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A study of the effects of pigments and fillers

on the properties of anticorrosive paints


A. Kalendova, D. Veselý and P. Kalenda
Department of Paints and Organic Coatings, University of Pardubice,
Pardubice, Czech Republic

Abstract
Purpose – To investigate the properties of coatings containing various types of fillers from the point of view of their physical-mechanical properties
and anticorrosive properties.
Design/methodology/approach – Research used fillers of different types varying in morphology and/or chemical composition; these were then
compared with selected pigments and zinc phosphate, an anticorrosive pigment. The following parameters were observed for all of the fillers and
pigments: oil absorption, CPVC value, density, extract pH, specific surface, particle size, and water-soluble substances. The morphology of particles was
observed by means of an electron-scanning microscope. The coatings of these fillers and pigments were formulated on an epoxy resin binder basis
cured with a polyamine hardener. The coatings prepared were subjected to the measurement of physical-mechanical properties such as hardness and
deepening resistance, flex resistance, adhesion to steel, and the gloss of the coatings. The coatings containing the fillers and pigments studied
underwent corrosion tests in a condenser chamber and in a salt-spray cabinet.
Findings – The results obtained through the tests allowed the selection of the optimum filler for an epoxy coating with barrier anticorrosive properties.
As per respective findings, some fillers in these coatings of significant thickness can be comparable to their zinc phosphate counterparts.
Research limitations/implications – The anticorrosive properties of the coatings studied can also be tested in paints by means of atmospheric
exposure, for instance, with the aid of a Florida test.
Practical implications – The findings are helpful towards applications in the formulations of anticorrosive coatings of significant thickness that offer
an effective barrier mechanism.
Originality/value – The research presents the results of the properties of a whole range of industrially employed fillers and pigments contained in
paints. Based on this study, the formulation of steel protecting coatings can be optimised.

Keywords Paints, Pigments, Fillers, Oxides, Corrosion protection

Paper type Research paper

Introduction interlayer is inserted between the protected steel base and its
surrounding environment. In addition to the bonding agent,
Corrosion caused by the effects of the atmosphere leads to the the barrier mechanism is also strongly contributed by the
devaluation of all metal materials. The most significant and pigments and fillers used. Positive effects have been observed
economical way to prevent corrosive processes is the in case of employing lamellar particles (Kalendová, 2002).
application of organic coatings created by means of paints.
The purpose of the anticorrosive paints is to protect steel Inhibition protection
structures, machines and other equipment that are prone to This method of surface protection produces a chemical
rusting (Veleva et al., 1999). reaction that retards or completely stops corrosive processes.
Depending on the nature of the anticorrosive protective This method uses anticorrosive pigments as the effective
mechanism, the coatings can be divided into three groups: components of surface protection (Emira, 2005). These
1 barrier-protection coatings; substances reduce the speed of electrochemical processes –
2 inhibition-protection coatings; and they inhibit corrosive reactions. Depending on their working
3 electrochemical-protection coatings. mechanism, they can be either anodic or cathodic.

Barrier protection Electrochemical protection


Barrier protection is a type of metal surface treatment in This protection is based on the principle of the galvanic cell in
which the coating has only mechanical effects. The coating which corrosive processes are transferred onto an auxiliary
creates an inert film of sufficient thickness that is hard to electrode by means of changing the electric field.
permeate for the surrounding environment. In this way, an Electrochemical protection is often used in combination
with barrier protection (Kalendová, 2003).
The current issue and full text archive of this journal is available at Fillers and pigments to be used in paints
www.emeraldinsight.com/0369-9420.htm Fillers are natural or synthetic substances whose primary
purpose is to secure a required volume concentration (PVC)
within a certain system; their secondary purpose is to optimise
Pigment & Resin Technology certain properties or to achieve a system’s specific properties
35/2 (2006) 83– 94
q Emerald Group Publishing Limited [ISSN 0369-9420] (Yang et al., 2005). What makes them different from pigments
[DOI 10.1108/03699420610652377] is usually their poorer hiding power, as the refraction index of

