Accepted Manuscript

Experimental, quantum chemical calculations and molecular

dynamics (MD) simulation studies of methionine and valine as
corrosion inhibitors on carbon steel in phase change materials
(PCMs) solution

Zhe Zhang, Wenwu Li, Weipeng Zhang, Xiaodong Huang, Le

Ruan, Ling Wu

PII: S0167-7322(18)33792-9
DOI: doi:10.1016/j.molliq.2018.09.081
Reference: MOLLIQ 9687
To appear in: Journal of Molecular Liquids
Received date: 23 July 2018
Revised date: 7 September 2018
Accepted date: 17 September 2018

Please cite this article as: Zhe Zhang, Wenwu Li, Weipeng Zhang, Xiaodong Huang, Le
Ruan, Ling Wu , Experimental, quantum chemical calculations and molecular dynamics
(MD) simulation studies of methionine and valine as corrosion inhibitors on carbon steel in
phase change materials (PCMs) solution. Molliq (2018), doi:10.1016/j.molliq.2018.09.081

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 ACCEPTED MANUSCRIPT

Experimental, quantum chemical calculations and molecular

dynamics (MD) simulation studies of methionine and valine
as corrosion inhibitors on carbon steel in phase change
materials (PCMs) solution

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Zhe Zhang a,b, Wenwu Li a, Weipeng Zhang a, Xiaodong Huang a, Le Ruan a,b*, Ling Wu c

a Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional

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Materials, College of Chemistry and Bioengineering, Guilin University of Technology,

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Guilin 541004, PR China NU
b Guangxi Key Laboratory of Geomechanics and Geotechnical Engineering, Guilin

University of Technology, Guilin 541004, PR China

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c School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100,

PR China
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*Corresponding author. Tel.: +86 15296001527; Email: ruanle@glut.edu.cn.

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Abstract

Corrosion inhibition of methionine (Met) and valine (Val) molecules on carbon steel

was investigated in phase change materials solution. Electrochemical measurements

showed that these inhibitors can protect steel against corrosion, with a maximal protection

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efficiency up to 96.85% by the molar ratio of Met/Val is 1/1 and the concentration of Met

is 0.05 mol·L-1. All inhibitors acted as anode type inhibitors. The analysis result of

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scanning electron microscope (SEM) showed that the surface morphology of the carbon

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steel sample immersed in the phase change materials solution in the presence of the
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Met/Val inhibitor was significantly better than that of the uninhibited sample. The
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inhibition mechanism was theoretically investigated through the quantum chemical

calculation and molecular dynamic simulation, that showed the Methionine and valine
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molecules could adsorb on Fe (1 1 0) surface, N atoms, S atoms, and -COOH group were
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the main adsorption active sites. Finally, the migration rate of Cl- ions in the film of three
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corrosion inhibitors (concentration: 0.05 mol·L-1) was studied.

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Key words: Carbon steel; EIS; Polarization; Modeling study; Inhibition

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*Corresponding author. Tel.: +86 15296001527; Email: ruanle@glut.edu.cn.

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1. Introduction

Phase change materials (PCMs) are high-concentration ion mixed solutions

composed of inorganic salts and water and other additives, which can absorb and release a

large amount of heat from the environment during the phase change of temperature rise

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and decrease[1, 2]. Because of high latent heat, relatively high thermal conductivity,

non-toxicity, non-flammability and low cost[3], PCMs are widely used in solar energy

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storage[4-6], energy-saving buildings[2, 7, 8], storage and transportation of aquatic

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products[9-11]. However, as a kind of inorganic salt phase change cold accumulating
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material, PCMs have a high ion concentration liquid phase which will cause serious

corrosion of metal containers[12-16], so the development and application of PCMs are

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hindered.
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PCMs are usually hydrated salts containing additives such as pour point depressants
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(KCl, NaCl, NH4Cl, etc.) and nucleating agents (borax and nano-BaCl2, etc.), which have
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a liquid pH of 5 < pH < 8[17, 18]. The corrosion reaction of metal materials such as
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carbon steel in PCMs is completely different from the corrosion reaction in hydrochloric
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acid because of the more complicated composition. For this reason, the corrosion product

(Fe2O3 or NH4FePO4·nH2O) can be converted to soluble FeCl2 and dissolved in the PCMs,

making Cl- ions a key factor in the corrosion of carbon steel in PCMs[19]. At present,

there are a few methods to reducing the corrosion of carbon steel in PCMs solution. Ryo

Fukahori et al[20], studied the corrosion behavior of engineering ceramics (such as Al2O3,

AlN, Si3N4, SiC and SiO2) in high-temperature PCMs. Experiments showed that Al2O3,

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AlN and Si3N4 have high corrosion resistance to high-temperature PCMs and were

suitable for containers of PCMs. Moreno et al[21], studied the corrosion rate of copper,

aluminium, stainless steel 316 and carbon steel in contact with PCMs, and suggested the

use of different metals and metal alloys in PCMs based on the obtained corrosion rate and

observation of the sample. Ferrer et al[7]. Studied the corrosive effects of five metals

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(aluminium, copper, carbon steel, stainless steel 304 and stainless steel 316) when in

