Colloids and Surfaces A: Physicochem. Eng.

Aspects 252 (2005) 129–134

Preparation of BaSO4 nanoparticles with self-dispersing properties

Hari Balaa , Wuyou Fub , Jingzhe Zhaoa , Xuefeng Dinga , Yanqiu Jianga ,
Kaifeng Yua , Zichen Wanga,∗
a College of Chemistry, Jilin University, Changchun 130023, China
b National Laboratory of Superhard Materials, Jilin University, Changchun 130023, China

Received 16 March 2004; accepted 12 October 2004

Available online 19 November 2004

Abstract

BaSO4 nanoparticles with an average particle size of 24.3 nm were prepared by the precipitation method using (NH4 )2 SO4 and BaCl2 as
raw materials, and a water–alcohol solution as the reaction medium. The samples were characterized by photon correlation spectroscopy,
transmission electron microscopy, X-ray diffraction, thermogravimetric analysis and infrared analysis. The results indicate that the BaSO4
powder sample has few mesopores and can self-diffuse in water, thus forming a suspension with enhanced stability and longevity. The
preparation conditions that influenced the properties of the product were investigated and the mechanism of synthesis was also discussed.
Adding ethanol during the preparation process can control the growth of the particles, and washing the precipitates in ethanol can prevent
the particles from aggregating during the drying process. The powders are completely dried and treated at 200 ◦ C to get rid of any remaining
water in order to avoid subsequent aggregation of the particles. The samples can then be preserved for a long period. Ethanol combined with
BaSO4 forms a film through hydrogen bonding. The hydrogen bonds and mesopores trigger self-dispersal of the BaSO4 powder in water.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Barium sulfate; Nanoparticles; Precipitation method; Self-dispersal; Suspension

1. Introduction persing properties in water, in order to form a stable suspen-

Inorganic powders have been widely applied in many ar-
eas [1–6]; for example, as medicines, additives, functional
ceramics and catalysts. However, a key problem remains: can
the nanoparticles be dispersed stably and homogeneously in
media? The nanoparticles can easily aggregate into larger
particles because of the high surface activity and high sur-
face energy adsorption during the preparation. Controlling
the particle size during the preparation process, avoiding the
aggregation of particles during the drying and calcination pro-
cesses, and inducing the powders to redisperse in the medium
are current ‘hot topics’ in the field of nanomaterials [7–10]. In
addition, the development of novel materials requires smaller
sized particles and inorganic additive powders with good dis-
∗ Corresponding author. Tel.: +86 431 8499134; fax: +86 431 8499134.
E-mail address: wangzc@mail.jlu.edu.cn (Z. Wang).
sion [11–13].
Barium sulfate, which is commonly referred to as barite,
is used widely because of its high specific gravity, opaque-
ness to X-rays, inertness and whiteness [14]. Barite is one
of the most important fillers used in the plastics, rubber
and paint industries, and is also used in pharmaceutical
formulations. Recently, barite has been incorporated into
polymers to form electrical-insulating barite/epoxy compos-
ites with X-ray attenuation properties [15]. Some previous
papers have reported the synthesis of nanosized BaSO4 .
For example, Qi et al. [9] synthesized spherical and cubic
BaSO4 nanoparticles with a barite structure in Triton X-
100/n-hexanol/cyclohexane/water water-in-oil microemul-
sions containing (NH4 )2 SO4 and Ba(Ac)2 , respectively. Due
to their cage-like nature, the microemulsion droplets have a
controlling effect upon the size of the particles. However,
in the process mentioned above, many kinds of raw ma-
terials, organic solvents and surfactants are needed, which

