Progress in Organic Coatings 101 (2016) 309–321

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Progress in Organic Coatings

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

Introducing rice husk after utilizing new technology as anticorrosive

pigments in organic coatings
N.M. Ahmed a,∗ , W.M. Abd El-Gawad a , M.G. Mohamed a , A.A. Elshami b
a
Polymers and Pigments Department, National Research Centre, Dokki, Cairo, Egypt
b
Housing & Building National Research Centre, Dokki, Giza, Egypt

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

Article history: The aim of this study is to introduce rice husk after simple chemical modification as new eco-friendly
Received 15 April 2016 anticorrosive pigments. Uncontrolled burning of rice husk is often considered the most disposal method
Received in revised form 8 August 2016 in Egypt; this seasonal and highly localized massive burning generates excessive air pollution. The usage
Accepted 2 September 2016
of this waste as anticorrosive pigments will decrease the danger of environment pollutions. The new anti-
corrosive pigments based on rice husk as core comprising 80–85% of new pigment covered with thin shell
Keywords:
of ferrites that comprises about 15–20% were prepared using new technique called “core-shell”. The dif-
Core-shell
ferent ferrites/rice husk pigments were characterized using different analytical and spectro-photometric
Rice husk
Anticorrosive pigments
techniques, such as X-ray fluorescence (XRF), Energy dispersive X-ray (EDAX) and transmission electron
Ferrites microscopy (TEM). These core-shell pigments were then incorporated in solvent-based paint formula-
Impedance spectroscopy tions based on epoxy resin. The physico-mechanical properties of dry films were tested. The corrosion
properties using immersion test in 3.5% NaCl and electrochemical impedance spectroscopy (EIS) for
28 days were determined.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction With the development of the chemical preparation techniques,

The use of by-product and waste materials play a very impor-
tant role in solving present ecological problems. Rice husk is one of
the most important agro-wastes, which is produced in millions of
tons per year as a waste by-product in agricultural and industrial
processes. Rice husk are shells produced during the de-husking of
rice that one ton of rice can produce about 200 kg of husk, which
on combustion produces about 40 kg of ash [1,2]. Rice husk con-
stitutes about fifth of the 300 million metric tons of rice that are
produced annually in the world. Rice plant is one of the plants that
absorbs silica from the soil and assimilates it into its structure dur-
ing the growth, with high percentage of silica concentrated in its
husk that is more than 80–85%. Since rice husk is considered as one
of the most important agro-wastes and is rich in silica, many stud-
ies have been done to use it in many different fields due to its high
silica content which is a good advantage, especially in anticorrosive
coating industry [3–5].
In anticorrosive paint industry, silica is considered as highly
known and efficient material in corrosion protection and in enhanc-
ing coating properties such as abrasion and scratch resistance and
being high chemically durable in different media [6].
∗ Corresponding author.
E-mail address: niviahmed@yahoo.com (N.M. Ahmed).
core-shell technique comes in the front of the most developed
methods to reuse by-products and waste materials.
Core-shell structured particles are now attracting more and
more investigation interest, since these particles are constructed
of cores and shells having different chemical composition [7]. The
properties of core-shell particles in general, are different from both
of the pure core and the shell materials. The usage of this technique
in utilization of waste material is done by using the waste material
as the core comprising about 80–90% of the new composite. This
is done by precipitating a thin shell of active material on the core
surface which comprises 10–20% only to prepare novel compounds
with new properties which gathers the properties of both the core
and the shell materials at the same time. In coatings industry, the
pigments are considered as one of the most important components
that are used for different purposes such as decoration and pro-
tection. Generally, inhibitive pigments are introduced into organic
coatings as the main material for corrosion inhibition.
Ferrite pigments with spinel structure have been studied for
decades; they have the general formula MFe2 O4 , where M is a diva-
lent metallic ion [8]. They possess high hardness, coverage power,
insolubility and coloration. They usually lead to high thermal sta-
bility; high quality and are chemically and mechanically stable
pigments [9,10]. The proper choice of the cations present in the
oxide lattice can resolve the non-toxicity of the final compound
[11].

