Progress in Organic Coatings 86 (2015) 147163

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Investigation of the anticorrosion efciency of ferrites Mg1x Znx Fe2 O4

with different particle morphology and chemical composition in
epoxy-ester resin-based coatings
Andrea Kalendov , Petr Rysnek, Katerina Nechvlov
Faculty of Chemical Technology, University of Pardubice, 532 10 Pardubice, Czech Republic

a r t i c l e

i n f o

Article history:
Received 8 November 2013
Received in revised form 24 February 2015
Accepted 8 May 2015
Available online 2 June 2015
Keywords:
Ferrites
Anticorrosion pigment
Paint
Coating material
Epoxy-ester resin
Non-isometric particle

a b s t r a c t
Mixed metal oxides with the ferrospinel structure ZnFe2 O4 , Mg0.2 Zn0.8 Fe2 O4 and MgFe2 O4 were synthesised by the high-temperature solid-phase process. A series of pigments containing the metals
MgZnFe was prepared from 4 different starting iron oxides: viz. goethite (FeOOH), hematite (Fe2 O3 ),
magnetite (FeOFe2 O3 ) and specularite (Fe2 O3 ). The properties of the ferrites as pigments were examined in a solvent-based epoxy-ester resin-based coating material at a pigment volume concentration
PVCferrite = 10%. The anticorrosion efciency of the paints with the ferrites was examined by exposing
panels coated with the paints to atmospheres with SO2 , NaCl, or condensed moisture. Furthermore, the
physico-mechanical properties of paint lms containing the pigments were evaluated by standardised
tests. Ferrites prepared from the needle-shaped FeOOH or lamellar Fe2 O3 emerged as pigments with
the best anticorrosion properties. From the aspect of chemical composition, the paint lms containing
Mg0.2 Zn0.8 Fe2 O4 , i.e. combinations of the cations MgZn, were assessed as the best.
2015 Elsevier B.V. All rights reserved.

1. Introduction
A number of nontoxic anticorrosion pigment types are currently
available for application in coating materials [1,2], with their anticorrosion efciency in the paints being mostly adequate. The ability
of paint to provide anticorrosion protection to metal substrates is
governed by the chemical composition of the anticorrosion pigment, its concentration in the coating material binder [3], and on
the amounts of other pigments present, such as llers and special additives. The protective effect also depends on the method of
metal surface pre-treatment and a number of other factors [4,5].
The majority of available nontoxic pigments provide roughly the
same level of protection; however, the efciency of none of these
are close to that of the toxic chromate pigments [6]. The use of anticorrosion pigments whose particles possess a non-isometric shape
is an interesting approach. Such pigments in paints provide a high
barrier protection, and adhesion of the paint to the substrate is also
improved, meaning that the particles help to slow down corrosion
processes acting on the substrate. If the particles also exhibit active
chemical and corrosion inhibiting effects, the pigments may show
promise for use in anticorrosion protection paints [7].

Corresponding author. Tel.: +420 728994274.

E-mail address: andrea.kalendova@upce.cz (A. Kalendov).
http://dx.doi.org/10.1016/j.porgcoat.2015.05.009
0300-9440/ 2015 Elsevier B.V. All rights reserved.

The synthesis of ferrite-based pigments represents another

promising eld in the development of anticorrosion pigments.
Owing to their structure or chemical composition, ferrites have a
benecial effect of the paints anticorrosion properties and contribute to the stability of the coating system when exposed to
elevated temperatures [8]. Even more efcient than ferrite-type
spinel pigments [9,10], with combinations of 2 cations in the lattice (ZnFe2 O4 ), are Generation II spinel pigments with 3 cations
(Mg1x Znx Fe2 O4 and Ca1x Znx Fe2 O4 ). Their anticorrosion effect
is based their reaction with a suitable binder which produces
organometallic soaps [11]. Among their assets is their alkalinity,
owing to which they are able to neutralise acid binders, thereby
shifting the pH to a range which is less favourable for corrosion
reactions [12]. Their environmental friendliness is also an important aspect.
Spinel-type pigments are substances of crystalline nature whose
properties depend on the properties of the host lattices. The crystal structure of spinel pigments derives from the mineral spinel
(MgAl2 O4 ). Three oxidation state combinations are conceivable for
charge compensation in oxides with the general formula AB2 O4 :
A2+ B2 3+ O4 , A4+ B2 2+ O4 and A6+ B2 1+ O4 ; the anion is largely O2
[13,14]. The factors determining which atom combinations can
form a spinel structure include the formal charge of the cation,
the relative size of the cations [15]. A crystal lattice can be stable only if the ion radii and their ratios (valency and valency ratio,

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A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

concentration proportions of the ions present) do not exceed certain energy and space limits. Admissible radii assume the range
from 0.4 1010 m to 1.03 1010 m. For instance, because of their
radius, the concentration of Ca2+ ions in a spinel lattice cannot
exceed 30% [16]. Among the important properties of oxides possessing the spinel structure is their ability to mix together and form
solid solutions almost without limitation. Spinels of the same type
or different types (such as 2.3 and 4.2) can be combined in this manner. As a result, simple spinels are able to form mixed spinels, which
are also referred to as substitution solid solutions. Combinations of
divalent and trivalent cations are largely present in ferrospinels, i.e.
ferrites with a spinel structure. They can be usually described by the
formula xMea Ob yFe2 O3 , where Me = Mg or Zn. In the simplest case,
where x = y = 1 and a = b = 1, the formula simplies to MeOFe2 O3 ,
which can be written in the simple form MeFe2 O4 .

The starting materials were used to synthesise 3 spinel-type

pigments: ZnFe2 O4 , MgFe2 O4 and Mg0.2 Zn0.8 O4 . In the reaction
pathway, ferric oxide-hydroxide is rst transformed to Fe2 O3 at
180 C200 C (temperature T in reaction (1)), and this intermediate reacts further with the Zn (ZnO) or Mg (MgO) cations (reactions
(2)(4)):
T

2FeOOHFe2 O3 + H2 O

(1)

Fe2 O3 + ZnO ZnFe2 O4

(2)

Fe2 O3 + MgCO3 MgFe2 O4 + CO2

(3)

Fe2 O3 + 0.2MgCO3 + 0.8ZnO Mg0.2 Zn0.8 Fe2 O4 + 0.2CO2

(4)

The above equations were used to calculate the amounts (proportions) of the starting substances with respect to the desired
amount of the resulting pigment (Table 1).

1.1. Goal of the study

Pigments based on mixed metal oxides, or ferritesferrospinels
of the MgZnFe series (Mg1x Znx Fe2 O4 where x = 0. 0.8, and 1)
were synthesised. The spinel lattice structure was chosen owing to
the outstanding properties of ferrites, notably their chemical and
thermal stability, high covering power and insolubility [12,13]. The
quality and relevant properties of the pigments are affected by the
starting substances (oxide, carbonate, sulphate) and by the particle
size, specically surface area and morphology [17]. The synthesis
of ferrites by decomposition of carbonates to oxides leads to the
formation of oxides which are more reactive than those which are
used as the starting materials [18]. Alkaline earth (Ca) carbonates
are also more suitable starting materials for the preparation of pigments because the product cannot be contaminated by residues of
the unreacted starting substances, as is the case, e.g., with sulphates
and chlorides.
The modelling and inuencing of the properties of the nal
product was based on the principle of isomorphous ion substitution in the initial spinel lattice MgAl2 O4 . Targeted selection of
cations forming solid solutions can be employed to modify the
initial properties of the spinel lattice and change or create new
properties, especially those which affect the corrosion-inhibiting
behaviour of the pigment in the coating material binder [19]. Zinc
and magnesium ions were also selected owing to their favourable
properties affecting the structure and alkaline nature of the pigments. Four iron oxide types which differed in colour, structure,
and primary particle shape, viz. goethite, magnetite, hematite and
specularite, were used for the preparation of the spinel-type pigments. The spinel structure was obtained by reacting the oxides
with zinc oxide (ZnO) as the Zn2+ ion source and with magnesium
carbonate (MgCO3 ) as the Mg2+ ion source. Calcination of the pigments was achieved by the high-temperature solid-phase process
giving rise to ZnFe2 O4 , MgFe2 O4 and Mg0.2 Zn0.8 O4 . The aim of this
procedure was to obtain ferrites possessing a high anticorrosion
efciency, which is governed by a number of factors such as pigment particle morphology, acid-base properties, surface properties,
water soluble fraction, and the like.
2. Experimental
2.1. Preparation of the spinel type ferrites
2.1.1. Preparation of the ferrites from FeOOH
The needle-shaped FeOOH served as the source of ferric ions,
and zinc oxide (ZnO) and magnesium carbonate (MgCO3 ) were
the sources of the Zn2+ and Mg2+ . The starting ferric oxidehydroxide (FeOOH) was commercial Bayferrox 920 (Lanxess-Bayer
Leverkusen, Germany), which possesses the goethite structure,
with a mean particle size 0.10.6 m.