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contact with four different PCMs (one inorganic mixture, one ester and two fatty acid

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eutectics). The results indicated that aluminum samples were not suitable for inorganic

PCMs, copper could be used in fatty acid PCMs, and stainless steel was suitable for all
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PCMs.
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Amino acids are considered to be popular green corrosion inhibitors because of their

non-toxicity, low cost, etc[22-24]. In this paper, the corrosion inhibition properties of
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methionine and Valine on carbon steel in PCMs were investigated. The molecular
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information of methionine (Met) and Valine (Val) is shown in Table 1. Electrochemical

measurements were used to study corrosion inhibition efficiency. The characterization

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technique of SEM was used to verify the corrosion inhibition effect. The corrosion
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inhibition mechanism of the system was studied by quantum chemical calculation and

molecular dynamics simulation.

2. Experiments

2.1. Preparation of electrodes

A cylindrical carbon steel (composition, wt.%: C 0.45%, Si 0.17%, Mn 0.5%, S

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0.035%, P 0.035%, Cr 0.25%, Cu 0.25%, Ni 0.30%, and Fe 98%) having a length of 2.5

cm and an exposed geometrical area of 0.5024 cm2 was used as a working electrode to

which a copper wire was connected and epoxy resin was mounted in a suitable size glass

tube.

Before the experiment, metallographic sandpaper (300#, 800#, 1200#, 1400#) was

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used to grind the exposed end face of the working electrode step by step to the light level

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of the mirror. The polished working electrode was rapidly washed with distilled water and

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placed in anhydrous ethanol for ultrasonic cleaning for 5 minutes, and then replaced with
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fresh anhydrous ethanol and ultrasonically cleaned again for 1 minute. The cleaned

electrode was sealed in absolute ethanol for use.

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2.2. Preparation of phase change materials (PCMs)

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The composition (wt.%) and role of the phase change cold storage material in this
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experiment were as follows[19]: Na2SO4·10H2O (43.2%, main phase change material),

Na2HPO4·12H2O (12.3%, main phase change material), NH4Cl (6.2%, pour point
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depressant), KCl (3.1%, pour point depressant), NH4H2PO4 (3.1%, buffer), borax (1.9%,
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nucleating agent), CMC (2.5%, flocculant ), H2O (27.8%, solvent). Each component

material was placed in an Erlenmeyer flask and dissolved under magnetic stirring at a

water bath temperature of 40 oC to prepare a eutectic salt phase change virtual cold

material for use.

The corrosion inhibitors were methionine (> 99%, Macklin), proline (> 99%,

Mackline), and the combination of two corrosion inhibitors. A certain amount of corrosion
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inhibitor was weighed out and added to the prepared PCMs solution, and PCMs corrosion

solution samples containing different concentrations of corrosion inhibitors were prepared

and allowed to stand for 12 hours at 25 oC. The thermal physical properties of the prepared

PCMs were tested by the step cooling curve test method. The test results are shown in Fig.

1.

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From Fig. 1, it can be seen that the PCMS solution prepared in this experiment has a

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crystallization temperature of about 6.4 oC, a phase transition temperature of about 7.3 oC,

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and a degree of undercooling of less than 2 oC. At room temperature, it has phase change
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energy storage performance and good cycle performance. In addition, the PCMs had a pH

of 6.5 as measured by a pH meter. Therefore, there is no obvious effect on the

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performance of PCMs after the addition of inhibitors, so methionine and valine molecules

can be used as the research object for this experiment.

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2.3. Electrochemical measurements

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The traditional three-electrode test system was used to test the corrosion inhibitor of
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carbon steel corrosion inhibition performance in PCMs solution at constant temperature 25

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o
C. The volume of the electrolysis cell is 100 ml, the working electrode is a carbon steel

electrode, the auxiliary electrode is a platinum plate (1.0 cm × 1.8 cm), and the reference

electrode is a saturated calomel electrode (SCE). The electrode potentials described herein

are all relative to SCE.

The electrochemical impedance spectroscopy (EIS) measurements and the

potentiodynamic polarization measurements are all based on the IM6 electrochemical

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workstation (ZAHNER, Germany). Before testing, the working electrode was immersed in

the test solution for 1h until the open circuit potential (OCP) was stable. Impedance tests

were conducted at open circuit potential and a sinusoidal applied voltage of 5 mV was

applied to the electrode system. The test frequency range was 100 kHz to 0.1 Hz,

sweeping from high frequency to low frequency. The AC impedance test data was fitted

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using ZView 2 software. The potentiodynamic polarization curve test has a potential scan

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range of OCP ± 200 mV, sweeping from low potential to high potential, and scanning

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speed of 2 mV/s. The data of the potentiodynamic polarization curve test were all

processed by the Tafel extrapolation method from the electrochemical workstation's own
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fitting software.
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2.4. surface morphological studies

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The pretreated carbon steel specimens (3 mm × 3 mm × 1 mm) were soaked in blank

and PCMs solutions containing corrosion inhibitors for 48 h. Due to the large surface
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activity of the surface of the corroded carbon steel specimens, it is easily oxidized.
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Therefore, the etched specimens was quickly washed with distilled water, then placed in a

certain amount of absolute ethanol, and the sample was dried by evaporation under

reduced pressure. The surface morphology of specimens was observed and detected by a

HITACHI (SU 5000) scanning electron microscope (SEM).

