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Physica B 404 (2009) 36553661

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Physica B
journal homepage: www.elsevier.com/locate/physb

X-ray diffraction analysis for isothermal annealed powder Mg(OH)2


A. Ranaivosoloarimanana , T. Quiniou, M. Meyer, J.M. Boyer, F. Rocca
a Cedex, New Caledonia
Pole Pluridisciplinaire de la matie`re et de lEnvironnement (PPME EA 3325), Universite de la Nouvelle-Caledonie, BPR4 - 98851 Noume

a r t i c l e in fo

abstract

Article history:
Received 13 November 2008
Received in revised form
19 May 2009
Accepted 4 June 2009

In this paper, we use an XRD-based 100% approach method to quantify the activity evolution of phase
transformation from annealed powder Mg(OH)2 to MgO. The sample is chemically synthesized. The
isothermal phase transformation is carried out between 300 and 310 1C. The ratio of reacted magnesium
hydroxide is applied and compared with different existing models. The Avrami model An appears to be
the most close-tting. An order of reaction between 1.5 and 2 is observed that it could be considered as
a complex combination of different phenomenon, for which we test different models.
& 2009 Elsevier B.V. All rights reserved.

PACS:
61.05.cp
64.70.K
65.80.+n
Keywords:
Magnesium hydroxide
Powder X-ray diffraction
Kinetic
Thermal decomposition
100% approach

1. Introduction
Magnesium hydroxide and oxide are widely used for industrial
applications. Magnesium oxide is found as pigment in paints, in
neutralizing agents, pharmacological products and sport grips.
Magnesium hydroxide is a component used in re retardant and a
common component of pharmaceutical antiacids and laxatives.
Magnesium hydroxide is a soil constituent.
Magnesium oxide can be obtained in different ways but one of
the most widespread is the thermal decomposition of magnesium
hydroxide [13]. MgO is the product of the isothermal heating of
Mg(OH)2 by the following equation:
MgOH2 ) MgO H2 O:

(1)

The product of thermal decomposition behaviour depends on


the reaction temperature. The study of kinetic decomposition is
reported in numerous studies. The mechanism can be described
using physical and chemical models [4]. The chemical model is
based on two steps, i.e. nuclei formation and the growth of the
dehydrated phase. Several models, which have been developed
from different nucleation and growth laws, were listed by
Sharp et al. [5] and are noted as Dn, Rn, F1, An. In the case of an
 Corresponding author. Tel.: +687 26 58 00; fax: +687 25 48 29.

E-mail addresses: albert.ranaivosoloarimanana@univ-nc.nc,


albertranai@yahoo.com (A. Ranaivosoloarimanana).
0921-4526/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2009.06.043

instantaneous nucleation step, the kinetic of the dehydratation


reaction is controlled by the growth step, for which the ratelimiting step can be carried out using a diffusion mechanism or
interfacial reaction [6]. Dn and Rn models are the models that
consider the diffusion mechanism and the interfacial reaction,
respectively. n is a parameter that depends on the particle shape.
For the model F1, nucleation and growth remain two successive
steps but the growth is considered instantaneous. Unlike complex
models, which take the competition between the nucleation and
growth process into account, the three aforementioned models
are dened as limits. The An model is one of the complex models
developed from a volume random germination and an isotropic
nucleus growth. It was implemented by Kolmogorov et al. [7] and
is thus known as the KJMA model. n depends on both the particle
morphology and the nucleus shape.
Numerous studies have reported on the thermal decomposition of magnesium hydroxide over the past 70 years [812]. These
studies were carried out in order to obtain the activation energy of
magnesium hydroxide decomposition and led to the establishment of the rst kinetic decomposition models. These studies
include the work of Anderson et al. [9] who examined the
isothermal decomposition of precipitated magnesium hydroxide
by thermogravimetric analysis under vacuum. They modelled
their results by phase boundary controlled mechanism in 2D as a
kinetic model. Turner and Hoffman carried out a similar study at
atmospheric pressure with a differential thermogravimetric
device. Using an isothermal and non-isothermal experimental

