JOURNAL OF RARE EARTHS, Vol. 35, No. 1, Jan. 2017, P.

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Preparation of nanoscaled yttrium oxide by citrate precipitation method

CHEN Jinqing (陈金清)1, HUANG Bin (黄 彬)1,2, HUANG Chao (黄 超)1,2, SUN Xiaoqi (孙晓琦)2,*
(1. School of Metallurgy and Chemical Engineering, Jiangxi University of Science & Technology, Ganzhou 341000, China; 2. Xiamen Institute of Rare Earth
Materials, Haixi Institute, Chinese Academy of Sciences, Xiamen 361021, China)

Received 28 April 2016; revised 31 May 2016

Abstract: The nano-Y2O3 was prepared from YCl3 by the citrate precipitation method. The precursor powders were prepared by 0.1
mol/L YCl3 solution and 0.1 mol/L hydrochloric acid in the presence of 1% surfactant PEG2000, which was dried via an ethanol
azeotropic distillation method. The effects of reaction temperature, precursor concentration, hydrochloric acid concentration, surfac-
tant, and calcination temperature on the mean sizes of nano-Y2O3 were studied. It was found that the highest yield of precursor was
about 70% at the pH value of 5.0, and the yield decreased rapidly at the pH value below 4 or over 6. The reaction temperature re-
vealed no effect on the size of precursor. The optimized precursor concentration and hydrochloric acid concentration were both 0.1
mol/L. Several typical analytic techniques such as particle size analyzer, X-ray diffraction (XRD), thermogravimetric and differential
thermal analyses (TG-DTA) and scanning electron microscopy (SEM) were used to determine the characteristics of the prepared nano
powders. Homogeneous torispherical nano-Y2O3 with the smallest size (20 nm) could be obtained by calcining the precursor powders
at 800 ºC for an hour.
Keywords: nano; Y2O3; citrate precipitation; rare earths

With the booming development of nanotechnology,
the nano powders with regular morphology and narrow
size distribution have been widely studied[1]. The nano-
sized oxide particles possessed unique physicochemical
properties over common materials, such as optical, cata-
lytic and structural properties[2]. Considerable investiga-
tions on the preparation methods of nano-sized oxide
particles have been conducted[3]. It is worthwhile to mention
that rare earth oxides have been used in many advanced
technologies, such as magnets, lightings, sensors, lasers,
electronics, batteries, catalysts, alloys and communica-
tions[4]. As a result, the development of rare earth (RE)
oxides with nano-sizes, larger specific surface areas and
higher chemical activities comes to be very important[5,6].
Among the rare earth (RE) oxides, yttrium oxide
(Y2O3) possesses excellent heat resistance, corrosion re-
sistance, high temperature and photochemical stability[7].
Its melting point is higher than 2400 ºC and dielectric
constant is from 12 to 20[8,9]. As a result, Y2O3 is widely
used in ceramics, optical and laser materials. For exam-
ple, it was used as additive in many high performance
ceramics to improve their hardness[10], wear[11,12], corro-
sion resistance[13], and light transmission[14,15]. As laser
host material, the neodymium-doped yttrium aluminum
garnet laser was widely used in medical equipment[16].
Besides high purity, uniformity and dispersion of Y2O3
are essential for the high-tech materials.
As mentioned previously, the preparation of nano
Y2O3 can be summarized to be solid phase method[17,18],
liquid phase method (including precipitation method[19–25],
sol-gel method[26–29], microemulsion method[30–32], hydro-
thermal method[33–35]) and gas phase method[36]. Because
of low reaction temperature, simple equipment and low
energy consumption, the liquid phase precipitation
method is the most commonly used technology for the
preparation of nano-scale particles on the industrial scale.
The common precipitants in liquid phase precipitation
method are oxalic acid, carbonic acid, sodium hydroxide,
and citrate. The oxalic acid is one of the most commonly
used precipitants in industrial production, but it is still
expensive for industrial production. In addition, rare-
earth carbonate and rare-earth hydroxide precipitates are
amorphous, the resulting Y2O3 particles are prepared with
lower yields and broader size distributions. To develop
sustainable and efficient strategy for industrial applica-
tion, ammonium citrate was used as precipitant for the
preparation of nano-scale Y2O3 in this article. In a very
recent report, the precipitates revealed crucial influence
on the size and morphology of the prepared nano pow-
ders[37]. To obtain nano-Y2O3 powders with favorable
size and morphology, the effects of reaction temperature,
precursor concentration, hydrochloric acid concentration,