0927-7757/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.10.064
130 H. Bala et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 129–134
usually result in a high cost and environmental pollution. Jia
and Liu [11] synthesized nanosized BaSO4 particles using
a membrane reactor, in which the Na2 SO4 solution perme-
ated through the micropores of an ultrafiltration (UF) mem-
brane and gradually flowed into the BaCl2 solution to con-
trol the saturation ratio, nucleation and growth rates. How-
ever, because of its high viscidity, a colloidal suspension of
BaSO4 is likely to block the narrow-diameter pores of the UF
membrane. In the present study, we controlled the microen-
vironment during the preparation process in order to obtain
BaSO4 nanoparticles with self-dispersing properties without
the need for additional treatments.
2. Experimental
2.1. Materials
Analytical reagent (AR) grade ammonium sulfate, bar-
ium chloride and absolute alcohol were purchased from
the Beijing Reagent Factory, China. The solutions used in
the experiments were prepared using distilled or deionized
water.
2.2. Preparation and characterization
The synthesis of BaSO4 nanoparticles involved the fol-
lowing steps. In a typical process, 20 mL of 0.5 M BaCl2
solution and 20 mL of absolute ethanol were placed into a
250 ml three-necked flask. Then, 10 mL of 1.0 M (NH4 )2 SO4
solution was added dropwise into the flask while stirring at
room temperature. The steady drop rate was 20 drops/min.
Gelatinous white precipitates were formed instantly. The pre-
cipitates were separated from the mother liquid by centrifu-
gation and washed with absolute ethanol (or distilled water)
several times. The precipitates were then dried at 80 ◦ C and
calcined for 1 h at 200 ◦ C to obtain the final white powders
(sample 2).
Fig. 1. The process of self-dispersal of the sample in water over time (min): (a) 0; (b) 1.0; (c) 1.5; (d) 2.0; (e) 3.0; (f) 4.0; (g) 5.0.
Photon correlation spectroscopy (PCS) using laser-light
scattering is frequently used to determine the particle size
of a suspensoid [9,16]. Here we used a 3000 HSA analyzer
(Malvern) to monitor the hydrodynamic diameters (Dh ) of
the suspension system. Ten minutes after the suspension was
formed by the self-dispersed powder in water it was loaded
into 1 cm2 cubic cuvettes and placed in a thermostated scat-
tering chamber. Light scattering was monitored at a 90◦ scat-
tering angle and a temperature of 25 ◦ C.
The morphology and microstructure of the samples were
investigated by transmission electron microscopy (TEM; Hi-
tachi, H-800). For this analysis, the powder was dispersed in
absolute alcohol, dropped onto carbon-covered copper grids
placed on filter paper and dried at room temperature. The
infrared (IR) spectra of the powder presented on KBr films
were examined using a Bruker FT 5DX (Nicolet) spectropho-
tometer. The phase structure of the powder was identified us-
ing a Rigaku-2400 X-ray diffractometer (Cu K␣ radiation,
λ = 1.5418 Å). Thermogravimetric analysis (TGA) was per-
formed using a TGA/SDTA851e analyzer (Mettler Toledo)
over a temperature range of 30–1000 ◦ C in a nitrogen atmo-
sphere with a heating rate of 10 ◦ C/min.
3. Results and discussion
3.1. Powder self-dispersal in water and the Dh of the
suspension
The BaSO4 nanoparticles were prepared in a liquid
medium of ethanol–water, the precipitates were washed with
absolute ethanol and the powder sample was calcined for 1 h
at 200 ◦ C. The BaSO4 powders had a self-dispersing property
in water and formed a stable colloidal suspension. The dis-
persal process of the powder sample in water was observed
using the following method. A 90 vol.% of deionized water
was placed into a test tube to which several tens of milligrams
of BaSO4 powder had been added. Then, without stirring or
 H. Bala et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 129–134 131

Fig. 3. TEM micrograph of the BaSO4 nanoparticles.

Fig. 2. The particle-size distribution of a suspension prepared by the self-
dispersal of powder samples in water.
eral other samples are listed in Table 1. The small and narrow
distribution indicated that the size of the BaSO4 nanoparti-
cles was further reduced and that the particles had redispersed
in the water. Due to the small size and high dispersibility of
the sample prepared using this method, the self-dispersing
nanoparticles in water did not aggregate. We confirmed that
the powder sample obtained by this method was suitable for
various potential applications.

