International Journal of Minerals, Metallurgy and Materials

Volume 16, Number 5, October 2009, Page 592 Materials

Preparation of calcium carbonate particles coated with titanium dioxide

Hai Lin, Ying-bo Dong, and Le-yong Jiang

School of Civil and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
(Received 2008-12-23)

Abstract: The preparation of a new mineral composite material, calcium carbonate particles coated with titanium dioxide, was stud-
ied. The mechanism of the preparation process was proposed. The new mineral composite material was made by the mechanochemi-
cal method under the optimum condition that the mass ratio of calcium carbonate particles to titanium dioxide was 6.5:3.5. The mass
ratios of two different types of titanium dioxide (anatase to rutile) and grinding media to grinded materials were 8:2 and 4:1 respec-
tively, and the modified density was 60%. Under this condition, the new material was capable of forming after 120-min modification.
The hiding power and oil absorption of this new material were 29.12 g/m2 and 23.30%, respectively. The results show that the modi-
fication is based on surface hydroxylation. After coating with titanium dioxide, the hiding power of calcium carbonate can be im-
proved greatly. The new mineral composite materials can be used as the substitute for titanium dioxide.

Key words: calcium carbonate; mechano-chemical process; titanium dioxide film; hydroxylation

1. Introduction CaCO3 before and after modification were tested re-

Titanium dioxide (TiO2) is of relevance to a num-
ber of industrial products including dope, plastics, pa-
per, printing ink, rubber, chemical fiber, and cosmet-
ics. In recent years, the imbalance between the supply
and demand of TiO2 is more intensive because of the
increasing demand of it [1]. More research is needed
on TiO2, especially on looking for the substitute of it
to reduce the cost. In the United States, Britain, Ger-
many, Japan, and other industrialized countries, scien-
tists began this work from the 1970s and gained great
economic benefit. At present, this work is still in the
primary stage in China, and the product performance
is poor which can only replace 10%-30% of TiO2. The
main reason is that the hiding power of the product is
very low.
At present there are many reports on the organic
modification of calcium carbonate (CaCO3), but the
inorganic modification reports are few at home and
abroad. The modification of CaCO3 is coating TiO2 on
the surface of CaCO3 particles to improve the hiding
power of CaCO3 according to the application re-
quirement. In this work, TiO2 particles were used to
coat on the surface of CaCO3 particles by the mech-
anochemical modification method. The best coating
conditions were determined, and the hiding powers of
spectively. The study aims to use cheap CaCO3 in-
stead of expensive TiO2.
2. Experimental procedure
2.1. Material
Anatase TiO2 was provided by Panzhihua Titanium
Dioxide Plant in Sichuan Province, China. The per-
formance of the sample was: blue-ray whiteness, 93%;
particle size, 2 μm 93.66%; d50, 1.02 μm; specific
area, 64155.65 cm2/cm3; oil absorption value, 24.94%;
hiding power, 21.16 g/m2.
Rutile TiO2 (semi-finished products) was supplied
by Shanghai Xinrun Limited Company. The perform-
ance of the sample was: blue-ray whiteness, 88%; par-
ticle size, 2 μm 92.29%; d50, 1.07 μm; specific area,
61492.57 cm2/cm3; oil absorption value, 24.16%; hid-
ing power, 17.47 g/m2.
Different CaCO3 samples were bought from
Guangxi, Guangdong, Benxi, and Shanghai. The
whiteness of the samples were above 93% (blue-ray
brightness), and the oil absorption values and the size
of these samples were different.
Dispersant CHFS210M used for producing the ma-

