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Powder Technology 234 (2013) 2631

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Powder Technology
journal homepage: www.elsevier.com/locate/powtec

Rapid fabrication of nanostructured magnesium hydroxide and hydromagnesite via


microwave-assisted technique
Gary W. Beall a, c,, El-Shazly M. Duraia a, b, Farid El-Tantawy b, Faten Al-Hazmi c, Ahmed A. Al-Ghamdi c
a
b
c

Texas State University-San Marcos, Department of Chemistry and Biochemistry, 601 University Dr., San Marcos, TX 78666, USA
Suez Canal University, Faculty of Science, Physics Department, Ismailia, Egypt
Physics Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 24 April 2012
Received in revised form 14 August 2012
Accepted 15 September 2012
Available online 23 September 2012
Keywords:
Magnesium hydroxide
Hydromagnesite
Microwave-assisted technique

a b s t r a c t
Magnesium hydroxide and hydromagnesite nano and microstructures have been prepared by using
microwave-assisted technique. Magnesium chloride, magnesium acetate and magnesium metal have been
used as a magnesium source. Urea has been added to the solution with controlled pH = 10 while the temperature was 220 C. The hydrolysis of urea under these hydrothermal conditions leads to the production of
hydromagnesite instead of magnesium hydroxide. The as-prepared samples were investigated using scanning electron microscope (SEM), X-ray diffraction (XRD), thermographmetric analysis (TGA) and differential
scanning calorimetry (DSC). SEM shows a wide distribution of pseudo-hexagonal nanodisk up to microdisk.
Spherical rosette morphology has been noticed in the samples in which the urea has been used. XRD reveals
the existence of Mg(OH)2 with some impurities which can be attributed to the high concentrations of the initial materials and absorption of carbon dioxide from the air when urea is not employed and hydromagnesite
when urea is present in the synthesis. TGA showed a weight loss within the temperature range of 360450 C
with a total percentage of weight loss 29% which can be attributed to the (Mg(OH)2). However in the case of
synthesis with urea the weight loss was 57% which is the expected value for hydromagnesite. The production
of pure hydromagnesite utilizing hydrothermal methods has been reported; the synthesis reported here is
much simpler and faster.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Magnesium hydroxide (Mg(OH)2) has many applications due to
its outstanding physical and chemical properties. For example due
to it structural properties it can be formed in laminated form and its
good compatibility with many polymer matrices, it is widely used as
ller. Moreover, magnesium hydroxide (Mg(OH)2) possessing an advantageous arrangement for the formation of platelet-like crystals,
has high decomposition temperature and it is commonly used as a
ame retardant in the composite materials [14].
There are many methods that can be used for the Mg(OH)2 synthesis such as electrolysis from an aqueous magnesium salt solution,
hydration of magnesium oxide, precipitation of a magnesium salt in
alkaline solution, solgel technique, ammonia gas bubbling reactors
and microwave assisted synthesis [5].
For example, Mg(OH)2 with different morphologies such as rod
tube needle or lamina have been synthesized by hydrothermal reaction using different magnesium sources such as magnesium powder,

Corresponding author at: Texas State University-San Marcos, Department of Chemistry


and Biochemistry, 601 University Dr., San Marcos, TX 78666, USA.
E-mail address: gp11@txstate.edu (G.W. Beall).
0032-5910/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.powtec.2012.09.029

MgSO4 and Mg(NO3)26H2O. The authors found that the crystallite


size, shape, and structure, can be controlled well by choosing different solvents and reaction conditions [6].
Surfactants or structure directing agents have been used to control
the size and shape of the metal oxides nanostructures. In the open literatures, there are a few reports about using urea in order to control
the Mg(OH)2 synthesis. For example, Kumari, et al. found that the addition of urea together with PEG is advantageous in controlling the
nanoparticles' growth. These reports however were conducted at
below 110 C and only reported a small impurity of hydromagnesite
[7].
The crystallization behavior of the Mg(OH)2 also depends on the magnesium source; for example Gao et al. found that the sunower-like structures were obtained for magnesium Chloride (MgCl2) and with the
column-shaped superstructures when magnesium dodecyl sulfate
[Mg(DS)2] was used [8].
Hydromagnesite (Mg5(CO3)4(OH)24H2O) is one of the only stable hydrated hydroxy carbonates at room temperature. It is a better
ame retardant than Mg(OH)2 since it yields more water and CO2
per mass and has been widely used as a ller in polymer systems.
Microwave technique attracts more interest because it can generate heat internally inside the sample so the heat can be transferred
homogenously and rapidly. The microwave technique requires far

