Vol. 7(12), pp.

410-417, December, 2013

DOI: 10.5897/AJPAC2013.0530
African Journal of Pure and Applied
ISSN 1996 - 0840 ©2013 Academic Journals Chemistry
http://www.academicjournals.org/AJPAC

Review

Potentials of Nigerian calcined kaolin as paint pigment

Alabi F. M.* and Omojola. M. O.
Raw Materials Research and Development Council PMB 232, Garki Abuja, Nigeria.
Accepted 21 November 2013

Pigment is one of the main components in paint formulation which is dominated with the use of
titanium dioxide, due primarily to three important physical characteristics; which are high refractive
index, high opacity and chemical inertness. However, due to increasing demand of this important
pigment and the attendant increase in price, it has become imperative to develop cheaper alternative
source with similar properties. One such alternative is calcined kaolin. Knowing fully that not all kaolin
deposits can be calcined to meet the peculiar requirements, this paper therefore highlights the
potentials of some Nigeria kaolin deposits that can be calcined and utilized as alternatives to titanium
dioxide in paint formulation. The paper also highlights the other pigments used in the coating industry,
their advantages, disadvantages and their national and international market trends.

Key words: Pigments, calcined kaolin, titanium dioxide, refractive index, opacity.

INTRODUCTION

Pigment is one of the essential components of paint and oxides, mixed metal oxide and chrome oxide or organic
it serves three main functions which include the optical e.g Black, Bright yellow, Green, Orange, Violet, Magenta;
function of providing colour, opacity and gloss; a (2) Extender pigments, and
protective function with regard to the surface underneath (3) Anti-corrosive and special function pigments.
the paint and the binder which can be destroyed by UV;
and a reinforcing function for the paint itself helping the Inorganic pigments are of mineral origin and are usually
binder to stick. Pigments usually have a particle size of metal oxides. Many metal oxides are found naturally
about 0.5 to 5 µms in standard paints but can be as small such as red and yellow iron oxides. However, most are
as 0.01 µms in the case of some bright organic pigment, now made synthetically to get the cleanest colour. The
a size that enables them to refract light (Ghosh et al., advantages and disadvantages of some common
1990; Murray, 2007; Clark, 2013). A variety of natural inorganic pigments used in paint formulation are
and synthetic pigments are used in paints, providing a presented in Table 1.
complete spectrum of colours and finishes.
Reaction 1. 4ZnO +2CrO3 +K2Cr2O7 +H2O K2CrO4 +3ZnCrO4Zn(OH)2

Classification of pigments Reaction 2. 4Fe +2H2O +3O2 2Fe2O3H2O (spongy mass)

Reaction 3. 2Cr6+ + 2Fe +6OH- 2Cr3+ +Fe2O3 (hard, protective coating) + 3H2O
Pigments can be classified into three main groups: Reaction 4. ZnSO4 + BaS BaSO4(s) + ZnS(s)

(1) Inorganic e.g Titanium dioxide, red and yellow iron Organic pigments are based on the chemical element

*Corresponding author. E-mail: alabi_fortune@yahoo.co.uk.

 Alabi and Omojola 411

Table 1. Some common inorganic pigments.

Type Production Advantages Disadvantages Colour(s)

High strength, good colour, light and weather
Carbon black Decomposition of carbonaceous matter Thickens paint Black
resistant
High strength, high opacity, cheap, good UV Forms radicals that degrade the
Titanium dioxide Synthesised White
resistance binder
Usually mined although can be Yellow, red, brown,
Iron oxides Light and weather resistant, unreactive Cannot produce clean shades
synthesised black
Corrosion formed by reaction (2) is inhibited
Zinc chromates Synthesised according to reaction (1) Thickens paint Yellow
according to reaction (3)
Azurite Kaolin, Na2CO3, sulphur and carbon
Rich colours Fades on contact with acid Blue
Na7Al6Si4O24S2 heated together above 800°C
Light, weather, alkali and acid resistant;
Chromium oxides Doesn’t give clear colours Green, blue
thermally stable
Reacting cadmium salts with sodium Heat and light resistant, clear pigment, high Expensive, poor weather Greenish yellow to
Cadmium sulphides
sulphide opacity resistance red to Bordeaux
Lithopone
Pure tints when mixed with organics,
ZnS mixed with Synthesised according to reaction (4) Poor weather resistance white
unreactive, easily wetted
BaSO4
Source: (Clark, 2013).