Corresponding author: Hai Lin, E-mail: linhai@ces.ustb.edu.cn Also available online at www.sciencedirect.com
© 2009 University of Science and Technology Beijing. All rights reserved.
H. Lin et al., Preparation of calcium carbonate particles coated with titanium dioxide
terials was supplied by CHI HE Chemical Engineering
Limited Company, China.
2.2. Method
A SDF-400 sand mill was used to prepare the
modified product. A certain amount of CaCO3 (as the
core), water, grinding medium, and dispersant
CHFS210M were added in the sand mill and the
CaCO3 was grinded until its particle size reached 2
μm 90%. Then TiO2 was added in the SDF-400 sand
mill and the core and TiO2 were grinded together by
the mechanochemical method until their particle size
reached 2 μm 90%. The final modified products were
obtained by medium draining, filtration, and drying.
2.3. Index testing
Coating effects, hiding power, and oil absorption
value are the most important indexes reflecting the
performance of the white material, which were tested
in this work.
Coating effects were evaluated by transmission
electron microscopy (TEM). The core in the single
modified particle, the morphology, and the thickness
of the TiO2 film could be observed clearly by TEM. In
this test, the coating product acquired under the opti-
mum modifying conditions was used for TEM analy-
sis. After the treatment by the “ultrafine particles
ion-shear method”, the coating product was tested by
a HITACHI model H-800 transmission electron mi-
croscopy with a 0.204-nm resolution and a PV9100/75
spectrometer.
The modified effect usually can be evaluated by
hiding power and oil absorption values. In this work,
the hiding powder and oil absorption were tested ac-
cording to GB1709-79 [2] and GB1712-79 [3], re-
spectively.
3. Results and discussion
This work aims to coat TiO2 evenly on the surface
of ultra-fine CaCO3 particles through mechani-
cal-chemical modification and make the coated
CaCO3 particles have the performance of TiO2. The
production conditions were optimized to get the best
performance in this work.
3.1. Type of ground calcium carbonate (GCC) test
In this work, CaCO3 with the size of 43 μm were
from different regions. The size, hiding power, and oil
absorption value of CaCO3 from different regions
were different. To obtain the best performance,
CaCO3 should be in a certain size, neither too fine nor
too big.
593
To study the effect of different types of GCC on
coating, four different CaCO3 were used in the work.
The experimental result is shown in Figs. 1 and 2. The
particle sizes of four different products are up to 2
μm 90% after 90-min modification and have met the
requirements of the paint filler. Comparing the four
products, the hiding power of the GCC from Guangxi
is the highest, 32.80 g/m2, followed by the GCC from
Guangdong and Shanghai. The hiding power of the
GCC from Benxi is the lowest, 34.25 g/m2. For the oil
absorption value, the GCC from Guangxi has the
lowest, 23.35%. Therefore, the GCC from Guangxi is
the best core according to the performance of the
products.
Fig. 1. Effect of different types of CaCO3 on the hiding
power of modified products.
Fig. 2. Effect of different types of CaCO3 on the oil ab-
sorption of modified products.
3.2. Mass ratio of CaCO3 to TiO2
This test was to study the effect of different mass
ratios of CaCO3 to TiO2. The experiments were done
in the same modification conditions except the mass
ratios. The result is shown in Fig. 3.
Fig. 3. Effect of different mass ratios of CaCO3 to TiO2 on
the hiding power and oil absorption of modified products.
Fig. 3 shows that when the mass ratio of CaCO3 to
TiO2 is low, the hiding power is low and the oil ab-
sorption value is high, which are unfavorable. In the
modification system, if the core material is too much it
will lead to the coating process incompletely, and if
the core material is too little it will increase not only
594 International Journal of Minerals, Metallurgy and Materials, Vol.16, No.5, Oct 2009
