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Sublimation Kinetics of Zirconium Tetrachloride (ZrCl4) for Producing Zr

Sponge

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Materials Chemistry and Physics 143 (2014) 1075e1081

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Isothermal and non-isothermal sublimation kinetics of zirconium

tetrachloride (ZrCl4) for producing nuclear grade Zr
Jae Hong Shin a, Mi Sun Choi b, Dong Joon Min c, Joo Hyun Park a, *
a
Department of Materials Engineering, Hanyang University, Ansan 426-791, Republic of Korea
b
Research Institute of Industrial Science and Technology (RIST), Pohang 790-330, Republic of Korea
c
Department of Materials Science and Engineering, Yonsei University, Seoul 120-749, Republic of Korea

h i g h l i g h t s

Sublimation kinetics of ZrCl4 was quantitatively analyzed using TGA method.

Isothermal and non-isothermal sublimation kinetics were quantitatively evaluated.

Activation energies of isothermal and non-isothermal kinetics were obtained.

Sublimation mechanism was proposed from kinetic analyses and SEM observations.

This kinetic information will be very useful in production of nuclear grade Zr.

a r t i c l e i n f o a b s t r a c t

Article history: Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The
Received 10 April 2013 sublimation kinetics of ZrCl4 was investigated by thermogravimetric analysis under both isothermal and
Received in revised form non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under
25 September 2013
isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal
Accepted 3 November 2013
conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of
ZrCl4 sublimation under isothermal conditions was 21.7 kJ mol1. The activation energy for non-
Keywords:
isothermal sublimation was 101.4 kJ mol1 and 108.1 kJ mol1 with the Kissinger method and Flynn
Inorganic compounds
Thermogravimetric analysis
eWalleOzawa method, respectively. These non-isothermal activation energies were very close to the
Phase transitions heat of sublimation (103.3 kJ mol1). Sublimation occurs by two elementary steps: surface reaction and
Thermal properties desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8 (3.4) kJ mol1. The
Thermodynamic properties activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ mol1 and
Transport properties 21.7 kJ mol1, respectively.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction In zirconium production, the raw material is zirconium tetra-

Zirconium and its alloy are used extensively as nuclear fuel
cladding materials in water-cooled nuclear power reactors [1e3].
However, only a few countries in the world have access to
commercial-scale zirconium industries and have the capability to
manufacture reactor-grade zirconium. Metallic zirconium (sponge)
can be produced from a magnesiothermic reduction known as
Kroll’s process [4,5], which is similar to that used for titanium
production except that the raw material (TiCl4) is in the liquid state.
* Corresponding author.
E-mail address: basicity@hanyang.ac.kr (J.H. Park).
chloride (ZrCl4), which sublimates at about 330  C and melts at
about 440  C (triple point). The rate of ZrCl4 sublimation may
control the feeding rate of reactants in a vessel in a way that affects
production efficiency. According to the reports by Reshetnikov and
Oblomeev [6,7], the influence of the rate of ZrCl4 sublimation on the
feeding rate is greater than the influence of the chemical reaction
rate between ZrCl4 and liquid magnesium on the process rate.
An understanding of the mechanism of ZrCl4 sublimation and
the related kinetic data are required to optimize zirconium sponge
production. There have been a few reports on the overall process of
zirconium sponge production that include information on the
distillation process coupled with thermodynamic data of ZrCl4
sublimation [4e10]. The vapor pressures of ZrCl4 from 207 to 416  C
and from 437 to 463  C were originally reported by Palko et al. [8]

0254-0584/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2013.11.007
 Author's personal copy

