See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/303041663

Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and

synergistic intensifiers for mild steel

Article  in  Chinese Journal of Chemical Engineering · May 2016

DOI: 10.1016/j.cjche.2016.04.028

CITATIONS READS

33 292

4 authors, including:

Ekemini Ituen Abosede Olubunmi James

University of Uyo University of Port Harcourt
64 PUBLICATIONS   749 CITATIONS    12 PUBLICATIONS   308 CITATIONS   

SEE PROFILE SEE PROFILE

Onyewuchi Akaranta
University of Port Harcourt
167 PUBLICATIONS   1,116 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Enhancing Oil Recovery in Niger Delta View project

Formulation of Local materials for Chemical Enhanced Oil Recovery View project

All content following this page was uploaded by Ekemini Ituen on 12 May 2019.

The user has requested enhancement of the downloaded file.

CJChE-00530; No of Pages 6
Chinese Journal of Chemical Engineering xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

Chinese Journal of Chemical Engineering

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

Process System Engineering and Process Safety

Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic

intensifiers for mild steel
Ekemini Ituen 1,2,⁎, Abosede James 3, Onyewuchi Akaranta 2,3, Shuangqin Sun 1
1
Materials Physics and Chemistry Research Laboratory, College of Science, China University of Petroleum, Qingdao 266000, China
2
African Centre of Excellence in Oilfield Chemicals Research, Institute of Petroleum Studies, University of Port Harcourt, Nigeria
3
Department of Pure and Industrial Chemistry, University of Port Harcourt, Nigeria

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

Article history: Extracts of elephant grass (Pennisetum purpureum) blended with some intensifier halides like ammonium chlo-
Received 25 January 2016 ride (AMC) and potassium iodide (PTI) were investigated as corrosion inhibitor for mild steel. The corrosion pro-
Received in revised form 5 April 2016 cess was monitored in 3.5% HCl by mass loss and electrochemical techniques at 30, 40, 50, 60 and 90 °C. Addition
Accepted 5 April 2016
of AMC and PTI increased the inhibition efficiency with the highest inhibition efficiency obtained with PTI blend-
Available online xxxx
ed extract. The blends behaved as mixed type inhibitors and were spontaneously adsorbed on mild steel surface
Keywords:
in exothermic nature. Synergistic parameters of the intensifier ions revealed cooperative effect. Kinetic data treat-
Adsorption ment indicated increase in energy barrier by intensifier ions. The results demonstrate that elephant grass extract
Charge transfer resistance blended with halide ions can act as alternative ecofriendly inhibitor for mild steel at elevated temperatures.
Corrosion inhibitor formulations © 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
Electrochemical techniques
Elephant grass

1. Introduction would be cheap, readily available, renewable and non-toxic. Elephant

Corrosion inhibitors have been sourced from various materials in-
cluding plant biomass. The effectiveness of extracts from various plant
biomasses as corrosion inhibitors for metals in different aggressive
media has received much attention because of their non-toxic nature
[1–6]. The corrosion inhibition efficiency of many plant extracts howev-
er declines at high temperatures owing to degradation of their complex
phytochemicals [7]. This limits their application in the field since hydro-
carbon recovery from many rewarding pay zones requires high temper-
ature operations. It would be desirable that corrosion inhibitors from
plant extracts be optimized to be effective at high temperatures. Various
groups of synergistic chemicals like halide ions, surfactants, solvents
and polymers are getting increasing attention these days as intensifiers
[8–10]. They are used to enhance performance of corrosion inhibitors
sometimes at high temperatures. When the main corrosion inhibitor is
blended with these additives, a corrosion inhibitor formulation (CIF) is
obtained [11]. There are many reports on the use organic molecules as
the main corrosion inhibitor [12–14] but some of these molecules are
expensive and toxic.
In search for more sustainable, cost effective and eco-friendly source
of corrosion inhibitors, elephant grass extract (EGE) has been blended
with halide ions for investigation in this study. The blends from EGE
⁎ Corresponding author at: Department of Pure and Industrial Chemistry, University of
Port Harcourt, Nigeria.
E-mail address: ebituen@gmail.com (E. Ituen).
grass grows abundantly almost everywhere in Nigeria. It is not edible,
so using it as corrosion inhibitor source will not compete with food.
Electron donor sites like O, N, and π electrons which are regarded as po-
tential adsorption sites in other effective corrosion inhibitors are
present in its phyto-compounds like anthocyanins, lignin and flavo-
noids [15–19]. Commercial production of corrosion inhibitor from EGE
would reduce export, generate internal wealth and contribute to local
content development. The corrosion process is simulated in hydrochlo-
ric acid (HCl) using mild steel. Our study is also significant to the indus-
try because mild steel is used in construction of most hydrocarbon
production, transportation and storage facilities which is vulnerable to
corrosive attack. Likewise, HCl is usually employed as acidizing and
well stimulation fluids in enhanced oil recovery and is very corrosive
[20]. With a concentration of 3.5%, EGE can be applied in fluids requiring
intermediate acid concentration.
2. Materials and Method
2.1. Preparation of metal specimens
Mild steel sheet purchased from construction materials market in
Uyo, Nigeria, was used for the study. The chemical composition of the
mild steel was (wt%): C, 0.13; Si, 0.18; Mn, 0.39; P, 0.40; S, 0.04;
Cu, 0.025 and balance is Fe. It was mechanically press-cut into coupons
of dimensions 4 cm × 4 cm, degreased in ethanol, abraded using differ-
ent grades of silicon carbide papers and finished with CC-22F P1200

