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1. Introduction
Aluminum and its alloy is one of the materials, which has an
important role in the engineering structures and its usage
ranking stands only behind the ferrous alloys. Some special
properties of this metal include: its strength, density ratio,
toughness, and corrosion resistance (Ref 1). To attain appropriate attributes, aluminum can be alloyed with different metals,
such as: magnesium, silicon, copper, zinc, iron, manganese,
lithium (Ref 2-4). Aluminum alloy AA2024 is used greatly in
aerospace industries because of its excellent mechanical
properties and low density (Ref 5, 6). Materials such as copper,
magnesium, zinc, and iron in this alloy decrease the corrosion
resistance signicantly due to the formation of the intermetallic
compounds (IMCs) (Ref 7-11). Pure aluminum has a good
corrosion resistance due to the formation of a strong oxide
layer, but AA2024 involves IMCs which form small galvanic
cells in aluminum matrix and lead to localized corrosion
(Ref 12-15). One way to increase the corrosion resistance and
protect these alloys is coatings. Conversion coatings are an
important group of these coatings which usually have a thin
thickness, provide corrosion protection and enhance the
adhesion between different coating layers (Ref 16, 17). Chromate conversion coatings (CCCs) are the most common and
effective anti-corrosive treatments for aluminum alloys
(Ref 17-19). Although CCCs provide a great corrosion resistance, they are toxic and carcinogenic due to the presence of
hexavalent chromium; therefore, these coatings are under strict
regulations (Ref 20, 21). Due to the toxicity of Cr6+, several
studies have been done on the replacements for CCCs and the
extension of non-toxic coatings (Ref 22). Silicate conversion
coatings are one of the best superior alternatives for the CCCs
(Ref 23, 24). These coatings have a good durability against
each kind of corrosion and are safe for the humans and
environment (Ref 23, 25, 26). Many studies showed that the
silicate coatings provide good corrosion resistance for the
substrate metals (Ref 27-31). Alkali silicates are common and
general group of silicate coatings. Alkali silicate solutions
contain two fractions: (a) alkali ions, hydroxide ions, and
silicate ions (SiO44), (b) polymerized (colloidal) fractions. The
very large polymerized particles are a complex mixture of
polysilicate anions and their hydroxylated surfaces which
consist of silanol (-Si-OH) groups and siloxane bridges (-Si-OSi-). During the drying process, polymerization continues and
more silanol groups are converted to the siloxane bridges. The
produced layer on the substrate increases the corrosion
resistance (Ref 32-34). However, pristine silicate conversion
coatings are still permeable to corrosive agents such as water,
oxygen, and destructive ions like Cl, H+, SO42. This is due
to the porous structure of conversion coatings which lead to
increasing the susceptibility to pitting corrosion. In order to
enhance the barrier properties of these conversion coatings,
various methods and additives have been used by a great
number of researchers (Ref 23, 25, 28, 34). Min et al. (Ref 23)
studied the effect of potassium methyl siliconate on the anticorrosion properties of the silicate conversion coating on
galvanized steel. They veried that the addition of potassium
methyl siliconate into silicate coatings increased the corrosion
protection ability of coatings due to the formation of the more
hydrophobic surface. The substantial concentration of K ion at
the coating surface was decreased by the addition of potassium
methyl siliconate which decreased the hydrophobic properties.
2.1 Materials
Aluminum alloy 2024 was purchased and the major alloying
elements are: Cu: 3.8-4.6, Mg: 1.3-1.6, Mn: 0.5-0.8, Si: < 0.5,
Fe: < 0.5, Zn: < 0.25, Ti: < 0.15, Cr: < 0.1, V: < 0.05, Zr:
< 0.05, others: < 0.15%wt and Al: Rest. Samples were
subjected to mechanical polishing with sand papers of 400 to
2000 grades, and cleaned with acetone. To remove any trace of
surface oxides, the samples were immersed in NaOH for 30 s
and then immersed in dilute H2SO4 solution for 30 s. Between
each step, the panels were rinsed with deionized water.
A 40 wt.% aqueous solution of potassium silicate with
silicate/alkali molar ratio of 2 was prepared from the Iran Silis
Company. A 30 wt.% aqueous solution of colloid nano-silica
with 20-30 nm particle size was prepared from Iranian
Nanomaterials Pioneers. Different concentrations of potassium
silicate solution and nano-silica colloidal solution were mixed
and different silica ratios, 2:11, 2:16, 2:22, 2:33, and 2:44, were
provided. Silicate conversion coatings were obtained by dip
immersion method. Aluminum samples were immersed for
400 s in prepared water-based coating solution in different
silica ratios, and the coated samples were cured in oven at
150 C for 30 min. The coated samples were stored at room
temperature for 1 h.
