J Bio Tribo Corros (2017) 3:53
DOI 10.1007/s40735-017-0114-z
Inhibition and Adsorption of Polyvinyl Acetate (PVAc)
on the Corrosion of Aluminium in Sulphuric and Hydrochloric
Acid Environment
S. C. Nwanonenyi1 · H. C. Obasi1 · E. E. Oguzie2 · I. C. Chukwujike3 · C. K. Anyiam4
Received: 28 July 2017 / Revised: 28 September 2017 / Accepted: 14 October 2017 / Published online: 23 October 2017
© Springer International Publishing AG 2017
Abstract  The performance of PVAc as a safe inhibitor for
corrosion of aluminium in 2 M H ­ 2SO4 and 0.5 M HCl solu-
tion at varying temperatures was investigated by weight loss,
polarization measurement and computational technique.
Weight loss measurements showed that PVAc exhibited
excellent inhibitory character within the studied environ-
ment and efficiency of inhibition increased with increasing
concentration of PVAc, but decreased with rise in tempera-
ture. Also, it is observed that aluminium displayed higher
susceptibility to dissolution in the hydrochloric compared to
sulphuric acid. Results of free energy of adsorption suggest
physical adsorption. The adsorption of PVAc on the alumin-
ium surface followed Langmuir adsorption isotherm, thus
showing evidence of physisorption mechanism. Polarization
results revealed that PVAc functions as a mixed-type inhib-
itor with absolute control of the anodic reaction. Results
of computational technique showed the apparent correla-
tion between corrosion inhibition efficiency and electronic
molecular structure regarding frontier molecular orbital
theory.
* S. C. Nwanonenyi
simeonnwanonenyi@gmail.com
1 enabling the alloy to retain its resistance to deterioration.
Department of Polymer and Textile Engineering, Federal
University of Technology, Owerri, Nigeria
2 is guaranteed only in aqueous solutions with the pH range
Electrochemistry and Materials Science Research Laboratory,
Department of Chemistry, Federal University of Technology,
Owerri, Nigeria
3
Department of Polymer and Textile Engineering, Nnamdi
Azikiwe University, Awka, Nigeria
4
Department of Prosthetics and Orthotics, Federal University
of Technology, Owerri, Nigeria
 
