SURFACE ENERGY

RELAXATION
RECONSTRUCTION
CHEMICAL AND PHYSICAL ADSORPTION
FACETING
WULFF CONSTRUCTION
SINTERING VERSUS OSTWALD RIPENING
 MECHANISMS OF SINTERING

1. Solid-state diffusion
• Surface (low temperature)
• Volume (moderate temperatures – densification)
• Cross-boundary (high temperature)
2. Evaporation-condensation/dissolution-precipitation
3. Viscous flow
4. Dislocation creep
dn atoms transferred from flat surface to spherical particle of radius R
Atomic volume is Ω
 Change of volume, dV, of the particle is Ω dn

V=(4/3)π R3

From the definition of chemical potential:

From the definition of surface energy:

 The work per atom transferred (Δμ)

Combining with
A=4 π R2
Convex: R is +ve
Concave: R is -ve
(Young-Laplace Equation)

For arbitrarily curved surface with principal radii of curvature, R1and R2

Effect of curvature on vapor pressure

For spherical particle (Kelvin Equation)

 Effect of curvature on solubility

(Gibbs-Thompson Equation)
Ostwald Ripening
Agglomeration
STABILIZATION OF NANOPARTICLES IN SOLUTION

•Electrostatic Stabilization (Kinetically stable)

•Steric Stabilization (Thermodynamically stable)

 STABILIZATION OF NANOPARTICLES IN SOLUTION

•Electrostatic Stabilization (Kinetically stable)

Reasons for surface charge on a solid:

1. Preferential adsorption of ions
2. Dissociation of surface charged species
3. Isomorphic substitution of ions
4. Accumulation or depletion of electrons at the surface
5. Physical adsorption of charged species onto the surface
 STABILIZATION OF NANOPARTICLES IN SOLUTION

•Electrostatic Stabilization (Kinetically stable)

For a solid surface in a liquid medium:

Fixed surface electrical charge density or electrode potential develops:

Nernst equation

Eo:standard electrode potential when concentration of ions is unity ni:

valence state of the ions ai: activity of the ions (effective concentration)
activity depends on pressure, temperature, composition of mixture taken
as unity for a pure substance in condensed phases
Rg: Gas constant
T: temperature
F: Faraday’s constant
Surface potential of a solid varies with the concentration of ions in surrounding
solution and maybe positive or negative
 STABILIZATION OF NANOPARTICLES IN SOLUTION

•Electrostatic Stabilization (Kinetically stable)

Considering only oxide surfaces for now

Reasons for surface charge in oxides:

1. Preferential adsorption of ions (Charge determining
species – called co-ions or coions) e.g. protons or OH-
species
Concentration given by pH (pH = -log[H+])

2. Dissociation of surface charged species

 STABILIZATION OF NANOPARTICLES IN SOLUTION

•Electrostatic Stabilization (Kinetically stable)

Point of zero charge (p.z.c.) or Zero point charge (z.p.c.)

The concentration of charge determining ions (co-ions)
corresponding to a neutral or zero-charged surface)

When pH > pzc, surface is negatively charged (OH-groups)

When pH < pzc, surface is positively charged (H+groups)

 STABILIZATION OF NANOPARTICLES IN SOLUTION

•Electrostatic Stabilization (Kinetically stable)

Nernst equation in terms of pH and p.z.c.

So, surface charge density or surface potential can now be written as:

E=2.303 RgT[(p.z.c.) – pH]/F

Which at Room Temperature can be simplified as:

E~0.06[(p.z.c.) – pH]
Co-ions
Counter ions
Solvent molecules /shear plane
The distributions of both ions are mainly controlled by a combination of the
following forces:

(1) Coulombic force or electrostatic force

(2) Entropic force or dispersion

(3) Brownian motion

In the solution, there always exist both surface charge determining ions and
counter ions, which have charge opposite to that of the determining ions.
 In the Stern layer:
the electric potential drops linearly through the tightly bound
layer of solvent and counter ions

In Gouy layer:

where h ≥ H, which is the thickness of the Stern layer, is known as

the Debye--Huckel screening strength and is also used to describe the
thickness of double layer, and K is given by

where F is Faraday's constant, is the permittivity of vacuum, r , is the

dielectric constant of the solvent, and Ci and Zi are the concentration and
valence of the counter ions of type i.

