Corrosion Science 52 (2010) 602–611

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Active protection coatings with layered double hydroxide nanocontainers

of corrosion inhibitor
M.L. Zheludkevich a,*, S.K. Poznyak a, L.M. Rodrigues a,b, D. Raps c, T. Hack c, L.F. Dick b, T. Nunes d,
M.G.S. Ferreira a,e
a
University of Aveiro, CICECO, Dep. Ceramics and Glass Eng., 3810-193 Aveiro, Portugal
b
Rio Grande do Sul Federal University, 91501-970 Porto Alegre, Brazil
c
EADS Innovation Works, 81663 Munich, Germany
d
University of Aveiro, Department of Environment, 3810-193 Aveiro, Portugal
e
Technical University of Lisbon, IST, ICEMS, Av. Rovisco Pais, 1049-001 Lisbon, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Novel LDH-based nanocontainers of corrosion inhibitor are developed in the present work. The reservoirs
Received 12 July 2009 are composed by nanostructured layered double Mg/Al and Zn/Al hydroxides with divanadate anions
Accepted 13 October 2009 located in the interlayer regions. The nanocrystalline LDHs (layered double hydroxides) are able to
Available online 17 October 2009
release vanadate ions in a controllable way.
XRD, EDS and SEM methods were used in this work to study morphological and structural properties of
Keywords: the synthesized LDH powders. Corrosion protection effect of the LDH powders directly added to corrosive
A. Layered double hydroxides
electrolyte or to commercial coatings used for aeronautical application has been studied by electrochem-
A. Nanocontainers
A. Corrosion inhibitor
ical impedance spectroscopy and standard accelerated corrosion tests. Aluminium alloy 2024 was used
A. Protective coating here as substrate.
C. Self-healing The results demonstrate that both of the LDH pigments being added to corrosive media confer corro-
sion inhibition effect, especially Zn/Al based nanocontainers obtained by the anion-exchange approach.
The coatings doped with Zn/Al LDH-nanocontainers provide well-defined self-healing effect and confer
corrosion protection properties superior than currently used environmentally unfriendly chromate-based
systems.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction The anticorrosion inhibitors are added to polymer coatings in

The application of protective polymer coatings is the most
widespread approach used nowadays for corrosion protection of
different metallic materials. The main role of the anticorrosion
coating is to protect metal forming effective barrier against corro-
sive species present in different environments. The aging of the
polymer together with various mechanical impacts lead to forma-
tion of defects interrupting the barrier and providing direct ingress
of the corrosive species to naked metal surface [1]. Also, exposure
of these coatings to aqueous electrolyte solutions causes many
coatings to swell and to develop conductive pathways not present
in the coating before the exposure. After corrosion started the poly-
mer coating itself cannot protect the defective zone and is not able
to stop propagation of the defect. Therefore, an active ‘‘self-heal-
ing” of defects in coatings is necessary to provide long-term pro-
tection effect and to prolong the maintenance intervals [2].
* Corresponding author. Tel.: +351234370255; fax: +351234378146.
E-mail address: mzheludkevich@ua.pt (M.L. Zheludkevich).
order to provide additional active corrosion protection and to hin-
der the corrosion activity in defect sites [3,4]. However, the normal
inhibiting pigments are prone to uncontrollable leaching of an ac-
tive component leading to fast exhausting of self-healing potential
and to osmotic blistering of polymer films [5]. Even chromates, the
most used in past, can cause such problems. Moreover, due to very
high carcinogenic potential of chromates, they are banned since
2007. Only aeronautical industry is allowed to use chromate-based
systems until appropriate solution will be found. Thus develop-
ment of new active corrosion protection systems with self-healing
ability becomes now a very important challenging issue for many
industries.
Several new approaches based on encapsulation of inhibiting
compounds before addition of them to corrosion protection system
have been recently suggested [6]. Porous oxide interlayer applied
to the metal surface and doped with organic corrosion inhibitor
provides additional active corrosion protection for thin hybrid
sol–gel films on an aluminium alloy substrate [7,8]. The inhibi-
tor-containing oxide nanoparticles introduced to the hybrid coat-
ing were also used as nano-carriers of corrosion inhibitor [9].

