WETTABILITY OF SOLIDS

Emil Chibowski

Department of Physical Chemistry-Interfacial

Phenomena, Faculty of Chemistry, Maria Curie-
Skłodowska University,
20-031 Lublin, Poland
 OUTLINE

Introduction

Thermodynamics of wetting process

The surface tension of pure liquids

Types of wetting processes:
spreading
immersional
adhesional.

Wetting of solid surface in adsorption process

Wetting contact angle

Contact angle and the work of adhesion

General problem of surface free energy
formulation and determination

Other approaches to the surface free energy
determination

Contact angle hysteresis

Superhydrophobic surfaces

Examples of practical application of solid
surface wettability

Summary
 Introduction

Process of wetting of a solid by a liquid, usually by water,

is often applied or it occures naturally.
Some examples:
• We wet our hands and body with water.
• After having a meal we need to clean the dishes, thus
wetting them.
• Often we put dirt clothing into a washing machine
adding some detergent. At first it is wetted.
• The soil has to be wetted for plants to grow up.
The plant leaves have to be wetted with appropriate
solution, emulsion or suspension of chemical
substances to protect them against insects or fungus.
 • Pharmaceutical and cosmetic products are needed to wet
tissues or skin well.

• Glues and adhesive tapes must also wet well a solid

surface to strongly keep together the parts.

• Painting of solid surfaces to protect them against

corrosion, dyeing of fibres, lubrication, coatings.

• One of most important industrial processes, which is totally

based on the differences in wettability of the surfaces, is
flotation process of mineral ores enrichment.
 Important:

In all wetting processes the surface free energy of

solid and liquid, and obviously the interfacial
solid/liquid free energy, play a fundamental role.
Therefore, to understand the wetting processes description of
the interfacial interactions should be known too.
Wetting process can be investigated as a static or dynamic
one. The dynamics of wetting is of great importance in many
practical processes.
Here we will be mostly involved in description of the static
wetting, that is, description of the process that has attended
equilibrium.
 Thermodynamics of wetting process
Wetting of a solid surface occurs when one fluid phase repel
another (liquid or gas) being present on the surface.
gas γl liquid
γs γsl
///////////////////////////////////////////////////////////
solid

Fig.1. Scheme of wetting process of solid surface by a liquid.

At T, p = const. the differential of Gibbs’ free energy ‘G ‘ for a

pure liquid ‘l ’ wetting a solid surface ‘s’ determined by the
changes in the surface area ‘ A’ equals:
∂G ∂G ∂G
dG = dA s + dA sl + dA l (1)
∂A s ∂A sl ∂A l

Where subscript ‘sl‘ means solid/liquid interfacial area.

However, dA l = − dA s = dA sl (2)

∂G ∂G ∂G
And; = γl = γs = γ sl (3)
∂A l ∂A s ∂A sl

Sl/s = Ws = γs – γsl – γl (4)

Sl/s is the spreading coefficient, Ws is the work of

spreading wetting.
 The surface tension of pure liquids

The surface tension (or surface free energy) of pure liquids, or

surface free energy of solids, results from uncompensated
forces acting between the molecules (atoms) in the surface
layer being of a few molecular diameters thick.

Fig.2. A scheme of intermolecular forces acting between molecules in bulk liquid

and in the surface layer.
The resulting net force is normal to the surface and directed
toward the bulk; as well another force, tangential to the surface,
is present.
The surface tension γ is the force needed to enlarge a liquid
surface by unit, or, it is the energy (work) needed to transport a
unit area of the molecules from the bulk to the surface, i.e. to
enlarge the surface area by a unit (numerically the same value).
Surface of liquid Movable side
Movable side
Liquid (F)orce
F/ l = γ [N/m]
(W)ork