Foundation item: Project supported by “Hundreds Talents Program” from Chinese Academy of Sciences, National Natural Science Foundation of China
(21571179), Science and Technology Major Project of the Fujian Province, China (2015HZ0101), Xiamen Universities, Research Insti-
tutions Jointing Enterprise Projects (3502Z20152009), Research Institutions Jointing Enterprise Projects (3502Z20152009)
* Corresponding author: SUN Xiaoqi (E-mail: xqsun@fjirsm.ac.cn; Tel.: +86-592-6376370)
DOI: 10.1016/S1002-0721(16)60164-3
80
surfactant, and calcination temperature on the mean size
of nano-Y2O3 were discussed in this article. It is the first
attempt to dry precipitate via an ethanol azeotropic dis-
tillation method under reduced pressure of 0.01 MPa,
which contributes to the sample dried quickly without
agglomeration.
1 Experimental
1.1 Reagents and materials
The Y2O3 (99.999%) was provided by Fujian Chang-
ting Golden Dragon Rare Earth Co., Ltd., China. Am-
monium citrate (purity>98.5%) and PEG2000 were ob-
tained from Sinopharm Chemical Reagent Co., Ltd. All
the chemicals used in this study were of analytical grade
without further purification.
1.2 Preparation of nano-Y2O3
(1) The YCl3 solution was prepared by dissolving the
Y2O3 in muriatic acid (1:1). The pH value of solution
was kept to be 4–5. Y3+ concentration in the solution was
determined by EDTA compleximetry.
(2) The YCl3 solution was dropped to a stirred ammo-
nium citrate solution, and then ammonia was used to in-
crease the pH until the precipitate disappeared. Subse-
quently, the hydrochloric acid was dropwisely added
with stirring till the generation of precipitation. By ad-
justing the pH value, the highest rate of precipitation was
obtained. Then the precipitate was filtered and washed
with deionized water for removing chloride.
(3) The precipitate was dispersed in the ethanol by ul-
trasonic and azeotropic distillation under reduced pres-
sure at 40 ºC to obtain precursor without adsorbed water,
which was subsequently heated at various temperatures
to get the Y2O3 powder.
1.3 Characterizations
The particle size of Y2O3 dispersed in ethanol was
measured by dynamic light scattering (Nanobrook Omni,
Brookhaven). The morphologies of nano-Y2O3 were ob-
served by scanning electron microscopy (SEM, Hitachi
su8010). Simultaneous thermogravimetric and differen-
tial thermal analyses (Mettler Toledo, TGA/DSC1) with
a heating rate of 10 ºC/min in a static air atmosphere
were used to study thermal decomposition behavior of
Scheme 1 Preparation process of nano-Y2O3 powder
JOURNAL OF RARE EARTHS, Vol. 35, No. 1, Jan. 2017
the dried precursor. Crystalline phase present was identi-
fied by Rigaku Miniflex 600 XRD system, which gener-
ated monochromated Cu Kα radiation with continuous
scanning mode at a rate of 8 (°)/min ranging from 5° to
85°, and operating conditions of 40 kV and 15 mA were
used to obtain XRD patterns.
2 Results and discussion
2.1 Effects of pH and molar ratio on precipitation rate
Citric acid (H3Cit) is hydroxyl tribasic acid, which has
multi-level complexing abilities with RE at different pH
values and molar ratios. In the acidic solution, the anion
complex was formed by RE ions (H2Cit)– and (HCit)3–.
When the pH values arrived at 6–8, the precipitation
(RECit) of neutral complex salt was produced. In the pre-
cipitation (RECit), the molar amount of RE was equal to
that of citric acid. When the molar amount of citric acid
was higher than RE, [RE2(Cit)3]3– and [RE(Cit)2]3– ani-
ons came to be formed. Moreover, hydroxyl of RE citrate
was neutralized to form [Y(Cit)’]– in alkaline solu-
tion[38,39]. Fig. 1 shows the precipitation rates of precursor
[(RECit)·nH2O] at different pH values when the molar
ratio (RE3+/Cit3–) is 0.9 or 1. The highest yield is about
70% at the pH value of 5.0, the yield decreases rapidly at
the pH value below 4 or over 6. The different molar ra-
tios reveal little effect on the precipitation rates.
2.2 Effect of temperature
As can be seen in Fig. 2, the effect of reaction tem-
perature on the mean size (D50) of precursor was studied.
It is found that the size of precursor changes slightly with
the temperature increased from 25 to 90 ºC. The com-
parison indicates that the mean size of precursor is not
