Corrosion Science 53 (2011) 481486

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

Corrosion inhibition of aky aluminium powders prepared through solgel process

Hongwei Zhu a, Xiaoyue Qu b, Yu Hu a, Hui Xie b, Zhenxing Chen a,
a
b

School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, PR China
Department of Chemistry and Biology, Zhongshan Institute, University of Electronic Science and Technology of China, Zhongshan 538402, PR China

a r t i c l e

i n f o

Article history:
Received 5 July 2010
Accepted 29 September 2010
Available online 8 October 2010
Keywords:
A. Aluminium
C. Alkaline corrosion
B. SEM
B. IR spectroscopy
B. XPS

a b s t r a c t
In order to prevent corrosion of aluminium pigment in water, coated aky aluminium powder was prepared through the solgel process, in which tetraethoxysilane (TEOS) and tris(2-methoxyethoxy)vinylsilane (VTMOEO) were adopted as precursors. The inuences of the dosage of precursors, ethylenediamine,
water and ethanol, as well as the reaction temperature and reaction time on the corrosion inhibition efciency were investigated. Under the optimum conditions, the corrosion inhibition efciency reached
99.2% in alkaline media of pH 11. The analysis with SEM, FTIR, EDS and XPS showed that solgel coatings
had successfully encapsulated on the surface of clear aky aluminium powders.
2010 Elsevier Ltd. All rights reserved.

1. Introduction

2. Experimental

Flaky aluminium powders have been widely used as solventborne metallic paints, printing inks, roof coatings and anticorrosion
paints for many years [1] due to their excellent metallic appearance
[2]. For environment protection, water-borne metallic paints and
inks should be developed to reduce the emission of volatile organic
compounds (VOC) to atmosphere during their application [3,4].
A severe problem of water-borne aluminium paints is that aluminium can react with water and form hydrogen gas, which probably results in the deterioration of metallic luster, the separation of
coatings from substrates and even the building up of dangerous
pressure [5,6]. Encapsulation of aluminium akes with protective
coatings [7] is a valid method for the stabilization of aky aluminium powders in aqueous media. Organic coatings, such as saccharides, styrene-maleic anhydride copolymers and plant extracts,
show excellent compatibility with resins but have poor stability in
alkaline media [812]. While, inorganic coatings, such as SiO2, show
excellent stability but have poor compatibility with resins [13,14].
The solgel lm formed through the hydrolysis and condensation of alkoxides can protect the aluminium surface from corrosion
[15,16]. Nevertheless silane coupling agents can improve the compatibility with resins by cross-linking [17]. Hence, we prepared
water-borne aky aluminium powders with high stability in alkaline media and good compatibility with resins through the solgel
process, in which tetraethoxysilane (TEOS) and tris(2-methoxyethoxy)vinylsilane (VTMOEO) were used as alkoxide and silane
coupling agent, respectively.

2.1. Materials

Corresponding author. Tel.: +86 20 84113159.

E-mail address: chenzx65@mail.sysu.edu.cn (Z. Chen).
0010-938X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.09.062

Clear aky aluminium powders were prepared by immerging

solvent-borne aky aluminium pigments (Produced by Zuxing
Metallic Pigments Co. Ltd., China) into acetone, and then drying
under vacuum at 80 C for 6 h to remove organic compounds.
The size of clear aky aluminium powders is 16.86 lm(d50) and
the purity is higher than 99%. Tetraethoxysilane (TEOS) and
tris(2-methoxyethoxy)vinylsilane (VTMOEO) were puried
through distillation before use. Ethylenediamine and ethanol were
used as received.
2.2. Encapsulation process
Clear aky aluminium powders (mAl = 2 g) and ethanol were
poured into a reactor tted with a reux condenser and an agitator.
When the reaction temperature was in the range of 3055 C, the
mixture of TEOS, VTMOEO, ethylenediamine and distilled water
was added into the reactor drop-by-drop for 1 h. After reacted for
318 h, the slurry was ltered, then washed with ethanol and distilled water, respectively. Finally, coated aky aluminium powders
were dried under vacuum at 80 C for 6 h.
2.3. Characterization
To evaluate the corrosion inhibition efciency of coated aky
aluminium powders, the stability test was carried out, in which
0.5 g of coated aky aluminium powders and clear aky aluminium powders were respectively dispersed in KOH solution of pH

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H. Zhu et al. / Corrosion Science 53 (2011) 481486

11 at room temperature for 24 h. The corrosion inhibition efciency (g, %) was calculated according to the following formula:

V0  V
 100%
V0

Where V0 and V represent the volume of the hydrogen gas

evolved during the stability test for clear aky aluminium powders
and coated aky aluminium powders, respectively. V0 was measured to be 231.0 mL.
The surface morphology was observed with a eld emission
scanning electron microscope (SEM). The particle size was measured using a Mastersizer 2000 particle size analyzer. Fourier
transformation infrared measurement (FTIR) was used to characterize the functional groups, for which the powders were ground
with dried potassium bromide powders and then compressed into
a disc. The component of coated aky aluminium powders was
analyzed with energy dispersive spectroscopic (EDS). X-ray photoelectron spectroscopy (XPS) was analyzed using an ESCALab250
photoelectron spectrophotometer.

efciency gradually improves with increasing total dosage of precursors, and reaches the maximum at mTEOS+VTMOEO/mAl = 1.8. If
the total dosage continues to increase, the corrosion inhibition efciency does not improve any further, but metallic gloss is greatly
affected.
Ethylenediamine works as a catalyst in the solgel process and
its dosage has a great inuence on the hydrolysis and condensation
of silane. Under the conditions of mTEOS+VTMOEO(mTEOS/
mVTMOEO = 2):mwater:methanol:mAl 1.8:6:50:1, the reaction temperature 40 C and the reaction time 12 h, the effect of ethylenediamine
dosage on the corrosion inhibition efciency was studied and the
result is shown in Fig. 3. With the increase of ethylenediamine dosage, the corrosion inhibition efciency gradually improves due to
the accelerated hydrolysis and condensation of TEOS. However, excess ethylenediamine might induce the agglomeration of aky aluminium powders due to the increased ionic strength. As
methylenediamine/mAl = 1.5, coated aky aluminium powders exhibit
99.2% of corrosion inhibition efciency.
The effect of water dosage on the corrosion inhibition efciency
is shown in Fig. 4, in which mTEOS+VTMOEO(mTEOS/mVTMOEO = 2):

3. Results and discussion

100

3.1. Optimization of reaction conditions

98

(%)

3.1.1. Effect of the dosage of precursors (TEOS and VTMOEO),

ethylenediamine, water and ethanol
Under the conditions of the mass ratio among precursors, ethylenediamine, water, ethanol and clear aky aluminium powders
(mTEOS+VTMOEO:methylenediamine:mwater:methanol:mAl) 1.8:1.5:6:50:1,
the reaction temperature 40 C and the reaction time 12 h, the effect of the mass ratio between TEOS and VTMOEO (mTEOS/mVTMOEO)
on the corrosion inhibition efciency was investigated. As shown
in Fig. 1, with the increase of mTEOS/mVTMOEO, the corrosion inhibition efciency gradually increases, due to the improved hydrolysis
and condensation reaction. As mTEOS/mVTMOEO approaches 2, the
corrosion inhibition efciency reaches 99.2%. mTEOS/mVTMOEO cant
be larger than 2, otherwise an inefcient cross-linking lm might
be formed, resulting in poor compatibility between the lm and
the resins. Under the conditions of mTEOS/mVTMOEO = 2, methylenediathe reaction temperature
mine:mwater:methanol:mAl = 1.5:6:50:1,
40 C and the reaction time 12 h, the effect of the total dosage of
precursors (mTEOS+VTMOEO) on the corrosion inhibition efciency
was investigated. As shown in Fig. 2, the corrosion inhibition

96

94
0.5

1.0

1.5

2.0

2.5

3.0

mTEOS+VTMOEO/mAl
Fig. 2. Effect of the total dosage of precursors (TEOS and VTMOEO) on the corrosion
inhibition efciency of coated aky aluminium powders in alkaline media of pH 11.

99.2

99.2

98.8

(%)

(%)

98.8

98.4

98.4

98.0

mTEOS/mVTMOEO
Fig. 1. Effect of the mass ratio between TEOS and VTMOEO on the corrosion
inhibition efciency of coated aky aluminium powders in alkaline media of pH 11.

0.5

1.0

1.5

2.0

methylenediamine/mAl
Fig. 3. Effect of ethylenediamine dosage on the corrosion inhibition efciency of
coated aky aluminium powders in alkaline media of pH 11.

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H. Zhu et al. / Corrosion Science 53 (2011) 481486

100
99.2

99.0

(%)

(%)

98

98.8

98.6

96

98.4
3

30

35

40

mwater/mAl
Fig. 4. Effect of water dosage on the corrosion inhibition efciency of coated aky
aluminium powders in alkaline media of pH 11.

