JOURNAL OF

ELSEVIER Journal of Non-Crystalline Solids 204 (1996) 32-37

The study of relaxational properties and crystallization of the

metallic glass Fe80Si l0B 10
Predrag Tomid a, Milorad Davidovid b,c,,
a Institute of Materials, Zvornik, Republic of Srpska
b Vin~a Institute of Nuclear Sciences, Vinca, PO Box 522, 11001 Belgrade, Yugoslavia
c Faculty of Electrical Engineering, PO Box 816, llO01 Belgrade, Yugoslavia

Received 1 January 1995; revised 24 October 1995

Abstract

The three-component amorphous alloy FesoSi~oB 10 was prepared on the surface of copper roller by rapid quenching in
the vicinity of the eutectic point. Changes of the obtained spin-glass metastable phase were investigated by differential
scanning calorimetric analysis (DSC), as a function of the relaxation temperature, and by X-ray diffraction (XRD)
measurements, in the crystallization phase of the metallic glass. The crystallization kinetics and the corresponding activation
energies, E a, were determined using the dynamic thermal treatment. For the study of the crystallization process, the XRD
measurements were done before and after crystallization. On the basis of these data, the products of the investigated metallic
glass crystallization have been determined. The Curie temperature of the ferromagnetic transition has been determined from
the DSC measurements in the low temperature region. The Johnson-Melh-Avrami dynamic model for non-isothermal
conditions, and the DSC measurements were used for determination and definition of the parameter n, responsible for the
mechanism of crystallization, whereas the Vogel-Fulcher model for isothermal conditions and the DSC measurements were
used to determine the characteristic time of crystallization, r(t). The obtained results for E a, n and r(t) are in good
agreement with other authors' results.

1. Introduction called metallic glasses. Combination of amorphous

Amorphous metals are in a non-equilibrium
metallic solid state, in contrast to the crystalline
state, which is the state of smallest internal energy
for metals, with a structure similar to that of frozen
(undercooled melt) liquid metals. When produced by
ultrarapid quenching from melt, they are usually
* Corresponding author. Tel.: + 381-11 444 0871 ; fax: + 381-11
444 0195; e-mail: edavidmi@ubbg.eff.bg.ac.yu.
structure and metallic bond gives a new quality
which cannot be found in pure metals and regular
glasses. The new quality is a combination of differ-
ent properties that make a metallic glass interesting
for possible applications. Stability, an important fac-
tor of amorphous metallic structures, is related to
relaxation phenomena and crystallization, which is
usually a thermally activated process of transition
from a disordered amorphous structure to an ordered
crystal structure. Studying the low-temperature relax-
ations it is possible to determine the Curie tempera-

0022-3093/96/$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved.

