Colloids and Surfaces A: Physicochem. Eng.

Aspects 498 (2016) 98105

Contents lists available at ScienceDirectX

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www . elsevier . com/locate/colsurfa

Mass production and application of TiO2@CaCO3 composites in

interior emulsion coatings

Zhen Li, Chunying Huang, Lijie Guo, Lei Cui, Bing Zhou

College of Chemistry, Jilin University, Changchun 130012, PR China

highlights graphical abstract

The results of FESEM and XRD showed that a coating layer of rutile TiO 2 NPs was formed on the surface of calcite CaCO3 .

The whiteness of TiO2 @CaCO3 is similar to commercial rutile TiO2 par-ticles.

The contrast ratios of the coatings were high and it remained 0.934 when rutile TiO 2 @CaCO3 -15 com-pletely substituted TiO2 .

Rutile TiO2 @CaCO3 could partly sub-stitute TiO2 applied as pigments in interior emulsion coatings.
alkaline Ca(OH)2 slurry via a convenient and
Interior easy industrialized carbonation method. Field
emulsion emission scanning electron microscopy and
coatings X-ray diffraction were applied to charac-terize
the surface morphology and crystalline
article info phases of the TiO2 @CaCO3 composites, and
the results showed that a coating layer of
Article history: abstra rutile TiO2 nanoparticles was formed on the
ct surface of calcite CaCO3 . As confirmed by
Received 30 December 2015 the thermal gravimetric analysis and acid-
resistance, the composites had better thermal
In this stability and acid-resistance compared with
Received in revised form 1 March 2016 Accepted 14 March paper, rutile
CaCO3 . The UVvis absorption spectra
2016 TiO2
Available online 15 March 2016 showed that rutile TiO2 @CaCO3 composites
@CaCO3 possessed similar ultraviolet absorption
composites
capacity with TiO2 . The contrast ratios of the
Keywords: were in-situ
coatings were high enough, and it remained
TiO2 synthesized
by 0.934 when rutile TiO2 @CaCO3 -15
CaCO3
disaggregati completely sub-stituted TiO2 . Therefore, rutile
on and
TiO2 @CaCO3 could partly substitute TiO2
Deposition deposi-tion
of applied as pigments in interior emulsion
commercial coatings.
Contrast ratio
TiO2 in
2016 Elsevier B.V. All rights reserved.
TiO2 nt attention due to its whiteness and
excellent pig-ment stability [1,2].
has
properties, such as Conse-quently,
attra Corresponding author.
1. Introduction high refractive index, TiO can be used
cted 2
preferable covering E-mail address:
signi in coatings, paper
power, nontoxicity, high zhoubing@jlu.edu.cn
fica making, rubber,
(B. Zhou). X abo drastically reducing and significant. mica [7],
ut and environmental wallastonite [8],
high contamination kaolin [9] and
http://dx.doi.org/10.1016/j.colsurfa.2016. ener For decades,
problems. Therefore, calcium carbonate
03.038 0927-7757/ 2016 Elsevier B.V. gy preparation and various TiO2 [10] have been
All rights reserved.
con application of TiO2 /inorganic used as
sum composites have substrates to
com-posites which
ptio been investigated prepare TiO2
possess similar
by numerous
electronic material, and so on [3 n, properties with TiO2 /inorganic
reso researchers, in
5]. However, the increasing composites and
urce have become valuable which barite [6],
demands of TiO2 have brought
Z. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 498 (2016) 98105
99

