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Synthesis of Scandium Oxide Nanoparticles from Solution

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DOI: 10.4028/www.scientific.net/AST.62.70

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Advances in Science and Technology Vol. 62 (2010) pp 70-75
Online available since 2010/Oct/27 at www.scientific.net
© (2010) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AST.62.70

Synthesis of scandium oxide nanoparticles from solution

N. Poirot (1,a), P. Boy (2,b), P. Belleville (2,c), L. Bianchi (2,d)

1
LEMA, UMR 6157, CNRS-CEA, IUT de Blois, 3 place J. Jaurès, 41029 Blois cedex
Université F. Rabelais, Parc Grandmont, F- 37200 Tours
2
CEA-DAM, /Le Ripault, F- 37260 Monts
a
nathalie.poirot@univ-tours.fr, bphilippe.boy@cea.fr,
c
philippe.belleville@cea.fr, dluc.bianchi@cea.fr

Keywords: sol-gel synthesis, ScOOH, Sc2O3, nanoparticles, laser ceramic

Abstract: Scandium oxides nanopowders have been synthesized using a sol-gel route.
ScOOH nanoparticles have been first prepared in solution using ScCl3, xH2O as precursor.
Influence of pH and reflux time on particles size and shape has been studied. Sc2O3
nanoparticles were then obtained after ScOOH sol drying.
Sols were characterized by laser granulometry, thermogravimetry and differential
analysis (TGA- DSC). Depending on pH, 40 to 1000 nm size ScOOH particles can be
obtained. At a given pH, the reflux time duration also influences the ScOOH particles size.
The ScOOH sol can be used to prepare highly pure Sc2O3 nanopowders. X-ray
diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Transmission
Electron Microcopy (TEM), were used to characterize Sc203 nanopowders obtained from the
various ScOOH solutions. The DSC and laser granulometry data indicate a strong relation
between the nanoparticles size and the temperature of transformation of γ-ScOOH to Sc2O3.
Depending on the sol preparation various particles Sc2O3 size can then be obtained allowing
the selection of the more suitable powder for transparent ceramic preparation.

Introduction
The cubic sesquioxide crystals Ln2O3 with Ln = Y3+, Lu3+ and Sc3+ are attractive laser
matrices due to favourable properties, like high transparency in a large frequency range, high
thermal conductivity and the possibility of doping with rare earth ions. Due to its high melting
point (2420°C), the Sc2O3 crystal growth from melt is complex, then ceramic materials are a
good alternative to single crystals. The preparation of transparent scandium oxide ceramics
has been already reported [1-4]. One of the key to obtain highly dense Sc2O3 ceramics (>99%)
is the control of inter-grain pores density. By consequence, the particles shape and size
control is essential.
To prepare nanocrystalline Sc2O3 powders, different routes can be used as the oxalate
precipitation technique [5], the called propellant synthesis [6,[7], electrochemical deposition
method, reverse-strike precipitation technique and hydrothermal synthesis [8-[10].
The main objective of this work is to prepare oxohydroxide nanoparticles by a sol-gel
route with controlled size and then annealed at higher temperature to obtain scandium oxide
Sc2O3. The sol-gel process allows the preparation of oxide nanoparticles directly in solution,
without additives. Good oxide homogeneity, high purity and size control are some advantages
of solution process. By wet-chemical route, J-G. Li et al. [2,3,11,12] have previously studied
the influence of Sc precursor preparation on Sc2O3 powder. The monodispersed Sc2O3
precursor particles are prepared via homogeneous precipitation from various Sc precursors

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 Advances in Science and Technology Vol. 62 71

(nitrate, chloride, sulfate) [11]. NO3- and Cl- lead to ScOOH after precipitation with urea at
90°C. The same authors [12] reported that ScOOH is obtained by precipitation of scandium
nitrate in ammonia whatever the preparation conditions (reaction temperature between room
temperature and 70°C), aging and pH.
In this work the precursor used is ScCl3. ScOOH is prepared by precipitation with
NaOH and reflux at 100°C at constant volume. In this condition, only pH and reflux time
duration are controled. The salt elimination is processed by water dialysis leading to obtain a
stable pure ScOOH sol depending on pH and reflux time duration. The influence of pH and
time preparation on the ScOOH size is clearly put into evidence as well as the impact of
ScOOH preparation conditions on final Sc2O3 features.
To study the scandium oxide preparation and the experimental parameters which
influence the final size of Sc2O3 particles, laser granulometry, X-Ray Diffraction, TDA/TGA
thermal analysis and Fourier Transformed Infra-Red (FTIR) Spectroscopy studies have been
carried out on ScOOH sol dried from 100°C to 500°C.