W = γ ⋅ l⋅ dx = γ ⋅ dA [J/m2 ]
Liquid film
Fig.3. Mechanical analogy to the
relationship between surface tension Fig.4. Illustration of surface
and surface free energy. tension of a soup film stretched
across a wire frame.
(Figs. 3 and 4 are from A.W. Adamson and A.P. Gast, Physical Chemistry of
Surfaces).
Consider a hypothetical system shown in Fig.5. It consists of a
pure liquid placed in a box with sliding cover made of a
material that does not interact with the liquid (zero interfacial
tension). If at T, p, n = const. the cover is slid back to create
an uncovered surface dA, the reversible work done on this
system equals, W = γdA, and it is just equal to the increase in
free energy of this system:
dG = γ ⋅ dA (6)

dA W

Fig.5. Model of the system for surface tension (Gibbs surface free energy) deter-
mination (from A.W. Adamson and A.P. Gast, Physical Chemistry of Surfaces).
Because the number of moles has not changed, the increase
in the energy is in fact due to the dA increase.
 ∂G 
Gs = γ =   (7)
 ∂A  T ,p

For the reversible process the accompanying heat gives the

surface entropy ss (per the unit area).

dq = T⋅ss ⋅dA (8)

From a general thermodynamic relationship it results;

 ∂ s 
− Ss = 
G  = dγ (9)
 ∂T 
  p dT
 Because Hs = Gs + TSs, where superscript s means ‘surface’,
we have:
s dγ
H =γ−T (10)
dT

The surface enthalpy is usually larger than the surface free

energy (surface tension). This is because the free energy is a
decreasing function of temperature.

Note: Surface tension of liquids can be measured by several

more or less direct methods which are described in a
handbook.
 Types of wetting processes
Spreading wetting
It occurs when a drop of liquid is settled on a solid surface
and enlarges its contact perimeter (spreads) (Fig.1). The
specific work of spreading (in J/m2) for this process describes
Eq.(4).

Ws = γs – γsl - γl (4)

gas γl liquid
γs γsl
///////////////////////////////////////////////////////////
solid

Fig.1. Scheme of wetting process of a solid surface by a liquid

 Its value can be positive or negative, depending on the surface
free energy of the solid and the liquid used for the wetting.

Ws > 0 if γs > (γsl + γl) Ws < 0 if γs < (γsl + γl)

If the work of spreading is negative, the liquid drop will not

spread but rest on the surface and form a definite wetting
contact angle.
 Immersional wetting
γs
γl Immersional wetting process
occurs, for example, when a
γsl plate of a solid is in a reversible
Fig.13. A scheme of process dipped into a liquid
immersional wetting normally to the liquid surface
process.
(Fig.13). Then, because the
The work of immersion liquid surface tension vector is
equals: normal to the solid surface it
does not contribute to the work
WI = γs – γsl (11) of immersion WI.
 Adhesional wetting
This is a process in which two unit areas are contacted in
reversible way thus forming the interface of solid/liquid or
liquid/liquid.
The value of work of adhesion in solid/ liquid system
equals:

WA = γs + γl – γsl (12)

Fig.14.An illustration of the adhesion wetting process between phases A and B

(from A.W. Adamson and A.P. Gast, Physical Chemistry of Surfaces).
If the process deals with the same phase (e.g. a column of
liquid) this work is equal to the work of cohesion WC, and
Eq.(12) reduces to Eq. (13).

WC = 2γl (13)

Comparison of the work of wetting in

particular processes : WS = (γs – γsl) – γl
It is clearly seen that:: WI = (γs – γsl)

Ws < WI < WA WA = (γs– γsl) + γl

Then: WS = (γs – γsl) – γl = WA {= (γs– γsl) + γl} – 2γl

WS = WA – WC (14)
Wetting of solid surface in adsorption process

During the adsorption process the solid surface free energy is

changed depending on the nature of adsorbing molecules.
This change is termed as the surface pressure (or film
pressure) π. In general it may be negative or positive.

The resulting work of adsorption process may correspond

to the work of spreading, immersional or even
adhesional wetting.

The shape of adsorption isotherm depends on whether the

liquid wets the surface completely or only partially, i.e.
whether the liquid forms definite contact angle or not.
For complete wetting the adsorption isotherm at p/po = 1
approaches to infinity and macroscopically thick layer is
formed.
In case of partial wetting the adsorbed amount is finite, and
the film thickness is about few monolayers. Here,
metastable and unstable regions may appear in the super-
saturation regions and condensation of the vapor may also
occur. Hence in a closed system at p/po = 1 the adsorbed
film may be in equilibrium with the liquid droplet.

