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Innovations in Corrosion and Materials Science, 2018, 8, 60-66
RESEARCH ARTICLE
ISSN: 2352-0949
eISSN: 2352-0957

Corrosion Inhibition of Copper in Sea Water Using Derivatives of


Tetrazoles and Thiosemicarbazide

Abdul-Khalek Younes1, Ibrahim Ghayad2,*, Emel B. Ömer3 and Fatma Kandemirli1


Innovations in Corrosion and Materials Science

1
Department of Material Science, Kastamonu University, Kastamonu, Turkey; 2Central Metallurgical Research &
Development Institute, Helwan, Egypt and 3Department of Chemistry, Halisdmir University, Nigde, Turkey

Abstract: Background: The present paper investigates the corrosion inhibition of copper using six cor-
rosion inhibitors namely: 4-phenyl thiosemicarbazide (PTSC), Salicylaldehydethiosemicarbazone
(STSC). 5-Mercapto-1-methyle tetrazole (MMT), 5-(3-Pyridyl)-1H-tetrazole (PyTA), 5-phenyl-1-H-
ARTICLE HISTORY tetrazole (PTA) and 5-Amino-tetrazole monohydrate (ATA).
Received: April 27, 2018
Revised: August 08, 2018
Method: Copper samples were tested using potentiodynamic polarization technique in the absence and
Accepted: August 29, 2018 in the presence of corrosion inhibitors.
DOI:
10.2174/2352094908666180830123952
Results: Results show that tetrazole derivatives show high inhibition efficiencies (90%) in comparison
to thiosemicarbazide derivatives (<80%). The highest inhibition efficiency of 92.9% was shown by
ATAH at 2000 ppm. The order of inhibition efficiencies of the tested compounds was as follows:
PTAATA >PyTA> MMT > STC > PTSC.
Keywords: Corrosion inhibition, copper, sea water, thiosemicarbazides, tetrazoles, inhibition efficiency.

1. INTRODUCTION The corrosion inhibition of Cu using1-phenyl-5-


mercapto-1,2,3,4-tetrazole (PMT) in 0.1M HNO3 has been
Copper and its alloys possess excellent thermal, electrical investigated [10]. PMT behaves as a mixed type inhibitor
and mechanical properties [1, 2]. These properties make them and is chemisorbed on the copper surface and follows Lang-
suitable choices for construction materials including tubes,
muir isotherm. Other papers [11-13] investigated 5-(3-
pumps, valves, fittings, interconnects, circuit boards,…etc. Aminophenyl) tetrazole 5-Substituted,(E)-3-phenyl-2-(1H-
However, copper alloys suffer from some forms of corrosion tetrazole-5-yl)acrylonitrile (PTA), (E)-3-(4-nitrophenyl)-2-
which limit their performance [3-6].
(1Htetrazole-5-yl)acrylonitrile (NTA), and (E)-3-(4-
Tetrazoles are a family of organic heterocyclic com- hydroxyphenyl)-2-(1H-tetrazole-5-yl)acrylonitrile (HTA) for
pounds composed of a 5-member ring having four nitrogen the corrosion inhibition of copper and steel in seawater, hy-
and one carbon atoms in addition to hydrogen atoms [7]. drochloric and sulfuric acid environments. The relation be-
Substitution of H atom attached to the carbon or the nitrogen tween the adsorption bonding and corrosion inhibition of
atoms of the tetrazole ring with other function groups like copper was also addressed [11-13].
NH2, CH3, SH, phenyl result in the synthesis of a huge num-
Semicarbazide, known as carbohydrazide, is the chemical
ber of tetrazoles. Tetrazoles possess a high tendency to ad-
compound with the formula OC(NH2)(N2H3). It is a water-
sorb on copper due to lone pairs of electrons on the nitrogen
atoms of the tetrazole ring. The coordination of these lone soluble white solid. It is a derivative of urea prepared by
pairs of electrons with the Cu(I) ions, produced from copper treating urea with hydrazine [14]:
oxidation, results in the formation of a protective complex. OC(NH2)2 + N2 H4  OC (NH2)(N2 H3) + NH3 (1)
The effect of 2-mercaptobenzothiazole (MBT) and te-
trazole (TTA) on the corrosion inhibition of copper in the A thiosemicarbazide is an analog to semicarbazide with
ethanol solution and 0.1 M NaOH was investigated [8, 9]. the sulfur atom in place of oxygen atom. Semicarbazones are
0.001 M of MBT lead to reduction of current density 4 derived by the condensation reaction between a ketone (or
times. The inhibition efficiency is strongly dependent on the aldehyde) and a semicarbazide. Thiosemicarbazide and its
structure and chemical properties of the species formed un- derivatives are used as corrosion inhibitors for different me-
der the specific experimental conditions. tallic substrates [15-27]. Thiosemicarbazide and thiocarbo-
hydrazide functionalized chitosan were evaluated as eco-
*
friendly corrosion inhibitors for carbon steel in hydrochloric
Address correspondence to this author at the Central Metallurgical
Research & Development Institute, Helwan, Egypt;
acid solution [15]. Al-Bonayan [16] used thiosemicarbazide
Tel: 955884842; E-mail: ighayad@yahoo.com and 4-phenyl thiosemicarbazide as corrosion inhibitors of

