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Desalination 398 (2016) 198207

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Desalination

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

A natural extract of tobacco rob as scale and corrosion inhibitor in


articial seawater
Hefang Wang a,, Meidan Gao a, Yong Guo b, Yongfang Yang a,, Rongbin Hu a
a
School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
b
NOOC Tianjin Chemical Research Design Institute, Tianjin 300131, China

H I G H L I G H T S

TRE as corrosion inhibitor for Q235 was investigated in articial seawater.


TRE on Q235 surface has been conrmed by SEM and XPS analysis.
TRE has an excellent scale inhibition in articial seawater.
SEM and XRD implied that the scale deposits were changed in the presence of TRE.

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

Article history: The corrosion inhibition performance of tobacco rob extract (TRE) for Q235 corrosion in articial seawater was
Received 25 March 2016 investigated by potentiodynamic polarization. The experimental results indicate that TRE has good corrosion in-
Received in revised form 20 July 2016 hibition performance and the inhibition efciency increased with the increase of TRE concentration. Scanning
Accepted 25 July 2016
electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) indicated that the corrosion inhibition
Available online 31 July 2016
is due to the formation of a chemisorbed lm on the steel. The anti-scale property of TRE in articial seawater
Keywords:
was also studied by static tests for scale and the scale deposits were analyzed by X-ray diffraction (XRD) and
Tobacco rob SEM, respectively. The results showed that the scale deposits surface morphology and size were changed in
Articial seawater the presence of TRE. The corrosion and scale inhibition results indicated the potential use of TRE as an efcient
Scale inhibition corrosion and scale inhibitor in articial seawater.
Corrosion inhibition 2016 Elsevier B.V. All rights reserved.

1. Introduction xyphenol (DMP) [11], 2-(2-{[2-(4-Pyridylcabonyl) hydrazono] methyl}


phenoxy) acetic acid (PMA) [12] 3-amino-1.2,4-triazole-5-thiol (ATAT)
Water is the most essential substance for all life on earth and a pre- [6], and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) [13] were
cious resource for human civilization [1]. The demand of water in indus- used as corrosion inhibitors due to the adsorption of hetero atoms on
trial processes has increased signicantly with the development of iron metal surface. Most corrosion and scale inhibitors are synthetic poly-
and steel production, power generation, chemicals production, which mers containing phosphate groups, sulfonate groups and carboxylic
has intensied the shortage of water resources. Therefore, seawater acids [14], such as poly (acrylic acid) (PAA) as scale inhibitors in seawa-
has been used for as cooling water or desalination to alleviate the pres- ter [14] and Phosphonic Chitosan (Ph-Ch) as corrosion inhibitor for car-
sure on water supply in recent years. However, seawater with high sa- bon steel in seawater [15]. Recently, polyaspartic acid derivative [3]
linity and a great variety of micro-organism result in corrosion and with functional group of carboxylic acid had good corrosion and scale
scale formation [2,3], which lead to many operational problems, eco- inhibition performance in natural seawater. Although the above men-
nomic losses and even risk of lives [4,5]. tioned synthetic compounds had good anti-corrosion and anti-scaling
The use of corrosion and scale inhibitors is one of the most common performance, most of them are non-biodegradable and expensive,
methods to control corrosion and scale deposition [68]. Synthetic or- which conne their development and applications in industry. Besides,
ganic compounds containing hetero atoms nitrogen such as benzotri- traditional treatment methods of used seawater are for the production
azole (BTA) [9,10], 2-((dehydroabietyla-mine) methyl)-6-metho of salt [16] or discharge to sea [17,18]. The above mentioned synthetic
compounds are nutrients during the eutrophication process after dis-
charge to sea, which lead to eutrophication. With the increasing envi-
Corresponding authors. ronmental awareness, the exploitation of environmental friendly
E-mail address: whf0618@163.com (H. Wang). corrosion and scale inhibitors is one of the focus researches.

http://dx.doi.org/10.1016/j.desal.2016.07.035
0011-9164/ 2016 Elsevier B.V. All rights reserved.
H. Wang et al. / Desalination 398 (2016) 198207 199

