ARTICLE IN PRESS

Journal of Physics and Chemistry of Solids 69 (2008) 16911697

www.elsevier.com/locate/jpcs

A new method to study the crystallization or chemical reaction

kinetics using thermal analysis technique
Nasser Afy
Physics Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
Received 13 August 2007; received in revised form 15 December 2007; accepted 21 December 2007

Abstract
In this work, a new method to study the transformation kinetics is introduced. With this method, the activation energy, Ec, for
crystallization (phase transition or chemical reaction), the pre-exponential coefcient of effective overall reaction rate, ko, and the
reaction order, n, can be determined. No approximation has been used in this method. This method can be used for isothermal and
non-isothermal study. It is deduced from Avramis equation without any approximation. This new method has been tested to study
the amorphous-crystalline transformation kinetics under isothermal and non-isothermal conditions in the context of glassy selenium.
The source of error is discussed. The calculated values of Ec, under isothermal and non-isothermal conditions are 75.372.5 and
79.472.3 kJ/mol, respectively. The predominant crystallization mechanism of the amorphous phase of glassy selenium in isothermal or
non-isothermal conditions is one-dimensional growth. The deduced values of ko were found to be 19.470.9 and 20.870.7 s1 for
isothermal and non-isothermal conditions, respectively. Resulting values of the parameter, n, are compared with values obtained from
other known methods used to study the reaction kinetics in thermal analyses. The difference in the results obtained with this method and
the results obtained with other known methods is acceptable or lie within the experimental error range.
r 2008 Elsevier Ltd. All rights reserved.
PACS: 05.70.Fh; 64.60.I; 64.70.Kb; 81.30.Hd; 81.70.Pg; 82.20.w; 82.37.j; 82.39.k; 82.40.g

1. Introduction
Thermal analysis techniques are used to study the
kinetics of amorphous-crystalline transformation (phase
transition or chemical reaction). The differential scanning
calorimetry (DSC) and the differential thermal analysis
(DTA) are precise methods to record variation of heat ow
or temperature difference in isothermal and non-isothermal
heating. Many methods are used to analyze DSC and DTA
thermograms to obtain the amorphous-crystalline kinetics,
especially activation energies, pre-exponential coefcient of
effective overall reaction rate, reaction order and types of
crystal growth [112].
The aim of this work is to introduce a new method to
determine the crystallization (phase transition or chemical
reaction) activation energy, Ec, the pre-exponential coefcient
Tel.: +20 88 2320998; fax: +20 88 2342708.

E-mail address: afy@aun.edu.eg

0022-3697/$ - see front matter r 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2007.12.016

of effective overall reaction rate, ko, and the reaction order

of crystallization, n, under isothermal and non-isothermal
conditions. To realize this aim, the new method has been
applied to results of amorphous selenium under isothermal
and non-isothermal conditions.
2. Theortical basis
The theoretical basis for interpreting DTA or DSC data
is provided by the formal theory of transformation kinetics
or chemical reaction as the volume fraction (w) crystallized
(transformed or interacted) in time (t), using Avrami
equation [15]
w 1  expktn ,

(1)

where n is an integer or half-integer which depends on

the mechanism of growth and the dimensionality of the
crystal [15], k is dened as the effective overall reaction
rate, which is usually assumed to have an Arrhenian

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N. Afify / Journal of Physics and Chemistry of Solids 69 (2008) 16911697

temperature dependence:
k ko expE c =RT,

(2)

where ko is the pre-exponential coefcient of effective

overall reaction rate, Ec is the effective activation energy
describing the overall crystallization process and R is the
gas constant. The overall effective activation energy for
crystallization (Ec) is expressed as
E c  E N mE G =n,

(3)

where EN and EG are the effective activation energies for

nucleation and growth, respectively, and n=m for the
nucleation frequency Iu=0 [4,5], and n=m+1 for Iu60
[4,5]. If EN is negligible over the temperature range of
concern in the thermo-analytical study [4,5], then
E c  m=nE G .

(4)

To determine the effective activation energy for crystallization, Ec, under isothermal or non-isothermal conditions, Eq. (1) can be written as
Ln1  w ktn .

