
by field cooling from 520 °C, shown together with
TC ( - - - ) [41].
 159

Appreciable values of K~ are observed magnitude. However, if the alloy is slowly

when either iron or cobalt is the only metal
component, suggesting directional CSRO
between the metal and metalloid. Adding
nickel to cobalt does not increase the value of
K~. This may be related to the fact that the
annealing results in a magnetic inhomogeneity,
probably almost a phase separation, in the
Ni-Co system [63].
4.3. Combined effects on magnetic
permeability
4.3.1. Effect of anisotropies
As has been discussed earlier, the magnetic
permeability of amorphous alloys depends
primarily on the magnetostrictive anisotropy
and the field-induced anisotropy. This is
clearly illustrated in the results given in
Fig. 27 [41]. In this experiment the com-
position of iron, cobalt and nickel is adjusted
so that the Curie temperature is about 300 °C
but the magnetostriction changes from
12 X 1 0 -e for (Feo.4Nio.6)7sSiaB14 to --4 X
10 -6 for (Co0.65Ni0.as)78SisB14.
The permeability in the as-quenched state
is low except for the X ~ 0 composition,
indicating that the magnetostrictive aniso-
tropy is the main factor in determining the
value of ~ . The magnetostrictive anisotropy
can be largely removed by annealing at
temperatures 50 - 80 K below Tx and, if the
alloy is water quenched so that there is little
chance for the induced anisotropy to develop,
the value of p~ is increased by an order of
105
i i i i
5
3
2 Water
cooled through Tc, an induced anisotropy
develops and I~e is significantly reduced.
In this particular case, #e is independent of
the metal composition and is certainly un-
related to the magnetostriction.
In the second experiment (Fig. 28) [64]
the magnetostriction was kept at nearly zero
but the Curie temperature was changed by
adjusting the composition. If the alloys are
water quenched from 450 °C, ~/e is nearly
independent of composition and therefore of
Tc. If the alloys are air cooled or slowly
cooled in the furnace, however, p~ is a strong
function of Tc. Since Ku is induced only be-
low Tc, if Tc is too low for diffusion to
occur, the reduction in pe does not happen
even when the sample is cooled slowly.
Therefore, reducing the value of Tc is one
method of reducing the aging effect on
~e, or the disaccommodation effect. The
main disadvantage of this is that the room
temperature magnetization is also reduced.
4.3.2. Dependence on metalloid
composition
The behavior of #e described above is
qualitatively understandable in terms of
magnetostrictive and induced anisotropies.
The value of ge, however, depends on com-
position in a more indirect way. Figure 29
shows the value of Pe for (Co,Fe)To(B,Si)ao
alloys both as quenched and after a heat
treatment [43]. As the ratio of cobalt to iron
is changed, the alloy goes through a zero-
i
magnetostriction line and Pe becomes max-
imum. The value of p~, however, is not con-

o 10~ ~051
E ,ff o
o
5 Cooting Qt the rQte of 150°C/h /~ ~e o @ Water quenched
E ~ c from 450~C
---i ...... ,r . . . . . . ~--/-:~--¢-
~ 2
:~ 2 oo~yro
"\\
¢n
:~ 10a As-Quenched State/.~ @" '~
c '\
.o " -
-~-10
51
3 ~6
2
102 ., i i i i I I -. I 2 \ 150'C/h
Fe40 35 25 15 10 5 0 +
CoO 15 25 40 50 55 65
103 ' ' 0 L J L
Ni 6 0 50 50 45 40 4O 35 100 200 3 0 400 500 600
Atomic Froction of (Fe, Co. N i ) ( % ) Curie temperature (°C)

Fig. 27. P e r m e a b i l i t y o f various ( F e , C o , N i ) T s S i s B 1 4 Fig. 28. P e r m e a b i l i t y o f (Fe,Ni,Co)74Si10B16

alloys w i t h T C ~ 300 °C, as q u e n c h e d , w a t e r quenched z e r o - m a g n e t o s t r i c t i o n (k s = 0) alloys, as a f u n c t i o n o f
f r o m 450 °C o r slowly c o o l e d (150 °C h - 1 ) f r o m TC, w h e n w a t e r q u e n c h e d , air c o o l e d o r f u r n a c e
450 °C [ 4 1 ] . c o o l e d at 150 °C h - 1 f r o m 450 °C [ 6 4 ] .
160

