A
long read, but for anyone who is interested in the 'Why' and 'How' silica
coating work the way they do - read on
[:
The hydrophobicity of a surface is determined by the contact angle. The higher
the contact angle the higher the hydrophobicity of a surface. Surfaces with a
contact angle < 90° are referred to as hydrophilic and those with an angle
>90° as hydrophobic. Some plants show contact angles up to 160° and are
called super-hydrophobic meaning that only 2-3% of a drop's surface is in
contact. Plants with a double structured surface like the lotus can reach a
contact angle of 170° whereas a droplet’s actual contact area is only 0.6%. All
this leads to a self-cleaning effect.
Dirt
particles with an extremely reduced contact area are picked up by water
droplets and are thus easily cleaned off the surface. If a water droplet rolls
across such a contaminated surface the adhesion between the dirt particles,
irrespective its chemistry, and the droplet is higher than between the particle
and the surface].
Wilhelm Barthlott of the University of
Bonn in Germany, discoverer and developer of the “lotus effect,” has a vision
of a self-cleaning Manhattan, where a little rain washes the windows and walls
of skyscrapers as clean as the immaculate lotus. Elsewhere, he sees tents and
marquees using new textiles that stay equally spotless with no intervention
from a human cleaner. He is not the only one with his sights set on a future
populated with objects that rarely if ever need washing: in Japan,
technologists are developing self-deodorizing and disinfectant surfaces for
bathrooms and hospitals.
Michael Rubner and Robert Cohen of the
Massachusetts Institute of Technology (MIT) envisage similar technologies
keeping bathroom mirrors un-fogged and controlling micro fluidic “labs on a
chip” (in which fluids move through microscopic pathways). Already with us are
shirts, blouses, skirts and trousers that shrug off ketchup, mustard, red wine
and coffee. A revolution in self-cleaning surfaces is under way.
The story of self-cleaning materials
begins in nature with the sacred lotus (Nelumbo
nucifera), a radiantly graceful aquatic
perennial that has played an enormous role in the religions and cultures of
India, Myanmar, China and Japan. The lotus is venerated because of its
exceptional purity. It grows in muddy water, but its leaves, when they emerge,
stand meters above the water and are seemingly never dirty. Drops of water on a
lotus leaf have an unearthly sparkle, and rainwater washes dirt from that leaf
more readily than from any other plant.
It is this last property that drew
Barthlott’s attention. In the 1970s he became excited by the possibilities of
the scanning electron microscope, which had become commercially available in
1965 and offered vivid images down to the nanometre realm. At that scale of
magnification, specks of dirt can ruin the picture, and so the samples have to
be cleaned.
But Barthlott noticed that some plants
never seemed to need washing, and the prince of these was the lotus. Barthlott
realized that the effect is caused by the combination of two features of the
leaf surface: its waxiness and the microscopic bumps (a few microns in size)
that cover it. He knew from basic physics that the waxiness alone should make
the leaves hydrophobic, or water-hating. On such a material, drops of water sit
up high to minimize their area of contact with the material. Water on a more
hydrophilic, or water-loving, substance spreads across it to maximize the
contact area for a hydrophilic surface, the contact angle (where the droplet’s
surface meets the material) is less than 30 degrees; a hydrophobic surface has
a contact angle greater than 90 degrees.
In addition, he understood that the
innumerable bumps take things a step further and cause the lotus surface to be
super hydrophobic—the contact angle exceeds 150 degrees, and water on it forms
nearly spherical droplets with very little surface contact that roll across it
as easily as ball bearings would. The water sits on top of the bumps like a
person lying on a bed of nails. Air trapped between the water and the leaf
surface in the spaces around the bumps increases the contact angle, an effect
that is described by the Cassie-Baxter equation, named after A.B.D. Cassie and
S. Baxter, who first developed it in the 1940s –
Due to their high surface tension, water
droplets tend to minimize their surface by trying to achieve a spherical shape.
On contact with a surface, adhesion forces result in wetting of the surface.
Either complete or incomplete wetting may occur depending on the structure of
the surface and the fluid tension of the droplet. The cause of self-cleaning
properties is the hydrophobic water-repellent double structure of the surface.
This enables the contact area and the adhesion force between surface and droplet
to be significantly reduced resulting in a self-cleaning process.
