3986 Ind. Eng. Chem. Res.

2010, 49, 3986–3991

Cigarette Butts and Their Application in Corrosion Inhibition for N80 Steel at 90
°C in a Hydrochloric Acid Solution
Jun Zhao,*,† Ningsheng Zhang,†,§ Chengtun Qu,§ Xinmin Wu,§ Juantao Zhang,‡ and Xiang Zhang†
School of Energy and Power Engineering, Xi’an Jiaotong UniVersity, 710049, Xi’an, PR China, Tubular Goods
Research Center of CNPC, 710065, Xi’an, PR China, and Xi’an Shiyou UniVersity, 710065, Xi’an, PR China

Cigarette butts, one of the most ubiquitous forms of garbage in the world, need to be recycled because their
toxicity can kill saltwater and freshwater fish. In this study, the cigarette butts are applied as corrosion inhibitors
for N80 steel at 90 °C in hydrochloric acid. Weight loss and electrochemical techniques are used to evaluate
the corrosion inhibitive effect of cigarette butt water extracts. Results show that the inhibition efficiencies
arrive at 94.6% and 91.7% in 10% and 15% (wt %) HCl solution, respectively, by adding 5% (wt %) inhibitor.
In 20% HCl solution, they show a maximum inhibition efficiency of 88.4% by adding 10% inhibitor.

1. Introduction The apparatuses used in this study are as follows: The IR

Cigarette butts, one of the most ubiquitous forms of garbage
in the world, have been found to be toxic to saltwater and
freshwater fish.1-3 Novotny4 indicates that the toxic chemical
substances in one cigarette butt can kill half of the fish in 1 L
of water every 96 h. Without tobacco, it takes about 4 smoked
filters to do the same job.
Still, humans are inadvertently carpeting the planet in cigarette
butts. That is billions of cigarettes flicked, one at a time, on
our sidewalks, beaches, nature trails, gardens, and other public
places every single day. According to one estimate, some 4.5
trillion cigarette butts from spent smokes make their way into
the environment every year. Some states and municipalities have
begun moving toward legislation that would ban smoking on
beaches, where butts are commonly discarded.1-3 Judging from
the present condition, such measures have had little effect.
One of effective ways to reduce pollution is introduced by
recycling the cigarette butts. However, there are few reports on
reusing cigarette butts.5-7 In this study, the cigarette butts are
applied as corrosion inhibitor for N80 steel at 90 °C in
hydrochloric acid. The chemical compositions of the cigarette
butt water extracts are detected by LC (liquid chromatography)/
MS (mass spectrometry) and an IR (infrared) reaction analysis
system. Weight loss and electrochemical techniques (such as
potentiodynamic polarization and impedance measurements) are
used to the evaluate corrosion inhibitive effect of cigarette butt
water extracts on N80 steel at 90 °C in a hydrochloric acid
solution. In this investigation, the influences of different
concentrations of hydrochloric acid and cigarette butt water
extracts on corrosion inhibition are taken into account.
2. Experimental Section
The tested material is N80 oil tube steel discs with the
chemical composition of C 0.24, Mn 1.19, Si 0.22, S 0.004, P
0.013, Cr 0.036, Mo 0.021, Ni 0.028, V 0.017, Ti 0.011, Cu
0.019, Nb 0.006, and Fe the rest. Before the corrosion test, the
surfaces of the sample are mechanically polished by grit
sandpaper progressively up to 1200# (# stand for the mesh
number), rinsed with alcohol and then stove-dried.
* To whom correspondence should be addressed. E-mail:
zhaojun_286@163.com. Tel. and Fax: +86 29 88382693.
†
Xi’an Jiaotong University.
§
Xi’an Shiyou University.
‡
Tubular Goods Research Center of CNPC.
10.1021/ie100168s  2010 American Chemical Society
Published on Web 03/26/2010
reaction analysis system is made by Mettler-Toledo Co.,
Switzerland. The chemical compositions of the cigarette butt
water extracts are detected by liquid chromatography (Agilent
2100)/mass spectrometry (Agilent 6410) with the following
determination conditions: C18 column (2.1 mm × 50 mm, 3.5
µm, Agilent), column temperature -30 °C, mobile phase
methanol + 0.1% formic acid, flow rate 0.4 mL/min, sampling
amount 2 µL, ion source model ESI+, atomizing gas pressure
15 psi, atomizing gas flow rate 6 L/h, atomizing gas temperature
350 °C, capillary voltage 150 V, scanning model full scanning
model, direct sampling after filter by 0.45 µm microporous
membrane. The electrochemical techniques such as potentio-
dynamic polarization and impedance are investigated by a
potentiostat (M273A, Princeton instrument Co., USA) and lock-
in amplifier (M5210, Princeton instrument Co., USA).
The cigarette butts used in this study all came from the road
or the garbage. Most of them are Virginian-type cigarettes.
3. Results and Discussion
3.1. IR and LC/MS. The aging process is synchronously
monitored by an IR reaction analysis system. Air is used as the
background, and the spectrum is collected every 6 h. Figure 1
is the IR plots of the 5 cigarette butts in 100 mL distilled water.
From Figure 1, the absorbance in 1630-1690 cm-1 region may
be the CdO stretching vibration, the absorbance in the
2700-3700 cm-1 may be the NsH or OsH bond stretching
vibration, and the absorbance intensity in these two regions is
increased with the aging time elapsing until 24 h. These indicate
that the compounds in the aging solution may contain CdO,
NsH, or OsH groups. Table 1 is the effect of the aging time
on the inhibition efficiency of the aging solution. It can be seen
from Table 1 that the inhibition efficiency arrives at the highest
over aging 24 h. So, the best aging time is 24 h and the method
and procedure for making corrosion inhibitor with cigarette butt
water extracts is as follows: 5 cigarette butts were added into
100 mL distilled water and aged for 24 h. The aged solution
was then used for corrosion inhibition studies using weight loss
and electrochemical methods.
The aged solution has been also determined by the LC/MS.
Figure 2 is representative LC graph of the aged solution, i.e.,
cigarette butts water extracts. Table 2 is the LC/MS results of
the cigarette butts water extracts. In the rough, nine compounds
with the heteroatom (N, O) and π-bonds in favor of metal