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protocol, the model employed to describe the kinetic of precipitate magnesium hydroxide decomposition is a two thirds
order reaction model. More recently Halikia et al. [13] implemented the isothermal thermogravimetric method on pure
magnesium hydroxide. They showed that the kinetic mechanism
depends on temperature. At 350 1C, the data can be tted by a F1
kinetic law, while at 400 1C it is the A2 Avrami model that provides
the best t. At 450 and 500 1C, it was found that the controlling
mechanism remains the nucleus production as described by the
An model. The use of the An model is reported again by Yue et al.
[14] who studied magnesium dehydratation with a non-isothermal thermogravimetric analysis. Thus, the determination of
kinetic behaviour and parameters as activation energy remains
unclear in the case of magnesium hydroxide as for another
crystallized phase [15].
In other studies, the quantitative X-ray powder diffraction is
applied to different experimentations as monitoring phase
analysis [16] or in situ following crystallization, using classical
X-ray apparatus combined with synchrotron radiation [17,18]. The
recent development of an X-ray detector, which reduced the time
needed to perform the data acquisition (curved detector, for
example) enables thermal kinetic monitoring using a laboratorys
X-ray apparatus.
Moreover, previous studies have presented MgO thermal
kinetic investigation based on a Jensen treatment [19]. Recent
studies present suitable quantitative phase determination, which
is based on the 100% approach that takes into account the
intensity of all diffraction peaks [20]. In this study, we propose to
use it for the data treatment of the thermal analysis of magnesium
hydroxide particles carried out in situ X-ray diffraction equipped
with a curved detector.
The second section of this article details the technical
characterization of the particles and the experimental procedure
for the data treatment. The third and fourth sections demonstrate
the data obtained and their application to a literature model in
order to determine the most suitable model.

detector, INEL CPS 120, between 01 and 120 2y at a step size of


0.031.
Using both an X-ray diffractometer and a furnace, it becomes
possible to investigate the phase evolution of hydroxide while it
transforms into oxide. Compared to more traditional methods,
such as thermo-gravimetry or calorimetry, X-ray diffraction
allows us to follow up the phase evolution of every diffraction
plane [h k l]. [h k l] are Millerss indices. However, far more time is
required to perform a full-pattern analysis, but this can be
reduced using a curved detector. During our experiments, each
diffraction pattern containing full-pattern diffractogram was
cumulated over 10 min period. The nal output le included all
diffraction patterns, the rst one being the hydroxide and the last
one the oxide.
(c) Data treatment: The diffraction le is analysed using
laboratory-made software developed under Matlab (V7.0 (R14)).
It is designed to automatically enable the processing of multiple
diffraction patterns. The nal purpose of this software is to
investigate the thermal decomposition kinetic of a sample using
an X-ray diffractometer. Particular emphasis is given to the design
and implementation of the user interface.
In the rst stage, diffraction patterns are extracted individually
from the output le. Each diffractogram is then processed and
tted using analytical pseudo-voigt functions [22]. The background, linear in a rst approximation under each peak or group
of peaks, is jointly tted and removed. All of the detected
diffraction peaks are indexed to Mg(OH)2 or MgO crystal planes
from ICDD PDF-2 cards [23]. The software can display different
gures, such as variations of peak intensity, peak position, and
particle size versus time for a given temperature (isothermal
mode) or versus temperature for non-isothermal mode. It can also
display the evolving phase fraction during the Mg(OH)2 sample
transformation. Finally, the experimental curves are compared to
the most important rate equation used in the kinetic analysis of
solid state reactions.

