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Full download Fabrication of heterostructured β-Bi2O3-TiO2 nanotube array composite film for photoelectrochemical cathodic protection applications Zi-Chao Guan & Hai-Peng Wang & Xia Wang & Juan Hu & Rong-Gui Du file pdf all chapter on 2024
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Corrosion Science 136 (2018) 60–69
Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
A R T I C L E I N F O A B S T R A C T
Keywords: An ordered TiO2 nanotube array (NTA) film was first fabricated on a Ti substrate by anodization, β-Bi2O3
A. Titanium nanoparticles were then electrodeposited on the film for obtaining a heterostructured β-Bi2O3-TiO2 NTA com-
A. Stainless steel posite film with enhanced photocathodic protection performances. Compared to the bare TiO2 NTA film, the
B. EIS composite film showed a wider light absorption region and higher charge carrier separation efficiency. Under
B. XPS
white light illumination, the composite film as a photoanode made the potential of 403 stainless steel in a 0.5 M
C. Cathodic protection
C. Oxide coatings
NaCl solution decrease by 450 mV relative to its corrosion potential, showing an effective photoelectrochemical
cathodic protection effect.
⁎
Corresponding author.
E-mail address: rgdu@xmu.edu.cn (R.-G. Du).
https://doi.org/10.1016/j.corsci.2018.02.048
Received 25 August 2017; Received in revised form 10 February 2018; Accepted 20 February 2018
Available online 21 February 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.
Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
corrosion damage [42]). which had passed through a quartz window. The time evolution of the
In this work, a β-Bi2O3-TiO2 NTA composite film was fabricated by photocurrent and photopotential were recorded under dark and illu-
electrochemical anodization combined with ultrasonic-assisted elec- mination conditions for several cycles. Under dark conditions, the
trodeposition for its application in photoelectrochemical cathodic pro- current density-potential (i-E) curves of the prepared films in the 0.5 M
tection. The protection effects and mechanisms of the composite film on Na2SO4 solution were measured in the above three-electrode cell with
403 stainless steel (403SS) were especially investigated. the film working electrode, SCE reference electrode and platinum
counter electrode at a scan rate of 10 mV s−1 from −1.2 V to 1.2 V (vs.
2. Experimental SCE). All the measurements were performed by a model 263A po-
tentiostat/galvanostat (Princeton Applied Research, USA).
2.1. Preparation of β-Bi2O3-TiO2 NTA films 403SS specimens with dimensions of 15 mm × 10 mm × 1 mm
were prepared and used as the metal to be protected by the prepared
Ti foils (99.8% purity) were processed into the specimens with di- films. The composition of 403SS was (wt%): 0.95 C, 0.08 P, 0.94 Si,
mensions of 15 mm × 10 mm × 0.1 mm and used as the substrates to 0.53 Mn, 0.96 Ni, 13.03 Cr and balance Fe. Before use, the specimen
fabricate β-Bi2O3-TiO2 NTA composite films. Before use, the specimens was mechanically abraded by SiC paper from 600 to 1200 grit gradually
were ultrasonically cleaned in acetone, ethanol, and deionized water and polished with 1.0 μm Al2O3 powder, and ultrasonically cleaned
for 20 min successively and then dried. sequentially in ethanol and deionized water. Then, each specimen was
A TiO2 NTA film was directly prepared on the Ti substrate through clamped to a Cu core wire and covered with nail polish leaving a single
anodization in a classical two-electrode system with a Ti foil specimen working surface with an area of 1 cm2 to act as an electrode.
as the working electrode, and a platinum sheet as the counter electrode. The potential measurements and electrochemical impedance spec-
The anodization was conducted at a constant voltage of 20 V for 30 min troscopy (EIS) tests were conducted for the 403SS specimen coupled
in a 0.5 wt% HF solution at room temperature. After the anodization, with the different films (as photoanodes) to investigate the photoelec-
the sample was rinsed with deionized water, and then heated from trochemical cathodic protection performances of the prepared films.
room temperature to 450 °C (heating rate of 5 °C min−1) in air and The schematic diagram of the experimental setup is shown in Scheme 1,
annealed at 450 °C for 2 h to obtain a crystalline anatase TiO2 NTA film. which is similar to the measurement system reported previously by our
A desired β-Bi2O3-TiO2 NTA composite film was prepared via an group [43]. In this setup, there were two electrolytic cells connected by
ultrasonic-assisted pulse current electrodeposition technique. The as- a salt bridge (saturated KCl in agar in a flexible glass tube). One was a
prepared TiO2 NTA film was first soaked in a 3 M HCl solution con- corrosion cell with the 403SS plate working electrode, the SCE re-
taining 0.1 M Bi(NO3)3 and 0.04 M EDTA (ethylenediaminetetraacetic ference electrode and the platinum sheet counter electrode in a 0.5 M
acid) for 20 min under ultrasonication (frequency of 40 kHz) to remove NaCl solution for electrochemical measurements. The other was a
air in the nanotubes and let the electrolyte enter into the nanotubes. photoelectrochemical cell with a photoanode (namely the prepared film
Then the TiO2 NTA film was transferred to the electrolytic cell with the sample) in a 0.5 M Na2SO4 solution, and a quartz window as an optical
same HCl solution and acted as the working electrode in the electro- channel. The photoanode was coupled to the 403SS plate by a copper
deposition procedure, while a saturated calomel electrode (SCE) and a wire. The light source was a 150 W Xe lamp. A computer-controlled
platinum sheet served as the reference and counter electrodes, respec- potentiostat/galvanostat (model 263A, Princeton Applied Research,
tively. The electrodeposition was carried out by applying a USA) was employed for photoelectrochemical and electrochemical
−80 mA cm−2 cathodic current for 20 ms and an 80 mA cm−2 anodic measurements. The corrosion potential (open circuit potential) change
current for 2 ms alternately for 100 cycles, and the break time (no of the uncoupled 403SS was measured in the corrosion cell with a 0.5 M
applied current) was 1 s between each cycle. Finally, the sample was NaCl solution. The photopotential (photo-induced open circuit poten-
heated from room temperature to 550 °C in air with a heating rate of tial) change of the 403SS in the same NaCl solution coupled with the
5 °C min−1 and annealed at 550 °C for 2 h. TiO2 NTA or β-Bi2O3-TiO2 NTA film photoanode under intermittent
white light illumination was measured in open-circuit situations (no
2.2. Characterization
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Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
Fig. 1. SEM images of (a) top-view, (b) cross-sectional view of the TiO2 NTA film, (c) top-view and (d) cross-sectional view of the β-Bi2O3-TiO2 NTA composite film. The inset in (c) shows
the magnified view of the nanotube of the β-Bi2O3-TiO2 NTA film.