Figure 1. IR plots of the aging process of the 5 cigarette butts in 100 mL distilled water.
Table 1. Effect of the Aging Time on Inhibition Efficiencya
aging time 6h 12 h
inhibition efficiency 63.7% 82.9%
a
The inhibition efficiency was detected by using the weight loss method on N80 steel in a 10% HCl solution with a 5% (wt %) aging solution.
Figure 2. Representative LC graph of the cigarette butts water extracts.
corrosion inhibition are detected in the LC/MS results. There
may also be others we have not detected.
3.2. Weight Loss Studies. Weight loss study was carried
out at 90 °C for 4 h time duration in HCl solution. The size of
N80 steel specimens used in weight loss study is 50 × 20 × 4
mm. The inhibition efficiency (IE) is determined by following
equation:9-11
W0 - Wi
IE(%) ) × 100
W0
where W0 and Wi are the weight loss values in absence and in
presence of inhibitor. The calculated results are shown in Table
3. From Table 3, the inhibition efficiency in different concentra-
tion of HCl solutions enhances with increase in amount of the
inhibitor until reaches the highest value. In 10% and 15% (wt
%) HCl solution, the optimum amount of the inhibitor is 5%
(wt %), and in 20% HCl solution, the optimum amount is 10%
(wt %).
3.2. Electrochemical Studies. For polarization and electro-
chemical impedance studies, the specimen is exposed a geo-
metrical surface area of 0.785 cm2 to electrolyte. The aggressive
solutions (10%, 15%, 20% HCl, wt %) are prepared by dilution
of analytical grade 37% HCl. The concentration range of the
inhibitor is 3%, 5%, 10%, 15% (wt %), in 10%, 15%, 20%
HCl, respectively. The platinum electrode and saturated calomel
electrode (SCE) are used as the counter electrode and reference
electrode, respectively. Polarization is performed at (150 mV
from the corrosion potential with a scan rate of 2 mV/s. The
Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010 3987
18 h 24 h 30 h 36 h
93.8% 94.6% 94.6% 94.6%
impedance measurements are carried out at the open circuit
potential (Eocp) in the frequency range from 100 kHz to 0.01
Hz with a signal amplitude perturbation of 5 mV by using a
computer controlled potentiostat. All experiments are performed
in atmospheric conditions without stirring, and the thermostat
is used to keep temperature at 90 °C.
3.2.1. Potentiodynamic Polarization Measurements. Figure
3 shows typical Tafel curves for N80 steel in 10% HCl without
and with different concentrations of inhibitor. Figure 4 is the
(1) polarization curves for N80 steel in different concentration of
HCl without and with 5% inhibitor. The values of associated
electrochemical parameters, i.e., corrosion potential (Ecorr),
corrosion current density (Icorr), anode Tafel slopes (ba), cathodic
Tafel slopes (bc), and percentage inhibition efficiency (IE (%))
are calculated from polarization curves and, then, listed in Table
3. The inhibition efficiency IE (%) is calculated from polariza-
tion measurements according to the relation given below:12-16
( )
Icorr - Icorr
′
IE(%) ) × 100 (2)
Icorr
′ are uninhibited and inhibited corrosion
where Icorr and Icorr
current densities, respectively. They are determined by extrapo-
lating Tafel lines of the respective corrosion potentials.
