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A green multifunctional anti-scaling inhibitor for crystallization control of Ca

scale crystals
1 1 1 1 2 1,3
Jianxin Chen *, Hao Xu , Jian Han *, Cai Wang , Qing Wu , Chunli Li
1
School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
2
School of Artificial Interlligence, Hebei University of Technology, Tianjin 300130, China
3
National-Local Joint Engineering Laboratory for Energy Conservation of Chemical Process Integration and
Resources Utilization, Tianjin 300130, China
*Correspondence: Jianxin Chen (E-mail: chjx2000@126.com), Jian Han (E-mail: superhj@sohu.com), School of
Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
Abstract
Histidine-polyaspartic acid (His-PASP), an effective anti-scaling inhibitor, was synthesized by polysuccinimide
(PSI) and histidine. His-PASP exhibited promising anti-scaling effect by inhibiting the reaction crystallization of
Ca scale crystals. The crystal form and surface morphology of Ca scale crystals were changed after the addition
of His-PASP. The hard scale was turned into soft dirt and can be easily washed away. The binding between His-
PASP and calcite was exothermic and the energy was higher than the traditional adsorption energy. His-PASP
possessed a favorable anti-corrosion efficiency for carbon steel in cooling water and achieved to 90% at 200 mg
-1
L . In the test of dispersing Fe2O3, the transmittance of the supernatant was dropped with the increasing of
His-PASP dosage.
Keywords: His-PASP, Inhibition reaction crystallization, Ca scale crystals, Anti-corrosion, Dispersion Fe2O3
1. Introduction
Currently, the demand for water in industrial production has greatly increased and the shortage of
global freshwater resources has become the most urgent issue [1]. The recycling of water resources
is considered to be the best way to resolve the contradiction [2]. In industry cooling water, the Ca2+
react with other ions to form Ca scale crystals and adheres to the tube, resulting in not only
reduction of heating transfer efficiency but also acceleration the corrosion of pipe [3,4]. Various anti-
scaling inhibitors for industrial application have been developed to inhibit the reaction crystallization
of Ca scale crystals [5]. The resulting small amount crystals are also easily washed away by water and
no longer attached to the tube. But the most widely used phosphorus-containing inhibitors such as
amino trimethylene phosphonic acid (ATMP) and polyether polyaminomethylene phosphonate
(PAPEMP) usually lead to eutrophication of water after discharging to river [6-10]. With the
improvement of people's environmental awareness, the phosphorus-free green high-efficiency anti-
scaling inhibitors have received tremendous attention [11,12].

Received: August 20, 2018; revised: October 16, 2018; accepted: December 04, 2018

This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the final Version of Record (VOR). This
work is currently citable by using the Digital Object Identifier (DOI) given below. The final
VoR will be published online in Early View as soon as possible and may be different to this
Accepted Article as a result of editing. Readers should obtain the final VoR from the
journal website shown below when it is published to ensure accuracy of information. The
authors are responsible for the content of this Accepted Article.