2352-0957/18 $58.00+.00 © 2018 Bentham Science Publishers


Corrosion Inhibition of Copper in Sea Water Using Derivatives Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 61

carbon steel in 2 N H3PO4 solutions. The inhibition efficien- fixed in the corrosion cell so that an area of 0.785 cm2 was
cy increases with increase in inhibitors concentrations and exposed to the testing solution. Specimens were polished
decreases with rising temperature. The influence of thio- using SiC papers successively up to 2400 grits to acquire a
semicarbazide, phenylthiosemicarbazide on the corrosion mirror-like finish. After polishing, specimens were thorough-
rate of steel in 2MHCl was investigated [17]. Results showed ly washed with distilled water and dried in air.
that all the compounds investigated acted as cathodic-type
Potentiodynamic polarization curves were measured on
inhibitors. The corrosion inhibition efficiency of synthesized
the Cu electrodes using a conventional three-electrode cell
2-(1-methyl-4-((E)-(2-methylbenzylidene)amino)-2-phenyl-
with an Ag/AgCl reference electrode and a Pt sheet counter
1H-pyrazol-3(2H)-ylidene)-hydrazineecarbothioamide (HCB) electrode. The potential was controlled using a computerized
on mild steel in 1.0 M HCl was investigated [18]. The results
potentiostat (AutoLab PG STAT 30). The potential was
showed that HCB inhibited mild steel corrosion in acidic
scanned from -0.3 V below the Ecorr towards 1 V above the
solution and inhibition efficiency increased with an increase
Ecorr at a scan rate of 1 mVs-1. Experiments were carried out
in the concentration of the inhibitor. The inhibition efficien-
in 0.6 mol L-1NaCl solution simulating sea water environ-
cy of 1,4-bis (2-nitrobenzylidene) thiosemicarbazide (BBTS)
ment. Corrosion parameters: corrosion current (Icorr), corro-
on the corrosion of mild steel in 1 mol/L HCl was investigat-
sion potential (Ecorr) and corrosion rate (CR) were deduced
ed [19]. The results showed that this compound had good
from the analysis of polarization curves using the AutoLab
inhibiting properties for mild steel corrosion in hydrochloric
software.
acid and BBTS was a mixed-type inhibitor. In the study of
Wazzan [20], thiosemicarbazide, aryl isothiocyanates, and 1- Six corrosion inhibitors namely: 4-phenyl thiosemicarba-
aryl-2,5-dithiohydrazodicarbonamides were investigated as zide, Salicylaldehydethiosemicarbazone. 5-Mercapto-1-methyle
corrosion inhibitors of copper in an aqueous chloride tetrazole, 5-(3-Pyridyl)-1H-tetrazole,5-phenyl-1-H-tetrazole
solution. (PTAH) and 5-Amino-tetrazole monohydrate (ATAH) from
Aldrich were investigated. The inhibitor solutions were dis-
It is obvious that literature mostly investigated the use of
solved in the least amount of dimethylformamide (DMF) or
thiosemicarbazides as corrosion inhibitors for mild steel with
sodium hydroxide. Measurements were performed at 20 ± 1oC
little work on copper. Mean whiletetrazoles were tested as
while the testing solution was open to air. The structural formu-
corrosion inhibitors of copper in acid media but not salt wa-
la and their molecular weight are shown in Table 1
ter. The present paper investigates and compares the corro-
sion inhibition of copper in sea water environment using
4. RESULTS AND DISCUSSION
some tetrazoles and thiosmicarbazide derivative.
Potentiodynamic polarization curves are used to illustrate
2. OBJECTIVES the corrosion behavior of the alloy under test and to show the
effect of the corrosion inhibitor, i.e. if the corrosion inhibitor
• Comparing the corrosion inhibition efficiencies of some
leads to the appearance of a passive region or not. Poten-
tetrazoles and thiosmicarbazide derivative.
tiodynamic polarization curves are used also to deduce cor-
• Corelating the inhibition efficieny to the inhibitor molec- rosion parameters: corrosion potential (Ecorr), corrosion cur-
ular structure and its functionality. rent (icorr) and corrosion rate (CR) in the presence of the cor-
rosion inhibitors compared to those obtained in the absence
3. METHOD of corrosion inhibitor and thus, determining the corrosion
inhibition efficiency. The corrosion inhibition efficiency of
Disc specimens were prepared from electrolytic copper
the corrosion inhibitor can be calculated using the following
(99.9%) having a diameter of 1.5 cm2. Disc specimens were
equation:

Table 1. Names and structural formula of tested inhibitors.

salicylaldehydethiosemicarbazone (MW =195.24) 5-(3-Pyridyl)-1H-tetrazole (MW =147.14)

4-phenylthiosemicarbazide (MW = 167.23) 5-phenyl-1-H-tetrazole (PTAH) (MW=146.15)

S
NH2
N N
H H

5-Mercapto-1-methyltetrazole (Mwt =116.14) 5-Amino-tetrazole.H2O (ATAH) (MW=103.08)


62 Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 Younes et al.

icorr(b) - icorr(inh) Figs. (2-6) present the Potentiodynamic polarization


Efficiency = ------------------------------ X 100 (2) curves of cu in 3.5% NaCl solution at 1mvs-1 and 20°C and
icorr(b) in presence of the investigated corrosion inhibitors: 4-
phenylthiosemicarbazide, 5-mercapto-1-methyltetrazole, 5-
where icorr(b), icorr(inh)represent corrosion current densities in (3-pyridyl)-1H-tetrazole, 5-amminotetrazolemonohydrate &
the absence and in the presence of the inhibitor, respectively. 5-phenyl-1H-tetrazole, respectively. The blank curve (in
absence of corrosion inhibitor) is included for comparison.
Table 2 presents the electrochemical parameters deduced
0.8 500 ppm (a) from these Potentiodynamic polarization curves.
1000 ppm
2000 ppm
4-phenylthiosemicarbazid inhibitor shows better behavior
0.6
Blank compared to the blank (Fig. 2) but the reduction in the cur-
0.4 rent density is not satisfactory. No inhibition is shown by the
Potential / V

inhibitor at all concentrations (Table 2). The corrosion poten-


0.2 tials were shifted markedly in the active direction in the
presence of the inhibitor compared to the blank. The shift in
0.0 Ecorr mostly related to the adsorbed species on the copper
surface.
-0.2
5-Mercapto-1-methyltetrazolecorrosion inhibitor reveals
-0.4 an appreciable reduction in the current density compared to
the current density obtained in the solution without the inhib-
10-8 10-7 10-6 10-5 10-4 10-3 10-2 itor (Fig. 3). Increasing the inhibitor concentration brings a
-2 mild decrease in the current density. Corrosion rate obtained
Current /Acm
is decreased from 0.097 to 0.05 mm/y upon increase of in-
0.8
hibitor concentration from 0.0043 to 0.0086 M. Further in-
1000 ppm-0.1 M NaCl (b) crease of inhibitor concentration up to 0.0172 M led to an
1000 ppm-0.4 M NaCl
0.6 1000 ppm-0.6 M NaCl
increase of the corrosion rate up to 0.066 mm/y. The corro-
sion inhibition efficiency reaches as high as 70% at 0.0086
0.4 M of the inhibitor. Corrosion potentials are more or less the
Potential / V

same as the blank.