Recently, plant extracts have again been used as environmentally ac- polarization measurements conduct from scans 500 mV relative to
ceptable, renewable and readily available scale inhibitors. Plant extracts the open circuit potential (OCP) at scan rate of 0.57 mV s1.
can be extracted conveniently with lower cost, which is more ecological
compared with conventional synthetic inhibitors [1921]. The use of 2.3.2. Static tests for scale inhibition
plant extracts such as olive leaf [4], saffron [22], Vernonia amygdalina Static tests for scale were conducted according to the Chinese Na-
[23], leaves extract of African star apple [24], damsissa [25] and lupine tional Standard method [3]. The tests were maintained for 10 h at a cer-
seed [26] as effective scale and corrosion inhibitors have been reported. tain temperature with a certain amount of TRE. The remaining Ca2+ was
The inhibition performance of plant extracts is due to the presence of al- determined by EDTA titration after cooling to room temperature. The
kaloid, tannin, glycosides and amino acids [23]. scale inhibition efciency was calculated as follows:
The tobacco extracts are biodegradable, environmentally friendly and
renewable [27]. The main constituents identied in tobacco are organic
acids, phenolic compounds, carbohydrate compounds and nicotine [27 1 2
 100% 1
31]. Previous work indicated that tobacco extract had inhibitive property N0 2
for steel or aluminium in 13.5% NaCl solution or HCl solution [2730,32,
33]. Tobacco rob accounts for more than 60% weight of the tobacco plants,
which was usually treated by burning as agricultural waste. So the reuti- Where 1 is mass concentration of Ca2 + with TRE after heating
lization and the exploitation for potential bio-energy would be necessary. (mg L1); 2 is mass concentration of Ca2+ without TRE after heating
Our previous work showed that TRE had good scale and corrosion in- (mg L1); 0 is the mass concentration of Ca2+ of the blank solution be-
hibition properties for carbon steel in circulating cooling water [34]. No fore heating (mg L 1); and N is a concentration factor for articial
information on tobacco rob used as corrosion inhibitor and scale inhibi- seawater.
tor for seawater has been reported. Herein, we studied scale and corro-
sion performance of TRE in articial seawater. The corrosion inhibition 2.4. Infrared spectroscopy
and anti-scale properties of TRE in articial seawater were investigated
by potentiodynamic polarization and static tests. The surface of Q235 Fourier transform infrared spectroscopy (FT-IR) spectra were re-
steel was observed by SEM and XPS analyses. And the scale inhibition corded on a FT-IR spectrometer (Bruker Tensor 27) using the KBr pellet
mechanism was also proposed according to the results of SEM and XRD. technique. The sample of TRE adsorbed on Q235 steel was obtained after
the immersion of the test coupons in articial seawater with
150 mg L1 TRE for 12 h. After the immersion, the test coupons were
2. Experimental
dried at 60 C for 10 h. The lm formed on test coupons was carefully
scratched off and analyzed by the FT-IR spectrometer.
2.1. Preparation of TRE

The dried TR powder (8.0 g) was soaked in ask of three necked with 2.5. Surface analysis
distilled water (100 mL) and reuxed for 2 h at 100 C. After cooling to
room temperature, the mixture was ltered and then the ltrate diluted 2.5.1. Surface analysis for corrosion inhibition
to 100 mL. The residue was dried at 105 C for the removal of water for The test coupons were immersed in 200 mL of articial seawater
12 h. The concentration of extract was 34 mg mL1, which was deter- with TRE 150 mg L1 at 60 C and washed with distilled water and
mined according to the weight of the dried residue. then dried in air at 25 C. The structural and topographical information
was obtained using scanning electron microscope (SEM NOVA NA
NOSEM 450) and X-ray photoelectron spectroscopy (XPS UIVAC-PHI
2.2. Preparation of articial seawater PHI5000 VERSAPROBE). The monochromatized Al-K X-ray source was
operated in the constant analyzer energy mode. The internal calibration
The standard seawater solution was prepared according to (ASTM was referenced to the C 1s energy at 285 eV for aliphatic like species.
standard D1141-98(2013) American Society for Testing Materials)
(shown in Table 1) [35]. 0.1 M NaOH solution was used to adjust the
pH of seawater solution to 8.2. All articial seawater used in the exper-
iments was obtained through evaporation of the above mentioned stan-
dard seawater to two fold of its original concentration.