methylenediamine:methanol:mAl is 1.8:1.5:50:1, the reaction temperature is 40 C and the reaction time is 12 h. For mwater/mAl = 6, the
corrosion inhibition efciency reaches the maximum. As the water
content increases, the hydrolysis rate is promoted while the condensation rate is reduced, therefore an optimum water dosage
exists.
Ethanol also plays an important role in the solgel process. The
effect of ethanol dosage on the corrosion inhibition efciency is
shown in Fig. 5, in which mTEOS+TMOEO(mTEOS/mVTMOEO = 2):
mwater:methanol:mAl is 1.8:1.5:6:1, the reaction temperature is
40 C and the reaction time is 12 h. Low ethanol dosage will lead
to the formation of viscous slurry and a possible agglomeration.
However, high ethanol dosage will lead to the inefcient encapsulation of aky aluminium powders. The optimum methanol/mAl is
found to be 50.
3.1.2. Effect of reaction temperature
The effect of reaction temperature on the corrosion inhibition
efciency was also studied and the result is shown in Fig. 6. Here,
mTEOS+TMOEO(mTEOS/mVTMOEO = 2):methylenediamine:mwater:methanol:mAl
is 1.8:1.5:6:50:1 and the reaction time is 12 h. Reaction temperature has a great effect on the stability of coated aky aluminium

50

55

Fig. 6. Effect of reaction temperature on the corrosion inhibition efciency of

coated aky aluminium powders in alkaline media of pH 11.

powders because it can greatly inuence the hydrolysis rate of TEOS

and the condensation rate of siloxane. When the reaction temperature is 40 C, the maximum corrosion inhibition efciency occurs.
That is because the condensation rate of siloxane is faster than
the hydrolysis rate of TEOS at this temperature, which can enhance
the cross-linker density and the compact degree of the solgel lm.
3.1.3. Effect of reaction time
Under the conditions of mTEOS+VTMOEO(mTEOS/mVTMOEO = 2):methyand the reaction
lenediamine:mwater:methanol:mAl = 1.8:1.5:6:50:1
temperature 40 C, the effect of reaction time on the corrosion
inhibition efciency is shown in Fig. 7. As the reaction time is increased to 12 h, coated aky aluminium powders exhibits high stability. However, if the reaction time further increases, the corrosion
inhibition efciency decreases due to the separation of some coatings from aluminium powders.
3.2. Characterization of coated aky aluminium powders prepared
under the optimum conditions
Based on the previous results, the optimum conditions to
prepare coated aky aluminium powders are shown as follow:

100

100

98

98

(%)

(%)

45
o

T ( C)

96

96
40

50

60

methanol/mAl
Fig. 5. Effect of ethanol dosage on the corrosion inhibition efciency of coated aky
aluminium powders in alkaline media of pH 11.

12

15

18

t (h)
Fig. 7. Effect of reaction time on the corrosion inhibition efciency of coated aky
aluminium powders in alkaline media of pH 11.

H. Zhu et al. / Corrosion Science 53 (2011) 481486

mTEOS+VTMOEO(mTEOS/mVTMOEO = 2):methylenediamine:mwater:methanol:
mAl = 1.8:1.5:6:50:1, the reaction temperature 40 C and the reaction time 12 h. Under these conditions, the corrosion inhibition efciency can reach 99.2%.
The surface morphology of coated aky aluminium powders
and clear aky aluminium powders is shown in Fig. 8. Compared
with the smooth surface of clear aky aluminium powders, a dense
surface lm is formed on coated aky aluminium powders.
The particle size distribution of coated aky aluminium powders and clear aluminium powders is shown in Fig. 9. The average
diameter (d50) of coated aky aluminium powders is found to be
18.04 lm, which is slightly larger than that of clear aluminium
powders (d50 = 16.86 lm). It is the solgel lm which makes the
average particle size of coated aky aluminium powders 7.0% larger than that of clear aluminium powders.
The FTIR spectra of coated aky aluminium powders, TEOS,
VTMOEO and clear aky aluminium powders are shown in
Fig. 10. For clear aky aluminium powders, there is only a hydroxyl

3.0

a
b

2.5

2.0

V (%)

484

1.5

1.0

0.5

0.0
0

20

40

60

80

d (m)
Fig. 9. Particle size distributions of (a) coated aky aluminium powders prepared
under optimum condition and (b) clear aky aluminium powders.

Transmittance

4000

3500

3000

2500

2000

1500

1000

500

-1

Wavenumber (cm )
Fig. 10. FTIR spectra of (a) clear aky aluminium powders, (b) pure TEOS, (c) pure
VTMOEO and (d) coated aky aluminium powders prepared under optimum
condition.

