Prof. Dr.

Sérgio Duarte Brandi Text for class in Aalto University

1

4) THE SURFACE TENSION CONCEPT, SURFACE ENERGY AND FREE ENERGY SURFACE.
This chapter discusses the different terminologies and concepts related to the surface tension and
their equivalents, the mechanical and thermodynamic point of view.
After a historical overview related to the development of capillary action and surface tension, it is
important to know the conceptual differences that exist with some of the terms applied in this area
of expertise. Definitions will be shown that are not standardized and involving concepts used
sometimes erroneously or inaccurately. In the text, the concepts will be addressed in a historical
way. Thus, the mechanical approach will be presented, followed by thermodynamic approach the
surface tension to then compare the terms to each other.
The concept 'surface tension' is originated from an evolution of the concepts that led to the 'An
essay on the cohesion of fluids' of Young [15] and 'Sur l'action capillaire' Laplace [18]. With the
exception of Young's work, all other employed the concept of surface tension in a generic way, i.e.
there was particularization which currently exist, the surface tension between each different system
interfaces, such as solid / vapor interface liquid / vapor and solid / liquid, for example. The focus, it
seems, was in liquid interface / vapor, although the surface tension term has, in these cases, a purely
mechanical connotation [22, 32, 34, 75]. In other words, the interface can be considered like a child's
party rubber bladder, which is curved as its internal pressure increases, not changing the number of
chemical species that move to the surface. The curvature of the interface appears to balance the
difference between the internal pressure and the external pressure of the bladder. The equations
governing this curvature, and any other surface deformable curve, were presented in Chapter 3 and
are the equations (3.9) and / or (3.10).

4.1) DIFFERENT UNITS FOR SURFACE TENSION.

Surface tension is a quantity that can be dimensionally expressed by "energy per area unit
'or' force per unit length 'which, though not appear are identical units. Thus, the surface tension is
measured in SI units, J/m2 or N/m, depending on the phenomenon of approach. Let's look at two
different situations, but involving the expansion of the area of an interface.

Consider a liquid film on a wire frame with a movable side, as shown in Figure 4.1 [76].

F
Prof. Dr. Sérgio Duarte Brandi Text for class in Aalto University
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x
Figure 4.1 Liquid film in a frame with a movable side, being stretched by a force F [76].

Assuming that the film is stretched by a force F, counterbalanced by a force F per unit length
'l', called ''. If there is an increase dx in the extension of the film and, consequently, in the area A,
the work (DW) to this expansion occurs is given by equation (4.1):

dW   .l.dx   .dA (4.1)

The work done per unit area is equivalent to the surface tension '' of the liquid film.
Consider a soap bubble of radius 'r' which undergoes expansion 'dr', as shown in Figure 4.2.
In the case of soap bubble exists a pressure difference p through the film, which is counterbalanced
by the surface tension of the film (), which attempts to contract the bubble. In this case one obtains
the equation (4.2):

2 (4.2)
Δp.4. .r 2dr  8. .r. .dr  Δp 
r

Equation (4.2) has a very important result. The smaller the radius of the bubble, the greater
its pressure difference for the same , that is higher internal pressure compared with the outside
pressure.
Prof. Dr. Sérgio Duarte Brandi Text for class in Aalto University
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Figure 4.2 - Expansion of a soap bubble of initial radius 'r' [76].

As previously stated, according to the approach of the case, the surface tension can be expressed
by a dimensional unit. Thus, if the approach to the problem is the film being stretched by a force,
formulated by equation (3.17), the surface tension is measured in unit of energy per area (J / m2 or
erg / cm2). On the other hand, if the approach is the expansion of the soap bubble area, shown by
equation (3.18), the surface tension is measured in unit of force per unit of length (N/m or mN/m).

4.2) MECHANIC CONCEPT OF SURFACE TENSION: THE LAPLACE'S EQUATION. .

Figure 4.3 shows an infinitesimal section of a surface, so that the radii of curvature R1 and R2, which
are perpendicular to each other are constant. Assuming that the pressure is varied from p 'in the
z direction and, consequently, the sectional area is increased from `dA`.

Figure 4.3 - Condition for mechanical equilibrium of a surface arbitrary curve [76].

