Facile fabrication of SnO2 modified

TiO2 nanorods film for efficient

photocathodic protection of 304
stainless steel under simulated solar
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 Corrosion Science 176 (2020) 108927

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

Facile fabrication of SnO2 modified TiO2 nanorods film for efficient T

photocathodic protection of 304 stainless steel under simulated solar light
Juantao Zhanga,c, Hualong Yangb, Yuan Wanga, Xiaohu Cuib, Zhang Wenb, Yunpeng Liua,c,*,
Lei Fana,*, Jiangtao Fengc,*
a
NPC Tubular Goods Research Institute, State Key Laboratory for Performance and Structure Safety of Petroleum Tubular Goods and Equipment Materials, Xi’an, Shaanxi
710077, China
b
Petro China Traim Oilfield Company, Korla, 841000, China
c
Department of Environmental Science & Engineering, Xi’an Jiaotong University, Xi’an, 710049, China

A R T I C LE I N FO A B S T R A C T

Keywords: SnO2/TiO2 nanorods (TNRs) composite film was successfully fabricated. The results showed that the SnO2 na-
TiO2 nanorods array noparticles were deposited onto the surface of the TNRs film, and this composite film exhibited excellent light
SnO2 absorption ability. Meanwhile, the SnO2/TNRs composite film exhibited the superior photoelectrochemical
304 stainless steel performance. With white light illumination, this composite film made the potential of the coupled 304 stainless
Photocathodic protection
steel (304SS) in a 0.5 mol·L−1 NaCl solution drop by 240 mV, exhibiting more efficient photocathodic protection
(PCP) effect. What’s more, it could provide delay protection for the steel in darkness attributing to the “electron
pool” effect of SnO2.

1. Introduction
304SS is widely used as engineering steel in industrial production
due to its outstanding anti-corrosion property. Nevertheless, pitting and
crevice corrosion on the metals are barely to be avoided in the presence
of Cl− [1–3]. So far, many anti-corrosion technologies have been de-
veloped, such as anti-corrosion coatings, corrosion inhibitors, electro-
chemical protection, etc [4,5]. These traditional protection technolo-
gies are limited because of the consumption of material and energy, and
the environmental pollution. On behalf of green steel-protection
methods, the PCP is commonly considered as the one of the most ef-
fective technology [6]. When the photoanode is irradiated, the photo-
excited electrons are immigrated to the connected steel, and the surface
potential of the protected steel shifted negatively below its corrosion
potential, resulting in the cathodic protection effect for metals [7].
TiO2 has attracted many attentions in field of photocatalysis, owing
to its low cost, low toxicity and large specific surface area properties.
Compared with traditional TiO2 particles and TiO2 nanotubes (TNTs)
array, TNRs array has been extensively exploited in pollution de-
gradation, hydrogen production and solar cells due to one-dimensional
(1D) electron transmission shortcut and excellent electronic mobility
[8]. However, TNRs still suffers the inherent flaws of TiO2, namely, the
wide band gap (3.1 eV) of rutile TiO2 limits its PCP application only in
the UV region and decrease the utilization ratio of solar light [9].
Meanwhile, the rapid recombination of photogenerated electrone/hole
(e−/h+) pairs will happen after cutting off the light, resulting in the
lose effectiveness of the cathodic protection in darkness [10]. Thus, in
order to enhance the PCP performance, it is necessary to sensitize TNRs
as a visible light absorber. At present, the combination of TNRs and
narrow band-gap semiconductors (such as Bi2S3, WO3, CdSe, etc.) have
been proved to be effective methods to hinder with these problems
[11].
SnO2, a kind of stable and nontoxic n-type (3.5 eV) semiconductor,
has be used to combine with TiO2 to form photoanode in some PCP
researches [12]. The stagger band structure between SnO2 and TiO2,
benefits the separation of the e−/h+ pairs to enhance photoelectric
performance. In addition, since the conduction band (CB) of TiO2 is
more positive than that of SnO2, SnO2 can serve as an “electron pool” to
storage e− in the binary photoanode material, to ultimately provide
delay protection for the coupled steel in darkness [13]. Hu et al. have
synthesized SnO2 nanoparticles modified TiO2 nanotube films, and
provided an effective cathodic protection for 403 stainless steel [9].
Zhang et al. have fabricated nanoflower like SnO2-TiO2 nanotubes
photoanode, and the delay protection for 304SS was achieved in
darkness [13]. However, as the excellent succedaneous materials of
TNTs film, there have been no reports on the PCP efficiency effects of

⁎
Corresponding authors.
E-mail addresses: liuyunpeng1994@stu.xjtu.edu.cn (Y. Liu), damifan198802@163.com (L. Fan), fjtes@xjtu.edu.cn (J. Feng).

https://doi.org/10.1016/j.corsci.2020.108927
Received 7 April 2020; Received in revised form 12 July 2020; Accepted 2 August 2020
Available online 07 August 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
J. Zhang, et al. Corrosion Science 176 (2020) 108927

the SnO2/TNRs composite for 304SS.

Therefore, in this work, the main objective is to synthesize the
SnO2/TNRs film via hydrothermal treatment and electrodeposition
method on the conductive fluorine-doped tin oxide (FTO) substrates, to
achieve excellent PCP efficiency for 304SS. Meanwhile, their photo-
electrochemical properties and PCP mechanism for 304SS were also
proposed.

