Oxid Met (2014) 81:299–313

DOI 10.1007/s11085-013-9413-z

ORIGINAL PAPER

Non-Isothermal Kinetic Analysis of Oxidation of Pure

Aluminum Powder Particles

S. Hasani • M. Panjepour • M. Shamanian

Received: 21 December 2012 / Revised: 19 January 2013 / Published online: 9 August 2013
Ó Springer Science+Business Media New York 2013

Abstract Non-isothermal kinetic analysis of oxidation of aluminum powder particles

(100–200 lm) was investigated by simultaneous thermogravimetry (TG) and differ-
ential thermal analysis under linear temperature programming (ranging from 25 to
1,400 °C) at different heating rates (10, 20 and 30 °C/min). In addition, the rate of
oxidation reaction (rate of thermogravimetry; RTG) was obtained by the RTG curves. It
was found that the oxidation of aluminum powders took place over several stages and
the complete oxidation process did not occur even up to 1,400 °C. Among different
stages, the temperature ranging from 1,000 to 1,150 °C was identified as the main stage
for oxidation process. Hence, kinetic analysis of non-isothermal was determined to be
carried out in this region only. Therefore, non-isothermal kinetic analysis of oxidation of
pure aluminum powder particles was performed using isoconversional methods (Flynn–
Wall–Ozawa, Kissinger–Akahira–Sunose, Friedman ), Markworth and Coats–Redfern
methods. Also, the empirical kinetic triplets [Ea, A, and f(a)] have been calculated.

Keywords Kinetic analysis  Oxidation  Aluminum particles 

Non-isothermal

Introduction

Oxidation of aluminum powders has been widely used in aluminothermic reactions,

fuel additives in propellants, explosives, and pyrotechnics over the recent few decades
[1–5]. Due to the wide range of application of the aluminum powder particles
oxidation, many studies have been done in this area. The studies have shown that non-

S. Hasani  M. Panjepour (&)  M. Shamanian

Department of Materials Engineering, Isfahan University of Technology, 84156-83111 Isfahan, Iran
e-mail: panjepour@cc.iut.ac.ir
S. Hasani
e-mail: s.hasani@ma.iut.ac.ir

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300 Oxid Met (2014) 81:299–313

isothermal oxidation of aluminum powders occur at different stages [6–9]. In addition,

the results indicated that the temperature ranging from 1,000 to 1,150 °C was the main
stage for oxidation process [6, 8]. Therefore, in this research work the non-isothermal
kinetic analysis of aluminum particles oxidation was performed at this stage.
Measurements of the metals and alloys oxidation kinetics are of great practical
and theoretical importance since they supply information about the physicochemical
properties of the oxidation products formed during the reaction [10].
However, oxidation kinetics is usually studied by performing isothermal oxidation
experiments. In order to understand the kinetics and mechanisms of oxidation over a
temperature range, a number of oxidation tests need to be conducted at different
temperatures, and Arrhenius plot is used to calculate the diffusion activation energies
[11]. Also, there were several studies on the kinetics of non-isothermal oxidation of
metals over the last 40 years [12]. Kofstad [13] proposed a method with which the
activation energy can be determined by performing non-isothermal oxidation instead
of isothermal oxidation. Wolf and Grochowski [14] developed a model (W–G model)
to describe non-isothermal oxidation kinetics on the basis of isothermal oxidation
kinetics. Markworth [15, 16] re-developed the W–G model also based on the above
assumptions. However, it should be noted that the W–G and Markworth models were
both developed based on the linear relationship between temperature and time.
Therefore, a numerical model was developed by Liu and Gao [17] for non-linear
temperature–time relationship. However, the oxidation kinetic of pure aluminum
powder particle is usually studied by isoconversional [18, 19] and Coats and Redfern
[18] methods. Therefore, in this study, not only Markworth model, but also
isoconversional and Coats and Redfern methods were used.
For kinetic analysis, the results of the non-isothermal TG and DTA are often
used. Kinetic analysis aims to calculate kinetic parameters of the investigated
process, i.e. the activation energy (Ea), the pre-exponential factor (A) and kinetic
model (f(a)), the so-called ‘‘kinetic triplets’’. Ea of oxidation of aluminum powder
particles has already been studied and reported to range from 77.9 to 418 kJ/mol
[20–25], while no accurate study has been performed for the two other kinetic
parameters. Therefore, one of the major goals of this article is to calculate the true
kinetic triplets of the non-isothermal oxidation of pure aluminum powder particles.
For this purpose, Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS),
Friedman (FR) and Coats–Redfern (C–R) methods were used.

