J. Mater. Sci. Technol., 2011, 27(4), 309-316.

Antibacterial Properties and Corrosion Resistance of Nitrogen-doped

TiO2 Coatings on Stainless Steel

Hefeng Wang1,2) , Bin Tang1)† , Xiuyan Li1) and Yong Ma1)

1) Research Institute of Surface Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2) School of Physics and Electronic Science, Shanxi Datong University, Datong 037009, China
[Manuscript received December 15, 2010, in revised form January 23, 2011]

The Nitrogen-doped TiO2 (N–TiO2 ) coatings were fabricated on 304 austenitic stainless steel (SS) substrates
by oxidation of titanium nitride coatings, which were prepared by plasma surface alloying technique. Mi-
crostructural investigation, corrosion tests and antibacterial tests were conducted to study the properties of
N–TiO2 coatings. Composition analysis shows that the SS substrates were shielded by the N–TiO2 coatings
entirely. The N–TiO2 coatings are anatase in structure as characterized by X-ray diffraction. The corro-
sion properties of N–TiO2 coated SS samples in Hanks’ solution were investigated by a series of tests. The
electrochemical measurements indicate that the corrosion potential positively shifts from −0.275 V for un-
trated SS to −0.267 V for N–TiO2 , while the corrosion current density decreases from 1.3×10−5 A/cm2 to
4.1×10−6 A/cm2 . The corrosion resistance obtained by fitting the impedance spectra also reveals that the
N–TiO2 coatings provide good protection for SS substrate against corrosion in Hanks’ solution. Electrochem-
istry noise tests indicate that the N–TiO2 coatings effectively retard the local pitting and crevice corrosion of
the SS substrate. The results of the antibacterial test reveal that N–TiO2 coatings give 304 austenitic SS an
excellent antibacterial property.

KEY WORDS: Titanium dioxide; Nitrogen doping; Stainless steel; Corrosion; Antibacterial
property

1. Introduction tive approach to antibacterial agents was performed

Since the sanitation and health are increasingly
given particular attention today, daily appliances
are increasingly being designed with antibacterial
features. Austenitic stainless steels, such as 304
austenitic, are widely applied in industrial and suit-
able for biomedical applications, because they exhibit
superior corrosion resistance and workability. How-
ever, they do not possess antibacterial properties. In-
flammation and infection, which are usually caused by
adherence and colonization of bacteria on biomateri-
als, make patients develop serious complication[1–3] .
Thus, in order to enhance the antibacterial capabil-
ity on the surfaces of biomedical devices, an effec-
† Corresponding author. Prof., Ph.D.; Tel.: +86 351 6010540;
Fax: +86 351 6018760; E-mail address: tangbintyut@163.com
(B. Tang).
by means of surface coating techniques to increase its
antibacterial and mechanical properties[4–10] .
Titanium nitride coatings have become universally
accepted coatings due to their good mechanical prop-
erties, such as hardness and wear resistance and bio-
compatibility. The major applications of the coatings
are protective coatings on steels, diffusion barriers in
integrated circuit industry, and decorative coatings.
Recently, it has been reported that TiN oxidation
is an effective way to synthesize N-TiO2 . Morikawa
et al. synthesized N-doped rutile TiO2 by oxidation
of TiN[11] . Cui et al. also reported the synthesis of
Nitrogen-doped titanium dioxide by oxidative anneal-
ing the resulted TiN thin film in air[12] . If the method
of TiN oxidation is used for the formation of N-doped
TiO2 coatings on SS substrate, the adhesion strength
between coatings and substrate should be taken into
310 H.F. Wang et al.: J. Mater. Sci. Technol., 2011, 27(4), 309–316

