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Reversibly Light-Switchable Wettability of Hybrid
Organic/Inorganic Surfaces With Dual Micro-/
Nanoscale Roughness
By Gianvito Caputo, Barbara Cortese, Concetta Nobile, Marco Salerno,
Roberto Cingolani, Giuseppe Gigli, Pantaleo Davide Cozzoli, and
Athanassia Athanassiou*
1. Introduction
Over the past decade, the control of the wetting properties of solid
surfaces has attracted considerable attention due to its implica-
tions in technological fields, such as microelectronics, sensing,
fabrication of self-cleaning and antifogging materials, manipula-
tion of biomolecules and cells, and microfluidics.[1–50]Since the
by the joint effects of their inherent
chemical nature and surface geometrical
arrangement, tailored surfaces that exhibit
specific wetting characteristics can be
obtainedby appropriate
and structuralengineering.To thispurpose,
a variety of organic and inorganic materials
with texturedroughness
chemical features have been engineered
by exploiting, on one hand, different
fabrication tools—such as chemical-vapor
or sol–gel deposition, lithographic pattern-
ing, programmed assembly of colloidal
nanoparticles—and, on the other hand,
refined chemicalsurface
techniques—including plasma-assisted or
reactive-ion etching
A more challenging direction in this
field of research deals with the fabrication
and wet-chemical
of surfaces capable of switching their wettability under suitable
external stimulation. One class of strategies involves surface
functionalization with particular organic molecules that can
exhibit conformational transitions and/or dipole moment
variation upon exposure to external stimuli, such as light,
electrical potential, heating, solvent, or pH changes.[13–19]
Another approach exploits the ability of some semiconductor
[*] Dr. A. Athanassiou, Prof. R. Cingolani
NNL-National Nanotechnology Laboratory of CNR-INFM
Distretto Tecnologico ISUFI
Via per Arnesano, 73100 Lecce (Italy)
IIT-Italian Institute of Technology
Via Morego 30, 16152 Genova (Italy)
E-mail: firstname.lastname@example.com
G. Caputo, B. Cortese, Dr. C. Nobile, Prof. G. Gigli
NNL-National Nanotechnology Laboratory of CNR-INFM
Distretto Tecnologico ISUFI
Via per Arnesano, 73100 Lecce (Italy)
Dr. M. Salerno
IIT-Italian Institute of Technology
Via Morego 30, 16152 Genova (Italy)
Dr. P. D. Cozzoli
NNL-National Nanotechnology Laboratory of CNR-INFM
Distretto Tecnologico ISUFI
Via per Arnesano, 73100 Lecce (Italy)
Scuola Superiore ISUFI
Universita ` del Salento, Distretto Tecnologico ISUFI
Via per Arnesano km 5, 73100 Lecce (Italy)
DOI: 10.1002/adfm.200800909
Here, an approach to realize ''smart'' solid substrates that can convert their
wetting behavior between extreme states under selective light irradiation
conditions is described. Hybrid organic/inorganic surfaces are engineered by
exploiting photolithographically tailored SU-8 polymer patterns as templates
for accommodating closely packed arrays of colloidal anatase TiO2nanorods,
which are able to respond to UV light by reversibly changing their surface
chemistry. The TiO2-covered SU-8 substrates are characterized by a dual
micro-/nanoscale roughness, arising from the overlapping of surfactant-
capped inorganic nanorods onto micrometer-sized polymer pillars. Such
combined architectural and chemical surface design enables the achievement
of UV-driven reversible transitions from a highly hydrophobic to a highly
hydrophilic condition, with excursions in water contact angle values larger
than 1008. The influence of the geometric and compositional parameters of
the hybrid surfaces on their wettability behavior is examined and discussed
within the frame of the available theoretical models.
Adv. Funct. Mater. 2009, 19, 1149–1157
? 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Page 2
oxides, such as TiO2, WO3, ZnO, and V2O5, to
increase the degree of surface hydroxylation
and, hence, hydrophilicity, under band-gap
photoexcitation. Most commonly, a recovery of
the initial condition takes place upon storage in
the dark under air.[20–32]As compared to
stimuli-responsive organic molecules, such
light-sensitive transition metal oxides are
characterized by a higher structural and
photochemical stability and can exhibit inher-
ently larger wettability changes (of the order of
30–708) already in the form of selected single-
line films.
More recently, significant progress in the
manipulation of the light-induced wettability
changes of inorganic oxides has been reported.
For example, amplification of the photochemi-
cally driven response has been demonstrated
for wet-chemically prepared nanostructured
films that consist of organized arrays of oxide
such cases, reversible superhydrophobic to
superhydrophilic conversions have been ulti-
mately attained.[27–30]Further developments
include the realization of hydrophobic and
hydrophilic micron-sized patterns over contin-
uous nanometer-sized roughened oxide films
by means of photomask-controlled illumina-
tion[33–37]or photocatalytic lithography,[38,39]or
by preparation of substrates that exhibit
alternating regions of dissimilar oxides upon
combination of photolithography and plasma-
enhanced chemical vapor deposition.[40]The
resulting surfaces exhibit large wettability
contrast properties, which can be exploited to
guide water condensation and selective deposi-
tion of polymer nanoparticles.[33,35,36,40]How-
ever, although the ability to directly generate
micron-scale patterns made of oxide nano-
structure arrays on suitably treated substrates
has been advanced remarkably,[10,41–50]it has
only occasionally been exploited to enable
dynamic wettability behavior.[46]
Here, we describe an approach to realize ''smart'' solid
surfaces that can modify their wetting behavior under selective
light irradiation conditions. In particular, hybrid organic/
inorganic surfaces were engineered by exploiting photo-litho-
graphically tailored SU-8 polymer patterns as templates for
accommodating close-packed thin films of colloidal anatase TiO2
nanorods, which are able to respond to UV light by reversibly
changing their surface chemistry. The SU-8/TiO2 substrates
prepared offer a dual micro-/nanoscale roughness, arising from
the superimposition of the surfactant-capped inorganic nano-
crystals onto the micrometer-sized polymer pillars. Such suitably
combined architectural and chemical surface design enables the
achievement of UV-driven transitions from a highly hydrophobic
angle (WCA) of more than 1008. A dark storage period of a few
weeks allows the native hydrophobicity of the surfaces to be
restored.The influence of the structuraland chemicalparameters
of the hybrid surfaces on their wettability behavior is examined
combining the light-induced and reversible wettability changes of
inorganic oxides with micron-scale patterned polymeric systems,
which may be promising in various applicative fields, such as
2. Results and Discussion
In this work, we have realized smart surfaces exhibiting light-
switchable wettability that can reversibly change from a highly
hydrophobic to a highly hydrophilic state. Our strategy,
summarized in Scheme 1, aims at achieving surfaces with a
Scheme 1. Sketch illustrating the general strategy to achieve dual-scale roughened organic/
inorganic surfaces exhibiting reversibly light-switchable wettability: I) deposition of a SU-8 film
onto a SiO2/Si substrate, which is characterized by a water contact angle WCAI; II) micropattern-
ing of the SU-8 film by photolithography, leading to WCAII>WCAI; III) surface functionalization
of the patterned substrates with pre-synthesized surfactant-capped TiO2NRs by a dip-coating
regions),whichprovides a surface withWCAIII>WCAII; IV)UV irradiation producesan increased
TiO2hydroxylation, resulting in a surface with WCAIV ?WCAIII. After irradiation, prolonged
exposure to air reverts the surface condition back to the native status.
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dual scale roughness arising from the combination of organic
micrometer-sized patterns with UV-responsive colloidal inor-
ganic oxide nanocrystals. Specifically, patterns consisting of
micron-sized polymeric pillars are fabricated by photolitho-
graphic processing of SU-8 on SiO2/Si supporting wafers.
Patterning of SU-8 results in masters with desirable require-
ments, such as selected geometric parameters, elevated mechan-
ical toughness, and chemical resistance to most common organic
solvents, making them suitable for microfluidic structures.[50b–d]
The micrometric structuring offers a tool to increase the
hydrophobicity of the organic surface, compared to the
corresponding flat counterpart in a gradual and systematic
manner (WCAII>WCAI) by proper tailoring of the pillar
geometry (Scheme 1, panels I and II). Following this stage,
wet-chemically synthesized anatase TiO2nanorods (NRs), which
hexane) due to their tightly bound surfactant (oleic acid) capping,
were used as building blocks to form a dense thin inorganic
coating onthe patterns by a controlled-rate dip coating procedure.
The TiO2 NRs served two purposes:[31,32]first, they further
enhanced the hydrophobicity (WCAIII>WCAII) of the micro-
meter-sized pattern (Scheme 1, panel III), since they super-
impose a layer of nanometer-scale roughness with a quite
hydrophobiccharacter,due tothe NRsurfactant capping,ontothe
organic surface; second, they provided the patterns with a
photochemically active coating platform that could progressively
change its surface chemical composition from a poorly to a richly
hydroxylated state under selected UV illumination (WCAIV
?WCAIII) and revert back upon storage at ambient condi-
tions[31,32](Scheme 1, panel IV). This hybrid organic–inorganic
surface design strategy should ultimately allow the achievement
of large reversible excursions between opposite hydrophobic/
hydrophilic wetting regimes (i.e., DWCA¼WCAIII– WCAIV?1),
the extent of which should be purposely controllable by
combining suitable surface design and regulating illumination
conditions (i.e., time and intensity).