1076 J.H. Shin et al. / Materials Chemistry and Physics 143 (2014) 1075e1081

They also determined the heats of vaporization and sublimation for f ðaÞ ¼ am $ð1  aÞn $½  lnð1  aÞp (3)
ZrCl4. More recently, Liu et al. [9] measured the vapor pressure of
ZrCl4 from room temperature to 340  C. To the best of our knowl-
where n, m, and p are empirically obtained exponent factors, one of
edge, only equilibrium thermodynamic data on ZrCl4 sublimation
which is always equal to zero [11,12]. All functions covered in this
have been reported, whereas the kinetics of ZrCl4 sublimation has
work are listed in Table 1 in differential and integral form [11e16].
not yet been investigated.
Eq. (3) can be represented in the integral form, function g(a), at
In the present study, we attempted to confirm the sublimation
constant temperature as follows:
mechanism of ZrCl4 based on a kinetic study of its sublimation
using thermogravimetic analysis (TGA). The activation energy of Za
ZrCl4 sublimation was measured under both isothermal and non- da
gðaÞ ¼ ¼ kðTÞ$t (4)
isothermal conditions. f ðaÞ
0

The slope of a line g(a) against time t at a fixed temperature, i.e.

2. Experimental
Eq. (4), is used to calculate the rate constant k(T), which is given by
the Arrhenius equation as follows:
Thermogravimetric analysis (TGA) was employed to measure
the rate of sublimation for reagent-grade zirconium tetrachloride  
Ea
(99.99% purity). An electronic balance set on a kanthal super elec- kðTÞ ¼ A$exp  (5)
RT
tric furnace was connected to a computer to record the weight loss
of the sample due to sublimation. The temperature was calibrated
Ea 1
using a K-type thermocouple in an alumina sheath placed in the hot lnkðTÞ ¼ lnA  $ (6)
zone of the furnace. The experimental temperature ranged from R T
300 to 550  C. A fused alumina crucible (ID: 14 mm, OD: 18 mm, HT:
where A is the pre-exponential factor, Ea is the activation energy, R
40 mm) filled with ZrCl4 powder (1.0 g) was connected to the
is the gas constant, and T is the absolute temperature. Thus, the
electronic balance sensor by molybdenum wire and was hung in
activation energy can be deduced from an Arrhenius plot.
the hot zone of the furnace. ZrCl4 weight loss by sublimation was
automatically recorded every second at each temperature
3.2. Non-isothermal kinetics
(300, 330, 350, 400, 450, 500, and 550  C) for the isothermal
experiments.
3.2.1. Kissinger method
ZrCl4 weight loss was also measured under non-isothermal
For non-isothermal conditions, the heating rate b is given by
conditions with heating rates of 17  C min1 and 8  C min1. Af-
ter the experiments, the morphology of whole samples was
examined by scanning electron microscopy coupled with an energy dT
dispersive spectroscope. b¼ (7)
dt
In the preliminary experiments, the effect of the flow rate of Ar
carrier gas on the ZrCl4 sublimation rate by varying the Ar flow rate Combining Eqs. (1) and (5) gives
from 200 to 500 ml min1 at 330  C. It was founded that the sub-  
limation behavior of ZrCl4 was not noticeably affected by Ar flow da Ea
¼ A$exp  $f ðaÞ (8)
rate within analytical error limit. Hence, an inert atmosphere was dt RT
maintained in the reaction chamber during the experiments by
purging with purified Ar gas of which flow rate was 400 ml min1. Thus, under non-isothermal conditions, the basic equation of
Here, the Ar gas was purified by passing it through Mg turning solid-state decomposition kinetics is obtained from Eqs. (1) and (8)
furnace at 450  C. as follows.
 
da A Ea
¼ $exp  $f ðaÞ (9)
3. Theoretical considerations dT b RT

3.1. Isothermal kinetics

Table 1
Solid-state decomposition kinetics is usually described by the Algebraic expressions of f(a) and g(a) for kinetic models considered in this study.
following basic equation [11]: Model f(a) g(a) Observations

da F0, R1, P1 Constant a Zero-order kinetics;