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.10.020
 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611
Yang and van Ooij encapsulated triazole inhibitor using plasma
polymerization to produce PP-perfluorohexane and PP-pyrolle lay-
ers employing RF plasma discharge [10]. The plasma-treated tria-
zole was used as a pigment in a water-based epoxy coating,
slowly releasing the inhibitor and providing a long-term corrosion
protection. In both cases the release of the inhibitor from the
capsule is possible only when it is mechanically damaged. The
damaged capsule releases the entire active agent very fast in a
non-controllable way.
A very interesting alternative which allows a controllable leach-
ing triggered by a corrosion related stimuli is the use of Layer-by-
Layer (LbL) assembled shells. Nanocontainers with regulated
storage/release of the inhibitor can be constructed with nanome-
ter-scale precision employing the layer-by-layer deposition
approach [11]. The possibility to create such a smart self-healing
anticorrosion coating based on LbL assembled nanocontainers
has been recently demonstrated by Zheludkevich et al. [12–14].
The storage of corrosion inhibitors in the polyelectrolyte multilay-
ers has two advantages: isolation of the inhibitor avoiding its neg-
ative effect on the integrity of the coating and providing of an
intelligent release of the corrosion inhibitor regulating the perme-
ability of polyelectrolyte assemblies by changing local pH due to
started cathodic and anodic corrosion processes. Thus, a ‘‘smart”
coating containing polyelectrolyte containers can detect the begin-
ning of the corrosion and start the self-healing process in the
corrosion defect [15]. However, these developments are still in
lab-scale and too far from industrialization due to complex
technologies involved.
Another possibility recently reported is the use of ion-exchange
clays as reservoirs of corrosion inhibitors. Inhibiting inorganic cat-
ions can also be incorporated as exchangeable ions associated with
cation-exchange solids [16–18]. The advantage of this approach is
that the cation-exchange pigment is completely insoluble avoiding
osmotic blistering. Calcium (II) and cerium (III) cation-exchanged
bentonite anticorrosion pigments were prepared by exhaustive ex-
change of naturally occurring Wyoming Bentonite and used then
as anticorrosion pigments [18].
The anion-exchange pigments can also be used to immobilize
anionic inhibitors [19–23]. The release of inhibitor anions can be
provoked in this case by exchange with aggressive corrosive chlo-
ride ions. The anion-exchange pigment can play a double role
absorbing the harmful chlorides and releasing the inhibiting ions
in response. Even only the ‘‘trap” function can already provide
the additional anticorrosion effect in filiform corrosion tests when
non-inhibited pigments with carbonates and sulfates are used in
organic coatings [23]. Absorption of chlorides from an aggressive
electrolyte in a vicinity of a defect decreases the aggressiveness
of the corrosive medium, and thereby reduces the rate of the
corrosion processes. The use of an inhibiting anion-exchanged
pigment additionally can confirm the active feed-back conferring
a self-healing ability.
Layered double hydroxides (LDHs), also known as anionic clays
or hydrotalcite (HT)-like compounds, are typical anion-exchange
materials consisting of stacks of positively charged mixed metals
hydroxide layers between which anionic species and solvent mol-
ecules are intercalated. The hydrotalcite layers were demonstrated
to offer an anticorrosion protection even when applied as a surface
conversion films on Mg alloys [24]. Buchheit et al. synthesized
decavanadate-intercalated Al–Zn LDH pigments and added them
to the polymer coatings applied to AA2024 aluminium alloy
[21,22]. Results of the corrosion tests illustrate an additional corro-
sion protection by the hydrotalcite-like pigment due to the deca-
vanadate release, accompanied by the uptake of the chloride ions
in the exchange reaction. The ability of HT-like compounds to act
as a generic anion delivery system creates a possibility to immobi-
lize organic anion inhibitors intercalating them between hydroxide
603
layers [25]. A hydrotalcite pigment doped with benzotriazolate,
ethyl xanthate, and oxalate anions was developed and tested in
terms of inhibiting efficiency in respect to filiform corrosion on
organic coated AA2024. Inhibitor efficiency increases in the order
ethyl xanthate < oxalate < benzotriazole. However, it is not as
efficient as chromate-based pigment and its practical usefulness
remains unproven. Nevertheless, HT-like pigments doped with
organic inhibitor anions appear worthy of further investigation as
inhibitors for self-healing anticorrosion coatings.
The main goal of this paper is to develop inhibitor-containing
LDH-nanocontainers which can be added to the commercial paint
formulations for aeronautical applications. Two types of LDH nano-
pigments were synthesized in the present work using two different
approaches, namely, the direct synthesis in the presence of corro-
sion inhibitor and the anion exchange of precursor NO3 -contain-
ing LDH in inhibitor solution. Zn/Al and Mg/Al nanocrystalline
LDHs pillared with divanadate anions were tested as possible
anticorrosion inhibiting pigments in the chloride-containing elec-
trolyte. In contrast to decavanadates, metavanadates have been re-
cently proven to be better corrosion inhibitors [26].
2. Experimental
2.1. Synthesis of layered double hydroxides intercalated with vanadate
All the chemicals were obtained from Aldrich, Fluka and Riedel-
de Häen, with P98% of ground substance, and used as received.
In the present work two strategies of LDHs synthesis were as-
sessed. The principal strategy for the preparation of pillared LDHs
is based on conventional anion exchange. Another approach (the
direct synthesis by precipitation in the presence of the pillaring an-
ion) has been also described previously for vanadate-containing
LDHs, but the structure of the obtained compounds was found to
depend strongly on the preparation conditions [27,28]. The LDH
samples in the present paper are designated ZnXAlY or MgXAlY,
where X stands for the nominal Zn/Al or Mg/Al atomic ratio and
Y for the interlayer anion.
In the direct synthesis of Zn2AlVO3 LDH, 0.050 M of Zn(NO3)2