Fig. 1 shows the SEM images of different film samples with good
reproducibility. It can be seen that an ordered NTA film was formed on
the Ti foil surface by the electrochemical anodization (Fig. 1a). The film
was composed of single-wall TiO2 nanotubes with average internal
diameter of about 100 nm. Fig. 1b provides a lateral view image of the Fig. 2. EDS spectrum of the β-Bi2O3-TiO2 NTA composite film, the inset shows the
TiO2 NTA film, in which the TiO2 nanotubes were arranged perpendi- magnified view of the spectrum between 2.0 keV and 3.2 keV.
cularly to the Ti substrate surface, and the tube length ranged from
300 nm to 400 nm. After the deposition of Bi2O3 (which would be desired Bi2O3-TiO2 composite through the ultrasonic-assisted electro-
confirmed below) on the TiO2 NTA film, the SEM images of the top- deposition method. The ultrasonication process could efficaciously re-
view and cross-sectional views of the Bi2O3-TiO2 composite film are move air from the TiO2 nanotube surfaces, and simultaneously force the
shown in Figs. 1c and d, respectively. The ultrasonic treatment and electrolyte to diffuse quickly into the pores of the nanotubes. The
electrodeposition procedures did not destroyed the intrinsic structure of subsequent electrodeposition procedure was intended to make the
the TiO2 NTA film. Some nanoparticles were evenly distributed on the electropositive Bi3+ ions be adsorbed onto both the exterior and in-
NTA surface without blocking the nanotube orifices, and the tube wall terior surfaces of the nanotubes, and finally they were transformed into
thickness increased. During the SEM observation, the EDS measurement the Bi oxide.
was accomplished to confirm the elemental composition of the com- The XPS measurements were performed to further confirm the
posite film. Fig. 2 shows the corresponding EDS result, which indicated chemical compositions and oxidation states of the composite film,
the presence of Ti, O and Bi elements in the composite film. The pre- especially for the Bi oxide deposited on the TiO2 NTA film. XPS wide
sence of Bi provided an important evidence for the formation of the scan spectra for both the bare TiO2 and Bi2O3-TiO2 films are presented
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Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
Fig. 3. XPS spectra of the TiO2 NTA and β-Bi2O3-TiO2 NTA films, (a) full spectra for both films, (b–d) high-resolution spectra of the β-Bi2O3-TiO2 NTA film for: (b) Ti 2p, (c) Bi 4f and (d) O
1s.
in Fig. 3a, and the high-resolution narrow scan spectra of the Bi2O3- peaks, suggesting that there were different chemical states of O element
TiO2 composite film for Ti 2p, Bi 4f and O 1s are presented in in the composite film [47]. Specifically, the peak at 528.5 eV belonged
Figs. 3b–d, respectively. In the wide scan spectra, the peaks for C 1s to the O of Bi-O, and the peak at 529.5 eV was attributed to the O from
(284.2 eV), Ti 3s (60.7 eV), Ti 2p (458.2 eV), Ti 2s (580.0 eV) and O 1s Ti-O. These two chemical states of O were considered as lattice O, and
(529.5 eV) could be observed both for the bare TiO2 and composite indicated the existence of Bi2O3 and TiO2, respectively. The peak at
Bi2O3-TiO2 films, and the corresponding AES peaks of O KLL and Ti 531.2 eV could be ascribed to the adsorbed oxygen brought by irre-
LMM appeared at 975.6 eV and 1071.4 eV, respectively. While the versibly adsorbed H2O on the film surface [48,49].
peaks at 160.6 eV and 442.1 eV corresponding to Bi 4f and Bi 4d could XRD analyses were also performed to study the crystalline phase of
be observed for the composite film, respectively. The C 1s peak was film samples. Fig. 4 presents the XRD patterns of the Ti foil, TiO2 NTA
thought to be caused by the adventitious hydrocarbon contamination and Bi2O3-TiO2 NTA films. The additional peaks were ascribed to TiO2
[36]. The high-resolution narrow scan spectrum of Ti 2p of the com- or Bi2O3 in the TiO2 NTA and/or Bi2O3-TiO2 composite films besides
posite film is displayed in Fig. 3b. The two peaks centered at 458.1 eV the main diffraction peaks of Ti from the films. To be specific, the
and 463.8 eV were ascribed to Ti 2p3/2 and Ti 2p1/2, respectively, and diffraction peaks at 25.3° and 48.1° for the bare TiO2 NTA film (Fig. 4b)
the doublet separation of Ti 2p was 5.7 eV, which had good agreement could be indexed to the (101) and (200) planes of anatase TiO2 phase
with the reported value [44], indicating the existence of Ti4+ in the (PDF #02-0387), respectively. At the same time, no peaks corre-
composite film. As presented in Fig. 3c, the high resolution XPS spec- sponding to rutile TiO2 were detected, demonstrating that the TiO2
trum of the Bi 4f region exhibited two peaks located at 158.7 eV and obtained by anodization and 450 °C calcination was anatase phased
164.1 eV, which belonged to Bi 4f7/2 and Bi 4f5/2, respectively. Fur- TiO2. As shown in Fig. 4c, after the electrodeposition of Bi2O3, a dif-
thermore, the energy difference between the two peaks was exactly fraction peak at 27.5° originated from the composite film was indexed
5.4 eV in agreement with the data reported in the literature [36]. So, to the (121) plane of β-Bi2O3 (PDF #72-0398). So the Bi2O3 deposited
the XPS data in Fig. 3c provided a convincing proof that the valence on TiO2 NTA film was confirmed as β-Bi2O3.
state of Bi was +3 in the composite film, indicating the existence of Based on the above analyses and discussions, we concluded that the
Bi2O3 [36,45,46]. In Fig. 3d, the narrow spectrum of O 1s contained desired β-Bi2O3-TiO2 NTA composite film has been fabricated by an
only one broad peak, which could be fitted into three peaks with anodization combined with ultrasonic-assisted electrodeposition
binding energies of 528.5 eV, 529.5 eV and 531.2 eV, respectively. method. Additionally, the above characterization results showed the
Apparently, there were some overlapping parts among these three good reproducibility of the preparation method of the composite film.
