21/02/2011

Interface and colloidal science-Colloidal stability

Colloidal Stability
• Particles collide due to the Brownian motions (random) or convection or sedimentation.
• The rate of aggregation is in general determined by the frequency of collisions and the
probability of cohesion during collision.
• The probability of cohesion depends on the chemical interactions acting among the
particles.
• These interactions can be tuned to increase the colloidal stability.

BUT ….

Thermodynamics fights against us!

Thermodynamically the particles tend to aggregate

Interface and Colloidal Science 1

Stability of colloidal solutions- Ostwald ripening

In colloidal solutions a barrier of 15-25 kT is sufficient to give colloid stability (with a
Debye length > 20 nm)
However the system is not THERMODYNAMICALLY stable
Over time solid or liquid solutions change their inhomogeneous structure: over time
the emulsions may coarsen in size and small particles aggregate into larger ones.
This growth is called Oswald ripening

Larger crystals are more energetically favored than smaller crystals

Small crystals have a larger surface area to volume ratio than large crystals.
Molecules on the surface are energetically less stable than the ones already well
ordered and packed in the interior
MonteCarlo numerical simulation of the Ostwald ripening

An everyday example is the re-crystallization of water within ice cream which gives
old ice cream a gritty, crunchy texture.

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 21/02/2011

Interface and colloidal science-Surface modification

Surface modifications
The modification of the surface changes the surface properties

Higher contact angle lower wetting

Wetting effects play a major role in

microfluidics.
Application examples from daily life range from
diapers over ink jet printers to the never-dripping
outlet of a tea pot.

From University of Erlangen (D)

http://www.youtube.com/watch?v=agiTkQyD43M

Interface and Colloidal Science 3

Interface and colloidal science-Surface modification

Surface modifications Hydrophobic
Superhydrophobic coatings polymer

Increase of the contact angle

http://www.youtube.com/watch?v=riXp_Q-
fDv8&feature=player_detailpage http://wn.com/superhydrophobic
University of Missouri College of Engineering

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Stability of colloidal solutions-Effect of Polymers

Adding polymers to the colloidal suspension is a way to stabilize it.
Polymers can be adsorbed or chemically attached to the particle.

Limitations of charge stabilization

•Use of polar solvent
•Very sensible to addition of salt (high valency counter-ion)
•The suspension are only stabilize KINETICALLY (problems with high concentrations
or under shear

The addition of polymers can provide three different type of stabilization

•Steric stabilization: polymer is adsorbed or chemically attached to the surface of
the particle (particle repulsion)
•Depletion interactions: where non-adsorbing polymers in solution induce
attraction
•Bridging interactions: where adsorbing polymers induce particle attraction by
adsorbing to two particles at the same time

Interface and Colloidal Science 5

Introduction to polymer physics

• Macromolecules MW = 103 – 106 g/mol

• Repeat units

• 1 type: homopolymer

• A-A-A-A-A

• few types: copolymer

• A-B-B-A-B-B-B
monomer
• many types: e.g. proteins

• Sequence macromolecule

• Connectivity, topology: linear, branched, comb, star, ring,

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 21/02/2011

Introduction to polymer physics-Molecular weight

Due to the high Mw and the high number of chains all the properties a polymeric
material are expressed in term of averaged properties
Molar mass distribution
In the case of Mw the weighted averages can be taken with the weight fraction or the
mole fraction:
Mn: Number average molecular weight

N M 
 N i i


Mn  i
  i
M i   n i M i
N N

i
i i
i
i 

i

Can be determined by gel permeation chromatography or viscosimetry

Mw: Weight average molecular weight

N M i
2
i
Mn  i

N Mi
i i

Interface and Colloidal Science 7

Introduction to polymer physics-Molecular weight

• Polydispersity index
Mn / Mw=1 for monodisperse polymers

Example:
MW = 1000 (20%), MW = 10 000 (60 %), MW = 100 000 (20 %)

M n  0.2 1000  0.6 10000  0.2 100000  26200

M w  0.2 1000 2  0.6 10000 2  0.2 100000 2  78633

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Introduction to polymer physics-Polymer interactions

Entanglements and effect of the Mw on dynamic properties (viscosity)

Polymers can physically entangle. This property is Mw dependent.

Non-Newtonian
behaviour

Newtonian
behaviour

η  M for M  M c
η  M 3.4 for M  M c

Interface and Colloidal Science 9

Introduction to polymer physics- Radius of gyration

Radius of gyration
Structural property that describes the distribution of masses and give an
indication of the size of an object.
It is calculated as the root mean square distance of the objects' parts from its
center of gravity
N
 
 r  r 
For a polymer chain: 1
Rg2 
2
i m
N i 1

 1 N

rm 
N
r
i 1
i

For polymer chain with the same Mw

More expanded chain larger Rg
More coiled chain smaller Rg

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Introduction to polymer physics-Polymer solutions

In solution the conformation of the single polymer chain depends on the solvent.

Good solvent: the chain is more expanded and try

to maximize the number of contacts with the fluid.

Bad solvent the chain segments stay close to each

other and the polymer chain is packed to limit the
polymer-fluid contacts. In the limit of a very bad
solvent the polymer chain merely collapses to form a
hard sphere.

The radius of gyration scales with the number of polymer segments

R g  Nυ
For a good solvent n=3/5; For a bad solvent n=1/3; for q solvent n=1/3
Interface and Colloidal Science 11

Introduction to polymer physics-Polymer solutions

Ideal Chains
In bulk, polymers behave like ideal chains: the polymer chain can be
described as a random walk (no excluded volume). Any monomer interaction
is neglected.