titanium isopropoxide [24],

titanium sulfate [25] and
it has belonged to the category of new functional
titanium tetrachloride [26].
nanocompos-ite materials [11]. From those
However, those precursors of
papers reported previously, it was found that
TiO2 can increase the costs of
TiO2 /inorganic composites with comparable
production and cause
pigment properties of TiO2 were the effective environmental pollution and in
method to alleviate above mentioned problems. strongly acidic or basic
Several methods of preparing TiO2 /inorganic conditions, rutile TiO2 is more
composites are utilized, such as stable phase compared with
mechanochemical method [12], precipitation anatase [27]. The refractive
method [13] and solgel method [14]. However, index of rutile (2.93) is higher
as for mechanochemical method, the internal than that of anatase (2.488),
uniformity is difficult to control, and coating layers and so the outstanding effect
tends to be uneven [15]. Precipitation and sol of color and luster can be
gel method processes are unsuitable for mass obtained when TiO @CaCO
2 3
production [16]. In contrast with other methods,
composite pigments comprise
carbonation technology is productive, relatively
pure rutile layers [7,28].
simple and prone to be industrialized at the base
of manufacturing equipment of CaCO3 industry.
In this paper, a facile method
of depositing rutile TiO2
In the course of extensive researches, TiO2 nanopar-ticles (NPs) onto
@CaCO3 has been con-sidered as an ideal CaCO3 substrate at 50
candidate for TiO2 in a variety of fields. CaCO3
exhibits the properties of low cost, abundant
reserves and stabil-ity at high temperatures,
which has been frequently used as one of the
major ingredients in coatings, plastics, rubber,
adhesive, cos-metics, paper, construction
materials, and so on [17]. Therefore, CaCO3 can
be used as substrate to prepare TiO2 @CaCO3
composite to replace TiO2 , which has been
investigated in more researches. For example,
Tao et al. [18] prepared core-shell CaCO3 @TiO2 2. Experimental
nanocom-posite via a direct precipitation method
and the whiteness of the CaCO3 @TiO2 filler- 2.1. Materials
containing paper sheet was similar to TiO2 -
incorporated paper. Chen et al. [19] proposed a
Rutile TiO2 with diameter of
sol-gel method to prepare TiO2 /CaCO3 200300 nm, were obtained
composites using tetrabutyl titanate as tita-nium from Nanjing Titanium Dioxide
resource. Lin et al. [20] synthesized a new kind Plant in Jiangsu Province. The
of mineral composite material, CaCO3 coated analytical grade calcium oxide
(CaO) was purchased from
with TiO2 by the mechanochem-ical method and
Xilong Chemical Co., Ltd.
this new mineral composite can be used as the
Carbon dioxide (CO2 ) and
substitute for TiO2 . Tanabe et al. [21] prepared
nitrogen (N2 ) were provided by
TiO2 @CaCO3 com-posites whose whiteness
Changchun Xinguang Gas
and covering power tallied with the standards in Manufacture Co., Ltd.
pigment by carbonation method. Ethylenedi-

