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
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 “If as I suppose I am to understand, you mean that I’m naturally a
hypocrite,” returned the doctor rather stiffly, “you are mistaken. Miss
Page is the best, the most generous woman I have ever met.
Whatever her life may have been, that is the result. The rest doesn’t
concern me.”
A sudden light sprang into the other man’s eyes.
“I beg your pardon,” he said simply, in a tone of sincerity.
He looked round the room which was now hot, crowded, and
noisy with the clink of glasses, and the babel of talk.
“Have you anything to do this evening? If not, will you come
round to my club where we can smoke in peace?”
“I should like nothing better,” returned Dr. Dakin.
 XVII
“I’m going to tell you the story of Anne Page as I know it,” said
Fontenelle, as they sat in a corner of the almost deserted smoking-
room. “You may hear all sorts of versions, and I should like you to
listen now to the true one.”
He smiled, as he lighted a cigarette.
“You, also, are a student of psychology, doctor, and it has always
seemed to me that Anne Page is a singularly interesting study.
“Nowadays in this age of modern thought, perhaps I should
rather say in this age of fads and cranks, through which men and
women are groping towards a different conception of life, her
conduct would not have been so amazing.
“If she had been a modern woman, filled with the latest ideas of
the sanctity of passion, whatever that may mean; the duty of leading
her own life, and so forth, one might class her with a number of
earnest feminine enthusiasts whose brains, like the old bottles of
Scripture, are unequal to the strain of the new wine of recent ideas.”
“She doesn’t fit in there,” returned the doctor, smiling.
“Think of it!” exclaimed François with sudden animation. “A
simple gentle woman of twenty years ago. A woman who had led the
narrowest of lives; ignorant of men; ignorant of passion—till at the
age of thirty-seven she falls in love, and is loved by a man ten years
younger than herself. And that man, René Dampierre.”
The doctor started. “You mean the painter?”
François nodded. “She was his mistress for three years.”
Both men smoked in silence for a few moments.
 “One might have guessed,” said the doctor quietly, “that she
would choose a lover worthy of her.”
“Anne is an unconscious artist,” returned Fontenelle. “It was the
most beautiful love affair I have ever known. The only perfect one—
thanks to her courage and self-sacrifice.
“Anne is a simple woman in the sense that all her emotions are
unsophisticated, original, generous. But she is also the wisest
woman I ever met.
“She knew René better than he knew himself. That is to say, she
knew men—or rather divined their natures, by her sixth sense of
intuition.
“She might have married him. He wanted to marry her. But she
knew what the result would be.
“Oh, René was not a brute,” he exclaimed in answer to his
companion’s sudden movement. “Far from it. Except for his genius,
he was the average kindly natured man. But Anne very wisely took
his genius into account. He was not the man to marry, and she knew
it. She is proud, as only a woman of her type can be proud. And then
—here felt the artist in life—this was her first and last passion, the
only vital emotion she had ever experienced in an existence
otherwise incredibly grey, incredibly monotonous. She wanted to
make it a perfect memory for herself, as well as for him.”
He paused a moment, throwing back his head against the
padded chair, while he watched the rings of smoke he was blowing.
“And so,” he went on presently, “she made a resolve which few
women would have found the courage either to make, or what is
more important—to keep. She determined to stay with him only while
his first passion lasted. She made up her mind to go even before the
first cloud was in the sky,—at any rate before it was visible to him.
Women have keener eyes than men for rising clouds.”
The doctor was silent. “Rightly or wrongly,” he went on, “she felt
that only in this way, only by running no risk of injuring either him or
his career, she was justified in taking her little measure of happiness.
She knew him very well,” he added meditatively. “René was as weak
as most of us, weaker than some perhaps, where women are
concerned. He would have been unfaithful, but he could never take
his unfaithfulness callously. He would have been torn perpetually
between his desires, and his dread of hurting her. And his work
would have suffered terribly. Anne was right to go.”
“You speak as an artist,” remarked the doctor drily.
“I can speak in no other way,” returned François. “René
Dampierre was a great man with a definite work to do.”
“But Dampierre,—René Dampierre?” The doctor uttered the
name with respect. “He must have died soon afterwards, surely?”
“Eighteen months afterwards. But not, I regret to tell you, of a
broken heart.”