the costs, but also the oil absorption value. Consider-
ing the cost, the product index, and other factors, the
mass ratio of CaCO3 to TiO2 should be 6.5:3.5. At this
mass ratio, the hiding power is 32.00 g/m2 and the oil
absorption value is 22.50%.
3.3. Modified concentration
The slurry concentration is a key factor in the
modification process. Too high or too low concentra-
tions are unfavorable for coating.
The effect of slurry concentration on the coating is
shown in Fig. 4. The hiding power and the oil absorp-
tion value both decreases at first and then increases.
When the concentration is 60%, the hiding power
reaches 31.30 g/m2 and the oil absorption value is the
minimum (22.44%). In addition, the product size test-
ing shows that in the concentrations of 50% and 55%,
the percent of the particle size of 2 Pm is lower than
that of the product obtained in the concentrations of
60% and 65%. In these four different concentrations,
the particle size of the final product can reach 2 μm
93%. This size has met its requirement as the paint
filler. The result suggests that the optimal modified
concentration is 60%.
Fig. 4. Effect of modified concentration of the hiding
power and oil absorption of modified products.
3.4. Time for modification
Time for modification is another important factor.
Modification for a short time will be incomplete. Too
long time modification would lead to the aggregates of
fine particles, which would deteriorate the modifica-
tion efficiency. In the same grinding and modified
conditions, the effect of modification time on the coat-
ing is shown in Fig. 5.
Fig.5. Effect of modification time on the hiding power and
oil absorption of modified products.
The result shows that when the modification time is
120 min, the hiding power and oil absorption of the
product have optimal values. With 120-min modifica-
tion, the hiding power and oil absorption value of the
modification product are 30.48 g/m2 and 22.37%, re-
spectively.
3.5. Mass ratio of grinding media to grinded mate-
rials
The mass ratio of media to materials refers to the
mass ratio of grinding media to slurry materials. This
mass ratio reflects the contact opportunity among me-
diums and grinding materials [4]. In the system of
agitation mill, if the loadings of grinding mediums and
materials can be effectively driven by a churn-dasher,
the grinding efficiency will be proportion to the ratio
of mediums to materials. The smaller the ratio, the
less the contact opportunities among the materials and
mediums. On the contrary, when the mass ratio of
mediums to materials is high, the grinding effect will
be good [5]. When the mass of grinding media is ex-
cess, the loadings of the grinding medium and materi-
als are too high to be driven by a churn-dasher, and
the contact opportunities among grinding mediums
will decrease, which can lead to low grinding effi-
ciency [6]. Fig. 6 shows the effect of the mass ratio of
mediums to materials. When the ratio is 4:1, the hid-
ing power is the lowest (30.00 g/m2), the lowest oil
absorption value is 22.44%. This suggests that the
mass ratio should be 4:1.
Fig. 6. Effect of the mass ratio of grinding media to mate-
rials on the hiding power and oil absorption of modified
products.
3.6. Mass ratio of anatase TiO2 to rutile TiO2
Anatase and rutile titanium dioxides were used as
the coating materials in the experiment. The hiding
power of rutile TiO2 is better than that of anatase TiO2.
The hiding power of the products can be improved if
more rutile TiO2 is used.
The effect of mass ratio of anatase TiO2 to rutile
TiO2 on the coating is shown in Fig. 7. The experi-
ment was done in the same grinding and modification
conditions. The hiding power is better when the pro-
portion of rutile TiO2 increases. However, the oil ab-
sorption value is higher and the cost is higher. The
H. Lin et al., Preparation of calcium carbonate particles coated with titanium dioxide 595

