PIGMENTS FOR COATING

Dr. Surendra P. Singh

Ideal pigment
Chemically stabile and
low solubility in water
High reflectance at all
wavelengths brightness and
whiteness
Free from impurities
Appropriate particle size
and particle size
distribution
High refractive index good opacity
Low binder demand

Good flow properties as

an aqueous suspension
Mixes easily with water
(dispersability)
Good glossing
properties
Compatibility with other
coating components
Low density
Non-abrasive
Low water absorption
Cheap

Classification of pigments
Main pigments: major fraction of the pigment part
Special pigments: similar to main pigments, but with
limited applications
Additional pigments: minor fraction of the pigments - as
a rule of thumb, < 10%.
Main pigments

Kaolins, Ground calcium carbonates

(GCC), Talcs

Special pigment

Gypsum, Barium sulfate

Additional
pigments

Precipitated calcium carbonates (PCC),

Calcined kaolins, Plastic pigments,
Alumina trihydrates, Titanium dioxides

Particle size and size distribution

In practice, dp = a few m
Customary to express as percentage of particles smaller
than 2 m rather than average particle size.
For "normal" sized pigments, this figure is around 80%.
For "fine" pigments, it is over 90% and, for "coarse"
pigments, less than 70%.
Particle size influences paper smoothness, gloss, ink
absorption etc a specific particle size is desired for
each application.
A high amount of fines can influence binder demand, ink
absorption, ink setting, and ink density.

Particle shape
The basic particle shapes are:
Spherical or cubic, most isometric
Rod-like or needle-like
Platy.

Real shapes are often complicated

By mixing pigments with different particle shapes
in favorable proportions, the porosity and
bulkiness of the coating layer can be increased.
It is quite common to mix kaolin and ground
calcium carbonate.
The particle shape depends on the crystalline
structure of the mineral, which in turn depends
on the chemical composition.

Light Scattering
For most effective scattering, the particle diameter
should be roughly one half of the wavelength of the light
to be scattered. If the particles are too small, the light
waves pass the particles without bending. If the particles
are too large, scattering of light by diffraction is
ineffective due to fewer particles per unit weight.
If the refractive indices of a medium and a particle are
the same, no scattering of light occurs.
The refractive indexes of kaolin clay, talc, gypsum, and
calcium carbonate are nearly the same. The differences
in opacity between pigments are due to the structure of
the coating and not to the pigment material itself.

Hardness and Abrasivity

Hardness impacts the abrasivity of the pigment slurry or coating color.

Moh's scale of hardness: 1: Talc, 2: Rock salt or gypsum, 3: Calcite, 4: Fluorite,

5: Apatite, 6: Feldspar, 7: Quartz, 8: Topaz, 9: Corundum and 10: Diamond.

Besides hardness, abrasivity depends on the amount and size of the impurities.

Particle size and distribution also have effect on abrasivity

Kaolin and talc have relatively low abrasivity even when the amount of impurities
is high, because these minerals are soft and platy and not sharpedged. GCC is
harder and more abrasive than talc and clay.

PCC can be produced having a very low amount of impurities. Kaolin usually
contains a higher impurity content than the carbonate. If kaolin contains a high
quartz content, it can be very abrasive. Among TiO2 pigments, anatase grades
are regarded as less abrasive than rutile grades and chloride pigments more
abrasive than their sulfate equivalents.

Coating color rheology

Coating color rheology depends largely on the rheology of the pigment(s)

used. However, the presence of additives such as binders, co-binders,
water, and retention aids will modify the flow characteristics, particularly if
there are chemical interactions between the various components.
The size, size distribution, specific surface area, surface chemistry, and
shape of the particles affect the viscosity of the pigment slurry.
Generally, low viscosity at relatively high solid content can be maintained if
the particle size is big, the size distribution is wide, and particle shape is
roundish.
In general, the dilatancy (shear thickening) of the coating color is observed
at lower rate of shear when the particles are platier. Due to rheology
limitations linked to lamellarity, current coating talc slurries can only reach
solids content of 65%.
Aggregation of pigment particles, e.g., by calcination of clay, to form a
relatively narrow size distribution of larger particles also increases viscosity.