http://dx.doi.org/10.1016/j.porgcoat.2016.09.004
0300-9440/© 2016 Elsevier B.V. All rights reserved.
310 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321
In this work core-shell technique was used as a method for
utilization of rice husk as pigment, by using it as source of silica
precipitating on its surface a layer of ferrite pigments which is well
known anticorrosive pigments. The prepared core-shell pigments
contain only (10–20%) of ferrite pigments as shell material precip-
itated on (80–90%) rice husk as core. These pigments were tested
as anticorrosive pigments in paints. The modification of rice husk
was done by precipitating thin layer of (Zn, Mn and Zn·Mn) ferrites
on its surface. Ferrite pigments (Fe) are known as efficient anticor-
rosive pigments and they are present in the shell which is in direct
contact with the surrounding materials. The anticorrosive perfor-
mance of the new ferrites/rice husk (Fe/RH) core-shell pigments
was measured to prove their efficiency as anticorrosive pigments in
the different epoxy-based paint formulations. The results showed
that core-shell pigments based on rice husk are highly efficient in
their anticorrosive performance.
2. Experimental
2.1. Materials
• Zinc, manganese and ferric nitrates are powders of high purity and
were obtained from Win-lab, Sigma-Aldrich, ALPHA CHEMIKA,
respectively.
• Rice husk is a by-product obtained from rice plant in Egypt. The
obtained rice husk was ground to the finest form as preparatory
step to outfit the preparation of the new pigments [12].
Rice husk and prepared core-shell ferrites/rice husk (Fe/RH)
photos are represented in Fig. 1.
2.2. Preparation of core-shell ferrites/rice husk
Zn, Mn and/or Zn·Mn nitrates were mixed with Fe nitrate in situ
in the presence of ground rice husk at 100 ◦ C for 1 h; in this step
oxy-hydroxy iron compounds are formed. The formed paste was
then heated up to 400 ◦ C, after this temperature the iron oxides are
formed. Then, grinding of the paste was done. At last, calcinations
of the powder took place at 1000 ◦ C, and in this last step the ferrites
were formed on the surface of rice husk. A flow chart of the prepa-
ration process is presented in Fig. 2. From the preparation process it
can be deduced that the burning then calcinations process is essen-
tially for the formation of ferrites that are precipitated on the rice
husk surface and there was not initial burning step to the rice husk
before the ferrite precipitation.
Fig. 1. Rice husk (RH) and ferrite/rice husk (Fe/RH) core-shell prepared pigments.
2.3. Methods of instrumental analysis
2.3.1. X-ray fluorescence
The different concentrations of each element in the prepared
pigments were determined using an Axios, sequential WDX-ray
fluorescence (XRF) spectrometer, PANalytical 2005, USA.
2.3.2. Transmission electron microscopy (TEM) analysis
Various pigments were examined using JEOL JEM 2100 (Japan)
technique with micro-analyzer electron probe to determine the
particle shapes and sizes of the prepared pigments.
2.3.3. Scanning electron microscopy (SEM) and energy-dispersive
X-ray (EDAX) analysis
Energy-dispersive X-ray analysis technique and scanning elec-
tron microscopy (JEOL JX 2840) micro-analyzer electron probe
(Japan) was used in this work to estimate the particle shapes and
elements deposited on silica surface
2.4. Anti-corrosive paint formulations of ferrite/rice husk
core-shell pigments
The prepared core-shell ferrites/rice husk pigments were incor-
porated in paint formulations beside paint formulation free of rice
husk as blank for comparison. Paint film thicknesses range from
120 to 150 ␮m. All paint formulations were based on epoxy resin,
and the formulations were divided into three groups with different
pigment loadings from 30 to 50% of the total solids.
2.5. Mechanical properties of paint films containing the prepared
pigments
A variety of physical and mechanical evaluations of the paint
films were carried out. Relevant methods of sample preparation
and evaluations include;
• Determination of the resistance of paints against impact (ASTM
D5638-00, 2007)
• Determination of paint resistance against cupping in Erichsen
apparatus (ASTM D 5638-00, 2007)
• Determination of paint hardness (ASTM D 6577-00, 2007)
2.6. Corrosion studies
The corrosion behavior of coating containing different prepared
pigments was evaluated using two methods as following;
2.6.1. Immersion in salt solution 3.5% NaCl (ASTM D 870)
After 28 days of exposure, the coated steel panels were evalu-
ated for the;
• Degree of rusting (ASTM D 6294-98, 2007),
• Degree of blistering on painted steel surfaces according to (ASTM
D 714-07, 2007),
• Determining the degree of coating adhesion by means of a cross-
cut test (ASTM D 3359-97, 2007).
2.6.2. Electrochemical impedance spectroscopy (EIS)
The corrosion protective performance of coatings was investi-
gated using EIS (SP-150), which is obtained from biologic science
instruments, (France). EIS is one of the most powerful techniques
used for the investigation and prediction of corrosion protec-
tive performance of coatings. The impedance spectra for different
Nyquist plots were analyzed by fitting the experimental data to a
simple equivalent circuit mode [Cf/Rf/(Cdl + Rct)] for steel, which is
protected with coatings containing the prepared pigments (Fig. 3).
 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 311