0.8 / I ~- t . ~ 10 5 85

05 2oooo ,,
/ i 30.0C )
Si

i\ ~°:,.5oo,
',\',
,oi /~ ~ , / ~
~, ~ /s I l~

o.2 "x,,~,, /
Pe : ( 1 kHz, 0BAIt

I ,
o I ii /
0.85 0.9 0.95 1.0 ,0 ,~ 2~ 2~ 30 35
Co/(Fe.Co) B ~

Fig. 29. Permeability of (Co,Fe)70(SI,B)30 alloys,
as quenched (]2eAQ~or heat treated at 450 °C and
water quenched (]2eHT) in a combined pseudobinary
diagram [43 ].
stant along the zero-magnetostriction com-
position line but is dependent on the ratio
of silicon to boron. Since the Curie tem-
perature and magnetization stay more or
less constant along this line, the origin of
this variation in/% must be sought in the
degree of structural inhomogeneity in the
alloy. As shown in Fig. 2, replacing boron
by silicon drastically increases T~ and simul-
taneously decreases the critical cooling rate,
making it easier to produce the alloy. It is
most likely that this increase in the glass-
forming tendency directly causes Pe to be a
m a x i m u m near the composition Sio.4Bo.s.
Furthermore, the ratio between the per-
meability pe HT after heat treatment and the
as-quenched permeability /%AQ is less than
10 for (Co,Fe)voB3o alloys but is more than
20 for (Co,Fe)70 (Sio. a Bo. e )3o alloys, indicat-
,o s,
Si /,//'~"~'~500"-"'03--..~
/ ~/ !,,~__,~--T'-~,o~'...~._...
f'-"¢-¢--~-~,o, ~ ~"C-V °
v----.--.:~,
\ m u m when the concentrations of the two
v / i /
10 15 20 25
B ---.-~.
Fig. 30. Permeability of the Co-B-Si system after heat
treatment to maximize Pe (-- " --) shown together
with T c (°C) ( ) (1 kHz; 10 mOe) [41].
Fig. 31. Permeability/2 e (-- • --) and crystallization
temperature T x (°C) ( ) in the C o - B - S i system
(1 kHz; 10 mOe) [41].
ing that the increased glass-forming tendency
is also concomitant with the better response
to annealing. Similar results for the Co-B-Si
system are given in Figs. 30 and 31. In the
central portion of the glass-forming region,
Pe is related to Tc; however, near the bound-
ary the value of Pe rapidly decreases, accom-
panied by a decrease in Tx.
4.4. Embrittlement and composition
The embrittlement behavior is also com-
position dependent, in both direct and in-
direct ways. As has been mentioned earlier,
the embrittlement occurs only when the alloy
contains transition metals with unfilled d
bands, and in that sense it is directly com-
position dependent. However, the composi-
tion influences the embrittlement behavior
also in a more indirect way. Figures 32 and
33 [75] show for some iron-base alloys the
metalloid composition dependence of the
85 embrittling temperature TB which is the
annealing temperature at which the alloy
becomes brittle after a specified time (2 h)
and should not be confused with the ductile-
Co
to-brittle transition temperature discussed
earlier. In general, TB is slightly increased by
the addition of the second metalloid element
but is decreased afterwards to reach a mini-
metalloid elements are about the same. A
similar behavior was observed on alloying the
/ / metal elements [69]. The initial rise in TB is
30
best explained by the increased tendency of
glass formation by alloying the third element.
As shown in Fig. 2, Tx is increased, and the
ease of amorphous alloy formation is also