2. Materials and methods

2.1. Chemicals

Hydrochloric acid (HCl), nitric acid (HNO3), stannic chloride

(SnCl2), sodium hydroxide (NaOH), sodium chloride (NaCl), sodium
sulphide (Na2S), sodium nitrate (NaNO3) and titanium butoxide
(C16H36O4Ti) were all purchased from Sinopharm Chemical Regent Co.
Ltd, (Shanghai, China). All the chemicals were analytical reagent
without any purification and distilled water (DW) was used in the
preparation of all solutions.
FTO glass (7 Ω cm−2, 2.2 mm-thick) was bought from Guluo Glass
Co. Ltd, (Luoyang, China). Before using of the testes, the FTO glasses
were cleaned ultrasonically by DW, followed by acetone and alcohol for Fig. 2. Schematic of photoelectrochemical test device.
30 min each. In the end, those structures were air-dried in ambient
condition. different electrodeposition time (0.5, 1 and 1.5 h) was synthesized,
denoting as SnO2/TNRs-0.5 h SnO2/TNRs-1 h and SnO2/TNRs-1.5 h,
2.2. Synthesis of SnO2/TNRs composite films respectively .

2.2.1. Preparation of TNRs film

The TNRs array film was fabricated on FTO substrate by the tradi-
tional hydrothermal reaction following these steps. In the first place, 60
mL HCl aqueous solution (6 mol·L−1) injected with 1.0 mL C16H36O4Ti,
was poured into a 100 mL Teflon-lined stainless-steel autoclave. Then a
sheet of FTO structure was put at an angle against the wall of the above
autoclave with the conducting side facing down, and being heated at
150 °C in an electric oven (for 10 h). Finally, the film was washed with
DW, and placed in a muffle furnace at 500 °C in air (for 2 h).
2.2.2. Preparation of SnO2/TNRs composite film
SnO2/TNRs composite films were prepared in a traditional three-
electrode system. The work electrode (WE), the reference electrode
(RE) and the counter electrode (CE) are corresponded to the TNRs film,
Ag/AgCl electrode and Pt foil, respectively. The electrodeposition so-
lution comprised 25 mmol·L−1 SnCl2 and 50 mmol·L−1 HNO3. The
electrodeposition method was carried out potentiostatically (CHI660D,
Shanghai Chinstruments co., Ltd, China) at 0.5 V under room tem-
perature condition. After thoroughly rinsed with deionized water and
dried in a vacuum drying oven at 50 °C (for 12 h), these as-deposited
composite films were annealed at 450 °C under air atmosphere (for 2 h).
Fig. 1 display the schematic illustration for preparing these composites.
To compare the PCP performances of the SnO2/TNRs composite films
with different deposition time, the SnO2/TNRs composite films with
2.3. Characterizations
All the as-prepared samples were characterized by scanning electron
microscope (SEM Zeiss Gemini SEM 500, Germany), X-ray diffraction
instrument (Bruker D8 ADVANCE, Germany), Raman spectra (LabRAM
HR Evolution with an excitation of 325 nm laser light, France), X-ray
photoelectron spectroscopy (XPS, Thermo Scientific EscaLab 250Xi.,
USA), UV–vis diffuse reflectance absorption spectra (DRS, PE
Lambda950, USA). The photoluminescence (PL) spectra were measured
using an Edinburgh FLS9 luminescence spectrofluophotometer with a
Xe lamp presenting an excitation light of 340 nm. The time resolved
photoluminescence (TRPL) was also studied on a FLS9 series of fluor-
escence spectrometers.
2.4. Photoelectrochemical tests
In the photoelectrochemical experiments (as shown in Fig. 2), the
test rig consisted of a corrosion cell (3.5 wt% NaCl solution) and a
photoelectrode cell (0.1 mol·L−1 Na2S +0.2 mol·L−1 NaOH mixed so-
lution), and the two cells were connected by a salt bridge (saturated KCl
in agar gel). In the corrosion cell, the 304SS electrode, Ag/AgCl elec-
trode and Pt foil were connected to WE, RE and CE poles of the
CHI660D electrochemical workstation, respectively, and the as-

Fig. 1. Schematic illustration of the construction process of SnO2/TiO2 nanorods array composite.