In the following, the validity of our preliminary assumptions is
indeed proven by systematic examination of the influence of
wettability dynamics.
as a function of their geometric parameters (Scheme 1, panel II).
We discuss here structures featured by the same pillar size
(42?42mm in width, 25mm in height), and different inter-pillar
spacing, the latter ranging from 14 to 77mm. Figure 1 shows
representative low-magnification scanning electron microscopy
(SEM) images of three kinds of pillared
substrates, along with a photograph of a water
droplet laying on the respective surface. The
diameter of each droplet is of the order of
millimeters and, thus, experiences many
periods of each pattern.
on the micropatterned SU-8 substrates are
increased compared to that measured for the
corresponding flat surface (WCA ?808), and
they decrease monotonically from 118.08?18
to 82.08?18 as the inter-pillar spacing is
enlarged, as demonstrated in Figure 2 (note
that the errorbars in the figure equal the thickness of the symbols
used). In the same figure, this behavior is compared to that
predicted by two well-known models—Cassie–Baxters'[51]and
Wenzel's[52]—that describe the wetting behavior of rough
surfaces by invoking different mechanisms.
Cassie–Baxters' model assumes that a water droplet can wet a
rough surface only partially, due to the trapping of air underneath
the droplet at the recessed regions of the surface.[51]In such
circumstances, the contact angle of the liquid droplet, uCB, can be
calculated by the following expression:
cosðuCBÞ ¼ fs½cosðuYÞ þ 1? ? 1(1)
where fsis the fraction (always smaller than 1) of the solid surface
on which the liquid is lying, and uYis Young's angle, that is,
the contact angle of the liquid on the corresponding flat surface
with the same chemical characteristics. In our case, uY¼808,
as found experimentally for a flat SU-8, and fs is calculated
according to:[53,54]
ðb=a þ 1Þ2
where a is the width and b the spacing of the pillars. Equation 2 is
valid for the smooth cutting surface of the pillars. Therefore, a
Figure 1. Low-magnification top-view SEM images of pillared SU-8 patterns fabricated onto
SiO2/Si wafers,eachcomprisingequally sized 42?42mmpillarsthat arespacedfrom eachother
by different distances: a) 14, b) 28, and c) 77mm. In the corresponding insets, the optical images
of a water droplet in contact with each surface are shown.
Figure 2. Comparison between WCA values determined experimentally
and those calculated theoretically by applying Cassie–Baxters' and Wen-
zel's models, for the SU-8 pillared structures (42?42mm) with different
inter-pillar distances. The WCA recorded for a flat SU-8 substrate is also
Adv. Funct. Mater. 2009, 19, 1149–1157
? 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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be expected in the cases of less regular pillars since. Indeed,
atomic force microscopy (AFM) measurements reveal that many
of the prepared pillar top sides exhibit a characteristic curvature
(most often concave in shape), due to the lithographic process
According to Wenzel's model,[52]the water seeps within the
recessed regions of the surface, tending to increase the interfacial
contact area shared with the solid until a complete wetting
condition is eventually achieved. The wettability behavior of a
rough surface is then described by the following equation:
cosðuWÞ ¼ rcosðuYÞ
where uWis the value of the contact angle of the liquid on the
rough surface, and r is the roughness of the surface, defined as
the ratio between the actual area of the rough surface and the
geometrically projected area (note that r is always greater than 1,
becoming equal to 1 for flat surfaces). Wenzel's model predicts
that when the contact angle of the flat surface is uY<908(as inthe
case of our samples), then the WCA of the rough (patterned)
surface will be lower than the one of the flat surface. For the pillar
geometries used in this work the roughness is defined as:[53,54]
r ¼ 1 þ
where fsis the same factor as in Cassie–Baxters' model, and H is
the height of the pillars. As previously mentioned in the case of
Equation 2, Equation 4 also applies to the flat top surfaces of the
prepared pillars. Since the pillar-tops most often exhibit a concave
curvature and less frequently a convex one, the roughness
calculated by Equation 4 is a close approximation to the overall
roughness of the surface under examination. In the case of the
patterned pillars used herein, an additional approximation is
made in the calculation of the WCA following Wenzel's model.
Indeed, it is assumed that the water drop lays always on SU-8,
whereas a part of it is in contact with the SiO2/Si at the bottom of
the structures which is actually more hydrophilic than SU-8.
It is clearly inferred from Figure 2 that the monotonic decrease
in the measured WCAs from 118.08?18 to 82.08?18 for
increasingly large inter-pillar spacings, is in contrast with the
trend predicted by both theoretical models. The above discre-
pancy can be rationalized by considering that the wettability
response of the pillared microstructures would reflect the
occurrence of a gradual transition across different wetting
regimes, the latter being dependent on the specific geometries of
the involved patterns. On one side, it should be considered that,
within the frame of the Cassie–Baxter model, the air fraction of
the surface (i.e.; 1?fs), on which the water droplet is deposited,
should scale up with the inter-pillar distances, thereby leading to
increased WCA values. On the other hand, upon assuming
Wenzel's model, the interfacial contact area between the water
dropletandtheSU-8substrate withuY<908shoulddecreasewith
increasing the inter-pillar spacing, explaining the increase of the
WCA values. Careful examination of our data reveals that the
WCA values associated with the SU-8 micrometer-sized patterns
with the shortest spacings (14, 21mm) are close to the theoretical
values predicted by Cassie–Baxters' model. Under such extreme
circumstances, the liquid can be reasonably assumed to lay
mainly on the top of the pillars without penetrating into the
recessed regions. On the contrary, the WCA value measured on
the sample characterized by the largest inter-pillar distance
(77mm) is close to the value predicted by Wenzel's model,
indicating that water is able to wet these types of microstructures
completely. Finally, for the patterns with intermediate spacings
calculated on the basis of the two theoretical models, which
suggests that in these cases a partial wetting could actually occur
on the microstructured surfaces. In summary, these results allow
us reasonably to assume that, as the inter-pillar spacing becomes
larger than a critical size threshold (about ?20mm), the wetting
mechanism progressively switches from a Cassie–Baxter to a
Wenzel type, crossing an intermediate regime, whereby water
starts seeping into the pillars, partially wetting their vertical walls,
most likely due to the gravitational forces that become larger than
the interfacial tension force between air and water.
Subsequently, the surfaces of the SU-8 patterns were
functionalized with a crystalline TiO2nanomaterial (Scheme 1,
panel III) in order, ultimately, to render the wettability of the
resulting organic/inorganic hybrid substrates switchable by UV
light. For this purpose, we selected single-crystalline anatase TiO2
NRs capped with oleic acid[55]as the building blocks for
constructing a compact thin-film coating onto the pillared
structures. A representative low-magnification transmission
electron microscopy (TEM) image is shown in Figure 3a, which
demonstrates that the colloidal samples consist of unidirection-
ally elongated uniformnanoparticles witha rod-likeprofilewhose
average short- and long-axis dimensions are of ?3nm and ?20–
25nm, respectively. As discussed elsewhere,[31,55]such TiO2NRs
are characterized by a preferential elongation along the c-axis of
Figure 3. a) Low-magnification TEM image of the as-synthesized
3?20nm TiO2nanorods. b) Low-resolution SEM image of 21-mm-spaced
TiO2-coated SU-8 pillars, collected at a 458 tilt angle. c and d) High-
magnification SEM images of a bare and TiO2-nanorod-coated top surface
of a pillar, respectively. In the corresponding top-right insets, the optical
images of a water droplet in contact with such surfaces are shown for the
respective cases. It is apparent that upon TiO2coating the substrates
acquire enhanced hydrophobic character.
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the anatase lattice, and expose stepped longitudinal sidewalls
dominantly made of crystallographically equivalent (011)/(101)
facets, whereas their apexes terminate exclusively with (001)
facets. As a primary practical advantage, such nanocrystals are
entirely processable in the liquid phase, so that they can be easily
deposited onto any desired substrate from their optically clear
nonpolar solution by an inexpensive and simple controlled-rate
dipcoating technique (see the Experimental Section). Figure 3b–d
reports typical results of SEM inspection performed on SU-8
patterns (with a 21-mm inter-pillar spacing) before and after the
application of the TiO2deposition procedure. The low-magnifica-
tion overview taken at a 458 tilt angle in Figure 3b reveals
preservation of the initial flat morphology of the top sides of the
pillars, which preliminarily indicates that the employed dip-
layerontothe patternswithoutinducing any noticeableformation
of sub-micron particle aggregates. Spontaneous adhesion of the
surfactant-passivated NRs to the patterned surfaces should be
promoted by the inherent character of the available types of
surfaces. The higher degree of hydrophobicity of the exposed
surfaces of the prominent SU-8 pillars (i.e., the top and lateral
sidewalls) relative to that of the bottom polymer-free areas of the
underlying SiO2/Si wafer (the WCAs on the corresponding
smooth materials are about 808 and 508, respectively) is expected
to result in a denser TiO2coverage on the former rather than the
latter regions. This is indeed proven by high-magnification SEM
inspection of the top surfaces of the pillars. Comparative
examination of Figure 3c–d clearly confirms that a continuous
as large as several squared micrometers. The compact films
enclose tightly packed arrays of NRs, most of which are
preferentially accommodated in a roughly parallel orientation
with respect to the substrate underneath. The self assembly of the
NRs in such types of densely laterally arranged superstructures is
promoted bythe concurrent effectsof theanisotropic shapeofthe
nanocrystals and of the surfactant capping at their surface.