François placed the end of his cigarette in the ash-tray before
him, and ground it to powder. His smile was a curious blend of
sadness and irony.
“It was an accident, wasn’t it?”
“Yes. The result of a fall from his horse. He was riding at
Chantilly.”
“And you mean that——?”
“That Anne was right to go. She knew the woman before René
himself guessed the truth. She suffered I know, or perhaps as I don’t
know. But not so horribly, I think, as they would both have suffered if
she had stayed. And she made her exit with dignity.” He smiled
again. “I am a Frenchman, doctor, and I suppose the love of le beau
geste is in my blood. I take off my hat to Anne Page.”
When Dr. Dakin spoke, it was in a voice from which he could not
banish indignation.
“It seems incredible! That he could forget a woman like that, I
mean.”
His own faithful nature rose up in revolt at the outrage to all his
sentiments of enduring love.
“He didn’t,” returned François quickly. “Anne had no real rival.
She may rest in peace. Fate was kind to her—and perhaps to him,”
he added. “Their love while it lasted, was perfect, and death settled
the future. You are thinking that if any woman was worthy of fidelity it
was Anne Page? I agree with you. But when a woman late in life falls
in love with a genius——” he made a gesture with his hand, and left
the sentence unfinished.
“Tragic, doctor, I admit. But it’s life,—and Anne knew and
accepted it.”
 The faint irony which he could seldom keep out of his voice, was
almost submerged by something that sounded like real emotion.
“You knew them both very well, of course?” asked Dr. Dakin, after
quite a long silence. “When they were together, I mean.”
“I was with them nearly every evening, when they entertained all
the men best worth knowing, in Paris. It must have struck you that
Anne is a woman of unusual mental distinction?”
“She is a very brilliant woman.”
“That is easily discernible when, as with you, she has a chance of
real conversation. She has naturally a keen quick mind, and she
learnt to talk in a very admirable school.
“The evenings at the flat in the Rue de Fleurus are still
remembered in Paris.”
He smiled to himself, as though in thought he had gone back to
those evenings.
“I wish I could put before you doctor, the charm of their home life.
There has been nothing like it since. That sounds terribly middle-
aged, doesn’t it? I realize that I’m growing old, when I think of the
society of twenty years ago, as incredibly brilliant and fascinating.
“At any rate it was composed of the men and women who have
since made their mark on our age. They are well known names, at
any rate to a man like you who interests himself in our countrymen
as well as in your own.
“Among the painters there were Giroux, and Bussières, and
Deslon. All men associated with the Impressionist movement.
Thouret the novelist, and Dacier the poet, were intimate friends.
They met Anne first at Fairholme Court, with me, and they were
always devoted to her. Then there was Matignon the critic, a fine old
man, who adored her. And Bellet, and Courtois—I could go on
quoting indefinitely. They had a flat in the Rue de Fleurus, beautiful
as only Anne knows how to make a home beautiful. It overlooked the
Luxembourg gardens, and was close to my present studio. I
remember it always full of sunshine, and I can see Anne arranging
the flowers, (every room was full of flowers), and looking up from
them to laugh.
“She was so radiantly happy it was a joy to see her. And she
grew so beautiful. She learnt to dress, of course. Beautiful dress is
one of her instincts, as you see even now. What a hostess she was!
She became the fashion in our set,—René’s and mine. The men
raved about her. They found piquante, that touch of English shyness
and modesty which she combines so oddly with dignity. She held a
real salon, and a very brilliant one too, in the Rue de Fleurus. Those
were her beaux jours.”
“I can imagine it,” said the doctor.
“That sort of ménage is only possible in Paris,” observed
François. “Even there, it’s not without its difficulties. But she
surmounted them by her very unconsciousness and simplicity. Some
of the women even, were won over. One or two of the wives of men
in René’s circle were her intimate friends. They went to her as we all
did, for advice and sympathy.”
“Just as we all go now to be consoled,” put in Dr. Dakin.
“Precisely. And one of the secrets of her power of drawing
confidence, is that Anne is by nature a maternal woman—a mother.”
“That’s the pity of it.”
“I agree. Life hasn’t given her everything. But at least it gave her
three unforgetable years, and a memory which has kept her sweet
and fresh and young as in her girlhood she could never have been.”