¼ kðTÞ$f ðaÞ (1) one-dimensional advance
dt of reaction interface
F1/2, R2 (1  a)1/2 2[1  (1  a)1/2] One-half-order kinetics;
where k(T) is the rate constant at absolute temperature T, t is the two-dimensional advance
reaction time, and a is a degree of reaction, which is defined as of reaction interface
follows: F2/3, R3 (1  a)2/3 3[1  (1  a)2/3] Two-thirds-order
kinetics; three-dimensional
advance of reaction
ðWi  Wt Þ
a ¼
 (2) interface
Wi  Wf F1 (1  a) ln(1  a) First-order kinetics
F2 (1  a)2 a/(1  a) Second-order kinetics
P2 a1/2 2a1/2 Power law
where Wi and Wf are the initial and final sample mass, respectively, A2 (1  a)[ln 2[ln(1  a)]1/2 AvramieYerofeyev equation

and Wt is sample mass at any time t. According to Sesták [11], the (1  a)]1/2
kinetic function f(a) is related to the reaction mechanism, and can D1 1/a a2/2 Parabolic law
P-T a (1  a) ln[a/(1  a)] ProuteTompkins equation
be written in the following general form:
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J.H. Shin et al. / Materials Chemistry and Physics 143 (2014) 1075e1081 1077

The Kissinger method is based on the rate equation at the from the slope of a plot of the natural logarithm of the heating rate
maximum reaction rate [17]. At this point, ðd2 a=dt 2 Þ or ðd2 a=dT 2 Þ is lnbi versus 1=Ta i .
equal to zero. Thus, Eq. (10) is obtained from Eq. (8).
3.2.3. CoatseRedfern method
     CoatseRedfern method is an integral method as likely as
d a
2
Ea b A Ea dT
¼ $ $exp  $f ða Þ$ FlynneWalleOzawa method and it involves the function of re-
dt 2 RT 2 b RT dt action model. In the CoatseRedfern method, an asymptotic
     (10)
0 Ea da approximation is used for solution of the p(x) function as
þ A$f ðaÞ$exp  $ ¼ 0
RTm dt follows [22].
 
2 expð  xÞ
From Eqs. (9) and (10), the following equation is deduced. pðxÞy 1  $ (18)
x x2
 !  
d2 a Ea b 0 Ea da Therefore, Eq. (19) is obtained by combining Eqs. (14) and (18).
¼ þ A$f ð aÞ$exp  $ ¼ 0 (11)     
dt 2 RTm 2 RTm dt
gðaÞ AR 2RT Ea
ln ¼ ln $ 1   (19)
T2 bEa Ea RT
where Tm is the temperature at which the second derivatives of
ðd2 a=dt 2 Þ or ðd2 a=dT 2 Þ equal zero. As follows from Eq. (11), Thus, the activation energy can be obtained by plotting the left-
hand side (including the model, g(a)) versus T1.
 
Ea b 0 Ea 4. Results and discussion
2
¼ A$f ð aÞ$exp  (12)
RTm RTm
4.1. Thermogravimetric analysis

The weight loss of ZrCl4 as a function of time at each isotherm in

Eq. (12) can be rearranged after inserting logarithms into the
the temperature range of 300e550  C is shown in Fig. 1. Weight loss
Kissinger equation:
drastically increased with increasing temperature. Approximately
!  
b AR Ea
ln 2
¼ lnðf 0 ðaÞÞ þ ln   (13)
Tm Ea RTm

A plot of the left side of this equation as a function of reciprocal

temperature gives a straight line with slope equal to the activation
energy [17].

3.2.2. FlynneWalleOzawa method

The kinetics of sublimation was also studied using the iso-
conversional method of FlynneWalleOzawa [18,19]. In a non-
isothermal system, f(a) can be expressed in integral form as the
function g(a) as follows:

Za ZT  
da A Ea AEa
gðaÞ ¼ ¼ $ exp  $dT ¼ $pðxÞ (14)
f ðaÞ b RT bR
0 0

where x is Ea =RT and the p(x) function is defined as follows

Zx
expð  xÞ
pðxÞy  $dx (15)
x2
N

Eq. (15) has no analytical solution but has many approximations

[18e21]. The FlynneWalleOzawa method is one of the most pop-
ular one. The p(x) function was described by Flynn, Wall, and Ozawa
using Doyle’s approximation as follows [18e20]:

pðxÞy0:0048$expð1:0516$xÞ (16)
Eq. (14) is then rearranged for b,
 
Aa Ea Ea
lnbi ¼ ln  5:331  1:0516 (17)
RgðaÞ RTa

where subscripts i and a denote a given heating rate and value of

conversion, respectively. The activation energy is then calculated Fig. 1. Weight loss (%) vs. time under (a) isothermal and (b) non-isothermal conditions.
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1078 J.H. Shin et al. / Materials Chemistry and Physics 143 (2014) 1075e1081

Table 2
Slope of g(a) vs. time for each kinetics model at 300  C. Slope of g(a) vs. time for each
kinetics model at 300  C.

