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
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Titanium Dioxide (TiO2) and Its Applications Francesco

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 Corrosion Science 136 (2018) 60–69

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Fabrication of heterostructured β-Bi2O3-TiO2 nanotube array composite film T

for photoelectrochemical cathodic protection applications
⁎
Zi-Chao Guan, Hai-Peng Wang, Xia Wang, Juan Hu, Rong-Gui Du
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China

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.

1. Introduction remarkable dielectric permittivity and photoluminescence property.

Titanium dioxide (TiO2), an n-type semiconductor, has been at-
tracting much attention since it was found to have the ability to de-
compose H2O under illumination by Fujishima and Honda in 1972 [1].
TiO2 shows many special properties, such as low toxicity, easy fabri-
cation, low cost, high stability and excellent photosensitivity [2]. As a
result, it has been widely applied in photodegradation of organics [3,4],
photocatalytic water splitting [5], dye-sensitized solar cells [6], gas
sensors [7], photoelectrochemical cathodic protection (namely photo-
cathodic protection) [8,9], biomedical materials [10], etc. Compared to
a TiO2 nanoparticle or nanowire film, a vertically oriented anatase TiO2
nanotube array (NTA) film prepared by a simple electrochemical ano-
dization method possesses higher photoelectrochemical activity owing
to its large interfacial area and excellent electron transport property
[11]. However, TiO2 has a wide band gap of 3.2 eV and can absorb only
UV light which makes up a small portion of sunlight. Moreover, the
photogenerated charge carriers in TiO2 easily recombine, which ad-
versely affects the photoelectrochemical performance of TiO2.
In recent years, various methods have been developed to modify
TiO2 NTA films for enlarging the spectral response and suppressing the
fast recombination of photogenerated carriers, such as metal doping (Fe
[12], Mo [13], Co [14] and Cr [15]), non-metal doping (N [16,17], S
[18], B [19] and C [20]) and semiconductor heterostructure fabrication
(CdS-TiO2 [21], WO3-TiO2 [22], SnO2-TiO2 [23], Bi2S3-TiO2 [24] and
NiO-TiO2 [25]). Bi2O3 (a p-type semiconductor) is the simplest Bi-based
oxide, and is used in extensive photoelectrochemical applications due
to its excellent properties [26–29], such as the high refractive index,
There are six polymorphic forms for Bi2O3: α-Bi2O3 (monoclinic), β-
Bi2O3 (tetragonal), γ-Bi2O3 (body-centered cubic), δ-Bi2O3 (face-cen-
tered cubic), ε-Bi2O3 (orthorhombic), and ω-Bi2O3 (triclinic)
[27,30,31]. Among these polymorphs, β-Bi2O3 has a distinctive crystal
structure, which gives it a narrower band gap [32] and further provides
the transfer channels for the photogenerated electrons and holes [33].
Consequently, β-Bi2O3 is usually recommended as a promising visible-
light-driven photocatalyst, thanks to its relatively narrow band gap
(2.3–2.8 eV) [34], strong light absorption over the UV–vis region and
high separation efficiency of photogenerated carriers [35]. So β-Bi2O3
should be a suitable candidate for TiO2 nanotube modification for their
matching energy levels. More importantly, a p-n heterojunction will be
formed at the interface between the p-type Bi2O3 and the n-type TiO2 if
they are combined into a composite, which can significantly improve
the separation efficiency of photogenerated electrons and holes.
There have been some reports about Bi2O3-TiO2 nanotube compo-
sites for their photocatalytic or photoelectrocatalytic applications
[36–41]. For example, Ge et al. [36] developed an ultrasonication-as-
sisted successive ionic layer adsorption and reaction (SILAR) method to
synthesize a uniform p-Bi2O3-TiO2 nanotube p-n heterojunction that
showed commendable photocatalytic degradation performance for
methyl orange. Other methods such as chemical bath deposition [38],
dip-coating [39,40] and vacuum-assisted impregnation [41] were also
reported to prepared Bi2O3-TiO2 NTA composites for the purpose of
photocatalytic and other applications. However, there have been no
reports on Bi2O3-TiO2 NTA composite films applied for photocathodic
protection (a photoelectrochemical approach for preventing metal