During solvent evaporation, the NRs tend to strengthen the
hydrophobic interactions among each other as a means of
decreasing the overall surface energy of the system.[31,32]
As demonstrated in the insets of Figure 3c and d and in
Figure 4, the TiO2coating attained has a remarkable impact on
the wettability response of the SU-8 structures, which indeed
exhibit enhanced hydrophobicity, as compared to the correspond-
ing bare polymer surfaces (Scheme 1, panel III). Such modified
properties should reasonably result from the contribution of the
additional nanometer-sized roughness that the TiO2NRs, which
expose the hydrophobic long alkyl chain of the capping
surfactants, induce onto the SU-8 surfaces because of their
nanometer-scale dimensions and peculiar packing arrangement.
It is worth mentioning here that the patterning process does not
introduce any additional nanometer-sized roughness to the SU-8
surfaces before the functionalization with the TiO2NRs. Notably,
the increase in WCA measured after NR addition ranges from
about 208 up to 408 for patterns with progressively larger inter-
pillar distances, which suggests a clear synergy between the
micro- and nanoscale surface structuring in the modification of
the wetting properties of the TiO2-functionalized substrates. In
Figure 4 a comparison is also shown between the WCAs
measured on the NR-covered pillars and the theoretical values
predicted by the Cassie–Baxter model. By using the WCA
measured on the TiO2-covered flat SU-8 surface, uY¼968, as the
Young's angle in Equation 1, it is demonstrated that the
experimental values are greater than the theoretical ones, except
fromthe value measured onthestructure with thelargest spacing
of 77mm. Therefore, with the exception of the 77-mm inter-pillar
spacing,wecan safely assumethat the waterdropletslay explicitly
on the top of the patterned pillars after their coverage with the
TiO2NRs. The dual-scale roughness achieved appears to enable
the trapping of more numerous air pockets underneath the water
droplet, thus preventing the liquid from seeping into the void
spaces amongthe pillars. This effect is similar to that observedon
lotus leaves, on which the association of micro-/nanoscale
morphological features is ultimately responsible for their
superhydrophobic properties.[56,57]
The mismatch between the experimental and the theoretical
WCA values on the NR-functionalized SU-8 pillars can plausibly
be ascribed to the attainment of an enhanced degree of
nanometer-sized roughness on the SU-8 micropillars compared
to the one achieved on the flat SU-8 after the dipping procedure.
Such a hypothesis implies that the use of the WCA obtained on
the NR-covered flat SU-8 as the Young angle (uY¼968) in
Equation 1 would introduce an error in the theoretical calculations,
since in Cassie–Baxters' picture the Young's angle is defined as
the WCA measured on the corresponding flat surface possessing
the same physicochemical characteristics. Instead, the actual
Young's angle could exhibit a higher value due to the increased
surface nanometer-sized roughness.
To check the validity of the above assumption, we used AFM.
Indeed, the measurements[6,58,59]of TiO2-covered substrates
showed enhanced roughness in the case of the micropillars with
respect to the flat SU-8 sample. The root mean square (RMS) of
the distribution of height values in the AFM images was taken as
an estimation of the roughness. In Table 1, the average values of
RMS are reported for the flat and patterned SU-8 surfaces coated
with TiO2NRs. For the pillared SU-8 substrates the RMS values
Figure 4. Experimental WCA values for the SU-8 pillared (42?42mm)
microstructures before (circles), and after TiO2coating (squares), respect-
ively, and theoretical WCA values for TiO2-coated pillars calculated follow-
ing the Cassie–Baxter model (diamonds) as a function of the inter-pillar
spacing. The WCA values recorded for an uncoated and TiO2-coated flat
SU-8 substrate are also reported. The error bars in the figure are equal to
the thickness of the used symbols.
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do not change significantly with the inter-pillar spacing and are
quite similar for all the pillar geometries examined. The overall
RMS embodies the contributions from both the nanometer-sized
roughness (high frequency RMS) and waviness (low frequency
RMS) of the surface, whereas the high-frequency RMS, extracted
after subtraction of the wavy background, reflects the nanometer-
sized roughness only (see the Experimental Section). For the NR-
identical. In contrast, for the NR-coated SU-8 pillared patterns,
the overall RMS is almost twice as much as the high-frequency
RMS component only. Indeed, the pillar-top sides exhibit a
characteristic curvature (most often concave in shape), which is
believed to be imparted by the lithographic process itself.
Interestingly, even after removal of such (low-frequency)
waviness, the residual nanometer-sized roughness (high-
frequency RMS) of the NR-coated pillared samples is still four times
as high as that found for the NR-coated flat SU-8 samples. Such
values may be explained by considering that the curvature of the
top surfaces of the pillars may disturb the process of nanocrystal
self assembly during the solvent evaporation stage, eventually
causing a relatively larger fraction of NRs to be deposited and
trapped under unparallel orientations with respect to the
substrate underneath. It turns out that such NRs protruding
out of the attained nanocrystal thin film could actually impart a
higher degree of nanometer-sized roughness to the top surfaces
films achieved on flat polymer substrates.[31]Therefore, in
agreement with our preliminary hypothesis, it can be concluded
that the discrepancy between the experimental WCA values and
the ones calculated by the Cassie–Baxter equation is due to the
nonequivalence of the inherent physicochemical surface proper-
on the micropatterned SU-8 substrates, respectively.
Finally, the samples were exposed to pulsed UV laser light
irradiation to verify the possibility of controllably changing the
wettability properties of TiO2-coated SU-8 patterns in a reversible
manner on the basis of the light-driven hydrophilization
mechanism of TiO2 surfaces (Scheme 1, panel IV). This
conversion is generally believed to be initiated by photogenerated
holes that create oxygen vacancies at the semiconductor surface.
These defects are then able to promote dissociative adsorption of
atmospheric water, which results in an increased degree of
surface hydroxylation. The coordinated hydroxyl groups promote
the adhesion of further water molecule multilayers, making the
surfaces highly hydrophilic.
For the hybrid organic/inorganic patterns here, the organized
NR arrays onto the SU-8 surfaces should preferentially expose
(011)/(101) anatase facets that are particularly effective in the
light-induced hydrophilization mechanism of TiO2.[20–32]In
addition, under the specific irradiation conditions used in this
work (see the Experimental Section), a remarkable increase in
hydrophilicity can be observed, which is correlated with the
increase in the degree of surface hydroxylation of TiO2, while the
surfactant molecules anchored to the NR surfaces are not
subjected to noticeable photocatalytic degradation.[31,32]There-
fore, the porous TiO2 NRs-film is expected to embody a
distribution of alternating highly hydrophilic and quite hydro-
–OH groups, and the latter being associated with surfactant-
protected TiO2areas. Such surface arrangements could lead to
nanometer-sized capillary infiltration, allowing water droplets to
spread out over such TiO2-based coatings.[31]This mechanism
ultimately ensures the highest wettability excursion to be
achieved with a net illumination time of only 0.216ms, and
guarantees full recovery of the initial hydrophobic state in the
We calculated the surface energy of our samples, before and
after the introduction of the TiO2NRs on the SU-8 pillars and
after UV irradiation of the covered pillars, in order to quantify the
variations in its polar component. The calculation of the surface
energies is based on the equation introduced by Owens and
Wendt,[60]using a particular piece of software. The surface
tension s is separated into polar and dispersive components, sP
and sD, respectively, where the polar part describes the
hydrophilic character and the dispersive part the hydrophobic
character of the surface:
s ¼ sPþ sD
In our measurements, two liquids were used: water and
di-iodomethane. The values of the dispersive and polar compo-
nents of the surface tensions are shown in Table 2. An increase in
the surface energies of the TiO2-coated surface can clearly be
surface coated with TiO2before UVirradiation exhibitsa very small
polarcomponent. However, after UVirradiation,the polar share of
Table 1. Surface roughness calculated on the basis of 41?41-mm areas
scannedby AFM on NR-coated(both flat and micropillared) SU-8surfaces.
The overall RMS embodies the contributions from both nanometer-sized
roughness and waviness of the surface, whereas the high-frequency RMS
represents only nanometer-sized roughness, after waviness background
41-mm-wide AFM scanOverall
RMS [nm]
High-frequency RMS
(nanometer-sized roughness) [nm]
TiO2NR-coated flat SU-8
TiO2NR-coated pillared SU-8
Table 2.SurfaceenergybetweenSU-8surfacecoatedwithTiO2beforeandafterirradiation,withthedispersivepartandthepolarpartofthesurfaceenergy,
SurfaceSurface tensions [mN m?1]Dispersive component [mN m?1] Polar component [mN m?1]
Surface coated with TiO2before UV irradiation
Surface coated with TiO2after UV irradiation
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Page 7
the surface energy assumes a significant component itself in
relation to the total surface energy. Indeed, Figure 5a demon-
strates that, upon UV irradiation, the TiO2-coated SU-8 patterns
exhibit a very hydrophilic character (WCA ?15–308), with a
decrease in the WCA values by more than 1008 (the error bars in
the figure are within the thickness of the symbols). It is worth
remarking that the light-driven WCA excursions measured on
the micropillared structures are larger than those found for
the corresponding flat substrate (DWCA ?658), demonstrating
the beneficial effect of the micrometer-scale texturing on the
ultimate degree of hydrophilicity achievable. In this respect, it is
conceivable that the droplet spreading over the substrate is
facilitated by its front experiencing the highly hydrophilic TiO2
film located both on the top surfaces and on the sidewalls of the
SU-8 pillars. The WCA values are expected to be smaller for
narrower inter-pillar spacing, since the interfacial area of contact
between the drop and the highly hydrophilic surfaces is larger.