2.3. Decomposition analysis


2. Experimental technique
2.1. Particle synthesis [21]
Magnesium hydroxide Mg(OH)2 particles are synthesized by
adding 50 ml of an alkaline solution to 50 ml of a magnesium
nitrate Mg(NO3)2 solution, the molar ratio of base to magnesium
is 50%. This mixture is heated at 80 1C for 60 min under vigorous
stirring. After cooling, the precipitate is isolated by centrifugation and stirred in water. Isolation of precipitate and redispersal in water is performed ve times. Then water is
evaporated at 40 1C.
2.2. Particle characterization
(a) TEM: The morphology of the particles is determined by
transmission electron microscopy (JEOL 100 CX2). Dilute suspensions of Mg(OH)2 particles are dispersed in ethanol using
ultrasonic vibrations and deposited on a carbon-covered grid,
then ethanol is evaporated.
(b) X-ray diffraction: The thermal decomposition of magnesium
hydroxide is carried out in air in an Anton-Paar TTK450 furnace.
During calcination, the powder X-ray diffraction patterns are
acquired using an INEL diffractometer operating at 30 kV and
30 mA. The transmitted X-ray beam is produced from a ltered
cobalt source Ka1 (l 0.178897 nm). The intensity of the
diffracted beam is recorded with a curved position-sensitive

Some literature reported the possibility of inuence by the


sample quantities and by the moisture. To avoid this interference,
all of our data are obtained from 25 mg of Mg(OH)2 and our
furnace is maintained at 150 1C for a period of 2 h prior to each
experiment to dry the sample [1].
(a) Selection of a suitable isothermal temperature: As a rst step,
linear temperature scanning measurements are carried out to
determine the best temperature interval for the next step, i.e.
isothermal analysis. The temperature for the isotherm experiments are chosen just before a phase transformation (Fig. 1). The
choice is made to avoid a long-time measurement if the
temperature is too low; the beginning of phase transformation
is lost if the temperature is too high.
In order to evaluate the suitable temperature range, diffraction
patterns are measured at regular scanning temperature intervals
between 200 and 400 1C. Fig. 2 shows the diagram evolution
for this rst step. The average temperature variation is
dT/dt 0.5 1C/min.
The second step involves the implementation of the X-ray
diffraction analysis and characterizations for the isothermal phase
shift from Mg(OH)2 to MgO. The selected temperatures for the
isothermal analysis of the magnesium hydroxide sample are 300,
305 and 310 1C. Fig. 3 shows isothermal phases diagram evolution
of Mg(OH)2 to MgO chosen between 300 and 310 1C.
Once the method, the main parameters of analysis and the
isothermal temperature interval have been chosen and determined, an isothermal measurement is carried out. The processing

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of the acquired data enables us to establish the evolution of each


crystalline plane and the concentrations of Mg(OH)2 and MgO.
Thus the Mg(OH)2 fraction reacted ratio on isothermal annealing
can be determined.
(b) Ratio a determination: We denote by a the ratio of MgO
product. The empiric value of the Mg(OH)2 fraction reacted ratio is
determined using the ratio of the modelled surface peaks of
Mg(OH)2 and MgO. The relation of the X-ray powder diffraction
peak, the structural factors and scattering factor, and their
application for mixed phases can be found in the literature [24].
Another method for the calculation of the phase ratio used by
Jensen [19] can be found using the following formula:

at

Fig. 1. Evolution of Mg(OH)2 and MgO phases versus temperature scanning


(non-isothermal measurement).

Ii t  Imin 
,
Imax  Imin 

(2)

where Ii is the intensity for peak i and a the ratio of phase i on


mixture phases.
Another method, which is slightly different to Eq. (2), is used to
determine the ratio a in this study. The method uses the tted and
modelled integral intensity peaks so-called 100% approach.
The 100% approach method is described by Kahle [20]
introducing mineral intensity factors (MIFs), denoted by Z. To
adopt Kahles denitions, the mineral intensity factor describes
the relationship between the intensity ratio of specic X-ray
diffraction peaks and the weight fraction ratio of two phases in a
mixture. The term 100% approach means that the sum of all of the
phase quantities identied in a sample is 100%.
We also use full-pattern methods to perform quantitative
phase analysis. Full-pattern methods consist in tting complete
experimental diffraction. In our case, we use the entire 1201
aperture for diffraction angle 2y.
According to the Kahle equation [20], the integral intensity I of
the specic diffraction peak of the given phase is
I K  W  U,

(3)

where K is constant, W is the weight fraction of the mineral and


U is function of the mean mass absorption coefcient and the
structure factor of the mineral.
Then in a mixture of the two phases i and j, a peak intensity
ratio could be described as
  
Ii
Wi
Ui
.
(4)

Ij
Wj
Uj
Fig. 2. Temperature ramp for annealed Mg(OH)2.