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Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
where α, h, ν are the absorption coefficient, Planck's constant and light Compared to the traditional cathodic protection (sacrificial anode
frequency, respectively. A is a constant related to temperature, photon and impressed current cathodic protection), the photoelectrochemical
energy and phonon energy. Eg is the band gap and η value is determined cathodic protection has high research value and inviting application
by the transition type of electrons in the semiconductor, i.e., η = 1/2 is prospects because it does not consume anode materials and external
for the direct transition and η = 2 is for the indirect transition. Here η is electric energy. The basic mechanism of photoelectrochemical cathodic
protection is that a semiconductor photoanode is used as a replacement
Fig. 5. (a) UV–vis absorption spectra of the TiO2 NTA and β-Bi2O3-TiO2 NTA films, (b) the corresponding plots of (αhν)1/2 versus hν.
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Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
stability during the entire test period, which is also propitious to their
applications in photoelectrochemical cathodic protection. Fig. 7b dis-
plays the photopotential (photo-induced open circuit potential) varia-
tions of the TiO2 NTA and β-Bi2O3-TiO2 NTA films in the 0.5 M Na2SO4
solution under intermittent white light illumination and open-circuit
conditions. Before the white light illumination (dark conditions), the
potentials of TiO2 NTA and β-Bi2O3-TiO2 NTA films were about
−110 mV (vs. SCE) and −200 mV (vs. SCE), respectively. When the
films were separately illuminated, their potentials shifted in the nega-
tive direction because of the generation of photoelectrons in these two
semiconductor films. For the bare TiO2 NTA film, its photopotential was
about −280 mV (vs. SCE), which was 170 mV lower than its original
open-circuit potential (namely the potential before illumination).
Especially, the photopotential of the β-Bi2O3-TiO2 NTA film reached
about −460 mV (vs. SCE), which was 260 mV lower than its original
open-circuit potential. That is to say, the photopotential of the β-Bi2O3-
TiO2 NTA film was more negative than that of the bare TiO2 NTA film
under white light illumination, which indicated that the β-Bi2O3-TiO2
Fig. 6. Photoluminescence spectra of (a) the TiO2 NTA film and (b) the β-Bi2O3-TiO2 NTA NTA film might provide a more effective photoelectrochemical cathodic
film with the excitation wavelength of 370 nm, the inset shows the fitting result of the protection effect than the bare TiO2 NTA film. When the light was
peak between 440 nm to 520 nm. turned off, the potentials of the two films immediately shifted positively
due to the electron-hole recombination, which was in accordance with
for the traditional sacrificial anode, and provides CB electrons gener- the results of photocurrent density measurements. Furthermore, the
ated from the VB under illumination for a metal to be protected. In a potential response of both the bare TiO2 and β-Bi2O3-TiO2 films was
photoelectrochemical cathodic protection system, the semiconductor almost repeatable, showing good photosensitivity and high stability
photoanode supplies the metal with a photocurrent resulting from during the entire test period, which is important for the application in
photoelectric conversion to protect the metal cathodically from corro- photoelectrochemical cathodic protection.
sion [23,24,42]. As is known to all, when a metal is under cathodic protection, its
In order to inhibit the metal corrosion by the photoelectrochemical actual potential is more negative than its open circuit potential (OCP).
approach, the photoanode under illumination must have the ability to In this work, the changes of the 403SS potential under different con-
provide enough cathodic current for the metal. Fig. 7a compares the ditions were measured to evaluate the photoelectrochemical cathodic
instantaneous photocurrent densities of the TiO2 and β-Bi2O3-TiO2 NTA protection performance of the TiO2 and β-Bi2O3-TiO2 NTA films as
films in the 0.5 M Na2SO4 solution under white light illumination in photoanodes. The potential changes of 403SS in the 0.5 M NaCl solution
open-circuit situations for evaluating the sensitivity of the film to the are presented in Fig. 8. Before coupling, the corrosion potential of
light. The currents as recorded were anodic on the Ti specimen. The β- 403SS stabilized at about 50 mV vs. SCE (Fig. 8a). As seen in Fig. 8b and
Bi2O3-TiO2 NTA composite film showed a photocurrent density of c, when 403SS was coupled to the TiO2 and β-Bi2O3-TiO2 NTA films
80 μA cm−2, which was about 4 times as high as that of the bare TiO2 under dark conditions, the potentials were negatively shifted to
NTA film (about 20 μA cm−2). The enhancement of the photocurrent −150 mV vs. SCE and −190 mV vs. SCE, respectively, because of the
density for the composite film presaged higher photoelectrochemical galvanic effect. When the white light illumination was provided, po-
conversion efficiency. And this enhancement could be attributed to the tentials showed further negative shifts to −250 mV vs. SCE and
deposition of β-Bi2O3, leading to the faster transfer and higher se- −400 mV (vs. SCE) for the 403SS electrode coupled with the TiO2 and
paration efficiency of the photogenerated electron-hole pairs. In addi- β-Bi2O3-TiO2 films, respectively. Under these illumination conditions,
tion, the photocurrent densities of the two samples immediately the 403SS were under cathodic protection. The potential of the 403SS
changed once the light was turned on or off, indicating the high sen- coupled with the β-Bi2O3-TiO2 composite film was 150 mV more ne-
sitivity of the films to the light. The two films also showed excellent gative than that coupled with the bare TiO2 NTA film, showing more
effective photoelectrochemical cathodic protection by the β-Bi2O3-TiO2
Fig. 7. (a) Transient photocurrent density and (b) photopotential (photo-induced open circuit potential) responses of the TiO2 NTA and β-Bi2O3-TiO2 NTA films served as anodes in the