carbon. Most organic pigments are not naturally cheap way of reducing the cost of a can of paint. worldwide to find anti-corrosive pigments which
occurring and are made from petroleum by- These mineral are usually produced bymining. are as effective as red lead. Anti-corrosive
products. Organic pigments are the brightly Table 3 shows the advantages and disadvantages pigments for iron and steel commonly in use
coloured ones used for clean colours red, yellow, of some common extender pigments. Anti- include zinc chromate, zinc phosphate and zinc
bright green and blue, purple and magenta. They corrosive pigments are a very important area of molybdate and barium metaborate, although
sprung into prominence in the last 10 to 20 years study. Steel requires the greatest protection alternatives to chromates are being sought as
due to the awareness of the dangers of lead in the against corrosion and the development of they are toxic and environmentally hazardous
older bright red and yellow lead chromate type pigments to inhibit the corrosion of steel has (Resene, 2013). Special purpose pigments such
pigments and the advancing technology in occupied chemists for many years. The anti- as copper can be used in anti-fouling paints for
manufacturing and chemical engineering in the corrosive pigment which has been used for many ships. Another area for specialty pigments is in
organic pigment industry. Some advantages and years is red lead, Pb3O4. In combination with intumescent coatings. These pigments break
disadvantages of organic pigments are highlighted linseed oil, red lead has in the past been the down when heated and initiate chemical reactions
in Table 2. Extender pigments are usually standard anti-corrosive primer for iron and steel. that eventually results in the formation of a thick
naturally occurring minerals such as clay, mica, Unfortunately, red lead is toxic and much research skeleton of carbon about 50 to 100 times the
talc and limestone. They are often used as a has been carried out and is still being carried out original paint thickness (Resene, 2013). This
412 Afr. J. Pure Appl. Chem.

Table 2. Advantages and disadvantages of organic pigments.

Advantages Disadvantages
They are available in bright vivid colours to match all
They are very expensive
shades of the rainbow
They have greater tinting strength and cleaned toned Very difficult to get clean reds and yellows with good opacity and good
except black exterior light fastness
Pigments are generally low in density and not prone to
They are very difficult to grind into paint millbases
settling out
Organic pigments often have a very high oil absorption or demand for
binder which results in paint with poor opacity
They have low density and may tend to float to top of paint
Some organic pigment absorbs UV light thereby
preventing it from damaging the binder Very small particle size of 0.01 to 0.1 µms. This makes handling in
the factory difficult as spilling just a few grams can contaminate a
large area
They are often not heat stable
Source: (Clark, 2013).

Table 3. Some common extender pigments.

Type Advantage Disadvantage Colour(s)

Mica Chemical and solar resistant Poor adherent to surface and rapid Transparent
settling leading to inhomogeneity in
aqueous paint
Barytes Wear resistant It appears darker when wet with less Colourless, white, light shades
covering power than after drying of blue, yellow, grey and brown
Calcium carbonate Helps flatten the gloss of semi- Does not contribute much in film White
gloss and low sheen paints. integrity and its chemistry makes it
Usually a very cheap pigment subject to acid attack. High ionic
content that adversely affects paint
stability
Talc Assists titanium dioxide It leads to high viscosity Pale green, white, grey and
dispersion and improves sanding colourless
Silica Good flattening agent and wear High viscosity and less adherent to White
resistant. It gives extra hardness surface
to paint
Clay Helps to prevent settling and Usually has coarse particle and low white
increases bulk density of paint hiding power
Source: (Clark, 2013).

skeleton forms a physical barrier, which save the titanium dioxide as paint pigment is desirable. One such
substrate from burning for long enough for people to alternative is calcined kaolin with its physical and
escape from a fire. Other special pigments are the non- chemical properties compare favourably with those of
leafing aluminium flake pigments and the special effect, titanium dioxide.
iridescent, pearl afflair pigments used in automotive With regard to the environmental impact, the process
finishes. for production of calcined kaolin does not have any
Of all the various pigments, titanium dioxide is regarded negative effect on the environment and requires less
as the most important. Therefore, as a result of capital investment. On the other hand, the production
increasing demand for titanium dioxide, its price has been process for titanium dioxide using the sulphate method
increasing. Titanium dioxide price rose about 35% in has great negative impact on the environment. It also
2011 and is expected to increase at an average annual requires huge capital investment which probably
rate of about 7% for the near future (Huntsman, 2013). translates to its high cost. Also, the eco-friendly chloride
For this reason, the search for an alternative to substitute process is associated with negative economic factors and
 Alabi and Omojola 413

Table 4. Trade summary of various pigments imported into Nigeria between 2008 and 2011.

