Electrochimica Acta 50 (2005) 3401–3406

Photocathodic protection effect of TiO2 films for carbon steel in

3% NaCl solutions
Moucheng Lia,∗ , Suzhen Luob , Pengfei Wua , Jianian Shena
a Institute of Materials, Shanghai University, P.O. Box 269, 149 Yanchang Road, Shanghai 200072, PR China
b State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, PR China

Received 22 September 2004; received in revised form 13 December 2004; accepted 18 December 2004
Available online 25 January 2005

Abstract

Titanium dioxide (TiO2 ) films were prepared by anodization of titanium foils at different voltages in dilute NaOH solutions and characterized
by XRD and scanning electron microscopy (SEM) techniques. The thin TiO2 films are mainly composed of anatase phase in the form of
nano-crystallites. The photoelectrochemical behavior and photocathodic protection effect for these films were also investigated in 3% NaCl
solutions by using electrochemical measurement techniques and coupling test. The tremendous decrease of film resistance and open circuit
potential of each TiO2 film takes place under ultraviolet (UV) illumination. TiO2 film formed at 120 V can serve as photoanode and supply
a protective photocurrent about 8 ␮A/cm2 to carbon steel, when it is connected to carbon steel in test solution with an area ratio of 2:1. But
TiO2 films can accelerate the corrosion of carbon steel in the dark. In addition, electrochemical impedance spectroscopy (EIS) characteristics
and coupling behaviors for TiO2 films were discussed in detail.
© 2005 Elsevier Ltd. All rights reserved.

Keywords: Titanium dioxide; Photocathodic protection effect; EIS; Corrosion; Anodization

1. Introduction solutions [1–6]. Nevertheless, carbon steel is difficult to be

Under ultraviolet (UV) illumination, electron–hole pairs
are created in titanium dioxide (TiO2 ) film. The electrons can
transfer to some metals in contact with the TiO2 films, and
then inhibit corrosion of the metals. This behavior is similar
to that of sacrificial anodes such as zinc in cathodic protec-
tion systems for metals, which can be called photocathodic
protection effect of TiO2 semiconductor. Unlike sacrificial
anodes in corrosion system, TiO2 can theoretically act as a
non-sacrificial photoanode because the anodic reaction is not
the decomposition of TiO2 itself but the oxidation of water
(H2 O) and/or adsorbed organic species by photogenerated
holes [1–3]. Thus, the photocathodic protection effect of TiO2
has already received special interest.
The photocathodic protection ability of TiO2 coatings had
been confirmed on stainless steel and copper in aqueous NaCl
∗ Corresponding author. Tel.: +86 2156034450; fax: +86 2156335353.
E-mail address: mouchengli@yahoo.com.cn (M.C. Li).
protected from corrosion by this effect, because its corrosion
potential is more negative than that of stainless steel. Though
the photoprotection effect of TiO2 coatings could be achieved
on carbon steel in alkaline solutions (pH = 11) [7] or on preox-
idized carbon steel in NaCl solutions [8,9], these conditions
were of insignificance in practice. In other ways, Ohko et
al. [10] recently showed that SrTiO3 photoanodes (SrTiO3
coatings on indium-tin oxide glass plate) were effective to
photo-protect carbon steels in NaCl solutions, owing to the
much lower flatband potential of SrTiO3 than that of TiO2 . In
addition, composite coatings composed of TiO2 and electron
storage materials (e.g., WO3 [11] and SnO2 [12]) could have
cathodic protection effect under both UV illumination and
dark conditions. Of course, these semiconductor coatings are
inert barriers for shielding the substrate metals from corrosive
environments. Furthermore, TiO2 films can be used as sepa-
rated photoanode to supply photogenerated electrons through
external circuit to protect metals from corrosion. Park et al.
[13] had reported that the corrosion of carbon steel could be

