Materials Science and Engineering A 445–446 (2007) 170–179

Effect of various factors on the particle size of calcium

carbonate formed in a precipitation process
Bo Feng ∗ , Andrew K. Yong, Hui An
School of Engineering, The University of Queensland, St. Lucia, Qld. 4072, Australia
Received 13 June 2006; received in revised form 22 August 2006; accepted 10 September 2006

Abstract
The effect of various factors on the particle size of precipitated calcium carbonate formed in a wet carbonation process has been investigated
experimentally. The calcium carbonate particles were fabricated in a glass reactor by bubbling CO2 through a calcium hydroxide solution of 2.5%
by weight. The particle size distribution of the particles was determined using a laser technique. The operating factors investigated include the
CO2 bubble size (with frit pore size of 17–40 or 101–160 ␮m), the CO2 gas flow rate (3.5 and 4 L/min), the CO2 concentration (25 and 100%), the
reaction temperature (25 and 80 ◦ C) and the additives (terpineol 0.1 and 1 vol%, EDTA 0.25 and 1 wt%). It was found that the average particle size
was between 1 and 3 ␮m. The particle size was reduced slightly with the decrease of the CO2 bubble size, and decrease of the CO2 concentration.
The particle size distribution was affected significantly by the addition of terpineol and EDTA, but not necessarily reduced as reported previously.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Precipitated calcium carbonate; Carbonation

1. Introduction
Calcium carbonate (CaCO3 ) is a natural occurring and abun-
dant mineral comprising approximately 4% of the earths crust
[1]. The ability to manufacture CaCO3 with specific morphol-
ogy, structure, and particle size is invaluable due to its wide
application as filler in composite materials such as plastics, rub-
bers, paper, paints, etc. [2]. The attention given to synthesising
superfine precipitated calcium carbonate (PCC) is in increasing
due to its excellent properties and market demand.
Techniques to manufacture CaCO3 include precipitation or
wet carbonation [3], using emulsion membranes [4] and novel
technologies such as high-gravity reactive precipitation [5]. The
precipitation method is studied in this work because it is rel-
atively simple and it has already been demonstrated that it is
possible to fabricate superfine PCC particles using this method.
There are two precipitation methods in the literature with the
only difference being the chemicals used. The first method is
mixing calcium hydroxide (Ca(OH)2 ) and water into a slurry and
carbonating the solution with CO2 bubbles to form CaCO3 . The
alternative chemical combination used is a mixture of sodium
∗ Corresponding author. Tel.: +61 7 3346 9193; fax: +61 7 3365 4799.
E-mail address: b.feng@uq.edu.au (B. Feng).
carbonate (Na2 CO3 ) and calcium chloride (CaCl2 ) which would
also form CaCO3 . The first precipitation method is investigated
in the work, i.e. using calcium hydroxide and CO2 .
There have been a number of studies on the precipitation
process in the literature. It has been shown that the charac-
teristics of the particles such as the morphology and particle
size can vary greatly in the process. According to Xiang et
al. [3], there are various forms of CaCO3 morphology namely
rhombic calcite, needle like aragonite and spherical vaterite that
vary according to precipitation conditions such as the carbona-
tion solution and the dispersion of CO2 . Reddy and Nacollas
[6] observed that the initial supersaturation and temperature
of the Ca(OH)2 slurry determined the proportion of calcite,
aragonite and vaterite shaped particles. Chakraborty and Bhatia
[7] concluded that supersaturation level and the ionic ratio of
[Ca2+ ]/[CO3 2 ] in the solution affect the crystalline form and the
particle size distribution. Tai and Chen [8] described the CaCO3
morphology change as being related to the pH and supersatura-
tion levels of the Ca(OH)2 solution. The precipitation process
usually produces precipitated CaCO3 particles that are of spindle
shape and having a particle size of more than 2 ␮m [3], however,
much finer particles of different morphologies can be produced
in the process as to be discussed below. It is therefore desirable to
understand how the operating parameters affect the particle size
of the particles produced, so that the carbonation process can

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.09.010
 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
be optimized to fabricate particles of desired size, particularly
superfine size. This paper reviewed briefly the literature work on
the effect of various factors on the particle size and conducted
experimental work to identify the most important factors.
2. Literature review
2.1. Effects of surfactants and additives
Using surfactants and additives during the precipitation pro-
cess can modify certain properties of the final precipitate.