(5)

The important condition in this method is at

w 0.63205, Ln(1w) 1. This condition has been
discussed in early work [7]. The advantage of this condition
is that the results at k0.63 are independent of the value of n,
contrary to Avramis method, which is dependent on the
value of n. Eq. (5) at w 0.63205, gives
l k0:63 t0:63 n ,

(6)

k0:63 1=t0:63 .

(7)

The value of the effective overall reaction rate at

w 0.63205, (k0.63), can be determined from Eq. (7), i.e.
from the inverse of the time at w 0.63205, (1/t0.63). The
values of w 0.63205, t0.63 has been determined using the
partial area technique [6] described in the experimental
techniques.
The effective overall reaction rate at w 0.63205 (k0.63)
can be written as
k0:63 ko expE c =RT 0:63 ,

3. Experimental techniques
Amorphous selenium has been prepared using the wellknown melt-quench technique [4,5]. Selenium of 99.999%
purity from Aldrich Co., USA, was sealed into quartz glass
ampoules under a vacuum of 105 Torr. The ampoules were
heated in Heraeus programmable tube furnace-type R07/50.
The amorphousity, the crystallization kinetics and the
homogeneity of the sample were conrmed by X-ray
diffraction (Philips type1710 chart diffractometer) and
DSC (Shimadzu DSC 50). The accuracy of the heat ow is
70.01 mW. The temperature was determined with an
accuracy of 70.1 K using the microprocessor of the
thermal analyzer.
The thermal analysis study was carried out under
isothermal and non-isothermal conditions.
The crystallization fraction, w, has been determined using
the partial area technique [6]. The fraction w crystallized at
any temperature T or time t is given as w (At/A) in
isothermal condition or by w (AT/A) in non-isothermal
condition. Here A is the total area of the exothermic peak
between temperature Ti or time ti on which crystallization
begins and the temperature Tf or time tf at which the
crystallization is completed, shown in Fig. 1. At is the area
between ti and t as shown by the hatched portion in Fig. 1.
On the other hand, AT is the area between Ti and T as
shown by the same hatched portion in Fig. 1. Using the
partial area technique [6], the temperature or time at
w 0.63205 can be determined. The time at w 0.63205 is
denoted by t0.63 and the temperature at w 0.63205 is
T (K)
330

340

350

360

370

380

390

T0.63
Exo

(8)

where Ec can be determined from the slope of Ln(k0.63) vs.

1/T0.63 graphs, obtained from different thermograms. In
the isothermal condition, the thermograms are carried out
at different temperatures, but in case of non-isothermal
condition, the thermograms are carried out at different
heating rates.
The pre-exponential coefcient of effective overall
reaction rate, ko, can be determined also from the
intersection of the k0.63 axis in the above graph.
To determine the reaction order, n, Eq. (5) can be written as
LnLn1  w n Lnk n Lnt.

condition, the graph is carried out, at constant temperature,

from different thermograms, i.e. different heating rates.

T
Q

Tf

t
Endo

tf

t
i

(9)

At constant temperature (k is constant), the relation

between Ln[Ln(1w)] and Ln(t) gives the reaction order,
n. In the isothermal condition, the above graph is carried out
from one thermogram, but in the case of non-isothermal

600

700

800

900

1000

0.63

1100

1200

t (sec)
Fig. 1. Schematic diagram illustrates the partial area and the area at
w 0.63205.

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N. Afify / Journal of Physics and Chemistry of Solids 69 (2008) 16911697

denoted by T0.63. A computer program written in Basic

Language has been designed to calculate all the thermal
parameters used in this work.

1693

Tp

a-Se

Exo.

(K/min)

Tc

Tg

40

4. Results and discussion

30

4.1. Sample examination

25

20

4.2. Isothermal study

The three important parameters (Ec, ko and n) in
transformation kinetics were determined under isothermal
condition.

15
10
7
5
2.5

Endo.
300

350

400

450

T (K)
Fig. 3. DSC traces of as-prepared Se glass at different heating rates, a.