G.W. Beall et al. / Powder Technology 234 (2013) 2631


Table 1
Reactant proportions for synthesis experiments.
Experiment

Mg metal
(g)

Reaction 1
Reaction 2

Reaction 3

MgCl2
(g)

Mg(C2O2H4)2
(g)

1 in 100 ml
H2O
6.44 in 100 ml
H2O

NaOH
(g)

Urea
(g)

16.5 in 25 ml H2O
1.8 in 25 ml
H2O
1.2 in 25 ml
H2O

27

less energy than resistive heating and is less polluting than gas or oil
red heaters and is therefore more environmentally friendly. Moreover the rapid initial heating of the microwave can enhance the kinetics of the reaction due to the formation of high temperature
throughout the sample [9].
Herein, Mg(OH)2 has been synthesized via the microwave-assisted
technique using Magnesium Chloride, urea and water. In addition
Magnesite in high purity with ne nanostructure has been synthesized b addition of urea to the reaction mixture. The as-synthesized

Fig. 1. Wide angle X-ray diffraction pattern of reactor sample 1.

Fig. 2. TGA plot of sample 1.

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G.W. Beall et al. / Powder Technology 234 (2013) 2631

Fig. 3. X-ray diffraction pattern of sample 2 that matches hydromagnesite.

materials were characterized by the X-ray diffraction, scanning electron microscopy, DSC and TGA.
2. Experimental
2.1. Synthesis
The samples of material reported in this paper were produced
utilizing a microwave assisted hydrothermal process. All chemical

reagents were analytical grade and were utilized without any further purication. In two experiments the magnesium acetate or
magnesium chloride was dissolved in distilled water under stirring
for 30 min. In a second step either a solution of sodium hydroxide
or urea was added drop wise to the solution with pH being controlled to 10. In one experiment the NaOH solution was added directly to magnesium metal. The above solutions were then placed
in a microwave hydrothermal Teon cell. The cell was then placed
in a microwave oven and heated from room temperature to 220 C

Fig. 4. TGA plot of sample 2 that is consistent with hydromagnesite.

G.W. Beall et al. / Powder Technology 234 (2013) 2631

29

Fig. 5. X-ray diffraction pattern of sample 3.

for 10 min and maintained at the same temperature for 30 min. The
microwave oven was operated at 1000 W. The precipitates formed in
this process were then washed and ltered with distilled water and
then air dried. Table 1 gives the proportion of reagents for the
three experiments performed under these conditions.

2.3. Thermal analysis


The thermal gravimetric analysis was carried out on a TA instruments TGA Q50 at a scan rate of 10/min from room temperature up
to 800 C. The differential scanning calorimeter analysis was carried
out on a TA instruments DSC Q200 at a scan rate of 10/min from
room temperature up to 400 C.

2.2. X-ray diffraction


2.4. Scanning electron microscopy
The X-ray analysis was carried out on a Bruker D-8 diffractometer
utilizing Cu Ka radiation. The patterns were scanned from 2 to 60 2
at a step size of 0.03 and step time of 2 s.

The samples have been investigated using the eld emission scanning electron microscopy (FESEM), Helios Nano lab 400 equipped

Fig. 6. TGA plot of sample 3.

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G.W. Beall et al. / Powder Technology 234 (2013) 2631

Sample 3

Sample 2

Sample 1

Fig. 7. SEM images for the as prepared samples with low and higher magnications; the inset is the EDAX analysis for the three samples.