account.
The plasma surface alloying technique is a very
promising surface engineering technique[13] . One of
its advantages lies in no element mutation between
surface alloying layer and substrate interface. A du-
plex surface alloying layer composed of surface coat-
ings and inner diffusion layer can be formed by using
this technique. The component of elements in the dif-
fusing layer changes gradually which can enhance the
load-bearing capacity to the coatings and ensure the
durability of the coatings.
In principle, N–TiO2 coatings on metal substrate
could be directly obtained by using the plasma sur-
face alloying technique, in which titanium target is
sputtered in Ar/O2 /N2 mixture gas. Here two key Fig. 1 Sketch of plasma surface alloying technique
points should be taken into account. Firstly, oxygen
and nitrogen would lead to “target poisoning”, which temperature of 950◦ C for 3 h. All the resulted TiN
affects the stability of the process parameters and the coatings were subsequently annealed in air at 450◦ C
deposition rate. Secondly, in glow discharge sputter- for 2 h to oxidize and crystallize the samples.
ing, the temperature of the substrate is higher than
800◦ C, which would result in the formation of rutile 2.3 Characterization
TiO2 coatings, rather than the anatase TiO2 coatings
with good photocatalytic properties. The surface morphology of the N–TiO2 coatings
was observed by scanning electron microscopy (SEM,
Based on these considerations, the N–TiO2 coat-
LEO438VP). The chemical composition of the alloyed
ings were prepared by a two-step processing in this
layer was examined by glow discharge optical emission
work. Firstly, the TiN coatings on SS substrate were
spectrometry (GDOES-750). The composition was
deposited by plasma surface alloying technique. All
determined by VG ESCALAB Mark II X-ray photo-
the resulted TiN coatings were subsequently annealed
electron spectroscopy (XPS) with AlKα X-ray as the
in air at 450◦ C for 2 h to oxidize. The antibacterial
radiation source. An X-ray diffraction (XRD, Siemens
property and corrosion resistance of the N–TiO2 coat-
D500) with the 0.154 nm CuKα line as the excitation
ings were studied.
source was employed to identify the crystal structure
of the coatings.
2. Experimental
2.4 Corrosion experiments
2.1 Experiment materials
The electrochemical behaviors of the samples were
The 304 SS samples (Φ20 mm×5 mm) were measured using an Electrochemical Interface System
grounded with No. 80-1500 emery papers, and then (PS-168) in a three-electrode cell with Hanks solu-
polished with 0.3 and 0.05 μm alumina powder, re- tion as the electrolyte. The electrolyte composition
spectively. Finally, the surfaces of samples were of Hanks solution is listed in Table 1. The N-TiO2
cleaned by ethanol and acetone. The target was a
titanium plate (110 mm×70 mm×5 mm) of 99.9% Table 1 Chemical composition of the Hanks solution
purity.
Components Concentration / (g/L)
NaCl 8.0
2.2 Preparation of the nitrogen-doped TiO2 coatings CaCl2 0.14
KCl 0.4
The N–TiO2 coatings were prepared by a two-step NaHCO3 0.35
processing. Firstly, the TiN coatings were deposited Glucose 1.0
on SS substrates by using plasma surface alloying MgCl2 ·6H2 O 0.1
technique, in which titanium target were sputtered Na2 HPO4 ·2H2 O 0.06
in the Ar/N2 mixture gas. The sketch of the tech- KH2 PO4 0.06
nique is shown in Fig. 1. The process parameters were MgSO4 ·7H2 O 0.06
as follows: the Ar/N2 mixture gas pressure was 30–
40 Pa (flow rate ratio N2 :Ar=1:2), the source voltage coatings coated SS (or untreated SS) was used as the
for supplying Ti elements has been set from −1100 to working electrode, a platinum plate as the counter
−1150 V, the cathode (specimen) voltage was ranging electrode, and a saturated calomel electrode (SCE)
from −500 to −550 V, the distance from the source as a reference to measure the electric potential across
target to the substrate sample was 15 mm, the process the electrochemical interface. The corrosion potential
temperature was raised up to and kept at the desired was determined at a sweeping rate of 1×10−3 V/s in
 H.F. Wang et al.: J. Mater. Sci. Technol., 2011, 27(4), 309–316 311
the range from −1 to 1 V.
The electrochemical impedance spectroscopy
(EIS) measurements were carried out at open circuit
potential, and the applied frequency ranged from 105
to 10−2 Hz.
Electrochemistry noise (EN) monitoring instru-
ment was used to analyze the crevice and pitting cor-
rosion mechanism of N–TiO2 coatings and SS sub-
strate in Hanks solution. For this purpose, an
arrangement consisting of two identical working elec-
trodes and a saturated calomel reference electrode was
used. Electrochemical noise was measured by record-
ing potential and current fluctuations at the free cor-
rosion potential, with a sampling rate of 1 point per
second for a period of 1800 s by using a zero resistance
ammeter connected to a personal computer. Dur-
ing the electrochemical measurements the backsides
of the samples were shielded by corrosion-resistance
silica gels to avoid any possible interference to the
corrosion behaviors of the coatings.