⁎
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 damage [42]).
In this work, a β-Bi2O3-TiO2 NTA composite film was fabricated by
electrochemical anodization combined with ultrasonic-assisted elec-
trodeposition for its application in photoelectrochemical cathodic pro-
tection. The protection effects and mechanisms of the composite film on
403 stainless steel (403SS) were especially investigated.
2. Experimental
2.1. Preparation of β-Bi2O3-TiO2 NTA films
Ti foils (99.8% purity) were processed into the specimens with di-
mensions of 15 mm × 10 mm × 0.1 mm and used as the substrates to
fabricate β-Bi2O3-TiO2 NTA composite films. Before use, the specimens
were ultrasonically cleaned in acetone, ethanol, and deionized water
for 20 min successively and then dried.
A TiO2 NTA film was directly prepared on the Ti substrate through
anodization in a classical two-electrode system with a Ti foil specimen
as the working electrode, and a platinum sheet as the counter electrode.
The anodization was conducted at a constant voltage of 20 V for 30 min
in a 0.5 wt% HF solution at room temperature. After the anodization,
the sample was rinsed with deionized water, and then heated from
room temperature to 450 °C (heating rate of 5 °C min−1) in air and
annealed at 450 °C for 2 h to obtain a crystalline anatase TiO2 NTA film.
A desired β-Bi2O3-TiO2 NTA composite film was prepared via an
ultrasonic-assisted pulse current electrodeposition technique. The as-
prepared TiO2 NTA film was first soaked in a 3 M HCl solution con-
taining 0.1 M Bi(NO3)3 and 0.04 M EDTA (ethylenediaminetetraacetic
acid) for 20 min under ultrasonication (frequency of 40 kHz) to remove
air in the nanotubes and let the electrolyte enter into the nanotubes.
Then the TiO2 NTA film was transferred to the electrolytic cell with the
same HCl solution and acted as the working electrode in the electro-
deposition procedure, while a saturated calomel electrode (SCE) and a
platinum sheet served as the reference and counter electrodes, respec-
tively. The electrodeposition was carried out by applying a
−80 mA cm−2 cathodic current for 20 ms and an 80 mA cm−2 anodic
current for 2 ms alternately for 100 cycles, and the break time (no
applied current) was 1 s between each cycle. Finally, the sample was
heated from room temperature to 550 °C in air with a heating rate of
5 °C min−1 and annealed at 550 °C for 2 h.
2.2. Characterization
A field emission scanning electron microscope (FE-SEM, Hitachi
S4800) was employed to observe the morphologies of the prepared
films. The energy dispersive X-ray spectroscopy (EDS) instrument at-
tached to the FE-SEM was used for the film surface elemental analyses.
The crystalline structures of the films were characterized by X-ray dif-
fraction (XRD, Rigaku Ultima IV) and the surface chemical composi-
tions were determined by X-ray photo-electron spectroscopy (XPS, PHI
Quantum 2000).
Light absorption efficiencies were detected by a UV–vis-NIR spec-
trophotometer (Varian, Cary 5000). The photoluminescence (PL)
measurements were performed with a fluorescence spectrometer
(Hitachi F-7000) with the excitation at 370 nm.
2.3. Photoelectrochemical and electrochemical measurements
The time-dependent photocurrent density (in open-circuit situa-
tions) and photopotential (photo-induced open circuit potential) for the
TiO2 NTA and β-Bi2O3-TiO2 NTA films were measured separately in a
three-electrode cell with the prepared film as the working electrode, an
SCE as the reference electrode and a platinum coil as the counter
electrode. The electrolyte in the cell was a 0.5 M Na2SO4 solution. A Xe
lamp was used as the light source to provide white light from 190 nm to
1100 nm, and the prepared film was illuminated with the white light
61
Corrosion Science 136 (2018) 60–69
which had passed through a quartz window. The time evolution of the
photocurrent and photopotential were recorded under dark and illu-
mination conditions for several cycles. Under dark conditions, the
current density-potential (i-E) curves of the prepared films in the 0.5 M
Na2SO4 solution were measured in the above three-electrode cell with
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.
SCE). All the measurements were performed by a model 263A po-
tentiostat/galvanostat (Princeton Applied Research, USA).
403SS specimens with dimensions of 15 mm × 10 mm × 1 mm
were prepared and used as the metal to be protected by the prepared
films. The composition of 403SS was (wt%): 0.95 C, 0.08 P, 0.94 Si,
0.53 Mn, 0.96 Ni, 13.03 Cr and balance Fe. Before use, the specimen
was mechanically abraded by SiC paper from 600 to 1200 grit gradually
and polished with 1.0 μm Al2O3 powder, and ultrasonically cleaned
sequentially in ethanol and deionized water. Then, each specimen was
clamped to a Cu core wire and covered with nail polish leaving a single
working surface with an area of 1 cm2 to act as an electrode.
The potential measurements and electrochemical impedance spec-
troscopy (EIS) tests were conducted for the 403SS specimen coupled
with the different films (as photoanodes) to investigate the photoelec-
trochemical cathodic protection performances of the prepared films.
The schematic diagram of the experimental setup is shown in Scheme 1,
which is similar to the measurement system reported previously by our
group [43]. In this setup, there were two electrolytic cells connected by
a salt bridge (saturated KCl in agar in a flexible glass tube). One was a
corrosion cell with the 403SS plate working electrode, the SCE re-
ference electrode and the platinum sheet counter electrode in a 0.5 M
NaCl solution for electrochemical measurements. The other was a
photoelectrochemical cell with a photoanode (namely the prepared film
sample) in a 0.5 M Na2SO4 solution, and a quartz window as an optical
channel. The photoanode was coupled to the 403SS plate by a copper
wire. The light source was a 150 W Xe lamp. A computer-controlled
potentiostat/galvanostat (model 263A, Princeton Applied Research,
USA) was employed for photoelectrochemical and electrochemical
measurements. The corrosion potential (open circuit potential) change
of the uncoupled 403SS was measured in the corrosion cell with a 0.5 M
NaCl solution. The photopotential (photo-induced open circuit poten-
tial) change of the 403SS in the same NaCl solution coupled with the
TiO2 NTA or β-Bi2O3-TiO2 NTA film photoanode under intermittent
white light illumination was measured in open-circuit situations (no
Scheme 1. Schematic diagram of the experimental setup for photoelectrochemical
cathodic protection measurements in open-circuit situations. Potential variations and EIS
spectra of 403SS uncoupled and coupled to different films as photoanodes with time were
measured under illumination and dark conditions. The electrolytes in the corrosion cell
and photoelectrochemical cell were a 0.5 M NaCl solution and a 0.5 M Na2SO4 solution,
respectively. 403SS was coupled with the photoanode by a Cu wire. A 150 W Xe lamp was
used to provide white light.
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.