2.1.2. Preparation of the ferrites from FeOFe2 O3

Magnetite Fe3 O4 with isometric particles was used as the starting source of ferric ions in this case. Again, ZnO and MgCO3 served
as the sources of the other cations. The starting iron oxide was
commercial Bayferrox 316 (Lanxess-Bayer Leverkusen, Germany),
chemically ferrous-ferric oxide FeOFe2 O3 , with a magnetite structure. The proportions of the starting substances are given in Table 1.
The reactions of the starting substances are described by the following equations:
2Fe3 O4 + 3ZnO + 1/2O2 3ZnFe2 O4

(5)

2Fe3 O4 + 3MgCO3 + 1/2O2 3MgFe2 O4 + 3CO2

(6)

2Fe3 O4 + 0.6MgCO3 + 0.4ZnO + 1/2O2

3Mg0.2 Zn0.8 Fe2 O4 + 0.2CO2

(7)

2.1.3. Preparation of the ferrites from -Fe2 O3

Two iron oxide types possessing identical structures and differing in their colour and, in particular, particle shape were used in
the preparation of the ferrites from ferric oxide. The one iron oxide
type was red Fe2 O3 with an isometric particle shape. The material was commercial Bayferrox 130 M (Lanxess-Bayer Leverkusen,
Table 1
Amounts (weight and molar fractions with respect to the nal product) of the starting substances taken to the synthesis.
Starting material: FeOOH
Pigment

ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4

FeOOH

ZnO

MgCO3

Wt.%

Mol.%

Wt.%

Mol.%

Wt.%

Mol.%

68.59
67.82
68.43

66.6
66.,6
66.6

31.41

25.08

33.3

26.6

32.18
6.49

33.3
6.6

Starting material: Fe3 O4

Pigment

ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4

Fe3 O4

ZnO

MgCO3

Wt.%

Mol.%

Wt.%

Mol.%

Wt.%

Mol.%

65.47
64.68
65.31

40
40
40

34.53

27.56

60

48

35,32
7.13

60
12

Starting materials: -Fe2 O3 , lam. -Fe2 O3

Pigment

ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4

Fe2 O3

ZnO

MgCO3

Wt.%

Mol.%

Wt.%

Mol.%

Wt.%

Mol.%

66.23
65.45
67.37

50
50
50

33.77

26.95

50

40

34.55
5.75

50
10

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

Germany), which is synthetic -Fe2 O3 , with a hematite structure.

The other oxide type was also -Fe2 O3 hematite, but its particles
had a lamellar shape (lam. Fe2 O3 ). The material used was commercial Specularite MIOXSp44, which is natural -Fe2 O3 with a
lamellar particle shape, containing very small amounts of the mica
clinochlore. The two iron oxide types served as the source of Fe3+
ions for the formation of the spinel structure. Again, ZnO and MgCO3
were the other reaction components. The reactions are represented
by Eqs. (2)(4). The starting substance weight proportions are given
in Table 1. The morphology of the particles of the starting iron
oxides is illustrated by Fig. 1.
2.2. Laboratory procedure for the preparation of the pigments
The calculated amounts of the starting materials were weighed
with a precision of 0.01 g, were mixed, and then subjected to dry
homogenisation in an agate mortar for 30 min. The homogeneous
mixtures were transferred to refractory ceramic crucibles made
of sintered corundum and subjected to stepwise calcination in an
electric furnace. The synthesis of ZnFe2 O4 included two calcination
steps. The rst step was conducted at 600 C, with a temperature
ramp of 5 C/min and the holdup time at the maximum temperature
of 2 h. The second calcination step was conducted at 1000 C, with
a temperature ramp of 10 C/min and the holdup time at the maximum temperature of 3 h. In the synthesis of ferrites containing Mg,
i.e. MgFe2 O4 and Mg0.2 Zn0.8 Fe2 O4 , the calcination process encompassed three steps, which were conducted at higher temperatures
because MgO is a more difcult starting point for the formation
of spinels. The rst step was conducted at 1050 C, the temperature ramp was 5 C/min and the holdup time at the maximum

149

temperature was 2 h. In the second step, the calcination temperature was increased to 1150 C, the temperature ramp was kept at
5 C/min, and the holdup time was extended to 2.5 h. In the third
step, the calcination temperature was again increased, to 1180 C,
the temperature ramp was left at 5 C/min, and the holdup time
at the maximum temperature was extended to 3 h. The calcination
temperatures were selected based on previous X-ray analysis.
The pigments obtained by the calcination process were subjected to wet milling in ethanol. The pigment in ethanol was
transferred to a 500 ml zirconium oxide vessel containing milling
balls that were 1 cm in diameter and were made of corundum. The
vessel was placed in a Pulversitte 6 planetary mill and milled at
400 rpm for 1.5 h (ZnFe2 O4 ) or 3.5 h (MgFe2 O4 , Mg0.2 Zn0.8 Fe2 O4 ).
The product was then ltered through a Bchner funnel equipped
with a KA 4 type (Czech product) lter paper for qualitative analysis. The ltration cake was rinsed with 2 litres of distilled water
at 60 C in order to remove water-soluble substances. Finally, the
ltration cake was rinsed with 100 ml of ethanol. The product was
dried at 80 C for 24 h to remove ethanol and at 105 C for another
48 h to remove all moisture.

2.3. Elucidation of the pigment particle structure and morphology

X-ray diffraction spectra were measured on an XPert PRO MPD
1880 X-ray diffractometer (PANanalytical, The Netherlands). The
diffraction data were evaluated by means of the XPert programs
(XPert HighScore Plus Software version 2.1b and XPert Industry Software version 1.1g); the phases were identied using data
from the ICCD PDF2 diffraction database. The pigment surface and

Fig. 1. Morphology of the particles of the starting Fe oxides: (a) goethite (-FeOOH, ferric oxide-hydroxide), BEC detector; (b) magnetite (Fe3 O4 , ferrous-ferric oxide), SEI
detector; (c) hematite (-Fe2 O3 , ferric oxide), SEI detector; (d) specularite (lam -Fe2 O3 ), SEI detector.

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A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

particle shape were examined on a JEOL-JSM 5600 LV scanning

electron microscope (JEOL, Japan) in the secondary electron mode.
2.4. Examination of the physico-chemical properties of the
pigments
A helium AutoPycnometer 1320 (Micromeritics, USA) was used
to determine the pigments specic weight. Linseed oil consumption was measured by the pestle-mortar method [20]. The result of
the measurement, the oil number (in g/100 g), is a necessary quantity for calculation of the CPVC and for the formulation of coating
materials (paints). The pH of aqueous extracts of the pigments was
measured in accordance with ISO 789-9 by preparing 10 wt.% pigment suspensions in redistilled water (pH = 7), measuring their pH
periodically over a period of 30 days, ltering the suspensions off
after that period (i.e. after the pH had reached a constant value), and
measuring the nal pH of the ltrate (pH30 ). A WTW 320 pH meter
(WTW, Germany) was used in conjunction with calibration buffers
(pH 4.01, 7.00. 10.01 and 12 at 25 C) for the measurements. Specic
electric conductivity of aqueous extracts was measured conductometrically in 10% suspensions of the pigments in redistilled water
(specic electric conductivity = 3 S/cm) using a Handylab lF1 conductometer (SCHOTT, Germany) in conjunction with calibration
solutions (conductivity 37 and 1413 S/cm at 25 C). This procedure was based on the ISO 787-14 standard. Measurements were
taken periodically over a period of 30 days, after which the ultimate (steady-state) specic conductivity (30 ) was recorded. The
ltrates of the 10% pigment suspensions obtained in this manner
were used to determine corrosion losses of steel panels submerged
in them [21]. The water-soluble fraction was determined gravimetrically by extraction of the powdered pigment (weighed with
a precision of 0.01 g) in boiling distilled water (W100 ). This pro
cedure was derived from the CSN
EN ISO 787-3 standard [22]. A
MASTERSIZER 2000 particle size analyser was used for determination of the particle size distribution. This measurement is based on
the interaction of electromagnetic radiation with the particles of
the dispersion system. Particle size is represented by the diameter
of the equivalent sphere, i.e. sphere whose laser radiation dispersion patterns are identical with those of the particle in question.
2.5. Assessment of the anticorrosion efciency of the pigments in
the paints
Model solvent-based epoxy-ester resin-based paints were formulated for investigation of the pigments anticorrosion properties.
As model systems, the paints did not contain any other llers or
additives that might appreciably affect the resulting efciency of
the paint. The pigment volume concentration (PVC) in the paints
was invariably 10%.
The binder for the paint formulation was epoxy-ester resin, a
60% solution of a medium molecular weight epoxy resin esteried
with a mixture of fatty acids of dehydrated ricin oil and soy oil
(60% epoxide, 40% conjugated fatty acid), acidity 4.1 mg KOH, density 1.07 g/cm3 viscosity 2.55.0 Pa s, ow time (DIN 53211-4 200)
250 s, commercial name WorleDur D 46. Co-octoate in a fraction
of 0.3 wt.% was used as the siccative.
The paints were prepared by dispersing the powders in the liquid binder in a Dispermat CV pearl mill (WMA GETZMANN GmbH
Verfahrenstechnik, Germany). Bentonite (0.5 g) was added to suppress unwanted sedimentation of the pigment particles.