3.2. TEM analysis

shaking, we observed the dispersal of the BaSO4 powder in
the water; photographs taken at different time points during
The TEM micrograph (Fig. 3) shows that the BaSO4 parti-
the process are shown in Fig. 1. When the BaSO4 powder was
cles are nearly elliptical and have a round shape. The particle
placed into water, it initially floated on the surface and then,
size is between 25 and 52 nm, with an average size of 36 nm.
after several seconds, it started to disperse slowly through-
This value is larger than the Dh of the suspension, because
out the solution. This property is clearly different from those
the BaSO4 particles are not completely spherical, whereas the
of other inorganic nanoparticles. The self-dispersal process
PCS analysis assumes the shape of the particles to be spheri-
of the powder in water was apparently similar to that of the
cal [9,16]. In addition, there are some uniform mesopores in
color real solution added to the blank solution. Fig. 2 shows
the particles and the diameter of the cavities is about 6–8 nm.
the typical size and the size distribution of the suspension that
These regions appear brighter because they have absorbed
was produced when the BaSO4 powder (sample 2 in Table 1)
fewer electrons than their surroundings. The larger particles
self-diffused in water. The average Dh of this suspension is
contain more pores, and the number of pores decreases as
24.3 nm and the full-width at the half-maximum intensity of
the diameter of the particles decreases, especially in small
the distribution peak is 11.7 nm. The average Dh values of sev-
particles that only contain one pore.
The high dispersibility of the powder in water might be
Table 1
Preparation parameters and properties of the products related to the mesopores of the particles and the high rate of
adsorption of ethanol onto their surfaces. The formation of
Sample no. CB CS DhE (nm) DhW (nm)
the mesoporous structure is related both to nucleation and
1 0.5 1.2 47.2 137.1
to the growth mechanism of the BaSO4 particles. Judat and
2 0.5 1.0 24.3 86.5
3 0.5 0.8 35.4 134.6 Kind [17] investigated the particle morphology and inter-
4 0.5 0.6 44.7 109.4 nal structure (the cavities contained within the particles) of
5 0.5 0.4 54.4 205.6 precipitated BaSO4 . They showed that BaSO4 grows accord-
6 0.5 0.2 71.3 281.7 ing to a combined mechanism involving molecular and ag-
7 0.25 1.0 85.4 264.3
gregative growth. The pore size increases with increasing
8 0.65 1.0 73.3 348.5
supersaturation. In the present work, we prepared the BaSO4
CB and CS represent the concentration of the BaCl2 and (NH4 )2 SO4 solutions
in mol L−1 (M), respectively. The BaCl2 solution and ethanol volume ratio
nanoparticles using an ethanol and water solution, and the ini-
is 1:1. DhE and DhW denote hydrodynamic diameters (Dh ) of the suspension tial supersaturation was high. Therefore, the resultant BaSO4
for precipitates washed in ethanol and water, respectively. particles had a porous structure.
132 H. Bala et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 129–134
Fig. 4. Changes in the Dh of samples with the amount of ethanol.
3.3. The effect of ethanol
Ethanol has two effects in the preparation of BaSO4
nanoparticles. In order to investigate the influence of ethanol
on the Dh of the particles, the volume ratio (R) of the
ethanol/BaCl2 solution was varied from 0 to 1.5, and the con-
centrations of BaCl2 and (NH4 )2 SO4 were fixed. Fig. 4 shows
how the Dh of samples changed with R: when the R was less
than 1:1, the Dh of the samples decreased as the R increased;
by contrast, when the R was more than 1:1, the Dh increased
as the R increased. The R of the ethanol/BaCl2 solution di-
rectly influenced the environment of the reaction, which, in
turn, led to the initial nucleation and growth of the particles.
Table 1 shows comparisons of the particle sizes of precipitates
washed in ethanol and water: those washed in ethanol were
much smaller than those washed in water. Fig. 5 shows the
XRD patterns of the BaSO4 powders (sample 2); the samples
display the typical orthorhombic structure of BaSO4 (JCPDS
Card Files No. 83-2053). No impurity peaks were detected,
indicating that the powders had high purity. The intensity
and width of the diffraction peaks differed between the pre-
cipitates washed in water (Fig. 5(a)) and ethanol (Fig. 5(b)).
Fig. 5. XRD patterns of BaSO4 powders (sample 2) obtained from precipi-
tates washed in (a) water and (b) ethanol.
The average grain sizes estimated using the Scherrer formula
from the broadening of the XRD were 16.3 and 37.6 nm for
the {2 1 0} diffraction peak of precipitates washed in ethanol
and water, respectively. This suggested that precipitates of the
BaSO4 powders washed in ethanol contained crystal grains
that were much smaller than those washed in water, which
might be related to the adsorption of the ethanol onto the
surface of the BaSO4 particles. When the precipitate was
washed by ethanol, it was further adsorbed onto the surface
and then encapsulated into the pores of the BaSO4 particles.
Thus, the Gibbs free energy of the particles was reduced,
which restrained the growth of the crystal. During the dry-
ing process, the rapid volatilization of ethanol inhibited any
subsequent aggregation of the BaSO4 particles. As a result,
the powder had high dispersibility and small particle size.
The ethanol therefore improved the reaction conditions by
favoring the formation of small particles, and by restraining
particle growth during the precipitation and drying processes.
Washing the precipitate with ethanol also affected the surface
properties of the BaSO4 particles. The lower aggregation rate
is attributed to the presence of an ethoxide group on the sur-
face, which is formed by replacing the coordinated water on
the surface with ethanol. As a result, ethanol has dispersive
and protective effects on the powders. It is therefore essen-
tial during the preparation of BaSO4 nanoparticles that the
precipitate is washed in ethanol.
3.4. The effect of stability of the suspension
To investigate the stability of the suspension, the BaSO4
powder (sample 2) was dispersed with deionized water in
a 1200 mm long test tube and allowed to age for various
time periods. We discovered that the BaSO4 powder ini-
tially self-diffused in water and then a milky suspension
formed, in which the Tyndall phenomenon was observed.
In addition, the suspension persisted in water over a long
period of time. Fig. 6 shows the Dh of the suspension at
different stages. Initially, when the ageing time increased,
the Dh of the suspension became larger. However, the sys-
tem reached equilibrium after 150 h, when the Dh of the
Fig. 6. The Dh of the suspension at different stages.
 H. Bala et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 129–134 133