Using the Gibbs adsorption equation thermodynamic

relationship between vapor adsorption and wetting can be
derived, assuming ideal behavior of the vapor.
 Γ
π sv = RT ∫Γ =o Γd ln(p / p o ) (15)

Where: πsv = γs – γsv is the adsorbed film pressure.

The film pressure equals to the difference between the

surface free energy of bare solid γs, and the solid surface free
energy with adsorbed film γsv. The adsorbed amount is
determined by the surface excess Γ.
 Wetting contact angle

Fig.15. Schematic representation of liquid drop/solid/gas system showing

contact angle θ.
The equilibrium system corresponds to partial spreading wetting.

Tomas Young described this system in 1805 and formulated

(only in words) the relationship, which is now known as the
Young equation.

γs = γlcosθ + γsl (16)

 The original text “An Essay on the Cohesion of Fluids”
published in Phil. Trans. Roy. Soc. in 1805 year by Young:
“we may therefore inquire into conditions of equilibrium of the three forces
acting on the angular particles, one in the direction of the surface of the
fluid only, a second in that of the common surface of the solid and fluid,
and the third in that of the exposed surface of the solid. Now supposing
the angle of the fluid to be obtuse, the whole superficial cohesion of the
fluid being represented by the radius, the part of which acts in the direction
of the surface of the solid will be proportional to the cosine of the
inclination; and this force, added to the force of the solid, will be equal to
the force of the common surface of the solid and fluid, or to the difference
of their forces… And the same result follows when the angle of the fluid is
acute.”
From Eq.(16) one would expect that for an insoluble in the
liquid flat solid surface only one contact angle value should
describe the liquid drop/solid/gas (vapor) system. Such
contact angle is termed as the ‘equilibrium contact angle’
θe, or ‘Young’s contact angle’.
If the solid surface behind the liquid droplet is bare, the contact
angle is termed as the ‘advancing contact angle’ θa.
Practically in all systems when the three-phase line has
retreated, for example by sucking a volume of the liquid drop,
the contact angle at this new equilibrium is smaller, and it is
termed the ‘receding contact angle’ θr.
The equilibrium contact angle value lies somewhere between
the advancing and receding contact angle values.

θa > θe < θr

The difference between the advancing and receding contact

angles is named ‘contact angle hysteresis’, H.

H = θa - θr
 Contact angle and the work of adhesion

In the Young equation: γs = γlcosθ + γsl

contact angle θ
liquid surface tension γl
} - measurable
solid surface free energy γs
interfacial solid/liquid free energy γsl } - unknown
However, the work of adhesion can be determined.

γs = γlcosθ + γsl ⇒ γsl = γs – γlcosθ

WA = γs + γl – γsl = γs + γl – γs + γlcosθ

(17)
WA = γl (1+ cosθ)
Having determined WA then work of spreading WS can be
calculated for such ‘contact angle system’.
WS = WA – WC = WA - 2γl = γl (1+ cosθ) - 2γl

WA = γl (1+ cosθ) WS = γl (cosθ -1)

However, still the surface free energy of solids cannot be

determined in this way.
This is possible if the work of adhesion is formulated in such a
way that it involves the solid surface free energy. This problem
is not fully solved yet. Intermolecular forces have to be
considered, which are: dispersion, dipole-dipole, π-electrons,
hydrogen bonding, or generally Lewis acid-base, i.e.
electron-donor and electron-acceptor.
F.M. Fowkes in 1960 took into account that between paraffin
hydrocarbon molecules only dispersion forces interacted and
assumed that the same was true for n-alkane/water molecules
interactions. Applying the Berthelot’s rule (u11u22)1/2 = u12 for the
interfacial dispersion interactions between two phases Fowkes
expressed the work of adhesion for hydrocarbon/water as:

WA = 2(γHd γWd)1/2 (18)

Because: WA = γH + γW – γHW

Hence: γHW = γH + γW – 2(γHd γWd)1/2 (19)