Value (N)
Type of pigment
2008 2009 2010 2011
Dye 130,311,757 215,000,783 394,199,941 183,461,121
Organic pigments 185,679,432 237,346,081 487,522,555 458,957,593
Metallic pigments 229,026,522 422,056,834 520,309,509 406,210,647
Inorganic pigment (others) 2,222,759,520 6,818,715,214 2,783,398,429 4,525,305,180
Titanium dioxide 822,075,763 1,883,243,736 4,141,382,689 3,388,338,441
Inorganic carbon 6,988,250 246,858,511 2,947,283 1,942,292
Organic black 49,917,883 78,000,447 43,559,436 47,202,583
Total 3,646,759,127 9,901,221,606 8,373,319,842 9,011,417,857
Source: (NFTS, 2008, 2009, 2010 and 2011).

requires much more capital investment than the sulphate rose to $2,500/MT in 2012. The price rose about 11% in
process. 2011(IHS Chemical, 2013).
Similarly, China is also the largest single consumer of
organic pigment in the World and the fastest growing
INTERNATIONAL MARKET TREND OF PIGMENTS national market. The specialty pigment market is also
growing at approximately 7% per year and is estimated to
The global market for pigment has been forecast to reach be worth $2.1billion in 2013 (IHS Chemical, 2013).
9.0million MT valued at $24.2billion by 2015 (Joses,
2011). This increase in market growth is expected to be
fuelled by growth in the paints, coatings, ink and MARKET TREND OF PIGMENTS IN NIGERIA
construction industries. Asian pacific represents the
largest regional market for pigments worldwide both in The paint industry in Nigeria is highly import dependant
terms of volume and value. Europe trails behind Asia as over 70% of the raw materials for the sector are
while US constitute the next largest market. China is the imported. The major reason for non-availability of local
largest and fastest growing market for pigment across the raw materials for the sector is absence of the
globe. Petrochemical industry in the country which is expected
Segment wise, inorganic pigments represent the to produce most of the chemicals used in the industry.
largest segment in volume and value terms, closely Also, it is because most beneficiating plants that process
followed by organic pigment and then the specialty locally available non-metallic raw materials for the
pigment representing a promising market due to their industry are operating below installed capacity due to the
eco-friendly characteristics. Amongst the inorganic obsolete technology and equipment still being used.
pigment, titanium dioxide is the most important pigment in Furthermore, there is a low level of R&D in the
the world accounting for approximately 70% of total processing of metallic, non-metallic and agro-based raw
volume (IHS Chemical, 2013). About 96% of titanium materials needed in the sector (PMA, 2010). According to
produced is used as feedstock for titanium dioxide National Bureau of Statistics, Nigeria spent about N3.6b
pigment (Huntsman, 2013). Currently, the major on the importation of paint pigment in 2008. This figure
producing feedstock regions are Australia, South Africa, rose to N 9.9b (NFTS, 2008, 2009, 2010 and 2011).
Canada and India, with Australia being the largest Table 4 shows a breakdown of various paint pigment
producer. imported for 2008, 2009, 2010 and 2011.
The major consumers of titanium dioxide for paint
production is China where consumption doubled from
2004 to 2011 and is still expected to grow at an average POTENTIALS OF USING CALCINED KAOLIN AS
annual rate of 7% in the next decade (IHS Chemical, PIGMENT
2013). Western European and Japanese consumption of
titanium dioxide has remained stagnant whereas North Pigments for paint formulations are submicron particles
American consumption declined in the last decade due to which must possess certain properties such as good
decrease in coatings consumption caused by poor opacifying strength (commonly called hiding power) and
construction and manufacturing markets. There has also brightness. Other important features are excellent
been a steady price increase of titanium dioxide. The resistance to chemical attack, good thermal stability and
price of titanium dioxide was about $500/MT in 2010 and resistance to UV degradation.
414 Afr. J. Pure Appl. Chem.

Unit cell of Rutile TiO2 unit cell of calcined kaolin (mullite)

Figure 1. Chemical structures of TiO2 and calcined kaolin.