Researchers have used modifiers such as terpineol, Calcium Lig-
nosulphate, Dispex A40V, Dispex A40, poly acrylic acid and
octadecyl dihydrogen phosphate, the effect of which are dis-
cussed briefly below.
• Terpineol: Xiang et al. [3] used terpineol, a widely used
vesicant in hydrometallurgy to accelerate the absorption of
CO2 and achieved nano sized particles. In the experiment,
the diameter of CaCO3 decreased from 150 to 90–120 nm
after adding 0.1–1.0 vol% terpineol. Higher amounts of ter-
pineol resulted in larger particle size with irregular shapes.
This is due to the fact that terpineol has the ability to reduce
surface tension of bubbles significantly thus preventing aggre-
gation and improving the stability of small bubbles. Main-
taining small bubbles benefits the mass transfer of CO2 into
the Ca(OH)2 solution hence producing finer particles. How-
ever, excess levels of terpineol may inhibit the mass trans-
fer rate of CO2 and lead to unwanted reactions such as a
reduction in carbonation rate and formation of bigger CaCO3
particles.
• Calcium Lignosulphonate: Experiments by Kirchgessner and
Lorrain [9] and Wei et al. [10] used Calcium Lignosulphonate
an anionic surfactant which is available as a dry powder
under the trade name of Lignosite. Kirchgessner and Lorrain
[9] varied the Calcium Lignosulphonate amount between 0
and 3% and the mass median particle diameters ranged from
2.9 ␮m for the unmodified slurry to 2.2 ␮m for the one with
3% Calcium Lignosulphonate. Their results suggest that the
Lignosulphonate should be kept below the optimum level of
1.5 wt%. Wei et al. used 2 wt% Calcium Lignosulphonate and
found that the sample tested had the same particle distribu-
tion of 1–2 ␮m as the sample modified with Dispex A40 and
Dispex A40V.
• Poly acrylic acid (PAA): Cheng et al. [11] used PAA and
reported that there were strong interactions between the car-
boxylic groups of PAA and the Ca2+ ions, which had a
significant effect on crystal morphology by influencing the
nucleation and growth of CaCO3 particles. SEM observations
by Yu et al. [12] added that PAA had the most significant influ-
ence on the morphology of CaCO3 at 25 ◦ C.
• Dispex A40 and Dispex A40V: Wei et al. [10] used Dispex A40
and Dispex A40V and achieved a particle size distribution
between 1 and 2 ␮m very similar to samples with Calcium
Lignosulphonate.
• Octadecyl dihydrogen phosphate: Sheng et al. [13] used
octadecyl dihydrogen phosphate as a size controlling addi-
171
tive and modifier. The optimum amount was suggested to be
1% and added during the digestion time. This could reduce
the particle sizes to approximately 75 nm and help maintain
a uniform size. octadecyl dihydrogen phosphate added at the
beginning of the reaction had little effect and totally no effect
at pH 9.
• Polyethylene glycol (PEG): Yu et al. [12] used PEG and
commented that PEG showed no obvious influence on the
morphology (plate-like) and size of CaCO3 particles at 25 ◦ C
but at 80 ◦ C the edges and corners of the plate-like particles
in PEG were slightly dissolving, resulting in irregular shapes
but there was no change in particle size. This was linked to
the fact that the OH groups of PEG might be ionized at higher
temperatures.
• CTAB: Yu et al. [12] used CTAB and recorded that CTAB
had no obvious effects on the morphology of CaCO3 at 25 ◦ C
but displayed great influence on the morphology and phase
structures of the CaCO3 at 80 ◦ C. Aragonite whiskers were
observed in SEM micrographs. Theses particles with whiskers
are in demand in the paint and paper industries. When used as
filler or for reinforcing materials these particles are desired for
the high electrical resistance and elastic modulus they confer
to the composite.
• Polyvinyl alcohol (PVA): According to Yu et al. [12], there
were no effects of PVA on CaCO3 particles at 25 ◦ C. How-
ever at a temperature of 80 ◦ C there was formation of
unusual dendrite-shaped CaCO3 aggregates consisting of two
dendrite-like heads composed of radially aligned crystals.
• EDTA: Xiang et al. [2] concluded from experiments that
EDTA (C10 H16 N2 O8 ) helped accelerate the carbonation rate
which reduced the reaction time from 80 to 40 min. The faster
carbonation rate was deduced to be favorable for the formation
of superfine CaCO3 particles. Varying the amount of EDTA
too had an effect on the morphology of the particles. The
particle size decreased from 70 to 50 nm when the EDTA
concentration was increased from 0.25 to 1%.