Keywords  Aluminium · Corrosion · Weight loss ·
Polarization measurement · Computational technique
1 Introduction
The utilization of aluminium extensively in various engi-
neering designed projects ranging from industrial to domes-
tic products is better or more beneficial only with the alu-
minium alloys. These could be attributed to the presence
of wide range of specific properties possessed by the alu-
minium alloys due to the presence of two or more metals,
additives and heat treatment combined during their purifica-
tion to achieve the desired objectives. Pure aluminium is soft
and weak, while aluminium alloy possesses a broad range
of mechanical properties and the composition of the alloy is
considered as one of the most crucial factors that affect the
corrosion behaviour of the metal. In structural and industrial
designs, aluminium alloys are mainly used perhaps due to
its cost, light weight, mechanical and thermal properties,
availability, etc. [1]. Aluminium is a reactive metal which
forms a passive film (natural oxide alumina) on its surface
in an oxygen-containing environment, and this helps it to
resist corrosion in that environment. Undoubtedly, sufficient
removal of this oxide film by scratching may lead to the
rapid reappearance of a new film in most conditions, thereby
According to Pourbaix [2], the stability of this oxide film
of 4.5–8.5, whereas in strong acids or alkalis it is soluble
leading to a rapid attack of the aluminium surface. Alumin-
ium hydroxide is the initial corrosion product of aluminium
in aqueous solutions, but with time it changes a hydrated
aluminium oxide, and the susceptibility of aluminium in a
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corrosive environment could be attributed to its high elec-
tronegative potential.
Having seen that aluminium alloys do not have a stable
shelf life in strong acids or alkalis, it is imperative to prof-
fer means of regulating corrosion damage on the surfaces
of aluminium products in that said environment. Survey
through the literature concerning corrosion studies revealed
that use of corrosion inhibitors remains a dominant strat-
egy in controlling corrosion menace on hollow profile
aluminium surfaces exposed in a corrosive environment.
Examples of the inhibitors reported by some researchers
that have corrosion inhibition potentials include: methanol,
ethanol, isopropanol and ethylene glycol [3], salicylalde-
hyde-2-hydroxy acetophenone ethylenediamine, phenyl-
hydrazine-2-hydroxyacetophenone, N-isonicotinamidosal-
icylaldimine and benzaldehyde-2-hydroxyzine [4], surface
active substances (dodecanoyl-N-methylglycine, dodecyl
benzene sulphonate, dodecylsulphate and N-dodecanoyl-
N-methyltaurine) [5], 1-hexadecylpyridinium chloride
[6], 1-hydroxyimidazole-3-N-oxide, 1-hydroxy-2-ben-
zoyl-5-phenylimidazole-3-N-oxide and 1-hydroxyimi-
dazole-2,4,5-trimethyl-3-N-oxide [7], cadmium sulphate
[8], 2-picoline and 4-picoline [9], triazoline derivatives
[10], plasma polymer of tetraethoxysilane [11], imidazo-
line derivatives [12], pyridine and its selected derivatives
(2,5-dibromopyridine and symmetric collidine) [13], phenols
(phenol, resorcinol and pyrogallol) [14], metacryloxypro-
pylmethoxy silane [15], tetradecyl-1,2-diolpropeneoxylates
[16], vanillin [17], ethoxylated fatty acids [18], methylene
blue [19], Opuntia extract [20], mercaptoacetic acid [21],
organic compounds (sulphonic acid, sodium cumene sulpho-
nate and sodium alkyl sulphate) [22], amino acids (alanine,
leucine, valine, proline, methionine and tryptophan) [23],
propargyl alcohol (2-propyn-1-ol) and potassium sodium
tartrate [24], tetrazole derivatives [25], doxycycline hydro-
chloride drug) [26].
Among these inhibitors stated above, those from organic
sources or polymer background are of the paramount inter-
est. And this could be ascertained from the fact that these
inhibitors pose no negative challenge to the environment
and human beings. Furthermore, there is the presence of
hetero-atoms, cyclic structures and multiple bonding sites
within the chemical structure of some of these inhibitors
which help to boost their inhibition potentials. It is evident
from the scientific literature that much has not been pub-
lished concerning the corrosion inhibition of aluminium
using polymers [27–37]. To our knowledge, no work has
been published on corrosion inhibition of any known metal
using PVAc as inhibitor save in our previous work [38].
Therefore, the present study seeks to explore the corrosion
inhibition of aluminium in sulphuric and hydrochloric acid
solutions using PVAc as a contribution to the recent demand
for environmentally safe corrosion inhibitors using various
13
J Bio Tribo Corros (2017) 3:53
experimental conditions and techniques. Such experimen-
tal conditions include inhibitors concentration, temperature
variations, immersion time and experimental techniques
(such as weight loss, potentiodynamic polarization and
computational).
2 Experimental
2.1 Materials
The PVAc used was the product of Sigma-Aldrich, Fluka
Analytical, Germany. HCl and H ­ 2SO4 acids used were BDH
AR grade. An aluminium sheet (type AA 1060 and purity
98%) used was press-cut mechanically into 4 × 3 × 0.2 cm
coupons and polished with fine emery papers. The coupons
were further rinsed with acetone, washed with double-dis-
tilled water, dried in hot air and weighed. 0.5 M HCl and
2 M ­H2SO4 acid solutions used as clear (blank) solutions
were prepared with double-distilled water. The inhibitor
solutions used ranged from 0.5 to 2.5 g/L concentration.
2.1.1 Experimental Techniques
The prepared aluminium coupons were immersed in test
solutions (200 mL) contained in 250-mL capacity beakers
with the aid of a nylon thread, glass rod, and hook. The
beakers were kept at a room temperature at 30 ± 1 °C. After
the end of 24-h interval, the coupons were retrieved, and
this continued progressively for 144 h. Also, to investigate
the effect of temperature variations the beakers were equil-
ibrated at 35–65 °C in a thermostatic water bath and the
coupons were retrieved at 8-h interval. The weight loss val-
ues (obtained from the difference between the initial weight
of coupons before immersion in the test solution and the
final weight of coupons after immersion in the test solution)
recorded were mean values of triplicate determinations.
Polarization study was conducted using conventional
glass electrolytic cell and PARC-2273 advanced electro-
chemical instrument. The glass cell assembly consists of
electrodes (counter electrode—platinum plate, reference
electrode—saturated calomel electrode, and working elec-
trode—aluminium coupon), electrolytes and copper wire.
The metal electrodes were connected to a copper wire for
electrical contact and embedded in epoxy resin leaving a
surface area of 1  cm2 uncovered. Before each polariza-
tion measurement, a stabilization period of 30  min was
allowed for a steady-state open-circuit potential (OCP) to
be established. We took polarization measurements over a
potential range − 250 to + 250 mV at corrosion potential
of 0.333 mV/s scan rate. Each experiment was carried out
in triplicate, and the average values of corrosion parameters
were reported.
J Bio Tribo Corros (2017) 3:53 Page 3 of 13  53

The computational technique was utilized to ascertain

the role played by electronic structure of PVAc molecule
in improving its efficiency as inhibitor. It was done by opti-
mizing the geometry of the PVAc molecule using density
functional theory (DFT) through the Mulliken population
analysis within the framework of the ­DMol3 electronic struc-
tural program as contained in Materials Studio 7.0 software
(Accelrys Inc.). Restricted spin polarization, DNP basis
set and the Perdew–Wang (PW) local correlation density
functional form are the electronic parameters used for the
modelling. This technique assessed the molecular orbital
of the PVAc molecule and predicted the energy of HOMO
orbital (EHOMO), the energy of LUMO orbital (ELUMO),
the energy gap (Egap) between the EHOMO and ELUMO and
other chemical reactivity of the PVAc molecule. Also, the
molecular dynamic modelling was performed to determine
the interfacial binding energy between the PVAc (single
molecule and multiple molecules) and charges on the sur-
face aluminium crystal at the molecular level. Also, density
functional theory (DFT) within the framework of the For-
cite electronic structural program as contained in Materials
Studio 7.0 software (Accelrys Inc.) was used. Electronic
parameters utilized for the simulation are COMPASS force
field, Al crystal (density packed surface, cleaved along the
(110) plane), constrained Al slab, Forcite quench dynamic
simulation. Other parameters used include optimized PVAc
structure, 12 × 10 supercell, QEq charge, a smart algorithm
with NVE (microcanonical) ensemble, time step (1 fs) and
simulation time (5 ps), temperature (fixed at 298.0 K) and
quenching (every 250 steps).