UK) with a size of 150 mm 100 mm 0.9 mm by means of a boxtype application ruler 200 m slot width, as per ISO 1514. After
the layer had dried, a second layer was applied so that the total
dry lm thickness (DFT) was 95 10 m. The dry lm thickness
was measured with a Minitest 110 magnetic thickness gauge tted with a F16 type probe (Elektrophysik, Germany) in accordance
with ISO 2808. Ten panels were prepared for each paint. A test line
8 cm long and penetrating through to the substrate was cut into
the paint lm in the lower half of each test panel.
The paint lms on the panels were allowed to dry in standard
conditions (20 C 2 C, 50% RH) for 6 weeks in an air-conditioned
laboratory. Paint lms were also prepared on polyethylene sheets,
allowed to dry, peeled off, and cut into pieces 1 mm 1 mm size.
The squares of the unsupported lms were used to prepare 10%
aqueous suspensions of the paint lms in redistilled water.
2.7. Laboratory corrosion tests
Cyclic three-phase corrosion test in atmospheres with condensation of water, with NaCl, and with SO2 was performed. In this
test, the test samples, i.e. steel panels coated with the paints, were
exposed to condensed water at 40 C for 12 h (Phase 1 Stage 1) and

EN ISO 6270 (Phase 1

allowed to dry at 23 C for 12 h, as per CSN
Stage 2). Following exposure for 1152 h, the samples were removed
from the condensation chamber and inserted for 240 h into a test
chamber with a salt mist of 5% NaCl (ISO 7253). This was test Phase
2, which was followed by Phase 3, for which the samples were

placed into a test chamber with SO2 for 240 h, as per CSN
EN ISO
3231. The complete test took 1632 h.
Corrosion test with condensation of water in the presence of SO2
was performed. This test was performed in 24-h 2-stage cycles, as

per CSN
EN ISO 3231. In the rst stage, the samples were exposed
to an environment with condensation of distilled water containing
SO2 (0.2 mg/l) for 8 h. In the second stage, the samples were allowed
to dry at 23 C for 16 h. The rst test panel batch was exposed for
800 h, and the second, for 1600 h. Subsequently, the samples were
evaluated.
Corrosion test in an environment with sprayed solution of NaCl
was performed. This test, which was based on ISO 7253, comprised
three stages. First, the test panels were exposed to the mist of a
neutral 5% NaCl solution at 35 C for 10 h (Stage 1) and then to an
environment with condensation of water at 40 C for 1 h (Stage 1).
Subsequently, the samples were allowed to dry at 23 C (Stage 3)
[19]. The rst test panel batch was evaluated following exposure for
800 h, while the exposure was extended to 1600 h for the second
test panel batch.
2.8. Corrosion test evaluation methods
The corrosion tests were evaluated in accordance with the stan
dards ASTM D 714-87, CSN
ISO 2409, ASTM D 610-85, and ASTM
D 1654-92. The methods were based on a comparison of the paint
lm degradation effects between the sample and the standard. The
following corrosion effects were assessed: formation (=size and frequency of occurrence) of blisters on the lm surface, both across
the paint lm area and near the test cut made in the lm; extent of
substrate metal surface corrosion (corrosion-affected surface area
fraction in %); and propagation (in mm) of corrosion in the vicinity
of the test cut. Adhesion of the paint lm to the substrate (glass
plate) following the corrosion test and subsequent drying for 24 h

was also examined, as per CSN

ISO 2409.

2.6. Preparation of samples for testing the anticorrosion

properties

2.9. Determination of steel weight loss due to corrosion

The test samples were prepared by coating the paints onto steel
panels (deep-drawn cold-rolled steel manufactured by Q-panel,

In this test, steel panels of dened size and known weight

were submerged for 10 days (a) in ltrates of 10 wt.% aqueous

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

suspensions of the powdered pigments and (b) in aqueous extracts

of 10 wt.% suspensions of pieces of the unsupported paint lms containing the pigments tested [23]. In both cases, the suspensions had
been allowed to stand for a period long enough (30 days in this case)

151

for steady-state pH and specic electric conductivity levels to be

established. The observed corrosion weight losses were converted
to relative data (%) with respect to the values in water. The relative
data obtained from the suspensions of the powdered pigments and

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A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

Fig. 2. (a) Results of X-ray diffraction analysis of ZnFe2 O4 (starting substance: FeO(OH)). (b) Results of X-ray diffraction analysis of MgFe2 O4 (starting substance: FeO(OH)). (c)
Results of X-ray diffraction analysis of Mg0.2 Zn0.8 Fe2 O4 (starting substance Starting substance FeO(OH)). (d) Results of X-ray diffraction analysis of ZnFe2 O4 (starting substance
magnetite FeOFe2 O3 ). (e) Results of X-ray diffraction analysis of MgFe2 O4 (starting substance magnetite FeOFe2 O3 ). (f) Results of X-ray diffraction analysis of Mg0.2 Zn0.8 Fe2 O4
(starting substance Starting substance magnetite FeOFe2 O3 ). (g) Results of X-ray diffraction analysis of ZnFe2 O4 (starting substance hematite. -Fe2 O3 )). (h) Fig Results of
X-ray diffraction analysis of MgFe2 O4 (starting substance: hematite -Fe2 O3 ). (i) Results of X-ray diffraction analysis of Mg0.2 Zn0.8 Fe2 O4 (starting substance Starting substance
hematite. -Fe2 O3 ). (j) Results of X-ray diffraction analysis of ZnFe2 O4 (starting substance specularite lam. -Fe2 O3 ). (k) Results of X-ray diffraction analysis of MgFe2 O4
(starting substance: specularite lam. -Fe2 O3 ). (l) Results of X-ray diffraction analysis of Mg0.2 Zn0.8 Fe2 O4 (starting substance Starting substance specularite lam. -Fe2 O3 ).

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

of the unsupported paint lms are denoted Xp and Xf , respectively

[24].
Tests were also performed to examine the paints adhesionbarrier properties. The factors measured included adhesion to the
substrate, hardness, and strength. Because unsupported paint lms
are difcult to prepare, the properties of the paints were measured
directly on metal substrates in accordance with standardised tests.
The tests imitate mechanical stresses in the external environment,
such as an object being dropped onto the surface (impact test) and
deformations caused by bending and elongation (bending test and
cupping test).
Degree of adhesion of the paints was performed by the cross-cut
test (ISO 2409). The lattice pattern was cut into the paint by means
of a special cutting instrument with cutting blades that were 2 mm
apart. The degree of adhesion of the 1 mm 1 mm squares to the
substrate was assessed.
Impact resistance (ISO 6272) measured the maximum height of
free drop of a weight (1000 g) at which the paint lm still resisted
damage. The test was performed by dropping the weight onto both
the adverse and reverse sides of the test panel.
Resistance of the paint lm against cupping was made in an
Erichsen cupping tester (ISO 1520). The objective of this test was to
identify the resistance of the paint lm against on-going deformation of a coated steel panel caused by indentation by a 20 mm steel
ball. The cupping (in mm) giving rise to the rst signs of disturbance
of the paint lm was measured.
Resistance of the coating during bending over a cylindrical mandrel (ISO 1519) provides the largest diameter of the mandrel (in
mm) causing disturbance of the paint lm when the test panel is
bent over it.