2
J. Zhang, et al.
Fig. 3. The Raman spectra (a) and the XRD patterns (b) for the TNRs and STNRs-1.0.
prepared photoelectrode as the photoanode was immersed in photo-
electrochemical cell, which was coupled with the steel electrode via a
copper wire, as described previously [3]. The photoanodes with an
effective irradiation area of 1 cm2 were radiated by a 500 W Xenon arc
lamp (CHF-XM-500W, Beijing Changtuo technology Co., Ltd. Beijing,
China) coupled with an AM 1.5 G filter calibrated to 100 mW cm−2.
The scanning rates of open circuit potentials (OCP) and Tafel curves
were 1 mV/s. Meanwhile, no bias voltage was applied in the test of
photocurrent density of the photoelectrode. The Tafel result was fitted
to calculate the corrosion potential (Ecorr) and the corrosion current
density (Icorr). The efficient area of 304SS was 1 cm2, which was ground
with 2000-mesh abrasive paper and rinsed with acetone.
3. Results and discussion
3.1. Structural characteristics
The structural information was provided by their Raman spectra
and XRD patterns. As displayed in Fig. 3a, three strong characteristic
Raman peaks (the curve of TNRs) were found to located at 230, 446 and
610 cm−1, ascribed to the B1g, Eg, A1g modes of rutile TiO2, respectively
[14]. Moreover, any the characteristic peaks of anatase TiO2, cannot be
observed, indicating pure rutile phase was obtained after hydrothermal
treatment. In the curve of STNRs-1.0, these characteristic peaks of SnO2
were overlapped by the rutile TiO2 signal for this composite film, so
there is no difference between TNRs and STNRs-1.0. Furthermore, to
confirm the composition of the STNRs-1.0 film, the XRD results of the
TNRs and STNRs-1.0 were displayed in Fig. 3b. The diffraction peaks of
the TNRs at 27.5°, 36.1°, 39.3°, 41.3°, 54.5° 62.9° and 69.8°correspond
well to the (1 1 0), (1 0 1), (2 0 0), (1 1 1), (2 1 1), (0 0 2) and (1 1 2)
planes of rutile TiO2 (JCPDS card no: 65-0912), respectively, which is
consistent with the above Raman result [15]. After the electrodeposi-
tion of SnO2 on the surface of TNRs film, the XRD curve of the STNRs-
1.0 exhibits new diffraction peaks at 33.7°, 61.6° and 65.5°, which
matches well with the characteristic XRD peaks ((1 1 0), (3 1 0) and (3 0
1)) of cassiterite SnO2 (JCPDS card no: 41-1445) [16]. The XRD result
demonstrates the successful deposition of SnO2 on the surface of TNRs
film.
Fig. 4 displays the SEM images with two different magnifications of
TNRs film before and after SnO2 loading. From the images of TNRs
(Fig. 4a and b), the TNRs grew uniformly and densely on the surface of
FTO glass, and the mean diameter of nanorods is about 150 nm. After
electrodeposition treatment, there are amount of SnO2 nanoparticles on
the surface of TNRs film as shown in Fig. 4c. Moreover, the rod-like
structure of TNRs maintains good property during the electrodeposition
process (Fig. 4d). This result also indicates that the SnO2 nanoparticles
are successfully loaded on the TNRs film.
To further confirm the chemical compositions and elemental che-
mical statuses of the composite film, the as-synthesized STNRs-1.0 film
3
Corrosion Science 176 (2020) 108927
was characterized by XPS, and the result is displayed in Fig. 5a-d. From
the survey spectra shown in Fig. 5a, the Ti, Sn and O were present in the
sample, and the C 1s peak in the figure is due to the surface pollution of
C. High resolution XPS spectra for Sn 3d, O 1s and Ti 2p are displayed in
Fig. 5b, c and d, respectively. The two peaks at 495.6 and 487.2 eV are
ascribed to Sn 3d3/2 and Sn 3d5/2, respectively (Fig. 5b), implying that
the main valence state of Sn in this sample is +4 [17]. As shown in
Fig. 5c, binding energies at 530.4 eV and 531.8 eV, are corresponding
to the contribution of lattice oxygen in TiO2 and SnO2 crystal lattice,
and surficial hydroxyl groups (OeH), respectively [18,19]. As shown in
the XPS comparison curves of Ti 2p of TNRs and STNRs-1.0 (Fig. 5d),
the binding energies at 463.9 eV and 458.2 eV of TNRs are ascribed to
Ti 2p1/2 and Ti 2p3/2, respectively [20]. Compared with the previous
reports [21], both of the Ti 2p peaks of the TNRs slightly shifted to the
lower banding energy, which is ascribed to the destroy of Ti-O-Ti lin-
kages of the TiO6 octahedra in strong acid solutions, generating a small
amount of oxygen vacancies (OVs) in the synthesis process of nanorods
[22]. However, the content of OVs is not sufficient to impact the pure
rutile phase of TNRs, according to the results of Raman and XRD
spectra. After electrodeposition of SnO2, all the Ti 2p peaks of the
STNRs-1.0 films shifted negatively, indicating the interaction between
TiO2 and SnO2. With the formation of heterojunction, the redistribution
of valence electrons between TiO2 and SnO2 occurs [23], and the po-
sitive shift of Ti 2p indicates that the transfer tendency from SnO2 to
TiO2.
UV–vis DRS was employed to study the optical properties of TNRs
and SnO2/TNRs films. As displayed in Fig. 6, the TNRs shows a typical
absorption band-edge at about 390 nm, which agrees well with the
band gap of rutile TiO2 (Eg = 3.10 eV) [3,24]. After deposition of SnO2,
the as-prepared STNRs-1.0 composite shows much stronger absorption
ability to the UV light, and slight red-shift of the absorption edge to the
longer wavenumber region compared with the pure TNRs. The mea-
sured band-gap value of STNRs-1.0 composite is narrowed to be about
3.06 eV. This result demonstrates that the combination of TNRs and
SnO2 not only improve the solar-energy utilization efficiency of this
photoanode, but also efficiently suppress the bulk recombination and
surface recombination of the e−/h+ pairs, and finally promote its PCP
properties for 304SS. Meanwhile, SnO2 nanoparticles cannot absorb
visible light due to its relatively wide band gap [25], resulting in the
very slight optical absorption red-shift of STNRs-1.0 composites.
In order to study the influence of the SnO2 nanoparticles, PL emis-
sion spectrum and TRPL spectrum measurements were applied to reveal
the migration, transfer and recombination processes of the e−/h+ pairs
in the interface between SnO2 and TNRs. As shown in Fig. 7a, the main
emission peak is located at 435 nm for the pure TNRs, which can be
contributed to the band-to-band recombination process of the e−/h+
pairs [26]. The higher PL intensity, the faster recombination rate of
photocarriers. The PL peak intensity of the STNRs-1.0 was much lower
for comparison with that of the pure TNRs, implying that the separation
J. Zhang, et al. Corrosion Science 176 (2020) 108927

Fig. 4. SEM images of the TNRs (a and b) and STNRs-1.0 (c and d).

