Surfaces and Interfaces 6 (2017) 33–39

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Surfaces and Interfaces

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

An EIS analysis on corrosion resistance of anti-abrasion coating

Zhide Wang∗, Jing Li, Yan Wang, Zhiyong Wang
Beijing institute of aviation material, Beijing 100095, China

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

Article history: A coating for anti-corrosion and anti-abrasion application was fabricated successfully. And the ratio
Received 16 April 2016 among fillers, which would affect the function of coating, was studied in this paper by orthogonal ex-
Revised 27 October 2016
periments. Physical property, corrosion resistant performance and anti-abrasion property were compre-
Accepted 3 November 2016
hensively evaluated. Due to the alternating structure with soft and hard, the addition of antiseptic fillers
Available online 18 November 2016
has no effect on anti-abrasion property. However, the corrosion resistant performance revealed remark-
Keywords: able improvement in comprehensive salt fogging test. EIS was also conducted to analyze the corrosion
EIS process, the impedance values showed first decreasing then increasing on behalf of corrosion resistance.
Corrosion resistance The results showed the coating revealed best performance when the ratio of hard fillers and antiseptic
Anti-abrasion fillers is 1:1. What’s more, the small particle showed better shielding action in the corrosion process.
Coating © 2016 Elsevier B.V. All rights reserved.

1. Introduction sion resistant performance of coating and observe the process of

corrosion [8].
Organic coatings are used widely to protect material form de-
struction. Turbine blade, water pipe and pump impeller [1] are
2. Experimental
enduring severe abrasion from hard solid particles and corrosion
from corrosive medium. The corrosion accelerates the abrasion
2.1. Materials and preparation of specimens
process and the defect produced by abrasion expedites the cor-
rosion. Due to the domino effect, destruction goes quickly. How-
Aiming to fabricate multifunctional coating, four kinds of func-
ever, the corrosion resistance coatings on service show poor anti-
tional filler were selected in this experiment. Al2 O3 and silica
abrasion property, and the anti-abrasion coatings lack outstanding
sand were selected as hard filler, zinc phosphate and aluminum
corrosion resistant performance.
tripolyphosphate were selected as antiseptic filler. Then experi-
In fact, various studies [2–4] have investigated protected coat-
ment formula was set as Table 1, according to the L9 (34) orthog-
ings. Yang Hu et al. [5] compared the anti-erosion performance
onal array (Table 2) [9]. All the materials were bought in business
of Ni-P-SiC and Ni60JH, they found that the major damage style
way.
of coating is abrasion, which has a better anti-corrosion property,
The metal substrate used was steel sheet, with a size of
and that of another one which has bad anti-corrosion property is
70 × 150 mm. The substrate surface was abraded manually with
corrosion. A coating [6] developed by MTU company consisted by
240# abrasive paper and cleaned with acetone. The coating was
two part, the one is hard layer, the other is soft one, two parts
sprayed on the substrate. The coated samples were kept in air for
were deposited layer-by-layer. Yangping Wang [7] invented a coat-
24 h at room temperature, and then cured in 155◦ C for 1 h the
ing consisted of three layer, the precoated layer improves binding
coating thickness was measured with a thickness meter and was
force, protective layer provides function and ektexine decreases the
42 ± 5 μm.
force of friction. However, the protective coatings are too complex.
Hence, it is an urgent to develop a coating, which have both anti-
abrasion property and corrosion resistant performance.In order to 2.2. Measurement methods
achieve multifunctional coating, hard fillers and antiseptic fillers
were selected to be added in it. The ratio of two fillers was sys- Adhesive force was tested according ASTM D3359. A lattice pat-
tematically studied in this paper. EIS was used to evaluate corro- tern with six cuts in each direction is made in the coating to the
substrate, 3 M tape is applied over the lattice and then removed,
and adhesion is evaluated by comparison with description and il-
∗
Correspondence author. lustrations. All showed coating meet fundamental using condition
E-mail address: wzd911110@163.com (Z. Wang). and were 5B.

http://dx.doi.org/10.1016/j.surfin.2016.11.003
2468-0230/© 2016 Elsevier B.V. All rights reserved.
34 Z. Wang et al. / Surfaces and Interfaces 6 (2017) 33–39

Table 1
Experiment formula.