To be cited as: Chem. Eng. Technol. 10.1002/ceat.201800417

Link to final VoR: https://doi.org/10.1002/ceat.201800417

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Polyaspartic acid (PASP), as a green multifunctional polymeric material, has attracted an increasing
attention [13,14]. PASP contains a large number of carboxyl groups so as to possess favorable
property of chelating and dispersing [15]. However, the anti-scaling effect is limited at high Ca2+
concentration and against Ca3(PO4)2 [16]. In order to improve its performance, the functional groups
(hydroxyl, carboxyl, sulfonic acid and mercapto) are introduced by grafting side chains [17]. For
example, Sun et al. have synthesized Poly(aspartic acid)-tryptophan grafted copolymer to introduce
carboxyl and unsaturated heterocyclic that enhanced the anti-scaling effect [18]. Xu et al. have found
polyaspartic acid/5-aminoorotic acid graft copolymer possesses promising anti-scaling and anti-
corrosion performance [19].
The heat transfer equipment based on carbon steel material have been widely used in industrial
circulating cooling water system [20,21]. The Fe2O3 that generated by pipe corrosion adheres to the
pipe wall, also resulting in a decrease of heating transfer efficiency [22]. Therefore, it is urgently to
design inhibitors have excellent functions of anti-corrosion and dispersion. Unsaturated heterocyclic
compounds, especially the imidazole derivatives, are easily adsorbed on the metal surface to
suppress the destruction of corrosive ions [23,24]. In previous work, Zhang et al. synthesized
polyaspartic acid/3-amino-1H-1,2,4-triazole-5-carboxylic acid hydrate graft copolymer and found it
possesses good anti-scaling and anti-corrosion properties [25]. Histidine, an essential human amino
acid, is non-toxic and contains the functional groups of carboxyl, amino and imidazole. Grafting
histidine to the side chain of PASP not only improves the properties of chelating Ca2+ and dispersing
Fe2O3 but also enhances the anti-corrosion efficiency for carbon steel.
In this work, histidine was introduced to the side chain of PASP by simple ring-opening grafting
reaction between histidine and PSI. The anti-scaling effect was tested by static scale inhibition
method. XRD and SEM were used to analyze the changes in crystal form and surface morphology of
Ca scale crystals, respectively. The binding energy and the interaction mechanism of His-PASP/calcite
system were explored by Molecular dynamics simulation. The anti-corrosion efficiency of His-PASP
was calculated according to electrochemical polarization curve and impedance spectra. The surface
morphology and elemental composition of carbon steel were analyzed by SEM and EDX, respectively.
The performance of dispersing Fe2O3 was obtained by measuring the light transmittance of the
specimen.

2. Experimental
2.1. Materials and Instruments
Histidine (99%) and maleic anhydride (99%) were supplied by Heowns (Tianjin, China). Ammonia
solution (28%-30%), N-N dimethylformamide (≥99.5%), sodium hydrate (96%) and ethanol (≥99.7)
were purchased from Guangfu Fine Chemical Research Institute (Tianjin, China).
The structure of the product was characterized by FTIR (BRUKER VERTEX 70) and 1H-NMR (Avance III
plus 400 MHz). CHI660E electrochemical workstation was used for electrochemical tests.

2.2. Synthesis of His-PASP

PSI (5×10-5 mol) and deionized water (5 mL) were stirred in a flask to form a suspension. According to
molar ratio, histidine and sodium hydroxide dissolved in distilled water was slowly added to the PSI
suspension with a constant pressure dropping funnel, and reacted at 313 K for 3 h. The reacted
solution was adjusted to neutral with HCl and poured into ethanol, the final yellow precipitate was
His-PASP. Relevant synthesized route was expressed in Fig. 1.
Fig. 1

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2.3. Static anti-scaling experiment

The anti-scaling performance was tested by static scale inhibition experiment according to GB/T
16632-2008 [26]. In this experiment, three most common types of Ca scale crystals of CaCO3, CaSO4
and Ca3(PO4)2 were considered. The specimen of CaCO3 was ρ(Ca2+) = ρ(HCO3−) = 500 mg L-1 (as
CaCO3); specimen of CaSO4 was ρ(Ca2+) = 6800 mg L-1 (as CaSO4) and ρ(SO42−) = 6800 mg L-1; specimen
of Ca3(PO4)2 was ρ(Ca2+) = 250 mg L-1 (as CaCO3), ρ(PO43−) = 10 mg L-1, and the pH adjusted to 9.1 with
borax buffer. Then, different dosage of His-PASP was added and incubated at 353 K for 10 h. For
CaCO3 and CaSO4, the free Ca2+ was titrated with EDTA (0.01 mol L-1). The anti-scaling efficiency was
calculated as formula (1):
2  1
   100% (1)
0  1
where ρ2 was mass concentration of Ca2+ with inhibitor after heating for 10 h; ρ0 and ρ1 were mass
concentration of Ca2+ without inhibitor before and after heating for 10 h.
For Ca3(PO4)2, the chromogenic reagent was added and kept standing for 10 min. An UV
spectrophotometer was used to test the absorbance at 710 nm. The anti-scaling efficiency was
calculated as formula (2):
A2  A1
   100% (2)
A0  A1
where A2 was the absorbance of solution with inhibitor after heating for 10 h; A0 and A1 were the
absorbance of solution without inhibitor before and after heating for 10 h.