“And she went away,” said the doctor gently, “in the midst of her
happiness?”
“She went away quietly, simply, with no fuss, as she does
everything. With no farewell scene, or anything of that sort. She left
him a letter, and with me, a message. The hardest I ever had to
deliver in my life.”
Fontenelle got up, and threw the end of his cigarette into the fire.
“And then she travelled?”
“For years. When they were together, she and Dampierre went to
Italy every spring. I believe she has gone over all the old ground
since then. She seems to have gone half over Europe as well. I used
to get letters from Athens, from Constantinople, from Naples, Rome,
Florence. Fortunately she was a rich woman, able to work off her
restlessness.”
He laughed a little. “That was one of her adorable simplicities. It
never occurred to her that the possession of a fortune made any
difference to the situation. She only looked upon it as a means of
independence and freedom when her happiness should come to an
end. And she was right. René never thought of it either. In some
ways he was as childlike and as unworldly a creature as she. He had
inherited a fairly good income from his father. He would not have
known what to do with more. That’s Anne Page’s story, doctor. I don’t
know how it strikes an Englishman, but to me it seems rather a
wonderful one because of the type of woman to whom it belongs.”
“Yes,” returned Dr. Dakin meditatively. “One would have thought
that convention, or religious prejudice——”
Fontenelle laughed. “She is untouched by either. C’est un vrai
caractère, cette chère Anne Page! Until she came to Paris, she
hadn’t mixed enough with the world even to know its conventions.
Religion? Well, ‘by their fruits ye shall know them,’ and if the fruits of
the Spirit are faith and hope, and the charity which suffers long and
is kind, there never was a woman who has more absolutely attained
the results of religion. It’s not a satisfactory result for the moralist, I
admit,” he added.
“But in this very interesting and amazing world, the moralists
don’t have it all their own way,” observed the doctor.
“So far as creeds and dogmas are concerned, Anne is a born
pagan. It is not that she has examined and rejected them. They
simply don’t appeal to her nature. When as young men we first met
her, we called her Flora, amongst ourselves. She struck us even
then as a curious blend of Madonna and goddess. And the physical
appearance has a mental and moral parallel. I remember once when
I wanted to tease her, I asked what had become of her religion.
“She looked at me with those childlike eyes of hers and said:
“‘I never had any,—in the sense you mean. By being with René
I’m not hurting any one. And it’s only by hurting people one does
wrong.’
“Then—I admit it was cruel of me, but I was curious—I said that
some people had refrained from doing what she had done, for the
sake of example to humanity. Her reply was ‘But apart from religion,
people haven’t yet decided what is the right way to arrange their
lives.’”
Dr. Dakin smiled. “In view of the modern ferment of opinion, she
was right there.”
 François pushed his chair back, with a movement of impatience.
“Well now what’s to be done? The tale of her incredibly evil past
will spread I suppose, and Dymfield will become impossible.”
He laughed rather savagely.
“It’s quite an amusing notion that scandal should attack a gentle
woman of Anne’s age. Yet I imagine that few of the natives of a
village possess a sense of humour.”
“I don’t think the story will spread. The vicar as I told you is
absolutely incredulous, and no one else has heard it.”
“Except Madame?” hinted François. “I don’t wish to suggest an
unkindness. But women, you understand? A whisper to a dear friend
—hein?”
“My wife is devoted to Miss Page,” said the doctor shortly. “I shall
warn her; but she will be indignant at the mere suggestion of
betrayal.”
“Parfaitement!” returned François with a bow. “Pardon me. You
will probably find Miss Page in Paris,” he added. “She was expected
to-day.”
“So much the better. It will be a great pleasure.”
The doctor rose. “Good-night,” he said, extending his hand
cordially. “And thank you for this talk. Perhaps if you decide not to go
to Egypt, you will do us the honour of staying with us a little later,
when my wife comes back? Our friendship for Miss Page makes a
bond between us,” he added, in his pleasant sincere voice.
François met his eyes for an instant. They were full of the
kindliness and instinctive liking he felt for the man he was
addressing.
“A thousand thanks. But I think I am almost certain to go to
Egypt.”
“Another time then. I shall only say au revoir.”
François followed him into the hall, and watched him step into a
hansom, and give the address of his hotel to the driver.