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

fillers is generally less than 1.7. In case of some substances, consist of a mixture of various types of mica and talc
the terms “filler” and “pigment” overlap, because the use of accompanied by other minerals. A relatively recent trend
the fillers in an environment with a low refraction index introduced the use of specular hematite in top paint coats.
secures sufficient hiding power. Quite common is the use of specially modified pyrogenous
The systems in which the fillers are used most often are silicas and hydrophobised silicas as well as rheological
paints, plastics, rubber, paper and construction materials, etc. additives or fillers for the achievement of high hiding power
In these applications, the fillers are designed to modify or whiteness in combination with titanium dioxide. The other
technological and utility properties; i.e. compared to a non- types of special fillers encompass glass lamellar scales
filled product, to improve certain properties, to create specific (Kalendová et al., 2002).
as well as new properties (reflectivity or a certain surface
structure). They should definitely have a favourable cost Experimental
effect; i.e. they should make a product cheaper by sense of the
classical definitions. Both of these properties cannot always be Materials
met simultaneously. The properties of the final products Wollastonite
depend, more or less, on all powder fillers and pigments used Composition ¼ Metha calcium silicate
where every single type of filler has its specific function CaSiO3
(Murray, 2000). Density ¼ 2.65 g cm2 3
The production of fillers for individual, specific applications Oil consumption ¼ 16.3/100 g
is based mainly on their chemical composition and their pH ¼ 8.7
application properties, whereas their availability and price are Water-soluble substances ¼ 1.07 per cent
also of importance (Rodrı́guez et al., 2004). An effective Specific surface
substance content – i.e. the purity of chemical composition – BET-isotherm ¼ 0.8590 m2 g2 1
is another relevant criteria, especially in natural fillers. The Distribution median ¼ 54.33 mm
application properties of the filler depend mainly on its CPVC ¼ 83.8 per cent (Figure 1)
physical-chemical properties. General evaluation of the fillers
assesses especially the distribution of the size of the particles Talc
that affects, amongst others, hiding power, colour hue, gloss, Composition ¼ Magnesium silicate
paint consistency and sedimentation. The value of the specific Mg3(OH)2(Si4O10)
surface of the particles influences the viscosity and the Density ¼ 2.78 g cm2 3
rheological properties of the system, the easy accomplishment Oil consumption ¼ 40.2/100 g
of dispersion, etc. (Fletcher, 2002). pH ¼ 8.7
Water-soluble substances ¼ 0.53 per cent
Function of the fillers in paints Specific surface
Fillers are used in paints in relatively large amounts. BET-isotherm ¼ 6.5475 m2 g2 1
Compounds of excellent chemical resistance are used as Distribution median ¼ 1.69 mm
fillers. Unlike the synthetic fillers, fillers of natural origin CPVC ¼ 45.4 per cent (Figure 2)
claim lower oil consumption, thus yielding more glossy
coatings. Furthermore, it is important that the fillers be easy
to disperse, with a minimum content of inherent moisture Calcite
(less than 0.5 per cent), with a neutral pH extract (7-8.5), and Composition ¼ Calcium carbonate CaCO3
with a water-soluble salt content of up to 1 per cent. The Density ¼ 2.82 g cm2 3
lowest medium size of particles is required in fillers for paint Oil consumption ¼ 25.6/100 g
matting and in anti-sedimentation additives, which is
hundredths to tenths of mm. The production of top paints Figure 1 Micrograph of wollastonite from an electron raster
usually calls for greater-size particles, falling within the orders microscope (magnification 1,000 £ )
of the tenths of micrometers and averaging to 0.2-5 mm. Basic
paints and cements even consist of particles that are up to
scores of mm in size. Fillers of greater size are used for
flushing cements.
Together with the pigments, fillers are primarily designed to
modify pigmentation, to facilitate the preparation of highly
pigmented paints, to achieve certain required properties of
paints and films such as a matt appearance, thixotrophy, and
low tendency to sediment, etc.
The most frequently used fillers in the paints industry are
both traditional natural fillers such as barite and white barite
and/or synthetic barium sulphate – blanc fix. Other widely
used fillers are calcite, dolomite, and chalk as well as talc,
standard kaolin and calcine kaolin, mica, bentonite or
hectorite (Ray and Okamoto, 2003). Less frequent is the
use of slate, vermiculite, huntite and wollastonite, etc. Other
natural fillers include mixed types consisting of several kinds
of mineral at a certain mutual ratio, for instance, they can