In previous researches, the phases of TiO2 in amine tetraacetic acid

TiO2 /inorganic composites were anatase or disodium salt (Na2 EDTA) was
rutile-anatase, and titanium source was from provided by Sinopharm
titanium tetrabutoxide [22], tetrabutyltitanate [23], Chemical Reagent Co., Ltd.
Eriochrome Black-T (EBT), ammonium chloride
and polyethylene glycol (1000) phosphate were
all of analytical degree. Calcined kaolin, talc,
ground calcium carbonate, precipitated calcium
carbonate, glycol, hydroxy ethyl cellulose and
styrene-acrylic emulsion were all industrial
grades. Dispersant agent, defoaming agent,
wetting agent, film-forming agent and thickening
agent were coatings assistants.
2.2. Synthesis of rutile TiO2@CaCO3
composites
Rutile TiO2 @CaCO3 composites with different
weight ratios of TiO2 were prepared through in-
situ carbonization method. Briefly, 500 g CaO
was digested with certain 100 C distilled water,
standing for 12 h to form a 10% (mass fraction) Contrast ratio = Reflectance
Ca(OH)2 slurry. After being filtered through a
200-mesh sieve, different loadings of TiO2 (the
mass ratios of TiO2 to the expected yield of
CaCO3 were set as 0.05, 0.10, 0.15 and 0.20),
and PEG1000 phosphate (used as dispersant)
were added into Ca(OH)2 slurry under
mechanical stirring for half an hour at 50 C.
CO2 /N2 gas mixture (volume ratio was 1:2) was
introduced into the slurry under 50 C by a glass
tube. The reac-tion was terminated when the pH
value of the slurry approach 7, then the
precipitates were collected by filtration, cleaned were dissolved in distilled
with distilled water and dried at 80 C for 12 h in water under mechani-cal
vacuum oven. The obtained samples were
named as TiO2 @CaCO3 -5, TiO2 @CaCO3 -
10,TiO2 @CaCO3 -15, and TiO2 @CaCO3 -20.
2.3. Contrast ratio test method
Contrast ratio was determined
in accordance with the
standards of interior wall
coatings (GB/T 97562009)
[32]. Paint films with different
percentages replacement of
TiO2 with rutile TiO2 @CaCO3
- 15 were applied on hiding
chart and dried for 24 h.
Reflectance measurement was
performed on both black and
white surface using the
reflectance instrument.
Contrast ratio was calculated
with the following equation
[33].
of film over black
Reflectance of film over white
2.4. Synthesis of interior
emulsion coatings
The interior emulsion coatings
were prepared as follows, and
the percentage replacement of
TiO2 is 40%. Firstly, defoaming
agent and wetting agent were
added after hydroxy ethyl
cellulose and dispersant agent
stirring for 5 min. Then, rutile
TiO2 @CaCO3 -15,
commercial TiO2 and other
fillers were added into the
mixture under rapid stirring for
40 min at room temperature.
Film-forming agent, thickening
agent and styrene-acrylic
emulsion were added under
stirring to obtain the interior
emulsion coatings with suitable
viscosity.
2.5. Characterization
techniques
Field emission scanning
electron microscopy (FESEM)
was applied to study the
morphology of the TiO2
@CaCO3 composites via an
FEI XL-30 ESEM FEG. The
crystalline phases of the
composites were characterized
by X-ray diffraction (XRD) with
Cu K radi-ation and scanned
for 2 values from 20 to 60 .
The elemental composition
analysis was carried out by
energy dispersive X-ray
analysis (EDX) which was
performed by Genesis 2000
EDAX Com-pany. Thermal
gravimetric analysis (TGA) was
measured through a DTG-60H
(SHIMADZU) analyzer. Acid-
resistance of the composites
was obtained as follows:
0.0200 g sample was dissolved
in excess 60 ml HCl solution
(pH = 2) under ultrasonic for 30
min and its pH value was
adjusted to 10 with NH3 H2
O/NH4 Cl buffer solution
100 Z. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 498 (2016) 98105