Fig. 5. Full scan survey XPS spectrum (a) and high-resolution spectra of (b) Sn 3d and (c) O 1s of STNRs-1.0 composite film, and the XPS comparison spectrum of Ti
2p (d) of TNRs and STNRs-1.0 films.

efficiency of the e-/h+ pairs in the composite film has been enhanced in the interface can efficiently improve the transfer of photo-induced
because of the deposition of SnO2. For more insights into the photo- electrons and simultaneously hindered the recombination of the e−/h+
generated charges, TRPL analysis was displayed in Fig. 7b, and the pairs.
lifetime of STNRs-1.0 (8.30 ns) is higher than that of pure TNRs (5.34
ns), indicating rapid charge immigration between SnO2 and TNRs.
These results demonstrated that the formation of built-in electric field

4
J. Zhang, et al.
Fig. 6. UV–vis absorption spectra (a) and the plots of (αhν)2 versus hν (b) for the TNRs and STNRs-1.0 films.
3.2. Photoelectrochemical properties of TNRs and SnO2/TNRs film
The transfer of photoinduced electrons play an important role in
PCP process, so it’s essential for assessing the PCP efficiency of a pho-
toanode to investigate the photocurrent density [27]. Fig. 8a shows the
photocurrent density of the TNRs, and STNRs-0.5, STNRs-1.0 and
STNRs-1.5 films connected with metal with intermittent white light
irradiation. Before illumination, the photocurrent values of the four
samples were almost zero. After the light source was turned on, the
photoelectric response of SnO2/TNRs composite (31–84 μA cm−2) were
higher compared with the unmodified TNRs film (27 μA cm−2), in-
dicating that photon-to-current conversion efficiency of SnO2/TNRs
film was outstandingly improved. Namely, more electrons can be
photoexcited in this composite film under white light illumination,
suggesting that the SnO2/TNRs film might provide more effective
cathodic protection for 304SS than the TNRs film. From Fig. 8a, the
value order of photocurrent density is as follows: STNR-1.0 > STNR-
1.5 > STNR-0.5, suggesting that the STNR-1.0 might exhibit superior
PCP performance on 304SS. In addition, the SnO2/TNRs photoanode
has a stable and reproducible photoelectrochemical property during
three on-off cycles of the illumination. Therefore, the SnO2/TNRs film
has an advantage for an excellent photocatalytic performance.
To assessing the PCP performances of as-prepared photoelectrodes
on the steel, the materials (TNRs, STNRs-0.5, STNRs-1.0 and STNRs-1.5
films) serve as photoanode in the photo-induced OCP tests via mon-
itoring the change of steel surface potential under white light illumi-
nation (as displayed in Fig. 8b). The result shows the corrosion po-
tential of bare steel is about −180 mV vs. Ag/AgCl, meanwhile, the
OCP value of 304SS coupled to TNRs film shifts slightly to negative
values (−320 mV vs. Ag/AgCl). Nevertheless, for SnO2/TNRs films, the
much more negative OCP value (−400 mV vs. Ag/AgCl) of the steel can
be observed when this photoanode is irradiated by white light firstly.
After then, the surface potential of the steel connected to SnO2/TNRs
films go on dropping slightly, and sustain finally a negative value
(−350 to −420 mV vs. Ag/AgCl). As explained above, the formation of
n-n heterojunction between SnO2 and TiO2 can improve the separation
efficiency of e−/h+ pairs, and then more photoelectrons are
Fig. 7. PL emission spectra (a) and TRPL spectra (b) of TNRs and STNRs-1.0 composite films.
5
Corrosion Science 176 (2020) 108927
immigrated to the connected steel to decrease its surface potential,
resulting in superior PCP efficiency. Additionally, after cutting off the
light, the OCP value of 304SS connected to TNRs film returns to the
initial level before illumination (about 190 mV vs. Ag/AgCl), indicating
that it can’t provide valid delay protection for 304SS. Nevertheless, it is
obvious that all the surface potential of the steel coupled with SnO2/
TNRs composite films are more negative than the corrosion potential of
304SS in darkness (−210 to −230 mV vs. Ag/AgCl), which can be
ascribed to the effect of “electron pool”. Meanwhile, the potential of
304SS coupled with STNRs-1.0 is significantly lower than that when it
is coupled with pure STNRs-0.5 and STNRs-1.5 with light illumination,
implying that STNRs-1.0 is optimal for anti-corrosion of 304SS. This
result could be attributed to the appropriate deposition content of SnO2
nanoparticles coordinated with the sustainability of the 1D electron
transmission shortcut of the TNRs, therefore enhancing the photon-to-
electron conversion efficiency and insuring abundant generation and
rapid immigration of photoelectrons. For STNRs-0.5, because of the low
deposition content of SnO2 nanoparticles, it is unsatisfactory to gen-
erate sufficient photoelectrons to the maximum extent. For STNRs-1.5,
owing to the excessive coverage of SnO2 nanoparticles onto the surface
of TNRs film, the light-absorption ability is reduced, and sectional SnO2
nanoparticles may be the recombination center of the e−/h+ pairs.
More interestingly, the OCP value of 304SS coupled to the STNRs-1.0
composite keeps going down to a fixed state (approximately −250 mV
vs. Ag/AgCl) after cutting off the light source for the second and third
time. When the STNRs-1.0 film is irradiated for the first time, extra
electrons was temporarily stored in SnO2 and then released to achieve
dark-state protection. These unconsumed electrons in darkness will be
continued to transferred to the coupled steel when the light is provided
again, resulting in more negative surface potential of 304SS. After the