2.3. Methods for evaluation the corrosion and scale inhibition of TRE

2.3.1. Electrochemical studies for corrosion inhibition


CHI660C electrochemical analyzer was used for electrochemical
measurements. The working electrode was a square cut of Q235 steel
coupons with surface area 1 cm2. A platinum sheet and a saturated calo-
mel electrode (SCE) were used as auxiliary and reference electrodes re-
spectively. The working electrode and the reference electrode were
connected via a salt bridge. In order to minimize the ohmic voltage
error, the salt bridge was as close as possible to the electrode surface.
The working electrode was polished mechanically, washed with acetone,
distilled water and dried before measurement. The potentiodynamic

Table 1
Chemical composition of articial seawater.

Compound MgCl2 NaCl NaF NaHCO3 H3BO3 CaCl2 SrCl2 KCl KBr Na2SO4
Fig. 1. FT-IR spectra of samples: (A) TRE adsorbed on Q235 steel, (B) TRE, and (C) Q235
C(g L1) 5.20 24.5 0.003 0.201 0.027 1.16 0.025 0.695 0.101 4.09
steel.
200 H. Wang et al. / Desalination 398 (2016) 198207

Table 2
Peaks from FT-IR spectra of samples: (A) TRE adsorbed on Q235 steel, and (B) TRE.

Wavenumber (cm1) Possible groups Reference

Q235 in TRE TRE

3445 3373 OH/NH [36]


2927 Aliphatic or Aromatic CH [36,37]
2856 CH3O and/or CH2O [38]
1636 1624 C_N or C_O [38]
1385 1406 Framework vibration of pyridine ring [38]
1201 COH [38]
1161 COC [38]
1078 10981046 CN Tertiary amine (Nicotine) [38]
601 Fe2O3 [39]

2.5.2. Characterization of scale deposits


Crystals of CaCO3 and CaSO4 were collected in articial seawater in
the presence (TRE 100 mg L 1) and the absence of TRE for 10 h at
80 C. The scale deposits were characterized by SEM (NOVA NA Fig. 3. Nyquist plots for Q235 in articial seawater with different concentrations of TRE.
NOSEM 450) and X-ray diffraction (XRD D8 FOCUS).
in ethers [38]. The results of FT-IR show that the extracts from tobacco rob
3. Results and discussion include OH, C\\H, C\\O\\C, which indicate TRE may contain carbohy-
drate compounds. The 1406 cm1 band is assigned to the framework vi-
3.1. Characterization of TRE bration of pyridine ring [38]. The band at 1098 cm1 and 1046 cm1 is
due to the stretching mode of C\\N (tertiary amine) [37]. The framework
Fig. 1 shows the FT-IR spectra of the TRE, TRE adsorbed on Q235 steel vibration of pyridine ring and stretching mode of C_N indicates the pres-
and Q235 steel. The respective peaks of FT-IR are given in Table 2. The ab- ence of nicotine. The results indicate that TRE may contain mixtures of
sorption band at 3373 cm1 is attributed to N-H/O-H bond stretching vi- compounds such as carbohydrate compounds and nicotine.
bration [36]. The peak at 2927 cm1 indicates the presence of aliphatic or The FT-IR peaks of TRE were also observed in the spectra of TRE
aromatic C\\H groups [36,37]. The stretching mode of CH3-O and/or CH2- adsorbed on Q235 steel. The peaks at 1636 cm 1, 1385 cm 1 and
O is observed at 2856 cm1 [38]. The peaks at 1624 cm1 are correspond 1078 cm1 indicate nicotine was adsorbed on the Q235 steel surface.
to the stretching mode of C_N or C_C in aromatic hydrocarbon [38]. The The band at 601 cm1 probably originates from -Fe2O3 [39]. This indi-
peak at 1201 cm1 is attributed to C\\OH bond stretching vibration. The cates that nicotine may be responsible for corrosion inhibition.
absorbance at the 1161 cm1 is assigned to stretching mode of C\\O\\C The total carbohydrate compounds of TRE by high performance liq-
uid chromatography [40] (HPLC SHIMADZU LC-10 A) was 65.4 wt%, and
the content of nicotine of TRE analyzed by ultraviolet -visible absorption
spectrometry [41] (UV INESA L5) was 4.20 wt%. The others are pigments
and some unknown water-soluble constituents.