PII S 0 0 2 2 - 3 0 9 3 ( 9 6 ) 0 0 1 9 3 - 7
 P. TomiL M. Davidovi(/Journal of Non-C~stalline Solids 204 (1996) 32-37
ture of the ferromagnetic transition and observe its
functional correlation with the relaxation mecha-
nisms, i.e., to determine the optimal low-temperature
treatment for ferromagnetic amorphous ribbons [1].
Investigating crystallization phenomena, which are
related to the activation energy, E,, of crystalliza-
tion, i.e., parameters related to the crystallization
dynamics, such as n, responsible for the mechanism
of crystallization or r(t), characteristic time of crys-
tallization, it is possible to evaluate the thermal
stability of amorphous metals and the life-time of the
glass state at different temperatures.
Transformations in solids and, accordingly crys-
tallization of metallic glasses, can be described by
the JMA (Johnson-Melh-Avrami) kinetic model in
non-isothermal conditions [2,3] as
da/dt=An(1 - a)[-ln(l - ol)] " - ' / "
× exp( - E J R T ) , (1)
where a is the transforming fraction, t is time, T is
absolute temperature, R is the gas constant and A is
the pre-exponential factor. Combining the JMA
model with Kissinger's method for determination of
activation energies, E a [4]:
ln(TmZ//3 ) = Ea/RT-'~ C, (2)
where Tm is the maximal temperature which corre-
sponds to the maximum of the reaction, i.e., when
d(dol/dt)dt= 0 and /3 is the heating rate d a / d t .
E a and the coefficient n can be simultaneously deter-
mined. Using the method suggested by Kissinger,
where the experimental results are plotted as
In(Tin2//3 ) against I / T m, straight lines with the coef-
ficient EJ R are obtained. These lines are called
Kissinger's directions. From the JMA model, pre-
sented by equation [2], applying Doyl's approxima-
tion [5,6], one obtains
In[In( 1/1 - a ) ] = n ln(AE,//3R)
+ 5.33n - 1.05nEa/RT. (3)
Thus, drawing In[-ln(1 - a)] against 1 / T one gets
directions with the coefficient nEa. With a given
value of E~, it is easy to determine the coefficient n.
Using the combination of the Arrhenius and Vogel-
Fulcher equation, which are systematically given in
[7], the time of crystallization, ~-(t), is determined as
follows:
~.-I= ~'o' exp[ E a / k B ( T - T~)], (4)
33
where ~" is the time of crystallization, r 0 is the
characteristic time of crystallization, k B is the Boltz-
mann constant and Tg is the glass transition. Given
the activation energy, the characteristic time of crys-
tallization in isothermal conditions can be deter-
mined, and the obtained values compared to those of
dynamic relaxation conditions in metallic glasses.
X-ray diffractograms of recently obtained amor-
phous alloys show a broad maximum, characteristic
for amorphous structure, whereas the absence of
sharp crystalline peaks indicates that the cooling
rates during experimental processing of metallic
glasses were sufficiently high to prevent crystalliza-
tion [1,8,9]. It is therefore necessary to check by
XRD measurements the quality of the ribbons. The
same method is applied to determine the type of
crystallization of metallic glass.
2. Experimental procedures
The amorphous Fes0Si~0B~0 made in vacuum by
alloying of highly pure initial elements, was melted
inductively in a furnace under an He overpressure.
The melt was processed in the form of metallic
ribbons by ultra-rapid cooling on the surface of a
rotating copper wheel, whose peripheral speed was
changed from 25 to 30 m / s . The ribbons were about
3 mm wide and 15-25 ~m thick, depending on the
wheel speed. X-ray diffraction studies have been
done on a Philips APD 1700 automated diffractome-
ter to verify amorphous structures and determine the
products of crystallization. Diffraction data were col-
lected in the 0~c scattering angle (Osc= 20 B, where
0 B is the Bragg angle) range from 5 to 70 °, by
counting for 2 rain at each 0.2 ° 0s~ step. The radia-
tion source was Cu K s , with wavelengths 0.15406
and 0.154439 nm. The thermal investigations of the
samples weighing 10-20 rag, in the protective argon
atmosphere, were performed using a Perkin-Elmer
DSC-4 calorimeter, and also showed the samples to
be amorphous. Kinetics of crystallization was ana-
lyzed by dynamic thermal treatment, at scanning
rates 5, 10, 20, 40, 80 K/rain, in the interval 50-
590°C. The calorimeter sensitivity was adjusted to
the sample weight in order to get the optimal calori-
metric measurements. Processing of the differential
scanning calorimetry (DSC) data was done on
Perkin-Elmer TADS DSC-4 Advanced Software.
34 P. Tomi(, M. Davidovid / Journal of Non-C~'stalline Solids 204 (1996) 32-37