2.4. Molecular dynamics simulation

Although the anti-scaling effect of His-PASP had been proved by experiment, the interaction
mechanism between His-PASP and scale needs further study. The computational study involved in
this work was performed by Materials Studio 8.0. Visualizer module was employed to build the
model and Molecular dynamics simulation was applied to simulate the interaction between calcite
and His-PASP using the Forcite module along with COMPASS Ⅱ force field. His-PASP was designed as
different degree of polymerization (DP = 1, 3 and 5), the torsion angle between the monomers was
set as 0°, ±45°, ±90°, ±135°, and 180°. Geometry optimization was utilized for optimizing the
configuration of His-PASP and found the minimum energy configuration. Calcite crystal with the
lattice parameters: a = b = 4.99 Å, c = 17.06 Å, α = β = 90°, γ = 120° was built [27]. The calcite crystal
was cleaved the (104) and (110) surfaces along the specific crystal directions and built a 3×5 super
cell. A vacuum layer (about 20 Å) was set to eliminate the influence of other periodic atoms. The top
layer of crystal was annealed from 303 K to 1053 K with a step size of 50 K [28]. The optimized His-
PASP molecule was placed near to the calcite surface (about 3-4 Å) and carried out geometry
optimization. Molecular dynamics simulation (100 ps total simulation time with a time step of 1 fs at
353 K) was performed in NVT ensemble to calculate the binding energy between His-PASP and calcite
crystal. The interaction energy (Einteration) between His-PASP and calcite crystal was calculated as
formula (3):
E interation  E total  (E calcite  E His- PASP ) (3)
where Etotal was the energy of the system, Ecalcite and EHis-PASP was the energy of calcite and His-PASP,
respectively.

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2.5. Electrochemical tests

The test solution was simulated industrial circulating cooling water and the chemical composition
was shown in Table 1 [29]. Q235 carbon steel with an exposed area of 1 cm2 was utilized for the work
electrode [30]. A saturated calomel electrode served as reference electrode and connected to the
solution by a bent luggin capillary tube. The platinum was employed as the counter electrode. The
work electrode was soaked in testing solution at 298 K for 1 h to establish a steady state [31]. Versus
to a stable OCP, in the range of ±300 mV with a constant scan rate of 1 mV/s to obtain
potentiodynamic polarisation curves [32]. The EIS was tested under the OCP over the frequency
range from 100000 Hz to 0.01 Hz in the AC signal with a disturbance amplitude of 5 mV [33]. The
anti-corrosion efficiency was calculated as formula (4) and (5):
I corr  I corr(inh)
IE %   100% (4)
I corr
where Icorr(inh) and Icorr were the corrosion current density with and without His-PASP, respectively.

Rct(inh)  Rct
IE %   100% (5)
Rct(inh)
where Rct(inh) and Rct were the charge transfer resistance with and without His-PASP, respectively.
Table. 1

2.6. Dispersion test

The CaCl2.2H2O and (NH4)2FeSO4 were configured to the specimen (Ca2+ = 150 mg L-1 (as CaCO3), Fe2+
= 10 mg L-1, pH = 9.1). Different dosage of inhibitor was added and was vigorous stirred for 15 min.
Then, it was placed in a water bath at 323 K and shaken at 100 r min-1 for 5 h. After standing for 3 h,
the transmittance of the supernatant was tested with an UV spectrophotometer at 320 nm.