externally supplied currents or potentials). EIS spectra of the 403SS

electrode were recorded at its corrosion potential over a frequency
range from 100 kHz to 0.01 Hz with an applied AC voltage of 10 mV for
the stainless steel uncoupled or coupled with the prepared film pho-
toanode under white light illumination. The EIS data were analyzed by
using ZView−Impedance Software.
All the chemicals used in this work were analytical grade. All
measurements were carried out at room temperature (typically
25 ± 2 °C) and repeated at least three times to check the reproduci-
bility.

3. Results and discussion

3.1. Materials characterization

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
confirmed below) on the TiO2 NTA film, the SEM images of the top-
view and cross-sectional views of the Bi2O3-TiO2 composite film are
shown in Figs. 1c and d, respectively. The ultrasonic treatment and
electrodeposition procedures did not destroyed the intrinsic structure of
the TiO2 NTA film. Some nanoparticles were evenly distributed on the
NTA surface without blocking the nanotube orifices, and the tube wall
thickness increased. During the SEM observation, the EDS measurement
was accomplished to confirm the elemental composition of the com-
posite film. Fig. 2 shows the corresponding EDS result, which indicated
the presence of Ti, O and Bi elements in the composite film. The pre-
sence of Bi provided an important evidence for the formation of the
desired Bi2O3-TiO2 composite through the ultrasonic-assisted electro-
deposition method. The ultrasonication process could efficaciously re-
move air from the TiO2 nanotube surfaces, and simultaneously force the
electrolyte to diffuse quickly into the pores of the nanotubes. The
subsequent electrodeposition procedure was intended to make the
electropositive Bi3+ ions be adsorbed onto both the exterior and in-
terior surfaces of the nanotubes, and finally they were transformed into
the Bi oxide.
The XPS measurements were performed to further confirm the
chemical compositions and oxidation states of the composite film,
especially for the Bi oxide deposited on the TiO2 NTA film. XPS wide
scan spectra for both the bare TiO2 and Bi2O3-TiO2 films are presented