3. R e s u l t s
8,0i
--___~esoB,0Si,0
Fig. 1 shows the X-ray diffractogram of amor-
phous alloys as a function of 0~c. The wide diffrac-
tion maximum, characteristic of an amorphous struc-
ture, indicates that during the experimental process- ,<
v!
4,0 -~ ~ M ~~
I
382,42
(9

ing of ribbons the quenching rates were sufficiently ----._ O)

high, i.e., that the sample was made completely
amorphous.
Estimation of the cooling rate was done through
analysis of the Newton cooling of solution on the
substrate [ 10,11] according to the relation
d T / d t = V(CpAT+ mg)//gCp.
dT/dt is the cooling rate, v is the linear speed of the
wheel surface, Cp is the specific heat of the melt, AT
is the temperature difference between the melt and
surface, A H is the latent melting temperature of
melt material and L is the length of the melt and
surface contact zone. According to Ref. [ 12]
In R = In R c - b / ( T m -- Tx.c) 2,
where R is the heating rate, R~ is the critical cooling
rate, b is the characteristic constant, Tm is the melt-
ing temperature and T~, is the temperature of solidi-
fication. According to the values obtained for these
parameters, the cooling rates were found to be 105 to
l06 K / s , which are the values necessary for the
applied processing technique for metallic amorphous
systems [ 13,14].
At low-temperature relaxation of the metallic glass
FesoSilo B10, the Curie temperature of the ferromag-
netic transition is determined, and it can be noticed
that it is dependent on the heating rate and previous
thermal relaxation. Fig. 2 shows that the Curie tem-
perature of the ferromagnetic transition determined
from the DSC thermograms is 382°C (655 K), and is
i * 40 M , 203
' ~l - 20 K/min
i , i
0,O~ 360 370 380 '90 400 T/°C
Fig. 2. The Curie temperature of the ferromagnetic alloy
Fe80 Sit 0 B m, determined at different heating rates.
(5)
not dependent on the cooling or heating rate. After
thermal relaxation at temperatures 10-20 K below
655 K, the Curie temperature is increased by several
K, which points to the fact that the metallic glass has
relaxed from a less stable to a more stable amor-
phous state.
Heating of the metallic glasses leads to crystal-
lization and releasing of excess of free energy in
(6)
disordered amorphous structure compared to the cor-
responding crystal structure. Observing the DSC
crystallization kinetics of the investigated metal glass,
two exothermic peaks are noted, corresponding to
the formation of two different phases during crystal-
lization. In contrast to the amorphous state, the
diffractogram of the crystalline sample shows sharp
peaks, characteristic for the corresponding crystal
phases of the treated samples. Considering that
Fe80SiloB10 belongs to the hypo-eutectic region of
Fe-Si-B metal glasses (region rich with Fe) and by
inspecting the diffractogram of crystallized
Fe80 Si l0B 10 metal glass (Fig. 3), we identify phases
that are formed during the crystallization process.
This identification can be accomplished by using
JCPDS - International Center for Diffraction Data
[15] and the diffraction picture so that a-(FeSi) and

,.->
<L
20O

150
X-RAY: Cu-Kot
.4 80
I Sample: Fes0Si10B10 ~ _

100'
40
Z
5o
z
20 40 80 20
0
25 45 65 85 105 0sc
Fig. 3. X-ray diffractogram of the amorphous alloy Fe8oSiloBio
Fig. 1. X-ray diffractogram of the starting alloy FesoSiloBio. after the thermal treatment and crystallization.
 P. Tomi(, M. Davidovi( / Journal of Non-Crystalline Solids 204 (1996) 32-37 35

200,0 I DSC:FesoBl0Sil0
TmI I 15,~[ Tin2 , / T m I
~ ~ ~--~ ~min
;~ i (~) 13=10K/min
~= 14'00i
l 0O.0
®
<~
13,00? /'=332 KI/mol 7 E1=354KI/mol
® 1,16 1,20 1,24 1,28 1,32
0,0 (1/T).10-3 (l/K)
300 400 500 T/°C
Fig. 5. Kissinger's plots for some phases of crystallization. The
Fig. 4. Crystallization thermogram of the metallic glass curves are fits of the data to a linear function, ln(T2/~)= A +
FesoSiloBio. 8/T.