Fig. 8. TGA micrograph of samples obtained from precipitates washed in

(a) water and (b) ethanol.

the powder sample was calcined for 1 h at 200 ◦ C, so there

Fig. 7. The IR spectra of (a) the BaSO4 precursor and (b)–(f) the precursor was less adsorbed water. When the precipitates were washed
calcined for 1 h at different temperatures: (b) 150 ◦ C, (c) 200 ◦ C, (d) 250 ◦ C, in ethanol (Fig. 8(b)), a total weight loss of 1.68 wt.% was
(e) 350 ◦ C and (f) 450 ◦ C (Curves (a), (b), (c), (d), (e) and (f) are from top
observed on heating from room temperature to 600 ◦ C. When
to bottom).
the sample was heated from room temperature to 220 ◦ C, a
slow loss of the adsorption water and ethanol was observed
suspension was about 90 nm, which indicated that it had a
from the surface of the BaSO4 . When the temperature was
relatively high stability. This phenomenon might be related
changed from 220 to 600 ◦ C, the main weight loss was due to
to the surface properties and the mesoporous structure of the
the loss of the adsorbed ethanol (IR in Fig. 7) on the surface
particles (Fig. 3). The initial gravity of the BaSO4 is large,
of the BaSO4 . A comparison of the loss curves of (a) and (b)
but it decreases with the adsorption of air into the porous
showed that the quantity of ethanol adsorbed onto the surface
cavities. By contrast, the protective films on the surface of
of the BaSO4 was about 1.12 wt.%. The high temperatures
the particles remain intact. The particle size is small and
did not lead to the complete desorption of ethanol due to its
the Brownian movement is strong, which counteracts the
strong binding force, which further indicated that a hydrogen
gravity of the particles and causes them to disperse in the
bond was formed.
water.
Additionally, powder samples were calcined for 1 h at
different temperatures, self-diffused into water and the Dh
3.5. The mechanism values of the suspensions were characterized. Fig. 9 shows
the particle sizes of samples at different calcination temper-
In order to study the surface characteristics, the BaSO4 atures. It can be seen that the Dh of the suspension decreased
powders were calcined at different temperatures for 1 h after with an increase in the temperature. Above 200 ◦ C, the Dh
the infrared (IR) spectra were examined. Fig. 7 shows the of the suspension tended to increase. This can be explained
presence of a broad absorption band at 3150–3400 cm−1 (A as the water could not be eliminated when the temperature
area), which is due to an internal molecular hydrogen band was below 200 ◦ C. A hydrogen bond therefore formed be-
(O H· · ·O). The weak absorption peaks at 2950–2850 cm−1 tween the water and ethanol on the surface of the powder,
(B area) are due to stretching vibrations of the methyl and leading to the aggregation of the particles. However, when
ethyl groups. The absorption band at 1403 cm−1 is due to the temperature was above 200 ◦ C, the amount of ethanol
O H bending vibrations internal face. As the calcination tem-
perature increase, the intensity of ethanol-specific absorption
peaks (A, B and C) decreases, but the absorption of ethanol
still occurs at higher temperatures (Fig. 7(f)). It was suggested
that the ethanol was highly adsorbed onto the surface of the
particles and then encapsulated in their pores. As a result, we
conclude that ethanol integrates with the hydrogen bonds on
the surface of the BaSO4 powder.
In order to measure the quantity of ethanol being adsorbed
onto the powder, TGA was used to investigate the precipi-
tates washed in water and ethanol, respectively. The weight
of the sample decreased (Fig. 8(a)) in precipitates washed in
