Progress in Organic Coatings 89 (2015) 5766

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Progress in Organic Coatings

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

Corrosion behaviour of AA2024 coated with an acid-soluble

collagen/hybrid silica solgel matrix
Mohamed Gobara a, , Hesham Kamel b , Robert Akid c , Ahmad Baraka a
a
b
c

Department of Chemical Engineering, Military Technical Collage, Cairo, Egypt

Department of Mechanical Engineering, Military Technical Collage, Cairo, Egypt
School of Materials, The University of Manchester, Sackville Street, Manchester M13 9PL, UK

a r t i c l e

i n f o

Article history:
Received 3 December 2014
Received in revised form 28 July 2015
Accepted 30 July 2015
Available online 22 August 2015
Keywords:
Corrosion
Collagen
Sol gel
FTIR
AA2024
EIS

a b s t r a c t
Collagen is a potential corrosion inhibitor for aluminium alloy 2024 (AA2024), being derived from sh
scale, as conrmed by FTIR analysis. The extracted collagen powder was dissolved within a hybrid silica solgel to produce an environmental friendly (green) coating. The corrosion behaviour of the silica
solgel (SOL) and collagen/silica solgel (CSOL) coated AA2024 in 3.5% NaCl solution was investigated by
electrochemical impedance spectroscopy (EIS). In addition, the mechanical properties of both coatings
were evaluated using hardness, micro-hardness resistance and a cross cut adhesion test. Results showed
that collagen improves the corrosion resistance of the coated AA2024, while maintaining the mechanical
properties of the non-doped silica solgel coating.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Aluminium, with its high negative standard electrode potential
(1600 mV vs SHE), has a high afnity for oxygen forming a stable uniform passive oxide lm on its surface. This passive oxide
lm prevents corrosion of the underlying metal on the basis that,
if this lm is scratched, the underlying metal is re-oxidized with a
new oxide lm generated at the scratch site. However, aluminium
alloys are usually susceptible to localized corrosion (pitting corrosion) caused by the breakdown of the passive lm [1]. Aluminium
alloy 2024 (AA2024) is one of the most widely used alloys in the
aerospace industry due to its high strength to weight ratio and good
fatigue resistance [2]. However, this alloy suffers from a lack of corrosion resistance due to the presence of copper (3.84.9 wt%) being
the main alloy strengthening addition. Chromate(VI) conversion
coatings have been successfully used for many decades to protect aluminium alloys from corrosion. However, due to their toxic
and carcinogenic nature, they are becoming increasingly restricted
within Europe and North America [3].
Consequently, the new trend in corrosion protection technology
is to replace these coatings with environmental friendly ones such
as solgel coatings [46]. These coatings can be formulated as either
fully inorganic structures or as hybrid organic/inorganic network

Corresponding author. Tel.: +020 1144919619; fax: +0020 224485583.

E-mail address: m gobara@yahoo.com (M. Gobara).
http://dx.doi.org/10.1016/j.porgcoat.2015.07.026
0300-9440/ 2015 Elsevier B.V. All rights reserved.

structures. These hybrid coatings combine properties associated

with inorganic coatings such as scratch, wear resistance, durability and impact strength [79], with ones associated with organic
coatings such as exibility, low temperature curability and adhesion [10,11].
Silica solgel coatings can form van der Waals bonds with the
metallic surface, which can be transformed to a stable covalent
Me O Si bond during the drying process. Applying silica solgel
coatings can protect aluminium from corrosion due to the formation of silica rich Al-oxide lm which blocks the pores of Al
oxide lm hence, forming a highly corrosion-resistant layer [12,13].
Appropriate additives are required to provide the active corrosion inhibition offering self-healing properties of the coated surface
[14]. Most of these effective inhibitors can be adsorbed on the metal
surface [15,16] forming a strong co-ordination bond with the metal
atom and/or forming a passive lm on the surface [17]. However,
to date, only a few environmental friendly compounds have been
investigated as corrosion inhibitors [1821].
Collagen is the most abundant protein in vertebrates comprising about 30% of the total proteins. It is present in many
locations throughout a mammals body and is the main component
of connective tissue [22]. It has a wide range of uses in cosmetic,
biomedical and pharmaceutical applications [2325]. In general,
28 types of collagen have been identied and described according to structure and each type is abundant in certain tissues. It
is a macromolecule composed mainly of the basic units, proline
(Pro), glycine (Gly) and hydroxyproline (Hyp) (Fig. 1). It has a