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2.5. Quantum chemical calculations

Using the DFT/B3LYP method in Gaussian 03w software[25], the geometric

configuration and single-site energy calculation of amino acid molecules were performed

at the 6-311G (d, p) unit level. The quantum chemical parameters such as the highest

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occupied orbital energy (E HOMO), the lowest unoccupied orbital energy (ELUMO), the

energy gap (∆E =ELUMO - EHOMO), the dipole moment (μ), and the surface charge

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distribution of each amino acid molecule were obtained. Finally, Gaussian View 5.0

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software was used to visualize the results of quantum chemistry calculations, and the
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differences in properties caused by structural changes were visually demonstrated.
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2.6. Molecular dynamic (MD) simulations

The interaction of Met, Val and Met/Val compound corrosion inhibitors and Fe
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crystals in PCMs solution was simulated and studied by Accerrys Inc.'s Material Studio
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6.0 software[26]. In addition, the diffusion of Cl- ions in three corrosion inhibitor films

was simulated and analyzed. The steps and parameters of the simulation system
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construction have been detailed in Zhang Zhe's work[19].

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The first simulation system was built using an amorphous cell module. The most

stable and dense Fe (1 1 0) surface was selected for supercell creation[27, 28]. The

composition of the solution layer is 30 Na+, 10 SO42-, 5 PO43-, 5 H3O+, 5 NH4+, 5 Cl-, 500

H2O and a corrosion inhibitor molecule. The second simulation system consists of 50

corrosion inhibitor molecules and one Cl- ion.

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The optimized after the system was built. Finally, the molecular dynamics simulation

process was performed before the temperature and energy of the entire system were

stabilized.

3. Results and discussion

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3.1. Electrochemical impedance spectroscopy (EIS) measurements

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As shown in Fig. 2, the impedance plots for the absence and presence of different

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concentrations (0.001 mol·L-1, 0.005 mol·L-1, 0.01 mol·L-1, 0.02 mol·L-1, 0.03 mol·L-1,

0.04 mol·L-1 and 0.05 mol·L-1) of inhibitor samples have been tested in PCMs solution at
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25 ◦C, with an immersion time of 1 h (The working electrode (WE) was immersed in the
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test solution for 1 h to obtain a stable open circuit potential before each test). It can be

clearly seen from the Nyquist plots that all curves exhibit a concave semicircular in the
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high frequency region, the diameter of which is represents the charge transfer resistance
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(Rct). Usually, the measured impedance loop is a concave semicircle whose center is lower

than the real axis. This phenomenon is called dispersing effect[29-31]. In addition, it is
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found from the Bode plots that the phase angle of the corrosion inhibitor is larger than the
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blank sample, and the phase angle value of the corrosion inhibitor increases as the

concentration of the corrosion inhibitor increases. It is shown that the corrosion inhibitor

molecules form an adsorption film on the surface of carbon steel, and the coverage of the

corrosion-inhibiting film layer increases with the increase of the corrosion inhibitor

concentration[32].

The impedance experimental data were fitted to obtain the parameters of each circuit
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component in the equivalent circuit by ZView 2 software. The equivalent circuit was

shown in Fig. 3, with the parameters of each component were listed in Table 2. Excellent

fit results can be obtained with this equivalent circuit. In the equivalent circuit diagram, Rs

is the solution resistance between the working electrode and the reference electrode. It is

considered that the PCMs solution with high-concentration salt contains a large amount of

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PO43- and SO42- anions capable of strong adsorption on the iron surface. C1 and R1 are the

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electric double layer capacitance and charge transfer resistance between the solution and

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an anion concentration layer such as PO43- and SO42-, respectively. Rct is the charge

transfer resistance between the working electrode surface and the solution layer. The
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electric double layer resistor does not appear to be an ideal capacitor in consideration of
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the dispersion effect. Therefore, CPE is used as a substitute for capacitors and is used to

explain the deviation caused by surface roughness[33-37]. The admittance (Y) of the CPE
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is defined as[36]:
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Y CPE  Y 0  j 
n
(1)
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Where Y0 and n are modulus and deviation parameters, respectively. ω represents the

angular frequency at the maximum imaginary part of the impedance.

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The inhibition efficiencies (ηR) of inhibitors is calculated according to the Eq (2):

%  Rct  Rct 100

0
 (2)
Rct

where R0ct is the charge transfer resistances of Working electrode in the absence of

inhibitors and Rct is the charge transfer resistances of Working electrode in the presence of
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inhibitors.