Pigments from mineral sources offer opacity and resultant physical and chemical properties that determine
brightness because they have the ability to scatter light. its industrial application (Murray and Lyon, 1956).
The degree to which minerals scatter light depends on Calcination increases the silica and alumina content of
their intrinsic index of refraction and also on the structure kaolin. The silica content determines the texture of the
they form in the coating (Imerys, 2013). Titanium dioxide paint while aluminium content and particle size the
has high refractive index, strong absorption in the UV brightness and opacity of the paint. Absence of iron oxide
region of light spectrum and strong reflectance in the improves the brightness (Duval et al., 2008; Raw
visible spectrum thereby giving it a very high light Materials Research and Development Council (RMRDC)
scattering properties which, when combined with its 2004). The ideal composition of silica and alumina in
particle size creates an effective pigment for brightness calcined kaolin for paint pigment is of the range of 45 to
and opacity (Imerys, 2013) (Figure 1). 47% and 37 to 39% respectively, while that of iron oxide
Calcined kaolin also exhibit properties similar to content should be less than 2% (American, 2013). Silica
titanium dioxide and therefore can be used as an content higher than the above range increases the
alternative pigment to titanium dioxide. These properties abrasion of the calcined kaolin pigment. Reduction of the
include brightness and opacity. Calcined kaolin effectively silica content to the required level can be carried out by
scatters light due to its porous structure, hence when light controlled leaching of the silica from the calcined kaolin
encounters it, some of the light gets reflected off the using caustic solution which dissolves the silica out of the
planar surfaces, a portion of the light enters the structure calcined kaolin (Engelhard, 2013). The removal of the
and these rays upon reflection encounter other crystals in iron oxide can be carried out using hydrosulphite, high
close proximity. This light then undergoes multiple intensity magnetic separation and the froth flotation
internal reflections and diffractions giving excellent optical technique. The brightness, opacity or both of calcined
scatter (Imerys, 2013). The similarities in properties can kaolin can be increased by increasing the fineness of the
be attributed to the similarity in their chemical structure as kaolin feed supplied to the calciner (Engelhard, 2013).
shown in Figure 1. According to the structure, the rutile Also there is a correlation between brightness and
TiO2 form has TiO6 octahedrons that form columns by degree of crystal perfection of kaolin. Poorly crystalline
sharing two edges. Titanium has six oxygen nearest kaolin is expected to contain more impurities on their
neighbours and oxygen has three titanium nearest surfaces because of more available valence charges
neighbours. Adjacent columns are linked through sharing (Murray and Lyon, 1956). Tables 5 and 6 show the
corners of other octahedra. Likewise, the mullite structure chemical composition and physical properties of kaolin
consists of chains of distorted edge-sharing Al-O suitable for pigment, while Table 7 is a comparison of the
octahedral at the corners and centre of each unit cell. properties of titanium dioxide and calcined kaolin useful
These chains are further cross-linked by Si-O and Al-O in paint formulation. Table 7 shows a comparison of the
corner-sharing tetrahedra. properties of titanium dioxide and calcined kaolin useful
in paint formulation.

EFFECT OF CALCINATION ON THE

PHYSICOCHEMICAL PROPERTIES OF KAOLIN NIGERIAN KAOLIN DEPOSITS WITH POTENTIALS AS
PAINT PIGMENT
For kaolin to be suitable for pigment, several empirical
tests are run on the kaolin to determine its suitability. The Nigeria has a huge reserve of kaolin with an estimated
mineralogical composition and fundamental structure of reserve of about 3 billion metric tonnes scattered in
the kaolin are very important since they control the different parts of the country (Edomwonyi-Out et al.,
 Alabi and Omojola 415

Table 5. Chemical composition of kaolin suitable for calcined

kaolin as pigment.

Component Weight percent

SiO2 45-47
Al2O3 37-39
Fe2O3 0.3-1.9
TiO2 0.4-0.8
CaO Trace
MgO Trace
Na2O 0.2-0.3
K2O 0.1-0.3
Loss on ignition 14.45-14.50
Source: (Glass, 1957; Ghosh et al., 1990; Mesbah et al.,
2011; Murray, 2007).

Table 6. Physical properties of kaolin suitable for paint formulation.

Property Raw kaolin Calcined kaolin

Oil absorption 44 43
pH 5.6 6.95
-1 -1
Conductivity (Ω cm ) 111.3 34.32
Bulk density (gcm-1) 0.64 0.48
Relative density 2.55 2.71
Refractive index 1.56 1.55
Reflectance 82.7 90.1
Source: (Ghosh et al., 1990).