6H2O and 0.025 M of Al(NO3)3
9H2O were dissolved in 100 ml of
deionized water. This solution was then added dropwise to
200 ml of 0.25 M NaVO3 solution (pH of this solution was adjusted
to 9.5) under vigorous stirring by a magnetic stirrer. The pH of the
slurry was held constant at 9.5 ± 0.3 during the synthesis by the
addition of 2 M NaOH solution. The addition was over 90 min
and the reaction mixture was kept at 25 ± 1 °C. To exclude the
CO2 presence, purified argon was preliminarily purged through
all solutions for 1 h and Ar was bubbled through the slurry during
the synthesis. Carbonate-free water obtained by boiling deionized
water was used for the solution preparation. The formation of a
yellow–orange precipitate was observed during the synthesis. A
half of the resultant slurry was centrifugated and washed four
times with carbonate-free distilled water (this sample will be de-
signed as ‘as-deposited’). Another part of the slurry was kept at
65 °C for 24 h in a closed Ar-purged vessel for crystallization of
the LDH and then was also centrifugated and washed (this sample
will be designed as ‘after heating at 65 °C’). Then the washed pre-
cipitates were frozen and dried under vacuum in a freeze dry sys-
tem (Labconco Co.). Mg2AlVO3 LDH was prepared using the similar
procedure but Mg(NO3)2
6H2O was used as a starting reagent.
In the second method, the vanadate-pillared LDHs were pre-
pared by anion exchange from precursor nitrate-containing LDHs.
Nitrate was chosen as the gegenion due to the relative ease with
which the nitrate anions can be displaced from the interlayer.
The procedure of synthesis of the precursor Zn2AlNO3 LDH was
similar to that described above, but instead of 0.25 M NaVO3
604 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611
solution, 0.25 M NaNO3 solution with the pH adjusted to 10 was
used. The pH of the slurry was held constant at 10 ± 0.3 during
the synthesis. The resultant slurry was kept at 65 °C for 24 h in a
closed Ar-purged vessel for crystallization of the LDH particles
and then was centrifugated and washed four times with carbon-
ate-free deionized water. To diminish the mean size of LDH parti-
cles, the gel obtained after final centrifugation was ultrasonically
treated for 30 min after addition of a small amount of deionized
water. For the anion-exchange reaction, 0.1 M NaVO3 deaerated
solution (pH 8.4) was prepared, with the total amount of VO3 an-
ions within the solution being double the theoretical value re-
quired to balance the positive charge of the layers in the treated
LDH. This solution was divided into two portions. First portion
was added to total amount of the prepared precursor Zn2AlNO3
LDH and the suspension was held for 24 h with a constant stirring.
The reaction products were then isolated and washed as described
above. Then the second portion of 0.1 M NaVO3 solution was added
to the precipitate and the procedure of replacement was repeated.
Finally the washed pale yellow precipitate was frozen and dried
under vacuum in a freeze dry system.
2.2. Coating and substrate preparation
Before immersion tests in LDH-loaded and pure 0.05 M NaCl
solutions, the aluminium alloy 2024 substrates were cleaned and
etched according to the standard commercial procedure (alkaline
cleaning in Metaclean T2001 at 68 °C for 25 min, alkaline etching
in Turco Liquid Aluminetch N2 at 60 °C for 45 s, acid etching in Tur-
co Liquid Smutgo NC at 30 °C for 7 min each followed by washing
in distilled water).
The paint used in this study was a non-inhibited water-based
epoxy-primer (Mankiewicz SEEVENAX, thickness 25 lm) and a
water-based epoxy topcoat (thickness 30 lm). The primer was
doped with inhibitors (LDH-nanocontainers or strontium chromate
pigment) in amounts of 10 wt.% inhibitor in dry coating.
Before the application of polymer coating, tartaric sulphuric
acid (TSA) anodising was carried out after acidic pickling of the
AA2024 samples followed by a final rinse. The anodising parame-
ters were set to obtain a coating thickness of 3 lm. The concentra-
tion of tartaric acid and sulphuric acid in the electrolyte was 80 and
40 g/l, respectively. The anodising process was carried out at a volt-
age of 14 ± 1 V for 25 min in a temperature range of 37–43 °C.
The paints were sprayed with a Sata Jet 2000 HVLP Digital spray
pistol using 4.5 bar on a 1.3 spray valve. The primers and top coats
were mixed with the curing agents according to the technical data
sheets. After applying the primer system, the top coat was depos-
ited within 24 h afterwards. Then the samples were stored at room
temperature for 72 h before the tests were carried out.
2.3. Examination methods
Electrochemical impedance spectroscopy (EIS) measurements
were carried out at room temperature in a three-electrode cell con-
sisting of a saturated calomel reference electrode, a platinum foil as
the counter electrode and the working electrode with a horizontal
