Korean J. Chem. Eng.

, 32(6), 1009-1022 (2015) pISSN: 0256-1115

DOI: 10.1007/s11814-015-0057-3 eISSN: 1975-7220
REVIEW PAPER INVITED REVIEW PAPER

A strategy of precipitated calcium carbonate (CaCO3) fillers for enhancing

the mechanical properties of polypropylene polymers
Thriveni Thenepalli*, Ahn Young Jun**, Choon Han**, Chilakala Ramakrishna***, and Ji Whan Ahn*,†

*Mineral Processing Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 305-350, Korea
**Chemical Engineering Department, Kwangwoon University, Nowon-gu, Seoul 139-050, Korea
***Hanil Cement, 302, Maepo-ri, Maepo-eup, Danyang-gun, Chungbuk 395-903, Korea
(Received 18 November 2014 • accepted 25 March 2015)

Abstract−A wide variety of fillers are currently used in more than twenty types of polymer resins, although four of
them alone (polypropylene, polyamides, thermoplastic polyesters, and polyvinyl chloride) account for 90% of the mar-
ket of mineral fillers in plastics. Polypropylene (PP) and PVC dominate the market for calcium carbonate. PP is a ver-
satile reinforcement material that can meet engineering and structural specifications and is widely used for automotive
components, home appliances, and industrial applications. Talc, mica, clay, kaolin, wollastonite, calcium carbonates,
feldspar, aluminum hydroxide, glass fibers, and natural fibers are commonly used in fillers. Among these, calcium car-
bonate (both natural and synthetic) is the most abundant and affords the possibility of improved surface finishing, control
over the manufacture of products, and increased electric resistance and impact resistance. Meeting the global challenge
to reduce the weight of vehicles by using plastics is a significant issue. The current the global plastic and automobile
industry cannot survive without fillers, additives, and reinforcements. Polypropylene is a major component of the mod-
ern plastic industry, and currently is used in dashboards, wheel covers, and some engine parts in automobiles. This
article reports that the use of calcium carbonate fillers with polypropylene is the best choice to enhance the mechanical
properties of plastic parts used in automobiles.
Keywords: Carbonation Mechanism, Calcium Carbonates, PCC, Fillers, Polypropylene Polymers, Mechanical Proper-
ties, Plastics

INTRODUCTION coating pigments for paper, rubbers and plastics, adhesives, and
paints, calcium carbonate forms in three polymorphs: calcite, ara-
Limestone (calcium carbonate (CaCO3)) is an abundant min- gonite, and vaterite. The most thermodynamically stable form at
eral, occupying 5% of the earth’s crust. Used as functional filler and ambient temperatures is calcite. Generally, calcite shows a variety

Table 1. Physical properties of calcium carbonate fillers (calcite and aragonite)

Calcite Aragonite GCC
Properties
Rhombohedral Scalenohedral (Orthorhombic) Fine ground Ultrafine ground
−9 −9
Solubility product (Ksp) 3.36×10 6×10
Density (g/cm3) 2.71 2.93
Hardness (Mohs scale) 3.0 3.0 3.5-4 3 3
Refractive index 1.58 1.58 1.63 1.58 1.58
Coordination number 6 9
Specific gravity 2.71 2.71 2.92 2.71 2.71
TAPPI brightness 99 99 99 95 95
Surface area (m2/g) 6-8 9-15 9-13 5-7 10-12
Particle size2 - 2
+5 µm (%) 99 45
−2 µm (%) 0.7 1.0-3.0 0
Mean (µm)

†
To whom correspondence should be addressed.
E-mail: [email protected]
Copyright by The Korean Institute of Chemical Engineers.

1009
1010 T. Thenepaili et al.

of morphologies, the most common being trigonal, rhombohedral,

colloidal, needle-like [1], and scalenohedral forms [2,3]. Aragonite
is a metastable polymorph under ambient temperature and high
pressure. The aragonite precipitated calcium carbonate morphol-
ogy is orthorhombic, needle-like (acicular) [4-10], flower-like, and
flake-like. Lastly, vaterite, a less stable form, shows a hexagonal mor-
phology. Control of the crystal shape and morphology of CaCO3
is important for industrial applications. The main differences be-
tween the polymorphs in terms of their physical properties are pro-
vided in Table 1. The superior performance of aragonite is attributed
to its morphological differences (e.g., particle aspect ratio and density).

