Journal Pre-proofs

Development of a nanostructured film based on samarium (III)/polydopamine

biopolymer on the steel surface with superior anti-corrosion and water-repel-
lency properties

Farshad Bahremand, Taghi Shahrabi, Bahram Ramezanzadeh

PII: S0021-9797(20)31082-1
DOI: https://doi.org/10.1016/j.jcis.2020.08.039
Reference: YJCIS 26816

To appear in: Journal of Colloid and Interface Science

Received Date: 15 June 2020

Revised Date: 9 August 2020
Accepted Date: 10 August 2020

Please cite this article as: F. Bahremand, T. Shahrabi, B. Ramezanzadeh, Development of a nanostructured film
based on samarium (III)/polydopamine biopolymer on the steel surface with superior anti-corrosion and water-
repellency properties, Journal of Colloid and Interface Science (2020), doi: https://doi.org/10.1016/j.jcis.
2020.08.039

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover
page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version
will undergo additional copyediting, typesetting and review before it is published in its final form, but we are
providing this version to give early visibility of the article. Please note that, during the production process, errors
may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2020 Published by Elsevier Inc.

Development of a nanostructured film based on
samarium (III)/polydopamine biopolymer on the
steel surface with superior anti-corrosion and
water-repellency properties
Farshad Bahremanda, Taghi Shahrabia1*, Bahram Ramezanzadehb**
a
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, P.O.

Box: 14115-143, Tehran, Iran

b
Department of Surface Coatings and Corrosion, Institute for Color Science and Technology,

P.O. Box 16765-654, Tehran, Iran

Abstract

Hypothesis

The application of various hydrophobic/superhydrophobic coatings on the surface of metals has

become the hot topic of the recent studies. The corrosion protection effectiveness and

environmental issues are two important factors that should be taken into consideration when

developing advanced surface coatings. Recently, the rare-earth elements (i.e., samarium) and

biopolymers (i.e., polydopamine) have attracted much attention in the metals' corrosion control

field.

1
Corresponding authors:
*T.Shahrabi (Professor), tshahrabi34@Modares.ac.ir , Tel: +98 2296977, fax: +98 2294 7537
**B.Ramezanzadeh (Assistant Professorramezanzadeh@aut.ac.ir , , Tel: +98 2296977, fax: +98 2294
7537

1
Experiments

The Sm(NO3)3 containing solution was sprayed to the steel (St-12) sheets. Then, the Sm-modified

plates were post-modified by polydopamine biopolymers that were synthesized by the self-

polymerization (using tris (hydroxymethyl) aminomethane as a buffer), and oxidant-induced

(using CuSO4 as an oxidant) approaches. The structural analysis was carried out by different

techniques such as contact angle (CA) test. Moreover, the electrochemical impedance

spectroscopy (EIS) and polarization tests were performed to investigate the anti-corrosion

performance of various samples.

Findings

The CA test results revealed that by applying the nanostructured Sm-based film, the surface of the

metal becomes near superhydrophobic (CA>140°). EIS results evidenced the significant impact of

the post-treatment of the Sm-treated samples by polydopamine (PDA) nanoparticles (NPs) on its

corrosion protection ability enhancement. Also, the polarization test results confirmed that all

treatments could retard the corrosion of steel via a mixed-type inhibition mechanism.

Keywords: Bio-compatible film; superhydrophobic surface; nanostructured film; anti-corrosion;

polydopamine biopolymer.

1. Introduction

Corrosion, which is one of the destructive phenomena, results in enormous economic damages to

the industries every year. There are many practical approaches, i.e., application of inhibitors and

coatings, to increase the corrosion resistance of the metals [1, 2]. Steel is the most widely used

metals in many industrial applications; however, it has a significant tendency to corrosion, and

because of that, its application has been limited. Among the various methods applied for the

2
corrosion control of metals, the ceramic-based conversion coatings have attracted more attention

due to their simplicity in operation and cost-effectiveness. Besides, the conversion coatings (CCs)

are used as the pre-treatment for metals to improve the adhesion of the organic coatings to the

metals' surface [3–7].

For many years, the traditional chromate/phosphate-based CCs have been used as coatings for the

pre-treatment of the metals. However, the recent usage of these CCs has been restricted by the

environmental protection agency (EPA) because of the toxicity of the hexavalent chromium ions

[8–10]. The rare-earth-based CCs have been introduced as a more promising alternative for

chromate due to their non-toxicity and environmental compatibility [11–13]. Among these

elements, cerium is the most extensively used element for this purpose because of its availability

[14–17]. There are also numerous studies on the application of the rare earth elements such as Nd

[18,19], Pr [20], La [21,22], Gd [23], and Sm [24,25] for development of the thin anti-corrosive

CCs on the steel surface [26–28].

In recent years, the metals corrosion resistance improvement via application of the

superhydrophobic films has drawn much attention [29-32]. There are many industrial applications

for the superhydrophobic coatings, i.e., anti-fouling paints [33], self-cleaning [34] and snow anti-

sticking [35] films for window and antenna, anti-frosting metals' surface [36], anti-staining fabrics

[37], anti-soiling coatings [38], oil-water separation [39] and so on. Many approaches, i.e.,

chemical etching [40], hydrothermal method [41], anodizing [42], electrodeposition [43],

inorganic-organic sol-gel coatings [44], nanocomposite coatings [45], templating [46], direct

application of the superhydrophobic compounds on the surfaces [47] or as the post-treatment [48]

etc. [49,50] have been used to obtain superhydrophobic surfaces. Pan and coworkers [51]

developed superhydrophobic films via spraying a poly(methyl methacrylate) and waterproof silica

3
nanoparticles mixture onto the steel surface. They also investigated the corrosion resistance of the

film in the NaCl solution and revealed a significant reduction of the corrosion current density of

steel. Cao et al. [52] increased the corrosion resistance of the brass subjected to the 3% NaCl

solution by applying a polydopamine film on its surface. They also found that via the film

functionalization with 1H, 1H, 2H, 2H perfluorodecanehiol, the surface becomes more

superhydrophobic, leading to a better corrosion protection performance.