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M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

regular arrangement of amino acids in three polypeptides strands.

The three polypeptides (amides) strands contribute to the helical shape of collagen (the strands are in left-handed helices form,
and these strands are twisted together into a right-handed triple
helix stabilized by many hydrogen bonds). The sequence often follows the pattern GlyProX or GlyXHyp, where X may be any of
various other amino acid residues [26].
Fish have collagen in different tissues, (bone, skin, scales, etc)
and extraction of these collagens is an ongoing research activity
[2730].
Continuing our work on collagen [31] as a green organic
inhibitor, in the current study, collagen has been used as an additive to silica solgel coatings in order to form a protective lm on
AA2024 alloy which is subject to immersion in neutral 3.5% NaCl.
The corrosion behaviour of the prepared solgel/collagen coating
has been compared with an identical silica solgel coating without
the addition of collagen. In addition, the mechanical properties,
namely macro and micro hardness, of both coatings have been
investigated using an ASTM standard test method. Finally, a crosshatch test has been used to evaluate the adhesion of the coating to
the metallic surface.
2. Experimental
2.1. Material
Aluminium alloy 2024-T3 samples (obtained from Q-panel
2.54 10.16 0.156 cm) were cleaned with deionized water followed by ultrasonic cleaning in acetone and then dried for 30 min
at 70 C before applying the coating at room temperature.
2.2. Preparation of collagen

Collagen was extracted from sh scale according to that prepared by Singh et al. [32]. The scales of Nile tilapia sh were
washed with distilled water at 5 C then mixed with 0.1 M sodium
hydroxide, at a ratio of 1:10 sh scales to alkali solution, to remove
non-collagenous proteins. The mixture was continuously stirred
for 6 h in an ice bath. The treated scales were continuously washed
with distilled water until a neutral pH of the washed water was
reached. The scales were then soaked in 0.5 M acetic acid for 24 h
and ltered and the ltrate collected. Finally, the collagen was precipitated by adding NaCl to the ltrate in the presence of 0.05 M
tris-(hydroxymethyl) aminomethane to neutralize the solution (pH
7.0) and then the collagen powder was collected by centrifuging
the solution. The powder was then washed with distilled water
followed by centrifuging to collect the white collagen powder; this
step was repeated 5 times to avoid the presence of any impurities. Extracted collagen was analysed by Fourier Transform Infrared
spectroscopy (FTIR, JASCO 4100). For spectra analysis, the collagen
powder was mixed with KBr powder forming a tablet which was
mounted in the sample holder of the FTIR spectrometer. The spectra are in the range of 4004000 cm1 with automatic signal gain
collected over 128 scans at 4 cm1 resolution. The background spectrum was recorded from the clean empty cell at 25 C and was taken
into consideration during analysis of collagen sample.
The surface morphology of the coated metal samples was investigated using scanning electron microscopy (SEM, Philips XL30 FEG)
equipped with an energy dispersive X-ray spectroscopy (EDS) analyzer.
2.3. Preparation of collagen/silica solgel coating
The silica solgel solution was prepared by an acidcatalyzed hydrolysis and condensation process, using the following