62
Z.-C. Guan et al.
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-
TiO2 composite film for Ti 2p, Bi 4f and O 1s are presented in
Figs. 3b–d, respectively. In the wide scan spectra, the peaks for C 1s
(284.2 eV), Ti 3s (60.7 eV), Ti 2p (458.2 eV), Ti 2s (580.0 eV) and O 1s
(529.5 eV) could be observed both for the bare TiO2 and composite
Bi2O3-TiO2 films, and the corresponding AES peaks of O KLL and Ti
LMM appeared at 975.6 eV and 1071.4 eV, respectively. While the
peaks at 160.6 eV and 442.1 eV corresponding to Bi 4f and Bi 4d could
be observed for the composite film, respectively. The C 1s peak was
thought to be caused by the adventitious hydrocarbon contamination
[36]. The high-resolution narrow scan spectrum of Ti 2p of the com-
posite film is displayed in Fig. 3b. The two peaks centered at 458.1 eV
and 463.8 eV were ascribed to Ti 2p3/2 and Ti 2p1/2, respectively, and
the doublet separation of Ti 2p was 5.7 eV, which had good agreement
with the reported value [44], indicating the existence of Ti4+ in the
composite film. As presented in Fig. 3c, the high resolution XPS spec-
trum of the Bi 4f region exhibited two peaks located at 158.7 eV and
164.1 eV, which belonged to Bi 4f7/2 and Bi 4f5/2, respectively. Fur-
thermore, the energy difference between the two peaks was exactly
5.4 eV in agreement with the data reported in the literature [36]. So,
the XPS data in Fig. 3c provided a convincing proof that the valence
state of Bi was +3 in the composite film, indicating the existence of
Bi2O3 [36,45,46]. In Fig. 3d, the narrow spectrum of O 1s contained
only one broad peak, which could be fitted into three peaks with
binding energies of 528.5 eV, 529.5 eV and 531.2 eV, respectively.
Apparently, there were some overlapping parts among these three
63
Corrosion Science 136 (2018) 60–69
peaks, suggesting that there were different chemical states of O element
in the composite film [47]. Specifically, the peak at 528.5 eV belonged
to the O of Bi-O, and the peak at 529.5 eV was attributed to the O from
Ti-O. These two chemical states of O were considered as lattice O, and
indicated the existence of Bi2O3 and TiO2, respectively. The peak at
531.2 eV could be ascribed to the adsorbed oxygen brought by irre-
versibly adsorbed H2O on the film surface [48,49].
XRD analyses were also performed to study the crystalline phase of
film samples. Fig. 4 presents the XRD patterns of the Ti foil, TiO2 NTA
and Bi2O3-TiO2 NTA films. The additional peaks were ascribed to TiO2
or Bi2O3 in the TiO2 NTA and/or Bi2O3-TiO2 composite films besides
the main diffraction peaks of Ti from the films. To be specific, the
diffraction peaks at 25.3° and 48.1° for the bare TiO2 NTA film (Fig. 4b)
could be indexed to the (101) and (200) planes of anatase TiO2 phase
(PDF #02-0387), respectively. At the same time, no peaks corre-
sponding to rutile TiO2 were detected, demonstrating that the TiO2
obtained by anodization and 450 °C calcination was anatase phased
TiO2. As shown in Fig. 4c, after the electrodeposition of Bi2O3, a dif-
fraction peak at 27.5° originated from the composite film was indexed
to the (121) plane of β-Bi2O3 (PDF #72-0398). So the Bi2O3 deposited
on TiO2 NTA film was confirmed as β-Bi2O3.
Based on the above analyses and discussions, we concluded that the
desired β-Bi2O3-TiO2 NTA composite film has been fabricated by an
anodization combined with ultrasonic-assisted electrodeposition
method. Additionally, the above characterization results showed the
good reproducibility of the preparation method of the composite film.
Z.-C. Guan et al.
Fig. 4. XRD patterns of (a) Ti foil, (b) the TiO2 NTA film and (c) the β-Bi2O3-TiO2 NTA
film.
3.2. Light absorption properties
In order to investigate the photoelectrochemical performances of
the prepared films, their UV–vis absorption spectra and photo-
luminescence (PL) emission spectra were measured. Fig. 5a presents the
UV–vis absorption spectra of the TiO2 and β-Bi2O3-TiO2 NTA films. The
bare TiO2 NTA film exhibited an absorption edge about 380 nm caused
by the electron transition from the valence band (VB) of O 2p to the
conduction band (CB) of Ti 3d in anatase TiO2 [50]. Compared with the
bare TiO2 NTA film, the absorption edge of the β-Bi2O3-TiO2 NTA
composite film showed a significant red shift to about 490 nm in the
visible light region. Furthermore, the absorption performance of the