related to the preparation temperature. Accordingly, the
precursor powders were prepared at room temperature in
this study.
2.3 Effect of precursor and hydrochloric acid
According to LaMer model for the crystal nucleation
Fig. 1 Effect of pH values and molar ratios of citric acid with
RE on the precipitation rate
CHEN Jinqing et al., Preparation of nanoscaled yttrium oxide by citrate precipitation method
Fig. 2 Particle sizes obtained at different temperatures
process[40,41], nanocrystal formation comprises the fol-
lowing three steps: (1) the atoms start to aggregate into
nuclei via self-nucleation with the increase of reactant
concentration; (2) the reactant aggregates on the pre-ex-
isting nuclei or seed, leading to gradual decrease of reac-
tant concentration; (3) the nuclei continue to grow into
nanocrystals. To obtain a high yield of shape-monodis-
perse nanocrystals, nucleation must occur rapidly and in-
stantaneously, and then the concentration of reactants
must be kept below the critical level without nucleation
happens. At the same time, the nanocrystals grow slowly
to uniform monodisperse nano-particles. As can be seen
in Fig. 3, the concentration effects of precursor and hy-
drochloric acid on the mean size of precursor were stud-
ied. It is obvious that the higher concentrations of pre-
cursor solution and hydrochloric acid result in pro-
nounced increases of the mean sizes.
When the concentration of precursor solution was in-
creased from 0.05 to 0.4 mol/L, the sizes of Y2O3 in-
creased from 322 to 1130 nm. Similar increasing trend of
Y2O3 size from 538 to 1624 nm could also be observed
by increasing the concentration of hydrochloric acid. It is
worthwhile to mention that there existed serious ag-
glomeration phenomena among the prepared Y2O3 pow-
ders when the sizes of precursors were below 400 nm.
Based on the above mentioned studies, the optimized con-
ditions were 0.1 mol/L precursor solution and 0.1 mol/L
Fig. 3 Concentration effect of precursor and hydrochloric acid
81
hydrochloric acid.
2.4 Effect of calcination temperature
Fig. 4 shows the typical TG and DTA curves of dried
precursors. There are endothermic peak at 116 ºC and
exothermic peak at 400 ºC within the DTA curve. The
strong endothermic peak at 116 ºC can be attributed to
the loss of crystal water and residual ethanol. The exo-
thermic peak at 400 ºC is due to the combustion reaction
of organic groups and formed oxide. Subsequently, there
is no exothermic peak below 100 ºC, indicating that no
absorbed water remains in the precursor. The ethanol
azeotropic distillation method can remove the absorbed
water effectively at low temperature.
It can be seen from TG curve that the powders of pre-
cursors reveal two times of obvious weightlessness in the
whole roasting process. The total weight loss of the pre-
cursor is around 60%. The weight loss above 100 ºC can
be mainly attributed to the removal of crystal water and
residual ethanol, which can be observed by the existence
of endothermic peak centered at 116 ºC in the DTA
curve. The weight loss in the temperature range of
350–650 ºC is due to the burnout of the organic group of
yttrium citrate. Moreover, there is no obvious weight loss
calcined upon 700 ºC. To achieve a complete calcination,
the results from TG-DTA analysis reveal that the calci-
nation temperature needs to be above 700 ºC.
The mean sizes of Y2O3 calcined from 700 to 1000 ºC
for an hour are revealed in Fig. 5(a). In this study, both
the precursor solution and hydrochloric acid concentra-
tions were 0.1 mol/L. As revealed in Fig. 5(a), the nano-
Y2O3 with the smallest size can be obtained at 800 ºC.
Fig. 5(b) shows the XRD pattern of Y2O3 calcined at dif-
ferent temperatures. With the increase of calcination
temperature, the intensities of characteristic peaks were
increased and peak widths at half height were narrowed.
The temperature effects reveal that higher calcination
temperature contributes to the crystals growth. The
powder calcined at 700 ºC was incompletely crystallized,
and the completely crystallized form can be obtained at
800 ºC. As revealed in Fig. 5(b), the nano-Y2O3 is apt to
form hard agglomeration when the temperature arrives
Fig. 4 TG-DTA plots of precursor powder
82 JOURNAL OF RARE EARTHS, Vol. 35, No. 1, Jan. 2017