3.2. Corrosion inhibitive action of TRE

3.2.1. Potentiodynamic polarization measurements


Potentiodynamic polarization curves were measured for Q235 steel in
articial seawater in the absence and presence of different concentrations

Fig. 2. Polarization curves for Q235 in articial seawater with different concentrations of Fig. 4. Equivalent electrical circuit diagram. Rs: solution resistance; Rct: charge transfer
TRE. resistance; and Cdl: double layer capacitance.

Table 3
Polarization and EIS parameters for the corrosion of Q235 with different concentrations of TRE.

C EIS Polarization
(mg L1)
Rct IE% Ecorr (V vs SCE) Icorr (A cm2) IE% a (mV/dec) c (mV/dec)
( cm2 )

0 117 0.968 3.40 104 396 154


50 398 70.6 0.873 8.77 105 74.2 200 79.7
100 568 79.4 0.869 5.45 105 83.9 113 122
125 593 80.3 0.845 5.22 105 84.6 85.9 107
150 689 83.0 0.768 4.65 105 86.3 93.7 85.3
H. Wang et al. / Desalination 398 (2016) 198207 201

Table 4
Comparison of the IE of TRE with other natural products extracts.

Natural products Metal exposed Test media Concentration IE(%) Reference

Tobacco rob Q235 steel Described by 2.2 0.10 g L1 83.9a This study
Saffron Copper Natural seawater 0.10 g L1 67.0a [22]
Damsissa Aluminium 2 M NaOH + 0.5 M NaCl 0.16 g L1 45.9a [25]
Olive leaf Mild steel 0.7 M NaCl + 0.0025 M NaHCO3 + 0.028 M Na2SO4 + 0.01 M CaCl2 0.20 g L1 34.2b [4]
Lupine seed Aluminium 2 M NaOH + 0.5 M NaCl 0.16 g L1 45.9a [26]
Burley tobacco dust Steel/Al 3.5% NaCl 0.1 wt% ~90c [27]
Tobacco Al-Cu 1% NaCl 0.1 wt% 63.6a [29]
Tobacco Aluminium 3.5% NaCl 1.0 wt% 96.6c [32]
a
Values from the potentiodynamic polarization measurements
b
Values from electrochemical impedance spectroscopic measurement.
c
Values from the weight loss method.

of TRE at 60 C (Fig. 2). According to the method reported by Mansfeld in Fig. 2 and Table 3, the corrosion potential (Ecorr) positively shifted
[42], Tafel slopes a and c were derived through nonlinear least-squares and current densities decreased with increase of the concentration of
tting of data to the corresponding theoretical equation within the TRE, which indicated that TRE was a mixed-type inhibitor with predom-
(Ecorr 20) mV potential window. Tafel slopes can be obtained by com- inantly control of anodic reaction [45]. Similar results were reported by
puter analysis of polarization curves obtained in the vicinity of Ecorr. The Rosliza et al. using natural honey corrosion inhibitor on AlMgSi alloy
analysis based on the computer program CORFIT [43]. The electrochemi- in seawater [45]. High slope of Tafel indicates weak impact of potential
cal parameters derived from polarization curves are presented in Table 3. shift on corrosion rate [46]. The results in Fig. 2 and Table 3 showed that
Inhibition efciency (IE) was calculated using the following equation: the anodic slopes of TRE decreased more sharply than the cathode
slopes, which indicated the decrease in anodic reaction rates were
I0corr Icorr more obvious than the corresponding cathodic ones. TRE is a mixed-
IE%  100 2
I0corr type inhibitor with predominantly control of anodic reaction.
Fig. 3 shows the Nyquist plots of Q235 in articial seawater with differ-
Where I0corr and Icorr are represent corrosion current densities in the ent concentration of TRE. Nyquist plots were analyzed by tting the ex-
absence and presence of TRE, respectively. perimental data to a simple circuit model (Fig. 4). All the obtained plots
From Table 3, the decrease of the Icorr values with increasing TRE show one capacitive loop and the diameter of the semicircle increases
concentration indicated that TRE had corrosion inhibition performance with increase of TRE concentration, which suggests that the TRE lm
for Q235. IE increases with increase in concentration of TRE and 83.9% was formed on Q235 steel surface [47]. These results are in agreement
was obtained with 100 mg L1 TRE. Inhibitors can be classied to ca- with the results of polarization measurements, indicating that the TRE
thodic, anodic or mixed type according to changes observed in the po- does not alter the electrochemical reactions responsible for corrosion.
larization curves after addition of the inhibitor [44]. From the results The results of EIS measurements for the Q235 in articial seawater in

Fig. 5. Effect of temperature on IE.


