Carbonates Evaporites (2018) 33:331–346
https://doi.org/10.1007/s13146-017-0341-x
REVIEW ARTICLE
Synthesis of precipitated calcium carbonate: a review
Onimisi A. Jimoh1 • Kamar Shah Ariffin1 • Hashim Bin Hussin1 • Adesuji E. Temitope2
Accepted: 13 February 2017 / Published online: 9 March 2017
Ó Springer-Verlag GmbH Germany 2017
Abstract The current high global demand for high-quality
paper, paint, adhesive/sealant, and plastic, filler industries
cannot survive without unique and high-quality precipitated calcium carbonate (PCC). They are used as fillers,
additives, and reinforcements. PCC is a key constituent of
the modern paper and plastic industry. This article reports
the effect of various organic and inorganic additives used
in the synthesis of the different polymorph of calcium
carbonate. The use of precipitated calcium carbonate fillers
is the recommended choice in enhancing optical properties,
durability, smoothness and ink adsorption in papermaking
and improving the mechanical properties of plastic. PCC
can best be synthesized using solid–liquid route or the gas–
solid–liquid carbonation route, which consists of bubbling
gaseous CO2 through a concentrated calcium hydroxide
(Ca(OH)2) and/or calcium magnesium hydroxide
(CaMg(OH)2) slurry with suitable organic additives. The
use of several organic and synthetic additives in conjunction with different reaction parameters for the synthesis of
the various polymorph of precipitated calcium carbonate is
reported. Depending on the desired end use, PCC polymorphs such as aragonite, vaterite and calcite are vital in
the plastic and rubber industries.
& Kamar Shah Ariffin
kamarsha@usm.my
1
School of Materials and Mineral Resources Engineering,
Universiti Sains Malaysia, Engineering Campus,
14300 Nibong Tebal, Pulau Pinang, Malaysia
2
Department of Chemistry, Federal University Lafia, PMB
146, Lafia, Nasarawa state, Nigeria
Keywords Precipitated calcium carbonate (PCC) Surfactants as additives Fillers Papermaking Vaterite Carbonation
Introduction
Precipitated calcium carbonates (PCC) are derived from
carbonate rocks. Carbonates are made of particles (composed [50% carbonate minerals) embedded in a cement or
clast. Most carbonate rocks result from the accumulation of
bioclasts created by Calcareous organisms. Carbonate
rocks usually are formed in area favoring biological
activity, i.e., in shallow and warm seas, in areas with little
to no siliciclastic input. Metacarbonates are metamorphosed calcareous (limestone and dolomite) rocks in which
the carbonate component is predominant, with granoblastic
polygonal texture (Bucher and Grapes 2011). Carbonate
and metacarbonates are the most frequently used raw
materials in construction applications since recorded history. The carbonate and metacarbonate rocks are usually
converted into lime after calcination, such as quick lime
(CaO) and slaked lime Ca(OH)2. Both forms have several
industrial uses, i.e., to neutralize acid waste, as fillers in the
pulp and paper industry, and as a flux in the steel industry
(Onimisi et al. 2016), in addition to uses in road construction, gold recovery and other environmental applications (Chakraborty et al. 1994; Jung et al. 2000; Xyla and
Koutsoukos 1989). Carbonate and metacarbonate rocks
usually occur as limestone, marble, travertine, chalk,
coquina, tufa, stalactites and stalagmites in karst regions.
Marble is one of the most common metacarbonate rocks
formed under intense pressure interaction with chemically
active fluid and temperature (Jimoh et al. 2016a). The
parent sedimentary carbonate rocks for marble formation
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are most commonly limestone or dolostone composed of
recrystallized carbonate minerals (Leontakianakos et al.
2013).
Low-grade carbonate rock like dolomite is widely distributed and can be used as one of the best options to
replace expensive and consumable high-grade calcitic
rocks to synthesize amorphous calcium carbonate (ACC)
nanoparticles with optimum quality to meet with industrial
requirements (Mantilaka et al. 2014). In the last few years,
several synthesis routes and methods have been proposed
to produce precipitated calcium carbonate using some lowgrade carbonate rocks like dolomite independently at the
laboratory, with or without focusing on specific applications or simply to carry out basic research on the crystal
precipitation processes (Mantilaka et al. 2013a). Studies
are performed to improve existing methods and/or develop
innovative routes to synthesize well-controlled shapes and
sizes of nanometer-to-submicrometer precipitated calcium
carbonate particles.
Calcium carbonate (CaCO3) occurs in different crystalline polymorphs at ambient pressure. There are anhydrous phases of aragonite, vaterite, calcite and hydrated
phases of monohydrocalcite and hexahydrocalcite (GomezVillalba et al. 2012). The anhydrous CaCO3 can be classified as rhombic calcite, needle-like aragonite or spherical
vaterite. Among them, calcite is known to be the most
stable phase under ambient atmospheric conditions (Knez
et al. 2006). The formation of any of these three polymorphs is strictly dependent on some parameters such as
the temperature, supersaturation and pH of reaction solution (Ibrahim et al. 2014; Montes-Hernandez et al. 2010).
Carbonate rocks have been used in the cement industries
and construction engineering for several years in a form of
ground calcium carbonate (GCC). PCC and GCC have the
same chemical composition. PCC is purer than the carbonate rock from which it is produced, and is lower in
silica, magnesium and lead. PCC’s morphology and size
are different from that of GCC. GCC is seen to be irregularly rhombohedral in shape under high magnification
(Chen and Nan 2011). The PCC crystal morphology
depends on the end product, and the particles are mostly
uniform and regular compared to GCC.
In recent time, carbonate rocks are used in many
industries for the production of PCC. PCC is made of either
fine or very fine nanoparticles that are synthesized either by
carbonation or solution process after calcination and
hydration reaction of a carbonate rock (Arai and Yasue
1990). The need to manufacture precipitated calcium carbonate with definite morphology, structure, and particle
size is necessary due to its wide application in various
industries (Xiang et al. 2002). The multiplex, intricate
action of its structural isomerism, crystal morphology and
phase changes attract the continuous study of calcium
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Carbonates Evaporites (2018) 33:331–346
carbonate (Arai and Yasue 1990; Chen et al. 1997; Hostomsky and Jones 1991).
Global consumption of precipitated calcium
carbonate (PCC) and fine ground calcium
carbonate (FGCC)
There are different types of PCC morphology and particle
sizes, each of which possesses different properties (ElSherbiny et al. 2015). PCC can be marketed in more than one
grade by varying the particle size, particle size distribution,
surface area, and particle morphology (Stratton 2012).