Fig.  1  a Plot of weight loss against time for aluminium corrosion in
2 M ­H2SO4 in the absence and presence of different concentrations of
3 Results and Discussion PVAc at 30 ± 1 °C. b Plot of weight loss against time for aluminium
corrosion in 0.5 M HCl in the absence and presence of different con-
3.1 Gravimetric Measurement centrations of PVAc at 30 ± 1 °C

3.1.1 Weight Loss
The material loss during the dissolution of aluminium cou-
pons in both 2 M H ­ 2SO4 and 0.5 M HCl acid, respectively,
with and without different concentrations of PVAc was
determined at 30 ± 1 °C and 24-h interval progressively
for 144 h, and the representative variations in weight loss
versus time are shown in Fig. 1a, b. It is evident from the
figure that aluminium coupons showed more dissolution in
blank solutions compared to inhibited solutions, and hydro-
chloric acid compared to sulphuric acid. This behaviour is
certain that PVAc regulated the dissolution of aluminium
coupons exposed to 2 M ­H2SO4 and 0.5 M HCl acid, and
that chloride ion is more aggressive to aluminium than sul-
phide ion. This is attributed to the stability of aluminium
oxide in sulphuric acid compared to hydrochloric acid due
to variation in the electronegative potential of sulphide and
chloride ion [2]. It could be inferred from the lower val-
ues of material loss exhibited in the inhibited solution that
PVAc molecules adsorbed onto the aluminium surface ini-
tially impeded the dissolution process thereafter, but gradual
weakening effect sets in with time on the adsorbed layer.
Also, it is observed that the material loss varies linearly with
time in both blank and inhibited solutions. However, the
linear relationship could be attributed to the fact aluminium
coupons did not show any sign of passive character within
the time of exposure.
3.1.2 Corrosion Rates
The presence of oxygen or air and water in an environment
empowers aluminium to form a self-protective oxide (film)
which makes it resistant to corrosion in that environment.

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However, in an acidic environment (such as hydrochloric
acid and sulphuric acid) this protective film dissolves, and
corrosion is initiated spontaneously at the weak sites on
the aluminium surface [39, 40], and anodic reaction sets in
according to Eq. (1) stated as follows:
Al → Al3+ + 3e− (1)
Normally, there must be a cathodic reaction or reduction
process to utilize the electrons produced. The significant
reduction process results in hydrogen evolution as follows:
2H+ + 2e− → 2Hads → H2 (2)
The atomic hydrogen adsorbed on the aluminium surface
­(Hads) reacts by combining with other adsorbed hydrogen
(H) atom to form hydrogen gas (­ H2) which bubbles from
the surface [41]. The corrosion of aluminium in blank and
inhibited solutions was characterized by rapid effervescence
resulting from evolved hydrogen gas, but the corrosion rates
of the aluminium coupons in the absence and presence of
PVAc were thus monitored by measuring the amount of
material loss (gravimetric measurement) during the corro-
sion reaction. This gravimetric technique provides an effi-
cient, sensitive, visual and rapid means for assessing any
interruption by an inhibitor about weight or material loss
according to Eq. (3):
[ ]
8.76 × 104 × ΔW
CR(mm∕year) = (g/ )
Density of coupon cm3 × surface area of coupon cm2 × exposed time (h)
slow pace of material dissolution at the beginning of the
reaction and after an incubation period, which corresponds
to the time interval required by the corrodents to rupture the
pre-immersion oxide layer on the aluminium surface [42].
Moreover, the results showed that aluminium displayed
high corrosion resistance in the sulphuric acid compared to
hydrochloric acid, and corrosion rates increased with rise in
temperature for all systems, but decreased with increasing
concentration of PVAc (that is, reduced rates of material dis-
solution on the introduction of the PVAc to the corrodents).
This behaviour suggests that the inhibiting effect of PVAc
is concentration dependent.
3.1.3 Inhibition Efficiency
Corroding metal surface has multiple adsorption sites with
distinct activation energies and heats of adsorption due to
inherent non-homogeneous nature of the surfaces arising from
the presence of lattice defects and dislocations [36]. Inhibitor
molecules retard corrosion process by adsorbing more readily
onto the corrosion sites on the metal surface, and the result-
ing adsorption film reduces the rate at which corrosive agents
diffuse into the metal surface. Hence, the action or effect of
corrosive agents responsible for the propagation of corrosion
(3)
( )

where ∆W is the weight loss (g). processes (rate-determining steps) is curtailed with resultant
Table 1 compares the rates of aluminium corrosion in 2 M suppression of dissolution of aluminium by the protective
­H2SO4 and 0.5 M HCl, respectively, in the absence and pres- film. The degree of surface coverage (θ) and the inhibition
ence of PVAc at different temperatures. The result reveals efficiency (%) were calculated according to Eqs. (4) and (5):