700
600
500
0
, J i i
10
,i, ~"~0
X
Fig. 32. D e p e n d e n c e o f embrittling t e m p e r a t u r e TB
o n the m e t a l l o i d c o m p o s i t i o n of the F e s 0 P 2 0 _ x M x
alloys [ 75 ].
700
,~ 600
Be
500
10 20
X amorphous alloys is their mechanical prop-
Fig. 33. D e p e n d e n c e o f T B on t h e m e t a l l o i d composi-
tion o f the F e s 0 B 2 0 _ x M x alloys [75 ].
improved. This increase in the glass-forming
t e n d e n c y results in a higher density of defects
in the alloy and thus an increase in ductility.
However, if the concentrations of the t w o
metalloid elements b e c o m e comparable, the
CSRO b e t w e e n them starts to provide resis-
tance to the flow of atoms, or defects, just
as in ordered crystalline alloys. A metalloid
element probably has no other metalloid
as a nearest neighbour [ 7 6 ] , b u t the composi-
tion of the metalloid in the second nearest-
neighbour shell can be quite important for
the stability of the alloy. If the metalloid
a t o m prefers to have like atoms there, it
signals a t e n d e n c y to phase separation. If
unlike atoms are preferred, the mixture of
metalloids will provide a more stable amor-
phous state. The composition dependence of
Tx indicates that the latter case m a y be more
likely. In either case, however, mechanical
deformation must disturb the CSRO b e t w e e n
metalloids, and it costs additional energy of
deformation. Therefore the mixture of
metalloid elements, and also often metal
elements, results in a reduction in TB. Further-
161
more, the improved atomic packing when a
mixture of metalloid elements is used may
well result in a decrease in the activation
volume of the defects. This can also cause
a reduction in TB.
Thus, as has been illustrated in the two
examples above, the composition of the alloy
can affect the properties and the thermal
behavior of the amorphous alloy, not only
through a direct chemical or physical effect
b u t also through the structural short-range
order.
5. A P P L I C A T I O N A N D A L L O Y D E S I G N
5.1. High permeability alloys
For application in electronic devices such
as tape recorder heads or current leak detec-
tors, an alloy has to have a high permeability
over a wide frequency range, at least above
104 up to 1 kHz. At present, there is little
choice b u t to use zero-magnetostriction
alloys for this purpose. They contain a high
concentration of cobalt and are therefore
expensive. However, the special merit of
erties. For the tape recorder head application,
C o - F e - B - S i alloys are quite well suited
because of their excellent wear resistance, as
shown in Fig. 34 [77]. Other combinations
of metalloid elements result in less effective
wear resistance. The superiority of the Si-B
combination is due to its high value of Tx
and high hardness. The surface of a tape re-
corder head can be heated significantly
locally during use so that, if the composition
is inappropriate, embrittlement or even partial
~ f ol
30 o~PerrnaUoy Core
~ 2o
N lo
Fe~oP13C?
AmorphOUS
~
MnZn Ferr ire
50 100 150 200 300
Test time, h
Fig. 34. Tape recorder head wear of various materials
in use at 19 era s - 1 w i t h 7 - F e 2 0 3 tape and a back
tension o f 300 gf [77 ].
162
surface crystallization can occur, contributing
to the flaking-off of the surface.
In choosing the composition, it is most
important to make Tc significantly below
Tx, so that it is possible to anneal above
Tc. As shown in Figs. 30 and 31, in cobalt-
base alloys Tc is above T~ unless the metal-
loid content is more than about 25%. The
addition of chromium, m o l y b d e n u m , vana-
dium or tungsten reduces Tc drastically
[5, 78] and it was found that this increases Pe
m o r e effectively than increasing the metalloid
c o n t e n t does. The value of pe after annealing
exceeds 2 X 105 as shown in Fig. 35 [42].
The favorable effect o f m o l y b d e n u m is known
[ 7 9 ] , but the reason for it is unclear.
Probably the most disturbing problem with
the use o f the amorphous alloys as high per-
meability materials is the aging effect. This is
particularly severe in the tape recorder head
application. One of the solutions is, as men-
tioned earlier, to reduce Tc. This, however,
has the undesirable consequence of lowering
the r o o m temperature magnetization. An-
other solution is to try to design a composi-
tion and heat t r e a t m e n t which reduce the
short-range diffusivity. Unfortunately, very
little work reported to date aids in attempt-
ing such a design. A systematic study of the
after-effect is awaited.
For other applications such as magnetic
shielding and small transformers the per-
,,~fle
0 5 0 ~ 4 , ~ 0 2
'/,,
Fig. 35. Permeability of zero-magnetostriction
(~ks= 0) (Co,FeJVI)TsSisB14 after heat t r e a t m e n t s
[ 4 2 ] : o, M ~ V ; A , M =- C r ; O , M o ; " , M ~ W.
meability requirement is less severe, and it
is possible to use Fe-Ni-base alloys which
are less expensive than cobalt-base alloys.
In particular the Deltamax-type crystalline
alloys (FesoNis0) could be replaced by iron-
base amorphous alloys which m a y be lower in
cost, are easier to handle and have higher
permeabilities.
5. 2. High magnetic induction alloys
The requirement for a power transformer
core material is that it has a high msgnetic
flux density, in addition to low magnetic
losses. When a material with a low saturation
induction is used for a core, we need a larger
core and therefore a larger copper winding,
which means a higher production cost and a
higher resistivity loss. At present, the room
temperature saturation induction B s above
17 kG has been reported only for F e - B - C
alloys [80] while other iron-base alloys have
values of Bs around 16 kG [64]. The F e - B - C
alloys, however, are difficult to produce, and
the alloys with a low concentration of iron
(below 82%) show a slight aging effect even at
room temperature. To improve these deficien-
cies, silicon is added [81]. The F e - B - C - S i
system is stable and easy to produce and has
very low values of magnetic loss.
F e - B - S i alloys have slightly lower values of
saturation magnetization; nevertheless t h e y
are much superior to other iron-base alloys
in terms of stability and ease o f production
[64]. They may well be the best alloys for
mass production of devices when all the prac-
tical factors are considered.
There are still a n u m b e r of problems to be
overcome before these alloys can be used in
power transformers, particularly because the
technology of grain-orientated Si-Fe is very
advanced and heavily invested in; it is there-
fore not easy for any new materials to replace
it. One problem is the stacking factor. Because
of the uneveness of the surfaces, the stacking
factor of the as-quenched amorphous ribbons
hardly reaches 85%. Here, however, a know-
ledge of annealing behavior may be of great
help. For instance, h o t rolling at temperatures
slightly below Tg followed by cooling under
tensile stress could improve both the surface
quality and the magnetic properties. Since the
market for power transformers is huge and the
cost of energy is steadily increasing, research
in this field is expected to become more active.