0.2
Table 2. Corrosion parameters including corrosion current
0.0 (Icorr), corrosion potential (Ecorr) and corrosion rate
(CR) derived from potentiodynamic curves of copper
-0.2
in 0.6 M NaCl in the absence (blank) and in the
-0.4 presence of corrosion inhibitors.

-0.6 Inhibition
Inhibitor/
icorr ( A/cm2) Ecorr (V) CR (mm/y) Efficiency
10 -9
10 -8
10 -7
10 -6
10 -5
10
-4
10 -3
10-2
M
(%)
-2
Current /Acm
Blank 1.479E-5 -0.236 0.1716

Fig. (1). (a) Potentiodynamic polarization curves of Salicylaldehydethiosemicarbazone


salicylaldehydethiosemicarbazonecorrosion inhibitor in 3.5% NaCl
at 1 mVs-1 scan rate and 20oC. (b) represents the effect of NaCl 0.0026 6.46 x10-6 -0.196 0.075 56.32
concentration on the efficiency of the inhibitor. 0.0051 4.27x10-6 -0.236 0.050 71.13
Fig. (1a) shows potentiodynamic polarization curves of
0.0102 2.79x10-6 -0.188 0.032 81.14
Cu in presence of Salicylaldehydethiosemicarbazone inhibi-
tor. The inhibitor shows better behavior compared to the 4-phenyl thiosemicarbazide
blank as shown by the lower current density, however, the
reduction in the current density is not significant. On the 0.0030 1.85x10-5 -0.412 0.21 --
other hand, with increasing inhibitor concentration, current 0.0060 2.14x10 -5
-0.438 0.25 --
density slightly decreases. Fig. (1b) shows the effect of sodi-
-5
um chloride concentration on the potentiodynamic polariza- 0.0120 1.711x10 -0.446 0.198 --
tion curves of the copper electrode in the presence of 0.0051
5-Mercapto-1-methyltetrazole
ppm inhibitor. An obviously low current density is obtained
in 0.1 M NaCl indicating high corrosion resistance of copper. 0.0043 8.33x10-6 -0.272 0.097 43.68
The current density is also increased upon increasing of
NaCl concentration from 0.1 to 0.4 then 0.6 M NaCl. The 0.0086 4.36x10-6 -0.226 0.050 70.52
tested inhibitors show Ecorrvalues comparable to that shown 0.0172 5.71x10-6 -0.262 0.066 61.39
by the blank.
Table (2) contd….
Corrosion Inhibition of Copper in Sea Water Using Derivatives Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 63

5-(3-Pyridyl-1H-tetrazole
5-(3-Pyridyl)-1H-tetrazole corrosion inhibitor shows bet-
ter behavior compared to the blank (Fig. 4), however, the
0.0034 1.28x10-6 -0.233 0.015 91.34 reduction in the current density is not much appreciable.
Concentrations of 0.0068&0.0136M show higher current
0.0068 2.99x10-6 -0.191 0.035 79.78
densities compared to 0.0034 M. Corrosion inhibition effi-
0.0136 1.63x10 -6
-0.203 0.019 88.79 ciency is as high as 91% at 0.0192 ppm inhibitor.
5-phenyl-1-H-tetrazole(PTA)
0.8
0.0034 2.36x10-6 -0.204 0.027 84.04 500 ppm
1000 ppm
0.6 2000 ppm
0.0068 2.22x10-6 -0.35 0.026 84.98 Blank

0.4
0.0137 1.19x10-6 -0.239 0.014 91.95

Potential / V
5-Amino-tetrazole mono hydrate (ATA) 0.2

0.0048 6.96x10-6 -0.191 0.081 52.94 0.0

0.0096 4.63x10-6 -0.208 0.054 68.69 -0.2


-6
0.0192 1.05x10 -0.234 0.012 92.90 -0.4

-0.6
10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2
0.6 Current /Acm
-2