Where: H - hydrocarbon (n-alkane); W - water

- For n-alkanes: γH = γHd
- The interfacial tension n-alkane/water γHW can be measured.
- Fowkes determined in this way contribution of the dispersion
interactions to water surface tension, i.e. the dispersion
component of water surface tension γWd = 21.8 ± 0.7 mN/m.
- The total surface tension of water equals 72.8 mN/m at 20oC.
- The difference between the two γWn = 51 mN/m results from
the presence of nondispersion forces originating from water
molecules.
- These nondispersion forces are dipole-dipole and hydrogen
bonding.
Fowkes (and later others) considered that surface tension
(surface free energy) of a liquid or solid can be expressed as a
sum of several components, of which not necessarily all are
present at a surface.
d p i h π da e
γ=γ +γ +γ +γ +γ +γ +γ (20)

The superscripts mean interactions: d – dispersion, p – dipole-

dipole, i – dipole-induced dipole, h – hydrogen bonding, π – π-
electrons, da – donor-acceptor, e – electrostatic.
 General problem of surface free energy
formulation and determination
Recently Lyklema has revisited fundamental aspects of
phenomenological thermodynamics of surface excess energy
and entropy in relation to the surface and interfacial tensions of
liquids and arrived at some important conclusions.

According to Lyklema the work of adhesion WA = 2(γ1d γ2d)1/2

expressed by geometric mean of dispersion interactions has a
weak thermodynamic background, because it is formulated like
the energy u12 (Berthelot’s rule (u11u22)1/2 = u12) .
He states that thermodynamic quantities, here the surface
tensions, are mixed up with mechanical ones, i.e. internal energy.
The description of thermodynamic parameters involves
temperature, while the mechanical quantity does not. The term
(γ1d γ2d)1/2 is formulated as temperature independent, because the
Helmholtz energy (U-TS) is actually considered as the energy
(U), which is obviously not true.

However, for many systems γHW = γH + γW – 2(γHd γWd)1/2 well

describes wetting and adhesion processes in conjunction with
contact angles.

Lyklema considers two reasons for such behavior:

1 - the same type of approximation made for two coupled
phenomena, i.e. surface tension and contact angle, which
may lead to compensation of the errors and thus pointing to
the consistency,
2 - for most liquids the surface entropy is a generic property
(i.e. remains practically the same within the range of
experimental errors).and combination of different pair of
liquids give the same error.

His final statement is that there is a reason to continue using

equation the equation, but the data should be reconsidered.
However, over-interpretation of this equation, by adding extra
terms (like acid-base interactions), or combination of γ values
with contact angle data, by introducing an additional empirical
terms to obtain solid-liquid interfacial tensions is not justified.

A correct equation describing the interfacial tension γ12 should

be following:

γ12 = γ1+ γ2 – 2(U1,aσ,d U2,aσ,d)1/2 + T∆adhSaσ (21)

From Eq.(21) it would result that for water the dispersion

component of its surface tension, γwd = 21.8 mN/m (as
determined by Fowkes) is probably underestimated by ca. 8%.
 Other approaches to the surface free energy
determination

Despite Lyklema’s criticizm there are several different

equations in which geometric mean of polar (dipole-dipole) or
hydrogen bonds interactions have been added. They are still
used sometimes. Often an equation like (21) was used in
which all non-dispersion interactions (polar) γp were
expressed by the geometric mean.

γ12 = γ1 + γ2 – 2(γ1d γ2d)1/2 -2(γ1p γ2p)1/2 (21a)

In the late 80th of past century van Oss, Good and Chaudhury
introduced a new formulation of the surface and interfacial free
energy.
γi = γiLW + γiAB = γiLW +2(γi– γi+)1/2 (22)

γiLW – apolar Lifshitz-van der Waals component a phase ‘i ‘

γiAB - polar Lewis acid-base interactions (hydrogen bonding).
γi– - electron-donor
γi+ - electron-acceptor
}– mostly hydrogen bonding

Note that the polar interactions are expressed by the geometric

mean.
 H γ1– Fig.16. A scheme of hydrogen bonding
•x ••
• • • • γ1+ between two water molecules. The ‘free’
• O•
−H O H
x x electron-donor γ1– and electron-acceptor
•x ••
γ1+ interactions are also shown.
H
Interfacial solid/liquid free energy is derived basing on Eq.(22) .