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Figure 2 Micrograph of talc from an electron raster microscope Figure 4 Micrograph of natural barite from an electron raster
(magnification 1,000 £ ) microscope (magnification 3,000 £ )

pH ¼ 8.5
Water-soluble substances ¼ 1.02 per cent Barium sulphate
Specific surface Composition ¼ Barium sulphate – synthetic
BET-isotherm ¼ 3.6212 m2 g2 1 BaSO4
Distribution median ¼ 2.88 mm Density ¼ 4.36 g cm2 3
CPVC ¼ 56.3 per cent (Figure 3) Oil consumption ¼ 16.9/100 g
pH ¼ 7.9
Water-soluble substances ¼ 0.18 per cent
Barite Specific surface
Composition ¼ Barium sulphate – natural BET-isotherm ¼ 2.1455 m2 g2 1
BaSO4 Distribution median ¼ 1.87 mm
Density ¼ 4.12 g cm2 3 CPVC ¼ 56.7 per cent (Figure 5)
Oil consumption ¼ 12.1/100 g
pH ¼ 8.5 Muscovite
Water-soluble substances ¼ 0.39 per cent Composition ¼ Aluminium potassium
Specific surface silicate
BET-isotherm ¼ 2.1049 m2 g2 1 KAl2(OH)2(AlSi3O10)
Distribution median ¼ 1.12 mm Density ¼ 2.77 g cm2 3
CPVC ¼ 65.1 per cent (Figure 4)

Figure 3 Micrograph of calcite from an electron raster microscope Figure 5 Micrograph of synthetic barium sulphate from an electron
(magnification 2,000 £ ) raster microscope (magnification 9,000 £ )

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Oil consumption ¼ 50.46/100 g pH ¼ 6.7


pH ¼ 7.4 Water-soluble substances ¼ 1.98 per cent
Water-soluble substances ¼ 0.43 per cent Specific surface
Specific surface BET-isotherm ¼ 5.4546 m2 g2 1
2 21
BET-isotherm ¼ 7.1012 m g Distribution median ¼ 0.544 mm
Distribution median ¼ 9.31 mm CPVC ¼ 40.9 per cent (Figure 9)
CPVC ¼ 39.9 per cent (Figure 6)

Mixed filler Titanium dioxide


Composition ¼ Muscovite(1), chlorite(2), Composition ¼ Titanium dioxide – rutile
silica(3) TiO2
Density ¼ 4.40 g cm2 3
¼ KAl2(OH)2(AlSi3O10)
Oil consumption ¼ 23.98/100 g
¼ Mg5Al(OH)8(AlSi3O10)
pH ¼ 6.0
¼ SiO2
Water-soluble substances ¼ 0.36 per cent
Density ¼ 2.75 g cm2 3
Specific surface:
Oil consumption ¼ 34.08/100 g
BET-isotherm ¼ 14.6416 m2 g2 1
pH ¼ 8.2
Distribution median ¼ 0.445 mm
Water-soluble substances ¼ 0.09 per cent
CPVC ¼ 49.8 per cent (Figure 10)
Specific surface
BET-isotherm ¼ 4.333 m2 g2 1
Distribution median ¼ 6.33 mm Zinc orthophosphate
CPVC ¼ 49.8 per cent (Figure 7) Composition ¼ Zinc orthophosphate
hydrate Zn 3(PO4) 2x H 2O
(x ¼ 2-4)
Zinc oxide Density ¼ 3.50 g cm2 3
Composition ¼ Zinc oxide ZnO Oil consumption ¼ 22.14/100 g
Density ¼ 5.62 g cm2 3 pH ¼ 7.2
Oil consumption ¼ 20.14/100 g Water-soluble substances ¼ 0.66 per cent
pH ¼ 7.2 Specific surface
Water-soluble substances ¼ 0.15 per cent BET-isotherm ¼ 5.2389 m2 g2 1
Specific surface Distribution median ¼ 1.611 mm
BET-isotherm ¼ 7.972 m2 g2 1 CPVC ¼ 54.6 per cent (Figure 11)
Distribution median ¼ 0.554 mm
CPVC ¼ 50.8 per cent (Figure 8)

Binder
Hematite The binder in the paints prepared was epoxy resin CHS-
Composition ¼ Ferric oxide a-Fe2O3 Epoxy 210 £ 75w (Spolchemie a.s., Ústı́ nad Labem, Czech
Density ¼ 5.06 g cm2 3 Republic). This was a solution of the above-referenced epoxy
Oil consumption ¼ 26.67/100 g resin in xylene with an epoxy weight equivalent of
472 g mol2 1, a dry matter of 75 wt per cent, and a viscosity
of 1,550 mPa s.
Polyamine hardener Telalit 160w (Spolchemie a.s., Ústı́
Figure 6 Micrograph of muscovite from an electron raster microscope nad Labem, Czech Republic) with an amine number of
(magnification 5,000 £ ) 123 mg KOH g2 1 was used for hardening. The ratio of
the epoxy resin to the amine hardener remained constant at
10: 4.