PRECIPITATED CALCIUM CARBONATES

The controllable synthesis of calcium carbonate (CaCO3) has

received considerable attention owing to the wide variety of appli-
cations of CaCO3 in industrial fields such as paper, rubber, plas-
tics, and paints [11]. Calcium carbonate also plays an important
role in reduction of flue gases and waste water treatment [11]. The
applications of CaCO3 particles are determined by a number of par-
ameters, including specific surface area, morphology, size, bright-
ness, oil adsorption, and purity. Particle morphology plays an im-
Fig. 1. (a) Estimated consumption and forecast demand for GCC
portant role in industrial applications. Control of crystal shape and
and PCC by market, 2011 and 2016 (000t), USA ((source:
size is therefore a basic requirement from the viewpoint of applica- Adapted from reference 14). (b) Estimated consumption and
tions. forecast demand for PCC by market, 2011 and 2016 (000t),
Polymers filled with aragonite filler show improved mechanical USA (source: Adapted from reference 14).
properties such as impact resistance, tensile strength, glass tem-
perature, and decomposition temperature, while aragonite-con-
taining paper coating shows benefits including improved brightness, two methods: i) solid-liquid-gas; solid Ca(OH)2 is added to a MgCl2
opacity, strength, and printability. The morphology of CaCO3 par- solution and gaseous CO2 is injected into a suspension of MgCl2-
ticles plays an important role in paper and painting industries, espe- Ca(OH)2 or ii) liquid-liquid-gas (Fig. 2(a)); gaseous CO2 is injected
cially cubic shaping. These particles may also lend high electric in- to a mixture of MgCl2 and Ca(OH)2 solutions. The general mecha-
sulation and a high elasticity modulus to composites [12]. nism involved in the carbonation process can be expressed as follows:
A newly identified source of aragonite calcium carbonates is bivalve
[CO2+H2O→H2CO3→H++HCO3− →2H++CO32− ] (1)
shell waste, which is available from marine aquaculture and is cur-
−
rently dumped into landfills. Recently, some value added products [Ca(OH)2→Ca +2 OH ]
2+
(2)
(calcium carbonates) have been obtained from bivalve shell waste
[Ca2++CO32− →CaCO3] (3)
in efforts to control the disposal problem and in particular the waste
has been utilized as a filler for polymers [13]. The overall reaction is given as
1. Global Consumption of Ground Calcium Carbonates and Pre-
cipitated Calcium Carbonates (PCC) [Ca(OH)2+CO2→CaCO3+H2O] (4)
The global demand for calcium carbonates has been rising con- The carbonation reaction starts from the hydration of carbon
tinuously and is expected to reach 108.5 million tons (Mt) by roughly dioxide and ionization of calcium hydroxide, as shown in Eqs. (1)
2016. Demand for both ground calcium carbonates (GCC) and and (2). The calcium and carbonate ions react together to form a
precipitated calcium carbonates (PCC) continue to increase for paper calcium carbonate precipitate. Calcium carbonate also can be syn-
coating applications as well as mineral fillers for plastics industries thesized by a solution process in which an aqueous solution of car-
(Fig. 1(a). Recently, precipitated calcium carbonate (PCC) and nano bonate salts instead of gaseous CO2 is added to the reactants. In
calcium carbonates have been used for polypropylene composites the solution process,
in both the paper and plastic industries (Fig. 1(b)) [14]. Among (CaCl2-Na2CO3, CaCl2-(NH4)2CO3, CaCl2-K2CO3 system), CaCO3
the global consumers of calcium carbonates, Asia is expected to can be formed through the following reactions:
occupy a major share, particularly in the paper industries, in the
near future. [CaCl2+Na2CO3→CaCO3+2NaCl] (5)
2. Synthetic PCC Production by Carbonation Process [CaCl2+(NH4)2CO3→CaCO3+2NH4Cl] (6)
Calcium carbonate is synthesized by a carbonation method in
which gaseous CO2 is injected to a Ca2+ ion solution/slurry to precipi- Aragonite can be synthesized either by a carbonation process
tate calcium carbonate. The carbonation process can be conducted by [15] or by a solution process [16]. However, carbonation is prefer-

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 A strategy of PCC (CaCO3) fillers for enhancing the mechanical properties of PP polymers 1011

Fig. 2. (a) Flow chart for the synthesis of PCC by carbonation pro-
cess (b) synthesis of PCC by solution process (source: Adapted
from references 15 & 16).

able because precipitated calcium carbonate is produced through a

carbonation process in industrial settings. Na+ ions also promote
the formation of aragonite in a solution process in which an aque-
ous solution of Na2CO3 is added to a slurry of Ca(OH)2 at 75 oC
[17]. Single phase aragonite PCC also can be synthesized by a solu-
tion process by the addition of an Na2CO3 solution at a rate of 3 ml/
min to a slurry of Ca(OH)2 and NaOH at 75 oC [17] (Fig. 2(b)).
3. From Limestone
The precipitation of calcium carbonate (CaCO3) by a carbon-
ation process is one of the most economically efficient processes Fig. 3. (a) Instrument record for atmospheric carbon dioxide (CO2)
at the Mauna Loa Observatory, (b) seasonal fluctuations of
existing today. Calcium oxide and carbon dioxide are formed from
atmospheric carbon dioxide (CO2) at the Mauna Loa Obser-
limestone by means of calcination between 900 oC-1,000 oC. After vatory (source: Adapted from reference 18).
the calcified lime has been treated with water, the resulting milk of
lime is purified and carbonated with the carbon dioxide obtained
from the calcination process. tion technologies are required.
In recent decades, numerous studies have been carried out to
Calcination of limestone CaCO3→CaO+CO2] (1)
reduce vehicle weight, displacement, engine power, and CO2 At the
Slaking of quicklime CaO+H2O→Ca(OH)2 (2) same time, global manufacturers have been designing new engines
for less fuel consumption. These developments reflect that lower
Precipitation Ca(OH)2+CO2→CaCO3 (PCC)+H2O (3) CO2 emissions are possible if vehicle weight and engine size are
reduced. In Europe, in 2013, for the first time the average vehicle
CO2 EMISSIONS FROM CARS-GLOBAL SCENARIO weight decreased, falling by nearly 10 kg (Fig. 4(b)) [20].