2.5 Antibacterial test

The antibacterial activity of coatings obtained

against S.aureus was studied by using the antibacte-
rial drop-test. Microorganisms were cultured on the
culture medium at 37◦ C for 24 h. Cultured bacteria
were added in 10 ml saline solution to reach approx-
imately the concentration of bacteria corresponding
to 108 colony forming units per milliliter (CFU/ml).
A portion of the saline solution containing the bacte-
ria was diluted to 106 CFU/ml for the drop-method
antibacterial experiments. Samples contained one N-
TiO2 coated SS sample and one uncoated SS used
as a blank. The samples were placed into sterilized
80 mm Petri dishes. Then 100 μl saline solutions
with S.aureus at a concentration of 106 CFU/ml were
added onto the surface of each specimen. The sam-
ples were illuminated with a fluorescent lamp (80 W)
at room temperature and cultured for 4 h. The lamp
was perpendicular to the surface at a distance of 50
cm. After time period, the drops containing bacte-
ria were washed from the sample surface using 5 ml
saline solution in the sterilized Petri dishes. Then 10 Fig. 2 X-ray photoelectron spectral details collected
μl of each bacteria suspension was dispersed on the from N-TiO2 coatings: (a) N 1s, (b) Ti 2p, and
Brain Heart Infusion Agar medium and incubated for (c) O 1s peaks
24 h at 37◦ . The number of surviving bacteria on the
mediums was counted after incubation. N–Ti–N, O–Ti–N and Ti–N–O linkage, respectively.
Sakthivel and Kisch[15] observed an intense peak at
3. Results and Discussion 400.1 eV that was assigned to hyponitrite species and
concluded that the higher binding energy is due to
3.1 Structural characterization the lower valence state of N in N doped TiO2 . Many
researches showed that intense peak at 400 eV are due
The XPS spectra of N–TiO2 coatings are shown to oxidized nitrogen like Ti–O–N or Ti–N–O linkages.
in Fig. 2 for N 1s, Ti 2p and O 1s peaks. Fig- Recently, Gopinath observed N 1s binding energy at
ure 2(a) shows the chemical binding state of N 401.3 eV and claimed the presence of Ti–N–O linkage
1s of the sample. The peak is observed at 399.9 on the surface of N doped TiO2 nano particles[16] .
eV. Dong et al.[14] observed three peaks of N1s at Based on the literature, in the present investigation,
397.8, 399.9 and 401.9 eV which were attributed to the peak at 399.9 eV is ascribed to O–Ti–N, Ti–N–O
312 H.F. Wang et al.: J. Mater. Sci. Technol., 2011, 27(4), 309–316

Fig. 4 SEM images of untreated SS (a) and N-TiO2

coated on SS (b)

Fig. 3 XRD patterns for TiN (a) and N–TiO2 (b) coated
SS samples

linkages in the TiO2 lattice. Figure 2(b) presents that

Ti 2p peaks appear at 458.0 eV and 463.6 eV, which
are attributed to O–Ti–O linkages in TiO2 . Figure
2(c) shows that O 1s peaks appear at 529.3 eV and
531.5 eV, respectively. The O 1s peak at 529.3 eV
is assigned to the lattice oxygen atom of TiO2 , and
the peak at 531.5 eV is closely related to the hydroxyl Fig. 5 Component distribution of N–TiO2 coated SS
groups (–OH) resulting mainly from chemisorbed wa-
ter. The increase in surface hydroxyl content has ad-
vantageous for trapping more photogenerated holes Figure 5 demonstrates the gradient distributions
and thus preventing electron–hole recombination[14] . of elements Ti, N, O, Fe, Cr and Ni in the Ti–N–O
The structural properties of TiN coated SS and N– coatings. The surface modified layer with a thick-
TiO2 coated SS were characterized by XRD, as shown ness of approximate 4.5 μm is composed of a nitrogen
in Fig. 3. Anatase TiO2 phase is formed after anneal- doped TiO2 layer and an inner diffusion layer of about
ing of TiN coatings and no specific peaks of TiN and 3.5 μm and 1 μm thick, respectively. In internal diffu-
SS substrate are detected for the N–TiO2 coated SS sion region, mutual diffusion of Ti and substrate alloy
sample. The results show that the SS is entirely cov- elements occur, causing the mixing of the elements at
ered by the N–TiO2 coatings. the interface between the surface modified layer and
the substrate, which can significantly improve bond-
The SEM image of the as-synthesized N–TiO2
ing strength of the nitrogen doped TiO2 coatings with
coatings is shown in Fig. 4(b). Many three-
SS substrate. It is shown that oxygen content in in-
dimensional homogenous and dense protuberances
terface is obviously higher than that in the surface
can be seen for the N–doped TiO2 coatings. Though
layer. The characteristics of Ti with obvious inside
some polished scratches are also observed in the SEM
oxidation (surface oxygen easily moves to inside) and
image of the untreated SS substrate, as evidenced in
Cr in the substrate with antioxidant migration result
Fig. 4(a). However, scratches, cracks or pinholes can-
in the oxygen gathering phenomena in the interface.
not be seen on the surface of the coatings.
 H.F. Wang et al.: J. Mater. Sci. Technol., 2011, 27(4), 309–316 313