water as the heating temperature increased. A total weight
loss of 0.56 wt.% occurred when the sample was heated from
room temperature to 600 ◦ C, due to a loss of the adsorbed
water from the surface of the BaSO4 . In the present work, Fig. 9. Changes in the particle sizes of samples with calcination temperature.
134 H. Bala et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 129–134
Table 2
Changes in the Dh of BaSO4 powder (sample 2) with preservation time
Time
1 day 7 days 15 30 90 120
days days days days
Dh (nm) 24.3 25.4 28.6 26.1 33.5 31.7
absorbed onto the particles decreased, which destroyed the
protective film and the mesoporous structure at the bottom of
the BaSO4 particles, causing them to aggregate. Thus, 200 ◦ C
is the optimum temperature for the calcination of the resultant
powders.
The above analysis confirmed that the BaSO4 was linked
to the ethanol by hydrogen bonds. A compact ethanol layer
existed on the surface of the BaSO4 with outward-facing ar-
rays of ethoxy groups, making particles hydrophobic softly.
As a result, when the powder was placed into the water it
initially floated on the surface. Hydrogen bonds were then
formed between the ethanol adsorbed onto the surface of
the BaSO4 particles and the water. This stimulated the self-
dispersal and induced the BaSO4 particles to diffuse in the
water to form a stable suspension.
3.6. The effects of preservation time
The aggregation of nanoparticles during the preservation
process is spontaneous, due to their large surface areas and
high surface energy. This is a case of a G < 0 being used
to decrease the surface area and the surface energy of the
nanoparticles. After being preserved for a long period of time,
the nanoparticles will aggregate and the particle sizes will
exceed 100 nm (micron or submicron ranges), so they will
lose the specific functions of nanomaterials. In the present
work, we examined the particle size of samples according
to preservation time. The powder was sealed in a polyvinyl
chloride (PVC) bag that was placed in the desiccators. The
particle sizes of the samples were characterized by PCS at
various time periods and the results are listed in Table 2. It
can be seen that the Dh of the sample shows little change
when the preservation time is prolonged for up to half an
year, which indicates that it has little effect on the particle
size. The ethanol adsorbed onto the surface of the particles
prevented them from aggregating.
4. Conclusion
BaSO4 nanoparticles with an average Dh of 24.3 nm were
180 prepared by the precipitation method, using (NH4 )2 SO4 and
days BaCl2 as raw materials, and a water–alcohol solution as the
54.6 reaction medium. The BaSO4 powder samples have rela-
tively few mesopores. A suspension of BaSO4 can be formed
by self-diffusion of the powders in water, which has en-
hanced stability and can be preserved for long periods of
time. The ethanol added during the preparation system im-
pedes the growth of the particles, and washing the precipi-
tates in ethanol prevents the particles from aggregating dur-
ing the drying process. The powders are treated at 200 ◦ C to
remove any remaining water, which avoids any subsequent
aggregation. The ethanol and BaSO4 forms a film through
hydrogen bonding, which stimulates the self-dispersal of the
particles. A lower carbon alcohol is added during the prepa-
ration process to disperse the particles and to wash the precip-
itate, and the intrinsic hydrophilic properties of the particles
prevent their subsequent aggregation, thus enhancing their
dispersibility.
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