• Zinc chloride (ZnCl2 ): Xiang et al. [2] noticed that there was
an obvious decrease in CaCO3 particle size when 1% (w/w) of
ZnCl2 was added. Spherical CaCO3 particles with diameter
of 0.2 ␮m were formed.
• Magnesium chloride (MgCl2 ): Xiang et al. [2] noticed that
micrometer-sized spindle and spherical-shaped particles was
obtained when MgCl2 was added.
2.2. Effect of CO2 flow rate
Research by Agnihotri et al. [14] has shown that particle size
is affected by the CO2 gas flow rate during carbonation. The
particles size is found to decrease with increasing flow rate. The
reduction in particle size with an increasing gas flow rate is due to
the increased shear stress effects as dictated by the gas flow rate
and solids concentration [15]. Wei et al. [10] also noticed that
the time required for completion of the reaction decreases with
increasing CO2 flow rate. The reaction is considered complete
when pH levels show slight acidity. Xiang et al. [2] reported
that the use of a radial sparger used to bubble CO2 gas through
the Ca(OH)2 slurry improved the gas dispersion which led to a
172 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
relative higher carbonation rate and produced superfine CaCO3
particles.
2.3. Effect of pH level
In the carbonation process, the initial pH levels of the solution
does have effects on the morphology of the particles as shown in
a study conducted by Cheng et al. [11]. The influence of pH on
the CaCO3 particles were slight at low pH levels (pH 9) but at
higher initial pH levels of 12, the particles produced were irreg-
ular aggregates. Cheng et al. attributes the loss of morphology
control at high pH levels to the high supersaturation levels of the
initial solution. The size of the primary particles too decreased
with increasing pH and is the result of the increase in nucle-
ation rate of the primary particles. Although pH levels affected
the crystal morphologies, X-ray diffraction (XRD) performed
by Cheng et al. showed that all the products consisted of calcite
crystals.
2.4. Effect of temperature during carbonation
Yu et al. [12] carried out precipitations at 25 and 80 ◦ C and
reported that temperature slightly influenced the morphology
and size of the CaCO3 particles. At 25 ◦ C, the particles were
regular plate-like shaped and size ranged between 6 and 12 ␮m
whereas at 80 ◦ C the particles became slightly smaller (about
4–10 ␮m) and had a rhombohedra shape. Yu et al. attributed this
to the fact that temperature alters the solubility of the calcite
and the increased solubility changes the morphology. Cheng et
al. [11] reported that temperature had an obvious influence on
the morphology of the CaCO3 particles. Experiments carried out
showed that higher temperatures increased the solubility and as a
result changed the morphology of the calcites. Cheng et al. also
noted that when temperature was increased from 25 to 80 ◦ C,
particle size decreased from approximately 6–12 to 4–8 ␮m. It
is interesting to note that Vucak et al. [16] reports that at higher
temperatures, particles with coarser particle size are formed.
This does not agree with the previous two authors.
2.5. Effect of initial concentration
From experiments conducted by Wei et al. [10], suspension
concentration of Ca(OH)2 was seen to have effects on the par-
ticle size distribution. Lower suspension led to much larger
particles and wider particle size distributions. Agnihotri et al.’s
[14] findings agreed with those of Wei et al. that larger parti-
cle sizes and wider particle size distributions were caused by
lower suspension concentrations. This was attributed to nucle-
ation predominating over crystal growth at higher suspension
levels leading to a decrease in particle size. Therefore, suspen-
sion concentrations are to be high if finer particles are to be
produced.
Suspension concentration also had an effect on the morphol-
ogy of the CaCO3 particles produced, as can be seen in the
investigation of the effects of CaCO3 concentration on crystal
crystallization by Cheng et al. [11]. At lower concentrations
(4 mM), the particles had very defined cubic shapes and when
increased to 16 mM, the particles still maintained their cubic
shape but showed a slight increase in size. As concentration lev-
els reach 32 mM, plate-like and irregular particles were obtained.
It is interesting however to note that the results of Cheng et al.
[11] do not agree with Agnihotri et al. [14] and Wei et al.’s
[10] report of particle size decreasing with increasing concen-
trations. In Cheng et al.’s experiment, the particle size seems to
be increasing with concentration.