http://dx.doi.org/10.1016/j.cjche.2016.04.028
1004-9541/© 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

Please cite this article as: E. Ituen, et al., Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild
steel, Chin. J. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.cjche.2016.04.028
2 E. Ituen et al. / Chinese Journal of Chemical Engineering xxx (2016) xxx–xxx

grade. The coupons were cleaned with acetone, air-dried, weighed and 2.5. Potentiodynamic polarization measurement
immediately immersed in appropriate test solution. Coupons for elec-
trochemical studies were prepared by polishing about 1.44 cm2 exposed The electrochemical same set up was used to obtain Tafel polariza-
area to mirror finishing. tion curves at (28 ± 2) °C by changing electrode potential automatically
from −250 mV to +250 mV vs. SCE at open circuit potential (OCP) with
2.2. Preparation of test solutions a scan rate of 1.0 mV·s−1. The inhibition efficiency (εPD) was calculated
from corrosion current density values (Eq. (5)) obtained from data
The corroding medium was simulated using 3.5% HCl prepared by fitting with the software mentioned.
diluting 37% analytical grade HCl in distilled water. Mature elephant
grass shoots harvested within University of Uyo community, Nigeria,  

was washed in distilled water, air-dried in the laboratory, grounded to ε PD ¼ 100 1−ICORRi I ; ð5Þ
CORRb
powdery form and extracted in acetone by maceration, percolation
and infusion [21]. The main inhibitor from EGE was prepared to concen-
tration of 5.0 g·L−1 in the acid. Ammonium chloride (AMC) and potas- where ICORRb and ICORRi are the corrosion current densities in the ab-
sium iodide (PTI) at concentration of 0.1 mol·L− 1 each were used as sence and presence of the inhibitor respectively.
additives to obtain the blends. The blends are coded EGE/AMC for ele-
phant grass extract blended with ammonium chloride and EGE/PTI for 2.6. Linear polarization resistance
elephant grass extract blended with potassium iodide.
This measurement was conducted using an electrode potential of
2.3. Weight loss technique ± 20 mV vs. OCP maintained at a scan rate of 1.0 mV·s−1 at (28 ±
2) °C. Inhibition efficiency (εRP) was calculated from the polarization re-
The procedures reported by Hussin and coworkers [22] according to sistance obtained using Eq. (6).
NACE Recommended Practice RP-0775 and ASTM G-1 & G-4 for weight
loss experiment were employed in this study. However, different tem-
 
peratures (30 °C, 40 °C, 50 °C, 60 °C and 90 °C) were obtained using R −RPi
ε RP ¼ 100 Pb ; ð6Þ
water bath. As a modification, the immersed coupons were retrieved RPb
after six (6) hours, washed in detergent solution, rinsed with distilled
water, dipped in acetone to facilitate fast air-drying and then
reweighed. All masses were measured using Sartorius CPA225D analyt- where RPb and RPi are the polarization resistances in the absence and
ical balance of sensitivity ± 0.01 mg. Denoting the initial and final presence of the inhibitor respectively.
weights of the coupons with w1 and w2 respectively, corrosion rates
(CR) (mg·cm−2·h−1)), percentage inhibitor effectiveness (inhibition 3. Results and Discussion
efficiency), εWL, and degree of surface coverage (θ) was calculated re-
spectively as follows: 3.1. Weight loss technique

w1 −w2 The corrosion rates calculated from mass loss data were highest in
CR ¼ ð1Þ
At 3.5% HCl at all temperatures but reduced in the presence of inhibitor so-
  lutions as shown in Fig. 1. Addition of the blends reduces corrosion rate
R −Ri of mild steel at all temperatures studied. The extent of reduction is esti-
ε WL ¼ 100 b ð2Þ
Rb mated using inhibition efficiency values (Table 1). Effectiveness of EGE
alone declines markedly at high temperatures than when treated with
θ ¼ 0:01ε inh ð3Þ halide additives. Similar results were obtained by Anupama and co-
workers [1] and others [23,24]. There are also cases where opposing
where Rb and Ri are the corrosion rates (g·cm−2·h−1) in the absence and trend is reported [25,26]. The inhibition efficiency follows the trend
presence of the inhibitor respectively and A is the surface area (cm2) of EGE/PTI N EGE/AMC N EGE and decreases as temperature increases.
the metal specimens.

