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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].
148
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 .
2FeOOHFe2 O3 + H2 O
(1)
(2)
(3)
(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).
(5)
(6)
(7)
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
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
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
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.
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.
150
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
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
The test samples were prepared by coating the paints onto steel
panels (deep-drawn cold-rolled steel manufactured by Q-panel,
151
152
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 ).
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.
154
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
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
*
CPVC ()
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
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
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
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
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)
(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
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
157
Table 6
Results of mechanical tests of the paint lms (DFT = 60 10 m).
Pigment
Cupping [mm]
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
lam. Fe2 O3
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
158
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
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
ZnFe2 O4
MgFe2 O4
ZnFe2 O4
MgFe2 O4
ZnFe2 O4
MgFe2 O4
Mg0.2 Zn0.8 Fe2 O4
MgFe2 O4
Epoxy-ester lm
8F
FeOOH
8F
FeOFe2 O3
6F
Fe2 O3
8F
lam. Fe2 O3
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
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.
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
FeOOH
8F
FeOFe2 O3
8F
Fe2 O3
8F
lam. Fe2 O3
8F
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
ZnFe2 O4
MgFe2 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
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
160
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
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.
162
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.
(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 )
163
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
A. Kalendov, J. S nuprek,
P. Kalenda, Dyes Pigm. 30 (2) (1996) 129140.
R. Alizadeh, J.J. Beaudoin, V.s. Ramachandran, L. Raki, Adv. Cem. Res. 21 (2)
(2009) 5966.
P. Benda, A. Kalendov, Phys. Proc. 44 (2013) 185194.
P. Kalenda, Appl. Clay Sci. 48 (2010) 581588.
A. Kalendov, D. Vesely,
O.K. Abiola, A.O. James, Corros Sci. 52 (2010) 661664.
J. Stejskal, M. Trchov, Prog. Org. Coat. 63 (2008)
A. Kalendov, D. Vesely,
209221.
Prog. Org. Coat. 57 (2006) 110.
A. Kalendov, P. Kalenda, D. Vesely,
I. Sapurina, J. Stejskal, Prog. Org. Coat. 63 (2008)
A. Kalendov, D. Vesely,
228238.
A. Kalendov, Prog. Org. Coat. 62 (2008) 520.
D. Vesely,
A. Kalendov, Prog. Org. Coat. 39 (2000) 199206.
A. Kalendov, Pigm. Resin Technol. 29 (2000) 215221.
J. Mleziva, J. S nuprek,
Polymery; vyroba,
struktura, vlastnosti a pouzit,
Sobotles, Praha, 2000.
A. Kalendov, J. Snuprek,
P. Kalenda, in: G.P. Bierwagen (Ed.), ACS Book on
Organic Coatings for Corrosion Control, American Chemical Society, Washington, DC, 1998, pp. 366382.
K. Krishnamurti, Prog. Org. Coat. 11 (1983) 167197.