Density
Low density pigments are preferred
because they will result in thicker and
more voluminous coatings for the same
coat weight. TiO2 pigments have higher
specific gravity than most other coating
pigments; 3.9 for anatase and 4.2 for
rutile, while it is 2.6 for clay and 2.7-2.8 for
calcium carbonate. Gypsum has 10%-15%
lower density than that of kaolin and
calcium carbonate.

KAOLIN
Kaolin is one of the most widely occurring
minerals. Kaolinite, the principal
constituent of kaolin is a layered
aluminosilicate having the chemical
formula: AI4Si4O10(OH)8

Kaolins
a. Kaolin stack
b. English kaolin
c. North American
kaolin
d. Brazilian kaolin from
Yari area
e. Brazilian kaolin from
Capim
f. Calcined kaolin

Physical properties of English coating kaolins

Type
High Bright Ultrafine
Ultrafine
High Bright Fine
Fine (SPS)
Medium
Rotogravure 1
Rotogravure 2

Brightness
ISO
88.0
86.5
87.5
85.5
83.5
83.0
79.8

Percent < Slurry solids

2m
(wl.%*)
92
92
80
66.5
80
66.5
65
66.0
65
62.5
53
-

* Solids at which slurries are typically supplied

Physical properties of typical North American

coating kaolins.
Brightness
GE**

Percent <
2m

Slurry solids
(wl.%*)

NO.1 (ultrafine)

90-92

95-100

70

NO.1

90-92

90-94

70

NO.2

90-92

80-86

70

NO.1 (ultrafine)

86-88

94-98

70

NO.1

86-88

90-94

70

NO.2

85-87

78-84

70

NO.3

85-86

73-75

70

Fine Particle

87-89

96-98

69.5

Regular Particle

87-89

96-98

67.5

Coarse Particle

84-86

45-55

63

High-brightness

Regular brightness

Delaminated

* Solids at which slurries are typically supplied.

Shape of clay particles

Kaolin particles are platy (pseudo-hexagonal ).
Average aspect ratios can vary between 10:1
and 80:1. Secondary kaolins from the Georgia
deposit tend to be somewhat less platy (aspect
ratios: 6:1 - 20:1) than English kaolins.
Brazilian kaolins from the Capim area have a
very low amount of fine particles below 0.2 m.
The deposit at the Yari River shows the finest
grades at particles below 2 m.

Calcined, structured, and engineered

kaolins

Kaolins can be aggregated by either thermal or

chemical means. The aim is twofold:
1. Increase in light-scattering: Particles smaller than
0.3 m do not scatter light. Aggregation of ultrafines
into larger particles enhance light scatter
2. The intra-particle pores formed by aggregation are
capable of absorbing printing inks besides
scattering light improve strike-through.

As an alternative to aggregation, the particle

size distribution can be "engineered" to
maximize the number of particles in the
optimum particle size range for light scatter with few coarse or ultra fine particles.

Thermal aggregation
Heating to about 550C-1100C using large
multiple hearth or rotary kilns
Dehydroxylates the kaolin and converts it to a
noncrystalline aluminum silicate sintering ultrafine
particles into aggregates with open but rigid
structure.
The end products normally have very steep size
distributions; typically coating grades have most
particles in the size range 1 to 5 m.
Calcined clays have different rheological properties
from conventional hydrous clays and slurry solids
are generally limited to a maximum of about 50 %
by weight.

Chemical structuring of clay

Aggregating through chemical routes - normally
involving the use either of polymers or of
precipitation reactions to form an insoluble
binder.
Increased scattering coefficient resulting from a
more optimized particle size distribution does
lead to improved optical properties.
Aggregates tend to be somewhat weaker than
calcined clays.
Less abrasive than calcined kaolin
Worse rheology than standard hydrous clays

GROUND CALCIUM CARBONATE

Natural CaCO3 occurs mainly as the mineral calcite in
various rock forms: chalk, limestone, and marble. All
consist of individual rhombohedral calcite crystals.
Chalk: Loosely layered sedimentary rock of biogenic
origin. Age: about 80-110 million years.
Limestone: Stronger layered sedimentary rock of
biogenic origin. The crystal size is between chalk and
marble. Age: about 110-150 million years.
Marble: Metamorphic carbonate rock formed through
tectonic changes (recrystallization) of limestone. Age:
about 300-500 million years.