2.4. Electrochemical impedance spectroscopy

EGE/PTI
Gamry Reference 600 Potentiostat/Galvanostat/ZRA REF600-18042 100 EGE/AMC
electrochemical workstation with conventional three electrode ar- EGE
rangement: saturated calomel electrode (SCE) as reference, platinium HCl
Corrosion rate/%

electrode as counter and mild steel as working electrode was used.

The potential was stabilized for 30 min at room temperature (28 ±
2) °C) at frequency range of 10 mHz to 100 kHz and amplitude voltage
of 5 mV peak to peak using AC perturbation signal at Ecorr. Experiments 50
were conducted by complete immersion without stirring. The inhibition
efficiency was calculated from charge transfer resistance values
(Eq. (4)) which was obtained using Echem Analyst version Gamry Ap-
plication software package and data fitting of Nyquist and Bode plots.
 
RCTI −RCTB
εEIS ¼ 100 ; ð4Þ 0
RCTI 30 40 50 60 70 80 90
Temperature /oC
where RCTB and RCTI are charge transfer resistances in the absence and
presence of inhibitors respectively. Fig. 1. Variation of corrosion rates of mild steel in 3.5% HCl with temperature.

Please cite this article as: E. Ituen, et al., Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild
steel, Chin. J. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.cjche.2016.04.028
 E. Ituen et al. / Chinese Journal of Chemical Engineering xxx (2016) xxx–xxx 3

Table 1
Inhibition efficiency evaluated using weight loss technique

System 30 °C 40 °C 50 °C 60 °C 90 °C

EGE 83.5 81.7 76.6 67.2 19.3

EGE/AMC 88.3 86.0 83.9 82.6 46.4
EGE/PTI 94.9 94.2 92.7 88.9 57.6

3.2. Electrochemical techniques

Fitting of EIS data into Nyquist (Fig. 2) and Bode (Fig. 3) plots pro-
duce imperfect single depressed semicircles, a behavior which [27]
also observed and attributed to surface roughness or inhomogeneity
of the mild steel. The single capacitive loop signifies that the corrosion
process is mainly controlled by charge transfer process [28]. It also indi-
cates that presence of inhibitors does not change the mechanism of steel
dissolution. Data obtained were also fitted into equivalent circuits and
the best fit obtained is shown in Fig. 4. Surface roughness or heterogene-
ity is compensated by using the constant phase element (CPE), a non-
90
80
70 HCl
EGE
60 EGE/AMI
(/ZRE/ )/Ω·cm-2
Fig. 4. Equivalent electrical circuit used for fitting of data for corrosion of mild steel in 3.5%
HCl in the absence and presence of the different inhibitors.
integer element dependent on frequency, with magnitude given by Y0
and n, related to impedance by:
Z CPE ¼ ðY 0 Þ−1 ðjwÞ−n ð7Þ
where Y0 is the CPE constant, w is the angular frequency, j is an imag-
inary complex number, ( j2 = − 1)α is the phase angle of CPE and n =
2α ⁄ π is the CPE exponent.
The values of n is used to predict the degree of heterogeneity or
roughness of mild steel surface. The inhibitor is believed to act by diffu-
sion from the bulk phase, condensation and adsorption on metal sur-
face. Some results from electrochemical impedance studies provide
considerable evidence that the inhibitor was adsorbed at the interface,
and a thin insulating film was formed. Increase in n values on addition

EGE/PTI
50
of inhibitor than free acid and EGE solution is an indication of possible
40 reduction of surface roughness by adsorption of inhibitor [29]. The coef-
ficient, n, also indicates a shift to capacitive behavior initiated by inter-
30
ference of an insulator or dielectric at the metal/solution interface on
20 addition of inhibitor. That insulator is considered to be the thin surface
protective inhibitor film responsible for the corrosion inhibition.
10
The charge transfer resistances obtained increased in the presence of
0 inhibitor than the free acid (Table 2), also pointing to presence of a re-
-10 sistive dielectric layer at the interface. Increase in peak heights of Bode
0 10 20 plots also indicates more capacitive response of the interface caused
(/ZIM/) /Ω·cm-2 by presence of adsorbed inhibitor layer. The magnitude of the capaci-
tance is calculated from peak angular frequency (wmax) using Eq. (8).
Fig. 2. Nyquist plot for the corrosion of mild steel in 3.5% HCl in the absence and presence
of the different inhibitors. C dl ¼ Y 0 ðw max Þn−1 ð8Þ

