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Application of Polyaniline in Corrosion Protection of Metals
Application of Polyaniline in Corrosion Protection of Metals
Polyaniline is probably the most investigated electroconducting polymer. This popularity is a result of
its important features: existence of various oxidation states, electrical and optical activity, low cost
monomer, red/ox reversibility, environmental stability, ease of both chemical and electrochemical
synthesis etc. These unique features are partly inherited from its polymeric origin and partly aroused
from its conductivity and could be considered for practical application in: electrochemical systems for
energy storage and conversion, electronic devices, electromagnetic and microwave shielding
materials, sensors, biosensors and corrosion protection as well. The motivation of application of
polyaniline in corrosion protection of metals and alloys is replacement of environmentally hazardous
materials, e.g. chromates in coating systems. Up to day, lot of studies on various metals both on iron,
steels and non-ferrous metals and alloys were performed. The studies involve investigation on
individual polyaniline coatings and polyaniline in coating systems. Owing to variation in experimental
procedure (substrate, substrate preparation, coating type, corrosion environment, test method etc..) it
is unlikely to propose unique mechanism for corrosion protection of metals in the presence of
polyaniline. However, most of the literature is interpreted in terms of general mechanisms of corrosion
protection, barrier and anodic protection.
Key words: electroconducting polymers, polyaniline, coatings, corrosion protection
1. INTRODUCTION 1600
containing polyaniline powders [2, 3]. Polyaniline can monomer, are high and provokes either dissolution, or
be obtained by both chemical and electrochemical formation of non-conducting passive layers on active
oxidative polymerization of aniline monomer [4-7]. metals.
Chemical polymerization is used when large quan- The comprehensive insight into the mechanisms
tities of polymer are required, to date; it has been the of corrosion protection of metals by polyaniline is
major commercial method of polyaniline preparation. very difficult owing to the variations in experimental
Electrochemical polymerization allows direct depo- approach, involving different coating types, metal
sition of polyaniline in the form of coating, facilita- preparation prior to coating, differences in both com-
ting further analysis. On the other hand, electro- position of corrosion environment and test methods
chemical synthesis can also be useful for production etc. Most of the literature is interpreted relying to
of polyaniline powder [7]. classical mechanism of corrosion protection, although
some alternative mechanisms were also reported,
especially in the case of iron and steels [2, 3, 8, 9].
38.23% 22.56%
2. POLYANILINE
The unique property of polyaniline, unlike all
other electroconducting polymers, is existence in dif-
ferent forms depending on degree of oxidation,
4.86%
corrosion 1.74% known as: leuoemeraldine, emeraldine and perningra-
1.39%
batteries niline. Leucoemeraldine, eg. leucoemeraldine base,
sensors refers to fully reduced form; emeraldine, eg. Emerald-
solar cells 31.23%
electrocnics
dine base, is half-oxidized, while perningraniline, eg.
other perningraniline base, is completely oxidized form of
polyaniline. The most conducting form of polyaniline
Figure 2 - Scientific papers published on application is emeraldin salt, obtained by doping or protonation
of polyaniline categorized into various topics. of emeraldine base [8].
The mentioned polyaniline forms can be easily
Although easily performed on inert anodes, elec- mutually converted by both chemical and electro-
trochemical synthesis of polyaniline faces problems chemical reactions, as seen in Figure 3 [6,9].
when deposition is required on active metals, since
the potentials, necessary for oxidation of aniline
Apart from the changes in oxidation levels, all the For the purposes of corrosion protection, poly-
transitions among polyaniline forms are manifested aniline, obtained by chemical polymerization, is used
by color and conductivity changes. The conducting in the form of powders lately mixed into common
protonated emeraldine in the form of green binders, or polyaniline is deposited or from organic
emeraldine salt, obtained as a product of both chemi- solvents (usually toluene or N-methyl-2-pyrrolidone).