precursors; tetraethoxysilane (TEOS) and 3-Glycidyloxypropyl

trimethoxysilane (GPTMS) purchased from Sigma Aldrich, USA.
TEOS and GPTMS were mixed in ethanol with the molar ratio
of 0.02: 0.09: 5.0, respectively. 100 ml of mixture was stirred for
30 min. before the addition of the HNO3 catalyst. The pH was
adjusted to a value of 2 by adding 20 2 ml of 0.1 M HNO3 . The mixture was then stirred vigorously at 80 C until it turned to a clear
sol (SOL). For the collagen/silica (CSOL), a similar procedure was
carried out; with the exception that 0.5 g of collagen was dissolved
in 20 ml of 0.1 M HNO3 , prior to adding acid to the precursor mixture. Both sols were allowed to stand for approximately one week
before they were used to deposit a lm on the Al alloy substrate.
The coating was applied using a spray coating technique, and dried
at 80 C for 16 h. The thicknesses of cured SOL/CSOL coatings are
typically 15 2 m.

2.4. Corrosion measurements

Corrosion tests were carried out in a three-electrode cell using
the sample as the working electrode with a saturated calomel electrode (SCE) and platinum electrode as the reference and counter
electrodes, respectively. Electrochemical impedance spectroscopy
(EIS) measurements were obtained at the measured open circuit potential value, (Eocp ), applying 10 mV perturbation in the
frequency range from 105 to 102 Hz. Electrochemical corrosion
measurements were performed separately in naturally aerated
3.5% NaCl at room temperature using a Gamry 600 instrument.
The impedance data was analysed in terms of an equivalent circuit, using a nonlinear least squares t technique provided by the
Gamry software.

2.5. Mechanical testing

The mechanical properties of the coatings were evaluated in
order to estimate the behaviour of the proposed coating under
normal service operating conditions. Several mechanical tests have
been conducted in accordance with ASTM standards. For each test,
triplicate measurements were conducted and the average test value
was calculated. The Rockwell C macro-hardness test has been performed according to the ASTM E18-12 standard, while the Knoop
indentation has been used to measure the micro-hardness according to the ASTM D1474-98 standard. The Knoop indenter uses a
rhombic-based pyramidal diamond, loaded with a 50 g test weight
to create an indent in the surface, the size of which is measured
using a high magnication microscope. For micro-hardness testing, the thickness of the coatings was 25 m, in order to avoid the
effect of the hardness of the underlying metal. To evaluate the adhesion of a coating, a cross-hatch technique is used. Thin cross-hatch
cuts are applied to the coating. This is followed by the application
of a pressure-sensitive tape to this area, which is then removed
and visually inspected for the presence of any delaminated coating
attached to the tape.

3. Results and discussion

3.1. Collagen characterization
Collagen powder prepared from the skin of tilapia sh was
characterized by Fourier Transmission Infra Red (FTIR) and is presented in Fig. 2. The bands recorded at wavenumbers of 1460, 1408,
1060 and 590 cm1 correspond to CH2 bond bend, COO symmetrical stretch, C O stretch and skeletal stretch, respectively. The

M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

59

Fig. 1. Chemical structure of glycine, proline and hydroxyproline.

Fig. 2. FTIR spectrum of the prepared acid soluble collagen.

Fig. 3. SEM image of AA2024 coated with (a) SOL and (b) CSOL.

amide I band is found at 1658 cm1 and is associated with the

stretching vibrations of the carbonyl group (C O bond). The amide
A was found at a wavenumber of 3430 cm1 and represents a
free N H stretch vibration of a peptide which involves a hydrogen bond. The amide B band is found at wavenumbers of 2928 and
2075 cm1 representing the asymmetrical stretch of CH2 . The FTIR
results indicate that the prepared sample is an acid-soluble collagen
[6,23,3234]

3.2. Morphology of the coatings

Before studying the corrosion performance of the solgel coated
AA2024, scanning electron microscopy (SEM) was used to investigate the solgel surface morphology. The SEM images of the SOL
and CSOL coated AA2024 samples presented in Fig. 3a and b, show
that the surfaces of the coatings were free from cracks and appeared
to be uniform.

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M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

Fig. 4. SEM image of cross section of AA2024 coated with (a) SOL and (b) CSOL.