γSL = γS + γ L − WA = γS + γ L − 2 (
γS γ L )
LW LW 1 / 2
(
−2 )
+ − 1/ 2
γS γ L −2 ( )
− + 1/ 2
γS γ L (24)

And the work of adhesion reads:

WA = γl (1+ cosθ) =2 (LW LW 1 / 2

γS γ L ) +2 (+ − 1/ 2
γS γ L ) +2 ( )
− + 1/ 2
γS γ L (25)

If one has measured contact angles of three liquids, whose

surface tension components are known, then three equations
of type (25) can be solved simultaneously and the surface free
energy components of the solid can be determined.
Van Oss et al. assumed for water at room temperature equal
electron-donor and electron-acceptor interactions.
Because: γwAB = 2(γw– γw+)1/2 = 51 mN/m,
Hence: γ1– = γ1+ = 25.5 mN/m.
Basing on this value the relative values for other liquids have
been determined.
Table 1. Surface tension and its components, in mN/m, of some liquids, usually used as
the probe liquids for solid surface free energy determination.
Liquid γlTOT γlLW γl+ γl-
Diiodomethane 50.8 50.8 0 (0.4-0.7) 0
α-Bromonaphthalene 44.4 43.6 0.4 0.4
Decane 23.8 23.8 0 0
Water 72.8 21.8 25.5 25.5
Formamide 58.0 39.0 2.28 39.0
Ethylene glycol 48.0 29.0 1.92 47.0
Glycerol 64.0 34.0 3.92 57.4
Dimethylsulfoxide 44 44 0 30
 In the literature there are several other ‘scales’ of the
liquid tension components, more or less justified, which are
based on the assumption that for water γ1– ≠ γ1+.
 In general, this approach is controversial one.
It always gives large γ1– and small γ1+ values.
The authors explain it as a generic nature of surfaces.
Thus determined solid surface free energy components
depend to some extent on the kind of three probe liquids used.
 Such values should be considered as relative ones, but they
are useful to observe changes of the surface free energy.
To obtain reasonable and comparable results, one of the three
probe liquids should be apolar, e.g. diiodomethane, and the two
polar, usually water and formamide, or ethylene glycol.
 Contact angle hysteresis

The difference between advancing

contact angle θa and receding con-
tact angle θr is termed ‘contact

Fig.17. Illustration of advancing and

angle hysteresis.
receding contact angle measurements H = θa - θr

• The hysteresis was explained (and still it is) by roughness of real

surfaces and/or their chemical heterogeneity.
• Later it appeared that even on molecularly flat surfaces and on
self-assembled monolayer the hysteresis also appears.
• This author considered that contact angle hysteresis may also
result from the liquid film left behind the droplet during retreat of
its three-phase contact line.
Basing on this assumption an equation for calculation of total
surface free energy of a solid from three measurable parame-
ters, i.e. advancing and receding contact angles and the
liquid surface tension, has been derived.
Using the Young equation it can be written:

γs = γsl + γl cosθa (16)

γsf = γsl + γl cosθr (26)

Where γsf is free energy of the solid surface on which the liquid
film is present.
γsf = γs + π
Combining Eqs.(16) and (26):

π = γl (cosθr – cosθa) (27)

 The work of adhesion for both advancing (A) and receding
(R) modes can be expressed:

WAA = γl (1+ cosθa) (28)

WAR = γl (1+cosθr) (29)

Hence: WAR – WAA = γl (cosθr - cosθa) = π (30)

The work of adhesion can also be expressed with a help of so

called Good’s parameter:

WAA = 2Φ γ s γ l (31)

WAR = 2Φ γ sf γ l (32)
Taking ratio of the works of adhesion and the relationships
expressed by Eqs.(27)-(29) one obtains.