500 ppm
0.4 1000 ppm Fig. (4). (a) Potentiodynamic polarization curves of 5-(3-Pyridyl)-
2000 ppm
1H-tetrazole corrosion inhibitor in 3.5% NaCl at 1 mVs-1 scan rate
Blank
0.2 and 20oC.
Potential / V

In the case of 5-Aminotetrazole monohydrate (ATAH)


0.0 corrosion inhibitor (Fig. 5), anodic current density is consid-
erably reduced compared to the blank. The extent of reduc-
-0.2 tion of the current density is increased with the increase of
the inhibitor concentration. The inhibition efficiency reaches
-0.4 as high as 92% at 0.0192 ppm inhibitor concentration.

0.8
-0.6 Blank
500 ppm
0.6 1000 ppm
-0.8 2000 ppm
Potential / V

0.4
Fig. (2). Potentiodynamic polarization curves of 4- 0.2
phenylthiosemicarbazide corrosioninhibitor in 3.5%.
0.0
0.8 500 ppm
-0.2
1000 ppm
0.6 2000 ppm
Blank vs Col 8 -0.4
0.4
-0.6
Potential / V

0.2 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2

0.0 Current / A cm-2

-0.2 Fig. (5). Potentiodynamic polarization curves of copper in the pres-


ence of 5-Aminotetrazole monohydrate (ATAH)corrosion inhibitor
-0.4 in 3.5% NaCl at 1 mVs-1 scan rate and 20oC.

-0.6 The enhancement in corrosion resistance of copper in the


10-8 10-7 10-6 10-5 10-4 10-3 10-2 presence of ATAH can be attributed to the formation of a protec-
-2 tive layer on copper surface. In the pH range 6-8, the inhibitor
Current /Acm
form a protective film of Cu(I) ATA complex [27-29] on the
copper surface according to the following equation:
Fig. (3). Potentiodynamic polarization curves of 5-Mercapto-1-
methyltetrazole corrosioninhibitor in 3.5% NaCl 1 mVs-1 scan rate Cu + ATAH = Cu(1)ATA + e- (3)
and 20oC.
64 Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 Younes et al.

The degree of surface coverage at different concentra- It is obvious to note that 5-phenyl-1H-tetrazole (PTAH)
tions of ATAH can be obtained from the following expres- corrosion inhibitor behaves more or less in the same trend as
sion: ATA (Fig. 7). Moreover, a clear passive region was obtained
at concentrations  0.0068 ppm inhibitor. No passivation
Icorr(b) - Icorr(inh)
was shown at higher potentials due to the degradation of the
 = ------------------------------ X 100 (4)
protective film formed on copper surface. The corrosion in-
Icorr(b) hibition efficiency reaches as high as 92% at 0.0137 ppm.
Where icorr(b), icorr(inh) represent corrosion current densities 0.8
in the absence and in the presence of the inhibitor, respec- Blank
500 ppm
tively. The adsorption of ATAH on the surface of Cu was 0.6 1000 ppm
best illustrated using the Langmuir isotherm [30, 31]: 2000 ppm
0.4 4000 ppm

Potential / V
/1- = AC exp [–E#/RT] = KC (5)
0.2
where  is the surface coverage, E# is the activation energy,
0.0
C is the concentration in mol L-1 and K is the constant of the
adsorption process. Rearranging equation 5 gives: -0.2
C/  = 1/K + C (6)
-0.4

Table 3. The degree of surface coverage against -0.6


concentration of the inhibitor. 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2

