Bull. Mater. Sci., Vol. 31, No. 1, February 2008, pp. 37–41. © Indian Academy of Sciences.

Chemical treatment of zinc surface and its corrosion inhibition studies

S K RAJAPPA†, T V VENKATESHA* and B M PRAVEEN

Department of PG Studies and Research in Chemistry, School of Chemical Sciences, Kuvempu University,
Shankaraghatta 577 451, India
†
Department of Chemistry, Kalpataru Vidya Samsthe, Tiptur 572 202, India

MS received 22 August 2007; revised 11 October 2007

Abstract. The surface treatment of zinc and its corrosion inhibition was studied using a product (BTSC)
formed in the reaction between benzaldehyde and thiosemicarbozide. The corrosion behaviour of chemically
treated zinc surface was investigated in aqueous chloride–sulphate medium using galvanostatic polarization
technique. Zinc samples treated in BTSC solution exhibited good corrosion resistance. The measured electro-
chemical data indicated a basic modification of the cathode reaction during corrosion of treated zinc. The cor-
rosion protection may be explained on the basis of adsorption and formation of BTSC film on zinc surface.
The film was binding strongly to the metal surface through nitrogen and sulphur atoms of the product. The
formation of film on the zinc surface was established by surface analysis techniques such as scanning electron
microscopy (SEM–EDS) and Fourier transform infrared spectroscopy (FTIR).

Keywords. Corrosion; inhibitors; electrochemical measurement; zinc.

1. Introduction metal from the corrosive medium (Praveen et al 2007).

This reduced the formation of white rust. Several chelat-
Zinc is an important metal with numerous industrial appli- ing agents showed corrosion inhibition of zinc. These
cations and is mainly used for the corrosion protection of substances form stable, almost insoluble films with zinc
steel (Barcelo et al 1988; Lin et al 1991; Rajendran et al surface through their electro active groups and acts as
1997; Bozzini et al 1999). The zinc coated steel materials protective coatings (Leroy and Zavorski 1977; Leroy 1977).
provide a greater resistance to corrosion, but when exposed In the present investigation, a compound, BTSC, was
to humid atmosphere, it undergoes rapid corrosion with synthesized and used for anticorrosion of zinc. This syn-
the formation of corrosion products known as white rust. thesized molecule contains nitrogen and sulphur atoms
This is generally observed on galvanized materials and and favours the formation of a film on zinc surface. The
renders the plated zinc materials unsuitable for industrial inhibition effect was studied in aqueous corrosive solu-
applications. The formation of the white rust on zinc sur- tion using polarization technique. The mechanism of co-
face is prevented by the application of chromate treat- rrosion inhibition was explained on the basis of formation
ment (Muller et al 2004). The effluent obtained during of protective layer on the zinc surface.
chromate treatment induces the environmental pollution.
But recent environmental regulations restrict the use of
chromate solution and recommended its replacement with 2. Experimental
other non-toxic and, non-polluting agents (Hinton and
Wilson 1989). Therefore, there is a need for change in the The pure zinc plate (Cu = 0⋅185, Al = 0⋅006%, Fe = 0⋅004%,
formulation of corrosion inhibition by an increasing de- Mn = 0⋅3%, Sn = 0⋅003%, Pb = 0⋅002%, Cd = 0⋅002% and
mand for reduced environmental impact. the rest zinc) was selected and coupons of desired shapes
The zinc or zinc-coated materials treated with a solution (5 cm × 1 cm × 4 mm) were prepared. These samples were
of organic compounds provided effective corrosion protec- polished with SiC papers of different grit sizes (200–
tion. These compounds containing nitrogen and sulphur 1200). The electrodes were degreased with trichloroethylene
elements are capable of forming thin film or molecular vapours to remove oil and grease. The samples were
layers on the metal surface (Abdel Aal et al 1983; Lakhan rinsed with ethanol, followed by distilled water wash. The
Jha et al 1991; Maja et al 1993; Rajappa and Venkatesha prepared samples were immersed in the treatment solu-
2003). The role of this film is to isolate the corroding tion for different time intervals.
Benzaldehyde thiosemicarbazone (BTSC) was synthe-
sized from the addition reaction followed by loss of water
*Author for correspondence ([email protected]) between benzaldehyde and thiosemicarbozide (Morrison