composite film in both the UV and visible light regions was also en-
hanced. That is to say, the β-Bi2O3-TiO2 composite film exhibited a
broader and stronger light absorption, the main reason for which is the
synergistic absorption effect of the Bi2O3 photosensitizer and the for-
mation of p-n heterojunction [36,37,51,52]. Based on the absorption
data from the UV–vis spectroscopic measurements, the band gap of the
film can be estimated from the following equation [53]:
αhν = A(hν − Eg)η
where α, h, ν are the absorption coefficient, Planck's constant and light
frequency, respectively. A is a constant related to temperature, photon
energy and phonon energy. Eg is the band gap and η value is determined
by the transition type of electrons in the semiconductor, i.e., η = 1/2 is
for the direct transition and η = 2 is for the indirect transition. Here η is
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.
Corrosion Science 136 (2018) 60–69
taken as 2 because of the indirect transition in TiO2 semiconductor [9].
Based on the absorption data from the UV–vis measurements and Eq.
(1), the (αhν)1/2-hν curves of the prepared films could be obtained (as
shown in Fig. 5b) and their band gaps could be determined from ex-
trapolating the straight lines to α = 0 [54]. According to the UV–vis
spectroscopic results and the above estimation method, the band gap
energy of the bare TiO2 film was 3.21 eV, close to the theoretical band
gap of anatase TiO2 (3.2 eV), while the band gap energy of the β-Bi2O3-
TiO2 composite film was 2.55 eV, which was noticeably narrowed by
the deposition of β-Bi2O3 nanoparticles. The presence of Bi orbit might
efficiently decrease the energy gap between Ti and O orbitals of TiO2 in
the composite film [55]. The smaller band-gap energy could lead to the
broader light absorption region and induce the red shift of the ab-
sorption edge of the β-Bi2O3-TiO2 NTA film (Fig. 5a).
Fig. 6 presents the PL spectra of the bare TiO2 and β-Bi2O3-TiO2
NTA films. The two film samples showed the similar peak positions in
the PL spectra, but they differed in the peak intensity. The peak located
at 440–520 nm could be fitted into three peaks separately at 465 nm,
474 nm and 486 nm (inset of Fig. 6). The two peaks at 465 nm and
474 nm were mainly ascribed to the emission peaks caused by the
oxygen vacancies in TiO2 [56], while the peaks of 486 nm and 580 nm
came from the electron capture emission by surface states (Ti4+-OH)
[57]. The PL peaks result from the recombination of photogenerated
electron-hole pairs, the lower PL peak intensity implies the higher se-
paration and transfer efficiency of electron-hole pairs and the better
photoelectrochemical performance of a semiconductor material
[58,59]. The β-Bi2O3-TiO2 NTA composite film showed the lower PL
intensity than the bare TiO2 NTA film, indicating that the recombina-
tion of electron-hole pairs in the composite film was efficiently reduced
and the separation and transfer efficiency of electron-hole pairs was
enhanced, which is really essential for photoelectrochemical applica-
tions.
According to the foregoing discussion, the incorporation of β-Bi2O3
into the TiO2 NTA film could optimize the energy band structure of
TiO2, narrow the band-gap and extend the light absorption to the
visible region, which would be beneficial to generate more electron-
hole pairs in the β-Bi2O3-TiO2 NTA composite film under illumination.
These properties would be very important for photoelectrochemical
cathodic protection applications.
3.3. Photoelectrochemical cathodic protection effect
(1)
Compared to the traditional cathodic protection (sacrificial anode
and impressed current cathodic protection), the photoelectrochemical
cathodic protection has high research value and inviting application
prospects because it does not consume anode materials and external
electric energy. The basic mechanism of photoelectrochemical cathodic
protection is that a semiconductor photoanode is used as a replacement
64
Z.-C. Guan et al.
Fig. 6. Photoluminescence spectra of (a) the TiO2 NTA film and (b) the β-Bi2O3-TiO2 NTA
film with the excitation wavelength of 370 nm, the inset shows the fitting result of the
peak between 440 nm to 520 nm.
for the traditional sacrificial anode, and provides CB electrons gener-
ated from the VB under illumination for a metal to be protected. In a
photoelectrochemical cathodic protection system, the semiconductor