Fig. 1. FESEM images of (a) CaCO3 , (b) TiO2 , (c) TiO2 @CaCO3 -5, (d)(e) TiO2 @CaCO3 -10, (f) TiO2 @CaCO3 -15, (g)-(h)TiO2 @CaCO3 -20.
1 Acid resistance capacities of
mol L Na2 EDTA aqueous
the composites were indicated
(pH = 10). The Ca
2+
in the solution was titrated with 0.01 and the titration was terminated
by the consumed volume of
when the solu-tion turned blue.
Na2 EDTA. UVvis absorption spectra were obtained CaCO3 particles were partly
through a 2550 SHIMADZU UVvis spec-trophotometer coated by 5080 nm TiO2 NPs
from 200 to 800 nm. The whiteness analysis was evaluated
by YQ-Z-48B (Hangzhou Boke Automation Technology Co., as to TiO2 @CaCO3 -5 in Fig.
Ltd.). A reflectance instrument (C84, Shanghai Rongshida 1(c). It could be distinctly seen
Lab-oratories Ltd.) was used to measure the reflectance of that most CaCO3 particles were
the film over black and white surface. Size distribution of
samples was detected by the ZETASIZER 3000HSA Laser densely coated by TiO2 NPs,
Particle Size Analyzer (MANERN Company in England). while few CaO3 particles
possessed sparse TiO2 NPs
3. Results and discussion from Fig. 1(d). Besides, Fig.
1(e) showed that those TiO2
3.1. FESEM analysis particles deposit-ing on the
surface of CaCO3 had formed
FESEM images of TiO2 @CaCO3 composites with different holes on CaCO3 particles,
which was likely contributed to
TiO loadings are shown in Fig. 1. The CaCO particles
2 3
were spindle- the deficiency of TiO2 NPs. For
TiO2 @CaCO3 -15 (Fig. 1(f)),
shaped with smooth-surface as shown in Fig. 1(a). The abundant TiO2 NPs were
commercial rutile TiO2 particles had smooth surface and deposited on the surface of
good dispersibility in the bulk (Fig. 1(b)). Only a few of CaCO3 and performed good
Z. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 498 (2016) 98105
101
Fig. 4. TGA curves of (a) CaCO3 and (b) TiO2 @CaCO3 -15.
Fig. 2. XRD pattern of (a) TiO2 , (b) CaCO3 , (c) TiO2 @CaCO3 -15.
Table 1
Fig. 3. EDX spectrum of TiO2
@CaCO3 -15.
fore, the appropriate mass
ratio of TiO2 to CaCO3 for
TiO2 @CaCO3 composites
was 0.15, which led to a
uniform deposited layer on
CaCO3 particles.
uniformity. Moreover, the
thickness and density of the
deposited TiO2 layer in TiO2
@CaCO3 -15 were better than
other composites (Fig. 1(c)
(e)). As for the sample TiO2
@CaCO3 -20 (Fig. 1(g)), the
thickness and density of TiO2
NPs deposited layer had no
visible changes, which
indicated that when the amount
of TiO2 particles reached a
certain degree, there was no
extra space around the surface
of CaCO3 particles for the
redundant TiO2 to deposit, so
that some unaided spherical
TiO2 particles with original size
about 0.20.3 m could be
observed in Fig. 1(h). There-
3.2. XRD analysis
The phases present in the
commercial rutile TiO2 , as-
prepared CaCO3 and TiO2
@CaCO3 -15 have been
determined by XRD analysis in
Fig. 2. The narrow diffraction
peaks of commercial TiO2
(Fig. 2(a)) at 2 values 27.4 ,
36.9 , 39.1 , 41.9 , 44.2 ,
55.5 and 58.9 accorded well
with (110), (101), (200), (111),
(210), (211) and (220) crys-tal planes of rutile titanium dioxide 16.99 EDTA of all TiO2 @CaCO3
(JCPDS #No. 21-1276) [34]. In Fig. 2(b), the diffraction peaks com-posites were less than

at 2 = 23.1 , 29.5 , 31.6 , 35.9 , 39.5 , 43.2 , 47.1 , 47.7 , ratio of TiO2 to CaCO3 was CaCO3 , which illustrated that

48.7 , 56.6 and 57.4 , corresponded to (102), (104), (006), 0.149), which corroborated
rutile TiO2 NPS deposited
(110), (113), (202), (024), (018), (116), (211) and (122), that TiO2 existed in the TiO2 layer can improve the acid-
indicating the existence of calcite (JCPDS #No. 88-1807) in
the composites [35]. Comparing all the XRD curves, the peaks @CaCO3 composites, as well resistance of CaCO3 for the
as the XRD analysis.
of TiO2 and CaCO3 were still observed in TiO2 @CaCO3 -15 better stability of rutile TiO2 . In
compos-ites (Fig. 2(c)), so it could be concluded that the addition, the consumed Na2
3.4. TGA analysis
crystal structure of TiO2 was retained during the carbonation EDTA volumes decreased
gradually when the amount of
process in Ca(OH)2 slurry. Moreover, according to the results
The thermal gravimetric TiO2 increased in the
of FESEM study, the only change of commercial TiO2 particle images of the CaCO and
3 composites, so that in a
was the size distribution, not the crystal structure during the
TiO2 @CaCO3 - 15 are shown certain range, the more the
whole reaction process.
amount of rutile TiO2 in
in Fig. 4. The sample TiO2
composites was added, the
3.3. EDX analysis @CaCO3 -15 (Fig. 4(b)) better the thickness and
showed a higher thermal
density of deposited rutile TiO2
Ulteriorly to verify the XRD analysis results, EDX analysis of stability (decomposition layer were.