0013-4686/$ – see front matter © 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2004.12.031
3402 M.C. Li et al. / Electrochimica Acta 50 (2005) 3401–3406
suppressed substantially in alkaline solution (pH = 11) as long
as it was connected to the TiO2 photoanode, and the organic
substances (e.g., formate) in the photoanode cell markedly
increased protective current. Due to the depletion of organic
substances with time, the practical application of this tech-
nology will be seriously limited.
In this work, TiO2 films were prepared by anodization, a
traditional method to modify the surface structure and proper-
ties of titanium for photocatalyst. The electrochemical char-
acteristics of these films and their coupling behaviors to car-
bon steel electrodes were investigated under UV illumination
in simulated seawater, too. The main purposes were to make
a new type of anodes for photocathodic protection systems,
and to get a deeper understanding of the photocathodic pro-
tection effects of TiO2 films.
2. Experimental
2.1. Preparation of TiO2 films
Commercial titanium foils (purity > 99.7 wt.%) with di-
mensions of 60 mm × 10 mm × 0.2 mm were used in exper-
iments. The initial surface treatment was to grind with 800
grit waterproof abrasive paper and rinse with tap water. Prior
to anodization, titanium plates were pickled in dilute HF so-
lutions (5 vol.%) [14] and cleaned with ethanol and distilled
water. Titanium was anodized with a direct current power
in 0.1 M NaOH solutions (60 ◦ C) at given voltages (40, 80
and 120 V) for 5 min to form TiO2 films. The anodized films
were characterized by scanning electron microscopy (SEM,
Philips XL30) and X-ray diffraction (XRD, Rigaku D/max
2550 V) with Cu K␣ radiation.
2.2. Electrochemical tests
Each electrochemical experiment was performed at room
temperature in a three-electrode system which was estab-
lished on a beaker containing 500 mL test solution (3 wt.%
NaCl solutions, i.e., simulated seawater) without pH con-
trol and any aeration. A saturated calomel electrode (SCE)
and a platinum foil served as the reference electrode and
counter electrode, respectively. TiO2 film was bended to im-
merse horizontally an area of 2 cm2 into test solution and
5 mm lower than the solution surface, being used as work-
ing electrodes. One thin aluminum (Al) plate with a rect-
angular hole about 15 mm × 25 mm and two small circular
holes lidded the beaker to prevent the solution from irradi-
ation of UV lamp. The electrodes were fixed on Al plate
through the holes. A 125 W high pressure mercury lamp
was located above the solution surface about 6 cm as an
illuminant.
Measurements by electrochemical impedance spec-
troscopy (EIS) were conducted using an electrochemical
measurement system from PAR (Princeton Application Re-
search, AMETEK Inc.), which comprised an M273A po-
tentiostat, an M5210 lock-in amplifier and the PowerSine
software. An alternating current signal with the frequency
range from 98 kHz to 10 mHz and an amplitude of 10 mV
(rms) was applied to the working electrode at the open cir-
cuit potential (OCP). EIS spectra were interpreted using the
non-linear least square (NLLS) fitting procedure developed
by Boukamp [15]. Values of OCP, polarization curves and
coupling current (Icc ) were obtained with an electrochemi-
cal measurement system, which included an M273A and the
M352 software. Polarization curves were determined poten-
tiodynamically with a potential scan rate of 60 mV/min. All
experiments were repeated by using different specimens to
confirm reproducibility of the results.
Coupling tests were carried out through connecting TiO2
films (2 cm2 as anode) to carbon steel electrodes (1 cm2 as
cathode) (Fe, balance; C, 0.46; Mn, 0.85; Si, 0.27; Cu, 0.2;
S, 0.035, wt.%). Before each experiment, the square carbon
steel specimen embedded in epoxy resin was ground with
700 grit waterproof abrasive paper and cleaned with ethanol
and distilled water. Each coupling test was performed after
the OCP measurement under illumination about 90 min.
3. Results and discussion
3.1. Characteristics of TiO2 films
Fig. 1 gives the SEM morphologies of TiO2 films formed
at different voltages. The surface formed at 40 V still showed
small terraces left by anodic dissolution of titanium substrate
because the oxide film was very thin on it. The specimens
anodized at 80 and 120 V were obviously covered by oxide
films. Many white points appeared on the films, which im-
plied that severe breakdown took place in the films during the
anodizing process. It was reported that the breakdown favored
crystallization of the films [16–18]. Due to the development
of breakdown, some small pores formed in the film at 120 V,
but the pores did not evolve as large holes through the film.
The crystalline structure of anodic TiO2 films was charac-
terized by XRD, as shown in Fig. 2. The XRD patterns only
showed one peak of anatase phase in the film formed at 120 V,
from which the crystallite size of anatase was calculated by
using Scherrer’s formula and the result was about 26 nm.
It was known that TiO2 photocatalyst in anatase phase had
much higher photocatalytic properties than in other phases
[19]. Anatase in photoanode should also be important for
the photocathodic protection effect because this effect came
from the photoelectrochemical reactions on TiO2 photocata-
lysts. According to literatures [14,18,20], anatase crystallites
were the major components for the films formed at 40 and
80 V because crystallization in the anodized films occurred at
these voltages, though a certain amount of amorphous phase
might exist. However, the signals from these two films were
almost not detected, which could be attributed to the very low
film thickness. It was estimated that all films were less than
300 nm in thickness, simply assumed a growth constant of
2.34 nm/V and an initial film thickness of about 1 nm [21].
 M.C. Li et al. / Electrochimica Acta 50 (2005) 3401–3406 3403