cal and electrochemical polymerization of aniline in Similarly, electrochemical synthesis is used for direct
acidic electrolytes, can be easily transformed by deposition onto metals and alloys, but electroche-
further oxidation to fully oxidized dark blue mical synthesis can also be used for production of
perningraniline salt, which can be treated by alkali to polyaniline powder. The mechanism of chemical and
form violet perningraniline. Emeraldine salt can also electrochemical synthesis procedures is quite similar,
be reduced to transparent leucoemeraldine, or can be involving redox initiated formation of radical cation.
transformed by alkali to blue non conducting The advantage of electrochemical synthesis is avoi-
emeraldine. Both reduction of emeraldine salt to dance of usage of oxidants, while the advantage of
leucoemeraldine and oxidation to perningraniline chemical synthesis is capability of obtainning large
states are followed by decrease in conductivity [9]. quantities of polyaniline. Commercially available,
The existence of polyaniline in various oxidation products for corrosion protection, based on po-
forms and knowledge on its mutual transformations is lyaniline, such as: Versicon, CorrPassiv or
of great importance for the interpretation of possible PANDA, all uses polyaniline obtained by chemical
corrosion protection mechanisms. Fact that synthesis [2].
polyaniline possess redox activity, and that relative
2.1. Chemical synthesis
electrode potential of polyaniline, as seen in Table 1.
is grater than those of active metals, alloys and Chemical synthesis of polyaniline requires
chromate couple, implies its beneficial interaction oxidizing force supplied by chemical oxidant (redox
with active metals and alloys altering their corrosion initiator). The most widely employed oxidant is
behavior [2] (NH)4S2O8, but other oxidants can also bi used such
Table 1 - Relative electrode potentials for different as: FeCl3, Ce(SO4)2, K2Cr2O7, H2O2 etc. [11].
redox couples involved in corrosion Strong acidic solution is required for assist the
Redox couple Er (vs. SHE at pH 7) solubilization of aniline and to avoid formation of low
molecular weight oligomers and branching [4,5]. The
Fe/Fe2+ -0.62 chemical polymerization of aniline proceeds
2+
Zn/Zn -0.76 according to schematic presentation in Figure 4.
Al/Al2O3 -1.96
2+
Mg/Mg -2.36
2-
CrO4 /Cr2O3 0.42
POLIANILINE 0.60 - 1.0
protective coatings. As stated before, the main since the potential required for initiation of the pyrole
advantage of electrochemical synthesis is avoidance monomer polymerization is significantly lower [13].
of oxidants, leading to a high purity product. Direct Other approach involves used of chelating agents,
deposition of polyaniline onto so called inert anodes, such as alizarine [14]. The use of chelating agents is
such as: graphite, Pt, various carbons, ITO glass etc. common procedure in the electroplating industry.
is easy to perform. The electrolyte is consisted of With respect to its nature, which can be hydrophilic
aqueous solution of aniline monomer and acid. The or hydrophobic, chelating agent can lead to
polymerization of aniline proceeds together with passivation of the metal by a salt, or by a blocking
insertion of anions (dopants) originated from the acid, compound. Alizarin is hydrophobic type chelating
according to: agent, and its role is explained by the formation of
(PANI)n + nyA- [PANIy+ (A-)]n + nye- (1) more than one coordinate bond with a metal and by
suppressing of the hydrogen evolution reaction by
Where y refers to doping degree, ratio between blocking the metallic surface for hydrogen adsorption
the number of charges in the polymer and the number [18].
of monomer units [12].