mechanical force is the main reason leading to surface on the coating, and TiO2 are shown in Table 1. The
modification. Mechanochemical variation of the coat- result shows that CaCO3 after modification can be
ing material during the grinding process is the main used to substitute some TiO2.
reason leading to the different effects of modification.
In addition, the result of the size analysis test shows
that the content (2 μm) of modified products can be
93% at least after 90-min modification. So the ratio of
anatase TiO2 to rutile TiO2 has little effect on the ul-
timate size of products. Therefore, the mass ratio of
anatase TiO2 to rutile TiO2 is more important than the
hiding power and the oil absorption value. Taking the
product performance and the cost into account, the
most suitable condition is 4:1 for the ratio of anatase
TiO2 to rutile TiO2 where the hiding power is 29.12
g/m2 and the oil absorption value is 23.30%.
Fig. 9. TEM energy spectrum of the core.

Fig. 7. Effect of different mass ratios of anatase TiO2 to

rutile TiO2 on hiding power and oil absorption of modified
products.

3.7. Coating effect and performance evaluation

A TEM image of the coating material is shown in
Fig. 8. The results of the energy spectra of the core
Fig. 10. TEM energy spectrum of the coating film.
and the coating film are shown in Figs. 9-10. The pic-
tures show that there is a TiO2 layer on the surface of Table 1. Main performance evaluation indexes of three
CaCO3 particles. The layer of TiO2 is uniform and materials
dense.
Content of Hiding Oil absorp-
Material the 2 μm power / tion value /
particles / % (g˜m2) %
Calcium
7.02 180.00 13.37
carbonate
Final product
93.32 29.12 23.00
on the coating
Titanium
95.60 23.68 20.36
dioxide

Fig. 8. TEM image of the coating materials.
Through the optimization of influencing factors, the
hiding power and the oil absorption value of modified
products can reach 29.12 g/m2 and 23.00%, respec-
tively, and the content of 2 μm particles is 93.32%.
The performance indexes of CaCO3, the final product
4. Coating mechanisms
The mechanism of coating is proposed as follows.
Large proportions of CO 32 on the surface of CaCO3
particles react with water (absorbed in atmosphere)
and produce CaCO3 hydroxyl compounds. These hy-
droxyl compounds are the active point to promote
modification [7].
Crystal TiO2 is one of the most typical oxides to
ˉ
form hydroxyl surface. The density of OH on the
surface of anatase TiO2 is as high as 2.8-4.5 nm2 [8].
596 International Journal of Minerals, Metallurgy and Materials, Vol.16, No.5, Oct 2009
In aqueous condition, Ti4+ on the surface of TiO2 par-
ticles hydrolyzes and generates hydroxylation hy-
drolysis products. With combined actions of each fac-
tor, the surface morphology is formed, which is hy-
droxyl-based and has the features of the active oxygen
and electronic acceptance field [9-10].
Many studies show that mechanic-chemical effects
promote phase reactions of solid particles. The active
state of the particle surface generated from me-
chanic-chemical effects promotes the direct or indirect
phase reactions. The effect of mechanic-chemical
on phase reactions between solid particles can be ex-
plained by thermodynamics and dynamics between
materials [11].
When solid particles in the ultra-fine process pre-
sent the mechanochemical properties of crystal con-
stitution integrated transfiguration, crystal lattice ab-
errance and amorphization, there will be part of en-
ergy existed on the surface. Therefore, solid matters
can easily achieve the high energy state of reaction
compensatory with surrounding particles [12]. Besides,
chemical reactions could be promoted because of the
high active surface of solid particles synchronously
generated from the mechanic-chemical effect, in-
creasing the unsaturated bond and strong compensate
trend. Mechanic-chemical effects provide dynamic
guarantee for the enhancement of modification iso-
phase reaction [13]. Fine particles and crystal lattice
limitation generated from mechanic-chemical effects
reduce the activation energy of dissolution reaction
and phase reaction, which could lead to the increase in
the reaction velocity constant [14].
In aqueous conditions, both of the surfaces of
CaCO3 and TiO2 particles present strong hydroxyl
properties. The IR spectra of CaCO3 before and after
coating with TiO2 show that a chemical bond forms
between CaCO3 and TiO2 through the surface hy-
droxyl [15]. Based on the studies of surface morphol-
ogy and the formation of chemical bonds, the reaction
model between CaCO3 and TiO2 is proposed, as
shown in Fig. 11.
Fig. 11. Reaction model between CaCO3 and TiO2.
4. Conclusions
(1) In the optimum condition, the hiding power and
the oil absorption value of the coating materials are
29.12 g/m2 and 23.30%, respectively.
(2) The materials after coating can be used to some
substitute TiO2 because of the similar properties com-
pared to pure TiO2. From economic aspects, coating
materials are better than pure TiO2. This work gives a
reference for combined mineral materials with other
non-metallic minerals for further use.
(3) The mechanism of coating TiO2 on the surface
of CaCO3 is based on the chemical bonding between
hydroxyl compounds on the surface of the particles
under mechanochemical reactions.
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