TiO2 @CaCO3 -15 has been shown in Fig. 3. The EDX tempera-ture = 710 C) than
spectrum revealed the existence C, O, Ca and Ti elements CaCO3 (decomposition 3.6. UVvis absorption
with atomic per-centages of 18.91%, 54.04%, 22.8% and analysis
temperature = 696 C) (Fig.
4.25%, respectively (mass
4(a)). These different
decomposition temperatures The UVvis absorption spectra
2+
Acid resistance of the samples (the titrations of Ca by visual detection of of samples are shown in Fig.
manifested that the rutile TiO2
end-pointing using EBT indicators, pH = 10, CNa2 EDTA = 0.01 M). 5. It could be seen obviously
NPs deposited layer had
successfully located on the that commercial TiO2 (Fig.
Samples 5(a)) exhib-ited strong
surface of CaCO3 and made
V /mL
Na2 EDTA absorption for the ultraviolet
TiO2 @CaCO3 -15 have a
CaCO3 light in the wavelength of 200
higher thermal stability.
20.39 400 nm because rutile TiO2
TiO2 had a band gap of 2.99 eV
@CaCO3 -5 3.5. Acid resistance analysis [36], so it could create electron
19.42
hole pairs under ultraviolet
TiO2
The relationship between the light irradiation. However, the
@CaCO3 -10
18.53 TiO2 @CaCO3 with different absorption of pure CaCO3
TiO2 (Fig. 5(f)) was remarkably
load-ings of TiO2 NPs and
@CaCO3 -15 lower than TiO2 in this
17.73
acid-resistance is shown in
TiO2
Table 1. It can be seen that wavelength range. The TiO2
@CaCO3 -20 the consumed volume Na2 NPs deposited
102 Z. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 498 (2016) 98105
3.8. Reaction mechanism Disaggregated TiO2 Nps
1724.9
of TiO2@CaCO3 100
composites