-5.6

Isothermal

a-Se

R = -0.99752

-5.7
-1

Ln [K 0.63 (sec )]

The glassy state and the homogeneity of the selenium

sample have been examined using X-ray diffraction and
DSC techniques. The diffractogram of the as-prepared
selenium sample is shown in Fig. 2. A typical DSC trace of
selenium glass obtained at non-isothermal condition at
different heating rates is shown in Fig. 3.
From the X-ray diffractogram, it is clear that the sample
is in the amorphous state. In the non-isothermal DSC
thermogram, three characteristic phenomena are resolved
in the studied temperature region. The rst one corresponds to the onset glass transition temperature, Tg; the
second one corresponds to the extrapolated onset crystallization temperature, Tc, and the last one to the peak
temperature of crystallization, Tp. This behavior is typical
for glass-crystalline transformation. The glass transition
peak has only one onset temperature, which means that the
sample is homogenous [7].

-5.8
-5.9
-6.0
-6.1
-6.2

4.2.1. Crystallization activation energy, Ec, and preexponential coefficient of effective overall reaction rate, ko
According to Eq. (8), and from the relation between
Ln(k0.63) and 1000/T0.63, as shown in Fig. 4, the value of
crystallization activation energy, Ec, and the value of the
pre-exponential coefcient of effective overall reaction rate,

2.76

2.77

2.78

2.79

2.80

2.81

2.82

-1

1000/T 0.63 (K )
Fig. 4. Ln(K0.63) vs 1000/T0.63 for glassy Se sample under isothermal
condition.

ko, have been determined. The values of Ec and ko are

75.372.5 kJ/mol and 19.470.9 s1, respectively.
a-Se

Intensity [arb.unit]

4.2.2. Reaction order, n

The reaction order, n, for different isothermal thermograms
was deduced using Eq. (9). Fig. 5 shows the relation between
Ln[Ln(1w)] and Ln(t) deduced from isothermal thermogram carried out at temperature 357 K as an example. The
value of n at T 357 K is 1.8570.10. This means that the
predominated crystallization mechanism is one-dimensional
growth [5]. The difference in the values of n deduced for all
thermograms is about 75%. This difference has no signicant inuence on the type of the crystallization mechanism.
4.3. Non-isothermal study

10

20

30

40

50

2 [deg.]
Fig. 2. X-ray diffraction of as-prepared Se sample.

60

The three important parameters (Ec, ko and n) in

transformation kinetics were estimated under non-isothermal condition.

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N. Afify / Journal of Physics and Chemistry of Solids 69 (2008) 16911697

1694

Isothermal

a-Se

-5.5

T = 357K
R = -0.999

Non-isothermal

0
Ln [-Ln (1-)]

-6.0
Ln [-Ln (1-)]

a-Se
T = 375 K
R = -0.99382

-6.5

-7.0

-2

-4

-6

-7.5
3.2

3.4

3.6

3.8

4.0

4.2

4.4

Ln [t (sec)]
Fig. 5. Ln(Ln(1w)) vs Ln(t) at T 357 K for glassy Se sample under
isothermal condition.

-3.0

a-Se
R = -0.99709

-1

Ln [K0.63 (sec )]

-4.5
-5.0
-5.5

2.55

2.60

3
4
Ln [t (sec)]

Fig. 7. Ln(Ln(1w)) vs. Ln(t) at T 375 K for glassy Se sample under

non-isothermal condition.

Firstly, the difference in the values of Ec, ko and n

deduced under isothermal and non-isothermal condition is
acceptable and may be due to difference in the measuring
technique.
In other words, three well-known methods have been
used to calculate the above three parameters to compare
their results with the results obtained with the suggested
new method. The comparison is carried out in the case of
non-isothermal condition.

-4.0

2.50

4.4. Comparison with other methods

Non-isothermal

-3.5

-6.0

-8

2.65

2.70

2.75

2.80

-1

1000/T0.63 (K )
Fig. 6. Ln(k0.63) vs 1000/T0.63 for glassy Se sample under non-isothermal
condition.

4.3.1. Crystallization activation energy, Ec, and preexponential coefficient of effective overall reaction rate, ko
According to Eq. (8) and from the relation between Ln(k0.63) and 1000/T0.63, as shown in Fig. 6, the
value of crystallization activation energy, Ec, and the
value of the pre-exponential coefcient of effective
overall reaction rate, ko, have been determined. The values
of Ec and ko are 79.472.3 kJ/mol and 20.870.7 s1,
respectively.
4.3.2. Reaction order, n
According to Eq. (9), Fig. 7 shows the relation between
Ln[Ln(1w)] and Ln(t) at temperature 375 K deduced
from non-isothermal thermograms carried out at different
heating rates. The value of n is 1.7570.09 which means
that the predominated crystallization mechanism is onedimensional growth [5].