Fig. 2. XRD patterns of TiO2 films.

of photogenerated electrons and formation of surface states

such as titanium peroxide (Ti4+ O2 2− ) species [23]. And
eventually steady states were attained with approximately un-
changing OCP values, owing to the balancing rate between
creation and depletion of photogenerated carriers. It also can
be seen from Fig. 3 that the relatively stable OCP values at
90 min decreased with the increase of the film forming volt-
ages, and OCP of 120 V-formed film reached −720 mVSCE or
more negative values. According to the principle of cathodic
protection, OCP values of TiO2 photoanodes must be lower
than the corrosion potentials of metals to be protected. Thus,
the 120 V-formed TiO2 film should be possible to protect car-
bon steel (its corrosion potential at about −700 mVSCE [24])
to a certain extent from corrosion in seawater.
Fig. 4 shows the potentiodynamic polarization curves
for a 120 V-formed film before and after UV illuminations
and for a carbon steel electrode in 3% NaCl solutions. The
titanium/TiO2 film electrode was in perfectly passive state
under dark condition with a passive current density no more
than 0.5 ␮A/cm2 . When the UV lamp was turned on, the OCP
was shifted to −730 mVSCE and the anodic polarization be-
came very easy. The significant changes in these two polar-
ization curves were caused by the presence of a new anodic

Fig. 1. SEM morphologies of anodic TiO2 films formed at (a) 40 V; (b) 80 V

and (c) 120 V.

3.2. Electrochemical performance

Fig. 3 shows OCP versus UV-illumination time curves

for anodic TiO2 films in 3% NaCl solutions. OCP dropped
rapidly down to much more negative values as a result of the
sudden creation of electron–hole pairs in the films [22]. After
about 2 min of rapid drop, OCP decreased slowly and tended Fig. 3. Variation of open circuit potential with time for TiO2 films in 3%
to stabilize, which could be attributed to further accumulation NaCl solutions under UV illumination.
3404 M.C. Li et al. / Electrochimica Acta 50 (2005) 3401–3406

Fig. 4. Polarization curves for a 120 V-formed TiO2 film in the absence and
presence of UV light and for a carbon steel electrode in 3% NaCl solutions.