In this relation U i =U j is referred to as the MIF ratio Zi =Zj [20],


and the weight fraction W i of phase i mixed with any phase n is
determined by
I =Z
.
Wi P i i
n In =Zn

Fig. 3. Diagram evolution for annealed Mg(OH)2 chosen between 300 and 310 1C.

(5)

Thus, in our case the ratio of created oxide magnesium can be


determined using the following formula:
P
hkl IMgO
P
a P
,
(6)
f S hkl IMgOH2 hkl IMgO
P
where
intensity sum of all [h k l] tted
hkl IMgO is the integral
P
MgO peaks for MgO and hkl IMgOH2 for all [h k l] tted Mg(OH)2
peaks. To make this calculation, as shown, for example in Figs. 6
and 7, the background is already removed during pseudo-voigt
tting.
Our empiric MIF ratio called fS is determined by
P
IMgOpure
f S P hkl
,
(7)
hkl IMgOH2 pure
P
where hkl IMgOpure is the integral intensity measurement from a
P
pure sample of MgO and hkl IMgOH2 pure is the integral intensity
measurement from the same mass of Mg(OH)2 pure sample.

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3. Experimental results
The TEM micrograph of the magnesium hydroxide sample is
shown in Fig. 4. The morphology sample is platelet-like.
Fig. 5 shows the size distribution. The mean size value is
79.5 nm.
The XRD pattern of the magnesium hydroxide is shown in
Fig. 6. All diffraction peaks can be indexed as the hexagonal
structure of magnesium hydroxide (JCPDS le number 86-0441)
[24]. There is no additional diffraction peak in the pattern,
indicating that the sample has no measurable impurity.
The XRD pattern of the magnesium oxide obtained at the end
of the calcination is shown in Fig. 7. All diffraction peaks can be
indexed as the cubic structure of magnesium oxide (JCPDS le
number 78-0430) [24]. There is no additional diffraction peak in
the pattern, thus indicating that the decomposition is complete.
Integral intensity at 310 1C: An example of [h k l] integral
intensity peaks at 310 1C is shown in Fig. 8. The curve has a
sigmoid shape. This data type allows us to determine the
evolution of the ratio a with the formula (6) using all
simultaneous [h k l].

Variation of 2y at 310 1C for MgO: The peak position of MgO can


be extracted using acquisition data. For each peak, the rst
appearance of their position is taken as reference. Fig. 9 shows the
difference position during MgO growth.
Thus Fig. 9 shows that a complex phenomenon appears during
calcination, at least during germination and growing crystallization. It appears that cell size changes during the phase
transition.

4. Model tting
As the experimental method used is somewhat original in this
context, a large number of the most commonly used kinetic
models were tested and compared, to solve the kinetic equation of
a solid state reaction
da
k  f a:
dt

(8)

Cumulative quadratic method: The reduced time parameter t0 at


time t as t 0 t=t 0:5 is introduced. To analyse our data t 0:5 , whereby

Fig. 4. TEM micrograph of the magnesium hydroxide sample.

Fig. 5. Size distribution of the sample.

Fig. 6. Mg(OH)2 full-pattern diffractogram.

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the half of magnesium hydroxide is reacted, is taken as reference.