Compared to GCC, PCC has better physical properties,
including high brightness, opacity and purity (Hubbe and
Gill 2016). PCC has internal porosity and a higher specific
area, together with a very good chemical absorption and
binding performance. However, PCC has a high degree of
aggregation, with several crystals growing together forming
a single particle (D’Haese et al. 2013). Particle size distribution is also more uniform than with GCC, providing
smoothness and low abrasion (El-Sherbiny et al. 2015).
Precipitated calcium carbonate (PCC) as well as fine ground
calcium carbonate (FGCC) is used as fillers and extenders in
various types of applications, comprising paper, paint,
plastics and adhesives among many others. The adhesive and
sealant usage incorporates a wide range of products
extending from household caulks to joint cement compounds
and carpet backings. The use of FGCC accounts for 75% of
total collective FGCC and PCC usage. Asia is by far the
highest regional world consumer of FGCC and PCC (Doelle
2012). China tops the world in FGCC usage, with about 26%
of entire FGCC consumption, trailed closely by the United
States of America, with about 25%. Asia is also currently the
world’s major consumer of PCC; China accounts for over
half of global PCC consumption. The United States is the
second-largest PCC consumer, with 16%. Just a little
beneath with 13%, Western Europe is also a large consumer
(Adams 2009). In 2013, PCC demand by papermaking
industries in Western Europe accounted for roughly 85% of
overall European demand (Fig. 1a, b). In Europe, the paper
industry has remained the driving force behind the growth of
PCC market (Ihs.com 2014). The impending growth of PCC
in Europe rests on the capacity of new PCC on-site plants,
which can be cost-competitive with fine ground calcium
carbonate producers.
Precipitated calcium carbonate (PCC)
Calcium carbonate (CaCO3) is widely found in almost all
living creatures, as well in some human tissues. Compared
with other inorganic materials, over the years, CaCO3 has
Carbonates Evaporites (2018) 33:331–346
333
Fig. 1 a Estimated global
consumption of PCC by 2013
and b estimated global
consumption of FGGC by 2013
shown auspicious potential for the development of smart
carriers for various anti-malignant neoplastic drugs. It is
biodegradable, biocompatible and also a good pH-sensitive
material. These properties make CaCO3 suitable for controlled degradability both in vitro and in vivo (Ajikumar
et al. 2005; Barhoum et al. 2015b; Helmlinger et al. 1997;
Wei et al. 2008).
Precipitated calcium carbonate can be handily and
flawlessly produced in a precipitation reaction by reacting
aqueous calcium hydroxide, Ca(OH)2 known as milk of
lime (MOL) with carbon dioxide (CO2) (‘‘carbonation’’).
Synthesis of PCC under certain reaction parameters, such
as reaction temperature of 7–18 °C, may yield ‘‘basic
calcium carbonate’’ that, if desired, can be used as a
forerunner for further conversion to other forms of calcium
carbonate, such as aragonite or calcite, by increased carbonation. In most cases, basic calcium carbonate is a
desirable form of the material because it has a ‘‘flaky’’
structure that is exceptionally good at imparting desirable
functional properties such as whiteness, opacity and high
gloss when prepared as part of filler in paint or paper.
Generally, it is desired to produce precipitated calcium
carbonate in specific forms and particle sizes such as the
nanoparticle size calcite form (Jimoh et al. 2016b). Calcite
mineral exists in a trigonal crystalline form with crystal
habits such as rhombohedral, hexagonal prism, scalenohedral, cubic and prismatic (Xiao et al. 2009). These
specific morphologies are necessary because the coating
properties, such as light dispersion, of a calcium carbonate
material are highly correlated to its morphology, structure
and particle size (Chan et al. 2002). Precipitated calcium
carbonate produced with a Prismatic and rhombohedral
shape has maximum light dispersion at 0.4–0.5 lm sized
particles. On the other hand, scalenohedral-shaped
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precipitated calcium carbonate has a maximum light dispersion of 0.9–1.5 lm particles (Liu and Hart 2008). PCC
of nanometer sized with rhombohedral morphology is
highly effective for use as a coating on paper production
(Price et al. 2010). In food and foodstuffs industries, calcium carbonate is utilized not only because it provides the
body system with an important nutrient (calcium), but also
useful as a conditioner in the prevention of caking in food
powders. Apart from food products, precipitated calcium
carbonates are also used to a great degree in dentifrices,
particularly toothpaste, where they serve as both abrasives
and fillers (Kuhlmann 2001). PCCs are much less expensive when compared to other dentifrice abrasives such as
silica and di-calcium phosphate. PCCs have the same
chemical formula with its precursor material such as
limestone, chalk and marble; CaCO3 (Huwald 2001). PCCs
have a lot of advantages over natural and ground calcium
carbonate with their unique properties of smaller particle
size, high purity, narrow particle size distribution and
regular crystal shape (Gill 1995). Unlike ground calcium
carbonate, PCCs can be produced in different crystal
shapes and in ultrafine particle sizes. PCC is increasingly
used in industries such as paper, rubber, paint, textile,
plastic, sealant, cosmetic, toothpaste and food mainly as a
filler product Ghaffari-Moghaddam et al. (2014). There is a
continuing need for the production of precipitated calcium
carbonate that will bestow maximum lifespan and optical
performance properties to paper, paint, textile, etc., when
included in their coating composition. The desired precipitated calcium carbonate materials should preferably be
in a definite crystal form that is most likely to enhance such
needed performance, and have other important properties
such as particle size and particle size distribution that
further enhance the performance in terms of brightness and
durability of the end product. ISO brightness of 95% is
required for a precipitated calcium carbonate coating pigment; this can only be achieved using very pure carbonate
rocks as raw material (Imppola 2000; Neimo and Yhdistys
1999). The world demand for precipitated calcium carbonate has been on the increase.
PCC production processes
Precipitated calcium carbonates are usually produced, either
in the industries for commercial purpose or in the laboratory
for research using two main methods: by the solid–liquid
route, which involves a direct reaction between Ca2? and
CO32- in an aqueous solution (Kim et al. 2005; Kimura and
Koga 2011), and the solid–liquid–gas route, where CO2 is
bubbled through a slurry of Ca(OH)2 or slake lime (Meldruma and Hyde 2001; Morsy et al. 2014; Sada et al. 1977;
Xiang et al. 2004a; Yagi et al. 1984).