Dopamine, which is a hormone and neurotransmitter, can be readily oxidized in the alkaline

environments. The oxidized form of dopamine is named polydopamine [53]. Polydopamine has

been used for various applications i.e. drug delivery [54], photo-thermal treatment [55], energy

[56], etc. [57-60]. However, the polydopamine usage as a corrosion inhibitor has been rarely

studied. For example, Habibiyan et al. [61] have examined the polydopamine effectiveness on the

steel corrosion mitigation in the acidic solution. They evidenced that the polydopamine could

effectively increase the corrosion resistance of steel. Besides, the polydopamine synthesized via

the oxidant-induced polymerization approach in the presence of sodium periodate oxidant resulted

in the highest inhibition efficiency.

In general, the rare-earth-based CCs have been proposed as the less toxic alternative for the

chromate/phosphate-based CCs replacement. However, the rare-earth-based CCs include

structural defects that weaken their corrosion protection performance in corrosive environments.

The use of green biopolymers to improve the rare-earth-based CCs properties is one of the ideas

that have not been well explored. On the other hand, the superhydrophobic surfaces have been

designed for different applications such as corrosion control of the metals. Therefore, combining

polydopamine biopolymer with samarium-based CC for the construction of a robust

superhydrophobic anti-corrosion coating is the major novelty of this study.

4
In this research, polydopamine was synthesized by two approaches and used for the post-treatment

of the Sm-based CC. The impact of two synthesis methods of polydopamine on the Sm-based CC

properties has been studied by CA, scanning electron microscope/energy-dispersive X-ray

spectroscopy (SEM/EDS), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction

(XRD), atomic force microscope (AFM) as well as EIS and potentiodynamic (Tafel) polarization

tests. For this purpose, the samarium salt-based solution was sprayed on the steel surface and then

through the self-polymerization (air-exposed), and the oxidant-assisted approaches the

hydrophobic polydopamine films were deposited on the samarium-treated substrates.

2. Experimental

2.1. Materials

The details of the test materials used for the construction of the superhydrophobic film are given

in Table S1. The St-12-based steel panels with the chemical composition (wt%) of 0.10% C,

0.035% P, 0.45 % Mn, 0.035% S, 0.007% N, and the rest of Fe were cut to the size of 12 cm × 4

cm.

Table S1

2.2. Fabrication of nanostructured Sm-coating

The steel specimens' surfaces were deoxidized by sandpapers and then carefully degreased by

acetone. The prepared samples were preheated to 65 °C. Then, the chemical treatment solution

(Table 1) was continuously sprayed on the specimens for 60 s. For spraying the solution, an air-

spray instrument was used. The spraying process was performed at a 45̊ angle to the sample at a

constant distance of about 10 cm. The pH of the Sm-solution was fixed at 3 by adding the adequate

amounts of a 40% sodium hydroxide solution. Afterward, the samples treated by the Sm-based

5
film were washed by pure water. The washed samples were then dried by clean air. After that, all

samples were heat-treated at 140 °C for 3 h [25].

Table 1

2.3. The Sm-treated samples post-modification by PDA

The polydopamine was synthesized according to two well-known methods, including a self-

polymerization approach in an air-exposure condition by using tris (hydroxymethyl)

aminomethane as a buffer (PDAT) [62] and the oxidant-induced method by using copper sulfate

as an oxidant (PDAC) [63]. The polydopamine synthesis solution composition is given in Table

2. The samples modified with the nanostructured Sm-film were subjected to the dopamine-

containing solution for 24 hours. During 24 hours of exposure, the PDA molecules could adsorb

on the samarium-treated surface. The Sm-film deposition mechanism and the polydopamine

synthesis route are presented in Fig.1. After that, all of the samples were washed by pure water

and dried. Then, the heat-treatment was carried out on the samples at 140 °C for 3 h.

Table 2

Fig.1

2.4. Characterization

2.4.1. Structural analysis

SEM model VEGA/TESCAN-XMU, EDS model Mira III/TESCAN-SAMX, XRD analysis

(X’Pert MPD, Holland) at 2θ range of 5̊ to 90̊, FT-IR spectroscopy (Perkin-Elmer Frontier, USA)

(400-4000 cm-1) and AFM (VEECO CP II, USA) (tapping mode) analysis were respectively

carried out to evaluate the deposited film morphology/microstructure, chemical structure, and

surface topography. AutoProbe image software (Ver. 2.1.15) was employed to extract the

roughness parameters. Besides, the characterizations of the Sm-hydroxide and PDA-film and the

6
surface functional groups of different samples (untreated, Sm-treated, Sm-PDAT, and Sm-PDAC)

were done after 10 days of exposure to the 3.50% NaCl solution. The contact angle test was also

performed to determine the γs (surface free energy) of the samples. For this purpose, about 50 μL

of pure water was placed on the samples, and the contact angle of the water was recorded by a

digital camera.

2.4.2. Corrosion properties evaluation

EIS and polarization tests were carried out to investigate the corrosion resistance of the steel

specimens modified by the Sm-based coating as well as the PDAT and PDAC. The reference

(saturated Calomel) and the platinum electrodes were utilized for the measurements. In this system,

the untreated and Sm-treated samples were employed as working electrodes (1 cm2). EIS was done

by an Auto lab PGSTAT302n instrument at open circuit potential (OCP) and in the frequency

range of 100 kHz to 10 mHz with ±10 mV potential perturbation. Also, Nova software (version

1.8) was utilized for the impedance data analysis, and a Zview software (version 3.1) was used for

the obtained data modeling. The reproducibility of all parameters was examined on three identical

samples, and the average of the results was reported. In the case of the polarization test, the

experiment was performed after 10 days of exposure to the 3.50% NaCl solution. This test was

carried out in the potential range of ±250 mV around the OCP with a 0.001 V/s scan rate.

3. Results and discussion

3.1. Sm-film investigation

3.1.1. The γs evaluation

7
The γs can be obtained by measuring the CA using pure water. Through the Neumann's formula

and Young's equation [64], the γs of the substrate was calculated. The CA test results are presented

in Fig.2 and Table 3. Results depict that through the creation of the Sm-based coating on the metal

surface, the γs value was significantly affected. According to the obtained results, it is evident that

with the formation of the Sm-based layer, the CA increased, indicating that the surface becomes

less hydrophilic. This is due to the nano-scale roughness of the Sm-coating. Furthermore, through

the heat treatment process, a large amount of Sm-oxides can be created, causing a further water-

repellency enhancement of the surface. Due to the lower tendency of oxides than hydroxides to

make hydrogen bonding with water molecules, the surface became more hydrophobic, and the CA

increased. In the samples containing polydopamine-based polymer, the CA increased much more

than the samarium treated specimen, and subsequently, the γs remarkably decreased. This can

evidence that the deposited metal-organic complexes could provide a superhydrophobic surface

with significant water-repellency properties. Among the samples, the Sm-PDAC showed the

highest Ө and the lowest γs. The increases in the CA for the Sm-treated, Sm-PDAT, and Sm-PDAC

samples are about 21.50%, 41.80%, and 67% compared with the untreated sample. The

mechanisms of the CA changes in the Sm-PDAT and Sm-PDAC samples are almost different. In

the Sm-PDAC sample, the air can be trapped in the grooves [65, 66] that were produced by the

