Showcasing the work of functional nanostructures presented As featured in:

by Prof. Masahide Takahashi, Graduate School of Engineering,

Osaka Prefecture University.

Title: Switchable and reversible water adhesion on

superhydrophobic titanate nanostructures fabricated on soft
substrates: photopatternable wettability and thermomodulatable
adhesivity

A titanate nanotube film is demonstrated to provide a switchable

and adhesive hydrophobic surface. The surface adhesivity is
switched from an adhesive to repellent by mild heating and
spontaneous rehydration, and vice versa. A persistent
superhydrophobic/superhydrophilic pattern can be fabricated
on the TNT films coated on soft substrates. See Y. Tokudome et al.,
J. Mater. Chem. A, 2014, 2, 58.

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Switchable and reversible water adhesion on
superhydrophobic titanate nanostructures
Cite this: J. Mater. Chem. A, 2014, 2, 58
fabricated on soft substrates: photopatternable
Received 4th September 2013 wettability and thermomodulatable adhesivity†
Accepted 28th October 2013
Yasuaki Tokudome,* Kenji Okada, Atsushi Nakahira and Masahide Takahashi*
Published on 29 October 2013. Downloaded on 30/10/2014 04:30:41.
DOI: 10.1039/c3ta13536e
www.rsc.org/MaterialsA
A titanate nanotube (TNT) film is demonstrated to provide a switchable
and adhesive hydrophobic surface. The surface adhesivity is reversibly
switched from adhesive to repellent by mild heating and spontaneous
rehydration. A persistent superhydrophobic/superhydrophilic pattern
can be fabricated on the TNT films coated on soft substrates.
Introduction
Extensive exploration dedicated to surface wettability has
revealed that a superhydrophobic surface with controllable
liquid-adhesion is a potential tool for versatile water manipu-
lation.1–3 A water droplet, for example, can strongly attach onto a
superhydrophobic surface with a high adhesion force, and
thereby the droplet can be transferred from the surface without
losing its original mass.4 Water manipulation is expected in
microuidics to open up applications, such as microreactors
and oil/water separation.5–7
Superhydrophobic surfaces with controlled adhesion force
have been demonstrated on lms made of polystyrene,8 poly-
propylene (PP),9 poly(dimethyl siloxane),10–12 organically modi-
ed oxides (TiO2,13 ZnO,14 ZrO2 (ref. 15 and 16)), carbon
nanotubes,17 epoxy resin,18 polydopamine-coated micro-
patterns,19 and so on.20–23 The controlled adhesion force therein
is based on tunable surface nanomorphologies in the respective
systems.24,25 For further manipulation, reversible and switch-
able adhesion with a single surface offers considerable promise.
This type of “smart” surface with reversible and switchable
adhesion is one of the central issues in this eld and indeed
developed to date. On the other hand, the smart surface is
generally dictated by functionality of organics, making it still
challenging to achieve water manipulation in a system free from
Department of Materials Science, Graduate School of Engineering, Osaka Prefecture
University, Sakai, Osaka, 599-8531, Japan. E-mail: tokudome@photomater.com;
masa@photomater.com; Fax: +81-72-254-9309; Tel: +81-72-254-9309
† Electronic supplementary information (ESI) available: Experimental methods
and additional data. See DOI: 10.1039/c3ta13536e
58 | J. Mater. Chem. A, 2014, 2, 58–61
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stimuli-responsive organic molecules and/or particles.20 A
hydrophobic organic layer on nanostructured oxides, such as
ZnO and TiO2, is photocatalytically decomposed, which allow
wettability change without using stimuli-responsive organics.
However their wetting transitions are not reversible and
switchable. Elegant strategies reported on TiO2 nanorod/tube
lms26,27 and a Pd-coated Si nanowire lm28 overcame this