As can be seen from Table 2, the values of C1 and R1 obtained were small and did not

change, indicating that the electric double layer of sulfate and phosphate ions is not

resistant to corrosive ions such as Cl- ions. In addition, as the concentration of the inhibitor

increases, the value of Y0 decreases and the charge transfer resistance increases. This can

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be attributed to a decrease in the local dielectric constant or an increase in the thickness of

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the electric double layer. The decrease in the Y0 value may be due to the replacement of

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water molecules and other molecules adsorbed on the iron surface by the corrosion
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inhibitor molecules. It was confirmed that the corrosion inhibitor molecules act by

adsorption at the metal/solution interface[38]. The value of the deviation parameter (n) can
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be used as an indicator to predict the dissolution mechanism in the system[39]. The

stability of the n value indicates that the charge transfer process controls the dissolution
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mechanism in the system without and with different concentrations of corrosion inhibitor.
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The order of the maximum charge transfer resistance values of the three corrosion

inhibitors is Met/Val (17861 Ω cm2) >Met (4262 Ω cm2) >Val (2165 Ω cm2), as shown in Fig.
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2 (g).
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The synergistic parameter (S) obtained from the corrosion inhibition efficiency value

(η) was used to evaluate the interaction relationship and synergistic inhibition effect of the

mixed corrosion inhibitor. According to previous experience[40-44], the following

equation can be used to calculate the synergistic parameter:

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1   12 
S  (3)
1   1 2 

where η(1+2) = (η1 + η2 ) − (η1 ×η2 ), η1 and η2 are the inhibition efficiency values

representing Met and Val, respectively. η(1/2) is the inhibition efficiency of the mixed

inhibitor. Table 2 shows that the S of Met/Val compound inhibitor is less than 1 when the

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inhibitor concentration is less than 0.03 mol·L-1. Moreover, charge transfer resistance of

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the Met/Val compound inhibitor is less than the single inhibitor. This result indicates that

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the competitive adsorption exists between Met and Val molecules. When the inhibitor

concentration is greater than 0.04 mol·L-1, the S of the Met/Val compound inhibitor is
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greater than 1, and charge transfer resistance of the Met/Val compound inhibitor is greater
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than the single inhibitor. This indicates that the interaction between Met and Val molecules

is synergistic adsorption.
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3.2. Potentiodynamic polarization measurements

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As shown in Fig. 4, the polarization curves for the absence and presence of different
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concentrations of inhibitor samples have been tested in PCMs solution at 25 ◦C. The

electrochemical parameters such as corrosion potential (Ecorr), Tafel slopes of cathodic and
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anodic (βc and βa), corrosion current density (icorr) and inhibition efficiencies (ηi) were

received from processing polarization curves and are showed in Table 3. The ηi are

calculated according to Eq. (4)[38]:

icorr  icorr
0
 i %  0
100 (4)
icorr

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where i0corr and icorr are corrosion current density in absence and presence of inhibitors,

respectively.

From Fig. 4 and Table 3, it is apparent that as the concentration of the three corrosion

inhibitors increases, the anode and cathode current densities are significantly reduced and

the anode current density is suppressed to a greater extent than the cathode current density.

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It indicates that the Met and Val inhibitor molecules can adsorb on the iron surface to form

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a corrosion inhibitor film, which effectively slows down the anode dissolution rate and

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prevents Cl- ions erosion[45, 46]. These results demonstrates that the three corrosion
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inhibitors are anode type corrosion inhibitors[47].
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In addition, from the value of icorr in Table 3, it is clear that the addition of each

corrosion inhibitor leads to a significant reduction in corrosion current density (icorr). This
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indicates that as the inhibitor concentration increases, the amount of inhibitor molecules
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adsorbed on the surface of the WE increases during the same immersion time, making the
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inhibitor film layer denser and more effectively reduce the contact between carbon steel
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and solution, reducing the corrosion rate of carbon steel. The maximum corrosion

inhibition efficiency of the three inhibitors is Met/Val (96.85%) >Met (87.66%) >Val
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(63.71%), as shown in Fig. 4 (d). This result is consistent with the EIS results.

3.3. SEM characterization-inhibition effect

From Fig. 5, it can be seen that the carbon steel sheet is immersed in the PCMs

solution in the absence of the inhibitor for 48 h, and its surface is severely corroded to

have obvious corrosion cracks and deep pores. The surface morphology of the sample
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immersed in the PCM solution in the present of the Met/Val inhibitor is superior to the

surface morphology of the uninhibited sample. In contrast, in the presence of the Met/Val

inhibitor the appearance of the carbon steel sheet surface is significantly improve, with

almost no pores except for the polishing lines. Therefore, the results showed that the

Met/Val inhibitor has good inhibition performance.

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3.4. Quantum chemical calculation

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In order to study the influence of electronic properties and molecular structure on the

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corrosion inhibition efficiency of Met and Val inhibitors and to prove that the inhibitor
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molecules can adsorb on the iron surface, quantum chemical calculation technology was
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used. In this work, the molecular structure of Met and Val inhibitors was optimized and

the single point energy was calculated by B3LYP/6-311G (d, p) algorithm in Gaussian
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03W software. And obtained the highest occupied molecular orbital (HOMO) and lowest
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unoccupied molecular orbital (LUMO) map of each inhibitor molecule (As shown in
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Table 4). In addition, the EHOMO, ELUMO, ΔE (ΔE= ELUMO-EHOMO) and μ (diple moment)
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directly affects the electronic interaction between the corrosion inhibitor molecule and the

metal surface[48, 49]. The calculated quantum chemical parameters are listed in Table 5.
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In general, the EHOMO represents the electron donating ability of a compound. If the

EHOMO value is larger, the electron donating ability of the compound molecule is stronger.