0.5 M Na2SO4 solution in open-circuit situations under intermittent white light illumination.
65
Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
Fig. 9A. In the presented equivalent circuit model, Rs, Rct and CPE re-
present the solution resistance, charge transfer resistance and constant
phase element, respectively. The main objective of the EIS measure-
ments is to obtain the Rct value of the coupled 403SS in the corrosion
cell for the comparison between illumination and dark conditions. For
simplicity, the EIS analysis focused on the effect of the film under white
light illumination on the coupled steel. The fitting results showed that
the Rct of the uncoupled 403SS was 287.70 ± 4.32 kΩ cm2, but de-
creased sharply to 19.53 ± 0.23 kΩ cm2 and 6.24 ± 0.25 kΩ cm2
when the 403SS was coupled with the bare TiO2 and β-Bi2O3-TiO2 NTA
composite films under white light illumination, respectively. When the
403SS was coupled with the film photoanode under illumination, the
photogenerated electrons were transferred from the photoanode to the
steel to participate in the electrochemical reactions, which accelerated
the cathodic reaction at the steel/solution interface and showed a lower
Rct value. Therefore, the 403SS was polarized cathodically and its
corrosion was reduced. Furthermore, the Rct value of the 403SS coupled
with the composite film was lower than that coupled with the bare TiO2
film, suggesting that the composite film under illumination could pro-
vide more electrons due to its superior photoelectrochemical perfor-
mance, which was in agreement with the foregoing analysis results.
Thus, it is conclusive that the prepared β-Bi2O3-TiO2 NTA composite
film could provide a higher cathodic current density under white light
Fig. 8. Potential changes of 403SS in the corrosion cell with a 0.5 M NaCl solution in
illumination relative to the bare TiO2 NTA film, and more effectively
open-circuit situations, (a) corrosion potential of uncoupled 403SS, (b) 403SS coupled
inhibit the corrosion of 403SS.
with the TiO2 NTA film and (c) 403SS coupled with the β-Bi2O3-TiO2 NTA film under
intermittent white light illumination. The inset shows the potential change of 403SS
coupled with the β-Bi2O3-TiO2 film under 6 light on/off cycles. The films as photoanodes 3.4. Mechanism
were in the photoelectrochemical cell with a 0.5 M Na2SO4 solution.
Based on the above results and discussions, the mechanism of the
enhanced photoelectrochemical cathodic protection provided by the β-
composite film. When the illumination was turned off, the potential of Bi2O3-TiO2 composite film for 403SS is illustrated in Scheme 2.
the 403SS coupled with the TiO2 film immediately shifted back to the TiO2 is a recognized n-type semiconductor, while β-Bi2O3 belongs to
value (−150 mV vs. SCE) before illumination and remained stable, a p-type semiconductor. In the β-Bi2O3-TiO2 NTA film, a p-n hetero-
while the potential of the 403SS coupled with the composite film junction was built between the p-type Bi2O3 and the n-type TiO2, which
shifted positively to a potential level (−240 mV vs. SCE) lower than could be proved by the i-E curves shown in Fig. 9D. The dark current of
that (−190 mV vs. SCE) before illumination, indicating that the com- the bare TiO2 film was almost zero, showing the poor p-n heterojunction
posite film remaining some cathodic protection effect. When the illu- effect. However, the current of the β-Bi2O3-TiO2 NTA film was asym-
mination was provided again, the potential of the 403SS coupled with metric in forward and reverse scans, showing an obvious diode beha-
TiO2 or β-Bi2O3-TiO2 film decreased to the same value as before and vior. This result provided reliable evidence that the p-n heterojunction
was stable, showing good sensitivity to light. After cutting off the light, was built and there was an internal electrostatic field at the interface
the 403SS potential again rose sharply to the same value as before between TiO2 and Bi2O3 [61]. When the p-n heterojunction was formed,
(Figs. 8b and c). But the potential of the 403SS coupled with the β- electrons transferred from n-type TiO2 to p-type Bi2O3, while holes
Bi2O3-TiO2 composite film increased gradually to the level as that be- transferred in the opposite direction until the system reached equili-
fore the first illumination, indicating that the composite film could bration because of the diffusion effect of carriers. This carrier diffusion
provide some degree of cathodic protection even after the light was cut results in the formation of internal electrostatic field in the p-n het-
off during this period (about 15 h). To investigate the stability of the erojunction (shown in Scheme 2), which made the n-type TiO2 be po-
composite film in the photoelectrochemical cathodic protection appli- sitively charged and the p-type Bi2O3 be negatively charged [62,63].
cation, the potential response of the 403SS coupled with the composite As shown in Scheme 2, when the β-Bi2O3-TiO2 NTA film was irra-
film to 6 on/off cycles of illumination was recorded as shown in the diated by white light (Xe lamp, 190–1100 nm), TiO2 could absorb the
inset of Fig. 8. The results showed that the composite film was quite UV light to excite its VB electrons to the CB, while the photogenerated
stable and its protecting effect on the 403SS did not evidently attenuate holes migrated from the TiO2 VB to the β-Bi2O3 VB due to the driving
during the illumination for the 6 cycles. force of the internal electrostatics in the p-n heterojunction. Meanwhile,
EIS can provide valuable electrochemical information of the metal/ β-Bi2O3 could absorb UV light and part of visible light due to its narrow
solution interface. So, EIS measurements were executed to evaluate the band-gap, and more photoelectrons were generated in the CB of the
photoelectrochemical cathodic protection effects of the prepared films excited β-Bi2O3. Similarly, the photoelectrons were transferred from the
[23,24,60]. The Nyquist, Bode-phase and Bode-modulus plots of 403SS β-Bi2O3 CB to the TiO2 CB due to the driving force of the internal
in the 0.5 M NaCl solution uncoupled and coupled with different film electrostatics. Taken as a whole, the photogenerated electron-hole pairs
photoanodes are presented in Fig. 9A–C, respectively. The Nyquist plots in the β-Bi2O3-TiO2 composite film were separated effectively, the
featured only one capacitive loop, and the Bode plots showed only one photogenerated electrons were transferred from the TiO2 CB to the
time constant accordingly. The radius of the capacitive loop in the 403SS to provide cathodic protection, and the photogenerated holes in
Nyquist plot decreased when 403SS coupled with the film photoanode the β-Bi2O3 VB were consumed by hole scavengers in the solution. So,
under white light illumination, and showed the smallest radius when the β-Bi2O3-TiO2 NTA film had a higher charge carrier separation and
403SS coupled with the β-Bi2O3-TiO2 composite film. The similar var- transfer efficiency and superior photoelectrochemical performance
iation trend was observed in Bode plots. Therefore, the EIS spectra compared with the unmodified TiO2 film. Therefore, the deposition of
could be modeled by the equivalent circuit shown in the inset of β-Bi2O3 nanoparticles on the TiO2 nanotubes could improve the
66
Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
Fig. 9. (A) Nyquist, (B) Bode-phase and (C) Bode-modulus plots of 403SS in the 0.5 M NaCl solution uncoupled and coupled with different film photoanodes under white light
illumination at open-circuit potential conditions: (a) uncoupled, (b) coupled with TiO2 NTA film and (c) coupled with the β-Bi2O3-TiO2 NTA film. The scatter plots are experimental data
and solid lines are the fitting results. The two insets in (A) show the simulating equivalent circuit of 403SS with the above conditions and the magnified plots, respectively. (D) i-E curves
of the TiO2 NTA and β-Bi2O3-TiO2 NTA films in the 0.5 M Na2SO4 solution at a scan rate of 10 mV s−1 under dark conditions.