Sm-PDA complexes deposition. These grooves can be modified with the PDA NPs (70-400 nm),

causing the air-trapping ability of the coating. However, in the Sm-PDAT sample, the Sm-PDA

compounds have appeared in the form of micro-spheres (with 1-2 μm diameters) covered with

PDA NPs. These fine particles produce more places for air entrapment between the metal and the

water droplet, causing a further increase in the CA. In both specimens, the synergistic effect of the

samarium film nano-scale roughness and the micro/nano roughness's of the PDA-film, along with

8
the presence of hydrophobic PDA compounds are responsible for the increase of CA in these

samples. This event is schematically illustrated in Fig.3. Also, the type and amount of polar

functional groups in the PDA structure could affect the deposited film hydrophobicity degree.

PDAC has less hydroxyl and amine groups than PDAT. Therefore, the Sm-PDAC sample could

provide less hydrogen bonding with water than Sm-PDAT, leading to more waterproof property

[61].

Fig.2

Fig.3

Table 3

3.1.2. Surface characterization

The surface morphology of various specimens was investigated by SEM/EDS analyses. Fig.4

illustrates the SEM images of the bare and modified steel samples. Also, Fig.5 represents the

results of the EDS analysis. As it is clear from the SEM images, in the Sm-treated samples, a

uniform layer with plate-like morphology of particles was formed. A higher coverage was obtained

in the Sm-PDAC sample. In this sample, a denser (more compact) coating is generated on the steel

surface. However, in the Sm-PDAT sample, the formed layer is not uniform enough compared

with the Sm-PDAC treated one. According to Fig. S1, it is clear that the morphology of the

complexes created in various samples is different. As the provided images reveal, the Sm-PDAs

are in the form of parallel layers in the Sm-PDAC sample. However, in the Sm-PDAT sample,

9
they are in the form of microspheres of various sizes. This is the reason for the higher CA value

of the later.

The EDS achievements evidenced that the use of samarium film could significantly reduce the Fe

content, which is related to the steel surface coverage by the samarium oxide/hydroxide particles.

The presence of samarium and the increase in oxygen content in this sample compared to the bare

steel also confirm the presence of samarium oxide/hydroxide. On the other hand, in the specimens

modified by polydopamine, an increase in the iron content and a decrease in the oxygen and

samarium contents are evident. The iron cations, generated via the iron oxidation reaction, could

form the Fe-PDA complexes. The presence of these complexes on the surface is the reason for the

increase of the iron content in the post-treated specimens than the Sm-treated one. Besides, the

degradation of the Sm-oxide/hydroxide film in the PDA secondary bath is another reason for the

increase in the iron content and a decrease in the samarium and oxygen amounts in these

specimens. This degradation is thought to be mainly due to the more change in the solution pH.

Also, the coverage of the samarium oxides/hydroxides by a layer of polydopamine may justify the

reduction of oxygen and samarium in the post-treated samples. The carbon and nitrogen atoms

come from the polydopamine molecules. The further depletion of oxygen and samarium contents

alongside the increase of the iron and carbon contents in the Sm-PDAC sample compared with the

Sm-PDAT can indicate that the more area of the samarium coating is covered by the polydopamine

molecules and more Fe-PDA complexes were produced. Therefore, the iron content enhancement

in the Sm-PDAT sample is thought to be due to the coating porosity enhancement through the Sm-

film degradation in the PDAT secondary bath. In addition, the EDS and EDS-2D maps analysis

were carried out on the treated samples' surface before immersion in the corrosive environment,

and the obtained results are presented in Fig. S2, and Fig. S3, respectively. Moreover, Figs. S4-

10
S5 show the EDS and EDS-2D maps results of the cross-section of the modified specimens. The

SEM cross-section images, along with the combined EDS-2D maps of various samples, are

demonstrated in Fig. S6. The results indicate the formation of the samarium-oxide film via Sm-

modification and the development of a denser (more compact) coating by PDA post-modification.

To investigate the functional groups and phase composition of the film formed on the surface

through the Sm and Sm-PDA modification, FT-IR and XRD analyses were done, respectively. The

outcomes revealed that the samarium and polydopamine films covered the steel surface. FT-IR

and XRD results are demonstrated in Fig. S7, and Fig. S8, respectively. Furthermore, the AFM

analysis was performed to check the surface topography, and the obtained results are presented in

Fig. S9 and Table S2. In summary, the results of the AFM analysis showed that the steel surface

becomes rougher after the Sm-PDA treatment. Besides, a detailed discussion about them is given

in the supplementary file.

Figs.4 & 5

Figs. S1-S9

Table S2

3.2. Coatings anti-corrosion performance screening

3.2.1. EIS studies

The OCP values of the as-received and Sm-treated samples were measured (vs. saturated Calomel

electrode) as a function of exposure time (Fig. S10).

EIS test was applied to investigate the corrosion resistance of the metal substrates coated with the

superhydrophobic coatings. The EIS test was carried out at various immersion times (from 2 hours

to 10 days) on the bare steel, Sm, Sm-PDAT, and Sm-PDAC coated samples. The Bode plots

corresponded to the bare steel, and the treated samples are given in Fig.6. Besides, the data

11
obtained from the modeling of the plots are presented in Tables S3 and S4. Also, the Nyquist

curves for different samples are displayed in Fig. S11. Besides, the charge transfer resistance (Rct)

and coating resistance (Rc) plots versus immersion time are presented in Fig.7. The equivalent

circuits with a one-time constant for bare steel and Sm-treated samples and two-time constant for

the Sm-PDAT and Sm-PDAC samples were used to fit the plots. The elements of these equivalent

circuits were introduced in Table S5. CPE (constant phase element) was used instead of C due to

the porous nature of the deposited coating and the heterogeneous characteristic of the surface. For

the bare steel and Sm-treated samples, an only one-time constant was seen in the plots, indicating

that the metal corrosion reaction is under charge transfer control. The Rct of the bare steel has

increased with the exposure time progress due to the oxidized iron compounds formation on the

metal surface. In the long exposure times, the bare steel's Rct decreased/increased frequently due

to the continuous generation/destruction of the oxidized iron products. The steel surface coverage

with the samarium coating caused the Rct enhancement. The increase in Rct is due to the barrier as

well as the insulating (poor electron conductivity) nature of the samarium film, which makes the

restriction of the corrosive agents access to the metal surface and reduction of the electron mobility

between the cathodic and anodic sites. These all cause metal corrosion resistance improvement.