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The liquid–liquid route
The liquid–liquid route is a very fast reaction employing a
rapid mixing under turbulent conditions, and the precipitation occurs on a time scale of seconds, rendering detailed
kinetics study. Precipitated calcium carbonate can also be
produced by a solution process using an aqueous solution
of carbonate salts as a substitute to the gaseous CO2 added
to the reactants in the earlier carbonation process. This
process is often utilized in laboratory production owing to
its easiness in the control of its operating variables (Xiang
et al. 2004b). The most common PCC polymorph obtained
through solid–liquid route is rhombohedral calcite (Ibrahim
et al. 2012; Ukrainczyk et al. 2007). In this process, calcium carbonate can be formed through the following
reactions (Wen et al. 2003):
CaCl2 þ Na2 CO3 ! CaCO3 þ 2NaCl
ð1Þ
CaCl2 þ ðNH4 Þ2 CO3 ! CaCO3 þ 2NH4 Cl
ð2Þ
The solid–liquid–gas route
The solid–liquid–gas route, also known as the carbonation
method, is mostly used in industries as a result of its simple
procedure, low cost, higher yield, and higher purity (Barhoum et al. 2015a). However, the carbonation method is a
slow process compared to solution process, due to the low
CO2 solubility used for PCC synthesis in water (Domingo
et al. 2015). Synthesis of precipitated calcium carbonate by a
carbonation process is one of the most efficient and cheaply
methods being adopted in the industries nowadays. In this
process, the carbonate-rich rock is calcined using furnace
temperatures between 900 and 1000 °C depending on the
rock geochemical composition to produce calcium oxide
(lime) and carbon dioxide, respectively (Miller 2003). The
calcified lime is then treated with distilled water to produce
calcium hydroxide called milk of lime. The resulting milk of
lime is then purified and carbonated with the earlier carbon
dioxide (CO2) obtained from the calcination process.
Calcination of limestone CaCO3 ! CaO þ CO2
ð3Þ
Slaking of quicklime CaO þ H2 O ! Ca ðOHÞ2
ð4Þ
Precipitation CaðOHÞ2 þ CO2 ! CaCO3 ðPCCÞ þ H2 O
ð5Þ
The usual sources of CO2 gas for the solid–liquid–gas
process are the pile of gases from power plants, recovery kilns
or lime kilns. The gas is usually cooled and made clean by
scrubbing before it is compressed and channelled into the
carbonation reactor; it is then bubbled through the slurry as it
dissolves into the water phase (Fig. 2a). During the carbonation reaction, the calcium hydroxide slurry is unceasingly
Carbonates Evaporites (2018) 33:331–346
335
A
B
Additives (PEG, PVC. etc.)
Ca (OH)2 slurry + NaOH
Ca (OH)2 slurry
Stirring (300-400) rpm
Stirring (300-400) rpm
NaCO Solution
CO2 gas
Carbonation
Solution Process
Washing & Filtering
Washing & Filtering
Drying (60°C, 14hrs)
Drying (60°C, 14hrs)
PCC Powder
PCC Powder
Characterization (XRD, SEM)
Characterization (XRD, SEM)
Fig. 2 a Flow chart for the synthesis of PCC by carbonation process, b synthesis of PCC by solution process
under high shear agitation (Krammer et al. 2002; Teir et al.
2005). Depending on the parameter, the solid content of the
slurry is typically about 20% (Virtanen 2002). Sometimes
when no additives or surfactants are added, it is referred to as a
green process. It can be regarded as a green approach because
of the utilization of CO2 gas (Barhoum et al. 2015b). The
general reaction mechanism associated with the carbonation
route process can be expressed as follows:
CO2 þ H2 O ! H2 CO3 ! H þ HCO3 ! 2H þ CO3
ð6Þ
CaðOHÞ2 ! Ca þ 2OH
ð7Þ
Ca þ CO3 ! CaCO3
ð8Þ
The overall chemical reaction is given as:
CaðOHÞ2 þCO2 ! CaCO3 þ H2 O
ð9Þ
Several polymorphs of calcite such as aragonite can be
synthesized using either carbonation process (Ahn et al.
2002; Thenepalli et al. 2015) or by solid–liquid route
(solution process) (Fig. 2b).
Polymorph of PCC
Precipitated calcium carbonate has been reported by several authors to exist in three basic phases: calcite, aragonite, and vaterite. Table 1 shows the common availability
of PCC polymorphs (Wolf and Günther 2001).
Table 1 Availability of calcium carbonate polymorphs
Polymorphs
Non-biological
Biological
Calcite
Very common
Very common
Aragonite
Rare
Very common
Vaterite
Very rare
Rare
Additives and organic surfactants are usually used to
manipulate the particle size and morphology of precipitated
calcium carbonate (Wise 1997). This mostly results in the
change in the structure (polymorph) and the characteristics
of the calcite crystals. Sometimes depending on the additives or organic solvent used, the remaining additives might
not be desired.
Various researchers have been able to produce precipitated calcium carbonate, aragonite precipitated calcium
carbonate, vaterite precipitated calcium carbonate and
amorphous precipitated calcium carbonate using various
methods and different surfactants, chemical additives to
either stabilize, synthesize or modify certain properties or
attributes of the resultant precipitates (Cölfen 2003; Qi
et al. 2002).
Polymorphism of PCC has remarkable technological
significance owing to the dependence of mineral properties
like dissolution kinetics, solubility, hardness, density,
optical properties and morphology on the solid-state
structural arrangement. The control of polymorphism in
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crystalline calcium carbonate has been the area of attention
for several researchers. However, the skill to predict and
control factors such as polymorphism, particle size and
particle size distribution in the course of crystallization
remains one of the significant challenges. The control of
calcium carbonate polymorphism is an intricate interplay
amid thermodynamic and kinetic factors (De Beer 2014).
Subject to reaction conditions, traditional approaches for
selection of calcium carbonate polymorphs usually involve
altering parameters, such as temperature, mixing or stirring
conditions, pH, initial supersaturation, solvents, and the use
of additives either organic or inorganic. Calcium carbonate
crystals can be formed as either spherical polycrystalline
particles of vaterite, needle-like crystals of aragonite and
cube-like or plate-like crystals of calcite, in aqueous
solution. Studies carried out by (Chakraborty et al. 1994)
suggested that the type of calcium carbonate polymorph
form and the particles size distribution are subject to the
supersaturation level and ionic ratio of [Ca2?]/[CO32-] in
solution.
Carbonates Evaporites (2018) 33:331–346
Calcite polymorph
Calcite polymorph is the most efficient and nontoxic, and
is thermodynamically more stable over a broad range of
temperature among the three polymorphs of calcium
carbonate (Kitamura 2001; Wolf and Günther 2001).