position and an exposed area of appr. 3 cm2. The cell was placed in
a Faraday cage to avoid any interference with external electromag-
netic fields. The working electrolyte in the cell (volume – 10 ml)
was quiescent and in equilibrium with air. The EIS measurements
were performed using a Gamry FAS2 Femtostat with a PCI4 Con-
troller in a frequency range from 5  104 to 7  10 5 Hz with a step
of 7 points per decade. All the spectra were recorded at open circuit
potential with applied 10 mV sinusoidal perturbation. The imped-
ance plots were fitted using different equivalent circuits by means
of the Elchem Analyst software from Gamry.
Scanning electron microscopy (SEM) observations coupled with
Energy dispersive analysis (EDS) were performed on Hitachi S-
4100 system with an electron beam energy of 25 keV. X-ray dif-
fraction patterns were obtained from powder samples using Riga-
ku D/Max-B diffractometer (Cu Ka radiation). Zn, Al and V
elemental chemical analyses and determination of the concentra-
tion of released zinc, magnesium and vanadate ions were per-
formed by the method of successive additions using flame atomic
absorption spectroscopy (Perkin Elmer AAS model 3100). For
chemical analysis the LDH powders were dissolved in 1 M HCl
solution.
Filiform corrosion test (FFT) was performed according to EN ISO
3665. After initiation with concentrated HCl according to EN ISO
3665, the samples are placed in the test chamber at an angle of
6° from the vertical. The samples are inspected within 30 min after
removal from the test chamber. The degree of filiform corrosion is
rated by counting the filiform sites of different size categories. The
maximum length of filiform site is noted. In occurrence of blisters
or delamination, the number and size of failure are recorded. Mac-
roscopic pictures of the samples were taken at each inspection.
Two samples per specimen type were tested. Inspections were
made after 336 and 960 h.
Salt spray test (SST) was performed according to ISO 9227. The
samples are supported in holders at an angle of 15° from the ver-
tical. For inspections, samples are washed with deionized water,
dried with nitrogen and examined within 30 min after removal
from the chamber.
Q-Panel condensation test (QCT) was carried out at 41 °C: con-
tinuous condensation without dry off according to ASTM D 4585–
99. The surface of the test specimens was examined for blistering
according to ISO 4628–2.
3. Results and discussion
3.1. LDH structure
XRD and elemental chemical analysis were used to verify the
results of LDH synthesis. The XRD patterns of the synthesized
LDH powders are shown in Fig. 1. All diffractograms demonstrate
the typical pattern of a hydrotalcite-type clay, the structure of
which consists of layers of mixed Me(II)–Me(III) hydroxide sepa-
rated by layers of anions and water molecules. The most intensive
peaks of the LDH diffractograms in the range of 2H values between
4° and 35° originate from diffraction on these hydroxide layers.
XRD pattern shown in Fig. 1b (curve 1) corresponds to precursor
Zn2AlNO3 LDH and shows well-defined peaks at 9.86°, 19.92°
and 30°, which can be ascribed to diffraction by planes (003),
(006) and (009). The unit cell height calculated using (003) peak
position is 8.96 Å. This corresponds to a gallery height (anion layer
thickness) of 4.19 Å, assuming a thickness of 4.77 Å for the cationic
sheets (brucite-like layers) [29]. This gallery height is slightly high-
er than the diameter of NO3 anion (3.78 Å) and can be attributed
to the vertical alignment of NO3 planar groups with respect to the
host layer [30]. Presence of water molecules in the gallery may
cause some increase in the interlayer spacing. Similar XRD pattern
(Fig. 1a, curve 1) was also obtained for Mg2AlNO3 LDH because the
ionic radii of Mg2+ (0.72 Å) and Zn2+ (0.74 Å) are close.
After the procedure of anion exchange of nitrate anions for van-
adate ones the peak positions on the XRD pattern of LDH are chan-
ged (Fig. 1b, curves 1 and 4). Comparison of these two diffrac-
tograms clearly indicates that the gallery height increases from
4.19 Å (d(003) = 8.96 Å) to 4.81 Å (d(003) = 9.22 Å) as NO3 ions are
replaced by vanadate ones. No residual reflections corresponding
to the nitrate-containing LDH are evident after anion exchange,
indicating complete exchange. Since the polymerization degree of
 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611
Fig. 1. X-ray diffraction patterns of Mg–Al (a) and Zn–Al LDHs (b): nitrate-
intercalated LDHs (curve 1), vanadate-intercalated LDHs obtained by direct
synthesis (curve 2 – as deposited, curve 3 – after heating at 65 °C) and by anion
exchange (curve 4).
oxovanadates is pH-dependent, changes in the pH are expected to
result in species with different polymerization degrees incorpo-
rated into the gallery. We performed the anion exchange proce-