The hydrophobicity of a surface can be
measured by its contact angle. The higher the contact angle the higher the
hydrophobicity of a surface. Surfaces with a contact angle < 90° are
referred to as hydrophilic and those with an angle >90° as hydrophobic.
Dirt particles with an extremely reduced
contact area are picked up by water droplets and are thus easily cleaned off
the surface. If a water droplet rolls across such a contaminated surface the
adhesion between the dirt particle, irrespective of its chemistry, and the
droplet is higher than between the particle and the surface. As this
self-cleaning effect is based on the high surface tension of water, but it does
not work with organic solvents. Therefore, the hydrophobicity of a surface is no
protection against graffiti.
Wetting [:
the ability of a liquid to maintain contact with a solid surface, resulting
from intermolecular interactions when the two are brought together. The degree
of wetting (wettability) is determined by a force balance between adhesive and
cohesive forces]
Dirt, Barthlott saw, similarly touches
only the peaks of the lotus leaf’s bumps. Raindrops easily wet the dirt and
roll it off the leaf. This discovery that microscopic bumps enhance cleanliness
is wonderfully paradoxical. I learned at my mother’s apron that “nooks and
crannies harbour dirt”—capturing the conventional folk wisdom that if you want
to keep things clean, keep them smooth. But contemplation of the lotus showed
that this homily is not entirely true.
First and foremost a botanist, Barthlott
initially did not see commercial possibilities in his observation of how the
minuscule bumps keep lotus leaves spotless. In the 1980s, though, he realized
that if rough, waxy surfaces could be synthesized, an artificial lotus effect
could have many applications. He later patented the idea of constructing
surfaces with microscopic raised areas to make them self-cleaning and
registered Lotus Effect as a trademark.
Engineering a super hydrophobic surface
on an object by using the lotus effect was not easy—the nature of a hydrophobic
material is to repel, but this stuff that repels everything has to be made to
stick to the object itself. Nevertheless, by the early 1990s Barthlott had
created the “honey spoon”: a spoon with a homemade microscopically rough
silicone surface that allows honey to roll off, leaving none behind. This
product finally convinced some large chemical companies that the technique was
viable, and their research muscle was soon finding more ways to exploit the
effect.
The leading application so far is the facade
paint for buildings, introduced in 1999 by the German multinational Sto AG and
a huge success. “Lotus Effect” is now a household name in Germany; last October
the journal Wirtschafts*woche named it as one of the 50 most significant German
inventions of recent years.
No More Restaurant Disasters
Say “self-cleaning...,” and many people
would add “clothes” as the missing word. We do not clean the outside of our
houses very often, but washing clothes is always with us. After a tentative
start, self-cleaning fabrics are popping up all over. It began with Nano-Care.
Nano-Care is a finish applied to fabrics
developed by inventor and entrepreneur David Soane, now made by his company
Nano-Tex. Think of the fuzz on a peach; put the peach under the tap, and you
will see the Nano-Care effect. Nano-Care’s “fuzz” is made of minuscule whiskers
and is attached to the cotton threads. The whiskers are so small—less than a
thousandth of the height of lotus bumps—that the cotton threads are like great
tree trunks in comparison.
Nano-Tex’s rival is the Swiss firm
Schoeller Textile AG, which calls its technology NanoSphere. The system has
nanoscopic particles of silica or of a polymer on the clothing fibres and these
particles provide the lotus like bumpy roughness.
Because many untested claims have been
made to support nanotechnology products, standards institutions are beginning
to set stringent tests for self-cleaning clothing that are based on these
innovations.
In October 2005 the German Hohenstein
Research Institute, which offers tests and certifications to trade and industry
around the world, announced that NanoSphere textiles were the first of such
fabrics to pass a whole range of tests, including those examining water
repellence and the ability of the fabric to maintain its performance after
ordinary wash cycles and other wear and tear. In a test of my own, samples of
NanoSphere showed an impressive ability to shrug off oily tomato sauces, coffee
and red wine stains—some of the worst of the usual suspects.
Easy-clean clothes are becoming widely
available, but buyers of marquees, awnings and sails are expected to constitute
the biggest market (in terms of money spent) for lotus effect finishes. No one
really wants to have to clean these large outside structures.