Mathematically, the infinitesimal increase in area is given by:

dA  (x  dx ).(y  dy )  x.dy  y.dx (4.3)
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The work performed to expand the surface (S) is given by:

W   .dA   .( x.dy  y.dx ) (4.4)

As the expansion was caused by an increase in pressure, the work surface is given by:
W  p.x.y.dz (4.5)

In figure 4.3 for similarity of triangles we have:

axis x:

x  dx x x.dz (4.6)
  R1.x  R1.dx  R1.x  x.dz  dx 
R1  dz R1 R1

axis y:

y  dy y y.dz (4.7)
  R2.y  R2.dy  R2.y  y.dz  dy 
R2  dz R2 R2

As the system is in mechanical equilibrium, the two expressions of the work can be matched:

p.x.y.dz   .( xdy  ydx ) (4.8)

Substituting expressions for `dx` and `dy` in the above equation we have:
y.dz x.dz (4.9)
p.x.y.dz   .( x y dx )
R2 R1

After simplifications, we obtain the Laplace equation:

1 1 (4.10)
p   .(  )
R2 R1

The mathematical expressions for radii of curvature are:

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d 2y (4.11)
1 dx 2
 3 /2
R1  2


1   dy 
 
  dx  

and
dy (4.12)
1 dx
 1/2
R2   dy  
2

x 1   
  dx  


4.3) THERMODYNAMIC CONCEPT.

To relate the mechanical concept of surface tension with thermodynamic properties is necessary
that the surface used for thermodynamic considerations coincide with the interface that is set
mechanically. Only obeying this requirement is that you can relate a purely mechanical magnitude
with thermodynamic properties.
This item will be deduction using the concept of the first interface and Gibbs.

4.3.1) SURFACE FREE ENERGY.

Some thermodynamics definitions:

F= U - TS

G= H-TS

H= U + pV

U= TS-pV +iµiNi for a multicomponent system

µi = chemical potential = `partial derivative of free energy with respect to the amount of species`

µi = (G/Ni)p,T,Nj≠1 = (F/Ni)V,T,Nj≠1
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G = F + pV

Helmholtz and Gibbs free energy are thermodynamics functions that can be used to study the
concept of surface tension. For a capillary system, the mechanical work may be performed or a
change in volume or a change of the interface area. Thus, employing the Helmholtz free energy (F)
for this capillary system is obtained:

dF  SdT  pdV  dA   i dni  C1dc1  C2dc2 (4.13)

i

where: S = entropy, T = temperature; p = pressure; V = volume;  = surface tension; A = area; i =

thermodynamic potential; ni = number of moles; C = constant; ci = curvature (reciprocal of the
radius).

Assuming that the system is in temperature, volume and number of moles constant and its surface
is flat or of a spherical cap shape, deriving 'F' to the area 'A' on the surface are obtained:

 F  (4.14)
  
 A  T , V ,n

In the case of using the Gibbs free energy (G) in place of the Helmholtz free energy (F), equation
(4.13) becomes:

dG  SdT  Vdp  dA   i dni  C1dc1  C 2 dc2 (4.15)

i

Employing the same assumptions, but replacing the volume constant by the constant pressure is
obtained:

 G  (4.16)
  
 A  T ,p ,n

The Gibbs interface concept applied on a flat interface or spherical cap.

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If employed the concept of Gibbs interface presented in chapter 3, equation (4.13) becomes:

dFexc  S exc dT  dA   iexc dniexc  C1dc1  C 2 dc2 (4.17)

i

Assuming the temperature, the volume and number of moles contained in addition to the flat
interface or spherical cap shape, deriving from 'F exc' to the area 'A' on the surface are obtained:

 F exc  (4.18)
   
 A  T ,n

The same procedure can be done to Gexc, assuming temperature, pressure, number of moles
constant and using equation (4.15). Comparing all results comes to:

 F   F exc   G   G exc  (4.19)

          
 A  T , V ,n  A  A   A 
 T ,n T ,p,n   T ,n

The equalities shown in (4.19) represents the thermodynamic definition of surface tension. It is
important to note that the surface tension is not equal to surface free energy per unit area.
According to Gibbs, the surface tension is equal to the surface energy per unit area only if the
adsorption surface is null [27].
The equivalence between the surface tension and the surface free energy is best seen by integrating
equation (4.17), assuming constant temperature and flat surface or spherical cap shape, you obtain:

F exc (4.20)
F exc  A   iexc niexc or     i iexc or   f s   i iexc
i A i i

where: fs = Fexc / A = surface free energy; n iexc = number of moles of phase "i" per unit area.

exc exc
As  i is function of ni may seem that the validity of the equations presented as (4.20) is limited.
exc
If ni increases with increasing surface area, the molar fraction of 'i' will remain constant, the
numbers of moles of other components will increase proportionally [75]. Furthermore, in the case
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of thermodynamic equilibrium, all phases present in the system of interest are equal. Thus, there is
no limitation with respect to equations (4.20).

5) WETTING AND SPREADING.