Nevertheless, the results presented in Figure 5a show that the
lower WCA after UVirradiation of the surfaces is achieved for the
pillar arrangement with the larger spacing. A plausible explana-
tion could be that comparatively large spacing between the SU-8
structures may facilitate functionalization with a uniform TiO2
films on both the top and the sidewalls of the SU-8 pillars, as well
as on the recessed SiO2/Si regions. On the contrary, as the inter-
pillarspacing is reduced,itis likely thatthe processof nanocrystal
self organization in continuous films may be perturbed, resulting
the bottom of the pillars. Thus, it can be expected that, after UV
irradiation of the different pillar arrangements, the most
hydrophilic surfaces should actually be those that have been
covered with a more densely and uniformly packed TiO2NR
coating, that is, the larger-spaced pillars.
As reported previously,[20–32]the OH groups newly implanted
onto the TiO2surfaces upon illumination are neither thermo-
dynamically nor kinetically stable. In fact, once UV irradiation is
halted, O2substitution for the newly implanted hydroxyl moieties
becomes the prevalent chemical reaction under air in the dark,
leading to progressive attenuation of the
hydrophilicity gained under light. Figure 5b
confirms that, subsequent to the light stimula-
tion, during prolonged storage of the samples
in the dark under ambient conditions they
revert back to their initial hydrophobic condi-
tions, close to those encountered in freshly
prepared TiO2-coated SU-8 substrates. Inter-
estingly, the average recovery time is generally
faster for the micropatterned samples (from
the figure: t1?25 days) than for the flat surface
counterpart (from the figure: t2?40 days),
which presumably indicates easier access of
atmospheric oxygen to all the substrate regions
functionalized with the TiO2NRs. The process
of reversibly changing the WCA can be carried
out over several cycles of irradiation/dark
storage, proving that the NR coatings exhibit
excellent reversibility in their wettability prop-
erties without being affected by any significant
photochemical fatigue. Work is in progress to
understand the dynamics of the recovery of the
samples towards their hydrophobic state, as well as to control the
time of the recovery using external stimuli.
3. Conclusions
We have studied the wettability response of purposely engineered
photolithographically patterned SU-8 micropillars covered by
TiO2nanorods. The as-derived hybrid organic/inorganic struc-
tures exhibit a highly hydrophobic character due to the
combination of the microroughness of the SU-8 pillars with
the nanometer-sized roughness of the surfactant-passivated
nanorods coating. The system changes its wettability upon
pulsed UV laser irradiation into a highly hydrophilic state, in
which water is allowed to seep into the recessed regions among
the pillars. The change is primarily due to the increased
hydroxylation degree of the TiO2NR films upon irradiation with
UV light. The ultimate wettability excursions achievable are as
large as about 1008 due to the micro-/nanoscale amplification
effect. The hybrid structures can fully recover their initial
hydrophobicity after a few weeks upon storage in the dark in air.
The reversible wetting behavior of the hybrid surfaces can be
repeated without any apparent fatigue upon successive cycles of
alternated UV irradiation and dark storage.
scale patterning in polymeric substrates and nanometer-scale
roughness introduced by nanocrystals of light sensitive semi-
conductor oxides is a key factor in enhancing the switchable
wettability of artificial surfaces over a broad WCA range. By an
appropriate choice of geometry and control over the wettability
switching time, it should be possible to devise substrates
exhibiting challenging capabilities in the realization of smart
liquid responsive surfaces and microfluidic reactors operating
under external light stimulation. Indeed, this work presents a
systematic study towards the understanding of the mechanisms
and the geometrical features needed for the realization of such
Figure 5. a) Experimental WCA values for the SU-8 pillared (42?42mm) microstructures
covered with TiO2NRs before any irradiation (circles), and after a subsequent 120min of pulsed
UV irradiation (triangles), as a function of the inter-pillar distance (note that an overall 120min
duration of the pulsed UV experiment corresponded to an actual irradiation time of 0.216 ms).
The WCA values recorded for the TiO2-coated flat SU-8 substrate before and after irradiation are
also reported. b) Reversible wettability changes during cyclic alternations of 120-min pulsed UV
illumination, and 40- or 20-day storage in the dark under ambient conditions for the flat and the
patterned SU-8 respectively. Note that the lines connecting the values of the WCA in (b) are just
guides for the eye and are not related to any temporal evolution within the relevant cycles.
Adv. Funct. Mater. 2009, 19, 1149–1157
? 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Page 8
systems. The pillar geometries were chosen on the basis of their
radial symmetry essential for enabling WCA data analysis with
existing theoretical models. Among other polymers, SU-8 was
selected because of its high processability, elevated mechanical
toughness, and chemical resistance, characteristics that make it a
promising candidate for microfluidic systems.
4. Experimental
Materials: All chemicals were of the highest purity available and were
used as received. Titanium tetraisopropoxide [Ti(OPri)4or TTIP, 97%],
trimethylamine N-oxide dihydrate [(CH3)3NO?2H2O or TMAO, 98%] and
oleic acid (C17H33CO2H or OLAC, 90%) were purchased from Aldrich.
SiliconwaferswerepurchasedfromJocam. SU-82010was purchasedfrom
MicroChem. All solvents used were of analytical grade and were also
purchased from Aldrich. Water was bidistilled (Millipore Q).
Preparation of SU-8 Masters: SU-8 micropatterns were prepared on
silicon wafer substrates by photolithography. Due to the formation of a
henceforth referred to as SiO2/Si. First, the substrates were cleaned by
ultrasonication in acetone for 10min and in propan-2-ol for 10min, after
which they were dried under a nitrogen airflow. SU-8 was processed
according to a procedure reported in the manual of MicroChem Corp. [61].
Each substrate was spin-coated with the polymer in order to obtain a
Karl Suss MJ B3 mask-aligner with UV illumination and a photomask
containing the patterns. Post-exposure bake (PEB) was performed on a hot
plate to achieve ultimate crosslinking of the resist, which was then allowed
to cool down in order to improve adhesion of SU-8 to the substrate. The
wafers were then developed by immerging them into a SU-8 developer and
Synthesis of TiO2 Nanorods (NRs): The nanocrystal synthesis was
carried out under nitrogen flow using a standard Schlenk line set-up.
Anatase TiO2nanorods (NRs) with an average diameter of ?3–4nm and a
mean length of ?20–25nm were obtained by low-temperature TMAO-
catalyzed hydrolysis of TTIP [55]. Typically, 10 mmol of TTIP was dissolved
in 70g of degassed oleic acid (OLAC) and the resulting solution was then
reacted with 3.5mL of an aqueous 2 M TMAO solution at 1008C for 72h.
addition and were subsequently subjected to repeated cycles of re-
dissolution in toluene and precipitation with acetone to wash out
surfactant residuals. Finally, optically clear TiO2stock solutions in toluene
were prepared and stored under ambient conditions.
Preparation of TiO2Film Coatings on the SU-8 Patterns: The TiO2NR
coatings were fabricated under ambient laboratory conditions as follows.
The SU-8 patterns were dipped into a 0.4 M (expressed in TiO2molecular
units, according to ICP-AES analysis) toluene TiO2solution, using a dip
coater system (NIMA, Nima Technology, Coventry). The sample was
dipped up to fifty times and withdrawn with a rate of 1cm min?1. The as-
prepare films were gently dried with a nitrogen flow and stored at ambient
Irradiation Experiments: The TiO2coatings were irradiated with the third
harmonic wavelength (355nm) of a pulsed Nd-YAG laser, with pulse
duration of 3ns, a repetition rate of 10Hz, and energy density of 5 mJ cm?2.
The total duration of the irradiation experiments, which was required to
detect thelargest wettabilitychanges, was foundto be120min. Thisperiod
of UV photons with the TiO2 samples of only 0.216 ms. Additional
Elemental Analysis: The Ti atomic content of the nanocrystal solution
was measured by inductively coupled plasma atomic emission spectro-
scopy (ICP-AES) measurements with a Varian Vista AX spectrometer. The
samples for analyses were digested in concentrated HCl/HNO3(3/1v/v).
Contact Angle Measurements: Contact angle characterization was
performed on the substrates by the sessile drop method using a
CAM200-KSV instrument (equipped with a digital camera for acquiring
magnified images of the microdroplets). Bidistilled water was used for
volume was 3mL. The WCA value was the average of 10 measurements
recorded on different neighboring surface locations. The estimated error
on a single measurement was ?18. Measurements were carried out on
uncoated and TiO2-coated substrates before irradiation and immediately
after subjecting the samples to a known number of laser pulses, as well as
after storing the samples in the dark under ambient conditions (relative
humidity 30–40%).
Transmission Electron Microscopy (TEM): Low-magnification TEM
images of TiO2NRs were recorded with a Jeol Jem 1011 microscope
operating at an accelerating voltage of 100kV. The samples for TEM
analyses were prepared by dropping a dilute solution of the NRs dissolved
in toluene or chloroform onto carbon-coated copper grids and then
allowing the solvent to evaporate.
Scanning Electron Microscopy (SEM): Low-resolution SEM characteriza-
tion ofTiO2coatingsdepositedonto siliconsubstrateswas performedwith
a RAITH 150 EBL instrument. Typically, the images were acquired at low
accelerating voltages (less than 5kV) using short exposure times.