Fig. 5. Bode plots of SOL coated AA2024 in 3.5%NaCl.

Fig. 6. SEM image of SOL coated AA2024 sample after immersion in 3.5% NaCl solution for (a) 10 days and (b) 14 days

Fig. 4 presents SEM images, of the cross sections of the SOL

and CSOL coated AA2024 samples indicating the coatings to have a
thickness around 1416 m. Images of both coatings conrm that
contain no voids and each appear to show good adhesion to the
metal substrate (Note: adhesion properties will be discussed later).
Due to the development of an adherent interfacial layer between
the sol gel and AA2024 substrate, in addition to the low thickness of
the sol gel layer itself, this hybrid coating system may be considered

for use as a pre-treatment/primer layer, being applied prior to the

application of subsequent paint top coats.

3.3. Corrosion behaviour of the coated samples

Electrochemical impedance spectroscopy measurements
provide simple-quantitative data about the corrosion processes

M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

61

Fig. 7. EDX mapping of the pitting corrosion after 14 days immersion, area, as shown in the gure.

90
1hr
24 hr
3 days
10 days
14 days
21 days
28 days
35 days

1e+6

1e+5

75

60

1e+4

45

1e+3

30

1e+2

15

1e+1
1e-2

1e-1

1e+0

1e+1

1e+2

1e+3

1e+4

Phase angle [deg]

1e+7

Impedance [Ohm.cm2]

and coating degradation that occur during the exposure to an

environment.
The corrosion behaviour of the SOL coated sample in 3.5%
NaCl, was investigated using EIS. Fig. 5 shows the Bode plots of
the SOL sample over a 14 day period of immersion. Although, in
the early stages of immersion (after 1 hr), the impedance is high
(ca. 5 106  cm2 ), the impedance value decreases by more than
one order of magnitude within 14 days of immersion. This value
decreases in the mid to low frequency range, indicating degradation
of the SOL coating.
Fig. 5 also presents the phase angle plot of the SOL coated
AA2024 where a broad peak, extended from mid to low frequencies, is observed to decrease with prolonged immersion time. A
broad phase angle peak can be divided into at least two time
constants, i.e. two processes, taking place during immersion [35].
These two time constants are more clearly dened after 7 days
of immersion. The rst time constant represents the outer layer
of coating, which shows a decrease in the capacitive behaviour,
with immersion time, being related to a loss of the hydrophobic
property of the SOL [3638]. The second time constant represents
the charge transfer resistance and the electric double layer capacitance, which are also, seen to decrease with prolonged immersion;
inferring diffusion of electrolyte through the coating [39]. Finally
a new time constant, at low frequency (0.5 Hz), appears after
seven days of immersion. With prolonged immersion, the magnitude of the new time constant increases. This, combined with a
decrease in both capacitive and resistive impedance values, suggests an increase in the area of the substrate being exposed to the
electrolyte, reective of a sign of breakdown of the SOL coating
[40].
This behaviour was accompanied by the appearance of pits
(Fig. 6a) after 10 days immersion. Furthermore, it is noted that
an increasing number of pits are observed on the coating surface
(indicated by arrows in Fig. 6b) signifying breakdown of the solgel
coating. The colour of the pits changed from white, after 10 days,
to dark brown after 14 days. EDX mapping of the pitting corrosion,

0
1e+5

Frequency [Hz]
Fig. 8. Bode plots of CSOL coated AA2024 in 3.5%NaCl.