However, calcite has been observed to have the least
soluble phase over a temperature range of 0 and 90 °C
among other polymorphs (Plummer and Busenberg 1982).
It is used as a filler in plastics to decrease surface energy
and opacity, and to increase surface gloss in paint. Calcite
is mostly preferred in industries due to the superior
appearance and sparklingly color it gives the end product
when used as filler compared to others (Fairchild and
Thatcher 2000). Under the scanning microscope calcite,
PCC is often identified by the rhombohedral crystal
shapes (Fig. 3a). When specific calcite particle size such
as nano calcite particle is utilized as filler, this helps to
increase the flexibility, impact strength and stiffness of
the material.
Fig. 3 SEM micrographs: (a) calcite PCC, (b) vaterite PCC, (c) aragonite PCC
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Aragonite polymorph
Aragonite precipitated calcium carbonate (A-PCC) is
another polymorph of calcium carbonate which is slightly
thermodynamically stable at certain controlled temperature. The average refraction index of aragonite PCC is
slightly greater than calcite. This attribute makes it a better
filler material when compared to the calcite polymorph
(Dalas et al. 1988); Konno et al. 2002). Synthesized aragonite PCC is often used in industries as a filler/additive in
paper, rubber, plastic, paint and pigment. Controlled synthesized aragonite PCC is often characterized by needleshaped appearance when viewed in scanning electron
microscope (Fig. 3c) (Tai and Chen 1998; Wang et al.
1999; Yu et al. 2004a). The aragonite particles with a very
high aspect ratio improve the impact strength and elasticity
of rubber and plastics (Wenyu et al. 2000).
Vaterite polymorph
Vaterite is the least thermodynamically stable form of
calcium carbonate. Under normal standard and geological
conditions, vaterite will transform into calcite until it
completely disappears (Addadi et al. 2003; de Leeuw and
Parker 1998; Nancollas and Sawada 1982). It has a density
of 2.54 g/cm3 and belongs to the hexagonal crystal system
(Plummer and Busenberg 1982). Organic additives play a
significant role on the vaterite crystal growth rate, and
could prevent the transformation from vaterite to calcite
(Katsifaras and Spanos 1999; Malkaj and Dalas 2002).
With respect to solubility, vaterite is observed to be the
most soluble among the calcium carbonate polymorph. The
particles of vaterite do not show distinct morphology and
usually cluster into spherical particles that are not well
defined (Fig. 3b) (Xu et al. 2006). In biomedical, personal
care and advanced biomaterials industries, vaterites are
utilized as coating agents for manipulating rapid degradation, biocompatibility and also material application in
building and construction (Demichelis et al. 2013; Trushina
et al. 2014; Yamada et al. 2014).
Effect of surfactants and additives on PCC
Over the years, significant efforts have been made by
several researchers in the quest to produce and improve the
quality of precipitated calcium carbonate using various
sources such as marble waste, carbonatites, sparingly soluble calcium sulfate, sparingly soluble magnesium carbonate, and calcium chloride. Also, different carbonation
reactors have also been developed to produce a betterprecipitated calcium carbonate. The use of either organic or
inorganic additives, control of functional variables and
337
special procedures/techniques during the crystallization
process PCC are vital for modifying the crystal form
(polymorphism) and particle shape (morphology), which
are the utmost key parameters to the properties and performance of the PCC products if additional processing is
required.
Several surfactants and chemical additives, such as
polyacrylic acid (PAA), terpineol, polyethylene glycol
(PEG), EDTA, polyvinyl alcohol (PVA), magnesium
chloride, zinc chloride, and dispex A40 (Table 2), have
been used in the synthesis of precipitated calcium
carbonate.
Mantilaka et al. (2013b) used polyacrylic acid (PAA),
synthetic high molecular weight polymers of acrylic acid,
to stabilize amorphous calcium carbonate nanoparticle at a
temperature of 40 °C, pH of PAA at 4.5 and concentration
of 10-2 M. They reported that increase of PAA concentration tends to increase the yield of amorphous calcium
carbonate (ACC) due to the complexation of PAA and
Ca2? ions. Similarly, Cai et al. (2010), Hwang et al. (2015),
Yu et al. (2004b) reported that PAA had the most significant influence on the attributes of PCC. Cheng et al. (2004)
also reported that there was a strong interaction between
the carboxylic groups of PAA and the Ca2? ions, thereby
exhibiting a significant effect on crystal morphology by
influencing the growth of the CaCO3 particles, while the
influence of pH on the CaCO3 particles was slight at low
pH levels (pH 9) but at higher initial pH levels of 12, the
particles produced were irregular aggregates. Xiang et al.
(2002) conducted a series of carbonation experiment at a
temperature of 298 K using a water bath and radial sparger
to investigate the influence of additives such as EDTA,
ZnCl2 and MgCl2 on precipitated calcium carbonate particle sizes. They reported that EDTA was found to be the
most effective by accelerating the carbonation rate, thereby
reducing the reaction time from 80 to 40 min. The faster
carbonation process is favorable for the formation of nuclei
and also led to the formation of superfine precipitated
calcium carbonate particles. Varying the concentration of
EDTA from 0.25 to 1.0% had a significant effect on the
particle morphology by decreasing it from 70 to 50 nm.
Similarly, Westin and Rasmuson (2005) reported that
EDTA notably influences the induction time of PCC
nucleation; however, EDTA showed little influence on the
morphology of PCC when used as an additive.
Xiang et al. (2002) also reported that addition of 1% (w/
w) ZnCl2 shows an obvious decrease in precipitated calcium carbonate particle size and 0.2 lm diameter of
spherical precipitated calcium carbonate particles was
formed. The addition of MgCl2 resulted in synthesizing a
micrometer-sized spindle and spherical-shaped particles.
Park et al. (2008) studied the effect of magnesium
chloride on the synthesis of aragonite precipitated calcium
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Table 2 Summary of effect of different additives/surfactant on precipitated calcium carbonate syntheses
Additives/surfactants
Parameters
Effects
Synthesises
process
References
Poly acrylic acid (PAA)
40–25 °C,
pH 4.5
Crystallization of irregular aggregates PCC
particles
Carbonation
Mantilaka et al. (2013a, b),
Yu et al. (2004a, b)
Ethylenediaminetetraacetic acid
(EDTA)
25 °C,
0.25–1%
conc.
Formation of nanoparticle (PCC)
Carbonation
Xiang et al. (2002)
Zinc chloride (Zncl)
25 °C, 1%
conc.
Formation of spherical nanoparticle size
(PCC) 0.2 lm
Carbonation
Xiang et al. (2002)
Magnesium chloride (Mgcl2)
25 °C, 1%
conc.
