Calcium Carbonate Fillers

7
Roger Rothon and Chris Paynter

Contents
Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Basic Properties Relevant to Filler Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Ground (Natural) Calcium Carbonates (GCC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
GCC Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
GCC Specification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Polymer Applications of GCCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Thermosets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Precipitated Calcium Carbonates (PCCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
PCC in Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
Environmental Impact and Sustainability of GCC and PCC Production . . . . . . . . . . . . . . . . . . . . . . 158
Future Direction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Cross-References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160

Abstract
Calcium carbonate fillers have ideal properties for many polymer applications
and the world consumption is over ten million tonnes annually. Both natural
(ground (natural) calcium carbonates, GCC) and synthetic forms are in use and
can be derived from abundant and widely occurring natural deposits. The natural

R. Rothon (*)
Rothon Consultants and Manchester Metropolitan University, Guilden Sutton, Chester, UK
e-mail: rogerrothon@btinternet.com
C. Paynter
Imerys Carbonates – Global Research and Development, Carbonates Global Technology Center,
Marietta, GA, USA
e-mail: chris.paynter@imerys.com

# Springer International Publishing Switzerland 2017 149

R. Rothon (ed.), Fillers for Polymer Applications, Polymers and Polymeric Composites:
A Reference Series, DOI 10.1007/978-3-319-28117-9_35
150 R. Rothon and C. Paynter

forms are available with a wide particle-size range (0.5 to over 100 μm), are less
expensive to manufacture, and have the bulk of the market. They are widely used
in thermoplastics, thermosets, and elastomers. The synthetic (precipitated) forms
used in polymer applications fall into the nano-size range (under 100 nm) and are
used where such small particles are beneficial. Their main use is in elastomers and
PVC. Fatty acid surface coatings are often added and there are also specialized
coupling agents available.
Ground (natural) calcium carbonates (GCC) is a critical and functional mineral
for plastics, and there is no doubt that it will continue to be one of the principal
fillers used by the polymer industry. While GCC fillers are long established, they
continue to evolve. Developments in grinding are likely to result in even finer
forms and increased opportunities. Examples of recent developments include an
innovative mineral additive for fibers and nonwovens from Imerys known as
FiberLink ®. FiberLink increases softness, reduces luster, improves opacity, and
improves tensile strength of the fabric/web.

Keywords
Calcium carbonate • Elastomers • Filler • Ground calcium carbonate • Ploymers •
Precipitated calcium carbonate • Thermoplastics • Thermosets

Definition

Calcium carbonate is the chemical compound CaCO3 and occurs widely in nature.
Calcium carbonate fillers are finely divided forms of this chemical and are derived
from various mineral sources. As such they usually contain significant levels of other
materials, especially magnesium carbonate (MgCO3) and dolomite (CaCO3.
MgCO3). They are one of the most widely used fillers in all types of polymer and
can be either natural or synthetic in origin. The natural forms are often referred to by
the acronym GCC (ground (natural) calcium carbonates) and the synthetic ones as
PCC (precipitated calcium carbonate).

Introduction

Calcium carbonate is one of the principal mineral fillers used in polymer applica-
tions, with the world consumption being over ten million tonnes annually. It is an
abundant natural material; with ideal properties for use as a filler in all types of
polymer. It occurs in large, relatively pure, deposits, close to the surface and easily
mined. It is nontoxic, with good color, and also relatively soft and easily milled down
to a fine size.
There are three different crystal modifications of calcium carbonate, as well as
an amorphous form. The crystalline forms are calcite, aragonite, and vaterite,
with calcite being the most commonly used form for filler applications.
7 Calcium Carbonate Fillers 151

Two types of calcium carbonate filler can be recognized, natural and synthetic
(precipitated).

Basic Properties Relevant to Filler Applications

The specific gravity of pure calcite is 2.7, while that of aragonite is slightly higher at
2.8–2.9. Calcite and aragonite are both birefringent with refractive indices suffi-
ciently different from most common polymers for them to give some white pigmen-
tation. The two crystal forms are relatively soft. Calcite has a Mohs hardness of
three, while that of aragonite is slightly higher at 3.5–4. Calcite usually occurs as
rhombohedral crystals, while aragonite frequently occurs in acicular or needlelike
form. Vaterite is a relatively rare crystal form and not met with as a polymer additive.