No Resin TiO2 Al2 O3 Silica sand Aluminum tripolyphosphate Zinc phosphate Adjuvant Solvent

1 31 3 5 5 5 5 1.8 44.2
2 31 3 7 3 3 7 1.8 44.2
3 31 3 3 7 7 3 1.8 44.2
4 31 3 8 7 1 4 1.8 44.2
5 31 3 10 5 4 1 1.8 44.2
6 31 3 5 10 2.5 2.5 1.8 44.2
7 31 3 2.5 2.5 10 5 1.8 44.2
8 31 3 4 1 7 8 1.8 44.2
9 31 3 1 4 5 10 1.8 44.2

Table 2 Fig. 1a shows the pendulum hardness of all samples. It can be

The orthogonal array.
seen the hardness of LC samples are lower than that of HC, indi-
Factor The ratio between hard filler The ratio among The ratio among cating the hardness would decrease with the addition of antiseptic
and antiseptic filler hard fillers antiseptic fillers fillers. It reveals hard fillers play an importance role in hardness
Level 1:1 1:1 1:1 of coating. What’s more, the increasing could be divided into two
3:1 2:1 2:1 part (Fig. 1b). When the ratio of hard fillers is less than 50%, the
1:3 1:2 1:2 speeding of increasing is slowly, and it increased quicker with the
addition continue.

The hardness of all coated samples were tested with pendulum
hardness tester BYK® Gardener 5854. The blank panel was tested
firstly and then the coated samples were tested. The hard values
was calculated via that the values of coated samples divide that of
blank panel.
Taber® Abrader 5155 was applied to characterize anti-abrasion
behavior of coatings basing on weight losing after certain circles.
The process goes under the condition of 500 g loading and H-18
abrasive wheel. Samples were weighted when the sample surface
is smooth after certain circles. Then Samples were weighted again
after 10 0 0 rounds’ abrasion.
Comprehensive salt fogging test was performed to evaluate the
corrosive protection function of coatings to metal substrates fol-
lowing standard method ASTM B117. Coatings covered steel were
placed in the salt fogging chamber (Q-FOG CCT). 3.5 wt. % of
sodium chloride solution was used for fogging, and the tempera-
ture of the salt fogging chamber was set at 35 ± 1 ◦ C. Laboratorial
coatings (LC) and a hard coating on services (HC) were tested.
In the process of salt fogging test, the coated samples were re-
moved from the salt fogging clamber for different exposure times,
and electrochemical impedance spectra (EIS) measurements were
carried out in 3.5% NaCl solution at room temperature with a
PARSTAT 2273 electrochemical system (Princeton Applied Research,
USA). EIS is a technique with signal that has small perturbation
and the surface damage of the sample is very little [10]. EIS were
obtained at open circuit potential with a 10 mV sine perturba-
tion. The measuring frequency range was 10−2 ∼105 Hz. The ex-
posed area of the working electrode was about 1 cm2 . The ref-
erence electrode was saturated silver chloride electrode (SCE). A
graphite electrode was used as a counter electrode. Each test was
repeated three times at least. ZSimpWin software was used to an-
alyze the electrochemical impedance spectra in order to study the
corrosion process of coatings.
3. Results and discussion
3.1. The hardness of all coated samples
Anti-abrasion coating could be divided into two types: elastic
coating and hard coating. Hardness is an importance parameter of
hard coating. In some way, it could indicate the potency to resist
abrasion form hard particles. The higher hardness is, the more ex-
cellent anti-abrasion property show.
3.2. The anti-abrasion property of all samples
Anti-abrasion test is an immediate method to characterize abra-
sion resistance according to mass loss. Fig. 2a shows the mass loss
of all samples. It can be seen the mass loss of LC samples are less
than that of HC, indicating the wear resistance property of LC sam-
ples are quite to that of the HC sample. So, addition of antisep-
tic fillers almost has no effect on anti-abrasion property. It may
be because the alternating structure with soft and hard improves
the property of anti-abrasion similarly. From Fig. 2b, a large im-
provement is showed when the ratio of hard fillers attain to 75%.
It agrees with the results of hardness.
3.3. Comprehensive salt fogging test
Fig. 3 shows the morphology of all LC and HC samples after
912 h It can be seen the HC sample bubbles and LC samples are
intact. With the extending of exposure time, HC sample aggravates
heavily and few bubbles appear on the LC samples after 1416 h as
Fig. 4.
This could be due to the role of antiseptic fillers in LC which
makes it better corrosion resistant to 3.5% NaCl solution than HC.
The mechanism reported for corrosion resistance of phosphate is
that reaction of enriched phosphorous surface with water to form
a layer of adsorbed phosphate anions, which in turn will block the
supply of water to the substrate. So, protecting time was extended
and anti-corrosion performance was improved.
3.4. The EIS during failure process of coatings
Fig. 5 shows the Bode plots of LC samples at initial stage. It
can be seen the impedance values for LC samples are a straight
line with the slope equal to −1 versus frequency. Meanwhile, the
impedance values at low frequency are high, about 1010 ohms cm2 .
And the phase angles are almost − 90° at high frequency region,
capacitive behavior can be seen in the Bode phase diagrams of
these samples in a wide frequency range from 105 Hz to 10−2 Hz.
These indicate the coating systems amount to a shielding layer
with a high impedance, showing good barrier characteristics of the
coatings at the initial stage of immersion. The coatings can hinder
the direct contact between corrosive medium and metal substrate
effectively, giving a good protection to metal. As the immersion
time elapsed, the coating barrier performance declined. This can
 Z. Wang et al. / Surfaces and Interfaces 6 (2017) 33–39 35