(1 + cos θa ) 2
γ stot = γ l (cos θr − cos θa ) (34)
2 2
(1 + cos θr ) − (1 + cos θa )

2
γ (1 + cos θ )
Or: γ stot = l a (35)
(2 + cos θr + cos θa )

In Table 2 and 3 are shown the surface free energy values of

glass surface determined from van Oss et al.’s and hysteresis
appro-aches . The average values from both methods agree
very well, and standard deviation from the contact angle
hysteresis is even less than from the components.
 Table 2. Total surface fee energy of the glass surface calculated from Eq.35.
Liquid surface Adv. contact angle Rec. contact angle Total surface free
Liquid tension, mN/m θa , deg θr, deg. energy, mJ/m2
Water 72.8 42.14 ± 3.25 37.40 ± 2.54 62.4
Glycerol 64 42.36 ± 1.46 36.50 ± 0 54.6
Formamide 58 36.94 ± 2.23 33.33 ± 2.38 51.7
Diiodomethane 50.8 48.13 ± 0.74 34.37 ± 0.74 40.4
Ethylene glycol 48 31.83 ± 2.48 26.67 ± 2.05 43.9
Average: from the components 50.9 ± 9.1 mJ/m2 (Table 3) 50.6 ± 7.8

Table 3. Total surface free energy and its components (mJ/m2) of glass calculated
from Eq.(25), using θa, and surface tension of probe liquids listed in Table 1, in mJ/m2.
Probe Liquid Triads
Energy
D-W-F D-W-G D-W-EG W- G – F W-F-EG
γsLW 35.3 ± 0.4 35.3 ± 0.4 35.3 ± 0.4 23.4 ± 1.7 58.3 ± 1.4
γs+ 0.85 ± 0.04 1.57 ± 0.06 0.23 ± 0.01 4.2 ± 0.52 0.63 ± 0.6
γs- 37.6 ± 2.7 33.7 ± 3.1 43.3 ± 3.1 36.4 ± 2.8 39.5 ± 2.9
γstot 46.6 ± 1.1 49.9 ± 1.3 41.6 ± 0.7 48.1 ± 4.3 68.3 ± 2.3
Av. γstot 50.9 ± 9.1 mJ/m2
Key: D- diiodomethane, W –water, F – formamide, G –glycerol, EG – ethylene glycol
Other examples of the hysteresis approach application for surface
free energy determination (Eq.35) show Figs.18 and 19.

80
70
60
50
Silicon grafted with (CH3)3Si-////
1. After 6-min, γstot = 33.5
2

mJ/m2 , 54 % reduction
Surface free energy, γs , mJ/m

1
34
tot

32 2. After 1-2.5 h, γstot = 29

2
mJ/m2, 60% reduction
30
3
28 3. After 48 h - 196 h (8
26
days), γstot = 24.5 mJ/m2,
66% reduction
24
0 1 2 3 4 5 24 48 72 96 120 144 168 192
Reaction time, h

Fig. 18. Total surface free energy, γstot , of silicon surface grafted at room
temperature with (CH3)3Si– in toluene solution depending on the reaction time as
determined form water contact angle hysteresis (A.Y. Fadeev, T.J. McCarthy,
Langmuir, 15 (1999) 375).
 Wettability of trialkylchloro–, dialkyldichloro– and
alkyltrichloro– silane layers
40
Silicon grafted with the silanes 1. For methylsilanes monolayers
38
- R(CH3)2SiCl
γstot in mJ/m2 :
2
Surface free energy, γs , mJ/m

36
- R CH3 SiCl2 (CH3)3Si– 23
34 (CH3)2Si= 33
- RSiCl3
tot

32 CH3Si≡ 39
30
28 2. For R = –C6H11 to –C18H35
26 γstot practically the same.
24 These alkyl chains shield the
22 silicon surface to similar degree.
20 Methylene groups determine
0 2 4 6 8 10 12 14 16 18 20
the free energy giving 22–24
Number of carbon atoms in R chain
mJ/m2.

Fig. 19. Total surface free energy, γstot , of the silyl layers versus the number
of carbon atoms in the alkyl chain (R) determined from water contact angle
hysteresis (A.Y. Fadeev and T. McCarthy, Langmuir, 16,7268(2000)).
.
 1 ///-Si

45 2 ///-Si
As determined from water contact angle hysteresis
3 ///-Si
40

4 ///-Si
2
Surface free energy, mJ/m

35
5 ///-Si

30 6 ///-Si

25
7 ///-Si

8 ///-Si
20
9 ///-Si

15
10 ///-Si

10
1 2 3 4 5 6 7 8 9 10 11 12 11
///-Si C18H37
Type of sylane monolayer
12 ///-Si C8H17

From: A.Y. Fadaeev and T.J. McCarthy, Langmuir, 15, 3759 (1999), Tabl.6
 Superhydrophobic surfaces
If one takes water contact angle as a measure of surface
hydrophobicity, then ‘Superhydrophobic’ means that the
surface becomes abnormally more hydrophobic. For example,
on a hydrophobic surface water contact angle is, say, 100-120o,
so on the superhydrophobic surface the contact angle increases
up to 150o and more. This is possible if micro- or nano- size
roughness are produced on the surface. Therefore, a water
droplet rests on it like on a brash, and in fact, the droplet contact
with the surface is much smaller than on the same flat surface.