CO2 gas emissions are the main source of global warming (Fig. PLASTICS IN AUTOMOBILE INDUSTRY
3) [18], and 10% of total global CO2 emissions come from cars,
trucks, and motorbikes. As long as CO2 concentrations continue Plastics are highly demanded in almost every industry, includ-
to rise, we can expect severe global warming and faster climate ing automotive, medical, electrical, and packaging, as well as in con-
change. The European Commission has proposed forcing carmak- struction, consumer goods, and electronics. They show good mech-
ers to increase the fuel efficiency of new cars by 20% (Fig. 4(a)) anical properties when combined with polymers and polymer com-
[19]. Between 2000 and 2050 the fuel consumption and CO2 emis- posites. Nowadays, on this basis, plastics are widely used to make
sions by cars is expected to double, as estimated by the Interna- cars more energy efficient by reducing weight, together with pro-
tional Energy Agency (IEA). In non-OECD countries, transportation viding design flexibility, elasticity, toughness, corrosion resistance,
is the major source of the overall greenhouse gas (GHG) emissions breaking strength hardness, and durability.
and CO2 emissions. To control the CO2 emissions from the trans- During the enormous growth of plastic components use in the
port sector, new policies and new eco-friendly sustainable innova- automotive industry, the advantages of using plastics have changed.

Korean J. Chem. Eng.(Vol. 32, No. 6)

1012 T. Thenepaili et al.

Fig. 4. (a) CO2 emissions from passenger cars (source: Adapted from reference 19). (b) CO2 emissions by branded passenger cars (source:
Adapted from reference 20).

Fig. 6. Average plastics weight in total vehicle weight (source: Adapt-

Fig. 5. Average plastics weight in total vehicle weight (source: Adapt- ed from reference 22).
ed from reference 21).

fuel consumption, but also allowing the production of safety sys-

Different kinds of polymers and polymer composites are used for tems without excessive cost. Fig. 5 [21] and Fig. 6 [22] show car
automotive parts having different sizes and shapes. The major ad- manufacturers use 200-300 kg of plastics in today’s cars. Tables 2
vantage of plastics is not only controlling the car’s body weight and [19] and 2-1 [20] show the relation between CO2 emissions and

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 A strategy of PCC (CaCO3) fillers for enhancing the mechanical properties of PP polymers 1013

Table 2. Relation between the car weight and CO2 emissions (source: Adapted from ref. 19)
Average Average CO2/km
Manufacturer
mass (kg) 2011 2010 2009
Maruti Suzuki India Ltd. 0,934 104 104 104
Chevrolet Italia 1,092 113 118 122
Mitsubishi Motor Europe BV (MME) 1,046 120 127 *
Honda Automobile China CO 1,146 125 126 *
Magyar Suzuki Corporation Ltd. 1,163 128 137 138
Honda Motor CO 1,372 142 144 *
Suzuki Motor Corporation 1,242 148 144 146
Audi Hungaria Motor KFT 1,444 149 * *
BMW M GmbH 1,629 153 156 *
Mitsubishi Motors Corporation (MMC) 1,589 154 165 *
Saab Automobile AB 1,699 155 175 184
Honda of the UK Manufacturing 1,450 161 162 *
Fuji Heavy Industries Ltd. 1,582 170 179 178
Jaguar Cars Ltd. 1,900 189 197 196
Chrysler Group LLC 2,005 192 215 216

Table 2-1. Average plastics weight among total vehicle weight (source:
Adapted from ref. 20)
Worldwide top selling vehicles Average Average CO2 g/km
manufacturer mass (kg) 2013
Ford F150 (USA) 2,359 255
Toyota Corolla (Australia) 1,280 154
Volkswagen Golf (EU) 1,180 085
Wuling Hong Guang (China) 1,106 171
Chevrolet Aveo (Mexico) 1,080 144
Toyota Aqua (Japan) 0,970 061
Volkswagen Gol (Brazil) 0,845 151
Maruti Alto 800 (India) 0,565 103 Fig. 7. Global polypropylene supplies to outstrip demand in 2015
(source: Adapted from reference 23).