Atomic Force Microscopy (AFM): AFM measurements were carried out
using an Asylum Research MFP3D instrument, operating in contact mode
with standard silicon probes CSG10 (NT-MDT). The nominal tip apex
diameter was ?10nm, the tip length was ?4mm, and the nominal
cantilever spring constant was ?0.1N m?1. As the pillar height
(H¼25mm) was larger than the Z-range of the AFM actuator
(?15mm) and much larger than the tip height (?4mm), it was not
possible to track the pillar top surfaces in constant force mode, under
which the probes,in fact, were frequently broken. Instead, the AFM contact
mode was operated in constant height, and the deflection was used to
extract thetopographyof the topmost pillars,after propercalibration ofthe
optical-lever detection system. Removal of the low-frequency RMS (i.e., the
waviness) from the AFM images was performed by subtracting the best
fitting second-order polynomial surface, instead of the standard plane
subtraction (first-order polynomial).
G. Caputo and B. Cortese contributed equally to this work. This work was
partially supported by the Italian Ministry of Research (contract no.
Received: July 3, 2008
Revised: November 3, 2008
Published online: March 9, 2009
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? 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


text:
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in Anti-Aging
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Rise in Cumbria's unemployment rate
Published at 10:31, Wednesday, 20 February 2013
Unemployment in Cumbria rose sharply in January, ending a run of five consecutive monthly falls.
Official figures show there were 8,982 people claiming Jobseeker's Allowance, 544 more than in December.
The county's unemployment rate jumped from 2.7 per cent to 2.9.
Allerdale's jobless total increased by 131 to 2,032, giving the borough an unemployment rate of 3.4 per cent.
Carlisle's climbed 155 to 2,223 (3.2 per cent), Copeland's by 76 to 1,576 (3.5 per cent), Eden's by 30 to 408 (1.3 per cent), Barrow's by 82 to 1,843 (4.2 per cent) and South Lakeland's by 70 to 900 (1.4 per cent).
There is always a sharp rise in unemployment in January following a shake out of seasonal jobs in food production and retailing after Christmas.
Wages, meanwhile, continue to lag behind inflation.
Average earnings increased by 1.4 per cent in the year to December, well below CPI inflation at 2.7 per cent.
Published by http://www.newsandstar.co.uk
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text:
WANTED: Aptenia
nhhoneyJuly 13, 2009
I am looking for rooted cuttings of aptenia....red or pink flowers. I have things I can trade if anyone has any.
domehome(9 CA)
My entire front yard is done in aptenia cordifolia, pink. I could send you cuttings but anything with roots would be difficult as they get heavy as the get larger. They root easily . . . I've never had a cutting that didn't root. I'd be interested in your Euphorbia max., all of my Euphorbias died in a frost and well this one looks like it might make it outside in zone 9b.


text:
107th out of 124 books — 111 voters
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Start by marking "Fairy Tales of Oscar Wilde: The Birthday of the Infanta" as Want to Read:
Fairy Tales of Oscar Wilde: The Birthday of the Infanta
by Oscar Wilde
One of comic art's most respected and pioneering artists, well known for his opera adaptations and beautiful fantasy work, P. Craig Russell is in the process of adapting Oscar Wilde's famous fairy tales in a series of landmark volumes.
Hardcover, 32 pages
Published September 1st 1998 by NBM Publishing
(first published 1891)
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(showing 1-30 of 287)
Jun 15, 2010 D.M. rated it 4 of 5 stars
Recommends it for: cynics of every age
This is the only volume of the series that is entirely occupied with just one tale (the others are two apiece), and frankly I don't think it's justified. A great deal of time is spent on the festivities of the infanta's birthday party, as well as the dwarf's lounging and being mocked by wildlife, but of course this is merely a fault of the original material...and who am I to criticise Wilde? The story otherwise is slightly less cynical than, say, Nightingale... or Devoted Friend, but still a VER ...more
Jun 15, 2013 Sneh Pradhan rated it 4 of 5 stars
Armed with a sharp sword of irony, this story by Wilde will probably slice into even the most insensitive of hearts. The end brought to mind not a similar, but somehow stirring a verisimilitude of emotion , another story "The Postmaster" by Rabindranath Tagore. Though " The Postmaster" does not share the theme or the sudden end of the above story, the irony, the unfairness and the tragic brutality of emotion rend the heart alike. Though I do concede that Wilde was more intellectual and much more ...more
Sep 04, 2014 Anne rated it 3 of 5 stars
Shelves: 2014, graphic-novels, washyarg-reviews, young-adult
Russell turned one of Wilde's short stories into a graphic novel. Nicely done; I think students will check it out. I'll put it on the shelf and see...
Jun 21, 2014 Hannah rated it 5 of 5 stars · review of another edition
Shelves: fantasy-fairytale
Like all fairy tales, this horribly sad story is true to life. People can discuss the painful things of life more honestly in a fairy tale type story, and Wilde tells us about something we all recognize--emotional shallowness and bullying. This tale, along with The Happy Prince, show Oscar Wilde's sensitive side.
Apr 18, 2014 Tia rated it 4 of 5 stars
What a fairy tale without a happy ending. Fantastic yet believable. Well done.
Nov 03, 2014 Anastasia rated it 2 of 5 stars
Shelves: audio-books
This review has been hidden because it contains spoilers. To view it, click here.
Jun 12, 2014 Bella rated it 3 of 5 stars · review of another edition
That poor little Dwarf! Mirrors are a terrible thing for some..
Jun 14, 2008 Emilia P rated it 4 of 5 stars
Shelves: comic-books
Wow, I really love Russell's art style.
And I love Wilde's fairy tales. This isn't my favorite (actually, I'd never heard it before and probably for a good reason)...but the art really captured Wilde's intent.
And I love Wilde's fairy tales. This isn't my favorite (actually, I'd never heard it before and probably for a good reason)...but the art really captured Wilde's intent.
Oscar Fingal O'Flahertie Wills Wilde was an Irish playwright, poet and author of numerous short stories and one novel. Known for his biting wit, and a plentitude of aphorisms, he became one of the most successful playwrights of the late Victorian era in London, and one of the greatest celebrities of his day. Several of his plays continue to be widely performed, especially The Importance of Being E ...moreMore about Oscar Wilde...
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- List of properties
- Properties on map
1000+ commercial properties for sale found
- 6
- 0
13,044 sq ft
Hotel for sale Queens Avenue, Muswell Hill, London
A substantial town house hotel consisting of 3 adjoining converted Victorian terraced houses totalling 19,561 sq ft GIA and 13,044 sq ft NIA. The property is arranged over 4 floors and comprises a large lobby area, 50 en-suite bedrooms and conference facilities for up to 180 people, a substantial... More details ›
87,120 sq ft
Industrial Development for sale 18-21 Penhall Road, London, SE78RX
The property is in an ESTABLISHED industrial area off Woolwich Road, in the close proximity to the regeneration areas around the Olympics and the Dome. CHARLTON STATION is nearby and there are plans to extend the East London section of the DLR through to Woolwich. More details ›
4,669 sq ft
Commercial Property for sale Lee Road, London
The building is set in mid terrace between retail units. Ground Floor GIA 281 Sq M (3,024 Sq Ft) Floor to ceiling height of 3.5 m approx Basement GIA 153 Sq M (1,645 Sq Ft) Our client has had architects plans drawn up to develop the commercial element of the building... More details ›
3,605 sq ft
Office for sale 106 Weston Street, London, SE1 3QB
This NEWLY BUILT SPLIT LEVEL OFFICE has open plan floors with full height windows. The floors have excellent height and volume which is ideal for creative office and/or showroom space. located in South East London MINUTES FROM London Bridge and Borough stations. More details ›
£1,925,000 Offers in Region of
Offers in Region of £1,925,000
38,433 sq ft
Light Industrial for sale Kenrich House, Elizabeth Way, Harlow, Essex, CM19
The property provides a detached 1960s LIGHT INDUSTRIAL WAREHOUSE / FACTORY and offices over ground, first and mezzanine level. The front of the building is over ground and first floors, and faces onto Elizabeth Way. It consists of offices, STORE ROOMS, training rooms and a LARGE FRONT RECEPTION. More details ›
£1,750,000 Offers in Excess of
- 5
- 0
Offers in Excess of £1,750,000
4,040 sq ft
Showroom for sale 31 Pear Tree Street, London, EC1V 3AG
Fantastic self-contained OFFICE/SHOWROOM SPACE with several amenities, equidistant between both CLERKENWELL and SHOREDITCH. The area is surrounded by EXCELLENT TRANSPORT links and numerous cafés, BARS AND RESTAURANTS. Perfect for OWNER OCCUPIERS AND INVESTORS. More details ›
16,000 sq ft
Light Industrial for sale Bearwalden Business Park, Royston Road, Wendens Ambo, CB11
This substantial range of manufacturing premises falls into two main buildings, being OFFICES and MANUFACTURING accommodation INCORPORATING WORKSHOP and LABORATORIES. PARKING is included. The property is ideally situated on this established business park. More details ›
21,170 sq ft
Warehouse for sale Rippleside Commercial Estate, Ripple Road, Barking, IG11
The property COMPRISES a SINGLE STOREY industrial / warehouse unit of steel portal frame construction. The A13 Approach is situated on the south side of the A13, a SHORT DISTANCE to the east of the junction with Renwick Road. Electric ROLLER shutter loading DOOR. More details ›
£1,350,000 Guide Price
Guide Price £1,350,000
6,914 sq ft
Office for sale High Street, Cheshunt
Pair of adjoining office buildings comprising firstly, Riverdene House (the front most building), which is arranged over ground, first and second floor. There are 9 office rooms plus kitchen and WC facilities. The second floor has been converted into a two bedroom apartment with separate acces... More details ›
4,994 sq ft
Convenience Store for sale Former Co-Op Bakery, Star Street, Bowling Road, Kibes Lane, Ware, Herts, SG12 9BX
New-built convenience store investment opportunity secured by Sainsbury's covenent. More details ›
Thank you.