5. 3. Corrosion-resistan t alloys
Corrosion-resistant magnetic alloys would
be of great value in some applications, such as
in high gradient magnetic separation. Amor-
phous alloys containing chromium and phos-
phorus are much superior to magnetic stain-
less steels which are at present used as a par-
ticle-collecting material for magnetic separa-
tion [ 8 2 ] . It is found that the ribbon shape of
the sample is advantageous for this application
because of the large field gradient near the
edge of the ribbon [82]. For applications in
electronic devices, n o t only a higher magneti-
zation b u t also a high permeability is required.
As shown in Fig. 35, the cobalt-base alloys
with chromium or m o l y b d e n u m have very
high permeabilities. Although similar research
on alloys containing both phosphorus and
chromium or m o l y b d e n u m is incomplete,
it appears to be possible to develop highly
corrosion-resistant high permeability alloys.
Such alloys with excellent mechanical proper-
ties may prove to be valuable for use in various
devices. The addition of chromium or molyb-
denum, however, significantly reduces the sat-
uration magnetization [5, 6 1 ] , so that these
alloys are n o t suited for applications which
require very high induction.
5.4. Magne tomechanical applications
As has been discussed earlier, some iron-
base amorphous alloys show Invar and Elinvar
characteristics at r o o m temperature. It is
easily recognized that the Invar behavior is pri-
marily dependent only on composition and is
little affected by heat treatment, while the
Elinvar behavior is much more sensitive to heat
treatment since it is dependent on the magni-
tude of the permeability and the elastic mod-
uli, b o t h of which are changed b y annealing.
Therefore by an appropriate heat treatment
it is possible to produce an alloy which shows
both Invar and Elinvar characteristics at the
same time. Furthermore, the addition of chro-
mium makes the alloy corrosion resistant. An
alloy designed according to this logic,
(Fe0.e2Cr0.os)ssBz5 , shows both Invar and
Elinvar characteristics after heat treatment
and a corrosion resistance as good as the crys-
talline Invar alloy Fe~Nia~ or the Elinvar
alloy Fe55Nia6Cr 9 [ 4 6 ] .
The AE effect in the amorphous alloys is
generally quite large owing to the high mag-
netic permeability. This leads to various appli-
163
cations such as variable-delay lines [83] or
stress sensors [84]. A high yield stress and a
low acoustic loss [85] are further advantages
in this application. Factors to be considered
in designing alloys for such applications are,
in addition to the magnetostriction and per-
meability for magnetization rotation which
determine the magnetomechanical coupling
factor, the embrittlement and aging effects.
Si-B-base alloys with high concentrations of
metalloids are again preferred for these reasons.
ACKNOWLEDGMENTS
Part of this research was supported by the
Electric Power Research Institute under Con-
tract RP-932-1. One of the authors (T.E.)
acknowledges the hospitality of the Max-
Planck-Institut fiir Metallforschung during his
sabbatical leave.
REFERENCES
1 P. Duwez, Annu. Rev. Mater. Sci., 6 (1976) 86.
2 J. J. Gilman and H. J. Leamy (eds.), Metallic