When he turned away, there was a curious expression about his
lips, which presently deepened into a smile that was partly cynicism,
partly something else.
He was reflecting on the curious encounters liable to befall a man
like himself. He thought of the evening’s conversation, and smiled
again to think how completely till this moment he had failed to realize
the humour of its friendly nature.
“C’est un honnête homme. Il ne méritait pas ça——”
François dismissed the subject of Dr. Dakin’s deserts with a
mental shrug, as he went upstairs to his room, in which a bright fire
was burning.
 XVIII
François drew up an armchair close to the blaze, and lighted his
pipe.
His thoughts at first dwelt upon the man with whom he had just
parted—a loyal straight, good fellow if ever there was one, he
decided. The verdict was accompanied by a greater sense of self-
dissatisfaction, a sensation nearer to shame and regret that he had
for years experienced.
It was an uncomfortable attitude of mind, and with characteristic
love of ease, he hastened to obliterate it, by turning his attention
elsewhere.
His conversation with the doctor had conjured up so many mental
pictures of the past, that he scarcely knew which of them to examine
first.
The salon in Anne Page’s flat, rose before him. With the retentive
memory of a painter, François recalled minutely every detail of the
charming room.
He saw the deep-red curtains drawn across the three windows,
the rose-coloured carpet, the lights shining like stars between the
flowers. He saw Anne standing near the table at which coffee was
served, receiving her guests with her lovely smile, and eager words
of welcome.
He remembered to the smallest detail of lace and trimming, a
dress she often wore in the evening, a gown of purple silk which
suited so admirably, her hair and the soft whiteness of her neck.
Giroux and Bussières were talking to her, and he watched with
amusement their excited faces, and vehement gestures.
 It was the evening after René had shown his new pictures.
There had been a crowd of his friends in the studio all the
afternoon; a crowd of eager interested men and women, standing
before the canvases now so well known, so greatly prized.
Bussières and Giroux he knew were talking of the latest picture,
his masterpiece—the famous picture of the lady in the green dress,
leaning back upon the sofa.
François looked round the room already filled with people.
He saw the white head of Matignon the critic, towering above the
rest. He saw the dark alert face of Thouret bent towards Madame
Valory, the painter of pastels delicate and fragile as herself. He saw
Courtois the sculptor, in animated discussion with Bellet the new
poet of audacities in rhythm. He heard René’s sudden amused
laugh, and turned to look at him, as he moved from one group to the
other, a little flushed and excited, his fair hair ruffled, his slim yet
athletic figure suggesting the Englishman of sport and open-air
pastimes, rather than the brilliant French painter he had even then
become.
Conspicuous among the crowd was the lady whose portrait he
had recently painted.
Blanche Aubriot was the wife of an elderly roué, who regarded
her very pronounced flirtations with an indifference equal to that
which she on her side extended towards his infidelities.
She was a beautiful young woman of two or three and twenty,
childless, soulless, and much admired.
To-night she wore the green dress of the picture, and held her
court with her usual piquante vivacity.
François regarding the scene with critical and observant eyes,
noticed how frequently her glance wandered in René’s direction, and
with amusement, her oft-repeated efforts to attract his attention.
His own eyes turned again to Anne, where she stood surrounded
by friends, laughing and talking.
He watched her to-night with peculiar admiration.
Curiously enough Dampierre had never painted her.
Once soon after they had settled in their apartment, François had
spoken of it as a foregone conclusion.
“She’s just your type—the essentially feminine type of woman.”
 Greatly to his surprise, René shook his head.
“C’est impossible,” he said conclusively.
François wondered, but the conversation turned immediately
upon other matters, and it was only just before he took leave, when
Anne was out of the room, that his friend took a book from one of the
shelves, and turning over the leaves, handed it to him at an open
page.
“That’s why I can’t paint her,” he said.
The poem he touched with his forefinger was Browning’s song
beginning—

“Nay, but you who do not love her,

Is she not pure gold, my mistress?”

François read it aloud, and came to the last few lines—

“Then why not witness, calmly gazing,

If earth holds aught—speak truth—above her?
Above this tress, and this, I touch
But cannot praise, I love so much!”

“For praise, read paint,” said René, taking the book and closing it.