200

180

160

140 H
HCl
E
EGE E
120 E
EGE E/AM
MC
Zmod /Ω·cm-2

100
E
EGE E/PT
TI

80

60

40

20

-
-20
0.01 0.1 1 10 100 1000 10000 100000
lgf

Fig. 3. Bode plot for the corrosion of mild steel in 3.5% HCl in the absence and presence of the different inhibitors.

Please cite this article as: E. Ituen, et al., Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild
steel, Chin. J. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.cjche.2016.04.028
4 E. Ituen et al. / Chinese Journal of Chemical Engineering xxx (2016) xxx–xxx

Table 2 Table 3
Parameters obtained from EIS measurement for mild steel in 3.5% HCl in absence and pres- Parameters obtained from PDP measurement for mild steel in 3.5% HCl in the absence and
ence of different inhibitors presence of different inhibitors

Parameters 0.0EGE 5.0EGE EGE/AMC EGE/PTI Parameters 0.0EGE 5.0EGE EGE/AMC EGE/PTI

RCT/Ω·cm2 17.4 113.3 178.0 191.9 βA/mV·dec−1 89.1 75.5 71.9 66.4
RS ×10−3/Ω·cm2 565.0 337.0 187.3 163.3 βC/mV·dec−1 159.5 126.6 138.7 99.7
Y0 ×10−6 412.9 204.5 175.8 145.4 ICORR/μA·cm−2 1390.1 151.0 129.0 54.6
α × 10−3 855.0 876.6 864.1 884.8 ECORR/mV·s−1 −404.1 −474.0 −436.0 −470.0
n 0.5 0.6 0.6 0.5
wmax 31.6 100.2 126.0 126.0
Cdl 1.99 0.56 0.11 0.01
Table 4
Parameters obtained from LPR measurement for mild steel in 3.5% HCl in absence and
presence of different inhibitors
The Cdl values decrease more with the inhibitors than free acid and
Parameter 0.0EGE 5.0EGE EGE/AMC EGE/PTI
EGE perhaps due to decrease in local dielectric or an increase in thick-
ness of the electrical double layer (adsorbed protective film), or both. Rp/Ω·cm2 22.2 191.2 219.1 619.4
Similar trend is reported in literature [30]. The direction of decrease in
Cdl also coheres with the trend of inhibition efficiency implying that
the thickness of the film is improved by the synergistic effects of halide Table 5
compounds added. Inhibition efficiencies obtained using different electrochemical techniques
Tafel plots (Fig. 5) also reveal that the corrosion current densities
EIS PDP LPR
shifted to lower values (Table 3) which indicate that the inhibitors func-
EGE 84.64 89.13 88.39
tion by the adsorption mechanism and geometric blocking of active
EGE/AMC 90.22 90.72 89.87
sites on the steel surface. The linear polarization resistances obtained EGE/PTI 90.93 96.07 96.42
decrease in the presence of inhibitor (Table 4). Calculated values of inhi-
bition efficiency obtained using the various techniques are comparable
(Table 5), with slight differences which can be attributed to differences molecules is also estimated using Eq. (11). All these parameters are cal-
in immersion time. culated and presented in Table 6.

3.3. Thermodynamic and kinetic study logðCR=TÞ ¼ ðRT=NhÞ expðΔS =RÞ expð−ΔH =RTÞ ð9Þ

Stability of each of the adsorbed inhibitor film is important and was

ΔGads ¼ ΔH ads −TΔSads ð10Þ
evaluated using thermodynamic transition state equation (Eq. (9)). In-
T Þ vs. 1/T afford thermo-
tercepts and slopes of linear plots (Fig. 6) of lgðCR −ΔGads

dynamic parameters, namely, enthalpy change (ΔHads) and entropy K ads ¼ 0:018e RT ð11Þ
change (ΔSads) of the adsorption process. The free energy change of ad-
sorption (ΔGads) is calculated from Eq. (1)0 for each temperature. Equi- where h (6.62 × 10− 34 J·s) is the Planck's constant, N
librium constant of adsorption (Kads) which can give insights on the (6.02 × 1023 mol−1) is the Avogadro's number, R is the molar gas con-
strength of interaction between the adsorbed film and surface iron stant and T (K) is the absolute temperature.