Glasses, American Society for Metals, Metals Park,
OH, 1977.
3 H. S. Chen, Rep. Prog. Phys., 43 (1980) 353.
4 T. Masumoto and R. Maddin, Mater. Sci. Eng., 19
(1975) 1.
5 C. D. Graham, Jr., and T. Egami, Annu. Rev.
Mater. Sci., 8 (1978) 423.
6 F. E. Luborsky, P. G. Frischmann and L. A. John-
son, J. Magn. Magn. Mater., 8 (1978) 318.
7 D. Turnbull and M. H. Cohen, J. Chem. Phys., 34
(1961) 120.
8 D. R. Uhlmann, J. Non-Cryst. Solids, 7 (1972)
337.
9 H. A. Davies, J. Aucote and J. B. HuH, Scr.
Metall., 8 (1974) 1179.
10 B. C. Giessen,J. Hong, L. Kabacoff, D. E. Polk,
R. Ramanand R. St. Amand, in B. Cantor (ed.),
Proc. 3rd Int. Conf. on Rapidly Quenched Metals,
Brighton, 1978, Vol. 1, Metals Society, London,
1978, p. 249.
11 I. W. Donald and H. A. Davies, J. Non-Cryst.
Solids, 3ff(1978) 77.
12 M. Naka and T. Masumoto, Sci. Rep. Res. Inst.,
Tohoku Univ., Set. A, 27 (1979) 118-
13 A. Inoue, T. Masumoto, S. Arakawa and T. Iwa-
dachi, in B. Cantor (ed.), Proc. 3rd Int. Conf. on
Rapidly Quenched Metals, Brighton, 1978, Vol. 1,
Metals Society, London, 1978, p. 265.
14 M. Hagiwara, A. Inoue and T. Masumoto, unpub-
lished data, 1980; Annu. Meet. o f Japan Institute
o f Metals, 1980.
164
15 M. Naka, S. Tomizawa, T. Watanabe and T. Masu-
moto, in N. J. Grant and B. C. Giessen (eds.),
Proc. 2nd Int. Conf. on Rapidly Quenched Metals,
Cambridge, MA, 1975, Vol. 1, Massachusetts In-
stitute of Technology Press, Cambridge, MA,
p. 273.
16 J. Balogh, I. D6zsi, B. Fogarassy, L. GrSnfissy, D.
L. Nagy, I. Vincze and S. Arajs, J. Phys., Colloq.
I, Suppl. (1980) C1-253.
17 H. S. Chen, Acta MetaU., 24 (1976) 153.
18 J. J. Gilman, J. Appl. Phys., 46 (1975) 1625.
19 L. A. Davies, in J. J. Gilman and H. J. Leamy
(eds.), Metallic Glasses, American Society for
Metals, Metals Park, OH, 1977.
20 T. Masumoto, Sci. Rep. Res. Inst., Tohoku Univ.,
Ser. A, 26 (1977) 246.
21 T. Minemura, Thesis, Tohoku University, 1977.
22 T. Masumoto, K. Hashimoto and M. Naka, in B.
Cantor (ed.), Proc. 3rd Int. Conf. on Rapidly
Quenched Metals, Brighton, 1978, Vol. 2, Metals
Society, London, 1978, p. 435.
23 K. Hashimoto, M. Naka, J. Noguchi, K. Asami
and T. Masumoto, Proc. 4th Int. Syrup. on Passiv-
ity, Aerie, 1977, Electrochemical Society, Prince-
ton, NJ, 1977, p. 156.
24 K. Hashimoto, M. Naka, K. Asami and T. Masu-
m o t o , Boshoku Gijutsu, 27 (1978) 279.
25 M. Naka, K. Hashimoto and T. Masumoto, J.
Non-Cryst. Solids, 28 (1978) 403.
26 M. Naka, K. Hashimoto and T. Masumoto, J.
Non-Cryst. Solids, 31 (1974) 355.
27 T. Masumoto and H. Kimura, Sci. Rep. Res. Inst.,
Tohuku Univ., Ser. A, 27 (1979) 172.
28 F. E. Luborsky, in Encyclopedia o f Chemical
Technology, Vol. 2, Wiley, New York, 1979,
p. 537.
29 R. Hasegawa and R. Ray, J. Appl. Phys., 49
(1978) 4174.
30 R. Hasegawa and R. Ray, J. Appl. Phys., 50
(1979) 1586.
31 M. Mitera, M. Naka, T. Masumoto, N. S. Kazama
and K. Watanabe, Phys. Status Solidi A, 49
(1978) K163.
32 M. Mitera and T. Masumoto, unpublished data,
1978.
33 N. S. Kazama, M. Mitera and,T. Masumoto, in B.
Cantor (ed.), Proc. 3rd Int. Conf. on Rapidly
Quenched Metals, Brighton, 1978, Vol. 2, Metals
Society, London, 1978, p. 164.
34 K. Fukamichi, M. Kikuchi, S. Arakawa and T.
Masumoto, Solid State Commun., 23 (1977) 955.