In summary, the parameters that contribute to the change in
the particle size of CaCO3 are additives, CO2 flow rate, ini-
tial concentration, temperature and initial pH level. The two
additives that showed the most potential of producing superfine
particles are terpineol and EDTA. The particle sizes achieved
from using terpineol range from 90 to 120 nm after adding
0.1–1.0 vol% terpineol. Higher amounts of terpineol resulted
in larger particle size with irregular shapes. Particle sizes of
70–50 nm were achieved when the EDTA concentration was at
1%. The flow rate can be seen from literature as one of the main
factors in controlling the reaction speed which in turn influences
particle size. The flow rate used in the reports reviewed ranged
form 0.95 to 3.81 L/min. The composition of the flow varied with
each researcher from pure CO2 , 25% CO2 in air and 25% CO2
in nitrogen. Literature review also highlights that high initial pH
levels produce smaller particles. The higher pH level as men-
tioned in literature review is caused by the supersaturation level
or the concentration of Ca(OH)2 in water. This correlates well
with the findings of researchers who report finer particles with
higher initial concentration. Wei et al. [10] reported that pre-
vious researchers have conducted studies with initial Ca(OH)2
slurry concentrations of as high as 20%. Temperatures investi-
gated in literatures reviewed were 25 and 80 ◦ C. Temperature is
an important parameter in the carbonation process due to the fact
that it has effects on the final morphology of the particles pro-
duced and at higher temperatures particle size tends to become
smaller. There is an agreement among the literatures reviewed
that smaller particle sizes are due to the solubility of calcite
increasing at higher temperatures.
In spite of the above results, there is still a lack of clear
understanding of how the PCC particles of desired size can be
produced with a combination of the above operating parameters.
This work studied the effect on the particle size distribution of
the PCC particles of the following operating factors: the CO2
flow rate, the CO2 bubble size, the CO2 concentration, the reac-
tion temperature, and the additives such as EDTA and terpineol.
The interest of the work was to produce superfine particles in
nanometer size. Therefore, the initial pH level was maintained
at about 12, which is known to be favourable for the production
of superfine particles.
3. Experimental
3.1. Procedure of particle manufacturing
The reactor used to manufacture the PCC particle is schemat-
ically shown in Fig. 1. The design of the reactor was adapted
from Zakin and Fan [17]. The glass reactor was essentially a
cylindrical container, with a porous frit at the bottom to support
 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
Fig. 1. The carbonation reactor used to produce PCC particles.
the Ca(OH)2 solution in the container while allowing the CO2
gas to pass through. Some glass beads were placed under the
porous frit in order to distribute the gas flow evenly. When the
CO2 gas passes through the porous frit CO2 bubbles will be gen-
erated and the bubble size is directly related to the pore size of
the frit. A series of frit with various pore sizes were used to study
the effect of CO2 bubble size on the particle size of the produced
PCC particles. CO2 dissolving in water provides carbonate ions
that react with Ca2+ ions to form CaCO3 through the following
overall chemical reaction
Ca(OH)2 + CO2 = CaCO3
Due to CaCO3 having a much lower solubility in water
(∼0.0012 g/100 g of water) [18] than Ca(OH)2 , it precipitates
out. At the beginning stages of the reaction, the pH levels remain
alkali for some time due to the suspended Ca(OH)2 replenish-
ing the consumed Ca2+ ions. As the reaction continues, Ca(OH)2
becomes depleted and the concentration of Ca2+ ions is no longer
able to maintain at its solubility limit. However, as CO2 is con-
tinuously being dissolved into the solution, the accumulation of
H+ ions leads to the solution becoming acidic. This is an indica-
tion that all the Ca(OH)2 has been totally carbonated. A typical
pH behaviour during carbonation is shown in Fig. 2.
The standard procedure of a typical experiment is as follows:
first of all, 5 g of Ca(OH)2 was mixed with 200 ml of distilled
Fig. 2. The behaviour of pH value during carbonation. Temperature: ambient,
flow rate: 3.5 L/min pure CO2 , no additives.