photoanode supplies the metal with a photocurrent resulting from
photoelectric conversion to protect the metal cathodically from corro-
sion [23,24,42].
In order to inhibit the metal corrosion by the photoelectrochemical
approach, the photoanode under illumination must have the ability to
provide enough cathodic current for the metal. Fig. 7a compares the
instantaneous photocurrent densities of the TiO2 and β-Bi2O3-TiO2 NTA
films in the 0.5 M Na2SO4 solution under white light illumination in
open-circuit situations for evaluating the sensitivity of the film to the
light. The currents as recorded were anodic on the Ti specimen. The β-
Bi2O3-TiO2 NTA composite film showed a photocurrent density of
80 μA cm−2, which was about 4 times as high as that of the bare TiO2
NTA film (about 20 μA cm−2). The enhancement of the photocurrent
density for the composite film presaged higher photoelectrochemical
conversion efficiency. And this enhancement could be attributed to the
deposition of β-Bi2O3, leading to the faster transfer and higher se-
paration efficiency of the photogenerated electron-hole pairs. In addi-
tion, the photocurrent densities of the two samples immediately
changed once the light was turned on or off, indicating the high sen-
sitivity of the films to the light. The two films also showed excellent
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
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
NTA film might provide a more effective photoelectrochemical cathodic
protection effect than the bare TiO2 NTA film. When the light was
turned off, the potentials of the two films immediately shifted positively
due to the electron-hole recombination, which was in accordance with
the results of photocurrent density measurements. Furthermore, the
potential response of both the bare TiO2 and β-Bi2O3-TiO2 films was
almost repeatable, showing good photosensitivity and high stability
during the entire test period, which is important for the application in
photoelectrochemical cathodic protection.
As is known to all, when a metal is under cathodic protection, its
actual potential is more negative than its open circuit potential (OCP).
In this work, the changes of the 403SS potential under different con-
ditions were measured to evaluate the photoelectrochemical cathodic
protection performance of the TiO2 and β-Bi2O3-TiO2 NTA films as
photoanodes. The potential changes of 403SS in the 0.5 M NaCl solution
are presented in Fig. 8. Before coupling, the corrosion potential of
403SS stabilized at about 50 mV vs. SCE (Fig. 8a). As seen in Fig. 8b and
c, when 403SS was coupled to the TiO2 and β-Bi2O3-TiO2 NTA films
under dark conditions, the potentials were negatively shifted to
−150 mV vs. SCE and −190 mV vs. SCE, respectively, because of the
galvanic effect. When the white light illumination was provided, po-
tentials showed further negative shifts to −250 mV vs. SCE and
−400 mV (vs. SCE) for the 403SS electrode coupled with the TiO2 and
β-Bi2O3-TiO2 films, respectively. Under these illumination conditions,
the 403SS were under cathodic protection. The potential of the 403SS
coupled with the β-Bi2O3-TiO2 composite film was 150 mV more ne-
gative than that coupled with the bare TiO2 NTA film, showing more
effective photoelectrochemical cathodic protection by the β-Bi2O3-TiO2
Z.-C. Guan et al.
Fig. 8. Potential changes of 403SS in the corrosion cell with a 0.5 M NaCl solution in
open-circuit situations, (a) corrosion potential of uncoupled 403SS, (b) 403SS coupled
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
were in the photoelectrochemical cell with a 0.5 M Na2SO4 solution.
composite film. When the illumination was turned off, the potential of
the 403SS coupled with the TiO2 film immediately shifted back to the
value (−150 mV vs. SCE) before illumination and remained stable,
while the potential of the 403SS coupled with the composite film
shifted positively to a potential level (−240 mV vs. SCE) lower than
that (−190 mV vs. SCE) before illumination, indicating that the com-
posite film remaining some cathodic protection effect. When the illu-
mination was provided again, the potential of the 403SS coupled with
TiO2 or β-Bi2O3-TiO2 film decreased to the same value as before and
was stable, showing good sensitivity to light. After cutting off the light,
the 403SS potential again rose sharply to the same value as before