Table 1 Electrochemical parameters of the silicate coatings in 3.5 wt.% NaCl solution
Samples
Ecorr, V
Icorr, A/cm2
ba, V/dec
bc, V/dec
R p, X
Vcorr, mm/y
Bare
1M
2M
3M
0.668
0.609
0.572
0.617
8.47 9 107
4.19 9 107
1.45 9 108
4.11 9 109
0.005
0.095
0.03
0.17
0.012
0.113
0.144
0.151
1.82 9 103
5.34 9 104
7.39 9 105
8.46 9 106
4.14 9 103
4.92 9 103
1.71 9 104
4.16 9 105
Coatings were obtained from different concentrations of potassium silicate solution in ratio 2
Fig. 2 SEM images of silicate coated AA2024 sample after polarization test. Silicate conversion coating was obtained from (a) 1 M and
(b) 3 M potassium silicate solution. Some pits are shown in this gure
Rp
ba bc
1
:
2:303ba bc Icorr
Table 2 Electrochemical parameters of the silicate coatings in 3.5 wt.% NaCl solution
Samples
Ecorr, V
Icorr, A/cm2
ba, V/dec
bc, V/dec
R p, X
Vcorr, mm/y
0.5 M
1M
2M
3M
0.985
1.083
1.142
1.225
6.09 9 109
9.93 9 1010
3.17 9 109
8.98 9 109
0.138
0.096
0.252
0.209
0.087
0.212
0.285
0.257
3.80 9 106
3.07 9 107
1.82 9 107
5.57 9 106
3.76 9 105
2.46 9 105
3.22 9 105
5.05 9 105
Coatings were obtained from different concentrations of potassium silicate solution in ratio 2.16
Table 3 Electrochemical parameters of the silicate coatings in 3.5 wt.% NaCl solution
Samples
Ecorr, V
Icorr, A/cm2
ba, V/dec
bc, V/dec
R p, X
Vcorr, mm/y
Ratio
Ratio
Ratio
Ratio
Ratio
0.609
1.079
1.132
1.082
1.235
4.19 9 107
3.88 9 109
8.93 9 1010
1.26 9 1010
1.74 9 109
0.095
0.114
0.115
0.066
0.04
0.113
0.265
0.347
0.085
0.259
5.34 9 104
8.91 9 106
4.19 9 107
1.28 9 108
0.96 9 107
4.92 9 103
4.56 9 105
1.17 9 105
1.48 9 106
2.04 9 105
2
2:11
2:22
2:33
2:44
Fig. 6 Electrochemical impedance spectroscopy diagrams of potassium silicate coatings in 3.5 wt.% NaCl solution. (a) Coatings were
obtained from 1 M potassium silicate solution and ratio 2. (b) Coatings were obtained from 1 M potassium silicate solution in different
ratios: (1) 2:11, (2) 2:22, and (3) 2:33
Table 4 EIS parameters of the silicate coatings in 3.5 wt.% NaCl solution
Sample
Ratio
Ratio
Ratio
Ratio
2
2:11
2:22
2:33
Rs, X
Rct, X
Qdl, F
17
18
18
16
9.2 9 105
3.2 9 107
5.3 9 107
1.4 9 108
7 9 105
3 9 107
2 9 108
4 9 108
0.80
0.75
0.83
0.83
Fig. 8 (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating obtained from 1 M potassium silicate with ratio 2
Fig. 9 (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating obtained from 1 M potassium silicate with ratio
2.16
Weight% of Si
Weight% of K
Weight% of O
29.76
33.85
30.58
18.75
16.67
13.15
51.49
49.48
56.27
Fig. 10 (a) SEM and (b) EDX analysis of the potassium silicate
conversion coating obtained from 1 M potassium silicate with ratio
2:33
Fig. 13 Visual aspect of 60 9 55 mm silicate coated samples after 8 days of exposure to SST. Coatings were obtained from 1 M potassium silicate solution in different silica ratios: (a) 2 and (b) 2:33
4. Conclusion
The corrosion behavior of nano-silica potassium silicate
conversion coatings on the 2024 aluminum alloy was investigated in 3.5 wt.% NaCl solution. Potassium silicate coatings
improved the corrosion resistance of the aluminum due to the
formation of silicate lm. But this protective barrier had some
discontinuities and defects which led to decreasing its stability
and increasing the pitting corrosion probability. Presence of
nano-silica improved the silicate networks and decreased the
existing defects. The ratio of nano-silica played an important
role to provide a high corrosion protection. Silicate conversion
coatings from 1 M potassium silicate solution with silica ratio
2:33 was more protective and continuous. The high corrosion
resistance was mainly due to the formation of compact and
perfect silicate layers on the surface in the presence of nanosilica.
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