As it can be seen from Figure 3, obvious passivation regions
occur in the anodic branches when the addition of inhibitor is
equal or greater than 5%. And the anodic branches are all shifted
to positive direction in the presence of inhibitor. Contrasts to
anodic branches, the cathodic branches are shifted to passive
3988 Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010
Table 2. LC/MS Results of the Cigarette Butt Water Extracts8
direction in the presence of inhibitor. These results demonstrate
that the inhibitor of cigarette butts water extracts mainly acts
as a mixed type (cathodic/anodic) inhibitor, i.e., the addition of
the inhibitor retards the rate of metal dissolution and hydrogen
evolution on N80 surface. As shown in Figure 4, the corrosion
potential (Ecorr) of N80 steel at different concentrations of HCl
without inhibitor has not changed obviously. The anodic branch
appears in passivation region in 10% HCl with 5% inhibitor,
but there’s no passivation in 15% and 20% HCl with 5%
inhibitor. It indicates that there may be some oxidants in the
inhibitor.17-19 When the concentration of HCl is not very high,
the oxidants oxidize metal forming the insoluble salt covered
on the metal, thus appearing in passivation region. In contrast,
the oxygenizement grows weaker and cannot form the passi-
vation region.
At first, it is clear that the corrosion current (Icorr) values
decrease and the IE values increase with the addition of inhibitor
from the Table 3, and then, they proceed in the reverse direction
with increase in concentration of inhibitor. The anodic Tafel
slopes (ba) and cathodic Tafel slopes (-bc) decrease in the
presence of inhibitor. The changes of ba and bc also suggest
that the inhibitor mainly acts as mixed type (cathodic/anodic)
inhibitor. The inhibition effect of the inhibitor in 10% HCl is
the best, the second is in 15% HCl, and the last is in 20% HCl.
These are in agreement with weight loss results.
3.2.2. Electrochemical Impedance Spectroscopy. The ef-
fects of the inhibitor concentration on the impedance behavior
of N80 steel in different quantity of HCl solution have been
studied. The representative Nyquist plots are presented in
Figures 5 and 6. Electrochemical Impedance Spectroscopy (EIS)
 Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010 3989
Table 3. Potentiodynamic Polarization Parameters and Weight Loss Results of N80 Steel in Different HCl Solution with Various
Concentrations of Inhibitors
method
polarization weight loss
aggressive inhibitor
solutions concentration -Ecorr -bc ba Icorr Wcorr
(wt %) (wt %) vs SCE (mV) (mV dec-1) (mV dec-1) (mA cm-2) IE (%) (mg cm-2 h-1) IE (%)
10% HCl blank 408 169.88 163.68 12.43 18.26
3% 426 138.48 127.21 3.39 72.7 4.10 77.5
5% 488 137.59 125.14 0.46 96.3 0.99 94.6
10% 469 140.85 120.27 1.21 90.3 2.83 84.5
15% 497 141.72 124.33 0.95 92.4 2.17 88.1
15% HCl blank 411 183.46 118.68 20.40 23.63
3% 424 176.21 111.34 7.78 61.9 8.15 65.5
5% 441 175.85 105.47 1.73 91.5 1.95 91.7
10% 461 177.36 113.74 5.37 73.7 4.10 82.6
15% 476 176.63 110.58 3.65 82.1 3.29 86.1
20% HCl blank 409 224.50 163.39 43.10 48.83
3% 416 217.34 161.63 17.75 58.8 21.84 55.3
5% 424 209.85 155.37 11.13 74.2 11.78 75.9
10% 457 206.18 150.82 5.83 86.5 5.65 88.4
15% 473 209.46 158.79 9.81 77.2 8.71 82.2