Fig. 7, shows that the solgel coating is completely ruptured where

pitting has occurred on the substrate. This rupturing of the coating is due to the jacking stress effect resulting from the volume
expansion of the corrosion products formed.
This corrosion behaviour is related to the diffusion of the chloride electrolyte through to the metal/coating interface resulting in
pitting; where pit formation is associated with the inhomogeneous
distribution of Cu-containing and other intermetallic particles creating local galvanic cells that can act as anodic or cathodic sites with
respect to aluminium matrix [41].
Investigation of the corrosion performance of the CSOL sample (Fig. 8), was carried out using EIS in 3.5% NaCl solution for
up to ve weeks exposure. The impedance of the CSOL coating from the start of immersion appears to be under capacitive
control, as suggested by the line at slope = 1, in the low frequency range. This response indicated that this coating possessed a

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M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

Fitting the EIS data to an equivalent electrical circuit allows

an understanding of the progress of the corrosion process occurring within the coating system. The EIS equivalent circuit shown in
Fig. 10 is typical of an organic barrier coating, and is considered to be
applicable to this coating. This circuit contains the following components; an electrolyte resistance (Rs ); pore SOL layer resistance
(Rp ); SOL coating capacitance (Qc ), double layer capacitance (Qdl )
and charge transfer resistance (Rct ). Furthermore, constant phase
elements (CPEs) were used instead of pure capacitors.
The CPE can be transformed to a pure capacitor, Cdl , according
to the following equation [44].
Cdl =

Fig. 9. SEM image of CSOL coated AA2024 sample after immersion for 32 days in
3.5%NaCl solution.

certain degree of corrosion resistance. Fig. 8 further shows that the

coating impedance undergoes a small change in the high frequency
range (103 104 Hz) during the period of immersion. However, the
impedance at mid and low frequency range (102 102 Hz) remains
stable, changing by less than a half order of magnitude during ve
weeks of immersion. In addition, the spectra exhibit a linear slope
approaching 1, over a wide range of frequencies (102 102 Hz),
indicating a capacitive behaviour of the CSOL coating. These results
suggest the corrosion resistance of the CSOL coating in the NaCl
electrolyte is relatively stable.
In comparing the impedance values at low frequency, notably
102 Hz, after a period of over 14 days immersion, (Fig. 5) with that
of the CSOL coating (Fig. 8), it can be seen that the impedance of
the SOL coating decreases by one order of magnitude.
The phase angle plot for the CSOL sample is also represented in
Fig. 8. This plot shows a low phase angle at high frequency region
(104 Hz) reecting the porous nature of the sol gel coating, as indicated in the low impedance over the same frequency range. In
general, sol gel coatings contain a porous outer layer and an inner
barrier layer [42,43]. The porous layer is produced as a result of the
differences in evaporation rate of the solvent from the surface compared to that from the inner layer [43]. Moreover, a broad capacitive
peak is observed during the rst 3 days of immersion, extending
from mid to low frequency range. This peak is clearly separated
into two distinguishable time constants after 10 days of immersion.
The rst time constant, at 102 Hz, increases slightly with immersion time, representing the coating/solution interface consisting of
coating layer resistance (Rp ) and coating capacitance (Cc ). Notwithstanding a decrease in the capacitive behaviour, represented by this
time constant, which reects electrolyte uptake, the coating capacitance increases from 45o to 70o , indicating good barrier properties
and stability of the CSOL coating during the immersion period.
The position of the second time constant, at 0.4 Hz, remains unaltered during the immersion period, being representative of the
double layer capacitance (Cdl ) and charge transfer resistance (Rct ).
Although the capacitive behaviour of this time constant shows a
decrease during the ve weeks of immersion, this behaviour was
not reected in the corrosion performance of coating; as indicated
through visual inspection of the CSOL coated AA2024, where no
signs of pitting or delamination were observed, see Fig. 9.
Fig. 9 presents an SEM image of AA2024 coated with CSOL after
32 days of immersion in 3.5%NaCl solution. The image conrms the
stability of the coating indicating no signs of pitting or delamination.