35 T. Egami, J. Appl. Phys., 50 (1979) 1564.
36 M. Mitera, N. S. Kazama and T. Masumoto, J.
Magn. Magn. Mater., 15 - 18 (1980) 1331.
37 H. S. Chen, R. C. Sherwood and E. M. Gyorgy,
IEEE Trans. Magn., 13 (1977) 1 5 3 8 . .
38 R. O'Handley, Phys. Rev. B, 18 (1978) 930.
39 R. C. Sherwood, E. M. Gyorgy, H. S. Chen, S. D.
Ferris, G. Norman and H. J. Leamy, AIP Conf.
Proc. 24 (1975) 745.
40 T. Jagielinski, K. I. Arai, N. Tsuya, S. Ohnuma
and T. Masumoto, IEEE Trans. Magn., 13 (1977)
2553.
41 S. Ohnuma, K. Watanabe and T. Masumoto, Phys.
Status Solidi A, 44 (1977) K151.
42 S. Ohnuma and T. Masumoto, J. Appl. Phys., 50
(1979) 7597.
43 S. Ohnuma and T. Masumoto, in B. Cantor (ed.),
Proc. 3rd Int. Conf. on Rapidly Quenched Metals,
Brighton, 1978, Vol. 2, Metals Society, London,
1978, p. 197.
44 K. Fukamichi, T. Masumoto and M. Kikuchi,
IEEE Trans. Magn., 15 (1979) 1404.
45 B. S. Berry and W. C. Pritchet, Phys. Rev. Lett.,
34 (1975) 1022.
46 M. Kikuchi, F. Fukamichi and T. Masumoto, Sci.
Rep. Res. Inst., Tohuku Univ., Ser. A, 27 (1979) 210
47 T. Egami, Mater. Res. Bull., 13 (1978) 557.
48 T. Egami, K. Maeda and V. Vitek, Philos. Mag.
A, 41 (1980) 883.
49 T. Egami, J. Mater. Sci., 13 (1978) 2587.
50 Y. Waseda and T. Egami, J. Mater. Sci., 14 (1979)
1249.
51 H . H . Liebermann, C. D. Graham, Jr., and P. J.
Flanders, IEEE Trans. Magn., 13 (1977) 1541.
52 Y.-N. Chen and T. Egami, J. Appl. Phys., 50
(1979) 7615.
53 H. S. Chen, L. C. Kimerling, J. M. Poate and W.
L. Brown, Appl. Phys. Lett., 32 (1978) 461.
54 P. M. Anderson III and A, E. Lord, Mater. Sci.
Eng., 44 (1980) 279.
55 F. E. Luborsky, J. J. Becket and R. O. McCary,
IEEE Trans. Magn.
56 T. Egami and P. J. Flanders, AIP Conf. Proc. 29
(1976) 220.
57 H. Fujimori, Y. Obi, T. Masumoto and H. Saito,
Mater. Sci. Eng., 23 (1976) 281.
58 F E. Luborsky and J. L. Walter, IEEE Trans.
Magn., 13 (1977) 953.
59 H. Fujimori, H. Morita, Y. Obi and S. Ohta, in
R. A. Levy and R. Hasegawa (eds.), Amorphous
Magnetism II, Plenum, New York, 1977, p. 393.
60 J. J. Becket, IEEE Trans. Magn., 14 (1978) 938.
61 F. E. Luborsky and J. L. Walter, Mater. Sci. Eng.,
28 (1977) 79.
62 W. Chambron and A. Chamberod, Solid State
Commun., 33 (1980) 157.
63 H . J . Leamy, E. M. Gyorgy, R. C. Sherwood, T.
Wakiyama and H. S. Chen, A I P Conf. Proc. 29
(1976) 211.
64 H. Fujimori and T. Masumoto, Sci. Rep. Res.
Inst.,Tohoku Univ., Set. A, Suppl., 26 (1978)181.
65 H. Fujimori, S. Ohta, T. Masumoto and K. Naka-
moto, in B. Cantor (ed.), Proc. 3rd Int. Conf. on
Rapidly Quenched Metals, Brighton, 1978, Vol. 2,
Metals Society, London, 1978, p. 232.
66 N. Moser and Kronmiiller, J. Magn. Magn. Mater.,
19 (1980) 275; personal communication, 1980.
67 K. Ohta, T. Matsuyama, M, Kajiura and T. Tera-
nishi, J. Magn. Magn. Mater., 19 (1980) 165.
68 J. L. Walter, F. Bacon and F. E. Luborsky, Mater.
Sci. Eng., 24 (1976) 239.
69 H. S. Chert and K. A. Jackson, in J. J. Gilman and
H. J. Leamy (eds.), Metallic Glasses, American
Society for Metals, Metals Park, OH, 1977, p. 174.
70 J. L. Walter and F. E. Luborsky, Mater. Sci. Eng.,
33 (1978) 91.
71 H. S. Chen, Scr. Metall., 11 (1977) 367.
72 R. S. Williams and T. Egami, in B. Cantor (ed.),
Proc. 3rd Conf. on Rapidly Quenched Metals,