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text:
Generate beautiful release notes from a git log.
Release Notes
Generate release note pages from git commit history.
It's preferable to install it globally through
npm install -g git-release-notes
The basic usage is
cd <your_git_project>
git-release-notes <since>..<until> <template>
<since>..<until>specifies the range of commits as in
git log, see gitrevisions(7)
<template>is an ejs template file used to generate the release notes
Two templates are included as reference,
markdown and
This are for instance the release notes generated from
joyent/node running
git-release-notes v0.9.8..v0.9.9 html > changelog.html
Custom template
The second parameter of
git-release-notes can be any path to a valid ejs template files.
The only available template local variable is
commits that is an array of commits, each containing
sha1commit hash (%H)
authorNameauthor name (%an)
authorEmailauthor email (%ae)
authorDateauthor date (%aD)
committerNamecommitter name (%cn)
committerEmailcommitter email (%ce)
committerDatecommitter date (%cD)
titlesubject (%s)
messageLinesarray of body lines (%b)
More advanced options are
pathGit project path, defaults to the current working path
branchGit branch, defaults to
titleRegular expression to parse the commit title (see next chapter)
meaningMeaning of capturing block in title's regular expression
fileJSON Configuration file, better option when you don't want to pass all parameters to the command line, for an example see options.json
Title Parsing
Some projects might have special naming conventions for the commit title.
The options
t and
m allow to specify this logic and extract additional information from the title.
For instance, Aria Templates has the following convention
fix #123 Title of a bug fix commit
feat #234 Title of a cool new feature
In this case using
git-release-notes -t "^([a-z]+) #(\d+) (.*)$" -m type -m issue -m title v1.3.6..HEAD html
generates the additional fields on the commit object
typefirst capturing block
issuesecond capturing block
titlethird capturing block (redefines the title)
Another project using similar conventions is AngularJs, commit message conventions.
git-release-notes -t "^(\w*)(?:\(([\w\$\.]*)\))?\: (.*)$" -m type -m scope -m title v1.1.2..v1.1.3 markdown


text:
This table shows an overview of the main industry associations that are developing information necessary for Manufactures/Importers for the preparation of the Chemical Safety Report. The table consists of one column per sector association where the main activities are mentioned. It also includes links to the information (if available) and a contact person for further information. There is a worksheet 'Acronyms' with the list of associations. It may help you to indentify the relevant association Should you wish to make the activities of your association included in this table, please contact Cefic: Mercedes Viñas email@example.com Disclaimer: The information contained in this paper is intended for guidance only and whilst the information is provided in utmost good faith and has been based on the best information currently available, is to be relied upon at the user's own risk. No representations or warranties are made with regards to its completeness or accuracy and no liability will be accepted CEFIC nor any company participating in CEFIC for damages of any nature whatsoever resulting from the use of or reliance on the information. ease contact Cefic: Overlook associations activities - key identifiers Please note that this is a living document and will be updated as soon as new information is available. updated December 2010 List of Associations ATIEL - Technical Association of the Concawe - The oil companies' European AISE - International Association for Soaps, European Lubricants Indsutry /ATC - CEFS - European Committee of Sugar CEPE - European Council of producers and importers of paints, Colipa - European Cosmetics Association association for Environment, Health and ECCA - European Coil Coating Association Detergents and Maintenance Products Technical Committee of Petroleum Manufacturers printing inks and artists' colours Safety in refining and distribution Association/Project Name Additive Manufacturers in Europe (see acronyms sheets) Sector Detergents- soaps Lubricants / Lubricant additives Sugar factory products Coatings, Inks, Artist colors Cosmetics Petroleum Coil Coatings 1. Use Descriptor Mapping X X x X X x 1.1. Use of an specific template using the DUCC template and have developed our maps following the DUCC template DUCC Template DUCC Template DUCC template DUCC Template Use of templates from Cefic GES process work of CEPE 1.2. Does your Use descriptor mapping include X No jargon intended No jargon intended, but inevitably will be some No X We have tried to avoid it wherever possible and stuck to the use sector-specific jargon descriptors (eg PROCs and ERCs) given in ECHA guidance documents Human Exposures: typical worst cases published for: 1. the manufacture of coatings, inks and artists's colours. 2. the industrial, professional application of coatings, inks and artists' colours. 3. the consumer application of coatings. Environmental emissions: Specific Exposure 2. Operational conditions Release Categories (SpERCs) and Fact Sheets for the manufacture of Exposure duration: 8 h/day. Consumer exposure not covered (addressed e.g. exposure duration, process Temperature, X - X x coatings, inks and artists' colours published; SpERCs and Fact Sheets under the cosmetics legislation) etc. published for a consumer application of coatings and for a number of professional and industrial application processes. (http://www.cepe.org/EPUB/easnet.dll/ExecReq/Page?eas:template_im =100087&eas:dat_im=101AED) Human exposures: typical industry standards and best practices published for: 1. the manufacture of coatings, inks and artists' colours. 2. the industrial, professional application of coatings, inks and artists' colours. 3. the consumer application of coatings. Environmental 3. Risk Management Measures exposures: Specific Exposure Release Categories (SpERCs) and Fact e.g. presence of Local Exhaust Ventilation, use X* X - Sheets for the manufacture of coatings, inks and artists' colours Not specified. X x of gloves, googles, etc. published; SpERCs and Fact Sheets published for a consumer application of coatings and for a number of professional and industrial application processes. (http://www.cepe.org/EPUB/easnet.dll/ExecReq/Page?eas:template_im =100087&eas:dat_im=101AED) 4. Generic Exposure Scenario * - X - X* X x if you are cooperating with suppliers associations Liaison with suppliers (ATC/ESIG/ to develop GES, please indicate the name of the with ESIG/ESVOC Concawe) and DU Assns included in the with ESIG/ESVOC, ethanol manufacturers X Liaison with DU Assns included in the process CEPE and AISE association(s) you are working with process 5. Standard Phrases** - X - X X X - 5.1. Standard phrases of Operational conditions X In progress X X 5.2. Standard phrases of RMM X In progress X X 5.3. Standard phrases of other fields of the ES X In progress X X Overview SpERCs for coatings and inks manufacture and for coatings and inks application for sectors not covered by active user associations 6. spERCs http://www.aise.eu/reach/exposureass_sub4.ht http://www.atiel.org/Reach_GES.htm available: X X m http://www.cepe.org/EPUB/easnet.dll/ExecReq/Page?eas:template_im= 100087&eas:dat_im=101AED ATC contact: Malcolm Evans T. Newbould Gary Minsavage 7. Contact Peter Freunscht email@example.com Oscar Ruiz Yvonne Barcelona. firstname.lastname@example.com +32 2 513 email@example.com Manuela Coroama (firstname.lastname@example.com, +32 2 227 66 22) email@example.com (include email and phone number) email@example.com ATIEL Contact: Howard Hayes firstname.lastname@example.com 60 52 +44 7525025241 +32-2-566.91.63 email@example.com 7. Status In progress In progress All actions complete In progress In progress In progress All actions complete http://www.comitesucre.org/files/34e833b http://www.colipa.eu/safety-a-science-colipa-the-european-cosmetic- 9. Link to relevant information http://www.cepe.org/EPUB/easnet.dll/ExecReq/Page?eas:template_im= http://www.aise.eu/reach/exposureass.htm http://www.atiel.org/Reach_GES.htm a85481d3d8ff626a9617c1030_1259934309 cosmetics-association/reach-and-chemicals-/use-and-exposure- Only for Concawe members www.prepaintedmetal.eu/reach (if available) 100087&eas:dat_im=101AED .xls information-.html 10. Latest update Nov-09 Dec-10 Dec-09 02 December 2010 April 2010 Jun-09 Dec-10 Information in English only. Information available in English only Information available in English only 11. Comments * for mixtures * A Generic Exposure Scenario is applicable for a group of substances with a similar risk profile and aggregates individual Exposure Scenarios for a particular area of application such as a process chemical, cleaning agent or coating. More information Guidance on ES on: http://cefic.org/en/reach-for-industries-documents- and-tools.html ** Standard phrases are phrases for RMM, OC or others which have been developed by the associations with a consolidation, review process in place ETAD - The Ecological EDANA - International and Toxicological Eurometaux - European FECC - European FEICA - Association of ISOPA - European PEST - Plastics PPRM - Polyester SRM - Solvent TEGEWA - ECMA - European Catalyst Manufacturers ECPA - European Crop association serving the EIGA - European Industrial EFCC - European Federation for EPMA - European Powder EPRA - European Phenolic ERMA - European Resin IFRA - International I&P Europe - Imaging and RECONSILE - TEGEWA and ESIG - European Solvents Industry Group Association of Dyes ETRMA - European Tyre & Rubber Manufacturers' Association Association of non-ferrous Association of Chemical European adhesives and Diisocyanates and Polyols Exposure Scenarios Powder Resin Resins German Textiles TEGEWA Association Protection Association nonwovens and related Gases Association Construction Chemicals Metallurgy Association Resins Association Manufacturers Association Fragrance Association Printing Association Silicon consortia FEDERCHIMICA/AISPEC and Organic Pigments metals Distributors sealants manufacturers Producers Association Team Manufacturers Manufacturers association industries Manufacturers Product manufacturers and Fragrance Material Polyester Powder Uses of spin finishes technology providers for the Solvent resins Processing of Catalysts Crop protection Nonwovens Industrial Gases Construction Powder metallurgy Phenolic Resins Resin Solvents Pigments Rubber Metals Distributors Adhesives and sealants Manufacturers and Diisocyanates and polyols Plastics Resin Silicone industry in the fibre processing Processing of leather Laboratory imaging and printing manufacturers Textiles Compounders Manufacturers