Experimental
The ScOOH nanoparticles were produced with hexahydrated scandium chloride
dissolved in water. The initial pH of the chlorhydrate aqueous solution is around 2. The
condensation/peptization reaction leading to ScOOH sol is processed by adjusting the pH with
10% NaOH solution at room temperature and then refluxing the Sc(OOH) solution at 100°C
and pH>6. The resulting suspension is dialyzed in water to remove the salts. The ScOOH
particles size is measured by laser granulometry (Malvern Nano ZS) after dispersion by
ultrasonic bath during 15 min.
Various pH and reflux time durations have been studied respectively from 7 to 13 and
2 to 24h.
The excess water in ScOOH sol is removed by drying at 100°C in air. Dehydration
takes place above 400°C in a furnace to yield Sc2O3 powders. Thermogravimetry and
differential thermal (TG-DTA) analyses of dried precursor were performed with a Diamond
TG/DTA analyser at a heating rate of 10°C.min-1, from room temperature to 1000°C, using α-
Al2O3 as a reference. The phase identification is performed by X-ray diffractometry with a
Rikagu diffractometer in a θ–2θ geometry using Cu-Kα radiation (λ= 1.5406 Å). FTIR
analysis allows to determine the ScOOH to Sc2O3 temperature formation and to control the
powder purity (Nicolet, 550 serie II spectrometer).

Results
Influence of pH and reflux time duration on the particles size
Experimental parameters (pH, concentration, reflux time) and their influences on the
particle size are reported in table1.
When the sol preparation is processed at initial pH 11 or 13, a precipitate is formed. The
granulometry is above 1 µm in each case. Indeed, too high leads to larger particles, the basic
catalysis favoring the hydroxide condensation.

pH initial (pHi) 7 7 9 9 11 13
Reflux time(h) 4 24 4 24 4 4
40 160 70 180 >1000 >1000
Particle size (nm)

Table 1: Influence of pH and reflux time on the particles size.

72 12th INTERNATIONAL CERAMICS CONGRESS PART A

When sol-gel process is carried out at pH 7 or 9, homogeneous sols are generally formed
with a monodisperse distribution. Depending on the reflux time duration, 40 to 70 nm
diameter size particles can be formed.
As can be seen on Table 1, the best preparation conditions are for pH 7 or 9 and 4h reflux
time duration.

Characterization
a. XRD
The Figure1 shows XRD patterns of γ−ScΟΟΗ prepared at pH 7 with 4h reflux time
duration and after sol drying respectively at 100, 300, 400 and 500°C.

(222)

(440)

(622)
(211)

(543) (640)
Intensity (a.u.)

(322)

(631)
(431)

(541)
(411)

(512)

(433)

(611)
(400)
(321)

(444)
500°C

400°C

300°C
(020)

(031)

(051)

(231)
(120)

(151)

(020)

100°C

10 20 30 40 50 60 70
2θ (degree)

Figure 1: XRD-patterns of γ-ScOOH and its calcinations products. The reference XRD-
pattern for cubic Sc2O3 is included for comparison (red line).

The system is well crystallized at 100°C and indexed to γ-ScOOH with orthorhombic
structure (JCPDS N°17-941, Amam). No α-ScOOH phase is detected. The XRD patterns of
dried ScOOH at 100 and 200°C being the same, only the spectra at 100°C has been
represented. At temperatures below 400°C, γ-ScOOH orthorhombic phase is mainly present.
Between 300 and 400°C, a peak appears as indicated by the filled circle. The last one can be
attributed to the (211) plane of the Sc2O3 cubic phase, whereas the peaks attributed to the γ-
ScOOH phase disappears gradually. At 500°C, only cubic Sc2O3 phase is observed with Ia3
space group. The compound is a well crystallized pure Sc2O3 powder, which is consistent
with the results of DTA/TG and FTIR as discussed later. By comparison with the Sc2O3
nanopowder preparation using a homogeneous precipitation method [5], Sc2O3 appears here at
lower temperature, the grain germination beginning between 300 and 400°C. The same study
has been realized on ScOOH synthesized at pH 9 and show similar results.
The X-ray line broadening analysis from Debye-Scherrer equation on the Sc2O3 powders
obtained at pH 7 and 9 gives an average crystallite size of 10-15 nm. TEM studies still in
progress should confirm this result.
As a conclusion, the XRD studies indicate that the gradual transformation from γ-ScOOH
into Sc2O3 takes place between 300 and 500°C. Whatever the pH value and annealing
temperature, no signature of α-ScOOH is observed. Our results are similar with those
obtained by V. Ripert et al.[14] but different from the observations of Zhang et al.[10] which
observed the one or the other ScOOH phase according to pH value.
 Advances in Science and Technology Vol. 62 73

b. Thermal analysis
Thermal analysis on ScOOH sol prepared at pH 7 with 4h reflux time duration and
dried at 100°C in air during one hour is shown in figure 2.