202 H. Wang et al. / Desalination 398 (2016) 198207

the absence and presence of TRE are given in Table 3. Table 3 shows that
the charge transfer resistance increases with the presence of TRE, which is
attributed to a decrease in local dielectric constant and/or an increase in
the thickness of electrical double layer [48]. IE obtained from this tech-
nique is also in agreement with those obtained from polarization
measurements.
Table 4 shows a comparison of the IE of TRE with other natural prod-
ucts extracts The IE of TRE is 83.9% at a relatively low concentration of
TRE (0.10 g L1) in articial seawater. However, the IE of Saffron
(0.10 g L 1) is only 67.0% in seawater. The IE of Damsissa
(0.16 g L1), Olive leaf (0.20 g L1) and Lupine seed (0.37 g L1) are
only 45.9%, 34.2% and 45.4%, respectively. A comparison of these data
with the results of previous investigation indicates that TRE has good in-
hibition performance in articial seawater.

3.2.2. Effect of temperature on the corrosion inhibition performance of TRE


The effect of temperature on the corrosion inhibition performance of
TRE in articial seawater was studied by potentiodynamic polarization
in the range of 2560 C (Fig. 5). IE increases from 28.2% to 83.9% in
the presence of 100 mg L 1 TRE with the increase of temperature
from 25 C to 60 C, which indicates that the chemical adsorption of
TRE components onto Q235 steel surface [49]. According to results of
the FT-IR, chemisorption of the nicotine to Q235 provides more effective
protection because of reduction of the reactivity of the metal at the sites
where it attached [50,51]. The chemisorption of the nicotine to Q235 en-
hances with increase in temperature, which leads to high IE.

3.2.3. Surface morphology of Q235 steel surface exposed to TRE


SEM images of Q235 steel (Fig. 6a), Q235 steel immersed in articial
seawater in the absence (Fig. 6b) and presence of 150 mg L1 TRE (Fig.
6c) are shown in Fig. 6. Fig. 6a exhibits nely polished characteristic sur-
face and some scratches after polishing. Fig. 6b shows that the Q235 sur-
face is severely damaged in the absence of the TRE in articial seawater.
While in the presence of TRE (Fig. 6c), smooth surface of Q235 com-
pared with that of the surface immersed in articial seawater medium
alone, which is due to the a protective layer formed by adsorption the
constituent of TRE on the Q235 steel surface [12].