EN ISO 24624) was performed on

Pull-off adhesion test (CSN
an Elcometer 106 pull-off adhesion tester (Elcometer, Germany).
First, the paint lm was roughened and degreased, and then a test
roller was glued to it. The adhesive was allowed to dry and then
the roller was attached to the measuring instrument and the pressure acting on the paint lm was slowly increased. The value (in
MPa) measured at the moment at which the lm was pulled off
was recorded.
Reference experiments: for comparison, paints containing the
starting iron pigments and paints containing the non-pigmented
coating materials were also subjected to the same tests.
3. Results and discussion
3.1. Particle morphology and structure of the ferrites
The results of the X-ray diffraction analysis of the pigments synthesised are given in Fig. 2al). Morphology of the pigment particles
synthesised is shown in the SEM photographs in Fig. 3.
The pigments prepared were based on ferrites involving divalent cations: zinc ferrite (ZnFe2 O4 ), (its solid solution with Mg,
Mg0.2 Zn0.8 Fe2 O4 ), and magnesium ferrite (MgFe2 O4 ). A total of 12
ferrites were prepared from 4 different iron oxides differing in composition, i.e. cation combinations (ZnFe, MgFe, and MgZnFe),
and particle shape. The shape of the pigment particles followed
that of the starting iron pigment (Fig. 3). Particles of the ferrites
prepared from FeOOH were needle-shaped; this shape was most
pronounced in ZnFe2 O4 (Fig. 3). The ferrites prepared from specularite consisted of lamellar particles, which were smaller than those
of the starting substance owing to the efcient milling. The ferrites prepared from magnetite and hematite had isometric nodular
particles. The cubic structure of ZnFe2 O4 was conrmed in all samples irrespective of the starting Fe oxide. The ferrites ZnFe2 O4 were
free from the starting substances, except for the pigment prepared
from specularite, in which small amounts of the unreacted starting
ZnO and Fe2 O3 were present. Magnesium ferrite (MgFe2 O4 ) was

153

cubic. Where magnesium ferrite had been prepared from specularite, magnetite or hematite, the product contained a small amount
of Fe2 O3 as a minority phase. The Mg0.2 Zn0.8 Fe2 O4 solid solution
prepared from specularite, goethite or magnetite was free from
minority phases. The synthesis when using FeOOH type oxides as
the starting materials was most complete.

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A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

3.2. Physico-chemical properties of the pigments

Fig. 3. SEM photographs showing the morphology of particles of the pigments.

(a1) ZnFe2 O4 (FeOOH); (a2) ZnFe2 O4 (FeOOH); (b1) MgFe2 O4 (FeOOH); (b2)
MgFe2 O4 (FeOOH); (c1) Mg0.2 Zn0.8 Fe2 O4 (FeOOH); (c2) Mg0.2 Zn0.8 Fe2 O4 (FeOOH);
(d1) ZnFe2 O4 (FeOFe2 O3 ); (d2) ZnFe2 O4 (FeOFe2 O3 ); (e1) MgFe2 O4 (FeOFe2 O3 ) (e2)
MgFe2 O4 (FeOFe2 O3 ); (f1) Mg0.2 Zn0.8 Fe2 O4 (FeOFe2 O3 ); (f2) Mg0.2 Zn0.8 Fe2 O4 (z
FeOFe2 O3 ); (g1) ZnFe2 O4 (-Fe2 O3 ); (g2) ZnFe2 O4 (-Fe2 O3 ); (h1) MgFe2 O4 (Fe2 O3 ); (h2) MgFe2 O4 (-Fe2 O3 ); (i1) Mg0.2 Zn0.8 Fe2 O4 (-Fe2 O3 ); (I2) Mg0.2 Zn0.8
Fe2 4 (-Fe2 O3 ,); (j1) ZnFe2 O4 (lam. Fe2 O3 ); (j2) ZnFe2 O4 (lam. Fe2 O3 ); (k1) MgFe2 O4
(lam. Fe2 O3 ); (k2) MgFe2 O4 (lam. Fe2 O3 ); (l1) Mg0.2 Zn0.8 Fe2 O4 (lam. Fe2 O3 ); (l2)
Mg0.2 Zn0.8 Fe2 O4 (lam. Fe2 O3 ). SEI detector.

The basic parameters of the pigments prepared from the various starting materials are summarised in Table 2. The parameters
include density, oil number, CPVC, and particle size distribution.
The particle size distribution values D(0.5), D(0.9), and D(0.1) show
that the size of 50%, 90% or 10% particles, respectively, in the volume is smaller than the specied value. D(4.3) is the mean particle
size. The physico-chemical properties of the powdered pigments,
pH, specic electric conductivities of pigment extracts and of the
unsupported paint lm extracts (in S/cm), and fractions of substances soluble in boiling water, W100 (in wt.%), are given in Table 3.
The pH and conductivity data refer to Day 30, after the steady states
of the two parameters had established.
Milling was a successful way to reduce the ferrite particles to a
size that is suitable for use as pigments in paints forming homogeneous lms free from aggregations. The mean particle size of
all ferrites lay within the range of 2.573.50 m (Table 2). As follows from the particle size distribution measurements, the mean
particle size of pigments synthesised from starting substances possessing the needle shape or nodular shape lay within the range of
1.202.49 m. The mean particle size was smallest in the ferrites
prepared from FeOOH, whereas ferrites prepared from specularite
consisted of larger particles.
The pH and specic electric conductivity levels of the ferrite
pigments are given in Table 3. The highest pH values on day 30
were observed for ferrites prepared by reacting Fe2 O3 with MgCO3
(represented by the formula MgFe2 O4 ), followed by mixed ferrites (Mg0.2 Zn0.8 Fe2 O4 ). The lowest pH values were found for
pigments containing either zinc ions (ZnFe2 O4 ) or the starting ferric oxides (FeOOH, Fe3 O4 , Fe2 O3 and lamellar Fe2 O3 ). The nding
of the previous study [25], that ferrites whose particles possess a
non-isometric shape give rise to basic solutions, was conrmed by
the present investigation. The pH of aqueous extracts of the paint
lms containing the ferrites tested exhibited an increasing trend
during the initial 30-day period, due to the slow release of ions
which increased the alkalinity of the water. Magnesium ions were
released most readily (from the ferrites MgFe2 O4 ), and the pH of
their extracts lay within the range of 6.18.11.
The specic electric conductivity levels increased with time, due
to the release of ions from the pigments or paint lms. Ferrites
which release ions give rise to a higher conductivity than the starting Fe oxides. An increase in conductivity during the 30-day period
was also observed in aqueous extracts of the paint lms containing ferrites which had been prepared from FeOOH (Table 3). Once
again, magnesium ions (MgFe2 O4 ) were found to be released most
readily. Generally, increasing conductivity accelerates the corrosion process; in this specic case, however, the corrosion rate was
slowed down by the higher pH, at which corrosion was less severe
owing to the properties of the steel.
The fraction of substances that are soluble in hot water is a
parameter characterising the efciency of the product rinsing step
and also an indicator of usability of the pigment in binder systems that are sensitive to the water-soluble salt content. Since
the water-soluble fraction never exceeded 1%, the hazard of the
occurrence of osmotic blisters was nearly negligible. The watersoluble fraction was lowest in the ferrite MgFe2 O4 prepared from
lamellar Fe2 O3 (MgFe2 O4 /lam. Fe2 O3 ). It is noteworthy that the
water-soluble fraction of the ferrites prepared from FeOOH never
exceeded 0.04%, which is the level exhibited by the starting FeOOH
(Table 3).
3.3. Corrosion-induced steel panel weight loss
The data of the steel panel corrosion losses in the aqueous
extracts of the pigments (Xp ) and of the paint lms (Xf ) are given

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

155

Table 2
Physical properties (density, oil number, CPVC, and particle size distribution) of the powdered pigments.
Pigment

Density* (g/cm3)

Goethite (FeOOH)
ZnFe2 O4
5.151
MgFe2 O4
4.411
5.049
Mg0.2 Zn0.8 Fe2 O4
Magnetite (FeOFe2 O3 )
5.077
ZnFe2 O4
4.347
MgFe2 O4
4.824
Mg0.2 Zn0.8 Fe2 O4
Hematite (-Fe2 O3 )
ZnFe2 O4
5.077
4.323
MgFe2 O4
4.894
Mg0.2 Zn0.8 Fe2 O4
Specularite (lam. -Fe2 O3 )
10.73
ZnFe2 O4
15.98
MgFe2 O4
10.5
Mg0.2 Zn0.8 Fe2 O4
Starting oxides
4.09
FeOOH
Fe2 O3
4.97
4.71
FeOFe2 O3
lam. -Fe2 O3
4.88
*

Oil consumption* (g/100 g)

CPVC ()

Particle size Per cent fraction below the specied

size in m
D(0.1)

D(0.5)

D(0.9)

D(4.3)

13.72
14.76
11.63

56.82
58.82
61.3

0.456
0.891
1.457

1.079
2.188
3.206

2.131
4.449
1.701

1.206
2.446
1.701

14.68
13.08
11.79

55.18
62.06
62.05

0.546
0.871
0.489

1.788
1.939
1.597

4.101
3.763
4.057

2.123
2.157
2.009

19.58
15.76
11.03

48.33
57.72
63.27

0.343
0.955
0.489

1.018
2.208
1.597

3.666
4.444
4.057

2.166
2.484
2.009

62.65
57.59
64.34

0.552
0.828
0.550

2.569
2.357
1.978

7.656
5.424
5.363

3.496
2.814
2.572

39.81
40.89
46.24
58.54

0.120
0.210
0.421
1.230

1.012
1.230
1.114
2.334

1.201
3.21
2.350
7.612

0.12
0.17
0.3
5.3

5.167
4.285
4.91
35.67
27.05
22.96
13.5

Parameters are given as arithmetic averages within 10 measured values.