173
water to form a standard slurry of 2.5 wt% concentration in a
beaker. The distilled water was heated to the desired temperature
before Ca(OH)2 was added. Secondly, the initial pH level and
temperature of the solution was recorded. Thirdly, the CO2 gas
flow rate was adjusted to the desired value and the slurry poured
into the reactor. The reaction process was timed and pH level
and temperature recorded at 10 min intervals. Fourthly, after the
reaction was complete indicated by a stable and low pH value
as shown in Fig. 2, the CaCO3 solution was left to stand for
10 min before vacuum filtering. When terpineol was added as
an additive, the oil on the surface was removed using a pipette
before filtration. Fifthly, the filtered particles were dried in an
oven and characterised for the particle size distribution. After
every sample manufactured, the reactor was washed and water
forced through the sintered glass plate to dislodge any trapped
particles. In the case of severe blockage, hydrochloric acid (HCl)
was introduced into the reactor and the PCC particles were safely
removed from the frit pores.
3.2. Precipitation parameters
The parameters that have been investigated are CO2 flow rate,
bubble size, CO2 concentration, temperature and chemical addi-
tives. The CO2 flow rate and CO2 concentration were controlled
by rotameters. The bubble size was changed by using a reactor
with a frit of different pore size. The temperature of the solution
was controlled by a thermocouple and a heating plate. The addi-
tives used were terpineol and EDTA. Table 1 lists the parameters
and the values. It should be mentioned here that the bubble size
in the figures to follow refers to the pore size of the porous frit,
rather than the actual CO2 bubble size. The actual CO2 bubble
size may be calculated using the equation as in Xiang et al. [3].
3.3. Characterisation of particles
The particle size distribution of the manufactured particles
was determined using a particle sizing machine Malvern Mas-
tersizer 2000. This machine utilizes low angle light scattering
technique to determine the particle size based on the Mie the-
ory [19] that is a complete mathematical–physical theory of the
scattering of electro magnetic radiation by spherical particles.
The machine is ready for measurement as soon as the laser
obscuration by the particles is sufficient. As the sample is fed
through the machine, the particles will pass by a laser beam.
As the laser hits an individual particle, there will be a slight
deflection of the beam. This deflection is then registered by
Table 1
Experimental conditions
Temperature: ambient, 80 ◦ C
CO2 flow rate: 3.5 L/min, 4 L/min
Bubble size (controlled by pore ∼101–160 ␮m, ∼17–40 ␮m
size of sintered glass plates):
Additives: no additives, Terpineol 0.1 vol%,
Terpineol 1 vol%, EDTA 0.25 wt%,
EDTA 1 wt%
CO2 concentration: 100%, 25%
174 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
Fig. 3. Particle size distribution of sample before and after ultrasound.
the photodiode sensor. This process essentially assigns the laser
deflection to a predetermined corresponding particle size that
would cause the laser to deflect by that amount.
During the particle sizing it was found that the particles were
highly agglomerated and ultrasound can break up the particles
effectively, as can be seen in Fig. 3. The samples were subjected
to ultrasound in 3 min blocks before readings were taken again.
The ultrasound was repeated if the change after the first 3 min
were quite obvious. It was noticed that ultrasound had little to
no effect on the particle size distribution after 6 min. Therefore,
each sample was subject to ultrasound for at least 6 min before
the characterisation of its particle size distribution. The result is
consistent with the report of Vucak et al. [16] who found that
agglomeration occurred when pure CO2 was used in the carbon-
ation process. It was observed in this work that agglomeration
was not significant when a mixture of CO2 and nitrogen (N2 )
(CO2 concentration 25%) was used.
4. Results and discussion
4.1. Effect of CO2 bubble size
As shown in Fig. 2, the carbonation reaction rate became
faster when smaller CO2 bubble size was generated. This can
be explained by the fact that with the same amount of CO2 gas,
utilizing smaller bubbles increases the overall surface area the
Fig. 5. The value of pH during carbonation at 25 ◦ C (a) and 80 ◦ C (b). Bubble size: 17–40 ␮m, flow rate: pure CO2 3.5 L/min, () EDTA 0.25 wt%, (䊉) terpineol
1 vol%, () EDTA 1 wt%, () terpineol 0.1 vol%.
Fig. 4. Effect of CO2 bubble size on particle size distribution. Temperature:
ambient, flow rate: 3.5 L/min pure CO2 , no additives.
bubbles have for contact with the Ca(OH)2 solution as compared
with bigger bubbles. The particle size appeared to be slightly
smaller when the pore size of the frit decreased from 101–160
to 17–40 ␮m, as shown in Fig. 4. This indicates that the particle
size is not sensitive to the frit pore size although smaller pore
size tends to produce finer particles. The average particle size
was found to be around 1.5 ␮m, which is consistent with the
literature data.