reaction. Under UV illumination, the anodic reaction should

be the oxidation of H2 O by the photogenerated holes in the
valence band of TiO2 , instead of the passivation of titanium
substrate as in the dark. Certainly, the cathodic reactions were
the reduction of dissolved oxygen (O2 ) in both test cases. In
addition, it can be assumed from these results that titanium
substrate had negligible influence on the photoelectrochem-
ical measurements of anodic TiO2 films. Fig. 4 also showed
that the corrosion potential of carbon steel was nobler than
the OCP of TiO2 film under UV illumination. As a result, the
two polarization curves intersected at about −707 mVSCE at
which the TiO2 electrode was polarized as an anode if con-
nected to the steel electrode [25]. The polarizing behavior of
the films formed at 40 and 80 V were similar to that of 120 V-
formed film (not shown here), but their OCP values under
Fig. 5. Impedance plots for the different TiO2 films in 3% NaCl solutions un-
UV illumination were higher than the corrosion potential of der illumination and in the dark. (a) Nyquist plots; (b) Bode plots. Symbols:
carbon steel. experimental data; lines: fitted values.
In order to obtain further information on TiO2 films and
the electrochemical reactions at interface TiO2 /solution under ble layer capacitance, respectively. In addition, both Cf and
steady state conditions, the impedance plots were determined Cdl were replaced with constant phase element (CPE) in the
at OCP potentials and are shown in Fig. 5. For a clear observa- fitting procedure due to the non-ideal capacitive response of
tion, impedance plots for the films formed at 40 and 80 V were the interface TiO2 film/solution [30,31]. The impedance of
not presented here, which had similar features. Some points CPE is given by
at initial high-frequency part were omitted because of the ap-
pearance of high-frequency phase shift [26]. Experimental 1
ZCPE = (1)
data were also compared with the fitted values obtained from Y0 (jω)α
data processing as described later. The lines represent the
model calculations. Each Nyquist plot was composed of a ca- where Y0 is the admittance magnitude of CPE, and α is the
pacitive arc. Bode plots showed that the electrode systems had exponential term. Pure capacitance behavior is represented
two-time constants feature, especially under dark conditions, by α = 1. In practice, α is in the range from zero to one.
which merged in the Nyquist plots. Due to the significant de-
crease of impedance, the time constant from TiO2 film itself
became very difficult to be defined under illumination con-
ditions. Therefore, based on the existence of thin TiO2 films
on the titanium substrates, the equivalent circuit [27–29] in
Fig. 6 was proposed as a model for the electrochemical system
TiO2 film/solution. Rs represents the electrolyte resistance, Rf Fig. 6. Equivalent circuit of the electrochemical system TiO2 film/solution.
and Cf represent the resistance and capacitance of TiO2 film, Rs , electrolyte resistance; Rf and Cf , resistance and capacitance of TiO2 film;
Rt and Cdl represent the charge transfer resistance and dou- Rt , transfer resistance; Cdl , double layer capacitance.
 M.C. Li et al. / Electrochimica Acta 50 (2005) 3401–3406 3405

Table 1
Fitted results of EIS spectra for TiO2 films formed at different anodizing voltages
Voltage (V) Rs ( cm2 ) Y0−f (s␣  cm−2 ) αf Rf ( cm2 ) Y0−dl (s␣  cm−2 ) αdl Rt ( cm2 )
In the dark
40 14.8 3.20 × 10−4 0.62 261 1.36 × 10−5 0.96 9.31 × 106
80 16.6 1.34 × 10−4 0.56 760 2.10 × 10−5 0.90 1.93 × 106
120 14.1 1.19 × 10−4 0.53 997 4.34 × 10−5 0.86 1.82 × 106
Under UV illumination
40 14.6 2.01 × 10−2 0.26 15.8 1.12 × 10−3 0.87 6806
80 12.1 6.17 × 10−3 0.37 56.4 1.99 × 10−3 0.79 4176
120 10.2 1.09 × 10−2 0.33 11.8 1.06 × 10−3 0.75 2782