Fig. 8. Surface morphology of (a) coated aky aluminium powders prepared under
optimum condition and (b) clear aky aluminium powders.

absorption peak at 3400 cm1. For coated aky aluminium powders, the vibration bands of vinyl group at 3060 cm1,
1407 cm1, 769 cm1 and 564 cm1, suggest that VTMOEO has taken part in the encapsulation reaction. For coated aky aluminium
powders, the new peaks at 3435 cm1 and 960 cm1 are attributed
to the Si-OH asymmetric stretching vibration and Si-OH stretching
vibration, respectively. For TEOS and VTMOEO, the vibration peaks
of ethoxy group and methoxy group appear around 2981 cm1,
2932 cm1, 2881 cm1, 2821 cm1, 2727 cm1, 1294 cm1,
1276 cm1, and 1201 cm1. However, these characteristic peaks
disappear in the FTIR spectrum of coated aky aluminium powders, indicating that the ethoxy and methoxy groups were consumed. Compared with TEOS and VTMOEO, Si-O-Si asymmetric
stretching vibration bands at 1140 cm1 and 1120 cm1 shifted
to 1190 cm1 and 1140 cm1, respectively, indicating that TEOS
and VTMOEO might react and cross-link in the solgel process.
In order to conrm the component of coated aky aluminium
powders, EDS was used to analyze the relative elemental percentage. Compared with clear aky aluminium powders (Fig. 11a), the
content of silicon and oxygen in coated aky aluminium powders

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H. Zhu et al. / Corrosion Science 53 (2011) 481486

Fig. 11. EDS spectrum of (a) clear aky aluminium powders and (b) coated aky aluminium powders prepared under optimum condition.

O 1s

80000

Counts (s)

(Fig. 11b) increases while the content of aluminium decreases,

indicating that SiO2 has been grafted onto the surface of aluminium powders.
XPS full-survey spectra of clear aky aluminium powders and
coated aky aluminium powders are illustrated in Fig. 12 and the
surface elemental composition is listed in Table 1. For clear aky

100000

60000

16000
15000
14000

40000

13000

C 1s

0
800

600

400

200

Counts (s)

11000

Al 2p
O 2s
1000

Binding Energy (eV)

12000

Al 2s

20000

10000
9000
8000
7000
6000
5000

4000

140000

3000
2000

O 1s

120000

1000
0
538

100000

536

534

532

530

528

Counts (s)

Binding Energy (eV)

80000

Fig. 13. High-resolution O 1s XPS of (a) clear aky aluminium powders and (b)
coated aky aluminium powders prepared under optimum condition.

60000

40000

1200

C 1s Si 2s Si 2p
Al 2p
O 2s

20000

1000

0
800

600

400

200

Binding Energy (eV)

Fig. 12. XPS full-survey spectra of (a) clear aky aluminium powders and (b) coated
aky aluminium powders prepared under optimum condition.

Counts (s)

1000

800

600

400

Table 1
Surface elemental composition of clear aky aluminium powders and coated aky
aluminium powders.
Samples

Al (wt.%)

C (wt.%)

O (wt.%)

Si (wt.%)

Clear aky aluminium powders

Coated aky aluminium
powders

30.03
4.84

31.37
18.93

38.60
57.86

0
18.37

200

0
78

76

74

72

70

Binding Energy (eV)

Fig. 14. High-resolution Al 2p XPS of (a) clear aky aluminium powders and (b)
coated aky aluminium powders prepared under optimum condition.

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H. Zhu et al. / Corrosion Science 53 (2011) 481486

aluminium powders, the mass content of Al, C, O and Si is 30.03%,

31.37%, 38.60% and 0, respectively. These values are 4.84%, 18.93%,
57.86% and 18.37% for coated aky aluminium powders. This indicates that SiO2 has been encapsulated on the surface of aluminium
powders.
High-resolution XPS spectrum of the O 1s and Al 2p are shown
in Fig. 13 and Fig. 14, respectively. For clear aky aluminium powders, the O 1s peak at 531.78 eV is induced by Al2O3. This peak
changes to 532.81 eV after coating. Besides, the Al 2p peak of
Al-O also shifts from 74.39 eV to 74.10 eV, and the intensity of
the Al 2p peak of pure Al element signicantly decreases, which
indicates that clear aky aluminium powders have been encapsulated through the formation of Si-O-Al bond.
4. Conclusion
TEOS and VTMOEO can be used as precursors to prepare a protective lm on the surface of clear aky aluminium powders
through the solgel process. The dosage of precursors (TEOS and
VTMOEO), ethylenediamine, water and ethanol, as well as the reaction temperature and reaction time have great effect on corrosion
inhibition efciency of coated aky aluminium powders. The optimum conditions for this are mTEOS+VTMOEO(mTEOS/mVTMOEO =
2):methylenediamine:mwater:methanol:mAl = 1.8:1.5:6:50:1, the reaction
temperature 40C and the reaction time 12 h, under which coated
aky aluminium powders exhibit 99.2% of corrosion inhibition efciency in alkaline media of pH 11. The analysis with SEM, FTIR, EDS
and XPS suggests that solgel coatings based on TEOS and VTMOEO
successfully encapsulated on the surface of clear aky aluminium
powders.
Acknowledgments
This work was supported by The National Natural Science
Foundation of China (20876182) and The Science and Technology
Project of Guangdong Province (2010B010800022).

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