This section will be highly wetting and spreading of a liquid on a solid. The wetness is the equilibrium
condition that affects a liquid on a solid, while the spreading kinetics is related to this phenomenon.
According to Eustathopoulos [82] wetting of metals or ceramics is divided into two types: non-
reactive and reactive. In the first case, the mass transport through the surfaces is very limited, very
little influence on surface tensions involved. In the second case occurs some kind of reaction at the
interface, is the formation of a new phase is the partial dissolution of the solid in the liquid.
The wetting can also be classified as spontaneous or forced. In spontaneous wetting drop wets and
spreads without the action of any external agent. In wetting forced the liquid spreads without water,
since a force acts on the drop. This force is applied by relative movement or a phase with respect to
each other, or by gravity for liquids with higher density and mass.

5.1) WETTING.

Wetting to occur there must be an affinity between the liquid and the solid, whether the origin is
physical, chemical or physicochemical [84]. If there is no type of interaction, the liquid will be
mechanically adhered to the roughness and porosity of the surface, after its solidification, what we
called `mechanical interlocking`.
The mechanical interaction is much less resistant than other types when the system is subjected to
external efforts. A drop of liquid wetting a solid substrate has three interfaces: solid / vapor, solid /
liquid and liquid / vapor with their surface tensions. Figure 5.1 shows this arrangement. It is noted
in Figure 5.1 the presence of three surface tensions: SV (solid surface tension / vapor), SL (solid /
liquid surface tension) and LV (surface liquid / vapor pressure), and the contact angle .

LV

SV 
SL
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Figure 5.1 - Scheme of surface tensions caused by the presence of a liquid to a solid.

It is said that the liquid wets the solid when  <90. In this case there is some kind of interaction
between the liquid and the solid. If > 90 °, the liquid does not wet the solid. In other words, there
is no type of interaction, except mechanics. It was from a design similar to that which has been
proposed Young's equation, originally present in the item 3 of this text, and reproduced below:
 SV   SL (3.7)
cos  
 LV

Analyzing the Young equation comes to the conclusion that only SV acts to favor the reduction of
the contact angle. The other two surface tensions (LV and SL) act to prevent the reduction of the
contact angle. Figure 5.2 illustrates this. In other words:
(5.1)
 SV   SL   LV cos 

when  < 90º

and
(5.2)
 SV   SL   LV cos 

when  > 90º

(a)

(a) (b)

Figure 5.2 - Condition for wetting (a) and non-wetting (b) of a liquid over a solid.

Looking in greater detail in Figure 5.1, Eustathopoulos et alli [82] divided wetting of a solid
by a liquid into two types: primary and secondary. The primary is associated with the main direction
of wetting, where the solid / vapor interface is replaced by solid / liquid interface. The secondary
wetting is slower and occurs after the primary wetting, at grain boundaries in contact with the liquid
in the contact line.
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Secondary
wetting

L
S 

S
Primary
L
wetting

Grain boundary
wetting

Figure 5.3 - Wetting primary and secondary wetting according to I Stathopoulos [82].

In this chapter will basically treated the primary wetting.

5.1.1) DEDUCTION FROM THE THERMODYNAMICS, THE PRIMARY WETTING YOUNG EQUATION.

It is very usual find the deduction of Young's equation from the resulting components of the 'vectors'
in the axis x. It can also be deduced by thermodynamics [84, 85], using equation (4.17) to 'F', and
assuming that the temperature is constant and gravitational attraction is negligible, it has:

dFexc  γdA   μ iexcdn iexc  C1dc1  C2dc2 (5.4)

i

In the case of a drop with a spherical cap geometry, d(c1  c 2 )  0 , and applying the equation (5.4)
in Figure 5.2:

dFexc  γSVdASV  γSLdASL  γLVdALV  μexc dnSV

exc

 dnSL
exc
 dn exc
LV  μ 
exc

dnSexc  dn exc
L  dn V
exc
 (5.5)

Assuming that the mass of the system is constant:

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dFexc  γSVdASV  γSLdASL  γ LV dALV (5.6)

Geometrically dASL = - dASV and the drop in the form of spherical cap dALV = dASL.cos. Substituting
these expressions in equation (5.6) we have:
dF exc  ( SV   SL   LV cos  )dASL (5.7)

In thermodynamic equilibrium conditions, the variation of the Helmholtz free energy should be
minimal with respect to the solid / liquid area:

F exc (5.8)
 ( SV   SL   LV cos  )  0
ASL

Equation (5.8) is identical to Young's equation (equation 3.7). It is important to discuss some of the
assumptions in the deduction from the thermodynamics of Young's equation, which are as follows:
• thermodynamic equilibrium.
• Gibbs interface (the interface volume is negligible).
• constant temperature.
• only primary wetting (monocrystalline material).
• ideal interface (grain boundary, surface roughness, sharp edges and possible physical and chemical
changes).
• mass of the constant system.
• gravity action negligible (forced spreading).
• drop with spherical cap geometry.
• values of surface tension obtained far from the line of contact (applying the Poisson hypothesis
raised in 1831).
• there is no adsorption elements for interfaces ( iexc  0 ).