The effect of surfactant contributes to the reduced ag-

glomeration of precipitate and collapse of the network
during calcination procedures, which would help reduce
the size of final product[43]. As can be seen in Table 1, the
182 nm (D50) nano-Y2O3 powders can be obtained by
adding 1 wt.% PEG2000 into the precursor solution.

2.6 Particle sizer and SEM analysis of nano-Y2O3

Fig. 5 Mean size (a) and XRD pattern (b) of Y2O3 calcined at
different temperatures
above 800 ºC. The agglomeration tendency results in the
change of nano-particle morphology.
Furthermore, the obtained intensities and positions of
XRD diffraction peaks were compared with those of
JCPDS card. It is found that the Y2O3 product was cubic
crystal structure, which was consistent with the Y2O3
standard diffraction data (JCPDS card No.: 65-3178).
Calculated from the full width at half maximum (FWHM)
using Scherrer’s equation[42], the crystallite sizes of Y2O3
calcined at 800 ºC were found to be around 15 nm.
To characterize the prepared nano-Y2O3 powders, size
distribution of the nano-Y2O3 powders are given in Fig.
6(a) and their SEM pictures are revealed in Fig. 6(b) on
the scales of 200 and 60 nm. In this study, the precursor
precipitates were prepared by 0.1 mol/L solution and hy-
drochloric acid in presence of 1 wt.% PEG2000. Then
the precursor precipitate was calcined at 800 ºC for an
hour. As shown is Fig. 6(a), the size distribution of
nano-Y2O3 powders is monodisperse and very narrow.
The product powder has a mean size of 180 nm. As for
the morphologies of nano-Y2O3 powders, SEM pictures
shown in Fig. 6(b) reveal that the product is torispherical
particle and has a good size distribution around 20 nm.
Nanoparticles are the particles between 1 and 100 nano-
meters in size, the sizes of ultrafine particles are the same
as those of nanoparticles. Fine particles are sized be-
tween 100 and 2500 nanometers, and coarse particles
cover a range between 2500 and 10000 nanometers[44,45].
In this study, the final products are nano-Y2O3 powders
of 20 nm with torispherical morphologies, which can be
called nanoparticles or ultrafine particles. Their sizes are
smaller than the latest report on nano-Y2O3 powders[37].

2.5 Effect of surfactant on nano-Y2O3

Table 1 lists the effect of surfactant on size distribution
of nano-Y2O3. The Y2O3 powers were calcined at 800 ºC,
which were prepared by the same precursor solution and
hydrochloric acid but different surfactants. The com-
parison in Table 1 indicates that the surfactants can de-
crease the surface tension of water contained in the pores.

Table 1 Effect of surfactant on size distribution of nano-Y2O3

No. Surfactant/wt.% D10/nm D50/nm D90/nm
1 – 170.10 293.30 505.83
2 3% Ethanol 173.38 260.94 392.72
3 5% Ethanol 147.28 230.79 361.65
4 10% Ethanol 147.54 227.00 349.27
5 1% PEG2000 118.65 182.87 281.85
6 3% PEG2000 184.51 277.90 418.55
7 5% PEG2000 193.37 321.39 534.17
Fig. 6 Size distribution (a) and SEM photos (b) of Y2O3 product
CHEN Jinqing et al., Preparation of nanoscaled yttrium oxide by citrate precipitation method 83

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