“It’s the same thing. You’re the man to paint her. Ask her to sit for
you.”
François had always delayed to avail himself of the suggestion.
To-night he determined to delay no longer. Crossing the room, he
joined the little group round Anne, and presently drew her away.
“I haven’t had a word with you this evening,” he said. “And now
you must give me one, or even two. About that portrait. I think the
time has come. When will you sit for me?”
Even at the moment, he was struck by the curious expression
which crossed her face.
When afterwards he tried to analyze it, he could only think of the
face of a woman who expecting a signal of some sort, had heard,
and accepted it.
“When would you like me to come?” she asked.
She was standing at the end of the room by the fire, and as she
raised her eyes, François saw in them the look which did not escape
him when he came to paint them.
They discussed the matter for a few moments. Various
engagements on both sides postponed the first sitting for a fortnight,
but a day was finally arranged.
“How long will it take?” asked Anne.
He made a gesture of ignorance. “I don’t know. A month perhaps,
with luck. But this is going to be my masterpiece, Anne. I shall
succeed, or perish in the attempt. Have you got that flowered gown
you used to wear in the garden at Dymfield? I suppose not. Yes?
Très bien! Bring it, I want to try an effect.”
He was interrupted by René, who came up at the moment, and
laid his hand lightly on Anne’s arm.
“I want you to go and talk to Matignon, dear,” he said in a low
voice. “He’s always bad tempered if you don’t pay him enough
attention. Go and make love to the old boy.”
A vague uneasiness passed from François’s mind at the sound of
his friend’s voice, always gentle when he spoke to Anne. It was even
gentler than usual now, and he did not fail to notice the caress of his
hand on her sleeve, nor the look of happy understanding between
them, as she moved away, smiling, to obey him.
“I’m arranging for her to come and pose. I’m going to begin the
picture at once,” he said.
“Bon!” returned René, his face lighting up. “You’ve taken your
time about it.”
“One hesitates to begin one’s masterpiece,” François retorted.
“You who do nothing else, except finish them, ought to have
compassion on the weaker brethren.”
René made a laughing gesture of menace.
“Allons, mes amis ... mais calmez-vous donc!” exclaimed Blanche
Aubriot at his elbow.
François looked down at her white shoulders, and experienced a
momentary feeling of repugnance which passed into self-ridicule, for
glancing at her indolent brown eyes soft as velvet, at her full red lips,
at her glossy hair, he acknowledged her beauty.
“Come and talk to me, Monsieur René,” she urged with the
insistence of a spoilt child. “You’re a great man, I know, but the lion
condescends to the mouse sometimes, doesn’t he?”
 François followed them with his eyes as they moved away
together.
“If she had said cat, I should have found no difficulty in reversing
the parts,” was his inward reflection.

The fire had died down, but as he sat before the smouldering
ashes, François was very far in space and time from the club
bedroom in which he was dreaming.
He was passing through successive stages of satisfaction and
despair, hope and baffling discouragement, while he painted Anne’s
portrait. After the first fortnight, she came every day, and every day
she was more silent.
He remembered this afterwards. At the time, engrossed heart
and soul in his picture, he did not notice her quietude. He was only
half consciously perplexed by a subtle difference in her expression
which he found hard to reconcile with his previous impression of her
—a difference which was at once his inspiration, and his despair.
“If only I can get that, I shall paint a great picture!” he exclaimed
one day involuntarily, breaking a long silence.
“What?” asked Anne.
He started, forgetting that he had spoken aloud.
“I don’t know.”
She smiled a little. “Then I’m afraid you won’t get it.”
“But I have!”
He almost shouted the words, one afternoon a week afterwards,
when she had stood patiently almost as long as the daylight lasted.
She looked at him with inquiring eyes, as he threw down his
brush.
“I won’t touch it again! It’s there! It’s all right. Mon Dieu! Anne, do
you hear me? I’ve painted a great picture.”
He came towards the stand, both hands outstretched, and helped
her down.
“Come and look before the light goes,” he urged. “Why Anne
——” his triumphant tone changed abruptly to consternation. “You’re
not ill, dear? You’re trembling so. What a brute I am! I’ve kept you
posing too long. I forgot. Come and sit in this chair. Here’s a cushion.
I’ll get you some water.”