The common experimental techniques used for
In order to produce powders of polyaniline, elec- electrochemical polymerization of aniline are: cyclic
trochemical polymerization is performed on graphite voltammetry (potentiodynamic), galvanostatic and
plates (anode) in aqueous acidic electrolytes, and the potetntiostatic techniques. Polymerization using
polymer product is peeled of the electrode and lately cyclic voltammetry is characterized by cyclic regular
transformed to emeraldine or eleraldine salt. change of the electrode potential and the deposited
Since the potential required for initiation of ani- polymer is, throughout the experiment, changing
line polymerization is high ( 0.9 V) direct deposition between its non-conducting and conducting (doped)
of polyaniline on metals and alloys to be protected, is state, followed by exchange of the electrolyte through
faced to specific problems of, either metal disso- polymer [19]. Potetiostatic technique provides
lution, or formation of low conductive oxides at the polymerization at constant potential, this technique is
potentials required for oxidation of aniline monomer less used since the potential required for initiation of
[13-17]. These problems can be overcome by the pro- the aniline polymerization, as already stated, is high,
per choice of electrolyte, or by surface pre-treatment. which can lately caused overoxidation of the film and
formation of degradation products. Galvanostatic
Electrolyte has to meet the requirement of passi-
technique enables polymerization to occur at constant
vating the metal with non insulating passive (or pseu-
rate (current), so the mass or thickness of the polymer
dopassive) film that could enable further undisturbed
can be adjusted by altering the polymerization time.
deposition of polyaniline.
The most popular electrolyte for electrochemical 4. CORROSION PROTECTION IN THE
deposition of polyaniline on steel, aluminum its al- PRESENCE OF POLYANILINE
loys, copper and brass is doubtless oxalic acid. The
formation of pseudo-passive film based on oxalate is It is experimentally evidenced that polyaniline
evidenced, enabling efficient deposition of polyani- was efficient in corrosion protection of active metals
line [2]. Recently, it was observed that aqueous ele- and their alloys. The literature dealing with protective
ctrolyte containing aniline and sodium-benzoate can features of polyaniline is extremely rich; polyaniline
be used for galvanostatic electrochemical synthesis of is applied in the form of individual coating or as a
protective polyaniline on mild steel, aluminum and component of a coating system. Owing to variety of
copper as well [3, 15-17]. materials, corrosion environments, differences in coa-
The surface pre-treatment involves either depo- ting procedure and coating types, different substrate
sition of electroconducting polymer obtained from pre-treatments, and differences in testing methods, it
easily oxidized monomer e.g. polypyrrole, after is practically impossible to establish the unique mec-
which the deposition of polyaniline was facilitated, or hanism of corrosion protection in the presence of po-
pre-treatment with some chelating agent. lyaniline based coatings. Moreover, there are contra-
dictory reports on which form, emeraldine base or
Polyaniline was impossible to grow onto zinc emeraldine salt provides better protection [2].
electrode from acidic electrolyte containing aniline
monomer. Camalet et al. was observed that aniline 4.1. Experimental techniques
was easily polymerized onto zinc from acidic aqueous The estimation of protective properties of poly-
electrolyte onto previously deposited thin layer of aniline based coatings often involves visual obser-
polypirrole. The polypyrrole pretreatment was chosen
vation and application of both electrochemical and Electrochemical impedance spectroscopy (EIS) is
non-electrochemical experimental techniques. intensively used in determination of the protection
The results of visual observation are usually gi- efficiency of commercial protective coatings [20], but
ven as photographs of simples with polyaniline based it is also very popular in the field of corrosion pro-
coatings exposed to the corrosion environment; these tection by electroconducting polymers. The operation
results unambiguously indicate protection by poly- principle of EIS involves interpretation of the system
aniline. response to the application of an input signal in the
The most popular electrochemical techniques form of sinusoidal potential of small amplitude. The
used for estimations of the protection efficiency of response of the system is obtained in the form of
polyaniline based coatings involve determination of sinusoidal current. Impedance is practically transient
the open circuit potentials, polarization measurements function of this non linear system. Impedance data are
and electrochemical impedance spectroscopy. referred in either complex plane (Nyquist diagrams)
or in frequency plane (Bode diagrams). These results
Determination of the open circuit potentials is
probably the first step in a corrosion study. The can be interpreted qualitatively or quantitatively using
movement of the corrosion potential to a more model called electrical equivalent circuit, whose
positive region for simples protected by polyaniline parameters are related to corrosion process and
based coatings and its dependences during exposure features of the coating [20]. EIS experiments for
to corrosion environment is used as a evidence of corrosion studies are practically always performed at
protection, moreover it is not rarely used to support open circuit potentials.
the mechanism of anodic protection. The common electrical equivalent circuit used in
Polymerization measurements are used to deter- interpretation of EIS results of commercial organic
mine corrosion current density and sometimes the coating is given in Figure 6., but it is very often used
corrosion potential, which are the most reliable para- for modeling of the corrosion process of the metals in
meters for the precise information on protection effi- the presence of polyaniline based coatings.
ciency of a coating. In Figure 5. determination of the
protection efficiency of the benzoate doped polya-
niline coating on copper exposed to 0.5 mol dm-3
NaCl is given [14].