The reaction mechanism of

the deposition of TiO2 NPs tion of commercial TiO2
on the surface of CaCO3 original particles and TiO2
particles is shown in Fig. 7. NPs released from
It was well known that in the commercial TiO2 in water
industrial production are shown in Fig. 8 and
process of commercial TiO2 Table 2. The size of
, the particle size in the commercial TiO2 particles
form of sol was dozens of (Fig. 8(a), Table 2) was
nanometers and con- about 200.9 nm. However,
glomeration of these TiO2 the released TiO2 NPs (Fig.
NPs would occur to 8(b), Table 2) tended to
generate particle of 200 agglomerate as a bigger
300 nm in the process of sphere (1724.9 nm) by
calcination [37]. The size hydrolysis and stirring effect.
distribu- The mechanical stirring
process of Ca(OH)2 slurry
and commercial rutile TiO2
was further investigated to
verify if there was any new
product. The XRD of the
mixture of Ca(OH)2 slurry
Fig. 5. UVvis absorption spectra of (a) TiO2 , (b) TiO2
and commercial TiO2 for
@CaCO3 -20, (c) TiO2 @CaCO3 - 15, (d) TiO2
different stirring time is
@CaCO3 -10, (e) TiO2 @CaCO3 -5, (f) CaCO3 .
shown in Fig. 9. The curves
of the mixture for 5 min, 10
layer was able to significantly affect the min, 15 min, 20 min, 25 min
composites absorption, so that the ultraviolet and 30 min were identical
light absorption of TiO2 @CaCO3 and the diffraction peaks
strengthened gradually as the amount of were assigned to Ca(OH)2
commercial TiO2 rose. Although the (JCPDS #No. 87-0673) and
rutile TiO2 (JCPDS #No. 21-
absorption of TiO2 @CaCO3 composites
1276) without any other
was lower than TiO2 , it was beneficial to its peaks, which indicated that
application because the slightly lower there were no new phases
photocat-alytic activity of TiO2 may help to formed during mechanical
solve the problem of chalking in coatings stirring [3840]. The XRD
analysis results of the
industry. Therefore, the TiO2 @CaCO3 -15
mixture of Ca(OH)2 slurry
was more suit-able to be applied in the
coatings based on the similar properties of and commercial TiO2 proved
ultraviolet absorption. that the TiO2 NPs were
released from commercial
3.7. Whiteness analysis Fig. 6. Whiteness of (a) CaCO3 ,
TiO2 particles without any
(b) TiO2 @CaCO3 -5, (c) TiO2
possible phase transition
@CaCO3 -10, (d) TiO2 @CaCO3
Fig. 6 shows the whiteness of the CaCO3 , -15, (e) TiO2 @CaCO3 -20, (f) process, but those
commercial TiO2 particles
TiO2 and TiO2 @CaCO3 composites with TiO2 .
may disaggregate to TiO2
varying TiO2 loadings. It was clear that the
Table 2 NPs once being dispersed in
white-ness of all TiO2 @CaCO3 composites Size distribution of commercial
the alkaline Ca(OH)2 slurry
was higher than CaCO3 due to the formation TiO2 and disaggregated TiO2 NPs. (pH value was 13) under
of TiO2 deposited layer. An increase in TiO2 mechanical stirring for 30
load-ing led to the improvement of Samples min.
Mean size (nm)
whiteness, which further indicated that the Percent quantity (%)
deposited layer of TiO2 NPs on the surface In order to study the
of CaCO3 played an efficient role. Moreover, synthesis process of CaCO3
particles, the FESEM
the whiteness of TiO2 @CaCO3 -15 and
images of (a) Ca(OH)2 , (b)
TiO2 @CaCO3 -20 were identical, meaning carbonation intermediate of
that the coating effect was similar when the
Commercial TiO2 Ca(OH)2 and TiO2 mixture,
addition of TiO2 exceeded a certain amount. 200.9
100 (c) TiO2 @CaCO3
composites at the end

Z. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 498 (2016) 98105
103
Fig. 8. Size distribution images of (a) commercial TiO2 and (b) disaggregated TiO2 NPs.
Fig. 9. XRD pattern of (a) TiO2 ,
(b) Ca(OH)2 , (c) the mixture of
TiO2 and Ca(OH)2 stirring for 5
min, (d) the mixture for 10 min, (e)
the mixture for 15 min, (f) the
mixture for 20 min, (g) the mixture
for 25 min, (h) the mixture for 30
min.
of carbonation are shown in
Fig. 10. It could be clearly
seen that Ca(OH)2 particles
were composed of the
aggregation of different
sized sheets. In Fig. 10(b),
a small segment of the
Ca(OH)2 sheet was
spindled, which was the
evidence for the transform
process of Ca(OH)2 to
Fig. 7. The reaction
mechanism of TiO2
@CaCO3 composites.
CaCO3 . However, when
the carbonation finished,
there was no sheet material
in Fig. 10(c). Therefore,
Ca(OH)2 provided the
original template for the
synthesis of CaCO3 during
carnation process. In the
following deposition
process of the TiO2 NPs,
the CaCO3 particles played
a role as hard template for
the abundant absorbing
OH on the surface of both
TiO2 [41] and CaCO3
particles [42]. When the
surface of TiO2 was fully
hydroxylated in Ca(OH)2
slurry, a special crystal face
bore equal quantities of two
types of OH groups: a
bridging OH group bound to
4+
a surface Ti ion which
was four coordinates with respect to the mentioned interaction
particle absorbed the OH
lattice and a terminal OH group bound to a forces. The generation of
ions carried the negative
4+
Ti ion which was five coordinates with CaCO3 and the deposition
charge in alkaline Ca(OH)2
respect to lattice oxide ions [43]. So, the of TiO2 NPs on the surface
slurry, so CaCO3 and TiO2
hydroxyl groups on the surface of CaCO3 and
molecules could combine of CaCO3 particles were
TiO2 promoted the deposition of TiO2 NPs on by means of Van der Waals almost simultaneous when
CaCO3 sur-face through dehydration. forces. Thus, TiO2 NPs the CO2 /N2 gas mixture
2+ with a volume ratio of 1:2
Moreover, CaCO3 particle absorbed Ca could deposit on CaCO3
was introduced into the
ions possessed the positive charge and TiO2 surface through the above
slurry. Therefore,