5.1.2) PHYSICO-CHEMICAL MODIFICATIONS IN THE INTERFACE.

With respect to the type of change that occurs at the interface during the wetting of a solid by a
liquid material, Okamoto [89] proposed a classification of ceramic-metal interfaces, but they may
be extended for all combinations of materials. He classifies interfaces into four types:
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• non-reactive interface and non-penetrating = is microscopically flat and is consistent or

inconsistent.
• penetrating Interface = is rough and materials interpenetrating in the interface.
• reactive interface = reaction layer, or the formation of an intermetallic phase or a dissolution
reaction, forming a solid solution.
• diffusive = Interface is rough, the interdiffusion of atoms or macromolecules in the interface, but
does not form reaction products.

In the case of brazing and welding mild interfaces are of the type 'reactive' in both the brazing metal
/ metal as the brazing metal / ceramic. In the case of welding or polymers junction interfaces are
generally of the type 'diffusive', may have a reactive component depending on the type of
modification in the material [90].
One way to ensure that the physico-chemical there is contact by the solubility of any component of
one phase in the other. For this purpose, a dissolution reaction should take place and, depending
on the Hume-Rothery rule for solubility of a component (A) in another component (B) is formed or
a solid solution or an intermetallic compound. Tunca and colleagues [91] proposed the following
expression for dissolving a solid metal in a liquid metal at a given temperature:

dC k m A SL (C s  C) (5.19)

dt VL

where:
C = Concentration of compound A dissolved in the liquid B at temperature T;
km = mass transfer coefficient;
ASL = area of the solid / liquid interface;
Cs = solubility in B at a given temperature T;
VL = volume of the liquid.

The change in the liquid concentration versus time is directly proportional to mass transport
coefficient, the area of the solid / liquid interface and the difference in the solubility test
temperature and inversely proportional to the volume of liquid.
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Equation (5.19) shows that if the wetness of a binary or multicomponent alloy, there will be a
variation in chemical composition of the liquid, forming a reaction at the interface and changing the
composition of the liquid to reach equilibrium chemical composition. In the wetting test, V L is
generally constant, but ASL increases with decrease in the contact angle. Likewise, the mass
transport phenomenon occurs in increasingly smaller. It is difficult for a binary or multicomponent
wet a solid without a change in the composition of the interface and the net, making the chances of
ideal surface and adsorption on the surface virtually zero unlikely.
Depending on the type of reaction that occurs in the solid / liquid interface, wetting and spreading
can be facilitated or completely prevented. Figure 5.12 shows the two conditions where there are
changes at interface [92].

(a)

(b)

Figure 5.12 - Contact Line Photography for Cu-Bi system to 280oC and Cu-Sn to 350oC [92].
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The wetting analysis based only on the phase diagram Cu-Bi system shows that the solubility of
bismuth on copper and copper bismuth in is greatly reduced. Even so, it forms a solid solution at the
interface, creating a contact angle close to 80 degrees. This fact is represented by the contact angle
bismuth copper. Furthermore, Cu-Sn system presents a greater solubility of tin in copper, besides
the formation to occur of different intermetallic phases, depending on system chemistry. These
features influence the final contact angle. Thus, the interaction between the elements that make up
the liquid and the solid also determine the wetting and spreading of a liquid on a solid.
The effect of chemical composition change can also cause an isothermal solidification of the liquid
which is filling the gap in the soft brazing or welding, interfering with the wetting and spreading of
liquid.
Depending on the interaction between the reaction products formed at the interface, the liquid /
solid area decreases with time, after reaching a maximum value, the dewetting occurring
phenomenon. This phenomenon is very important in many manufacturing processes, and in welding
soft for application in electronics [93] and is detailed in this section. The surface contamination or
change in composition of the fluid also cause the same effect [93].

5.1.3) SEGREGATION IN THE LIQUID / VAPOR INTERFACE ( iexc  0 ).