the bare TiO2 NTA film, the β-Bi2O3-TiO2 NTA composite film exhibited
a broader light absorption region and a higher photogenerated carrier
separation and transfer efficiency. The photocurrent density of the
composite film in the 0.5 M Na2SO4 solution under white light illumi-
nation was 4 times as high as that of the bare TiO2 film, indicating that
the photoelectrochemical performance of the composite film was lar-
gely enhanced. The potential of 403SS in the 0.5 M NaCl solution de-
creased by 300 mV and 450 mV compared to its corrosion potential
when it was coupled to the TiO2 and β-Bi2O3-TiO2 films in the 0.5 M
Na2SO4 solution under white light illumination, respectively, indicating
that the β-Bi2O3-TiO2 composite film could provide a more effective
photoelectrochemical cathodic protection for 403SS than that provided
by the bare TiO2 film.
Acknowledgement
Scheme 2. Schematic illustration of the energy band structure and the electron-hole pair
separation/transfer mechanism in the β-Bi2O3-TiO2 NTA composite film under white light
Financial support from NSFC (Nos. 21573182, 21173177, 21073151,
illumination for the photoelectrochemical cathodic protection application.
and 21621091) is gratefully acknowledged.
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Z.-C. Guan et al. Corrosion Science 136 (2018) 60–69
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KÓWAM AND GÁHGA
CHARACTERS
Gáhga Heron
Kówam Red-billed Duck
Lok Bear
Kówam and his little brother lived on the south side of Klamath Lake.
The little boy’s name was Gáhga.
Kówam had a nice-looking wife, and when he went to fish in the lake,
he always told her that if any one came to bother her she must send
Gáhga to tell him.
One morning, when Kówam had gone to the lake, and his old
mother-in-law was out gathering wood, Kówam’s wife sat down by
the fire and began to make a reed basket for Kówam to put fish in.
After a while the old woman ran in and cried: “The big-footed people
are coming!”
Soon the five Lok brothers came in and sat down by the fire. The
eldest brother put his head on the young woman’s lap.
Gágha began to cry, and Lok said: “Why do you cry, little boy? Are
you sorry for me because I haven’t a wife? This woman is my wife.”
Gágha kept crying. At midday his eyes were so swollen that he could
hardly open them. “Stop crying,” said his sister-in-law. “Go and find
your brother and tell him that the big-footed men are here. Maybe
nothing has happened, and he doesn’t know there is trouble at
home.”
Gágha cried all the time he was going to the lake. When he found his
brother Kówam asked: “What’s the matter? What makes you cry?
Did you hurt yourself?”
“No,” said Gágha, “five of the big-footed people from the north side
of the lake are in our house, and one of them has his head on my
sister-in-law’s knees.” [285]
“No, but I’ve cried all the time, I’m so sorry they have taken my
sister-in-law away from me.”
“If she isn’t crying, she doesn’t care for us, and there is no use in
crying. If they had made her cry, I should kill those men.”
Kówam sat still a long time; he was thinking what he could do. Then
he said to Gágha: “Stop crying and get some wood; we will cook fish
to eat. You must hurry, so we can go home before it’s dark.”
Little Gágha could hardly stand; he had cried so long that he was
dizzy.
Kówam said: “Don’t cry any longer. I know what I will do to those big-
footed people.”
They built a fire and cooked fish. Gágha’s tears were dropping all the
time he was eating.
“Stop crying and finish eating!” said his brother. “Whenever a man
has a nice wife he is bothered. It will always be that way.”
Kówam filled an old basket with fish, picked it up, put it on his back,
and said: “Now we will go home.”
When they were part of the way home, Kówam said: “Little brother,
take my bow and arrow and shoot me in the heart.”
“You are my own brother, all the one I have. I won’t do it,” said
Gágha.
“It will kill you; then I shall be all alone,” said Gágha.
Kówam talked a long time, asked in every way, but Gágha always
said: “You are my brother; I won’t kill you.” At last Kówam said: “If
you don’t shoot me and make me strong, I will let the big-footed
people have your sister-in-law; I [286]won’t try to kill them. You can’t
kill me. Nobody can kill me; I shall live always.”
At last Gáhga took the bow and arrow and shot Kówam in the heart,
killed him; then he ran, for he felt scared. Right away Kówam
overtook him, and said: “Now shoot me in the heart and tear my
body to pieces.” Gáhga did as Kówam told him to and then ran away.
Again Kówam overtook him. That time he said: “Kill me and pound
my body to pieces; then mix the pieces with dirt and stones.” Gáhga
did as he was told. Soon his brother caught up with him, and said:
“Kill me, then pound my body up and throw the pieces away.” Gágha
did that, and went on; he didn’t run that time, he just walked; he
didn’t feel scared any longer. Kówam came up behind him, and said:
“Now, little brother, try again. Kill me, then build a big fire and burn
up my body and let the wind carry the ashes away.” Gáhga did that.