Y0 .n1

sin n/2

(1)

where Y0 is the CPE constant, is the angular frequency (rad/s),

j2 = 1 and n is the CPE exponent. For ideal electrodes, CPE is equal
to an ideal capacitor when n = 1.
Fig. 11 shows the change of SOL coating pore resistance during 14 days of immersion in 3.5% NaCl solution. It can be seen that
the pore resistance decreases dramatically during the immersion
period. In the same gure, the SOL coating capacitance shows a continuous increase during the 14 days period of immersion. The rapid
decrease of pore resistance and increase of coating capacitance is
considered to be due to electrolyte uptake within the coating.
The charge transfer resistance, Rct , of the SOL coated AA2024 system decreases continuously during the exposure period, as shown
in Fig. 12, which also shows that the double layer capacitance (Cld )
gradually increases with immersion time. The decrease of charge
transfer resistance and increase of double layer capacitance may
be attributed to electrolyte ingress through the coating to the coating/metal interface. These experimental results indicate a rapid
break down of the SOL coating in 3.5% NaCl solution and pitting of
the AA2024 within 7 days of immersion, with the coating showing
little sign of long-term protection within the articial seawater.
To understand the corrosion behaviour of the CSOL coatings, the
EIS data of the CSOL coated AA2024 was tted to the equivalent
circuits, as shown in Fig. 10. Here, the equivalent circuit consists of
an electrolyte resistance (Rs ), pore CSOL layer resistance (Rp ), CSOL
coating capacitance (Qc ), double layer capacitance (Qdl ) and charge
transfer resistance (Rct ).
Fig. 13 shows the change of pore resistance and coating capacitance with immersion time for the CSOL coated AA2024. The gure
shows a slight decrease in Rp during the rst 3 days of immersion; during the same period the value of the coating capacitance
increases with immersion time. Following this, both the pore layer
resistance and coating capacitance remain stable until the end of
the test. This behaviour explains the slight decrease of impedance
at high frequency, 104 Hz, (see Fig. 8). This slight change in Rp
and Cc may be related to the loss of hydrophobic properties of the
collagen/solgel coating during the rst few days of immersion. The
stability of the coating resistance and capacitance is an indication of
not only the homogeneity and defect-free nature of the CSOL coating, but it also indicates the improvement of diffusive resistance to
the corrosive electrolyte, being attributed to the presence of collagen within the sol gel coating. In addition the presence of collagen
within the sol gel matrix may have a corrosion inhibiting effect.
Whilst conrmation of this inhibition effect requires further investigation, comments on this aspect of the coating are given later in
the paper.
For the same period of time, it is evident from Fig. 13 that the
pore layer resistance and coating capacitance of CSOL remain stable
when compared to that of the SOL coating, (Fig. 12), reecting the
improved diffusion resistance of the CSOL coating.
The improved resistance to electrolyte diffusion is reected in
the gradual increase of double layer capacitance (Cdl ) and decrease

M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

63

Fig. 10. Equivalent circuits used for numerical tting of the EIS data for CSOL coated AA2024 in 3.5%NaCl solution (a) before 24 h and (b) after 24 h (Note: gure not to scale).

Fig. 11. Change of coating capacitance and pore resistance of SOL coated AA2024 in 3.5%NaCl solution with immersion time.

Cdl[Frad.cm-2]

1e+5
0

10

12

14

Time [days]
Fig. 12. Change of double layer capacitance and charge transfer resistance of SOL
coated AA2024 in 3.5%NaCl solution with immersion time.

of charge transfer resistance (Rct ) as shown in Fig. 14. The interaction of the electrolyte with the metal surface takes up to 5 weeks,
before a decrease in the impedance (one half an order of magnitude) is observed. This can be explained by the presence of collagen

1e-7

1e+5

1e-8

1e+4

1e-9

1e+3

1e-10

Rp[Ohm.cm-2]

1e-6

Rct[Ohm.cm-2]

1e+6

Cc [Frad.cm-2]

1e+7

1e-5

1e+2
0

10

20

30

Time [days]

Fig. 13. Change of coating capacitance and pore resistance of CSOL coated AA2024
in 3.5%NaCl solution with immersion time.

in the coating, which may form an active barrier to electrolyte diffusion thus hindering the interaction between the electrolyte and
metal substrate, (note the mechanism of corrosion protection will
be discussed later).