(Figs. 8b and c). But the potential of the 403SS coupled with the β-
Bi2O3-TiO2 composite film increased gradually to the level as that be-
fore the first illumination, indicating that the composite film could
provide some degree of cathodic protection even after the light was cut
off during this period (about 15 h). To investigate the stability of the
composite film in the photoelectrochemical cathodic protection appli-
cation, the potential response of the 403SS coupled with the composite
film to 6 on/off cycles of illumination was recorded as shown in the
inset of Fig. 8. The results showed that the composite film was quite
stable and its protecting effect on the 403SS did not evidently attenuate
during the illumination for the 6 cycles.
EIS can provide valuable electrochemical information of the metal/
solution interface. So, EIS measurements were executed to evaluate the
photoelectrochemical cathodic protection effects of the prepared films
[23,24,60]. The Nyquist, Bode-phase and Bode-modulus plots of 403SS
in the 0.5 M NaCl solution uncoupled and coupled with different film
photoanodes are presented in Fig. 9A–C, respectively. The Nyquist plots
featured only one capacitive loop, and the Bode plots showed only one
time constant accordingly. The radius of the capacitive loop in the
Nyquist plot decreased when 403SS coupled with the film photoanode
under white light illumination, and showed the smallest radius when
403SS coupled with the β-Bi2O3-TiO2 composite film. The similar var-
iation trend was observed in Bode plots. Therefore, the EIS spectra
could be modeled by the equivalent circuit shown in the inset of
66
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
illumination relative to the bare TiO2 NTA film, and more effectively
inhibit the corrosion of 403SS.
3.4. Mechanism
Based on the above results and discussions, the mechanism of the
enhanced photoelectrochemical cathodic protection provided by the β-
Bi2O3-TiO2 composite film for 403SS is illustrated in Scheme 2.
TiO2 is a recognized n-type semiconductor, while β-Bi2O3 belongs to
a p-type semiconductor. In the β-Bi2O3-TiO2 NTA film, a p-n hetero-
junction was built between the p-type Bi2O3 and the n-type TiO2, which
could be proved by the i-E curves shown in Fig. 9D. The dark current of
the bare TiO2 film was almost zero, showing the poor p-n heterojunction
effect. However, the current of the β-Bi2O3-TiO2 NTA film was asym-
metric in forward and reverse scans, showing an obvious diode beha-
vior. This result provided reliable evidence that the p-n heterojunction
was built and there was an internal electrostatic field at the interface
between TiO2 and Bi2O3 [61]. When the p-n heterojunction was formed,
electrons transferred from n-type TiO2 to p-type Bi2O3, while holes
transferred in the opposite direction until the system reached equili-
bration because of the diffusion effect of carriers. This carrier diffusion
results in the formation of internal electrostatic field in the p-n het-
erojunction (shown in Scheme 2), which made the n-type TiO2 be po-
sitively charged and the p-type Bi2O3 be negatively charged [62,63].
As shown in Scheme 2, when the β-Bi2O3-TiO2 NTA film was irra-
diated by white light (Xe lamp, 190–1100 nm), TiO2 could absorb the
UV light to excite its VB electrons to the CB, while the photogenerated
holes migrated from the TiO2 VB to the β-Bi2O3 VB due to the driving
force of the internal electrostatics in the p-n heterojunction. Meanwhile,
β-Bi2O3 could absorb UV light and part of visible light due to its narrow
band-gap, and more photoelectrons were generated in the CB of the
excited β-Bi2O3. Similarly, the photoelectrons were transferred from the
β-Bi2O3 CB to the TiO2 CB due to the driving force of the internal
electrostatics. Taken as a whole, the photogenerated electron-hole pairs
in the β-Bi2O3-TiO2 composite film were separated effectively, the
photogenerated electrons were transferred from the TiO2 CB to the
403SS to provide cathodic protection, and the photogenerated holes in
the β-Bi2O3 VB were consumed by hole scavengers in the solution. So,
the β-Bi2O3-TiO2 NTA film had a higher charge carrier separation and
transfer efficiency and superior photoelectrochemical performance
compared with the unmodified TiO2 film. Therefore, the deposition of
β-Bi2O3 nanoparticles on the TiO2 nanotubes could improve the
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.