Fig. 2. Schematic diagram for the preparation of ferrite/rice husk (Fe/RH) core-shell pigments.

Fig. 3. Equivalent electrical circuit used to fit the EIS data.

The circuit includes film capacity (CF) which is placed in parallel to

the film resistance (RF), [double layer capacitance (Cdl) and charge
transfer resistance element (Rct)] which are placed in parallel to the
film resistance (Rf). The double layer capacitance (Cdl) is arranged
in row to charge transfer resistance element (Rct).

3. Results and discussion

3.1. Characterization of the prepared pigments

3.1.1. X-ray fluorescence

XRF analysis represented in (Table 1) expresses the concentra-
tion of the oxides as a whole in the compound. The results revealed
that the concentration of ferrites increased drastically and oxides
of (Zn, Mn and Fe) were of higher concentrations than in the rice
husk. Also, it was noticed that silica concentration decreased in
the prepared core-shell pigments than the rice husk which is logic
because of the deposition of ferrites layer on its surface. This is a
confirmation of the formation of the core-shell pigment.
3.1.2. Transmission electron microscopy (TEM) analysis
Transmission electron microscope (TEM) technique was used to
identify the morphology of the rice husk (RH) and Fe/RH pigment
particles. Fig. 4 showed that, ferrite particles possess well-defined
dimensional plates that surround the spheres of silica which is the
main constituent of rice husk, and this was due to that transmission
microscopy takes cross-section view of the particles. It can be seen
that, the platelet shapes of ferrites that surround the silica parti-
cles have blocked the intersection positions between the spherical
plates of silica. Also, these plates provide a tortuous path to the
Fig. 4. TEM micrographs of ferrite/rice husk (Fe/RH) pigments.
corroding materials which prolonging their path to reach the steel
surface [13].
3.1.3. Scanning electron microscopy/energy dispersive x-ray
analysis (SEM/EDAX)
SEM photos were taken from two positions to insure the par-
ticle sizes and at the same time confirm the core-shell structure
formation. The overview on the rice husk showed that there are
particles sticking on its surface as can be seen from Fig. 5(b–d), then
focusing on these sticking particles showed the platelet particles of
ferrites. This was confirmed by an EDAX analysis of ferrites/rice
husk (Fe/RH) to show and ensure the formation of ferrites on the
rice husk surface.
Fig. 6 is taken as an example to show the calculations of the
concentration of (Zn·MnFe/RH) to be compared to XRF results and
show their real presence on the surface only.
312 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321

Fig. 5. SEM/EDAX analysis of ferrite/rice husk (Fe/RH) pigments.