Table 1  Calculated values Conc Corrosion (mm/year) Inhibition efficiency (%) Surface coverage (θ)
of corrosion rate (mm/year) (g/L)
and inhibition efficiency (%) 35 °C 45 °C 55 °C 65 °C 35 °C 45 °C 55 °C 65 °C 35 °C 45 °C 55 °C 65 °C
for aluminium corrosion in
0.5 M HCl and 2 M ­H2SO4 H2SO4
acid solutions in the absence  Blank 24.53 29.34 37.08 44.14 – – – – – – – –
and presence different  0.5 7.12 9.61 13.98 18.43 70.97 67.25 62.30 58.25 0.71 0.67 0.62 0.58
concentrations of PVAc at
35–60 °C  1.0 5.85 7.83 11.75 15.26 76.15 73.31 68.31 65.43 0.76 0.73 0.68 0.65
 1.5 4.51 6.53 9.89 13.85 81.61 77.74 73.33 68.62 0.82 0.78 0.73 0.69
 2.0 3.67 5.21 8.03 11.25 85.04 82.24 78.34 74.51 0.85 0.82 0.78 0.75
 2.5 2.37 4.65 6.85 9.55 90.34 84.15 81.53 78.36 0.90 0.84 0.82 0.78
HCl
 Blank 26.34 31.06 39.03 47.44 – – – – – – – –
 0.5 9.45 11.87 16.98 21.85 64.12 61.78 56.50 53.93 0.64 0.62 0.57 0.54
 1.0 7.84 10.85 14.85 20.26 70.24 65.07 61.95 57.29 0.70 0.65 0.62 0.57
 1.5 6.91 10.15 13.85 18.95 73.77 67.32 64.51 60.05 0.74 0.67 0.65 0.60
 2.0 6.23 9.21 12.76 17.53 76.35 70.35 67.31 63.05 0.76 0.70 0.67 0.63
 2.5 5.68 8.32 10.88 15.67 78.44 73.21 69.56 66.97 0.78 0.73 0.70 0.67

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J Bio Tribo Corros (2017) 3:53 Page 5 of 13  53

[ ( )] in 2 M ­H2SO4 and 0.5 M HCl observed from corrosion rate

CRinh
𝜃 = 1− (4) data was found to follow adsorption isotherm of Langmuir,
CRuninh
given by Eq. (7):
[ (
CRinh
)] C 1
%IE = 1 − × 100 (5) 𝜃
=
Kads
+C (7)
CRuninh

where ­CRinh and ­CRuninh are corrosion rates in the presence where Kads is the equilibrium adsorption constant; C, inhibi-
and absence of inhibitor, respectively. tor concentration; and θ, degree of surface coverage. The lin-
Table 1 shows the inhibition efficiency and degree of ear plot obtained from the correlation between the inhibitor
surface coverage of different concentrations of PVAc in concentration and degree of surface coverage in Fig. 2a, b
2 M ­H2SO4 and 0.5 M HCl at different temperatures. The suggests that PVAc species hinder specific adsorption sites
results revealed that PVAc inhibited the acid-induced cor- at the solid/liquid interface. In both systems, the equilib-
rosion of aluminium, inhibition efficiency increased with rium adsorption constant (K) represents the binding power
increasing concentrations, whereas the efficiency of inhibi- or adsorption strength of the PVAc species on the aluminium
tion decreased with increasing temperature at all systems. It surface. Also, results from Fig. 2a, b show that Kads values
suggests that degree of protective action of PVAc increased are 0.96 and 0.83 for aluminium in 2 M ­H2SO4 and 0.5 M
with an increase in concentration due to more surface cover-
age obtained from enhanced inhibitor adsorption. Further-
more, the trend of inhibition efficiency with temperature
according to Martinez and Stern [43] and Popova et al. [44]
implies physical adsorption of PVAc on the aluminium sur-
face in both corrodents which created an adsorption film
that retarded the charge and mass transfer process [45]. The
behaviour possibly indicates among other reasons that the
adsorption complexes formed at the aluminium/solution
interphase possess distinct features of electrostatic charac-
ter and become soluble at increased temperature leading to
desorption of some adsorbed PVAc, uncovering of some
protected areas on the aluminium surfaces and aiding the
attack of the corrosive agents.

3.2 Adsorption Considerations

The regulatory action of inhibitors on the corroding metal

surface in an unfriendly medium seems to be occurred by
physical or chemical adsorption and could be regarded as
displacement process between the inhibitor species and
adsorbed water molecules on the metal surface [46] accord-
ing to Eq. (6):
Inh(sol) + XH2 O(ads) ↔ Inh(ads) + XH2 O(sol) (6)
where ­Inh(sol), ­Inh(ads), ­H2O(ads) and X represent the inhibi-
tor molecules in the aqueous solution, inhibitor molecules
that are adsorbed to the metal surface, water molecules on
the metal surface and some water molecules replaced by
the inhibitor molecules, respectively. Any inhibitor has its
means of adsorption which is dependent on the nature of
metal, corrodent composition, concentration and structure of
inhibitor and temperature influence. The adsorption interac-
tion between the inhibitor species and charge on the metal
surface can be described using adsorption isotherms [47]. Fig.  2  a Langmuir isotherm for PVAc adsorption on aluminium in
The adsorption of PVAc on the corroding aluminium surface 2 M ­H2SO4 solution at 35 °C. b Langmuir isotherm for PVAc adsorp-
tion on aluminium in 0.5 M HCl solution at 35 °C

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Page 6 of 13 J Bio Tribo Corros (2017) 3:53

HCl, respectively. The linear correlation coefficient (R2) is

close unity in all systems, and positive values of K confirm
that PVAc species are adsorbed on the aluminium surfaces.
Also, the successful applications of using regression mod-
els in analysing corrosion results have also been reported
[48–52] to justify the advantages of using regression models
and its methodology in the study

3.3 Temperature Effect

To investigate the effect of temperature on inhibition and

adsorption performance of inhibitors on metals exposed
in the aggressive medium, the kinetic parameters of the
free energy of adsorption, (∆Gads), enthalpy of adsorption,
(∆Hads), the entropy of adsorption (∆Sads) and energy of acti-
vation (Ea) are used.

