Precipitated Calcium Carbonate

Precipitated Calcium Carbonate (PCC) is known as purified, refined or synthetic calcium

carbonate. It has the same chemical formula as other types of calcium carbonate, such
as limestone, marble and chalk: CaCO3. The calcium, carbon and oxygen atoms can
arrange themselves in three different ways, to form three different calcium carbonate
minerals. The most common arrangement for both precipitated and ground calcium
carbonates is the hexagonal form known as calcite. A number of different calcite crystal
forms are possible: Scalenohedral, Rhombohedral and Prismatic. Less common is
Aragonite, which has a discrete or clustered needle orthorhombic crystal structure.
Rare and generally unstable is the Vaterite calcium carbonate mineral.

Features of Precipitated Calcium Carbonate (PCC)

Precipitated calcium carbonate (PCC) by definition is a synthetic chemical material, and

the main features that cause it to be useful in paper are derived from its synthetic
nature. The ability to reproducibly manufacture PCC made to a particular size, shape or
other specifications is called crystal engineering. The combination of chemical synthesis
and crystal engineering allows for five distinct characteristics of the product to be
tailored to meet customer needs.

1. Shape, or more specifically, morphology. Put simply, morphology is shape in 3-

dimensions, which can be plates or cubes or any of several distinct shapes that
provide various functionality in paper. Scalenohedral PCC, by virtue of the size of
its individual crystallites, is exceptionally efficient at scattering light and lends
itself well to applications where high opacity and brightness are required.
Prismatic or barrel-shaped PCC is generally least disruptive to interfiber bonding
in the sheet. Other morphologies are useful when sheet bulk, porosity or some
other property is paramount.

2. Size. Smaller particles usually scatter light more efficiently, while larger particles
usually provide better sheet bulk. Only a synthetic process like precipitation is
capable of producing a particular shape in a particular size. For papermakers,
this allows balancing the important properties of the sheet in a way that natural
pigments cannot.

3. Size Distribution. The average size of PCC particles is important, but so is the
distribution of those sizes. Particles that are distributed over a narrow range of
sizes are useful in obtaining maximum bulk. Particles that exhibit broad size
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 distributions tend to pack well and thus interfere less with interfiber bonding and
sheet strength. Intermediate sizes, or blending of different morphologies of
different sizes, allow tailoring of performance properties that cannot be
accomplished with other pigments.

4. Surface Area. Though specific surface area, expressed as m²/g, is somewhat

dependent on particle size, it can also, within limits, be varied independently of
other factors. This is usually less important for paper filled or coated with PCC,
but can be very important for other materials, such as filled plastics.

5. Surface Chemistry. PCC is a “clean” material that is largely free of impurities.

When freshly made, the particles usually carry a slightly positive charge called
the zeta potential that can affect PCC's bonding to the paper fibers. However, by
using selected chemical agents, this charge can be increased, or neutralized and
made negative, making PCC particularly flexible in this regard. PCC is unreactive
toward most optical brightening agents (OBAs) used in the paper industry, and
this causes OBA to be more effective when used in conjunction with PCC, which
in turn lowers the manufacturer’s overall cost of production. PCC is also very
compatible with a variety of dispersants and other chemical agents, which makes
it useful in both paper and non-paper applications.

Aside from these five degrees of freedom, PCC, as a synthetic material, exhibits
brightness, whiteness and chemical purity. These features, along with the five degress
of freedom make PCC the calcium carbonate of choice in papermaking operations
throughout the world. And, papermakers continue to find ways of leveraging the unique
properties of this material.

Precipitated Calcium Carbonate (PCC) v/s Ground Calcium Carbonate (GCC)

In chemical composition, GCC & PCC are the same. PCC is purer than the limestone
from which it is made, and is lower in silica and lead.

PCC’s shape and size are different from that of ground calcium carbonate (GCC).
Under high magnification, GCC is seen to be irregularly Rhombohedral in shape. The
PCC crystal shape depends on the product, and the particles are more uniform and
regular.

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The distribution of particle sizes in a GCC is much broader than for a PCC of the same
size—that is, there are many more large particles and many more small particles than in
a PCC, and the size of the largest of the particles (the "top size") is much greater for a
GCC than for a PCC. The lower top size of a PCC gives better impact resistance in
plastics than with a GCC. The narrower particle size distribution allows the generation of
high oil absorptions, useful in certain applications.

These differences can be quickly seen in these photos of a PCC and a GCC of the
same median particle size, 0.7 microns.

Precipitated Calcium Carbonate (PCC) Manufacturing Process

The manufacturing of PCC using limestone as raw material consists of four steps viz.

1. Calcination.

2. Hydrolisation

3. Carbonation

4. Drying & Packing.

1. Calcination:

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 • High purity limestone lumps and boulders are properly sized. If required they are
washed with water to remove any foreign matter adhering to the surface and then
charged into the vertical kiln by means of an electric hoist & mechanical winch.
The fire is maintained in the kiln by burning producer gas.
• At 1850° F temperature, the limestone (Calcium Carbonate, CaCO3) is Calcined
in the kiln to form lime (CaO) and carbon dioxide gas (CO2). The carbon dioxide
can be captured for reuse.

CaCO3 + Heat CaO + CO2

2. Hydrolisation:

• Discharged lime from the kiln is hydrolyzed in a Slaker under agitation. The
hydrolyzed slurry under slow agitation is diluted to desired density. This is than
transferred to lime lime slurry preparation tanks through a vibratory screen for
eliminating grits.
• Hydrolyzed lime slurry is diluted, heated or cooled depending upon the grade of
precipitated calcium carbonate to be made.