The model fitted the experimental data very well in spite

of the approximations made, as shown in Fig. 5. It can be
concluded that the model provided a reliable description for
the electrochemical systems. Table 1 gives the fitted results
of EIS spectra for different TiO2 films in 3% NaCl solutions
in the absence and presence of UV light. The relative errors
from the fitting can reach 50% for Y0−f and Rf because of the
poor separation of the two-time constants, and are less than
5% for other parameters.
For a simple comparison, the values of Rf in the dark tend
to increase with anodizing voltage, resulted from the thicken-
ing of TiO2 film on titanium substrate with the film forming
voltage. Each Rt in the dark is of the order of 106  cm2 ,
due to the passive state of titanium/TiO2 film electrodes in
test solutions as shown in Fig. 4. However, Rt in the dark
decreases with anodizing voltage, which does not increase
with the thickening of TiO2 film as expected. This abnormal
change can be attributed to a certain extent to the formation
of more defects such as pores at higher anodizing voltages
(see Fig. 1), which can be further proved by the changes
of αf and αdl The values of αf and αdl in the dark become
smaller with increasing the film forming voltage, being in-
dicative of the increase of the defects and surface roughness
of TiO2 film [32,33]. The values of Rf and Rt under UV il-
lumination are significantly smaller than those in the dark,
respectively. From dark to UV illumination, the photoeffect
in TiO2 films results in the huge changes of Rf [34], while
the appearance of oxidation of H2 O as anodic reaction on
TiO2 films reduces each Rt by a factor of 500 or more. Under
UV illumination, Rt also decreases with anodizing voltage.
This change mainly results from the increase of the amount
of anatase phase and the thickness of TiO2 film, which tend
to produce more electron–hole pairs.
3.3. Coupling behavior between TiO2 films and carbon
steel electrodes
To observe the actual effect of photocathodic protection
from TiO2 , the variations of coupling current (Icc ) were
recorded between different TiO2 films (2 cm2 ) and carbon
steel electrodes (1 cm2 ) in 3% NaCl solutions and are shown
in Fig. 7. The values of Icc for TiO2 films formed at 40, 80
and 120 V are about −21, −3.5 and 8 ␮A under UV illu-
mination conditions respectively, and about −25.5, −16 and
Fig. 7. Variations of coupling currents with time for the TiO2 film-carbon
steel galvanic couples under conditions of light on and off.
−14 ␮A under dark conditions respectively. It is obvious that
120 V-formed TiO2 film does exhibit cathodic protection ef-
fect under illumination, though its Icc is only about 8 ␮A and
must be improved for complete protection of carbon steel
[24]. These results are consistent with above OCP and po-
larization curve results. The Icc for 120 V-formed TiO2 film
dropped rapidly from 8 to −11 ␮A once the UV lamp was
turned off. This important change indicated that, in the dark,
the film served as cathode again in the “galvanic couple” and
did accelerate the corrosion rate of carbon steel.
The coupling behaviors for different TiO2 films can be
explained to a certain extent by OCP curves in Fig. 3 and EIS
fitted results in Table 1. In illumination cases, the main in-
fluence on Icc was from photogenerated carriers. When more
electron–hole pairs were produced in TiO2 films formed at
higher voltages, the photoelectrochemical reactions by holes
became easier with lower Rt values, and more photogener-
ated electrons were accumulated in the films, resulting in
lower OCP values as shown in Fig. 3. Because the potential
difference between 40 V-formed TiO2 film and carbon steel
is larger than that between 80 V-formed TiO2 film and car-
bon steel, 80 V-formed TiO2 film showed smaller absolute
values of Icc than 40 V-formed TiO2 film. As the OCP of
TiO2 film became lower than the corrosion potential of car-
bon steel, some photogenerated electrons could transfer to
carbon steel, with positive Icc values as 120 V-formed TiO2
film in Fig. 7. Film resistance Rf had slight influence on Icc
3406 M.C. Li et al. / Electrochimica Acta 50 (2005) 3401–3406
under illumination, due to its low values as shown in Table 1.
In dark cases, on the contrary, all TiO2 films served as cath-
odes in the “galvanic couples”, with reduction reaction of O2