Theory

The results of the non-isothermal thermogravimetry (TG) can be used to calculate

the kinetic parameters of the investigated process.
The fractional reaction (a) can easily be specified at this stage by TG curves and
the following equation [19, 26, 27]:
mt  mi
a¼ ð1Þ
mf  mi
where, mi, mf and mt are the initial, final and current sample mass at the moment t,
respectively.

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Oxid Met (2014) 81:299–313 301

Curve a versus T can be used for the kinetic analysis and the description of the
reaction mechanism. For this reason, it is possible to analyze the non-isothermal
kinetic data by combining the equations bellow:
(I) The differential form of the kinetic equation:
da=dt ¼ k:f ðaÞ ð2Þ
where, t time, k reaction rate constant, f(a) an algebraic function depending on the
reaction mechanism (or differential reaction model).
(II) The Arrehenius equation:
k ¼ A: expðEa =RTÞ ð3Þ
Where T and R are absolute temperature and gas constant, respectively.
(III) Temperature changes in terms of time:
T ¼ T0 þ b:t ð4Þ
where T0 is the initial temperature and b is constant heating rate.
Therefore, with a view to Eq. (4) we will have:
dT=dt ¼ b
ð5Þ
i:e: dt ¼ dT=b
The basic kinetic equation for non-isothermal kinetic data is thus obtained by
combining Eqs. (2), (3) and (5).
da=dT ¼ ðA=bÞ: expðEa =RTÞ:f ðaÞ ð6Þ
Equation (6) cannot be integrated analytically and hence some of the methods of
approximate solution of the equation (i.e. the model-free (isoconversional) and
model-fitting methods) were proposed by several researchers. All these methods aim
to determine a sufficient number of kinetic parameters, usually at least the kinetic
parameters and a conversion function or kinetic model, so that accurate extrapo-
lations of kinetic behavior can be made [28–32]. In this work isoconversional
methods (i.e. KAS [33, 34], FWO [35, 36], and FR [37]) were used to calculate the
activation energy of the non-isothermal oxidation of aluminum powders. Isocon-
versional methods can determine Ea without the knowledge or assumption of kinetic
model and, unlike model-fitting approach, they can reveal the dependence of Ea on
a. The dependence of Ea on a is considered as a reliable criterion of the process
complexity [38, 39]. If Ea does not depend on a; the investigated process is simple
and can be described by unique kinetic triplet. But, if Ea depends on a, the process is
complex and the shape of the curve Ea vs. a indicates the possible reaction
mechanism [38–40]. It is suggested that dependence of Ea on a should be
investigated by isoconversional methods prior to calculation of the kinetic
parameters by any method [39]. On the other hand, isoconversional methods do
not provide any information about A and f(a). Therefore, for the calculation of the
kinetic parameters of the non-isothermal oxidation of aluminum powders, C–R was
employed in this study [41].

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The values of A are calculated by C–R method under the assumption of the
nth order reaction [42]. C–R method is a model-fitting method, using single a-
T data, obtained at a certain heating rate for the determination of the kinetic
parameters. The methods that use single a-T data for the determination of the
kinetic parameters should be avoided, [29, 43] because they generally fail to
distinguish true from false kinetic model and tend to produce highly uncertain
values of Ea and A. Therefore, to solve this problem, the activation energies
calculated by C–R method were verified by Ea calculated by isoconversional
methods. Thus, the reported kinetic model calculated by C–R method is accepted
because its activation energy is in accordance with Ea calculated by isoconver-
sional methods.

KAS Method [33, 34]

The standard Eq. (6) is represented as follows:

da=f ðaÞ ¼ ðA=bÞ: expðEa =RTÞdT ð7Þ
which is integrated with the initial condition of a = 0 at T = T0 to obtain the
following expression:
Z a Z
da A T Ea A:Ea Ea
gðaÞ ¼ ¼ expð ÞdT ¼ :pð Þ ð8Þ
0 f ðaÞ b T0 RT b:R RT
Essentially the technique assumes that A, f(a) and Ea are independent of T, and
also A and Ea are independent of a. The KAS method is based on the C–R
approximation [41] and Eq. (8):
b A:R Ea
ln ¼ ln  ð9Þ
T2 Ea :gðaÞ RT
Thus, the plot lnb/T2 versus 1/T for a constant value of a should be a straight line
whose slope can be used to evaluate the apparent activation energy.