Spindle and spherical-shaped PCC
Carbonation
Park et al. (2008)
25 °C, 75%
conc.
Single phase aragonite PCC
70–50 nm
Reduction of reaction time from 80 to 40 min
Citrate and malate
Rod-like shape aragonite PCC
Solution
Park et al. (2008)
Phthalic acid
Rhombohedral shape aragonite PCC
Solution
Park et al. (2008)
Sodium dodecyl sulfate (SDS)
Calcite with vaterite PCC
Solution
Szcześ et al. (2007)
Dodecyltrimethylamonium
bromide (DDTAB)
Increase transformation from vaterite to
calcite with slow crystal growth
Solution
Szcześ et al. (2007)
Poly (N-vinyl-2-pyrrolidone)
PVP
High conc.
Favor calcite PCC, prevent formation of
vaterite
Solution
Wei et al. (2003)
Ammonium citrate
0.3 M/l,
10 °C
Calcite PCC 40–90 nm
Solution
Zhang et al. (2012)
Polydiallyldimethylammonium
chloride (PDDA)
1 g/l,
30–50 °C
Rhombohedral calcite PCC
Solution
Altay et al. (2007)
90 °C
Rectangular prism calcite PCC 10 lm
0.1 g/l, 90 °C
25% aragonite PCC
1 g/l,
30–50 °C
Calcite PCC
Solution
Altay et al. (2007)
0.1 g/l, 90 °C
19% aragonite
0.1 g/l
30–70 °C
100% calcite
Solution
Altay et al. (2007)
Solution
Liang et al. (2004)
Cetyl trimethylammonium
bromide (CTAB)
Ethylenediaminetetraacetic acid
(EDTA)
Carboxymethyl chitosan
(CMCS)
0.1 g/l 90 °C
27% aragonite PCC
2.0 g/l
100% calcite PCC
1000 ppm
Spherical PCC particle
10000 ppm
Peanut PCC shape
Dodecyl sulfonate (DDS)
Calcite PCC
Solution
Wei et al. (2004)
Sodium dodecyl
benzenesulfonate (SDBS))
Vaterite PCC
Solution
Wei et al. (2004)
Non-ionic dextran
35–40 °C
Rhombohedral and scalenohedral calcite PCC
Carbonation
Kontrec et al. (2011)
Poly (N-vinyl-1-pyrrolidone)
(PVP)
0.0005%
conc.
Calcite PCC
Solution
Kim et al. (2005)
0.005%
Aragonite PCC
Konopacka-Łyskawa et al.
(2015)
Konopacka-Łyskawa et al.
(2015)
Glycerol
0.05%
Calcite ? aragonite PCC
20%
Calcite PCC of 0.1–0.59 lm
Carbonation
Calcite PCC of 2.5 lm
Carbonation
Calcite PCC
Solution
Isopropyl alcohol and n-butanol
Polyacrylamide (PAAM)
0.50–50%
carbonate; they reported that increment of Mg2? ions leads
to a low yield of Mg-calcite and higher yield of aragonite
concomitantly, when MgCl2 concentration is 75 mol%,
123
Kim et al. (2005)
Mg-calcite was absent and only single-phase aragonite was
obtained. But as the concentration of MgCl2 is increased,
the longitude and aspect ratio of the aragonite crystals
Carbonates Evaporites (2018) 33:331–346
decrease. Park et al. (2008) also studied the effect of adding
organic additives along with Mg2?; they found out that
citrate and malate promote the formation of rod-shaped
aragonite crystals, whereas phthalic acid promotes the
formation of rhombohedral aragonite. However, when
glucose or sucrose was added, the synthesis of aragonite
was inhibited. They presumed that these findings are
related to the structural characteristics of the respective
organic additive. Feng et al. (2007) studied the effect of
particle size distribution of precipitated calcium carbonate
particles by considering the additives such as EDTA and
terpineol, CO2 flow rate, the CO2 bubble size, the CO2
concentration and the reaction temperature in a wet carbonation process. They reported that there was a particle
size decrease with a decrease in bubble size of CO2 which
also corresponds to the decrease of CO2 concentration.
However, more contradictory results were reported compared with previous literature data: this includes the drastic
reduction of precipitated calcium carbonate particle size
when EDTA and terpineol were used as additives; the
effect of temperature was affected by the additives and also
the addition of terpineol and EDTA sometimes results in
the precipitation of larger particles. Feng et al. (2007)
reported an average particle size of 1–3 lm at ambient
temperature. The particle size decreased slightly with a
decrease in CO2 bubble size and decrease in CO2 concentration, while the addition of EDTA increases the
average particle size. The addition of terpineol also
increased the average particle size at ambient temperature
but showed significant reduction in size with increase of
temperature to 80 °C. The CO2 flow rate was reported to
have a significant effect on the additive. When terpineol
was used, there was a slight reduction in particle size with
increase in CO2 flow rate. However, the addition of EDTA
resulted in the increase of particle size with the increase of
flow rate.
Kemperl and Maček (2009) studied the precipitation of
calcium carbonate from the hydrated lime of variable
reactivity, granulation and optical properties. They reported that optical properties are necessary for the end use of
precipitated calcium carbonate and, therefore, it is very
important to choose the most suitable lime source. And
also, the optical properties of the end product (precipitated
calcium carbonate) are also affected by the ground or
pulverized grain sizes. They reported that coarse particle
sizes have better optical properties than finer particle sizes,
which is a result of the impurities that adhere to a greater
extent to the finer particles with a larger specific area. The
initial temperature of the hydration water does not have a
great impact on the optical properties of the precipitated
calcium carbonate particles, but it has a huge influence on
the particle size of the calcium hydroxide obtained. At
lower temperatures, more coarse particles were obtained
339
than at higher temperatures. The source of lime also
influences the reactivity of lime. The maximum temperatures of hydration under the same conditions do not differ
significantly, but their kinetics of hydration are different
and so consequently the time needed for the suspension of
lime to each maximum temperature. The granulation of the
lime does not have a significant effect on the maximal
temperature, but again it has an impact on the kinetics of
hydration.
The effect of hydraulic activity on crystallization of
precipitated calcium carbonate using lime-soda process
was studied by Narayanan and Park (2015). They reported
that the crystallization of precipitated calcium carbonate
(PCC) is more dependent on the hydraulic activity of the
limestone than the CaO content, which is a common factor
used in classifying limestone ores according to quality. In
their report, only calcite which is the most stable polymorph was crystallized at hydraulic activity under 10 °C.