spectra are analyzed by using the equivalent circuit in Figure
7, and the representative simulated plots of N80 steel in 10%
HCl solution with 3% inhibitor is shown in Figure 8. In the
equivalent circuit model, Rs represents solution resistance
between the working and reference electrodes, CPE, a power-
law-dependent capacity term known as the constant phase
element may be brought by surface roughness,20,21 Rt represents
charge transfer resistance and corresponds to the resistance
between the metal and outer Helmholtz plane,22-24 L is inductive

Figure 3. Tafel curves for N80 steel in 10% HCl with and without different Figure 5. Nyquist plots of the inhibitor concentration effects on the
concentrations of inhibitor at 90 °C. impedance behavior of N80 steel in 10% HCl solution at 90 °C.

Figure 4. Polarization curves for N80 steel in different concentration of Figure 6. Nyquist plots for N80 steel in different concentration of HCl
HCl without and with 5% inhibitor at 90 °C. without and with 5% inhibitor at 90 °C.
3990 Ind. Eng. Chem. Res., Vol. 49, No. 8, 2010

1 1
ZCPE ) × (3)
Y0 (jω)n

where Y0 is the magnitude of the CPE, n is the CPE exponent

(phase shift), ω is the angular frequency (ω ) 2πf, where f is
the AC frequency), and j here is the imaginary unit. The
correction of capacity to its real values is calculated from the
equation as follows:12-19
Figure 7. Equivalent circuit model for the studied inhibitor.
Cdl ) Y0(ωmax))n-1 (4)

where ωmax is the frequency at which the imaginary part of

impedance (-Zi) has a maximum. According to the equivalent
circuit model in Figure 7, the impedances of the electrodes for
all cases are given by

Z(ω) ) Rs + 〈{[Rt-1 + (RL + jωL)-1]-1 + (RC-1 +

jωC)-1}-1 + jωCdl〉-1 (5)

The inhibition efficiency IE (%) is calculated from impedance

measurements according to the relation given below:25-30

Figure 8. Representative simulated plots of N80 steel in 10% HCl solution

with 3% inhibitor.
25,26
reactance related to active dissolution of film, RL is the
inductive resistance, RC represents the resistance of corrosion
film, and C stands for constant phase element of capacity caused
by corrosion product film. The fitting parameters of impedance
data obtained by using the equivalent circuit model in Figure 7
are listed in Table 4.
As shown in Figure 5, the spectra of N80 steel exhibits similar
behavior including a semicircular shape of dispersing capacitive
loop in high frequency region, a semicircular shape of inductive
loop in low frequency region, and a little capacitive reactance
arc in the low frequency region. At first, the diameter of
depressed capacitive semicircle increases with the addition of
inhibitor and then decreases when inhibitor is over 5%, this
trend indicates that the corrosion attack has been reduced to
the minimum at the inhibitor concentration of 5% in 10% HCl
solution. From Figure 6, the diameter of the depressed capacitive
semicircle decreases with the increase of HCl which indicates
the increased corrosion attack. The impedance of CPE is given
as follows:19-21
IE(%) ) (
1/Rp - 1/Rp′
1/Rp
× 100 ) (6)
Rp ) Z(ω ) 0) (7)
where Rp and Rp′ are uninhibited and inhibited polarization
resistances, respectively. They are calculated by eqs 7.
In Table 4, the Rp value decreases steadily with the increase
of the amounts of HCl which suggests the addition of HCl can
enhance the corrosion attack on the electrodes. At the same time,
the Rp shows maximum value when 5% inhibitor is added in
10% and 15% HCl solution, and 10% inhibitor is added in 20%
HCl solution. The result indicates that inhibition efficiencies
are related to the concentration of cigarette butt water extracts.
From the above weight loss and electrochemical studies,
cigarette butt water extracts may establish its inhibition action
via the adsorption onto the metal surface. The adsorption of
the inhibitor could be occurred due to the formation of oxidation
film or the electrostatic interactions. The oxidants in inhibitor
may oxidize the iron atoms forming the insoluble salt (oxidation
film) covered on the iron surface. The lonely electron pairs
present on the N and O atoms of the heterocyclic compounds
in the inhibitor may also adsorb through the electrostatic
interactions between the acid solution and the metal surface.