3.2. Mechanical properties of paint films containing the prepared
pigments
The paint formulations of ferrite/RH pigments were shown in
Tables 2–4 . Different mechanical tests (Ductility, Impact resis-
tance and hardness) which are represented in Figs. 7–9 , were
carried out to determine the effect of rice husk and the three core-
shell pigments on the mechanical properties of paint films. Paint
films containing prepared core-shell pigments showed (higher duc-
tility and impact resistance) than that containing rice husk. In
case of core-shell pigments some of the carbon-containing mate-
rials (organic materials) existing in rice husk were evaporated
through the granulated ferrite shell during calcinations of ferrites.
Therefore, the core-shell particles have silica now as predominant
constituent of rice husk with its spherical shapes, which can move
freely through the matrix of paint film providing superior tactile
effect, and thus better mechanical properties can be obtained. This
is also supported by the assumption that, the plate structures of
zinc and manganese ferrites around and on the silica surface can
enhance adhesion, elasticity and reinforce the polymeric matrix of
the paint film [14,15].
3.3. Corrosion studies
3.3.1. Immersion test in 3.5% NaCl salt solution
From the data given in Tables 5–7 and Figs. 10–12 , it is obvious
that paint formulations containing rice husk and core-shell pig-
ments showed high corrosion protection performance. The degree
of rusting of paint films containing core-shell pigments was less
than 3% and 10% for paints containing rice husk (untreated). This is
 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 313

Fig. 6. EDAX analysis of (Zn·Mn)Fe/RH pigments.

Table 1 Table 2
XRF results of the different Ferrites/Rice husk (Fe/RH) pigments. Paint formulations of ferrite/rice husk (Fe/RH) pigments with Epoxy resin (Group I).

(Zn·Mn)Fe/RH MnFe/RH ZnFe/RH RH Concentration Ingredients/paint Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)Fe/RH
(wt,%) numbers (RH)

18.30 23.61 21.31 38.247 SiO2 Epoxy Resin 32

0.64 0.48 0.54 1.277 Al2 O3 Epoxy: Hardner 5:3
0.04 0.05 0.06 0.394 TiO2 Fe2 O3 20 15 15 15 15
38.16 39.77 40 3.098 Fe2 O3 TiO2 7 5 5 5 5
0.015 0.012 0.013 – Cr2 O3 Kaolin 30 22 22 22 22
16.72 23.03 0.21 0.305 MnO ZnO 11 5 5 5 5
– – – 0.056 CuO Rice husk (RH) – 21 – – –
14.89 1.48 23.05 0.082 ZnO ZnFe/RH – – 21 – –
0.017 0.011 0.018 0.040 NiO MnFe/RH – – – 21 –
1.26 1.76 1.65 2.010 MgO (Zn·Mn)Fe/RH – – – – 21
2.23 3.24 4.01 9.979 CaO Total pigment 68
0.019 0.019 0.018 0.070 SrO Total 100
3.93 0.98 0.87 2.193 Na2 O P/B 2.21
0.36 0.41 0.46 1.566 P2 O5
2.07 2.35 3.09 23.070 K2 O
1.30 2.56 2.6 3.443 SO3
0.03 0.04 0.04 12.300 Cl supported by the good film adhesion of most samples, which can
– – – 0.073 Br enhance the corrosion resistance. Also, it can be noticed that the
– – 1.52 1.798 ZrO2
pigments loading show no noticeable effect on the corrosion per-
formance of paint films containing them and the blank formulation
314 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321

Fig. 7. Hardness of paint films containing the prepared core-shell pigments.

Fig. 8. Impact resistance of paint films containing the prepared core-shell pigments.

(free of anticorrosive pigments) was the least in its anticorrosive
performance.
3.3.2. Electrochemical impedance spectroscopy (EIS)
Data obtained from electrochemical impedance spectroscopy
confirmed the immersion test results. There was no noticeable
difference in the corrosion resistance between the three groups
containing different pigment loadings. Also, it was clear that all
paints containing core-shell pigments showed high corrosion resis-
tance, this is indicated by the wide semicircles of capacitive type
and the high Rf values (charge transfer resistance).
Tables 8–10 and Figs. 13–15 showed that, the Rf values for all
samples during the 28 days of immersion. The data revealed that,
Rf values for coatings containing core-shell pigments were higher
than that of rice husk and the blank, also it is noticeable that paint
films containing ZnFe/RH showed the highest Rf values. The corro-
sion resistance of paint films decreased with time in the first two
weeks of immersion (due to the high attack of corrosive materi-
als), and then started to be almost steady. This is due to the good
 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 315

Fig. 9. Ductility of paint films containing the prepared core-shell pigments.

