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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


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

structure and metallic bond gives a new quality
Amorphous metals are in a non-equilibrium which cannot be found in pure metals and regular
metallic solid state, in contrast to the crystalline glasses. The new quality is a combination of differ-
state, which is the state of smallest internal energy ent properties that make a metallic glass interesting
for metals, with a structure similar to that of frozen for possible applications. Stability, an important fac-
(undercooled melt) liquid metals. When produced by tor of amorphous metallic structures, is related to
ultrarapid quenching from melt, they are usually relaxation phenomena and crystallization, which is
usually a thermally activated process of transition
from a disordered amorphous structure to an ordered
* Corresponding author. Tel.: + 381-11 444 0871 ; fax: + 381-11
crystal structure. Studying the low-temperature relax-
444 0195; e-mail: 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 33

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

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

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


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

20 40 80 20
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 Ref. [16]. It is shown in Fig. 7 that the crystallization
process becomes slower as the temperature is de-
1.00 1,10 120 1,30 creased. This feature of relaxation processes in the
10ootr (l/K)
glassy state has been described in detail [7].
Fig. 6. l n [ - l n ( 1 - a)] as a function of 1 / T for the examined The thermal stability of metallic glasses is also
metal glass at a heating rate 10 K / s . The curves are a fit of the investigated in order to calculate the life-time, r,, of
data to a linear function, l n [ - l n ( l - a ) ] = C + D / T .
the amorphous state at the same temperatures. Com-
bination of the isothermal and dynamic treatment in
the analysis of the relaxation and crystallization pro-
[6,23], where the value of n was determined by cess enables a determination of the time of the
isothermal measurements. The value n = 2.3 sug- appropriate isothermal transformation on the basis of
gests a diffusion controlled three-dimensional crys- the data obtained by dynamical analysis. So the time
tallization mechanism. This result could have been necessary for isothermal crystallization of an amor-
expected since we are dealing with a metal glass phous structure, z~, at temperature T can be obtained
with low metalloid content. The result obtained for by the relation
the activation energy, E, = 354 kJ/mol, points out
high thermal stability of this metal glass, which % : ( R / E a ) exp[ - ( Ea/RT + C)]. (7)
makes it attractive for technological applications. Taking the values for E a and the corresponding
The characteristic time of crystallization, r(t), constant, C, the life-time ~-~ has been calculated for
was determined by the Vogel-Fulcher relation, Eq. FeB0Si 10B 10 at different temperatures. The calculated
(4). By isothermal measurements at several charac- values are given in Table 2 Owing to high values of
teristic temperatures, the characteristic time of crys- activation energy and relatively high temperatures of
tallization z(t) at appropriate temperature is calcu- crystallization, we calculate that the life-time of the
lated. Having the values for the activation energy of amorphous alloy is satisfactory below 620 K.
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. 5. Concluding remarks
By the measurements, %1 = 2.67 × 10 -1° s -1 is
obtained, which is in good agreement with results in 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.
i , 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-
16,000 i
magnetic transition was determined and found to be
12,o00~ 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
,®ol . . . . . . . i
723 733 "743 753 763 773 maximum value for a given composition, i,e., for the
T (K) system to reach its maximum stability in the amor-
Fig. 7. Functional dependence ~'(t) on the temperature of isother- phous phase. The results of the study of the crystal-
mal treatment. The line is drawn as a guide to the eye. lization phase of the system FeB0Si L0B10 show that
P. TomiC, M. Davidovid / Journal of Non-Co,stalline Solids 204 (1996) 32-37 37

we are dealing with a metallic glass with a relatively providing financial assistance under project No. 323
high temperature of crystallization, Tm, = 792.07 K, FRY to enable this work to be carried out.
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- References
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