FWO Method [35, 36]

This method is derived from integral isoconversional method. Using Doyle’s

approximation [44] for the integral which allows lnp(Ea/RT) & -5.331–1.052 Ea/
RT
A:Ea Ea
ln b ¼ ln  5:331  1:052 ð10Þ
R:gðaÞ RT
Thus, for a = const., the plot lnb versus 1/T, obtained from TG recorded at
several heating rates, should be a straight line whose slope can be used to evaluate
the apparent activation energy.

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Oxid Met (2014) 81:299–313 303

FR Method [37]

This method is a differential isoconversional method and is directly based on Eq. (7)
whose logarithm is:
da da Ea
¼ ln b
ln ¼ ln½A:f ðaÞ  ð11Þ
dt dT RT
From this equation, it is easy to obtain values for Ea over a wide range of
conversions by plotting ln (b da/dT) against 1/T for a constant a value.

Markworth Method [15, 16]

The isothermal oxidation kinetics followed a parabolic law:

DW 2 ¼ kp t ð12Þ
where DW, t, and kp are the mass gain per unit area due to oxidation, time and the
rate constant, respectively. In this equation, the rate constant, kp, changes with
temperature according to an Arrhenius-type relationship and taken to be of the form
[as same as Eq. (3)]:
kp ¼ A: expðEa =RTÞ ð13Þ
where A is the pre-exponential factor, Ea is the activation energy, R is the gas
constant, and S is the absolute temperature. Also, according to Eq. (4), the tem-
perature varies linearly with time. Therefore, by substituting the relationship
between time and temperature into Eqs. (12) and (13), the following equation can be
obtained:
Ea
DW 2 ¼ A:t: expð Þ ð14Þ
R:ðT0 þ btÞ
But, in the Markworth model, the derivation is started with the mass gain rate:
dW Kp
¼ ð15Þ
dt 2W
Therefore, the mass gain due to non-isothermal oxidation by the Markworth
model is described as:
 
A:Ea eZm eZi
Wm2  
r:R Zm2 Zi2
ð16Þ
Ea Ea
Zi ¼ ; Zm ¼ ; Tm ¼ Ti þ ðtm  ti Þ:b
R:Ti R:Tm
where Ti is the initial temperature of reaction (t = ti) and Tm is temperature of
reaction in t = tm (tm [ ti).
Thus, according to this method, the plot of Wm2 versus Tm for the prediction and
the experimental results must be coincided (for the non-isothermal oxidation data).

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However, in this study, the Markworth model was investigated for the data of
aluminum micro-size particles oxidation, but results were not acceptable. Because
of this model is basis of the rate low (Parabolic rate law) and most of the rate laws
seem to be satisfactory only over a very limited oxide thickness range [12].
Therefore, in this study, results of isoconversional and C–R methods were
published.

C–R Method [41]

In this method, using an asymptotic approximation for the resolution of Eq. (8)
(2RT/Ea  1), the following equation can be obtained:
gðaÞ A:R Ea
ln ¼ ln  ð17Þ
T2 b:Ea RT
The algebraic expressions of f(a) and g(a) for the kinetic models have been
exhibited in many references (e.g. [45, 46]).
Earlier studies showed that, there were little errors in calculating kinetic
parameters such as A and Ea by this method. In this way, two problems were
encountered: the models gave nearly acceptable fits (R [ 0.93) and also, based on
the quality of the fit, some models were indistinguishable (i.e., all R-values equal).
‘‘R’’ is the correlation coefficient of the linear regression corresponding to use
method. Therefore, according to some authors, quality of fit is a poor indicator of
the best model when using model-fitting methods [47, 48], because these methods
were least affected by experimental variables causing curve shifts. However, they
simultaneously determine Ea and A from a single TG curve, which could lead to
inaccuracies, such as indistinguishable models based on statistical criteria.
Additionally, model-fitting methods cannot reveal reaction complexity as they
assume a constant value of Ea and A [47]. These drawbacks of C–R method can be
avoided by using isoconversional methods which require a-T data obtained from at
least three different heating rates [49]. Hence, in order to resolve this problem in this
study, the kinetic model (specified by C–R method) was reported that its activation
energy had coincided with the results of isoconversional methods.