dure at pH 8.4. Under these pH conditions for a 0.1 M aqueous
vanadate solution, the predominant oligovanadate species in the
reaction mixture are V2O74 and HV2O73 [31]. The V2O74 anions
are composed of two VO4 tetrahedra (VO3–O–VO3) sharing a ver-
tex, and in the interlayer gallery, two different arrangements are
possible [28,32], one with anion is standing up (perpendicular to
the brucite-like layers) and another with anion is lying down (par-
allel to the layers). Taking into account that the expected gallery
heights for the V2O74 anion corresponding to the perpendicular
arrangement and to the parallel one are 7.8 and 5.0 Å [33], we
can conclude that in the synthesized vanadate-containing LDHs,
the anions should be in parallel arrangement.
XRD patterns of vanadate-containing LDHs prepared by direct
synthesis demonstrate significantly less intensive and wider reflec-
tions as compared with those obtained by anion exchange, indicat-
ing that these LDHs have a smaller size of crystals and probably
also include an amorphous phases (Fig. 1). Additional heating of
the LDH suspension after synthesis leads to an increase in the
Table 1
Elemental analysis data for different vanadate-intercalated LDHs.
Sample Content, wt.%
Mg or Zn
exp. theor.
Mg2AlVO3 (direct synthesis) 12.34 15.55
Zn2AlVO3 (direct synthesis) 26.74 33.12
Zn2AlVO3 (after replacement) 32.96 33.12
605
relative intensity of the reflections originating from the layered
structure (compare curves 2 and 3 in Fig. 1a and b). The average
size of LDH nanocrystallites was estimated using Sherrer’s equa-
tion and found to be 14 ± 2 nm for Zn2AlVO3 LDH obtained by an-
ion exchange, and 9 ± 3 nm for Mg2AlVO3 and Zn2AlVO3 powders
prepared by direct synthesis.
Elemental analysis data for the synthesized LDHs are summa-
rized in Table 1. Theoretical values of the metal content were cal-
culated for the LDH formula Me2Al(OH)6VO3
2H2O, where Me is Mg
or Zn. For the Zn2AlVO3 LDH obtained by anion exchange, the
experimental content of metals and the Zn/Al and V/Al atomic ra-
tios are close to the theoretical values. At the same time, for the
Mg2AlVO3 and Zn2AlVO3 powders prepared by direct synthesis,
the atomic ratios of Mg/Al or Zn/Al are less than the theoretical val-
ues. The V/Al ratio in these powders is slightly higher as compared
with the theoretically expected one. These results indicate that the
LDH powders obtained by direct synthesis have a more disturbed
structure and may include an admixture of amorphous aluminium
vanadates.
Fig. 2 shows typical SEM micrographs of the LDH particles
deposited on a single crystal silicon substrate from LDH suspen-
sions. As-deposited Mg2AlVO3 and Zn2AlVO3 products prepared
by direct synthesis consist of agglomerates of finest globular parti-
cles (Fig. 2a and c). Heating of these products at 65 °C for 1 day
leads to appearance of leaf-like nanocrystals (Fig. 2b and d). Unlike
these patterns, the precursor nitrate-containing LDHs and the van-
adate-pillared LDHs obtained by anion exchange demonstrate the
well-defined crystalline structure with thin and rather broad
plate-like crystals (Fig. 2e and f).
3.2. Ion-exchange properties of vanadate-containing LDH powders
As mentioned previously, LDHs are anion-exchange compounds
and the inhibiting anions such as vanadate anions can be ex-
changed by the corrosion-active ions such as chlorides present in
the aggressive environment. Moreover, some metal cations present
in LDHs can offer additional inhibiting effect on Al alloys.
Ion-exchange capacities of the synthesized vanadate-loaded
LDHs were assessed according to the following procedure. A defi-
nite amount of the LDH powder (50 mg) was accurately weighted
and added to 10 ml of 0.05 M NaCl aqueous decarbonated solution.
The suspension was agitated for 24 h at 25 °C to reach an ion-ex-
change equilibrium, then centrifuged at 10,000 rpm and the equi-
librium concentrations of vanadate and Mg2+ or Zn2+ ions in the
supernatant were determined by AAS method. To study the kinet-
ics of vanadate anion release, the LDH suspension was agitated for
a definite time followed by centrifugation.
The results of ion release studies on different LDHs in neutral
aqueous NaCl solutions are shown in Table 2 and Fig. 3. As can
be seen from Table 2, under these conditions the highest concen-
tration of released vanadate anions can be reached for Mg2AlVO3
LDH prepared by direct synthesis. In the case of Zn2AlVO3 LDHs,
significantly better anion-exchange properties were found for the
sample prepared from nitrate-containing precursor in comparison
with directly synthesized LDH. For former, appr. 0.68 mmol l 1 of
Atomic ratio
Al V Mg/Al or Zn/Al V/Al
exp. theor. exp. theor. exp. theor. exp. theor.
8.17 8.63 17.52 16.30 1.68 2 1.14 1
5.96 6.84 12.48 12.90 1.85 2 1.11 1
6.92 6.84 12.68 12.90 1.97 2 0.97 1
606 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611