barrier and demonstrated reversible and switchable water
adhesion on the lms without any stimuli-responsive
substances. Especially, the TiO2 nanorod/tube lms should be
highlighted. The system could afford the adhesion switching
under an ambient condition (air atmosphere). The switchable
adhesion therein shows cycle characteristics by taking advan-
tage of photo-induced hydrophilization and subsequent ther-
mally activated hydrophobization. Nevertheless, there still
remains considerable demand for switchable adhesion surfaces
via an alternative route; light stimulus is indispensable in the
TiO2 system, which limits the possibility to use non-photo-
active oxides/hydroxides with functional properties. Another
technological challenge of the TiO2 system is how to use so
substrates. It is generally difficult to nanofabricate oxides
(including TiO2) on plastic substrates29 because techniques,
such as anodic oxidation, etching of templates, and lithography
used in the nanofabrication of oxides,26,27 are hardly fused with
using so substrates. The use of so substrates opens up
attractive applications, such as mechanically tunable trans-
parency and wettability.30
Herein, we develop a novel multifunctional oxide lm, which
is controllably nanofabricated on the so substrate as well as
operated by another stimulus. Nanostructured titanate is
demonstrated to produce a superhydrophobic surface with
switchable adhesivity. The functional surface is made up of
vertically oriented titanate nanotubes (TNTs) with a high aspect
ratio. Aer uoroalkylsilane (FAS) modication, the surface
exhibits superhydrophobicity with a high adhesion force. The
FAS-modied TNT lm shows a sticky superhydrophobic surface
upon exposure to moisture, whereas it becomes slippy on mild
heating. The adhesive force of the lm is increased by water
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Communication
molecules adsorbed onto the TNT surface; the mild heating
dehydrates the TNT surface and the exposure to moisture
recovers physically adsorbed water.
Another important nding in the present work is that TNTs
can grow on plastic/so substrates because the protocol does
not require severe conditions, such as anode oxidation,
template removal at higher temperatures, and lithographic
processing.31 The spontaneous growth of TNTs is simply
induced by carrying out a mild hydrothermal reaction on
amorphous TiO2 used as a precursory lm. Photopatternability
is provided by a photocatalytic nature of TNTs with a band gap
of 3.87 eV.32,33 Because of the large band gap compared with
TiO2, the pattern remains for more than a year under uores-
cent tube radiation in a laboratory atmosphere. As a result,
TNTs create the patternable and switchable surface through the
Published on 29 October 2013. Downloaded on 30/10/2014 04:30:41.
process applicable to so substrates. The obtained TNT lm can
be potentially used for water manipulation in lab-on-a-chip,
microuid devices and water/oil separation.27,34 As a proof of
concept, here we show that the TNT surface can controllably
catch and repel a water droplet. Deformable so substrates are
expected to induce morphological change of nanostructures on
the top of the substrate. This allows anisotropic wettability35
and mechanicallytunable wettability.30
Results and discussion
TNT is a tubular nanoarchitecture formed by scrolling a titanate
single layer with cations inserted between adjacent walls.36
Generally, it is impossible to grow TNTs on substrates which are
less resistant to highly basic conditions, because the growth of
TNTs takes place under highly basic hydrothermal conditions.37
We have recently reported that vertically aligned TNTs can be
grown on amorphous TiO2 lms under mild hydrothermal
conditions.38 The previous protocol was further developed in
the present study using an amorphous and crack-free TiO2 lm