Table 4. EIS Spectra Parameters of N80 Steel in Different HCl Solutions with Various Concentrations of Inhibitors
impedance
aggressive inhibitor
solutions concentration QY0 Cdl Rt RL L RC C RP
(wt %) (wt %) Rs(Ω cm2) (S · sn cm-2) n (µF cm-2) (Ω cm2) (Ω cm2) (µH cm2) (Ω cm2) (µF cm-2) (Ω cm2) IE (%)
-3
10% HCl blank 0.012 1.20 × 10 0.80 393.50 1.27 10.08 722.13 4.98 271.16 6.12
3% 0.015 4.70 × 10-4 0.72 66.09 5.38 0.075 1.24 12.65 12.17 12.73 57.9
5% 0.017 2.31 × 10-4 0.72 36.74 1.79 0.010 0.44 123.09 1.20 123.12 95.0
10% 0.021 5.40 × 10-4 0.65 49.83 4.73 0.056 1.07 40.73 4.88 40.79 85.0
15% 0.026 3.36 × 10-4 0.67 46.32 2.91 0.037 0.98 70.86 3.79 70.91 91.4
15% HCl blank 0.0017 5.05 × 10-3 0.65 620.6 2.48 2.43 846.01 2.29 582.21 3.52
3% 0.0033 4.59 × 10-4 0.75 81.46 3.41 1.87 3.02 9.86 66.91 11.08 68.2
5% 0.0065 3.72 × 10-4 0.73 51.66 1.94 2.25 0.97 45.59 6.03 46.64 92.5
10% 0.011 6.74 × 10-4 0.65 71.30 4.53 1.12 2.36 18.86 9.75 19.77 82.2
15% 0.015 5.93 × 10-4 0.66 66.41 5.38 1.05 1.04 30.81 8.37 31.27 88.7
20% HCl blank 0.0010 2.02 × 10-3 0.67 863.62 1.11 6.96 952.93 1.01 770.93 1.96
3% 0.0021 2.55 × 10-4 0.81 89.66 1.38 0.023 4.41 6.51 68.48 6.54 70.1
5% 0.0054 4.61 × 10-4 0.74 76.52 2.24 0.014 3.82 8.84 8.76 8.88 77.9
10% 0.014 5.83 × 10-4 0.69 60.32 1.58 3.62 1.01 16.02 7.17 17.12 88.6
15% 0.026 3.97 × 10-4 0.74 67.33 1.78 2.39 3.12 10.34 9.84 11.38 82.8

Thus, the metal surface can be protected and the iron atom’s
further dissolution can be prevented.23-30
4. Conclusion
Cigarette butts are extracted as inhibitor for the corrosion of
N80 steel in HCl solutions at 90 °C. All studies on cigarette
butt water extracts show good inhibition properties. The
inhibition efficiency of cigarette butt water extracts from EIS,
polarization curves, and weight loss has the same trend.
Inhibition efficiencies are related to the concentration of cigarette
butt water extracts. It shows maximum inhibition efficiency of
94.6% and 91.7% in 10% and 15% HCl solution, respectively,
with 5% inhibitor. In a 20% HCl solution, it shows maximum
inhibition efficiency 88.4% by adding 10% inhibitor. The
corrosion attack increase with increase the concentration of the
HCl. Potentiodynamic polarization shows that it is a mixed type
of inhibitor.
Acknowledgment
The authors want to thank the Key Laboratory for Corrosion
and Protection in Tabular Goods Research Center of China
National Petroleum Corporation for supports to this work.
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ReceiVed for reView January 25, 2010
ReVised manuscript receiVed March 9, 2010
Accepted March 14, 2010
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