Drop Shape Analysis: Drop shape analysis (DSA) is an image analysis method for determining the

contact angle from the shadow image of a sessile drop and the surface tension or interfacial tension
from the shadow image of a pendant drop
Background: A drop is metered onto a solid sample (sessile drop) or is located at the tip of a needle
(pendant drop). An image of the drop is recorded with the help of a camera and transferred to the
drop shape analysis software. A contour recognition is initially carried out based on a grey-scale
analysis of the image. In the second step, a geometrical model describing the drop shape is fitted to
the contour.
Contact angle: The contact angle is given by the angle between the calculated drop shape function
and the sample surface, the projection of which in the drop image is referred to as the baseline


Sessile drop with fitted contour (shown in green)

Several methods for determining the contact angle with different measuring ranges and
applications are available when modelling the drop shape:


Surface Tension
The surface tension is always calculated with the help of a
Young-Laplace fit to the contour of a pendant drop
determined by image analysis. The image scale and the
difference in density between drop phase and bulk phase
must be known for this (for more information, see under
pendant drop).

Measuring methods
A contact angle goniometer is used to measure the contact angle.
The static sessile drop method
The sessile drop method is measured by a contact angle goniometer using an optical
subsystem to capture the profile of a pure liquid on a solid substrate. The angle formed
between the liquid/solid interface and the liquid/vapor interface is the contact angle. Older
systems used a microscope optical system with a back light. Current-generation systems
employ high resolution cameras and software to capture and analyze the contact angle.
Angles measured in such a way are often quite close to advancing contact angles.
Equilibrium contact angles can be obtained through the application of well defined
vibrations.

The dynamic sessile drop method
The dynamic sessile drop is similar to the static sessile drop but requires the drop to be
modified. A common type of dynamic sessile drop study determines the largest contact
angle possible without increasing its solid/liquid interfacial area by adding volume
dynamically. This maximum angle is the advancing angle. Volume is removed to produce the
smallest possible angle, the receding angle. The difference between the advancing and
receding angle is the contact angle hysteresis.
The dynamic sessile drop method
Dynamic Wilhelmy method
A method for calculating average advancing and receding contact angles on solids of uniform
geometry. Both sides of the solid must have the same properties. Wetting force on the solid
is measured as the solid is immersed in or withdrawn from a liquid of known surface tension.
Also in that case it is possible to measure the equilibrium contact angle by applying a very
controlled vibration. That methodology, called VIECA, can be implemented in a quite simple
way on every Wilhelmy balance.
[7]

Single-fiber Wilhelmy method
Dynamic Wilhelmy method applied to single fibers to measure advancing and receding
contact angles.
Washburn's equation capillary rise method
Enables measurement of average contact angle and sorption speed for powders and other
porous materials. Change of weight as a function of time is measured.
[8]
Dynamic contact angle
The dynamic contact angle is the contact angle which occurs in the course of wetting (advancing
angle) or de-wetting (receding angle) of a solid.
Background
The advancing angle in particular is used for investigating solid surfaces, as in doing so the
contact angle is measured at a surface which is repeatedly being re-wetted and also at several
positions which are very close to one another. This minimises time effects, such as evaporation,
and averages out local inhomogeneities.
The receding angle which occurs on de-wetting is usually smaller than the advancing angle. This
difference, referred to as hysteresis, is used as a measure of the roughness of the solid.
One criterion for deciding between dynamic and static contact angle is the technical wetting
process observed. Dynamic processes, such as coating, are better modelled by means of
dynamic measurements. Static contact angles are often more meaningful for assessing quasi-
static processes, e.g. bonding in semiconductor technology.
The speed chosen for dynamic measurements must not be too great in order to avoid falsifying
the measurement by the introduction of mechanical energy. However, on the other hand, it must
not be too small in order to rule out the time effects described above.
Methods
1) Increasing and reducing the volume of a sessile drop during drop shape analysis
2) Measurement of the Wilhelmy contact angle by measuring the force on a vertically
immersed plate
3) Shape analysis of a drop which moves over the inclined surface of a solid