4.4.1. Crystallization activation energy, Ec

To compare between Ec obtained with the suggested
method and the other well-known methods, Kissingers
method has been used. In Kissingers method [49] the
crystallization activation energy, Ec, can be expressed as
!


a
m Ec
Ln
Lnk,
(10)


n RT p
T 2p
where a is the heating rate and Tp is the peak temperature
of crystallization. Fig. 8 shows the relation between
Ln(a/T2p) and 1000/Tp. The deduced value of Ec is
80.071.9 kJ/mol.
It is clear that the value of Ec deduced with the suggested method under non-isothermal condition is approximately equal to that calculated with Kissingers method
and the difference lies in the experimental error range
(0.75%).
4.4.2. Pre-exponential coefficient of effective overall
reaction rate, ko
Augis and Bennetts method has been used to determine
ko which is compared with those obtained with this
method. In Augis and Bennetts method [47,10] the preexponential coefcient of effective overall reaction rate, ko

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N. Afify / Journal of Physics and Chemistry of Solids 69 (2008) 16911697
-8.0
Non-isothermal

a-Se
R = -0.99795

Ln [ /Tp2 (min-1 K-1)]

-8.5
-9.0
-9.5
-10.0
-10.5
-11.0
2.50

2.55

2.60

2.65

2.70

2.75

2.80

-1

1000/Tp (K )
Fig. 8. Ln(a/T2p) vs. 1000/Tp for glassy Se sample under non-isothermal
condition.

Ln [/(Tp-Ti) (min-1)]

-2.0

Non-isothermal

-2.5

a-Se
R = -0.99813

1695

method (JMA) [47,11] has been used. JMAs equation can

be written as
LnLn1  w n Lna  1:052mE c =RT constant:
(12)
Fig. 10 shows the relation between Ln[Ln(1w)] and
Ln(a) at constant temperature (T 375 K). The deduced
value of n is 1.5670.05.
The new method to determine n has the advantage that
all the represented points in Figs. 5 and 7 are measured
points but in JMAs method the represented points in
Fig. 10 are calculated from the extrapolation of the linear
part in the relation between Ln[Ln(1w)] and 1000/T at a
constant heating rate.
It is clear that the difference between the value of n
deduced with the suggested method under non-isothermal
condition and that obtained by JMAs method is about
0.19. This difference can be attributed to the uncertainty in
the calculation of the JMAs method.
Generally, the results of the suggested method are
acceptable. The suggested method is valid for isothermal
and non-isothermal study.
4.5. Source of error

-3.0
-3.5
-4.0
-4.5
-5.0
2.50

2.55

2.60

2.65

2.70

2.75

2.80

1000/Tp (K )
-1

Fig. 9. Ln[a/(TpTi] vs. 1000/Tp for glassy Se sample under nonisothermal condition.

It is very important to determine the exact value of the

time ti or temperature Ti at which the crystallization just
begins.
An error in the value of ti causes effective error in the
value of t0.63. The three curves in Fig. 11 are calculated for
exothermic crystallization peak at the heating rate 5 K/min.
Curves A and C are calculated, respectively, at ti values
lower than the exact value of ti (60 s) and at values higher
(+60 s) than the exact value of ti. But curve B is calculated
at the exact value of ti. It is clear that the values of t0.63
for the three curves are different. The error in t0.63 deduced
from curve A is about 29.3% and that in curve C is
about +34.5%. This error causes an effective error in the

can be calculated from the following equation:

(11)

where Ti is the temperature at which the crystallization just

begins. Fig. 9 shows the relation between Ln[a/(TpTi)]
and 1000/Tp. The deduced value of ko is 23.870.6 s1.
It is clear that the difference between the value of ko
deduced with the suggested method under non-isothermal
condition and that obtained by Augis and Bennetts
method is about 3.0 s1. This difference in value of ko
may be due to the effect of approximation in Augis and
Bennetts method, in which they considered that the initial
temperature, Ti, is very small in comparison with the
sample temperature, T. Therefore they neglect the effect of
the ratio (Ti/T) in their method [4,5, 10].
4.4.3. Reaction order, n
To compare between n obtained with this method
and another well-known method, JohnMehlAvramis