3. Results and discussion

3.1. FTIR and 1H-NMR analysis of His-PASP
The FTIR spectrum is shown in Fig. 2a, the band at 3300-3500 cm-1 is attributed to the stretching
vibration of N-H in the secondary amide. The band at 1600 cm-1 indicates the stretching vibration of
C=O in amide. The band at 1400 cm-1 represents the bending vibration of N-H and the stretching
vibration of C-N in -CONH. These signals are confirmed the successful synthesis of PASP. The band at
1635 cm-1 is assigned to the stretching vibration of C=N and the band at 1462 cm-1 is corresponded to
the stretching vibration of C=C in imidazole ring. The above evidences are verified that histidine
successfully modified PASP.
The 1H-NMR spectrum is shown in Fig. 2b, the solvent peak of D2O appears at 4.75 ppm. Except for
the peaks of PASP, the peak at 3.0 ppm is assigned to the -CH2- and the peak at 3.7 ppm is attributed
to the -CH- in side chain. The peaks at 6.9 and 7.7 ppm are ascribed to the -CH- in imidazole ring.
These changes indicate the successful synthesis of His-PASP.
Fig. 2

3.2. Anti-scaling performance of His-PASP

3.2.1. Anti-scaling efficiency against Ca scale crystals
In Fig. 3a, the anti-scaling efficiency of His-PASP against CaCO3 is significantly higher than that of
PASP and reaches up to 100% at 6 mg L-1. This is attributed to the introduction of carboxyl groups and
imidazole rings as well as the amides that formed by the ring-opening reaction. These groups contain

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a large number of negative charges and lone pairs of electrons, which can chelate with Ca2+ to form
stable complexes, reducing the possibility of Ca2+ to bind inorganic anions. At the same time, His-
PASP is adsorbed on the crystal surface and doped in the lattice lattice, which causes the lattice to be
distorted [34]. The lattice distortion inhibits the growth of the crystal. Fig. 3b reveals that both His-
PASP and PASP have favorable anti-scaling effect against CaSO4 and the anti-scaling efficiency
achieves to 100% at 5 mg L-1 and 6 mg L-1, respectively. The anti-scaling efficiency of His-PASP against
Ca3(PO4)2 is significantly higher than PASP (Fig. 3c), and the anti-scaling efficiency of His-PASP is about
90% at 20 mg L-1. The anti-scaling efficiency at high Ca2+ concentration is shown in Fig. 3d and
dropped continuously with the increase of Ca2+ concentration. It can be considered that the
probability of collision between ions is increased with the increase of Ca2+ concentration, thereby
accelerating the formation of Ca scale crystals. However, the anti-scaling efficiency of His-PASP is still
higher than 70% when the Ca2+ concentration as high as 800 mg L-1. This proves that His-PASP can be
applied for high hardness water.
Fig. 3

3.2.2. SEM images of Ca scale crystals

Fig. 4 shows the SEM images of CaCO3 and CaSO4 crystals. Fig. 4a is CaCO3 crystal before the addition
of His-PASP. Because the crystal form of CaCO3 is affected by temperature, the CaCO3 obtained at
353 K is not only a single calcite [35]. The CaSO4 crystal in Fig. 4c exhibits a needle-type crystal with
smooth surface in the absence of His-PASP [36]. After the addition of His-PASP, the CaCO3 crystal in
Fig. 4b become irregular small particles and joined together, the bubbles are easily to get into the
gaps, which caused the crystal floats on the water [37]. It can be also observed that the shape of
CaSO4 become clusters and the surface of is corroded, resulting in a fragile structure (Fig. 4d) [38]. In
summary, the hard scale turns into soft dirt after the addition of His-PASP and can be easily removed
[39].
Fig. 4

3.2.3. XRD analysis of Ca scale crystals

Fig. 5 is the XRD spectrum of CaCO3 and CaSO4 crystals. In Fig. 5a, the spectrum of CaCO3 without His-
PASP only contains the characteristic peaks of calcite and aragonite. In the presence of His-PASP,
some vaterite characteristic peaks appear in the spectrum, which confirmed that the scaling process
of CaCO3 can be affected by His-PASP and the crystal form changes from calcite to vaterite. In Fig. 5b,
the major characteristic peaks of CaSO4 appear in the same position. However, the peak intensity is
decreased after the addition of His-PASP. This reveals that His-PASP cannot change the crystal form
of CaSO4 but change its particle size and surface morphology [40]. Consequently, the crystals are
transformed into floppy and can be washed away.
Fig. 5