3. Carbonation

• The measured hydrolyzed Lime slurry is pumped to agitated reaction vessel

(Carbonator) in batches. The cleaned and cooled flue gas from lime kiln is blown
to the reaction vessels in which a batch of lime slurry is taken and kept under
agitation. With the carbonation of lime slurry under strictly controlled conditions
reaction start which is exothermic in nature. The reaction gets completed when
the carbonation temperature indicates a dropping trend. The slurry thereafter is
drawn into a receiving tank equipped wit an agitator from where it is pumped into
settling tanks through a vibratory screen so that grits are eliminated. After settling
of the thick slurry and agitated and allowed to settle again. In this process the
PCC is washed off the water soluble alkalinity and also the slurry is ultimately
thickened to appropriate concentration for drying.

Ca(OH)2 + CO2 CaCO3 + H2O

4. Drying & Packing.

The thickened slurry is pumped to a feed tank from where it is directly fed to film
dryer where steam at a pressure of 40-50 psig is used as the drying medium.

The dryer drum picks up a film of PCC slurry from the slurry feed through at one end
and the material gets dried up by the time drum rotates to the other end where

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 material falls directly in a dry material screw conveyor which is continuously runnig &
the power is taken to blending and final sieving system for final packing.

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 Products and Their application
The different shapes allow PCC to act as a functional additive in sealants, adhesives,
plastics, rubber, inks, paper, pharmaceuticals, nutritional supplements and many other
demanding applications. A formulator can choose a shape, and the physical properties
that result from that shape, that gives the best performance in the end use.

In the PCC process, products can be made with very small sizes, with high surface
areas, high oil absorptions, and/or with different powder bulk densities— from ultra-
low to super-high powder densities.

The type of calcium carbonate used by various Indian industries, are namely activated
and precipitated calcium carbonate. The activated type is produced in one grade only,
whereas PCC is produced mainly in three grades such as light, medium and heavy.

All the three grades of PCC are same as far as chemical analysis (Purity) is concerned
physical characteristics are much different as shown in the specification of product in
later chapter.

As such there is no present or possible competition from the substitute product in the
long run. To be more specific it should be discussed sector wise.

PLASTIC INDUSTRY:

The selected grades of PCC are used by most of the plastic compounds. Calcium
Carbonate is used as the most popular filler for PVC compounds. It imparts more
brightness and binding power than the other fillers. PCC is fast replacing all other fillers
for polyesters compression moulding compound, epoxy compound, polyethylene and
polyolefin compound, phenolic compound and polyurethenene foams.

TOOTHPASTE AND DENTIFICE:

PCC possess special surface properties namely its capacity to form stable dispersion in
glycerin water mixture to have a mild and controllable detergent action on the tooth and
above all, to chemically inert and physically harmless to tooth surface. It has been well
established that PCC has an abrasive action on tooth structure. This industry uses
heavy grade PCC.

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CIGERATTE TISSUE PAPERS AND OTHER TISSUE PAPERS:

Medium grade is commonly used as filler in the manufacture of cigarette tissue papers.
The selected particle size of PCC gives to this paper a good white appearance and
helps to promote uniform burning of the paper.

COSMETIC

PCC is now a recognized ingredient of face powder. It renders remarkably smooth and
free flowing properties with high covering power and absorbency adhesiveness and slip.
This industry uses light grade PCC

RUBBER INDUSTRY

There are three grades of calcium carbonate commonly used in the rubber industry and
are classified in three categories:-

1. Dense grade lower the cost of compound.

2. Medium grades: general are semi-reinforcing in nature.
3. Ultrafine grades are specially coated for improved dispensability and thus
help improving the physical properties.

PAINT INDUSTRY

Most paint grades are generally of the coarse particle size as the large size tends to
promote low sheen and film flatness.

Their low oil absorption and low water demand permit formulating at higher pigment
volume levels. The special resin coated grades improve the in enamels to maintain
gloss, improve pigment suspension and reduce pigment flooding, and streaking.

PRINTING INK INDUSTRY

This industry uses medium/heavy grade PCC as transparent pigment.

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HYGENE PRODUCTS

Basically all detergent use PCC to provide bay to their product because of its specific
properties. Till date this is cheapest and best raw material for this sector.

PHARACEUTICAL AND HEALTH PRODUCT

Most of the pharmaceutical use PCC for neutralization of midacidic preparations and
also removal of some impurities with the substitute Cation. Generally light grade PCC is
used.

In comparison to other calcium carbonate is rich and suitable for human consumption
natural source of calcium lactate etc, PCC is the cheapest and best source. Even US
food and drug Administration which has got stringent standards world over has
approved use of PCC in Antacids, tonics, Multivitamins, Health food such as HORLICS
etc. Recently some grades have been developed by reputed manufacture suitable for
ingectables.

Apart of all these sectors PCC and ACC are widely used in Pan Masala, Gutka, Dags
foods, Cattle feeds etc.

MARKET APPRAISAL & DEMAND POTENTIAL

The demand estimation for Precipitated grades of Calcium Carbonate has been
established utilizing the relevant information from DGTD on the Planning Commission.
Consumption pattern by different industries has been established based on the market
survey; the demand is more established on the basis of market appraisal by personal
discussion, business contact and data from CMIE.

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