Chapter 2: Thermodynamics of the Interface

2.1 Surface energy and absorption

2.1.1 Surface energy

Surface: the plane between condensed

matter (solid or liquid) and a vapour phase
or vacuum.
Interface: the dividing plane between two
phases e.g. solid/vapour interface

= broken bond
Surface (interfacial) energy: the excess energy
at the surface (interface) of a material
compared to the bulk

Driving force for sintering = the reduction of total interfacial energy

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 α α
Interface phase

β
β
Ideal system Real system

The interface is represented as an abrupt dividing surface  between phases α and β.

Thermodynamically, the interface is 2-dimensional i.e. zero volume.
In reality, the change in chemical composition from α to β takes place over several atomic layers.

For any extensive thermodynamic property  U (or E), S, G, V etc.

area & curvature of the interface (2.1)

(an extensive property is proportional to the size of the system / amount of material in the system)
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If we consider an infinitesimal change dE in the internal energy at a surface:

(2.2)

E = surface internal energy (we assume that the effect of


S = surface entropy surface curvature is negligible)
i = chemical potential of component i
ni = no. of moles of component i at the surface
γ = surface energy
A = surface area

γ is the partial derivative of E with respect to A.

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Surface energy can also be expressed as the change in the total internal energy of the
system.

(2.3)

P = pressure
V = volume

 (2.4)

γ is the reversible work required to create a unit area of the surface.

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 The internal energy at a surface E is expressed as:

(2.5)

From this equation and equation (2.2):

ni
i = = number of moles of i
A (2.6)
per unit of surface area

i is called the surface excess

At constant T
γ can change with chemical composition at
the interface
Gibbs adsorption equation (Gibbs adsorption isotherm)
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 2.1.2 Surface energy and thermodynamic potential

The thermodynamic potential*  is defined as:

 = Landau (grand) potential (2.7)

F = Helmholtz free energy

F represents the reversible work in a system at const. temp, volume and chemical potential.

For bulk homogenous phases,

G = Gibbs free energy (2.8)

Therefore, and

*thermodynamic potential: a scalar function used to represent the thermodynamic state of a system. 6
The Landau potential  at the surface is expressed as:

(2.9)

(2.10)

Surface energy = work needed to create a unit surface area under const.
temp, volume and chemical potential.

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 2.1.3 Relative adsorption

Relative adsorption is defined as:

i(1)  relative adsorption of component i with respect to component 1

 Ci  Ci  Ci  no. of moles of component i in unit volume of 

i(1)  i  1   
  Ci  no. of moles of component i in unit volume of 
 C1  C1  C1  no. of moles of component 1 in unit volume of 
C1  no. of moles of component 1 in unit volume of 

is independent of the position of the dividing surface;

 :
i
(1)
is the plane where 1 = zero;
is the adsorption of i at the surface where the absorption of component 1 is zero.

F
For a single-component system,    f
A

For a multi-component system, γ is affected by the adsorption of all components except

component 1.
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For monolayer adsorption at a solid/vapour or solid/liquid interface:

i(1)  relative adsorption of component i with respect to component 1

X i( m )  mole fraction of component i in the monolayer
X 1( m )  mole fraction of component 1 in the monolayer
X i  mole fraction of component i in 
X 1  mole fraction of component 1 in 

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What does all this mean?

B B

A-B
In systems with  2 components, the
A
components will distribute in a way that A
minimizes .

dγ
B   Gibbs adsorption isotherm
RTd ln c B

B = surface excess of component B

 = surface energy
cB = bulk concentration of component B

If addition of B causes  to decrease, B will B has a low surface tension

concentrate in surface layer e.g. SiO2 layer on Si.

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2.2 Surface tension and surface energy

• Capillary forces are surface forces exerted

by the external and internal surfaces of
condensed phases.
• Capillary forces direct much of
microstructural development

A force is required to extend a liquid surface due to attractive forces between the
atoms at the surface (surface tension)*.

A disturbed surface will move towards its centre of curvature.

*the terms “surface tension” and “surface energy” are often used synonymously, but they are not always the
same.
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Consider a liquid film attached to a moveable wire. To extend the film area, work
must be done.
The film has two sides.

(2.13)

W = work done by the extension

xx = surface tension (force used per unit
length of wire to extend the film
area). Units: N/m
l = length of wire
dx = increase in length of liquid film

The atom density at the film surface does not change – atoms in the liquid have high mobility
so can easily move from the bulk to the surface.

Due to const. surface atom density: E  A  2ldx (2.14)

The surface tension acts as a force to

oppose the increase in area. E = increase in total surface
energy due to surface area increase
For liquids: surface tension  surface energy A = increase in area
γ = surface energy. Units: J/m2
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Surface tension in a liquid is determined by the atom arrangement at the surface.

In a liquid, interatomic distance at surface > bulk interatomic distance.