Fe3B phases can be identified as products of the

crystallization process. These products mean that the ture Tm,, i.e., Tin: as a function of a, one obtains
crystallization of Fe80Sii0B]0 takes place in two data from which it is possible to calculate activation
phases. First, ct-(FeSi) is formed and only at higher energies for different phases of crystallization [4,17-
temperatures complete crystallization takes place 19] according to Eq. (2). Experimental data for the
through the formation of the Fe3B phase. These calculation of activation energies for different crys-
results agree with the results of analogous investiga- tallization stages are given in Table 1. Experimental
tions [16]. It should be pointed out that in both cases data, if plotted as l n ( T 2 / f l ) versus 1 / T , give straight
the crystallization process is irreversible. lines with slopes E J R , which gives the possibility
The intensity of the crystallization peak and the to calculate the activation energy, E a. The obtained
temperature at which it is formed on DSC, depend straight lines, called Kissinger plots, are shown in
on the heating rate, type and weight of the sample Fig. 5. The calculated values of activation energy are
and the instrument sensitivity. Fig. 4 presents the in agreement with the results of other authors about
crystallization thermogram of the studied metallic the crystallization behavior of FesoBl0Si]0 glass
glass, on which pronounced peaks corresponding to [20-22], which are obtained also by thermal or
certain temperatures are observed. It is seen that the dilatometric analyses.
values of the crystallization temperature are depen-
dent on the heating rate.
Varying the sample heating rate, a, on the DSC 4. Discussion
changes the position of crystallization peaks as a
function of the increase of the temperature of crystal- It is very interesting to prove the obtained relation
lization, i.e., with increasing the heating rate. From for simultaneous calculation of activation energy, E a,
that, by using appropriate dynamic treatment and and coefficient n, responsible for the crystallization.
following the changes of the crystallization tempera- The method of simultaneous determination of E a and
n, which determines the crystallization mechanism,
has not been so far applied in investigation of F e - S -
Table 1
Experimental data for calculation of activation energies of crystal-
B metal glasses. Plotting l n [ - l n ( 1 - a ) ] against
lization 1 / T , we should obtain straight lines with slope nE a,
/3 (K/s) T~, Tm~ as in Eq. (3). The value of activation energy being
known it should be then possible to determine the
T(K) ln(T2/fl) T(K) ln(T2/fl)
value of n. The results obtained in the way are
0.166 774.0 15,099 805.3 15.178 shown in Fig. 6. As the coefficient of the straight
0.333 782.4 14.424 815.6 14.507
0.666 792.1 13.576 827.0 13.842 line is nE a = 814.20 kJ/mol, n = 2.3, with activa-
1.333 803.0 13.089 839.1 13.177 tion energy E a = 354 kJ/mol. This value for n is in
good agreement with results already obtained in Ref.
36 P. TomiL M. Davidovig / Journal of Non-Crystalline Solids 204 (1996) 32-37

-0,8!i Table 2
The values r~ tor the investigated observed alloy
-0,9 T (K): 370 420 470 520 570 620 670
7e (s): 1027 1021 1017 1013 101° 107 105