Preparation of paints
The paints prepared consisted of an epoxy resin, amine
hardener and a respective filler or pigment. The paints were
formulated so that the powder filler content in a dry film
corresponded to the PVC value of 40 vol. per cent (volume
concentration of the pigment). Each paint always contained
just one type of the fillers and pigments investigated. With
most of the fillers, the selected value of PVC in a paint lies
within 10-15 volumetric per cent based on the value of their
critical pigment volumetric concentration (CPVC). The
paints were obtained through dispersion in a pearl
laboratory mill according to standard procedures.
The paints prepared were applied onto
150 £ 100 £ 0.9 mm steel panels. The paints were made

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Figure 7 Micrograph of the mixed filler from an electron raster microscope (magnification 4,500 £ )

Figure 8 Micrograph of zinc oxide from an electron raster microscope (magnification 5,000 £ )

Figure 9 Micrograph of hematite from an electron raster microscope Figure 10 Micrograph of titanium dioxide from an electron raster
(magnification 10,000 £ ) microscope (magnification 13,000 £ )

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Figure 11 Micrograph of zinc orthophosphate from an electron raster moment of the very first disturbance of coating film cohesion.
microscope (magnification 2,000 £ ) Deepening in millimetre occurring during the first
interference with the coating is taken for a test result.
Table I indicates the properties required in order to secure
overall physical-mechanical resistance and the method of their
evaluation.
Calculation of overall physical-mechanical properties of
coatings:
A1 þ B1 þ C 1
X mech: ¼
3

Accelerated corrosion test in atmosphere containing


SO2 and condensing water vapour
In this test, corrosion processes are accelerated in a special
condenser chamber due to the effects of condensing
humidity and SO2 (0.03 g SO2/dm3 distilled water) at a
temperature of 38 ^ 18C. Samples of epoxy paints were
subjected to a continuous exposure of 1,500 h in the
condenser chamber.

Cycle test in the mist of the 5 per cent neutral solution


of sodium chloride with condensation
by means of applicators with a varying opening so that the This test is based on changing the exposure of samples in the
final dry film was 150 mm thick. mist of NaCl (10 h at a temperature of 358C) created by
spraying the solution of sodium chloride (5 per cent weight of
Gloss measurement sodium chloride) and subsequent exposure to condensing
During a gloss measurement, a beam of light falls on the humidity at a temperature of 408C (1 h) ad the subsequent
tested sample at a certain defined angle and the reflected drying of the samples at 238C (1 h). The epoxy samples of the
beam is measured in a photoelectrical manner. The result is paints were subjected to 1,000 h of exposure.
stated in percentage and is related to a standard material, i.e.
black glass with a defined reflex index of 1.567. Geometry at
858 was employed for measurement.
Table I Scale for calculation of overall physical-mechanical properties
Determination of the hardness of coatings by means of of coatings
a pendulum apparatus (pendulum hardness) Scale for
The test focuses on measuring the time of the attenuation of Bend test Deep-drawing Lattice physical-mechanical
the pendulum that rests on a measured film, contacting it with
on bending test adhesion test properties
two steel balls. The specific units of hardness are percentages
pin (mm) A1 (mm) B1 (degree) C1 evaluation Xmech.
related to the hardness of a glass standard object. The
measurement was carried out by means of a pendulum 4 10 0 100
apparatus, type Persoz. 95
6 8 1 90
Determination of the adhesion of coatings by means of 85
a lattice method (the tape test) 80
The test is accomplished with the aid of a special cutting 8 6 2 75
blade. The lattice is formed by two mutually perpendicular 70
sections. The appearance of the so created lattice is assesses 65
by means of a 0-5 scale. 60
10 4 3 55
50
Determination of the resistance of a coating film during
45
bending (cylindrical mandrel bend test)
40
The test consists of bending a sample over pins of varying
35
diameters. The diameter of the pin diminished gradually until
the coating breaks or chips off its base. The diameter of the 12 2 4 30
specific pin, in millimetre, is the result of the test. 25
20
15
Determination of the resistance of coatings by deep- 10
drawing in an Erichsen’s apparatus (cupping test) 5
This method identifies the depth to which a steel ball can be 16 0 5 0
pressed into a base plate applied with a coating until the