Current / A cm-2
ATAH Concentration, ppm 0.0048 0.0096 0.0192
Fig. (7). Potentiodynamic polarization curves of copper in the pres-
Surface Coverage / 52.94 68.69 92.90
ence of 5-phenyl-1-H-tetrazole(PTA) corrosion inhibitorin 3.5%
NaClat 1 mVs-1 scan rate and 20oC.
Table 2 shows the surface coverage at different ATAH Ɵ values for various PTA concentrations can be shown
inhibitor concentrations. A plot of C/ versus C (Fig. 6) on Table 3. (Go) of -36.582 kJ mol-1 was observed at 20oC.
yields a straight line with intercept 1/K. Linear regression of
the obtained straight line was used to obtain 1/K and conse- Table 4. The degree of surface coverage versus concentration
quently, K the standard free energy of adsorption (Go) can of the inhibitor.
be calculated after determining the adsorption constant (K)
using the following expression [31]: K=1/55.55exp[- Go PTAH Concentration, ppm 0.0034 0.0068 0.0137
/RT] [7] Where R is the universal gas constant and T is the
absolute temperature. The standard free energy of adsorption Surface Coverage / 84.04 84.98 91.95
(Go) of -35.14 kJ mol-1 was obtained at 20oC. The negative
value of Go indicates that ATAH is spontaneously chemi-
sorbed on the surface of copper. A co-ordinate bond was Thiosemicarbazide and tetrazole derivatives inhibit the
formed through charge sharing or transfer from the ATAH corrosion of copper by adsorption at the metal/solution inter-
molecules to the copper surface. face. Corrosion inhibition results from the presence of free
electron pairs in the S and the N atoms, p -electrons on the
240x10-6 b[0] 2.96742066e-5 aromatic rings, inhibitor molecular size and the formation of
b[1] 0.010767442
r ² 0.9978453165 copper complexes. The free and p-electrons interact with d-
orbital of Cu to provide a protective film. The corrosion in-
200x10-6 hibition of thiosemicarbazide and tetrazole derivatives in-
creases with the increase of the electron densities around the
C/

active center [11, 32].


160x10-6

5. SURFACE INVESTIGATION
120x10-6 The effect of inhibitors on the surface morphology of the
copper electrode was investigated. An illustrative example is
80x10-6
shown in Fig. (8). The figure shows the SEM micrograph of
copper treated in 0.6 M NaCl in the absence (Fig. 9a) and in
0.004 0.008 0.012 0.016 0.020 the presence of 0.0137mol L-1PTA (Fig. 8b). The copper
C/ mol L-1 surface shows very good appearance with no corrosion at-
tack in the presence of PTA whereas a high degree of surface
Fig. (6). Langmuir adsorption isotherms of copper in 0.6 mol L- roughness is shown in the absence of the inhibitor. The high
1
NaCl in the presence of ATA at 20ºC. surface roughness indicates general corrosion attack.
Corrosion Inhibition of Copper in Sea Water Using Derivatives Innovations in Corrosion and Materials Science, 2018, Vol. 8, No. 1 65

(a) CONCLUSION
Tetrazole derivatives show higher corrosion inhibition ef-
ficiency (>90%) than thiosemicarbazide derivatives (<80%).
The order of inhibition efficiencies of the tested compounds
is as follows: PTAATA >PyTA> MMT > STC > PTSC.
The high inhibition efficiency of tetrazoles can denote the
formation of a protective film of Cu(I)Tetrazole complex on
the copper surface. The inhibition efficiency of Tetrazole
derivatives obeys Langmuir adsorption isotherms while the
calculated free energy of adsorption indicates chemisorptions
of the inhibitor on the copper surface.

ETHICS APPROVAL AND CONSENT TO PARTICI-


PATE
Not applicable.
(b)
HUMAN AND ANIMAL RIGHTS
No Animals/Humans were used for studies that are the
basis of this research.

CONSENT FOR PUBLICATION


Not applicable.

CONFLICT OF INTEREST
The authors declare no conflict of interest, financial or
otherwise.

ACKNOWLEDGEMENTS
The authors of the present work acknowledge the revi-
-1 sion of the manuscript by Prof. Dr. Nabil Nassif, emeritus
Fig. (8). SEM micrographs of copper treated in 0.6 mol L NaCl
Prof. of Corrosion, CMRDI. The authors also acknowledge
under the following conditions: a) 0.6 M NaCl only (b) In the pres-
that there is no conflict of interest regarding the performed
ence of 10-2 mol L-1 PTAH.
research work.
The present work reveals that tetrazoles derivatives ex-
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