The Sm3+ cations that exist in the structure of the coating have an inhibitory nature, causing the

passivation of the un-protected areas of the metal surface. These interactions may justify the

increase in the Sm sample Rct over time up to 72 hours. In the immersion times ranged from 72

hours to 168 hours, a decrease in Rct is observed, indicating a drop in the coating barrier property.

Besides, the increase of Rct after 168 hours elucidates the corrosion product generation. Based on

the extracted data, the Sm-PDAC sample revealed the highest Rct values among the samples. This

increase corresponds to the Sm-PDA complexes formation on the anodic region and their

12
adsorption to the surface, resulting in a denser and more compact coating. Upon the synthesis of

polydopamine from dopamine molecules in the synthesis solution, the Sm3+ cations that present in

the coating could covalently coordinate with the polydopamine molecules. The Sm-PDA complex

growth on the metal (iron) surface causes the coverage of the anodic region. Thus, the samarium

coating becomes denser. The EIS results showed that in the early hours, the Sm-PDA sample is

less resistive even compared to the Sm sample itself. These two observations are in contradiction.

The samarium coating was partially damaged in the PDA secondary bath, and some of the formed

oxides were degraded. Therefore, some part of the sample surface becomes unprotected and in

connection with the corrosive agents. So, the resistance of the Sm-PDAC sample is less than that

of the Sm sample. In general, the inhibition mechanisms of the organic inhibitors can be classified

into three categories; i) the geometrical obstruction effect of the adsorbent compounds, ii) blocking

the active site/area by the adsorbent compounds, and iii) electro-catalytic effect of the inhibitor

[67]. In this case, the first and second classes appear to be predominant. The oxygen heteroatom

and catechol presented in the polydopamine inhibitor structure are the electron-rich elements. The

lone-pair orbitals of the oxygen heteroatom can create an organic-inorganic complex with the Fe

atoms [68]. After 24 hours, the Rct of the Sm-PDAC sample has increased remarkably. This

increase is about 10 times greater than that of early times. Probably, the formation of a lot of Fe-

polydopamine complexes on the bare areas of the metal surface has resulted in better surface

coverage and corrosion resistance improvement. The rise and fall of the corrosion resistance at

different immersion times are due to the frequent detachment and formation of these complexes.

The detachment of these complexes is probably due to the poor adhesion of the film to the surface.

Furthermore, the Rc increased up to 24 hours. This increase reflects the development of a compact

coating through the Fe-PDA compounds creation on the anodic regions. The formation of these

13
complexes caused the generation of a robust hybrid (Sm-PDA) coating with water repellency

potency. The Rc drop after 24 hours till 144 hours suggests the coating deterioration in the corrosive

electrolyte. The continuation of the complex formation process and coating degradation caused the

Rc values oscillations over time. In the Sm-PDAT sample, the resistance of the Sm-PDAC sample

is low, so that in the long exposure times, the Rct is even lower than the Sm sample. As the

SEM/EDS results show, the Sm-PDAT coating is porous and non-dense because fewer metal-

organic complexes and PDA molecules are formed on it. This can be related to the synthesis and

oligomerization of the PDA particles. The low Rc relative to the Sm-PDAC also confirms the low

density of the Sm-PDAT coating. Via the formation of the complexes, coating begins to compact

and hydrophobic, so its resistance increased up to 72 hours. In the long exposure times, the coating

is partially destroyed, and its resistance diminished. The Rc changing trend is variable at various

times due to the formation and degradation of the complexes and coating, respectively. The

samarium coating compactness improvement through the formation of more Fe-PDA complexes

and PDA as well as uniform distribution of PDA particles are the reasons for the better corrosion

resistance of the Sm-PDAC sample than other specimens. Utilizing the data extracted from the

fitted EIS diagrams, the inhibition efficiency variations over immersion time have been drawn in

Fig.8. The inhibition efficiency calculation was done by Eq. (1) [22].

η (%) = ((Rt-Rtb)/Rt) ×100 Eq. (1)

In this equation, Rt is the sum of the Rct and Rc of the treated sample, and Rtb is Rct+Rc of the un-

treated steel, respectively. It is observed from this figure that the inhibition efficiency (η) of the

Sm-PDAC sample are higher than other samples at all exposure times. These observations

14
demonstrate the creation of the inhibitive complexes on the weak parts of the surface, leading to

better corrosion protection performance.

Figs. 7 & 8

Figs. S10 & S11

Tables S3-S5

3.2.2. Potentiodynamic polarization analysis

The potentiodynamic polarization test results are presented in Fig.9 (Fig.9a). The test was taken

for all samples after 240 hours. All curves were shifted to Ecorr=0 in order to better investigate the

inhibition mechanism of different samples (Fig.9b). By applying the samarium coating, the Ecorr

displaced to the negative values compared with the untreated sample, demonstrating the cathodic

inhibition action of the samarium cations. The shift of Ecorr to more negative values usually

indicates the cathodic reaction inhibition, and the change of it to a more positive amount confirms

the anodic inhibition activity [69]. The rare earth elements form metal hydroxide containing film

on the cathodic regions, blocking these sites [70]. It can be seen from Fig.9a and b that the Sm

treated samples provided a mixed-inhibition with the anodic branch current density reduction

dominancy. It is evident that in the post-treated samples, the anodic reaction is more affected than

the cathodic reaction, causing a more suppression of the current density of the anodic branch. This

means that the reaction of polydopamine with the iron cations on the anodic regions affected the

iron oxidation reaction. The change in the Tafel slope also reflects the change in the mechanism

of the anodic (iron oxidation) and cathodic (O2 reduction) reactions. The anodic branch slope

change is much more significant for the treated samples, especially for the post-treated samples.