There are several natural superhydrophobic surfaces, and the

most known is that of lotus leaf on which θ equals up to 170o.
 A B

Fig.19. A). A water droplet on a lotus leaf. (From: http://www.botanik. unibonn.de/

system/lotus/en/ prinzip.html.html). B) SEM-image of lotus leaf. The micro structural
epidermal cells are covered with nanoscopic wax crystals. Bar: 20 µm. (from W.
Barthlott and C. Neinhuis, Planta 202, 1(1997).

The air trapped between the wax roughness on the leaf

surface minimizes the contact area of the water droplet. For
suchs system description, instead the Young equation often
Wenzel or Cassie equation is applied.
 Young equation
γs – γsl = γlcosθ

Wenzel equation
r>1 r (γs – γsl) cosθ’= r cosθ

real ⋅ surface ⋅ area

r=
apparent ⋅ surface ⋅ area

Cassie equation

f cosθ’= f cosθ + (1-f) cos180o =

f cosθ’= f (1+ cosθ) –1

Fig.20. Illustration of Young, Wenzel and f = area fraction of solid surface

Cassie equations. From A. Nakajima et al.,
Monatshefte fur Chemie, 132, 31 (2001)
Wenzel - roughness factor r > 1 the surface
roughness increases apparent hydrophobicity of a hydropho-
bic surface, but also hydrophilicity of a hydrophilic surface.

Cassie - contact angle θ’ – the surface consists of solid and air

The solid fraction under the droplet is described by the factor f.
On the fraction occupied by air the contact angle is180o.

For superhydrophobic surfaces the apparent surface free

energy can be calculated from contact angle hysteresis Such
values delivers interesting information about properties of the
surface. Some examples of model superhydrophobic surfaces,
produced by photolithography method, are shown in Figs.21
and 22
 30
25
1

Surface free energy, mJ/m2

20
15 2
10
3
5

0,4
0,3
1- ODMCS
0,2 2- DMDCS
0,1 3- FDDCS

0,0
0 20 40 60 80 100 120
Size of square post, µm
Fig.2. SEM images of surface
containing 8 µm × 8 µm Fig.22. Changes in apparent surface
square posts with different free energy of silicon wafer roughed
spacings. surfaces treated with dimethyl-
(DMDCS), n-octyl- (ODMCS), or
heptadecafluoro-1,1,2,2-tetrahydro-
decyl- (FDDCS) dimethylchlorosilane.
From: D. Öner and T.J. McCarthy, Langmuir ,16 (2000) 7777.
For the surfaces shown in Figs.21and 22:
The advancing water contact angles were: θa = 166-173o,

The receding contact angles were: θr = 131-138o.

The free energy of smooth silicone surfaces covered with the

silane depending on its kind was: 16-26 mJ/m2.

The apparent free energy of the rough surfaces was less than
0.2 mJ/m2.
Up to ca. 40µm of the square post size the energy increased
only a little.

If the post size was larger than 120 µm the surfaces behaved
as flat ones.
 x
0.18 ODMCS surface
1- 16x16 µm x
0.16 2- 32x32 µm
2x
2

0.14
Surface free energy, mJ/m

0.12

0.10

0.08
2
0.06

0.04

0.02 1

0.00
20 40 60 80 100 120 140
Post height, µm
Post Advancin Receding Advancin Receding
height g contact contact g contact contact
angle, θa, angle, θr, angle, θa, angle, θr,
µm deg deg deg deg
20 173 138 170 137