on their surfaces. The rate of O2 reducing reaction on differ-
ent TiO2 film surfaces might be of insignificant changes. The
big differences in Icc among these films mainly resulted from
the influence of Rf . The higher anodizing voltage the lager Rf
is observed in Table 1. As the lager Rf was connected into the
coupling circuit, the absolute values of Icc should be smaller,
as shown in Fig. 7.
4. Conclusions
Thin TiO2 films prepared in 0.1 M NaOH solutions
through anodizing at different voltages mainly consist of
anatase nano-crystallites, especially for 120 V-formed TiO2
film. Under dark conditions, the anodized films are in pas-
sive state at open circuit potentials, and have acceleration
effect on the corrosion of carbon steel in 3% NaCl solutions.
Under UV illumination conditions, the film resistances are
very low, only about several 10  cm2 . Photogenerated elec-
trons are gradually accumulated in the TiO2 films, resulting
in negative shift of the open circuit potentials of the films
and the higher film forming voltage the lower open circuit
potential. As the 120 V-formed TiO2 film is connected to car-
bon steel in test solution, it shows photocathodic protection
effect. Because the protective coupling current is relatively
small, further effort is required for a complete photocathodic
protection of carbon steel by anodic TiO2 films.
Acknowledgments
The financial support provided by Natural Science Foun-
dation of China (NSFC) in combination with Shanghai BaoS-
teel Company (Grant no. 50471105), Shanghai Municipal
Education Commission (04AE96), and Shanghai Science and
Technology Council (0352 nm074) is greatly appreciated.
References
[1] J. Yuan, S. Tsujikawa, J. Electrochem. Soc. 142 (1995) 3444.
[2] Y. Ohko, S. Saitoh, T. Tatsuma, A. Fujishima, J. Electrochem. Soc.
148 (2001) 24.
[3] J. Yuan, R. Fujisawa, S. Tsujikawa, Zairyo-to-Kankyo 43 (1994)
433.
[4] T. Konishi, S. Tsujikawa, Zairyo-to-Kankyo 44 (1995) 534.
[5] T. Imokawa, R. Fujisawa, A. Suda, S. Tsujikawa, Zairyo-to-Kankyo
43 (1994) 482.
[6] T. Konishi, S. Tsujikawa, Zairyo-to-Kankyo 46 (1997) 709.
[7] J. Yuan, S. Tsujikawa, Zairyo-to-Kankyo 44 (1995) 627.
[8] J. Huang, T. Shinohara, S. Tsujikawa, Zairyo-to-Kankyo 46 (1997)
651.
[9] J. Huang, T. Konishi, T. Shinohara, S. Tsujikawa, Zairyo-to-Kankyo
47 (1998) 193.
[10] Y. Ohko, S. Saitoh, T. Tatsuma, A. Fujishima, Electrochem. Solid-
State Lett. 5 (2002) 9.
[11] T. Tatsuma, S. Saitoh, Y. Ohko, A. Fujishima, Chem. Mater 13
(2001) 2838.
[12] R. Subasri, T. Shinohara, Electrochem. Commun. 5 (2003)
897.
[13] H. Park, K.Y. Kim, W. Choi, J. Phys. Chem. B 106 (2002)
4775.
[14] J.R. Birch, T.D. Burleigh, Corrosion 56 (2000) 1233.
[15] B.A. Boukamp, in: Proceeding of the 9th European Corrosion
Congress, Utrecht, The Netherlands, October 1989, EFC, vol. 1,
Paper no. FU-252.
[16] J. Yahalom, J. Zahavi, Electrochim. Acta 15 (1970) 1429.
[17] C.K. Dyer, J.S.L. Leach, J. Electrochem. Soc. 125 (1978)
1032.
[18] M. Pang, D.E. Eakins, M.G. Norton, D.F. Bahr, Corrosion 57 (2001)
523.
[19] A. Sclafani, J.M. Herrmann, J. Phys. Chem. 100 (1996) 13655.
[20] L.D. Arsov, C. Kormann, W. Plieth, J. Electrochem. Soc. 138 (1991)
2964.
[21] Y.T. Sul, C.B. Johansson, Y. Jeong, T. Albrektsson, Med. Eng. Phys.
23 (2001) 329.
[22] J.A. Byrne, A. Davidson, P.S.M. Dunlop, B.R. Eggins, J. Photochem.
Photobiol. A: Chem. 148 (2002) 365.
[23] N. Beermann, G. Boschloo, A. Hagfeldt, J. Photochem. Photobiol.
A: Chem. 152 (2002) 213.
[24] S.X. Hu, Handbook of Cathodic Protection Engineering, Chemical
Industry, Publishing House, Beijing, China, 2000.
[25] D.A. Jones, Corrosion 40 (1984) 181.
[26] M.C. Li, C.L. Zeng, H.C. Lin, C.N. Cao, Bull. Electrochem. 17
(2001) 299.
[27] J. Bisquert, G. Garcia-Belmonte, F. Fabregat-Santiago, N.S. Fer-
riols, P. Bogdanoff, E.C. Pereira, J. Phys. Chem. B 104 (2000)
2287.
[28] D. Vanmaekelbergh, Electrochim. Acta 42 (1997) 1121.
[29] F. Mansfeld, J. Appl. Electrochem. 25 (1995) 187.
[30] X. Wu, H. Ma, S. Chen, Z. Xu, A. Sui, J. Electrochem. Soc. 146
(1999) 1847.
[31] M.C. Li, C.L. Zeng, S.Z. Luo, J.N. Shen, H.C. Lin, C.N. Cao, Elec-
trochim. Acta 48 (2003) 1735.
[32] J.R. Park, D.D. MacDonald, Corros. Sci. 23 (1983) 295.
[33] U. Rammlet, G. Reinhard, Corros. Sci. 27 (1987) 373.
[34] A.M. Eppler, I.M. Ballard, J. Nelson, Phys. E. 14 (2002) 197.