on various substrates. The substrates coated with the TiO2 lm
was covered with a reactive NaOH liquid lm, and processed at
110
C in a closed vessel (Methods and Fig. S1, ESI†). The TiO2
lm works as a protective coating for substrates as well as a Ti
source for TNTs. The amorphous nature of the lm allows the
use of plastic substrates because no thermal treatment is
required for preparing precursory TiO2 lms. As a result, TNTs
successfully grow on various substrates, such as rutile TiO2, PP,
poly(ethylene terephthalate), and poly(tetrauoro ethylene)
(PTFE). A eld emission scanning electron microscopic
(FE-SEM) image of TNTs on a PTFE substrate is presented in
Fig. 1a. A close look at the image reveals that the tubular
nanoarchitecture is formed at the top of the lm. A trans-
mission electron microscopic (TEM) image and an X-ray
diffraction pattern conrm that the obtained nanoarchitecture
is composed of a layered titanate with a tubular shape, TNTs
(H2Ti4O9) (Fig. S2, ESI†).39 The formation of TNT proceeds by
scrolling at the top end of the nanosheet as shown in Fig. S3.† A
well-grown nanosheet starts scrolling to decrease excess surface
energy on the top of the sheet.40 Fig. 1b shows the lm
appearance on a bendable PTFE substrate. The so and bend-
able substrates are promising candidates to produce a surface
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Journal of Materials Chemistry A
Fig. 1 (a) FE-SEM and (b) optical images showing TNTs fabricated on a
flexible PTFE substrate; the yellow arrows in the magnified image
indicate TNTs. (c and d) FE-SEM images showing TNTs prepared on a
rutile TiO2 substrate under a condition of 110
C for 24 h in 1.00 M
NaOH aq.: (c) before and (d) after FAS modification. The inset images in
(c) and (d) represent water droplets on the corresponding films.
with mechanically tunable wettability.30 TNTs formed on all of
the substrates used in this study, suggesting the process
versatility to substrates with less durability against basic
conditions. The obtained TNTs are identical on all the
employed substrates. Hereaer, detailed discussion on the lm
surfaces is given in the case of a rutile substrate. Fig. 1c and d
show FE-SEM images of TNTs before and aer FAS modica-
tion. The images conrm that FAS modication leads to no
morphological change of TNTs. On the other hand, the modi-
cation forms a surface with a very low surface free energy and
drastically changes surface properties. Pristine TNTs show a
superhydrophilic nature, while a superhydrophobic surface
with considerable adhesion force is formed by the FAS modi-
cation (the inset images of Fig. 1c and d).
Contact angle, qCA, and sliding angle, qSA, of a water droplet
on the lms are tunable by changing the NaOH concentration
employed in the hydrothermal treatment (Fig. 2a). FE-SEM
images of Fig. 2b and S3, ESI,† clarify that the surface properties
are dictated by different nanomorphologies. Although the
relatively random alignment of TNTs prevents precise theoret-
ical evaluation, we can qualitatively state that the change of qCA
with NaOH concentration is due to vertical elongation of the
nanostructure, which increases a roughness factor value
involved in Wenzel’s mode;25 indeed, surface roughness
increases with NaOH concentration (Table S1, ESI†). The values
of qSA were estimated using a quite large water droplet (30 mL) in
this case. The adhesion forces of the lms are suggested to be
>60 mN considering a previous report.8 Relatively small water
droplets are strongly stuck irrespective of the nanostructures
(see Fig. S4, ESI†). It is worth noting that the simple tuning of
crystal growth kinetics achieves tunable surface properties
without any templates. The FAS-modied TNT surface can be
transformed again to a superhydrophilic surface (qCA ¼ 0
) by
UV illumination with a xenon lamp (Fig. 2c). The variation of
J. Mater. Chem. A, 2014, 2, 58–61 | 59