Table 3
Physico-chemical properties (pH, specic electric conductivity and water-soluble fraction) of the powdered pigments.
Pigment

Particle shape

pH

Pigment
Goethite (FeOOH)
ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
Magnetite (FeOFe2 O3 )
ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
Hematite (-Fe2 O3 )
ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
Specularite (lam. -Fe2 O3 )
ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
Reference Fe oxides
FeOOH
Fe2 O3
FeOFe2 O3
Lam-Fe2 O3

Specic electric
conductivity 30 (S/cm)
Paint

Pigment

Paint

Water-soluble fraction
W100 102 (%)

Needles

7.05
9.28
8.56

6.28
7.07
6.24

37.6
145.8
150.5

21.2
106.8
28

3.48
1.59
2.69

Nodular

7.29
8.85
8.65

6.38
6.7
5.68

48.4
131.5
103.1

19.1
45.8
17.1

1.09
6.54
1.67

Isometric

5.69
8.76
8.42

6.06
6.1
5.44

47.3
131.5
75.1

11.3
42.4
21.3

8.79
7.79
1.97

8.53
11.13
8.98

5.91
8.11
6.65

178.4
300
224

14.2
339
29.2

11.53
0.60
7.95

4.18
6.19
6.5
8.07

5.48
5.68
6.17
6.37

349
36.9
406
191

18.8
24
34.6
36

3.82
2.47
16.54
3.23

Lamellar

Needles
Isometric
Nodular
Lamellar

in Table 4. For illustration, the pH and specic electric conductivity

levels measured on Day 10 of the test (pH10 and 10 , respectively)
and are also displayed.
Study of anticorrosive pigment properties always assumes a
complex view on the anticorrosive pigment/binder interactions
or those between the functional binder groups and surrounding
medium. The greatest simplication from this point of view is
presented by following the corrosion losses and corrosion velocities of anticorrosive pigment alone in the aqueous suspension
form [26]. The corrosion losses were determined after 10 days of
steel panel submersion in aqueous extracts of the pigments or of
the paint lms. The pH and conductivity of the extracts play a
major role in the corrosion of the steel panels, as reected by the
panel weight loss data. The tabulated data are relative (per cent)
values with respect to the weight loss in demineralised water,
taken as 100%. Corrosion inhibition by the pigments was most

pronounced for the ferrites prepared from FeOOH (Table 5). The
corrosion loss in the paint lm extracts was 13% higher if the paint
initially contained FeOOH than if the paint contained a ferrite prepared from it. Paints containing ferrites prepared from lamellar
Fe2 O3 also exhibited outstanding corrosion-inhibiting properties.
In this respect, all paints containing the ferrites synthesised were
superior to the non-pigmented epoxy-ester coating material. Outstanding results were obtained with the paint lms containing
the ferrite MgFe2 O4 prepared from FeOFe2 O3 or from lamellar Fe2 O3 (MgFe2 O4 /FeOFe2 O3 , MgFe2 O4 /lam. Fe2 O3 ) and with
the paint lms containing the ferrite Mg0.2 Zn0.8 Fe2 O4 prepared
from lamellar Fe2 O3 (Mg0.2 Zn0.8 Fe2 O4 /lam. Fe2 O3 ). Outstanding
corrosion-inhibiting capacity was observed for paints containing
ferrite pigments prepared from lamellar Fe2 O3 .
The method of following the corrosion losses in the suspensions of organic coatings containing spinels gives evidence on the

156

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

Table 4
Relative corrosion-induced weight losses of steel panels submerged in aqueous extracts of the pigments (Xp ) and of the paint lms (Xf ), and pH and specic electric conductivity
() levels of the extracts.
Pigment

Aqueous extract of the pigments

pH ()

Goethite (FeOOH)
7.26
ZnFe2 O4
7.95
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
7.78
Magnetite (FeOFe2 O3 )
ZnFe2 O4
7.05
8.06
MgFe2 O4
7.77
Mg0.2 Zn0.8 Fe2 O4
Hematite (-Fe2 O3 )
ZnFe2 O4
6.78
MgFe2 O4
7.73
7.26
Mg0.2 Zn0.8 Fe2 O4
Specularite (lam. -Fe2 O3 )
7.44
ZnFe2 O4
7.56
MgFe2 O4
8.15
Mg0.2 Zn0.8 Fe2 O4
Nonpigmented lm, reference pigments

Epoxy-ester lm
6.64
FeOOH
7.59
Lamellar Fe2 O3
6.76
Fe2 O3
6.72
FeOFe2 O3
6.75
H2 O (blank)

Aqueous extract of the paint lm

 (S/cm)

Xp (%)

pH ()

 (S/cm)

Xf (%)

49.7
208
196.5

59.80
75.81
48.09

6.74
7.0
6.89

32.8
101.2
51.1

30.48
29.74
28.69

64.5
207
159.1

29.82
52.51
49.05

6.74
6.91
6.69

32.6
74.1
44.8

40.63
24.43
40.66

52.5
210
122.7

38.92
44.82
32.94

6.45
6.78
6.53

26.8
63
52.6

44.71
31.72
41.85

227
111.8
313

49.77
71.01
48.91

6.61
7.55
6.67

30.3
333
48.4

35.30
25.74
25.22

357
184.2
67.9
416
9.3

56.79
66.78
28.08
40.57
100

5.19
6.68
6.80
6.59
6.76

10.0
43.8
49.3
44.3
46.9

69.48
43.01
26.95
33.38
34.09

Table 5
Surface hardness data for the paint lms on glass (DFT = 60 10 m).
Pigment

Surface hardness (%)

Day 1

FeOOH
9.51
ZnFe2 O4
MgFe2 O4
11.37
9.98
Mg0.2 Zn0.8 Fe2 O4
FeOFe2 O3
ZnFe2 O4
8.35
10.67
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
9.05
Fe2 O3
ZnFe2 O4
12.76
9.28
MgFe2 O4
10.21
Mg0.2 Zn0.8 Fe2 O4
lam-Fe2 O3
ZnFe2 O4
11.14
8.82
MgFe2 O4
10.44
Mg0.2 Zn0.8 Fe2 O4
Nonpigmented lm. reference pigments
9.05
Epoxy-ester lm
9.28
FeOOH
9.74
FeOFe2 O3
8.82
Fe2 O3
9.74
Lam. Fe2 O3

Day 2

Day 3

Day 7

Day 14

Day 21

Day 100

13.70
15.53
13.70

14.32
15.70
20.32

24.35
30.97
27.90

35.83
34.89
37.24

40.09
40.79
41.96

46.64
43.24
43.76

11.19
13.93
12.33

12.70
14.78
13.86

18.20
28.37
25.30

31.85
34.66
34.89

35.20
39.16
39.16

44.85
42.27
44.08

17.58
12.33
13.24

24.25
13.63
15.24

31.44
22.46
29.08

33.49
32.32
37.70

38.46
38.46
41.96

44.90
40.82
44.55

15.75
12.10
13.24

18.01
14.09
15.01

33.10
23.64
28.61

40.52
34.66
37.00

45.45
38.00
41.72

48.49
42.45
45.48

12.79
12.33
13.47
12.33
13.01

14.32
14.09
13.86
13.63
15.01

23.64
22.46
26.00
18.44
27.66

38.88
36.53
35.13
31.85
33.72

40.09
41.00
39.63
36.83
35.66

41.10
41.00
41.01
41.32
43.98

possible reactions inside the coating, namely that yet in the liquid state, on the formation of lm and partially also on ageing the
lm already in the hardened state [27]. In an epoxy ester resin
binder, the acidic COOH binder groups are present, except the
hydroxyl groups. Epoxy esters are obtained by esterifying part of
the hydroxyl groups and the addition of fatty acids to epoxy groups
at higher temperatures (200220 C). To obtain optimum properties of the binder is used only 4060% of the esterication resin
ability and the products contained a part of the hydroxyl groups
unesteried [28]. The carboxyl groups, contained in the epoxy ester
resin binder, cause the acidity; the hydroxyl groups, contained in
the epoxy ester binder, cause the reduction of acidity. It was found
that the lm which does not contain any pigments and which was
transferred to the aqueous suspension, affects the water extract
pH value in such a way, that the resulting pH value is 5.2. When

this slightlyacidic binder contains a spinel pigment, then the pH

extract values are rising with most pigments used to a region of pH
value = 6.57.5.
3.4. Mechanical tests of the paint lms
The surface hardness data for the paint lms on glass panels,
determined with a Perzos pendulum, are displayed in Table 5. The
ultimate values were read 100 days after the paints were coated
onto the glass substrate.
In the group of paints containing the pigment ZnFe2 O4 , the highest hardness was observed with the paint containing the ferrite
prepared from lamellar Fe2 O3 (ZnFe2 O4 /lam. Fe2 O3 ). In the group
of paints containing the ferrite MgFe2 O4 , the highest hardness
was observed with the paint containing FeOOH (MgFe2 O4 /FeOOH),