40 174 134 170 132

60 169 138 168 139

From: D. Öner and T.J.
McCarthy, Langmuir 16 80 169 136 167 134

(2000) 7777 100 173 138 173 134

140 168 136 166 131

 Examples of practical application of solid
surface wettability
One of very important applications of wetting process is flotation
method of mineral ores enrichment.
It is based on the differences in wettability of the mineral grains
and those of gangue.
In this case the mineral surface is needed to be hydrophobic.
From the work of spreading, WS = WA – WC = γl (cosθ -1), it
results that Ws > 0 (hydrophobic surface), if a water droplet
forms defined contact angle on the mineral grain surface.
Generally, mineral surfaces are rather hydrophilic. Therefore to
convert them into hydrophobic ones the use of appropriate
surfactant is needed.
It adsorbs from the solution of flotation pulp onto the mineral
surface with its polar head to the surface and the hydrophobic
tail directed toward the liquid phase, thus lowering the solid
surface free energy γs, as well as the interfacial mineral-water
free energy γsl.
In this way the surfactant can reverse the work of spreading
from positive to negative. The surfactants used in the flotation
process are called ‘collectors’.

Fig.23 shows how flotation recovery of several minerals

depends on the value of the work of spreading.
Fig.24 presents flotation activity of barite samples precovered
with different amounts of anionic sodium dodecyl sulfate (SDS)
or cationic tetradecyl ammonium chloride surfactant.
 Volume of nitrogen, cm3
110 10
Marble/0.62 TDACl
100 1.06 Sulfur
20
0.53 Barite/1.0 SDS
90
30
0.265
80 Quartz/DDACl
40
70 Barite/0.4 SDS 80
Recovery, %

60

Recovery, %
60
1 2
50 Coal 33
40
40 Barite/1.0 TDACl
Marble 20
30
0
20 Barite/0.25 TDACl 0 1 2 3 4
Chalcocite
10 Barite Quartz Statistical monolayers: SDS - 1 or TDACl - 2
Quartz/1.0 SDS
0
-120 -100 -80 -60 -40 -20 0 20 40 60 80 100 120

Work of water spreading, WS, mJ/m

2 Fig.24. Dependence of the flotation
recovery of barite on the number of
Fig.23. Dependence of the flotation statistical monolayers of SDS or
recovery of mineral on the value of TDACl (upper part shows the nitrogen
work of spreading of water. volumes needed for 100% flotation of
the sample).

Fig.24 - more effective is cationic TDACl than anionic SDS

collector. The complete flotation of the sample with TDACl is
achieved even below coverage of one calculated monolayer.
An example of the surface free energy changes of mineral as
a function of its surface coverage with a collector is shown in
Fig. 25 for apatite.

The decrease in its surface free energy due to the adsorption

of oleic acid is shown at different temperatures and pH
values.

The energy values were calculated from water contact angle

hysteresis.

The minimum energy of fluorite occurs at about monolayer

coverage of the surface, assuming vertical orientation of the
molecules.
 65
60
Apatite/Oleate pH=8, 20 C
o
55 o
pH=9.5, 20 C

2
Surface frre enrgy, mJ/m
50 o
pH=9.5, 65 C
45
40
35
2
30 21.3 A /molec.

25 O
20
15 2
25A /molec.
10
0 1 2 3 4 5 6 7 8 9 10 11 12
2
Adsorption, µmol/m

J. Drelich et al, J. Colloid Interface Sci.,

202, 462-476 (1996)

Fig.25.Total surface free energy for apatite as a function of oleate

adsorption calculated at two different temperatures and pHs. The contact
angles data were from Y. Lu, J. Drelich and J.D. Miller, J. Colloid Interface
Sci. 202, 462 (1998). The arrow shows monolayer coverage suggested by
the authors (25 Å2/molec.), and the vertical dotted line shows the
monolayer coverage assuming 21.3 Å2/molec.
 Summary

 The presented examples show an important role of

wetting in everyday life and industrial processes.
 Understanding of wetting processes is based on the
knowledge of solid and liquid surface free energy.
 Knowing the energies and their components
prediction whether the solid surface will be wetted, and
to which extent, is possible.

Note: There are solids that occur only in a powdered state, e.g.: soils,
clays, pigments. For such solids real contact angle cannot be measured
directly. There are methods based on measurements of penetration rates
of a liquid into porous layer or column of the tested solid.
One more way of wetting