second on-off cycle, the dark-state OCP shift more negatively to a fixed
value due to no need of more electrons to be stored. Therefore, the
STNRs-1.0 film can serve as a potential photoelectrode in the PCP ap-
plications for 304SS.
The Tafel polarization curves of 304SS in the 0.5 mol·L−1 NaCl
solution were also employed to evaluate the PCP efficiency of the as-
prepared samples under white light illumination (Fig. 8c). It is obvious
J. Zhang, et al.
that the Ecorr value of 304SS connected to the as-prepared sample is
more negative than that of bare 304SS (−187 mV vs. Ag/AgCl), and the
Ecorr of 304SS coupled with STNRs-1.0 film exhibits the most negative
value (-421 mV vs. Ag/AgCl), which is in agreement with the OCP re-
sults. This result indicate that STNRs-1.0 film possess the higher photo-
electric conversion efficiency than pure TNRs film, and more electrons
are immigrated to the coupled steel under white light irradiation. It is
well known that the higher Icorr value, the more effective anti-corrosion
property will be. The Icorr of STNRs-1.0 is markedly higher than those of
the other samples/304SS and bare 304SS, since superior solar light
utilization capacity and separation efficiency of the e-/h+ pairs. Ac-
cording to the above analysis, the STNRs-1.0 composite could be sup-
posed to display remarkable PCP efficiency for 304SS.
3.3. The stability evaluation of STNRs-1.0 film in PCP system of 304SS
As shown in Fig. 9a, the relationship between the illumination time
of white light and the dark-state delay PCP performance of 304SS
coupled with STNRs-1.0 is investigated. After coupled with the STNRs-
1.0 composite, the 304SS potential negatively shifts to around −200
mV vs. Ag/AgCl before illumination because of the galvanic effect.
When provided with white light irradiation, all the potential values
rapidly dropped to −440 mV vs. Ag/AgCl, which are consistent with
the above results. When the STNRs-1.0 film was only irradiated with
white light for 5 min, the OCP value of the 304SS recovered to its the
initial potential (−200 mV vs. Ag/AgCl) after 20 min (about 0.34 h).
After extending the illumination time to 30 min, the duration of the
delay protection could be effectively increased to 4.71 h. However,
when the illumination time was extended to 60 min further, the dura-
tion of the delay protection (about 4.92 h) is almost identical to that of
the above result (illumination for 30 min). These results demonstrate
that the increase of illumination time is in favor of the dark-state pro-
tection of 304SS, nevertheless, the enhancement extent of delay pro-
tection is limited and the STNRs-1.0 film can provide certain degree of
delay protection even when the light source is turned off during this
period.
In order to estimate the photoresponse stability of SiO2/TNRs film
in the PCP system, the OCP value changes of the 304SS coupled with
STNRs-1.0 film to intermittently white light irradiation were measured
6
Corrosion Science 176 (2020) 108927
Fig. 8. (a) The photoinduced current density
between the as-prepared samples and 304SS
under intermittent light illumination. (b) The
potential change of the 304SS electrodes cou-
pled with the as-prepared films. Polarization
curves (c) of bare 304SS, and 304SS coupled
with TNRs, and SnO2/TNRs films electrodes
under illumination.
(as shown in Fig. 9b). This result displays that the STNRs-1.0 film can
prevent continuously and effectively 304SS from corrosion, and the
OCP value (around −220 mV vs. Ag/AgCl) of 304SS is still lower for
comparison with its initial value (around −200 mV vs. Ag/AgCl) and
corrosion potential under 8 h’ intermittent light irradiation, displaying
distinguished stability of this composite films. The SEM image of
STNRs-1.0 film measured in the above stability evolution experiment,
are exhibited in Fig. 9c. It can be obviously seen that a mass of SnO2 are
still steadily anchored on the surface of TNRs film, and there isn't much
mass SnO2 to strip from the substrate. Therefore, such composite film
has good potential in PCP application.
In the PCP system, the S2− of the electrolyte of the photoelec-
trochemical cell plays an extremely key role to eliminate h+ (Eq. (2)),
aiming to promote the separation of photocarriers and further enhance
the PCP efficiency [28]. However, the accompanying elemental sulfur
(S) may deposit onto the surface of the composite film to hinder the
immigration of free carrier. The XPS survey spectrum of the STNRs-1.0
film after PCP experiment is shown in Fig. 9d, and there is no peaks for
elemental S, which suggests that the reaction-generated elemental S
forms dissolvable polysulfide ions in the solution (Eq. (3) and (4)) [29].
Therefore, the elemental S originated from the oxidation reaction of
S2− does not exist onto the surface of the electrode, and have little
influence on the PCP performance.
S 2 − + 2h+ → S (2)
(x − 1) S + S 2 − → Sx2 − (x = 2 − 5) (3)
S+ Sx2 − → Sx2+−1 (x = 2 − 4) (4)
3.4. Mechanism
After evaluating the PCP performances of the TNRs and SnO2/TNRs
films, the e−/h+ separation and immigration mechanism for this SnO2/
TNRs composite electrode with and without white light irradiation in
the PCP application for 304SS were described in Fig. 10. The band gap
of SnO2 is wider than that of rutile TiO2, and the CB and valance band
(VB) of SnO2 can match well with those of TiO2 [14]. When the white
light illumined this composite film, the photogenerated electrons in the
VB of TiO2 and SnO2 were photoexcited and immigrated to their CB,
J. Zhang, et al. Corrosion Science 176 (2020) 108927