Ground (Natural) Calcium Carbonates (GCC)

The majority of the filler market is taken by the natural forms of calcium carbonate,
with calcite being the main crystal form encountered. Most natural deposits of
calcium carbonate are largely derived from sediments made up of the accumulation
of minute calcite crystals derived from marine microorganisms. These deposits come
in three distinct forms: chalk, limestone, and marble. All three forms are readily
converted into useful polymer fillers, usually by grinding and some purification
(often referred to as beneficiation). Poor color and the presence of other mineral
phases are the main limitations of many potential deposits. Drying is almost always
necessary to create a useful polymer filler, and simple surface treatments, notably
fatty acids, are frequently also applied to hydrophobize the surface and to make the
finely milled particles dispersible in, and compatible with, particular polymer
systems.
Chalks are the softest and least altered form of the original sediment and still
contain the recognizable remains of the original marine microorganisms, with the
individual calcite crystallites easily distinguished (see Fig. 1). These deposits are

Fig. 1 An SEM image of a

coccolith microfossil from a
UK chalk deposit – each
individual calcite crystallite
making up the spherical body
is around 3 μm in dimension
152 R. Rothon and C. Paynter

Fig. 2 Fine chalk-based filler

formed by breaking apart the
calcite crystallites in a
wet-grinding process

readily ground to release the basic crystals which, being only a few microns in size,
are ideal for most polymer applications without needing to be further broken down
(see Fig. 2). Chalk-derived powders are frequently referred to as whitings.
Limestones have undergone significant densification, as a result of geological
processes. They are thus much more compact, harder to grind to fine size, and with
no recognizable marine organisms present.
Marble is a metamorphic rock and has undergone the severest geological trans-
formation. Marbles vary markedly in color and find many decorative uses in bulk
form. Filler grade marble is usually produced from industrial mines tailored for
industrial mineral applications but can also be sourced from the fine dust from
cutting marble for architectural use – in this case it usually comes from processing
of the whiter grades.

GCC Production

After mining, the main processes are crushing, grinding to reduce particle size,
removal of undesirable impurities (beneficiation), and, where required, coating and
drying. Grinding is carried out in either the dry or wet state. Dry grinding is less
expensive for the coarser grades, but wet grinding becomes more economic at the
finer end, even though the water has to be removed by a combination of filtration and
drying. A variety of grinding aids may be employed and can remain in the final
product. Various beneficiation processes are used, depending on the quality of the
deposit and the applications for the final product. These can include froth flotation,
chemical bleaching, magnetic separation, sedimentation, and classification.
The most widely used surface treatments are fatty acid types, especially those
based on stearic acid (C18) known as stearates (see Rothon 2010). They are usually
applied on the final finished product but can be applied at various stages of the
processing. For example, they may be added during size reduction, as they can act as
grinding aids. The fatty acid treatments are intended to react with the calcium
carbonate surface to produce bound monoacid salts; but this is difficult to achieve
7 Calcium Carbonate Fillers 153

in practice. Recent studies have shown that the treatment can result in the presence of
various other forms of fatty acid, including the full salt and free acid (Khanna and
Xanthos 2010). In some applications even small amounts of these other forms can be
detrimental, and where this is so, the coating process has to be carefully controlled to
minimize them.

GCC Specification

The main properties, with usual ranges given for commercial grades of GCC, are
presented in Table 1.

Polymer Applications of GCCs

GCC is an ideal, low cost, and easily used filler for many polymer applications. The
low cost makes it possible to reduce raw material costs by replacing polymer by
GCC, although the savings are not as great as it appears possible on first sight, as the
higher specific gravity means that 2.5–3 times as much weight of filler is needed to
replace polymer on a volumetric basis, and additional cost is often incurred to
incorporate and efficiently disperse the particulate GCC.