M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

1.5

/W

0.04
1.0
0.03

0.02
0.5
0.01

CSOL
SOL
Relative water absorption

1e-7

1e+5
0

10

20

0.00

30

Relative volume of water absorption [W

1e+6

Water absorption volume fraction W

1e-6

Rct[Ohm.cm-2]

Cdl[Frad.cm-2]

0.05

CSOL

1e+7

1e-5

SOL

64

0.0
0

10

Time [days]

Time [hr]

Fig. 14. Change of double layer capacitance and charge transfer resistance of CSOL
coated AA2024 in 3.5%NaCl solution with immersion time.

Fig. 15. Water absorption volume fraction, Wv , and ratio of water absorption
(SOL:CSOL) versus time (t) for the various coating systems.

In contrast to the continuous decrease of Rct of the SOL coating, the Rct of the CSOL coating initially shows a decrease, but then
remains stable over the following 4 weeks of immersion. In addition, compared with the Cdl of SOL coating, the Cdl of CSOL coating
is more stable over the same period of immersion. These results
suggest that there is an interaction between collagen in the CSOL
coating with the metal surface, which reduces the rate of coating
degradation and subsequent substrate corrosion.
In terms of mechanisms, it is accepted that the aluminium oxide
layer cannot protect Al from corrosion in severe corrosive environments such as 3.5% NaCl, whereupon aluminium undergoes pitting
corrosion. The pitting of aluminium is mainly due to the low negative potential and presence of Cl . The mechanism of the pitting
corrosion of Al in NaCl medium includes reduction of oxygen as a
cathodic reaction. The anodic reaction taking place in this solution
was assumed as one of the following reactions [4547]:
Al + 3H2 O Al(OH) + 3H+ + 3e

(2)

(3)

(4)

Al + 2H2 O AlO(OH) + 3H + 3e
Al + 3/2H2 O Al2 O3 + 3H + 3e

This follows the formation of Al(OH)+2 which will react with

chloride ion to form a soluble complex as follows:
Al(OH)+2 + Cl Al(OH)Cl+ + 3H+ + 3e

Fig. 15. It is clear that initially, within 30 min, CSOL coating showed
a slightly greater uptake of water then the SOL coating adsorbed a
greater amount of water than the CSOL coating. Moreover, after 6 h
of immersion, absorption of water in the SOL sample signicantly
increases, and it stabilizes after 9 h. The absorption of water in CSOL
sample seems to reach saturation after 6 h. In addition, neither of
the samples showed delamination or corrosion during the water
uptake measurements. Fig. 15 also shows the relative volume of
water absorption of SOL to CSOL coatings. After 30 min., the volume
of water uptake in SOL coating is greater than CSOL coating, i.e.
(WSOL /WCSOL ) > 1.
From these results it is apparent that, introducing collagen
within the silica solgel coating improves the barrier property that
is resistance to water uptake within the coating.
Polar organic compounds that contain nitrogen, oxygen and
sulphur are considered as corrosion inhibitors [52] whereby the
efciency of the inhibitor is improved with increasing molecular
weight. The molecular structure of collagen contains amide-type
organic compounds which contain nitrogen, which may in part give
rise to the inhibition properties of collagen due to the formation of
an insoluble complex [53] via a coordination bond (N Al) [52,54].

(5)

Cl

The concentration of
increases the production of these soluble complex ions, Al(OH)Cl+ , thus increasing the corrosion rate of
aluminium [48].
This corrosion mechanism of aluminium can be inhibited by
means of a barrier layer that hinders the diffusion of electrolyte
and/or formation of insoluble salt with the aluminium substrate.
To investigate further the role of collagen within the silica
solgel coating, water uptake was measured for both SOL and
CSOL coated samples. This property is a good indicator to evaluate the resistance to diffusion of electrolyte through the coating,
which in turn, is related to the anticorrosive protection behaviour.
Water uptake can be calculated according to the following equation
[4951]:

Wv =

log Ct /Co
log(w )

(6)

where Ct is the coating capacitance at immersion time t, Co is the

dry coating capacitance at the beginning of immersion and w is
the dielectric constant of water, taken as a value of 80 [50].
The capacitance of SOL and CSOL coated lms was measured
using EIS at a xed frequency of (1 Hz) at room temperature for
10 h in a 3.5% NaCl solution [49]. The water uptake ratio is shown in

Fig. 16. Change of both Rockwell macro-hardness and Knoop indentation microhardness of SOL and CSOL samples.