His brother overtook him again.
“What kind of a man are you?” asked Gáhga. “Is there any way to kill
you?”
“I wasn’t made to die,” said Kówam, “I shall live always. Now kill me
and cut off my feet and hands and carry them away. Hold them tight.”
Gáhga shot Kówam in the heart, cut off his hands and feet, held
them tight in his own hands, and traveled on, went fast. Right away
his brother called to him. Gáhga’s hands were shut, but the feet and
hands that he had been carrying were gone, and Kówam was by his
side. Then he cut Kówam’s head off and threw it away. At once the
head and body came together.
The brothers were almost home now and Kówam said: “You must
take my bow and quiver and wait on top of the house; I will go in
alone. Don’t be scared when they throw me out; they can’t hurt me.”
Kówam went in, pulled Lok’s head off from the woman’s knees, and
threw him out of the house. Lok came in, caught Kówam, killed him,
and threw the pieces on the fire.
Right away Kówam had Lok by the throat. He choked him and threw
him out. [287]
The fight lasted all night. Just as daylight came, Lok tore Kówam’s
head off; he kicked the body out and held tight to the head. That
moment Kówam said to his brother: “Now I am ready to fight. I was
just waiting for another sun to come up.”
He took his bow and arrows and shot at the Loks through the smoke
hole, and killed them all. Then he covered the house with dry grass,
piled up wood around it, and set it on fire.
CHARACTERS
Two brothers, Tskel and Tcûskai, lived together not far from Klamath
Lake. Tskel’s wife was Skóŭks. Tcûskai was a little fellow. One day
when Skóŭks was outside cooking deer meat and was blowing the
fire to make it burn, she saw Tcûskai watching her; that made her
mad and she threw the meat into the fire. Tskel hit Tcûskai and told
him to stay in the house when Skóŭks was cooking; then he said to
Skóŭks: “Cook more meat; Tcûskai and I are going to the mountain
to hunt for deer. If I kill a big deer, we will camp and stay all night.”
Tskel never killed a deer; no matter how many he saw, he always let
them get away.
When they got to the mountain, they saw a large deer; Tcûskai killed
it, and they camped in sight of a big hole between the rocks. Tskel
wouldn’t camp very near the hole, for he was afraid his brother would
go into it and get hurt. Tcûskai would go anywhere, he wasn’t afraid
of anything.
Tskel cut up the deer; then he and Tcûskai lay down, one on each
side of the fire. As soon as Tcûskai was asleep, Gopher came and
ran across him, just to tease him. Tcûskai [289]woke up and called his
brother: “Come here! Come and see this little fellow! I will give him a
piece of our meat, and we will catch him.”
Tskel didn’t move or say a word. Tcûskai gave Gopher all the roots
Tskel had brought from home; then he took off Tskel’s belt and gave
it to him. Gopher carried it under the rocks. He gave him Tskel’s
deerskin cap and his rabbit-skin blanket.
In the morning when Tskel woke up, the north wind was blowing and
he was almost frozen. He asked Tcûskai where the blanket was.
Tcûskai said: “Gopher took it.”
“Then you gave it to him,” said Tskel; “Gopher couldn’t unwrap me.”
Tcûskai began to feel cold; he wanted to get into Tskel’s ear, but
Tskel was mad, and threw him out. Then he tried to get under Tskel’s
arm, but Tskel pushed him away and sat with his arms folded across
his breast, for he had no blanket and he was cold.
“Why are you so mad?” asked Tcûskai. “I will get those things back;
they are over there under the rocks.”
It was near daylight; Tcûskai was freezing to death. Tskel made a fire
and told him to lie down near it and get warm. Then he made himself
a bark blanket. When Tcûskai was warm, his brother said: “Now you
must get back the things you gave to Gopher.”
Tcûskai ran to the rock and looked into the hole; he thought it was
awful deep, but he ran back, and said: “The hole isn’t deep; we can
build a fire and drive Gopher out.”
“I want my blanket,” said Tskel; “maybe you can crawl in and get it.”
The mountain was Gopher’s house. The rocks were only [290]the roof
of it. Tcûskai saw his brother’s belt, but he was afraid to go and get it.
Tskel said: “Make a fire and blow the smoke into the hole. How long
can you fan the fire without getting tired?”
“But there are many holes,” said his brother. “You will have lots of
trouble. Do you think you can fill the holes with stones?”
“I can fill them quickly,” said Tskel. He ran around, threw stones into
the holes, then came back and blew the fire. But the smoke came
out through other holes, and Tskel said: “Go and stop up every hole
you can find.”
Tskel, to make Tcûskai sorry for what he had done, hid all the water
in a hole where he couldn’t find it. Little Tcûskai got very thirsty. He
ran from one spring to another but couldn’t find water; then he knew
that his brother had hidden it and he said: “I want some water.”
“You can’t have any until you have killed Gopher,” said Tskel. “When
he is dead, I will give you some.”
Tcûskai filled all the little holes and fanned smoke into the big hole.
At midday he said to his brother: “I am stronger than you are; you
never could have filled all these holes.” He went again to hunt for
water. At last he found the place where Tskel had hidden it; then he
drank and drank, drank nearly all the water there was in the hole.
Tskel caught hold of Tcûskai and threw him against the rocks so hard
that he killed him; then he scattered the water. There was only a little
left, but it spread fast, spread until there were rivers and lakes. Then
Tskel went to his brother, took off the string of rattles he wore around
his neck, and struck him five times with it. Tcûskai came to life. Tskel
said: “The holes are stopped up; now I will help you kill Gopher.
[291]He is terrible to look at when he is mad. You must keep your
eyes closed; if you see him, you will die.”
Tskel had two stone knives. He gave one to Tcûskai, then he built a
fire and blew the smoke into the big hole. Tcûskai listened; there was
a noise of some one moving around in the hole. He was so scared
that he died. Tskel brought him to life, and said: “You mustn’t get
scared. That was only a young Gopher; old Gopher hasn’t moved
yet.”