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

157

Table 6
Results of mechanical tests of the paint lms (DFT = 60 10 m).
Pigment

Cupping [mm]

Starting substance: goethite (FeOOH)

ZnFe2 O4
9.79*
9.84*
MgFe2 O4
9.54*
Mg0.2 Zn0.8 Fe2 O4
Starting substance: hematite (-Fe2 O3 )
9.81*
ZnFe2 O4
9.82*
MgFe2 O4
9.49*
Mg0.2 Zn0.8 Fe2 O4
Starting substance: magnetite (FeOFe2 O3 )
9.48*
ZnFe2 O4
MgFe2 O4
9.81*
Mg0.2 Zn0.8 Fe2 O4
9.73*
Starting substance: specularite (lamellar -Fe2 O3 )
>10*
ZnFe2 O4 (S)
9.31*
MgFe2 O4
>10*
Mg0.2 Zn0.8 Fe2 O4
Nonpigmented lm. reference pigments
>10*
Epoxy-ester lm
9.78*
FeOOH
9.8*
Fe2 O3
FeOFe2 O3
9.79*
9.85*
Lamellar Fe2 O3
*

Bending [mm]

Impact

Adhesion (deg.)

Pull-off (MPa)

>100
>100
>100

0
0
0

1.1
1.5
1.9

>100
>100
>100

>100
>100
>100

0
0
0

1
1.6
1

<4
<4
<4

>100
>100
>100

>100
>100
>100

0
0
0

1
2
1.8

<4
<4
<4

>100
>100
>100

>100
>100
>100

0
0
0

1.8
1.8
1.3

<4
<4
<4
<4
<4

>100
>100
>100
>100
>100

>100
>100
>100
>100
>100

1
2
2
0
2

1.6
1.9
1.1
2
1.2

Reverse (cm)

Averse (cm)

<4
<4
<4

>100
>100
>100

<4
<4
<4

Panel break.

Table 7
Corrosion effects on panels coated with the paints (DFT = 95 10 m), observed following 800 h of exposure to the atmosphere with NaCl mist.
Pigment

Blisters on the lm
surface

Starting substance: goethite (FeOOH)

8F
ZnFe2 O4
8F
MgFe2 O4

Mg0.2 Zn0.8 Fe2 O4

Starting substance: hematite (-Fe2 O3 )
8F
ZnFe2 O4
MgFe2 O4
8F
Mg0.2 Zn0.8 Fe2 O4

Starting substance: magnetite (FeOFe2 O3 )

ZnFe2 O4
8F
8F
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4

Starting substance: specularite (lamellar -Fe2 O3 )

ZnFe2 O4
8F
MgFe2 O4
8F

Mg0.2 Zn0.8 Fe2 O4

Nonpigmented lm, reference pigments
8F
Epoxy-ester lm
6F
FeOOH
Fe2 O3
8F
4M
FeOFe2 O3

lam. Fe2 O3

Blisters in the cut

(deg.)

Adhesion (deg.)

Corrosion in the
cut (mm)

Corroded metal
surface fraction (%)

4M
4M
6M

1
0
0

0.13
0.22
0.11

0.3
0.1
0.01

4D
6MD
6M

0
0
0

0.09
0.4
0.22

1
0.03
0.1

2M
4MD
4M

1
0
0

0.06
0.23
0.1

1
0.1
0.03

2M
4F
8M

0
0
0

0.07
0.42
0

0.3
0.3
0.03

4F
6D
6F
2M
2M

2
0
1
0

2
0.56
0.75
0.5
0.13

0.3
3
3
10
1

while in the group of paints containing Mg0.2 Zn0.8 Fe2 O4 , the highest hardness was observed with the paint containing lamellar Fe2 O3
(Mg0.2 Zn0.8 Fe2 O4 /lam. Fe2 O3 ). Clearly, ferrites prepared from specularite contribute most to the surface hardness of the paint
lms.
The spinel-type pigments are also capable of reacting with the
carboxyl binder groups, which results in the formation of metal
soaps [29]. The formation of soaps is however lower compared with
the alkyd resin. The formation of metal soaps becomes evident from
the hardness values, which increase with the time. The lowest surface hardness was found for the non-pigmented coating material
epoxy-ester resin (where all the samples were desiccated in presence of constant amounts of siccatives). Due to the fact that the
hardness of coatings pigmented with starting iron oxides Fe2 O3 is
lower than that of those pigmented with spinel-type pigments the
formation of the zinc and magnesium soaps can be supposed to
take place.

The results of mechanical tests of the paint lms on metal substrates are given in Table 6. Films of the non-pigmented binder
and of the paints containing the starting ferric pigments are also
included for comparison. The data include the following tests: cupping (Erichsen) test, bending test, impact test (with weight drop
onto both the adverse and reverse sides of the panel), adhesion
test by the cross-cut method (blade spacing 1 mm), and pull-off
test. The mechanical tests (cupping, pending, impact, adhesion,
and pull-off) of the various paints had a nearly identical course.
The non-pigmented epoxy-ester resin lm exhibited outstanding
properties. Non-pigmented coating materials possess high physical
properties, determined by the nature of the binder. The mechanical
properties of paint lms are affected by the pigments contained in
the paints [30]. Many of the ferrites tested improved the adhesion
of paint lms; the results are given in Table 7. In the cupping test,
the panels invariably broke before any paint lm cracking could be
observed. The paint lm never cracked in the test which involved

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A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

Table 8
Corrosion effects on panels coated with the paints (DFT = 95 10 m), observed following 1600 h of exposure to the atmosphere with NaCl mist.
Pigment

Blisters on the lm
surface

Starting substance: goethite (FeOOH)

ZnFe2 O4
4M
MgFe2 O4
6F
Mg0.2 Zn0.8 Fe2 O4
8F
Starting substance: hematite (-Fe2 O3 )
ZnFe2 O4
6F
MgFe2 O4
4M
Mg0.2 Zn0.8 Fe2 O4
6F
Starting substance: magnetite (FeOFe2 O3 )
4M
ZnFe2 O4
6M
MgFe2 O4
6F
Mg0.2 Zn0.8 Fe2 O4
Starting substance: specularite (lamellar -Fe2 O3 )
8M
ZnFe2 O4
MgFe2 O4
6M
Mg0.2 Zn0.8 Fe2 O4
4M
Nonpigmented lm, reference pigments
Epoxy-ester lm
8F
FeOOH
4M
FeOFe2 O3
4MD
Fe2 O3
6M
lam. Fe2 O3
4F

Blisters in the cut

(deg.)

Adhesion (deg.)

Corrosion in the
cut (mm)

Corroded metal
surface fraction (%)

2MD
2MD
2M

4
0
0

0.1
0.1
0.15

1
0.3
0.1

4MD
4MD
4MD

5
3
1

0.12
0.6
0.18

0.1
3
0.1

2D
4D
4MD

5
4
1

0.11
0.1
0.21

1
0.3
0.1

4M
4F
4F

2
4
4

0.09
0.2
0.08

0.3
1
0.1

4F
4D
2D
2F
2MD

3
5
5
5
0

0.75
0.7
0.56
1
0.8

1
3
16
10
100

Table 9
Corrosion effects on panels coated with the paints (DFT = 95 10 m), observed following 600 h of exposure to the atmosphere with SO2 .
Pigment

Blisters on the lm
surface

Starting substance: goethite (FeOOH)

ZnFe2 O4

MgFe2 O4

Mg0.2 Zn0.8 Fe2 O4

Starting substance: hematite (-Fe2 O3 )

ZnFe2 O4
MgFe2 O4

Mg0.2 Zn0.8 Fe2 O4

Starting substance: magnetite (FeOFe2 O3 )

ZnFe2 O4

MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4

Starting substance: specularite (lamellar -Fe2 O3 )

ZnFe2 O4

MgFe2 O4

Mg0.2 Zn0.8 Fe2 O4

Nonpigmented lm, reference pigments

Epoxy-ester lm
8F
FeOOH
8F
FeOFe2 O3
6F
Fe2 O3
8F
lam. Fe2 O3

Blisters in the cut

(deg.)

Adhesion (deg.)