Super-wettability
The exploration of the lotus effect
began as an attempt to understand the self-cleaning powers of one type of
surface—waxy ones with microscopic or even nanoscale structures. This research
has now broadened into an entire new science of wet ability, self-cleaning and
disinfection.
Researchers realized that there might be many
ways to make super hydrophobic surfaces and that super-hydrophobicity
reverse—super-hydrophobicity—might also be interesting. The leading player in
super-hydrophobicity is the mineral titanium dioxide, or Titania.
Titania’s journey to stardom began more
than four decades ago with a property that has nothing to do with wet ability.
In 1967 Akira Fujishima, then a graduate
student at the University of Tokyo, discovered that when exposed to ultraviolet
light, Titania could split water into hydrogen and oxygen. The splitting of
water powered by light, or photolysis, has long been something of a holy grail
because if it could be made to work efficiently, it could generate hydrogen
cheaply enough to make that gas a viable, carbon-free substitute for fossil
fuels. Fujishima and other researchers pursued the idea vigorously, but
eventually they realized that achieving a commercial yield was a very distant
prospect.
The studies did reveal that thin films
of Titania (in the range of nanometres to microns thick) work more efficiently
than do larger particles. And, in 1990, after Fujishima teamed up with Kazuhito
Hashimoto of the University of Tokyo and Toshiya Watanabe of the sanitary
equipment manufacturer TOTO, he and his colleagues discovered that nanoscale
thin films of titania activated by ultraviolet light have a photo catalytic
effect, breaking down organic compounds—including those in the cell walls of
bacteria—to carbon dioxide and water.
Titania is photo catalytic because it is
a semiconductor, meaning that a moderate amount of energy is needed to lift an
electron from the mineral’s so-called valence band of filled energy levels
across what is known as a band gap (composed of forbidden energy levels) into
the empty “conduction band,” where electrons can flow and carry a current.
In titanic’s case, a photon of
ultraviolet light with a wavelength of about 388 nanometres can do the trick,
and in the process it produces two mobile charges: the electron that it hoists
to the conduction band as well as the hole that is left behind in the valence
band, which behaves much like a positively charged particle. While these two
charges are on the loose, they can interact with water and oxygen at the
surface of the titania, producing superoxide radical anions (O2–) and hydroxyl
radicals (OH)—highly reactive chemical species that can then convert organic
compounds to carbon dioxide and water.
In the mid-1990s the three Japanese
researchers made another crucial discovery about Titania when they prepared a
thin film from an aqueous suspension of Titania particles and annealed it at
500 degrees Celsius. After the scientists exposed the resulting transparent
coating to ultraviolet light, it had the extraordinary property of complete wet
ability—a contact angle of zero degrees—for both oil and water.
The ultraviolet light had removed some
of the oxygen atoms from the surface of the Titania, resulting in a patchwork
of nanoscale domains where hydroxyl groups became adsorbed, which produced the
super-hydrophobicity. The areas not in those domains were responsible for the
great affinity for oil. The effect remained for several days after the
ultraviolet exposure, but the Titania slowly reverted to its original state the
longer it was kept in the dark.
Although it is the very opposite of the
lotus leaf’s repulsion of water, Titania’s super-hydrophobicity turns out also
to be good for self-cleaning: the water tends to spread across the whole
surface, forming a sheet that can carry away dirt as it flows. The surface also
resists fogging, because condensing water spreads out instead of becoming the
thousands of tiny droplets that constitute a fog. The photo catalytic action of
Titania adds deodorizing and disinfection to the self-cleaning ability of
coated items by breaking down organics and killing bacteria.
The titania-coating industry is now
burgeoning. TOTO, for instance, produces a range of photo catalytic
self-cleaning products, such as outdoor ceramic tiles, and it licenses the
technology worldwide.
Because nanocoating of Titania is
transparent, treated window glass was an obvious development. In 2001 Activ
Glass, developed by Pilkington, the largest glass manufacturer in the U.K.,
became the first to hit the market. In general, glass is formed at about 1,600 degrees
C on a bed of molten tin.
To make Activ Glass, titanium
tetrachloride vapour is passed over the glass at a later cooling stage,
depositing a layer of Titania finer than 20 nanometres thick. Activ Glass is
fast becoming the glass of choice for conservatory roofs and vehicles’ side
mirrors in the U.K.