Materials and Methodology

The aluminum powder (produced by Fluka Company) with a purity of more than
99 % and grain size of 100–200 lm was used in this study. The mechanism of
aluminum oxidation was investigated by means of the simultaneous thermal
analysis (STA) device (STA503, Bahr), in ambient air. The samples of
*35.5 ± 0.5 mg were pressed in aluminum pans and were oxidized directly (in
ambient air) within the STA device, at a temperature ranging from ambient
temperature to 1400 °C, using various heating rates: 10, 20 and 30 °C/min. In the
next stage, the results obtained from these processes were studied to calculate

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Oxid Met (2014) 81:299–313 305

kinetic parameters. Also the microstructure of the products was analyzed by SEM
(XL30 SERIES, Philips).

Results and Discussion

The typical TG–DTA curves of the sample (at a heating rate of 20 °C/min) are
shown in Fig. 1. This figure is presented to better understand and gain enough
recognition of the phenomena performed on the basis of these curves, including the
characteristic temperatures of oxidation process. Each TG–DTA curve can be
divided into different regions (I to V). Hence, the results obtained from the thermal
analysis experiments, consisting of TG–RTG and the characteristic points of the
reaction curves, performed on aluminum powders at the heating rates of 10, 20, and
30 °C/min are presented in Fig. 2a–c. In the initial stage, the rate of oxidation was
very negligible; wherein the amorphous oxidation crust properly protected
aluminum up to this limit (stage I in Figs. 1, 2a–c). In continuation, the amorphous
oxide crust was changed into crystalline phase by increasing the temperature up to
the limit of 600 °C. Because of the formation of grain boundary in the structure of
the crust through crystallization, the oxidation rate is increased (stage II in Figs. 1,
2a–c). However, by increasing the temperature up to 700 °C, the diffusion paths
were destroyed by the effect of oxidation process so that the rate of oxidation was
abruptly reduced (stage III). Hence, there was no noticeable sign of mass gain
increase resulting from oxidation. In addition, during this stage, the remaining
aluminum present in the particles was melted (DTA curve in Fig. 1). In continuation
(stage IV), the melt within the crust was expanded by an increase in temperature. In
addition, at this stage, the shrinkage of crust occurred during c-Al2O3 to a-Al2O3
transformation. Due to expansion of molten aluminum and shrinkage of crust, it
created an intense tension on the crust [8]. Within the temperature range of

Fig. 1 Typical results of TG–DTA curves and definitions of characteristic regions and temperatures for
the oxidation process of aluminum powders, with a constant heating rate of 20 °C/min

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Fig. 2 TG and RTG curves for the oxidation process of Aluminum powder at a 10 °C/min, b 20 °C/min,
and c 30 °C/min

1,000–1,150 °C, the melt ruptured the crust and permeated outward. The contact of
this melt with oxide atmosphere made an intense oxidation (RTG curves in Fig. 2a–
c). According to RTG curves in Fig. 2a–c, the main stage of the oxidation of
aluminum powder particles was oxidized at this stage. Therefore, in this study, only
the kinetic study of this region (non-isothermal kinetic analysis) is performed.
Kinetic analysis for simulated and real data sets is described below.

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Oxid Met (2014) 81:299–313 307

Fig. 3 The a versus T curves

for the oxidation reaction of
aluminum powder, ranging from
1,000 to 1,150 °C, obtained at
different heating rates (extracted
from TG curves)