Fig. 1. The hardness of all samples (a) and the effect of filler ratio on hardness (b).

Fig. 2. The mass loss of all samples (a) and the effect of filler ratio on anti-abrasion property (b).

Fig. 3. Morphology of all LC and HC samples after 912 h (The LC samples were white and the HC sample was yellow).
36 Z. Wang et al. / Surfaces and Interfaces 6 (2017) 33–39

Fig. 4. Morphology of all LC and HC samples after 1416 h (The LC samples were white and the HC sample was yellow).

Fig. 5. The Bode plots of LC samples at initial stage (0 h).

Fig. 6. Impedance values at 0.1 Hz of all LC samples (a) and HC sample (b).
 Z. Wang et al. / Surfaces and Interfaces 6 (2017) 33–39 37

Fig. 7. EIS bode plots of HC during failure process.

be understood from the decrease of |Z|0.1 Hz . This might be due to

the coating degradation after exposure to NaCl solution, resulting
in electrolyte pathways creation to the steel substrate [11]. From
Fig. 6a, it can be seen that the impedance values at 0.1 Hz firstly
descend and then increase, as salt fogging test going. The first de-
scent shows corrosive medium was permeating through the coat-
ing system. The corrosion process is very complex, controlled by
the velocity of permeability, and it usually dissatisfies Fick’s First
Diffusion Law [12], relating to the resin system. With the test go-
ing, the impedance values revealed a tendency of increasing. It in-
dicated antiseptic fillers reacted, forming a phosphate layer. The
phosphate layer impeded permeating process of corrosive medium,
playing a passivation role [13,14].
EIS bode plots of HC are showed in Fig. 7. As the time of salt
fogging elapses, one time constant is appeared due to the coating
protection. It can be seen the capacitive response in the high fre-
quency range and the corresponding resistive response in the low
frequency range due to the coating protection [15]. From Fig. 6b, it
can be seen the impedance values of HC at 0.1 Hz decrease in the
process of salt fogging test. At the beginning, the impedance val- Fig. 8. Percentage of impedance decrease.
ues at 0.1 Hz for HC are 1.42 × 109 ohms cm2 (0 day) while later
on, they start to decrease attaining to 1.16 × 108 ohms cm2 after 59
days of salt spraying. All process is divided into two parts, the first
one decreases slowly, due to the protection of coating; and as time
of salt fogging extending, the second one decreases quickly, mean-
ing the destruction of coating; the shifting point is 31 days, agree-
ing with the time of bubbling in salt fogging test. It indicates cor-
rosion medium have permeated through coating, causing the loss
of adhesive force. Finally, the coating will failure and fall off.
From Fig. 8, it can be seen the impedance of all samples de-
creases seriously, the coating which fall biggest is HC, about 91.8%.
Relatively speaking, the anti-corrosion performance of LC samples
improve. The average percentage of impedance decrease is 76.1%
when the ratio of hard fillers and antiseptic fillers is 1:3; and
the percentage is 23.4% and 55.4% when the ratio is 1:1 and 3:1,
respectively. The samples which ratio is 1:1 revealed best anti-
corrosion performance, due to the least decrease. However, it’s the
reason why the samples which have more antiseptic fillers are not
best that the barrier property of them is worse and not all anti-
septic fillers play role.
Fig. 9. Bode plots of No. 1, No. 2 and No. 3.
38 Z. Wang et al. / Surfaces and Interfaces 6 (2017) 33–39
Fig. 10. Equivalent circuit used for numerical simulation of the EIS datum.
To compare the Bode plots of three formulas those ratio all is