-0.1

HCl
-0.2
EGE
EGE/AMC
-0.3 EGE/PTI
E (vs. Ref)/V

-0.4

-0.5

-0.6

-0.7

-0.8
1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 10
lgI

Fig. 5. Tafel plot for the corrosion of mild steel in 3.5% HCl in the absence and presence of different the inhibitors.

Please cite this article as: E. Ituen, et al., Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild
steel, Chin. J. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.cjche.2016.04.028
 E. Ituen et al. / Chinese Journal of Chemical Engineering xxx (2016) xxx–xxx 5

2.5
-0.5

2.0
-1.0
1.5
-1.5
lg (CR/T)

1.0

lg CR
-2.0
HCl 0.5
EGE HCl
-2.5 EGE/AMC EGE
EGE/PTI 0.0 EGE/AMC
-3.0 EGE/PTI
-0.5

-3.5
-1.0
2.8 3.0 3.2 3.4
(1000/T) /K-1 2.7 2.8 2.9 3.0 3.1 3.2 3.3
(1000/T) /K-1
Fig. 6. Transition state plot for the corrosion of mild steel in 3.5% HCl in the absence and
presence of different the inhibitors. Fig. 7. Arrhenius plot for the corrosion of mild steel in 3.5% HCl in the absence and
presence of different the inhibitors.

The negative ΔGads values show that the inhibitors are spontaneous-
ly adsorbed on mild steel surface while negative Δ H⁎ shows that ad- Table 7
sorption was exothermic, with the evolution of heat. The range of Activation parameters obtained from Arrhenius plot
ΔGads values (b− 20 kJ·mol−1) signifies physical adsorption mecha-
Parameters 3.5% HCl EGE EGE/AMC EGE/KI
nism [31]. Adsorption becomes more spontaneous as temperature
−1
increases judged from the increasing magnitude of ΔGads. The spontane- Ea/J·mol 70.576 89.850 96.355 109.814
A × 109 3.257 0.096 0.089 0.081
ous adsorption favors EGE/PTI at all temperatures more than EGE and
EGE/AMC, hence the higher interactive strength. Also, Kads values re-
main fairly constant in HCl implying no possibility of interaction due Activation parameters were calculated from slope and intercept of
to the absence of an adsorbed film. However, the values change in linear plots (Fig. 7) of lg CR vs. 1/T Addition of the halide ions increased
each of the blends demonstrating the presence of adsorbed film. Trend the activation energy as shown in Table 7. Inhibitory action can be at-
of inhibitor interaction with metal surface (Kads) is similar to that of in- tributed to deactivation of some of the acid molecules by formation of
hibition efficiency. a barrier by the adsorbed molecules. The barrier is higher in the pres-
For desorption of inhibitors at high temperatures, Kads values should ence of the halide ions than with EGE because the activation energy fol-
decrease considerably as temperature increases [11]. Our results show lows the trend EGE/PTI N EGE/AMC N EGE N HCl. Similar explanations
that Kads changes rather ‘sluggishly’ with temperature. This kind of have also been given in previous report [33].
behavior instructs that the decline in inhibition efficiency at high tem-
perature is perhaps not due to desorption. The decline is therefore at- 3.4. Synergistic halide ions effect
tributed to degradation of some phytochemicals of EGE by heat. The
physically adsorbed inhibitors could form monolayer films that would The degree of cooperative enhancement of the inhibition efficiency
be fairly thermally stabilized by the synergistic ions. Further study of EGE is estimated using synergism parameter (SP) equation
would be required to validate this claim. (Eq. (13)) [34] proposed by Amaraki and Hackermann.
The corrosion inhibition process was also examined kinetically to
further explain its dependence on temperature. The idea of collision 1−ðIi þ I a Þ
SP ¼ ð13Þ
theory and activation energy is used to explain inhibitive effects of the 1−ðIiþa Þ
inhibitors. The acid molecules was considered to first collide with the
steel surface using a minimum energy (Ea) required to cause corrosion where Ii is inhibition efficiency of EGE, Ia is inhibition efficiency of the
[32]. This energy is obtained by fitting corrosion rate data into Arrheni- synergistic additive and Ii+a is inhibition efficiency of blend. According
us' kinetic model (Eq. (12)). to the equation, there is no interaction between the additives and EGE
when SP approaches or is unity; there is synergistic adsorption and in-
 teractions when SP is greater than unity and antagonistic adsorption
lg CR ¼ lg A− Ea 2:303RT
ð12Þ
when less than unity [12,35]. Values of SP calculated using mass loss
data are 1.23 and 1.29 for chloride and iodide ions respectively, meaning
where A is the Arrhenius pre-exponential frequency factor, R and T re- that the additives actually exhibited synergistic effect on adsorption of
tain their usual meanings. EGE. Iodide ions (radius 0.134 nm) give greater synergistic effect than