Fig. 2. SEM micrographs of the LDH particles: (a) Mg2AlVO3 prepared by direct synthesis (as deposited); (b) Mg2AlVO3 prepared by direct synthesis (after heating at 65 °C);
(c) Zn2AlVO3 prepared by direct synthesis (as deposited); (d) Zn2AlVO3 prepared by direct synthesis (after heating at 65 °C); (e) Zn2AlNO3 (after heating at 65 °C); (f)
Zn2AlVO3 prepared from Zn2AlNO3 by anion exchange.

vanadate anions was detected in supernatant solution after centri-
fugation which corresponds to the release of 5.4% VO3 ions con-
taining in the LDH. Zn2+ release was also found for zinc-
containing LDHs, but the released percent of Zn2+ is essentially less
in comparison with vanadate one (Table 2). Moreover, a higher
fraction of Zn2+ was released from directly synthesized Zn2AlVO3
LDH as compared with the LDH obtained by replacement. We
found a relatively high concentration of Mg2+ in solutions after
contact with Mg2AlVO3 LDH (Table 2). This effect may be associ-
ated with dissolution of some magnesium salts present in Mg2Al-
VO3 LDH, prepared by direct synthesis, as an admixture.
Fig. 3 shows the evolution of vanadate anion concentration in
solution during immersion of the replacement-prepared Zn2AlVO3
LDH powder in 0.5 M NaCl solution. The vanadate release from the
LDH proceeds rapidly (during first several hours); after 20 h there
is no significant variation in the anion concentration because of the
attained chemical equilibrium. Here it is important to note that if
we add the Zn2AlVO3 LDH powder used in the first release exper-
iment again in a fresh portion of 0.5 M NaCl solution, the release of
vanadate anions is again observed with slightly lower saturation
limit. In the second release experiment the saturation concentra-
tion is 60% and in the third experiment – 42% of that observed in