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Methods of evaluating appearance and corrosion degree hardness (22.4 per cent) and the coating with the highest
after exposure in a corrosive environment hardness (63.8 per cent) increased in proportion to the time
The evaluation of samples after their exposure to the above- of coating ageing. The fillers affected the hardness of a film
referenced corrosion tests was completed according to not only by their presence (their composition, texture, etc.)
standards ASTM D 714-87, ASTM D 610, and ASTM D but also by somewhat catalytic effects on the hardening
1654-92. reaction (Figure 12).
The gloss (Table III) of the pigmented coatings indicates the
nature of their surface. Coatings with a higher gloss are
Overall corrosion test evaluation smoother while the coatings with a low gloss are rougher on the
The general evaluation was made by means of a method that surface. The most relevant factors affecting the gloss of the
combined the results obtained in the corrosion tests (Table II) coatings are the degree of pigmentation, the size and specific
and resulted in a single numerical value – total anticorrosion surface of the particles of the filler. These properties of the fillers
efficiency (Xcorr.). can be quantified as one value for each type of filler and
The following relation refers to total anticorrosion
efficiency for corrosion tests in a salt-spray cabinet and in a
Figure 12 Hardness of epoxy coatings containing various fillers from
condenser chamber:
making a coating
2A2 þ B2 þ 2C2
X corr: ¼
5

Results and discussion


The hardness of paint coatings was measured after seven days
from their application. The measurement identified different
hardness between 24 and 42 per cent. The minimum
hardness (24.1 per cent) was identified for a coating
pigmented with hematite while the maximum hardness was
shown by an epoxy coating pigmented with zinc phosphate.
Another measurement of coating hardness took place after
168 of the maturing of the films and it repeated the course of
hardness observed during the initial stages of hardening.
However, the difference between the coating with the lowest

Table II ASTM standards-base evaluation system


Corrosion changes of metal
Degree of blistering A2 Average cut failure (mm) B2 primer (per cent) C2 Anticorrosion efficiency Xcorr.
ASTM D 714-87 Degree ASTM D 1654-92 Degree ASTM D 610-85 Degree Degree
– 100 0 100 0.01 100 100
– 95 – 95 0.1 95 95
– 90 0.0-0.5 90 0.3 90 90
– 85 – 85 – 85 85
– 80 0.5-1.0 80 1 80 80
8F 75 – 75 – 75 75
6F 70 1.0-2.0 70 3 70 70
4F 65 – 65 – 65 65
2F 60 2.0-3.0 60 10 60 60
8M 55 – 55 – 55 55
6M 50 3.0-5.0 50 – 50 50
4M 45 – 45 – 45 45
2M 40 5.0-7.0 40 16 40 40
8MD 35 – 35 – 35 35
6MD 30 7.0-10 30 – 30 30
4MD 25 – 25 – 25 25
2MD 20 10.0-13.0 20 33 20 20
8D 15 – 15 – 15 15
6D 10 13.0-16 10 – 10 10
4D 5 – 5 – 5 5
2D 0 16 0 50 0 0

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Table III Results of physical-mechanical tests of epoxy coatings (film thickness 150 ^ 5 mm)
Adhesion through Flex resistance Deep-drawing Mechanical
Filler Gloss 858 (degree) lattice (degree) (mm) zresistance (mm) properties evaluation (degree)
Wollastonite 44.3 1 12 2.8 53.3
Talc 14.7 0 10 2.6 65.0
Calcite 79.5 2 16 1.2 31.6
Barite-natural 82.4 1 14 2.6 48.3
Barium sulphate – synthetic 57.1 1 14 1.3 41.6
Muscovite 9.2 1 14 0.3 35.0
Mixed filler 65.1 1 16 2.1 40.0
Zinc oxide 76.5 5 18 0.9 5.0
Hematite 75.3 2 8 1.9 60.0
Titanium dioxide 85.3 3 12 2.3 40.0
Zinc phosphate 89.0 5 16 1.5 6.6