3.3.1 Energy of Activation (Ea)

The dissolution or corrosion of metals in free acid solu-

tion is a chemical or electrochemical reaction process which
requires a certain amount of energy regarded as the energy
of activation to initiate the reaction process. Also, the energy
of activation is utilized effectively to ascertain the mecha-
nism of inhibition adsorption process during metal corro-
sion in the inhibited aggressive environment according to
Oguzie et al. [53]. The relationship between corrosion rate
and energy of activation based on temperature dependence
during corrosion of metals in the aggressive medium is illus-
trated using Arrhenius Eq. (8):
[ ]
−Ea
CR = Aexp (8)
RT
where CR is the corrosion rate, A is the pre-exponential fac-
tor, Ea is the energy of activation, T is the absolute tem-
perature and R is the universal gas constant. The plots of
variation in the logarithm of corrosion rate with reciprocal of
absolute temperature for aluminium in 2 M H ­ 2SO4 and 0.5 M
HCl, respectively, are presented in Fig. 3a, b, and the cal-
culated values of Ea obtained from the slope (− Ea/2.303R)
are given in Table 2. Figure 3a, b illustrates the corrosion
rate of aluminium in both the free acid and inhibited solu-
tions increased with rise in temperature. Linear plots and
values of energy of activation (Ea) obtained are higher in the
inhibited solutions compared to free acid solutions. The vari-
ation in Ea values seen in both 2 M ­H2SO4 and 0.5 M HCl
environments in the absence and presence PVAc as shown
in Table 2 is an indication that energy barrier is needed to
be overcome for the corrosion reactions to begin. Thus, high
values of Ea bring low corrosion rate, whereas small values
of Ea give a high rate of corrosion. Data in Table 2 revealed
that results of Ea are in full agreement with the corrosion rate
Fig.  3  a Arrhenius plot for variation in logarithm of corrosion rate
with reciprocal of absolute temperature for aluminium in 2 M H ­ 2SO4
in the absence and presence of PVAc. b Arrhenius plot for variation
in logarithm of corrosion rate with reciprocal of absolute temperature
for aluminium in 0.5 M HCl in the absence and presence of PVAc
results in Table 1. Also, it is seen from the results obtained
that Ea values in both blank and inhibited solutions in the
2 M ­H2SO4 environment are higher than those in 0.5 M
HCl environment and this is also a strong confirmation that
mild steel coupon exhibited more corrosion susceptibility in
0.5 M HCl environment than in the 2 M ­H2SO4 environment.
Furthermore, the variations in Ea values observed may be
linked to the modification of the mechanism of corrosion
process in the presence of adsorbed PVAc species in both
environments. This scenario evidently supports that there is
the existence of increased energy barrier for the aluminium
dissolution process. It could be deduced from the observed
increase in Ea values due to the increase in the presence
of PVAc in both 2 M ­H2SO4 and 0.5 M HCl. Also, this
behaviour may suggest that PVAc species did not change
the rate-determining hydrogen (­ H2) adsorption pattern of the

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J Bio Tribo Corros (2017) 3:53 Page 7 of 13  53

Table 2  Some kinetic System ∆Hads ∆Sads ∆Ea ∆Gads (KJ/mol)

parameters for dissolution of Conc (g/L) (KJ/mol) (KJ/mol) (KJ/mol)
aluminium in 2 M ­H2SO4 and 35 °C 45 °C 55 °C 65 °C
0.5 M HCl in the absence and
presence of PVAc at different H2SO4
temperatures  Blank 14.56 − 71.43 17.25 – – – –
 0.5 25.20 − 47.17 27.88 − 4.35 − 14.32 − 14.18 − 14.14
 1.0 25.66 − 147.38 28.34 − 13.24 − 13.25 − 13.67 − 13.03
 1.5 29.99 − 135.39 32.67 − 13.13 − 12.89 − 12.56 − 12.40
 2.0 30.07 − 136.92 32.75 − 12.95 − 12.80 − 12.51 − 12.43
 2.5 37.14 − 116.80 39.82 − 13.57 − 12.58 − 12.59 − 12.27
HCl
 Blank 14.50 − 171.10 17.18 – – – –
 0.5 22.07 − 155.08 24.76 − 13.53 − 13.75 − 13.61 − 13.69
 1.0 24.65 − 148.10 27.33 − 12.45 − 12.26 − 12.29 − 12.08
 1.5 25.98 − 144.58 28.91 − 11.93 − 11.42 − 11.54 − 11.29
 2.0 27.03 − 142.15 29.71 − 11.46 − 11.03 − 10.99 − 11.33
 2.5 26.00 − 146.33 28.68 − 11.18 − 10.83 − 10.76 − 11.09