Fig. 10. Corrosion laboratory test results of Group I containing ferrite/rice husk (Fe/RH) core-shell pigments after 28 days immersion in 3.5% NaCl.

building of the compact film and the different corrosion protection
mechanisms offered by the pigments.
The results obtained from immersion test and confirmed by
EIS showed that, paint formulations containing rice husk exhibited
lower corrosion protection than paint formulations containing the
prepared core-shell anticorrosive pigments [16]. This may be due to
that, the modified rice husk is arranged in loose honeycombed fash-
ion and contain large number of holes which facilitate the passage
of corrosive materials to the substrate.
The good corrosion protection of the paint formulations con-
taining prepared core-shell anticorrosive pigments reveals the
interference between ferrites and rice husk. The presences of fer-
rites helped in overcoming the disadvantages of rice husk, and their
performance can be related to more than one mechanism as follow;
316 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321

Fig. 11. Corrosion laboratory test results of Group II containing ferrite/rice husk (Fe/RH) core-shell pigments after 28 days immersion in 3.5% NaCl.

Table 3 Table 5
Paint formulations of ferrite/RH pigments with Epoxy resin (Group II). Corrosion characteristics of ferrite/RH pigments in Group I.

Ingredients/paint Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn) Test Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)
numbers (RH) Fe/RH (RH) Fe/RH

Epoxy Resin 32 Adhesion Gt0 Gt3 Gt1 Gt1 Gt1

Epoxy: Hardner 5:3 Degree of blistering 10 10 10 6F 8F
Fe2 O3 20 15 15 15 15 Degree of rusting 4G, 10% 8-G, 3% 10 7-P, 0.3% 5S, 3%
TiO2 7 5 5 5 5
Kaolin 30 16 16 16 16
ZnO 11 5 5 5 5
Rice husk (RH) – 27 – – –
ZnFe/RH – – 27 – –
MnFe/RH – – – 27 –
(Zn·Mn)Fe/RH – – – – 27
Total pigment 68
Total 100
P/B 2.21

Table 4
Paint formulations of ferrite/RH pigments with Epoxy resin (Group III).

Ingredients/paint Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)Fe/RH

numbers (RH)

Epoxy Resin 32
Epoxy: Hardner 5:3
Fe2 O3 20 15 15 15 15
TiO2 7 5 5 5 5
Kaolin 30 9 9 9 9
ZnO 11 5 5 5 5
Rice husk (RH) – 34 – – –
ZnFe/RH – – 34 – –
MnFe/RH – – – 34 –
(Zn·Mn)Fe/RH – – – – 34
Total pigment 68
Total 100
P/B 2.21

Fig. 12. Corrosion laboratory test results of Group III containing ferrite/rice husk
• Passivating the steel substrate through the formation of an oxide
(Fe/RH) core-shell pigments after 28 days immersion in 3.5% NaCl.
layer on the substrate with a stoichiometry approximately the
same as Fe3 O4 [10].
• Buffering the medium and the corrosive reactions on the cathode, layer can be hydrated and exists as Fe2 O3 + H2 O or oxy-hydroxide
thereby stimulating its hydrolysis. The Fe3+ oxide in the external FeOOH [17].
 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 317

Fig. 13. EIS measurement of Group I containing rice husk and the core-shell pigments in 3.5% NaCl.

Table 6
Corrosion characteristics of ferrite/RH pigments in Group II.

Test Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)Fe/RH

(RH)

Adhesion Gt0 Gt3 Gt0 Gt0 Gt1

Degree of blistering 10 8M 10 8M 10
Degree of rusting 4G, 50% 4G, 10% 10 4G, 0.3% 5G, 3%

Table 7
Corrosion characteristics of ferrite/RH pigments in Group III.