In contrast, the ELUMO represents the electron-accepting ability of a compound. The

smaller the ELUMO value, the stronger the electron-accepting ability of a molecule.

Moreover, the lower ΔE can infer that the inhibitor molecules have strong chemisorption

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on the metal surface[50, 51].

It can be seen from Table 4 that the highest occupied molecular orbital (HOMO) of

the Met and Val molecules mainly covers on the N atoms and S atoms, while the lowest

unoccupied molecular orbital (LUMO) covers on the -COOH group. As seen from Table 5,

the EHOMO of Met is higher than that of Val molecule, which indicates that the electron

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donation capability of Met molecule is stronger than that of Val molecule. Furthermore,

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the ELUMO of Met is lower than that of Val molecule, which suggests that the electron

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accepting capability of Met molecule is stronger than that of Val molecule. According to
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the ΔE values in Table 5, the ΔE of Met is lower than Val, so that the chemisorption

capacity of Met and Val follow the order of Met > Val. This is consistent with the
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experimental results and also satisfies the number of transferred electrons (ΔN) from the

inhibitor to the metal surface calculated by Eq. (5)[52, 53]:

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 Fe   inh
N 
2 Fe   inh
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(5)
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Where, χFe (7 eV) and γFe (0 eV) are the electronegativity and chemical hardness value of

the iron atom, respectively. χinh and γinh are the electronegativity and global chemical
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hardness value of the inhibitor molecules, respectively[54, 55].

The ionization potential (I) and electron affinity (A) were calculated according to the

Koopmans’ theorem and the the Hartree-Fock theorem[31, 56, 57]. Their operation and

approximation were defined as Eq. (6) and Eq. (7):

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IA
  (6)
2

IA
  (7)
2

The relationship between the energies of the HOMO and the LUMO and ionization

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potential and affinity was established, respectively. The frontier orbital energy is given as

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Eq. (8) and Eq. (9):

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I   E HOMO (8)
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A   E LUMO (9)
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As shown in Table 5, the ΔN value represents the ability of the compound to supply

electrons to the metal surface, and the inhibitory effect of the inhibitor molecule can be
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directly evaluated. If ΔN < 3.6[28, 58], the ηi value increases with increasing of the ΔN
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value. From Table 5, it is shown that the ΔN of Met is higher than that of Val, which is
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consistent with the inhibition efficiency of the inhibitor molecules.

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3.5. Molecular Dynamic (MD) simulation

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Molecular dynamics (MD) simulation has become the primary tool for studying the

interaction between inhibitors and metal surfaces. Molecular dynamics (MD) simulations

can reasonably predict the optimal molecular structure of inhibitor molecules on metal

surfaces[31, 56, 59, 60]. In addition, it can provide a basis for judging the inhibition

performance of the inhibitor by obtaining the values of adsorption energy (Eadsorption) and

binding energy (Ebinding) between the inhibitor molecule and the metal surface. In this
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experiment, the interaction between the Met and Val molecules and Fe (1 1 0) surface was

studied by molecular dynamics simulation, and the adsorption configuration of each

inhibitor molecule on the iron surface was obtained, as shown in Fig. 6. Obviously, the

inhibitor molecules are absorbed almost flat on the Fe (1 1 0) surface. This parallel or flat

position on the iron surface can be attributed to the nearly equal distribution of the density

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of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular

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orbital (LUMO) over the entire molecule. In addition, the entire inhibitor molecule can

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provide electrons to the unoccupied orbital of the iron surface to form stable coordination

bonds, and can also accept electrons from the d orbitals of iron with π bonds[61].
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Generally, if the bond distance is less than 3.5 Å, it indicates that a strong chemical bond
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has formed between the atoms. Conversely, a longer bond length indicates that the

interaction force between atoms is Van der Waals force[62]. The values of the shortest
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bond distance between the heteroatoms of the three inhibitors (Met, Val and Met/Val) and
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the Fe (1 1 0) surface were calculated as follows:

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Met-Fe adsorption model: (N-Fe = 4.07 Å, S-Fe = 3.37 Å, O-Fe = 3.13 Å);
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Val-Fe adsorption model: (N-Fe = 3.13 Å, O-Fe = 3.05 Å);

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Met/Val-Fe adsorption model: (N-Fe = 3.11 Å, S-Fe = 3.27 Å, O-Fe = 3.11 Å).

These values confirm the presence of chemical bonds between the three corrosion

inhibitors and the Fe (1 1 0) surface. Longer bond distances indicate van der Waals forces

in the adsorption of inhibitors and Fe. In addition, the S atoms and -COOH group of the

corrosion inhibitor molecules in the frontier molecular orbital map were also verified as
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the main adsorption sites.

To study the degree of interaction between the corrosion inhibitors and the Fe crystal.