Table 1 The main properties usually given for GCC fillers and the normal ranges encountered
Property Normal range Comments
Calcium carbonate 90–98 Best products are >96%. Main impurity is magnesium
content% carbonate
Color brightness 70–95 Importance varies according to application
(e.g., ISO R 457) 1.4–7.0 Good color usually attracts a premium
Yellowness
Particle size 0.5–10.0 The two values give an indication of the width of the
Average <10–100 particle-size distribution. Premium products are at the
(D50, microns) bottom end of the size range and the lower end of the “top-
Top cut cut” range. Some applications require a narrow
(D98, microns) distribution, while others require special distributions to
maximize packing
Specific surface area <1–10
(BET, m 2.g 1)
Oil absorption 15–25 This is an important indication of how much of the filler
(ml/100 g) can be incorporated into the polymer. The lower the oil
absorption, the higher the obtainable loading, which is
important where the filler is being used for pure cost
reduction
Powder density 400–900
(aerated) kg.m 3 800–1,700
(tapped) kg.m 3
154 R. Rothon and C. Paynter

Table 2 Estimated use of GCC fillers by the various polymer types and application (world basis)
% of total
Polymer type tonnage Comments
Thermosets 20 Mainly used in uncoated form
Unsaturated polyester resin formulations
(Sheet molding and bulk molding compounds)
Elastomers 20 Widespread use, especially in carpet backing
Mixture of coated and uncoated
Thermoplastics 60 Flexible PVC is the largest market (especially cable insulation and
flooring). Significant use also in rigid PVC (pipes and extrusions),
polypropylene (garden furniture, household appliances, and
automotive), and polyethylene (microporous film and cables).
Again, both coated and uncoated forms are used

The world market for GCCs in polymer applications is over ten million tonnes,
and Table 2 gives the estimated breakdown by polymer type and application.
The more important applications of GCC in the different polymer types are
outlined below.

Thermoplastics

GCC is widely used in thermoplastics, especially PVC and polyolefins. The biggest
use is in plasticized PVC applications, especially in cable insulation, carpet backing,
and floor tiles. Cost is a major consideration together with low oil absorption.
Plasticized PVC can accept high levels of filler and loadings can be as high as
400 parts per hundred of resin (phr) in some applications. In cable insulation, very
low levels of conductive soluble impurities are required.
Rigid PVC (unplasticized or u-PVC) can only accept lower filler loadings, and
GCC levels are typically 2–40 phr, although low-grade products containing up to
100 phr can be found. The main applications are in extrusions, such as pipes, cable
management systems, vinyl sidings and window, and other building profiles.
Processing of u-PVC is a complex operation. Due to the thermal instability of
PVC, the polymer granules need to be fused together rather than melted as is the case
with other thermoplastics, and the speed and completeness of this process are
critical. Fillers have a significant effect on this fusion process, and this has to be
taken into account. The finer particle sizes usually give the most rapid and complete
fusion. Fatty acid treatments also help. The finer particle-size grades also give the
best physical and mechanical properties in u-PVC, especially when fatty acid is
coated. Although u-PVC used to be a significant market for the very fine PCC,
advances in milling technologies have led to this largely being displaced by GCC
today.
GCCs are the main filler used in polypropylene (PP) compounds. Apart from cost,
their main role is to increase stiffness without too much detriment to other properties,
especially impact resistance. Higher aspect ratio fillers, such as talc and wollastonite,
7 Calcium Carbonate Fillers 155

Fig. 3 An SEM image of a

breathable film showing the
polymer debonding from the
GCC surface

are more effective at increasing stiffness, but have a greater detrimental effect on
impact strength. Fatty acid coating aids processing and properties and is frequently
used. The finer grades also give the best mechanical properties.
Microporous film is a special application for GCC in both PP and polyethylene
(PE). The GCC particles are used to generate the micropores by debonding from the
film when it is being stretched during production (see Fig. 3). In order to achieve the
best results, a fatty acid-coated GCC with 1–2 μm particle size and a narrow particle-
size distribution are required, and special grades are offered for this application. One
of the major uses for microporous film is in disposable diapers.

Thermosets

GCC is also widely used in bulk thermoset applications, especially in unsaturated

polyester (UPR) formulations such as sheet and bulk molding compounds. In many
of these applications, it is used in conjunction with glass fiber. The main require-
ments of the GCCs used in these applications are low cost, low moisture content,
absence of troublesome impurities, and low oil absorption. The latter is particularly
important as high filler loadings are usually required. UPR polymers contain high
levels of polar groups which can interact strongly with the filler, and so surface
treatments of the fatty acid type are not usually used, although the formulation may
contain dispersants to reduce viscosity.