Brighton, 1978, Vol. 1, Metals Society, London,
1978, p. 214.
73 R. S. Williams and T. Egami, unpublished, 1979.
74 A. Inoue, T. Masumoto and H. Kimura, Sc£ Rep.
Res. Inst., Tohoku Univ., Ser. A, 27 (1979) 159.
75 M. Naka, T. Masumoto and H. S. Chen, J. Phys.,
Colloq. 8, Suppl., 41 (1980) C8-839.
76 Y. Waseda, H. Okazaki and T. Masumoto, J.
Mater. Sci., 12 (1977) 1927.
77 Y. Makino, K. A,so, A. Kamidaira and M. Itoh,
Rep. 78-01, 1978 (in Japanese) (Sony Research
Center).
78 T. Mizoguchi, K. Yamanchi and H. Miyajima, in
H. O. Hooper and A. M. de Graaf(eds.),Amorphous
165
Magnetism, Plenum, New York, 1973, p. 325.
79 R. Hasegawa, M. C. Narasimhan and N. DeCristo-
faro, J. Appl. Phys., 49 (1978) 1712.
80 S. Hatta, T. Egami and C. D. Graham, Jr., Appl.
Phys. Lett., 34 (1979) 113.
81 M. Mitera, T. Masumoto and N. S. Kazama, J.
Appl. Phys., 50 (1979) 7609.
82 Densoken News 350, 1979 (in Japanese).
83 K. I. Arai and N. Tsuya, J. Appl. Phys., 49 (1978)
1918.
84 K. Mohri and S. Korekoda, IEEE Trans. Magn.,
14 (1978) 1071.
85 M. Dutoit and H. S. Chen, Appl. Phys. Lett., 23
(1973) 357.