car weight.
depending on the structure and balance of end uses in the indus-
GLOBAL DEMAND FOR POLYPROPYLENE tries in each region. Fig. 8(a) [24] and Fig. 8(b) [25] show the global
consumption growth rate by polymer (2005-2012 and 2012-2017,
Globally, polymer demand has been rising at different ratios in respectively) and Fig. 8(c) presents the global polypropylene con-
various regions. Among the major thermoplastics, polypropylene sumption growth rate by region [26].
shows the highest demand. Fig. 7 shows the global supply/demand/ Globally, the major polypropylene and polyethylene (PE) con-
forecast of polypropylene (2014) [23]. sumption growth centers are Asia, Central and Eastern Europe,
From a survey of the literature, several types of polymers are used South America, Central and South America, and the Middle East.
in automobiles: high density polyethylene (HDPE), low density Based on Platts petrochemical analysis, Asia and Africa are both
polyethylene (LDPE), polyvinyl chloride (PVC), polystyrene (PS), expected to have the strongest growth polypropylene consump-
polypropylene (PP), polyethylene terephthalate (PET), composites, tion rates, 6% and 5%, respectively. Within Asia, consumption of
and acrylonitrile-butadiene-styrene (ABS). Among all the automo- polypropylene in China exceeded eight million metric tons from
tive polymers, polypropylene has the highest consumption owing to 2005-2013. Global PP consumption is growing in terms of key end-
its easy forming properties and availability at lower prices than other use sectors in the region. The PP demand and consumption rate
materials, followed by polyurethanes (17.6%), ABS (12.8%), com- are also positive in Europe, as PP usage has increased in various
posites (11.5%), HDPE (10.2%), polycarbonates (7%), and PMMA fields. PP compounds are widely used in automotive applications,
(4.4%). electronics and electrical industries, and building and construction.
1. Global Consumption of Polypropylene by Region In general, major polypropylene consumption lies in injection-
Polypropylene consumption patterns vary from region to region molding applications in industrialized countries (Table 3) [27]. The

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1014 T. Thenepaili et al.

applications of polypropylene have also widely spread into the agri-

cultural sector for making agricultural bags, tarpaulins, and fishing
nets along with other uses such as stockings and home appliances.
2. Polypropylene for Plastics
Polypropylene is a homogeneous material that has the same cor-
rosion resistant properties throughout, thus eliminating the need
for additional treatments such as re-coating the inside or outside
to guard against corrosion. Handling, installation, and relocation
of polypropylene equipment are easier because polypropylene is
lighter than most other materials used in fabrication. The light weight
allows for less expensive structural supports and concrete floors.
Meanwhile, more than one-third of communities collect plastic
beyond bottles. In the US, polypropylene recycling rates are increas-
ing, even in the absence of a “formal stream”.
The advantages of polypropylene include low density, good stiff-
ness/impact balance, chemical and thermal resistance, reduced envi-
ronmental impact, good moisture vapor barrier properties, hot fill
and retort capability, and microwavable properties. The low den-
sity of polypropylene reduces the environmental impact. Polypro-
pylene produces less solid waste by weight than PET, PS, and PVC,
respectively. Polypropylene and high-density polyethylene (HDPE)
produce significantly less CO2 equivalent by weight than PET, PS,
and PVC. Recycled polypropylene is being used in many diverse
applications. In the US, polypropylene recycling rates are increas-
ing dramatically.
Recent studies support the evaluation of thermal behavior by
thermo-gravimetric analyzer for rejected polypropylene, plastic
pellets and plastic films collected from the chemical industry, plas-
tic packaging industry and Municipal Solid Waste Plants. These
researchers investigated the kinetic parameters also by using sev-
eral methods such as Coats-Redfern, Ozawa and Kissinger meth-
ods [28] and compared them. Based on their comparisons between
Coats-Redfern and Ozawa methods, they concluded that magni-
tudes of activation energy varied, and it indicates the thermal deg-
radation of plastic waste follows a two-dimensional diffusion mech-
anism. By Ozawa method, thermal degradation of plastic waste fol-
Fig. 8. (a) Global consumption of polypropylene in passenger cars lows three-dimensional diffusion mechanisms.
(source: Adapted from reference 24). (b) Global consump- 3. Global Scenario of Polypropylene in Automobiles
tion growth rate, by polymer (2005-2012) and 2012-2017) There are many examples in modern cars of weight savings made
(source: Adapted from reference 25). (c) Global consump- possible by plastics: plastic bumpers are up to 10.4 kilograms lighter,
tion of polypropylene growth rate by region (2014) (source: engine covers are 4.2 kilograms lighter, and plastic fuel tanks are
Adapted from reference 26).