Model Slope R-squared

F0, R1, P1 0.0368 0.995

F1/2, R2 0.0559 0.980
F2/3, R3 0.0670 0.958
F1 0.1067 0.849
F2 1.7627 0.251
P2 0.0838 0.970
A2 0.1349 0.991
D1 0.0152 0.951
P-T 0.0854 0.350

80% of the initial weight of ZrCl4 was sublimated when temperatures

were lower than 350  C, while approximately 90% of the initial
weight of ZrCl4 was sublimated at temperatures greater than 400  C.
ZrCl4 weight loss with time under non-isothermal conditions with
heating rates of 8  C min1 and 17  C min1 is also shown in Fig. 1.
Weight loss drastically increased after about 330  C, the sublimation
temperature of ZrCl4. Maximum sample loss was higher with a
heating rate of 8  C min1 than with a heating rate 17  C min1.

4.2. Reaction model of sublimation of ZrCl4 compound under

isothermal conditions

According to Eq. (4), g(a) should have a linear relationship with

time. The slope of the plot of g(a) versus time at 300  C is listed in
Table 2. Slope was calculated by linear regression analysis, and R-
squared represents the coefficient of determination for each reac-
tion model. The F0 and A2 models (R-squared is 0.995 and 0.991,
respectively) show a good linear relationship between g(a) and
time. However, the A2 model involves random nucleation and
subsequent growth, which is not applicable to the sublimation
mechanism.
The F0 model for chemical decomposition is called ‘zero-order
kinetics’. Dollimore suggested necessary assumptions for the
application of a model based on zero-order kinetics as follows [23]:
Fig. 3. SEM images of samples at different degrees of reaction (a) at 550  C.

1. The existence of a reaction interface.

2. The rate of reaction for a unit area of interface is constant at any A schematic illustration of ZrCl4 sublimation in the present
given temperature. experimental conditions is presented in Fig. 2. The area of the
3. For a small incremental change in temperature or time, the area interface of ZrCl4 samples is constant to the cross-sectional area of
of the reaction interface does not change. the crucible and the interface moves one dimensionally,

For zero-order kinetics, the movement of the sample interface

under isothermal conditions should only be one-dimensional and
the interface area should not change.

Fig. 2. Schematic illustration of ZrCl4 sublimation. Fig. 4. g(a) vs. time under isothermal conditions at different temperatures.
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J.H. Shin et al. / Materials Chemistry and Physics 143 (2014) 1075e1081 1079

Table 3
Slope of g (a) vs. time at each temperature for zero-order process.

Temp ( C) k(T) (min1) Intercept R-squared

300 0.0368 0 0.995

330 0.0453 0 0.993
350 0.0582 0 0.993
400 0.0758 0 0.992
450 0.0889 0 0.992
500 0.1199 0 0.991
550 0.1562 0 0.995

representing zero-order kinetics. SEM analysis was performed to

observe the morphology of all samples, and the results are shown
in Fig. 3. The crucible was initially filled with pure ZrCl4 powder,
which has widely variable particle diameters. From the particle size
distribution during and after the sublimation process, each particle
was initially sintered and then sublimated. In other words, ZrCl4
compact in the crucible behaved as a bulk solid. A number of pre-
vious studies have reported that the reaction mechanism for the
evaporation or sublimation of the condensed phase follows zero-
order kinetics [12,23e27].