Corrosion in the
cut (mm)

Corroded metal
surface fraction (%)

6F
4M
8M

0
0
0

0.95
0.88
0.94

1
0.3
0.03

8MD
8M
6F

0
0
0

0.73
0.25
0.46

0.3
0.3
0.03

6MD
8MD
8F

0
0
0

1.13
0.68
0.15

0.1
0.1
0.1

6F
8M
8F

0
0
0

0.72
0.78
0.43

0.1
1
0.3

8F
8F
6M
2F
6M

4
0
0
1
0

0.4
0.69
0.88
0.18
1

0.1
1
1
1
3

bending the panel over the 4 mm diameter mandrel. The paint lm

never cracked during the impact test, either when dropping the
weight from a height of 100 cm onto the reverse side or the adverse
side of the panel. The adhesion of all paints with the pigments tested
was degree 0, while that of the non-pigmented epoxy-ester resin
lm was degree 1. The adhesion degree was 2 for the paints with
the starting oxides FeOOH and Fe2 O3 and with the lamellar Fe2 O3 .
The pull-off strength was between 1 and 2 MPa. The best result in
the pull-off test (pull-off strength 2 MPa) was obtained with the
paint containing MgFe2 O4 (FeOFe2 O3 ).
3.5. Corrosion tests of the paint lms on steel panels
The results of the corrosion tests of the paints containing the pigments examined are included in Tables 710. Corrosion changes
on the paint lms and on the substrate metal were assessed.
The effects included the formation of blisters on the paint lm,

corrosion of the metal surface, and corrosion of the metal at the

cut made in the lm. The evaluation was based on the following
standards: ASTM D 714-87 (blister size and frequency of occurrence), ASTM D 610-85 (corroded fraction of the metal surface
area), and ASTM D 1654-92 (corrosion propagation near the test
cut). Scores which are acceptable according to the standards are
shown in parentheses. The degree of paint lm adhesion measured
by the cross-cut test (1 mm 1 mm squares) was assessed as per

the CSN
ISO 2409 standard 24 h after removing the panels from the
corrosion environment.
The data obtained from the tests consisting of 800 h and 1600 h
of exposure to the atmosphere with the NaCl mist are given in
Tables 7 and 8, respectively. The data obtained from the tests consisting of 600 h and 1200 h of exposure to the atmosphere with
SO2 are given in Tables 9 and 10, respectively. The data obtained
from the 1632-hours cyclic test comprising exposure to the various
corrosion environments are given in Table 11.

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

159

Table 10
Corrosion effects on panels coated with the paints (DFT = 95 10 m), observed following 1200 h of exposure to the atmosphere with SO2 .
Pigment

Blisters on the lm
surface

Starting substance: goethite (FeOOH)

ZnFe2 O4
8F
MgFe2 O4
8F
Mg0.2 Zn0.8 Fe2 O4

Starting substance: hematite (-Fe2 O3 )

ZnFe2 O4
8F
MgFe2 O4
8F
Mg0.2 Zn0.8 Fe2 O4
8F
Starting substance: magnetite (FeOFe2 O3 )
8F
ZnFe2 O4
8F
MgFe2 O4
8F
Mg0.2 Zn0.8 Fe2 O4
Starting substance: specularite (lamellar -Fe2 O3 )
8F
ZnFe2 O4
MgFe2 O4
8F
Mg0.2 Zn0.8 Fe2 O4
8F
Nonpigmented lm, reference pigments
Epoxy-ester lm

FeOOH
8F
FeOFe2 O3
8F
Fe2 O3
8F
lam. Fe2 O3
8F

Blisters in the cut

(deg.)

Adhesion (deg.)

Corrosion in the
cut (mm)

Corroded metal
surface fraction (%)

6MD
6MD
6M

0
0
0

2.06
2.11
1.98

1
0.1
0.03

6MD
6MD
6M

1
0
0

2.58
2.08
2.07

1
1
0.1

4MD
6MD
6MD

0
0
0

2.45
2.44
2

0.3
0.3
1

4MD
6M
6M

0
0
0

2.82
1.79
2.08

0.3
1
0.3

4MD
4D
4D
6D
6MD

5
0
0
0
1

1
1.94
2.02
2.19
2.43

1
3
3
3
3

Table 11
Corrosion effects on panels coated with the paints (DFT = 95 10 m), observed following 1632 h of cyclic exposure to the various corrosive atmospheres.
Pigment

Blisters on the lm
surface

Starting substance: goethite (FeOOH)

ZnFe2 O4

MgFe2 O4

Mg0.2 Zn0.8 Fe2 O4

Starting substance: hematite (-Fe2 O3 )
ZnFe2 O4
6F
6F
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
6M
Starting substance: magnetite (FeOFe2 O3 )
8F
ZnFe2 O4

MgFe2 O4
8F
Mg0.2 Zn0.8 Fe2 O4
Starting substance: specularite (lamellar -Fe2 O3 )
6F
ZnFe2 O4
MgFe2 O4

6F
Mg0.2 Zn0.8 Fe2 O4
Nonpigmented lm, reference pigments
Epoxy-ester lm

6M
FeOOH
6M
FeOFe2 O3
6M
Fe2 O3

lam. Fe2 O3

Blisters in the cut

(deg.)

Adhesion (deg.)

Corrosion in the
cut (mm)

Corroded metal
surface fraction (%)

4M
8F
4F

1
1
0

0.35
0.2
0.4

3
0.1
0.03

4F
4F
8F

1
2
3

0.3
0.4
1.2

1
0.3
0.3

4MD
4F
4M

0
5
0

0.5
0.6
0.3

0.3
0.1
3

4F
6F
8F

0
1
0

0.1
0.25
1.25

0.1
0.1
3

4F
6MD
4MD
4M
6M

5
4
3
2
3

0.8
0.4
0.6
0.55
1.3

0.1
0.3
1
16
10

3.5.1. Cyclic corrosion test in the combined test chamber with salt
mist
This test encompassed total exposure for 800 h and 1600 h. The
observed data are included in Tables 7 and 8. The best results
(in nearly all parameters) for 800 h of exposure were obtained
for the paint with ferrite ZnFe2 O4 prepared from lamellar Fe2 O3
(ZnFe2 O4 /lam. Fe2 O3 ), both in comparison with the other zinc ferrite types synthesised and with the starting ferric pigments.
The group of paints with MgFe2 O4 gave better overall results
than the paint with ZnFe2 O4 ; the only parameter where this was
not true was corrosion in the cut. The best results were obtained
for paints containing Mg0.2 Zn0.8 Fe2 O4 . The weakest parameter was
resistance to the formation of blisters on the lm near the cut,
which was affected by the disturbance of the protective coating
and penetration of chloride ions beneath the lm.
The corrosion effects observed following 1600 h of exposure
were very similar to those observed after 800 h of exposure with

regard to the inuence of the various groups of pigments. The

results are given in Table 8. Examples of corrosion effects on the
panels after the exposure and after removing the paint lm are
shown in Fig. 4. Once again, the best results were obtained with
the paints containing the ferrite Mg0.2 Zn0.8 Fe2 O4 .
Conclusions from the exposure of the panels to the environment
with NaCl mist:
Paints containing ferrites prepared from starting oxides of lamellar shape (lam. Fe2 O3 ) or needle shape (FeOOH) are superior to
paints with ferrites possessing an isometric particle shape.
All of the paints containing the ferrites are superior to those containing the starting ferric oxides.
3.5.2. Cyclic corrosion test in the condensation chamber with SO2
Evaluation of the corrosion effects following 600 h of exposure to the environment with SO2 is presented in Table 9.

160

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

Fig. 4. Examples of corrosion effects of the NaCl mist on a steel panel coated with a paint containing MgFe2 O4 prepared from Fe2 O3 . (A and B) Paint lms following 800 h (A)
and 1600 h (B) of exposure; (C and D) Steel substrate surface after removing the paint lm, following 800 h (C) and 1600 h (D) of exposure.

The presence of any pigment in the epoxy-ester resin system appreciably improved the degree of adhesion of the paint lm to the
substrate following exposure to the corrosion environment. Outstanding results were obtained with the paints containing the
ferrites prepared; corrosion blisters never developed. The corroded
fraction of the substrate metal surface is very small and largely
decreases from paints containing the Zn ferrite (ZnFe2 O4 ) to those
with the Mg ferrite (MgFe2 O4 ), and was lowest when using the
paint with the mixed ferrite MgZn (Mg0.2 Zn0.8 Fe2 O4 ). Due to the
easier diffusion of the mobile SO2 , corrosion in the cut was more
pronounced on this exposure than on that exposed to salt mist. The
corrosion effects observed after 1200 h of exposure to the environment with SO2 are listed in Table 10. From the corrosion effects
listed, corrosion in the cut was the most marked. The best results
in this respect were observed with the paint containing MgFe2 O4

(MgFe2 O4 /lam. Fe2 O3 ). As regards protection against corrosion of

the substrate metal surface, paints with any of the ferrites were
superior to those with the starting ferric oxides. The formation of
blisters was nearly negligible. A comparison of changes on panels
exposed to the corrosion environment for 600 h and for 1200 h is
presented in Fig. 5.
3.5.3. Accelerated corrosion test of consecutive exposure to
various corrosion environments
This test served to assess how the coating responds to a changing corrosion environment. The coated panels were exposed to
an environment with condensed water for 1152 h, then to a salt
mist environment for 240 h and nally to an SO2 environment for
another 240 h. The results are listed in Table 11. Photographs of
two paint lms and the steel substrates are presented in Fig. 6.