3.2.4. Binding energy of His-PASP on calcite surface

The optimal configurations of His-PASP on calcite surface are shown in Fig. 6. His-PASP moves toward
calcite surface and covers on the surface after the MD simulation, which proved that His-PASP
emerges a strong interaction with calcite. As can be seen in Table 2, the binding energy of His-
PASP/calcite system is negative, demonstrating that the combination between His-PASP and calcite is
exothermic, and the energy is much higher than the traditional adsorption energy [41]. The more
negative the binding energy, the more beneficial the combination between His-PASP and calcite. The
binging energy between His-PASP and (110) surface is higher than between His-PASP and (104)
surface, revealing that the binding between His-PASP and (110) surface is more powerful, which is
consistent with the surface activity of calcite.
Fig. 6

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Table. 2

3.2.5. Interaction mechanism of His-PASP/calcite system

In order to analyze the interaction mechanism between His-PASP and calcite, the intermolecular
interactions are shown in Fig. 7. The H-atoms of the carboxyl group, amino group and imidazole form
many H-bonds with the O-atoms of the calcite. The distance between the O-atom of His-PASP and
the Ca-atom of the calcite is between 2.2-2.6 Å, which is similar to the internal structure of calcite
[27,42]. The electrostatic forces play an important role in the binding between His-PASP and calcite.
In addition, the π 34 delocalization bonds of carboxyl group and imidazole ring interact with the π 64
delocalization bonds of calcite also have obvious influence on changing the crystal form.
Fig. 7

3.3. Anti-corrosion performance of His-PASP

3.3.1. Anti-corrosion efficiency for carbon steel
The Tafel polarization plots are exhibited in Fig. 8a. Potentiodynamic polarization parameters
including corrosion current density (Icorr), corrosion voltage (Ecorr), anodic slope (βa), cathodic slope
(βc) were obtained by Tafel extrapolation method and presented in Table 3. The corrosion current
density decreased with the increasing of His-PASP, suggesting that the anti-corrosion effect for
carbon steel is enhanced after the addition of His-PASP. The corrosion voltage shifts toward the
anodic, the anodic slope is increased and the cathodic slope is decreased, demonstrating that His-
PASP is a mixed-type anti-corrosion inhibitor with synergistic effect, which can delay metal
dissolution and cathodic process [8].
Fig. 8b shows the Nyquist plots. The Nyquist plots are analyzed using the ZSimpWin 3.50 software
and the parameters are fitted to a suitable equivalent circuit that presented in Fig. 8c. The fitted
parameters are listed in Table 4. Rct is the charge transfer resistance between electrode surface and
outer Helmholtz plane. Rs is the uncompensated solution resistance. The constant phase element
(CPE) is used to simulate the double layer capacitance at the interface of carbon steel and the
solution in the film pores. The phase shift (n) represents the surface unevenness. The Rct value is
small in the absence of His-PASP and increased with the His-PASP dosage. The increase of Rct value
and the drop of Y0 are ascribed to the decrease of local dielectric constant or the increase of the
electrical double layer thickness [33]. This proves that His-PASP is adsorbed on the carbon steel
surface to form a protective film, which can inhibit the corrosive ions to damage of carbon steel. Due
to the carbon steel surface is not perfect and the frequency dispersion at low-frequency area, the
Nyquist plots is not an ideal semicircle. The small tail in low frequencies may be related to metal
dissolution. The CPE is introduced into equivalent circuit owing to the frequency dispersion, surface
unevenness and the formation of adsorbed layers. The n value is also enhanced compared to the
absence of His-PASP, His-PASP is adsorbed on the active sites to improve the surface heterogeneity.
The Cl- in the solution results in a deterioration defect on the electrode surface. The strong binding
force between His-PASP and carbon steel surface prevents the corrosive ions from oxidating to the
carbon steel surface, resulting in forming a corrosion resistance. The anti-corrosion efficiency is
achieved to 90% with a His-PASP dosage of 200 mg L-1. The anti-corrosion efficiency is increased may
be related to the barrier film is formed on the carbon steel surface. The adsorption of His-PASP on
the carbon steel surface is attributed to the π-electrons in the imidazole, carboxyl and amide. The d-
electrons of Fe-atom interact with the vacant orbital of the N, O-atom and the unshared electron
pairs of N, O-atom interact with the vacant d-orbital of Fe-atom [43]. The corrosion resistance is
enhanced in the presence of His-PASP and significantly affected by the dosage.
Fig. 8