0 200 400 600 800 1000

100

5
96

0
92
heat flow endo down (mW)

-5
88

weight loss( %)
1

-10 0,0

84
0

derivative of DSC data

derivative of ATG data

-0,2

-15 -1
80
-0,4

-2

-20 -0,6
76
0 200 400 600 800 1000
Temperature (°C)

72
-25

0 200 400 600 800 1000

Temperature (°C)

Figure 2: Thermal analysis of ScOOH annealing at 100°C. In the insert, derivatives of DTA
and TGA signals are represented.

ScOOH thermal decomposition proceeds through three steps. The first one, between
100 and 200°C, corresponds to water release. The second step, between 190 and 320°C,
associated with the departure of water linked to γ-ScOOH, corresponds to a 6.44% weight
loss. This step indicated that the γ-ScOOH precursor is hydrated and can be expressed by γ-
ScOOH.0.28 H2O. The last step is attributed to the conversion of γ-ScOOH into Sc2O3 with
one-step weight loss of about 9 % below 530°C. This step corresponds to the loss of hydroxyl
group of γ-ScOOH yielding to Sc2O3. On the DTA curve, an endothermic reaction peak at
457°C is observed corresponding to the Sc2O3 formation (see insert in figure 2). The evolution
of crystallization temperatures of Sc2O3 phase versus particle size indicates a good correlation
between these two parameters. When the γ-ScOOH particle size decreases from 180 to 40 nm,
the Sc2O3 crystallization temperature drops from 460°C to 430°C.

c. FTIR
The figure 3 shows the evolution of FTIR spectra versus temperature when ScOOH is
prepared at pH 7 and 4h reflux time duration. γ−ScOOH, α−ScOOH, Sc(OH)3 can be
discriminated on IR spectra due to the γOH and Sc-O-Sc vibration bands respectively at 675,
826 and 751 cm-1 and 472, 460 and 481 cm-1. The samples exhibit only typical absorption
bands of γ−ScOOH up to 300°C. Indeed, no α−ScOOH and Sc(OH)3 absorption bands are
observed confirming the XRD data. The absorption bands at 3216 cm-1 and 3073 cm-1 are
typical of hydroxyl stretching (νOH) whereas the δOH hydroxyl bending modes appear at 1084
cm-1 and 937 cm-1. The absorption band at 1640 cm-1 is characteristic of H-O-H bending
mode in water. The γOH bands are located below 500 cm-1. At 400°C a vibration mode appears
close to 633 cm-1 attributed to Sc2O3. At this temperature, two compounds are still present:
γ−ScOOH and Sc2O3. At 500°C only the absorption bands of the Sc2O3 are observed. These
results confirm the previous data obtained by XRD and DTA/DSC analyses. The same study
has been realized at pH 9, 4h reflux time duration. The results are similar with those obtained
at pH 7.
74 12th INTERNATIONAL CERAMICS CONGRESS PART A

4000 3500 3000 2500 2000 1500 1000 500

633
431

500°C

400°C

Transmission (a.u)
300°C
100°C

1640 1084

675
937
3216 3073 472

4000 3500 3000 2500 2000 1500 1000 500

-1
Frequency (cm )

Figure 3: FTIR spectra of γ-ScOOH and its calcinations products. The FTIR peaks
below 500cm-1 are assigned to vibrational modes of Sc-O.

Whatever the pH and reflux time, only γ−ScOOH absorption bands are observed. This work is
in agreement with the observation of reference [14] where the γ−ScOOH phase prepared by
hydrothermal synthesis (200 °C, 10 h) using ScCl3.6H2O as starting material is only observed.
Here the conversion of ScOOH phase into Sc2O3 doesn’t follow the order γ−ScOOH into
α−ScOOH as observed by Y.W. Zhang et al.[10] One can suggest that the conversion from
Sc(OH)3 to γ−ScOOH phase is neither influenced by the pH nor by the reflux time, but rather
by the nature of initial precursor.

Conclusion

In this study it has been shown that ScOOH nanoparticles can be obtained at low
temperature and pressure conditions without hydrothermal conditions. It was shown that the
control of ScOOH and Sc2O3 nanoparticles size can be achieved by controlling pH and reflux
time duration. The better synthesis conditions are found at pH 7 and a 4 h reflux time
duration. ScOOH particles have then an average dimension below 70 nm with a monodisperse
distribution. As confirmed by XRD, FTIR and DTA/DSC studies, after drying at 100°C, the
colloidal sol resulting product is the γ−ScOOH phase, while annealing at 500°C allows the
formation of the pure Sc2O3 compound.
The γ-ScOOH into Sc2O3 phase formation is dependent on particle size whatever the
pH. The pH is then the main factor which controls the nanoparticles size. TEM studies are in
process to study the influence of synthesis parameters on the size and shape of nanoparticles.
These results will be significant because the precursor shape plays a key role for the control of
the sintering conditions.

References
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 12th INTERNATIONAL CERAMICS CONGRESS PART A
doi:10.4028/www.scientific.net/AST.62

Synthesis of Scandium Oxide Nanoparticles from Solution

doi:10.4028/www.scientific.net/AST.62.70

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