-t ,0

! NE=814,20
-1,1 = n=2,3
1.00 1,10 120 1,30
10ootr (l/K)
Fig. 6. l n [ - l n ( 1 - a)] as a function of 1 / T for the examined
metal glass at a heating rate 10 K / s . The curves are a fit of the
data to a linear function, l n [ - l n ( l - a ) ] = C + D / T .
[6,23], where the value of n was determined by
isothermal measurements. The value n = 2.3 sug-
gests a diffusion controlled three-dimensional crys-
tallization mechanism. This result could have been
expected since we are dealing with a metal glass
with low metalloid content. The result obtained for
the activation energy, E, = 354 kJ/mol, points out
high thermal stability of this metal glass, which
makes it attractive for technological applications.
The characteristic time of crystallization, r(t),
was determined by the Vogel-Fulcher relation, Eq.
(4). By isothermal measurements at several charac-
teristic temperatures, the characteristic time of crys-
tallization z(t) at appropriate temperature is calcu-
lated. Having the values for the activation energy of
crystallization of the investigated system and for the
time of isothermal crystallization at the same temper-
atures we obtained the value %, shown in Fig. 7.
By the measurements, %1 = 2.67 × 10 -1° s -1 is
obtained, which is in good agreement with results in
2O,O00
i ,
16,000
12,o00~
,®ol . . . . . . .
723 733 "743 753 763 773
T (K)
Fig. 7. Functional dependence ~'(t) on the temperature of isother-
mal treatment. The line is drawn as a guide to the eye.
Ref. [16]. It is shown in Fig. 7 that the crystallization
process becomes slower as the temperature is de-
creased. This feature of relaxation processes in the
glassy state has been described in detail [7].
The thermal stability of metallic glasses is also
investigated in order to calculate the life-time, r,, of
the amorphous state at the same temperatures. Com-
bination of the isothermal and dynamic treatment in
the analysis of the relaxation and crystallization pro-
cess enables a determination of the time of the
appropriate isothermal transformation on the basis of
the data obtained by dynamical analysis. So the time
necessary for isothermal crystallization of an amor-
phous structure, z~, at temperature T can be obtained
by the relation
% : ( R / E a ) exp[ - ( Ea/RT + C)]. (7)
Taking the values for E a and the corresponding
constant, C, the life-time ~-~ has been calculated for
FeB0Si 10B 10 at different temperatures. The calculated
values are given in Table 2 Owing to high values of
activation energy and relatively high temperatures of
crystallization, we calculate that the life-time of the
amorphous alloy is satisfactory below 620 K.
5. Concluding remarks
On the basis of two phenomenological relations
the necessary cooling rate for the melt was esti-
mated, so as to obtain a completely amorphous state.
The obtained value of 10 6 K / s is in good agreement
with experimentally obtained values. In the low-tem-
perature region, the Curie temperature of the ferro-
i
magnetic transition was determined and found to be
independent of the heating rate; it was also noticed
that a thermal treatment of an as-quenched ribbon
was necessary for the Curie temperature to reach its
i
maximum value for a given composition, i,e., for the
system to reach its maximum stability in the amor-
phous phase. The results of the study of the crystal-
lization phase of the system FeB0Si L0B10 show that
 P. TomiC, M. Davidovid / Journal of Non-Co,stalline Solids 204 (1996) 32-37
we are dealing with a metallic glass with a relatively
high temperature of crystallization, Tm, = 792.07 K,
i.e,, Tin2= 827 K. The J M A kinetic relation and
Kissinger's method were simultaneously used to de-
termine the corresponding activation energy of crys-
tallization, Eal = 354 k J / m o l , i.e., Ea2 = 332
k J / m o l , and the parameter n, responsible for the
crystallization mechanism, was found to be n = 2.3.
By using isothermal measurements, combining the
Arrhenius and the V o g e l - F u l c h e r relation, the char-
acteristic time of crystallization for the investigated
alloy was determined to be ~'o ~ = 2.67 × 10 l° s -~.
The X R D measurements of the crystallized amor-
phous ribbon Fe80Si~0BI0 showed that this system
crystallizes polymorphously and that the crystalliza-
tion products of the composition are a - ( F e S i ) and
Fe3B. On the basis of the determined crystallization
activation energy, the thermal stability of the amor-
phous state was determined in terms of evaluation of
the 'life-time' (7~) at different temperatures. W e
concluded, on the basis o f the obtained values, that
at temperatures to 620 K the life-time of the studied
metallic glass is quite suitable for its potential appli-
cations. The F e - S i - B compositions are of interest as
materials of exceptional magnetic properties, appli-
cable in electronics and energetics. That is why the
knowledge of crystallization kinetics and thermal
stability, which are important and often limiting
factors, appears to be a necessary prerequisite for
potential applications. The DSC and XRD are reli-
able methods for characterization and investigation
of metallic glasses, their thermal behavior and crys-
tallization kinetics.
Acknowledgements
This paper was partly supported by the Serbian
Research Fund and the authors are indebted for
37
providing financial assistance under project No. 323
FRY to enable this work to be carried out.
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