Fig. 9. (a) The potential change of the 304SS electrodes coupled with the STNRs-1.0 film under different-time intermittent visible light illumination. (b) The potential
change of the 304SS electrodes coupled with the STNRs-1.0 film under 4 light on/off cycles. The SEM images (c) and the full scan survey XPS spectrum (d) of the
STNRs film, which was used in the above stability evaluation experiments for 8 h under intermittent visible light illumination.

respectively. Meanwhile, a majority of photoelectrons were rapidly
transferred to the 304SS through FTO substrate because of a lower
potential (304SS) [30], resulting in that the protected steel was in the
state of thermodynamic stability. Compared with the pure TNRs pho-
toanode, both of the photoexcited electrons of two kinds materials
could immigrated to the coupled steel, leading to a better PCP perfor-
mance
At the same time, sectional electrons in TiO2 CB could be im-
migrated to SnO2 CB under white light illumination, because the CB of
the latter is more negative than that of the former. And the photo-
generated holes assembled in TiO2 VB in the opposite direction are
vanished by S2− at the photoanode/electrolyte interface. The ordered
band-gap structure is favour of the separation of e-/h+ pairs, resulting
in that more electrons of SnO2 and TiO2 are immigrated to the steel
surface. Meanwhile, sectional electrons could be served in SnO2 CB
temporarily, due to its inherent property via a reduction reaction as
follows [13,31–33]:
SnO2 + xe− + xM+ ⇄ Mx SnO2 (M = Na or H , x = 1 or 2)
with white light illumination, the electrons will be saved in SnO2
temporarily. After cutting off the light, above reaction reverses to dis-
charge the photoelectrons. Meanwhile, there are a small amount of OVs
in the TNRs, and the energy levels of OVs have been reported to be
about 1.18 eV below the CB of the rutile TiO2 [34]. Therefore, the

Fig. 10. The sketch of the proposed charge photogeneration and transfer mechanism in the SnO2/TNRs film for the PCP application with and without solar light
illumination.

7
J. Zhang, et al.
electron transitions from the CB of SnO2 to the OVs levels of TiO2
contributed to the electron transfer from SnO2 to TiO2 along the 1D
electron shortcut. And this is the principal factor to achieving the delay
protection for 304SS in the dark.
4. Conclusion
In this research, SnO2/TNRs composite film was successfully syn-
thesized with enhanced PCP performances and electrons storage ability
via hydrothermal treatment combined with electrodeposition method.
Compared with the pure TNRs film, the SnO2/TNRs composite film
possesses superior light response ability and photoelectrochemical ef-
ficiency. The photocurrent density of this composite film is almost three
times higher than that of the pure TNRs based on the deposition of SnO2
nanoparticles. With white light irradiation, the SnO2/TNRs film could
exhibit superior cathodic protection performance for the 304SS in a 0.5
mol·L−1 NaCl solution compared with the pristine TNRs film. More
importantly, the SnO2/TNRs film could achieve the delay protection
owing to the electrons storage property of SnO2 material, even after
cutting off the light. In a word, SnO2/TNRs composite can be regarded
as a potential photoelectrode in the PCP applications for 304SS.
CRediT authorship contribution statement
Juantao Zhang: Writing - original draft, Methodology. Hualong
Yang: Project administration. Yuan Wang: Formal analysis. Xiaohu
Cui: Data curation. Zhang Wen: Conceptualization. Yunpeng Liu:
Supervision, Writing - review & editing. Lei Fan: Funding acquisition.
Jiangtao Feng: Investigation, Methodology, Resources, Software.
Declaration of Competing Interest
We declare that we have no financial and personal relationships
with other people or organizations that can inappropriately influence
our work, there is no professional or other personal interest of any
nature or kind in any product, service and/or company that could be
construed as influencing the position presented in, or the review of, the
manuscript entitled.
Acknowledgements
The authors gratefully acknowledge the Basic Research and
Strategic Reserve Technology Research Fund of China National
Petroleum Corporation Project (Grant No. 2018Z-01), Shaanxi Key re-
search and development projects, China (Grant No. 2017SF-386) and
the Fundamental Research Funds for the Central Universities of China.
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 The Backstop is Taken Down between Seasons, and can be Raised Quickly
by Means of the Supporting Cables