37
38 S K Rajappa, T V Venkatesha and B M Praveen

and Boyd 1973). The purity of the compound was moni- The corrosion of untreated zinc in aerated chloride–
tored by TLC and then characterized by IR studies. The sulfate solution was found to be cathodically controlled
chemical structure of the BTSC compound is given in (Deslouis et al 1989). The corrosion current density was
figure 1. The zinc specimens were degreased and their obtained by extrapolation of Tafel lines. The corrosion
surface activated by dipping in 10% HCl for 1 min. The current density, Icorr and corrosion potential, Ecorr, were
activated zinc surface was water washed before subject- found to be 89 μA cm–2 and –1005 mV, respectively.
ing it into surface treatment process. The concentrations The polarization curves of the zinc samples treated at
of 2%, 4% and 6% BTSC solution were prepared in etha- 298 K for 3 h in 2% and 4% BTSC solutions (curves 2
nol and used as zinc treatment solution. The zinc speci- and 3) are also presented in figure 2. The corrosion po-
mens were immersed in these solutions for different tential of treated zinc shifted positively by 20–40 mV in
immersion periods (1–3 h) at room temperature. After the comparison to untreated zinc. The zinc samples treated in
treatment, the zinc samples were washed with water and 4% BTSC solution exhibited higher corrosion resistance,
dried in air. The treated samples were subjected to elec- indicating that the surface exposed to the corrosive me-
trochemical studies. dium is less active, due to the improvement of the surface
The electrochemical investigations were performed in coverage by the compound. Further the cathodic curves 2
aqueous solutions of 0⋅2 M NaCl + 0⋅2M Na2SO4 by means and 3 revealed that the second plateau of curve 1 progre-
of a galvanostatic technique. A conventional three-electrode ssively disappears with the concentration of BT solution.
cell consisting of zinc sample (exposed surface area, This indicated a basic modification in the cathodic beha-
1 cm–2) as working electrode, saturated calomel and plati- viour of zinc metal. The second plateau of curve 1 be-
num were used as reference and counter electrodes, re- comes almost linear in curve 3. This may result from the
spectively. The anodic and cathodic polarization curves formation of porous layer during the preliminary hold
for the treated and untreated zinc electrodes were taken time at the free corrosion potential and decreasing the
using a potentiostat/galvanostat (Elico CL 95). Anodic electron transfer rate. In this case, Icorr and Ecorr were ob-
and cathodic polarization potentials were recorded in the tained by extrapolation of the linear part of the cathodic
current density range of 0–10 mA/cm2. polarization curves. Further the Ecorr values indicated that
The surface morphology of the treated and untreated the treated zinc surface is relatively more noble than un-
zinc samples was investigated by scanning electron mi- treated zinc.
croscopy using a SEM–JSM–850 (Jeol) machine with The percentage inhibition efficiency (%IE) was calcu-
EDS link. Fourier transform infrared spectroscopy (FTIR) lated using the relation,
spectra were recorded using KBr pellets to characterize 1
the reaction product and scrapped compound of the cor- I corr − I corr
%IE = × 100,
roded surface. I corr

where Icorr and I1corr denote the corrosion current densities

3. Results and discussion for the untreated and treated zinc.
Table 1 shows the values of Ecorr, Icorr and %IE of the
3.1 Electrochemical investigation
treated and untreated zinc. The values of Ecorr shifted to-
Figure 2 gives the cathodic and anodic polarization
curves for treated and untreated zinc. Curve 1 of cathodic
polarization exhibits two diffusion plateaus for untreated
zinc. This was due to reduction of dissolved oxygen. The
oxygen reduction (first plateau) occurs in the vicinity of
the corrosion potential through a more or less porous layer.
This layer consists of corrosion products and it is formed
during the short preliminary hold time at the free corrosion
potential. At higher cathodic over potentials the whole
surface becomes active, hence oxygen reduction at higher
rate takes place (at the layer solution interface) resulting
in an increase in current density (second plateau) (Deslouis
et al 1984).