Tskel blew more smoke into the hole. There was a roar as though
the mountain was going to burst open. Tcûskai died again. Tskel
brought him to life, and said: “You have played with these people
and made all this trouble; now you must stay here till it is over. Don’t
get scared every time you hear a noise.”
Just then old Gopher moved and the earth shook. Tcûskai was
dreadfully frightened. (He was on one side of the hole and Tskel was
on the other.) There was a shaking and roar, then a great, red, fiery
head came out of the hole. Tskel cut the head off with his long knife,
skinned it, and made a cap of the skin; then he buried the head
under great flat rocks. Right away the rocks were as red as blood.
(They are red to this day.)
In the hole where Gopher was it is always hot, no matter how cold it
is outside. Gopher’s body, turned to stone, is still in the hole.
After Tskel killed Gopher, he and Tcûskai went home, but Tskel didn’t
want to stay there. He thought about his cousin, Kaiutois. One day
he said to Skóŭks: “I am going to see my cousin,” and he sent
Tcûskai to ask Gäk if he would go with them. Gäk was willing and the
three started off. As they traveled, people told them they mustn’t go
near the Leméis family, that they were killing everybody, that each
day they carried off men to eat. Tskel said: “I am traveling around the
world to see people; I’m not afraid of Leméis.” [292]
When they got near Leméis’ house, Tskel put on his gopher-skin cap
and put little Tcûskai under his arm, where he couldn’t do any
mischief. Then he gave Gäk a sharp bone, and said: “When they
give you dead men’s meat to eat, make a hole in your throat and let
it out; don’t swallow it.”
The five Kaiutois brothers and old man Leméis with his wife and five
boys lived in one house. The five Kaiutois lived on one side of the
house and old Leméis on the other. When Tskel went to the house,
the Kaiutois brothers and Leméis boys were off hunting for deer.
Old Leméis and his wife saw Tskel’s gopher-skin cap and they were
so scared that they ran out of the house. They built a fire and began
cooking; they were afraid to go inside. The wives and children of the
Kaiutois brothers were frightened, too.
Tskel sat in the house with his head down. Tcûskai teased him to let
him put the cap on and run out and scare the old man, but Tskel
pinched him and told him to keep still where he was, under his arm.
Gäk was lying on the ground and looking at Tskel.
Soon old Leméis’ eldest son came home. When he saw his father
and mother outside, he asked: “What are you doing out here?”
“What is there stronger than I am?” asked the son. “I have been off
killing men. I am not afraid of this thing.”
“You haven’t seen it,” said old Leméis. “You can’t go into the house.”
The young man went to the house. He took one step down the
ladder, saw Tskel’s cap, and turned back, screaming so loud that the
ground shook. He said to his father, “There is something there
stronger than I am; I can’t go in.”
The second brother came home. He saw his father outside and
asked: “Why are you out here?”
One after another the five brothers came home. Each brother got
one step farther into the house; each one screamed and ran out. The
fourth brother said: “I am stronger than anybody. If this man had ever
heard of me, he wouldn’t have come here.” He took four steps into
the house, roared with fright, and ran away. The fifth brother was the
strongest of all the brothers. There were five steps down into the
house; he was on the last step when he saw Tskel’s cap. He roared
and with one step was out.
The five Kaiutois brothers came home just at sundown. When Tskel
saw them, he looked up and they knew him. He took off his cap, put
it behind him, and they all went in. Then they called their wives, and
asked: “Why didn’t you cook for this man? He is hungry. Come in
and cook deer meat for him.”
Tskel said: “Tell Leméis and his sons to come in. It is cold outside.”
They were glad; they went in, and right away they began to cook
dead men.
Kaiutois’ meat was done first, and Gäk and Tskel ate deer meat.
Little Tcûskai said: “Let me down, brother; I want to eat. I am
hungry.” Tcûskai pinched him and told him to keep still, but Tcûskai
said: “I can’t, you don’t give me enough to eat.”
When Leméis’ meat was done, the eldest son gave some of it to
Gäk. Gäk put it in his mouth, but it came out of the hole in his throat
and dropped on the ground.
Tskel put some strong sticks in Gäk’s arms, for he knew that the
Leméis brothers would try to kill him. They sat down by the fire and
asked Gäk to come and sit near them. Then they said to one
another: “Let’s twist arms,” and the eldest brother said: “Come and
play with us, Gäk.”
Gäk said: “I never play that way.” After they had teased him a long
time, Tskel said: “Play with them; I won’t let them hurt you.” [294]
The eldest brother took hold of Gäk, twisted his arm hard, but
couldn’t break it; it was soft. “Stiffen your arm,” said Leméis. Gäk
stiffened his arm, but Leméis couldn’t break it. Then Gäk took hold of
Leméis’ arm, twisted it hard, and broke it. Leméis ran out of the
house and died.
Gäk killed four of the brothers; then the youngest and strongest
wanted to try. Gäk didn’t want to twist arms with him, but Tskel said:
“Don’t be afraid, he can’t kill you.” Gäk held out his arm and Leméis
twisted it terribly. Gäk screamed; he couldn’t help it, it hurt so.
Then Tskel said to Leméis: “Let me twist your arm.” He took hold of
Leméis’ hand with a tight grip and broke every bone in it; then he
twisted his arm and broke it.
When all five of the old man’s sons were dead, Tskel said: “Hereafter
you will be of no use in this world. You will be persons no longer. You
will go up to the sky and all you will do there will be to frighten people
by making a big noise.”
He told the five Kaiutois brothers not to live in the house with old
Leméis and his wife. “Their house is dirty,” said he. “It smells of dead
people. The juice of dead people runs on to your meat; you have the
taste of it now, and in after times you will try to kill people.”
The Kaiutois brothers moved away. Old Leméis and his wife felt
badly; they were lonesome for their children. Tskel said: “You can go
to your sons; you are of no use in this world,” and he sent them to
the sky.
Now Tskel and Tcûskai went home. Skóŭks was mourning; she
thought they were dead.
The next day Tskel went to hunt. He killed five deer and was home at
midday. He was dry and he sent his brother to bring him some water.