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

161

Fig. 5. Corrosion effects on a panel coated with the paint containing MgFe2 O4 prepared from Fe2 O3 , observed after exposure to the environment with SO2 . (A and B) Paint
lm after 600 h (A) and 1200 h (B) of exposure; (C and D) steel panel after removing the paint lm, following 600 h (C) and 1200 h (D) of exposure.

The corroded fraction of the substrate metal surface was considerably higher when using paints with ferrites based on the
starting oxides Fe2 O3 and lamellar Fe2 O3 than when using any of
the remaining paints. The non-pigmented epoxy-ester lm exhibited very good properties, except for adhesion, which undoubtedly
ranks amongst the most important parameters of protective
coatings [30].
The best anticorrosion properties were found for paints with
MgFe2 O4 (MgFe2 O4 /FeOOH and MgFe2 O4 /lam. Fe2 O3 ) and with
ZnFe2 O4 (ZnFe2 O4 /lam. Fe2 O3 ). The corroded fraction of the substrate metal surface was 0.1% and the adhesion degree was 1.
The adhesion degree of the paint with ZnFe2 O4 was 0. The results
attained with the paints containing isometric shape ferrites were
not as good as those attained with the non-isometric ferrites. This
difference is illustrated by Fig. 6.

3.6. Conclusions from the corrosion tests and mechanical

resistance tests of the paint lms
(1) The pigment particle shape was found to substantially affect
surface hardness of the paint lms. Surface hardness was
highest for the paint lm containing ZnFe2 O4 prepared from
lamellar Fe2 O3 (ZnFe2 O4 /lam. Fe2 O3 ). The same hardness
degree was found for the paint lms containing ZnFe2 O4
or MgFe2 O4 , both prepared from FeOOH (ZnFe2 O4 /FeOOH,
MgFe2 O4 /FeOOH). Paints with any of the pigments prepared
showed a better degree of adhesion than those with the starting
ferric oxides.
(2) Corrosion-induced weight losses of steel panels submerged
in aqueous extracts of the powdered pigments and in aqueous extracts of the unsupported paint lms serve to assess

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A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

Fig. 6. Corrosion effects on panels coated with two chemical identically pigments, Mg0.2 Zn0.8 Fe2 O4 , differing in their particle morphology: (A and C) pigment prepared from
FeOOH, (B and D) pigment prepared from FeOFe2 O3 . (A and B) Paint lms, (B and D) Substrate metal after removing the paint lm.

the effect of the cation which is slowly released from the

pigment and possesses basic properties. The corrosion losses
in the powdered pigment extracts were higher than in the
paint lm extracts, due to the higher electric conductivity,
which affects corrosion appreciably. The best results in this
test were obtained with paint lms containing MgFe2 O4 or
Mg0.2 Zn0.8 Fe2 O4 prepared from lamellar Fe2 O3 (MgFe2 O4 /lam.
Fe2 O3 and Mg0.2 Zn0.8 Fe2 O4 /lam. Fe2 O3 ). Low corrosion losses
were also measured for the paint with MgFe2 O4 prepared from
FeOFe2 O3 (MgFe2 O4 /FeOFe2 O3 ). Results of such a measurement give us information on the alkalinity of the pigment
considered and the solubility thereof in water medium. This
results can be summarized as follows: the synthetised spinel
pigments exhibit alkaline nature and differ by solubilities in
aqueous phases; they shift the pH water extract value of the

(3)

(a)

(b)
(c)

coating lms to the alkaline region also on using a binder showing acid reaction; the binder containing carboxy groups/spinel
pigment interactions lead to the appearance of metal soaps.
The orders of corrosion effects on the test panels subjected to
1600-hours exposure to the atmosphere with the mist of a
5% NaCl solution were as given below, starting with the pigment for which the corrosion effects were least pronounced.
The respective starting ferric oxides are given in parentheses:
Blister formation on the paint lm: Mg0.2 Zn0.8 Fe2 O4
(FeOOH) < MgFe2 O4 (FeOOH), Mg0.2 Zn0.8 Fe2 O4 (FeOFe2 O3 ,
Fe2 O3 ), ZnFe2 O4 (Fe2 O3 )
Propagation of corrosion in the cut: ZnFe2 O4 (lam.
Fe2 O3 ) < ZnFe2 O4 (FeOOH), MgFe2 O4 (FeOOH, FeOFe2 O3 )
Corrosion of the substrate metal surface: Mg0.2 Zn0.8 Fe2 O4
(FeOOH, FeOFe2 O3 , Fe2 O3 , lam. Fe2 O3 )

A. Kalendov et al. / Progress in Organic Coatings 86 (2015) 147163

(4) The orders of corrosion effects on the test panels subjected to

1200-hours exposure to the atmosphere with SO2 , again starting with the pigment for which the corrosion effects were least
pronounced, are listed below:
(a) Blister formation on the paint lm: Mg0.2 Zn0.8 Fe2 O4
(FeOOH) < all the remaining pigments
(b) Propagation of corrosion in the cut: MgFe2 O4 (lam.
Fe2 O3 ) < Mg0.2 Zn0.8 Fe2 O4 (lam. Fe2 O3 ) < ZnFe2 O4 (FeOOH)
(c) Corrosion of the substrate metal surface: Mg0.2 Zn0.8 Fe2 O4
(FeOOH) < MgFe2 O4 (FeOOH), Mg0.2 Zn0.8 Fe2 O4 (Fe2 O3 )
(5) The orders of corrosion effects on the test panels subjected to
consecutive exposure to the 3 corrosion environments (condensed H2 O, NaCl mist, SO2 ) were as outlined below, starting
with the pigment for which the corrosion effects were least
pronounced:
(a) Blister formation on the paint lm: ZnFe2 O4 (FeOOH), MgFe2 O4
(FeOOH, FeOFe2 O3 , lam. Fe2 O3 ), Mg0.2 Zn0.8 Fe2 O4 (FeOOH)
(b) Propagation of corrosion in the cut: ZnFe2 O4 (lam.
Fe2 O3 ) < MgFe2 O4 (FeOOH) < MgFe2 O4 (lam. Fe2 O3 )
(c) Corrosion of the substrate metal surface: Mg0.2 Zn0.8 Fe2 O4 (lam.
Fe2 O3 ) < ZnFe2 O4 (FeOOH), MgFe2 O4 (FeOOH, FeOFe2 O3 , lam.
Fe2 O3 )
(6) The above results show that the pigment particle shape has a
major effect on the pigments corrosion resistance. Irrespective of the corrosive environment, pigments prepared from the
needle-shaped FeOOH or from the lamellar Fe2 O3 were found
to be the most resistant. The cations in the pigments also play
a role in the corrosion protection properties. Paints containing the mixed pigment Mg0.2 Zn0.8 Fe2 O4 . were among the best.
Good protection against corrosion in the cut caused by the NaCl
mist was also found for ZnFe2 O4 .
4. Conclusion
The anticorrosion efciency of some ferrites as pigments in
epoxy-ester resin-based paints was examined depending on their
structure and chemical composition. The ferrites synthesised
included ZnFe2 O4 , MgFe2 O4 and Mg0.2 Zn0.8 Fe2 O4 prepared from
ferric oxides possessing different structures and primary particle
shapes, viz. -FeOOH, FeOFe2 O3 , FeOFe2 O3 , and lam. -Fe2 O3 .
The paints tested contained the pigment s at a pigment volume
concentration (PVC) = 10%. Two types of tests were performed:
physico-mechanical tests of the paint lms and accelerated corrosion tests of steel panels coated with the paints exposed to
environments with salt mist, with SO2 , and with condensation of
water. The best anticorrosion efciency was found for ferrites prepared from ferric oxides consisting of non-isometric particles.
The accelerated corrosion tests provided evidence that all paints
containing the pigment Mg0.2 Zn0.8 Fe2 O4 prepared from FeOOH,

163

FeOFe2 O3 , Fe2 O3 or lam. Fe2 O3 are well suited to use in corrosion

environments of category C5-I (according to CSN

EN ISO 12994).
Those paints have medium-to-long lifetimes. Hence, the pigments
are very high quality and can be recommended for application in
industrial high humidity/moisture environments with aggressive
atmospheres. The pigments synthesised can be used in coating
materials that are designed to protect metal substrates from corrosion in harsh corrosion conditions.
Nontoxic pigments can be obtained based on a suitable choice of
the cations in the oxide lattice. Solubility and toxicological effects
are important aspects from the environmental protection point of
view. It is concluded that the starting substances used are toxicologically insignicant and virtually insoluble.
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