Advancing angle
The advancing angle between a liquid and a solid is the contact angle which is produced in the
course of the wetting process, in contrast to the static contact angle with which the contact area
between liquid and solid is not changed from the outside during the measurement. The
advancing angle - like the receding angle - is described as the dynamic contact angle.
Background
The advancing angle is frequently used for investigating solid surfaces, as in doing so the contact
angle is measured at a surface which is freshly wetted and also at several positions which are
very close to one another. This minimises time effects, such as evaporation, and averages out
local inhomogeneities.
Methods
Increasing the volume of a sessile drop during drop shape analysis. The volume of the
drop is increased by hand or with a motorised piston. At the same time, images are
recorded and evaluated. In practice, a drop of about 3-5 L is formed on the surface of
the solid with the help of a syringe needle and then slowly enlarged. In doing so, the
interface migrates outwards.
At the beginning, the contact angle measured is not independent of the drop size, as the
contact with the needle affects the drop shape. Only after this stage can the advancing
angle be measured sensibly. Instruments: DSA100, DSA30, DSA25

Measurement of the advancing angle by increasing the volume
Measurement of the Wilhelmy contact angle by measuring the force on a vertically
suspended plate which is immersed and withdrawn during the measurement. The
receding angle is measured at the same time using this method. Instruments: K100
Shape analysis of a drop which moves over the inclined surface of a solid. Instruments:
DSA100 or DSA30 with tilting table
Young-Laplace fit

The Young-Laplace-fit is a Method for determining the contact angle in drop shape analysis.
The drop shape is analysed based on the shape of an ideal sessile drop, the surface curvature
of which results only from the force equilibrium between surface tension and weight.

Background

According to the Young-Laplace equation, with a curved liquid surface, there is a relationship
between the radii of curvature r
1
and r
2
, the surface tension and the Laplace pressure p:

With a sessile drop under the effect of gravity, the curvature is affected by the hydrostatic
pressure resulting from the weight of the liquid. At the same time, the radii of curvature of the
surface change as a function of height. With the Young-Laplace fit, parameters of an equation
system which models the shape of the sessile drop are determined by means of numerical
analysis. The point of intersection of the modelled contour with the baseline (three-phase
point) is determined in order to measure the contact angle.

In the case of a symmetrical, undistorted drop on a level, smooth surface, the Young-Lapace
fit gives the best correspondence between the theoretical drop shape and the real drop shape.
In addition, the surface tension of the liquid can be calculated if the scale of the video image
of the drop and the density of the liquid are known.

As the shape of the drop deviates from the elliptical form for large contact angles and
volumes, in these cases the Young-Laplace fit is preferred to the conic section method. The
Young-Laplace fit is not suitable for asymmetrical drops (e.g. when measuring the dynamic
contact angle) or for samples which are not level (e.g. for measurements on a tilting table).
Three-phase point
In the two-dimensional projection of a three-phase system, a three-phase point is a point which is
common to the three phase boundary lines. In the frequently considered case of a sessile drop on
a solid surface in air when measuring the contact angle, this is the transition point between the
liquid/solid, liquid/gaseous and solid/gaseous boundary lines.

Static contact angle
The static contact angle is the contact angle with which the contact area between liquid and solid is not
changed from the outside during the measurement, in contrast to the dynamic contact angle which is
produced in the course of wetting (advancing angle) or de-wetting (receding angle).
Background
A pure liquid in the saturated vapor phase forms the Young contact angle on an ideal, chemically and
topologically homogeneous solid as described by Young's equation. In this case, the static and dynamic
contact angles would be equal.
With real solids, liquids and ambient conditions, the contact angle can vary as a function of time and
location. Inhomogeneities and changes of wetting over time can therefore be detected by means of the
static contact angle.

If, on the other hand, the effect of location and time is to be minimized, then the advancing angle is usually
measured.
A further criterion for deciding between static and dynamic contact angle is the technical wetting process
observed. Dynamic processes, such as coating, are better modelled by means of dynamic measurements.
Static contact angles are often more meaningful for assessing quasi-static processes, e.g. bonding in
semiconductor technology.
Measuring methods
Drop shape analysis on sessile drops: Analysis of the image of a sessile drop deposited on a solid.
Instruments: DSA100, DSA30, DSA25, MobileDrop
Captive bubble method: Analysis of the image of an air bubble in a liquid beneath a solid.
Instruments: DSA100, DSA30, DSA25
Top-view distance method: The curvature of the drop surface associated with the contact angle is
measured using the distance between light spots which are reflected on the top of a drop surface.
Instrument: TVA100
Roll-off angle
The roll-off angle is the angle of inclination of a surface at which a drop rolls off it. As a rule, it is
used to characterize ultrahydrophobic surfaces with very high contact angles (>>90) where the
drop is approximately spherical. With smaller contact angles, although a drop can also move
from the surface, it is usually initially deformed and then slides over the surface.
The roll-off angle is an empirical variable which is highly dependent on the particular measuring
conditions, such as drop size and tilt speed.
Biomimetic things in nature
















1. Anti -fogging propert y
The steam fogs a mi rror and a gl ass easi l y, because moi sture i n the ai r i s cool ed down and
numerous waterdrops form on the surface of the usual materi al s. However, uti l i zi ng the super -
hydrophi l i c coati ng, the water cannot exi st i n the shape of a drop, but spreads fl atl y on the
super-hydrophi l i c surface. Fi gure 4. shows the dependence of the anti -foggi ng abi l i ty on the
contact angl e of water.