Table 6
Calculated thermodynamic parameters for mild steel in 3.5% HCl in the absence and presence of different inhibitors

Corrosion inhibitor ΔH⁎/kJ·mol−1 ΔS⁎/kJ·mol−1 −ΔGads × 103/kJ · mol−1 Kads × 10−3/mol−1

30 °C 40 °C 50 °C 60 °C 90 °C 30 °C 40 °C 50 °C 60 °C 90 °C

HCl −53.4 15.8 4.8 5.0 5.2 5.3 5.8 0.123 0.123 0.123 0.123 0.122
EGE −85.7 28.7 8.8 9.1 9.3 9.6 10.5 0.586 0.586 0.585 0.584 0.582
EGE/AMC −86.3 27.5 5.2 8.4 8.7 9.0 10.1 0.510 0.509 0.509 0.508 0.507
EGE/PTI −94.1 45.8 14.0 14.4 14.9 15.3 16.7 4.619 4.611 4.606 4.602 4.589

Please cite this article as: E. Ituen, et al., Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild
steel, Chin. J. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.cjche.2016.04.028
6 E. Ituen et al. / Chinese Journal of Chemical Engineering xxx (2016) xxx–xxx
chloride ions (radius 0.090 nm) which may be attributed to differences
in hydrophobicity due to larger ionic radius. Atoms and ions with large
atomic radii are assumed to be more susceptible to adsorption and also
promote cooperative adsorption of other molecules.
The synergistic effect exhibited by both halides is attributed to either
(1) initial adsorption of the halide anions on the steel surface followed
by enhanced adsorption of EGE cations or (2) the halides initially mod-
ifies the chemical structures of some phyto-compounds in EGE and im-
prove their affinity for the metal surface. The former has been reported
for synergistic inhibition between halide ions and xanthan gum [12].
There may also be a possibility of the later taking place by converting
some EGE phytochemicals to composites. The chemically modified com-
posites perhaps possess more adsorption sites with improved binding
affinity for the mild steel surface. It is however difficult to ascertain
the exact mechanism from results obtained and techniques used. Fur-
ther studies with structural characterization techniques may give
more insights on the chemical identities of these composites.
4. Conclusions
From the results of this study, it is concluded that corrosion inhibitor
blends from EGE and halide ions inhibits mild steel corrosion in 3.5%
HCl. The formulation with PTI is the most efficient with inhibition effi-
ciencies of 94.9% and 57.6% at 30 °C and 90 °C respectively. Addition of
PTI and AMC optimizes the effectiveness of EGE at high temperatures.
The inhibitors inhibit mild steel corrosion by physical spontaneous ad-
sorption with the release of heat. The formulations could be applied as
effective alternative anti-corrosive additives for well acidizing and stim-
ulation fluids.
Acknowledgements
The authors gladly acknowledge the financial support provided by
World Bank Robert S. McNamara Fellowship Program 2015 to carry
out this research abroad. The Materials Physics and Chemistry Research
Laboratory of China University of Petroleum, Qingdao and members of
the research group are also acknowledged for providing the facilities
and assistance for this research. We also appreciate the assistance of
African Centre of Excellence in Oilfield Chemicals Research, Institute
of Petroleum Studies, University of Port Harcourt, Nigeria and Ubong
Jerome Etim of State Key Laboratory of Heavy Oil Processing, UPC,
Qingdao.
References
[1] K.K. Anupama, K. Ramya, K.M. Shainy, A. Joseph, Adsorption and electrochemical
studies of Pimenta dioica leaf extracts as corrosion inhibitor for mild steel in hydro-
chloric acid, Mater. Chem. Phys. 167 (2015) 28–41.
[2] N. El Hamdani, R. Fdil, M. Tourabi, C. Jama, F. Bentiss, Alkaloids extract of Retama
monosperma (L.) Boiss. seeds used as novel eco-friendly inhibitor for carbon steel