As the temperature of the hydraulic activity increases from
10 to more than 20 °C, aragonite polymorphs were crystallized and constituted more than 90 wt% of the precipitated calcium carbonate. But no single-phase aragonite was
crystallized from any limestone ore samples.
Yang et al. (2014) investigated the effect of the geological properties of limestone on the hydraulic activity and
synthetic characteristics of precipitated calcium carbonate.
They reported that limestone with higher formation age
tends to have lower hydraulic activity leading to the production of more calcite polymorph than aragonite when
synthesizing. The presence of larger calcite twins in
limestone is also related to older formation age.
Park et al. (2008) investigated the formation behavior of
precipitated calcium carbonate in three different supersaturation levels to synthesize a single-phase aragonite precipitated calcium carbonate in Ca(OH)2–Na2CO3–NaOH
reaction system. They reported the formation of mainly
vaterite polymorph with some little calcite at high supersaturation; calcite was believed to form primarily at medium supersaturation. At low supersaturation, aragonite
polymorph was predominately formed. They concluded
that single-phase aragonite can be synthesized by adding an
Na2CO3 solution to Ca(OH)2 slurry having different concentration of NaOH solution at 75 °C and under the addition rate of Na2CO3 at 3 ml/min.
Seo et al. (2005) synthesized precipitated calcium carbonate using a pure ethanol and aqueous ethanol solution
as the solvent via a carbonation reaction. From their report,
different shapes of PCC such as calcite, aragonite and
vaterite can be synthesized with half particle size when
compared to PCC synthesized using pure water.
Szcześ et al. (2007) studied the effect of sodium dodecyl
sulfate (SDS) and dodecyl trimethyl ammonium bromide
(DDTAB) in the synthesis of precipitated calcium
123
340
carbonate from aqueous solutions of CaCl2 and Na2CO3.
They found that the introduction of SDS caused more
calcite crystals of smaller size to appear in comparison to
the reference system but suppressed transformation of
vaterite to calcite. While the DDTAB surfactant increased
the transformation from vaterite to calcite, but slow down
the crystal growth.
Wei et al. (2003) reveal that the addition of poly (N-vinyl2-pyrrolidone) PVP in PCC production has no direct influence
on the polymorphs of CaCO3 precipitation, but at high concentration, it shows a significant effect on the morphology of
vaterite and calcite. The poly (N-vinyl-2-pyrrolidone) molecules prevent the formation of vaterite. There was an increase
in the formation of calcite and also the rate of the solventmediated transformation from vaterite to calcite.
Research by Zhang et al. (2012) shows that superfine
powder of precipitated calcium carbonate with high purity
can be produced from calcium carbide residue via a liquidphase process with the aid of ammonium chloride as
extraction agent and ammonium carbonate agent. In their
report, optimum preparation conditions were determined as
follows: the concentration of calcium ion 0.3 mol/l, the
mass ratio of ammonium citrate and calcium ion 0.1,
temperature of carbonization 10 which resulted in precipitation of particle size of calcium carbonate between 40 and
90 nm, in the form of calcite.
Altay et al. (2007) studied the influence of Cetyl
trimethylammonium bromide (CTAB), Ethylenediaminetetraacetic acid (EDTA) and Polydiallyldimethylammonium chloride (PDDA) additives on the morphology
of CaCO3 at variable temperature. From their reports, the
addition of 1 g/l concentration of PDDA at 30 and 50 °C
resulted in the formation of rhombohedral calcite particles.
The increase of the reaction to 70 °C resulted in precipitation of prismatic particles shape of calcite. As the temperature was further raised to 90 °C, rectangular prism
calcite with a particle size of approximately 10 lm was
observed. However, when the concentration of PDDA was
reduced to 0.1 g/l at a temperature of 90 °C, 25% of rodlike aragonite morphology was observed. Similarly, the
addition of CTAB at a concentration of 1.0 g/l and temperature of 30 °C and 50 °C resulted in synthesizing only
calcite particles. When the reaction temperature was
increased to 70 °C, the synthesized particle was seen to
contain about 6% aragonite crystals in the midst of 94%
calcite. Further increase in reaction temperature to 90 °C
resulted in an increase in the formation of aragonite to
10%. However, when the concentration of CTAB was
lowered to 0.1 g/l at a reaction temperature of 90 °C, 19%
of a branch-like aragonite crystal shape was observed.
From their findings, the addition of EDTA at a concentration of 1.0 g/l with a reaction temperature of 30, 50 and
70 °C resulted in the precipitation of 100% calcite. But at
123
Carbonates Evaporites (2018) 33:331–346
90 °C, about 5% aragonite crystals were observed. However, when the concentration was reduced to 0.1 g/l with a
reaction temperature of 90 °C, about 27% aragonite crystals were precipitated. Further increase in the concentration
of EDTA to 2.0 g/l resulted in the precipitation of 100%
calcite particles.
Chen and Nan (2011) studied the effect of combined
surfactants (CTAB and SDS) in the nucleation and precipitation of CaCO3 crystals. They observed that at constant SDS concentration of 0.1 mM, there was a
transformation from vaterite crystals to absolute aragonite
crystal with increase in the concentration ratio of the
CTAB to SDS. However, Tavakkoli et al. (2015) reported
that only calcite polymorph can be synthesized when
CTAB and SDS are used as an additive in PCC synthesis.
Also, SDS has more influence on the morphology of PCC
than CTAB. On the other hand, De Beer (2014) reported
the full transformation of calcite polymorph to aragonite
when a mixture of PAM and CTAB was used as additive in
synthesizing PCC at a temperature of 90–120 °C.
From the research performed by Liang et al. (2004), they
studied the influence of carboxymethyl chitosan (CMCS)
on the morphology and size of precipitated calcium carbonate using a mixed aqueous solution of Na2CO3 and
CaCl2. They reported that without the CMCS addition, a
rhombohedral crystal of CaCO3 was observed. The introduction of CMCS at a concentration greater than 1000 ppm
transformed the crystal size and morphology from rhombohedral to spherical crystal particle. The further increment
of the additive concentration to 10000 ppm, resulted in a
dumbbell PCC crystal shape.
Wei et al. (2004) investigated the effect of sodium
dodecyl sulfonate (DDS), sodium dodecyl benzenesulfonate (SDBS) and poly (N-vinyl-1-pyrrolidone) (PVP) on
precipitated calcium carbonate using solution route (calcium chloride (CaCl3) and sodium carbonate (Na2CO3).