4.2. Effect of temperature during carbonation
Fig. 5 shows the variation of the pH value during carbona-
tion at 25 and 80 ◦ C. It can be observed that when temperature
is increased, the process takes less time to complete. Also at
higher temperature the pH levels drop rapidly from the initial
slow stage to near completion in a shorter span of time. Another
observation is at higher temperatures, the initial pH levels of the
slurry tend to be lower (although the concentration of Ca(OH)2
is the same). This lower initial pH level could have an impact
on particle size due to the fact that a higher initial pH level
contributes to the formation of smaller particles, as discussed
earlier.
The effect of temperature on the particle size distribution is
shown in Figs. 6 and 7. The difference between Figs. 6 and 7 is
that the flow rate of pure CO2 is 3.5 L/min in Fig. 6 and 4 L/min
in Fig. 7. The following observations may be made:
 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
Fig. 6. Effect of temperature on particle size distribution, under the flow rate of 3.5 L/min pure CO2 .
• Temperature had a pronounced effect on the particle size dis-
tribution of the produced particles.
• The effect of temperature was different for EDTA and terpi-
neol addition. The effect of temperature was more significant
when terpineol was added.
• When terpineol was added, the particle size distribution
curves moved to the lower side at higher temperature. The
average particle size changed from about 2.5 ␮m at 25 ◦ C to
about 1 ␮m at 80 ◦ C. Apparently more nanosized particles
were formed at 80 ◦ C.
• It appears that the effect of temperature was not sensitive to
the amount of terpineol added in the range of 0.1 and 1 vol%.
• When EDTA was added, the effect of temperature was not
consistent in all cases. It appears that the particle size distri-
bution became narrower at 80 ◦ C and the average particle size
became slightly larger.
• The effect of temperature was not sensitive to the amount of
EDTA added in the range of 0.25 and 1 wt%.
The above results are different from those reported in the lit-
erature. The average particle size (1–3 ␮m) observed is smaller
than that reported in some papers (6–8 ␮m) [11,12], but much
larger than that in the other papers (<120 nm) [2,3]. It was
175
also found that higher reaction temperature did not necessar-
ily produce smaller particles. The effect of temperature could
be different when different additives were added. This is most
likely due to the chemical effects of the additives.
4.3. Effects of CO2 flow rate
The effect of CO2 flow rate on the particle size distribution
is depicted in Fig. 8 (with terpineol added) and Fig. 9 (with
EDTA added). It appears that the particle size decreased slightly
with the increase of CO2 flow rate when terpineol is added, and
the effect of CO2 flow rate was not sensitive to the amount of
terpineol added. However, when EDTA was added the particle
size appeared to decrease with the increase of CO2 flow rate at
ambient temperature and increase with the increase of CO2 flow
rate at 80 ◦ C. Also the effect of CO2 flow rate changed slightly
with the amount of EDTA added.
4.4. Effect of addition of EDTA
The effect of EDTA addition on the particle size distribution
is summarised in Fig. 10. The following observations may be
made:
176 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
Fig. 7. Effect of temperature on particle size distribution, under the flow rate of 4 L/min pure CO2 .
• The sample with no additives had three peaks, two of which
were in the large particle size range. These two peaks represent
the agglomerates that could be due to some primary particles
lumped together or some large particles. Addition of EDTA
helped eliminate the two peaks and achieved a more even
distribution of particles.
• After adding EDTA of various amounts, the primary particle
sizes of the samples with EDTA became slightly larger than
the sample without additives.
• When the amount of EDTA increased from 0.25 to 1 wt%, the
primary particle size appeared to increase slightly, and the par-
ticle size distribution became wider. This is in contradiction
with the result of Xiang et al. [3] who reported that there was
a reduction of particle size when the amount of EDTA was
increased.
4.5. Effect of addition of terpineol
The effect of terpineol addition on particle size distribution
is summarised in Fig. 11. The following observations may be
made:
• With the addition of terpineol, the particle size distribution
became more even.
• The particle size was increased after adding terpineol at ambi-
ent temperature. However the particle size became smaller at
80 ◦ C.
• When the amount of terpineol was increased from 0.1 to
1 vol%, the particle size appeared to decrease slightly. This
does not agree with the result of Xiang et al. [3] who found
a pronounced reduction in particle size when the amount of
terpineol increased from 0.1 to 1 vol%.