1:1 further, it is worth mentioning, the impedance values of No. 3
decease 2 orders of magnitudes when the time enduing salt spray-
ing is 912 h, then ascend with the time goes on (Fig. 9c). Whereas,
the decreasing amplitude of No. 1 and No. 2 are 1 order of magni-
tudes (Fig. 9a and b). Aiming at understanding the condition which
emerge in the barrier period of coating, the size of all fillers is sur-
veyed and results show the size of Al2 O3 is smaller. Going back, it
can be seen form formulation in Table 1 that the amount of Al2 O3
is diverse, which is the most important reason for the diversity of
impedance values. Hence, Al2 O3 provide better barrier property, in-
dicating the small particles showed better shielding action in the
corrosion process.
The interpretation of the EIS results obtained during salt fog-
ging test was performed by numerical fitting, using the equivalent
circuit illustrated in Fig. 10. In those equivalent circuit models, con-
stant phase elements were used instead of pure capacitors. This
modification is obligatory in the case the phase shift of a capacitor
is different from 90° [16], the deviation of phase is call dispersion
effect due to crude and adsorption of electrode pole [17]. Among
them, A represent the initial stage of corrosion, B is interim of cor-
rosion and later stage of corrosion is C. W is Warburg impedance
which revealing diffusion process.
All the initial samples satisfy equivalent circuit model A and er-
ror is less than 5%, when the samples didn’t contract with corro-
sive medium. After 17 days salt fogging, the samples No. 4, No.
5 and No. 6 still satisfy model A, others satisfy equivalent circuit
model B 3 and the goodness of fitting model A declines. It in-
dicates the barrier properties of samples No. 4, No. 5 and No. 6
are excellent, others are entering into the interim of corrosion and
the corrosive medium penetrated inward slowly, which agree with
the appearing of W in model B 3. With the extending of salt fog-
ging time, all samples don’t meet previous equivalent circuit model
and be in line with model B 4. A new resistance and capacitance
can be seen in model B 4, which represent the formation of phos-
phate film. The stage of film formation agrees with the appearing
time of second time constant, which proved the passivation role
of antiseptic fillers in the corrosion process again. With test goes
on, some samples start to meet model C, meaning the entrance of
the later corrosion stage. W can be seen again in model 5, which
meaning the process of diffusion. Diffusion in the stage reveals
the arriving of corrosive medium to substrate, which in accordance
with the phenomenon of bubbling.
4. Conclusion
1. The mass loss was essentially constant in anti-abrasion test,
and hardness of coating decreased, with the addition of anti-
septic filler. It may be because the alternating structure with
soft and hard improve the property of anti-abrasion similarly,
although hardness is affected.
2. The anti-corrosion performance revealed remarkable improve-
ment in salt fogging test, the enduring time of LC was 1416 h,
while the time of a hard coating on service was 912 h;
3. In the corrosion process, the impedance values showed first de-
creasing then increasing on behalf of anti-corrosion property, it
is because barrier property of coating and passivation role of
antiseptic fillers.
4. Multifunctional coating for anti-corrosion and anti-scouring ap-
plication were fabricated successfully, and the coating revealed
best performance when the ratio of hard fillers and antiseptic
fillers is1:1.
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