Fig. 6 Polarization curves of untreated SS (a) and N-

TiO2 coated SS (b) in Hanks solution

3.2 Corrosion resistance in Hanks’ solution

Figure 6 shows the Tafel polarization curves of un-

treated SS and the N-TiO2 coated SS. For the un-
treated SS, the corrosion potential (Ecorr ) is about
−0.275 V, while the value is −0.267 V for the N-
TiO2 coated sample. The reason for the shift may
lie in the fact that the existence of the entirely shield-
ing N–TiO2 coatings can diminish the accessibility of Fig. 7 Nyquist plots for untreated SS (a) and N–TiO2
coated SS (b)
the corrosive media to the SS substrate. Corrosion
current density is an important parameter to assess
the kinetics of corrosion reaction, and it is normally
proportional to the corrosion rate[17] . The corrosion
current density of the N–TiO2 coated sample is about
4.1×10−6 A/cm2 , while that of the untreated SS is
1.3×10−5 A/cm2 . The significant reduction in corro-
sion current density implies that the N–TiO2 coatings
can help to decrease the corrosion rate of the SS.
The EIS spectra of the N–TiO2 coated SS and un-
treated SS have also been obtained under open circuit
in Hanks solution. The Nyquist plots of the N–TiO2
coated SS and the untreated SS are shown in Fig. 7, in
which the real axis indicates the resistance to corro- Fig. 8 Bode diagrams for untreated SS (a) and N–TiO2
sion. As shown in the figure, the corrosion resistance coated SS (b)
of the N–TiO2 coated SS (30.23 kΩ) is much larger
than that of the untreated SS (5.45 kΩ), which re- ings. It shows that the coatings acts as an iso-
veals the better corrosion resistance of the SS coated lation layer with large resistance value and small
with N–TiO2 . capacitance[18] . It can be attributed to dense coat-
The Bode impedance plots of the untreated SS ings which are able to inhibit anodic reaction of the
and N–TiO2 coated SS are shown in Fig. 8. Bode Z corrosion process.
impedance plots of N–TiO2 coated SS sample shifts The impedance diagrams are interpreted in terms
towards a higher direction compared with that of the of the equivalent circuit shown in Fig. 9, where Rs is
untreated SS sample at the same frequency. In ad- the resistance of solution, Q1 and Q2 are the constant
dition, it can be observed that Bode Z impedance phase element (CPE). Here, CPE is commonly used
plots showed linear portions at intermediate frequen- to represent capacitance, because it is hardly pure ca-
cies. The slopes of these linear portions were close to pacitance in the real electrochemical process, which
−2.0 (from −0.50 to −0.99). EIS spectra for N–TiO2 can be expressed by admittance Y0 and power index
coated SS exhibit only a near capacitive response il- number n using the following formula[19] :
lustrated by a phase angle close to −90◦ over a wide Q = Y0 (jω)n
frequency range indicating a compact passive coat-
314 H.F. Wang et al.: J. Mater. Sci. Technol., 2011, 27(4), 309–316

Table 2 Values of equivalent circuit parameters determined by modeling impedance

spectra of untreated SS and N–TiO2 coated SS in Hanks solution

Electrode Rs Q1 R1 Q2 R2
Y0 n Y0 n
/(Ω·cm2 ) /(Ω−1 ·cm−2 ·s−n ) /(Ω·cm2 ) /(Ω−1 ·cm−2 ·s−n ) /(Ω·cm2 )
SS 3.5 / / / 5.0 0.88 1.40×104
N-TiO2 4.7 5.8×10−11 0.41 1.0×10−2 3.2×10−5 0.92 2.39×105