N number of monomers
L: length of the monomer

The energy of the polymer is taken to be independent of its shape, which means
that at the thermodynamic equilibrium, all of its shape configurations are equally
likely to occur as the polymer fluctuates in time, according to the Maxwell-
Boltzmann distribution.
Average end-to-end distance and relation with the radius of gyration

2 R2
R  Nl R g2 
6
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 21/02/2011

Introduction to polymer physics-Polymer solutions

Theta (q) solvent, q temperature
In solution the polymer chain behaves like a real chain (with excluded volume
taken into account): self avoiding walk.

but ..
at the theta conditions the chain behaves like an ideal chain.
The polymer-solvent (positive or negative) and polymer-polymer interactions are
counterbalanced.
Each solvent has a specific temperature (theta) at which the polymer chain
behaves like an ideal chain.

Interface and Colloidal Science 13

Introduction to polymer physics-Polymer interactions

Polymer interactions and  parameter: Mixing polymers
The conformation of polymer chains in solution depends on their architecture and solvent
quality. Flory and Huggins developed a theory for the solubility of polymers that predicts the
free energy of mixing from the polymer and solvent volume fractions and the net solvent-
polymer interaction energy (the  (Flory) parameter).

 p 
ΔA m  k BTN  s ln s  ln  p  s p  
 rs rp 

The mixing depends on the

Negative entropic contribution
value of  parameter

i volume fraction
N number density of molecules
ri chain length

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Introduction to polymer physics-Polymer interactions

Polymer interactions and  parameter: Polymer at the interface

In a similar way we can define a Flory surface parameter s

 
 s   u2 s  u1s   u11  u22  k BT
1
 2 
uij: pairwise contact energy normally attractive (<0)

Adsorption occurs when s is

larger than a critical value that
takes into account the fact that
when the polymer is adsorbed
the total entropy of the system
(polymer+solvent) decrease
(penalty in the configurational
entropy)

Interface and Colloidal Science 15

Introduction to polymer physics-Polymer interactions

Copolymers and amphiphilic molecules
When the polymeric chain is formed by different monomeric species
Block copolymer: AAAABBBBBAAAA
Random copolymer: ABBBAABBABAAB
Alternating: ABABABABA

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Stability of colloidal solutions-Effect of Polymers

Steric stabilization: polymer is adsorbed or chemically attached to the surface of the
particle (particle repulsion)
Cover the colloidal particle with a dense polymer layer (typically adsorbed from solution).
Steep repulsion between particles
Polymers at surface may be adsorbed or depleted depending of the value of the surface
s parameter
If s > sc adsorption; If s < sc depletion

Adsorption isotherm  adsorbed amount per Polymer volume fraction () vs.
unit per surface vs. ceq (equilibrium distance from the surface (Z)
concentration of the polymer in solution)

Few mg/m2

Interface and Colloidal Science 17

Stability of colloidal solutions-Effect of Polymers

Steric stabilization
Polymers can be either chemically attached or physically adsorbed.
Constant polymer volume fraction j
L0

The polymer Concentration of the

concentration is D=2L0
polymer increases
doubble

Same concentration value

as initially in the gap

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Stability of colloidal solutions-Effect of Polymers

Steric stabilization

In a good solvent the local increase in polymer concentration carries a free energy
penalty and then a repulsion steric interaction between particles

The repulsion is felt as soon as D < 2L0 (D: surface separation; L0: unperturbed layer
thickness) and increases steeply as D< L0

An analytical expression for the steric interaction (Vster) says that it scales as the
squared of the surface coverage

Vster2

Importance of the high surface coverage of an effective stabilization

Van der Waals attractions still operate between colloidal particles but stability can be
achieved if they are weak at D≈L0

Interface and Colloidal Science 19

Stability of colloidal solutions-Effect of Polymers

Steric stabilization
PEO(Rg=13 nm) is adsorbed in onto mica surface

PEO: -(-CH2-CH2-O-)n-

Force much less:

Slow adjustment
Compression
of the polymer Compression after decompression
Repulsion D≈ 6Rg
conformation

The polymer
chains have to
be in a well
relaxed and
stable
conformation
(importance of
solvent and
temperature)

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Stability of colloidal solutions-Effect of Polymers

Steric stabiliser design
•High surface coverage 
•Strong adsorption (s > sc )
•Good solvent for stability of the chain ( < 0.5)
•Low free polymer concentration (Ceq≈ 0)

The adsorption needs to be at the plateau region of the isotherm

Low free polymer is to avoid depletion attraction

Copolymers usually more efficient then homopolymers

(A would absorb and B will stick out into the solution and provide steric
stabilization)

Interface and Colloidal Science 21

Stability of colloidal solutions-Effect of Polymers

Depletion Interactions: addition of free non-adsorbing polymer in solution
Polymer chains occupy a volume whose value depends on their conformation and they
interact with the colloidal particles as hard spheres (excluded volume).
In q solvent -> polymer coils can be approximated as a sphere of diameter 2L0
Polymer coils are excluded from a depletion layer of L0 thickness around each particle
When two particles approach to a separation less than 2L0, the depletion layer overlap
and the free volume for the polymer increase.
Due the polymer osmotic pressure an effective attraction results between the particles

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Stability of colloidal solutions-Effect of Polymers

Depletion Interactions

Vster-P

Vdep: depletion potential

x: rpol/rcolloid
r/d: particle separation/rcol

Smaller polymer narrow

attraction region

Depletion mechanism allows for switching on particle attractions in a very controlled

manner
Interface and Colloidal Science 23

Stability of colloidal solutions-Effect of Polymers

Bridging interactions: adsorbing polymers induce particle attraction by adsorbing to
two particles at the same time

At low  (surface coverage) a polymer chain may attach to more than one colloidal
particle.
This can lead to attraction
The bridging interactions can be used to maximize colloidal aggregation (polymeric
flocculants)

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