Table 2
Results of ion release studies for different vanadate-intercalated LDHs in 0.05 M NaCl (50 mg of LDH per 10 ml of chloride solution).
1
Sample Released ion concentration in solution, mmol l Ratio of the released ion amount to the total ion amount in LDHs
2+ 2+
Mg or Zn VO3 Mg2+rel/Mg2+tot or Zn2+rel/Zn2+tot VO3 rel/VO3 tot

Mg2AlVO3 (direct synthesis) 0.89 1.28 0.035 0.074

Zn2AlVO3 (direct synthesis) 0.012 0.16 0.0006 0.013
Zn2AlVO3 (after replacement) 0.0047 0.68 0.0002 0.054
 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611
Fig. 3. Vanadate release kinetics from Zn2AlVO3 LDH, prepared by replacement,
into 0.5 M NaCl aqueous solution (pH 7).
the first experiment. This indicates that the exchange reaction is
chemical in nature and the vanadate concentration in solution is
governed by ion-exchange equilibrium rather than solubility
equilibrium.
3.3. Inhibiting activity of vanadate-containing LDH-based
nanocontainers
The developed Zn2AlVO3 and Mg2AlVO3 nanocontainers were
tested from standpoint of the corrosion inhibition offered to
Fig. 4. Impedance spectra of AA2024 samples taken after 1 h, 1 day, 1 and 2 weeks of immersion in 0.05 M NaCl without additives (d) and with addition of a powder of
different LDHs (50 mg per 10 ml of solution): (a) Mg2AlVO3 prepared by direct synthesis; (b) Zn2AlVO3 prepared by direct synthesis; (c) Zn2AlVO3 prepared from Zn2AlNO3
by anion exchange.
607
aluminium alloy 2024. The tests were performed in 0.05 M NaCl
electrolyte loaded with the synthesized pigment (50 mg per
10 ml of solution). The suspension was agitated before testing,
and the electrolyte was quiescent during the test. Electrochemical
impedance spectroscopy was used during the immersion tests to
assess condition of the alloy surface and degree of the corrosion
impact. Fig. 4 presents Bode plots taken after different immersion
times in pure sodium chloride solution and in solutions loaded
with different nanocontainers under study. At the beginning of
test, only one broad time constant can be observed on the spectra
obtained in the nanocontainer-containing electrolytes. This relaxa-
tion process originates from the capacitance of the dense oxide
film present on the surface of aluminium alloy. Only the first signs
of another time constant can be revealed at low frequencies. This
weak-defined pick can be attributed to the started corrosion attack.
The high impedance values at low frequencies demonstrate passive
character of the oxide film. In the case of the samples tested in pure
NaCl solution without any pigments, situation is different. After
only 1 h the Bode plots already show two well-defined time con-
stants related to the oxide and to corrosion process, respectively.
The impedance values at low frequencies are 1.5 orders of magni-
tude lower than those for the samples tested in the nanocontainer-
containing electrolyte. Moreover, the impedance values drop very
fast during 7 days of immersion demonstrating rapid degradation
of the alloy surface and strong corrosion impact. Further immer-
sion leads to a slight increase of impedance associated with devel-
opment of a diffusion barrier layer formed by corrosion products.
The impedance values for the alloy immersed in pigment-contain-
ing electrolytes show much more stable behavior, especially in the
608 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611
case of Zn2AlVO3 LDHs. The highest low-frequency impedance was
observed in the case of Zn2AlVO3 LDH prepared by anion exchange,
showing values above 1 MOhm cm2 even after 2 weeks of immer-
sion. This is almost 10 times higher than the impedance in the case
of the Mg2AlVO3 LDH.
The EIS results are in good accordance with visual observation
of the immersed samples as shown on optical photos taken after
completing the tests (Fig. 5). The sample immersed for 2 weeks in
Mg2AlVO3-containing electrolyte is covered with dark film and
has several pitting-like defects on the surface. Coloration of the
alloy surface tested in the presence of Zn2AlVO3 LDH prepared
by direct synthesis is sufficiently less pronounced but two small
defects are still present on the sample surface. Both mentioned
specimens demonstrate a sufficiently lower corrosion impact as
compared to the AA2024 immersed in LDH-free NaCl solution.
The last sample (Fig. 5d) is completely corroded and covered with
a thick layer of corrosion products. The best performance was ob-
served in the case of Zn2AlVO3 LDH prepared by anion exchange.
In this case the alloy surface is intact without any defects. Only
slight darkening of the specimen is evident due to the formation
of a passive oxide film.
The EIS tests and the visual observations show superior inhib-
iting performance of Zn2AlVO3 LDHs in comparison to Mg2AlVO3
ones, although the latter demonstrate an enhanced release of
vanadate anions. This effect may be due to a synergetic inhibi-
tive action of both vanadate and Zn2+ ions [21]. Comparison of
the Zn2AlVO3 LDHs obtained by different methods showed
better performance of replacement-prepared Zn2AlVO3 LDH.
Therefore, this best LDH powder was selected to be tested as
corrosion inhibiting pigment in commercial aeronautical paint
formulation.
Fig. 5. Photos of AA2024 samples after 2-week immersion in 0.05 M NaCl without additives (d) and with addition of different LDHs (50 mg per 10 ml of solution): (a)
Mg2AlVO3 prepared by direct synthesis; (b) Zn2AlVO3 prepared by direct synthesis; (c) Zn2AlVO3 prepared from Zn2AlNO3 by anion exchange.
3.4. EIS measurements on painted AA2024 samples
The commercial primer modified with Zn2AlVO3 LDH-nanocon-
tainers was applied to anodized aluminium alloy panels as de-
scribed in Section 2. Two reference samples were also prepared.
One sample was coated with undoped commercial primer and
the second one with commercial primer containing chromate-
based pigment. All three systems were over painted with undoped
top coat and immersed in 0.5 M NaCl solution.
Fig. 6a presents impedance spectra of three coated systems
after 4 months of immersion in 0.5 M NaCl. Two main capacitive
regions can be detected on Bode plots at low and high frequencies
being separated by a resistive plateau at about 1 Hz. The high-fre-
quency part can be associated with the capacitance of polymer
coatings. Two relaxation processes can be revealed on EIS spectra
in this region because of the response from two polymer coating
layers deposited on the anodized alloy. The low-frequency part is
ascribed to the response of a dense oxide film formed on the alloy
surface. This oxide layer is a last barrier for corrosive species before
reaching the alloy surface. Thus the resistance of this layer is very
important from standpoint of corrosion protection. To estimate the
parameters of different components of the protective system after
long immersion test, the impedance spectra were fitted using
equivalent circuit depicted in Fig. 6b.
The results of fitting are depicted as solid lines demonstrating a
good quality of fitting as shown in Fig. 6a. The calculated oxide film
resistance is maximal for the sample coated with LDH-containing
primer (2.4 GOhm cm2). It is slightly higher than that of the chro-
mated specimen (1.9 GOhm cm2) and is almost two times above
the resistance of oxide for alloy coated with undoped primer
(1.4 GOhm cm2). The high resistance of the oxide film suggests that
 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611 609

water and chloride uptake. LDH-containing coating demonstrates

sufficiently better stability of barrier properties and keeps one or-
der of magnitude higher values than the other coatings during
about 750 h.