photoelectrochemical cathodic protection performance of the TiO2 References

composite film.
4. Conclusions
In this study, a method containing anodization and electrodeposi-
tion has been developed to fabricate a β-Bi2O3 nanoparticle modified
TiO2 NTA composite film with a p-n heterostructure. Compared with
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Another random document with
no related content on Scribd:
 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]

“Is she crying?” asked Kówam.

“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.”

“How can we go home while those big-footed people are there?”

asked Gágha. He was crying again.

“I am not afraid of those men,” said Kówam. “That is my house; I will

drive them out of it or I will kill them.”

When they were part of the way home, Kówam said: “Little brother,
take my bow and arrow and shoot me in the heart.”

“How can I do that? You are my brother.”

“It won’t hurt me. I want you to practise shooting.”

“You are my own brother, all the one I have. I won’t do it,” said
Gágha.

“You must,” said Kówam. “It won’t hurt me.”

“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]

When Kówam was killed and thrown out, his mother-in-law

screamed: “I am glad you are dead, old Black Legs!” When Lok was
thrown out, she screamed, “Now you are killed, old Big Feet, my
son-in-law is a great man!”

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.

Gáhga screamed and cried; he wanted his sister-in-law saved.

Kówam wouldn’t listen to him and wouldn’t let his wife out. Then
Gáhga got mad at his brother, and said: “Hereafter you won’t have a
person for a wife. You will be an animal. People will call you by
different names, and you will always live in the woods and make a
great noise talking.”

Kówam said: “Punch a stick in where your sister-in-law was sitting.”

She was dead, but a voice spoke out of the fire and said to Kówam:
“You will always stick your bill up in the sun and look off on the water.
And you, my little boy, will be like your brother.”—Ningádaniak. [288]
[Contents]
 MINK AND WEASEL

CHARACTERS

Blaiwas Eagle Lok Bear

Gäk Crow Moi Squirrel
Gapni Louse Näníhläs Bat
Kāhkaas Stork Skóŭks Woodtick
Kaiutois Wolf Súbbas Sun
Kaltsik Spider Sukas
Kéis Rattlesnake Tcûskai Weasel
Kékina Lizard Tskel Mink
Kówe Frog Tusasás Skunk
Kûlta Otter Wŏn Elk
Leméis Thunder

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; he was asleep. Tcûskai gave Gopher a small

piece of meat. He took it and ran off to the rocks, then came back for
more, carried that off and came back again. Each time he came
Tcûskai gave him a larger piece. At last all the deer meat was gone;
then Tcûskai went to Tskel, shook him, and said: “Get up! Get up!
This little fellow has carried off all of our meat.”

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?”

“I can fan it till Gopher comes out,” said Tcûskai.

“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 wondered why Tcûskai didn’t come back. At last he thought:

“Maybe he has found the water; I will go and see.” Tcûskai was still
drinking, and only a little water was left. If Tskel hadn’t thought of the
water and gone to look for his brother, he would have drunk it all and
there would have been no water in the world.

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.)

Tskel said to Gopher: “Hereafter you will be of no account. You will

dig in the ground and people will make fun of you.”

If Tskel hadn’t killed Gopher, there would be no one living in the

world now.

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?”

The old man said: “There is something strange in our house. We

can’t stay there. We have never seen anything like it before. It is
terrible!”

“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?”

“There is something in our house stronger than we are. We can’t go

in,” said the father. [293]
The young man laughed, and asked: “What is there stronger than I
am? There is nothing I can’t kill.” He was down two steps of the
ladder when he saw the cap; he screamed and ran out.

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.

The second brother was ashamed. He said: “That is the way my

brother always does. If he gets beaten, he runs away. Try me.” He
twisted Gäk’s arm, but no matter how he twisted he couldn’t break it.
Then Gäk twisted his arm and broke it, and he ran outside 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.

“Why didn’t you bring me some water?” asked Tskel.

“There is an old man sitting in the spring,” said Tcûskai. “He won’t let
me get a drop of water.”

“Go back and get me some water!” said Tskel.

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]

When he was through talking, he rolled Tskel up again, put him on

his horns, and started. Tskel moved a little.

“What are you doing?” asked the old man.

“I am scratching myself.”

“You needn’t scratch; you will die soon.”

“I itch; I can scratch while I live,” said Tskel. He moved again.

“What are you doing now?” asked the old man.

“I don’t lie easy.”

“Why bother about that? you will die soon.”

“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.

One day when he was out hunting, he heard somebody singing a

beautiful song; he listened and wondered who it was. Then he
followed the sound. It drew him along till he came to a big cedar tree.
A woman was sitting on a bough of the tree and throwing cedar
berries on to a blanket spread under the tree. When she saw Tskel,
she called out: “Come and sit on the blanket!” He knew she was the
old man’s daughter, and he wouldn’t go near her; he went home.

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.”

“Don’t go near that place,” said Tskel.

Tcûskai thought: “Why does my brother tell me not to go to those

bushes? I am going.” He went around the house, out of Tskel’s sight,
and crept toward the bushes. He found a woman sitting on a low
stump; as he went up to her she spat out beautiful beads. The
second time she spat, Tcûskai picked up some of the beads. Each
time she spat the beads were more beautiful than before.

“What kind of a woman are you?” asked Tcûskai. She didn’t answer.

Tcûskai went home, and said: “Oh, brother, there is a beautiful

woman over there in the bushes. You must have her for a wife. Send
Skóŭks off and take her.” Tskel said: “Why don’t you get her for a
wife; she must have come for you.” He [298]was sleepy. He had been
in a half dream since the first day he heard the woman’s song.

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?”

“I like it. I have been here before,” said Tskel.

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.”

“Do you think you will ever go home?”

“No.”

“What do you think you will do when you die? Will you come to life,
or will you stay dead?”

“I don’t know,” said Tskel.

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