Unfortunately, ordinary window glass
blocks the ultraviolet wavelengths that drive Titania’s photo catalytic
activity, so titania nano layers are less useful indoors than out. The answer
is to “dope” the Titania with other substances, just as silicon and other
semiconductors are doped for electronics. Doping can decrease the material’s
band gap, which means that the somewhat longer wavelengths of indoor lighting
can activate photo catalysis.
In 1985 Shinri Sato of Hokkaido
University in Japan serendipitously discovered the benefit of doping Titania
with nitrogen. Silver can also be used to dope the Titania. Only in recent
years, however, have these approaches been translated into commercial
processes.
The antibacterial and deodorizing
properties of doped Titania are expected to have wide applications in kitchens
and bathrooms. Titania is also being used in self-cleaning textiles and offers
the advantage of removing odours. Various techniques have been devised to
attach it to fabrics, including via direct chemical bonds.
Convergence of Opposites
The lotus-inspired materials and the
titania-based thin films can be seen as opposite extremes rarely found in our
everyday world where, as English poet Philip Larkin said, “nothing’s made / as
new or washed quite clean.” For a long time, the techniques and materials were
entirely different, and studies of the super hydrophobic effect and photo
catalytic super-hydrophobicity were totally separate.
More recently, a remarkable convergence
has occurred, with investigators working on combining the two effects and on
producing both of them with very similar materials. Researchers are even
exploring ways to get the same structure to switch from being super hydrophobic
to being super hydrophilic, and vice versa.
An early hint of the convergence came in
2000 from Titania pioneers Fujishima, Watanabe and Hashimoto. They wanted to
use Titania to extend the life of lotus effect surfaces. At first blush, this
approach sounds destined for failure: Titania’s photo catalytic activity would
be expected to attack the hydrophobic, waxy coatings of lotus surfaces and
destroy the effect. And indeed, such attacks do happen with large
concentrations of Titania.
But the group found that adding just a
tiny amount of Titania could significantly prolong lotus effect activity
without greatly changing the high contact angle needed for the strong
repellence.
In 2003 Rubner and Cohen’s laboratory at
M.I.T. discovered how a minor change in construction could determine whether a
super hydrophobic or super hydrophilic surface was produced. During a visit to
China that year, Rubner recalls, he “got excited about some super hydrophobic
structures” that were mentioned at a meeting. On his return, he directed some
of his group’s members to attempt to make such structures.
His lab had developed a layer-by-layer
technique for making thin films out of a class of compounds called
polyelectrolytes. Ordinary electrolytes are substances that when dissolved in
water split up into positively and negatively charged ions; common salt or
sulphuric acid would be examples.
Polyelectrolytes are organic polymers,
plastic materials that, unlike most polymers, carry charge, either positive or
negative. Rubner and Cohen stacked up alternating layers of positively charged
poly (allylamine hydrochloride) and negatively charged silica particles. (In
earlier work they had used coatings with silica particles to mimic the lotus’s
rough hydrophobic surface.)
To these multilayers’, they added a
final coating of silicone (a hydrophobic material), but along the way they
noticed something intriguing: before they applied the silicone, the layer cake
was actually super hydrophilic. In Rubner and Cohen’s experiments, the silica
layers had created a vast warren of nanopores, forming a sponge that soaked up
any surface water instantly, a phenomenon called nanowicking.
The silica-polymer multilayer’s they
developed will not fog even if held over steaming water. If the pores get
saturated, water starts running off the edge. When the wet conditions abate,
the water in the nanowicks slowly evaporates away.
Because glass itself is mostly silica,
the multilayers are well suited for application to glass. The super hydrophilic
coatings are not only transparent and antifogging but are also antireflective.
Rubner’s team is working with industrial partners to commercialize the
discovery. Applications of this work include bathroom mirrors that never fog
and car windshields that never need a blower on cold, wet winter mornings.
Unlike Titania, Rubner’s surfaces work equally well in the light or dark.
Smart Beetles
Millions of years before scientists put
together the lotus effect and super wet ability for technological applications,
a small beetle of the Namib Desert in southern Africa was busy applying the two
effects to another end: collecting water for its own survival.
