gaber zeta potential

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Zeta Potential and particle size By Professor Mohamed H. Gaber

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Page 1: Gaber Zeta Potential

Zeta Potential and particle size

By

Professor Mohamed H. Gaber

Page 2: Gaber Zeta Potential

Origins of Surface Charge

1) Ionization of surface functional groups

Organic/molecular:

e.g. RCOOH <--> RCOO-, RNH2<--> RNH3+, etc

As in protein/peptide C-terminus, N-terminus,

certain side groups (aspartic acid, etc.)

Note: can be intrinsic to the particle and/or surface-

functionalized/derivatized (biotin, etc.)

Inorganic/ionic:

e.g. SiOH <> SiO-)

(For example, glass beads, hydroxyapatite)

2) Adsorption of charged species

Charged/ionizable molecules:

e.g. surfactants, phospholipids

(For example: SDS, constituents of DPPC)

Small ions:

e.g. Ca++, Mg++, etc.

(For example in certain physiological processes)

Page 3: Gaber Zeta Potential

Diffuse Layer:

Also called Electrical Double

Layer: Ionic concentration not the

same as in bulk; there is a gradient

in concentration of ions outward

from the particle until it matches

the bulk

Stern Layer: Rigid layer of ions

tightly bound to particle; ions travel

with the particle

Plane of hydrodynamic shear:

Also called Slipping Plane:

Boundary of the Stern layer:

ions beyond the shear plane do

not travel with the particle

Particle surface

Characteristics of Surface Charge: Definitions

Page 4: Gaber Zeta Potential

Characteristics of Surface Charge: Definitions

Zeta potential:

The electrical

potential that

exists at the

slipping plane

The magnitude of the zeta potential gives an indication of the

potential stability of the colloidal system

* If all the particles have a large zeta potential they will repel each other

and there is dispersion stability

* If the particles have low zeta potential values then there is no force to

prevent the particles coming together and there is dispersion instability

A dividing line between stable and unstable aqueous dispersions is

generally taken at +30 or -30mV

Page 5: Gaber Zeta Potential

Zeta Potential and Electrophoretic Mobility

In an applied electric field, charged particles travel

toward the electrode of opposite charge.

When attractive force of the electric field is balanced

by the viscous drag on the particle, the particle

travels with constant velocity.

UE = 2 z f(Ka)/3

= dielectric constant (of electrolyte)

= viscosity (of electrolyte)

f(Ka) = Henry’s function

= ~1.5

for particles >~ 200 nm and electrolyte ~> 1 x 10-3 M

= ~1.0

for smaller particles and/or dilute/non-aqueous dispersions

z = Zeta potential

+ - +

-

This velocity is the partlcle’s electrophoretic mobility, UE

Page 6: Gaber Zeta Potential

Determination of Zeta Potential

Measure the Electrophoretic Mobility, UE (and know viscosity, dielectric constant; and choose a Henry function)

Solve Smoluchowski/Huckel Equation for

Zeta Potential

Predominant Methods:

Laser Doppler Velocimetry

Phase Analysis Light Scattering (PALS)

Method for particles with lower mobilities

Page 7: Gaber Zeta Potential

Determination of Zeta Potential

Principles of PALS:

Similar to particle sizing by dynamic light scattering

I.e. what is measured is temporal fluctuations in intensity of light

scattered by the particles in the dispersion.

In light scattering, the fluctuations are related to

Brownian motion of particles.

In PALS for ZP, the fluctuations are related to the

movement of the particle in the applied field, i.e. to UE;

The ZP is then calculated from the UE that is

determined by the PALS measurement.

(As in light scattering, the instrument’s autocorrelator

and software take care of the data reduction.)

Page 8: Gaber Zeta Potential

Zeta Potential vs pH

pH dependency of ZP

is very important!

Remember, dispersion

stability (or

conversely, ability of

particles to approach

each other) is

determined by ZP, with

~ 30 mV being the

approximate cutoff.

[In this example, the dispersion is stable below pH ~4 and above pH ~7.5]

At ZP=0, net charge on particle is 0.

This is called the isoelectric point

Typical plot of Zeta Potential vs

pH.

Ze

ta P

ote

nti

al,

mV

pH

Page 9: Gaber Zeta Potential

Example: Zeta Potential Measurements

Particle diameter Zeta potential

At low values of

Zeta potential

(near pH 6), the

dispersion de-

stabilizes and

the particles

agglomerate

Optimizing a

process for

preparing human

serum albumin

nanoparticles

(from the assigned

paper, K.Langer et al.)

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