Isoconversional Methods

For kinetic analysis, a can easily be specified at this stage by TG curves (Fig. 2a–c)
and Eq. (1). The curves of a versus T at different heating rates for the oxidation
reaction of aluminum powder (through region IV) are shown in Fig. 3.
In order to evaluate the dependence of Ea on a for the non-isothermal oxidation
of pure aluminum powder particle, FWO, KAS and FR methods were used. For
selected a = const., the plots log b versus 1/T, ln(b/T2) versus 1/T and ln[b da/dT]
versus 1/T were obtained and from their slopes values of Ea were calculated by
means of FWO, KAS and FR method, respectively and the dependences of Ea on a
have been shown in Fig. 4a–c. Also, the average values of Ea in the conversion
range in which Ea values are practically constant (0.10 \ a \ 0.90) have been
shown in Table 1. According to data presented in Table 1, the activation energy of
oxidation in this stage was equal to 150–160 kJ/mol.
The obtained activation energy in this research is compared with the values of
other references [21, 24, 25, 50–52] in Table 2. According to data presented in
Table 2, several parameters (for example: atmosphere type, particles size, and shape
of particles) can be effected in activation energy of aluminum particles oxidation.
As it is observed, the oxidation activation energy of the spherical aluminum particle
in air is raised with increase of particles size. Therefore, there is a good conformity
between the results obtained from different references and this study.
Isoconversional methods can determine Ea without the knowledge or assumption
of kinetic model. Therefore, in the same of this study, the kinetic model of this
reaction was determined by model-fitting results (C–R method).

Model-Fitting Results (C–R Method)

According to Eq. (17), the ln(g(a)/T2) curve slope in terms of 1/T activation energy
and width from its origin provides the A. In addition, by this method, kinetic model
[f(a) or g(a)] can be specified. The results obtained by the CR method for various

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308 Oxid Met (2014) 81:299–313

Fig. 4 Dependence of Ea on a
evaluated by means of FWO (a),
KAS (b) and FR (c) method for
non-isothermal oxidation of pure
aluminum powder particle

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Oxid Met (2014) 81:299–313 309

Table 1 Average values of Ea

Kinetic methods Ea (kJ/mol)
obtained by isoconversional of
FWO, KAS and FR methods
Flynn–Wall–Ozawa (FWO) 160
Kissinger–Akahira–Sunose (KAS) 160
Friedman (FR) 151

Table 2 Comparison of the activation energy of the oxidation of aluminum in different references
Ref. [21] [24] [25] [50] [51] [52] This
work

Atmosphere Air CO2– O2 CO2, O2, Air CO2– Air

H2O Ar H2O
Shape of Spherical Spherical Spherical Spherical Spherical Spherical Spherical
particles flake
Size of particles 20–25 70–140 3–5 3–4.5 0.1–0.2 4.5–14 100–200
(lm) 20–30
Ea (kJ/mol) 95.7 134.4 251.9 84–418 73.6 200–300 150–160
251.9

kinetic models are shown in Table 3. This table shows that at different thermal
velocities and for different models, different values have been reported for kinetic
parameters. For this reason, the results obtained from isoconversional methods were
used to specify the correct kinetic model. According to the data in Table 2, the
results obtained from iso-conversional methods show that the average Ea value for
this reaction is about 150–160 kJ/mol. Therefore, oxidation of these aluminum
powdery particles are controlled by Avrami–Erofe’ev (r = 5/2) under non-
isothermal conditions. Figure 5 shows ln(g(a)/T2) curve in terms of 1/T for this
model. This model shows that the grain growth rate is proportional to diffusion [49].
According to reported results in other previous studies [12], this mechanism can be
accepted for aluminum oxidation. Therefore, the oxidation of aluminum powder
particles in the temperature ranging from 1,000 to 1,150 °C is controlled by phase
transformation of c-Al2O3 to a-Al2O3 in the crust of aluminum powder particles. In
fact, it can be seen that aluminum oxidation in this stage is controlled by diffusion
controlled growth rate of nuclei of a-Al2O3 in c-Al2O3 crust.
Additionally, these results show that the average Ea value for this reaction at
three heating rates is 160 kJ/mol. Also, the average value of lnA for the three
heating rates has been reported to be 17 min-1. Figure 6 is related to aluminum
particles after being exposed to heating conditions up to 1,400 °C. As it is observed
in this figure, the needle-shaped tubercles and plates are observed on the surface of
particles. These tubercles are related to oxides from the melt dripped from inside the
particles. This melt finds its way outside the scale through the voids and cracks
produced on the surface resulting from internal tension caused by the melt. In fact,
by an increase in temperature (1,000–1,150 °C), the volume of the molten
aluminum is also increased in a way that it exerts great tension on the oxide crust.
Additionally, at this stage, the shrinkage of the alumina scale during the c-Al2O3 to

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 Table 3 Results of non-isothermal kinetics analysis for oxidation of aluminum powder using the Coats–Redfern method
310