corrosion process. However, the protective action of PVAc
primarily occurred through physical adsorption of the PVAc
species on the aluminium surface with the deactivation of
these surfaces to hydrogen ­(H2) atom recombination [41].
3.3.2 Enthalpy of Adsorption (∆Hads) and Entropy
of Adsorption (∆Sads)
These kinetic parameters were utilized in this research work
to characterize the thermodynamic process and adsorption
mechanism of the corrosion inhibition process. The positive
enthalpy value in both the free acid and inhibited solutions,
respectively, reveals that dissolution of aluminium occurred
via endothermic process, whereas negative value implies an
exothermic process. Also, the increase in enthalpy values in
the presence of inhibitor compared to the blank acid solu-
tion indicates physical adsorption. A negative value of ∆Sads
reflects the free movement of inhibitor molecules within the
bulk solution and the decrease in the disorderly manner of
adsorption of inhibitor molecules on the metal surface and
association steps in the rate-determining steps of the acti-
vated complex. But the positive value of ∆Sads indicates an
increase in the degree of disorderliness of corrosion inhibi-
tion system in the presence of inhibitor [30]. The estimate of
enthalpy and entropy of adsorption for the corrosion inhibi-
tion process was obtained from the trend of corrosion rate
with temperature according to transition-state Eq. (9):
) [ ( ) ( ΔS ) ( )]
(
CR R ads ΔHads
Log = Log + −
T Nh 2.303RT 2.303RT
(9)
where ∆Hads and ∆Sads are enthalpy and entropy of adsorp-
tion process, respectively; CR is corrosion rate; R, universal
gas constant; N, Avogadro’s constant; h, Planck’s constant;
and T, absolute temperature. The variation in log (CR/T)
against 1/T for aluminium corrosion in 2 M ­H2SO4 and
0.5  M HCl, respectively, at different concentrations of
PVAc is plotted in Fig. 4a, b. Linear plots were obtained.
Slope and intercept are equal to (− ∆Hads/2.303R) and [(log
(R/Nh) + ∆Sads/2.303R)], respectively, from which the values
of ∆Hads and ∆Sads were calculated and are listed in Table 2.
Data in Table 2 suggest that dissolution of aluminium in
both corrodents exhibited endothermic features, adsorption
mechanism occurred via physical adsorption process and
orderly manner of adsorption of PVAc species on the alu-
minium surface. Also, the variation in the values of ∆Sads
observed in both 2 M H ­ 2SO4 and 0.5 M HCl environments
in the absence and presence PVAc as shown in Table 2 is a
revelation that there is more reduction in the disorderliness
of corrosion reaction process in 0.5 M HCl environment
compared to 2 M ­H2SO4 environment. This is due to more
negative values of ∆Sads obtained in 0.5 M HCl environment.
3.3.3 Free Energy of Adsorption (∆Gads)
The free energy of adsorption ∆Gads values were estimated
using Eq. (10) and are listed in Table 2.
(10)
( )
ΔGads = −RTIn 55.5Kads
where Kads is equilibrium adsorption constants and is given
by
𝜃
Kads = (11)
C(1 − 𝜃)
where θ is the degree of surface coverage; C, concentration
of the inhibitors in g/L; R, gas constant; and T, absolute

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Page 8 of 13
Fig.  4  a Variation in log (CR/T) against 1/T for aluminium corrosion
in 2 M H ­ 2SO4 at different concentrations of PVAc. b Variation in log
(CR/T) against 1/T for aluminium corrosion in 0.5 M HCl at different
concentrations of PVAc
temperature. The negative ∆Gads values obtained indicate
the stability of the adsorbed PVAc on the aluminium sur-
face and the spontaneity of the corrosion inhibition process.
Also, the values of ∆Gads obtained in this present study are
consistent with electrostatic behaviour exhibited by the inter-
action between the PVAc species and the charge on the alu-
minium surface which is an indication of physical adsorption
[54]. Also, ∆Gads becomes more negative with increase in
temperature as a function of temperature, and this also sug-
gests spontaneous reaction via physical adsorption.
3.4 Polarization Results
The polarization measurement was used to establish the
nature of inhibition adsorption process exhibited by PVAc
on the aluminium coupon in 2 M ­H2SO4 and 0.5 M HCl,
13
J Bio Tribo Corros (2017) 3:53
Fig.  5  a Polarization curves of aluminium corrosion in 2  M ­H2SO4
in the absence and presence of PVAc. b Polarization curves of alu-
minium corrosion in 0.5 M HCl in the absence and presence of PVAc
respectively. The changes observed in the polarization
behaviour after introducing PVAc into aluminium/corrodent
system were usually used as criteria to classify PVAc as
anodic, cathodic or mixed inhibitor according to [55]. Fig-
ure 5a, b illustrates the anodic and cathodic polarization
curves of AA 1060 alloy exposed in 2 M ­H2SO4 and 0.5 M
HCl, respectively, in the absence and presence of differ-
ent concentrations of PVAc. It is evident from the figure
that shift in corrosion potential (Ecorr) was towards posi-
tive direction (that is, displacement was more in the anodic
region compared to cathodic counterpart) with a reduc-
tion in the current densities upon addition of PVAc. These
results indicate that PVAc behaved as mixed-type inhibitor
during the corrosion inhibition process and predominantly
controlled anodic dissolution of aluminium. This behaviour
also suggests that PVAc has a significant effect on retard-
ing the anodic reaction and cathodic hydrogen gas evolution
J Bio Tribo Corros (2017) 3:53 Page 9 of 13  53