2013). There are at least 45 known deposits of kaolin in temperatures. It loses its (OH) lattice water between 500
Nigeria. There is no state in the country without at least to 600°C (Quinfu et al., 2002; Schieltz and Soliman,
one deposit (Badmus and Olatinsu, 2009). 1964). The loss of lattice water breaks up the regular
The market for kaolin in Nigeria is large, sustainable periodicity in the kaolinite structure, along the c-axis
and expanding because of the numerous applications of producing a dehydrated phase known as metakaolin
the product. Also there is an outright ban on the (Schieltz and Soliman, 1964). By further heating,
importation of kaolin into the country in order to stimulate metakaolin transforms to a crystalline phase, indicated by
the growth of the local industry. The major kaolin deposit the first exothermic peak at about 980°C to form primary
in the country and their chemical composition are shown mullite crystalites. Further heating to approximately
in Table 8. It can be observed from the table that Nahuta, 1200°C produces secondary mullite crystalites and this is
Kankara, Onibode, Ifon and Major porter deposits have followed at approximately 1350°C by a third exothermic
the potentials to meet industrial quality as pigment reaction to the formation of beta-cristobalite (Wahl and
because their Alumina, Silica and Iron contents almost Grim, 2012) (Figure 2).
fall within the required range. The chemical composition
of these deposits can be improved to achieve the ideal if Kaolinite 550-600˚C Metakaolin 980 – 1050˚C Mullite 1100-1350˚C Cristoballite
the kaolin undergoes the process of beneficiation and
calcination. Al2O3.2SiO2.2H2O Al2O3.2SiO2 Al2O3.SiO2 SiO2

Mullite being the only stable intermediate phase in the

PHASE CHANGES OF KAOLINITE DURING HEAT Al2O3-SiO2 system, is an important material for both
TREATMENT conventional and high-technology applications (Temuujin
et al., 2000; Titanium and titanium dioxide, 2013). Most
Kaolinite, Al2O32SiO2.2H2O, undergoes some significant pigment grade calcined kaolin is heated to temperature
changes in its structure when heated to higher between 1000 and 1050°C which indicates the mullite
416 Afr. J. Pure Appl. Chem.

Table 7. Comparative properties of Titanium dioxide and calcined kaolin.

Property Titanium dioxide Calcined kaolin

Chemical stability Stable Stable
Crystal structure Tetragonal Triclinic with hexagonal flaky layers
Durability Good Good
Particle size (µm) 0.2-0.3 0.1-1.0 (thickness)
Brightness 95% 92%
Refractive index 2.76 1.56
Source: (Ghosh et al., 1990; Murray, 2007).

Table 8. Chemical composition of major Nigerian kaolin deposits.

Chemical composition (%)

Deposit
SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O SO2 L.O. I Colour
White, light grey and dark
Ozubulu 60 26 5 5 Trace Trace Trace Trace - -
brown
White yellow, pink, grey and
Nahuta 47 32 1.3 2.4 Trace Trace Trace Trace 0.55 12-18
brown
Jagalwa River 50 30 1.4 2.4 Trace Trace Trace trace - - -
Orange, pink, brown, white and
Darazo 51.9 32.9 2.9 - 0.39 0.29 Trace 0.89 0.13 -
grey
Off-white with pink and brown
Kankara 43.3 36.7 0.21 Nil Trace 1.49 Trace 0.7 - 11.10
patches
Onibode 43.1 36.1 3.1 1.9 Trace Trace Trace Trace - 12.65 -
Ifon 48 33.2 0.06 1.72 Trace Trace Trace Trace - - Pink
Okitipupa 50 29 - - - - - - - 10 -
Major porter 45.6 35.2 2.7 - Trace Trace Trace 0.97 - - -
Source: (RMRDC, 2004).

The Kaolinite structure Average structure of mullite

Figure 2. Structural transformation of kaolinite to mullite.

phase (Murray, 2007) (Figure 3).

consideration. The cost of titanium dioxide is about six
times the cost of calcined kaolin products (Murray, 2007).
CONCLUSION The similarities in both the physical and chemical
properties of calcined kaolin and titanium dioxide indicate
In any production process, cost reduction is an important that calcined kaolin could effectively be used as pigment
 Alabi and Omojola 417

Surface
Surface
structure
structure
of calcined
of calcined
kaolinkaolin Surface
Surface
structure
structure
of TiOof
2 TiO2

Figure 3. Structure of Calcined kaolin and TiO2.

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