Table 3. PP global consumption by region - 2011-2015 (source: Adapted from ref. 27)
Country name 2011 kt 2012 kt 2013 kt 2014 kt 2015 kt AAGR growth 15×10 %World 2015
North America 7,758 7,940 8,133 8,338 8,553 02.5% 13.4%
Central/South America 2,772 2,965 3,177 3,395 3,624 06.9% 05.7%
Western Europe 7,620 7,772 7,933 8,100 8,273 02.1% 12.9%
Japan 2,543 2,666 2,798 2,908 3,026 04.5% 04.7%
China 2,567 2,678 2,744 2,769 2,795 01.5% 04.4%
Other Asia/Pacific 14,965 16,049 17,195 18,426 19,735 07.2% 30.8%
Middle East 6,551 6,855 7,165 7,474 7,794 04.6% 12.2%
Africa 3,476 3,363 3,810 4,003 4,200 04.7% 06.6%
India 1,281 1,344 1,419 1,506 1,601 04.7% 02.5%
Total World 2,936 3,251 3,600 3,985 4,403 10.7% 06.9%

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Table 4. Polymers used in a typical cars (source: Adapted from ref. 29)
Component Main types of plastics Weight in av. car (Kg)
Bumpers PP, ABS, PC/PBT 010.0
Seating PUR, PP, PVC, ABS, PA 013.0
Dashboard PP, ABS, SMA, PPE, PC 007.0
Fuel systems HDPE, POM, PA, PP, PBT 006.0
Body (incl. panels) PP, PPE, UP 006.0
Under-bonnet components PA, PP, PBT 009.0
Interior trim PP, ABS, PET, POM, PVC 020.0
Electrical components PP, PE, PBT, PA, PVC 007.0
Exterior trim ABS, PA, PBT, POM, ASA, PP 004.0
Lightening PC, PBT, ABS, PMMA, UP 005.0
Upholstery PVC, PUR, PP, PE 008.0
Liquid reservoirs PP, PE, PA 001.0
Total 105.0

five kilograms lighter than their conventional counterparts (Table use polypropylene with different combinations of filler compos-
4) [29]. ites for car body parts. The key advantage of polypropylene is an
Plastics utilization in the automobile industry is mainly targeted excellent balance of high impact strength/stiffness, improved func-
at mass reduction and simultaneous reduction of carbon dioxide tion integration capability, noise reduction, lighter components,
emissions according to automobile manufacturers. These factors possibility of reducing overall system costs, vibration resistance, a
affect the material cost and research activity investments by com- wide operating temperature range (−40 oC to +120 oC), and chem-
panies. Some global automobile manufacturers (GM, BMW, Nis- ical resistance. Fig. 9(a) shows the PP compounds used in automo-
san, Chrysler, Mercedes, Volkswagen, Toyota, Ford, and Honda) tive applications, and the effects of PP compounds on mechanical
properties are presented in Fig. 9(b) [30].
4. Effects of Polypropylene Composites on Mechanical Prop-
erties
PP composites have significant effects on mechanical proper-
ties in automotive applications depending on the mineral fillers
with different particle shapes and sizes. Polypropylene with suit-
able functional mineral fillers or additives can provide higher stiff-
ness and impact resistance for desired automobile applications. There
are many research reports available about polypropylene with dif-
ferent coated and uncoated fillers. Researchers have investigated
the influence of nano clay (other than calcium carbonates) on mech-
anical properties of polypropylene by applying dihydroxylation at
high temperature. Based on their analysis, flexural modulus and
the deflection temperature for the pp nano composites were much
higher than the virgin pp [31].
Micron size powdered filler materials are widely used in the plas-
tics industry. Based on detailed research investigations [32], the most
influential mechanical properties such as tensile strength, impact
resistance, and flexural modulus of a polymer are all affected by
the addition of a filler. The flexural modulus rises as filler aspect
ratio is increased. A high aspect ratio of particles and a higher modu-
lus lead to higher composite stiffness.
The major final conclusions from the above research investiga-
tions are as follows:
i) The mechanical properties of PP/filler composites depend on
a uniform dispersion of the mineral particles;
ii) Micro-sized particles are suitable for achieving higher impact
Fig. 9. (a) Component of pp compound for automotive application and tensile strength;
(b) mechanical properties of PP compounds (source: Adopt- iii) The stiffness of composites is enhanced by high loading and
ed and modified data from Ref. 29). a high aspect ratio;

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1016 T. Thenepaili et al.