Foundations of brick, anchored into the ground, were made for the
towers. End braces of heavy wire, fastened to the top, and guyed to
the sunken anchors at the ground, support the towers against the
weight of the netting and wire rigging. This is convenient in setting up
the arrangement, as a ladder can be leaned against the end of the
tower, guyed securely. To withstand side motion at the top edge of
the netting, the supporting wires are carried on crossarms of 1 by 1-
in. pieces of wood, 2 ft. long. This rigging is suspended between the
towers and wired to the netting. When this is drawn up tightly, the
netting is fairly taut. Additional supporting wires, with vertical leaders
to the netting, are used to draw up the entire length of the netting
tautly, as desired.
The netting extends under the towers, and is supported there by
wires. As the netting extends nearly to the end guy wires, players
cannot be harmed easily by running into the wires particularly if a
white flag is attached to the guy wires, about 6 ft. from the ground.
Number 20 gauge wire was used for the supporting cables, and No.
9 for the end braces extending to the anchored fastenings.
 A Folding Ground Seat with Back Rest

This Seat Is Useful Out of Doors and Also for Special Purposes Indoors

Those who enjoy sitting or lying upon the grass while reading will
find the device shown in the illustration convenient and comfortable.
With this, one may enjoy the coolness of the ground without harm to
the person or clothing. The adjustable back rest supports the body in
various positions. The device is light, compact, and readily
transported. It is useful also in the home and elsewhere. By placing it
across the bed, or on a trunk, a good substitute for an extra chair is
provided. The seat proper may be folded under and the back rest
used as a prop for reading in bed.
Oak is a suitable wood, and other common woods may be used.
First construct, according to the dimensions given, three rectangular
frames, with mortise-and-tenon joints. Cover the seat and back
frames with heavy duck, turning it in ¹⁄₂ in. at the edges. The base is
an open frame, provided with adjusting notches, spaced 2 in apart.
Next make the adjusting frame, as detailed. Hinge the back and the
seat to the base, and fasten the adjusting frame to the back with
screws, permitting it to fold, as shown.—T. H. Linthicum, Annapolis,
Md.
 Bicycle Carried on Automobile as Tender
Steam yachts often carry a motorboat tender, and an automobile
may carry a bicycle for emergencies. An autoist whose duties require
him to travel through rural districts, had numerous unhappy
experiences with a stalled car until he hit upon this scheme. The
bicycle is strapped on the running board of the car, its handlebars
turned flat against the side, and its wheels in tire sockets in the
running board. A tank in the bicycle frame holds several gallons, and
if the owner runs out of gasoline, he uses the tender to get a supply,
filling the auto tank by siphoning the gasoline through a flexible tube.
—John Miller Bonbright, Philadelphia, Pa.
 Heater Keeps Developer at Proper Temperature

Having had trouble with developer cooling down and failing to

work properly, while developing in the dark room, I constructed the
apparatus shown. A small light-tight box was made slightly larger
than the tray, with a removable top having an opening to hold the
tray. An electric-light socket was fastened inside at one end of the
box and a lamp fitted to it. A wire was attached across the middle of
the lower side of the box, so that the latter and the tray could be
rocked. The box was lined with black paper and varnished black.
The edges of the opening in the top were fringed with felt to guard
against light leakage. A thermometer is used to determine the
temperature. When the developer cools, turn on the light until it
reaches the required temperature.—John Hoeck, Alameda,
California.
 Steam-Propelled Motorcycle Made by
Mechanic
By L. L. VOELEHERT

As ana vehicle,
example of the application of steam power to the propulsion of
the motorcycle shown in the illustration is interesting.
While it does not embody the many refinements of gasoline
motorcycles manufactured commercially, and makes no pretense of
competing with them, the machine has a striking individuality. It was
made by a mechanic in his spare time, with only the facilities of a
small machine shop. Tests and hard usage over typical roads have
shown it to be easy riding, partly by reason of its weight, and to give
very steady power. The machine can be reversed quickly and no
clutch is used. It has a wheel base of 75 in., and weighs about 350
pounds.
The upper portions of the frame are made of 1-in. steel tubing,
strongly riveted at the fork and other joints. The lower section, from
the fork to the rear axle, is made of a double bar of 1¹⁄₂ by ¹⁄₂-in.
steel, spread and braced to carry the tank, engine, and boiler. The
fork is forged from strips of steel, and fitted to standard motorcycle
wheels. The handlebars, seat, transmission chains and gears, as
well as other fittings, are of the ordinary motorcycle type. The seat
may be moved and clamped at various places along the upper bar of
the frame, and an extra seat may be installed, or a bundle carrier
may be fitted behind the driver.
Gasoline, with which to heat water for the generation of steam, is
carried in the long round tank, hung below the frame at the top. The
water supply is contained in the square flat tank under the lower part
of the frame. The engine is supported on the frame immediately
above the water tank, and drives a shaft, which is geared to the rear
wheel by a chain and sprocket.

This Motorcycle is Propelled by a Steam Plant and was Built in a Small Shop
by a Mechanic in His Spare Time

The round boiler, with gasoline burners beneath it, is carried on

the lower part of the frame, which is spread, immediately behind the
front wheel. The boiler is 16 in. in diameter and 12 in. high. It is fitted
with valves, whistle, water gauge, and the usual fittings of a boiler.
The engine is of the horizontal type, and the working parts are
largely inclosed, so as to protect them from dust and to avoid
possible danger to the operator.
 Sideboard Converted into Kitchenette
Living in rooms, in which it was necessary to use the small living
room as a kitchen and dining room as well, the storage of the
cooking equipment became a problem. It was unsightly in the room
when not in use, and there was no convenient place in which to store
it out of sight. The kitchenette, shown in the sketch, was made from
an old sideboard, and served the purpose admirably, being useful
also for other needs.