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Table. 3
Table. 4

3.3.2. SEM and EDX analysis of carbon steel surface

The surface morphology of carbon steel is characterized by SEM images. Fig. 9a has smooth surface
and clear lines. In Fig. 9b, the Ca scale crystals and corrosion products adhere to the carbon steel
surface. The carbon steel surface in Fig. 9c possesses a better degree of smoothness and less
corrosion products. It is probably that His-PASP inhibits the formation of Ca scale crystals and forms a
protective film on the surface to inhibit the corrosion [44].
We further explore the elemental composition of carbon steel surface by EDX. Fe peak with different
intensity appears in all samples. Compared with Figure 9d, the increase of O element content and the
appearance of Ca peaks in Fig. 9e are the results of the formation of corrosion products and Ca scale
crystals. As can be seen from Fig. 9f, the increase of C element content and the appearance of N
peaks are confirmed that His-PASP is absorbed on the carbon steel surface. The Ca element content
decrease from 9.02% to 1.57% indicates that His-PASP inhibits the formation of Ca scale crystals.
Fig. 9

3.4. The effect of dispersing Fe2O3

The reduction of heating transfer efficiency caused by Fe2O3 brings lots of non-productive
consumption. The anti-scaling inhibitor with the function of dispersing Fe2O3 is valuable. As shown in
Fig. 10, the transmittance of the supernatant in the presence of His-PASP decrease from 100% to
30% with the dosage from 10 mg L-1 to 40 mg L-1 and significantly lower than PASP, demonstrating
that His-PASP is a favorable dispersant. The carboxyl groups and imidazole rings are introduced in the
side chain of PASP that significantly enhanced the ability of dispersing Fe2O3. In particular, the lone
pairs that contained in His-PASP can complex with Fe3+, changing the crystallization process of Fe2O3
crystal. His-PASP is absorbed on the crystal surface and repelled each other under the static
electricity, thereby the crystal is uniformly dispersed in the solution.
Fig. 10

4. Conclusions
His-PASP is successfully synthesized by a simple ring-opening modification of PSI. His-PASP exhibits
favorable anti-scaling effect by inhibiting reaction crystallization of Ca scale crystals. The anti-scaling
efficiency of His-PASP against CaCO3 and CaSO4 reaches up to 100% at 6 mg L-1 and 5 mg L-1,
respectively. After the addition of His-PASP, the crystal form of CaCO3 is changed from calcite to
vaterite and the surface morphology of CaSO4 is corroded. The anti-scaling efficiency of His-PASP
against Ca3(PO4)2 is significantly increased compare with PASP and approached to 90% at 20 mg L-1.
The functional groups derived from His-PASP can chelate with Ca2+ to inhibit the reaction
crystallization of Ca scale crystals, thereby the Ca2+ is uniformly dispersed in the solution. His-PASP,
as an anti-scaling inhibitor, also has promising anti-corrosion effect by controlling the anode reaction.
The anti-corrosion efficiency for carbon steel increases with the His-PASP dosage and achieves to
90% at 200 mg L-1. In addition, His-PASP exhibits favorable dispersibility for Fe2O3 that avoid the
influence in heating transfer. The anti-scaling and anti-corrosion performances as well as the
dispersion ability prove that the potential application of His-PASP in industrial circulating cooling
water.