iv) High aspect ratio fillers create large stresses in the polymer
near the filler edges;
v) Low aspect ratio fillers lend medium stiffness but enhance
the impact strength.
Polymer processing by radiation or irradiation influence the poly-
mer physical, thermal and mechanical properties. PP/LLDE blends
with different monomers are highly influenced in their rheologi-
cal and thermal properties by electron beam irradiation. After in-
troducing irradiation, LLDPE/PP is highly effective for crosslink-
ing or branching [33].
The size and shape of the mineral particles can affect the mech-
anical properties, such as the stiffness, tensile, and impact strength.
In recent years, diverse nanomaterials with wide unique proper-
ties have been used as filler materials for polypropylene. Due to
their higher surface area, nanomaterials combined with polymers
are advantageous to form nanocomposites. Based on various research Fig. 10. Effect of calcium carbonate type on impact strength (source:
investigations, micro-sized particle sizes have a limited influence Adopted and modified data from Ref. 31).
on the Young’s modulus of composites, but with nano-size parti-
cles the modulus can be increased. Nanocomposites show superior
mechanical properties over composites with micro-sized particles. morph over a wide range of temperature. Calcite is used as an addi-
tive in plastics, and helps to decrease surface energy, opacity, and
CALCIUM CARBONATE FILLERS FOR surface gloss. Calcite filler provides superior appearance and color
POLYPROPYLENE consistency among various available fillers. In addition, if the par-
ticle size is carefully controlled, calcite can help increase the impact
Calcium carbonate (CaCO3) is one of the most abundant min- strength, elongation at break, notched izod impact strength, and
eral fillers used in the plastics industry with a specific particle size, flexural modulus (stiffness). Accordingly, calcite is the preferred
to meet polymer resins requirements. Among the various mineral filler in many industries and has advantages over other commer-
fillers, calcium carbonate (CaCO3) is one of the most important, cial fillers. IMERYS, a world leading international supplier of white
versatile and widely used fillers for polypropylene in terms of weight. minerals, fillers and extenders based on calcite calcium carbon-
The main motivation to use this mineral is economical. The auto- ates, measured the mechanical properties of different calcium car-
motive industry has been one of the driving forces for the increased bonates (different sizes and shapes) with polypropylene (see Fig.
consumption of functional fillers in plastics. Precipitated calcium 10) [34].
carbonate is widely used in different industries including paper- The addition of calcite-filled calcium carbonate provides an ex-
making, plastics, coating, etc. [11]. cellent balance of stiffness and impact, and can enhance tough-
1. Calcite Filled Polypropylene ness with polypropylene resins. In Table 5, the mechanical proper-
Among the three polymorphs of calcium carbonate, calcite is an ties of calcium carbonates fillers with polypropylene are presented
economical, nontoxic, and thermodynamically more stable poly- [35-57]. Fig. 11 shows the dispersion of calcium carbonates in PP

Table 5. Summary of calcite calcium carbonate as fillers in polypropylene/calcium carbonate composites

CaCO3 polymorph Size (µm or nm) Selected resins Remarks Ref.
Calcite 100 nm Polypropylene Improvement of stiffness, toughness and synergistic 35
homopolymers improvement of mechanical properties
Calcite 70 nm Isotactic Polypropylene Improvement of mechanical properties such as Young’s 36
homopolymers modulus, tensile yield stress and impact strength
Calcite 1.2 µm Isotactic Polypropylene CaCO3 treated with stearic acid and admicellar treated 37
displayed lower tensile strength, Young’s modulus,
and flexural strength, but higher impact strength
Calcite 50 nm Isotactic Polypropylene Addition of nm-CaCO3 increases the crystallization 38
rate of iPP from the molten state
Calcite 50-100 nm, 40-70 nm, Isotactic Polypropylene CaCO3 nanoparticles coated with maleated 39
100-250 nm, 1 µm polypropylene can promote nucleation of iPP
crystals
Calcite 21-39 nm Polypropylene Mechanical property of tensile strength is enhanced 40
as the amount of nano CaCO3 is increased

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Table 5. Continued
CaCO3 polymorph Size (µm or nm) Selected resins Remarks Ref.
Calcite 44 nm Polypropylene Izod impact tests suggest that the addition of CaCO3 41
nanoparticles to polypropylene significantly
increases its impact strength (by almost 300%)
Calcite 2.8 µm Polypropylene The creation of agglomerates can be suppressed by 42
composite fibers establishing calcite homogenization conditions
during spinning with a shear rate of 100-250 s−1
Calcite 1.85 µm Polypropylene Enhancement of toughness and ductility 43
homopolymer
Calcite 4.0 µm and 2.9 µm Polypropylene Addition of lower content of CaCO3 with lower 44
homopolymer particle size tends to decrease the composite viscosity
Calcite 70 nm Maleic anhydride- Young’s modulus increased significantly (25%) when 45
modified polypropylene unmodified, 9-wt% commercial grade CaCO3 was
Licomont AR 504 used with PP-g-MA
(PP-g-MA)
Calcite 1.32-4.20 µm Polypropylene Larger CaCO3 particle size (4.20 µm) with PP showed 46
higher impact strength
Calcite 2.5 µm iPP powder Pimelic acid (PA), a new surface modifier treated 47
CaCO3 to make PP/CaCO3 composites showed
better tough ness and a notched impact strength
value, 19.79 kJ/m2, which is 3.64 times greater than
that of pure PP
Calcite 0.07-1.9 µm Polypropylene A polypropylene-CaCO3 composite showed a 48
significantly higher modulus and improved
toughness, and the notched Izod fracture energy
was raised from 2 up to 40-50 kJ/m2
Calcite 1.1 µm Copolypropylene 50 wt% calcite with copolypropylene showed higher 49
elongation at break and the impact strength
Calcite 1.9 µm-10.5 µm Syndiotactic poly Untreated CaCO3 with syndiotactic poly propylene 50
propylene showed a higher Young’s modulus with an
increasing amount of CaCO3, whereas treated
CaCO3 (with stearic acid) showed the reduced
mechanical properties such as tensile strength and
Young’s modulus, but improved impact resistance
Calcite 1.1 µm Poly(propylene-co- Calcite filled CoPP and TerPP composites showed 51
ethylene) CoPP) and good improvement in Young’s modulus by
poly(propylene- successive increments of the filler but at the same
coethylene-co-1- time higher loadings of filler decrease the yield
butene) (TerPP) stress, elongation at break, and impact strength in
both systems
Calcite 0.07, 0.7 & 3.5 µm iPP Accpro 9346 The 0.7 µm diameter CaCO3 particles enhanced the 52
mechanical properties such as modulus and Izod
impact energy beyond those that of an unfilled
matrix. Initial addition of fillers enhanced strain at
break but at higher loadings it decreased
Calcite 0.07 µm PP1 is a homopolymer, Precipitated calcium carbonate filled with PP1 with 53
PP2 is a propylene- average particle size 0.07 µm enhanced the yield
ethylene copolymer, strength. When the filler content was appropriate,
and PP3 is a mixture of the three pp nano composites improved impact
PP1 and PP2 (PP1 : strength
PP2=1 : 1, weight ratio)
Calcite 0-0.135 µm Iso-polypropylene with The coated CaCO3 with PP composite dispersed 54
4.5 wt% of ethylene homogeneously and improved the mechanical
KS001P properties such as stiffness and toughness