Therefore, the mechanism of inhibition in all samples is mixed-type with anodic reaction

dominancy. Ecorr, icorr, βa, and βc values for the as-received (non-coated) and Sm-treated samples

15
are obtained from the polarization curves using the Tafel extrapolation approach (Table 4). As the

results show, the surface modification by the Sm film reduced the icorr. Among the samples, the

Sm-PDAC sample has the lowest icorr, indicating the best protection against corrosion compared

to the other treated samples. This sample's better corrosion protection performance than the other

samples was also observed from the EIS test outcomes. The difference between the Sm-PDAC and

Sm-PDAT treated samples corrosion resistance can be attributed to the different structures of the

polydopamine particles formed on the iron surface as well as their water stability differences. The

oxidized groups of the polydopamine structure are involved in the adsorption process of the PDA

molecules on the metal (iron) surface through an electron (of heteroatoms) sharing mechanism

between the iron cations and the oxygen/nitrogen heteroatoms [71]. The Cu2+ cations provide the

repulsion forces between the polydopamine NPs, causing their oligomerization prevention [72].

Thus, the high PDAC particles' stability in water is due to the presence of Cu2+ ions. The lower

water stability of the PDAT can be the reason for the poor corrosion inhibition performance of the

PDAT in long exposure times [61].

Fig.9

Table 4

4. Conclusion

According to the previous studies, it can be understood that the hydrophobicity index of the metal

surface can influence its corrosion resistance [29-32, 40-48]. This study has shown that by

chemical modification of the steel surface via the Sm-PDA, a rough anti-corrosion film with good

superhydrophobicity nature can be formed on the steel surface. Some studies have used

biopolymers to control metal corrosion [61]. Moreover, a secondary bath, including an organic

inhibitor, has also been used to improve the properties of the rare earth element-based CCs [25].

16
But in none of them, the film formed on the surface showed superhydrophobic nature. However,

in this study, all treated specimens were hydrophobic compared to the bare steel. The further

hydrophobicity has been obtained through the Sm-treated sample post-modification by PDA

(especially post-modification via PDAC). The SEM micrographs exhibited that the size and

distribution of the polydopamine particles created in the post-modified samples varied, and this

difference affected the surface roughness and hydrophobicity. Small particles with uniform

distribution in the Sm-PDAC sample caused greater surface micro-roughness. Thus, the Sm-PDAC

sample surface has become near superhydrophobic. Furthermore, due to the attendance of less

polar functional groups (such as hydroxyl and amine) in the PDAC structure than PDAT, the Sm-

PDAC sample showed more water-repellency performance. Among all specimens, the Sm-PDAC

showed the best anti-corrosion performance. In general, different methods of polydopamine

synthesis through the establishment of the PDAs with different structures, as well as the differences

in the distribution of the produced particles and their stability in water (their oligomerization), have

affected the hydrophobicity and anti-corrosion properties of the generated coatings. These results

revealed the better corrosion protection performance of the Sm-PDA film compared with those

reported in the literature. It is worth mentioning that most of the methods reported in the previous

studies for achieving superhydrophobicity effects are not environmentally friendly [29-32, 40-48].

Moreover, the eco-friendly surface chemical modification methods applied have resulted in the

hydrophobic surfaces with contact angles in the range of 87°-110° [73, 74]. Even in some cases,

the surface has become hydrophilic [25]. What makes this research achievement superior

compared with the other studies is the conversion of the steel surface characteristic to a near

superhydrophobic (CA>140°( via employing a facile eco-friendly (biomimetic) route. As future

work, other methods of PDA synthesis can be used to improve the properties of the other REE-

17
based CCs. In addition, the impact of Sm-based CC application via the immersion method can be

surveyed as new methods for future studies.

References

[1] I. Santana, A. Pepe, W. Schreiner, S. Pellice, S. Ceré, Hybrid sol-gel coatings containing

clay nanoparticles for corrosion protection of mild steel, Electrochim. Acta. 203 (2016)

396–403.

[2] K.W. Cho, V. Shankar Rao, H.S. Kwon, Microstructure and electrochemical

characterization of trivalent chromium based conversion coating on zinc, Electrochim.

Acta. 52 (2007) 4449–4456.

[3] J.B. Bajat, V.B. Mišković-Stanković, N. Bibić, D.M. Dražić, The influence of zinc surface

pretreatment on the adhesion of epoxy coating electrodeposited on hot-dip galvanized

steel, Prog. Org. Coatings. 58 (2007) 323–330.

[4] S. Palraj, M. Selvaraj, P. Jayakrishnan, Effect of phosphate coatings on the performance

of epoxy polyamide red oxide primer on galvanized steel, Prog. Org. Coatings. 54 (2005)

5–9.

[5] Z. Zou, N. Li, D. Li, H. Liu, S. Mu, A vanadium-based conversion coating as chromate

replacement for electrogalvanized steel substrates, J. Alloys Compd. 509 (2011) 503–507.

[6] B. Díaz, L. Freire, M. Mojío, X.R. Nóvoa, Optimization of conversion coatings based on

zinc phosphate on high strength steels, with enhanced barrier properties, J. Electroanal.

Chem. 737 (2015) 174–183.

[7] M.F. Morks, Magnesium phosphate treatment for steel, Mater. Lett. 58 (2004) 3316–3319.

[8] W. Zhu, W. Li, S. Mu, N. Fu, Z. Liao, Comparative study on Ti/Zr/V and chromate

18
 conversion treated aluminum alloys: Anticorrosion performance and epoxy coating

adhesion properties, A.S. Science. 405 (2017) 157-168.

[9] Y. Chang, N. Wen, W. Chen, M. Ger, G. Pan, The effects of immersion time on

morphology and electrochemical properties of the Cr (III)-based conversion coatings on

zinc coated steel surface, Corr. Sci. 50 (2008) 3494-3499.

[10] Z. Zou, N. Li, D. Li, H. Liu, S. Mu, A vanadium-based conversion coating as chromate

replacement for electrogalvanized steel substrates, J. of A. and Compounds. 509 (2011)

503-507.

[11] A. Phelps, J. Sturgill, J.T. Swartzbaugh, Non-toxic corrosion-protection conversion coats

based on rare earth elements, US Patent. (2008).

[12] Y. Xingwen, C. Chunan, Y. Zhiming, Z. Derui, Y. Zhongda, Corrosion behavior of rare

earth metal (REM) conversion coatings on aluminum alloy LY12, Mater. Sci. and Eng. A.

284 (2000) 56-63.

[13] M. Bethencourt, F.J. Botana, M.J. Cano, M. Marcos, Advanced generation of green

conversion coatings for aluminium alloys, A.S. Science. 238 (2004) 278-281.