Fig. 10. FESEM images of (a) Ca(OH)2 ,

(b) carbonation intermediate of Ca(OH)2
and TiO2 mixture, (c) TiO2 @CaCO3
composites at the end of carbonation.
104 Z. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 498 (2016) 98105
0.90
0.95
Alkali resistance (24 h)
Normal
pass
Scrub resistance
300
500
these composites showed
similar properties to TiO2 ,
which relied on the
deposited layer of the rutile
NPs on the surface of
CaCO3 .
3.9. The basic properties of
interior emulsion coatings
The contrast ratio of interior
emulsion coatings with
different percentage
replacement of TiO2
@CaCO3 -15 to TiO2 is
shown in Fig. 11. Contrast
ratio at a specified film
Fig. 11. The contrast ratios of interior emulsion coatings with different percentage thickness was an impor-tant
replacement of TiO2 @CaCO3 -15 to TiO2 . hiding power parameter in
coating field, which showed
the ability of a coating to
prevent the transmission of
Table 3 light [44]. As Fig. 11
The basic properties of interior emulsion coatings. showed, the contrast ratio
was high enough in all
samples, although the
Properties contrast ratio declined
GB/T 97562009the indoor gradually as the loadings of
Rutile TiO2 @CaCO3 increase.
When TiO2 @CaCO3
coatings standard of synthetic
completely substituted TiO2
TiO2 @CaCO3
as pigment, the contrast
ratio was 0.934 which was
resin emulsion still higher than the
standards of interior wall
coatings (GB/T 9756-2009).
Considering the cost of
production and the
performance of the interior
State in container emulsion coatings, the
No caking, uniform after percentage replacement of
pass TiO2 @CaCO3 -15 to
commercial TiO2 was
stirring selected as 40%. The basic
properties of the coatings
and the standards of interior
Application property
emulsion coatings (GB/T
No barrier to brush spreads
9756-2009) are shown in
pass
Table 3. The results indi-
cated that the performance
two times of the interior emulsion
coatings with rutile TiO2
Drying time (h) @CaCO3 was up to the
2 standard of GB/T 9756-
pass 2009 and the contrast ratio
Appearance
and scrub resistance
Normal
increased effectively. There-
pass fore, rutile TiO2 @CaCO3
Contrast ratio
could partly substitute TiO2
as pigments in interior
emulsion coatings.
4. Conclusions
In summary, we successfully
fabricated rutile TiO2
@CaCO3 pig-ments by
disaggregation and
deposition of commercial
TiO2 in
alkaline Ca(OH)2 slurry
during a carbonation
process. It was found that
TiO2 NPs were successfully
deposited on the surface of
CaCO3 with good coating
effect and dispersity in the
bulk. Furthermore, the
excellent whiteness and UV
absorption of TiO2 @CaCO3
-15 was opportune to
replace TiO2 in the
applications of coatings. The
con-trast ratio was 0.934
when TiO2 @CaCO3 -15
completely substituted TiO2
as pigment in interior
emulsion coatings.
Considering the cost and
performance, we prepared a
type of interior emulsion
coatings (the percentage
replacement of nano-TiO2
@CaCO3 -15 to commer-
cial TiO2 was selected as
40%) with excellent contrast
ratio and scrub resistance
properties, which was up to
the standard of GB/T 9756-
2009. Therefore, rutile TiO2
@CaCO3 could partly
substitute TiO2 as pigments
in interior emulsion
coatings.
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