When a liquid metal wets the solid metal B is the solid part of dissolution. From this point the metal
becomes a dilute alloy B A. If the surface tension of B is smaller than that of the liquid at the same
temperature B surface segregate to the liquid / vapor. Thus, B modify the surface tension of the
pure. One way to theoretically calculate the change in surface tension and the concentration of
solute in the liquid surface / vapor is through the equation proposed by Buttler [94]. To use this
model uses it the ideal solution concept or regular solution. Figure 5.15 shows the change of the
surface tension with the Ag composition for the Cu-Ag system at temperature 1223 oC [84]. In this
case is shown the ideal solution and regular solution.
Analyzing figure 5.15 one can note that the silver segregates to liquid interface / vapor, depending
on its concentration in the alloy. Thus, it presents a surface tension gradient which induces
convection due to the Marangoni effect.
With this brief example we tried to show that, in fact, there is an excess of one of the alloying
elements to the surface, and that the hypothesis of no adsorption on the surface is hardly fulfilled.
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Liquid/vapor surface
tension (N/m) Ideal solution

Regular Solution

Ag molar fraction

Ag molar fraction at
liquid/vapor surface
Ideal solution

Regular Solution

Ag molar fraction

Figure 5.15 - In (a) theoretical calculation of the variation of the surface tension of liquid / vapor to
Cu-Ag system, the temperature 1223oC, depending on the molar fraction of silver; and (b)
calculation of the silver concentration in the surface as a function of the molar fraction of silver alloy
[84].

5.2) THE SPREADING.

The spreading is the transient phenomenon of a fixed volume of liquid with a solid until it reaches
the equilibrium contact angle (), which define, generally, a solid / liquid maximal area. Figure 5.16
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shows schematically the evolution of the format, the contact angles and solid / liquid interface from
a parallelepiped, until an equilibrium contact angle of 30 °.

Beginning

End

Figure 5.16 - Scheme spreading phenomenon starting with a solid in a parallelepiped format to
achieve equilibrium contact angle of 30o [85].

Spreading can have a thermodynamic approach [22, 32, 89, 94-97] or hydrodynamic [23, 89, 95, 98-
102] which will be described below, in a succinct manner.

5.2.1) THERMODYNAMIC APPROACH SPREADING.

The spreading coefficient (S) is defined by De Gennes [62] as:

S   SV   SL   LV (5.22)

Physically, the equation (5.22) shows that the work to consume the solid surface / vapor is equal to
the work done to create the solid surface / liquid and liquid / vapor. Substituting equation (5.22) in
(5.8), and assuming that cos = 1 (ideal wetting), we have:

 F  (5.23)
   S
 A SL  T,V

When the liquid wets a solid completely, there is a decrease in the Helmholtz free energy,
ie:

 F  (5.24)
  0
 A SL  T,V

Comparing equations (5.23) and (5245) note that, whenever there is wetting, spreading coefficient
will be positive.
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5.2.2) HYDRODYNAMIC APPROACH SPREADING.

The hydrodynamic approach has been widely used for very viscous fluids in non-metallic substrates.
The changes in the contact lines are classified into two categories [98]: spontaneous spreading and
forced spreading.
The spreading rate is determined by the balance of forces acting on the contact line. The equation
governing the wetting is determined by the continuity equation and balance the amount of
movement in a thin layer of a viscous liquid.
The continuity equation in the direction x and in a constant volume is given by:

(u)  (5.25)
 
x t
where:
 = density of the liquid;
or = liquid velocity in the direction 'x';
t = time.

The balance of the momentum in a cubic element in the direction x, is given by:

 (.u.u) (.u.v) (.u.w)    xx  yx  zx  P (.u) (5.26)

           gh  0
 x x x   x y z  x t

where:
 = density of the liquid;
u = velocity of the liquid in the direction 'x';
v = velocity of the liquid in the direction 'y';
w = liquid velocity in the direction 'z';
ii = shear stress in the direction 'ij';
P = spreading potential;
g = acceleration due to gravity;
h = drop height.
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Assuming that: the density of the fluid is constant, the system is steady, the flow is unidirectional,
the substrate is horizontal and the solid / liquid system is unreactive, equation (5.26) becomes:

   yx  zx  P (5.27)
  xx     0
 x y z  x

u
 (
Substituting the expression for shear stress ) in the three directions, and assuming that u
x
= u (z), we have:

 2u P (5.28)
  0
z 2 x
where:
 = viscosity.

By integrating twice in relation to 'z', and if (P / x) is constant, we obtain:

 1  P (5.29)
u    z 2  C1z  C 2
 2  x

To determine the integration constants C1 and C2 applies the boundary conditions: u z = 0 to z = vt

and h = the shear stress is zero. In this case, equation (5.29) becomes:

 1  P  hz  P (5.30)
u    z 2    z  v t
 2  x    x
where:
vt = contact line speed for the drop spreading.

Ruckenstein and Dunn [100] proposed that the speed of the contact during drop spreading line is
given by:

 D  P (5.31)
v t   S 
 nlkT  x
where:
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DS = surface diffusion coefficient;

nl = number of moles of the liquid;
k = Boltzmann constant;
T = temperature.