[14] M. Dabalà, E. Ramous, M. Magrini, Corrosion resistance of cerium-based chemical

conversion coatings on AA5083 aluminium alloy, Mater. Corros. 55 (2004) 381–386.

[15] D. Chen, J. Wu, Y. Liang, S. Ye, W. Li, Preparation of cerium oxide based environment-

friendly chemical conversion coating on magnesium alloy with additives, T. of

Nonferrous Met. Soc. of China. 21 (2011) 1905-1910.

[16] B. Valdez, S. Kiyota, M. Stoytcheva, R. Zlatev, J. Bastidas, Cerium-based conversion

coatings to improve the corrosion resistance of aluminium alloy 6061-T6, Corr. Sci. 87

(2014) 141-149.

19
[17] A. Shashikala, R. Umarani, S. Mayanna, K. Sharma, Chemical conversion coatings on

magnesium alloys-A comparative study, Int. J. Electrochem. Sci. 3 (2008) 993 - 1004.

[18] G. Jin, Y. Yang, X. Cui, E. Liu, Z. Wang, Q. Li, Chrome-free neodymium-based

protective coatings for magnesium alloys, Mater. Letters. 65 (2011) 1145-1147.

[19] Z. Dingzang, Z. Dingfei, L. Yuping, H. Guangshan, G. Yinning, P. Fusheng, Neodymium-

based conversion coating on AZ31 magnesium alloy, R.E. Mater. and Eng. 46 (2017) 289-

295.

[20] S.S. Jamali, S.E. Moulton, D.E. Tallman, M. Forsyth, J. Weber, Corrosion protection

afforded by praseodymium conversion film on Mg alloy AZNd in simulated biological

fluid studied by scanning electrochemical microscopy, J. of Elec. Chemistry. 739 (2015)

211-217.

[21] A.L. Rudd, C.B. Breslin, F. Mansfeld, The corrosion protection afforded by rare earth

conversion coatings applied to magnesium, Corr. Sci. 42 (2000) 275-288.

[22] G. Kong, L. Lingyan, J. Lu, C. Che, Z. Zhong, Corrosion behavior of lanthanum-based

conversion coating modified with citric acid on hot dip galvanized steel in aerated 1 m

NaCl solution, Corr. Sci. 53 (2011) 1621-1626.

[23] X.F. Cui, G. Jin, Y.Y. Yang, L.L. Lin, H.D. Wang, B.S. Xu, Study of gadolinium based

protective coating for magnesium alloys, Surf. Eng. 28 (2012) 719–724.

[24] G. Jin, Y. Yang, L. Hou, X. Cui, L. Lin, Q. Xiao, Chrome-free Samarium-based Protective

Coatings for Magnesium, Phys. Procedia. 50 (2013) 261–266.

[25] P. Riazaty, R. Naderi, B. Ramezanzadeh, Enhancement of the Epoxy Coating

Corrosion/Cathodic Delamination Resistances on Steel by a Samarium Based Conversion

Coating, J. Electrochem. Soc. 166 (2019) 353–364.

20
[26] Y. Ye, D. Yang, H. Chen, S. Guo, Q. Yang, L. Chen, H. Zhao, L. Wang, A high-

efficiency corrosion inhibitor of N-doped citric acid-based carbon dots for mild steel in

hydrochloric acid environment, J. Hazard. Mater. 381 (2020).

[27] C.M. Taylor, A. Ramirez-Canon, J. Wenk, D. Mattia, Enhancing the photo-corrosion

resistance of ZnO nanowire photocatalysts, J. Hazard. Mater. 378 (2019).

[28] N. Yang, T. Yang, W. Wang, H. Chen, W. Li, Polydopamine modified polyaniline-

graphene oxide composite for enhancement of corrosion resistance, J. Hazard. Mater. 377

(2019) 142–151.

[29] J. Song, Y. Li, W. Xu, H. Liu, Y. Lu, Inexpensive and non-fluorinated superhydrophobic

concrete coating for anti-icing and anticorrosion, J. of Collo. and Inter. Sci. 541 (2019)

86-92.

[30] B. Zhang, W. Xu, Q. Zhu, Y. Li, B. Hou, Ultrafast one step construction of non-fluorinated

superhydrophobic aluminum surfaces with remarkable improvement of corrosion

resistance and anti-contamination, J. of Collo. and Inter. Sci. 532 (2018) 201-209.

[31] Y. Cheng, B. Wu, X. Ma, S. Lu, W. Xu, S. Szunerits, R. Boukherroub, Facile preparation

of high density polyethylene superhydrophobic/superoleophilic coatings on glass, copper

and polyurethane sponge for self-cleaning, corrosion resistance and efficient oil/water

separation, J. of Collo. and Inter. Sci. 552 (2018) 76-85.

[32] X. Gao, Z. Guo, Mechanical stability, corrosion resistance of superhydrophobic steel and

repairable durability of its slippery surface, J. of Collo. and Inter. Sci. 512 (2018) 239-248.

[33] A. Scardino, R.D. Nys, O. Ison, W. O'Connor, P. Steinberg, Microtopography and

antifouling properties of the shell surface of the bivalve molluscs mytilus galloprovincialis

and pinctada imbricata, The J. of Bioad. and Biofilm Res. 19 (2003) 221-230.

21
[34] D. Quere, Non-sticking drops, Rep. Prog. Phys. 68 (2005) 2495.

[35] H. Saito, K. Takai, H. Takazawa, G. Yamauchi, Relationships between water wettability

and ice adhesion, Mater. Sci. Res. Int. 3 (2010), 3100-3110.

[36] Z. Youfa, Y. Xinquan, Z. Quanhui, L. Kangning, Fabrication of superhydrophobic steel

surface and its anti-frosting performance, J. of Southeast Uni. (Nat. Sci. Ed.). 6 (2010).

[37] S. Chatterjee, P. Das, U. Tripathy, B.P. Singh, L. Besra, Development of polymer-based

superhydrophobic coating on cloth, Bull Mater Sci. 43 (2020) 130.

[38] M. Zielecka, E. Bujnowska, Silicone-containing polymer matrices as protective coatings:

Properties and applications, Prog. Org. Coat. 55 (2006) 160-167.

[39] J. Guo, F. Yang, Z. Guo, Fabrication of stable and durable superhydrophobic surface on

copper substrates for oil–water separation and ice-over delay, J. of Coll. and Inter. Sci.

466 (2016) 36-43.

