JOURNAL OF RARE EARTHS, Vol. 26, No. 2, Apr. 2008, p.

158

Preparation of large particle rare earth oxides by

precipitation with oxalic acid
LIU Zhaogang (柳召刚), LI Mei (李 梅), HU Yanhong (胡艳宏), WANG Mitang (王觅堂),
SHI Zhenxue (史振学)
(School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, China)
Received 15 August 2007; revised 15 December 2007

Abstract: The large particle CeO2 and Y2O3 were prepared using oxalic acid as precipitator. The effects of operational parameters such as
stirring velocity, precipitation temperature, feeding speed, aging time, precipitation method, and calcination temperature on particle size and
loose density of CeO2 were studied. Under the particular conditions, particle median size of D50≥30μm, loose density of ≥2.0 g/ml of CeO2,
and particle median size of D50≥20 μm of Y2O3 were prepared. This technology had advantages of simple process, less equipment investment,
ease of use, and suitability for industrialization products.
Keywords: large particle; oxalate; loose density; rare earths

Rare earths have a distinct character because of a particu-
lar electron configuration and are said to be the treasury of
new materials. The physicochemical characteristics of rare
earth material has a lot of effect on its application, so the
control to the physicochemical property index of rare earth
products becomes the key in the development of the rare
earth industry[1,2]. The particle size of rare earth powder di-
rectly determines its application effects. Different particle
size of powder materials can be used to prepare different
requirements of ceramics materials, fluorescent materials,
electronic materials, and so on. The particle size of polishing
powders directly determines polishing efficiency and final
achievable degree of polishing. So the particle size and dis-
tribution are very important performance indices of rare
earths powders[3–5]. Presently, with the development of new
materials, rare earth compounds with controllable particle
size exhibit good market prospects. Fine particle rare earth
compounds have specific application fields; large particle
rare earth compounds have extensive market application.
The manufacturers of decorative products wish to purchase
CeO2 powders with particle size larger than 30 μm and
loose density more than 2.0 g/ml. When rare earth oxide is
used to prepare metal by electrolytic method, big particles,
good distribution, and rather high loose density of oxide
powders are used to avoid splashing in electrolyzation proc-
ess. In the glass industry, large particle size and high loose
density of CeO2 powders are used in place of classical white
arsenic for admixture with glass in best[6]. Rare earth manu-
facturers with rare earth oxide products of general particle
size equal to 3–5 μm and loose density less than 1.2 g/ml
cannot meet the user’s demand. There are enough investiga-
tive reports about nanometer or superfine rare earth oxides
[7~11]
, but studies of large particles are very few. The CeO2
powders with loose density equal to 2.01 g/ml was prepared
by precipitation using oxalate in the literature[6]. In the Chi-
nese patent 5–10 μm particle size of CeO2 was prepared us-
ing the same method[12]. The preparation of much larger par-
ticle size of rare earth oxide is not reported till today. The
oxalate precipitation commonly used in industry to prepare
rare earth oxide has properties such as good deposition
crystal type, easy filtration, and so on, but the particle size of
rare earth oxide still falls short of big particle requirement.
In this article, the particle size equal to or larger than 20 μm
of rare earth oxide was prepared and the effects of precipita-
tion and calcination conditions on the particle size and loose
density of CeO2 powders were investigated.
1 Experimental
1.1 Sample preparation
A certain concentration solution was prepared by using