The binding energy (Ebinding) and adsorption energy (Eadsorption) values of the three

corrosion inhibitors can be calculated according to Eq. (10) and Eq. (11)[27]:

Eadsorption  Etotal  Esurfacesolution  Einhibitorsolution  Esolution

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(10)

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Ebinding   Eadsorption (11)

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Herein, Etotal is the total energy of the entire simulation system. It includes iron
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crystals, adsorbed corrosion inhibitor molecules and solutions. The Esurface+solution and the

Einhibitor+solution represent the total energy of the system without corrosion inhibitor and the
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total energy of the system without iron crystals, respectively. The Esolution is the energy of

the PCMs solution.

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The values of binding energy (Ebinding) and adsorption energy (Eadsorption) are listed in
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Table 6. The order of the values of the binding energies of the corrosion inhibitors is:
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Met/Val (6.108 eV) > Met (3.732 eV) > Val (2.438 eV). According to theoretical analysis,
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the higher value of Ebinding indicates that the adsorption system is more stable, and the

corrosion inhibitors should have higher corrosion inhibition efficiency, such as: Met/Val >

Met > Val. This is consistent with the experimental results. In addition, the Ebinding value of

Met/Val is less than the Ebinding value of a single Met and Val, namely: Ebinding (Met) + Ebinding

(Val) =3.732 + 2.438 eV = 6.170 eV > Ebinding (Met/Val) =6.108 eV, this may be caused by the

competitive adsorption of Met molecules and Val molecules in the system[63].

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In order to verify the experimental results more accurately and truthfully, we studied

and calculated the velocity of Cl- ions in the corrosion inhibitor film formed by three

corrosion inhibitors with the concentration of 0.05 mol·L-1 (the best corrosion inhibition

efficiency) by molecular dynamics simulation. Because pitting of Cl- ions is a major factor

in the corrosion of carbon steel in PCMs solution.

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Generally, the value of the diffusion coefficient (D) can be used to assess the rate of

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migration of corrosive materials in the inhibitor film. A small value of the diffusion

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coefficient means that the inhibitor film has a good inhibitory effect, which results in high
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corrosion inhibition efficiency. The formula for calculating the diffusion coefficient (D) is

as shown in Eq. (12) and Eq. (13)[64, 65]:

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1 N 2
MSDt     Ri t   Ri 0  (12)
 N i1 
D

 
E

D  lim  Rit  Ri0

1 d n 2
(13)
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6 t  dx i
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Where, Ri(t), Ri(0) represent the positions of corrosive species at time t and 0,

respectively. |Ri(t) − Ri(0)|2 stands for mean-square displacement (MSD).

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It can be seen from Fig. 7 that the corrosion inhibitor film layer of Met/Val is more

compact than the corrosion inhibitor film layers of Met and Val, and can better reduce the

migration rate of Cl- ions and achieve good inhibition efficiency. Further, as shown in Fig.

8 and Table 7, the order of the migration rate values of Cl- ions in each of the corrosion

inhibitor film layers is Met/Val<Met<Val, and the order of the values of the respective

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inhibitors is confirmed to be Met/ Val>Met>Val. At the same time, from the value of the

diffusion coefficient of the corrosion inhibitor, the value of Met/Val (0.000018×10-9 m2 s-1)

is much smaller than the value of Met (0.004089×10-9 m2 s-1) and the Val (0.004885×10-9 m2

s-1). This may be due to the similar structure of Met and Val, both of which are chain

molecules. Besides, the corrosion inhibitor molecules act synergistically under high

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concentration conditions, stacking on each other to supplement the adsorption on the iron

RI
surface, making the corrosion inhibitor film layer tighter and greatly reducing the

SC
migration rate of Cl- ions in the corrosion inhibitor film, achieving good Corrosion

inhibition efficiency. This confirms that in the electrochemical test results, when the
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Met/Val corrosion inhibitor reaches 0.05 mol·L-1, the corrosion inhibition performance is
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better than that of the single corrosion inhibitor.

4. Conclusion
E D

The corrosion inhibition performance of carbon steel in PCMs solution was evaluated
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by electrochemical method using Met, Val and Met/Val corrosion inhibitors. The inhibition
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mechanism of Met, Val and Met/Val was studied by SEM, quantum chemical calculation

and molecular dynamics simulation. In addition, the results of this experiment are
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compared with the results of research on the corrosion inhibition performance of carbon

steel in PCMs solution by methionine (Met) and proline (Pro)[19].

Electrochemical test results show that both Met and Val inhibitors can reduce the

corrosion of carbon steel in PCMs solution, and the inhibition efficiency is positively

correlated with the concentration. The highest corrosion inhibition efficiencies of Met and

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Val inhibitors are 87.66% and 63.71%, respectively. However, Met/Val has the highest

corrosion inhibition efficiency, which is 96.85%, which is higher than the inhibition

efficiency (94.3%) of Met/Pro. In addition, the results of compounding effect analysis

showed that there was competitive adsorption between Met and Val inhibitors at a

concentration of less than 0.03 mol·L-1, and when the concentration was greater than 0.04

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mol·L-1, synergistic adsorption occurred between Met and Val. The polarization curve test

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shows that Met, Val and Met/Val are both anode type inhibitors, and the corrosion

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inhibition efficiency is consistent with the EIS test results.
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Quantum chemical calculations and molecular dynamics simulations show that both