Applying the equation of continuity in a axisymmetric drop, making all replacements, one arrives at
the expression of drop height variation (h) with time, which is the equation of spreading a liquid
droplet on a solid:

h 1     h2   DS  P   (5.32)
 xh     
t x x 
  3   nlkT  x 

It is observed that the spreading is inversely proportional to the viscosity of the liquid () and
temperature T, is directly proportional to surface diffusion coefficient and the spreading potential
gradient (P / x).
If this approach could be applied to a reactive system and the potential for thermodynamic
quantities involving spreading, spreading potential would be a function of the spreading coefficient,
the pressure of the thermodynamic potential.

5.3) THE DEWETTING.

The dewetting is a phenomenon in which the wetting and spreading of liquid becomes unstable,
reverting them. This phenomenon can cause problems, as the case of dewetting soldered terminal
electronic components on printed circuit boards. Moreover, the process is very important as
nanoparts manufacturing process materials [105,106].
Thinking in terms of implementation of the sessile drop test, may occur for some surface
phenomenon, the droplet does not have the shape of a spherical cap. In this case it is important to
consider the drop of two views, front and top view. Usually the analysis is done only in the front
view, with the measure of equilibrium contact angle. It is important that the top view of the drop is
examined to see if wetting is occurring in the conventional manner. Figure 5.20 shows schematically
two views of the sessile drop test wetting and when dewetting occurs.
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WETTING DEWETTING

(a)
(b)
Figure
5.20 - Scheme front view and top of a drop spreading over a solid. In (a) when wetting occurs in a
stable manner. In (b) when there are areas of the drop that exhibit unstable behavior.

Figure (5.20.a) schematically shows the result of a drop wetting and spreading steadily. In this case
the angle  is constant around the entire perimeter of the droplet, as in the case of a spherical cap.
In the figure (5.20.b) drop presents a change of curvature. In this case, the region with angle 1 
present a contact angle reverse (greater than 90) in the front view, with a convex curvature. On the
other hand, the region with an angle 2 present  advance angle (less than 90), presenting a concave
curvature. The concave region is likely to continue spreading and the convex region tends to
contract. This behavior may be due to contamination on the solid surface or by precipitation of an
intermetallic phase which are not wetted by the liquid.
In the case of thin films of polymer materials with a thickness of less than 60 um, the dewetting has
two mechanisms: by spinodal and heterogeneous nucleation [105-107]. Figure 5.21 shows these
two dewetting mechanisms of thin film.
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Figure 5.21 - Thin film dewetting mechanisms of polymeric material. In (a) spinodal dewetting and
(b) dewetting second nucleation layer [106].
In the case of spinodal dewetting, the wavelength of surface disturbance (s) is related to the
second derivative of the surface potential () as a function of film thickness ((2/h2). The value of
s wavelength can be calculated by the equation 5:33 [106, 107]. For the occurrence of the spinodal
 2
dewetting must be less than zero. Thus, any disturbance on the surface ends up growing
h 2
until the spinodal dewetting is complete. In (5.20.a) it is important to note the scale on which the
phenomenon occurs. Moreover, this dewetting mechanism depends on the thickness of the thin
film.

 8 (5.33)
s (h) 
2
h2
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The dewetting by heterogeneous nucleation occurs when a second phase is not wet by the liquid.
In this case the contact angle is greater than 90 and, consequently, the contact angle is reverse. The
net ends up being expelled from the region is growing where the second phase, forming a hole in
the liquid film.

5.4) ADHESION WORK.

When a surface is created from a portion of a material it is necessary to perform work to break the
chemical bonds, as shown schematically in Figure 5.22.


 1-2



Figure 5.22 - Scheme of the formation of two surfaces per unit area. In (a) for a pure material, and
(b) to an interface between two different pure materials.

In the case of a single-phase material, this work is called 'cohesion work', given by the expression
5.34 and shown in the figure (5.22.a). If there are two different materials joined by a surface, the
work performed to separate this surface is called the 'work of adhesion' represented by the
equation shown in the figure and 5:35 (5.22.b).

W1cohesion
1   1   1  0  2 1 (5.34)

W1adhesion
2   1   2   12 (5.35)

From equation 5:35, surface energies and 1 2 may be related to the binding energy 11 and 22
within the material and the surface 12, using the interaction model between nearest neighbors.
Therefore, you should make some additional assumptions such as the solids are monatomic; They
are physical and chemically inert; has the same crystal lattice, the same atomic volume, the interface
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between the two is consistent, the contributions of entropy in surface tension is negligible [85].
Thus:
Zm1  11 (5.36)
1  
 2
Zm1  22
2  
 2
Zm1     22 
 12    12  11 
  2 
where:
 = atom surface area;
Z = number of nearest neighbors,
m1 = the number of chemical bonds broken by atom on the surface 1 or 2
i = binding energy, defined as negative values.