• A –ve pressure parallel to the surface is

exerted, causing surface tension.
• Stress perpendicular to surface = zero
• Liquid surface is in state of plane stress.

For a liquid, yy = xx

In general, =(xx + yy)/2 = surface tension of any surface

yy = surface tension in y-direction

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For liquids: increase in surface area happens by atom supply from bulk;
surface atom arrangement does not change as surface area increases;
atom arrangement is isotropic;
 does not change with area.

For solids: increase in surface area happens by atom supply from bulk and by
increase in interatomic distance at the surface;
surface atom arrangement can change as surface area increases;
 can change with area.

γ

For solids,  = γ when surface atom arrangement is independent of external stress.

This condition is satisfied when atom mobility is high.

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Relationship between  and γ

ij = surface tension

ij = Kronecker delta (ij = 1 for i = j, ij = 0 for i  j)
γ = surface energy
εij = strain per unit length

If γ/εij = zero in a reasonable time span, then surface tension  surface energy.

For sintering at T > 2/3  TH, atom mobility is high enough to allow this.

TH = homologous temp = T/Tm

For metals and ceramics γ ~ 1 J/m2

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 Surface energy anisotropy

For liquids: For solids:

(José Manuel Suárez)

(T.R. Padden)

• γ does not change with • γ can change with

orientation of the orientation of the surface
surface • γ can be anisotropic
• γ is isotropic • Solid particles can have a
• Liquid droplets have a faceted shape
spherical shape • facets are crystallographic
planes with lowest values of γ.
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2.1 Thermodynamics of curved interfaces

Pressure difference across a curved surface Phase β

Phase α
If V (total volume), T and i are const., then an
infinitesimal movement of the interface causes
no change in . Interface

Since dV=0, dVβ = -dVα, therefore:

r1, r2 = perpendicular
radii of curvature
K : average curvature of the interface

For a sphere:

N.B. pressure inside a phase with a convex surface

Young-Laplace equation
> pressure outside
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 Alternate derivation of Young-Laplace equation

Consider the pressure required to blow a

spherical bubble in a liquid.

The work of expanding the spherical surface Pdv

equals the increase in surface energy γdA.

Pdv = γdA P = pressure difference across

curved surface

For a sphere of radius r:

r
dv = 4r2dr dA = 8rdr
bubble If r is equal,
then P is
8rdr equal.
 dA 2
P       
dv 4r 2 dr r r
water drop
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Atom activity at curved surfaces

Phase α Phase β
For a single component system (e.g. water/steam),
with α and β phases in equilibrium:

Interface
α (T, Pα) = β (T, Pβ) = α (T, Pβ + γK)

For an incompressible α phase:

 Taylor series expansion

Vm  molar volume of 

Rearranging the above equations gives:

α (T, Pβ) - β (T, Pβ) + γK Vm = 0

 r = chemical potential of curved
which can be expressed as:
surface of phase α
  = chemical potential of planar
surface of phase α
Gibbs-Thompson equation 19
 N.B. Gibbs-Thompson eqn. correct only when the effect of the interface is
exerted solely on the α phase i.e. the interface belongs only to the α phase.

 r  

If the Gibbs-Thompson eqn. is expressed in terms of atom activity:

ar = atom activity at curved surface

a = atom activity at planar surface

If

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 Application to sintering
For a single component system with α and β phases in equilibrium, for an
infinitesimal and reversible change between α and β phases at const. temperature:
 (2.26) dG = -SdT + Vdp

and (2.27)

Since Pα - Pβ = γK, by integrating Eqn. (2.27) from 0 to K and from P0 to Pβ we get:

P0 =P =
and pressure at
planar interface

If α = condensed phase (solid, liquid) and β is a gas following ideal gas law, then:

and pβ p p

because .
pβ = vapour pressure of α phase (system is single component)
p = vapour pressure of α phase above planar interface
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 -ve r

+ve r

If local equilibrium is maintained:

Region I  positive r  high P in region I and high p above region I

Region II  negative r  low P in region II and low p above region II

For vacancies (dispersed phase of vacuum), Region I has negative r and Region II has
positive r. Therefore equilibrium vacancy conc. in Region II > Region I.
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Thermodynamic driving force for sintering = the reduction of total interfacial energy

Sintering kinetics (material transport) is induced by the differences in

bulk pressure
due to interface
vapour pressure
curvature
vacancy concentration

All three differences operate simultaneously and independently.

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Energy change due to a curved interface

We have assumed that: no energy change in condensed phase due to capillary pressure
condensed phase is incompressible (V does not change with Pα)

But condensed phases are compressible and energy increases with capillary pressure.

The energy increase by deformation of a condensed phase of 1 mole:

Vm = molar volume
κ = compressibility
W is negligible compared with total surface energy for powders > nanometer size.
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