Thus, at this time t 0:5 , the ratio a is equal to 0.5 and the reduced
time is equal to 1. This method is well-known for many solid state
reactions [5]. The ratio a and the quadratic differences from the
experimental results are evaluated (Figs. 1015) by introducing
this common reduced time in the F 1 , Dn , Rn , An . Details of those
models are described by Halikia [13].
With different models, the following gures show at different
temperatures, rst, the ratio of reacted magnesium hydroxide a
versus time [5] and, second, the cumulated quadratic difference
between experimental data and different models.
For the reduced time less than 1, the quadratic difference is
then accumulated from 1 to 0. And for the reduced time greater
than 1, the accumulation is from 1 to the end.
Figs. 1012 show the reduced time plot for the sample and the
most important rate equations.
Figs. 1315 show the cumulated quadratic difference between
data and rate equations.
Fig. 7. MgO full-pattern diffractogram.

Fig. 8. Integral intensity peaks during phase transformation (310 1C).

Fig. 10. The reduced time plot for the sample and the most important rate
equations at 300 1C.

Fig. 9. Evolution of peak position during the transformation phase (310 1C).

Fig. 11. The reduced time plot for the sample and the most important rate
equations at 305 1C.

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At the three temperatures 300, 305 and 310 1C for the reduced
time less than 1, A1.5 model (n 1.5) is the best t for our data. For
the reduced time greater than 1, at temperature 300 and 310 1C,
A1.5 model (n 1.5) is the best t but at 305 1C, A2 model (n 2)
becomes the best t.
AvramiErofeevs tting: We conrm in this analysis that
AvramiErofeevs models [15], dened by
 ln12a1=n kt

or

a 12 expktn 

(9)

are the most appropriate choices for the decomposition of


magnesium hydroxide, as already quoted in the literature [13,14].
Thus, our analysis is focused on determining, as described in
the previous AvramiErofeevs equation (9), the best values of n
for each temperature T at 300, 305 and 310 1C. To make it, a is
determined using full-pattern diagram that requires the 100%
approach method. The value n 1.51 for 300 1C, n 1.75 for
305 1C and n 1.52 for 310 1C are obtained, which are shown in
Fig. 16.
Fig. 12. The reduced time plot for the sample and the most important rate
equations at 310 1C.

Fig. 13. The cumulated quadratic difference between data and rate equations at
300 1C.

Fig. 14. The cumulated quadratic difference between data and rate equations at
305 1C.

Fig. 15. The cumulated quadratic difference between data and rate equations at
310 1C.

Fig. 16. Curves with AvramiErofeevs model tting.

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5. Discussion and conclusion

Acknowledgements

This result is in qualitative agreement with some reports, in


particular with those of Yue et al. [14] describing a non-isothermal
experiment, in which the mechanism of decomposition changes
between A1.5 and A2, in this case according to the rising heating
rate.
It is known that AvramiErofeevs models are especially
adapted for random nucleation and nuclei growth process. If the
growth is essentially limited by interfacial reactions, the models
are suitably adapted with integer values of the coefcient n which
appears in the denition (9) of these models. If the growth is
notably limited by diffusion effects, the best models are obtained
with half-integer value of n [25]. It appears that the temperature
interval 300310 1C contains some critical and complex phenomena. It may certainly be expected that, during the experiment
time, which is important (for example 5 h to obtain a 12 for
T 305 1C), both previous mechanisms occur concurrently, and
consequently that the true kinetic equation would be suitably
described using some linear combination of the two models A1.5
(with n 1.5) and A2 (with n 2).
Moreover, other external parameters are to be considered. In
particular, the importance of water vapour is well known [14].
We may conclude that the decomposition mechanism of
magnesium hydroxide would be well described, at least in the
temperature interval [300, 310 1C], taking the AvramiErofeev
model with a coefcient n, which is a function of the temperature
T and some external parameter j, with numerical values in the
interval between 1.5 and 2. So, the equation of the decomposition
takes the form

We would like to thank P. Baunier and V. Godichon for their


help with the experimental work and C. Metayer for his
bibliographical support.

a 1  expktnT;j .

(10)

In this relation, the rate decomposition grows with n, and n(T,j)


theoretically describes the change of the crystalline microstructure during the reaction. In this way, new experiments in nonisothermal situation can be now expected.

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