Journal of Materials Chemistry A
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Fig. 2 (a) Variations of contact (qCA) and sliding (qSA) angles with NaOH
concentration used in the hydrothermal treatment. qSA was measured
using a 30 mL water droplet. (b) FE-SEM images showing FAS-modified
TNTs grown in 0.05 and 1.00 M NaOH aq. solutions. (c) qCA vs. UV
illumination time, t. C: FAS-modified TNTs; B: reference FAS-
modified Si substrate. (d) Optical images showing films UV-illuminated
for 90 min through a mask. The lower patterned image represents
selective wetting only on UV-illuminated areas. 1.00 M NaOH aq. was
used for the TNTs growth in (c) and (d).
qCA with increasing UV illumination time is due to photo-
catalytic decomposition of FAS molecules; the reference FAS-
modied Si substrate is intact under the UV illumination. The
decomposition of FAS molecules is conrmed by Fourier
transform infrared spectroscopy (FTIR) analysis (Fig. S5, ESI†).
UV illumination through a mask extends this capability of
producing patterned lms as shown in Fig. 2d. Super-
hydrophilic wetting occurs space-selectively at UV-illuminated
areas. The patterned wetting was obtained by shaking off waters
on the hydrophobic areas aer the substrate had been
immersed into a solution. It should be mentioned that the large
band gap of TNTs (3.87 eV) would avoid vanishing the pattern
under near UV illumination. This provides another capability of
using near UV light to induce photochemical reaction only at
wetting areas (Fig. S6, ESI†).
In addition to the features which have been discussed so far:
(1) structure-directed wettability tuning and (2) UV patternability,
FAS-modied TNT lms show reversible and switchable water
adhesion on a single TNT lm. Interestingly, the super-
hydrophobic lm has a response to moisture/water and change
the wettability. Reversible change of qCA is observed by alter-
nating mild heating (80
C, 30 min) and hydration (30 min in
water) as shown in Fig. 3a; the hydrated lm was dried at room
temperature prior to the contact angle measurement. The lm is
nearly superhydrophobic (qCA > 149  2
) aer heating at 80
C,
while it becomes less hydrophobic (qCA ¼ 137  2
) aer hydra-
tion. The change of qCA between the two states is so large that the
surface with modulated wettability can catch and repel a falling
water droplet (8 mL) (Fig. 3b and Video 1, ESI†). The transition
also takes place even when the hydration is performed under an
60 | J. Mater. Chem. A, 2014, 2, 58–61
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Fig. 3 (a) Reversible water adhesion of the FAS-coated TNT film by
alternating thermal-treatment (80
C, 30 min) and hydration (30 min in
water). (b) Optical images of the FAS-coated film repelling and
catching a water droplet after heating (80
C) and hydration, respec-
tively. (c) A schematic illustration showing reversible water adhesion.
ambient air condition. The process is much slower compared to
the case of using hydration in water. The moderate rehydration
under an ambient air condition (23
C, 85% RH, 3 h) affords to
control the water repelling/catching transition in the super-
hydrophobic regime (qCA > 150
) as shown in Video 2, ESI.†
Adhesion energy of a water droplet was estimated to be 8.94 and
8.51 mJ m2 for the hydrated and the heated TNT surfaces,
respectively. These results conrm that the hydrated TNTs form
the sticker surface to catch a water droplet.
A mechanism for the reversible adhesive surface is
proposed in Fig. 3c. Adsorption/desorption of water molecules
on the TNT lm induces a slight change of surface hydro-
philicity and adhesive force. Thermogravimetric (TG) analysis
was performed on TNTs (Fig. S7, ESI†); powdery TNTs was
used considering sample mass. The cycles 1 and 3 show
weight losses measured on heated powdery TNTs, while the
cycles 2 and 4 correspond to weight losses measured on
hydrated powder TNTs. The clear reversible trend observed in
Fig. S7† indicates that desorption of physically adsorbed water
takes place at 80
C and the hydration fully recovers water
molecules onto the TNT surface. It is well-known that TNTs
possess water molecules which are physically adsorbed on the
surface and trapped in the interlayer; the water molecules
dehydrate below 100
C and over 150
C, respectively (Fig. S8,
ESI†).41 The dehydration of physically adsorbed water is not
accompanied by structural reconstruction in contrast to that
of interlayer water,42 and thus the mild heating allows the
reversible cycle characteristics. Water molecules are adsorbed
on the FAS-modied TNT lm as well as the TNT powder; OH
vibration is detected by FTIR analysis, as shown in Fig. S9,
ESI.† A previous report demonstrated that qCA has reached to
120
on a FAS-coated at substrate,43 whereas qCA is below
110
on the at FAS-modied Si substrate as shown in Fig. 2c.
The coverage of FAS is 85% in the present case. The partial
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Communication
FAS coverage on the surface ensures available adsorption sites
on the TNT lm.
Conclusions
We have demonstrated that the TNT lm on various substrates
is a novel material providing superhydrophobic surfaces with
switchable adhesivity. The adhesive surface is switched by
heating (80
C) and spontaneous rehydration. This allows
reversible water manipulation without using a light stimulus.
Fig. 3c represents a schematic illustration summarizing the
reversible water adhesion on the TNT surface. The mechanism
behind is possibly applicable to other materials with high water
affinity. Additionally, the procedure demonstrated here can
fabricate nanostructured oxides on bendable substrates with
Published on 29 October 2013. Downloaded on 30/10/2014 04:30:41.
patterned wettability. Further study is expected to open up
applications taking both advantages of novel nanostructured
materials and functional substrates.
Acknowledgements
The present work is partially supported by JSPS KAKENHI (no.
22360276, no. 24750206, no. 2510817). M. T. is also supported
by a research grant from the Murata Scientic Foundation.
Special thanks go to Dr H. Uchiyama, Kansai University, Japan,
for adhesion energy measurement.
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