idustry industry X x x x X X X X X x X X x X X X X X x x x x x use of specific GES template use of specific GES template aligning with basic DUCC DUCC template DUCC template aligning with basic DUCC - - X DUCC template X DUCC Template DUCC DUCC DUCC-Template DUCC-Template DUCC-Template DUCC-Template elements elements X X X No jargon intended - X* X X - - x - x - link with GES by process and concept in the proposed tool for exposure modelling MEASE:http://www.ebrc.de/ebrc X X (exposure duration) X X X X X - X X X x x x x /ebrc-mease.php; and DU scaling tool: http://www.arche- consulting.be/Metal-CSA- toolbox/du-scaling-tool X link with GES by process and concept in the proposed tool for exposure modelling MEASE:http://www.ebrc.de/ebrc X X (LEV, use of gloves, googles) X X X X X X - X X X x x x x X /ebrc-mease.php; and DU scaling tool: http://www.arche- consulting.be/Metal-CSA- toolbox/du-scaling-tool X Generic exposure scenario templates have been developped X X X X X X X - X X - T:\PRODUCT T:\PRODUCT STEWARDSHIP\3 - STEWARDSHIP\3 - in progress in progress in progress FEDERCHIMICA/A ISPEC; Gesamtverband der deutschen Textil- und Modeindustrie e. V.; Verband der ETRMA has been closely cooperating with ERCA (European Rubbe Nordwestdeutsche Chamical Association). The work focused on the practical Our downstream Our downstream n implementation of the Tyre/Rubber Industry GES for the CSA/ES/RC TEGEWA and with eurometaux and metal REACH consortia - with ESIG/ESVOC entire plastics chain users are memebrs users are members Textil- und TEGEWA and IVC of specific substances. By means of this cooperation, new FEDERCHIMICA/AISPEC of CEPE, etc. of CEPE, FEICA etc. Bekleidungsindustr information/data have been also generated for further refining the ie e.V.; TVI- original GES. Verband e.V. Gesamtverband der deutschen Textilveredlungsind ustrie Will be developped in 2011 x BDI standard phrases - X X X - X - - - - x X - X X X - - - - - x X - X X X x x - - - x X - X x x - - - http://www.arche- http://www.feica.eu/ehs- ECPA SpERC Fact No spERCs from EDANA at http://info.vci.de/user_cc/SpERCs/Forms/ http://www.esig.org/en/regulatory- work in progress; draft available on request Sheet_26th Oct 20 this stage AllItems.aspx http://www.etrma.org/public/activitieschemreach.asp consulting.be/Metal-CSA- sustainability/reach/feic X - information/reach/ges-library/ges-spercs-2 toolbox/spercs-tool-for-metals a-use-descriptors For ERMA: J. Hemmings Dr. Volker Paul Becker email@example.com Schröder Dr. Volker Schröder Dr. Volker Schröder Rocky Rowe Oliver Bisazza E. Setien Olivier Coube firstname.lastname@example.com For Véronique Schoune Dr. Pierfrancesco Fois Lorenzo Zullo Ophélie Roblot Cristina Arregui Bjoern-Markus Sude Pierre Germain Michel De Poortere Pierre Germain email@example.com firstname.lastname@example.com firstname.lastname@example.com Dr. Gunther Uhlhorn Dominique de Halleux - email@example.com +32 2 Pierre WOLFS V. Verougstraete Jana Cohrs Wolfram Frank W. Claes +32 2 663 1550 firstname.lastname@example.com email@example.com firstname.lastname@example.com copy to : Methacrylates/Acrylates/ERMA email@example.com firstname.lastname@example.com technical@etrma@org +32 2 679 02 62 email@example.com firstname.lastname@example.com email@example.com email@example.com firstname.lastname@example.com +49 (0)69-2556- +49 (0)69-2556-1343 +49 (0)69-2556-1343 email@example.com 676 72 12 +32 2 2177098 firstname.lastname@example.com firstname.lastname@example.com firstname.lastname@example.com email@example.com firstname.lastname@example.com +32 2 740 18 21 +3226767416 +33 4 42 12 47 44 Tom McKellar-Smythe GES project: +32 2 676 72 69 + 41 616909963 +32 2 218 4940 firstname.lastname@example.com +32 2 214 20 45 +49 69 2556 1410 +3226767377 +3226767369 +3226767377 1343 +49 7329 97 2330 email@example.com M. Pemberton email@example.com +441625548059 All actions All actions In progress No feedback All actions complete In progress All actions complete All actions complete All actions complete In progress All actions complete In progress All actions complete In progress All actions complete In progress In progress All actions complete In progress All actions complete In progress In progress In progress In progress All actions complete complete complete http://www.tegewa. C:\Documents and http://www.tegewa.de/re Settings\CA\My Documents\IFRA Exposure scenarios Final report 3 Feb 2010.pdf de/reach/verwendu http://www.sigmaaldrich.co http://www.fecc.org/fecc/com ach/verwendungen-in- http://www.tegewa.de/reac http://www.cefic.be/T http://www.cefic.be/T ngen-in-der- m/etc/medialib/docs/Sigm mittees/safety-health-a- http://www.feica.eu/index.php? der- h/verwendungen-in-der- http://cefic.be/files/Downloads/ECMA-2009-10- http://www.edana.org/Content/ http://www.epma.com/New_non_m http://www.esig.org/en/regulatory- http://www.isopa.org/isopa/inde http://pestpublic.plastics. emplates/shwAssoc Only for Reconsile emplates/shwAssoc textilindustrie-uses- a- www.eiga.org http://info.vci.de/user_cc/default.aspx http://www.epra.eu/50.html http://www.etrma.org/public/activitieschemreach.asp http://www.reach-metals.eu/ environment-she/171- option=com_content&view=arti chemiefaserherstellungu lederindustrie-uses-of- 30-GES-mapping-website-version-3.xls Default.asp?PageID=498 embers/tools.htm information/reach/ges-library/ x.php?page=reach net/public/ Details.asp?NID=473 members Details.asp?NID=473 of- Aldrich/General_Informatio mapping-of-uses-of-the- cle&id=103&Itemid=195 ses-of-spin-finishes-in- auxiliariescolourants-in- &HID=359&ID=185 &HID=359&ID=184. auxiliariescolourant n/1/sial_laboratory_use_m chemical-distribution-sector the-fibre-processing- leather-industry.html http://www.ip- s-in-textile- apping.xls industry.html europe.com/files/use_descript industry.html or_system_ip_europe.xls Dec-10 Mar-10 Jun-09 Dec-10 Dec-10 Jun-09 Mar-10 Nov-09 Dec-10 Jun-09 Dec-10 Dec-10 Jul-09 Dec-10 May-10 Sep-10 Jul-09 May-09 Dec-09 Dec-09 Feb-10 Jan-10 Jan-10 Jan-10 Apr-10 Guidance on how to prepare GES for the metals sector as Use descriptors for spin well as a draft list of GES have finishes in the fibre been developed by the processing industry The ETRMA generic exposure scenario document (link above) is Use descriptors Eurometaux ES taskforce in have been discussed in intended to provide necessary inputs required by REACH regitrants have been 2009. GES are developed by the frame of the CEFIC for developing substance specific exposure scenarios. developed in the Use descriptors have been Use mappings available in the REACHpage only for EIGA process in the metals sector. Textiles and Apparel frame of the CEFIC developed by laboratory field of: members for list of uses with Several metal consortia have * Description is clear and Value Chain Platform by ETRMA shall be considered as a platform for discussing substance Textiles and Use descriptors have been chemical distributors - nonwovens uses descriptors; used the GES concept and list simple, but some phrases the Belgian, German specific issues which may emerge during the registration process in Information only available in Apparel Value developed by the German (Sigma-Aldrich, B.Kraft, - superabsorbent applications not decided which support for to develop metal-specific ES by are considered as jargon for no restricted access no restricted access and Italian associations English Chain Platform by and Italian leather Honeywell) in cooperation - components for absorbent RMM and standard phrases relation to the tyre and rubber industry. Associations and process. Eurometaux has been the sector (although and CIRFS. The the Belgian, auxiliaries associations. with SGCI considering hygiene products, and but will be for members only registrants invovled in the development of registration focusing afterwards on the understandable) published version on the German and Italian information from - wet wipes English only dossiers are encuraged to contact ETRMA in case of deviation development of tools to support TEGEWA-website is a textile and textile customers from OCs and RMMs described in the ETRMA Rubber Industry the development of GES: proposal from auxiliaries GES: suport will be provided for data/information refinement. mapping & user descriptor tool TEGEWA. The other associations. (multimetallic questionnaire), involved associations do exposure assessment tools not have agreed upon it (MEASE), DU scaling tool, at the moment. SPERCs Background Background information is information is available in English available in English language. For an Italian language. For an version please contact Italian version email@example.com . please contact Leather use descriptors v.servizi@federchi Background information explained in leather mica.it . Textile is available in English specific jargon are use descriptors language. available in English and explained in textile German language specific jargon are (TEGEWA-Website) and available in in Italian language ( German language email@example.com) (TEGEWA- Website) and in Italian language ( AISE ATC ATIEL CEFS CEPE COLIPA Concawe ECCA ECMA ECPA EDANA EIGA EFCC EPMA EPRA ERMA ESIG ESVOC ETAD ETRMA Eurométaux FECC FEICA IFRA I&P Europe ISOPA PEST PPRM RECONSILE SRM TEGEWA International Association for Soaps, Detergents and Maintenance Products Technical Committee of Petroleum Additive Manufacturers in Europe Technical Association of the European Lubricants Indsutry European Committee of Sugar Manufacturers European Council of producers and importers of paints, printing inks and artists' colours European Cosmetics Association The oil companies' European association for Environment, Health and Safety in refining and distribution European Coil Coating Association European Catalyst Manufacturers Association European Crop Protection Association International association serving the nonwovens and related industries European Industrial Gases Association European Federation for Construction Chemicals European Powder Metallurgy Association European Phenolic Resins Association European Resin Manufacturers Association European Solvents Industry Group European Solvents Industry Platform The Ecological and Toxicological Association of Dyes and Organic Pigments Manufacturers European Tyre & Rubber Manufacturers' Association European Association of non-ferrous metals European Association of Chemical Distributors Association of European adhesives and sealants manufacturers International Fragrance Association Imaging and Printing Association European Diisocyanates and Polyols Producers Association Plastics Exposure Scenarios Team Polyester Powder Resin Manufacturers Silicon consortia Solvent Resins Manufacturers German Textiles association
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ADD & ADHD Health Center
Stimulant Drugs for ADHD
In this article
Stimulant drugs are the most commonly used treatment for ADHD.