numerically expressed as the consumption of oil (bonding agent Looking at the sequence of fillers shown above, it is necessary
absorption) stated in grams of the bonding agent required for to realise that zinc phosphate is an anticorrosion pigment that
the soaking of 100 gm of the filler or the pigment. is used in much lower concentrations in real coatings. Also,
Fillers with smaller particles and a greater value of specific zinc oxide is a pigment that is primarily used in coatings as a
surface are better bonding agents, which affect the surface of white pigment with relatively high hiding power. It is also
the coating much more than fillers with relatively small interesting to compare zinc oxide with titanium dioxide that
particles. This is why the natural filler barite did not reduce gives – even in relatively high concentrations – coatings with
the gloss of the coating as much as synthetic barium sulphate, much better mechanical properties.
which produced coatings with a markedly worse shine. The time of the exposure of epoxy coatings containing the
The non-isometric shape of muscovite particles also fillers and pigments tested in the salt-spray cabinet was
impaired the gloss of the final coating films. Talc-filled 1,000 h. The exposure of the coatings in the condenser
epoxy coatings showed excellent adhesion to the substrate. Its chamber was 1,500 h long. The exposure time was selected in
lamellar structure gave talc great armouring qualities. order to achieve demonstrable differences between individual
Similarly, we can explain the very good adhesion of coatings samples. The thickness of the coatings was always constant
containing muscovite that also has a lamellar structure. and met requirements for a barrier-protecting coating
A similar mechanism applies to mixed fillers with a high (150 ^ 5 mm). The results of both corrosion tests are
muscovite content. The needle-like shape of wollastonite contained in Tables IV and V.
reinforces epoxy resins as well. The regular particles of very The evaluation of the anticorrosion efficiency of paints
tiny size found in barite, synthetic barium sulphate, and doubled the accent put on the surface corrosion of the base
hematite used in an epoxy bond agent result in the very good metal as well as on osmotic blisters. The osmotic blisters – if
adhesion of coating films to a base metal. they occur on a coating – cause the loss of adhesion in the
The relatively high concentration of the tested fillers place of their occurrence. The osmotic blisters offer good
(PVC ¼ 40 of vol. per cent) leads to the substantially poorer conditions for corrosion environments (water, oxygen, and
adhesion of coatings to a base in case of certain pigments/ ions) that penetrate the coating from surface to protected
fillers (TiO2, ZnO, Zn3(PO4)2x H2O). metal. The calculation of anticorrosion efficiency ascribed
The mechanical properties of the coatings containing a relatively less meaning to corrosion in an artificially created
selected bonding agent correspond to the results obtained cut.
through the measurement of adhesion. When measuring the
bending resistance of the coatings, an observed quality is
positively affected mainly by talc and hematite. Whereas, talc,
wollastonite and natural barium sulphate prove to be excellent ‘. . .The best resistance against the occurrence of
fillers for epoxy coatings in case of a deep-drawing resistance osmotic blisters was displayed by epoxy
test. coatings pigmented with wollastonite and a
Calculation and insertion of the values from Table III can mixed filler and talc. . .’
provide a picture of overall mechanical properties, including
adhesions of coatings, impact resistance and deep-drawing
resistance.
The fillers can then be divided into three groups: The best resistance against the occurrence of osmotic blisters
1 Fillers providing coatings with excellent mechanical was displayed by epoxy coatings pigmented with wollastonite
properties (talc, wollastonite, hematite). and a mixed filler and talc.
2 Fillers providing coatings with good mechanical The anticorrosion properties of coatings are also enhanced
properties (natural barite, synthetic barite, fixed filler, by hematite and the anticorrosion pigment of zinc phosphate
titanium dioxide, muscovite, calcite). and zinc oxide.
3 Fillers providing coatings with impaired mechanical High corrosion resistance was provided by films pigmented
properties (zinc phosphate, zinc oxide). with wollastonite, talc and hematite. As per general