She shook her head. “I’m all right,” she assured him, trying to
smile. “I want to see the picture.”
He turned the easel towards her, and she looked at it a long time
in silence.
“Do you like it?” asked François at last anxiously.
“It’s too good for me. It’s idealized,” she said. “But it’s the best
thing you’ve ever done, François. I congratulate you. You’re right. It’s
your masterpiece.”
He felt a warm glow of pleasure. Anne as he had often
acknowledged was an admirable critic, instinctively a connoisseur,
and her life amongst painters had trained and sharpened her natural
perception. Secretly François stood in greater awe of Anne’s verdict
on his work, than on that of many of his fellow-craftsmen.
“You have suggested all the Dymfield garden in those flowers,”
she said after another silence.
“In you,” he returned quickly, wondering at the tone in her voice.
“I’m going to give you this, Anne,” he went on, speaking gaily to
avert an uneasy fear. “I hope you appreciate the compliment. I lay
my masterpiece at your feet, and you can pick it up and hang it in
your salon, between the two long windows. That’s the place for it.”
She turned slowly from the picture, and her eyes met his, while
she shook her head.
“No,” said she in a low voice. “I can’t take it, François.”
“Why not?”
She leant back in her chair, and a smile so sad that involuntarily
he turned away, came creeping round her lips.
“Because I’m a woman,” she replied.
He made no reply. The meaning of her words did not escape him,
but in a moment she translated them.
“You’ve painted me at the end of my beaux jours,” she said.
“Before they are quite over—but at the end. I’m very grateful. But I
couldn’t live with that picture, it would be too——”
She did not finish the sentence.
“Besides,—there’s another reason,” she added after a further
pause.
 “What’s this?” asked François, suddenly taking a book from the
table. With a sort of blind haste, he strove to hinder her next words
by snatching at any pretext to arrest them.
“It’s a book you lent me, nearly three years ago, I’m ashamed to
say. When I first came to Paris. I’ve always forgotten to return it. But
to-day,” she paused as though her mind were wandering away from
the present. “To-day I remembered it.”
François took it up.
“Mademoiselle de Maupin. I forgot I’d ever lent it to you.”
“You remember the story?”
He nodded. “Of course.”
“It’s very different from my story, isn’t it? But the way she found, I
had already discovered for myself before I read the book. It’s the
right way. In my case, the only way.”
François had just lighted a cigarette. He threw it away with a
sudden jerk, and looked at her without speaking.
“I’m going to-morrow.”
Her voice was steady, but quite colourless.
“René,” stammered her friend, “René is going to-morrow?”
“Yes. Into the country for a few days, for the background of his
new picture.”
François drew up a chair, and sat down close to her.
“Anne,” he began gently, “There hasn’t been anything? Any...?”
She shook her head. “Nothing. But it’s coming. This has been in
my mind for weeks. It was there though I scarcely knew it, before
you wanted me to sit to you. When you asked me, I knew certainly.”
The spring twilight lingered in the studio, and he could still see
her face, white against the cushion he had put into the chair.
As he listened to her quiet low voice, all she was saying seemed
to him like the illusion of a dream.
Anne to be talking of leaving René! It was an absurd hallucination
on his part—a trick of his imagination.
“But René?” he asked nevertheless. “He doesn’t know? Why, I
saw him early this morning, and he spoke of you——”
For the first time, her voice trembled, and he watched her slim
hands travelling aimlessly over the frills on her dress.
 “He doesn’t know,” she said. “That’s why I’m telling you.” There
was a long silence, and he saw her fighting for composure.
“François,” she began at last in a whisper. “He won’t understand
at first. He’ll think me cruel, and wicked and inexplicable.” She
caught her breath, but went on bravely. “You are far sighted too. You
know as well as I do, the woman who will—who will——
“He doesn’t know it yet himself. He still loves me. Now, to-day.
And that’s why I’m going. I couldn’t bear.... He must be quite free. It
was only on those terms I agreed with myself to—to——” She was
shivering now from head to foot, and the words came in gasps like
the words of a dying woman. “It has lasted for three years, and I
thought it might only be three months. I have had quite ... quite a
long life, François.”
He turned away so that he should not see her smile.