4.6. Effect of CO2 concentration
The effect of CO2 concentration is shown in Fig. 12. The
particle size was slightly smaller when 25% CO2 was used.
This is consistent with the literature report that the particle size
decreases with the decrease of CO2 concentration.
4.7. Relationship between pH value and particle size
It has been reported in the literature that the particle size
correlates well with the carbonation reaction rate. A higher
 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179 177

Fig. 8. Effect of CO2 flow rate (pure CO2 ) on particle size distribution with terpineol added.

Fig. 9. Effect of CO2 flow rate (pure CO2 ) on particle size distribution with EDTA added.
178 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
Fig. 10. Effect of EDTA addition on particle size distribution. Line only: No
additives, T 25 ◦ C, pure CO2 3.5 L/min; () T 25 ◦ C, pure CO2 3.5 L/min; () T
80 ◦ C, pure CO2 3.5 L/min; () T 25 ◦ C, pure CO2 4 L/min; (×) T 80 ◦ C, pure
CO2 4 L/min.
Fig. 11. Effect of terpineol addition on particle size distribution. Line only: No
additives, T 25 ◦ C, pure CO2 3.5 L/min; () T 25 ◦ C, pure CO2 3.5 L/min; () T
80 ◦ C, pure CO2 3.5 L/min; () T 25 ◦ C, pure CO2 4 L/min; (×) T 80 ◦ C, pure
CO2 4 L/min.
Fig. 12. Effect of CO2 concentration on particle size distribution.
carbonation rate results in a smaller particle size. This work did
not confirm this. As shown in Fig. 5 when EDTA was added
at 80 ◦ C the carbonation rate was high but the particle size
was large. However it was found that the particle size appeared
to correlate very well with the pH value during carbonation.
Fig. 13 shows the effect of flow rate on the pH value during
carbonation. The particle size distributions corresponding to
the pH curves can be found in the previous figures. It seems that
a higher pH value always corresponds with a smaller average
particle size. When the pH values are very close to each other
it can be found that the particle size distributions are also very
close to each other. The results seem to suggest that the absolute
pH value should be a better indicator of particle size than the pH
changing rate.
4.8. Discussion
This work confirmed the following literature results: the par-
ticle size decreases with the decrease of bubble size, and the
decrease of CO2 concentration. However more contradictory
results were obtained compared with the literature data. These
include that the particle size was not as small as reported in the
literature when terpineol and EDTA were added, the increase of
CO2 flow rate did not always result in a smaller particle size, the
effect of temperature was affected by the additives, and the addi-
tion of EDTA and terpineol sometimes produced larger particles.
It is difficult to identify the causes of the discrepancies in this
work, indicating clearly the need of further investigation. It is
believed that the precipitation process is controlled by the mass
transfer at the gas–liquid interface [20,21]. The results obtained
in this work seem to suggest that the additives affect the mass
transfer process significantly.
There was a good correlation between the pH value and
the average particle size, and a higher pH value corresponds
with a smaller particle size. This is perhaps due to the effect
 B. Feng et al. / Materials Science and Engineering A 445–446 (2007) 170–179
Fig. 13. The behaviour of pH value during carbonation at various conditions. () Flow rate 3.5 L/min of pure CO2 , () flow rate 4 L/min of pure CO2 .
of pH on the nucleation rate of CaCO3 [22]. Precipitation takes
place immediately at high pH, whereas with decreasing pH the
induction time of CaCO3 precipitation increased considerably
[22].
5. Conclusions
The average particle size of calcium carbonate fabricated in
a precipitation process at ambient temperature was typically
between 1 and 3 ␮m. The particle size decreased slightly with
the decrease in CO2 bubble size, and decrease in CO2 concentra-
tion. The addition of EDTA increased the average particle size
although the particle size distribution became more even. The
addition of terpineol increased the average particle size at ambi-
ent temperature but decreased the particle size pronouncedly at
80 ◦ C. The effect of flow rate was affected by the additive. When
terpineol was added, the particle size was reduced slightly with
the increase of flow rate. However when EDTA was added, the
particle size increased with the increase of flow rate. The pH
value during carbonation appeared to be a good indicator of par-
ticle size, with a higher pH value indicating a smaller particle
size.
Acknowledgements
The authors are grateful to Prof. Max Lu and Mr. Luke
Matthew for their support in laboratory work. The authors also
thank Prof. Jim Litster and Mr. David Page for the access of the
particle sizing machine.
179
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