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Acknowledgments
Thanks for the supports by the National Natural Science Fund of China (No. 21476059, and
21276063), Hebei Science and Technology Support Program (No. 16273101D), Colleges and
Universities in Hebei Science and Technology Research Program (No. QN2015022).

Symbols
A absorbance of solution
Ecalcite interaction energy (KJ mol-1) of calcite
EHis-PASP interaction energy (KJ mol-1) of His-PASP
Einteration interaction energy (KJ mol-1) between His-PASP and calcite
Etotal interaction energy (KJ mol-1) of the system
Icorr corrosion current density (μA cm-2) without His-PASP
Icorr(inh) corrosion current density (μA cm-2) with His-PASP
IE% anti-corrosion efficiency
η anti-scaling efficiency
ρ mass concentration (mg L-1) of Ca2+

Abbreviations
EDX Energy Dispersive X-Ray Spectroscopy
EIS electrochemical impedance spectroscopy
FTIR Fourier transform infrared spectrometer
1
H-NMR Nuclear Magnetic Resonance
OCP open circuit potential
SEM Scanning electron microscope
XRD X-ray diffraction

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Figures

Fig. 1 Synthesis route of His-PASP.

Fig. 2 FTIR and 1H NMR spectrum of PASP and His-PASP.

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Fig. 3 The anti-scaling efficiency against CaCO3 (a), CaSO4 (b) and Ca3(PO4)2 (c) with different dosage of
inhibitor, and (d) is the anti-scaling efficiency for different Ca2+ concentration (as CaCO3) with a
dosage of 2 mg L-1 inhibitor.

Fig. 4 SEM images of CaCO3 and CaSO4 in the absence and presence of His-PASP.

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Fig. 5 XRD spectrums of CaCO3 and CaSO4 crystal with and without His-PASP.

Fig. 6 Optimized geometry of systems that His-PASP (DP = 3) on calcite surface.

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Fig. 7 The interaction between His-PASP and calcite: (a) hydrogen bonds between H-atom of
His-PASP and O-atom of calcite; (b) distance between O-atom of His-PASP and Ca-atom of
calcite.

Fig. 8 Polarization curves (a) and Nyquist plots (b) for carbon steel with different dosage of His-PASP,
Equivalent circuit (c) for fitting the impedance spectrum.

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Fig. 9 SEM (a) and EDX (d) are polished carbon steel, SEM (b) and EDX (e) are immersed in the
solution without His-PASP, SEM (c) and EDX (f) are immersed in the solution with His-PASP

Fig. 10 The performance of dispersing Fe2O3.

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Tables
Table. 1 The chemical composition of test solution.

. .
Substance CaCl2 2H2O MgSO4 7H2O NaCl NaHCO3
-1
Content (g L ) 0.555 0.493 0.168 0.168

Table. 2 Binding energy of the His-PASP/calcite systems.

Einteration(DP=1) Eintreation(DP=3) Einteration(DP=5)

(KJ mol-1) (KJ mol-1) (KJ mol-1)

(104) -365.33 -690.12 -1274.27

(110) -474.85 -992.88 -1370.87

Table. 3 Polarization parameters of carbon steel with different dosage of His-PASP .

Concentration Ecorr Icorr βa -βc IE

(mg L-1) (mV vs. SCE) (μA cm-2) (mV dec-1) (mV dec-1) (%)

Blank -533 36.75 92.43 399.04 0

50 -500 10.96 107.47 269.76 70.17

100 -487 8.90 167.06 239.18 75.78

150 -381 6.98 177.43 158.70 81.01

200 -367 3.73 138.81 143.51 89.85

Table. 4 Impedance parameters of carbon steel with different dosage of His-PASP.

Concentration Rs CPE Rct IE

(mg L-1) (Ω cm2) Y0 n (Ω cm2) (%)

(10-4 Ω-1 cm-2 s-1)

Blank 22.07 7.08 0.720 689 0

50 19.17 4.53 0.623 1792 61.55

100 37.96 1.50 0.837 2633 73.83

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150 21.76 1.11 0.812 4772 85.56

200 30.73 1.43 0.809 6257 88.99

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