Attributes of ground calcium carbonate.

Refractive index
Mohs' hardness
Density (g/cm3)
pH of a 10% suspension
Solubility
Particle-size
Brightness

1.48 - 1.66
3
2.6 - 2.8
About 9
Dissolves under acidic
conditions
40- 98% < 2 m
80-96%

Product characteristics of GCC

GCC is preferred to improve the rheological behavior, to
increase the brightness of the paper, and to reduce costs.
Because of the dense packing, the binder level is lower
(compared with clays) even for the extremely fine calcium
carbonates.
Thus, the important reasons for using ground CaCO3 as a
coating pigment are:
Favorable rheological properties
High coating solids
Better runnability (coater)
Energy savings (coater) - Lower binder demand
High brightness
Better optical brightener efficiency
Good print qualities and high print gloss.

PCC
High brightness, whiteness, light scattering, and
bulking effect - good fiber coverage, adjustable
ink setting properties - good printability, and low
blistering tendency.
The improved printability occurs because we
can select the proper particle size, size
distribution, and shape to obtain the desired
particle packing and pore-size distribution within
the coating layer.
In practice, this is accomplished by producing
specific morphologies via controlled synthesis.

Simplified PCC process

1. Calcination: CaCO3 + energy CaO + CO2
2. Slaking: CaO + H2O Ca(OH)2 + energy
Screening easily removes impurities from the limestone deposit
since the impurities are much larger than the calcium hydroxide
particles. For this reason, commercial PCC pigments typically have
CaCO3 contents higher than 97%: The remainder is MgCO3 and
other residues
3. Carbonation: Ca(OH)2 + CO2 CaCO3 + H2O + energy
The usual sources of CO2 are stack gas of a power plant, recovery
kiln, or lime kiln. In this process step, we can control the particle
size, particle size distribution, and particle shape. Also, surface
properties of the calcium carbonate particles can be changed if so
needed.

Particle shape
PCC can be obtained as aragonite's
needle-like particle form (high aspect ratio)
or calcite form.
Aragonite is beneficial in paper coating good fiber coverage and loose coating
layer packing with these needles.
Prismatic calcite, which has a lower aspect
ratio than aragonite, can be used to adjust
other paper properties, e.g., paper gloss.

PCC pigment

Aragonitic

Prismatic

Physical properties of the major PCC coating pigments.

Kaolin
86

Talc
85

GCC
93

PCC
95

3.5

3.0

1.0

0.8

3.0
0.7
6
67-72

6.0
2.0
5.0
67-70

2.0
0.8
11
74-78

0.8-3.0
0.4-2.0
4-11
71-75

Specific gravity

2.65

2.71

2.71

2.71-2.83

Refraction index

1.551.57

1.551.60

1.491.66

1.49-1.67

ISO -brightness (%)

b* -value (%) [Ratio of
yellowness to blueness
90% < (m)
Av particle size (m)
Sp surface area (m2/g)
Slurry solids (%)

Note: Kaolin clay, GCC, and talc have rather typical property values;
whereas, PCC has a range values according to the different PCC grades.

Coating applications of PCC

Fine PCC (0.3-0.4 m) is the best choice in high glossing double- or
triple-coated papers.
Coarser PCC (0.6-0.8 m) recommended for precoating - to open
the structure more light-scattering voids. With this open structure,
water retention can be a concern and it may be necessary to
compensate by adding some long chain length CMC or synthetic
thickener to the coating color.
With the narrow particle size PCC, it is possible to produce matte
papers having good smoothness, low paper gloss, high printed
gloss, and sufficient ink setting, which is a combination of properties
known to be very difficult to produce.
PCC with high aspect ratio and narrow particle size distribution
mounts more rheological challenges than roundish and wide particle
size distribution pigments like GCC. Yet PCC has lower viscosity
than delaminated clay at the same solid content.