“I’m not going to be coward enough to spoil it—for both of us,”
she went on after minutes which seemed like hours. François had
been mechanically counting the strokes of the clock which ticked
maddeningly in the gloom. He had never noticed it before, and was
seized with a sudden mad desire to smash it into fragments.
“But I want you,—will you, François?—in a little while, when he
will listen, to say what you can for me?”
He got up, and began to walk about the room, stumbling against
the chairs in the way.
At last he turned abruptly, and stood before her.
“Must you, Anne?” His voice was an entreaty. It shook almost as
much as her own.
She got up slowly, and gave him both hands.
“Good-bye, François.”
He held them close, without speaking.
“I shall write to you,” she said, “—later on. I’m going to be a great
traveller. You will hear of me from—from all sorts of wonderful
places. And I shall see you again, my dear friend. But I don’t think I
shall ever see——” she stopped, and he felt her hands shaking in
his.
“Anne!” he implored. “Don’t go.”
“Don’t say anything more,” she implored. “I have to get through
the evening. It’s our—last. So you see it must be quite—It must be
quite a happy——”
She stretched out a trembling hand for her cloak, and he
wrapped it round her, fastening it for her as though she were a child.
Then he took her downstairs, and called a closed fiacre.
In the darkness of the courtyard, by the door, he put his arm
round her shoulders, and taking both her hands in one of his, he
kissed them.
They were wet with the tears she had tried to brush aside.
 XIX
Two or three mornings before the conversation between Dr.
Dakin and François Fontenelle, Anne, the peaceful Anne of to-day,
received by the same post, three letters which interested her.
She knew the handwriting on the envelopes of each, and
hastened first to learn what her brother had to say. Hugh, as she had
known for some months, was returning to England.
His farm had prospered, and anxious to launch his sons, boys of
sixteen and eighteen, in the professions they had chosen, he had
determined to retire, and end his days in the old country.
The letter, an affectionate one, stated that he was already in
London where he had taken a furnished house, to give him and his
wife time to look round, and decide upon their future home.
Anne must come to see them the moment she returned. They
were all looking forward to her visit.
She put down the closely written pages with an air of content,
and turned smiling to the envelope inscribed in the large childish
characters which recalled Sylvia Carfax.
“My dearest dear Miss Page,
“I must write to you because I’m so happy and excited.
I’ve got splendid plans. Just yet, I can’t tell even you what
they are, because it’s a secret for the present. But it means a
simply magnificent chance for me, and of course it has
something to do with my work. Mother and father will be very
angry, I’m afraid, but I can’t help it. It’s too good to lose, and
one can’t sacrifice the whole of one’s future because of one’s
 parents. Besides later on, they will see how wise I’ve been.
Oh dear Miss Page, when are you coming back? I want to see
you so much, because by that time everything will be settled,
and I can tell you all about it. I’m too excited to write any
more. Only I want you very badly. Do, do come home soon.
“Your ever loving
“Sylvia.”
Anne returned the note to its envelope with a slightly worried
look.
What folly was the child considering? She must write to her at
once, and insist upon a full explanation.
In the meantime she opened the other letter, which bore the Paris
stamp-mark, and was evidently from Madge Dakin. It was very short,
and very incoherent, but when Anne raised her head and let the lilac-
tinted paper slip from her hand, her face was rather white.
She was at breakfast in her sitting-room, whose window
overlooked Rome.
The sunshine flooded the room, and the anemones, purple, white
and scarlet, in a bowl placed on the snowy cloth, glowed with the
colour of jewels.
The air was sweet with the scent of violets which almost covered
a small table near the open window, and outside, over-arching the
city, the Roman sky was gloriously, passionately blue.
Anne sat with her elbows on the table, her chin resting on her
open palms, lost in thought.
Suddenly she rose, and rang the bell.
“Burks,” she said when the maid appeared, “can you pack, and
be ready to start for Paris to-day?”
Burks stared. “But I thought we weren’t leaving for another
month, ma’am,” she gasped.
“I know. But I find it’s necessary to go at once. Can you manage
it?”
The maid beamed with satisfaction. “It’ll be a rush, but I’ll do it,
ma’am, and be thankful. I’m about tired of foreigners,” she added,
alluding thus with a sniff of scorn to the Italian cook with whom she
lived on terms of ill-concealed warfare.