3.2.4. XPS analysis


The XPS measurement is used to obtain the further surface informa-
tion on the Q235 steel with TRE. For comparison, the XPS spectra were
obtained from the pure TRE, and the Q235 steel containing
Fig. 6. SEM images of Q235 steel: (a) polished surface (b) Q235 steel immersed in articial
150 mg L1 TRE in articial seawater (Figs. 7 and 8). For the pure TRE, seawater and (c) Q235 steel immersed in articial seawater with 150 mg L1 of TRE.
in the O 1s spectrum, a single peak appeared at 532.5 eV is mainly attrib-
uted to the bond of C\\O [52], which originates from carbohydrate com-
pounds. The N 1s spectrum of the pure TRE was a single peak appeared oxidized species (Fe3+) [56,57]. Therefore, the oxide layer thickness in-
at 399.3 eV is mainly attributed to the bond of C\\N_C [21] in pyridine crease with the addition of TRE, which may reduce ions diffusion.
ring, which originates from nicotine. The deconvoluted C 1s spectrum The O 1s spectrum for Q235 carbon steel surface in articial seawater
for pure TRE showed three main peaks, The rst peak at 285.0 eV has containing TRE could be deconvoluted into three main peaks labeled as
the largest contribution and is attributed to the C\\H, C\\C and C_C 1, 2 and 3. The peak 1 at 529.5 eV is ascribed to O2 and relates to oxygen
bonds from TRE molecules [53]. The peak at 286.5 eV can be ascribed atoms bonded to Fe3 + in the Fe2O3 and/or Fe3O4 oxides [58]. Peak 2
to C\\O (alcoholic hydroxyl and ether) in carbohydrate compounds (531.4 eV) is attributed to OH, which associates to the presence of hy-
[54]. The third peak at 288.1 eV may be ascribed to the carbon atoms drous iron oxides, such as FeOOH [58]. The third peak at 532.9 eV may
bonded to nitrogen C_N in the pyridine ring [21]. be assigned to oxygen of adsorbed water [56]. In N 1s spectrum, a single
The Fe2p spectrum for Q235 steel surface after immersion exhibits peak appeared at 399.1 eV was mainly attributed to the bond of
two peaks, 710 eV (Fe2p3/2) and 724 eV (Fe2p1/2), with an associated C\\N_C [21] in pyridine ring, which originates from nicotine. This indi-
ghost structure on the high energy side, indicated the subsequent oxida- cated that complex of Fe-plant extract formed directly on the basis of
tion of Q235 steel surface. The Fe 2p3/2 XPS spectrum was deconvoluted donor acceptor interactions between the vacant d orbital of iron and N
into three peaks. The peak l obtained at lower binding energy (708.4 eV) atoms in nicotine. Indeed, the C 1s spectrum was deconvoluted into
can be attributed to metallic iron (Fe0) as previously reported [53,55]. The three components. The peak at 285.0 eV can be attributed to C\\H,
peaks at 710.5 eV assigned to Fe3+ is attributed to Fe2O3 and/or FeOOH C\\C and C_C bonds from TRE molecules [53]. The peak at 286.3 eV
[56]. The formation of oxide layer can improve the corrosion of Q235 can be ascribed to C\\N and/ or C_N in nicotine [21]. The third peak
steel in articial seawater by reducing ions diffusion. The last peak at at 288.7 eV may be ascribed to the carbon atoms bonded to nitrogen
714.5 eV may be ascribed to the satellite of Fe(III) [53,56]. Compared C_N in the pyridine ring [21].
with that Q235 steel without TRE, the Fe2p3/2 XPS results of Q235 steel The XPS results provide direct evidence of the chemical interactions
in articial seawater with TRE showed the increase of the amount of between the nicotine of TRE and Q235 steel surface. The chemisorption
H. Wang et al. / Desalination 398 (2016) 198207 203

Fig. 7. X-ray photoelectron spectra of (a) O 1s, (b) N 1s and (c) C 1s for pure TRE.

mechanism was involved by displacing water molecules from the Q235 calcium scale increased. An inhibition efciency of 100% and 91.7%
surface and the sharing electrons between nitrogen and vacant d-orbital was obtained at 70 C and 80 C respectively with 140 mg L 1 TRE.
of iron. The nicotine of TRE adsorbed onto Q235 surface to form a pro- The results suggest that TRE has a good performance for scale inhibition,
tective lm to keep steel from corrosion. This could be conrmed by which is also conrmed the results of SEM. In general, present used
the results of FT-IR and SEM. polyphosphonate scale inhibitor hydrolyzes easily when temperature
is above 70 C [14]. High inhibition efciency at 70 C and 80 C indicates
3.3. Antiscalant behavior of TRE that TRE has good scale inhibition performance at a relatively high tem-
perature compared with polyphosphonate additives.
3.3.1. Performance of TRE for scale inhibition
The effect of temperature and concentration of TRE on scale inhibi- 3.3.2. SEM images of CaCO3 and CaSO4 crystals
tion efciency was studied (Fig. 9). With the increase of the concentra- The CaCO3 and CaSO4 scale deposits were observed by SEM in articial
tion of TRE from 20 mg L1 to 140 mg L1, the inhibition efciency of seawater. As shown in Fig. 10, regular shape and glossy surface of CaCO3

Fig. 8. X-ray photoelectron spectra of Q235 steel in articial seawater of TRE.