4.3. Isothermal kinetics

Since ZrCl4 sublimation is a zero-order process, the mass frac-

tion sublimated is equal to the product of time and the rate con-
stant, i.e. gðaÞ ¼ a ¼ kðTÞ$t. Fig. 4 shows g(a) vs. time curves at
each temperature. According to Eq. (4), the rate constant k(T) was
calculated from the slope of fitted lines at each temperature. The
calculated rate constants, listed in Table 3, increase with increasing
temperature. Based on Eq. (5), the activation energy of ZrCl4 sub-
limation was obtained from an Arrhenius plot, as shown in Fig. 5.
The activation energy is 21.7 kJ mol1.

4.4. Non-isothermal kinetics
To determine Tm at different heating rates, ðda=dTÞ was plotted
against temperature at heating rates of 17  C min1 and 8  C min1,
as shown in Fig. 6. At a heating rate of 17  C min1, ðd2 a=dT 2 Þ
equaled zero at Tm ¼ 423.2  C, whereas Tm ¼ 397.6  C at a heating
rate of 8  C min1. The Kissinger method was adopted to calculate
the activation energy of ZrCl4 sublimation under non-isothermal
conditions. Fig. 7 shows a plot of ðlnb=Tm2 Þ versus ð1=TÞ, in which
the slope equals activation energy. The activation energy was
calculated to be 101.4 kJ mol1.
Fig. 6. da/dT vs. temperature under non-isothermal conditions at heating rate of (a)
17  C min1 and (b) 8  C min1.
Alternatively, the isoconversional plots based on the FlynneWalle
Ozawa method is appeared in Fig. 8. The calculated activation energies
of ZrCl4 sublimation at each conversion rate are summarized in
Table 4. The average activation energy of ZrCl4 sublimation obtained
from the Flynn-Wall-Ozawa method is 108.1 kJ mol1, which is very
close to that obtained with the Kissinger method.

-1.0

-1.5

-2.0
lnk (T )

-2.5

-3.0

-3.5 -2.622

-4.0
1.00 1.25 1.50 1.75 2.00
-1
1000/T (K )
Fig. 5. Arrhenius plot of rate constant against reciprocal temperature. Fig. 7. ðlnb=Tm
2 Þ vs. T1 curve.
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1080 J.H. Shin et al. / Materials Chemistry and Physics 143 (2014) 1075e1081

Fig. 9. Kinetic plot indicating F1 model by using CoatseRedfern method.

Fig. 8. ln (b) vs. T1 curve.

Table 4
Activation energy of ZrCl4 sublimation under non-isothermal conditions obtained by these values are relatively close to the heat of ZrCl4 sublimation
Kissinger and FlynneWalleOzawa methods. ðDHsub
ZrCl4
¼ 103:3 kJ mol1 Þ reported by Palko et al. [8] Neverthe-
Method Activation energy (kJ mol1) less, the activation energy of ZrCl4 sublimation is inconsistent for
Kissinger 101.4
non-isothermal and isothermal conditions.
According to Somorjai [28], a sublimation reaction has two
FlynneWalleOzawa Degree of reaction 0.2 99.6
elementary steps. First, atoms break away from their neighbors
(a) 0.3 107.5
0.4 95.4 in the crystal lattice, and second, atoms are removed into the gas
0.5 129.5 phase. The first step, called the surface reaction step, involves
0.6 112.4 atoms breaking away from a kink site and then diffusing on the
0.7 104.1 surface until they are ready to vaporize. The second step, called
Average 108.1
the desorption step, involves the diffusion of atoms into gas
phase after desorbing sublimation substance from the sublima-
tion surface. Thus, sublimation probably has two activation
The calculated activation energies for different models at each energies.
heating rate by using CoatseRedfern method are listed in Table 5. As discussed above, the activation energy of ZrCl4 sublimation
The A2 model (R2 ¼ 0.981 and 0.994 for heating rate ¼ 8  C min1 measured under non-isothermal conditions in the present study
and 17  C min1, respectively) show a good linear relationship (Ea ¼ 104.8 (3.4) kJ mol1) is close to the heat of ZrCl4 sublimation.
between lngðaÞ=T 2 and 1=T. However, in view of the activation This indicates that the activation energy of ZrCl4 sublimation under
energy as shown in Table 5 and Fig. 9, the F1 model (R2 ¼ 0.969 and non-isothermal conditions represents overall activation energy
0.965) is more consistent with the experimental results than A2 that involves two energy barriers for two steps. The activation
model. Consequently, the F1 model, viz. first-order kinetics, is energy of ZrCl4 sublimation under isothermal conditions is low
acceptable for ZrCl4 sublimation kinetics under non-isothermal (Ea ¼ 21.7 kJ mol1) compared to the heat of ZrCl4 sublimation. This
condition. indicates that one of the two steps was skipped, because ZrCl4 was
suddenly subjected to high temperatures when loaded into the
4.5. Multistep sublimation furnace.