Korean J. Chem. Eng.(Vol. 32, No. 6)

1018 T. Thenepaili et al.

Table 5. Continued
CaCO3 polymorph Size (µm or nm) Selected resins Remarks Ref.
Calcite t-PCC (1-5 µm), Polypropylene Strong interaction of ns-PCC with the matrix caused 55
n-PCC (40-50 nm) an increase in yield and tensile strength
and ns-PCC
(40-50 nm (width)
and 150-200 nm
length)
Calcite 1 µm Polypropylene Surface modified PCCs considerably enhanced the 56
(GWE 27 PP) impact strength and flexural modulus
Calcite 70-90 nm Polypropylene CaCO3 nanoparticles greatly affected the mechanical 57
Homopolymer (grade properties such as elastic modulus and yield stress
H501-HC)
Calcite (from 2.27 µm Polypropylene PP with different filler weight ratios (100 : 0, 95 : 5, 58
recycled clam 93 : 7, 90 : 10, 85 : 15, 80 : 20 and 70 : 30) tested the
shell waste mechanical properties and it is enhances the as
impact strength, flexural modulus and flexural
strength of pp composite
Calcite mixed with <4 µm Polypropylene (T30S) Calcite mixed with little quantity of aragonite with pp 59
little aragonite composite (5, 7 and 15 wt%, respectively) to achieve
(from modified better mechanical properties such as good fracture
clam shell waste toughness & stiffness
such as CS, FCS,
ACS)
Calcite (from 2-4 µm Polypropylene (T30S) Calcite with pp composite (15 wt%) to achieve better 60
modified clam mechanical property toughness
shell waste FCS)
Calcite (from 2-4 µm Polypropylene (T30S) Calcite with pp composite (15 wt%) to achieve better 61
furfural modified mechanical property toughness
clam shell waste
F-MCS)

Fig. 11. SEM micrographs (a) pure PP and (b) nanocomposite with 9.2 vol% filler (source: Adopted and modified data from Ref. 40).

composites [43]. with lower particle size leads to decreased composite viscosity due
A statistical analysis and a 22 factorial experimental design were to better dispersion of the filler in the polymer matrix.
employed to evaluate the effects of the rheological performance of A recent study evaluated the feasibility of using recycling clam
polypropylene/calcium carbonate composites (Fig. 12) [46]. From shell waste containing calcite with an average particle size of 2.27
this analysis, we observed that the addition of lower content of filler µm for use as a filler in the polymer industry. The recycled bivalve

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 A strategy of PCC (CaCO3) fillers for enhancing the mechanical properties of PP polymers 1019

Fig. 12. Effects on grade and content of mineral fillers in the composite melt flow index values (source: Adopted and modified data from
Ref. 43).