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Effects of pigments and fillers on the properties of anticorrosive paints Pigment & Resin Technology
A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Table IV Results of corrosion tests of epoxy coatings after 1,000 h of exposure in a salt-spray cabinet (thickness of films 150 ^ 5 mm)
Blistering Lower corrosion Substrate corrosion Failure in cut
Filler ASTMa (degree) ASTMb (degree) ASTMb (degree) ASTMc (degree)
Wollastonite – 100 – 100 – 100 0 100
Talc 6M 50 1 80 10 60 1-2 70
Calcite 4MD 25 33 20 10 60 1-2 70
Barite – natural 4D 5 33 20 33 20 1-2 70
Barium sulphate – synthetic 4MD 25 33 20 24 30 1-2 70
Muscovite 4M 45 10 60 50 0 2-3 60
Mixed filler – 100 – 100 – 100 2-3 60
Zinc oxide 6F 70 – 100 10 60 1-2 70
Hematite 8F 75 – 100 – 100 1-2 70
Titanium dioxide 4MD 25 – 100 1 80 1-2 70
Zinc phosphate – 100 – 100 – 100 1-2 70
Notes: aASTM D 714-87; bASTM D 610-85; cASTM D 1654-92

Table V Results of corrosion tests of epoxy coatings after 1,500 h of exposure in a condenser SO2 chamber (thickness of films 150 ^ 5 mm)
Blistering Lower corrosion Substrate corrosion Failure in cut
Filler ASTMa (degree) ASTMb (degree) ASTMb (degree) ASTMc (degree)
Wollastonite – 100 – 100 – 100 0-0.5 90
Talc – 100 – 100 10 60 0 100
Calcite 8MD 55 – 100 16 40 0.5-1 80
Barite – natural 6MD 30 – 100 33 20 0.5-1 80
Barium sulphate – synthetic 6D 10 – 100 50 0 0.5-1 80
Muscovite – 100 – 100 10 60 0 100
Mixed filler – 100 – 100 10 60 0.5-1 80
Zinc oxide – 100 – 100 – 100 0.5-1 80
Hematite 8F 75 – 100 3 70 0.5-1 80
Titanium dioxide 8D 15 – 100 10 60 0.5-1 80
Zinc phosphate – 100 – 100 1 80 0-0.5 90
Note: aASTM D 714-87; bASTM D 610-85; cASTMD 1654-92

expectations, the coatings pigmented with zinc phosphate coating film, the following were considered as the most
and zinc oxide were also very resistant against corrosion. effective ones:
Overall corrosion resistance (Figure 13) was also affected
by the degree of paint failure in an artificially created cut. wollastonite . zincphosphate . talc . mixed filler
From this point of view, the most effective appears to be the
ðfillerÞ ðanticorrosion pigmentÞ ðfillerÞ ðfillerÞ
fillers such as wollastonite, talc and an anticorrosion
pigment with inhibiting effects; i.e. zinc phosphate.
Figures 14 and 15 show photographs of steel bases, after
From the point of view of the physical-mechanical properties
the removal of their coatings that have been exposed
of the pigmented epoxy coatings, the following appear to be
in corrosion tests. The figures display obvious corrosion on
the most convenient fillers for achieving the optimal qualities
the surface of the steel sample as well as lower corrosion near
of the coatings:
the cut.
talc . wollastonite . hematite
ðfillerÞ ðfillerÞ ðfillerÞ
Conclusion
Based on overall evaluation of anticorrosion efficiency, i.e. of These fillers show positive effects of a beneficial physical-
the most efficient filler whose properties contribute to the chemical property, the alkaline pH value of the extract and the
overall adhesion-barrier and corrosion inhibition effect of the needle-like shape of particles in case of wollastonite and the

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A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Figure 13 Overall anticorrosion efficiency of epoxy coatings containing various fillers in a condenser SO2 chamber and in a slat-spray cabinet

Figure 14 Photographs of steel bases after removing a pigmented coating exposed in a condenser SO2 chamber for 1,500 h

lamellar shape of particles in case of talc. The mixed filler also typical anticorrosion pigment, serves as a standard agent to
acquires excellent properties in epoxy coatings, which is due to which all of the tested fillers have to be related.
the ideal ratio of lamellar particles to isometric particles. It has This research proved that the application of an epoxy with high
particles of convenient size and contains highly inert particles of chemical and corrosion resistance facilitates the preparation of
silica dioxide. In this study, zinc phosphate, which represents a coatings with high protective capacity provided that a film

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A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