The work of adhesion on this model would be:

Zm1 (5.37)
W1adhesion   12

2

Dupre, in 1866 defined the work of adhesion between a solid and a liquid per unit area as reversible
work per unit area for separating solid from liquid, leaving a liquid film adsorbed onto the solid in
equilibrium with the vapor liquid. He proposed an equation, the equation of Young-Dupré, using
equations 3.7 and 5.35.

adhesion
WSLV   LV (1  cos  ) (5.38)

The equation 5:38 allows to make a correlation between the mechanical properties of tensile
strength of a junction between two materials and work of adhesion.

6) METHODS TO CALCULATE AND MEASURE THE LIQUID / VAPOR SURFACE TENSION.

This item will be presented theoretical calculation methods and experimental methods of
measurement of liquid surface tension / vapor.

6.1) THE LIQUID / VAPOR SURFACE TENSION CALCULATION .

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There are several methods to calculate the three types of surface tension [22,32,95,134-146]. In this
chapter the emphasis will be given to the liquid surface tension / vapor.
The surface tension liquid / vapor may be calculated in different ways from semi-empirical equations
and empirical [134,135], passing through the origin thermodynamic equations [134-143] by the
equations that use solid state physics [135-146] . Some of these methods are presented in this
document, divided on the application in pure metals, binary systems, and multicomponent systems.

6.1.1) PURE METALS.

In the case of pure metals, the surface tension of liquid / vapor may be expressed in various ways
[32,95,135]. One is based on the concept of critical temperature Tc [32], which is defined as the
temperature above which, for a given critical pressure (pc), there is no distinction between liquid
phase and gas phase. Consequently, as the temperature approaches the critical temperature, there
is more distinction between liquid and gas forming a supercritical fluid. The main characteristics of
a superfluid (supercritical fluid) are solid diffuses like a gas dissolved materials like a liquid and has
a surface tension equal to zero. As example, water has a critical temperature of approximately
374oC and critical pressure of 217.7 atm. Based on the concept of critical temperature in 1886
Eötvös, has developed the following equation to calculate the surface tension of pure substances
[32]:


d  (MV )2 / 3 
 kE
(6.1)
dT

By integrating the equation with lv = 0 to T = Tc is obtained:

kE T  Tc  (6.2)
 
MV 2 / 3

where:
kE = constant Eötvös;
Tc = critical temperature;
M = molar mass;
V = specific volume
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Later, van der Waals proposed in 1894, a relationship to calculate the surface tension due to the
critical temperature given by [32]:

n
 T  (6.3)
   0 1  
 Tc 

where:
0 = constant for each liquid and independent of temperature;
n = constant = 1.23 (for organic liquids).

The constant 0 is calculated by the expression:

 0  .Tc1 / 3 pc2 / 3 (6.4)

where:
 = universal constant of the liquid (which has small variations from liquid to liquid) = 2.1 ergs / K.

Comparing equations (6.2) and (6.3) gives the following value for the constant k E Eötvös:
n 1
 T  (6.5)
 0 1  
Tc 
kE  
Tc (MV )2 / 3

According Murr [32], in equation (6.5), the Eötvös constant entropy associated with the surface
interatomic forces (intermolecular) through 0, and the interatomic distance intermolecular)
through the average values MV2 / 3. Moreover, 0 is the surface free energy at 0 K temperature

6.1.2) Binary systems.

In the case of binary systems A-B, the surface tension of liquid / vapor can be calculated from
thermodynamic properties [96,141,142]. Butler [94], using the concept of Gibbs interface,
concluded that:
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RT  1  x B'  1  exc ' (6.9)

 LV  A  ln     G A ( T , x B' )  exc G A ( T , x B ) 
 A  1  x B 
 A 


RT  x B'  1  exc '

 B  ln     GB ( T , x B' )  exc GB ( T , x B )
B  x B  B 
 

where:
1 2
i = 1,091.N 3.V 3
=surface tension of component 'i';

i = surface area of the monolayer of the pure liquid component 'i' (N = Avogadro's number, V =
molar volume);
x B = Concentration of B within the bulk of the liquid;

x B' = concentration at the surface of the liquid;

'
exc Gi ( T , x B' ) = Partial molar free energy component of Gibbs 'i' in the T function in surface and

x B' ;

exc Gi ( T , x B ) = Free partial molar Gibbs energy component 'i' in the T function and x B .