The Namib Desert is extremely
inhospitable. The daytime temperatures can reach 50 degrees C (about 120
degrees Fahrenheit), and rain is very scarce. About the only source of moisture
are thick morning fogs, typically driven by a stiff breeze. The beetle,
Stenocara sp., has developed a way to harvest the water in those mists: it
squats with its head down and it’s back up, facing the foggy wind. Water
condenses on its back and trickles down into its mouth. The scientific
rationale behind the Stenocara beetle’s technique has inspired ideas for
water-collecting technology in arid regions.
As so often happens, the beetle’s
mechanism was discovered by a researcher looking for something else. In 2001
zoologist Andrew R. Parker, then at the University of Oxford, came across a
photograph of beetles eating a locust in the Namib Desert. The locust, which
had been blown there by the region’s strong winds, would have perished from the
heat as soon as it hit the sand. Yet the beetles feasting on this literal
windfall were obviously comfortable. Parker guessed that they must have
sophisticated heat-reflection surfaces.
Indeed, Stenocara beetles do reflect
heat, but when Parker examined their backs, he immediately suspected that some
adaptation of the lotus effect was at work in their morning water-collection
process. Most of the back of a Stenocara beetle is a bumpy, waxy, super
hydrophobic surface. The tops of the bumps, though, are free of wax and are
hydrophilic. Those hydrophilic spots capture water from the fog, forming
droplets that quickly grow large enough for gravity and the surrounding super
hydrophobic area to dislodge them. In lab experiments with glass slides, Parker
found that this arrangement of regions is about twice as efficient as a smooth,
uniform surface, regardless of whether it is hydrophilic or hydrophobic.
Parker has patented a design to imitate
the beetle’s process, and the U.K. defence contractor QinetiQ is developing it
for fog harvesting in arid regions. Others are also trying to mimic Stenocara.
In 2006 Rubner and Cohen’s team created super hydrophilic spots of silica on
super*hydrophobic multilayer’s. This is one better than the beetles, whose
spots are merely hydrophilic.
The new science of super-hydrophilic (
wet ability), as exemplified by the artificial Stenocara surfaces, makes it
possible to control liquid flows at the micro scale and the nanoscale, for use
in applications that go well beyond that of keeping a surface clean. Rubner
says: “Once you realize that textured surfaces can be either super hydrophobic
or super hydrophilic depending on the top’s surface chemistry, all sorts of
possibilities open up.” Of particular use would be switchable surfaces—ones
whose wet ability can be reversed at precise locations.
Such tenability might be achieved by
many means: ultraviolet light, electricity, temperature, solvent and acidity.
In 2006 a team led by Kilwon Cho of Pohang University of Science and Technology
in South Korea achieved complete switch ability by adding a compound based on
the molecule azobenzene to the silicon zed (super hydrophobic) surface of a
silica-polyelectrolyte multilayer. The new surface is also super*hydrophobic, but
under ultraviolet light the azobenzene compound changes configuration and
converts it to super hydrophilic.
Visible light reverses the change. This
kind of control could have major applications in the field of micro fluidics,
such as the microarrays now used for drug screening and other biochemical tests
Staying Dry Underwater
It is one of the pleasant surprises of
the 21st century that the radiance of the lotus is penetrating into previously
unknown nooks and crannies, as well as beyond self-cleaning applications.
Barthlott, who saw the potential in a
drop of water on a lotus leaf, now sees almost limitless vistas. But he warns
those who want to translate from nature to technology that they are likely to
encounter great scepticism, as he did. “Do trust your own eyes and not the
textbooks, and if your observation is repeatedly confirmed, publish it,” he
advises. “But take a deep breath—expect rejections of your manuscript.”
He is, not surprisingly, a passionate
advocate for biodiversity, pointing out that many other plants and animals may
have useful properties—possibly including species unknown to science and in
danger of extinction. His current research involves super-hydrophobicity
underwater.
After studying how plants such as the
water lettuce Pistia and the floating fern Salvinia trap air on their leaf
surfaces, Barthlott created fabrics that stay dry underwater for four days. An
un-wettable swimsuit is in prospect. The big prize would be to reduce the drag
on ships’ hulls. The lotus collects no dirt, but it is garnering an impressive
string of patents
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