ing the equivalent circuits, the impedance parameters

Fig. 9 Equivalent circuit diagrams of impedance spectra
for untreated SS (a) and N-TiO2 coated SS (b)
can be obtained, as listed in Table 2. As shown in the
table, the obtained corrosion resistance R2 for the un-
treated SS and N–TiO2 coated SS is 1.4×104 Ω·cm2
and 2.39×105 Ω·cm2 , respectively. The much higher
resistance value of the N–TiO2 coated SS confirms
that the corrosion resistance of the substrate has been
significantly improved after surface modified. In ad-
dition, due to diffusion effects, n, Q1 and Q2 values of
the coatings are less than 1. The capacitance of the
N–TiO2 coatings is very low (approximately 10−11 F)
and Q2 is nearly pure capacitance. It is indicated
that N–TiO2 coatings have a good corrosion protec-
tion performance to SS substrate.
Figure 10 shows the potential and current fluctu-
ations with time of untreated SS and N–TiO2 coat-
ings measured by electrochemical noise in Hanks so-
lution. The potential of untreated SS reduces quickly
and then recovers slowly, and current rises rapidly,
which agrees well with theoretical pitting corrosion
results obtained by electrochemical noise. The poten-
tial noise peak caused by pitting corrosion often pos-
sesses the features of reducing quickly and recovering
slowly. Current noise peak has the features of rising
or reducing quickly and recovering slowly[20,21] . For
the N–TiO2 coated SS sample, the potential decreases
and current rises both slowly with time, which indi-
cates that uniform corrosion occurred for the sample
in Hanks solution. The N–TiO2 coatings completely
covers on SS surface and isolates SS from environment
solution, which results in the uniform corrosion of N–
TiO2 coated SS. What s more, the burr phenomenon
is shown in Fig. 10(b), and the variation range is from
several tens nA to hundreds of nA. As corrosion went
on, the continuing consumption of N–TiO2 coatings
near the SS substrate and recovery of a passive film
induced the noise to occur in Hanks solution. The N–
TiO2 coatings obviously retard the local pitting and
crevice corrosion.

3.3 Antibacterial test

Fig. 10 Potential and current fluctuations with time mea-
sured in Hanks solution for untreated SS (a) and
N-TiO2 coated SS (b)
where ω is the angular frequency (2πf ) and j is the
square root of −1, for n=0, it denotes resistance, If
n =1, it is capacitance, representing a capacitive be-
havior of the interface. By fitting the EIS spectra us-
Table 3 summarizes the relative number of
S.aureus survived after the photo-catalytic experi-
ment. The bacterial test results for S.aureus are
shown in Fig. 11, as photographs.
According to standard reduction of bacteria crite-
rion, less than 0–20% reductions indicates no bacteri-
cidal effect; between 20%–50% reduction indicates a
low bacteriocidal effect; between 50%–70% reduction
 H.F. Wang et al.: J. Mater. Sci. Technol., 2011, 27(4), 309–316
Table 3 Bacterial test results for untreated SS and N-TiO2 coated SS at different
solid ratios
a
Sample CFU for S.aureus
SS 4.8×105
N-TiO2 1.3×104
a
Note: CFU: colony formation units
Fig. 11 Photo images for the results of S.aureus test for
untreated SS (a) and N-TiO2 coated SS (b)
indicates an expressive bacteriocide; greater than
70% reductions is considered a powerful bacteriocidal
effect[22] . According to this criterion, SS has no bacte-
riocidal effect. But, the N–TiO2 coatings denote pow-
erful bacteriocidal effect (Fig. 11(b)), suggesting that
severe damage has occurred to the bacterium. At-
tack on bacteria is caused by the exposure to reactive
intermediates that transferred from the surface of N–
TiO2 coatings to the outside of the bacteria, such as
superoxide anions (O− 2 ), hydrogen peroxide (H2 O2 ),
and hydroxyl radicals (·OH), which can damage pro-
teins, nucleic acids, etc.[23] . Initial attack takes place
on the cell wall, where the bacteriocide makes first
contact with an intact bacterium[24] . Damage on cell
wall will lead to the perturbation of different cellu-
lar processes, and then the leakage of the cytoplasm,
finally bacteria inactivation and death[25] .
4. Conclusions
(1) N–TiO2 coatings have been successfully fab-
ricated onto 304 SS by oxidative annealing of sput-
tered TiN coatings, which were prepared by using the
plasma surface alloying technique on SS.
(2) The electrochemical measurements show that
315
Reduction of S.aureus/%
52
98.7
N–TiO2 coatings are effective in providing protection
for SS substrates against corrosion in Hanks solution.
N–TiO2 coatings retard the local pitting and crevice
corrosion of SS.
(3) The bacterial tests show that the N–TiO2 coat-
ings have high antibacterial activity eliminating the
S.aureus after 2 h illumination with visible radiation.
Initial studies indicate that the coatings are effective
against S.aureus with a 98.7% kill.
(4) N–TiO2 coatings coated SS not only obtains
excellent antibacterial property, but also keeps good
corrosion resistance.
Acknowledgements
This work was supported by the National Natural Sci-
ence Foundation of China (No. 50771070), the National
High-Tech Research and Development Program of China
(863 Program, No. 2007AA03Z521) and the Excellent
Graduate Innovational Project of Shanxi (No. 20093038).
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