corrosion in 1 M HCl solution: Electrochemical and surface studies, Appl. Surf. Sci.
357 (2015) 1294–1305.
[3] M. Shabani-Nooshabadi, M.-S. Ghandchi, Introducing the Santolina
chamaecyparissus Extract as a Suitable Green Inhibitor for 304 Stainless Steel Corro-
sion in Strong Acidic Medium, Metall. Mater. Trans. A 46 (11) (2015) 5139–5148.
[4] M. Shabani-Nooshabadi, M.S. Ghandchi, Santolina chamaecyparissus extract as a
natural source inhibitor for 304 stainless steel corrosion in 3.5% NaCl, J. Ind. Eng.
Chem. 31 (2015) 231–237.
[5] M. Bozorg, T.S. Farahani, J. Neshati, Z. Chaghazardi, G.M. Ziarani, Myrtus Communis
as Green Inhibitor of Copper Corrosion in Sulfuric Acid, Ind. Eng. Chem. Res. 53 (11)
(2014) 4295–4303.
[6] Q. Hu, Y. Qiu, G. Zhang, X. Guo, Capsella bursa-pastoris extract as an eco-friendly in-
hibitor on the corrosion of Q235 carbon steels in 1mol· L− 1 hydrochloric acid, Chin.
J. Chem. Eng. 23 (8) (2015) 1408–1415.
[7] M. Sangeetha, S. Rajendran, T.S. Muthumegala, A. Krishnaveni, Green corrosion in-
hibitors–An overview, Zastita Materijala 52 (1) (2011) 3–19.
[8] L. Bai, L. Feng, H. Wang, Y. Lu, W. Lei, F. Bai, Comparison of the synergistic effect of
counterions on the inhibition of mild steel corrosion in acid solution: electrochem-
ical, gravimetric and thermodynamic studies, RSC Adv. 5 (6) (2015) 4716–4726.
Please cite this article as: E. Ituen, et al., Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild
steel, Chin. J. Chem. Eng. (2016), http://dx.doi.org/10.1016/j.cjche.2016.04.028
View publication stats
[9] S. Shen, C. Zhu, X. Guo, C. Li, Y. Wen, H. Yang, The synergistic mechanism of phytic
acid monolayers and iodide ions for inhibition of copper corrosion in acidic media,
RSC Adv. 4 (21) (2014) 10597–10606.
[10] Z. Wu, Z. Fang, L. Qiu, W. Zhang, X. Jiang, Synergistic inhibition effect of cationic
gemini surfactant and chloride ion on the corrosion of steel in 0.5 M H2SO4 solution,
Chem. Eng. Commun. 200 (1) (2013) 50–64.
[11] M. Finšgar, J. Jackson, Application of corrosion inhibitors for steels in acidic media for
the oil and gas industry: A review, Corros. Sci. 86 (2014) 17–41.
[12] M. Mobin, V. Rizvi, Inhibitory effect of xanthan gum and synergistic surfactant addi-
tives for mild steel corrosion in 1 M HCl, Carbohydr. Polym. 136 (2016) 384–393.
[13] X. Pang, X. Ran, F. Kuang, J. Xie, B. Hou, Inhibiting effect of ciprofloxacin, norfloxacin
and ofloxacin on corrosion of mild steel in hydrochloric acid, Chin. J. Chem. Eng. 18
(2) (2010) 337–345.
[14] K. Krishnaveni, K. Sampath, J. Ravichandran, C. Jayabalakrishnan, N-methyl-2-(2-
nitrobenzylidene) hydrazine carbothioamide—A new corrosion inhibitor for mild
steel in 1mol• L− 1 hydrochloric acid, Chin. J. Chem. Eng. 23 (11) (2015) 1916–1922.
[15] Y. Li, Y. Zhang, H. Zheng, J. Du, H. Zhang, J. Wu, H. Huang, Preliminary evaluation of
five elephant grass cultivars harvested at different time for sugar production, Chin. J.
Chem. Eng. 23 (7) (2015) 1188–1193.
[16] Z. Tessema, R.M.T. Baars, Chemical composition, in vitro dry matter digestibility and
ruminal degradation of Napier grass (Pennisetum purpureum (L.) Schumach.) mixed
with different levels of Sesbania sesban (L.) Merr, Anim. Feed Sci. Technol. 117 (1–2)
(2004) 29–41.
[17] N.P. Akah, J.C. Onweluzo, Evaluation of Water-soluble Vitamins and Optimum
Cooking Time of Fresh Edible Portions of Elephant Grass (Pennisetum purpureum
L. Schumach) Shoot, Niger. Food J. 32 (2) (2014) 120–127.
[18] J.C. del Río, P. Prinsen, J. Rencoret, L. Nieto, J. Jiménez-Barbero, J. Ralph, A.T. Martínez,
A. Gutiérrez, Structural Characterization of the Lignin in the Cortex and Pith of Ele-