Stimulants are an effective way of managing ADHD symptoms, such as short attention span, impulsive behavior, and hyperactivity. They may be used alone or in combination with behavior therapy.
Recommended Related to ADD-ADHD
Attention-Deficit/Hyperactivity Disorder: Causes of ADHD
The exact causes of ADHD are not known. Experts do know that ADHD has a strong genetic component. In addition, they think that genes that control the levels or functioning of certain chemicals in the brain called neurotransmitters seem to be different in those with ADHD. In some cases, though, there is no genetic link to ADHD, but other common behaviors, such as smoking or drinking during pregnancy, as well as other obstetrical complications have been linked to ADHD in children. Babies with low...
Read the Attention-Deficit/Hyperactivity Disorder: Causes of ADHD article > >
These drugs improve ADHD symptoms in about 70% of adults and 70% to 80% of children. They tend to reduce interruptive behavior, fidgeting, and other hyperactive symptoms, as well as help a person finish tasks and improve his or her relationships.
Improvements in behavior and attention span usually continue as long as the medication is taken, although benefits in social adjustment and school performance have not yet been shown to endure over the long term.
Stimulants are not considered to be habit-forming in the doses used to treat ADHD in children and adolescents, and there is no evidence that their use leads to drug abuse. Nonetheless, there is a potential for abuse and addiction with any stimulant medication, especially if a person has a history of substance abuse and addiction.
Common Stimulants for ADHD
There are many stimulants available to treat ADHD: short acting (immediate-release), intermediate-acting, and long-acting forms. Common stimulants include:
- Adderall (intermediate-acting)
- Adderall XR (long-acting)
- Concerta (long-acting)
- Dexedrine (short-acting)
- Dexedrine spansule (intermediate-acting)
- Daytrana (a patch that delivers the drug on a long- or shorter-acting basis)
- Metadate CD (long-acting)
- Metadate ER (intermediate-acting)
- Methylin ER (intermediate-acting)
- Ritalin (short-acting)
- Ritalin LA (long-acting)
- Ritalin SR (intermediate-acting)
- Vyvanse
- Quillivant XR (long-acting)
The short-acting forms of the drug are usually taken two or three times a day and the long-acting ones just once a day.
Newer forms of some stimulant drugs may reduce side effects and relieve symptoms for a longer period of time. They include Concerta (10-12 hour duration), Daytrana patch (7- 10 hours, depending on how long it is worn), Ritalin LA (6-8 hours), Metadate CD (6-8 hours), and Adderall XR (10-12 hours).
How Do Stimulants Work for ADHD?
For someone with ADHD, stimulants regulate impulsive behavior and improve attention span and focus by increasing the levels of certain chemicals in the brain, such as dopamine and norepinephrine, which help transmit signals between nerves.


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Report: Raptors to amnesty Linas Kleiza
Jul 16, 2013, 9:00 AM EDT
Linas Kleiza has played just 20, 49 (of 66) and 39 games the last three seasons – including none in the 2013 calendar year – as he's battled injury and below-average play. So, the Raptors forward made a sensible choice by opting into the final year of a contract that will pay him $4.6 million next season. Of course, by taking the guaranteed salary, Kleiza lost the opportunity to hunt for a more-desirable situation.
Now, Kleiza will have his freedom and his money.
Marc J. Spears of Yahoo! Sports:
The Toronto Raptors plan to amnesty forward Linas Kleiza on Tuesday, a league source told Yahoo! Sports.
Kleiza played for Olympiakos of the Greek League during the 2009-10 season, and a source said his preference is to return to play overseas again.
Perhaps, there will be a market for Kleiza among NBA teams, but I don't see why. He has a reputation for being a good shooter, but his career 3-point percentage is just 33.5. Really, Kleiza is a mediocre-at-best player with no specialty. Good teams could probably use someone who fills a more specific role, and bad teams could probably use someone with more upside than the 28-year-old Kleiza.Kleiza was successful in Greece between his four years with the Nuggets and three years with the Raptors. If his preference is to play overseas next season, that might be for the best.
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Boulangerie Patisserie: Dessert at the France Pavilion in Epcot
One of the best things about the World Showcase in Epcot is the range of dining choices available.
In part one of the Boulangerie Patisserie (that would be the boulangerie), quiches and a small variety of other savoury dishes are available from behind the counter. But, it being the France Pavilion (to the immediate right of the exterior Boardwalk entrance), everyone in line is waiting to get to part two – the patisserie – which contains trays of cookies, mousse cups, miniature cakes, tarts, and, of course, pastries.
Coffee, tea, and hot chocolate are always on hand for those surprisingly cool nights. If you're loitering around the World Showcase after Future World has closed, waiting, perhaps, for IllumiNations: Reflections of Earth, dessert is an excellent time (and tummy) filler, and can help reduce the boredom of waiting for the show to start.
IllumiNations occurs primarily at the adjacent shore of the World Showcase Lagoon from the Boulangerie Patisserie, but if you'd rather not fight for a seat, eat your dessert at one of the café tables by the water; you'll have a view similar to standing in the middle of the crowd, and you'll be more comfortable.
Cafeteria style. No indoor seating; patio seating available.
- Food and Dining
- Theme Park Trips
- Work Abroad
Le Cellier Steakhouse: Dining at the Canadian Pavilion in Epcot
One of the best things about the World Showcase in Epcot is the range of dining choices available.
In "the cellar" of one of two chateaus at the Canadian Pavilion (first on the right from the Future World entrance), you'll find probably the best steakhouse on park property.
Whether or not you can correctly answer the trivia question of the day (which will win you a small prize, or praise, depending on your age), your meal will begin with a complimentary vase of warm breadsticks, including sourdough and pretzel. Caesar salad is a wonderful choice for light vegetarian eaters, or is otherwise the perfect appetizer for the steak of your choice. Not much variety to this menu.
Lunch and dinner only.
Reservations recommended. Call up to 180 days in advance.
- Theme Park Trips
- Food and Dining
- Work Abroad
Rose and Crown Dining Room: Dining at the United Kingdom Pavilion in Epcot
One of the best things about the World Showcase in Epcot is the range of dining choices available.
If you're craving some traditional comfort food, look no further than the Rose and Crown Dining Room in the United Kingdom Pavilion (second on the right from the Future World entrance). Yorkshire pudding, potatoes, and gravy accompany most items on the menu, including steak, roast, and shepherd's pie.
Fish and chips are available here and at the take-out window around the corner. (Caution: patrons of the take-out window often haven't a place to eat in the shade.)
On a hot day (most days) the cheese and fruit platter is a refreshing and light vegetarian choice.
Lunch and dinner only. Patio seating available.
Reservations recommended. Call up to 180 days in advance.
- Work Abroad
- Food and Dining
- Theme Park Trips
Rainforest Cafe: Oasis
We had one family dinner on Saturday night at the Rainforest Cafe at Animal Kingdom. The Cafe is accessible without entering the park. We had a reservation for a large group, and after a short wait while we were collecting the group, we were seated. Each family ordered for their own children.
Chef Mickey: Breakfast with Mickey
We arranged to have "Breakfast with Mickey" on Sunday morning. After waiting for our 'time', we had our photos taken (I arranged for us to do 4 generation family groups - all of my children individually had a group shot with me and my mother, and their children), and then had breakfast. The various Disney characters came around to the children and signed their autograph books and made photo ops.
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