204 H. Wang et al. / Desalination 398 (2016) 198207

which are consistent with Joint Committee on Powder Diffraction Stan-


dards (JCPDS) 41-1475. The results show that CaCO3 deposits in the ab-
sence of TRE are mainly aragonite. In spectrum (b), the characteristic
peaks of aragonite disappeared, while diffraction peaks of 31.7, 45.4
and 56.5 was observed as well as in spectrum (e). The changes in
peaks illustrate that CaCO3 crystals are modied in form and structure
in the presence of TRE, which indicates that the crystal growth of
CaCO3 is blocked by the TRE compared with (Fig. 11(a)). This is due to
the action of chelating water-soluble \\OH groups of carbohydrate
compounds on the crystal growth of CaCO3, which is in agreement
with the previous study by Wang et al. [60].
XRD spectrum of CaSO4 deposits in the absence and presence of TRE
are shown in Fig. 11. In the absence of TRE (Fig. 11(c)), the strong diffrac-
tion peaks at the 22.9, 25.6, 31.6, 36.5, 38.8, 41.1, 43.0, 65.7 and
66.7 are characteristic peaks of CaSO4 (JCPDS) 03-0377. The crystal struc-
ture diffraction peaks became weak with the addition of TRE, which im-
Fig. 9. Effects of TRE concentration and temperature on scale inhibition efciency and
images of scale deposits in blank (a) articial seawater and with 140 mg L1 of TRE (b).
plied the change of surface morphology and particle size [59] (Fig.
11(d)). The change of CaSO4 crystal forms morphology (according to
the results of SEM) after the addition of TRE indicates that TRE retard
the growth of CaSO4 crystals and distorted the CaSO4 crystals.
deposits were obtained in the absence of TRE (Fig. 10(a)), while CaSO4 de- [59]. Such changes lead to the loose of CaSO4 crystals. The soft de-
posits have a regular shape of spindle (Fig. 10(c)). In the presence of TRE, posits can be removed easily and have poor adhesion to the beaker in
the shapes of CaCO3 and CaSO4 deposits are irregular and ne (Fig. 10(b) the presence of TRE.
and (d)). According to the previous reported results, dirt is easily washed The mechanisms for scale inhibition of TRE (Fig. 12) have been associ-
away by water at certain water scouring velocity or temperature [59,60]. ated with active functional group (\\OH). It is likely that the active func-
tional group of carbohydrate compounds from TRE can obstruct the
3.3.3. XRD analysis scale formation process by threshold inhibition, crystal dispersion and
XRD spectrum of CaCO3 crystals is shown in Fig. 11. Diffraction peaks modication of the growth of microcrystal morphology. During the pro-
at 26.22, 27.22, 33.13, 36.18, 37.26, 38.48, 42.91, 45.85, 48.32 cess, the active crystal growth sites are blocked with the increase of surface
and 50.22 are characteristic peaks of aragonite in spectrum (a), anionic charge and inhibition of the crystal growth by altering the shape of

Fig. 10. SEM images of CaCO3 (a), CaSO4 (b) deposits without TRE and CaCO3 (c), and CaSO4 (d) deposits with 100 mg L1 TRE.
H. Wang et al. / Desalination 398 (2016) 198207 205

Fig. 11. XRD pattern of the CaCO3 crystals: (a) in the absence of TRE and (b) in the presence of 100 mg L1 TRE and the CaSO4 crystals: (c) in the absence of TRE and (d) in the presence of
100 mg L1 TRE and (e) the TRE.

the micro-crystals, respectively [3]. This could be also conrmed by the compounds and nicotine. The main constituents responsible for corro-
SEM and XRD results. sion inhibition in articial seawater were found to be nicotine of TRE.
The IE of Q235 steel increases with increase of TRE concentration and
4. Conclusions temperature. IE up to 83.9% in articial seawater has been achieved
with 100 mg L 1 TRE at 60 C. The good corrosion inhibition perfor-
Combined with different analyses to characterization of TRE, it mance of TRE in articial seawater was obtained with the temperature
shows that TRE contain mixtures of compounds i.e. carbohydrate range of 25 C60 C. Polarization studies showed TRE acts as a mixed

Fig. 12. The mechanisms for scale inhibition.


206 H. Wang et al. / Desalination 398 (2016) 198207

type inhibitor. TRE also showed the promising performance of scale in- [23] A.S. Abdulrahman, Effect of Vernonia amygdalina extract on corrosion inhibition of
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hibition in seawater, the scale inhibition was 100% achieved with [24] M. Omotioma, S.O. Egbuna, Leaves extract of African star apple as corrosion inhibitor
140 mgL 1 TRE at 70 C. SEM and XRD implied that the CaCO3 and of mild steel in natural and oil polluted seawater, Int. J. Environ. Sci., Manage. Eng.
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