Recentl y, the opposi te way to remove waterdrops from the surface of materi al has been
proposed. For exampl e, super -hydrophobi c coati ng i s appl i ed for wi ndshi el d to remove the
waterdrops easi l y. However, super -hydrophobi c surface cannot stop foggi ng of the wi ndshi el d
unl ess the waterdrops i s removed wi th wi nd power or vi brati on. On the contrary, the super -
hydrophi l i c surface never fogs on condi ti on of no wi nd nor vi brati on

Appl yi ng the super-hydrophi l i c photocatal yst for a surface of a mi rror or a gl ass, they remai n
the cl ear surface wi thout f oggi ng semi permanentl y. Fi gure 5. shows the di fference of the
foggi ng wi th steam bet ween normal gl ass and the photocatal yst coated gl ass.


Though the normal gl ass fogs wi th steam, the super -hydrophi l i c gl ass remai ns transparent. In
thi s way, the super-hydrophi l i c technol ogy easi l y real i zes the anti -foggi ng gl ass products and
mi rrors wi th l ow costs.
2. Self-cleaning by a rai nfall
Usual l y, i t i s very di ffi cul t to remove oi l from resi ns wi th water unl ess usi ng detergent. Whi l e,
uti l i zi ng the super-hydrophi l i c coati ng, oi l can be easi l y removed from the surface, because the
surface has so much stronger affi ni ty wi th water than oi l . Therefore, the oi l on the super-
hydrophi l i c surface i s easi l y removed by soaki ng the materi al i n water, as shown on Fi g. 6.

In thi s way, oi l can be easi l y removed onl y by washi ng wi th water wi thout detergent.

In urban area, al most di rty marks on the exteri or wal l are mai nl y caused by t he exhaust of
automobi l es and factori es, whi ch are hydrophobi c and oi l y. Uti l i zi ng the super -hydrophi l i c
coati ng, these hydrophobi c di rty marks can be sel f -cl eaned wi th a rai nfal l , and you can keep
the wal l cl ean semi permanentl y.

Fi g. 7 shows the di fference of sel f -cl eani ng abi l i ty by a rai nfal l bet ween the super -hydrophi l i c
coated and normal si l i cone coated cement pl ates.

It i s obvi ous that the ori gi nal pl ates remarkabl y get di rty, whi l e the super -hydrophi l i c coated
pl ates remai n al most cl ean. By the accel erated weatheri ng test, the super -hydrophi l i c coati ng
can keep the sel f -cl eani ng abi l i ty more than 3000 hours, whi ch means the coati ng has
durabi l i ty of more than 10 years i n the usual envi ronment.
Si l i cone seal ant i s used to seal the gap of al umi num panel s and wi ndows of a bui l di ng.
Because some components of the seal ant are washed away wi th a rai nfal l , they soi l the exteri or
wal l s. The super-hydrophi l i c coati ng al so can be appl i ed to keep off the hydrophobi c di rty
marks caused by si l i cone seal ant from the wal l s, as shown on Fi g. 8.

3. Other applications
In addi ti on to the above-menti oned appl i cati ons, the super -hydrophi l i ci ty can be appl i ed for
many other products uti l i zi ng secondary properti es. For exampl e, the super -hydrophi l i c surface
dri es qui ckl y uti l i zi ng the property of that the water cannot fl atl y spreads on i t. Thi s effect can
be appl i ed to preventi ng dewdrops formi ng i nsi de a wi ndowpane and a greenhouse, for the
purpose of protecti ng vegetabl es from rotti ng by dewdrops. Besi des, bubbl es hardl y sti ck on
the super-hydrophi l i c surf ace i n the water. Thi s eff ect al so shoul d have many appl i cati ons.

Suggested appl i cati on of super -hydrophi l i c technol ogy are shown i n Tabl e 1.
The basi c patents for the super -hydrophi l i c technol ogy have been resi stered on March
13,1998.The worl dwi de patent appl i cati ons and resi strati ons are i n progress.The total number
of patents i s 350.