G.W. Beall et al. / Powder Technology 234 (2013) 2631

with energy dispersive X-ray (EDX) spectrometer. The maximum accelerating voltage was 30 kV while the working distance was 4 mm.
3. Results and discussion
The rst synthesis where magnesium metal was dissolved in sodium hydroxide yielded a nanostructured white powder which yielded
an X-ray diffraction pattern that is predominately Mg(OH)2 as can be
seen in Fig. 1. All of the larger peaks can be indexed for the brucite
structure with the b 001> at 0.474 nm, b100 > at 0.262 nm, b 101>
at 0.237 nm, b102 > at 0.180, and the b 110> at 0.158 nm, JCPS
7239 with lattice constants of a = 3.148 , b = 4.787 [10].
The peaks are sharp which indicates that the Mg(OH)2 grain
boundaries is large. There are a number of small peaks that indicate
a minor impurity. These peaks match reasonably well with sodium
carbonate decahydrate which would be a possibility since the sodium
hydroxide could absorb carbon dioxide from the air. The TGA of sample 1 can be seen in Fig. 2. The theoretical weight loss for Mg(OH)2 is
31.03% and the observed is 31.02% which is a very good agreement.
The DSC yields a single large endotherm centered on 365 C. This endotherm peak corresponds to the major onset of weight loss in the
TGA. Synthesis one presents a very straight forward story. This however is not the case for syntheses 2 and 3.
Synthesis 2 incorporates urea into the synthesis and at the hydrothermal conditions employed in the reaction it would be expected
that urea would fully hydrolyze into carbonate and ammonium ions.
When the X-ray diffraction pattern was examined (see Fig. 3) it was
found to be much more complex than sample 1. The X-ray diffraction
pattern matches hydromagnesite, Mg5(CO3)4(OH)24H2O, which has
been reported by Li et al. However, Li used lower temperature and
much longer aging times. In looking at the formula of hydromagnesite
one could expect three peaks in the thermal decomposition graph.
The rst would be the loss of hydrated waters followed by the dehydration and the loss of carbonate [5].
The TGA for sample 2 given in Fig. 4 does indeed have three areas
where the sample is losing weight. The total theoretical weight loss
should be 56.9% the observed is 57.0% when corrected for a small
amount of absorbed water. The loss of the waters of hydration should
result in the loss of 15.4% by weight and there is a denite weight loss
starting around 150 C and extending up to about 350 C which
matches fairly well. The dehydroxylation and loss of carbonate
should yield a total loss of 41.5% and in the thermogram of sample
2 there is a weight loss of 41.2%. The onset of this region is around
350 C and extends to around 600 C. There is some structure to
this region but it is impossible to resolve dehydroxylation from loss
of carbonate [11,12].
The DSC has two endotherms below 400 C with rst centered on
275 C and the second larger one around 370 C. All of these measurements are consistent with those measured by Li, et al. on synthetic hydromagnesite and by Hollingbury and Hall on natural samples
from Greece [5].
The results for sample 3 are almost identical to those obtained for
sample 2. The X-ray diffraction pattern (Fig. 5) ts hydromagnesite
perfectly and the TGA thermogram (Fig. 6) yields the same weight
loss pattern with a total weight loss of 56.7%.

31

The scanning electron microscopic analysis of the three samples can be seen in Fig. 7. It can be seen that the morphology of
sample 1 is radically different from samples 2 and 3. Sample one
exhibits a pseudo-hexagonal blocky morphology with the particles
in the range of 250 to 500 nm. In contrast samples 2 and 3 are
characterized as rosettes with diameters in the 50 micron range.
The inset is the EDAX analysis of the three samples, as one can
see there are two intensive peaks for the Mg and Oxygen for the
three samples and a small peak for carbon and no other peaks
can be detected. Similar morphology has been obtained by Kumari
et al. at 200 C [7]. Range that is composed of interlocking plates is
tens of nanometers thick but micron size in the other two dimensions. This rosette morphology is consistent with that reported by
Li, et al. [5].
4. Conclusions
From this work it is clear that in the synthesis of hydrous magnesium
compounds that the presence of urea in the synthesis under hydrothermal conditions that the crystalline phases produced is dominated by the
urea hydrolysis reaction. In particular hydromagnesite in high purity is
the only crystalline phase produced when urea is present. Secondly
the microwave method gives a very highly crystalline hydromagnesite
and brucite in a very short time. This could be of substantial commercial
value since hydromagnesite has many commercial applications.
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