3.5. Standard accelerated corrosion tests

The EIS results presented above demonstrate that the coating

Fig. 6. Bode plots of AA2024 samples, coated with primer and top coat without
additives, with chromate and with LDH particles Zn2AlVO3 prepared from
Zn2AlNO3 by anion exchange), taken after 4 months of immersion in 0.5 M NaCl.
Solid lines show the fitting results.
nanocontainer-containing coating confers additional active corro-
sion protection improving the stability of oxide layer and, in turn,
passive behavior of the coated alloy.
One can also mark the higher resistance of the coating after pro-
longed immersion in the case when Zn2AlVO3 LDH-nanocontainers
are added to the primer. Thus, the addition of Zn2AlVO3 powder
remarkably improves the long-term barrier properties of the
epoxy-primer. Fig. 7 presents the evolution of the coating resis-
tance in course of immersion for three samples under study. At
the commencement of immersion all coatings show nearly the
same resistance. However, it drops very fast during first days in
the case of undoped coating and coating with chromates due to
doped with LDH-nanocontainers performs in immersion corrosion
better than even traditional chromate-containing one. However,
immersion test not always correctly simulate conditions during
exploitation of coated structures. Therefore, additional standard
accelerated corrosion tests were carried out.
In neutral salt spray test, the best results after 2000 h were ob-
served on the samples coated with chromate pigment in the pri-
mer (not shown). The LDH-containing system and undoped
coating perform in similar way but with higher corrosion impact
than chromated one.
One of the important issues for aeronautical coatings on alu-
minium alloys is filiform corrosion which can propagate under
the coating leading to its fast deterioration. Filiform corrosion test
was conducted to estimate susceptibility of the coatings under
study toward the filiform attack. Two samples were tested per each
type of coatings. Table 3 summarizes the results of this test after
336 and 960 h. LDH-based coating and chromate-containing one
pass the aeronautical requirements (max length 2.2 mm after
960 h). The samples coated with undoped formulation have longer
filaments. The amount of defects is also higher in this case. Photos
of samples taken after 960 h are presented in Fig. 8. Corrosion at-
tack is maximal under undoped coatings. The appearance of verti-
cal scratch is very similar in the case of both inhibitor-containing
coatings. However, the horizontal scratch of chromated system is
sufficiently more attacked than in the case of LDH-containing coat-
ing. Thus the coating modified with nanocontainers confers the
best protection against filiform corrosion when compared to tradi-
tional commercial coatings.
Resistance to osmotic blistering is another very important point
for anticorrosion pigments is as it was already discussed above.
Condensation test was performed to check if coatings under study
suffer the osmotic blistering. Fig. 9 demonstrate all three coatings
after 1000 h of QCT test. The undoped coating and coating with
chromate pigment show only formation of very small blisters
which are not visible on the presented picture. However, the coat-
ing with nanocontainers is much more degraded after test demon-
strating single blisters all over the surface (Fig. 9c). One of the
reasons of the blistering may be the local alkalization of the metal
substrate in the presence of LDHs. This result demonstrates that
the problem of osmotic blistering still has to be solved when
LDH-nanocontainers are introduced to the polymer coating. It is
important to note that the detrimental effect arising from the local
alkalization in presence of LDHs can be neglected when the corro-
sive medium will be acidified.

Table 3
Results of filiform corrosion tests.

Sample 960 h 336 h

Max filament Amount Max filament Amount
length [mm] M1. . .M5 length [mm] M1. . .M5
Zn2AlVO3 LDH – 1 1.6 M3 1.0 M2
Zn2AlVO3 LDH – 2 2.0 M3 1.0 M2
Undoped – 1 2.3 M3–4 1.4 M2
Undoped – 2 2.5 M3 1.2 M3
Fig. 7. Time evolution of the pore resistance of top coat and primer layer without Chromate – 1 1.6 M3 0.7 M3
additives and with chromate and LDH additives, which were deposited on the Chromate – 2 1.9 M3 0.8 M3
AA2024 samples, during the immersion in 0.5 M NaCl.
610 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611

Fig. 8. Photos of AA2024 samples coated with undoped (a), chromate-containing (b) and LDH-doped (c) coatings after 960 h in filiform corrosion test.

Fig. 9. Photos of AA2024 samples coated with undoped (a), chromate-containing (b) and LDH-doped (c) coatings after 1000 h of QCT corrosion test.

4. Conclusions tive inhibition of corrosion processes on aluminium alloy 2024.

The new Mg/Al and Zn/Al LDH-nanocontainers doped with
divanadate anions as corrosion inhibitor are prepared in the present
work using direct synthesis and anion-exchange approaches. The
nanocontainers being added to corrosive media demonstrate effec-
The Zn/Al LDH prepared by anion-exchange method confers the best
active corrosion protection.
Addition of the Zn/Al LDH-nanocontainers to commercial pri-
mer used for aeronautical application leads to significant improve-
ment of the corrosion protection performance providing an
 M.L. Zheludkevich et al. / Corrosion Science 52 (2010) 602–611
additional active protection effect as shown by electrochemical
and accelerated corrosion tests. The developed LDH-nanocontain-
ers are promising candidates for substitution of chromate-based
anticorrosive pigments since they provide comparable or even
superior corrosion protection than the traditional chromates.
Acknowledgements
This work is supported by EU FP6 project ‘‘Multiprotect” NMP3-
CT-2005-011783 and EU FP7 project ‘‘MUST” NMP3-CP-IP 214261-
2. The authors acknowledge the financial support of Portuguese–
Brazilian collaborative program CAPES-GRICES (Contract No. 154/
06).
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