Figure 15 Photographs of steel bases after removing a pigmented coating exposed in a salt-spray cabinet for 1,000 h

thickness of about 150 mm was used. However, the research Ray, S.S. and Okamoto, M. (2003), “Polymer/layered silicate
identified the significant dependence of the protective function of nanocomposites: a review from preparation to processing”,
coatings on the type of filler applied. Progress in Polymer Science, Vol. 28 No. 11, pp. 1539-641.
Rodrı́guez, M.T., Gracenea, J.J., Saura, J.J. and Suay, J.J.
(2004), “The influence of the critical pigment volume
References
concentration (CPVC) on the properties of an epoxy
Emira, H.S. (2005), “A novel approach to the synthesis of a coating. Part II. Anticorrosion and economic properties”,
non-toxic, platy pigment for anticorrosive paints”, Pigment Progress in Organic Coatings, Vol. 50 No. 1, pp. 68-74.
& Resin Technology, Vol. 34 No. 3, pp. 132-8. Veleva, L., Chin, J. and del Amo, B. (1999), “Corrosion
Fletcher, T.E. (2002), “A simple model to describe relationships electrochemical behaviour of epoxy anticorrosive paints
between gloss behaviour, matting agent concentration and the based on zinc molybdenum phosphate and zinc oxide”,
rheology of matted paints and coatings”, Progress in Organic Progress in Organic Coatings, Vol. 36 No. 4, pp. 211-6.
Coatings, Vol. 44 No. 1, pp. 25-36. Yang, L.H., Lin, F.C. and Han, E.H. (2005), “Effects of P/B
Kalendová, A. (2002), “Surface-treated mica based on on the properties of anticorrosive coatings with different
muscovite for anticorrosive coatings”, Pigment & Resin particle size”, Progress in Organic Coatings, Vol. 53 No. 2,
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About the authors
Progress in Organic Coatings, Vol. 46 No. 4, pp. 324-32.
Kalendová, A., Tamchynová, P., Štengl, V. and Šubrt, J. A. Kalendová is currently an Associate
(2002) in Adler, H-J.P. and Potje-Kamloth, K. (Eds), Quo Professor and a guarantor of the research
Vadis-Coatings, Wiley, Weinheim, pp. 367-76. laboratory for pigments and fillers operating in
Murray, H.H. (2000), “Traditional and new applications for the framework of the Institute of Polymeric
kaolin, smectite, and palygorskite: a general overview”, Materials at the University of Pardubice. She
Applied Clay Science, Vol. 17 Nos 5-6, pp. 207-21. graduated in the field of Analytical Chemistry

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A. Kalendova, D. Veselý and P. Kalenda Volume 35 · Number 2 · 2006 · 83 –94

with emphasis on the environment protection in 1987 and anticorrosive coatings. The main areas of his interest as a
gained her PhD at the Institute of Chemical Technology of specialist are anticorrosive pigments, the syntheses thereof,
the University of Pardubice in 1996. She devotes her efforts to the properties in connection with organic coatings.
the research activities in the field of anticorrosive organic
P. Kalenda graduated from the Institute of
coatings and to the research and development of advanced
Chemical Technology at Pardubice in 1985,
non-toxic anticorrosive pigments. Besides syntheses, she also
studied mechanisms of anticorrosion actions of pigments in completed the PhD degree thesis in 1990, and
the coatings. Further, she is engaged in the development of habilitated by defending the appropriate thesis
corrosion methods for evaluation of the organic coatings. Her in 1995. He is a Professor of Technology of
experimental work resulted in 40 publications, Macromolecular Compounds and is presently
overwhelmingly in foreign journals. A. Kalendova is the working at the Institute of Polymeric Materials
corresponding author and can be contacted at: andrea. at the University of Pardubice as the head of the Department
kalendova@upce.cz of Paints and Organic Coatings. He is engaged in research of
D. Veselý graduated in the field of General anticorrosive systems and action-mechanisms thereof and
Inorganic Chemistry at the Institute of further in investigating the chemical resistances of organic
Chemicals Technology of the University of coating binders and formulating the coating compositions. He
Pardubice in 1998. He is currently studying his is an author or co-author of 60 papers published in
PhD at the Institute of Polymeric Materials. A international and national journals. He has also delivered a
great deal of his attention is devoted to the further 110 papers. He has help to apply a whole series of
research activities in the region of the processes and technologies in industry.

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