As the i ntensi ty of UV l i ght i n a room i s not strong enough to reach the super -hydrophi l i ci ty, we
are now i mprovi ng the materi al that reaches super -hydrophi l i ci ty wi th l ess UV l i ght, i n addi ti on,
we are exami ni ng the effi ci ent l i ghti ng to the photocatal yst.


Table 1 Suggested appli cations of super -hydrophilic technology

Di vi si on Functi on Appl i cati on
Materi al s for a
road
Cl eani ng easi ness
Tunnel l i ghti ng,
Tunnel wal l ,
Cl ear soundproof wal l
Sel f Cl eani ng by a
rai nfal l
Traffi c si gn, Li ghtni ng,
Soundproofed wal l , Guardrai l ,
Decorati ve l ami nated panel and
Refl ector on a read
Anti -foggi ng
property
Road mi rror
Materi al s for a
house
Cl eani ng easi ness
Parts of a Ki tchen, a Bathroom
and Interi or furni shi ngs
Sel f Cl eani ng by a
rai nfal l
Exteri or ti l es, Si di ng boards,
Wi ndow, Sash, Screen door,
Gate door, Roof , Sun parl or,
Handrai l of a verandah
Anti -foggi ng
property
Mi rror of a Bathroom and a
Dresser
Accel erated dryi ng Toi l et, Wi ndow, Bathroom
Materi al s for a
tal l bui l di ng
Sel f Cl eani ng by a
rai nfal
Wi ndow, Sash, Curtai n wal l ,
Pai nted steel pl ate, Al umi num
panel , Ti l e, Bui l di ng stone,
Crystal l i zed gl ass, Gl ass fi l m
Materi al s for a
store
Cl eani ng easi ness Showcase
Sel f Cl eani ng by a
rai nfal l
Si gnboard, Fi ngerpost, Show
wi ndow, The exteri or of a store
Anti -foggi ng
property
Refri gerated showcase
Materi al s for
agri cul ture
Sel f Cl eani ng by a
rai nfal l , Preventi ng
dewdrops formi ng
Pl asti c and Gl ass greenhouse
Materi al s for an
el ectri c and
el ectroni c
i nstrument
Cl eani ng easi ness Computer di spl ay
Sel f Cl eani ng by a
rai nfal l
Upper gl ass of a sol ar
cel l ,Insul ator
Preventi ng
dewdrops formi ng
Heat exchanger of an ai r
condi ti oner,Hi gh-vol tage cabl e
Materi al s for
vehi cl es
Sel f Cl eani ng by a
rai nfal l
Pai nti ng and Coati ng of vehi cl es,
The outsi de of wi ndows,
Headl i ghts
Anti -foggi ng
property
The i nsi de of wi ndows, Gl ass
fi l m,Hel met vi sor
Preventi ng
dewdrops formi ng
Si devi ew mi rror, Rearvi ew mi rror
and Wi ndshi el d of a motorcycl e,
Si demi rror fi l m
Materi al s for an
opti cal
i nstrument
Anti -foggi ng
property
Opti cal l ens
Materi al s for
medi cal
i nstruments and
suppl i es
Bi o-compati bi l i ty Contact l ens, Catheter
Dai l y necessi ti es
and Consumer
products
Cl eani ng easi ness Tabl eware, Ki tchenware
Sel f Cl eani ng by a
rai nfal l
Spray of anti -foul i ng coat
Anti -foggi ng
property
Spray of anti -foggi ng coat, Anti -
foggi ng fi l m
Pai nt
Al l properti es
menti oned avobe
Pai nt,Coat


It i s obvi ous that the ori gi nal pl ates remarkabl y get di rty, whi l e the super -hydrophi l i c coated
pl ates remai n al most cl ean. By the accel erated weatheri ng test, the super -hydrophi l i c coati ng
can keep the sel f -cl eani ng abi l i ty more than 3000 hours, whi ch means the coati ng has
durabi l i ty of more than 10 years i n the usual envi ronment.
Si l i cone seal ant i s used to seal the gap of al umi num panel s and wi ndows of a bui l di ng.
Because some components of the seal ant are washed away wi th a rai nfal l , they soi l the exteri or
wal l s. The super-hydrophi l i c coati ng al so can be appl i ed to keep off the hydrophobi c di rty
marks caused by si l i cone seal ant from the wal l s, as shown on Fi g. 8.