They reported that the introduction of DDS promotes the
transformation of CaCO3 to calcite. However, the introduction of SDBS induced the formation of vaterite in the
PCC. The addition of PVP has a profound effect on the
CaCO3 morphology. Similarly, Hwang et al. (2011)
investigated the influence of SDBS on the crystal face and
morphology of PCC particles from CaO and Na2CO3. They
reported that the addition of SDBS resulted in PCC formation with over 98% porous sphere vaterite polymorph
from an initial cubic calcite polymorph.
Kontrec et al. (2011) were able to synthesize precipitated calcium carbonate using semicontinuous carbonation
route with the aid of dextrans. In their reports, the addition
of non-ionic dextran at 35 and 45 °C showed a great effect
on the carbonation process, which leads to the rampant
increase of dissolved calcium concentration. Also, the
morphology of the resultant precipitated calcium carbonate
Carbonates Evaporites (2018) 33:331–346
was observed to be rhombohedral calcite crystal and
scalenohedral calcite crystals. However, the introduction of
anionic dextran at same conditions of carbonation process
did not show any significant influence on the physical
characteristics of the resultant calcite crystals.
Kim et al. (2005) studied the influence of water soluble
non-ionic polymers on the precipitation of calcium carbonate.
They reported that without the addition of polyvinyl alcohol
(PVA) and the addition of 0.0005% concentration of PVA to
0.020 M of calcium carbonate, resulted in precipitation of
only distinctive crystal of calcite. However, when the concentration of PVA was increased to 0.0050%, aragonite
crystal polymorph was of needle-like shape and a high aspect
ratio was formed exclusively without any calcite crystals.
With further increment in PVA concentration to 0.050%, a
distinctive formed polycrystalline vaterite mixed with few
needle-like shaped aragonite crystals was noticed. The addition of 0.50, 1.0 and 50% polyacrylamide (PAAM) to 0.10 M
of calcite carbonate resulted in the formation of only calcite
crystals with rough textures, truncated rhombohedral shapes
and inverted concave surface appearance. From their work,
the addition of polyethylene oxide (PEO), poly-N-isopropyl
acrylamide (PIPAAM) and poly-N-vinyl pyrrolidone (PVP)
additives on precipitation of calcium carbonate resulted in
crystallization of only calcite crystal both at high and low
concentrations. The effect of these additives was minimal
compared to the effect of PAAM and PVA. When ethylene
glycol and glycerol including dextran were used, only calcite
polymorph without any other polymorph was observed.
Konopacka-Łyskawa et al. (2015) synthesized PCC
particles using aqueous isopropyl alcohol, n-butanol and
glycerol as a solvent on lime slurry using carbonation
process. They reported that an increment of a reactive
mixture of isopropyl alcohol and n-butanol concentration
resulted in the high yield of smaller PCC particles of
approximately 2.5 lm. However, finer PCC particles size
of 0.1–0.59 lm was formed when a single solution of 20%
glycerol concentration was used. Song and Kim (2011)
studied the effect of aspartic acid and lysozyme in PCC
synthesis. They reported the formation of a hexagonal
crystal of vaterite when aspartic acid was used. However,
calcite polymorph with rhombohedral phase was formed
without any vaterite when lysozyme was used. Similarly,
Kim et al. (2010) reported the formation of vaterite polymorph when excess aspartic acid was used as additive.
Precipitated calcium carbonate applications
Precipitated calcium carbonate is widely used as fillers, and
finds uses in many products from asphalt to paper. The
higher value, nano-grade PCC (top cut-off size 100 nm) is
used as an efficient filler in the paper, pharmaceutical,
341
paint, plastic, caulk and sealants industries (Domingo et al.
2006; Song et al. 2009).
Precipitated calcium carbonate fillers for papers
Papers are generally made of cellulosic pulp fibers, a
derivative of renewable natural bio-resources comprising
wood and non-wood lignocellulosic constituents. In the
production of paper grades such as papers for printing and
writing, fillers are commonly the second most essential
piece of the paper stock provided their added volumes are
taken into consideration. Worldwide, the application of
fillers in papermaking is now a very common practice to
meet the needs of paper industries. The addition of fillers in
papers can bring about numerous benefits, such as cost and
energy savings, improvement in optical properties, printability, and appearance of paper products (Deng et al.
2008).
The purpose of adding PCC fillers to papers is to reduce
cost and also to increase functional roles such as optical
properties, smoothness, ink adsorption, durability and sheet
formation. Other fillers such as talc, kaolin, grounded
calcium carbonate and titanium oxide have several limitations and disadvantages listed below:
1.
2.
3.
4.
5.
Titanium oxide is highly expensive.
Under certain conditions, the above-mentioned
fillers can cause abrasion and dusting.
They have low optical properties when compared to
PCC fillers.
A higher solid content of the circulating system with
increased loading level of these fillers.
Poor filler retention.
Evans and Slozer (2003) reported that alkaline nature
PCC has a huge benefit in wood-free paper grade produced
from chemical pulp. This is because it creates a
stable buffered system with strength improvement for most
papers. Studies by Passaretti (1991) show that modification
of PCC with weak acid and calcium chelating agent greatly
improves acid-tolerant properties of papers. Lattaud et al.
(2006) reported that the refractive index of paper can be
enhanced by adding solution of zinc chloride in calcium
carbonate suspension, which produces aragonite shape
PCC filler under certain parameters with coated zinc carbonate surface. Shen et al. (2008) used chitosan, acetic
acid, and hydroxide to modify precipitated calcium carbonate filler for making paper. The strength properties of
the filled papers were improved significantly by encapsulated chitosan on the PCC filler surfaces through alkali
precipitation. Shen et al. (2010) reported that the use of
carboxymethyl cellulose and alum on PCC filler resulted in
the enhancement of brightness, opacity, strength as well as
the air permeability of the paper. Allan et al. (1997)
123
342
Carbonates Evaporites (2018) 33:331–346
believed that the addition of certain fillers like PCC in
papermaking can improve drainage and increase water
removal rates in the pressing and drying processes. Liimatainen et al. (2006) reported that the filtration resistance
of compressed pulps was abridged by adding PCC fillers,
which results in enhanced drainage properties of the paper.
Gerteiser and Laufmann (1989) also showed that the utilization of definite rhombohedral calcium carbonate fillers
could aid drainage.
calcium carbonate was added to it. Work by Lazzeri et al.
(2005) showed that Young’s modulus of polyethylene can
be increased by about 70% as 10 vol% nano-sized precipitated calcium carbonate was introduced to it. Also,
Sahebian et al. (2008) presented that dimensional stability
of HDPE was improved by addition of nano-sized precipitated calcium carbonate.