Met and Val and Met/Val inhibitors can adsorb on Fe (1 1 0) surface, and N atoms, S
MA

atoms, and −COOH group are the main adsorption active sites. Met/Val has a stronger

adsorption capacity than Met and Val single inhibitors. However, the adsorption capacity
E D

of Met/Val is less than the sum of the adsorption energies of the single inhibitors,
PT

indicating that there is a competitive adsorption between the Met and Val inhibitors when

the concentration of the inhibitor is low. In addition, the migration rate of Cl- ions in the
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film of three corrosion inhibitors (concentration: 0.05 mol·L-1) was studied. It was found
AC

that the migration rate of Met/Val was the smallest, and it was also much smaller than the

migration rate of Met/Pro(inner salt). It shows that the corrosion inhibition performance of

Met/Val is stronger than that of Met/Pro. This is attributed to the fact that the chain

inhibitor molecule (Val) is more suitable for compounding with Met than the heterocyclic

inhibitor molecule (Pro).

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Acknowledgements

This work was funded by the Nature Science Foundation of Guangxi Province of

China (No. 2016GXNSFAA380061), Guangxi Key Laboratory of Electrochemical and

Magnetochemical Functional Materials (EMFM20161104, EMFM20161203).

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SC
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E D
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CE
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Figure

Fig. 1 Cooling curves of phase change materials, (a) bare, (b) Met/Val.

Fig. 2 Nyquist plots (a), (c), (e) and the Bode and phase angle plots (b), (d), (f) of carbon

steel in PCMs solutions with and without inhibitors at 25 °C, and (g) concentration-Rct/η

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diagram of Met, Val and Met/Val inhibitors.

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Fig. 3 Equivalent circuit used to calculate the impedance measurement of carbon steel in a

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PCMs solution with and without inhibitors at 25 °C.
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Fig. 4 Potentiodynamic polarization curves of carbon steel in PCMs solution, with and
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without inhibitors at 25 °C, (a) Met inhibitors, (b) Val inhibitors, (c) Met/Val compound

inhibitors and (d) concentration-icorr/η diagram of Met, Val and Met/Val inhibitors.
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Fig. 5 The SEM micrographs of corrosion surfaces formed by the CS sheets immersed in
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various PCMs solution for 48 h, (a) blank PCMs solution, (c) PCMs solution in presence

of Met/Val inhibitor, and the (b),(d) ere the detail view of (a), (c) respectively.
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Fig. 6 Molecular simulation of the most favorable adsorption mode obtained by Inhibitors
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on Fe (1 1 0) surface in PCMs solution, (a and b) is Met, (c and d) is Val and (e and f) is

Met/Val.

Fig. 7 Simulation model of Cl- ion diffusion in three inhibitor films: (a and b) is Met, (c
and d) is Val and (e and f) is Met/Val.

Fig. 8 The MSD curves of Cl- ion corrosive species in the three kinds of dynamic
simulation systems.
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Table

Table 1 Chemical names, structural formulas, symbols and molecular weight of the two

inhibitor molecules.

Table 2 EIS parameters for corrosion of carbon steel in PCMs solution, with and without

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inhibitors at 25 ° C.

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Table 3 Potentiodynamic polarization parameters of Met, Val and Met/Val inhibitor

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molecules at 25 °C.
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Table 4 Optimized geometry and and frontier molecular orbital density distribution of Met

and Val inhibitor molecules.

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Table 5 Quantum chemical parameters of Met and Val molecules.

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Table 6 Adsorption and binding energies of the Met, Val and Met/Val inhibitor molecules
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to the Fe (1 1 0) surface are in the simulated system.

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Table 7 The diffusion coefficient of Cl- ion in the three kinds of inhibitor film dynamic

simulation systems.
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Table 1

Chemical names, structural formulas, symbols and molecular weight of the two inhibitor

molecules.

Molecular weight
Inhibitor Structure Symbol

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(g·mol-1)

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L-Methionine Met 149.21

L-Valine
SCVal 117.15
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Table 2

EIS parameters for corrosion of carbon steel in PCMs solution, with and without inhibitors

at 25 ° C.

Conc.inh Rs C1 R1 CPE Rct ηR

PT
Inhibitors S
-1 2 -2 2 2
(mol L ) (Ω cm ) (μF cm ) (Ω cm ) -1 n
Y0(μΩ S cm ) -2
n (Ω cm ) (%)

RI
bare 0 6.292 3.265 5.880 53.410 0.659 877 -- --

SC
0.001 5.353 6.959 5.180 31.792 0.765 1848 52.56 --

0.005 6.367 7.549 6.236 23.630 0.782 2351 62.71 --

NU
0.01 6.046 4.847 5.851 17.354 0.792 2823 68.94 --
MA

Met 0.02 6.652 6.634 6.603 17.223 0.801 3067 71.42 --

0.03 6.676 4.561 6.668 15.706 0.806 3244 72.97 --

D

0.04 6.002 4.387 5.952 16.477 0.802 3723 76.45 --

E
PT

0.05 6.744 3.842 6.986 13.703 0.823 4262 79.43 --

0.001 6.356 6.326 5.830 33.177 0.721 1502 41.63 --

CE

0.005 6.411 6.426 6.043 29.995 0.738 1563 43.91 --

AC

0.01 6.376 6.493 6.053 28.130 0.749 1646 46.74 --

Val 0.02 6.943 6.678 6.464 33.337 0.728 1728 49.27 --

0.03 6.337 6.141 5.912 29.993 0.736 1830 52.09 --

0.04 7.288 6.869 6.643 24.266 0.722 1895 53.74 --

0.05 6.179 6.925 5.871 26.123 0.751 2165 59.51 --

Met/Val 0.001 6.508 8.134 6.430 26.653 0.771 1741 49.64 0.55

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0.005 6.531 7.593 6.373 26.882 0.759 2132 58.88 0.51