Symbol g(a) Ea (kJ/mol) ln A (min-1) R

mechanism

123
b = 10 (°C/ b = 20 (°C/ b = 30 (°C/ b = 10 (°C/ b = 20 (°C/ b = 30 (°C/ b = 10 (°C/ b = 20 (°C/ b = 30 (°C/
min) min) min) min) min) min) min) min) min)

D1 a2 665 650 588 75.7 72.1 63.6 0.8861 0.8671 0.8817

D2 (1 - a) ln(1 - 724 704 641 82.2 78.1 69.5 0.9065 0.8889 0.9035
a) ? a
D3 [1-(1 - a)1/3]2 827 805 737 93.6 88.8 79.4 09394 0.9252 0.9388
D4 (1-2a/3) - 1527 1485 1356 172.0 162.6 144.6 0.9167 0.9026 0.9168
(1 - a)2/3
P1 a1/4 68 66 58 5.2 5.2 4.47 0.8424 0.8150 0.8255
P2 a1/3 97 93 83 8.9 8.7 7.5 0.8569 0.8323 0.8447
P3 a1/2 153 149 140 16.1 15.3 12.7 0.8697 0.8575 0.8612
P4 a3/2 511 467 421 58.5 52.4 46.2 0.9756 0.9841 0.9834
R1 a 335 332 301 37.7 36.9 32.7 0.9748 0.9796 0.9825
R2 [1-(1 - a)1/2] 378 368 334 42.1 40.1 35.8 0.9207 0.9040 0.9180
R3 [1-(1- a)1/3] 405 394 360 45.1 42.9 38.4 0.9370 0.9222 0.9358
A1/2 [-ln(1 - a)]2 997 987 903 116.6 112.7 101.1 0.9649 0.9579 0.9601
A3/2 [-ln(1 - a)]2/3 321 317 289 36.5 35.6 31.9 0.9624 0.9549 0.9569
A2 [-ln(1 - a)]1/2 206 195 182 22.9 21.2 19.2 0.9953 0.9975 0.9987
A5/2 [-ln(1 - a)]2/5 166 159 156 17.6 16.7 15.8 0.9927 0.9962 0.9836
A3 [-ln(1 - a)]1/3 127 124 113 12.9 12.5 11.4 0.9931 0.9972 0.9984
A4 [-ln(1 - a)]1/4 110 108 97 12.8 10.8 9.6 0.9460 0.9550 0.9470
F1 -ln(1 - a) 490 484 472 56.6 55.1 49.4 0.9636 0.9564 0.9585
F2 (1 - a)-1-1 820 736 628 87.3 83.7 71.4 0.9844 0.9625 0.9848
Oxid Met (2014) 81:299–313
Oxid Met (2014) 81:299–313 311

Fig. 5 Curves of ln[-ln(1 - a)2/5/T2] versus 1/T for different heating rate using values of a extracted
from Fig. 3 (0.05 \ a \ 0.95)

Fig. 6 a and b SEM micrographs of aluminum particles (by various magnifications) after being oxidized
at the maximum temperature of 1,400 °C at the heating rate of 20 °C/min with; the needles and plate on
the surface of particle aluminum

a-Al2O3 transformation increases tension on the oxide crust. The molten Al can now
penetrate outside through the pores and cracks and is immediately oxidized when
getting in contact with air. The presence of this amount of tension can provide the
condition of the exit of the melt outside the curst for oxidation by making cracks or
voids on the curst. Therefore, at this stage, the oxidation reaction can be controlled
by the diffusion of reactant (oxygen and aluminum).

Conclusions

Non-isothermal kinetic of oxidation of aluminum powder particles (ranging from

1,000 to 1,150 °C) was analyzed by isoconversional methods and model-fitting

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312 Oxid Met (2014) 81:299–313

results (C–R method). The results of isoconversional methods: KAS, FWO, and FR
showed that Ea of this reaction does not depend on a and a value about 150–160 kJ/
mol has been reported for it. Furthermore, in this section of the study it was tried to
determine the kinetic model of this reaction by the use of C–R model-fitting method.
These results also showed that within the limit where Ea is constant, the non-
isothermal oxidation of these particles follow Avrami-Erofe’ev model. This model
shows that the oxidation in this stage is controlled by the grain growth rate of a-
Al2O3 that is proportional to diffusion. In addition, by the use of this method, Ea and
lnA were reported to be 160 kJ/mol and 17 min-1 for this reaction, respectively.

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