Precipitated calcium carbonate fillers for plastics
Precipitated calcium carbonate fillers are largely used to
reduce the consumption of expensive TiO2 in various paint
formulations. A typical formulation may contain a mixture
of PCC, combined with micronized talc or calcined clay.
Studies by Lourenço et al. (2015) showed that certain
carbonate grade fillers can save 10–30% of the cost using
expensive TiO2. GCC is the main extender in the paint
industry, particularly where the requirements and specifications are not strict. However, high whiteness and
brightness are progressively becoming the norm so more
PCC is now being used. PCC is well established as the low
price extender with a range of other valuable properties,
such as its brightness and its good weather resistance
(Hassas et al. 2013). The good dispensability of PCC in
water-based systems makes it ideal for low solvent paints,
while its low oil absorption is an advantage for high-solid
coating (Karakaş et al. 2015). PCC is particularly well
suited for interior decorative low-gloss paint. About
10–35% by volume of carbonate filler is typically incorporated into basic solvent or water-based emulsion paints
depending on the final application and the sheen required
(Ciullo 1996).
The nano-precipitated calcium carbonate is used to
control the flow properties, to provide body, and to maintain dispersion. Most commonly, 5–14 lm PCC is used in
flat and semi-gloss paints, while 5–1 lm ultrafine sizes
may be used in gloss finishes to help adjust consistency and
minimize paint sag.
Plastic products are found almost everywhere in homes,
cars and workplaces. Plastic manufacturers have developed
whole ranges of polymers with ever increasing performance and/or economy which have helped plastics replace
more traditional materials such as wood, metal and glass
for many applications.
PCC has been extensively used as filler in plastic
industries with the main purpose of reducing cost. However, the addition of PCC as fillers in plastic can also lead
to greater impact resistance associated with higher elastic
modulus, improved thermal conductivity and shortening of
production cycle (Lin et al. 2008). PCC is one of the most
abundant fillers used in the plastics industries with a definite particle size to meet polymer resins requirements.
Precipitated calcium carbonate is usually used in plastics as
a bulking agent to substitute the costly polymers (Gorna
et al. 2008). Most properties of the unadulterated polymer
are subject to transformation as a result of filling and, as a
result, different material is produced by the amalgamation
of polymer with inorganics. The properties of the resulting
fused material are determined by the properties of the
constituents, type of resin and filler, filler crystal size,
shape and modulus, the absorption of filler in the polymer
medium and the kind of interaction amid the filler bits as
well as filler particles and host polymer (Gorna et al. 2008;
Pukanszky and Moczo 2004).
Dai Lam et al. (2009) reported that due to surface
modification of PCC, a good dispersity of PCC in a
polypropylene (PP) medium was attained and, therefore,
thermal stability was improved. The strong interface of
PCC with PP matrix also produced an increase in yield and
tensile strength of the polypropylene (PP). Sahebian et al.
(2009) investigated the effect of PCC fillers on the properties of high-density polyethylene (HDPE) and its
nanocomposite through differential scanning calorimetry
(DSC) and thermomechanical analyzer (TMA) tests. The
results of DSC tests showed that the addition of nano-sized
precipitated calcium carbonate to HDPE caused an increment in the heat capacity, sensible heat and crystallinity
index. The TMA results showed an increase in the
dimensional steadiness of HDPE as nano-sized precipitated
123
Precipitated calcium carbonate fillers for paint
Precipitated calcium carbonate fillers for sealants
and adhesives
Adhesives and sealant are widely utilized in modern
industrial manufacturing processes. The former are used
mostly to hold or bind together various substrates, while
the latter are employed to stop the movement of water, dirt,
and air through joints (Hubert and Lukanich 2000). PCCs,
when used as fillers in a liquid system such as sealants and
adhesives, effectively control the shrinkage, sag, and the
thixotropic properties Lyu et al. (1999).
Precipitated calcium carbonate fillers are broadly used in
adhesive and sealant composites for cost reduction, rheology modification and strengthening. Carbonate filler grades
Carbonates Evaporites (2018) 33:331–346
used range from coarse (45–30 lm) for the paste to fine
(15–1 lm) for adhesives, caulk and sealants (Said et al.
2013). Usually, the PCC rhombohedral crystal form with a
particle size less than 0.1um is used, although in powder
form these crystals are aggregated largely to [1 lm.
However, scalenohedron PCC is used in sealant production, and PCC loading can be up to 85% by weight.
343
Acknowledgements The authors wish to show appreciation to the
technical staff of the School of Materials and Mineral Resources
Engineering, Malaysia, for their technical support and Okoye Patrick,
School of Chemical Engineering, Universiti Sains Malaysia, for his
encouragement and useful suggestions which improved the
manuscript.
Compliance with ethical standards
Conflict of interest The authors wish to declare that they have no
conflict of interest.
Conclusion
Fine-grade PCC shows a significant improvement in
physical parameters of end product materials when used
as filler compared to other grades of carbonates such as
limestones and marbles used as grounded calcium carbonates (GCC), which typically display a broader and
irregular particle size distribution. Owing to their swift
controllable particle size and shape during synthesis,
calcium carbonate is the most important material for use
as a filler in the production of paper, rubber, plastic,
pharmaceuticals, food, paint, textiles and many other
materials pigments. Fillers such as talc, kaolin, and titanium oxide are frequently more expensive, may have
toxic properties, and are of lesser quality when used. This
can have a momentous influence on energy production
and water treatment costs. The recent increment in the use
of polymer favors increased use of calcium carbonate as a
functional filler in various composites. Calcite is used
widely as a functional filler composite among the three
polymorphs of calcium carbonates due to its thermodynamic stability under ambient conditions. Aragonite precipitated calcium carbonate is metastable and has seen
growing use as a functional mineral filler in many
industries mainly owing to its needle-like particle morphology, which is similar to the needle-like morphology
of muscovite and biotite. Calcium carbonate is a safe and
abundant mineral that offers cost benefit in terms of its
use as coating and fillers in composites and polymers.
With expansion and growing demand within the paper
industry in the present and coming years, the demand for
high-quality precipitated calcium carbonate fillers is
anticipated to grow immensely.
The solid–liquid–gas route (carbonation process) is
more economical and rapid than the solid–liquid (solution process) for synthesizing various calcium carbonate
polymorphs with a wide variety of particle morphologies. Organic and inorganic additives, solution concentration, carbonation parameters and temperatures clearly
influence the crystal systems and morphologies of precipitated calcium carbonate. Subject to controlled
experimental conditions, numerous useful shapes of
calcium carbonate, such as plate and rhombohedral, can
be attained.
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