Foundation item: Project supported by National Key Basic Research Program (NKBRP 2004CCA03900); the National Natural Science Foundation of China
(50662002)
Corresponding author: LIU Zhaogang (E-mail: liuzg65@163.com)
LIU Z G et al., Preparation of large particle rare earth oxides by precipitation with oxalic acid
Ce2(CO3) (REO≥45%, CeO2/ΣREO≥99%) or Y2O3
(Y2O3/REO≥99.9%). The solution was ready to be used after
getting rid of impurities and adjusting. The precursor com-
pound was prepared with oxalic acid solution by different pre-
cipitation conditions in solution diluted to required concentra-
tion in advance. The precursor turned into large particle CeO2
or Y2O3 after filtrating, washing, drying, and calcinating.
1.2 Test and characterization
The particle distribution of samples was tested by Coulter
LS-230 type laser particle size analyzer. The morphology
and dispersity of samples were characterized by S360 type
scanning electron microscope. The crystal type and phase of
the samples was analyzed by Philips PW1700 type XRD.
The loose density of samples was tested by BT-1000 type
powder comprehensive characteristic tester with the national
criterion (GB/T16913.3) measurement method of powder
loose density, in which the loose density can be obtained by
taking arithmetical mean of three testing results.
2 Results and discussion
2.1 Effect of stirring speed
Excessively slow stirring speed increases instant local satu-
ration and does not facilitate particles to grow; so it results
in broad distribution of generated particles. A suitable stir-
ring speed prevents local supersaturation and helps mass
transport process; therefore stirring facilitates precipitation
of bigger particles to some extent. However, the excessively
quick stirring speed may not permit particles to grow and
may break up the particles into pieces, resulting in uniform
and small particles. Thus stirring speed directly influences
the particle size. Different stirring speeds were chosen in the
experiments. From the results as shown in Figs.1 and 2, it is
seen that loose density of CeO2 increased, particle size
changed in regularity along with augmented stirring speed,
and there was rather large loose density, rather large particle
size, and good distribution of CeO2 as the stirring speed was
300 r/min as shown in Fig.2.
Fig.1 Effect of stirring speed on particle size and loose density of
CeO2
159
Fig.2 Particle size distribution of CeO2 at different stirring speeds
2.2 Effect of precipitation temperature
The temperature is one of the important factors in the pre-
cipitation reaction. When the solute content is fixed, the su-
persaturation of solution usually decreases with increasing
temperature according to the relationship between supersatu-
ration and temperature. The supersaturation may be larger at
very low temperature, but the crystal particles of generation
speed may be very low owing to the low energy of solute
molecule. With the increase in temperature, the crystal parti-
cle generation can reach maximum. If the temperature con-
tinually increases, on the one hand, the supersaturation of so-
lution may decrease; on the other hand, the crystal particles of
generation speed tend to decrease because the molecular ki-
netic energy increases too quickly to inhibit forming stable
crystal particles. So it is important to choose a suitable tem-
perature to control the precipitate particle size in the precipita-
tion reaction. The experiment was done at different tempera-
tures. The result as shown in Figs.3 and 4 indicates that the
effect of temperature on particle size was probably similar to
that on loose density. The particle size and loose density in-
creased with the increase in temperature in the middle and
low temperature zones. With the temperature continually in-
creased after that, the particle size and loose density of CeO2
decreased somewhat in the beginning stage and they did not
obviously change later. So the optimum temperature should
be chosen in the middle and low temperature zones.
Fig.3 Effect of temperature on the particle size and loose density
160
2.3 Effect of aging time
Aging is defined as resting time for precipitate and mother
liquid after completing precipitation. When the large and
small crystal particles exist in solution at the same time, the
solution already reaches saturation for the large particles but
not for small particles because the solubility of small parti-
cles is larger than that of large particles. So the small parti-
cles dissolve gradually. As dissolution happens at a certain
stage, the solution reaches saturation for the small particles
and supersaturation for the large particles; thus the ion
forming crystals in solution deposits on the large crystal par-
ticles. When the solution reaches saturation for the large
particles and not for small particles, the small particles dis-
solve continually again. In doing so, the small particles
gradually vanish and the big particles gradually grow. So the
aging process is favorable for the growth and uniformity of
the particle size and distribution. The experiment was done
under different aging times. The results in Figs.5 and 6 in-
dicate that the particle size and loose density of CeO2 tend-
edto increase with the increase in aging time. The particles
had narrow and uniform distribution.
2.4 Effect of feeding speed
The effect of precipitator feeding speed on the particle
size and loose density of CeO2 is shown in Table 1 and
Fig.7. It can be seen that the maximum of particle size
and loose density of CeO2 appeared when the feeding
speed was 10 ml/min. As feeding all precipitator at a time,
Fig.4 Particle size distribution CeO2 at different temperatures
Fig.5 Effect of aging time on the particle size and loose density
JOURNAL OF RARE EARTHS, Vol. 26, No. 2, Apr. 2008
the CeO2 had a rather large particle size too. It was owing to
the the fact that if the feeding speed was very low, the rate
of growth was larger than the rate of nucleation resulting in
the growth of particles. If the feeding speed was too fast, the
rate of nucleation was larger than the rate of growth, result-
ing in generation of fine particles. If the precipitators were
fed at the same time, the local precipitator concentration was
so high that aggregates were formed and there were a lot of
porosities in it; therefore it led to 1.53 g/cm of loose density.
It was seen that D50 of particles was relatively large, but the
particles had a broad distribution as a result of a lot of small
particles generated. Taking the synthesis factor of loose
density and particle size into consideration, suitable feed
speed should be 10 ml/min.
2.5 Effect of precipitator feeding mode
Experiments of positive feeding and reverse feeding were
done, and the results are shown in Table 2. In positive feed-
ing, the precipitator is added to metal ion solution. In reverse
feeding, the metal ion solution is fed into precipitator solu-
Table 1 Particle size and loose density of CeO2 at different
feeding speeds
Feeding speed / Feeding all precipi-
6 10 25
(ml/min) tator at one time
D50/μm 29.96 46.51 34.41 45.55
Loose density/(g/ml) 2.06 2.28 1.86 1.53
Fig.6 Particle distribution of CeO2 under different aging times
Fig.7 Particle distribution of CeO2 at different feeding speeds
LIU Z G et al., Preparation of large particle rare earth oxides by precipitation with oxalic acid 161