shell is a calcite calcium carbonate source that can potentially be sizes. The mechanical properties such as the yield strength, flex-
used as a bio-filler for polymers. Researchers evaluated the surface ural strength, modulus, and impact strength of PP/CC25/CC0.07
free energies of the surfaces of clam shell waste (CS) by using inverse hybrid composites were higher than those of single filler compos-
gas chromatography with the Dorris-Gray method and the Schultz ite. The authors used 25 µm needle-like aragonite precipitated cal-
method and also investigated clam shell waste with polypropylene cium carbonates [53]. While making PP composites with CaCO3
(PP) composites and measured the mechanical properties. The re- polymorphs, the morphology of the polymorphs has a significant
sults demonstrated that clam shell waste (CS) significantly enhances impact on the mechanical properties and the thermal properties.
the mechanical properties of PP composites, including the impact Aragonite calcium carbonates (particle size is 57 µm) were ex-
strength, flexural modulus, and flexural strength [58]. Furthermore, tracted from the conch shell of rapana thomsiana and used as a
modified clamshell waste (CS), furfural modified filler (FCS) and filler for epoxy resin. This resin was modified with diglycidyl ether
acid modified filler (ACS), enhances the mechanical properties of bisphenol A (DGEBA), p-aminobenzoic acid (p-ABA), and tri-
(good fracture toughness and stiffness of PP composites) relative ethylbenzylammonium chloride (TEBAC) systems were applied
to commercial calcium carbonate [59-61]. for the evaluation of thermal behavior of composite [65].
2. Aragonite Precipitated Calcium Carbonate Filled Polypro- Recently, aragonite pcc filler was applied for both polypropylene
pylene and polyvinyl alcohol composites [66]. The morphology of aragonite
Aragonite-precipitated calcium carbonate is the second poly- precipitated calcium carbonate is similar to wollastonite (needle-
morph of calcium carbonate and is a thermodynamically metastable like, aspect ratio 20 µm-100 µm). Recently, wollastonite has been
form. Aragonite PCC has a slightly greater average index of refrac- used as a filler for polypropylene, especially for bumpers. In the
tion than calcite. Hence aragonite is expected to have better per- same manner, aragonite PCC is versatile mineral filler for polypro-
formance properties as a filler in the paper and plastics industries pylene composites in the automobile industry due to its needle-like
when compared with calcite [62,63]. Aragonite PCC is often used morphology. Aragonite PCC with PP (mixed with other polymorph
as a filler in the rubber, plastic, paint, pigment, and paper indus- calcite) (Table 6) enhances the mechanical properties of plastics.
tries. In particular, aragonite PP, which is characterized by needle- 4. Vaterite-Precipitated Calcium Carbonate Filled Polypropylene
shaped particles with a very high aspect ratio, increases the bend- Vaterite is the thermodynamically least stable form of calcium
ing and impact strength of rubber and plastics. Aragonite whiskers carbonate and it can be converted into calcite over time. The geo-
are much better than calcite as fillers in polyvinyl or polypropylene logical origin of this bio-mineral is rare. Some researchers [67] re-
(PP) composites, enhancing the tensile strength, impact strength, ported that vaterite is available with carbonate dust grain forma-
glass transition temperature, and decomposition temperature [64]. tion in astrophysical implications. The aforementioned study sug-
Some researchers used mixed composites with different particles gested that vaterite could be a mineral component combined with

Table 6. Summary of aragonite precipitated calcium carbonate as fillers in polypropylene/calcium carbonate composites
CaCO3
Size (µm) Selected resins Remarks Ref.
polymorph
Aragonite 25 µm Polypropylene homopolymers The mechanical properties such as yield strength, flexural strength, 53
(F401, homopolymer) modulus and impact strength of the PP/CC25/CC0.07 composites
was higher than that of single filler composite
Vaterite 100 nm Polypropylene Enhanced tensile strength and Young’s modulus with vaterite composite. 88
The crystallization temperature and crystallinity of the composite
were higher than those of other composite forms

Korean J. Chem. Eng.(Vol. 32, No. 6)

1020 T. Thenepaili et al.

carbonate dust and it is possible to form its polymorphs on plane- compared to other conventional methods.
tary surfaces. A recent study [68] demonstrated the synthesis of The purpose of the present review on calcium carbonate fillers
vaterite in the presence of the organic additive diethylene triamine for polypropylene composites is to realize further economical and
penta acetic acid (DTPA) at higher temperatures with different environmental advantages. Calcium carbonate manufacturing is
morphologies, and in the presence of leucine (L-leucine) [69], N-(2- not complicated. The findings of the present study are quite signif-
hydroxy ethyl) ethylene diamine-N, N, N1-triacetic acid (HEDTA) icant in the polymers industry. Overall, the outlook for calcium
[70], poly(acrylic acid) PAA [71,72], and dyes [73]. Several papers carbonate fillers is bright. With expansion and growing demand
have specified the characteristics of vaterite in terms of thermody- within the automobile industry in coming years, the demand for
namic aspects [74], structure [75], crystal growth, nucleation, and calcium carbonate fillers in the plastics industry (bumpers and other
orientation at a molecular level [76,77]. High aspect ratio single body parts of cars) is expected to grow vastly.
crystal rods of vaterite were obtained within membranes [78].
Synthetically, vaterite is often observed as a transient phase that ACKNOWLEDGEMENTS
converts into calcite via dissolution-precipitation [79], and some
evidence has been presented on the structural variability and the The authors are very grateful to the Korea Institute of Energy
origin of synthetic vaterite with multiple structures [80-82]. In the Technology Evaluation and Planning through the ETI program,
absence of organic additives or membranes synthesis of pure vater- Ministry of Trade, Industry and Energy (Project No. 2013T100100021)
ite is particularly rare. Nevertheless, vaterite has wide advantages in for financial support of this research.
biomedical applications, personal care, advanced biomaterials, as
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