Figure 1. Structure of BTSC compound. Figure 2. Polarization curves for treated and untreated zinc.
 Chemical treatment of zinc surface and its corrosion inhibition studies 39

wards noble direction and the values of Icorr were found to jected to corrosion study at different temperatures. The
decrease in treated zinc surface. The %IE was greater in %IE was decreased regularly with rise of temperature.
4% BTSC than in 2% solution for the same immersion The decrease of %IE was more at temperature, 308 on-
period. The concentration of BTSC is increased to 6% wards. Therefore, the formation of protective film is more
and the percentage inhibition efficiency was found to be predominant at relatively low temperature. The variation
slightly increased. Therefore, 4% BTSC solution was of %IE with temperature is shown in figure 6.
taken as optimum concentration.
4. Surface analysis techniques
3.2 Effect of treatment time
Surface analysis technique was carried out to confirm the
Figure 3 shows the cathodic and anodic polarization curves formation of a protective film on the zinc surface and
of zinc at different treatment times. Figure 4 shows the also to investigate the establishment of chemical bonds
influence of immersion time on percentage inhibition between the electro active groups (–NH, –SH) of the
efficiency. The inhibition efficiency was gradually in- compound with zinc surface. The following techniques
creased with increase in immersion period up to 3 h in were used.
4% BTSC solution. The increase in the inhibition effi-
ciency values was related to the progressive formation of
4.1 SEM–EDS examination
a protective film on the electrode surface. The inhibition
efficiency after 3 h was stabilized and reached a maxi-
Scanning electron microscopic study was performed to
mum value of 88%.
investigate the change of morphology of the zinc surface.

3.3 Effect of temperature

Figure 5 shows the cathodic and anodic polarization

curves of zinc at different temperatures. The zinc speci-
mens were treated in 4% BTSC solution for 3 h and sub-

Table 1. Values of Icorr, Ecorr and %IE of treated zinc for 3 h

at 298 K.
Conc. of inhibitor Ecorr (mV) I1corr (µA cm–2) %IE

Blank –1005 89 (Icorr) –

2% –975 27 69
4% –962 12 87
6% –960 11 88
Figure 4. Influence of immersion time on percentage inhibi-
tion efficiency.

Figure 3. Cathodic and anodic polarization curves of zinc at Figure 5. Cathodic and anodic polarization curves of zinc at
different intervals of time. different temperatures.
40 S K Rajappa, T V Venkatesha and B M Praveen

Figure 7a shows the photomicrograph taken after 10 min

of anodic polarization in 0⋅2 M NaCl + 0⋅2 M Na2SO4
solution at 298 K. The surface contained small cavities,
which are distributed over the entire surface and a needle-
like deposit (corrosion product) was observed. In the case
of treated sample taken after 10 min of anodic polariza-
tion, needle type of deposit was not observed (figure 7b).
The surface shows only a few pits covered with corrosion
products. This indicates a film of BTSC which hindered
the dissolution of metal during anodic polarization. So
Figure 6. Temperature effect on Icorr and % IE of treated zinc. less pits and corrosion products were noticed. Figure 7c
showed a passive film, which was not subjected to the
corrosion process.

4.2 EDS studies

Figure 8a shows the EDS spectra of corroded zinc sur-

face. Chloride peak was observed due to the possible
formation of zinc salts of chloride around the anode sites
of the corroding surface. For the treated zinc, the chloride
peak was not observed and the observed sulphur signal
originated from the BTSC molecule as shown in figure
8b. This observation inferred that the molecule interacted
strongly with the metal through sulphur atom.

Figure 7. SEM micrographs of a. anodic polarized untreated

zinc surface, b. anodic polarized treated zinc surface and c. Figure 8. EDS spectra of a. corroded untreated zinc and b.
treated zinc surface. corroded treated zinc.
 Chemical treatment of zinc surface and its corrosion inhibition studies 41

sorption frequencies of IR spectra supported the interac-

tion between functional group of BTSC with surface of
metal.

5. Conclusions

Electrochemical study showed that zinc treated with

BTSC molecule has good corrosion resistance in aqueous
chloride–sulphate solution. Maximum inhibition effi-
ciency of 87% was obtained in 4% BTSC solution at
298 K. The treatment induced a basic modification in the
cathodic behaviour of zinc and controls the corrosion by
decreasing the electron transfer rate. The SEM photo-
graphs showed the formation of a passive film on the
treated zinc surface. The spectral data confirmed the for-
mation of a stable film and it is strongly attached to the
zinc surface through the establishment of chemical inter-
actions with N and S atoms. The synthesized BTSC
molecules modified the zinc metal surface and provided
good corrosion protection.

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