An Old Sideboard was Converted into a Useful Kitchenette, Which

Economises Space
 The top was removed and hinged to one end, the supports being
removable, for storing them in the cabinet. The hinged top provided
a support for the dishes while cooking. The partition between the top
drawers was removed and the fronts of the drawers fastened in
place with screws. The space thus made available was lined with
asbestos, and a small gas stove was fitted into it. The gas line was
connected to the stove and two pieces of asbestos sheeting were
hinged to fold under the cover and to be leaned against the wall as a
protection while cooking. The top could be hinged at the back to
protect the wall, or cut in two and the parts hinged one at each end
of the cabinet. The lower drawers of the kitchenette were fitted to
hold the cooking materials and equipment.
When the kitchenette is closed it is useful as a stand or table, for
dining, or for other purposes, including ironing. In the latter
operation, it is often desirable to have the hinged top open to give
free access around the end of the top.—J. S. Hagans, Toledo, Ohio.
 Bee Feeder for Winter Use
The use of a feeder, like that shown in the sketch, makes the
feeding of bees in winter convenient. Sirup is fed to the bees from
inverted glass jars, the openings of which are covered with muslin,
the jars being incased in a packing of chaff in a wooden covering.
The wooden box is made to fit over the hive, as shown in the sketch,
and a 2-in. strip is nailed over the joint.
 Sirup is Fed to the Bees in Winter and Protected from the Cold by the
Feeding Jars Inclosed in the Box

The device is made as follows: Use wood smoothed on both sides;

pine basswood, or other soft wood being satisfactory. Make two
pieces, ⁷⁄₈ in. thick, and the same size as the top of the hive. Into one
of these cut two round holes, as shown, to fit the necks of the jars.
Make two pieces, 6³⁄₄ in. wide, for the sides, and two for the ends,
the length being suited to the hive, the dimensions given in the
sketch being suggestive only. Make four strips, 2 in. wide, and long
enough to fit the four sides of the box. Nail the pieces of the box
together, as shown, nailing the sides over the end pieces, and the
top over the frame of sides and ends. Pack chaff into the box, and,
after filling the jars with sirup and covering their openings with
muslin, pack the jars into the box so that their openings will be level
with the bottom through which the holes have been cut. Fasten the
board, with holes for the jars, into place with screws, so that it may
be removed when it is desired to remove the jars for refilling. Nail the
2-in. strips around the lower edge of the box so as to cover the joint
between the box and the hive. The feeder is then fitted into place,
the bees feeding from the surface of the muslin. The chaff prevents
the sirup from congealing in cold weather and so it is always
available for the bees. The use of this simple device will prove
economical and practical in keeping bees over the winter, assuring
them a good food supply, with little effort on the part of the keeper.—
Gus Hansen, Peachland, B. C., Can.
 Kink for Driving Nails
Nails, or spikes, may be driven into hard wood without causing
them to buckle by applying a coating of vaseline, beeswax, and
rosin, mixed in equal portions. A convenient method of applying the
mixture is to bore a hole in the end of the hammer handle and fill it
with the material. The nails may be pressed into the hole to coat
them.—O. Root, Lorain, Ohio.
 Porch Gate Folds into Hollow Pillar
The porch is a convenient play spot for the children, but must be
properly safeguarded to prevent not uncommon accidents and injury
by falls. The folding gate shown in the sketch provides substantial
barrier to the head of the stairs, and may be quickly folded out of the
way. It is hardly noticeable when set in the side of the pillar, and
does not mar the finish or general effect of the latter.
 The Gate is Folded When Not in Use and is Concealed in the Hollow Porch
Pillar

The gate is made of strips of band iron, although wood may be

used. The strips are fastened with bolts, or rivets, and the forward
end is fitted to the section of the pillar, which forms the cover for the
recess in which the gate is housed. The cover is hooked to the
opposite pillar when the gate is opened. Any suitable height may be
chosen for the gate, but, for the purpose suggested, 24 to 30 in. is
satisfactory. The device may be adapted to a variety of other uses by
providing a box or chamber for the collapsed gate, when no hollow
recess is otherwise available.
 A Homemade Book Holder

Nails Driven in a Board and Bent in the Shape of Screw Hooks to Hold a
Book

A piece of board and four finishing nails furnished me with the

necessary materials to construct a book-holding apparatus when in a
hurry. Each nail, being driven through the board, could be turned to
release, and pulled out far enough to accommodate a thicker book.
In fact the device was adjustable.
 The Enchanted Card Frame
A mystifying card trick, in which the performer makes use of the
enchanted card frame shown in detail in the illustration, is as follows:
A pack of playing cards is given to one of the spectators, who selects
a card, noting the number and suit. The card is then placed in an
envelope and burned by the spectator. The performer takes the
ashes and loads them into a pistol, which he aims at a small frame,
shown as empty, and set upon a table a few feet distant. The frame
is covered with a handkerchief, and the pistol is fired at the frame.
On removing the handkerchief the selected and destroyed card
appears in the frame, from which it is taken at the back.