From Table 4, the Kissinger and Flynn-Wall-Ozawa methods

afford similar activation energies for ZrCl4 sublimation. Moreover,

Table 5
Activation energy of ZrCl4 sublimation under non-isothermal conditions by Coatse
Redfern method. Activation energy of ZrCl4 sublimation under non-isothermal
conditions by CoatseRedfern method.

Model 8  C min1 17  C min1

1
Ea (kJ mol ) R-squared Ea (kJ mol1) R-squared

F0, R1, P1 25.1 0.738 54.7 0.973

F1/2, R2 45.6 0.921 64.1 0.988
F2/3, R3 37.2 0.869 67.5 0.991
F1 99.2 0.969 95.0 0.965
F2 243.7 0.970 121.6 0.997
P2 6.7 0.434 21.5 0.954
A2 37.1 0.981 31.6 0.994
D1 61.8 0.814 121.2 0.978
P-T 132.7 0.820 252.4 0.780
Fig. 10. Schematic diagram of activation energy of ZrCl4 sublimation.
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J.H. Shin et al. / Materials Chemistry and Physics 143 (2014) 1075e1081
The activation energy for vacuum sublimation can be approxi-
mated by the heat of sublimation. Equilibrium can likely be estab-
lished in all surface reaction steps, leading to vaporization. In
addition, the desorption of substance atoms from the surface re-
quires no extra activation energy [28]. Under atmospheric pressure,
the desorption step may have an activation energy, although it has a
relatively low value, as shown in Fig. 10. Thus, activation energy
measured under isothermal conditions can be considered the en-
ergy barrier for the desorption step. There is a difference between
non-isothermal activation energy, or the overall energy barrier of
ZrCl4 sublimation, and isothermal activation energy, or the energy
barrier for desorption. The activation energy for the surface reaction
step is estimated to be about 83.1 kJ mol1.
From these results one can conclude that the sublimation of ZrCl4
under isothermal condition is mainly controlled by desorption step.
However, because the activation energy of surface reaction step is
higher than that of desorption step, the sublimation of ZrCl4 is
limited by surface reaction step under non-isothermal condition.
5. Conclusions
The sublimation kinetics of ZrCl4 was investigated using the TGA
method under isothermal and non-isothermal conditions. The
sublimation rate of ZrCl4 increased with increasing temperature
under isothermal conditions. ZrCl4 sublimation was confirmed to be
a zero-order process under isothermal condition, and its activation
energy under isothermal conditions was determined to be
21.7 kJ mol1. The activation energy of non-isothermal sublimation
was determined to be 101.4 kJ mol1 and 108.1 kJ mol1 using the
Kissinger and FlynneWalleOzawa methods, respectively. By
employing the CoatseRedfern method, the sublimation of ZrCl4 was
confirmed to be a first-order reaction under non-isothermal con-
ditions. The non-isothermal activation energies were very close to
the heat of sublimation (103.3 kJ mol1). Sublimation occurs by the
two elementary steps of surface reaction and desorption. Therefore,
the overall activation energy of ZrCl4 sublimation is 104.8
(3.4) kJ mol1. The activation energy of the surface reaction and
desorption steps were proposed to 83.1 kJ mol1 and 21.7 kJ mol1,
respectively. Thus, the sublimation of ZrCl4 under isothermal con-
dition is mainly controlled by desorption step, whereas it is limited
by surface reaction step under non-isothermal condition.
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