reaction. The polarization parameters corrosion potential
(Ecorr), corrosion current densities (score), cathodic Tafel
slope ­(bc) and anodic Tafel slope (­ ba) obtained from the
polarization curves are listed in Table 3. The data exhibit
that the values of the Ecorr shift to more positive values as
the concentration of PVAc increased, and corrosion current
densities and numerical values of cathodic and anodic Tafel
slopes, respectively, demonstrated pronounced decrement
on the addition of PVAc. Hence, the extent of decrement is
dependent on the concentration of PVAc.
3.5 Computational Studies
The introduction of computational techniques in this present
study is to use the theoretical framework (density functional
theory, DFT) to assess the impact of electronic molecular
structure in the inhibitive performance of PVAc during the
corrosion inhibition process. This assessment is necessary
because the effectiveness or performance of inhibitors has a
co-relation with the quantum chemical parameters. And these
parameters are (a) energy of the highest occupied molecular
orbital (EHOMO), (b) energy of the lowest unoccupied molecu-
lar orbital (ELUMO), (c) energy gap (ΔE = ELUMO − EHOMO)
between the LUMO and HOMO obtained from the different
chemical structures of the inhibitors [56]. These energies of
frontier molecular orbital (EHOMO and ELUMO) predict the
ability of the inhibitor molecule to either accept an electron
or donate an electron from the charge on the metal surface.
High values of EHOMO represent the better electron donat-
ing potential, whereas small values of ELUMO depict well the
electron accepting capability. Also, lower values of energy
gap predict high or good protection efficiency because, at this
state, small energy is required to remove an electron from the
last occupied orbital.
3.5.1 Geometrical Optimization
The electronic molecular structure of PVAc molecule was
geometrically optimized, and the geometrically optimized
structure of PVAc molecule, the total electron density of the
molecule, energy of molecular orbitals and Fukui indices FI
(that is, active adsorption sites) regarding local reactivity
were obtained. The outcome of computational modelling is
presented in Fig. 6 which establishes the spatial arrangement
of the molecule and ascertains the adsorption orientation,
values of EHOMO and ELUMO and active adsorption sites of
the PVAc molecule. The calculated values of ELUMO, EHOMO
and ∆E obtained are − 1.5831, − 6.3544 and 4.7713 eV,
respectively. Hence, it is seen clearly that these results agree
with the statement made earlier that PVAc has good cor-
rosion inhibition tendency from the molecular viewpoint.
Furthermore, the electron density saturates all around the
PVAc single molecule suggesting a flat-lying adsorption ori-
entation, whereas LUMO and HOMO orbitals are distrib-
uted over the vinyl and acetate group as shown in Fig. 6b–f.
The local reactivity analysed by Fukui indices indicates that
­F+ sites are connected to the LUMO locations, and ­F− sites
conform to HOMO locations, thus showing the expected
sites through which electron interchange would likely occur
between PVAc single molecule and charge on the aluminium
surface to form complex ion that inhibits the corrosion pro-
cess via adsorption.
3.5.2 Molecular Dynamic (MD) Simulation

Table 3  Polarization parameters aluminium corrosion in 2 M ­H2SO4 This process was performed to investigate the adsorption
and 0.5 M HCl in the absence and presence of PVAc at 30 ± 1 °C interaction existing between PVAc single molecule and charge
Conc Ecorr Icorr IE bc ba on the aluminium surface at the molecular level and compute
(g/L) (EvsSCE (μA cm−2) (%) (mV dec−1) (mV dec−1) the binding energy or energy of adsorption between them.
(V)) In performing the simulation, different conformations of the
H2SO4 low-energy adsorption or most stable representative adsorp-
 Blank − 489.67 98.89 – 72 56 tion configurations for a single PVAc molecule on aluminium
 0.5 − 492.45 26.45 73.23 84 63 crystal (110) surface were sampled, and the average of the
 1.0 − 495.67 22.65 77.10 87 67 energies of the corresponding binding energy of adsorption
 1.5 − 498.08 19.78 80.00 91 69 was computed according to Eq. (12) stated as follows:
 2.0 − 500.67 16.09 83.73 96 71
(12)
[ ]
 2.5 − 503.45 11.01 88.87 103 75 EBinding energy = ETotal − EPVAc repeat unit + EAl
HCl
where EPVAc is repeat unit, and EAl and ETotal = energy of
 Blank − 493.56 116.78 – 78 68
PVAc single molecule are the energy of Al surface with
 0.5 − 496.67 37.19 68.15 93 71
no adsorption and total energy of the system containing
 1.0 − 498.78 33.23 71.54 98 74
PVAc single molecule and Al surface, respectively. Fig-
 1.5 − 500.32 29.43 74.80 105 75
ure 7 illustrates the top, front and side view, respectively, of
 2.0 − 506.98 27.94 76.07 108 78
the lowest energy of adsorption interaction between PVAc
 2.5 − 510.55 24.23 79.25 111 80
single molecule and aluminium crystal (110) surface at a