0.01 6.741 7.678 6.674 23.259 0.782 2294 61.78 0.43

0.02 6.210 5.736 6.047 21.605 0.769 2799 68.68 0.46

0.03 6.879 5.232 6.820 13.306 0.796 5317 83.51 0.79

0.04 6.498 4.444 6.288 10.431 0.797 12246 92.84 1.52

PT
0.05 6.711 3.794 6.484 10.122 0.780 17861 95.09 1.70

RI
SC
NU
MA
E D
PT
CE
AC

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Table 3

Potentiodynamic polarization parameters of Met, Val and Met/Val inhibitor molecules at

25 °C.

Conc.inh Ecorr -βc βa icorr η

Inhibitors S
-1 -1 -1 -2
(mol L ) (V vs.SCE) (V dec ) (V dec ) (μA cm ) (%)

PT
bare 0 -0.675 0.303 0.296 37.20 -- --

RI
0.001 -0.675 0.293 0.107 17.90 51.88 --

SC
0.005 -0.675 0.269 0.069 11.20 69.89 --

0.01 -0.675 0.236 0.062 7.88 78.82 --

NU
Met 0.02 -0.678 0.210 0.058 6.68 82.04 --
MA

0.03 -0.676 0.208 0.053 5.23 85.94 --

0.04 -0.677 0.222 0.060 4.87 86.91 --

D

0.05 -0.673 0.206 0.059 4.59 87.66 --

E
PT

0.001 -0.676 0.345 0.139 23.40 37.10 --

0.005 -0.678 0.328 0.134 23.00 38.17 --

CE

0.01 -0.678 0.309 0.133 22.10 40.59 --

AC

Val 0.02 -0.675 0.296 0.110 20.10 45.97 --

0.03 -0.678 0.259 0.097 17.30 53.49 --

0.04 -0.674 0.247 0.097 17.10 54.03 --

0.05 -0.675 0.246 0.083 13.50 63.71 --

0.001 -0.667 0.297 0.100 16.90 54.57 0.66

Met/Val
0.005 -0.679 0.241 0.080 13.90 62.63 0.50

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0.01 -0.669 0.240 0.079 11.30 69.62 0.41

0.02 -0.678 0.234 0.065 8.22 77.90 0.44

0.03 -0.674 0.204 0.056 3.73 89.97 0.65

0.04 -0.678 0.198 0.061 1.96 94.73 1.14

0.05 -0.675 0.155 0.058 1.17 96.85 1.42

PT
RI
SC
NU
MA
E D
PT
CE
AC

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Table 4

Optimized geometry and and frontier molecular orbital density distribution of Met and Val

inhibitor molecules.

Inhibitors Structure HOMO LUMO

PT
Met

RI
SC
Val
NU
MA
E D
PT
CE
AC

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Table 5

Quantum chemical parameters of Met and Val molecules.

EHOMO ELUMO △E μ
Assembly molecules χ=(I+A)/2 γ=(I-A)/2 △N
(eV) (eV) (eV) (Debye)

PT
Met -6.035 -0.181 5.854 2.427 3.108 2.927 0.665

RI
Val -6.855 -0.075 6.780 1.318 3.465 3.390 0.521

SC
NU
MA
E D
PT
CE
AC

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Table 6

Adsorption and binding energies of the Met, Val and Met/Val inhibitor molecules to the Fe

(1 1 0) surface are in the simulated system.

Eadsorption Ebinding ηmax

Inhibitors

PT
(eV) (eV) (%)

RI
Met -3.732 3.732 87.66

SC
Val -2.438 2.438 63.71

Met/Val -6.108 6.108 96.85

NU
MA
E D
PT
CE
AC

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Table 7

The diffusion coefficient of Cl- ion in the three kinds of inhibitor film dynamic simulation

systems.

Diffusion coefficient /(10-9 m2s-1) ηmax

PT
Inhibitors
Cl- (%)

RI
Met 0.004089 87.66

SC
Val 0.004885 63.71

Met/Val 0.000018 96.85

NU
MA
E D
PT
CE
AC

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Highlights

1. The methionine and valine were used as corrosion inhibitors for carbon steel.

2. The inhibition performance of inhibitors in phase change materials solution.

3. EIS, Polarization and SEM were used to investigate the inhibition performance.

PT
RI
4. The inhibition mechanism was studied by computer modeling studies.

SC
5. Simulated the migration rate of Cl- ion in the corrosion inhibitor films.
NU
MA
E D
PT
CE
AC

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Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8