0.0
2 1
-0.2
The equivalent circuit presented in Figure 6. is
particularly useful for evaluation of corrosion
protection enchainment of organic coatings when
-0.3
jcorr = 3.1 A cm
-2 polyaniline modification is used.
The meaning of the circuit parameters is as
folows: Rel, electrolyte resistance, Rp, electrolyte
-0.4
10
-8
10
-7
10
-6
10
-5
10
-4 -3
10
-2
10
-1
10 resistance in the pores of the coating, Rct, charge
-2 transfer resistance related to corrosion process (often
j / A cm
called polarization resistance), Cc, coating capa-
Figure 5 - Potentiodinamic polarization curves citance, CPE, constant phase element that can be
(v = 1 mV s-1) of: 1- copper and 2- copper with sometimes substituted with double layer capacitance.
polianiline coating in 0.5 mol dm-3 NaCl.
Other electrical equivalent circuits can be also
found in the literature. Shauer et al [21]. used
Using data on corrosion current density from the modified electrical equivalent circuit for steel with
Figure 5 it was possible to determine the protection polyaniline commercial (Omecron) based primer
efficiency, which was estimated to nearly 96 %. and epoxy top coat, given in Figure 7.
2
-8
10
Rp, Rct / cm
Rp
tion of the physical meaning of these elements. For
Cc / F cm
similar coating system with deliberately made defect,
4
10
Kinlen et al. [22] used even more complex equivalent
-2
circuit, given in Figure 8. New resistance, Rox, origin- Rct -9
10
nated from the oxide formed in the defect and 3
10 Rp
polyaniline capacitance, CPANI, were added to the
equivalent circuit.
-10
2
10 10
0 100 200 300 400 500 600 700 800
t / days
given in studies when deliberately made defects were polymer/solution, altering the passive state of the
introduced into polyaniline based coatings. Pud et al. metal. Cathodic and anodic half reactions were
have studied corrosion protection of mild steel coated separated and the increase in pH at the metal surface
by polyaniline primers with epoxy top coat and epoxy is prevented which helped in maintaining stabile
alone, a hole was drilled through coatings to the metal oxides [21].
surface [27]. The corrosion rate for mild steel coated
by polyaniline/epoxy was significantly lower 5. CONCLUSIONS
comparing to epoxy coating alone. The similar It is experimentally evidenced that polyaniline
foundlings were observed for scribed samples with based coatings had offered ability of corrosion
polyaniline based primers [22, 28]. protection of metals. The establishment of a unique
Anodic protection mechanism is widely used to mechanism of corrosion protection is practically
describe protection of metals in the presence of impossible, since it is dependent on type of metal,
polyaniline based coatings. It means that polyaniline coating, corrosion environment etc. However, some
metal interface is modified to produce passivating general concepts are known, and most of the literature
layers with charge transfer reaction occurring is interpreted in terms of barrier and anodic protection
between the metal and polyaniline. The anodic mechanisms. There is a still growing interest in
protection mechanism is recognized by moving of investigation of polyaniline for the purposes of
corrosion potential to passive region for the chosen corrosion protection.
metal and corrosion environment. This means that, in
6. Acknowlegment
order to achieve passivation, the corrosion potential
must be shifted anodically (ennobled), to the passive This work was supported by the Ministry of
region. However, the value of the passivation Education and Science, Republic of Serbia, Project
potential is dependent on the composition and nature No. 172046
of the corrosion media and type of the coated metal or
alloy. 7. REFERENCES
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IZVOD