Elastomers

GCC is also frequently used in commodity elastomer applications, especially carpet

backing based on lattices such as styrene butadiene rubber (SBR) and in general
156 R. Rothon and C. Paynter

Table 3 Effect of calcium carbonate particle size (as indicated by specific surface area) on the
properties of a sulfur-cured SBR compound
With 100 phr of With 100 phr of PCC (stearate
GCC GCC coated)
Property of cured specific surface area specific surface area specific surface area
elastomer 1.8 m 2g 1 6.0 m 2g 1 20.5 m 2g 1
Hardness (IRHD) 59 59 65
Tensile strength MPa 4.4 11.7 13.2
Modulus at 300% MPa 2.1 2.4 1.7
Elongation at break% 610 730 784
Tear strength 30 46 74
(BS) N/2 mm

rubber goods (GRG). It is little used in tire applications. Most elastomers are
inherently weak unfilled and require small particle-size fillers to provide sufficient
strength for most applications. Because of their size, only the finest GCCs are able to
provide much reinforcement, and so they are commonly used in conjunction with
more reinforcing fillers, such as carbon black or precipitated silica. Both uncoated
and fatty acid-coated GCCs are used, and fatty acids are also frequently present in
the formulation and able to coat the filler surface “in situ.” The effect of calcium
carbonate particle size on reinforcement of an SBR rubber is illustrated in Table 3. It
can be seen how reducing the particle size of the GCC brings its performance closer
to that of PCC, although the magnitude of the effect varies with the property being
measured.

Precipitated Calcium Carbonates (PCCs)

Although generally more expensive to carry out than grinding of the natural min-
erals, precipitation has several advantages. The main ones are:

Ability to produce various crystal forms and shapes

Ability to carry out significant levels of purification
Ability to produce very small particles, which would be prohibitively expensive
using the GCC approach

Today these advantages, especially manipulation of crystal form, size, and shape,
are most utilized in making products for paper applications, which is outside of the
scope of this article. Even so, significant amounts of PCC are used in polymers,
although this is declining, as enhanced grinding methods allow GCCs to compete
more successfully.
Several processes can be used to precipitate calcium carbonate from solution. The
two main ones are double decomposition and carbonation.
Double decomposition is carried out by adding a solution of sodium carbonate to
one of a calcium salt, most commonly calcium chloride. This precipitates calcium
7 Calcium Carbonate Fillers 157

carbonate, leaving sodium chloride in the solution. The calcium carbonate is sepa-
rated by filtration, washing, and drying. The washing has to be very thorough to
remove the coproduct salt. Optionally a surface treatment can be applied to the
product at some stage.
While originally quite popular, the double decomposition process has largely
been superseded by carbonation. In this process, a form of natural calcium carbonate,
usually limestone, is heated (calcined) to decompose it, producing lime (calcium
oxide) and carbon dioxide. The lime is reacted with water (slaked) to produce a
slurry of calcium hydroxide (milk of lime) which is then reacted (carbonated) with
the carbon dioxide driven off in the first-stage calcination. This leads to the precip-
itation of calcium carbonate. As with the double decomposition, the product is
separated by filtration and drying; but unlike the double decomposition, there is no
need for washing as no coproduct salt is involved. This is a very significant
advantage. A surface treatment is nearly always applied for polymer applications
and is usually done before filtration, as it aids both this stage and the drying stage. By
far the most common surface treatment used is a fatty acid, although carboxylated
polymers can be used for specialist elastomer applications.
The crystal form, size, and shape can be manipulated by careful attention to the
precipitation conditions in both processes, and the patent literature abounds with
examples of different forms including vaterite. Polymer grade PCCs are almost
exclusively produced as calcite, with crystals in the range 0.02–0.1 μm. A typical
elastomer grade PCC is shown in Fig. 4.

Fig. 4 A typical precipitated

calcium carbonate used in
polymers
158 R. Rothon and C. Paynter

Table 4 An illustration of Property Uncoated MPBD coated

the effectiveness of MPBD
Hardness IRHD 56 57
coating on the performance
of PCC in a sulfur-cured Tensile strength MPa 7.8 10.8
EPDM elastomer (PCC Modulus at 300% MPa 2.0 3.8
20 m2g 1 at 150 phr Elongation at break% 600 685
loading) Tear strength Nmm 1 14.2 25.5

PCC is relatively expensive to produce compared to GCCs and, as is illustrated in

Table 3, is frequently under threat from improved forms of the latter.