Test Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)Fe/RH

(RH)

Adhesion Gt0 Gt3 Gt0 Gt0 Gt0

Degree of blistering 10 10 8F 10 10
Degree of rusting 4G, 50% 8-G, 10% 7-P, 0.3% 10 5G, 3%
 318
N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321
Fig. 14. EIS measurement of Group II containing rice husk and the core-shell pigments in 3.5% NaCl.
 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321
Fig. 15. EIS measurement of Group III containing rice husk and the core-shell pigments in 3.5% NaCl.
• Reducing the concentration of corrosive compounds penetrating
through the film. Thus, they can bind Cl− , O2 , H2 O, and NOx which
could otherwise cause the substrate corrosion [18].
It is clear that, ZnFe/RH pigment showed the best corrosion pro-
tection in the whole groups. This may be due to, Zn2+ ions that can
reach the anodic regions on the metal surface causing a significant
decrease in the metal oxidation reaction rate, which leads to an
increase in the protection efficiency.
4. Conclusions
• New class of core-shell ferrite/rice husk pigments containing dif-
ferent cations was prepared in this work.
319
• The anticorrosive and physico-mechanical properties of the
prepared pigments were studied in anticorrosive epoxy paint
formulations.
• The results revealed excellent physico-mechanical and corrosion
protection properties of paint films containing the new core-
shell Ferrites/RH. These pigments are considered economically
feasible, besides possessing high efficiency in protecting metal
substrates. These results were confirmed via electrochemical
impedance spectroscopy measurements.
• The performance of ZnFe/RH pigment was the best among the
prepared pigments.
• Using RH as core in the new pigments created extra routs for
saving the environment and protecting it from air pollution by
avoiding their burning.
320 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321

Table 8 Table 9 (Continued)

EIS results for different paint formulations containing ferrite/rice husk core-shell
pigments of group I. Blank

Blank Time Rp (Ohm Cm2 )

Coating containing (Zn·Mn)Fe/RH

Time Rp (Ohm cm2 )
Time Rp (Ohm Cm2 )
1 day 588 1 day 1150
7 days 452 7 days 1007
14 days 320 14 days 1315
21 days 752 21 days 1416
28 days 475 28 days 1650

Coating containing RH
Time Rp (Ohm cm2 )
1 day 695
7 days 1338 Table 10
14 days 904 EIS results for different paint formulations containing ferrite/rice husk core-shell
21 days 752 pigments of group III.
28 days 522
Blank
Coating containing ZnFe/RH
Time Rp (Ohm cm2 )
Time Rp (Ohm cm2 )
1 day 8452 1 day 588
7 days 6199 7 days 452
14 days 4264 14 days 320
21 days 3068 21 days 752
28 days 1733 28 days 475
Coating containing MnFe/RH Coating containing RH
Time Rp (Ohm cm2 ) Time Rp (Ohm cm2 )
1 day 1221 1 day 524
7 days 4206 7 days 1280
14 days 3230 14 days 1227
21 days 2513 21 days 1026
28 days 1733 28 days 842
Coating containing (Zn·Mn)Fe/RH Coating containing ZnFe/RH
Time Rp (Ohm cm2 ) Time Rp (Ohm cm2 )
1 day 1150 1 day 6740
7 days 3514 7 days 4426
14 days 1044 14 days 6251
21 days 1416 21 days 2933
28 days 1677 28 days 2114

Coating containing MnFe/RH

Time Rp (Ohm cm2 )
Table 9 1 day 1684
EIS results for different paint formulations containing ferrite/rice husk core-shell 7 days 1513
pigments of group II. 14 days 1138
21 days 2320
Blank
28 days 928
Time Rp (Ohm Cm2 )
Coating containing (Zn·Mn)Fe/RH
1 day 588 Time Rp (Ohm cm2 )
7 days 452 1 day 1345
14 days 320 7 days 1242
21 days 450 14 days 1301
28 days 590 21 days 980
28 days 1011
Coating containing RH
Time Rp (Ohm Cm2 )
1 day 869
7 days 781
14 days 709 Acknowledgment
21 days 670
28 days 412 This work was supported by Science and Technology develop-
Coating containing ZnFe/RH ment Fund in Egypt (STDF) under project number 12650.
Time Rp (Ohm Cm2 )
1 day 1365
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