Double layer thicknesses: ~ 10 nm

INTERACTION BETWEEN CURVED SURFACES
When S<<r
What is distance dependence for attraction between two molecules?

For molecules
DLVO – Derjaguin, Landau, Verwey and Overbeek

Assumptions of DLVO Theory

CONDITIONS FOR DLVO VALIDITY
LIMITATIONS OF ELECTROSTATIC STABILIZATION
STERIC STABILIZATION
POLYMERIC STABILIZATION

Thermodynamically stable
 ADVANTAGES OF STERIC STABILIZATION

(5) Produces narrow size distribution of nanoparticles since the adsorbed

polymer layer acts as a diffusion barrier and prevents growth of nuclei.
 Types of solvents

Aqueous
Non-Aqueous
(organic)

Protic– which can exchange protons

Methanol, ethanol

Aprotic– which cannot exchange protons

Benzene, Acetone
 Types of solvents

Good solvents – polymer expands to

reduce overall

Poor solvent – polymer coils up or

collapses to reduce overall
 Polymers

Solvable – which can interact with the

solvent (Soluble?)

Interaction depends on the polymer –

solvent system as well as on the
temperature

Non-solvable– not discussed as they

cannot be used for steric stabilization
How do we decide for a given system if a solvent is good or poor?

Temperature!!!!!

High T –“good” – polymer expands

Low T –“poor” – polymer coils up

So, what is called High T and low T?

Flory-Huggins Theta Temperature (or simply ‘Theta

temperature’)

At T = ,
Gibbs free energy does not change whether polymer expands or collapses
 Polymer –particle interactions

Typically, diblock polymers

Also, Non-adsorbing polymers –don’t help with stabilization

Chemical bonds – strong

Physical adsorption – weak
All other interactions – polymer –solvent or polymer-polymer are
ignored
Interactions between particles

Good solvent
Interactions between particles

Poor solvent
 SURFACE TENSION,
SUPERHYDROPHOBICITY AND
SUPERHYDROPHILICTY
Surface tension in liquids
 Contact angle

Hydrophobic and Hydrophilic surfaces

For larger particles, we can neglect the term

Young’s Equation
 The difference between r and a is the hysteresis

Force that will cause droplet to slide down

The smaller the difference between the two angles, the easier for the drop to slide
down  Self cleaning surfaces
Hierarchical structures for superhydrophobicity and superhydrophilicity
 Wenzel State

Consider situation (a)

(Wenzel’s
modification of
Young’s
Equation)
Combining with Eqn 2.14

Wenzel Equation

If surface is hydrophobic, then > 90. So, * will be more hydrophobic – superhydrophobic
If surface is hydrophilic, then < 90. So, * will be more hydrophilic – superhydrophilic
 Cassie-Baxter state

f1 and f2are the area fractions of the solid and vapor in contact with the liquid
and are the contact angles of the liquid with the solid and the vapor, respectively
Taking,
f1+ f 2= 1
(for the solid liquid interface)
= 180ofor the liquid-air interface (almost straight line)

Cassie-Baxter Equation
MELTING POINT OF NANOPARTICLES
 Assumption: Nanoparticle made of a pure element, is spherical,
isotropic and homogeneous
Chemical potential (free energy per mole) : expressed as series
expansion about melting point and pressure of bulk crystal, To and Po,
respectively

Gibbs-Duhem Relationship
S: entropy
n: no. of moles
: density
In the bulk, chemical potentials of solid and liquid are same at
melting point

Expanding and as in (A 2.1.1) and using (A2.1.2)

and neglecting higher order terms, the difference between the
two can be written as:
 Taking T and P to be the melting point and pressure
experienced by nanoparticles,

Also, at the melting point of the bulk crystal,

G  H  T0 S  0
where, L is the latent heat of fusion

We get,

Using, (A2.1.2), (A2.1.3), (A2.1.5) and (A2.1.6) and writing

PLand PSare pressures experienced by the nanoparticle in the liquid and solid state
POis the pressure experienced in the bulk
The difference in pressure, is given by the Laplace Equation as

=
The mass of the nanoparticle remains unchanged on melting

Then from (A2.1.7)

Where,