Table 2 Particle size and loose density of CeO2 with different are 1000 °C and 2 h, respectively.
feeding modes of precipitators
2.7 Preparation of large particles of CeO2 and Y2O3
Feed mode Positive feeding Reverse feeding
According to experiment results, the optimum preparation
D50/μm 29.96 9.826
conditions for large particle CeO2 was fixed. Accordingly,
Loose density/(g/ml) 2.06 1.01 particles of median size D50≥30 μm and loose density of
≥2.0 g/ml CeO2 were obtained, and particle size distribution
tion. Under the reverse feeding mode, the pH of solution and SEM are shown in Figs.10 and 11, respectively. It can
remained constant favoring the formation of small particles, be seen that large particle size and high loose density of
such that particle size and loose density of CeO2 were small. CeO2 was prepared with oxalate in a six-rowed cylinder, and
The particle size and loose density of CeO2 were relatively had narrow and normal particle size distribution on the
large with positive feeding mode. whole.
The large particle Y2O3 was prepared with the same
2.6 Effect of calcination temperature method. Its particle median size of D50 can exceed 20 μm
The effect of calcination temperature on the particle size and its particle size distribution is shown in Fig.12; it also
and loose density of CeO2 is shown in Table 3, Figs.8 and 9. had narrow and normal particle size distribution on the
The calcination temperature is an important factor influenc- whole.
ing the particle size. With the calcination temperature rising,
the diffraction apex gradually moved sharply and the half
pick breadth gradually turned large. If the calcination tem-
perature rose too rapidly, the particle size of CeO2 was af-
fected because the crystals developed imperfectly and the
crystal face was easy to rupture, resulting in broad distribu-
tion. It can be seen from Fig.9 that the spike of particle dis-
tribution was highest at 800 °C, but its loose density was
less than that at 1000 °C. According to experimental results,
it is ideal if the calcinations temperature and the time required
Fig.9 Particle size distribution of CeO2 at different calcinations
Table 3 Particle size and loose density of CeO2 at different cal- temperatures
cination temperatures
Calcinations 500 800 1000 1000 1000 1000
temperature/°C