PCC in Polymers

PCC has a long and varied history in polymer applications, having frequently been
forced to reinvent itself, due to improvements in the production of GCCs. It was first
introduced as a filler for use in elastomers, especially natural rubber, a market which
has now largely been lost. Next it became very important in PVC, especially rigid
(unplasticized) PVC, where its small size aids fusion and processing and can give
improvements in important properties such as impact resistance, but again this
market has been significantly eroded by competition from GCC. Most recently,
PCC has found significant application as a rheology control agent in sealant appli-
cations, especially in plasticized PVC, where it competes with products such as
fumed silicas. So far this market has resisted erosion by GCC.
The reinforcing ability of PCC in elastomers has already been exemplified and
compared with GCCs in Table 3. While it is significantly better than all but the finest
GCCs, it still falls well short of many other fillers. Part of the reason for this is the
poor interaction between the filler and the elastomer. This low interaction is partly
due to the fatty acid coatings usually employed. The weak interaction is common for
many minerals and usually remedied by the use of a coupling agent able to react with
both the filler surface and the polymer and so couple the two together. Organosilanes
are the state-of-the-art products for this, but unfortunately they are not effective with
calcium carbonates. In the 1980s an effective coupling agent system was discovered
(maleinized polybutadiene, MPBD), the effectiveness of which is exemplified in
Table 4. Despite this breakthrough the use of PCC remains a relatively expensive
option compared to other white fillers, and so MPBD-coated PCCs only occupy a
niche position today.

Environmental Impact and Sustainability of GCC and PCC

Production

While it is inescapable that calcium carbonate filler production depletes resources

and consumes energy, it must be looked at in a more holistic way. The fillers replace
polymers in the final products, and life cycle analysis has shown that in most cases
7 Calcium Carbonate Fillers 159

production of the filler is less detrimental to the environment than that of the polymer
it is replacing.

Future Direction

Ground (natural) calcium carbonates (GCC) is a critical and functional mineral for
plastics, and there is no doubt that it will continue to be one of the principal fillers
used by the polymer industry. Developments in grinding are likely to result in even
finer forms and increased opportunities. As an example, it has recently expanded into
a new market, fibers and nonwovens, and this opens up a large potential market in
polyolefins. Imerys has engineered an innovative mineral additive for fibers and
nonwovens based on GCC known as FiberLink ®. This new technology is incorpo-
rated into the polymer during extrusion and is dispersed in the fiber. It can be added
directly to powdered polymer or as a masterbatch with pelletized resins for fiber,
spunlace, spunmelt (SMS), and meltblown applications. FiberLink increases soft-
ness, reduces luster, improves opacity, and improves tensile strength of the fabric/
web. For example, in diaper and hygiene products, adding FiberLink to the
spunbond layers of SMS increases the strength in core wrap and leg cuffs. In
addition to the optical and mechanical property benefits, FiberLink enables faster
throughput or reduced processing temperatures leading to increased productivity or
energy savings. An image of a polypropylene nonwoven fiber containing a
FibreLink surface-treated GCC is given in Fig. 5.
The picture for PCC is less clear. While it will remain a major filler in paper
applications, where the ability to manipulate shape and crystal form and the possi-
bility to introduce satellite production installations utilizing the waste CO2 from the
papermaking process protect it from encroachment by GCC to some extent, the use
in polymers is expected to remain relatively minor.

Fig. 5 Polypropylene
nonwoven fibers containing a
surface-treated GCC
160 R. Rothon and C. Paynter

Cross-References

▶ Particulate Fillers, Selection, and Use in Polymer Composites

▶ Surface Modifiers for Use with Particulate Fillers

References
Khanna YP, Xanthos M (2010) Calcium carbonate, Chapter 16. In: Xanthos M (ed) Functional
fillers for plastics, 2nd edn. Wiley-VCH, Weinheim, pp 291–306
Rothon RN (2010) Functional polymers and other modifiers, Chapter 6. In: Xanthos M
(ed) Functional fillers for plastics, 2nd edn. Wiley-VCH, Weinheim, pp 115–140