[40] N. Wang, D. Sheng Xiong, Y. Shi, Mechanically Robust Superhydrophobic Steel Surface

with Anti-Icing, UV-Durability, and Corrosion Resistance Properties Superhydrophobic

coatings, ACS Publ. 7 (2015) 6260–6272.

[41] L. Li, Y. Zhang, J. Lei, J. He, R. Lv, N. Li, F. Pan, A facile approach to fabricate

superhydrophobic Zn surface and its effect on corrosion resistance, Corr. Sci. 85 (2014)

174-182.

[42] F. Xiao, S. Yuan, B. Liang, G. Li, S.O. Pehkonen, T. Zhang, Superhydrophobic CuO

nanoneedle-covered copper surfaces for anticorrosion, J. Mater. Chem. A. 3 (2015) 4374–

4388.

[43] Z. She, Q. Li, Z. Wang, C. Tan, J. Zhou, L. Li, Highly anticorrosion, self-cleaning

superhydrophobic Ni–Co surface fabricated on AZ91D magnesium alloy, S. and C.

22
 Technology. 251 (2014) 7-14.

[44] A. Rao, S. Latthe, S. Mahadik, C. Kapenstain, Mechanically stable and corrosion resistant

superhydrophobic sol–gel coatings on copper substrate, A.S. Science. 257 (2011) 5772-

5776.

[45] Y. Qing, C. Yang, C. Hu, Y. Zheng, C. Liu, A facile method to prepare superhydrophobic

fluorinated polysiloxane/ZnO nanocomposite coatings with corrosion resistance, A.S.

Science. 362 (2015) 48-54.

[46] D. Qin, Y. Xia, G.M. Whitesides, Soft Lithography for Micro-and Nanoscale Patterning,

Nat. Protoc. 5 (2010) 491–502.

[47] T. Liu, Y. Yin, S. Chen, X. Chang, S. Cheng, Super-hydrophobic surfaces improve

corrosion resistance of copper in seawater, Electrochem. Acta. 52 (2007) 3709-3713.

[48] T. Ishizaki, Y. Masuda, M. Sakamoto, Corrosion resistance and durability of

superhydrophobic surface formed on magnesium alloy coated with nanostructured cerium

oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution, Langmuir.

27 (2011) 4780–4788.

[49] A. Anjum, M. Ali, K. Sun, R. Riaz, S. Jeong, Self-assembled nanomanipulation of silica

nanoparticles enable mechanochemically robust super hydrophobic and oleophilic textile,

J. of Coll. and Inter. Sci. 563 (2020) 62-73.

[50] H. Kang, X. Zhang, L. Li, B. Zhao, F. Ma, J. Zhang, Polydopamine and

poly(dimethylsiloxane) modified superhydrophobic fiberglass membranes for efficient

water-in-oil emulsions separation, J. of Coll. and Inter. Sci. 559 (2020) 178–185.

[51] S. Pan, N. Wang, D. Xiong, Y. Deng, Y. Shi, Fabrication of superhydrophobic coating via

spraying method and its applications in anti-icing and anticorrosion, A.S. Science. 389

23
 (2016) 547-553.

[52] N. Cao, Y. Miao, D. Zhang, R. Boukherroub, X. Li, H. Ju, H. Li, Preparation of mussel-

inspired perfluorinated polydopamine film on brass substrates: Superhydrophobic and

anticorrosion application, Prog. in Org. Coatings. 125 (2018) 109-118.

[53] B. Fei, B. Qian, Z. Yang, R. Wang, W. Liu, C. Mark, J. Xin, Coating carbon nanotubes by

spontaneous oxidative polymerization of dopamine, Carbon. 46 (2008) 1795-1797.

[54] G. Zeng, T. Chen, L. Huang, M. Liu, Surface modification and drug delivery applications

of MoS2 nanosheets with polymers through the combination of mussel inspired chemistry

and SET-LRP, J. of the Taiwan Ins. of Chem. Eng. 82 (2018) 205-213.

[55] G. Zeng, L. Huang, Q. Huang, M. Liu, D. Xu, Rapid synthesis of MoS2-PDA-Ag

nanocomposites as heterogeneous catalysts and antimicrobial agents via microwave

irradiation, A.S. Science. 459 (2018) 588-595.

[56] Y. Liu, K. Ai, L. Lu, Polydopamine and its derivative materials: Synthesis and promising

applications in energy, environmental, and biomedical fields, Chem. Rev. 114 (2014)

5057–5115.

[57] J. Hu, Q. Wang, Y. Wang, G. You, P. Li, L. Zhao, H. Zhou, Polydopamine-based surface

modification of hemoglobin particles for stability enhancement of oxygen carriers, J. of

Collo. and Inter. Sci. 571 (2020) 326-336.

[58] R. Li, J. Liu, A. Shi, X. Luo, J. Lin, R. Zheng, H. Fan, S. Selasie, H. Lin, A facile method

to modify polypropylene membrane by polydopamine coating via inkjet printing

technique for superior performance, J. of Collo. and Inter. Sci. 552 (2019) 719-727.

[59] W. Yang, K. Zeng, J. Liu, L. Chen, M. Wang, S. Zhuo, X. Ge, Fabrication of inverse-opal

lysozyme-imprinted polydopamine/polypyrrole microspheres with near-infrared-light-

24
 controlled release property, J. of Collo. and Inter. Sci. 548 (2019) 37-47.

[60] F. Tang, L. Liu, H. Wang, X. Gao, Z. jin, The combination of metal-organic frameworks

and polydopamine nanotubes aiming for efficient one-dimensional oxygen reduction

electrocatalyst, J. of Collo. and Inter. Sci. 552 (2019) 351-358.

[61] A. Habibiyan, B. Ramezanzadeh, M. Mahdavian, M. Kasaeian, Facile size and chemistry-

controlled synthesis of mussel-inspired bio-polymers based on Polydopamine

Nanospheres: Application as eco-friendly corrosion inhibitors, J. Molec. Liq. 298 (2020).

[62] A. Postma, Y. Yan, Y. Wang, A.N. Zelikin, E. Tjipto, F. Caruso, Self-polymerization of

dopamine as a versatile and robust technique to prepare polymer capsules, Chem. Mater.

21 (2009) 3042–3044.

[63] C. Zhang, Y. Ou, W.X. Lei, L.S. Wan, J. Ji, Z.K. Xu, CuSO4/H2O2-Induced Rapid

Deposition of Polydopamine Coatings with High Uniformity and Enhanced Stability,

Angew. Chemie - Int. Ed. 55 (2016) 3054–3057.