The relationship between the free partial molar Gibbs energy component 'i' in function of T and x B

and free energy and partial molar component of Gibbs 'i' in function of T and x B' in surface and is

given by the relationship:

' Z sup exc (6.10)

exc G A ( T , x B' )   GA ( T, x B )
Z seio
where:
9 = Zsup = coordination number on the liquid surface assuming a similar arrangement to simple cubic;
12 = Zbulk =Coordination number within the liquid assuming a similar arrangement to the simple
cubic.

Another way to calculate the surface tension was proposed by Guggenheim [26,35,135] using the
regular solution model assuming the atoms randomly distributed and a  parameter, called the
energy exchange that takes into account the change in system power when AB pairs are formed
from AA and BB pairs, using the expression:
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    (6.11)
  ZN  AB  AA BB 
 2 
where:
Z = the average coordination number of the liquid;
N = Avogadro's number;
ij = peer interaction energy 'ij' atoms.

The equation for LV calculation becomes:

 LV   A 
RT  1  x B'
ln 
m  1  x B
  
 m2  ' 2 2
m 2
xB  xB  1 xB 
(6.12)
 m m
RT  x B'  m2 
B  ln   
m  x B  m
 m
(1  x B' ) 2  (1  x B ) 2  1 (1  x B ) 2
m

where:
 m = surface area of the monolayer of the pure liquid component "i" (which is equal to the
component 'j');
mi = constants defined in Figure 6.1

bonding
Z.m1

Bonding

bonding
Z.m1

Figure 6.1 - Definition of nearest neighbors in the same plane and in adjacent planes, for a material
with coordination number Z [135].

6.2) TESTS TO MEASURE THE LIQUID / VAPOR SURFACE TENSION.

There are several tests to measure the liquid surface tension / vapor [22,32,141]. This text focuses
only some trials, which are directly related to the subject developed. The assays can be divided into:
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tests which determine the surface tension of the droplet from the equilibrium shape and tests that
are based on other characteristics related to the liquid. In the first group are the trials of the sessile
drop and drop pendant. In the second group are testing the maximum pressure of the gas bubble
and the balance of Wilhelmy (wetting balance). These tests measure the static surface tension. The
dynamic surface tension can be measured by the test for determining the instability of an elliptical
fluid jet [22].

6.2.1) PENDANT DROPLET TEST.

The pendant droplet test is present in nature, just watch Figure 6.3, which shows a rain drop
hanging from a pine branch.

Figure 6.3 - Photo of a rain drop hanging from a pine branch (www.photos.com).

The principle of this test is the formation of a drop at the end of a small tube and the drop of the
geometry measures after equilibration. Figure 6.4 shows a test setup.

(a) (b) (c)

Figure 6.4 - the pendant drop test of the Scheme (a); the drop size (b) and a photo of a test of a drop
of water [22].
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The equation governing this test is:

1 1  2 (6.19)
 LV     gz  LV
 R1 R 2  b

where:
LV = liquid/vapor surface tension;
Ri = radius of curvature;
 = density difference;
g = acceleration due to gravity;
z = drop height;
b = radius of curvature at the apex drop.

Figure 6.5 - Drawing of the steps of the detachment a drop subject to weight force[141].

6.2.2) SESSILE DROPLET TEST.

The test of the sessile drop is also present in our day-to-day. Figure 6.6 shows a rain drop of water
on a leaf of a plant.

Figure 6.6 - Photo of a rain drop of water on a leaf of a plant (www.photos.com).

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The principle of this test consists of placing a drop on a solid substrate horizontally. The sessile name
means. "[From latim sessile = which is not supported.." [79]. In other words, the drop is not
supported at the side and can wet and spread freely. Figure 6.7 shows a test setup.

Figure 6.7 - sessile drop test Schema showing the coordinate axes [22].

This test is represented by the following equation:

:

1 1  2 (6.21)
 LV     gz  LV
 R1 R 2  b

where:
LV = liquid/vapor surface tension;
Ri = radius of curvature; = density difference;g = acceleration due to gravity;
z = drop height;
b = radius of curvature at the apex drop.

6.2.3) Wilhelmy balance test (wetting balance).

The Wilhelmy test to determine the surface tension of a liquid was proposed in 1863 [22, 32]. This
test consists of immersing a plate of a material in a liquid bath and measuring the weight of the
meniscus, from the time of immersion. Figure 6.11 shows a test setup.
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(a) (b)

Figure 6.11 - Wilhelmy test (or wetting balance) [22]. In (a) the meniscus reaching a height 'h'; in (b)
is an example for adding soft soldering using a flow [148].

This test is represented by the equation:

2 (6.23)
h gh2
   1  sen 
a 2 LV

Analyzing this equation, it is seen that the greater the height of the meniscus on the surface of the
plate, the lower the contact angle and hence the greater the weight of the meniscus.