Tcûskai ran to the spring, and there, sitting in the spring, was an old,
white-haired man.
“What are you here for?” asked Tcûskai. “We don’t [295]want old men
in our spring. My brother is dry. I am after water for him. Get out of
our spring!” He told him two or three times to get out. The old man
didn’t move, but at last he said: “Go and tell your brother to come
and wrestle with me.” Tcûskai ran back to the house.
“There is an old man sitting in the spring,” said Tcûskai. “He won’t let
me get a drop of water.”
Tcûskai went back and screamed: “Get out of there, old man! You
are all dirt; you’ll spoil our water!”
The old man didn’t move, but he said: “Tell your brother to come and
wrestle with me. I hear that he has killed all the Leméis people. I am
their kin. I have come to wrestle with him.”
Tcûskai said: “Let my brother have some water to drink; then he will
come.”
The old man turned around and let Tcûskai take a little water out of
the spring. Tcûskai carried it to his brother, and said: “That old man
has come to fight you for killing the Leméis people. He wants you to
come to the spring and wrestle with him.”
Tskel drank the water and ate pounded seed. Then he went to the
spring and wrestled with the old man. They wrestled till dark, then
the old man threw Tskel, rolled him up in a skin blanket, took his own
form,—an animal with great horns,—put Tskel on his horns, and
carried him down in the water and off under the ground. He carried
him a long distance, then came out near a large lake. He took Tskel
off his horns, unrolled him, and said: “Look around, before I kill you.”
Tskel saw that they were on a narrow ridge of rock that ran, like a
little trail, to the middle of the lake.
The old man said: “When I get to the end of this trail, I will cut you
into small pieces and throw you to my children. They are hungry for
your flesh. As I throw the pieces, I will say: ‘Here is a piece of Tskel.
Eat it.’ They will be glad, and all my kin will be glad that you are
dead.” [296]
“I am scratching myself.”
“I don’t want to suffer while I live,” said Tskel. He was getting his
stone knife out. It was tied up in his hair and the old man hadn’t seen
it. With the knife Tskel cut holes in the skin blanket for his eyes and
his hands, and just as he got to the end of the trail, he stuck the knife
into the old man and killed him. Then he cut the body up and threw it
piece by piece into the lake. As he threw the pieces, he called out:
“Here is Tskel’s shoulder! Here are Tskel’s ribs! Here are his legs!
Here are his arms!” As fast as he threw the pieces, the old man’s
children caught and ate them. At last he threw the head. It was an
awful-looking thing, enough to scare any one.
When the children saw it and knew that they had eaten their father,
they were so mad that they sent everything they had to find Tskel
and kill him. They sent what they thought he would like,—knives,
hatchets, beads, shells, blankets—to lie in his path. If he took up any
one of them, he would die.
Tskel passed them all till he came to the last, a stone knife sharp on
both edges, that looked so nice that he picked it up. Right away the
ends of his fingers were burned off. He dropped the knife, rubbed his
fingers with his own stone knife, and they were well again. Then he
went on till he reached home. Skóŭks and little Tcûskai had covered
their hair with deer fat and pounded coal; they were mourning for
him.
When Tskel saw Tcûskai, he asked: “What are you doing? Why are
you so dirty?”
Tcûskai said: “I was just going to look for you.”
Skóŭks said: “He should be whipped for telling lies. He [297]has been
everywhere in the world hunting for you. Just now he came home
and put coal on his head, for when he couldn’t find you he thought
you were dead.”
Tskel was chief in the Klamath country. He was the strongest person
living. No other man could have killed the old man of the lake.
Now Tskel stayed at home for a long time. He killed deer and dried
the meat and told his brother many things about the people in the
world.
The next day he heard the song again, but he didn’t follow it. He
went home and told Skóŭks that the old man’s daughter had come to
kill him. He didn’t hunt again. One day the woman came and sat in a
clump of bushes near Tskel’s house and told the crows to fly over
her. Little Tcûskai saw the crows and said to his brother: “The crows
are eating something. You had better go and see what it is.”
“What kind of a woman are you?” asked Tcûskai. She didn’t answer.
Tcûskai went three or four times to see the woman and each time
she spat beads. When she found that Tskel wouldn’t come to her,
she went to the house. Skóŭks saw her coming and she fixed herself
up. She had power and could do things. Tskel was lying on the
ground. When the woman came in, she sat down by him and began
spitting beads. Then Skóŭks spat, and her beads were nice. The
woman was frightened a little; she spat long white beads; Skóŭks
spat more beautiful beads. They kept spitting beads till, just as the
sun went down, the woman by her power made sleep come over
Tskel and Tcûskai, and made Skóŭks grow so sleepy she could
scarcely see. When darkness came the woman began to wrap Tskel
in a skin blanket to carry him off.
Right away Skóŭks was wide awake. She jumped on the woman and
fought with her. They fought all night. First one would have Tskel and
then the other. He was sound asleep all the time. There was such a
dust from their fighting that Tcûskai was covered with it. Just at
daylight Skóŭks gave out; she couldn’t fight any longer.
The woman snatched up Tskel and carried him off. She went under
the ground, and as she went she made a furrow on the surface.
Skóŭks followed for a long time, but she couldn’t get at the woman,
for she couldn’t travel underground. At last she went home, struck
Tcûskai with his neck rattles, and said: “You had better get up and
follow your brother. You found him a nice wife, nicer than I am. Now
you can go and live with them!”
Tcûskai woke up and went off to look for his brother. The trail had
disappeared; he couldn’t find even one track.
When the woman went into the ground, she was just such an animal
as her father had been. She carried Tskel on her horns till she came
out at the lake, then she put him down and said: “I will let you rest
twice before I kill you. How do you like this place?”
She carried him to the middle of the trail in the lake, then [299]she put
him down, and asked: “What did you do when you were here
before?”
“Nothing.”
“No.”
“What do you think you will do when you die? Will you come to life,
or will you stay dead?”
She took him up to carry him to the end of the trail where she could
throw him into the lake. He got his knife out, a little at a time, and just
as she was going to put him down again, he cut her head off. From
each side of the ridge the water rushed up; the ridge shook and
made a terrible noise. Tskel cut the woman’s body up, and threw the