[64] D. Li, A. Neumann, A reformulation of the equation of state for interfacial tensions, J. of

Coll. and Inter. Sci., 137 (1990) 304-307.

[65] E. Bormashenko, T. Stein, G. Whyman, Y. Bormashenko, R. Pogreb, Wetting Properties

of the Multiscaled Nanostructured Polymer and Metallic Superhydrophobic Surfaces,

Langmuir. 22 (2006) 9982-9985.

[66] T. L. Liu, Z. Chen, C. J. Kim, A dynamic Cassie–Baxter model, S. Matter. 11 (2015)

1589-1596.

[67] B.E. Amitha Rani, B.J. Bai Basu, Green Inhibitors for Corrosion Protection of Metals and

Alloys: An Overview, Int. J. Corros. 2012 (2012) 15.

[68] S. Cheng, S. Chen, T. Liu, X. Chang, Y. Yin, Carboxymenthylchitosan as an ecofriendly

25
 inhibitor for mild steel in 1 M HCl, Mater. Letters. 61 (2007) 3276-3280.

[69] M. Izadi, T. Shahrabi, B. Ramezanzadeh, Active corrosion protection performance of an

epoxy coating applied on the mild steel modified with an eco-friendly sol-gel film

impregnated with green corrosion, A.S. Science. 440 (2018) 491-505.

[70] A.J. Aldykewicz, The Investigation of Cerium as a Cathodic Inhibitor for Aluminum-

Copper Alloys, J. Electrochem. Soc. 142 (1995) 3342.

[71] J. Jiang, L. Zhu, L. Zhu, B. Zhu, Y. Xu, Surface characteristics of a self-polymerized

dopamine coating deposited on hydrophobic polymer films, Langmuir. 27 (2011) 14180–

14187.

[72] S. Hong, Y.S. Na, S. Choi, I.T. Song, W.Y. Kim, H. Lee, Non-covalent self-assembly and

covalent polymerization co-contribute to polydopamine formation, Adv. Funct. Mater. 22

(2012) 4711–4717.

[73] N. Follain, R. Saiah, K. Fatyeyeva, N. Randrianandrasana, N. Leblanc, S. Marais, L.

Lecamp, Hydrophobic surface treatments of sunflower pith using eco-friendly processes,

Cellulose. 22 (2015) 245–259.

[74] L. Lei, J. Shi, X. Wang, D. Liu, H. Xu, Microstructure and electrochemical behavior of

cerium conversion coating modified with silane agent on magnesium substrates, A.S.

Science. 376 (2016) 161-171.

Figures caption:

Figure 1. Schematic of a) samarium film formation mechanism, b) PDAT and c) PDAC secondary

bath

26
Figure 2. The contact angle of pure water on the surface of a) bare steel, b) Sm, c) Sm-PDAT, d)

Sm-PDAC specimens

Figure 3. Schematic of CA increasing mechanism via Sm and Sm-PDA coating compared with

bare steel

Figure 4. SEM images of the 10 days immersed a) bare steel, b) Sm, c) Sm-PDAT and d) Sm-

PDAC samples into 3.50%-based NaCl media

Figure 5. EDS spectrum of a) bare steel, b) Sm, c) Sm-PDAT and d) Sm-PDAC after 10 days

subjection to 3.50%-based NaCl corrosive medium

Figure 6. Bode plots of a) bare steel, b) Sm, c) Sm-PDAT and d) Sm-PDAC samples immersed in

3.50%-based NaCl for various time

Figure 7. a) Rct and b) Rc variations of different specimens over immersion time

Figure 8. Inhibition efficiency variations of various samples over immersion time

Figure 9. a) Polarization plots of untreated and treated samples immersed in 3.50%-based NaCl

for 10 days at ambient temperature, b) shifted plots to Ecorr = 0

27
 Table 1

Sm chemical treated bath composition

Composition Content

Samarium(III) nitrate hexahydrate 2 (gr/L)

Hydrogen peroxide 5 (mL/L)

Hydrochloric acid 11.30 (mL/L)

Table 2

Bath composition of different polydopamine synthesis methods

Method Bath composition pH

Self-induced (PDAT) 2 mg/mL dopamine hydrochloride + 10 mM tris (hydroxymethyl) - 8.50

aminomethane

Oxidant-induced (PDAC) 2 mg/mL dopamine hydrochloride + 10 mM tris (hydroxymethyl) - 8.50

aminomethane + 5 mM CuSO4 + 19.60 mM H2O2

28
Table 3

Contact angle test measurements

Sample θ (deg) WA (mJ/m2) γsv (mJ/m2)

Bare steel 83.35 ± 3.50 81.17 ± 4.40 33.35 ± 1.90

Sm 101.25 ± 5.85 58.60 ± 7.30 22.28 ± 3.50

Sm-PDAT 118.25 ± 1.43 38.36 ± 1.60 12.51 ± 0.76

Sm-PDAC 138.65 ± 2.80 18.20 ± 2.40 3.73 ± 0.87

Table 4

Data extract from polarization curves for different samples

Sample -Ecorr (mV) icorr (μA/cm2) _

βc (mV/decade) βa (mV/decade)

Bare steel 820 13.50 108.67 81.06

Sm 838.30 8.53 118.02 10.22

Sm-PDAT 842.80 9.03 121.52 1.97

Sm-PDAC 889 5.92 132.30 1.28

29
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

31
Farshad Bahremand: Writing - review & editing, Taghi Shahrabi: Writing - review & editing,
Bahram Ramezanzadeh: Writing - review & editing,

32
5: Figure
Figure 1

(a)

(b) (c)
H
5: Figure
Figure 2
a b

c d
5: Figure
Figure 3
5: Figure
Figure 4 (a) (b)

(c) (d)
5: Figure
Figure 5

Fe 92.85% 82.94%

O 1.15% 7.55%

Sm 1.8%

C 3.69%

N 4.01%

62.71% 87.11%

33.52% 4.44%

3.77% 0.83%
4.67%

2.94%
Figure 6
5: Figure 68 70

48 50

1.50 28 30

0.50 8 10
(a) (b)
50

50 40

30
30
20

1.50 10 10
(c) (d)
5: Figure
Figure 7

Blank (a) (b)

500
5: Figure
Figure 8
5: Figure
Figure 9

(a) (b)
*3: Graphical Abstract