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53 
Page 10 of 13
Fig. 6  Electronic properties of PVAc single molecule: a Optimized
structure, b total electron density, c HOMO orbital, d LUMO orbital,
e electrophilic attack (f −), f Nucleophilic attack ­(f+) (atom identifica-
tion: where C, H and O = grey, white and red, respectively). The dif-
molecular level from our simulations. The value of bind-
ing energy obtained between the adsorption interaction of
PVAc repeat unit and aluminium crystal (110) surface is
− 5.19980690 kcal/mol. The binding energy of adsorption
obtained has a negative value, suggesting that there is stable
and strong adsorption interaction between PVAc repeat unit
and aluminium crystal (110) surface. However, the magni-
tude of binding energy obtained is not in full agreement with
the strong PVAc–Al interaction as predicted experimentally
from the ∆Gads values.
Additionally, the adsorption interaction between a cluster
of PVAc molecules and aluminium crystal (110) surface at
the molecular level was modelled using molecular dynamic
simulation to decipher their binding energy of adsorption.
The essence is to illustrate the clear picture of adsorption
characteristics between a cluster of PVAc molecules and
aluminium crystal (110) surface within the adsorbed inhibi-
tor film. The vinyl acetate repeat unit was used to generate
the cluster of PVAc molecules (which contained a sequence
13
J Bio Tribo Corros (2017) 3:53
ference in electron density is shown by blue and yellow isosurfaces,
the yellow regions signify electron loss, whereas blue regions signify
electron accumulation (Color figure online)
of vinyl groups and acetate groups as the backbone chains
and side chains, respectively) through the aid of Polymer
Builder program. The somewhat unrealistic PVAc structure
obtained was modified using geometrical optimization to
produce a spatial arrangement of PVAc structure typical to
those found in an ideal or actual situation [57]. The geo-
metrically optimized polymeric cluster of PVAc molecules
(Fig. 8) was subsequently placed on the Al (110) slab. The
built Al (110) slab had an improved surface area and its
periodicity changed by constructing a 12 × 10 supercell with
a vacuum slab of thickness 20 Å. The resulting layered struc-
ture (Fig. 8) contains the Al (110) slab, a polymeric cluster
of PVAc molecules and the vacuum.
Quantitative evaluation of binding energy of adsorp-
tion ­(EBinding energy) between the polymeric cluster of PVAc
molecules and the Al crystal (110) surface was computed
according to Eq. (13):
[ ]
EBinding energy = ETotal − EAl + EPVAc
(13)
J Bio Tribo Corros (2017) 3:53 Page 11 of 13  53

Fig. 7  Representative of snapshots of a side view, b front view and c the Al slab). The purple dotted lines depict close contact interactions
top view of PVAc single molecule on the Al crystal (110) surface (Al between the molecule and the surface (Color figure online)
atoms on the surface plane are represented by the larger spheres on

Fig. 8  Representative of snapshots of a polymeric cluster of opti- plane are represented by the larger spheres on the Al slab). The pur-
mized PVAc molecules, b front view side and c side view of PVAc ple dotted lines depict close contact interactions between the mole-
molecules on the Al crystal (110) surface (Al atoms on the surface cule and the surface (Color figure online)

ETotal is the energy of the polymeric cluster of PVAc Then, E PVAc is the energy of the polymeric cluster of
molecules and Al crystal (110) surface and E Al is the PVAc molecules without the Al crystal (110) surface and
energy of the Al crystal (110) surface without the polymer. EBinding energy = − 834.08373208 kcal/mol. The negative

13
53 
Page 12 of 13
value of binding energy obtained corresponds to a stable
adsorption structure. The binding energy of adsorption is
enhanced by increasing the number of PVAc molecules on
the Al surface as expected, thus suggesting that polymeric
cluster of PVAc molecules interacts more strongly with the
Al (110) surface than the single molecule. This scenario
could be linked to the observed fashion of rapidly increasing
inhibition efficiency with increase in PVAc concentration
and probably responsible for the enhanced inhibition effi-
ciency of PVAc as observed experimentally.
4 Conclusions
The use of vital tools such as weight loss measurement,
polarization measurement and computational techniques to
study the corrosion of aluminium in 2 M ­H2SO4 and 0.5 M
HCl solution has indicated that PVAc is a good inhibitor
within the medium. Results of weight loss showed that PVAc
retarded aluminium corrosion in 2 M H ­ 2SO4 and 0.5 M HCl
solution. The inhibition efficiency was found to increase as
the inhibitor concentration increases, but decreased with a
rise in temperature in the both acid environments, thus show-
ing that increase in the inhibitor concentration increased the
charge transfer resistance of the aluminium surface, whereas
an increase in temperature decreased the resistance. Also,
aluminium coupons showed better stability in sulphuric acid
compared to hydrochloric acid, and calculated values of
thermodynamic studies suggest physical adsorption. Polari-
zation measurements have shown that PVAc is a mixed-type
inhibitor and regulated both the cathodic and anodic partial
reactions with predominant control of anodic effect. Calcu-
lated values of some quantum chemical parameters such as
the energy of highest occupied molecular orbital (EHOMO),
the energy of lowest unoccupied molecular orbital (ELUMO),
an energy gap (∆E = ELUMO –EHOMO) and electronic density
showed that the PVAc molecule should be adsorbed readily
on a corroding aluminium surface. Finally, it could deduce
from the study that performance of PVAc as a corrosion
inhibitor for aluminium in 2 M ­H2SO4 and 0.5 M HCl solu-
tion is dependent on concentration inhibitor, temperature,
time and corrosion agent.
Acknowledgements  The authors are grateful to Electrochemistry
and Materials Science Research Laboratory, FUTO and Department
of Polymer and Textile Engineering, Federal University of Technology,
Owerri Imo State Nigeria, for providing some equipment that made this
research work successful.
Compliance with Ethical Standards  the corrosion of aluminium in hydrochloric acid. Mater Chem Phys
Conflict of interest  Authors declare no conflict of interest regarding
the publication of the article on behalf of all authors.
13
J Bio Tribo Corros (2017) 3:53
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