Non-isothermal

a-Se
T = 375 K
R = -0.99686

2
Ln[-Ln (1-)]

Lna=T p  T i  Lnko  E c =RT p ,

-1

-2
1

2
Ln[ (K/min)]

Fig. 10. Ln(Ln(1w)) vs. Ln(a) at T 375 for glassy Se sample under
non-isothermal condition.

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N. Afify / Journal of Physics and Chemistry of Solids 69 (2008) 16911697

1696
a-Se
= 5 K/min

higher

exact

0.9

inuence on the value of the partial area w and the value of

t0.63 and T0.63. The positive error in tf or Tf does not have
any effect on the values of w, t0.63 or T0.63.

lower

t 0.63

t 0.63

0.3

t 0.63

5. Conclusion
0.6

0.0
0

100

200
t (sec)

300

400

Fig. 11. The relation between w and t at different ti.

a-Se
= 5 K/min

0.9

exact

T 0.63

lower

0.3

T 0.63

0.6

higher

This suggested method can be used to study the

transformation kinetics of crystallization, phase transition
or chemical reaction under isothermal or non-isothermal
conditions. With this method, the activation energy, Ec, for
crystallization (phase transition or chemical reaction), the
pre-exponential coefcient of effective overall reaction rate,
ko, and the reaction order, n, can be determined. No
approximation has been used in this method. The accuracy
of this method is practically the same as of the other known
methods. The time ti and the temperature Ti must be
determined with high accuracy. The calculated values of Ec
under isothermal and non-isothermal conditions are
75.372.5 and 79.472.3 kJ/mol, respectively. The deduced
values of ko were found to be equal to 19.470.9 and
20.870.7 s1 for isothermal and non-isothermal study,
respectively. The predominated crystallization mechanism
of the amorphous phase of glassy selenium in isothermal or
non-isothermal conditions is one-dimensional growth. The
difference in the results obtained under isothermal and
non-isothermal condition is acceptable or lies within the
experimental error range. The advantage of this method is
that the results at k0.63 are independent of the value of n,
unlike in contrary to Avramis method, which is dependent
on the crystallization mechanism, n.

0.0
350

360

370

380

Acknowledgements

T (K)
Fig. 12. The relation between w and T at different Ti.

value of k0.63 and is reected on the accuracy of the

deduced value of Ec.
In other words, a negative error on the value of Ti
(5 K) (i.e. the value of Ti being lower than the exact value
of Ti) does not have any effect on the value of T0.63. But a
positive error in Ti (+5 K) (i.e. the value of Ti being higher
than the exact value of Ti) has a small inuence on the
value of T0.63. Fig. 12 shows three curves calculated at
different Tis for the same exothermic peak used in Fig. 11.
Curve A is calculated at Ti lower than the exact value. The
value of T0.63 is the same as that calculated at exact value of
Ti (curve B). Curve C is calculated at Ti slightly higher than
the exacted value. It is clear that the value of T0.63 is
slightly higher than the correct value of curve B (1.1%). In
all cases, an error in Ti has inuence on the determination
of ko using Augis and Bennetts method.
A negative error in the value of time tf or temperature Tf,
at which the crystallization is completed (i.e. values of tf or
Tf being lower than their corresponding exact values causes
an error in the value of the total area. This error has an

The author would like to acknowledge Mrs. N. Fathy

and Ms. Gh. Abbady Assistant lecturers in the Physics
Department, Assiut University, for their helpful assistant.
Prof. W.W. Bishara, Assiut University, is acknowledged
for language revision of this work. The Deutsche Gessellschaft fur Technishche Zusammenarbeit (GTZ) and
the Deutsche Akademische Austauschdienst (DAAD),
Germany, are acknowledged for partly supporting this
work by a grant-in-aid (Project nos. PN 87.2061.7-01.100
and PN 87.2061.7-02.300-9314).
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