phant Grass (Pennisetum purpureum) Stems, J. Agric. Food Chem. 60 (14) (2012)
3619–3634.
[19] P. Prinsen, A. Gutiérrez, J.C. del Río, Lipophilic Extractives from the Cortex and Pith of
Elephant Grass (Pennisetum purpureum Schumach.) Stems, J. Agric. Food Chem. 60
(25) (2012) 6408–6417.
[20] M. Finšgar, 2-Mercaptobenzimidazole as a copper corrosion inhibitor: Part II. Sur-
face analysis using X-ray photoelectron spectroscopy, Corros. Sci. 2013 (72)
(2013) 90–98.
[21] S.S. Handa, S.P.S. Khanuja, G. Longo, D.D. Rakesh, Extraction technologies for medic-
inal and aromatic plants, Earth Environ. Mar. Sci. Technol. (2008).
[22] M.H. Hussin, A.A. Rahim, M. Nasir, M. Ibrahim, N. Brosse, The capability of
ultrafiltrated alkaline and organosolv oil palm (Elaeis guineensis) fronds lignin as
green corrosion inhibitor for mild steel in 0.5 M HCl solution, Measurement 78
(2016) 90–103.
[23] V. Rajeswari, D. Kesavan, M. Gopiraman, P. Viswanathamurthi, K. Poonkuzhali, T.
Palvannan, Corrosion inhibition of Eleusine aegyptiaca and Croton rottleri leaf ex-
tracts on cast iron surface in 1 M HCl medium, Appl. Surf. Sci. 314 (2014) 537–545.
[24] C.B. Kumar, K.N. Mohana, Phytochemical screening and corrosion inhibitive behav-
ior of Pterolobium hexapetalum and Celosia argentea plant extracts on mild steel in
industrial water medium, Egypt. J. Pet. 23 (2) (2014) 201–211.
[25] L. Li, W. Xu, J. Lei, J. Wang, J. He, N. Li, F. Pan, Experimental and theoretical investiga-
tions of Michelia alba leaves extract as a green highly-effective corrosion inhibitor
for different steel materials in acidic solution, RSC Adv. 5 (114) (2015)
93724–93732.
[26] H.Z. Alkhathlan, M. Khan, M.M.S. Abdullah, A.M. AlMayouf, A.Y. Hadj-Ahmed, A.Z.
Al-Othman, A.A. Mousa, Anticorrosive assay-guided isolation of active
phytoconstituents from Anthemis pseudocotula extracts and a detailed study of
their effects on the corrosion of mild steel in acidic media, RSC Adv. 5 (67) (2015)
54283–54292.
[27] J. Zhang, et al., Investigation of Diospyros Kaki Lf husk extracts as corrosion inhibi-
tors and bactericide in oil field, Chem. Cent. J. 7 (1) (2013) 109.
[28] A. Yurt, S. Ulutas, H. Dal, Electrochemical and theoretical investigation on the corro-
sion of aluminium in acidic solution containing some Schiff bases, Appl. Surf. Sci. 253
(2) (2006) 919–925.
[29] M. Behpour, S.M. Ghoreishi, N. Mohammadi, N. Soltani, M. Salavati-Niasaria, Inves-
tigation of some Schiff base compounds containing disulfide bond as HCl corrosion
inhibitors for mild steel, Corros. Sci. 52 (12) (2010) 4046–4057.
[30] H. Zarrok, A. Zarrouk, B. Hammouti, R. Salghi, C. Jama, F. Bentiss, Corrosion control of
carbon steel in phosphoric acid by purpald–Weight loss, electrochemical and XPS
studies, Corros. Sci. 64 (2012) 243–252.
[31] S.M. Shaban, I. Aiad, M.M. El-Sukkary, E.A. Soliman, M.Y. El-Awady, Inhibition of
mild steel corrosion in acidic medium by vanillin cationic surfactants, J. Mol. Liq.
203 (2015) 20–28.
[32] I. Obot, N. Obi-Egbedi, Anti-corrosive properties of xanthone on mild steel corrosion
in sulphuric acid: Experimental and theoretical investigations, Curr. Appl. Phys. 11
(3) (2011) 382–392.
[33] S.A. Umoren, M.M. Solomon, Effect of halide ions on the corrosion inhibition effi-
ciency of different organic species – A review, J. Ind. Eng. Chem. 21 (2015) 81–100.
[34] S.A. Umoren, I.B. Obot, Synergistic inhibition between 1-octadecanethiol and iodide
ions on X60 pipeline steel for corrosion protection, J. Adhes. Sci. Technol. 28 (20)
(2014) 2054–2068.
[35] T. Salmi, Chapter Four - Chemical Reaction Engineering of Biomass Conversion, in:
M.D. Yu (Ed.) Adv. Chem. Eng.Academic Press 2013, pp. 195–260.