M. Gobara et al. / Progress in Organic Coatings 89 (2015) 5766

65

Fig. 17. Adhesion, tape, pull-off test results (a) with Collagen and (b) without Collagen following 24 h immersion in 3.5% NaCl solution.

This complex therefore may be responsible for the formation of an

insulating lm layer, which in turn reduces the discharge of H+ and
dissolution of the substrate and, inhibits the formation of soluble
chloride complexes, resulting in a decrease in the corrosion rate.
From the above results, it can be concluded that the addition of
collagen to silica sol gel coating improves the corrosion resistance of
AA2024 in 3.5%NaCl. This can be ascribed to two mechanisms; rst:
blocking the pores of silica solgel coating and decreasing ionic
diffusion, which takes place during the early stages of immersion.
Second, as the electrolyte reaches the metal/coating interface, collagen interacts with the metal surface to form an insoluble metallic
complex [21] which inhibits the corrosion reactions.
3.4. Mechanical testing
The mechanical properties of a coating play a key role in
the engineering performance of that coating. Among the various
properties, hardness and adhesion have been extensively used to
determine the quality of coatings.
The hardness of coating/substrate samples has been obtained
using the Rockwell C hardness test. Test samples have been tested
under 15 N loads and silica coated samples scored an average of 43
HRC value where collagen coated ones scored 36.
Results of the Knoop indentation hardness testing showed an
average value for the SOL and CSOL coated samples of 258 and 224,
respectively. Since higher Knoop values indicate higher hardness,
these results suggest that the addition of collagen causes a slight
decrease in the coating hardness. Both macro- and micro-hardness
results are summarized in Fig. 16.
The cross-hatch adhesion test has been applied to both coating
types to evaluate the adhesion performance, both before and after
immersion, of the coatings in 3.5% NaCl solution for 24 h. The wet
adhesion was performed in order to assess the inuence of water
uptake on the adhesion properties of coatings. The cross-hatch cut
test of the dry samples did not show any signs of delamination
after performing the test ten times on the same area (gures not
presented here). When performing the test on wet samples, the
CSOL samples did not exhibit any distinguishable differences in
behaviour when compared to the SOL samples, where delamination
is only visible at two scratch lines (arrowed) as shown in Fig. 17.
From these results it can be concluded that the addition of collagen to the silica solgel coating has not signicantly changed the
mechanical adhesion properties of the coating.
4. Conclusions
Collagen has successfully been extracted as a powder from sh
scales. The extracted collagen powder dissolved completely in an

acid catalysed silica solgel coating. EIS results showed that the
sol gel coating alone cannot withstand long term of immersion in
the NaCl corrosive solution. The addition of collagen to the silica
solgel coating improved the long-term corrosion resistance of the
coated AA2024 substrate, forming a barrier against the corrosive
solution hence hindering the interaction between the electrolyte
and the metal surface. Furthermore, collagen appears to interact
with metal substrate forming insoluble complex that inhibits the
pitting corrosion of AA2024. The mechanical properties of the new
collagen/silica solgel coating remained almost unchanged with
respect to the un-modied silica solgel coating.

Acknowledgments
The authors would like to thank the Egyptian Armed Force for
providing access to the testing facilities to undertake this project.
Moreover, the authors would also like to thank Prof. Saied Hassanien, Military Technical College, Cairo, Egypt, for their invaluable
advices during this work.

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