Heating up 1 1 1 2 4 5
time/h
D50/μm 26.99 37.31 35.41 38.18 38.82 37.44

Loose density/ 1.24 2.08 2.42 2.395 2.36 2.37

(g/ml)
Fig.10 Particle size distribution of large particle CeO2

Fig.8 XRD of CeO2 at different calcinations temperatures Fig.11 SEM of large particle CeO2
162
Fig.12 Particle size distribution of Y2O3
3 Conclusions
1. The operational factors such as stirring speed, precipi-
tation temperature, feeding speed, aging time, precipitate
method, and calcination temperatures all had an important
effect on particle size and loose density, when the large par-
ticle CeO2 was prepared using oxalic acid as precipitator.
2. Under the special preparation conditions, the large par-
ticle and high loose density CeO2 was prepared in a
six-rowed cylinder and had narrow and normal particle size
distribution on the whole, with its median size of D50≥30 μm
and loose density of >2g/ml.
3. Under the special preparation conditions, Y2O3 of the
particle median size D50≥20 μm was prepared and it had
narrow and normal particle size distribution on the whole.
4. This method with which large particle CeO2 and Y2O3
was prepared with oxalic acid had advantages of simple
process, less equipment investment, easy of use, suitability
for industrialization products and applicability in preparing
large particles of other rare earth oxides.
References:
[1] Li Yongxiu. Physical characteristics control of rare earth prod-
uct and development of rare earth industry. Chinese Rare
Earths (in Chin.), 1998, 19(6): 73.
JOURNAL OF RARE EARTHS, Vol. 26, No. 2, Apr. 2008
[2] Lin Yaling, Xiao Kongqing, Zhang Anqiang, Wang Lianshi.
Preparation and properties of rare earth modified carbon
black/natural rubber composites. Journal of the Chinese Rare
Earth Society (in Chin.), 2005, (6): 708.
[3] Garside J. Industrial crystallization from solution. Chem. Eng.
Sci., 1985, (40): 3.
[4] Huo Di, Sun Xudong, Xiu Zhimeng, Li Xiaodong. Influence
of processing conditions on morphologies and sinterability of
uotrafine Y2O3 powders. Journal of the Chinese Rare Earth
Society (in Chin.), 2007, 25(5): 566.
[5] Su Jing, Zhang Qingli, Wang Zhaobing, Sun Dunlu, Gu
Changjiang, Shao Shufang, Zhang Xia, Yin Shaotang. Prepa-
ration and spectral characteristics of Nd:YAG nano-powder.
Journal of the Chinese Rare Earth Society (in Chin.), 2007,
25(4): 500.
[6] Xu Zhizhen, Yang Yuxia, Yuan Shuanglong, Zhao Lianguo,
Xin Moliang. Study and preparation of high bulk density ce-
rium dioxide. Journal of the Chinese Rare Earth Society (in
Chin.), 2002, 20: 119.
[7] Ming-Shyong Tsaii. Formation of nanocrystalline cerium ox-
ide and crystal growth. Journal of Crystal Growth, 2005,
274(3): 632.
[8] Hirano, Masanori, Kato. Hydrothermal synthesis of nanocrys-
talline cerium (IV) oxide powders. Journal of the American
Ceramic Society, 1999, 82(3): 786.
[9] Gao Wei, Gu Hongche. Control of mean particle size of rare
earth oxalate in precipitation process. Chinese Rare Earths (in
Chin.), 2000, 21(1):11.
[10] Zhao Xiaoshan, Feng Jiangchuan. Relationship between solu-
bility of rare earth oxalate and its Particle size of oxide and
particle size control. Chinese Journal of Rare Metals (in
Chin.), 2003, 22(1):167.
[11] Gao Jieming, Zhang Xiyan, Qi Linlin, Zhou Shijie, Jiang Feng.
Dimensional factors of nano-powder CeO2 in liquid reaction
process. Journal of the Chinese Rare Earth Society (in Chin.),
2003, 21: 59.
[12] Daiwei C. The production method of rare earth bi-ammonium
oxalate and its application in producing the rare earth oxide
and rare earth oxide being produced. Chinese Patent (in Chin.):
CN1061403A, 1991.